Method for producing aryl compound containing triphenylmethylthio group

Abstract

Provided are a substrate for efficiently synthesizing a triphenylmethylthio group-containing aryl compound, a method for producing an SF5 group-containing compound using the substrate, and the like. The present invention is a method for producing an aryl compound containing a triphenylmethylthio group by reacting a compound represented by general formula (1) (wherein A1 represents an optionally substituted aryl group or an optionally substituted heteroaryl group, R2 represents an optionally substituted aryl group or an optionally substituted heteroaryl group, and R3 represents an optionally substituted aryl group or an optionally substituted heteroaryl group) using potassium [(triphenylmethyl) thio] or sodium [(triphenylmethyl) thio] potassium or sodium [(triphenylmethyl) thio] sodium. X represents a halogen atom] to produce a triphenylmethylthio group-containing aryl compound represented by general formula (2) [in the formula, A1 is the same as A1 in general formula (1), and Ph represents a phenyl group]. A1-X (1) # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a method for producing an aryl compound having a tritylthio group in which a tritylthio group is introduced into an aryl group.

[0002] This application claims priority based on Japanese Patent Application No. 2023-33954 filed on March 6, 2023 and Japanese Patent Application No. 2023-190006 filed on November 7, 2023, and incorporates their contents herein. Background Art

[0003] Pentafluorothio (SF5) is regarded as "super trifluoromethyl (CF3)" having excellent properties because of its small size, high electron-withdrawing property, excellent hydrolytic stability, and improved lipophilicity. On the other hand, it is difficult to introduce an SF5 group into existing compounds. Therefore, despite its high attractiveness, the use of the SF5 group in pharmaceutical and pesticidal active ingredients or organic materials has been slow to progress.

[0004] As a method for synthesizing a compound in which SF5 is introduced into an aryl group such as a phenyl group, there are various methods. For example, there are the following methods: a method of directly fluorinating an aryl disulfide using fluorine gas (F2) (Patent Document 1); a method of fluorinating an aryl disulfide using chlorine gas (Cl2) and potassium fluoride to obtain an arylthiotetrafluorochloride (Ar-SF4Cl), and then fluorinating it with zinc fluoride (ZnF2) or the like to obtain an aryl pentafluorosulfide (Ar-SF5) (Patent Document 2). In addition, as a method using silver(II) fluoride (AgF2), there is a method of synthesizing an aryl compound having a pentafluorothio group from a thioaryl compound in a single step by using silver(II) fluoride and a tetraalkylammonium halide (Patent Document 3).

[0005] On the other hand, tritylthio group is a commonly used protecting group for free thiols. Compounds obtained by introducing tritylthio group into an aryl or heteroaryl group (aryl compounds containing tritylthio group) are mostly synthesized mainly by reacting triphenylmethanol or trityl halide with aromatic thiols. Aryl compounds containing tritylthio group can also be synthesized by reacting tritylthiol with aromatic halides using cross-coupling reactions or the like, but the difficulty of this reaction is high. For example, in Non-Patent Document 1, phenyl(trimethylsilyl)sulfide was synthesized by reacting triphenylmethanethiol with phenyl iodide, but this reaction was carried out under severe conditions of reacting at 110 °C for 15 hours. In addition, in Non-Patent Document 2, phenyl(trimethylsilyl)sulfide was synthesized by reacting triphenylmethanethiol with phenyl fluoride, but this reaction required 36 hours at room temperature. In Patent Document 4, tritylthio group was introduced into imidazo[1,2-b]pyridazine by reacting triphenylmethanethiol with 1-chloroimidazo[1,2-b]pyridazine, but it required reacting at 90 °C for 5 hours.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 10-507206

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 2010-522213

[0010] Patent Document 3: WO 2022 / 186304

[0011] Patent Document 4: WO 1998 / 28299

[0012] Non-Patent Documents

[0013] Non-Patent Document 1: Yoshida et al., European Journal of Organic Chemistry, 2014, vol. 19, p. 3991-3995.

[0014] Non-Patent Document 2: Satyanarayana et al., Chemical Communications, 2012, vol. 48, p. 1461-1463. Summary of the Invention

[0015] In a method for synthesizing an aryl compound containing pentafluorothio group in a single step using silver(II) fluoride and tetraalkylammonium halide, by optimizing the thioaryl compound as a substrate, more efficient synthesis of an aryl compound containing pentafluorothio group can be expected.

[0016] An object of the present invention is to provide a method for producing a thioaryl compound suitable as a substrate for synthesizing an aryl compound containing a pentafluorothio group.

[0017] The present inventors found that a tritylthio group bonded to an aryl or heteroaryl group is efficiently fluorinated by silver(II) fluoride and a tetraalkylammonium halide. Therefore, a compound in which a tritylthio group is introduced into an aryl or heteroaryl group is suitable as a substrate for synthesizing a compound in which a pentafluorothio group is introduced into an aryl or heteroaryl group. Furthermore, it was found that by using potassium [(triphenylmethyl)thio] or sodium [(triphenylmethyl)thio], a halogen atom bonded to an aryl or heteroaryl group can be substituted with a tritylthio group under milder conditions, and thus the present invention was completed.

[0018] That is, the present invention is as follows.

[0019] [1] A method for producing an aryl compound containing a tritylthio group, which comprises subjecting a haloaryl compound represented by the following general formula (1) to tritylthiolation using potassium [(triphenylmethyl)thio] or sodium [(triphenylmethyl)thio] to produce an aryl compound containing a tritylthio group represented by the following general formula (2).

[0020] A 1 -X (1)

[0021] [In the formula, A 1 is an aryl group which may have a substituent or a heteroaryl group which may have a substituent, and X is a halogen atom]

[0022]

[0023] [In the formula, A 1 is the same as A in the general formula (1), and Ph is a phenyl group] 1

[0024] [2] The method for producing an aryl compound containing a tritylthio group according to the above [1], wherein the tritylthiolation of the haloaryl compound represented by the general formula (1) is further carried out using a palladium catalyst.

[0025] [3] The method for producing an aryl compound containing a tritylthio group according to the above [2], wherein the palladium catalyst is Pd[cinnamyl]( t BuXPhos)OTf or Pd[allyl](AlPhos)OTf.

[0026] [4] The method for producing an aryl compound containing a tritylthio group according to any one of the above [1] to [3], wherein the above A 1An aryl group that may have one or more substituents selected from a halogen atom, an alkyl group, a fluoroalkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, a hydroxyl group, a carboxyl group, an acyl group, a cyano group, a fluorocarbonyl group, an amino group, a nitro group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, a pyrazolidinyl group, an imidazolidinyl group, a tetrahydrofuranyl group, a 1,3-dioxolanyl group, a tetrahydrothienyl group, a 1,2-oxathiolanyl group, a morpholinyl group, and a tetrahydropyranyl group, or

[0027] A as described above 1 A heteroaryl group that may have one or more substituents selected from a halogen atom, an alkyl group, a fluoroalkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, a hydroxyl group, a carboxyl group, an acyl group, a cyano group, a fluorocarbonyl group, an amino group, a nitro group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, a pyrazolidinyl group, an imidazolidinyl group, a tetrahydrofuranyl group, a 1,3-dioxolanyl group, a tetrahydrothienyl group, a 1,2-oxathiolanyl group, a morpholinyl group, and a tetrahydropyranyl group.

[0028] [5] The method for producing an aryl compound containing a tritylthio group according to any one of the above [1] to [4], wherein the thiotritylation reaction is carried out at 0 to 80 °C.

[0029] [6] A method for producing an aryl compound containing a pentafluorothio group, wherein the aryl compound containing a tritylthio group represented by the above general formula (2) is produced from the haloaryl compound represented by the above general formula (1) by the method for producing an aryl compound containing a tritylthio group according to any one of the above [1] to [5],

[0030] By using a metal fluoride with a valence of 2 or more and an organic salt containing a quaternary ammonium cation or a quaternary cation, the aryl compound containing a pentafluorothio group represented by the following general formula (3) is synthesized by an oxidative fluorination reaction of the aryl compound containing a tritylthio group.

[0031] A 1 -SF5 (3)

[0032] [In the formula, A 1 is the same as A in the general formula (1) 1

[0033] [7] The method for producing an aryl compound containing a pentafluorothio group according to the above [6], wherein the oxidative fluorination reaction is carried out at -40 to 130 °C.

[0034] According to the method of the present invention, a tritylthio group can be introduced into various aryl compounds under relatively mild conditions, and an aryl compound containing a tritylthio group can be efficiently synthesized. Detailed implementation mode

[0035] In the present invention and the specification of this application, "C​p1-p2 "(where p1 and p2 are positive integers satisfying p1 < p2) represents a group having p1 to p2 carbon atoms."

[0036] In the present invention and the specification of this application, "C" 1-6 "alkyl" is an alkyl group having 1 to 6 carbon atoms, which may be linear, branched, or cyclic. As examples of C 1-6 alkyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, cyclohexyl, etc. can be cited.

[0037] In the present invention and the specification of this application, "C" 1-6 "alkoxy" refers to a group in which an oxygen atom is bonded to the terminal of the bond of C 1-6 alkyl. C 1-6 alkoxy may be linear or branched. As examples of C 1-6 alkoxy, methoxy, ethoxy, propoxy, butoxy, tert-butoxy, pentyloxy, hexyloxy, etc. can be cited.

[0038] In the present invention and the specification of this application, "C" 2-6 "alkenyl" refers to a group in which at least one carbon-carbon bond of an alkyl group having 2 to 6 carbon atoms becomes an unsaturated bond. As C 2-6 alkenyl, it may be linear, branched, or cyclic. As examples of C 2-6 alkenyl, vinyl, allyl, butenyl, pentenyl, hexenyl, cyclohexenyl, etc. can be cited.

[0039] In the present invention and the specification of this application, "C" 2-7 "acyl" refers to a group in which the hydrocarbon group obtained by removing the carbonyl group from the acyl group is C 1-6 alkyl, C 2-6 alkenyl, an aryl group having a 5-membered or 6-membered ring, or a heteroaryl group having a 5-membered or 6-membered ring. The hydrocarbon group of this acyl group may be linear or branched. As C 2-7 acyl, formyl, acetyl, propionyl, acryloyl, benzoyl, etc. can be cited.

[0040] In the present invention and the specification of this application, "halogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. "Halogen atom other than fluorine atom" refers to a chlorine atom, a bromine atom, or an iodine atom. As an example of "halogen atom other than fluorine atom", a chlorine atom or a bromine atom is preferred, and a chlorine atom is particularly preferred.

[0041] In addition, hereinafter, "compound (n)" refers to the compound represented by formula (n).

[0042] <Method for producing an aryl compound containing a tritylthio group>

[0043] The method for producing an aryl compound containing a tritylthio group (hereinafter sometimes referred to as "aryl compound containing STr") of the present invention is a method for producing an aryl compound containing STr represented by the following general formula (2) by subjecting a haloaryl compound represented by the following general formula (1) to tritylthiolation using potassium [(triphenylmethyl)thio] or sodium [(triphenylmethyl)thio].

[0044] A 1 —X (1)

[0045]

[0046] In the general formula (1), X is a halogen atom. As the haloaryl compound (1), X is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom or a bromine atom.

[0047] In the general formula (2), Ph represents an unsubstituted (having no substituent) phenyl group.

[0048] In the general formulas (1) and (2), A 1 is an aryl group which may have a substituent or a heteroaryl group which may have a substituent. In the present invention and the specification of the present application, the "aryl group which may have a substituent" includes both an unsubstituted aryl group and an aryl group having at least one substituent. Similarly, the "heteroaryl group which may have a substituent" includes both an unsubstituted heteroaryl group and a heteroaryl group having at least one substituent.

[0049] As the aryl group and heteroaryl group of A 1 , as long as the ring structure to which X is bonded is an aromatic ring, it may be a group having a condensed ring of an aryl ring or a heteroaryl ring and a non-aromatic ring. For example, as the aryl group of A 1 , it may be a monovalent group of a benzodialkane ring formed by condensing a benzene ring and a dialkane ring.

[0050] A 1 When A is an aryl group which may have a substituent, there is no particular limitation on the aryl group. For example, a phenyl group, a naphthyl group, an anthryl group, a 9-fluorenyl group, etc. may be mentioned, and a phenyl group is particularly preferred. When A 1 is a heteroaryl group which may have a substituent, there is no particular limitation on the heteroaryl group. For example, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazolyl group, a quinolinyl group, an isoquinolinyl group, a pyrrolyl group, an imidazolyl group, an indolyl group, a furyl group, a benzofuryl group, a thienyl group, a benzothienyl group, an oxazolyl group, a benzoxazolyl group, an isoxazolyl group, a benzisoxazolyl group, a benzodioxolyl group Azolyl, benzodioxolyl, benzodioxanyl (benzodioxolanyl group), quinazolinyl, quinoxalinyl, thiazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, thiazinyl, benzothiazinyl, benzothienyl, chromenyl, dibenzofuranyl, carbazolyl, fluorenyl, phenazinyl, phen azinyl and the like.

[0051] "Aryl having a substituent" is a group in which one or more, preferably 1 to 3, of the hydrogen atoms bonded to the carbon atoms of the aryl are substituted by other functional groups. Similarly, "heteroaryl having a substituent" is a group in which one or more, preferably 1 to 3, of the hydrogen atoms bonded to the carbon atoms of the heteroaryl are substituted by other functional groups. When there are two or more substituents, the substituents may be the same or different from each other.

[0052] As the aryl or heteroaryl of A 1 , the substituents are not particularly limited as long as they do not interfere with the tritylation of the halogen atom of the haloaryl compound (1). Examples of such substituents include a halogen atom, an alkyl group, a fluoroalkyl group, an alkenyl group, an alkoxy group, an aryl group, a heteroaryl group, an acyl group, a hydroxyl group, a carboxyl group, a cyano group, a fluorocarbonyl group (-C(=O)F), an amino group, a nitro group, and a non-aromatic heterocyclic group. As the alkyl group, preferably a C 1-6 alkyl group, as the alkenyl group, preferably a C 2-6 alkyl group, as the alkoxy group, preferably a C 1-6 alkoxy group, as the acyl group, preferably a C 2-7 acyl group. As the fluoroalkyl group, preferably a group in which one or two or more hydrogen atoms of a C 1-6 alkyl group are substituted by fluorine atoms, more preferably a perfluorinated C 1-6 alkyl group in which all hydrogen atoms are substituted by fluorine atoms, and particularly preferably a trifluoromethyl group. As the aryl group and the heteroaryl group, groups similar to those exemplified as the aryl group and the heteroaryl group of A 1 are respectively exemplified, and preferably a phenyl group or a pyridyl group. As the non-aromatic heterocyclic group, pyrrolidinyl, piperidinyl, piperazinyl, pyrazolidinyl, imidazolidinyl, tetrahydrofuranyl, 1,3-dioxolanyl, tetrahydrothienyl, 1,2-oxathiolanyl, morpholinyl, tetrahydropyranyl and the like can be exemplified.

[0053] A 1 When the substituents of the aryl or heteroaryl are an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a heteroaryl group, or an amino group, these substituents may further have substituents. Examples of such substituents include the same groups as those described above. For example, as A 1 , it may be an aryl group having an unsubstituted C 1-6 alkyl group as a substituent, or it may be an aryl group having a C 1-6 alkyl group in which one hydrogen atom is substituted by a phenyl group.An aryl group having an alkyl group as a substituent. In addition, as A 1 , it may be an aryl group having an unsubstituted amino group as a substituent, or an aryl group having an amino group in which one or two hydrogen atoms are substituted by a phenyl group as a substituent.

