DE1950600A1 - Benzimidazo-isoquinoline-aldehydes - Google Patents

Abstract

Benzimidazo-isoquinoline-aldehydes of formula:- (where R1 and R2 each = H, halogen, (ar)aliphatic, aromatic, alkoxy, carbonamide, sulphonamide or sulphonic acid grps. or N(R3)2; R3 = (ar)aliphatic or aromatic or one R3 may be H), are prepd. by reaction of benzimidazo-isoquinolines or homophthalic acid cpds. with HCOOH. The products are fluorescent cpds.

Description

Process for the preparation of benzimidazo-isoquinolone aldehydes The invention relates to a process for the preparation of benzimldazo-isoquinolone-aldehydes by reacting benzimidazoisoquinolones or homophthalic acid compounds with Formic acid It is known that chlorobenzene is formed in the presence of aluminum chloride with formic acid to p-chlorobenzaldehyde and in the presence of acetic acid to form 4-amino-1,5-dimethyluracil convert to the 5-formyl compound. (Industrial and Engineering Chemistry 26, 1517 (1934); Liebigs Annalen der Chemie 612, 175 (1958); Chemical Reports 97, 1405 (1964)).

3-Oxythionaphthen (Journal Practical Chemistry (2) 103, 104 (1921)) or 2-methylindole (reports of the German Chemical Society 46, 2158 (1913)) result in methine compounds when reacted with formic acid; Connections with at least one free hydrogen atom on the amino group is generally set to N-formyl derivatives. A formylation on a carbon atom more aromatic or heterocyclic compounds with arne: isenic acid without a condensing agent however not yet described.

It has now been found that benzimidazo-isochinolone aldehydes of the general formula in which R1 and R2 can be the same or different and each represents a hydrogen atom, a halogen atom, an aliphatic, araliphatic, aromatic radical, an alkoxy group, a carbonamide group, a sulfonamide group, a sulfonic acid group or the radical mean, in which the individual radicals R5 can be equal or different and each denote an aliphatic, araliphatic or aromatic radical, one of the two radicals R3 can also mean a hydrogen atom, advantageously obtained when benzimidazoisoquinols of the general formula or homophthalic acid compounds of the general formula in which R1 and R2 have the aforementioned meaning, reacts with formic acid.

In the case of using benzoylaminobenzyl)) benzimidazole-2-carboxylic acid, the reaction can be represented by the following formulas: The process according to the invention provides a large number of new benzimidazo-isoquinolone aldehydes in a simple manner in good yield and purity. These advantageous results are surprising in view of the prior art; one would have expected, in analogy to other acylating agents such as acetic anhydride, benzoyl chloride, chloroformic acid esters, as the end product, N-formyl compounds.

The starting materials II, III or IV are reacted with the formic acid in a stoichiometric amount or with a preferably up to 50-fold excess over the stoichiometric amount of formic acid. Preferred starting materials II, IIt and IV and correspondingly preferred end materials I are those in whose formula R1 and R2 can be identical or different and each have a hydrogen atom, a chlorine atom, 1 allyl group with 1 to 6 carbon atoms, a carboxyl group, an aralkyl group with 7 to 12 carbon atoms, a phenyl group, an alkoxy group having 1 to 4 carbon atoms, a carbonamide group, a sulfonamide group, a sulfonic acid group or the remainder mean in which the individual radicals R can be identical or different and each denotes an alkyl radical with 1 to 4 carbon atoms, an aliphatic acyl radical with 2 to 5 carbon atoms, a benzyl radical, a benzoyl radical or a phenyl radical, and one of the two radicals R3 as well may represent a hydrogen atom. The radicals mentioned can also be replaced by organic groups which are inert under the reaction conditions, e.g. B. alkyl groups or alkoxy groups each having 1 to 3 carbon atoms may be substituted.

There are, for example, the following starting materials II, III and IV in Consideration: 11-oxo-5.11-dihydro-benzimidazo- (1,2 - b) isoquinoline, 11-oxo-2-chlorine, 11-oxo-3-ethyl-, 11-oxo-4-butyl-, 11-oxo-1-phenyl-, 11-oxo-7-methyl-, 11-oxo-8-tert-butyl-, 11-oxo-9-phenyl-, 1 1-oxo-10-propoxy, 11-oxo-2-carboxy-, 1 1-oxo-3-sulfo-, 11-oxo-2-sulfonamido, 11-oxo-3-carbonamido, 11-oxo-7-methoxy, 11-oxo-8-benzyl, 11-oxo-8-dimethylamino, 11-Oxo-9-α-benzylamino-, 11-Oxo-9-phenyl-amino-, 11-Oxo-8-acetamino-, 11-Oxo-9-benzamino-5,11-dihydro-benzimidazo (1,2 -b) isoquinoline, 2 (2-carboxy-benzyl) -benzimidazole, 2- (2-carboxy-benzyl) -5-chlorobenzimidazole, 2- (2-carboxy-4-benzaminobenzyl) -benzimidazole, 2-amino- (2-carboxy-phenyl) -acetanilide, 2-amino-4-methyl- (2-carboxy-phenyl) -acetanilide.

