-~ Case lSO-3699
~ 66~72
The invention relates to mono azo dyestuffs
having a pyrazole diazo component radical. ; ~ -
Thus, the invention provides disperse dyes of
5 formula I, 1 ~ ~`2 ~ -
=N-K I . .
k3 ~ ~
. . .:
in which Rl is (Cl_4)alkyl; (Cl-q)alkYl mono- ;~
substituted by chlorine, bromine, ; - .
cyano or (Cl ~)alkoxy; phenyl; .
phenyl substituted by one or two
substituents selected from chlorine,
bromine, cyano, nitro, (Cl 4)alkyl : -~
:~ and (Cl_4)alkoxy;
aminocarbonyl; aminocarbonyl ~:
substituted by one or two (Cl 4)-
alkyl groups; (Cl 4~alkoxy; or .:
alkoxy(Cl 4)carbonyl;
R2 ls an unsubstituted alkoxy-(Cl 4)-
carbonyl radical or cyano, with the
. .
provlso that it ls cyano only when
at least one of Rl and R3 is other
than methyl,
R3 is hydrogen; (Cl_4)alkyl; (Cl_4)alkyl
monosubstituted by chlorine, bromine, -
cyano, hydroxy, (Cl_4)alkoxy,
alkyl(Cl 4)carbonyloxy, phenyl, :~
cyclohexyl or a heterocyclic radical; ~ :
~ 1 ~
.: ~ : , . .. . .. . .
50-3699
;6~,'72
: !
. cycloalkyl; phenyl; or phenyl subst-
ltuted by one or two substituents
selected from chlorine, bromine,
cyallo~ (Cl_4)alkyl, (Cl_4)alkoxy,
tr1fluoromethyl and n~tro.
K is the radical of a coupling
component selected from the amino-
benzene, amino-naphthalene, pyrazo-
lone-5, 5-amlnopyrazole, pyridone,
pyrimidone, tetrahydroquinoline~ ; -
. .
coumarine or pyrrole series or o
the activated methylene group-
containing aliphatic series.
Any substituent on the coupling component K is chosen -
.
15 go as to be compatlble wlth t~le utlllty of the compounds as
dl perse dye~.
Substituted alkyl radicals of Rl are preferahly mono
~ substituted by chlorine, bromine or cyano and more partic-
`-~ ularly by cyano. Any phenyl raldical of Rl is preferably
20 unsubstitu~ed, The preferred significances of R1 are methyl
and cyanomethyl.
-~ Any alkoxycarbonyl of R2 preferably contains 1 or 2
carbon atoms in the alkoxy moiety, The preferred slgnificance
of R2, however, is cyano, asæuming, of course, at least one
25 of Rl and R3 is other than methyl,
Any substituted phenyl radical of R3 ls preferably
~ ~ubstituted by preferably one substituent selected from
- chlorine, bromine, cyano, Cl_4alkyl t Cl_4alkoxy ~ .
:~.
tri~luoromethYl and nitro. Any cycloalkyl of R3 i~
30 p~eferably cyclohexyl, The preferred signlfi-
~ B
- 3 - 150-3699
;6Z7'~
-~ cances of R3 are unsubstituted phenyl and monochlorophenyl.
; As examples of coupling components of the
activated methylene group-containing aliphatic series may be ~-~
given the acetoacetic acid anilides and the indane-diones.
The preferxed coupling component radicals as K
are those o~ the aminobenzene series, e.g. of formula (a),
R5
N\ (a)
R7 6
in which R4 is hydrogen, methyl, chlorine, bromine,
Cl 4alkoxy or phenoxy,
R5 is hydrogen or a Cl 4alkyl radical, unsub-
- 10 - stituted or substituted by a substituent ;
selected from cyano, chlorine t hydroxyl,
, Cl 4alkoxy, formyloxy, chloroacetoxy,
:` ' alkyl(Cl 4)carbonyloxy, alkoxy(Cl 4)carbonyl,,alkoxy(Cl 4)carbonyloxy and benzoyloxy,
R6 is Cl_4alkyl, unsubstituted or substituted
~- by a substituent selected rom hydroxy,
Cl 4alkoxy, cyano, phenyl, phenoxy, formylcxy,
: : , :.. .
chloroacetoxy, alkyl(Cl 4)carbonyloxy,
. alkoxy(Cl 4)carbonyl, alkoxy(Cl 4)carbonyloxy, :.
benzoxyloxy, phenylaminocarbonyloxy, phthal-
~ .
imidyl, ben20sulphomidyl, pyridyl and henzo-
thiazolylmercapto; or phenyl, unsubstituted
or suhstituted by up to two substituents
selected from chlorine, bromine, methyl,
methoxy and ethoxy,
'
;~ :
...i. , ,.: , .,: . . ., . .: .
