DE1263770B - Process for the preparation of 2-hydroxy-3-chloropropyl carboxylic acid esters - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

Number: File number: Registration date: Display day:

C07c

German class: 12 ο -27

1,263,770
F43833IVb / 12o
August 27, 1964
March 21, 1968

It is known that hydroxyhaloalkyl carboxylic acid esters can be produced by the addition of epihalohydrides to carboxylic acids to manufacture. This reaction can be carried out by adding acidic or basic catalysts, such as iron chloride, aluminum chloride, pyridine, diethylamine and triethylamine or through quaternary ammonium salts are accelerated (cf. German patent specification 708 463, USA patent specification 2 224026). as Besides the carboxylic acid 2-hydroxy-3-halo-alkyl esters, by-products are formed also isomeric compounds, such as 3-hydroxy-2-halo-alkyl and 1-hydroxy-3-halo-acyl-oxy compounds. Further By-products are the polyadducts of epihalohydrins, as they are known under the Influence of the above-mentioned catalysts arise.

The invention now relates to a process for the preparation of carboxylic acid 2-hydroxy-3-chloropropyl esters by adding epichlorohydrin to compounds containing at least one carboxy group in the presence of catalysts, characterized in that the catalysts are thioethers of the general formula R ₁ - S - R ₂ and / or sulfonium salts of the general formula

uses, in which R ₁ , R ₂ and R _{3 can be} identical or different and

a) alkyl, C ₁ to C ₁₂ , cycloalkyl, aralkyl,

b) ω-hydroxyalkyls formed by heteroatoms, such as O, S, can be interrupted,

c) cyano-ethylated oxyalkyls,

d) epoxypropyl

and X ^{e can be} a monovalent anion, preferably a halide ion.

In this process, for example, the following compounds containing carboxyl groups can be used: aliphatic monocarboxylic acid, such as acetic acid, butyric acid, stearic acid, unsaturated aliphatic monocarboxylic acids, such as acrylic acid, methacrylic acid, oleic acid, linoleic acid, elaidic acid, elaostearic acid, hydroaromatic carboxylic acid, aromatic carboxylic acids, such as hexahydrobenzoic acid such as benzoic acid, chlorobenzoic acid, nitrobenzoic acid, anisic acid, cinnamic acid, naphthoic acid, and also aliphatic di- and polycarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dichlorosuccinic acid, maleic acid, fumaric acid. In addition, di-processes for the production of
Carboxylic acid 2-hydroxy-3-chloropropyl esters

Applicant:

Paint factories Bayer Aktiengesellschaft,

5090 Leverkusen

Named as inventor:

Dr. Robert Schmitz-Josten,

5000 Cologne-Stammheim;

Dr. Gunter Frank,

Dr. Rolf Kubens, 5090 Leverkusen;

Dr. Roland Gipp, 5000 Cologne-Buchheim

merized fatty acids, such as dilinolenic acid, copolymers of unsaturated fatty acids with vinyl aromatic compounds, such as styrene or vinylbenzene, for example styrenated linseed oil fatty acids. In addition, polycarboxylic acids such as can be obtained by the addition of maleic anhydride to unsaturated fatty acids, resin acids, olefins, vinyl aromatic compounds or alkyl aromatics, such as. B. isobutenylsuccinic acid, triisobutenylsuccinic acid, dodecenylsuccinic acid, toluylsuccinic acid, a, a - [9,10 - dihydroanthrylene- (9,10)] - succinic acid or 1,2,3,4-tetrahydronaphthalene-3,4-dicarboxylic-1-succinic acid.

Aromatic di- and polycarboxylic acids are also possible, such as ortho-, iso- and terephthalic acid, Tetrachlorophthalic acid, trimesic acid, pyromellitic acid, naphthalene-2,6-dicarboxylic acid, naphthalic acid, Diphenyl-o, o'-dicarboxylic acid, Diphenyl-p ^ '- dicarboxylic acid, Diphenylmethane-p ^ '- dicarboxylic acid, stilbene, p' - dicarboxylic acid or naphthalenetetracarboxylic acid 1,4,5,8.

