Note: Descriptions are shown in the official language in which they were submitted.
ll~Z515
3-11698+
Azo dyestuff sulfonic acid salts, process for their manufacture
and their use.
-
The invention relates to azo dyestuff sulfonic acid salts of theformula
~ A ~ ~P== ~ ) ~ (S03 BB)m (1)
or of a tautomer thereof, wherein A represents a carbocyclic or
heterocyclic aromatic radical, B represents an aliphatic, cyclo-
aliphatic or araliphatic amine, X represents a hydrogen atom or an
alkyl group, which is unsubstituted or substituted by a hydroxyl
group, an alkoxy group of 1 to ~ carbon atoms, a phenyl radical, which
is unsub8tituted or substituted by chlorine, methyl or -S03~1, by
a methoxycarbonyl, ethoxycarbonyl or phenoxycarbonyl group, or if n
is 1 by a radical of the formula
~ ~ (S3-~B~m (2),
further X represents a cycloalkyl, aral~yl or aryl group, Y re-
presents a hydrogen or halogen atom or an electrophilic group, for
example a nitro, cyano, acyl, sulfonic acid, arylsulfonyl, alkoxy-
carbonyl group,Or an alkyl ~roup which is unsubstit~ted or substituted
by a sulfonic acid group or an alkanoylamino group of 2 to 7 carbon
~'~*
515
atoms, or a sulfamoyl or carbamoyl group, Z represents an alkyl group,
which is unsubstituted or substituted by a sulfonic acid group or a
phenyl radical, or an aryl radical, and m and n are 1 or 2.
If n is 1, A represents a monovalent, preferably carbocyclic,
aromatic radical, for example a naphthalene radical, but in particular
a substituted phenyl radical. If n is 2, A represents a divalent
radical, preferably a diphenyl, tiphenyl ether or diphenylsulfonyl
radical.
An alkyl group X is preferably a Cl-C18alkyl group.
A cycloalkyl group X is in particular cyclohexyl. An aralkyl
group X is in particular a phenylalkyl group containing 1 to 4 carbon
atoms in the alkyl moiety. An aryl group X is preferably phenyl which
i6 unsubstituted or substituted by chlorine, methyl or -S03H. An
alkyl group Y is preferably a Cl-C6alkyl group. An acyl group Y is
preferably an alkanoyl group of 2 to 7 carbon atoms or a benzoyl
group. Carbamoyl or sulfamoyl represented by Y can be unsubstituted
or substituted by one or two Cl-C6alkyl groups or a phenyl radical
which is unsubstituted or substituted by chlorine atoms or methyl
groups. An alkoxycarbonyl group Y preferably contains 2 to 7 carbon
atoms. As an arylsulfonyl group, Y is preferably a phenylsulfonyl
group. An alkyl group Z preferably contains I to 6 carbon atoms. As
an aryl radical, Z is preferably a phenyl radical which can be substi-
tuted by chlorine, methyl or Cl-C6alkoxy. The -S~3-HB group or groups
are preferably in the radical A and A~.
`` ~l'~Z515
Preferrred dye salts are those of the formula
O3~H3N - ~ - 3 ~3
L ~1 a3m
Xl ~
wherein Al represents a phenyl radical which can be subst;tuted by
halogen atoms, methyl, nitro or sulfonic acid groups, alkoxy groups
of 1 to 6 carbon atoms, alkoxycarbonyl groups of 2 to 7 carbon
atoms, or phenoxy, phenylazo or phenylsulfonyl groups which are un-
substituted or substituted by halogen atoms, methyl or sulfonic acid
groups, or by a naphthalene radical which contains 1 to 2 sulfonic
acid groups, Rl, R2 and R3 represent alkyl radicals containing
together 7 to 24 carbon atoms, Xl represents a hydrogen atom, an
alkyl, hydroxyalkyl, alkoxyalkyl or cyanoalkyl group of 1 to 18
carbon atoms, a cycloalkyl group of 6 to 10 carbon atoms, an
aralkyl group of 7 to 10 carbon atoms or a phenyl group which
is unsubstituted or substituted by halogen atoms, alkyl or alkoxy
groups of 1 to 6 carbon atoms, Yl represents a hydrogen atom, a
cyano or sulfomethyl group, an alkoxycarbonyl group of 2 to 6 carbon
atoms or a group of the formula -CONR4R5, wherein R4 and R5 repre-
sent hydrogen atoms or alkyl groups of 1 to 6 carbon atoms and m
is 1 or 2, and, in particular, those of the formula (3) wherein
Al represents a radical of the formula U
V~
wherein U represents a chlorine atom, a methyl, nitro or sulfonic
acid group, an alkoxy group of 1 to 4 carbon atoms, an alkoxycarbonyl
group of 2 to 5 carbon atoms, V represents a hydrogen atom or a
sulfonic acid group, and W represents a hydrogen atom, a methyl
iS
group or an alkoxy group of 1 to 4 carbon atoms.
The dye salts of the present inventi~n are obtained by re-
acting the corresponding azo dyestuff monosulfonic or disulfonic acid
with 1 or 2 moles respectively of the amine B.
The azo dyestuff sulfonic acids are known compounds which
are described, for example, in the following publications:
German Offenlegungsschriften:
1 924 570, 2 004 487, 2 050 901, 2 134 453, 2 150 817,
2 237 006,. 2 533 723, 1 930 491, 2 004 488, 2 115 449, 2 141 449,
2 162 612, 2 238 795, 2 545 828, 1 956 142, 2 033 281, 2 123 061,
2 141 453, 2 216 206, 2 349 709, 2 701 290
British patent specifications:
1 296 857, 1 331 261, 1 345 864.
The azo dyestuff sulfonic acids are obtained by coupling
a diazotised or tetraazotised carbocyclic or heterocyclic aromatic
amine with a pyridone of the formula
H ~ (~)
or of a tautomer thereof, wherein Q represents a hydrogen atom or
an easily removable radical, for example the carbamoyl group and
X, Y and Z have the given meanings, the components being so chosen
that the resulting azo dye contains at least one sulfonic acid
group.
