CA2912235C - Process for producing arylsulfur pentafluorides - Google Patents

Abstract

The invention relates to an arylsulfur chlorotetrafluoride represented by formula (IV'): (see formula IV') 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 wherein, 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.

Description

PROCESS FOR PRODUCING ARYLSULFUR PENTAFLUORIDES
TECHNICAL FIELD
[0001] The invention relates to methods and compositions useful in the preparation of aryl sul fur pentafluorides.
BACKGROUND OF THE INVENTION

[0002] Arylsulfur pentafluorides compounds are used to introduce one or more sulfur pentafluoride groups into various commercial organic molecules. In particular, arylsul fur 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.

[0003] 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; Fur. J. Org. Chem., Vol. 2005, pp. 3095-3100; and USP
5,741,935]; (3) fluorination of diaryl disulfides or arenethiois with F1, CF30F, or CF2(0F)2 in the presence or absence of a fluoride source (see US Patent Publication No. 2004/0249209 Al);

(4) fluorination of diaryl disulfides with XeF2 [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-1-cyclohexene with followed by dehydrochlorination [see Organic Letters, Vol. 6 (2004), pp. 2417-2419 and PCT
WO 2004/011422 Al]; and (7) reaction of SF5C1 with acetylene, followed by bromination, dehydrobromination, and reduction with zinc, giving pentafluorosulfanyIacetylene, 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].

[0004] 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, CF30F, or CF2(0F)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, CF30F, and/or CF2(0F)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 SF5Br, and have narrow application because the starting cyclohexene derivatives are limited. Finally, method (7) requires the expensive reactant SF5C1 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.

[0005] Phenylsulfur chlorotetrafluoride, p-methylphenylsulfur chlorotetrafluoride, and p-nitrophenylsulfur chlorotetrafluoride were detected in the reaction of diphenyl disulfide, bis(p-methylphenyl) 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.
[00061 The present invention is directed toward overcoming one or more of the problems discussed above.
SUMMARY OF THE INVENTION
[00071 The present invention provides novel processes for the production of arylsulfur pentafluoride, as represented by formula (I):

R3 * SF5 ------------------------------- (I) Embodiments of the invention include reacting at least one aryl sulfur compound, having a formula (11a) or (Hb), R3 * S¨S * R3 ----------------------------- (Ha) R3 * SR6 (lib) with a halogen selected from the group of chlorine, bromine, iodine and interhalogens, and a fluor salt (IvrF", formula III) to form an arylsulfur halotetrafluoride having a formula (IV):

R3 * SF4X --------------------------------- (IV) The arylsulfur halotetrafluoride (formula IV) is reacted with a fluoride source to form the arylsulfur pentafluoride (formula H.
[0008j 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 (Ha) or (lib), with a halogen selected from the group of chlorine, bromine, iodine and interhalogens, and a fluor salt (M+F, formula III) to form an arylsulfur halotetrafluoride having a formula (IV):

R3 it SF4X -------------------------------- (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).
100091 Embodiments of the present invention also provide processes for producing arylsulfur pentafluorides (formula I) by reacting an arylsulfur trifluoride having a formula (V):

R3 SF3 (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):

R3 * SF4X (IV) The arylsulfur halotetrafluoride (formula IV) is reacted with a fluoride source to form the arylsulfur pentafluoride (formula I).
[00101 Embodiments of the present invention also provide processes for producing arylsulfur pentafluorides (formula I) by reacting an arylsulfur trifluoricle having a formula (V):

R3 SF3 (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).
100111 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).
[0012j 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 (Ha) or (Jib) 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 atm.
[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'):
R2' R1' R3. SF4CI ---------------- (IV) R4. R6 F
R3. * SF5 ------------ (r) [0015a] In accordance with another aspect, there is provided an arylsulfur chlorotetrafluoride represented by formula (IV'):
R2' R1' R3' * SF4CI ---------------------------------------- (IV') R4' R5' wherein le, 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 wherein, when R3' is a hydrogen atom, a methyl group, or a nitro group, at least one of RI', R2', R4', and R5' is a halogen atom, a linear or branched alkyl group having one to four carbon atoms, or a nitro group.

10016] 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
100171 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 5a 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 C12, Br2, and 12.
[00191 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 (Ha) or a formula (Hb) 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 (0.
Scheme 1: (Processes I and II) Rµ R1 R2 R3 s¨s R4 R5 R5 R4 Process I R7 IR, Process II
R2 R' aid/or (11a) R3 it SFAX _____________________ R' __ SF5 halogen fluoride R2 R' m+ R R5 source R4 R5 *
SR J
(IV) (I) R` R5 (lib) [0020] With regard to formulas (I), (Ha), (Jib), (III), and (IV):
substituents RI, 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 Ito 18 carbon atoms, preferably from Ito 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

6 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 phosphoniurn moiety, and with regard to X, X is a chlorine atom, a bromine atom, or an iodine atom.
100221 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.
[00231 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.
[0026j 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

7 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.
[00271 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.
[00281 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.
[00291 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.
[00301 The term "substituted arenesulfonyloxy" as used herein means an arenesulfonyloxy 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.
[00311 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.
(00321 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.
(00331 The term "substituted carbamoyl" as used herein means a earbamoyl 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)

8 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 alk.anesulfonyl group, a substituted or unsubstituted arenesulfonyl 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.
[00351 Among the substituents, R', 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.
10036] 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-C1-C6F14-SF5 is named sulfur, (4-chloroplienyl)pentafluoro-; and p-CH3-C61-14-SF5 is named sulfur, pentafluoro(4-methylpheny1)-. C6H5-SF4C1 is named sulfur, chlorotetrafluorophenyl-; p-CH3-C6F14-SF4C1 is named sulfur, chlorotetrafluoro(4-methylphenyl)-; and p-NO2-C61-14-SF4C1 is named sulfur, chlorotetrafluoro(4-nitropheny1)-.
10037] Arylsulfur halotetrafluoride compounds of formula (IV) include isomers such as trans-isomers and cis-isomers as shown below; arylsulfur halotetrafluoride is represented by ArSF4X:
FF
\/
Ar S¨X ....................... tans-Isomer F \F
r Ar \I F ...................... cls-Isomer X F
[00381 Table 1 provides structure names and formulas for reference when reviewing Schemes 1, 3-10 and Examples 1-34:

9 [0039] Table 1: Formulas (1¨V) Name Structure/Formula Number Arylsulfur pentafluoride R2 R1 R3 4110 SF5 (I) Aryl sulfur compound R2 R1 R1 R2 R3 S¨S 41, R3 (Ha) Aryl sulfur compound R2 R1 R3 11 SR6 (hlb) Fluoro salt rir F (III) Arylsulfur halotetrafluoride R2 RI
R3 II SF4X --------------------------------------------------- (IV) Arylsulfin- trifluoride R2 R1 R3= SF3 ----------------------------------------------------- (V) Process I (Scheme 1) [0040] Process I includes reacting at least one aryl sulfur compound, having a formula (ha) or (Ilb), with a halogen selected from the group of chlorine, bromine, iodine and interhalogens, and a fluor salt (1\44F-, formula III) to form an arylsulfur halotetrafluoride having a formula (IV).
[00411 The substituent(s), RI, 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 formulas (IIa) and/or (11b). Thus, embodiments of this invention include transformation of the RI, R2, R3, R4, and R5 to different R1,R2,R34and 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 ¨SEIX group(s).
[0042] Illustrative aryl sulfur compounds, as represented by formula (Ha), 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(bromo fluoroplienyl) disulfide, each isomer of bis(brornochlorophenyl) disulfide, each isomer of bis(fluoroiodophenyl) disulfide, each isomer of bis(toly1) disulfide, each isomer of bisf(rnethoxymethyl)phenyl]
disulfide, each isomer of bis{[(cyclohexyloxy)methyl]phenyl) disulfide, each isomer of bis[(phenylmethyl)phenyll disulfide, each isomer of bis[(cyanomethyl)phenyl]
disulfide, each isomer of bis[(nitromethyl)phenyl] disulfide, each isomer of bis {Rmethanesulfonyl)methyllphenyl} disulfide, each isomer of bis(Rbenzenesulfonyl)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[brorno(methyl)phenyl] disulfide, each isomer of bisr(trifiuoromethyl)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(trimethylphenyl) 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-trifluoroethypphenyl] 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(isopropylphenyl) disulfide, each isomer of bis(butylphenyl) disulfide, each isomer of bis(sec-butylphenyl) disulfide, each isomer of bis(isobutylpheny-1) 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 bisfRcyclohexyncyclohexyl]phenyll disulfide, each isomer of bis(biphenyl) disulfide, each isomer of bis(tolylphenyl) disulfide, each isomer of bis[(chlorophenyl)phenyll disulfide, each isomer of bisRbromophenyl)phenyl] disulfide, each isomer of bis[(nitrophenyl)phenyl]
disulfide, each isomer of bis(terphenyly1) disulfide, each isomer of bist(phenyl)terphenylyll disulfide, each isomer of bisj(methauesulfonyl)phenyl] disulfide, each isomer of I' bis[(trifluoromethanesulfonyl)phenyl] disulfide, each isomer of bis[(benzenesulfonyl)phenyl]
disulfide, each isomer of bisKtoluenesulfonyl)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 bisRtetrafiuoroethoxy)phenyll disulfide, each isomer of bist(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(nitrophenyloxyphenyl) disulfide, each isomer of bis[(dinitrophenyloxy)phenyl] disulfide, each isomer of bis[(pentafluorophenyloxy)phenyli disulfide, each isomer of bis(trifluorornethylphenyloxyphenyI) disulfide, each isomer of bis(cyanophenyloxyphenyl) disulfide, each isomer of bis(naphthyloxylphenyl) disulfide, each isomer of bis[(heptafluoronaplithyloxy)phenyl] disulfide, each isomer of bisracetoxyphenyll disulfide, each isomer of bisj(benzoyioxy)phenyl] disulfide, each isomer of bisRmethanesulfonyloxy)phenyl) disulfide, each isomer of bisRbenzenesulfonyloxy)phenyl]
disulfide, each isomer of bis[(toluenesulfonyloxy)phenyl] disulfide, each isomer of bis[(methoxycarbonyl)phenyl] disulfide, each isomer of bisKethoxycarbonyl)phenylj disulfide, each isomer of bis{(phenoxycarbonyl)phenylj disulfide, each isomer of bis[(N,N-dimethylcarbamoyl)phenylj 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-methylarnino)phenyl] disulfide, each isomer of bis[(N-methanesulfonyl-N-methylarnino)phenyl} disulfide, each isomer of bis[(N-toluenesulfonyl-N-methylamino)phenyl] disulfide, each isomer of bis[(N-toluenesulfonyl-N-benzylamino)pheny1] disulfide, and each isomer of bisRpentafluorosulfanyl)phenyli disulfide. Each of the above formula (Ha) compounds is available (see for example Sigma, Acros, ICI, 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 (lib), of the invention include, but are not limited to: benzenethiol, each isomer of fluorobenzenethiol (o-, m-, and p-fluorobenzenethiol), each isomer of chiorobenzenethiol, 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 methyibenzenethiol, each isomer of (trifluoromethyl)benzenethiol, each isomer of dimethylbenzenethiol, each isomer of bis(trifluorometyl)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-trifluoroethypbenzenethiol, each isomer of (perfluomethyl)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 (chloroplienyl)benzenethiol, each isomer of (bromophenyl)benzenethiol, each isomer of (nitrophenypbenzenethiol, each isomer of (methanesulfonyl)benzenethiol, each isomer of (0 ifluoromethanesulfonyl)benzenethiol, each isomer of (benzenesulfonyl)benzenethiol, each isomer of (toluenesulfonyl)benzenethiol, each isomer of (methoxycarbonyl)benzenethiol, each isomer of (ethoxycarbonypbenzenethiol, each isomer of (phenoxyearbonyl)benzenethiol, each isomer of (N,N-dimethylcarbamoyl)benzenethiol, each isomer of (N,N-dieth ylcarbarnoyl)benzenethiol, each isomer of (N,N-dibenzylcarbamoyl)benzenethiol, each isomer of (N,N-diphenylcarba.moyl)benzenethiol, each isomer of (N-acetyl-N-rnethylamino)benzenethiol, each isomer of (N-acetyl-N-phenylamino)benzenethiol, each isomer of (N-acetyl-N-,, benzylamino)benzenethiol, each isomer of (N-benzoyl-N-methylamino)benzenethiol, each isomer of (N-methanesulfonyl-N-methyiamino)benzenethiol, each isomer of (N-toluenesulfonyl-N-metbylamino)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, tetramethylammonium, tetraethylammonium, tetrapropylarn. monium, 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, S-triethylsilyl, S-tripropylsilyi, S-dimethyl-t-butylsilyl, and S-dimethylphenvIsily1 derivative of the benzenethiol compounds exemplified here. Examples of aryl sulfur compounds of formula (Ilb) 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 (III)) compounds is available (see for example Sigma, Acros, Ta, Lancaster, Alfa Aesar, etc.) or can be prepared in accordance with understood principles of synthetic chemistry.
[00441 Typical halogens employable in the present invention include chlorine (C12), bromine (Br2), iodine (I2), and interhalogens such as CIF, BrF, CIBr, CII, C134, and Br!.
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, tetrapropylphosphoni urn fluoride, tetrabutylphosphoniurn 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.
00461 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.
100471 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 aininonium 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 Exchange reaction tvr F- + (Mr A
M' A' (1v1.)4 (AF - or an anion pan other than F-) [0048] The combination of these salts may accelerate the reactions in Process I, because the reaction may depend on the solubility of the fluor 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, aininonium 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 are, but are not limited to, CF, Br', 1-, BF4-, PF6-, SO4-, -000C1-13, OCOCF3, OSO2CH3, OSO2CF3, 0S02C4F9, 0S02C6H5, -0S02C6H4CH3, -0S02C6H4Br, and so on. Among them, the anion parts (other than F) which do not have an oxygen anion(s) are preferable, and Cr, BF4- and PF6- are more preferable because of high yield reactions. In addition, Cl' 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, nitrites, ethers, nitro compounds, and so on, and mixtures thereof. Illustrative nitrites 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.
100501 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.
100511 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 combined with about I 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 mot of halogen are combined with 1 mol of aryl sulfur compound of formula Ilb (R6=a hydrogen atom, a sily1 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 mot 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 mot of aryl sulfur compound of formula (Ha) to obtain economically good yields of product. The amount of a fluoro salt (formula III) used in embodiments of Process I can be in the range of from about 4 to about 12 mol against I mol of aryl sulfur compound of formula (lib) to obtain economically good yields of product.
(00521 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.
lb =

