EP0000535B1 - Procédé de préparation de vinyloxirannes substitués par un ou plusieurs halogènes - Google Patents

Procédé de préparation de vinyloxirannes substitués par un ou plusieurs halogènes Download PDF

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Publication number
EP0000535B1
EP0000535B1 EP78100421A EP78100421A EP0000535B1 EP 0000535 B1 EP0000535 B1 EP 0000535B1 EP 78100421 A EP78100421 A EP 78100421A EP 78100421 A EP78100421 A EP 78100421A EP 0000535 B1 EP0000535 B1 EP 0000535B1
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Prior art keywords
vinyl
halogen
chlorine
alkyl
polyene
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EP78100421A
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German (de)
English (en)
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EP0000535A1 (fr
Inventor
Gebhard Dr. Rauleder
Hermann Dr. Seifert
Helmut Dr. Waldmann
Wulf Dr. Schwerdtel
Wolfgang Dr. Swodenk
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Bayer AG
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Bayer AG
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    • 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
    • C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
    • 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
    • C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals

Definitions

  • the present invention relates to a process for the preparation of halogen-substituted oxiranes from halogen-substituted polyenes and percarboxylic acids and to new 2-chloro-2-vinyl and 2-chloro-3-vinyl-oxiranes.
  • vinyl oxiranes substituted on the oxirane ring or on the vinyl group by halogen are particularly important as monomers. They can therefore be used in the field of paints and plastics, organic intermediates and in crop protection, which is particularly important for the new compounds with 2-chloro-2-vinyl-oxirane and 2-chloro-3-vinyl oxirane structure is of interest.
  • the French patent application relates to the reaction of ethylene, propylene, chlorine- or hydroxy-substituted propylene, butene, pentene and higher alkenes with percarboxylic acid to form oxiranes.
  • the only halogen-containing feed described is allyl chloride. In contrast to the compounds which can be used according to the invention, this contains halogen on a saturated carbon atom. From D. Swem, Organic Peroxides, vol. 11, page 490 it is known that epoxides which contain a chlorine atom on the epoxy ring rearrange extremely easily into ⁇ -chloro ketones and in many cases that epoxide cannot be isolated.
  • 1,3-dichlorobutadiene, 2,3-dichlorobutadiene, 1-chlorobutadiene and 2-chlorobutadiene are very particularly suitable for reaction with percarboxylic acids by the process according to the invention.
  • the various hydrocarbons can be used as organic solvents, for example aliphatic and cycloaliphatic hydrocarbons such as hexane, heptane, octane, 2-ethylhexane, decane, dodecane, cyclohexane, methylcyclopentane, petroleum ether; aromatic hydrocarbons such as benzene, nitrobenzene, toluene, ethylbenzene, cumene, diisopropylbenzene, xylene, chlorobenzene; oxygen-containing hydrocarbons such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, pyran, acetone, Methyläthyliketon, ethyl acetate, methyl acetate, propyl acetate, butyl acetate, methyl propionate, propionic acid, ethy
  • Preferred solvents are the chlorinated hydrocarbons methyl chloride, chloroform, carbon tetrachloride and 1,2-dichloropropane, the aromatic hydrocarbons benzene, nitrobenzene, toluene and chlorobenzene, the hydrocarbons 2-ethyl-hexane, cyclohexane, methyl-cyclopentane and the oxygen-containing hydrocarbons Acetone, tetrahydrofuran, ethyl propionate.
  • Particularly preferred solvents are 1,2-dichloropropane and carbon tetrachloride from the chlorinated hydrocarbons, benzene and chlorobenzene from the aromatic hydrocarbons, cyclohexane from the hydrocarbons and ethyl propionate from the oxygen-containing hydrocarbons.
  • Solvent mixtures of the various organic solvents specified above can also be used.
  • Peracids which can be used according to the invention are perpropionic acid, perbutyric acid and perisobutyric acid. Perpropionic acid and perisobutyric acid are preferably used. Perpropionic acid is particularly preferred.
  • the preparation of the mineral acid-free peracids in one of the organic solvents mentioned can e.g. according to the procedure described in DOS 2 262 970.
  • the process according to the invention is carried out in a temperature range of -20-100 ° C. It is preferred to work at 0-60 ° C, particularly preferably at 10-40 ° C. In special cases, the specified temperatures can also be exceeded or fallen short of.
