Methods for capturing thiocarbonyl fluoride

Abstract

The present invention is a method for capturing SCF2, wherein compound A-SCF3 [wherein A is (C6~C] 10 The present invention relates to a method comprising the steps of reacting a compound [selected from the group consisting of aryl groups, heteroaryl groups, and vinyl compounds] with a nucleophile in the presence of a metal complex, ligand and solvent containing nickel, palladium or rhodium(I), to cause the formation of compound AH or compound AZ [wherein Z is a hydrocarbon group optionally containing at least one heteroatom such as S, N or O and / or at least one atom other than C or H such as Se, Si, B or P] and SCF2, and reacting SCF2 with compound RH [wherein R is a hydrocarbon group optionally containing at least one heteroatom] to obtain a compound having the formula RC(=S)-F.

Description

[Technical Field]

[0001] The present invention relates to a method for capturing thiocarbonyl fluoride or similar substances. [Background technology]

[0002] In societies concerned with environmental, global, and aquatic pollution, as well as the circular economy, the development of new technologies to achieve such objectives is a pressing issue and a hot topic throughout the chemical industry today.

[0003] Organofluorine chemistry is an unavoidable field, and fluorinated compounds hold great significance in many areas, including materials science, pharmaceuticals, and the agrochemical industry. Indeed, the incorporation of fluorine atoms or fluorinated units can significantly alter the physicochemical properties of organic molecules, explaining the scientific community's interest in this research area. However, the widespread use of these compounds raises questions about their future and degradation. Recently, there has been strong recognition from the scientific and societal community regarding chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), and perfluoroalkyl and polyfluoroalkyl substances (PFAs). Now, it is even more important to pay close attention to the future of emerging fluorinated groups, such as derivatives containing SCF3 units (e.g., tollazuryl and fipronil), which have become essential.

[0004] In this context, developing methods to enhance the value of these fluorinated derivatives, which are used once and then considered waste, by converting them into high-value-added compounds would have an undeniable ecological impact and enable cost reduction. Therefore, it is essential to develop innovative methods to address this challenge and unlock the synthetic key.

[0005] Currently, (hetero)aromatic derivatives or C(sp) on the vinyl position are available. 2 )-SRf bond, or C(sp 3There is currently no technology that allows for the selective cleavage of )-SRf bonds, and any advances in this area would have a significant impact from both scientific and environmental perspectives.

[0006] N. Barbero et al., Organic Letters, 2012, 14, pp. 796-799 (Supporting Information, S1-S78), discusses the catalytic reductive cleavage reaction of inactivated C-SMe bonds. As shown on page 797, left column of the final section, the SMe group, i.e., the electron-donating sulfur atom, was reported to be the most efficient in the reductive cleavage reaction of C-CS bonds. The optimization method reported in Tables 1-6 of the Supporting Information (pp. S3-S5) was performed specifically for this particular thioether. Table 7 of this document (p. S5) confirms that the SMe group yields the highest yield for C-CS bond cleavage, while electron-withdrawing groups such as Ac and CONMe2 were inefficient.

[0007] Surprisingly, it was found that in the presence of electron-withdrawing fluorinated groups such as CF3 or similar fluorine-containing groups, it is possible to selectively cleave CS bonds and analogues of such bonds in organic molecules.

[0008] In today's world, with a circular economy in mind, which is an important part of industrial objectives, there is a particular need to reuse the fluorinated residues released during the defluorination reaction through the logic of the 3Rs (Reduce, Reuse, Recycle). [Prior art documents] [Non-patent literature]

[0009] [Non-Patent Document 1] Organic Letters, 2012, 14, pp. 796-799 [Overview of the project] [Problems that the invention aims to solve]

[0010] Therefore, one of the objects of the present invention is to provide a method for capturing fluorinated residues, thiocarbonyl fluoride (SCF2), SCF3 - or F - .

Means for Solving the Problems

[0011] The present invention is a method for capturing SCF2, comprising: - Formula (I) A-SCF3 (I) [In the formula, A is .(C6-C 10 ) aryl group {The aryl group is preferably halogen, (C1-C6) alkyl, (C1-C6) alkoxy, -CN, -CF3, -OCF3, -NR a R b , -SiR a R b R c , -BR a R b , (C2-C6) alkenyl, (C2-C6) alkynyl, -C(=O)-NR a R b and -C(=O)-O(C1-C6) alkyl, and is optionally substituted with at least one substituent selected from the group consisting of; R a and R b are each independently H or a (C1-C6) alkyl group; R c is a (C1-C6) alkyl group}; .a heteroaryl group containing 5-10 atoms and at least one heteroatom selected from O, N and S {The heteroaryl group is preferably halogen, (C1-C6) alkyl, (C1-C6) alkoxy, -CN, -CF3, -OCF3, -NR a R b , -Si(R c )3, -BR a R b , (C2-C6) alkenyl, (C2-C6) alkynyl, -C(=O)-NR a R band are optionally substituted with at least one substituent selected from -C(=O)-O(C1~C6)alkyl groups, R a , R b and R c This is as defined above; and .Following formula (III):

