US 2011 0160488A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0160488 A1 Umemoto et al. (43) Pub. Date: Jun. 30, 2011

(54) FLUORINATION PROCESSES WITH Related U.S. Application Data ARYLSULFUR HALOTETRAFLUORDES (60) Provisional application No. 61/041,415, filed on Apr. (75) Inventors: Teruo Umemoto, Westminster, CO 1, 2008, provisional application No. 61/034,600, filed (US); Rajendra P. Singh, on Mar. 7, 2008. Broomfield, CO (US) Publication Classification (73) Assignee: IM&T RESEARCH, INC., (51) Int. Cl. Denver, CO (US) C07C 319/20 (2006.01) (21) Appl. No.: 12/525,714 (52) U.S. Cl...... 568/74 (22) PCT Fled: Mar. 6, 2009 (57) ABSTRACT (86) PCT NO.: PCT/USO9/36305 New fluorination processes for introducing one or more fluo rine atoms into target Substrate compounds with arylsulfur S371 (c)(1), halotetrafluorides are disclosed. Also disclosed are methods (2), (4) Date: Aug. 4, 2009 for preparation of arylsulfur trifluorides. US 2011/0160488 A1 Jun. 30, 2011

FLUORINATION PROCESSES WITH reported as fluorinating agents U.S. Pat. No. 7,265.247 B1. ARYLSULFUR HALOTETRAFLUORDES Requirement for pentafluorophenyl and multi-substituted phenyl parts increases the cost. In addition to the above TECHNICAL FIELD mentioned drawbacks, most of the fluorinating agents men tioned above are extremely or substantially sensitive to mois 0001. The present invention relates to new fluorination ture. Therefore, production and handling of these materials is processes using arylsulfur halotetrafluoride as a fluorinating extremely troublesome since moisture or wet conditions eas agent. ily decompose the fluorinating agents. Recently, it appeared that multi-substituted phenylsulfur trifluorides such as 4-tert BACKGROUND OF THE INVENTION butyl-2,6-dimethylphenylsulfur trifluoride in solid state are 0002 -containing compounds have found wide not sensitive to water (see, for example, U.S. Pat. No. 7.381, use in medical, agricultural, electronic and other like indus 846 B2). However, 4-tert-butyl-2,6-dimethylphenylsulfur tri tries (see Chemical & Engineering News, June 5, pp 15-32 in solution is very sensitive to water; immediate (2006); Angew. Chem. Ind. Ed., Vol. 39, pp. 4216–4235 decomposition occurs on contact with water. (2000)). These compounds show specific biologic activity or 0005 Each of these conventional, illustrative fluorinating physical properties based on the presence of one or more agents, or production methods, allows for room for improve fluorine atoms. A particular drawback in their usefulness is ment on providing easy, safe, effective, and less costly fluo the scarcity of natural fluorine-containing compounds, rination agents or methods for the production of these impor requiring most Such compounds to be prepared through tant fluorine-containing compounds. organic synthesis. 0006. As such, there is a need in the field to provide, safe, 0003 Fluorinating agents are compounds that selectively reactive, less hazardous, easily produced/stored, cost effec introduce fluorine atom(s) into target compounds through one tive, fluorinating reagents or methods, especially fluorinating or more chemical reactions to produce fluorine-containing agents and methods that selectively introduce fluorine atoms compounds. Particularly useful fluorinating agents have the into compounds in high yields and that are insensitive to capacity to replace oxygen or oxygen-containing groups or moisture. or Sulfur-containing groups in the target compound 0007. The present invention is directed toward overcom with fluorine. A number of fluorinating agents have been ing one or more of the problems discussed above. discovered; however, as discussed in more detail below, these agents generally have significant drawbacks based on Safety, SUMMARY OF THE INVENTION reactivity, stability, production, handling, storage and/or dis 0008. The present invention provides new fluorination posability. processes with arylsulfur halotetrafluorides as fluorinating 0004 Illustrative examples of known fluorinating agents agents for the introduction of fluorine atoms into target com include: (SF), a highly toxic gas that is pounds. The resultant target compounds, i.e., fluorine-con often utilized under pressure J. Am. Chem. Soc., Vol. 82, pp taining compounds, have shown tremendous potential in the 543-551 (1960): N,N-diethylaminosulfur trifluoride medical, agricultural, electronic and other like industries. (DAST), an unstable liquid agent having a highly explosive 0009. In general, arylsulfur halotetrafluoride compounds nature, i.e., low thermal stability and large amounts of ther are used as fluorinating agents. Typical arylsulfur halotet mal energy upon decomposition J. Org. Chem. Vol. 40, pp rafluoride compounds are substituted or unsubstituted phe 574-578 (1975) and Chem. & Eng. News, Vol. 57, No. 19, p nylsulfur halotetrafluorides. Among these compounds, Sub 4 (1979); bis(methoxyethyl)aminosulfur trifluoride (Deoxo stituted or unsubstituted phenylsulfur chlorotetrafluorides are Fluorr) or its N-aryl analogs, compounds that have low ther preferred. The substituted or unsubstituted phenylsulfur hal mal stability U.S. Pat. No. 6,222,064 B1; Chem. Commun., otetrafluorides are shown herein to have substantial func pp. 215-216 (1999); J. Org. Chem. Vol. 65, pp. 4830-4832 tional, safety, and ease of handling advantages over com (2000); selenium tetrafluoride (SeF), a highly toxic sele pounds and methods utilizing conventional fluorinating nium compound J. Am. Chem. Soc., Vol. 96, pp. 925-927 agents. (1974); and various other designed fluorinating agents that 0010. In particular, compounds of the present invention provide greater safety but have provided substantially have enhanced stability due to capacity to avoid degradation reduced reactivity and yields: e.g., phenylfluorophosphane due to moisture or wet conditions. reagents Ph.PFs (n=1-3), Chem. Pharm. Bull. Vol. 16, p 0011. The present invention also provides new and useful 1009 (1968), C.C.-difluoroalkylamino reagents preparative processes for unsubstituted or substituted phenyl CICFHCFNEt, Organic Reactions, Vol. 21, pp 158-173 sulfur trifluorides. (1974); CFCFHCFNEt, Bull. Chem. Soc. Jpn. Vol. 52, pp 0012. These and various other features as well as advan 3377-3380 (1979); CFHCFNMe, J. Fluorine Chem. Vol. tages which characterize the invention will be apparent from 109, pp 25-31 (2001), 2,2-difluoro-1,3-dimethylimidazoli a reading of the following detailed description and a review of dine Chem. Commun., pp 1618-1619 (2002), and (m-me the appended claims. thylphenyl)difluoromethyldiethylamine (Tetrahedron, Vol. 60, pp 6923-6930); phenylsulfur trifluoride was used as a DETAILED DESCRIPTION OF THE INVENTION fluorinating agent, but its fluorination yields have proven low and its applicability narrow J. Am. Chem. Soc., Vol. 84, pp 0013 The present invention provides new processes for 3058-3063 (1962); Acta Chimica Sinica, Vol. 39, No. 1, pp introducing one or more fluorine atoms into target com 63-68 (1981). Pentafluorophenylsulfur trifluoride was used pounds with arylsulfur halotetrafluorides as fluorinating only for conversion of benzaldehyde to (difluoromethyl)ben agents. In the present invention the term “target compound Zene J. Fluorine Chem. Vol. 2, pp 53-62 (1972/73) and, includes any substrate that once fluorinated is useful in the recently, multi-substituted phenylsulfur trifluorides were medical, agricultural, biological, electronic materials or US 2011/0160488 A1 Jun. 30, 2011

other like field, i.e., is a fluorine-containing compound. In 0018 Note that according to the nomenclature of Chemi preferred instances, the target compound(s) of the invention cal Abstract Index Name, for example, CHs SFC1 is include one or more oxygen atom(s) and/or one or more named Sulfur, chlorotetrafluorophenyl-, p-CH CH oxygen-containing group(S), and/or one or more Sulfur atom SFC1 is named sulfur, chlorotetrafluoro(4-methylphenyl)-; (s) and/or one or more Sulfur-containing group(s) for selec and p-NO C.H. SFC1 is named sulfur, chlorotet tive replacement by the fluorine atom(s). The target com rafluoro(4-nitrophenyl)-. pound(s) of the invention also include other functional groups 0019 Arylsulfur halotetrafluoride compounds as repre or moieties for substitution or addition by one or more fluo sented by the formula (I) are stable and insensitive to mois rine atoms. In some cases, the fluorination may occur with ture, and thus safe and easy to handle. Phenylsulfur chlorotet other halogenation such as chlorination. Preferred illustrative rafluoride maintains high stability on contact with water. target compounds include alcohols, silyl ethers, aldehydes, When a solution of phenylsulfur chlorotetrafluoride in chlo ketones, carboxylic acids, acid halides, esters, acid anhy roform-d is contacted with water at room temperature, about drides, amides, imides, epoxides, lactones, lactams, Sulfonic 74% of phenylsulfur chlorotetrafluoride remains after 3 acids, sulfinic acids, sulfinyl halides, Sulfenic acids, Sulfenyl hours, and the half life time of phenylsulfur chlorotetrafluo halides, thiols, , Sulfoxides, thioketones, thioesters, ride in chloroform-d in contact with water is estimated to be dithioesters, thiocarboxylic acids, thiocarbonyl halides, approximately 8 hours. Conventional fluorinating agents dithiocarboxylic acids, thiocarbonates, dithiocarbonates, such as DAST, Deoxo-Fluor, and phenylsulfur trifluoride trithiocarbonates, thioketals, dithioketals, thioacetals, dithio decompose immediately and violently with Sound emission acetals, thioamides, thiocarbamates, dithiocarbamates, and fume production when placed in contact with water. orthothioesters, phosphines, phosphine oxides, phosphine When a solution of useful fluorinating agent, 4-tert-butyl-2, Sulfides, phosphonic acids, and other like compounds, and 6-dimethylphenylsulfur trifluoride (see, for example, U.S. salts thereof. Pat. No. 7,381,846 B2) in a solvent (chloroform-d) is con 0014 Typical fluorination processes herein include: a one tacted with water, immediate decomposition occurs. There step process, a one-step process with reducing agent, and a fore, the arylsulfur halotetrafluorides of the invention is easily two-step process with a reducing Substance. isolated during production and can easily be used as a fluori 0015. In general, the invention provides processes for nating agent. In one embodiment, the arylsulfur halofluorides introducing one or more fluorine atoms into a target com are prepared at low cost by treating the corresponding diary1 pound with arylsulfur halotetrafluoride represented by the disulfides or arylthiols with chlorine (Cl) in the presence of formula (I): a metal fluoride (see Examples 1-12). 0020. With reference to Formula (I) again (including the trans and cis-isomers): Preferably, X is a chlorine atom from (I) a viewpoint of cost. (0021. A halogen atom of R', R. R. R. or R refers to a fluorine, chlorine, bromine, or iodine atom. Among them, fluorine, chlorine, and bromine atoms are preferable, and R3 SFX chlorine is most preferable from a viewpoint of cost. (0022. When used herein, the term “alkyl” includes all straight, branched, and cyclic isomers. Representative examples of alkyl groups having one to ten carbon atoms 0016 wherein X is a chlorine atom, bromine atom, or include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, iodine atom, and R',R,R,R, and Reach is independently isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, a hydrogen atom, a halogen atom, a Substituted or unsubsti tert-pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, tuted alkyl group having one to ten carbon atoms, a nitro nonyl, decyl, and so on. More preferred alkyl groups have one group, a cyano group, a Substituted or unsubstituted aryl to four carbon atoms, and methyl, ethyl, propyl, isopropyl. group having six to sixteen carbon atoms, a Substituted or butyl, isobutyl, sec-butyl, tert-butyl are exemplified. Among unsubstituted alkanesulfonyl group having one to ten carbon them, methyl and tert-butyl are furthermore preferred. atoms, a Substituted or unsubstituted arenesulfonyl having six 0023 Preferred substituted alkyl groups include; fluori to sixteen carbonatoms, a Substituted or unsubstituted alkoxy nated and/or chlorinated alkyl groups such as CF, CC1, group having one to ten carbonatoms, a Substituted or unsub CFH, CFH, CCIH, and CFCF, and alkoxy-substituted stituted aryloxy group having six to sixteen carbon atoms, or alkyl groups such as CHOCH, CHCHOCH, a SF's group. CHCHCHOCH, (CH)CHOCH, CH(CH) 0017 Arylsulfur halotetrafluoride compounds of formula CHOCH, (CH) CHCHOCH, CHCH(CH.) (I) include isomers such as trans-isomers and cis-isomers as CHOCH, CHOCHCH, and CHCHOCHCH. shown below: arylsulfur halotetrafluoride is represented by 0024 Substituted and unsubstituted aryl groups herein have six to sixteen carbon atoms. The term “aryl' includes ArSFX: phenyland naphthyl, with preferred aryl groups being phenyl. Preferred substituted aryl groups include: alkylated, fluori F F nated, chlorinated, brominated, nitrated, and/or trifluorom V / V / ethylated phenyl groups such as methylphenyl, ethylphenyl, Air-S-X Air-S-X A V / V propylphenyl, butylphenyl, dimethylphenyl, fluorophenyl, F F X F chlorophenyl, nitrophenyl, (trifluoromethyl)phenyl, and so trans-Isomer cis-Isomer O 0025. Substituted and unsubstituted alkanesulfonyl groups have one to ten carbon atoms. The term "alkanesulfo US 2011/0160488 A1 Jun. 30, 2011 nyl' is a binding of “alkyl described above and a sulfonyl independently selected from a group consisting of a halogen (SO) group, that is, alkylsulfonyl. As “alkyl in alkanesulfo atom, a substituted or unsubstituted linear or branched alkyl nyl (alkylsulfonyl) group, these are exemplified the same as group having one to four carbonatoms, and a nitro group, and alkyl above. Preferred examples of alkanesulfonyl groups the remainders of R. R. R. R. and Rare a hydrogenatom. include CHSO, CH (CH),SO (n=1-3), (CH). CHSO, Additionally preferably, arylsulfur halotetrafluoride is CHCH(CH)CHSO, and (CH),CHCHSO. Preferred selected form a group consisting of arylsulfur chlorotet examples of substituted alkanesulfonyl groups include fluori rafluorides in which R', R. R. R', and Rare all a hydrogen nated alkanesulfonyl groups such as CFSO. atom and at maximum three of R', R. R. R. and Reach is 0026. Substituted and unsubstituted arenesulfonyl groups independently selected from a group consisting of a halogen herein have six to sixteen carbon atoms. The term “arene atom, a substituted or unsubstituted linear or branched alkyl sulfonyl is a binding of “aryl' described above and a sulfonyl group having one to four carbonatoms, and a nitro group, and (SO) group, that is, arylsulfonyl. For “aryl' in arenesulfonyl the remainders of R', R,R,R, and Rarea hydrogenatom. (arylsulfonyl) group, these are exemplified the same as aryl 0031. Furthermore preferably embodiments herein above. Arylsulfonyl groups include phenylsulfonyl and naph include, arylsulfur halotetrafluoride selected from a group thylsulfonyl, with preferred arylsulfonyl groups being phe consisting of phenylsulfur chlorotetrafluoride, o-, m-, and nylsulfonyl. Preferred examples of substituted arenesulfonyl p-alkylphenylsulfur chlorotetrafluoride wherein the alkyl is a groups include alkylated, fluorinated, chlorinated, bromi linear or branched alkyl group having one to four carbon nated, nitrated, and/or trifluoromethylated phenylsulfonyl atoms, o-, m-, and p-fluorophenylsulfur chlorotetrafluorides, groups, e.g. methylphenylsulfonyl, dimethylphenylsulfonyl, o-, m-, and p-chlorophenylsulfur chlorotetrafluorides, o-, m-, fluorophenylsulfonyl, chlorophenylsulfonyl, bromophenyl and p-bromophenylsulfur chlorotetrafluorides, o-, m-, and Sulfonyl, and nitrophenylsulfonyl. p-nitrophenylsulfur chlorotetrafluoride, and each isomer of 0027 Substituted and unsubstituted alkoxyl groups herein difluorophenylsulfur chlorotetrafluoride. Isomers of difluo have one to ten carbonatoms. The term “alkoxy” is a binding rophenylsulfur chlorotetrafluorides include 2.3-, 2,4-, 2.5-2. of “alkyl described above and an oxygenatom, that is, alky 6-, 3,4-, and 3,5-difluorophenylsulfur chlorotetrafluorides. loxyl. Representative examples of alkoxy (alkyloxy) groups Among these, phenylsulfur chlorotetrafluoride, p-meth having one to ten carbon atoms include CHO, CH (CH), O ylphenylsulfur chlorotetrafluoride, p-(tert-butyl)phenylsul (n=1-9), (CH),CHO, (CH) CHCHO, CHCH (CH) fur chlorotetrafluoride, p-fluorophenylsulfur chlorotetrafluo CHO, (CH),CO, CHCH (CH)CHCHO, and (CH) ride, p-chlorophenylsulfur chlorotetrafluoride, CCHO. More preferred alkoxyl groups have one to four p-bromophenylsulfur chlorotetrafluoride, and p-nitrophenyl carbonatoms, and CHO, CHCHO, CHCH2CH2O, (CH) sulfur chlorotetrafluoride are more preferable, and phenylsul CHO, CHCHCHCHO, CHCH (CH)CHO, (CH) fur chlorotetrafluoride, p-methylphenylsulfur chlorotet CHCHO, and (CH)CO are exemplified. rafluoride, p-(tert-butyl)phenylsulfur trifluoride, 0028 Preferred substituted alkoxyl groups include: fluori p-chlorophenylsulfur chlorotetrafluoride, and p-nitrophenyl nated and/or chlorinated alkoxyl groups such as CFO, sulfur chlorotetrafluoride are furthermore preferable, and CFCHO, CC1, CHO, CFCFO, CFHCFO, and (CF) additionally, phenylsulfur chlorotetrafluoride is most prefer CHO, and alkoxy-Substituted alkoxy groups such as able because of cost. CHOCHCHO. 0032. In one embodiment, a one-step process for introduc 0029 Substituted and unsubstituted aryloxy groups herein ing one or more fluorine atoms into a target compound is have six to sixteen carbon atoms. The term “aryloxy' is a provided comprising contacting a target compound with aryl binding of “aryl” described above and an oxygen atom. As sulfur halotetrafluoride represented by the formula (I). With “aryl” in aryloxy group, which is exemplified the same as aryl respect to compounds represented by formula (I): above. Aryloxy groups include phenyloxy and naphthyloxy, with preferred aryloxyl groups being phenyloxyl. Preferred examples of Substituted aryloxy groups include alkylated, (I) fluorinated, chlorinated, brominated, nitrated, and/or trifluo romethylated phenyloxy groups such as methylphenyloxy, fluorophenyloxy, chlorophenyloxy, bromophenyloxy, nitro R3 SFX phenyloxy, and (trifluoromethyl)phenyloxy. 0030 Preferably, from a cost perspective, arylsulfur hal otetrafluoride is selected from a group consisting of arylsulfur halotetrafluorides in which R', R. R. R', and Reach is independently selected from a group consisting of a hydrogen 0033 X, R. R. R. R. and Rare the same as described atom, a halogenatom, a Substituted or unsubstituted linear or and exemplified above. branched alkyl group having one to four carbonatoms, and a 0034. This method is a one-step fluorination of a target nitro group. More preferably, arylsulfur halotetrafluoride is compound with an arylsulfur halotetrafluoride. selected from a group consisting of arylsulfur chlorotet 0035. The target compounds are described as above. rafluorides in which R', R. R. R', and Reach is indepen Among them, preferable target compounds for this one-step dently selected from a group consisting of a hydrogen atom, fluorination are Sulfur-containing compounds such as thioke a halogen atom, a Substituted or unsubstituted linear or tones, thioesters, dithioesters, thiocarboxylic acids, thiocar branched alkyl group having one to four carbonatoms, and a bonylhalides, dithiocarboxylic acids, thiocarbonates, dithio nitro group. Furthermore preferably, arylsulfur halotetrafluo carbonates, trithiocarbonates, thioketals, dithioketals, ride is selected form a group consisting of arylsulfur halotet thioacetals, dithioacetals, thioamides, thiocarbamates, rafluorides in which R', R. R. R. and Rare all a hydrogen dithiocarbamates, orthothioesters, sulfenyl halides, thiols, atom and at maximum three of R', R. R. R. and Reach is Sulfides, and other like compounds. US 2011/0160488 A1 Jun. 30, 2011