  • the reaction can also be carried out with the formation of a so-called temperature gradient, which generally increases with the progress of the reaction.
  • the reaction can also be carried out in such a way that a gradient of falling temperature is formed as the reaction proceeds.
  • the molar ratio of halogen-substituted polyene to percarboxylic acid is 1.0: 1.0 to 10 or 1.0 to 10: 1.0.
  • a molar ratio of ofefin to percarboxylic acid of 1.0: 1.0 to 5 or 1.0 to 2: 1.0 can also be used.
  • a molar ratio of 1.0: 1 to 5 is preferably used. It is particularly advantageous to use a molar ratio of 2.0 to 3.0 moles of halogen-substituted polyene per mole of peracid.
  • the method according to the invention can be carried out at a wide variety of pressures. Generally one works at normal pressure; however, the process can also be carried out under negative or positive pressure.
  • the water content of the percarboxylic acid used for the epoxidation is up to 5% by weight.
  • a percarboxylic acid with a water content of up to 1% by weight is suitable.
  • a percarboxylic acid solution which contains less than 0.5% by weight of water is preferably used.
  • the hydrogen peroxide content of the percarboxylic acid used is up to 2% by weight. It is advantageous to work with a content of less than 1% by weight. It is particularly advantageous to carry out the reaction with a percarboxylic acid solution which has a hydrogen peroxide content below 0.3%, e.g. 0.01 to 0.3% by weight.
  • the mineral acid content of the percarboxylic acid solution being implemented is less than 50 ppm.
  • a mineral acid content of less than 10 ppm is particularly advantageous.
  • the reaction can be carried out batchwise or continuously in the devices customary for reactions of this type, such as stirred tanks, boiling reactors, tubular reactors, loop reactors or loop reactors.
  • Heavy metal ions in the reaction mixture catalyze the decomposition of the percarboxylic acid. Substances are therefore generally added to the percarboxylic acid solution which inactivate the heavy metal ions through complex formation.
  • Known substances of this type are gluconic acid, ethylenediaminetetraacetic acid, sodium silicate, sodium pyrophosphate, sodium hexametaphosphate, disodium dimethyl pyrophosphate or Na 2 (2-ethylhexyl), (P l o ll ) 2 (DAS 1 056 596, column 4, line 60 ff.).
  • the halogen-substituted polyene can be introduced into the device used for the reaction in various ways. It can be added to the reactor together with the percarboxylic acid solution, or the two components can be fed to the reactor separately. It is also possible to feed the olefin and the percarboxylic acid solution into the reactor unit at various points. When using several reactors connected in cascade, it may be expedient to introduce all of the olefin into the first reactor. However, the olefin can also be divided between the various reactors.
  • the heat of reaction is dissipated by internal or external coolers.
  • the reaction can also be carried out under reflux, i.e. in boiling reactors.
  • the reaction is advantageously carried out with the most complete possible conversion of the percarbonic acid. In general, more than 95 mol% of the percarboxylic acid is reacted. It is expedient to convert more than 98 mol% of peracid.
  • the reaction mixture is worked up in a manner known per se, for example by distillation.
  • an approximately 20% by weight perpropionic acid solution in benzene is added with stirring to the double molar amount of halogen-substituted polyene which is thermostatted at 30 ° C.
  • the perpropionic acid solution contains less than 10 ppm mineral acid; it has a water content of less than 0.1% and a hydrogen peroxide content of less than 0.3%.
  • To complex heavy metal ions about 0.05% by weight of Na 5 (2-ethylhexyl) 5 (P 3 O 10 ) 2 was added to the perpropionic acid before the reaction. The progress and the end of the reaction are checked by taking samples from the reaction solution at intervals and determining the content of percarboxylic acid still present by titration. After the reaction has ended, the reaction mixture is fractionated.
  • the peracid conversion was 99%.
  • the two oxiranes were again formed in a ratio of -3: 2 with an overall selectivity of 84.5%.
  • the reaction mixture was worked up by distillation. First, chloroprene, benzene and the two oxiranes were taken off as top product in a distillation column equipped with a thin-layer evaporator, while propionic acid was obtained at the bottom.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Compounds (AREA)

