METHODS FOR PREPARING FLUOROALKYL ARYLSULFINYL COMPOUNDS
AND FLUORINATED COMPOUNDS THERETO
TECHNICAL FIELD
[0001] The invention relates to preparative method for fluoroalkyl arylsulfinyl
compounds and to useful fluorinated compounds thereto.
BACKGROUND OF THE INVENTION
[0002] Fluorine-containing compounds have found wide use in medical, agricultural,
and electronic materials as well as in other like industries [see Chemical & Engineering
News, June 5, pp. 15-32 (2006); Angew. Chem. Ind. Ed., Vol. 39, pp. 4216-4235 (2000)].
These compounds show specific biologic activity or physical properties based on the
presence of one or more fluorine atoms. A particular drawback in their usefulness is the
scarcity of natural fluorine-containing compounds, requiring most such compounds to be
prepared through organic synthesis. Therefore, there has been extensive study and research
on synthetic methodologies for the preparation of fluorine-containing compounds [see, for
example, Chem, Rev., Vol. 108, pp. PR1-PR43 (2008); Chem. Rev., Vol. 105, pp. 827-856
(2005); Tetrahedron, Vol. 52, pp. 8619-8683 (1996); Chem. Rev., Vol. 92, pp. 505-519
(1992)].
[0003] Examples of widely known methods of preparation of fluorine-containing
compounds include a method of direct fluorination with fluorine gas (F2); halogen exchange
reaction by action of hydrogen fluoride (HF) or an alkali metal salt of fluorine such as KF;
Schiemann reaction in which an aryldiazonium tetrafluoroborate derived from an arylamine
is tranformed to an aryl fluoride; a method using a mixture of HF and a base such as pyridine
or triethylamine; a method using an interhalogen fluoride or a hypervalent fluoride such as
ClF, BrF, IF, XeF2, BrF3, IF5, and ArIF2; a method using a specific nucleophilic fluorinating
agent such as SF4, DAST, DeoxoFluor™ reagent; FAR (fluoroalkylamino reagent) such as
Yarovenko-Raksha reagent, Ishikawa reagent, 2,2-difluoro-l,3-dimethylimidazolidine, N,N-
diethyl-a,a-difluoro-(m-methylbenzyl)amine, and N,N-dimethyl-1,1,2-trifluoroethylamine; a
method using a specific electrophilic fluorinating agent such as N-fluoropyridinium salts, N-
chloromethyl-N-fluorodiazoniabicyclo[2.2.2]octane salt, and N-
fluorobis(phenylsulfonyl)amide; and a method of electrolytic fluorination [see, for example,
Chem. Rev., Vol. 92, pp. 505-519 (1992); Chem. Rev., Vol. 86, pp. 997-1018 (1986);
Chemistry and Industry, Vol. 21, pp. 56-63 (January 1978); Israel Journal of Chemistry, Vol.
17, pp. 71-79 (1978); Organic Reactions, Vol. 5, pp.193-228 (1968); J. Fluorine Chem., Vol.
109, pp. 25-31 (2001); Chem. Rev., Vol. 96, pp. 1737-1755 (1996)].
[0004] However, conventional methods that utilize F2, HF, SF4, and DAST have
safety problems because of their highly toxic, corrosive, or explosive nature. In addition,
Deoxo-Fluor™ reagent has low thermal stability. The method using a mixture of HF and a
base usually requires a large excess of the mixture to obtain a high yield. The FAR reagents
have low reactivity, so the scope of their application is narrow. Methods using an
electrophilic fluorinating agent are limited to the fluorination of a nucleophilic substrate such
as a carbanion, an electron-rich aromatic compound, and a trimethylsilyl enol ether. The
electrolytic fluorination is also limited to a specific substrate because selectivity is low in the
fluorination.
[0005] Examples of methods of fluorinating a diol or an amino alcohol include
fluorination with DAST, Deoxo-Fluor™ reagent, N,N-diethyl-a,a-difluoro-(m-
methylbenzyl)amine, or acyclic acetal of N,N-diethyl-4-methoxybenzamide [J. Org. Chem.,
Vol. 40, pp. 574-578 (1975); J. Fluorine Chem., Vol. 125, pp.1869-1872 (2004); Chem.
Commun., 2005, pp. 3589-3590; Synlett, 2006 (11), pp. 1744-1746; J. Fluorine Chem., Vol.
128, pp.1121-1125 (2007)]. The fluorination of a diol or an amino alcohol with DAST or
Deoxo-Fluor™ reagent produces a corresponding or rearranged difluoro compound. The
fluorination of a diol or an amino alcohol with N,N-diethyl-a,a-difluoro-(m-
methylbenzyl)amine or a cyclic acetal of N,N-diethyl-4-methoxybenzamide produces a
fluoroalkyl arylcarboxylate or a fluoroalkyl arylamide. The fluoroalkyl arylcarboxylate or
arylamide is derived to a fluoro alcohol or a fluoro amine.
[0006] However, DAST and Deoxo-Fluor™ reagent have the same problems as
described above. N,N-Diethyl-a,a-difluoro-(m-methylbenzyl)amine and a cyclic acetal of
N,N-diethyl-4-methoxybenzamide require microwave irradiation or high reaction temperature
because of low reactivity.
[0007] From an alternative point of view, there are basically two methodologies to
prepare a fluoro organic compound: (1) a fluorination methodology includes an available
non-fluoro compound fluorinated with a fluorinating agent to produce a desired fluoro
compound, or the fluorination is conducted at the final or almost final stage in the preparation
processes to give a desired fluoro compound; and (2) a fluorinated building block (fluorinated
synthon) methodology where a desired fluoro compound is constructed by multi-step
preparation processes starting from a fiuorinated building block (a fluorinated synthon), " a
fluorinated molecule possessing a reactive site" [see, for example, Chemical & Engineering
News, June 5, pp.15-32 (2006): Fluorine-containing Synthons; ed by V.V. Soloshonok; ACS
Symposium Series 911, American Chemical Society, Washington, DC, 2005, pp. 119-134].
Thus, new developments of useful fluorination techniques, fluorinated intermediate
compounds (fluorinated building blocks), and synthetic methods using the fluorinated
intermediates are particularly important for synthesizing desired fluoro organic compounds
which possess a fluorine atom(s) at a specific position in a stereo structure. The position and
stereo chemistry of a fluorine atom in a molecule is very important for appropriate biologic
and/or physical activity.
[0008] However, there are still many problems in conventional methodologies, for
example, selectivity in fluorination is not sufficient, so regio and/or stereo isomeric fluoro
compounds are produced, which are difficult to separate/isolate; also, there is a lack of safe,
ease-to-handling, cost-effectiveness, and selectivity for preparing a desired fluoro compound;
and many preparative steps are required to prepare a desired fluoro product due to the lack of
suitable fluorinated intermediates or building blocks (fluorinated synthons), so total yield is
low.
[0009] Therefore, problems with the production methods for fluoro organic
compounds have made it difficult to prepare fluoro materials in which a fluorine atom is
located in a correct position and stereo chemistry, especially in a safe, cost effective and
timely fashion.
[0010] The present invention is directed toward overcoming one or more of the
problems discussed above.
SUMMARY OF THE INVENTION
[0011] The present invention provides a new and useful method for preparing a
fluoroalkyl arylsulfinyl compound having a formula (I):

by reacting an oxygen-containing compound having a formula (II) with arylsulfur
trifluoride having a formula (HI):

[0012] Embodiments of the present invention also include methods wherein the
arylsulfur trifhioride of formula (HI) is prepared by a method comprising reacting arylsulfur
halotetrafluoride of formula (IV) with a reducing substance.

[0013] The present invention also provides a useful method(s) for preparing a
fluoroalkyl arylsulfinyl compound having a formula (I) by reacting an oxygen-containing
compound having a formula (II) with arylsulfur halotetrafluoride having a formula (IV) in
the presence of a reducing substance.
[0014] The present invention also provides novel fluoroalkyl arylsulfinyl compounds
of formulas (Ia), (Ib), (Ic), and (Id):

[0015] In addition, the present invention provides useful methods for preparing
fluoroalkyl arylsulfinyl compounds of formulas (Ie) and (If).

[0016] These and various other features as well as advantages which characterize
embodiments of the invention will be apparent from a reading of the following detailed
description and a review of the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The invention provides novel processes for preparing fluoroalkyl arylsulfinyl
compounds, as well as provides useful fluoroalkyl sulfinyl compounds thereto.
[0018] The present invention provides a method (Scheme 1, Process I) for preparing a
fluoroalkyl arylsulfinyl compound having a formula (I), which comprises reacting an oxygen-
containing compound having a formula (II) with an arylsulfur trifluoride having a formula
(III):
Scheme 1, Process I

in which:
R1, R2, R3, and R4 each is independently a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, a
substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, preferably 2 to
14 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon
atoms, preferably 2 to 14 carbon atoms, a substituted or unsubstituted aryl group having 6
to 20 carbon atoms, preferably 6 to 14 carbon atoms, a substituted or unsubstituted
heterocyclyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy
group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, a substituted or
unsubstituted acyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, a
substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms,
preferably 2 to 14 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group
having 7 to 20 carbon atoms, preferably 7 to 14 carbon atoms, a substituted or
unsubstituted (heterocyclyl)oxycarbonyl group having 2 to 20 carbon atoms, preferably 2
to 14 carbon atoms, or a cyano group;
Ra, Rb, Rc, Rd, and Re each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 4
carbon atoms, a nitro group, or a cyano group;
A is an oxygen atom or NR5 in which R5 is a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, a
substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 14
carbon atoms, a substituted or unsubstituted heterocyclyl group having 1 to 20 carbon
atoms, preferably 1 to 14 carbon atoms, a substituted or unsubstituted acyl group having
1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, a substituted or unsubstituted
alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or unsubstituted
aryloxycarbonyl group having 7 to 20 carbon atoms, preferably 7 to 14 carbon atoms, a
substituted or unsubstituted (heterocyclyl)oxycarbonyl group having 2 to 20 carbon
atoms, preferably 2 to 14 carbon atoms, a substituted or unsubstituted alkylsulfonyl group
having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, a substituted or
unsubstituted arylsulfonyl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon
atoms, a substituted or unsubstituted (heterocyclyl)sulfonyl group having 1 to 20 carbon
atoms, preferably 1 to 14 carbon atoms, or a R14R15R16Si group in which R14, R15, and R16
each is independently an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4
carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to
10 carbon atoms;

in which:
R6, R7, R8, R9, R10, R11, R12 and R13 each is independently a hydrogen atom, a
halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
preferably 1 to 14 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to
20 carbon atoms, preferably 2 to 14 carbon atoms, a substituted or unsubstituted alkynyl
group having 2 to 20 carbon atoms, preferably 2 to 14 carbon atoms, a substituted or
unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms, a
substituted or unsubstituted heterocyclyl group having 1 to 20 carbon atoms, preferably 1
to 14 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon
atoms, preferably 1 to 14 carbon atoms, a substituted or unsubstituted aryloxy group
having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms, a substituted or
unsubstituted (heterocyclyl)oxy group having 1 to 20 carbon atoms, preferably 1 to 14
carbon atoms, a substituted or unsubstituted acyl group having 1 to 20 carbon atoms,
preferably 1 to 14 carbon atoms, a substituted or unsubstituted acyloxy group having 1 to
20 carbon atoms, preferably 1 to 14 carbon atoms, a substituted or unsubstituted
alkoxycarbonyl group having 2 to 20 carbon atoms, preferably 2 to 14 carbon atoms, a
substituted or unsubstituted aryloxycarbonyl group having 7 to 20 carbon atoms,
preferably 7 to 14 carbon atoms, a substituted or unsubstituted (heterocyclyl)oxycarbonyl
group having 2 to 20 carbon atoms, preferably 2 to 14 carbon atoms, a substituted or
unsubstituted amino group having 20 or less carbon atoms, preferably 14 or less carbon
atoms, a substituted or unsubstituted carbamoyl group having 1 to 20 carbon atoms,
preferably 1 to 14 carbon atoms, a substituted or unsubstituted alkylthio group having 1
to 20 carbon atoms, preferably 1 to 14 carbon atoms, a substituted or unsubstituted
arylthio group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms, a
substituted or unsubstituted (heterocyclyl)thio group having 1 to 20 carbon atoms,
preferably 1 to 14 carbon atoms, a substituted or unsubstituted alkylsulfinyl group having
1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, a substituted or unsubstituted
arylsulfinyl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms, a
substituted or unsubstituted (heterocyclyl)sulfinyl group having 1 to 20 carbon atoms,
preferably 1 to 14 carbon atoms, a substituted or unsubstituted alkylsulfonyl group
having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, or a substituted or
unsubstituted arylsulfonyl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon
atoms, a substituted or unsubstituted (heterocyclyl)sulfonyl group having 1 to 20 carbon
atoms, preferably 1 to 14 carbon atoms, a nitro group, or a cyano group;
h, i, and j each is independently 0 or 1;
Rx and Ry each is independently a hydrogen atom, a silyl group, a metal atom, an
ammonium moiety, or a phosphonium moiety, or Rx and Ry combine to form a metal
atom or a silyl group; and
two or more of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11, or two or more of R1,
R2, R3, R4, R5, R12, and R13 may be linked with or without a heteroatom(s) to form any
ring structure.
[0019] A halogen atom herein is a fluorine atom, a chlorine atom, a bromine atom, or
an iodine atom.
[0020] The silyl group(s) for Rx and/or Ry above can include a R14' R15' R16' Si group
and other like silyl groups, in which R14', R15', and R16' each is independently an alkyl group
having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, an aralkyl group having 7 to 10
carbon atoms, or an aryl group having 6 to 10 carbon atoms. The silyl group that Rx and Ry
combine to form can include a -Si(R17)(R18)- group and other like silyl groups, in which R17
and R18 each is independently an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4
carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10
carbon atoms.
[0021] The metal atom(s) above can include an alkali metal atom, alkali earth metal
atom, and/or transition metal atom. Among them, alkali metal atoms such as Li, Na, K, Rb,
and Cs are preferable. Preferably when Rx and Ry combine to form a metal atom an alkali
earth or transition metal atom such as Mg, Ca, Cu, and Zn atom is used.
[0022] The ammonium moieties above can include tetraalkylammonium such as
tetramethylammonium, tetraethylammonium, tetrabutylammonium, and so on. The
phosphonium moieties above can include tetraalkylphosphonium such as
tetramethylphosphonium, tetraethylphosphonium, and so on, and tetraarylphosphonium such
as tetraphenylphosphonium, tetra(tolyl)phosphonium, and so on.
[0023] The term "alkyl" as used herein refers to a linear, branched, or cyclic alkyl.
The alkyl part of alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl, or alkylsulfonyl group as
used herein also refers to a linear, branched, or cyclic alkyl part. When an acyl or acyloxy
group contains an alkyl part, the alkyl part is also linear, branched, or cyclic.
[0024] The term "substituted" as used in, for example, "substituted alkyl",
"substituted alkenyl", "substituted alkynyl", "substituted aryl", "substituted heterocycly",
"substituted acyl", "substituted alkoxycarbonyl", "substituted aryloxycarbonyl", "substituted
(heterocyclyl)oxycarbonyl", "substituted alkoxy", "substituted aryloxy", "substituted
(heterocyclyl)oxy", "substituted acyloxy", "substituted amino", "substituted carbamoyl",
"substituted alkylthio", "substituted arylthio", "substituted (heterocyclyl)thio", "substituted
alkylsulfinyl", "substituted arylsulfinyl", "substituted (heterocyclyl)sulfinyl", "substituted
alkylsulfonyl", "substituted arylsulfonyl", and "substituted (heterocyclyl)sulfonyl" herein
means each basic moiety (alkyl, alkenyl, alkynyl, etc.) having one or more substituents such
as a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted
alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl
group, a substituted or unsubstituted heterocyclyl group, and/or any other group with or
without a heteroatom(s) such as an oxygen atom(s), a nitrogen atom(s), and/or a sulfur
atom(s), wherein the substitution does not substantially limit reactions of this invention.
[0025] The term "heterocyclyl group" or "heterocyclyl" as used herein refers to
univalent groups formed by removing a hydrogen atom from any ring atom of a heterocyclic
compound which includes saturated as well as unsaturated heterocyclic compounds [see,
Glossary of class names of organic compounds and reactive intermediates based on structure
(IUPAC Recommendations 1995); Pure & Appl. Chem., Vol. 67 (Nos 8/9), pp 1307-1375
(1995)], incorporated herein by reference.
Process I
[0026] The starting materials, i.e., oxygen-containing compounds having formula (II),
are commercially available or can be prepared in accordance with understood principles of
synthetic chemistry.
[0027] Illustrative oxygen-containing compounds of Process I, as presented by
formula (II), include: diols, amino alcohols, silyl derivatives of diols and amino alcohols, and
metal, ammonium, or phosphonium salts of diols and amino alcohols. These oxygen-
containing compounds used for Process I include any stereoisomers such as diastereoisomers,
enantioisomers, and racemates. Illustrative diols and their salts include, but are not limited to:
ethylene glycol (1,2-ethanediol), LiOCH2CH2OH, NaOCH2CH2OH, KOCH2CH2OH,
LiOCH2CH2OIi, NaOCH2CH2ONa, KOCH2CH2OK, (CH3)4NOCH2CH2OH,
(C4H9)4NOCH2CH2OH, (C6H5)4POCH2CH2OH, 1,2-propanediol, LiOCH2CH(OLi)CH3, 1,3-
propanediol, LiOCH2CH2CH2OLi, NaOCH2CH2CH2ONa,
(C4H9)4NOCH2CH2CH2ON(C4H9)4, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-
butanediol, 1,2-pentanediol, 1,3-pentandiol, 1,4-pentanediol, 1,5-pentanediol, 2,3-
pentanediol, 2,4-pentanediol, 3-pentene-1,2-diol, 4-pentene-1,2-diol, 1,2-hexanediol, 1,2-
heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1,2-
dodecanediol, 1,2-pentadecanediol, 1,2-hexadecanediol, 1,2-icosanediol, 1,2-docosanediol, 1-
(cyclopropyl)-1,2-ethanediol, 1 -(cyclopentyl)-1,2-ethanediol, 1 -(cyclohexyl)-1,2-ethanediol,
1-phenyl-1,2-ethanediol, 1,2-diphenyl- 1,2-ethanediol, 1 -(a- or ß-naphthyl)- 1,2-ethanediol, 1-
(a-, ß- or ?-pyridyl)-1,2-ethanediol, 1-(a- or (5-furyl)-1,2-ethanediol, 1-(a- or ß-thienyl)-1,2-
ethanediol, 1-(a- or ß-pyrrolyl)-1,2-ethanediol, N-benzyl-2-(l',2'-dihydroxyethyl)pyrrole, 1-
(2'-quinolyl)-1,2-ethanediol, 3,4-epoxy-1,2-butandiol [(l',2'-dihydroxylethyl)oxirane], 2-
(1',2'-dihydroxyethyl)aziridine, 2-( 1',2'-dihydroxyethyl)azetidine, 1 -(imidazol-2'-yl)-1,2-
ethanediol, 1-(1'-methylimidazol-2'-yl)-1,2-ethanediol, 1-( oxazol-2'-yl)-1,2-ethanediol, 1-
(thiazol-2'-yl)-1,2-ethanediol, 1-(2'-, 4'-, or 5'-pyrimidyl)-1,2-ethanediol, 1-(2'-, 3'-, or 4'-
piperidinyl)-1,2-ethanediol, 1-(2'- or 3'-pyrrolidinyl)-1,2-ethanediol, 1-(2'- or 3'-
tetrahydrofuryl)- 1,2-ethanediol, 1-(2'- or 3'-tetrahydrothienyl)-1,2-ethanediol, 1-(2'-, 3'-, or
4'-tetrahydropyranyl)-1,2-ethanediol, 1-(2'-, 3'-, or 4'-tetrahydrothiopyranyl)-1,2-ethanediol,
1-(2'- or 3'-morpholinyl)-1,2-ethanediol, 1-(2'-decahydroquinolinyl)-1,2-ethanediol, 1-
phenyl-1,2-propanediol, 3-chloro-1,2-propanediol, 3-phenyl-1,2-propanediol, 3-methoxy-1,2-
propanediol, 3-benzyloxy-1,2-propanediol, 3-phenoxy-1,2-propanediol, 3-acetyloxy-1,2-
propanediol, 3-methylthio-1,2-propanediol, 3-phenylthio-1,2-propanediol, 3-methylsulfinyl-
1,2-propanediol, 3-phenylsulfinyl-1,2-propanediol, 3-methylsulfonyl-1,2-propanediol, 3-
phenylsulfonyl-1,2-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-
cyclopentyl-l,3-propanediol, 2-allyl-1,3-propanediol, 2-phenyl-1,3-propanediol, 2-methoxy-
1,3-propanediol, 2-benzyloxy-1,3-propanediol, 2-phenoxy-l,3-propanediol, 2-chloro-l,3-
propanediol, 2-cyano-1,3-propanediol, 2-vinyl-1,3-propanediol, 2-ethynyl-1,3-propanediol,
2-bromo-2-nitro-1,3-propanediol, 2-methylthio-1,3-propanediol, 2-phenylthio-1,3-
propanediol, 2-phenylsulfinyl-1,3-propanediol, 2-phenylsulfonyl-1,3-propanediol, 2-(2'-
tetrahydrofuranyl)-1,3-propanediol, methyl 2,3-dihydoxypropanoate, ethyl 2,3-
dihydroxybutanoate, dimethyl tartrate, di-tert-butyl tartrate, 2,3-dihydroxypropionitrile, 1,2-
cyclopentanediol, 1,3-cyclopentanediol, 1,2-dihydroxy-4-cyclopentene, 1,2-cylcohexanediol,
1,3-cyclohexanediol, 1,4-cyclohexanediol, 1-phenylcyclohexane-1,2-diol, 2-cyclohexene-l,4-
diol, 3-cyclohexene-1,2-diol, 4-cyclohexene-1,2-diol, 1,2-cycloheptanediol, 1,3-
cycloheptanediol, 1,4-cycloheptanediol, 1,2-cyclooctanediol, 1,4-cyclooctanediol, 1,2-
cyclononanediol, 1,2-cyclodecanediol, 1,2-cycloundenanediol, 1,2-cyclododecanediol, 3,4-
dihydroxy-1-butene, l,4-dihydroxy-2-butene, 3,4-dihydroxy-l-butyne, 1,2-dihydroxy-4-
phenyl-3-betene, 1,2-dihydroxy-4-pentene, 3,5-dihydroxy-l-pentene, 1,2-dihydroxy-4-
methyl-3-pentene, 1,2-dihydroxy-4-phenyl-3-pentene, 3,6-dihydroxy-l-hexene, 3,7-
dihydroxy-1 -heptene, 1,2-dihydroxy-1 -vinyl-cyclopentane, 1,2-dihydroxy-1 -vinyl-
cyclohexane, 1,2-bis(hydroxymethyl)benzene, N-(tert-butoxycarbonyl)-3-hydroxy-4-
(hydroxymethyl)pyrrolidine, N-(benzyloxycarbonyl)-3-hydroxy-4-
(hydroxymethyl)pyrrolidine, N-(9-fluorenylmethyl)-3-hydroxy-4-
(hydroxymethyl)pyrrolidine, cis-1,2-dihydro-1,2-naphthalenediol, 1,4-dihydro-1,4-
naphthalenediol, estriol, dianhydro-D-glucitol, dianhydro-D-mannitol, and other like
compounds.
[0028] Illustrative silyl derivatives of diols are exemplified by silyl derivatives of
the diols listed above. Illustrative silyl derivatives of diols include, but are not limited to:
(CH3)3SiOCH2CH2OSi(CH3)3, (C2H5)3SiOCH2CH2OSi(C2H5)3, ((CH3)3C)
(CH3)2SiOCH2CH2OSi(CH3)2(C(CH3)3), (C6H5) (CH3)2SiOCH2CH2OSi(CH3)2(C6H5),
(C6H5CH2)(CH3)2SiOCH2CH2OSi(CH3)2(CH2C6H5), (CH3)3SiOCH2CH2CH2OSi(CH3)3,
(CH3)3SiOCH2CH2CH2OSi(CH3)3, (CH3)3SiOCH2CH2CH2CH2OSi(CH3)3,
(CH3)3SiOCH2CH2CH2CH2CH2OSi(CH3)3,CH3CH(OSi(CH3)3)CH2OSi(CH3)3,
CH3CH2CH(OSi(CH3)3)CH2OSi(CH3)3,C6H5CH(OSi(CH3)3)CH2OSi(CH3)3,
C6H5CH(OSi(CH3)3)CH(OSi(CH3)3)C6H5,CH2=CHCH(OSi(CH3)3)CH2OSi(CH3)3,
CH = CHCH(OSi(CH3)3)CH2OSi(CH3)3,