[0054] A 1 The substituents of the aryl group and heteroaryl group of A may be protected by a protecting group. As the protecting group, a group generally used in organic synthesis can be appropriately used. For example, when the substituent is an amino group, before being subjected to a tritylthiolation reaction, two hydrogen atoms of the amino group can be previously substituted with tert-butoxycarbonyl, benzyloxycarbonyl, 9-fluorenylmethoxycarbonyl, 2,2,2-trichloroethoxycarbonyl, allyloxycarbonyl, trifluoroacetyl, phthaloyl, p-toluenesulfonyl or 2-nitrobenzenesulfonyl. Similarly, when the substituent is a carboxyl group, for the carboxyl group, a hydrogen atom can be previously substituted with a benzyl group or a tert-butyl group.

[0055] A 1 When A is a heteroaryl group which may have a substituent, the heteroatom in the heteroaryl group may also be protected by a protecting group. As the protecting group, the same groups as those described above can be cited.

[0056] In the present invention, as the haloaryl compound (1), A 1 is preferably a phenyl group which may have a substituent, a benzoxazolyl group which may have a substituent, a benzodioxolyl group which may have a substituent, a dibenzofuranyl group which may have a substituent, an indolyl group which may have a substituent, a quinoxalinyl group which may have a substituent, a pyridyl group which may have a substituent, a pyrimidinyl group which may have a substituent, a furanyl group which may have a substituent. In addition, when these groups have a substituent, it is preferably a group having 1 to 3 substituents selected from a C alkyl group which may have a substituent, a C 1-6 alkoxy group which may have a substituent, a C 1-6 acyl group which may have a substituent, a halogen atom, an amino group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a piperazinyl group which may have a substituent and a cyano group. 1-6 alkyl group which may have a substituent, a C 1-6 alkoxy group which may have a substituent, a C 2-7 acyl group which may have a substituent, a halogen atom, an amino group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a piperazinyl group which may have a substituent and a cyano group.

[0057] In the present invention, the tritylthiolation reaction of the haloaryl compound (1) uses potassium [(triphenylmethyl)thio] or sodium [(triphenylmethyl)thio] as the STr group source. In the present invention, by using the sodium salt or potassium salt of STr as the STr group source, the tritylthiolation reaction can be carried out under milder conditions, specifically in the range of a reaction temperature of 0 to 80 °C.

[0058] In the present invention, the thiotriphenylmethylation reaction of the haloaryl compound (1) can also be carried out using a catalyst. As such a catalyst, a palladium catalyst is preferred, and a catalyst composed of a palladium complex is more preferred, and a catalyst composed of a palladium complex coordinated with a phosphine ligand is further preferred. The phosphine ligand is not particularly limited. For example, there can be mentioned t BuXPhos (2-Di-tert-butylphosphino-2’,4’,6’-triisopropylbiphenyl: CAS No. 564483-19-8), AlPhos (Di-1-adamantyl(4”-butyl-2”,3”,5”,6”-tetrafluoro-2’,4’,6’-triisopropyl-2-methoxy-m-terphenyl)phosphine: CAS No. 1805783-60-1), Xphos (2-Dicyclohexylphosphino-2’,4’,6’-triisopropylbiphenyl: CAS No. 564483-18-7), BrettPhos (2-(Dicyclohexylphosphino)-3,6-dimethoxy-2’,4’,6’-triisopropyl-1,1’-biphenyl: CAS No. 1070663-78-3), Ad-BrettPhos (Bis(adamantan-1-yl)[3,6-dimethoxy-2’,4’,6’-tris(propan-2-yl)-[1,1’-biphenyl]-2-yl]phosphine: CAS No. 1160861-59-5), Ad-BippyPhos (5-[Bis(adamantan-1-yl)phosphino]-1’,3’,5’-triphenyl-1’H-1,4’-bipyrazole: CAS No. 1239478-87-5), RuPhos (2-(Dicyclohexylphosphino)-2’,6’-isopropoxybiphenyl: CAS No. 787618-22-8), Me3(OMe) t BuXPhos (2-Di-tert-butylphosphino-4-methoxy-3,5,6-trimethyl-2’,4’,6’-triisopropylbiphenyl: manufactured by Sigma Aldrich, 792470-250MG), Sphos (2-Dicyclohexylphosphino-2’,6’-dimethoxybiphenyl: CAS No. 657408-07-6), t Bu-BrettPhos (3,6-Dimethoxy-2’,4’,6’-tris(1-methylethyl)[1,1’-biphenyl]-2-yl)bis(1,1-dimethylethyl)phosphine: CAS No. 1160861-53-9), Me4 t BuXPhos (2-Di-tert-butylphosphino-3,4,5,6-tetramethyl-2’,4’,6’-triisopropyl)-1,1’-biphenyl: CAS No. 857356-94-6), MePhos (2-Dicyclohexylphosphino-2’-methylbiphenyl: CAS No. 251320-86-2), tBu-BippyPhos (5-(Di-tert-butylphosphino)-1’,3’,5’-triphenyl-1,4’-bi-1H-pyrazole: CAS No. 894086-00-1), JohnPhos ((2-biphenyl)di-tert-butylphosphine: CAS No. 224311-51-7), t BuDavePhos (2-Di-tert-butylphosphino-2’-(N,N-dimethylamino)biphenyl: CAS No. 224311-49-3), XantPhos (4,5’-Bis(diphenylphosphino)-9,9’-dimethylxanthene: CAS No. 161265-03-8), CyXantPhos (4,5-Bis(dicyclohexylphosphino)-9,9-dimethylxanthene: CAS No. 940934-47-4), t BuXantPhos (2-Di-tert-butylphosphino-2’,4’,6’-triisopropylbiphenyl: CAS No. 564483-19-8), DPEPhos ((Oxybis(2,1-phenylene))bis(diphenylphosphine): CAS No. 166330-10-5), etc., preferably t BuXPhos, AlPhos, t Bu-BippyPhos, CyXantPhos, XantPhos, Ad-BrettPhos, Ad-BippyPhos, BrettPhos, t Bu-BrettPhos. As the catalyst composed of a palladium complex, for example, Pd[cinnamyl]( t BuXPhos)OTf or Pd[allyl](AlPhos)OTf can be cited.

[0059] In the present invention, the amount of the STr group source ([(triphenylmethyl)thio]potassium or [(triphenylmethyl)thio]sodium) added to the reaction system of the thiotriphenylmethylation reaction of the haloaryl compound (1) may be a stoichiometric amount or more. From the viewpoints of reaction efficiency and cost, the usage amount of [(triphenylmethyl)thio]potassium or [(triphenylmethyl)thio]sodium in this thiotriphenylmethylation reaction is preferably 1 to 10 equivalents, more preferably 1 to 6 equivalents, of the haloaryl compound (1).

[0060] In the present invention, when a catalyst is used in the thiotriphenylmethylation reaction of the haloaryl compound (1), the amount of the catalyst added to the reaction system is not particularly limited. From the aspect of reaction efficiency, the concentration in the reaction system is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and further preferably 1.0 mol% or more. In addition, from the viewpoint of cost, the amount of the catalyst used is preferably 20 mol% or less, more preferably 15 mol% or less, and further preferably 10 mol% or less.

[0061] The thiotriphenylmethylation reaction of the haloaryl compound (1) can be carried out in a solvent that is inactive to the reaction. As such an inactive solvent, there is no particular limitation, and an aprotic polar solvent is preferred. Examples of the aprotic polar solvent include acetonitrile (MeCN), N,N'-dimethylformamide (DMF), N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), dichloromethane (DCM), diethyl ether, and the like. The solvent used in the reaction can be a mixed solvent of two or more solvents.

[0062] The thiotriphenylmethylation reaction of the haloaryl compound (1) is a reaction in which a reaction solution prepared by mixing the haloaryl compound (1), the STr group source (potassium [(triphenylmethyl)thio] or sodium [(triphenylmethyl)thio]) and, if necessary, a catalyst in a reaction solvent is reacted at an appropriate temperature and for an appropriate time. The thiotriphenylmethylation reaction proceeds under relatively mild conditions. For example, as long as the reaction temperature is a temperature at which the reaction solvent is liquid, there is no particular limitation, and it can be carried out at -40 to 130 °C, preferably at 0 to 80 °C, and particularly preferably at 40 to 70 °C from the viewpoint of both excellent reaction efficiency and reaction convenience. For example, by carrying out the thiotriphenylmethylation reaction at 0 to 80 °C for 1 to 24 hours, the target aryl compound (2) containing STr can be obtained in an essentially quantitative yield.

[0063] <Method for producing aryl compound containing pentafluorothio group>

[0064] The aryl compound containing pentafluorothio group (aryl compound containing SF5) can be produced by oxidative fluorination of the above-mentioned aryl compound (2) containing STr. This oxidative fluorination reaction can be carried out, for example, under the conditions described in Patent Document 3.

[0065] Specifically, the method for producing the aryl compound containing SF5 of the present invention produces the aryl compound (2) containing STr from the haloaryl compound (1) by the above-mentioned method for producing the aryl compound containing STr, and by using a metal fluoride with a valence of 2 or more and containing a quaternary ammonium cation or a quaternary The oxidative fluorination reaction of the organic salt of a cation synthesizes the aryl compound containing SF5 represented by the following general formula (3) from the above-mentioned aryl compound containing tritylthio group. In general formula (3), A 1 is the same as A in general formula (1). 1 Same.

[0066] A 1 —SF5 (3)

[0067] As the metal fluoride with a valence of 2 or more used as a catalyst, fluorides of the first transition element, the second transition element, or the third transition element can be cited. Specifically, as the fluorinating agent used in the present invention, fluorides of silver, niobium, manganese, cobalt, copper, hafnium, tantalum, or cerium with a valence of 2 or more are preferred, and examples include AgF2, manganese(III) fluoride (MnF3), cobalt(III) fluoride (CoF3), copper(II) fluoride (CuF2), niobium(V) fluoride (NbF5), hafnium(V) fluoride (HfF5), tantalum fluoride (TaF5), cerium(IV) fluoride (CeF4), etc. In the present invention, as the metal fluoride with a valence of 2 or more used as a fluorinating agent, AgF2 is particularly preferred from the aspect of good reactivity.

[0068] The organic salt used as the fluorinating agent in the above oxidative fluorination reaction is not particularly limited as long as it is an organic salt containing a quaternary ammonium cation or a quaternary cation. As such an organic salt, for example, compounds represented by the following general formulas (s1) to (s7) can be cited.

[0069]

[0070] In general formulas (s1) to (s5), R 12 is an alkyl group or an aryl group. As such an aryl group, it can be the same group as the group cited for the above A 1-6 . When there are multiple Rs in one molecule, they can all be the same group or different groups from each other. 1 12

[0071] In general formulas (s6) to (s7), R 13 is an alkyl group, an aryl group, a C 1-6 alkoxy group, or a C 1-6 alkylamino group. As such an aryl group, it can be the same group as the group cited for the above A 1-6 . As such a C 1 alkylamino group, as long as it is a group in which one or two hydrogen atoms of the amino group are substituted by a C 1-6 alkyl group, it is not particularly limited. As such a C 1-6 alkylamino group, for example, dimethylamino can be cited. When there are multiple Rs in one molecule 1-6 ​​​13 They can all be the same group or different groups from each other.

[0072] In general formulas (s1) to (s7), as X 1 , as long as it is a monovalent anion that forms a salt with a quaternary ammonium cation or a quaternary cation, there is no particular limitation. As this X 1- , examples include iodide ion (I - ), bromide ion (Br - ), chloride ion (Cl - ), fluoride ion (F - ), hydrogen difluoride ion (HF2 - ), tribromide ion (Br3 - ), azide ion (N3 - ), cyanide ion (CN - ), cyanate ion (OCN - ), etc.

[0073] As the organic salt used as a fluorinating agent in the above oxidative fluorination reaction, tetraalkylammonium halide (NR 11 4X) is particularly preferred. As the NR 11 4X used in the above oxidative fluorination reaction, as long as it is a halide in which 4 alkyl groups are bonded to a nitrogen atom, there is no particular limitation. As the halide, chloride or bromide is preferred, and chloride is particularly preferred. In addition, as the alkyl group bonded to the nitrogen atom, it can be linear or branched, and the 4 alkyl groups can all be the same group or different groups from each other. As this alkyl group, C 1-6 alkyl group is preferred, and methyl, ethyl or propyl is more preferred. Among them, as NR 11 4X, N(Et)4Cl (tetraethylammonium chloride) (CAS No: 56-34-8) or N(Et)4Br (tetraethylammonium bromide) (CAS No: 71-91-0) is preferred, and N(Et)4Cl is more preferred.

[0074] The amount of the organic salt such as NR 11 4X added to the reaction system only needs to be a stoichiometric amount or more. From the aspects of reaction efficiency and cost, the usage amount of the organic salt such as NR 11 4X in the above oxidative fluorination reaction is preferably 1 to 10 equivalents of the aryl compound (2) containing STr, and more preferably 1 to 6 equivalents.

[0075] The amount of metal fluorides with a valence of 2 or more, such as AgF2, added to the reaction system is not particularly limited. From the perspective of reaction efficiency, it is preferably 5 equivalents or more, more preferably 8 equivalents or more, and further preferably 10 equivalents or more of the aryl compound (2) containing STr. Additionally, from the perspective of cost, the usage amount of metal fluorides with a valence of 2 or more, such as AgF2, in the above oxidative fluorination reaction is preferably 100 equivalents or less, more preferably 50 equivalents or less, further preferably 30 equivalents or less, and even more preferably 20 equivalents or less of the aryl compound (2) containing STr.

[0076] The above oxidative fluorination reaction can be carried out in a solvent that is inert to the reaction. As such an inert solvent, there is no particular limitation, and aprotic polar solvents are preferred. As aprotic polar solvents, the solvents listed above can be used. The solvent used in the reaction can be a mixed solvent of two or more solvents.

[0077] The above oxidative fluorination reaction causes a reaction solution prepared by mixing an aryl compound (2) containing STr, an organic salt such as NR 11 4X, and a metal fluoride with a valence of 2 or more, such as AgF2, in a reaction solvent to react at an appropriate temperature and time. The oxidative fluorination reaction proceeds under mild conditions. For example, as long as the reaction temperature is a temperature at which the reaction solvent is in a liquid state, there is no particular limitation, and it can be carried out at -40 to 130 °C, preferably at 0 to 80 °C, or it can also be carried out at room temperature (0 to 30 °C). For example, the above oxidative fluorination reaction can obtain the target aryl compound (3) containing SF5 in an essentially quantitative yield by reacting at room temperature for less than 1 hour.

[0078] Through the above oxidative fluorination reaction, metal fluorides with a valence of 2 or more, such as AgF2, undergo defluorination to generate metals such as Ag. By recovering metals such as Ag generated by the reaction and performing fluorination, metal fluorides with a valence of 2 or more, such as AgF2, can be regenerated. The regenerated metal fluorides with a valence of 2 or more, such as AgF2, can be reused in the above oxidative fluorination reaction. The fluorination of metals such as Ag can be carried out by conventional methods such as heating in fluorine gas.

[0079] The above oxidative fluorination reaction can synthesize the aryl compound (3) containing SF5 in one - pot with high yield through a single step under relatively mild reaction conditions. Additionally, in this oxidative fluorination reaction, in most cases, partial fluorides such as aryl compounds containing the SF4Cl group are not generated. Therefore, it also has the advantage that there is no need to separate the aryl compound containing the SF4Cl group from the reaction product to purify the target aryl compound (3) containing SF5.

[0080] Examples

[0081] The present invention will be described below by way of examples, but the present invention is not limited to these examples.

[0082] Unless otherwise specified, all reagents were purchased from a dealer and used without further purification.

[0083] All reactions under argon were carried out using dried and degassed solvents. Unless otherwise specified, all yields reported refer to spectroscopically and chromatographically pure compounds.