0036. The arylsulfur halotetrafluorides are described perfluoropentane, perfluorohexane, perfluoroheptane, per above. fluorooctane, perfluorononane, and perfluorodecane; per 0037. In some cases, the one-step fluorination is con fluorodecalin; and other like compounds. Illustrative ethers ducted in the presence of an acid such as a Brónsted acid or a include diethyl ether, dipropyl ether, di(isopropyl)ether, dibu Lewis acid in order to accelerate reaction or to increase fluo tyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane, rination yields. The amount of acid used in any given reaction glyme (1,2-dimethoxyethane), diglyme, triglyme, and other depends on the target compound(s), other chemical com like compounds. Illustrative nitriles include acetonitrile, pro pounds and/or reaction conditions. Preferably, the Brönsted pionitrile, benzonitrile, and other like compounds. Illustrative acid is at least one member selected from a group consisting aromatics include benzene, toluene, Xylene, and other like of (HF), HBF, HBC1, HBFC1, HSbF, compounds. Illustrative nitro compounds include HSbFC1, HSbF, HSbFC1s, HSbFC1, HN(SOCF), and nitromethane, nitroethane, nitrobenzene, and other like com other like acids, and their complexes with organic compounds pounds. Illustrative esters include methylacetate, methyl pro Such as ethers, amines, and so on, and mixtures thereof. As pionate, ethyl acetate, ethyl propionate, propyl acetate, iso complexes of HF with amines, there are preferably exempli propyl acetate, butyl acetate, isobutyl acetate, Sec-butyl fied a mixture of HF and pyridine, a mixture of HF and C. B. acetate, tert-butyl acetate, and other like compounds. and/or Y-methylpyridine, a mixture of HF and dimethylpyri 0041 Preferably, reaction temperature for fluorination can dine, a mixture of HF and trimethylpyridine, a mixture of HF be selected in the range of about -80° C. to about +200°C., and trimethylamine, a mixture of HF and triethylamine, and and more preferably, about -50° C. to about +150° C. The so on. Among complexes with amines, an about 70:30 wt % reaction temperature depends on the use of arylsulfur halotet mixture of HF and pyridine, a 3:1 molar ratio mixture of HF rafluorides, target compounds, Solvents, catalysts and/or and triethylamine, and a 5:1 molar ratio mixture of HF and additives. Therefore, the temperature is determined from the triethylamine are more preferable because of availability. reaction conditions necessary for the reaction. Preferably, Lewis acids used herein include a member 0042. The reaction time is also dependent on reaction tem selected from a group consisting of BF, BC1, SbF, SbCl, perature, target compounds, arylsulfur halotetrafluorides, SbF, SbCl, SbFC1, SnCl4, SnF, SnClF. TiFi, TiCl, and Solvents, catalysts or additives, and their amounts used. other like acids, and their complexes with organic compounds Therefore, one can choose the time necessary for completing Such as ethers, nitriles, and so on, as well as mixtures thereof. each reaction by modifying one or more these parameters, but As the preferred complexes, BF, etherates are exemplified. is generally from about 1 minute to several days, and is 0038. In some cases, the one-step fluorination is con preferably within a few days. ducted in the presence of a base in order to increase produc 0043. In another embodiment, a one-step process with tion yields, or when starting materials and/or products are reducing agent is provided for introducing one or more fluo sensitive to acid conditions. Preferable bases are exemplified rine atoms into a target compound, comprising contacting a with metal such as , potassium fluo target compound with arylsulfur halotetrafluoride repre ride, cesium fluoride, and other like compounds; carbonates sented by the formula (I) in the presence of a reducing Sub Such as sodium carbonate, sodium bicarbonate, potassium Stance. carbonate, potassium bicarbonate, and other like compounds. The amount of base used in any given reaction depends on the 0044) This method is a one-step fluorination of a target target compound(s), other chemical compounds and/or reac compound with an arylsulfur halotetrafluoride in the presence tion conditions. of a reducing Substance. 0039. The amount used of arylsulfur halotetrafluoride is 0045. The target compounds and arylsulfur halotetrafluo dependent on the kind and nature of the target compound and rides are described as above. reaction conditions such as temperature, solvent, and catalyst 0046. A reducing substance in accordance with this or additive used. Therefore, one can choose the amount nec embodiment is an element or an organic or inorganic com essary for obtaining an adequate yield of the fluorinated com pound which reduces arylsulfur halotetrafluoride of the for pound from the target compound in each reaction. An illus mula (I) used in the reaction or of which reduction potential is trative amount used of arylsulfur halotetrafluoride per one lower than that of arylsulfur halotetrafluoride of the formula mole of a target compound is from about 0.5 moles to about (I) used in the reaction. One or more reducing compounds can ten moles and more typically about one mole to about five be used in a reaction. moles. 0047 Reducing substances herein include elements such 0040 Fluorination is conducted in the presence or absence as: metals such as alkali metals (elements in Group 1 of the of a solvent. In some cases, reaction can preferably be con Periodic Table), alkali earth metals (elements in Group 2 of ducted without a solvent. In other cases, solvent may be used the Periodic Table), transition metals and inner transition for mild or selective fluorination, and solvent is preferably metals (elements in Groups 3-12 of the Periodic Table), and selected from the group consisting of hydrocarbons, halocar metals in Groups 13-15 of the Periodic Table such as Al, Ga. bons, ethers, nitriles, aromatics, nitro compounds, esters, and In, T1, Sn, Pb, and Bi; semi-metals such as B, Si, Ge. As, Sb, mixtures thereof. Example hydrocarbons include normal, Te, Po, and At; nonmetal elements in Groups 13-17 of the branched, cyclic isomers of pentane, hexane, heptane, octane, Periodical Table (C. P. S. Se, I, and so on). Among these, nonane, decane, dodecane, undecane, and other like com preferred elements are alkali metals, alkali earth metals, tran pounds. Illustrative halocarbons include; dichloromethane, sition metals, metals in Groups 13-15 of the Periodic Table, chloroform, carbon tetrachloride, dichloroethane, trichloro semi-metals, and nonmetals. ethane, terachloroethane, trichlorotrifluoroethane, chlo 0048 Reducing substances herein also include inorganic robenzene, dichlorobenzene, trichlorobenzene, hexafluo compounds such as; hydrogen, metal compounds, semi-metal robenzene, benzotrifluoride, and bis(trifluoromethyl) compounds, and nonmetal compounds. Among these, pre benzene; normal, branched, cyclic isomers of ferred inorganic compounds include; metal salts; semi-metal US 2011/0160488 A1 Jun. 30, 2011

salts; nonmetal salts; inorganic chloride salts; inorganic bro 0055 Preferred substituted and unsubstituted aromatic mide salts; inorganic iodide salts; ammonia (NH); inorganic hydrocarbons are exemplified with benzene, toluene, xylene, Sulfur compounds; and so on. mesitylene, durene, hexamethylbenzene, anisole, dimethoxybenzene, aniline, N,N-dimethylaniline, phe 0049 Preferred inorganic chloride salts are exemplified nylenediamine, phenol, salts of phenol, hydrobenzoquinone, with metal chlorides (LiCl, NaCl, KC1, RbCl, CsCl, MgCl, naphthalene, indene, anthracene, phenanthrene, pyrene, and MgClF, CaCl, TiCl, VC1, CrCl FeC1, CuC1, SnCl2, and SO. O. other metal salts containing chloride anions), ammonium 0056 Preferred substituted and unsubstituted heteroaro chloride, and otherinorganic salts containing chloride anions. matic compounds are exemplified with pyridine, methylpy Preferred inorganic bromide salts are exemplified with metal ridine, dimethylpyridine, trimethylpyridine, fluoropyridine, bromides (LiBr, NaBr, KBr, RbBr, CsBr, MgBr, MgBrC1, chloropyridine, dichloropyridine, pyrrole, indole, quinoline, MgBrF, CaBr, FeBr, CuBr, SnBr, and other metal salts isoquinoline, carbazole, imidazole, pyrimidine, pyridazine, containing bromide anions), ammonium bromide, and other pyrazine, triazole, furan, benzofuran, thiophene, ben inorganic salts containing bromide anions. Preferred inor Zothiophene, thiazole, phenothiazine, phenoxazine, and so ganic iodide salts are exemplified with metal iodides (LiI. O. NaI, KI, Rb, CsI, Mg1, MgBrI, MgClI. MgFI, Cal, FeI. 0057 Preferred substituted and unsubstituted unsaturated CuI, SnI, and other metal salts containing iodide anions), aliphatic hydrocarbons are exemplified with; substituted and ammonium iodide, and other inorganic salts containing unsubstituted alkenes such as ethylene, propene, butene, iodide anions. Preferred inorganic Sulfur compounds are isobutylene, 2-methyl-2-butene, 2,3-dimethyl-2-butene, 2.3- exemplified with hydrogen , salts of hydrogen sulfide, dimethyl-1-butene, butadiene, pentene, 2-methyl-1-pentene, salts of sulfide, salts of hydrogen sulfite, salts of sulfite, salts 2-methyl-2-pentene, hexene, cyclohexene, 1-methyl-1-cy of thiosulfate, salts of , and other inorganic com clohexene, 1,2-dimethyl-1-cyclohexene, 2-N,N-diethy pounds containing Sulfur (valence state II or IV). lamino-1-propene, 1-N,N-dimethylamino-1-cyclohexene, 0050. Among these, more preferred inorganic compounds 1-N,N-diethylamino-1-cyclohexene, 1-pyrrolidino-1-cyclo include: inorganic chloride salts, inorganic bromide salts, and hexene, 1-pyrrolidino-1-cyclopentene, styrene, C- and B-me inorganic iodide salts. thylstyrene, Stilbene, 2-methoxy-1-propene (methyl 2-prope 0051 Preferred reducing substances also include organic nyl ether), ethyl vinyl ether, 2,3-dihydrofuran, 2,3-dihydro compounds Such as: organic chloride salts, organic bromide 5-methylfuran, 3,4-dihydro-2H-pyran, and so on; and salts, organic iodide salts, Substituted and unsubstituted aro Substituted and unsubstituted alkynes such as acetylene, pro matic hydrocarbons, Substituted and unsubstituted heteroaro pyne, phenylacetylene, diphenylacetylene, and so on. matic compounds, Substituted and unsubstituted unsaturated 0.058 Preferred substituted and unsubstituted nitrogen aliphatic hydrocarbons, substituted and unsubstituted nitro containing aliphatic hydrocarbons are exemplified with gen-containing aliphatic hydrocarbons, organic Sulfur com methylamine, ethylamine, diethylamine, triethylamine, pro pounds, organic selenium compounds, organic phosphorous pylamine, butylamine, pyrrolidine, N-methylpyrrolidine, compounds, salts or complexes of Substituted or unsubsti piperidine, N-methylpiperidine, morpholine, N-methylmor tuted heteroaromatic compounds and hydrogen fluoride pholine, ethylenediamine, N.N.N'N'-tetramethylethylenedi (HF), salts or complexes of substituted or unsubstituted nitro amine, triethylenediamine, urea, tetramethylurea, and so on. gen-containing aliphatic hydrocarbons and hydrogen fluoride 0059 Preferred salts or complexes of substituted and (HF), and so on. unsubstituted heteroaromatic compounds and hydrogen fluo 0052 Preferred organic chloride salts are exemplified ride (HF), are exemplified with pyridine. HF, pyridine. 2HF, with methylammonium chloride, dimethylammonium chlo pyridine. 3HF, methylpyridine.HF, dimethylpyridine.HF, tri ride, trimethylammonium chloride, tetramethylammonium methylpyridine.HF, and so on. chloride, ethylammonium chloride, diethylammonium chlo 0060 Preferred salts or complexes of nitrogen-containing ride, triethylammonium chloride, tetraethylammonium chlo aliphatic hydrocarbons and hydrogen fluoride (HF), are ride, propylammonium chloride, tripropylammonium chlo exemplified with triethylamine.HF, triethylamine.2HF, tri ride, tetrapropylammonium chloride, butylammonium ethylamine.3HF, triethylamine.4HF, triethylamine.5HF, tri chloride, tributylammonium chloride, tetrabutylammonium methylamine.HF, and so on. chloride, anilinium chloride, N,N-dimethylanilinium chlo 0061 Preferred organic sulfur compounds are exemplified ride, pyridinium chloride, N-methylpyridinium chloride, pyr with organic Sulfides, organic disulfides, organic polysul rolidinium chloride, piperidinium chloride, and other organic fides, organic Sulfenyl halides, and organic thiols and their salts containing chloride anions. salts. 0053 Preferred organic bromide salts are exemplified 0062 Preferred organic sulfides are exemplified with dim with methylammonium bromide, dimethylammonium bro ethylsulfide, diethylsulfide, dipropyl sulfide, dibutyl sulfide, mide, trimethylammonium bromide, tetramethylammonium di(tert-butyl) sulfide, tetrahydrothiophene, methyl phenyl bromide, triethylammonium bromide, tetraethylammonium sulfide, trimethylsilyl phenyl sulfide, diphenyl sulfide, bis(o, bromide, tripropylammonium bromide, tributylammonium m, and p-methylphenyl) sulfides, bis(o, m, and p-ethylphe bromide, tetrabutylammonium bromide, pyridinium bro nyl) sulfide, bis(o, m, and p-n-propylphenyl)sulfide, bis(O. m. mide, and other organic salts containing bromide anions. and p-isopropylphenyl)sulfide, bis(o, m, and p-butylphenyl) 0054 Preferred organic iodide salts are exemplified with Sulfide, bis(o, m, and p-isobutylphenyl) sulfide, bis(o, m, and methylammonium iodide, dimethylammonium iodide, trim p-sec-butylphenyl) sulfide, bis(o, m, and p-tert-butylphenyl) ethylammonium iodide, tetramethylammonium iodide, tri sulfide, each isomer of bis(dimethylphenyl) sulfide, each iso ethylammonium iodide, tetraethylammonium iodide, tributy mer of bis(trimethylphenyl) sulfide, bis(4-tert-butyl-2,6-dim lammonium iodide, tetrabutylammonium iodide, pyridinium ethylphenyl) sulfide, bis(O. m., and p-fluorophenyl) sulfides, iodide, and other organic salts containing iodide anions. bis(o, m, and p-chlorophenyl) sulfide, bis(o, m, and p-bro US 2011/0160488 A1 Jun. 30, 2011

