DE2355967A1 - POLYCYCLIC COLORS, METHOD FOR MANUFACTURING AND USING them - Google Patents

Description

FARBWERKE EOSCuST AG yorüials, iioister Lucius. & Brüaing File number: HOE 73 / F 3 ^ f .2355967

Date: November 8, 1973 · Dr.ST/pR '' ■

Polycyclic dyes, process for their preparation and their delusion

The present invention relates to new polycyclic compounds, . Processes for their production and their use,

The new compounds correspond to the general formula I.

wherein A is a mononuclear or omnuclear heterocyclic ring and B represents an aromatic or heterocyclic ring.

These substances are obtained in such a way that in'an dyes of the formula II - '. ■ Y /. . .- · -.

(H)

where A and B have the meaning given above and Z a removable group, for example a hydroxy, alkoxy, optionally substituted amino or a sulfo group

INAL IMSPECTED. 509830 / O90S

or denotes a halogen atom, c; -elidated and then optionally quaternized or sulfated.

The cyclization can be carried out by heating in a suitable solvent, for example in water or an organic Solvents such as ethyl alcohol, amyl alcohol, ethylene glycol, Acetone, dichlorobenzene, chloroform, acetic acid, propionic acid or dimethylformamide, expediently in the presence of an organic one Acid or a base.

r t

The compounds of the formula II used as starting compounds can be obtained by coupling diazotized amines of the formula III

(in)

wherein Ά has the meaning given above, with azo components of formula IV ■

H _ (\ D ι (IV)

in which B and Z have the meanings given above, or by condensation of amines of the formula III with the corresponding p-nitroso compounds of tertiary amines of the formula IV are obtained. ■

Examples of amines of the formula III include pyrazolopyridines. T ^ razolo-triazolo-pyridine, pyrazolo-pyrazole or pyrazoloquinoxaline into consideration. -

As azo components of the formula IV, for example, hydroxy- ^ Alkoxy, amino, mono- or dialkylamino compounds of the benzene, naphthalene, pyrimidine, pyridine, quinoline or Pyrazole series into consideration.

«■ 55 -

609830/0908

The diazotization of the amines of the formula III can be carried out according to known methods Methods, for example with alkali nitrite and an inorganic one Acid, for example hydrochloric acid, sulfuric acid or phosphoric acid, or by means of nitrosylsulfuric acid ".

The coupling with the aso components of the formula IV can also in a manner known per se, e.g. in a neutral to acidic environment, optionally in the presence of sodium acetate or similar buffer substances which influence the coupling rate or Catalysts, e.g. diethylformamide, pyridine or its salts, be made.

Of these new connections, those that should be emphasized are do not have any water-solubilizing groups and are particularly suitable for dyeing polyester fibers.

Of the new compounds of the present invention are as preferred to mention those of the formulas (v) and (VI)

(V)

5098313/0908

(VI)

ι '

wherein X ₁ and X "are a secondary or tertiary amino group, 'Y
a lower alkyl radical, W hydrogen, a halogen atom, a nitro or cyano group and V a lower alkyl radical, an alkoxy or aryloxy group or a primary, secondary or tertiary amino group, R · a lower alkyl radical, an aralkyl or aryl radical, X a secondary or tertiary amino group, Y is a lower alkyl radical, W is hydrogen, a halogen atom, a nitro or cyano group and V is a lower alkyl radical, an alkoxy or aryloxy group or a primary, secondary or tertiary amino group. "-

These compounds can be made according to the above-mentioned method from amines of the formula (VIl)

NH,

(VII)

where V, ¥ and Y have the meanings given above,

509830/0 90

as diazo components or from pyrimindine compounds of the formula (viii)

^X 1 p | Γ ^Χ 1 (VIII)

^X 2

or from pyridine compounds of the formula (iX)

(ix).

as coupling components in which X ₁ , X ", X- and R ¹ the
Have the above meanings, and subsequent cyclization of the azo dyes are prepared. "

In particular, are of the new compounds of the general formula (l) of the present invention those dyes as preferred and to be mentioned as advantageous in which the radical A has the general formula (x), (Xl), (XIl) or (XIIl)

(X)

609830/0906

(Xu) r ^ f ^ _(XIII)

owns; therein R ₁ , Rp, R and R ^ have the following meanings:

R ₁ is a hydrogen atom or an alkyl group with 1-4 carbon atoms, especially the methyl or ethyl group,

Rp is a hydrogen atom, an alkyl group with 1-4 carbon atoms, in particular the methyl or ethyl group, or - the phenyl radical,

R "is a bromatora or the cyano group,

Rr is a hydrogen atom, an alkyl group with 1-4 carbon atoms, especially the methyl or ethyl group, an alkoxy group with 1-4 carbon atoms, especially the Methoxy or ethoxy group, the amino, benzylamino, phenylaraino, 1-morphovlino-, the piperidino-, a monoalkylamino-, Dialkylamino or an N-phenyl-rN-allc3'-lamino group in which the alkyl groups each have a radical of 1-4 carbon atoms and are replaced by chlorine, cyano, hydroxy or an alkoxy group with 1-4 carbon atoms can be substituted, or the phenoxy group,

and the radical B is the pyrimidin-ylen- (5> 6) radical of the formula (XIV) or the pyridin-ylene (5i6) radical of the formula

/ 7 609830 / 0S08

X
NN

• X

means in which the radical X is a substituted amino group the formula

-N

represents, in which Rg and SR- are the same or different and each is an alkyl radical of 1 - 6 carbon atoms, preferably 1 - h carbon atoms, the through-chlorine, hydroxy, cyano or alkoxy groups with 1 - h carbon atoms, preferably methoxy - and ethoxy groups, by which sulfato - (- OSOJE), aminb, a monoalkylamino or a dialkylamino, each with 1 - k carbon atoms in the alkyl radical or by a trialkylaniino group with 1 - 3 carbon atoms in each alkyl radical, can be substituted, a cyclohexyl radical, the benzyl - or phenyl radical, which can be substituted in the nucleus by chlorine, methoxy, ethoxy, methyl7, ethyl, nitro, sulfo, amino, monoalkylamino or dialkylamino groups with 1 - h Kojlenstoffatomen in the alkyl radical, mean, R _{1 can} also be hydrogen and R ₁ and R together with the nitrogen atom form a morpholine or piperidine ring, and R ^ is the methyl or benzyl group.

