CA1222510A

CA1222510A - Azo compounds

Info

Publication number: CA1222510A
Application number: CA000449594A
Authority: CA
Inventors: Hansrudolf Schwander; Jean-Marie Adam
Original assignee: Ciba Geigy Investments Ltd
Current assignee: BASF Schweiz AG
Priority date: 1983-03-16
Filing date: 1984-03-14
Publication date: 1987-06-02
Also published as: ES8606896A1; EP0122458B1; ES530648A0; EP0122458A1; DE3475918D1; BR8401200A

Abstract

Abstract 1-14355/14527/+

Azo compounds Novel basic and cationic azo compounds of the formula [F-A]-(B)x in which the symbols F, A, B and x are as defined in claim 1, are described, as are processes for their preparation and their use, in particular as dyes for dyeing and printing textile materials, leather and, in particular, paper, materials which have been dyed red with good overall fastness properties being obtained.

Description

i2225'LO
1 - ~
, 1-14355/14527/~
_~ ...

Azo compounds The invention relates to novel azo compounds, pro-cesses for their preparation and their use as dyes for dye;ng and Pr;nt;ng textile materials, leather and~ ;n part;cular, paper.
. The novel azo compounds have the formula I

[F A ~B)x ~ I ) . .
;n which F is the radical of an azo comPound containing sulfonic acid grouPs, A is a radical of the formula ~ ' :, !

~ NR-C-Rl~ R-co-cH(NR-co-Rl-)2l -NR-co-R2-l -N~
~ R3" \ R \
! N
N N
: -N-C0-N-X- and -N-! !-N-X-Rl" R2" Rl" l R2ll ~;:, !
1:
.~ .
in which R ;s hydrogen or C1-C4-alkyl, R1 ;g a linear or branched C1-C6-alkylene radical or a C1-C6-vinylene radical, R2 is a heterocyclic radical, R1" and R2"
' `:~

` ''"`

.

- 2 - ~2~
independently of one another are hydrogen or C1-C4-alkyl, it being possible, in the case of R2 , for the C~ C4 alkyl group to be substituted by an -N group in which R7' is hydrogen or c1-C4-alkY~ which is 3nsubstltuted or substi-tuted by hydroxyl, phenyl or carbamoyL~ or is cyclohexyl which is unsubstituted or substituted by 1 to 3 methyl groups, or is a Phenyl radical, and Rg' is hydrogen or C1-C4-alkyl which is unsubstituted or substituted by hydroxyl, phenyl or carbamoyl, or the rad;cals R7' and R8', together w;th the common N atom, form a pyrrolidine, piperi-dine, morphol;ne or piperazine ring, R3" is halogen, hydroxyl, alkoxy, alkyl, aryl or an amino group which is unsubstituted or monosubstituted or disubstituted and ;n which the sub-stituents can, ;f appropr;a~e, be cycl;sed via a hetero-atom, and X is the d;rect bond lead;ng to B or is a C1~C6~
; alkylene rad;cal, a tr;az;nyl rad;cal, a pyr;midyl radical, a halogen-substituted pyr;midyl radical or a phenylene radi-cal, ~ is a bas;c or cationic radical and x is at least 1, preferably 1 or 2 and especially 1, subject to the proviso that the number of groups B present in the molecule is equal ~ to or greater than the number of sulfonic acid groups.
; $n the radical of an azo compound containing sulfonic acid groups and defined under F, the diazo component belongs, in particular, to the aromatic, carbocyclic series, for example the aniline, aminonaphthalene, aminodibenzofuran, benzth;azoleaminophenyl or aminoazobenzene ser;es. The d;azo component can, however, also be der;ved from d;am;nes of the formula 2 ~~ NH2 \D ~ D ~/
~ ~ z o \ / \ /
~=~ o=~

~ .

: ` `

~222~1 0 in which Z is a direct bond or a d;valent rad;cal; the fol-lo~ing are mentioned as ~xamples of d;valent radicals Z of this type:
0--O o O
// ~ 11 11 -`;O NH-, -SO -NH- ; ^-NH-SO -, -N-G-~CH ) -C-N-~=~R' R' O O O
Il 11 11 .
: -N-C-CH=CH-C-N-, -N-C-N-, -C-NH-NH-C-, -CH -C-NH-NH-C-CH -I I I I 1l 1l 2 1l 1l 2 R' R' R' R' O O O O
. / 2 2\ CH -CH
-CH=CH-C-NH-NH-C-CH-CN , -N N-, -O-C-N N-C-O-, Il 11 \ / 11 \ / 11 o o CH2-CH2 o CH -CH O

N - N
Il 11 -C C- , -O-C-O- , -C-O-, -C-C-, -O(CH ~ -O-, -C- , -NH-C-NH- , \ / 11 ll llll 2 m ll ll \ /
~ NH-C-o/ \~ O
-S-, -O-, -CH-CH-, -S-S-, ¦ H ¦ , -C-NH-\ / O .=.

~-- N . N R' R' -C-NN-! -Tl~ -N- k ~ --- 1 -- -lcl l ( cH2)m-~
O = R' N N R' N N O O
\// ~/
NH-C- -` 11 1 1 o T2 T2 R' R' R' CH3 R' I l l l I
-C-N-(cH2) -o-(CH2) -N-C-, -(CH2)m-. -C-N-(CH2)m~N~(CH2)m~N~¦C¦~ r O O O O

~ 4 ~

R' R' -c-N-(cH2) o-(CH2) -o-(CH2) -N-C-I -So2-' -NH-I -C~
O O O R' NH-C- ! -C-NH-, -N=N- or -NH-CO-NH-.
Il \ / 11 O =- O

In these formulae, the radical R' is hydrogen or an alkyl rad;cal having 1 to 4 C atoms; T1 is a halogen atom, such as fluorine, chlorine or bromine, an alkyL radical 5 having 1 to 4 C atoms or an alkoxy radical hav;ng 1 to 4 C
atoms; T2 is a halogen atom, such as fluorine, chlorine or bromine, or a radical of the formula -NHCH2CH20H or -N(CH2CH20H)2 or ;s also as defined for the basic or cationic group B, and the index m ;s 1, 2, 3 or 4.
In the Preferred azo compounds, the diazo component is derived from the aminoazobenzene ser;es. The coupling component preferably forms part of the naphthalene series;
it is preferably 1-hydroxy-6-aminonaphthalene-3-sulfonic acid, 1-hydroxy-7-aminonaphthalene 3-sulfonic acid, 1-15 hydroxy-8-aminonaphthalene-3,6-d;sulfonic acid, 1-hydroxy-6-~benzoylamino)-naphthalene-3-su~fonic acid and 1-hydroxy-7-(benzoylamino)~naphthalene-3-sulfonic acid.
Both the diazo component and the coupling component can be further substituted; the following substituents are 20 possible: the subs~ituents customary in azo dyes, such as C1-C4-alkyl (linear and branched), for example methyl, ethyl9 isopropyl or n-propyl; C1-C4-alkoxy (linear and b~anched)~
for example methoxyO ethoxy, n-ProPoXy and tert.-butoxy, phen-oxy; and S02NH-alkyl-C1-C4, NHC0-~lkyl-C1-C4, ,., _ 5 _ ~2225~
-~_~ o--r // ~
S02NU-; and NHCO~
=r =-In the Preferred azo compounds of the formula I, F is the radical of a disazo comPound conta;n;ng sulfonic ac;d groups.
In a radical A of the formula -NR-CO-R1- in which R
is hydrogen or C1-C4-alkyl and R1 is C1-C6-alkylene or C1-C6-vinylene, the C1-C4-alkyl radical and the C1-C6-alkyLene radical can be e;ther l;near or branched; the - C1-C6-alkylene rad;cal R1 can a~so be substituted (for example by OH or halogen, such as F, Cl or 3r~; the follow-;ng are ment;oned as exampLes of rad;cals A of th;s type:
-NH-CO-CH2-, -NH-CO-CH2CH2-, -NH-CO-C=CH2, -NH-CH-CH2-CCl2 ; and -NH-CO-CH-CH2.
A rad;cal A of the formula -NR-CO-CH~NR-CO-R1- )2 ;n ~h;ch R and R1 are as def;ned, ;s, for example, one of the ~; 15 follo~ing compounds:

NH-CO-CH2_ NH-CO-CH2- ~H-CO-C H~--NH-CO-CH , -N-CO-CH and -NH-CO-CH
: \ I \ \

: .

