Note: Descriptions are shown in the official language in which they were submitted.
~V~ 69
The present invention relates to metal-containing disazomethine com-
pounds, to a process for preparing them and to their use as colorants.
The novel compounds have the general formulae ~Ia), (Ib), and (Ic)
X ~ O - M - Z Z - M - O _ ~ X (Ia)
CH = N A N = CH
X ~ O _ M _ O ~ (Ib)
CH = N 1~ = CH
X ~ ,~ X
= ' ` CH
CH N N CH (Ic)
X~ ~ X
wherein A is a straight-chain or branched alkylene radical which may be
interrupted by one or more moieties selected from the group consisting of
hetero atoms, isocyclic rings and other bivalent groups, or is a cycloalky-
lene radical or an arylene radical, R is a covalent bond or is defined
as A, Z as a group capable of forming a metal complex is an -O-, -COO-
or a lower alkoxy group, for example a methoxy or ethoxy group, or an aminogroup optionally substituted by lower alkyl or aryl radicals such as phenyl
-2-
.
7~
.. , .,. -
... . .. . ~ . .. .. . . .
: . . . ~ . :. .
1~89869
radicals, for example the -N~phenyl)-group, or a carboxylic acid- (Cl-C5)-
alkyl ester radical, for example the carboxylic acid methyl ester group, or Z
stands for a carbonamide group or for a sulfonic acid amide radical optionally
substituted at one or two nitrogens by lower alkyl or aryl groups (phenyl
groups), X is a carboxylic acid group, carboxylic acid ester group, an option-
ally substituted carboxylic acid amide or carboxylic acid hydrazide group and
M is a bivalent copper, cobalt, nickel, zinc or manganese atom.
The invention especially concerns the compounds of the above-mention-
ed formulae (Ia) to (Ic), in which the radicals X in the same molecule have
the same meaning and each Z represents identical groups.
There are especially preferred compounds of the formulae (Ia) to (Ic),
in which R is a covalent bond, or A and R each are an alkylene radical having
2 to 8 carbon atoms which may be interrupted by a phenylene or cyclohexylene
radical, or is a cyclohexylene radical or a phenylene radical, which may be
substituted preferably by 1 or 2 substituents thereof, by chlorine atoms,
lower alkyl, especially methyl, ethyl, lower alkoxy, especially methoxy and
ethoxy, nitro, trifluoromethyl, carboxylic acid-(C1-C5)-alkyl ester groups,
carboxylic acid amide, carboxylic acid phenyl amide, acetylamino, benzoylamino,
sulfonic acid amide, sulfonic acid-(Cl-C5)-alkylamide and/or sulfonic acid phenyl
amide groups, or A or R represents a naphthylene, quinoline, benzimidazolone
or phthalimide radical.
There are furthermore especially preferred compounds of the formula
(Ia), wherein A stands for the diphenylene radical, Z is oxygen or the radical
of the formula -C0-0-, the carbonyl group of it being bound to the radical A,
the X groups are identical or different, preferably identical, and each stands
for a carboxylic acid group, a carboxylic acid-(Cl-C4)-alkyl-ester group, car-
boxylic acid amide or carboxylic acid methyl amide group, and M is a copper
atom, furthermore compounds of the formula (Ib) wherein R is an alkylene radi-
__
~ , -3-
.. . ~ .
. ~ - .
.. .. .
' . . . '- . - .. . . - :
.
10~9~9
cal having 2 to 6 carbon atoms which may be interrupted by, preferably 1 or 2,
groups of the formula -NH- or -NtCH3)-, or is the ortho-phenylene radical which
may be substituted by preferably 1 or 2, substituents selected from the group
consisting of chlorine, methyl, ethyl, nitro, carboxy, carbomethoxy, carbeth-
oxy, from the two last compounds preferably carbomethoxy, carboxylic acid
amide, carboxylic acid phenylamide, acetylamino, benzoylamino, and sulfonic
acid phenylamide, and the X are identical or different, preferably identical,
and each of it represents the carboxylic acid group, a carboxylic acid-(Cl-C4-
alkyl)-ester group, the carboxylic acid amide group, a carboxylic acid-tCl-C4-
alkyl)-amide group, carboxylic acid-di-(Cl-C4-alkyl)-amide group, carboxylic
acid phenylamide or carboxylic acid phenylhydrazide group, and M stands for
nickel, as well as compounds of the formula (Ic) wherein the X are identical
or different, preferably identical, and each of it stands for the carboxylic
acid group, carboxylic acid amide, carbomethoxy or carbethoxy group and M is
nickel.
