DESCRIPTION
This application is divided . out of Indian Patent Application number 3309/KOLNP/2009 dated
17/09/2009
TECHNICAL FIELD
[001] The invention relates to methods and compositions useful in the
preparation of arylsulfur pentafluorides.
BACKGROUND OF THE INVENTION
[002] Arylsulfur pentafluorides compounds are used to introduce one or more
sulfur pentafluoride groups into various commercial organic molecules. In
particular, arylsulfur pentafluorides have been shown as useful compounds (as
product or intermediate) in .the development of liquid crystals, in bioactive
chemicals such as fungicides, herbicides, and insecticides, and in other like
materials [see Fluorine-containing Synthons (ACS Symposium Series 911), ed by
V. A. Soloshonok, American Chemical Society (2005), pp. 108-113]. However, as
discussed herein, conventional synthetic methodologies to produce arylsulfur
pentafluorides have proven difficult and are a concern within the art.
[003] Generally, arylsulfur pentafluorides are synthesized using one of the
following synthetic methods: (1) fluorination of diaryl disulfies or arylsulfur
trifluoride with AgF2 [see J. Am. Chem. Soc, Vol. 84 (1962), pp. 3064-3072, and
J. Fluorine Chem. Vol. 112 (2001), pp. 287-295]; (2) fluorination of
di(nitrophenyl) disulfides, nitrobenzenethiols, or nitrophenylsulfur trifluorides with
molecular fluorine (F2) [see Tetrahedron, Vol. 56 (2000), pp. 3399-3408; Eur. J.,:
Org. Chem., Vol. 2005, pp. 3095-3100; and USP 5,741,935]; (3) fluorination of
diaryl disulfides or arenethiols with F2, CF3OF, or CF2(OF)2 in the presence or
absence of a fluoride source (see US Patent Publication No. 2004/0249209 Al); (4)
fluorination of diaryl disulfides withXeF2 [see J. Fluorine Chem., Vol. 101 (2000),
pp. 279-283];.(5) reaction of 1,4-bis(acetoxy)-2-cyclohexene with SF5Br followed
by dehydrobromination or hydrolysis and then aromatization reactions [see J.
Fluorine Chem., Vol. 125 (2004), pp. 549-552]; (6) reaction of 4,5-dichloro-l-
cyclohexene with SF5CI followed by dehydrochlorination [see Organic Letters,
Vol. 6 (2004), pp. 2417-2419 and PCT WO 2004/011422 Al]; and (7) reaction of
SF5Cl with acetylene, followed by bromination, dehydrobromination, and reduction
with zinc, giving pentafluorosulfanylacetylene, which was then reacted with

butadiene, followed by an aromatization reaction at very high temperature [see J.
Org. Chem., Vol. 29 (1964), pp. 3567-3570].
[004] Each of the above synthetic methods has one or more drawbacks making it
either impractical (time or yield), overly expensive, and/or overly dangerous to
practice. For example, synthesis methods (1) and (4) provide low yields and require
expensive reaction agents, e.g., AgF2 and XeF2. Methods (2) and (3) require the use
of F2, CF3OF, or CF2(OF)2, each of which is toxic, explosive, and corrosive, and
products produced using these methods are at a relatively low yield. Note that
handling of these gasses is expensive from the standpoint of the gasses production,
storage and use. In addition, synthesis methods that require the use of F2, CF3OF,
and/or CF2(OF)2 are limited to the production of deactivated arylsulfur
pentafluorides, such as nitrophenylsulfur pentafluorides, due to their extreme
reactivity, which leads to side-reactions such as fluorination of the aromatic rings
when not deactivated. Methods (5) and (6) also require expensive reactants, e.g.,
SF5CI or SFsBr, and have narrow application because the starting cyclohexene
derivatives are limited. Finally, method (7) requires the expensive reactant SF5CI
and includes many reaction steps to reach the arylsulfur pentafluorides (timely and
low yield). Therefore, problems with the production methods for arylsulfur
pentafluorides have made it difficult to prepare the material in a safe, cost effective
and timely fashion.
[005] Phenylsulfur chlorotetrafluoride, p-methylphenylsulfur chlorotetrafluoride,
and p-nitrophenylsulfur chlorotetrafluoride were detected in the reaction of
diphenyl disulfide, bis(p-mefhylphenyl) disulfide, and bis(p-nitrophenyl) disulfide,
respectively, with XeF2 in the presence of tetraethylammonium chloride (see Can.
J. Chem., Vol. 75, pp. 1878-1884). Chemical structures of the chlorotetrafluoride
compounds were assigned by analysis of the NMR data of the reaction mixtures,
but these compounds were not isolated. Therefore, the physical properties of the
chlorotetrafluorides were unknown. This synthesis method using XeF2 was
industrially impractical because XeF2 is overly expensive for large scale
production.
[006] The present invention is directed toward overcoming one or more of the
problems discussed above.

SUMMARY OF THE INVENTION
[007] The present invention provides novel processes for the production of
arylsulfur pentafluoride, as represented by formula (I):

Embodiments of the invention include reacting at least one aryl sulfur compound, having a
formula (IIa) or (IIb),

with a halogen selected from the group of chlorine, bromine, iodine and interhalogens, and a
fluoro salt (M+F", formula III) to form an arylsulfur halotetrafluoride having a formula (IV):

The arylsulfur halotetrafluoride (formula IV) is reacted with a fluoride source to form the
arylsulfur pentafluoride (formula I).
[008] Embodiments of the present invention also provide processes for producing
an arylsulfur pentafluoride (formula I) by reacting at least one aryl sulfur
compound, having a formula (IIa) or (IIb), with a halogen selected from the group
of chlorine, bromine, iodine and interhalogens, and a fluoro salt (M+F", formula III)
to form an arylsulfur halotetrafluoride having a formula (IV):


The arylsulfur halotetrafluoride (formula IV) is reacted with a fluoride source in the presence
of a halogen selected from the group of chlorine, bromine, iodine, and interhalogens to form
the arylsulfur pentafluoride (formula I).
[009] Embodiments of the present invention also provide processes for producing
arylsulfur pentafluorides (formula I) by reacting an arylsulfur trifluoride having a
formula (V):

with a halogen selected from the group of chlorine, bromine, iodine and interhalogens, and a
fluoro salt (formula III) to form an arylsulfur halotetrafluoride having a formula (TV):

The arylsulfur halotetrafluoride (formula IV) is reacted with a fluoride source to form the
arylsulfur pentafluoride (formula I).
[0010] Embodiments of the present invention also provide processes for
producing arylsulfur pentafluorides (formula I) by reacting an arylsulfur trifluoride
having a formula (V):

with a halogen selected from the group of chlorine, bromine, iodine and interhalogens, and a
fluoro salt (formula III) to form an arylsulfur halotetrafluoride having a formula (IV).

[0011] The arylsulfur halotetrafluoride (formula IV) is reacted with a fluoride
source in the presence of a halogen selected from the group of chlorine, bromine,
iodine, and interhalogens to form the arylsulfur pentafluoride (formula I).
[0012] Embodiments of the present invention further provide processes for
producing arylsulfur halotetrafluoride (formula IV) by reacting at least one aryl
sulfur compound having a formula (IIa) or (IIb) with a halogen selected from a
group of chlorine, bromine, iodine and interhalogens, and a fluoro salt having a
formula (III) to form an arylsulfur halotetrafluoride having a formula (IV).
[0013] Embodiments of the present invention provide processes for producing
an arylsulfur pentafluoride (formula I) by reacting an arylsulfur halotetrafluoride
having a formula (IV) with a fluoride source. In some embodiments the fluoride
source has a boiling point of approximately 0°C or more at 1 arm.
[0014]. Finally, embodiments of the present invention provides processes for
producing an arylsulfur pentafluoride (formula I) by reacting an arylsulfur
halotetrafluoride having a formula (IV) with a fluoride source in the presence of a
halogen selected from the group of chlorine, bromine, iodine, and interhalogens to
form the arylsulfur pentafluoride.
[0015] In addition, the present invention provides novel arylsulfur
chlorotetrafluoride represented by formula (IV') and fluorinated arylsulfur
pentafluoride represented by formula (I'):

[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] Embodiments of the present invention provide industrially useful
processes for producing arylsulfur pentafluorides, as represented by formula (I).
Prepared arylsulfur pentafluorides can be used, for among other things, to
introduce one or more sulfur pentafluoride (SF5) groups into various target organic
compounds. Unlike previous methods in the art, the processes of the invention
utilize low cost reagents to prepare moderate to excellent yields of arylsulfur
pentafluoride compounds. Further, methods of the invention provide a greater
degree of overall safety in comparison to most prior art methodologies (for
example the use of F2 gas).
[0018] A distinction of the present invention is that the processes herein are
accomplished at a low cost as compared to other conventional methods. For
example, the reagents to perform Xe based reactions are cost prohibitive, whereas
the present invention utilizes low cost materials: halogens such as Cl2, Br2, and I2.
[0019] Embodiments of the invention include processes which comprise (see
for example Scheme 1, Processes I and II) reacting at least one aryl sulfur
compound having a formula (IIa) or a formula (IIb) with a halogen selected from
the group of chlorine, bromine, iodine, and interhalogens, and a fluoro salt having a
formula (III), to form an arylsulfur halotetrafluoride, represented by formula (IV).
The arylsulfur halotetrafluoride is then reacted with a fluoride source to form the
arylsulfur pentafluoride having a formula (I)._
Scheme 1: (Processes I and II)

[0020] With regard to formulas (I), (IIa), (IIb), (III), and (IV): substituents R1,
R2, R3, R4, and R5 each is independently a hydrogen atom; a halogen atom that is a
fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a substituted or
unsubstituted alkyl group having from 1 to 18 carbon atoms, preferably from 1 to

10 carbon atoms; a substituted or unsubstituted aryl group having from 6 to 30
carbon atoms, preferably from 6 to 15 carbon atoms; a nitro group; a cyano group;
a substituted or unsubstituted alkanesulfonyl group having from 1 to 18 carbon
atoms, preferably from 1 to 10 carbon atoms; a substituted or unsubstituted
arenesulfonyl group having from 6 to 30 carbon atoms, preferably from 6 to 15
carbon atoms; a substituted or unsubstituted alkoxy group having from 1 to 18
carbon atoms, preferably from 1 to 10 carbon atoms; a substituted or unsubstituted
aryloxy group having from 6 to 30 carbon atoms, preferably from 6 to 15 carbon
atoms; a substituted or unsubstituted acyloxy group having from 1 to 18 carbon
atom, preferably from 1 to 10 carbon atoms; a substituted or unsubstituted
alkanesulfonyloxy group having from 1 to 18 carbon atom, preferably from 1 to 10
carbon atoms; a substituted or unsubstituted arenesulfonyloxy group having from 6
to 30 carbon atoms, preferably from 6 to 15 carbon atoms; a substituted or
unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms, preferably from
2 to 10 carbon atoms; a substituted or unsubstituted aryloxycarbonyl group having
7 to 30 carbon atoms, preferably from 7 to 15 carbons; a substituted carbamoyl
group having 2 to 18 carbon atoms, preferably from 2 to 10 carbon atoms; a
substituted amino group having 1 to 18 carbon atoms, preferably from 1 to 10
carbon atoms; and a SF5 group; and R6 is a hydrogen atom, a silyl group, a metal
atom, an ammonium moiety, a phosphonium moiety, or a halogen atom.
[0021] With regard to M, M is a metal atom, an ammonium moiety, or a
phosphonium moiety, and with regard to X, X is a chlorine atom, a bromine atom,
or an iodine atom.
[0022] The term "alkyl" as used herein is linear, branched, or cyclic alkyl.
The alkyl part of alkanesulfonyl, alkoxy, alkanesulfonyloxy, or alkoxycarbonyl
group as used herein is also linear, branched, or cyclic alkyl part. The term
"substituted alkyl" as used herein means an alkyl moiety having one or more
substituents such as a halogen atom, a substituted or unsubstituted aryl group, and
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), which does not limit reactions of this
invention.
[0023] The term "substituted aryl" as used herein means an aryl moiety,
having one or more substituents such as a halogen atom, a substituted or
unsubstituted alkyl group, and 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), which does
not limit reactions of this invention.
[0024] The term "substituted alkanesulfonyl" as used herein means an
alkanesulfonyl moiety having one or more substituents such as a halogen atom, a
substituted or unsubstituted aryl group, and 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), which does not limit reactions of this invention.
[0025] The term "substituted arenesulfonyl" as used herein means an
arenesulfonyl moiety having one or more substituents such as a halogen atom, a
substituted or.unsubstituted alkyl group, and 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), which does not limit reactions of this invention.
[0026] The term "substituted alkoxy" as used herein means an alkoxy moiety
having one or more substituents such as a halogen atom, a substituted or
unsubstituted aryl group, and 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), which does not
limit reactions of this invention.
[0027] The term "substituted aryloxy" as used herein means an aryloxy
moiety having one or more substituents such as a halogen atom, a substituted or
unsubstituted alkyl group, and 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), which does
not limit reactions of this invention.
[0028] The term "substituted acyloxy" as used herein means an acyloxy
moiety having one or more substituents such as a halogen atom, a substituted or
unsubstituted alkyl group, a substituted or unsubstituted aryl group, and 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), which does not limit reactions of this invention.
[0029] The term "substituted alkanesulfonyloxy" as used herein means an
alkanesulfonyloxy moiety having one or more substituents such as a halogen atom,
a substituted or unsubstituted aryl group, and 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), which does not limit reactions of this invention.
[0030] The term "substituted arenesulfonyloxy" as used herein means an
arenesulfonyloxy moiety haying one or more substituents such as a halogen atom, a

