WO1979000485A1 - Method of preparing e-4-acetoxy-2-methyl-2-butenal - Google Patents

Method of preparing e-4-acetoxy-2-methyl-2-butenal Download PDF

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Publication number
WO1979000485A1
WO1979000485A1 PCT/US1979/000028 US7900028W WO7900485A1 WO 1979000485 A1 WO1979000485 A1 WO 1979000485A1 US 7900028 W US7900028 W US 7900028W WO 7900485 A1 WO7900485 A1 WO 7900485A1
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WO
WIPO (PCT)
Prior art keywords
methyl
reaction mixture
buten
acetoxy
acetate
Prior art date
Application number
PCT/US1979/000028
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English (en)
French (fr)
Inventor
J Babler
Original Assignee
J Babler
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 J Babler filed Critical J Babler
Publication of WO1979000485A1 publication Critical patent/WO1979000485A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/64—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by simultaneous introduction of -OH groups and halogens
    • C07C29/66—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by simultaneous introduction of -OH groups and halogens by addition of hypohalogenous acids, which may be formed in situ, to carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • 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
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • 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
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers

Definitions

  • the present invention relates to a method of preparing E-4-acetoxy-2-methyl-2-butenal ( ⁇ -formylcrotyl acetate) .
  • This compound can be used in a synthesis of Vitamin A acetate.
  • the final step of the synthe ⁇ sis involves a reaction between a C, ⁇ triphenylphosphon- ium alt and a C c acetate:
  • the present invention relates to an improved pro-
  • An initial step in applicant's process of synthe ⁇ sizing E-4-acetoxy-2-methyl-2-butenal involves the prepara ⁇ tion of a 4-halo-3-methyl-2-buten-l-ol acetate intermediate.
  • This intermediate may be prepared directly, in a one-step reaction by the addition of a source of positive halogen, X+, to a solution of isoprene in acetic acid according to a process described by applicant and his co-worker [J. Babler and W. Buttner, Tetrahedron Lett., 239 (1976)].
  • Compounds providing suitable sources of positive halogen for this reaction include acid solutions of N-bromosuccinimide or a hypochlorite such as tert-butyl hypochlorite, as illustra ⁇ ted in the following reactions.
  • the first reaction yields approximately 75% by weight of the allylic halide as the desired 1,4 adduct and 25% as a 1,2 adduct.
  • Both the 1,4 adduct (systematically named 4-bromo-3-methyl-2-buten-l-ol acetate) and the 1,2 adduct (l-bromo-2-acetoxy-2-methyl-3-butene) are readily separable both from the reaction mixture and from one another by frac tional distillation.
  • the first step involves the synthesis of 1-chloro- 2-methyl-3-buten-2-ol, which may be synthesized from iso- prene in accordance with a process suggested in British
  • Patent 978,892 to Dunlop Rubber Company
  • the optimum route to the desired product, E-4- acetoxy-2-methyl-2-butenal depends which primary halide ⁇ intermediate is used.
  • the primary bromide 4- bromo-3-methyl-2-buten-l-ol acetate
