PROCESSES FOR PREPARING POLY(PENTAFLUOROSULFANYL)AROMATIC
COMPOUNDS
TECHNICAL FIELD
[0001] The invention relates to methods for preparing an aromatic compound
substituted with two or three pentafluorosulfanyl groups.
BACKGROUND OF THE INVENTION
[0002] Arylsulfur pentafluorides compounds are used to introduce one or more
sulfur pentafluoride groups into various organic molecules in the development of medicines,
agrochemicals, and new materials. 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]. In particular, aromatic
compounds having two or more pentafluorosulfanyl groups (SF5) are of increased interest
because they are more useful in these applications as compared to aromatic compounds
having one pentafluorosulfanyl group. Presently, few such compounds have been
successfully synthesized, for example 3,5-bis(pentafluorosulfanyl)nitrobenzene, 3,5-
bis(pentafluorosulfanyl)aniline, l,3,5-tris(pentafluorosulfanyl)benzene, and 1,2,4-
tris(pentafluorosulfanyl)benzene have been synthesized to date, illustrating the difficulty of
their production. As such, and as discussed further herein, conventional synthetic
methodologies to prepare aromatic compounds having two or three pentafluorosulfanyl
groups have proven difficult to prepare and are a concern within the art.
[0003] Conventionally, aromatic compounds having two or three
pentafluorosulfanyl groups are synthesized by one of the following methods: (1) fluorination
of a poly(nitrobenzenedisulfide) with AgF2 [see J. Am. Chem. Soc, Vol. 82 (1962), pp.
3064-3072]; or (2) reaction of SF5Cl with acetylene, followed by bromination with Br2 under
hv irradiation, dehydrobromination, and reduction with zinc, giving
pentafluorosulfanylacetylene (HC = CSF5). The pentafluorosulfanylacetylene is then reacted
with Co2(CO)8, giving a complex, Co(CO)4(HC=CSF5)3, and the complex decomposing in
the presence of Br2 to give l,2,4-tris(pentafluorosulfanyl)benzene [see Chem. Ber., Vol. 119,
pp. 453-463 (1986)]. Photoreaction of pentafluorosulfanylacetylene in the presence of SF5CI
gives l,3,5-tris(pentafluorosulfanyl)benzene [see Chem. Ber., Vol. 119, pp. 453-463 (1986)].
[0004] Each of the above synthetic methods has one or more drawbacks making
them industrially impractical. For example, the former method provides a very low yield and
requires an expensive reaction agent, AgF2. The latter method requires an expensive and
toxic gas, SF5CI, and many reaction steps to reach a final product at low yield.
[0005] In addition, it has been reported that related compounds, p- and m-
(pentafluorosulfanyl)nitrobenzene, were prepared by reacting a bis(nitrophenyl) disulfide
with molecular fluorine (F2), CF3OF, or CF2(OF)2 [Tetrahedron, Vol. 56, 3399-3408 (2000);
USP 2004/0249209 Al]. However, F2, CF3OF, and/or CF2(OF)2 are extremely toxic,
corrosive, and dangerous gasses and their handling is expensive from the standpoint of gas
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 (pentafluorosulfanyl)aromatic
compounds, such as nitro-substituted (pentafluorosulfanyl)aromatic compounds, due to their
extreme reactivity, which leads to side-reactions such as fluorination of the aromatic rings
when not deactivated. It has also been reported that (pentafluorosulfanyl)benzene and p-
(pentafluorosulfanyl)tolune were prepared by reacting diphenyl disulfide and di(p-tolyl)
disulfide with XeF2, respectively [J. Fluorine Chem., Vol. 125 (2004), pp. 549-552].
However, this method requires an expensive reagent, XeF2. Therefore, problems with the
production methods known for the pentafluorosulfanylaromatic compounds have made it
difficult to prepare the material in an industrially safe, cost effective and timely fashion.
[0006] The present invention is directed toward overcoming one or more of the
problems discussed above.
SUMMARY OF THE INVENTION
[0007] The present invention provides novel processes for the production of
poly(pentafluorosulfanyl)aromatic compounds, as represented by formula (I):

in which one or two of R1, R2, R3, R4, and R5 are a pentafluorosulfanyl (SF5) group
and each of the remainders is selected from a group consisting of a hydrogen atom, a
halogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms,
a nitro group, and a cyano group.
Embodiments of the invention include reacting an aryl sulfur compound, having a formula
(H):

in which one or two of R1, R2, R3 , R4, and R5 are a SR6 group and each of
the remainders is selected from a group consisting of a hydrogen atom, a halogen
atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro
group, and a cyano group, and R is a hydrogen atom, a silyl group, a metal atom, an
ammonium moiety, a phosphonium moiety, or a halogen atom, or R6 combines with
another R6 of its own molecule or another molecule to form a single bond;
with a halogen selected from the group of chlorine, bromine, iodine and interhalogens, and a
fluoro salt (M+F, formula III) to form a poly(halotetrafluorosulfanyl)aromatic compound.
The poly(halotetrafluorosulfanyl)aromatic compound has a formula (IV):

in which one or two of R1 , R2 , R3 , R4 , and R5 are a SF4X group and each of
the remainders is selected from a group consisting of a hydrogen atom, a halogen
atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro
group, and a cyano group, and X is a chlorine atom, a bromine atom, or an iodine
atom.
Poly(halotetrafluorosulfanyl)aromatic compounds (formula IV) are reacted with a fluoride
source to formpoly(pentafluorosulfanyl)aromatic compounds (formula I).
[0008] Embodiments of the present invention also provide processes for producing
a poly(pentafluorosulfanyl)aromatic compound (formula I) by reacting an aryl sulfur
compound, having a formula (IT), with a halogen selected from the group of chlorine,
bromine, iodine, and interhalogens, and a fluoro salt (M+F, formula HI) to form a
poly(halotetrafluorosulfanyl)aromatic compound having a formula (IV). The
poly(halotetrafluorosulfanyl)aromatic compound (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 a poly(pentafluorosulfanyl)aromatic compound (formula I).
[0009] Embodiments of the present invention also provide processes for producing
poly(pentafluorosulfanyl)aromatic compounds (formula I) by reacting an arylsulfur
trifluoride having a formula (V):

in which one or two of R1 , R2 , R3 , R4 , and R5 are a SF3 group and each
of the remainders is selected from a group consisting of a hydrogen atom, a halogen
atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro
group, and a cyano group;
with a halogen selected from the group of chlorine, bromine, iodine and interhalogens, and a
fluoro salt (formula III) to form a poly(halotetrafluorosulfanyl)aromatic compound having a
formula (IV). The poly(halotetrafluorosulfanyl)aromatic compound (formula IV) is reacted
with a fluoride source to form a poly(pentafluorosulfanyl)aromatic compound (formula I).
[0010] Embodiments of the present invention also provide processes for producing
poly(pentafluorosulfanyl)aromatic compounds (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 HI) to form a
poly(halotetrafluorosulfanyl)aromatic compound having a formula (IV). The
poly(halotetrafluorosulfanyl)aromatic compound (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 a poly(pentafluorosulfanyl)aromatic compound (formula I).
[0011] Embodiments of the present invention further provide processes for
producing a poly(halotetrafluorosulfanyl)aromatic compound (formula IV) by reacting an
aryl sulfur compound having a formula (II) with a halogen selected from a group of chlorine,
bromine, iodine and interhalogens, and a fluoro salt having a formula (III) to form an
poly(halotetrafluorosulfanyl)aromatic compound having a formula (IV).
[0012] Embodiments of the present invention provide processes for producing a
poly(halotetrafluorosulfanyl)aromatic compound (formula IV) by reacting an arylsulfur
trifluoride having a formula (V) with a halogen selected from a group of chlorine, bromine,
iodine and interhalogens, and a fluoro salt having a formula (III) to form an
poly(halotetrafluorosulfanyl)aromatic compound having a formula (IV).
[0013] Embodiments of the present invention provide processes for producing a
poly(pentafluorosulfanyl)aromatic compound (formula I) by reacting a
poly(halotetrafluorosulfanyl)aromatic compound having a formula (IV) with a fluoride
source to form a poly(pentafluorosulfanyl)aromatic compound.
[0014] In addition, embodiments of the present invention provide processes for
producing a poly(pentafluorosulfanyl)aromatic compound (formula I) by reacting a
poly(halotetrafluorosulfanyl)aromatic compound 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 a poly(pentafluorosulfanyl)aromatic compound.
[0015] Embodiments of the present invention also provide processes for producing
a halogenated poly(pentafluorosulfanyl)aromatic compound as represented by formula (I)(R2
= Y) by reacting a poly(pentafluorosulfanyl)aromatic compound having a formula (I)(R2 = H)
with a halogenating agent and an acid to form the poly(pentafluorosulfanyl)aromatic
compound of formula (I)(R2 = Y).

