EP0000555B1 - Procédé de préparation d'oxirannes substitués par des groupes halogénoalcoyle - Google Patents

Procédé de préparation d'oxirannes substitués par des groupes halogénoalcoyle Download PDF

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Publication number
EP0000555B1
EP0000555B1 EP19780100457 EP78100457A EP0000555B1 EP 0000555 B1 EP0000555 B1 EP 0000555B1 EP 19780100457 EP19780100457 EP 19780100457 EP 78100457 A EP78100457 A EP 78100457A EP 0000555 B1 EP0000555 B1 EP 0000555B1
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Prior art keywords
alkyl
dichloro
substituted
acid
dibromo
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EP19780100457
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German (de)
English (en)
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EP0000555A1 (fr
Inventor
Gebhard Dr. Rauleder
Helmut Dr. Waldmann
Willi Hofen
Rolf Dr. Wirthwein
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Bayer AG
Evonik Operations GmbH
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Bayer AG
Degussa GmbH
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    • 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
    • C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
    • 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

Definitions

  • the present invention relates to an improved process for the preparation of haloalkyl-substituted oxiranes from haloalkyl-substituted olefins and percarboxylic acids.
  • Haloalkyl-substituted oxiranes are used in the field of paints and plastics and as organic intermediates.
  • Haloalkyl-substituted olefins can therefore not be epoxidized easily with percarboxylic acids . Due to the low reactivity of their double bond, high temperatures and long reaction times are required, which gives rise to the formation of undesirable by-products such as dihydroxy and hydroxyacyloxy derivatives of the starting products. (S.N. Lewis in R.L. Augustin, "Oxidation", vol. 1, page 233, in particular 3. 6-11, Marcel Dekker, New York 1969).
  • the structure and mode of preparation of the percarboxylic acid used is of great importance, in particular with regard to the type and implementation of the reaction between a haloalkyl-substituted olefin and a percarboxylic acid.
  • Performic acid can be prepared from hydrogen peroxide and formic acid without an additional catalyst (S. N. Lewis in R. L. Augustin, "Oxidation", Vol. I, p. 217, first paragraph, Marcel Dekker, New York 1969).
  • the reaction of a-chloroalkyl-substituted olefins with this mineral acid-free percarboxylic acid also gave the corresponding epoxide only in low yields.
  • performic acid made from 90% formic acid and 85% hydrogen peroxide was used for the epoxidation of 3,4-dichlorobutene- (1).
  • a process for the production of aliphatic chlorine epoxides by reacting an allyl chlorohydrocarbon which has a chlorine atom adjacent to the double bond with an organic per compound which is free from inorganic impurities has recently become known (DAS 1 056 596).
  • the per compounds used here are "pure peracetic acid, perpropionic acid or acetaldehyde monoperacetate in a mixture with acetaldehyde and / or acetone".
  • DAS 1 056 596 Epoxidation in accordance with the DAS 1 056 596 process of allyl-chlorine-substituted olefins with acetaldehyde monoperacetate yields the corresponding oxiranes in yields based on the per-compound of between 17% and 56%.
  • DAS 1 056 596 columns 5 to 7, lines 35 ff., Examples 1, 3, 4 and 6).
