CH623343A5 - Process for the preparation of new azo dispersion dyes - Google Patents

Description

The subject of the invention is a new process for the preparation of azo compounds which are insoluble or very sparingly soluble in water, which can be used in particular as dispersion dyes.

The dyes obtained by the process according to the invention can be represented by the general formula:

R,

50

55

d - n = n

CH2CH2 "E3

(I)

N <(

-NOT

/ r1

CH2CH2 ~ R * 3

2

(v)

in which U 'and V' are the same or different and each represents a hydrogen, chlorine or bromine atom or a cyano or nitro radical, R'3 represents a cyano radical or in which D represents the remainder of an amine diazotizable aromatic, homocyclic or heterocyclic, devoid of 60 sulfonic acid group, R 1 and R 2 each represent an alkyl radical optionally substituted by a halogen atom or by a hydroxy, alkoxy, acyloxy or carbalkoxy group, R 3 represents a cyano, carbamoyl radical, carboxy or carbalkoxy, and R4 represents a hydrogen or halogen atom (preferably chlorine or bromine) or an alkyl or alkoxy radical.

The alkyl or alkoxy radicals can contain 1 to 4 carbon atoms and are preferably those containing 1 or 2 carbon atoms. When R3 represents a carbalkoxy radical, the latter

3

623,343

may contain 2 to 5 carbon atoms and is preferably the carbomethoxy or carbethoxy radical. As optional substituents of the alkyl radicals R, and R2, mention may, for example, be made of halogen atoms (preferably chlorine or bromine), but above all hydroxy, carbalcoxy (preferably carbomethoxy or carboethoxy), alkoxy (preferably methoxy or ethoxy) and alkyloxy (preferably acetoxy or propionyloxy).

The dyes of formula (I) are prepared by coupling of the diazo derivative of an amine of formula: D-NH2 (II)

with a coupler of formula:

R4-

ch2ch2-r3

(III)

in which R ,, R2, R3 and R4 have the same meanings as above.

The diazotization of the amine of formula (II) can be carried out for example using a mineral acid and sodium nitrite or using a solution of nitrosylsulfuric acid in concentrated sulfuric acid at a temperature between —10 ° C and + 40 ° C, preferably between —10 ° C and + 5 ° C.

The coupling is generally carried out in an optionally buffered acid medium, at a temperature between −10 ° C. and + 40 ° C., preferably between 0 ° C. and 5 ° C. As buffering agent, sodium acetate is generally used .

The amine of formula (II) can be mono- or bicyclic, homocyclic or heterocyclic. Like homocyclic amines, in particular aminobenzenes are suitable, mainly those which carry negative substituents, for example those of formula:

x u

(IV)

in which U represents a hydrogen or halogen atom (preferably chlorine or bromine) or an alkyl, alkoxy, carbalkoxy, acyl, nitro, cyano or sulfamoyl radical, V represents a hydrogen or halogen atom or an alkyl, cyano or trifluoromethyl radical, W represents a hydrogen or halogen atom or an optionally substituted nitro, cyano, carbalkoxy, acyl or arylazo radical, and X represents a hydrogen or halogen atom or a radical alkyl, alkoxy, carbalkoxy, acylamino, nitro or cyano.

As examples of homocyclic amines of formula (II), non-limiting examples that may be mentioned are the following compounds: 1-amino-4-chloro-benzene; 1-amino-4-bromo benzene; 4-amino-4-methylene benzene; 4-amino-4-nitro benzene; 1-amino-4-cyano benzene; 1-amino-2,5-dicyano benzene; 1-amino-4-carbomethoxy benzene; 1-amino-4-carbethoxy benzene; 2,4-amino-2,4-dichloro benzene; 1-amino-2,4-dibromo benzene; 1-amino-2-methyl-4-chloro benzene; 1-amino-2-trifluoromethyl-4-chloro-benzene; 1-amino-2-cyano-4-chloro benzene; 1-amino-2-cyano-4-nitro benzene; amino-1 cyano-2 nitro-4 bromo-6 benzene; 1-amino-2-carbomethoxy-4-chloro benzene; 1-amino-2-carboxy-4-nitro-benzene; 1-amino-2-chloro-4-cyano benzene; 1-amino-2-bromo-4-cyano benzene; 1-amino-2-chloro-4-nitro benzene; 1-amino-2-chloro-4-carbethoxybenzene; 1-amino-2,4-dinitro benzene; 2,4-amino-2,4-dicyano benzene; 1-amino-2,6-dichloro-4 cyano-benzene; 2,6-amino-2,6-dichoro-4-ni-benzene; 1-amino-2,6-dibromo-4-nitro benzene; 1-amino-2,4-dicyano-6 choro-benzene; 1-amino-2,4-dinitro-6-chloro-benzene; 1-amino-3-chloro-4-cyano benzene; amino-1 cyano-2 5 chIoro-5 benzene; 2,4-amino-2,4-dicyano benzene; 1-amino-2-cyano-4,5-trichloro benzene; 1-amino-2-methoxy-4-nitro benzene; 1-amino-2-cyano-4-nitro-6-chloro-benzene; 1-amino-2,4-dinitro-6 cyano-benzene; 1-amino-2,4-dinitro-6 bromo-benzene; 1-amino-2,6-dicyano-4-nitro benzene; amino-1 dicyano-! " 2.6 4-chloro benzene; 1-amino-2,6-dicyano-4-carbomethoxy benzene; 1-amino-2,6-dicyano-4-methyl benzene; 1-amino-2-methyl-4-nitro benzene; 1-amino-2-bromo-4-nitro benzene; 1-amino-2-mesyl-4-nitro benzene; 1-amino-2,5-dichloro-4-cyano benzene; 1-amino-2-cyano benzene; 4-amino diphenyl; ami-15 no-4 diphenyl ether; 4-amino-4-acetylamino benzene; cyclo-hexyl-1 amino-4 benzene; cyclohexyl-1 nitro-3 amino-4 benzene; 4-amino benzophenone; 1 N-amino, N-dimethyl-sulf-4-amoyl benzene; 1-amino-2-nitro, N-dimethylsulfamoyl-4 benzene; 1-amino-2,5-dichloro-4-nitro benzene; 4-amino-azo-benzene ^ 3,2-dimethyl-4 'amino-azobenzene; 2-methyl-5-meth-oxy-4 amino azobenzene; 4-amino-2-nitroazobenzene; 2,5-di-methoxy-4 amino azobenzene; 4-methoxy-4-amino azobenzene; 2-methyl-4-methoxy-4-amino azobenzene; trimethoxy-2,5,4 '4-amino azobenzene; chloro-2 ', 3' or 4'-amino-4 azobenzene '; 3-nitro-4-amino 2-dichloro, 4 'azobenzene; 4-amino-4-sulfamoyl azobenzene.