in which Y is a halogen atom which is a fluorine atom, chlorine atom, bromine
atom, or iodine atom; and one or two of R1, R3, R4, and R are a pentafluorosulfanyl
(SF5) group and each of the remainders is selected from a group consisting of a
hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to
18 carbon atoms, a nitro group, and a cyano group.
[0016] In addition, the present invention provides novel
poly(chlorotetrafluorosulfanyl)aromatic compounds represented by formula (IV'):

wherein one or two of R1', R2', R3', R4', and R5' are SF4Cl and each of the
remainders is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl
group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably
1 to 4 carbon atoms, a nitro group, or a cyano group.
[0017] Finally, the present invention provides novel
bis(pentafluorosulfanyl)benzene compounds represented by formula (I"):

wherein one of Ra, Rb, Rc, Rd, and Re is a SF5 group and each of the
remainders is selected from a group consisting of a hydrogen atom and a halogen
atom.
[0018] 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
[0019] Embodiments of the present invention provide industrially useful processes
for producing poly(pentafluorosulfanyl)aromatic compounds, as represented by formula (I).
Poly(pentafluorosulfanyl)aromatic compounds can be used as products or intermediates in the
development of bioactive chemicals, in the materials science, and in other like applications.
Unlike previous methods in the art, the processes of the invention utilize short processes, i.e.,
limited number of steps, and low cost reagents to prepare better yields of
poly(pentafluorosulfanyl)aromatic compounds. Further, methods of the invention provide a
greater degree of overall safety in comparison to most prior art methodologies (for example
methodologies that require the use of F2 gas).
[0020] 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 silver or xenon based reactions are cost prohibitive, whereas the present
invention utilizes relatively cheap materials: for example, a halogen such as chlorine (Cl2)
and a fluoro salt such as potassium fluoride (KF).
[0021] Embodiments of the invention include processes which comprise (see for
example Scheme 1, Processes I and II) reacting an aryl sulfur compound having a formula
(II) with a halogen selected from the group of chlorine, bromine, iodine, and interhalogens,
and a fluoro salt having a formula (HI), to form a poly(halotetrafluorosulfanyl)aromatic
compound, represented by formula (IV). The poly(halotetrafluorosulfanyl)aromatic
compound is then reacted with a fluoride source to form poly(pentafluorosulfanyl)aromatic
compounds having a formula (I).
Scheme 1: (Processes I and II)

[0022] With regard to formulas (I), (II), (III), and (IV): one or two of R1, R2, R3,
R4, and R5 are a SF5 group and each of the remainders is selected from a group consisting of a
hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having from 1 to
18 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon
atoms, a nitro group, and a cyano group; one or two of R1', R2', R3', R4', and R5' are a SR6
group and each of the remainders is selected from a group consisting of a hydrogen atom, a
halogen atom, a substituted or unsubstituted alkyl group having from 1 to 18 carbon atoms,
preferably from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms, a nitro
group, and a cyano group; one or two of R1'', R2'', R3'', R4'', and R5'' are a SF4X group and each
of the remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having from 1 to 18 carbon atoms, preferably from 1
to 10 carbon atoms, more preferably from 1 to 4 carbon atoms, a nitro group, and a cyano
group; and R6 is a hydrogen atom, a silyl group, a metal atom, an ammonium moiety, a
phosphonium moiety, or a halogen atom or R6 combines with another R6 of its own molecule
or another molecule to form a single bond. The halogen atom herein is a fluorine atom, a
chlorine atom, a bromine atom, or an iodine atom.
[0023] With regard to M, M is a metal atom, an ammonium moiety, or a
phosphonium moiety; with regard to X, X is a chlorine atom, a bromine atom, or an iodine
atom.
[0024] The term "alkyl" as used herein is a linear, branched, or cyclic alkyl. 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/or any
other group with or without a heteroatom(s) such as an oxygen atom(s), a nitrogen atom(s),
and/or a sulfur atom(s), which does not limit reactions of this invention.
[0025] Poly(halotetrafluorosulfanyl)aromatic compounds of formula (IV) include
stereoisomers composed of trans-conformation and cis-conformation based on a SF4X
substituent as shown below; an aromatic compound having a SF4X group is represented by
ArSF4X:

[0026] Aromatic compounds having two SF4X substituents of this invention, as
represented by XF4S-Arylene-SF4X, are shown as follows;

[0027] Similarly, aromatic compounds having three SF4X groups of this invention
include stereoisomers such as trans,trans,trans-isomers, trans,trans,cis-isomers, trans,cis,cis-
isomers, and cis,cis,cis-isomers.
[0028] Table 1 provides structure names and formulas for reference when
reviewing Schemes 1, 3-10:
[0029] Table 1: Formulas (I), (II), (III), (TV), (V), (I)(R2=Y), and (I)(R2=H)

Process I (Scheme 1)
[0030] Process I includes reacting an aryl sulfur compound, having a formula (II),
with a halogen selected from the group of chlorine, bromine, iodine and interhalogens, and a
fluoro salt (M+F, formula IE) to form a poly(halotetrafluorosulfanyl)aromatic compound
having a formula (IV).
[0031] When one or two of R1', R2', R3', R4', and R5' are a SR6 group, R6 is a
hydrogen atom, a silyl group, a metal atom, an ammonium moiety, or a phosphonium moiety,
and each of the remainders is selected from a group consisting of a hydrogen atom, a halogen
atom, a substituted or unsubstituted alkyl group having from 1 to 18 carbon atoms, preferably
from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms, a nitro group, and a
cyano group; illustrative aryl sulfur compounds, as represented by formula (II), of the
invention include, but are not limited to: each isomer of benzenedithiol, each isomer of
methylbenzenedithiol, each isomer of ethylbenzenedithiol, each isomer of n-
propylbenzenedithiol, each isomer of isopropylbenzenedithiol, each isomer of n-
butylbenzenedithiol, each isomer of sec-butylbenzenedithiol, each isomer of
isobutylbenzenedithiol, each isomer of tert-butylbenzenedithiol, each isomer of
pentylbenzenedithiol, each isomer of hexylbenzenedithiol, each isomer of
heptylbenzenedithiol, each isomer of octylbenzenedithiol, each isomer of
nonylbenzenedithiol, each isomer of decylbenzenedithiol, each isomer of
fluorobenzenedithiol, each isomer of difluorobenzenedithiol, each isomer of
trifluorobenzenedithiol, each isomer of tetrafluorobenzenedithiol, each isomer of
chlorobenzenedithiol, each isomer of bromobenzenedithiol, each isomer of
iodobenzenedithiol, each isomer of nitrobenzenedithiol, each isomer of cyanobenzenedithiol,
each isomer of benzenetrithiol, each isomer of fluorobenzenetrithiol, each isomer of
difluorobenzenetrithiol, each isomer of trifluorobenzenetrithiol, and other like compounds; S-
trimethylsilyl, S-triethylsilyl, S-tripropylsilyl, 5-dimethyl-tert-butylsilyl, and S-
dimethylphenylsilyl derivatives of the benzenedithiol or benzenetrithiol compounds
exemplified here; lithium, sodium, and potassium salts of the benzendithiol or benzenetrithiol
compounds exemplified here; ammonium, diethylammonium, triethylammonium,
trimethylammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium,
and tetrabutylammonium salts of the benzenedithiol or benzenetrithiol compounds
exemplified here; tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium,
tetrabutylphosphonium, and tetraphenylphosphonium salts of the benzenedithiol or
benzenetrithiol compounds exemplified here. Examples of aryl sulfur compounds of formula
(II), where R6 is a halogen atom, are each isomer of benzenedi(sulfenyl chloride), each
isomer of nitrobenzenedi(sulfenyl chloride), and other like compounds. Each of the above
formula (IT) compounds can be prepared in accordance with understood principles of
synthetic chemistry or according to the literature [see for example J. Org. Chem., Vol. 46, pp.
3070-3073 (1981); Chem. Ber. Vol. 106, pp. 719-720 (1973); Chem. Ber., Vol. 106, pp.
2419-2426 (1973); J. Org. Chem., Vol. 45, pp. 4376-4380 (1980), each of which is
incorporated herein by reference for all purposes] or may be available from appropriate
vendors (see for example Sigma-Aldrich, Acros, TCI, Lancaster, Alfa Aesar, etc.).
[0032] When one or two of R1', R2', R3', R4', and R5' are SR6, R6 can combine with
another R of its own molecule or another molecule to form a single bond, and each of the
remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having from 1 to 18 carbon atoms, preferably from 1
to 10 carbon atoms, more preferably from 1 to 4 carbon atoms, a nitro group, and a cyano
group; illustrative aryl sulfur compounds, as represented by formula (IT), include, but are not
limited to: polymeric or dimeric compounds of units exemplified by the following formulas:

[0033] Each of the above formula (II) compounds of the polymeric or dimeric
compounds can be prepared in accordance with understood principles of synthetic chemistry
or according to the literatures [see for example J. Am. Chem. Soc, Vol. 82, pp. 3064-3072
(1962), incorporated herein by reference for all purposes].
[0034] Typical halogens employed in the present invention include: chlorine (Cl2),
bromine (Br2), iodine (I2), and interhalogens such as ClF, BrF, ClBr, CII, Cl3I, and BrI.
Among these, chlorine (Cl2) is preferable due to its relative low cost.
[0035] Fluoro salts, having a formula (III), are those which are easily available and
are exemplified by metal fluorides, ammonium fluorides, and phosphonium fluorides.
Process I can be carried out using one or more fluoro salts. 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, and ammonium
fluorides, such as tetramethylammonium fluoride and tetrabutylammonium 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.
[0036] Fluoro salts (formula EH) can be used as a mixture of a metal fluoride and
an ammonium fluoride or a phosphonium fluoride, a mixture of an ammonium fluoride and a
phosphonium fluoride, or a mixture of a metal fluoride, an ammonium fluoride, and a
phosphonium fluoride.
[0037] 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"; or a mixture of an ammonium salt
having an anion part other than F and a phosphonium fluoride. Furthermore, there can be 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 themselves (for example, see Scheme 2).
Scheme 2: Mutual anion exchange reaction between salts

