JPH0367114B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel butadiene compounds. For more details, use formula (1) (In formula (1), X represents hydrogen, methyl group, methoxy group, or ethoxy group, Y represents hydrogen or cyano group, _{R 3} represents hydrogen, methyl group, hydroxyl group, methoxy group, or ethoxy group, and R ₁ and R ₂ each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, a chloroethyl group, or an alkoxyalkyl group having 3 to 6 carbon atoms.However, R ₁ and R ₂ are not both hydrogen.) The present invention relates to the butadiene-based compound shown. The butadiene compound of the present invention is used for dyeing synthetic fibers, as well as for coloring plastics, waxes, mineral oils, organic solvents, and the like. The butadiene compound represented by formula (1) of the present invention is synthesized according to the following reaction formula. (In the above reaction formulas (1), (2) and (3), X, Y, R ₁ ,
(R ₂ and R ₃ have the same meanings as above) In other words, 3-phenyl-3-imino-propionitriles and malonitrile are heated and condensed in an organic solvent, and in the subsequent step, pheinyl aldehydes and an organic solvent are condensed. Condense by heating at medium temperature to 100℃. Furthermore, equation (1)
A compound in which Y is a cyano group can be easily synthesized by adding sodium cyanide to the product in an aproc solvent, followed by oxidation. In the reaction formula (1), specific examples of 3-phenyl-3-imino-propionitriles include:
3-phenyl-3-imino-propionitrile,
3-(4-methoxyphenyl)-3-imino-propionitrile, 3-(4'-methylphenyl)-3-
Examples include imino-propionitrile, 3-(2'-methylphenyl)-3-imino-propionitrile, and the like. Further, specific examples of aldehydes in reaction formula (2) include 4-(N,N-dimethylamino)-benzaldehyde, 4-(N,N-di-β-methoxyethyl-amino)-benzaldehyde, 4-(N,N-dimethylamino)-benzaldehyde, −
(N,N-diethylamino)-3-methyl-benzaldehyde, 4-(N-methyl-N-β-chloroethyl-amino)-3-methyl-benzaldehyde, 4-(N,N-diethylamino)-3-hydroxybenzaldehyde , 4-(N,N-dibutylamino)-3-methoxybenzaldehyde and the like. The condensation of malonitrile and phenyl-imino-propionitriles proceeds by heating at 180°C within 50°C in an alcohol such as ethanol, diethylene glycol, or methylcellosolve, and after the reaction is complete, the reaction solution is poured into water. Separate the precipitated crystals. The condensation of the condensate and benzaldehydes in the next step proceeds very easily in organic solvents such as alcohols and even at room temperature, but if necessary,
It may be heated from room temperature to 100° C. in the presence of an organic base such as piperidine, triethylamine, or sodium alcoholate. In addition, when converting H into a cyano group, the raw material compound is dissolved in an aprotic solvent such as dimethylformamide or dimethyl sulfoxide, added by adding sodium cyanide to it at room temperature to 50°C, and then oxidized by adding bromine. You can reach your goal by The butadiene compound (1) of the present invention is extremely clear, has strong coloring power, and can be used in various organic solvents, mineral oils,
It has good solubility in paraffin, wax, etc., and is useful as an indicator for these materials, but it is also useful for dyeing synthetic fibers such as polyester fibers, acetate fibers, and polyamide fibers, and for coloring various plastics. Useful. It is also useful as a dye for so-called thermal transfer printing of textiles. The present invention will be explained below with reference to synthesis examples, where "part" and "%" indicate "part by weight" and "% by weight", respectively. Example 1 7.2 parts of 3-phenyl-3-imino-propionitrile (synthesized according to the method described in JP-A-58-62169) and 3.6 parts of malonitrile are refluxed in 20 parts of ethanol for 3 hours. After cooling, pour into 300 parts of ice water, add hydrochloric acid to adjust pH to 2, and stir. The solidified crystals are separated and dried to obtain 8 parts of 4,4-didiano-3-phenyl-allyl nitrile. To 5.8 parts of allylnitrile and 4.5 parts of 4-N,N-dimethyl-benzaldehyde are added 2 drops of piperidine in 30 parts of alcohol, and the mixture is stirred at 20°C for 2 hours.
The precipitated crystals were separated, washed with a small amount of ethanol, and dried to obtain 7.8 parts of a compound with the following structure. mp207-209℃ λmax (85% acetone aqueous solution) 527nm Dyeing hue of polyester fiber Blueish red Example 2 3-phenyl-3-imino described in Example 1
The following compound was obtained by substantially the same procedure as in Example 1, except that 8.7 parts of 3-(4'-methoxyphenyl)-3-imino-propionitrile was used in place of propionitrile. λmax (85% acetone aqueous solution) 520 nm Dyeing hue of polyester fiber Red Example 3 2.9 parts of 4,4-dicyano-3-phenyl-allyl cyanide, 4-(N-methyl-N-β-chloroethyl-amino)-3-methyl -benzaldehyde
Add 3 drops of piperidine to 3.2 parts in 20 parts of alcohol and stir at 20°C for 2 hours. The precipitated crystals were separated, washed with a small amount of ethanol, and dried to obtain 5.0 parts of a compound having the following structure. λmax (85% acetone aqueous solution) 530nm Dyeing hue of polyester fiber Blueish red 2.9 parts of the above compound was dissolved in 20 parts of dimethylformamide, and while stirring, 0.9 parts of sodium cyanide was added at 10°C.
Add as follows and stir at 10°C to 15°C for 1 hour. Then add 2.3 parts of bromine at below 10°C and 1 part at 10 to 15°C.
Stir for an hour. This was poured into 300 parts of ice water to separate the precipitate, washed with water, and dried to obtain 3.0 parts of a compound having the following structure. λmax (85% acetone aqueous solution) 575 nm Dyeing hue of polyester fiber Navy blue Example 4 2.9 parts of 4,4-2 dicyano-3-phenyl-allyl cyanide, 4-(N,N-diethylamino-3
Add 2 drops of piperidine to 2.9 parts of -hydroxy-benzaldehyde in 20 parts of alcohol and stir at 20°C for 1 hour. The precipitated crystals were separated and washed with a small amount of ethanol to obtain 4.7 parts of a compound with the following structure. λmax (85% acetone aqueous solution) 536 nm In addition, during the above condensation, after stirring at 20°C for 1 hour, the temperature was raised to 75°C for about 1 hour, refluxed for 1 hour, cooled, and the precipitated dye was separated, converting it into a dye with the following structure. .

[Formula] or λmax (85% acetone aqueous solution) 537 nm Examples 5 to 15 Butadiene compounds of formula (1) were obtained by substantially the same procedure as in Examples 1 to 4 using cyano-imino-propyl nitriles and benzaldehydes.
λmax (85% acetone in water) using the obtained compound
measurements and dyeing of polyester fibers.

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Claims (1)

[Claims] 1 Formula (1) (In formula (1), X represents hydrogen, methyl group, methoxy group, or ethoxy group, Y represents hydrogen or cyano group, _{R 3} represents hydrogen, methyl group, hydroxyl group, methoxy group, or ethoxy group, and R ₁ and R ₂ each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, a chloroethyl group, or an alkoxyalkyl group having 3 to 6 carbon atoms.However, R ₁ and R ₂ are not both hydrogen.) Butadiene compounds shown.