As heterocycic amines of formula (II), there may be mentioned those which contain a pentagonal or hexagonal nucleus containing 1,2 or 3 heteroatoms such as sulfur, oxygen and especially nitrogen. Examples of such amines include the following compounds:

2-amino thiazole; 2-amino-4-methyl thiazole; 2-amino-4-phenyl thiazole; 2-amino-4-chlorophenyl thiazole; 2-amino-4-ni-trophenyl-4 thiazole; 2-amino-5-nitro thiazole; 2-amino-35-methyl 4-nitro-5 thiazole; 2-amino-5-cyano thiazole; 2-amino-5-mesyl thiazole; 5-amino-3-methyl isothiazole; 2-amino ben-zothiazole; 2-amino-6-methyl benzothiazole; 2-amino-6-meth-oxy benzothiazole; 2-amino-6-chloro benzothiazole; 2-amino-6-cyano benzothiazole; 2-amino-6-nitro benzothiazole; amino-4o 2-6 thiocyanato benzothiazole; 2-amino-6-carbethoxy benzothiazole; 2-amino-4-mesyl benzothiazole; 2-amino-6-mesyl benzothiazole; 3-amino-2, benzisothiazole; 3-amino-5-chloro-benzisothiazole-2,1; 3-amino-5-nitro-benzisothiazole-2,1; ami-no-3 methyl-6 benzisothiazole-2,1; 3-amino-5-chloro-7-bromo 45 benzisothiazole-2,1; 3-amino-5-nitro-7-chloro-benzisothiazole-2,1; 3-amino-5-nitro-7-bromo benzisothiazole-2,1; 2-amino thiadiazole-1,3,4; 5-amino-1,2-thiadiazole; 5-amino-3-methyl-thiadiazole-1,2,4; 5-amino-3-phenyl thiadiazole-1,2,4; 2-amino-5-phenylthiadiazole-1,3,4; 2-amino-3-nitro-5-mesyl thiophene; so 2-amino-3,5-dimesyl thiophene; 2-amino-3-cyano-4-methyl-5-nitro thiophene; 2-amino-3-cyano-4-methyl-5-carbethoxy-thiophene; 2-amino-3,5-dicarbethoxy-4-methyl thiophene; 2-amino-3-cyano-4,5-tetramethylene thiophene; 2-amino-3-carbethoxy-4,5-tetramethylene thiophene; 3-amino indazole; amino-3 ni-55 tro-5 indazole; 3-amino-6 chloro indazole; 2-amino benzimida-zole.

Among the dyes of formula (I) have been found to be particularly interesting:

1 °) Azobenzene dyes of formula:

u. , r4

ch2ch2- r.

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4

in which U 'and V' are the same or different and each represents a hydrogen, chlorine or bromine atom or a cyano or nitro radical, R'3 represents a cyano or carbalkoxy radical and R1; R2 and R4 have the same meanings as above, as well as

2) the dyes of formula:

not,

D '- N =

h2n p-

NO.

(X-

CH2CH2-R »3

(vi)

io in which R4 has the same meaning as above.

By the action of acrylonitrile or an alkyl acrylate on a diazonium halide of an m-nitraniline of formula (X) in the presence of a copper salt as catalyst, a compound is obtained according to the Meerwein reaction of formula:

* 4

in which Rb R2, R'3 and R4 have the same meanings as above and D'represent a heterocyclic residue corresponding to one of the following formulas: ^ "20

NO.

2 I -3

Hai

(XI

(vn)

(vm)

(IX)

35

wherein each Y represents a hydrogen atom or a nonionic substituent and the B rings can be substituted with one or two nonionic substituents.