[0038] 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 a
catalytic amount to any amount that does not interfere with the reactions or does not
dramatically decrease the yield 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. Examples of the anion parts other than F" include, but are not limited to: Cl-, Br-, I-,
BF4-, PF6-, SO4-, -OCOCH3, -OCOCF3, -OSO2CH3, -OSO2CF3, -OSO2C4F9, -OSO2C6H5,-
OSO2C6H4CH3, -OSC2C6H4Br, and so on. Among them, the anion parts (other than F) which
do not have an oxygen anion(s) are preferable, and Cl-, BF4- and PF6- are more preferable
because of relatively high yield reactions. In addition, Cl- is most preferable because of its
cost.
[0039] 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. A preferable solvent will not substantially react with the starting
materials and reagents, the intermediates, and/or 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 relatively higher yields of the products, as
compared to other suitable solvents.
[0040] 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.
[0041] Reaction conditions of Process I are optimized to obtain economically good
yields of product. When one of R1', R2', R3', R4', and R5' is SR6 (R6 = a hydrogen atom, a silyl
group, a metal atom, an ammonium moiety, or a phosphonium moiety), about 6 mol to about
30 mol of halogen are combined with about 1 mol of aryl sulfur compound (formula II) to
obtain a good yield of a poly(halotetrafluorosulfanyl)aromatic compound (formula IV). When
two of R1, R2, R3 , R4, and R5 are SR6 (R6 = a hydrogen atom, a silyl group, a metal atom,
an ammonium moiety, or a phosphonium moiety), about 9 mol to about 45 mol of halogen
are combined with about 1 mol of aryl sulfur compound (formula II) to obtain a good yield of
a poly(halotetrafluorosulfanyl)aromatic compound (formula IV).
[0042] When one of R1', R2', R3', R4', and R5' is SR6 (R6 = a halogen atom), about
4 mol to about 20 mol of halogen are combined with about 1 mol of aryl sulfur compound
(formula II) to obtain a good yield of a poly(halotetrafluorosulfanyl)aromatic compound
(formula IV). When two of R1', R2', R3', R4', and R5' is SR6 (R6 = a halogen atom), about 6
mol to about 30 mol of halogen are combined with about 1 mol of aryl sulfur compound
(formula IT) to obtain a good yield of a poly(halotetrafluorosulfanyl)aromatic compound
(formula IV).
[0043] When one of Rr, R2', R3', R4', and R5' are SR6 in which R6 forms a single
bond with another R6, about 5 mol to about 25 mol of halogen are combined with about 1 mol
of one unit of aryl sulfur compound (formula IT) to obtain a good yield of a
poly(halotetrafluorosulfanyl)aromatic compound (formula IV). When two of R1', R2', R3', R4',
and R5' are SR6 in which R6 forms a single bond with another R6, about 7.5 mol to about 37.5
mol of halogen are combined with about 1 mol of one unit of aryl sulfur compound (formula
H) to obtain a good yield of a poly(halotetrafluorosulfanyl)aromatic compound (formula IV).
[0044] When one of R1', R2', R3', R4', and R5' is SR6, the amount of a fluoro salt
(formula HI) used in embodiments of Process I can be in the range of from about 8 to about
40 mol against 1 mol of aryl sulfur compound or 1 mol of a unit of aryl sulfur compound of
formula (II) to obtain economically good yields of product. When two of R1' , R2', R3', R4',
and R5' are SR6, the amount of a fluoro salt (formula III) used in embodiments of Process I
can be in the range of from about 12 to about 60 mol against 1 mol of aryl sulfur compound
or 1 mol of a unit of aryl sulfur compound of formula (II) to obtain economically good yields
of product.
[0045] Note that the reaction time of 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 hour (h) to several days, preferably, within a few days.
Process II (Scheme 1)
[0046] Embodiments of the invention include Process II, a reaction of a
poly(halotetrafluorosulfanyl)aromatic compound, obtained in Process I, with a fluoride
source, as shown in Scheme 1.
[0047] Fluoride sources employable in Process II are compounds that display
fluoride activity to the poly(halotetrafluorosulfanyl)aromatic compounds (formula IV).
Anhydrous fluoride sources are used preferably because byproducts, arylsulfonyl fluorides
[aromatic compounds with a SO2F substituent(s)], are not formed or their formation is
suppressed. The SO2F substituent may be derived from a SF4X substituent when water
molecules (H2O) are present.
[0048] Process II can be carried out using one or more fluoride sources. 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.
[0049] The fluoride sources include mixtures or compounds of fluoride sources
with fluoride source-activating compounds. The combination of a fluoride source and a
fluoride source-activating compound is beneficial to cost performance, because a relatively
cheap fluoride source-activating compound can activate a relatively cheap fluoride source,
which will not work satisfactorily by itself, as a fluoride source for the
poly(halotetrafluorosurfanyl)aromatic compound (formula IV) (owing to its low reactivity).
[0050] In addition, 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.
[0051] 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 (alkali earth metal fluorides) such as
BeF2, MgF2, MgFCl, CaF2, SrF2, BaF2 and so on; fluorides of Element 13 such as BF3, BF2Cl,
BFCl2, AlF3, AlF2C1, AlFCl2, GaF3, InF3, and so on; fluorides of Element 14 such as SiF4,
SiF3Cl, SiF2Cl2, SiFCl3, GeF2, GeF4, GeF2Cl2, SnF2, SnF4, PbF2, PbF4, and so on; fluorides of
Element 15 such as PF3, PF5, AsF3, AsF5, SbF3, SbF5, SbF4Cl, SbF3Cl2, SbFCl3, SbFCl4, BiF3,
BiF5, and so on; fluorides of Element 16 such as OF2, SF4, SeF4, SeF6, TeF4, TeF6, and so on;
fluorides of Element 17 such as F2, ClF, ClF3, BrF, BrF3, IF5, and so on. Among these, the
fluorides of the Elements 13-15 are preferable because of product yields, availability, and
cost, and BF3, AlF3, AlF2Cl, SiF4, PF3, PF5, SbF3, SbF5, SbF4Cl, and SbF3Cl2 are preferably
exemplified.
[0052] Suitable examples of fluorides of the transition elements (transition metal
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, NbFs, TaFs, and so on; fluorides of Element 6 such as CrF3, MoF6, 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, CoF3, RhF3, IrF6, and so on; fluorides of Element 10 such as NiF2, PdF2, PtF2, PtF4,
PtF6, and so on; fluorides of Element 11 such as CuF2, CuFCl, AgF, AgF2, and so on; and
fluorides of Element 12 such as ZnF2, ZnFCl, CdF2, HgF2, and so on. Among the fluorides of
transition elements, 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, yield, and cost.
[0053] Suitable examples of mixtures 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,
(C2H5)4NF/HF, (C4H9)4NF/HF, ZrJVHF, CuF2/HF, BF3/HF, A1F3/HF, SiF4/BF3, SiF4/PF5,
SiFVSbFs, PF3/PF5, AsF3/AsF5, SbF3/SbF5, SbF3/SbF5/HF, ZnF2/SbF5, ZnF2/SbF5/HF,
KF/SbF5, KF/SbF5/HF, and so on.
[0054] Fluoride source-activating compounds usable in this invention include, but are not
limited to, SbCl5, AlCl3, PCl5, BCl3, and other like compounds. Suitable examples of
mixtures or compounds of the fluorides with fluoride source-activating compounds include,
but are not limited to, SbF3/SbCl5, BF3/SbCl5, AlF3/SbCl5, SiF4/SbCl5, GeF4/SbCl5,
SnF4/SbCl5, PbF2/SbCl5, BiF3/SbCl5, HF/SbCls, ZnF2/SbCl5, CuF2/SbCl5, FeF3/SbCl5,
TiF4/SbCl5, SbF3/AlCl3, BF3/AlCl3, AlF3/AlCl3, SiF4/AlCl3, GeF4/AlCl3, SnF4/AlCl3,
PbF2/AlCl3, BiF3/AlCl3, HF/AlC13, ZnF2/AlCl3, CuF2/AlCl3, FeF3/AlCl3, Tif4/AlCl3,
SbF3/PCl5, BF3/PCl5, A1F3/PCl5, SiF4/PCl5, GeF4/PCl5, SnF4/PCl5, PbF2/PCl5, BiF3/PCl5,
HF/PCl5, ZnF2/PCl5, CuF2/PCl5, FeF3/PCl5, SbF3/BCl3, BF3/BCl3, AlF3/BCl3, SiF4/BCl3,
GeF4/BCl3, SnF4/BCl3, PbF2/BCl3, BiF3/BCl3, HF/BCl3, ZnF2/BCl3, CuF2/BCl3, and other
like compounds combinations. Among these mixtures or compounds of fluorides with
fluoride source-activating compounds, mixtures or compounds of fluorides of the Elements
13-15 with fluoride source-activating compounds are preferable from a viewpoint of product
yields and cost performance, and among them, SbF3/SbCls, AlF3/AlCl3, and PF3/PCl5 are
more preferable from an additional viewpoint of recovery and recycling of elements such as
Sb, Al, and P. The amount used of a fluoride source-activating compound against a fluoride
source is from a catalytic amount to any amount that does not hurt the reactions of this
invention. The preferable amount of a fluoride source-activating compound against 1 mol of
the fluoride source can be selected in the range of from about 0.005 mol to about 1.5 mol,
more preferably about 0.01 mol to about 1 mol, furthermore preferably about 0.03 mol to
about 0.5 mol, from a viewpoint of cost performance and reaction efficiency and yields.
[0055] Among the organic molecules usable for the mixtures, salts, or complexes with the
fluorides, pyridines such as pyridine, methylpyridine, dimethylpyridine, trimethylpyridine,
and so on, ethers such as dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, and
so on, alkylamines such as trimethylamine, triethylamine, and so on, nitriles such as
acetonitrile, propionitrile, and so on are preferable. Among these, pyridine, dimethyl ether,
diethyl ether, triethylamine, and acetonitrile are more preferable because of availability and
cost. Suitable examples of mixtures, salts, or complexes of the fluorides with organic
molecules include, but are not limited to: BF3 diethyl etherate [BF3- O(C2H5)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),
HF/methylpyridine, HF/dimethylpyridine, HF/trimethylpyridine, HF/trimethylamine,
HF/triethylamine, HF/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.
[0056] Among these examples of fluoride sources mentioned above, hydrogen fluoride,
fluorides of transition elements in the Periodical Table, fluorides of the Elements 13-15 in
the Periodical Table, and mixtures or compounds thereof, as well as mixtures or compounds
of these fluorides with fluoride source-activating compounds are preferable. Among these,
fluorides of the Elements 13-15 are furthermore preferable for the reactions of Process II.
The fluorides of the Elements 13-15 can be preferably used with the fluoride source-
activating compounds.
[0057] In some embodiments, since the reaction of a (halotetrafluorosulfanyl)aromatic
compound with a fluoride source can be slowed down by flowing an inactive gas (such as
nitrogen (see Example 2)), 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 may be a case that it is preferable that
the reaction of a poly(halotetrafluorosulfanyl)aromatic compound of formula (IV) with a
fluoride source 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.
[0058] Process n can be carried out with or without a solvent. The use of solvent is
preferable for mild and efficient reactions. Where a solvent is utilized, alkanes, halocarbons,
aromatics, ethers, nitriles, nitro compounds can be used. Example alkanes include normal,
branched, cyclic isomers of pentane, hexane, heptane, octane, nonane, decane, dodecane,
undecane, and other like compounds. Illustrative halocarbons include dichloromethane,
chloroform, carbon tetrachloride, dichloroethane, trichloroethane, terachloroethane,
trichlorotrifluoroethane, perfluoropentane, perfluorohexane, perfluorocyclohexane,
perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecane, perfluorodecalin,
Fluorinert® FC-72, FC-75, FC-77, FC-84, FC-87, FC-104, and FC-40, and other like
compounds. Fluorinert® FC series are perfluorinated organic compounds, which are produced
by 3M Company. Illustrative aromatics include benzene, toluene, xylene, fluorobenzene,
chlorobenzene, dichlorobenzene, trichlorobenzene, hexafluorobezene, benzotrifluoride, and
other like compounds. Illustrative ethers include diethyl ether, dipropyl ether, di(isopropyl)
ether, dibutyl 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. Among them, alkanes and halocarbons are preferable. 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.
[0059] 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 -80°C to about
+200°C.
[0060] 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 one unit of SF4X of a poly(halotetrafluorosulfanyl)aromatic compound (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).
[0061] As described for 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 1 minute to several days,
preferably, within a few days.
[0062] Process n is preferably carried out under anhydrous conditions. Anhydrous
conditions are preferable because byproducts, compounds having a -SO2F group(s), are not
formed or their formation is suppressed. Hydrous or moist conditions may produce the
byproducts depending on the amount of water contained and on the nature of the reagents,
solvents, and other reaction conditions. When the product obtained is contaminated with the
byproduct(s), the product can be purified by hydrolysis, preferably by alkaline hydrolysis
with or without a phase transfer catalyst. The byproducts are hydrolyzed to the corresponding
sulfonic acids or sulfonic acid salts which are easily separated from the product.
[0063] Process II may also be carried out under hydrous or moist conditions. In some
cases, hydrous or moist conditions may accelerate the reaction. Hydrous or moist conditions
herein can be prepared in many ways, for example: (1) a hydrous or moist fluoride source
mentioned above is used; (2) a moist solvent mentioned above is used; (3) a moist
poly(halotetrafluorosulfanyl)aromatic compound (formula IV) is used; (4) an adequate
amount of water, steam, or water vapor is added to a fluoride source, a
poly(halotetrafluorosulfanyl)aromatic compound (formula IV), solvent, and/or a reaction
mixture or a reaction system; (5) moist air is introduced to a fluoride source, a
poly(halotetrafluorosulfanyl)aromatic compound (formula IV), solvent, and/or a reaction
mixture or a reaction system; and/or (6) the reaction is run in moist air, and so on. When the
product obtained is contaminated with byproducts, compounds having a -SO2F group, the
product can be purified by hydrolysis, preferably by alkaline hydrolysis with or without a
phase transfer catalyst. The byproducts are hydrolyzed to the corresponding sulfonic acids or
sulfonic acid salts which are easily separated from the product.
[0064] Embodiments of the invention include processes which comprise (see for
example Scheme 3, Processes I and II') reacting an aryl sulfur compound having a formula
(II) with a halogen selected from the group of chlorine, bromine, iodine, and interhalogens,
and a fluoro salt having a formula (III), to form a poly(halotetrafluorosulfanyl)aromatic
compound, represented by formula (IV). The poly(halotetrafluorosulfanyl)aromatic
compound 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
poly(pentafluorosulfanyl)aromatic compound as represented by a formula (I).

