DE1041029B - Process for the preparation of vic-acyloxy-halogen derivatives of aliphatic fatty acids having 16 to 22 carbon atoms or their esters which are suitable as plasticizers - Google Patents

Description

GERMAN

The invention relates to a method for production of vic.-acyloxy-halogen derivatives of aliphatic fatty acids having 16 to 22 carbon atoms, the at least one group in the chain

X RCO-OR

CH

CH

own. Here, X denotes chlorine or bromine and R denotes hydrogen or a lower alkyl group, in particular Methyl. The acids can also optionally with 1- to tetrahydric saturated aliphatic alcohols be esterified.

The vic.-acyloxy-halostearic acids are particularly important and their alkyl esters, which have the general formula

X RCO-O

CH- (CH ₂ ) ₇ -COOR '

CH ₃ (CH ₂ ) ₇ - CH

Process for the production of als
Plasticizer suitable vic-acyloxy-

Halogen derivatives of aliphatic

Fatty acids with 16 to 22 carbon atoms

or their esters

Applicant:

Rohm & Haas Company,
Philadelphia, Pa. (V. St. A.)

Representative: Dr.-Ing. Dr. jur. H. Mediger, patent attorney, Munich 9, Aggensteinstr. 13th

Claimed priority:
V. St. v. America April 16, 1954

own. R is a hydrogen atom or a lower alkyl group, preferably methyl or ethyl, R 'is a 1-valent hydrocarbon radical with 1 to 14 carbon atoms, and X can be chlorine or bromine.

The compounds mentioned and their structural and geometric isomers are advantageously suitable as Plasticizers for plastics such as polyvinyl halide resins. They also provide valuable intermediates that can be converted into a variety of useful derivatives. For example, let they can easily be converted into the corresponding dioxycarboxylic acids with the aid of dilute aqueous alkali lye; these in turn can then be esterified and converted into the corresponding carbonic acid ester by treatment with phosgene are converted, which are also excellent Plasticizers for vinyl halide resins. The acyloxy halogen derivatives can also with caustic alkali melted and thereby converted into mono- and dicarboxylic acids, for which there is great demand. With the help of alcoholic potassium hydroxide solution, the acyloxy halo stars also produce the corresponding epoxy esters, which are widely used as plasticizers Stabilizers for polyvinyl halide resins can be used.

The acyloxy-halogen derivatives of aliphatic fatty acids with 16 to 22 carbon atoms are prepared according to the invention by adding a corresponding unsaturated fatty acid or its ester with tertiary alkyl hypochlorite, preferably tert-butyl hypochlorite, and circr saturated aliphatic acid such as ameicarboxylic acid Acetic acid, propionic acid, is reacted. The use of formic or acetic acid, which leads to formoxj? - cder acetoxy-halogen-Edward Francis Riener, Haddonfield, NJ (V. St. A.
has been named as the inventor

derivatives is by far preferable for reasons of effectiveness and economy.

The reaction can be carried out at a temperature which is between 0 ° C. and the boiling point of the reaction mixture. When working on an industrial scale, a temperature range is preferable from about 20 to about 6O ⁰ C. The tertiary alkyl hypohalite is expediently added at such a rate that the temperature remains below its boiling point. We recommend using an organic solvent such as tert-butanol, benzene or toluene.

The starting material is unsaturated fatty acids with 16 to 22 carbon atoms and one or multiple double bonds in question. Such acids are e.g. B. oleic acid, erucic acid, eleostearic acid, linoleic, Linolenic, clupanodonic, palmitolic and palmitolenic acids.

All of these acids come in animal and vegetable sources Oils, e.g. B. in sardine oil, whale oil and soybean oils, rapeseed and linseed. They are easily obtained by saponifying the natural oils. the Esters of fatty acids, which are produced according to the method of

5c finding converted into vic.-acyloxy-halogenated fatty acid ester are those of oil-hydric alcohols, e.g. B. ethyl, n-isopropyl, η-butyl, sec. Butyl, tert. Butyl, tert. Amyl, n-octyl, 2-ethylhexyl, Octadecyl, lauryl, cyclohexyl and benzyl alcohol,

«09 658/415

or of polyhydric alcohols, such as ethylene glycol, 1,2-propylene glycol, 2-ethylhexanediol-1,3, butanediol-1,2, Biitanediol-1,3, butanediol-1,4, dodecanediol-1,12, or from Polyalkylene glycols, such as diethylene glycol, glycerol, pentaerythritol, and the isomers and homologues of the named alcohols.

