FR2466491A1 - Naphtho-styril dyes with nitrogen-heterocyclic substit. - used for dyeing, printing and bulk colouring of polymers - Google Patents

Abstract

New naphthostyril dyes (I) have formula: (where Y is . R is H, alkenyl, (ar)alkyl, cycloalkyl, aryl or a 2- or 3-membered alkylene gp. attached to the adjacent o-position of ring a. Q is aryl or an o-arylene gp. attached to the adjacent peri-position of ring b. X is =C(W)- or =N-; W is CN, C0NW1W2, C00W3 or Y; W1-3 are H or alkyl or W1 and W2 together with the N atom can form a satd. 5- or 6-membered heterocycle. A completes a 5- or 6-membered quasi-aromatic, opt. benz-anellated heterocycle. The cyclic and acyclic gps. can have substits. usual in dyestuff chemistry). (I) contg. cationic gps. are suitable for dyeing and printing acid-modified substrates, e.g. polyacrylonitrile, acid modified polyesters and polyamides and paper, whilst those contg. acid gps. can be used for dyeing and printing polyamides and wool. The pref. (I), which are free from ionic gps., are valuable dispersion dyes, suitable for dyeing and printing hydrophobic textiles and for bulk colouring of organic polymers, e.g. polystyrene and polyesters, esp. polyethylene terephthalate. Sublimable (I) can be used for thermal dyeing and printing processes, esp. transfer printing. (I) give brilliant orange, red, violet or blue shades with good affinity and fastness esp. to light.

Description

(oA - R est un atome d'hydrogène ou un radical alkyle, alcényle, aralkyle, cycloalkyle ou aryle ou un radical alkylène
comportant deux ou trois chaînons et qui est relié à la position ortho voisine du noyau (a) ;
- Q est un radical aryle ou un radical o-arylène relie à la position péri voisine du noyau (b)
- X represente =C(W)- ou =N - W représente CN , CONW1W2 , COOW3 ou un radical de formule

The present invention relates to dyes of general formula (I):

(oA - R is a hydrogen atom or an alkyl, alkenyl, aralkyl, cycloalkyl or aryl radical or an alkylene radical
having two or three links and which is connected to the neighboring ortho position of the core (a);
Q is an aryl radical or an o-arylene radical connected to the peri-neighbor position of the nucleus (b)
X represents = C (W) - or = N - W represents CN, CONW1W2, COOW3 or a radical of formula

- W1, W2 and W3 each represent, separately, a hydrogen atom or an alkyl radical and W1 and W2 can also form with the nitrogen atom to which they are attached a saturated five or six-membered cyclic ring; and
A represents the remaining knuckles of a 5- or 6-membered, quasi-aromatic heterocyclic radical optionally comprising a fused benzene ring; cyclic and acyclic radicals which may contain the usual substituents in dye chemistry), as well as a process for their production, application to the dyeing and dyeing of high molecular weight organic materials, and dyed or colored materials using these dyes.

 By the expression "substituents customary in dye chemistry" is meant within the scope of the present invention, in addition to cationic and anionic radicals, in particular nonionic radicals, that is to say those which do not do not cause solubilization in water.

Suitable cationic radicals are radiolabels
ammonium, cycloammonium and guanidinium. Anio radicals
Suitable solvents are sulfo, sulfinato, sulfato, disulfimide and carboxylate groups. Suitable nonionic desradicals are in particular those which are the subject of a more complete definition below.

The alkyl radicals R preferably have 1 to 8 carbon atoms and they can be interrupted by 1 or 2 oxygen atoms. Particularly preferred are alkyl radicals having 1 to 6 carbon atoms and, in particular, radicals.
alkyl having 1 to 3 carbon atoms may be substituted once with a radical-OH, C1, Br, CN, alkoxycarbonyl (1 to 4 carbon atoms), carboxyl, carbamoyl, alkylcarbonyl (1 to 4 carbon atoms in the alkyl group) or phenoxy.

 For example, methyl, ethyl, beta-cyanoethyl, beta-chloroethyl, beta-hydroxyethyl, betahydroxy-n-propyl, beta-hydroxy-gamma-chloro-n-propyl, betacarboxy-ethyl, beta-carbomethoxy may be mentioned; ethyl, beta-carbethoxy-ethyl, beta-carbobutoxy-ethyl, beta-phenoxy-ethyl, beta-carbamoyl-ethyl, beta-acetoxy-ethyl, -beta methoxy-ethyl, beta ethoxy-ethyl, beta-N-butoxy- ethyl, n-propyl, n-butyl, isobutyl, isoamyl or n-hexyl.

 As the alkenyl radical R, mention may be made of the allyl radical.

Suitable aralkyl radicals R are, for example, phenyl-alkyl radicals whose alkyl group contains 1 to 3 carbon atoms and which may be substituted in the phenyl nucleus by chlorine or bromine or by alkyl groups.
(1 d 4 carbon atoms) or alkoxy (1 or 2 carbon atoms) for example.

 its preferred cycloalkyl radicals are cyclohexyl radicals which can also carry one to three methyl groups.

 As aryl radicals R, there may be mentioned phenyl radicals, which may be substituted for example with chlorine or bromine or with alkyl groups (1 to 4 carbon atoms) or alkoxy (1 to 4 carbon atoms).

Preferred alkylene radicals R which are connected to the ortho position adjacent to the ring (a) correspond to the formula
-CH2-CH2- or -CH2-CH2-CH2
Suitable aryl radicals Q are especially phenyl radicals which may be substituted with one or two alkyl groups (1 to 4 carbon atoms), an alkoxy group (1 or 2 carbon atoms), 1 to 5 chlorine atoms, 1 to 5 bromine atoms, an amino group, acylamino as alkylcarbonylamino (1 to 4 carbon atoms in the alkyl group), alkylsulphonylamino (1 to 4 carbon atoms in the alkyl group), phenylcarbonylamino, phenylsulphonylamino , acyloxy as alkylcarbonyloxy (1 to 4 carbon atoms in the alkyl group), phenyl-carbonyloxy or phenyl-sulphonyloxy (which may include, as substituents, for example, an alkyl radical (1 to 4 carbon atoms), alkoxy (1 or 2 carbon atoms) or chloro) and alkylsulphonyloxy groups having at least 4 carbon atoms in the alkyl group, hydroxy, nitro or -SO2-T radicals, where T is Cl, O-T1 or NT2T3;
T1 is a hydrogen atom, an optionally substituted alkyl radical having at least 4 carbon atoms, preferably an alkyl radical having 4 to 6 carbon atoms, an optionally substituted cycloalkyl radical, preferably a cyclohexyl radical optionally substituted by one to three methyl groups, a phenyl-alkyl radical (1 to 3 carbon atoms in the alkyl group) or an optionally substituted aryl radical, preferably a phenyl radical optionally substituted with CH 3, Cl or CH 3 O; T2 is an alkyl radical having 1 to 4 carbon atoms (optionally substituted with OH, C1, CN, an alkoxy radical (1 to 4 carbon atoms), a dialkylamino radical or trialkylammonium radical (each alkyl group having 1 or 2 carbon atoms or T2 is a phenyl-alkyl radical (1 or 2 carbon atoms in the alkyl group), cyclohexyl, cyclohexylmethyl or a phenyl radical (optionally substituted with C1, CH3, OCH3 or OC2Hg), and T3 is a hydrogen atom. hydrogen, an alkyl radical having 1 to 4 carbon atoms (optionally substituted by
OH, C1, CN, or an alkoxy radical having 1 to 4 carbon atoms), a phenyl-alkyl radical in which the alkyl group contains 1 or 2 carbon atoms or else T3 forms, with T2, the remaining knuckles of a heterocyclic ring comprising five, six or seven members such as a pyrrolidine, piperidine, perhydro-azepine, morpholine, piperazine,
N'-alkyl-piperazine of which the alkyl group has 1 to 4 carbon atoms and in particular the N'-beta-hydroxy-ethyl derivative, or of an N ', N'-dialkyl-piperazinium radical of which each alkyl group comprises 1 to 4 carbon atoms.

