DE715112C - Process for the preparation of esters substituted in the acid radical - Google Patents

Description

A method for representation on the v Sä acid residue substituted esters have been found to be valuable DAB passes to a new class of organic compounds _ when the oxygen b.zw. Sulfur alkylated, cycloalkylated, aralkylated or arylated oxy or mercapto fatty acids or their derivatives and substitution products are esterified with aliphatic or resin or nitrous compounds containing at least one hydroxyl or mercapto group and at least 12 carbon atoms.

As derivatives of the oxygen or sulfur in the Way substituted oxy or mercapto fatty acids come z. B: by halogen, oxy, Sulphonic acid, carboxyl groups or hydrocarbon radicals or basic radicals and the like. Like. Substituted products of the type mentioned into consideration, the fatty acid residue : may contain a normal or branched chain.

Aliphatic, resin or naphtha compounds containing hydroxyl groups you can use alcohols with a straight or branched carbon chain, so z. B. the products made by hydrogenation of fatty acids, naphthenic acids, resin acids, Oxidation of paraffins, cleavage of waxy substances and the like. Man can also use the appropriate mercapto compounds. Also polyhydric alcohols or mercaptans can be built with the same success. of connections of the class claimed above. The hydroxyl groups or mercapto groups containing compounds can be saturated or unsaturated in nature.

The compounds mentioned which contain the hydroxyl or mercapto groups contain, in turn, substituents of all kinds, such as carboxyl groups or their derivatives, halogens. Ether groups, sulfonic acid groups and the like.

The components are esterified in a manner known per se with the free acids, optionally in the presence of catalysts. One can also use functional derivatives of acids such as chlorides, anhydrides, salts or apply the principle of L esterification.

You can also proceed in such a way that instead of the oxy compounds their reactive derivatives, such as mineral acid esters or ester salts or alcoholates, applies.

The new compounds have z. T. emulsifying properties. You can z. B. in the fragrance industry or as a plasticizer and the like. Use. Insofar as they have water-solubilizing groups, they have soap-like properties. They also serve as starting materials for further conversion products. Example i 186 parts by weight of dodecanol- (i) are dissolved in approximately the same volume of carbon tetrachloride. One leads to this solution ter stirring 17.3 parts by weight Plietiövacety-1- chloride at normal temperature. The soon under warming. any reaction supports inanan. slow heating to about 70 °, where salt, acid escapes in the stream. After finished (#i, Implementation is distilled the tetrachlor coal stalls with or without a vacuum. Of the remaining esters solidify when put in cold water as soon as a colored to solve. waxy pale; he melts at 31-. The new @ "connection has a , # cbwacIlen pleasant smell. example To .2 () and Oetadecanol- (i), in the same Amount of 7. carbon dioxide dissolved at about 40` 126 g @henoyacetyl chloride added dropwise with stirring. the rapid reaction is prevented by heat to boiling temperature in 2 to 3 hours which led to the end. After evaporation of the Carbon tetrachloride is often used later stood in ice water and sucks this then from the rapidly solidifying ; \ - aclis-like mass ah. .from alcohol to- crystallized, the ester shows the melting point 55 ' . Like dodecanol- (i) and octadecanol- (i) are also @ esadec.a.nol- (1 = 1, tetradecanol- (i) as well as ;: niche of these alcohols by means of Esterified plienoxvacetyl chloride. The esters of the higher alcohols form waxy : Masseil. The phenoxy acetic acid lexadecyl ester melts at about 4; 7 '; the corresponding corresponding F'lienoxv-acetic acid tetradec # -lester be sits the melting point 39 ' . Example 3 509 oleine coliol, which in 6n cin3 tetra- chlorocarbon are dissolved, 32 - 1'lieno @ yacetylclilorid to 75 ° with stirring up to the @ ufliöreii of the hydrochloric acid development heated. After evaporation of the solution means of the ester thus obtained, the one syrupy, almost colorless oil, too @ i-other implementations can be used. Example 1 400 tons by hydrogenation of the coconut alcohol mixture available in fatty acids clell nlit 30-19 Plieno-xvacetic acid in the hydrochloric acid flow or ini nitrogen flow with liata- Iy-sators, such as boric acid, Zn Cl. o. the like .. on 1000 heated; with gradual increase the temperature of 150 °, the esterification was completed within 5 hours. The disfiguring ester mixture forms a slightly brownish oil. Instead of the Plieno_-xyessig- siitire can be used in the example above also core-self-related plienoxy-acetic acid, such as B. the -a-carboxyplienoxyacetic acid, the Naphtlioxyessigsäuren, the mono- or 1'.clvchlc: rphenoyacetic acids, the mono- or 1 @ isulfophenoyessi-acid and d-1. more, further die _ithotyacetic acid, S -: @ t @ v @ t @ i @ g @ vkol- acid. S-Plienvltliioglylcolic acid and nutrients Connect, use lun-en, which is on a sour- o (1, -r i; it-substituted alkyl-, aryl. Arallcyl or : lvdroar @ best wear. Example 5 i II g one by oxidation of paraffin available -ill: oholgeinisclies (Acetylzalil --- 12) «-erden finit 76g phenoxyacetic acid ini Hydrochloric acid stroin to 12 @ - # for 6 hours heated. here I'lieno #: vessigsäul-e is dar acii VoIlkoirinien disappeared and a syrup feed A little ester mixture was formed. Läl: lt one 1701.f ' 1'henoLVacetvlc111 «rid aiif a solution of 2 ::? g one by Ox -, - datiol available from paraffin _ @ alcohol mixes in 50o cni @ L'etr-aclilorlzolileiistof with stirring hi 75 - two hours lall- act, so he one holds after evaporation of the 1st by means of a finite quantitative yield same syrupy mixture of the 1st. Example 6 A mixture of equal parts Tliiodigiyi-zol- acid (COOH # CH.># S # CH, # COOH) and priln.-n-Dodecylalkoliol is ini stick- rush current for about 10 to 15 hours heated. The temperature -is all- I IE ' like that. increased from 126 # to 170- . That The reaction mixture is poured out of ice, finite Soda neutralized and the N atriunisalz des llonododecyl ester of thiiodolvlcalic acid, # precipitated with table salt. It represents a white, dough-like mass. The aqueous solutions "s of the salts foam well. example 6o parts of thiodiglycolic acid "earths in similar Licher way as in Example 6 with 90 parts Oleinal coliol, optionally in the presence of esterification catalysts while about 12 hours on idn to 2oor in weak A stream of nitrogen heated with stirring, whereby: @i. the higher temperatures only for a short time held «- ground. - The resulting ester represents a brown that freezes in the cold Oil. It is in water after adding Slightly cloudy soda soluble: #lie Solution foams well. Example 8 95 parts by weight of primary n-dodecylall,: oli (_) l. «-Erden with 54 parts by weight of the lactone l; - Oxyäthoxvessigsiiure in a nitrogen stream heated to 150 to 16o ° for about 6 hours with thorough stirring. The result is B-Oxyäthoxy acetic acid n-dodecyl ester in very good yield. The ester tends to decompose during distillation. EXAMPLE 9 100 parts by weight of primary n-octadecyl alcohol are reacted with 42 parts by weight, by weight, of the lactone mentioned in Example 8 within 7 hours at 160 to 150 degrees. The resulting ß-Oxyäthoxyessigsäure-n-octadecyl ester is of a waxy consistency ..

