Note: Descriptions are shown in the official language in which they were submitted.
10940SS
Although water-insoluble monoazo dyes are known in
general, no prior disclosure of the dyes of this invention is
known.
The invention provides a new class of water-insoluble
monoazo dyes, in particular such dyes having the general
formula:
X-C-H2CO-~ 3 (I)
Rl
wherein
3 3, 3R4 in which R3 and R4 may form a
ring having 5 or 6 carbon atoms, or NHR5
R1 iS H, C1 to C5 alkyl, tCH2)20H or (CH2)3OR3,
2 , 3, CONHR3 or CONR3R4 in which R3 and R
may form a ring having 5 or 6 carbon atoms;
R3 and R4 are C1 to C5 alkyls; and
R5 is a C5 or C6 cycloalkyl.
The new dyes are prepared, as described in more
detail hereinafter, by reacting a compound of formula II :
O CH3
HO-C ~ N = ~ 2 (II)
HO / N
with a halogenated compound of formula III :
Alg-CH2-CO-X Alg = Cl, Br (III)
That the compounds of formulae (II) and (III) react
to produce the dye of formula (I) is surprising and unexpected,
since, as is known, usually in the nucleophile reactions, an
OH of phenolic type is more reactive than a COOH groupe
1094055
/cfr. J. 0. Edwards, JACS, 76, 1540 (1954) ~.
In accordance with this inver.tion, the compounds of
formulae (II) and (III) are reacted in the presence of an acid
acceptor, such as, e.g., K2C03 or CH3COONa, in a protic or
aprotic solvent, such as, e.g., water, tert. butyl alcohol,
DMF, N-methyl-pyrrolidone, N,N-diethyl-aniline, nitrobenzene or
sulpholane, or mixtures of such solvents. The reaction is
carried out at a temperature ranging from room temperature to
the boiling point of the solvent, and depending on the mobility
of the halogen atom in compound (III), optionally also under
pressure, in the presence of an alkaline iodide or of an
alkaline iodide and a base or quaternary ammonium salt, e.g.,
benzyltrimethyl ammonium hydroxide or tetrabutyl ammonium iodide.
If an alkaline salt of compound (II) is used, the
acid acceptor can be omitted.
The products (III) which are useful in the practice
of this invention include:
methyl chloroacetate ClCH2COOCH3:
ethyl bromoacetate BrCH2COOC2H5,
butyl chloroacetate ClCH2COO(CH2)3CH3,
neopentyl chloroacetate ClCH2COOCH2C(CH3)3,
chloroacetic acid diethylamide ClCH2CON-(C2H5)2;
chloroacetic acid cyclohexylamide ClCH2CONHC6Hll, and
chloroacetic acid piperidinoamide ClC~2CONC5Hlo.
The preferred concentration of compound ~II) in the
reaction medium can vary from 1~ to 70%. The dye (I) is
isolated, at the conclusion of the reaction, by filtra~ion
carried out in water, by dilution with water if the solvent is
water-miscible or by distillation in a vapor stream, after
neutralization of the alkalinity, if necessary (e.g., with
H3P04), if the solvent is water-insoluble. Finally the dye is
filtered and washed. Generally the dyes (I) possess a high
10940S5
degree of purity and do not require after-purification.
If necessary, the dyes can be purified from the un-
reacted intermediate (II) by crystallization in suitable solvents
(e.g., DMF), or by treatment with weak alkali.
The intermediates (II) are prepared according to
conventional techniques by diazo-coupling between aminobenzoic
acids and 6-hydroxy-4-methyl-2-pyridones substituted at po~ition
3 and on the nitrogen atom by groups R2 and Rl respectively,
as defined hereinabove.
The diazotizable bases used for preparing (II) are,
preferably, anthranilic acid, m-aminobenzoic acid or p-amino-
benzoic acid.
The coupling compounds used to obtain the compounds
(II) are prepared by well-known condensations, for example,
between H3CCOCH2COO-alkyl, RlNH2 compounds and R2CH2COO-alkyl
compounds (cfr. for Rl = CH3, R2 = CN Guareschi, Zentralblatt
1907 I 875), or between H3CCOCH2C00-alkyl compounds and R2CH2
CONH-Rl compounds.
The 6-hydroxy-4-methyl-2-pyridones useful in the
practice of this invention include the following ~eriJatives:
3-cyano,
l-methyl-3~cyano,
l-ethyl-3-cyano,
1-butyl-3-cyano,
l-(beta-hydroxyethyl)-3-cyano,
l-(Y-methoxypropyl)-3-cyano,
l-ethyl-3-carboethoxy,
l-ethyl-3-(N,N-diethylcarbamoyl)
l-methyl-3-(piperidinylcarbamoyl).
The dyes of the present invention are particularly
suited for dyeing and printing synthetic fibers, especially
polyester fibers.
