WO2020136961A1 - ３－アセトキシスチレンの製造方法 - Google Patents

３－アセトキシスチレンの製造方法 Download PDF

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Publication number
WO2020136961A1
WO2020136961A1 PCT/JP2019/027089 JP2019027089W WO2020136961A1 WO 2020136961 A1 WO2020136961 A1 WO 2020136961A1 JP 2019027089 W JP2019027089 W JP 2019027089W WO 2020136961 A1 WO2020136961 A1 WO 2020136961A1
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WO
WIPO (PCT)
Prior art keywords
acetoxystyrene
reaction
palladium
acetoxyhalobenzene
present
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2019/027089
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English (en)
French (fr)
Japanese (ja)
Inventor
尚文 木下
森　浩章
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Chemical Corp
Original Assignee
JFE Chemical Corp
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 JFE Chemical Corp filed Critical JFE Chemical Corp
Priority to CN201980003869.2A priority Critical patent/CN111201213A/zh
Priority to KR1020197038325A priority patent/KR20210110418A/ko
Publication of WO2020136961A1 publication Critical patent/WO2020136961A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/14—Acetic acid esters of monohydroxylic compounds
    • C07C69/145—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols
    • C07C69/157—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium

Definitions

  • the present invention relates to a method for producing 3-acetoxystyrene.
  • 3-Acetoxystyrene is a compound used for pharmaceutical intermediates, photoresist materials, and the like.
  • Several patents describe the method of synthesizing 3-acetoxystyrene. Chandros et al. synthesize 3-acetoxybenzaldehyde by reacting 3-hydroxybenzaldehyde with acetyl chloride in a methylene chloride solution and then obtain 3-acetoxystyrene by Wittig reaction with methyltriphenylphosphonium bromide ( Patent Document 1).
  • this method has a problem that the overall yield is as low as 55.0%, and that triphenylphosphine oxide is produced as a by-product in the second reaction, so that a large amount of waste is generated and the treatment is heavy. is there.
  • Tsujimoto et al. also prepared 3-acetoxybenzaldehyde by reacting 3-hydroxybenzaldehyde with acetic anhydride in a toluene solution, followed by reaction with dibromomethane in the presence of zinc metal and active chloride.
  • -Acetoxystyrene is obtained (Patent Document 2).
  • Patent Document 2 shows that this method also has a problem that the overall yield is as low as 48.5% and the burden of waste treatment is large.
  • Kawaguchi et al. obtained 3-acetoxystyrene by reacting mt-butoxystyrene with acetic anhydride in the presence of an aliphatic carboxylic acid such as formic acid and oxalic acid (Patent Document 3).
  • This method has a high yield of about 90%, but since the main raw material, mt-butoxystyrene, is relatively expensive, it is disadvantageous in terms of cost.
  • Patent Document 5 a method for producing 4-acetoxystyrene by subjecting 4-acetoxyhalobenzene to a Heck reaction is already known (Patent Document 5).
  • 4-acetoxystyrene is obtained in a high yield of about 90% using relatively inexpensive raw materials.
  • the document does not describe the production of 3-acetoxystyrene, and it is unclear whether this method can be applied to the production of 3-acetoxystyrene.
  • An object of the present invention is to provide an industrially advantageous production method of 3-acetoxystyrene which could not be satisfied by the conventional method.
  • the present invention is a method for producing 3-acetoxystyrene represented by the following formula (2), which comprises subjecting 3-acetoxyhalobenzene represented by the following formula (1) to a Heck reaction. According to the present invention, 3-acetoxystyrene can be produced inexpensively and in high yield.
  • the 3-acetoxyhalobenzene used in the present invention is synthesized from 3-halophenol, and the 3-halophenol is not particularly limited. That is, examples of the 3-halophenol include 3-fluorophenol, 3-chlorophenol, 3-bromophenol, and 3-iodophenol.
  • the 3-acetoxyhalobenzene used in the present invention can be easily synthesized by reacting 3-halophenol with acetic anhydride in the presence of triethylamine.
  • the palladium-based catalyst used in the present invention is palladium(II) chloride, palladium(II) bromide, palladium(II) halide such as palladium(II) iodide, palladium(II) acetate, palladium(II) propionate.
  • Examples thereof include divalent palladium compounds such as organic acid palladium(II), palladium(II) acetylacetonate, palladium(II) cyanide, palladium(II) nitrate, and palladium(II) sulfate.
  • the amount of the palladium catalyst used is preferably 0.001 to 10 mol, and more preferably 0.005 to 2 mol, based on 1 mol of 3-acetoxyhalobenzene. If the amount of the catalyst is too small, the yield will decrease, while if it is too large, the palladium catalyst will be expensive, and the production cost will increase.
  • the phosphine ligand used in the present invention is triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, triarylphosphine such as diphenyl-p-tolylphosphine, diethylphenyl.
  • Alkylarylphosphines such as phosphine, ethyldiphenylphosphine, dimethylphenylphosphine and methyldiphenylphosphine, trialkylphosphines such as tributylphosphine and triethylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenyl) Examples thereof include bidentate phosphines such as phosphino)propane and 1,4-bis(diphenylphosphino)butane.
  • triphenylphosphine, tri-o-tolylphosphine, tri Preferred are -m-tolylphosphine and tri-p-tolylphosphine.
  • the phosphine ligand is used so that the phosphorus/palladium (atomic ratio) is preferably in the range of 1 to 50, more preferably 1 to 25.
  • reaction solvent used in the present invention an ether solvent, an oxygen-containing solvent, a nitrogen-containing solvent, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an organic halogen solvent alone or a mixture thereof.
  • acetonitrile is particularly preferable from the viewpoint of reactivity.
  • a basic substance is present to immediately neutralize the hydrogen halide generated in the system during the reaction.
  • the basic substance used include trimethylamine, triethylamine, tributylamine, diethylamine, pyridine, organic bases such as DBU (1,8-diazabicyclo[5,4,0]undecene-7), and strongly basic ion exchange resins.
  • organic bases such as DBU (1,8-diazabicyclo[5,4,0]undecene-7
  • trialkylamines such as triethylamine and tributylamine are more preferable.
  • the method of the present invention is carried out in an ethylene gas atmosphere, and the pressure of ethylene gas is carried out at atmospheric pressure or higher. However, a pressure of 0.3 to 3 MPa is preferable in consideration of reactivity and equipment problems. Further, the method of the present invention is preferably carried out at a temperature of 170° C. or lower in consideration of the thermal stability of 3-acetoxystyrene.
  • the hydrogen halide salt of the organic base in the reaction solution cooled to room temperature is filtered off, and the residue is washed with the solvent and the same composition solution. Then, the filtrate and the washing solution are combined, the solvent is distilled off under reduced pressure, and a solvent immiscible with water such as ethyl acetate is added to the concentrate to dissolve it. The precipitated crystals are filtered off and the filtrate is washed with aqueous ammonium chloride solution and then with water.
  • the organic phase is dried over anhydrous sodium sulfate, a polymerization inhibitor such as tertiary butyl catechol is added thereto, and the mixture is distilled to obtain the target 3-acetoxystyrene.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
PCT/JP2019/027089 2018-12-28 2019-07-09 ３－アセトキシスチレンの製造方法 Ceased WO2020136961A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201980003869.2A CN111201213A (zh) 2018-12-28 2019-07-09 3-乙酰氧基苯乙烯的制造方法
KR1020197038325A KR20210110418A (ko) 2018-12-28 2019-07-09 3-아세톡시스티렌의 제조 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018247163A JP2019210274A (ja) 2018-12-28 2018-12-28 ３−アセトキシスチレンの製造方法
JP2018-247163 2018-12-28

