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Патент USA US3093638

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,.
ace
3,093,628
2
1
ation of the process for the production of the ‘amines of
general Formula 111 used as starting products and in the
second mode of operation, are cyanuric chloride, cyanuric
3,093,628
MONOAZO DIPHENYL TRIAZINE DYESTUFFS
Jakob Benz, Munchenstein, Basel, August Schweizer,
rMuttenz, Base], and Walter Wehrli, Riehen, Basel,
Switzerland, assignors to Sandoz Ltd, Basel, Swim
erland
_
‘ Patented June 11, 1963
'
bromide, Z-methyl- or 2-phenyl-4.6-dichlorotriazine and
primary condensation products of cyanuric chloride or
cyanuric bromide with ammonia or amines.
Suitable amines which with cyanuric chloride or bro
t
No Drawing. Filed Aug. 18, 1959, Ser. No. 834,392
mide yield the desired primary condensation products are,
Claims priority, application Switzerland Aug. 2%, 1958
e.g., methylamine, dimethylamine, ethylamine, diethyl
6 Claims. (Cl. 260-—15I§)
10
This invention relates to waterasoluble monoazo dye
stu?s of the general formula
'
SIOaH
amine, Z-hydroxyethylamine, die(2-hydroxyethyl)-amine,
n-propyiamine, iso-propylamine, 2- or 3-hydroxypropyl
amine, S-methoxypropylamine, 3- or 4-methoxybutyla
mine, Z-ethoxyethylamine, aminobenzene, N-methyl- or
N-ethylaminobenzene, and amines with water-solubilizing
15 groups such as l-aminobenzene-S- or -4-sulfonic acid, 1
aminobenzene-‘2-, -3- or -4-carboxylic acid, l-aminoben
x
zene-3- or ~4-sulfonic acid amides, l-amino-3- tor -4—meth
(I)
ylsulfonylbenzenes, aminoacetic acid, and 2- or S-aminoa
propionic acid.
wherein
the two x’s stand for a low molecular aikyl (methyl, ethyl) 20
or alkoxy (mothoxy, ethoxy) radical which may be fur
for example, byreacting diaminodiphenyl compounds of
ther substituted, or a halogen atom, preferably chlorine
or bromine,
I
The amines of general Formula II which are used in
the ?rst mode of operation of the process can be obtained,
the general formula
‘
R for the radical of a symmetrical triazme compound,
‘ which radical contains at least one reactive halogen 25
a:
I
atom, preferably chlorine or bromine, which is com
S0311
l,
bined to a carbon atom,
and
11
30
A for the radical of a coupling component.
wherein x has the aforementioned meaning, with a sym
The new monoazo dyestuffs are obtained by coupling
metrical triazine compound of the above-described type
1 mole oi the diazo compound of an amine of the general
containing at least two mobile halogen atoms in [a Weakly
formula
1‘
acid aqueous medium at temperatures between 0° and
35 20° C. Examples of suitable diaminodiphenyl com
re
:1 :
pounds of the cited type are 4.4'-diamino-2.2'-dimethyl
(II)
40
wherein the two x’s and R possess the aforestated mean
ings, with 1 mole of a coupling component and if desired,
1.1'-diphenyl-5-sulfonic 'aoid, 4.4’-diamino-‘2.2'-diethyl—
l.l'-diphenyl-5-sulfonic acid, 4.4’-diamino-2.2’-dibromo~
l.l'-diphenyl-5asulfonic acid, 4.4’-diamino-‘2.2'-dichloro
l.l’-diphenyl-5-sulfonic acid and 4.4'-diamino-2.2’-di
methoxy-l.‘1'-diphenyl-5-sulfonic acid.
The amines of general Formula H which are used in
the ?rst mode Eof operation of the process are converted
R contains two further reactive halogen atoms, with am
45 into their diazo compounds by one of the known methods
monia or an amine.
of ram dyestull chemistry, e.g., in aqueous solution or sus
A second mode of operation of the process consists in
pension by means of hydrochloric acid and sodium nitrite
condensing 1 mole of a monoazo compound of the general
at temperatures between ‘0° and 15° C. Depending upon
reacting the monoazo dyestuff formed, provided its radical
formula
the type of coupling component used, the coupling re
\
S0311
I
i
I
action can be conducted in an aqueous acid, neutral or
alkaline medium, the temperature being kept in the range
of "0° to 20° C.
