CH647239A5 - Triazine-containing dye intermediates - Google Patents

Abstract

New triazine compounds conform to the formula I <IMAGE> where A, R1, X and Y are each as defined in Claim 1. They are prepared by condensing cyanuric chloride in any desired order with - a compound of the formula II or III <IMAGE> where R1, Ad and Ak are each as defined in Claim 5, - a compound X-H and optionally - alkali or a compound Yx-H, wherein Yx is NH2 or an aliphatic or aromatic amine radical, in the corresponding stoichiometric molar ratios, and if a compound of the formula II was used thereafter reducing the NO2 group. The compounds of the formula I are diazo or coupling components and intermediates for azo dyes.

Description

The invention relates to triazine compounds. They represent intermediate dye products and are used, for example, to produce valuable mono- and disazo dyes, as disclosed in Swiss Patent No. 640 874, which are used in particular in the field of paper dyeing.

The invention accordingly relates to compounds of the formula I

N- (A-N— (ON

i. M

4th

NH

is in which the amino group is in position 3 or 4 and the phenyl ring may be further substituted by 1 or 2 substituents from the series chlorine, bromine, methyl and methoxy.

i If the remainder Ai is further substituted, there are for the remainder (Aia)

wherein

A the residue of a diazo component from the aminobenzene, aminonaphthalene, aminodibenzofuran or benzothiazole aminophenyl series or the residue of a coupling component from the naphthalene series,

Ri is hydrogen or (1-4C) alkyl, see

X the group -NRi-alk-NRjR-i or -NRz-alk-NRsRöR?

A ;,

R: hydrogen or (1-4C) alkyl,

alk linear or branched (2-6C) alkylene,

R? and R4 are independently hydrogen,

(1-6C) alkyl, substituted (2-6C) alkyl, phenyl- (1-3C) alkyl, the phenyl radical of which may be substituted, mean unsubstituted or substituted (5-6C) cycloalkyl or Rî and R4 together with the one bonded to them N atom form a 5- or 6-membered, optionally including a further heteroatom including a saturated ring,

Rs and R (independently of one another have one of the meanings of R3 and R4 except hydrogen, R? (1-4C) alkyl or benzyl,

A is an anion, and

Y is CI, OH, NH;, an aliphatic or aromatic amine radical or has one of the meanings of X.

A as the residue of a diazo component preferably represents the residue of a diazo component from the aminobenzene series. A as the residue of a coupling component preferably represents the rest of the formula, an additional substituent, preferably in positions 2, 4 or 6, and two additional substituents, preferably in positions 2.5; for the rest (Aib)

<Aib>

with the sulfo group particularly preferred in position 3. Preferred compounds correspond to formula Ia,

N "(

VMOj

1 y

Ia, there is preferably only one additional substituent 30 which can be in either the 2 or 3 position. Compounds of the formula Ib are also preferred,

Ib wherein Ri, X and Y are as defined above; the sulfo group is particularly preferably in position 3.

The radicals R 1 and R 2 as alkyl are preferably methyl.

Ri or R2 preferably represents Ria or R2a in the meaning of hydrogen or methyl, in particular hydrogen.

The alkylene radical -alk- represents a linear radical - (CH2) 2-6-, but it can also be branched and then, for example, as -CH-CH2-, -CH2-CH- or -CH2-CH-CH2-

CH3

CH3

ch3

wherein Ri, X and Y are as defined above and Ai is for the remainder; preferably -alk- represents an unbranched SS alkylene radical and particularly preferably an ethylene or propylene radical.

The radicals R3 and R4 can be the same or different and are preferably identical. As unsubstituted or substituted alkyl radicals, they can be linear or branched; As unsubstituted alkyl radicals, they preferably contain 1-4 C atoms, in particular they represent methyl or ethyl; as substituted alkyl radicals they are preferably substituted by hydroxy, in particular they are hydroxy- (C2-3) alkyl.

Phenylalkyl radicals are preferably benzyl; halogen, preferably chlorine, (1-4C) alkyl and / or (1-4C) alkoxy are to be considered as substituents of the phenyl radical, but the phenyl radical is preferably unsubstituted.

647239

4th

Cycloalkyl is preferably cyclohexyl which is unsubstituted or substituted by 1 to 3 (1-4C) alkyl groups, preferably methyl groups.

If R.3 and R.4 form a ring together with the N atom, this is preferably a pyrrolidine, piperidine or morpholine ring.

