Process for producing arylthiol ester compounds

Abstract

The present invention provides a production method by which an arylthiol ester compound can be quickly synthesized at a high yield under mild conditions. The present invention pertains to a production method of an arylthiol ester compound represented by general formula (1) that comprises subjecting a diazonium compound represented by general formula (2) and a thiol ester compound represented by general formula (3) to a Sandmeyer-type coupling reaction with the use of a catalyst to give the arylthiol ester compound [in the formulae: A1 and A2 independently represent an optionally substituted aryl group or an optionally substituted heteroaryl group; X1 represents a monovalent anion; and M1 represents a monovalent cation].

Description

Technical Field

[0001] The present invention relates to a method for producing an arylthiol ester compound. This application claims priority based on Japanese Patent Application No. 2021-032819 filed in Japan on March 2, 2021, and incorporates the content herein by reference.

Background Art

[0002] Arylthiol ester compounds have a high electrophilicity of the carbonyl group and can be used as electrophilic reagents in acyl transfer processes and carbanion precursors in condensation reactions. Arylthiol ester compounds are useful as intermediates in synthesizing organic compounds that are raw materials for organic materials, biochemical industrial products, pharmaceuticals, etc. Therefore, the development of a more efficient production method is required.

[0003] Arylthiol ester compounds can be synthesized, for example, by utilizing the nucleophilic reaction of thiolate with carboxylic acid derivatives. For compounds that are difficult to synthesize by this method, it is necessary to try another synthesis method. For example, there are a synthesis method using the thermal rearrangement of O-arylthioesters and a method of reacting an organometallic catalyst with an electrophilic substrate such as diaryliodonium salt or aryl halide. However, since these methods have severe reaction conditions, a method that can be synthesized under mild conditions is desired. As a method of synthesizing under milder conditions, for example, it has been reported that various S-arylthioacetates can be synthesized in a yield of 40 to 60% by treating aryldiazonium tetrafluoroborate with potassium thioacetate in DMSO at room temperature (Non-Patent Document 1, Non-Patent Document 2).

Prior Art Documents

Non-Patent Documents

[0004]

Non-Patent Document 1

[0005] An object of the present invention is to provide a production method capable of synthesizing an arylthiol ester compound quickly and in high yield under mild conditions. [Means for Solving the Problems]

[0006] The present inventors have found that, in the synthesis of an arylthiol ester compound, by using Sandmeyer-type coupling reactions, it can be quickly synthesized from a diazonium compound and a thiol ester compound under mild conditions, and further, the yield can be improved by using a catalyst, thus completing the present invention.

[0007] That is, the present invention is as follows. [1] The following general formula (2)

[0008] [Chemical formula]

[0009] [In the formula, A 1 is an aryl group which may have a substituent or a heteroaryl group which may have a substituent; X 1 is a monovalent anion.] A diazonium compound represented by the following general formula (3)

[0010] [Chemical formula]

[0011] [wherein, A 2 is an aryl group which may have a substituent or a heteroaryl group which may have a substituent; M 1 is a monovalent cation.] From the thiol ester compound represented by the following general formula (1) by a Sandmeyer-type coupling reaction using a catalyst, the following general formula (1)

[0012] [Chemical formula]

[0013] [wherein, A 1 and A 2 are the same as those described above.] A method for producing an arylthiol ester compound, which produces an arylthiol ester compound represented by the formula: [2] The method for producing an arylthiol ester compound according to [1], wherein the catalyst is a transition metal complex. [3] The method for producing an arylthiol ester compound according to [2], wherein the transition metal complex is a copper complex. [4] The method for producing an arylthiol ester compound according to [2] or [3], wherein the transition metal complex contains a bidentate nitrogen chelate ligand. [5] The method for producing an arylthiol ester compound according to any one of [2] to [4], wherein the transition metal complex is composed of copper(I) ions and one or more ligands selected from the group consisting of 1,10-phenanthroline, 2,2'-bipyridine, and derivatives thereof. [6] Before the Sandmeyer-type coupling reaction, the following general formula (4)

[0014] [Chemical formula]

[0015] [wherein, A 1 is the same as that described above.] A method for producing an arylthiol ester compound according to any one of [1] to [5], comprising diazotizing an aminoaryl compound represented by the formula to produce a compound represented by the general formula (2).