10053) Scheme 3: Reaction mechanism for Process I
R2 FO R, R2 R2 hal ogen # S S R3 ---*" R3 it SX' (11a) (11b.) QC-a halogen atom) .\\4) ,algoen halogen 1A*F
(R6 except R2 Fe R' a halogen halogenhalogen atom) (R6 except a halogen atom) H3 11 SF3 fR3 sF,x NeF-R2 11' (V) (IV) halogen 124 R5 fser (Ilb) [0054) A more complete reaction mechanism of Process I is shown in Scheme 3 above. Aryl sulfur compound of formula (ha) reacts with halogen to form arylsulfur halide (lIb'=Ilb 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 arylsul fur 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 (Jib') 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 (IIb 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 (Ha) 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 (Ha) or (Jib') 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) (00551 Embodiments of the invention include Process 11: a reaction of arylsulfur halotetrafluoride, obtained by the process I, with a fluoride source, as shown in Scheme 1.
100561 The substitucnt(s), R', R2, R3, R4, and R5, of the products represented by the formula (I) may be different from the substituent(s), RI, R2, R3, R4, and R5, of the materials represented by the formula (IV). Thus, embodiments of this invention include transformation of the R', R2, R3, R4, and R5 to different RI, 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.
100571 Fluoride sources employable in Process II are anhydrous compounds that display fluoride activity to the arylsulfur balotetrafluoride (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 SbCI5, AlC13, PC15, BC13, and so on.
Process 11 can be carried out using one or more fluoride sources.
[00581 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, NaF, KF, RbF, and CsF; fluorides of Element 2 (alkaline earth metal fluorides) such as BeF2, MgF2, MgFCI, CaF2, SrF2, BaF2 and so on; fluorides of Element 13 such as BF3, BF2C1, BFC12, AIF3, AlFCl, AIFC12, GaF3, InF3, and so on; fluorides of Element 14 such as SiF4, SiF3C1, SiF2C12, SiFCI3, GeF4, GeF2C12, SnF4, PbF2, PbF4, and so on; fluorides of Element 15 such as PF5, AsF5, SbF3, SbF5, SbF4C1, SbF3C12, SbF2C13, SbFCL4, 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, C1F3, BrF, BrF3, IF6, and so on.
[00591 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 such as VF3, VF5, NbF5, TaF5, and so on; fluorides of Element 6 such as CrF3, MoF6, WF6, and so on; fluorides of Element 7 such as MnF2, MriF3, ReF6, and so on;
fluorides of Element 8 such as FeF3, RuF3, RuFa, 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, PdF,, PtF2, PtF4, PtF6, and so on; fluorides of Element 11 such as CuF2,CuFC1, AgF, AgF2, and so on;
fluorides of Element 12 such as ZnF2, ZnFC1, CdF2, HgF2, and soon.
[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 8F3], 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, (C4f19)41\IF/HF, ZnF2/HF, CuF2/EIF, SbF5/SbF3, SbF5/SbF3/HF, ZnF2/SbF5, ZnF2/SbF5fHF, KF/SbF5, KF/SbF5/HF, and so on.
[00611 Suitable examples of mixtures, salts, or complexes of the fluorides with organic molecules include, but are not limited to, BF3 diethyl etherate [BF3-0(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/trirnethylamine, HF/triethylamine, HF/dirnethyl 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.
100621 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.
100631 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, AlF3, AlF2C1, SbF3, SbF5, SbF4C1, and SbF3C12 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 trirnethylamine 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.
100641 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.
[00651 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, alkalies, halocarbons, ethers, nitrites, 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 halo-carbons include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, terachloroethane, trichlorotrifluoroethane, chlorobenzene, dichlorobenzene, trichlorobenz,ene, hexafluorobenzene, benzotrifluoride, bis(trifluoromethypbenzene, 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 (ha) or a formula (Ilb) 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 (1).
Scheme 4 (Processes I and II') RI R1 R' Fe # s¨s # R3 R4 Fe' R5 fe Process I , 2 R Process II' and/or {lia) R3 it õ4, R3 4, SF 5 halogen fluoride R2 R1 F(111) R4 R5 SOUfCC. R4 R5 R3 41, sR6 0V) halogen (1) R4 FE5 (Jib) [00701 Process I is as described above.
[00711 Process II' 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).

[0072j The substituent(s), RI, R2, R3, R4, and R5, of the products represented by the formula (1) may be different from the substituent(s), RI, R2, R3, R4, and R5, of the materials represented by the formula (IV). Thus, embodiments of this invention include transformation of the RI, R2, R3, R4, and R5 to different RI, 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.
100731 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 disproportionation-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 (C12) 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) Process III R2 CI Proc.ess H R2 R1 R3-V¨SF.3 ¨1'1- R3 SF4X Rj SF5 halogen fluoride F(III) R4 R5 izource R4 R5 QV) 0) [0076) With regard to formulas (I), (III), (IV), and (V), Ri, R2, R3, R4, R5, 0, 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 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).
[0078] The substituent(s), RI, R2, Rs, R4, and R5, of the products represented by the formula (IV) may be different from the substituent(s), RI, R2, R3, R4, and R5, of the starting materials represented by the formula (V). Thus, embodiments of this invention include transformation of the RI, R2, R3, R4, and R5 to different RI, 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 ¨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 fluorophenylsul fur trifluoride, each isomer of difluorophenylsulfur trifluoride, each isomer of trifluorophenylsulfur trifluoride, each isomer of tetrafluorophenylsulfur trifluoride, pentafluorophenylsulfur trifluoride, each isomer of chlorophenylsulfur tri fluoride, each isomer of bromophenylsulfur trifluoride, each isomer of chlorofluorophenylsul fur trifluoride;
each isomer of bromofluorophenylsul fur trifluoride, each isomer of tolylsulfur trifluoride, each isomer of chloro(methyOphenylsulfur 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 tri fluoride, each isomer of butylphenylsulfur trifluoride, each isomer of nitrophenylsulfur trifluoride, each isomer of dinitrophenylsulfur trifluoride, and so on.
100801 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 I described above except for the amount used for the reaction.
[0082] Fluor 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.
[0083j 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 ¨ +50.C. 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 I 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 I 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.
100881 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 (IV) 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 fonn the arylsulfur pentafluoride having a formula (I). Scheme 6 showing Processes III and IF are shown as follows:
Scheme 6 (Processes ill and H') g2 Process III R7 R' Process IF
R3 # 5E2 ________ 3 SF4X # SF5 halogen 111 fluoride F(111) source, (V) (1V) halogen 0) [0090] With regard to formulas (I), (III), (IV), and (V), RI, R2, R3, R4, R5, R6, and X have the same meaning as defined above.
[0091] Processes Ill and 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 (ha) or a formula (Jib) 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 7 (Process I) R2 R' RI R2 R3 11, S¨S *
R5 Rs R.
Process I R2 R' (Ha) I.
and/or R3 _____________________ SF4X
haloeen R2 R' R' R5 R3 .11 SR5 (IV) 124 R5 (11b) (0093) In the formulas (Ha), (lib), (III), and (IV), Ri, R2, R3, R4, R5, R6, M and X
represent the same meaning as defined above.
[0094] Process I is described above.
10095] Furthermore, the present invention includes a process (Scheme 8, Process III) for preparing an arylsulfur halotetrafluoride 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 (III) to form the arylsulfur halotetrafluoride.
Scheme 8 (Process III) Rz IR' Process III R2 R' R3 ip sõ __________ R3 SF4X
halogen R5 r-010 R4 R5 (V) (IV) [0096] In the formulas (III), (IV), and (V), RI, R2, R3, R4, R5, M and X
represent the same meaning as defined above.
10097j 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 OT or more to form the arylsulfur pentafluoride.
Scheme 9 (Process H") SF4X Process IP' ¨ SF5 fluoride source o'f 11 R4 R' --bp 0 C or mere R4 R6 (IV) [00991 In the formulas (I) and (IV), R1, 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.
[001011 The substituent(s), R1, R2, R3, R4, and R5, of the products represented by the formula (I) may be different from the substituents, 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, Rel, 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.
[001021 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 O'C at 1 atm.
[001031 Furthermore, the present invention includes a process (Scheme 10, 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 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') R2 R' process IT R2 R
Sra ______________________ R3 SF5 fluoride R4 R5 source, R4 R5 (IV) halogen [001041 For formulas (I) and (IV), R/, R2, R3, R4, Rs, and X represent the same meaning as defined above.
[001051 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 (IV') as useful intermediates;
R2. RI' R3. * SF4CI --------------------------------- (IV') R4. IS5 wherein RI', 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 RI., R2', R4', and Rs' 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 difluorophenylsulfur chlorotetrafluoride, each isomer of trifluorophenylsul fur chlorotetrafluoride, and 2,3,4,5,6-pentafluorophenylsulfur chlorotetrafluoride are preferable, and 4-tert-butylphenylsulfur chlorotetrafluoride, 4-fluorophenylsulfur chlorotetrafluoride, 2-fluorophenylsulfur chlorotetrafluoride, 4-chlorophenylsul fur chlorotetrafluoride, 4-bromophenylsulfur chlorotetrafluoride, 3-bromophenylsulfur chlorotetrafluoride, 2,6-difluorophenylsulfur chlorotetrafluoride, 2,4,6-tri fluorophenylsulfur chlorotetrafluoride, and 2,3,4,5,6-pentafluorophenylsulfur chlorotetrafluoride are more preferable.
The present invention also provides novel and useful fluorinated arylsulfur pentafluorides represented by formula (I');

