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WO2008066033A1 - Dérivé de benzène substitué par alkylthio et son procédé de fabrication - Google Patents

Dérivé de benzène substitué par alkylthio et son procédé de fabrication Download PDF

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Publication number
WO2008066033A1
WO2008066033A1 PCT/JP2007/072839 JP2007072839W WO2008066033A1 WO 2008066033 A1 WO2008066033 A1 WO 2008066033A1 JP 2007072839 W JP2007072839 W JP 2007072839W WO 2008066033 A1 WO2008066033 A1 WO 2008066033A1
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group
reaction
benzene
benzene derivative
solvent
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English (en)
Japanese (ja)
Inventor
Shinya Maehara
Hideyuki Murakami
Satoshi Hobara
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Hokko Chemical Industry Co Ltd
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Hokko Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides

Definitions

  • the present invention relates to a novel method for producing a substituted benzene derivative having an alkylthio group, which is important as an intermediate for pharmaceuticals and agricultural chemicals.
  • Non-patent document 1 Non-patent document 2
  • methanethiol sodium salt used is anhydrous, and no examples of using aqueous solutions have been reported.
  • 1,2-dichlorobenzene was added dropwise in polyethylene glycol at 135 ° C over 1 hour with 1 / 3-fold moles of 30% aqueous methanethiol sodium salt solution over 1,4 dichlorobenzene over 135 hours.
  • lower alkanethiols have a low boiling point and have a unique odor that is difficult to handle, requiring special equipment.
  • Alkaline metal salts of lower alkanethiols are easier to handle! / Than thiols themselves, but they are expensive as anhydrides and have problems in terms of economy in industrial production.
  • An aqueous salt solution is easy to synthesize and is inexpensive.
  • the reaction yield decreases because the reactivity decreases due to the presence of a large amount of water. It is necessary to use a large excess of alkali metal salt in order to obtain the desired product in high yield. It is also known that alkylthio group dealkylation occurs as a side reaction due to the presence of excess alkanethiol alkali metal salt.
  • Non-Patent Document 1 Synthesis, 1982, Vol. 6, 475–478
  • Non-Patent Document 2 Tetrahedron Letters, 21, 3099-3100, 1980 Patent Document 1: JP-A-9 40636
  • Patent Document 2 Japanese Patent Laid-Open No. 948752
  • Patent Document 3 Japanese Patent Laid-Open No. 2001-302616
  • the ability to use an aqueous solution of a lower alkanethiol alkali metal salt from the economical aspect is advantageous in producing an alkylthio group-substituted benzene derivative.
  • the concentration of the aqueous solution is about 10 to 30%. If it is used as it is, the reactivity decreases due to the presence of a large amount of water, and it is difficult to use it industrially because the reaction efficiency is poor.
  • azeotropic dehydration means that water and an azeotropic solvent (which is a solvent that can be removed from the reaction system by distillation together with water) are distilled simultaneously to distill water present in the reaction system. It means to remove.
  • R, R, R, R and R are the same or different hydrogen atoms
  • X represents a halogen atom.
  • R represents a methyl group or an ethyl group
  • M represents an alkali metal cation
  • An azeotropic solvent (which can be removed from the reaction system by distillation together with water) which may be the same as the halogenated benzene derivative, the reaction solvent and the halogenated benzene derivative represented by the formula (1);
  • the mixture of water and azeotropic solvent was distilled by distillation while adding an aqueous solution of the above lower alkanethiol alkali metal salt without adding a surfactant to the mixed solution of Including the first reaction step in which the reaction is carried out by removing the water present to reduce the water content in the reaction mixture to 10% by mass or less, and if necessary, the following general formula (3)
  • a method for producing an alkylthio group-substituted benzene derivative comprising a second reaction step in which an alkyl carbonate represented by the formula
  • the process for producing an alkylthio group-substituted benzene derivative which is particularly useful in the present invention, first comprises a halogenated benzene derivative represented by the above general formula (1) and a lower alkyl represented by the above general formula (2). Reacting the lucanthiol strength metal salt.
  • R, R and R can each independently be any of the substituents described above.
  • Examples of the straight-chain or branched alkyl group having 1 to 6 carbon atoms include, for example, methyl group, ethyl group, n propyl group, isopropyl group, n butyl group, isobutyl group, sec butanol group, tert butyl group, n pentyl group, isopentyl group, 2-methylbutyl group, neopentyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 3,3-dimethylbutyl group, 1,1-dimethylbutyl group, 1 , 3-dimethylenobutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 1-methyl-1-ethylenopropyl group, 1,2-dimethylbutyl group, 2-methyl-1-ethylpropyl group, 2,2-dimethylbutyl group, etc.
