Process for producing aryl thiolester compound

Abstract

The present application provides a production method capable of rapidly and with high yield synthesizing an aryl mercaptan ester compound under mild conditions. The present application is a production method of an aryl mercaptan ester compound, in which a diazo compound represented by the following general formula (2) and a mercaptan ester compound represented by the following general formula (3) are subjected to a Sandmeyer type coupling reaction using a catalyst to produce an aryl mercaptan ester compound represented by the following general formula (1) [in the formula, A 1 and A 2 Each independently is aryl which can have a substituent or heteroaryl which can have a substituent; X 1 is a monovalent anion; M 1 is a monovalent cation].

Description

Technical Field

[0001] This invention relates to a method for manufacturing an aryl thiol ester compound.

[0002] This application claims priority based on Japanese Patent Application No. 2021-032819, filed in Japan on March 2, 2021, the contents of which are incorporated herein by reference. Background Technology

[0003] Aryl thiols have highly electrophilic carbonyl groups, making them suitable as electrophilic reagents in acyl transfer processes and as carbanion precursors in condensation reactions. Aryl thiols are useful intermediates in the synthesis of organic compounds that are raw materials for organic materials, biochemical products, and pharmaceuticals; therefore, there is a need to develop a more efficient manufacturing method.

[0004] Aryl thiolates can be synthesized, for example, via nucleophilic reactions of thiolates with carboxylic acid derivatives. Compounds that are difficult to synthesize using this method require alternative synthetic approaches. For instance, there are synthetic methods utilizing the thermal rearrangement of O-aryl thiolates, and methods involving the reaction of organometallic catalysts with diaryliodic acids. Methods involving the reaction of electrophilic substrates such as salts and aryl halides are used. However, these methods require harsh reaction conditions, necessitating a method that can synthesize under milder conditions. One method for synthesizing under milder conditions has been reported, for example, by reacting aryl diazotized aryl halides in DMSO at room temperature. Various S-aryl thioacetic acid esters can be synthesized in yields of 40–60% by treating tetrafluoroborate with potassium thioacetate (Non-Patent Literature 1, Non-Patent Literature 2).

[0005] Existing technical documents

[0006] Non-patent literature

[0007] Non-patent literature 1: Petrillo et al., Tetrahedron Letters, 1988, vol. 29(33), p. 4185-4188.

[0008] Non-patent literature 2: Petrillo et al., Tetrahedron, 1989, vol.45(23), p.7411-7420. Summary of the Invention

[0009] The purpose of this invention is to provide a method for rapidly synthesizing aryl thiol ester compounds under mild conditions and in high yield.

[0010] The inventors have discovered that by utilizing Sandmeyer-type coupling reactions during the synthesis of aryl thiol esters, it is possible to synthesize aryl thiol esters from diazo compounds. The present invention is achieved by rapidly synthesizing compounds and thiol ester compounds under mild conditions, and by using a catalyst to improve the yield.

[0011] That is, the present invention is as follows.

[0012] [1] A method for producing an aryl thiol ester compound, comprising a diazo compound represented by the following general formula (2). The aryl thiol ester compound represented by the following general formula (3) is prepared by using a Sandmayer-type coupling reaction with a catalyst.

[0013]

[0014] [In the formula, A] 1 It can be an aryl group that may have substituents or a heteroaryl group that may have substituents; X 1 It is a monovalent anion.

[0015]

[0016] [In the formula, A] 2 It can be an aryl group that may have substituents or a heteroaryl group that may have substituents; M 1 It is a monovalent cation.

[0017]

[0018] [In the formula, A] 1 and A 2 Same as above.

[0019] [2] The method for manufacturing aryl thiol ester compounds according to [1] above, wherein the catalyst is a transition metal complex.

[0020] [3] According to the method for manufacturing the aryl thiol ester compound described in [2] above, the transition metal complex is a copper complex.

[0021] [4] The method for manufacturing the aryl thiol ester compound according to [2] or [3] above, wherein the transition metal complex comprises a bidentate nitrogen chelate ligand.