[0084] Analytical thin-layer chromatography (TLC) was performed on pre-coated glass plates with silica gel (layer thickness 0.25 nm, Kiesel gel 60F254, manufactured by Merck) and visualized by UV lamp (254 or 365 nm) and / or appropriate staining reagents.

[0085] Column chromatography was carried out using Kanto silica gel 60N (spherical, neutral).

[0086] Unless otherwise specified, 1 H, 13 C, 19 F, 31 P nuclear magnetic resonance (NMR) spectra were measured at ambient temperature using an NMR instrument (manufactured by JEOL, JNM-ECZ400S) or an NMR instrument (manufactured by JEOL, ECZ500R). The solvents used and their respective measurement frequencies are shown in each experiment. The resonance multiplicity is expressed as s (singlet), d (doublet), t (triplet), q (quartet), p (quintet), m (multiplet), br (broad). The residual deuterated solvent signal relative to tetramethylsilane (e.g., for CDCl3 = 1 7.26 ppm for 13 H and 1 77.160 ppm for 13 C) is used as the internal standard for

[0087] H and

[0088] [Synthesis Example 1] Synthesis of Pd[cinnamyl]( t BuXPhos)OTf catalyst (Catalyst 1)

[0089]

[0090] In a 15 mL volumetric glass vial inside a glove box under an argon atmosphere, silver trifluoromethanesulfonate (AgOTf, 308.3 mg, 1.2 mmol, 2.0 equivalents) was added to a stirred mixture of THF (6.0 mL) and Pd[cinnamyl]Cl dimer (310.8 mg, 0.6 mmol, 1.0 equivalent). The mixture, in which silver chloride formed as a white precipitate, was stirred at room temperature for 1 hour. The white precipitate in the reaction mixture was removed using a syringe filter, and the filtrate was added to a 50 mL volumetric glass vial containing t BuXPhos (509.6 mg, 1.2 mmol, 2.0 equivalents). After stirring at room temperature for 2 hours, hexane (30 mL) was added to the reaction solution, giving an orange precipitate. The supernatant was removed by decantation, and the residue was washed 3 times with hexane (10 mL). The residue was evaporated under reduced pressure to give Pd[cinnamyl]( t BuXPhos)OTf (937.3 mg, yield 98%) as an orange powder.

[0091] 1 H NMR (400 MHz, CDCl3) δ 7.96 (t, J = 7.2 Hz, 1H), 7.54 (t, J = 8.0 Hz, 2H), 7.47 (tt, J = 7.3, 1.5 Hz, 1H), 7.35 (t, J = 7.7 Hz, 2H), 7.13 (br, 3H), 6.82 - 6.62 (m, 1H), 5.71 (br, 1H), 4.91 (br, 1H), 2.62 - 2.10 (m, 2H), 1.67 - 0.71 (m, 39H).

[0092] 19 F NMR (376 MHz, CDCl3) δ -78.0.

[0093] 13 C NMR (101 MHz, CDCl3) δ 153.1, 151.7, 147.1, 146.8, 135.6, 135.4, 135.1, 133.8, 133.7, 131.6, 131.5, 130.4 (doublet), 129.8 (doublet), 128.1, 128.0, 125.4, 123.3, 122.7, 119.5, 119.0, 116.3, 110.2, 39.4, 39.3, 32.3, 31.5, 31.4 (doublet), 31.1, 25.9, 25.7, 25.1, 24.9, 24.6, 22.8, 22.5, 14.3. [Complexity due to C - P and C - F coupling was observed].

[0094] 311P NMR (162 MHz, CDCl3) δ 76.7.

[0095] [Synthesis Example 2] Synthesis of Pd[allyl](AlPhos)OTf Catalyst (Catalyst 2)

[0096]

[0097] In a 15 mL volumetric glass vial in a glove box under an argon atmosphere, silver trifluoromethanesulfonate (AgOTf, 25.7 mg, 0.1 mmol, 2.0 equivalents) was added to a stirred mixture of THF (1.0 mL) and palladium(II) allyl chloride dimer (18.3 mg, 0.05 mmol, 1.0 equivalent). The mixture, which formed silver chloride as a white precipitate, was stirred at room temperature for 1 hour. The white precipitate in the reaction mixture was removed using a syringe filter, and the filtrate was added to a 50 mL volumetric glass vial containing AlPhos (81.5 mg, 0.1 mmol, 2.0 equivalents). After stirring at room temperature for 2 hours, hexane (10 mL) was added to the reaction solution to obtain an orange precipitate. The supernatant was removed by decantation, and the residue was washed 3 times with hexane (5 mL). The residue was evaporated under reduced pressure to obtain Pd[allyl](AlPhos)OTf as an orange powder (108.5 mg, yield 98%).

[0098] 1 1H NMR (400 MHz, CDCl3) δ 7.75 (d, J = 12.9 Hz, 1H), 7.53 (t, J = 8.0 Hz, 1H), 7.19 - 7.10 (m, 1H), 6.38 - 6.24 (m, 1H), 6.09 - 5.83 (m, 1H), 5.75 - 5.49 (m, 1H), 4.73 (dd, J = 61.4, 6.1 Hz, 1H), 4.03 (s, 3H), 3.89 (dd, J = 13.6, 9.0 Hz, 1H), 3.48 (dd, J = 14.3, 8.2 Hz, 1H), 3.05 (dd, J = 23.9, 12.1 Hz, 2H), 2.84 (t, J = 7.4 Hz, 2H), 2.77 - 2.60 (m, 1H), 2.52 - 1.92 (m, 20H), 1.70 (m, 14H), 1.57 (s, 1H), 1.44 (m, 4H), 1.32

[0099] -1.14 (m, 6H), 1.07 - 0.95 (m, 4H), 0.90 (t, J = 6.5 Hz, 4H), 0.80 (d, J = 6.7 Hz, 1H), 0.69 (d, J = 5.9 Hz, 1H).

[0100] 1919F NMR (376 MHz, CDCl3) δ -78.0 (s, 3F), -135.5--136.2 (m), -136.8 (dd, J = 23.8, 12.3 Hz), -138.6 (dd, J = 23.9, 12.1 Hz), -142.9 (ddd, J = 98.4, 23.6, 12.3 Hz), -143.7 (ddd, J = 45.7, 23.8, 12.4 Hz).

[0101] 13 13C NMR (101 MHz, CDCl3) δ 161.8 (dd, J = 3.6, 2.2 Hz), 155.1, 154.6, 154.5, 153.8, 152.0, 148.4 (dd, J = 24.9, 21.3 Hz), 146.0, 134.0, 127.5, 127.3 (d, J = 11.2 Hz), 126.9, 126.01, 122.7, 122.6-121.3 (m), 120.2 (d, J = 3.8 Hz), 119.5, 118.7, 111.5 (d, J = 2.6 Hz), 102.0 (dd, J = 25.1, 6.4 Hz), 98.0 (dd, J = 26.6, 10.1 Hz), 68.0, 60.4, 57.4, 54.9, 45.8 (dd, J = 11.5, 2.0 Hz), 44.9 (dd, J = 36.3, 10.3 Hz), 43.1-40.9 (m), 36.2 (d, J = 8.3 Hz), 34.2, 32.9 (dd, J = 60.7, 51.0 Hz), 31.4, 30.9, 30.0-28.3 (m), 26.1, 25.9-25.6 (m), 25.5, 24.3 (d, J = 11.1 Hz), 23.9, 23.8, 23.2, 22.9, 22.4, 22.4-22.3 (m), 21.5 (d, J = 3.1 Hz), 14.1, 13.8. [Observed due to the complexity of C-P and C-F couplings].

[0102] 31 31P NMR (162 MHz, CDCl3) δ 88.2 (d, J = 101.6 Hz).

[0103] [Synthesis Example 3] Synthesis of Potassium [(Triphenylmethyl)thio] or Sodium [(Triphenylmethyl)thio]

[0104]

[0105] In a 100 mL round-bottom flask in a glove box under an argon atmosphere, triphenylmethanethiol (8.29 g, 30 mmol, 1.0 equiv) was dissolved in THF (60 mL). The resulting solution was cooled to -30 °C, and potassium hydride (KH, 1.80 g, 45 mmol, 1.5 equiv) was added little by little while stirring vigorously. Next, the flask was taken out of the cold bath and stirred vigorously at room temperature for 12 hours. Next, the reaction mixture was filtered to remove the excess KH and concentrated under reduced pressure to obtain potassium [(triphenylmethyl)thio] (KSTr) (9.34 g, 99% yield) as a yellow powder.

[0106] 1 H NMR (500 MHz, THF-d8) δ 7.55 (dd, J = 7.5, 0.9 Hz, 6H), 6.98 (t, J = 7.7 Hz, 6H), 6.90 - 6.85 (m, 3H).

[0107] By using sodium hydride instead of potassium hydride and carrying out the reaction in the same manner, sodium [(triphenylmethyl)thio] (NaSTr) (8.95 g, 99% yield) was obtained.

[0108]

[0109] [Synthesis Example 4] Synthesis of Pd[cinnamyl](DPEPhos)OTf Catalyst (Catalyst 3)

[0110]

[0111] In a 15 mL glass vial in a glove box under an argon atmosphere, silver trifluoromethanesulfonate (AgOTf, 256.9 mg, 1.0 mmol, 2.0 equiv) was added to a stirred mixture of THF (10.0 mL) and Pd[cinnamyl]Cl dimer (259.0 mg, 0.5 mmol, 1.0 equiv). The mixture that formed silver chloride as a white precipitate was stirred at room temperature for 1 hour. The white precipitate in the reaction mixture was removed using a syringe filter, and the filtrate was added to a 50 mL glass vial containing DPEPhos (538.6 mg, 1.0 mmol, 2.0 equiv). After stirring at room temperature for 2 hours, hexane (30 mL) was added to the reaction solution to obtain an orange precipitate. The supernatant was removed by decantation, and the residue was washed 3 times with hexane (10 mL). The residue was evaporated under reduced pressure to obtain Pd[cinnamyl](DPEPhos)OTf (907.1 mg, 99% yield) as an orange powder.

[0112] 11H NMR (400 MHz, DMSO-d6) δ 7.68 - 7.01 (m, 24H), 6.96 - 6.78 (m, 6H), 6.69 (t, J = 7.6 Hz, 1H), 6.61 (dd, J = 8.1, 4.7 Hz, 2H), 6.08 (t, J = 7.8 Hz, 1H), 5.43 (br, 1H), 3.90 (t, J = 11.6 Hz, 1H).

[0113] 19 19F NMR (376 MHz, CDCl3) δ -77.7.

[0114] [Production Example 1] Typical production method A for synthesizing aryl triphenylmethyl sulfide compounds (aryl compounds containing triphenylmethylthio group)

[0115]

[0116] Transfer the test tube dried in an oven into a glove box under an argon atmosphere. After adding aryl bromide (0.2 mmol) to a mixture of catalyst 1 (8.0 mg, 5 mol%) and toluene (0.4 mL, 0.5 M) in the test tube, cool the test tube in a refrigerator at -30 °C for 0.5 hour. While vigorously stirring at room temperature, add KSTr (KSCPh3) (94.3 mg, 0.3 mmol, 1.5 equivalents) to the mixture. After sealing with an aluminum cap with a septum using a vial sealer, take the test tube out of the glove box and stir at 40 °C (oil bath) for 12 hours. Remove the solvent of the reaction mixture using a rotary evaporator, and purify the crude product by silica gel column chromatography to obtain the corresponding aryl triphenylmethyl sulfide.

[0117] [Production Example 2] Typical production method B for synthesizing aryl triphenylmethyl sulfide compounds

[0118]

[0119] Transfer the test tube dried in an oven into a glove box under an argon atmosphere. After adding aryl bromide to a mixture of catalyst 2 and toluene (0.5 M) in the test tube, cool the test tube in a refrigerator at -30 °C for 0.5 hour. While vigorously stirring at room temperature, add KSTr (1.5 equivalents) to the mixture. After sealing with an aluminum cap with a septum using a vial sealer, take the test tube out of the glove box and stir at 70 °C (oil bath) for 18 hours. Remove the solvent of the reaction mixture using a rotary evaporator, and purify the crude product by silica gel column chromatography to obtain the corresponding aryl triphenylmethyl sulfide.

[0120] [Production Example 3] Typical production method C for synthesizing aryl triphenylmethyl sulfide compounds

[0121]

[0122] Transfer the test tube dried in an oven into a glove box under an argon atmosphere. After adding aryl chloride to the mixture of catalyst 1 or catalyst 2 (5 mol%) and toluene (0.5 M) in the test tube, cool the test tube in a refrigerator at -30 °C for 0.5 h. While stirring vigorously at room temperature, add KSTr (1.5 equivalents) to the mixture. After sealing with an aluminum cap with a septum using a vial sealer, take the test tube out of the glove box and stir at 40 °C (for catalyst 1) or 70 °C (for catalyst 2) (oil bath) for 18 h. Dilute the reaction mixture with CDCl3 and use 1 1H NMR to determine the yield of the aryl chloride raw material.

[0123] [Example 1]

[0124] Synthesize 4-methoxyphenyltrityl sulfide by production method A described in Production Example 1 or production method A' using NaSTr.

[0125]

[0126] (1) Production method A

[0127] Prepared from 4-bromoanisole (1.0 mmol, 187.0 mg) using catalyst 1 (5 mol%, 39.9 mg) according to production method A. After the reaction, purify by silica gel column chromatography (hexane / EtOAc = 40 / 1 → 20 / 1 → 10 / 1 (volume ratio)) to obtain 4-methoxyphenyltrityl sulfide (369.9 mg, yield 97%) in the form of a white powder.

[0128] 1 1H NMR (400 MHz, CDCl3) δ 7.41 - 7.36 (m, 6H), 7.25 - 7.15 (m, 9H), 6.91 - 6.85 (m, 2H), 6.58 - 6.52 (m, 2H), 3.70 (s, 3H).

[0129] 13 13C{ 1 1H} NMR (101 MHz, CDCl3) δ 160.2, 144.8, 137.9, 130.1, 127.7, 126.7, 124.4, 113.8, 70.9, 55.3.

[0130] (2) Production method A' (production method using NaSTr)

[0131] Using 4-bromoanisole (0.2 mmol, 37.4 mg) as the aryl bromide, and using NaSTr (NaSCPh3) (89.5 mg, 0.3 mmol, 1.5 equivalents) instead of KSTr, a reaction mixture containing 4-methoxyphenyltrityl sulfide was obtained in the same manner as in Production Method A. The resulting reaction mixture was diluted with CDCl3, and 1,4-bis(trifluoromethyl)benzene (15.5 μL, 0.1 mmol) was added as an internal standard, and the NMR yield of 4-methoxyphenyltrityl sulfide was determined. The result was 61%.

[0132] Compared with the NMR yield of the reaction using KSCPh3 (NMR yield 99%), from the viewpoints of reaction efficiency and cost, the STr group source used in this thiotritylation reaction is preferably potassium [(triphenylmethyl)thio]ate.

[0133] [Example 2]

[0134] 3,5-Dimethoxyphenyltrityl sulfide was synthesized by Production Method A described in Production Example 1.

[0135]

[0136] Specifically, according to Production Method A, it was prepared from 1-bromo-3,5-dimethoxybenzene (0.2 mmol, 43.4 mg) and Catalyst 1 (10 mol%, 16.0 mg). After the reaction, purification by silica gel column chromatography (hexane / DCM = 10:1 (volume ratio)) gave 3,5-dimethoxyphenyltrityl sulfide (66.1 mg, yield 80%) as a white powder.

[0137] 1 H NMR (400 MHz, CDCl3) δ 7.41 - 7.37 (m, 6H), 7.27 - 7.18 (m, 9H), 6.22 (t, J = 2.3 Hz, 1H), 6.14 (d, J = 2.3 Hz, 2H), 3.49 (s, 6H).

