DE1945053B2 - BASIC COLORS, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE FOR COLORING, PRINTING AND MADE-TO-MEASURE INKING OF POLYACRYLNITRILE, SAUER MODIFIED POLYESTERS OR MODIFIED POLYAMIDES - Google Patents

Description

C- (CH = CH) _1n R

C N

wherein

R, R ₁ , R ₂ and m have the meaning given above

C = C-CHO

wherein

A, R ₃ , R ₄ and η have the meaning given above,

condensed in an acidic medium supplying an anion X ^s or with the addition of a condensing agent which forms an anion X.

4. The method according to claim 3, characterized in that glacial acetic acid is used as the acidic medium used with or without the addition of hydrochloric acid.

5. Process for dyeing, printing and mass dyeing (spin dyeing) of materials which are whole or predominantly from polymerized acrylonitrile, from acid-modified polyesters or from acid modified polyamides, characterized in that dyes of claim I used.

The present invention relates to new basic dyes of the formula (I) and a process for their preparation, which is characterized in that compounds of the formula (II) are mixed with heterocyclic aldehydes of the formula (511) or their functional derivatives in one an anion X. supplying acidic medium or with the addition of a condensation agent which forms an anion X °.

-C- (CH = CH) ₁₁₁ R

H
R,

C ^ N

H N

(11)

R, H H

/ ^C " ^Rl

C-C = CH-N

N R, N C

in

(CH = CH -) ", R

10

20th

In the formulas (I), (II) and (111) means

A the remaining links of a possibly common in the field of basic dyes, nonionic residues of substituted indolenine ring,

R Phenyl which is _{substituted by C, -C 4} -alkyl, cyclohexyl, phenyl, fluorine, chlorine, bromine, trifluoromelhyl, acetyl, cyano, melhoxy- or ethoxycarbonyl, methylsulf; nyl, methylsulfonylamino, C, -C ₃ -alkoxy or phenoxy can be, thienyl, which can be substituted by methyl, furyl, which can be substituted by dichlorophenyl,

Pyridyl, benzoxazolyl, benzthiazolyl or naphthyl,

R, hydrogen or phenyl,

R _{2 is} hydrogen, phenyl, which can be substituted by chlorine or

R, and R ₂ together tetramethylene or R and R, together 1,2,3,4-tetrahydro-naphtho- (1,2),

R ₃ hydrogen or cyano,

R ₄ C _r C ₆ -alkyl, phenyl, benzyl, / ί-phenylethyI, cyclohexyl, methoxycarbonylmethyl,

X 'an anion and
m is the number 0 or 1.

Compounds of the formula II suitable for carrying out the claimed process are, for example, jo way

3-phenylpyrazoline - (.: 12),

3- (4'-methylphenyl) pyrazoline - (/! 2), 3- (2'-ethylphenyl) pyrazoline - (, 12), 3- (4'-Isopropylphenyl) pyrazoline - (. L2), 3- (4'-tert-butylphenyl) pyrazoline- (. 12), 3- (4'-CyclohexylphenyI) -pyrazoline- (. 12), 3- (4'-Biphenylyl) -pyrazoline - (/ 12), 3- (4'-chlorophenyl) -pyrazoline - (, J2), 3- (3'-chlorophenyl) -pyrazoline - (/ 12), 3- (2'-chlorophenyl) pyrazoline - (./ i2), 3- (2 ', 4'-dichlorophenyl) pyrazoline - (/ 12), 3- (3 ', 4'-dichlorophenyl) pyrazoline - (/ 12), 3- (4'-bromophenyl) pyrazoline - (/ 12), 3- (4'-fluorophenyl) -pyrazoline - (/ l2), 3- (4'-trifluoromethyl) -pyrazoline- (zl2), 3- (4'-Acetylphenyl) pyrazoline - (/ 12), 3- (4'-Cyanophenyl) pyrazoline - (/ 12), 3- (4'-methoxycarbonylphenyl) pyrazoline- (12), 3- (4'-ÄlhoxycarbonylphenyI) -pyrazoline- (12), 3- (4'-MethylsulfonylphenyI) -pyrazoline- (12), 3- (4'-methylsulfonylaminophenyl) pyrazoline- (12),

