Note: Descriptions are shown in the official language in which they were submitted.
s~
Case 1~-4687
IMPROVEMENTS IN OR RE-ATING TO ORGANIC COMPOUNDS
The invention relates to compounds suitable for use
as dyestuffs and to intermediates for making such dyestuffs.
According to ~he invent,on there is provided a
compound of formula ~I)
R .
1 (I)
B
in metal-free; l:l or 1:2 metal complex form or acid addition
salt form
in which P~ is hydrogen; C1 ~alkyli C5 6cyclo
alkyl unsubstituted or substituted by one or two C1 4-alkyl
groups; phenyl, benzyl or phenyl-ethyl, the phenyl group of
the latter three substituer,~s heing unsubstituted or substi-
tuted by one or two groups selected frcm methyl, ethyl,
meihoxy and ethoxy,
T is hydrogen; -CN, -N ~ A~ 9
-COOP4; -CoN~Rs)2i -52~l(Rs)2
~z~s~
- 2 - 150-~587
IIH C~l A~ - ~ ~ R A~
\ Nl /
R6
B is -A-NH-R2; hydrogen; Cl 4alkyl unsubstituted or
substituted by a C1 ~alkoxy, C2 4alkyl substituted by
hydroxy; C5 6cycloalkyl unsubstituted or substituted by one
to three Cl 4alkyl groups, phenyl Cl 3alkyl, the phenyl
group of which is unsubstituted or substituted by one to
three groups selected from Cl 4alkyl, C1 4alkoxy and
9 , A4 N(R7)2; -A4-~(R8)2Rg A~3 or -N(R7)2,
R1 ;5 a group a
-N=N-A1-N-N~ ~--~ S3H)n
R19
or, when B is -A-NH-R2, hydrogen or -N=N-D ;
where Xa is -0-, -N(R5) or -S-;
R3 is hydrogen5 C1 4alkyl~ -~(R5)2 or C ~ 5 2
R4 is C1 6alkyl or phenyl-C1 3alkyl;
R5 is hydrogen or C1 ~alkyl, or when two R5's are
present attached to a nitrogen atom both R5's
together ~ith the N-atom to which they are
attached form a saturated ring
which contains one to three heteroatoms;
R6 is C1-~alkYli
Al is a residue of a tetrazo component;
~2~751
- 3 - 1~Q-4687
n is O, 1 or 2;
A4 is C2 8alkylene or C2 8alkenylene;
A¢ is a direct bond Cl 8alkylene or C2 8alkenylene:
D is a diazo component,
where A is C2 8alkylene which may be interrl~pted by up to
t~lo hetero atoms; C2 8alkenylene which may be interrupted by
up to two hetero atoms, phenylene or cyclohexylene;
t NH- R12
R11 q
q is n or 1;
R1t is hydrogen, halogen, NO2, Cl ~alkyl or
C1 4alkoxY
~ çR13
R12 i S --~0
14
.~ .
-C~(C.H23a~Z
or hydrogen,
a is an integer 1 to 3.
R14 is an aliphat.ic, cycloaliphatic,aromatic or
heterocyclic amine group in which the N--atom is attached
to the triazinyl ring
Rl~ has a significance of R14 halogen, OH, -NH2
Cl 4alkoxy, phenyl or
~z~
_ ~ 150 46~7
GH R `~
-NR5-A2-~ ~
,
A2 is a linear or branched C2 6alkylene or -NH-CO-CH2-
where the starred N-atom is attached to ~he -NR5 group;
Z is -N(R7)2 or -N(R8)2R9
each R7, independently, is hydro~en, C1 ~lkyl, C2 6-
~lkyl substituted by an halo~en, -OH or -CN group, phenyl-
(Cl 3)alkyl, the phenyl ring of which is llnsubst,tuted or
substituted by 1 to 3 groups selected from halogen, Cl 4-
alkyl and Cl 4alkoxy; or C5 6cycloalkyl, unsubstituted or
substituted by l or 3 C1 4alkyl groups;
or both R7's together with the N-atom to whi~h they are
attached form a 5- or 6-membered saturated ring which contains
one to three heteroatoms,
each R8 independently, has one of the non-cyclic signi-
ficances of R7 except hydrogen and Rg is Cl 4alkyl unsubsti-
tuted or substituted by phenyl or
both R8's , R9 and the N-atom to which they are attached
~orm a pyridinium group (attached by its N-a~.om) unsubstituted
or substituted by one or two C1 4alkyl groups; or a 5- or 6-
~embered saturated ring which contains l to 3 heteroatomsi
R17 is hydrogen, a group
~q ~ ~
-N-N-K1 ; -~=N-A10-N=~-Kl or .
OH
-XO ~ N=N-Al-N=N-K
( 03H)n
lZ~
- 5 - 150-4687
where XO is a bridging group and Alo has a signifi-
cance of Al defined above or is a coupling componenti
Kl is a diazo or coupling component;
Rlg is hydrogen or when R~7 is -N=N-Kl or -N=N-A
-N=N-Kl additionally -OH, -NH2, Cl 4alkyl-carbonylamino,
benzoylamino or phenylamino, the phenyl group of the latter
two substituents bein~ unsubstituted or substituted by
l or 2 substituents selected from halogen, -N02, -NH2,
Cl 4alkyl and Cl 4alkoxys
R20 ( NR5)q Ql ~(R7)2; -~-NP~s)q Q2 N(28)2R9 ~ r
-NR5 -~o ~ Rl3
~14 ç~ ~3
Ql is -CH2CO- , -NHCOCH2- or C2 6alkylene ~Ihere
the starred atom is attached to -r,R5 (if present)
or the phenyl ring to ~hich R20 is attached.
~2 is -c~N~cqBH2-or a significance of Q1;
A~ is a non-chromophoric anion;
with the provisos that:
ij when ihe compound of formula I is sulpho-free at
least one water-solubilising basic or cationic
group is present if the compound of formula I is a
monoazo compound; and at least two water-solubil.-
sing groups are present if the compound of formula I
is other than monoazo;
ii) ~Ihen one or more sulpho groups are present in the
compound of formula I, the number of cationic and
basic groups present is at least the number of
sulpho groups ~ 1;
iii) when B is -A-NH-R2, Rl is hydrogen, A is C2 8-
alkylene; T is -CN then R2 is not hydrogen.
Preferably ir. the co~pounds o~ for!nula I when B is
-A-NH-R2 then group B is sulpho-free.
Preferably Alo has only a significance of Al.
In the specificatior) halogen means fluorine~
- 6 - 150-4687
chlorine, bromine or iodine, preferably chlorine.
For the avoidance of doubt the group D includes the
group a.
Where any symbol appears more than once in a formula
unless indicated to the contrary its significances are
inclependent of one another.
Any al~yl, alkylene or alkenylene present is linear
or branched unless indicated other~lise. The alkyl group of
any alkoxy group is linear or branched unless indicated to
the contrary.
Any aliphatic amine group is preferably a mono Cl 4-
alkyl- or a di-~C1 4alkyl)-amino group. The alkyl group may
he substituted by l to 3 grGups selected from halo~en, phenyl
hydroxy or C5 6cycloalkyl.
Any cycloaliphatic amine group present is preferably
C5 6cycloalkylamine, the cycloalkyl ~roup of which may be
substituted by one or two Cl 2alkyl groups.
Any aromatic amine grcup present is preferably aniline~
the phenyl ring of which is unsubstituted or substituted by
one to three substituents selected from Cl 4alkyl, C1 4alkoxy
halogen, hydroxy and phenoxy.
Any heterocyclic amine present is preferably pyridine,
triazine , pyridazine, pyrimidine, pyrazine or a group of
the formula
T ~
0 ~ ~ ~ H
(when unsaturated) and morpholine , pyrrolidine, piperidine,
piperazine ~N-methyl piperazine (when satllrated). Each group
may be substituted by one to three R6 aroups;
R is preferably R' where R' is me~hyl, ethyl,
751
- - 7 - 150-a6g7
unsubstituted phenyl unsubstituted benzyl or unsubstituted
cyclohexyl. More preferably P~ is R where R is methyl or
unsubstituted phenyl.
is preferably T where T is hydrogen CN
A~3 or CONtR5 )2 where R3 and R5 are
defined below. More preferably T is T where T is CN or
~ N ~ A~ where R3 is defined below.
- e iS preferably B where B is -A -NH-R2 hydrosen
-CH3 C2H5 -C2H40H unsubstituted cyclohexyl benzyl
(CH2)2 3N(R7)2; ~(CH2)2-3N(R8)2R9 A 7
where the symbols are defined below. B is more prefer-
ably B where B is -A -NH-R2~ hydrogen -CH3 -C2H~ benzyl
-(CH2)bN(R7)2 -(C~12 )bN (R8)2R3
where the symbols are defined below and b is 2 or 3.
Rl is preferably Rj where R~ is
OH R17
-N=N-Al--N-N ~
so3~)q
or when 3 is -A-NH-R2 hydrogen or -N=N-D
and where the symbols are defined below.
Preferably A is A ~Jhere ~ is C2 8alkylene or un-
substitu~ed phenylene. More preferably A is A where A
- 8 - 150-4687
is 1,2-ethylene, 1~3-propylene or unsub,tituted meta or
para phenylene.
Preferably R2 is R2' wheré R2' is a group of formula
where the symbols Rll and R12 are defined below.
More preferably R2 is R2 where R2 is hydrogen or
~ C ~ NH ~ R12
where R12 is defined below.
Preferably R3 is R3 where R3 is hydrogen, methyl, ethyl,
-NH2 or -N(CH3)2. More preferably R3 is R3 where R3 is
hydrogen or methyl.
Preferably R5 is R5 where R5 is hydrogen~ methyl or
ethyl. Preferably R5 is hydrogen or methyl.
Prel~erably R7 is R7 where R7 is hydrogen, linear or
branched Cl 6alkyl, unbranched hydroxy C2 3alkyl, benzyl,
2-cyanoethyl or both R7's together with ~he N-atom to which
they are attached ~orm a pyrrolidine, piperidine~ morpholine,
piperazine or N-methylpiperazine group;
Mor2 preferably R7 is R7 where R7 is hydrogen,
~ethyl or ethyl, 2-hydrox~yethyl or both R7' s toset!leY
~iith the N-atom to ~h~ch they are attached form a morpholin-e
- 9 - 150-4687
piperidine, piperazine or N-methylpiperazine;
Preferably R8 is R8 where R8 is one of the signifi-
cances of R7 e~cept hydrogen and Rg is Rg where Rg is methyl,
ethyl, propyl or benzyl or both R8 and Rg together with the
N-atom to which they are attached foim a pyridiniuln ring un-
substituted or substituted by one or two methyl groups or
a group ~ O ~ where Zo is -0-, direct bond -CH2-;
6 ~(R6~2 A , -SO2- , -SO~, -S- More pr f b
R8 is R8 where Rg is one of the s;gnificances of R7 except
hydrogen and Rg is Rg where Rg is -CH35 -C2H5 or benzyl or
both R8 and Rg together with the N-atom to which they are
attached form a pyridinium ring, unsubsti~uted or substituted
by one or two methyl groups, or is a group ~ defined above.
Preferably R1l is R11 where R1'j is hydrogen, chloro,
nitro, methyl or methoxy.
Preferably Rl2 isRI2 where Rl2 is
R1~ or-CO(CH2)~ 2 Z
or hydrogen;
More preferably R12 is Rl2 where R12 is C0 2
13
14
where Rl3, Rl4 ~nd Z" are defined below.
Preferably R13 is P~l3 wher~ R~j3 is chloro5 -~H5 -NH23
R ~ -N ~ mono Cl 4alkylainino,
t;~
- 10 - 150-4~87
di-(C1 2)alkylamino, monohydroxy(C2 4)alkylamino, bis-
[hydroxy(C2_4)alkyl]an;ino or N-R
R5
where R2l is Cl t2alkyl,unsubstituted or sub,tituted
by -OH and uninterrupted or ir,terrupted by one to three
grou~s selected fro~ -N(R7)- and-~(R8)2 A ; NHCOCH2-Z;
-CH2C~NH-Yl-Z~ 1 Z;
CH3 Rz~
24 ~ Y1 ~ i ~6 A
--Yl ~ N-R5 ~ ~ çl,,~6
-Y1-, ~ N-Y1-z -Yl - N ~ - Y - Z 2
-CH2CONH-Y ~ ; R& R6
wllere Y1 is a Cl 8alkylene or a C3 8alkenylene group
Z is -N(R7)2 or -N(R8)2R9 A
R23is ha70g~n5 -OH5 -NO2, C1 4alkyl or C1_4alkOXY;
R24 is a 97'0Up -N(R7)2 or -~(R~)2Rg h~or a
group -CO-Y2-Z', -NHCO-Y2-Z', , -CONH-Y2-Z',
52N~-Y2-Z ; -r2-Z or -NHNHcocH
where Y2 is C1 ~alkylene
S~
- 11 - 150 4h87
More preferably R13 is R13 where R13 is -N-R
R'5
where R21 is -ICH~)2 3-;~(R7)-(C~I2)2 3 ( 7) 2 5
(CH2)2-3 t~(Rg)-(CH2)2_3-~(R8)C2H5 2A~3
-(CH2)2_3-N(R7)-C2~5
-(CH2)2-3-N(Rg~2 C2 5
-NHCOCH2 -Z"
-CH2-CONH-Y2 -Z"
-CH2-CO~;H-Y2--~ --~\N Q5
~CH3
~ Y1 ~ - R24 \'-~/ \ C~3
where Y2 is (Cl ~)alkylene.
Preferably Z is Z' where Z' is -N(R7)2 or -N(R8)2Rg ,4~3,
More preferab1y Z is Z" where Z" is N(R'j)2 or
N(R,3)2Rg A
P~ferc~lY R14 is P~ here P~14 is -N-221 w
R5
where R5 a~d R21 are defined above. t~,ore preferably R14 is
R14 where Rl4 is -N(R~) R2~
- ~2 - ~50-45g7
Preferably Rig is hydrogen.