Correspondingly, they are preferred for the preparation of these compounds to name those from the formula (ill), - the "general

509830/0906

Formulas (XVl), (XVIl), (XVIIl) or (XIX) have:

NH,

(XVI)

NH

2 (XVIl)

NH,

(XVIIl)

(XIX)

in which R ₁ , R ₂ , R "and R ^ have the above meanings. Preferred compounds from the formula (III) are pyrimidine compounds which have the same or different amino groups of the formula in the 2-, k- and 6-positions

-N

^l 7

contain, in which R, - and R "are identical or different and the have the above meanings. Also to be mentioned as preferred are the 3-cyano-4-methyl- and 3-cyano-4-benzyl-pyridine compounds, which in the 2- and 6-positions are identical or different from one another aniinorest of the formula -NR ^ -R-, the above meaning contain.

/ 9 50983G / G90G

The compounds of the formula I obtained according to the invention are obtained new, valuable dyes, which, if they are free of sulfonic acid groups, are excellent for dyeing and printing of synthetic fibers, for example from polyacrylonitrile or from copolymers of acrylonitrile with other vinyl compounds, such as acrylic esters, acrylamides, vinyl pyridine, vinyl chloride or vinylidene chloride, or from copolymers of dicyanethylene and vinyl acetate, as well as from acrylonitrile block polymers, Fibers made from polyurethane, polypropylene, cellulose triund-2 1/2 acetate and especially fibers made of polyamides, such as polyamide-6, Polyamide-6, '6 or polyamide-12 and from aromatic polyesters, such as those made from terephthalic acid and ethylene glycol or 1, 4-dimethylolcyclo.hexane, and copolymers from Tereph.th.al7 and Isophthalic acid and ethylene glycol are suitable, they produce predominantly yellow, intensely fluorescent colors of high color strength and brilliance, which have excellent temperature resistance and in some cases also good light and wet fastness properties.

509830/0906

.If the dyes of the formula I are water-solubilizing, ^V; _;
Groups such as sulfonation groups _; contain,
they are suitable for dyeing solid and polyamide fibers.

• The new dyes of the formula I are also suitable for ^

Dyeing of synthetic polymers, such as polystyrene, poly-
_: . vinyl chloride, polymethacrylate, polyethylene or polypropylene
in bulk. . . ·, /

For dyeing in aqueous liquors, the water- '.' ■■ '·] ... insoluble dyes of the formula I are advantageously used in fine form

distributed form and colors with the addition of dispersants
· "Examples temperatures between 95 ° and 12O ⁰ C.- '. 7. ■■ *; .- ·; "". ^r "* Γ ^\: \\ ifi - ^.

The dyes can also be used in dye baths, the organic
Contain solvents, are used.

The new dyes of the formula I, which quaternary groups
have, can be obtained in such a way that the
Dyes of the formula I which contain quaternizable groups,
treated with alkylating agents. Preferred Quaternary Groups

are ammonium residues and the hydrazinium groups. ;

Alkyl halides, aralkyl halides, haloacetamides, ß-halopropionitriles, halohydrins, / '"' ..; Alkylene oxides, acrylic acid amides, alkyl esters of sulfuric acid; · or alkyl esters of organic sulfonic acids. -:"·;

Suitable alkylating agents are, for example Hethyl ~ · Λ chloride, bromide or iodide, A'thylbromid or iodide, propyl · bromide or iodide, benzyl chiorid, chloroacetamide, ß ~ chloropropionitrile, ethylene chlorohydrin, dimethyl sulfate, methyl benzenesulfonate, p- Toluolsulfonsäureraethyl-, -äthyl-, -propyl- or '. butyl · The alkylation is advantageously carried out in "one,: .-; ^-

ORIGINAL INSPECTED
509830/0906

-.11- '

indifferent organic solvents, for example in a hydrocarbon, chlorinated hydrocarbon or nitro hydrocarbon, such as benzene, toluene, xylene, tetrachloroethane, chloroform Carbon tetrachloride, mono- or dichlorobenzene or nitrobenzene, in an acid amide or acid anhydride, such as dimethyl- formamide, N-methylacetamide or acetic anhydride, in dimethyl « sulf oxide or in a ketone such as acetone or methyl ethyl ketone. Instead of an organic solvent, a "Excess alkylating agent can be used.

The alkylation is carried out at elevated temperature, optionally with the addition of acid-binding agents such as magnesium oxide, magnesium carbonate, soda, calcium carbonate or sodium bicarbonate and optionally under pressure. The most favorable conditions in each case can easily be determined by means of a preliminary test. · \ ■ ... "-" ■ "

If appropriate, the alkylation can also be carried out in water. The new dyes that have quaternary groups contain 'preferably' the remainder of a strong ■ anion Suture, for example of sulfuric acid or its half-esters, an arylsulfonic acid or a hydrohalic acid. "These Anions introduced according to the method can also be replaced by anions of other acids, for example phosphoric acid, acetic acid, Oxalic acid, lactic acid or tartaric acid can be replaced. The dyes can also be in the form of their double salts with zinc or Cadmium halides are obtained. \

The dyes of the formula I according to the invention with an optionally quaternized amino 'or hydrazino groups are suitable for dyeing or printing tannic cellosis fibers, silk, Leather or 'fully synthetic fibers, such as acetate silk, polyamide; fibers or acid modified polyamide or polyester fibers, In particular, however, of polyacrylonitrile or polyvinylidene- · 'J; 5 cyanide containing fibers. . ...:. ■ ..,. .... -_l. ._- ,. p

The colorings available on these fibers are usually very strong in color and generally have good light and ITaß- '· fastness, beispielsvieise good wash, milling, dyeing, ■ .. carbonizing, chlorine and Schvreißechtheiten, as well as good decatising

50 9830/0 90 6 bathroom original

Steam ", ironing, friction and complementary and ^{telechtheitene-l} The dyes are generally to a change of the;.. The pH of the dyebath largely insensitive and can be as well applied in a strongly acid bath therefore both acid in weakly They are also as applied at temperatures above 100 C at ₁ Hochtomperaturfarberei V7erden _t resistant. Full durGh is under the dyes. normal dyeing conditions completely reserved. '.''.

