SU1680687A1 - Method for obtaining @-oxyethyl ethess of cyclohexene carboxylic acids - Google Patents

Abstract

The invention relates to esters of neftenic acids, in particular to the preparation of the ./3-hydroxyethyl esters of cyclohexenecarboxylic acids of the general formula (CH2) 2-CR, CH-ChЈ-CR-C (O) -OCH2 CCH2-OH, where a) b) and R, H; c) n R, CH3 g), rH3, used as wastes, plasticizers of synthetic oils. The goal is to increase the yield of the target product and simplify the process. It is carried out by the reaction of acrylic or methacrylic acid with divinyl or isoprene and ethylene oxide at their molar ratio (1-2) :( 1.2-2.4): 1, in the presence of a catalyst — triethylamine or pyridine, taken in amount of 0.5% by weight of the acid, and a poly-, merization-hydroquinone inhibitor at a temperature of 170-180 ° C. These conditions increase the yield of the target products from 80 to 98.1-98.6%, simplify the process by carrying out the synthesis in one stage without preliminary preparation of cyclohexenecarboxylic acid, and also reduce the time of synthesis from 7-8 hours to 20 -25 min 1 z.p, f-ly. cl

Description

Sencarboxylic acid has been proven using IR and PMR spectra.

In the IR spectrum, taken on an IKS-14 device with a sodium chloride prism, intense absorption bands with a frequency of 1770-1740, 1070 and 3600-3400 were detected.

thirty

, characterizing the presence in the test substance, respectively, С-О-С and ОН-groups.

In the PMR spectrum, it is recorded on the radio spectrum (5, 20., "1Q ,,", ..,, t., "-" ".., Tola and ™ ™" a ™ ",. D4. 1 0727 PG M851; schrinailry 180 ° C,

As a result of vacuum distillation, 190.5 g or 98.08% of the theoretical jb-octyl 4-methyl-D-cyclohexenecarboxylic acid ester was isolated.

The synthesized ether has the following physico-chemical parameters: t, kip. 176-177 ° С (with Hummert);

December 49.17, calculated 49.15; saponification number 298 mg KOH / g; essential number 297.3 mg KOH / g; hydroxyl number is 40 9.23%; iodine number 156 kg per 100 t; Found,%: C 65.21; H 8.620 Calculated,%: C 65.22; H 8.70 „Structure and structure of the received

Tesla's meter, the following characteristic groups of resonant absorption signals were observed: the signal in the Region and 3.5-3.6 ppm corresponds to the group -O-CHg, the signal in the region of G 4.5-5.) Oh ppm belongs to the OH group connected to the CH "group in the fragment

Example 2, Preparation of β-oxyethyl ether P ° kaza ™ analogously to example 2, 1-mWl-D cyclohexene-45 lamide ether. 4. Preparation of 3-oxycarboxylic acid. Ethyl ester 1 The 4-dimethyl-D-cyclo method is carried out in a manner analogous to that of hexenecarboxylic acid. measure 1, with the difference that, using Cn ° C °, methacrylic acid is shelled in a similar way in the amount of 2 with that of Difference, which is used as the starting diene - isoprene in the amount of 81.6 g (1.2 g mol) and, as a catalyst, pyridine in the amount of 0.43 g, the reaction is carried out at 25 minutes.

86 g (1 g mol), and triethylamine in the amount of 0.43 g is taken as a catalyst and the reaction is carried out at 180 ° C. As a result of vacuum distillation, 181.5 g or 98.6% of the theoretical p -oxyethyl ether was obtained.

55 As a result of vacuum distillation

195 g or 98.5% of the theoretical p-oxyethyl ester of 1.4 A -t 1 -mu m-h lots were isolated cyclohexenecarboxylic-i-i.

. The resulting ester is characterized by the following indicators; , bp.183 dimethyl- 6 -cyclohexenecarboxylic acid.

0

180 ° C,

As a result of vacuum distillation, 190.5 g or 98.08% of the theoretical jb-octyl 4-methyl-D-cyclohexenecarboxylic acid ester was isolated.