Preferably ~ is Dl ~here D' is
(R26)~ --Al-N=I ~ S03H)q
(R26a)
l=N-'~a
(/26a)2 (l20a)2
N=N-Ra
where each R251independently, is selected from
hydroger" halogen, ~I2~ -NH2, ~1 4alkyl, Cl 4alkoxy, -CN,
trifluoromethyl, pnenyl, anilino, benzoyl, carbamoyl,
phenoxy, halophenoxy, dihalophenoxy, Cl 4alkylsulphonyl,
phenylsulphonyl, Cl 4alkylsulphonylamino, di~ C1_4alkyl-
aminosulphonyl or C1 4alkylsulphonyl;
each R26a independen~ly, is hydrogen, hàlogen, C1 4-
alkyl or Cl ~alkoxy and
X is any one of X~ to Xl~8 below in ~hich X1 is a
direct bond, X, is a lir,ear cr branched C1 4alky7ene group;
'1
X3 C0--, X4 -~H-C-~H-, X~ -S-, X~ -0-~
X7 -C~=C~ 8 S-S-, Xg -S02 ,
Xl~ -NH-, X~ -CO-~ X12 i~ C
Crl3
.5~
- 1 3 - 1 50 -4687
~ CO-
X~3 ~ , X14 -cn-~
X~5 -CO-NH ~ ~ R ~ X16 -NH-CO- ~ CO-~H^,
NH-CO^
X17 -S02-l`lH-, Y'~8 S2 ~H ~ ~ so2 ,
X7~ ~-C~-R43--CO~ X20 -~!-C~-c~,=cH_co-N-5
R44
X21 -~`-CO-~ X22 -
r~44 r~4~
23 -CH2CO-NH-NH-CO-CH2-, X~4 -CH=CH CO-NH-NH-CO-CH=CH-,
,C~,2-C~2~ ~C~12-CH2~
X -N N-, X -O-CO-N N-CU-O-,
~ CH2-CH2 / 26 ~ CH2-CH2~
X27 -C C ' X23 ,C, O ~ X2~ ,C, O, X;~o ,C, ,C"
`o' . o o
X31 -- ( CH2 ) g~O~,
X32 -N -C, ,C,- N-- , X33 --O-C~ ~ C-O-
Rq~ N~C ,~ r~4 11~ , N
R45 R45
X34 -CQ-N-R43-N-CO-, X35 -Co-N-(c~2)~-o-(cH~) -M-CO-
R44 R44 R~!~ R44
5~
- 14 - 150-4687
X36 CO-N-~C~2)9-1~-(CH2ig~N~CO,
R44 R44 R44
X37 -CO-N-(CH2)9-0-(CH2)9-0-(C~'2)9-N
R44 R44
R33-C!~2-C0~ -,R39 -CH=CH-C0-N-,
R~l 4 R4a
X40 ~N-N~ X4l -CH2~S-C1~2- ~ X42 S
X,,j3 -CH2-SO-CH2-,
44 C~2 S~2-CH2- , ~45 -cH2-NH-co-NH-cH2-,
X46 ~C~'2-~ -Cs-~ C~2
-CP-~I~CH C - N-C2'~ H-C-~
Xfi~, -CH2-CH2-co-N_~ Xa~g -CHz-Co CHz
R44
X50 -C!~=CH-CH-~ X~ CO-,
X52 _Co @~-CH ~ ~ X53 C~_C
X54 -CO-NH @)-CH2-NH-Co->
X55 -CO-N!I-Clt2 ~ CH2-NH-CO-,
~ CH2 -N" - CO--
X~6 ~CO-iYH~
C~
150-L687
~57 -Cn-~'H ~ ~ 58 -C~t2-CO-~
<~ .
X59 -C~=CH-CO-C~=CH-, X60 ~CH ~ ~ CH ,
X61 ~C~I2 ~ ~ CH~_, XD2 ~~C~2~C~'2~~'
~HJ
X53 _O CH2_0 , X~ C~N~H~P~3~C~h~
70 -NH-C~ H-, X71 -C~ -C;)-,
~:72 -CO-NH~P`~2a
,-CO-
X73 _N~-C~_CH2_r~_C~
X74 ~NH~C0~~H=C~-C0-5;.H-,
X7~ H-c~-(cLl2)A-co-7
76 ' C3 (CH2)2-c~
CH3 C~3
X77 -I~-CO-C~=C~-co-;~_,
CH3 ~H3
X7~ -N-CO-N-,
C1~3 C~3
X N--C~5Y~ ~ ~i`l~
CH3 N~ 3 rl~ C--IY
P'4:~a P~45a
- 16 -- ~50-~687
X81 CH2-~ ~Z2 -(CH2)2-~ X33 -(CH2)3-,
X84 -(CH2)~-, X~s -CO~ -(cl~2)2 ~!
X8~; -CO-I~H-(CH2)3-N~I-CO-~ X~3, -Cn~ -(CI~2)~ H-CO-~
88 ,N (C~2)2-N-co-~ ~8~ -CO-NH-CH2-CH-rl~i co
CH3 C~3 - c~3
Xgo -CO-~ -CH--~CH-I~H-CO-
H3C CH3
X~ oo -CO- ~H-R43-cO-NH-R43-NH-co-,
lol 4~ ~H CO CH2 CH2 CO-NH-R43-NH-CQ_~
X -CO-NH-R43-NH-CO-CH=CH-CO-NH-R43 ~,H
R45
X104 -So2-~R~ H2 ) o -1lR4 4 -
'`105 CO-NP~44-R43-
X~06 -O CO- ~ CQ-O-,
107 ( ~ '
108 C~NH-R~3-NH-co-~ -R~-N~-c~-
each R42 independently, ia halosen, C1 4alkyl or C1 4alkoxy,
each R43 independently, is a linear or branched C1 4 alkylene
group,
- each R44 independently, is hydrogen or Cl 4alkyl group,
each R42a independently, is hydrogen, -Cl, -CH3 or -OCH3 and
eac'n R45a independen,ly, iâ -Cl ~ -NH-CH2-OH ~ OCH3, OH, -NH2,
~N(CH2-CH20l~29 -r~-(CH2)3N(C2H5)2' QC2H5'
3L23~ ,5~
1 50-4687
CH3 C~13
each R45 independently, is haloge1l, -NH-C~12-CH2 Q~l~
N ( CH -CH -~H ~ 7, -~H2 ~ ~OH, - NH - ( CH2 ) 2 _3N ( 2 5 2
CH3 C~3 ' ~~ -OC~3 or
-OC2H5 '
g is t, 2, 3 or 4.
More preferably X, ~hen one of R26a is not hydrogen, is
a direct bond, Xz~ X2~' ~32 or 40
Preferably when ~e pnenyl rings to which X is
attached are substit~ie~ the substitution is in an ortho
position to the azo bri~ges . attached to the sai~ rings.
Ka is a diazo Gr c~uplir,g component of the pyrazolone,
5 series~ 5-aminopyr~z31e series~ a- or ~-naph~.hol series5
aniline series, phenol series5 a- or ~-amino naphthalene
series, aminonaphthol ;~ries, acetoacetyl alkyl or an aryl-
amide series, barbituric ~c~d or dimedone series, a dimedone
carboxylic acid ester, a pyridone, a group
~'
or diaminopy~^idine~
S~
~ 150-¢687
In the various CXZ~3n2nt series mentioned above the
component may be subs~ Z~ed by such groups as R1 to R~o
hereinbefore or hereir~ r defined.
Preferably ~a ~ here K~Z j S a group of any one
of the formula a) to ~ elo~
~ (R28~2 ~ ~ Ch' -C-C.-CO-NH-R29 (b)
... . .
- 18 - 150-~,687
R32 CN
33 33
?~f 35
R36
[~ ~37 (f)
01
~__ R37 ( 9 ) _~/R3
\R39
~- R37 ~h) ~/( 4)2 ~k
NH2 R
237
2 ~
- 19 ~ 150-~6~7
More pref~rably ~ -is D~ here n~ is
@, (P~26)2
OH R17
~ 2 ~Al-r~=~ ~ Rlg
or
R2~)2 ~R2~)2
I N=N-Ka
~ ~--X~'
where each R28 indeper.dently, is hydrogen, halogen, Cl 4-
alkyl or C1 4alkoxy and X' is defined above and Ka is
defined belo~.
Kd is more pre,erab'y Ka w~ere Ka iS a group of one
of the formula al to k~ ~elGw:
~ ~ H (al)
OH O
C~3-C=~-C-NH R29 (bl)
R28)2
b (Cl )
s~
- ~ - 150-4687
1''
OH ~ (dl)
~CH3
~ N (~1)
R33-NH ¦ NH 33
CH3
~34 ~ /
R '
~ ,OH (g1)
(R37 )q~ R37~l_q
R3
37
\R3a ( j 1 )
tR~rO)2
~ ~kl )
~ 21 - 1 5G-4687
~here R29 i s a group
-(CH2)m-Z ~ -
(R47)2
3 ~C I ~r~
( CH3)~N,~C--
( CH3 )~ ~C--
~ C~ ~C\~(cH3)
~z~s~
- 22 - 150-4687
R~48
or ``~
CH2-Z R13
where R46 is hydrogen, -NH ~ N ~
14
-NHCO(CH2)2_3-Z~ -S02NH(C~2)2-3
each R47 independently, is hydrogen, halogen, C1 4-
alkyl, Cl 4alkoxy, -N02 or-CN,
R48 is Cl-4alkXY and
each q, independently, is ~ or 1 and R13, R14, Y and Z
are defined above,
R32 is Cl 4alkyl or phenyl;
each R33 independently, is selEcted from hydrogen,
C1 4alkyl, -(CH2)2 30CH3, ~(CH2)20H, -(CH2)2-3~( 3)2
~CH2)2-3N(CH3)3 A R33 is pr~ferablY P~33 where R33 is
y g , (CH2)2oH~ -(CH2~3 ~ OCH3; -(CH2)2 3 - ~(CH3)2 or
-(CH2)~ 3N(CH3)3 A~,
R34 is -OH or -NH2'
35 is C1-4al~Yl~ -~OOR6, -CON(R5)2 or -CONH-Yl-z,
where R5 is Cl 4alkyl or hydrogen and R~; is C1 4alkyl
/ ~H2 ~ R4
R36 is hydrogen, -C or ~
\ I`~H2 '-~r~50~2
~z~s~
- 23 - 150-4687
where R49 is hydro~e~, -CONH-Yl-Z, -S02-NH-Yl-Z,
-NHco(cH2)2-3 Z or Rj3
N--~
_.;,~0
N ~
`Rl 4
each R5G inde~en~en~ly, is selected from hydrogen5
halogen, C1_~alko~ i;0~; -NH2 or C1 4~1kyl;
,n~l3
R37 is -NH ~ -NHCO(CH2)1 3-Z,
~14
S2N~I-Y~ -CONH-~1-z~ -CO~ 2, -NH-Yl-Z, -CH2-Z ,
NHNH-C0 CH2-Z -CC1!~' ~ or hydrogen;
R38 is C1_4alkyl~ -CH ~ or (C~2)2~N
Y 3~ ~38 ~.her2 R38 is -~H3~ -C2~5~CH2)2CN
or benzyl;
R39 is Cl 4al~yl or -(CH2)m-Z; preferably R39 is R39
where R3g is -CH3~ C~ or ~C~2)m'z'
Rqo is hydrocen, ~1 ~al~yl or Cl qalkoxy,
m is an inte~er 1 ta 6 and m is preferably m'
- where m' is 2n integer 2 to 4
ICb is a componen~ of fcrmula (a),
~b) or ~d) ta ~13 f c~m?3nent Ka and KD jS a
component ~alr~ ~13 ~` (dl~ ~ (~
Sl
- 24 - l50-4687
Preferably R29 is R2g where R29 is (CH2)m
R46
47)z
C ~ S\ ~ or
R,
CH2-Z
wnere R46 is hydrogen~
~ l3
-NH~ NtiCO(C'rl2)2_3-Z or -SO2-NH-(CH2)2 3 ~ ;
~14
each R47 independently, is hydrogen, chlorine, bromine,
methyl, ethyl, methoxy, ethoxy, -NO2 or -Cll;
and R48 is methoxy or ethoxy;
m' is 2, 3 or 4.
Preferably K~ is K; where K1 is a group of the
formula
Il OH
- 25 - 150-4687
or a coupling component of the aniline series, nydrcxy-
benzene series, aminonaphthalene series, hydroxynaphthalene
series or aminohydroxynaphthalene series, aminopyrazole
series, pyrazolone series, N-alkyl or N-aryl acetoacetamide
series.
Preferably Kj is a grou~ o~ the ~ormula
T ~
O I OH
Preferably A1 or A10 is A1 ~here A~ is
R5l R53 R~53
\~ \~Yo~
52
or ~ ~< ~
where P51 is hydroaen~ halogen, C1 4alkyl or C1 4~
alkoxy~,
R52 is OH, halogen~ -CN5 -CONH~, -NHCOCl 4alkyl,
-NHCONH2, -COOH, -5O3H, hydrogen, Cl ~alkyl
or -Cl 4alkoxy,
each R53 independentlyS is hydrogen, halog~n, -CN,
Cl 4alkyl, Cl 4alkoxy, -COOH or -SO~H or-OH;
Yo is a direct bond, (CH2)~ 3, -O-, S ,
-SO2-, -NH-C0- 3 -NH~C0NH-, -NH-C0(CH2)2 3-
~z~ s~
- 26 - 150-46~7
-CONH-, -CONH(CH2)~ 3NHCO-, -O-(CH2i2_3-o-,
-N=N-or -CH=CH-CO-CH=CH-.
- More preferably Al or Alo is Al' where A~' is
or ~ _yO _ ~ {~ ~
where R52 is hydrogen, chlorine, -OH, methyl or methoxy;
R53 is hydrogen, -Cl, -CH3, -OH or -OCH3;
Yo is a direct bond, -NH-CO- or -NHCONH-.