 Another suitable aryl radical Q is the naphthyl radical.

appartiennent de préférence à la série de la 3,3-diméthyl-indolénine, de l'imidazole, du benzimidazole, du pyrazole, de l'indazole, de l'oxazole, du benzoxazole, du thiazole, du benzothiazole, du 1,3,4-thiadiazole, du 1,2,4-triazole, de la pyridine, de la quinoléine, de la pyrimidine ou de la quinazoline, ces radicaux pouvant porter de préférence des substituants non ioniques comme un radical alkyle ayant 1 à 4 atomes de carbone, alcoxy ayant 1 ou 2 atomes de carbone, amino, nitro, chloro, bromo, cyano ou phényle.The o-arylene radicals Q, which are connected to the neighboring position in the peri of the ring (b), are preferably o-phenylenic radicals which may be substituted by an alkyl radical (1 to 4 carbon atoms), alkoxy (1 at 4 carbon atoms), chloro, bromo or SO2-T
Heterocyclic radicals

preferably belong to the series of 3,3-dimethylindolenine, imidazole, benzimidazole, pyrazole, indazole, oxazole, benzoxazole, thiazole, benzothiazole, 1,3 , 4-thiadiazole, 1,2,4-triazole, pyridine, quinoline, pyrimidine or quinazoline, which radicals may preferably carry nonionic substituents such as an alkyl radical having 1 to 4 carbon atoms. carbon, alkoxy having 1 or 2 carbon atoms, amino, nitro, chloro, bromo, cyano or phenyl.

représente de préférence un radical de formule

où - Z représente O , S , NR1 , C(CH3)2 ou -NH-CO- et
- R1 est un atome d'hydrogène ou un groupe alkyle.If X represents = C (W) -, the symbol

preferably represents a radical of formula

where - Z represents O, S, NR1, C (CH3) 2 or -NH-CO- and
- R1 is a hydrogen atom or an alkyl group.

 Preferred substituents in the ring (d) are for example one or two alkyl groups having 1 to 4 carbon atoms and especially a trifluoromethyl group, an alkoxy group having 1 to 4 carbon atoms, one or two chlorine atoms, an atom bromine or cyano, cyclohexyl, phenyl, phenylalkyl (1 to 3 carbon atoms in the alkyl group), alkylsulfonyl having 1 to 4 carbon atoms, phenyl sulfonyl or 502 T (where T has the above meaning).

The nucleus (a) may contain, as other substituents, for example a chlorine or bromine atom or an alkyl group having 1 or 2 carbon atoms or a radical of the genus Q-Set. The nucleus (b) may contain, for example, an alkoxy radical. (1 or 2 carbon atoms), chloro, bromo or a radical of the genus QS-
Preferred alkyl radicals W 1, W 2 and W 3 contain 1 to 4 carbon atoms and in particular W 3 may also contain a substituent such as an alkoxy radical having 1 to 4 carbon atoms or chloro. Particularly preferred alkyl radicals W 1, W 2 and W 3 are methyl, ethyl, n-propyl and n-butyl.

où - E est un atome d'hydrogène ou un radical méthyle, éthyle, bêta-cyanéthyle, bêta-chloréthyle, bêta-acétoxy-ethyle, bêta-méthoxy-éthyle, bêta-éthoxy-éthyle, bêta-hydroxy-éthyle, bêta-carbométhoxy-éthyle, bêta-carbéthoxy-éthyle, n-propyle,-is iso-propyle, n-butyle, n-pentyle, benzyle, bêta-phénylethyle, phényle ou, pris avec E , il forme -CH2-CH2-CH2 -
- M est un radical phényle (éventuellement substitué par 1 à 5 atomes de chlore, pa-r 1 ou 2 atomes de brome, par 1 ou deux radicaux alkyles (1 à 4 atomes de carbone), par 1 radical phényle, méthoxy, éthoxy, phénoxy, carboxylate d'alkyle dont le groupe alkyle comporte 1 ou 2 atomes de carbone, amino ou acétylamino), un groupe naphtyle ou bien M forme avec E2 un radical o-phénylène (éventuellement substitué par un radical méthyle, chlore, bromo, méthoxy ou éthoxy)
- E1 est un atome d'hydrogène ou un radical éthyle, chlore, bromo, phényl-mercapto ou son dérivé méthylé ou chloré
- E2 est un atome d'hydrogène, de chlore ou de brome ou un radical méthoxy, éthoxy, phényl-mercapto ou son dérivé méthylé ou chloré ;;
- X représente =C (w) - ou =N
- W' représente CN , COOH , COO-alkyle (ayant 1 ou 2 atomes de carbone dans le groupe alkyle)ou un radical

W is preferably CN, a COOalkyl radical (in which the alkyl group has 1 or 2 carbon atoms) or COOH, and in particular W represents CN
Preferred dyes of formula (I) correspond to formula (II):

where - E is a hydrogen atom or a methyl, ethyl, beta-cyanethyl, beta-chloroethyl, beta-acetoxy-ethyl, beta-methoxy-ethyl, beta-ethoxy-ethyl, beta-hydroxy-ethyl, beta- carbomethoxy-ethyl, beta-carbethoxy-ethyl, n-propyl, iso-propyl, n-butyl, n-pentyl, benzyl, beta-phenylethyl, phenyl or, taken with E, form -CH2-CH2-CH2 -
M is a phenyl radical (optionally substituted with 1 to 5 chlorine atoms, with 1 or 2 bromine atoms, with 1 or two alkyl radicals (1 to 4 carbon atoms), with 1 phenyl, methoxy or ethoxy radical; , phenoxy, alkyl carboxylate of which the alkyl group has 1 or 2 carbon atoms, amino or acetylamino), a naphthyl group or else M forms, with E2, an o-phenylene radical (optionally substituted by a methyl, chlorine or bromo radical, methoxy or ethoxy)
- E1 is a hydrogen atom or an ethyl, chlorine, bromo, phenyl-mercapto radical or its methylated or chlorinated derivative
E2 is a hydrogen, chlorine or bromine atom or a methoxy, ethoxy, phenylmercapto radical or its methylated or chlorinated derivative;
X represents = C (w) - or = N
- W 'represents CN, COOH, COO-alkyl (having 1 or 2 carbon atoms in the alkyl group) or a radical

 B represents the remaining members of a radical of the thiazole- (2), 1,2,4-thiadiazole- (3), 1,3,4thiadiazole- (2), 1,2,4- -triazole- (3), pyrimidine- (2), quinoline- (2), 3,3-dimethyl-indolein- (2), pyridine- (2), benzothiazole- (2) ), benzoxazole- (2), benzimidazole- (2), which may have as substituents one or two alkyl groups (1 to 4 carbon atoms each), one or two chlorine atoms, a bromine atom or an alkoxy radical (1 or 2 carbon atoms), alkylsulphonyl (1 or 2 carbon atoms), dialkylamino-sulphonyl (1 or 2 carbon atoms in each alkyl group), phenyl, cyclohexyl, nitro or amino.

où - Z1 est un atome d'oxygène ou de soufre ou un radical NH ou C(CH3)2 ;
- cl représente un atome d'hydrogene ou un radical méthyle ou bien il forme avec S2 -CH=CH-CH=CH
est S est un atome d'hydrogène ou un radical alkyle ayant 1 à 4 atomes de carbone, cyclohexyle, phényle, chloro, bromo, alcoxy (1 ou 2 atomes de carbone), alcoxy-carbonyle (1 ou 2 atomes de carbone dans le groupe alcoxy), alkyl-sulfonyle (1 ou 2 atomes de carbone) ou dialkylamino (1 ou 2 atomes de carbone dans chaque groupe alkyle) ;
-S3 est un atome d'hydrogène ou un radical alcoxy (1 ou 2 atomes de carbone), méthyle, chloro ou dialkylaminosulfonyle (1 ou 2 atomes de carbone dans chaque groupe alkyle) ; et
- S4 est un atome d'hydrogène ou de chlore.If X represents = C (W ') -, the symbol B preferably represents the remaining members of a radical of formula (II a)

where - Z1 is an oxygen or sulfur atom or an NH or C (CH3) 2 radical;
- Cl represents a hydrogen atom or a methyl radical or it forms with S2 -CH = CH-CH = CH
is S is a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms, cyclohexyl, phenyl, chloro, bromo, alkoxy (1 or 2 carbon atoms), alkoxy carbonyl (1 or 2 carbon atoms in the alkoxy group), alkylsulphonyl (1 or 2 carbon atoms) or dialkylamino (1 or 2 carbon atoms in each alkyl group);
-S3 is a hydrogen atom or an alkoxy radical (1 or 2 carbon atoms), methyl, chloro or dialkylaminosulfonyl (1 or 2 carbon atoms in each alkyl group); and
S4 is a hydrogen or chlorine atom.

