DE1188067B - Process for the production of unsaturated aliphatic aldehydes and ketones - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C07c

German class: 12 ο -7/03

Number: 1188 067

File number: D 35238IV b / 12 ο

Filing date: January 24, 1961

Opening day: March 4, 1965

The present invention relates to the preparation of unsaturated aliphatic aldehydes and Ketones.

The production of acrolein by reacting propylene with aqueous acidic mercury sulfate is already known. In this process the mercury salt is reduced to mercury sulfate.

The inventive method for the preparation of unsaturated aliphatic aldehydes and ketones by reaction of olefins with acidic aqueous ίο solutions of mercury salts is now characterized by that the olefin with an aqueous solution or suspension of mercuric perchlorate or the mercury salt of a sulfonic acid at a temperature of 50 to 150 ° C, the said solution or suspension nor the acid corresponding to the mercury salt in one concentration from 0.1 to 10 normal and the mercury salt in a proportion between 0.1 and 100 percent by weight, Calculated as mercury metal based on the weight of the acid solution.

The olefin used in the process of the invention is suitably a lower monoolefin up to 6 carbon atoms, ζ. Β. Propylene, butene- (I) or isobutene. The use of propylene, that is converted to acrolein is particularly preferred.

Suitable sulfonates are e.g. B. Mercuri-p-toluenesulfonate and mercurimethanesulfonate.

The reaction can optionally be carried out under pressure.

The reaction can e.g. B. be done by adding propylene to a heated aqueous solution or suspension of the Mercury salt introduced into the corresponding acid and the acrolein from the exiting gas is won. The propylene can also be used in a first stage in a cold solution of the mercury salt absorbed and the reaction mixture can then be heated in a second stage, the produced Acrolein is distilled off; the distillation can be facilitated by adding propylene or an inert Gas is passed through the mixture.

In one embodiment of the invention, the mercury perchlorate or sulfonate is formed in situ in the reaction mixture by oxidation of the corresponding mercury salt or of metallic mercury with corresponding ferric salts as the oxidizing agent. In this case, the mercury salt need only be present in catalytic amounts and can be added either as a mercury salt, as a mercury salt or as metallic mercury, since the ferric salt is used by oxidation of the olefin for the process of producing unsaturated
aliphatic aldehydes and ketones

Applicant:

The Distillers Company Limited,
Edinburgh (Great Britain)

Representative:

Dr. W. Schalk, Dipl.-Ing. P. Wirth,
Dipl.-Ing. GEM Dannenberg
and Dr. V. Schmied-Kowarzik, patent attorneys,
Frankfurt / M., Große Eschenheimer Str. 39

Named as inventor:

George William Godin, London;

John Bentley Williamson, Sutton, Surrey

(Great Britain)

Claimed priority:
Great Britain 30 January 1960
(3375, 3376)

Aldehyde formed mercurous salt is constantly oxidized back into the mercuric form. The amount of ferric salt is expediently 5 to 50 times the mercury salt present, calculated as metallic Mercury. During the reaction, the ferric salt is converted into the ferric form.

Suitable ferric salts are ferric perchlorate and ferric toluenesulfonate and ferrimethanesulfonate.

It was already known to produce acrolein by adding propylene to a solution of mercury sulfate initiates. In this process, the insoluble mercurosulphate is produced, which is then subsequently produced must be converted back into the mercury sulfate. This oxidation now causes considerable difficulties, there z. B. the use of air as an oxidizing agent is not possible. Through the present Invention, this difficulty is eliminated, since the mercuroperchlorate or the mercurosulfonates are more easily soluble and thus an oxidation of the monovalent mercury compounds to the divalent ones Mercury compounds can easily be made with air.

The problem of overcoming the difficulties encountered when using mercurosulfate

509 517/485

Claims (5)