Preferably in A'j the free bonds shown are in a meta
or para position to each other (in the phenyl ring) or to
YO (in the YO-containing group).
In the compounds of formula I preferably 0 to 4 sulpho
groups are present, more preferably up to 2 sulpho groups
are present.
Preferably XO is XO ~here XO is NH-, -NHCONH-,
-NHCOCH=CHCONH-, -NHCO(Ctl2)~ 3CONH-, NHCD CONH-~
~/ .
-NHCO ~ r~ ~ONH- or
R ~
13
where ~13 is defined above.
More preferably XO is XO where XO ;s -NH, -NHCOGH=CHCONH~
or -NHcQ(cH2)
- 26a - 150-4687
Preferably Rl7 is hydrogen, a grollp
NR5-CO ~ ~ ~ ~
q
-N=N-Kj; -N-N-Aj-N=N-Kf or
OH
-Xo~ [~ ~ N=N-Al-N=N-K
~S3H)r~
R~ Ql N(R7)2 or -NR5-Q2-N(R8)2R3 A~3 or -~R5 ~ N ~ ~3
and the other symools are defined above.
More preferably R17 is hydrogei;~, a grollp
NR5'-CO ~ :~ - 20
- q
-N=N-.;'f`; -N=N-Aj-N=N-Y~'f' or
O~f
(S~ 3H
~20 is -NR~-Ql N(R7~2 or ~NRs-Q2-N(R~)2R9 A or -NR5__
ar,d the othe~ symbols are defined above~ R14
~LZ~Sl
- 27 - 150-4687
Y Ql s C2_6alkylene more preferably
C2 3al~ylene most prefer3bly C3 alkylene.
Preferably R33 jS R33 where R33 jS hydrogen~
-(CH2)20H; -(CH2) 30CH3; -~ CH2)2 3-N~ CH3) 2 or ( 2 2~3-
~(CH3)3 A~3
Preferably R3A jS R36 ~here R36 is hydrogen
-C ~ A~ ; or - ~ R49
\ ~YH2 ~ R50)2
~here R49 is hy~r~gen~ -C0 ~NH-(CH2)m -Z ;
-NHcO(cH2)2.~-z or
5 ~ ,R~3
t~
each R50 indep_ndently is hydrogen chlorine
methyl or methoxy.
Preferably R37 is R37 where R37 is
.3
~ff
R~'~
~LZ~
- 27a - 150-4687
.,
Further according to tne invention there is provided
an azo co~pound, in metal-free, 1:1 or 1:2 metal complex
form5in free acid or acid addition salt form of formula II
R OH
T ~ 10 ~ __R17 (II)
O ~ ~ ~ H ~ --- (S03H)n
1 19
in which Bl is hydro~en, Cl 4alkyl, C2 4alkyl substi
tuted by hydroxy, C5_6cycloalkyl unsubstituted or subs~ituted
by 1 or 2 methyl groups, phenyl C1 3al~yl~-A4-N(R732
-A4 ~(R~)2Rg AQ, o~ -N(R7)2
and where the other symbols are defined above.
Preferred compounds of formula II are of formula Ila
R' OH R17
T ~ N=N-Aj-N=N ~ ~ (IIa)
o"~N OH S ~ ~ S03H)q
Bi
where Bl is hydrcgen, -CH3, ~C2H5, -C~H40H~ cyclohe~yl,
ben7yl, -(CH2)2_-3N(R7)~ -(CH2)2-3~(R8)R9 A
and ~here the o~her symbols are defined above.
- 28 - 1~-4S~7
Preferred compoullds of formula II are of formula lIa'
R" OH R17
T ~ ~ 1 ~ O ~ ~ IIa'
F S3 ~ (S03H)q
B~'
in which E'l is hydrogen, -CH3, C2H5, benzyl, -~CH2)2_3-
N(R7)2, or -(C~2)2_3N(R~)2R9 A
where the symbnls are defined abo~e.
Alternatively, preferred compounds of -formula II are
of the formu1a lIb
~H ~17a
=N-A1 N-N ~ ~ 5o3(ll)H~2)q IIb
where R17 is a group of the formula OH
a ~ 1 N=~-A1-~ !-
-N-N-Kl , -N=N-A1-N=N-Kl or -X
. . SO~
where the symbols are de~ined above.
Preferred compounds of formula lIb are those in wh;ch
R17a is R17a where R17a
R' R'
- N=N ~ T' -t~-N-A"-N=N
o I ~ F
Bj Bi
s~
- 2~ - 150-~&~7
';
B~
Al~ernatively, preferred compounds of fo.mula I are
of formula III in n1etal free, l:l or 1:2 metal complex forrn,
in free acid or acid addition salt form
T~ R 1
OH III
A ' -NH- R2
~ Yhere Rl is hydrogen or -N--N-D and the other symbols
are as defined above.
Preferred compounds of formula III are of the formula
IIIa
R'
~ IIIa
O 1 OH
A'-NH-R2
where R1' is hydro~en or -N=N- D'and the other symbols
are defined above.
More preferred cormpollnds of forinula III are of the
forrnula IIIb
R"
i IIIb
~y OH
5~
- 30 - 150-4687
where Rl' is hydrogen or -N=N-D"
and the other symb~ls are defined above.
Preferred compoul~ds of formula IIIb are of formula
IIIc
CH
T ~ Rll~ (IIIc)
O IN~H
A"-NH-R2
where RliY is hyd)~gen or -N=N-D"
where D"' is ~ 2
(R25a)
-Al-N-N,~
R27a R27a
~=N-Ka'
~7b
or ~ _ ~ 7a
~ =I~-K"
R27b a
3 ~ 75~
- 31 - 150-~687
here R26 is hydrogen, -N02,chloro, rnethyl, methox~ or
chlorophenoxy;
R27a is hycirogen~ chloro, methyl or methoxy;
R27b is hydrogen, methyl or methoxyi
~ ne of R26a is nitro, chloro or metrloxy and the other
01^ R26a iS nitro, chloro or methyl or both R26a's are the
same and are methyl or methoxy;
X" when both the substituents R27a and the substituent
R27b are hydro5en, is X1~ Xs~ X6~ X7~ X10~ Xll' X12' X16' X179
22' 25' X26' X27, X30, X3l, X49, X50, Xrjt, X5~, X53, X5~,
58' 59~ X62~ X63~ X64~ ~70 90, XlOl where R43 = -(CH2)l 2
X ~where P is -(CH2)l-2 and R4si~ NH(CH2)2 3 ( 2 5 2)~
Xl04~where R44 is hydrogen and y is 2 or 3) and Xl~(where
R43 is -(C~2)1-2 )~
or X", when one of R27a and R27h, is not h~drogen is
Xl~ X40, X70~ X7l~ X80, X8~, X82 or X85
Preferably when the phenyl rin~s to which X is
attached are substituted, the substituents selected from
chloro, methyl or methoxy are in an ortho position to the
azo groups attached to said rin~s.
Preferred metallisabie groups are -~H~, -OH or
-O(Cl ~alkyl) which are situated ortho to an azo bridge on a
benzo or a phenyl group. Ihis can he represented belo~.r: -
7 ~
~,<~1., <~
~2~1~S:~
- 32 - 150 4687
R6 ~ As- Miea- A ~ R66
~ N'N _ ~
R67 \R66
or ~ N ~
in which each A5independently~ is -O- or -NH-
Mea is a l:l or 1:2 metal complex forming
metal l~oth R66's and R67's are ortho
to each other and to~ether form an
arolllatic rin9 s~st~m (for example
together with the two carbon atoms to
which they are attached form a
gro~lp~,
Preferred compounds of formula I when in metall1sed
form are of formulae ~IVa) to (IVf):
R 151
~N~o ~ Y - Ka (IVa)
B 52
~ 33 - 150-4687
~,\N = U~
(IVb
R51
R ¦ /Q ~ e - ~)
T ~ N = ~ ~R
b~ N~ ~R
B (S03~) 19
( IVc)
.
R51
N = N~ y
B
TC~yN = N~
O-~le- 0 Rs2 52 (IVe)
B
5~
- 34 - 150-4687
T ~ N ~ C>S ~-n ~ ~ A'/N
~here Ya is -- or -NH-
Me is copper, chromium, cobalt, nickel or iron,
manganese or zinc for 1:1 metal complexes (Me is
preferably copper in this case) or ~le is chromium,
cobalt,iron or nickel for 1:2 metal complexes
~Me is preferably iron in this case)~
Compounds of formula I ~here Rl is hydroaen may be
prepared by reacting a compound of formula V
~ V
I OH
A-~iH-R
with a compound of formula V
I~L_~Rl 3
R~ a
R14
where R60 is halogen and R~l is hydrogen or a group
of the formula
~IL21~75~
- 3~ - 150-46~7
~H2
--ICi <~
R
11
or by reacting a compound of formula V where R61 is
--C~ ~--CO (CH2)1 3-R60
~ith a compound of formula YI or VII
NH(R7)2 ~YI~
N(R8)2 Rg (YII)
Compounds of formula `i can be prepared by known mei.hods,
for example where R61 ~s
--IC~?'H2
11
the compound of formula IY can be prepared by reactiny a
compound of formula `JIII
T - C~2 - ~ - t~H - A - NH - R63 (VIII)
where R63 is - C0 ~ N~2
`1 1
with a compound of forrllul~ IX
~H 0
R - ~=G - C - 0 Cl 4al~yl (IX)
S~
- 36 - 1~0-4687
to -form a compound of formula X
R
T ~
O ~ OH ~Rll (X)
A NH- CO ~
2.
followed by reduction of the nitro group to an amino group
or where R61 is hydrogen by saponification of the compound
of formula X.
- Compounds of formula I where Rl is
OH
-N=N-A1-N=N` ~ ~ R
- (so3~)n
R~9
can be prepared by coupling to a diazotised compound of
formula XI
T~N=N-A-N~i2 XI
0~1~`0~1
a compound of formula XIII
3l2~L~
- 36a - 150-46S7
OH
( S03H ) n
Rlg
by known methods.
Compounds oF-formula I where Rl is other than
hydrogen can be prepared by reacting a diazotised compound
of formula XIa or XIIa
OH
NH2-A~N=~ ~so3H)n
19
NH2- K XIIa
.
witll a compound of Formula XIIIa -~
XlIIa
~ ~vv~oH
according to knowr1 methods.
~2~75~
- 37 - 15Q ~687
Couplins to form compounds o~ formula 1 1~here ~1 is
other than hydrogen can be carried out according to knoi.m
methods. Advantageously, coupling is carried out in aqueous
(acid, nelltral Ot` alkali)nledium at a temperature fronn -10C
to room temperature, if necessary in the preser,ce of a
coupling accelerator such as pyridine or urea. Alternatively,
coupling may be effected in a mixture of solvents, for
example~ water and an orcanic solvenl.
Metallisation of the compounds of formula I when R1
is other than hydrogen can be achieved by known metho{ls.
lhe azo compounds of formula I in 1:1 metal complex
form May be prepared by rnetallising compoullds of Formula I
in metal-free form with a metal selected -From copper, cobalt,
iron, nickel, manganese, chromium ancl zinc.
The azo compounds or forlnula I in 1:2 metal complex
form may be prepared by metallising compouncls of formula I
in metal-fr~e form with a metal selected from chromium,
nickel, cobalt and iron.
A flJr-~her method for the preparation of an a~o Compound
of formula I in-1:2 metal complex fornl is ~y reacting
an azo compound of formula I in Inei:al-free form with an
azo compound 1:1 metal complex when the metal is chromium,
nickel, cobalt or iron.
The metallisation process to form a 1:1 metal complex
is advantayeously carried out by treating 1 mole of azo
compound ~/ith a metallising agent containing 1 equivalent
of metal.
Metallisation is carried out
advantageously in aqueous medium or a mixture of wa~er ancl
a water miscible organic solvent, for example acetone,
lower alkyl alcohols, dimethylFormal,1ide, formamide, glycols
or acetic acid at a pH range from 1.0 to 8.0, preferably
pH 2 to 7. The metallisation process na~ be carried out at
a tempera~ure from room t~emperature to the boilir,g po-int of
~z~
- 38 - 150 46&7
the reaction medium.
~ lternatively, metallisation may be effected in a
wholly organic medium (for example dimethylTormamide)~ Advan-
tageollsly, for instance, cobaltisation may be carried out
in the presence of an inorganic nitrite such as lithium,
sodium, ammoniunl or potassium nitrite in the ratio of .' to
6 moles of nitrite per gram atom of cobalt.
Suitable cobalt-yielding compounds are, -for e>;ample,
cobalt (II) or Co (III) sulphate, acetate, formate or
chloride.
Copper-~ieldin~ compounds are~ for example cupric
sulphate, cupric formate, cupric acetate and cupric
chloride.
ThQ nickel-yielding compounds are Ni (II) or Ni (III)
compoullds, such as nickel formate, nickel acetate and nickel
sulphate.
Pre~erred nnanganese-yi21dinq compounds are Mn (IIj
compounds and iron-yielding compounds are Fe (II) or Fe
(III~ compounds. Examples of these and zinc-yielding
compounds are manganes~, iron and zinc formate, acetate
and sulphate.
Preferred chromium-yielding compounds are Cr (II) and
Cr (III) fol^mate~ acetate and sulphate.
In tlle compounds of formula I the anions A~can be
any non-chromophoric anions such as those conventional in
basic dyestu~f chemistry. Suitable anion, include chloride,
bromide, sulphate, bisulph~te, me~hylsulphate,aminosulphonate,
perchlorate, benzenesulphonate, oxalaie~ maleate, acetate,
propionate, lactate~ succinate, tartrate, malate, methane.
sulphonate and ben70ate, as w211 as complex anions, fur
5~
- 39 - 150-4687
example, zinc chloride dou~le salts and anions of ~oric
acid, citric acid, glycollic acid, diglycollic acid and
adipic acid or addi~ion products of orthoboric acid ~lith
polyalcohols with at least one cis diol group present. These
anions can be exchanged for each other by ion exchange resins
or by reaction with acids or salts (for exaMple via the
hydroxide or bicarhonate or according to German Of~enlegungs-
schrift 2,001,7~8 or 2,001,816.