As amines there are preferably used aminobenzenes, in
particular those of the formula
1142S15
(6)
wherein U, V and W have the given meanings.
Examples of such amines are:
aniline
2-, 3- or 4-nitroaniline
2-, 3- or 4-chloroaniline
2- or 4-methylaniline
2- or 4-methoxyaniline
methyl anthranilate
ethyl anthranilate
aniline-2-, 3- or 4-sulfonic acid
aniline-2,4-disulfonic acid
aniline-2,5-disulfonic acid
2-nitroaniline-4-sulfonic acid
4-nitroaniline-2-sulfonic acid
2-nitro-6-methoxyaniline-4-sulfonic acid
4-nitro-2-methoxyaniline-6-sulfonic acid
4-methylaniline-2-sulfonic acid
2-methylaniline-4-sulfonic acid
2-chloroaniline-5-sulfonic acid
4-chloroaniline-3-sulfonic acid
2-amino-4,4'-dichloro-diphenyloxide-2'-sulfonic acid
2-amino-3'-sulfo-diphenylsulfonic acid
4-amino-4-'nitrostilbene-2,2'-disulfonic acid
4-aminoazobenzene
4-aminoazobenzene-4'-sulfonic acid
4-aminoazobenzene-3,4'-disulfonic acid
l-aminonaphthalene
ll~Z~ilS
l-aminonaphthalene-4,5,6,7- or 8-sulfonic acid
2-aminonaphthalene-1,5- or 6-sulfonic acid
l-aminonaphthalene-3,6-disulfonic acid
2-aminonaphthalene-1,5-, 3,6-, 4,8-, 5,7- or 6,8-disulfonic acid
l-amino-4-phenylazonaphthalene-3'-sulfonic acid
3,3'-dichloro-4,4'-diaminodiphenyl
4,4'-diamino-diphenylsulfone.
The pyridones used as coupling components preferably
ha~e the formula
C313 c~3
HO ~ ~ O (5) or ~ 1 (6)
Xl
wherein Xl and Yl have the above meanings. A great number of such
pyridones are described in the literature, for example in British
patent specification 1,296,857.
The following coupling components are particularly
suitable for obtaining the dyes of the present invention:
2,6-dihydroxy-4-methylpyridine
2,6-dihydroxy-5-cyano-4-methylpyridine
2,6-dihydroxy-5-sulfo-4-methylpyridine
2,6-dihydroxy-5-cyano-4-ethylpyridine
1,4-dimethyl-2-hydroxy-5-cyano-pyridone-6
l-ethyl-2-hydroxy-4-pheny1-5-cyano-pyridone-6
l-ethyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
l-ethyl-2-hydroxy-4-methyl-pyridone-6
l-isopropyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
l-n-butyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
l-n-octyl-2-hydroxy-4-methy1-5-cyano-pyridone-6
l-n-octadecyl-2-hydroxy-4-methyl-S-cyano-pyridone-6
515
-- 7 --
l-benzyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
1-3'-sulfobenzyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
l-cyclohexyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
l-phenyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
l-p-toluyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
l-hydroxyethyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
l-cyanoethyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
l-methoxyethy1-2-hydroxy-4-methy1-5-cyano-pyridone-6
l-methoxypropyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
l-isopropoxypropyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
l-methoxycarbonylethyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
l-ethoxycarbonylmethyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
l-phenoxycarbonylethyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
l-ethyl-2-hydroxy-4-methyl-5-ethoxycarbonyl-pyridone-6
l-ethyl-2-hydroxy-4-methyl-5-carbamoyl-pyridone-6
l-ethyl-2-hydroxy-4-methyl-5-sulfomethyl-pyridone-6
l-ethy12-hydroxy-4-methyl-5-dimethylcarbamoyl-pyridone-6
l-ethyl-2-hydroxy-4-methyl-5-di-n-butylcarbamoyl-pyridone-6
l-ethyl-2-hydroxy-4-methyl-5-nitro-pyridone-6
l-ethyl-2-hydroxy-4-methyl-5-chloro-pyridone-6
l-ethyl-2-hydroxy-4-methyl-5-sulfo-pyridone-6
l-ethyl-2-hydroxy-4-methyl-5-acetylaminomethyl-pyridone-6
l-ethyl-2-hydroxy-4-methyl-5-acetyl-pyridone-6
l-ethyl-2-hydroxy-4-sulfomethyl-5-cyano-pyridone-6
l-ethyl-2-hydroxy-4-~ulfomethyl-5-carbamoyl-pyridone-6
l-ethyl-2-hydroxy-4-phenyl-5-cyano-pyridone-6
1,2-bis-(2'-hydroxy-4'-methyl-5'-cyano-pyridone-6'-yl-1')-ethane
1,6-bis-(2'-hydroxy-4'-methyl-5'-cyano-pyridone-6'-yl-1')-hexane
l-ethyl-2-hydroxy-4,5-dimethyl-pyridone-6
l-ethyl-2-hydroxy-4-methyl-5-phenylsulfonyl-pyridone-6
l-ethyl-2-hydroxy-4-methyl-5-~,~-dimethylsulfamoyl-pyridone-6
~ he diazo~osation is carried out in the usual manner
with nitrite in a mineral acid solution. The coupling is
~1~2515
-- 8 --
advantageously carried out in a weakly acid to weakly alkaline
medium. The azo dyes can be precipitated by salting them out and
removed by filtration or they can be converted direct by addition
of the amine into the amine salt, whicll is only poorly soluble in
water and can be isolated by filtration.