~ 3
10940~5
When these dyes are applied according to the uqual
dyeing methods (for example in an aqueous bath under pressure
at 130C) and printing methods (for example the known Thermosol
method), the synthetic fibers are dyed or printed to intense
and bright greenish yellow shades having excellent fastness
characteristics, particularly to sunlight and to sublimation.
Furthermore, these dyes are very suitable for obtain-
ing discharge effects, either white or colored, through the
"alkaline reserve" method, i.e., treatment of the padded cloth
with alkaline pastes based on Na2C03 or NaHC03, optionally
additioned with alkali-resistant dyes, suitable for carrying
out determined drawings, and steaming.
The discharge effects are superior to those obtain-
able by means of disperse dyes, already known and selected for
such application and prepared from 6-hydroxy-2-pyridones, for
example, the disperse dyes described in Italian Patent N.
866,676 and having the formula:
(CH2)n 1
A-N = N ~ X2
H0 1 0
z
in which A may be ~alkyl Cl-C5)-OOC ~
The stabilities to sublimation of the present dyes
appear to be equally superior.
In use, the dyes, either in the dry state or in the
form of pastes, are ground in the presence of appropriate
dispersing agents such as, for example, sodium lignin sulphonate,
up to particle sizes of 0.5-1 ~ and are applied to the fibers
according to the techniques mentioned above, e.g., in an aqueous
bath by exhaustion, or by padding, optional printing of the
reserve, steaming.
-- 4 --
-` 10940SS
The following examples, in which the parts are by
weight, unless otherwise specified, are given to illustrate
the invention in more detail and are not intended to be limiting.
EXAMPLE 1
A mixture consisting of 11 parts of intermediate II
(p-COOH, Rl = CH3 R2 = CN), 5 parts of anhydrous K2C03, 0.6
parts of KI and 30 parts by vol. of dimethylformamide (DMF)
was heated to 70C. At that temperature, 4.5 parts of ethyl
chloroacetate were added.
After heating the total mixture to 90C for 1 hour,
it was allowed to cool to room temperature, poured into
acidulated water at room temperature, stirred, filtered and
washed. After drying, 13 parts of the dye of formula:
H5C20-C-H2CO-C ~ N = ~ ~ CN
7 o
CH3
were obtained.
EXAMPLE 2
A mixture consisting of 18.7 parts of intermediate
II (p-COOH, Rl = CH3; R2 = CN), 10 parts of anhydrous K2CO3,
1.3 parts of KI, 2 parts by vol. of a 40% solution of Triton B
(benzyltrimethyl ammonium hydroxide) in methanol, 14.4 parts
by vol. of ethyl chloroacetate and 100 parts by vol. of nitro-
benzene was heated for 3 hours under stirring to 120-160C.
After neutralization with H3PO4 and distillation of
the solvent in a vapor stream, a good yield of the dye of
Example 1 was obtained.
EXAMæLE 3
A mixture consisting of 9.4 parts of intermediate
II (p-COOH, Rl = CH3, R2 = CN), S parts of anhydrous K2C03,
O.65 parts of KI, 20 parts by vol. of DMF and 5.5 parts of
-- 5 --
-" 1094055
N,N-diethylchloroacetamide was heated 1 hour to 90C under
stirring. The mass was poured into acidulated water, it was
filtered and the solid was washed.
A dye of formula :
H5C2)2N-C-CH2O-C ~ N = N ~ CN
H N
CH3
was obtained in good yield.
EXAMPLE 4
5.4 parts by vol. of ethyl chloroacetate were
additioned under stirring at 90C to a mixture consisting of 15
parts of the sodium salt of (II) (p-COOH, Rl = CH3, R2 = CN),
0.3 parts of anhydrous K2CO3, 0.9 parts of KI, 1.8 parts of
tetrabutyl ammonium iodide and 50 parts by vol. of nitrobenzene.
The temperature was then brought to 130C. After l hour at
that temperature, the rough (total) reaction mass revealed,
on chromatographic analysis, the transformation to the dye of
Example 1.
EXAMPLE 5
7 parts by vol. of ethyl chloroacetate were added
under stirring at 70C to a mixture consisting of 9.3 parts of
the sodium salt of compound (II) (p-COOH, Rl = CH3, R2 = CN),
4.2 parts of K2CO3, 0.7 parts of KI, 10.8 parts of tetrabutyl-
ammonium iodide and 100 parts of water.
The temperature was then raised to 90C. After
filtering and treatment o~ the rough (total) reaction product
with boiling water, 10.3 parts of the dye of Example 1 were
obtained.
EXAMPLE 6 (Application ~xample)
In an apparatus for dyeing under pressure, 100 g of a
109405S
polyester cloth, previously scoured, were treated, for 10-15
minutes, in 2 liters of a dyeing bath at 50C containing 2 g/l
of ammonium sulphate and 1 g/l of Emulson ELU ta non-ionogenic
surfactant produced by Montedison, S.p.A., Milan, Italy).