According to the process according to the invention, the derivatives of mixed esters, such as ethylene oleate linoleate, Glycerol dioleate monolinoleate, butylene linoleate oleate, etc., getting produced. The naturally occurring vegetable and animal oils can also be converted into vic.-acyloxy haloesters be transferred. These oils are mixed esters of glycerine and a mixture of the above Acids. In particular, the oils from soybean, corn, cottonseed, safflower, sunflower, Sesame, poppy seeds, walnut, peanut, linseed, sardine oil, perilla oil and fish oils in general. There All of these esters contain unsaturated aliphatic compounds, they can easily be incorporated into the compounds with Convert halogen and acyloxy substituents.

The method of the invention differs fundamentally from a known method in which by reacting tetrahydrofuran carboxylic acid or its esters with acyl halides, l-halo-4-acyloxy compounds which are not as useful as those obtained by the present process are vic.-Halogenacyloxyverbindungen and z. B. do not epoxidize.

According to another known process, haloalkoxy compounds are obtained by reacting free halogen and an alcohol with unsaturated aliphatic carboxylic acids or their esters. The temperature must not exceed ^{25 ° C.}

The advantage of the process of the invention is that it requires neither free halogen nor alcohols or heterocyclic compounds for its implementation, but uses a tert-alkyl hypochlorite and takes place at temperatures between ⁰ ° C. and the boiling point of the reaction mixture. Tert-alkyl hypochlorites can be obtained in a simple manner, for example by the action of an organic hypochlorite, ζ. B. calcium hypochlorite on a tert-alkanol, such as. B. tert-butanol.

The products of the process are very reactive. You can z. B. easily epoxidize and are in this form superior and valuable plasticizing and stabilizing agents for vinyl halide resins. The products of the process can also be converted into cyanohydrins, for which purpose the halogenacyloxy compounds are not capable.

According to an older process, it was known by reacting simple, one ethylene group-containing Compounds such as ethylene, propylene, butylene with tert-butyl hypochlorite in the presence of a strong Acid to produce chlorohydrin ester. However, the process does not work with compounds of higher molecular weight executable.

It should be mentioned that mixtures of isomeric compounds are normally obtained as it is practical it is impossible to carry out the reaction in such a way that the halogen and the acyloxyl substituents are always the same Carbon atoms of the double bonds occur.

The following examples describe the preparation of vic.-formoxy-chlorine and acetoxy-chlorine derivatives Fatty acids and their allyl esters as well as a vegetable oil, which is an ester of a polyhydric alcohol (glycerin) represents. The corresponding bromine derivatives are prepared by adding an equivalent amount of one tert-alkyl hypobromite instead of tert-butyl hypochlorite is applied. Since the alcoholic groups of the esters are intact under the conditions described and since all products are oils, the different esters are used according to the same in the examples specified method.

example 1

A mixture of 141.3 g (0.5 mol) of oleic acid, 0.3 1100% formic acid and 1 g of p-toluenesulfonic acid is cooled to 12 ° C. in a reaction vessel equipped with a thermometer, stirrer and reflux condenser and, with stirring, at 12 ° C. 60 g (0.55 mol) of tert-butyl hypochlorite were added up to 16 ^{° C. within one hour.} The cooling is then stopped, the temperature of the mixture is allowed to rise to about 30 ^° C. with stirring and stirring is continued for 17 hours at about this temperature. Then it is poured into 1 l of water and extracted with 11 benzene. The benzene solution is carefully washed with water and then freed from the benzene. The yield is 179 g (theory: 181.5 g) of a mixture of 9,10- and 10,9-formoxychlorostearic acid. It is a straw-colored oil with a refractive index η ² S = 1.4690. The composition was confirmed by analysis. Iodine number: calculated 0, found 0.1. Acid number: calculated 154, found 145.Saponification number: calculated 464, found 430.