Among these compounds, those of the formula
~ ..
CH = N N = CH
~ O -- Ni--O =
X X
are particularly interesting in which Y stands for hydrogen, methyl or carboxy,
ant the X groups are identical or different, preforably identical, and each
represents a carboxy, carboxylic acid amide or carboxylic acid phenylamide
group; the nickel complex compounds of the Examples 24, 28, 32, 36 and 39 may
....,"~,
- :- , : - .: . - :
~, . .~ . . . . .
.' . ~' ' ., '" .;, '' ' . :, ' .: . '
1~)89~9
be particularly mentioned.
The compounds of the invention may be prepared by condensing one mol
of one or several amines of the formula (IIa) or (IIb)
H2N - A - NH2 (IIa)
H2N - R - NH2 (IIb)
wherein A and R have the above meaning and 2 groups ~ are bound to A, with 2
ls of one or several compour,ds of the formula (III)
X ~ (!11)
CHO
wherein X has the above meaning, and metallizing the disazomethine compounds
simultaneously or in a following process step by means of a copper, cobalt,
nickel, zinc or manganese-yielting agent.
The condensation of the diamines of the formulae (II) with compounts
of the for~ula III m~y be carried out in water aDd iD
.
B~
-5-
. ~ . .. . - . .. . .
~ , ~ . ,. :. - : . :
10~ 9 HCE 75/F 190
an organic solvent, such as an aliphatic alcohol, an aliphatic
carboxylic acid, dimethylformamide, xylene, chlorobenzene, o-di-
chlorobenzene,nitrobenzene or glycol ethers. It generally proceeds
fast and quantitatively, at a temperature of 50 to 100C. It may
be useful to work in a solvent or in a mixture of solvents at
a higher temperature, for example at 150C or above, and to ef-
fect simultaneously an azeotropic distillation of the water set
free by condensation.
The preparation of metal complex compounds may be carried
out as follows: the condensation described above of the amine
of the formula II with compounds of the formula III takes place
in the presence or with the addition of the metal-yielding agents,
or the metalfree dyestuff prepared first and optionally isolated
is subsequently treated with the metal-yielding agents, using
water or in an organic solvent or solvent mixture, for example
one of the above solvents, and optionally maintaining exact pH
conditions and defined temperatures.
Metallization is generally carried out according to usual
analogous processes, for example at temperatures between 60C
and ~20C and at a pH value of from 3 to 9, preferably 3,5 to
6; but in the preparation of the compounds of the formula (Ic)
a pH value above 7, preferably fro~ 7 to 9 has to be observed.
Instead of the free amines of the formula (II), also their
salts, for example the chlorhydrates or sulfates, may be used
for the reaction with the compounds of the formula (III), option-
ally in the presence of an acid-binding agent, such as an alka-
line or alkaline earth carbonate or -hydroxide.
- The diamines of the formula (II) to be used as starting
2~ compounds are for example hydrazine, aliphatic diamines having a
-- 6 --
. : ; - .
,
. . .
HOE 7S/F 190
m~s~6s
straight-chained or branched alkylene radical of 2 to 8 carbon
atoms which may be interrupted by hetero atoms, such as oxygen,
sulfur or nitrogen atoms, by isocyclic radicals, for example
cycloalkylene or a phenylene radical or by other bivalent groups
or are cycloaliphatic diamines, such as cyclopentylene or cyclo-
hexylene diamines, aromatic diamines of the benzene, naphthalene
or anthraquinone series as well as those of the general formulae
NH2 ~ D ~ ~~- NH ~ NH2
wherein D is a single bond, an oxygen or sulfur atoms, a -NH-
group, -N(alkyl-1-4)-, -C~2-, -CH-CH-, -CO-, -CONH-, -NHCONH-,
-CO-NH-CO-NH-, -SO-, -SO2-, -SO2NH- or -N=N- group, E is an oxy-
gen or sulfur atom, a -NH-, -N(alkyl 1-4)-, -CH2-, -CO-, -C~=CH-,
-CONH-, -NHCONH-, -SO2-, -SO2NH- or -N=N- group and the aromatic
nuclei , each may be substituted by one or several, preferably
1 or 2 substituents selected from a group consisting of halogen,
such as chlorine, bromine, nitro, lower alkyl, cy ano, trifluoro-
methyl, hydroxy, amino, lower alkylamino, arylamino such as phenyl-
amino, lower alkoxy, carboxy, carboxylic acid -(C1-CS-alkyl)-
ester, carboxylic acid hydrazide, hydroxamic acid, sulfonic
acid ester, sulfonic acid amide optionally substituted/such as
by lower alkyl and/or phenyl and acylamino of an aliphatic lower
carboxylic acid or aromatic carboxylic acid, such as acetyl
amin~, propionyl amino or benzoylamino; furthermore suitable
amines are heterocyclic diamines, for example diaminopyridines.