and other like compounds.
[0029] Illustrative amino alcohols and their salts include, but are not limited to: 2-
amino-1-ethanol, LiOCH2CH2NH2, NaOCH2CH2NH2, KOCH2CH2NH2, 2-methylamino-1-
ethanol, LiOCH2CH2N(Li)CH3, 2-ethylamino-1-ethanol, 2-propylamino-1-ethanol, 2-
butylamino-1-ethanol, 2-phenylamino-1-ethanol, 2-benzylamino-1-ethanol, 2-acetylamino-1-
ethanol, 2-benzoylamino-1-ethanol, 2-(methoxycarbonyl)amino-1-ethanol, 2-(tert-
butoxycarbonylamino)-1-ethanol, 2-(9'-fluorenylmethoxycarbonyl)amino-2-ethanol, 2-
[(phenyloxycarbonyl)amino-1 -ethanol, 2-(methylsulfonyl)amino-1 -ethanaol, 2-
(phenylsulfonyl)amino-1 -ethanol, 2-benzylamino-1 -phenyl-1 -ethanol, 2-benzylamino-2-
phenyl-1-ethanol, 1-amino-2-propanol, 1-benzylamino-2-propanol, 2-methylamino-1-
propanol, 2-benzylamino-1 -propanol, 3-benzyloxy-2-(tert-butoxycarbonylamino)-1 -propanol,
2-benzylamino-1-butanol, 2-methylamino-1-butanol, 2-benzylamino-2-butanol, 3-
benzylamino-1-butanol, 4-benzylamino-1-butanol, 4-methylamino-2-buten-1-ol, 4-
benzylamino-2-buten-1-ol, 1-methylamino-2-hydroxy-3-butene, 1-benzylamino-2-hydroxy-3-
butene, 1-methylamino-2-hydroxy-4-phenyl-3-butene, 2-amino-1-pentanol, 2-methylamino-
1-pentanol, 2-benzylamino-1-pentanol, 1-methylamino-2-penten-4-ol, 1-ethylamino-2-
hydroxy-3-pentene, 1-benzylamino-2-hydroxy-4-methyl-3-pentene, 2-benzylamino-1-
hexanol, 2-benzylamino-heptanol, 2-benzylamino-1-octanol, 2-benzylamino- 1-nonanol, 2-
benzylamino-1 -decanol, 2-methylamino-1 -phenyl-1 -ethanol, 1 -cyclopentyl-2-methylamino-
1-ethanol, 1-cyclohexyl-2-methylamino-1-ethanol, 1-vinyl-2-methylamino-1-ethanol, 1-
(N,N-dimethylcarbamonyl)-2-methylamino-1-ethanol, 2-benzylamino- 1-cyclopentanol, 2-
phenylamino- 1-cyclopentanol, 3-benzylamino-1 -cyclopentanol, 2-methylamino-1 -
cyclopentanol, 2-benzylamino- 1-hydroxymethyl-cyclopentane, 4-methylamino-2-
cyclopenten-1-ol, 2-methylamino-1-cyclohexanol, 2-benzylamino- 1-cyclohexanol, 2-
phenylamino-1 -hydroxymethyl-cyclohexane, 4-ethylamino-2-cyclohexne-1 -ol, 2-
benzylamino-1-cycloheptane, 2-hydroxyazetidine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 3-
hydroxypiperidine, 4-hydroxypiperidine, 2-piperidinemethanol, 3-piperidinemethanol, 4-
piperidinemethanol, 2-piperidineethanol, 3-piperidineethanol, 4-piperidineethanol, 1-
piperazinepropanol, 1-(2-hydroxyethyl)piperazine, phenylephrine, and other like compounds.
[0030] Dlustrative silyl derivatives of amino alcohols are exemplified by silyl
derivatives of the amino alcohols listed above. Illustrative silyl derivatives of amino alcohols
include, but are not limited to: (CH3)3SiNHCH2CH2OSi(CH3)3,
((CH3)3Si)2NCH2CH2OSi(CH3)3,NH2CH2CH2OSi(CH3)3,
CH3N(Si(CH3)3)CH2CH20Si(CH3)3,CH3N(Si(CH2CH3)3)CH2CH2OSi(CH2CH3)3,
CH3N(Si(CH3)2(tert-C4H9))CH2CH2OSi((CH3)2(tert-C4H9)),
CH3N(Si(CH3)2(C6H5))CH2CH2OSi((CH3)2(C6H5)),CH3NHCH2CH2OSi(CH3)3,
C6H5CH2N(Si(CH3)3)CH2CH2OSi(CH3)3,CH3N(Si(CH3)3)CH(CH3)CH2OSi(CH3)3,
CH3CH(OSi(CH3)3)CH2N(Si(CH3)3)CH3,C6H5CH2N(Si(CH3)3)CH(CH2CH3)CH2OSi(CH3)3,
CH3CH2CH(OSi(CH3)3)CH2N(Si(CH3)3)CH2C6H5,

and other like compounds.
[0031] For each of R1-4, a hydrogen atom, a cyano group, or a substituted or
unsubstituted alkyl, alkenyl, alkynyl, aryl, alkoxy, acyl, alkoxycarbonyl, or aryloxycarbonyl
group is preferable because of availability. For R5, a hydrogen atom or a substituted or
unsubstituted alkyl, aryl, acyl, alkoxycarbonyl, or aryloxycarbonyl group is preferable
because of availability. For each of R6-13, a hydrogen atom, a halogen atom, a nitro group, a
cyano group, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy,
acyl, acyloxy, alkoxycarbonyl, or aryloxycarbonyl group is preferable because of availability.
[0032] Illustrative arylsulfur trifluorides of Process I, as represented by formula (III),
can be prepared as described in the literature [see J. Am. Chem. Soc, Vol. 82 (1962), pp.
3064-3072; Synthetic Communications, Vol. 33 (2003), pp.2505-2509; and US 7,265,247 B1
and US 7,381,846 B2, each of which is incorporated by reference herein for all purposes].
Arylsulfur trifluorides have high thermal stability (see US 7,381,846 B2). The arylsulfur
trifluorides are exemplified, but are not limited by, phenylsulfur trifluoride, each isomer (o,
m, and p-isomers) of methylphenylsulfur trifluoride, each isomer of dimethylphenylsulfur
trifluoride, each isomer of trimethylphenylsulfur trifluoride, each isomer of ethylphenylsulfur
trifluoride, each isomer of n-propylphenylsulfur trifluoride, each isomer of
isopropylphenylsulfur trifluoride, each isomer of n-butylphenylsulfur trifluoride, each isomer
of isobutylphenylsulfur trifluoride, each isomer of sec-butylphenylsulfur trifluoride, each
isomer of (tert-butyl)phenylsulfur trifluoride, each isomer of di(isopropyl)phenylsulfur
trifluoride, each isomer of tri(isopropyl)phenylsulfur trifluoride, each isomer of (tert-
butyl)dimethylphenylsulfur trifluoride, each isomer of (methoxymethyl)phenylsulfur
trifluoride, each isomer of bis(methoxymethyl)phenylsulfur trifluoride, each isomer of
bis(methoxymethyl)-(tert-butyl)phenylsulfur trifluoride, each isomer of bis(ethoxymefhyl)-
(tert-butyl)phenylsulfur trifluoride, each isomer of bis(isopropoxymethyl)-(tert-
butyl)phenylsulfur trifluoride, each isomer of fluorophenylsulfur trifluoride, each isomer of
chlorophenylsulfur trifluoride, each isomer of bromophenylsulfur trifluoride, each isomer of
iodophenylsulfur trifluorode, each isomer of difluorophenylsulfur trifluoride, each isomer of
trifluorophenylsulfur trifluoride, each isomer of tetrafluorophenylsulfur trifluoride,
pentafluorophenylsulfur trifluoride, each isomer of dichlorophenylsulfur trifluoride, each
isomer of dibromophenylsulfur trifluoride, each isomer of chlorofluorophenylsulfur
trifluoride, each isomer of bromofluorophenylsulfur trifluoride, each isomer of
chloro(methyl)phenylsulfur trifluoride, each isomer of chloro(dimefhyl)phenylsulfur
trifluoride, each isomer of nitrophenylsulfur trifluoride, each isomer of dinitrophenylsulfur
trifluoride, each isomer of cyanophenylsulfur trifluoride, and other like compounds. Among
them, phenylsulfur trifluoride, 4-(tert-butyl)-2,6-dimefhylphenylsulfur trifluoride, p-
methylphenylsulfur trifluoride, p-fluorophenylsulfur trifluoride, p-chlorophenylsulfur
trifluoride, p-bromophenylsulfur trifluoride, o- and p-nitrophenylsulfur trifluoride, p-(tert-
butyl)phenylsulfur trifluoride, 2,6-bis(methoxymethyl)phenylsulfur trifluoride, 2,6-
bis(methoxymethyl)-4-(tert-butyl)phenylsulfur trifluoride, and 2,4,6-
tri(isopropyl)phenylsulfur trifluoride are preferable because of availability and cost
considerations.
[0033] The reaction of an oxygen-containing compound of formula (II), in which at
least one of R* and Ry is a hydrogen atom, with an arylsulfur trifluoride of formula (IH) may
be conducted in the presence of a base, which may increase the yield of the product. In
particular, when an oxygen-containing compound of formula (II), in which A=NR5 and RX=H
and/or Ry=H, is used, a base is preferable. Preferable bases are exemplified by amines such as
trimethylamine, triethylamine, tripropylamine, isopropyldimethylamine, N,N-
diisopropylethylamine, tributylamine, l,8-diazobicyclo[5.4.0]undec-7-ene, 1,4-
diazobicyclo[4.3.0]non-5-ene, l,4-diazobicyclo[2.2.2]octane, pyridine, methylpyridine,
dimethylpyridine, trimethylpyridine, (N,N-dimethylamino)pyridine, quinoline, isoquinoline,
and other like compounds; carbonates such as sodium carbonate, sodium bicarbonate,
potassium carbonate, potassium bicarbonate, lithium carbonate, lithium bicarbonate, and
other like compounds; fluorides such as lithium fluoride, sodium fluoride, potassium fluoride,
cesium fluoride, tetramethylamrnonium fluoride, tetraethyammonium fluoride,
tetrabutylammonium fluoride, and other like compounds. The amount of base used for a
reaction of this type can preferably be selected from about 0.5 mol base to about 5 mol base
per 1 mol of an oxygen-containing compound of formula (II).
[0034] When an oxygen-containing compound of formula (II), in which at least one
of Rx and Ry is a silyl group, or Rx and Ry combine to form a silyl group, is used, the reaction
of the oxygen-containing compound with an arylsulfur trifluoride of formula (HI) can
preferably be conducted in the presence of a silicon atom-activating agent. Illustrative silicon
atom-activating agents include: fluorides containing a fluoride anion such as potassium
fluoride, cesium fluoride, tetramethylamrnonium fluoride, tetraethylammonium fluoride,
tetrabutylammonium fluoride, and other like fluorides; oxide salts such as sodium methoxide,
potassium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, and
other like oxides; cyanide salts such as sodium cyanide, potassium cyanide,
tetraethylammonium cyanide, tetrabutylammonium cyanide, and other like cyanides. Among
these, fluorides are preferable because of high yield of product(s). The amount of silicon
atom-activating agent used for a reaction can preferably be selected from a catalytic amount
to an amount in excess. A catalytic amount is preferable because of cost and yield.
[0035] The reaction of an oxygen-containing compound of formula (II), in which A is
an oxygen atom, with an arylsulfur trifluoride of formula (III) may be conducted in the
presence of hydrogen fluoride or a mixture of hydrogen fluoride and an amine compound(s),
which may increase the yield of the product. The hydrogen fluoride may be in situ generated
by addition of a necessary amount of water, an alcohol such as methanol, ethanol, propanol,
isopropanol, butanol, sec-butanol, isobutanol, tert-butanol and so on, or a carboxylic acid
such as acetic acid, propionic acid, and so on. The water, alcohol, or carboxylic acid is added
into the reaction mixture, since an arylsulfur trifluoride (ArSF3) reacts with water, an alcohol,
or a carboxylic acid to generate hydrogen fluoride, as shown in the following reaction
equations, however, this in situ generation method of hydrogen fluoride requires ArSF3 be
consumed at equimolar amounts of water, an alcohol, or a carboxylic acid.

[0036] The mixture of hydrogen fluoride and amine compound(s) is preferably
exemplified by a mixture of hydrogen fluoride and pyridine (for example, a mixture of about
70wt% HF and about 30wt% pyridine) or a mixture of hydrogen fluoride and triethylamine
[for example, a 3:1 (molar ratio) mixture of hydrogen fluoride and triethylamine, Et3N(HF)3].
The amount of hydrogen fluoride or a mixture of hydrogen fluoride and an amine
compound(s) may be a catalytic amount to an amount in excess for the reaction of this
invention, dependent on reaction conditions.
[0037] The reaction of an oxygen-containing compound of formula (II), in which A is
an oxygen atom, with an arylsulfur trifluoride of formula (III) can also be conducted in the
presence of a tetraalkylammonium fluoride-hydrogen fluoride such as tetrabutylammonium
fluoride-hydrogen fluoride [for example, tetrabutylammonium dihydrogentrifluoride,
(C4H9)4NH2F3]. The amount of a tetraalkylammonium fluoride-hydrogen fluoride may be a
catalytic amount to an amount in excess for the reaction of this invention, dependent on
reaction conditions.
[0038] Process I can be carried out in the presence of one or more solvents or in the
absence of solvent. The use of solvent is preferable for mild and efficient reactions. When
solvent is used, a preferable solvent will not substantially react with the starting material(s)
and/or reagents, the intermediates, and/or the final product(s). Suitable solvents include, but
are not limited to: alkanes, halocarbons, ethers, nitriles, aromatics, nitro compounds, esters,
and so on, and mixtures thereof. Example alkanes include normal, branched, cyclic isomers
of pentane, hexane, heptane, octane, nonane, decane, dodecane, undecane, and other like
compounds. Illustrative halocarbons include: dichloromethane, chloroform, carbon
tetrachloride, dichloroethane, trichloroethane, terachloroethane, rrichlorotrifluoroethane,
chlorobenzene, dichlorobenzene, trichlorobenzene, hexafluorobenzene, benzotrifluoride, and
bis(trifluoromethyl)benzene; normal, branched, cyclic isomers of perfluoropentane,
perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, and perfluorodecane;
perfluorodecalin; and other like compounds. Illustrative ethers include: diethyl ether, dipropyl
ether, di(isopropyl) ether, dibutyl ether, tert-butyl methyl ether, dioxane, glyme (1,2-
dimethoxyethane), diglyme, triglyme, and other like compounds. Illustrative nitriles include:
acetonitrile, propionitrile, benzonitrile, and other like compounds. Illustrative aromatics
include: benzene, toluene, xylene, and other like compounds. Illustrative nitro compounds
include: nitromethane, nitroethane, nitrobenzene, and other like compounds. Illustrative
esters include: methyl acetate, methyl propionate, ethyl acetate, ethyl propionate, propyl
acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, and other like
compounds.
[0039] In order to obtain good yield of product in Process I, the reaction temperature
can preferably be selected in the range of about -100°C - +200°C; more preferably, the
reaction temperature can be selected in the range of about -80°C ~ +150°C; and furthermore
preferably, the reaction temperature can be selected in the range of about -80°C ~ +120°C.
[0040] Reaction conditions of Process I are optimized to obtain economically good
yields of product. In one illustrative embodiment, from about 0.5 mol to about 2 mol, more
preferably, from about 0.8 mol to about 1.5 mol, furthermore preferably about 0.9 to about
1.2 mol of arylsulfur trifluoride (formula ITT) are combined with 1 mol of oxygen-containing
compound (formula II) to obtain a good yield of fluoroalkyl arylsulfinyl compound (formula
I).
[0041] Note that the reaction time for Process I varies dependent upon reaction
temperature, and the types and amounts of substrates, reagents, and solvents. As such,
reaction time is generally determined as the amount of time required to complete a particular
reaction, but can be from about 1 minute to about several days, preferably, within a few days.
[0042] R1, R2, R3, R4, R3, R6, R7, R8, R9, R10, R11, R12 and/or R13 of the products
represented by the formula (I) may be different from R1, R2, R3, R4, R5, R6, R7, R8, R9, R10,
R11, R12 and/or R13 of the starting materials represented by the formula (II). Thus,
embodiments of this invention include transformation of the R1, R2, R3, R4, R5, R6, R7, R8, R9,
R10, R11, R12 and/or R13 to different R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and/or R13
which may take place during the reaction of the present invention or under the reaction
conditions as long as both the fluorination and the arylsulfinylation take place.
[0043] The present invention also includes a method wherein the arylsulfur
trifluoride of formula (III) used in Process 1 (Scheme 1) is prepared by the method
comprising reacting arylsulfur halotetrafluoride of formula (IV) with a reducing substance.
Thus, embodiments of the present invention provide a method (Scheme 2, Processes II and
Ia) for preparing a fluoroalkyl arylsulfinyl compound having a formula (I), which comprises
(Process II) reacting an arylsulfur halotetrafluoride having a formula (IV) with a reducing
substance that reduces the arylsulfur halotetrafluoride and (Process la) reacting a resulting
arylsulfur trifluoride having a formula (HI) with an oxygen-containing compound having a
formula (II):
Scheme 2, Processes II and Ia

[0044] For the compounds represented by formulas (I), (II), (III), and (IV), R1, R2, R3,
R4, Rx, Ry, A, B, Ra, Rb, Rc, Rd, and Re are the same as described above. X is a chlorine atom,
a bromine atom, or an iodine atom. Preferably X is a chlorine atom to minimize cost.
Process II
[0045] The starting materials, arylsulfur halotetrafluorides used for Process n, may be
prepared according to the method shown in the literature (see Can. J. Chem., Vol. 75,
pp. 1878-1884, incorporated herein by reference for all purposes). Arylsulfur
halotetrafluorides can be prepared industrially at low cost using the methods shown in
Examples 47~62 (as well as methodologies provided throughout the disclosure).
[0046] Note that according to the nomenclature of Chemical Abstract Index Name,
and in accordance with the present disclosure, for example, C6H5-SF4Cl is named sulfur,
chlorotetrafluorophenyl-; P-CH3-C6H4-SF4Cl is named sulfur, chlorotetrafluoro(4-
methylphenyl)-; and P-NO2-C6H4-SF4Cl is named sulfur, chlorotetrafluoro(4-nitrophenyl)-.
[0047] Arylsulfur halotetrafluoride compounds of formula (IV) include isomers such
as trans-isomers and cis-isomers as shown below; arylsulfur halotetrafluoride is represented
by ArSF4X:

[0048] Illustrative arylsulfur halotetrafluorides include: phenylsulfur
chlorotetrafluoride, each isomer (o, m, and p-isomers) of methylphenylsulfur
chlorotetrafluoride, each isomer of dimethylphenylsulfur chlorotetrafluoride, each isomer of
ethylphenylsulfur chlorotetrafluoride, each isomer of n-propylphenylsulfur
chlorotetrafluoride, each isomer of isopropylphenylsulfur chlorotetrafluoride, each isomer of
n-butylphenylsulfur chlorotetrafluoride, each isomer of sec-butylphenylsulfur
chlorotetrafluoride, each isomer of isobutylphenylsulfur chlorotetrafluoride, each isomer of
(tert-butyl)phenylsulfur chlorotetrafluoride, each isomer of fluorophenylsulfur
chloroteterafluoride, each isomer of chlorophenylsulfur chlorotetrafluoride, each isomer of
bromophenylsulfur chlorotetrafluoride, each isomer of iodophenylsulfur chlorotetrafluoride,
each isomer of difluorophenylsulfur chlorotetrafluoride, each isomer of trifluorophenylsulfur
chlorotetrafluoride, pentafluorophenylsulfur chlorotetrafluoride, each isomer of
nitrophenylsulfur chlorotetrafluoride, and so on. Among them, phenylsulfur
chlorotetrafluoride, p-methylphenylsulfur chlorotetrafluoride, p-(tert-butyl)phenylsulfur
chlorotetrafluoride, p-chlorophenylsulfur chlorotetrafluoride, p-fluorophenylsulfur
chlorotetrafluoride, p-bromophenylsulfur chlorotetrafluoride, and p-nitrophenylsulfur
chlorotetrafluoride are preferable so as to minimize cost.
[0049] A reducing substance used in Process II is: 1) an element or an organic or
inorganic compound which reduces an arylsulfur halotetrafluoride of the formula (I) used in
the reaction; or 2) of which reduction potential is lower than that of arylsulfur
halotetrafluoride of the formula (I) used in the reaction. One or more reducing substances can
be used in a reaction, including mixtures thereof.
[0050] Reducing substances herein include elements such as: metals such as alkali
metals (elements in Group 1 of the Periodic Table), alkali earth metals (elements in Group 2
of the Periodic Table), transition metals and inner transition metals (elements in Groups 3~12
of the Perioidic Table), and metals in Groups 13-15 of the Periodic Table such as Al, Ga, In,
Tl, Sn, Pb, and Bi; semi-metals such as B, Si, Ge, As, Sb, Te, Po, and At; nonmetal elements
in Groups 13-17 of the Periodical Table (C, P, S, Se, I, and so on). Among these, preferred
elements are alkali metals, alkali earth metals, transition metals, metals in Groups 13-15 of
the Periodic Table, semi-metals, and nonmetals.
[0051] Reducing substances herein also include inorganic compounds such as:
hydrogen, metal compounds, semi-metal compounds, and nonmetal compounds. Among
these, preferred inorganic compounds include: metal salts, semi-metal salts, nonmetal salts,
inorganic chloride salts, inorganic bromide salts, inorganic iodide salts, ammonia (NH3),
inorganic sulfur compounds, and so on.
[0052] Preferred inorganic chloride salts are exemplified with metal chlorides (LiCl,
NaCl, KC1, RbCl, CsCl, MgCl2, MgCIF, CaCl2, TiCl2, VC12, CrCl2, FeCl2, CuCl, SnCl2, and
other metal salts containing chloride anions), ammonium chloride, and other inorganic salts
containing chloride anions. Preferred inorganic bromide salts are exemplified with metal
bromides (LiBr, NaBr, KBr, RbBr, CsBr, MgBr2, MgBrCl, MgBrF, CaBr2, FeBr2, CuBr,
SnBr2, and other metal salts containing bromide anions), ammonium bromide, and other
inorganic salts containing bromide anions. Preferred inorganic iodide salts are exemplified
with metal iodides (LiI, NaI, KI, RbL, CsI, MgI2, MgBrI, MgCII, MgFI, CaI2, FeI2, CuI, SnI2,
and other metal salts containing iodide anions), ammonium iodide, and other inorganic salts
containing iodide anions. Preferred inorganic sulfur compounds are exemplified with
hydrogen sulfide, salts of hydrogen sulfide, salts of sulfide, salts of hydrogen sulfite, salts of
sulfite, salts of thiosulfate, salts of thiocyanate, and other inorganic compounds containing
sulfur (valence state II or IV).
[0053] Among these, more preferred inorganic compounds include: inorganic
chloride salts, inorganic bromide salts, and inorganic iodide salts.
[0054] Preferred reducing substances also include organic compounds such as:
organic chloride salts, organic bromide salts, organic iodide salts, substituted and
unsubstituted arenes, substituted and unsubstiruted heteroarenes, substituted and
unsubstituted unsaturated aliphatic hydrocarbons, substituted and unsubstituted nitrogen-
containing aliphatic hydrocarbons, salts or complexes of substituted or unsubstituted
heteroarenes and hydrogen fluoride (HF), salts or complexes of substituted or unsubstiruted
nitrogen-containing aliphatic hydrocarbons and hydrogen fluoride (HF), organic sulfur
compounds, organic selenium compounds, organic phosphorous compounds, and so on.
[0055] Preferred organic chloride salts are exemplified with methylammonium
chloride, dimethylammonium chloride, trimethylammonium chloride, tetramethylammonium
chloride, ethylammonium chloride, diethylammonium chloride, triethylammonium chloride,
tetraethylammonium chloride, propylammonium chloride, tripropylammonium chloride,
tetrapropylammonium chloride, butylammonium chloride, tributylammonium chloride,
tetrabutylammonium chloride, anilinium chloride, N,N-dimethylanilinium chloride,
pyridinium chloride, N-methylpyridnium chloride, pyrrolidinium chloride, piperidinium
chloride, and other organic salts containing chloride anions.
[0056] Preferred organic bromide salts are exemplified with methylammonium
bromide, dimethylammonium bromide, trimethylammonium bromide, tetramethylammonium
bromide, triethylammonium bromide, tetraethylammonium bromide, tripropylammonium
bromide, tributylammonium bromide, tetrabutylammonium bromide, pyridinium bromide,
and other organic salts containing bromide anions.
[0057] Preferred organic iodide salts are exemplified with methylammonium iodide,
dimethylammonium iodide, trimethylammonium iodide, tetramethylammonium iodide,
triethylammonium iodide, tetraethylammonium iodide, tributylammonium iodide,
tetrabutylammonium iodide, pyridinium iodide, and other organic salts containing iodide
anions.
[0058] Preferred substituted and unsubstituted arenes are exemplified with benzene,
toluene, xylene, mesitylene, durene, hexamethylbenzene, anisole, dimethoxybenzene, aniline,
N,N-dimethylaniline, phenylenediamine, phenol, salts of phenol, hydrobenzoquinone,
naphthalene, indene, anthracene, phenanthrene, pyrene, and so on.
[0059] Preferred substituted and unsubstituted heteroarenes are exemplified with
pyridine, methylpyridine, dimethylpyridine, trimethylpyridine, fluoropyridine,
chloropyridine, dichloropyridine, pyrrole, indole, quinoline, isoquinoline, carbazole,
imidazole, pyrimidine, pyridazine, pyrazine, triazole, furan, benzofuran, thiophene,
benzothiophene, thiazole, phenothiazine, phenoxazine, and so on.
[0060] Preferred substituted and unsubstituted unsaturated aliphatic hydrocarbons are
exemplified with substituted and unsubstituted alkenes such as ethylene, propene, butene,
isobutylene, 2-methyl-2-butene, 2,3-dimethyl-2-butene, 2,3-dimethyl-1-butene, butadiene,
pentene, 2-methyl-1-pentene, 2-methyl-2-pentene, hexene, cyclohexene, 1-methyl-1-
cyclohexene, 1,2-dimethyl-1-cyclohexene, 2-N,N-diethylamino-1 -propene, 1-N,N-
dimethylamino-1 -cyclohexene, 1-N,N-diethylamino-1 -cyclohexene, 1 -pyrrolidine-1 -
cyclohexene, 1-pyrrolidino-1-cyclopentene, styrene, a- and ß-methylstyrene, stilbene, 2-
methoxy-1-propene, ethyl vinyl ether, 2,3-dihydrofuran, 2,3-dihydro-5-methylfuran, 3,4-
dihydro-2H-pyran, and so on, and substituted and unsubstituted alkynes such as acetylene,
propyne, phenylacetylene, diphenylacetylene, and so on.
[0061] Preferred substituted and unsubstituted nitrogen-containing aliphatic
hydrocarbons are exemplified with methylamine, ethylamine, diethylamine, triethylamine,
propylamine, butylamine, pyrrolidine, N-methylpyrrolidine, piperidine, N-methylpiperidine,
morpholine, N-methylmorpholine, ethylenediamine, N,N,N'N'-tetramethylethylenediamine,
triethylenediamine, urea, tetramethylurea, and so on.
[0062] Preferred salts or complexes of substituted or unsubstituted heteroarenes and
hydrogen fluoride (HF), are exemplified with pyridine- HF, pyridine- 2HF, pyridine- 3HF,
methylpyridine- HF, dimethylpyridine- HF, trimethylpyridine- HF, and so on.
[0063] Preferred salts or complexes of substituted or unsubstituted nitrogen-
containing aliphatic hydrocarbons and hydrogen fluoride (HF), are exemplified with
triethylamineHF, triethylamine-2HF, triethylamine-3HF, trimethylamine-HF, and so on.
[0064] Preferred organic sulfur compounds are exemplified with organic sulfides,
organic disulfides, organic polysulfides, organic sulfenyl halides, and organic thiols and their
salts.
[0065] Preferred organic sulfides are exemplified with dimethyl sulfide, diethyl
sulfide, dipropyl sulfide, dibutyl sulfide, di(tert-butyl) sulfide, tetrahydrothiophene, methyl
phenyl sulfide, trimethylsilyl phenyl sulfide, diphenyl sulfide, bis(o, m, and p-methylphenyl)
sulfides, bis(o, m, and p-fluorophenyl) sulfides, bis(o, m, and p-chlorophenyl) sulfide, bis(o,
m, and p-bromophenyl) sulfide, bis(o, m, and p-nitrophenyl) sulfide, and so on.
[0066] Preferred organic disulfides are exemplified with dimethyl disulfide, diethyl
disulfide, diisopropyl disulfide, di(tert-butyl) disulfide, diphenyl disulfide, bis(o, m, and p-
methylphenyl) disulfides, bis(o, m, and p-ethylphenyl) disulfide, bis(o, m, and p-n-
propylphenyl) disulfide, bis(o, m, and p-isopropylphenyl) disulfide, bis(o, m, and p-
butylphenyl) disulfide, bis(o, m, and p-isobutylphenyl) disulfide, bis(o, m, and p-sec-
butylphenyl) disulfide, bis(o, m, and p-tert-butylphenyl) disulfide, each isomer of
bis(dimethylphenyl) disulfide, each isomer of bis(trimethylphenyl) disulfide, bis(4-tert-butyl-
2,6-dimethylphenyl) disulfide, bis(o, m, and p-fluorophenyl) disulfides, bis(o, m, and p-
chlorophenyl) disulfide, bis(o, m, and p-bromophenyl) disulfide, bis(o, m, and p-iodophenyl)
disulfides, bis(o, m, and p-nitrophenyl) disulfide, and so on.
[0067] Preferred organic polysulfides are exemplified with diphenyl trisulfide,
dimethyl trisulfide, and so on.
[0068] Preferred organic sulfenyl halides are exemplified with phenylsulfenyl
fluoride, phenylsulfenyl chloride, o, m, and p-fluorophenylsulfenyl chloride, o, m, and p-
chlorophenylsulfenyl chloride, o, m, and p-bromophenylsulfenyl chloride, o, m, and p-
nitrophenylsulfenyl chloride, and so on.
[0069] Preferred organic thiols and their salts are exemplified with methanethiol,
ethanethiol, propanethiol, isopropanethiol, butanethiol, sec-butanethiol, isobutanethiol, tert-
butanethiol, thiophenol, o, m, and p-methylbenzenethiols, o, m, and p-ethylbenzenethiol, o,
m, and p-n-propylbenzenethiol, o, m, and p-isopropylbenzenethiol, o, m, and p-
butylbenzenethiol, o, m, and p-isobutylbenzenethiol, o, m, and p-sec-butylbenzenethiol, o, m,
and p-tert-butylbenzenethiol, each isomers of dimethylbenzenethiol, each isomer of
trimethylbenzenethiol, 4-tert-butyl-2,6-dimethylbenzenethiol, o, m, and p-
chlorobenzenethiols, o, m, and p-fluorobenzenethiols, o, m, and p-bromobenzenethiols, o, m,
and p-nitrobenzenethiol, and metal salts, ammonium salts, phosphonim salts of these organic
thiols.
[0070] Preferred organic selenium compounds are exemplified with benzeneselenol,
diphenyl selenide, diphenyl diselenide, and so on.
[0071] Preferred organic phosphorous compounds are exemplified with
trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine,
triphenylphosphine, trimethylphosphite, triethylphosphite, tripropylphosphite,
tributylphosphite, triphenylphosphite, and so on.
[0072] Preferred reducing substances in general include: the elements such as alkali
metals, alkali earth metals, transition metals, metals in Groups 13-15 of the Periodic Table,
and semi-metals, the inorganic compounds such as inorganic chloride salts, inorganic
bromide salts, and inorganic iodide salts, and the organic compounds such as organic chloride
salts, organic bromide salts, organic iodide salts, substituted and unsubstituted arenes,
substituted and unsubstituted heteroarenes, substituted and unsubstituted unsaturated aliphatic
hydrocarbons, substituted and unsubstituted nitrogen-containing aliphatic hydrocarbons,
organic sulfur compounds, salts or complexes of substituted or unsubstituted heteroarenes
and hydrogen fluoride, and salts or complexes of substituted or unsubstituted nitrogen-
containing aliphatic hydrocarbons and hydrogen fluoride.
[0073] Among the reducing substances exemplified above, substituted or
unsubstituted heteroarenes are preferable, and among these, substituted or unsubstituted
pyridines such as pyridine, methylpyridine, dimethylpyridine, trimethylpyridine,
chlororpyridine and other like pyridines are more preferable; pyridine is furthermore
preferable due to its low cost, mild reactions, and high yields of arylsulfur trifluoride of
formula (III) and of the final products of formula (I).
[0074] Process II can be carried out in the presence of one or more solvents or in the
absence of solvent. In some cases, the use of solvent is preferable for mild and efficient
reactions. When solvent is used, the preferable solvents will not substantially react with the
starting materials and reagents, the intermediates, and/or the final products. Suitable solvents
include the same solvents as were discussed in Process I above.
[0075] In order to obtain good yield of product in Process II, the reaction temperature
is preferably selected in the range of about -100°C ~ +200°C; more preferably, the reaction
temperature is selected in the range of about -80°C ~ +150°C; and furthermore preferably, the
reaction temperature is selected in the range of about -80°C - +120°C.
[0076] Reaction conditions of Process II are optimized to obtain economically good
yield of product. The amount of a reducing substance greatly varies dependent on the nature
and reactivity of the reducing substance. However, in one illustrative embodiment, from
about 0.1 mol to about 5 mol, more preferably, from about 0.15 mol to about 3 mol of a
reducing substance can be selected against 1 mol of arylsulfur halotetrafluoride (formula IV)
to obtain a good yield of arylsulfur trifluoride (formula IE).
[0077] Note that the reaction time for Process II varies dependent upon reaction
temperature, and the types and amounts of substrates, reagents, and solvents. As such,
reaction time is generally determined as the amount of time required to complete a particular
reaction, but can be from about 1 minute to several days, preferably, within a few days.
Process Ia
[0078] Process Ia is the same as Process I except that arylsulfur trifluoride of formula
(III) as used in Process Ia is prepared by Process II.
[0079] Illustrative oxygen-containing compounds, represented by formula (II), used
in Process II are the same as exemplified in Process I above.
[0080] It is preferable that the arylsulfur trifluoride prepared by Process II can be
used without isolation for the next process, Process Ia. Accordingly, the reaction mixture
obtained in Process II can be used for the next process, Process Ia. In this case, the use of a
silyl activating catalyst such as potassium fluoride and tetrabutylammonium fluoride is not
necessary when an oxygen-containing compound of formula (II) (Rx and Ry each is a silyl
group or Rx and Ry combine to form a silyl group) is used for this process (Process la).
[0081] R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and/or R13 of the products
represented by the formula (I) may be different from R1, R2, R3, R4, R5, R6, R7, R8, R9, R10,
R11, R12 and/or R13 of the starting materials represented by the formula (II). Thus,
embodiments of this invention include transformation of the R1, R2, R3, R4, R5, R6, R7, R8, R9,
R10, R11, R12 and/or R13 to different R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and/or R13
which may take place during the reaction of the present invention or under the reaction
conditions as long as both the fluorination and the arylsulfinylation take place.
[0082] Embodiments of this invention also include transformation of Ra, Rb, Rc, Rd,
and/or Re of the starting materials of formulas (III) or (IV) to different Ra, Rb, Rc, Rd, and/or
Re of the products, which may take place during the reaction of the present invention or under
the reaction conditions.
[0083] The present invention also provide a method (Scheme 3, Process III) for
preparing a fluoroalkyl arylsulfinyl compound having a formula (I), which comprises reacting
an oxygen-containing compound having a formula (II) with arylsulfur halotetrafluoride
having a formula (IV) in the presence of a reducing substance that reduces the arylsulfur
halotetrafluoride:
Scheme 3, Process III

Process III
[0084] Oxygen-containing compounds of formula (II) used for Process in are the
same for Process I. Arylsulfur halotetrafluorides of formula (IV) used for Process III are the
same as for Process II. Reducing substances used for Process III are the same as for Process
II. Arylsulfur halotetrafluoride of the formula (IV) may be derived by an existing reducing
substance to another compound(s) that can more effectively fluorinate an oxygen-containing
compound having a formula (II). The compound(s) include any derived compounds that can
fluorinate an oxygen-containing compound having a formula (II) to form the product
(formula I). A preferrable derived compound is an arylsulfur trifluoride represented by the
formula (III).
[0085] The reaction of an oxygen-containing compound of formula (II) with the
arylsulfur halotetrafluoride in the presence of a reducing substance, wherein at least one of Rx
and Ry is a hydrogen atom or a silyl group, or Rx and Ry combine to form a silyl group, may
be conducted furthermore in the presence of a base or a silicon atom-activating agent. The
base or silicon atom-activating agent is exemplified by the same as for Process I. The amount
of the base or silicon atom-activating agent may be a catalytic amount to an amount in excess
for the reaction of this invention, dependent on reaction conditions.
[0086] The reaction of an oxygen-containing compound of formula (II) with the
arylsulfur halotetrafluoride in the presence of a reducing substance, wherein A is an oxygen
atom, may also be conducted furthermore in the presence of hydrogen fluoride, a mixture of
hydrogen fluoride and an amine(s), or a tetraalkylammonium fluoride-hydrogen fluoride. The
hydrogen fluoride may be in situ generated in the same manner as described for Process I.
The mixture of hydrogen fluoride and an amine(s), or the tetraalkylammonium fluoride-
hydrogen fluoride, is exemplified as in Process I. The amount of the hydrogen fluoride, a
mixture of hydrogen fluoride and an amine(s), or tetraalkylammonium fluoride-hydrogen
fluoride, may be a catalytic amount to an amount in excess for the reaction of this invention,
dependent on reaction conditions.
[0087] Process III can be carried out in the presence of one or more solvent(s) or in
the absence of solvent. The use of solvent is preferable for mild and efficient reactions. When
solvent is used, the preferable solvents will not substantially react with the starting materials
and reagents, the intermediates, and/or the final product(s). Suitable solvents include the
same solvents as were described in Process I above.
[0088] In order to obtain good yield of product in Process III, the reaction
temperature can preferably be selected in the range of about -100°C ~ +200°C; more
preferably, the reaction temperature can be selected in the range of about -80°C - +150°C;
and furthermore preferably, the reaction temperature can be selected in the range of about -
80°C - +120°C.
[0089] Reaction conditions of Process III are optimized to obtain economically good
yield of product. In one illustrative embodiment, from about 0.5 mol to about 2 mol, more
preferably, from about 0.8 mol to about 1.5 mol, furthermore preferably, from about 0.9 mol
to about 1.2 mol of arylsulfur halotetrafluoride (formula IV) are combined with 1 mol of
oxygen-containing compound (formula II) to obtain a good yield of fluoroalkyl arylsulfinyl
compound (formula I).
[0090] The amount of a reducing substance greatly varies on the nature and reactivity
of the reducing substance used. However, in one illustrative embodiment, from about 0.1 mol
to about 5 mol, more preferably, from about 0.15 mol to 3 mol of a reducing substance can be
selected against 1 mol of arylsulfur halotetrafluoride (formula IV) to obtain a good yield of
the product (formula I).
[0091] Note that the reaction time for Process III varies dependent upon reaction
temperature, and the types and amounts of substrates, reagents, and solvents. As such,
reaction time is generally determined as the amount of time required to complete a particular
reaction, but can be from about 1 minute to several days, preferably, within a few days.
[0092] R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, Ru, R12 and/or R13 of the products
represented by the formula (I) may be different from the R1, R2, R3, R4, R5, R6, R7, R8, R9,
R10, Rn, R12 and/or R13 of the starting materials represented by the formula (II). Thus,
embodiments of this invention include transformation of the R1, R2, R3, R4, R5, R6, R7, R8, R9,
R10, R11, R12 and/or R13 to different R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and/or R13
which may take place during the reaction of the present invention or under the reaction
conditions as long as both the fluorination and the arylsulfinylation take place.
[0093] Embodiments of this invention also include transformation of Ra, Rb, Rc,
Rd, and/or Re of the starting materials of formula (IV) to different Ra, Rb, Rc, Rd, and/or Re of
the products, which may take place during the reaction of the present invention or under the
reaction conditions.
[0094] The fluoroalkyl arylsulfinyl compounds of formula (I) can be used as useful
fluorinated compounds, intermediates, and building blocks (fluorinated synthons) for
preparation of other useful fluorine-containing compounds (for example, see Examples 72 ~
83). Fluorine-containing compounds have wide application in medical, agricultural, and
electronic materials as well as other like industries because the fluoro compounds show
specific biological activity or physical properties based on the presence of one or more
fluorine atoms [see Chemical & Engineering News, June 5, pp 13-22 (2006); Angew. Chem.
Int. Ed., Vol. 39, pp 4216-4235 (2000)].
[0095] The fluoroalkyl arylsulfinyl compounds have an arylsulfinyl group, ArS(O)-,
which is an excellent protecting group of a hydroxy or an amino group in organic synthesis.
The arylsulfinyl group can easily be deprotected under mild conditions without altering other
functional groups in a molecule (for example, see Examples 82 and 83). Accordingly, the
arylsulfinyl compounds produce useful fluorine-containing alcohols having formula (V) or
amines having formula (VI) as shown in Scheme 4 (which shows examples of the fluoroalkyl
arylsulfinyl compounds of formula I).
Scheme 4

[0096] In Formulas (I), (V), and (VI), R1, R2, R3, R4, A, B, R5, Ra, Rb, Rc, Rd, and Re
are the same as defined above.
[0097] In particular, 3-fiuoropyrrolidine or its salt as shown in Example 83, is an
important fluorine-containing compound [see, Bioorganic & Medicial Chemistry Letters,
Vol. 15, pp.4770-4773 (2005) and Vol. 14, pp.1265-1268 (2004); Synlett, 1995, pp.55-57].,
The present invention shows a surprisingly useful preparation of 3-fluoropyrrolidine (or its
salt) from 3-pyrrolidinol via the compound and preparative methods of the present invention
(see Examples 44, 45, and 83). A conventional preparative method of 3-fluoropyrrolidine is
that 3-pyrrolidinol includes conversion with benzyl halide to N-benzylpyrrolidinol, which is
then reacted with p-toluenesulfonyl chloride to give N-benzyl-3- (p-
toluenesulfonyloxy)pyrrolidine, and treated with spray-dried potassium fluoride to give N-
benzyl-3-fluoropyrrolidine, which is then deprotected by hydrogenation at 45 psi in the
presence of 10% Pd/C catalyst to produce 3-fluoropyrrolidine or its salt (see Synlett, 1995,
pp.55-57). However, the conventional method for 3-fluoropyrrolidine is a multi-step method
and provides a more costly product. As such, embodiments of the present invention provide
significantly improved methodologies for preparation of, for example, 3-fluoropyrrolidine.
[0098] Furthermore, the arylsulfinyl group can easily be transformed to another
functional group such as arylsulfonyl group, ArSO2-. As shown in Scheme 5 and Examples
72-79, a fluoroalkyl arylsulfinyl compounds having a formula (I) is converted to a
fluoroalkyl arenesulfonate having a formula (VII) or fluoroalkyl arenesulfonamide having a
formula (VIII), which are useful fluorinated intermediates and building blocks (synthons) for
the preparation of useful fluorine-containing compounds. For example, a fluoroalkyl
arenesulfonate is typically transformed to another fluoroalkyl derivative (see Examples 80
and 81).