If X is = N-, the symbol B preferably represents the remaining links of a thiazole- (2) 1,2,4-thiadiazole- (3), 1,3,4-thiadiazole- (2), 1 , 2,4-triazole (3), pyrimidine- (2), quinoline- (2) and in particular of a
dical pyridine- <2) or benzothiazole- (2), optionally subs
with a methyl, chloro, bromo, alkoxy (1 to 2 carbon atoms), nitro, amino, or phenyl radical.

 Preferred substituents on the two last-named cyclic radicals are methoxy, ethoxy, methyl, chloro and amino.

où - V est un atome d'hydrogène ou un radical méthyle, éthyle, bêta-cyanéthyle, bêta-chloréthyle, n-propyle, n-butyle, benzyle ou bêta-phGnyléthyle ;
- U est un radical phényle (éventuellement substitué par 1 à 5 atomes de chlore, par 1 ou 2 atomes de brome, par 1 ou 2 radicaux méthyles ou par un radical p-tertio-butyle, méthoxy ou amino), un groupe naphtyle ou bien U forme avec U2 un radical o-phénylène (éventuellement substitué par un radical méthyle, chloro, bromo, méthoxy ou éthoxy)
- U1 et U2 représentent chacun, isolément l'un de l'autre, un atome d'hydrogène, de chlore ou de brome ou un radical phényl-mercapto, tolyl-mercapto ou chlorophényl-mercapto ;;
- x2 représente =C(CN)- -C(COO-alkyle)- dont le groupe alkyle comporte 1 ou 2 atomes de carbone ou =N
- D représente les chaînons restants d'un radical pyridyle (2) ou d'un radical 6-aminopyridyle-(2) ou d'un radical azole de formule (IV) :

où - Z représente O , S ou NH
- U3 représente un atome d'hydrogène ou un radical méthyle, p-tertio-butyle, méthoxy, chloro, phényle ou éthylsulfonyle ;
- U4 représente un atome d'hydrogène ou un radical méthyle, méthoxy, éthoxy ou chloro ; et
- U5 représente un atome d'hydrogène ou de chlore.Compounds having a particular technical or industrial value correspond to formula (III)

where - V is a hydrogen atom or a methyl, ethyl, beta-cyanoethyl, beta-chloroethyl, n-propyl, n-butyl, benzyl or beta-phenylethyl radical;
U is a phenyl radical (optionally substituted with 1 to 5 chlorine atoms, with 1 or 2 bromine atoms, with 1 or 2 methyl radicals or with a p-tert-butyl, methoxy or amino radical), a naphthyl group or U is an o-phenylene radical (optionally substituted with a methyl, chloro, bromo, methoxy or ethoxy radical)
U1 and U2 each represent, independently of one another, a hydrogen, chlorine or bromine atom or a phenyl-mercapto, tolyl-mercapto or chlorophenyl-mercapto radical;
- x2 represents = C (CN) - -C (COO-alkyl) - whose alkyl group contains 1 or 2 carbon atoms or = N
D represents the remaining links of a pyridyl radical (2) or a 6-aminopyridyl- (2) radical or an azole radical of formula (IV):

where - Z represents O, S or NH
U 3 represents a hydrogen atom or a methyl, p-tert-butyl, methoxy, chloro, phenyl or ethylsulfonyl radical;
U 4 represents a hydrogen atom or a methyl, methoxy, ethoxy or chloro radical; and
U5 represents a hydrogen or chlorine atom.

 If X is = N-, the symbol Z preferably represents S and the symbols V, U3 and U5 preferably each represent a hydrogen atom.

 If X 2 is = C (CN) - or = C (COO-alkyl), the symbol D preferably represents the remaining members of an azole radical of formula (IV).

 Particularly preferred radicals V are, in addition to a hydrogen atom, a methyl and ethyl radical.

(où - R, Q, (a) et (b) ont le sens précite ; et
- Y represente =O , =Cl2 , =S ou son dérivé de type -S-lkyle ayant 1 à 3 atomes de carbone)) avec des composés de formule (VI)

(où X et A ont les sens précités).The novel compounds of formula (I) can be produced according to processes known per se in themselves. One of these methods consists in condensing compounds of formula (V)

(where - R, Q, (a) and (b) have the above meaning, and
Y represents = O, = Cl 2, = S or its derivative of the -S-alkyl type having 1 to 3 carbon atoms) with compounds of formula (VI)

(where X and A have the above meanings).

 The condensation is carried out under conditions known per se, as indicated for example in the French patent application N 74 06 701, in the French patents N 2 014 429 and N 1 526 430, in the patent of the Federal Republic of Germany. No. 1,247,513 and in French Patent 1,388,599.

 If Y represents = 0, the condensation is carried out in the presence of POU13 in an inert organic solvent such as chlorobenzene, dichlorobenzene or perchlorethylene in a temperature range between 600 and 1400 C, preferably between 800 and 1150 C.

 The compounds (V) and - (VI) are used in an approximately equimolar ratio; an excess (eg 2 to 15 percent) of the compound (VI) generally does not interfere.

 The molar ratio between POCl3 and the compounds (V) and (VI) may be between about 0.65 and 1.1, but a larger excess also does not interfere.

 The dyes are often present mainly in the form of their acid salts that can be passed in neutral form by subsequent treatment with the usual acid binding agents such as K 2 CO 3, NaHCO 3, pyridine; or possibly also can be obtained in neutral form during recrystallization in a polar solvent such as ethyl glycol or dimethylformamide.

 However, these dyes can also be produced immediately in this desired neutral form when working from the start in the presence of a tertiary base such as a trialkylamine (1 to 4 carbon atoms in each alkyl group) or pyridine.

 If X is Cl 2, S or its S-alkyl derivative (1 to 3 carbon atoms in each alkyl group), the compounds, preferably without a condensing agent, are heated in an inert solvent to temperatures of about 65 "at 1600 ° C, preferably between 800 and 1300 ° C.

As inert solvents, it is possible to use, for example
benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dichlorotoluene, chloroform, 1,2-dichloroethane, perchlorethylene, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, butyrolactone, monomethyl ether glycol, monoethyl ether glycol or pyridine.

 If Y is = alkyl, anion (the alkyl group having 1 to 3 carbon atoms), an additional acid acceptor is preferably used.

As acceptor or acid fixer, one can use
organic bases such as pyridine, triethylamine or diethylaniline, dimethylformamide or mineral acid binding agents such as potassium carbonate, sodium hydrogen carbonate, magnesium oxide, calcium, sodium carbonate, sodium methoxide or potassium hydroxide.

< où - R, A, X, (a) et (b) ont le sens précité ; et
- Hal est un atome de-chlore, d'iode ou de préférence un atome de brome) avec des composés mercapto de formule (VIII) :
Q - SH (VIII) (oÙ - Q a le sens précité) et avec une base minérale ou organique et à effectuer éventuellement la cyclisation.A second process consists in reacting dyes of formula (VII)

where R, A, X, (a) and (b) have the above meaning; and
Hal is a chlorine, iodine or preferably a bromine atom) with mercapto compounds of formula (VIII):
Q - SH (VIII) (where - Q has the above meaning) and with a mineral or organic base and optionally carry out the cyclization.

 Polar organic solvents, aprotic or protic, but having no group having an acid reaction in water are preferably used. It operates in a temperature range of 50 to 1850 C, preferably between 850 and 1200 C.

 The alkali metal or ammonium hydroxides, carbonates, alkoxides or acetates, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and ammonium hydroxide, may be used as bases. sodium methoxide, potassium acetate, or organic bases, in particular tertiary bases such as pyridine or triethylamine, as well as anion-exchange resins. The compounds and the base are used in approximately equivalent proportions.

The cyclization is carried out giving the compounds of formula (I) in which Q represents an o-arylene radical connected to the neighboring position peri of the ring (b) according to methods known per se (as described, for example, in the French patent NO 2,192,109) by diazotization and Sandmeyer reaction with Cu- (II) salts.
The starting compounds for the processes indicated for the manufacture are known or they can be obtained according to known processes. The compounds of formula (VIII) are described in the aforementioned French Patent No. 2,192,109.