R2"
R3" SF5 (V) R4"
õ
wherein at least one of R2, R ,and R are a halogen atom and the remainders are a hydrogen atom. The halogen atom here is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom_ Among these, 2,3,4,5,6-pentafluorophenyIsulfur pentafluoride, 2,4,6-trifluorophenylsulfur pentafluoride, 3-chloro-2,4,6-trifluorophenylsulfur pentafluoride, and 3-chloro-2,6-difluorophenyisulfur pentafluoride are preferable.
[001081 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
[001091 The following examples are provided for illustrative purposes only and are not intended to limit the scope of the invention. Table 2 provides structure names and formulas for reference when reviewing the following examples:
Table 2: Arylsulfur lIalotetrafluorides (Formulas Ia,b,d-n and IVa-j,l,n):
Formula Name Structure Number la Phenylsulfur pentafluoride (1) SF5 lb p-Methylphenylsulfur pentafluoride CH3SF5 _ Id p-Fluorophenylsulfur pentafluoride F SF5 = _____________________________________________________________ le o-Fluorophenylsulfur pentafluoride = SF5 If p-ChlorophenylsuIfur pentafluoride CI 111 SF5 Ig p-BronmphertylsuIfur pentafluoride Br = SF5 lh m-Brornophenylsulfur Br pentafluoride Ii p-Nitrophenylsulfur pentafluoride o2N SF5 Ij 2,6-Difluorophenylsulfur pentafluoride Ik 3 -Chloro-2,6- CI
difluorophenylsulfur pentafluoride 2,4,6-Trifluorophenylsul fur pentafluoride Im 3-Chloro-2,4,6- CI
trifluorophenylsulfur pen tafl uoride In 2,3,4,5,6-Pentafluorophenylsulfur pentafluoride Table 2 (continued) Formula Name Structure Number TVa Phenylsulfur chlorotetrafluoride IVb p-Methylphenylsulfur chlorotetrafluoride CH3 SF4CI
IVc p-(tert-Butyl)phenylsul fur chlorotetrafluoride SF4Cl lVd p-Fluorophenylsul fur chlorotetrafl uoride F 41, SF4CI
We o-Fluorophenylsul fur ch I orotetrafl uoride 411 SF4Ci IV f p-Chlorophenylsul fur ch lorotetrafluori de CI SF4CI
IVg p -Bromophenylsul fur ch I orotetra fl uoride Br SF4CI
Rth m -B romoph en yl sul fur Br ch I orotetrafl uoride IVi p-Nitrophenylsulfur chlorotetrafluoride 02N SF4CI

IVj 2,6-Difluorophenylsulfur chlorotetrafluoride IV1 2,4,6-Trifluorophenylsulfur chlorotetrafluoride No 2,3,4,5,6-Pentafluorophenylsulfur chlorotetrafluoride Example I. Synthesis of phenylsulfur pentafluoride from cliphenyl disulfide Process I Process It S¨S # SF40 _________________________________ SF5 Cl2 ZnF2 KF IVa la [00110j (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 rriL of dry CH3CN.
The stirred reaction mixture was cooled on an ice/water bath under a flow of N2 (18 mUmin).
After N2 was stopped, chlorine (Cl2) was bubbled into a reaction mixture at the rate of about 70 mL/min. The C12 bubbling took about 6.5 h. The total amount of C12 used was about 1.2 mol. After C12 was stopped, the reaction mixture was stirred for additional 3 h. N2 was then bubbled through for 2 hours to remove an excess of C12. The reaction mixture was then filtered with 100 mL of dry hexanes in air. About 1 g of dry KY was added to the filtrate.. The 1CF 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 A) of phenylsulfur chlorotetrafluoride: b.p. 80 020 mmHg; 1H NMR
(CD3CN) 7.79-7.75 (in, 211, aromatic), 7.53-7.49 (m, 3H, aromatic); '9F NMR (CD3CN) 136.7 (s, SF4C1). The NMR analysis showed phenylsulfur chlorotetrafluoride obtained is a trans isomer.

.(001111 (Process II) A 100 rriL fluoropolym.er (TEFLON -PFA) vessel was charged with PhSF4C1 (44 g, 0.2inol) and dry ZnF2 (12.3 g, 0.12 mop in a dry box filled with N. 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; 1H NMR(CDC13) 7.77-7.74 (m, 2H, aromatic), 7.60-7.40 (m, 3H, aromatic); I9F NMR (CDC13) 85.20-84.13 (m, 1F, SF5), 62.91 (d, 4F, SF5).
Examples 2-10. Synthesis of arylsulfur pentafluorides (1) from aryl sulfur compounds (ha) R Process IR Process R
C12 ZnF2 R=a substituted group KF
IV
ha [00112] Substituted arylsulfur pentafluorides (1) were synthesized from the corresponding aryl sulfur Compounds (Ha) by the similar procedure as in Example I. Table 3 shows the synthesis of the substituted arylsul fur 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 (Fluorinert0) was used as a solvent in Process II in Examples 9 and 10. The Fluorinerte FC-72 was a perfluorinated organic compound having a boiling point of 56 C, which was a product made by Company.
Table 3: Production of Arylsulfur pentafluorides (I) from Aryl sulfur compounds (Ha) , , Nocess I
I Process II
Es.
(Ha) Halogen (III) Solvent Conditions (IV) Yield ,A11-1;(1a,nir Fwirmxide Solo. Conditions (I) Yield , (o-s)-- a, KF CH,CN 0-5 C c -..,C1 80%44g Zn112 non a -I .2rnol 14 4 300mL -9.3 h (0_222,1) 12.34 120 C 0-SF, 73%

33-03 (0-158/8117 (2.4mol) 13/2 58g (OA 2mol) la 306e (CH,-0-5)- a, KF CH,CN 0 C C21/40-5F2C1 73, 34 Z-nF2 non 90 C C1-5,0-SF, 2 1 a 6 1 (I37mnol) g-474 0.73nol 44 L 0.51 1Vb 7g (82mm ol) ovrig 234 (05rnol) ,0mol, lb 21.4 0-5"C
3 (F-0-5)- C12 KF CH2C'N 2511 8-0-5F.C1 67% 108 ZnF, 1201r _0...
iSFs 62%
'./ o.28mol 36 g I Qaaal- and ra' (42mmol) 2.6g /6 It F
(0.63rnol) overnight 1Vd I2.5g (25mmol) id 5.8g I0.0g (0.039mon 4 (C) - )- CI 2 KF CH7CN I.8h 0-5F,,C1 80% 41,7,,,,,) Z:1!) 00,, 120^C 0_sF, 59%
2 0.31mol 36-gg 100ml and ra. 2-59g 1511 . (063mol