mophenyl) sulfide, bis(o, m, and p-iodophenyl) sulfides, bis unsubstituted aromatic hydrocarbons, Substituted and unsub (o, m, and p-nitrophenyl) sulfide, and so on. stituted heteroaromatic compounds, Substituted and unsub 0063 Preferred organic disulfides are exemplified with stituted unsaturated aliphatic hydrocarbons, Substituted and dimethyl disulfide, diethyl disulfide, diisopropyl disulfide, unsubstituted nitrogen-containing aliphatic hydrocarbons, di(tert-butyl) disulfide, diphenyl disulfide, bis(o, m, and organic Sulfur compounds, salts or complexes of Substituted p-methylphenyl) disulfides, bis(o, m, and p-ethylphenyl) dis or unsubstituted heteroaromatic compounds and hydrogen ulfide, bis(o, m, and p-n-propylphenyl) disulfide, bis(o, m, fluoride, and salts or complexes of substituted or unsubsti and p-isopropylphenyl) disulfide, bis(o, m, and p-butylphe tuted nitrogen-containing aliphatic hydrocarbons and hydro nyl) disulfide, bis(o, m, and p-isobutylphenyl) disulfide, bis gen fluoride. (o, m, and p-sec-butylphenyl) disulfide, bis(o, m, and p-tert 0070 Arylsulfur halotetrafluoride of the formula (I) may butylphenyl) disulfide, each isomer of bis(dimethylphenyl) be derived by an existing reducing Substance to another com disulfide, each isomer of bis(trimethylphenyl) disulfide, bis pound(s) that can more effectively fluorinate a target com (4-tert-butyl-2,6-dimethylphenyl) disulfide, bis(o, m, and pound. The compound(s) includes any derived compounds p-fluorophenyl) disulfides, bis(o, m, and p-chlorophenyl) dis that can fluorinate a target compound. A preferable derived ulfide, bis(o, m, and p-bromophenyl) disulfide, bis(o, m, and compound is an arylsulfur trifluoride represented by the for p-iodophenyl) disulfides, bis(o, m, and p-nitrophenyl) disul mula (II) shown below. fide, and so on. 0071. In one embodiment, preferred reducing substance 0064 Preferred organic polysulfides are exemplified with herein is a substance which reduces arylsulfur halotetrafluo diphenyl trisulfide, dimethyl trisulfide, and so on. ride of the formula (I) to arylsulfur trifluoride represented by 0065 Preferred organic sulfenyl halides are exemplified the formula (II): with phenylsulfenyl fluoride, phenylsulfenyl chloride, phe nylsulfenyl bromide, phenylsulfenyl iodide, phenylsulfinyl chloride, o, m, and p-methylphenylsulfenyl chloride, o, m, (II) and p-ethylphenylsulfenyl chloride, o, m, and p-n-propylphe nylsulfenyl chloride, o, m, and p-isopropylphenylsulfenyl chloride, o, m, and p-butylphenylsulfenyl chloride, o, m, and p-isobutylphenylsulfenyl chloride, o, m, and p-sec-butylphe nylsulfenyl chloride, o, m, and p-tert-butylphenylsulfenyl chloride, 2,4-dimethylphenylsulfenyl chloride, 2,5-dimeth ylphenylsulfenyl chloride, 2,4,6-trimethylphenylsulfenyl chloride, 4-tert-butyl-2,6-dimethylphenylsulfenyl chloride, 0072 in which R', R. R. R', and R are the same as o, m, and p-fluorophenylsulfenyl chloride, o, m, and p-chlo described above. rophenylsulfenyl chloride, o, m, and p-bromophenylsulfenyl 0073. A further preferred reducing substance is a sub chloride, o, m, and p-iodophenylsulfenyl chloride, o, m, and stance which reduces arylsulfur halotetrafluoride of the for p-nitrophenylsulfenyl chloride, and so on. mula (I) to arylsulfur trifluoride represented by the formula 0066 Preferred organic thiols and their salts are exempli (II) in high yields without reducing or with limited reducing fied with methanethiol, ethanethiol, propanethiol, isopro arylsulfur trifluoride represented by the formula (II). panethiol, butanethiol, sec-butanethiol, isobutanethiol, tert 0074. In this aspect, reducing substances include the same butanethiol, thiophenol, o, m, and p-methylbenzenethiols, o, reducing Substances as above. Preferred reducing Substances m, and p-ethylbenzenethiol, o, m, and p-n-propylben include; the elements such as alkali metals, alkali earth met Zenethiol, o, m, and p-isopropylbenzenethiol, o, m, and p-bu als, transition metals, metals in Groups 13-15 of the Periodic tylbenzenethiol, o, m, and p-isobutylbenzenethiol, o, m, and Table, and semi-metals; inorganic compounds Such as inor p-sec-butylbenzenethiol, o, m, and p-tert-butylbenzenethiol, ganic chloride salts, inorganic bromide Salts, inorganic iodide each isomers of dimethylbenzenethiol, each isomer of trim salts; and the organic compounds such as organic chloride ethylbenzenethiol, 4-tert-butyl-2,6-dimethylbenzenethiol, o, salts, organic bromide salts, organic iodide salts, Substituted m, and p-chlorobenzenethiols, o, m, and p-fluorobenzenethi and unsubstituted aromatic hydrocarbons, Substituted and ols, o, m, and p-bromobenzenethiols, o, m, and p-iodoben unsubstituted heteroaromatic compounds, Substituted and Zenethiol, o, m, and p-nitrobenzenethiol, and metal salts, unsubstituted unsaturated aliphatic hydrocarbons, Substi ammonium salts, phosphonium salts of these organic thiols. tuted and unsubstituted nitrogen-containing aliphatic hydro 0067 Preferred organic selenium compounds are exem carbons, organic Sulfur compounds, salts or complexes of plified with benzeneselenol, diphenyl selenide, diphenyl dis Substituted or unsubstituted heteroaromatic compounds and elenide, and so on. hydrogen fluoride, and salts or complexes of Substituted or 0068 Preferred organic phosphorous compounds are unsubstituted nitrogen-containing aliphatic hydrocarbons exemplified with trimethylphosphine, triethylphosphine, and hydrogen fluoride; and mixtures thereof. tripropylphosphine, tributylphosphine, triphenylphosphine, 0075. As more preferred reducing substances, there are trimethylphosphite, triethylphosphite, tripropylphosphite, exemplified alkali metals, alkali earth metals, transition met tributylphosphite, triphenylphosphite, and so on. als, metals in Groups 13-15 of the Periodic Table, semi 0069 Preferred reducing substances in general include: metals, inorganic chloride Salts, inorganic bromide salts, the elements such as alkali metals, alkali earth metals, tran inorganic iodide salts, organic bromide salts, organic iodide sition metals, metals in Groups 13-15 of the Periodic Table, salts, Substituted and unsubstituted aromatic hydrocarbons, and semi-metals; the inorganic compounds such as inorganic Substituted and unsubstituted heteroaromatic compounds, chloride Salts, inorganic bromide salts, inorganic iodide salts; Substituted and unsubstituted unsaturated aliphatic hydrocar and the organic compounds such as organic chloride salts, bons, Substituted and unsubstituted nitrogen-containing ali organic bromide salts, organic iodide salts, Substituted and phatic hydrocarbons, organic Sulfur compounds, salts or US 2011/0160488 A1 Jun. 30, 2011

complexes of substituted or unsubstituted heteroaromatic halocarbons, ethers, nitriles, aromatics, nitro compounds, compounds and hydrogen fluoride, and salts or complexes of esters, and mixture thereof. These solvents are exemplified as Substituted or unsubstituted nitrogen-containing aliphatic described above. hydrocarbons and hydrogen fluoride, and mixtures thereof. I0081 Preferably, reaction temperature for the fluorination can be selected from the range of about -80° C. to about 0076. The amount used of reducing substance is depen +200° C., and more preferably, about -50° C. to about +150° dent on the kind and nature of the reducing Substance and C. The reaction temperature is dependent on the arylsulfur reaction conditions such as temperature and solvent in addi halotetrafluorides, reducing Substances, target compounds, tion to arylsulfur halotetrafluorides. Therefore, one can Solvents, and catalysts or additives used. Therefore, one can choose the amount necessary for obtaining an adequate yield choose the temperature necessary for the reaction. of the fluorinated compound in each reaction. An illustrative I0082. The reaction time is also dependent on reaction tem amount used of reducing Substance per one mole of an aryl perature, arylsulfur halotetrafluorides, reducing Substances, sulfur halotetrafluoride is from about 0.1 moles to about ten target compounds, Solvents, catalysts or additives, and their moles and more typically about 0.1 moles to about five moles. amounts used. Therefore, one can choose the time necessary 0077. The amount used of arylsulfur halotetrafluoride is for completing each reaction by modifying one or more of dependent on the kind and nature of the target compound or these parameters, but can be from about 1 minute to several reducing Substance and reaction conditions such as tempera days, and is preferably within a few days. ture and solvent. Therefore, one can choose the amount nec I0083. In another embodiment, a two-step process is pro essary for obtaining an adequate yield of the fluorinated com vided for introducing one or more fluorine atoms into a target pound from the target compound in each reaction. An compound comprising (step 1) contacting arylsulfur halotet illustrative amount used of arylsulfur halotetrafluoride per rafluoride represented by the formula (I) shown above with a one mole of a target compound is from about 0.5 moles to reducing substance that reduces the arylsulfur halotetrafluo about ten moles and more typically about one mole to about ride; and (step 2) contacting a target compound with the five moles. resulting mixture from step 1. 0078. In some cases, fluorination is conducted in the pres I0084. This method consists of two processes; the first step ence of an acid Such as a Brónsted acid or a Lewis acid in being a reaction of an arylsulfur halotetrafluoride with a order to accelerate reaction or to increase fluorination yields. reducing Substance, and the second step fluorination of a The amount of acid used in any given reaction depends on the target compound with the resulting mixture. target compound(s), other chemical compounds and/or reac I0085. In the first step, arylsulfur halotetrafluoride of the tion conditions. Preferably, the Brönsted acid is at least one formula (I) may be derived by a reducing Substance to another member selected from a group consisting of hydrogen fluo compound(s) that can more effectively fluorinate a target ride (HF), HBF, HBC1, HBFC1, HSbF, HSbFC1, HSbF. compound. The compound(s) includes any derived com HSbFC1s, HSbFC1, HN(SOCF), and other like acids, pounds that can fluorinate a target compound. A preferable and their complexes with organic compounds Such as ethers derived compound is an arylsulfur trifluoride represented by and amines. Complexes of HF with amines are preferably the formula (II) shown below. illustrated as mixtures of HF and pyridine, a mixture of HF I0086 A preferred reducing substance in this two-step and C, B, and/or Y-methylpyridine, a mixture of HF and dim reaction is a Substance which reduces arylsulfur halotet ethylpyridine, a mixture of HF and trimethylpyridine, a mix rafluoride of the formula (I) to arylsulfur trifluoride repre ture of HF and trimethylamine, a mixture of HF and triethy sented by formula (II): lamine, and so on. Among complexes with amines, an about 70:30 wt % mixture of HF and pyridine, a 3:1 molar ratio mixture of HF and triethylamine, and a 5:1 molar ratio mix (II) ture of HF and triethylamine are more preferable because of availability. Preferably, the Lewis acid is at least one member selected from a group consisting of BF, BC1, SbF5, SbCl, SbF, SbCl, SbFC1, SnCl4, SnF, SnClF. TiFi, TiCl, and other like acids, and their complexes with organic compounds Such as ethers, nitriles, and so on. As the preferred complexes, BF, etherates can be exemplified. 0079. In some cases, fluorination is conducted in the pres I0087 in which R', R. R. R', and R are the same as ence of a base in order to increase production yields, or when previously described. starting materials and/or products are sensitive to acid condi I0088. In this alternative aspect, the method consists of two tions. Preferable bases are exemplified by metal fluorides processes; the first step is a reaction of an arylsulfur halotet Such as sodium fluoride, , cesium fluoride, rafluoride with a reducing substance to form an arylsulfur and other like compounds; carbonates such as sodium car trifluoride; the second is the fluorination of a target compound bonate, Sodium bicarbonate, potassium carbonate, potassium with the reaction mixture obtained from the first step. bicarbonate, and other like compounds. The amount of base I0089. The arylsulfur halotetrafluorides are described as used in any given reaction depends on the target compound above. (s), other chemical compounds and/or reaction conditions. 0090 Reducing substances usable in this embodiment are 0080. The fluorination is typically conducted in the pres the same as described above. The amount used of reducing ence or absence of a solvent. In some cases, reaction can be Substance is dependent on the kind and nature of the reducing preferably conducted without a solvent. In other cases, sol Substance and reaction conditions such as temperature and vent is used for mild or selective fluorination, and solvent is solvent in addition to arylsulfur halotetrafluorides. Therefore, preferably selected from a group consisting of hydrocarbons, one can choose the amount necessary for obtaining an US 2011/0160488 A1 Jun. 30, 2011 adequate yield of the fluorinated compound in the second in any given reaction depends on the target compound(s), fluorination step. An illustrative amount used of reducing other chemical compounds and/or reaction conditions. substance per one mole of an arylsulfur halotetrafluoride is 0097. The amount used of target compound is dependent from about 0.1 moles to about ten moles and more typically on the kind and nature of the target compound and the aryl about 0.1 moles to about five moles. sulfur halotetrafluoride and reducing substance of the first 0091. The first step reaction is conducted in the present or step and reaction conditions such as temperature, solvent, and absence of a solvent. In some cases, reactions can be prefer catalyst or additive used. Therefore, one can choose the ably conducted without a solvent. In some cases, solvent is amount necessary for obtaining an adequate yield of the flu used for mild or selective fluorination, and solvent is prefer orinated compound from the target compound in each reac ably selected from a group consisting of hydrocarbons, halo tion. An illustrative amount used of target compound per one carbons, ethers, nitriles, aromatics, nitro compounds, esters, mole of an arylsulfur halotetrafluoride used in the first step is and mixture thereof. These solvents are exemplified as from about 0.1 moles to about 2 moles and more typically described above. about 0.2 moles to about one mole. 0098. The fluorination is conducted in the presence or 0092. The reaction temperature can be selected in the absence of a solvent. In some cases, reactions can be prefer range of about -80° C. to about +200° C., and more prefer ably conducted without a solvent. In some cases, solvent is ably, about -50° C. to about +150°C. The reaction tempera used for mild or selective fluorination, and solvent is prefer ture is dependent on the arylsulfur halotetrafluorides, reduc ably selected from a group consisting of hydrocarbons, halo ing Substances, and solvents used. Therefore, one can choose carbons, ethers, nitriles, aromatics, nitro compounds, esters, the temperature necessary for the reaction. and mixture thereof. These solvents are exemplified as 0093. The reaction time is also dependent on reaction tem described above. perature, arylsulfur halotetrafluorides, reducing Substances, 0099 Reaction temperature of the fluorination step can be Solvents, and their amounts used. Therefore, one can choose selected from the range of about -80°C. to about +200°C., the time necessary for completing each reaction by modifying and more preferably, about -50° C. to about +150° C. The one or more these parameters, but can be from about 1 minute reaction temperature is dependent on the target compounds, to several days, preferably, within a few days. arylsulfur halotetrafluorides and reducing substances of the 0094 For the second fluorination step, the target com first step, solvents, and catalysts or additives used. Therefore, pounds are described above. one can choose the temperature necessary for the reaction. 0.095. In some cases, fluorination is conducted in the pres 0100. The reaction time is also dependent on reaction tem ence of an acid Such as a Brónsted acid or a Lewis acid in perature, target compounds, arylsulfur halotetrafluorides and order to accelerate reaction or to increase fluorination yields. reducing Substances of the first step, solvents, catalysts or The amount of acid used in any given reaction depends on the additives, and their amounts used. Therefore, one can choose target compound(s), other chemical compounds and/or reac the time necessary for completing each reaction by modifying tion conditions. Preferably, the Brönsted acid is at least one one or more these parameters, but can be from about 1 minute member selected from a group consisting of hydrogen fluo to several days, preferably within a few days. ride (HF), HBF, HBC1, HBFC1, HSbF, HSbFC1, HSbF. 0101. In one embodiment, a process of introducing one or HSbFC1s, HSbFC, HN(SOCF), and other like acids, more fluorine atoms into a target compound comprises: (step and their complexes with organic compounds Such as ethers 1) contacting arylsulfur halotetrafluoride represented by the and amines. Illustrative complexes of HF with amines formula (I) with a reducing substance to form arylsulfur tri include: a mixture of HF and pyridine, a mixture of HF and C. fluoride represented by the formula (II), and then (step 2) B, and/ory-methylpyridine, a mixture of HF and dimethylpy contacting a target compound with the arylsulfur trifluoride ridine, a mixture of HF and trimethylpyridine, a mixture of obtained from the first step. HF and trimethylamine, a mixture of HF and triethylamine, and so on. Among complexes with amines, an about 70:30 wit % mixture of HF and pyridine, a 3:1 molar ratio mixture of HF (II) and triethylamine, and a 5:1 molar ratio mixture of HF and triethylamine are more preferable because of availability. Preferably, the Lewis acid is at least one member selected from a group consisting of BF, BC1, SbF, SbCl, SbF. SbCl, SbFC1, SnCl, SnF, SnClF, TiFi, TiCl, and other like acids, and their complexes with organic compounds Such as ethers, nitriles, and so on. As the preferred complexes, BF etherates can be exemplified. 0096. In some cases, fluorination is conducted in the pres 01.02 in which R', R. R. R. and Rare the same as ence of a base in order to increase product yields, or when above. starting materials and/or products are sensitive to acid condi 0103) This method consists of two processes; the first step tions. Preferable bases are exemplified with metal fluorides is a reaction of an arylsulfur halotetrafluoride with a reducing Such as sodium fluoride, potassium fluoride, cesium fluoride, Substance, and the second step is the fluorination of a target and other like compounds; carbonates such as sodium car compound with the arylsulfur trifluoride obtained from the bonate, Sodium bicarbonate, potassium carbonate, potassium first step. The arylsulfur trifluoride may be isolated and used bicarbonate, and other like compounds; amines such as pyri for the next fluorination (step 2) or may be used without dine, chloropyridine, fluoropyridine, methylpyridine, dim isolation for the next step 2. The use without isolation is ethylpyridine, trimethylpyridine, diethylamine, triethy preferable because arylsulfur trifluorides are sensitive to lamine, and other like compounds. The amount of base used moisture or wet conditions. US 2011/0160488 A1 Jun. 30, 2011