[0065] With regard to formulas (I), (II), (HI), and (IV), R1, R2, R3, R4, R5, R6, R1',
R2', R3', R4', R5', R1", R2", R3", R4", R5", M, and X have the same meaning as defined above.
[0066] Process I is as previously described.
[0067] Process II' is the same as Process II above, except for the following
modifications: the reaction of a poly(halotetrafluorosulfanyl)aromatic compound and a
fluoride source is conducted in the presence of a halogen selected from the group of chlorine,
bromine, iodine, and interhalogens. Since the reaction of a (halotetrafluorosulfanyl)aromatic
compound with a fluoride source is activated in the presence of a halogen as shown in
Example 8, it is expected that the reaction of a poly(halotetrafluorosulfanyl)aromatic
compound with a fluoride source is activated in the presence of a halogen.
[0068] It is expected that a halogen activates a fluoride source and/or prevents
disproportionation or reduction of a poly(halotetrafluorosulfanyl)aromatic compound
(formula rV), which may occur during this reaction. Therefore, other fluoride source-
activating and/or disproportionation or reduction-preventing compounds are within the scope
of this invention. The reaction in the presence of a halogen may be carried out by filling a
reactor with a halogen gas, 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 (Cl2) is preferable due to cost.
[0069] In some cases, during reactions of Process II' which are conducted in the
presence of a halogen, halogenation at the aromatic ring of the starting compounds or
products may occur dependent on the substrates, reagents, and reaction conditions, forming
newly halogenated products. This invention also includes such reactions and newly
halogenated products.
[0070] The amount of halogen is from a catalytic amount to an amount in large
excess. From the viewpoint of cost, a catalytic amount to about 5 mol of the halogen,
preferably selected against 1 mol of one unit of SF4X of
poly(halotetrafluorosulfanyl)aromatic compound (formula IV).
[0071] Embodiments of the present invention include processes which comprise
(Process HI) reacting an arylsulfur trifluoride having a formula (V) with a halogen (chlorine,
bromine, iodine, or interhalogens) and a fluoro salt having a formula (HI) to form a
poly(halotetrafluorosulfanyl)aromatic compound having a formula (IV) and (Process II)
reacting the obtained poly(halotetrafluorosulfanyl)aromatic compound with a fluoride source
to form the poly(pentafluorosulfanyl)aromatic compound having a formula (I). Scheme 4
showing Processes HI and II are presented as follows:

[0072] With regard to formulas (I), (III), (IV), and (V), R1, R2, R3, R4, R5, R1", R2",
R3", R4", R5", R1'", R2"', R3'", R4'", R5'", M, and X have the same meaning as defined above.
Process III (Scheme 4)
[0073] Embodiments of the present invention provide processes for producing a
poly(pentafluorosulfanyl)aromatic compound (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 a
poly(halotetrafluorosulfanyl)aromatic compound having a formula (IV).
[0074] 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. 82
(1962), pp. 3064-3072, and J. Fluorine Chem. Vol. 33 (2003), pp.2505-2509, incorporated
herein by reference for all purposes] and are exemplified, but are not limited to, each isomer
of benzenedi(sulfur trifluoride) and each isomer of benzenetri(sulfur trifluoride).
[0075] Based on consideration of the reaction mechanism, arylsulfur trifluorides
(formula V) can be the intermediates in Process I.
[0076] A halogen employable in the present invention for Process III is the same as
for Process I described above except for the amount used in the reaction.
[0077] Fluoro salts having a formula (III) for Process III are the same as for
Process I described above, except for the amount used in the reaction.
[0078] 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.
[0079] In order to obtain economically good yields of the product, the reaction
temperature of 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 ~ +50°C. Furthermore preferably, the
temperature can be selected in the range of -20°C - +40°C.
[0080] When one of R1'", R2'", R3'", R4'", and R5'" is SF3, about 2 mol to about 10
mol of halogen are combined with about 1 mol of arylsulfur trifluoride (formula V) to obtain
a good yield of a poly(halotetrafluorosulfanyl)aromatic compound (formula IV). When two
of R1'", R2'", R3'", R4'", and R5'" are SF3, about 3 mol to about 15 mol of halogen are
combined with about 1 mol of arylsulfur trifluoride (formula V) to obtain a good economical
yield of a poly(halotetrafluorosulfanyl)aromatic compound (formula IV).
[0081] 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.
Process n (Scheme 4)
[0082] Process E is as described above.
[0083] Embodiments of the present invention include processes which comprise
(Process III) 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 a
poly(halotetrafluorosuflanyl)aromatic compound having a formula (IV), and (Process II')
reacting the obtained poly(halotetrafluorosulfanyl)aromatic compound with a fluoride source
in the presence of a halogen selected from the group of chlorine, bromine, iodine, and
interhalogens to form the poly(pentafluorosulfanyl)aromatic compound having a formula (I).
Scheme 5 showing Processes IE and II' are as follows:

[0084] With regard to formulas (I), (III), (IV), and (V), R1, R2, R3, R4, R5, R1", R2",
R3", R4", R5", R1'", R2'", R3'", R4'", R5'", M, and X have the same meaning as defined above.
[0085] Processes III and II' are as described above.
[0086] Furthermore, the present invention includes a process (Scheme 6, Process I)
for preparing a poly(halotetrafluorosulfanyl)aromatic compound having a formula (IV),
which comprises reacting an aryl sulfur compound having a formula (II) with a halogen
selected from the group of chlorine, bromine, iodine, and interhalogens, and a fluoro salt
having a formula (III) to form the poly(halotetrafluorosulfanyl)aromatic compound.