Suitable amines are lower aliphatic, araliphatic or
cycloaliphatic amines, for example methylamine, trimethylamine,
ethylamine, diethylamine, triethylamine, propylamine, isopropyl-
amine, 2-isopropoxy-n-propylamine, n-butylamine, isobutylamine, ethyl-
n-bu~ylamine, pentylamines, n-hexylamine, cyclohe~ylamine, N-methyl-
cyclohexylamine or benzylamine. Preferred amines, llowever, are
aliphatic or cycloaliphatic amines containing at least 7 carbon
atoms, for example octylamines, tri-n-butylamine, tri-(2-ethylhexyl)
amine, 3-(2'-ethylhexoxy)propylamine-1, dicyclohexylamine,
dehydroabietylamine, stearylamine, the reaction product of 1 mole
of stearylamine and 50 moles of ethylene oxide, and esp~cially the
products obtainable under the trade names Primene 81-R~Jand
Primene JM- ~ f Rohm L Haas. These products are a mixture of amines
of the formula
1 1
H2N--I--R2
R3
wherein Rl, R2 and R3 represent alkyl radicals containing
together 12-1~ (Primene81- ~ and 18-22 carbon atoms
(Primene JM- ~ .
Preferred an~ines are also those vf ~he formllla
~ ~5
4 ~ 6
wherein R4 represents hydrogen, an alkyl radical of I to 4 c~rbon
;lt~ms, .Ill ;llko~ynlkyl r;ldic ;ll or 3 t~ 6 ~;lrllol~ ms ~"- a (y~ e~yl
r~ R5 r~pr~ nL.~ I~y~ ) or ~ Ll~yl ~r~ -, R6 ~ -r~ t~ ;~
-' ll'~Z5~5
g
saturated or unsaturated hydrocarbon radical of 8 carbon atoms, and
R7 represents an alkyl radical of 2 to 10 carbon atoms, an alkoxyalkyl
radical of 2 to 4 carbon atoms or a cycloalkyl radical.
. Examples of such amines are:
3-amino-2-methyl-undecane, 4-cyclohexylamino-dodecane, 3-methylamino-
2-methyl-undecane, 1-(2'-propylamino)-1-cyclohexyl-nonane, 4-(1'-
butylamino)-dodecane, 4-(1'-butylamino)-6,9,11-dodecatriene, 4-(1'-
propylamino)-6,9,11-dodecatriene, 3-amino-2-methyl-5,10-undecadiene,
2-(2'-propylamino)-1-methoxy-2-methyl-decane, l-amino-10-methyl-1-
phenyl-undecane, 9-amino-octadecane, l-amino-l-cyclohexyl-nonane,
3-(3'-methoxy-1'-propylamino)-2-methyl-undecane.
Preferred amines are also those of the formula
3 ~1
2 ~ 4 2 E (C~2~2 E---C~2 ~ CO OR (7~
wherein each of R and R independently represents hydrogen or a
straight chain or branched alkyl radical of 1 to 8 carbon atoms,
R represents a straight chain or branched alkyl radical of 1 to 8
carbon atoms and R represents a straight chain or branched alkyl radical
of 1 to 1~ carbon atoms, or R and R and~or R and R together
with the carbon atom to which they are attached form a cycloaliphatic
ring containing 4 to ~ carbon atoms, and wherein each E represents
one of the radicals ~5 ~6 ~5 ~6
- H- H- and -
in which each of R and R6 independently represents hydrogen or
alkyl of 1 to 4 carbon atoms and R represents a straight chain or
branched alkyl radical con~aining altogether 1 to 18 carbon atoms,
and, in particular, those wherein E represents the radical
R15 R~6
-CH----CH-
Z515
-- 10 --
Examples of such amines are: methyl ll-amino-2,2-dimethyl-
tridecanoate (b.p. 78-80C/0.05 torr, ~ - 1.4494; n-pentyl
ll-amino-2,2-dimethyl-tridecanoate (b.p.126-128C/0.02 torr,
nD = 1,4494; isopropyl 11-amino-2,2-dimethyl-tridecanoate
(b.p.95C~0.01 torr, nD = 1.4469); methyl 11-amino-2,2,12-trimethyl
tridecanoate (b.p. 106-107C/0.03 torr, nD = 1,4511); n-pentyl
ll-amino-2,2,12-trimethyl-tridecanoate (b.p. 138-139C~0.01 torr,
nD ~ 1.4505); methyl 11-amino-trideca-4,8-dienate (b.p.106-108~C~
0.3 bar, nD = 1.4754).
The compounds of the formula (7) are obtained by reacting
a l-azacyclododecene of the formula (8)
R ~ /
~ ; (8)
R i\ ,t~ /
~6
or a l-aza-1,5,9-cyclododecatriene of the for~ula
R ~R
Rl\ ~ t~ R6
R6
in a~ueous or a~ueous-organic medium, in the presence of an
inorganic acid, by methods known per se, to produce compounds of
_ the formula
R3 R - H ~3
; 2 1 2 E (CH2~2 ~ E - CH2 - C - C~0 X2~3n
(10)
ll'~Z515
-- 11 --
in which formulae (8) to (10), Rl to R6 and E are as defined for
formula (7), X is the anion of the inorganic acid and n is an integer
corresponding to the valency of X2, and subsequently oxidising the
compounds of the formula (10) to the respective ll-amino-undecanoic
acids or ll-amino-undeca-4,8-dienoic acids, and, in a third reaction
step, reacting these acids by known methods with an alcohol of the
formula R OH, wherein R7 represents a straight chain or branched
alkyl radical of altogether 1 to 18 carbon atoms, to produce the
corresponding esters of the formula (7).
The salt formation is advantageously carried out by
reacting a solution or suspension of an alkali metal salt of the dye-
stuff sulfonic acid with the aqueous solution of a water-soluble
salt of the amine, preferably one with a lower fatty acid, in
particular formic acid or acetic acid. It is advantageous to carry
out this reaction at temperatures between 40 and 80C and at a
pH value below 7.
As the dye salts are insoluble in the aqueous reaction
medium, they can be isolated by filtration.
The reaction can also be carried out, however, in
organic solvents alone or in mixtures thereof with water. A
preferred embodiment consists in adding the solution of the amine
in an organic solvent of only limited water-solubility to an
aqueous solution or suspension of an alkali metal salt of tne dye-
stuff sulfonic acid, acidifying the resulting mixture with an
inorganic or organic acid and mixing it thoroughly, whereupon the
amine salt of the dyestuff sulfonic acid passes into the organic
phase and can be isolated, after separating the layers, by evapo-
rating off the solvent. The reac'ion in the two-phase system is
carried out at temperatures between lO~C and the boiling point of
the solven Vwater mixture. As organic solvents there are preferably
used chlorinated hydrocarbons, such as methylene chloride, chloroform
515
- 12 -
or chlorobenzene, ethers, such as diisopropyl or dioctyl ether, keto-
nes, such as methyl isobutyl ketone or diisopropyl ketone, esters,
such as ethyl acetate, butyl acetate or tert-butylpropionate, or
alcohols, such as n-butanol, iso- or tert-amyl alcohol.