substituted or unsubstituted alkyl group, and 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), which does not limit reactions of this invention.
[0031] The term "substituted alkoxycarbonyl" as used herein means an
alkoxycarbonyl moiety having one or more substituents such as a halogen atom, a
substituted or unsubstituted aryl group, and 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), which does not limit reactions of this invention.
[0032] The term "substituted aryloxycarbonyl" as used herein means an
aryloxycarbonyl moiety having one or more substituents such as a halogen atom, a
substituted or unsubstituted alkyl group, and 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), which does not limit reactions of this invention.
[0033] The term "substituted carbamoyl" as used herein means a carbamoyl
moiety having one or more substituents such as a substituted or unsubstituted alkyl
group, a substituted or unsubstituted aryl group, and 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), which does not limit reactions of this invention.
[0034] The term "substituted amino" as used herein means an amino moiety
having one or more substituents such as a substituted or unsubstituted acyl group, a
substituted or unsubstituted alkanesulfonyl group, a substituted or unsubstituted
arenesulfonyl groups and 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), which does not
limit reactions of this invention.
[0035] Among the substituents, R1, R2, R3, R4, and R5, described above, a
hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a
substituted or unsubstituted aryl group, a nitro group, a cyano group, a substituted
or unsubstituted alkanesulfonyl group, a substituted or unsubstituted arenesulfonyl
group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted
aryloxy group, a substituted or unsubstituted acyloxy group, and a substituted or
unsubstituted alkoxycarbonyl group are preferable, and a hydrogen atom, a halogen
atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl
group, and a nitro group are more preferable from the viewpoint of availability of
the starting materials..

[0036] Note that according to the nomenclature of Chemical Abstract Index
Name, and in accordance with the present disclosure, for example, C6H5-SF5 is
named sulfur, pentafluorophenyl-; p-Cl-C6H4-SF5 is named sulfur, (4-
chlorophenyl)pentafluoro-; and P-CH3-C6H4-SF5 is named sulfur, pentafluoro(4-
methylphenyl)-. C6H5-SF4Cl is named sulfur, chlorotetrafluorophenyl-; p-CH3-
C6H4-SF4Cl is named sulfur, chlorotetrafluoro(4-methylphenyl)-; and p-NO2-C6H4-
SF4CI is named sulfur, chlorotetrafluoro(4-nitrophenyl)-.
[0037] Arylsulfur halotetrafluoride compounds of formula (IV) include
isomers such as trans-isomers and cis-isomers as shown below; arylsulfur
halotetrafluoride is represented by ArSF4X:



Process I (Scheme 1)
[0040] Process I includes reacting at least one aryl sulfur compound, having a
formula (IIa) or (IIb), with a halogen selected from the group of chlorine, bromine,
iodine and interhalogens, and a fluoro salt (M+F", formula III) to form an arylsulfur
halotetrafluoride having a formula (IV).
[0041] The substituent(s), R1, R2, R3, R4, and R5, of the products represented
by the formula (IV) may be different from the substituent(s), R1, R2, R3, R4, and R5,
of the starting materials represented by the formulas (IIa) and/or (IIb). Thus,
embodiments of this invention include transformation of the R1, R2, R3, R4, and Rs
to different R1, R2, R3, R4, and R5 which may take place during the reaction of the
present invention or under the reaction conditions as long as the -S-S- or -S-moiety
is transformed to a -SF4X group(s).
[0042] Illustrative aryl sulfur compounds, as represented by formula (IIa), of
the invention include, but are not limited to: diphenyl disulfide, each isomer of
bis(fluorophenyl) disulfide, each isomer of bis(difluorophenyl) disulfide, each
isomer of bis(trifluorophenyl) disulfide, each isomer of bis(tetrafluorophenyl)
disulfide, bis(pentafluorophenyl) disulfide, each isomer of bis(chlorophenyl)
disulfide, each isomer of bis(dichorophenyl) disulfide, each isomer of
bis(trichlorophenyl) disulfide, each isomer of bis(bromophenyl) disulfide, each
isomer of bis(dibromophenyl) disulfide, each isomer of bis(iodophenyl) disulfide,
each isomer of bis(chlorofluorophenyl) disulfide, each isomer of
bis(bromofluorophenyl) disulfide, each isomer of bis(bromochlorophenyl)
disulfide, each isomer of bis(fluoroiodophenyl) disulfide, each isomer of bis(tolyl)
disulfide, each isomer of bis[(methoxymethyl)phenyl] disulfide, each isomer of
bis{[(cyclohexyloxy)methyi]phenyl} disulfide, each isomer of
bis[(phenylmethyl)phenyl] disulfide, each isomer of bis[(cyanomethyl)phenyl]
disulfide, each isomer of bis[(nitromethyl)phenyl] disulfide, each isomer of
bis.{[(methanesulfonyl)methyl]phenyl} disulfide, each isomer of
bis{[(benzenesulfonyl)methyl]phenyl} disulfide, each isomer of bis(ethylphenyl)

disulfide, each isomer of bis[(methoxyethyl)phenyl] disulfide, each isomer of
bis[(nitroethyl)phenyl] disulfide, each isomer of bis[(phenylethyl)phenyl] disulfide,
each isomer of bis[chloro(methyl)phenyl] disulfide, bis[bromo(methyl)phenyl]
disulfide, each isomer of bis[(trifluoromethyl)phenyl] disulfide, each isomer of
bis(dimethylphenyl) disulfide, each isomer of bis[chloro(dimethyl)phenyl]
disulfide, each isomer of bis[di(trifluoromethyl)phenyl] disulfide, each isomer of
bis(trimethy I phenyl) disulfide, each isomer of bis[chloro(trimethyl)phenyl]
disulfide, each isomer of bis(tetramethylphenyl) disulfide, each isomer of
bis[chloro(tetramethyl)phenyl] disulfide, bis(pentamethylphenyl) disulfide, each
isomer of bis(ethylphenyl) disulfide, each isomer of bis[(2,2,2-
. trifluoroethyl)phenyl] disulfide, each isomer of bis[(perfluoroethyl)phenyl]
disulfide, each isomer of bis(diethylphenyl) disulfide, each isomer of
bis(ethylmethylphenyl) disulfide, each isomer of bis(propylphenyl) disulfide, each
isomer of bis(isopropylphenyn disulfide, each isomer of bis(butylphenyl) disulfide,
each isomer of bis(sec-butylphenyl) disulfide, each isomer of bis(isobutylphenyl)
disulfide, each isomer of bis(tert-butylphenyl) disulfide, each isomer of
bis(cyclopropylphenyl) disulfide, each isomer of bis(cyclopentylphenyl) disulfide,
each isomer of bis(cyclohexylphenyl) disulfide, each isomer of
bis{[(cyclohexyl)cyclohexyl]phenyl} disulfide, each isomer of bis(biphenyl)
disulfide, each isomer of bis(tolylphenyl) disulfide, each isomer of
bis[(chlorophenyl)phenyi] disulfide, each isomer of bis[(bromophenyl)phenyl]
disulfide, each isomer of bis[(nitrophenyl)phenyl] disulfide, each isomer of
bis(terphenylyl) disulfide, each isomer of bis[(phenyl)terphenylyl] disulfide, each
isomer of bis[(methanesulfonyl)phenyl] disulfide, each isomer of
bis[(trifluoromethanesulfonyl)phenyl] disulfide, each isomer of
bis[(benzenesulfonyl)phenyl] disulfide, each isomer of
bis[(toluenesulfonyl)phenyl] disulfide, each isomer of bis(methoxyphenyl)
disulfide, each isomer of bis(ethoxyphenyl) disulfide, each isomer of
bis(propoxyphenyl) disulfide, each isomer of bis(butoxyphenyl) disulfide, each
isomer of bis(cyclopropylphenyl) disulfide, bis(cyclohexyloxylphenyl) disulfide,
each isomer of bis[(trifluoromethoxy)phenyl] disulfide, each isomer of
bis[(perfluoroethoxyl)phenyl] disulfide, each isomer of
bis[(trifluoroethoxy)phenyl] disulfide, each isomer of
bis[(tetrafluoroethoxy)phenyl] disulfide, each isomer of

bis[(perfluoropropoxy)phenyl] disulfide, each isomer of bis(phenyloxyphenyl)
disulfide, each isomer of bis(fluorophenyloxyphenyl) disulfide, each isomer of
bis(chlorophenyloxyphenyl) disulfide, each isomer of bis(bromophenyloxyphenyl)
disulfide, each isomer of bis(nitrophenyloxyphenyi) disulfide, each isomer of
bis[(dinitrophenyloxy)phenyl] disulfide, each isomer of
bis[(pentafluorophenyloxy)phenyl] disulfide, each isomer of
bis(trifluoromethylphenyloxyphenyl) disulfide, each isomer of
bis(cyanophenyloxyphenyl) disulfide, each isomer of bis(naphthyloxylphenyl)
disulfide, each isomer of bis[(heptafluoronaphthyloxy)phenyl] disulfide, each
isomer of bis[acetoxyphenyl] disulfide, each isomer of bis[(benzoyloxy)phenyl]
disulfide, each isomer of bis[(methanesulfonyloxy)phenyl] disulfide, each isomer
of bis[(benzenesulfonyloxy)phenyl] disulfide, each isomer of
bis[(toluenesulfonyloxy)phenyl] disulfide, each isomer of
bis[(methoxycarbonyl)phenyl] disulfide, each isomer of
bis[(ethoxycarbonyl)phenyl] disulfide, each isomer of
bis[(phenoxycarbonyl)phenyl] disulfide, each isomer of bis[(N,N-
dimethylcarbamoyl)phenyl] disulfide, each isomer of bis[(N,N-
diethylcarbamoyl)phenyl] disulfide, each isomer of bis[(N,N-
diphenylcarbamoyl)phenyl] disulfide, each isomer of bis[(N,N-
dibenzylcarbamoyl)phenyl] disulfide, each isomer of bis[(N-acetyl-N-
methylamino)phenyl] disulfide, each isomer of bis[(N-acetyl-N-
phenylamino)phenyl] disulfide, each isomer of bis[(N-acetyl-N-
benzylamino)phenyl] disulfide, each isomer of bis[(N-benzoyl-N-
methylamino)phenyl] disulfide, each isomer of bis[(N-methanesulfonyl-N-
methylamino)phenyl] disulfide, each isomer of bis[(N-toluenesulfonyl-N-
methylamino)phenyl] disulfide, each isomer of bis[(N-toluenesulfonyl-N-
benzylamino)phenyl] disulfide, and each isomer of
bis[(pentafluorosulfanyl)phenyl] disulfide. Each of the above formula (IIa)
compounds is available (see for example Sigma, Acros, TCI, Lancaster, Alfa
Aesar, etc.) or can be prepared in accordance with understood principles of
synthetic chemistry.
[0043] Illustrative aryl sulfur compounds, as represented by formula (IIb), of
the invention include, but are not limited to: benzenethiol, each isomer of
fluorobenzenethiol (o-, m-, and p-fluorobenzenethiol), each isomer of