In a rad;cal A of the formula -NR-CO-R2- , poss;b~e heterocycl;c R2 rad;cals are unsubstituted or subst;tuted ~for examp~e by halogen, such as fLuor;ne, chlor;ne or bro-m;ne); the following are ment;oned as examples of radicals A of this type:

..

.

~22~

/

N- ~-N
// ~ // ~
~HCO-- N ~ -NHCO-- D-, \ / \ /
.=; -N

I
O N
-NHCO-! 5 N , -NHCO-! N a n cl -NHCO~
l 11 1 11 1 1 11 1 ~
N ~ N O
~/\D \// ~/\//\
N

If A is a rad;cal of the formula ,, /~
N
-NR--* I
\D~
N
this heterocyclic radical can also be further substituted - ~for example by halogen, in part;cular Cl).
If A is a radical of the formula ~N-CO-N-X-the following are examples of possible radicals of this type:

-NH-Co-MH-, 1 0 -NH-co-NH-cH2-cH2- --NN-CO-NH-( CH2) 6- ~

// ~
-NH-CO-NH-; - , =~

, _ 7 - ~22~5~
N

/~
NH-C0-NH-NH_ - , and Il I
N N
\~

-N(cH3~-co-NH-cE~2 C 2 Finally, ;n a radical A of the formula R3~
/~
N N

-N-- -N-X-I \D I
Rl" N R2l~

R1", R2'l and X are as def;ned. If R3" is halogen, it is the 5 fLuorine, chlorine or bromine atom~ if it is C1-C4-alkoxy or C1-C4-a~kyl, it is a linear or branched alkoxy or alkyl radi-cal, and if it is aryl, it is, ;n Particular, a phenyl or naphthyl radical; ;f R3" i5 a monosubstituted or disubstituted am;no group, the follow;ng groups are possible examples:

, R2 ' -N ; ,~
o o \ /
^=^
R2 ' ~! ` -N R ' j 2 [(CH2)n o} N\
R

. ,, - - 8 - ~2~25~

and ~R2 ~(CH2)n k I R3 A

in wh;ch R2' and R3' ;ndepenclently of one another are:
hydrogen, C1-C4-alkyl tl;near and branched), C3-C4-alkenyl, benzyl or phenylethyl wh;ch can be subst;tuted by OH, C1-C4-alkoxy, halogen (F, Cl or 3r), CN, am;no, mono-C1-C4-alkyl-am;no and d;-C1-C4-alkylam;no or ammon;um compounds thereof or tr;a~kyl(C1-C4)-ammon;um, and the benzyl and phenylethyl rad;cals can add;tionally be substituted by c1-C4-alkyl; R4 ;s the rad;cal R2' and is also phenyl or naphthyl which ;s unsubst;tuted or subst;tuted by halogen, C1-C4-alkyl, OH
or C1--C4-alkoxy, or ;s the group -N ; n ;s the numbers 2 or 3 and O~ ;f o ;s 1, o ;s the numbers O, 1 or 2 and A~
;s an an;on.
The rad;cal A is advantageously attached to the coupl;ng component of the azo compound F d;rect or v;a a br;dge member, f~or example O
D ~
-NHCO~
: \ /

the -NR group or -NR1" group of the rad;cal A correspond;ng to the amino group of the coupl;ng component in the dye 2û rad;cal F.
In the preferred azo compounds of the formula I, A ;s a rad;cal of the formula ' ~ ~' :
:

.

Z~
9 _ !
/~
o N
-NR-CO-R -, -NR-- ! and -N-CO-N-X-\//\ I I
N R " R "

;n wh;ch R1", R2" and X are as defined under formula I; dyes of part;cular ;nterest are those ;n which X is a C1-C6-alkylene group~
Su;tabl~ bas;c or cationic radicals B are, in par-t;cular, am;no groupsO hydrazine grouPs or hydroxylamino grouDs. In Particular, they are the following groups:

3 ~ / 7 2 -~--R ~ , -N--~-R6 or ~~\
R2' R5~ R2' R8, ;n which R1' to R4' indePendently of one another are a C1-C4-alkyl rad;cal wh;ch is unsubst;tuted or subst;tuted by a hydroxyl group, R5' and R6' independently of one another are a C1-C4-alkyl rad;cal, R7' ;s hydrogen, C1 C4-alkyL~
wh;ch ;s unsubstituted or subst;tuted by hydroxyl, phenyl or carbamoyl, or cyclohexyl which is unsubsti~uted or subs~i-tuted by 1 to 3 methyl groups, or R7' ;s a phenyl radical,and R8l is hydrogen or C1-C4-alkyl which is unsubstituted or substituted by hydroxyl, phenyl or carbamoyl, or the rad;cals R1' and R2' or the rad;cals R3' and R4' or the radicals R7' and R8l, together with the common N atom, form a pyrrol;dine, p;per;d;ne, morpholine or piperazine ring, and the radicals R3', R4' and R5', together with the common N atom, form a pyrid;n;um r;ng or a rad;cal of the formulae ~'' ' .

- 10 - i2,2Z5~LC) CH -CH . CH -CH
0~ 2 2~ 2 2~, N~ 2 2/ and -N-CH2-CH2-N-R.

If B is a cationic hydrazine radical of the formula Rl ~
-~H2 the radicals R1' and R2' indePendently of one another are alkyl radicals having 1 to 4 C atoms. The alkyl radicaLs can be unsubstituted or substituted by a hydroxyl group, or~
together with the common nitrogen atom, can form a pyrroli-dine, piperidine, morphol;ne or p;perazine r;ng.
For example, the follow;ng rad;cals are possible:
CH3 ~C2H5 0/ 2 4 \ 2 ' \ -~H2-: CH3 C2H5 C2H40H

0 ~ O---- 9--0 ' ~/ ~/ \~/ \ ~/ \
-N H , -N H , -N H O -N H N .
¦~- ¦ o ! ¦~ ! and ¦~ /
NH2 NH2 NH2 ~H2 If B ;s an amino grouP of the formula ~/R3 R5 ~

:; '-' .

