DE1117581B - Process for the production of epoxies - Google Patents

Description

The invention relates to a process for the production of epoxides from ethylenically unsaturated organic compounds Links.

The production of epoxides by reacting ethylenically unsaturated compounds with an aldehyde monoperacylate is known. This reaction can be carried out by reacting a solution of the Aldehydmonoperacylates in an inert organic solvent such as acetone or acetic acid, with the ethylenically unsaturated compound at a temperature between 25 and 200 ⁰ C, the formed during the epoxidation aldehyde from the reaction mixture removed and the epoxide is then recovered from the reaction mixture by fractional distillation.

According to the present invention, a process for the preparation of epoxides is ethylenically unsaturated Compounds using aldehyde monoperacylates have been proposed which have better yields of epoxides than the known Procedure supplies.

The inventive method for the production of epoxies by converting an ethylenic unsaturated organic compound containing at least 3 carbon atoms in the molecule with the Monoperacylate of a low molecular weight, aliphatic aldehyde in the liquid state at a temperature between 25 and 200 ° C, preferably in the presence of an inert organic solvent and expedient with removal of the aldehyde released during the epoxidation from the reaction mixture now characterized in that the epoxidation in the presence of a Lewis acid or a Lewis base performs as a catalyst.

According to the invention, many ethylenically unsaturated organic compounds that at least Containing 3 carbon atoms in the molecule, are epoxidized. Suitable starting compounds are, for. B. Olefins, unsaturated aldehydes, ketones or carboxylic acids, esters, alcohols, ethers and halogenated Hydrocarbons that contain ethylenically unsaturated bonds. The method is particularly suitable for the epoxidation of propylene, butylenes, pentenes, hexenes, heptenes, octenes, butadiene and Styrene.

The monoperacetates or monoperpropionates of the low molecular weight aliphatic are preferred Aldehydes, especially acetaldehyde monoperacetate or propionaldehyde monoperpropionate, are used.

The reaction of the aldehyde monoperacylate with the ethylenically unsaturated compound is preferred in the presence of a for the production of the

Process for the production of epoxies

Applicant:

The Distillers Company Limited,
Edinburgh (Great Britain)

Representative: Dr. W. Schalk, Dipl.-Ing. P. Wirth,

Dipl.-Ing. G. E. M. Dannenberg

and Dr. V. Schmied-Kowarzik, patent attorneys,

Frankfurt / M., Große Eschenheimer Str. 39

Claimed priority:
Great Britain of January 10, 1957 (No. 933/57)

John Bentley Williamson, Epsom, Surrey

(Great Britain),
has been named as the inventor

Monoperacylates suitable solvent, especially acetic acid, carried out. The reaction temperature at which good yields are obtained is preferably between 40 and 120 ° C. In any case, the optimal epoxidation temperature, which is determined by the type of compound to be oxidized, determined in a preliminary test. According to a preferred embodiment, a cold solution of the aldehyde monoperacylate is added to the heated Introduced reaction mixture of the ethylenically unsaturated compound.

The catalysts used in the process according to the invention are acids or bases, according to the assumption of Brönsted, Lowry and Lewis (see Journal of the Franklin Institute, Philadelphia, Vol. 226, pp. 293 to 313) Acid compounds that release a proton from the molecule, and base compounds, that can accommodate a proton in the molecule are. Examples of those which can be used in acetic acid solution acidic catalysts are organic and inorganic acids that are stronger than acetic acid, such as formic acid and sulfuric acid, and acid salts such as ferric chloride. Examples of in acetic acid solution basic catalysts that can be used are ammonia, tertiary organic amines, such as pyridine, and alkali salts weak organic and inorganic acids, alkaline earth salts of weak organic and inorganic acids Acids and the oxides, hydroxides, carbonates, and bicarbonates of these metals, which in the presence of

109 740/575

Acetic acid easily provides the corresponding metal acetate.

The optimum catalyst concentration depends on the type of individual catalyst. For sodium acetate the suitable concentration range is about 0.001 to 1.0 weight percent, preferably from 0.005 to 0.1 percent by weight, based on the reaction mixture.

When using an acidic catalyst, the catalyst concentration should be low so that a notable reaction between the epoxy produced and that also formed during the epoxidation Carboxylic acid, e.g. B. acetic acid is avoided.