Nonionic substituents represented by Y or carried by the nuclei B are, for example, halogen atoms or alkyl (optionally substituted), alkoxy, carbalkoxy, aryl (optionally substituted) radicals; nitro, cyano, sulfamoyl, carbamoyl, acyloxy, acyl, acylamino.

In the definitions of formula (IV) and in remuneration of the nonionic substituents represented by Y in formula (VII) or carried by the nuclei B in formulas 40 (Vin) and (IX), the alkyl or alkoxy radicals contain 1 with 4 and preferably 1 or 2 carbon atoms and the carbalkoxy radicals contain 2 to 5 and preferably 2 or 3 carbon atoms; the acyl radicals are, for example, alkylcarbonyl or alkylsulfonyl radicals in which the alkyl group contains 45 1 to 4 and preferably 1 or 2 carbon atoms; the nitrogen atom of the sulfamoyl and carbamoyl radicals can be mono- or disubstituted by alkyl groups containing 1 to 4 and preferably 1 or 2 carbon atoms; the acylamino radicals are in particular alkylcarbonylamino, alkylsulfonylamino, benzoylamino or phenylsulfonylamino radicals in which the alkyl group contains 1 to 4 (preferably 1 or 2) carbon atoms and may, as well as the phenyl group of the benzoylamino and phenylsulfonylamino radicals, be mono- or disubstituted by halogen atoms (preferably chlorine or bromine) or hydroxy, cyano, methoxy, ethoxy, acetyloxy or propionyloxy groups; the acyloxy radicals are, for example, alkylcarbonyloxy radicals in which the alkyl group contains 1 to 4 and preferably 1 or 2 carbon atoms; finally, suitable aryl groups are, for example, phenyl groups optionally substituted by a halogen atom or a nitro or alkoxy group containing 1 or 2 carbon atoms.

The couplers of formula (III) are new products. Their preparation is the subject of the patent filed the same day by the holder for "New N-substituted anilines". They can be obtained according to methods known per se (Meerwein reaction, reduction, alkylation, hydrolysis, acylation, esterification) from m-nitranilines of formula:

in which "Hai" - denotes a halogen atom and R'3 represents a cyano radical with carbalkoxy.

By reduction of the compounds of formula (XI), the anilines of formula are then obtained:

CH2CH2-R »3

(XII

50

in which R'3 and R4 have the same meanings as above.

By treating the anilines of formula (XII) using an alkylating agent such as, for example, dimethyl or diethyl sulfate, methyl or ethyl bromide, glycol hydrochloride, methyl acrylate or ethyl, couplers are obtained according to the invention of formula:

^ <1;

CH0CI-U ~ R V

2 2-3 (xiii;

in which R'3 and R4 have the same meanings as above, R '! represents an alkyl, hydroxyalkyl or carb-alkoxyalkyl radical and R'2 represents a hydrogen atom or an alkyl, hydroxyalkyl or carbalkoxyalkyl radical. The monoal-kylation leads to the couplers of formula (XIII) in which R'2 is a hydrogen atom and the dialkylation to the compounds of formula (XIII) in which R'2 is an alkyl, hydroxyalkyl or carbalkoxyalkyl radical. To obtain a compound of formula (XIII) in which R ^ and R'2 represent different radicals (for example R '(= ethyl and R'2 = hydroxyethyl), it suffices to follow a monoalkylation by an alkylation with using an alkylating agent different from that used for monoalkylation.

5

623,343

The compounds of formula (III) in which R3 represents hyde with naphthalenesulfonic acid as well as the sulfonates a carbamoyl or carboxy radical can be obtained by lignin.

hydrolysis of the corresponding compounds of formula (III) in The appropriate cationic dispersants are compounds in which R3 represents a cyano radical. However, if it is desired to quaternary ammonium which contain alkyl residues or to prepare a compound of formula (III) where R3 represents s aralkyl having 8 to 20 carbon atoms.

carbamoyl or carboxy radical and at least one of the symbols R [The dye preparations may also contain, in and R2 represents a hydrolysable radical, for example a radical plus dispersants, organic solvents especially those boiled

acyloxyalkyl or carbalkoxyalkyl, it is necessary to carry out above 100 ° C., which are advantageously miscible with

hydrolysis of the cyano radical (R3) before the introduction of the water radical such as mono- and dialkylglycol ethers, dioxane,

(Rj and / or R2) hydrolyzable. To prepare such compounds, dimethylformamide or -acetamide, tetramethylenesulfone, is sufficient, for example, to first hydrolyze a compound of the formula dimethylsulfoxide. It is advantageous to grind the dye, the (III) where R3 is a cyano group and at least one of the symbols Rt dispersing and the solvent together. It is also possible to use and R2 represents a hydroxyalkyl radical, then to follow only solvents in place of the dispersant, but hydrolyses them by acylation. dye preparations must contain either a dispersant

The compounds of formula (III) in which R] and / or R2 is or else a solvent.

represents an alkyl radical substituted by an alkoxy group or The dyeing of polyester fibers with dyes according to acyloxy can be prepared from the compounds of formula the invention is carried out in aqueous dispersion according to the methods