The reaction is carried out at a temperature between 80 and 200 ° C, preferably between 100 and 1500C, unpressurized or under pressure, continuous or discontinuous carried out. In general, the starting material formic acid is also used at the same time as a solvent, it can be mixed with water, usually with no more than 15% by weight of water, based on formic acid, are used. Possibly can still inert organic solvents such as under the reaction conditions Alkanecarboxylic acids, e.g. B. acetic acid, propionic acid; aromatic hydrocarbons, z. B. mono-, di-, trichlorobenzene, nitrobenzene; used cii.

The reaction can be carried out as follows: A mixture of starting material II, III or IV and formic acid and optionally another solvent is held at the reaction temperature for 4 to 8 hours. Possibly can add a condensing agent to the mixture, e.g. B. sodium formate, for acceleration Are added to the reaction advantageously in an amount of 1 to 15% by weight, based on formic acid. The end product is then extracted from the reaction mixture in the usual way, e.g. by filtration or removal of the solvent, digestion of the residue with water or aqueous mineral acid and filtration, isolated.

The novel compounds which can be prepared by the process of the invention are fluorescent agents and valuable starting materials for the production of dyes. So show the z. B. in an amount of 0.05 wt.% In dimethylformamide in daylight and UV light have a very strong fluorescence. The fluorescence has in the case of aromatic Hydrocarbons as solvents have a bluish tint, in the case of tertiary amines and cyclic acid.

amides as solvents have a greenish yellow tint. As a fluorescent agent can the new end materials I, for example, mineral oils, hydraulic and brake oils, Paints, paints, printing inks, daylight phosphors, marking agents or Road marking paints are added.

The parts listed in the following examples represent the most important parts. They relate to parts by volume like the kilogram to the liter.

Example 1 254 parts II-0xo-5,11-dihydro-benzimidazo (1,2-b) isoquinoline are introduced into 3000 parts by volume of formic acid and reflux for 8 hours be cooked at 1000C. After cooling, the mixture is suctioned off, the filter material with it Formic acid and washed with water and dried. 256 parts of 11-oxo-5,11-dihydro-benzimidazo (1,2-b) isoquinoline-carbaldehyde- (6) are obtained in the form of greenish-yellow crystals with a melting point of 302-3050C (from nitrobenzene). The elemental analysis is correct here and in the following examples agrees with the calculated values within the error limits.

Example 2 252 parts of 2- (2-carboxy-benyl) -benzimidazole according to the method described in J.org. Chemistry 31, 1498 (1966), 150 parts of sodium formate and 3750 parts by volume of formic acid are refluxed at 100 ° C. for 6 hours. After re-embedding as in Example 1, 242 parts of that described in Example 1 are obtained End product.

Example 3 If the 2- (2-carboxy-benzyl) -benzimidazole des Example 2 by 270 parts of 2-amino- (2-carboxy-phenyl) -acetanilide, prepared according to the distributor described in Helv.Chim.Acta 6, 519 (1923) is obtained from Example 2 analogous procedure 199 parts of the end product described in example 1.

Example 4,248 parts of 11-oxo-2-methyl-5,11-dihydro-benzididazo- (1,2-b) @@@ quinoline be kl eln mixture of 1200 parts by volume of formic acid and 1200 parts by volume Glacial acetic acid registered. After refluxing for eight hours, the mixture is analogous Example 1 worked up. 226 parts of 11-oxo-2-methyl-5,11-dihydrobenzimidazo (1,2-b) isoquinoline-carbaldehyde- (6) are obtained in the form of yellow-tinged crystals, melting point: 276 - 278 ° C (from dimethylformamide).

Example 5 264 parts of 11-oxo-2-methoxy-5,11-dihydro-benzimidazo (1,2-b) Isoquinoline, 50 parts of sodium formate and 2500 parts of formic acid are 6 hours boiled under reflux at 100 ° C. After working up as in Example 1, one obtains 242 parts of 11-oxo-2-methoxy-5,11-dihydro-benzimidazo (1,2-b) isoquinoline-carbaldehyde- (6) in the form of greenish-yellow crystals which melt at 338 - 34200 with decomposition.

Example 6 A mixture of 268.5 parts of 11-oxo-2-chloro-5,11-dihydro-benzimidazo (1,2-b) isoquinoline and 5000 parts of formic acid is refluxed at 1000 C for 8 hours and Worked up analogously to Example 1. 283 parts of 11-oxo-2-chloro-5,11-dihydrobenzimidazo (1,2-b) isoquinoline-carbaldehyde are obtained - (6). The compound melts after recrystallization from nitrobenzene at 298 - 2990C with decomposition.

