SU883007A1

SU883007A1 - Method of preparing diester derivatives of p-oxybenzoic acid

Info

Publication number: SU883007A1
Application number: SU792875143A
Authority: SU
Inventors: Владимир Иванович Титов; Юрий Александрович Москвичев; Галина Николаевна Тимошенко; Герман Севирович Миронов
Original assignee: Ярославский политехнический институт
Priority date: 1979-12-25
Filing date: 1979-12-25
Publication date: 1981-11-23

Description

Изобретение относится к .органической химии, конкретно к новому способу получения простых диэфиров п-оксибензойной кислоты, которые используются в качестве модификаторов для различных типов волокон, .например полиэфирных.The invention relates to .organic chemistry, and specifically to a new method for producing p-hydroxybenzoic acid diesters, which are used as modifiers for various types of fibers, for example polyester.

Наиболее близким по технической сущности к изобретению является спо- ^υсоб получения простых диэфиров, например 2,2-бис-(карбоксифенокси)диэтилового эфира, который получают путем взаимодействия метилового эфи-. ра п-оксибензойной кислоты с изоами- 15 латом калия при кипении реакционной массы, е последующим добавлением хлорекса и водного раствора КОН, отгонкой изоамилового спирта с водяным паром и подкислением остатка. Про- 20 цесс обычно протекает 9-10 ч. Выход 2,2-бис-(карбоксифенокси)диэтилового эфира 85% [1].The closest in technical essence to the invention is a spo- ^υ GSS producing diethers such as 2,2-bis (carboxyphenoxy) diethyl ester which is prepared by reaction of methyl ethers. p-hydroxybenzoic acid with potassium isoamylate 15 while boiling the reaction mixture, followed by the addition of chlorex and an aqueous KOH solution, distillation of isoamyl alcohol with steam and acidification of the residue. The process usually takes 9-10 hours. The yield of 2,2-bis (carboxyphenoxy) diethyl ether is 85% [1].

Недостатком йзвестного способа 25 является сложность и длительность процесса.The disadvantage of the known method 25 is the complexity and duration of the process.

Цель изобретения заключается в упрощении и интенсификации процесса. 30The purpose of the invention is to simplify and intensify the process. thirty

Поставленная цель достигается способом получения простых диэфиров п-оксибенэойной кислоты общей формулыThis goal is achieved by the method of producing diesters of p-hydroxybenoic acid of the general formula

путем взаимодействия п-оксибензойной кислоты с соединением формулы Q1-X-C1, где X имеет указанные выше значения, в присутствии карбоната щелочного металла в среде диметилформамида, или диметилацетамида, или диметилсульфоксида при 130-160°С, обычно с последующим выливанием реакционной массы в воду и ее подкислением. Процесс обычно проводят в течение 3-5 ч. Выход целевых диэфиров 85-89%.by reacting p-hydroxybenzoic acid with a compound of the formula Q1-X-C1, where X is as defined above, in the presence of an alkali metal carbonate in a medium of dimethylformamide or dimethylacetamide or dimethyl sulfoxide at 130-160 ° C, usually followed by pouring the reaction mass into water and its acidification. The process is usually carried out within 3-5 hours. The yield of the target diesters is 85-89%.

Указанный ёпособ отличается от известного тем, что в реакции используется не эфир п-оксибензойной кислоты, а сама кислота. Это упрощает процесс, так как отпадает необходимость предварительной этерификации кислоты. С этим же связано упроще3 ние стадии выделения целевого продукта - не требуется стадия омыления эфира. *The specified method differs from the known one in that the reaction does not use p-hydroxybenzoic acid ester, but the acid itself. This simplifies the process, since there is no need to pre-esterify the acid. A simplification of the stage of isolation of the target product is associated with this — the stage of ether saponification is not required. *

Пример 1. В трехгорлую колбу, снабженную мешалкой, термометром и обратным холодильником, пдме- щают 10,76 г(0,075 мол)хлорекса, 22,.85 г (0,15 мол)п-оксибензойной кислоты, 15,9 г(0,15 мол) безводного карбоната Na и 200 мл диметилформамида (ДМФА). Содержимое нагревают до 145°С и выдерживают при этой ·^υ температуре 4 ч. Затем охлаждают до 50°С, выливают в 500 мл воды и подкисляют 10%-ным раствором соляной ’кислоты. После переосаждения из 5%ного раствора NagCOj получают 23,1 г 15 (89 мол.%) 2,2-бис-(п-карбоксифенокси)диэтилового эфира. Т.пл. 301-303°С^Example 1. 10.76 g (0.075 mol) of chlororex, 22, .85 g (0.15 mol) of p-hydroxybenzoic acid, 15.9 g (0 , 15 mol) of anhydrous Na carbonate and 200 ml of dimethylformamide (DMF). The contents were heated to 145 ° C and kept at this temperature for 4 · ^υ h. It was then cooled to 50 ° C, poured into 500 ml of water and acidified with 10% hydrochloric 'acid. After reprecipitation from a 5% solution of NagCOj, 23.1 g of 15 (89 mol%) 2,2-bis- (p-carboxyphenoxy) diethyl ether are obtained. Mp 301-303 ° C ^