10.04 (00398m1) ) overight lye 14.9g (25mrnol) In 5.5g (61-0-5)-C12 Kr cH3CN ast, er-O-sF,a 30g Z F7 ge171.oe reflux Br-0-5F, 'no, , 0,72,,,,i 948 200rta, and EL = ' '. (1100nunor) 6,18g 20,L. 17 h ' - -(1.6mol) 3767 (0.1 ool) ov ism Pig 46.2g (60nsrnol) 18 22.3g . f D-5.55b*C 8SFa CI 86% (131rnmol) 2Z.IF2 nc" 07 1132 I:C 7S%
Or 6 ( 8'0-4 a, 1(1 CH-CN 6 0_sg, 2 0.88rn01 1104 250mL and r.1 (20mrnol) 47.7g (0_127inol) (2.0mol) overnight IVII 65.7g lit 6.8g 0-5^C

7 (0-,NO-Sy Cl, 4.5b (it4190--SF,C1 60% 2-6.5g Z
Kin nr, lyrc 0_0_ SF, 36%

21-43m1.- and xi. (10Ornmol) 6.180 72 la .
7 0_72mo1 (1.6risol) 30.8g (O. / Ind) overnight 1Vi 32.4 (601;imol) 1i 9.0g Table 3 (continued) Process I Process 11 .
Ex_ (ho) Halogen (III) SOIYCM Conditions (Tv) Yield c,ArXT ,F,,,,,I 6,,,,Ida Solo. Concitions (1) Yield F \ F

CsF CH -CN 0-5 C C.1-51:sCi 87% 30 C
41.877 Zitt F., g (C:3)-2- el' (0.1110101) 18.1 g 80" 411 0 SF, 52%

F F (0 1 imol) 2 -1 02inol 279.3-.e :,,F7 203m1 h tarl 0 i) and rt.

Overnight 'VI 4237 29.1g (0.1moll 69 li 20.0g . 8 S8, 60%
= 9 ( 8-4 4.; Cl, gy CH,CN 0-511C F
SF,CI 67% 4.097 SbF, FC-i2 ri. --C--(14 91nmol) 0.5-0.6mL 70m1 lb F

11 90g 306ml. fan F F
-I ,02''9I ( I .3tool) and rx. (-8mmol) ci F
22.9g (0.071no/) overnight /VI 25.87 F
.-.SF, 204 F bri 3.197 (total) F
KYCH,CN 0-PC F SbF FC-72 r.,.
i 0 el, Sin F40 .,,,,, 9.47g 5 "' (30.5mmoi) 3.41g 40mL lb F F ' -1 '''''4 024 3 rni-i .1.1 r-'= F F (30.nytt ol) (1 41mol F-. F In FS.:_isti 67 Q%
overnight 26 1g (0.065rnot) 1Vn 34.94 1001131 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; 1H NMR.
(CD3CN) 7.65 (d, 2H, aromatic), 7.29 (d, 2H, aromatic), 2.36 (s, 3H, CH3); 19F
NMR

(CD3CN) 137.66 (s, SF4CI); 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.
[001151 p-Methylphenylsulfur pentafluoride; b.p. 95-96 C/80 mmHg; IH NMR
(CDC13) 7.63 (d, 2H, aromatic), 7.24 (d, 2H, aromatic), 2.40 (s, 31-1, CH-3);
'9F NMR (CDC13) 86.55-84.96 (in, IF, SF), 63.26 (d, 4F, SF4).
[00116) p-Fluorophenylsulfur chlorotetrafluoride; b.p. 60 C/8 mmHg; IFI
NMR
(CD3CN) 7.85-7.78 (in, 2H, aromatic), 7.25-7.15 (in, 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 A) (calcd for C61-L4F5S35C1;
237.964241). The NMR shows that p-fluorophenylsulfur chlorotetrafluoride obtained is a trans isomer.
1001171 p-Fluorophenylsulfur pentafluoride; b.p. 71 C/80 mmHg; 1H NMR
(CDC13) 7.80-7.73 (in, 2H, aromatic), 7.17-7.09 (m, 2H, aromatic); '9F NMR (CDC13) 87.78-83.17 (in, IF, SF), 63.81 (d, 4F, SRO, -107.06 (s, 1F, CF); GC-MS m/z 222 (M4).
[001181 o-Fluorophenylsulfur chlorotetrafluoride; b.p. 96-97 C/20 mmHg; 1H
NMR
(CD3CN) 7.77-7.72 (m, 1H, aromatic), 760-7.40(m, 1H, aromatic), 7.25-7.10 (ni, 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
(CDC13) 7.78-7.73 (m, 1H, aromatic), 7.55-7.48 (in, 1H, aromatic), 7.27-7.17 (in, 2H, aromatic); 19F NMR (CDC13) 82.38-81.00 (in, IF, SF), 68.10 (dd, 4F, SF4), -108.07+108.35) (m, IF, CF).
[001201 p-Bromophenylsulfur chlorotetrafluoride (X); m.p. 58-59 C; 'H NMR
(CD3CN) 5 7.67 (s, 4H, aromatic); '9F NNIR (CD3CN) 5 136.56 (s, SF4C1); High resolution mass spectrum; found 301.877066 (16.5%) (calcd for C6H481Br 37C1F4S;
301.879178); found 299.880655 (76.6 ,4) (calcd for C6H48IBr35C1F4S; 299.881224 and calcd for C6H479Br37C1F4S;
299.882128), found 297.882761 (77.4%) (calcd for C6H479Br35CIF4S; 297.884174).
Elemental analysis; calcd for C6H4BrC1F4S; 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; 1H NMR
(CDC13) 7.63 (s, 4H, aromatic); 19F NMR (CDC13) 84.13-82.53 (in, 1F, SF), 63.11 (d, 4F, SF4).
[00122] m-Bromophenylsulfur chlorotetrafluoride; b.p. 57-59 C/0.8 mmHg; 1H NMR
(CD3CN) 7.90-7.88 (m, 1H, aromatic), 7.70-7.50 (in, 2H, aromatic), 7.40-7.30 (in, 1H, -aromatic); 19F NMR (CD3CN) 136.74 (s, SF4C1). High resolution mass spectrum;
found 301.878031 (29.1%) (calcd for C6H481Br37C1F4S; 301.879178), found 299.881066(100%) (calcd for C6H481Br35C1F4S; 299.881224 and calcd for C6H479Br37C1F4S;
299.882128), found 297.883275 (77.4%) (calcd for C611479Br35C1F4S; 297.884174). The NMR showed that m-bromophenylsulfur chlorotetrafluoride obtained was a trans isomer.
[00123] m-Bromophenylsulfur pentafluoride; lip. 69-70 C/10 mmHg; 1H NMR
(CDC13) 7.91 (t, 1H, aromatic), 7.72-7.64 (m, 2H, aromatic). 7.35 (t, 1H, aromatic); '9F NMR
(CDC13) 83.55-82.47 (m, IF, SF), 63.13 (d, 4F, SF4), [00124] p-Nitrophenylsulfur chlorotetrafluoride; m_p. 130-131 C; 1H NMR
(CD3CN) 8.29 (d, J=7.8 Hz, 2H, aromatic), 8.02 (d, J=7.8 Hz, 2H, aromatic);