Preferred diamines are diamines with carbonamide groups, especial-
ly with cyclic carbonamide groups, especially diamines of the
-- 7 --
10d9'd~
general formula
~[ (CO)3
wherein R2 is hydrogen, a lower alkyl or phenyl radical, and m and n, identical
or different, are each 1 or 2, whereby the sum of m and n is 3 or 4, and the
group of the formula L (NR2)n(CO)m~ in which -NR2- and -CO- are in any de-
sired arrangement to each other, forms together with two ortho-standing carbon
atoms of the ring system B a five- or six-membered heterocyclic ring; further-
more there are especially preferred diamines of the formulae (II) which are
substituted in o-position - to one of the amino groups by a ligand Z which
is hydroxy, lower alkoxy, carboxy amino, amino substituted by lower alkyl ant/
or aryl radicals (phenyl radicals), a carboxylic acid-(Cl-C5)-ester group,
carboxylic acid amide or a sulfonic acid amide unsubstituted or substituted
st the one or two N-atoms by lower alkyl and/or aryl groups (phenyl groups).
As metals M are preferred zinc and cobalt and especially preferred
are copper and nickel.
The aldehyde of the formula (III) used as starting compounds are
compounds easy to prepare. For preparing them, for example compounds of the
formula IV
~ -8-
.. , - . . :, . -
.: : ` `. .. :: , ., ` . . `.
` . . ` ~ .` . .. . .
. - . ~ ~ ; . , .
`, .
,
HOE 75/F 190
69
X~
~ OH (IV)
in which X has the above meaning, are reacted in lower aliphatic
carboxylic acids with hexamethylene tetramine.
The novel compounds are valuable colorants, preferably as
pigments, and are suitable, - especially after a conditioning
usual for pigment dyestuffs - , for example for coloring plastic
masses which are masses which either are free from solvents and
contain a solvent or are free from softening agents or contain
a softening agent of plastics or synthetic resins, for the pig-
mentation of paints on an oily or aqueous base as well as of
lacquers of different types, for the spin-dyeing of viscose and
cellulose acetate or for the pigmentation of polyethylene, poly-
styrene, polyvinyl chloride, caoutchouc and synthetic leather.
They may also be used in printing pastes for graphic industry,
for coloring paper masses, for the coating of textiles or pig-
ment printing.
The dyeings obtained have an excellent fastness to migration,
to light, to weather and to solvents; they shows an excellent
fastness to heat and are characterized by a high tinctorial
strength, a good transparency and frequently by surprisingly pure
shades.
The following Examples illustrate the invention. Parts
and percentages are by weight unless stated otherwise.
E X A M P L E 1:
21.6 Parts of 1-formyl-2-hydroxy-6-naphthoic acid are added,
while stirring, to a solution of 3.0 parts of 1,2-diaminoethane,
_ g _
. . - - - -
. .-
: . . - - . - . .
- . .
HOE 75/F 190
1()t~9~ 3
in 250 parts of ethanol and 10 parts of glacial acetic acid,
and heated for 3 hours at the boil. After cooling the yellow
compound is suction-filtered and washed well with ethanol. The
moist product is then introcuded into 150 parts of dimethylform-
amide, mixed with 9.0 parts of nickel diacetate and heated for
4 hours at 120C. The yellow pigment thus obtained is filtered
hot, washed well, first with water, then with ethanol. After
drying 30.2 parts of the yellow pigment of the formula
C~ - N ~ (CH2)2- ~ ~ CH
~ ~ O - Ni 0 ~
HOOC COOH
with the analysis: Ni calculated: 11.4 %
found: 11.3 %,
are obtained, which dyes polyvinyl chloride in a clear yellow
shade having excellent fastness properties.