[0099] In Formulas (I), (VII), and (VIII), R1, R2, R3, R4, R5, A, B, Ra, Rb, Rc, Rd, and
Re are the same as defined above.
[00100] The compounds of the invention may comprise one or more chiral centers so
that the compounds may exist as stereoisomers, including diasteroisomers, enantiomers, and
rotamers (rotational isomers). All such compounds are within the scope of the present
invention, including all such stereoisomers, and mixtures thereof, including racemates.
[00101] Another embodiment of the present invention provides novel useful
fluoroalkyl arylsulfinyl compounds represented by formula (la):

in which:
R1', R2', R3' , and R4' each is independently a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, a
substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, preferably 2 to
14 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
preferably 6 to 14 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group
having 2 to 20 carbon atoms, preferably 2 to 14 carbon atoms, a substituted or
unsubstituted aryloxycarbonyl group having 7 to 20 carbon atoms, preferably 7 to 14
carbon atoms, or a cyano group;
Ra', Rb', Rc', Rd', and Re' each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 4
carbon atoms, or a nitro group;
A' is an oxygen atom or NR5 in which R5 is a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, a
substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 14
carbon atoms;
B'is

in which:
R6', R7' ,R8', R9', R10', R11', R12' and R13' each is independently a hydrogen atom, a
halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
preferably 1 to 14 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to
20 carbon atoms, preferably 2 to 14 carbon atoms, a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms, a substituted or
unsubstituted alkoxy group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms,
a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, preferably 6 to
14 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20
carbon atoms, preferably 2 to 14 carbon atoms, a substituted or unsubstituted
aryloxycarbonyl group having 7 to 20 carbon atoms, preferably 7 to 14 carbon atoms, a
nitro group, or a cyano group;
h, i, and j each is independently 0 or 1; and
two or more of R1', R2', R3', R4', R5', R6', R7', R8', R9', R10', and R11' or two or more of
R1', R2', R3', R4', R5', R12', and R13' may be linked with or without a heteroatom(s) to form
any ring structure.
[00102] A preferable total number of h, i, and j of formula (Ia) is 2 or less, more
preferably, 1 or 0, as based on availability and cost considerations.
[00103] The present invention also provides a method (Scheme 6; Process I') for
preparing a fluoroalkyl arylsulfinyl compound having a formula (Ia), which comprises
reacting an oxygen-containing compound having a formula (IIa) with an arylsulfur trifluoride
having a formula (IIIa):
Scheme 6, Process I'

For the compounds represented by formulas (Ia), (IIa), and (IIIa), R1', R2', R3', R4', Rx, Ry, A',
B', Ra', Rb', Rc', Rd', and Re' are the same as described above.
Process I'
[00104] Process I' is the same as Process I except that compounds (IIa) and (IIIa) are
used instead of compounds (II) and (III), respectively. Illustrative compounds of formulas
(IIa) and (IIIa) are exemplified in Process I above.
[00105] The present invention also includes a method wherein the arylsulfur trifluoride
of formula (IIIa) used for the Process 1' (Scheme 6) is prepared by the method comprising
R1'' and R4'' each is independently a hydrogen atom, a substituted or unsubstituted
alkyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, a substituted
or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms,
a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms,
preferably 2 to 14 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group
having 7 to 20 carbon atoms, preferably 7 to 14 carbon atoms, or a cyano group;
R6 , R7 , R8 , R9 , R10 and R11 each is independently a hydrogen atom, a
substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 14
carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
preferably 6 to 14 carbon atoms;
h, i and j each is independently 0 or 1;
n is 1, 2, 3, or 4; and
Ra', Rb', Rc', Rd', and Re' are the same as described above.
[00113] Preferable total number of h, i, and j of formula (lb) is 2 or less, more
preferably 1 or 0, most preferably 0, as based on availability.
[00114] The fluoroalkyl arylsulfinyl compound of formula (Tb) can be prepared
according to Process I', Processes II' and Ia', or Process III'.
[00115] Embodiments of the present invention provide useful fluoroalkyl arylsulfinyl
compounds represented by formula (Ic) as follows:

in which:
R1'' , R3'' and R4'' each is independently a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, a
substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 14
carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon
atoms, preferably 2 to 14 carbon atoms, a substituted or unsubstituted aryloxycarbonyl
group having 7 to 20 carbon atoms, preferably 7 to 14 carbon atoms, or a cyano group;
R6 and R7 each is independently a hydrogen atom, a substituted or unsubstituted
alkyl group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms, a substituted
or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms;
h is 0 or 1;
n is 1, 2, 3, or 4; and
Ra', Rb', Rc', Rd', and Re' are the same as described above.
[00116] The fluoroalkyl arylsulfinyl compound of formula (Ic) can be prepared
according to Process I', Processes II' and Ia', or Process III'.
[00117] Embodiments of the present invention provide a fluoroalkyl arylsulfinyl
compound having a formula (Id) as follows:

in which:
R is a hydrogen atom, a substituted or unsubstituted alkoxycarbonyl group having
2 to 20 carbon atoms, preferably 2 to 14 carbon atoms, a substituted or unsubstituted
aryloxycarbonyl group having 7 to 20 carbon atoms, preferably 7 to 14 carbon atoms, or
a cyano group; and
Ra', Rb', Rc', Rd', and Re' are the same as described above.
[00118] The fluoroalkyl arylsulfinyl compound of formula (Id) can be prepared
according to Process I', Processes II' and Ia', or Process III'.
[00119] The fluoroalkyl arylsulfinyl compound (formula (I)) of the present invention is
also prepared by reaction of a fluorine-containing compound having a formula (EX) with an
arylsulfinyl fluoride having a formula (X) in the presence of a base, as shown in Scheme 9
(Process IV) (also, see Examples 70 and 71).
Scheme 9, Process IV

[00120] For the compounds represented by formulas (I), (IX), and (X), R1, R2, R3, R4,
A, B, Ra, Rb, Rc, Rd, and Re are the same as described above.
[00121] The arylsulfinyl fluoride (formula (X)) is prepared in a high yield from
arylsulfur trifluoride (formula (III)) by reaction with a carboxylic acid, as shown in Example
69.
[00122] A fluoroalkyl arylsulfinyl compound having a formula (Ie) can also be
prepared by Process V (Scheme 10) (also, see Example 31). Thus, the present invention
provides a method (Scheme 10, Process V) for preparing a fluoroalkyl arylsulfinyl compound
having a formula (Ie), which comprises reacting an oxygen-containing compound having a
formula (IIb) with arylsulfur trifluoride having a formula (III):
Scheme 10, Process V

[00123] Compound (IIb) is compound (II) wherein the B is -C(R12)=C(R13)-.
[00124] For the compounds represented by formulas (IIb), (III), and (Ie), R1, R2, R3,
R4, R12, R13, A, Rx, Ry, Ra, Rb, Rc, Rd, and Re are the same as described above.
Process V
[00125] Process V is the same as Process I except that compound (IIb) is substituted
for compound (II). Illustrative compounds of formula (IIb) are exemplifed in Process I above.
[00126] The present invention includes a method wherein the arylsulfur trifluoride of
formula (III) used in Process V is prepared by the method comprising reacting arylsulfur
halotetrafluoride of formula (IV) with a reducing substance. These processes are the same as
Process II and Process Ia except that compound (IIb) is used instead of compound (II).
[00127] The present invention also provides a method for preparation of a compound
of formula (Ie), which comprises reacting a compound of formula (IIb) with arylsulfur
halotetrafluoride of formula (IV) in the presence of a reducing substance that reduces the
arylsulfur halotetrafluoride. This process is the same as Process HI except that compound
(IIb) is used instead of compound (II).
[00128] A fluoroalkyl arylsulfinyl compound having a formula (If) can also be
prepared by Process VI (scheme 11) (also, see Example 22). Thus, the present invention
provide a method (Scheme 11, Process VI) for preparing a fluoroalkyl arylsulfinyl compound
having a formula (If), which comprises reacting an oxygen-containing compound having a
formula (IIc) with arylsulfur trifluoride having a formula (III):
Scheme 11, Process VI

[00129] Compound (IIc) is the same as compound (II) wherein R1 is -
C(R19)=C(R20)(R21).
[00130] For the compounds represented by formulas (Uc), (III), and (If), R2, R3, R4, A,
B, Rx, Ry, Ra, Rb, Rc, Rd, and Re are the same as described above. R19, R20, and R21 each is the
same as defined for R6-13 described above.
Process VI
[00131] Process VI is the same as Process I except that compound (IIc) is substituted
for compound (II). Illustrative compounds of formula (IIc) are exemplified in Process I
above.
[00132] The present invention includes a method wherein the arylsulfur trifluoride of
formula (III) used in Process VI is prepared by the method comprising reacting arylsulfur
halotetrafluoride of formula (IV) with a reducing substance. These processes are the same as
Process II and Process Ia except that compound (IIc) is used instead of compound (II).
[00133] The present invention also provides a method for preparation of a compound
of formula (If), which comprises reacting a compound of formula (IIc) with arylsulfur
halotetrafluoride of formula (IV) in the presence of a reducing substance that reduces the
arylsulfur halotetrafluoride. This process is the same as Process III except that compound
(IIc) is used instead of compound (II).
[00134] The present invention provides preparative methods for fluoroalkyl
arylsulfinyl compounds having a formula (I) and in addition, provides novel fluoroalkyl
arylsulfinyl compounds having a formula (Ia), (Ib), (Ic) and/or (Td). The present invention
also provides preparative methods for fluoroalkyl arylsulfinyl compounds having a formula
(Ie) and/or (If). The preparative methods herein provide surprisingly good results, timely and
convenient processes, improved safety, enhanced yields, and lower costs as compared to
other conventional methods. The fluoroalkyl arylsulfinyl compounds are useful fluorinated
compounds, fluoro intermediate compounds, or fluorinated building blocks, i.e., useful for
the preparation of a desired fluoro compound.
[00135] The following examples will illustrate the present invention in more details,
but it should be understood that the present invention is not deemed to be limited thereto.
EXAMPLES
[00136] The following examples are provides for illustrative purposes only and are
not intended to limit the scope of the invention.
Example 1. Preparation of 2-fluoroethyl benzenesulfinate (1-1)