(III) in which R! and / or R2 represents a hydroxyal- radical used for polyesters. The polyesters of kyl acid are dyed by etherification using an alcohol or by aromatic polycarboxylic ester and polyalcohol, preferably

tion by means of an acid chloride or anhydride. 20 temperatures above 100 ° C and under pressure. We can

The dyes according to the invention are perfectly suitable for also carrying out dyeing at the boiling point of the dye bath in the dyeing and for printing all dyeable textile materials in the presence of carriers such as, for example, polyphenols,

in dispersion dyes, in particular those based on fibers of diphenyl-polychlorobenzene compounds, or hydrophobic products such as polyurethane fibers, fibers of similar auxiliaries or also according to the Thermosol process,

polyolefins such as polypropylene modified or not by 25, that is to say by padding with subsequent heat treatment,

basic or nickel treatment, the fibris "of diacetate or of, for example, a heat setting at 180-210 ° C. The cellulose triacetates and especially the polyamide fibers are dyed as cellulose diacetate fibers advantageously at temperatures

Nylon-6, Nyîon-èTô and Nyîon-12, aromatic polyesters of 80-850 C, while cellulose triacetate fibers such as those of terephthalic acid and ethylene glycol or are dyed with l of the dye bath. For dyeing 1,4-dimethylol cyclohexane or mixed polymers of cellulose diacetate acids or polyamide fibers, it is not terephthalic and isophthalic with ethylene glycol. necessary to use carriers.

For heat setting the dye, or heats the fabric

For dyeing in aqueous baths, the fouled colo-polyester is used, advantageously after prior drying,

rants according to the invention insoluble or very slightly soluble in water, for example in a stream of hot air at temperatures advantageously in finely divided form and the operation is carried out above 35 ° C., advantageously between 180 and presence of dispersants such as residual cellulose detergent 210 ° C. The dyes obtained according to the process of the invention sulfite or synthetic detergents and a combination can undergo a subsequent treatment, for example by heating

various wetting and dispersing agents. In general, it is advantageous in an aqueous solution of a nonionic detergent,

to transform the dyes to be used before their application in. Instead of impregnation, it is also possible to apply them a dye preparation containing the dispersant and the dye 40 dyes according to the invention by printing. For this purpose, a finely divided form is used in such a way that a printing color is obtained by dilution containing in addition auxiliary agents.

of the preparation with water a fine dispersion. Such usual agents, such as wetting and thickening agents, dye preparations can be obtained in a finely dispersed dye.

naked for example by grinding the dye in dry form or The dyes according to the invention can also be ap-wetted with or without the addition of dispersants during this grinding. 45 plicated in a solvent medium, for example in perchlorethylene

After wet grinding, it is obtained by subsequent drying alone or in a mixture with 5-10% of dimethylformamide or of dye preparations containing methanol auxiliary agents.

textiles and dye. With the dyes according to the invention, dyes are obtained

As advantageous dispersants of the non-ionic category and full-bodied impressions having good solidities, in particular we can mention the adducts of 8 moles of oxide 50 bind to the heat setting, sublimation, pleating, gas ethylene with 1 mole of p.-tertio-octylphenol, 15 to 16 smoke, overdyeing, dry cleaning, chlorine and moles of ethylene oxide with castor oil, 20 moles wet, for example with water, washing and perspiration,

of ethylene oxide with alcohol C16H33OH, the additives The dyes according to the invention can also be used

tion of ethylene oxide with di- [a-phenylethyl] phenols, used for dyeing in the spinning mass of polyamides, polyethylene oxide-tertio-dodecyithioethers, polyamid polyesters and polyolefins. The nes-polyglycol ethers and the adducts of 15 or 30 polymer to be dyed in the form of powder, grains, chips, moles of ethylene oxide are preferably mixed with a mole of dodecylamine or spinning solutions all prepared or in the molten state with stearylamine. dye which is incorporated in the dry state or in the form of a

As anionic dispersants, there may be mentioned the esters dispersion or solution in an optionally volatile solvent. sulfurics of fatty alcohols having 8 to 10 carbon atoms, the 6 "After homogeneous distribution of the dye in the solution or sulfuric esters of the adducts of ethylene oxide in the polymer melt, the mixture is treated from the corresponding fatty amides or from alkylated phenols in a known manner by molding, pressure or extrusion, to obtain

having 8 to 12 carbon atoms in the alkyl residue, the esters of fibers, threads, monofilaments, films, etc. We obtain sulfonic containing alkyl residues having 8 to 20 atoms of with the dyes according to the invention of intense and carbon colorations, the sulfation products of fatty acids and non-united oils having good light fastnesses and good saturates, phosphoric esters containing alkyl residues general fastnesses, in particular in washing, in sweat and with the having 8 to 20 carbon atoms, fatty acid soaps, sublimation. The dyes in accordance with the invention have alkylarylsulfonates, the condensation products of formaldehyde, also good stability in a wide pH range,

623,343

6

good affinity, and good resistance to scouring. In addition, these new dyes generally reserve wool and other natural polyamide fibers well.

In the nonlimiting examples below, the parts and the percentages are by weight, unless otherwise stated. The parts by weight and the parts by volume are in the same ratio as the gram and the milliliter.