The compounds of formula (VI), where X has the meaning = C (W) ->, are described, for example, in French Patent Nos. 1,361,778 and 2,402,045, in the patent application of the Federal Republic of Germany. Germany NOI) T-OS 1 207 937, in the French patent
No. 2,014,429, cited in German Offenlegungsschrift No. 2,665,552 and German Offenlegungsschrift No. 2,332,449, as well as in Journal Org. Chem. 35, (1970) 31143119 and in Chem. Abstracts 67, (1967) 64 126m.

The compounds of formula (V) are described in the aforementioned French Patent No. 2,192,109 and in the French patent.
N 2 274 663. The compounds of formula (VII) are described in the aforementioned French patent application N 74 06 701 and in the aforementioned French patents N 2 014 429 and N 1 388 599.

 Halogenation can be carried out before or after condensation with (VI). The mercapto compounds of formula QSH are for the most part known compounds in general.

 Optionally substituted thiophenols are described for example in French Patent No. 72 12 327 or they can be easily obtained, under the conditions indicated in the aforementioned French patent, from aromatic sulfochlorides.

 The dyes of formula (I), which contain cationic groups, are well suited for dyeing and printing acid-modified substrates or substrates such as polyacrylonitrile, acid-modified polyester fibers or acid-modified polyamides, as well as for color the paper.

 The dyes of formula (I) containing acid groups are particularly suitable for dyeing and printing polyamides and wool.

 The preferred dyes of formula (I) not containing ionic groups are, for example, valuable dispersible dyes which make it possible to dye and color advantageously hydrophobic fibers or fabrics. Because of their good stability, they are suitable for coloring in their mass organic polymeric materials such as polystyrene.

 The dyes of formula (I) have particularly valuable characteristics when applied to or in polyester materials, particularly polyethylene glycol terephthalates. Bright dyes or prints are obtained in the field of orange, red, violet and blue, for the most part characterized by a good power of rise and good fastness, in particular a very good fastness to light. Comparable and proposed dyes so far do not possess these benefits to the same degree.

 Sublimable dyes of formula (I), therefore dyes which do not contain ionic substituents and which would make them resistant to sublimation, such as sulfamoyl radicals, are also suitable for a thermal process of dyeing and dry printing, in particular for what is known as report printing.

Example 1
61 grams of 1-ethyl-6-phenylmercapto-benzocid-indolin-2-one (the production of which is described in French Patent No. 2,192,109) and 40 grams of benzothiazolyl-2- acetamide suspended in 280 milliliters of anhydrous chlorobenzene, 60 grams of phosphorus oxychloride are added dropwise at 900 ° C. and the mixture is stirred for 6 hours at 1050.degree.

 After cooling to room temperature, the crystalline precipitate is filtered off and vacuum-dried, washed with toluene, dissolved in 500 milliliters of dimethylformamide at 600 ° C., introduced dropwise and slowly in 1.5 g. 1 liter of 8% NaHCO 3 solution and stirred for three hours at room temperature.

sous forme d'une poudre cristalline rouge foncé.The precipitate is filtered off and vacuum-dried, washed with water, recrystallized from ethylene glycol monoethyl ether, washed with ethanol and dried at 600 ° C. under vacuum. 68 grams of the compound of formula

in the form of a dark red crystalline powder.

 On polyester fibers (1300 C), a red-colored dye with good fastnesses is obtained.

indiqués dans le tableau suivant. TABLEAU
R U1 Q U2 Z S1 S2 S3 S4
Exemple Nuance (poly
Numéro ester) 130 C

In a similar manner, the dyes of formula (IX) are produced:

indicated in the following table. BOARD
R U1 Q U2 Z S1 S2 S3 S4
Example Nuance (poly
Ester number 130 C

<tb><SEP> t
<tb> o <SEP> CH3 <SEP> H <SEP> o <SEP> H <SEP> O <SEP> H <SEP> CH3 <SEP> o <SEP> p:
<tb> m <SEP> CH26H5 <SEP> SFFC \ H33 <SEP>: <SEP> ms <SEP> Cl <SEP> m <SEP> m <SEP> X <SEP> m
<tb><SEP> n
<tb><SEP> P: <SEP> n
<tb><SEP> N <SEP> e <SEP> Cl <SEP> | <SEP> ç <SEP> U
<tb> x <SEP> 3: <SEP> H <SEP> OCH3 <SEP> O <SEP> H <SEP> C (CH3) 3 <SEP> H <SEP> H
<tb><SEP> Red
<tb> g <SEP> u <SEP><SEP> H <SEP> CF / \ H <SE> O <SEP> H <SEP><SEP> E <SEP>: c
<tb> s: <SEP> C2H4Cl <SEP> H <SEP> oe2H5 <SEP> S <SEP> H <SEP> H <SEP> OCH3 <SEP> H <SEP> Red
<tb><SEP> m <SEP> t <SEP> m <SEP>>: <SEP> x <SEP> m <SEP>:;
<tb> o <SEP> C2H4000OCH3 <SEP> H <SEP> Br <SE> OCH3 <SEP> o <SEP><SEP> H <SEP> Cl <SE> m <SEP> Red
<tb><SEP> H
## EQU1 ## <SEP> H
<tb><SEP><SEP> m <SEP> m <SEP> c
<tb><10)<SEP> C2H4C0OC2H5 <SEP> H <SEP> H <SEP> S <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> Red
<tb><SEP> Cl
<tb><SEP> O <SEP> O <SEP> O <SEP> O
<tb><SEP> m <SEP> rn <SEP> U <SEP> m <SEP> m <SEP> m <SEP> m <SEP> 8
<tb><SEP> mn
<tb><SEP> e <SEP> U <SEP> m <SEP> U <SEP> t <SEP> z <SEP> r
<tb><SEP> g <SEP> 6 <SEP> 9 <SEP> rD <SEP> g <SEP> ru <SEP> 0 <SEP> o <SEP>
<tb><SEP> :: tt <SEP> mt <SEP> mt
<tb><SEP> rt <SEP> r <SEP> r
<tb><SEP> N <SEP> n <SEP> n <SEP> n <SEP> W <SEP>><SEP> O <SEP>
<tb> TABLE (continued)
R U1 Q U2 Z S1 S2 S3 S4
Example Nuance (poly
Ester number 130 C

<tb><SEP> o <SEP> zozo <SEP> SE <o>SEP> o <SEP> o <SEP> CH3 <SEP> H <SEP> H <SEP> H
<tb><SEP> p <SEP> t <SEP> tr
<tb><SEP> 1 <SEP> 1 <SEP> 1
<tb><SEP><12)<SEP> H <SEP> C2H5 <SEP> H <SE> O <SEP> No <SEP> Xo <SEP> H
<tb><SEP> Red
<tb> (13) <SEP> C2H5 <SEP> H <SEP> CH3 <SEP> H <SEP> O <SEP> CHCH = CH- <SEP> H <SEP> H
<tb><SEP> Red
<tb> 5: <SEP> CH3 <SEP> m <SEP> / <SEP> c <SEP> 3:
<tb><SEP> Red
<tb>: <SEP> C2H4oeN <SEP><CH3) 2 <SEP> -S1Cl <SEP> m <SEP> m <SEP> m <SEP> H <SEP> e <SEP> e
<tb><16)<SEP> C2H5 <SEP> H <SEP> H3 <SEP> -S <SEP> O <SEP> H <SEP> H <SEP> H <SEP> Red
<tb><SEP> (17) <SEP> H <SEP> H <SEP> H <SEP> H <SEP> H <SEP> H <SEP> H
<tb><SEP> m
<tb> m <SEP> C2H4CN <SEP> Cl <SEP> OC2H5 <SEP> H <SEP> O <SEP> H <SEP> Br <SEP> H <SEP> H <SEP> Red
<tb><SEP> o <SEP> o <SEP> o <SEP> rn <SEP> o <SEP> o <SEP> m <SEP> O
<tb><SEP> v
<tb><SEP> Sc <SEP> m <SEP> m <SEP> m <SEP> tC <SEP> rgn
<tb><SEP>><SEP><SEP> m <SEP><SEP> rln <SEP> tc <SEP> = <SEP> rs
<tb><SEP> Cf
<tb><SEP> XZ <SEP>
<tb><SEP> mu <SEP> IrX <SEP> One <SEP> n <SEP> 6
<tb><SEP> (g <SEP> mc <SEP> i <SEP> I <SEP> rD
<tb><SEP> m
<tb><SEP> ONE
<tb><SEP> es <SEP> n <SEP> v <SEP> n <SEP> W <SEP> rv <SEP> oo
<Tb>
Example 19
44.7 grams of 1-ethyl-2-methyl-mercapto-6-phenyl-mercaptobenzoic acid, dI-indolium methosulfate are suspended in 350 milliliters of ethylene glycol monoethyl ether. 9 grams of pyridine and 20.4 of 6-methoxybenzothiazolyl-2-acetonitrile are added, heated for 3 hours at 1000 ° C. and cooled.

sous forme d'une poudre cristalline rouge foncé.The crystalline precipitate is filtered off with suction and washed with ethanol and dried under vacuum at 600 ° C. 32 g of the compound are obtained.

in the form of a dark red crystalline powder.