The synthesized ether has the following physico-chemical parameters: t, kip. 176-177 ° С (with Hummert);

(5, 20., „1Q ,,„, ..,, t d4 .1 0727 PG M851; 49.17 were found, 49.15 were calculated; saponification number was 298 mg KOH / g; ester number 297.3 mg KOH / g; hydroxyl number 40 9.23%; iodine number 156 kg per 100 t; Found,%: C 65.21; H 8.620 Calculated,%: C 65.22; H 8.70 “Structure and structure of the obtained

 195 g or 98.5% of theoretical p -oxyethyl ether 1 was isolated,

 And-d dimethyl-6-cyclohexenecarboxylic acid.

five

The synthesized ether has the following physico-chemical parameters: so kip. 194-195 ° С (with 10 mm of mercury "St,); ten

.20

i f 1.0501; tip 1,4795;

found 53.51, calculated 53.80; saponification number 283 mg KOH / g; essential number 282.3 mg KOH / g; hydroxyl number is 8.53%; Iodine number 136mg per 100 g

Found,%: C 66.63; H 9.00.

Calculated,%: C, 66.67; H 9.09.

The structure and structure of the synthesized ether were proved analogously to example 2.

EXAMPLE 5 The experiment was carried out analogously to example 1, with molar ratios of indivisible acid, dine, and ethylene oxide 1.5: 1.8: 1. For this purpose, acrylic acid, polyvinyl chloride and triethylamine are taken as catalyst in the amount of 109 g (1.5 g-mol), 97.5 g (1.8 g-mol) and 0.54 g, respectively. As a result of vacuum distillation 167.3 or 98.3% of theoretical A -oxyethyl ester of D-cyclohexenecarboxylic acid. The reaction is carried out analogously to example 1, at a molar ratio of unsaturated acid, diene and ethylene oxide 2: 2.4; 1. For this purpose, acrylic acid, divinyl and triethylamine are taken as catalyzate in the amount of 144 g (2 g-mol), 130 g (2.4 g-mol) and 0.72, respectively.

where is h

To do this, take acrylic acid, divinyl and triethylamine as catalysis yur in the amount of 180 g (2.5 g mol) l 162 $ 5 g (3 g-mol) and 039 Guo respectively. 167.75 g or 98.63% of theoretical ft -oxyethyl ether and cyclohexenecarboxylic acid.

Thus, an increase in the molar ratios of unsaturated acid and diene above 2 and 2.4, respectively, is impractical, since an excess of these reagents does not affect the yield of the target product.

The proposed method allows to increase the yield of the target products to 98.1-98.6% compared to 80% in the known method, to simplify the process by carrying out the synthesis in one steel, ™ without first obtaining cyclohexenecarboxylic acid, and also reduce the synthesis time to 20 -25 min

against 7-8 hours in a known way.

Claims (2)

Invention Formula 35 where H, one . The method of obtaining the / 3-hydroxyethyl 30 esters of cyclohexenecarboxylic acids of the general formula / R n Ch Usoosn2sn2on (i) V / As a result of vacuum distillation, 167.7 g or 98.6% of the theoretical A-hydroxyethyl D-cyclohexenecarboxylic ester was isolated. Example The experiment was carried out as in Example 1 with molar ratios of unsaturated acid, diene and ethylene oxide 0.5: 0.6: 1. To do this, take acrylic acid, divinyl and triethylamine as a catalyst in an amount of, respectively, 36 g (0.5 g mol), 32.5 g (0.5 g mol) and 0.18 g. As a result of vacuum distillation 70.5 g or 82.8% of theoretical fl-oxyethyl ester of D-cyclohexenecarboxylic acid. Example8. The experiment was carried out analogously to example 1, with molar ratios of unsaturated acid, diene and ethylene oxide 2.5: 3.0: 1. R-CH -2 s R - H ,  take off at elevated temperature, characterized in that, in order to increase the yield of the target products and simplify the process, acrylic or methacrylic acid is reacted with divinyl or isoprene and ethylene oxide at a molar ratio of reagents (1-2): (1,): 1 a tertiary amine catalyst and a polymerization inhibitor — hydroquinone at 170–180 ° C, followed by isolation of the product by vacuum distillation. 2. The method of pop. 1, I distinguish gc and u with the fact that triethylamine or pyridine is used as a tertiary amine.