  • peracetic acid and perpropionic acid used for this epoxidation process are used dissolved in an inert organic solvent.
  • typical inert solvents in this process include acetone, ethyl acetate, butyl acetate and dibutyl ether (U.S. Pat. No. 3,150,154, column 3, lines 1-3).
  • Allyl chlorohydrocarbons can be epoxidized with the peracids produced according to the process of DAS 1 056 596; however, the yields of oxiranes are low; the peracid conversion is incomplete. In the examples given it is only about 90% and the purity of the isolated oxiranes is insufficient for industrial use.
  • the DAS 1 056 596 in Example 5, column 7, lines 5 ff. Describes the epoxidation of 3-chloro-1-butene with a solution of peracetic acid in acetone. The peracid conversion is 91% after a reaction time of ten hours. The oxirane is isolated with a purity of 90.5% in 68% yield.
  • GB-PS 784 620 only acetone, ethyl acetate, acetic acid, butyl acetate and dibutyl ether are described as solvents for peracids, and only the reaction of aldehydes with oxygen via peroxides as intermediates as a production method for peracids.
  • Benzene is not mentioned or suggested as a solvent since, unlike the solvents mentioned, benzene is non-polar.
  • the yields of dichloropoxibutanes are 75 and 82% according to the process of GB-PS (see Examples III and VII). This yield cannot be described as satisfactory and is considerably higher in the process according to the invention.
  • DE-OS 26 02 776 (corresponds to FR-OS 2 300 085) discloses a process for the epoxidation of alkenes or their derivatives by reaction with peracid, in which a solution of a peracid in a chlorinated hydrocarbon is first prepared, this with the Alken or its derivative is fed to a reactor in cocurrent and the product mixture is worked up in a special way.
  • the reaction temperature is preferably about 100 ° C. If longer reaction times or lower yields are tolerated, it is also possible to work at 50 to 150 ° C., but a range from 90 to 120 ° C. is desirable (see DE-OS 26 02 776, pages 10/11).
  • Examples include: allyl chloride, 2-chloromethyl-propene, 3-chloro-2-chloromethyl-propene, 3-chloro-1-butene, 1-chloro-2-butene, 1,4-dichloro-2-butene, 3,4-dichloro-1-butene, 3-chloro-1-pentene, 4-chloro-2-pentene, 1-chloro-2-pentene, 1,4-dichloro-2-pentene, 3,4-dichloro- 1-pentene, 1,2-dichloro-3-pentene, 3-chloro-1-hexene, 1-chloro-2-hexene, 1,4-dichloro-2-hexene, 3,4-dichloro-1-hexene, 2-chloro-3-hexene, 2,5-dichloro-3-hexene, 3-chloro-1-cyclohexene, 1,4-dichloro-2-cyclohexene; Ally
  • 1,4-dichloro-2-butene, 1,4-dibromo-2-butene and 3,4-dichloro-1-butene are very particularly suitable for reaction with percarboxylic acids by the process according to the invention.
  • Benzene is used as solvent in the process according to the invention.
  • 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 benzene can e.g. according to the procedure described in DOS 2 262 970.
  • the process according to the invention is carried out at 60-80 ° C., particularly preferably at 65-75 ° C. In special cases, the specified temperatures can 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 olefin to peracid is 1.1: 1 to 10: 1.
  • a molar ratio of 1.25: 1 to 5: 1 is preferably used. It is particularly advantageous to use a molar ratio of 1.5 to 3.0 moles of olefin 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 2% by weight is suitable.
  • a percarboxylic acid solution which contains less than 1% by weight of water is preferably used.
  • a water content of less than 0.1% by weight is particularly preferred.
  • 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%.