[0022] [5] The method for manufacturing any of the aryl thiol ester compounds in [2] to [4] above, wherein the transition metal complex is composed of cuprous ions and one or more ligands selected from 1,10-phenanthroline, 2,2'-bipyridine and their derivatives.

[0023] [6] The method for producing any of the aryl thiol ester compounds in [1] to [5] above, wherein, prior to the above Sandmayer type coupling reaction, the amino aryl compound represented by the following general formula (4) is diazotized to produce the compound represented by the above general formula (2).

[0024] A 1 —NH2 (4)

[0025] [In the formula, A] 1 Same as above.

[0026] According to the method of the present invention, aryl thiol ester compounds can be synthesized in high yield and with high efficiency. Detailed Implementation

[0027] In this invention and the specification of this application, "C" p1 - p2 "(p1 and p2 are positive integers that satisfy p1 < p2) refers to a group with a carbon atom number of p1 to p2.

[0028] In this invention and the specification of this application, "C" 1－6 Alkyl groups are alkyl groups with 1 to 6 carbon atoms, and can be straight-chain or branched. As a C... 1－6 Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, and n-hexyl.

[0029] In this invention and the specification of this application, "C" 1－6 "Alkoxy" refers to C 1－6 The alkyl group has an oxygen atom bonded to its terminal. C 1－6 Alkyl groups can be straight-chain or branched. As a C... 1－6 Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, and hexoxy.

[0030] In this invention and the specification of this application, "C" 2－6 "Alkenyl" refers to an alkyl group having at least one unsaturated carbon-carbon bond, consisting of 2 to 6 carbon atoms. As a C 2－6 Alkenyl groups can be straight-chain or branched. As a C... 2－6 Examples of alkenyl groups include vinyl, allyl, butenyl, pentenyl, and hexenyl.

[0031] In this invention and the specification of this application, "C" 2－7 "Acyl" refers to the hydrocarbon group remaining after removing the carbonyl group from the acyl group, where the hydrocarbon group is C. 1－6 Alkyl, C 2－6An alkenyl, five-membered or six-membered aryl, or five-membered or six-membered heteroaryl group. The hydrocarbon moiety of the acyl group can be straight-chain or branched. As a C 2－7 Acyl groups include formyl, acetyl, propionyl, acryloyl, benzoyl, etc.

[0032] In this invention and in this application specification, "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 examples of "halogen atom other than fluorine atom", chlorine atom or bromine atom is preferred, and chlorine atom is particularly preferred.

[0033] Additionally, in the following, "compound(n)" refers to the compound represented by formula (n).

[0034] The method for producing the aryl thiol ester compound of the present invention is based on diazotized esters represented by the following general formula (2). The compound (hereinafter, sometimes referred to as "diazo") A method for producing an aryl thiol ester compound (hereinafter, sometimes referred to as "aryl thiol ester compound (1)") by means of a Sandmeier-type coupling reaction of a thiol ester compound represented by compound (2)” and a thiol ester compound represented by the following general formula (3)”. The Sandmeier-type coupling reaction is an aromatic nucleophilic substitution reaction based on a free radical mechanism. The aryl thiol ester compound (1) can be rapidly produced under relatively mild conditions of 0–40 °C by means of the Sandmeier-type coupling reaction.

[0035]

[0036] In general formulas (1), (2), and (3), A 1 and A 2 Each can be an aryl group or a heteroaryl group that can have substituents. There is no particular limitation on the aryl group; examples include phenyl, naphthyl, anthracenel, 9-fluorenyl, etc., with phenyl being particularly preferred. There is no particular limitation on the heteroaryl group; examples include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyrazolyl, quinolinyl, isoquinolinyl, pyrroleyl, imidazolyl, indolyl, furanyl, benzofuranyl, thiophene, benzothiophene, etc. azole group, iso Azolium, thiazolyl, isothiazolium, etc.