[0012] [ka]

[0013] {where, R 1 These include halogens, (C1-C6) alkyls, (C1-C6) alkoxys, -CN, -CF3, -OCF3, and -NR. a R b , -Si(R c )3, -BR a R b (C2~C6) alkenyl, (C2~C6) alkynyl, -C(=O)-NR a R b And selected from the group consisting of -C(=O)-O(C1~C6)alkyl, R a , R b and R c Vinyl compounds having the above definition A compound having [selected from the group consisting of] A step of reacting a nucleophile with a metal complex containing nickel, palladium, or rhodium(I), a ligand, and a solvent, A step that causes the formation of compound AH or compound AZ [wherein Z is a hydrocarbon group optionally containing at least one heteroatom such as S, N, or O and / or at least one atom other than C or H such as Se, Si, B, or P] and SCF2, and - A step to obtain a compound having the formula RC(=S)-F by reacting the SCF2 obtained in the previous step with compound RH [wherein R is a hydrocarbon group optionally containing at least one heteroatom]. Regarding methods including

[0014] In particular, the present invention is A method for capturing SCF2, - Equation (I) A-SCF3(I) [In the formula, A is, .(C6~C 10 ) Aryl group {The aryl group is preferably a halogen, (C1-C6)alkyl, (C1-C6)alkoxy, -CN, -CF3, -OCF3, -NR a R b , -SiR a R b R c ,-BR a R b (C2~C6) alkenyl, (C2~C6) alkynyl, -C(=O)-NR a R b and optionally substituted with at least one substituent selected from the group consisting of -C(=O)-O(C1~C6)alkyl groups; R a and R b These are independently H or (C1-C6) alkyl groups; R c It is a (C1-C6) alkyl group; A heteroaryl group containing 0.5 to 10 atoms and at least one heteroatom selected from O, N, and S. {The heteroaryl group is preferably a halogen, (C1-C6)alkyl, (C1-C6)alkoxy, -CN, -CF3, -OCF3, -NR a R b , -Si(R c )3, -BR a R b (C2~C6) alkenyl, (C2~C6) alkynyl, -C(=O)-NR a R b and are optionally substituted with at least one substituent selected from -C(=O)-O(C1~C6)alkyl groups, R a , R b and R c This is as defined above; and .Following formula (III):

[0015] [ka]

[0016] {where, R 1 These include halogens, (C1-C6) alkyls, (C1-C6) alkoxys, -CN, -CF3, -OCF3, and -NR. a R b , -Si(R c )3, -BR a R b (C2~C6) alkenyl, (C2~C6) alkynyl, -C(=O)-NR a R b And selected from the group consisting of -C(=O)-O(C1~C6)alkyl, R a , R b and R c Vinyl compounds having the above definition A compound having [selected from the group consisting of] A step of reacting a nucleophile with a nickel-containing metal complex, ligand, and solvent, A step that causes the formation of compound AH or SCF2, and - A step to obtain a compound having the formula RC(=S)-F by reacting the SCF2 obtained in the previous step with compound RH [wherein R is a hydrocarbon group optionally containing at least one heteroatom]. Regarding methods including

[0017] The present invention provides various methods for improving the value of fluorinated residues generated in-situ during defluorination reactions. These residues may exist in various forms, including HSCF3 (where X is any countercation such as Na or H), for example, HSCF3 which is a highly volatile gas (bp = approximately -30°C), or thiocarbonyl fluoride in equilibrium with a fluoride anion. HSCF3, or thiocarbonyl fluoride / F - These molecules can be captured with a simple process, or they can be reacted with other compounds to obtain other fluorinated related molecules.

[0018] The present invention also provides a method for capturing fluorinated residues such as HSCF3 or fluoride anions, - Equation (I) A-SCF3(I) A compound having [wherein A is as defined above] A step of reacting a nucleophile with a nickel-containing metal complex, ligand, and solvent, A process that causes the release of fluorinated residues such as HSCF3 or fluoride anions. - A step of reacting the fluorinated residue, such as HSCF3 or the fluoride anion obtained in the previous step, with compound RH [wherein R is a hydrocarbon group optionally containing at least one heteroatom]. Regarding methods including

[0019] The following definitions are provided to explain and define the meaning and scope of various terms used in describing the present invention in this specification.

[0020] Expression “C t ~C z "C1" refers to a carbon chain that can have carbon atoms from t to z, for example, C1 to C3 refers to a carbon chain that can have 1 to 3 carbon atoms.

[0021] The term "alkyl group," unless otherwise specified, refers to a linear or branched, saturated hydrocarbon aliphatic group containing 1 to 12 carbon atoms. Examples may include methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl, or pentyl groups.

[0022] The term "aryl group" refers to a cyclic aromatic group containing 6 to 10 carbon atoms. Examples of aryl groups may include the phenyl or naphthyl group.