0104. The arylsulfur halotetrafluorides of formula (I) are fluoropyridine, chloropyridine, dichloropyridine, and so on, described as above. are preferable because of cost and mild and high yield reac 0105. The R', R. R. R., and R of the arylsulfur trifluo tions. Among Substituted and unsubstituted unsaturated ali rides (products) represented by the formula (II) may be dif phatic hydrocarbons, alkylalkenyl ethers such as 2-methoxy ferent from the R', R. R. R. and Rof the starting materials 1-propene (methyl 2-propenyl ether), ethyl vinyl ether, 2.3- represented by the formula (I). Thus, embodiments of this dihydrofuran, 2,3-dihydro-5-methylfuran, 3,4-dihydro-2H invention include transformation of the R. R. R. R. and R' pyran, and so on, are more preferable because of high yield to another R', R. R. R', and R which may take place under reactions. the reaction conditions or during the reaction of the present invention as long as the SFX group is transformed to a SF 0109) Other furthermore preferred reducing substances group. include arylsulfur compounds having a formula (IIIa) and/or 0106 Reducing substances are described and exemplified a formula (IIIb) as shown below. There are two advantages to above. Preferred reducing substances for this embodiment these compounds: (1) in most cases, products other than include any substance which reduces arylsulfur halotetrafluo arylsulfur trifluorides can be gaseous compounds such as ride of the formula (I) to arylsulfur trifluoride represented by chlorine gas (Cl), which is easily removed from the arylsul the formula (II) in high yields without reducing or with lim fur trifluorides that are liquid or solid, and (2) an arylsulfur ited reducing arylsulfur trifluoride represented by the formula trifluoride or a total amount of arylsulfur trifluorides can be (II). Preferable reducing substances include: the elements prepared in a more molar amount than that of arylsulfur Such as alkali metals, alkali earth metals, transition metals, halotetrafluoride used as a starting material, as seen in Eqs metals in Groups 13-15 of the Periodic Table, and semi 1-4 and Examples 71-74 below. The arylsulfur trifluorides metals; the inorganic compounds such as inorganic chloride obtained can be used for the second step reaction. salts, inorganic bromide salts, inorganic iodide salts; and the organic compounds such as organic chloride Salts, organic bromide salts, organic iodide salts, Substituted and unsubsti (IIIa) tuted aromatic hydrocarbons, substituted and unsubstituted R2 RI RI R2 heteroaromatic compounds, Substituted and unsubstituted unsaturated aliphatic hydrocarbons, Substituted and unsubsti tuted nitrogen-containing aliphatic hydrocarbons, organic R3 S-S R3 Sulfur compounds, salts or complexes of substituted or unsub stituted heteroaromatic compounds and hydrogen fluoride, and salts or complexes of substituted or unsubstituted nitro gen-containing aliphatic hydrocarbons and hydrogen fluo R2 RI (IIIb) ride; and mixtures thereof. 0107 As more preferred reducing substances, there are exemplified alkali metals, alkali earth metals, transition met R3 SR6 als, metals in Groups 13-15 of the Periodic Table, semi metals, inorganic chloride Salts, inorganic bromide salts, inorganic iodide salts, organic chloride salts, organic bromide salts, organic iodide salts, Substituted and unsubstituted aro matic hydrocarbons, Substituted and unsubstituted heteroaro 0110 wherein R. R. R. R', and Rare the same as R', matic compounds, Substituted and unsubstituted unsaturated R. R. R. and R above, and R is a hydrogen atom, a aliphatic hydrocarbons, substituted and unsubstituted nitro halogen atom, a metal atom, an ammonium moiety, a phos gen-containing aliphatic hydrocarbons, organic Sulfur com phonium moiety, or a silyl moiety. pounds, salts or complexes of Substituted or unsubstituted 10111. The halogenatom of R is a fluorine, chlorine, bro heteroaromatic compounds and hydrogen fluoride, and salts mine, or iodine atom. Among them, a chlorine atom is pre or complexes of Substituted or unsubstituted nitrogen-con ferred in viewpoint of cost. As a metal salt, alkali metals, taining aliphatic hydrocarbons and hydrogen fluoride, and alkali earth metals, and transition metals are exemplified, and mixtures thereof. among them, alkali metals such as Li, Na, Ka, and Cs are 0108. In addition, among the reducing Substances, inor preferably exemplified. As an ammonium moiety, ammo ganic chloride salts, inorganic bromide salts, inorganic iodide nium, trimethylammonium, triethylammonium, tetramethy salts, organic chloride salts, organic bromide salts, organic lammonium, tetraethylammonium, tetrabutylammonium, iodide salts, organic sulfides, organic disulfides, organic thi benzyldimethylammonium, and pyridinium are preferably ols or their salts, organic Sulfenyl halides, Substituted and exemplified. As a phosphonium moiety, tetraphenylphospho unsubstituted heteroaromatic compounds, and Substituted nium is preferably exemplified. As a silyl moiety, trimethyl and unsubstituted unsaturated aliphatic hydrocarbons, are silyl, tert-butyldimethylsilyl, triethylsilyl, tripropylsilyl, and more preferable. Among the chloride, bromide, and iodide tributylsilyl are preferably exemplified. salts, inorganic chloride salts are more preferable, and addi 0112. When Ar—Ar", the reaction of arylsulfur halotet tionally, among inorganic chloride salts, alkali metal chlo rafluoride of formula (I) (represented as ArSFX) and a reduc rides such as LiCl, NaCl, KC1, RbCl, and CsCl are more ing Substance (IIIa) (represented as ArSSAr) can give a preferable. Among these, LiCl, NaCl, KC1, and CsCl are more single product (ArSF) as represented by the formula (II). preferable, and KCl is furthermore preferable because of cost When ArzAr", the reaction of (I) and (IIIa) provides a product and high yield reactions. Among Substituted and unsubsti of a mixture of (II) and (II) shown below. Formula (II) is tuted heteroaromatic compounds, pyridine and its derivatives represented as ArSF. Both ArSF and ArSF can be used for Such as methylpyridine, dimethylpyridine, trimethylpyridine, the second step fluorination process. US 2011/0160488 A1 Jun. 30, 2011 10

R—F. Other amounts for each reaction can be used, but the above numbers provide relative levels that translate into (II) adequate production yields. R2 RI' 0.125. The amount used of reducing substance other than the arylsulfur compound (IIIa) or (IIIb) can be selected for each reaction to obtain an adequate yield of arylsulfur trifluo R3 SF ride because the necessary amount of reducing Substance is dependent on the kind and nature of the reducing Substance R4' R5 and reaction conditions such as temperature and solvent in addition to arylsulfur halotetrafluorides. An illustrative amount used of reducing Substance per one mole of an aryl 0113. Similarly, when Ar—Ar", the reaction of arylsulfur sulfur halotetrafluoride is from about 0.1 moles to about ten halotetrafluoride (I) (represented as ArSFX) and a reducing moles and more typically about 0.1 moles to about five moles. substance (IIIb) (represented as ArSR) can give a single 0.126 The first step reaction is conducted in the present or product (ArSF) as represented by the formula (II). When absence of a solvent. In some cases, reactions can be prefer ArzAr", the reaction of (I) and (IIIb) provides a product of a ably conducted without a solvent. In other cases, solvent is mixture of (II) and (II'). used for mild or selective fluorination, and solvent is prefer 0114. When arylsulfur compound having a formula (IIIa) ably selected from a group consisting of hydrocarbons, halo (ArSSAr") is used, the reaction equation of the reaction of (I) carbons, ethers, nitriles, aromatics, nitro compounds, esters, and (IIIa) may be shown with the following: and mixture thereof. These solvents are exemplified as described above. I0127. The reaction temperature of the first step reaction 0115 Thus, an illustrative total amount of arylsulfur trif can be selected in the range of about -80°C. to about +200° luorides (ArSF and ArSF) is 4/3 moles for every one mole C., and more preferably, about -50° C. to about +150°C. The of ArSFX used. reaction temperature primarily depends on the arylsulfur hal 0116. When arylsulfur compound having a formula (IIIb) otetrafluorides, reducing Substances, and solvents used. Therefore, one can choose the temperature necessary for the (ArSR) is used, the reaction equation of reaction of (I) and reaction. When arylsulfur compounds having a formula (IIIa) (IIIb) may be the following: or a formula (IIIb) (Rahalogenatom) are used as a reducing 0117 1, Rza halogen atom; Substance, the reaction temperature is preferably selected (Eq. 2) from the range of about room temperature to about +150°C., and more preferably, about +50° C. to about +120° C. When 0118. Thus, an illustrative total amount of arylsulfur arylsulfur compounds having a formula (IIIb) (Rza halogen trifluorides (ArSF and ArSF) is 5/4 moles for every atom) are used as a reducing Substance, the reaction tempera one mole of ArSFX used. ture can be preferably selected from the range of about -80° I0119) 2, R=X (a chlorine, bromine, or iodine atom); C. to about +150° C., and more preferably, about -50° C. to ArSFX--/3. Ar'SX->ArSF+/3. Ar'SF +24.X. (Eq. 3) about +120° C. When inorganic or organic chloride salts are used as a reducing Substance, the reaction temperature is I0120 Thus, an illustrative total amount of arylsulfur preferably selected from the range of about +40° C. to about trifluorides is 4/3 moles for every one mole of ArSFX +150° C., more preferably, about +50° C. to about +120° C. used. When heteroaromatic compounds are used as a reducing Sub 0121 3, R=a fluorine atom; stance, the reaction temperature is preferably selected in the range of about -50° C. to about +100° C., preferably, about ArSFX--/3. Ar'SF->ArSF+/3. Ar'SF+/3.X. (Eq. 4) -20°C. to about +70° C. When other reducing substances are 0122) Thus, an illustrative total amount of arylsulfur trif used, the reaction temperature can be selected so that the luorides is 3/2 moles for every one mole of ArSFX used. reaction is finished in a reasonable time. (0123. The R. R. R. R', and R of the products I0128. The reaction time is also dependent on reaction tem (ArSF) represented by the formula (II) may be different perature, reducing Substances, arylsulfur halotetrafluorides, from the R. R. R. R', and R of the starting materials Solvents, and their amounts used. Therefore, one can choose represented by the formulas (IIIa) and/or (IIIb). Thus, the time necessary for completing each reaction by modifying embodiments of this invention include transformation of the one or more of these parameters, but can be from about 1 R. R. R. R', and R to another R. R. R. R', and R' minute to several days, preferably, within a few days. which may take place during the reaction of the present inven I0129. For the second fluorination step, the arylsulfur trif tion or under the reaction conditions as long as the —S-S- luorides obtained by the first step may be used without isola or —S— moiety is transformed to a —SF group(s). tion or the isolated arylsulfur trifluorides may be used. It is 0.124. In order to get adequate production yields, the preferable that the arylsulfur trifluorides are used without amount used of arylsulfur compound having a formula (IIIa) isolation because it is convenient since the arylsulfur trifluo is around /6 moles per one mole of ArSFX. The amount used rides are sensitive to moisture or wet conditions. of arylsulfur compound having a formula (IIIb) is around 1/4 0.130 For the second fluorination step, the target com moles per one mole of ArSFX when Riza halogenatom. The pounds are the same as described above. amount used of arylsulfur compound having a formula (IIIb) I0131. In some cases, fluorination is conducted in the pres is around 4 moles per one mole of ArSFX when R-Cl, Br, ence of an acid Such as a Brönsted acid or a Lewis acid in or I. The amount used of arylsulfur compound having a for order to accelerate reaction or to increase fluorination yields. mula (IIIb) is around /2 moles per one mole of ArSFX when The amount of acid used in any given reaction depends on the US 2011/0160488 A1 Jun. 30, 2011 target compound(s), other chemical compounds and/or reac pleting each reaction by modifying one or more these param tion conditions. Preferably, the Brönsted acid is at least one eters, but can be from about 1 minute to several days, prefer member selected from a group consisting of hydrogen fluo ably within a few days. ride (HF), HBF, HBC1, HBFC1, HSbF, HSbFC1, HSbF. 0.137 The present invention also provides a process for HSbFC1s, HSbFC, HN(SOCF), and other like acids, preparing arylsulfur trifluorideas represented by formula (II). and their complexes with organic compounds Such as ethers 0.138. In one embodiment, a process for preparing arylsul and amines Illustrative complexes of HF with amines, include fur trifluoride represented by the formula (II) comprises con a mixture of HF and pyridine, a mixture of HF and C, B, and/or tacting arylsulfur halotetrafluoride represented by the for Y-methylpyridine, a mixture of HF and dimethylpyridine, a mula (I) above with a reducing Substance. mixture of HF and trimethylpyridine, a mixture of HF and 0.139 Reducing substances are described and exemplified trimethylamine, a mixture of HF and triethylamine, and so on. as above. Preferred reducing Substances include any Sub Among complexes with amines, an about 70:30 wt % mixture stance which reduces arylsulfur halotetrafluoride of the for of HF and pyridine, a 3:1 molar ratio mixture of HF and mula (I) to produce arylsulfur trifluoride represented by the triethylamine, and a 5:1 molar ratio mixture of HF and tri formula (II) in high yields without reducing or with limited ethylamine are more preferable because of availability. Pref reducing arylsulfur trifluoride represented by the formula erably, the Lewis acid is at least one member selected from a (II). Preferable reducing substances include; the elements group consisting of BF, BC1, SbF, SbCl, SbF, SbCl, Such as alkali metals, alkali earth metals, transition metals, SbFC1, SnCl, SnF, SnClF, TiFi, TiCl, and other like metals in Groups 13-15 of the Periodic Table, and semi acids, and their complexes with organic compounds such as metals; the inorganic compounds Such as inorganic chloride ethers, nitriles, and so on. As the preferred complexes, BF salts, inorganic bromide salts, inorganic iodide salts; and the etherates are exemplified. organic compounds such as organic chloride Salts, organic 0.132. In some cases, fluorination is conducted in the pres bromide salts, organic iodide salts, Substituted and unsubsti ence of a base in order to increase production yields, or when tuted aromatic hydrocarbons, substituted and unsubstituted starting materials and/or products are sensitive to acid condi heteroaromatic compounds, Substituted and unsubstituted tions. Preferable bases are exemplified with metal fluorides unsaturated aliphatic hydrocarbons, Substituted and unsubsti Such as sodium fluoride, potassium fluoride, cesium fluoride, tuted nitrogen-containing aliphatic hydrocarbons, organic and other like compounds; carbonates such as sodium car Sulfur compounds, salts or complexes of substituted or unsub bonate, Sodium bicarbonate, potassium carbonate, potassium stituted heteroaromatic compounds and hydrogen fluoride, bicarbonate, and other like compounds; amines such as pyri and salts or complexes of substituted or unsubstituted nitro dine, chloropyridine, fluoropyridine, methylpyridine, dim gen-containing aliphatic hydrocarbons and hydrogen fluo ethylpyridine, trimethylpyridine, diethylamine, triethy ride; and mixtures thereof. lamine, and other like compounds. The amount of base used 0140. As more preferred reducing substances, there are in any given reaction depends on the target compound(s), exemplified alkali metals, alkali earth metals, transition met other chemical compounds and/or reaction conditions. als, metals in Groups 13-15 of the Periodic Table, semi 0133. The amount used of target compound is dependent metals, inorganic chloride Salts, inorganic bromide salts, on the kind and nature of the target compound and reaction inorganic iodide salts, organic chloride salts, organic bromide conditions such as temperature, solvent, and catalyst or addi salts, organic iodide salts, Substituted and unsubstituted aro tive used. Therefore, one can choose the amount necessary for matic hydrocarbons, Substituted and unsubstituted heteroaro obtaining an adequate yield of the fluorinated compound matic compounds, Substituted and unsubstituted unsaturated from the target compound in each reaction. An illustrative aliphatic hydrocarbons, substituted and unsubstituted nitro amount used of target compound per one mole of an arylsul gen-containing aliphatic hydrocarbons, organic Sulfur com furtrifluoride obtained in the first step is from about 0.1 moles pounds, salts or complexes of Substituted or unsubstituted to about two moles and more typically about 0.2 moles to heteroaromatic compounds and hydrogen fluoride, and salts about one mole. or complexes of Substituted or unsubstituted nitrogen-con 0134. The fluorination reaction can be conducted in the taining aliphatic hydrocarbons and hydrogen fluoride, and presence or absence of a solvent. In some cases, reactions are mixtures thereof. conducted without a solvent. In other cases, a solvent can be 0.141. In addition, among the reducing Substances, inor used for mild or selective fluorination, and solvent is prefer ganic chloride salts, inorganic bromide Salts, inorganic iodide ably selected from a group consisting of hydrocarbons, halo salts, organic chloride salts, organic bromide salts, organic carbons, ethers, nitriles, aromatics, nitro compounds, esters, iodide salts, organic sulfides, organic disulfides, organic thi and mixture thereof. These solvents are exemplified as ols or their salts, organic Sulfenyl halides, Substituted and described above. unsubstituted heteroaromatic compounds, and Substituted 0135 Preferably, reaction temperature for the fluorination and unsubstituted unsaturated aliphatic hydrocarbons, are can be selected in the range of about -80°C. to about +200° more preferable. Among the chloride, bromide, and iodide C., and more preferably, about -50° C. to about +150°C. The salts, inorganic chloride salts are more preferable, and addi reaction temperature primarily depends on the target com tionally, among inorganic chloride salts, alkali metal chlo pounds, the arylsulfur trifluorides, catalysts, additives, Sol rides such as LiCl, NaCl, KC1, RbCl, and CsCl are more vents, reducing Substances, or the arylsulfur halotetrafluo preferable. Among these, LiCl, NaCl, KC1, and CsCl are more rides used. Therefore, one can choose the temperature preferable, and KCl is furthermore preferable because of cost necessary for the reaction. and high yield reactions. Among Substituted and unsubsti 0136. The reaction time is also dependent on reaction tem tuted heteroaromatic compounds, pyridine and its derivatives perature, target compounds, arylsulfur trifluorides or halotet Such as methylpyridine, dimethylpyridine, trimethylpyridine, rafluorides, solvents, catalysts or additives, and their amounts chloropyridine, dichloropyridine, and so on, are preferable used. Therefore, one can choose the time necessary for com because of cost and mild and high yield reactions. Among US 2011/0160488 A1 Jun. 30, 2011