[0037] "Substitutable aryl group" refers to a group in which one or more, preferably one to three, hydrogen atoms bonded to the carbon atom of an aryl group are substituted with other functional groups. Similarly, "substitutable heteroaryl group" refers to a group in which one or more, preferably one to three, hydrogen atoms bonded to the carbon atom of a heteroaryl group are substituted with other functional groups. When there are two or more substituents, the substituents can be of the same type or different types.

[0038] A 1 and A 2 The aryl and heteroaryl groups may have one or more substituents besides the sulfur atom used for fluorination. Examples of such substituents include halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, acyl groups, hydroxyl groups, carboxyl groups, cyano groups, amino groups, and nitro groups. As for the alkyl group, C4 is preferred. 1－6 Alkyl groups, preferably C10, are preferred as alkenyl groups. 2－6 Alkyl groups, preferably C14 as alkoxy groups. 1－6 Alkoxy groups, as acyl groups, are preferably C. 2－7 Acyl group.

[0039] In general formula (2), X 1 It is a monovalent anion. As X 1 For example, BF4 can be cited. － PF6 － wait.

[0040] In general formula (3), M 1 It is a monovalent cation. As M... 1 For example, sodium ions and potassium ions can be cited.

[0041] As a diazoonium compound (2), A in general formula (2) is preferred. 1 The compound may be a phenyl or pyridyl group having substituents, more preferably A. 1 It is a compound having 1 to 3 substituents selected from halogen atoms, alkyl, alkenyl, alkoxy, aryl, acyl, hydroxyl, carboxyl, cyano, amino and nitro groups, or having pyridyl groups selected from halogen atoms, alkyl, alkenyl, alkoxy, aryl, acyl, hydroxyl, carboxyl, cyano, amino and nitro groups.

[0042] As a thiol ester compound (3), A in general formula (3) is preferred. 2 It can be a phenyl or pyridyl group that has substituents and M 1 for Na + or K + The compound, more preferably A 2It can be a phenyl group having 1 to 3 substituents selected from halogen atom, alkyl, alkenyl, alkoxy, aryl, acyl, hydroxyl, carboxyl, cyano, amino, and nitro, or a pyridyl group having 1 to 3 substituents selected from halogen atom, alkyl, alkenyl, alkoxy, aryl, acyl, hydroxyl, carboxyl, cyano, amino, and nitro, and M 1 for Na + or K + Compounds.

[0043] A in general formula (1) can be synthesized by reacting these diazoonium compounds (2) with thiol ester compounds (3). 1 and A 2 Each is an aryl thiol ester compound that may have a substituted phenyl group or a substituted pyridyl group (1).

[0044] The amounts of diazoonium compound (2) and thiol ester compound (3) added to the reaction system are not particularly limited, as long as they are above stoichiometric amounts. Considering the reaction efficiency and cost, the amount of thiol ester compound (3) present in the reaction solution of the above-mentioned Sandmeier type coupling reaction at the beginning of the reaction is preferably 1 to 5 equivalents of thioaryl compound (2), more preferably 1 to 2 equivalents.

[0045] In this invention, the Sandmeier-type coupling reaction that bonds the diazoonium compound (2) to the thiol ester compound (3) is carried out using a catalyst. The aryl thiol ester compound (1) can be synthesized in high yield via the Sandmeier-type coupling reaction using a catalyst. The catalyst used is not particularly limited as long as it can catalyze the Sandmeier-type coupling reaction; however, since the reaction can be carried out efficiently at temperatures ranging from 0 to 40°C, transition metal complexes are preferred as catalysts.

[0046] For example, copper, silver, palladium, gold, and nickel can be used as the transition metal constituting the transition metal complex. Furthermore, the ligand constituting the transition metal complex is not particularly limited as long as it has a lone pair of electrons capable of chelating and coordinating with the transition metal used; it can be a monodentate ligand, a bidentate ligand, or a multidentate ligand. As the transition metal complex used in this invention, a copper complex is preferred, a complex composed of a cuprous ion and a bidentate ligand is more preferred, and a complex composed of a cuprous ion and a bidentate nitrogen-chelating ligand is even more preferred.