[0023] The term "heteroaryl group" refers to a 5- to 10-membered aromatic monocyclic or bicyclic group containing 1 to 4 heteroatoms selected from O, S, or N. Examples may include imidazolyl, thiazolyl, oxazolyl, furanyl, thiophenyl, pyrazolyl, oxadiazolyl, tetrazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridadinyl, indolyl, benzofuranyl, benzothiophenyl, benzoxazolyl, benzimidazolyl, indazolyl, benzothiazolyl, isobenzothiazolyl, benzotriazolyl, quinolinyl, and isoquinolinyl groups.

[0024] As heteroaryl groups containing 5-6 atoms including 1-4 nitrogen atoms, the following representative groups may be mentioned in particular: pyrrolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, and 1,2,3-triazinyl.

[0025] As heteroaryls, thiophenyl, oxazolyl, flazanil, 1,2,4-thiadiazolyl, naphthilidinil, quinoxalinil, phthalazinil, imidazo[1,2-a]pyridine, imidazo[2,1-b]thiazolyl, sinnolinil, benzoflazanil, azaindol, benzimidazolyl, benzothiophenyl, thienopyridyl, thienopyrimidinil, pyrrolopyridyl, imidazopyridyl, benzoazaindole, 1,2,4-triazinil, indolidinil, isoxazolyl, isoquinolinil, isothiazolyl, purinyl, quinazolinil, quinolinil, isoquinolinil, 1,3,4-thiadiazolyl, thiazolyl, isothiazolyl, carbazolyl, and also the corresponding groups resulting from their condensation or condensation with a phenyl nucleus.

[0026] When an alkyl group is substituted with an aryl group, the terms "arylalkyl" or "aralkyl" are used. An "arylalkyl" or "aralkyl" group is an arylalkyl group defined above, where the aryl group and alkyl group are arylalkyl groups. Among arylalkyl groups, benzyl or phenethyl groups may be specifically mentioned.

[0027] The term "halogen" refers to fluorine, chlorine, bromine, or iodine.

[0028] The term "alkoxy group" refers to an -O-alkyl group where the alkyl group is as previously defined. Examples may include -O-(C1-C4) alkyl groups, particularly the -O-methyl group, -O-ethyl group, -O-propyl group and -O-isopropyl group as -O-C3 alkyl groups, and -O-butyl, -O-isobutyl, or -O-tert-butyl group as -O-C4 alkyl groups.

[0029] As used herein, the term "alkynyl" includes an unsaturated, non-aromatic hydrocarbon group having 2 to 6 carbon atoms and containing at least one triple bond. Preferably, the alkynyl group is linear. Preferably, the alkynyl group is -(CH2) where m is an integer ranging from 1 to 4. m -C≡CH group

[0030] As used herein, the term "alkenyl" refers to an unsaturated non-aromatic hydrocarbon group having 2 to 6 carbon atoms and containing at least one double bond. Preferably, the alkenyl group is linear. Preferably, the alkenyl group is -(CH2) where m is an integer ranging from 1 to 4. m It has two -CH=CH groups.

[0031] The aforementioned "alkyl," "aryl," and "heteroaryl" groups can be substituted with one or more substituents. Among these substituents, the following groups may be mentioned: amino, hydroxyl, thiol, oxo, halogen, alkyl, alkoxy, alkylthio, alkylamino, aryloxy, arylalkoxy, cyano, trifluoromethyl, carboxy, or carboxyalkyl.

[0032] The term "alkylthio" refers to an alkyl group where the alkyl group is defined as an -S-alkyl group as described above.

[0033] The term "alkylamino" refers to the -NH-alkyl group defined above.

[0034] The term "aryloxy" refers to the -O-aryl group as defined above.

[0035] The term "arylalkoxy" refers to an arylalkoxy group defined above, where the aryl group and alkoxy group are the same.

[0036] The term "carboxyalkyl" means that the alkyl group is an HOOC-alkyl group as defined above. Examples of carboxyalkyl groups may include, in particular, carboxymethyl or carboxyethyl.

[0037] The term "haloalkyl group" refers to the alkyl group defined above, where one or more hydrogen atoms are replaced by halogen atoms. Examples may include fluoroalkyl groups, particularly CF3 or CHF2.

[0038] The term "carboxyl" refers to the COOH group.

[0039] The term "oxo" means "=O". [Modes for carrying out the invention]

[0040] In one embodiment, compound RH is selected from the group consisting of amines, alcohols, thiols, phosphines, phosphonates, Grignard reagents, R'Li, selenol, R'2B(OH), and R'3SiOH [wherein R' represents an optionally substituted alkyl, aryl, vinyl, or alkynyl group, the alkyl, aryl, and alkynyl groups being as defined above].

[0041] In one embodiment, compound RH is selected from the group consisting of secondary alkylamines, aniline, alkyl alcohols, alkylthiols, arylthiols, arylselenols, phosphine oxides, arylphosphines, and Grignard reagents.