The new dye salts have excellent solubility in
alcohols, especially in lower alkanols, such as methanol, ethanol,
n-propanol or isopropanol, in alkylene glycol monoalkyl ethers,
for example in ethylene glycol monomethyl or monoethyl ether,
in alkylene glycols, for example in propylene glycols, or in arali-
phatic alcohols, for example in benzyl alcohol, or in mixtures
of such alcohols, in lower aliphatic ketones, for example
acetone, methyl ethyl ketone, methyl isobutyl ketone or also in
cyclohexanone, in carboxylic acid esters, for example methyl
acetate, ethyl acetate, butyl acetate or glycol monoacetate, and
also in halogenated hydrocarbons, preferably lower aliphatic
hydrocarbons, such as chloroform, methylene chloride, ethylene
chloride or carbon tetrachloride.
Because of their good solubility in the above-
mentioned ketones, especially acetone, the dye salts of the present
invention are suitable for the spin-dyeing of cellulose 2 L/2-acetate;
and because of their good solubility in halogenated lower aliphatic
hydrocarbons, especially chloroform, and methylene chloride~
msthanol (9:1),they can also be used for the spin dyeing of
cellulose triacetate. The spin-dyed fabric is distinguished by
purity and depth of shade, by excellent distribution of the
colourant, and by very good astness properties, suchas Eastness
to washing, water, bleaching, cross-dyeing, dry-cleaning, rubbing,
ironing, dry heat and light.
On account of their good solubility in alcohols,
esters and mixtures thereof, the dye salts of the invention are
particularly suitable for colouring film-forming polymers. `
Z515
- 13 -
By alcoholic and~or ester-containing solutions of film-
forming polymers are meant in this context in particular those
liquid vehicles which are suitable for use in printing inks for
flexographic printing. As polymers, these solutions contain, for
example, neutral resins such as shellac or Manila copal, or
cellulose derivatives, for example cellulose ethers, such as
ethylcellulose or cellulose esters, such as nitrocellulose; and
also maleate resins or phenol-formaldehyde resins which are preferably
modified with colophonium, such as the products described in US
patent specification 2,347,923; polyamide resins, i.e. polyconden-
sation products of polyamines withpolycarboxy compounds, which
are described, for example, in US patent specification 2,663,649;
further urea~ormaldehyde and melamine-formaldehyde condensation
products, ketone-formaldehyde condensation products, poly~inyl
acetates or polyacrylic acid resins, for example polybutyl acrylate
resin, or their mixtures; polycondensation products of polyvalent
alcohols, such as glycerol or pentaerythritol, with polybasic
acids, such as maleic acid or phthalic acid alone or in combination
with unsaturated fatty acids, such as those of linseed oil and
castor oil.
In addition, the solutions of film-forming polymers
can contain conventional assistants employed in the
lacquer sector, such as wetting agents, for example higher fatty
acid bis-hydroxy-alkylamides, such as coconut oil fatty acid
bis-(~-hydroxyethyl)amide, plasticisers, for example phthalates,
and further ingredients, such as silicone oils.
~ hese solutions of film-forming polymers containing dye
salts of the invention are suitable, for example, for printing
a variety of materials, such as metal foils, for example aluminium
foils, paper, glass, synthetic resin sheets and films and the like.
They are also suitable for coating a wide variety of surfaces, e.g.
of metal parts, plastic mouldings or wooden boards. They are
S15
- 14 -
storable and provide level,strong and water-resistant coatings
on the above materials.
Compared with the starting materials of the dye salts of
the present invention, for example with the alkali salts described
in British patent specification 1 296 857, the dye salts of the
invention possess the advantage of greater solubility in organic
solvents.
~l~Z515
_ 15 -
Example 1 : 38.4 g (0.1 mole) of the motla~o dye of the formula
S03Na C~3
H
C~H5
are suspended in 1000 ml of warm water of 40nC. A solution of
19.5 8 (0.1 mole) of Primene 81-R~(Rohm & Haas) in 200 ml of water
and 6 ml of 85 % formic acid is added dropwise to the above homo-
geneous suspension. The reaction mixture is acidified by the
addition of further formic acid (litmus paper test) and stirred ~or
several hours at 40-45C. The dye salt is then removed by filtration,
washed thoroughly with water and dried in vacuo at 80-90C, affording
53 g of a yellow powder which dissolves very readily in lower
alcohols and ketones.
Examples 2 to 6 : Similar dye salts also having good solubilities
are obtained by repeating the procedure of Example 1, but using
0.1 mole of one of the amines listed in Table 1 instead of
Primene 81-
Table 1
Example Amine
2 tri-(n-dodecy~ Dine
3 3-amino-3,7-dimeLI~yloctane
4 isododecylam~ne (isomer mixture)
Primene JM- ¦
_ . d~hydroabiPtylamine ¦
114Z515
Example 7 : 48.6 g (0.1 mole) of the sodium salt of tlle monoazo
dye obtained by coupling aniline-2,4-disulfonic acid to 1-ethyl-2-
hydroxy-4-methyl-5-cyano-pyridone-5 are stirred in 300 ml of water
and 300 ml of methyl isobutyl ketone. Then 38.8 g (0.2 mole) of
Primene 81-R~(Rohm & Haas) and formic acid are added to the above
mixture dropwise until a pH value of 3.5-4 is attained. The
reaction mixture is stirred for 1 hour at 40-45C, both phases
are separated and the organic phase is washed with 250 ml of water.