[0047] Examples of bidentate nitrogen chelating ligands include, for example, 1,10-phenanthroline, 2,2'-bipyridine, and their derivatives. Examples of derivatives of 1,10-phenanthroline include those in which one or more hydrogen atoms bonded to the carbon atom are halogenated, C... 1－6Compounds obtained by substituting alkyl, aryl, heteroaryl, nitro, amino, hydroxyl, carbonyl, carboxyl, etc. Similarly, as derivatives of 2,2'-bipyridine, examples include those in which one or more hydrogen atoms bonded to the carbon atom are replaced by halogen atoms, C... 1－6 Compounds obtained by substitution with alkyl, aryl, heteroaryl, nitro, amino, hydroxyl, carbonyl, carboxyl, etc. As halogen atoms, C... 1－6 Alkyl, aryl, heteroaryl, and other groups that are the same as those listed above can be given examples.

[0048] As derivatives of 1,10-phenanthroline, specific examples include 2-methyl-1,10-phenanthroline (CAS No: 3002-77-5), 5-methyl-1,10-phenanthroline hydrate (CAS No: 002-78-6), 4,7-dimethyl-1,10-phenanthroline (CAS No: 3248-05-3), 5,6-dimethyl-1,10-phenanthroline (CAS No: 3002-81-1), and 3,4,7,8-tetramethyl-1,10-phenanthroline (CAS No: 1660-93-1). 4,7-Diphenyl-1,10-Phenanthroline (CAS No.: 1662-01-7), Bathocuproine (2,9-Dimethyl-4,7-Diphenyl-1,10-Phenanthroline (CAS No.: 4733-39-5), 2-Bromo-1,10-Phenanthroline (CAS No.: 22426-14-8), 3-Bromo-1,10-Phenanthroline (CAS No.: 66) 127-01-3), 5-bromo-1,10-phenanthroline (CAS No.: 40000-20-2), 2-chloro-1,10-phenanthroline (CAS No.: 7089-68-1), 4,7-dibromo-1,10-phenanthroline (CAS No.: 156492-30-7), 3,8-dibromo-1,10-phenanthroline (CAS No.: 100125-12-0), 2,9-dichloro-1,10 - Phenanthroline (CAS No.: 29176-55-4), 1,10-phenanthroline-5,6-dione (CAS No.: 27318-90-7), 4,7-dihydroxy-1,10-phenanthroline (CAS No.: 3922-40-5), 5-nitro-1,10-phenanthroline (CAS No.: 4199-88-6), 5-amino-1,10-phenanthroline (CAS No.: 54258-41-2), etc.

[0049] As derivatives of 2,2'-bipyridine, examples include 4,4'-dimethyl-2,2'-bipyridine (CAS No.: 1134-35-6), 6,6'-dimethyl-2,2'-bipyridine (CAS No.: 4411-80-7), 4,4'-di-tert-butyl-2,2'-bipyridine (BBBPY) (CAS No.: 72914-19-3), and 4,4'-bis(trifluoromethyl)-2,2'-bipyridine (CAS No.: 142946-79-0). ), 5,5'-bis(trifluoromethyl)-2,2'-bipyridine (CAS No.: 142946-80-3), 6-bromo-4,4'-dimethyl-2,2'-bipyridine (CAS No.: 850413-36-4), 5-bromo-2,2'-bipyridine (CAS No.: 15862-19-8), 4,4'-dibromo-2,2'-bipyridine (CAS No.: 18511-71-2), 5,5'-dibromo-2,2'-bipyridine (CAS No.: 15862) -18-7), 6,6'-dibromo-2,2'-bipyridine (CAS No.: 49669-22-9), 4,4'-bis(5-hexyl-2-thiophene)-2,2'-bipyridine (CAS No.: 1047684-56-9), 4,4'-diamino-2,2'-bipyridine (CAS No.: 18511-69-8), 6,6'-diamino-2,2'-bipyridine (CAS No.: 93127-75-4), 2,2'-bipyridine-3,3'- Diols (CAS No.: 36145-03-6), 2,2'-bipyridine-5,5'-diol (CAS No.: 2326-78-5), 2,2'-bipyridine-6,6'-diol (CAS No.: 103505-54-0), 2,2'-bipyrazine (CAS No.: 10199-00-5), 2,2'-biquinoline (CAS No.: 119-91-5), 4,4'-dimethyl-2,2'-biquinoline (CAS No.: 7654-51-5), etc.