[0042] Preferably, compound RH is HNRd R e and OR f [wherein, R d and R e are independently selected from the group consisting of (C1-C6) alkyl groups and (C6-C 10 ) aryl groups; R f is a (C1-C6) alkyl group or a (C6-C 10 ) aryl (C1-C6) alkyl group] and is selected from the group consisting of].

[0043] In one embodiment of the method according to the invention, the nucleophile is a hydride.

[0044] In one embodiment of the method according to the invention, the nucleophile is of the formula R 2 (R 3 )2SiH [wherein, R 2 and R 3 are independently of each other selected from (C1-C6) alkyl, (C1-C6) alkoxy and (C6-C 10 ) aryl groups, and the aryl group is: (C1-C6) alkyl, (C1-C6) alkoxy, -CN, -OCF3, -NR a R b , -Si(R c )3, -BR a R b , (C2-C6) alkenyl, (C2-C6) alkynyl, -C(=O)-NR a R b , -C(=O)-O(C1-C6) alkyl, and is optionally substituted with at least one substituent selected from CF3, R a , R b and R c are as defined above] and is a silane compound.

[0045] In one embodiment of the method according to the invention, the nucleophile is a silane compound of the formula R 2 [[ID=​​​​​​​The aryl groups are independently selected from each other, and the aryl groups are optionally substituted with at least one substituent selected from (C1-C6)alkyl, (C1-C6)alkoxy, -C(=O)-O(C1-C6)alkyl, and CF3.

[0046] In one embodiment of the method according to the present invention, the nucleophile is selected from the group consisting of EtMe2SiH, Me(OMe)2SiH, Me(OEt)2SiH, (OEt)3SiH, Et3SiH, tBuMe2SiH, Me2PhSiH, Me2BnSiH, MePh2SiH, Ph3SiH, Me2(p-CF3(C6H4))SiH, Me2(p-tBu(C6H4))SiH, and 1,1,3,3-tetramethyldisiloxane (TMDSO).

[0047] In one embodiment, the nucleophile is Me2(p-CF3(C6H4))SiH or Me2BnSiH, and preferably the nucleophile is Me2(p-CF3(C6H4))SiH.

[0048] In one embodiment of the method according to the present invention, the nucleophile is selected from the group consisting of alkylamines, cycloalkylamines, arylamines, alkylthiols, thiophenol compounds, arylselenols, phosphine oxides, phosphines, Grignard reagents, alcohols, or esters. The alkylamines, cycloalkylamines, and arylamines may be primary and / or secondary amines.

[0049] In particular, the nucleophile is a ZH group [wherein Z is (C1~C6)alkyl, -O-(C1~C 12 )alkyl, heterocycloalkyl, -S-cyclo(C3~C 10 )alkyl, -P(=O)-Z 1 Z 2 , and -X 1 -Ar 1 , X 1 -(C1~C 12 ) Alkyl-Het 1 Selected from the group consisting of X 1is S, Se, NH or N-alkyl, and Ar 1 (C6~C 10 ) is an aryl group, Het 1 is an optionally substituted heteroaryl group, Z 1 and Z 2 These are (C1~C6) alkyl groups or (C6~C) 10 It is an aryl group.

[0050] Preferably, Z is (C1-C6) alkyl, heterocycloalkyl, -S-cyclo(C3-C) 10 )alkyl, -P(=O)-Z 1 Z 2 and -X 1 -Ar 1 Selected from the group consisting of, in the formula, X 1 is S, Se or NH, Ar 1 (C6~C 10 ) It is an aryl group, Z 1 and Z 2 These are (C1~C6) alkyl groups or (C6~C) 10 It is an aryl group.

[0051] The terms "alkyl," "aryl," "heterocycloalkyl," "heteroaryl," and their optional substituents are defined above.

[0052] More preferably, the nucleophile is selected from the group consisting of heterocycloalkyl groups containing at least one nitrogen and / or sulfur atom, such as morpholine, aniline groups and their derivatives, such as 4-methylaniline, HS-(cyclo)-alkyl groups, such as CySH, HS-aryl groups, such as 4-methylthiophenol, HSearyl groups, such as benzene selenol, phosphine oxides such as HP(=O)Ph2, phosphines such as HPPh2, and Grignard reagents such as Alk-MgBr, particularly iPrMgBr.

[0053] According to one embodiment, if the nucleophile is selected from the group consisting of alkylamines, cycloalkylamines, arylamines, alkylthiols, thiophenol compounds, arylselenole compounds, phosphine oxides, phosphines, Grignard reagents, alcohols, or esters, the method of the present invention as defined above may further include the use of a hydrogenated compound such as LiHMDS. In this embodiment, compound A-SCF3 of formula (I) is reacted with the nucleophile in the presence of a metal complex, ligand, and solvent, and together with the hydrogenated compound.

[0054] In this embodiment, the nucleophile is particularly a Grignard reaction product.

[0055] According to one embodiment, in the method of the present invention, the ligand is selected from the group consisting of 1,5-cyclooctadiene (COD), 1,2-bis(dicyclohexylphosphino)ethane (dcype), 1,1'-bis(diphenylphosphino)ferrocene (dppf), 1,1'-bis(di-tert-butylphosphino)ferrocene (DTBPF), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xanthophos), triphenylarsine (AsPh3), and triphenylphosphan (PPh3).