The azo compounds of formula I are suitably worked up
into solid or liquid preparations, for example by granulatiGn
or by dissolving in a suitable solvent. The compounds of
formula I are suitablQ for dyeing, padding or prin~ing on
fibres, threads or textile materi~ls particularly natural
or regenerated cellulose materials for example cotton, or
synthetic poly~mides or svnthetic polyesters in which tho
acid groups have been modified. Such a polyamide is
described in Belgian Paten~ 706,104 ancl such a synthetic
polyester is described in US Patent 3,37g,723.
The compounds of formula I may also be applied to
bast fibres such as hemp, flax, sisal, jute, coir or straw.
The compounds of formula i are also used for dyeint~,
padding or printing fibres, threads or ~extiles producecl
therefrom which consist of or contain homo- or mixed
polymers of acrylonitrile or of 1,1-dicyanoethylene.
The textile material is dyed, printed or pad-dyed
in ac:cordance with known rnethods. hcid modified-polyamide
is dyed particularly advaniageously in an aqueolls, neutral
or acid medium, at temperatur~s of 60~ to boiling point
or a~ temperatures abo~e 100C under pressure.
The textile material may also be dyed by the compounds
of formula I in organic solvents, e.g. in accordance with the
directio!ls given in German O~rerlegungschrift 2,437,549.
S~
- 40 - 150-4687
Cellulose material is mainly dyed by the exhaust
process i.e. from a long or short bath at rooll1 temperature
to boiling temperature optionally under pressure whereby
the ratio of the bath is from 1:1 to 1:100 and preferably
from 1:20 to 1:50. IF dyeing is effected from a short bath~
then the liquor ratio is 1:5 to 1:15. The pH of the dye batn
varies between 3 and 10 ~for short and long dyebaths).
Dyeing preferably ~akes place in the presence of electrolytes.
Printing may be effec~ed by impregnation ~ith a
printing paste produced by known me1~nods.
The dyes of formul~ I are also suitable for dyeing or
printing paper e.g. for the production of bulk-dyed5 sized
and unsized paper. The dyestuffs may similarly be used for
dyeing paper by the dipping process. The dyeing of paper is
effected by known methods.
The dyes of fo~ula I are also suitable for dyeing
or printing leather b~ known methods.
Dyeings ~lith good fastness are obtained on both paper
and leather.
Dyeings made with the dyes of formula I on leather have
good light fastness properties good diffusion properties
~ith PVC good water- wash and sweat-fastness prop~Qrties~
good fastness to dry cleanin~ good fastness to drops of
water and good fastness to hard water.
Dyeings prepared with dyes of formula I (where Rl is
other than hydrogen) on paper produce a substantially clear
spent li~uor which is important for en\!-ironmental reasons.
Th~ dyes of formula I have good ~uild-up properties do
11 Z~
1 50-46P,7
not run cnce applied to paper and are not pH sensitive.
Dyeings produced with dyes of formula I have good light
fastness and the nuance on exposure for a long time io light
fades tone in tone. The dyes of formllla I have good ~ie-t-
fas~ness properties not only for water but also for milk~
soapS water, sodium chloride solution, fruit juice, and
sweetenecl mineral water. Further dyeings made with dyes of
formula I are fast for alcoholic beverages due to a good
alcohol Tastness. Further the dyes of formula I have good
nuance stability.
The dyes of formula I may be converted into dyeing
preparations. Processing into stable liquid cr solid
dyeing preparations may take place in a generally known
manner, advantageously by grinding or granulating or by
dissolving in suitable solvents, optionally adding an
assistant, e~g. a stabiliser or dissolving intermediary such
as urea. Such preparations may be obtained, for example,
as described in French Patent Specificatiorls 1,572,030 and
1,581,900 or in accordànce with German DOS 2,0015~48 and
2,00~816,
Liquid preparations of the compounds of formula I
preferably comprise 10 to 30 /0 by weight of a compound of
formula I and to 30 ~ of a solubilisins agent such as urea,
lactic acid or acetic acid, the rest of the composition being
water. Solid preparations preferably comprise 20 to 80 %
dyestuff, 20 to 80 % solubilising agent such as urea or
Na2SO4 and 2 to 5 ~ water.
In the following Examples all parts and percentages
given are by weigllt and the temperatures giverl are in
degrees Centigrade, unless indicated ~o the contrary.
s~
- 42 - 150-4687
EXAMPLE 1
390 Parts (2 moles) of para-ni~robenzoic acid ethyl ester
are warmed in 3200 parts of ethanol ancl 360 parts (6 moles) of
ethylene diamine at 60-65. After stirring for several hours
a fine crystalline product results which after filtration
produces 350 parts of a compound of forn;ula la)
02N ~ CONHC2H4NH2 la)
having a melting point (of the unpurified product) of 132-134.
A compollnd of formula lb)
NO ~ O ~ -~O',~H-C2H4-N'nCOCH2 ~ C1~3 1b3
is formed by reacting the compound of formula 1a with the
product of slight excess pyridlne and 1 mole of chloroacetic
acid methyl ester, in ethanol at 55C.
Without isolating the corr,pound 1b) 1 mole of acetic acid
methyl ester is added to the reaction mixture and this is
treated at 25C in the presence of base by known methods to
produce a compound of formula lc)
~ ~ ~ Ic)
OH
C2H4NHC ~lo2
hich can be reduced by the Bécharnps method to t'ne corres-
ponding amine.
3L2 ~ 7 S~L
- ~.3 - 15~-~687
After adding water to the reaction mixture, the compound
of formula lc) precipitates out.
The compound of fo!-mula lc) is ~aponified in 5-7 %
hydrochloric acid according to kno~n methods to form an amine
of -formulald)
~H3 ~ ~
~ Cl~ Id)
HO I ~
C2H4NH2
The compound of formula ~d is reacted according to l~nown
methods in water at about 9Q and a pH of 9 with a compound
of formula Ie)
N_~NH-~C~ 3-~t~3)2
C1 ~NO ~ Ie)
NH ~CH2t3 ~(CH3)2
to form a compound of formu1a If)
H2)3-~(CH3~2
C2H~-NH ~
NH~C.~ )3-N(GH3)2
The compound of ~ormula If~ is very ~a~er soluble particularly
in acid medium and can be used as a coupling component in the
prep~ration of azo dyestllffs.
s~
- 44 - 15~-4687
EX~lPLE 2
In a similar manner to the me~hod of Example 1 a
compound o-f the formulâ
~ ~ 2Cl~
o~ l~b
(CH2)~ilHCOCH2N(CH3)3
is formed using 1 3-diaminopropane instead of ethylene di-
amine and chloroâcetylchloride and trimethylamine instead
of the compound of formula le)~
EXhMPLE 3
225 Parts (1.5 moles) of meta amino acetanilide in the
form o~ the acid addition salt are placed in a mixture of
equivoluminar glacial ~cetic acid and ~ater together with
sodium acetate. On cooling to D-5C 254 parts of chloro-
acetylchlor,de (2.25 moles) are added over 2 hours. A product
of the formllla 3a
H ~lHCOCH3
Cl-CH2-CO-N ~ (3a)
is formed. 1 mole of the compound of formula 3a is reacted
according to known methods ~ith 1 mole of pyric,ine to form a
compound OT formula 3b
NHCOCH3
N CH2C-NH ~ Cl~ (3b)
~lithout the need to isolate the compouncl of formula 3b 1 mole
of acetic acid methyl ester is added to the reaclion mixture
and according to kno~m methods al room ~emperature in the
- 4~ - 150-4687
presence of bas2 a compound of formula 3c
~ ~ C1~3 (3c)
o~ rl o
~\
~ HCOCH3
is forrned.
At 95-98C the compound of formula 3c is saponified with
about 5 % hydrochloric acid to form a compound of ~ormula 3d
~ ( ~ (3d
OH 11 O
~ .
~2
The compound of formula 3d is conYerted into that of
form~la 3e
- ~ C7~3 (3e)
OH N O
H(CH2)3 N!C~'3)2
N
NH(cH2)3 ~(C~3)2
S~
- 46 - 150-4~7
in a sir,lilar way to that described in Example 1.
EXAMPLES 4 to 12
Compollnds of the ,ormllla
,¢~ Cl~
OH ~ O
~here R is defined in Ta51e 1 belo~ may be prepared by a
me~hod analosous to th- of Example 1
TABLE 1
__ ________. ___ . __ _ .
Exanlple _
No~ ~
. NHtCH2)3N(C~3)2
4 -(CH2)-2-NHC0 ~ N~ ~ N
- NH(CH2)3N(CH3)2
.. .
~H(CH2)3N(CH3)3
-(CH2)2 NHC ~ '~H ~ ~ N ~ -
_ ~H(cH~)3N(cH3)3
. ~
6 -(CH2)-2-~'H- ~IO~l 2~1 !
NH~`,H2~3N(C'~3)3
12~S~
- 47 - 'I 50-46~7
Tabl~ No 1 continued
Exampl e R ~ ._
N__ NHC~
_ ___ _
8 ~ ~C~ Cl~
H(CH2)3N(CH3)2
NH~CH2)3~(CH3)2
¦ 10 ~ 2 ) 3N ~ C; 13 ?3
~NH~3 2Cl
- ~ CH2 ) 3~ ( C~i3 )3
~ ~ .. ,
NH(CH2)3N(CH3)2
11 ~ ~3
NH(C112 '3N~CH3)2
~2~
- ~a - 15C-46~7
Table No. l continued
__ _ __
No. R
_. _ . _. ..
12~ H(CH2)3N(C~3)2
-CH2CI~=C.~1-0~2-'3H~O~
_ _ _ _ N~1(c1/~l(cll3)2
~XAilPLES 13 to 44
In the followillg ~xamples compollnds of the for~lula
C~,T
0~
A-;'l:.-R2
where T, A and P~2 ar~ giv~rl in Table 2 below, may be
prepared by a method analo~ous to Example l. In Table 2,
T2 to T7 and A2 to A32 ar as given below and A~?is CH3COO~;
T2 represellts -C?~
T3 . do. -CO~'~2
T4 do.
T5 do~
53~
~ ~9 - 1 50 -4687
T6 repres~nts ~3C ~ ~
T7 do . ~~ A(3
'I~CH3
N~--NH(CH2)3~N(C2H5)2
A2 represents ~o ~
"~NH(CH2 )3-''Y(C2H5)2
'(C~2)3-N(C'~3)2
A3 do. -~,O~
l'~t~(CH2)3~ (C~3)2
A4 do. -COCH2-N~CH ) A~
A5 i - CO~O} ~H2
A6 do, -CO ~>--NH-CGC~2-~(CH3!3 A
`t~CI~2)3-N(C2~15)2
A7 cio. -CO-~~
lYH ( CH2 )3~ C2~ ~s ) 2
~'~2)3~ (C2~i5)2
o~ i~
--Cl
N~NH(CH2)3 ~(C2115)2
A~3 do. ~O~
N. 1 C2H~,tO,Y
.... ..
~2~
- 50 - 1 5,r,-46~7
Al o represen~s ~N~o~ J '3
r ~ N - CH3
y,'ii~ iC~)-CIi2-~!(C2!-i5)2
Al 1 do- ~OJl
N~NHNHCO-C~2-ri(C2H5)2
A~2 do. ~ ~ ,'1,'1~'`'(CH3)3 A
N~ ,H~ (C~13)3 A
A13 do. -Co4~ H~o~ ~CONH(CH?)3-~'(C2'i5~2
---,NiH--~CO,YH(Ch'2)3-1l(C2Hs)2
A14 do, ~0~ <~CONH(C~ 2)3-N(C2~5~2
iY,'l--~--CON,Ui(c~-i2)3-N(c2H5)2
AlS do. -CO~> ~NO~ ~N CH
/ \0 CY3
A16 to" _<~o~ ~ --C,-,3 2 A
CH~
~ CH3
~2~.S~
4~7
Rl 7 represents --<~)~
N~
Al ~ do. ~,`1 N-CH3
~lH(CH2)3 ~1(C2~5)2
A~ d --<~ ~J 2 4
N~-C2~ 0~
~-C3~61'~(CH3)2
h~o do. ~N P
-C3~6~(CH3)2
f ~-N(C~13)3
{O~) 2 A
~( c~3)3
~_ NH~--CH2N(CH3)3
~NH~ 2 A~3
C'12~ ~ C~'3 )3
A23 do. ~ ~~ C~ ) A
3~ ( C2~ 2
S~
- 52 - 1~-~0 ~o87
A24 repreâellts ~t~C~
N(CH3)2
A d ~N--~ NH ~ ~
( ~\ ~ 2 ( 3 ) 3
CH ',1 ( i-H
A26 do. -C~ ~ t~C3u61'~(C2,l5)2
NHC3H6N ( C2H5 ) 2
^C~H& ~Il ( CH3 ) 2
A27 do . ~CO--~0~--N~
N'-~-C3~6 -t~ 3 )2
A28 do. -c~<~I~H-~ \~C~12!~(cH3)3
C!.2N ( C,~3 ~3
h23
~2i 14 ~it2
S:~
- 53 - 150-4587
~--13HCOC~2-N(c~3)3
A30 represen ~s ~C~ 2 A
~3~_ Q
NHCOC~2 -~ ( CH3 )3
A31 ~ '.C.O-C~2-~
~N"-C3H6-~(CH,3)2
A32 do. ~O~ ~H24~ 2 A~
NH-C3~-16-~,3(C~)2
CH2 '~
~ 54 - 150-4687
TABLE 2
Example T A R2
___ _
13 H -C2H4- H
14 T2 do. A2
T3 do. A3
16 T~ do~ A4
17 T6 do. A5
.18 T7 do. A6
l9 T4 ~ A7
T4 do. A8
21 T5 do. Ag
22 T4 _ ~ Alo
23 T4 -CH2-CH=CH-CH2- All
24 T2 do. Al2
T4 -C2H4- A13
26 T4 do. Al4
27 T4 do. Al5
28 T4 do. Al6
29 T4 do. h17
T4 do. Al8
31 do. do. A19
32 do. do. A20
33 do. do. A2l
34 do. do. A22
do. do. A23
36 do. do. A2~
37 do. do. ~25
38 do. do. A26
39 do. do. A27
do. do. A28
D, 1 do. do. A29
2 ~L~ L
- 55 - 150-4687
Table No. 2 continued
EXamP~ T A I R2
_ _ _ ___ _j
42 T4 -C2H4- A30
43 . do. do. A31
44 dQ do. A32
EXAMPLE 45
A compound of the formula 45a
~O.~ N=N~NHCOCH3
O ¦ OH ~ H(CH2)3~(CH3)2
C2H4NH~
liH(CH2)3N(CH3)2
is prepared by diazotising 1 mole of 4-amino acetanilide
and coupling with l mole of the compound If of ExaMple l.