~22~

the rad;cals R3', R4' and R5' ;ndependently of one another are an alkyl rad;cal hav;ng 1 to 4 C atoms, and the rad;cals R3' and R4' can also be substituted by a phenyl or hydroxyl group. The radicals R3' and R4', together with the common N atom, can also form a pyrrolidine, p;per;dine, morpholine or piperaz;ne ring.
The follow;ng are examples of cation;c amino groups of th;s type:

-N(CH3)3-N(C2H40H)3 ~ N H o -N(CH3)2 o-- o-o .-.
C2H5 1 .H2 !' ~o \ /
1 û ~,_. ._.
-N(C H ~ -N(C H OH) -N H o -N H O -N(-CH ) 3 ~ CX2CX20H

CH~ ~--o 9/ 0/ J ~)/
-N(C2H5)2 -N H -~----CH OH -N H -N-(CH3)2 CH3 ~--- C2H5 C H 2 5 o-o 2 5 -N H O
l\ /
G----If the rad;cal ~ is a cat;on;c hydroxylam;no radical of the formula Rl ~
/

-~OR6 ' ~2225~L~

the radicals R1' and R2' are as defined above. The radical R6' is an alkyl rad;caL having 1 to 4 C atoms. The follow;ng cation;c hydroxylam;no der;vat;ves are ment;oned as examples:

CH3 C2H5 CH3 ~_ ~/ ~/ 0/
\ 3 ~ N\ OCH3 ' --N--OC2H5 , -N H

--0 4 ~
~9/ \ ~9/ \~/ \
-N H , -N H O and -N H M
l\ / I\ / I\ /

Finally, the rad;cal B ;s an am;no group of the formula -N\

The rad;cals R7' and R8' are hydrogen or alkyl having 1 to 4 carbon atoms; in th;s connect;on the alkyl rad;cal can also be subst;tuted by a hydroxyl, phenyl or carbamoyl group. Furthermore, the rad;cal R7' ;s a cyclo-hexyl rad;cal wh;ch ;s unsubstituted or substituted by-1 to 3 methyl groups~ or ;s a phenyl radical. F;nally, the radi-cals R7' and R8', together ~;th the common N atom, can form a pyrrolid;ne, p;per;dine, morphol;ne or piperazine ring.
The following are ment;oned as examples of am;no groups of this type:
Cyc lohexyl =N ~
-N(CH ) -11 -11 ~ -N H ~ -N(C2H5)2 ~; :22~

=N ~ - o C H
/ \ / / \ /37 -NH-CH H o -11 -N H -N
3 /\ / \ \ /
2 7 1 /; N=~ C3H7 ~ O o--o ,,_. ._.
-~ N-(CH2)2-C-NH2 ~ ~ H o ._. -- -N o-- o--/C4Hg _ O_; j_. CH2-CH-CH3 -N -M-- H- -N - H -N OH
C4Hg H ~ \ / / \ / \CH CH CH

-N-CH2-^ ~ and -N(C2H40H)2 C2H40H H ~=9 ~: In addition to these basic or cationic radicals, B
can also be the radical of a basic or cationic polyamineO
From the large number of possible polyamine radicals, 5 the following are mentioned as examples:

-HN-CH CH ~N(C H ), -HM-CH CH2-CH2-N(C2H5)2, -HN-cH2cH2cH2ocH2cH2ocH2cH2cH2 2 ' -HN CH2cH2cH2ocH2cH2cH2cH2 ( CH2) 3 2 -H~-cH2cH2cH2ocH2cH2-cH-cH2-cH2ocH2cH2cH2NH2 -' ~2~:2510 CH2CH20H ~CH3 -HN-(CH2)6NH2~ -HN-CH2CH2 2 ~ -HN-CH -CH -N

.. . ~CH3 Ca2CH2-NH2 HN C 2 2 ~ ' -HN-CH2CH2CH2N , -N

/CH2 2 2 2 ~CH3 -N , -N ~ 2 5 CH2cH2cH2NHcH2cH2cH2Nx2 (C 2)4 \

CH2CH2NH2 - ; CH2CH2CH2N(c2H5)2 -N , -N~ ~ 2 2 2' CH2CH2NHCH2CH2NH2 CH2CH2CH2N(c2u5)2 CH2cH2NHcH2cH2N 2 CH2cH2-NH-cH-cH2cH-c2~5 -N , -N
( 2)1? 3 \CH CH ~H-CH-CH CH-C2H5 : CH3 ICH3 -N , -N , -N
f CH-CH2-NH2 CH2CH2NHCH2CH2NHCH2CH2NH2 CH2CH2NHCH2CH2NH2 jCH2CH2NH2 -N ` , -N
CH2CH2NHCH2CH2NH2 \CH CH NH-CH CH NH-CH CH2NH-CH2CH2NH2 ~.

CH2CH2NHCH2CH2NH2 ~ 2 2 2 2 ~ 2 2 2 2 -N , -N , -N
CH2cH2NH-cH2cH2NH-cH2cH2NH2 CH2CH2NH2 2 2 2 2 CH
~ 2 2 2 2 /( 2)6 2 l CH2CH2CH2N(c2H5)2 -N , -N , -N
~\
CH2CH2NHCH2CH2CH2NH2 ( CH2~1 6NH2 CH2CH2CH2NH2 CH3 ¦ CH2CH2CH2NH2 e~H2CH20H
-N , -N , -N
0\ (3\ (~\
CH2CH2CH2-NH2 . CH2CH2CH2NH2 CH2CH2CH2NH2 CN CH
~H2CH2N( CH3) 2 ¦ CH2CH2-N--6H2CH2N( CH3) 2 -N , -N
0\
2CH2N( CH3) 2 3 CH~ CH
¦CH2CH2CH2NH2 ¦ CH2CH2CH2NH2 /Ca3 -N . -N -N-- 2 2 2 and ~\

In cases where an -NH-CH2- grouping is present, the N atom can also, by means of 2 ;ndividual bonds (N-CH2) leading to A, be a constituent of an aziridine ring of the S formula -CH-CH-.
N
The following are aLso possible:

1~22~

NH-(CH2)3-N(c2H5)2 N! ( 2)2 ( 2 5)2 N N N .N
Il l 11 1 -NH-~ -NH-- -~ NH-(CH2)3-N~c2H5)2 M NH-(CH2)2 N(C2 5)2 r~ N-CH2-CH2-MH2 NH-(Ca2)3-N(CH3)2 N N ~-- N N
Il I / \ 11 1 -NH- ~-M N-CH -CH -NH -NH-2 2 2 \ // \
N ._. ( 2)3 ( 3)2 o--o N~ --CH2-N(CH3)~ S04CH3 ~.=--N N --N =~

NH-(CH2)3-~cH3)3 g S04CH3 N
Il I
-NH--\//\ ~
: N NH-(CH2)3-N(cH3)3 SO CH

:~

'1~22~S~

D ~
NH~ N(CH3)3~S04CH3 =0 / ~ , .
N N -~

\ // \ /
N ~=9 and 1l /~

/ \ 11 1 -N N-- ~
\ / \//\
~-o N R2 ;n ~h;ch R1 and Rz are NH(CH2)3-N(C2H5)2;

._~, 2 2)3 N(C2H5)2; -N~ -CH2N(C~3~3 =- Anion 0_. ._~, `~ / \ //
-N N-CH -CH -N~l or~NH~ ; -N(GH3)3 -9 =- Anion ~:
' The group B is attached to the radical A by at least one bond and can, additionally, also be located in the azo compound F (even in the diazo component), being attached by a direct bond or, in particular, via a.substituent, for example an alkyl, alkoxy, acylamino or sulphonamido group.

If C ;s~a cat;onic group, the azo compounds of the formula I are in the form of the;r inorganic or organic salts.

:

~25~

Possible counter-;ons are ;norgan;c an;ons as well as organ;c an;ons; the follow;ng are ment;oned as examples:
hal;de, such as chlor;de, brom;de or ;od;de, boron tetra-fluor;de, sulfate, methylsulfate, am;nosulfatej perchlorate, carbonate, b;carbonate, phosphate, phosphomolybdate, phospho-tungstate, phosphotungstomolybdate, benzenesulfonate, naph thalenesulfona~e, 4-chlorobenzenesulfonate~ oxalate, maleate, formate, acetate~ prop;onate, lactate~ succ;nate, chloro acetate, tartrate, methanesulfonate or benzoate ;ons, or complex an;ons, such as the anion of z;nc chlor;de double saltsO
The Preferred an;ons depend on the mode of use of the compounds: for example the formate, acetate, lactate and chloride ions are preferred for textile and paper materials; the chloride ion ;s preferred for the preparation of inks.
In ~he azo compounds of the formula I, the sulfonic acid groups can also form an internal salt w;th the cat;onic groups B.
The azo compounds, accord;ng to the invent;on, of the formula I ;n wh;ch A ;s a rad;cal of the formulae -NR-C0-R1, -NR-C0-CH(NR-C0-R1-)2), -NR-C0-R2 and /~
O N
-NR ~

// \
N
are obta;ned, for example, by coupl;ng a d;azot;sed am;ne w;th a coupl;ng component, the rad;cal A-halogen already be;ng present ;n the d;azo comPonent or ;n the coupl;ng com-ponent, and react;ng the compound F-A-halogen w;th a com-pound (H)y~-B (y = 0, 1 or 2) wh;ch ;ntroduces the rad;cal B, and, ;f desired, quatern;sing the result;ng compound; ;f A
;s a rad;ccal of~ the formula -r-C0-N-X-, these compounds are R1" 2"
.