3- (4'-Melhoxyphenyl) -pyrazoline- (12), 3- (4'-Ethoxy phenyl (-pyrazoline 12), 3- (4'-Phenoxyphenyl) -pyrazoline- (. 12), 3- (4'-Isopropoxyphenyl) -pyrazoline- (12), 3-styryl-5-phenyl) -pyrazoline- (. 12), 3- (p-chlorostyryl) -5 - ('4'-chlorophenyl) -pyrazoline - (. J 2),

3- (o, p-dich! Orstyryl) -5- (2 ', 4'-dichlorophenyl) -pyrazoline - (, J2),
3- (2'-thienyl) pyrazoline- (12),
3- (5'-methylthienyl-2 ') -pyrazoline- (12), 3- (2'-furyl) -pyrazoline- (12),
3- [5 '- (o, p-dichlorophenyiruryl-2'] - pyrazoline- (J2),
3- (4'-pyridyl) -pyrazoline- (. 12),
3- (2'-Benzoxazolyl) pyrazoline- (12). 3- (2'-Benzlhiazolyl) -pyrazoline - (, 12), 3- (l'-naphthyl) -pyrazoline - (/ 12), 3- (2'-naphthyl) -pyrazoline - (/ 12), 3- Phenyl-4,5-tetramelhylenepyrazoline- (12), 3,4-diphenyl-pyrazoline- (12),
3,5-Diphenyl-pyrazoline- (12) and the pyrazoline equivalent (IV).

N N-H

(IV)

40 Suitable compounds of formula (III) are aldehyde Indohn-Ri-for example, summarized in Table 1 below.

Suitable functional derivatives of the compounds (III) are, for example, acetates, nitrones and azomethines and enamines and their salts, such as anilinovinyl compounds and the primary products of the Vilsmeier Aldehyde synthesis, also the corresponding geminal dihalogen compounds.

hydrogen methyl hydrogen hydrogen hydrogen hydrogen Cyan methyl hydrogen hydrogen hydrogen hydrogen Cyan methyl hydrogen Methoxy hydrogen hydrogen C vii η methyl hydrogen Ethoxy hydrogen hydrogen

Fortset / urm

hydrogen ethyl hydrogen Phenyl hydrogen Benzyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen methyl hydrogen ethyl hydrogen methyl hydrogen methyl

hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen methyl hydrogen hydrogen hydrogen hydrogen methyl hydrogen hydrogen hydrogen hydrogen methyl hydrogen hydrogen hydrogen hydrogen methyl hydrogen hydrogen hydrogen ethyl hydrogen Methoxy hydrogen hydrogen hydrogen Ethoxy hydrogen hydrogen hydrogen Trifluoromethyl hydrogen hydrogen hydrogen fluorine hydrogen hydrogen hydrogen chlorine hydrogen hydrogen hydrogen chlorine hydrogen chlorine hydrogen chlorine hydrogen Methoxy hydrogen Methylsulfonyl hydrogen Methoxy amino hydrogen Dimethylamino hydrogen Methoxy Methoxy hydrogen hydrogen Methoxy carbonyl hydrogen Cyan hydrogen Methoxy hydrogen Methoxy hydrogen Methoxy carbonyl hydrogen Acetyl hydrogen Methoxy hydrogen Phenyl hydrogen Methoxy hydrogen hydrogen hydrogen Phenyl hydrogen Cyclohexyl hydrogen hydrogen hydrogen hydrogen Methoxy hydrogen carbonyl chlorine hydrogen chlorine hydrogen Methoxy hydrogen Methoxy hydrogen 4,5-benzo 4,5-benzo hydrogen hydrogen hydrogen 5,6-benzo 5,6-benzo ethyl hydrogen hydrogen 6,7-benzo 6,7-benzo

The acidic medium is preferably anhydrous or water-containing organic and inorganic Acids, for example acetic acid, formic acid, propionic acid, chloro-, di- and trichloroacetic acid, hydrochloric acid, Sulfuric acid and phosphoric acid and mixtures of such acids. If you use an organic Acid, it is possible - but generally not required - to accelerate the condensation an acid anhydride, e.g. B. acetic anhydride to add.