Preparation of couplers

Example A

Diethylamino-3 hydrocinnamonitrile (or N, N-di6thyl-ß-cyanethyl-3 aniline)

a) Meerwein's reaction

In a mixture of 50 parts by volume of glacial acetic acid, 100 parts by volume of acrylonitrile and 15 parts by volume of methyl ethyl ketone, a freshly prepared acidic aqueous solution of 138 diazo is introduced in parallel flows. parts of metanitraniline and a solution of 5 parts of cuprous chloride in 20 parts by volume of hydrochloric acid 19 ° Bé. The mixture is heated to 35-40 ° C and maintained at this temperature until the diazonium salt disappears (about 2 hours). After cooling and filtration, 180 parts of chloro-2 (3-nitro-phenyl) -3 propanenitrile (mp = 90 ° C) of formula:

The retention time Tr of N, N-diethyl ß-cyanöthyI-3 aniline, measured at 220 ° C. on a Chromosorb W 15% SE 30 column 1.5 m long and 2 mm inside diameter with a flow rate 25 ml / min nitrogen, is 191 seconds.

5

Example B

The procedure is as in Example A, but replacing the acrylonitrile with an equivalent molar amount of ethyl acrylate. This gives N, N-diethyl P-carbethoxyethyl-3 m aniline (or ethyl diethylamino-3 hydrocinnamate), the retention time Tr, measured as in Example A, is 251 seconds.

Example C

i5 N, N-bis (P-hydroxyethyl) 3-amino hydrocinnamonitrile

A mixture consisting of 100 parts of water, 100 parts of calcium carbonate, 160 parts of chlorohydrin glycol and 73 parts of 3-amino hydrocinnamonitrile is heated at reflux for 29 hours. It is filtered hot and washed with hot water. After decantation, 103 parts of N, N-bis (ß-hydroxyethyl) to crude 3-hydrocinnamonitrile of formula:

25

o n. (c2h40h)

ch _, - ch ~ cn 2 i •

Cl „

b) Reduction

105 parts of boiling water, to which 100 parts of iron powder and 6 parts by volume of crystallizable acetic acid have been added, are introduced in small quantities, while maintaining the temperature in the region of 95 ° C., 105 parts of chloro-2 (3-nitro-phenyl) -3 propanenitrile. Then stirred for 1 to 2 hours at reflux. At the end of the reaction, followed by chromatography on a thin layer of silica, extraction is carried out using 100 parts by volume of chlorobenzene, then neutralized with sodium hydroxide and filtering the iron sludge. After decantation and distillation of the chlorobenzene, 57 parts of crude amino-3 hydrocinnamonitrile (or ß-cyanothyl-3-aniline) are obtained in the form of an oil which can be purified by subsequent distillation (b.p. = 168 ° C / 4 mm Hg).

c) Alkylation

430 parts by volume of diethyl sulphate are added dropwise to a mixture of 146 parts of p-cyanethyl-3 aniline, 1000 parts of water and 233 parts of sodium carbonate. It is heated to 40 ° C and maintained at this temperature for about 12 hours. 1200 parts of water are then added to the reaction mixture, stirred for 30 minutes, then decanted.

220 parts of N, N-diethyI ß-cyarathyI-3 crude aniline of formula:

ch2ch2cn

30 in the form of an oil which can be purified by distillation (Tr = 898 s). This oil can also be used directly without purification for the preparation of dyes.

35

40

45

Example D

N, N-bis $ -acetoxyethyl) 3-amino hydrocinnamonitrile A mixture of 52 parts of N, N-bis $ -hydroxyethyl (3-amino-hydrocinnamonitrile) is brought to reflux for 8 hours, 100 parts by volume of glacial acetic acid and 56 parts of acetic anhydride. By vacuum distillation, the N, N-bis $ -acetoxyethyl) amino-3 hydrocinnamonitrile of formula:

/ -

ch2ch2cn

Analysis

50

Calculated for Q7H22N2O4 Found

C% 64.1 63.8

H% N% 6.92 8.80 6.87 8.63

<oV-

/ "C2H5

not

) 'XsC2H5

cu ch CN 2 2

in the form of a brownish oil which can be purified by distillation (m.p.E. = 142 ° C / 3 mm Hg).

Example E 55 N-ethylamino-3 hydrocinnamonitrile

143 parts by volume of diethyl sulfate are introduced dropwise into a mixture of 146 parts of 3-amino hydrocinnamonitrile, 1000 parts of water and 160 parts of sodium carbonate. It is heated to about 30 ° C and maintained at this temperature until the reaction is complete, easily followed by thin layer chromatography on silica. After decantation and distillation under vacuum, 140 parts of N-ethylamino-3 hydrocinnamonitrile are obtained which boils at 153 ° C. under 2.5 mm of mercury and whose retention time, measured as at h? Example A is 154 seconds.