L2225~0 obtained eithero a) by subjecting a compound of the formula II

[F~-N - C - O - R3 ( I I ) Rl7~ 0 in wh;ch R1" and F are as defined and R3 ;s unsubstituted phenyl, halogen-subst;tuted phenyl, C1 C4-alkyl-substituted phenyl, C1-C4-alkoxy-substituted phenyl, C1-C4-alkyl or C1-C4-alkylenephenyl, to a condensation reaction w;th a com-pound of the formula III
H-B'~R (III) ;n wh;ch R ;s as defined and B' is a bridge member carrying the radical (B)x, or b) by react;ng a compound of the formula VIII

[F]-7.~a (VIII) ~1 w;th a compound of the formula III ;n the presence of phos-gene, the symbols F and R1" be;ng as defined, or c) by subject;ng a compound of the formula VIII

~-NH
R " (VIII) .

to a condensat;on react;on w;th a compound of the formula IX
Cl-C0-B'-R (IX) or R30C0-B'-R (Ixa) ~ ;n wh;ch F, R1"~ R3, B' and R are as def;ned;
; 20 ;f A is a rad;cal of the f~rmula - 20 ~

/~
N N
Il I
-N-~ -X-l ! /Y

these compounds are obtained:
a) by d;azotis;ng a diazo component and coupl;ng the product w;th a coupL;ng component to g;ve an azo compound F, a rad;-S cal of the formula /~
~ N N
Il I
~ -N-9 -N-~s~
I \R I X
Rl" N R2l~

~ - be;ng present ;n the diazo component or the coupl;ng com-; ponent, or b) by d;azotising a diazo component and coupling the product :
w;th a coupling component to form an azo compound F, the radi-cal of the formula R3"
/~
N N
-N-- !-Hal I \ //
R1" N

be;ng present ;n the d;azo component or coupl;ng component~
and then subject;ng the product to a condensat;on react;on :: :

- 21 - ~ ~2251 with H~ R, the symbols being as def;ned.
The starting materials are obtained as follows:
- I) Coupling components (CC) which conta;n the rad;cal A-halogen and are used to prepare the azo compound F are prepared, for example, by sul)jecting a coupling component wh;ch contains the rad;cal -NH-R or -NH-R1" (;n which R and R1" are as defined) to a condensation reaction with a com-pound of the formula A'-(halo9en)2 to 5 in which A' is a radical of the formulae -C0-R1-, -Co-cH(NR-co-R1-)2~ -C0 R2 and ! ;n which the /~
~ N
~ I

N

symbols R, R1 and R2 are as defined, in a known manner, in an aqueous or aqueous-organic med;um in the presence of an acid accePtor (base), to gi~e a compound CC-A-(halo-gen)1 to 4-II) Diazo components (DC) which contain the radical A
halogen and are used to prepare the azo compound F are pre-pared, for example, by subjecting a d;azo component which contains the radical -NH-R or -NH-R1" (in which R and R1"
are as defined) to a condensation reaction with a compound of the formula Al-thalogen)2 to 5 in which A' is a radical of the formulae -C0-R1-, -C0-CH(NR-C0-R1-)2, -C0-R2- and ! in which the /~
I
\ /i\
N

symbols R~ R1 and R2 are as defined, in a known manner, in .

~22~5~ r~

an aqueous or aqueous-organic medium in the presence of an acid acceptor (base~, to g;ve a compound DC-A-(halogen)1 to 4-III) Examples of su;table compounds wh;ch ;ntroduce the radical B are the compounds B as such (for example pyridine or triethylenediam;ne) or H-B or H2B. 3-Diethylam;nopro-pylam;ne and d;propylenetr;am;ne are ment;oned as examples.
IV~ Compounds of the formula II are prepared by sub-jecting a comPound of the formula F - N - H
I

Rl ll in wh;ch F and R1" are as def;ned, to a condensat;on react;on ;n an aqueous or aqueous-organ;c medium in the presence of an ac;d acceptor, w;th a compound of the formula halogen-COO-R3 ;n wh;ch R3 is as def;ned.
Y) The compounds of the formula III H-B'-R in wh;ch R
is as def;ned and 8' is a bridge member carry;ng the rad;cal tB)~ are obta;ned by stepwise synthesis. The following are possible bridge members:
H-N-N-l l R R
/~
N N
H-N- ( C 1 -C6) -al'~ylene~- _! !_ R R \R
N
R or j- . N- _ ~ N
H-N-; . I! !
R 1~-~ 23 - ~2~

or Hal (cl-c6)-a~ky~ene~R

/ \ // \

in which R ;s as defined.
One poss;ble means of preparat;on is to react B, H-B
or ~H)2-~ with cyanuric chloride, tr;chloropyr;m;d;ne or tetrachloropyr;m;d;ne and then to subject the product to a condensation reaction w;th the d;amines ment;oned prev;ously as a br;dge member, the free valency be;ng replaced by a hydrogen atom.
VI) Compounds of the formula VIII are known and can be prepared by known methods, as can VII) Compounds of the formu~a IX or Ixa.
VIII) Coupl;ng components (CC) and d;azo components (DC) wh;ch contain the rad;cal R3"
I
.. O
/~
~ ~ N

-N-o -Halogen : 1 \~
Rl" N
and are used to prepare the azo compound F, are obtained, for example, by subjecting compounds of the formula j:
C C -N-H DC -N-H
o r Rl" Rl"

225~!~

to a condensat;on reaction with a tr;azine o~ the formula R3~
!

/~
N
l! !
/\//\
Halogen N Halogen All these processes of preparation are processes known per se. Accord;ngLy, the coupling reaction ;s carried out in a manner which is customary per se, advantageously in an aqueous, slightly acid to slightly alkaline medium. Con-densation reactions and the phosgenation reaction of the compound VIII with the compound III are similarly carried out by methods which are customary and known per se.
1û The resulting azo compounds of the formula I are isolated from the reaction mixture in a manner known per se.
The basic groupds B in the azo compounds of the for-mula I can also be converted in a known manner into cationic groups B by the action of su;table alkylating agents.
ExamPles of suitable alkylating agents are alkyl halides, ~-halogenopropionitriles, halohydrins, alkylene oxides, alkyl esters of sulfuric acid or alkyl esters of organic sulfonic acids, such as methyl chloride, bromide or iodide, ethyl chloride, bromide or iodide, propyl bromide or iodide, benzyl chloride or bromide, ~-chloropropionitrile, ethylene chlorohydrin, ethylene oxide, proPylene oxide, dimethyl sulfate, diethyl sulfate, methyl benzenesulfonate, methyl, ethyl, propyl or butyl p-toluenesulfonate, allyl chloride or bromide, methallyl chloride or bromide, tri-methyloxonium borofluoride, 1,4-dichloro-2-propene, 1-chloro-Z-butene, 1,2-dichloro-2-propene and acrylonitr;le.
The reaction can be carried out either in water or in an organic s`olvent~ for example ;n acetone, methyl ethyl ::
:

- 25 - ~ ~2~
ketone or d;methylformam;de, but preferably ;n water.
Magnes;um ox;de, magnes;um carbonate, sod;um car-bonate, calc;um carbonate, sod;um b;carbonate or sod;um hydroxide solut;on, for example, can be employed as an acid-bind;ng agent. The alkylation react;ons are usually carriedout at room temperature; the quatern;sat;on reactions can either be carried out at this temperature also or at an ` elevated temperature and, if necessary, under pressure.
The azo compounds of the formula I are used e;ther as preparations of Powders or granules or ;n the form of concentrated solut;ons. Powder preparat;ons are standar-d;sed ;n a customary manner w;th standard;sing agents, such as sodium sulfate, phosphate, chloride or acetate, in the presence of anti-dust agents, or the azo compounds are marketed, w;thout further treatment, as spray-dr;ed prepara-t;ons. Concentrated dye solut;ons can be of an aqueous or aqueous-organ;c nature, and customary additives which are as read;ly degradable as poss;ble, such as organic acids, preferably acetic acid, formic acid, lactic acid or c;tr;c ac;d, amides, such as formamide, dimethylformamide or urea, alcohols, such as glycol or d;glycol, or d;glycol ethers, preferably methyl or ethyl ethers, are preferred.
The azo compounds of the formula I are used, ;n par-t;cuLar, as dyes for dye;ng and pr;nt;ng text;le mater;als, paPer and leather and for prepar;ng ;nks. Suitable text;le mater;als are natural and synthet;c mater;als hav;ng an aff;n;ty for cat;onic dyes. The new azo compounds are pre-ferably used for dyeing and printing paper, th;n board and cardboard ;n the pulp stage and on the surface, and also text;le materials which, for example~ advantageously consist of homopolymers or copolymers of acrylon;trile or synthet;c Polyamides or polyesters which have been mod;f;ed by ac;d groups. These text;le mater;als are preferably dyed ;n an aqueous, neutral or ac;d med;um by the exhaust;on process, ;f des;red under pressure, or by the continuous process. The textile ma1er;a~l can be in a very w;de var;ety of forms ;n these processes, for example ;n the form of fibres, .

- 26 _ ~2 ~2 S~ ~
filaments, woven fabrics, kn;tted fabrics, p;ece goods and f;n;shed goods, such as sh;rts or pullovers.
The dyes accord;ng to the ;nvention make it poss;ble to produce level dyeings or pr;nts which are distinguished by very good overall fastness propert;es, in particular a very degree of exhaustion and good fastness to water.
Furthermore, the novel azo compounds of the formula I can also be used for dyeing and printing natural and re-generated cellulose mater;als, ;n part;cular cotton and v;scose, deep dyeings being similarly obtained.
On these text;le mater;als, the novel azo compounds of the formula I have a good aff;n;ty and a good degree of exhaust;on, and the result;ns dyeings have very good fastness properties, in part;cular fastness to wet process;ng.
Furthermore, the novel azo compounds are used for sp;n-dye;ng polya~rylon;tr;le mater;als, and for dyeing poly-acrylon;tr;le never-dr;ed tow. They can also be employed for mark;ng ;nks and ;n jet pr;nt;ng.
A preferred use of the novel azo compounds of the formula I cons;sts of using them for dyeing paper of all types, ;n particular bleached, unsized and sized, l;gnin-free paper, it being possible to start from bleached or unbleached pulp and to use hard wood pulp or soft wood pulp, such as birch and/or pine sulfide and/or sulfate pulp. These com-pounds are very particularly su;table for dyeing unsizedpaper (for example serv;ettes, table cloths and hygienic paper) as a consequence of the;r very h;gh affinity for this substrate.
The novel azo compounds of the formula I are absorbed very well on to these substrates, and the effluents rema;n colourless, wh;ch ;s a great advantage, particularly ;n respect of present-day effluent legislation.
The result;ng dye;ngs are d;st;ngu;shed by good overall fastness propert;es~ such as good fastness to l;ght, wh;le having at the same t;me a h;gh degree of clar;ty and depth of colour~and fastness to wet process;ng, that ;s to say they show no tendency to bleed when dyed paper ;n a wet :

:

~22~:5~L~

condition is brought into contact with moist white paper.
In addition, they have good fastness to alum, ac;ds and alkalis. The fastness to wet processing does not relate only to water, but also to m;lk, fruit juices and sweetened 5 mineral water; they are also resistant to alcoholic bever-ages because of their good fastness to alcohol. This pro-perty is particularly desirable, for example, for serviettes and table cloths, in the case of which it can be expected that the dyed ~aper will come, in a wet state (for example soaked in water, alcohol or surfactant solution etc.), into contact with other surfaces, such as textiles, paper and the l;ke, which have to be protected against soiling.
The high affinity of the novel dyes for paper and their high rate of exhaust;on are a great advantage for the continuous dye;ng of paper.
In conclusion, ;t ;s also poss;ble to use the novel azo compounds of the formula I for dye;ng leather (for example by spray;ng, brushing and d;pping) and for prepar;ng inks.
The examples which follow iLlustrate the invention without limiting it thereto. Unless otherwise specified, parts are Parts by weight and the temperatures are quoted in degrees Centigrade.
Example 1: 9.9 parts of 4-aminoazobenzene are suspended in 125 parts of water and 13 parts of concentrated hydrochloric acid, and the mixture is cooled to 0-5. 12.5 parts of an aqueous 4 N sodium nitrite solution are then added dropwise.
A solution of 23 parts of dibromopropionyl-J acid (obtained by acylating J-acid with dibromopropionyl chloride) in 150 ml of water is initially taken in a second reaction vessel, and the above diazo solution is added dropwise at pH 6-7. The m;xture ;s st;rred overn;ght to complete the react;on, and 7 Parts of 3-diethylaminopropylamine are then added; the dye is isolated in the form of powder by salt;ng out from the solut;on with sodium chlor;de, and has the formula: ~

:~.2~25~

OH
_ o = ~
~-N=N~ N=N- ~
\ / ~ R I 11 1 o o ~ o ~ ~ ~
03S ~ NH-C-C~CH
Il \/ 2 O N ~C2H5 2 ) 3 H~

The dye is readily soluble in water and dyes paper in red shades; the dyeings have good fastness to light and wet processing.
: S Further diazo compounds of analogous structures~ for which the coupl;ng component and the shade of the dyeing on paper are ;ndicated in Table 1 below, are obtained by th;s p ocedure.

: ` .

:: .

25~L0 Table 1 Elaem Coupling component Shade .
. OH _ .

2 //; /;\ red ~ 0 /~/\//\// ~
; / 8 1 =- O Br Br OH
! o 3 //\ / ~
i il I red , O 0--/~/\R\ // ~
~. HO3S NHCO- ; ~
=;

O Br Br 0~1 : NH-C-CH-CH
//\ / ~ 2 bluish-

4 o O Br Br ti nged ! ! red . HO3S/ \\~/ '!' 1~25~ ~

Table 1 (continued) Exam Coupling component Shade . P _ , .