Example 10 10 parts by weight of the alcohols corresponding to the coconut oil fatty acids (average molar weight 2oo) are reacted with 61.2 parts of the lactone of β-oxyethoxyacetic acid at 125 ° to 175 ° within 9 hours. EXAMPLE 100 parts by weight of primary n-dodecyl mercaptan are dissolved in 300 parts by weight of pyridine. 85 parts by weight of phenoxyacetyl chloride are slowly added to this solution with simultaneous heating. This is followed by heating to 10 ° for an hour.

The S-dodecyl ester of phenoxythioesetic acid of the formula Ce, H5 # O # CH @ CO # S # C , 2 H; 2, is a colorless liquid with a very faint odor. Bp = 2090. Example 12 182 parts by weight of S-benzylthioglycolic acid and 268 parts by weight of oleic alcohol are heated for a prolonged period to about 150 ° while stirring and passing through an inert gas. The mixture is then allowed to cool and then washed out with soda solution. After the unreacted oleic alcohol has been distilled off in vacuo, the S-benzylthioglycolic acid ester of oleic alcohol is obtained as a clear, pale brown oil. EXAMPLE 13-158 parts by weight of cyclohexyloxyacetic acid are heated to about 150 ° with 268 parts by weight of oleic alcohol while stirring and passing through an inert gas. That. The reaction mixture washed with soda solution is purified in vacuo. The cyclohexyloxyacetic acid ester of oleic alcohol passes over under 2 mm diameter at 225 to 235 ° as an almost colorless C51. EXAMPLE 14 550 parts by weight of phenoxyacetic acid chloride are slowly added at 0 ° to a solution of 100 parts by weight of the tri- [12-oxystearic acid] glycerol ester in 300 parts by weight of pyridine. The solution is then heated to the boil until the reaction is complete. After the pyridine has been distilled off and washed with water, the di- [phenoxyacetyl] derivative of the tri- [i2-oxystearin] glycerol ester is obtained as a pale, wax-like mass.

It has already become known, esters of such oxy fatty acids, which are etherified on the oxygen by an isoalkyl radical. It deals These are esters in which lower aliphatic alcohols, such as ethyl alcohol and isopropyl alcohol, or benzyl alcohol or phenols are used to form esters. The esters obtained are intended to be used as solvents. With the present Invention, however, such substituted esters are produced, with your: higher, Saturated or unsaturated, aliphatic, containing at least 12 carbon atoms or hydroaromatic alcohols can be used for icing.

By introducing higher aliphatic or hydroaromatic According to the present invention, residues are obtained from substances which have a lipophilic character own. This property is similar to that obtained with that known method of operation Products not to.

Claims (2)

PATENT CLAIMS: i. Process for the representation of voii substituted in the acid residue Esters of aliphatic or hydroaromatic oxy or mercapto compounds, thereby characterized in that one alkylated on the oxygen or on the sulfur, cycloallcylated, aralkylated or arylated oxy or mercapto fatty acids or their derivatives and Substitution products with such aliphatic or resin or \ taphthene compounds esterified, the at least one hydroxyl or mercap, togruppe and at least Contain i2 carbon atoms. 2. The method according to claim i, characterized in that there .ß one alkyloxy, aryloxy, aralkyloxy or cycloalkyloxyacetic acids or the corresponding mercapto compounds used as acid components.