Example F

(N-ethyl N-P-hydroxyethyl amino) -3 hydrocinnamonitrile

7

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Ori heats at reflux for about 24 hours a mixture of 174 parts of N-ethylamino-3 hydrocinnamonitrile, 330 parts of chlorohydrin glycol, 200 parts of water and 200 parts of calcium carbonate. It is filtered hot, washed with 60 parts of hot water, decanted and distilled under vacuum. 150 parts of (N-ethyl N-ß-hydroxyöthyl amino) -3 hydrocinnamonitrile of formula:

yc2u5

fi

\ ch2ch2oh ch2ch2cm in the form of an oil which boils at 205 ° C under 2 mm of mercury.

Example G

(N-ethyl N-3-acetoxyethylamino) -3 hydrocinnamonitrile A mixture of 218 parts of (N-ethyl N-ß-hydroxy6thylamino) -3 hydrocinnamonitrile, 100 parts by volume of acetic acid crystallizable and is refluxed for 4 hours. 115 parts by volume of acetic anhydride. At the end of the reaction, easily followed by chromatography on a silica mine layer, neutralized using sodium carbonate and 200 5 parts of (N-ethyl N ^ -acetoxyethylamino) -3 hydrocinnamonitrile of formula:

/ C2! L5

n n <xch2ch2ocdch3 ch2ch2cn i5 in the form of an oil which boils at 192 ° C under 20 mm of mercury.

Table I below brings together other examples of compounds of formula (III) prepared as in the previous examples. The results of the elemental analyzes of these products are in accordance with theory.

Table I

Ex.

Ri r2

R3

r4

Preparation

following the

examples h

c2h5

c2h5

cn ch3

AT

J

id id id och3

AT

K

id id cooc2h5

h

AT

L

ch2ch2oh ch2ch2oh cn ch3

Aa + Ab + C

M

id id id och3

id n

id id cooc2h5

h id o

id id id och3

id

P

ch2ch2ococh3

ch2ch2ococh3

cn ch3

Aa + Ab + C + D

Q

ch2ch2ococh3

ch2ch2ococh3

cn och3

Aa + Ab + C + D

r id id cooc2h5

h id

S

id.

id id och3

id

T

QH5

ch2ch2oh id h

E + F

U

id ch2ch2ococh3

id h

E + F + G

V

ch2ch2oh ch2ch2oh cooch3

h

Aa + Ab + C

w ch2ch2ococh3

ch2ch2ococh3

id h

Aa + Ab + C + D

X

IT

id id h

E + F + G

Example Y

N, N-bis ^ -carbomethoxyethyl) 3-amino hydrocinnamonitrile

A mixture of 146 parts of 3-amino hydrocinnamonitrile, 350 parts of glacial acetic acid, 344 parts of methyl acrylate and 1 part of hydroquinone is heated at reflux for 15 hours. Then allowed to cool to room temperature, then flows over 3000 parts of water and neutralized to pH 7.5 by adding a concentrated solution of sodium hydroxide. After decantation, 280 parts of N, N-bis (ß-carbomethoxyethyl) 3-amino hydrocinnamonitrile of formula:

n (ch ch2c00ch3) 2

: h2ch2cn

Analysis:

Calculated for Ci7H22N204 Found

vs%

64.10

64.26

H% 6.92 6.90

N% 8.80 8.95

45 If we replace methyl acrylate with ethyl acrylate, we obtain in the same way N, N-bis (-carbethoxyethyl) 3-amino hydrocinnamonitrile.

Example Z

50 Hydrocinnamic diethylamino-3 acid

A mixture of 60.6 parts of 3-diethylamino hydrocinnamonitrile, 250 parts by volume of denatured ethyl alcohol, 100 parts of water and 60 parts by volume of a solution is heated to reflux until the evolution of ammonia is stopped. 55 sodium hydroxide at 35 ° Be. After the evolution of ammonia has ceased, the mixture is cooled and then the reaction mixture is neutralized by adding hydrochloric acid at 19 ° Bé. After filtration and drying, 3-diethylamino hydrocinnamic acid of formula:

65 Analysis:

ch2ch2cooh

C2H5

C2H5

Calculated for CI3H19N02 Found

C% 70.5 71.0

H% 8.59 8.63

N% 6.34 6.28

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8

Example AA Diethylamino-3 hydrocinnamamide A mixture of 40 parts of diethylamino-3 hydrocinnamonitrile is heated to 100—105 ° C. for one hour,

34 parts by volume of sulfuric acid at 66 ° Bé and 6 parts of water. The reaction mixture is then allowed to cool to about 60 ° C, then poured over 500 parts of ice. Neutralization is carried out by adding approximately 160 parts by volume of a sodium hydroxide solution at 35 ° Bé, taking care that the temperature of the mixture does not exceed 20 ° C. After filtration and washing with water, 3-diethylamino hydrocinnamamide of formula:

o n (c2h5) 2

ch2ch2co? jh2_

Preparation of dyes and their application s Example 1

7 parts of sodium nitrite are dissolved in 120 parts of sulfuric acid at 66 ° Bé then 20.7 parts of 2,6-dichloro-4 nitro aniline are slowly introduced. It is stirred for 3 hours at 50 ° C., then poured over 400 parts of water and 400 parts of ice. It is filtered and then the excess nitrous acid is destroyed by the addition of urea. A solution of 32 parts of N, N-bis (P-acetoxyethyl) P-cyanethyl-3 aniline in 100 parts of glacial acetic acid is slowly added. Brew for 30 minutes, then filter and wash with water until neutral.