Advantages of the Invention

[0016] According to the method of the present invention, an arylthiol ester compound can be efficiently synthesized in a high yield.

Embodiments for Carrying Out the Invention

[0017] In the present invention and the present specification, "C" p1-p2 (where p1 and p2 are positive integers satisfying p1 < p2) means a group having p1 to p2 carbon atoms.

[0018] In the present invention and the present specification, "C" 1-6 alkyl group" is an alkyl group having 1 to 6 carbon atoms, which may be linear or branched. C 1-6 Examples of the C alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an n-hexyl group, and the like.

[0019] In the present invention and the present specification, "C" 1-6 alkoxy group" refers to a group in which an oxygen atom is bonded to the bonding terminal of a C 1-6 alkyl group. The C 1-6 alkoxy group may be linear or branched. C 1-6 Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, and the like.

[0020] In the present invention and the present specification, "C" 2-6 alkenyl group" refers to a group in which at least one carbon-carbon bond of an alkyl group having 2 to 6 carbon atoms is an unsaturated bond. C2-6 The alkenyl group may be linear or branched. C 2-6 Examples of the alkenyl group include vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group and the like.

[0021] In the present invention and the specification of the present application, "C 2-7 acyl group" means a group in which the hydrocarbon group portion excluding the carbonyl group from the acyl group is a C 1-6 alkyl group, a C 2-6 alkenyl group, 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 portion of the acyl group may be linear or branched. C 2-7 Examples of the acyl group include formyl group, acetyl group, propanoyl group, propenoyl group, benzoyl group and the like.

[0022] In the present invention and the specification of the present application, "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. "Halogen atom other than fluorine atom" means 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 preferable, and a chlorine atom is particularly preferable.

[0023] Also, hereinafter, "compound (n)" means a compound represented by formula (n).

[0024] The method for producing an arylthiol ester compound according to the present invention is a method for producing an arylthiol ester compound represented by the following general formula (1) (hereinafter sometimes referred to as "arylthiol ester compound (1)") from a diazonium compound represented by the following general formula (2) (hereinafter sometimes referred to as "diazonium compound (2)") and a thiol ester compound represented by the following general formula (3) (hereinafter sometimes referred to as "thiol ester compound (3)") by a Sandmeyer-type coupling reaction. The Sandmeyer-type coupling reaction is an aromatic nucleophilic substitution reaction based on a radical mechanism. By using the Sandmeyer-type coupling reaction, the arylthiol ester compound (1) can be rapidly produced under relatively mild conditions of 0 to 40°C.

[0025]

Chemical formula

[0026] In general formula (1), general formula (2) and general formula (3), A 1 and A 2 are each independently an aryl group which may have a substituent or a heteroaryl group which may have a substituent. The aryl group is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, a 9-fluorenyl group, etc., and a phenyl group is particularly preferable. The heteroaryl group is not particularly limited, and examples thereof include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazolyl group, a quinolyl group, an isoquinolyl 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, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, etc.

[0027] The "aryl group which may be substituted" is a group in which one or more, preferably 1 to 3, of the hydrogen atoms bonded to the carbon atoms of the aryl group are substituted with other functional groups. Similarly, the "heteroaryl group which may be substituted" is a group in which one or more, preferably 1 to 3, of the hydrogen atoms bonded to the carbon atoms of the heteroaryl group are substituted with other functional groups. When having two or more substituents, the substituents may be of the same kind or different kinds from each other.

[0028] A 1 and A 2 The aryl group and heteroaryl group of A may have one or two or more substituents in addition to the sulfur atom for the purpose of fluorination. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an acyl group, a hydroxy group, a carboxy group, a cyano group, an amino group, and a nitro group. As the alkyl group, a C 1-6 alkyl group is preferred, and as the alkenyl group, a C 2-6 Alkenyl group is preferred, and as the alkoxy group, a C 1-6 alkoxy group is preferred, and as the acyl group, a C 2-7 acyl group is preferred.