[0056] The term "ligand" refers to a chemical component that can bond to the metal in a metal complex. The initial state of a metal complex is the state in which the metal complex is used in the reaction medium. In the initial state of a metal complex, ligands can bond to the metal.

[0057] Alternatively, ligands can be added to the reaction medium in addition to the metal complex. In such cases, the ligands bind to the metal in the reaction medium.

[0058] According to one embodiment of the method, the ligand is bonded to the metal in the initial state of the metal complex.

[0059] According to another embodiment of the method, the ligand is added to the reaction medium in addition to the metal complex.

[0060] According to one embodiment of the method, at least one first ligand is bonded to the metal in the initial state of the metal complex, and at least one second ligand is added to the reaction medium in addition to the metal complex, wherein the first and second ligands are either the same or different.

[0061] Preferably, the metal complex is a Ni(0) complex such as bis(1,5-cyclooctadiene)nickel (Ni[cod]2) or bis(triphenylphosphine)nickel (Ni[PPh3]2).

[0062] In another embodiment, the metal complex may include nickel, palladium, or rhodium(I). For example, the metal complex may be a Pd(0) complex such as tris(dibenzylideneacetone)dipalladium(0) of formula Pd2dba3 or tetrakis(triphenylphosphine)palladium(0) of formula Pd(PPh3)4. In particular, the metal complex may be a Pd(II) complex such as [1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene](3-chloropyridyl)palladium(II) dichloride (PEPSI Pd IPr, 905459-27-0), palladium(II) acetate of formula Pd(OAc)2, or allylpalladium(II) chloride dimer of formula [Pd(π-allyl)Cl]2. Alternatively, the metal complex may be an Rh(I) complex such as carbonyl rhodium chloride of formula [Rh(CO)2Cl]2 or hydroxy(cyclooctadiene) rhodium(I) dimer of formula [Rh(OH)COD]2.

[0063] According to one embodiment, the solvent used in the reaction of the compound of formula (I) with the nucleophile according to the present invention is selected from ordinary solvents used in the art. Preferably, the solvent for this step according to the present invention is toluene.

[0064] According to one embodiment of the method according to the present invention, the reaction of the compound of formula (I) with a nucleophile is carried out at a temperature of 90°C to 140°C. Preferably, this reaction may be carried out at 90°C, 110°C, 120°C, and 140°C.

[0065] According to one embodiment, in formula (I) defined above, A is selected from heteroaryl groups containing 5 to 10 atoms, and contains at least one heteroatom selected from O, N, and S, wherein the heteroaryl group is a halogen, (C1-C6) alkyl, (C1-C6) alkoxy, -CN, -CF3, -OCF3, -NR a R b , -Si(R c )3, -BR a R b (C2~C6) alkenyl, (C2~C6) alkynyl, -C(=O)-NR a R b , and are optionally substituted with at least one substituent selected from -C(=O)-O(C1~C6)alkyl, R a , R b and R c This is as defined above.

[0066] The present invention also relates to a compound of formula (I) as follows:

[0067] [ka]

[0068] The present invention relates to a compound having the method defined above. [Examples]

[0069] (Example 1: Method for capturing thiocarbonyl fluoride in the presence of secondary aniline as compound RH)

[0070] [ka]

[0071] Scheme 1: Reaction conditions: Tank A: 12 (0.5 mmol, 1 equivalent), Ni(cod)2 (10 mol%), Me2(p-CF3(C6H4))SiH (4 equivalents), toluene (0.25 M), 140°C, 16 hours; Tank B: 20 ​​(0.1 mmol), THF (0.07 M), -70°C, 16 hours, then 21°C, 1 hour. The yields shown are the yields of the isolated product.

[0072] Two oven-dried, two-chamber tubes (chamber A: 10 mL and chamber B: 2 mL), both equipped with stirring bars and connected to a reflux condenser, were packed as follows: Chamber A was packed under argon with Ni(cod)2 (14 mg, 0.05 mmol, 10 mol%), 2-((trifluoromethyl)thio)benzo[d]thiazole 12 (118 mg, 0.5 mmol, 1 equivalent), Me2(p-CF3(C6H4))SiH (408 mg, 2 mmol, 4 equivalents), and toluene (2 mL); and Chamber B was packed under argon with secondary aniline (0.1 mmol) and THF (1.5 mL). The resulting solutions were stirred at 140°C for 16 hours (chamber A), -70°C for 16 hours, and then at 21°C for 1 hour (chamber B). The residue in chamber B was concentrated under vacuum and purified by silica gel flash column chromatography to obtain the desired product.