15

which melts at 59 ° C.

Put in dispersed form, the dye thus obtained of formula:

0-

N- \ ö> —N = "- (oV-'i

Cl c2h4cw

* /c_h.0c0ch_ 2 4 3

kc, h4ocach3

dyes polyester fibers in a very full-bodied brown shade, with excellent light fastness and sublimation.

Table II below brings together other examples of dyes according to the invention, prepared as in Example 1, by

30 coupling of the diazo derivative of the amine indicated in the second column with the coupler of formula (III) defined in the third, fourth, fifth and sixth columns of the table.

Table II

Ex. Amine of formula (II)

Copulant of formula (III) ri r2

Color on polyester

2

2-amino-5-nitro benzonitrile c2h4ococh3

cäocochj cn h

ruby

3

id id id cn ch3

purple

4

id id id cn och3

id

5

id id id cooc, h5

h ruby

6

id id id conh,

h id

7

id id id cooh h

id

8

id qhj qjhj cn h

purple

9

id id id cn ch3

blue

10

id id id cn och3

id

11

id id id coocjhj h

purple

12

id id id conh2

h id

13

id id id cooh h

id

14

id c2h4oh c2h4oh cn h

id

15

id id id cooqhj h

id

16

id id id conh2

h id

17

2-amino-5-nitro benzonitrile c2h4oh c2h4oh cooh h

purple

18

id qhj id cn h

id

19

id id id cooc2h5

h id

20

id id cyeîjtococilj cn h

id

21

id id id cooc2h5

h id

22

id id id conh2

h id

23

2-chloro-4-nitro aniline c2h4ococh3

c2h4ococh3

cn h

red

24

id id id cooqh,

h id

25

id c2h5

c2h5

cn h

ruby

26

id id id cooc2hs h

id

27

id id id conh,

h ruby

28

id id id cooh h

id

9

623,343

Table II (continued)

Ex. Amine of formula (II)

29 chloro-2 nitro-4 aniline

30 id

31 id

32 id

33 2,6-dichloro-4 nitro aniline

34 id

35 id

36 id

37 id

38 id

39 id

40 id

41 nitro-4 aniline

42 id

43 id

44 id

45 dinitro-2,4 bromo-6 aniline

46 id

47 id

48 id

49 id

50 id

51 id

52 id

53 id

54 id

55 id

56 dinitro-2,4 chloro-6 aniline

57 id

58 id

59 id

60 id

61 4-nitro-2-carbethoxy aniline

62 id

63 id

64 id

65 2-amino-3-bromo-5-nitro benzonitrile

66 id

67 id

68 id

69 id

70 id

71 id

72 id

73 2-amino-3,5-dinitro benzonitrile

74 id

75 id

76 id

77 id

78 id

79 4-amino azobenzene

80 id

81 2-amino-6-nitro benzothiazole

82 id

83 id

84 3-amino-5-nitro-benzisothiazole-2,1

85 id

86 id

87 id

88 id

89 id

Copulant of formula (III)

R, R2 R3 R4 Grade on polyester c2h4oh c2h4oh cn h

red

bluish

id id cooc2h,

h id c, h5

c2h4ococh3

cn h

id qhs qhtococh-,

cooqhs h

red

bluish

c2h4ococh3

id id h

c2h5 brown

c2h5

cn h

ruby id id cooc2h5

h id id c2h4oh cn h

id c2h4oh id cn h

brown id id cooc2h5

h id c2h5

qhtococh ;,

id h

ruby id id cn h

id c2h4ococh3

id cn h

scarlet id id cn ch3

id id id cn och3

red id id cooc2h5

h id c2h5

c2h4oh cn h

purple id c2h4ococh3

cn h

id id

. id cooç2h5

h id c2h4ococh3

c2h4ococh3

cn h

id id id cn ch3

blue id id cooc2h5

h purple

IT

qh5

cn h

blue id id cn ch3

id id id cn och3

id id id cooc2h5

h id q, h4oh q, H4OH

cn h

purple c2h4ococh3

c2h4ococh3

cn h

id

QH5

c2h5

cn h

blue id id cooc2h5

h purple c2h4oh c2h4oh cn h

id id id cooc2h,

h id c, h4ococh3

q, h4ococh3

cn h

red c2h5

c2h5

cn h

ruby id id cooc2h5

h id id id cooh h

id c, h4ococh3

c2h4ococh3

cn h

purple c2h5

c2h5

cn h

blue id id cn och3

id id c2h4oh cn h

purple id c2h4ococh3

cn

H

id id id

COOC2H5

H

id c2h4oh c2h4oh cn h

blue id id cn och3

id c2h4ococh3

c2h4ococh3

cn h

purple c, h4oh c2h4oh cn h

blue c2h5

c2h5

cn h

id id id cooc2h5

h id id id conh2

h id id id cooh h

id c2h4ococh3

c2h4ococh3

cn h

orange

id id cooc2h,

h id id id cn h

ruby id id cooc2h5

h id c2h5

qh5

cn h

purple c2h4ococh3

c2h4ococh3

cn h

blue id id cooc2h,

h id c2h4oh c2h4oh cn h

id id id cooc, h,

h id id id cooh h

id c2h,

c2h,

cn h

id

623,343

10

Table II (continued)