The epoxidation is preferably carried out with an excess of the ethylenically unsaturated compound carried out. If acetaldehyde monoperacetate is used as an epoxidation agent, then in the implementation Acetaldehyde and acetic acid were formed in addition to the epoxide. The acetaldehyde becomes appropriate immediately after its formation from the reaction mixture continuously, e.g. B. by distillation or Extraction with a solvent.

The epoxide can be extracted from the reaction mixture in a manner known per se, e.g. by fractional distillation and crystallization.

The epoxides prepared according to the invention are valuable intermediates for the preparation of many other substances, for example from resins and lubricants, they can also act as solvents, plasticizers or pesticides are used.

It is known that ethylenically unsaturated compounds by acetic acid solutions of peracetic acid and sodium acetate can be epoxidized. However, it could not yet be deduced from this be that sodium acetate or Lewis bases generally also when using monoperacylates of aliphatic aldehydes for the production of epoxides are suitable catalysts. From the following The very high yields achievable according to the invention can be seen in examples. Furthermore, it was undoubtedly also very surprising that Lewis acids were used as catalysts according to the invention are useful because it is known that acidic compounds readily cause cleavage of epoxy rings.

The following examples illustrate the process of the invention.

example 1

A solution containing acetaldehyde monoperacetate was prepared in a known manner in that equimolar amounts of acetaldehyde dissolved in acetic acid are added at a temperature of about 3 ° C and peracetic acid mixed so that the peroxide concentration of the finished solution is 2.7 moles per liter fraud. The mixture was allowed to stand for about 1 hour at a temperature of about 3 ° C.

The acetaldehyde monoperacetate solution was used in the presence of various amounts of sodium acetate The catalyst was added to a solution of 1-octene in acetic acid kept at 80 ° C. and the reaction mixture was stirred for 5 minutes. The octene-1 was in a ratio of about 50 percent by volume, based on the reaction mixture, present. That at the Reaction formed octene-1-oxide was due to treatment of the reaction product with pyridine hydrochloride after the determination of epoxy groups known procedures.

Comparatively, the procedure was carried out in the absence of a catalyst using the same Acetaldehyde monoperacetate solution carried out.

There have also been various approaches using different concentrations of the various Catalysts and carried out without a catalyst. The results are given in Table 1.

Tabel

approach
No. catalyst catalyst
concentration
in percent by weight Added
acetaldehyde
monoperacetate
in moles per liter Educated
Epoxy
in moles per liter (Molars)
yield
in ° / " Molar yield
at a
comparative
approach
without a catalyst
in ° / o 1
2
3
4th
5
6th
7th
8th
9
10
11
12th
13th
14th Sodium acetate
Sodium acetate
Sodium acetate
Sodium acetate
Barium acetate
Barium acetate
Ammonium acetate
Ammonium acetate
Pyridine
Pyridine
sulfuric acid
sulfuric acid
Ferric chloride
Ferric chloride 0.007
0.018
0.036
0.071
0.019
0.048
0.0077
0.015
0.016
0.040
0.001
0.002
0.001
0.005 0.411
0.410
0.444
0.438
0.392
0.424
0.377
0.380
0.416
0.413
0.377
0.382
0.411
0.395 0.275
0.282
0.292
0.292
0.268
0.268
0.239
0.235
0.265
0.269
0.239
0.264
0.267
0.260 66.9
68.9
65.8
66.7
68.3
63.2
63.4
62.1
63.7
65.1
63.4
69.1
65.0
65.8 58.7
59.8
58.8
61.7
58.1
59.5
57.3
55.8
58.1
59.5
57.3
55.8
63.3
61.4

Example 2

A solution containing acetaldehyde monoperacetate was prepared by taking gaseous molecular Oxygen through a mixture of equal parts by volume of acetaldehyde and acetic acid at one temperature of 2 ° C was passed through. The mixture was in a quartz vessel and was irradiated with UV light; oxygen was passed in for 4 hours

and so the acetaldehyde is converted into acetaldehyde monoperacetate.

The acetaldehyde monoperacetate solution thus prepared was as in Example 1 in the presence of a catalyst added to a 50 volume percent solution of octene-1 in acetic acid.

For comparison, the procedure was carried out in the absence of a catalyst using the same acetaldehyde monoperacetate solution carried out.