chlorobenzenethiol, each isomer of bromobenzenethiol, each isomer of
iodobenzenethiol, each isomer of difluorobenzenethiol, each isomer of
trifluorobenzenethiol, each isomer of tetrafluorobenzenethiol,
pentafluorobenzenethiol, each isomer of dichlorobenzenethiol, each isomer of
chlorofluorobenzenethiol, each isomer of methylbenzenethiol, each isomer of
(trifluoromethyl)benzenethiol, each isomer of dimethylbenzenethiol, each isomer
of bis(trifiuorometyl)benzenethiol, each isomer of
methyl(trifluoromethyl)benzenethiol, each isomer of trimethylbenzenethiol, each
isomer of tetramethylbenzenethiol, pentamethylbenzenethiol, each isomer of
ethylbenzenethiol, each isomer of (2,2,2-trifluoroethyl)benzenethiol, each isomer
of (perfluoroethyl)benzenethiol, each isomer of diethylbenzenethiol, each isomer of
ethylmethylbenzenethiol, each isomer of propylbenzenethiol, each isomer of
isopropylbenzenethiol, each isomer of butylbenzenethiol, each isomer of sec-
butylbenzenethiol, each isomer of isobutylbenzenethiol, each isomer of tert-
butylbenzenethiol, each isomer of nitrobenzenethiol, each isomer of
dinitrobenzenethiol, each isomer of cyanobenzenethiol, each isomer of
phenylbenzenethiol, each isomer of tolylbenzenethiol, each isomer of
(chlorophenyl)benzenethiol, each isomer of (bromophenyl)benzenethiol, each
isomer of (nitrophenyl)benzenethiol, each isomer of
(methanesulfonyl)benzenethiol, each isomer of
(trifluoromethanesulfonyl)benzenethiol, each isomer of
(benzenesulfonyl)benzenethiol, each isomer of (toluenesulfonyl)benzenethiol3 each
isomer of (methoxycarbonyl)benzenethiol, each isomer of
(ethoxycarbonyl)benzenethiol, each isomer of (phenoxycarbonyl)benzenethiol,
each isomer of (N,N-dimethylcarbamoyl)benzenethiol, each isomer of (N,N-
diethylcarbamoyl)benzenethiol, each isomer of (N,N-
dibenzylcarbamoyl)benzenethiol, each isomer of (N,N-
diphenylcarbamoyl)benzenethiol, each isomer of (N-acetyl-N-
methylamino)benzenethiol, each isomer of (N-acetyl-N-phenylamino)benzenethiol,
each isomer of (N-acetyl-N-benzylamino)benzenethiol, each isomer of (N-benzoyl-
N-methylamino)benzenethibl, each isomer of (N-methanesulfonyl-N-
methylamino)benzenethiol, each isomer of (N-toluenesulfonyl-N-
methylamino)benzenethiol, each isomer of (N-toluenesulfonyl-N-
benzylamino)benzenethiol, and each isomer of (pentafluorosulfanyl)benzenethiol;

lithium, sodium, and potassium salts of the benzenethiol compounds exemplified
here; ammonium, diethylammonium, triethylammonium, trimethylammnoim,
tetramethyl ammonium, tetraethylammonium, tetrapropylammonium, and
tetrabutylammonium salts of the benzenethiol compounds exemplified here;
tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium,
tetrabutylphosphonium, and tetraphenylphosphonium salts of the benzenethiol
compounds exemplified here; and S-trimethylsilyl, 5-triethylsilyl, S-tripropylsilyl,
S-dimethyl-t-butylsilyl, and S-dimefhylphenylsilyl derivative of the benzenethiol
compounds exemplified here. Examples of aryl sulfur compounds of formula (IIb)
where R6 is a halogen atom are benzenesulfenyl chloride, each isomer of
nitrobenzenesulfenyl chloride, each isomer of dinitrobenzenesulfenyl chloride, and
other like compounds. Each of the above formula (IIb) compounds is available
(see for example Sigma, Acros, TCI, Lancaster, Alfa Aesar, etc.) or can be
prepared in accordance with understood principles of synthetic chemistry.
[0044] Typical halogens employable in the present invention include chlorine
(CI2), bromine (Br2), iodine (I2), and interhalogens such as C1F, BrF, ClBr, C1I,
CI3I, and BrI. Among these, chlorine (Cl2) is preferable due to low cost.
[0045] Fluoro salts, having a formula (III), are those which are easily
available and are exemplified by metal fluorides, ammonium fluorides, and
phosphonium fluorides. Examples of suitable metal fluorides are alkali metal
fluorides such as lithium fluoride, sodium fluoride, potassium fluoride (including
spray-dried potassium fluoride), rubidium fluoride, and cesium fluoride. Examples
of suitable ammonium fluorides are tetramethylammonium fluoride,
tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium
fluoride, benzyltrimethylammonium fluoride, benzyltriethylammonium fluoride,
and so on. Examples of suitable phosphonium fluorides are
tetramethylphosphonium fluoride, tetraethylphosphonium fluoride,
tetrapropylphosphonium fluoride, tetrabutylphosphonium fluoride,
tetraphenylphosphonium fluoride, tetratolylphosphonium fluoride, and so on. The
alkali metal fluorides, such as potassium fluoride and cesium fluoride, are
preferable from the viewpoint of availability and capacity to result in high yield,
and potassium fluoride is most preferable from the viewpoint of cost.
[0046] As a fluoro salt (formula III), there can be used a mixture of a metal
fluoride and an ammonium fluoride or a phosphonium fluoride, a mixture of an

ammonium fluoride and a phosphonium fluoride, and a mixture of a metal fluoride,
an ammonium fluoride, and a phosphonium fluoride.
[0047] As a fluoro salt (formula III), there can also be used a mixture of a
metal fluoride and an ammonium salt having an anion part other than F"; a mixture
of a metal salt having an anion part other than F" and an ammonium fluoride; a
mixture of a metal fluoride and a phosphonium salt having an anion part other than
F"; a mixture of a metal salt having an anion part other than F" and a phosphonium
fluoride; a mixture of an ammonium fluoride and a phosphonium salt having an
anion part other than F"; and a mixture of an ammonium salt having an anion part
other than F" and a phosphonium fluoride. Furthermore, there can be used a mixture
of a metal fluoride, an ammonium fluoride, and a phosphonium salt having an
anion part other than F"; a mixture of a metal fluoride, an ammonium salt having an
anion part other than F", and a phosphonum fluoride; a mixture of a metal salt
having an anion part other than F", an ammonium fluoride, and a phosphonium
fluoride; a mixture of a metal fluoride, an ammonium salt having an anion part
other than F", and a phosphonium salt having an anion part other than F"; and so on.
These salts can undertake a mutual exchange reaction of the anion parts between
and among these salts (for example, see Scheme 2).
Scheme 2: Mutual anion exchange reaction between salts

[0048] The combination of these salts may accelerate the reactions in Process
I, because the reaction may depend on the solubility of the fluoro salts to the
solvent used. As such, a high concentration of fluoride anions (F") will increase the
available fluoride anion during the reaction. Therefore, one may choose a suitable
combination of these salts in order to increase the effective concentration of F". The
amount (used against the amount of the metal fluoride, ammonium fluorides,
and/or phosphonium fluorides) of the metal, ammonium, and phosphonium salts
having anion parts other than F" can be chosen from the catalytic amounts to any
amounts that do not interfere with the reactions or do not so decrease the yields of
the products. The anion parts other than F" can be chosen from any anions which do
not limit the reactions or do not so decrease the yields of the products. The
examples of the anion parts other than F" are, but are not limited to, Cl-, Br-, I-, BF4-,

PF6-, S(V, OCOCH3, 'OCOCF3, -OSOiCHs, -OSO2CF3, -OSO2C4F9, -OS02C6H5,
"OSO2C6H4CH3, "OS02C6H4Br, and so on. Among thern, the anion parts (other than
F") which do not have an oxygen anion(s) are preferable, and CI", BF4" and PFe" are
more preferable because of high yield reactions. In addition, CI" is most preferable
because of the cost.
[0049] From the viewpoint of efficiency and yields of the reactions, Process I
is preferably carried out in the presence of one or more solvents. The solvent is
preferably an inert, polar, aprotic solvent. The preferable solvents will not
substantially react with the starting materials and reagents, the intermediates, and
the final products. Suitable solvents include, but are not limited to, nitriles, ethers,
nitro compounds, and so on, and mixtures thereof. Illustrative nitriles are
acetonitrile, propionitrile, benzonitrile, and so on. Illustrative ethers are
tetrahydrofuran, diethyl ether, dipropyl ether, dibutyl ether, t-butyl methyl ether,
dioxane, glyme, diglyme, triglyme, and so on. Illustrative nitro compounds are
nitromethane, nitroethane, nitropropane, nitrobenzene, and so on. Acetonitrile is a
preferred solvent for use in Process I from a viewpoint of providing higher yields
of the products.
[0050] In order to obtain good yields of product in Process I, the reaction
temperature can be selected in the range of about -60°C ~ +70°C. More preferably,
the reaction temperature can be selected in the range of about -40°C ~ +50°C.
Furthermore preferably, the reaction temperature can be selected in the range of
about -20°C ~ +40°C.
[0051] Reaction conditions of Process I are optimized to obtain economically
good yields of product. In one illustrative embodiment, from about 5 mol to about
20 mol of halogen are combinedjwith about 1 mol of aryl sulfur compound
(formula Ha) to obtain a good yield of arylsulfur halotetrafluorides (formula IV).
In another embodiment, from about 3 to about 12 mol of halogen are combined
with 1 mol of aryl sulfur compound of formula lib (R6=a hydrogen atom, a silyl
. group, a metal atom, an ammonium moiety, or a phosphonium moiety) to obtain
good yields of arylsulfur halotetrafluorides (formula IV). From about 2 to about 8
mol of halogen are combined with 1 mol of aryl sulfur compound of formula lib
(R6=a halogen atom) to obtain good yields of arylsulfur halotetrafluorides (formula
IV). The amount of a fluoro salt (formula III) used in embodiments of Process I
can be in the range of from about 8 to about 24 mol against 1 mol of aryl sulfur

compound of formula (IIa) to obtain economically good yields of product. The
amount of a fluoro salt (formula I'll) used in embodiments of Process I can be in the
range of from about 4 to about 12 mol against 1 mol of aryl sulfur compound of
formula (IIb) to obtain economically good yields of product.
[0052] 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 0.5 h to several
days, preferably, within a few days.
[0053] Scheme 3: Reaction mechanism for Process I

[0054] A more complete reaction mechanism of Process I is shown in Scheme
3 above. Aryl sulfur compound of formula (IIa) reacts with halogen to form
arylsulfur halide (lib'—lib when R6=a halogen atom), which then reacts with
halogen and fluoro salt (M+F") to form arylsulfur trifluoride (formula V). The
arylsulfur trifluoride further reacts with halogen and fluoro salt to give the
arylsulfur halotetrafluoride (formula (IV)). As such, the compounds as represented

by formula (V) act as intermediates in the formation of compounds of formula
(IV). The compounds as represented by formula (lib') also act as intermediates.
The starting aryl sulfur compound of formula (lib when R6=a halogen atom) reacts
with halogen and fluoro salt to form the arylsulfur trifluoride. Aryl sulfur
compounds as represented by formula (lib when R6=a hydrogen atom, a metal
atom, an ammonium moiety, or a phosphonium moiety) react with halogen to form
aryl sulfur compounds as represented by formula (IIa) or formula (lib'), which then
reacts with halogen and fluoro salt to give the arylsulfur trifluoride (formula V). As
such, the compounds as represented by formula (IIa) or (lib') act as intermediates
in the formation of compounds of formula (IV) from aryl sulfur compounds of
formula (lib; R6 except for a halogen atom). The reaction mechanism for the
production of arylsulfur halotetrafluoride (formula IV) via arylsulfur trifluoride
(formula V) was confirmed by 19F NMR of an intermediate reaction mixture. In
addition, the arylsulfur trifluoride can be converted to the arylsulfur
halotetrafluoride (formula IV) under the similar reaction conditions as
demonstrated by at least Example 14.
Process II (Scheme 1)
[0055] Embodiments of the invention include Process II: a reaction of
arylsulfur halotetrafluoride, obtained by the process I, with a fluoride source, as
shown in Scheme 1.
[0056] The substituent(s), R1, R2, R3, R4, and R5S of the products represented
by the formula (I) may be different from the substituent(s), R1, R2, R3, R4, and R5,
of the materials represented by the formula (IV). Thus, embodiments of this
invention include transformation of the R1, R2, R3, R4, and R5 to different R1, R2,
R3, R4, and R5 which may take place during the reaction of the present invention or
under the reaction conditions as long as the —SF4X is transformed to a-SFs group.
[0057] Fluoride sources employable in Process II are anhydrous compounds
that display fluoride activity to the arylsulfur halotetrafluoride (formula IV). The
fluoride sources can be selected from fluorides of typical elements in the Periodic
Table, fluorides of transition elements in the Periodic Table, and mixture or
compounds between or among these fluorides of typical elements and/or transition
elements. The fluoride source may be a mixture, salt, or complex with an organic