[0138] 13 C{ 1 H}NMR (101 MHz, CDCl3) δ 160.0, 144.6, 136.7, 130.2, 127.8, 126.9, 111.4, 101.2, 70.7, 55.3.

[0139] [Example 3]

[0140] 3,4,5-Trimethoxyphenyltrityl sulfide was synthesized by Production Method A described in Production Example 1.

[0141]

[0142] Specifically, according to production method A, it was prepared from 5-bromo-1,2,3-trimethoxybenzene (0.2 mmol, 49.4 mg) and catalyst 1 (5 mol%, 8.0 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / EtOAc = 100 / 1 → 40 / 1 → 20 / 1 (volume ratio)), and 3,4,5-trimethoxyphenyltrityl sulfide (67.2 mg, yield 76%) was obtained in the form of a white powder.

[0143] 1 H NMR (400 MHz, CDCl3) δ 7.41 - 7.34 (m, 6H), 7.27 - 7.18 (m, 9H), 6.21 (s, 2H), 3.77 (s, 3H), 3.50 (s, 6H).

[0144] 13 C{ 1 H}NMR (101 MHz, CDCl3) δ 152.5, 144.6, 138.5, 130.2, 128.7, 127.8, 126.9, 112.7, 71.0, 61.0, 56.0.

[0145] [Example 4]

[0146] 6-[(Trityl)thio]-1,4-benzodioxane was synthesized by the production method A described in Production Example 1. alkane.

[0147]

[0148] Specifically, according to production method A, it was prepared from 6-bromo-1,4-benzodioxane (0.2 mmol, 43.0 mg) and catalyst 1 (5 mol%, 8.0 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / EtOAc = 10 / 1 → 5 / 1 (volume ratio)), and 6-[(trityl)thio]-1,4-benzodioxane (68.2 mg, yield 83%) was obtained in the form of a white powder. alkane. alkane.

[0149] 1 H NMR (400 MHz, CDCl3) δ 7.43 - 7.37 (m, 6H), 7.26 - 7.15 (m, 9H), 6.52 - 6.42 (m, 3H), 4.19 - 4.10 (m, 4H).

[0150] 1313C NMR (101 MHz, CDCl3) δ 144.8, 144.3, 142.9, 130.1, 129.6, 127.7, 126.7, 125.5, 125.0, 116.9, 71.0, 64.5, 64.2.

[0151] [Example 5]

[0152] 4-Chlorophenyl triphenylmethyl sulfide was synthesized by Production Method A described in Production Example 1.

[0153]

[0154] Specifically, according to Production Method A, it was prepared from 1-bromo-4-chlorobenzene (0.2 mmol, 38.3 mg) and Catalyst 1 (5 mol%, 8.0 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / DCM = 20 / 1 (volume ratio)), and 4-chlorophenyl triphenylmethyl sulfide was obtained in the form of a yellow powder (51.8 mg, yield 67%).

[0155] 1 1H NMR (400 MHz, CDCl3) δ 7.39 (ddd, J = 6.0, 2.2, 0.9 Hz, 6H), 7.29 - 7.18 (m, 9H), 6.98 - 6.94 (m, 2H), 6.89 - 6.84 (m, 2H).

[0156] [Example 6]

[0157] 4-Fluorophenyl triphenylmethyl sulfide was synthesized by Production Method A described in Production Example 1.

[0158]

[0159] Specifically, according to Production Method A, it was prepared from 4-bromofluorobenzene (0.2 mmol, 35.0 mg) and Catalyst 1 (5 mol%, 8.0 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / EtOAc = 100 / 1 → 40 / 1 → 20 / 1 (volume ratio)), and 4-fluorophenyl triphenylmethyl sulfide was obtained in the form of a yellow powder (66.8 mg, yield 90%).

[0160] 1 1H NMR (500 MHz, CDCl3) δ 7.41 - 7.38 (m, 6H), 7.25 - 7.17 (m, 9H), 6.94 - 6.90 (m, 2H), 6.72 - 6.67 (m, 2H).

[0161] 13 C{ 11H NMR (126 MHz, CDCl3) δ 163.0 (d, 1JC-F = 248.8 Hz), 144.5, 137.6 (d, 3JC-F = 8.4 Hz), 130.0, 127.8, 126.8, 115.3 (d, 2JC-F = 21.5 Hz), 71.1.

[0162] 19 19F NMR (471 MHz, CDCl3) δ -112.8.

[0163] [Example 7]

[0164] 2-[(Triphenylmethyl)thio]-dibenzofuran was synthesized by Production Method A described in Production Example 1.

[0165]

[0166] Specifically, according to Production Method A, it was prepared from 2-bromodibenzofuran (0.2 mmol, 49.4 mg) and Catalyst 1 (5 mol%, 8.0 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / EtOAc = 40 / 1 → 20 / 1 → 10 / 1 (volume ratio)) to obtain 2-[(triphenylmethyl)thio]-dibenzofuran (86.3 mg, yield 97%) in the form of a white powder.

[0167] 1 1H NMR (400 MHz, CDCl3) δ 7.67 (ddd, J = 7.7, 1.3, 0.6 Hz, 1H), 7.52 - 7.35 (m, 9H), 7.30 - 7.13 (m, 12H).

[0168] 13 13C{ 1 1H} NMR (101 MHz, CDCl3) δ 156.5, 156.4, 144.7, 135.3, 130.2, 128.9, 128.1, 127.8, 127.4, 126.8, 124.5, 123.9, 123.0, 120.7, 111.8, 111.4, 71.3.

[0169] [Example 8]

[0170] 5'-[(Triphenylmethyl)thio]m-terphenyl was synthesized by Production Method A described in Production Example 1.

[0171]

[0172] Specifically, according to production method A, it was prepared from 5'-bromo-m-terphenyl (0.2 mmol, 61.8 mg) and catalyst 1 (5 mol%, 8.0 mg). After the reaction, it was purified by silica gel column chromatography (hexane / DCM = 20 / 1 → 10 / 1 → 5 / 1 (volume ratio)) to obtain 5'-[(triphenylmethyl)thio]-m-terphenyl (88.7 mg, yield 88%) in the form of a white powder.

[0173] 1 H NMR (400 MHz, CDCl3) δ 7.56 (t, J = 1.7 Hz, 1H), 7.44 (m, 6H), 7.40 - 7.19 (m, 21H).

[0174] 13 C{ 1 H}NMR (101 MHz, CDCl3) δ 144.6, 141.6, 140.5, 135.8, 132.0, 130.3, 128.8, 127.9, 127.6, 127.2, 127.0, 125.5, 71.0.

[0175] [Example 9]

[0176] 1-[(Triphenylmethyl)thio]-4-(trans-4'-propylcyclohexyl)benzene was synthesized by the production method A described in Production Example 1.

[0177]

[0178] Specifically, according to production method A, it was prepared from 1-bromo-4-(trans-4-propylcyclohexyl)benzene (0.5 mmol, 140.6 mg) and catalyst 1 (5 mol%, 19.9 mg). After the reaction, it was purified by silica gel column chromatography (hexane / DCM = 0 / 1 → 50 / 1 → 20 / 1 → 10 / 1 (volume ratio)) to obtain 1-[(triphenylmethyl)thio]-4-(trans-4'-propylcyclohexyl)benzene (234.5 mg, yield 98%) in the form of a white powder.

[0179] 1 H NMR (500 MHz, CDCl3) δ 7.45 - 7.36 (m, 6H), 7.24 - 7.13 (m, 9H), 6.88 - 6.80 (m, 4H), 2.38 - 2.23 (m, 1H), 1.78 (t, J = 15.0 Hz, 4H), 1.40 - 1.13 (m, 7H), 1.05 - 0.92 (m, 2H), 0.88 (t, J = 7.2 Hz, 3H).

[0180] 13 C{ 11H NMR (101 MHz, CDCl3) δ 148.2, 144.9, 135.4, 130.9, 130.2, 127.7, 126.8, 126.7, 70.9, 44.4, 39.8, 37.1, 34.3, 33.6, 20.2, 14.5.

[0181] [Example 10]

[0182] 4-[(Triphenylmethyl)thio]-4'-(diphenylamino)biphenyl was synthesized by Production Method A described in Production Example 1.

[0183]

[0184] Specifically, according to Production Method A, it was prepared from 4-bromo-4'-(diphenylamino)biphenyl (0.2 mmol, 80.1 mg) and Catalyst 1 (5 mol%, 8.0 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / EtOAc = 100 / 1 (volume ratio)) to obtain 4-[(triphenylmethyl)thio]-4'-(diphenylamino)biphenyl (101.0 mg, yield 85%) in the form of a white powder.

[0185] 1 1H NMR (500 MHz, CDCl3) δ 7.44 - 7.41 (m, 6H), 7.38 - 7.35 (m, 2H), 7.28 - 7.17 (m, 15H), 7.12 - 7.06 (m, 6H), 7.05 - 6.97 (m, 4H).

[0186] 13 13C{ 1 1H}NMR (101 MHz, CDCl3) δ 147.7, 147.5, 144.7, 140.0, 135.1, 134.1, 132.9, 130.2, 129.4, 127.8, 127.6, 126.8, 126.2, 124.6, 123.8, 123.2, 71.0.

[0187] [Example 11]

[0188] tert-Butyl 4-{4-[(triphenylmethyl)thio]phenyl}piperazine-1-carboxylate was synthesized by Production Method A described in Production Example 1.

[0189]

[0190] Specifically, according to production method A, it was prepared from tert-butyl 4-(4-bromophenyl)piperazine-1-carboxylate (0.2 mmol, 68.2 mg) and catalyst 1 (5 mol%, 8.0 mg). After the reaction, purification was carried out using silica gel column chromatography (hexane / EtOAc = 100 / 1 → 50 / 1 → 20 / 1 (volume ratio)) to obtain tert-butyl 4-{4-[(triphenylmethyl)thio]phenyl}piperazine-1-carboxylate (98.2 mg, yield 91%) in the form of a red powder.

[0191] 1 H NMR (500 MHz, CDCl3) δ 7.40 - 7.37 (m, 6H), 7.24 - 7.14 (m, 9H), 6.84 (d, J = 8.9 Hz, 2H), 6.53 (d, J = 8.9 Hz, 2H), 3.51 (t, J = 5.0 Hz, 4H), 3.06 (t, J = 5.0 Hz, 4H), 1.47 (s, 9H).

[0192] 13 C{ 1 H}NMR (101 MHz, CDCl3) δ 154.8, 144.9, 137.5, 130.1, 127.6, 126.6, 115.6, 80.1, 70.8, 48.6, 28.5 (Three carbon signals overlap.)

[0193] [Example 12]

[0194] N-Boc-5-[(triphenylmethyl)thio]-indole was synthesized by the production method A described in Production Example 1.

[0195]

[0196] Specifically, according to production method A, it was prepared from N-Boc-5-bromoindole (0.2 mmol, 59.2 mg) and catalyst 1 (5 mol%, 8.0 mg). After the reaction, purification was carried out using silica gel column chromatography (hexane / DCM = 10 / 1 → 5 / 1 (volume ratio)) to obtain N-Boc-5-[(triphenylmethyl)thio]-indole (61.1 mg, yield 62%) in the form of a white powder.

[0197] 11H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 8.6 Hz, 1H), 7.47 (d, J = 3.7 Hz, 1H), 7.39 (m, 6H), 7.24 - 7.11 (m, 9H), 7.05 (d, J = 1.5 Hz, 1H), 6.98 (dd, J = 8.7, 1.8 Hz, 1H), 6.30 (dd, J = 3.7, 0.6 Hz, 1H), 1.62 (s, 9H).

[0198] 13 C{ 1 13C{1H} NMR (101 MHz, CDCl3) δ 144.8, 131.9, 130.7, 130.2, 130.2, 130.2, 129.2, 127.7, 127.7, 127.7, 127.3, 126.7, 126.3, 114.7, 107.3, 71.0, 28.3

[0199] [Example 13]

[0200] 4'-Chloro-4-[(triphenylmethyl)thio]-1,1'-biphenyl was synthesized by Production Method B described in Production Example 2.

[0201]

[0202] Specifically, according to Production Method B, it was prepared from 4-bromo-4'-chloro-1,1'-biphenyl (0.2 mmol, 53.5 mg) and Catalyst 2 (1 mol%, 2.2 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / DCM = 20 / 1 (volume ratio)) to obtain 4'-chloro-4-[(triphenylmethyl)thio]-1,1'-biphenyl (91.3 mg, yield 99%) in the form of a white powder.

[0203] 1 1H NMR (400 MHz, CDCl3) δ 7.45 - 7.32 (m, 10H), 7.27 - 7.17 (m, 11H), 7.03 - 6.98 (m, 2H).

[0204] 13 C{ 1 13C{1H} NMR (101 MHz, CDCl3) δ 144.6, 139.1, 138.9, 134.8, 134.3, 133.7, 130.2, 129.0, 128.3, 127.9, 126.9, 126.6, 71.0.

[0205] [Example 14]

[0206] 2-Fluoro-4-[(triphenylmethyl)thio]-1,1'-biphenyl was synthesized by Production Method B described in Production Example 2.

[0207]

[0208] Specifically, according to Production Method B, it was prepared from 4-bromo-2-fluorobiphenyl (0.2 mmol, 50.2 mg) and Catalyst 2 (2 mol%, 4.4 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / DCM = 40 / 1 (volume ratio)) to obtain 2-fluoro-4-[(triphenylmethyl)thio]-1,1'-biphenyl (67.1 mg, yield 75%) in the form of a white powder.

[0209] 1 H NMR (400 MHz, CDCl3) δ 7.45 - 7.36 (m, 10H), 7.29 - 7.16 (m, 10H), 7.08 (t, J = 8.2 Hz, 1H), 6.83 (dd, J = 8.1, 1.8 Hz, 1H), 6.69 (dd, J = 11.4, 1.8 Hz, 1H).

[0210] 13 C{ 1 H}NMR (101 MHz, CDCl3) δ 158.8 (d, 1JC-F = 250.2 Hz), 144.3, 136.0 (d, J = 8.1 Hz), 135.3 (d, J = 1.4 Hz), 130.1, 130.0 (d, J = 4.0 Hz), 129.8 (d, J = 3.4 Hz), 129.0, 129.0, 128.6, 128.0, 127.9, 127.1, 121.24 (d, J = 24.4 Hz), 71.3.

[0211] 19 F NMR (376 MHz, CDCl3) δ -117.83.

[0212] [Example 15]

[0213] 2-{4-[(Triphenylmethyl)thio]phenyl}benzoxazole was synthesized by Production Method B described in Production Example 2. azole.

[0214]

[0215] Specifically, according to Production Method B, from 2-(4-bromophenyl)benzoxazole It was prepared from oxazole (0.2 mmol, 54.8 mg) and catalyst 2 (2 mol%, 4.4 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / DCM = 20 / 1 (volume ratio)) to obtain 2-{4-[(triphenylmethyl)thio]phenyl}benzoxazole (79.8 mg, yield 85%).

[0216] 1 H NMR (400 MHz, CDCl3) δ 7.86 (d, J = 8.4 Hz, 2H), 7.76 - 7.67 (m, 1H), 7.56 - 7.47 (m, 1H), 7.42 (d, J = 8.1 Hz, 6H), 7.36 - 7.18 (m, 11H), 7.07 (d, J = 8.4 Hz, 2H).

[0217] 13 C{ 1 H}NMR (101 MHz, CDCl3) δ 162.8, 150.8, 144.2, 142.2, 140.4, 132.8, 130.1, 128.1, 128.0, 127.2, 125.4, 125.3, 124.7, 120.1, 110.7, 71.3.