[0087] In the formulas (II), (III), and (IV), R1', R2', R3', R4', R5', R6, R1", R2", R3",
R4 , R5 , M, and X represent the same meaning as defined above.
[0088] Process I is described above.
[0089] Furthermore, the present invention includes a process (Scheme 7, Process
IK) for preparing a poly(halotetrafluorosulfanyl)aromatic compound having a formula (IV),
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 (HI) to form a poly(halotetrafluorosulfanyl)aromatic compound.

[0090] In the formulas (III), (IV), and (V), R1", R2", R3", R4", R5", R1", R2'", R3'",
R4''' , R5''' , M, and X represent the same meaning as defined above.
[0091] Process III is as described above.
[0092] Furthermore, the present invention includes a process (Scheme 8, Process
II) for preparing a poly(pentafluorosulfanyl)aromatic compound having a formula (I), which
comprises reacting a poly(halotetrafluorosulfanyl)aromatic compound having a formula (IV)
with a fluoride source to form a poly(pentafluorosulfanyl)aromatic compound.

[0093] In the formulas (I) and (IV), R1, R2, R3, R4, R5, R1", R2", R3", R4", R5", and X
represent the same meaning as defined above.
[0094] Process II is as described above.
[0095] Furthermore, the present invention includes a process (Scheme 9, Process
II') for preparing a poly(pentafluorosulfanyl)aromatic compound having a formula (I), which
comprises reacting a poly(halotetrafluorosulfanyl)aromatic compound 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 a poly(pentafluorosulfanyl)aromatic compound.

[0096] For formulas (I) and (IV), R1, R2, R3, R4, R5, R1", R2", R3", R4", R5", and X
represent the same meaning as defined above.
[0097] Process II' is as described above.
[0098] According to the present invention, the poly(pentafluorosulfanyl)aromatic
compounds having the formula (I) can easily and cost-effectively be produced from available
starting materials.
[0099] Halogenated poly(pentafluorosulfanyl)aromatic compounds as represented
by formula (I)(R2=Y) among the poly(pentafluorosulfanyl)aromatic compounds of formula
(I), are also produced by reacting a hydro poly(pentafluorosulfanyl)aromatic compound
having a formula (I)(R2=H) with a halogenating agent and an acid to form a
poly(pentafluorosulfanyl)aromatic compound of formula (I)(R2=Y) (See Scheme 10, Process
IV).

[00100] With regard to formulas (I)(R2=H) and (I)(R2=Y), Y is a halogen atom
which is a fluorine atom, chlorine atom, bromine atom, or iodine atom; and one or two of R1,
R3, R4, and R5 are a pentafluorosulfanyl (SF5) group and each of the remainders is selected
from a group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted
alkyl group having from 1 to 18 carbon atoms, preferably from 1 to 10 carbon atoms, more
preferably from 1 to 4 carbon atoms, a nitro group, and a cyano group.
[00101] Process IV requires strong reaction conditions for halogenation because the
benzene ring is greatly deactivated by at least two strong electron-withdrawing SF5 groups.
Preferable halogenating agents employable for Process IV include: a halogen such as fluorine
(F2), chlorine (Cl2), bromine (Br2), and iodine (I2); a N-halo imide such as N-
chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 1,3-dibromo-5,5-
dimethylhydantoin, and so on; a halogen oxide such as sodium bromate, potassium bromate,
sodium iodate, potassium iodate, potassium chlorate, and so on; and mixtures thereof.
Preferable acids employable in Process TV include: sulfuric acid, fluorosulfuric acid,
chlorosulfuric acid, trifluoromethanesulfonic acid, methanesulfonic acid, trifluoroacetic acid,
trichloroacetic acid, and so on, and these aqueous solutions, and mixtures thereof.
[00102] Typically, an additional solvent for the reaction of Process IV is not
necessary since the acid or its aqueous solution used in Process IV acts as a solvent. When
another solvent is needed, water, acetic acid, acetic anhydride, propionic acid, methylene
chloride, chloroform, carbon tetrachloride and the like are usable.
[00103] In order to optimize yield with regard to Process IV, the reaction
temperature can be selected from about -30 °C to about +200 °C, preferably, -10 °C to about
+170 °C, more preferably about 0 °C to about +150 °C.
[00104] In order to obtain economically good yields of the products using Process
rV, the amount of a halogenating agent, which provides n number of reactive halogen atom
species (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 the molecule of formula (I)(R2=H). More typically, the
amount can be selected in the range of from about 1/n to about 10/n from the viewpoint of
yield and cost.
[00105] As described above, the reaction time of Process IV varies dependent on
reaction temperature, 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 IV, but can be from about 1 min to several days, preferably, within a few
days.
[00106] The present invention also provides novel
poly(chlorotetrafluorosulfanyl)aromatic compound represented by formula (IV') as useful
intermediates for preparing the poly(pentafluorosulfanyl)aromatic compounds of formula (I):

wherein one or two of R1, R2, R3, R4, and R5 are SF4Cl and each of the
remainders is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl
group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably
1 to 4 carbon atoms, a nitro group, or a cyano group. The remainders are preferably
selected from a group consisting of a hydrogen atom and a halogen atom. The halogen
atom can be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
[00107] Among these, 1,2-, 1,3-, and l,4-bis(chlorotetrafluorosulfanyl)benzene, 1,3-
bis(chlorotetrafluorosulfanyl)-5-fluoro-, -chloro-, -bromo-, and -iodo-benzene, 1,4-
bis(chlorotetrafluorosulfanyl)-2,5-difluorobenzene, l,4-bis(chlorotetrafluorosulfanyl)-2,3,5,6-
tetrafluorobenzene, 1,2,3-, 1,2,4-, and l,3,5-tris(chlorotetrafluorosulfanyl)benzene, and 1,3,5-
trifluoro-2,4,6-tris(chlorotetrafluorosulfanyl)benzene are preferable. 1,3- and 1,4-
Bis(chlorotetrafluorosulfanyl)benzene, 1,3-bis(chloroterafluorosulfanyl)-5-bromobenzene,
1,4-bis(chlorotetrafluorosulfanyl)-2,5-difluorobenzene, 1,4-bis(chlorotetrafluorosulfanyl)-
2,3,5,6-tetrafluorobenzene, and l,3,5-tris(chlorotetrafluorosulfanyl)benzene are more
preferable.
[00108] The present invention also provides a novel and useful
bis(pentafluorosulfanyl)benzene compound represented by formula (F);

wherein one of Ra, Rb, Rc, Rd, and Re is a SF5 group and each of the
remainders is selected from a group consisting of a hydrogen atom and a halogen
atom. The halogen atom can be a fluorine atom, a chlorine atom, a bromine atom, or
an iodine atom.
[00109] Among these, 1,2-bis(pentafluorosulfanyl)benzene, 1,3-
bis(pentafluorosulfanyl)benzene, 1,4-bis(pentafluorosulfanyl)benzene, 1,3-
bis(pentafluorosulfanyl)-5-fluoro-, -chloro-, -bromo-, and -iodo-benzene, 1,4-
bis(pentafluorosulfanyl)-2,5-difluorobenzene, and 1,4-bis(pentafluorosulfanyl)-2,3,5,6-
tetrafluorobenzene are preferable. l,3-Bis(pentafluorosulfanyl)benzene, 1,4-
bis(pentafluorosulfanyl)benzene, 1,3-bis(pentafluorosulfanyl)-5-bromobenzene, 1,4-
bis(pentafluorosulfanyl)-2,5-difluorobenzene, and 1,4-bis(pentafluorosulfanyl)-2,3,5,6-
tetrafluorobenzene are more preferable.
[00110] The following examples will illustrate the present invention in more detail,
but it should be understood that the present invention is not deemed to be limited thereto.
EXAMPLES
[00111] The following examples are provided for illustrative purposes only and are not
intended to limit the scope of the invention. Tables 2 and 3 provide structure names and
formulas for reference when reviewing the following examples:

Example 1. Synthesis of 1,3-bis(pentafluorosulfanyl)benzene(Ia) from 1,3-benzenedithiol