molecule(s) that does(do) not limit the reactions of this invention. The fluoride
sources also include mixtures or compounds of fluoride sources with fluoride
source-activating compounds such as SbCb, A1C13, PCI5, BCI3, and so on. Process
IT can be carried out using one or more fluoride sources.
[0058] Suitable examples of fluorides of the typical elements include fluorides
of Element 1 in the Periodic Table such as hydrogen fluoride (HF) and alkali metal
fluorides, LiF, NaF, KF, RbF, and CsF; fluorides of Element 2 (alkaline earth metal
fluorides) such as BeF2, MgF2, MgFCl, CaF2, SrF2, BaF2 and so on; fluorides of
Element 13 such as BF3; BF2C1, BFCl2j A1F3, A1F2C1, A1FC12, GaF3, TnF3, and so
on; fluorides of Element 14 such as SiF4, SiF3Cl, SiF2Cl2, SiFCl3, GeF4, GeF2Cl2,
SnF4, PbF2, PbF4, and so on; fluorides of Element 15 such as PF5, AsF5, SbF3, SbF5)
SbF4Cl, SbF3Cl2, SbFz,Cl3 , SbFCL,, BiF5) and so on; fluorides of Element 16 such
as OF2, SeF4, SeF6, TeF4, TeF6, and so on; fluorides of Element 17 such as F2, CIF,
CIF3, BrF, BrF3, IF6, and so on.
[0059] Suitable examples of fluorides of the transition elements (transition
meal fluorides) include fluorides of Element 3 in the Periodic Table such as ScF3,
YF3, LaF3, and so on; fluorides of Element 4 such as TiF4, ZrF3, ZrF4, HfF4, and so
on; fluorides of Element 5 such as VF3, VF5, NbF5, TaFs, and so on; fluorides of
Element 6 such as CrF3) M0F6, WF6, and so on; fluorides of Element 7 such as
MnF2, MnF3, ReF6, and so on; fluorides of Element 8 such as FeF3, RuF3, RuF4,
OsF4, OsF5, OsF6, and so on; fluorides of Element 9 such as CoF2, C0F3, RhF3, IrF6,
and so on; fluorides of Element 10 such as NiF2, PdF2, PfF2, PtF4, PtF6, and so on;
fluorides of Element 11 such as CuF2,CuFCI, AgF, AgF2, and so on; fluorides of
Element 12 such as ZnF2, ZnFCl, CdF2, HgF2) and so on:
[0060] Suitable examples of mixture or compounds between or among the
fluorides of typical elements and/or transition elements include, but are not limited
to, HBF4 [a compound of hydrogen fluoride (HF) and BF3], HPF6, HAsF6, HSbF6,
LiF/HF [a mixture or salt of lithium fluoride(LiF) and hydrogen fluoride(HF)],
NaF/HF, KF/HF, CsF/HF, (CH3)4NF/HF, (C2H3)4NF/HF, (C4H9) 4NF/HF, ZnF2/HF,
CuF2/HF, SbF5/SbF3, SbF5/SbF3/HF, ZnF2/SbF5, ZnF2/SbF5/HF, KF/SbF5, KF/SbFj/
HF, and so on.
[0061] Suitable examples of mixtures, salts, or complexes of the fluorides
with organic molecules include, but are not limited to, BF3 diethyl etherate
[BF3-0(C2H3)2], BF3 dimethyl etherate, BF3 dibutyl etherate, BF3 tetrahydrofuran

complex,BF3 acetonitrile complex (BF3-NCCH3), HBF4 diethyl etherate,
HF/pyridine (a mixture of hydrogen fluoride and pyridine), FIF/methylpyridine,
HF/dimethylpyridine, HF/trimethylpyridine, HF/trimethylamine, FIF/triethylamine,
FCF/dimethyl ether, HF/diethyl ether, and so on. As HF/pyridine, a mixture of about
70wt% hydrogen fluoride and about 30wt% pyridine is preferable because of
availability.
[0062] Among these examples of fluoride sources mentioned above, transition
metal fluorides, fluorides of the Elements 13-15, hydrogen fluoride, and mixtures
or compounds thereof, and mixtures, salts, or complexes of these fluorides with
organic molecules are preferable.
[0063] Among the transition metal fluorides, the fluorides of Elements 11 (Cu,
Ag, Au) and 12 (Zn, Cd, Hg) are exemplified preferably. ZnF2 and CuF2 are
furthermore preferable from the viewpoint of practical operation, yields, and cost.
Among the fluorides of the Elements 13-15, BF3, A1F3, A1F2C1, SbF3, SbF5,
SbF4Cl, and SbF3Ci2 are preferably exemplified. Fluorides of Elements 13-15 can
be used preferably for the preparation of polyfluorinated arylsulfur pentafluorides.
Among the organic molecules usable for the mixtures, salts, or complexes with the
fluorides, pyridine, ethers such as dimethyl ether, diethyl ether, dipropyl ether, and
diisopropyl ether, alkylamines such as trimethylamine and triethylamine, and
nitriles such as acetonitrile and propionitrile are preferable. Among these, pyridine,
diethyl ether, triethylamine, and acetonitrile are more preferable because of
availability and cost.
[0064] In. some cases, since the reaction of an arylsulfur halotetrafluoride and
a fluoride source can be slowed down by flowing an inactive gas such as nitrogen
(see Examples 18 and 19), it is not preferable that the vapor on the reaction mixture
and/or the gas which may be generated from the reaction mixture be removed, for
example by flowing an inactive gas on or through the reaction mixture or other
methods. This was an unexpected finding discovered by the inventor, as one would
not expect removal of the reaction vapor to slow the reaction. Therefore, there is a
case that it is preferable that the reaction be carried out in a closed or sealed
reactor, by maintaining the reactor at a constant pressure, or by equipping the
reactor with a balloon filled with an inactive gas such as nitrogen, or in any other
like manner. In this manner, embodiments of the invention facilitate the presence
of the reaction vapor.

[0065] Process II can be carried out with or without a solvent. However, in
many cases, unlike most organic reactions, the present invention typically does not
require a solvent. This presents an added advantage to performing embodiments of
the invention (due to lower cost, no solvent separating requirements, etc). In some
cases, the use of solvent is preferable for mild and efficient reactions. Where a
solvent is utilized, alkanes, halocarbons, ethers, nitriles, nitro compounds can be
used. Example alkanes include normal, branched, cyclic isomers of pentane,
hexane, heptane, octane, nonane, decane, dodecan, undecane, and other like
compounds. Illustrative halocarbons include dichloromethane, chloroform, carbon
tetrachloride, dichloroethane, trichloroethane, terachloroethane,
trichlorotrifluoroethane, chlorobenzene, dichlorobenzene, trichlorobenzene,
hexafluorobenzene, benzotrifluoride, bis(trifluoromethyl)benzene,
perfluorohexane, perfluorocyclohexane, perfluoroheptane, perfluorooctane,
perfluorononane, perfluorodecane, perfluorodecalin, and other like compounds.
Illustrative ethers include diethyl ether, dipropyl ether, di(isopropyl) ether, dibutyl
ether, t-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 nitro compounds
include nitromethane, nitroethane, nitrobenzene, and other like compounds. Where
the fluoride source used for the reaction is liquid, it can be used as both a reactant
and a solvent. A typical example of this is hydrogen fluoride and a mixture of
hydrogen fluoride and pyridine. Hydrogen fluoride and a mixture of hydrogen
fluoride and pyridine may be usable as a solvent.
[0066] In order to optimize yield with regard to Process II, the reaction
temperature is selected in the range of from about -100°C to about +250°C. More
typically, the reaction temperature is selected in the range of from about -80°C to
about +230°C. Most typically, the reaction temperature is selected in the range of
from about -60°C to about +200°C.
[0067] In order to obtain economically good yields of the products, the
amount of a fluoride source which provides n number of reactive fluoride
(employable for the reaction) per molecule can be selected in the range of from
about 1/n to about 20/n mol against 1 mol of arylsulfur halotetrafluoride (see
formula IV). More typically, the amount, can be selected in the range of from about
1/n to about 10/n mol from the viewpoint of yield and cost, as less amounts of a

fluoride source decrease the yield(s) and additional amounts of a. fluoride source do
not significantly improve the yield(s).
[0068] As described in Process I, the reaction time of Process II also varies
dependent on reaction temperature, the substrates, reagents, solvents, and their
amounts used. Therefore, one can modify reaction conditions to determine the
amount of time necessary for completing the reaction of Process II, but can be from
about 0.1 h to several days, preferably, within a few days.
[0069] Embodiments of the invention include processes which comprise (see
for example Scheme 4, Processes I and II') reacting at least one aryl sulfur
compound having a formula (IIa) or a formula (IIb) with a halogen selected from
the group of chlorine, bromine, iodine, and interhalogens, and a fluoro salt having a
formula (III), to form an arylsulfur halotetrafluoride, represented by formula (IV).
The arylsulfur halotetrafluoride is then reacted with a fluoride source in the
presence of a halogen selected from the group of chlorine, bromine, iodine, and
interhalogens to form the arylsulfur pentafluoride as represented by a formula (I).

[0070] Process I is as described above.
[0071] Process IP is the same as Process II above except for the following
modifications: The reaction of an arylsulfur halotetrafluoride and a fluoride source
can be accelerated by a halogen selected from the group of chlorine, bromine,
iodine, and interhalogens (see Examples 15-17).
[0072] The substituent(s), R1, R2, R3, R4, and R5, of the products represented
by the formula (I) may be different from the substituent(s), R1, R2, R3, R4, and R5,
of the materials represented by the formula (IV). Thus, embodiments of this
invention include transformation of the R1, R2, R3, R4, and R5 to different R1, R2,

R3, R4, and R5 which may take place during the reaction of the present invention or
under the reaction conditions as long as the -SF4X is transformed to a -SF5 group.
[0073] The acceleration of the reactions by the presence of a halogen in some
cases was an unexpected and surprising finding as discovered by the inventor.
While not wanting to be tied to a particular mechanism, it is believed that the
halogen activates a fluoride source and/or prevents disproportionation of an
arylsulfur halotetrafluoride (formula IV) which may occur during this reaction.
Therefore, other fluoride source-activating and/or dispropdrtionation-preventing
compounds are within the scope of the invention. The reaction in the presence of
the halogen may be carried out by methods such as by adding a halogen to the
reaction mixture, dissolving a halogen in the reaction mixture, flowing a halogen
gas or vapor into the reaction mixture or the reactor, or others like means. Among
the halogens, chlorine (CI2) is preferable because of cost.
[0074] The amount of halogen is from a catalytic amount to an amount in
large excess. From the viewpoint of cost, a catalytic amount to 5 mol of the
halogen, can be preferably selected against 1 mol of arylsulfur halotetrafluoride
(formula IV).
[0075] Embodiments of the present invention include a process (Process III)
which comprises reacting an arylsulfur trifluoride having a formula (V) with a
halogen (chlorine, bromine, iodine, or interhalogens) and a fluoro salt having a
formula (III) to form an arylsulfur halotetrafluoride having a formula (IV) and
(Process II) reacting the obtained arylsulfur halotetrafluoride with a fluoride source
to form the arylsulfur pentafluoride having a formula (I). Scheme 5 showing
Processes III and II are shown as follows:
Scheme 5 (Processes III and II)

[0076] With regard to formulas (I), (III), (IV), and (V), R1, R2, R3, R\ R5; R6,
M and X have the same meaning as defined above.
Process III (Scheme 5)

[0077] Embodiments of the present invention provide processes for producing
arylsulfur pentafluorides (formula 1) by reacting an arylsulfur trifluoride having a
formula (V) with a halogen selected from the group of chlorine, bromine, iodine,
and interhalogens and a fluoro salt (formula III) to form an arylsulfur
halotetrafluoride having a formula (IV).
[0078] The substituent(s), R1, R2, R3, R4, and R5, of the products
represented by the formula (IV) may be different from the substituent(s), R', R2, R3,
R4, and R5, of the starting materials represented by the formula (V). Thus,
embodiments of this invention include transformation of the R1, R2, R3, R4, and R5
to different R1, R2, R3, R4, and R3 which may take place during the reaction of the
present invention or under the reaction conditions as long as the -SF3 is
transformed to a —SF4X
[0079] Illustrative arylsulfur trifluorides, as represented by formula (V), of the
invention can be prepared as described in the literature [see J. Am. Chem. Soc,
Vol. 84 (1962), pp. 3064-3072, and Synthetic Communications Vol. 33 (2003),
pp.2505-2509] and are exemplified, but are not limited, by phenylsulfur trifluoride,
each isomer of fluorophenylsulfur trifluoride, each isomer of difluorophenylsulfur
trifluoride, each isomer of trifluorophenylsulfur trifluoride, each isomer of
tetrafluoro phenyl sulfur trifluoride, pentafluorophenylsulfur trifluoride, each isomer
of chlorophenylsulfur trifluoride, each isomer of bromophenylsulfur trifluoride,
each isomer of chlorofluorophenylsulfur trifluoride, each isomer of
bromofluorophenylsulfur trifluoride, each isomer of tolylsulfur trifluoride, each
isomer of chloro(methyl)phenylsulfur trifluoride, each isomer of
dimethylphenylsulfur trifluoride, each isomer of chloro(dimethyl)phenylsulfur
trifluoride, each isomer of trimethylphenylsulfur trifluoride, each isomer of
ethylphenylsulfur trifluoride, each isomer of propylphenylsulfur trifluoride, each
isomer of butylphenylsulfur trifluoride, each isomer of nitrophenylsulfur trifluoride,
each isomer of dinitrophenylsulfur trifluoride, and so on.
[0080] As mentioned in the reaction mechanism for the Process I, arylsulfur
trifluorides (formula V) can be the intermediates in the Process I.
[0081] A halogen employable in the present invention for Process III is the
same as for Process 1 described above except for the amount used for the reaction.
[0082] Fluoro salts having a formula (HI) for Process TTI are the same as for
Process I described above except for the amount used in the reaction.