. . . . . . . . . . . . . . .
- 4 - l50-369g
~(~6627Z :~
R7 is hydrogen, chlorine, bromine, cyano,
methyl, Cl 4alkoxy, formylamino, alkyl(C1 ~)
carbonylamino, benzoylamino, chIoro-, bromo-,
or phenoxy-aIkyl(Cl 4)carbonylamino, alkoxy-
(Cl 4)carbonylamino, benzyloxycarbonylamino,
~-a1koxy(cl 4)ethoxycarbonylamino or alkyl-
sulphonylamino, the radicals (a) being free
from -N-C-0- groups,
R4 is preferably hydrogen. R5 is preferably
o C2 3alkyl, substituted by cyano or alky](C1 2)carbonyloxy.
R6 is preferably C2 3alkyl substituted by alkyl(Cl 2)carbony-
loxy. R7 is preferably hydrogen, methyl or alkyl(Cl 4)-
carbonylamino.
The invention also provides a process for the
production of compounds of formula I, stated above, charact-
erised by reacting a diazotised derivative of an amine of
formula II,
Rl ~ 2~2 II
R3
with a compound of formula H-K.
^~ The diazotisation of the compounds of formula II
and the coupling with the compound HK may be carried out in
conventional manner, e.g. at a pH below 5, at a temperature
below 20~C, preferably from ~5 to ~5~C and in a medium
optionally buffered by an alkali metal salt of a low (e.g.
Cl 4)alkane acid, e.g. sodium acetate.
~ - 5 - 150-3699
` ~ ~0~6;~7;2
The resulting compounds of formula I may be
isolated and purified in conventional manner.
The amines of formula II and the compounds H-K
are either known or may be obtained in conventional manner
from available starting materials.
The disperse dyes of formula I are useful for
the dyeing or printing of substrates comprising or COnSiStillg ~-
of fully or semi-synthetic, hydrophobic, high-molecular
weight organic material, e.g. those conventionally dyed or
~ 10 printed using disperse dyes. They are particularly suitable
for dyeing or prlnting textile material, whether in fibre,
yarn,woven or other form, comprising or cohsisting of linear,
; aromatic polyester, cellulose-~/2-acetate, cellulose tri-
acetate and synthe~ic polyamides, on which they build-up well
from aqueous suspensions.
, . ..... . . . . . . .
It is especially advantageous to convert the
~ dyestuffs in known manner into dyestuff preparations pr1or
; to their use. For this purpose they are comminuted until
their average particle size is 0.01 to 10/u, especially 0.1
- 20 to 5 ~. This comminution may be carried out in the presence
-v of a dispersant or filler. For example, the dried dyestuff
is ground together with a dispersant, if desired or required -
in the presence of a filler, or kneaded with a dispersant to
form a paste and then dried under vacuum or spray-dried.
When a suitable proportion of water is added to a preparation
manufactured in this manner, it may be used for dyeing or
padding from a dilute liquor or for p~inting.
For dyeing from dilute liquors there axe
. - , . .
~ .
,- ~ . . . :
, '': ', , ~ ' . . " ' . , ,' , ' '
.
~`',
- 6 - 150-3699
~;6272
generally used up to about 50g of dyestuff per litre, for
paddin~ up to about 150g per litre, preferably up to 100 g
per litre, and for printin~ up to about 150 g per kilogram of
printing paste. The goods-to-liquor ratio may vary within
wide limits, for example from 1:3 to 1:200, pre~erably from
1:3 ~o 1:80.
Dyeing follows the usual practice: Polyester
fibres can be dyed in the presence of carriers at temperatures
from 80C to 125C or in the absence of carriers under
superatmospheric pressure at 100 to 140C,by the exhaustion
method. Furthermore, polyester fibres may be padded,
impregnated or printed with aqueous dispersions of the new
. ~ .
dyestuffs, the dyestuff being heat~set on the impregnated
material at 140 to 230C,for example with the aid of steam
or air. In the particularly favourable temperature ran~e
from 180 to 220C the dyestuffs diffuse rapidly into the
polyester fibre without subsequent sublimation, even when the
material under treatment is exposed to such a temperature for
a prolonged period. In this manner the objectionable fouling
of the dyeing apparatus is prevented. Secondary cellulose
acetate is preferably dyed between ~5 and 80C and cellulose
triacetate at a temperature of up to about 115C. The most
advanta~eous p~ range is from 2 to 9, especially from ~ to 8.
As a rule, the usual dispersants, which are
preferably anionic or nonionic and may also be used in the
form of mixtures of two or more, are added.
, . .. .