Найдено, %: С 62,26; Н 5,36.Found,%: C 62.26; H, 5.36.

С <g Н iqO f „C <g H iqO f „

Вычислено, %: С 62,43; Н 5,20. ^мП р и м е р 2. Реакцию проводят в условиях примера 1, но берутCalculated,%: C 62.43; H, 5.20. ^m PRI me R 2. The reaction is carried out under the conditions of example 1, but take

20,75 г (0,15 мол) безводного поташа и. 150 мл диметилсульфоксида. Реакционную массу перемешивают при 2520.75 g (0.15 mol) of anhydrous potash and. 150 ml of dimethyl sulfoxide. The reaction mass is stirred at 25

130°С 5 ч. Дальнейшая обработка, как в примере 1. Выход целевого продукта 87,5 мол.%.130 ° C for 5 hours. Further processing, as in example 1. The yield of the target product is 87.5 mol.%.

Пр и м е рЗ. Реакцию проводят в условиях примера 1, но берут 17,5 г 30 (0,1 мол)м-ксилилендихлорида,27,6 г (0,2 мол) п-оксибензойной кислоты,* 21,2 г (0,2 мол) безводного карбоната натрия и 200 мл ДМФА. Реакционную массу перемешивают 4 ч при 140°С. 35 Дальнейшая обработка, как в примере 1. Получают 32,15 г (85 мол 4) 4,4-(м-ксилилендиокси)бис-бензойной кислоты. Т. пл. 183-184,5°C.PRI me RZ. The reaction is carried out under the conditions of example 1, but take 17.5 g of 30 (0.1 mol) m-xylylenedichloride, 27.6 g (0.2 mol) of p-hydroxybenzoic acid, * 21.2 g (0.2 mol) anhydrous sodium carbonate and 200 ml of DMF. The reaction mass is stirred for 4 hours at 140 ° C. 35 Further processing, as in Example 1. 32.15 g (85 mol 4) of 4.4- (m-xylylenedioxy) bis-benzoic acid are obtained. T. pl. 183-184.5 ° C.

Найдено, %: С 69,72; Н 4,84Found,%: C 69.72; H 4.84

Вычислено, %: С 69,84; Н 4,76.. Пример4. Реакцию проводят в условиях примера 3, но берут 27,6 г безводного поташа и 250 мл диметилацетамида. Реакционную массу переме- 45 шивают 3 ч прй 160°С. Выход целевого продукта-86 мол %.Calculated,%: C 69.84; H 4.76 .. Example 4. The reaction is carried out under the conditions of example 3, but take 27.6 g of anhydrous potash and 250 ml of dimethylacetamide. The reaction mixture is stirred for 3 hours at 160 ° C. The yield of the target product is 86 mol%.

П р и м е р 5. Реакцию проводят в условиях примера 3, но берут 17,5 г (0,1 мол) п-ксилилендихлорида. Получают 32,5 г (86 мол %) 4,4-(п-ксилилендиокси)-бис-бензойной кислоты. Т. пл. 212-214°С.PRI me R 5. The reaction is carried out under the conditions of example 3, but take 17.5 g (0.1 mol) of p-xylylenedichloride. 32.5 g (86 mol%) of 4,4- (p-xylylenedioxy) bis-benzoic acid are obtained. T. pl. 212-214 ° C.

Найдено,%: С 69,75; Н 4,87 ^с2а^н ₁₀О₆ Found,%: C 69.75; H 4.87 ^s 2a ⁿ ₁₀ O ₆

Вычислено, %: С 69,84; Н 4,76.Calculated,%: C 69.84; H 4.76.

Таким образом, предлагаемый способ является одностадийным,основан на использовании более дешевой поксибензойной кислоты и обеспечивает высокий выход целевого продукта при его высоком качестве.Thus, the proposed method is one-stage, based on the use of cheaper poxybenzoic acid and provides a high yield of the target product with its high quality.