  • linear or branched alkoxy group having 1 to 6 carbon atoms examples include methoxy group, ethoxy group, n propoxy group, isopropoxy group, n butoxy group, isobutoxy group, se c butoxy group, tert butoxy group, n Pentyloxy group, isopentyloxy group, 2-methylbutoxy group, neopentyloxy group, n-hexyloxy group, 4-methylpentyl-oxy group, 3 methino-repentino-reoxy group, 2-methino-repentino-reoxy group, 3, 3— dimethylbutoxy group, 1, 1-dimethylbutoxy group, 1, 3 dimethylbutoxy group, 2, 3— Dimethylbutoxy group, 1-ethylbutoxy group, 1-methyl-1-ethylpropoxy group, 1,2-dimethylenobutoxy group, 2-methinole-1-ethinorepropoxy group, 2,2-dimethylenobutoxy group, etc.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a phenyl group substituted at 1 to 3 positions with a substituent selected from the group consisting of halogen atoms include, for example, 2 methylphenyl group, 3 methylphenyl group, 4 methylphenyl group, 2, 3 dimethylphenyl group, 2 , 4 Dimethyl phenyl group, 2, 5 Dimethyl phenyl group, 2, 6 Dimethyl phenyl group, 3, 4 Dimethyl phenyl group, 3, 5 Dimethino fenenore group, 2, 4, 6 Trimethino fenenore group, 3 , 4, 5 Trimethylolenyl, 2 ethenylphenyl, 3 ethenylphenyl, 4 ethenylphenyl, 2, 3 jetylphenyl, 2, 4 jetylphenyl, 2, 6 jetylphenyl Group, 3, 5 Jetyl phenyl group, 3, 4, 5 Trimethyl phenyl group, 2-n-propyl phenyl group, 3 Isoprop
  • halogen atom for X in the general formula (1) examples include a fluorine atom, a chlorine atom, and a bromine atom. Among them, a chlorine atom and a bromine atom are preferable from the viewpoint of easy availability.
  • halogenated benzene derivative represented by the general formula (1) for example,
  • the two halogen atoms may be the same or different.
  • chlorobenzene bromobenzene, fluorobenzene, odobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,3-difunoleobenzene, 1-bromo 2 Black mouth benzene, 1-Bromo 3 Black mouth benzene, 1-Bromo 4—Black mouth benzene, 1—Funoleo 2—Black mouth benzene, 1—Funoleo One mouth 3 Chlo mouth benzene, 1—Funoleo mouth one 4 Head Benzene, 1-odd 2 Black mouth benzene, 1-yod 3-Black-mouthed benzene, 1-yod 4 Black-mouthed benzene, 1 Bromo 2 Funole-aged lobenzene, 1-Bromo 3 Funore-aged robenzene, 1-Bromo 4-Funore O-benzene, 1-bromo 2 Black
  • the alkali metal cation represents a lithium ion, a sodium ion, a potassium ion, a noredium ion, a cesium ion or the like.
  • Examples of the alkali metal salt of the lower alkanethiol represented by the general formula (2) include, for example, a lithium salt of methanethiol, a sodium salt of methanethiol, a power methanethiol salt, a lithium salt of ethanethiol, and an ethanethiol. And sodium salt of ethane and the like.
  • the reaction solvent is a solvent that enables a reaction between a halogenated benzene derivative and a lower alkanethiol alkali metal salt without adding a surfactant, and has a high affinity for a cation and promotes the reaction.
  • Aprotic polar solvents that are preferably aprotic polar solvents from the standpoint of effectiveness include 1,3 dimethyl-2 imidazolidinone, N methyl-2-pyrrolidinone, N, N dimethylformamide, N, N dimethyl Amide solvents such as acetoamide and hexamethylphosphoric triamide; Sulfoxide or sulfone solvents such as dimethyl sulfoxide or phosphorane; Pyridine; 2 Methyl pyridine, 3 Methyl pyridine, 4 Methyl pyridine, 2, 6 dimethyl pyridine, 2 , 4 1-5 such as dimethyl pyridine Pyridine substituted with a linear or branched alkyl group having 1 to 6 carbon atoms; quinoline; and 1 to 5 linear or branched carbon atoms having 1 to 6 carbon atoms such as 2 methylquinoline
  • Use force S S to use one or more solvents selected from the group consisting of quinoline substituted with alkyl groups.