[0073] (Example 2: Method for capturing thiocarbonyl fluoride in the presence of an alkyl alcohol as RH)

[0074] [ka]

[0075] Scheme 2: Reaction conditions: Tank A: 12 (0.5 mmol, 1 equivalent), Ni(cod)2 (10 mol%), Me2(p-CF3(C6H4))SiH (4 equivalents), toluene (0.25 M), 140°C, 16 hours; Tank B: 22 (0.1 mmol), toluene (0.07 M), -70°C, 16 hours, then 21°C, 1 hour. The yields shown are the yields of the isolated product.

[0076] Oven-dried two-compartment tubes (compartment A: 10 mL and compartment B: 2 mL), both equipped with stirring bars and connected to reflux condensers, were packed as follows: Compartment A was packed under argon with Ni(cod)2 (14 mg, 0.05 mmol, 10 mol%), 2-((trifluoromethyl)thio)benzo[d]thiazole 12 (118 mg, 0.5 mmol, 1 equivalent), Me2(p-CF3(C6H4))SiH (408 mg, 2 mmol, 4 equivalents), and toluene (2 mL); Compartment B was packed under argon with alkyl alcohol (0.1 mmol) and toluene (1.5 mL). The resulting solutions were stirred at 140°C for 16 hours (compartment A), -70°C for 16 hours, and then at 21°C for 1 hour (compartment B). The residue in compartment B was concentrated under vacuum, purified by silica gel flash column chromatography, and the sample was dried and loaded. Elution was performed in the solvent system described below to obtain the desired product.

[0077] (Example 3: Step of reacting the compound of formula (I-1) in the presence of various nucleophiles, metal complexes and ligands)

[0078] [ka]

[0079] Schemes 3A and 3B: Reaction conditions: 12 (0.5 mmol, 1 equivalent), catalyst (X mol%), ligand (X mol%), LiHMDS (Xeq.), nucleophile (4 eq.), toluene under argon, T (°C), time (hours). The term "catalyst" refers to a metal complex.

[0080] A 10 mL oven-dried tube equipped with a stirring bar was packed under argon with a metal complex (catalyst, X mol%), ligand (X mol%), LiHMDS (Xeq.), 2-((trifluoromethyl)thio)benzo[d]thiazole 12 (118 mg, 0.5 mmol, 1 eq.), nucleophile (4 eq.), and toluene. The resulting solution was stirred at temperature T (°C) for 16 or 48 hours. The reaction conditions are reported in Table 1 below. The mixture was cooled to 21°C. 10 mL of toluene (10 mL) was added to the mixture, and the resulting solution was washed with an aqueous solution of NaOH (1 M, 10 mL). The aqueous phase was extracted with toluene (3 × 20 mL), and the combined organic layers were dried over MgSO4 and concentrated under vacuum. The residue was purified by silica gel flash column chromatography to obtain the desired products 2a and 2c-2i. The corresponding yields are reported in Scheme 3C and Table 1 below.

[0081] [Table 1]

[0082] [ka]

[0083] Scheme 3C: Compounds 2c to 2i were synthesized according to Scheme 3B in the presence of a nucleophile of formula ZH.

[0084] The results demonstrate that cleavage of the CS bond (a step that leads to the formation of compounds AH and SCF2 from the compound of formula (I) according to the present invention) can be achieved in high yield in the presence of various metal complexes, nucleophiles, and ligands. It can be expected that a method for capturing thiocarbonyl fluoride from the A-SCF3 compound using these reaction conditions can be achieved in favorable yield.

[0085] (Example 4: As A (C6~C 10 (A step of reacting an A-SCF3 compound having an aryl group.)

[0086] [ka]

[0087] Scheme 4: Reaction conditions: Under argon, 27 (0.5 mmol, 1 equivalent), Ni(cod)2 (5 mol%), dcype (5 mol%), toluene (5 equivalents), 1 M LiHMDS solution, morpholine (4 equivalents), 140°C, 48 hours. The yields shown are the isolated yields.

[0088] In oven-dried 10 mL tubes equipped with a stirring bar, Ni(cod)2 (7 mg, 0.025 mmol, 5 mol%), dcype (11 mg, 0.025 mmol, 5 mol%), LiHMDS (2.5 mL, 1 M, 418 mg, 2.5 mmol, 5 equivalents), 27 (0.5 mmol, 1 equivalent), and morpholine (2 mmol, 4 equivalents) were packed under argon. The resulting solution was stirred at 140°C for 48 hours. The mixture was cooled to 21°C. SiO (10 mL) was added to the mixture, and the resulting solution was washed with an aqueous solution of NaOH (1 M, 10 mL). The aqueous phase was extracted with SiO (3 × 20 mL), and the combined organic layers were dried over MgSO4 and concentrated under vacuum. The residue was purified by silica gel flash column chromatography to isolate the desired product 28.

[0089] These results indicate that cleavage of the CS bond (a step that leads to the release of fluorinated residue) is achieved in the presence of an aryl group. It can be expected that a method for capturing thiocarbonyl fluoride from A-SCF3 compounds where A is an aryl group can be achieved in high yield.

