GB784610A - Process for preparing -ß-ketoacetals - Google Patents

Process for preparing -ß-ketoacetals

Info

Publication number
GB784610A
GB784610A GB15402/54A GB1540254A GB784610A GB 784610 A GB784610 A GB 784610A GB 15402/54 A GB15402/54 A GB 15402/54A GB 1540254 A GB1540254 A GB 1540254A GB 784610 A GB784610 A GB 784610A
Authority
GB
United Kingdom
Prior art keywords
alkali metal
mixture
methyl
keto
formate
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.)
Expired
Application number
GB15402/54A
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.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
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 Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of GB784610A publication Critical patent/GB784610A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • C07C43/303—Compounds having groups having acetal carbon atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Saccharide Compounds (AREA)

Abstract

Dimethyl acetals of b -keto aldehydes, which aldehydes have the general formula R.CO.CH(R1)CHO, wherein R is an alkyl, vinyl or aralkyl group and R1 is hydrogen or an alkyl group, are prepared by adding an alkali metal enolate of the b -keto aldehyde with mixing to an anhydrous solution of such an amount of anhydrous hydrogen chloride in methanol that the pH of the mixture is maintained below 1 throughout the mixing, allowing the substantially anhydrous mixture to react at that pH at a temperature not above 25 DEG C., and thereafter raising the pH of the reacted mixture to from 6 to 7 by the addition of an alkali metal alkoxide which may be dissolved in an organic solvent and maintaining this pH in the mixture while recovering therefrom the resulting dimethyl acetal. The reaction is preferably carried out in methyl formate. The acetals may be recovered by adsorption but normally by distillation. The alkali metal enolates used as starting materials may be prepared by reacting a suitable ketone with an alkyl formate, such as methyl or ethyl formate, and an alkali metal or alkali metal alkoxide; preferably there is used methyl formate in excess whereby there is formed a slurry of the alkali metal enolate in methyl formate. A temperature of 15-25 DEG C. is preferred and an inert solvent may be present. Specified ketones are acetone, methyl ethyl ketone and methyl vinyl ketone. In examples: (1) sodium formyl acetone is prepared by reacting sodium or sodium methoxide with acetone and methyl formate and is then added in methanolic solution progressively to an anhydrous methanolic solution of hydrogen chloride with stirring at 15-25 DEG C.; the reacted mixture is neutralized with sodium methoxide in methanol to pH 6.0-6.5 whereupon after filtration the solvent is distilled off and the residue distilled under reduced pressure to yield the dimethyl acetal of b -keto butyraldehyde containing minor amounts of the b -keto vinyl ether; (2) as in (1), the enolate being in the form of a slurry prepared by adding acetone to a refluxing mixture of sodium methoxide and excess methyl formate. It is stated that substantial amounts of the vinyl ethers and triacyl benzene are formed if, in the process of the invention, ethanol replaces the methanol, the alcoholic hydrogen chloride is added to the enolate or the pH is not adjusted to 6-7 in the neutralization. The dimethyl acetals are useful in the synthesis of di-b -unsaturated aldehydes and pharmaceuticals. U.S.A. Specifications 2,091,373 and 2,570,713 and Japanese Specification 177,821 are referred to.
GB15402/54A 1953-05-26 1954-05-25 Process for preparing -ß-ketoacetals Expired GB784610A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US784610XA 1953-05-26 1953-05-26

Publications (1)

Publication Number Publication Date
GB784610A true GB784610A (en) 1957-10-09

Family

ID=22144168

Family Applications (1)

Application Number Title Priority Date Filing Date
GB15402/54A Expired GB784610A (en) 1953-05-26 1954-05-25 Process for preparing -ß-ketoacetals

Country Status (1)

Country Link
GB (1) GB784610A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4825008A (en) * 1986-12-30 1989-04-25 Hoeschst Aktiengesellschaft Acetylketene dialkyl acetals and a process for their preparation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4825008A (en) * 1986-12-30 1989-04-25 Hoeschst Aktiengesellschaft Acetylketene dialkyl acetals and a process for their preparation

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