[0050] As the catalyst used in the Sandmeier-type coupling reaction of the present invention, a copper complex consisting of a cuprous ion and one or more ligands selected from 1,10-phenanthroline, 2,2'-bipyridine and their derivatives is preferred; a copper complex consisting of a cuprous ion and one or more ligands selected from phenanthroline, red phenanthroline, 2,2'-bipyridine and BBBPY is more preferred.

[0051] The amount of catalyst added to the reaction system is not particularly limited, as long as it increases the yield of the product obtained from the Sandmeier-type coupling reaction compared to the case without catalyst. For example, the amount of catalyst added to the reaction solution relative to the diazoium compound (2) as the substrate is preferably 5 to 30 mol%, more preferably 5 to 25 mol%, even more preferably 5 to 20 mol%, and even more preferably 10 to 20 mol%.

[0052] In Sandmeier-type coupling reactions, transition metal complexes can be added to the reaction solution, or transition metal sources and ligands can be added to synthesize transition metal complexes in the reaction solution. As a transition metal source, a salt of the transition metal ion and anion constituting the target transition metal complex is preferred. For example, when using a copper complex composed of cuprous ions and ligands as a catalyst, cuprous thiocyanate (CuSCN), cuprous bromide-dimethyl sulfide complex (CuBr·SMe2), and cuprous cyanide (CuCN) can be cited as cuprous sources.

[0053] The aforementioned Sandmeier-type coupling reaction can be carried out in a non-reactive solvent. There are no particular limitations on the non-reactive solvent, but a protonated polar solvent is preferred. Examples of aprotonated polar solvents include acetonitrile (MeCN), N,N'-dimethylformamide (DMF), N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), dichloromethane (DCM), and diethyl ether. The solvent used in the reaction can be a mixture of two or more solvents.

[0054] The aforementioned Sandmeier-type coupling reaction involves reacting a reaction solution obtained by mixing a diazoonium compound (2) and a thiol ester compound (3) with a catalyst in a reaction solvent at an appropriate temperature and time. A transition metal source and ligands can be added instead of the catalyst. This Sandmeier-type coupling reaction is carried out under mild conditions. For example, the reaction temperature is not particularly limited as long as the reaction solvent is liquid, and can be carried out at -40 to 130°C, preferably at -30 to 80°C, and more preferably at room temperature (0 to 30°C). For example, this Sandmeier-type coupling reaction can yield the target aryl thiol ester compound (1) in a high yield, for example, more than 70%, by reacting at room temperature for less than 1 hour.

[0055] The synthesized aryl thiol ester compound (1) can be used as a substrate for the synthesis of other organic compounds. For example, aryl compounds containing pentafluorothio groups can be produced by using the aryl thiol ester compound (1) as a substrate and carrying out an oxidative fluorination reaction using AgF2.

[0056] When the synthesized aryl thiol ester compound (1) is used as a substrate for the synthesis of other organic compounds, the reaction solution containing the reaction product of the above-described Sandmeier-type coupling reaction can be used directly in the next reaction, or the aryl thiol ester compound (1) can be purified from the reaction solution and used in the next reaction. There are no particular limitations on the purification method; common purification methods such as filtration can be used.