The condensation can also be carried out in inert organic solvents such as methyl chloride, chloroform, Carbon tetrachloride, tetrachloride, benzene, toluene or chlorobenzene using a condensing agent such as phosphorus oxychloride, phosphorus trichloride, phosphorus tachloride or thionyl chloride are executed.

A preferred embodiment of the present invention consists in heating approximately more equivalently Quantities (II) and (III) in glacial acetic acid to about 40 "C to the boiling point, preferably to 75 ° -105" C. the Isolation of the resulting dye is done in the usual manner, e.g. B. by diluting with Wassei and salting out with table salt.

Preferred dyes are those of the formula (V

R ₂ H

C-CH ₂

CH = CH-N

N = C R

X '

wherein

R, R ₂ and X ° have the meaning given and R _{5 is} a C 1 -C 1 -alkyl radical.

CH ₃

CH ₃

CH-CH-N

M)

Cl ¹

ίο

The type of anion contained in the dyes (I) is important for their coloristic properties generally insignificant and due to the manufacturing process and any cleaning that may have been carried out of the raw dye given. In general, the dyes lie as halides (especially as chlorides or bromides) or as methosulphates, ethosulphates, sulphates, benzene or toluene sulphonates or as acetates before. The anions can be used in any way against other anions such as tetrafluoroborate. Phosphate-, Chlorozincate, nitrate, perchlorate, oxalate, propionate, formate, citrate, tartrate, lactate or benzoate ions be replaced.

The dyes according to the invention are suitable for dyeing, printing and mass dyeing of synthetic, semi-synthetic and natural materials, e.g. B. of polyamides, acetate silk, leather, coconut fibers, Jute, sisal, paper and silk, for making inks and ballpoint pen pastes, for use in rubber printing, but above all for dyeing, printing and mass dyeing (spin dyeing) of materials, soft entirely or predominantly made of polymerized, unsaturated nitriles such as acrylonitrile and / or Vinylidenecyanide or from acid-modified aromatic polyesters or from acid-modified polyamides exist. The dyeings and prints on these last-mentioned materials stand out due to excellent fastness properties, especially light; -, wet, over-dyeing, decatur, sublimation, exhaust and Rubbing fastness as well as good etchability. The new dyes are readily soluble, they can be very easily combine well in commercial dyes without compromising the fastness properties in such combinations of the other dyes, and thanks to their very good drawability, they enable J5 deep colorations. Another valuable property of the claimed dyes is their selective drawability on said substrates; so z. B. Polyester, cotton and wool not stained. Particularly noteworthy is also the extraordinary brilliance and purity of the color tones that come with it the new dyes - in particular with the indole derivatives of the formula (V) - can be achieved.

In the DT-PS 7 17 501, the DT-AS 1045 360, the US-PS 29 06 588, the FR-PS 15 63 531 and the GB-PS 749 193 basic methine dyes are described which are attached to the methine bridge instead of Pyrazolinyl (l) residues wear other nitrogen-containing rings. Compared to the closest comparable dyes of these publications, the new dyes have much more advantageous properties. For example possesses the dye of Example 1 compared to the dye of the formula

Brilliance, opposite the dye of the formula

CH = CH-N

Cl '

from the US patent mentioned a significantly higher color strength and a better build-up capacity Compared to the last-mentioned dye, de has a new dye of the formula

CH ₃

Cl ¹

CH = CH-N

CH ₃

a higher color strength, a higher drawing speed and a better build-up capacity.