[00137] Phenylsulfur trifluoride (414 mg, 2.49 mmol) was taken in a vessel made of
fluoropolymer (PFA) and dissolved in 2.5 mL of dry dichloromethane. The solution was
cooled to -78 °C, and into the solution was slowly added a solution of 155 mg (2.49 mmol) of
ethylene glycol in 2.5 mL of dry dichloromethane during about 20 minutes. The reaction
mixture was allowed to warm to room temperature and stirred at room temperature for 3
hours. An aqueous sodium carbonate solution was added to the reaction mixture. The organic
layer was separated, dried over anhydrous magnesium sulfate, and filtered. Removal of
solvent at reduced pressure gave 2-fluoroethyl benzenesulfinate (1-1), which was further
purified by chromatography on silica gel: Yield 80%; 1H-NMR (CDCl3) d 3.5-3.9 (m, 1H),
4.05-4.30 (m, 1H), 4.3-4.65 (dm, 2H, J = 50 Hz), 7.4-7.55 (m, 3H), 7.6-7.7 (m, 2H); 19F-
NMR (CDCl3) d-224.33 (m, IF); 13C-NMR (CDCl3) 63.03 (d, J = 20 Hz), 81.86 (d, J = 172
Hz), 125.34, 129.24, 132.51, 144.22.
Example 2~12. Prevaration of 2-fluoroethyl benzenesulfinate derivatives (1-1)~ (1-7)
[00138] Fluoroethyl benzenesulfinate derivates (1-1) - (1-7) were prepared by reaction
of arylsulfur trifluoride (III) with ethylene glycol, its salts or silyl derivatives in the same
manner as described in Example 1. In Example 3, the reaction was carried out in the presence
of a base (triethylamine). The results and reaction conditions are shown in Table 1 together
with those of Example 1. When a silyl derivative was used as in Examples 5-12, a solution of
catalytic amount (0.1 mmol) of tetrabutylammonium fluoride (a silicon atom-activating
agent) (1.0 M) in tetrahydrofuran (THF) was added to a solution of a silyl derivative and
arylsulfur trifluoride.
[00139] The properties and spectral data of the products are shown in the following:
[00140] 2-fluoroethyl 4-tert-butyl-2,6-dimethylbenzenesulfinate (1-2); 1H-NMR
(CDCl3) d 1.28 (s, 9H), 2.62 (s, 6H), 4.17-4.42 (m, 2H), 4.64 (dt, 2H, J = 47, 4 Hz), 7.04 (s,
2H); 19F-NMR (CDCl3) d -224.14 (m, IF); 13C-NMR (CDCl3) d 19.49, 31.09, 34.74, 67.15
(d, J = 20 Hz), 82.24 (d, J = 172 Hz), 127.27, 137.60, 137.91, 155.26. Elemental analysis
calculated for C14H21FO2S: C, 61.97%; H, 7.77%. Found; C, 61.97%; H, 7.73%.
[00141] 2-Fluoroethyl 4-methylbenzenesulfinate (1-3): 1H-NMR (CDCl3) d 2.38 (s,
3H), 3.75 (dq, 1H), 4.18 (dq, 1H), 4.50(dm, 2H, 7 = 47.5 Hz), 7.35 (d, 2H, 7 = 8.3 Hz), 7.56
(d, 2H, J = 8.3 Hz); 19F-NMR (CDCl3) d -224.16 (tt, 1F, 7 = 47.6, 28.1 Hz); 13C-NMR
(CDCl3): d 21.58, 62.62 (d, 7 = 20.2 Hz), 81.90 (d, J = 171.9 Hz), 125.35, 129.89, 141.23,
143.21.
[00142] 2-Fluoroethyl 4-fluorobenzenesulfinate (1-4): 1H-NMR (CDCl3) d 3.74 (dq,
1H), 4.16 (dq, 1H), 4.46 (dm, 2H, 7-47.0 Hz), 7.12 (m, 2H), 7.63 (m, 2H); 19F-NMR
(CDCl3) d-106.35 (s, 1F), -224.18 (tt, 1F, 7 = 47.6, 28.1 Hz); 13C-NMR (CDCl3) d 63.28 (d,
J = 20.2 Hz), 81.78 (d, J = 171.2 Hz), 116.44 (d, J = 22.4 Hz), 127.85 (d, J = 9.4 Hz), 140.15
(d, J = 2.8 Hz), 165.10 (d, J = 252.9 Hz).
[00143] 2-Fluoroethyl 4-Chlorobenzenesulfinate (1-5): 1H-NMR (CDCl3) d 3.75 (dq,
1H), 4.17 (dq, 1H), 4.48 (dm, 2H, 7 = 47.0 Hz), 7.42 (d, 2H, J = 8.6 Hz), 7.58 (d, 2H, J = 8.6
Hz); 19F-NMR (CDCl3) d -224.07 (tt, 1F, 7 = 47.6, 28.1 Hz); 13C-NMR (CDCl3) d 63.40 (d, 7
= 20.2 Hz), 81.76 (d, J = 171 Hz), 126.88, 129.49, 138.78, 142.83.
[00144] 2-Fluoroethyl 2,5-dimethylbenzenesulfinate (1-6): 1H-NMR (CDCl3) d 3.73
(dq, 1H), 4.18 (dq, 1H), 4.50 (dm, 2H, J = 47.1 Hz), 7.09 (d, 1H, J = 6.9 Hz), 7.21 (d, 1H, J =
6.9 Hz), 7.66 (s, 1H); 19F-NMR (CDCl3) d -223.87 (tt, IF, 7 = 47.0, 28.0 Hz); 13C-NMR
(CDCl3) d 17.54, 21.04, 63.08 (d, 7 = 21.0 Hz), 81.84 (d, J = 171.9 Hz), 124.59, 131.40,
133.27, 133.72, 136.38, 140.94.
[00145] 2-Fluoroethyl 2,6-bis(methoxymethyl)-4-tert-butylbenzenesulfinate (1-7): 1H-
NMR (CDCl3) d 1.32 (s, 9H), 3.39 (s, 6H), 4.15-4.40 (dm, 2H), 4.60 (dt, 2H, J = 46.7 HZ),
4.84 (d, AB type, 4H), 4.89 (s, 2H); 19F-NMR (CDCl3) (major isomer) d -223.95 (tt, 1F, J =
47.7, 28.1 Hz).
Examples 13-33. Preparation of fluoroalkvl arenesulfonates (1-8)~(I-32)
[00146] Various fluoroalkyl arenesulfinates were prepared by reaction of arylsulfur
trifluoride (III) with different diols and silyl derivates in the same manner as in Example 1.
The reactions were conducted in the presence or absence of a base or a silicon atom-
activating agent. The results and reaction conditions are shown in Table 2.
[00148] 2-Fluoropropyl benzenesulfinate (1-8): 1H-NMR (CDCl3) d 1.2-1.42 (m, 3H),
3.4-4.20 (m, 2H), 4.6- 5.0 (dm, 1H), 7.50-7.74 (m, 5H); 19F-NMR (CDCl3) d -180.45 (m, IF).
[00149] 2-Fluoropropyl 4-tert-butyl-2,6-dimefhylbenzenesulfinate (1-9): 1H-NMR
(CDCl3) d 1.20-1.40 (overlapped singlet with multiplet, 12H), 2.62 (s, 6H), 3.50-4.25 (m,
2H), 4.65-5.05 (m, 1H), 7.03 (s, 2H); 19F-NMR (CDCl3) d -180.48 (m, IF); 13C-NMR
(CDCl3) d 17.21(d, J = 22 Hz), 19.48, 31.09, 34.72, 71.08 (d, J = 22 Hz), 88.90 (d, J = 17
Hz), 127.22, 137.52, 138.12, 155.15.
[00150] 2-Fluorohexadecyl benzenesulfinate (1-10): 1H-NMR (CDCl3) d 0.86 (t, J =
6.5 Hz, 3H, CH3), 1.15-1.70 (br.m, 26H, (CH2)i3, 3.4-3.8 (m, 1H, CH), 3.95-4.25 (m, 1H,
CH), 4.4-4.8 (d m, J = 51 Hz, 1H, CHF), 7.45-7.60 (m, 3H, ArH), 7.20-7.80 (m, 2H, ArH);
19F-NMR (CDCl3) d -186.56 (m, IF, CF); 13C-NMR (CDCl3) d 14.23, 22.78, 24.74, 24.90,
28.37, 29.47, 29.60, 29.75, 31.11, 31.38, 21.02, 65.60 (d, J = 23 Hz), 91.8 (d, J = 173 Hz),
125.37, 129.19, 132.42, 144.46
[00151] 2-Fluorohexadecyl 4-tert-butyl-2,6-dimethylbenzenesulfinate (1-11): 1H-
NMR (CDCl3) d 0.88 (m, 3H, CH3), 1.2-1.35 (m, 35H, 13xCH2 & (CH3)3C), 2.63 (s, 6H,
2xCH3), 4.02-4.26 (m, 2H, CH2O), 4.67 (dm, J = 47.8 Hz, CHF), 7.04 (s, 2H, ArH); 19F-
NMR (CDCl3) (a mixture of distereomers or rotamers) d -186.99 (m, 0.75F), -186.36 (m,
0.25F); 13C-NMR (CDCl3) (major stereoisomer) 8 14.23, 19.49, 22.80, 24.82, 29.43, 29.48,
29.51, 29.61, 29.76, 31.09, 32.03, 34.72, (d, J = 22.3 Hz), 92.43 (d, J = 173.2 Hz), 127.21,
137.59,138.15,155.13.
[00152] 2-Fluoro-2-phenylethyl 4-tert-butyl-2,6-dimethylbenzenesulfinate (1-12): 1H-
NMR: (CDCl3): d 1.31 (s, 9H), 2.65 (s, 6H), 4.10-4.50 (m, 2H), 5.50-5.90 (m, 1H)
7.07 (s, 2H), 7.30-7.50 (m, 5H); 19F-NMR (CDCl3) d -183.86 (m, IF); 13C-NMR (CDCl3) d
19.51, 31.12, 34.71, 21.31, 22.07, 44.93, (d, J = 21 Hz), 73.23, 87.18 (d, J = 165 Hz), 127.16,
136.98, 138.75, 154.81.
[00153] 1,2-Diphenyl-2-fluoroethyl 4-tert-butyl-2,6-dimethylbenzenesulfinate (1-13):
1H-NMR (CDCl3) (as a mixture of two isomers of about 1:1 ratio) 8 1.29 and 1.31 (two
singlet, 9H), 2.38 and 2.45 (two singlet, 6H), 5.40-5.55 (m, 1H), 5.75 (m, 1H), 6.9-7.4 (m, 12
H); 19F-NMR (CDCl3) (as a mixture of two isomers of about 1:1 ratio): 8 -180.45 (dd, IF, J =
44.8, 13.0 Hz) and d-185.01 (dd, 1F, J = 46.5, 16.2 Hz); 13C-NMR (CDCl3) (a mixture of
two isomers of about 1:1 ratio) 8 19.13, 19.33, 31.14, 34.76, 81.32 (d, J = 26.7 Hz), 82.62 (d,
J = 28.2 Hz), 94.94 (d, J = 180.9 Hz), 95.04 (d, J = 180.6 Hz), 127.00, 127.08, 127.56,
127.62, 128.07, 128.32, 128.94, 135.12, 135.35, 135.63, 135.90, 137.44, 137.68, 138.06,
138.41, 139.44, 155.07, 155.22.
[00154] 3-Chloro-2-fluoropropyl benzenesulfinate (I-14): 1H-NMR (CDCl3) d 3.60-
3.86 (m, 3H, CH2C1 & CHO), 4.15-4.34 (m, 1H, CHO), 4.79 (dm, J = 46.1 Hz, CHO), 7.57
(m, 3H, ArH), 7.73 (m, 2H, ArH); 19F-NMR (CDCl3) d -188.03 (m, CF); 13C-NMR (CDCl3)
d 41.98 (d, J = 25.3 Hz), 61.89 (d, J = 24.5 Hz), 89.74 (d, J = 180.5 Hz), 125.40, 129.36,
132.75, 143.87; GC-MS (m/e, intensity): 236 (M+, 5), 142 (PhS02 + H, 35), 125 (M+-
ClCH2CHFCH2O, 100), 77 (C6H5+. 80), 45 (MeOCH2+, 100). Elemental analysis calculated
for C9H10ClFO3S: C, 45.67%; H, 4.26%. Found; C, 45.14%, H, 4.34%.
[00155] 2-Fluoro-(l-chloromethyl)ethyl benzenesulfinate (1-15): 1H-NMR (CDCl3) d
3.51 (m, 2H, CH2C1), 4.52-4.80 (m, 3H, CHO & CH2F), 7.58 (m, 3H, ArH), 7.77 (m, 2H,
ArH); 19F-NMR (CDCl3) d -231.93 (td, J = 47.5 Hz, 15.6 Hz, CH2F); 13C-NMR (CDCl3) d
41.57 (d, J = 7.2 Hz), 74.72 (d, J = 20.2 Hz), 82.11 (d, J = 173.9 Hz), 125.21, 129.32, 132.93,
144.50; GC-MS (m/e, intensity) 236 (M+, 5), 142 ( PhS02 + H, 10), 125 (M+-
C1CH2CHFCH2O, 100), 77 (C6H5+. 50).
[00156] 2-Fluoro-3-methoxy-1-propyl benzenesulfinate (1-16): 1H-NMR (CDCl3) d
3.38 (s, 3H, CH3), 3.50-3.68 (m, 2H, CH2O), 3.72-3.88 (m, 1H, CHOS), 4.15-4.30 (m, 1H,
CHOS), 4.74 (dm, J = 47.8 Hz, 1H, CHF), 7.57 (m, 3H, ArH), 7.74 (m, 2H, ArH); 19F-NMR
(CDCl3) d -193.51 (d, quin, J = 47.8, 22.4 Hz, CF); 13C-NMR (CDCl3) d 59.59, 62.99 (d, J =
23.8 Hz), 71.25 (d, J = 22.4 Hz), 90.32 (d, J = 173.1 Hz), 125.38, 129.29, 132.56, 144.21;
GC-MS (m/e, intensity): 232 (M+, 2), 125 (M+-MeOCH2CHFCH2O, 40), 91
(MeOCH2CHFCH2+, 75), 77 (C6H5+. 30), 45 (MeOCH2+, 100). Elemental analysis calculated
for C10H13FO3S: C, 51.71%; H, 5.64%. Found; C, 51.58%, H, 5.64%.
[00157] 2-Fluoro-(l-methoxymefhyl)ethyl benzenesulfinate (1-17): 1H-NMR
(CDCl3) d 3.28 (s, 3H, CH3), 3.40-3.49 (m, 2H, CH2O), 4.40-4.78 (m, 3H, CH2O & CHOS),
7.55 (m, 3H, ArH), 7.76 (m, 2H, ArH); 19F-NMR (CDCl3) d -230.55 (m, CH2F); 13C-NMR
(CDCl3) d 59.44, 70.91 (d, J = 7.2 Hz), 75.49 (d, J = 11.5 Hz), 82.86 (d, J = 172.5 Hz),
125.26, 129.14, 132.53, 145.07; GC-MS (m/e, intensity): 232 (M+, 2), 125 (M+-
MeOCH2CHFCH2O, 50), 91 (MeOCH2CHFCH2+, 90), 77 (C6H5+, 60), 45 (MeOCH2+, 100).
[00158] 2-Fluoro-3-phenoxy-propyl benzenesulfinate (1-18): 1H-NMR (CDCl3)d
3.78-4.00 (m, 1H, CHOS), 4.08-4.24 (m, 2H, CH2O), 4.24-4.44 (m, 1H, CHOS), 4.93 (dm, J
= 51.6 Hz, 1H, CHF), 6.88 (m, 2H, ArH), 6.99 (m, 1H, ArH), 7.29 (m, 2H, ArH), 7.56 (m,
3H, ArH), 7.73 (m, 2H, ArH); 19F-NMR (CDCl3) d -194.05 (d.quin, J = 51.6, 20.7 Hz, CF);
L3C-NMR (CDCl3) d 62.48 (d, J = 24.5 Hz), 66.48 (d, J = 24.5 Hz), 89.41 (d, J = 177.5 Hz),
114.64, 121.61, 125.42, 129.32, 129.66, 132.64, 144.04, 158.14; GC-MS (m/e, intensity): 294
(M+, 5), 201 (M+ - PhO, 10), 152 [( M+ - (PhSO2 + H), 45], 125 (M+-PhOCH2CHFCH2O, 70),
107 (PhOCH2+, 70), 77 (C6H5+, 100).
[00159] 2-Fluoro-1-(phenoxymethyl)ethyl benzenesulfinate (1-19): 1H-NMR
(CDCl3) d 4.04 (m, 2H, CH3O), 4.58-4.89 (m, 3H, CH2F & CHOS), 6.77 (m, 2H, ArH), 6.96
(m, H, ArH), 7.25 (m, 2H, ArH), 7.58 (m, 2H, ArH), 7.79 (m, 2H, ArH); 19F-NMR (CDCl3) d
-231.24 (dt, J = 47.5 Hz, 19.0 Hz), CH2F); 13C-NMR (CDCl3) d 65.84 (d, J = 6.5 Hz), 74.32
(d, J = 19.5 Hz), 82.74 (d, J = 173.2 Hz), 114.54, 121.54, 125.38, 129.23, 129.63, 132.70,
144.80, 157.91; GC-MS (m/e, intensity): 294 (M+, 5), 201 (M+ - PhO, 10), 152 [( M+ -
(PhSO2 + H), 45], 125 (M+-PhOCH2CHFCH2O, 70), 107 ( PhOCH2+, 70), 77 (C6H5+, 100).
[00160] 2-Fluoro-3-butenyl benzenesulfinate (1-20): 1H-NMR (CDCl3) (8): 3.48-3.82
(m, 1H, CHO), 4.04-4.22 (m, 1H, CHO), 4.95-5.48 (m, 3H, CHF and CH2=), 5.68-5.96 (m,
1H, CH=), 7.55 (m, 3H, ArH), 7.72 (m, 2H, ArH); 19F-NMR (CDCl3) d -185.48 (m, CHF).
[00161] 4-Fluoro-2-trans-butenyl benzenesulfinate (1-21): 1H-NMR (CDCl3) d 4.16
(m, 1H, CH=), 4.55 (m, 1H, CH=), 4.85 (dm, J = 48 Hz, 2H, CH2F), 5.86 (m, 2H, CH2O),
7.56 (m, 3H, ArH), 7.73 (m, 2H, ArH); 19F-NMR (CDCl3) d -215.67 (tm, J = 48 Hz. IF,
CHF); 13C-NMR (CDCl3) d 63.65, 82.18 (d, J=165.2 Hz), 125.35, 128.02 (d, J=11.5 Hz),
129.22, 129.45, 132.44, 144.48.
[00162] 2-Fluoro-7-octenyl benzenesulfinate (1-22): 1H-NMR (CDCl3) d 1.2-1.8 (m,
6H, (CH2)3), 2.02 (m, 2H, CH2), 3.45-3.78 (m, 1H, =CHH), 4.0-4.18 (m, 1H, =CHH), 4.59
(br.d, J = 50.5 Hz, 1H, CHF), 4.88-5.03 (m, 2H, CH2O), 5.67-5.84 (m, 1H, CH=), 7.53 (m,
3H, ArH), 7.73 (m, 2H, ArH); 19F-NMR (CDCl3) d -186.76 (m, CF); 13C-NMR (CDCl3) d
24.23, 28.51, 31.21 (d, J = 7.2 Hz), 33.51, 64.68, 64.98, 65.31, 65.61, 91.61 (d, J = 173.3 Hz),
114.75, 125.32, 129.51, 132.41, 138.48, 144.40.
[00163] 3-Fluoropropyl benzenesulfinate (1-23): 1H-NMR (CDCl3) d 1.70-2.10 (m,
2H), 3.30-4.70 (m, 4H), 7.45-7.75 (m, 5H); 19F-NMR (CDCl3) d -222.65 (m, IF); 13C-NMR
(CDCl3) d 30.86 (d, J = 19.5 Hz), 60.39 (d, J = 5.05 Hz), 80.25 (d, J = 165.4 Hz), 125.27,
129.20, 132.21, 136.36, 144.46.
[00164] 3-Fluoropropyl 4-tert-butyl-2,6-dimethylbenzenesulfinate (1-24): m.p. 62-63
°C; 1H-NMR (CDCl3) d 1.28 (s, 9H), 2.06-2.17 (dt, 2H, J = 25.7, 5.9 Hz), 2.62 (s, 6H), 4.21
(t, 2H, J = 6.2 Hz), 4.54 (dt, 2H, J = 46.7, 5.8 Hz), 7.03 (s, 2H); 19F-NMR (CDCl3) d -222.69
(tt, 1F, J = 58.5, 13 Hz); 13C-NMR (CDCl3) d 19.50, 31.10, 31.32 (d, J = 20.2 Hz), 43.73,
64.65 (d, J = 5.1 Hz), 80.29 (d, J = 165.4 Hz), 127.23, 137.38, 138.19, 155.08. Elemental
analysis calculated for C15H23FO2S: C, 62.90%; H, 8.09%. Found; C, 63.18%; H, 8.36%.
[00165] 3-Fluoro-1-methylbutyl 4-tert-butyl-2,6-dimethylbenzenesulfinate (1-25): 1H-
NMR (CDCl3) d 1.20-1.50 (singlet overlapped multiplets, 15H), 1.50-2.50 (m, 2H), 2.62 (s,
6H), 4.40-5.20 (m, 2H), 7.03 (m, 2H); 19F-NMR (CDCl3) d -175.08 (m, 1F); 13C-NMR
(CDCl3) d 19.48, 31.10, 31.32 (d, J = 20.2 Hz), 43.73, 64.65 (d, J = 5.1 Hz), 80.29 (d, J =
165.4 Hz), 127.23, 137.38, 138.19, 155.08. Elemental analysis calculated for C17H27FO2S: C,
64.93%; H, 8.65%. Found; C, 64.50%; H, 8.80%.
[00166] 3-Fluoro-1 -methylbutyl benzenesulfinate (1-26): 1H-NMR (CDCl3) d 0.50-
2.0 (m, 8H), 4.2-4.80 (m, 2H), 7.30-7.80 (m, 5H); 19F-NMR (CDCl3) (major isomer) 8 -
175.48 (dm, 1F);
[00167] 3-Fluoro-2-(benzyloxy)propyl benzenesulfinate (1-27): 1H-NMR (CDCl3) d
3.62-3.70 (m, 1H, CHOS), 3.80 (d.quint, J = 18.9 Hz, 4.6 Hz, 1H, CHO), 4.08-4.16 (m, 1H,
CHOS), 4.33-4.65 (m, 3H, CF2F & CHOS), 7.30 (m, 5H, ArH), 7.51 (m, 3H, ArH), 7.69 (m,
2H, ArH); 19F-NMR (CDCl3) d -230.66 (t,d J = 46.6 Hz, 19.0 Hz, CH2F); 13C-NMR (CDCl3)
d 61.71 (d, J = 7.2 Hz), 72.38, 75.88 (d, J = 20.2 Hz), 82.42 (d, J = 171.1 Hz), 125.43, 127.89,
128.03, 128.58, 129.30, 132.56, 137.76, 144.18.
[00168] 2-Bromo-3-fluoro-2-nitropropyl benzenesulfinate (1-28): 1H-NMR (CDCl3) d
4.0-5.34 (m, 4H, CH2), 7.5-7.8 (m, 5H, ArH); 19F-NMR (CDCl3) d -215.70 (m, 1F, CF); 13C-
NMR (CDCl3) d 61.94, 81.12 (d, J = 185.5 Hz), 87.52 (d, J = 20.2 Hz), 125.31, 129.57,
133.30, 143.06.
[00169] 4-Fluorobutyl benzenesulfinate (1-29): 1H-NMR (CDCl3) d 1.74 [m, 4H,
(CH2)2], 3.61 ( m, 1H, CHO), 4.06 (m, 1H, CHO), 4.40 (dm, J = 47 Hz, CF2H), 7.52 (m, 3H,
ArH), 7.68 (m, 2H, ArH); l9F-NMR (CDCl3) d: -218.98 (m, IF, CH2F); 13C-NMR (CDCl3) d
25.75 (d, J = 4.3 Hz), 26.92 (d, J = 20.2 Hz), 63.95, 83.44 (d, J = 164.5 Hz), 125.27, 129.16,
132.26, 144.60; GC-MS (m/e, intensity) 216 (M+, 2), 142 (M+-FCH2CH2CH2CH, 30), 125
(PhSO+, 50), 78 (C6H6+. 100), 55 (CH2CH2CH2CH+, 80).
[00170] 4-Fluoro-2-cis-butenyl benzenesulfinate (1-30): 1H-NMR (CDCl3) d 4.2 (m,
1H, CH=), 4.58 (m, 1H, CH=), 4.87 (dd, J = 47 Hz, 6.0 Hz, 2H, CH2F), 5.75 (m. 2H, CF2O),
7.57 (m, 3H, ArH), 7.73 (m, 2H, ArH); 19F-NMR (CDCl3) d -214.51 (t,d, J = 47 Hz, 14 Hz,
CH2F); 13C-NMR (CDCl3): 5: 59.30, 65.56 (d, J = 23 Hz), 79.66, 91.11 (d, J = 174.6 Hz),
125.38, 129.25, 132.55, 144.38.
[00171] [(o-Fluoromethyl)phenyl]methyl benzenesulfinate (1-31): 1H-NMR (CDCl3)
54.63 (d, J = 11.7 Hz, 1H, CHO), 5.13(d, J = 11.7 Hz, 1H, CHO), 5.40 (dm, J = 47.8 Hz, 2H,
CH2F), 7.35 (m, 4H, ArH), 7.56 (m, 3H, ArH), 7.74 (m, 2H, ArH); 19F-NMR (CDCl3) d -
208.04 (t, J = 47.8, CH2F); 13C-NMR (CDCl3) d 62.95, 82.26 (d, J = 165.3 Hz), 125.38,
129.02, 129.13, 129.22, 129.28, 129.36, 130.34, 132.53, 133.71, 135.14 (d, J = 15.8 Hz),
144.33; GC-MS (m/e, intensity) 264 (M+, 2), 123 (PhSO2+, 100), 77 (C6H5+, 10).
[00172] 5-Fluoropentyl benzenesulfinate (1-32): 1H-NMR (CDCl3) d 1.36-1.49 (m,
2H, CH2), 1.54-1.73 (m, 4H, 2xCH2), 3.58 (m, 1H, CHO), 4.02 (m, 1H, CHO), 4.38 (dt,
J=47.4, 5.8 Hz, CH2F), 7.52 (m, 3H, ArH), 7.68 (m, 2H, ArH); 19F-NMR (CDCl3) d -218.45
(tt, J=47.4, 25.2 Hz); 13C-NMR (CDCl3) d 21.68 (d, J=5 Hz), 29.32, 29.90 (d, J=19.5 Hz),
64.29, 83.84 (d, J=164.6 Hz), 125.29, 129.14, 132.20, 144.67; GC-MS (m/e, intensity) 230
(M+, 1), 143 (M+-F(CH2)4C, 100), 125 (PhSO+, 50), 78 (C6H6+, 70).
Examples 34-36. Preparation of a cyclic type of fluoroalkvl arenesulfinates (1-33) - (1-35)
[00173] A cyclic type of fluoroalkyl arenesulfinate was prepared by reaction of
arylsulfur trifluoride (III) with different cycloalkanediols or silyl derivatives in the same
manner as in Example 1. The results and reaction conditions are shown in Table 3.

[00174] The properties and spectral data of the products (I-33) ~ (I-35) are shown in
the following:
[00175] l-Fluoro-2-(phenylsulfmyloxy)cyclopentane (1-33): 1H-NMR (CDCl3) d
1.50-2.0 (m, 6H), 4.58-4.80 (m, 1H), 5.00 (dt, 1H, J = 51.6, 2.4 Hz), 7.35-7.55 (m, 3H), 7.58-
7.80 (m, 2H); 19F-NMR (CDCl3) (major isomer) 8 -179.68 (m, 1F); 13C-NMR (CDCl3) d
21.00, 30.25, 30.80, 81.36 (d. J = 28.9 Hz), 98.32 (d. J = 177.7 Hz), 125.80, 129.19, 132.44,
184.85.
[00176] 1-Fluoro-2-(4-tert-butyl-2,6-dimethylphenylsulfinyloxy)cyclopentane (1-34):
a mixture of two isomers (92:8); viscous liquid; spectral data of major isomer: 1H-NMR
(CDCl3) d 1.28 (s, 9H), 1.70-2.25 (m, 6H), 2.61 (s, 6H), 4.70-5.20 (m, 2H), 7.01 (s, 2H); 19F-
NMR (CDCl3) d -179.7 (m, 1F); 13C-NMR (CDCl3) d 19.47, 21.11, 30.34 (d, J = 21.0), 31.10,
34.73, 83.78 (d, J = 27.5 Hz), 98.24 (d, J = 178.4 Hz), 127.20, 137.26, 138.46, 155.09.
Elemental analysis calculated for C17H25FO2S: C, 65.35%; H, 8.09%. Found; C, 64.99%; H,
8.19%.
[00177] l-Fluoro-2-(4-tert-butyl-2,6-dimethylphenylsulfinyloxy)cyclohexane(I-35):
a mixture of two isomers (92:8): viscous liquid: Spectral data of major isomer: 1H-NMR
(CDCl3) d 1.20-1.33 (m, 11H), 1.35-2.38 (m, 6H), 2.62 (s, 6H), 4.20-4.27 (m, 2H), 7.02 (s,
2H); 19F-NMR (CDCl3) d -179.89 (br.d, 1F); 13C-NMR (CDCl3) d 19.42, 22.98 (d, J = 10.1
Hz), 23.65, 30.80 (d, J = 17.3 Hz), 31.12, -32.04, 34.70, 81.09 (d, J = 17.3 Hz), 93.50 (d, J =
179.2 Hz), 127.05, 137.22, 138.96.
Examples 37~43. Preparation of fluoroalkvl arenesulfinamide (I-36)~(I-42)
[00178] General procedure for Examples 37~42: An arylsulfur trifluoride was
dissolved in dichloromefhane in a vessel made of fluoropolymer (PFA) under nitrogen. A
solution of a trimefhylsilyl derivative of an amino alcohol in dichloromethane was slowly
added, at room temperature. The mixture was stirred at room temperature for 1 hour, and
poured on aqueous sodium carbonate solution and extracted with dichloromethane. The
organic layer was dried over anhydrous magnesium sulfate and filtered. Removal of solvent
at reduced pressure gave the desired product. The results and reaction conditions are shown
in Table 4.
[00179] Procedure for Example 43; Both reactants were dissolved in equal volume of
heptane (4ml each). About 17 ml of heptane was taken in a fluoropolymer (PFA) vessel and
heated to 100 °C. Both reactants were taken in separate syringe connected with Teflon tube
on the end. Both the Teflon tube ends were immersed in heptane in the PFA vessel. Addition
was done simultaneously for 2 hours. After complete addition the reaction mixture was
further stirred for 0.5 hour at 100 °C. After the reaction, insoluble black resin was removed,
and the solution was washed with aqueous sodium bicarbonate solution, dried on magnesium
sulfate, and filtered. Removal of solvent at reduced pressure gave the product. The results
and reaction conditions are shown in Table 4.