Cy the addition of 30 % hydrochloric acid to the
aqueous solution of compound 45a~a 7 % hydrochloric acid
containing solutinn is producecl and this is refluxed for lO
hours. A compound of the formula 45b results
- 56 - 150-~87
~N=N~NH2
o ¦ OH ~ ~(C~2)3~(CH3)~
C2H4NH~N
NH(CH2)3N(C~l3)2 ~
1 mole of the compound 45b is then dia~otised and then is
coupled to 1 mole of a compound of the formula 45c
OH
S03~r ~ ~ NHcocH2N(cH3)3 Cl (45c)
to form a compound of formula 45d
o~
N H S03H NHCOCH2N(CH3)3 Cl
C1~3 ¦ ~ iH(CH2)3N(CH3)2
C2H~ NH ~ (45d)
NH(CH2)3N(CH3)2
and this compound dyes paper a blue v^iolet tone.
A similar product can be obtained by using 1 mole of
a compoun~ of formula 45e
2~l~'7S:~l
- 57 150-4687
OH
so3~, < H(CH2)3N(C2H5)
NH(CH2)3(C2~5)2
instead of the compound of formula 45c
EXA~lPLE 46
6.~ Parts of 1-amino-4 nitrobenzene (l/20 rnole) is
diazotised in hydrochloric acid solution at-O to 5C with
3.5 parts(l/2n mole) sodium nitrite. Then l/40 mole of
the diazonium solutio;l is coupled LO 8 parts of l amino-8-
hydro~ynaphthalene-3,6-disulphonic acid (l/40 mole) at pHl.
The remaining l/40 mole diazonium solution is couplecl at
pH 9 to the monoazo dyesLuFf so formed to form a compound
of formula 46a
OH r~
o2r~ rl=N ~ =r~__ ~ NO2 (46a)
503H S03H
The nitro groups of the compound 45a are reduced
according ~o known methods, Ihen both -NH2 groups so formed
are diazotised and then 1 mole of the diazotised compound is
coupled to 2 moles the compound Ie of Example 1 to form a
compound of formula 46b,
23L~ S~L
- 58 - 150-4~7
46b)
I H ~ H(cH2)3 N(CH3)2 ~5~3H SO~H
C2H4-NH--<(~1 _ _
NH~CH2)3N(CH3)2
-- 2
The compound 46b dyes paper a black tone.
EXAMPLES 47 to 64
Compounds of t'ne formula
CH CH3
T.l\~,N=N-Kl -N=N-K2-il=N-K\3 ~N-~N~Tb
O ~ O ~ IN O
C2H4-NH-R2
in ~Jhich the symbo7s are defined in Table 3 belo~ here symbols
T4 7 and A2 ~ are defined under Exarnples 13 to 44 and the
symbols B2-11 are defined belol~l) can be made in an analogous
nanner to the method of Example 46.
~2 r~presentS -C~15
B3 do, C2H~
B~ do. -(CH2)3~ H3)2
B5 do, -(C~2)3N~c~3~3 CH3S~4
Bb do~ 2)~ I~H2
B7 do. ~'2)3 N~2
~2~S~
- 59 - ~ 50-46~7
~ NH ( C~12 ) 3 -~i ( C2~5 ~ 2
B8 ~2preselltS - ( C1~2 ) 2-~ O '~
.~`NH(CH2)3-~(C2~5~2
B9 do. -(Ci-12)2-~C0CH2-N(CH;~)3 Cl~
Blo do~ NH(CH2)3-1~(C2H5)2
-' NH~CH2)3-~(C2H5)2
N~--NH(C~2)3-''~(C2H5)2
E~ 1 do . - C~H4~'HC0--~>--N'~O~
I~H ( CH2 ) 3 N ( C2H5 ) 2
TA~L E 3
NoTa I R2 I Tb ~ Kl K3 K2
_ _ _ ____ .___ __._ _ ~H2 ~H
47 T5 1~2 T5 B8~/\~ ~> ~ [S03H
48 T4 h2 14 B4 do. Hp do. do.
49 T4 H T5 ~4do . ~_ do .
l-4 A2 T5 B4 ~ ~ clo .
51 T5 A2 T5 - B8 ~} ~'1 do .
52 T4 A2 T4 B~do . ~ do .
53 T5 A2 T5 B8do . do . do .
'iL~2 IL3~5~
- 60 - 1 50--4687
Table 3 (continued)
N__ r ~R ~,T ~, B K
54 T5A2 T6 ~8do . ~ ~ H03
-r4A2 -r~, e4do . do . do .
56 T7A4 T5 B8 ~ ~ do. OH do.
57 T4A2 T4 B,~<~ ~ do ~
~8 T4A2 T~ B~3do . do . do .
59 Tl~ A2 ¦ 4 B~ ~1~3
T5A2 T5 B8 do, do, do,
61 l-4h2 T7 B2do ~ _~ do .
62 T5A2 T4 11 do. do. OH do.
63 T4A2 T4 B4do . ~ do .
64 T5A2 T5 B8do . do . do .
The compounds o~ Examples 47 to 64 d~e paper a black tone.
s~
- 61 - 155-4~7
EXAMPLE 65
1/20 mol of para nitroaniline is diazo~ised and coupled
to 1/20 mol of 1-amino-8-hydroxy-naphthalene-3,6-disulphonic
acid. rO the resulting monoazo dyestu,f, 1j20 mol of diazotisecl
l-alllino 2-hydroxy-4 nitrobenzene is coupled to give a compo~lnd
of ~ormul3 65a
O~N ~ N= ~ ' ~ (65a)
S031J S03~1
The nitro groups of the compound 65a are reduced ~ith
sodium sulphide at pH 11-12. The diamino disazo compourld so
formed is tetrazo~ised as ir, Example 46 and coupled to 1/10
mol o-F the compound o~ Ie oF Example 1 to -Form a compound
of ,or~lula 65b
~? N=r~O}~ N~O~
~H S03~t 3 o N 2C13
¦ ~H(C~12~3N(CH3)2 C2H4-NH
C2H4NH ~ N
NH~CH ) N(CH ), ~~J~
2 3 3 (CH~)2N(CH2)3UN N~(C~l2)3N~ 3)2
This dyesturf dyes paper a bl~ck shade.
This compound may also be m2tallised ~ith copper~ iron5
chromium or cobalt to form a 1:1 metal complex or with chromium,
cobalt or iron to Form a 1:2 metal complex accordinq to known
methods .
5~
- 62 - '150--45~7
EXAMPLES 66 to 68
The follo~/iny compounds can be made by a method
analogous to that of Example 65 (or by other known met.hods)
From the corresponding starting compounds.
AMP1E 6
OH
3 ~N=N ~ N-- ~ ;N- ~ l
OH S03 3 0 ~j O
(C~2)3-~(CH3)~ (Clt2)3N(CH3)2
EXAMPLES 67 and 68
In these Ex(lmples the group Ra is of the fo~:nula
13 N=N ~ N=N ~ - ~
Cl ¦ N4(C112)3N(CH3)2
C2H4~H~O~
... , . . ~H(CH2)3N(CH3)~
-A compour1d of the forr,lula
R 0~1 NH-R2
~ ~ ~ (E,xample 67)
S03H 03H
~here P~2 is A2 (defined unoer Examples 13 to 44 ) r,lay
~L2~7
- 63 -
be prepared by an analogous method to that of Example 46 or by
any other known method.
A compound of the formula
R OH
- ~ (Example 68)
s~3 NH-R2
~ Ihere R2 is A2 (defined under Exainples 13 to 4~.) may be
prepared by an analogous method to that of Example 46 (or by
any otil2r known metllod).
ln Examples 67 and 6~ R2 may be replaced by hydrogen or
any oF the groups A3 to A32 defined under Examples 13 to ~6.
These dyestuffs dye paper a blue t;one.
EXAI~PLES 69 and 70
In tl1ese Examples Rb is a group oF the formula
C13 ~ ~ i 3 ~ -N ~ N=N -
Q 1~ OH
(CH2)3N(CH3)2
A compound of the formula of Example 67 in which Ra is
replaced hy Rb !Example 69) can be prepared by an analogous
method to that of Example 67.
A conlpound of the formula of Example 68 in which R is
replaced by Rb (Exarnple 70) may be prepared by an analogous
s~
- 6~ - 150-45~7
method to that cf Example 63.
In Examples 69 and 70~ R2 may be replaced by hydrogen
or any other group A3 - A32 deFinecl uncler Examples 13 to 44.
The dyeings produced from compounds of Examples 69 and 7n
are Olc a.hlue tone~
EXAMPIE 71
From the corresponding st~rtirlg compounds~ a compound
of the formula 71a
~3 1~ O}-N=~ \1 (71a~
(l~2)3-NtCH3)2
can he prepared by a method analogous to that of Example 45
and from correspollding ,tarting products a compol.lr.d oF formula
71b
OH NH
=N ~ ~ =N ~ ~ (71b)
~ H
(~H2)3-N(C~13)2
can be prepared by a method analogous to that of Example 45.
The compounds of formula 71a and 71b dye paper a blue tone.
EXAMPLE 72
From suitable starting compounds a compound o~ formula
72a
~Z~7.5~
- 65 150-4687
OH
C'l- ~ ~H3 N=N { } N=~ (72a)
N~2
~ 2)3-N(CH3j2
be prepared by a method analogous to that of Exan~p'le 45.
A ccmpound of formula 72b
OH
RC~N=~ N=N ~ ~ ~72b)
S031~ =N-Rc
where Rc is
Cl~
O N, OH
. ( 2)3 (CH3)2
may be formed by dia~otising the compound of formula '~2a
and coupling with a compound of the formula
Th~ compound of formula 72a is violet in colour ~nd the
cPnnpound o~ formu'la 72b dyes paper a black tone,
- 66 - 150-4687
EXAMPLES 73 to 106
B~y an analogous methocl to that or Example 65 (or by any
other knowll method) compounds of the for~ la
T ~ 3 N ~r~ 2~' ~3,`N=~ ~ o ~ ~N-N ~ ~ l
0~ ri~ ~ 0~1 S03~ - OH ~.1.
.
are produced in which the symbols are ci~fined in the l`able 4
below and T2 ~ are defined under Examples 13 to 44 ancl B~ 8
are defined under Examples 47 to 64 and B~i2 is
,NH(CH2)3N(C2H5)2
~O~-NH ~ ~
NH(CH2)3N(C2i~5)2
Sl
- 67 -- 15~-4~87
Table 4
__ _ ____ ____._. _ _ _ ~
_ ~ I _ position of~1,~posi-ticn of
EX~ T T floating ~loGting gp, B e
No.1 grollp in ir~ aphtlla-
_ _ _ _ _ _inq h _ _ _ene ring _ _ _ _
73 T4T4 4' 3-(CH2)3-N(c~l3)2 B~
74 T414 3' 2 do, B~
T4T~, 3' 3 do~ B~
76 T4T4 4' 3 do, H
77 T4-r2 4' 3 ~' e4
73 r4T2 4' 2 do~ B~
79 ~4¦ T2 4' 2 do~ ~4
8Q T4 ¦T2 3' 2 do, B~
81 T4I T4 4~ 2 ~8 B8
82 T4T4 3l 2 B8 B~
83 T4T4 3' 3 E8 B8
84 T~l-4 4' 3 B8
T4r4 4' 3 ~8 H
86 T4T4 4' 2 r38 H
87 T4T4 3' 3 B8 H
88 T4T4 . 3 2 B8 H
89 T4T4 4' 3 B8 R4
90 T4~4 4' 2 e8 B~
91 T4T4 3' 3 B~ E~
92 T4T~ 3' 2 B8 B4
93 T4T2 4' 3 e8 e4
- 6B - 150-4637
T_ble No. 4 contin led
pos i ti on o f
E:~. posi tion of floating gp B
'io l Tl floating gp. in naphtha- B
. . in rinq A lene g~oup
~_ __ ___ ___ .___ _ ___ _ ______ .
94 T4 T~, 4 ' 2 R8 ~
T4 T2 3 ' 3 B8 ~4
96 T4 ~2 3 ' 2 B8 B4
97 T2 T4 ~ ' 3 B4 B4
98 T2 ~4 4 ' 2 B~, B~,
99 T4 Tl~ 4 ' 2 ~4 B~
l O0 T4 T~ 4 ' 3 H 68
l O l T4 T4 4 ' 2 H B8
102 T4 T4 . 4' 2 Bl2 B8
103 T~,, ~4 4 ' 3 do. H
154 T4 T~, 4 ' 2 do~ B4
105 T4 T4 4' 3 do. Bl2
l 06 T4 T,f, 4 ' 2 B8 l 2
5~
.
