DE3902687A1 - Boron complexes - Google Patents

Abstract

Novel boron complexes of the formula <IMAGE> in which Y = halogen, OCOCH3 or OSO3H, R = a substituent, R1 and R2 = H, optionally substituted C1-C8-alkyl, C5-C6-cycloalkyl or phenyl, n = 0, 1 or 2 with the condition that R1 and R2 are not simultaneously hydrogen, their preparation and use for the preparation of dyestuffs.

Description

The invention relates to new boron complexes of the formula

wherein

Y = halogen, OCOCH₃ or OSO₃H,
R = a substituent,
R₁, R₂ = H, optionally substituted C₁-C₈-alkyl (unbranched and branched), C₅-C₆-cycloalkyl or phenyl,
n = 0, 1 or 2, with the condition that R₁ and R₂ are not simultaneously hydrogen

means, as well as their manufacture and use for manufacture of dyes.

If Y means halogen, it is primarily chlorine, bromine or preferably fluorine.

R can stand for a large number of substituents which determine the course of the Do not adversely affect manufacturing or further processing processes. Preferably come for R alkyl, alkoxy, -CO₂-alkyl and -CONH-alkyl into consideration, the alkyl and alkoxy radicals preferably 1 contain up to 6 carbon atoms. Furthermore, R can be an acid group such as e.g. B. -SO₃M and -CO₂M mean, where M is usually hydrogen, ammonium or is an alkali metal atom such as sodium or potassium. R can also for an electronegative group such as nitro, cyano or halogen, in particular Chlorine or bromine.  

Of particular interest are compounds of formula I in which Y = each F and / or R₁ and R₂ independently of one another hydrogen, optionally substituted with phenyl C₁-C₄-alkyl or substituted with C₁-C₄-alkyl, C₁-C₄-alkoxy or phenoxy Phenyl or cyclohexyl and n is the number zero. C₁-C₄-alkyl represents for example: methyl, ethyl, n-propyl, n-butyl and the corresponding isomeric radicals.

The boron complexes of the formula I according to the invention are prepared by reacting the compound of the formula

wherein R₁ and R₂ have the meaning given above, with boron compounds such as B. boron trifluoride etherate, preferably boron trifluoride ethyl etherate, BF₃ gas or with BCl₃, BBr₃, H₃BO₃ / H₂SO₄ and H₃BO₃ / acetic anhydride. At least 2 moles of the boron compound are used per mole of compound of the formula II used. The reaction is preferably carried out in aprotic non-polar solvents such as B. benzene, monochlorobenzene, dichlorobenzene, Trichlorobenzene or chlorinated hydrocarbons and at elevated temperature, preferably at 70-150 ° C.

The compounds of formula II are known and can be known Methods are made.

The boron complexes of the formula I obtained in this way are obtained in high yield, the isolation is carried out in the usual way, such as. B. by suction, Filter or centrifuge followed by washing and drying.

The boron complexes of the formula I according to the invention are intermediate products and can mainly be used to make dyes, especially Disperse dyes can be used. The production of the dyes takes place, for example, by combining the boron complexes of the formula I in one aprotic polar solvents such as dimethyl sulfoxide,  N, N-dimethylformamide, N-methylformamide, N-methylacetamide, formamide, Acetamide, N-methylpyrrolidone, 2-pyrrolidone, N-formylmorpholine, N-formylpiperidine, Pyridine or mixtures of these solvents with malononitrile, or compounds of the formula

wherein R₃ and R₄ are independently hydrogen and optionally C₁-C₄-alkyl substituted with phenyl. The implementation preferably takes place at temperatures of 10-60 ° C.

These dyes are new and represent another subject of the Invention represents. The implementation of the boron complexes of formula I and those in which R₁ and R₂ each represent hydrogen according to EP-A-2 39 538 new dyes obtained with malononitrile correspond to the Formula III

wherein R₂ is hydrogen, optionally substituted C₁-C₈ alkyl, C₅-C₆-cycloalkyl or phenyl.

The dyes by implementing the boron complexes of formula I and also those in which R₁ and R₂ each represent hydrogen according to EP-A-2 39 538 with the amines of the formula

are also new and correspond to the formula IV

wherein one X is hydrogen and the other X of X₁ and X₂ the rest

means in which R₃ and R₄ independently of one another hydrogen and optionally C₁-C₄-alkyl substituted with phenyl.

These dyes of the formulas III and IV can be used for Dyeing mainly polyester materials, with dyeings with good Overall realities can be obtained.

In the following examples, which explain the invention in more detail, without being limited to this, parts and percentages are always unless otherwise stated, parts by weight and percentages by weight.

example 1

13 parts of 1-amino-4-methylaminoanthraquinone are in 150 parts of o-dichlorobenzene dissolved at 140 ° and with 30 parts of boron trifluoride Ethyl etherate added. The reaction mixture is at 10 hours this temperature stirred. The suspension is sucked off hot and the Washed residue with o-dichlorobenzene and toluene and dried.

The boron complex of the structure is obtained:

The procedure is analogous, but instead of the 13 parts, 1-amino-4- Methylaminoanthraquinone equimolar amounts of those in the table below diaminoanthraquinones (II), the following boron complexes (I) receive:  

Table 1

Example 33

3.3 parts of bordifluoride complex according to Example 1 of EP-A-2 39 538 are in 50 parts of dimethyl sulfoxide with 10 parts of diethylamine Stirred for 2 hours at room temperature. The reaction mixture is with Diluted 100 parts of water and the precipitated reaction product sucked off, washed with water and dried. The raw product comes with Toluene cleaned. A dye of the formula is obtained:

which polyester material colors in violet shades.