[0083] It is preferable that the reaction of Process III be carried out using a
solvent. Examples of suitable solvents are the same as for Process I described
above.
[0084] In order to economically get good yields of the products, the reaction
temperature for Process III can be selected in the range of ~60°C ~'+70°C. More
preferably, the temperature can be selected in the range of-40°C ~ +50T.
Furthermore preferably, the temperature can be selected in the range of -20°C ~
+40'C.
[0085] In order to get good economic yields of product, the amount of a
halogen used can be preferably selected in the range of from about 1 to about 5
mol, more preferably from about 1 to about 3 mol, against 1 mol of arylsulfur
trifluoride (V).
[0086] In order to get good economic yield of the products, the amount of
fluoro salt (III) used can be preferably selected in the range of about 1 to about 5
mol against 1 mol of arylsulfur trifluoride (V).
[0087] The reaction time for Process III is dependent on reaction temperature,
the substrates, reagents, solvents, and their amounts used. Therefore, one can
choose the time necessary for completing each reaction based on modification of
the above parameters, but can be from about 0.5 h to several days, preferably,
within a few days.
[0088] Process II is as described above.
[0089] Embodiments of the present invention include a process (Process III)
which comprises reacting an arylsulfur trifluoride having a formula (V) with a
halogen (chlorine, bromine, iodine, or interhalogens) and a fluoro salt having a
formula (III) to form an arylsulfur halotetrafluoride having a formula (TV) and
(Process II') reacting the obtained arylsulfur halotetrafluoride with a fluoride
source in the presence of a halogen selected from the group of chlorine, bromine,
iodine, and interhalogens to form the arylsulfur pentafluoride having a formula (I).
Scheme 6 showing Processes III and IT are shown as follows:-
Scheme 6 (Processes HI and II')


[0090] With regard to formulas (I), (EI), (TV), and (V), R1, R2, R3, R4, R5, R6,
M and X have the same meaning as defined above. ■
[0091] Processes HI and II' are as described above.
[0092] Furthermore, the present invention includes.a process (Scheme 7,
Process I) for preparing an arylsulfur halotetrafluoride having a formula (IV),
which comprises reacting at least one aryl sulfur compound having a formula (IIa)
or a formula (Tib) with a halogen selected from the group of chlorine, bromine,
iodine, and interhalogens and a fluoro salt having a formula (IH) to form the
arylsulfur halotetrafluoride.
Scheme 7 (Process I)

[0093] In the formulas (IIa), (Hb), (HI), and (TV), R1, R2,R3,R4,R5,'R6,M and
X represent the same meaning as defined above.
[0094] Process I is described above.
[0095] Furthermore, the present invention includes a process (Scheme 8,
Process ITT) for preparing an arylsulfur halotetrafluoride having a formula (TV),
which comprises reacting an arylsulfur trifluoride having a formula (V) with a
halogen selected from the group of chlorine, bromine, iodine, and interhalogens
and a fluoro salt having a formula (III) to form the arylsulfur halotetrafluoride.

Scheme 8 (Process III)

[0096] In the formulas (III), (IV), and (V), R1, R2, R3, R\ R5, M and X
represent the same meaning as defined above.
[0097] Process III is as described above.
[0098] Furthermore, the present invention includes a process (Scheme 9,
Process II") for preparing an arylsulfur pentafluoride having a formula (I), which
comprises reacting an arylsulfur halotetrafluoride having a formula (IV) with a
fluoride source whose boiling point is approximately 0°C or more to form the
arylsulfur pentafluoride.
Scheme 9 (Process II")

[0099] In the formulas (I) and (IV), R\ R2, R3, R4, R5, and X represent the
same meaning as defined above.
Process II" (Scheme 9)
[00100] Process II" is a reaction of arylsulfur halotetrafluoride having a
formula (IV) with a fluoride source whose boiling point is approximately 0°C or
more at 1 atm, as shown in Scheme 9.
[00101] The substituent(s), Rl, R2, R3, R4, and R5, of the products represented
by the formula (I) may be different from the substituents, R', R2, R3, R4, and R5, of
the starting materials represented by the formula (IV). Thus, embodiments of this
invention include transformation of the R1, R2, R3, R4, and R5 to different R1, R2,
R3, R4, and R5 which may take place during the reaction of the present invention or
under the reaction conditions as long as the -SF4X is transformed to a -SF5 group.
[00102] Process II" is the same as Process II described above, and, the fluoride
sources employable in Process II" are the same as the fluoride sources previously
discussed with reference to Process II, with exception that Process II" fluoride
sources have boiling points equal to or above 0°C at 1 atm.

[00103] Furthermore, the present invention includes a process (Scheme 10,
Process IP) for preparing an arylsulfur pentafluoride having a formula (I), which
comprises reacting an arylsulfur halotetrafluoride having a formula (TV) with a
fluoride source in the presence of a halogen selected from the group of chlorine,
bromine, iodine, and interhalogens to form the aryl sulfurpentafluoride.
Scheme 10 (Process II')

[00104] For formulas (I) and (IV), R1, R2, R3, R4, R5, and X represent the same
meaning as defined above.
[00105] Process II' is as described above.
[00106] According to the present invention, the arylsulfur pentafluorides
having the formula (I) can be easily and cost-effectively produced from easily
available starting materials.
[00107] The present invention provides novel arylsulfur chlorotetrafluorides
represented by formula (TV') as useful intermediates;
R2' R1'
R3'^VSF4CI . — - (IV)
R4' R5'
R2' R1'
R3'^VsF4CI . — - (IV)
R4' R5'
wherein R1, R2, R3, R4, and R5' each is independently a hydrogen atom, a halogen
atom, a linear or branched alkyl group having one to four carbon atoms, or a nitro group; and
where, when R3' is a hydrogen atom, a methyl group, or a nitro group, at least one of R1, R2,
R4, and R5 is a halogen atom, a linear or branched alkyl group having one to four carbon
atoms, or a nitro group. The halogen atom here is a fluorine atom, a chlorine atom, a bromine
atom, or an iodine atom.
Among these, each isomer of tert-butylphenylsulfur chlorotetrafluoride, each isomer
of fluorophenylsulfur chlorotetrafluoride, each isomer of chlorophenylsulfur
chlorotetrafluoride, each isomer of bromophenylsulfur chlorotetrafluoride, each isomer of



Formu Name Structure
la 1 I

Example 1. Synthesis ofphenylsulfur pentafluoride from diphenyl disulfide

[00110] (Process I) A 500 mL round bottom glassware flask was charged with
diphenyl disulfide (33.0 g, 0.15 mol), dry KF (140 g, 2.4 mol) and 300 mL of dry
CH3CN. The stirred reaction mixture was cooled on an ice/water bath under a flow
of 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 h.
The total amount of Cl2 used was about 1.2 mol. After Cl2 was stopped, the
reaction mixture was stirred for additional 3 h. 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 hexanes in air. About 1 g of dry KF was added to the filtrate. The KP
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: b.p. 80°C/20
mmHg; 'H 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.
[00111] (Process II) A 100 mL fluoropolymer (TEFLON®PFA) vessel was
charged with PhSF4Cl (44 g, 0.2mol) and dry ZnF2 (12.3 g, 0.12 mol) in a dry box
filled with N2. The vessel was then equipped with a condenser made of
fluoropolymer and a balloon filled with N2. The reaction mixture was slowly
heated to 120°C over a period of one hour. The reaction mixture changed from
colorless to yellow, pink, and then eventually green. The reaction mixture was
stirred at 120°C for 20 h. After being cooled to room temperature, about 50 mL of
pentane was added to the reaction mixture. The mixture was filtered to remove all
insoluble solid to give a yellow solution, which was concentrated. The resulting
residue was distilled at reduced pressure to give 30.6 g (75%) of phenylsulfur
pentafluoride; b.p. 70-71°C/120 mmHg; JH NMR(CDC13) 7.77-7.74 (m, 2H,
aromatic), 7.60-7.40 (m, 3H, aromatic), 19F NMR (CDC13) 85.20-84.13 (m, IF,
SFS), 62.91 (d, 4F, SF5).
Examples 2-10. Synthesis of arylsulfur pentafluorides (I) from aryl sulfur compounds (IIa) . .

[00112] Substituted arylsulfur pentafluorides (I) were synthesized from the
corresponding aryl sulfur compounds (IIa) by the similar procedure as in Example
1. Table 3 shows the synthesis of the substituted arylsulfur pentafluorides. Table 3
also shows the starting materials and other chemicals necessary for the Processes I
and II, solvents, reaction conditions, and the results, together with those of
Example 1. FC-72 (Fluorinert®) was used as a solvent in Process II in Examples 9

and 10. The Fluorinert® FC-72 was a perfluorinated organic compound haying a
boiling point of 56 °C. which was a product made by 3M Company.
Table 3: Production of Arylsulfur pentafluorides (I) from Aryl sulfur
compounds (IIa)



[00113] The properties and spectral data of the products, (IV) and (I), obtained
by Examples 2-10 are shown by the following:
[00114] p-Methylphenylsulfur chlorotetrafluoride; b.p. 74-75°C/5 mmHg; lH
NMR (CD3CN) 7.65 (d, 2H, aromatic), 7.29 (d, 2H, aromatic), 2.36 (s, 3H, CH3);
19F NMR (CD3CN)D 137.66 (s, SF4C1); High resolution mass spectrum; found
235.986234 (34.9%) (calcd for C7H7F4S37C1; 235.986363), found 233.989763
(75.6%) (calcd for C7H7F4S35C1; 233.989313). The NMR shows that p-
methylphenylsulfur chlorotetrafluoride obtained is a trans isomer.
[00115] p-Methylphenylsulfur pentafluoride; b.p. 95-96°C/80 mmHg; 'H NMR
(CDCU) 7,63 (d, 2H, aromatic), 7.24 (d, 2H, aromatic), 2.40 (s, 3H, CH3); 19F NMR
(CDC13) 86.55-84.96 (m, IF, SF), 63.26 (d, 4F, SF4).
[00116] p-Fluorophenylsulfur chlorotetrafluoride; b.p. 60°C/8 mmHg; 'H NMR
(CD3CN) 7.85-7.78 (m, 2H, aromatic), 7.25-7.15 (m, 2H, aromatic); 19F NMR
(CD3CN) 137.6 (s, SF4C1), -108.3 (s, CF); High resolution mass spectrum; found
239.961355 (37.4%) (calcd for C6H4F5S37C1; 239.961291), found
237.964201(100%) (calcd for C^FjS^Cl; 237.964241). The NMR shows that p-
fluorophenylsulfur chlorotetrafluoride obtained is a trans isomer.
[00117] p-Fluorophenylsulfur pentafluoride; b.p. 71°C/80 mmHg; 'H NMR
(CDCI3) 7.80-7.73 (m, 2H, aromatic), 7.17-7.09 (m, 2H, aromatic); 19F NMR
(CDCb) 87.78-83.17 (m, IF, SF), 63.81 (d, 4F, SF4), -107.06 (s, IF, CF); GC-MS
m/z 222 (M+).