[0029] In general formula (2), X 1 is a monovalent anion. Examples of X 1 include, for example, BF 4 - , PF 6 - and the like.

[0030] In general formula (3), M 1 is a monovalent cation. Examples of M 1 include, for example, a sodium ion, a potassium ion and the like.

[0031] As the diazonium compound (2), a compound in which A 1 in general formula (2) is a phenyl group or a pyridyl group which may have a substituent is preferred, and A 1A compound which is a phenyl group optionally having 1 to 3 substituents selected from the group consisting of a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an acyl group, a hydroxy group, a carboxy group, a cyano group, an amino group, and a nitro group, or a pyridyl group optionally having 1 to 3 substituents selected from the group consisting of a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an acyl group, a hydroxy group, a carboxy group, a cyano group, an amino group, and a nitro group is more preferable. As the thiol ester compound (3), A in the general formula (3) 2 is a phenyl group or a pyridyl group which may have a substituent, and M 1 is Na + or K + is preferable, and A 2 is a phenyl group optionally having 1 to 3 substituents selected from the group consisting of a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an acyl group, a hydroxy group, a carboxy group, a cyano group, an amino group, and a nitro group, or a pyridyl group optionally having 1 to 3 substituents selected from the group consisting of a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an acyl group, a hydroxy group, a carboxy group, a cyano group, an amino group, and a nitro group, and M 1 is Na + or K + is more preferable. By reacting these diazonium compounds (2) with the thiol ester compound (3), in the general formula (1), A 1 and A 2 can be independently a phenyl group which may have a substituent or a pyridyl group which may have a substituent, and an aryl thiol ester compound (1) can be synthesized.

[0032] The amounts of the diazonium compound (2) and the thiol ester compound (3) added to the reaction system are not particularly limited as long as they are in a stoichiometric amount or more. From the viewpoints of reaction efficiency and cost, the amount of the thiol ester compound (3) present in the reaction solution of the Sandmeyer-type coupling reaction at the start of the reaction is preferably 1 to 5 equivalents, more preferably 1 to 2 equivalents, of the thioaryl compound (2).

[0033] In the present invention, the Sandmeyer-type coupling reaction for bonding the diazonium compound (2) and the thiol ester compound (3) is carried out using a catalyst. By the Sandmeyer-type coupling reaction using a catalyst, the arylthiol ester compound (1) can be synthesized in a high yield. The catalyst to be used is not particularly limited as long as it can catalyze the Sandmeyer-type coupling reaction, but since the reaction can proceed efficiently in a temperature environment of 0 to 40°C, it is preferable to use a transition metal complex as the catalyst.

[0034] As the transition metal constituting the transition metal complex, for example, copper, silver, palladium, gold, nickel, etc. can be used. Further, the ligand constituting the transition metal complex is not particularly limited as long as it has a lone pair of electrons capable of chelating coordination with the transition metal to be used, and it may be a monodentate ligand, a bidentate ligand, or a polydentate ligand. Among the transition metal complexes used in the present invention, a copper complex is preferable, a complex composed of copper(I) ions and a bidentate ligand is more preferable, and a complex composed of copper(I) ions and a bidentate nitrogen chelate ligand is even more preferable.

[0035] Examples of the bidentate nitrogen chelate ligand include 1,10-phenanthroline, 2,2'-bipyridine, and derivatives thereof. Examples of the derivative of 1,10-phenanthroline include one or more hydrogen atoms bonded to the carbon atoms of 1,10-phenanthroline being replaced with halogen atoms, C 1-6Examples of the compound include those substituted with an alkyl group, an aryl group, a heteroaryl group, a nitro group, an amino group, a hydroxy group, a carbonyl group, a carboxy group, and the like. Similarly, examples of the derivative of 2,2'-bipyridine include, for example, one or more hydrogen atoms bonded to the carbon atom of 2,2'-bipyridine being replaced with a halogen atom, C 1-6 Examples of the compound include those substituted with an alkyl group, an aryl group, a heteroaryl group, a nitro group, an amino group, a hydroxy group, a carbonyl group, a carboxy group, and the like. A halogen atom, C 1-6 Examples of the alkyl group, the aryl group, and the heteroaryl group include the same groups as those described above, respectively.