Publications (1)

Publication Number Publication Date
WO2020136961A1 true WO2020136961A1 (ja) 2020-07-02

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Country Status (4)

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JP (1) JP2019210274A (https=)
KR (1) KR20210110418A (https=)
TW (1) TW202012356A (https=)
WO (1) WO2020136961A1 (https=)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7407651B2 (ja) * 2020-04-20 2024-01-04 東ソー・ファインケム株式会社 ３－アセトキシスチレンの製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002179621A (ja) * 2000-12-08 2002-06-26 Adchemco Corp ４−アセトキシスチレンの製造方法
JP2007504191A (ja) * 2003-09-05 2007-03-01 ディーエスエム アイピー アセッツ ビー．ブイ． スチルベン誘導体を製造する方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2131507C (en) 1993-11-08 1999-11-02 Edwin A. Chandross Resist materials and related processes
JP3585277B2 (ja) 1994-12-05 2004-11-04 本州化学工業株式会社 スチレン誘導体の製造方法
JP4186237B2 (ja) 1997-05-20 2008-11-26 Ｊｓｒ株式会社 ヒドロキシスチレンエステル類の製造方法
JP2004331515A (ja) 2003-04-30 2004-11-25 Ihara Chem Ind Co Ltd ３−アセトキシスチレンの製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002179621A (ja) * 2000-12-08 2002-06-26 Adchemco Corp ４−アセトキシスチレンの製造方法
JP2007504191A (ja) * 2003-09-05 2007-03-01 ディーエスエム アイピー アセッツ ビー．ブイ． スチルベン誘導体を製造する方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HEINER DETERT ,ERLI SUGIONO: "Synthese substituierter 1,4-Divinylbenzole durch doppelte Heck-Reaktion mit Ethen unter Druck", JOURNAL FUR PRAKTISCHE CHEMIE, vol. 341, no. 4, 1 January 1999 (1999-01-01), pages 358 - 362, XP055722874, ISSN: 1436-9966 *
RICHARD F HECK: "Palladium-catalysed vinylation of organic halides", ORGANIC REACTIONS, vol. 27, 1 January 1982 (1982-01-01), pages 345 - 390, XP055722872 *
SAMUEL L. BOURNE, MATTHEW O’BRIEN, SIVARAJAN KASINATHAN,PETER KOOS, PIVI TOLSTOY,DENNIS X. HU, RODERICK W. BATES, BENJAMIN MARTIN,: "Flow Chemistry Syntheses of Styrenes, Unsymmetrical Stilbenes and Branched Aldehydes", CHEMCATCHEM, vol. 5, no. 1, 20 December 2012 (2012-12-20), pages 159 - 172, XP055722867, ISSN: 1867-3880, DOI: 10.1002/cctc.201200778 *

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Publication number Publication date
KR20210110418A (ko) 2021-09-08
TW202012356A (zh) 2020-04-01
JP2019210274A (ja) 2019-12-12

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