The dyeing with water-soluble dyes of the formula I is generally carried out in an aqueous medium at the boiling point or in closed vessels at temperatures above 100 ⁰ Q. and under pressure. The dyes can also consist of · ■ ";."/; organic solvents. ·, ■; '"'

If the dyes of the formula I have reactive radicals,. ϊ '""-'. such as vinyl sulfone, ß ~ sulfatoethyl sulfone, ^- _; · Mono- or dichlorotriazine, di- or tricnloro or -bromopyrimidine, cC- or ß-chloroacetyl or propionyl, oL , ß-di-: chloro or Λ, ß-dibromopropionyl or fluorocyclobutanecarbonyl groups , they can be used by the dyeing processes customary for reactive dyes. . * · · .-., ".;

The dyes can be used in the form of powders to prepare the aqueous dye baths and printing pastes. Both water-insoluble dyes, it is generally useful to convert the dyes into dye preparations before dyeing, which contain a dispersant and the finely divided Contain dye in such a form that a fine dispersion is formed when the dye preparations are diluted with water. Such Coloring preparations can be obtained in a known manner, for example by grinding the dye in a dry or wet form with surface-active dispersants and, if necessary, additional grinding aids. :

0FHG5NAL INSPECTED

509830/0906

-13- -._ ■ ". ■

Suitable anionic dispersants are, for example

Alkylarylsulfonates, condensation products of the formall de hy ds • with naphthalenesulfonic acids or ligninsulfonates. As non-ionogenic Dispersants are, for example, influence products from ethylene oxide to fatty alcohols or alkylphenols.

with a higher alkyl radical. . ·.

The water-soluble dyes, which are a quaternizable Contain amino group or a quaternary ammonium group, can also in the form of powders, which optionally contain adjusting agents, such as, for example, inorganic salts, dextrin and, if appropriate, further additives can be used.

It is more advantageous, however, to use .easier-to-use ·. ';, Concentrated aqueous solutions of the dyes, which _{contain about ·· -:} .ν, φ 20 to 60 % dye, one or more lower aliphatic. Carboxylic acids, · as formic acid, acetic acid, propionic ■. ^ Or lactic acid, and optionally further additives, such .- "'water-soluble polyhydric alcohols, their ethers or esters ,. polyethers, aliphatic carboxylic acid amides, Laktaiae, lactones, nitriles, dimethylsulfoxide, Diacetonalkphol, Contain dioxane, tetra ~ hydro for an or urea and water. / ■; ·; · '- pJny ~? -S} .. ·. · -'- ... *. · -. .. ·. ■ ·. - ... · ■ -. ■ ■.; ■ · · ■ -y ^ ·., ·. C-cv - rV ^ -i- ^ ^ C ^ gl ·:

·. i ■ ■ ■ · ■ ·. .

If the new dyes contain sulfonic acid or sulfate groups as water-soluble groups, they can be used . Preparation of the dye baths and printing pastes also used in the form of concentrated solutions which, in addition to the dye, contain a water-soluble anionic, cationic or nonionic surface-active agent and a water-soluble organic solvent, for example one of the solvents mentioned above. ·

The following examples serve to explain the invention »

5098 30/0006

Example 1:

9.4 parts by weight of the compound of formula

CH-

are concentrated in 30 parts by weight. Hydrochloric acid dissolved with 100 parts by weight of ice are added and the mixture is diazotized with 10 "parts by volume of 5N sodium nitrite solution. The diazonium salt solution becomes a solution of 14.7 parts by weight of 2,4,6-tris (diethylamino) pyrimidine in 20 parts by weight of conc. Hydrochloric acid stirred. After 1 hour, the reaction mixture is with 100 parts by weight of water diluted, filtered off with suction, washed neutral with bicarbonate solution and dried. After the recrystalli cation from ethanol are 14.7 parts by weight of a dye the formula ".

obtained in the form of yellow matted needles. The dye dyes polyethylene glycol terephthalate fibers from aqueous Dispersion in fluorescent yellow tones.

Analysis for C ₂ O ^H 25 ^N 11

Calculated: C-57.28 H 5.96 N 36.8

Found:. C. 57.14 H 5.87 N 36.5

509930/0900

Bel cpi e'J 2:

9.4 parts by weight of the compound of formula

CH-

N ^ NH '

HIL

are, as described in Example 1, diazotized. the Diazonium salt solution becomes a solution of 13 * 1 parts by weight of 2- (β-hydroxyethylamino) -3-cyano-4-methyl-6-morpholinopyridine dripped in 200 parts by weight of glacial acetic acid. The mixture is stirred for 1 hour at room temperature and the yellow precipitated is filtered off with suction Dye off, wash with water and bicarbonate solution and dries at 60 ° C. After recrystallization from dimethylformamide, 13.8 parts by weight of a dye are obtained Formula '■' ■. ,

KHCH ₂ CH ₂ OH

in the form of yellow needles. "-.-"". · · _:. " : .- ".'..-:

The dye dyes polyester fibers in bright yellow tones.

Analysis for

Calculated:
Found:

C 54.54 C 54.21

H H

(374)

3.74 3.68

37, '37,

S0383U / 0906

Example 3

9.4 parts by weight of the compound of formula

are diazotized according to the instructions in Example 1. The diazonium salt solution becomes a solution of 9 »0 parts by weight 3 ~ hydroxy-N, N-diethylaniline diluted in 50 parts by weight. Hydrochloric acid stirred. The deposited dye of the formula

is suctioned off, washed with water and dried. The dye thus obtained is in 100 parts by weight of glacial acetic acid and 70 parts by volume of 2N sulfuric acid heated on the steam bath for 10 hours. It is poured onto ice water, neutralized with soda and soaks up the precipitated brownish yellow product of the formula

■ ^{; : C} 2 ^H 5 ■ · ■ ">■■■■■; ■ ·

off, wash with water and dry.

The dye dyes polyester fibers from an aqueous dispersion in bright yellow shades.

. ■. . . · "509830/0906 _.. 0RlßlNAL ikspected _:: " _

In Table I below, there are further inventive features Listed fluorescent dyes, which are available according to the information in Examples 1 to 3, and those on polyester fibers available colors.

Table I.

Example diazo component, coupling component, color shade

CH-

N
I.

.NH,

NH-

IT

• N 2,4,6-tris-dimethyl-yellow amino-pyrimidine

ditto 2,4,6-Tri s-morpho linopyrimidine

yellow

ditto 2,4,6-tris-piperidino-pyrimidine

yellow

dito

ditto 2,4,6-tris ~ N-methyl- yellow N ~ ß-hydroxyäthylaminopyrimidin '.