- 6g - 1~0-46~7
Jhe compounds of Examples 73 to 106 may also contain
OH groups in positions 2', 3' or 4'. In these cases these com-
pounds can be metallised to form l:l metal complexes with
copper, chromium~cobalt or iron or 1:2 metal complexes with
chromium,cobalt or iron.
Compounds of Examples 73-106 may also contain OCH3 groups
in positions 2', 3' or 4'. In these cases these compounds may
be metallised to form l:l metal complexes, preferably with copper.
~ he compounds so formed are of the formula
T~ ~ N-,N~N~37 N N~
o~N~ M 0 3 OH
Bl
or of the formula
0~ ~oN$B ~T~
where Me is copper chromium cobalt or iron (to form 1:1 metal
complexes) or chromium cobalt or iron(to form 1:2 metal
complexes~,
~L2 ~l~L~Y S~L
- 70 - 1~0-46~7
FXAMPLF 107
._____
12.3 Parts of ortho anisidine (0.l mole) are ~liazo~ised
and then coupled to a compoulld of formula 107a
3 ~~
OH ~ ~ NH(cH2)3-~(cz~5)2 (107a)
2H4 NH ~NO~
NH(CH2)3.-N(C~H5)2
to Fornl a compoulld of the formula lQ7b
. ~ ~3~
OH ~ ~ NH(CH2)3-N (C2H5)2 (107b)
(,2H4-NH~
NH~CH2)3-~(C2~5)2
This dyestuf, dyes paper a yellow shade. The dyestur,
107b can be used for dyeing polyacrylonitrile in the mass.
EXAMPLES 10~ to 131
~on,pounds of the formula
H
(CH2i2-~2
3L~ 5~l
- 71 - 15G-46~7
in which T, R2, Ra and Rb are defin~d in Table 5 below and
significances T2 7 and h2 4 ;~re defined under Examples 13 tG
~, can be prepared by d m2tho~ analogous to that of Example
107,
rx. ¦ 1 R2 ¦ Si~llificance ~ ~a arld I Sisnificar,c2 of R~ and
~1 I ~C`s ~ tio~ Fh~ in~ I Ph~r~yl
.__ _~__ __ __ ~P_ __ _
108 H A2 l H
lû9 T2 A3 3-Cl H
11 r3 A2 4-Cl H
111 T4 H t'
112 T4 H 2-~;32 H
113 r~ ~ 2-'~0 4-Cl
-114 T4 ~2 H H
1 1 ~ -r9 A2 2~
116 T4 A2 2-Cl 4-t3(1
117 T4 ~2 4-0 ~ -Cl
118 T4 A3 H ~
119 T4 A4 2-~30? 4-Cl
120 T4 A4 ~-Gcn3 _~
121¦T5 ~ H ;~ ~ H
- 7Z - '150-~6~7
Tabl e No . , conti nue~
______ _ _ . _ _ _ _
EX. T R Sianifica1lca of P; and Significar,c2 o, Rb
No 2 dan-l ~os i tion in
_ _ _ position ,~n rn~;n~l rin~ rhenyl rin~
122 T5 ~'2 4-t~C2 -1~
123 T5 ~2 2-Cl 4-i~2
124 T5 A4 4~Q ~ Cl -H
125 T6 H _~
126 T6 A2 4~ H
127 T6 A4 2-Cl ~?-Nn2
12;3 T7 A2 2-,~ 4-Cl
129 T7 A4 4-~ ~ Cl H
130 T4 A2 2-C~3 ~-CH3
131 T~ A~ 2-OCH3 ~-nc~3
132 T4 A4 2-C~3 ~ 3-C113
The dyestufTs of Exa",ples 108 to 132 produce dyeings of
a ye11Ow tone. lhese dyestu.fs are also useful for dyeing poly-
acrylonitrile in the mass.
EXA~lPLE i 33
~
Using suitable s~ar;ing co-npounds3 a compound of
formula 133a
~Z~1~5~
- 73 - 150-46?l7
~ CO } ~=~ C~ (133a)
Cl 0~ ~`I ~OH N ~H(C~2)3~ CH2~3-l~(c2H5)2
C2~4~
.(CH2~3-1'(C2H5)2
may be prepared using an analogous metnod to Example 107.
3yeinys so produced are of a gold-yello~I tcne.
EX MP S 134 to 139
Compounds of the formul~
-IY- ~ IY N ~ ~ 45
C2H4 R~
in which the symbols are given in Table 6 belo~ may be prepared
by kno~n methods from suitable starting compounds.
TabIe 6
EX ~ 2 ¦ a Rb ¦ Rs ¦ t _
134 T5 A2 -OCH3 -CH3 4-CH3 H
135 T7 h2 do -OCH3 2 OCH3 H
136 T~ A~ do do 2-CH~ 5-CH3
137 T~ h~ oo -CH3 4-C4iIy H
13B T5 h4 d o -OCH3 2-OCH3 5-.~H3
139 T4 A2 -CH3 -OCH3 2-OCH3 ~
~Z~ 5~
- ~4 - 150-4687
The compounds of Examples 134 to 13~ produce dyeings of
gold-yellow to oranye tones and have good fastness properties.
EXAMPLES 140 to 162
Compo~ ds of the formula
N ~i ~ 3 r
1~ OH
C2H4 P'2
in ~hich the symbols are defined in Table 7 belo~/ (symbols
T2 7 and A2 4 are defined undel Exalllples 13 to 44 and symbols
B2 11 are defined under Examples 47 to 64) may be made by
analogous niethods to that oF Example 107 from suitable starting
compounds .
T ble 7
EX l T ¦ R2 ¦ Pf10atjjn9 IT1 B
_~ t r1Zn 9~P T4 6
141 H A2 - H H
142 12 A2 4 T3 B?
143 T3 A4 4 T4 3
144 T4 H 4 H 64
145 T5 H 4 H B~
146 H A2 4 T4 B6
147 T6 A2 4 T2 B7
1~ ~;~ /\~
7 ~L
. - 75 - ,~50-~5~7
~ble 7 co t.
E~ T T~ posit-.ion o, tTl e
No floati~
azo aroup
__. _ . __ .. . .. .. ~ . ~ . ~__
1~9 H ii ~, T~ e9
150 H A2 4 I~ ~8
151 H A4 4 ~ B9
152 T4 It 3 T4 B6
15~ T~ H 3 ~5 B6
154 T4 H 4 -r~ B6
155¦ T5 H 3 T5 B6
156 T~ A2 3 T5 H
157 T5 A4 3 T6 H
153 T3 A2 3 T5 B2
159 T4 H 4 T~ el
160 T5 A2 3 T4 B.l
161 T4 H 3 T~t Bl
162¦ T5 A2 4 T4 ~1 1
_, _ __ _
Compourlds of Examples 140 to 151, 154, 159 and 162 produce dyeings of
clyeings of a Yiolet tone ~hereas the conilpounds of Examples
152, 153, 155 ~o 158, 160 and 151 produce dyeings of a
reddish yellow to orange tone.
EXAMPLES 163 tn 1~6
Compounds of the formula
- 76 - 150-4687
/ N=N-~
t~N=N {~4
I `OH
C2H4 R2
in ~hich the symbols are defined in Table 8 below,nlay be
prepared by an analogous method to that of Exa~ple 107.
Symbols T2 4 and A2 ~ are defined under Examples 13 to 4
and symbols Kl 17 are given helow.
Compouncis of Examples 163 to 168, 179 and 185 produce
dyeings of a red shade, of Examples 169 to 175, 183 and 184
a yellow tone, of Examples 176 to 178 a blue tone and o~
Exarnples 180 to 182 and 186 ~n orarlge tone.
Kl represents -C = C >t~ri
~13C-C = ~
K2 do -C = C\t~l C ~ ~H2 AC3
CH3-C = tl N~l2
K3 do ~C C /rt_
i~3C-C = ~
H3C-C - t~ cocH2t~(cH3)3 A
/0~1
K5 do -C = C >
H C C = N '-- ~3
3 ~CO~H2~`1(Ci~
- 77 - 1 50-f~6~7
~ t~'~2
K6 -C --- C~
I~ C-C = ~
3 CH30
7 do CH3COCHCONH -
CH30
~`3 ~ C113COCI~C~
CH2N(CH3)3 Cl~
K9 do CH3COCHCO- NH - ~ ~NH(C~12)3r~(C2H5)2
NH < 0~
(C~12)3N(C2H~)2
H(CH2)3N(C2H5)2
Ylo do CH3COCHCONH ~ H-~ O N
(CI-i2)3~l(C2H5)2
~11 r~r~sents CH3COCHCON~ rHCOC~21~(CH3)3 C~
. NHcocH2N(cl~3)3 Cl
K12 do CH3COCHCO`rlH ~
13 C113COCI~COl~iH ~ S021H(C~2~3~(cH3)2
Kl4 do ~ OH
CO~H(C~i~)3N ! CH3)2
K15 do ~ \ C 'ri
3~2~L~L~5~L
_ ~2 _ 150-4687
~16 ~'e~ Sents - CO}~ Cl~3
C~ ."~ ~ ( C~3 )2
Kl 7 do ~3G~O~
~H~CH~)2
~`18 do - ~OH
~i')le 8
EX. T A ~ Positi3n oF,, :Oting
~o. I azo gr~ K
_ __ _
163 T4 A2 4 ~ Y~l
164 T5 A2 ~ ~ K2
l 65 T6 A~ 4 _ K3
166 T4 A~ 4-- K4
167 T5 A~ 4 - K5
168 T2 A2 K
169 H A2 4 - '~7
17G T4 h4 4 K8
171 H A4 4 - Kg
172 T5 H 4 - Klo
173 T5 h4 4 - Kl l
174 T6 A4 4 - Kl 2
175 T7 A2 4~ Kl ~
176 T4 A2 4~ Kl4
177 T4 A2 4 - K ~l 5
178 T5 A4 ~- Y~16
17~ T6 h2 4~~ Kl7
180 T5 A2 4-- Kl8
s~
- 79 - ~50-~87
Table No. 8 cont i nued
_ _ _ _, _ _ _ _ _
EX. T 1 2 Fosiiion o~ _ _
No. l f'loating azo group ~ .
181 T4 A2- - ---3~ K -- -
182 T6 H 3_ K5
183 T7 tl3_ K8
184 T3 A~3_ K12
185 T~ A~ 3 ~14
186 T5 F!_ _ ___ ~ _____ _ _ _ _ _
EXAilPLES 187 to 243
__ _ _______
According to a me-ttlod analogous to that of Example
107 compounds oF formula
T~~ --~X--~O~\~
o~ o~ c
(Ctl2)2-R2 ( H2)2 P~2
in ~Ihich the symbols are defined in Table 9 belo~ here the
symbols A2_4 and R2 7 are defined under Examples 13 to 44 ar,d
those symbols of Xl l08 used in Table 9 are defined below)
can be prepared.
The symbols Xl to Xln~ used in Tab'7e 9 are as ,ollo~ls: -
Xl is a di~ect bondX -S-, X6 -O-, X7 CHOCH-~ X,tO -NH-~ X11 N
X12 -~t-CO-,
X16 -NH CO ~ X17 -S02-Ntl-~ X22 -CO-N!-I-Nt-l-CO~
-, ~Z~l~Sl
- ~0 - 150-4687
~ GH2-CH2 \ N - N
X26 - C-CO- ~i-CO- O- , X27 -C~ ~C-,
\C~12-C~2~ 0
X30 ~ C , X~5 -CH~-NII-CO-NH-CH2-, X49 ~CH2-CO-C'-i2-,
n n
X50 -CH-CH-CH=CH-. X51 -CO { O } - ~ ~ CO
X52 -CO- ~ ~H2 ~ CO-, X53 -CO ~ CO-
X54 -C~ -CH2-NH-CO-, X5~ C~2 CO ,
X59 -CH-CH-CO-CH-CH- ! X60 -C~i\~cii-
X61 -CH~ ~ C~2-, X62 -0-C1~2-C~'2 '
~J .
X6~ -CO-~H~R43-~0-NH-, X70 -NH-CO-NH-
X7~ -CO-~ ~ -NH-CO-, X73 -NHCOCH2CH2CO-NH
X74 -NH-CO-CH-CH^CO~NH- X75 -N~'-CO(CH2)4~CO-NH-
X79 -N - C~ \ C - ~-, Xgo -Nli-C C-i`iH-,
CH~ N~ , N CH3 N~`C
R P~45a
4~
~z~s~
- 8 l - 1 50-4ij87
81 C~i2 ~ X82 -(C~2)?-~ X~5 -G0-NH-(CH2)2-NH-Co
X86Co-NH-(cH2)3-NH-l~o-~X87 C0 NH (C~l2)~
( H2, 2 l~ C:)-, X~g -CO-N,I -CH2-CH-NH-C~)-
C~ 13 Cr~3 c"3
X90 -C0-lNL,-C~-I-CH-N.i-C0- st~
~3C CH3
};100 CO ~ P~3 C~ N~ R4s Nl! C~,
)~101 -Co-~-R43~ -co-cl~2-c~2-~ H ~43 ~
X102 - CO- NH-R43-NH-C0 -C ~=C1t-C0- I\lH- R43 I~-C0-,
X j 03 -CO-N~-~43-NH-~o,`r~ ,3 N~ ~0
P'45
X104 S2~l`lRq~ 2~5-~3~ -S02-
Xl o~ -CO-I~R,,4-5~43-0-CO-,
Xl 06 ~~-C0 -~>-C0-0-,
xl07 -co-o~O~-n-co-,
. 1 0~ Co~H-p~q3-~H-co-!~ R4~ -co-
~Z~
1 5~-46g7
P g
EX I T R2 X EX T ¦ P2 X
___ ___ .. ____ _~ ____ . _ . ._
l ~7 H A2 X~ 211 -r.7 h~X62
1 ~8 T2 A2 X5 212 T4 A2~ 70
189 T3 A2 X6 213 H A2X7 I
190 14 A4 X7 214 IT2 A2¦ X73
191 T5 A4 Xlo 215 T4 2 74
192 T6 A2 Xl l 216 5 A4X75
193 T7 r~2 X12 217 T~ A2X79
194 T9 r~2 X~6 21& 1 Q~X~o
195 H A2 X17 21 ~ 15 A2 X~
196 ! ~ A4 X22 220 T,~ A2X82
1~7 ~I A2 X26 ?21 .r4 ~2 X~
198 1 -rfi ~4 ~27 2~'~ r5 A2X8~
199 I T5 ~ X33 223 T5 ll~87
! 6 A2 ~ 45 224 17 A3~88
201 T7 A2 X49 225 T2 A2X~9
202 T~ ¦ A~ X50 226 ' 3 A4Xgo
203 T5 ~ ~2 X~
204 T6 ¦ h~ X5~
205 T7 1 A2 X53
206 H ! A2 ~54
207 2 A2 X5
208 T4 A~; X~,9
209 T5 H j X60
210 ¦ ~6 A2 ¦ X61
Js~
- 83 - 150-~5~7
Ta_le No. 9 contillued
EX . T A X
No .