R.? and R4 independently of one another are preferably R3a and R4a in the meaning of hydrogen, linear or branched (1-6C) alkyl radical, unbranched hydroxy (C2-3) alkyl radical, benzyl, a pyrrolidine, piperidine or morpholine radical; more preferably for R3b and R4b in the meaning of hydrogen, linear or branched (1-4C) alkyl, hydroxyethyl, a piperidine or morpholine residue; especially for R3c and R4c in the meaning of methyl or ethyl.

The radicals Rs and Rf can also be the same or different and are preferably identical. The preferred meanings for R3 and R4 also apply to the radicals Rs and Rr>.

R? as alkyl is preferably methyl or ethyl, especially methyl.

R7 preferably represents R7a in the meaning of methyl, ethyl or benzyl, in particular methyl.

The anion Ae is to be understood to mean both organic and inorganic ions, for example Ae can be a chloride, bromide, iodide, methyl sulfate, ethyl sulfate or hydrogen sulfate.

Y as an aliphatic amine radical preferably represents the radical of a monoalkyl or dialkylamine, in which the alkyl group contains 1-4 carbon atoms and can be unbranched or branched, unsubstituted or substituted, where preferably halogen such as chlorine or bromine or phenyl is used as the substituent or in particular hydroxy, or the residue of a (5-6C) cycloalkylamine.

Y as the aromatic amine radical is preferably a phenylamino radical or a phenylamino radical which is substituted by 1 or 2 substituents in the phenyl ring by halogen or halogen, preferably chlorine, (1-4C) alkyl, (1-4C) alkoxy, hydroxy, phenoxy and sulfo represents.

Y preferably represents Ya in the meaning of CI, OH, NH2, monoalkyl- (1-4C) -amino, monohydroxyalkyl (2-4C) -amino, dialkyl (1--2C) -amino, bis [hydroxyalkyl (2-4C )] - amino, phenylamino or a radical X; further preferred for Yb in the meaning of CI, OH, phenylamino or a radical X; Y very particularly preferably represents Yc with the meaning of a radical X.

The radical X preferably represents the radical Xai or Xbi

-NR2a-alk-NR3aR4a (Xai) -NR2a-alk-NR5aR6aR7aAQ

(Xb i); more preferred for the rest Xa2 or Xb2

©

-NR2a-alk-NR3bR4b (Xa2) -NR2a-alk-NRsbR6bR7a A® (Xb2); more preferred for the rest Xa3 or Xb3

-NR2a- (CH2) 2-6-NR3bR4b (Xa3) -NR2a- (CH2) 2-6-NRsb R7a A (Xb3); and in particular for the radical Xa4 or Xb4 -NR2a- (CH2 or 3-NR3cR4c (Xa4) -NR2a- (CH2) 2 or

3-NR5cRf, cR7a ACl (Xb4), where R2a is preferably hydrogen.

preferably represents Za of the formula

Xa, / Xb-,

/ N—

! "NRla- <P ^

Ya

10 more preferably Ya is Yb; Ya particularly preferably represents Xai or Xbi;

more preferred for Zb of the formula

15

-nr ^ QN

N— (

Xa, / Xb, N— (2 '

Yc wherein Yc is Xa2 or Xb2; more preferred for Zc of the formula

25th

N ~ (

-NRi ^ QN

Xa3 / Xb3

Yc wherein Yc is Xa3 or Xb3; and particularly preferably for Zd of the formula

35

-NRir <ON

40

where Yc is the radical Xa4 or Xb4.

In the radicals Xbi to Xb4, R7a particularly preferably represents methyl and A9 preferably as chloride, 45 bromide, iodide, methyl sulfate, ethyl sulfate or hydrogen sulfate ion.

In the radical Xb4, Rsc, Róc and R7a are preferably methyl. The compounds of the formula I are prepared by, for the preparation of compounds of the formula Ic,

50

55

N— (

A-N - (O ^ 1 I N— (

R1 Y

I m

60

The radical Z of the formula in which A, Ri and X are as defined above and Ym is OH, NH2 or an aliphatic or aromatic amine radical, cyanuric chloride with the following components:

1

a compound of formula II or III,

M

-nr ^ ON

N ~ \

✓Ad-NHRi

II

Ak-NHRi

III

65N02

in which Ad is a radical from the benzene, naphthalene, dibenzo-furan or benzthiazole series,

5

647239

Ak is the remainder of a coupling component from the naphthalene series and R 1 is hydrogen or (1-4C) alkyl,

- a connection X-H and

an inorganic base or a compound Yx-H, in which Yx is NH2 or an aliphatic or aromatic amine radical,

in the corresponding stoichiometric molar ratios by condensation reactions in any order to give a compound of the formula Ic, and if a compound of the formula II is used after the condensation reactions, the NCh group present is reduced to the NH 2 group.

