WO2010058838A1 - Méthode de production d'un alcénylmercaptan - Google Patents

Méthode de production d'un alcénylmercaptan Download PDF

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Publication number
WO2010058838A1
WO2010058838A1 PCT/JP2009/069702 JP2009069702W WO2010058838A1 WO 2010058838 A1 WO2010058838 A1 WO 2010058838A1 JP 2009069702 W JP2009069702 W JP 2009069702W WO 2010058838 A1 WO2010058838 A1 WO 2010058838A1
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WO
WIPO (PCT)
Prior art keywords
formula
weight
parts
mercaptan
compound represented
Prior art date
Application number
PCT/JP2009/069702
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English (en)
Japanese (ja)
Inventor
俊明 鈴木
Original Assignee
住友化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to CN2009801463953A priority Critical patent/CN102224134A/zh
Priority to EP09827619A priority patent/EP2374793A1/fr
Priority to US13/128,488 priority patent/US20110218363A1/en
Publication of WO2010058838A1 publication Critical patent/WO2010058838A1/fr
Priority to IL212627A priority patent/IL212627A0/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C07C319/04—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by addition of hydrogen sulfide or its salts to unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
    • C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds

Definitions

  • an object of the present invention is to provide a method capable of producing the alkenyl mercaptan (2) having excellent quality by favorably suppressing the by-product (4).
  • the present invention provides the formula (1) (In the formula, R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X represents a chlorine atom, a bromine atom or an iodine atom.)
  • an alkali hydrosulfide By reacting the compound represented by formula (2) with an alkali hydrosulfide.
  • R 1 and R 2 each have the same meaning as described above.
  • a method for producing a compound represented by formula (3) wherein 100 parts by weight of the compound represented by formula (1) and the compound represented by formula (2) (In the formula, R 1 and R 2 each have the same meaning as described above.)
  • a compound represented by the formula [hereinafter sometimes referred to as disulfide (3) A compound represented by the formula [hereinafter sometimes referred to as disulfide (3).
  • the compound is represented by formula (2), wherein the reaction is carried out in an amount of 0.5 parts by weight or more.
  • the present invention also relates to a method for stabilizing alkenyl mercaptan (2), characterized in that 0.5 to 6.0 parts by weight of disulfide (3) is blended in alkenyl mercaptan (2) with respect to 100 parts by weight of alkenyl mercaptan. Is to provide.
  • the by-product of the by-product (4) can be satisfactorily suppressed, and an alkenyl mercaptan (2) with excellent quality can be produced. Moreover, alkenyl mercaptan (2) can be stabilized favorably.
  • R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • X represents a chlorine atom, a bromine atom or an iodine atom.
  • examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, s-butyl group, and t-butyl group. .
  • alkenyl halide (1) examples include 2-propenyl chloride (allyl chloride), 2-propenyl bromide (allyl bromide), 2-propenyl halide (allyl halide) such as 2-propenyl iodozide (allyl iodide), Examples include 2-butenyl chloride (crotyl chloride), 3-methyl-2-butenyl chloride, 2-pentenyl chloride, 2-hexenyl chloride, 2-heptenyl chloride, and the like.
  • the method of the present invention is advantageously employed when 2-propenyl halide (allyl halide) is used as a raw material.
  • alkali hydrosulfide examples include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide and the like. Among them, sodium hydrosulfide is preferable.
  • the alkali hydrosulfide may contain an alkali sulfide, an alkali carbonate, an alkali sulfite, or an alkali thiosulfate. Such alkali hydrosulfide may be flaky or may be an aqueous solution obtained by dissolving in water.
  • alkali sulfide it is preferable to carry out the reaction by adding 2.0 to 10.0 parts by weight of alkali sulfide to 100 parts by weight of alkali hydrosulfide in the reaction system.
  • a method for putting a predetermined amount of alkali sulfide into the reaction system include, for example, a method in which an alkali hydrosulfide containing a predetermined amount of alkali sulfide is put in the reaction system, or a predetermined amount of alkali sulfide separately from the reaction system in the reaction system. And the like.
  • the formula (3) (In the formula, R 1 and R 2 each have the same meaning as described above.)
  • the compound [disulfide (3)] represented by formula (4) is present in an amount of 0.5 parts by weight or more based on 100 parts by weight of the total of alkenyl halide (1) and alkenyl mercaptan (2).
  • the amount of alkali sulfide contained in the reaction system is 100 parts by weight of alkali hydrosulfide because the above-mentioned amount of disulfide (3) is present in the reaction system.
  • it is preferably 2.0 parts by weight or more, more preferably 8.0 parts by weight or more, particularly preferably 9.0 parts by weight or more, and preferably 10.0 parts by weight or less, more preferably 9.8 parts by weight.
  • It is 9.5 parts by weight or less, particularly preferably 9.5 parts by weight or less.
  • examples of disulfide (3) include diallyl disulfide and allylpropyl disulfide.
  • the amount of disulfide (3) added is preferably 1 to 4 parts by weight, more preferably 1.5 to 2.5 parts by weight, with respect to 100 parts by weight of alkenyl halide (1).
  • the amount of alkali hydrosulfide used is usually 1 mol or more, preferably 1.05 to 2 mol, per 1 mol of alkenyl halide (1).
  • the above reaction is usually performed in a solvent.
  • an organic solvent may be used alone, but an oil-water two-phase mixed solvent composed of an organic solvent and water is preferably used.