2,4-bis-ß-hydroxy yellow ethylamino-6-dimethyl-. amino-pyrimidine

ditto 2,6-bis-dimethylamino-4-propylaminopyrimidine

yellow

ίο

ditto 2,6-bis-dimethyl- yellow amino-4-phenylaminopyrimidine

ORIgBIAL BATHROOM

Example diazo component coupling coirip on en te color to η

11-

2,4-bis-isopropylamino-6-morpholino- pyrimidine

yellow

same as 2,4 bis bis cyclohexyl yellow amino-6-dimethylaminopyrimidine

CH,

N I.

N-

CH,

^C 6 ^H 5 2,4,6-tris-raorpliolino-yellow pyrimidine. .

2,4-bis-pnenylajnino-6 ~ dimethylamino-

pyrimidine

yellow

2-phenylamino-3-cyano yellow ^ -methyl-e-morpholinopyridine ■

dito

2- (4'-Metho3pyphenylamino) - ^ - cyano- ^
6-diethylamino-pyridine

yellow

503830/0966 ORiGSNAL INSPECTED

Example diazo component

■ Ü ^ li.J

m.

Coupling component "shade

2- (3'-methoxyprqpy 1-amino) -3-cyano-4-
methyl-6-piperidinopyridine

yellow

18th

dito

19th

20th

21

22nd

dito

dito

dito

dito

ditto 2-methylamino ~ 3 ~ cyano yellow 4-methyl-6-morpholinopyridine

2,6-bis-morpholino-3-yellow " cyano-4-methyl-pyridine

2,6-bis-diethylamino yellow 3-cyano-4-methyl-pyridine

2- (ß-Hydroxy-ethylamino) - yellow 3-carbonamido-4-phenyl-6-diethylamino-pyridine

2,6-bis-hydroxy-3-cyano-yellow 4-methyl-pyridine

Resorcinol

Yellow.

24 dito , ^: - Resorcm-mono- "..
; ■ methyl ether yellow 25th dito . . ß-Naphtol '" ^: - ^,:: Yellow 26th dito Λ -phenyl-3-methyl-
5-pyrazolone ^: yellow 27 dito 1-hienyl ~ 3-ynethyl-5-
aminopyrazole yellow

509830/0906

Example 28;

10 parts by weight of the dye of the formula

CH, -N- ^N N N _H i - ^ v-CH, I.
H = J NHCHpCHpOH

are concentrated in 40 parts by weight. Sulfuric acid added in portions at 20 C. After 4 hours, the homogeneous mixture is stirred on 200 parts by weight of ice. The precipitated crystalline yellow dye is filtered off, washed free of acid with V / ater and dried at 40 ⁰ C in vacuo. The dye of the formula

NHCH ₂ CH ₂ OSO ₃ H

dyes polyamide fibers in fluorescent yellow tones.

Example 29; ■. ''".. · ' ^:

9.4 parts by weight of the compound of the formula

ORIGINAL INSPECTED

are diazotized as described in Example 1.

509830/0906

The diazonium salt solution is added dropwise to a solution of 15 * 2 ^{parts by weight of 2- (3 l} -dimethyl "aminopropylamino) -3-cyano-.A-methyl-6-" morpholino-pyridine in 200 parts by weight of 2N hydrochloric acid. Han is stirred for 1 hour at room temperature and the dye precipitates out by adding chlorine-zinc liquor and 20 % sodium chloride, sucks off and dries at 40 ° C. in vacuo. The obtained dye "of the formula

^ N -CH ₂
3
-CN ZnCl ₄ ⁶⁹ Ν ^ Ύ
I I U ^ N ^N H-
) ®N-CH
^J ι ^J '2 NH
ί
(CH ₂ 3 •

dyes polyacrylonitrile and acid modified polyester fibers in fluorescent yellow tones. . .-, · ·. .: '

Example 30: ■ ■. · ■ ■ '. · ■ *

• i ...; ■ "-. ■.

9, ² I parts by weight of the compound of the formula

j if

^ nh- ¹ *

v; earth diazotized as described in Example 1. The diazonium salt solution is concentrated to a solution of 17.0 parts by weight of 2,6-bis-dimethyiamino-4- (3 ^l -sulfophenylaminu) pyrimidine in 200 parts by volume of methanol and 15 parts by volume. Caustic soda dripped. After the coupling is complete, conc. Hydrochloric acid is acidified, the methanol is distilled off, the precipitate which has separated out is filtered off with suction at room temperature and dried. ■ · -.- ..

• 509830/0906 «« Q ^ ^1NSPECTED

16.2 parts by weight of a dye from F.orsiöi are obtained

CH ₇ ,

X NH

N (CH ₅ ) ₂

in the form of yellow crystals, the polyamide fibers in fluorescent colored yellow tones

Beispi el

8.1 parts by weight of 3-amino ~ 4,6-dimethyl-1H-Oyrazolo pyridine are concentrated in 30 parts by weight. Dissolved hydrochloric acid at 60 ° C., mixed with 80 parts by weight of ice and diazotized with 10 parts by volume of 5N-liatric nitrite solution. A solution of 14.7 parts by weight of 2,4,6-tris (diethylamino) pyrimidine in 20 parts by weight of conc. It is cooled for 1 hour at room temperature, the yellow precipitate which has separated out is filtered off with suction, washed with dilute bicarbonate solution and dried at 60 ^° C. This gives 1.2 g of a yellow dye of the formula

After recrystallization from alcohol, yellow matted ones are obtained Needles.

Analysis for C ₂₀ H ₃₇ N ₉ : ·. oW & lN & l-

Calculated: C 61.1 H 6.87 N 32.1

Found: C 61.0 'H. 6.7 N 31.9 ORSSJNAL INSPECTS

The dye dyes polyester fibers in a greenish yellow fluorescent tones. The colorations are lightfast, washable, rub-proof and especially suitable for sublimation.

Example J2: -.-. '"_.

10.3 parts by weight of I-amino ^ -Biethyl-G-propylaraino-IH-pyrazolo- [3,4 ~ bj-pyridine are, as described in Example 1, diazotized. 14-.7 parts by weight of 2,4-, 6-tris- (diethylamine ^ -pyrimidine, in 20 parts by weight of conc. Dissolved hydrochloric acid. The mixture is stirred for 1 hour at room temperature, neutralized the solution by adding soda and sucks off the yellow crystalline precipitate. After recrystallization from ethanol 13.5 parts by weight of a dye of the formula are obtained

in the form of yellow needles with a melting point of 182-183 ° C

Analysis for C ₂₂ I. .60, 6th 4-56) 7, 3 _ N 32, 2 Calculated: C. 60, 3 H 7, 2 N 31, 9 Found: C. H

The dye dyes polyester fibers in bright fluorescent! yellow tones. .. ·;

INSPECTED.