[0036] Examples of derivatives of 1,10-phenanthroline include, specifically, 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), 3,4,7,8-tetramethyl-1,10-phenanthroline (CAS No: 1660-93-1), bathophenanthroline (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: 66127-01-3), 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.

[0037] Examples of derivatives of 2,2'-bipyridine specifically include 4,4'-dimethyl-2,2'-bipyridyl (CAS No: 1134-35-6), 6,6'-dimethyl-2,2'-bipyridyl (CAS No: 4411-80-7), 4,4'-di-tert-butyl-2,2'-bipyridyl (BBBPY) (CAS No: 72914-19-3), 4,4'-bis(trifluoromethyl)-2,2'-bipyridyl (CAS No: 142946-79-0), 5,5'-bis(trifluoromethyl)-2,2'-bipyridyl (CAS No: 142946-80-3), 6-bromo-4,4'-dimethyl-2,2'-bipyridyl (CAS No: 850413-36-4), 5-bromo-2,2'-bipyridyl (CAS No: 15862-19-8), 4,4'-dibromo-2,2'-bipyridyl (CAS No: 18511-71-2), 5,5'-dibromo-2,2'-bipyridyl (CAS No: 15862-18-7), 6,6'-dibromo-2,2'-bipyridyl (CAS No: 49669-22-9), 4,4'-bis(5-hexyl-2-thienyl)-2,2'-bipyridyl (CAS No: 1047684-56-9), 4,4'-diamino-2,2'-bipyridyl (CAS No: 18511-69-8), 6,6'-diamino-2,2'-bipyridyl (CAS No: 93127-75-4), 2,2'-bipyridine-3,3'-diol (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), and the like.

[0038] As the catalyst used in the Sandmeyer-type coupling reaction in the present invention, a copper complex composed of copper(I) ions and one or more ligands selected from the group consisting of 1,10-phenanthroline, 2,2'-bipyridine, and their derivatives is preferred, and a copper complex composed of copper(I) ions and one or more ligands selected from the group consisting of phenanthroline, bathophenanthroline, 2,2'-bipyridine, and BBBPY is more preferred.

[0039] The amount of the catalyst added to the reaction system is not particularly limited, and any amount can be used as long as it can increase the yield of the product obtained by the Sandmeyer-type coupling reaction compared to the case without adding the catalyst. For example, the amount of the catalyst added to the reaction solution is preferably 5 to 30 mol% based on the diazonium compound (2) as the substrate, more preferably 5 to 25 mol%, still more preferably 5 to 20 mol%, and even more preferably 10 to 20 mol%.

[0040] When performing the Sandmeyer-type coupling reaction, a transition metal complex may be added to the reaction solution, or a transition metal source and a ligand may be added to synthesize the transition metal complex in the reaction solution. As the transition metal source, a salt of a transition metal ion constituting the target transition metal complex and an anionic ion is preferred. For example, when a copper complex composed of copper(I) ions and a ligand is used as the catalyst, as the copper(I) source, copper(I) thiocyanate (CuSCN), copper(I) bromide-dimethyl sulfide complex (CuBr·SMe 2 )), copper(I) cyanide (CuCN), etc. can be mentioned.

[0041] The Sandmeyer-type coupling reaction can be carried out in a solvent inert to the reaction. The inert solvent is not particularly limited, but 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 may be a mixed solvent of two or more solvents.