A large number of aliphatic and aromatic compounds
,
‘
(III)
capable of coupling are suitable for use as coupling com
55 ponents.
wherein the two x’s and A possess the aforecited mean
ings, with 1 mole of a symmetrical triazine compound
which contains at least two reactive halogen atoms com—
Of special interest for the process of this in
vention are the l~aryl-3-alkyl-S-pyrazolones and their
water-soluble derivatives, hydroxynaphthalenesulfonic
acids, aminonaphthalenesulf-onic acids and aminohydroxy
naphthalenesulfonic acids.
bined to carbon atoms, and, if desired, reacting the result
The laminoazo dyestuffs of general Formula III used in
ing monoazo dyestuif, when the condensed radical of the 60
the
second mode of operation of the process can be pro
symmetrical triazine compound contains two further re
duced, for example, from the corresponding 2.2’-disub
active halogen atoms, with ammonia or an amine.
stituted 4.4’-diaminodiphenyl-5-sulfonic acid by mono
Examples of symmetrical triazine compounds with at
acylation of the amino group in the 4' position, diazotiza
least two reactive halogen atoms combined to carbon
tion of the resulting 4’-acylamino-4-aminodiphenyl-S-sul
atoms, such as are employed in the ?rst mode of oper
3,093,628
a
3
fonic acid, coupling of the diazo compound formed with
the coupling component to give the corresponding acylam
inomonoazo dyestuff, and saponi?cation of the acylamino
brought to the boil in 30 minutes and dyeing continued
at the boil for 1 hour. The dyed fabric is removed,
rinsed with Water and dried. It is dyed in a red shade
group.
of very good fastness to light, washing, milling and per
The reaction of these aminomonoazo dyestu?is with a
spiration.
symmetrical triazine compound of the above description
containing at least two reactive halogen atoms is carried
Example 2
out preferably in a weakly acid to neutral aqueous medium
at a pH value of 3 to 7. The reaction temperature is
9.2 parts of cyanuric chloride are suspended in 100
parts of water and 100 parts of ice. 26.3 parts of the
governed mainly by the reactivity of the triazine com 10 aminomonoazo dyestuff of general Formula IH, obtained
by coupling the diazo compound of 1 mole of 4’-acetyl—
When the monoazo dyestulfs of general Formula I pro
amino - 4 - amino - 2.2’ - dimethyl - 1.1’ - diphenyl - 5
duced according to either of the two modes of operation
sulfonic acid with 1 mole of 1-hydroxynaphthalene-4
of the process contain two further reactive halogen atoms,
sulfonic acid and subsequent splitting off of the acetyl
pound and varies from 0° to 80° C.
one of these atoms can be exchanged if desired for am 15
group, are dissolved in 300 parts of water at 0° and this
morria or an aliphatic cycloaliphatic or aromatic primary
neutral
solution is run into the suspension with vigorous
or secondary amine which may be further substituted.
stirring. A constant pH value of 3 to 4 is maintained by
The exchange is best effected in ‘a weakly acid to neutral
the ‘addition of a 15% sodium carbonate solution to the
aqueous medium at temperatures ranging from 20° to
reaction
medium. The condensation product is precipi
70° C. The same amines which are used for the produc 20
tated with sodium chloride, ?ltered OE and puri?ed with
sodium chloride solution. The dyestu? is dried with
tion of the primary condensation products from cyanuric
chloride or bromide are suitable for the exchange.
vacuum at 40—5 0°. It is ground to give a red-brown pow
der which dissolves in water with a scarlet coloration.
The monoazo dyestu?’s produced according to the dis—
closed process are new.
