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Патент USA US2105919

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2,105,919“
Patented Jan. 18, 1938
PATENT OFFICE
UNITED STATES
2,105,919
ORTHO-DISAZO DYE
WATER INSOLUBLE
STUFFS AND FIBER mmormmnwrrn
Erwin Ho?t'a and Hans Heyna, Frankfort-on-the
Main, Germany, assignors to General Aniline ‘
Works, Inc., New York, N. Y., a corporation of
Delaware
No Drawing. Application January 27, 1934, Se
rial No. 708,691. In Germany February 2,
1933
v
>
8 Claims.
(Cl. 260-84)
The present invention relates to Water-insolu
ble ortho-disazo dyestu?s and to ?ber dyed there
with; more particularly it relates to dyestuffs hav
ner it is possible to prepare dyestuffs which may
be used for the same purposes as the azo dyestuffs
hitherto known. The dyestuffs may be prepared
either in substance, on the ?ber or on any of the
ing the following general formula:
usual substrata adapted for the production of
lakes.
1
In comparison with the para-disazodyestuffs
which may be obtained according to U. S. Patent
No. 1,871,947 by coupling diazotized para—amino'
azo compounds of the benzene series with 2,3‘
10
hydroxynaphthoic acid arylides, the ortho-disazo
dyestuffs of the present invention are distin
guished by an essentially better fastness to boil
ing lye (boiling for 6 hours at atmospheric pres~
wherein R1 stands for a naphthalene, anthracene,
15
sure with 100 cc. of caustic soda solution of 40° 15
Bé. in 10,000 cc. of water per 1000 grams of ma
carbazole or benzocarbazole radical, R2 means a
radical of the benzene or naphthalene series and
wherein the nuclei signi?ed by I and II are sub
terial)
stituted by methyl, halogen, alkoxy, phenoxy, ni
tro, tri?uoromethyl, alkylsulfonyl, arylsulfonyl,
sulfonic acid-dialkyl-amino, N-methyl-ethane
.
1
'
'
'
-
The following examples serve to illustrate the
invention but they are not intended to limit it
thereto, the parts being by weight, unless stated
sulfamino or carboxylic acid-alkyl-ester groups.
We have found that valuable water-insoluble
otherwise:
(1) Cotton ?ber is padded in the usual man
ner with the following grounding liquor: 12 parts
of 1- (2’ ,3'-hydroXy-naphthoylamino) -2-methyl
orthodisazo dyestuffs are obtainable by diazotiz
ing substitution products of 2-amino-1,1'-azo
25 benzene and coupling them with hydroxy-aryl
ll-chlorobenzene, 36v parts by volume of caustic L
soda solution of 34° Bé., 24 parts by volume
of sodium Turkey red oil of 50% strength, 500
cene carboxylic acid, of ortho-hydroxycarbazole parts by volume of hot water are made up with
water to 1000 parts by volume. Thereupon,
carboxylic acids, of ortho-hydroxybenzocarba
the dyeing is developed with the following 130
zole carboxylic acids, or with compounds con
taining' a reactive methylene group capable of diazo solution: 2.8 parts1of 4-methyl-2-amino
coupling with diazo compounds, such as pyrazo
2’,4'-dichloroazobenzene are stirred together
with 5.2 parts by volume of hydrochloric acid
lone derivatives or arylides or esters of beta
keto-carboxylic acids, among which arylides of __of 22° Bé. and ice-cold water; 0.7 part of so
,carboxylic acid arylides, such as arylides of 2,3
hydroxynaphthoic acid, of 2,3-hydroxyanthra
a
_ -5
acetoacetic acid, benzoylacetic acid, terephthaloyb‘
dium nitrite are dissolved in water and added, .
diacetic acid and other acylacetic acids, or diacyl
acetyl arylamines, such as diacetoacetylbenzidine
thereto. When the diazotization is ?nished,
the whole is made up with water to 800 parts
or-tolidine, may be mentioned.
“ 40
The components _ by volume and rendered neutral by means of
used for preparing the dyestuffs must not con
tain any group lending solubility such as the sul
fonic acid or carboxylic acid group.
The dyestuffs correspond probably to the type:
/ N=N—R 1 (1)
; 45
‘sodium acetate. After washing and soaping at
the boil, the dyeing represents a Bordeaux-red: 4-0
tint having a very good fastness to washing and
to chlorine.
The dyestuff corresponds to the following for
R
(2)
wherein R and R1 represent substituted benzene I "
radicals and R2 means the radical of an hydroxy
'aryl-carboxylic acid arylide, of a p-keto-carbox
~ylic acid ester and of a B-keto-carboxylic acid. .
arylide or of a pyrazolone derivative.
