RU2105755C1 - Method of preparing 1,3-di-(arylaminophenoxy) propanols- 2 - Google Patents

Abstract

FIELD: technology of preparation of organic compounds, more particularly synthesis of stabilizers of polymeric materials. SUBSTANCE: 1,3-di- (arylaminophenoxy)-propanols-2 are prepared by reaction of p-oxyphenylaryl amines with epichlorohydrin and alkali at molar ratio of 1:0.5-0.59 0.55-0.65 in aliphatic C₂-C₃ alcohols at boiling point. Technical result of the present invention is to provide favorable conditions for synthesis of desired products and suppress formation of by-products. EFFECT: simplified process flow sheet, reduced consumable raw material rates both for synthesis and recovery stages, no fire hazard at drying stage and lower energy capacity of the process, and main reaction is conducted without nitric products. 2 tbl

Description

где
Ar фенил, нафтил, и может быть использовано для синтеза эффективных стабилизаторов полимерных материалов.The invention relates to a technology for producing organic compounds, in particular to methods for producing derivatives of bis-diarylamines of the general formula

Where
Ar phenyl, naphthyl, and can be used to synthesize effective stabilizers of polymeric materials.

 A known method for producing 1,3-di- (arylaminophenoxy) -propanol-2 by the interaction of n-hydroxyarylamines with 1,3-di-chlorohydrin glycerol and alkali in acetone or dioxane in boiling, followed by isolation of the target products from benzene (Auth. USSR No. 240711, class C 07 C 215/92, 04/01/69). The disadvantage of this method is its fire and explosion hazard due to the use of flammable solvents.

 The closest in technical essence and the result to the proposed method for producing 1,3-di- (arylaminophenoxy) -propanol-2 is the method (Ed. St. USSR N 496261, class C 07 C 217/0, 25.12.75).

According to this method, these products are obtained by the interaction of oxydiarylamines with epichlorohydrin (hereinafter referred to as ECG) and alkali at a ratio of 1: 0.5: 1.1 in the presence of a nonionic emulsifier and a salt of 4 substituted ammonium in an aqueous medium at a temperature of 95-100 ^o C The final products are isolated by pouring them into water, washing with a solution of sodium bisulfate on the filter, then again with water until neutral, then by pulsation, washing on the filter with alcohol and several times recrystallization from ethyl alcohol, followed by drying.

 The disadvantages of this method are: a large alkali consumption of more than 2 times in comparison with the theoretical; the need for a reaction in an inert atmosphere, nitrogen; the presence in the target products of a significant amount of the starting products and the subsequent cumbersome technology for their removal, the formation of large volumes of contaminated solvent, the need for its regeneration and, therefore, the high energy intensity of the process, as well as the fire hazard at the stage of drying the alcohol paste of the target products.

 The objective of the invention was to develop an effective method for producing 1,3-di- (arylaminofexi) -propanol-2.

The essence of the invention lies in the fact that these compounds are obtained by the interaction of n-hydroxyphenylarylamines with ECG and alkali at a ratio of 1: 0.51-0.59: 0.55-0.65 in the environment of aliphatic alcohols C ₂ -C ₃ at their temperature boiling.

 The technical result obtained by using the invention: the creation of optimal conditions for the main reaction of the formation of target products.

The positive effect provided by the proposed method is as follows:
greatly simplifies the process flow diagram;
the output and quality of the final products increases;
raw material consumption rates are reduced both at the synthesis stage and at the isolation stage;
fire and explosion hazard at the drying stage is excluded;
the energy intensity of the process is reduced;
the main reaction is carried out without a nitrogen blanket.

The proposed method for producing 1,3-di- (arylaminophenoxy) -propanol-2 is as follows: n-hydroxyphenylarylamine is successively loaded into the reactor, C ₂ -C ₃ aliphatic alcohol is heated to the boiling point of alcohol, alkali is added with stirring, and kept at boiling within an hour, then ECG is added, resulting in the formation of final products in a mixture with sodium chloride. The reaction mass is kept at boiling for 3-4 hours, then cooled to 20 ^o C, the precipitate is filtered off, washing it at the beginning with alcohol and then with water until there is no chlorine ion. The aqueous paste of the product is sent for drying. In this case, the molar ratio of n-oxidiarylamine ECG alkali is maintained, equal to 1 0.51-0.59 0.55-0.65.

 The method is illustrated by the following examples.

 Example 1. Obtaining 1,3-di- (phenylaminophenoxy) propanol-2.

65.6 g (0.34 g / mol) of technical n-oxydiphenylamine and 200 ml of isopropanol are charged into a 0.5-neck 4-necked flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel. The solution was heated to boiling (82 ^° C.) and 13.61 ml (0.22 g / mol) of a 44% aqueous solution of sodium hydroxide were added dropwise over half an hour. The reaction mass is kept at boiling for one hour, then 15.9 ml (0.2 g / mol) of technical ECG is poured over 0.5 hours, as a result of which a mixture of 1,3-di- (phenylaminophenoxy) - precipitates propanol-2 with sodium chloride. At the end of the ECG supply, the reaction mass is kept at boiling and constant stirring for 3-4 hours, then cooled to room temperature, filtered, washing the filter cake with 200 ml of isopropanol. Next, the filter cake is washed with water, heated to 60-80 ^o C, from chlorine ion. Water consumption is 1-1.2 liters. The aqueous paste of the final product is dried in an oven at 80-90 ^o C to a volatile content of not more than 0.5%
Get 61.5 g of 1,3-di- (phenylaminophenoxy) -proranol-2, which is 84.8% of theory, counting on n-oxydiphenylamine.

The final product is a gray powder with a pinkish or light brown tint with a melting point of 142-143 ^o C.

 With the described technology, a series of experiments was carried out to obtain 1,3-di- (phenylaminophenoxy) propanol-2, the results of which are presented in Table 1.

 Obtaining 1,3-di- (phenylaminophenoxy) propanol-2.

 Example 2. Obtaining 1,3-di- (beta-naphthylaminophenoxy) -propanol-2.

Under the conditions of Example 1, 83.65 g (0.32 g / mol) of 90% n-hydroxyphenyl-beta-naphthyl-amine and 200 ml of ethyl alcohol were charged into a flask, the reaction mixture was heated to boiling (78 ^° C), then add over 10-15 minutes 16 g (0.176 g / mol) of a 44% sodium hydroxide solution and kept at boiling for 3-4 hours. The precipitated precipitate of the target product and sodium chloride is filtered off and washed with 500 ml of ethyl alcohol. The precipitate is repulped in 300 ml of water, filtered and washed with water until no chlorion is present.

The aqueous paste of the product is dried at 80-90 ^o C to a volatile content of not more than 0.5%
65.8 g of 1,3-di- (beta-naphthylaminophenoxy) -propanol-2 are obtained, which is 78% yield based on the starting n-hydroxyphenyl-beta-naphthylamine.

The target product is a purple powder with a melting point of 162-163 ^o C.

 Obtaining 1,3-di- (beta-naphthylaminophenoxy) -propanol-2.

Claims (1)

The method of producing 1,3-di- (arylaminophenoxy) propanols-2 by the interaction of p-hydroxyphenylarylamines with epichlorohydrin and alkali in a solvent at elevated temperature, characterized in that the reaction is carried out at a molar ratio of p-oxydarylamine epichlorohydrin alkali equal to 1 0.51 0, 59 0.55 0.65, in the environment of aliphatic alcohols C ₂ C ₃ at the boiling point.

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