Example 7 286.5 parts of 2- (2-carboxy-benzyl) -5-chloro-benzimidazole, obtained from homophthalic anhydride and 1,2-n-1 amlno-4 - chlorobenzene in boiling Butanol, melting point 5600C> and 120 parts of sodium formate are in 4500 parts Formic acid entered. After 6 hours of heating at 101 ° C., the mixture becomes analogous Example 1 worked up. 218 parts of the end product described in Example 6 are obtained.

Example 8 314 parts of 11-oxo-5,11-dihydro-benzimidazo (1,2-b) isoquinoline-2-sulfonic acid, 240 parts of sodium formate and 5000 parts by volume of formic acid are under for 4 hours Boiled reflux at 100 ° C, the starting material goes completely into solution. The solution is then concentrated under reduced pressure and the residue with 2500 parts of 2% strength by weight aqueous hydrochloric acid digested. After vacuuming the filter material, Washing and drying gives 270 parts of 11-oxo-5,11-dihydro-benzimidazo (1,2-b) isoquinoline-6-carbaldellyd-2-sulfonic acid, which does not melt up to 560 0 Example 9 277 parts of 11-oxo-9-dimethylamino-5,11-dihydro-benzimidazo (1 isoquinoline and 5000 parts by volume of formic acid are refluxed for 8 hours 100 ° C cooked. The clear solution is poured into twice the volume of water, with the aldehyde precipitates. It is suctioned off and washed with water. After drying receives 284 parts of 11-oxo-9-dimethylamino-5,11-dihydro-benzimidazo- (1,2-b) isoquinoline-carbaldehyde- (6). After recrystallization from dimethylformamide, the end product is more greenish in shape Crystals that decompose when heated to 250 ° C.

Example 10 310 parts of II-oxo-9-phenyl-5, II-d-Hydro-benzimidazo (l, 2-b) isoquinoline and 5000 parts by volume of formic acid are refluxed at 100 ° C. for 8 hours and then worked up analogously to Example 1. 297 parts of II-oxo-9-phenyl-5, II-d-hydrobenzimidazo (1,2-b) isoquinoline-carbaldehyde are obtained - (6) in the form of greenish crystals with a melting point of 312-313 C (dimethylformamide).

Example 11 353 parts of II-oxo-9-benzamino-5, II-d-Hydro-benzimidazo (l, 2-b) isoquinoline, 4000 parts by volume of propionic acid and 1000 parts by volume of formic acid are 8 hours refluxed at 11200.

After working up the mixture as in Example 1, 331 parts are obtained II-Oxo-9-benzamino-5,11-d-hydrobenzimidazo (1,2-b) isoquinoline-carbaldehyde- (6) in Form of greenish crystals - which soften at 3250C and melt at 550 - 3600C (from dimethylformamide).

Example 12 371 parts of 2- (2-carboxy-4-benzyl) benzimidazole (obtained from 4-benzoylamino-homophthalic anhydride and o-phenylenediamine in boiling butanol, Melting point 305-308 ° C) and 200 parts of sodium formate are in 6000 parts by volume Entered formic acid and refluxed at 1010 C for 6 hours. After Working up the mixture as in Example 1 gives 298 parts of that in Example 11 described end product.

Example 13 383 parts of II-Oxo-2-methoxy-9-benzamino-5, II-d-Hydro-benzimidazo - (1,2-b) isoquinoline, 100 parts of sodium formate and 7000 parts by volume Formic acid are refluxed at 100 ° C for 6 hours. The mixture is worked analogously to the example l and receives 569 parts of ll-Oxo-2-methOxy-9-benzamino-5, ll-dihydro-benzLmidazo (l, 2-b) isoquinoline-carbaldehyde- (6), mp 360 ° C.

Claims (2)

Claims 1. Process for the preparation of benzimidazo-isoquinolone aldehydes of the general formula in which R1 and R2 can be identical or different and each represent a hydrogen, om, a halogen atom, an aliphatic, araliphatic, aromatic radical, an alkoxy group, a carbonamide group, a sulfonamide group, a sulfonic acid group, or the radical N # 3 by the individual R nen radicals R3 can be identical or different and each denote an aliphatic, araliphatic or aromatic radical, one of the two radicals R3 can also denote a hydrogen atom, characterized in that benzimldazo-isoquinolones of the general formula or homophthalic acid compounds of general formula 1 in which R1 and R2 have the aforementioned meaning, reacts with formic acid. 2. Benzimidazo-isoquinolone aldehydes of the general formula in which R1 and R2 can be the same or different and each have a hydrogen atom, a chlorine atom, an alkyl group with 1 to 6 carbon atoms, a carboxyl group, an aralkyl group with 7 to 12 carbon atoms, a phenyl group, an alkoxy group with 1 to 4 carbon atoms, a carbonamide group , a sulfonamide group, a sulfonic acid group or the radical -N-R3, in which the individual radicals R5 can be identical or different and each represent an alkyl radical with 1 to 4 carbon atoms, an aliphatic acyl radical with 2 to 5 carbon atoms, a benzyl radical, a benzoyl radical or denote a phenyl radical, one of the two radicals R5 can also denote a hydrogen atom.