OH j~"
o NHCO-- -NH-C-CH~CH bluish-D \ / ~ 2 tinged ~ o=-O Br Br F ed /~/\R

NHCO-- ~
//\ / ~ /\ / bluish-6 . O .=~ tinged ~ \ red NH-C-CH-CH
/ ~ 1 2 H93S o O Br Br ...... . ... _.
Example 7: The 9.9 parts of 4-aminoazobenzene in Example 1 are replaced by the same number of parts of p-phenetidine, affording the dye of the formula:
HO
I

0--~ D C
D ~ //\ /~
C H O-- -N=N--o 2 5 \ / l ll e /~/\D\
03S 5 o NH-C-CH----C 2 11 \/
O

2)31\

3 1 ~L2225~
It dyes paper in scarlet shades.
Example 8: The 7 parts of 3-diethylaminopropylamine in _ Example 1 are replaced by 7 parts of 3-dimethylaminopropyl-amine and quaternisation is then carried out with dimethyl sulfate, affording the dve of the formulao OH
~ O
D ~ // ~ //\ /~
-N=N-- N=N-- ~
\ / \ / 1 11 1 9 /~/\//\
O S NH-C-C~CH .
3 ll \ / 2 ~ 9 O N ( CH ) -N ( CH ) 4 3 Example 9: 24 parts of J-acid are dissolved at pH 7.5 in 220 Parts of water containing 11 parts of concentrated sodium hydroxide solution. 11 parts of sodium bicarbonate 1û and 14 parts of chloroacety~ chloride are added to this solu-t;on. A diazo solution prepared in accordance with Example 1 is added dropwise at pH 6-6.5; the mixture is stirred over-night to complete the reaction, 12 parts of triethylenedia-mine are added and the mixture is boiled for 4 hours at 95;
it is then cooled to room temperature and the dye is salted out with sodium chloride. It has the formula:

OH
o~ !
! . N=N ! . N=N !
\ / \ / 1 11 1 a /~/\//\ ~/ \
03S NH-c-cH2-N /\/ N
O ._.

~ 32 - ~ ~2~5~
xample 10: 6 parts of the dye obtained in accordance ~ith Example 9, in 100 parts of water, are treated with 2 parts of dimethyl sulfate at 30. The dye of the formula:

OH
_ I
~ - O
// ~ D ~ //\ /~
o ~-N=N-- ~-N=N-~ o \ / \ / 1 11 1 = 0 O ~ , 03S NH-C-CH2-N ~ N-CH3 SO4CH3 O ~ _ is obtainedO
Example 11: The 12 Parts of triethylenediamine in Example 9 are replaced by the same number of parts of dipropyLene-triamine, affording the dye of the formula:
OH

I

// ~ D ~ //\ /~
9-N=N-- -N-N-- -\ / \ / 1 11 1 .=. o=~ CH -CH -CH -NH
a /~/\D\ / 2 2 2 2 O S ~ NH-C-CH N
3 1! 2 \

Example 12: The 12 parts of triethylenediamine in Example 9 are replaced by the same number of Parts of aminoethyl-piperazine, affording the dye of the formula:
OH

I

~Y ~ D ~ R\ /~
~ 9-M=N-- -N=N-~ o \ / \ / 1 11 1 =o ~ CH -CH H
/~/\D\ / 2 ~2/

o CH -CH

" ~

~2~0 By us;ng the d;azo component of the formula //\ /~
~ NH
1! ! 2 "! '!' I

CH -NH

the dye of the formula:
HO
I

~ o .
//\ /~ D\ /~
~ N=N-4 4 0-0 H
11 1 'I 11 1 / \/
~ o -NH-COCH -N N-CH -CH -NH
~ /\D 2 ~ / 2 2 2 ~ 03S -~

wh;ch dyes paper ;n br;ll;ant orange shades is obtained analogously.
Example 13: The 14 parts of chloroacetyl chlor;de and the 12 parts of triethylened;am;ne in Example 9 are replaced by the same number of parts of 2,4-dichloropyrim;dine-S-carboxylic ac;d chlor;de and am;noethyLPiperaz;ne, affordingthe dye of the formula:
HO

. .
~_ o--~ o ~ / \
D ~ R \ i ~ 2 H2NH2 -N=N-o -N-N-~ \
\ / \ / I 11 1 o~
=~ -N _-HO S o NH-C-~ -N N-CH
3 11 \ / \ / 1 2 ~;; ' :, ~22~510 3~ _ By using 2,6-d;chloropyrimidine-4-carboxylic acid chlor;de, the dye of the formula:

/ \
O-~ O-- o N N-CH CH NH
// ~ // ~ D \ / ~ 2 2 2 ~ ~-N=N o ~-N=~ o--~ R ~
=- o=~ NH-G-~ N
~ /~/\D11 \ /
HO S O o-~
3 \ /

is obtained analogously. Both dyes dye paper in brilliant S red shades.
Example 14: 29.6 parts of 4-aminoazoben~ene are diazotised in accordance with Example 1.
A solution of 62 parts of the acylation product of J-acid with tr;fluorochloropyr;midine, ;n 5ûO ml of water, ;s ;n;tially taken ;n a second reaction vessel, and the above diazo solution is added drop~ise at pH 6-7. The mixture is stirred overnight to complete the reaction, and 43 parts of 3-d;ethylam;nopropylam;ne are added. The reaction mixture ;s heated to 95~ until thin-layer chromatography indicates that a single-substance condensation product has been pro-`1~ duced. 3ûX aqueous sodium hydroxide solution is then added slowly, so that the pH rises to 9. The dye of the for-mula H
OH NH(CH2)3-N(c2H5)2 ~ ~ Cl o D ~ D\ /~
~ -N=N-- -N-N-- N
'` ~ \ / \ / I 11 1 11 1 O
~ / \ D\ / \ D\
3 NH N NH(CH2)3-N(C2H5)2 . ~

25~L~

wh;ch has been precipitated is filtered off with suction and dried. It is readily soluble in a slightly acid to acid aqueous medium and dyes paper in bluish-tinged red shades;
the effluent is colourless.
The 3-diethylaminoPropylamine in the above example is replaced by the same number of parts of N-~Z-aminoethyl)-piperazine,-affording the dye of the formula __ O-- C1 o ~---N=N-- -N=N-~ o ~ N
\ / \ / 1 11 1 11 1 /\//\ /\R\ / \

It also has very good tinctorial properties on paper.
As a variant of th;s process of preparation, the tr;fluorochloropyrimidine can be replaced by equivalent parts of tetrachLoropyrimidine; the same dyes are obtained.
Further diazo compounds of analogous structures, which are shown in Table 2 below, together with their shades on paper, can be obtained by this procedure.
.

- 36 - ~:a22251() . _ O '3 ~ '3 ~'3 ~
1~ O aJO a~ o al Q_ c _ J c u~ Cl >. ~

,_ D~ ~ ~

o ~ O~ , ~ ~

N~

"`; `

.. ~ . .

~22~

, ~, , ~ aJ
C u~
o .. .. ..
3 ~:13 -D 3 ~ t o ~ o ~1 o a~
{~ G~ -- ~n _ ~ _ Q
t- ~) U~ Q
X~ ~ X~

~, t ~ ,t 12225~0 _ . . _ I ~ al I
C C- ~>
O ,~
a, ~ 3 ~ U) ~ 3 J O ~ ~-- ~ O
t~l Q _ ~ ~ C
~ n~ ~ C _., J c v~ Q ~IJ~ ~ ~ (L~
~ *' . _ - _ _ .. ~ _ __ -~ t ~ " I, ~ I

_ ....... . - . ..

P ~ t~

~ .
_ . .

~ ~ ` '-- '; ` -- S f aJ
8 X a~ _ I_ LIJ Q ~
_ _ .

_ 39 ~ 251~

, ~ , ~ , ~
s: a> ~ Q~ ~ 0 u~ c ~n ~ tn t_ o .. .. ..
3 ~ 3 ~ 3 Q~ c O ~ O ~ O
11 ~ _ ~ _ ~ _ ro Q
c~
Q
_ _ _ . _. _ -- _ - .
~ -=
i~ `S
~Z~ Z~ ' _ - . ___ __._ ......