- 7 - 150-3699
36627Z
... ~ . :
About 0.5 g of dispersant per litre of dyestuff
preparation will generally suffice ~hough larger amounts, for
example up to about 3 ~ per litre, may be used equally well.
Known anionic dispersants suitable for use in the present
process are, for example, condensates from naphthalenesul-
phonic acids and formaldehyde, especially dinaphthylmethane-
disulphonates, esters of sulphonated succinic acid, Turkey
red oil and alkali metal salts of sulphuric acid esters of
fatty alcohols, for example sodium laurylsulphate, sodium
cetylsulphate, sulphite cellulose waste liquor or alkali
metal sulphates of monoglycerides of fatty acids. Examples
of known and particularly suitable nonionic dispersants are
. . .
the adducts of 3 to 40 mols of ethylene oxide with alkyl-
phenols, fatty alcohols or fatty amines and neutral sulphuric
acid esters thereof.
In paddiny and printing,the conventional
thickeners may be used, for example modified or unmodified
natural products, for example alginates, British gum arabic,
-~ 20 crystal gum, locust bean flour, gum tragacanth, carboxy~
methyl cellulose, hydroxyethyl cellulose, starches or
synthetic products, for example polyacrylamides or poly-
vinyl alcohols.
;~''' ' , . ' ' ' ' '''~ ' ' ' ''. ''
~ ,
.. . ., . ,
'. ' ~ ' ':' ' , :
,
- 8 - 150-3699
- '10~62~72
.~
The dyeings obtained have satisfactory all-round
fastness properties, of particular interest being their fast-
-~ ness to light, thermofixation, sublimalion and pleating. Other
fastness properties which may be mentioned include fastness
to water, washing, perspiration, solvents, e.g. dry-cleaning
solvents, lubricants, rubblng, cross-dyeing, ozone, gas fumes
and chlorine. The dyeings show resistence to various
permanent-press processes and to soil release finishes. The
dyes show resistence to reduction (when dyeing wool containing
lo substrates) and they reserve wool and cotton.
The following Examples in which all parts are by
weight and temperatures in degrees centigrade, illustrate the
invention.
~ " .
,.~.
. .
:'
,
- 9 - 150-3699
~66'~'7Z
Example 1
20 Parts of 5-amino-4-cyano-1-~-cyanoethyl-3-
cyanomethyl-pyrazole are added slowly at 0-5~ to a mixture
of 107 parts of nltrosylsulphuric acid (produced by dissolving
7 parts of sodium nitrite in 100 parts of concentrated
sulphuric acid), 85 parts of ~lacial acetic acid and 15 parts
of propionic acid. A mixture of 85 parts of glacial acetic
acid and 15 parts of propionic acid is added at 0-5 to the
mixture obtained and it is subsequently stirred at 0-5
for 3 hours. A solution of 28.9 parts of-1-acetylamino-3-
N-(2'-ace~oxyethyl)-3-N-(2'-cyanoethyl)-aminobenzene in 85
parts of ylacial acetic acid and 15 parts pf propionic
acid is added in drops and the resulting coupling mixture
is stirred for 3 hours at 0-5. The reaction mixture is
` then poured with stirring into a mixture consisting of
600 parts of ice and 300 parts of water, whereby the
resultant dyestuff is precipitated. It is filtered off,
washed with water until free from acid and salt, and dried.
The dyestuff thus obtained dyes synthetic fibres in red
shades.
- Application Example
7 Parts of the dyestuff produced in accordance
with Example 1 are ground to a fine powder for 48 hours in
a ball mill together with 4 parts of dinaphthylmethanedisul-
phonic acid sodium, 4 parts of sodium cetyl sulphate and
5 parts of anhydrous sodium sulphate.
1 Part of the dyeing preparation thus obtained
: , ; ' ' : , . . .
. "' ' ' ' . ' :. '
- 10 - 150-3699
3L~6627Z
is made into a paste with a little water, and the suspension
obtained is added through a sieve to a dye bath containing
. , ,
3 parts of sodium lauryl sulphate in 4000 parts of water.
The liquor ratio is 1:40. Then, 100 parts of purified
polyester fibre material are added at 40-50 to the bath, 20
` parts of a chlorinated benzene, emulsified in water, are
added, the bath is heated slowly to 100 and dyeing takes
place for 1-2 hours at 95-100. T~e fihres which are dyed
in brilliant red are washed, soaped, washed again and dried.
o The even dyeing is very fast to light, cross-dyeing, washing,
water, sea water, perspiration, sublimation, gas,fumes,
thermofixation, pleating and permanent-pressing.
In the following Tables are given further
dyestuffs according to the invention, which may be produced
- 15 in a manner similar to that of Example 1.
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