The solvent is distilled off and the residue is dried in vacuo
at elevated temperature, affording 68 g of yellow dye salt which is
very readily soluble in the solvents cus~omarily employed in the
printing ink and lacquer sector, for example in acetone, methanol,
ethanol, isopropanol, n-butanol,benzyl alcohol, ethylene glycol
monomethyl and monoethyl ether, and in solvent mixtures, such as
ethanol~toluene (70:30), ethanol/ethylene glycol monoethyl ether
(~5:15), ethano Vethyl acetate (50:50), methylene chloride/methanol
(9:1). The printing inks, coloured lacquers and acetate fibres ob-
tained therewith are distinguished by a pure, yellow shade.
Examples 8 to 26 : Table 2 lists further dye salts wl-ich are ob-
tained by diazotising the amine of column II with the pyridone of
column III and reacting the sodium salt of the resulting azo
dyestuff sulfonic acid with the amine of column IV accordin~ to the
procedure of Example 7. Column V indicates the shade of the printing
inks obtained with the dye salt.
ll~Z515
~ ~ 3 oo
S ~
U~ ~ O
_ .__
E K .C ~ a -- K ~(~,
C X ~ X ~r~ ~ C --
~ e 8 a~ t~
a) o ~ ~ o ~ o o
C ~ I ~ ~ C C C C C C ~ ~ I --~ C
~J ~ U
~ E ;~ C~l g. ~ e ,E ,E3 ,e ,e e ~ s ~ 0 ~e
E ~ ~ h
¢ ~ ~1 ~ ~ 'O ~ ~ ~ I:L~ ~ ~ ~ ~ ~1 1:~, P~
.,
~ I ~ ' U
a ~ E
Ll ~
Oc, ,~ I ,e x I x I
c o c ~ o c o e
8 h O P~ C : ~, .,.1 ,~ h
~J I ~
~D ~ O. 'O ~ C~. ~ D,
C " rCJ '''I 1 8~ C
~ ~- I C ' ~ ~
O ~ y OJ ~
_1 U''l ' ~ ~ _l Ir~ ~ Ir'l
_ _ __ _ ._ __ . . _ _ _ . ..
. .~
,~
C oC ~ ~
~ ~ Qc)
C ' ''O 'O ,C't~
g
~ ,~
O ~ C o C C'C
_~ E :~ E :~
.,~1 ._
C
. . .. _ __
_~ ~ ~ O` O --< ~ ~ ~ ~ ~ I` ~ ~ O ~--
~~a ~
E-~ X
_ . _ ~ __ _ . . .. .
li~Z515
~ 3
a~ ~ o
~O ~ ~ :
00 --
S~
v~ O ?~
I .
a
.
r .C ~D ~
e ~ O ~ ,
V
~J I ~ I ~1 QJ I
c ~ ~ X ~ e
O h O 1~ 1 1
e ?' ~ ~ r O rC
J ~
~ ~ O
,~ ~ C ~ ~ O
v ?~ v ~ V ~r/
~ a) u ~ ~n D
O ~
,~ ~~1 u~ ~ t:l, ~ p,
.
c ~ 'a
~ V
rO
O
O ~J
~ ~ ~
O C
IJ ~ J O U~
~ V~ ~ .
C C O :1 1
O
1~ , ,~
R ~ rl rJ
O I~ ~ ~
O
V .~1 ~^ C C
O P, ~ rJ
V
r~
o~~3 r~ ~t u~ ~
D ~ r~ r~ r~ rJ
~ X ,
11'~'~515
-- 19 --
Example 27 : 40.1 g (0.1 mvle) of the potassium salt of the monazo
dye obtained by coupling sulfanilic acid to l-etllyl-2-hydroxy-4-methyl-
5-cyano-pyridone-6 are suspended in 1200 ml of water. A solution
of 32.8 g (0.1 mole) of Primene JM- ~ (Rohm 8 Haas, average molecular
weight 297, content from acid titration 90.S %) in 250 ml of water
and 7 ml of 85 % formic acid are added dropwise to the above sus-
pension at room temperature. Further formic acid is then added
to the reaction mixture until the pa is between 4 and 4.5, then
750 ml of butanol are added and the mixture is stirred until the
dye salt has dissolved in the butanol. The butanol phase is
separated in a separating funnel, washed twice with water and
concentrated. The residue is finally dried in vacuo, affording
67 g of a yellowish brown product which can be powdered. This
product is very readily soluble in ethanol, acetone, ethyl acetate
and in the solvent mixture methylene chloride/mctllanol (9:1).
Lacquer formulations which contain the dye salt, solvent and nitro-
cellulose or acetyl cellulose or an alkyd~melamine resin, produce
very strong, yellow colourations on paper or metal surfaces.
Tabel 3 lists further dye salts which are obtained by diazotising
the amine of column II with the pyridone of column III and reacting
the alkali salt of the resulting azo dyestuff sulfonic acid with
the amine of column IV by the procedure described in Example 27.
Column V indicates the shade of the printing ink obtained with
the dye salt.
l~Z515
_ O ~ O O ,
~ ~ : _ ~ ,_ _ ,_~ _ _ _
.C
u~
. . .
O
O
v ~ C
u E ~ E
C O ~ X
.o a~ ~ C æ c G
~ ~ e E Sv .a .E e
C ~ s
:~. O O
~ 4~ D r r u~
~ E e
J ' ' ~ E CO E e ~ e ~ ~
., ~ ~ ~, U ' ~ X ~ X ~
c ~ , e :~, O, O,
~ X ~ X O X :~ X ~ X ~ I X Q~
C O C o E O D~ 1~ C O O ~ g ~ C ~ OC
~ ~ ~ ~:) D~ ~ a ~ ~ ,c ~ S ra
e ~ .,, X r~
O ,C .r: ~ ~ O ~rt r
~ I ~ I t~I V I ~
OD ' ' ' ' ' e ' ' ' ~
~ ~ O ~ O _ O _ O ~ ~ ~ O U O V O
.,.~ ~ ~ a :~ a t- a
_~ S ro ~r ~,c ~ r ro :~ O : : S ~ D C~ O
~ v ~ al '~ ~ U V I ~ ~ ?` a ~ a
o I I I ~
,,. . , ... . __
c c
o ~ ~ .,,
c a
I I v
1 7~ o ~,~
x ~ ~:
~ c ~s~ .,~
O
P.