[0090] (Example 5: Step of reacting with an A-SCF3 compound having a vinyl group as A)

[0091] [ka]

[0092] Scheme 5: Reaction conditions: 29 (0.3 mmol, 1 equivalent), Ni(cod)2 (5 mol%), dcype (5 mol%), LiHMDS 1M solution in toluene (5 equivalents), morpholine (4 equivalents), under argon at 140°C for 48 hours. Yield: 1 The determination was made by 1H NMR using nitromethane as an internal standard.

[0093] In oven-dried 10 mL tubes equipped with a stirring bar, Ni(cod)2 (4 mg, 0.015 mmol, 5 mol%), dcype (6 mg, 0.015 mmol, 5 mol%), LiHMDS (1.5 mL, 1 M, 251 mg, 1.5 mmol, 5 equivalents), 47 (0.3 mmol, 1 equivalent), and morpholine (1.2 mmol, 4 equivalents) were packed under argon. The resulting solution was stirred at 140°C for 48 hours. The mixture was cooled to 21°C. SiO (10 mL) was added to the mixture, and the resulting solution was washed with an aqueous solution of NaOH (1 M, 10 mL). The aqueous phase was extracted with SiO (3 × 20 mL), and the combined organic layers were dried over MgSO4 and concentrated under vacuum. The yield of 30 was obtained. 1 The determination was made by 1H NMR using nitromethane as an internal standard.

[0094] This result indicates that cleavage of the CS bond (a step that leads to the release of fluorinated residue) is achieved in the presence of vinyl. It can be expected that a method for capturing thiocarbonyl fluoride from A-SCF3 compounds where A is vinyl can be achieved in high yield.

Claims

1. A method for capturing SCF2, - Equation (I) A-SCF 3 (I) [In the formula, A is, .(C 6 ~C 10 ) Aryl group {The aryl group is preferably optionally substituted with at least one substituent selected from the group consisting of halogen, (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, -CN, -CF 3 , -OCF 3 , -NR a R b , -SiR a R b R c , -BR a R b , (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, -C(=O)-NR a R b and -C(=O)-O(C 1 -C 6 )alkyl; R a and R b H or (C 1 ~C 6 ) is an alkyl group; R c is (C 1 ~C 6 ) is an alkyl group; A heteroaryl group containing 0.5 to 10 atoms and at least one heteroatom selected from O, N, and S. {The heteroaryl group is preferably a halogen, (C 1 ~C 6 ) alkyl, (C 1 ~C 6 ) Alkoxy, -CN, -CF 3 , -OCF 3 , -NR a R b , -Si(R c ) 3 ,-BR a R b , (C 2 ~C 6 ) Alkenil, (C 2 ~C 6 ) Alkinyl, -C(=O)-NR a R b and -C(=O)-O(C 1 ~C 6 )Optionally substituted with at least one substituent selected from alkyl, R a , R b and R c This is as defined above; and .Following formula (III): 【Chemistry 1】 {where, R 1 is halogen, (C 1 ~C 6 ) alkyl, (C 1 ~C 6 ) Alkoxy, -CN, -CF 3 , -OCF 3 , -NR a R b , -Si(R c ) 3 ,-BR a R b , (C 2 ~C 6 ) Alkenil, (C 2 ~C 6 ) Alkinyl, -C(=O)-NR a R b and -C(=O)-O(C 1 ~C 6 ) Selected from the group consisting of alkyl groups, R a , R b and R c Vinyl compounds having the above definition A compound having [selected from the group consisting of] A step of reacting a nucleophile with a metal complex containing nickel, palladium, or rhodium(I), a ligand, and a solvent, Compound AH or Compound AZ [wherein Z is a hydrocarbon group optionally containing at least one heteroatom such as S, N, or O and / or at least one atom other than C or H such as Se, Si, B, or P] and SCF 2 A process that causes the formation of, - To obtain a compound having the formula RC(=S)-F, SCF 2 A step of reacting with compound RH [wherein R is a hydrocarbon group optionally containing at least one heteroatom]. A method that includes this.

2. - Equation (I) A-SCF 3 (I) A compound having [wherein A is defined in claim 1] A step of reacting a nucleophile with a nickel-containing metal complex, ligand, and solvent; compound AH and SCF 2 A process that causes the formation of, - To obtain a compound having the formula RC(=S)-F, SCF 2 A step of reacting with compound RH [wherein R is a hydrocarbon group optionally containing at least one heteroatom]. The method according to claim 1, including the method described in claim 1.

3. The aforementioned compound RH is an amine, alcohol, thiol, phosphine, phosphonate, Grignard reagent, R'Li, selenol, R' 2 B(OH) and R' 3 The method according to claim 1 or 2, wherein SiOH is selected from the group consisting of [wherein R' means an optionally substituted alkyl, aryl, vinyl, or alkynyl group].

4. The method according to any one of claims 1 to 3, wherein the compound RH is selected from the group consisting of secondary alkylamines, aniline, alkyl alcohols, alkylthiols, arylthiols, arylselenols, phosphine oxides, arylphosphines, and Grignard reagents.