_ .___ _. ~
227 T4 ~2 ~;103 (ir ~-~2~ n~ H(C~2)2-3-N(C2~5)2
228 T5 A2 X107
229 1~ A2 -CO?t,Y(i' H ,)~^QN i(' H2)2~ CO-
2~ T2 A2 do
231 T3 A2 -CONH' 2~ IN '~Q~ =Ci'Cn,~HC2~4N~.'C0-
23~ T~ A3 -CO~H'i^ Ir, `;I`'CCIC H CONHC H NhC0-
233 T5 A4 X 1 Q~
1~ C~AN,-~CO-
234 rr h2 - CC?iH -C~'r' ';~ ~'O`r'
r~c2~ o
235 ¦ ~4 ~ 2 -CON,IC H~' r'~ ~ 2H4liH
236 T4 i:~ l
237 T4 H x~5
233 T4 H X~2
23g T4 H X71
24CI T4 ~2 Xl l
241 T~ A2 X~5
242 T4 h2 Xs2
243 T '~A2 ~71
~z~s~
- 84 - 150-46~7
Compoullds of Examples 187 and 212 dye paper a red tone;
Compound.; of Examples 188 to 190 194 to 197~ 1~9 to 201
203 to 211 214 to 216 and 219 to 235 237 23~ ~40 to
243 dye paper a yello~ tone; the compound of Example 191
clyes paper a blue tone and compounds of Examples 192 193
198 202 213~2.17 to 21B and 235 to 233 dye paper an
oran~e tolle.
EXAMPL.E 244
Using suitable starting compounds and a method
analo~olls ~o that of Exam?le 107 a compound of the forimll~
{ O } CO~H ~ O~ - ~;N-C-C~. ~ NIICOCH~I.(CIl ~3
21~4~ 2
may be prepared. This compound clyes paper a red-yellow tone.
EXAMPLES _45 to 258
Compounds of formula
~=N ~ X-- C ~ ~=N
t~ OH Oi
( H2)?-R2 B
in which the symbols are given in Table 10 belo~l and symbols
A2 ~ a~ld T2 7 are cgiven under Examples 13 to 44~ ~2 11 are
ciefined un(ler Examples 47 to 64; K~ 17 are defined under
Examples 163 to 186 and the symbols Xl l08 used in Table 10
are defin~d ur.der Examples 187 to 243.
~z~
- 85 - 150-4687
Compounds of Examples 245, 252 and 258 dye paper a red
tone, eolnpounds o~ Examples 246, 24S, and 257 dye paper
an oral~a tone, the compound ~f Example 247 dyes paper a
blue tone and ~he compounds of Examples 249 to 251 and 253
to 256 dye paper a yello~ tone.
_able 10
I~O I 2 1 ¦ ¦ X
___ _____. , _,___
245 H h2 T4 ~ I Xl
246 T2 A2 T5 ~2 X2
247 T3 A3 T6 B3 XlO
24B T4 t~ H e~4 Xll
249 15 A2 T~ B6 X51
250 T.6 A2 T5 B~ x53
251 T7 h~ H BS x59
252 T4 h4 T5 ~ ~70
253 T~ ~`2 H H X~l
254 ~4 h4 T2 B4 X82
255 T5 A2 T4 H X25
256 -~4 A4 T4 H X~6
257 T~ A2 T~ B~o Xll
258 ¦ T4 j A2 ¦ T4 Bll X70
7S~
86 - 15Q-~6~7
EXAMPL :S_259 to 26~3
Compounds o, the ~or~ l a
r~ =N _~~~ X--CO~ N=~ - K
o 1~
C2H ~N~'-22
hic~ 1;he symhols are gi~er. in Table 11 below5 may be
p~epared in a manner analcgous to that of Example lC7
abl e 11
FX T 1 l~2 I X I )~
259 T~ h2 X1 1~
260 r5 ~2 X6 1!~4
261 '' ~4 Xll ~'
262 T4 H Xl ~ ~ 7
253 T5 A4 X55 K8
264 T4 A2 X59 I`l 0
265 T6 A4 X70 Kl l
266 T7 A2 X82 ~ 16
267 T4 A2 X85 ~17
268 T5 A2 X~ 1 ~1 ~
The compound of Exampl e 262 d~es paper a red tcrl.e,
compounds c,f Examples 259 to 201 dye paper an ~ran}~ tone
~'7 S ~
- 87 - 15G-4687
and compounds o-f Exalnples 262 to 268 dye paper a yellow Lo)le.
EXAMPLE 269
_____. _
Starting ~lith a monoazo c.ompounfi Qf the fOrinllla(259
C1 ~ 269a)
OH
C21'4NH;~
and reactir)g ~ith~yanu)ic chloridela comPound o~ fnrmu'a
26g~
) ~ ~ N ~ N=N ~
OH N ~NH(CH2)3N(C2H~)2 269b
(CH2) -NH-~ O N
may be -formec;.
B~ reacting the compound of formula 269b with 269c
CH ~ ~ 269c
N
O I OH
) 2NI'12
in water at 90C and at pH 9, a compound of th~ formula
2&9d
~z~
1 50-G68 /
~H~
J ~ t~ (,69d)
C~2-Cli2~ C~2 C~2 ~3
NH~CH2)3~(C~)2
may be formed by a method anàlogous to that of Example '1.
The co,npourl~! oF Example 269d dyes paper a yello~,i tone.
EX.~MPIE 270
A compound o~ the fo~mula 27~a
Cl ~ t~ N'~2 (270a)
C 11 OH ~ tC~2)3N~C2H5~2
~ NH(CH2)3N(C~ )2
is diazotised and then coupled to 2-amino-1,4-d,rnethyl-
benzene. The resulting disazo compound is furthei diazotised
and then coupled to a compound o F the formula H K5
Q~
~ ~ H-K5
C~~ = N' NHCOCH2-~1(CI~3)3
to ~orm a compound of the formula 270b
3LZ~L~L~5~L
- ~9 - 150-46~7
CH
H . COCH N(CH )
_~~'N~I(C~2)3N(CH5)3 2C1~3 2 3
2H4NH ~ ~ (270b)
( 2)3N(CH5)2
This dyestuff dyes paper a brown tone. Instead of
coupling to 2-amino-1,4-dimethylbenzene, an equi~alent amount
of 2-methoxy-5~methylaniline will produce.a compound of the
formula 270c
N-N ~ ~ C
¦ H NH(CH2)3N(C2H5)2 2Cl~ COCH2N(CH3)
(CH2)2NH ~ (270c)
NH(CH2)3Nt (C2H5)2 '
r~sl.~lts.
The compound 270c dyes paper a brown ton~.
The compound Z70c can be metallised by known methods
with such metals as copper, to form a compound of formula 270d
~ILZ~5~
- 90 - 150-~687
N=N ~ N=N ~ ~ C - C
N C 3 CH3___c===N - ~
H NHCO~H N(CH~)
2Cl ~ NH(CH2)3N(c2H5)2 2C1~3 2 J
(Cl ~2)2N ~ O~ ` (270d)
~(CHz)3N (C2H5)2
where Me is copper~
EXAMPLES 271 to 283
Compounds of the formula
$~N=N_X_N=~T
H 0
(CH2)2-R2 B
where the symbols are defined in Table 12 below may be made by
a method analogous to that of Example 270 and then metallised.
Symbols B2 11 are given under Examples 47 to 64 and symbols
A2_4 and T2 7~are given under Examples 13 to 44.
The compounds of Examples 271 to 273 and 277 to 281 dye
paper a violet tone and compounds of Examples 274 to 276 and
282 to 283 dye paper a blue tone.
~2~1~S~
- 9 1 - 1 50-46~7
Table 12 cont~ ed
r~O T h T~ I R2 ¦ X
2~ rS ~2 1 T5 I B8 ~;
272 T4 4 3 ~ do 3
273 T~,A2 ~ ~ ~1 OCH
274 HA2 r4 ~8 ¦ ~--N r~
275 I ~ '~2 T ~ ¦
276 T~th2 l l ~CH3 3
277 I T4 ~ H ~ T4 ! B6 ~ =r ~
278 T~;A2 T4 ~ ¦ do
279 T4A2 T4 æ~ do
2gO T4A2 T4 ~ 3 1 ~o~ 3
281 T5A4 T7 h' do
282 1 T42 4 ~ g ~
283 T~h~ 1-7 ~ ~
EXAMPLES 284 t o 297
In a similar m3nnor .o the method Gf Exarnple "70
compounds of the ;ormula
- ~2 - 1~0-4687
CH
. 1 3
' ~ , ~ =N-X-N=N-K
0~" 1'J~`OH
(CH2)2-R2
~here the symbols are clerilled in Iable 13 below, can be pre--
pared. Symbols K2 17 are defined under Lxamples 163 to 186.
The compounds o~ Examples 284 to 289 and 292~to 295 d~e
paper a ~Jiolet tone and compollnds of Examples 290, 2gl,
296 and 297 d~e paper a blue tone.
Table 13
E~' ¦ T ¦ T~ X
__ _ ~ ~ _ _ _ Cl CH3
2û4 T5 A2 K5 ~ ~
285 T6 A4 K,3 do
286 H H ~`17 OC~
287 T4 A2 K3 CH3
288 T~ A2 Klo do
289 T6 A2 K~ do
290 T4 A2 K4 - ~ t~-~
OC~3
5~L
93 -1 50-46~7
EX _~ ~
291 ~r7 A4 Kl ~ do
292 T,~ 1~ ~--ri=i
293 ~5 Afi Kl ~ do
2g4 r4 A2 K~(~`4~
296~ ¦ 2 r 1O(~ tl ~
297A2 ~5 do
EXAlYiPLt.S 298 to 300
Compounds of the formula
3 ~ ~ N=N-K
N
,~ (C1~2)3~ ~21'5)2
( CH2) 2 NH~,~
~'~ ( C~2 )3~ ~ 5 h'
- 94 - 150-~5~7
may be formed .~y diazotising a co;npound of ,ormula 270a arld
then couplinq with a compound H-K
here K is
~ ~ NH ~ ~ NH(C~2)3N(C2~l5)2
ON EXaIn?1e 2~
NH(CH2)3N(C2~15)2
\ ~ NHrlHcocH~N(cH3)3 Example 29~
OH ~ ~ NHcocH~ c~3)3 Example 30C
The couplin~ components H-K can be Inade fron~ kno~"n
compounds by known methods.
EX~MPLE_301
a) Preparation o-F a coupling compon2nt of formula 301a
NH(CH2)3N(C2~l5)2
N ~
lH NH ~ ~ (301a)
SO H--~)~S NH(C~2)3N(C2H5)2
91 Parts of cyanuric ct,loride are suspended in 2~,0 parts
of an ice/water Mixture. 133 Parts of N,l~-diethylamino
propylamine is added dropwise at 5 to 10 and the ~nixtllre
is stirred for 3 hours a~',er ~/hich 1'77 parts of 1-hydroxy-
~ 2~S~
- g5 - ~50-46g7
8-aminonaphthalene-3 6~disulphonic acid is added~ The temper-
ature is raised t:o 90 and the pH is held at 2.5 to 3 by the
port.ionwise addition of 54 parts of sodium acetate. After 2
hours condensation is ~erminated. The solution is allo~ed to
cool whilst stirring to 20 wllere the desired crystalline
product deposits. The product is filtered and 265 parts of
a grey product results contalning 217 parts of the coupling
component 301a .
b) Preparation o-f an amino component of formula 301b
C~l~
~ ~ 1 N=N~ 2 (301b)
0~
30 Parts of 4-aminoacetani!ide are reacted in 500 parts
of an ice/water mixture at 0C with 50 parts o-f concentrated
hydrochloric acid. After tnis addition 55 parts of a 4N
sodium nitrite solution is added dropwise follo~ed ~y 42
parts of 6-hydroxy-9-methyl-3-pyridinium ?yrid-~-one and this
miV~ture is brought to pH ~ by the addition ofsodiumcarbonate.
Coupling occurs imrnediately and an orange dyestuff results.
After coupling is completed the compound is fillered and the
resulting press cake is suspended in 300 parts of water and
then reacted with 100 parts of concentrated hydrochloric acid
and heated to 95C. The splitting off of the acetyl group is
completed after 2 hours. ~~he resultillg solution is cooled ..o
room temperature by stirring and the dyestuff o-f formula
301b falls out as yellow crystals. This is -filtered washed
with brine and dried. 170 Parts of a yellow powder results.
containing 68 parts of the compound of formula 301b .
c) Preparation of a compound o-f the formula 301c
~Z~L~7S~
- g6 - 150-4687
NH(CH2)3NH(~2~'~)2
N-~l ~ N OH NH ~ ~ (301c)
OH ~ ~ ' ~ NH(CH2)3N~(C2H~)2
~ 0.5 Parts oF the compound of Formllla 301a are suspended
in 200 parts of water and dissolved therein by the addition of
sodi UM hydroxide.