[00180] The properties and spectral data of the products are shown in the following:
[00181] N-(2-Huoroethyl)-N-methyl-benzenesulfmamide (1-36): 1H-NMR (CDCl3) d
2.54 (s, 3H), 3.2-3.4 (m, 2H), 4.40 (dm, 2H, J = 44 Hz) 7.2-7.6 (m, 5H); 19F-NMR (CDCl3) d
-220.91 (tt, IF, J = 45, 26 Hz); 13C-NMR: (CDCl3): d 33.84, 52.82 (d, J = 21 Hz), 81.84 (d, J
= 170.5 Hz), 126.11, 128.93, 131.02, 143.57.
[00182] N-(2-Fluoroethyl)-N-methyl-p-fluorobenzenesulfinamide (1-37): 1H NMR
(CDCl3) d 2.54 (s, 3H), 3.2-3.4 (m, 2H), 4.45 (dm, 2H, J = 47.1 Hz) 7.08 (t, 2H, J = 8.6 Hz),
7.54 (m, 2H); 19F-NMR (CDCl3) d -109.22 (m, 1F), -220.11 (tt, 1F, J = 48.4, 24.2 Hz); 13C-
NMR (CDCl3) d 33.50, 52.14 (d, J = 20.2 Hz), 82.05 (d, J = 170.5 Hz), 116.1 (d, J = 22.4
Hz), 128.50 (d, J = 8.7 Hz), 139.28 (d, J = 2.8 Hz), 164.36 (d, J = 251.4 Hz).
[00183] N-(2-Ruoroethyl)-N-methyl-p-chlorobenzenesulfinamide (1-38): 1H-NMR
(CDCl3) d2.49 (s, 3H), 3.2-3.4 (m, 2H), 4.40 (dm, 2H, J = 47.1 Hz) 7.20-7.50 (m, 4H); 19F-
NMR (CDCl3) d -220.95 (tt, IF, J = 47.5, 26 Hz); 13C-NMR (CDCl3) d 33.52, 52.18 (d, J =
21 Hz), 81.77 (d, J = 170.5 Hz), 127.67, 129.13, 137.23, 142.24.
[00184] N-Benzyl-(2-fluoroethyl)-benzenesulfinamide (1-39): 1H-NMR (CDCl3) d
3.2-3.4 (m, 2H), 4.1-4.4 (m, 4H), 7.1-7.8 (m, 10H), 1.28 (s, 9H), 2.62 (s, 6H), 4.56 (m, 2H),
4.64 (td, 2H, J = 47, 4 Hz), 7.04 (s, 2H); 19F-NMR (CDCl3) d -220.51 (tt, 1F, J = 47, 25.4
Hz); 13C-NMR (CDCl3): 8 47.77 (d, J = 21 Hz), 52.54, 82.12 (d, J = 170.5 Hz), 126.27,
127.88, 128.73, 128.92, 129.07, 131.24, 136.41, 144.09.
[00185] N-Benzyl-(2-fluoroethyl)-p-fluorobenzenesulfinamide (1-40): 1H-NMR
(CDCl3) d 3.1-3.4 (m, 2H), 4.1-4.5 (m, 4H), 7.1-7.3 (m, 7H), 7.6-7.7 (m, 2H); 19F-NMR
(CDCl3) d -108.69 (s, 1F), -220.77 (tt, 1F, J = 47, 25.5Hz); 13C-NMR (CDCl3) d 47.81 (d, J =
20.2 Hz), 52.17, 81.89 (d, J = 170.5 Hz), 116.24 (d, J = 22.4 Hz), 127.94, 128.58, 128.71,
128.77, 128.86, 136.20, 139,68 (d, J = 2.2 Hz), 164.47 (d, J = 251.4 Hz).
[00186] N-Benzyl-(2-fluoroethyl)-p-chlorobenzenesulfinamide (1-41): 1H-NMR
(CDCl3) d 3.11-3.45 (m, 2H), 4.1-4.52 (m, 4H), 7.1-7.4 (m, 5H), 7.44 (d, 2H, J = 8.3 Hz), -
7.65 (d, 2H, J = 8.3 Hz); 19F-NMR (CDCl3) d -220.73 (tt, IF, J = 47, 25 Hz); 13C-NMR
(CDCl3) d47.90 (d, J = 21 Hz), 52.34, 81.89 (d, J = 170.5 Hz), 127.84, 127.99, 128.81,
128.89, 129.32, 136.12, 137.53.
[00187] N-Benzyl-(2-fluoroethyl)-4-tert-butyl-2,6-dimethylbenzenesulfinamide (I-
42): 1H-NMR (CDCl3) d 1.30 (s, 9H), 2.59 (s, 6H), 3.42 (td, 2H, J = 24.4, 5.5 Hz), 4.23-4.51
(m, 4H) 7.04 (s, 2H), 7.21-7.31 (m, 5H); 19F-NMR (CDCl3) d -219.68 (m, IF); 13C-NMR
(CDCl3) d 20.34, 31.18, 34.58, 48.66 (d, J = 21.6 Hz), 53.27, 82.24 (d, J = 170.5 Hz), 127.74,
127.83, 128.65, 128.88, 138.03, 153.89.
Example 44. Preparation of 3-fluoro-1-phenylsulfinyl-pyrrolidine (1-43)

[00188] Each of two reactants (4.63 mmol each) was dissolved in equal volume of
heptane (2 ml each). Each solution of the reactants was separately and simultaneously added
through a Teflon tube with a syringe pump to a stirred 20 mL dry heptane in a fluoropolymer
(PFA) vessel heated on 90 °C oil bath. The addition took 1 hour. After addition, the reaction
mixture was further stirred for 0.5 hour at 90 °C. After cooling, insoluble black resin was
removed, and the solution was washed with aqueous sodium bicarbonate solution, dried on
magnesium sulfate, and filtered. Removal of solvent at reduced pressure gave 3-fluoro-1-
phenylsulfinylpyrroline (T43) as a 1:0.88 mixture of stereoisomers: Yield, about 60%; 1H-
NMR (CDCl3) d 2.10-2.29 (m, 2H), 3.0-3.65 (m, 4H), 5.20 (dm, 1H), 7.25-7.80 (m, 5H); 19F-
NMR (CDCl3) d-174.74 (m, 1F); 13C-NMR (CDCl3) d 43.40, 50.34 (d, J=20 Hz), 52.27 (d,
J=20 Hz), 93.15 (d, J=176.8 Hz), 125.49, 128.97, 130.71, 136.58,
Example 45. Preparation of 3-fluoro-1 -(4-tert-butyl-2,6-dimethvlphenylsulfinyl)-pyrrolidine

[00189] 4-tert-Butyl-2,6-dimethylphenylsulfur trifluoride (6.0 mmol) was taken in a
Teflon vessel and dissolved in 20 ml of dry dichloromethane. Triethylamine (12.1 mmol) was
added at room temperature followed by the addition of a solution of (± )-3-pyrrolidinol (6.0
mmol) in 5 ml of dry dichloromethane. The reaction mixture was refluxed for 10 hours. After
cooling to room temperature, the reaction mixture was poured in aqueous sodium carbonate
solution. The mixture was extracted with dichloromethane, and the organic layer was
separated and dried on magnesium sulfate. After filtration, the filtrate was evaporated to
dryness and the residue was column-chromatographed on silica gel using a 2:1 mixture of
ether and hexane to give 1-(4-tert-butyl-2,6-dimethylphenylsulfinyl)-3-fluoropyrrolidine (I-
44): Yield 72%. 19F NMR showed that the product was a 1:0.66 mixture of two
stereoisomers. 19F-NMR (CDCl3) d - 173.28 (m) and -174.44 (m) in an integral ratio of
1:0.66; 1H-NMR (CDCl3) d 1.27 (s, 9H), 2.10-2.20 (m, 2H), 2.53 (s, 6H), 3.10-3.70 (m, 4H),
4.90-5.50 (m, 1H), 6.98 (s, 2H); 13C-NMR (CDCl3) major isomer: 8 19.98, 31.17, 34.48,
43.95, 53.43, (d, J = 23.8 Hz), 92.97 (d, J = 178.4 Hz) 127.48, 134.63, 137.44, 153.32, minor
isomer: 8 19.98, 31.13, 34.48, 46.24, 51.60 (d, J = 23.8 Hz), 93.22 (d, J = 178.4 Hz) 127.48,
134.94, 137.35, 153.32. Elemental analysis calculated for C16H24FNOS: C, 64.61%; H,
8.13%; N, 4.71%. Found; C, 64.08%; H, 8.21%; N, 4.53%.
Example 46. Preparation of 2-fluoromethyl-1-(phenylsulfinyl)pyrrolidine (1-45)

[00190] A solution of 3.55 mmol of 1-trimethylsilyl-2-[(trimethylsilyloxy)methyl]-
pyrrolidine in 2.5 mL of dry dichloromethane was slowly added to a solution of 3.55 mmol of
phenylsulfur trifluoride in 2.5 mL of dry dichloromethane at room temperature. 1-
Trimethylsilyl-2-[(trimethylsilyloxy)methyl]-pyrrolidine was prepared from (s)-(+)-2-
pyrrolidinemethanol by a usual method. The reaction mixture was stirred at room temperature
for 3 hours, and poured on aqueous sodium carbonate solution and extracted with
dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and
filitered. Romovel of solvent at reduced pressure gave 2-fluoromethyl-(l-phenylsulfmyl)-
pyrrolidine (1-45): Yield 78%. The product was a 6.25:1 mixture of two stereoisomers.
Spectral data for a major isomer are shown in the following: 1H-NMR (CDCl3) d 1.60-1.90
(m, 4H), 3.2-4.04 (m, 3H), 3.2-3.4 (m, 2H), 4.20-4.50 (dm, 2H, J = 51.5 Hz) 7.00-7.70 (m,
5H); 19F-NMR (CDCl3) d -224 (dt, 1F, J = 47.5, 17.3 Hz); 13C-NMR (CDCl3) d 24.94, 28.40,
42.12, 60.51 (d, J = 20 Hz), 84.83 (d, J = 174 Hz), 125.83, 128.94, 130.72, 144.38.
Example 47. Preparation of phenylsulfur chlorotetrafluoride (IV-I)

[00191] A 500 mL round bottom glassware flask was charged with diphenyl disulfide
(33.0 g, 0.15 mol), dry potassium fluoride (KF) (140 g, 2.4 mol) and 300 mL of dry
acetonitrile. The stirred reaction mixture was cooled on an ice/water bath under a flow of
nitrogen (N2) (18 mL/min). After N2 was stopped, chlorine (Cl2) was bubbled into a reaction
mixture at the rate of about 70 mL/min. The Cl2 bubbling took about 6.5 hours. The total
amount of Cl2 used was about 1.2 mol. After Cl2 was stopped, the reaction mixture was
stirred for additional 3 hours. N2 was then bubbled through for 2 hours to remove an excess
of Cl2. The reaction mixture was then filtered with 100 mL of dry hexane in air. About 1 g of
dry KF was added to the filtrate. The KF restrains possible decomposition of the product. The
filtrate was evaporated under vacuum and the resulting residue was distilled at reduced
pressure to give a colorless liquid (58.0 g, 88 %) of phenylsulfur chlorotetrafluoride (IV-1):
b.p. 80°C/20 mmHg; 1H NMR (CD3CN) 7.79-7.75 (m, 2H, aromatic), 7.53-7.49 (m, 3H,
aromatic); 19F NMR (CD3CN) 136.7 (s, SF4C1). The NMR analysis showed phenylsulfur
chlorotetrafluoride obtained is a trans isomer.
Examples 48-62. Preparation of arylsulfur chlorotetrafluorides (IV-1~12)
[00192] Substituted and unsubstituted arylsulfur chlorotetrafluorides (IV-1~12) were
synthesized from sulfur compounds shown in Table 5 by a similar procedure as in Example
47. Table 5 shows the synthesis of the substituted and unsubstituted arylsulfur
chlorotetrafluorides (IV-1~12). Table 5 also shows the starting materials and other chemicals,
solvents, reaction conditions, and results, together with those of Example 47.
[00193] The properties and spectral data of the product (IV-1) obtained by Examples
47-50 are shown in Example 47. The properties and spectral data of the products obtained by
Examples 51-62 are shown by the following:
[00194] p-Methylphenylsulfur chlorotetrafluoride (IV-2): b.p. 74-75°C/5 mmHg; 1H
NMR (CD3CN) d 7.65 (d, 2H, aromatic), 7.29 (d, 2H, aromatic), 2.36 (s, 3H, CH3); 19F NMR
(CD3CN) 5 137.66 (s, SF4C1); High resolution mass spectrum; found 235.986234 (34.9%)
(calcd for C7H7F4S37Cl; 235.986363), found 233.989763 (75.6%) (calcd for C7H7F4S35Cl;
233.989313). The NMR shows that p-methylphenylsulfur chlorotetrafluoride obtained is a
trans isomer.
[00195] p-(tert-Butyl)phenylsulfur chlorotetrafluoride (IV-3): b.p. 98 °C/0.3 mmHg;
m.p. 93 °C; 1H NMR (CDCl3) d 1.32 (s, 9H, C(CH3)3), 7.43 (d, J=9.2 Hz, 2H, aromatic), 7.64
(d, J=9.2 Hz, 2H, aromatic); 19F NMR d 138.3 (s, SF4Cl). High resolution mass spectrum;
found 278.034576 (8.8%) (calcd for C10H1337C1F4S; 278.033313), found 276.037526 (24.7%)
(calcd for C10H1335ClF4S; 276.036263). Elemental analysis; Calcd for C10H13ClF4S; C,
43.40%; H, 4.74%. Found; C, 43.69%, H, 4.74%. The NMR showed that p-(t-
butyl)phenylsulfur chlorotetrafluoride was obtained as a trans isomer.
[00196] p-Fluorophenylsulfur chlorotetrafluoride (IV-4): b.p. 60°C/8 mmHg; 1H NMR
(CD3CN) 7.85-7.78 (m, 2H, aromatic), 7.25-7.15 (m, 2H, aromatic); 19F NMR (CD3CN)
137.6 (s, SF4Cl), -108.3 (s, CF); High resolution mass spectrum; found 239.961355 (37.4%)
(calcd for C6H4F5S37Cl; 239.961291), found 237.964201(100%) (calcd for C6H4F5S35Cl;
237.964241). The NMR shows that p-fluorophenylsulfur chlorotetrafluoride obtained is a
trans isomer.
[00197] o-Fluorophenylsulfur chlorotetrafluoride (IV-5): b.p. 96-97°C/20 mmHg; 1H
NMR (CD3CN) 7.77-7.72 (m, 1H, aromatic), 7.60-7.40 (m, 1H, aromatic), 7.25-7.10 (m, 2H,
aromatic); 19F NMR (CD3CN) 140.9 (d, SF4Cl), -107.6 (s, CF); High resolution mass
spectrum; found 239.961474 (25.4%) (calcd for C6H4F5S37Cl; 239.961291), found
237.964375 (69.8%) (calcd for C6H4F5S35Cl; 237.964241). The NMR shows that o-
fluorophenylsulfur chlorotetrafluoride obtained is a trans isomer.
[00198] p-Chlorophenylsulfur chlorotetrafluoride (IV-6): b.p. 65-66 °C/2 mmHg; 1H
NMR (CDCl3) d 7.38 (d, 2H, J=9.1 Hz), 7.65 (d, 2H, J=9.1 Hz); 19F NMR (CDCl3) 137.4 (s,
4F, SF4Cl). High resolution mass spectrum; found 257.927507 (13.3%) (calcd for
C6H4F4S37Cl2; 257.928790), found 255.930746 (68.9%) (calcd for C6H4F4S37Cl35Cl;
255.931740), found 253.933767 (100.0%) (calcd for C6H4F4S35Cl2; 253.934690). The NMR
showed that p-chlorophenylsulfur chlorotetrafluoride obtained is a trans isomer.
[00199] p-Bromophenylsulfur chlorotetrafluoride (IV-7): m.p. 58-59 °C; 1H NMR
(CD3CN) d 7.67 (s, 4H, aromatic); 19F NMR (CD3CN) 8 136.56 (s, SF4Cl); High resolution
mass spectrum; found 301.877066 (16.5%) (calcd for C6H481Br37ClF4S; 301.879178), found
299.880655 (76.6%) (calcd for C6H481Br35ClF4S; 299.881224 and calcd for C6H479Br37CIF4S;
299.882128), found 297.882761 (77.4%) (calcd for C6H479Br35CIF4S; 297.884174).
Elemental analysis; calcd for C6H4BrClF4S; C, 24.06%; H, 1.35%; found, C, 24.37%; H,
1.54%. The NMR showed that p-bromophenylsulfur chlorotetrafluoride was obtained as a
trans isomer.
[00200] m-Bromophenylsulfur chlorotetrafluoride (IV-8): b.p. 57-59°C/0.8 mmHg; 1H
NMR (CD3CN) 7.90-7.88 (m, 1H, aromatic), 7.70-7.50 (m, 2H, aromatic), 7.40-7.30 (m, 1H,
aromatic); 19F NMR (CD3CN) 136.74 (s, SF4Cl). High resolution mass spectrum; found
301.878031 (29.1%) (calcd for C6H481Br37ClF4S; 301.879178), found 299.881066 (100%)
(calcd for C6H481Br 35CIF4S; 299.881224 and calcd for C6H479Br37CIF4S; 299.882128), found
297.883275 (77.4%) (calcd for C6H479Br35CIF4S; 297.884174). The NMR showed that m-
bromophenylsulfur chlorotetrafluoride obtained was a trans isomer.
[00201] p-Nitrophenylsulfur chlorotetrafluoride (IV-9): m.p. 130-131 °C; 1H NMR
(CD3CN) 8.29 (d, J=7.8 Hz, 2H, aromatic), 8.02 (d, J=7.8 Hz, 2H, aromatic); 19F NMR
(CD3CN) 134.96 (s, SF4Cl); High resolution mass spectrum; found 266.956490 (38.4%)
(calcd for C6H437ClF4NO2S; 266.955791), found 264.959223 (100%) (calcd for
C6H435ClF4NO2S; 264.958741). Elemental analysis; calcd for C6H4ClF4NO2S; C, 27.13%; H,
1.52%; N, 5.27%; found, C, 27.16%; H, 1.74%; N, 4.91%. The NMR shows that p-
nitrophenylsulfur chlorotetrafluoride obtained is a trans isomer.
[00202] 2,6-Difluorophenylsulfur chlorotetrafluoride (IV-10): The product (b.p. 120-
122 °C/95-1010mmHg) obtained from Example 14 is a 6:1 mixture of trans- and cis-isomers of
2,6-difluorophenylsulfur chlorotetrafluoride. The trans-isomer was isolated as pure form by
crystallization; mp. 47.6-48.3 °C; 19F NMR (CDCl3) d 143.9 (t, J=26.0 Hz, 4F, SF4), -104.1
(quintet, J=26.0 Hz, 2F, 2,6-F): 1H NMR (CDCl3) d 6.97-7.09 (m, 2H, 3,5-H), 7.43-7.55 (m,
1H, 4-H); 13C NMR (CDCl3) d 157.20 (d, J=262.3 Hz), 133.74 (t, J=11.6 Hz), 130.60 (m),
113.46 (d, J=14.6 Hz); high resolution mass spectrum; found 257.950876 (37.6%) (calcd for
C6H337C1F6S; 257.951869), found 255.955740 (100%) (calcd for C6H335ClF6S; 255.954819);
elemental analysis; calcd for C6H3ClF6S; C, 28.08%, H, 1.18%; found; C, 28.24%, H, 1.24%.
The cis-isomer was assig ned in the following; 19F NMR (CDCl3) d 158.2 (quartet, J=161.8
Hz, IF, SF), 121.9 (m, 2F, SF2), 76.0 (m, 1F, SF). The 19F NMR assignment of aromatic
fluorine atoms of the cis-isomer could not be done because of possible overlapping of the
peaks of the trans-isomer.
[00203] 2,4,6-Trifluorophenylsulfur chlorotetrafluoride (IV-11): trans-isomer; m.p.
55.8-56.7 °C; 19F NMR (CDCl3) d 144.07 (t, J=26.0 Hz, 4F, SF4), -99.80 (t, J=26.0 Hz, 2F, o-
F), -100.35 (s, IF, p-F); 1H NMR (CDCl3) d 6.79 (t, J=17.5 Hz, m-H); 13C NMR (CDCl3) d
164.16 (dt, J=164.2 Hz, 15.2 Hz, 4-C), 158.18 (dm, J=260.7 Hz, 2-C), 127.7 (m, 1-C), 102.1
(tm, J=27.8 Hz, 3-C). Elemental analysis; calcd for C6H2ClF7S; C, 26.24%; H, 0.73%; found,
C, 26.23%; H, 1.01%. The NMR shows that 2,4,6-trifluorophenylsulfur chlorotetrafluoride
obtained is a trans isomer.
[00204] 2,3,4,5,6-Pentafluorophenylsulfur chlorotetrafluoride (IV-12): The product
(b.p. 95-112 °C/100 mmHg) obtained from Experiment 16 was a 1.7:1 mixture of trans and
cis isomers of 2, 3, 4, 5, 6-pentafiuorophenylsulfur chlorotetrafluoride. The isomers were
assigned by 19F NMR: The trans isomer; 19F NMR (CDCl3) d 144.10 (t, J=26.0 Hz, 4F, SF4),
-132.7 (m, 2F, 2,6-F), -146.6 (m, 1F, 4-F), -158.9 (m, 2F, 3,5-F); 13C NMR (CDCl3) d 143.5
(dm, J=265.2 Hz), 141.7 (dm, J=263.7 Hz), 128.3 (m). The cis isomer; 19F NMR (CDCl3) d
152.39 (quartet, J=158.9 Hz, 1F, SF), 124.32 (m, 2F, SF2), 79.4 (m, 1F, SF), -132.7 (m, 2F,
2,6-F), -146.6 (m, 1F, 4-F), -158.9 (m, 2F, 3,5-F). High resolution mass spectrum of a 1.7:1
mixture of the trans and cis isomers; found 311.923124 (15.5%) (calcd for C637ClF9S;
311.923604), found 309.926404 (43.1%) (calcd for C635ClF9S; 309.926554).
Example 63. Preparation of fluoroalkvl benzenesulfinate (1-1) by two-step method from
phenylsulfur chlorotetrafluoride by action of pyridine as a reducing substance

[00205] Into a solution of 2.04 mmol of phenylsulfur chlorotrifluoride in 5 mL of dry
dichloromethane in a fluoropolymer vessel, was added 4.08 mmol of pyridine. The reaction
mixture was stirred at room temperature for 1.5 hours. 19F NMR showed complete
consumption of phenylsulfur chlorotetrafluoride and formation of phenylsulfur trifluoride.
Into the reaction mixture, a solution of 2.00 mmol of bis(trimethylsilyl ether) of ethylene
glycol in 1 mL of dry dichloromethane was slowly added during about 20 minutes. The
reaction mixture was stirred for 2 hours and poured on aqueous sodium carbonate solution.
The organic layer was washed with water and dried over anhydrous magnesium sulfate and
filtered. Removal of solvent at reduced pressure gave 2-fluoroethyl phenylsulfinate (I-1).
Examples 64-67. Preparation of fluoroalkvl arenesulfinate by a two-step method from
arylsulfur halotetrafluoride by action of a reducing substance.
[00206] Various fluoroalkyl arenesufinates were prepared in a similar manner as
described in Example 63. The results and reaction conditions are shown in Table 6 together
wth the results and reaction conditions of Example 63.

[00207] Spectral data of I-1, I-3 and I-5 are as shown before. Data of I-46 and I-47
are shown in the following:
[00208] 2-Fluoroethyl p-(tert-butyl)benzenesulfinate (1-46): 1H-NMR (CDCl3) d 3.75
(m, 1H), 4.20 (m, 1H), 4.48 (dm, 2H, J = 47 Hz), 7.51 (m, 3H), 7.63 (m, 2H); 19F-NMR
(CDCl3) d -224.15 (tt, J = 47.6 Hz, 28.4 Hz, 1F, CH2F); 13C-NMR (CDCl3) d: 31.10, 35.30,
63.0 (d, J = 20.0 Hz), 81.95 (d, J = 172 Hz), 125.19, 126.28, 128.25, 141.18.
[00209] 2-Fluoroethyl p-nitrophenylsulfinate (1-47): 1H-NMR (CDCl3) d 3.64-3.75
(m, 1H), 3.82-4.0 (m, 1H), 4.20-4.40 (m, 1H), 4.44-4.70 (m, 1H), 7.0-8.0 (m, 2H), 8.35-8.47
(m, 2H); 19F-NMR (CDCl3) d -224.75 (tt, 1F, J = 45.5, 28.2 Hz); 13C-NMR (CDCl3) d 64.59
(d, J = 20.2 Hz), 80.58 (q, J = 172.5 Hz), 124.48, 124.64, 126.90, 129.47, 150.37, 180.58.
Example 68. Preparation of 2-fluoroethyl p-nitrobenzenesulfinate (1-47) by a reaction of
Me3SiOCH2CH2OSiMe3 and p-nitrophenylsulfur chlorotetrafluoride in the presence of a
reducing substance (pyridine)

[00210] p-Nitrophenylsulfur chlorotetrafluoride (2.0 mmol) and
Me3SiOCH2CH2OSiMe3 (2.0 mmol) were dissolved in 4 ml of dichloromethane in a
fluoropolymer (PFA) vessel. Into the solution, pyridine (4.0 mmol) was added at room
temperature. The reaction mixture was stirred at room temperature for 5 hours and washed
with water. The organic dichloromethane layer is dried over anhydrous magnesium sulfate
and filtered. Removal of solvent gave a crude product, which was chromatographed using a
1:8 mixture of ether and hexane as an eluent to give 2-fluoroethyl p-nitrophenylsulfinate (I-
47): Yield 60%. The spectral data are shown in Example 67.
Example 69. Preparation of 4-tert-butyl-2,6-dimethylphenylsulfinyl fluoride.

