CS269038B1

CS269038B1 - Method of anthranilic acid's isopropylamide production

Info

Publication number: CS269038B1
Application number: CS886780A
Authority: CS
Inventors: Milan Ing Csc Polievka; Peter Ing Grolmus; Jozef Ing Csc Sojka; Ladislav Ing Uhlar
Original assignee: Polievka Milan; Peter Ing Grolmus; Jozef Ing Csc Sojka; Uhlar Ladislav
Priority date: 1988-10-13
Filing date: 1988-10-13
Publication date: 1990-04-11
Also published as: CS678088A1

Abstract

Riešenie sa zBoberé spSsobom výroby izopropylamidu kyseliny antranilovej. Na N-chlorftalimid v suspenzii sa posobí hydroxidom sodným při teplote -10 až +10 °C a následné zmesou izopropylaminu s izopropylamín hydrochloridom vo vodě. Po zahriatí reakčnej zmesi na 15 až 40 °C vznikne zrazenina izopropylamidu kyseliny antranilovej. Po izolácii sa získá produkt vysokej čistoty v dostatočnom výtažku, pričom sa zníži produkcia odpadového chloridu sodného.The solution is based on the method of manufacture anthranilic isopropylamide. On the The N-chlorophthalimide in suspension is prepared sodium hydroxide at -10 to + 10 ° C followed by a mixture of isopropylamine with isopropylamine hydrochloride in water. After heating the reaction mixture to 15-40 ° C an isopropyl amide precipitate is formed anthranilic. After isolation, it is obtained a product of high purity in sufficient extract, while reducing waste production sodium chloride.

Description

1 EN 269 038 B1

The present invention relates to a novel process for the production of anthranilic isopropylamide, which comprises reacting N-chlorophthalimide with sodium hydroxide at temperatures of from -10 to + 10 ° C and subsequent reaction of the resulting intermediate with an isopropylamine-hydrochloric acid solution.

For the synthesis of anthranil isopropylamide of formula I

have been proposed in the past. Especially known is the process of starting phthalimide (or phthalic anhydride) via sodium phthalamate with Hoffman's sodium chloride decomposition and condensation of the resulting intermediate with isopropylamine (EP 57424). A disadvantage is the large amount of sodium chloride waste and the associated ecological problems. Another process, starting from isate anhydride and iso-propylamine in dimethylformamide, makes it difficult to isolate and purify the amine, since the by-product is a substituted urea that contaminates the desired product (Staiger, R., Wagner, E., Org. Chem. 18, 1427 (1953); Jakobs R .; Hetroxyclic Chem. 1337 (1970)]. the more violet known process is based on the pericrylic acid itself, respectively. its methyl ester and isopropylamine (Schick MJ: Nonionic Surveyant, Marcel Decker, Inc. New York p. 215 (1967); U.S. Pat. No. 2,844,609). The disadvantage of the reaction is, however, a significant shift of its equilibrium to the starting solution side, in particular excess methanol.

These drawbacks are eliminated by the process for producing anthranium isopropylamide from N-chlorophthalimide according to the present invention by carrying out the N-chlorophthalimide in suspension at -10 to +10 ° C, preferably at 0 ° C, p8. with sodium hydroxide, followed by isopropylamine and isopropylamine hydrochloride in water, and after heating the reaction mixture to 15 to 40 ° C, preferably 20 to 30 ° C, a precipitate of anthranilic isopropylamide is formed which is recovered in isolation 75% to N-chlorophthalimide with a minimum purity of 97% determined by chromatography.

Said process for the preparation of anthranilic islamide provides a product of high purity in sufficient yield, not only reducing the production of waste sodium chloride, but also making it possible to use hydrogen chloride, resulting in the production of N-chlorophthalimide, to prepare the isopropylamine hydrochloride needed for the second stage of synthesis. N-chlorophthalimide is prepared by chlorine phthalimide with chlorine gas. However, 200 mesh size phthalimide is required. This method provides N-chlorophthalimide XI in sufficient purity (96%) and in high yield (95-98%) CO.

Cl

WHAT

(II) EN 269 038 B1

In the preparation of anthranilic acid isopropylamide, N-chlorophthalimide is first treated with sodium hydroxide at temperatures ranging from -10 to + 10 ° C. It is believed that this reaction results from the N-chlorophthalimide of an acid addition dianion of formula III (U.S. Pat. No. 3,828,038).