Substituted and unsubstituted unsaturated aliphatic hydrocar bons, alkylalkenyl ethers such as 2-methoxy-1-propene (me thyl 2-propenyl ether), ethyl vinyl ether, 2,3-dihydrofuran, (II) 2,3-dihydro-5-methylfuran, 3,4-dihydro-2H-pyran, and so on, are more preferable because of high yield reactions. 0142. Other furthermore preferred reducing substances include arylsulfur compounds having a formula (IIIa) and/or a formula (IIIb) as shown below, two advantages to these compounds include: (1) in most cases, products other than arylsulfur trifluorides can be gaseous compounds such as 0147 Similarly, when Ar—Ar", the reaction of (I) (repre chlorine gas (Cl), which is easily removed from the arylsul sented as ArSFX) and(IIIb) (represented as ArSR) can give fur trifluorides that are liquid or solid; and (2) another benefit a single product (ArSF) as represented by the formula (II). of the reducing substances is that an arylsulfur trifluoride or a When Arz Ar", the reaction of (I) and (IIIb) provides a product total amount of arylsulfur trifluorides can be prepared in a of a mixture of (II) (ArSF) and (II) (ArSF). more molar amount than that of arylsulfur halotetrafluoride 0.148. The R', R. R. R., and R of the products repre used as a starting material, as seen in Eqs 1-4 above and sented by the formula (II) may be different from the R', R, Examples 71-74 below. The arylsulfur trifluorides obtained R. R', and R of the starting materials represented by the can be used for the fluorination reaction of a target compound. formula (I). And, the R. R. R. R', and R of the products represented by the formula (II) may be different from the R', R. R. R', and R of the starting materials represented by (IIIa) the formulas (IIIa) and/or (IIIb). Thus, embodiments of this R2 RI RI R2 invention include transformation of the R',R,R,R, andR to another R', R,R,R, and R and of the R. R. R. R. and R to another R. R. R. R', and R, which may take R3 S-S R3 place during the reaction of the present invention or under the reaction conditions as long as the —SF.C1 and/or the —S—S - or - S - moiety is transformed to a —SF group (s). R2 RI (IIIb) 0149. In order to get adequate production yields, the amount used of arylsulfur compound having a formula (IIIa) is around /6 moles per one mole of ArSFX. The amount used R3 SR6 of arylsulfur compound having a formula (IIIb) is around 4 moles per one mole of ArSFX when Razahalogenatom. The amount used of arylsulfur compound having a formula (IIIb) is around 4 moles per one mole of ArSFX when R-Cl, Br, or I. The amount used of arylsulfur compound having a for 0143 wherein R. R. R. R', and Rare the same as R', mula (IIIb) is around /2 moles per one mole of ArSFX when R. R. R. and R above, and R is a hydrogen atom, a R—F. As above, other amounts can be used as long as the halogen atom, a metal atom, an ammonium moiety, a phos reaction proceeds. phonium moiety, or a silyl moiety. 0150. The amount used of reducing substance other than the arylsulfur compound (IIIa) or (IIIb) can be selected for I0144) The halogenatom of R is a fluorine, chlorine, bro each reaction to obtain an adequate yield of arylsulfur trifluo mine, or iodine atom. Among them, a chlorine atom is pre ride because the necessary amount of reducing Substance is ferred from the viewpoint of cost. dependent on the kind and nature of the reducing Substance 0145 As a metal salt, alkali metals, alkali earth metals, and reaction conditions such as temperature and solvent in and transition metals are exemplified, and among them, alkali addition to the arylsulfur halotetrafluoride. An illustrative metals such as Li, Na, Ka, and Cs are preferably exemplified. amount used of reducing Substance per one mole of an aryl As an ammonium moiety, ammonium, trimethylammonium, sulfur halotetrafluoride is from about 0.1 moles to about ten triethylammonium, tetramethylammonium, tetraethylammo moles and more typically about 0.1 moles to about five moles. nium, tetrabutylammonium, benzyldimethylammonium, and 0151. The reaction can be conducted in the absence or pyridinium are preferable exemplified. As a phosphonium presence of Solvent. In some cases, the reaction can prefer moiety, tetraphenylphosphonium is preferably exemplified. ably be conducted without a solvent. In other cases, solvent makes the reaction Smooth, and for these cases, solvent is As a silyl moiety, trimethylsilyl, tert-butyldimethylsilyl, tri preferably selected from a group consisting of hydrocarbons, ethylsilyl, tripropylsilyl, and tributylsilyl are preferably halocarbons, nitriles, aromatics, nitro compounds, esters, and exemplified. mixture thereof. These solvents are exemplified as described 0146 When Ar—Ar", the reaction of (I) (represented as above. ArSFX) and (IIIa) (represented as ArSSAr") can give a 0152 The reaction temperature primarily depends on the single product (ArSF) as represented by the formula (II). arylsulfur halotetrafluoride, reducing Substance, and solvent When ArzAr", the reaction of (I) and (IIIa) provides a product used. The reaction temperature can be selected in the range of of a mixture of (II) (ArSF) and (II) shown below. (II) is also about -80°C. to about +200° C. When arylsulfur compounds represented as ArSF. having a formula (IIIa) or a formula (IIIb) (R-a halogen US 2011/0160488 A1 Jun. 30, 2011 13 atom) are used as a reducing Substance, the reaction tempera 0153. The reaction time is also dependent on reaction tem ture is preferably selected from the range of about room perature, the arylsulfur halotetrafluorides, reducing sub temperature to about +150° C., and more preferably, about stances, solvent, and their amounts used. Therefore, one can +50° C. to about +120° C. When arylsulfur compounds hav choose the time necessary for completing each reaction by ing a formula (IIIb) (R'za halogenatom) are used as a reduc modifying one or more these parameters, but can be from ing Substance, the reaction temperature can be preferably about 1 minute to several days, preferably, within a few days. 0154 It will be understood by one of skill in the relevant selected from the range of about -80°C. to about +150°C., art that certain compounds of the invention may comprise one and more preferably, about -50° C. to about +120° C. When or more chiral centers so that the compounds may exist as inorganic or organic chloride salts are used as a reducing Stereoisomers, including diastereoisomers and enantiomers. Substance, the reaction temperature is preferably selected It is envisioned that all such compounds be within the scope from the range of about +40° C. to about +150° C., more of the present invention, including all such stereoisomers, and preferably, about +50° C. to about +120° C. When heteroaro mixtures thereof, including racemates. matic compounds are used as a reducing Substance, the reac tion temperature is preferably selected in the range of about EXAMPLES -50° C. to about +100° C., preferably, about -20°C. to about 0155 The following examples are provided for illustrative +70° C. When other reducing substances are used, the reac purposes only and are not intended to limit the scope of the tion temperature can be selected so that the reaction is fin invention. Table 1 provides structure names and formulas for ished in a reasonable time. reference when reviewing the following examples:

TABLE 1.

Substituted and Unsubstituted Phenylsulfur Halotetrafluorides (Formulas IV-XIV):

Formula Number Name Structure

IV Phenylsulfur chlorotetrafluoride SFCI

p-Methylphenylsulfur chlorotetrafluoride co-( )-se VI p-(tert-Butyl)phenylsulfur chlorotetrafluoride )-( )-se VII p-Fluorophenylsulfur chlorotetrafluoride -( )-se VIII o-Fluorophenylsulfur F chlorotetrafluoride (S- IX p-Chlorophenylsulfur chlorotetrafluoride C SFCI

p-Bromophenylsulfur chlorotetrafluoride Br -()– SF4Cl

XI m-Bromophenylsulfur Br chlorotetrafluoride ). SFCI US 2011/0160488 A1 Jun. 30, 2011 14

TABLE 1-continued Substituted and Unsubstituted Phenylsulfur Halotetrafluorides (Formulas IV.--XIV):

Formula Number Name Structure XII p-Nitrophenylsulfur chlorotetrafluoride ON -(-)- SFCI

XIII 2,6-Difluorophenylsulfur F chlorotetrafluoride

SFC

F XIV 2,3,4,5,6- F F Pentafluorophenylsulfur chlorotetrafluoride F SFCI

F F

Example 1 Example 2 Synthesis of Phenylsulfur Chlorotetrafluoride (IV) Synthesis of Phenylsulfur Chlorotetrafluoride (IV) from Diphenyl Disulfide from Thiophenol 0156 0158

Cl S-S - C B - SFCI SH - KF as SFC4 KF IV IV 0159. Chlorine (C1) was passed with a flow rate of 27 0157. A 500 mL round bottom glassware flask was mL/min into a stirred mixture of 10.0 g (90.8 mmol) of charged with diphenyl disulfide (33.0 g, 0.15 mol), dry KF thiophenol and 47.5 g (0.817 mol) of dry KF in 100 mL of dry (140g, 2.4 mol) and 300 mL of dry CHCN. The stirred acetonitrile at 6-10°C. Chlorine was passed for 3.7 hand the reaction mixture was cooledon an ice/water bathunder a flow total amount of chlorine passed was 10.2 L (0.445 mol). The ofN (18 mL/min). After N was stopped, chlorine (Cl-) was reaction mixture was filtered. After removal of the solvent in bubbled into the reaction mixture at a rate of about 70 vacuum, phenylsulfur chlorotetrafluoride (IV) (16.6 g., 83%) mL/min. The Clbubbling took about 6.5 h. The total amount as a light green-brown liquid was obtained. The physical of C1 used was about 1.2 mol. After C1 was stopped, the properties and spectral data of the product are as shown in reaction mixture was stirred for additional 3 h. Na was then Example 1. The product was a trans isomer. bubbled through for 2 hours to remove excess C1. The reac tion mixture was then filtered with 100 mL of dry hexanes in Examples 3-12 air. About 1 g of dry KF was added to the filtrate. The KF restrains possible decomposition of the product. The filtrate Synthesis of Arylsulfur Halotetrafluorides V-XIV was evaporated under vacuum and the resulting residue was from Diaryl Disulfides or Arenethiols distilled at reduced pressure to give a colorless liquid (58.0 g, 88%) of phenylsulfur chlorotetrafluoride (formula IV): b.p. (0160 80° C./20 mmHg: "H NMR (CDCN) & 7.79-7.75 (m, 2H, aromatic), 7.53-749 (m, 3H, aromatic); 'F NMR (CDCN) & 136.7 (s, SF Cl); High resolution mass spectrum; found Re o 221.970281 (38.4%) (calcd for CHFS Cl: 221970713), / S-S \ / O found 219.974359 (100%) (calcd for CHFSC1; 219.973663). The NMR analysis showed phenylsulfur chlo R = a substituted group rotetrafluoride obtained as a trans isomer. US 2011/0160488 A1 Jun. 30, 2011 15

(0161 Substituted arylsulfur chlorotetrafluorides V-XIV -continued were synthesized from the corresponding diaryl disulfides or arenethiols by a similar procedure as shown in Example 1 or R. A.R R 2. Table 2 shows the synthesis of the substituted arylsulfur SC SH S SC chlorotatrafluorides V-XIV together with IV (Examples 1 -e- SFCI and 2). Table 2 also shows the starting materials and other \ / KF \ chemicals necessary for the synthesis, Solvents, reaction con ditions, and the results, together with those of Examples 1 and 2.

TABLE 2

Preparation of Arylsulfur Halotetrafluorides.

Disulfide or Fluoride Ex Thiol Halogen SOUCC Solvent Temp Time ArS FX Yield

1 Cl2 KF CHCN O-5°C. 88% 2.4 mol 300 mL. ()- ~1.2 mol SFC 2 IV 0.15 mol 58 g

2 Cl2 KF CHCN 6-10°C. 83% SH O.445 O.817 100 mL. mol mol ()- SFC 0.0908 mol IV 16.6 g.

3 Cl2 KF CHCN Oo C. 7396 3.85 mol 8 mol 1000 mL. CH3 S C H3 SFCI

2 V 0.5 mol 170 g

4 Cl2 CSF CHCN --Sh 84% SH O452 O602 150 mL. mol mol SFCI

0.0602 mol VI 14g

5 Cl2 KF CHCN 2.5 67% 0.28 mol 0.63 mol 100 mL. F S Ol. SFCI

2 VII 0.039 mol 12.5g

6 F Cl2 KF CHCN 1.8h 80% 0.31 mol 0.63 mol 100 mL. Ol. S SFC 2 C VIII 0.039 mol 14.9 g

7 Cl2 KF CHCN S-8°C. 3.S. 88% 0.57 mol 1.48 mol 200 mL. C S SFC

2 IX 0.087 mol 39.5g US 2011/0160488 A1 Jun. 30, 2011

TABLE 2-continued

Preparation of Arylsulfur Halotetrafluorides.