[00112] (Process I) A 500 mL fluoropolymer (PFA) reactor was setup with
magnetic stirrer, ice bath, gas (N2, Cl2) inlet tube, and gas outlet tube protected by a CaCl2
tube. Gas flow was controlled by digital controller and measured by digital integrator. The
vessel was charged with anhydrous potassium fluoride (100g, 1.72 mol), and set up for
reaction under nitrogen flow. Anhydrous acetonitrile (300 mL) was added, followed by 1,3-
benzenedithiol (9.78 g, 68.7 mmol). After chilling in the ice bath with stirring under N2 flow
for 1 hour, N2 was stopped and then chlorine gas was introduced below the surface at 60-80
mL/min with vigorous stirring. Over approximately 6 hours, a total of 27.11 L(1.21 mol) of
Cl2 was added. The reaction was then allowed to come to room temperature with stirring.
After allowing to stir and react for two days, the reaction mixture was filtered, washed
through with dry acetonitrile (200 mL). The solvent was then removed at room temperature
under vacuum, leaving the crude product (23.2 g, crude yield 93%) as a white solid, which
was recrystallized from pentane in a freezer to give white crystals of 1,3-
bis(chlorotetrafiuorosulfanyl)benzene (IVa) (14.08g, yield 56%). To obtain a sample for
analysis, some of the crystals were further recrystallized. The properties and spectral data of
l,3-bis(chlorotetrafluorosulfanyl)benzene (IVa) are shown in the following: m.p. 82-83.5 °C
(in a sealed capillary); 19F NMR (CDCl3) d 136.14 (s, SF4Cl); 1H NMR (CDCl3) d 8.12 (t,
J=2.0 Hz, 1H, 2-H), 7.89 (dd, J=8.3, 2.0 Hz, 2H, 4,6-H), 7.58 (t, J=8.3 Hz, 1H, 5-H); 13C
NMR (CDCl3) d 155.12 (quintet, J=20.6 Hz), 129.25 (s), 129.04 (t, J=4.3 Hz), 124.12
(quintet, J=4.9 Hz). Elemental analysis; calcd for C6H4Cl2F8S2; C, 19.85%, H, 1.11%; found,
C, 20.30%, H, 1.20%. The NMR showed that l,3-bis(chlorotetrafluorosulfanyl)benzene
obtained is a trans,trans-isomer.
[00113] (Process II) A 130 mL fluoropolymer (PFA) reactor was set up with
magnetic stirrer, oil bath, gas (N2) inlet tube, outlet port and water condenser. The vessel was
charged with anhydrous ZnF2 (6.33 g, 61.2 mmol) and 1,3-
bis(chlorotetrafluorosulfanyl)benzene (IVa) (10.02 g, 27.6 mmol) prepared in Process I, and
set up for reaction. After a N2 purge, the set up was capped with a balloon (the water
condenser was connected to a balloon) and the reactor was heated to 140 °C for 17 hours. The
reaction mixture was then cooled to room temperature and extracted with pentane. The
pentane solution was filtered and removal of the solvent gave a solid (8.25 g). The 19F NMR
analysis of the solid showed that l,3-bis(pentafluorosulfanyl)benzene (Ia) is produced in 54%
yield from the starting material (IVa). The pure product was obtained as white crystals by
recrystallization from pentane in a freezer. The properties and spectral data of 1,3-
bis(pentafluorosulfanyl)benzene (Ia) are shown in the following: m.p. 62-62.8 °C (in a sealed
capillary); 19F NMR (CDCl3) d 81.88 (quintet, J=150.4 Hz, 2F, 2xSF), 62.95 (d, J=150.4 Hz,
8F, 2xSF4); 1H NMR (CDCl3) d 8.16 (t, J=2.0 Hz, 1H, 2-H), 7.93 (dd, J=8.2, 2.0 Hz, 2H, 4,6-
H), 7.63 (t, J=8.2 Hz, 1H, 5-H); 13C NMR (CDCl3) d 153.72 (quintet, J=19.1 Hz), 129.49 (s),
129.25 (t, J=4.7 Hz), 124.34 (m); GC-Mass m/z 330 (M+). Elemental analysis; calcd for
C6H4F10S2; C, 21.82%, H, 1.22%; found, C, 21.79%, H, 1.52%.
Examples 2-5. Synthesis of polypentafluorosulfanyl)aromatic compounds (Ic)~(If) from the
corresponding aryl sulfur compounds
[00114] (Process I) An aryl sulfur compound of formula (II) was reacted with
chlorine and potassium fluoride in acetonitrile in a similar way as in Process I of Example 1.
Table 4 shows the amounts of the aryl sulfur compounds, reagents, and solvents, reaction
conditions, and results for Examples 2-5 together with those of Example 1. Properties and
spectral data of the products, poly(halotetrafluorosulfanyl)aromatic compounds (IVc)-(rVf)
are shown below.
[00115] Regarding the chemical structure of SF4Cl of the products (IVc)-(rVf)
obtained from Process I: 19F NMR analysis showed that reaction in Example 2 gave product
(IVc) having a trans conformation at SF4Cl. Reaction in Example 3 gave products (IVd)
having trans and cis conformation in which a ratio of trans :cis is 93:7. Reaction in Example 4
gave products (IVe) having trans and cis conformation in which a ratio of transxis is 57:43.
Reaction in Example 5 gave product (IVf) having a trans conformation.
[00116] Regarding post-treatment of Process I: for Example 2, the reaction mixture
was filtered and washed through with dry dichloromethane. The filtrate was dried by vacuum
to give 17.2 g (yield 74%) of product (IVc) (trans,trans-isomer), which was washed with dry
dichloromethane to give an analytical sample of IVc. For Example 3, the reaction mixture
was filtered and washed through with dry acetonitrile then chloroform. The filtrate was dried
by vacuum to give a white solid, which was washed with a small amount of dry
dichloromethane to give 13.2 g (yield 52%) of IVd, which was mostly a trans,trans-isomer
(trans/cis=96/4). For Example 4, the reaction mixture was filtered and washed through with
dry chloroform. The filtrate was dried by vacuum to give a white solid. The solid was
recrystallized from a 1:1 mixture of dry dichloromethane and pentane and filtered to give
6.76g of pure IVe, which was a mixture of trans,trans- and cis,cis-isomers (trans/cis=80/20).
By repeated recrystallization of the solid obtained from the filtrate, additional 15.25g was
obtained. The total amount of IVe was 22.0g (yield 79%). For Example 5, the reaction
mixture was filtered and washed through dry acetonitrile then dichloromethane. The filtrate
was dried by vacuum to give a white solid, which was recrystallized from a mixture of
dichloromethane and pentane to give 10.55g (crude yield 84%) of crude product IVf, which
was purified by recrystallization from pentane.
[00117] (Process II) A fluoropolymer (PFA) vessel was charged with 9.89g (27.2
mmol) of IVc obtained from Process I and 320mL of Fluorinert® FC-72 (perfluorinated
organic compounds having b.p. 56°C, available from SynQuest laboratories, Inc.) under
nitrogen atmosphere and the mixture was cooled on a bath of around -80°C. A solution of
2.10mL (30mmol) of SbF5 in 35mL of FC-72 was added into the stirred mixture and the
mixture was allowed to warm gradually to room temperature over about 8 h. After stirring
overnight at room temperature, the reaction mixture was filtered and treated with KF, then
filtered. The solvent was removed by reduced pressure and the residue was recrystallized
from FC-72 to give 5.83g (65%) of product Ic. A pure sample of Ic was obtained by washing
with FC-72 thoroughly.
[00118] Products Id, Ie, and If were prepared in a similar way as in Process II above
used in the preparation of Ic. Table 4 shows the amounts of the starting materials rVd-f,
reagents, and solvents, reaction conditions, and results of Examples 2-5. Properties and
spectral data of the products (Ic)-(If) are shown below.
[00119] Regarding post-treatment of Process II: for Example 2, it was described
above. For Example 3, the reaction mixture was filtered and treated with KF, then filtered.
The solvent was removed under reduced pressure and the residue was crystallized from
pentane to give 5.27g (52%) of product Id. For Example 4, the reaction mixture was filtered
and treated with KF, then filtered. The filtrate was concentrated to give crystals (3.36g, yield
67%) of product Ie. For Example 5, the reaction mixture was filtered and treated with KF,
then filtered. The filtrate was dried up to give 0.87g of product If. The solid obtained from the
reaction mixture was quenched with KF and extracted with FC-72 to give an additional 1.1g,
which was found to be about 0.48g of the product by GC analysis. The total yield was about
1.35g (36%).

[00120] Properties and spectral data of the products (IVa) and (Ia) are as shown in
Example 1. Properties and spectral data of products (IVc)-(IVf) and (Ic)-(If) are shown in the
following:
[00121] 1,4-Bis(chlorotetrafluorosulfanyl)benzene (IVc); m.p. 200.8-201.6 °C; 19F
NMR (CDCl3) d 135.72 (s, 8F); 1H NMR (CDCl3) d 7.84 (s, 4H); 13C NMR (CDCl3) d
156.90 (quintet, J=20.2 Hz), 126.73 (m); GC-Mass m/z 330 (M+). Elemental analysis; calcd
for C6H4Cl2F8S2; C, 19.85%, H, 1.11%; found, C, 19.71%, H, 1.10%. NMR analysis showed
that product (IVc) obtained is a trans,trans-isomer.
[00122] 1,4-Bis(pentafluorosulfanyl)benzene (Ic); m.p. 108.8-109.7 °C; 19F NMR
(CDCl3) d 80.6-82.7 (m, 2F), 62.55 (d, J=149.9 Hz, 8F); 1H NMR (CDCl3) d 7.88 (s, 4H); 13C
NMR (CDCl3) d 155.53 (quintet, J=19.0 Hz), 126.91 (m); GC-Mass m/z 330 (M+). Elemental
analysis; calcd for C6H4F10S2; C, 21.82%, H, 1.22%; found, C, 21.59%, H, 1.23%.
[00123] l,4-Bis(chlorotetrafluorosulfanyl)-2,5-difluorobenzene (IVd); m.p. 161.5-
162.9 °C (a 96:4 mixture of trans and cis conformation); 19F NMR (CDCl3) (a 96:4 mixture of
trans and cis conformation) 5 155.63 (m, cis-SF), 138.52 (m, trans-SF4), 112.95 (m, cis-SF2),
71.37 (m, cis-SF), -109.25 (m, CF); 1H NMR (CDCl3) (a 96:4 mixture of trans and cis
conformation) 8 7.63 (m, 2H); 13C NMR (CDCl3) (a 96:4 mixture of trans and cis
conformation) 8 150.75 (d, J=263.3 Hz), 143.94 (m), 118.50 (m). Elemental analysis (a 96:4
mixture of trans and cis conformation); calcd for C6H2Cl2F10S2; C, 18.06%, H, 0.51%; found,
C, 18.01%, H, 0.51%.
[00124] l,4-Bis(pentafluorosulfanyl)-2,5-difluorobenzene (Id); m.p. 73.0-74.6 °C; 19F
NMR (CDCl3) 876.3-78.5 (m, 2F), 67.71 (dd, J=152.3, 24.8 Hz, 8F), -109.77 (m, 2F); 1H
NMR (CDCl3) d 7.67 (m, 2H); 13C NMR (CDCl3) d 151.07 (d, J=262.3 Hz), 142.76 (m),
118.54 (dm, J=26.0 Hz); GC-Mass m/z 366 (M+). Elemental analysis; calcd for C6H2F12S2; C,
19.68%, H, 0.55%; found, C, 19.33%, H, 0.58%.
[00125] l,4-Bis(chlorotetrafluorosulfanyl)-2,3,5,6-tetrafluorobenzene (IVe); m.p.
135-141 °C (a 80:20 mixture of trans and cis conformation); 19F NMR (CDCl3) (a 62:38
mixture of trans and cis conformation) 8 148.6-150.4 (m, cis-SF), 142.22 (m, trans-SF4),
122.9-124.2 (m, cis-SF2), 77.7-79.2 (m, cis-SF), -129.2 - -130.3 (m, CF, trans and cis); 13C
NMR (CDCl3) (a 62:38 mixture of trans- and cis-conformation) 8 143.7-144.7 (m), 140.2-
141.2 (m), 134.5 (m). Elemental analysis (a 80:20 mixture of trans and cis conformation);
calcd for C6CI2F12S2; C, 16.56%, H, 0.00%; found, C, 16.54%, H, <0.05%.
[00126] l,4-Bis(pentafluorosulfanyl)-2,3,5,6-tetrafluorobenzene (If); m.p. 129.2-
130.0 °C; 19F NMR (CDCl3) d 71.0-74.4 (m, 10F), -130.8 (m, 4F); 13C NMR (CDCl3) d 144.9
(m), 141.3 (m), 133.3 (m); GC-Mass m/z 402 (M+). Elemental analysis; calcd for C6F14S2; C,
17.92%, H, 0.00%; found, C, 17.99%, H, <0.05%.
[00127] l,3,5-Tris(cMorotetrafluorosulfanyl)benzene (IVf); 19F NMR (CDCl3) d
135.32 (s); 1H NMR (CDCl3) d 8.24 (s); 13C NMR (CDCl3) d 127.01 (m), 154.96 (quintet,
J=22.9 Hz). NMR analysis showed that product (IVf) obtained is a trans,trans,trans-isomer.
[00128] l,3,5-Tris(pentafluorosulfanyl)benzene (If); m.p. 132.8-133.5 °C; 19F NMR
(CDCl3) d 63.31 (dm, J=151.8 Hz, 12F), 78.3-80.5 (m, 3F); 1H NMR (CDCl3) d 8.31 (s); 13C
NMR (CDCl3) d 153.65 (quintet, J=21.3 Hz), 127.31 (m); GC-Mass m/z 456 (M+). Elemental
analysis; calcd for C6H3F15S3; C, 15.79%, H, 0.66%; found, C, 15.48%, H, 0.62%.

