DE1960376A1 - Isoquinolines for dye manu - Google Patents

Abstract

5-Oxo-1,2,3,5-tetradhydro-thiazolo 3,2-b isoquinolines of formula: in which the ring A may be further substituted e.g. by X and Y where X is H, Cl, Br, alkyl, alkoxy, alkylamino, dialkylamino, arylamino, acylamino, aryl or aryloxy, and Y is H, Cl, Br, alkyl or alkoxy. The cpds. are used in dye preparation.

Description

5-Oxo-1.2.3.5-tetrahydro-thiazolo L3 2-bJ isoquinolines and process for their preparation The invention relates to compounds of the general formula I. in which the ring A can still carry substituents and a process for their preparation.

Compounds of the general formula Ia are of industrial importance in which X is a hydrogen, chlorine or bromine atom or an alkyl, alkoxy, alkylamino, dialkylamino, arylamino, acylamino, aryl or aryloxy group and Y is a hydrogen, chlorine or bromine atom or an alkyl or Mean alkoxy group.

In addition to the substituents already mentioned individually, for X and Y named for example: methyl, ethyl, iso-propyl, t.-butyl, methoxy, ethoxy, methylamino, Ethylamino, butylamino, i3-ethylhexylamino, B-hydroxyethylamino, dimethylamino, Diethylamino dibutylamino, phenylamino, methylphenylamino, chlorophenylamino, phenyl, Methylphenyl, chlorophenyl, methoxyphenyl, phenyloxy, acetylamino, Propionylamino, Benzoylamino, chlorobenzoylamino or methylbenzoylamino.

Of particular importance are compounds of the formula Ia in which X and Y represent hydrogen or chlorine atoms or methyl or methoxy groups.

You can prepare the compounds of formula I by that Homophthalic acid or homophthalic anhydride or their substituted in the benzene nucleus Reacts derivatives with B-aminoethyl mercaptan (cysteamine) or salts thereof. As salts of the cysteamine are z. B. called the hydrochloride, hydrogen sulfate or hydrobromide.

The following working methods have proven to be useful: a) Man heats the components in a water-immiscible solvent, such as Benzene, toluene, xylene, chlorobenzene or etrachloroethane, in the presence of a trace Carboxylic acid and removes the water by circling.

b) The components are heated in a water-miscible aliphatic Carboxylic acid, such as glacial acetic acid or propionic acid, in the presence of a catalytic amount of the sodium salt of this carboxylic acid.

Molar ratio: equivalent amounts or an excess of up to 50% a component.

Reaction temperature: 80 to 200,000, preferably 100 to 150,000.

Working up: In a) the solvent is at normal pressure, under distilled off under reduced pressure or with steam and the residue is isolated; at b) is diluted with water, whereby the reaction product precipitates.

It was surprising and unforeseeable that the implementation of homophthalic acid compounds with cysteamine form compounds of the formula I, because one in the reaction of the corresponding hydroxy compound, the ß-aminoethanol, under the same conditions only the associated ß-hydroxyethyl homophthalimide receives.

The compounds of formula I are valuable intermediates, for. B. for the production of azo dyes, where they serve as coupling components.

Parts and percentages in the following examples relate to unless otherwise stated, on the weight.

Example 1 A mixture of 18 parts homophthalic acid, 8.5 parts Cysteamine, 5 parts of anhydrous sodium acetate and 100 parts by volume of glacial acetic acid Stirred at 120 ° for 12 hours. The clear solution is then poured into 250 parts of ice water, the reaction product precipitating colorless. It is filtered off with suction, washed with water and dried. 18.6 parts of 5-oxo-1.2.3.5-tetrahydro-thiazolo.2-bisoquinoline are obtained. The compound melts after recrystallization from ethanol at 122 ° C and shows following analysis values: 11 9 calc. C 65.1 H 4.4 N 6.9 0 7.9 S 15.8 Found 65.2 4.5 6.9 8.4 15.3 Example 2 16.2 parts homophthalic anhydride, 8.5 parts cysteamine and 5 parts of glacial acetic acid are boiled in 200 parts of chlorobenzene, using a Water separator removes the water formed during the reaction. After completion the elimination of water (4 to 5 hours) the chlorobenzene is driven off with steam and sucked off the remaining suspension after cooling. Receives after drying 17.9 parts of a colorless compound identical to that described in Example 1 is identical.

Comparative experiment with ß-hydroxyethylamine: 90 parts of homophthalic acid xylene and 5 parts by volume of glacial acetic acid are entered in 1000 parts by volume and 140 ° C stirred. To the 50 parts of the solution are added dropwise over the course of 4 hours 2-Hydroxyäthylamin and removes the water formed in the reaction via a Water separator. After the addition is complete, continue heating until no more water separates out in the separator (approx. 8 hours). Then the reaction mixture freed from xylene by steam distillation and mixed with enough methanol until a clear solution is obtained.

Crystallization sets in when it cools down. One lets stand overnight sucks up the crystals and washes them with cold water. Receives after drying one 86 parts of N- (B-hydroxyethyl) homophthalimide with a melting point of 146 to 147 0 (from Ethanol).

C11H11NO3 calc. C 64.4 H 5.4 N 6.8 0 23.4 Found 64.6 5.5 6.9 23.3 Example 3 29.9 parts of 2-carboxy-4-benzoylaminophenylacetic acid, 7.7 parts of cysteamine and 8 parts of anhydrous sodium acetate are added to 350 parts by volume of glacial acetic acid and stirred at 120 ° C for 16 hours. The reaction mixture is then diluted with 100 Parts of the room water, cools and sucks. After drying, 30 parts are obtained 5-Oxo-7-benzoylamino-1.2.3.5-tetrahydro-thiazolo [3.2-b] isoquinoline of melting point 232 to 23300 (from glacial acetic acid).

018H14N2O2S Ber. C 67.2 H 4.3 N 8.7 0 9.9 S 9.9 Found 66.9 4.6 9.0 10.3 9.6 Following the procedure described in Example 3, the following were made 5-Oxo-1.2.3.5-tetrahydro-thiazolo [3.2-b] isoquinoline produced: example Substituent Melting Point 4 6-Acetylamino 166-167 ° C 5 8-Methyl 107-108 oC 6 6-Bromo 154-155 OC 7 7-chloro 148-149 ° C 8 7-methoxy 134-135 ° C 9 7-phenyl 138-139 ° C 10 7-tert-butyl 115-116 ° C 11 7-phenylamino 177-178 ° C 12 6-acetamino-7-chloro 172-173 ° C

Claims (4)

Claims 1. 5-Oxo-1.2.3.5-tetrahydro-thiazolo [3.2-b] isoquinolines of the general formula in which the ring A can still carry substituents. 2. Compounds according to Example 1 of the general formula in which X is a hydrogen, chlorine or bromine atom or an alkyl, alkoxy, alkylamino, dialkylamino, arylamino, acylamino, aryl or aryloxy group and Y is a hydrogen, chlorine or bromine atom or an alkyl or Mean alkoxy group. 3. Compounds according to claim 2, wherein X and Y are hydrogen or Mean chlorine atoms or methyl or methoxy groups. 4. A process for the preparation of compounds according to claim 1, characterized in that homophthalic acids or homophthalic anhydrides of the formulas or with the compound of the formula H2N-CH2CH2 -SH or salts thereof.