$ 5,09830 / 090 - ■ - '' '.Γ

Example 33: - ^r - ■ '

8.9 parts by weight of 3-amino-4-methyl-6-methoxy-1H-pyrazolo-13 _t 4-b | ~ pyridine are, as described in Example 1, diazotized and form a solution of 15.0 parts by weight of 2,4- Bis- (propylamino) -6- (N-ynethyl-N-phenylamino) pyrimidine was added dropwise to 200 parts by volume of glacial acetic acid. The mixture is stirred for 1 hour at room temperature and then heated on a steam bath for 1 hour at 80-90 ⁰ C. After cooling to 10 ⁰ C, the fine yellow precipitate is filtered off, washed with bicarbonate solution and dried at 40 C. After recrystallization from dimethylformamide, 11.2 parts by weight of a dye of the formula are obtained

CH _x

NHC, H _P

in the form of fine yellow needles.
Analysis for C ₁₈ H ₂₅ NqO: (381)

Calculated: C. 56, 7th H 6, O N 33, 1 Found: C. 56, 58 H 5, 92 N 33, O

The dye dyes polyester fibers from aqueous dispersion in .leuchtend fluorescent yellow-green shades.

Table II below contains further dyes according to the invention and the shades of the dyeings on polyethylene glycol terephthalate fibers. ·. .

s -ihL i «t

509830/0908

Table IJ

Example diazo component coupling component e color

34

2,4,6-tris-dimethylamino-pyrimidine

Greenish yellow

35

ditto 2,4,6-tris-morpholino-green-tinged pyrimidine

yellow

36

ditto _i yy green tinting yamino-6-dimethynyl ~ ^ ^e · amino-pyrimidine ■

37

dito

¹ I.

ditto 2j6-bis-diinethylamino-4-ß-hydroxy- ethylamino-pyrimidine

2,4,6-Tris-N-methyl-N-ß-hydroxy-ethyl- amino-pyrimidine

Greenish yellow

Greens yellow

39

Br
CH,

CIL

Il

2,6 ~ bis-dimethylamino-4-phenyl-aminopyrimidine ■.,. .

yellow

ditto 2,6-bis-dimethylamino ~ 4- (4 * -methoxyphenylamino) -pyrimidine

yellow

41

ditto 2,4-bis-isopropyl-. yellow amino-6-dimethylarainopyriraidine *

5 09830/0906

INSPECTED--.

Example diazo component, coupling component, color shade

42

HH

2,4,6-tri s-dimethyl aminopyrimidine

ρ

.HN "Ii""15IH-I
C ₃ H ₇

M ₀ 2.6 ~ dimethylaraino-4- ^ benzylaraino-pyrimidine

ditto 2,4,6-tris-dimethylamino-pyrimidine

yellow

ditto 2,4-bis-cyclohexyl-

amino-6-dimethylanino-

pyrimidine

yellow

46

CH,

NI 2,4,6-tris-piperidino-yellow pyrimidine ^: '

.CH

2 ₄ 4 _> 6-rris-di ~ (β-b.ydr'oxy-yellow

HH
s 2 ethyl) -amino-pyrimidine

^HC -, r π

HIT - " ^Ιςί Η- ^Λ - KH- ^F

C ₃ H ₇

2,4,6-tris-diethylamino yellow pyrimidine. ■ '

509830/0908

ι ¹ }

At Gpi el Di azokcinponente 4-9

CH ₇ O

N 1IH ■ Clutch component color

2,4 - Bi s -phenyl aai.no-6-dimethylartiino- ■ pyrimidine

yellow

TM,

2,4-bis-benzylamino-6 ~ yellow morpholino-pyrimidine

51 ·

2 _t 4 "bis-ethylamino-. Greenish-6-dimethylane) iiio-

pyrimidine ■

'52

2 ', 6-Bi s-dimethylamino - ^ - i so-propylamino-pyrimidine

2,6-bis-dimethyl amino ~ 4-cycl oh amino pyriini d in

Greenish yellow

Greenish yellow

ditto 2,6-bis-dimethyl amino-4- (3-propyl amino) pyrimidine

Greenish yellow

55.

ditto 4,6-bis-dimethylamino-2-cyclohexylamino-pyrimidine

Greenish yellow

509830 / 09QS

2 β

Example diazo component

Coupling component color

4-, 6-bis-dimethylamino-2-iso-butyl- amino-pyrimidine

yellow

2,6 ~ bis ~ diyne ethylamino - ^ - tert-butyl- amino-pyrimidine

yellow

B ice piel% 8: ■ "'.

8.1 parts by weight of 3-amino-4,6-dimethyl-1H-pyrazolo- [3,4 - b] pyridine are, as described in Example 1, diaisotized. The resulting diazonium salt solution is added to a solution of 17.0 parts by weight of 2,6-bis-dimethylamino- ^ ~ (3'-sulfophenylamino) pyrimidine run in 200 parts by volume of methanol and 15 parts by volume of sodium hydroxide solution. After the coupling is completed acidified with conc. Hydrochloric acid, the methanol is distilled off, cools and the precipitate is filtered off. 18.9 parts by weight of yellow-brown crystals of a dye of the formula · ■ are obtained. ■,. * · - · - ■.:

the polyamide fibers and wool in fluorescent greenish yellow Tones colors.

hiiuu 4ίΐ / nnnc

:: ORIGINAL INSPECTED *

509830 / G90S

Po3.yc yell see dyes with similar properties are obtained if, instead of the diazo and coupling components given in the above) example, equivalent amounts of the in
Diazo and coupling components indicated in Table III below are used.

V ■ · Table III '■■. .

Example diazo component

Coupling component color

59

Br

CH ₇

r 2

CH-, N- "NH-3

2,6-bis-dimethylamino yellow 4- (3 * -sulfophenylamino) -. Pyriraidin * · ··.

60 -

-CH,

ί *>

, NH.

Il

.N

2-ethylamino ~ 6-dimethyl ~ yellow amino-4- (3! -sulfophenylamino) -pyrimidine -. ■ - ",.

61

dito

yellow

62

ch;

NH,

y ^c

yellow

phenyl amino) -6-dimethyl- ■ 'amino-pyrimidine.