  • the reaction solvent is usually used in a mass ratio of from 0.5 to 100 times the mass ratio of the halogenated benzene derivative as the raw material, but preferably from 0.5 to 10 times the amount. is there.
  • the reaction between the halogenated benzene derivative and the lower alkanethiol alkali metal salt is performed by distilling and distilling water derived from the aqueous solution of the lower alkanethiol alkali metal salt together with the azeotropic solvent. , While removing continuously from the reaction system.
  • an azeotropic solvent distilled off can be used as a method for removing water. Separation of the mixture with water can be performed using a mechanism in which only water is removed. At this time, the separated azeotropic solvent can be returned to the reaction system.
  • the azeotropic solvent has a low solubility in water and quickly separates from water.
  • a solvent is selected from benzene; a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a trifluoromethyl group.
  • benzenes include, for example, benzene, toluene, orthoxylene, metaxylene, noraxylene, mesitylene, ethynolebenzene, isopropylenobenzene, benzotrinoleolide, and anisole.
  • Examples of aliphatic alkanes include n-hexane, n-heptane, n-octane, n-decane, isooctane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, decalin, methylcyclohexane, etc. Is mentioned.
  • Examples of ethers include methyl-tert butyl ether, di-n-propyl ether.
  • solvents when the proportion of water in the azeotrope with water is relatively high and the specific gravity is smaller than that of water, it is separated into an upper solvent such as benzene, toluene, orthoxylene, One or more solvents selected from the group consisting of meta-xylene and para-xylene are preferred from the viewpoints of dehydration efficiency, reaction efficiency, and operability! /.
  • the halogenated benzene derivative represented by the general formula (1) which is the reaction substrate
  • the halogenated benzene derivative represented by the general formula (1) can be azeotroped with water, it is used as an azeotropic solvent, and the azeotropic solvent is added separately.
  • the ability to carry out the reaction without the addition Usually, in order to remove water more efficiently, an azeotropic solvent having a lower boiling point than the halogenated benzene derivative as the reaction substrate is added separately.
  • the addition amount of the azeotropic solvent is an amount by which the reflux of the mixture of water and the azeotropic solvent derived from the aqueous solution is maintained during the addition of the aqueous solution of the lower alkanethiol alkali metal salt, and varies depending on the capacity of the reactor. It is preferable to add within the range of the force S and the ratio with the reaction solvent described later.
  • reaction solvent and azeotropic solvent can be arbitrarily mixed and used.
  • the azeotropic solvent is the same as the halogenated benzene derivative represented by the above general formula (1), which is the reaction substrate, and other azeotropic solvents belonging to the above group are not added separately,
  • the “azeotropic solvent” means the halogenated benzene derivative represented by the general formula (1).
  • the reaction temperature between the halogenated benzene derivative and the aqueous solution of the lower alkanethiol alkali metal salt is preferably a force capable of using a temperature of 50 ° C to 200 ° C, more preferably the boiling point of the azeotropic solvent, or The temperature at which the solvent can be distilled off with water is used.
  • a preferred embodiment of the method for adding an aqueous solution of a lower alkanethiol alkali metal salt includes mixing the compound of formula (1), a reaction solvent and an azeotropic solvent, and adding the mixture with the azeotropic solvent. It is preferable to add an aqueous solution of a lower alkanethiol alkali metal salt in advance so that the mixture with water derived from the aqueous solution is heated in advance so that the mixture rapidly refluxs. At that time, the moisture contained in the reaction mixture is substantially 10% by mass or less, preferably substantially 5% by mass or less, more preferably substantially less than 5% by mass with respect to the entire reaction mixture. Add 3% by mass or less so that the reflux of the mixture of azeotropic solvent and water is maintained.
  • substantially means a range that does not affect the yield, and specifically, an amount of 50% by mass or more is preferably added to the amount of the lower alkanethiol alkali metal salt aqueous solution to be added. More preferably, it is a range in which an amount of 80% by mass or more is added, and most preferably a range in which an amount of 90% by mass or more is added.
  • the amount of water to be added and the amount of water to be added which can be dropped or added intermittently, either continuously or intermittently, are distilled. This should be done while measuring the amount of distilled water. In the case of continuous dripping, the amount of water added and distillate In the case of intermittent addition, where it is desirable to add dropwise so that the amount is almost the same amount, the amount of water added to the reaction mixture by one addition calorie should not exceed 10% by mass of the total reaction mixture
  • the power to do S is desirable. More preferably, it should be added in a range not exceeding 5% by mass, and most preferably not exceeding 3% by mass.