They ‘are suitable for dyeing,
padding and printing ?bers of animal or vegetable origin,
e.g. Wool, silk, and cotton, ?bers of regenerated cellulose,
25
Example 3
animalized cellulosic ?bers, synthetic polyamide ?bers,
9.2 parts of cyanuric chloride are suspended in 100
mixtures of these ?bers, and leather. Brilliancy of shade
parts of Water and 100 parts of ice. At 0° a neutral solu
characterizes these dyestuffs. The dyeings obtained on
tion of 8.65 parts of l-aminobenzene-S-sulfonic acid in
cellulosic ?bers are fast to light, washing, water and 30 100 parts of Water is run in with vigorous stirring. At
perspiration. The dyeings on Wool, silk ‘and synthetic
the same time the pH value of the reaction mixture is
polyamide ?bers are fast to light, washing, water, milling,
maintained between 3 and 4 by regular additions of an
perspiration and dry cleaning.
aqueous sodium carbonate solution. On completion of
Owing to the presence of at least one mobile halogen
the reaction, there is added a concentrated aqueous solu
atom in the triazine radical the dyestulf molecule reacts 3 tion of 26 parts of the aminomonoazo dyestu?, produced
with the ?ber to form a stable linkage between the dye
by coupling the diazo compound of 1 mole of 4’-acetyl
stufr" and the ?ber. The reaction of the mobile halogen
amino - 4 - amino - 2.2’ - dimethyl - 1.1’ - diphenyl - 5
atoms with the reactive hydrogen atoms of ?bers contain
sulfonic acid With 1 mole of 1-(2’-chloro-6’-methyl
ing amino groups already‘ takes place in the acid pH re
phenyl)-3-methyl-5-pyrazolone and saponifying the acetyl
gion, while with ?bers containing hydroxyl groups the 40 amino group, the solution then being stirred at 40—50°.
presence of an alkali, e.g. sodium carbonate or bicar
> By the addition of further sodium carbonate solution a
constant pH of 4 to 5 is maintained. The reaction com
bonate, is of crucial importance for securing a uniform,
smooth reaction. The dyestutfs possessing two mobile
halogen atoms can be reacted with the ?ber at room tem
pleted, the condensation product is precipitated from the
45 solution with sodium chloride, ?ltered off and dried “in
perature or at a slightly higher temperature, e.g. 40° (3.,
vacuo” at 40—50°. On grinding the dyestulf is obtained
whilst those which posses only one mobile halogen atom ‘ > as an orange-colored powder which dissolves in water to
are reacted at a higher temperature, eg 60° C. or above.
In the following examples the parts and percentages
are by weight and the temperatures in degrees centigrade. 50
Example 1
22. parts of the primary condensation product of the
general Formula II, obtained from 1 mole of cyanuric
chloride and 1 mole of 4.4'-diamino-2.2’-dimethyl-l.l’-di— 55
phenyl-S-sulfonic acid, are suspended in 300 parts of ice
cold water and diazotized at 0-5 ° by the addition of 14
parts of 30% hydrochloric acid and a concentrated aque
ous solution of 3.5 parts of sodium nitrite. The diazo
give yellow solutions.
A printing paste is prepared with:
40 parts of the dyestuif of this example,
100 parts of urea,
380 parts of Water,
450 parts of 4% sodium alginate thickening,
10 parts of sodium 1-nitrobenzene-3-sulfonate and
20 parts of sodium carbonate
1000 parts total
compound formed is coupled at O-5° with 12 parts of 60
The cotton fabric is printed and dried and then exposed
2-amino-8-hydroxynaphthalene-6-sulfonic acid suspended
to dry heat (150°) for 5 minutes, rinsed in cold and warm
in 100 parts of cold water. Crystallized sodium acetate
Water, soaped at the boil for 15 minutes, rinsed again in
is added to the reaction mixture in portions so that it
warm and cold water, and dried. A brilliant yellow print
reacts neutral to Congo Red indicator paper. When for
mation of the dyestuif is completed it is precipitated by 65 of excellent washing fastness is obtained.
In the following table further monoazo dyestuffs of
the addition of sodium chloride and ?ltered off. The
the formula
?lter residue is thoroughly washed with aqueous sodium
chloride solution and dried in vacuum at 40—50°. In
the ground state the dyestuif is a brown powder which
dissolves in water to give red solutions.
70
A typical dyeing method is as follows:
A dyebath is set with 5000 parts of water, 2 parts of
the above-described dyestu?, 4 parts of glacial acetic acid
and 2-3 parts of a commercial non-ionic levelling agent.