63

CH-

CH _x O

NH,

NH

.N

dito

yellow

509830 / 09QS

... ORIGINAL'INSPECTED .- ■ ·

example

Diazo component

Coupling component color

CH,

i NP "" **

2-Amino-4- (3 ^t ~ gulfophenylamino) ~ 6-dimethylamino-pyrimidine

yellow

Example 65: 8.1 Gev; ichtsteile ^ -

pyridine v; earth according to the information in Example 1 diazotized.

The diazonium salt suspension becomes a solution of .13.1 parts by weight of 2- (β-hydroxy-ethylamino) -6-morpholino-3-cyano-4-methylpyridine poured into 100 parts by weight of glacial acetic acid.

The mixture is stirred for 1 hour at room temperature, and the precipitated sucks yellow precipitate, washed with bicarbonate solution and dried.

15> 3 parts by weight of a dye of the formula are obtained

NHCH ₂ CH ₂ OH

After recrystallization from dimethylformamide, fine yellow needles. "· ·

Analysis for Calculated: Found:

C ^ H ^ NgO (348)

C 58.0 H 4.60 N 33.2 C 57.88 H 4.56 N 33.1

The dye dyes polyester fibers in a greenish yellow fluorescent tones.

609830 / 090S ~~ * »-.« V ^

Polycyclic dyes with similar properties obtained if you replace the one given in Example 55 Diazo ™ and coupling components are equivalent amounts of the diazo and coupling components given in Table IV below used:

Table IV '/;

Example diazo component, coupling component, color shade

66

67

CE

CH.

ditto 2- (ß ~ Hydroxyäthylaminο) -3 ~ cyano-4 ~ methyl-6-di-ethylaminopyridine

2,6-bis ~ iaorpholino-3-cyano ~ 4-methyl- pyridine

Green-

embroidered

yellow

Yellow

68

69

70

. dito

dito

dito

ditto 2,6- ^; Bis-N-methyl Ή-Β -hydroxyethyl

Yellow

methylpyridine

2-phenylamino-3-cyano-4-methyl-6- morpholinopyridine

2- (3 '"methoxypropyl yellow amino) -3-cyario-4 ~ methyl-6 ~ piperidino ~ pyridine

2 _i 6-bis-hydroxy-3-green

SO9830 / Q90S BAD ORIGINAL

Example diazo component

Coupling component color

72 Br-.
3 CH, __ ^ ^Μ 2 NH ₂ 2- (ß-Hyd r o> ^ yä t hyl -
amino) -3 ~ cyano-4 ~
methyl-6-morpholino-
pyridine Yellow - \ [ Il
^ -N 2-ethyl amino- 3-cyaiio—
4 ~ methyl ~ 6-dimethyl-
aminopyridine 73 HN " dito j ' _M r * π ^ τι * ΰ ^ ι ώτπτ τ ^ / ^ · «· τ ™» f ^^^ i ^ τι c \ ^ *
<Ti. i \. \? j ι Y J. (XIiX Xxi ν - ^ ^ 7 CA · ** W ^^
4-methyl 6 ~ ( N- methyl-IT-
phenylamino) pyridine Yellow CH ₇ Yellow

CH,

CH,

Jl

HH-

CH, - CH -CH-

2-Cyclohexylamino-3-yellow cyano-4-methyl-5-dimethyl aiaino-pyridine

.76

CH,

CH ₇

NH,

2 ~ isopropylamino-3-cyano-4 ~ methyl-6-piperidino-pyridine

yellow

77

78

CH,

N

CH-

HN
H-

NH,

NH

2,6-bis-dimethylamino ~ 'yellow

3- cyano -4 ~ -me thyl -

pyridine / "." . t

2,6-313- ^ 7-1116 ^ 1- ^ yellow (β-hydr oxy-ethyl aiiin ο) 3-cyano-dimethylpyridine
S09830 / 090S -o.raw & L INSPECTED

Example. Diazo component Coupling component color

79

CIL

NH

2,6-Bis ~ iuo rpholino ~ 5 ~ yellow cyano - ^ - methyl-pyridine

80

CH-

CH

CH ₂ CH ₂ OH 2- (ß-chloroethylaraino) ~ yellow

5-cyano-4-ethyl-6-morpholino-pyridine ·

.CH

HN (CHp) _x 2,6-bis-diethylamino · »yellow 3-cyano-4-methyl-pyridine

82

2,6-bis-morpholine-3- 'yellow cyano-4-phenyl-pyridine

85

CH

NC

HN I

2 ₁ 6-Bis-diethylamino ~ yellow 3> -cyanp- ^z ^ -äthyl- ■ '. ·
pyridine. '■' ■

84

■ 2,6-bis-dimethylamino-yellow Ϊ 5-cyano-4-benzyl-pyridine

509830/0900

8.1 parts by weight of 3 ~ amino-4,6-dimethyl-1H ~ .pyrazolo- | jj, 4 ~ 6] -pyridine are, as described in Example 1, diazotized. The diazonium salt solution is added dropwise to a solution of 150 parts by weight of 2- (3'-dimethylamino-propylamino) -3-cyano-4-methyl-6-morpholino-pyridine in 200 parts by weight of 2N hydrochloric acid and then stirred for 1 hour at room temperature. The dye is precipitated by addition of ChIorzinklauge with 20% sodium chloride, filtered off with suction and dried at 40 ⁰ C in vacuo. The brown-yellow dye of the formula

_H -Jj ₁₁₀₁ θ

_H Jj ₁₁₀₁

dyes polyacrylonitrile fibers and acid modified polyester fibers " in flowing greenish-yellow tones.

Obtain connections with similar properties v / earth, if, instead of the diazo and coupling components given in the above example, equivalent amounts are used in the following Table V indicated diazo and coupling components used.

Tabel

Example diazo component. · Coupling component color

86 CH ₅ ■ 2- (2'-dimethylamino yellow

s -r-- 2 ethylamino) -3-cyano-4-

"NH" "* methyl-6-diethylamino-. pyridine

^; '""'. -509830 / Ό906 "■ - .or! Qi"? Jälϊλ

For example, diazo component Coupling component color

87

CH.

CH-

.NH

CN.

N · NH "

Il

■ N 2- (4'-dimethylamino yellow phenylami no) -3-cyano-4 ~ methyl-6-morpholinO " pyridine;.