o '' ~ X~'c l -~
t~ '~ s
o ~ v : : v v ~ v ~ : ,~: ~ -
N ~~
a I c~ I I E ~
u~ ~ ~ ~O ~ ~;r ~ ~D ~ Ul
. _
~ . ~ 0~ ~ O ~ ~ ~ ~ I
D to ~
E-~ ~
_
515
-- 21 --
--o
,~
C ~:
~ -I
I o
~ ~ .,.
r
~J r
a
~ o
C ~ o ~ ~
~ ,~ U
O I ~ r
~1 ~1 ~ I
a I o ~1 1
.,, ~ C ~ C
C ~ r I
3 D cJ ~ ro
t~ ~
_ I
.J ~ O
C .,~
C
~ ~J I
Oa ".,
~J `C C
O
111 4~ ~_
3 ~:
C ~ ~ c3
V
~ ~ O -~
f-~ :~: ~t `$
2515
- 22 -
~xample 42 : 54.5 g (0.1 ~ole) of the sodium salt of the azo dye
obtained by coupling diazotised 2-amino-4,4'-dichloro-diphenyl oxide
to l-alkyl-2-hydroxy-4-methyl-5-cyano-pyridone-6 are suspended in
1000 ml of water and the suspension is stirred for 1 hour. Then a
solution of 19.4 g (0.1 mole) of Primene 81- ~ in 200 ml of water and
6 ml of 85 % formic acid are added dropwise. The reaction mixture is
acidified by adding furtllcr formic acid ~litmus paper test), then
strirred for several hours at room temperature. The dye salt is
converted by gentle heating into an easily filterable form and
collected by filtration. The product is washed firstly with dilute
formic acid and then thoroughly with water and dried in vacuo, afford-
ing 66 g of a brown powder which is readily soluble in ethanol,
acetone and ethyl acetate, and which produces reddish yellow lacquers
and printing inks.
Examples 43 to 67 : Table 4 lists furtller dye salts which are obtainedby di~zotising or tetraazotising the amine of column II with the
pyridone of column III and react;ng the sodium salt of the resul-
ting azo dyestuff sulfonic acid with the amine of column IV by
the method of Example 42. Column V indicates the shade of the
printing ink obtained with the dye salt.
515
~ . . . .
3 ~, _
,_ ~
U~ ~ s~
_ _
I ~ I ,c) ~
CO ~ oo .o C~7
C C ~: C
c E 13 E3 ~ a
.,1 .~
E~ )~ h
~; ~
. _
C
I ~ I ~ O ~ ~ D X
r u ~ I C .C r I O
, V I V , C ,. V.'~' C ~ C
V
V I X ~ I X ~ X C~. X ~ X :~ X
C ~ O C ~ O C O I O C O O O I :" I
O I ~ ~ O 1 ~1 0 ~ O ~ O S-' E3 ~ ~ '- O
9~:~ C ~ ~ ?` ~ ~ ~ v C
O X " r~ S ~ . S ~ ,C 1~ .C O
~J ~ IU I ~ I D X tJ
~:1 ~ ~ ~ ~ ~ CL t`I t~ C~ ~ ~ ~I L- O I
Ot) p, p, ~ I ~ h 11
~ S ~ --I O ~ C --I O ~ I --~ O --I ~ ~ t~ 'O I
_( C ~ C ,~ CV .C X .,C :'~
~ I C U ~ ~ V~ V ~ V~ S
O ~ ~ 1 I v I Q~
~
.~ C OC C C
C ~ ~ O ~ ~ ~ O
~ V c~ ~ u
3 :~
C C ~ C
~- I o o o o C ~ ~ ~>
C ~ 4~ ~ C ~ ~ ,, C C
G) C ~ ~ ~ ~ C
c ,~ 3
O ~ ~n ~n ,( o~ C ~
~ ,1 1 1 C ~ J C C
E3 C ~ r ~ ~ I C
o ~ o `~
~ C C O C r ~ C .s: o
O V `~ `r~ ~ ~rl ~ V V C~ ~ V _/
N _ _ ~
~C C C~ ~ C ~` C
. ~ ~
`J
o) C~ ~ ~ ~ ~ O ~ t
D ~ ~ ~-t ~t ~t ~ i ~ ~t
_ _ _ _ _ _ . _
l~Z515
-- 24 --
_
a~ o ~ O ~ c ~ oo o
~ ~ - : : c : ~ ~ c 3
~> ~ aJ
:~ o ~ ~ o.o ~1 o
._
o~ ~ X
.3 ~ c
.
_ . . . ._
I la)
~ ~ ~ , , C ~ ~
r r v C ~ 5
I ~ ~ ~ u
r~ I ~ I ~ I ~J ~ I
" a~ I c I I I ~ I ~;r c
~J I X ~r~l X I O O X ~ ~ X ~rl
C ~t O ~-I O ~ ~ C O I ~ O
O I ~ ~ ~ C ~ O
e- ~ ~ ~ D. ~ O ~ 1 X C ~ a.