[00118] o-Fluorophenylsulfur chlorotetrafluoride; b.p. 96-97°C/20 mmHg; 'H
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, SF4C1), -107.6 (s, CF); High .
resolution mass spectrum; found 239.961474 (25.4%) (calcd for C6H4F5S37C1;
239.961291), found 237.964375 (69.8%) (calcd for C6H4F5S35C1; 237.964241). The
NMR shows that o-fluorophenylsulfur chlorotetrafluoride obtained is a trans
isomer.
[00119] o-Fluorophenylsulfur pentafluoride; b.p. 91-94°C/120 mmHg; 'H NMR
(CDCI3) 7.78-7.73 (m, 1H, aromatic), 7.55-7.48 (m, 1H, aromatic), 7.27-7.17 (m,
2H, aromatic); 19F NMR (CDC13) 82.38-81.00 (m, IF, SF), 68.10 (dd, 4F, SF4),
-108.07-(-108.35) (m, IF, CF).
[00120] p-Bromophenylsulfur chlorotetrafluoride (X); m.p. 58-59 °C; 'H NMR
(CD3CN) 5 7.67 (s, 4H, aromatic); 19F NMR (CD3CN) 5 136.56 (s, SF4C1); 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 CeH^Br^Cu^S; 299.882128), found 297.882761 (77.4%) (calcd for
CsH^Br^ClF.S; 297.884174). Elemental analysis; calcd for CsH.BrClF.S; 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.
[00121] p-Bromophenylsulfur pentafluoride; b.p. 77-78°C/10 mmHg; 'H NMR
(CDCU) 7.63 (5, 4H, aromatic); 19F NMR (CDC13) 84.13-82.53 (m, IF, SF), 63.11
(d, 4F, SF4).
[00122] . m-Bromophenylsulfur chlorotetrafluoride; b.p. 57-59°C/0.8 mmHg; 'H
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, SF4C1). High resolution mass
spectrum; found 301.878031 (29.1%) (calcd for C6H481Br37ClF4S; 301.879178),
found 299.881066 (100%) (calcd for C6H48,Br35ClF4S; 299.881224 and calcd for
C6H479Br37ClF4S; 299.882128), found 297.883275 (77.4%) (calcd for
C6H479Br35ClF4S; 297.884174). The NMR showed that m-bromophenylsulfur
chlorotetrafluoride obtained was a trans isomer.
[00123] m-Bromophenylsulfur pentafluoride; b.p. 69-70°C/10 mmHg; 'H NMR
(CDCI3) 7.91 (/, 1H, aromatic), 7.72-7.64 (m, 2H, aromatic), 7.35 (t, 1H, aromatic);
l9F NMR (CDCU) 83.55-82.47 (m, IF, SF), 63.13 (d, 4F, SF4).

[00124] p-Nitrophenylsulfur chlorotetrafluoride; m.p. 130-131 °C; 'H 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, SF4C1); High resolution mass spectrum; found
266.956490 (38.4%) (calcd for C6H437C1F4N02S; 266.955791), found 264.959223
(100%) (calcd for CsH^Ctf^NCbS; 264.958741). Elemental analysis; calcd for
C6H4CIF4NO2S; 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.
[00125] p-Nitrophenylsulfur pentafluoride; b.p. 74-76°C/3 mmHg; 'H NMR
(CDCI3) 8.36-8.30 (m, 2H, aromatic), 7.99-7.95 (m, 2H, aromatic); 19F NMR
(CDCU) 82.32-80.69 (m, IF, SF), 62.76 (d, 4F, SF4).
[00126] 2,6-Difluorophenylsulfur chlorotetrafluoride: The product (b.p. 120-
122 °C/95-100mmHg) obtained from Example 8 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 (CDC13) 8
143.9 (t, J=26.0 Hz, 4F, SF4), -104.1 (quintet, J=26.0 Hz, 2F, 2,6-F): 'H NMR
(CDCI3) 5 6.97-7.09 (m, 2H, 3,5-H), 7.43-7.55 (m, 1H, 4-H); 13C NMR (CDC13) 8
157.20 (d, J=262.3 Hz), 133.74 (t, J=l 1.6 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 C6H335C1F6S; 255.954819);
elemental analysis; calcd for C6H3C1F6S; C, 28.08%, H, 1.18%; found; C, 28.24%,
H, 1.24%. The cis-isomer was assigned in the following; 19F NMR (CDC13) 8
158.2 (quartet, J-161.8 Hz, IF, SF), 121.9 (m, 2F, SF2), 76.0 (m, IF, 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.
[00127] 2,6-Difluorophenylsulfur pentafluoride: m.p. 40.3-41.1 °C; 'HNMR
(CDCU) 8 7.51 (m, 1H), 7.04 (m, 2H); ,9F NMR (CDCU) 82.32-80.69 (m, IF, SF),
62.76 (d, 4F, SF4); high resolution mass spectrum; found 239.984509 (calcd for
C6H3F7S; 239.984370); elemental analysis, calcd for C6H3F7S; C, 30.01%, H,
1.26%; found, C, 30.20%, H, 1.47%.
[00128] 2,4,6-Trifluorophenylsulfur chlorotetrafluoride: trans-isomer; m.p.
55.8-56.7 °C; 19F NMR (CDCU) 8 144.07 (t, J=26.0 Hz, 4F, SF4), -99.80 (t, J=26.0
Hz, 2F, o-F), -100.35 (s, IF, p-F); 'HNMR (CDC13) 8 6.79 (t, J=17.5 Hz, m-H);

13C NMR (CDC13) 8 164.16 (dt, J=164.2Hz, 15.2Hz,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
C6H2C1F7S; 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.
[00129] 2,4,6-Trifluorophenylsulfur pentafluoride and 3-chloro-2,4,6-
trifluorophenylsulfur pentafluoride: The product (b.p.~145°C) obtained from
Experiment 9 was a 3:1 (molar ratio) mixture of 2,4,6-trifluorophenylsulfur
pentafluoride and 3-chloro-2,4,6-trifluorophenylsulfur pentafluoride. These
products were identified by NMR and GC-Mass analysis. 2,4,6-
Trifluorophenylsulfur pentafluoride: 19F NMR (CDC13) 5 78.7-75.3 (m, SF), 73.8-
72.9 (m, SF4), -100.6 (m, 4-F), -100.7 (m, 2,6-F) ; 'H NMR (CDC13) 8 6.80 (t,
J=8.6 Hz, 3,5-H); GC-Mass m/z 258 (M+). 3-Chloro-2,4,6-trifluorophenylsulfur
pentafluoride: i9F NMR (CDC13) 8 78.7-75.3 (m, SF), 73.8-72.9 (m, SF4), -101.3
(m, 2 or 6-F), -102.3 (m, 4-F), -102.6 (m, 2 or 6-F); :H NMR (CDC13) 5 6.95 (br.t,
J=9.5 Hz, 5-H); GC-Mass m/z 294, 292 (M+).
[00130] 2,3,4,5,6-Pentafluorophenylsulfur chlorotetrafluoride: The product
(b.p. 95-112 °C/100 mmHg) obtained from Experiment 10 was a 1.7:1 mixture of
. trans and cis isomers of 2,3,4,5,6-pentafluorophenylsulfur chlorotetrafluoride. The
isomers were assigned by 19F NMR: The trans isomer; 19F NMR (CDC13) 8 144.10
(t, J=26.0 Hz, 4F, SF4), -132.7 (m, 2F, 2,6-F), -146.6 (m, IF, 4-F), -158.9 (m, 2F,
3,5-F); 13C NMR (CDC13) 8 143.5 (dm, J-265.2 Hz), 141.7 (dm, J=263.7 Hz),
128.3 (m). The cis isomer; 19F NMR (CDC13) 8 152.39 (quartet, J=158.9 Hz, IF,
SF), 124.32 (m, 2F, SF2), 79.4 (m, IF, SF), -132.7 (m, 2F, 2,6-F), -146.6 (m, IF, 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 C637C1F9S;
311.923604), found 309.926404 (43.1%) (calcd for C635C1F9S; 309.926554).
[00131] 2,3,4,5,6-Pentafluorophenylsulfur pentafluoride: b.p. 135-137 °C; 19F
NMR (CDC13) 8 74.8 (m; 5F, SF5), -133.4 (m, 2F, 2,6-F), -146.2 (m, IF, 4-F),
-158.6 (m, 2F, 3,5-F); 13C NMR (CDC13) 8 143.6 (dm, J=262.2 Hz), 137.9 (dm,
J=253.6 Hz), 126.7 (m). High resolution mass spectrum; found 293.956492 (calcd
for C6F,oS; 293.956104).

Example 11. Synthesis of phenylsulfur pentafluoride from diphenyl disulfide with a mixture of
hydrogen fluoride and pyridine as a fluoride source in Process II

[00132] (Process I) Phenylsulfiir chlorotetrafluoride was prepared in a high
yield in the same manner as in Process I in Example 1.
[00133] (Process II) A reaction vessel made of fluoropolymer was charged with
341 mg (1.54 mmol) of trans-phenylsulfur chlorotetrafluoride, and 0.5 mL of a
mixture of about 70wt% hydrogen fluoride and about 30wt% pyridine was added at
room temperature. The reaction mixture was stirred at room temperature for 1 hour
and heated at 50 °C for 3 hours. After the reaction, the reaction mixture was cooled
to room temperature. An analysis of the reaction mixture by 19F-NMR showed that
phenylsulfiir pentafluoride was produced in 93% yield.
Example 12. Synthesis of phenylsulfur pentafluoride from thiophenol as an aryl sulfur
compound of formula (IIb)

[00134] (Process I) Chlorine (Cl2) was passed with a flow rate of 27 mL/min
into a stirred mixture of 10.0 g (9Q.8 mmol) of thiophenol and 47.5 g (0.817 mol)
of dry KP in lOOrhL of dry acetonitrile at 6~10°C. Chlorine was passed for 3.7 h
and the total amount of chlorine passed was 10.2 L (0.445 mol). After 10 mL of
1,1,2-trichlorotrifluoroethane was added to the reaction mixture, the reaction
mixture was filtered. After removal of the solvent in vacuum, phenylsulfur
chlorotetrafluoride (16.6 g, 83%) as a light green-brown liquid was obtained. The
physical properties and spectral data of the product are shown in Example 1. The
product was a trans isomer.
[00135] (Process II) Phenylsulfur chlorotetrafluoride obtained in Process I
above may be allowed to react with ZnFj in the same procedure as Process II in
Example 1, giving phenylsulfur pentafluoride in good yield.

Example 13. Synthesis ofp-nitrophenylsulfur pentaflvioride from p-
nitrobenzenesulfenyl chloride as an aryl sulfur compound of formula (IIb)

[00136] (Process I) Chlorine (Cl2) was passed with a flow rate of 37 mL/min
into a stirred mixture of 5.00 g (26.4 mmol) of p-nitrobenzenesulfenyl chloride and
15.3 g (264 mmol) of dry KF in 40mL of dry acetonitrile at 5-11°C. The total
amount of chlorine passed was 2.54 L (113 mmol). After 5 mL of 1,1,2-
trichlorotrifluoroethane was added to the reaction mixture, the reaction mixture
was uiicicu. /-v.n.ei icinuvai ui u»e IUIVE»L III vacuum, jj-niu\jyiicnyiSuiTur
chlorotetrafluoride (4.69 g, 76%) as a solid was obtained. The physical properties
and spectral data of the product are shown in Example 7. The product was a trans
isomer.
[00137] (Process II.) p-Nitrophenylsulfur chlorotetrafluoride obtained in Process
I above may be allowed to react with ZnF2 in the same procedure as Process II in
Example 7, giving p-nitrophenylsulfur pentafluoride in good yield.
Example 14. Synthesis of phenylsulfur pentafluoride from phenylsulfur trifluoride

[00138] (Process III) Chlorine (CU) was passed with a flow rate of 34 mL/min
into a stirred mixture of 5.00 g (30.1 mmol) of phenylsulfur trifluoride and 8.74 g
(150 mmol) of dry KF in 20 mL of dry acetonitrile at 6~9°C. Chlorine was passed
for 43 min and the total amount of chlorine passed was 1.47 L (65.5 mmol). After
3 mL of 1,1,2-trichlorotrifluoroethane was added to the reaction mixture, the
reaction mixture was filtered. After removal of the solvent in vacuum,
phenylsulfur chlorotetrafluoride (5.62 g, 84%) as a colorless liquid was obtained.
The physical properties and spectral data of the product are shown in Example 1.
The product was a trans isomer.