  • the process according to the invention is carried out with a percarboxylic acid solution which has a mineral acid content below 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, sidereactors, tubular reactors, loop reactors or loop reactors.
  • Glass, stainless steel or enamelled material can be used as materials for carrying out the processes.
  • 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) 5 (P 3 O, o ) 2 (DAS 1 056 596, column 4, line 60 ff.).
  • the haloalkyl-substituted olefin 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 (boiling reactors).
  • the reaction is expediently carried out with the most complete possible conversion of the percarboxylic 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, e.g. B. by distillation. It is particularly advantageous to extract the reaction mixture with water before working up by distillation in order to separate off the carboxylic acid corresponding to the percarboxylic acid formed during the reaction.
  • the extraction can be carried out in the usual extractors such as mixer-separators, sieve tray extractors, pulsating sieve tray columns, turntable extractors or extraction centrifuges.
  • an approximately 20% by weight perpropionic acid solution in benzene is added with stirring to the triple-molar amount of haloalkyl-substituted olefin, which is thermostated at 70 ° 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, (2-ethylhexyl), (P301.) 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 cooled and washed three times with the same amount of water to remove the propionic acid. The propionic acid-free reaction mixture is then fractionated.
  • haloalkyl-substituted oxiranes can be prepared in high yields and with high purity.
  • reaction mixture was washed several times with water to remove the propionic acid, benzene was distilled off and then fractionated in a 10 cm packed column filled with 4 mm glass Rasching rings. 18.9 g of 2- (1,2-dichloroethyl) oxirane with a purity of 99.4% were isolated.
  • This reaction system was fed 2,137.5 g perpropionic acid as a 20% solution in benzene (4.75 mol) and 1,781.25 g (14.25 mol) 1,4-dichloro-2-butene per hour, which had an average residence time of corresponded to about 8 hours. Under these reaction conditions, 96.8% of the perpropionic acid was converted. The selectivity of the 2,3-bis (chloromethyl) oxirane formed was 96%, based on the perpropionic acid used.
  • the reaction mixture obtained after the third reactor had the following composition on average: 35.6% benzene, 30.8% 1,4-dichloro-2-butene, 16.24% 2,3-bis (chloromethyl) oxirane and 17 % Propionic acid.
  • This mixture was extracted in a pulsating sieve plate column with twice the amount of water to separate the propionic acid. Thereafter, the residual propionic acid content was 0.04%.
  • the reaction mixture obtained after this operation was separated on a distillation line. In a first column, benzene was distilled in an amount of 1,395 g per hour. The bottom product of this column, which consisted essentially of starting material and oxirane, was separated in a second column under reduced pressure.
  • 1,206.5 g of 1,4-dichloro-2-butene were obtained as the top product per hour.
  • the bottom product of this column was freed from high boilers in a third column under reduced pressure.
  • 629.5 g of 2,3-bis (chloromethyl) oxirane with a purity of over 99.9% were obtained as the top product per hour. This corresponds to a yield of 94%, based on the perpropionic acid used in the reaction system.

