JPS6260423B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel compound represented by the following formula. In this formula, R ¹ and R ² are a cyan group, a C ₁ -C ₄ -alkanoyl group, a benzoyl group, a group COOB ⁵ or

[Formula] R ³ is a methyl group, a CH ₂ -COO-C ₁ -C ₄ -alkyl group, a phenyl group, or one chlorine atom, bromine atom, a C ₁ -C ₈ -alkoxy group, or a C ₁ -C ₄ - a phenyl group substituted by an alkylmercapto group, X is a group CH, CR ⁵ or N, and R ⁴ is of the formula

【formula】

【formula】

[Formula] or

means a residue of the formula, where B ⁵ is a C ₁ -C ₈ -alkyl group or a C ₂ -C ₃ -alkoxy group substituted by a C ₁ -C ₈ -alkyl group, B ⁶
and B ⁷ are independently a hydrogen atom or C ₁ to _{C 8}
-alkyl group, ^R5 is _C1 - _C4 -alkoxycarbonyl group or group _C6H4N ( _CH3 ) ₂ , ^R6 is hydrogen atom, _methyl group, _C1 - _C4 -alkoxy group or _C1- C ₄ -alkanoylamino group, R ⁷ and R ⁸ are independently a hydrogen atom, a cyan group or a C ₁ -C ₄ -
A _C1 - _C5 -alkyl group or a phenyl group which may be substituted with an alkoxycarbonyl group, ^R9 means a chlorine atom or a bromine atom, and ^R10 means a phenyl group. In addition to those listed above, the individual groups R ¹ are, for example, those listed below. COCH ₃ , COC ₂ H ₅ ,
COC ₃ H ₇ , COC ₆ H ₅ , COOCH ₃ , COOC ₂ H ₅ ,
COOC ₃ H ₇ , COOC ₄ H ₉ , COOC ₆ H ₅ , COO
(CH ₂ ) ₃ OCH ₃ , COO(CH ₂ ) ₃ OC ₂ H ₅ ,
CONHCH ₃ , CONHC ₂ H ₅ , CONHC ₃ H ₇ ,
CONHC ₄ H ₉ , CON(CH ₃ ) ₂ , CON(C ₂ H ₅ ) ₂ ,
CONH ₂ or CONHC ₆ H ₅ . R ² may be the same as or different from R ¹ . The radical R ³ is, for example, as follows. _CH3 ,
C ₆ H ₅ , C ₁ -C ₄ -alkyl-O-C ₆ H ₄ , Cl-
_C6H4 , Br- _{C6H4 , C1} - _C4 - _alkyl - _S - _C6H4
or _CH2 -COO- _C1 - _C4 -alkyl. The radical R ⁵ is, for example, as follows.
COOCH ₃ , COOC ₂ H ₅ , COOC ₄ H ₉ or C ₆ H ₄ N
( _CH3 ) ₂ . The group R ⁴ is individually, for example, the residue of an aniline derivative of the formula: In this formula, R ⁶ is, for example, CH ₃ , OCH ₃ , OC ₂ H ₅ ,
OC ₃ H ₇ , NHCOCH ₃ , NHCOC ₂ H ₅ ,
NHCOC ₃ H ₇ and R ⁷ and R ⁸ are e.g. CH ₃ ,
C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , C ₂ H ₄ CN or C ₂ H ₄ COO−C ₁
~ _C4 -alkyl. To prepare a compound of the formula, the general formula

[Formula] or

A thiazole represented by the formula can be condensed with a compound represented by the general formula R ⁴ -X=O.
In these formulas, R ¹ , R ² , R ³ , R ⁴ and X have the above meanings. The condensation reaction is performed by combining the compound and
This can be carried out by heating to 30 to 160°C, preferably 60 to 100°C. Examples of the solvent include methanol, ethanol, propanol, butanol, methyl glycol, dioxane, acetone, acetonitrile, dimethylformamide, N
- Methylpyrrolidone, water, toluene, xylol, chlorbenzole or nitrobenzole are suitable. The condensation reaction is promoted by the addition of acidic or basic catalysts. Water produced during the reaction can be removed from the reaction mixture as an azeotrope. Suitable catalysts are, for example, inorganic acids, carboxylic acids, such as acid, acetic acid or trichloroacetic acid, as well as phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride or thionyl chloride. Basic catalysts include, for example, ammonium acetate or amines such as piperidine, pyrrolidine, pyridine, triethylamine or triethanolamine. For details of the preparation of the compounds, reference is made to the Examples. The compounds of the formula are largely new substances and can be prepared, for example, analogously to the instructions in DE 191 3 472 A1. Compounds of some of the formulas are described in Journal of Practical Chemistry, Vol. 316, p. 684 (1974). Of particular industrial importance are compounds represented by the following formula. In this formula, B ¹ and B ² are a cyan group, a C ₁ -C ₄ -alkoxycarbonyl group, a C ₁ -C ₄ -alkanoyl group, or the above-mentioned substituted carbamoyl group, and B ³ is a chlorine atom, a bromine atom, or a methoxy group. , a phenyl group optionally substituted with an ethoxy group or a _C1 - _C4 -alkylmercapto group, ^B4 is the following formula