Examples of hydroaromatic di- and polycarboxylic acids are: Tetrahydro phthalic acid, Hexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid as well as their halogen derivatives and a number of heterocyclic carboxylic acids. Instead of Polycarboxylic acids can also use the corresponding anhydrides in the presence of water or of Glycols are used (see German Auslegeschrift 1 168 907).

809 519/702

The carboxylic acids used as starting compounds can, in addition to the carboxyl group, also still have other substituents in the molecule, such as e.g. B. ester groups, ether groups, carboxyl groups or hydroxyl groups. For example, there may be mentioned: polycarboxylic acids containing ester groups, as they are by Esterification of polyhydric alcohols, such as glycol, trimethylolpropane or hexanetriol, with an excess obtained on di- or polycarboxylic acids or by reacting the polyhydric alcohols with the Polybasic acid anhydrides can be prepared; also polyesters with terminal carboxyl groups. Among the carboxylic acids containing ether groups, there may be mentioned diglycolic acid, by reaction of Halocarboxylic acids with diphenols or phenol carboxylic acids obtainable polycarboxylic acid, such as. B. Reaction products of 4,4'-dioxydiphenyldimethylmethane with chloroacetic acid, and also hydroquinone diacetic acid or salicylacetic acid, ethylene glycol bis (p-carboxyphenyl) ether or diphenyl ether ρ, ρ'-dicarboxylic acid.

Epichlorohydrin is used as the esterification component. The amount of epichlorohydrin is more than 1 mole per carboxyl group, preferably 5 to 10 moles. The unreacted epichlorohydrin can be recovered unchanged.

As catalysts for the addition of epichlorohydrin to compounds containing carboxyl groups are according to the invention thioethers and / or sulfonium compounds and other compounds of divalent sulfur is used, which is thioether and / or sulfonium salts with epichlorohydrin able to form, such as mercaptans, hydrogen sulfide and its alkali salts. The thioethers and / or sulfonium salts are used in amounts of 0.01 to 5 percent by weight, based on the carboxyl group-containing compound used. Preferably 0.01 to 0.1 moles of sulfur-containing compound is used per mole of carboxyl group.

The thioethers or sulfonium salts suitable as catalysts correspond to the general formulas

R ₁ -SR ₂

-SR ₂ I * Χ ^Θ

wherein R ₁ , R ₂ and R _{3 can be the} same or different and

a) Alkyl, C ₁ to C ₁₂ , also cycloalkyl, aralkyl, e.g. benzyl,

b) cu-hydroxyalkyls formed by heteroatoms, such as O, S, can be interrupted,

c) cyano-ethylated oxyalkyls, e.g. B.

- CH ₂ - CH ₂ - O - CH ₂ - CH,

■ CN

d) epoxypropyl

and X ^{e can be} a monovalent anion, preferably a halide ion, such as chloride or bromide ion.

As catalysts to the above definition may be mentioned are: Diäthylsulfid, / S-Hydroxyäthyläthylsulfid, ß-hydroxy-propyläthylsulfid, ω-hydroxytetramethylene-äthylsulfid, thiodiglycol, mono-.beta.-cyanoethyl-thiodiglykoläther, dibenzyl sulfide, Benzyläthylsulfid, Benzylbutylsulfid, trimethylsulfonium iodide, tri - (ß - hydroxyethyl) - sulfonium chloride, dibenzylmethylsulfonium bromide, 2,3 - epoxypropylmethylethylsulfonium iodide, dodecylmethylsulfide or dithiane.

Preference is given to using aliphatic thioethers

ίο not too large alkyl groups, especially with unbranched C ₁ - to C ₅ -alkyl radicals or oxyalkyl radicals, are used in order to avoid a reduction in the catalytic effectiveness due to sterically hindering substituents.