Z Z ~U~
~ 3~ Z~
t',-' t~,' , _ . _ . ...
::- 3 5: ~
, , ~ t ~ ' Z o o O i ~
a) _ _ _._. __ 8 e _ . ____ _ ' :

o ~22251.~

Exam~le 27: 58 parts of the compouncl of the formula:

HO
I

D ~ R ~ //\ /~
~-N=N-- ~-N=N-~ o \ / \ / 1 11 1 =- 0=~
/ ~ / \ D \
H03S ~ NH-jC-CH2C
O

obtained by acylat;ng I-acid w;th chloroacetyl chloride in accordance w;th Example 9 and coupling the product with diazot;sed p-aminoazobenzene, are suspended in SOO parts of water, and treated at room temperature w;th 43 parts of the polyam;ne of the formula 1}~ H2~3 \

N N

/\R\
; H2NCH2CH2H~ N N~--~ 2 3 \

The reaction m;xture ;s st;rred at 45 unt;l thin-layer chromatography no longer ;ndicates the presence of starting =ater;lL. The dye of the formuLa:

.

"' 1,2;225~0 HO
I

. ~
-N=N-~ -N=N~
\ / \ / 1 11 1 = - o = ~
/~/\R\
~103S NH-C-CH2-R

NH-(CH2)3-N(C2H5)2 /~
R = N N
Il I
o // \ ~\
--NHCH2ca2NH N NHtCH2)3 NtC2N5)2 which has been precipitated is readily soluble in an acid aqueous medium and dyes paper ;n red shades; the dye;ngs I have good fastness to light and wet processing, and the effluent is colourless.
The further dyes which can be seen in Tables 3 and 4 below are obta;ned by following a procedure analogous to that ;ndicated.
. . :

:

~ ~, ~2~2~10 . o ...
~3 ~ ~ ~_ ~=

,.,- .~ ~Z
::: _ ..

.

:` ' . ~ , ~2~si~

~C I ~ ~
~ ~ ~ {~n~ Q
~ n~ ~ v v~ _Q . . _ _ _ _ X I Z~ Z~

~-1 ~ Z~ ~Z~
X ~ o _ .. . ........ _ 0~ = = =
~_ . . . _ 3 ~
I I ~Q ~n : - - . .......... _ _ .0-~. .~-~. 0~ ~ ~o ~ ~ ~ z z z o ; o ~ Z z z ~ .
~, i ll l ll l ll .

- - 4 4 - ~3l2;~2~

.. ,. .. _ O ,, V~ ~_ J _ ~ o a, Q L a., ~, J ~

, _ __ - ~ _ .__ .... .-~ ~ ~ n __ ~c ~`
_ . ._............................. _ --¦ . ~ .

_ 45 _ ~ 22~

~ ~ s ~
, 3 a 3 3~ s_ O ~ O
Q)J ~ J
rr~ Q _ s 1 . .__ . ___ T" ~

.

~_ Z Z
C,~ =~
. .

3 ~' o ~' Co t~--D ~
X J

_ I~Q .`.

25~

c- ~ ~ a, ^~

~ ~ - _ : ~

~2225;~0 O 3 ~:1 aJ ~ o a aJ _ ~ Q ~ ~ -- C
S ~
v~ Q L.
- ~

0 Z~ oJ ~ , 2 S
C~ ~0 ~o ~0 ~,~
~ ~~ _ Z~ i~Z~i =~ ~" Z~

0 æ 0~ c~'~

O ~ ~ O ~ 1 i :i ' s~ s~

~ ~ e :1a ~ s~ ~; SS ~; ~

~o ~
_ _. .. .
~ 100~ .. `
_ _ _ _ _ _ _ _ _ _ _ _ . _ _ _ .

~22~5~.~

' I~
O V~ L ~1) S~
3n 3 n3 n a~ ~ o ~o ~ o al J -- cs~ -- ~ -- a>
Q J cJ ~ J c , a~ a, Q~
V~ Q
..
:~
_ Z Z
_~
C'~

_~
C~
Z; Z Z
_~ _~
~ ~ C~
Z ~ Z
.
~` ~
:' S ~ :~:
~ . 3C~
........................... ............ . . .
~ 0~ ~ ~ ~1~ ~1~
C l ll l ll l ll ~ ~ o~ ~ T
~1 , ~

:

~L22~:5~

~ V) t U) o .. ..
3~ 3 L. O ~ O a~
_ cn ~
Q _ c _ c , ~ a v~ Q

_ . . ~

C~
~ :

r ; ~ ~ ' ~

n,~ 'D , _ _ _ _ _ , .
!

_ 50 _ 1~225~
Example 49: The chloroacetyl chloride in Examples 27 to 48 ;s replaced by dibromopropionyl chloride, affording similar dyes ;n wh;ch the dibromopropionyl radical is converted into an az;r;d;ne system ;n accordance w;th Example 1.
ExamPle 50: 59 parts of the phenyl carbamate of the formula:

HO
o ! -N=N-! -N=N- .
'.=.' \o=~/ ! I! ! ..
H03S ! NH-C-O-! -Il \ /
O ~=-obtained by acylat;ng I-acid with phenyl chloroformate and coupling the Product with diazotised P-am;noazobenzene, are suspended ;n 500 parts of water and treated at room tempera-ture with 43 parts of the polyamine of the formula / ~ 2 5 N N
Il I
/; //; ~ /

The react;on mixture is stirred at 45 until thin-layer chromatography ;nd;cates that starting mater;al is no longer present. The dye of the formula 2~:51.0 HO
--0 2--O ~ O
D ~
-N=M-~ -N=N-- -\ / \ / 1 11 1 o = ~
/~/\//\

NF~CH2 ) 3-N ( C 2H5 ) 2 /~
N N
R = I! !
- / \ // \
-CH2CH2NH N NH(CH2)3 ~(C2H5~2 ~hich has been precip;tated is readily soluble in an acid aqueous medium and dyes paper ;n br;lliant red shades; the dyeings "ave good fastness to light and wet processing, and the effluent is colourless.
S The procedure of the above example is repeated under the same reaction conditions, except that the same number of parts of the ethyl, isobutyl or benzyl carbamate are used instead of the 59 parts of phenyl carbamate, afford;ng-the same dye with equally good propert;es.
The further dyes which can be seen in Tables S and 6 below are obtained by following a procedure analogous to that indicated.

~' ~%~

~-~

`
~; , :

- \

. .
~ al O L
a~ ~ o Q) J CJ~
J C
~U
. _ L ' L
_~

~ ~: t t t ~ ~ ~ Z~
__ _ = ~ O~ ~0 ~ ~fl ^~
Z o O
O~Z~ ~ ~Z~
C~
~~ ~Z~ ~Z~ ` ~Z ~
_ ~ ` 4 ~

x I t ~ ~ ~ D
- _ ~ .

l ll l ll l ll C Q æ z z . O .
o 0 O~ . ~ . , ~ ~ - o C~ 1 1~ 1 1~ 1 11 U~
~_ .. ..
~ ~1 ~ ~ - . ~ .

` ~

.

~2~2~0 -- 54 - .

, ~ , "
~ V) _ ~ ~
o .. ..
3~ 3 c O ~ O a~
QJ , J ~ J
1~ Q ~ _ ~ _ c~ ~ Ql a v~ Q
. __. . ~
~ l C~
C~
Z ~ ~
U~
S~
C~

..

3~
z z æ
^~

. . ..
.
:
., c C
o ~ o ~ o ~ D ~ D
~ . -_ _ - . - _. . _.

i 11 C`~
A ~ 9 ' ~ ~
~ Z I ~1 ~ "
~ o ~ E ~ , ~' s~ ~

QJ ¦ ~ ~ _ .~ ,-.

- i~2Z2~rilC3 I ~
~ ,a)~ o ~
o ~ o ~
aJ -- W -- W
~1 _ ~ _ ~ 5 Q
v~_Q _ . , 3Ul C~c~l . Z Z

N !~! ~1 _ 2~ 2 ~u~ æ z o :~
_. ._ ~C a~ 1~ 0 ~5 ~ O ~ O
:~ _ __ . _ . _ .
.

0 Q O ~~ ~ o ~ ~

~ C Z:
~ __ 2 _ ~ I X - ~ _._ _ .. . _ .