Disulfide or Fluoride Ex Thiol Halogen SOUCC Solvent Temp Time ArSFX Yield 8 Cl2 KF CHCN O-5°C 4.5h 770, 0.72 mol 1.6 mol 200 mL. and and n-()- rt. Ol. Br SFCI 2 X 0.1 mol 46.2g

9 Br Cl2 KF CHCN O-5°C 5.5 h Br 86% 0.88 mol 2.0 mol 250 mL. and and rt. Ol. S SFC

2 XI 0.127 mol 65.7g

10 Cl2 KF CHCN O-5°C 4.5h 60% 0.72 mol 1.6 mol 200 mL. and and os-()– S rt. Ol. os-()– SFCI 2 XII 0.1 mol 32g

11 F Cl2 CSF CHCN O-5°C Sh F 82% 1.02 mol 1.83 mol 200 mL. and and rt. O.l. S SF4Cl

2 F F 0.1 mol XIII 42.3g

12 F F Cl2 KF CHCN O-5°C Sh F F 86% -1 mol 1.41 mol 300 mL. and and rt. Ol. F S F SFCI

2 F F F F 0.065 mol XIV 34.9 g *rt. = room temperature; on. = overnight

0162 The properties and spectral data of the products, J=9.2 Hz, 2H, aromatic); 'F NMR 8138.3 (s, SFC1). The (V)-(XIV), obtained by Examples 3-12 are shown by the NMR showed that p-(tert-butyl)phenylsulfur chlorotetrafluo following: ride was obtained as a trans isomer. Elemental analysis; Calcd for CHCIFS: C, 43.40%; H, 4.74%. Found: C, 43.69%, 0163 p-Methylphenylsulfur chlorotetrafluoride (V); b.p. H, 4.74%. 74-75 C/5 mmHg: "H NMR (CDCN) & 7.65 (d. J=8.1 Hz, 0.165 p-Fluorophenylsulfur chlorotetrafluoride (VII); b.p. 2H, aromatic), 7.29 (d. J–8.1 Hz, 2H, aromatic), 2.36 (s.3H, 60° C./8 mmHg: "H NMR (CDCN) & 7.85-7.78 (m, 2H, CH); 'F NMR (CDCN) & 137.66 (s, SF Cl); High resolu aromatic), 7.25-7.15 (m, 2H, aromatic); 'F NMR (CDCN) tion mass spectrum; found 235.986234 (34.9%) (calcd for & 137.6 (s, SF,Cl), -108.3 (s, CF); High resolution mass C.H.F.S7C1; 235.986363), found 233.989763 (75.6%) spectrum; found 239.961355 (37.4%) (calcd for (calcd for CHFSC1; 233.9893.13). The NMR showed CHFS7C1; 239.961291), found 237.964.201 (100%) that p-methylphenylsulfur chlorotetrafluoride obtained was a (calcd for CHFSC1; 237.964241). The NMR shows that trans isomer. p-fluorophenylsulfur chlorotetrafluoride was obtained as a 0164 p-(tert-Butyl)phenylsulfur chlorotetrafluoride (VI); trans isomer. m.p. 93° C.; b.p. 98° C./0.3 mmHg: "H NMR (CDC1) & 1.32 0166 o-Fluorophenylsulfur chlorotetrafluoride (VIII); (s, 9H, C(CH)), 7.43 (d. J=9.2 Hz, 2H, aromatic), 7.64 (d. b.p. 96-97 C/20 mmHg: "H NMR (CDCN) & 7.77-7.72 (m, US 2011/0160488 A1 Jun. 30, 2011 17

1H, aromatic), 7.60-7.40 (m. 1H, aromatic), 7.25-7.10 (m, mp. 47.6-48.3° C.; F NMR (CDC1) & 143.9 (t, J=26.0 Hz, 2H, aromatic); 'F NMR (CDCN) & 140.9 (d. SFCI), 4F, SF), -104.1 (quintet, J=26.0 Hz, 2F, Ar F): "H NMR -107.6 (s, CF); High resolution mass spectrum; found 239. (CDC1) & 6.97-7.09 (m,2H,3,5-H), 743-7.55 (m. 1H, 4-H): 96.1474 (25.4%) (calcd for CHFS7C1; 239,961291), 'C NMR (CDC1) & 157.20 (d. J–262.3 Hz), 133.74 (t, found 237.964375 (69.8%) (calcd for CHFSC1; 237. J=11.6 Hz), 130.60 (m), 113.46 (d. J–14.6 Hz): elemental 964241). The NMR showed that o-fluorophenylsulfur chlo analysis, C, 28.24%, H, 1.24% (calcd for CHCIFS: C, rotetrafluoride was obtained as a trans isomer. 28.08%, H, 1.18%); High resolution mass spectrum; found 0167 p-Chlorophenylsulfur chlorotetrafluoride (IX); b.p. 257.950876 (37.6%) (calcd for CH,7CIFS: 257.951869), 65-66°C/2 mmHg: "H NMR (CDCN) & 7.65 (d. J=9.1 Hz, found 255.955740 (100%) (calcd for CHCIFS: 2H, aromatic), 7.83 (d. J=9.1 Hz, 2H, aromatic); 'F NMR 255.954819). The cis-isomer was assigned in the following: (CDCN) & 137.4 (s, SF,Cl); High resolution mass spectrum; 'F NMR (CDC1,) & 158.2 (quartet, J=161.8 Hz, 1F, SF), found 257.927507 (13.3%) (calcd for CHFS7C1; 257. 121.9 (m. 2F, SF), 76.0 (m, 1F, SF). The 'F NMR assign 928790), found 255,930746 (68.9%) (calcd for ment of aromatic fluorine atoms of the cis-isomer could not be CHFS7C1-C1; 255.931740), found 253.933767 done because of possible overlapping of the peaks of the (100.0%) (calcd for CHFSC1; 253.934690). The NMR trans-isomer. shows that p-chlorophenylsulfur chlorotetrafluoride was 0172 2,3,4,5,6-Pentafluorophenylsulfur chlorotetrafluo obtained as a trans isomer. ride (XIV): The product (b.p. 95-112° C./100 mmHg) 0168 p-Bromophenylsulfur chlorotetrafluoride (X); m.p. obtained from Experiment 12 was a 1.7:1 mixture of trans and 58-59° C.; H NMR (CDCN) & 7.67 (s, 4H, aromatic); 'F cis isomers of 2,3,4,5,6-pentafluorophenylsulfur chlorotet NMR (CDCN) & 136.56 (s, SF,Cl); High resolution mass rafluoride. The isomers were assigned by FNMR: The trans spectrum; found 301.877066 (16.5%) (calcd for isomer; F NMR (CDC1) & 144.10 (t, J=26.0 Hz, 4F, SF), C.H.'Br7CIFS: 301.879178), found 299.880655 (76.6%) -132.7 (m. 2F, 2.6-F), -146.6 (m. 1F, 4-F), -158.9 (m. 2F, (calcd for CHBrOIFS: 299.881224 and calcd for 3.5-F); C NMR (CDC1,) & 143.5 (dim, J-265.2 Hz), 141.7 CH'Br7CIFS: 299.882128), found 297.882761 (77.4%) (dim, J=263.7 Hz), 128.3 (m). The cis isomer; F NMR (calcd for CH'BrCIFS: 297.884174). The NMR (CDC1) & 152.39 (quartet, J=158.9 Hz, 1F, SF), 124.32 (m, showed that p-bromophenylsulfur chlorotetrafluoride was 2F, SF), 79.4 (m, 1F, SF), -132.7 (m. 2F, 2,6-F), -146.6 (m, obtained as a trans isomer. 1F, 4-F), -158.9 (m. 2F, 3.5-F). High resolution mass spec 0169 m-Bromophenylsulfur chlorotetrafluoride (XI); b.p. trum of a 1.7:1 mixture of the trans and cis isomers; found 57-59°C/0.8 mmHg: "H NMR (CDCN) & 7.90-7.88 (m, 1H, 311.923124 (15.5%) (calcd for C7ClFS: 311.923604), aromatic), 7.70-7.50 (m, 2H, aromatic), 7.40-7.30 (m, 1H, found 309.926404 (43.1%) (calcd for CCIFS: aromatic); 'F NMR (CDCN) & 136.74 (s, SF Cl); High 309.926554). resolution mass spectrum; found 301.878031 (29.1%) (calcd for C.H.' Br'CIFS: 301.879178), found 299.881066 Examples 13-29 (100%) (calcd for CHBrOIFS: 299.881224 and calcd for CH7Br 7CIFS: 299.882128), found 297.883275 (77. Fluorinations of Various Target Compounds with 4%) (calcd for CH'BrCIFS: 297.884174). The NMR Arylsulfur Halotetrafluorides by a One-Step Process showed that m-bromophenylsulfur chlorotetrafluoride in Accordance with the Present Invention obtained was a trans isomer. 0173 A typical procedure inaccordance with the embodi 0170 p-Nitrophenylsulfur chlorotetrafluoride (XII); m.p. ments of the present invention is as follows; a solution of 0.66 130-131° C.; H NMR (CDCN) & 8.29 (d. J=7.8 Hz, 2H, mmol of n-CHOC(S)SCH in 1 mL of dry methylene aromatic), 8.02 (d. J–7.8 Hz, 2H, aromatic); 'F NMR chloride was added to a solution of 1.66 mmol of phenylsulfur (CDCN) & 134.96 (s, SF,Cl); High resolution mass spec chlorotetrafluoride in 3 mL of dry methylene chloride in a trum; found 266.956490 (38.4%) (calcd for fluoropolymer (PFA) vessel under nitrogen atmosphere. The CH7CIFNOS: 266.955791), found 264.959223 (100%) mixture was stirred at room temperature for 5 hours. 'F (calcd for CHCIFNOS: 264,958741). The NMR NMR analysis of the reaction mixture showed that showed that p-nitrophenylsulfur chlorotetrafluoride was n-CHOCF was produced in a 96% yield. obtained as a trans isomer. 0.174 Fluorinations of various target compounds with (0171 2,6-Difluorophenylsulfur chlorotetrafluoride various arylsulfur halotetrafluorides were conducted in the (XIII): The product (bp. 120-122° C./95-100 mmHg) same manner as above. Various fluorinated compounds were obtained from Example 11 is a 6:1 mixture of trans- and produced in high yields. Tables 3 shows the results and the cis-isomers of 2,6-difluorophenylsulfur chlorotetrafluoride. detailed reaction conditions. The products were identified by The trans-isomer was isolated as pure form by crystallization; comparison with known samples and/or spectral analyses.

TABLE 3 Fluorination of Various Target Compounds with ArSFAC by a One-Step Process Temp & Fluorinated 19F-NMR Ex ArSFC Target Compound Solvent Time Product data Yield Ex IV n-CoH2OC(=S)SCH CH2Cl2 r.t., n-CoH2OCF -60.5 96% 13 (1.66 mmol) (0.66 mmol) (3 mL) Sh (s, CFs) CH2Cl2 r.t., n-CoH2OCF -60.5 quant. 14 (3.21 mmol) (2.14 mmol) (3 mL) 4h (S, CFs)

US 2011/0160488 A1 Jun. 30, 2011 19

TABLE 3-continued

Fluorination of Various Target Compounds with ArSFC by a One-Step Process Temp & Fluorinated 19F-NMR Ex ArSFC Target Compound Solvent Time Product data Yield Ex IV CH2Cl2 r.t. -85.8 75% 29 (1.86 mmol) (3 mL) 3h (S,CF), -79.8 S (S,CF) N-CF N-( V CF CF

(1.24 mmol) Quant, = quantitative yield.

Examples 30-41 vessel at room temperature. The reaction mixture was stirred for 1.5 hours at room temperature. 'FNMR analysis showed Fluorinations of Various Target Compounds with that benzoyl fluoride (PhCOF) was produced in a quantitative Arylsulfur Halotetrafluorides by a One-Step Process yield. in the Presence of a Reducing Substance and in 0176 Fluorinations of target compounds with a different Accordance with the Present Invention arylsulfur halotetrafluoride in the presence of a different 0.175. A typical procedure in accordance with embodi reducing Substance were conducted in the same manner as ments of the present invention is as follows: 1 mmol of aryl above. Table 4 shows results and detailed reaction conditions sulfur halotetrafluoride was added to a solution of 1 mmol for other like embodiments. The products were identified by benzoic acid and 1 mmol of pyridine in 2 mL of dry methylene spectral analysis or by comparison with authentic samples. chloride under nitrogen atmosphere in a fluoropolymer (PFA) The yields of products were determined by the NMR analysis.

TABLE 4 Fluorination of Various Target Compounds with ArSFX by a One-Step-Process in the Presence of a Different Reducing Substance. 19F Target Reducing Fluorinated NMR Ex ASFX Compound Substance Solvent Temp Time Product (ppm) Yield 30 IV PCOOH Pyridine CH2Cl2 rt. 1.5h PhCOF 8.0 (s, Quant (1 mmol) (1 mmol) (1 mmol) (2 mL) COF 31 IV PCOOH (C2H5)N(HF), CH2Cl2 rt. 1.5h PhCOF 8.0 (s, Quant (1 mmol) (1 mmol) (1 mmol) (2 mL) COF 32 IV PCOOH Aniline CHCl2 .. Sh PhCOF 8.0 (s, Quant (1 mmol) (1 mmol) (1 mmol) (2 mL) COF 33 IV PCOOH Anthracene CH2Cl2 .. Sh PhCOF 8.0 (s, Quant (1 mmol) (1 mmol) (1 mmol) (2 mL) COF 34 IV PCOOH 2,3-dimethyl-2- CH2Cl2 15h. PhCOF 8.0 (s, Quant (1 mmol) (1 mmol) butene (2 mL) COF (1 mmol) 35 IV PCOOH Diphenyl H2Cl2 15h. PhCOF 8.0 (s, Quant. (1 mmol) (1 mmol) sulfide (2 mL) COF (1 mmol) 36 IV PCOOH Thiophenol CH2Cl2 .. 1h PhCOF 8.0 (s, 91% (2 mmol) (2 mmol) (2 mmol) (2 mL) COF 37 IV PCOOH Mg (2.53 THF .. 3 h PhCOF 8.0 (s, 93% (2.53 (2.53 mmol) mmol), TBAI (4 mL) COF mmol) (cat.) 38 IV PCOOH Sn (1.75 mmol), THF 2h PhCOF 8.0 (s, 84% (1.75 (1.75 mmol) TBAI (cat.) (4 mL) COF mmol) 39 IV PCOOH Zn (1.48 THF 24h PhCOF 8.0 (s, 47% (1.48 (1.48 mmol) mmol), TBAI (4 mL) COF mmol) (cat.) 40 XIII PCOOH Pyridine CHCl2 15h. PhCOF 8.0 (s, Quant. (1.01 (1.01 mmol) (1.01 mmol) (2 mL) COF US 2011/0160488 A1 Jun. 30, 2011 20

TABLE 4-continued Fluorination of Various Target Compounds with ArSFX by a One-Step-Process in the Presence of a Different Reducing Substance. 19F Target Reducing Fluorinated NMR Ex ASFX Compound Substance Solvent Temp Time Product (ppm) Yield 41 XIV PCOOH Pyridine CHCl2 rt. 1.5h PhCOF 18.0 (s, Quant. (1.48 (1.48 mmol) (1.48 mmol) (3 mL) COF) mmol)

42 IV OB Pyridine CH2Cl2 rt. Sh OB -138.1 83% (1.25 (1.25 mmol) (2 mL) (B- mmol) BO BO isomer) BO O BO O -149.5 (C- isomer) BO OH BO F (1.25 mmol) C/B = 12/88 Quant, = quantitative yield, TBAI = tetrabutylammonioum iodide, cat, = a catalytic amount, THF = tetrahydrofuran.