The procedure is analogous, but instead of Diethylamine equimolar amounts of the amine of the formula

this gives a dye of the formula  

which dyes polyester materials in violet tones.

Example 34

3.3 parts of bordifluoride complex according to Example 1 are in 50 parts of dimethyl sulfoxide with 10 parts of diethylamine Stirred for 2 hours at room temperature. The reaction mixture is with Diluted 100 parts of water and the precipitated reaction product sucked off, washed with water and dried. The raw product is cleaned with toluene. A dye of the formula is obtained:

which colors polyester materials in violet shades.

The following dyes are obtained by the same process:

Example 42

3.3 parts of the boron difluoride complex according to Example 1 are at 50 ° in a mixture of 100 parts of dimethyl sulfoxide, 4.4 parts of potassium acetate and 6.6 parts of malononitrile. You leave them The temperature drops and stirs for a further 15 hours at room temperature. The The reaction mixture is then diluted with 200 parts of water, the Reaction product fails. The crude product is in dimethyl sulfoxide recrystallized, the blue dye of the formula

is obtained.

Example 43

The procedure is analogous to Example 42, but uses the Bordifluoride complex of 1-amino-4-phenylaminoanthraquinone according to Ex. 26, the main product is the blue dye Formula:

Example 44

3.3 parts of the bordifluoride complex according to Example 1 of EP-A-2 39 538 are at 50 ° in a mixture of 100 parts of dimethyl sulfoxide, 4.4 parts of potassium acetate and 6.6 parts of malononitrile registered. The temperature is allowed to drop and the mixture is stirred for a further 15 hours Room temperature. The reaction mixture is then with 200 parts of water diluted, the reaction product precipitates. The raw product is in Dimethyl sulfoxide recrystallized, the blue dye of the formula  

is obtained.

Claims (11)

1. Boron complex of the formula wherein
Y = halogen, OCOCH₃ or OSO₃H,
R = a substituent,
R₁, R₂ = H, optionally substituted C₁-C₈-alkyl, C₅-C₆-cycloalkyl or phenyl,
n = 0, 1 or 2 with the condition that R₁ and R₂ are not simultaneously hydrogen
means. 2. Boron complex according to claim 1, wherein Y = per F and (R) _n , R₁ and R₂ have the meaning given in claim 1. 3. boron complex according to claim 1 or 2, wherein R₁ and R₂ independently of one another hydrogen, optionally substituted with phenyl C₁-C₄-alkyl or with C₁-C₄-alkyl, C₁-C₄-alkoxy or phenoxy substituted phenyl or cyclohexyl and Y and (R ) _{n have} the meaning given in claim 1. 4. Boron complex according to one of claims 1 to 3, wherein Y = F and R₁ and R₂ have the meaning given in claim 3 and n represents the number zero. 5. A process for the preparation of a boron complex according to claim 1, characterized in that one mole of the compound of the formula wherein R is a substituent, n is the numbers 0, 1 or 2 and R₁ and R₂ are hydrogen, optionally substituted C₁-C₈-alkyl, C₅-C₆-cycloalkyl or phenyl, and wherein R₁ and R₂ are not simultaneously hydrogen with at least 2 moles of one Reacting boron compound. 6. The method according to claim 5, characterized in that as Boron compound boron trifluoride etherate used. 7. Use of the boron complexes according to claim 1 for the production of Dyes. 8. Compounds of the formula wherein R₂ is hydrogen, optionally substituted C₁-C₈-alkyl, C₅-C₆-cycloalkyl or phenyl. 9. Compounds of the formula wherein one X is hydrogen and the other X of X₁ and X₂ the rest means in which R₃ and R₄ independently of one another are hydrogen and C₁-C₄-alkyl optionally substituted with phenyl, and wherein R₁ and R₂ = H, optionally substituted C₁-C₈-alkyl, C₅-C₆-cycloalkyl or phenyl. 10. Process for the preparation of the compounds of formula wherein R₂ is hydrogen, optionally substituted C₁-C₈-alkyl, C₅-C₆-cycloalkyl or phenyl, characterized in that a boron complex of the formula wherein
Y = halogen, OCOCH₃ or OSO₃H,
R = a substituent,
R₁, R₂ = H, optionally substituted C₁-C₈-alkyl, C₅-C₆-cycloalkyl or phenyl,
n = 0, 1 or 2
is reacted with malononitrile. 11. Process for the preparation of the compounds of formula wherein one X is hydrogen and the other X of X₁ and X₂ the rest means in which R₃ and R₄ independently represent hydrogen and optionally substituted by phenyl C₁-C₄-alkyl, and R₁ and R₂ = H, optionally substituted C₁-C₈-alkyl, C₅-C₆-cycloalkyl or phenyl, characterized in that a boron complex of the formula wherein
Y = halogen, OCOCH₃ or OSO₃H,
R = a substituent,
R₁, R₂ = H, optionally substituted C₁-C₈-alkyl, C₅-C₆-cycloalkyl or phenyl,
n = 0, 1 or 2
is with an amine of the formula wherein R₃ and R₄ independently of one another are hydrogen and optionally substituted with phenyl C₁-C₄-alkyl, implemented.