[0042] In the Sandmeyer-type coupling reaction, a reaction solution obtained by mixing a diazonium compound (2), a thiol ester compound (3), and a catalyst in a reaction solvent is reacted at an appropriate temperature and for an appropriate time. Instead of the catalyst, a transition metal source and a ligand may be added. The Sandmeyer-type coupling reaction proceeds under mild conditions. For example, the reaction temperature is not particularly limited as long as the reaction solvent is in a liquid state, and the reaction 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, the Sandmeyer-type coupling reaction can be carried out at room temperature for less than 1 hour to obtain the target aryl thiol ester compound (1) in a high yield, for example, a yield of 70% or more.

[0043] The synthesized aryl thiol ester compound (1) can be used as a substrate for synthesizing other organic compounds. For example, by performing an oxidative fluorination reaction using the aryl thiol ester compound (1) as a substrate and AgF 2 a pentafluorosulfanyl group-containing aryl compound can be produced.

[0044] When the synthesized arylthiol ester compound (1) is used as a substrate for synthesizing other organic compounds, the reaction solution containing the reaction product of the Sandmeyer-type coupling reaction may be directly used in the next reaction, or the arylthiol ester compound (1) may be purified from the reaction solution and used in the next reaction. The purification method is not particularly limited, and general purification methods such as filtration treatment can be used.

[0045] The diazonium compound (2) used in the Sandmeyer-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 is the same as A in the general formula (2). 1

[0046]

Chemical formula

[0047] The diazotization reaction of the aminoaryl compound (4) can be carried out using various diazo coupling reactions. For example, boron trifluoride and nitrite are used to synthesize nitrosonium ion (NO + ) and tetrafluoroborate ion (BF 4 - ), and this is reacted with the amino group of the aminoaryl compound (4) to produce the tetrafluoroborate salt of the diazonium compound (2) (aryl diazonium tetrafluoroborate: A1-N2+ BF 4 - ). The diazotization reaction of the aminoaryl compound (4) can also be carried out with sodium nitrite and hydrochloric acid. In this case, the hydrochloride salt of the diazonium compound (2) is produced.

[0048] The diazotization reaction can be carried out in a solvent inert to the reaction at a temperature at which the reaction solvent is in a liquid state. As the inert solvent, the same solvents as those usable in the Sandmeyer-type coupling reaction can be used.

[0049] When the diazonium compound (2) synthesized by the diazotization reaction of the aminoaryl compound (4) is used in the Sandmeyer-type coupling reaction, the diazotization reaction and the subsequent Sandmeyer-type coupling reaction can also be carried out in one pot.

Examples

[0050] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples.

[0051] The NMR apparatus used for the analysis of the examples and comparative examples was JNM-ECZ400S (400 MHz) manufactured by JEOL Ltd. 1 In 1H NMR, tetramethylsilane was set to 0 PPM, 19 In 19F NMR, C 6 F 6 was used as a reference value of -162 PPM.

[0052] [Example 1] 4-Methoxyphenyl benzoate was synthesized as follows.

[0053] (1) Diazotization of Aminoaryl First, benzenediazonium salt was synthesized by a general synthetic method.

[0054]

Chemical formula

[0055] Boron trifluoride-diethyl ether complex (BF 3 ·OEt 2(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 the 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 solution was filtered to recover the precipitate (benzenediazonium salt), and the precipitate was washed with diethyl ether.

[0056] (2) Sandmeyer-type coupling reaction Allyl benzoate was synthesized from benzenediazonium salt and thiosalicylate by a Sandmeyer-type coupling reaction using a copper complex catalyst. As the copper(I) source, CuSCN, CuBr·SMe 2 , or CuCN·LiCl (THF solution) was used, and as the ligand, 1,10-phenanthroline (Phen), bathophenanthroline (Bathophen), or BBBPY was used.