Examples 43-67 on an oil bath heated at 85°C. After the addition of all the diphenyl disulfide, the reaction mixture was stirred for 0.5 hat Fluorinations of Various Target Compounds with 85°C. Chlorine (C1) as a gaseous product evolved and was Arylsulfur Halotetrafluorides by a Two-Step Process removed from the reaction mixture; and (step 2) 3 mL of dry with a Reducing Substance and in Accordance with methylene chloride and 2.63 mmol of n-dodecanol were the Present Invention added into the reaction mixture obtained by step 1, and the 0177. A typical procedure for Ex. 43-51 in accordance mixture was stirred at room temperature for 24 hours. 'F with embodiments of the present invention is as follows: (step NMR showed that n-dodecyl fluoride was produced in 80% 1) 2.22 mmol of pyridine was added to a solution of 2.22 yield. mmol of phenylsulfur chlorotetrafluoride in 2 mL of dry 0179 Fluorinations of various target compounds with methylene chloride in a fluoropolymer (PFA) vessel at room various arylsulfur halotetrafluorides and various reducing temperature under nitrogen atmosphere. The reaction mix Substances were conducted in the same manner as above. ture was stirred for 1.5 hours at room temperature. At this Table 5 showed the results and the detailed reaction condi point, 'F NMR analysis of the reaction mixture showed that tions. In Ex. 44-48, 52-67, in step 2, an additive and/or a phenylsulfur trifluoride was formed in highyield; and (step 2) solvent (shown in Table 5) was added into the reaction mix 1.8 mmol of benzoic acid was added into the reaction mixture ture in addition to a target compound. A Small amount of obtained by step 1, and the mixture was stirred at room ethanol added in step 2 of Ex. 54 and 55 reacted with aryl temperature for 0.5 hours. 'F NMR showed that benzoyl sulfur trifluoride to form ethyl fluoride and hydrogen fluoride fluoride was produced in a quantitative yield. (HF), and the HF catalyzed the fluorination of the target 0.178 A typical procedure for Ex. 52-67 is as follows: compounds with arylsulfur trifluoride which remained. The (step 1) a solution of 0.65 mmol of diphenyl disulfide in 0.6 products were identified by comparison with authentic mL of dry methylene chloride was added dropwise to a stirred samples and/or spectral analyses. The yields of products were liquid of 3.95 mmol of phenylsulfur chlorotetrafluoride in a determined by the NMR analysis. fluoropolymer vessel heated on an oil bath of 85°C. The 0180. The experimental examples of step 1 in Examples methylene chloride (bp 40°C.) was removed from the reac 43-67 are considered to be the experimental examples for the tion mixture just after the addition by means of vaporization methods for preparing arylsulfur trifluorides in this invention. US 2011/0160488 A1 Jun. 30, 2011 21

ÇHT8IVIL

TISTS US 2011/0160488 A1 Jun. 30, 2011 22

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Examples 68 Examples 70 Preparation of Phenylsulfur Trifluorides from Phe Preparation of Phenylsulfur Trifluoride from Phenyl nylsulfur Chlorotetrafluorides with Pyridine (as a sulfur Chlorotetrafluoride with KCl (as a Reducing Reducing Substance) Substance) 0185 0181 ()-se -- ()-se + pyridine -- ()—s, IV IV KC --> ()-s, -- c + KF

Phenylsulfur chlorotetrafluoride (3.5 g. 15.87 mmol), dry acetonitrile (7 mL), and potassium chloride (KC1, 3.5g, 47 0182 Under nitrogen atmosphere, pyridine (0.79 g, 10 mmol) were put in a fluoropolymer (PFA) reactor equipped with a magnetic stirrer, a condenser, and a gas exit. The mmol) was added to a solution of phenylsulfur chlorotet mixture was heated at 85°C. for 5h on an oil bath. During that rafluoride (2.205 g, 10 mmol) in 5 mL of dry methylene time, gas (chlorine, Cl) was evolved, which was detected chloride in a fluoropolymer (PFA) vessel at room tempera with a paper soaked with an aqueous KI Solution. After the ture. The reaction mixture was stirred at room temperature for reaction, the reaction mixture was cooled to room tempera 1.5 hours. After the reaction, the reaction solvent was ture and filtered under nitrogen atmosphere. Acetonitrile was removed under vacuum and the residue was distilled under removed at reduced pressure and the residue was distilled to reduced pressure to give 1.46 g (88%) of phenylsulfur trif give phenylsulfur trifluoride (2.2g, by 70-71°C./10 mmHg, luoride (bp. 70° C./10 mmHg). F NMR (CDCN) & 57.84 85% yield). NMR data are shown in Example 65. (bris, 2F), -41.99 (brs, 1F). Examples 71 Examples 69 Preparation of Phenylsulfur Trifluorides from Phe Preparation of 2,6-Difluorophenylsulfur Trifluoride nylsulfur Chlorotetrafluoride with Diphenyl Disul from 2,6-Difluorophenylsulfur Chlorotetrafluoride fide (as a Reducing Substance) with Pyridine (as a Reducing Substance) 0186. 0183) ()-sa -- F F IV

SFC + pyridine -> SF

F F 4,3 ()-s, -- act XIII 0187 Phenylsulfur chlorotetrafluoride (2.18 g., 9.87 mmol) was put in a fluoropolymer (PFA) reactor equipped with a magnetic stirrer, a condenser, and a gas exit. The 0184 Under nitrogen atmosphere, pyridine (75 mg. 0.93 reactor was heated to 85°C. on an oil bath, and a solution of mmol) was added to a solution of 2,6-difluorophenylsulfur 0.359 g (1.64 mmol) of diphenyl disulfide in 1 mL of dry chlorotetrafluoride (a 6:1 mixture of trans- and cis-isomers) methylene chloride was added dropwise for 10 min. Evolu (240 mg. 0.93 mmol) in 2 mL of dry methylene chloride in a tion ofgas (Cl) was started after about 15 min. Heating at 85° fluoropolymer (PFA) vessel at room temperature. The reac C. was continued till the evolution of chlorine stopped. It took tion mixture was stirred at room temperature for 1.5 hours. 0.75 h. After the reaction, the reaction mixture was distilled NMR analysis of the reaction mixture showed that 2,6-dif under reduced pressure to give 1.96 g (11.8 mmol) (90% luorophenylsulfur trifluoride was produced in 99% yield. 'F yield) of phenylsulfur trifluoride (bp. 70° C./10 mmHg). NMR (CDCN) & 65.85 (dt, J=72.9, 11.2 Hz, SF), -55.22 NMR data are shown in Example 65. The molaramount of the (m, SF), -110.6 (m, aromatic F), -112.9 (m, aromatic F). obtained product (phenylsulfur trifluoride) was 1.2 times US 2011/0160488 A1 Jun. 30, 2011

molar amount of the molar amount of the starting material Examples 73 (phenylsulfur chlorotetrafluoride) used. 0188 The gas (Cl) generated from the reaction was Preparation of Phenylsulfur Trifluoride and Chlo passed through a solution of trans-Stilbene (1.44g, 8 mmol) in rophenylsulfur Trifluoride from Phenylsulfur Chlo 10 mL of methylene chloride at ice water temperature. After rotetrafluorides with Thiophenol (as a Reducing Sub the reaction, the reaction Solution was evaporated up to dry stance) ness to give the solid (1.72 g). H NMR and GC-Mass analy ses of the solid showed that an about 1.5:1 mixture of two (0192 isomeric 1,2-dichlorostilbene was produced. The GC-Mass spectral data agreed with the authentic sample. The weight increase of the product (1.72 g) from stilbene (1.44 g) used was 280 mg (3.94 mmolas Cl) which corresponded to the ()-se -- amount of chlorine gas generated. The amount of C1 gener ated was calculated to be at least 80% yield on the basis of the IV theoretical amount (4.94 mmol). This experiment demon strated that chlorine (Cl) was generated from the reaction of PhSFC1 and diphenyl disulfide. 1.3 KX-st -e- Examples 72 Preparation of p-Chlorophenylsulfur Trifluorides from p-Chlorophenylsulfur Chlorotetrafluorides with Bis(p-Chlorophenyl) Disulfide (as a Reducing Sub ( )—s,SF -- Ky\ / SF stance) (0189 (0193 Phenylsulfur chlorotetrafluoride (2.732 g, 12.39 mmol) was put in a fluoropolymer (PFA) reactor equipped with a magnetic stirrer, a condenser, and a gas exit. The c-()-se -- reactor was heated to 85°C. on an oil bath, and a solution of IX 0.452 g (4.10 mmol) of thiophenol in 0.5 mL of dry methylene chloride was added dropwise for 10 min. Evolution of gas started immediately. The gas oxidized an aqueous KI Solu 1.6 c-()---()—a He tion. The gas was assumed to be a mixture of chlorine (Cl), hydrogen fluoride, and hydrogen chloride. Heating at 85°C. 4,3 Cl SF + act was continued till the evolution of gas stopped. It took about 0.5 h. After the reaction, the reaction mixture was distilled under reduced pressure to give 2.4 g of a liquid (bp 70-71 0.190 p-Chlorophenylsulfur chlorotetrachloride (2.55 g, C./10 mmHg), which was found that a 2:1 mixture of phenyl 10 mmol) was put in a fluoropolymer (PFA) vessel equipped sulfur trifluoride and chlorophenylsulfur trifluoride was pro with a magnetic stirrer, a condenser made of fluoropolymer duced in a total 81% yield, by NMR and GC-Mass analyses. (PFA), and a gas exit. A solution of bis(p-chlorophenyl) dis 'F-NMR (CDCN) of phenylsulfur trifluoride; 8 57.94 (d. ulfide (0.477 g, 1.67 mmol) in 0.5 mL of dry methylene J=58 Hz, SF), -41.73 (t, J=58 Hz, SF). F-NMR (CDCN) chloride was added in portion wise to the fluoropolymer of chlorophenylsulfur trifluoride; 8 57.75 (d. J=58 Hz, SF), -40.13 (t, J-58 Hz, SF). The position of the chlorine atom on vessel heated at 85° C. for 10 min. After about 20 min, the benzene ring was not determined. For the GC-Mass mea evolution of gas (Cl) was started, which was checked by a surement, the product was treated with methanol and the paper soaked with an aqueous KI Solution. Heating was con resulting reaction mixture was measured by GC-Mass. The tinued till the evolution of C1 ceased. It took about 2.25 GC-Mass detected methyl phenylsulfinate and methyl chlo hours. After that, the reaction mixture was cooled to room rophenylsulfinate, which were derived from phenylsulfur tri temperature and distilled under reduced pressure to give 2.38 fluoride and chlorophenylsulfur trifluoride by the reaction g (11.9 mmol) (89% yield) of p-chlorophenylsulfur trifluo with methanol, respectively. ride; bp. 56°C/1 mmHg. 'F NMR (CDCN) & 55.59 (brs, 0194 The total molar amount (12.8 mmol) of the obtained 2F), -40.60 (brs, 1F). products (phenylsulfur trifluoride and p-chlorophenylsulfur 0191 The molar amount of the obtained product (p-chlo trifluoride) was 1.03 times molar amount of the starting mate rophenylsulfur trifluoride) was 1.2 times molar amount of the rial (phenylsulfur chlorotetrafluoride) used. Both phenylsul starting material (p-chlorophenylsulfur chlorotetrafluoride) fur trifluoride and chlorophenylsulfur trifluoride are fluori used. nating agents. US 2011/0160488 A1 Jun. 30, 2011 26

Examples 74 Preparation of p-(Tert-Butyl)Phenylsulfur Trifluo (I) rides from p-(Tert-Butyl)Phenylsulfur Chlorotet rafluorides with Bisp-(Tert-Butyl)Phenyl Disulfide (as a Reducing Substance) SFX 0195 R4 R5