On polyester fibers, the dye gives 1300
Celsius a red shade with good solidity.

(dont la fabrication s'effectue selon le procédé indiqué à l'exemple 21 de la demande précitée de brevet français Nu 74 06 701) en suspension dans 400 millilitres de diméthyl-formamide, on ajoute 7,2 grammes de carbonate de potassium et 6,3 grammes de thiophenol, on chauffe durant dix minutes à l'ébullition au reflux, on verse sur 1 kilogramme d'acide acétique à 5 pour cent et l'on agite durant quinze minutes.Example 20
22.6 grams of the compound of formula

(whose production is carried out according to the process indicated in Example 21 of the aforementioned French patent application Nu 74 06 701) suspended in 400 milliliters of dimethylformamide, 7.2 grams of potassium carbonate and 6 3 grams of thiophenol are heated for 10 minutes to boiling under reflux, poured onto 1 kg of 5 percent acetic acid and stirred for 15 minutes.

sous forme d'une poudre cristalline rouge foncé.The crystalline precipitate is filtered off and dried under vacuum, washed with water, recrystallized from 560 milliliters of ethylene glycol monomethyl ether, washed with ethanol and dried under vacuum at 600 ° C. 21 grams of the compound of formula

in the form of a dark red crystalline powder.

 On polyester fibers (1300 C), the dye gives a red shade with good fastness.

In a similar manner, the dyes of formula (IX) given in the following table are obtained TABLE
R U1 Q U2 Z S1 S2 S3 S4
Nuance example (poly
Ester number 130 C

<tb><SEP> has, <SEP> has, <SEP> has, <SEP> (U <SEP> Q) <SEP> ar <SEP> has, <SEP> has,
<tb><SEP>tr><SEP> b <SEP> br <SEP> b <SEP> t <SEP> Ls <SEP> tr
<tb><SEP> 1 <SEP> 7 <SEP> 1 <SEP> 3 <SEP> 1 <SEP> 7 <SEP> 1 <SEP> 7
<tb><SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0
<tb><SEP> p:
<tb><SEP> e
<tb><SEP> 3: <SEP> 3: <SEP> m <SEP> C <SEP> 3rd <SEP> m <SEP> 3: <SEP> cu
<tb><SEP> U
<tb><SEP> v
<tb><SEP> fC <SEP> X <SEP> 3: <SEP> x <SEP> m <SEP> 3: <SEP> Z3 <SEP> X
<tb><SEP> 8
<tb><SEP> cY
<tb><SEP> H2N
<tb> (24) <SEP> C2H4Cl <SEP> 0g <SEP> g <SEP> m
<tb><SEP> 8
<tb> m <SEP> w <SEP> Fd <SEP> H <SEP> (CH3) 2 <SEP> m <SEP> H <SEP> m <SEP> m <SEP> Red
<tb><SEP> c \ t
<tb> o <SEP> -CH2-CH22- <SEP> o <SEP> o <SEP> t <SEP> o <SEP> \ <SEP> O <SEP> o <SEP> oeFL, <SEP> H <SEP> H <SEP> 3 =
<tb> m <SEP> CH3 <SEP> m <SEP> m <SEP>: <SEP> | <SEP> m <SEP> m
<tb><SEP> 3 <SEP> H
<tb> 1X3 <SEP> C2H5 <SEP> H <SEP> H <SEP> NH-C, <SEP> H <SEP> H <SEP> H <SEP> H <SEP> Red
<tb><SEP> n <SEP> In
<tb><SEP> m <SEP> Ph <SEP> U <SEP> ç
<tb><SEP> $ <SEP> Z 4zn
<tb><SEP> e <SEP><<SEP>) 1
<tb><SEP> m <SEP> m <SEP> CC <SEP> in <SEP>><SEP>: n <SEP> m
<tb><SEP> I <SEP>&verbar;<SEP> v
<tb><SEP> N
<tb><SEP> W <SEP> $ <SEP> A <SEP> X <SEP> ç <SEP> C <SEP> U
#####
<tb><SEP> 9
<Tb>
Example 29
To 19 grams of lactam of N-ethyl-4-aminobenzo- [k, 1] -thioaxanthenyl-3-carboxylic acid in 140 milliliters of anhydrous chlorobenzene was added 14 grams of 5-chloro-benzoxazolylacetamide and 800 C, 8 grams of phosphorus oxychloride are added and the mixture is stirred for five hours at 1000
Celsius.

 After cooling to room temperature, the crystalline precipitate is filtered off with suction, washed with toluene, recrystallized from 200 milliliters of N-methylpyrrolidone, washed with dimethylformamide and with ethanol and dried under vacuum at 800 ° C.

sous forme d'une poudre cristalline d'un bleu lumineux.8 grams of the compound of formula

in the form of a crystalline powder of a luminous blue.

 On polyester (process of padding "thermosol", thirty seconds of fixing, 2100 C) one obtains a shade of a reddish blue having good fastnesses.

TABLEAU
Exemple Nuance sur numéro R R' R" R" Z S1 S2 polyester

In a similar manner, the dyes of formula (X) indicated in the following table are obtained

BOARD
Example Nuance on RR 'R' number R "Z S1 S2 polyester

(dont la production est indiquée à l'exemple 7 du brevet fran çais précité N 1 388 599)en suspension dans 1 000 millilitres de diméthyl-formamide, on ajoute 15 grammes de carbonate de potassium et 12,1 thiophénol, on chauffe durant trente minutes à l'ébullition, on refroidit et 1 1on ajoute 10 grammes d'acide acétique cristallisable.(30) <SEP> CH3 <SEP> H <SEP> OCH3 <SEP> H <SEP> S <SEP> H <SEP> H <SEP> Blue <SEP> reddish
<tb> (31) <SEP> C2H4CN <SEP> H <SEP> OC2H5 <SEP> H <SEP> S <SEP> H <SEP> OC2H5 <SEP> Blue <SEP> reddish
<tb> (32) <SEP> C2H4Cl <SEP> Cl <SEP> Cl <SEP> H <SEP> O <SEP> CH3 <SEP> H <SEP> Blue <SEP> reddish
<tb> (33) <SEP> C2H4COOCH3 <SEP> H <SEP> Br <SEP> H <SEP> O <SEP> H <SEP> H <SEP> Blue <SEP> reddish
<tb> (34) <SEP> n-C4H9 <SEP> H <SEP> CH3 <SEP> H <SEP> NH <SEP> Cl <SEP> H <SEP> Blue <SEP> reddish
<tb> (35) <SEP> CH2-C6H5 <SEP> H <SEP> H <SEP> Cl <SEP> C (CH3) 2 <SEP> H <SEP> H <SEP> Blue <SEP> reddish
<tb> (36) <SEP> n-C3H7 <SEP> H <SEP> H <SEP> Br <SEP> O <SEP> C2H5SO2 <SEP> H <SEP> Blue <SEP> reddish
<tb> (37) <SEP> H <SEP> C2H5 <SEP> H <SEP> H <SEP> S <SEP> H <SEP> H <SEP> Blue <SEP> reddish
<tb> (38) <SEP> -CH2-CH2-CH2- <SEP> H <SEP> H <SEP> O <SEP> CH3 <SEP> CH3 <SEP> Blue <SEP> reddish
<Tb>
Example 39
38 grams of the compound of formula

(the production of which is indicated in Example 7 of the aforementioned French patent N 1,388,599) suspended in 1,000 milliliters of dimethylformamide, 15 grams of potassium carbonate and 12.1 thiophenol are added, the mixture is heated for 30 minutes. After boiling, the mixture is cooled and 10 grams of glacial acetic acid are added.

sous forme d'une poudre cristalline de couleur orange.The crystalline precipitate is filtered off and dried under vacuum, washed first with ethanol then with water and dried at 700 ° C. under vacuum. 36 grams of the compound of formula

in the form of an orange crystalline powder.