【formula】

[Formula] or

It means a residue of the formula, where R ⁶ to R ¹⁰ have the meanings given above. In that case, preferred groups as R ⁶ are a hydrogen atom, NHCOCH ₃ , CH ₃ , OCH ₃ or NHCOC ₂ H ₅ ,
R ⁷ and R ⁸ are hydrogen atoms, CH ₃ , C ₂ H ₅ ,
C ₂ H ₄ CH, C ₂ H ₄ COO−C ₁ -C ₄ -alkyl or
_C6H5 and ^R10 _{are C6H5 .} The dyes of the formula are purple to yellowish-green and are particularly suitable for dyeing polyester fibers. Glossy dyeings are obtained which have very good fastness properties, in particular light, wet and heat fastnesses. The new dye is used to coat polyester,
It is of particular industrial importance in that green shades can be prepared without the use of dye mixtures. Furthermore, this dye is
It is also suitable for printing or printing polyester/cotton blend fabrics, for example by the method described in German Patent No. 1 811 796. Parts and percentages in the examples below are by weight unless otherwise indicated. Example 1 21 parts of 4-phenyl-thiazol-2-yl-cyanoacetic acid methyl ester are mixed with 15 parts of p-nitroso-dimethylaniline hydrochloride, 10 parts of glacial acetic acid and 5 parts of ammonium acetate in 300 parts of toluene. Heat to reflux. Water generated during the reaction is removed from the system. After 4 hours it is cooled and the dye is suctioned off.
Yield: 35 parts, melting point: 246°C, λ _nax in dimethylformamide: 655 nm. In the same manner as in Example 1, the dyes shown in the following table are produced.

【table】

【table】

[Table] Example 26 6.4 parts of 4-phenyl-thiazol-2-yl-cyanoacetic acid methyl ester was added to chlorobenzole.
Combine 6.7 parts of Michler's ketone in 75 parts, add 2 parts of phosphorous oxychloride, and heat to 60°C.
After 3 hours the mixture is placed on ice and the organic phase is separated, dried and evaporated. Yield: 9 parts, melting point:
98℃. Example 27 11.6 parts of 4-phenyl-thiazol-2-yl-malondinitrile are heated under reflux for 1 hour with 16 parts of 3-methoxy-4-nitroso-diphenylamine and 1 drop of piperidine. After cooling, the dye is suctioned off. Yield: 18 parts as acicular crystals with metallic luster, melting point: >300
℃. Example 28 15 parts of 4-phenyl-thiazol-2-yl-cyanoacet-n-butylamide are boiled with 13 parts of 4-nitrosocyanethyl-ethylaniline hydrochloride in 100 parts of alcohol. After 2 hours it is cooled and the dye is filtered off with suction. Yield: 13 parts as dark blue needles, λ _nax : 650 nm in DMF. The compounds of Examples 29 to 46 shown in the table below are
Manufactured in the same manner as 28.

【table】

【table】

【table】

Claims (1)