The reaction temperature is from 30 to 120 ⁰ C, preferably at 50 to 8O ⁰ C, because at higher temperatures and in the substantial excess of epichlorohydrin already a part of the chlorohydrin can be converted into epoxide groups; these can react further with any carboxyl groups still present to form 1,3-diesters of glycerol or of the trihydric alcohol corresponding to epichlorohydrin. Any 2,3-epoxypropyl carboxylic acid ester groups which may form can easily be converted into chlorohydrin groups by the addition of hydrogen chloride after the unreacted epichlorohydrin has been removed. The process can also be carried out continuously. The sulfur-containing compounds used as catalysts can be removed from the reaction products by distillation, washing out with water, if appropriate after the prior action of oxidizing substances such as hydrogen peroxide, peracetic acid or cyclohexanone peroxide.

It was surprising that the addition of epichlorohydrin to compounds containing carboxyl groups by the above catalysts at such low temperatures and with practically no formation unwanted polymers of epichlorohydrin takes place. The method is particularly suitable for Addition of epichlorohydrin to di- and polycarboxylic acids, the chlorohydrin esters of which are no longer one another can be separated from by-products by distillation.

Compared to German patent specification 708 463, higher yields of 2-hydroxy-3-chloropropyl carboxylates are achieved according to the invention. In addition, as a result of the 'mild effect of the catalysts to be used according to the invention, a uniform addition of the carboxylic acid group to the epichlorohydrin with formation of the desired ester at the selected temperature, without there being an extraordinary temperature increase that occurs by itself as in the reference, which is the case with Working on an industrial scale can lead to extraordinary difficulties. Furthermore, the catalysts to be used according to the invention do not bring about any polymerization of the epichlorohydrin or the formation of undesired by-products. The table below compares the polymerizability of epichlorohydrin in the presence of known catalysts with the polymerizability in the presence of the catalysts of the invention. By 5 mol epichlorohydrin and 10 g of catalyst were heated for 40 hours 8O ⁰ C, the catalyst removed by distillation or washing with water, the residue was fractionally distilled and examined analytically.

Epichlorohydrin -> Catalyst and quantity Reaction conditions Chlorine-containing polymer 462.5 g 10 g N-methylpyridinium
iodide 40 hours 80 ⁰ C 74 g 462.5 g 10 g pyridine 40 hours 8O ⁰ C 76 g 462.5 g 10 grams of aniline 40 hours 80 ° C 41g 462.5 g 10 g dimethylaniline 40 hours 8O ⁰ C 26 g 462.5 g 10 g dimethylbenzylamine 40 hours 80 ⁰ C 14 g 462.5 g 10 g trimethylbenzyl
ammonium chloride 40 hours 80 ° C 8g 462.5 g 10 g trimethylsulfonium
iodide 40 hours 80 ° C - 462.5 g 10 g of 2-hydroxyethyl ethyl
sulfide 40 hours 80 ° C - 462.5 g 10 g thiodiglycol 40 hours 8.0 ° C - 462.5 g 10 g diethyl sulfide 40 hours 80 ° C - 462.5 g 10 g tri - ^ - hydroxyethyl
sulfonium chloride 40 hours 80 ° C -

By secondary reaction with epichlorohydrin, especially at higher temperatures and for a long time Reaction times, in the process of the invention, the 1-hydroxy-S-chloro-propylcarboxylic acid ester are partially converted into epoxy groups. However, the epoxides so formed are not as By-products in the true sense of the word are to be assessed, since they are extremely easy even at room temperature can be converted back into the chlorohydrin esters by treatment with aqueous hydrochloric acid. aside from that the chlorohydrin esters obtained according to the invention are often used to prepare the corresponding epoxides used, so that already formed epoxy is not to be regarded as a by-product in this case. It is however, it is easily possible to direct the reaction by suitable temperature control so that the Implementation proceeds practically only in terms of chlorohydrin ester formation.

The 2-hydroxy-3-chloro-propylcarboxylic acid esters prepared according to the invention are intermediate products for the production of high molecular weight compounds. They can be used, for example, according to known Easily convert methods into the corresponding mono- and polyepoxide compounds. aside from that they can be used as plasticizers for vinyl polymers. In combination with aliphatic They serve as textile auxiliaries, binders for pigment dyes or as agents for polyamines Increase in wet tensile strength.