E X A M P L E 2:
21.6 Parts of 1-formyl-2-hydroxy-6-naphthoic acid, 3.0 parts
of diaminoethane and 9.0 parts of nickel diacetate are heated in
300 parts of ethanol for 5 hours at the boil. The yellow com-
pound is then filtered hot and washed well with hot water and
ethanol. The product is then heated in 150 parts of dimethyl-
formamide for 1 hour at 120C, filtered hot and washed well
with hot water and ethanol. After drying 31.0 parts of a yellow
pigment are obtained which is identical with the pigment obtain-
ed according to Example 1.
In similar and analogous manner as described in the above
-- ~O --
.,
.
.
' ' ~.
` HOE 75/F 190
i~8~8~i9
Examples 1 or 2, also the following nickel complex compounds
listed in the subsequent Table 1 according to the following for-
mula with R and X indicated therein, can be prepared:
T A B L E
Shade in ~olyvinyl
Example R ~ chloride ~PVC)
.: - .
3 CH2C~2 -COOCH3 yellow
4 CH2CH2 , COOC~2C~2CH2CH3 yellow
-CH2CH2- -CON~2 yellow
CE2C~2 -CON~CH~ ye~Ilow~~~
7 C~2C~2 -CONXCH2CH2CH2CH3 yellow---
8 C~2CH2 -CON (C4 ~ )2 yeilow
9 -C~2CX2- -CONHCH2C~2~(C~3)2 ~eilow
-CH2CH2- -CONH ~ . _yeliow-g$een
11 - -C~2C~2- -CON~ . yellow-green
12 -(CH2)4- -COOH yeilow-grëer.
.
13 -(C~2)6- -COOH - yeiiow green
. . .. .. . .
.. . . . . . . . . . . .
HOE 75/F 190
iO~869
~xample R ~ vinyl chloride (PVC~
14 -(C~2)3NH(CH2)3 -COO~ y~llow-green
Cl 3
~(CH2)3N(CH2)3- -COOH yellow-green
.
16 ~C~2)6 -COOCH~ yellow-~ree~
E X A M P L E 17:
22.9 Parts of 1-formyl-2-hydroxy-6-naphthoic acid methyl
amide are introduced, while stirring, to 12.2 parts of 3,3'-di-
methoxy-4,4'-diaminodiphenyl in 200 parts of ethanol and 10 parts
of gla~ial acetic acid, and the whole i9 refluxed for 4 hours.
The red compound is suction-filtered, washed well with ethanol
and then introduced again into 300 parts of ethanol. 21.0 Parts
of copper acetate are added and the mixture is heated for 6 hours
at the boil. The yellow pigment is filtered hot and washed well
with hot water and ethanol. After drying 34.6 parts of the com-
pound of the formula
,,,
. - 12 -
,,, ': ' `'~ ~` '
HOE 75/F 190
,., 10~9~
CH ~ N - C~.
~ O ~O . 'O~ ~0~
~ CO~HCH
H3CNHOC . 3
are obtained.
Analysis: Cu calculated: 16.7 %
found: 16.9 %
The pigment thus obtained dyes polyvinyl chloride in a dull
yellow shade having very good fastness properties.
According to analogous processes as described above, the
copper complex compounds listed in the following Table 2 cor-
responding to the following general formula
Cu~ ~z~CU; ~X
with X and Z indicated therein, can be prepared:
- 13 -
HOE 75/F 190
9l~69
--T A B L E 2
_
Ex ~ e ~ z Shade ~n PVC
_
18 -COOH ~ -O- yellow brown
19 -COOCH3 -O- n n
--CONH2 ~C00~ ~~ n
21 --COO~I ~C00~ --- -
22 -COOC~3 -COO- ~ n
23 -co-OC~2CX2CH2CH~ -COO-
E X A M P L E 24:
5.4 Parts of 1.2-diaminobenzene are dissolved in 170 parts
of ethanol and 10 parts of glacial acetic acid. While stirring~
21.6 parts of l-formyl-2-hydroxy-6-naphthoic acid are introduced,
and the solution is heated at the boil for three hours.
The yellow bis-azomethine is filtered hot, washed well with
ethanol and then introduced in the moist state into 200 parts
of dimethylformamide. The mixture is heated to 100C, and
then 9.0 parts of nickel diacetate are added. After heating for
3 hours, the red pigment prepared is filtered and washed well
with hot water and ethanol. After drying 33.4 parts of the pig-
ment of the formula
.
: ' ` - ' '
.: .
HOE 75/F 190
lS)89~69
~ .
C~ - N N = C~
,J~ o'~i~o ~
~IOOC COO~I
.... .
are obtained.
Analysis: Ni calculated: 10.5 ~
found: 10.3 %
The pigment dyes polyvinyl chloride in a brownish red hav-
ing an excellent fastness to bleeding.