 On polyester vibes, the dye gives a shade of a bright orange with good fastness.

indiqués dans le tableau suivant TABLEAU
Exemple Nuance (polyester) numéro U1 Q A' 130 C

In a similar manner, the dyes of formula (XI) are obtained

indicated in the following table TABLE
Example Nuance (polyester) number U1 QA '130 C

<tb><SEP> 4J <SEP> 4S <SEP> W
<tb><SEP> 6 <SEP> E: <SEP> E:
<tb><SEP> Id <SEP> nl <SEP><6
<tb><SEP> rl <SEP> rl <SEP> C, <SEP> r (<SEP> + I
<tb><SEP> ri <SEP><SEP> ri <SEP> E:
<tb><SEP> sl <SEP> sl <SEP> rd <SEP> -r (<SEP><d
<tb><SEP> k <SEP> k <SEP> rl <SEP> k <SEP> rl
<tb><SEP> q <SEP> q <SEP> q <SEP> r
<tb><SEP> cl <SEP> a, <SEP> -rl
<tb><SEP> cU <SEP> 9) <SEP> k <SEP> + r <SEP> c, <SEP> Q) <SEP> J <SEP> k
<tb> (40) <SEP> H <SEP> ùk1Cl <SEP> orange <SEP> Q, <SEP> o <SEP> o
<tb><SEP> C <SEP> R <SEP> R <SEP> C <SEP> R <SEP> b,
<tb><SEP> 1 <SEP> 7 <SEP><SEP> rl <SEP> E: <SEP>
<tb><SEP> rb <SEP><SEP> I <SEP> LI <SEP> rb <SEP> (d <SEP> 0 <SEP> (d
<tb><SEP> h <SEP> Q <SEP> Q <SEP> ^ <SEP><SEP> z <SEP> 9
<tb> o <SEP> r <SEP> H <SEP> Q <SEP> Q <SEP> - <SEP> o
<tb><SEP> (9) <SEP> yellowish <SEP> brilliant
<tb><SEP> -tra, re <SEP> cua,
<tb><SEP> C <SEP> E <SEP> t <SEP> C <SEP> C <SEP> r =
<tb><SEP> (d <SEP> rd <SEP> 1 <SEP> rd <SEP><d<SEP> Id <SEP> 3 <SEP><d<SEP>
<tb> k <SEP> S <SEP> o <SEP> h <SEP> S <SEP> Red-orange <SEP> S <SEP> o <SEP> S <SEP> o
<tb><SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> O <SEP> p: <SE> O <SEP>&num;
<tb> (43) <SEP> Br <SEP><'eN5 ($ I <SEP>. <SEP> Orang <SEP> Brilliant
<tb><SEP> C <SEP> CH3 <SEP> 2 <SEP> Cl
<tb>'rl
<tb><SEP> k <SEP> U
<tb> FP7 <SEP> H <SEP> CCl <SEP>% N <SEP> Orange <SEP> Yellowish <SEP> Brilliant
<tb><SEP> CH
<tb> (46) <SEP> H <SEP> 2N <SEP> / NI <SEP> Z \ | /
<tb> V <SEP> Cl <SEP> Orange <SEP> reddish
<tb><SEP> cu
<tb><SEP> O <SEP> O <SEP> o <SEP> S <SEP> U <SEP> n
<tb><SEP> m <SEP> m <SEP>> 9 <SEP> m <SEP> C) <SEP> C <SEP> U
<tb><SEP> o <SEP><SEP> n <SEP> s
<tb> TABLE (continued)
Example Nuance (polyester) number U1 QA '130 C

<tb> (49) <SEP> -sl <SEP> Red-orange <SEP> brilliant
<tb><SEP><50)<SEP> gh <SEP> H <SEP> d <SEP> z
<tb> Q <SEP> h <SEP> h <SEP> z <SEP><SEP> z <SEP> -P <SEP> (d <SEP>
<tb><SEP> r <SEP><<SEP> o <SEP> eX <SEP> jazzS.
<Tb>

<SEP> cl
<tb> h <SEP> n <SEP><SEP><SEP> cdcdcd <SEP> (d
<tb><SEP> I <SEP>-r><SEP>'O<SEP> k <SEP> k <SEP> n <SEP> p <SEP> Fi
<tb><SEP><53)<SEP> a0 <SEP> 0 <SEP> hD <SEP> h0 <SEP> bD <SEP> O
<tb><SEP> tc <SEP> c:
<tb><SEP> 010 <SEP> Lg <SEP> o <SEP> kO <SEP> o
<tb> ~
<tb><SEP> N
<tb> U <SEP> H <SEP>IpP'3<SEP> N <SEP> Orang <SEP> yellow <SEP> bright
<tb> 9 <SEP> Q <SEP> H <SEP> xz <SEP> Brilliant
<tb><58)<SEP> H <SEP> NH <SEP> Red <SEP> orang <SEP> Brilliant
<tb><SEP> Cl <SEP> N2
<tb><SEP> .S <SEP> U
<tb><SEP> t <SEP> U
<tb><SEP> H
<tb><SEP> [$ <SEP> m <SEP> S <SEP> m <SEP> m <SEP> m
<tb><SEP> X
<tb><SEP> ffi <SEP> O <SEP> - <SEP> In <SEP> - <SEP> e
<tb> TABLE (continued)
Example Nuance (polyester) number 130 C
U1 QA '

(dont la fabrication est indiquée à l'exemple 7 du brevet fran çais précité NO 1 388 599) en suspension dans 850 millilitres de N-méthyl-pyrrolidone-(2), on ajoute 15 grammes de carbonate de potassium et 12,1 grammes de thiophénol, on chauffe sous agitation jusqu'à 1800 C en chassant par distillation du solvant aqueux, on refroidit, on verse sur 2,5 kilogrammes d'acide acétique à 5 pour cent et lion agite durant trente minutes.<tb><SEP> cr
<tb><SEP> b <SEP> b <SEP> b <SEP> b <SEP> H <SEP> rl
<tb><SEP> 3
<tb><SEP> (d <SEP> rd <SEP> k <SEP> (d <SEP> k
<tb><SEP> k <SEP> k <SEP> O <SEP> kq
<tb><SEP> (60) <SEP> o <SEP> \ a,
<tb><SEP> I <SEP> I <SEP> I <SEP> 2) <SEP> 1 <SEP> Eo
<tb><SEP> a) <SEP> o <SEP> o <SEP> b <SEP> o <SEP> b
<tb><SEP> c: <SE> E: <SEP> C <SEP> C <SEP> E: <SEP> C
<tb><SEP> 7 <SEP> 1 <SEP> = r <SEP><d<SEP> 7 <SEP> rd
<tb><61)<SEP> H <SEP> rd <SEP> k <SEP> Yellow- <SEP> orange
<tb><SEP> r, <SEP> r, <SEP> 0 <SEP> 0
<tb> ------------- '
<tb> ut <SEP> Cl <SEP>) ù1Cl <SEP>% L (1N02 <SEP> Yellow-orange
<tb><SEP> X <SEP> O <SEP> H
<tb><SEP> t <SEP> o <SEP> t <>t;<SEP> 0
<tb><SEP> tze <SEP> Xt <SEP> w
<tb><SEP> H
<tb><SEP> tXn <SEP> O <SEP> v <SEP> N <SEP> n
<Tb>
Example 65
41 grams of the compound of formula (65a)

(The manufacture of which is indicated in Example 7 of the aforementioned French Patent No. 1,388,599) in suspension in 850 milliliters of N-methyl-pyrrolidone (2), 15 grams of potassium carbonate and 12.1 grams are added. Thiophenol is heated with stirring to 1800 ° C by distilling off the aqueous solvent, cooled, poured over 2.5 kg of 5 percent acetic acid and stirred for thirty minutes.

sous forme d'une poudre cristalline de couleur orange.The crystalline precipitate is filtered off and filtered off with suction, washed with water, recrystallized from dimethylformamide, washed with ethanol and dried under vacuum at 70 ° C. 27 grams are obtained. compound of formula (65)

in the form of an orange crystalline powder.

 On a polyester fabric (at 1300 C), a bright orange shade with good fastnesses is obtained.

If, instead of the compound (65a), an equivalent amount of the homologous compound of the 6-ethoxy-benzothiazolyl type is used, the compound of the formula (66) is analogously obtained.