[Claims] 1. General formula (In the formula, R ¹ and R ² are a cyan group, a C ₁ -C ₄ -alkanoyl group, a benzoyl group, a group COOB ⁵ or [Formula] R ³ is a methyl group, a group CH ₂ -COO-C ₁ -C ₄ -alkyl) , a phenyl group or a phenyl group substituted by one chlorine atom, a bromine atom, a _C1 - _C8 -alkoxy group or a _C1 - _C4 -alkylmercapto group, X is a group CH, ^CR5 or N, and R ⁴ means a residue of the following formula [formula] [formula] [formula] or [formula], where B ⁵ is substituted by a C ₁ -C ₈ -alkyl group or a C ₁ -C ₈ -alkyl group _C2 - _C3 -alkoxy group, ^B6
and B ⁷ are independently hydrogen atoms or C ₁ to _{C 8}
-alkyl group, ^R5 is _C1 - _C4 -alkoxycarbonyl group or group _C6H4N ( _CH3 ) ₂ , ^R6 is hydrogen atom, _methyl group, _C1 - _C4 -alkoxy group or _C1- C ₄ -alkanoylamino group, R ⁷ and R ⁸ are independently a hydrogen atom, a cyan group or a C ₁ -C ₄ -
An organic compound represented by a _C1 - _C5 -alkyl group optionally substituted with an alkoxycarbonyl group or a phenyl group, ^R9 means a chlorine atom or a bromine atom, and ^R10 means a phenyl group. 2 General formula (In the formula, B ¹ and B ² are a cyan group, a C ₁ -C ₄ -alkanoyl group, a benzoyl group, a group COOB ⁵ or [Formula] B ³ is a phenyl group, or one chlorine atom, bromine atom, C ₁ - A phenyl group substituted by a C ₈ -alkoxy group or a C ₁ -C ₄ -alkylmercapto group, B ⁴ is a residue of the following formula [Formula] [Formula] or [Formula], B ⁵ is a C ₁ -C ₈ - An alkyl group or a _C2 - _C3 -alkyl group substituted by a _C1 - _C8 -alkoxy group, ^B6 and ^B7 independently of each other represent a hydrogen atom or
_C1 - _C8 -alkyl group, ^R6 is a hydrogen atom, methyl group, C1- _C4 -alkoxy group or _C1 - _C4 -alkanoylamino group, _R7 and ^R8 are independent of each ^other ,
Optionally substituted with a hydrogen atom, or a cyan group or a C1 _{- C4} -alkoxycarbonyl group
A compound according to claim 1, represented by a _C1 - _C5 -alkyl group or a phenyl group, ^R10 means a phenyl group. 3 B ¹ and B ² are a cyan group, the group COOB ⁵ or [Formula] B ³ is a phenyl group, or a phenyl group substituted with one chlorine atom or a C ₁ -C ₅ -alkoxy group, B ⁴ is the following formula A compound according to claim 2, in which B ⁵ , B ⁶ , B ⁷ , R ⁶ , R ⁷ and R ⁸ have the meanings given in claim 2 . 4 ^B5 is a _C1 - _C4 -alkyl group or a _{C2 - C3} -alkyl group substituted by a C1- _C4 -alkoxy group, ^B6 and ^B7 are independently a hydrogen atom or
_C1 - _C4 -alkyl group, the other substituents having the meaning given in claim 3;
A compound according to claim 3. 5 R ⁶ is a hydrogen atom, a methyl group, a methoxy group or an acetylamino group, R ⁷ and R ⁸ are independently a C ₁ -C ₅ -alkyl group, or a cyan group or a C ₁ -C ₄ -alkoxycarbonyl group 3. Compounds according to claim 3, meaning a substituted _C2 - _C3 -alkyl group, in which the other substituents have the meanings given in claim 3. 6 General formula [formula] or [formula] (in the formula, R ¹ , R ² and R ³ have the meanings given below)
It is characterized by condensing a thiazole compound represented by the following with a compound represented by the general formula R ⁴ -X=O (wherein R ⁴ and X have the meanings given below),
general formula (In the formula, R ¹ and R ² are a cyan group, a C ₁ -C ₄ -alkanoyl group, a benzoyl group, a group COOB ⁵ or [formula] R ³ is a methyl group, a group CH ₂ -COO-C ₁ -C ₄ -alkyl) , a phenyl group or a phenyl group substituted by one chlorine atom, bromine atom, _C1 - _C8 -alkoxy group or _C1 - _C4 -alkylmercapto group, X is a group CH, ^CR5 or N, and R ⁴ means a residue of the following formula [formula] [formula] [formula] or [formula], where B ⁵ is substituted by a C ₁ -C ₈ -alkyl group or a C ₁ -C ₈ -alkyl group _C2 - _C3 -alkoxy group, ^B6
and B ⁷ are independently hydrogen atoms or C ₁ to _{C 8}
-alkyl group, ^R5 is _C1 - _C4 -alkoxycarbonyl group or group _C6H4N ( _CH3 ) ₂ , ^R6 is hydrogen atom, _methyl group, _C1 - _C4 -alkoxy group or _C1- C ₄ -alkanoylamino group, R ⁷ and R ⁸ are independently a hydrogen atom, a cyan group or a C ₁ -C ₄ -
A method for producing an organic compound represented by a _C1 - _C5 -alkyl group optionally substituted with an alkoxycarbonyl group or a phenyl group, ^R9 means a chlorine atom or a bromine atom, and ^R10 means a phenyl group.