The results are given in Table 2.

Table 2

catalyst catalyst Added Educated (Molars) Molar yield concentration acetaldehyde Epoxy yield at a monoperacetate comparative approach sulfuric acid in percent by weight in moles per liter in ° / o approach Barium acetate 0.002 in moles per liter 0.247 63.0 without a catalyst No. 0.020 0.392 0.252 65.3 in ° / o 15th 0.386 56.1 16 56.1

Example 3

Acetaldehyde monoperacetate was produced by passing gaseous molecular oxygen through a mixture of equal parts by volume of acetaldehyde and an inert diluent (“Diluent A” in Table 3), which was kept at 2 ^° C. The mixture was placed in a quartz jar and was irradiated with ultraviolet light; the oxygen was passed in for 5 hours, thereby converting the acetaldehyde into acetaldehyde monoperacetate.

Then 1 ecm of the acetaldehyde monoperacetate thus produced containing solution to a mixture

from 5 ecm of the ethylenically unsaturated compound 4 ecm of an inert diluent (»Diluent B «in Table 3) and added to the catalyst. The mixture was kept at 80 ° C and stirred for the period of time indicated in Table 3 as the reaction time. Then the mixture became cooled and the amount of epoxide obtained is determined by adding the reaction product with pyridine hydrochloride was treated.

For comparison, the procedure was repeated in the absence of a catalyst. The results are recorded in Table 3; the concentrations relate to the total volume of the reaction mixture, namely 10 ecm.

Tabel

approach
No. Unsaturated
link Diluents
A. Diluents
B. catalyst 17th Octene-2 acetone acetic acid Barium acetate 18th Octene-2 benzene benzene Ferric chloride 19th Octene-2 benzene 3 ecm benzene Barium acetate 1 ecm acetic acid 20th oleic acid acetone acetic acid Barium acetate 21 Oleic acid acetone acetic acid Barium acetate 22nd Oleyl alcohol benzene 3 ecm benzene Barium acetate 1 ecm acetic acid 23 «-Methylstyrene benzene 3 ecm benzene Barium acetate 1 ecm acetic acid

Results of the comparative tests

catalyst
concentration Reaction time Added
Acetaldehyde mono
peracetate Educated
Epoxy Molars
yield Molar yield approach in %
at a
comparative in g / 100 ecm in minutes in moles per liter in moles per liter in Vo approach No. 0.021 5 0.340 0.297 87.4 without a catalyst 17th 0.007 5 0.305 0.265 86.9 80.0 18th 0.021 5 0.268 0.246 91.8 81.3 19th 0.021 5 0.336 0.269 80.1 87.0 20th 0.021 10 0.328 0.262 79.9 74.7 21 0.021 5 0.225 0.178 79.1 72.9 22nd 0.021 5 0.227 0.112 49.4 70.7 23 41.8

The epoxides of other ethylenically unsaturated hydrocarbons, non-conjugated carbonyl compounds, Ethers and halogenated hydrocarbons are produced in a similar manner. implementation made with acetaldehyde monoperacetate or propionaldehyde monoperpropionate.

Claims (4)

PATENT CLAIMS: 1. Process for the production of epoxies by reacting an ethylenically unsaturated organic compound containing at least 3 carbon atoms in the molecule with the monoperacylate of a low molecular weight, aliphatic aldehyde in the liquid state at a temperature between 25 and 200 ° C, preferably in the presence of an inert organic Solvent and expediently with removal of the aldehyde released during the epoxidation from the reaction mixture, characterized in that the epoxidation is carried out in the presence of a Lewis acid or a Lewis base as catalyst. 2. The method according to claim 1, characterized in that the inert organic solvent Acetic acid is used and the epoxidation is carried out with acetaldehyde monoperacetate. 3. The method according to claim 1 and 2, characterized in that there is a catalyst Lewis acid, which is stronger than acetic acid. 4. The method according to claim 1 and 2, characterized in that the Lewis base ammonia, a tertiary organic amine or an alkali or alkaline earth compound used in The presence of acetic acid can be converted into the corresponding acetates. Considered publications: German patent application 168030 IVd / 12 ο (= extracts German patent applications, chemistry, part I, p. 139); U.S. Patent No. 2,556,145;
Journal of the American Chemical Society, Vol. 72, 1950, p. 4316.