o o c .~? I c ~ ~1 ~ c ~ ~ I
~rl ~ ~2 C`l P` I ~ ~ I ~ ~ ~ C
~0 ~ I ~, _ I I q) ~ :~ I v
~ .~ ~ O ~ o ,~ C I ~ --~ ~
_~ ~ o, r 1.1 S Va~ ~ ~ O C O
~I ~ v ~au ~ , V ~ C
O~ ~ I y I C I I I ~
~ ~ ~ U ~
'C C C ~ C
O O O C I O
W
C C C ~
C~ I I I N o ~1 rl C
~U U O ~ ~ ~ U ~J tJ a~
-~ C C: C I ~ Ul t~l ~ ,c:
v ~ ~ C ,~ C ~ ~J
~ v
~J ~; o ~ O C ,r: r ~ 1 C ~
C ~ ~ JJ V V V~ O :~ O
O ~ O~ ~ ~C C I ._ ~! I W a~ C
S C~ - I v ~
o c '~ I ''' a C a I `~
CJ ~ O O O O O ro O
C C ~ C ~: C C C ~ C ~ C
o _ ~ ~ O
N ~ O E e^ e- -, e -
ro ~ ~ ~ O ~ ~
~ v
o
C~
~J ~ ~ o ~ t
D Xu~
E-' ~s~
,
il4Z515
- 25 -
Example 68 : A suspension of 52.5 g (0.1 mole) of the sodium salt
of the monoazo dye obtained by coupling diazotised 2-aminodiphenyl-
sulfone-3'-sulfonic acid to 1-ethyl-2-hydroxy-4-methyl-5-cyano-pyridone-6
in 500 ml of water is introduced into an acid solution of 19.4 g
(0.1 mole) of Primene 81- ~ (average molecular weight 185, content
95.4 %) in 500 ml of water and hydrochloric acid. The reaction
mixture is acidified with further hydrochloric acid and stirred for
serveral hours at room temperature. The dye salt is then collected
by filtration, ws6hed with water and drled in vacuo. The product
dissolves in ethanol, acetone and ethylene glycol monoethyl ether
to give a yellow solution and produces strong colourations when
applied. in printing inks.
Example 69 : 38.4 g (0.1 mole) of the sodium salt of the azo dye
obtained by coupling diazotised 2-aminobenzenesulfonic acid to
l-ethyl-2-hydroxy-4-methyl-5-cyano-pyridone-6 are suspended in 1000 ml
of warm water of 40C. Then a mixture of 25.4 g (0.1 mole) of
3-(3'-methoxy-1'-propyl-amino)-2-metllylundecane, 8 ml of 85 ~ formic
~nd 200 ml of water is added dropwise. The acid reaction mixture
is stirred for serveral hours at 40-45C and then filtered. The
filter cake is washed firstly with dilute formic acid, thcn with
water and dried in vacuo at 70-80~C, affording 58 g of a yellow
dye salt which is very readily soluble in ethanol, acetone, ethyl
acetate and ethylene glycol monoethyl ether.
ExamplP 70 : 38.4 ~ (0.1 mole) of the sodium salt of the azo dye
obtained by coupling dia~otised 2-aminobenzenesulfonic acid to
l-ethyl-2-hydroxy-4-methyl-5-cyano-pyriclolle-6 are suspendcd in
1000 ml of water. A mixture of 18.1 g ¦0.1 mole) of 3-amino-3-
methyl-5,10-undecadiene, 8 ml of 85 Z formic acid and 200 ml of
water is added to the above homogeneous susyension. The acid reaction
mixture is stirred for several hours and then filtered. lhe filter
cake is washed firstly with 1 ~ formic acid and thell with wat~r
3 1~Z5~5
_ 26 -
which is very readily soluble in ethanol, acetone and ethylene
glycol monoethyl ether.
Examples 71 to 82 : Similar dye salts also having good solubilities
are obtained by proceeding as described in the preceding Examples,
but using 0.1 mole of one of the amines listed in the following
table.
Examples
71 3-amino-2-methyl-undecane
72 4-cyclohexyl d no-dodecane
73 3-methylamino-2-methyl-undecane
74 1-(2'-propylamino)-1-cyclohexyl-nonane
l-amino-l-cyclohexyl-nonane
76 9-amino-octadecane
77 4-~1'-butylamino)-dodecane
78 4-~1'-butylamino)-6,9,11-dodecatriene
79 4-(1'-propylamino)-6,9,11-dodecatriene
3-methylamino-2-methyl-5-,10-undecadiene
81 2-(2'-propylamino)-1-methyoxy-2-methyldecane
82 l-amino-10-methyl-1-phenylundecane
Example 83 : 5 g of the dye salt obtained in Example 7 are added to
95 g of a nitrocellulose lacquer obtained from 15 ~ of alcohol-soluhle,
low viscosity nitrocellulose with about 18 % of dibutvl phthalate, 10
of ethylene glycol monoethyl ether, 20 ~ of ethyl acetate and 50 g of
94 % ethanol. The mixture is stirred until the colourant is evenly
distributed. The lacquer is then applied with a film applicator
(handcoater of RK Chemical C0. Ltd., Royston, England) t~ a wet film
thic~ness of about 12 ~m to opaline paper or an aluminium lined foil
and dried, producing a firmly adhering, uniform, strong yellow finish
which has excellent resistance to exposure and treatment with water
and butter.
ll~Z515
- 27 -
Example 84 : 5 g of the dye salt obtained in Example 7 are dissolved
in 33 ml of ethanol, 34 ml of ethylene glycol monoethyl ether and
33 ml of desalinated water. The solution is clarified by means of a
paper filter and then applied to a board of beech plywood. The solvent
is evaporated and the board is then spray-coated with a combination
lacquer prepared from 14.6 g of nitrocellulose with about 18 % of
dioctyl phthalate, 23 g of butyl acetate, 4 g of ethyl acetate,
8.5 g of butanol, 2 g of diacetone alcohol, 4 g of ethylene glycol
monoethyl ether, 12.5 g of a non-drying ~lkyd resin (Duraplex ND 7
of Rohm & Haas) in the form of a 60 % solution in xylene, 6 g of a
melamine~formaldehyde precondensate (Cibamin M 9 ~, Ciba-Geigy AG) in
the form of a 75 % solution in butanol, 3.4 g of dioctyl phthalate,
12.5 g of toluene and 9.5 g of xylene, and then dried once more. A
strong, lightfast, yellow finish is obtained.
Example 85 : A two-layer finish on sheet aluminium is obtained in the
following steps:
a) Binder: 67.S g of a non-drying alkyd resin in the form
of a 60 % solution in xylene (Alkydal F 27~,marketed by Bayer),
26.4 g of a partially esterified melamine/formaldehyde precondensate
in the form of a 55 % solution in butanoL/xylene 1:1 (Maprenal TTX~
marketed by Cassella), 1.1 g of xylene, 4 g of ethylene glycol mono-
ethyl ether and 1 g of a 1 % solution o a silicone oil in xylene,
are mixed to a l~omogeneous composition.
b) 1st Layer: 5 g of a co~nercially available fine alu-
minilml powdcr a--e sllspe~ d in 1() 1~ -L moLI~yL ~hyl Ic(~looe nnd 10 r~
of butyl acetate. Then 75 g of the binder described in a) are added
to the suspension. Tlle resulting dispcrsion is ad~usted to the
processing viscosity with a solvent mixture of 60 % o~ xylene, 20 %
of butanol and 20 % of ethylene glycol monoethyl ether, and applied
to an aluminium sheet.