22 ~ Parts of the compound of formula 301b is diazo~ised
by ~no~ln metnods and the resulting diazo solu-tion is added
drop~ise to the compound of formula 301a and the pH of the
reaction is held at 8 to 9 by the addition of sodiun1 hydroY~ide.
Coupling occurs immediately to give a blue dyestuff. After
termination of coupling the pH is reduced to 7.5 by the drop-
wise addition of concentrated hydrochloric acicl and the dye-
stuff falls out completely and therl is filtered and dried. The
dyestuff is blue in colour and in the form of its acid addition
salt dyes paper a blue colour. The remaining dyebath is colour~
less. The ~et-fastnesses of the dyeings so produced are good.
EXAMPLE 302
... .. .. _
The compound of formula 301c may be prepared by coupling
4-aminoacetanilide to the compound of formllla 301a followed
by saponifyiny in acid medium diazotising and then coupling
to 6-hydroxy~4-methyl 3-pyridinium-pyrid-2-one.
XAMPLE 303
Instead of using 4-amir,oanillne in the method of Example
3013 p-n;troaniline is used rollowed by reducing the nitro
group in an al ali medium of a sulphuric acid salt. The
resulting dyestuff is o-f formula 301c.
5~l
- 97 - 15Q-4687
EXAMPLES 304 to 34U
Compounds of tha ~or~lula
OH
R-N=N-X-N-I~ ~ S~)3~1)n
4 5
in ~/hich the symbols are de,ined in Table 1~ belo~l,can be
prepared by methods analoyol.ls to Examples 301 to 303.
In these EY~amples
IlH(cH2)3~(c2H5)2
Yl represen~s ~
liH~cll2~3N(c2H5)2
Y2 r~presents ~iH~CH2)3N(C~3)2
2~3N(CH3)2
Y3 reprPsents NH(CH2)2N(C2H5)2
\?~HICH2)2l~(c2H5)2
and
Y~,,, represellts ) ~ )
~ `~H(c~3N~cH3)
~Z~
- 98 - 150-4687
In group X the starred carbon atom is attached to the
azo ~roup a~tached to the pyridone.
In colunln I the numbers 1 to 9 represent the colour of
the compoul1d of the particular Example.
1 = orange 2 = bluc,ish-red 3 = reddish-blue
4 = blue 5 = grey~blue 6 = red-violet
7 = blue-violet 8 = violet 9 - bro~n
The position of grollps is given by a f-igllre in brackets.
ABLE 14
EX. R ¦ X i T S03H ~ ~.roup
,rouo _ _ _ la ~
3~4~ .,3 _. ~ 1 (3) -~ C31~6N~C~i3)2 8
305 d~. do. do. -~H~ (6) 7
306 do. do. s~o. -~3-~'2 (6~ 7
O do. do. do. -~H-~'4 (6) 7
3 8 do. do. do. -~H-~1 (7) 5
309 do. do. do. -NH-Y3 (7) - 5
310do . do . d o . -`~ CO~H (~ ) C 1~3 6
311 do. do.2 (3 j6) -~ ' (8) 4
312 do. do . do . -~ y3 (8) 4
313 do. do; do. ~ 54 (8) 4
31 4d o . ~- 1 (3 ) --~ 1 ( 6 )
31~ do. do. do. -~ -Y2 (6) 1
~2~
-- 99 -- 1 50--.607
Table No. 14 continued
___ _ _
EX, R X n and pos. R1 an~ pos. I
No, _ S()3H groupof '`1 a 5~UP
~~ c~;' ~------- _ .
31 6 C 1 O~J~3~oH ~ 2 ( 3; ~ ) ~ -Yl (8 ) G
317 do. do C133 do. 3 ( ) 6
318 d o . . r~ d o .--~EI~ ) 4
319 do. dcO; do. -~-Y~ (8) 4
320 do. .. ~ do.-~ih-Yl (8) 4
321 do. Cl do. do. 4
32'~ do . ~ do ~ do . 4
Ci~3cH3
323 do . ~ do, do . 4
324 do . ~ do .do . 4
C133
325 do. doO do.-'~l-Y2 ~8) 4
326 . do. ~ do.' ;; Yl (~') 3
OC~i3
~33
327 ¦ Cl ~11 ~ ¦ do. ¦ do. ~ 4
~,28 do. do. dio. -.;il-Y2 (~ 4
- 121~S~
-- 1 Q 0 -- 1 ~ 0 ~ c~7
-- T 1_No. 1_ontinu:d
EY~ 7 R ~i In and p3S.I Rl~ an~l DOS. I
~o 1f S~3~16f Rla 'Ircu~ j I
___ ..... _ __ ,, ,,~rsl~p~___ ~
329 ~ 'C'I3 j2~ 2 (3; 6~ YI 8) ~ 4
' ~ ~ O'l
~JC133 1 .
3 3 ~ ~ do . d o . 3 ~7
O l OH l ll
C3~6~ ,3~,3~
Cl
@ c~
331 ~3~f~`~' d c . d o . d o . 4
Ci~ `0.1
C3 6~(C~3)~1
332 do. dc. do. -3~H-Y (3) 4
_ '~') ~73~
3aa Cl O ~ OH do . d o Y -~H -~i (8) 4
CH3
334 ~1~'
O ~/ OH ~3 d o . d c3 . d o . 4
Cl .
~ C~i2~; (C~i3) 3 1
- 33:~ ~ d~. ~O. ~O. 4
0~
' ~ Yl ~ . ~7
51
- 1 31 - 1 5û-4687
Tab1e No. 14 conti,iu~d
_ . .. ~ _. __.. _
~ n anu ~ ~ ana pos
E X . R ,~ pos i -ti on of pOao i -t i on of
i~!o. ~ C.H . ___ SO~i groll,) Rla ~roup __¦
336 c]~lol ~c~ 2(3;6) -~-Y](8
337 do. ~:~i3 f~'~3do. -~ Y 3 (~3~ ~
338 d o . ~~~ d o . ~ ( 8) 4
33~3 ~ `Oi~ 1~{-~ ~(4) ~3 2
340 ; ~ ¦ do. C~
_ _ _ __ ,_.~
EYAMPLE 341
_
Sl;arting ~ith a coinl~ound of formula 341a
O , 0~ ( 341 a
c3~i5~ ~c~.3? ,~ ~cl ..
a coinpound of th~ fGr~ru1l 341b.
~2~1~5~L
- l 02 - l 5n-~r687
~ ~(C~l3)2 35 ~I-]
can be prepared as f'ollo~s.
The compound of ~ormllla 341a can be made by an an31Gsous
method lo that O-,c Example 45.
75 Parts oF a compound of formula 341aare diazotised
with 3 parts of a 4i~ sodium nitrice so'lution to ~.Yhich an a'lkali
solutioll containing 2.5 parts of ~95'-dihydroxy-7 7'-disulpho-
252'-dinaphthyl urea is adcled dropwise. Coupling is fully
coMpleted by the addition of 10 parts OlC NaOH and a compound of
formula 341b resul1;s having a blue tone.
EXAMPL.ES 34~ to 348
Colnpound of the fornlula
E Y~--
can L~e prepared by a rnethod analogous ~o that of Example 341
using suitable starting ma-terials. The symbols are deirined
in Table 15 belo~ In colurnn I the co'lour nunlberals in
colulnn 1 are as for Exarnples 304 to 340 ~ith additionally
lG = bro~nish-red and 11 - blac~.
3l2~1'75~1.
- l 03 - l 50-4587
_l t) 1 ~ 1 5
E~ l ~B _ L
3;Q ¦ ~ r~ -(C1l2)3~(C2~l5~2
34 3 d o . -- ( C~2~ ( C~3) 2 d o . 1 0
.. 0~
344 do. do. (5~ )
345 Ido. ! ~ 5 l~
346 ~O~ (Cl~2)3~CH3)2 ~ . l 1
~3 S03~ ~;03H
347 Cli . ~ do. 1 l
~ 1 .
348 do. ~ do. l l
, - ~n~ 2 ~ ___
__ ___ . _
~2~
- iO~ - 150-~6~7
.X~ P~ 9
From appropriate starting compounds ~ compound of the
for~ la 349a
~ ~ {O~ ~ (3~9a)
O 1`' OH O~S 1i~ C
]~ }I ~'
can he prepared. The co ~o~nd 34ga dyes paper a grey-violet
tone.
_XAMPi.E 350
10 Par-Ls of tile dyes~uff o, Example 318 are stirred in
200 parts of water and warmed to ~0. A solut~ion of 3 par~s
copper sulphate pencahydrate in 20 parts water and 15 parts of
concentrated ammonia is poured inko the dyestulCf solution and
tlle temperature is r3ised ro ~0 to 95. After ~. hou s metalli-
sation is termina~ed~ 33 pa~ts of NaCl are aclded the ~ixture
is cooled to room tempera~ure ~nd finally 5 parts OT sodium
hydroxide are added drGpwt e.
A dyestulf of TO~;Ula 35Ga
~-c~ 3~l6~(c21-~5~2
Ce3 ( 50 )
results. In acid addition sal~ form compourld ~50a dyes
paper a grey brown tone. The spent liquor is practica!ly
colourless and ~he we~ f~s~rlesses and ligh~ -fastresses
are excellent.
- 12~L7S~
- 105 150-~6~7
_XAMF'LF. 35A~
28 Parts of the conpour,d 301c powder are dissolved in 9Q
parts of wat~r and ,0 parts of lactic acid whilst stirring and
di ssol ve at 60. Then the dyes~ uff sol u~;i on i s cl ear -f i l tered .
One obtains 12~s parts of a filtrate wshicsh iS stable to storage
for several montils and ,,hich neiiher under ~Yarrn nor cold con-
c,itions allo~s the dyestufr t~S be deposited. This dyest.uff
solutioll may be used dir~ctly (or tilinned ~lit.h water) in dyeing
paper .
EXAMPLE 352
24 Parts of the compound 301c po~der are stirred into
500 parts of water and thell the rnixture is acidlfied with 5
parts of ylacial acetic acid. The dy~stuff dissolv~s in
solution and t.hen the solu~ion is dried. A compound of for,nula
352a
(c2~ )2
~N~ ~\O~ ( 35~)
~ ~3 ' 3~6~ ~C2I15) ~ ' crl13coo}~
resu~ts, having in po,lder for~ a high solubil1ty in cold water.
In Exanlpl2s 351 and 3,2 instead of the acids used, suc'n
acids as hydrochloric, sulphuric3 phosphoric and fornlic acids
may be used and instead o, the dyestuFf 301c anyone of the
compounds of Examples 302 to 3-,0 may be used.
EXAMPLE 353
80 Parts of the dyestuf. of 301c powder are stirred
into a solution of 20 parts dextrin, 20 parts of glacial
acetic acid and 30C parts 0' water and a homcc,~eneous suspension
suspension results. The mi.xtu,-e is ato~1lised and a blue
granulate results havir.g good handle properties and little
dust. Paper can be dyed a blue torle by addirlg the granulate
to a pâper mass.
5~L
- 106 - 15Q-4687
In a similar fashion a granulate may be made ,r~m any
one of compounds of Exalnples 1 to ~99 and 302 to B50.
Application Fxan le A
/0 Parts of chen1ically bleached sulphite cellulose
obtained from pil-le~ood and 30 parts of chernically bleached
sulphite cellulose obtained frGm birchwood a e ground in 2000
parts of ~ater in a ilollander. 0.5 Parts of the dyestufF from
Example 301 of formula 301c (as an acid addition salt e.g.
Example ~51) are sprinkled into this pulp. Paper is produced
from this pulp after mixing For 20 minutes. The absorbent
paper which is obtained in this manner is dyed in a blue ~one.
The waste watc?r is practically colourl~?ss.
Applical;ion Fxamp_e B
0.5 Parts of the dyestuff from Example 301 of formula
301c (as an acid addition salt~ e.g. Exall1ple 351) are added
to 100 parls of chenlically bleached sulphite cellulose which
ha~e been ground in a Hollander with 200 parts oF water.
Sizing ta~es place after thorollgll mixing for 15 minli~es. The
paper which is produced from tlis material has a blue -tone
and ~ood light- and ~et-fastnesses.
Application Example C
An absorbent length of unsized paper is drawn at 4U to
50C through a dyes~uff solution having the following
composition:
0.5 parts of the dyestuff from Example 314 (as an
acid addition salt)
0.~ parts or starch and
99.0 parts of water.
The excess dyestuff solution is squeezQd ou-~ through
two rollers. The dried length of paper is dved in an orange
~2~L~7~i~
107 - 150~ 7
tone.
Application Example D
_ __ _ . _
100 Parts freshly tanned and neut.ralised chrome leather
are agitcltecl for 30 minutes in a vessel with a dyebath of
250 parls water at 55C and 0.5 parts of the dyestuff of
Examples 34G in acid addition salt form and then treated in
the sanle bath for 30 minutes with 2 parts oF an anionic fat.-y
liquor based on sulphonated crain oil. The lea-ther is t;len
dried and prepared in the norinal way givir,g a leather evenly
dyed in a black tone.
Other lo~Y affinity vegetable-t3.llned leathers can
similarly be dyed by known methods.
Appl _ t _n_ExamE~e E
2 Parts of the dyestuff oF Example 350 ir. acid additioll
salt forln are dissolved in 4000 parts demineralised ~acer at
40C. lOQ Parts of a pre-wetted cotton texti 1e substrate are
added and ~he ba~.h is raised to boi.ling pointv over 30
minut2s and held at the boil for 1 hour~ After rinsing and
drying a greyish-blue dyeing is obtained having good light-
and ~let-fastnesses. The dye exhausts practically totally
and the waste wat.er is almost colourless.
The dyestuffs of any of the other Examples may be used
in place of the compound of the particular Example named in
ally one of Application Examples A to C (if Examples 301 to
353 then in acid addition salt form). The dyes so used may be
in the ,orm of solid or liquid preparations.