5. wherein the compound RH is HNR d R e and OR f [wherein, R d and R e are independently selected from the group consisting of (C 1 -C 6 ) alkyl groups and (C 6 -C 10 ) aryl groups; R f is a (C 1 -C 6 ) alkyl group or a (C 6 -C 10 ) aryl(C 1 -C 6 ) alkyl group) and is selected from the group consisting of], the method according to any one of claims 1 to 4.

6. The nucleophile, formula R 2 (R 3 ) 2 SiH [wherein, R 2 and R 3 (C 1 ~C 6 ) alkyl, (C 1 ~C 6 )alkoxy and (C 6 ~C 10 ) Selected from aryl groups, the aryl group is: (C 1 ~C 6 ) alkyl, (C 1 ~C 6 )alkoxy, -CN, -OCF 3 , -NR a R b , -Si(R c ) 3 ,-BR a R b , (C 2 ~C 6 ) Alkenil, (C 2 ~C 6 ) Alkinyl, -C(=O)-NR a R b , and -C(=O)-O(C 1 ~C 6 ) Alkyl, and CF 3 Optionally substituted with at least one substituent selected from R a , R b and R c The method according to any one of claims 1 to 5, wherein is a silane compound as defined in claim 1.

7. The nucleophile is EtMe 2 SiH, Me(OMe) 2 SiH, Me(OEt) 2 SiH, (OEt) 3 SiH, Et 3 SiH, tBuMe 2 SiH, Me 2 PhSiH, Me 2 BnSiH, MePh 2 SiH, Ph 3 SiH, Me 2 (p-CF 3 (C 6 H 4 ))SiH, and Me 2 (p-tBu(C 6 H 4 The method according to any one of claims 1 to 6, selected from the group consisting of SiH.

8. The nucleophile, Me 2 (p-CF 3 (C 6 H 4 ))SiH or Me 2 The method according to any one of claims 1 to 7, wherein BnSiH.

9. The nucleophile is Me 2 (p-CF 3 (C 6 H 4 The method according to any one of claims 1 to 8, wherein the material is SiH.

10. The method according to any one of claims 1 to 5, wherein the nucleophile is selected from the group consisting of alkylamines, cycloalkylamines, arylamines, alkylthiols, thiophenol compounds, arylselenols, phosphine oxides, phosphines, Grignard reagents, alcohols, and esters.

11. The nucleophile is a ZH group [wherein Z is (C 1 ~C 6 )alkyl, -O-(C 1 ~C 12 )alkyl, heterocycloalkyl, -S-cyclo(C 3 ~C 10 )alkyl, -P(=O)-Z 1 Z 2 , and -X 1 -Ar 1 , X 1 -(C 1 ~C 12 ) Alkyl-Het 1 Selected from the group consisting of X 1 is S, Se, NH or N-alkyl, and Ar 1 (C) was optionally replaced. 6 ~C 10 ) is an aryl group, Het 1 is an optionally substituted heteroaryl group, Z 1 and Z 2 (C 1 ~C 6 ) Alkyl alkyl group or (C 6 ~C 10 The method according to claim 10, wherein the group is an aryl group.

12. The method according to claim 10 or 11, further comprising the use of a hydrogenated compound such as LiHMDS.

13. The ligands are 1,5-cyclooctadiene (COD), 1,2-bis(dicyclohexylphosphino)ethane (dcype), 1,1'-bis(diphenylphosphino)ferrocene (dppf), 1,1'-bis(ditert-butylphosphino)ferrocene (DTBPF), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xanthophos), and triphenylarsine (AsPh 3 ), and triphenylphosphan (PPh 3 The method according to any one of claims 1 to 12, selected from the group consisting of ).

14. The method according to any one of claims 1 to 13, wherein the ligand is bonded to the metal in the initial state of the metal complex, and / or the ligand is added to the reaction medium in addition to the metal complex.

15. The method according to any one of claims 1 to 14, wherein the solvent is toluene.

16. The method according to any one of claims 1 to 15, wherein the reaction with the hydride of the compound of formula (I) is carried out at a temperature of 90°C to 140°C.

17. The method according to any one of claims 1 to 16, wherein the metal complex is a Ni(0) complex such as bis(1,5-cyclooctadiene)nickel.

18. A is selected from heteroaryl groups containing 5 to 10 atoms, and contains at least one heteroatom selected from O, N, and S, wherein the heteroaryl group is a halogen, (C 1 ~C 6 ) alkyl, (C 1 ~C 6 ) Alkoxy, -CN, -CF 3 , -OCF 3 , -NR a R b , -Si(R c ) 3 ,-BR a R b , (C 2 ~C 6 ) Alkenil, (C 2 ~C 6 ) Alkinyl, -C(=O)-NR a R b , and -C(=O)-O(C 1 ~C 6 )Optionally substituted with at least one substituent selected from alkyl groups, R a , R b and R c The method according to any one of claims 1 to 17, wherein is as defined in claim 1.

19. The compound of formula (I) is shown in formula (I-1): 【Chemistry 2】 The method according to any one of claims 1 to 18, wherein the compound is having the compound.

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