[00129] (Process I) A 240 mL fluoropolymer (PFA) reactor was set up with
magnetic stirrer, ice bath, gas (N2, Cl2) inlet tube, and gas outlet tube protected by a CaCl2
tube. Gas flow was controlled by digital controller and measured by digital integrator. The
reactor was charged with anhydrous potassium fluoride (30g, 0.51 mol) and 5-bromo-1,3-
benzenedithiol (2.97 g, 13.4 mmol), and set up for reaction under nitrogen flow. Anhydrous
acetonitrile (120 mL) was added, and the slurry was stirred at ambient temperature for about
1 hour, after which stirring was continued for about 1 hour on an ice bath. N2 was stopped
and then chlorine gas was introduced below the surface at about 30 mL/min with vigorous
stirring. For approximately 4 hours, a total of 7.91 L (0.35 mol) of Cl2 was added. The
reaction mixture was then allowed to come to room temperature overnight with stirring. The
reaction mixture was purged with nitrogen, then suction filtered, washing through with
acetonitrile. A small amount of potassium fluoride was added to the reaction solution, and the
solvents were then removed at ambient temperature under approximately 4 mmHg vacuum,
leaving a white solid. A small amount of dry dichloromethane was added to dissolve the
product, which was then filtered to remove potassium fluoride and other insolubles. Removal
of dichloromethane under vacuum yielded crude product (5.39 g, crude yield 91%) as a white
powder. Recrystallization from pentane in a freezer yielded 4.16 g (yield 65%) of 1,3-
bis(chlorotetrafluorosulfanyl)-5-bromobenzene; m.p. 146.1-148 °C (with decomposition); 19F
NMR d (CDCl3) 135.8 ppm (s); 1H NMR d (CDCl3) 8.05 (m, 1H), 8.02 (m, 2H); 13C NMR d
(CDCl3) 155.58 (quintet, J = 21.7 Hz, C-1,3), 132.20 (m, C-4,6), 122.79 (m, C-2), 122.29 (s,
C-5). NMR analysis showed that l,3-bis(chlorotetxafluorosurfanyl)-5-bromobenzene obtained
is a trans,trans-isomer.

[00130] A 30 mL capped fluoropolymer (PFA) reactor with a single port and
stopcock was charged with l,3-bis(pentafluorosulfanyl)benzene (Ia) (1.65 g, 5 mmol), N-
bromosuccinimide (NBS) (3.4 g, 19 mmol), and concentrated sulfuric acid (6 mL). The
stopcock was closed to seal the reaction and the mixture was heated on an oil bath at 60-65
°C with magnetic stirring for 22 hours. After cooling, the reaction mixture was quenched into
a mixture of dilute aqueous sodium carbonate solution and chloroform. After separation, the
aqueous phase was extracted with chloroform, the combined organic extract was dried over
magnesium sulfate and filtered. The filtrate was evaporated up to dryness to give a solid,
which was a 71:29 mixture of 1,3-bis(pentafluorosulfanyl)-5-bromobenzene and 1,3-
bis(pentafluorosulfanyl)benzene by GC analysis. The mixture was column-chromatographed
on silica gel using hexane as an eluent to give purel,3-bis(pentafluorosulfanyl)-5-
bromobenzene (Ib) (about 64% yield): m.p. 65.9~66.4 °C (in a sealed capillary); 19F NMR d
(CDCl3) 79.4-81.6 (m, 2F), 62.9-63.6 (m, 8F); 1H NMR d (CDCl3) d.05-8.10 (m); 13C NMR
d (CDCl3) 154.17 (p, J = 20.2 Hz), 132.41 (t, J = 4.3 Hz), 122.98 (p, J = 5.1, 4.3 Hz), 122.53
(s); GC-Mass m/z 410(M+), 408 (M+). Elemental analysis; calcd for C6H3BrF10S2; C, 17.62%,
H, 0.74%; found, C, 17.61%, H, 0.73%.

Run 1 with a balloon filled with N2 (no flow of N2):
[00131] In a dry box, a reaction vessel made of fluoropolymer was charged
with 1.0 g (4.54 mmol) of trans-(chlorotetrafluorosulfanyl)benzene (trans-PhSF4Cl) and 0.28
g (2.7 mmol) of anhydrous ZnF2. The reaction vessel was removed from the dry box and
equipped with a balloon filled with N2. The reaction mixture was stirred at 120°C for 4 hours.
The reaction mixture was analyzed by 19F NMR, results are shown in Table 5.
Run 2 with N2 flow of a rate of 5.4 mL/min (slow flow of N2):
[00132] 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 anhydrous ZnF2.
The reaction vessel was removed from the dry box, and equipped with a condenser made of
fluoropolymer and connected to a N2 gas flowing device. The reaction mixture was slowly
heated to 120°C with N2 flowing at the rate of 5.4 ml/minute. The reaction mixture was
stirred at 120°C with N2 flowing for 5 hours. After being cooled to room temperature, the
reaction mixture was analyzed with 19F NMR. The results are shown in Table 5.
Run 3 with N2 flow of a rate of 26.9 mL/min (fast flow of N2):
[00133] 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 anhydrous ZnF2.
The reaction vessel was removed from the dry box, and equipped with a condenser made of
fluoropolymer and connected to a N2 gas flowing device. The reaction mixture was slowly
heated to 120°C with N2 flowing at a rate of 26.9 mL/minute. The reaction mixture was
stirred at 120°C with N2 flowing for 5 hours. After being cooled to room temperature, the
reaction mixture was analyzed with 19F NMR. The results are shown in Table 5.
Run 4 with Cl2 flow of a rate of 4.6 mL/min (flow of halogen):
[00134] 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 anhydrous ZnF2.
The reaction vessel was removed from the dry box, and equipped with a condenser made of
fluoropolymer and connected to a Cl2 gas flowing device. The reaction mixture was slowly
heated to 120°C with Cl2 flowing at a rate of 4.6 mL/minute. The reaction mixture was stirred
at 120°C with Cl2 flowing. The progress of the reaction was monitored by 9F NMR. After 40
minutes at 120 °C, three major compounds (trans-PhSF4Cl, cis-PhSF4Cl, and PhSF5) 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 by 19F NMR. The reaction was completed within
1.7 h at 120°C. The NMR analysis showed that PhSF5 was produced in 92% yield. This
result is shown in Table 5. 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; the
cis-PhSF4Cl is converted to the product, PhSF5.