[0218] [Example 16]

[0219] 2-Methyl-5-[(triphenylmethyl)thio]pyrimidine was synthesized by Production Method B described in Production Example 2.

[0220]

[0221] Specifically, according to Production Method B, it was prepared from 5-bromo-2-methylpyrimidine (0.2 mmol, 34.6 mg) and catalyst 2 (5 mol%, 11.1 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / TEA = 100 / 1 (volume ratio)) to obtain 2-methyl-5-[(triphenylmethyl)thio]pyrimidine (64.9 mg, yield 88%).

[0222] 1 H NMR (400 MHz, CDCl3) δ 8.06 (s, 2H), 7.44 - 7.39 (m, 6H), 7.29 - 7.19 (m, 9H), 2.59 (s, 2H).

[0223] 13 C{ 11H NMR (101 MHz, CDCl3) δ 167.2, 161.9, 143.7, 129.7, 128.0, 127.2, 126.5, 71.7, 25.6.

[0224] [Example 17]

[0225] 2-Phenyl-5-[(triphenylmethyl)thio]-pyridine was synthesized by Production Method B described in Production Example 2.

[0226]

[0227] Specifically, according to Production Method B, it was prepared from 5-bromo-2-phenylpyridine (0.2 mmol, 46.8 mg) and Catalyst 2 (5 mol%, 11.1 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / DCM = 1 / 1 (volume ratio)) to obtain 2-phenyl-5-[(triphenylmethyl)thio]-pyridine (74.9 mg, yield 87%) in the form of a white powder.

[0228] 1 1H NMR (400 MHz, CDCl3) δ 8.32 (d, J = 2.1 Hz, 1H), 7.87 (dd, J = 8.0, 1.3 Hz, 2H), 7.48 - 7.42 (m, 8H), 7.37 - 7.12 (m, 12H).

[0229] 13 13 1 1H NMR (101 MHz, CDCl3) δ 147.0, 144.3, 142.8, 130.0, 129.3, 128.9, 128.1, 128.1, 128.0, 127.4, 127.1, 127.0, 119.8, 71.6.

[0230] [Example 18]

[0231] 4-Cyanophenyl triphenylmethyl sulfide was synthesized by Production Method B described in Production Example 2.

[0232]

[0233] Specifically, according to Production Method B, it was prepared from 4-bromobenzonitrile (0.05 mmol, 9.1 mg) and Catalyst 2 (5 mol%, 2.8 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / EtOAc = 10 / 1 (volume ratio)) to obtain 4-cyanophenyl triphenylmethyl sulfide (14.1 mg, yield 75%) in the form of a white powder.

[0234] 11H NMR (400 MHz, CDCl3) δ 7.39 - 7.35 (m, 6H), 7.30 - 7.19 (m, 11H), 6.99 (d, J = 8.3 Hz, 2H).

[0235] 13 13C{ 1 1H} NMR (101 MHz, CDCl3) δ 143.7, 143.4, 131.5, 131.3, 130.0, 128.2, 127.4, 118.9, 109.5, 71.5.

[0236] [Example 19]

[0237] Ethyl 5 - [(triphenylmethyl)thio] - 2 - furancarboxylate was synthesized by Production Method B described in Production Example 2.

[0238]

[0239] Specifically, according to Production Method B, it was prepared from ethyl 5 - bromo - 2 - furancarboxylate (0.05 mmol, 11.0 mg, 7.2 μL) and catalyst 2 (5 mol%, 2.8 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / Et2O = 20 / 1 (volume ratio)) to obtain ethyl 5 - [(triphenylmethyl)thio] - 2 - furancarboxylate (10.6 mg, yield 51%) in the form of a white powder.

[0240] 1 1H NMR (400 MHz, CDCl3) δ 7.38 - 7.34 (m, 6H), 7.28 - 7.17 (m, 9H), 6.83 (d, J = 3.5 Hz, 1H), 5.97 (d, J = 3.5 Hz, 1H), 4.27 (q, J = 7.1 Hz, 2H), 1.32 (t, J = 7.1 Hz, 3H).

[0241] 13 13C{ 1 1H} NMR (101 MHz, CDCl3) δ 158.2, 149.9, 146.9, 144.1, 130.0, 127.9, 127.2, 121.9, 118.7, 73.4, 61.1, 14.4.

[0242] [Example 20]

[0243] 4 - Nitrophenyl triphenylmethyl sulfide was synthesized by Production Method B described in Production Example 2.

[0244]

[0245] Specifically, according to Production Method B, it was prepared from 4-bromonitrobenzene (0.05 mmol, 10.1 mg) and Catalyst 2 (5 mol%, 2.8 mg). After the reaction, purification was carried out using silica gel column chromatography (hexane / Et2O = 20 / 1 (volume ratio)) to obtain 4-nitrophenyl triphenylmethyl sulfide (11.9 mg, yield 60%) in the form of a white powder.

[0246] 1 H NMR (400 MHz, CDCl3) δ 7.85 - 7.79 (m, 2H), 7.40 - 7.35 (m, 6H), 7.31 - 7.20 (m, 9H), 7.06 - 7.00 (m, 2H).

[0247] 13 C{ 1 H}NMR (101 MHz, CDCl3) δ 146.44, 145.67, 143.47, 130.37, 130.03, 128.22, 127.53, 123.12, 71.53.

[0248] [Example 21]

[0249] Methyl 3,5-bis[(triphenylmethyl)thio]benzoate was synthesized by the production method B described in Production Example 2.

[0250]

[0251] Specifically, according to Production Method B, it was prepared from 3,5-dibromobenzene (0.05 mmol, 14.7 mg) and Catalyst 2 (10 mol%, 5.6 mg). After the reaction, purification was carried out using silica gel column chromatography (hexane / EtOAc = 10 / 1 (volume ratio)) to obtain methyl 3,5-bis[(triphenylmethyl)thio]benzoate (28.2 mg, yield 82%) in the form of a white powder.

[0252] 1 H NMR (400 MHz, CDCl3) δ 7.33 - 7.28 (m, 12H), 7.22 (d, J = 1.7 Hz, 2H), 7.21 - 7.12 (m, 18H), 6.98 (t, J = 1.8 Hz, 1H), 3.68 (s, 3H).

[0253] 13 C{ 1 H}NMR (101 MHz, CDCl3) δ 165.7, 144.2, 143.9, 134.9, 134.9, 130.0, 129.6, 128.1, 128.1, 127.9, 126.9, 71.5, 52.0.

[0254] [Example 22]

[0255] 3,5-Bis[(triphenylmethyl)thio]chlorobenzene was synthesized by Production Method B described in Production Example 2.

[0256]

[0257] Specifically, according to Production Method B, it was prepared from 1,3-dibromo-5-chlorobenzene (0.05 mmol, 13.5 mg) and Catalyst 2 (10 mol%, 5.6 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / EtOAc = 20 / 1 (volume ratio)) to obtain 3,5-bis[(triphenylmethyl)thio]chlorobenzene (32.0 mg, yield 97%) in the form of a white powder.

[0258] 1 H NMR (400 MHz, CDCl3) δ 7.32 - 7.28 (m, 12H), 7.22 - 7.17 (m, 18H), 6.84 (t, J = 1.3 Hz, 1H), 6.42 (dd, J = 1.6, 0.5 Hz, 2H).

[0259] 13 C{ 1 H}NMR (101 MHz, CDCl3) δ 144.1, 135.7, 130.0, 129.4, 127.9, 127.5, 127.2, 127.0, 71.6.

[0260] [Example 23]

[0261] 4,4'-Bis[(triphenylmethyl)thio]-trans-stilbene was synthesized by Production Method B described in Production Example 2.

[0262]

[0263] Specifically, according to Production Method B, it was prepared from 4,4'-dibromo-trans-stilbene (0.05 mmol, 16.9 mg) and Catalyst 2 (10 mol%, 5.6 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / DCM = 10 / 3 (volume ratio)) to obtain 4,4'-bis[(triphenylmethyl)thio]-trans-stilbene (30.1 mg, yield 82%) in the form of a white powder.

[0264] 1 H NMR (400 MHz, CDCl3) δ 7.43 - 7.37 (m, 12H), 7.26 - 7.15 (m, 18H), 7.08 (d, J = 8.5 Hz, 4H), 6.91 (d, J = 8.5 Hz, 4H), 6.83 (s, 2H).

[0265] 13 C{ 1 1H NMR (101 MHz, CDCl3) δ 144.6, 136.4, 134.6, 134.1, 130.1, 128.3, 127.8, 126.8, 126.2, 71.0.

[0266] [Example 24]

[0267] 6-[(Triphenylmethyl)thio]quinoxaline was synthesized by Production Method B described in Production Example 2.

[0268]

[0269] Specifically, according to Production Method B, it was prepared from 6-bromoquinoxaline (0.05 mmol, 10.5 mg) and Catalyst 2 (5 mol%, 2.8 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / EtOAc = 1 / 1 (volume ratio)) to obtain 6-[(triphenylmethyl)thio]quinoxaline (17.4 mg, yield 86%) in the form of a white powder.

[0270] 1 1H NMR (400 MHz, CDCl3) δ 8.69 (q, J = 1.9 Hz, 2H), 7.72 (d, J = 8.9 Hz, 1H), 7.62 (d, J = 2.1 Hz, 1H), 7.46 (m, 6H), 7.35 (dd, J = 8.8, 2.1 Hz, 1H), 7.29 - 7.17 (m, 9H).

[0271] 13 C{ 1 1H NMR (101 MHz, CDCl3) δ 145.2, 144.5, 143.8, 142.6, 141.8, 139.4, 133.5, 131.6, 130.1, 128.5, 128.1, 127.2, 71.5.

[0272] [Example 25]

[0273] 4-Methoxyphenyltriphenylmethyl sulfide was synthesized by Production Method C described in Production Example 3.

[0274]

[0275] Specifically, according to Production Method C, it was prepared from 4-chloromethoxybenzene and Catalyst 1 or Catalyst 2. The yield was 4% when using Catalyst 1 and 16% when using Catalyst 2.

[0276] [Example 26]

[0277] 4-Nitrophenyl triphenylmethyl sulfide was synthesized by Production Method C described in Production Example 3.

[0278]

[0279] Specifically, according to Production Method C, it was prepared from 4-chloronitrobenzene and Catalyst 1 or Catalyst 2. The yield was 8% when using Catalyst 1 and 13% when using Catalyst 2.

[0280] [Production Example 4] Typical Production Method D for synthesizing aryl triphenylmethyl sulfide compounds

[0281] The test tube dried in an oven was transferred into a glove box under an argon atmosphere. After adding aryl iodide to the mixture of Catalyst 1 (5 mol%) and toluene (0.5 M) in the test tube, the test tube was cooled in a refrigerator at -30°C for 0.5 hour. While vigorously stirring at room temperature, KSTr (1.5 equivalents) was added to the mixture. After sealing with an aluminum cap with a septum using a vial sealer, the test tube was taken out of the glove box and stirred at room temperature for 12 hours. The obtained reaction mixture was diluted with CDCl3, and 1,4-bis(trifluoromethyl)benzene (15.5 μL, 0.1 mmol) was added as an internal standard to determine the NMR yield of the aryl triphenylmethyl sulfide compound.

[0282] [Example 27]

[0283] 4-Methoxyphenyl triphenylmethyl sulfide was synthesized by Production Method D described in Production Example 4.

[0284]

[0285] Specifically, according to Production Method D, it was prepared from 4-iodoanisole and Catalyst 1. The yield was 95%.

[0286] [Example 28]

[0287] 2-Methoxy-5-[(triphenylmethyl)thio]-pyridine was synthesized by Production Method D described in Production Example 4.

[0288]

[0289] Specifically, according to Production Method D, it was prepared from 5-iodo-2-methoxypyridine and Catalyst 1. The yield was 74%.

[0290] [Example 29]

[0291] 6-[(Triphenylmethyl)thio]quinoline was synthesized by Production Method D described in Production Example 4.

[0292]

[0293] Specifically, it is prepared from 6-iodoquinoline and catalyst 1 according to production method D. The yield is 53%.

[0294] [Example 30]

[0295] Methyl 4-(tritylthio)benzoate was synthesized by the production method D described in Production Example 4.

[0296]

[0297] Specifically, it is prepared from methyl 4-iodobenzoate and catalyst 1 according to production method D. The yield is 82%.

[0298] [Production Example 5] Typical production method E for synthesizing aryl trityl sulfide compounds

[0299]

[0300] The test tube dried in an oven was transferred into a glove box under an argon atmosphere. After adding aryl iodide (0.2 mmol) to a mixture of catalyst 3 (9.1 mg, 5 mol%) and toluene (0.4 mL, 0.5 M) in the test tube, KSTr (KSCPh3) (94.3 mg, 0.3 mmol, 1.5 equivalents) was added to the mixture while stirring vigorously at room temperature. After sealing with an aluminum cap with a septum using a vial sealer, the test tube was taken out of the glove box and stirred at room temperature for 12 hours. The solvent of the reaction mixture was removed by a rotary evaporator, and the crude product was purified by silica gel column chromatography to obtain the corresponding aryl trityl sulfide.

[0301] [Example 31]

[0302] 4-[(Tritylthio)benzophenone was synthesized by the production method E described in Production Example 5.

[0303]

[0304] Specifically, it is prepared from 4-iodobenzophenone (0.2 mmol, 61.6 mg) and catalyst 3 (5 mol%, 9.1 mg) according to production method E. After the reaction, 4-[(tritylthio)benzophenone (77.6 mg, yield 85%) was obtained in the form of a white powder by purification using silica gel column chromatography (hexane / ethyl acetate = 10:1 (volume ratio)).

[0305] 11H NMR (400 MHz, CDCl3) δ 7.71 - 7.66 (m, 2H), 7.59 - 7.52 (m, 1H), 7.47 - 7.38 (m, 10H), 7.30 - 7.18 (m, 9H), 7.06 - 7.00 (m, 2H).

[0306] 13 13C NMR (101 MHz, CDCl3) δ 196.2, 144.1, 142.2, 137.7, 135.2, 132.5, 131.2, 130.1, 130.0, 129.8, 128.4, 128.0, 127.2, 71.2.

[0307] [Example 32]

[0308] 4-Bromophenyl triphenylmethyl sulfide was synthesized by Production Method E described in Production Example 5.

[0309]

[0310] Specifically, according to Production Method E, it was prepared from 1-bromo-4-iodobenzene (0.6 mmol, 169.8 mg) and catalyst 3 (5 mol%, 27.3 mg). After the reaction, it was purified by silica gel column chromatography (hexane / dichloromethane = 10:1 (volume ratio)) to obtain 4-bromophenyl triphenylmethyl sulfide (221.1 mg, yield 85%) in the form of a white powder.

[0311] 1 1H NMR (400 MHz, CDCl3) δ 7.39 (dd, J = 8.2, 1.3 Hz, 6H), 7.34 - 7.17 (m, 9H), 7.12 (d, J = 8.5 Hz, 2H), 6.79 (d, J = 8.5 Hz, 2H).

[0312] [Example 33]

[0313] 4'-Bromo-4-[(triphenylmethyl)thio]-1,1'-biphenyl was synthesized by Production Method E described in Production Example 5.

[0314]

[0315] Specifically, according to Production Method E, it was prepared from 4-bromo-4'-iodobiphenyl (0.5 mmol, 179.5 mg) and catalyst 3 (5 mol%, 22.8 mg). After the reaction, it was purified by silica gel column chromatography (hexane / dichloromethane = 10:1 (volume ratio)) to obtain 4'-bromo-4-[(triphenylmethyl)thio]-1,1'-biphenyl (231.0 mg, yield 91%) in the form of a white powder.