occur, but is not simply to look for a more soluble monovalent mercury salt, since it has been found that the use of mercuric chloride, phosphate, nitrate or trichloroacetate, some of which can also be converted into relatively easily soluble mercury salts, for the present method is not useful. It is also known to produce acrolein from propylene in the gas phase by adding a mixture of propylene, oxygen and optionally inert gases at temperatures of, for. B. 300 to 500 ° C passes over certain catalysts. The yields achieved in these known processes to be carried out in the gas phase are consistently good. The difference between the known processes and the claimed process is that, according to the invention, work is carried out in the liquid phase at significantly lower temperatures and that, as a result, it is possible to work with significantly simplified and therefore much cheaper apparatus. The yields are roughly the same in both processes. The space and time yields are also comparable in the claimed process at corresponding reaction temperatures. Technology is enriched when a compound that can normally only be produced at high temperatures in the gas phase can be obtained with comparable yields even at lower temperatures in the liquid phase. The process according to the invention is further illustrated by the following examples, in which parts by weight and parts by volume have the same ratio to one another as kilograms to liters. Example 1 21.6 g (0.10 mol) of mercury dioxide were dissolved in 100 ecm of 2.2 normal aqueous perchloric acid. Propylene was then passed through the solution with stirring until it was no longer absorbed. The increase in weight indicated that 4.13 g (0.098 mol) of propylene had been absorbed into the solution. The mixture was heated to 95 ° C. and nitrogen was bubbled through the solution at a rate of at least 90 ecm. 0.91 g of acrolein (0.016MoI) and 2.85 g of propylene (0.068MoI) were obtained from the outflowing gases within 283 minutes. The acrolein formation efficiency based on the difference between absorbed and recovered propylene was 53%. Example 2 21.6 parts by weight of mercuric oxide (HgO) were dissolved in 100 parts by volume of aqueous 3N-perchloric acid, resulting in a solution of mercuric perchlorate in about 1N-perchloric acid. Propylene was added to the solution until nothing was absorbed. The mixture was then heated to 95 ° C. and propylene was passed through it at a rate of 90 parts by volume per minute. 0.81 parts by weight of acrolein were produced in 4 hours, which corresponded to a yield of 58% of theory, based on the conversion of the added mercuric salt into the mercuric form. An analysis of the gases flowing out of the reaction vessel showed that the acrolein is obtained in a space-time yield of 0.16 g of acrolein per liter of solution per minute. If the reaction temperature is increased by 40 to 45 ° C., the space-time yield increases by a factor of 10 to 12. Example 3 ο 21.6 parts by weight of mercury dioxide and 51.7 parts by weight of p-toluenesulfonic acid were dissolved in 100 parts by volume of water, which resulted in a solution of mercury-p-toluenesulfonate in about 1 n-p-toluenesulfonic acid. Propylene was added to the solution until nothing was absorbed. The mixture was then heated to 95 ° C. and propylene was passed through it at a rate of 90 parts by volume per minute. 1.04 parts by weight of acrolein were produced in 7 hours, which corresponded to a yield of 75% of theory, based on the conversion of the mercuric salt used into the mercuric form. Example 4 21.6 parts by weight of mercuric oxide (HgO) were dissolved in 100 parts by volume of aqueous 3N-methanesulphonic acid, resulting in a solution of mercurimethanesulphonate in about 1n-methanesulphonic acid. Propylene was added to the solution until nothing was absorbed. The mixture was then heated to 95 ° C. and propylene was passed through at a rate of 90 parts by volume per minute. 1.14 parts by weight of acrolein were obtained in 6 hours, which corresponds to a yield of 81% of theory, based on the conversion of the mercuric salt used into the mercuric form. Example 5 21.6 parts by weight of mercuric oxide were dissolved in 100 parts by volume of aqueous 3N-methanesulphonic acid, which resulted in a solution of mercurimethanesulphonate in about 1n-methanesulphonic acid. The solution was heated to 95 ° C. and a mixture of isobutene and nitrogen was passed through it at a rate of 10 parts by volume of isobutene and 90 parts by volume of nitrogen per minute. 0.43 parts by weight of methacrolein were obtained in 6 hours, which corresponds to a yield of 24% of theory, based on the conversion of the mercuric salt used into the mercuric form. Example 6 Propylene was passed at a rate of 90 parts by volume per minute with stirring through a mixture, heated to 95 ° C., of 30 parts by volume of a 2 molar solution of ferriperchlorate and 4 parts by weight of mercurooxide in 79 parts by volume of 1.4 n-perchloric acid. 0.45 parts by weight of acrolein were obtained from the escaping gas in 8 hours. g patent claims: 1. Process for the preparation of unsaturated aliphatic Aldehydes and ketones by reacting olefins with acidic aqueous ones I 188 067 Solutions of mercury salts, characterized in that that the olefin with an aqueous solution or suspension of mercuric perchlorate or the mercuric salt of a sulfonic acid at a temperature of 50 to 150 ° C, said solution or suspension nor the acid corresponding to the mercury salt in a concentration of 0.1 to 10 normal and the mercury salt in a proportion between 0.1 and 100 percent by weight, calculated as mercury metal, based on the weight of the acid solution. 2. The method according to claim 1, characterized in that the reaction with a low monoolefm with up to 6 carbon atoms, preferably propylene will. 3. The method according to claim 1 and 2, characterized in that the reaction with mercury-p-toluenesulfonate or mercurimethanesulfonate is carried out. 4. The method according to claim 1 to 3, characterized in that the mercuric perchlorate or sulfonate generated in situ in the reaction mixture by adding the corresponding mercury salts or the metallic mercury is oxidized with corresponding ferric salts. 5. The method according to claim 4, characterized in that the method with an opposite the mercury salt, calculated as mercury metal, 5 to 50 times the amount of ferric salt is carried out. Considered publications:
German documents No. 1103 911,
1001673; British Patent No. 821999;
U.S. Patents No. 2,197,258, 2,270,705,
334091; Comtes renduds hebdomadaires des seances de l'academie de France, 126, 1898, p. 1145; H. Remy, Textbook of Inorganic Chemistry, so 2, 1959, p. 549. Legacy Patents Considered:
German Patent No. 1109 659. 509 517/485 2.65 © Bundesdruckerei Berlin