[0057] The diazoonium compound (2) used in the above Sandmeier-type coupling reaction can be produced by diazotizing an aminoaryl compound represented by the following general formula (4) (hereinafter, sometimes referred to as "aminoaryl compound (4)"). In the following general formula (4), A 1 A in the above general formula (2) 1 same.

[0058] A 1 —NH2 (4)

[0059] The diazotization of aminoaryl compounds (4) can be carried out using various diazo coupling reactions. For example, nitrosium ions (NO3- ... + ) and tetrafluoroborate ions (BF4) － To produce the tetrafluoroborate of diazoium compound (2) by reacting it with the amino group of amino aryl compound (4) (aryl diazoium tetrafluoroborate: Al-N2+BF4). － The diazotization reaction of aminoaryl compound (4) can also be carried out with sodium nitrite and hydrochloric acid, in which case the hydrochloride salt of diazoonium compound (2) can be produced.

[0060] This diazotization reaction can be carried out in a solvent inert to the reaction at a temperature in which the reaction solvent is liquid. The same inert solvent that can be used in the aforementioned Sandmeier-type coupling reaction can be used as this inert solvent.

[0061] When the diazoonium compound (2) synthesized from the diazotization reaction of the aminoaryl compound (4) is used in the above Sandmeier-type coupling reaction, the diazotization reaction and the subsequent Sandmeier-type coupling reaction can also be carried out in a one-pot process.

[0062] Example

[0063] The present invention will now be described with reference to embodiments, but the present invention is not limited to these embodiments.

[0064] The NMR apparatus used in the analyses of the examples and comparative examples was a JNM-ECZ400S (400MHz) manufactured by Nippon Electronics. 1 In H NMR, tetramethylsilane is set as the reference value of 0 PPM. 19In F NMR, C6F6 is set as the reference value of -162 PPM.

[0065] [Example 1]

[0066] The following method synthesizes 4-methoxyphenylthiobenzoate.

[0067] (1) Diazotization of amino aryl groups

[0068] First, benzenediazaonium salts are synthesized using conventional synthetic methods.

[0069]

[0070] A boron trifluoride-diethyl ether complex (BF3·OEt2) (1.5 mmol, 1.5 equivalents) was added to a solution of 4-methoxyaniline (1 mmol, 1 equivalent) dissolved in 3 mL of THF at an ice bath temperature. After stirring for 5 minutes, tert-butyl nitrite (1.2 mmol, 1.2 equivalents) was added dropwise to the solution at 0 °C. After further stirring for 15 minutes, the precipitate (benzenediadiazonium salt) was recovered by filtration and washed with diethyl ether.

[0071] (2) Sandmeier-type coupling reaction

[0072] Allyl benzoate was synthesized from benzenediazonium salt and thiobenzoate via a Sandmayer-type coupling reaction based on a copper complex catalyst. CuSCN, CuBr·SMe2, or CuCN·LiCl (THF solution) were used as the copper source, and 1,10-phenanthroline (Phen), bathophen, or BBBPY were used as the ligands.

[0073]

[0074] In an argon-filled drying oven, a cuprous source (X mol%), a ligand (X mol%), potassium thiobenzoate (229 mg, 1.3 mmol), and a magnetic stir bar were placed in a glass vial, followed by the addition of MeCN (1 mL), and stirring for approximately 2 minutes. The reaction mixture was a red suspension containing insoluble potassium thiobenzoate. At room temperature, 4-methoxybenzyldiazamonium tetrafluoroborate (222 mg, 1.0 mmol) dissolved in MeCN (2 mL) was added dropwise to the reaction mixture using a syringe, resulting in the visible formation of nitrogen gas during the addition. The syringe was pre-cleaned with 1 mL of MeCN. After stirring the reaction mixture at room temperature or 0 °C for 1 hour, the resulting reaction mixture was transferred to a 50 mL flask. Silica was added to the flask, and the solvent was evaporated under vacuum. Next, column chromatography was performed (hexane:DCM = 2:1 to 1:1 (volume ratio)) to obtain 4-methoxyphenylthiobenzoate as a yellow solid.

