DE1905833A1 - Process for the preparation of formylmethylene phthalimidines - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG 1 QfI ^ QQ'S

Our reference: O.Z. 26 014 WB / IB

6700 Ludwigshafen, 5-2.1969 Process for the production of Pormylmethylenephthalimidinen

Addendum to patent (patent application P 17 70 826.6 -

O.Z. 25 669).

Subject of the main patent (patent application P 17 70 826.6

- O.Z. 25 669) is a process for the production of Pormylmethylenephthalimidinen the general formula

in which R 1 and R 1 can be the same or different and each denote an aliphatic, cycloaliphatic, araliphatic or aromatic radical, and R "also denotes an alkoxy group or denote a hydrogen atom by reaction of acetophenone-o-carboxamides of the general formula

II, '- CONH - R.

in which R. and Rp have the aforementioned meaning with the reaction product of a formamide of the general formula

\ H

N-C = O III,

in which R, and R ^ can be identical or different and each represent an aliphatic or aromatic radical, moreover. R, and R ₂ . also together with the neighboring nitrogen atom members

637/68 -2-

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O.Z. 26 014

a heterocyclic ring, and an acid halide in the presence of organic solvents and subsequent hydrolysis of the reaction product thus obtained.

It has now been found that the process of the main patent
Can be further developed if, instead of acetophenone-ο-carboxamides of the general formula II, phthalimidine compounds of the general formula

in which R and R_ have the aforementioned meaning. '

The starting materials of the general formula IV of the new process
can e.g. B. by the method described in Collection of Czechoslovak Chemical Communications, Volume 21, page 725 (1956). Preferred starting materials IV and correspondingly preferred end materials I are those in whose formulas R ^ and R can be the same or different and in each case an alkyl radical with 1, 2
or up to 6 carbon atoms, a cycloalkyl radical with up to
8 carbon atoms, an aralkyl group with up to 10 carbon atoms, a phenyl or naphthyl group, R ₂ can also denote an alkoxy group with up to 6 carbon atoms or a hydrogen atom. The radicals mentioned can also be replaced by groups and / or atoms which are inert under the reaction conditions, e.g. B. alkyl, alkoxy groups each with up to 4 carbon atoms, phenyl, nitro, pheny! Amino groups, dialky! Amino groups with up to
8 carbon atoms, chlorine, bromine atoms can be substituted.

It can e.g. B. the following phthalimidine compounds can be used as starting materials IV: 4-ethyl-, 5-cyclohexyl-, 6-benzyl-, ^ -phenyl-, 4-propoxy, 6-isobutyl-3-methylenphthalimidine, 3-methylenphthalimidine; and the corresponding N-cyclohexyl-, N-benzyl-, N-phenyl-, N-naphthyl-, N- (1-methoxy) -propyl- (3) ~, Np-toluyl-, Np-diphenyl-, Np- Ethoxyphenyl-, no-chlorophenyl-, Np-dimethylamino-phenyl-,
Np-diphenylamino, N- (p-nitrophenyl), N- (p-chlorophenyl), N- (2,4-dimethoxyphenyl) compounds. Otherwise, the procedure is according to
carried out the main patent. _,

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The parts given in the examples are parts by weight.

example 1

22/6 parts of N- (p-nitrophenyl) -3-methylenphthalimidine are introduced into a solution of 150 parts of chloroform, 10 parts of dimethylformamide and 15 parts of phosgene at 0-5 ° C. The mixture is kept at 0-5 ° C., at 25 ° C. and at 45 ° C. for one hour. The solvent is then distilled off, the remaining residue is dissolved in 150 parts of v / water, and the pH of the solution is then adjusted to about 9 by means of a soda solution. The precipitate formed is filtered off with suction, washed with water and dried. 22.8 parts (90 % of theory) of N- (p-nitrophenyl) -3- (formylmethylene) phthalimidine of pp. 200 ° C. are obtained.