After the reaction of the volatile N-chlorophthalimide (manifested by clarification of the suspension), a solution of isopropylamine and hydrochloric acid is added to the reaction mixture, at one time or at 10 to + 10 ° C for 10 minutes. After the blend, the mixture is stirred at this temperature for 0 to 5 minutes and then heated to ambient temperature or water bath to 30 to 40 ° C while the white precipitate begins to precipitate. anthranilic isopropylamide. This was washed with water (to pH about 7) and dried at 50 ° C. The reaction can be schematically described as follows, C0 NC1 +

CO NH "CH (CH 2)" HClNaOH —------------>

-10, + 10 ° C CO-NH-CH-CH, 3CH, nh 2 Example 1 9.4 g of N-chlorophthalimide (mp = 180 to 183 ° C, Mh = 181.58 g / mol) was suspended in 50 ml water and cooled to 0 ° C in an ice bath. Next, 4.2 g of hydroxide solution in 20 ml of water are dissolved and, after cooling to 0 ° C, N-chlorophthalimide is added to the suspension. The temperature rises to 4 ° C over 1.5 minutes following an exothermic reaction.

The mixture was stirred at 0 to +1 ° C for 14 minutes. After this time, a solution prepared from 8.8 g of isopropylamine, 9.8 g of concentrated hydrochloric acid and 90 ml of water was added in one portion. The entire reaction mixture was heated in a water bath and after reaching 38 ° C it was removed (in 3 min). A white precipitate begins to precipitate from the solution, which thickens. The mixture was stirred for a further 5 minutes and then cooled to 20 ° C. After filtration, washing and drying, 7.0 g of product are obtained, m.p. 146-148 ° C, containing 98.0% of anthranilic isopropylamide (determined by chromatography). Example 2

In the same manner as in Example 1, the same amount of N-chlorophthalimide and sodium hydroxide was reacted and a solution of isopropylamine and hydrochloric acid was prepared. between 0 and +2 ° C. After the addition of isopropylamine hydrochloride (after 5 minutes) the reaction mixture was stirred for a further 5 minutes. It is then continued as in Example 1. 6.9 g of product are obtained with a melting point of 145-148 ° C and a purity of 97.7%.

Claims

Example 3 6.0 g of N-chlorophthalimide was suspended in 30 ml of water and cooled to 10 ° C, a solution of 2.7 g of sodium hydroxide and 1.6 ml of water was prepared and also cooled to 10 ° C. Simultaneously, another solution is prepared by mixing 5.5 g of isopropylamine, 7.0 g of hydrochloric acid and 50 ml of water. The lysate solution is added to the N-chlorophthalimide suspension at 10 ° C. After 6.5 min, a solution of isopropylamine and hydrochloric acid is added to the reaction mixture and stirred at this temperature for 5 min. It is then continued as in Example 1. 4.2 g of anthranilic isopropyl amide are obtained (m.p. = 145-147 ° C). Example 4 9.4 g of N-chlorophthalimide are suspended in 50 ml of water and cooled to -1 ° C. Thereafter, 4.2 g of sodium hydroxide was dissolved in 25 ml of water, cooled to 0 ° C and added to a suspension of N-chlorophthalimide. The temperature is kept at

Low: 4 ° C. After 12 minutes from the addition of the hydroxide to the reaction mixture, a solution of 8.4 g of isopropylamine, 10.0 g of concentrated hydrochloric acid and 85 ml of water is added. The temperature is maintained between 0 and 0 during the addition

Low: 4 ° C. Upon completion of the dosing, the reaction mixture is allowed to warm to ambient temperature. After filtration, washing and drying, 7.0 g of anthranilic isopropylamide of 98.2% (m.p. = 147-149 ° C) is obtained. OBJECT OF THE INVENTION The process for producing anthranilic isopropylamide from N-chlorophthalimide, characterized in that the N-chlorophthalimide in suspension is treated with sodium hydroxide followed by a mixture of isopropylamine and isopropylamine at -10 to + 10 ° C, isopropylamine hydrochloride in water and after heating the reaction mixture to 15 to 40 ° C, preferably 20 to 30 ° C, an anthranilic isopropylamide precipitate is formed which is isolated.