The yields given in the examples below relate to the acids used.

example 1

282 g of oleic acid, 463 g of epichlorohydrin and 3 g / i-hydroxyethyl äthylsulfid are reacted for 20 hours at 6O ⁰ C. After the volatile components have been distilled off in vacuo, the 2-hydroxy-3-chloro-propyl ester of oleic acid is obtained with a chlorine content of 9.5% (calculated 9.47%). The yield is 99% of theory.

Example 2

128 g hexahydrobenzoic acid, 463 g of epichlorohydrin and 2 grams of .beta.-hydroxyethyl äthylsulfid at 6O ⁰ C

65 implemented for 20 hours. After distilling off the excess epichlorohydrin under reduced pressure gives the 2-hydroxy-3-chloro-propyl ester (calculated 16.1%) of the hexahydrobenzoic acid with a chlorine content of 16.1% i ⁿ a yield of 100% of theory.

Example 3

122 g of benzoic acid, 463 g of epichlorohydrin and 2 g of ß-hydroxyethyl ethyl sulfide are as in Example 2 implemented and processed. The reaction product has a chlorine content of 16.35% (calculated 16.55%). The yield is 99% of theory.

Example 4

146 g of adipic acid, 925 g of epichlorohydrin and 3 g / 3-hydroxyethyl-äthylsulfid are reacted for 24 hours at 6O ⁰ C and then removed in vacuo from volatile components. The reaction product contains 17.95% chlorine and 2.1% epoxy oxygen. The adipic acid - bis - (2 - hydroxy - 3 - chloro - propyl ester) is obtained in a yield of 83% of theory.

Example 5

1Ϊ6 g fumaric acid, 925 g epichlorohydrin and 3 g ß-Hydroxyäthylethylsulfid be on for 38 hours 60 ° C heated. Working up gives a reaction product with a chlorine content of 23.7% (calculated 23.6%) in quantitative yield.

B e i s ρ i e 1 6

116 g of maleic acid, 925 g of epichlorohydrin and 5 g of β - Oxyäthyl - äthylsulfid are heated 33 hours at 120 ⁰ C. After working up, the reaction product is obtained with a chlorine content of 23.4% (calculated 23.6%) in a yield of 98% of theory.

Example 7

134 g of diglycolic acid, 925 g of epichlorohydrin are mixed with 3 g of ß-hydroxyethyl ethyl sulfide for 24 hours 60 ° C heated. After work-up, a reaction product with 22.4% chlorine (calculated 22.3%) is obtained in a yield of 99% of theory.

Example 8

172 g of hexahydrophthalic acid, 925 g of epichlorohydrin are mixed with 5 g of N-dodecylethyl sulfide for 30 hours 60 ° C heated. After the volatile constituents have been distilled off, a reaction product is obtained with a chlorine content of 15.05% (calculated 19.9%) and an epoxy oxygen content of 2.2%. the Yield is 75% of theory of bis (2-hydroxy-3-chloro-propyl ester) hexahydrophthalic acid.

Example 9

172 g of hexahydrophthalic acid and 925 g of epichlorohydrin are mixed with 5 g / 5-hydroxyethyl-ethyl sulfide Heated to 40 ° C for 52 hours. The worked up reaction product contains 20.1% chlorine (calculated 19.9%). If the abovementioned components are heated to 120 ° C. for 2 hours, a Reaction product with 19.9% chlorine in quantitative yield.

Example 10

560 g of a half ester made from 3 moles of hexahydrophthalic anhydride and 1 mole of hexanetri oil-1,2,6 (0.94 mole) with 1305 g of epichlorohydrin and 5 g / 3-hydroxyethyl-ethyl sulfide was stirred at 60 ° C. for 24 hours. After the excess epichlorohydrin has been distilled off in vacuo, a chlorohydrin ester is obtained with 12.7% chlorine (calculated 12.2%) in 99% yield.