' ~:225~0 3~ o ~
r ~ S

~' X

l . .
n~ x al ~

3L2;~:25~L~

5 7 _ . I ~ I ~ I
O .u~ ,u) c ~n CJ 3 ~:S 3 ~ 3 O ~ O ~ O
~ ~ ~ ~ C J C _ C
V~ Q (11 al'~
_ ~-r~ ~ 1 Z
:~ ~ 5 . _ -- _ _ W~ o~ W~ W~ W~
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Example 72: 60 parts of the com~ouncl of the formula:

OH
,,, ~ C l // ~ D\ /~ I
-N=N-- ~-N=N--\ / \ / I 11 1 /~
=O ~ 5 N N
/~/\//\ 11 1 3 NH-~ -Cl \D
N

: obtained by subiect;ng I-ac;d to a condensation react;on w;th cyanur;c chlor;de and coupl;ng the product w;th d;azot;sed S p-am;noazobenzene~ are suspencled ;n 500 parts of water and treated at room temperature with 43 parts of the polyamine of the formula CzH5 NH~CH2) 3_1 e H
N N

.: /; //; C2H5 H2NCH2CH2HIl N N~CH2 ) 3-N
~' C2HS

The reaction m;xture ;s stirred at 45 until thin-layer chromatograPhy ;ndicates that starting material ;s no longer ~ present. The dye of the formula:

i~

~ ' :

:

: ~:

11 2~?,S~LO

OH Cl _.~ o ~
-N=N-- -N=N-- N N
\ / \ / 1 11 1 11 1 o ,~
/~/\//\ /\~\

NH~CH2) 3-N( C2H5 ) 2 /~
N N
R= I!
/\//\
-CH2CH2NH N NH( CH2 ) 3 N ( C 2H5 ) 2 wh;ch has been prec;pitated is readily soluble in an acid aqueous medium and dyes paper in br;lliant red shades; the dye;ngs have good~fastness to light and wet process;ng, and the effluent is colourless.
The dyes which can be seen in Tables 7 and 8 below ` are obtained by following a procedure analogous to that indicated.

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Example ~4: A paper web is produced from bleached beech-sulfite pulp (22 SR) on a continuously operating laboratory papermaking machine. An aqueous solution of the dye accord-ing to Example 1 is metered continuously, w;th vigorous turbulence~ into the low density pulp, ten seconds upstream of the head box (0.5% dyeing, liquor ratio 1:400, hardness of water 10 ~erman hardness~ pH 6, temperature 20).
A deep red shade of medium intensity is formed on the paper web. The effluent is completely colourless.
Example 95: 50 parts of chemically bleached beech sulfite pulp are m;xed with 50 parts of bleached RKN 15 (freeness 22 SR) and 2 parts of the dye according to Example 1 ;n water (pH 6, hardness of water 10 German hardness, temperature 20 liquor ratio 1:40). After stirring for 15 minutes, paper sheets are Produced on a Frank sheet former7 The paper is dyed in a very intensive shade of red.
The effluent is completely colourless~ The degree of exhaus-tion reaches virtually 100%. The fas~ness to wet processing and fastness to light are excellent.
Example 96: 10 parts of cotton fabric (bleached, mercerised cotton) are dyed in a laboratory beam dyeing machine in 200 Parts of a ~iquor (hardness of water 10 German hardness, pH 4, dye l;quor c;rculated 3 times per minute) containing 0.05 part of the dye according to Example 1. The temperature is raised from 20 to 100 ;n 60 minutes and is then kept constant for 15 minutes.
The dye liquor ;s completely exhausted. A deep red dye;ng which is dist;nguished by good fastness to light and very good fastness to wet Processing is formed on the cotton fabric.
A textile fabr;c composed of regenerated cellulose (viscose) is dyed by the same procedure, and a deep red dye-;ng which has good fastness to l;ght and very good fastness to wet process;ng ;s also obtained on this mater;al.

Claims

WHAT IS CLAIMED IS

1. An azo compound of the formula I

(I) in which F is the radical of an azo compound containing sulfonic acid groups, A is is radical of the formula or in which R is hydrogen or C1-C4-alkyl, R1 is a linear or branched C1-C6-alkylene radical or a C1-C6-vinylene radical, R1" and R2" independently of one another are hydro-gen or C1-C4-alkyl, it being possible, in the case of R2", for the C1-C4-alkyl group to be substituted by an group in which R7' is hydrogen or C1-C4-alkyl which is unsubstituted or substi-tuted by hydroxyl, phenyl or carbamoyl, or is cyclohexyl which is unsubstituted or substituted by 1 to 3 methyl groups, or is a phenyl radical, and R8' is hydrogen or C1 C4-alkyl which is unsubstituted or substituted by hydroxyl, phenyl or carbamoyl, or the radicals R7' and R8', together with the common N atom, form a pyrrolidine, pipe-ridine, morpholine or piperazine ring, B is a basic or cat-ionic radical and x is at least 1, subject to the proviso that the number of groups B present in the molecule is greater than the number of sulfonic acid groups.

2. An azo compound of the formula I, according to claim 1, wherein F is the radical of a disazo compound con-taining sulfonic acid groups.

3. An azo compound of the formula I, according to claim 1, wherein A is a radical of the formula -NR-CO-R1-.

4. An azo compound of the formula I, according to claim 1, wherein A is a radical of the formula

5. An azo compound according to claim 1, wherein A is a radical of the formula

6. An azo compound of the formula I, according to claim 1, wherein x is the numbers 1 or 2.

7. An azo compound of the formula I, according to claim 1, wherein x is the number 1.

8. A process for the preparation of an azo compound of the formula I according to claim 1, which comprises, if A
is a radical of the formulae -NR-CO-R1-, or coupling a diazotised amine with a coupling component, the radical A-halogen being already pre-sent in the diazo component or in the coupling component, and reacting the compound F-A-halogen with a compound (H).gamma.-B (y = 0, 1 or 2) which introduces the radical B, and, if desired, quaternising the resulting compound, or, if A
is a radical of the formula a) subjecting a compound of the formula II
(II) in which R1" and F are as defined and R3 is unsubstituted phenyl, halogen-substituted phenyl, C1-C4-alkyl-substituted phenyl, C1-C4-alkoxy-substituted phenyl, C1-C4-alkyl or C1-C4-alkylenephenyl, to a condensation reaction with a compound of the formula III
H-B'-R (III) in which R is as defined and B' is a bridge member carrying the radical (B)x, or b) reacting a compound of the formula VIII

(VIII) with a compound of the formula III in the presence of phos-gene, the symbols F and R1" being as defined, or c) subjecting a compound of the formula VIII

(VIII) to a condensation reaction with a compound of the formula IX
Cl-CO-B'-R (IX) or R3OCO-B'-R (1xa) in which F, R1", R3, B' and R are as defined.

9. A process for dyeing or printing textile materials, paper and leather, which comprises applying thereto an azo compound of the formula I as defined in claim 1.

10. A process for preparing inks which comprises incor-porating into a suitable vehicle an azo compound of the formula as defined in claim 1.

11. A process for dyeing and printing natural and regen-erated cellulose materials which comprises applying thereto an azo compound of the formula I as defined in claim 1.

12. A process according to claim 11 in which the cellu-lose material is viscose or cotton.

13. A process for dyeing or printing paper of all types which comprises applying thereto an azo compound of the formula I as defined in claim 1.

14. A process for dyeing or printing bleached, unsized, lignin free paper which comprises applying thereto an azo compound of the formula I as defined in claim 1.

15. A process for dyeing or printing polyacrylonitrile which comprises applying thereto an azo compound of the formula I as defined in claim 1.

16. Materials which have been treated or dyed or printed with an azo compound of the formula I according to claim 1.