wherein X is a chlorine atom, bromine atom, or iodine atom, and R', R. R. R. and Reach is independently > ()– SFCI -- a hydrogen atom, a halogen atom, a Substituted or unsubstituted linear, branched, or cyclic alkyl group VI having one to ten carbon atoms, a nitro group, a cyano group, a Substituted or unsubstituted aryl group having six to sixteen carbon atoms, a Substituted or unsubsti tuted alkanesulfonyl group having one to ten carbon atoms, a Substituted or unsubstituted arenesulfonyl group having six to sixteen carbon atoms, a Substituted 4,3 ) ()-st -- act or unsubstituted alkoxy group having one to ten carbon atoms, a Substituted or unsubstituted aryloxy group hav ing six to sixteen carbon atoms, or a SF's group. p-(tert-Butyl)phenylsulfur chlorotetrachloride (2.765 g, 10 2. The process of claim 1, wherein X is a chlorine atom. mmol) was put in a fluoropolymer (PFA) vessel equipped 3. The process of claim 1, wherein R. R. R. R', and R with a magnetic stirrer, a condenser made of fluoropolymer each is independently selected from a group consisting of a (PFA), and a gas exit. A solution of bisp-(tert-butyl)phenyl hydrogen atom, a halogen atom, a Substituted or unsubsti disulfide (0.548 g, 1.66 mmol) in 0.5 mL of dry methylene tuted linear or branched alkyl group having one to four carbon chloride was added in portion wise to the fluoropolymer atoms, and a nitro group. vessel heated at 95° C. for 10 min. After about 15 min, 4. The process of claim 1, wherein all of R. R. R. R. and Rare a hydrogen atom, or at maximum three of R', R. R. evolution of gas (Cl) was started, which was checked by a R, and Reach is independently selected from a group con paper soaked with an aqueous KI Solution. Heating was con sisting of a halogenatom, a Substituted or unsubstituted linear tinued till the evolution of C1 ceased. It took about 0.75 or branched alkyl group having one to four carbon atoms, and hours. After that, the reaction mixture was cooled to room a nitro group, and the remainders are a hydrogen atom. temperature and distilled under reduced pressure to give 2.71 5. The process of claim 1, wherein the arylsulfur halotet g (12.2 mmol) (92% yield) of p-(tert-butyl)phenylsulfur trif rafluoride is selected from a group consisting of phenylsulfur luoride; bp. 76° C./1 mmHg. H-NMR (CDC1) & 1.36 (s, chlorotetrafluoride, o-, m-, and p-alkylphenylsulfur chlo 9H), 7.58 (d. J=9 Hz, 2H), 7.95 (d. J=9 Hz, 2H), F NMR rotetrafluorides wherein the alkyl is a linear or branched alkyl (CDC1-EtO) & 55.91 (d. J=54.5 Hz, 2F), -37.01 (t, J=54.5 group having one to four carbon atoms, o-, m-, and p-fluo HZ, 1F). The molar amount of the obtained product p-(tert rophenylsulfur chlorotetrafluorides, o-, m-, and p-chlorophe butyl)phenylsulfur trifluoride was 1.22 times molar amount nylsulfur chlorotetrafluorides, o-, m-, and p-bromophenylsul of the starting material p-(tert-butyl)phenylsulfur chlorotet fur chlorotetrafluorides, o-, m-, and p-nitrophenylsulfur chlorotetrafluorides, and each isomer of difluorophenylsulfur rafluoride used. chlorotetrafluoride. 0196. It is understood for purposes of this disclosure, that 6. The process of claim 1, comprising contacting the target various changes and modifications may be made to the inven compound with arylsulfur halotetrafluoride as represented by tion that are well within the scope of the invention. Numerous the formula (I). other changes may be made which will readily suggest them 7. The process of claim 6, wherein X is a chlorine atom. selves to those skilled in the art which are encompassed in the 8. The process of claim 6, wherein R', R. R. R', and R spirit of the invention disclosed herein and as defined in the each is independently selected from a group consisting of a appended claims. hydrogen atom, a halogen atom, a Substituted or unsubsti tuted linear or branched alkyl group having one to four carbon 0197) This specification contains numerous citations to atoms, and a nitro group. references such as patents, patent applications, and publica 9. The process of claim 6, wherein all of R',R,R,R, and tions. Each is hereby incorporated by reference for all pur Rare a hydrogen atom, or at maximum three of R. R. R. poses. R, and Reach is independently selected from a group con sisting of a halogenatom, a Substituted or unsubstituted linear or branched alkyl group having one to four carbon atoms, and a nitro group, and the remainders are a hydrogen atom. What is claimed is: 10. The process of claim 6, wherein the arylsulfur halotet 1. A process for introducing one or more fluorine atoms rafluoride is selected from a group consisting of phenylsulfur into a target compound with arylsulfur halotetrafluoride as chlorotetrafluoride, o-, m-, and p-alkylphenylsulfur chlo represented by formula (I): rotetrafluorides wherein the alkyl is a linear or branched alkyl US 2011/0160488 A1 Jun. 30, 2011 27 group having one to four carbon atoms, o-, m-, and p-fluo reduce the arylsulfur halotetrafluoride represented by the for rophenylsulfur chlorotetrafluorides, o-, m-, and p-chlorophe mula (I) to arylsulfur trifluoride represented by the formula nylsulfur chlorotetrafluorides, o-, m-, and p-bromophenylsul (II): fur chlorotetrafluorides, o-, m-, p-nitrophenylsulfur chlorotetrafluorides, and each isomer of difluorophenylsulfur chlorotetrafluoride. (II) 11. The process of claim 1, comprising contacting the target compound with the arylsulfur halotetrafluoride repre sented by the formula (I) in the presence of a reducing Sub stance that reduces the arylsulfur halotetrafluoride. 12. The process of claim 11, wherein X of the halotet rafluoride is a chlorine atom. 13. The process of claim 11, wherein the arylsulfur halotet wherein R', R. R. R', and Reach is independently a rafluoride in which R', R. R. R., and Reach is indepen hydrogenatom, a halogen atom, a Substituted or unsub dently selected from a group consisting of a hydrogen atom, stituted linear, branched, or cyclic alkyl group having a halogen atom, a Substituted or unsubstituted linear or one to ten carbon atoms, a nitro group, a cyano group, a branched alkyl group having one to four carbonatoms, and a Substituted or unsubstituted aryl group having six to nitro group. sixteen carbon atoms, a Substituted or unsubstituted 14. The process of claim 11, wherein all of R', R. R. R. alkanesulfonyl group having one to ten carbon atoms, a and Rare a hydrogenatom, or at maximum three of R', R, Substituted or unsubstituted arenesulfonyl group having R. R', and Reach is independently selected from a group six to sixteen carbon atoms, a Substituted or unsubsti consisting of a halogen atom, a Substituted or unsubstituted tuted alkoxy group having one to ten carbon atoms, a linear or branched alkyl group having one to four carbon Substituted or unsubstituted aryloxy group having six to atoms, and a nitro group, and the remainders are a hydrogen sixteen carbon atoms, or a SFs group. atOm. 20. The process of claim 19, wherein the elements are 15. The process of claim 11, wherein the arylsulfur halotet alkali metals, alkali earth metals, transition metals, metals in rafluoride is selected from a group consisting of phenylsulfur Groups 13-15 of the Periodic Table, and semi-metals; the chlorotetrafluoride, o-, m-, and p-alkylphenylsulfur chlo inorganic compounds are inorganic chloride salts, inorganic rotetrafluorides wherein the alkyl is a linear or branched alkyl bromide salts, and inorganic iodide salts; and the organic group having one to four carbon atoms, o-, m-, and p-fluo compounds are organic chloride salts, organic bromide salts, rophenylsulfur chlorotetrafluorides, o-, m-, and p-chlorophe organic iodide salts, Substituted and unsubstituted aromatic nylsulfur chlorotetrafluorides, o-, m-, and p-bromophenylsul hydrocarbons, substituted and unsubstituted heteroaromatic fur chlorotetrafluorides, o-, m-, and p-nitrophenylsulfur compounds, Substituted and unsubstituted unsaturated ali chlorotetrafluorides, and each isomer of difluorophenylsulfur phatic hydrocarbons, Substituted and unsubstituted nitrogen chlorotetrafluoride. containing aliphatic hydrocarbons, organic Sulfur com pounds, salts or complexes of Substituted or unsubstituted 16. The process of claim 11, wherein the reducing sub heteroaromatic compounds and hydrogen fluoride, and salts stance is a Substance which has reduction potential that is or complexes of Substituted or unsubstituted nitrogen-con lower than that of arylsulfur halotetrafluoride as represented taining aliphatic hydrocarbons and hydrogen fluoride. by formula (I) used in the reaction. 21. The process of claim 1, comprising; (step 1) contacting 17. The process of claim 11, wherein the reducing sub arylsulfur halotetrafluoride represented by the formula (I) stance is at least one Substance selected from a group consist with a reducing substance that reduces the arylsulfur halotet ing of elements and inorganic and organic compounds that rafluoride, and then (step 2) contacting the target compound reduce arylsulfur halotetrafluoride as represented by formula with the resulting mixture from step 1. (I) used in the reaction. 22. The process of claim 21, wherein X of the arylsulfur 18. The process of claim 17, wherein the elements are halotetrafluoride is a chlorine atom. alkali metals, alkali earth metals, transition metals, metals in 23. The process of claim 21, wherein the arylsulfur halotet Groups 13-15 of the Periodic Table, and semi-metals; the rafluoride in which R', R. R. R', and Reach is indepen inorganic compounds are inorganic chloride salts, inorganic dently selected from a group consisting of a hydrogen atom, bromide salts, inorganic iodide salts; and the organic com a halogen atom, a Substituted or unsubstituted linear or pounds are organic chloride salts, organic bromide salts, branched alkyl group having one to four carbon atoms, and a organic iodide salts, Substituted and unsubstituted aromatic nitro group. hydrocarbons, substituted and unsubstituted heteroaromatic 24. The process of claim 21, wherein all of R', R. R. R. compounds, Substituted and unsubstituted unsaturated ali and Rare a hydrogenatom, or at maximum three of R', R, phatic hydrocarbons, Substituted and unsubstituted nitrogen R. R. and Reach is independently selected from a group containing aliphatic hydrocarbons, organic Sulfur com consisting of a halogen atom, a Substituted or unsubstituted pounds, salts or complexes of Substituted or unsubstituted linear or branched alkyl group having one to four carbon heteroaromatic compounds and hydrogen fluoride, and salts atoms, and a nitro group, and the remainders are a hydrogen or complexes of Substituted or unsubstituted nitrogen-con atOm. taining aliphatic hydrocarbons and hydrogen fluoride. 25. The process of claim 21, wherein the arylsulfur halotet 19. The process of claim 11, wherein the reducing sub rafluoride is selected from a group consisting of phenylsulfur stance is at least one Substance selected from a group consist chlorotetrafluoride, o-, m-, and p-alkylphenylsulfur chlo ing of elements and inorganic and organic compounds that rotetrafluorides wherein the alkyl is a linear or branched alkyl US 2011/0160488 A1 Jun. 30, 2011 28 group having one to four carbon atoms, o-, m-, and p-fluo salts, Substituted and unsubstituted aromatic hydrocarbons, rophenylsulfur chlorotetrafluorides, o-, m-, and p-chlorophe Substituted and unsubstituted heteroaromatic compounds, nylsulfur chlorotetrafluorides, o-, m-, and p-bromophenylsul Substituted and unsubstituted unsaturated aliphatic hydrocar fur chlorotetrafluorides, o-, m-, and p-nitrophenylsulfur bons, Substituted and unsubstituted nitrogen-containing ali chlorotetrafluorides, and each isomer of difluorophenylsulfur phatic hydrocarbons, organic Sulfur compounds, salts or chlorotetrafluoride. complexes of substituted or unsubstituted heteroaromatic 26. The process of claim 21, wherein the reducing sub compounds and hydrogen fluoride, and salts or complexes of stance is a Substance which has reduction potential that is Substituted or unsubstituted nitrogen-containing aliphatic lower than that of arylsulfur halotetrafluoride represented by hydrocarbons and hydrogen fluoride. the formula (I) used in the reaction. 31. The process of claim 1, comprising; (step 1) contacting 27. The process of claim 21, wherein the reducing sub arylsulfur halotetrafluoride represented by the formula (I) stance is at least one Substance selected from a group consist with a reducing substance to form arylsulfur trifluoride rep ing of elements and inorganic and organic compounds that resented by the formula (II), and then (step 2) contacting the reduce arylsulfur halotetrafluoride represented by the for target compound with the arylsulfur trifluoride obtained from mula (I) used in the reaction. step 1: whereinformula (II) is represented by: 28. The process of claim 27, wherein the elements are alkali metals, alkali earth metals, transition metals, metals in Groups 13-15 of the Periodic Table, and semi-metals; the (II) inorganic compounds are inorganic chloride salts, inorganic bromide salts, and inorganic iodide salts; and the organic compounds are organic chloride salts, organic bromide salts, organic iodide salts, Substituted and unsubstituted aromatic hydrocarbons, substituted and unsubstituted heteroaromatic compounds, Substituted and unsubstituted unsaturated ali phatic hydrocarbons, Substituted and unsubstituted nitrogen containing aliphatic hydrocarbons, organic Sulfur com pounds, salts or complexes of Substituted or unsubstituted wherein R', R. R. R', and Reach is independently a heteroaromatic compounds and hydrogen fluoride, and salts hydrogenatom, a halogen atom, a Substituted or unsub or complexes of Substituted or unsubstituted nitrogen-con stituted linear, branched, or cyclic alkyl group having taining aliphatic hydrocarbons and hydrogen fluoride. one to ten carbon atoms, a nitro group, a cyano group, a 29. The process of claim 21, wherein the reducing sub Substituted or unsubstituted aryl group having six to stance is at least one Substance selected from a group consist sixteen carbon atoms, a Substituted or unsubstituted ing of elements and inorganic and organic compounds that alkanesulfonyl group having one to ten carbon atoms, a reduce the arylsulfur halotetrafluoride represented by the for Substituted or unsubstituted arenesulfonyl group having six to sixteen carbon atoms, a Substituted or unsubsti mula (I) to arylsulfur trifluoride represented by the formula tuted alkoxy group having one to ten carbon atoms, a (II): Substituted or unsubstituted aryloxy group having six to sixteen carbon atoms, or a SFs group. (II) 32. The process of claim 31, the arylsulfur halotetrafluo ride in which X is a chlorine atom. 33. The process of claim 31, the arylsulfur halotetrafluo ride in which R', R. R. R', and Reach is independently selected from a group consisting of a hydrogenatom, a halo gen atom, a Substituted or unsubstituted linear or branched alkyl group having one to four carbon atoms, and a nitro group. 34. The process of claim 31, the arylsulfur halotetrafluo wherein R', R. R. R', and Reach is independently a ride in which all of R', R. R. R', and Rare a hydrogen hydrogenatom, a halogen atom, a Substituted or unsub atom, or at maximum three of R', R. R. R. and Reach is stituted linear, branched, or cyclic alkyl group having independently selected from a group consisting of a halogen one to ten carbon atoms, a nitro group, a cyano group, a atom, a substituted or unsubstituted linear or branched alkyl Substituted or unsubstituted aryl group having six to group having one to four carbonatoms, and a nitro group, and sixteen carbon atoms, a Substituted or unsubstituted the remainders are a hydrogen atom. alkanesulfonyl group having one to ten carbon atoms, a 35. The process of claim 31, wherein the arylsulfur halotet Substituted or unsubstituted arenesulfonyl group having rafluoride is selected from a group consisting of phenylsulfur six to sixteen carbon atoms, a Substituted or unsubsti chlorotetrafluoride, o-, m-, and p-alkylphenylsulfur chlo tuted alkoxy group having one to ten carbon atoms, a rotetrafluorides wherein the alkyl is a linear or branched alkyl Substituted or unsubstituted aryloxy group having six to group having one to four carbon atoms, o-, m-, and p-fluo sixteen carbon atoms, or a SFs group. rophenylsulfur chlorotetrafluorides, o-, m-, and p-chlorophe 30. The process of claim 29, the elements are alkali metals, nylsulfur chlorotetrafluorides, o-, m-, and p-bromophenylsul alkali earth metals, transition metals, metals in Groups 13-15 fur chlorotetrafluorides, o-, m-, and p-nitrophenylsulfur of the Periodic Table, and semi-metals; the inorganic com chlorotetrafluorides, and each isomer of difluorophenylsulfur pounds are inorganic chloride Salts, inorganic bromide salts, chlorotetrafluoride. and inorganic iodide salts; and the organic compounds are 36. The process of claim 31, wherein the reducing sub organic chloride salts, organic bromide salts, organic iodide stance is a Substance which has reduction potential that is US 2011/0160488 A1 Jun. 30, 2011 29 lower than that of arylsulfur halotetrafluoride represented by Substituted or unsubstituted arenesulfonyl group having the formula (I) used in the reaction. six to sixteen carbon atoms, a Substituted or unsubsti 37. The process of claim 31, wherein the reducing sub tuted alkoxy group having one to ten carbon atoms, a stance is at least one Substance selected from a group consist Substituted or unsubstituted aryloxy group having six to ing of elements and inorganic and organic compounds that sixteen carbon atoms, or a SFs group, and R is a hydro gen atom, a halogen atom, a metal atom, an ammonium reduce arylsulfur halotetrafluoride represented by the for moiety, a phosphonium moiety, or a silyl moiety. mula (I) to arylsulfur trifluoride represented by the formula 41. The process of claim 31, wherein the reducing sub (II). stance is LiCl, NaCl, KC1, RbCl, CsCl or mixture thereof. 38. The process of claim 37, wherein the elements are 42. The process of claim 31, wherein the reducing sub alkali metals, alkali earth metals, transition metals, metals in stance is at least one Substance selected from a group consist Groups 13-15 of the Periodic Table, and semi-metals; the ing of pyridine and its derivatives. inorganic compounds are inorganic chloride salts, inorganic 43. The process of claim 31, wherein the reducing sub bromide salts, and inorganic iodide salts; and the organic stance is at least one Substance selected from a group of alkyl compounds are organic chloride salts, organic bromide salts, alkenyl ethers. organic iodide salts, Substituted and unsubstituted aromatic 44. A process of preparation of arylsulfur trifluoride rep hydrocarbons, substituted and unsubstituted heteroaromatic resented by the formula (II): compounds, Substituted and unsubstituted unsaturated ali phatic hydrocarbons, Substituted and unsubstituted nitrogen containing aliphatic hydrocarbons, organic Sulfur com (II) pounds, salts or complexes of Substituted or unsubstituted heteroaromatic compounds and hydrogen fluoride, and salts or complexes of Substituted or unsubstituted nitrogen-con taining aliphatic hydrocarbons and hydrogen fluoride. 39. The process of claim 31, wherein the reducing sub stance is at least one Substance selected from a group consist ing of inorganic chloride salts, inorganic bromide salts, inor ganic iodide salts, organic chloride salts, organic bromide comprising contacting arylsulfur halotetrafluoride repre salts, organic iodide salts, Substituted and unsubstituted aro matic hydrocarbons, substituted and unsubstituted heteroaro sented by the formula (I) with a reducing Substance. matic compounds, Substituted and unsubstituted unsaturated aliphatic hydrocarbons, substituted and unsubstituted nitro gen-containing aliphatic hydrocarbons, organic Sulfur com (I) pounds, salts or complexes of Substituted or unsubstituted heteroaromatic compounds and hydrogen fluoride, and salts or complexes of Substituted or unsubstituted nitrogen-con R3 SFX taining aliphatic hydrocarbons and hydrogen fluoride. 40. The process of claim 31, wherein the reducing sub stance is at least one arylsulfur compound having a formula (IIIa) or a formula (IIIb) as follows: whereinX is a chlorine, bromine, or iodine atom, and R', R. R. R', and Reach is independently a hydrogen atom, a halogen atom, a Substituted or unsubstituted (IIIa) linear, branched, or cyclic alkyl group having one to ten carbon atoms, a nitro group, a cyano group, a Substituted or unsubstituted aryl group having six to sixteen carbon atoms, a Substituted or unsubstituted alkanesulfonyl group having one to ten carbonatoms, a Substituted or unsubstituted arenesulfonyl group having six to sixteen carbon atoms, a Substituted or unsubstituted alkoxy group having one to ten carbon atoms, a Substituted or unsubstituted aryloxy group having six to sixteen carbon atoms, or a SFs group. 45. A process of claim 44, wherein the reducing Substance is a Substance which has reduction potential that is lower than that of arylsulfur halotetrafluoride represented by the formula (I) used in the reaction. 46. A process of claim 44, wherein the reducing Substance is at least one Substance selected from a group consisting of wherein R. R. R. R', and Reach is independently a elements and inorganic and organic compounds that reduce hydrogenatom, a halogen atom, a Substituted or unsub arylsulfur halotetrafluoride represented by the formula (I) stituted linear, branched, or cyclic alkyl group having used in the reaction. one to ten carbon atoms, a nitro group, a cyano group, a 47. The process of claim 46, wherein the elements are Substituted or unsubstituted aryl group having six to alkali metals, alkali earth metals, transition metals, metals in sixteen carbon atoms, a Substituted or unsubstituted Groups 13-15 of the Periodic Table, and semi-metals; the alkanesulfonyl group having one to ten carbon atoms, a inorganic compounds are inorganic chloride salts, inorganic US 2011/0160488 A1 Jun. 30, 2011 30 bromide salts, and inorganic iodide salts; and the organic compounds are organic chloride salts, organic bromide salts, -continued organic iodide salts, Substituted and unsubstituted aromatic (IIIb) hydrocarbons, substituted and unsubstituted heteroaromatic R2 RI' compounds, Substituted and unsubstituted unsaturated ali phatic hydrocarbons, Substituted and unsubstituted nitrogen containing aliphatic hydrocarbons, organic Sulfur com pounds, salts or complexes of Substituted or unsubstituted heteroaromatic compounds and hydrogen fluoride, and salts or complexes of Substituted or unsubstituted nitrogen-con taining hydrocarbons and hydrogen fluoride. 48. The process of claim 44, wherein the reducing sub wherein R. R. R. R', and Reach is independently a stance is at least one Substance selected from a group consist hydrogenatom, a halogen atom, a Substituted or unsub ing of inorganic chloride salts, inorganic bromide salts, inor stituted linear, branched, or cyclic alkyl group having ganic iodide salts, organic chloride salts, organic bromide one to ten carbon atoms, a nitro group, a cyano group, a salts, organic iodide salts, Substituted and unsubstituted aro Substituted or unsubstituted aryl group having six to matic hydrocarbons, Substituted and unsubstituted heteroaro matic compounds, Substituted and unsubstituted unsaturated sixteen carbon atoms, a Substituted or unsubstituted aliphatic hydrocarbons, substituted and unsubstituted nitro alkanesulfonyl group having one to ten carbon atoms, a gen-containing aliphatic hydrocarbons, organic Sulfur com Substituted or unsubstituted arenesulfonyl group having pounds, salts or complexes of Substituted or unsubstituted six to sixteen carbon atoms, a Substituted or unsubsti heteroaromatic compounds and hydrogen fluoride, and salts tuted alkoxy group having one to ten carbon atoms, a or complexes of Substituted or unsubstituted nitrogen-con Substituted or unsubstituted aryloxy group having six to taining aliphatic hydrocarbons and hydrogen fluoride. sixteen carbon atoms, or a SFs group, and R is a hydro 49. A process of claim 44, wherein the reducing substance gen atom, a halogen atom, a metal atom, an ammonium is at least one arylsulfur compound having a formula (IIIa) or moiety, a phosphonium moiety, or a silyl moiety. a formula (IIIb) as follows: 50. A process of claim 44, wherein the reducing substance is LiCl, NaCl, KC1, RbCl, CsCl, or mixture thereof. (IIIa) 51. A process of claim 44, wherein the reducing substance R2 RI RI R2 is at least one Substance selected from a group consisting of pyridine and its derivatives. 52. A process of claim 44, wherein the reducing Substance is at least one Substance selected from a group consisting of alkyl alkenyl ethers.