  • the pro- duct may be obtained directly by the addition of dimethyl sulfoxide (DMSO) in the presence of a non-nucleophilic base such as sodium bicarbonate.
  • DMSO dimethyl sulfoxide
  • a non-nucleophilic base such as sodium bicarbonate.
  • the oxidation reaction proceeds at room temperature with yields of aldehyde in excess of 80%.
  • the DMSO oxidation of the primary allylic chloride to the desired ⁇ -formylcrotyl acetate will be suc ⁇ cessful when a different non-nucleophilic base is utilized in the reaction - a dibasic metal phosphate such as Na 2 HPO. or K 2 HP0 4 :
  • bromide salt such as sodium bromide and a monobas metal phosphate buffer is desirable, but not necessary.
  • N-bromosuccinimide N-bromosuccinimide
  • an alterna tive procedure could be used.
  • the desired 1,2- and 1,4-adducts can be remove from the reaction mixture by continuous extraction with heptane or hexane.
  • the acetic acid in turn, can be remov from the remaining aqueous layer by continuous extraction with benzene, ether, or chloroform.
  • the resultant aqueous layer will contain succinimide.
  • the product was iso ⁇ lated by pouring the mixture into ice-cold aqueous sodium hydroxide (enough to neutralize the acetic acid) and ex- tracting with ether. (The product can also be isolated by diluting the mixture with 10 volumes of iced water and con ⁇ tinuous extraction with cyclohexane.) The yield of 1° allylic acetate (containing no 3° acetate) was 1.94 g. (11.94 mmoles, 86% yield) .
  • the desired C-. acetate may be prepared by the general synthetic steps con ⁇ sisting of: (a) forming a first reaction mixture of iso ⁇ prene, acetic acid, and a source of positive halogen; (b) isolating 4-halo-3-methyl-2-buten-l-ol acetate as a reaction product from said first reaction mixture; and (c) forming a second reaction mixture of 4-halo-3-methyl-2-buten-l-ol acetate and dimethyl sulfoxide; (d) isolating E-4-acetoxy- 2-methyl-2-butenal as a reaction product from said second reaction mixture. More specifically, the particular steps employed in successful practice of the invention may involve the following in sequence:
  • N-bromosuccinimide was employed as the source of positive halogen in Example I, it is known that hypohalites such as tert-butyl hypochlorite may also be employed.
  • suitable non-nucleophilic bases other than sodium bicarbonate e.g., 2,4,6-trimethylpyridine (col dine)] may be employed in the synthesis illustrated in Ex ⁇ ample IV.
  • the DMSO oxidation proceeds much more favorably when a di ⁇ basic metal phosphate is used as the non-nucleophilic cata ⁇ lyst (Example V) .
  • a di ⁇ basic metal phosphate is used as the non-nucleophilic cata ⁇ lyst (Example V) .
  • all reactions may proceed at room temperature and under atmospheric pr although the formation and oxidation of primary chlorides is facilitated by use of moderate elevated temperatures (50° to 80°). It is expected, however, that obvious varia ⁇ tions in these reaction conditions may be desirable for large scale production, and such alterations are within the contemplation of the invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/US1979/000028 1978-01-20 1979-01-16 Method of preparing e-4-acetoxy-2-methyl-2-butenal WO1979000485A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US87107578A 1978-01-20 1978-01-20
US871075 1978-01-20
US06/001,075 US4175204A (en) 1978-01-20 1979-01-08 Method of preparing E-4-acetoxy-2-methyl-2-butenal