88

Br

■ 7

CH ₇ · 5

NH; 2- (5'-dimethylaminopropyl amino) -5-cyano-4-methyl-6 ~ diethylamino-pyridine

yellow

CH-

CH ₂ -HN

dito

yellow

90

CH,

HN

NH *

ΝΗ · ditto

yellow

CH ₇ -CH-CH ₂

NH,

C. ditto

Yellow

9.2

CH-

ι
H

NH, aito

'Yellow

ORIßlNAL INSPECTED

SO.9830 / 0906

example

, 36

Diazo component

Coupling component color

93

94

95

CH

-η «

CH ₇

CH

CH

W-

CHpCH ₉ OH 2- (3'-dimethylamino-

TiTT

propylamino) -3-cyano-4-methyl-6 ~ diethylamino-pyridine

dito

yellow

NH

Il yellow

dito

yellow

^: 96

CH

HH 2- (3 ^l ~ dimethylaminopropylamino) ~ 4,6-bis-morpholino-pyrimium

yellow

97

ditto 2,6-bis-diethylamino-yellow 4- (2 ^f ~ diethyl s.mino «ethylamino) -pyrimidine

98

2- (3'-dimethylamino yellow phenylamino) -4,6-bis-N - dimethylamino-

pyrimidine. _: ''. · "

99

CH

^1T

2,4-bis- (3 * -dimethyl- yellow aminopropylamino) -6-piperidino-pyriinidine

SO9830 / O906 ^or

example

Diazo component

Coupling component color

100

CH-

Il

2- (2'-amino-ethyl-. amino) -3 ~ cyano-4 - methyl-6 - morpholinopyridine

Yellow

Example 101: [

15 parts by weight of the dye prepared in Example 65 of the formula · ·. ·

CH ₂ CH ₂ OH · '■. . ■ '..; ■

vrden in 60 parts by weight of conc. Schvjef el acid stirred in, with external cooling a temperature of ^ 20 - 25 ° C adheres to. . ■ "■. ·"., '. ·. ...'-. .-; v ·.

When the dye is dissolved, the mixture is stirred for 3 hours, pours on ice, sucks off the precipitated dye and dries

at 6O ⁰ C in a vacuum * ■ '-... - ■ · ·. . -:

The obtained dye 'of the formula,';_; - '- ■ ·

CH ₀ CH ₀ OSO _x H

dyes polyamide fibers in brilliant greenish yellow tones.

509 ^ 30/0906

Example 102: ^ ®

8.1 parts by weight of 3 ~ amino- ^, 6-dimethyl ~ 1H-pyrazolopyridine are diazotized as described in Example 1. The diazo suspension obtained becomes a solution of 9.0 parts by weight of J-hydroxy-NjN-diethylaniline in 50 parts by volume Water and 12 parts by volume of 5N hydrochloric acid added «The deposited dye of the formula

CH _x

C ₂ H,

is suctioned off, washed with water and dried. '

16 parts by weight of the dye thus obtained are with 110 parts by volume of glacial acetic acid and 75 parts by volume of 2N sulfuric acid Heated on the steam bath for 13 hours. The mixture is stirred in ice water, adjusted to pH 5-6 with soda and sucks it off fallen brownish yellow product of the formula

off, wash with water and dry.

When incorporated into polystyrene, the dye gives a brilliant yellow coloration and colors from an aqueous dispersion Polyester fibers in fluorescent yellow tones.

IMSPEQTSD

509830/0906

Polycyclic compounds with similar properties are used obtained if, instead of the diazo and coupling components given in the above example, equivalent amounts of the in Diazo and coupling components indicated in Table VI below are used. ·

Table VI

Example diazo component

Coupling component color

103

CH.

CH

aimethylaniline

yellow

104-

dito

3-hydroxy-6-methylaniline

yellow

105 106

\ ■ ditto

CH,

HH

HH-

Il

3-norpholinophenol yellow

3-hydroxy-N-ethyl yellow H-ß-cyano-ethylaniline

10?

3-hydroxy-N-phenyl yellow aniline:

108

CH.

CI * G "H

.KH.

• N

3-Hydroxy-H-bensyl- yellow aniline -. ^: ·,. .

S09830./.0906

BATH

-4 ο -

example

eri te Κυρχ; Ι υ.ηρ:. '3Λ ο mp ο η ent e Fc -rb t on

109

CH ₇ O

CH ₇ ■ 3

Resorcinol

yellow

110

ß-naphthol

HH 'yellow

111

dito 3-hydroxy-N-dimethylaniline

yellow

112

ditto J-Hydroxy-carbazole Orange

(H ₅ C ₂ ) ₂ If

CH,

pyrazolcn-5

yellow

114-

3-Hydroxy-l'T-ethyl-N-ß-hydroxyethyl aniline

yellow

115

ditto 3-hydroxyani1ine

yellow

116

CH

CH.

NH,

IT 5-hydroxy-N, N-diethylaniline

yellow

BAD ORSQ.'NAL

S0883Ö / 0906

G parts by weight of the compound of the formula

are diazotized as described in Example 1 and with 14.7 Parts by weight 2, 4, 6- Iris- (diethyl ~ amino) ~ pyrimidine coupled «. A dye of the formula is obtained

which is recrystallized from ethanol. "

Analysis for O ₃₅ H ₂₈ N ₁₀ (444)

Calculated C 62.16 H 6.51 % 31.6 Found C 61.92 - H 6.21 N 51.1

The 3-amino-pyrazolo-pyrazole used in Example 123 of the formula ·. ". '..' '

I 111.

vmrde prepared as follows: 108.7 parts by weight of 1-phenyl-3-methyl "4-cyano-5-chloropyrazole are in 300 parts by weight of glycol with 100 parts by weight of hydrate (80 % )

£ 09830/0906

Heated to the boil for 20 hours. DER precipitated crystalline precipitate is filtered off, washed with water and 'dried at 60 ⁰ C.

81.5 parts by weight of the abovementioned compound with a melting point of 264 · 66 ^° C. dimethylformamide are obtained.

Analysis for C-, N L ^W ₅ (213) Calculated N 32 .9 Found 32 .5

1-Phenyl ~ 3-ethyl-4 ~ cyano-5 ~ chloro ~ pyrasol is converted by reaction of l-phenyl-S-mstlr / l - ^ - carbonamido-pyrazolon- ^ with phosphorus oxychloride obtained in the presence of diethylaniline at 14Q ° C in high yield.