1 g of the dye prepared according to Example 1,
microfined to liquid for 20% by means of ethylene glycol,
water, Saltetra SS (condensate of formaldehyde, m- and p-cresol
and Schaffer acid) was added to the bath.
The bath was brought to a pH = 5.5 with formic acid,
and heated to 90C in 20-30 minutes. The temperature was then
gradually raised to 130C and the bath was maintained at such
temperature for 60 minutes. At the conclusion of the dyeing,
it was cooled to 80-85C, the bath was discharged, the cloth
was rinsed and a reducing alkaline treatment was carried out for
20 r~nutes at 80C in a bath containing a ml/l of NaOH at 36Be,
2 g/l of Na2S204 at 85% and 0.5 g/l of DIAPAL CW( ) (a non-
lonogenic detergent). The dyed cloth was repeatedly rinsed
and dried.
The resulting greenish yellow dyeing was very intense
and exhibited excellent stabilities to sunlight, moisture and
heat treatments.
EXAMPLE 7 (Application Example)
25 parts of the liquid microfined product of Example
6 were mixed with 100 parts of Lamitex L10( ) (a thickener
based on sodium alginate), 2 parts of sodium chlorate, 2 parts
of citric acid and 745 parts of water.
The liquid so obtained was utilized to pad a pol~ester
cloth. After drying at 80-90C, the cloth was white discharge-
printed with a paste containing 90 parts of sodium bicarbonate,
66 parts of polyethylene glycol, 33 parts of glycerin, 400
parts of Lamitex L10( ), 210 parts of water and 200 parts of
an emulsion containing 80% of white SpiYit, 6% of emulsifier
- 10940SS
Diphasol EV(R) (based on a long-chain condensate of ethylene
oxide with a ramified alcohol C16-C18) and 14% of water. It
was then steamed at 170C for 8-10 minutes. After washing
and reducing cleaning with 4 g/l of NaOH and 2 g/l of hydro-
sulphite at 70-80C, a bright yellow dyeing having an intensity
of about 1/1 E.C.E. was obtained, that appeared perfectly white
in the areas subjected to discharge. The same observation on
the corrodibility was made by using 50 parts of the liquid
microfined product. In this case, the dyeing had an intensity
of about 2/1 E.C.E.
The dyeings obtained exhibited good stabilities to
sublimation and to wet washings, an excellent fastnesses to
sunlight.
The following Table contains a list of dyes (I)
according to the present invention and the color shade obtained
with them on a polyester cloth.
N. Dye tI) polyester
Rl = n-C4Hg, R2 = CN, X = OC2H5 sub- greenish
stitution on the para position of yellow
phenyl
9 Rl n C4 9, 2 ~ 4 9 greenish
substitution on the ortho position yellow
of phenyl
Rl = n-C2H4OH, R2 = CN, X = OC2H5 greenish
substitution on the para position yellow
of phenyl
11 1 ~CH2~30CH3, R2 = C~, X - greenish
OCH2C(CH3)3 substitution on the para yellow
position of phenyl
1094055
N Dye (I) polyester
12 Rl = CH3, R2 = CN, X = OC2H5 sub- greenish
stitution on the meta position of yellow
phenyl
13 Rl = CH3, R2 = CN, X = OC2H5 sub- greenish
stitution on the ortho position yellow
of phenyl
14 1 3, R2 COOC2H5, X = OC2H5 greenish
substitution on the para position yellow
of phenyl
R = CH R2 = CON(C2H5)2, X C2 5 g
substitution on the para position yellow
of phenyl / 2 5
16 Rl = CH3, R2 = CN, X = - N
substitution on the C4Hg greenish
meta position of phenyl / 4 9 yellow
17 1 CH3, R2 = CN, X = - N
substitution on the 4Hg greenish
para position of phenyl yellow
1 3' 2 ' ~
substitution on the para greenish
position yellow
19 1 CH3, R2 = CN, X = _ ~
substitution on the para greenish
position yellow
20Rl = CH3, R2 = CON(C2H5)2, X =
N(C2H5)2 substitution on the para greennish
position yellow
21Rl = CH3, R2 = CN, X = ~C2H5 sub- greenish
stitution on the para position yellow
1094055
Example Dye (I) polyester
22 Rl = CH3, R2 = CN, X = NHC4Hg sub- greenish
stitution on the meta position yellow
23 Rl = C2H5~ R2 = CN, X - NHC4Hg sub- greenish
stitution on the para position yellow
24 1 CH3~ R2 = CoNHc2H5~x = _ ~ greenish
substitution on the meta position yellow
Rl = CH3, R2 = CON ~
X = OC4Hg substitution on the para greenish
position yellow
26 1 3~ R2 = CC2H5, X = NHC4Hg greenish
substitution on the meta position yellow
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