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

Claims (9)

1. Procédé de production d'oxiranes à substituants halogénalkyle à partir de mono-oléfines à substituants chloralkyle ou bromalkyle de formule générale:
Figure imgb0012
dans laquelle:
R1 et R4 désignent, indépendamment l'un de l'autre, de l'hydrogène, un reste alkyl en C1 à C5, cycloalkyle en C5 à C7, monochloralkyle en C1 à C5, monobromalkyle en C1 à C5, dichloralkyle en C1 à C5, dibromalkyle en C1 à C5, monochlorocycloalkyle en C5 à C7, monobromocyclo-alkyle en C5 à C7, di- chlorocyclo-alkyle en C5 à C7, dbromocyclo-afkyle en C5 à C7, .
R2 et R3 désignent, indépendamment l'un de l'autre, l'hydrogène, un reste alkyle en C1 à C5, monochloralkyle en C1 à C5, monobromalkyle en C1 à C5, dichloralkyle en C1 à C5 et dibromalkyle en C1 à C5, les restes
R2 et R3 pouvant former conjointement avec les atomes de carbone de la double liaison C=C un noyau ayant jusqu'à 12 atomes de carbone, et au moins l'un des restes R1 à R4 étant un reste alkyl ou cycloalkyle du type mentionné contenant du chlore ou du brome,
et d'acides percarboxyliques à température élevée et en présence de solvants, caractérisé en ce qu'on conduit la réaction avec une solution d'un acide percarboxylique contenant 3 ou 4 atomes de carbone dans le benzène dans un rapport molaire de la mono-oléfine à l'acide percarboxylique de 1,1 : 1 à 10 : 1 et à une température de 60 à 80°C, l'acide percarboxylique contenant jusqu'à 5 % en poids d'eau et jusqu'à 2 % en poids de peroxyde d'hydrogène et la solution d'acide percarboxylique amenée à réagir ayant une teneur en acide minéral inférieure à 50 ppm.
2. Procédé suivant la revendication 1, caractérisé en ce qu'on utilise comme mono-oléfine à substituant chloralkyle ou bromalkyle une oléfine de formule:
Figure imgb0013
dans laquelle:
R7 et R8 désignent, indépendamment l'un de l'autre, de l'hydrogène, un reste alkyle en C1 à C5, monochloralkyle en C1 à C5, monobromalkyle en C1 à C5, dichloralkyle en C1 à C5 ou dibromalkyle en C1 à C5, R9 et R10 désignent, indépendamment l'un de l'autre, un reste méthylène, chlorométhylène, bromo- méthylène, 1,2-dichloréthylène ou 1,2-dibromométhylène,
n désigne un nombre entier de 1 à 6 et au moins l'un des restes R7-R10 représente un reste alkyle, cycloalkyle ou alkylène du type mentionné contenant du chlore ou du brome.
3. Procédé suivant la revendication 1, caractérisé en ce qu'on utilise le 1,4-dichloro-2-butène comme oléfine à substituant chloralkyle ou bromalkyle.
4. Procédé suivant la revendication 1, caractérisé en ce qu'on utilise le 3,4-dichloro-1-butène comme oléfine à substituant chloralkyle ou bromalkyle.
5. Procédé suivant la revendication 1, caractérisé en ce qu'on utilise le 1,4-dibromo-2-butène comme oléfine à substituant chloralkyle ou bromalkyle.
6. Procédé suivant les revendications 1 à 5, caractérisé en ce qu'on utilise comme acide percarboxylique l'acide perpropionique.
7. Procédé suivant les revendications 1 à 5, caractérisé en ce qu'on utilise comme acide percarboxylique l'acide perisobutyrique.
8. Procédé suivant les revendications 1 à 7, caractérisé en ce qu'on conduit la réaction à un rapport molaire de l'oléfine au peracide de 1,5 à 3 : 1.
9. Procédé suivant les revendications 1 à 8, caractérisé en ce qu'on extrait le mélange réactionnel avec de l'eau avant le traitement par distillation pour la séparation de l'acide carboxylique formé lors de la réaction, correspondant à l'acide percarboxylique.
EP19780100457 1977-07-28 1978-07-20 Procédé de préparation d'oxirannes substitués par des groupes halogénoalcoyle Expired EP0000555B1 (fr)

Applications Claiming Priority (2)

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DE2734086 1977-07-28
DE19772734086 DE2734086A1 (de) 1977-07-28 1977-07-28 Verfahren zur herstellung von halogenalkylsubstituierten oxiranen

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EP0000555A1 EP0000555A1 (fr) 1979-02-07
EP0000555B1 true EP0000555B1 (fr) 1982-02-10

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EP (1) EP0000555B1 (fr)
JP (1) JPS5427514A (fr)
AT (1) AT358058B (fr)
CA (1) CA1120048A (fr)
DD (1) DD138066A5 (fr)
DE (2) DE2734086A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2456096A1 (fr) * 1979-05-10 1980-12-05 Solvay Procede pour la fabrication d'oxydes d'olefines

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1535313A (en) * 1975-02-04 1978-12-13 Interox Chemicals Ltd Production of peracids and of epoxides
DE2519297B2 (de) * 1975-04-30 1981-05-14 Bayer Ag, 5090 Leverkusen Verfahren zur kontinuierlichen Herstellung von Propylenoxid

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AT358058B (de) 1980-08-25
EP0000555A1 (fr) 1979-02-07
DE2861620D1 (en) 1982-03-18
ATA544678A (de) 1980-01-15
CA1120048A (fr) 1982-03-16
JPS5427514A (en) 1979-03-01
JPS6236030B2 (fr) 1987-08-05
DE2734086A1 (de) 1979-02-22
DD138066A5 (de) 1979-10-10

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