  • the amount of the lower alkanethiol alkali metal salt aqueous solution added is preferably 0.;! To 4 times the amount of the lower alkanethiol alkali metal salt as a lower alkanethiol alkali metal salt with respect to 1 mol of the compound of the formula (1) which is the substrate used in the reaction. More preferably 0.5 to 3 times the amount is used, still more preferably 0.7 to 2 times the amount.
  • the lower alkanethiol alkali metal salt aqueous solution to be added a commercially available product can be used as it is, or an aqueous solution of the corresponding alkali metal hydroxide, alkanethiol, and other components prepared separately can be used.
  • the concentration of the lower alkanethiol alkali metal salt contained in the aqueous solution can be used in the range of 1% by mass to 80% by mass. Usually, the concentration is in the range of 5% by mass to 50% by mass.
  • the production method of the present invention is represented by the above formula (3), formula (4), or formula (5) where the alkyl group part is the same as the lower alkanethiol alkali metal salt used, if necessary. It includes a second reaction step in which the alkylthio group-substituted benzene derivative represented by the formula (6) is obtained by adding and alkylating an alkylating agent.
  • the alkylthiol introduced as a side reaction may be used.
  • a thiol derivative in which a part of the group is dealkylated is produced, but even in this case, as shown in the second reaction step, the thiol derivative by-produced by adding an alkylating agent is It can be easily converted into an alkylthio group-substituted benzene derivative represented by the formula (I), and the target product can be obtained in high yield.
  • the alkylating agent is added in a molar ratio of 0.1 to 5.0 times, preferably 0.3 to 1.5 times with respect to 1 mol of the compound represented by the formula (1) as a substrate.
  • the alkylating agent may be any of the compounds represented by formula (3), formula (4), or formula (5), but is preferably an alkylnolide power that is a compound of formula (3). Desirable in terms of ease and economy.
  • the reaction temperature of the alkylation with the alkylating agent is preferably a force at which a temperature from 0 ° C to 200 ° C can be used, more preferably from room temperature to 100 ° C.
  • the organic phase is separated by a method such as distilling off the solvent under reduced pressure as necessary, adding water to the residue for liquid separation, or adding an organic solvent for extraction. Further, if necessary, purification using means such as distillation, recrystallization, column chromatography and the like can provide a high-purity alkylthio group-substituted benzene derivative in a high yield.
  • Example 3 3 ⁇ 4 of 2-chloro-6-methylthiotoluene A 2 L 4-neck flask was charged with 161 g (1.0 mol) of 2,6-dichlorotoluene, 640 g of N-methylpyrrolidinone, and 80 g of toluene.
  • the mixture was blown at 0 ° C., stirred at the same temperature for 1 hour, and the reaction was completed after confirming that the demethylated product had disappeared by gas chromatography and that all were the title compound.
  • the reaction solution was transferred to a 2 L eggplant flask and concentrated under reduced pressure using a rotary evaporator.
  • a 1L 4-neck flask is charged with 73.5 g (0.5 mol) of 1,2-dichlorobenzene, 320 g of N-methyl-2-pyrrolidinone, and 80 g of benzene, and the internal temperature is 110 ° C with a mantle heater in a nitrogen atmosphere. Until warmed. Next, when 18 g of a 15% -methanethiol sodium salt aqueous solution was added dropwise, refluxing started by azeotropy. The dropping was continued to maintain 110-120 ° C with the power of removing water from the Dean-Stark apparatus.
  • Example 7 to 12 The raw material was a halogenated benzene derivative shown in Table 1, and in Example 8, a 20% -ethanethiol potassium salt aqueous solution was used instead of 15% -methanethiol sodium salt, and The reaction was carried out in the same manner as in Example 4 except that odoethane was added dropwise instead of blowing methane to obtain the corresponding alkylthio group-substituted benzene derivative. The results are shown in Table 1. The yield was calculated based on the halogenated benzene derivative as a raw material.
  • Example 2 the same operation as in Example 2 was performed to obtain 190 g of a concentrate.
  • the content of the title compound was analyzed by gas chromatography, it was 65.4 g (yield 37.9%, based on 2,6-dichloronitrone).
  • Example 2 the same operation as in Example 2 was performed to obtain 172 g of a concentrate.