 I1 gives on polyester also a shade of a very limpid orange having good solidities.

 Compounds having valuable analogous properties are obtained when, in place of thiophenol, an equivalent amount of 4-methyl-thiophenol, 4-chlorothiophenol, 2-aminothiophenol or 5-methoxy-2-amino-thiophenol is used.

avec deux équivalents du 4-méthyl-thiophEnol et avec du carbo-nate de potassium dans de la N-méthyl-pyrrolidone pour obtenir le composé de formule (67)

According to the same processes, the compound of formula (67a) is also reacted

with two equivalents of 4-methylthiophenol and with potassium carbo-nate in N-methylpyrrolidone to obtain the compound of formula (67)

 The substance is a red crystalline powder which gives by dyeing polyester fibers a bright scarlet shade with good fastness.

TABLEAU
Exemple Nuance (polyester) numéro U1 U2 Q A' 130 C

In a similar manner, the compounds shown in the following table are produced and which correspond to formula (XII)

BOARD
Example Nuance (polyester) number U1 U2 QA '130 C

<tb><SEP> ci
<tb><SEP> c <SEP>'ir4<SEP>
<tb><SEP> H <SEP> $ <SEP> H
<tb><SEP> dC <SEP> rd
<tb><SEP> rdm <SEP> rlrl <SEP>+><SEP> CI
<tb><SEP> rlrl <SEP> tk <SEP> rl
<tb><SEP> rlrl <SEP> cucua, <SEP> ari
<tb><SEP> rlrl
<tb><SEP> kk <SEP> Lik <SEP> i, <SEP> id <SEP>
<tb><SEP> \ q) \ q, <SEP> cdubcrdcrd <SEP><d<brl
<tb><SEP> CC173
<tb><SEP> mkoookm
<tb> Q) \ O) rO) U <SEP> Red "<SEP> U <SEP> rd
<tb><SEP> EEEbP
<tb><SEP> Ilmmm31
<tb><SEP> o <SEP> U <SEP> O.
<Tb>

<SEP><69)<SEP> P: <SEP><SEP> H <SEP> Cl <SEP> O <SEP> O <SEP> O <SEP> o <SEP> 14
<tb><SEP> 3
<tb><SEP> 8 <SEP> H <SEP>. "<SEP> S
<tb><SEP> d
<tb>Z; wZrRrn <SEP> z <SEP> x <SEP> n <SEP> z <SEP> (q <SEP> glCtS
<tb> (73) <SEP> H <SEP> CH3S <SEP> CH3 <SEP> Orange <SEP> Reddish <SEP> Brilliant
<tb> s <SEP> 900ss <SEP> bones
<tb> (75) <SEP> Cl <SEP> Cl <SEP> N5 <SEP> OCH3 <SEP> Orange <SEP> Brilliant
<tb> d <SEP>, m <SEP> M <SEP> I
<tb> u <SEP> u
<tb> r <SEP> H <SEP> fi4 <SEP> Red <SEP> orange
<tb><SEP> C) <SEP> g
<tb><SEP> t <SEP> t <SEP> 84 <SEP> m <SEP> r <SEP> 4 <SEP> x <SEP> 2 <SEP> = <SEP> t
<tb><SEP> tO <SEP> o <SEP> O <SEP> N <SEP> n <SEP> F <SEP> F <SEP> F <SEP> F <SEP> F
<Tb>
Example 79
27.5 grams of lactam of 4-amino benzo-lk, 1H-thioxanthenyl-3-carboxylic acid (the production of which is described in Example 68 of the aforementioned French Patent No. 2,192,109) and 15 grams of 2-amino-benzothiazole suspended in 200 milliliters of anhydrous chlorobenzene, 17 grams of POCl3 are added dropwise at 1000 ° C. and the mixture is stirred for 10 hours at 1050.degree.

sous forme d'une poudre cristalline rouge foncé.After cooling to room temperature, the crystalline precipitate is filtered off with suction, washed with toluene, recrystallized from dimethylformamide, washed with ethanol and dried under vacuum. at 700 ° C. 3.3 grams of the compound of formula (79) are obtained.

in the form of a dark red crystalline powder.

 This dye gives on polyester fibers (1300 Cp autogenous pressure) a shade of a brilliant red having good fastnesses.

 Dyestuffs with equally valuable properties are obtained when, instead of 2-aminobenzothiazole, an equivalent amount of 6-methoxy-2-aminobenzothiazole, 6-ethoxy-2-aminobenzothiazole, 2-aminobenzothiazole, is used. amino-pyridine or 2,6-diamino-pyridine.

que l'on peut obtenir par le procédé indiqué dans l'exemple 65.Example 80/81
In 150 grams of glacial acetic acid, 21.3 grams of the compound of formula (80) are

which can be obtained by the method indicated in Example 65.

25 milliliters of water and 15 grams of concentrated hydrochloric acid are added thereto and the mixture is diazotized at 0 ° C. with a solution of 4 grams of sodium nitrite in 20 milliliters of water.

The solution of the diazonium salt is poured into a boiling solution of 50 grams of copper (II) sulfate crystallized in 500 milliliters of 10 percent acetic acid.
The mixture is heated for a further hour before boiling under reflux, and the crystalline precipitate is filtered off with suction and washed with water, it is subjected to digestion (intended to eliminate copper ions) with 400 milliliters of water. a 10 percent boiling solution of "Trilon B" is filtered and filtered again under vacuum, washed with water and dried at 700 ° C. under vacuum.

sous forme d'une poudre cristalline de couleur rouge foncé.19 grams of the compound of formula (81) are obtained

in the form of a dark red crystalline powder.

 On polyester fibers, the dye gives 1300 C a shade of bluish red with good fastness.

sous forme d'une poudre cristalline rouge foncé.Example 82
The reaction is carried out according to the data of Example 1 but, instead of benzothiazolyl-2-acetamide, an equivalent amount of benzothiazolyl-2-ethyl acetate is used. 54 grams of the compound of formula (82) are obtained in this way.

in the form of a dark red crystalline powder.

 On polyester fibers, there is obtained at 1300 C a red tint having good fastness.

TABLEAU
R U1 Q W Z S2 S3
Exemple Nuance (polyester,
Numéro 130 C)

In a similar manner, the dyestuffs indicated in the following table, which correspond to formula (IXa), are produced

BOARD
R U1 QWZ S2 S3
Example Nuance (polyester,
Number 130 C)

<tb><SEP> X
<tb><SEP> p <SEP> tr <SEP> B <SEP> b <SEP> tn
<tb><SEP> 7 <SEP> 1 <SEP> 3 <SEP> 7 <SEP>
<tb><SEP>P; O <SEP> 4 <SEP> 0 <SEP> S <SEP> 4 <SEP> 0
<tb> b <SEP> C2H4C <SEP> H <SEP> CCl <SEP> -CO- <SEP> P:
<tb><SEP> e
<tb><SEP> C2H4Cl <SEP> 8 <SEP>'s:<SEP> m <SEP> ::
<tb> S <SEP> n-C4H9 <SEP> Cl <SEP>? lr "<SEP> = <SEP> 3:
<tb><SEP> x <SEP> u <SEP> B <SEP> o <SEP> 8
<tb> o <SEP> tq <SEP> o <SEP> H <SEP> H <SEP>, 01 <SEP> S <SEP> o <SEP> o
<tb><SEP> u <SEP> H <SEP> F1 <SEP> Y
<tb><SEP> t (Cu <SEP> CH3 <SEP> a <SEP>
<tb><SEP> m
<tb><SEP> f
<tb> TABLE (continued)
Example R U1 QWZ S2 S3 Grade (polyester, number 130 C)