[0316] 1 1H NMR (400 MHz, CDCl3) δ 7.55 - 7.47 (m, 2H), 7.45 - 7.39 (m, 6H), 7.36 - 7.31 (m, 2H), 7.31 - 7.12 (m, 11H), 7.05 - 6.95 (m, 2H).

[0317] [Example 34]

[0318] 4-[(Triphenylmethyl)thio]-benzonitrile was synthesized by Production Method E described in Production Example 5.

[0319]

[0320] Specifically, according to Production Method E, it was prepared from 4-iodobenzonitrile (0.5 mmol, 179.5 mg) and catalyst 3 (5 mol%, 22.8 mg). After the reaction, through purification using silica gel column chromatography (hexane / ethyl acetate = 10:1 (volume ratio)), 4-[(triphenylmethyl)thio]-benzonitrile (173.7 mg, yield 92%) was obtained in the form of a white powder.

[0321] 1 1H NMR (400 MHz, CDCl3) δ 7.39 - 7.35 (m, 6H), 7.30 - 7.19 (m, 11H), 6.99 (d, J = 8.3 Hz, 2H).

[0322] 13 13C NMR (101 MHz, CDCl3) δ 143.7, 143.4, 131.5, 131.3, 130.0, 128.2, 127.4, 118.9, 109.5, 71.5.

[0323] [Example 35]

[0324] 5-[(Triphenylmethyl)thio]-2,2-difluoro-1,3-benzodioxole was synthesized by Production Method B described in Production Example 2

[0325]

[0326] Specifically, according to Production Method B, it was prepared from 5-bromo-2,2-difluoro-1,3-benzodioxole (0.1 mmol, 23.7 mg) and catalyst 2 (5 mol%, 11.1 mg). After the reaction, through purification using silica gel column chromatography (hexane / dichloromethane = 10:3 (volume ratio)), 5-[(triphenylmethyl)thio]-2,2-difluoro-1,3-benzodioxole was obtained in the form of a white powder. ​Mao (22.1 mg, yield 51%).

[0327] 1 H NMR (400 MHz, CDCl3) δ 7.43 - 7.36 (m, 6H), 7.28 - 7.17 (m, 9H), 6.76 (dd, J = 8.3, 1.7 Hz, 1H), 6.70 (d, J = 8.3 Hz, 1H), 6.58 (d, J = 1.5 Hz, 1H).

[0328] 19 F NMR (376 MHz, CDCl3) δ -49.9 (s, 2F).

[0329] [Example 36]

[0330] Synthesize (3-{4-[(trityl)thio]-phenyl}-3-pyridin-2-yl-propyl)-dimethyl-amine by the production method A described in Production Example 1.

[0331]

[0332] Specifically, according to the production method A, it is prepared from brompheniramine (0.2 mmol, 63.9 mg) and catalyst 1 (10 mol%, 15.9 mg). After the reaction, through purification using silica gel column chromatography (dichloromethane), (3-{4-[(trityl)thio]-phenyl}-3-pyridin-2-yl-propyl)-dimethyl-amine is obtained in the form of a white powder (75.2 mg, yield 73%).

[0333] 1 H NMR (400 MHz, CDCl3) δ 8.52 (ddd, J = 4.9, 1.9, 0.9 Hz, 1H), 7.53 (td, J = 7.7, 1.8 Hz, 1H), 7.44 - 7.34 (m, 6H), 7.25 - 7.10 (m, 9H), 7.08 (ddd, J = 7.5, 4.9, 1.2 Hz, 1H), 7.02 (dt, J = 7.9, 1.1 Hz, 1H), 6.97 - 6.92 (m, 2H), 6.90 - 6.85 (m, 2H), 3.98 (t, J = 7.5 Hz, 1H), 2.39 - 2.23 (m, 1H), 2.18 (s, 6H), 2.16 - 2.04 (m, 3H).

[0334] [Example 37]

[0335] Synthesize 2’,3’,5’-tri-O-acetyl-6-chloro-2-[(trityl)thio]purine nucleoside by the production method E described in Production Example 5.

[0336]

[0337] Specifically, according to production method E, it was prepared from 2′,3′,5′-tri-O-acetyl-6-chloro-2-iodopurine riboside (0.2 mmol, 107.7 mg) and catalyst 3 (5 mol%, 9.1 mg). After the reaction, through purification using silica gel column chromatography (hexane / ethyl acetate = 2:1 (volume ratio)), 2′,3′,5′-tri-O-acetyl-6-chloro-2-[(triphenylmethyl)thio]purine riboside was obtained in the form of a white powder (121.4 mg, yield 89%).

[0338] 1 H NMR (400 MHz, CDCl3) δ 7.95 (s, 1H), 7.46 - 7.36 (m, 6H), 7.33 - 7.16 (m, 9H), 6.09 (d, J = 5.1 Hz, 1H), 5.73 (t, J = 5.3 Hz, 1H), 5.62 - 5.55 (m, 1H), 4.45 - 4.27 (m, 3H), 2.14 (s, 3H), 2.10 (s, 3H), 2.09 (s, 3H).

[0339] 13 C NMR (101 MHz, CDCl3) δ 170.4, 169.7, 169.5, 161.4, 148.6, 143.4, 140.5, 131.8, 130.3, 127.7, 127.1, 117.5, 86.4, 80.5, 73.4, 70.5, 21.0, 20.7, 20.6.

[0340] [Example 38]

[0341] 4-[(Triphenylmethyl)thio]-N-methoxy-N-methylbenzamide was synthesized by the production method E described in Production Example 5.

[0342]

[0343] Specifically, according to production method E, it was prepared from 4-iodo-N-methoxy-N-methylbenzamide (1.0 mmol, 291.1 mg) and catalyst 3 (5 mol%, 45.6 mg). After the reaction, through purification using silica gel column chromatography (hexane / ethyl acetate = 5:2 (volume ratio)), 4-[(triphenylmethyl)thio]-N-methoxy-N-methylbenzamide was obtained in the form of a white powder (357.6 mg, yield 81%).

[0344] 11H NMR (400 MHz, CDCl3) δ 7.43 - 7.37 (m, 6H), 7.31 (d, J = 7.9 Hz, 2H), 7.27 - 7.17 (m, 9H), 7.01 - 6.92 (m, 2H), 3.46 (s, 3H), 3.28 (s, 3H).

[0345] 4-Iodo-N-methoxy-N-methylbenzamide was prepared as follows.

[0346]

[0347] In a 50 mL round-bottom flask in a glove box under an argon atmosphere, N,O-dimethylhydroxylamine hydrochloride (1.07 g, 11 mmol, 1.1 eq) was added to a stirred suspension of 4-iodobenzoyl chloride (2.67 g, 10 mmol) and DCM (15 mL). The flask was sealed with a septum and removed from the glove box and cooled in an ice bath. A pyrimidine solution (1.8 mL, 22 mmol, 2.2 eq) dissolved in 5 mL of DCM was added to the stirred suspension at 0 °C. The reaction mixture was heated to room temperature and stirred for 12 h. Next, the resulting reaction solution was washed once with water and then twice with saturated sodium bicarbonate solution. The washed organic layers were combined, dried over anhydrous sodium sulfate, and the solvent was removed using a rotary evaporator to give 4-iodo-N-methoxy-N-methylbenzamide (2.05 g, yield 70%) as a colorless oil.

[0348] 1 1H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 6.7 Hz, 2H), 7.43 (d, J = 6.7 Hz, 2H), 3.54 (s, 3H), 3.35 (s, 3H).

[0349] 13 13C NMR (101 MHz, CDCl3) δ 169.0, 137.3, 133.5, 130.1, 97.5, 61.3, 33.6.

[0350] [Production Example 6] Typical production method F for the synthesis of an aryl compound containing SF5

[0351] An aryl compound containing SF5 can be synthesized by the following method using an aryltrityl sulfide compound as a substrate.

[0352]

[0353] In a glove box under an argon atmosphere, NEt4Cl or NEt4Br (0.2 mmol, 2.0 equivalents), an aryltrityl sulfide compound (0.1 mmol, 1.0 equivalent), and a magnetic stir bar were placed in a glass vial. MeCN or DCM (0.5 mL) was added, and the reaction mixture was stirred for 2 minutes. Then, AgF2 (1.0 mmol, 10.0 equivalents) was added all at once to the vigorously stirred solution at room temperature, and the vial was sealed with a screw cap. Within about 1 minute, the initially black suspension turned orange, and the organic layer turned red-violet. The reaction solution was stirred for 12 hours. The NMR yield was determined by adding 1,4-bis(trifluoromethyl)benzene (15.5 μL, 0.1 mmol) as an internal standard to the reaction mixture.

[0354] The NMR yield was determined by adding 1,4-bis(trifluoromethyl)benzene (BTB, 1.0 equivalent relative to the SF5 product) as an internal standard to the reaction mixture and filtering the reaction mixture.

[0355] Injected into an NMR tube through a PTFE syringe filter, integrating the F NMR signals of the SF5 and CF3 groups respectively. 19 After NMR measurement, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography to obtain the corresponding aryl compound containing SF5.

[0356] [Example 39]

[0357] 5'-(Pentafluorothio)m-terphenyl was synthesized by the production method F described in Production Example 6.

[0358]

[0359] Specifically, according to the production method F, using NEt4Br in DCM, 5'-tritylthiol m-terphenyl was synthesized (NMR yield: 75%). By purification with silica gel column chromatography using hexane as an eluent, 5'-(pentafluorothio)m-terphenyl was obtained in the form of a white powder (24.8 mg, yield: 70%).

[0360] 1 H NMR (400 MHz, CDCl3) δ 7.92 (m, 3H), 7.65 - 7.59 (m, 4H), 7.53 - 7.47 (m, 4H), 7.45 - 7.40 (m, 2H).

[0361] 1313C NMR (100 MHz, CDCl3) δ 155.5 - 154.7 (m), 142.9, 139.6, 129.3, 129.2, 128.5, 127.5, 123.6 (quint, 3JCF = 4.5 Hz).

[0362] 19 19F NMR (375 MHz, CDCl3) δ 84. (quint, 2JFF,ax = 149.3 Hz, 1F), 63.1 (d, 2JFF,eq = 149.3 Hz, 4F).

[0363] [Example 40]

[0364] 2-(Pentafluorothio)dibenzofuran was synthesized by Production Method F described in Production Example 6.

[0365]

[0366] Specifically, according to Production Method F, using NEt4Br in MeCN, 2-(triphenylmethylthio)dibenzofuran was synthesized (NMR yield: 85%). By purification using silica gel column chromatography with hexane as the eluent, 2-(pentafluorothio)dibenzofuran was obtained in the form of a white powder (21.5 mg, yield: 73%).

[0367] 1 1H NMR (400 MHz, CDCl3) δ 8.36 (d, J = 2.3 Hz, 1H), 8.02 - 7.96 (m, 1H), 7.87 (dd, J = 9.0, 2.3 Hz, 1H), 7.61 (m, 2H), 7.57 - 7.51 (m, 1H), 7.41 (td, J = 7.8, 1.0 Hz, 1H).

[0368] 13 13C NMR (100 MHz, CDCl3) δ 157.2, 156.7, 149.2 (quint, 2JCF = 18.2 Hz), 128.6, 125.0 (quint, 3JCF = 4.7 Hz), 124.4, 123.7, 123.4, 121.1, 119.3 (quint, 3JC-F = 4.7 Hz), 112.2, 111.6.

[0369] 19 19F NMR (375 MHz, CDCl3) δ 85.7 (quint, 2JFF,ax = 150.7 Hz, 1F), 65.3 (d, 2JFF,eq = 150.7 Hz, 4F).

[0370] [Example 41]

[0371] 4-(Pentafluorothio)-4'-chloro-1,1'-biphenyl was synthesized by the production method F described in Production Example 6.

[0372]

[0373] Specifically, according to the production method F, using NEt4Br in MeCN, 4' - chloro - 1,1' - biphenyl - 4 - trityl sulfide was synthesized (NMR yield: 95%). Through purification by silica gel column chromatography using hexane as the eluent, 4-(pentafluorothio)-4'-chloro-1,1'-biphenyl was obtained in the form of a white powder (29.8 mg, yield: 95%).

[0374] 1 H NMR (400 MHz, CDCl3) δ 7.85 - 7.79 (m, 2H), 7.64 - 7.59 (m, 2H), 7.54 - 7.48 (m, 2H), 7.47 - 7.41 (m, 2H).

[0375] 13 C NMR (100 MHz, CDCl3) δ 153.2 (quint, 2JCF = 18.2 Hz), 143.4, 137.6, 134.9, 129.4, 128.7, 127.3, 126.7 (quint, 3JCF = 4.6 Hz).

[0376] 19 F NMR (375 MHz, CDCl3) δ 84.6 (quint, 2JFF,ax = 150.5 Hz, 1F) 63.2 (d, 2JFF,eq = 150.5 Hz, 4F).

[0377] [Example 42]

[0378] 1-(Pentafluorothio)-4-(trans - 4 - propylcyclohexyl)benzene was synthesized by the production method F described in Production Example 6.

[0379]

[0380] Specifically, according to the production method F, using NEt4Br in MeCN, 1 - [4 - (trans - 4'-propylcyclohexyl)phenyl]trityl sulfide was synthesized (NMR yield: 86%). Through purification by silica gel column chromatography using hexane as the eluent, 1-(pentafluorothio)-4-(trans - 4 - propylcyclohexyl)benzene was obtained in the form of a white powder (23.6 mg, yield: 72%).

[0381] 11H NMR (400 MHz, CDCl3) δ 7.75 - 7.53 (m, 2H), 7.27 (d, J = 8.3 Hz, 2H), 2.59 - 2.41 (m, 1H), 1.88 (dd, J = 10.9, 1.7 Hz, 4H), 1.50 - 1.18 (m, 7H), 1.11 - 0.98 (m, 2H), 0.90 (t, J = 7.2 Hz, 3H).

[0382] 13 13C NMR (100 MHz, CDCl3) δ 151.9, 151.9 (quint, 2JCF = 18.2 Hz) 127.2, 126.0 (quint, 3JCF = 5.0 Hz), 44.4, 39.7, 37.0, 34.2, 33.5, 20.1, 14.5.

[0383] 19 19F NMR (375 MHz, CDCl3) δ 85.6 (quint, 2JFF,ax = 149.1 Hz, 1F), 63.3 (d, 2JFF,eq = 149.1 Hz, 4F).

[0384] [Example 43]

[0385] 4-(Pentafluorothio)-2-fluorobiphenyl was synthesized by Production Method F described in Production Example 6.

[0386]

[0387] Specifically, according to Production Method F, using NEt4Br in MeCN, 4-(tritylthio)-2-fluorobiphenyl was synthesized (NMR yield: 98%). After purification by silica gel column chromatography using hexane as the eluent, 4-(pentafluorothio)-2-fluorobiphenyl was obtained as a white powder (32.4 mg, yield: 94%).

[0388] 1 1H NMR (400 MHz, CDCl3) δ 7.61 (ddd, J = 12.6, 9.5, 2.2 Hz, 2H), 7.57 - 7.51 (m, 3H), 7.51 - 7.41 (m, 3H).

[0389] 1313C NMR (100 MHz, CDCl3) δ. 158.6 (d, 1JC-F = 251.7 Hz), 153.2 (d - quint, 2JC-F = 18.7, 3JCF = 8.1 Hz), 133.9 (d, J = 1.5 Hz), 132.9 (d, 2JC-F = 13.5 Hz), 130.8 (d, 3JC-F = 3.7 Hz), 129.1 (d, J = 3.2 Hz), 128.9 (d, J = 3.2 Hz), 122.3 - 121.9 (m), 115.0 (d - quint, 2JC-F = 28.5, 3JC-F = 4.9 Hz).