100 parts of a wool fabric are entered at 50°, the dyebath
3,093,628
11
12
Example 66
amino, benzylamino and disulfonaphthylamino, and A
0;
|
stands for the radical of a coupling component selected
from the group consisting of 1-chloropheny1-3Jmethy1
O
1?% \N
CH;
S0311
(13113
OH
|
5 - pyrazolone, 1 - (methylchlorophenyl) - 3 - methyl-5
|
t
5
("3_HNO_
pyrazolone, 1- (aminosulfonyl-phenyl ) -3 -methyl-5-pyrazo
N=N_
lone, l-dichlorophenyl-3-Inethy1 - 5 - pyrazolone-sulfonic
\N/
acid, l-(methyl-chloro-phenyl) - 3 - methyl-S-pyrazolonc
Ha
sulfonic acid,
—SO3H
l
S0311
1-phenyl-3-methyl-5-pyrazolone-sulfonic
acid, 1~hydroxy-naphthalene-mono-, -di- and -trisu1fonic
acids, 2-hydroXy-naphthalene-mono-, -di- and -trisulfonic
r
Example 67
01
('1
¢ \
7
1?
—NH-~O
SOaH
0H3
l'\|T
'
S0311
l
OH
I,
\N/ O-HNQ
—N=N
Ha
-—SO3H
S0311
Example 3
01
<5
¢ \
I?
011::
1F
I
O-NH-O
\ / O-ENO
1
N
S0311
0 _
||
80311
G1
/O\
I
—~N=N—OH
N|
|
C=N
,
|
CH3
I
0113
Having thus disclosed the invention what we claim is:
1. A water-soluble monoazo dyestutf of the formula
CH3
acids, Z-amino-naphthalene-mono- and -disulfonic acids,
ldamino - 8 - hydroxy - naphthalene - mono- and -disul
35 fonic acids, 2-amino-8-hydroxy-naphthalene-mono- and
~disulfonic acids and 2-amino-5-hydroxy-naphthalene
/ \
r
\N¢
503E
i
r
monosulfonic acid.
2. The water-‘soluble monoazo dyestuif of the formula
'
I
40
(I)
:5
I
N% \N
wherein each 1: represents a member selected from the
|
‘group consisting of low molecular alkyl, low molecular
CH:
(LB
914g / -HN-
alkoxy, chlorine and bromine, y represents ‘a member 45
selected from the group consisting of chlorine and bro-
SOSH
—SO3H
1
©-N=N
N
‘5
H3
$0111
3. The water-soluble monoazo dyestu? of the formula
01
OH
<5
/
OH
N/ \lrI
so H
I a
-
I a
ONE-d
\ / d-HN
|
N
503
n
-N=N
50311
H;
soar!
4. The water-soluble monoazo dyestutf of the formula
01
/ \
N/
N
CH
so 11
O
01
| a
l a
(“K
I
\
SIOaH
5H3
N
mine, z represents a m?mbef Selected from the group
consisting of chlorine, bromine, amino, lower alkylamino,
lower hydroxyalkylamino, lower alkoxyalkylamino, d-i
hydroxyethyl)-amino, di-(lower hydroxyalkyl)~amino,
iarboxymethylamino, dicarboxy-ethylamino, sulfo-ethyl- 70
amino, N-methyl-N-sulfoethyl-amino, phenylamino, methylphenyl - amino, lower alkoxyphenylamino, dimethylphenylamino, trimethylphenylamino, N-lower alkyl-N-
6H3 N
(.l l
:
5. The water-soluble monoazo dyestuff of the formula
C1
% \N
(EH3
SIOEH
0H
CHI) \ / g_HN®_©_N:N
N
(‘1H3
phenylamino, N-lower hydroxyalkyl-N-phenylamino, car
boxyphenylamino, sulfophenylamino, aminosulfonyl- 75
phenylamino, methylsulfonyl-phenylamino, cyclohexyl
Sloan
3,093,628
13
‘
6. The water-soluble monoazo dyestu? oi the formula
01
(I1
/
V
l
S0311
Ilq/ \1[\IT
,
0H
so H
] s
I a
011
I
\ /
N
H3
—SO3H
SIOaH
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,945,021
Fasciati et a1 __________ __ July 12, 1960‘
200,237
200,684
Austria ______________ __ Oct. 25, 1958
Austria _____________ _._ Nov. 25, 1958
FOREIGN PATENTS
14
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