[00135] 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.
CLAIMS
What is claimed is:
1. A process for preparing a poly(pentafluorosulfanyl)aromatic compound having a
formula (I) as follows:

the process comprising:
reacting an aryl sulfur compound having a formula (II):

with a halogen selected from the group consisting of chlorine, bromine, iodine, and
interhalogens, and a fluoro salt having a formula (HI), to form a
poly(halotetrafluorosulfanyl)aromatic compound having a formula (IV):

and reacting the obtained poly(halotetrafluorosulfanyl)aromatic compound with a fluoride
source to form the poly(pentafluorosulfanyl)aromatic compound;
in which: one or two of R1, R2, R3, R4, and R5 are a SF5 group and each of the
remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro group, and a
cyano group; one or two of R1, R2, R3, R4, and R5 are a SR6 group and each of the
remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro group, and a
cyano group; one or two of R1 , R2 , R3 , R4 , and R5 are a SF4X group and each of the
remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro group, and a
cyano group;
R is a hydrogen atom, a silyl group, a metal atom, an ammonium moiety, a
phosphonium moiety, or a halogen atom; or R combines with another R6 of its own molecule
or another molecule to form a single bond;
M is a metal atom, an ammonium moiety, or a phosphonium moiety; and
X is a chlorine atom, a bromine atom, or an iodine atom.
2. The process of claim 1 wherein the halogen reacted with the aryl sulfur compound is
chlorine (Cl2).
3. The process of claim 1 wherein the fluoro salt having a formula (III) is an alkali metal
fluoride.
4. The process of claim 1 wherein the fluoride source is at least one member selected
from a group consisting of 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, as well as mixtures, compounds,
salts, or complexes of these fluorides with fluoride source-activating compounds and/or
organic molecules.
5. The process of claim 1, further comprising the reaction of the obtained
poly(halotetrafluorosulfanyl)aromatic compound with a fluoride source being performed in
the presence of a halogen selected from the group of chlorine, bromine, iodine, and
interhalogens to form the poly(pentafluorosulfanyl)aromatic compound.
6. A process for preparing a poly(pentafluorosulfanyl)aromatic compound having a
formula (I):

the process comprising:
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) to form a
poly(halotetrafluorosulfanyl)aromatic compound having a formula (IV):

and reacting the obtained poly(halotetrafluorosulfanyl)aromatic compound with a fluoride
source to form the poly(pentafluorosulfanyl)aromatic compound;
in which: one or two of R1, R2, R3, R4, and R5 are a SF5 group and each of the
remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro group, and a
cyano group; one or two of R1 , R2 , R3 , R4 , and R5 are a SF4X group and each of the
remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro group, and a
cyano group; one or two of R1 , R2 , R3 , R4 , and R are a SF3 group and each of the
remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro group, and a
cyano group;
M is a metal atom, an ammonium moiety, or a phosphonium moiety; and
X is a chlorine atom, a bromine atom, or an iodine atom.
7. The process of claim 6 wherein the halogen reacted with the arylsulfur trifluoride is
chlorine (Cl2).
8. The process of claim 6 wherein the fluoro salt having a formula (IE) is an alkali metal
fluoride.
9. The process of claim 6 wherein the fluoride source is at least one member selected
from a group consisting of 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, as well as mixtures, compounds,
salts, or complexes of these fluorides with fluoride source-activating compounds and/or
organic molecules.
10. The process of claim 6, further comprising the reaction of the obtained
poly(halotetrafiuorosulfanyl)aromatic compound with a fluoride source being performed in
the presence of a halogen selected from the group of chlorine, bromine, iodine, and
interhalogens to form the poly(pentafluorosulfanyl)aromatic compound.
11. A process for preparing a poly(halotetrafluorosulfanyl)aromatic compound having a
formula (TV):

the process comprising:
reacting an aryl sulfur compound having a formula (II):

with a halogen selected from the group consisting of chlorine, bromine, iodine, and
interhalogens, and a fluoro salt having a formula (III), to form the
poly(halotetrafluorosulfanyl)aromatic compound,

in which: one or two of R1 , R2 , R3 , R4 , and R5 are a SF4X group and each of the
remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro group, and a
cyano group; one or two of R1, R2 , R3 , R4, and R5 are a SR6 group and each of the
remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro group, and a
cyano group;
R5 is a hydrogen atom, a silyl group, a metal atom, an ammonium moiety, a
phosphonium moiety, or a halogen atom; or R6 combines with another R6 of its own molecule
or another molecule to form a single bond;
M is a metal atom, an ammonium moiety, or a phosphonium moiety; and
X is a chlorine atom, a bromine atom, or an iodine atom.
12. The process of claim 11 wherein the halogen reacted with the aryl sulfur compound is
chlorine (Cl2).
13. The process of claim 11 wherein the fluoro salt having a formula (III) is an alkali
metal fluoride.
14. A process for preparing a poly(halotetrafluorosulfanyl)aromatic compound having a
formula (IV):

the process comprising:
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), to form the
poly(halotetrafluorosulfanyl)aromatic compound:

in which: one or two of R1 , R2 , R3 , R4 , and R5 are a SF4X group and each of the
remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro group, and a
cyano group; one or two of R1 , R2 , R3 , R4 , and R5 are a SF3 group and each of the
remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro group, and a
cyano group;
M is a metal atom, an ammonium moiety, or a phosphonium moiety; and
X is a chlorine atom, a bromine atom, or an iodine atom.
15. The process of claim 14 wherein the halogen reacted with the arylsulfur trifluoride is
chlorine (Cl2).
16. The process of claim 14 wherein the fluoro salt having a formula (III) is an alkali
metal fluoride.
17. A process for preparing a poly(pentafluorosulfanyl)aromatic compound having a
formula (I):

the process comprising:
reacting a poly(halotetrafluorosulfanyl)aromatic compound having a formula (IV):

with a fluoride source to form a poly(pentafluorosulfanyl)aromatic compound;
in which: one or two of R1, R2, R3, R4, and R5 are a SF5 group and each of the
remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro group, and a
cyano group; one or two of R1 , R2 , R3 , R4 , and R5 are a SF4X group and each of the
remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro group, and a
cyano group; and
X is a chlorine atom, a bromine atom, or an iodine atom.
18. The process of claim 17 wherein the fluoride source is at least one member selected
from a group consisting of 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, as well as mixtures, compounds,
salts, or complexes of these fluorides with fluoride source-activating compounds and/or
organic molecules.
19. The process of claim 17 wherein X is a chlorine atom.
20. The process of claim 17, further comprising the reaction of the
poly(halotetrafluorosulfanyl)aromatic compound with a fluoride source being performed in
the presence of a halogen selected from the group of chlorine, bromine, iodine, and
interhalogens to form the poly(pentafluorosulfanyl)aromatic compound.
21. A process for preparing a halogenated poly(pentafluorosulfanyl)aromatic compound
having a formula (I)(R2=Y):

the process comprising:
reacting a poly(pentafluorosulfanyl)aromatic compound having a formula (I)(R2=H);

with a halogenating agent and an acid;
in which: Y is a halogen atom; and one or two of R1, R3, R4, and R5 are a SF5 group and each
of the remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro group, and a
cyano group.
22. A poly(chlorotetrafluorosulfanyl)aromatic compound represented by formula (IV'):

in which one or two of R1", R2", R3", R4", and R5" are a SF4Cl group and each of the
remainders is selected from a group consisting of a hydrogen atom, a halogen atom, a
substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a nitro group, and a
cyano group.
23. The poly(chlorotetrafluorosulfanyl)aromatic compound of claim 22, wherein each of
the remainders is selected from a group consisting of a hydrogen atom and a halogen atom.
24. The poly(chlorotetrafluorosulfanyl)aromatic compound of claim 22 selected from a
group consisting of 1,2-, 1,3-, and l,4-bis(chlorotetrafluorosulfanyl)benzene, 1,3-
bis(chlorotetrafluorosulfanyl)-5-fluoro-, -chloro-, -bromo-, and -iodo-benzene, 1,4-
bis(chlorotetrafiuorosulfanyl)-2,5-difluorobenzene, 1,4-bis(chlorotetrafluorosulfanyl)-2,3,5,6-
tetrafluorobenzene, 1,2,3-, 1,2,4-, and 1,3,5-tris(chlorotetrafluorosulfanyl)benzene, and 1,3,5-
trifluoro-2,4,6-tris(chlorotetrafluorosulfanyl)benzene.
25. The poly(chlorotetrafluorosulfanyl)aromatic compound of claim 22 selected from a
group consisting of 1,3-bis(chlorotetrafluorosulfanyl)benzene, 1,3-
bis(chloroterafluorosulfanyl)-5-bromobenzene, 1,4-bis(chlorotetrafluorosulfanyl)benzene,
1,4-bis(chlorotetrafluorosulfanyl)-2,5-difluorobenzene, 1,4-bis(chlorotetrafluorosulfanyl)-
2,3,5,6-tetrafluorobenzene, and 1,3,5-tris(chlorotetrafluorosulfanyl)benzene.
26. A bis(pentafluorosulfanyl)benzene compound represented by formula (I"):

wherein one of Ra, Rb, Rc, Rd, and Re is a SF5 group and each of the remainders is
selected from a group consisting of a hydrogen atom and a halogen atom.
27. A bis(pentafluorosulfanyl)benzene compound of claim 26 selected from a group
consisting of 1,2-bis(pentafluorosulfanyl)benzene, 1,3-bis(pentafluorosulfanyl)benzene, 1,3-
bis(pentafluorosulfanyl)-5-fmoro-, -chloro-, -bromo-, and -iodo-benzene, 1,4-
bis(pentafluorosulfanyl)benzene, 1,4-bis(pentafluorosulfanyl)-2,5-difluorobenzene, and 1,4-
bis(pentafmorosulfanyl)-2,3,5,6-tetrafluorobenzene.
28. A bis(pentafluorosulfanyl)benzene of claim 26 is selected from a group consisting of
1,3-bis(pentafluorosulfanyl)benzene, 1,3-bis(pentafluorosulfanyl)-5-bromobenzene, 1,4-
bis(pentafluorosulfanyl)benzene, 1,4-bis(pentafluorosulfanyl)-2,5-difluorobenzene, and 1,4-
bis(pentafluorosulfanyl)-2,3,5,6-tetrafluorobenzene.

Novel processes for preparing poly(pentafluorosulfanyl)aromatic compounds are disclosed. Processes include reacting
an aryl sulfur compound with a halogen and a fluoro salt to form a poly(halotetrafluorosulfinyl)aromatic compound. The
poly(halotetrafluorosulfanyl)aromatic compound is reacted with a fluoride source to form a target poly(pentafluorosulfanyl)aromatic
compound.