Claims

The invention relates to organic chemistry, specifically to a new method for the preparation of p-hydroxy benzoic acid diesters, which are used as modifiers for various types of fibers, for example polyester. The closest to the technical essence of the invention is a method of producing diesters, for example 2,2-bis- (carboxyphenoxy) diethyl ether, which is obtained by reacting p-hydroxybenzoic acid methyl ester with potassium isoamylate at boiling of the reaction mass, followed by addition of chlorine and an aqueous KOH solution, stripping the isoamyl alcohol with steam and acidifying the residue. The process usually takes 9-10 hours. The yield of 2,2-bis- (carboxyfenrxy) diethyl ether is 85% 1. The disadvantage of this method is the complexity and duration of the process. The purpose of the invention is to streamline and intensify the process. The goal is achieved by the method of producing p-hydroxybenzoic acid diesters of the general formula (j C4Q-where X: -CHP | -CHN | by reacting p-hydroxybenzoic acid with the compound of the formula Q1-X-C1, where X is as defined above, in the presence of an alkali metal carbonate in dimethylformamide or dimethylacetamide or dimethyl sulfoxide at 130-160 ° C, usually followed by pouring the reaction mixture into water and acidifying it. 5 hours. The yield of the target diesters is 85-89%. The said method differs from the known fact that the reaction does not use p-hydroxybenzoic acid ester, but the acid itself. This simplifies the process, since it is not necessary to pre-esterifyic acid. Simplification of the stage of entraining the desired product - no stage of ether ethelation is required. For example, in a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 10.76 g (0.075 mol) of chlorine, 22, .85 g (0.15 mol) p- hydroxybenzoic acid, 15.9 g (O, 15 mol) anhydrous Na carbonate 200 ml dimetilfor mamida (DMF). The contents were heated to 145 ° C and kept at this temperature for 4 hours. Then cooled to 50 ° C, drunk in 500 ml of water and acidified with a 10% hydrochloric acid solution. After reprecipitation from a 5% solution, 23.1 (89 mol.%) Of 2,2-bis (p-carboxyphene si) diethyl ether is obtained. M.p. 301-303 Found: C, 62.26; H 5.36. С 8 Н veO 7 Calculated,%: с 62,43; H 5.20. PRI me R

2. The reaction is carried out under the conditions of example 1, but 20.75 g (0.15 mol) of anhydrous potash H 150 ml of dimethyl sulfoxide are taken. The reaction was stirred at 130 ° C for 5 hours. Further processing was carried out as in Example 1. The yield of the desired product was 87.5 mol%. The reaction is carried out under the conditions of Example 1, but taking 17.5 (0.1 mol) of m-xylylene dichloride, 27.6 g (0.2 mol) of p-hydroxybenzoic acid, 21.2 g (0.2 mole) of anhydrous sodium carbonate and 200 ml of DMF. The reaction mass is stirred for 4 hours at 140 ° C. Further processing is carried out as in Example 1. 32.15 g (85 mol 4) of 4.4- (m-xylylenedioxy) bis-benzoic acid are obtained. T. pl. 183-184.5 p. Found,% 1 C 69.72; H 4.84, 9 0. O t Calculated,%: s 69.84; H 4.76., Example4. The reaction is carried out under the conditions of Example 3, but 27.6 anhydrous potash and 250 ml of dimethylacetamide are taken. The reaction mass is stirred for 3 hours at 160 ° С. The yield of the target product .86 mol%. EXAMPLE 5 The reaction was carried out under the conditions of Example 3, but taking 17.5 g (0.1 msph) of p-xylylene dichloride. Radiate 32.5 g (86 mol%) of 4.4- (p-xy and dioxy) bis-benzoic acid. Found,%: C 69.75; And 4.87 S24N, in. Calculated,%: C 69.84; H 4.76. Thus, the proposed method is a one-step process. It is based on the use of cheaper, coxybenzoic acid and provides a HIGH yield of the target product at its high quality. DETAILED DESCRIPTION OF THE INVENTION Method for the preparation of d-P-hydroxybenzoic acid diesters of the general form. characterized in that, in order to simplify and intensify the process, p-hydroxybenzoic acid is reacted with a compound of the formula C1-X-C1, where X is as defined above, in the presence of alkali metal carbonate in dimethylformamide or dimethyl acetamide or dimethyl sulfoxide pu 130-160 ° C. Sources of information, rintye taken into account during e-examination 1. USSR author's certificate 415250, cl. C 07 C 41/00, published 974 (prototype)