Ex. Amine of formula (II)

Copulant of formula (HI) R, R2

r3

R4 Grade on polyester

90

3-amino-5-nitro-benzisothiazole-2,1

c2h5

qh,

cooqh,

h blue

91

id id id cooh h

id

92

id id q, h4oh cn h

id

93

id id id cooc2h5

h id

94

id id

QH + ococa,

cn h

id

95

id id id cooc2h,

h id

96

2-amino-3-cyano-4-methyl-5-nitro thiophene c2h4ococh3

id cn h

purple

97

id c2h5

c2h5

cn h

blue

98

2-amino-5-nitro benzonitrile c2h4cooch3

c2h4cooch3

cn h

ruby

99

id c2h4ococh3

c2h4ococh3

cooch3

h id

100

id qh5

qh5

id h

purple

101

chloro-2 nitro-4 aniline id id id h

ruby

102

id q, h4ococh3

c2h4ococh3

id h

red

103

id c2h4cooch3

c2h4cooch3

cn h

id

104

ichloro-2,6 nitro-4 aniline id id cn h

brown

105

id c2hs c2h5

cooch3

h ruby

106

nitro-4 aniline cjh / XDOCH-,

q, h4cooch3

cn h

scarlet

107

dinitro-2,4 bromo-6 aniline c2h5

C2hs conh2

h purple

108

2-amino-3-bromo-5-nitro benzonitrile id id cooch,

h blue

109

id c2h4cooch3

c2h4cooch3

cn h

purple

Example 110

A fabric of polyethylene terephthalate glycol fibers is printed with a printing paste containing 20 parts of the dye of Example 2,150 parts of a solid salt of sulphonated castor oil, 600 parts of a thickener and 250 parts of 'water. After drying, the fabric is thermofixed for one minute at 200 ° C, then subjected to a reducing treatment. We obtain a ruby nuance of good general solidities.

Example 111

A fabric of polyethylene terephthalate glycol fiber is sponged in a bath comprising 9 parts of the dye of Example 23,0.5 part of polyglycolic ether of oleic alcohol, 1.5 part of 'a Polyacrylamide and 989 parts of water. After drying, the fabric is heat-set for one minute at 200 ° C., then subjected to a reducing treatment using sodium dithionate. We obtain a red shade of very good general solidity.

VS

Claims (3)

623,343 2. Method according to claim 1, in which D is a residue of formula 35 where each Y represents a hydrogen atom or a nonionic substituent and the nuclei B can be substituted by one or two nonionic substituents. 6. The method of claim 1, wherein the alkyl and / or alkoxy radicals contain 1 or 2 carbon atoms. 7. The method of claim 1, wherein R4 is a hydrogen or chlorine atom or a methyl or methoxy group. 8. The method of claim 1, wherein at least one of the symbols R] and R2 is ethyl, ß-hydroxyöthyle, P-acetoxyethyl or P-carbomethoxyethyl. 9. Azo dyes of formula (I), obtained by the process according to claim 1. in which U represents a hydrogen or halogen atom or an alkyl, alkoxy, carbalkoxy, acyl, nitro, cyano or sulfamoyl radical, V represents a hydrogen or halogen atom or an alkyl, cyano or trifluoromethyl radical " , W represents a hydrogen or halogen atom or an optionally substituted nitro, cyano, carbalkoxy, acyl, or arylazo radical, and X represents a hydrogen or halogen atom or an alkyl, alkoxy, carbalkoxy, acylamino radical , nitro or cyano. 2 CLAIMS 1. Process for the preparation of azo dispersion dyes corresponding to formula (I) R, d - n = n ~ / Q ^ —1 CH2CH2 "R3 R, (I) in which D represents the remainder of a diazotizable, homocyclic or heterocyclic aromatic amine, devoid of sulfonic acid group, Rt and R2 each represent an alkyl radical optionally substituted by a halogen atom or by a hydroxy, alkoxy, acyloxy or carbalkoxy group, R3 represents a cyano, carbamoyl, carboxy or carbalkoxy radical, and R represents a hydrogen or halogen atom or an alkyl or alkoxy radical, which consists in copulating the diazo derivative of an aromatic amine D-NH2 with a composed of (ih) % carbalcoxy, and Rb R2 and R4 have the same meanings as dan; claim 1. 4. Method according to claim 1, in which D is a thiazolyl-2, benzothiazolyl-2 or benzisothiazol-2,1 yl- residue, optionally substituted by nonionic substituents. 5. Method according to claim 1, characterized in that the product corresponds to formula (VI) "* r D> - K = N (Q ^ _n ^ ' 15 CH, CH0-ni. R2 (VI) in which Rb R2 and R + have the same meanings as in claim 1, R'3 represents a cyano or carbalkoxy radical, and D'represents a heterocyclic residue corresponding to one of the following formulas: 25 N N Xjl CH2CH2 "R3 (or) 30 in which Rls R2, R3 and R4 have the same meanings as above. 3. Method according to claim 1, characterized in that the product corresponds to formula (V)