Publications (1)

Publication Number Publication Date
WO1979000485A1 true WO1979000485A1 (en) 1979-07-26

Family

ID=26668518

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1979/000028 WO1979000485A1 (en) 1978-01-20 1979-01-16 Method of preparing e-4-acetoxy-2-methyl-2-butenal

Country Status (3)

Country Link
US (1) US4175204A (en:Method)
EP (1) EP0008581A1 (en:Method)
WO (1) WO1979000485A1 (en:Method)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0268931A3 (en) * 1986-11-20 1988-10-05 Basf Aktiengesellschaft Process for preparing 2-substituted 4-acyloxy-2-butenals
US5527952A (en) * 1993-06-14 1996-06-18 Takeda Chemical Industries, Ltd. Process for producing aldehyde derivatives
CN102311339A (zh) * 2011-06-30 2012-01-11 绍兴文理学院 一种4-乙酰氧基-2-甲基-2-丁烯-1-醛的制备方法

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4579977A (en) * 1984-12-20 1986-04-01 Phillips Petroleum Company Process for the oxidation of organic halides to organic aldehydes
US5061819A (en) * 1988-10-31 1991-10-29 Loyola University Of Chicago Methods for synthesizing phosphonate reagents and retinoids
US4916250A (en) * 1988-10-31 1990-04-10 Loyola University Of Chicago Phosphonate reagent compositions
US5471004A (en) * 1993-06-14 1995-11-28 Takeda Chemical Industries, Ltd. Process for producing α,β-unsaturated aldehydes
US5905175A (en) * 1998-05-20 1999-05-18 The Nutrasweet Company Synthesis and purification of 3,3-dimethylbutyraldehyde via oxidation of 1-chloro-3,3-dimethylbutane with dimethyl sulfoxide
US6573409B1 (en) * 1999-07-02 2003-06-03 The Nutrasweet Company Process for the preparation of 3,3-dimethylbutanal
KR20020031297A (ko) * 2000-10-18 2002-05-01 고사이 아끼오 레티놀 및 이의 제조용 중간체 화합물의 제조 방법
EP1231197A1 (en) * 2001-02-07 2002-08-14 Sumitomo Chemical Company, Limited Process for producing allyl halide compound
CN112321421A (zh) * 2020-09-29 2021-02-05 宿迁科思化学有限公司 一种1-乙酰氧基-4-氯-3-甲基-2-丁烯的制备方法
CN114000170B (zh) * 2021-12-01 2023-03-24 万华化学集团股份有限公司 一种制备4-乙酰氧基-2-甲基-2-丁烯-1-醛的方法
CN114907212B (zh) * 2022-06-30 2023-08-11 万华化学集团股份有限公司 一种维生素a中间体的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2511870A (en) * 1945-12-08 1950-06-20 Ortho Pharmaceutical Corp. Method for producing esters of isoprene halohydrins
GB736488A (en) * 1952-12-24 1955-09-07 Roussel Uclaf Process for the preparation of an unsaturated aldehyde
US3213155A (en) * 1961-05-19 1965-10-19 Exxon Research Engineering Co Monoolefin isomerization process
US4048220A (en) * 1975-05-30 1977-09-13 Scm Corporation Process for preparation of 1,4-haloallylic esters from dienes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2511870A (en) * 1945-12-08 1950-06-20 Ortho Pharmaceutical Corp. Method for producing esters of isoprene halohydrins
GB736488A (en) * 1952-12-24 1955-09-07 Roussel Uclaf Process for the preparation of an unsaturated aldehyde
US3213155A (en) * 1961-05-19 1965-10-19 Exxon Research Engineering Co Monoolefin isomerization process
US4048220A (en) * 1975-05-30 1977-09-13 Scm Corporation Process for preparation of 1,4-haloallylic esters from dienes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Tetrahedron Letters, No. 11, issued March 1974, Pergamon Press, Great Britain, GANEM et al, Silver-Assisted Dimethylsulfoxide Oxidation, An Improved Synthesis of Aldehydes and Ketones, pp. 917-920. *
Tetrahedron Letters, No. 4, issued January 1976, Pergamon Press, Great Britain, BABLER et al, A Facile Route to E-Bromo-3-Methyl-2-Buten-1-ol; Application to Stereoselective Synthesis of Trisubstituted Olefins, pp. 239-42. *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0268931A3 (en) * 1986-11-20 1988-10-05 Basf Aktiengesellschaft Process for preparing 2-substituted 4-acyloxy-2-butenals
US4873362A (en) * 1986-11-20 1989-10-10 Basf Aktiengesellschaft Preparation of 2-substituted 4-acyloxy-2-butenals
US5527952A (en) * 1993-06-14 1996-06-18 Takeda Chemical Industries, Ltd. Process for producing aldehyde derivatives
CN102311339A (zh) * 2011-06-30 2012-01-11 绍兴文理学院 一种4-乙酰氧基-2-甲基-2-丁烯-1-醛的制备方法
CN102311339B (zh) * 2011-06-30 2014-06-04 绍兴文理学院 一种4-乙酰氧基-2-甲基-2-丁烯-1-醛的制备方法

Also Published As

Publication number Publication date
EP0008581A1 (en) 1980-03-05
US4175204A (en) 1979-11-20

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