Example 2

In I50 parts of ethylene chloride and 12 parts of dimethylformamide at 0 - 5 ⁰ C. 21 parts of phosphorus oxychloride was added portionwise, then 25, 6 entered methylenphthalimidin -3-parts of N- (p-chlorophenyl), and the mixture is 1 hour each at 0 - 5 ° C, kept at 30 ° C and at 50 ⁰ C. After working up as in Example 1, 25.2 parts (= 89 % of theory) of N- (p-chlorophenyl) -3- (formylmethylene) phthalimidine with a melting point of 137.degree.-138.degree. C. are obtained.

• Example 3

28.1 parts of N- (2,4-dimethoxyphenyl) -3-methylenphthalimidine are reacted analogously to Example 1 with the reaction product of dimethylformamide and phosgene. After working up, 27.1 parts (87 % of theory) of N- (2,4-dimethoxyphenyl) -3- (formylmethylene) phthalimidine are obtained.

Example 4

In 150 parts of dimethylformamide, 30 parts of phosgene are introduced at from 0 to +5 ⁰ C. After stirring for 2 hours, 20.3 parts of N- (carboxylate: ethyl; -3-methylenephthalimidine are introduced with cooling.

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O. Z. 26

. 1 3 0 ο d 3

The mixture is stirred for 1 hour at 0 to +5 ⁰ C, 1 hour at room temperature and 1 hour at 50 ° C. The mixture is then poured onto ice, adjusted to pH 9 to 10 with dilute sodium hydroxide solution and filtered. 17.3 parts (75 % of theory) of N- (carboxymethyl) -3- (formylmethylene) phthalimidine are obtained.

Example 5

20 parts of phosphorus oxychloride are added in portions at 0 to + 5 ° C. to a solution of 30 parts of N-pormyl-N-methylaniline in 150 parts of ethylene chloride. Then 30 parts of N- (2,4-dichlorophenyl) -3-niethylenphthalimidine are slowly introduced. The mixture is stirred for 1 hour at 0 to + 5 ° C, 1 hour at room temperature and 1 hour at 6O ⁰ C. The solvent is then distilled off, the residue is added to water and the resulting solution is brought to a pH of approx. 10 with potassium hydroxide solution. The precipitate formed is filtered off with suction and dried. 27 parts (82 % of theory) of N- (2,4-dichlorophenyl) -3- (formylmethylene) phthalimidine are obtained.

Example 6

As in Example 5, 17.3 parts of N-ethyl-3-methylenephthalimidine are reacted. 16.5 parts (83 % of theory) of N-ethyl-3- (formylmethylene) -phthalimidine are obtained.

Example 7

In a solution of 18.7 parts of N-isopropyl-3-methylenphthalimidin and 15 parts of N-Pormylpiperidin in 150 parts of trichlorethylene are introduced I5 parts of phosgene at 0 to +5 ⁰ C. The mixture is stirred for 1 hour each at 0 to +10 ⁰ C, at room temperature and at 55 ° C. The solvent is distilled off and the residue is introduced into 300 parts of 5N sodium hydroxide solution. The precipitate formed is filtered off with suction, washed with water and dried. 16.5 parts (77 % of theory) of N-isopropyl-3- (formylmethylene) phthalimidine are obtained.

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Claims (1)

O.Z. 26 014 Claim Further embodiment of the process for the preparation of formyl methylenphthalimidines of the general formula HC - CHO Il in the r and r _? may be the same or different and each denote an aliphatic, cycloaliphatic, araliphatic or aromatic radical, R ₂ can also denote an alkoxy group or a hydrogen atom, by reaction of acetophenone-o-carboxamides of the general formula CH
» CONH - in which R. and R _{2 have} the aforementioned meaning with the reaction product of a formamide of the general formula \ H N-C = O III, in the R, and R ₁ . may be the same or different and each denote an aliphatic or aromatic radical, in addition R, and Rj, together with the adjacent nitrogen atom, can denote members of a heterocyclic ring, and an acid halide in the presence of organic solvents and then Hydrolysis of the reaction product obtained in this way according to the patent (Patent application P 17 70 826.6 - OZ 25 669), characterized in that »instead of acetophenone-o-carboxamides of the general formula II, phthalimidine compounds of the general formula -6- 009836/2158 O.Z. 26th CH It R ₂ -IT Ij N - R, 'IV, ! I in which R. and R _{2 have} the aforementioned meaning, used Badische Anilin- & Soda-Fabrik AG 009836/2158