The cleaning is done by. Recrystallization from ethanol or by distillation of pesticides in an oil pump vacuum, melting point 122 - 24 ⁰ C (C ₂ H ₅ OH)

Analysis for C ₁₃ H ₈ Cl N ₅ (217.5)

Calculated Cl 16.3 N 19.3 Found * Cl 16.1 N 19.1

In Table VII below there are other inventions Dyes and their shades are listed. · ■ -. · ..

Table VII. .

Example diazo component, coupling component, color shade

124 ^u "3v / 2 2,4,6-trismorpholinO" yellow

pyriraidin

125, ditto 2,4,6-Trlsdimethylaminogolb

■ pyrimidine .... .

609830/0906 bathroom original

Example diazo component

Coupling component color

117

CK

EH-

Resorcinol

yellow

118

ditto resorcinol monomethylethyl "·

yellow

119

120

CH,

N-HH '

CH-

CH,

-HCHN

■ 'CH,

Ti

HH-

.N ß-naphthol

3-hydroxy-N, IT-dimethylaniline

yellow

yellow

121

ditto 2 "amino-hydroquinone ~ yellow · dime ethyl ether

122

ditto resorcinol dimethyl ether

yellow

Example diazo component · 'coupling component color shade

126

127

dito

2,4,6-Tris-N-methyl-N- β-hydroxyäthylaiainopyrimidin

2,6-bis-diä

yellow

yellow

128 129

dito

dito

2,6-bis-morpholino-4-methyl-5-cyano-pyridine

2-methylamino-3- cyano-4-methy1-6-morpholinopyridine "

yellow

yellow

130 dito ß-naphthol ' 131 dito . Resorcinol 132 dito
;! 3-hydroxy-W, N-diethyl
aniline 133 dito pyrazolone-5

yellow yellow yellow

yellow

example

18.5 parts by weight of 3-amino-pyrazolo ~ (3,4-b) -quinoxaline are dissolved in 20 parts by weight of concentrated hydrochloric acid and 100 parts by weight of glacial acetic acid, cooled to ⁰ ° C. by adding ice powder and diazotized with 21 parts by weight of 5N sodium nitrite solution . The diazonium salt solution is added to a solution of 26.2 parts by weight of 2- (β-hydroxyethylamino) -3-cyano-4-methyl-6-morpholinopyridine in 50 parts by weight of glacial acetic acid. After 3 hours, the precipitated dye is filtered off with suction, rait

SAD ORIGINAL

509830/0906

¹ f ~ *

Washed water and ethanol and dried at 60 ° C. ■ 31.2 parts by weight of a dye of the formula are obtained

from aqueous dispersion of polyethylene glycol terephthalate in fluorescent pink tones.

Analysis for C ₁₈ -H ₁₃ N 0 (371)

Calculates N 34.0 ■

Found N 33.6 '· ■

The 3-amino-pyrazolo · - · (3,4-b) -quinoxaline used as the diazo component was manufactured as follows: ■

37.9 parts by weight of 2-chloro-3-cyano ~ quinoxaline are added in ^{portions at HO 0} O to a mixture of 30 parts by weight of hydrasin hydrate (80 % ) with 140 parts by weight of glycol. The mixture is kept at 140 ^° C. for 30 minutes, cooled, the crystalline precipitate is filtered off with suction, washed with water and ethanol and dried. 31.2 parts by weight of golden yellow flakes are obtained, which slowly decompose above 285 ° C.

Analysis for C ₉ H ₇ N ₅ (185),. ::. ■:

Calculated N 37.8 /; · ./. ;

Found N 37.2 '. .'--: ■ '■ -.... · ^: ' .. ■ '■' ■ -. ^; - - "'' \

The following Table VII contains further dyes according to the invention which can be produced according to the instructions in Example 134, and the shades of the dyeings on polyethylene terophthalate fibers :., .-. ■ ^ - , · ",. '■ _ -

α Ο <ΛΛ Μ Λ ΑΛ

Table VII

Example diazo component, coupling component, color shade

135 '3-Amino-pyrazolo- (3,4 ~ b) quinoxaline 2,4 _t 6 ~ tris diethyl »
amino ~ py rimid in

pink

136

ditto 2,4-6 ~ tris-ffiorph.olincpyrimidine

pink

137

ditto 2,4,6 ^ Tris-N ~ metbyl-β-hydroxy ethylaminopyrimidine

pink

138

ditto 2-phenylamino-3-cyano- ^ -metnyl-6-idorpholinopyridine

pink

139 2- (3 "" methoxypropylamino) -3-cyano -4-ethyl-6-piperidino-pyridine

pink

140

ditto 2 ₁ 6-bis-morpholino-3-cyano-4 ~ pyridin ~ metliyl

pink

141

ditto ß-naphtol

-pink

142

ditto aniline

pink

fi o ü β 3 ύ i λ ο ο α

Claims (1)

HOE 73 / F 3> -i1 Patent claims: ο compounds of the general formula ■ where A is a mono- or polynuclear heterocyclic ring and B represents an aromatic or heterocyclic ring. 2. Compounds according to claim 1, characterized in that A a pyridine, triazolopyridine, pyrazole or quinoxaline residue and B a benzene, naphthalene, pyrimidine, pyridine, quinoline or pyrazole radical. 3. Compounds according to claim 1 or 2, characterized in that that they are free from water-solubilizing groups. H. Process for the preparation of compounds defined in Claim 1, characterized in that a diazoniura compound of an amine of the formula wherein A has the meaning given in claim 1, with an azo component of the formula 509330/0906 II
Z wherein B has the body indicated in claim 1 and Z a hydroxy, alkoxy, optionally substituted amino or a sulfo group, to an azo compound of F ο line 1 N = N t ι .NH in which A, B and Z have the meaning given, coupling, cyclizing this with elimination of HZ and then optionally quaternized or silfated. 5. The method according to claim 4, characterized in that one a diazonium compound of an amine of those specified in claim 4 Formula used in which A is a pyridine, triazolopyridine, pyrazole or quinoxaline radical. 6. The method according to claim 4, characterized in that one uses an azo component of the formula given in claim 4, in which B denotes a benzene, naphthalene, pyrimidine, pyridine, quinoline or pyrazole radical. 7. Use of the in claim 1, 2 or 3 or that of claim 4, 5 or 6 compounds produced for dyeing and printing synthetic fibers. 8. Use of the compounds prepared in claim 1, 2 or 3 or according to claim 4, 5 or 6 for dyeing synthetic compounds Polymers in bulk. 609830/0906