[00139] (Process II) Phenylsulfur chlorotetrafluoride obtained in Process III
above may be allowed to react with ZnF2 in the same procedure as Process II in
Example 1, giving phenylsulfur pentafluoride in good yield.
Example 15. Reaction of phenylsulfur chlorotetrafluoride and ZnF, under a slow flow of
chlorine (presence of halogen)

(Process IF) trans-Phenylsulfur chlorotetrafluoride (trans-PhSF4Cl) used for this
Process was prepared in high yields by the Process I or III as shown by Examples
1, 11, 12, or 14. In a dry box, a 50 mL reaction vessel made of fluoropolymer was
charged with 10.0 g (0.045 mol) of trans-PhSF4Cl and 2.8 g (0.027 mol) of dry
ZnF2. The reaction vessel was brought out from the dry box and connected to the
gas flowing system. The reaction mixture was slowly heated to 120°C while Cl2 gas
was added into the reaction vessel at the rate of 4.6 mL/minute. The progress of
the reaction was monitored by 19F NMR. After 40 minutes at 120°C, three major
compounds (trans-PhSF4Cl, cis-PhSF4Cl, and phenylsulfur pentafluoride (PhSFs))
were detected to be present in the reaction mixture. The mol ratio of trans-
PhSF4Cl: cis-PhSF4Cl: PhSF5 was 0.5 : 3.3 : 100. After additional 60 minutes at
120°C, trans- and cis-PhSF4Cl disappeared and only PhSF5 was detected from l9F
NMR. The reaction was completed within 1.7 h at 120°C. After N2 (5.4.
mL/minute) was flowed for 0.5 hour, the examination of the reaction mixture by
19F NMR using benzotrifluoride as a standard showed that phenylsulfur
pentafluoride was produced in 92% yield. This experiment showed that the
reaction is greatly accelerated by the presence of chlorine and the product is
obtained in a high yield. This experiment also showed that cis-PhSF4Cl is formed
intermediately by the isomerization of trans-PhSF4Cl, and cis-PhSF4Cl is converted
to the product, PhSF5.
Example 16. Reaction of phenylsulfur chlorotetrafluoride andZnFi under a fast flow of
chlorine (presence of halogen)


[00140] (Process IF) trans-Phenylsulfur chlorotetrafluoride (trans-PhSF4Cl)
used for this Process was prepared in high yields by the Process I or III as shown
by Examples 1,11, 12 or 14. In a dry box, a 50 mL reaction vessel made of
fluoropolymer was charged with 10.0 g (0.045 mol) of trans-PhSF4Cl and 2.8 g
(0.027 mol) of dry ZnF2. The reaction vessel was brought out from the dry box and
connected to the gas flowing system. The reaction mixture was slowly heated to
120°C while Cl2 gas was added into the reaction vessel at the rate of 23 mL/minute.
The progress of the reaction was monitored by 19F NMR. After 45 minutes at
120°C, three major compounds (trans-PhSF4Cl, cis-PhSF4Cl, and phenylsulfur
pentafluoride (PhSF5)) were detected to be present in the reaction mixture. The mol
ratio of trans-PhSF4Cl : cis-PhSF4Cl: PhSF5 was 18 : 83 : 100. After additional 45
minutes at 120°C, trans- and cis-PhSF4Cl disappeared and only PhSF5 was detected
from I9F NMR. The reaction was completed in about 1.5 h at 120°C. After N2
(26.9 mL/minute) was flowed for 1 hour, the examination of the reaction mixture
by 19F NMR using benzotrifluoride as a standard showed that phenylsulfur
pentafluoride was produced in 83% yield. This experiment showed that the
reaction is greatly accelerated by the presence of chlorine and the product is
obtained in a high yield. This experiment clearly showed that cis-PhSF4Cl is
formed intermediately by the isomerization of traiis-PhSF4Cl, and cis-PhSF4Cl is
converted to the product, PhSF5.
Example 17. Reaction of 2.6-difluorophenylsulfur chlorotetrafluoride andZnFi under a flow
of chlorine (presence of halogen)

[00141] (Process IF) A 6:1 mixture of trans and cis^^-difluorophenylsulfur
chlorotetrafluoride used for this Process was prepared in high yields by the Process

I or III as shown by Examples 8. In a dry box, a 100 mL reaction vessel made of
fluoropolymer was charged with 13.03 g (0.126 mol) of dry ZnF2- The reaction
vessel was brought out from the dry box and connected to the gas flowing system.
After nitrogen purge, Cl2 gas started to flow into the reaction vessel at the rate of
15 mL/minute as the reaction vessel was heated to 130-140°C, at which point
addition of 32.36 g (0.126 mol) of the mixture of trans- and cis-2,6-
difluorophenylsulfur chlorotetrafluoride was started. A total of 32.36 g (0.126 mol)
of the mixture of trans- and cis-2,6-difluorophenylsulfur chlorotetrafluoride was
added over 1 h. After this, heat and chlorine flow were maintained for an additional
3 hours. At this point, the NMR analysis of the reaction mixture showed that the
starting materials (trans- and cis-2,6-difluorophenylsulfur chlorotetrafluoride) were
consumed and 2,6-difluorophenylsulfur pentafluoride and 3-chloro-2,6-
difluorophenylsulfur pentafluoride were produced in 63:37 molar ratio. The
reaction mixture was then extracted with pentane and washed with aqueous sodium
carbonate solution. The extract was dried with dry Na2S04, filtered, and
concentrated to give a residue which was distilled at reduced pressure to give four
fractions of the product in the range of boiling point 75-120 °C at 110 mmHg. The
first three fractions (total 15.37g) was a 1:1 mixture (by GC) of 2,6-
difluorophenylsulfur pentafluoride and 3-chloro-2,6-difluorophenylsulfur
pentafluoride. The final fraction (the fourth fraction, b.p. 112-120 °C/110 mmHg)
had 6.22 g of 3-chlor6-2,6-difluorophenylsulfur pentafluoride (93% purity,
determined by GC). The spectral data of 3-chloro-2,6-difluorophenylsulfur
pentafluoride were as follows; 19F NMR (GDC13) 5 77.9-75.7 (m, IF, SF), 73.2-
72.5 (m, 4F, SF4), -103.3 (m, IF), -105.2 (m, IF); 'HNMR (CDC13) 5 7.60 (m,
1H), 7.04 (m, 1H); high resolution mass spectrum, found 275.942071 (36.0%)
(calcd for C6H237C1F7S; 275.942447), found 273.945943 (100%) (calcd for
C6H235C1F7S; 273.945397). The other product, 2,6-difluorophenylsuflur
pentafluoride was identified by the data obtained by Example 8 (Process II).
Example 18. Reaction ofphenvlsulfur chlorotetrafluoride andZnFi under a slow
flow of an inactive gas (nitrogen)


[00142] (Process II) trans-Phenylsulfur chlorotetrafluoride (trans-PhSF4Cl)
used for this Process was prepared in high yields by the Process I or III as shown
by Examples 1, 11, 12 or 14. In a dry box, a 50 mL reaction vessel made of
fluoropolymer was charged with 10.0 g (0.045 mol) of trans-PhSF4Cl and 2.8 g
(0.027 mol) of dry ZnF2. The reaction vessel was brought out from the dry box and
connected to the gas flowing system. The reaction mixture was slowly heated to
120°C with N2 flowing at the rate of 5.4 mL/minute. The reaction mixture changed
from colorless to light yellow, to pink, and eventually to brown in about 30
minutes. The reaction mixture was stirred at 120°C with N2 flowing for 5 hours.
After being cooled down to room temperature, the reaction mixture was checked
with 19FNMR. Three major compounds (trans-PhSF4Cl, cis-PhSF4Cl and PhSF5)
were present in the reaction mixture. The ratio of trans-PhSF4Cl: cis-PhSF4Cl:
PhSF5 was 15 : 20 : 100. PhCF3 (1.0 g) was added to the reaction mixture and the
NMR yield of each compound was determined. The yield of trans-PhSF4Cl was
2.4%, cis-PhSF4Cl was 14.6 %, and PhSF5 was 67.2 %. The reaction was not
complete in 5 h at 120°C. Therefore, this experiment showed that the reaction
under the flow of nitrogen was slowed down.
Example 19. Reaction ofphenylsulfur chlorotetrafluoride andZnFi under a fast
flow of inactive gas (nitrogen)

[00143] (Process II) trans-Phenylsulfur chlorotetrafluoride (trans-PhSF4Cl)
used for this Process was prepared in high yields by Process I or III as shown by
Examples 1, 11, 12 or 14. In a dry box, a 50 mL reaction vessel made of
fluoropolymer was charged with 10.0 g (0.045 mol) of trans-PhSF4Cl and 2.8 g
(0.027 mol) of dry ZnF2. The reaction vessel was brought out from the dry box and
connected to the gas flowing system. The reaction mixture was slowly heated to
120°C with N2 flowing at a rate of 26.9 mL/minute. The reaction mixture changed

from colorless to light yellow, to pink, and eventually to brown in about 30
minutes. The reaction mixture was stirred at 120°C withN2 flowing for 5 hours.
After being cooled down to room temperature, the reaction mixture was checked
with 19F NMR. Three major compounds (trans-PhSF4Cl, cis-PhSF4Cl and PhSF5)
were present in the reaction mixture. The ratio of trans-PhSF4Cl: cis-PhSF4Cl:
PhSF5 was 22 : 117 : 100. PhCF3 (2.8g) was added to the reaction mixture and the
NMR yield of each compound was determined by 19F NMR. The yield of trans-
PhSF4Cl was 6.7 %, cis-PhSF4Cl was 42.1 %, and PhSF5 was 38.4 %. The reaction
was not complete in 5 h at 120°C and the conversion of PhSF4Cl to PhSF5 was
lower than in Example 18. This reaction showed that the reaction under the fast
flow of nitrogen was slowed down more than the reaction under the slow flow of
nitrogen. In either case a flow of inactive gas has an inhibitory effect on reaction
yield.
Example 20. Synthesis of phenylsulfur pentafluoride by using SbF± as a fluoride
source

[00144] (Process II) trans-Phenylsulfur chlorotetrafluoride used for this Process
was prepared in high yields by the Process I or III as shown by Examples 1, 11, 12,
or 14. In a dry box, a reaction vessel made of fluoropolymer was charged with 1.0
g (4.54 rnmol) of trans-phenylsulfur chlorotetrafluoride and 0.397 g (2.22 mmol) of
dry SbF3. The reaction vessel was brought out from the dry box and equipped with
a balloon filled with N2. The mixture was stirred at 80°C for 5 h. The analysis of
the reaction mixture by 19F-NMR technique showed that phenylsulfur pentafluoride
was produced in 33% yield.
Example 21. Synthesis of phenylsulfur pentafluoride by using a mixture ofSbFi (fluoride
source) and SbCU (fluoride source-activating compound) as a fluoride source


[00145] (Process II) trans-Phenylsulfur chlorotetrafluoride used for this Process
was prepared in high yields by the Process I or III as shown by Examples 1,11,12,
or 14. In a dry box, a reaction vessel made of fluoropolymer was charged with 1.0
g (4.54 mmol) of trans-phenylsulfur chlorotetrafluoride, 0.349 g (2.01 mmol) of
SbF3, a trace amount of SbCls, and 2 mL of dry hexane. SbCl, is a fluoride source-
activating compound. SbCls (strong Lewis acid) can complex with SbF3 to form
SbF2(SbFCls), which can also be made by SbF2Cl and SbFCL both are fluoride
sources usable in this invention. The reaction vessel was brought out from the dry
box and equipped with a balloon filled with N2. The mixture was stirred at room
temperature for 3 days. The analysis of the reaction mixture by 19F-NMR showed
that phenylsulfur pentafluoride was produced in 54% yield.
Example 22. Synthesis of phenylsulfur pentafluoride by using SnF^as a fluoride source

[00146] (Process II) trans-Phenylsulfur chlorotetrafluoride used for this Process
was prepared in high yields by the Process I or III as shown by Examples 1, 11, 12,
or 14. In a box, a reaction vessel made of fluoropolymer was charged with 1.0 g
(4.54 mmol) of trans-phenylsulfur chlorotetrafluoride and 0.26 g (1.4 mmol) of dry
SnF4- The reaction vessel was brought out from the dry box and equipped with a
balloon filled withN2. The mixture was stirred at 80°C for 2 h. The analysis of the
reaction mixture by 1?F-NMR showed that phenylsulfur pentafluoride was
produced in 34% yield.
Example 23. Synthesis of phenylsulfur pentafluoride by using TiFj as a fluoride source

[00147] (Process II) trans-Phenylsulfur chlorotetrafluoride.used for this Process
was prepared in high yields by the Process I or III as shown by Examples 1, 11, 12,
or 14. In a dry box, a reaction vessel made of fluoropolymer was charged with 1.0

g (4.54 mmol) of trans-phenylsulfur chlorotetrafluoride and 0.17 g (1.4 mmol) of
dry T1F4. The reaction vessel was brought out from the dry box and equipped with
a balloon filled with N2. The mixture was stirred at 80°C for 16 h. The analysis of
the reaction mixture by 19F-NMR showed that phenylsulfur pentafluoride was
produced in 35% yield.
Example 24. Synthesis of phenylsulfur chlorotetrafluoride from diphenyl disulfide

[00148] (Process I) A 500 mL round bottom flask was charged with diphenyl
disulfide (21.8 g, 0.1 mol), dry CsF (243.2 g, 1.6 mol) and 200 mL of dry CH3CN.
The reaction mixture was cooled on an ice/water bath," and bubbled with N2 (18
mL/min) for 0.5 h. After the N2 flow was stopped, Cl2 was bubbled into a reaction
mixture at the rate of 63 mL/min for 4 h. The total amount of Cl2 used was 0.68
mol. The reaction mixture was then warmed to room temperature and stirred
overnight. Then, N2 (18 mL/min) was bubbled through for 2 hours to remove an
excess of chlorine. The reaction mixture was filtered with 100 mL of dry hexanes
in a dry box. The combined filtrate was evaporated under vacuum, and the residue
was distilled at reduced pressure to give a colorless liquid of phenylsulfur
chlorotetrafluoride (36.3 g, 83%). The physical properties and spectral data of the
product are shown in Example 1. The product was a trans isomer.
Example 25. Synthesis of p-chlorophenylsulfur chlorotetrafluoride from bis(p-chlorophenyl)
disulfide