(CD3CN) 134.96 (s, SF4C1); High resolution mass spectrum; found 266.956490(38.4%) (calcd for C6H437C1F4NO2S; 266.955791), found 264.959223 (100%) (calcd for C6H435C1F4NO2S; 264.958741). Elemental analysis; calcd for C61-14C1F4NO2S; 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 (in, 2H, aromatic), 7.99-7.95 (in, 2H, aromatic); 19F NMR
(CDC13) 82.32-80.69 (in, 1F, SF), 62.76 (d, 4F, SF4).
[00126] 2,6-Difluorophenylsulfur chlorotetrafluoride: The product (b.p. 120-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) 5 143.9 (t, J=26.0 Hz, 4F, SF4), -104.1 (quintet, J=26.0 Hz, 2F, 2,6-F): NMR (CDC13) 5 6_97-7.09 (m, 2H, 3,5-H), 7.43-7.55 (in, 111,4-H); 13C NMR (CDC13) 5 157.20 (d, J262.3 Hz), 133.74 (t, J=11.6 Hz), 130.60 (m), 113.46 (d, J=14.6 Hz); high resolution mass spectrum; found 257.950876 (37.6%) (calcd for C6H337C1F6S; 257.951869), found 255.955740 (100%) (calcd for C6H335C1F6S;
255.954819);

elemental analysis; calcd for C6113C1F6S; C, 28.08%, H, 1.18%; found; C, 28_24%, H, 1.24%.
The cis-isomer was assigned in the following; 19F NMR (CDC13) 5 158.2 (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; 1H NMR
(CDCI3) 67.51 (m, 1H), 7.04 (m, 2H); 19F NMR (CDCI3) 82.32-80.69 (in, 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 (CDCI3) 5 14-4.07 (t, J=26.0 Hz, 4F, SRI), -99.80 (t, J=26.0 Hz, 2F, o-F), -100.35 (s, IF, p-F); 1H NMR (CDCI3) 66.79 (t, J=17.5 Hz, m-H); 13C NMR (CDCI3) 164.16 (dt, J=164.2 Hz, 15.2 Hz, 4-C), 158.18 (dm, J=260.7 Hz, 2-C), 127.7 (m, 1-C), 102.1 (tm, J=27.8 Hz, 3-C). Elemental analysis; calcd for C6H2CIF7S; 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-Trifluorophenyisulfur pentafluoride: 19F NMR (CDCI3) 5 78.7-75.3 (in, SF), 73.8-72.9 (in, SF4), -100.6 (in, 4-F), -100.7 (m, 2,6-F) ; NMR (CDCI3) 66.80 (t, J=8.6 Hz, 3,5-H); GC-Mass inlz 258 (10. 3-Chloro-2,4,6-trifluorophenylsulfur pentafluoride: 19F NMR (CDCI3) 5 78.7-75.3 (m, SF). 73.8-72.9 (rn, SF4), -101.3 (m, 2 or 6-F), -102.3 (m, 4-F), -102.6 (m, 2 or 6-F); 1H NMR (CDCI3) 66.95 r.t, J=9.5 Hz, 5-H); GC-Mass rniz 294, 292 (1\41).
[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; '9F NMR (CDCI3) 8 144.10 (t, J=26.0 Hz, 4F, SF4)3 -132.7 (m, 2F, 2,64), -146.6 (m, IF, 4-F), -158.9 (m, 2F, 3,5-F); 13C NMR (CDCI3) 8 143.5 (dm, J=265.2 Hz), 141.7 (dm, J=263.7 Hz), 128.3 (m). The cis isomer; 19F NMR
(CDCI3) 8 152.39 (quartet, J=158.9 Hz, 1F, SF), 124.32 (m, 2F, SF2), 79.4 (n, IF, SF), -132.7 (n, 2F, 2,6-F), -146.6 (m, 1F, 4-F), -158.9 (m, 2F, 3,5-F). High resolution mass spectrum of a 1.7:1 mixture of the trans and cis isomers; found 311.923124 (15.5%) (calcd for C637C1F9S;
311.923604), found 309.926404 (43.10/) (calcd for C635C1F9S; 309.926554).
[001311 2,3,4,5,6-Pentafluoropheny1su1fur pentafluoride: b.p. 135-137 C;
'9F NMR
(CDC13) 6 74.8 (m, 5F, SF5), -133.4 (in, 2F, 2,6-F), -146.2 (m, IF, 4-F), -158.6 (in, 2F, 3,5-F); '3C NMR (CDC13) 6 143.6 (din, J=262.2 Hz), 137.9 (dm, J=253.6 Hz), 126.7 (m). High resolution mass spectrum; found 293.956492 (calcd for C6F10S; 293.956104).
Example 11. Synthesis of phenvlsulfur pentafluoride from diphenyl disulfide with a mixture of hydrogen fluoride and pyridine as afluoride source in Process II
Process I Process II
S¨S SF,CI SF5 az HF-pyridine KF IVa la [00132] (Process I) Phenylsulfur chlorotetrafluoride was prepared in a high yield in the same mariner 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 phenylsul fur pentafluoride was produced in 93%
yield.
Example 12. Synthesis of phenylsulfur pentafluoride from thiophenol as an aryl sulfur compound of formula (Jib) Process i Process 11 C12 ZnF2 KF 1Va la [001341 (Process 1) Chlorine (C17) was passed with a flow rate of 27 mUrnin into a stirred mixture of 10.0 g (90.8 mmol) of thiophenol and 47.5 g (0.817 mol) of dry KF in 100mL 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 chlorotetraflumide (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 I.
The product was a trans isomer.
[00135] (Process II) Phenylsulfur chlorotetrafluoride obtained in Process [above may be allowed to react with ZnF2 in the same procedure as Process II in Example I, giving phenylsulfur pentafluoride in good yield.
Example 13. Synthesis of p-nitrophenvlsulfur pentalluoride from p-nitrobenzenesulfenvl chloride as an aryl sulfur compound of formula _ Process T Process fl 02N II sCI _________ 02N SF4Cl ___ 1. 02N SF5 Cl2 Zn F2 KF lVi [00136J (Process I) Chlorine (02) 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 minol) of dry KF in 40mL of dry acetonitrile at 5-11 cC. The total amount of chlorine passed was 2.54 L (113 minO1). After 5 mL of 1,1,2-trichlorotrifluoroethane was added to the reaction mixture, the reaction mixture was filtered_ After removal of the solvent in vacuum, p-nitrophenylsulfur chlorotetra fluoride (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 ZnF, in the same procedure as Process II in Example 7, giving p-nitrophenylsulfur pentafluoride in good yield.
Example 14. Synthesis of phenvIsulfur pentafluoride from phenvlsulfur trifluoride Process III Process * SF3 _________________ SF4C1 SF5 C12 ZnF, KF 1Va la [001381 (Process III) Chlorine (C12) was passed with a flow rate of 34 inUrnin into a stirred mixture of 5.00 g (30.1 mmol) of phenylsulfur tifluoride and 8.74 g (150 mmol) of =