Example 11

■ 170g 1,2,3,6-tetrahydrophthalic acid, 925 g epichlorohydrin be 22 hours in the presence of

5 g / S-hydroxyethyl ethyl sulfide stirred at 60 ° C and then freed from volatile constituents in vacuo. The reaction product has a chlorine content of 16.4% (calculated 20.0%) and an epoxy oxygen content of 2.2%. The yield is 86% of theory of 1,2,3,6-tetrahydrophthalic acid chlorohydrin ester.

Example 12

286 g of endomethylene tetrahydrophthalic acid, 1388 g of epichlorohydrin are mixed with 6 g of ^ -hydroxyethyl ethyl sulfide Stirred for 17 hours at 60.degree. C. and worked up. The reaction product contains 18.4% chlorine (calculated 19.25%) · The yield is 94% of theory.

B e i s ρ i e 1 13

300 g camphoric acid, 1388 g epichlorohydrin and

6 g / 3-hydroxyethyl-ethyl sulfide yield after 17 hours Reaction at 60 ° C the corresponding chlorohydrin ester with a chlorine content of 17.6% (calculated 18.45%) in a yield of 95% of theory.

Example 14

168 g l ^ S / l-tetrahydronaphthalene-S ^ -dicarboxylic-1-succinic acid, 925 g of epichlorohydrin are in the presence of 5 g of ß-hydroxyethyl ethyl sulfide for 4 hours implemented at 120 ° C. After working up, a reaction product containing 17.25% chlorine is obtained (calculated 20.1%) and with an epoxy oxygen

65 content of 0.98% · The yield is 86% of theory of 1,2,3,4-tetrahydronaphthalene-3,4-dicarboxylic-1-succinic acid tetra (2-hydroxy-3-chloropropyl ester).

Example 15

166 g of terephthalic acid (1 mol), 925 g of epichlorohydrin are mixed with 3.3 g / 3-hydroxyethylsulfide at 60 ° C implemented. The acid has dissolved after 35 hours, after a reaction time of 70 hours the excess epichlorohydrin and a small amount of glycerol dichlorohydrin are distilled off. Yield: 337 g of an addition product which contains 16.75% chlorine (= 1.59 mol) and 1.98% epoxy oxygen (= 0.47 mol) contains. Based on the chlorine value, a yield of 83% is calculated Theory of terephthalic acid bis (2-hydroxy-3-chloropropyl ester).

Example 16

If phthalic acid is used instead of terephthalic acid, the result is analogous after 24 hours Example 15 333g adduct with 15.8% chlorine (= 1.49MoI) and 2.16% epoxy oxygen (= 0.45 mol). The yield of terephthalic acid bis (2-hydroxy-3-chloro-propyl ester) is 78% of theory.

Example 17

If isophthalic acid is used instead of terephthalic acid and the procedure is otherwise analogous to Example 15, 328 g of adduct with 14.8% chlorine (= 1.37 mol) and 2.3% epoxy oxygen (= 0.47 mol) are obtained in this way; this corresponds to a yield of 78% of theory of bis (2 - hydroxy - 3 - chloro - propyl ester) isophthalic acid.

Claims (1)

Claim: Process for the preparation of carboxylic acid 2-hydroxy-3-chloropropyl esters by addition of epichlorohydrin to compounds containing at least one carboxy group in the presence of catalysts, characterized in that the catalysts used are thioethers of the general formula R ₁ - S - R ₂ and / or sulfonium salts of the general formula R ₁ -SR ₂ uses, in which R ₁ , R ₂ 'and R ₃ -can be the same or different and a) alkyl, C ₁ to C ₁₂ , cycloalkyl, aralkyl, b) ω-hydroxyalkyls, which are replaced by heteroatoms, how O, S, can be interrupted, c) cyano-ethylated oxyalkyls, d) epoxypropyl and X ^{s can be} a monovalent anion, preferably a halide ion. Documents considered: German Patent No. 708 463. 809 519/702 3.68 © Bundesdruckerei Berlin