Compounds of the formula Id,

X

N- (

A-N - (ON 1 n

Id in which A, Ri and X are as defined above and Yn is Cl or has one of the meanings of X are prepared accordingly by using one or two moles of a compound XH as the second component, the reaction with the third Component (inorganic base or a compound Yx-H) is omitted.

The condensation reactions on the cyanuric chloride are carried out according to conventional methods.

The following examples serve to illustrate the invention; parts by weight or parts by volume and percentages mean percentages by weight; the temperatures are given in degrees Celsius.

nh2

Ö — S

, NH (CH2) 3N (CH3) 2

Jf

N \

NH (CH2) 3N (CH3) 2

Instead of the 3-nitroaniline used in Example 1, the following nitro compounds can also be used: 4-nitroaniline; 2-chloro or 2-bromo-4-nitroaniline, 2-methyl-4-nitroaniline, 2-methoxy-4-nitroaniline; 2-methyl-s 3-nitroaniline, 4-chloro-3-nitroaniline, 4-methyl-3-nitroaniline,

4-methoxy-3-nitroaniline; 2-methyl-5-nitroaniline, 2-methoxy

5-nitroaniline or 5-chloro-2-methoxy-3-nitroaniIin, with which corresponding solutions are obtained.

The diazo components obtained in solution according to the method of Example 1 can be processed directly without isolation and can be used, for example, for the production of mono- or diazo direct dyes for dyeing paper.

15 Example 2

125 parts of ice and water are mixed with 92 parts of cyanuric chloride to form a fine dispersion. Thereafter, 130 parts of 3-diethylaminopropylamine are added dropwise over a period of 3 hours in such a way that the temperature does not rise above 5 °. The mixture is then left to stir at 45-50 ° for 1 hour, 100 parts of 30% sodium hydroxide solution are added to the resulting solution, the product precipitating as a white mass which is filtered off with suction and washed with water. After drying in vacuo at 60 °, 150 parts of 2,4-diamino-N, N '-bis- (3-di-25 ethylaminopropyl) -6-chloro-l, 3,5-triazine are obtained. This product is dissolved in 600 parts of water and 106 parts of 30% hydrochloric acid. Then you wear 95 parts in a row

6-Amino-l-naphthol-3-sulfonic acid and 100 parts of sodium acetate and heated to 90-95 °, the pH drops from 4.5

30 to 3.7. The reaction is complete after about 3 hours. The mixture is cooled and a clear brown solution is obtained, which is the compound of the formula

example 1

92 parts of cyanuric chloride are dissolved in 750 parts of acetone and cooled to 0-5 °. 69 parts of 3-nitro-aniline are then introduced, 130 parts of a 4N sodium carbonate solution are then added dropwise over the course of one hour and the mixture is subsequently stirred for one hour; 600 parts of ice water are then added. The precipitated suspension is filtered and the moist residue is slowly added in small portions in 250 parts of 3-dimethylaminopropylamine. The mixture warms to 60-70 °, a syrupy solution is formed, which is stirred for a further 1.5 hours at 90-100 ° and then diluted with ice to about 1000 parts by volume. Two phases form, the aqueous phase is separated off, the resinous residue is stirred in 200 parts of water and 90 parts of 30% hydrochloric acid, so that a suspension with a pH of about 5 is formed. 300 parts of water, 70 parts of cast iron filings and 20 parts of 30% hydrochloric acid are placed in a second vessel and stirred at 90 ° for 1 hour. The weakly acidic suspension above is then run in and the temperature is kept at 95-98 ° for 2 hours. Then it is made brilliant yellow-alkaline with sodium carbonate and filtered hot. The yellow-brown filtrate contains the compound of the formula n— (

SO © NH (O ^

N- <

^ H (CH2) 3N (C2H5) 2

©

NH (CH2) 3N (C2H5) 2H

contains.

45 The coupling component obtained in solution according to the method of Example 2 can be processed directly without isolation and can be used, for example, to build up mono- or disazo compounds in the direct dye field.

50 Analogously to the methods described in Examples 1 and 2, further diazo and coupling components of the formula I can be prepared by a) the condensation product of cyanuric chloride and

55 one of the nitroanilines listed in Example 1 instead of 3-dimethylamino-propylamine with 3-diethylaminopropylamine or one of the diamines 1-12 listed below, resulting in a subsequent reduction of the nitro group diazo components;

60 b) the condensation product of cyanuric chloride and 3-dimethylaminopropylamine (instead of 3-diethylamino-propylamine) or one of the diamines 1 -12 listed below is reacted with 6-amino-1-naphthol-3-sulfonic acid, resulting in coupling components.