dry ICE in 20 rriL 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 inmol). 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.
[001391 (Process II) Phenylsulfur chlorotetrafluoride obtained in Process III above may be al.lowed to react with ZilF2 in the same procedure as Process II in Example 1, giving phenylsulfur pentafluoride in good yield.
Example 15. Reaction of phenvlsulfur chlorotetrafluoride and ZnF2 under a slowjlow of chlorine (presence of halogen) Process ll' SF,ci sF5 Zn:F2 / Cl2 IVa fa (Process II') trans-Phenylsulfur chlorotetrafluoride (trans-PhSF4C1) 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-PhSF4C1 and 2.8 g (0.027 rnol) of dry ZriF2. 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 C12 gas was added into the reaction vessel at the rate of 4.6 mUrninute. The progress of the reaction was monitored by 19F NMR. After 40 minutes at 120.C, three major compounds (trans-PhSF4C1, cis-PhSF40, and phenylsulfur pentafluoride (PhSF5)) were detected to be present in the reaction mixture_ The mol ratio of trans-PhSF4C1: cis-PhSF4C1 :
PhSF5 was 0.5; 3.3: 100. After additional 60 minutes at 120.C, trans- and cis-PhSF4C1 disappeared and only PhS F5 was detected from '9F NMR. The reaction was completed within 1.7 hat 120'C. After N2 (5.4 mUrninute) 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-PliSF4C1 is formed intermediately by the isornerization of trans-PhSF4CI, and cis-PhSF4C1 is converted to the product, PhSFs.
Example 16. Reaction of phenvlsulfur chlorotetrafluoride and ZnF2 under a fast flow of chlorine (presence of halogen) Process II' sF,ci sF5 Zii.F2 ICI, IVa la [00140] (Process II') trans-Plienylsulfur clalorotetrafluoride (trans-PhSRICI) used for this Process was prepared in high yields by the Process I or III as shown by Examples 1, II, 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-PhSF4C1 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 mUminute. The progress of the reaction was monitored by 19F NIVIR.
After 45 minutes at 120C, three major compounds (trans-PhSEICI, cis-PhSF4C1, and phenylsulfur pentafluoride (PhSF5)) were detected to be present in the reaction mixture.
The mo1 ratio of trans-PhSF4C1 : cis-PhSF4C1 : PhSFs was 18 : 83 : 100. After additional 45 minutes at 120C, trans- and cis-PhSF4C1 disappeared and only PhS F5 was detected from 19F NMR.
The reaction was completed in about 1.5 h at 120*C. After N2 (26.9 mUminute) was flowed for 1 hour, the examination of the reaction mixture by 19F NMR using benzotrifluoride as a standard showed that phenylsul fur 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-PhSF4CI is formed intermediately by the isomerization of trans-PhSF4C1, and cis-PhSF4C1 is converted to the product, PhSFs.
Example 17. Reaction of 2,6-difluorophenidsulfur chlorotetrafluoride and ZnF, under a flow of chlorine (presence of halogen) FF CI
Process 11' 111 SF4Ci _________ = sF5 + SF5 ZnF2 / C12 IVj ij [00141] (Process II') A 6:1 mixture of trans and cis-2,6-difluorophenylsulfur chlorotetrafluoride used for this Process was prepared in high yields by the Process I or III as shown by Examples 8. In a thy box, a 100 mL reaction vessel made of fluoropolymer was charged with 1103 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 mUminute as the reaction vessel was heated to I30-140 C, at which point addition of 32.36 g (0.126 mol) of the mixture of trans- and cis-2,6-di fluorophenylsulfur 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-difluorophenylsul fur 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 Na2SO4, 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-chloro-2,6-difluorophenylsulfur pentafluoride (93%
purity, determined by GC). The spectral data of 3-chloro-2,6-difluorophenylsulfur pentafluoride were as follows; 19F NMR (CDC13) 77.9-75.7 (m, IF, SF), 73.2-72.5 (m, 4F, SF4), -103.3 (m, 1F), -105.2 (m, IF); 1H NMR (CDC13) 8 7.60 (m, 1H), 7.04 (in, I Ff); high resolution mass spectrum, found 275.942071 (36.0%) (calcd for C6H237C1F2S; 275.942447), found 273.945943 (100%) (calcd for C6H235C1F2S; 273.945397). The other product, 2,6-difluorophenylsuflur pentafluoride was identified by the data obtained by Example 8 (Process H).
Example 18. Reaction of phenylsulfur chlorotetrafluoride and ZnFzunder a slow flow of an inactive as (nitraeen) -Process II
sF,ci SF5 ZnF2 IVa under a slow flow of la an inactive gas (N2) [001421 (Process II) trans-Phenyl sulfur chlorotetrafluoride (trans-PhSF4C1) 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-PhSF4C1 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 I20 C with N2 flowing at the rate of 5.4 mUminute. 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 19F
NMR. Three major compounds (trans-PhSF4CI, cis-PhSF4CI and PhSF5) were present in the reaction mixture. The ratio of trans-PhSF4C1 : cis-PhSF4CI: 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-PhSF4C1 was 2.4%, cis-PhSF4CI was 14.6 %, and PhSF5 was 67.2 A. The reaction was not complete in 5 hat 120.C. Therefore, this experiment showed that the reaction under the flow of nitrogen was slowed down.
Example 19. Reaction of pltenvlsulfur chlorotetrafluoride and Zrz1-7, under a fast flow of inactive gas (nitrogen) Process If SF,CI SF5 ZnF2 under a fast flow of IVala an inactive gas (N2) 1001431 (Process II) trans-Plienylsulfur chiorotetrafluoride (trans-P.118E1C!) used for this Process was prepared in high yields by Process I or III as shown by Examples I, 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-PhSF4C1 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 mUminute. 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 19F
1\11v1R. Tlu-ee major compounds (trans-PhSF4CI, cis-PhSF4C1 and PhSF5) were present in the reaction mixture. The ratio of trans-PhSF4C1 : cis-PhSF4CI : 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-PhSF4CI was 6.7 %, cis-PhSF4C1 was 42.1 %, and PhSF5 was 38.4%. The reaction was not complete in 5 hat 120 C and the conversion of PhSF4C1 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 ofphenylsulfur pentafluoride by using Sbfi as ajluoride source Process H
11/ SF4C1 s,6 SbF3 IVa fa (001441 (Process II) trans-Phenylsulfur chlorotetrafluoride used for this Process was prepared in high yields by the Process I or 111 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 0.397 g (2.22 mrnol) 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 technique showed that phenylsulfur pentafluoride was produced in 33% yield.
Example 21. Synthesis of phenylsuffur pentafluoride by using a mixture of SbFl (fluoride source) and Sbai (fluoride source-activating compound) as a fluoride source Process H

SbF3/SbC15 [Va la L00145] (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 SbC15, and 2 mL of dry hexane. SbCI5 is a fluoride source-activating compound. SbC15 (strong Lewis acid) can complex with SbF3 to form SbF2(SbFC15), which can also be made by SbF2C1 and SbFCI4 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 phenvlsulfur pentafluoride by using SnF4 as a fluoride source Process II
SF4ci SFs SnF4 IVa la [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 inmol) of dry SnF4. The reaction vessel was brought out from the dry box and equipped with a balloon filled with N2. The mixture was stirred at 80.0 for 2 h. The analysis of the reaction mixture by '9F-NMR
showed that phenylsulfur pentafluoride was produced in 34% yield.
_Example 23. Synthesis of phenylsulfur pentafluoride by using TiF4 as a fluoride source Process 11 TiF4 IVa fa [00147] (Process II) trans-Phenylsulfur chlorotetrafluoride used for this Process was prepared in high yields by the Process for III as shown by Examples 1, II, 12, or 14. In a dry box, a reaction vessel made of fluoropolymer was charged with 1.0 g (4.54 mmol) of trans-phenylsul fur chlorotetrafluoride and 0_17 g (1.4 ininol) of dry TiF4.
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 ofphenylsulfur chlorotetrafluoride from diphenvl disulfide .40 Process 1 S¨S 111 ________________________________ SF4CI
CsF 1Va [001481 (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 mUrnin) for 0.5 h. After the N2 flow was stopped, C12 was bubbled into a reaction mixture at the rate of 63 mUmin for 4 h. The total amount of C12 used was 0.68 mol. The reaction mixture was then warmed to room temperature and stirred overnight. Then, N2 (18 mUmin) 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 phenylsul fur 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 ofp-c-hlorophenylsulfur chlorotetrqfluoride from bis(p-chlorophenyl) disu(fide Process 1 CI 411 SS 4100 CI SF4Ci KF 1Vf [001491 (Process I) Chlorine (C12) was passed with a flow rate of 64 mL/min into a stirred mixture of 25.0 g (87.0 inmol) of bis(p-chlorophenyl) disulfide and 86.0 g (1.48 mol) of dry KF 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; 1H NMR (CDC13) 5 7.38 (d, 2H, .1=9.1 Hz), 7.65 (d, 2H, J=9.1 Hz); 19F
NMR (CDC13) 137.4 (s, 4F, SF4C1). 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 C6H4F4S3502;
253.934690). The NMR showed that p-chlorophenylsulfur chlorotetrafluoride obtained is a trans isomer.