Claims (7)

1. Procédé de production de vinyloxiranes substitués par des halogènes sur le noyau d'oxirane et/ou sur le groupe vinyle à partir de polyènes substitués par des halogènes et d'acides percarboxy- liques en solution organique, caractérisé en ce qu'on fait réagir un polyène substitué par un halogène, de formule:
Figure imgb0014
dans laquelle:
R, et R6 représentent, indépendamment l'un de l'autre, de l'hydrogène, un radical alkyle en C, à C4, vinyle ou phényle,
R2, R3, R4 et R5 représentent, indépendamment l'un de l'autre, de l'hydrogène un radical alkyle en C1 à C4, vinyle, cycloalkyle en C3 à C7, phényle, du fluor, du chlore ou du brome, et l'un au moins des restes R2 à R5 désigne du fluor, du chlore ou du brome, R1 pouvant former avec R2 ou R1 avec R3 ou R1 avec R4 ou R1 avec R5 ou R3 avec R4, un noyau carbocyclique,

avec une solution d'un acide percarboxylique dans un solvant organique dans un rapport molaire du polyène substitué par un halogène à l'acide percarboxylique de 1,0:1,0 à 10 ou de 1,0 à 10:1,0 et à une température de -20 à +100°C, l'acide percarboxylique contenant jusqu'à 5% en poids d'eau, jusqu'à 2% en poids de peroxyde d'hydrogène et la solution d'acide percarboxylique contenant moins de 50 parties par million d'acide minéral.
2. Procédé suivant la revendication 1, caractérisé en ce qu'on utilise comme polyène substitué par un halogène un polyène de formule:
Figure imgb0015
dans laquelle:
R11, R12 et R13 représentent, indépendamment l'un de l'autre, de l'hydrogène, un radical alkyle en C1 à C4, vinyle, cycloalkyle en C5 à C7, phényle, du fluor, du chlore ou du brome, l'un au moins des restes R11 à R13 représentant du fluor, du chlore ou du brome et
R14 désigne de l'hydrogène, un radical alkyle en C1 à C4, vinyle ou phényle,

n est un nombre entier de 2 à 10.
3. Procédé suivant les revendications 1 et 2, caractérisé en ce qu'on utilise comme polyène substitué par un halogène un polyène de formule:
Figure imgb0016
dans laquelle:
R15, R16 et R17 représentent, indépendamment l'un de l'autre, de l'hydrogène, un radical alkyle en C1 à C4, vinyle, cycloalkyle en C3 à C7, phényle, du fluor, du chlore ou du brome, l'un au moins des restes R15 à R17 étant du fluor, du chlore ou du brome, et
R18 est de l'hydrogène ou un radical alkyle en C, à C4, vinyle ou phényle, et
n est un nombre entier de 1 à 9.
4. Procédé suivant les revendications 1 à 3, caractérisé en ce qu'on utilise comme polyène substitué par un halogène, un polyène de formule:
Figure imgb0017
dans laquelle:
R19, R20, R21 et R22 représentent, indépendamment l'un de l'autre, de l'hydrogène, un radical alkyle en C1 à C4, vinyle, phényle, cycloalkyle en C5 à C7, du fluor, du chlore ou du brome, l'un au moins des restes R19 à R22 étant du fluor, du chlore ou du brome.
5. Procédé suivant les revendications 1 à 4, caractérisé en ce qu'on utilise comme polyène substitué par un halogène un polyène de formule:
Figure imgb0018
dans laquelle:
R23, R24, R25 et R26 représentent, indépendamment l'un de l'autre, de l'hydrogène, un radical alkyle en C1 à C4, un radical vinyle ou du chlore, l'un au moins des restes R23 à R26 représentant du chlore.
6. Procédé suivant les revendications 1 à 5, caractérisé en ce qu'on utilise comme polyène substitué par un halogène, le 1,3-dichlorobutadiène, le 2,3-dichlorobutadiène, le 1-chlorobutadiène ou le 2-chlorobutadiène.
7. Procédé suivant les revendications 1 à 6, caractérisé en ce qu'on utilise, comme solvant, du benzène, du chlorobenzène, du 1,2-dichloropropane, du tétrachlorure de carbone, du propionate d'éthyle ou du cyclohexane.
EP78100421A 1977-07-29 1978-07-18 Procédé de préparation de vinyloxirannes substitués par un ou plusieurs halogènes Expired EP0000535B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772734243 DE2734243A1 (de) 1977-07-29 1977-07-29 Verfahren zur herstellung von halogensubstituierten vinyloxiranen
DE2734243 1977-07-29

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EP0000535A1 EP0000535A1 (fr) 1979-02-07
EP0000535B1 true EP0000535B1 (fr) 1982-05-19

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JPS5840245A (ja) * 1981-08-31 1983-03-09 Nissan Motor Co Ltd 直動および回転、割出装置
DE102005019296A1 (de) 2005-04-26 2006-11-09 Deutsche Exide Gmbh Entgasungsventil für Säurebatterien
DE102007040368A1 (de) 2007-08-17 2009-02-19 Adolf Würth GmbH & Co. KG Spreizdübel
DE102021123420A1 (de) 2020-09-11 2022-03-17 Illinois Tool Works Inc. Notentgasungsventil
DE102023106792A1 (de) 2022-04-11 2023-10-12 Illinois Tool Works Inc. Notentgasungsventilvorrichtung

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GB1535313A (en) * 1975-02-04 1978-12-13 Interox Chemicals Ltd Production of peracids and of epoxides
GB1584355A (en) * 1976-10-26 1981-02-11 Propylox Sa Epoxidation
FR2369273A1 (fr) * 1976-10-26 1978-05-26 Propylox Sa Procede pour l'epoxydation d'olefines

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JPS5427515A (en) 1979-03-01
DE2734243A1 (de) 1979-02-08
DE2861847D1 (en) 1982-07-08

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