SU1109377A1 - Process for preparing indanyl phenols or their substitutes - Google Patents

Abstract

A method for producing indanylphenols or their substituted general formulas where R is hydrogen, methyl or hydroxy group by reacting the corresponding phenol with indene at a temperature of 120-140 ° C in the presence of an acidic catalyst using alkylate distillation under reduced pressure, characterized in that, in order to expand the range of target products, increasing their yield and simplifying the process, in the latter, oxalic acid in an amount (L 0.6–3.1 wt.% of the sum of the initial C phenol and indene) is used as an acidic catalyst.

Description

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The invention relates to a process for the preparation of indanylphenols or their substituted ones, which can be used as antioxidants. A known method of producing indanyl phenols by reacting phenol and indene at 120-140 ° C at atmospheric pressure (the molar ratio phenol: hinden is from 1: 1 to 2: 1) and a reaction time of 4 hours in the presence of a cation-exchange resin KU-2. The indene conversion is 60-80%, the selectivity is 70-80% Cl. The disadvantage of this method is the low yield of indanylphenols 70-80%. In addition, in the alkylation process, deactivation of the cation exchanger occurs, which ultimately leads to polunification of contaminated dark alkylate. The closest technical solution to the invention is the method for producing indanylphenols by the interaction of phenol with indene in the presence of AlClg. According to this method, hydrogen chloride gas is injected into the indene, then phenol is loaded and the AlC temperature is maintained at 40-55 ° C for 1 h, then it is raised to 14 and at this temperature the reaction is continued for an additional 2 h. Then the reaction mass is washed from AlClj and then the alkylate is distilled under vacuum. The output of the amount of mono-di- and tri-composition is 75-80% 2. However, the insufficiently high yield of the target products and the presence of a significant amount of waste in the alkylate formed from A1C1d do not ensure the efficiency of the process. The purpose of the invention is to increase the output of the target products and expand their range, as well as simplifying the process. The goal is achieved by the fact that according to the method of producing indanylphenols and their substituted general formulas where R is hydrogen, methyl oroxy group, by reacting the corresponding phenol with indene, oxalic acid, taken in an amount of 0.6-3, is used as an acid catalyst. 1 wt.% Of the initial reagents (phenol and indene), at 120-140 ° С with subsequent distillation of alkylate in vacuum. Using the proposed method reduces the reaction time to 1.5-2.0 hours (compared to 3.0 h in the famous case), get high yield up to 90% and above (75-80% in the well-known) phenyl phenols, eliminate the need for neutralization and rinsing of the reaction products in order to remove the acid catalyst, since oxalic acid decomposes the alkylate distillation process. Example 1. In a 1000 cm-5 reactor with a stirrer, a thermometer and a reflux condenser, 282 g of phenol and 19.5 g (3.1 masl) of oxalic acid dihydrate (COOH) x X 2 HjOj are placed. The mixture is then heated to 135 ° C and at this temperature 348 g of indene is gradually fed. The reaction mixture is stirred for 2 hours, then it is distilled under reduced pressure. First, unreacted phenol and indene are distilled off. The remaining alkylate (residue) is cMfjcb indanylphenols and can be used further on its own as an antioxidant or starting material for the preparation of other compounds. The indene conversion is 90-95%. If necessary, the residue is distilled at a pressure below the pressure of the graph, while the microindanyl phenols are distilled at 0.2-0–6 mm Hg. in the range of 160-210 ° С, and diindanilfeno sh - 260310 ° С. The obtained target product is a mixture of indanylphenols: monoindanylphenol consists on average of 35% by weight of 2-indanylphenol and 65% by weight of 4-indanylphenol, diindaiylphenol consists of 66% by weight 2.4 of diindanylphenol and 34% of 2.6% diindanylphenol, triindanylphenol contains about 68 wt.% 2,4,6-triindanylphenol. Pr PS m e p 2. 376 g of phenol and 9.9 g (2 wt.%) Oxalic acid dihydrate are loaded into the reactor, the mixture is heated to and at this temperature 116 g of indene is gradually fed. The reaction mixture is stirred at this temperature for 1.5 hours. After distilling off the excess phenol, the alkylate consists of 95% monoindannlphenols and 5% diin-danilphenols. Conversion of indene 98%. Example 3. According to the procedure described in Example 1, 108 g of p-cresol is reacted with 116 g of indene at 135 ° C. The reaction time is 1.5 hours. Conversion of indene 90% The output of indenyl-p-cresol 90-95%. Analysis of the reaction products was performed by GLC. Distillation of the alkylate under reduced pressure results in the allocation of 15 g of unreacted p-cresol and indene and 211 g of indanyl p-cresols, the latter being distilled at 205–310 ° С 0.1 mm Hg; To isolate 4-methyl-6-indanylphenyl of 98% purity, fraction 162-170 / 3 5 mm Hg. (p | 1.5952; 1.0953) is subjected to liquid adsorption chromatography in a column with A1 O. The 4-methyl-6-indanylphenol is added with a p of 1.5997; df 1, iUOi. Found, in wt.%: C 85.76-, OH 7.40; M 225. Calculated, in wt.%: C 85.71 H 7.14; OH 7.60; M 224. Benzoate, m.p. 118.5-119.0 ° С (from ethyl alcohol). Found, wt.%: C 84.15; H 6.08. С Н О. Calculation, ° wt.%: C 85.14, H 6.0 Example 4. According to the method and conditions described in example 1, 110 g of resorcinol react with 116 g of indene in the presence of 4.6 g ( 0.6 wt.%) Oxalic acid. Conversion of indene 85-90%. The output of indanyl resorcinol 90%. Analysis of the reaction products was carried out by thin layer chromatography. The isolation of the products was carried out by pressure chromatography. M.p. obtained indilresorcin. Indanilresorcinol consists of 90% by weight of monoindanylresorcin, 8% by weight of diindanylresorcin and 2% by weight of a substance of unknown composition. The hydroxyl number is 10.9. Material balances for examples 1-4 are given in tabl:;. Note: Continuation of the table Obtained: Monoindanyl 404, 564.2 Phenol Diindanyl 189, 030.0 Phenol Triindanyl25, 24.0 Phenol Ui31 8 Loss of BzoTo Too, о Too7o Received: 277,056.3 2,50,5 Monoindanyl 191, 939,0 phenol Diindanyl 10, 82.2 phenol 9.82.0 Losses: 492.0100.0 Example Example: 108.048.2 4-Methylphenol .0 Inden Too, about 224.0 Received: 10.04.4 4-Me typephol ol 4-Methyl-6200, 689.5-indanyl 5 1109377 Continuation of table

4-Methyl-2,6-diindanylphenol

Losses

p 4

110.0 48.7

51lZ

11§GO 226.0 100.0

8.4

19.0

.

.§.

226.0

100

Thus, by increasing the yield on indanylphenol, by eliminating the alkylate pretreatment stage (neutralization, washing with water, drying), it can be concluded that the proposed method is more economically viable, 1 which is known. Table continuation

Claims (1)

METHOD FOR PRODUCING INDANYLPHENOLS OR SUBSTITUTED THEREOF General Formula OH wherein R - is hydrogen, methyl or hydroxy group by reacting the appropriate phenol with indene at a temperature of 120-140 C ^s in the presence of an acid catalyst to alkylate using distillation under reduced pressure, characterized in that, in order to expand the range of target products, and increasing their yield simplification of the process, in the latter, oxalic acid is used as an acid catalyst in an amount of 0.6-3.1 wt.% of the sum of the starting phenol and indene.