Example 2

In the same manner as in Example 1, a mixture of 183.3 g (0.5 mol) n-hexyl oleate, 46 g (1,0MoI) 98 ° / ₀ formic acid and 0.5 g of p-toluenesulfonic acid under stirring at From 10 to 15 ° C., 60 g (0.55 mol) of tert-butyl hypochlorite were added dropwise over the course of about one hour. The mixture is then stirred at room temperature for 17 hours, after which it is worked up in the same manner as in Example 1. A total of 220 g of a light oil with a refractive index of 1.4590 is obtained. The analysis corresponds approximately to a mixture of n-hexyl-9,10- and 10,9-formoxychlorostearate.

Example 3

A mixture of 94 g (0.5 mol, calculated on the double bond content) of soybean oil, 0.2 198% formic acid and 0.5 g of p-toluenesulfonic acid are stirred at 10 to 15 ° C within about 45 minutes 60 g (0.55 mol) of tert-butyl hypochlorite were added. After cooling has stopped, the mixture is stirred at room temperature for 19 hours and then extracted and purified as in Example 1. 127.5 g of a Poty (formoxychlor) soybean oil with a refractive index n * g = 1.4802 are obtained. A chlorine content of 13.1% was found, calculated 13.2%.

Example 4

47.7 g ( 0.44MoI) tert-butyl hypochlorite added. The mixture is then stirred for 2 hours at 10 to 20 ° C, whereupon the temperature is allowed to rise and. stirred again at room temperature for 16 hours. Working up is carried out in the manner described. 188 g of a pale oil are obtained which, according to analysis, is a mixture of 9,10-acetoxychlorostearic acid and 10,9-acetoxychlorostearic acid n-hexyl ester, the refractive index n ² g of which is 1.4595.

Example 5

To a mixture of 376 g (2 mol, calculated on the double bond content) soybean oil, 0.41 glacial acetic acid, 2 g of p-toluenesulfonic acid and 240 g of tert-butyl alcohol 240 g of tert-butyl hypochlorite are slowly added

and the reaction mixture was stirred at room temperature for 17 hours. After the usual work-up, 554 g of a poly (acetoxychloro) soybean oil are obtained, the identity of which was confirmed by the analysis. Refractive ^{Index Wt 0} = 1.4774.

Example 6

In a funnel equipped with a stirrer, thermometer and dropping provided 500 cc flask, a mixture of 59.2 g {0.2 mol) of methyl oleate, 20 cc (0.435 mole) of 90 ° / ₀ formic acid and 0.5 g of p-toluenesulfonic acid 25.8 g (0.21 mol) of tert-amyl hypochlorite were added with stirring at 10 to 15 ° C. over the course of 15 minutes. A significant development of heat occurs here and the color of the reaction mixture lightens slightly towards the end of the addition. The temperature is allowed to rise slowly to 28 ° C. and stirring is continued for 18 hours. The mixture is then poured into 200 ecm of water, extracted with 150 ecm of benzene, the lower organic phase is separated off and the upper oily phase is washed seven times with 100 ecm of water each time until it is acid free. The acid-free organic phase is freed from benzene in a vacuum on a steam bath and 75 g (theory = 75.5 g) of a pale yellow liquid are obtained; (VZ = 400 found, 446 calculated; JZ = 0.60 found, 0 calculated; AN = 1.8 found, 0 calculated. Chlorine content = 10.0% found, 9.4% calculated).
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Claims (1)

PATENT CLAIM: Process for the preparation of vic.-acyloxy-halogen derivatives of aliphatic which are suitable as plasticizers Fatty acids with 16 to 22 carbon atoms or their esters, characterized in that that one is a mono- or polyunsaturated fatty acid or its esters or mixed esters with saturated 1- to tetrahydric alcohols with a tert-alkyl hypochlorite or bromite and a saturated aliphatic monocarboxylic acid, optionally in the presence an organic solvent and expediently at an elevated temperature below the boiling point of the hypohalite. Considered publications:
U.S. Patent Nos. 2,054,814, 2,333,771, 392,100.