X A M P L E 2 5:
2.8 Parts of 1,2-diaminobenzene and 11.3 parts of 1-formyl-
2-hydroxy-6-naphthoic acid are heated in 100 parts of dimethyl-
formamide for one hour at 120C. Then 4.5 parts of nickel di-
acetate are added and heated for 3 hours at 120C. The red com-
pound is filtered hot and washed well with hot water and etha-
nol. After drying 14.2 part of a red pigment are obtained,
which is identical with the pigment prepared according to Ex-
ample 24.
In corresponding way as described in the previous Examples
the nickel comples compounds listed in the following Table 3 and
correqponding to the following formula
CH ~ N N - C~
Ni /
- 15 -
: - . ,, - . ` - j . . '
.
.. , .. . .: .
.
HOE 75/F 190
lV~
with X and Y indicated in the Table, are obtained.
T A B L E 3
ExampIe-z~ ~ Y ~hade ~ PVC
. ~ . . .
26 -COOCH~; H or~nge
27 -COOCR2CH2C~I2C~3 H orange
28 -C~2 H red
29 --CON}ICX3 H . red
-CO~ICH2CH2C~2C~3 H red
31 -CO~CH CH2~ ~ 3
2 ~ CH3 re~~
32 -CON}I ~3 H . ora~ge
33 -CO~} ~3 ~ orange
34 . -COOH N02 ` r~d
-COOH Cl . -r~d
36 -COOH 3 re~
- 16 -
HOE 75/F 190
1~9~69
~x~mple- 2
y Shade -
r_ _ in~PVC
37 -COO~ -NHCOCH3 red -
38 -COOH -~HCO ~ n
39 -COOX -COO~ n
-COO~ . -CON~2 ~ --
4l -COOH -CON~
42 -COO~ -SO
43 -C~2 ~2
44 -CON~c~2cH2cH2c~3 -COOH n
--CO~IC~2C~2CH2C~3 --COOC~I3 n
-COOc~3
E X A M P L E 47:
11.5 Parts of formyl-2-hydroxy-6-naphthoic acid methyl
ester are added, while stirring, to 1.5 parts of a 80 % b. w.
hydrazine hydrate in 150 parts of ethanol. The mixture is
heated at the boil for 3 hours. The 3 parts of sodium-acetate
and 4.5 parts of nickel diacetate are added, and the whole is
heated again for S hours at the boil. The pH value is constantly
ma~ntained above 7 with the aid of diluted aqueous sodium hydro-
xide solution.
' ' ., ' . ~
. . - ` ~ , ' . ' - ~,
.
HOE 75/F 190
The yellow compound is then filtered hot, washed well with
hot water and ethanol. After drying 14.3 parts of a yellow pig-
ment is obtained which corresponds to the formula Ic wherein
R is a single bond, M is Ni and X is -COOCH3.
A lacquer pigmented therewith and having been used for
coating shows a good fastness to overvarnishing and to light.
E X A M P L E 48:
11.5 Parts of 1-formyl-2-hydroxy-6-naphthoic acid methyl
ester are added, while stirring, to 1.5 parts of a 80 ~ b.w.
hydrazine hydrate in 150 parts of ethanol. The mixture is heat-
ed at the ~oil for 3 hours, and the yellow compound is filtered
hot, washed well with ethanol and introduced in the moist state
into 100 parts of dimethylformamide. 5.0 Parts of nickel di-
acetate and 30 parts of sodium acetate are added at 100C, and
the mixture is stirred for 5 hours at this temperature. The yel-
low complex compound thus obtained is filtered at 30 - 40C and
washed well with hot water and ethanol. After drying, 9.8
parts of a yellow pigment are obtained which i5 identical to
the pigment obtained according to Example 47.
If in Example 47 the 1-formyl-2-hydroxy-6-naphthoic acid
methyl ester is replaced by one of the aldehydes listed in Table
4, the corresponding nickel complex compounds corresponding
to the general formula (Ic) with R and X indicated therein, are
obtained,
- ~8 -
HOE ?5/E 190
-` 108'38ti9
TA s LE 4
. . .
- '~ample_ ~ldeh~de R 2 Sha~e in
- lacquer~
C~O '
H2NC ~ C~2 ~ ~ellow
C~O
HO-C ~_ OH _ COOX yelI~
-- 19 --
, . ~ ,, . , - - :
. -, .. : :
-~ ~. . . . ..
