GB735974A - Improvements in the epoxidation of ethylenically unsaturated organic compounds - Google Patents

Improvements in the epoxidation of ethylenically unsaturated organic compounds

Info

Publication number
GB735974A
GB735974A GB21429/53A GB2142953A GB735974A GB 735974 A GB735974 A GB 735974A GB 21429/53 A GB21429/53 A GB 21429/53A GB 2142953 A GB2142953 A GB 2142953A GB 735974 A GB735974 A GB 735974A
Authority
GB
United Kingdom
Prior art keywords
mono
peracylate
acetaldehyde
ethylenic
propionaldehyde
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
GB21429/53A
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.)
Union Carbide Corp
Original Assignee
Union Carbide and Carbon 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 Union Carbide and Carbon Corp filed Critical Union Carbide and Carbon Corp
Publication of GB735974A publication Critical patent/GB735974A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals

Landscapes

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

Abstract

Ethylenic compounds as defined below are converted into the corresponding epoxides by reaction with an acetaldehyde mono-peracylate or propionaldehyde mono-peracylate at about 25-200 DEG C. Preferably a cold solution of the mono-peracylate is fed intermittently or continuously into a heated reaction chamber at 40-120 DEG C. containing the ethylenic compound or solution thereof, the reaction then occurring in the liquid or vapour phase. It is desirable to use more than the theoretical quantity of ethylenic compound and to remove as fast as it is formed the aldehyde and acid resulting from decomposition of the mono-peracylate. The ethylenic compound is one having the following characteristics: (1) having at least three carbon atoms; (2) containing no element other than carbon, hydrogen, oxygen, halogen, nitrogen (as amide, imide or nitrile) or phosphorus (as phosphoric ester), and (3) having attached to the >C=C< group only hydrogen or carbon not multiply linked to elements other than carbon or hydrogen; mesityl oxide is however included. A polymerization inhibitor may be added if desired. Examples show the preparation of epoxides of propylene, butadiene, styrene, 4-vinylcyclohexene and its monoxide, allyl alcohol, mesityl oxide, oleic acid, soybean oil, methallyl chloride, oleamide, D 3-tetrahydrobenzonitrile and N-(n-butyl)-D 3-tetrahydrophthalimide. A list is given of other ethylenic compounds, of the following types: alkenes, alkadienes, alkenylbenzenes, cycloalkenes, cycloalkadienes, indene, dihydronaphthalene, methylenecyclohexane, alkenyl chlorides, bromides and fluorides, chlorostyrenes, chloromethylstyrenes, 1 - chloro - 3 - vinylcyclohexane, trichloromethyl - cyclohexene, alkenols, cinnamyl alcohol, cyclohexenylmethanol, alkenylphenols, methylenecyclohexanol, alkenyloxy compounds, cyano-alkenes, vinylbenzonitriles, unsaturated ketones, acids and esters (including glycol dioleate and diallyl maleate), p-vinylbenzaldehyde, unsaturated amides, vinylbenzamides, N - alkenyl - imides, acetals of unsaturated aldehydes (including p-vinylbenzaldehyde), acetaldehyde diallyl acetal, alkenyl phosphates and tri-(crotylphenyl) phosphate. Acetaldehyde monoperacetate CH3CH(OH) OOCOCH3 is prepared by treating acetaldehyde with an oxygen-containing gas below 15 DEG C., preferably in a solvent. Salts of heavy metals such as cobalt, copper and iron are catalysts for the reaction, but excess tends to decompose the peroxide to acetic acid. Propionaldehyde monoperpropionate is made similarly. Experimental details are given in each case.ALSO:Ethylenic compounds, including unsaturated oils such as soybean oil and linseed oil, are converted into the corresponding epoxides by reaction with an acetaldehyde mono-peracylate or propionaldehyde mono-peracylate at about 25-200 DEG C. Preferably a cold solution of the mono-peracylate is fed intermittently or continuously into a heated reaction chamber at 40-120 DEG C. containing the ethylenic compound or solution thereof. It is desirable to use more than the theoretical quantity of ethylenic compound and to remove as fast as it is formed the aldehyde and acid resulting from decomposition of the mono - peracylate. Examples show the epoxidation of soybean oil with acetaldehyde mono-peracetate and propionaldehyde mono-perpropionate.
GB21429/53A 1952-08-07 1953-08-04 Improvements in the epoxidation of ethylenically unsaturated organic compounds Expired GB735974A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US735974XA 1952-08-07 1952-08-07

Publications (1)

Publication Number Publication Date
GB735974A true GB735974A (en) 1955-08-31

Family

ID=22114645

Family Applications (1)

Application Number Title Priority Date Filing Date
GB21429/53A Expired GB735974A (en) 1952-08-07 1953-08-04 Improvements in the epoxidation of ethylenically unsaturated organic compounds

Country Status (1)

Country Link
GB (1) GB735974A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1058987B (en) * 1957-04-26 1959-06-11 Studiengesellschaft Kohle Mbh Preparation of cyclododecadiene monoepoxide from cyclododecatrienes
US2948669A (en) * 1960-08-09 Production of superior neutral oils
DE1139486B (en) * 1957-06-04 1962-11-15 Pittsburgh Plate Glass Co Process for separating butadiene monoxide and carboxylic acids
DE1229072B (en) * 1957-06-04 1966-11-24 Pittsburgh Plate Glass Co Process for removing the carboxylic acid from butadiene monoxide-carboxylic acid mixtures
US3333010A (en) * 1962-05-18 1967-07-25 Basf Ag Production of cyclododecanol
DE1266302B (en) * 1962-08-30 1968-04-18 Celanese Corp Process for the oxidation of organic compounds
US9499505B2 (en) 2014-09-18 2016-11-22 Chang Chun Plastics Co., Ltd. Process for the epoxidation of olefins

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2948669A (en) * 1960-08-09 Production of superior neutral oils
DE1058987B (en) * 1957-04-26 1959-06-11 Studiengesellschaft Kohle Mbh Preparation of cyclododecadiene monoepoxide from cyclododecatrienes
DE1139486B (en) * 1957-06-04 1962-11-15 Pittsburgh Plate Glass Co Process for separating butadiene monoxide and carboxylic acids
DE1229072B (en) * 1957-06-04 1966-11-24 Pittsburgh Plate Glass Co Process for removing the carboxylic acid from butadiene monoxide-carboxylic acid mixtures
US3333010A (en) * 1962-05-18 1967-07-25 Basf Ag Production of cyclododecanol
DE1266302B (en) * 1962-08-30 1968-04-18 Celanese Corp Process for the oxidation of organic compounds
US9499505B2 (en) 2014-09-18 2016-11-22 Chang Chun Plastics Co., Ltd. Process for the epoxidation of olefins

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