The parts given in the following examples are parts by weight.

example 1

73 parts of 3-phenylpyrrazoline (.12) and 100 parts of 1,3,3-trimethyl-2-methyleneindoline-fu-aldehyde are heated to 80-90 ° C. with 450 parts of glacial acetic acid and 50 parts of concentrated hydrochloric acid for about 1 hour to cool to about 5O ⁰ C and the mixture diluted with 4000-8000 parts water the initially very finely divided precipitated Farbstofl is grobdispen after addition of saline, and can then be easily aspirated. It corresponds to the formula

CH2 CH2

CH = CH-N

CH ₃

N =

from US-PS 2906588 a surprisingly high and is suitable for dyeing, printing and bulk dyeing of polyacrylonitrile or acid modified Polyesters in extremely brilliant and very genuine greenish yellow tones. The yield is almost quantitative.

If, instead of the abovementioned aldehyde, the respective equivalent amount of one of the following is used Aldehydes are obtained with otherwise unchanged

Working method also very valuable yellow dyes with an analogous structure: 5-methoxy-, 5-ethoxy-, 5-methyl-, 5-ethyl, 5-phenyl, 5-chloro, 5-fluorine, 5-trifluoromethyl, 5-methylsulfonyl-, 7-methyl-, 7-ethyl-, 7-methoxy-, 7-chloro-, 5,7-dichloro-, 5,7-dimethoxy-, 4,6-dimethyl-, 4,6-dichloro- and 4,7-dimethoxy-1,3,3 - trimethyl - 2 - methylene - indoline - <»- aldehyde, I-ethyl-3,3-dimethyl-, I -benzyl-3,3-dimethyl- and l-phenyl-3,3-dimethyl-2-methyleneindoline- (o-aldehyde. These aldehydes are in the same way as the above-

The aldehyde mentioned can be obtained by Vilsmeier formylation of the corresponding 2-methylene indolines.

Example 2

100 parts of 1,3,3-trimethyl-2-methylene-indoline - <»- aI-dehyd and 88 parts of 3- (4'-methoxyphenyl-) pyrazo-Iin - (. I2) are heated to about 100 ° C with 500 parts of glacial acetic acid for 90 minutes. The work-up is carried out as in Example 1. One obtains in a very good yield

ίο the yellow dye of the formula

CH ₇ -CH ₂

OCH,

which is ideal for dyeing, printing and bulk dyeing of polyacrylonitrile and acid modified Polyesters.

The 3- (4'-methoxyphenyl-) pyrazoline- (J2) was prepared by heating the Mannich base obtained from 4-methoxyacetophenone, paraformaldehyde and dimethylamine with excess hydrazine hydrate in methanol with the addition of sodium hydroxide solution and purified by fractional distillation under reduced pressure (bp. _o8 = 160 ° C) The structure was confirmed by analysis and mass spectrum. In an analogous manner, the following pyrazolines were prepared, which - if you work in the manner described in Example 2 using the equivalent amount of one of these pyrazolines - also give very real yellow dyes with a corresponding structure:

3- (4'-ethoxyphenyl-pyrazoline- (z! 2),

3- (4'-methylphenyl) -pyrazoline- (J2),

3- (4'-EthylphenyI) -pyrazoIin- (zl2),

3- (4'-biphenylyl) -pyrazoline- (zJ2),

3- (3'-methoxyphenyl) pyrazoline - (/ | 2),

3- (3 ', 5'-Dimethyl-phenyl) -pyrazoline - (/ l2),

3- (4'-chlorophenyl) -pyrazoline- (zl 2),

3- (3 ', 4'-dichlorophenyl) -pyrazoline- (, 12),
3- (4'-bromophenyl) -pyrazoline- (z) 2),
3- (4'-cyanophenyl) pyrazoline - (/ 12),
3- (4'-fluorophenyl) pyrazoline - (/ l2),

J ₀ 3- (4'-trifluoromethyl-phenyl) -pyrazoline - (/ l 2),
3- (4'-methylsulfonylphenyl) pyrazoline - (/ 12),
3- (4'-methylsulfonylaminophenyl) -pyrazoline-

(/ 12),

3-styryl-5-phenyl-pyrazoline - (/ l2),
v, S-H'-chlorostyrylJ-S-H'-chlorophenyO-pyrazoline - (. J2) and
3-thienyl- (2 '-) - pyrazoline- ( Λ 2).