  • the content of the title compound was analyzed by gas chromatography, it was 65 g (yield 37.5%, 2,6-dichroic toluene based on toluene).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un dérivé de benzène substitué par alkylthio, d'utilité industrielle, à l'aide d'une solution aqueuse d'un sel de métal alcalin d'un alcanethiol inférieur qui est disponible à faible coût. L'invention concerne spécifiquement un procédé de fabrication d'un dérivé de benzène substitué par un alkylthio représenté par la formule générale (6), par réaction d'un dérivé de benzène halogéné représenté par la formule générale (1) avec un sel de métal alcalin d'alcanethiol représenté par la formule générale (2). Le procédé comprend : une première étape de réaction pour conduire la réaction par l'addition d'une solution aqueuse du sel de métal alcalin d'alcanethiol inférieur à une solution mélangée du dérivé de benzène halogéné, d'un solvant de réaction et d'un solvant azéotropique (un solvant qui peut être éliminé conjointement avec l'eau à partir d'un système réactionnel par distillation) qui peut être le même que le dérivé de benzène halogéné représenté par la formule (1) tout en distillant un mélange d'eau et du solvant azéotropique pour éliminer l'eau présente dans le système de réaction en continu, de telle sorte que la teneur en eau du mélange réactionnel devient de 10 % en masse ou moins ; et facultativement, une seconde étape de réaction pour l'addition d'un halogénure d'alkyle représenté par la formule générale (3), d'un ester sulfate d'alkyle représenté par la formule générale (4) ou d'un ester carbonate d'alkyle représenté par la formule générale (5) au système réactionnel.
PCT/JP2007/072839 2006-11-29 2007-11-27 Dérivé de benzène substitué par alkylthio et son procédé de fabrication Ceased WO2008066033A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106008295A (zh) * 2016-06-03 2016-10-12 北京颖泰嘉和生物科技股份有限公司 一种2-卤代-6-烷硫基甲苯的制备方法
CN111233721A (zh) * 2018-11-28 2020-06-05 沈阳科创化学品有限公司 一种2-烷硫基-6-卤代烷基苯的合成方法
CN115806515A (zh) * 2022-12-16 2023-03-17 启农生物科技(北京)有限公司 一种中间体2-甲基-3-甲硫基-氯苯的合成工艺
CN118184550A (zh) * 2024-05-17 2024-06-14 爱斯特（成都）生物制药股份有限公司 一种3-氟苯磺酰氯的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0656760A (ja) * 1992-08-03 1994-03-01 Sumitomo Seika Chem Co Ltd ２，５−ジクロロアルキルチオベンゼンの製造法
JP2002536433A (ja) * 1999-02-10 2002-10-29 オクシデンタル ケミカル コーポレイション メルカプト−ベンズアルデヒドの合成
WO2003101944A1 (fr) * 2002-05-30 2003-12-11 Shionogi & Co., Ltd. Procede de production d'un compose ayant un groupe biphenyle auquel est substitue un groupe alkylthio inferieur

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0656760A (ja) * 1992-08-03 1994-03-01 Sumitomo Seika Chem Co Ltd ２，５−ジクロロアルキルチオベンゼンの製造法
JP2002536433A (ja) * 1999-02-10 2002-10-29 オクシデンタル ケミカル コーポレイション メルカプト−ベンズアルデヒドの合成
WO2003101944A1 (fr) * 2002-05-30 2003-12-11 Shionogi & Co., Ltd. Procede de production d'un compose ayant un groupe biphenyle auquel est substitue un groupe alkylthio inferieur

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106008295A (zh) * 2016-06-03 2016-10-12 北京颖泰嘉和生物科技股份有限公司 一种2-卤代-6-烷硫基甲苯的制备方法
CN106008295B (zh) * 2016-06-03 2017-12-08 北京颖泰嘉和生物科技股份有限公司 一种2‑卤代‑6‑烷硫基甲苯的制备方法
CN111233721A (zh) * 2018-11-28 2020-06-05 沈阳科创化学品有限公司 一种2-烷硫基-6-卤代烷基苯的合成方法
CN111233721B (zh) * 2018-11-28 2022-12-13 沈阳科创化学品有限公司 一种2-烷硫基-6-卤代烷基苯的合成方法
CN115806515A (zh) * 2022-12-16 2023-03-17 启农生物科技(北京)有限公司 一种中间体2-甲基-3-甲硫基-氯苯的合成工艺
CN118184550A (zh) * 2024-05-17 2024-06-14 爱斯特（成都）生物制药股份有限公司 一种3-氟苯磺酰氯的制备方法

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