[00211] Acetic acid (240 mg, 4 mmol) was added to a stirred solution of 4-tert-butyl-
2,6-dimethylphenylsulfur trifluoride (1.00g, 4.00 mmol) in 5 mL of dichloromethane in a
fluoropolymer vessel cooled on an ice bath. The bath was removed after 0.5 hour and the
reaction mixture was stirred at room temperature for additional 0.5 hour. 19F-NMR analysis
of the reaction mixture showed that 4-tert-butyl-2,6-dimetylphenylsulfinyl fluoride was
produced in 89% yield. After the reaction, the reaction mixture was evaporated to dryness by
vacuum pump. 4-tert-Butyl-2,6-dimethylphenylsulfinyl fluoride was obtained as a solid and
used for the next reactions (Examples 70 and 71) without further purification. Another
product, CH3COF, was easily removed by vacuum pump because of its low boiling point (bp
20-21 °C).
Example 70. Preparation of(2S,4S)-N-(4-tert-butyl-2,6-dimethylphenylsulfinyl)-2-cyano-4-
fluoropyrrolidine (1-48).

[00212] A solution of (2S,4S)-2-cyano-4-fluoropyrrolidine hydrochloride (527 mg,
3.5 mmol) and triethylamine (3.5 mmol) in 2 mL of dichloromethane was slowly added to a
stirred solution of 4-tert-Butyl-2,6-dimethylphenylsulfinyl fluoride (799 mg, 3.5 mmol),
prepared in Example 53a, and triethylamine (3.5 mmol) in 3 mL of dichloromethane in a
fluoropolymer vessel cooled on an ice bath. The bath was removed after 0.5 hour and the
reaction mixture was stirred at room temperature for additional 0.5 hour. Into the reaction
mixture, were added 15 mL of dichloromethane and 40 mL of aqueous saturated K2CO3
solution, and the reaction mixture was stirred at room temperature for 0.5 hour. The organic
layer was separated and washed with water, dried with anhydrous magnesium sulfate, and
filtered. Removal of the solvent from the filtrate gave a solid, which was then mixed with
pentane and stirred for 15 minutes. Pentane was decanted off to obtain an insoluble solid
which was the product. The product was further purified by preparative thin-layered
chromatography using a 1:1 mixture of pentane and dichloromethane to give 902 mg (80%)
of (2S,4S)-N-(4-tert-butyl-2,6-dimethylphenylsulfinyl)-2-cyano-4-fluoropyrroridine (1-48):
19F NMR (CDCl3) (a mixture of stereoisomers) 8 -174 to 176 (m, 1F); 1H-NMR (CDCl3) d
1.28 (s, 9H), 2.20-2.8 (m, 8H), 3.0-4.0 (m, 2H), 4.68 (m, 1H), 5.26 (dm, 1H, J = 53 Hz), 7.10
(s, 2 H); 13C-NMR (CDCl3) (a major stereoisomer) d 19.93, 31.11, 34.64, 39.30 (d, J = 21
Hz), 49.20, 35.06, 55.21 (d, J = 23.8 Hz), 92.40 (d, J = 180.5 Hz), 117.91, 128.12, 133.01,
137.66, 154.88; (aminor stereoisomer) 8 19.86, 31.11, 34.64, 38.9 (d, J = 21 Hz), 49.51,
55.21 (d, J = 23.8 Hz), 92.30 (d, J = 180.5 Hz), 118.67, 127.94, 133.32, 137.74, 154.46.
Example 71. Preparation of(2S,4S)-N-(4-tert-butyl-2,6-dimethvlphenylsulfinvl)-4-fluoro-2-
(methoxvcarbonyl)pyrrolidine (1-49).

[00213] A solution of (2S,4S)-4-fluoro-2-(methoxycarbonyl)pyrrolidine
hydrochloride (3.31 g, 18 mmol) and triethylamine (18 mmol) in 10 mL of dichloromethane
was slowly added to a stirred solution of 4-tert-Butyl-2,6-dimethylphenylsulfinyl fluoride
(5.33 g, 21.3 mmol), prepared in Example 53a, and triethylamine (19 mmol) in 15 mL of
dichloromethane in a fluoropolymer vessel cooled on an ice bath. The bath was removed after
0.5 hour and the reaction mixture was stirred at room temperature for additional 0.5 hour.
Into the reaction mixture, were added 25 mL of dichloromethane and 50 mL of aqueous
saturated K2CO3 solution, and the mixture was stirred at room temperature for 0.5 hour. The
organic layer was separated and washed with water, dried with anhydrous magnesium sulfate,
and filtered. Removal of the solvent from the filtrate gave a solid, which was then washed
with pentane to give 5.0 g (78%) of (2S,4S)-N-(4-tert-butyl-2,6-dimethylphenylsulfinyl)-4-
fluoro-2-(methoxycarbonyl)pyrrolidine (1-49) as off-white solid: 19F-NMR (CDCl3) d-174.53
(m): 1H-NMR (CDCl3) d 1.27 (s, 9H), 2.20-2.8 (m with s, 8H), 3.0-3.2 (m, 1H), 3.7-4.0 (m
with s, 4H), 4.53 (dm, J = 10 Hz, 1H), 5.22 (dm, J = 52 Hz, 1H), 6.99 (s, 2H): 13C-NMR
(CDCl3) d 19.94, 31.15, 34.53, 38.04 (d, J = 21.7 Hz), 50.23 (d, J = 23.1 Hz), 52.49, 61.24,
92.93 (d, J = 179.9 Hz), 127.75, 134.17, 137.84, 153.84, 172.09.
Examples 72. Preparation of 2-fluoroethyl benzenesulfonate by oxidation of 2-fluoroethyl
benzenesulfinate.

[00214] 3-Chloroperbenzoic acid (3.7 mmol) was added into a solution of 2-
fluoroethyl phenylsulfinae (3.64 mmol) in 10 ml of anhydrous dichloromethane. The mixture
was stirred at room temperature for 3 hours. During this period insoluble 3-chlorobenzoic
acid is formed. Additional 5 ml of dichloromethane was added to the reaction mixture and the
mixture was washed with saturated sodium carbonate aqueous solution and then water and
dried over anhydrous MgSO4. Filtration and removal of solvent at reduced pressure gave 2-
fluoroethyl phenylsulfonate (VII-1). Yield 87%; 1H-NMR (CDCl3) d 5.58 (dt, 2H, J = 47 Hz,
J = 2.4 Hz), 4.29 (dt, 2H, J = 16 Hz, J = 2.4 Hz), 7.5-7.75 (m, 3H), 7.85-8.0 (m, 2H); 19F-
NMR (CDCl3) d -224.52 (tt, 1F, 7= 45, 28 Hz); 13C-NMR (CDCl3) d 68.77 (d, 7 = 21.0 Hz),
80.60 (d, J = 174.0 Hz), 128.01, 129.44, 134.16, 135.72.
Examples 73~79. Synthesis of various fluoroalkyl arenesulfonates and arenesulfonamides
from fluoroalkyl arenesulfinates and arenesulfinamides
[00215] Various fluoroalkyl arenesulfonates and arenesulfonamides were synthesized
by oxidation of the corresponding fluoroalkyl arenesulfinates and arenesulfinamides in the
same manner as in Example 72. The results and reaction conditions are shown in Table 7
together with Example 72.

[00216] Spectral data of the products are shown in the following:
[00217] 2-Fluoroethyl p-methylbenzenesulfonate (VII-2): 1H-NMR (CDCl3) d 3.36
(s, 3H), 4.18 (dm, 2H), .4.52 (dt, 2H, J = 47.1, 4.1 Hz), 7.30 (d, 2H, J = 8.6 Hz), 7.73 (d, 2H,
J = 8.3 Hz); 19F-NMR (CDCl3) d -224.49 (tt, 1F, J = 47.7, 28.1 Hz); 13C-NMR (CDCl3): d
21.59, 68.94 (d, J = 20.2 Hz), 80.74 (d, J = 173.4 Hz), 127.94, 130.10, 132.50, 145.41.
[00218] 2-Fluoroethyl p-fluorobenzenesulfonate (VII-3): 1H-NMR (CDCl3) d 4.24
(dt, 2H, J = 27.9, 4.1 Hz), 4.52 (dt, 2H, J = 47.1, 4.1 Hz), 7.10-7.30 (m, 2H), 7.80-7.94 (m,
2H); 19F-NMR (CDCl3) d -224.54 (tt, 1F, J = 45.5, 28.1 Hz); 13C-NMR (CDCl3) d 69.24 (d, J
= 20.2 Hz), 80.68 (d, J = 172.7 Hz), 116.67, 116.97, 130.87 (d, J = 10.1 Hz), 131.63 (d, J =
3.6 Hz).
[00219] 2-Fluoroethyl 4-tert-butyl-2,6-dimethylbenzenesulfonate (VII-4): 1H-NMR
(CDCl3) d 1.30 (s, 9H), 2.66 (s, 6H), 4.22 (dt, 2H, J = 29, 4.1 Hz), 4.60 (dt, 2H, J = 47, 4.1
Hz), 7.1f (s, 1H); 19F-NMR (CDCl3) d -223.94 (tt, 1F, J = 43.4, 26 Hz); 13C-NMR (CDCl3): d
23.00, 30.95, 34.79, 67.56 (d, J = 21 Hz), 80.70 (d, J = 173.3 Hz), 128.31, 130.24, 139.87,
156.40.
[00220] trans-1-(Phenylsulfonyloxy)-2-fluorocyclopentane (VII-5): 1H-NMR
(CDCl3) d 1.50-2.20 (m, 6H), 4.80-5.20 (m, 2H), 7.30-8.20 (m, 5H); 19F-NMR (CDCl3) d -
180.13 (m, IF); 13C-NMR (CDCl3): d 21.00, 30.25 (d, J = 21.0 Hz), 30.27, 85.49 (d, J = 31
Hz), 96.69 (d, J = 178. 8 Hz), 127.91, 129.43, 134.03.
[00221] trans-1-(4-tert-butyl-2,6-dimethylphenysulfonyloxy)-2-fluorocyclopentane
(VII-6): 1H-NMR (CDCl3) d 1.30 (s, 9H), 1.70-1.85 (, m, 6H), 2.65 (s, 6H), 4.70-8.20 (m,
2H), 7.15 (s, 2H); 19F-NMR (CDCl3) d -179.88 (m, 1F); 13C-NMR (CDCl3) d 21.10, 23.08,
30.31 (d, J = 23.1 Hz), 30.96, 34.78, 84.33 (d, J = 30.3 Hz), 97.16 (d, J = 177.7 Hz), 128.38,
131.15, 139.60, 156.30.
[00222] N-(2-Fluoroethyl)-N-methylbenzenesulfonamide (VIII-1): 1H-NMR (CDCl3)
8 2.74 (s, 3H), 3.25 (dt, 2H, J = 25.8, 24.8 Hz), 4.45 (dt, 2H, J = 47.1, 4.8 Hz), 7.30 -7.78 (m,
5H); 19F-NMR (CDCl3) d -220.75 (tt, 1F, J = 47.7, 24 Hz); 13C-NMR (CDCl3): d 36.25, 50.31
(d, J = 21.0 Hz), 82.59 (q, J = 170.4 Hz), 127.27, 129.30, 132.94, 137.44.
[00223] 1 -(4-tert-Butyl-2,6-dimethylphenylsulfonyl)-3-fluoropyrrolidine (VIII-2):
1H-NMR (CDCl3): d 1.29 (s, 9H), 1.90-2.4 (m, 2H), 3.15-3.65 (m, 4H), 5.25 (dt, 1H, J = 53.5,
2.0 Hz); 19F-NMR (CDCl3) d -175.0 (m, 1F); 13C-NMR (CDCl3): d 23.30. 31.00, 32.85 (d, J
= 21.7 Hz), 34.66, 44.68, 53.05 (d, J = 23.1 Hz), 36.25, 50.31 (d, J = 21.0 Hz), 92.64 (d, J =
178.4 Hz), 128.44, 132.65, 139.94, 155.40.

[00224] Sodium 2-naptholate was prepared in the following way: Sodium hydride
(1.50 mmol, 60% dispersion in mineral oil) was placed in dry flask and washed with 5 ml of
anhydrous hexane to remove oil. Anhydrous DMSO (5 ml) was added followed by the
addition of 2-naphthol (1.50 mmol) and the mixture was stirred at room temperature for 1
hour. Into the solution of sodium 2-naphtholate, was added a solution of 2-fluoroethyl
benzenesulfonate in 1 ml of DMSO. The reaction mixture was heated at 90 °C for 15 hours
and cooled to room temperature. After water was added to it, the mixture was extracted with
a 1:1 mixture of hexane and ether (25 ml). The extract was washed and dried over anhydrous
magnesium sulfate and filtered. Removal of solvent at reduced pressure gave ß-(2-
fluoroethoxy)naphthaene as white powder solid: Yield 92%; 1H-NMR (CDCl3) d 3.34 (dt,
2H, J = 27.9, 4.14 Hz), 4.85 (dt, 2H, J = 47.1, 3.0 Hz), 7.10-7.22 (m, 2H), 7.30-7.51 (m, 2H),
7.70-7.84 (m, 3H); 19F-NMR (CDCl3) d -223.50 (tt, 1F, J = 47.6, 28.2 Hz); 13C-NMR
(CDCb) 5 67.16 (d, J = 20.2 Hz), 82.01 (d, J = 170.5 Hz), 106.83, 118.94, 123.98, 126.57,
126.88, 127.79, 129.29, 129.71, 134.48, 156.46.
Example 81. Reaction of 2-fluoroethyl 4-tert-butyl-2,6-dimethylbenzenesulfonate with
sodium 2-naphtholate

[00225] A solution of sodium naphtholate (2 mmol) in DMSO (5 mL) was prepared
in the same manner as in Example 80. Into the solution of sodium naphtholate, was added a
solution of 2-fluoroethyl 4-tert-butyl-2,6-dimethylbenzenesulfonate (2.0 mmol) in DMSO (5
mL). The reaction mixture was heated at 45 °C for 24 hours and cooled to room temperature.
A 1:1 mixture of hexane and ether (25 ml) was added to the reaction mixture and the mixture
was washed with water (50 ml). The organic layer was separated out, washed with water (20
ml x 2), and dried over anhydrous magnesium sulfate. After filtration, removal of solvent at
reduced pressure gave 2-(2-fluoroethoxy)naphthol as white powder solid which was
crystallized from hexane: Yield: 75%. The spectral data of the product was shown in
Example 80.

[00226] Trifluoroacetic acid (8.0 mmol) was added slowly to a solution of N-benzyl-
N-(2-fluoroethyl)benzenesulfinamide in 3 ml of methanol. The reaction mixture was stirred at
room temperature for 1 hour. The mixture was concentrated and the residue was column-
chromatographed on silica gel (short column). It was eluted with a 3:7 mixture of ethyl
acetate and hexane (50 ml) and then methanol (50 ml). The amine salt was eluted with
methanol. Removal of methanol at reduced pressure gave a trifluoroacetic acid salt of N-(2-
fluoroethyl)benzylamine as a solid powder: Yield 78%; 1H-NMR (D2O) d 3.40 (dt, 2H, J =
27.2, 4.5 Hz), 4.61 (dt, 2H, J = 50.0, 4.8 Hz), 7.35 (s, 5H); 19F-NMR (D2O) d - 75.51 (s, 3F),
224.53 (tt, 1F, J = 45.5, 28.1 Hz); 13C-NMR (D2O) d 46.99 (d, J = 56.0 Hz), 51.16, 79.32 (d, J
= 165.4 Hz), 117.0 (q, J = 230 Hz), 129.30, 129.78, 129.85, 120.43, 163.26.
Example 83. Devrotection of 1-(4-tert-butyl-2,4-dimethylphenylsulfinvl)-3-fluoroprrolidine;
Preparation of 3-fluoropyrrolidine salt

[00227] Into a solution of 1-(4-tert-butyl-2,6-dimethylphenylsulfinyl)-3-
fluoropyrrolidine (1.0 mmol) in 3 ml of methanol, was added trifluoroacetic acid (8.0 mmol).
After it was stirred at room temperature for 3 hours, the reaction mixture was concentrated.
The residue was chromatographed on silica gel (short column). It was eluted with a 3:7
mixture of ethyl acetate and hexane (50 ml) and then with methanol (50 ml). The amine salt
was eluted with methanol (50 ml). Removal of methanol at reduced pressure gave a
trifluoroacetic acid salt of 3-fluoropyrrolidine as a solid powder: Yield 70%; 19F-NMR (D2O)
8 - 75.51 (s, 3F), -176.79 (m, 1F); 1H-NMR (D2O) 8 1.90-2.40 (m, 2H), 3.15-3.65 (m, 4H),
5.35 (dt, 1H, J = 51.6, 3.8 Hz); 13C-NMR (D2O) 8 31.08 (d, J = 21.7 Hz), 43.71, 51.45 (d, J =
23.1 Hz), 92.55 (d, J = 174.1 Hz), 116.36 (q, J = 291.1 Hz), 162.98 (q, J = 35.4 Hz).
[00228] It will be clear that the invention is well adapted to attain the ends and
advantages mentioned as well as those inherent therein. While presently preferred
embodiments have been described for purposes of this disclosure, various changes and
modifications may be made which are well within the scope of the invention. Numberous
other changes may be made which will readily suggest themselves to those skilled in the art
and which are encompassed in the spirit of the invention disclosed herein and as defined in
the appended claims.
[00229] All references including publications and patents are incorporated by
reference herein for all purposes.
CLAIMS
What is claimed is:
1. A process for preparing a fluoroalkyl arylsulfinyl compound having a formula (I) as
follows:

the method comprising reacting an oxygen-containing compound having a formula (II) with
arylsulfur trifluoride having a formula (III):

in which:
R1, R2, R3, and R4 each is independently a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group
having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20
carbon atoms, a substituted or unsubstituted heterocyclyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a
substituted or unsubstituted acyl group having 1 to 20 carbon atoms, a substituted or
unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted aryloxycarbonyl group having 7 to 20 carbon atoms, a substituted or
unsubstituted (heterocyclyl)oxycarbonyl group having 2 to 20 carbon atoms, or a cyano
group;
Ra, Rb, Rc, Rd, and Re each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a nitro group, or a
cyano group;
A is an oxygen atom or NR5 in which R5 is a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclyl group
having 1 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 20
carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon
atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 20 carbon atoms,
a substituted or unsubstituted (heterocyclyl)oxycarbonyl group having 2 to 20 carbon
atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted arylsulfonyl group having 6 to 20 carbon atoms, a substituted
or unsubstituted (heterocyclyl)sulfonyl group having 1 to 20 carbon atoms, or a
R14R15R16Si group in which R14, R15, and R16 each is independently an alkyl group having
1 to 10 carbon atoms, an aralkyl group haing 7 to 10 carbon atoms, or an aryl group
having 6 to 10 carbon atoms;

in which:
R6, R7, R8, R9, R10, R11, R12, and R13 each is independently a hydrogen atom, a
halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted
aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclyl group
having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20
carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, a
substituted or unsubstituted (heterocyclyl)oxy group having 1 to 20 carbon atoms, a
substituted or unsubstituted acyl group having 1 to 20 carbon atoms, a substituted or
unsubstituted acyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or unsubstituted
aryloxycarbonyl group having 7 to 20 carbon atoms, a substituted or unsubstituted
(heterocyclyl)oxycarbonyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted amino group having 20 or less carbon atoms, a substituted or unsubstituted
carbamoyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylthio
group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6
to 20 carbon atoms, a substituted or unsubstituted (heterocyclyl)thio group having 1 to 20
carbon atoms, a substituted or unsubstituted alkylsulfinyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 20 carbon atoms, a
substituted or unsubstituted (heterocyclyl)sulfmyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, or a
substituted or unsubstituted arylsulfonyl group having 6 to 20 carbon atoms, a substituted
or unsubstituted (heterocyclyl)sulfonyl group having 1 to 20 carbon atoms, a nitro group,
or a cyano group;
h, i, and j each is independently 0 or 1;
Rx and Ry each is independently a hydrogen atom, a silyl group, a metal atom, an
ammonium moiety, or a phosphonium moiety, or Rx and Ry combine to form a metal
atom or a silyl group; and
two or more of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11 or two or more of R1,
R2, R3, R4, R5, R12, and R13 may be linked with or without a heteroatom(s) to form any
ring structure.
2. The method of claim 1 wherein at least one of Rx and Ry is a hydrogen atom or a silyl
group, or Rx and Ry combine to form a silyl group, in which the reaction of the oxygen-
containing compound with the arylsulfur trifluoride is conducted in the presence of a base or
a silicon atom-activating agent.
3. The method of claim 1, wherein the arylsulfur trifluoride of formula (HI) is prepared
by the method comprising reacting arylsulfur halotetrafluoride of formula (IV) with a
reducing substance:

in which:
Ra, Rb, Rc, Rd, and Re each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a nitro group, or a
cyano group; and
X is a chlorine atom, bromine atom, or iodine atom.
4. The method of claim 3, wherein X is a chlorine atom.
5. The method of claim 3, wherein the reducing substance is a substituted or
unsubstituted heteroarene.
6. A process for preparing a fluoroalkyl arylsulfinyl compound having a formula (I) as
follows:

the method comprising reacting an oxygen-containing compound having a formula
(II) with arylsulfur halotetrafluoride having a formula (IV) in the presence of a reducing
substance that reduces the arylsulfur halotetrafluoride:

in which:
R1, R2, R3, and R4 each is independently a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group
having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20
carbon atoms, a substituted or unsubstituted heterocyclyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a
substituted or unsubstituted acyl group having 1 to 20 carbon atoms, a substituted or
unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted aryloxycarbonyl group having 7 to 20 carbon atoms, a substituted or
unsubstituted (heterocyclyl)oxycarbonyl group having 2 to 20 carbon atoms, or a cyano
group;
Ra, Rb, Rc, Rd, and Re each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a nitro group, or a
cyano group;
A is an oxygen atom or NR5 in which R5 is a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclyl group
having 1 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 20
carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon
atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 20 carbon atoms,
a substituted or unsubstituted (heterocyclyl)oxycarbonyl group having 2 to 20 carbon
atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted arylsulfonyl group having 6 to 20 carbon atoms, a substituted
or unsubstituted (heterocyclyl)sulfonyl group having 1 to 20 carbon atoms, or a
R14R15R16Si group in which R14, R15, and R16 each is independently an alkyl group having
1 to 10 carbon atoms, an aralkyl group haing 7 to 10 carbon atoms, or an aryl group
having 6 to 10 carbon atoms;
B is:

in which:
R6, R7, R8, R9, R10, R11, R12 and R13 each is independently a hydrogen atom, a
halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted
aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclyl group
having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20
carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, a
substituted or unsubstituted (heterocyclyl)oxy group having 1 to 20 carbon atoms, a
substituted or unsubstituted acyl group having 1 to 20 carbon atoms, a substituted or
unsubstituted acyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or unsubstituted
aryloxycarbonyl group having 7 to 20 carbon atoms, a substituted or unsubstituted
(heterocyclyl)oxycarbonyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted amino group having 20 or less carbon atoms, a substituted or unsubstituted
carbamoyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylthio
group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6
to 20 carbon atoms, a substituted or unsubstituted (heterocyclyl)thio group having 1 to 20
carbon atoms, a substituted or unsubstituted alkylsulfinyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 20 carbon atoms, a
substituted or unsubstituted (heterocyclyl)sulfinyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, or a
substituted or unsubstituted arylsulfonyl group having 6 to 20 carbon atoms, a substituted
or unsubstituted (heterocyclyl)sulfonyl group having 1 to 20 carbon atoms, a nitro group,
or a cyano group;
h, i, and j each is independently 0 or 1;
Rx and Ry each is independently a hydrogen atom, a silyl group, a metal atom, an
ammonium moiety, or a phosphonium moiety, or Rx and Ry combine to form a metal
atom or a silyl group;
X is a chlorine atom, bromine atom, or iodine atom; and
two or more of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11 or two or more of R1,
R2, R3, R4, R5, R12, and R13 may be linked with or without a heteroatom(s) to form any
ring structure.
7. The method of claim 6, wherein X is a chlorine atom.
8. The method of claim 6, wherein the reducing substance is a substituted or
unsubstituted heteroarene.
9. A fluoroalkyl arylsulfinyl compound having a formula (Ia) as follows:

in which:
R1, R2 , R3, and R4 each is independently a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group
having 6 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having
2 to 20 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 20
carbon atoms, or a cyano group;
Ra, Rb, Rc, Rd , and Re each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a nitro group;
A' is an oxygen atom or NR5 in which R5 is a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms;
B'is

in which:
R6', R7', R8', R9', R10', R11', R12', and R13' each is independently a hydrogen atom, a
halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted
alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group
having 6 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having
2 to 20 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 20
carbon atoms, a nitro group, or a cyano group;
h, i, and j each is independently 0 or 1; and
two or more of R1', R2', R3', R4', R5', R6', R7', R8', R9', R10' and R11' or two or more of
R1', R2', R3, R4', R5, R12', and R13' may be linked with or without a heteroatom(s) to form
any ring structure.
10. The fluoroalkyl arylsulfinyl compound of claim 9, wherein the total number of h, i,
and j is 2 or less.
11. A process for preparing a fluoroalkyl arylsulfinyl compound having a formula (Ia) as
follows:

the method comprising reacting an oxygen-containing compound having a formula (IIa) with
arylsulfur trifluoride having a formula (IIIa):

in which:
R1', R2', R3', and R4' each is independently a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group
having 6 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having
2 to 20 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 20
carbon atoms, or a cyano group;
Ra', Rb', Rc', Rd', and Re' each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a nitro group;
A' is an oxygen atom or NR5 in which R5 is a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms;
B'is

in which:
R6', R7', R8', R9' , R10', R11', R12' and R13' each is independently a hydrogen atom, a
halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted
alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group
having 6 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having
2 to 20 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 20
carbon atoms, a nitro group, or a cyano group;
h, i, and j each is independently 0 or 1;
Rx and Ry each is independently a hydrogen atom, a silyl group, a metal atom, an
ammonium moiety, or a phosphonium moiety; or Rx and Ry combine to form a metal
atom or a silyl group; and
two or more of R1', R2', R3', R4', R5', R6', R7', R8', R9', R10' and R11' or two or more of
R1', R2', R3', R4', R5', R12', and R13' may be linked with or without a heteroatom(s) to form
any ring structure.
12. The method of claim 11, wherein the arylsulfur trifluoride of formula (IIIa) is
prepared by a method comprising reacting arylsulfur halotetrafluoride of formula (IVa) with a
reducing substance:
reacting arylsulfur halotetrafluoride of formula (IVa) with a reducing substance. Thus,
embodiments of the present invention provide a method (Scheme 7, Processes II' and Ia') for
preparing a fluoroalkyl arylsulfinyl compound having a formula (Ia), which comprises
(Process II') reacting an arylsulfur halotetrafluoride having a formula (IVa) with a reducing
substance that reduces the arylsulfur halotetrafluoride and (Process Ia') reacting a resulting
arylsulfur trifluoride having a formula (IIIa) with an oxygen-containing compound having a
formula (IIa):
Scheme 7, Processes II' and Ia'

[00106] For the compounds represented by formulas (Ia), (IIa), (IIIa), and (IVa), R1',
R2', R3', R4', Rx, Ry, A', B', Ra', Rb', Rc', Rd', Re', and X are the same as described above.
Process II'
[00107] Process II' is the same as Process II except that compound (IVa) is used
instead of comound (IV). Illustrative compounds of formula (IVa) are exemplified in Process
II above.
Process Ia'
[00108] Process Ia' is the same as Process Ia except that compounds (IIa) and (IIIa) are
used instead of compounds (II) and (III), respectively. Illustrative compounds of formula (IIa)
are exemplified in Process I above.

in which:
Ra', Rb', Rc', Rd', and Re' each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a nitro group;
and
X is a chlorine atom, bromine atom, or iodine atom.
13. The method of claim 12, wherein X is a chlorine atom.
14. The method of claim 12, wherein the reducing substance is a substituted or
unsubstituted heteroarene.
15. A process for preparing a fluoroalkyl arylsulfinyl compound having a formula (Ia) as
follows:

the method comprising: reacting an oxygen-containing compound having a formula
(IIa) with arylsulfur halotetrafluoride having a formula (IVa) in the presence of a reducing
substance that reduces the arylsulfur halotetrafluoride:

in which:
R1, R2 , R3, and R4 each is independently a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group
having 6 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having
2 to 20 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 20
carbon atoms, or a cyano group;
Ra, Rb, Rc, Rd , and Re each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a nitro group;
A' is an oxygen atom or NR in which R is a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms;
B'is

in which:
R6', R7', R8', R9', R10', R11', R12' and R13' each is independently a hydrogen atom, a
halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted
alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group
having 6 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having
2 to 20 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 20
carbon atoms, a nitro group, or a cyano group;
h, i, and j each is independently 0 or 1;
Rx and Ry each is independently a hydrogen atom, a silyl group, a metal atom, an
ammonium moiety, or a phosphonium moiety; or Rx and Ry combine to form a metal
atom or a silyl group;
X is a chlorine atom, bromine atom, or iodine atom; and
two or more of R1', R2', R3', R4', R5', R6', Rr, R8' R9', R10' and R11', or two or more of
R1', R2', R3', R4', R5', R12', and R13' may be linked with or without a heteroatom(s) to form
any ring structure.
16. The method of claim 15, wherein X is a chlorine atom.
17. The method of claim 15, wherein the reducing substance is a substituted or
unsubstituted heteroarene.
18. A fluoroalkyl arylsulfinyl compound having a formula (Ib) as follows:

R1 and R4 each is independently a hydrogen atom, a substituted or unsubstituted
alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having
6 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20
carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 20 carbon
atoms, or a cyano group;
R6" , R7" , R8" , R9" , R10" andR11" each is independently a hydrogen atom, a
substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or
unsubstituted aryl group having 6 to 20 carbon atoms;
h, i and j each is independently 0 or 1;
n is 1, 2, 3 or 4; and
Ra', Rb' , Rc', Rd', and Re' each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a nitro group.
19. A fluoroalkyl arylsulfinyl compound having a formula (Ic) as follows:

in which:
R1 , R3 and R4 each is independently a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group
having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having
7 to 20 carbon atoms, or a cyano group;
R6" and R7" each is independently a hydrogen atom, a substituted or unsubstituted
alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having
6 to 20 carbon atoms;
h is 0 or 1;
n is 1, 2, 3, or 4; and
Ra', Rb', Rc', Rd', and Re' each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a nitro group.
20. A fluoroalkyl arylsulfinyl compound having a formula (Id) as follows:

in which:
R3 is a hydrogen atom, a substituted or unsubstituted alkoxycarbonyl group having
2 to 20 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 20
carbon atoms, or a cyano group; and
Ra', Rb', Rc', Rd', and Re' each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a nitro group.
21. A process for preparing a fluoroalkyl arylsulfinyl compound having a formula (Ie) as
follows:

the method comprising reacting an oxygen-containing compound having a formula
(IIb) with arylsulfur trifluoride having a formula (III):

in which:
R1, R2, R3, and R4 each is independently a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group
having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20
carbon atoms, a substituted or unsubstituted heterocyclyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a
substituted or unsubstituted acyl group having 1 to 20 carbon atoms, a substituted or
unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted aryloxycarbonyl group having 7 to 20 carbon atoms, a substituted or
unsubstituted (heterocyclyl)oxycarbonyl group having 2 to 20 carbon atoms, or a cyano
group;
Ra, Rb, Rc, Rd, and Re each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a nitro group, or a
cyano group;
A is an oxygen atom or NR5 in which R5 is a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclyl group
having 1 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 20
carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon
atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 20 carbon atoms,
a substituted or unsubstituted (heterocyclyl)oxycarbonyl group having 2 to 20 carbon
atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted arylsulfonyl group having 6 to 20 carbon atoms, a substituted
or unsubstituted (heterocyclyl)sulfonyl group having 1 to 20 carbon atoms, or a
R14R15R16Si group in which R14, R15, and R16 each is independently an alkyl group having
1 to 10 carbon atoms, an aralkyl group haing 7 to 10 carbon atoms, or an aryl group
having 6 to 10 carbon atoms;
R12 and R13 each is independently a hydrogen atom, a halogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group
having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20
carbon atoms, a substituted or unsubstituted heterocyclyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a
substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or
unsubstituted (heterocyclyl)oxy group having 1 to 20 carbon atoms, a substituted or
unsubstituted acyl group having 1 to 20 carbon atoms, a substituted or unsubstituted
acyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or unsubstituted
aryloxycarbonyl group having 7 to 20 carbon atoms, a substituted or unsubstituted
(heterocyclyl)oxycarbonyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted amino group having 20 or less carbon atoms, a substituted or unsubstituted
carbamoyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylthio
group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6
to 20 carbon atoms, a substituted or unsubstituted (heterocyclyl)thio group having 1 to 20
carbon atoms, a substituted or unsubstituted alkylsulfinyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 20 carbon atoms, a
substituted or unsubstituted (heterocyclyl)sulfinyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, or a
substituted or unsubstituted arylsulfonyl group having 6 to 20 carbon atoms, a substituted
or unsubstituted (heterocyclyl)sulfonyl group having 1 to 20 carbon atoms, a nitro group,
or a cyano group;
Rx and Ry each is independently a hydrogen atom, a silyl group, a metal atom, an
ammonium moiety, or a phosphonium moiety, or Rx and Ry combine to form a metal
atom or a silyl group; and
two or more of R1, R2, R3, R4, R5, R12, and R13 may be linked with or without a
heteroatom(s) to form any ring structure.
22. The method of claim 21, wherein the arylsulfur trifluoride of formula (HI) is prepared
by the method comprising reacting arylsulfur halotetrafluoride of formula (IV) with a
reducing substance:

in which:
Ra, Rb, Rc, Rd, and Re each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a nitro group, or a
cyano group; and
X is a chlorine atom, bromine atom, or iodine atom.
23. A process for preparing a fluoroalkyl arylsulfinyl compound having a formula (Ie) as
follows:

the method comprising reacting an oxygen-containing compound having a formula
(IIb) with arylsulfur halotetrafluoride having a formula (IV) in the presence of a reducing
substance that reduces the arylsulfur halotetrafluoride:

in which:
R1, R2, R3, and R4 each is independently a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group
having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20
carbon atoms, a substituted or unsubstituted heterocyclyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a
substituted or unsubstituted acyl group having 1 to 20 carbon atoms, a substituted or
unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted aryloxycarbonyl group having 7 to 20 carbon atoms, a substituted or
unsubstituted (heterocyclyl)oxycarbonyl group having 2 to 20 carbon atoms, or a cyano
group;
Ra, Rb, Rc, Rd, and Re each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a nitro group, or a
cyano group;
A is an oxygen atom or NR5 in which R5 is a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclyl group
having 1 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 20
carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon
atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 20 carbon atoms,
a substituted or unsubstituted (heterocyclyl)oxycarbonyl group having 2 to 20 carbon
atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted arylsulfonyl group having 6 to 20 carbon atoms, a substituted
or unsubstituted (heterocyclyl)sulfonyl group having 1 to 20 carbon atoms, or a
R14R15R16Si group in which R14, R15, and R16 each is independently an alkyl group having
1 to 10 carbon atoms, an aralkyl group haing 7 to 10 carbon atoms, or an aryl group
having 6 to 10 carbon atoms;
R12 and R13 each is independently a hydrogen atom, a halogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group
having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20
carbon atoms, a substituted or unsubstituted heterocyclyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a
substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or
unsubstituted (heterocyclyl)oxy group having 1 to 20 carbon atoms, a substituted or
unsubstituted acyl group having 1 to 20 carbon atoms, a substituted or unsubstituted
acyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or unsubstituted
aryloxycarbonyl group having 7 to 20 carbon atoms, a substituted or unsubstituted
(heterocyclyl)oxycarbonyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted amino group having 20 or less carbon atoms, a substituted or unsubstituted
carbamoyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylthio
group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6
to 20 carbon atoms, a substituted or unsubstituted (heterocyclyl)thio group having 1 to 20
carbon atoms, a substituted or unsubstituted alkylsulfinyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 20 carbon atoms, a
substituted or unsubstituted (heterocyclyl)sulfinyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, or a
substituted or unsubstituted arylsulfonyl group having 6 to 20 carbon atoms, a substituted
or unsubstituted (heterocyclyl)sulfonyl group having 1 to 20 carbon atoms, a nitro group,
or a cyano group;
Rx and Ry each is independently a hydrogen atom, a silyl group, a metal atom, an
ammonium moiety, or a phosphonium moiety, or Rx and Ry combine to form a metal
atom or a silyl group;
X is a chlorine atom, bromine atom, or iodine atom; and
two or more of R1, R2, R3, R4, R5, R12, and R13 may be linked with or without a
heteroatom(s) to form any ring structure.
24. A process for preparing a fluoroalkyl arylsulfinyl compound having a formula (If) as
follows:

the method comprising reacting an oxygen-containing compound having a formula
(IIc) with arylsulfur trifluoride having a formula (III):

[00109] The present invention also provides a method (Scheme 8, Process III') for
preparing a fluoroalkyl arylsulfinyl compound having a formula (Ia), which comprises
reacting an oxygen-containing compound having a formula (IIa) with arylsulfur
halotetrafluoride having a formula (IVa) in the presence of a reducing substance that reduces
the arylsulfur halotetrafluoride:
Scheme 8, Process III'

[00110] For the compounds represented by formulas (Ia), (IIa), and (IVa), R1, R2, R3,
R4', Rx, Ry, A', B', Ra', Rb', Rc', Rd', Re', and X are the same as described above.
Process III'
[00111] Process III' is the same as Process III except that compounds (IIa) and (IVa)
are used instead of compounds (II) and (IV), respectively. Illustrative compounds of formulas
(IIa) and (IVa) are exemplified in Processes I and II above, respectively.
[00112] Embodiments of the present invention also provide useful fluoroalkyl
arylsulfinyl compounds represented by formula (Ib) as follows:

in which:
R2, R3, and R4 each is independently a hydrogen atom, a substituted or unsubstituted
alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group
having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20
carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a
substituted or unsubstituted heterocyclyl group having 1 to 20 carbon atoms, a substituted
or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted
acyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl
group having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group
having 7 to 20 carbon atoms, a substituted or unsubstituted (heterocyclyl)oxycarbonyl
group having 2 to 20 carbon atoms, or a cyano group;
Ra, Rb, Rc, Rd, and Re each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a nitro group, or a
cyano group;
A is an oxygen atom or NR5 in which R5 is a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclyl group
having 1 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 20
carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon
atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 20 carbon atoms,
a substituted or unsubstituted (heterocyclyl)oxycarbonyl group having 2 to 20 carbon
atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted arylsulfonyl group having 6 to 20 carbon atoms, a substituted
or unsubstituted (heterocyclyl)sulfonyl group having 1 to 20 carbon atoms, or a
R14R15R16Si group in which R14, R15, and R16 each is independently an alkyl group having
1 to 10 carbon atoms, an aralkyl group haing 7 to 10 carbon atoms, or an aryl group
having 6 to 10 carbon atoms;
B is:

in which:
R6, R7, R8, R9, R10, R11, R12, R13, R19, R20 and R21 each is independently a hydrogen
atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a
substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted
heterocyclyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy
group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6
to 20 carbon atoms, a substituted or unsubstituted (heterocyclyl)oxy group having 1 to 20
carbon atoms, a substituted or unsubstituted acyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted acyloxy group having 1 to 20 carbon atoms, a substituted or
unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted aryloxycarbonyl group having 7 to 20 carbon atoms, a substituted or
unsubstituted (heterocyclyl)oxycarbonyl group having 2 to 20 carbon atoms, a substituted
or unsubstituted amino group having 20 or less carbon atoms, a substituted or
unsubstituted carbamoyl group having 1 to 20 carbon atoms, a substituted or
unsubstituted alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted
arylthio group having 6 to 20 carbon atoms, a substituted or unsubstituted
(heterocyclyl)thio group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkylsulfinyl group having 1 to 20 carbon atoms, a substituted or unsubstituted
arylsulfinyl group having 6 to 20 carbon atoms, a substituted or unsubstituted
(heterocyclyl)sulfinyl group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkylsulfonyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted
arylsulfonyl group having 6 to 20 carbon atoms, a substituted or unsubstituted
(heterocyclyl)sulfonyl group having 1 to 20 carbon atoms, a nitro group, or a cyano
group;
h, i, and j each is independently 0 or 1;
Rx and Ry each is independently a hydrogen atom, a silyl group, a metal atom, an
ammonium moiety, or a phosphonium moiety, or Rx and Ry combine to form a metal
atom or a silyl group; and
two or more of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R19, R20 and R21
may be linked with or without a heteroatom(s) to form any ring structure.
25. The method of claim 24, wherein the arylsulfur trifluoride of formula (III) is prepared
by the method comprising reacting arylsulfur halotetrafluoride of formula (IV) with a
reducing substance:

in which:
Ra, Rb, Rc, Rd, and Re each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a nitro group, or a
cyano group; and
X is a chlorine atom, bromine atom, or iodine atom.
26. A process for preparing a fluoroalkyl arylsulfinyl compound having a formula (If) as
follows:

the method comprising reacting an oxygen-containing compound having a formula
(IIc) with arylsulfur halotetrafluoride having a formula (IV) in the presence of a reducing
substance that reduces the arylsulfur halotetrafluoride:

in which:
R2, R3, and R4 each is independently a hydrogen atom, a substituted or unsubstituted
alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group
having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20
carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a
substituted or unsubstituted heterocyclyl group having 1 to 20 carbon atoms, a substituted
or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted
acyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl
group having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group
having 7 to 20 carbon atoms, a substituted or unsubstituted (heterocyclyl)oxycarbonyl
group having 2 to 20 carbon atoms, or a cyano group;
Ra, Rb, Rc, Rd, and Re each is independently a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a nitro group, or a
cyano group;
A is an oxygen atom or NR5 in which R5 is a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclyl group
having 1 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 20
carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon
atoms, a substituted or unsubstituted aryloxycarbonyl group having 7 to 20 carbon atoms,
a substituted or unsubstituted (heterocyclyl)oxycarbonyl group having 2 to 20 carbon
atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted arylsulfonyl group having 6 to 20 carbon atoms, a substituted
or unsubstituted (heterocyclyl)sulfonyl group having 1 to 20 carbon atoms, or a
R14R15R16Si group in which R14, R15, and R16 each is independently an alkyl group having
1 to 10 carbon atoms, an aralkyl group haing 7 to 10 carbon atoms, or an aryl group
having 6 to 10 carbon atoms;
B is:

in which:
R6, R7, R8, R9, R10, R11, R12, R13, R19, R20, and R21 each is independently a hydrogen
atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a
substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted
heterocyclyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy
group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6
to 20 carbon atoms, a substituted or unsubstituted (heterocyclyl)oxy group having 1 to 20
carbon atoms, a substituted or unsubstituted acyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted acyloxy group having 1 to 20 carbon atoms, a substituted or
unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or
unsubstituted aryloxycarbonyl group having 7 to 20 carbon atoms, a substituted or
unsubstituted (heterocyclyl)oxycarbonyl group having 2 to 20 carbon atoms, a substituted
or unsubstituted amino group having 20 or less carbon atoms, a substituted or
unsubstituted carbamoyl group having 1 to 20 carbon atoms, a substituted or
unsubstituted alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted
arylthio group having 6 to 20 carbon atoms, a substituted or unsubstituted
(heterocyclyl)thio group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkylsulfinyl group having 1 to 20 carbon atoms, a substituted or unsubstituted
arylsulfinyl group having 6 to 20 carbon atoms, a substituted or unsubstituted
(heterocyclyl)sulfinyl group having 1 to 20 carbon atoms, a substituted or unsubstituted
alkylsulfonyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted
arylsulfonyl group having 6 to 20 carbon atoms, a substituted or unsubstituted
(heterocyclyl)sulfonyl group having 1 to 20 carbon atoms, a nitro group, or a cyano
group;
h, i, and j each is independently 0 or 1;
Rx and Ry each is independently a hydrogen atom, a silyl group, a metal atom, an
ammonium moiety, or a phosphonium moiety, or Rx and Ry combine to form a metal
atom or a silyl group;
X is a chlorine atom, bromine atom, or iodine atom; and
two or more of R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R19, R20 and R21 may
be linked with or without a heteroatom(s) to form any ring structure.

Novel preparative methods for fluoroalkyl arylsulfinyl compounds are disclosed. Fluorinated compounds as useful
fluorinated compounds, intermediates, or builing blocks are disclosed. Useful applications of the fluoroalkyl arylsulfinyl compounds
are shown.