<SEP> (91) <SEP> CH3 <SEP> Br <SEP> Cl <SEP> CON <CH3) 2 <SEP> Y <SEP> CH3 <SEP> H <SEP> Red
<tb><SEP><92)<SEP> C2H5 <SEP>ffC'H3<SEP> cH3 <SEP> C0N <n-C4H9) 2 <SEP> O <SEP> H <SEP> H <SEP> Red
<tb><SEP> 4D <SEP> W <SEP> C2H5 <SEP> 4J
<tb><SEP> Q) <SEP> a, <SEP> o
<tb><SEP> rl <SEP>
<tb><SEP> 0 <SEP> 0 <SEP> 0
<tb><SEP> 3 <SEP>><SEP>><SEP> Red
<tb><SEP> I <SEP> I <SEP> I
<tb><SEP> e "e, N <SEP> 7 <SEP> 7 <SEP> z <SEP> z <SEP> ç <SEP> z <SEP> o <SEP> 6)
<tb><SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0
<tb><95)<SEP> H <SEP> g <SEP> g <SEP><SEP><SEP><SEP> H <SEP>
<tb><SEP> / N <SEP> H3
<tb> I
<tb><SEP> X <SEP> N
<tb><SEP> m <SEP> C2H5 <SEP> H <SEP> m <SEP> m <SEP> m <SEP> 3 ::
<tb><SEP> f <SEP> m <SEP> i) <SEP> m <SEP> 3 <SEP> c <SEP> f <SEP> m
<tb><SEP> (98) <SEP> C <SEP> H <SEP> H <SEP> Cl <SEP><SEP> CH3 <SEP> H <SEP> Rougo-purple
<tb><SEP> 0 <SEP> 0 <SEP> O <SEP> m <SEP> 00 <SEP> 0
<tb><SEP> x
<tb><SEP> N <SEP> N <SEP> L <SEP> r-7 <SEP>
<tb><SEP> B <SEP> o <SEP><SEP> O <SEP> / <SEP> Z
<tb><SEP> n
<tb><SEP> cJ <SEP> u
<tb><SEP> b
<tb><SEP> e
<tb><SEP> 8 <SEP> 8 <SEP> ONE <SEP>: x: <SEP> m <SEP> m <SEP> m <SEP> m <SEP> ::
<tb><SEP> tn <SEP> n <SEP> e
<tb><SEP> ç <SEP> i <SEP> x
<tb><SEP> U <SEP> U <SEP>: n <SEP> m <SEP> m <SEP> U <SEP> U <SEP> U <SEP> m
<tb><SEP> ~ <SEP> ts
<Tb>
Example 100
The procedure is carried out according to the data of Example 20 but, instead of the compound (20a), an equivalent amount of the compound of formula (100a) is used.

sous forme d'une poudre rouge foncé.In this way 24 grams of the compound of formula (100) are obtained:

in the form of a dark red powder.

rouge (polyester)

Similarly, compounds (101) and (102) are also produced:

red (polyester)

sous forme d'une poudre cristalline bleue.Red (polyester)
Example 103
The procedure is according to the data of Example 29, but instead of 5-chloro-benzoxazolyl-2-acetamide, an equivalent amount of benzoyazolyl-2-ethyl acetate is used. In this way 9.5 grams of the compound of formula

in the form of a blue crystalline powder.

 On polyester (thirty seconds at 2100 C) we obtain a shade of a reddish blue with good fastness.

 Dyestuffs with similar dyeing characteristics are obtained when, in place of benzothiazolyl-2-ethyl acetate, the equivalent amount of methyl 5-chloro-benzoxazolyl-2-acetate, acid methylamide, is used in each case. methyl benzoxazolyl-2-acetic acid, benzoxazolyl-2-acetic acid piperidide, ethyl 6-methoxy-benzothiazolyl-2-acetate or benzimidazolyl-2-ethyl acetate.

Claims (9)

 1 - Dyes characterized in that they correspond to the general formula

 where - R is a hydrogen atom or an alkyl, alkenyl, aralkyl, cycloalkyl, aryl radical or a two or three-membered alkylene radical and which is connected to the ortho position adjacent to the nucleus (a)  Q is an aryl radical or an o-arylene radical connected to the perimeter position of the ring (b);  X represents = C (W) - or = N-;  - W represents CN, CONW1W2, COOW3 or a radical of formula

 cyclic and acyclic radicals may contain the usual substituents in dye chemistry.  A represents the remaining members of a 5 or 6 membered, substantially aromatic, terocyclic he radical and optionally comprising a fused benzene ring; and  when taken singly, W1, W2 and W3 each represent, singly, a hydrogen atom or an alkyl radical; and W 1 and W 2 may also form with the aeot atom to which they are attached a 5- or 6-membered saturated heterocyclic ring  2 - dyes according to claim 1, characterized in that they correspond to the formula

 where - when taken alone, E is a hydrogen atom or a methyl, ethyl, beta-cyanethyl, beta-chloroethyl, beta-acetoxy-ethyl, beta-methoxy-ethyl, beta-ethoxy-ethyl, beta-hydroxy group ethyl, beta-carbomethoxy-ethyl, beta-carbethoxy-ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, beta-phenylethyl or phenyl and, when E is taken with E1, may form a radical - CH2-CH2-CH2  when taken alone, M is a phenyl radical (optionally substituted with 1 to 5 chlorine atoms, with 1 to 2 bromine atoms, with 1 or 2 alkyl radicals having 1 to 4 carbon atoms, with a phenyl radical; methoxy, ethoxy, phenoxy, alkyl carboxylate of which the alkyl group has 1 or 2 carbon atoms, amino or acetylamino) or a naphthyl radical; and M can form with E2 an o-phenylene radical (optionally substituted with a methyl, chloro, bromo, methoxy or ethoxy radical)  X1 represents = C (W ') - or = N-  W 'is a CN, COOH, COO-alkyl radical (1 or 2 carbon atoms in the alkyl group) or a radical

 E is a hydrogen atom or an ethyl, chloro, bromo, phenylmercapto or its methylated or chlorinated derivative and E2 is a hydrogen, chlorine or bromine atom or a methoxy, ethoxy or phenyl radical; mercapto or its methylated or chlorinated derivative.  B represents the remaining links of a radical of the thiazole- (2), 1,2,4-thiadiazole- (3), 1,3,4-thiadiazole- (2), 1,2-series; 4-triazole- (3), pyrimidine- (2), quinoline- (2), 3,3-dimethyl-indolenine- (2), pyridine- (2), benzothiazole- ( 2), benzoxazole- (2), or benzimidazole- (2), which may contain as substituents one or two alkyl radicals (1 to 4 carbon atoms), one or two chlorine atoms, a bromine atom or a radical alkoxy (1 or 2 carbon atoms), alkylsulphonyl (1 or 2 carbon atoms), dialkylamino-sulphonyl (each alkyl group has 1 or 2 carbon atoms), phenyl, cyclohexyl, nitro or amino  3 - dyes according to claim 1, characterized in that they correspond to the formula

 where - V is a hydrogen atom or a methyl, ethyl, beta-cyanoethyl, beta-chloroethyl, n-propyl, n-butyl, benzyl or beta-phenylethyl radical  when taken alone, U is a phenyl radical (optionally substituted with 1 to 5 chlorine atoms, with 1 or 2 bromine atoms, with 1 or 2 methyl radicals, or with a p-tert-butyl, methoxy radical; or amino), or a naphthyl radical; and when taken with U2, U may form an o-phenylene radical (optionally substituted with a methyl, chloro, bromo, methoxy or ethoxy radical);  Each of U1 and U2 is a hydrogen, chlorine or bromine atom or a phenylmercapto, tolylmercapto or chlorophenylmercapto radical;  - X2 represents = C (CN) -, = C (COO-alkyl) - or -N- (the alkyl group having 1 or 2 carbon atoms);  D represents the remaining links of a py-ridyl- (2) or 6-aminopyridyl- (2) radical or of an azole radical of formula

 U5 is a hydrogen or chlorine atom.  U 4 represents a hydrogen atom or a methyl, methoxy, ethoxy or chloro radical; and  U 3 represents a hydrogen atom, a methyl radical, p-tert-butyl, methoxy, chloro, phenyl or ethylsulphonyl;  Z represents O, S or NH  4 - dye according to claim 1, characterized in that it meets the formula

 5 - dye according to claim 1, characterized in that it meets the formula

 6 - Process for producing dyes according to claim 1, characterized in that compounds of formula

 (where - R, Q, (a) and (b) have the meanings given in claim 1, and  Y represents = 0, = C12, = S or its alkyl derivative (1 to 3 carbon atoms) with compounds of formula

 (where X and A have the above meaning).  7 - Process for producing dyes according to claim 1, characterized in that compounds of formula

 (where - R, A, X, (a) and (b) have the meanings given in claim 1, and  Hal is a chlorine, iodine or preferably a bromine atom) with mercapto compounds of formula  Q - SH (where Q has the meaning indicated in claim 1) in the presence of bases.  8 - Application of dyes according to claim 1 for dyeing and staining high molecular weight materials.  9 - High molecular weight materials, dyed or stained with at least one dye according to claim 1.