[0390] 19 19F NMR (375 MHz, CDCl3) δ 83.3 (quint, 2JFF,ax = 150.5 Hz), 63.2 (d, 2JFF,eq = 150.5 Hz), - 114.2 (t, J = 7.5 Hz).

[0391] [Example 44]

[0392] 3,5 - Dimethoxyphenyl - pentafluorosulfide was synthesized by the production method F described in Production Example 6.

[0393]

[0394] Specifically, according to the production method F, using NEt4Br in MeCN, 3,5 - dimethoxyphenyltriphenylmethyl sulfide was synthesized (NMR yield: 39%).

[0395] 1 1H NMR (400 MHz, CDCl3) δ 6.91 (d, J = 2.1 Hz, 2H), 6.68 (s, 2H), 3.78 (s, 6H).

[0396] 19 19F NMR (375 MHz, CDCl3) δ 84.5 (quint, 2JFF,ax = 148.5 Hz, 1F), 62.3 (d, 2JFF,eq = 148.5 Hz, 4F).

[0397] [Example 45]

[0398] 3,4,5 - Trimethoxyphenyl - pentafluorosulfide was synthesized by the production method F described in Production Example 6.

[0399]

[0400] Specifically, according to production method F, using NEt4Br in MeCN, 3,4,5-trimethoxyphenyl triphenylmethyl sulfide was synthesized (NMR yield: 7%).

[0401] 1 1H NMR (only composite signals detected).

[0402] 19 19F NMR (375 MHz, CDCl3) δ 81.1 (quint, 2JFF, ax = 148.8 Hz, 1F), 57.3 (d, 2JFF, eq = 148.8 Hz, 4F).

[0403] [Example 46]

[0404] 4-Bromophenyl-pentafluorosulfide was synthesized by production method F described in Production Example 6.

[0405]

[0406] Specifically, according to production method F, using NEt4Cl in MeCN, 4-bromophenyl triphenylmethyl sulfide was synthesized (NMR yield: 87%). By purification using silica gel column chromatography with hexane as the eluent, 4-bromophenyl-pentafluorosulfide was obtained in the form of a white powder (21.2 mg, yield 75%).

[0407] 1 1H NMR (400 MHz, CDCl3) δ 7.68 - 7.54 (m, 4H).

[0408] 13 13C NMR (100 MHz, CDCl3) δ 153.2 - 152.4 (m), 132.1, 127.7 (quint, 3 J CF = 4.7 Hz), 126.3 (quint, 4 J CF = 1.3 Hz).

[0409] 19 19F NMR (375 MHz, CDCl3) δ 83.6 (quint, 2 J FF,ax = 151.2 Hz, 1F), 63.1 (d, 2 J FF,eq = 152 Hz, 4F).

[0410] [Example 47]

[0411] 4'-Bromo-4-(pentafluorosulfanyl)-1,1'-biphenyl was synthesized by production method F described in Production Example 6.

[0412]

[0413] Specifically, according to production method F, using NEt4Cl in MeCN, 4'-bromo-4-[(triphenylmethyl)thio]-1,1'-biphenyl was synthesized (NMR yield: 86%). Through purification by silica gel column chromatography using hexane as the eluent, 4'-bromo-4-(pentafluorothio)-1,1'-biphenyl was obtained in the form of a white powder (27.6 mg, yield: 77%).

[0414] 1 H NMR (400 MHz, CDCl3) δ 7.87 - 7.79 (m, 2H), 7.66 - 7.57 (m, 4H), 7.48 - 7.41 (m, 2H).

[0415] 13 C NMR (100 MHz, CDCl3) δ 153.2 (quint, 2 J CF = 17.3 Hz), 143.4, 138.1, 132.4, 129.0, 127.2, 126.7 (quint, 3 J CF = 4.6 Hz), 123.1.

[0416] 19 F NMR (375 MHz, CDCl3) δ 84.6 (quint, 2 J FF,ax = 150.4 Hz, 1F). 63.2 (d, 2 J FF,eq = 150.1 Hz, 4F).

[0417] [Example 48]

[0418] 4-(Pentafluorothio)-benzonitrile was synthesized by production method F described in Production Example 6.

[0419]

[0420] Specifically, according to production method F, using NEt4Cl in MeCN, 4-[(triphenylmethyl)thio]-benzonitrile was synthesized (NMR yield: 91%). Through purification by silica gel column chromatography using hexane as the eluent, 4-(pentafluorothio)-benzonitrile was obtained in the form of a white powder (19.0 mg, yield: 83%).

[0421] 11H NMR (400 MHz, CDCl3) δ 7.90 (dd, J = 8.7, 1.3 Hz, 2H), 7.80 (d, J = 8.9 Hz, 2H).

[0422] 13 13C NMR (100 MHz, CDCl3) δ 156.6 (quint, 2 J CF = 19.1 Hz), 132.9, 127.2 (quint, 3 J CF = 4.8 Hz), 117.1, 116.0.

[0423] 19 19F NMR (375 MHz, CDCl3) δ 81.5 (quint, 2 J FF,ax = 150.7 Hz, 1F), 62.2 (d, 2 J FF,eq = 150.7 Hz, 4F).

[0424] [Example 49]

[0425] 4-(Pentafluorothio)-N-methoxy-N-methylbenzamide was synthesized by Production Method F described in Production Example 6.

[0426]

[0427] Specifically, according to Production Method F, using NEt4Cl in MeCN, it was synthesized from 4-[(triphenylmethyl)thio]-N-methoxy-N-methylbenzamide. By purification with silica gel column chromatography using (hexane / diethyl ether = 1:1 (volume ratio)) as the eluent, 4-(pentafluorothio)-N-methoxy-N-methylbenzamide was obtained in the form of a white powder (17.8 mg, yield 61%).

[0428] 1 1H NMR (400 MHz, CDCl3) δ 7.83 - 7.75 (m, 4H), 3.55 (s, 3H), 3.38 (s, 3H).

[0429] 13 13C NMR (100 MHz, CDCl3) δ 167.8, 155.0 (quint, 2 J CF = 17.6 Hz), 137.4, 128.7, 125.8 (quint, 3 J CF = 4.6 Hz), 61.3, 33.2.

[0430] 19 19F NMR (375 MHz, CDCl3) δ 83.5 (quint, 2 J FF,ax = 149.3 Hz), 62.6 (d, 2 J FF,eq = 149.6 Hz).

[0431] [Example 50]

[0432] 4-(Pentafluorothio)benzophenone was synthesized by Production Method F described in Production Example 6.

[0433]

[0434] Specifically, according to Production Method F, using NEt4Cl in MeCN, it was synthesized from 4-[(triphenylmethyl)thio]benzophenone. By purification with silica gel column chromatography using (hexane / dichloromethane = 10:1 (volume ratio)) as the eluent, 4-(pentafluorothio)benzophenone was obtained in the form of a white powder (22.3 mg, yield 72%).

[0435] 1 1H NMR (400 MHz, CDCl3) δ 6.68 - 6.58 (m, 1H), 6.55 (dd, J = 8.4, 1.3 Hz, 0H), 6.42 - 6.36 (m, 0H), 6.30 - 6.19 (m, 1H).

[0436] 19 19F NMR (375 MHz, CDCl3) δ 83.1 (quint, 2 J FF,ax = 151.3 Hz), 62.6 (d, 2 J FF,eq = 150.2 Hz).

[0437] [Example 51]

[0438] 5-Methoxy-1-[4-(pentafluorothio)phenyl]pentan-1-one was synthesized.

[0439]

[0440] Specifically, under nitrogen, THF (3.6 mL) was added to a 15 mL volumetric vial containing 4-(pentafluorothio)-N-methyl-N-methoxybenzamide (0.34 mmol, 100 mg), and a Grignard reagent solution (0.29 M, 3.6 mL) was further added thereto while stirring at 0 °C. Subsequently, the solution was taken out of the ice bath and stirred at room temperature for 2 hours. Thereafter, 6 M hydrochloric acid (3.0 mL) was added to the solution at 0 °C, and the mixture was stirred for 10 minutes. The resulting reaction solution was neutralized with saturated sodium bicarbonate and extracted with DCM. Subsequently, all the organic layers were combined, dried over anhydrous sodium sulfate, and the solvent was removed using a rotary evaporator to obtain 5-methoxy-1-[4-(pentafluorothio)phenyl]pentan-1-one (108.2 mg, yield 99%). It should be noted that this compound was used in the next synthesis without further purification.

[0441] 1 H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.5 Hz, 2H), 7.86 (d, J = 8.5 Hz, 2H), 3.43 (t, J = 6.3 Hz, 2H), 3.33 (s, 3H), 3.03 (t, J = 7.2 Hz, 2H), 1.84 (m, 2H), 1.67 (m, 2H).

[0442] 19 F NMR (376 MHz, CDCl3) δ 83.0 (quint, 2 J FF,ax =150.2 Hz, 1F), 62.5 (d, 2 J FF,eq =149.0 Hz, 4F).

[0443] 13 C NMR (101 MHz, CDCl3) δ 198.7, 139.2, 132.4 (quint, 2 J CF =61.9 Hz), 128.6, 126.6 (quint, 3 J CF =4.7 Hz), 72.6, 58.8, 38.8, 29.2, 21.0.

[0444] The Grignard reagent solution used was the solution prepared as follows.

[0445]

[0446] In a 100 mL two-necked round-bottom flask equipped with a 0 °C cooler and containing flaky magnesium (0.47 g, 1.1 equivalents) and iodine (20 mg), anhydrous THF (30 mL) and 1-bromo-4-methoxybutane (3 g, 18 mmol) were added with stirring at room temperature. The reaction mixture was heated to 50 °C by an oil bath and stirred overnight. After the reaction, the resulting Grignard reagent solution (0.29 M according to titration experiment) was used for the synthesis of 5-methoxy-1-[4-(pentafluorothio)phenyl]pentan-1-one without further purification.

[0447] [Example 52]

[0448] Synthesize N-{5-methoxy-1-[4-(pentafluorothio)phenyl]pentylidene}hydroxylamine.

[0449]

[0450] Specifically, hydroxylamine hydrochloride (47.3 mg, 0.68 mmol, 2.0 equivalents) and sodium acetate (55.8 mg, 0.68 mmol, 2.0 equivalents) were added to 5-methoxy-1-[4-(pentafluorothio)phenyl]pentan-1-one (108.2 mg, 0.34 mmol) dissolved in ethanol (1.7 mL), and the mixture was stirred at room temperature. After 3 hours, the solution was quenched with water and extracted with DCM. All the organic layers were combined, dried over anhydrous sodium sulfate, and the solvent was removed using a rotary evaporator to obtain N-{5-methoxy-1-[4-(pentafluorothio)phenyl]pentylidene}hydroxylamine (101.1 mg, yield 89%). It should be noted that this compound was used for the next synthesis without further purification.

[0451] 1 H NMR (400 MHz, CDCl3) δ 7.75 (d, J = 9.0 Hz, 2H), 7.68 (d, J = 8.7 Hz, 2H), 3.41 (t, J = 6.0 Hz, 2H), 3.33 (s, 3H), 2.84 (t, J = 7.4 Hz, 2H), 1.65 (m, 4H).

[0452] 19 F NMR (376 MHz, CDCl3) δ 84.2 (quint, 2 J FF,ax = 150.0 Hz, 1F), 62.8 (d, 2 J FF,eq = 150.0 Hz, 4F).

[0453] 13 C NMR (101 MHz, CDCl3) δ 158.1, 154.2 (quint,2 J CF = 17.3 Hz), 139.0, 126.6, 126.4 (quint, 3 J CF = 4.6 Hz), 72.4, 58.8, 29.6, 25.7, 23.0.

[0454] [Example 53]

[0455] Synthesis of pentafluorosulfanyl - fluvoxamine.

[0456]

[0457] Specifically, in a 15 mL volumetric glass vial filled with argon in a glove box, sodium hydride (5.8 mg, 0.24 mmol, 2.0 equiv) was added to N-{5 - methoxy - 1 - [4 - (pentafluorosulfanyl)phenyl]pentylidene}hydroxylamine (40.1 mg, 0.12 mmol) dissolved in DMF (0.7 mL), and the mixture was stirred at room temperature for 3 hours. Subsequently, 2 - chloroethylamine hydrochloride (14.0 mg, 0.12 mmol, 1.0 equiv) was added to the reaction mixture, and the mixture was taken out of the glove box and stirred at room temperature for 12 hours. The resulting reaction mixture was quenched with water and extracted with DCM. All the organic layers were combined, dried over anhydrous sodium sulfate, the solvent was removed using a rotary evaporator, and the crude product was purified by silica gel column chromatography (DCM / methanol = 10:1) to obtain pentafluorosulfanyl - fluvoxamine (12.0 mg, yield 32%) in the form of a colorless oil.

[0458] 1 1H NMR (400 MHz, CDCl3) δ 7.75 - 7.70 (m, 4H), 4.24 (t, J = 4.7 Hz, 2H), 3.38 (t, J = 5.8 Hz, 2H), 3.32 (br, 2H), 3.04 (s, 1H), 2.79 (t, J = 6.6 Hz, 2H), 1.67 - 1.58 (m, 4H).

[0459] 19 19F NMR (376 MHz, CDCl3) δ 84.3 (quint, 2 J FF,ax = 151.3 Hz, 1F), 62.8 (d, 2 J FF,eq = 151.0 Hz, 4F).

[0460] 13 13C NMR (101 MHz, CDCl3) δ 157.1, 154.1 (quint, 2 J CF= 17.5 Hz), 139.0, 126.6, 126.3 (quint, 3 J CF = 4.7 Hz), 76.6, 72.3, 58.8, 41.6, 29.7, 26.1, 23.2.

[0461] [Example 54]

[0462] 2-Methyl-5-[(triphenylmethyl)thio]pyrimidine was synthesized using a Pd[cinnamyl](L)OTf catalyst or a Pd[allyl](L)OTf catalyst composed of a palladium complex coordinated with various phosphine ligands (L). As the phosphine ligand, the compounds described in Table 1 were used.

[0463] (1) Synthesis of Pd[cinnamyl](L)OTf catalyst and Pd[allyl](L)OTf catalyst

[0464] In a 15 mL volumetric glass vial in a glove box under an argon atmosphere, silver trifluoromethanesulfonate (AgOTf, 0.1 mmol, 2.0 equivalents) was added to a stirred mixture of THF (1.0 mL) and allyl palladium chloride dimer or Pd[cinnamyl]Cl dimer (0.05 mmol, 1.0 equivalent). The mixture that formed silver chloride as a white precipitate was stirred at room temperature for 1 hour. The white precipitate in the reaction mixture was removed using a syringe filter, and the filtrate was added to a 50 mL volumetric glass vial containing the phosphine ligand (0.1 mmol, 2.0 equivalents). After stirring at room temperature for 2 hours, hexane (10 mL) was added to the reaction solution to obtain a powdery or crystalline precipitate. The supernatant was removed by decantation, and the residue was washed 3 times with hexane (5 mL). The residue was evaporated under reduced pressure to obtain the target Pd[cinnamyl](L)OTf catalyst or Pd[allyl](L)OTf catalyst in the form of a powder or crystal.

[0465] (2) Synthesis of 2-Methyl-5-[(triphenylmethyl)thio]pyrimidine

[0466]

[0467] Transfer the oven-dried test tube into a glove box under an argon atmosphere. After adding 5-bromo-2-methylpyrimidine (0.2 mmol) to a mixture of Pd[cinnamyl](L)OTf catalyst or Pd[allyl](L)OTf catalyst (5 mol%) and toluene (0.5 M) in the test tube, cool the test tube in a refrigerator at -30 °C for 0.5 h. While stirring vigorously at room temperature, add KSTr (KSCPh3) (94.3 mg, 0.3 mmol, 1.5 equiv) to the mixture. After sealing with an aluminum cap with a septum using a vial sealer, take the test tube out of the glove box and stir at room temperature for 18 h. Dilute the reaction mixture with CDCl3 and use 1 1H NMR to determine the NMR yield of 2-methyl-5-[(triphenylmethyl)thio]pyrimidine.