  • the organic solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; dichloromethane, chloroform, Halogenated aliphatic hydrocarbons such as 1,2-dichloroethane; Halogenated aromatic hydrocarbons such as monochlorobenzene and dichlorobenzene; Ethers such as diethyl ether and dibutyl ether; Esters such as ethyl acetate and butyl acetate Is mentioned. Of these, aromatic hydrocarbons are preferably used.
  • the amount of the solvent used is usually about 0.5 to 10 times the weight of the alkenyl halide (1).
  • the amount of the organic solvent used is usually about 0.5 to 5 times the weight of the alkenyl halide (1).
  • it is usually about 0.5 to 5 times by weight.
  • the use ratio of the organic solvent to water is usually about 1/5 to 5/1 in terms of the weight ratio of the organic solvent / water.
  • phase transfer catalyst examples include tetra-n-ethylammonium bromide, tetra-n-ethylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, and tetra-n-butylammonium hydrogensulfate.
  • phase transfer catalyst used in addition to quaternary ammonium salts such as triethylbenzylammonium chloride and quaternary phosphonium salts such as tetra-n-butylphosphonium bromide, crown ethers, cryptands, and the like. Of these, quaternary ammonium salts are preferably used.
  • the amount of the phase transfer catalyst used is usually 0.001 to 0.2 mol times, preferably 0.05 to 0.1 mol times, relative to the alkenyl halide (1).
  • the reaction method is appropriately selected, but it is preferable to carry out the above reaction by supplying alkenyl halide (1) to a mixture of alkali hydrosulfide and a solvent.
  • disulfide (3) when disulfide (3) is added directly to the reaction system, disulfide (3) may be added to any of the solvent, alkenyl halide (1), and alkali hydrosulfide.
  • phase transfer catalyst when a phase transfer catalyst is used, the phase transfer catalyst may be added to any of the solvent, alkenyl halide (1), and alkali hydrosulfide.
  • the cooling temperature is usually about ⁇ 20 to 50 ° C., although it depends on the type of alkenyl halide (1).
  • the reaction temperature between the alkenyl halide (1) and the alkali hydrosulfide is usually 0 to 100 ° C., preferably 30 to 50 ° C.
  • the reaction is usually performed at around normal pressure, but may be performed under pressure or under reduced pressure as necessary.
  • reaction mixture containing alkenyl mercaptan (2) can be obtained.
  • known means such as washing and distillation can be employed.
  • Disulfide (3) is a compound that improves the storage stability of alkenyl mercaptan (2). 0.5 parts by weight or more, preferably 5.0 parts by weight or more, more preferably 5.4 parts by weight or more and 6.0 parts by weight or less, preferably 100 parts by weight of the alkenyl mercaptan (2) obtained.
  • the alkenyl mercaptan (2) can be well preserved by adding 5.8 parts by weight or less, more preferably 5.6 parts by weight or less of the disulfide (3) to the alkenyl mercaptan (2).
  • the alkenyl mercaptan (2) is usually stored under a nitrogen atmosphere. The storage temperature is about 0 ° C. to room temperature.
  • the alkenyl mercaptan (2) may be diluted with the organic solvent described above and stored.
  • Sodium sulfide / sodium hydrosulfide 5.3 wt%) 184.91 g (1.484 mol)
  • the obtained reaction solution was cooled to 0 to 10 ° C., and 120.02 g of water was added to dissolve the precipitated sodium chloride. Thereafter, oil-water separation was performed to obtain 177.72 g of an allyl mercaptan xylene solution as an organic phase.
  • the content of diallyl disulfide with respect to allyl chloride and allyl mercaptan in the solution was 3.72% by weight, and the content of by-product (4) was 0.02% by weight.
  • the yield of allyl mercaptan with respect to allyl chloride was 94.19%.
  • Sodium sulfide / sodium hydrosulfide 1.3 wt%) 179.06 g
  • Nitrogen was introduced into the gas phase portion in the reactor and a nitrogen stream was applied.
  • the total amount of sodium sulfide added is 9.3% by weight with respect to the amount of sodium hydrosulfide added.
  • 100.03 g (1.281 mol) of allyl chloride was placed in a jacketed dropping funnel and cooled to ⁇ 2 to 5 ° C.
  • the cooled allyl chloride was added dropwise over 7 hours while maintaining the temperature of the reaction solution at 40 ° C., and further kept at 40 ° C. for 3 hours.
  • the content of diallyl disulfide in the organic phase after 0 hour of incubation was 1.04% by weight.
  • the obtained reaction solution was cooled to 0 to 10 ° C., and 120.08 g of water was added to dissolve the precipitated sodium chloride. Thereafter, oil-water separation was performed to obtain 169.09 g of an allyl mercaptan xylene solution as an organic phase.
  • the content of diallyl disulfide with respect to allyl chloride and allyl mercaptan in the solution was 1.12% by weight, and the content of by-product (4) was 0.23% by weight.
  • the yield of allyl mercaptan with respect to allyl chloride was 75.36%.
  • the content of diallyl disulfide with respect to allyl chloride and allyl mercaptan in the solution was 0.43% by weight, and the content of by-product (4) was 2.53% by weight.
  • the yield of allyl mercaptan with respect to allyl chloride was 90.66%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne une méthode de production d'un alcénylmercaptan (2) par réaction d'un halogénure d'alcényle (1) avec un hydrosulfure alcalin. La méthode de production d'un alcénylmercaptan (2) est caractérisée en ce que la réaction est mise en œuvre en présence d'une quantité au moins égale à 0,5 part en masse d'un disulfure (3) pour 100 parts en masse de la somme de l'halogénure d'alcényle (1) et de l’alcénylmercaptan (2).
PCT/JP2009/069702 2008-11-20 2009-11-20 Méthode de production d'un alcénylmercaptan WO2010058838A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN2009801463953A CN102224134A (zh) 2008-11-20 2009-11-20 烯基硫醇的制造方法
EP09827619A EP2374793A1 (fr) 2008-11-20 2009-11-20 Méthode de production d'un alcénylmercaptan
US13/128,488 US20110218363A1 (en) 2008-11-20 2009-11-20 Method for producing alkenyl mercaptan
IL212627A IL212627A0 (en) 2008-11-20 2011-05-02 Method for producing alkenyl mercaptan