Example 26. Synthesis of p-(tert-butvl)phenvlsulfur chlorotetrafluoride from p-(tert-butvl)benzenethiol Process SH ______________________________ 110 sF4Ci CsF
IVc [001501 (Process I) Chlorine (C12) was passed with a flow rate of 35 mlimin 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; 1H NMR
(CDC13) 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); I9F NMR 138.3 (s, SF4C1). High resolution mass spectrum; found 278.034576 (8.8%) (calcd for C10H1337CIF4S; 278.033313), found 276.037526 (24.7%) (calcd for C10lI1335C1F4S; 276.036263). Elemental analysis; Calcd for C131-1-13C1F4S; C, 43.40%;
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 phenvlsulfur chlorotetrafluoride and ZnF2 Process II or II"
SF4CI41. SF-5 ZnF2 IVa fa [00151] (Process II or II-) In a dry box, a reaction vessel made of fluoropolyrner was charged with 1.0 g (4.54 mmol) of trans-phenylsulfur chlorotetrafluoride and 0.281 g of dry ZnF2 (solid, rrip 872.C, bp 1500C). The reaction vessel was brought out from the dry box and equipped with a balloon filled with N2. The mixture was heated at 80.0 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 phenvIsulfur pentafluoride from phenylsulfur chlorotetrafluoride and ZnF2 Process II or II"

ZnF2 IVa ía [001521 (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 ofphenylsulhur pentafluoride from phenylsulfur chlorotetrafluoride and CuF2 Process 11 or 11"
SF4ci SF5 Cu F2 IVa fa [001531 (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 chlorotetrafluonde and 0.284 g (2.79 inmol) 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 An analysis of the reaction mixture by 19F-NMR showed that phenylsulfur pentafluonde was produced in 57% yield.
Example 30. Synthesis of p-inethylphenvIsulfur pentafluoride from p-nzethylphenvisulfur chlorotetrafluoride and ZnF7 Process ii or II"
cH3 * sF4ci c H3 1, SF5 znF2 IVb lb [001541 (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-methylphenyls.ulfur chlorotetrafluoride and 0.266 g (2.57 mmol) of dry ZnF, (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 phenvlsulfur chlorotetrafluoride and HBF4 diethyl etherate Process H or II"
SFiCI SF5 HBF40Et2 IVa Ia (Process II or II") In a dry box, a reaction vessel made of fluoropolyrner was charged with 1.0 g (4.5 mmol) of trans-phenylsulfur chlorotetrafluoride (trans-PhSF4C1) 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) (HBF40Et2) (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-PliSF4C1, cis-PhSF4C1 and PliSF5) were present in the reaction mixture. The ratio of trans-PhSF4C1: cis-PhSF4C1 : PhSFc was 156: 716: 100.
After 21 hours, the ratio of trans-PhSF4C1 : cis-PhSF4C1 : PhSF5 changed to 3 6 : 100.
An analysis of the reaction mixture by 19F-NMR showed that phenylsul fur pentafluoride (PliSF5) was produced in 40% yield.
Example 32. Synthesis of phenylsulfur pentafluoride from phenylsulfur chlorotetrafluoride by using a mixture of ZnF2(fluoride source) and SbC1i (fluoride source-activating compound) as a fluoride source Process H or H"
SF,Ci ___________ > SF5 ZOF2/SbCis IVa la 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), SbC15 (liquid) (0.41 g, 0.17 mL, 1.36 mmol) was added into the mixture. To this, trans-phenylsulfur chlorotetrafluoride (trans-PhSF4C1) (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. SbC15 is a fluoride source-activating compound.
SbC15 (strong Lewis acid) can complex with ZnF2 to form ZnF(SbFC15), which can also be made by ZnFCl and SbFCI4 both are fluoride sources usable in this invention.
The reaction =

mixture was stiri-ed at room temperature. The progress of the reaction was monitored by 19B
NMR. After 10 minutes, the ratio of trans-PhSF4C1 : cis-PhSF4C1 : PhSF5 was 385 : 0: 100.
After 90 minutes, the ratio of trans-PhSF4C1 : cis-PhSF4C1 : PhSF5 changed to 63 : trace:
100. After 180 minutes, the ratio of trans-PhSF4C1: cis-PhSF4C1: PhSF5 changed to 34:
trace: 100. After 17 hours, the ratio of trans-PhSF4CI : cis-PhSF4C1 : 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-PhSF4C1 (9.4 %) remained.
Example 33. Reaction of phenylsulfur chlorotetrafluoride and BF 2 gas (Comparative Example) sF4ci _________ As Polymeric residue IVa [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 aim) was introduced into the reaction vessel till the pressure reached 18 psi. The reaction mixture was then warmed to FOOM 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 BFiRas in methylene chloride (Comparative Example) [001561 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 pheny1sulfur pentafluoride was formed in 28% yield.

[001571 Examples 33 and 34 show that as Ou et al. reported, it was found that, when boron tri fluoride (boiling point -100'C at 1 atm) was flowed through a solution of phenylsulfur chlorotetrafluoride in a deuterium methylene chloride, phenylsul fur 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 product was 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.
[001581 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 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 (3)

What is claimed is:

1. An arylsulfur chlorotetrafluoride represented by formula (IV'):
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 wherein, 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.

2. The arylsulfur chlorotetrafluoridc of claim is selected from the group consisting of 2-tert-butylphenylsulfur chlorotetrafluoride, 3-tert-butylphenylsulfur chlorotetrafluoride, 4-tert-butylphenylsulfur chlorotetrafluoride, 2-fluorophenylsulfur chlorotetrafluoride, 3-fluorophenylsulfur chlorotetrafluoride, 4-fluorophenylsulfur chlorotetrafluoride, 2-chlorophenylsulfur chlorotetrafluoride, 3-chlorophenylsulfur chlorotetrafluoride. 4-chlorophenylsulfur chlorotetrafluoride, 2-bromophenylsulfur chlorotetrafluoride, 3-bromophenylsulfur chlorotetrafluoride, 4-bromophenylsulfur chlorotetrafluoride, 2,3-difluorophenylsulfur chlorotetrafluoride, 2,4-difluorophenylsulfur chlorotetrafluoride, 2,5-difluorophenylsulfur chlorotetrafluoride, 2,6-difluorophenylsulfur chlorotetrafluoride, 3,4-difluorophenylsulfur chlorotetrafluoride, 3,5-difluorophenylsulfur chlorotetrafluoride, 3,6-difluorophenylsulfur chlorotetrafluoride, 2,3,4-trifluorophenylsulfur chlorotetrafluoride, 2,3,5-trifluorophenylsulfur chlorotetrafluoride, 2,3,6-trifluorophenylsulfur chlorotetrafluoride, 2.4,6-trifluorophenylsulfur chlorotetrafluoride, 2,4,5-trifluorophenylsulfur chlorotetrafluoride, 3.4,5- trifluorophenylsulfur chlorotetrafluoride, and 2,3,4,5,6-pentafluorophenylsulfur chlorotctrafluoride.

3. The arylsulfur chlorotctrafluoride of claim 1 is 4-tert-butylphenylsulfur chlorotetrafluoride, 4-fluorophenylsulfur chlorotetrafluoride, 2-fluorophenylsulfur chlorotetrafluoride, 4-chlorophenylsulfur chlorotetrafluoride, 4-bromophenylsulfur chlorotetrafluoride, 3-bromophenylsulfur chlorotetrafluoride, 2,6-difluorophenylsulfur chlorotetrafluoride, 2,4,6-trifluorophenylsulfur chlorotetrafluoride, or 2,3,4,5,6-pentafluorophenylsulfur chlorotetrafluoride.