[0468]

[0469]

[0470] [Table 1]

[0471] Catalyst Phosphine ligand Yield (%) 4-1 AIPhos 99 4-2 <![CDATA t BuXPhos]]> 15 4-3 Sphos <1 4-4 Xphos <1 4-5 BrettPhos 19 4-6 <![CDATA t Bu - BrettPhos]]> 15 4-7 <![CDATA[Me4 t BuXPhos]]> 11 4-8 Ad - BrettPhos 25 4-9 RuPhos <1 4-10 <![CDATA[Me3OMe t BuXPhos]]> 9 4-11 Ad - BippyPhos 20 4-12 <![CDATA t Bu-BippyPhos]]> 50 4-13 MePhos <1 4-14 <![CDATA t BuDavePhos]]> <1 4-15 XantPhos 33 4-16 <![CDATA t BuXantPhos]]> <1 4-17 DPEPhos 11 4-18 CyXantPhos 48 4-19 JohnPhos <1

[0472] The NMR yields of 2-methyl-5-[(triphenylmethyl)thio]pyrimidine synthesized using each Pd[cinnamyl](L)OTf catalyst are shown in Table 1. The synthesis of 2-methyl-5-[(triphenylmethyl)thio]pyrimidine was confirmed in any case of using the catalyst. With t BuXPhos, A1Phos, t Bu-BippyPhos, CyXantPhos, XantPhos, Ad-BrettPhos, Ad-BippyPhos, BrettPhos or t Bu-BrettPhos as the phosphine ligand, the Pd[cinnamyl](L)OTf catalyst has good yields.

[0473] [Example 55]

[0474] Synthesize methyl 4-[(triphenylmethyl)thio]benzoate by the production method E described in Production Example 5.

[0475]

[0476] Specifically, it was prepared from methyl 4-iodobenzoate (0.2 mmol, 52.4 mg) and catalyst 3 (5 mol%, 9.1 mg) according to production method E. After the reaction, it was purified by silica gel column chromatography (hexane / ethyl acetate = 10:1 (volume ratio)) to obtain methyl 4-[(triphenylmethyl)thio]benzoate (74.7 mg, yield 91%) in the form of a white powder.

[0477] 1 H NMR (400 MHz, CDCl3) δ 7.63 (d, J = 8.3 Hz, 2H), 7.44 - 7.34 (m, 6H), 7.29 - 7.13 (m, 9H), 7.02 - 6.94 (m, 2H), 3.81 (s, 3H).

[0478] 13 C NMR (101 MHz, CDCl3) δ 166.9, 144.1, 142.5, 131.4, 130.1, 129.2, 128.0, 127.2, 71.1, 52.2.

[0479] [Example 56]

[0480] 2-Benzyloxy-5-[(triphenylmethyl)thio]pyrimidine was synthesized by the production method E described in Production Example 5.

[0481]

[0482] Specifically, it was prepared from 2-benzyloxy-5-iodopyrimidine (0.2 mmol, 62.4 mg) and catalyst 3 (5 mol%, 9.1 mg) according to production method E. After the reaction, it was purified by silica gel column chromatography (hexane / ethyl acetate = 10:1 (volume ratio)) to obtain 2-benzyloxy-5-[(triphenylmethyl)thio]pyrimidine (83.8 mg, yield 91%) in the form of a white powder.

[0483] 1 H NMR (400 MHz, CDCl3) δ 7.92 (s, 2H), 7.46 - 7.37 (m, 8H), 7.36 - 7.08 (m, 12H), 5.32 (s, 2H).

[0484] 13 C NMR (101 MHz, CDCl3) δ 165.4, 164.5, 143.8, 136.2, 129.8, 128.5, 128.1, 128.0, 127.2, 121.6, 71.7, 69.4.

[0485] [Example 57]

[0486] 2,4-Dimethoxy-5-[(triphenylmethyl)thio]pyrimidine was synthesized by the production method E described in Production Example 5.

[0487]

[0488] Specifically, according to the production method E, it was prepared from 2,4-dimethoxy-5-iodopyrimidine (0.2 mmol, 53.2 mg) and catalyst 3 (5 mol%, 9.1 mg). After the reaction, it was purified by silica gel column chromatography (hexane / ethyl acetate = 10:1 (volume ratio)) to obtain 2,4-dimethoxy-5-[(triphenylmethyl)thio]pyrimidine (72.1 mg, yield 87%) in the form of a white powder.

[0489] 1 H NMR (400 MHz, CDCl3) δ 7.76 (s, 1H), 7.50 - 7.39 (m, 6H), 7.27 - 7.12 (m, 9H), 3.88 (s, 3H), 3.63 (s, 3H).

[0490] 13 C NMR (101 MHz, CDCl3) δ 171.5, 165.3, 144.2, 130.0, 127.7, 126.9, 107.8, 71.7, 55.1, 54.1.

[0491] [Example 58]

[0492] 2-Fluoro-5-[(triphenylmethyl)thio]pyridine was synthesized by the production method E described in Production Example 5.

[0493]

[0494] Specifically, according to the production method E, it was prepared from 2-fluoro-5-iodopyridine (0.2 mmol, 44.6 mg) and catalyst 3 (5 mol%, 9.1 mg). After the reaction, it was purified by silica gel column chromatography (hexane / ethyl acetate = 20:1 (volume ratio)) to obtain 2-fluoro-5-[(triphenylmethyl)thio]pyridine (64.6 mg, yield 87%) in the form of a white powder.

[0495] 1 H NMR (400 MHz, CDCl3) δ 7.95 - 7.69 (m, 1H), 7.46 - 7.37 (m, 6H), 7.31 - 7.14 (m, 10H), 6.54 (ddd, J = 8.5, 3.0, 0.6 Hz, 1H).

[0496] 1313C NMR (101 MHz, CDCl3) δ 163.5 (d, J = 241.8 Hz), 153.9 (d, J = 14.9 Hz), 147.9 (d, J = 8.6 Hz), 144.0, 129.9, 128.1, 127.1, 109.1 (d, J = 37.7 Hz), 71.7.

[0497] 19 19F NMR (376 MHz, CDCl3) δ -67.9 (d, J = 6.7 Hz).

[0498] [Example 59]

[0499] 2-Fluoro-4-[(triphenylmethyl)thio]pyridine was synthesized by Production Method E described in Production Example 5.

[0500]

[0501] Specifically, according to Production Method E, it was prepared from 2-fluoro-4-iodopyridine (0.2 mmol, 44.6 mg) and Catalyst 3 (5 mol%, 9.1 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / ethyl acetate = 20:1 (volume ratio)) to obtain 2-fluoro-4-[(triphenylmethyl)thio]pyridine (54.9 mg, yield 74%) in the form of a white powder.

[0502] 1 1H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 5.6 Hz, 1H), 7.35 (dd, J = 8.1, 1.6 Hz, 6H), 7.32 - 7.21 (m, 9H), 6.71 (dt, J = 5.5, 1.5 Hz, 1H), 6.34 (t, J = 1.4 Hz, 1H).

[0503] 13 13C NMR (101 MHz, CDCl3) δ 163.22 (d, J = 238.6 Hz), 154.21 (d, J = 8.7 Hz), 146.16 (d, J = 16.0 Hz), 143.1, 130.0, 128.3, 127.7, 120.85 (d, J = 3.8 Hz), 108.54 (d, J = 40.4 Hz), 71.1.

[0504] 19 19F NMR (376 MHz, CDCl3) δ 68.5.

[0505] [Example 60]

[0506] N-(3-chloro-4-(3-fluorobenzyloxy)phenyl)-6-[(triphenylmethyl)thio]quinazolin-4-amine was synthesized by Production Method E described in Production Example 5.

[0507]

[0508] Specifically, according to Production Method E, it was prepared from N-(3-chloro-4-(3-fluorobenzyloxy)phenyl)-6-iodoquinazolin-4-amine (0.2 mmol, 101.1 mg) and catalyst 3 (10 mol%, 18.2 mg). After the reaction, purification was carried out using silica gel column chromatography (hexane / ethyl acetate = 2:1 (volume ratio)) to obtain N-(3-chloro-4-(3-fluorobenzyloxy)phenyl)-6-[(triphenylmethyl)thio]quinazolin-4-amine (87.7 mg, yield 67%) in the form of a white powder.

[0509] 1 H NMR (400 MHz, CDCl3) δ 8.64 (s, 1H), 7.75 (d, J = 2.6 Hz, 1H), 7.72 - 7.59 (m, 2H), 7.50 - 7.40 (m, 6H), 7.41 - 7.33 (m, 3H), 7.33 - 7.22 (m, 9H), 7.03 (td, J = 8.1, 1.6 Hz, 1H), 6.98 (d, J = 8.9 Hz, 1H), 6.89 (d, J = 1.5 Hz, 1H), 6.55 (s, 1H), 5.17 (s, 2H).

[0510] [Example 61]

[0511] 5-{2-Ethoxy-5-[(triphenylmethyl)thio]-phenyl}-1-methyl-3-propyl-6H-pyrazolo[4,3-d]pyrimidin-7-one was synthesized by Production Method E described in Production Example 5.

[0512]

[0513] Specifically, according to Production Method E, it was prepared from (5-(2-ethoxy-5-iodo-phenyl)-1-methyl-3-propyl-6H-pyrazolo[4,3-d]pyrimidin-7-one 0.2 mmol, 87.7 mg) and catalyst 3 (5 mol%, 9.1 mg). After the reaction, purification was carried out using silica gel column chromatography (hexane / ethyl acetate = 2:1 (volume ratio)) to obtain 5-{2-ethoxy-5-[(triphenylmethyl)thio]-phenyl}-1-methyl-3-propyl-6H-pyrazolo[4,3-d]pyrimidin-7-one (99.7 mg, yield 85%) in the form of a white powder.

[0514] 11H NMR (400 MHz, CDCl3) δ 10.88 (br, NH), 8.16 (d, J = 2.4 Hz, 1H), 7.49 - 7.41 (m, 6H), 7.28 - 7.11 (m, 9H), 6.94 (dd, J = 8.7, 2.4 Hz, 1H), 6.64 (d, J = 8.7 Hz, 1H), 4.25 (s, 3H), 4.22 - 4.04 (m, 2H), 2.95 - 2.85 (m, 2H), 1.84 (h, J = 7.4 Hz, 2H), 1.53 (t, J = 7.0 Hz, 3H), 1.04 (t, J = 7.4 Hz, 3H).

[0515] [Example 62]

[0516] 4-[(Triphenylmethyl)thio]-N,N-dipropylbenzenesulfonamide was synthesized by Production Method E described in Production Example 5.

[0517]

[0518] Specifically, according to Production Method E, it was prepared from 4-iodo-N,N-dipropylbenzenesulfonamide (0.2 mmol, 73.46 mg) and Catalyst 3 (5 mol%, 9.1 mg). After the reaction, purification was carried out by silica gel column chromatography (hexane / ethyl acetate = 20:1 (volume ratio)) to obtain 4-[(triphenylmethyl)thio]-N,N-dipropylbenzenesulfonamide (98.0 mg, yield 95%) in the form of a white powder.

[0519] 1 1H NMR (400 MHz, CDCl3) δ 7.42 - 7.35 (m, 8H), 7.29 - 7.16 (m, 9H), 7.03 (d, J = 8.3 Hz, 2H), 3.01 - 2.92 (m, 4H), 1.47 (h, J = 7.5 Hz, 4H), 0.83 (t, J = 7.4 Hz, 6H).

[0520] 13 13C NMR (101 MHz, CDCl3) δ 143.9, 141.6, 138.0, 132.2, 130.0, 128.0, 128.0, 127.2, 126.6, 71.4, 50.0, 22.0, 11.3.

[0521] Industrial Applicability

[0522] The present invention provides a production method capable of synthesizing a compound obtained by introducing a tritylthio group into various aryl compounds under milder conditions. In addition, the aryl compound containing a tritylthio group produced by the production method of the aryl compound containing a tritylthio group of the present invention can be easily converted into an aryl compound containing an SF5 group by an oxidative fluorination reaction, and is suitable as a raw material substrate for an aryl compound containing an SF5 group. Therefore, the present invention is useful for introducing an SF5 group into a pharmacologically active ingredient of a pharmaceutical or agricultural chemical, an organic material, or the like.

Claims

1. A method for producing an aryl compound containing a tritylthio group, which comprises subjecting a haloaryl compound represented by the following general formula (1) to tritylthiolation using potassium [(triphenylmethyl)thio] or sodium [(triphenylmethyl)thio] to produce an aryl compound containing a tritylthio group represented by the following general formula (2). A 1 —X (1) In formula (1), A 1 is an aryl which may have substituents or a heteroaryl which may have substituents, X is a halogen atom, In formula (2), A 1 is the same as A in general formula (1), and Ph is phenyl. 1 ​ 2. The method for producing an aryl compound containing a tritylthio group according to claim 1, wherein, Furthermore, the tritylthiolation of the haloaryl compound represented by the general formula (1) is carried out using a palladium catalyst.

3. The method for producing an aryl compound containing a tritylthio group according to claim 2, wherein, The palladium catalyst is Pd[cinnamyl]( t BuXPhos)OTf or Pd[allyl](AlPhos)OTf.

4. The manufacturing method of the aryl compound containing triphenylmethylthio according to claim 1, wherein, The said A 1 is an aryl group that can have one or more substituents selected from halogen atoms, alkyl groups, fluoroalkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, hydroxy groups, carboxyl groups, acyl groups, cyano groups, fluorocarbonyl groups, amino groups, nitro groups, pyrrolidinyl groups, piperidinyl groups, piperazinyl groups, pyrazolidinyl groups, imidazolidinyl groups, tetrahydrofuranyl groups, 1,3-dioxolanyl groups, tetrahydrothienyl groups, 1,2-oxathiolanyl groups, morpholinyl groups, and tetrahydropyranyl groups, or The said A 1 is a heteroaryl which may have one or more substituents selected from a halogen atom, an alkyl group, a fluoroalkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, a hydroxy group, a carboxyl group, an acyl group, a cyano group, a fluorocarbonyl group, an amino group, a nitro group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, a pyrazolidinyl group, an imidazolidinyl group, a tetrahydrofuranyl group, a 1,3-dioxolanyl group, a tetrahydrothienyl group, a 1,2-oxathiolanyl group, a morpholinyl group, and a tetrahydropyranyl group.

5. The method for producing an aryl compound containing a tritylthio group according to claim 1, wherein, The tritylthiolation reaction is carried out at 0 to 80 °C.

6. A method for producing an aryl compound containing a pentafluorothio group, which comprises producing an aryl compound containing a tritylthio group represented by the general formula (2) from the haloaryl compound represented by the general formula (1) by the method for producing an aryl compound containing a tritylthio group according to any one of claims 1 to 5. By using a metal fluoride having a valence of 2 or higher and an organic salt containing a quaternary ammonium cation or a quaternary cation, the aryl compound containing a tritylthio group is synthesized into an aryl compound containing a pentafluorothio group represented by the following general formula (3) through an oxidative fluorination reaction, A 1 —SF5 (3) In formula (3), A 1 is the same as A in general formula (1). 1 ​ 7. The method for producing an aryl compound containing a pentafluorosulfanyl group according to claim 6, wherein, The oxidative fluorination reaction is carried out at -40 to 130 °C.

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