.. ~
` 11~'~515
- 28 -
c) 2nd Layer: 1 g of the dye salt obtained in Example 7
is dissolved in 99 g of the binder described in a) and the solution
is adjusted to spray viscosity with the solvent mixture referred to
in b). The solution is applied to the pretreated aluminium sheet as
second layer using a spray gun. The coloured coating is then finished
by drying for 30 minutes and stoving at 130C. A brilliant yellow
finish of good lightfastness is obtained.
Example 86 : 20 g of the dye salt of Example 7, 30 g of bleached
wax-free shellac, 5 g of dibutyl phthalate and 45 g of ethanol are
mixed. The resulting printing ink has a good shelf life and can be
used as obtained or diluted with ethanol for flexographic printing
on paper and aluminium foils. Brilliant and strong yellow prints of
good adherence are obtained with this printing ink on the above
materials.
Example 87 : 10 g of the dye salt obtained in Example 2 are stirred
into 90 g of a solution consisting of 2~ % of an alcohol-soluble poly-
amide resin modified with esters and prepared, for example, in
accordance with Example 7 of US patent specification 2 663 649, 2 %
of water, 5 % of the petroleum fraction boiling at 80-100C, 48 %
of ethanol and 20 % of isopropanol, to produce a printing ink which,
in flexographic printing, colours cellophane in a yellow shade of
good adherence and great purity.
Example 88 : 1.3 g of the dye salt of Example 7 are sprinkled into
a solution of acetyl cellulose in acetone with a solids content of
26 %. Then 20 ml of acetone are added and the mixture is rolled in a
well sealed bottle on a roller block until the dye is completely
dissolved. The coloured spinning solution is then forced through
jets. The filsment obtained runs through a long heated tube and can
then be spooled directly. The coloured material has a bright, yellow
shade and has excellent fastness properties, especially excellent
fastness to washing, water, bleaching, cross-dyeing, dry-clesning,
~l~Z515
- 29 -
rubbing, ironing, dry heat and light.
Examples for the manufacture of compounds of the formula (7)
Examples 89 :
C2H5 ~ 3 0
~2 (CH2)8 C C \ OC~
CH3
a) With stirring, 975 g (4.37 moles) of 3,3-dimethyl-12-
ethyl-l-azacyclododecene are added dropwise in the course of about
35 minutes to a solution of 450 g (4.6 moles) of sulfuric acid in
600 g of water. The clear, slightly yellowish solution is then
treated with steam for 20 minutes in order to remove any aldehyde
impurities. The aqueous solution is subse~uently stirred in an
autoclave for 3 hours at 50C under an oxygen pressure of 20 bar.
The acid reaction mixture is neutralised with sodium hydroxide
solution, affording 820 g (3.2 moles) of 11-amino-2,2-dimethyl-
tridecanoic acid, corresponding to a yield of 73 % of theory. Melting
point: 164-165~C.
Analysis for C15H31N02 Molecular weight: 257,42)
calculated: C 69.99 % ~ 12.14 % N 5.44 % 0 12.43 %
found: C 70.03 % H 12.10 % N 5.54 %
MS spectrum: molecular peak 257, fragment masses 228, 182, 140, 58.
b) 51.4 g (0.2 mole) of 11-amino-2,2-dimethyl-tridecanoic
acid and 200 ml of methanol and 22 g (0.224 mole) of sulfuric acid
are refluxed for 3 hours. Excess methanol is then distilled off,
the residue is diluted with about 200 ml of water and the reaction
solution is made weakly alkaline (pH 8-10) with aqueous sodium
ZSl~
- 30 -
hydroxide, whereupon the aminoacid ester separates as upper organic
phase. Subsequent distillation yields 48.5 g (0.179 mole) of
ll-amino-2-,2-dimethyl-tridecanoic acid methyl ester, corresponding
to a yield of 89.5 % of theory.
The further compounds of the formula (7) referred to in
the description can be prepared by an entirely analogous procedure.
Example 90 : 19.2 g (0.05 mole) of the monoazo dye obtained by
coupling diazotised 2-aminobenzenesulfonic acid to 1-ethyl-2-hydroxy-
4-methyl-5-cyano-pyridone-6 (sodium salt) are suspended in 500 ml
of water. A mixture of 17.1 g (0.05 mole) of 11-amino-2,2,12-trimethyl-
tridecanoic acid pentyl ester,4 ml of 85 % formic acid and 80 ml of
water is then added dropwise to the above suspension. The suspension
is stirred for several hours at 45-50C and filtered. 2he filter
cake is washed firstly with dilute formic acit and then with water
and dried at 60C in vacuo. The yield of isolated solvent dye of the
above formula is 35.7 g. 2he dye is very readily soluble in ethanol,
acetone, ethyl acetate and ethylene glycol monoethyl ether.
Valuable yellow solvent dyes are also obtained in
analogous manner by using the equivalent amount of one of the amines
of formula (7) instead of the 0.05 mole of 11-amino-2,2,12-trimethyl-
tridecanoic acid pentyl ester.
Example 91 : 48.6 g (0.1 mole) of the sodium salt of the monoazo
dye obtained by coupling diazotised aniline-2,4-disulfonic acid to
l-ethyl-2-hydroxy-4-methyl-5-cyanopyridone-6 are stirred in 300 ml
of water and 300 ml of methyl isobutyl ketone. 68.4 g (0.2 mole)
of 2,2-dimethyl-11-iso-propyl-11-amino-undecanoic acid pentyl ester
and formic acid are added dropwise until a p~ value of 3.5-4 is
attained.