[0057]

Chemical formula

[0058] In a dry box filled with argon, a glass vial was charged with a copper(I) source (X mol%), a ligand (X mol%), potassium thiobenzoate (229 mg, 1.3 mmol), and a magnetic stir bar. Further, MeCN (1 mL) was added and stirred for approximately 2 minutes. The reaction mixture was a red suspension containing undissolved potassium thiobenzoate. To the reaction mixture, 4-methoxybenzenediazonium tetrafluoroborate (222 mg, 1.0 mmol) dissolved in MeCN (2 mL) was added dropwise using a syringe at room temperature, and visible nitrogen gas formation occurred during the addition. The syringe was pre-washed with 1 mL of MeCN. After stirring the reaction mixture at room temperature or 0 °C for 1 hour, the resulting reaction product was transferred to a 50 mL flask. After adding silica to the flask, the solvent was evaporated under vacuum. Subsequently, column chromatography (hexane:DCM = 2:1 to 1:1 (volume ratio)) was performed to obtain 4-methoxyphenyl benzoate as a yellow solid.

[0059] 1H NMR (400 MHz) δ 8.06 - 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).

[0060] The copper complex catalysts (copper(I) source and ligand), the amount of copper complex used ("X mol%" in the above reaction formula), the reaction temperature, and the yield (%) of 4-methoxyphenyl benzoate used in each test section are shown in Table 1. In Table 1, " / " indicates no addition. For example, in test section 8 CuSCN (12 mg, 0.1 mmol) was used as the copper(I) source and 1,10-phenanthroline (18 mg, 0.1 mmol) was used as the ligand, and 4-methoxyphenyl benzoate (195 mg) (yield 80%) was obtained.

[0061]

Table 1

[0062] For Test Section 1 without using a catalyst, in Test Sections 2 to 4 using copper that did not form a complex as a catalyst, the yield was not improved or only slightly improved. In contrast, in Test Sections 5 to 11 using a copper complex catalyst, regardless of the type of copper(I) source and ligand used, a clear improvement in yield was observed. In particular, the test section 8 using 10 mol% of a copper complex catalyst composed of CuSCN and 1,10-phenanthroline with respect to the benzenediazonium salt (4-methoxybenzenediazonium tetrafluoroborate) had a very excellent yield of 80%.

[0063] Comparing Test Sections 8, 10, and 11, Test Section 8 had the highest yield, but sufficient yield improvement was also observed in Test Sections 10 and 11. Thus, it was also confirmed that the effect of improving the yield by using a transition metal complex as a catalyst can be obtained even in a low-temperature environment with a reaction temperature of -30°C to 0°C.

Industrial Applicability

[0064] The present invention provides a production method capable of synthesizing an arylthiol ester compound quickly and in a high yield under relatively mild conditions. Further, since the arylthiol ester compound produced by the present invention is useful as an intermediate for producing various organic compounds, the present invention is useful for producing pharmaceutical and agricultural active ingredients, organic materials, and the like.

Claims

1. A diazonium compound represented by the following general formula (2) and a thiol ester compound represented by the following general formula (3) are subjected to a Sandmeyer-type coupling reaction using a catalyst to produce an aryl thiol ester compound represented by the following general formula (1). 【Chemical 1】 [wherein, A １ is an aryl group which may have a substituent or a heteroaryl group which may have a substituent; X １ is a monovalent anion.] The manufacturing method of the aryl thiol ester compound, wherein the catalyst is a transition metal complex containing a bidentate nitrogen chelate ligand. 【Chemical 2】 [wherein, A ２ is an aryl group which may have a substituent or a heteroaryl group which may have a substituent; M １ is a monovalent cation.]

2. [Chemical Formula 3] [wherein, A １ and A ２ are the same as described above.] The manufacturing method of the aryl thiol ester compound according to Claim 1, wherein the transition metal complex is a copper complex.

3. The manufacturing method of the aryl thiol ester compound according to Claim 1 or 2, wherein the transition metal complex consists of copper (I) ions and one or more ligands selected from the group consisting of 1,10-phenanthroline, 2,2'-bipyridine, and derivatives thereof.

4. Before the Sandmeyer-type coupling reaction, an aminoaryl compound represented by the following general formula (4) is diazotized to produce a compound represented by the general formula (2). The manufacturing method of the aryl thiol ester compound according to any one of Claims 1 to 3. ​ ​ ​ [Chemical Formula 4] [wherein, A １ is the same as described above.] ​

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