65

List of diamines 1-12:

Diamine 1 H2N- (CH2) 2-N (CH3) 2

647239

Diamine 2 h2n- (CH2) 2-N (C2Hs> diamine 3 H2N- (CH2) 2-N (CH3) 2C1 ©

/ CH3

Diamine 4 1 H2N- (CH2) 2-N <

Diamine 5 H2N- (CH2) 2-N <

^ Ms

-CH (CH3>

Diamine 6 H2N- (CH2) 2-N

CH (CH3) 2

^ / CH2CH2CH (CH3) 2 -CH2CH2CH (CH3) 2

CfL

Diamine 7 H2N-

/ (CH2). ^ (CH2) sCH3

Diamine 8 H2N- (CH2) 2 -N H

ch3 I

io Diamine 9 HN- (CH2) 4-N (C2Hs) 2 diamine 10 H2N- (CH2) 5-N (C2H5) 2 diamine 11 H2N- (CH2) 6-N (CH3) 2

15

Diamine 12 H2N- (CH2) 3-N (CH2CH2OH) 2

B

Claims (5)

647 239 2nd PATENT CLAIMS 1. triazine compounds of the formula I, X / N- ( A-N— (ON 1 R N ~ < R1 Y wherein A the residue of a diazo component from the aminobenzene, aminonaphthalene, aminodibenzofuran or benzothiazole aminophenyl series or the residue of a coupling component from the naphthalene series, Ri is hydrogen or (1 -4C) alkyl, © X the group -NR2-alk-NR3R4 or -NR ^ -alk-NRsRóR? A% R2 is hydrogen or (1-4C) alkyl, alk linear or branched (2-6C) alkylene, R3 and R4 independently of one another are hydrogen, (1-6C) alkyl, substituted (2-6C) alkyl, phenyl- (1-3C) alkyl, the phenyl radical of which can be substituted, denote unsubstituted or substituted (5-6C) cycloalkyl or R3 and R4 together with the N atom bound to them form a 5- or 6-membered, optionally including a further heteroatom, saturated ring, Rs and Rö independently of one another have one of the meanings of R3 and R4 except hydrogen, R7 (1-4C) alkyl or benzyl, A 3 is an anion, and Y is CI, OH, NH2, an aliphatic or aromatic amine radical or has one of the meanings of X. 2. Compounds according to claim 1, wherein A is the residue of a diazo component from the aminobenzene series. 3. Compounds according to claim 2, according to formula Ia, N - ( a, MON 1 y la Formula le, X , N ~ ( sa-n- <On R, N ~ A 1 Y le m 10 wherein A, Ri and X are as defined in claim 1 and Yrr is OH, NHa or an aliphatic or aromatic amine radical, characterized in that cyano chloride with the following building blocks: ls - a compound of formula II or III, ^, Ad-NHRi II Ak-NHRi NO2 III 20th in which Ad is a radical from the benzene, naphthalene, dibenzo-furan or benzthiazole-phenyl series, Ak is the residue of a coupling component from the naphthalene series and Ri is hydrogen or (1-4C) alkyl, 25 - a compound X-H and - an inorganic base or a compound Yx-H, where Yx is NH2 or an aliphatic or aromatic amine residue, in the corresponding stoichiometric molar ratios 30 by condensation reactions in any order to give a compound of the formula Ic, and if a compound of the formula II is used, the NO 2 group present is reduced to the NH 2 group after the condensation reactions. 35 6. Process for the preparation of compounds of the formula Id, ..A-Ij— <Q> R, n ~ \ Id wherein Ri, X and Y are as defined in claim 1 and Ai for the rest j®- NH23 is in which the amino group is in position 3 or 4 and the phenyl ring may be further substituted by 1 or 2 substituents from the series chlorine, bromine, methyl and methoxy. 4. Compounds according to claim 1, wherein A represents the rest of the formula. 5. Process for the preparation of compounds 45 wherein A, Ri and X are as defined in claim 1 and Yn is Cl or has one of the meanings of X, characterized in that cyanuric chloride with the following components: 50 - a compound of formula II or III, ^ / Ad-NHRi II Ak-NHRi NO2 III 55 in which Ad is a radical from the benzene, naphthalene, dibenzo-furan or benzthiazole-phenyl series, Ak the rest of a coupling component from the naphthalene series 60 and R 1 are hydrogen or (1-4C) alkyl, and - one or two moles of a compound XH are converted by condensation reactions in any order to give a compound of the formula Id, where, if a compound of the formula II is used, 65 is used Condensation reactions the present N02 group is reduced to the NH2 group. 3rd 647 239