[00149] (Process I) Chlorine (Cl2) was passed with a flow rate of 64 mL/min
into a stirred mixture of 25.0 g (87.0 mmol) of bis(p-chlorophenyl) disulfide and
86.0 g (1.48 mol) of dry KP in 200 mL of dry acetonitrile at 5~8°C. Chlorine was
passed for 3.5 h and the total amount of chlorine passed was 12.8 L (571 mmol).
After that, the reaction mixture was filtered and rinsed with dry hexane. After

removal of the solvent in vacuum, p-chlorophenylsulfur chlorotetrafluoride (39.5 g,
88%) as a colorless liquid was obtained; b.p. 65-66 °C/2 mmHg; 'H NMR (CDC13)
5 7.38 (d, 2H, J=9.1 Hz), 7.65 (d, 2H, J=9.1 Hz); l9F NMR (CDC13) 137.4 (s, 4F,
S.F4C1). High resolution mass spectrum; found 257.927507 (13.3%) (calcd for
C6H4F4S37C12; 257.928790), found 255.930746 (68.9%) (calcd for C6H4F4S37C135C1;
255.931740), found 253.933767 (100.0%) (calcd for C6H4F4S35C12; 253.934690).
The NMR showed that p-chlorophenylsulfur chlorotetrafluoride obtained is a trans
isomer.
Example 26. Synthesis ofp-(tert-butyl)phenylsulfur chlorotetrafluoride from p-(tert-
butyDbenzenethiol

[00150] (Process I) Chlorine (CI2) was passed with a flow rate of 35 mL/min
into a stirred mixture of 10.0 g (60.2 mmol) of p-(tert-butyl)benzenethiol and 91.6
g (602 mmol) of dry CsF in 150 mL of dry acetonitrile at 5~10°C. Chlorine was
passed for 3.5 h and the total amount of chlorine passed was 10.1 L (452 mmol).
After that, the reaction mixture was stirred at room temperature for 24 h. The
reaction mixture was filtered under dry nitrogen. After removal of the solvent at
reduced pressure, the residue was distilled to give 14 g (84%) of p-(tert-
butyl)phenylsulfur chlorotetrafluoride; b.p. 98 °C/0.3 mmHg; m.p. 93 °C; :H NMR
(CDCI3) 5 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 8 138.3 (s, SF4C1). High resolution mass spectrum;
found 278.034576 (8.8%) (calcd for C10H,337C1F4S; 278.033313), found
276.037526 (24.7%) (calcd for C10H)335C1F4S; 276.036263). Elemental analysis;
Calcd for C10H13C1F4S; 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.
Example 27. Synthesis of'phenylsulfur pentafluoride from phenylsulfur chlorotetrafluoride
and ZnF?


[00151] (Process II or II") In a dry box, a reaction vessel made of fluoropolymer
was charged with 1.0 g (4.54 mmol) of trans-phenylsulfur chlorotetrafluoride and
0.281 g of dry ZnF2 (solid, mp 872°C, bp 1500°C). The reaction vessel was
brought out from the dry box and equipped with a balloon filled with N2. The
mixture was heated at 80°C for 20 h. An analysis of the reaction mixture by 19F-
NMR showed that phenylsulfur pentafluoride was produced in 85% yield.
Example 28. Synthesis of phenylsulfur pentafluoride from phenylsulfur chlorotetrafluoride
and ZnFo

[00152] (Process II or II") In a dry box, a reaction vessel made of fluoropolymer
was charged with 1.0 g (4.54 mmol) of trans-phenylsulfur chlorotetrafluoride and
0.28 g (2.7 mmol) of dry ZnF2 (solid, mp 872°C, bp 1500°C). The reaction vessel
was brought out from the dry box and equipped with a balloon filled with N2. The
mixture was heated at 120°C for 4 h. An analysis of the reaction mixture by 19F-
NMR showed that phenylsulfur pentafluoride was produced in 88% yield.
Example 29. Synthesis of phenylsulfur pentafluoride from phenylsulfur chlorotetrafluoride
and CuFi

[00153] (Process II or II") In a dry box, a reaction vessel made of fluoropolymer
was charged with 1.0 g (4.54 mmol) of trans-phenylsulfur chlorotetrafluoride and
0.284 g (2.79 mmol) of dry CuF2 (solid, mp ~785°C). The reaction vessel was
brought out from the dry box and equipped with a balloon filled with N2. The

mixture was heated at 80°C for 22 h. An analysis of the reaction mixture by 19F-
NMR showed that phenylsulfur pentafluoride was produced in 57% yield.
Example 30. Synthesis of p-methylphenylsulfur pentafluoride from p-methylphenylsulfur
chlorotetrafluoride and ZnFi

[00154] (Process II or II") In a dry box, a reaction vessel made of fluoropolymer
was charged with 1.01 g (4.26 mmol) of trans-p-methylphenylsulfur
chlorotetrafluoride and 0.266 g (2.57 mmol) of dry ZnF2 (solid, mp 872°C, bp
1500°C). The reaction vessel was brought out from the dry box and equipped with
a balloon filled with N2. The mixture was heated at 80°C for 16 h. An analysis of
the reaction mixture by 19F-NMR showed that p-methylphenylsulfur pentafluoride
was produced in 79% yield.
Example 31. Synthesis of phenylsulfur pentafluoride from phenylsulfur chlorotetrafluoride
and HBF4 diethyl ether ate

(Process II or II") In a dry box, a reaction vessel made of fluoropolymer was charged with 1.0
g (4.5 mmol) of trans-phenylsulfur chlorotetrafluoride (trans-PhSF4Cl) and 4.5 mL of dry
methylene chloride. The reaction vessel was brought out from the dry box and equipped with
a balloon filled with nitrogen. Into the solution, HBF4 diethyl etherate (liquid) (HBF4OEt2)
(0.88 g, 0.74 mL, 5.4 mmol) was slowly added. The reaction mixture was stirred at room
temperature. The progress of the reaction was monitored by 19F NMR. After 7 hours, three
major compounds (trans-PhSF4Cl, cis-PhSF4Cl and PhSF5) were present in the reaction
mixture. The ratio of trans-PhSF4Cl : cis-PhSF4Cl: PhSF5 was 156 : 716 : 100. After 21
hours, the ratio of trans-PhSF4Cl : cis-PhSF4Cl : PhSF3 changed to 3 : 6 : 100. An analysis of
the reaction mixture by l9F-NMR showed that phenylsulfur pentafluoride (PhSF5) was
produced in 40% yield.

Example 32. Synthesis of phenylsulfur pentafluoride from phenylsulfur chlorotetrafluoride by
using a mixture of ZnF^(fluoride source) andSbCl-Jfluoride source-activating compound) as
a fluoride source

In a dry box, a reaction vessel made of fluoropolymer was charged with dry
heptane (5 mL) and ZnF2 (solid) (0.84, 8.2 mmol), SbCl5 (liquid) (0.41 g, 0.17 mL,
1.36 mmol) was added into the mixture. To this, trans-phenylsulfur
chlorotetrafluoride (trans-PhSF4Cl) (3.0 g, 13.6 mmol) was slowly added. The
reaction vessel was brought out from the dry box and equipped with a balloon
filled with nitrogen. SbC^ is a fluoride source-activating compound. SbCls (strong
Lewis acid) can complex with ZnF2 to form ZnF(SbFCl5), which can also be made
by ZnFCl and SbFCU both are fluoride sources usable in this invention. The
reaction mixture was stirred at room temperature. The progress of the reaction was
monitored by 19F NMR. After 10 minutes, the ratio of trans-PhSF4Cl: cis-
PhSF4Cl: PhSF5 was 385 : 0 : 100. After 90 minutes, the ratio of trans-PhSF4Cl :
cis-PhSF4Cl : PhSF5 changed to 63 : trace : 100. After 180 minutes, the ratio of
trans-PhSF4Cl : cis-PhSF4Cl : PhSF5 changed to 34 : trace : 100. After 17 hours, the
ratio of trans-PhSF4Cl : cis-PhSF4Cl : PhSF5 changed to 18 : 2 : 100. An analysis of
the reaction mixture by 19F-NMR showed that phenylsulfur pentafluoride (PhSF5)
was produced in 53% yield. A small amount of the starting trans-PhSF4Cl (9.4 %)
remained.
Example 33. Reaction of phenylsulfur chlorotetrafluoride and BF± gas (Comparative
Example)

[00155] A reaction vessel made of steel was charged with 1.0 g (4.5 mmol) of
trans-phenylsulfur chlorotetrafluoride and cooled on a dry ice-acetone bath. The
reaction vessel was evacuated by a vacuum pump and boron trifluoride gas (BF3;
this boiling point is -100°C at 1 atm) was introduced into the reaction vessel till the

pressure reached 18 psi. The reaction mixture was then warmed to room
temperature and stood for 3 days. During the time, the pressure was increased to
100 psi with additional BF3 gas. After the reaction, it was found that all the
reaction mixture became a solid residue. Phenylsulfur pentafluoride was not
detected.
Example 34. Reaction ofphenylsuflur chlorotetrafluoride and BFi gas in
methylene chloride (Comparative Example)
[00156] A reaction vessel made of steel was charged with 1.42 g (6.44 mmol)
of trans-phenylsulfur chlorotetrafluoride and 6.4 mL of dry methylene chloride and
cooled to about -100°C by using a liquid nitrogen bath. The reaction vessel was
evacuated by a vacuum pump and BF3 gas (boiling point is -100°C at 1 atm) was
introduced into the reaction vessel till the pressure reached 80 psi. The reaction
mixture was warmed to room temperature and stood for 5 h. During this time, the
pressure was increased to 100 psi with additional BF3 gas. An analysis of the
reaction mixture by 19F-NMR showed that phenylsulfur pentafluoride was formed
in 28% yield.
[00157] Examples 33 and 34 show that as Ou et al. reported, it was found that,
when boron trifluoride (boiling point -100X at 1 atm) was flowed through a
solution of phenylsulfur chlorotetrafluoride in a deuterium methylene chloride,
phenylsulfur chlorotetrafluoride was slowly transferred to phenylsulfur
pentafluoride (see Can. J. Chem., Vol. 75, pp.1878-1884). As shown herein,
however, the yield was very low or the desired:productwas not obtained because
an undesired polymerization occurred. Examples 33 and 34 show the utility of the
present invention over the conventional art production method using a fluoride gas
such as boron trifluoride whose boiling point is -100°C at 1 atm. The present
invention preferably uses fluoride liquids or solids at least at 0°C and at 1 atm, as
compared to a gaseous reactant. A liquid or solid is preferable because it is easy to
handle and reacts more completely than a gaseous reactant. Also, the reactant of
Ou et al., although shown to react at atmospheric pressure, would require high
pressure to proceed at an appreciable rate with a necessary and minimum amount
of the reactant.
[00158] While the invention has been particularly shown and described with
reference to a number of embodiments, it would be understood by those skilled in

the art that changes in the form and details may be made to the various
embodiments disclosed herein without departing from the spirit and scope of the
invention and that the various embodiments disclosed herein are not intended to act
as limitations on the scope of the claims.

WE CLAIM:
1. A process for preparing an arylsulfur pentafluoride having a formula (I):

the process comprising:
reacting an arylsulfur halotetrafluoride having a formula (IV);

with a fluoride source, wherein the fluoride source is a solid or liquid at 0°C and 1 atm to
form the arylsulfur pentafluoride;
in which: R1, R2, R3, R4, and R5 each is independently a hydrogen atom, a halogen
atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or
unsubstituted aryl group having 6 to 30 carbon atoms, a nitro group, a cyano group, a
substituted or unsubstituted alkanesulfonyl group having 1 to 18 carbon atoms, a substituted
or unsubstituted arenesulfonyl group having 6 to 30 carbon atoms, a substituted or
unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted
aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted acyloxy group
having from 1 to 18 carbon atoms, a substituted or unsubstituted alkanesulfonyloxy group
having from 1 to 18 carbon atoms, a substituted or unsubstituted arenesulfonyloxy group
having from 6 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group
having 2 to 18 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7
to 30 carbon atoms, a substituted carbamoyl group having 2 to 18 carbon atoms, a substituted
amino group having 1 to 18 carbon atoms, and a SF5 group;
and
X is a chlorine atom, a bromine atom, or an iodine atom,

wherein the arylsulfur halotetrafluoride having a formula IV is prepared by reacting
an arylsulfur trifluoride having a formula (V):

with a halogen selected from the group consisting of chlorine, bromine, iodine, and
interhalogens and a fluoro salt having a formula (IU):

2. The process as claimed in claim 1, wherein the arylsulfur halotetrafluoride having
the formula IV is prepared by reacting an arylsulfur trifluoride having a formula (V);

with a halogen selected from the group consisting of chlorine, bromine, iodine, and
interhalogens and a fluoro salt having a formula (III):