[0075] 1H NMR (400MHz) δ8.06-8.02(m,2H),7.63-7.58(m,1H),7.52-7.46(m,2H),7.46-7.41(m,2H),7.02-6.98(m,2H),3.85(s,3H).

[0076] Table 1 shows the copper complex catalysts (cuprous source and ligand) used in each experimental group, the amount of copper complex used ("X mol%" in the above reaction formula), the reaction temperature, and the yield (%) of 4-methoxyphenylthiobenzoate. In Table 1, " / " indicates no addition. For example, in experimental group 9, using CuSCN (12 mg, 0.1 mmol) as the cuprous source and 1,10-phenanthroline (18 mg, 0.1 mmol) as the ligand, 4-methoxyphenylthiobenzoate (195 mg) (yield 80%) was obtained.

[0077] [Table 1]

[0078]

[0079] Compared to test group 1, which did not use a catalyst, the yields of test groups 2–4, which used copper without a complex as a catalyst, were not improved, or only slightly improved. In contrast, test groups 5–11, which used copper complex catalysts, showed significant improvements in yield regardless of the type of copper source or ligand used. In particular, test group 9, which used a 10 mol% copper complex catalyst composed of CuSCN and 1,10-phenanthroline, achieved a very excellent yield of 80%, compared to phenyldiazeonium salt (4-methoxyphenyldiazeonium tetrafluoroborate).

[0080] When comparing experimental groups 8 with 10 and 11, experimental group 8 had the highest yield, but experimental groups 10 and 11 also showed significant yield improvement. Therefore, it was confirmed that the yield improvement effect brought about by using transition metal complexes as catalysts can also be obtained in a low temperature environment with a reaction temperature of -30℃ to 0℃.

[0081] Industrial availability

[0082] This invention provides a method for rapidly synthesizing aryl thiol ester compounds under relatively mild conditions and in high yield. Furthermore, the aryl thiol ester compounds produced by this invention are useful as intermediates for the manufacture of various organic compounds; therefore, this invention is useful for the manufacture of pharmaceuticals, pesticide active ingredients, organic materials, etc.

Claims

1. A method for producing an aryl thiol ester compound by using a Sandmeier-type coupling reaction with a catalyst to produce a diazo compound represented by the following general formula (2). The compound and the thiol ester compound represented by the following general formula (3) are used to prepare the aryl thiol ester compound represented by the following general formula (1). In equation (2), A 1 It can be an aryl group that may have substituents or a heteroaryl group that may have substituents; the A 1 The substituents are selected from one or more of the following: halogen atom, alkyl, alkenyl, alkoxy, aryl, acyl, hydroxyl, carboxyl, cyano, amino, and nitro; X 1 BF4 － or PF6 － , In equation (3), A 2 It can be an aryl group that may have substituents or a heteroaryl group that may have substituents; the A 2 The substituents are selected from one or more of the following: halogen atom, alkyl, alkenyl, alkoxy, aryl, acyl, hydroxyl, carboxyl, cyano, amino, and nitro; M 1 It consists of sodium or potassium ions. In equation (1), A 1 and A 2 As mentioned above, The catalyst is a copper complex composed of cuprous ions and one or more ligands selected from 1,10-phenanthroline, 2,2'-bipyridine and their derivatives. The derivatives are 4,7-dimethyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 4,4'-dimethyl-2,2'-bipyridine, 4,4'-di-tert-butyl-2,2'-bipyridine, 4,4'-bis(trifluoromethyl)-2,2'-bipyridine, or 6-bromo-4,4'-dimethyl-2,2'-bipyridine.

2. The method for producing the aryl thiol ester compound according to claim 1, wherein, Prior to the Sandmeier-type coupling reaction, the aminoaryl compound represented by the following general formula (4) is diazotized to prepare the compound represented by general formula (2). A 1 -NH2 (4) In equation (4), A 1 Same as above.

Images