Example 3

25.9 parts of 1-4 trimethyl-S-methoxycarbonyl-2-methylene-indoline-w-aldehyde and 14.6 parts 3-phenylpyrazoline - (/ l2) are in 150-200 parts of chloroform heated to boiling with 15-20 parts of phosphorus trichloride or phosphorus oxychloride for 30-40 minutes. After distilling off the chloroform and recrystallizing the residue from water under The addition of activated charcoal gives the dye of the formula

CH ₇ -CH,

CH = CH-N

N =

the very real and clear yellow dyeings and prints on polyacrylonitrile and acid modified polyester

Claims (3)

Claims: Basic dyes of the general formula R, H H C CR ₁ C-C = CH-N I \ Rj N = R4 (CH = CH-LR 20th A the remaining members of an indolenine ring, which may be substituted by non-ionogenic radicals customary in the field of basic dyes, 2 ^r > R phenyl which is _{substituted by C 1 -C 4} alkyl, cyclohexyl, phenyl, fluorine, chlorine, bromine, trifluoromethyl, acetyl, cyano, methoxy or ethoxycarbony I, methylsulfonyl, methylsulfonylamino, C 1 -Cj -alkoxy or phenoxy so can, Thienyl, which can be substituted by methyl, Furyl, which can be substituted by dichlorophenyl, r> Pyridyl, benzoxazolyl, benzthiazolyl or naphthyl, R _{1 is} hydrogen or phenyl, R _{2 is} hydrogen, phenyl, which can be substituted by chlorine or R ₁ and R ₂ together are tetramethylene or
R and R ₁ together are 1,2,3,4-tetrahydronaphtho- (1,2), Rj hydrogen or cyan, R ₄ C, -C _ft -alkyl, phenyl, benzyl, / ί-phenylethyl Cyclohexyl, methoxycarbonylmethyl,
X "is an anion and
»I means the numbers 0 or 1. 2. Basic dyes of the general form CHj R ₅ = CH R ₂ - Ν \ H ΓΎ ^{€ Ηί} \ C-CH, V /
/ CH = N = C F. L. wherein R, R ₂ and X "have the meaning of claim I. have and
R _{5 represents} a C _r C 1 -alkyl radical. 3. Process for the preparation of basic dyes of the general formula R, A- C-C = CH-N / I CR ₁ (CH = CH -) ", R X ' A the remaining links of an optionally due in the field of basic dyes common, nonionic radicals of substituted indolenine ring. R phenyl, which _{can be substituted by C 1 -C 4} alkyl, cyclohexyl, phenyl, fluorine, chlorine, bromine, trifluoromethyl, acetyl, cyano, methoxy or ethoxycarbonyl, methylsulfonyl, methylsulfonylamino, C 1 -Cj alkoxy or phenoxy. Thienyl which may be substituted by methyl Furyl, which can be substituted by dichlorophenyl, Pyridyl, benzoxazolyl, benzthiazolyl or naphthyl, R _{1 is} hydrogen or phenyl,
R _{2 is} hydrogen, phenyl, which can be substituted by chlorine or R ₁ and R ₂ together are tetramethylene or
R and R ₁ together 1,2,3,4-tetrahydronaphthol 1,2), R ₃ hydrogen or cyano, R ₄ C ₁ -C ₆ -AIlCyI, phenyl, benzyl, / f-phenylethyl, Cyclohexyl, methoxycarbonylmethyl,
Χ ^Θ an anion and
m means the number 0 or 1, characterized in that one compounds of the general formula with aldehydes of the formula