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008296436A JP2010120883A (ja) 2008-11-20 2008-11-20 アルケニルメルカプタンの製造方法
JP2008-296436 2008-11-20

Publications (1)

Publication Number Publication Date
WO2010058838A1 true WO2010058838A1 (fr) 2010-05-27

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Country Status (7)

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US (1) US20110218363A1 (fr)
EP (1) EP2374793A1 (fr)
JP (1) JP2010120883A (fr)
CN (1) CN102224134A (fr)
IL (1) IL212627A0 (fr)
TW (1) TW201024255A (fr)
WO (1) WO2010058838A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023003011A1 (fr) * 2021-07-20 2023-01-26 昭和電工株式会社 Composition contenant un thiol, composition photodurcissable et composition thermodurcissable

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107522729A (zh) * 2017-08-30 2017-12-29 永修县艾科普新材料有限公司 一种硫代羧酸酯硅烷偶联剂的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007204453A (ja) 2006-02-06 2007-08-16 Sumitomo Chemical Co Ltd アルケニルメルカプタンの製造法
JP2008296436A (ja) 2007-05-31 2008-12-11 Nippon Kayaku Co Ltd 感熱記録材料

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
US3055946A (en) * 1960-10-07 1962-09-25 Phillips Petroleum Co Stabilization of unstable mercaptans
US3156731A (en) * 1961-02-23 1964-11-10 Phillips Petroleum Co Stabilization of vinylcycloalkanethiols
GB1215994A (en) * 1968-07-03 1970-12-16 British Petroleum Co Disulphides and their use as load-carrying additives
US3859360A (en) * 1970-02-11 1975-01-07 Exxon Research Engineering Co Allylic sulfide reaction products
JPH0710829B2 (ja) * 1986-06-13 1995-02-08 日産化学工業株式会社 ベンジルメルカプタン誘導体の製造法
JP3332561B2 (ja) * 1994-03-17 2002-10-07 イハラケミカル工業株式会社 チオアリール化合物の製造方法
AU2004299131B2 (en) * 2003-12-17 2010-05-13 Bionumerik Pharmaceuticals, Inc. Process for synthesizing disulfides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007204453A (ja) 2006-02-06 2007-08-16 Sumitomo Chemical Co Ltd アルケニルメルカプタンの製造法
JP2008296436A (ja) 2007-05-31 2008-12-11 Nippon Kayaku Co Ltd 感熱記録材料

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023003011A1 (fr) * 2021-07-20 2023-01-26 昭和電工株式会社 Composition contenant un thiol, composition photodurcissable et composition thermodurcissable

Also Published As

Publication number Publication date
IL212627A0 (en) 2011-07-31
TW201024255A (en) 2010-07-01
JP2010120883A (ja) 2010-06-03
CN102224134A (zh) 2011-10-19
EP2374793A1 (fr) 2011-10-12
US20110218363A1 (en) 2011-09-08

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