SU755788A1 - Method of preparing naphthylphosphorl dichlorides - Google Patents

Description

The invention relates to the field of chemistry of organophosphorus compounds, and in particular to a new method for producing dichlorohydrides of naphthylphosphoric acid intermediates in the synthesis of diamides of naphthylphosphoric acids, which are stabilizers of polyheteroarylenes, ⁵ and naphthylphosphoric acids used in histochemistry for the study of hydrolytic enzymes.

A known method of producing dichlorohydrides of naphthylphosphoric acids by boiling a mixture of naphthol with phosphorus oxychloride at a molar ratio of reagents 1. (1-2) for 20 hours [1]. The yield of target products is up to -70.5%.

The disadvantages of this method are the long reaction time (20 h) and the low yield of dichlorohydrides of naphthylphosphoric acids.

The closest to the invention in terms of technical essence and achieved results _χ is a method for producing dichlorohydrides of naphthylphosphoric acids by reacting naphthol with phosphorus oxychloride at a molar ratio of reagents 1: 6 in the presence of potassium chloride catalyst at 110 ° C for 10 h (2). To absorb the resulting hydrogen chloride use 1 N. sodium hydroxide solution. Target products are obtained in 84.6-85% yield.

The disadvantage of this method is the use of a large excess of phosphorus oxychloride, harsh process conditions (110 ° C) and a long process time.

The aim of the invention is to simplify the process of producing dichlorohydrides of naphthylphosphoric acids.

The goal is achieved by the proposed method for the preparation of dichlorohydrides of naphthylphosphoric acids, which consists in the fact that naphthol is reacted with phosphorus oxychloride at a molar ratio of reactants 1: (2-3) with anhydrous aluminum chloride as a catalyst and the process is carried out by preliminary maintaining the reaction mass at room temperature followed by heating to 5O-8O ° C.

A distinctive feature of the method is that naphthol and phosphorus oxychloride are taken in a molar ratio of 1: (2-3), anhydrous aluminum chloride is used as a catalyst, and the process is carried out at a preliminary $. keeping the reaction mass at room temperature, followed by heating to 50-80 ° C.

The proposed method allows to simplify the process of obtaining dichlorohydric acid naphthyl- ¹⁰ phosphoric acids by reducing the amount of phosphorus oxychloride introduced into the reaction by 2–3 times, to reduce the reaction time by 3 times, and to reduce the temperature of the process from 110 to 5 ° –8 ° C. Target products ¹⁵ are obtained with a yield of 74-87%.

Example 1. Obtaining dichlo ranks of the / 3-naphthalephosphoric acid dride.

In a three-necked flask equipped with a mechanical stirrer, thermometer and reflux holo- dilnikom ²⁰ with outlet tube was placed

144.16 g (1 mol) of β-naphthol, 306, 68 g (2 mol) of phosphorus oxychloride, 1.34 g (0.01 mol) of anhydrous aluminum chloride, the reaction mass is kept at room temperature for 2 hours, ²⁵ then for 30 minutes the temperature of the reaction mass is raised to 75 ° C and maintained at this temperature. 1 h. Hydrogen chloride released is absorbed with a 10% alkali solution. At the end of the exposure, ³⁰ excess of phosphorus oxychloride is distilled off, the residue is subjected to / vacuum distillation. 219.59 g (84.1% of theory) of β-naphthylphosphoric acid dichloride are obtained. Boiling point 152155 ° С / 1 mm Hg, t. Ha. 39-40 ° C. ²⁵

Example 2. Obtaining dichloride (3-naphthalephosphoric acid.

Under the conditions of Example 1, from 144.16 g (1 mol) of (3-naphthol, 460.02 g (3 mol) of phosphorus oxychloride in the presence of 1.34 g (0.01 mol) of non-40 aqueous aluminum chloride, 229.18 is obtained d. (87.8% of theory) of dichlorohydride (b-naphthylphosphoric acid. Boiling point 152-155 ° С / 1 mm Hg, mp 39-40 °.

PRI me R 3, Preparation of dichlorohydride ⁴⁵ da (3-naphthylphosphoric acid.

And a three-necked flask equipped with a mechanical stirrer, a thermometer, a reflux condenser with a branch tube is placed

144.16 g (1 mol) (3-naphthol, 460.02 g (3 mol) of phosphorus oxychloride, 1.34 g (0.01 mol) of anhydrous aluminum chloride. The reaction mass is kept at room temperature for 3 hours, then the temperature is increased up to 50 ° C and incubated for another 1 h. Isolation of the product is carried out in the usual manner (Example 1). 223.33 g (85.5% of theory) of dichlorohydride / 3-naphthylphosphoric acid are obtained, b.p. 152155 ° / 1 mm Hg Art., mp 39-40 ° C.

Example 4. Obtaining dichloride anaphthylphosphoric acid.

In a three-necked flask., Equipped with a mechanical stirrer, thermometer, reflux condenser with a branch tube

144.16 g (1 mol) of wasp-naphthol, 306.68 g (2 mol) of phosphorus oxychloride, 134 g (0.01 mol) of anhydrous aluminum chloride. The reaction mass was kept at room temperature for 3 hours, then the temperature was raised to 70 ° C and held for 1.5 hours. The product was isolated in the usual way (> Example 1). 191.88 g (73.5% of theory) of a-naphthylphosphoric acid dichloride are obtained, i.e. 148151 ° C / 1 mmHg

Claims (1)

Claim A method of producing dichlorohydridosis of naphthylphosphoric acids by reacting naphthol with an excess of phosphorus oxychloride in the presence of a catalyst upon heating, which is so that, in order to simplify the process, the reagents are taken in a molar ratio of 1: (2-3 ), anhydrous aluminum chloride is used as a catalyst, and the process is carried out by preliminary maintaining the reaction mass at room temperature, followed by heating to 50-80 ° C.