Method of producing substituted phenols, containing hem-dichlorocyclopropyl substitute

FIELD: chemistry.

SUBSTANCE: process of alkylating phenols with alkenyl-hem-dichlorocyclopropanes is carried out in the presence of a boron trifluoride etherate catalyst at temperature 50-65°C. The process with phenol is carried out with the following ratio of components in wt %: boron trifluoride etharate 18-19; alkenyl-hem-dichlorocyclopropanes 18-21. The process with 2,6-di-tert-butylphenol is carried out with the following ratio of components in wt %: boron trifluoride etherate 10-11; alkenyl-hem-dichlorocyclopropanes 10-13.

EFFECT: high output as well as quality of the end product.

3 cl, 1 ex, 1 tbl

 

The invention relates to organic chemistry, specifically to obtain substituted phenols, containing in its composition hem.-dichlorocyclopentane Deputy, which are used in the polymer industry as stabilizers and additives.

A method of obtaining substituted aromatic compounds containing heme.-dichlorocyclopentane fragment, dichlorocarbanilide relevant alkenylphenol at a temperature of 40-45°C for 4 hours in the presence of a phase transfer catalyst catamine AB and sodium hydroxide (Galiullina E.R., Slotsky SS, Voronenko B. I., Kuttawa A. Abbadi. Carmeniluvana arilalkilamin esters. // BHG - 2007 - T-No. 3 - P.44-46).

The disadvantages of this method are the difficulty of obtaining and high cost of the required source alkenylphenol and low selectivity of their cyclopropylamine, the formation of large quantities of by-products - polyalkylphenols. The latter is associated with the reaction of dichlorocarbanilide by phenolic hydroxyl.

The technical problem whose solution is proposed in the present invention is to develop a method of producing substituted phenols, containing in its composition hem.-dichlorocyclopentane Deputy, characterized by low quantity of generated by-products and increase the yield of the target product.

Specify the second task is solved by the method of obtaining substituted phenols containing heme.-dichlorocyclopentane Deputy, the alkylation of phenols alkenyl-heme.-dichlorocyclopentane carried out in the presence of epirate boron TRIFLUORIDE as a catalyst at a temperature of 50-65°C for 6 to 17 hours.

The reaction with phenol differs in that it is conducted in the following ratio, wt.%: epirate boron TRIFLUORIDE 18-19; alkenyl-heme.-dichlorocyclopentane 18-21.

Reaction with 2,6-di-traga-butylphenol carried out in the following ratio, wt.%: epirate boron TRIFLUORIDE 10-11; alkenyl-heme.-dichlorocyclopentane 10-13.

The method is as follows.

Catalyst - apirat boron TRIFLUORIDE - before the reaction is cleaned by atmospheric distillation (TKIP=126°C).

Used in the reaction of alkenyl-heme.-dichlorocyclopentane with quantitative yield are formed at dichlorocarbanilide dienes available reagents (chloroform, alkalis) (Kostikov P.P., A.P. Molchanov Interaction dichloro - and dibromocarbene with cyclic diene hydrocarbons. // Gorg. Chem. - 1975 - T - S).

Alkenyl-heme.-dichlorocyclopentane get when dichlorocarbanilide various dienes (butadiene, isoprene, and other). This reaction is carried out at cooling. Dien placed in a flask with chloroform and interfacial catalyst for TABAH (treati is benzylammonium chloride). Under vigorous stirring and cooling, to the reaction mass was added dropwise a 50% NaOH solution for one hour. Then the reaction mass is stirred for further 1 hour at 20°C. After which the mixture is washed with water until neutral. The lower organic layer is dried svezheproseyannym magnesium sulfate, filtered and, after removal of chloroform, the reaction mixture was subjected to atmospheric distillation.

Source reagents must meet the following requirements:

- NaOH - GOST 4328-77;

- Chloroform - GOST 20015-88;

- BF3-(C2H5)2O - TU-6-09-804-77

- 2,6-di-tert-butylphenol - TU 38.5901237-90

- Phenol - GOST 23519-93

- Triethylmethylammonium chloride - TU 05763458-146-92

Phenols add the catalyst (apiret boron TRIFLUORIDE), under stirring and heating the mixture up to 50-65°C in the flask was slowly added dropwise alkenyl-heme.-dichlorocyclopentane. The molar ratio of alkenyl-heme.-dichlorocyclopentane: phenol: catalyst =1:5:1. After completion of the addition the reaction mass is heated for from 6 to 17 hours under vigorous stirring. Upon completion of the reaction the reaction mass is then cooled to 20-25°C and extracted with a suitable solvent. The organic layer is washed with water, then the solution of NaHCO3and dried MgSO4after evaporation of the solvent.

Example

In chetyrehosnuju flask equipped mesalc the nd with the trap, reflux condenser, dropping funnel and thermometer, download 9.4 g (0.1 mol) of phenol and 2.82 g (0.02 mol) of catalyst epirate boron TRIFLUORIDE, with stirring and heated to 50-65°C is slowly added dropwise 0.0146 mol of 1,1-dichloro-2-vinylcyclopropanes.

After completion of the addition the reaction mass is heated at 50-65°C for 17 hours under vigorous stirring. Upon completion of the reaction the reaction mass is then cooled to 20-25°C and extracted with a solvent. The organic layer is washed with water, then the solution of NaHCO3and dried MgSO4after evaporation of the solvent.

Output 4-[1-(2,2-dichlorocyclohexyl)ethyl]phenol is a mixture of n - and o-isomers 97%.

The results of the syntheses with other alkenyl-heme.-dichlorocyclopentane and 2,6-di-tert-butylphenol shown in the table, the syntheses carried out analogously to example 1.

The table shows that the proposed method will allow you to reach exit substituted phenols containing heme.-dichlorocyclopentane fragment, 95% in comparison with the prototype, where the output reaches 90%, reduce the amount of by-products - polyalkylphenols that make wide use of it as stabilizers and additives in the polymer industry.

1. The method of obtaining substituted phenols containing heme.-dichlorocyclopentane Deputy, alkylation f is NOlow of alkenyl-heme.-dichlorocyclopentane carried out in the presence of epirate boron TRIFLUORIDE as a catalyst at a temperature of 50-65°C for 9-17 o'clock

2. The method according to claim 1, characterized in that the reaction with the phenol is carried out at the following ratio, wt.%: epirate boron TRIFLUORIDE 18-19; alkenyl-heme.-dichlorocyclopentane 18-21.

3. The method according to claim 1, characterized in that the reaction with 2,6-da-tert-butylphenol carried out in the following ratio, wt.%: epirate boron TRIFLUORIDE 10-11; alkenyl-heme.-dichlorocyclopentane 10-13.



 

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