The smooth course of the diazotization and the "
coupling must be regarded as highly surprising.‘
(Cf. “Kiinstliche organische Farbsto?e” of Fierzl »
i115
David, 1926, IIIrd vol., page 106).
In this man
2
2,105,919
(2) Cotton ?ber is grounded as stated in Ex
ample 1 with 5 parts of 2,3-hydroxynaphthoyl
aminobenzene, 7.5 parts by volume of caustic soda
solution of 30° Bé., 10 parts by volume of Turkey
red oil of 50% strength and 5 parts by volume
tered by suction and washed out; it formsa red
powder and possesses the following formula:
Cl
of formaldehyde of 33% strength. The dyeing
is developed with the following diazo solution:
3.1 parts of 5-methyl-4-methoxy-2—amino-2’,4'dichloroazobenzene are diazotized as described in
10 Example 1 and the diazo solution is rendered
10
neutral. The dyeing is washed‘and soaped at the
boil and represents a red-brown tint of very good
fastness to washing and to chlorine.
The dyestuif correspondsto the following for
15 mula:
CH:
O1
20
(5) Cotton ?ber, is grounded as described in
Example 2. The dyeing is developed with the
following diazo solution: 3.2 parts of 5-methyl
4- methoxy -2- amino -2’- chloro-4'-nitroazoben
I
IIII
N
zene are diazotized as described in Example 1
and the diazo solution obtained is neutralized.
The dyeing which has been washed and soaped at
25
(3) 3.1 parts of 5-methyl-4-methoxy-2vamino
2’,5'-dichloroazobenzene are stirred with 5.2 parts
the boil represents a deep brown shade of very
good fastness to washing and to chlorine, and
of very good dischargeability. The dyestuff cor
responds to the following formula:
CH:
30 by volume of hydrochloric acid of 22° Bé. and
ice-cold water and 0.7 part of sodium nitrite,
dissolved in water, is added thereto. When the
diazotization is ?nished, water is added until the
whole has become dissolved; then the product
35 is coupled in acetic acid solution with 2.2 parts
of ?nely divided aceto-acetic acid-ortho-chloro—
anilide. The dyestu? is ?ltered by suction and
washed out; it represents a yellow powder and
has the following constitution:
40
01
0 CH:
\
C]
45
II
N
OHr-C 0-4111-0 O—NH®
c4
50
OH
CH;
ON:
'
OCH:
By using, instead of 2,3-hydroxynaphthoyl
aminobenzene, 1 -( 2’, 3'- hydroxynaphthoylami
no) -2-methylbenzene for the grounding liquor,
a dark olive-brown dyeing is obtained; by using
1 -(2', 3’- hydroxynaphthoylamino) -4- methoxy
benzene there is obtained a deep ye1l0wish~brown.
Both dyeings possess a very good fastness to
washing and to chlorine, and a very good dis
chargeability.
(4) The diazo solution mentioned in Example 3
vis coupled with 1.8 parts of ?nely divided l-phen
'y1-3-methyl-5-pyrazolone. The dyestu? is ?l
The following table indicates a further number
of other ortho-disazo-dyestu?s, obtainable ac
cording to the present invention:
_
Diazo compound from:
55
Coupled with the following
arylide of 2,3 - hydroxy-
,
Shade
naphthoic acid:
1
5‘meth) l-é-methoxy-Z-aminm4'-chloro-
2
S-methyH-methoxy-2amino-2’-methoxy-
_._-_do _____________________ __ Y el 1 o w i s h
Anilide ____________________ __
Red-brown.
azobenzene
5~methyl-4-methoxy-2-.amino-4’-methoxy-
V
--___do _____________________ ..
azobenzene
. 3
30 ,
.' 65
.
T0
4
5-methyl-4-methoxy-2-amino- 2’,4’ - di-
Reddish brown.
5
5-methyl-4-methoxy-2iamino-3’-nitro-4’-
Ye ll o w i sh
methylazobenzene
6
methoxyazobenzene
?-methyl-i-methoxy-Mmino-W-methoxy-
7
5-methyl~4-methoxy-2~amino-4'-nitroazo-
?f-nitroazobenzene
Y e l l o w i s h.
brown.
8 _5-methyl-4-methoxy-2»amino-2’,6'-dich1oro-4’-hitroazohenzene
'
Deep reddish
'
brown.
9
5-methyl-4'methoxy-Z-amino-Y-methoxy4’-nitroazobenzene
l0
5-methyl~4~met_hoxy-24amino-2',5’-di-
. 11
5 - methyl - 4 - methoxy - 2 - amino - 2’-
Deep
12
5 - methyl - 4 - methoxy - 2 - amino - 3’-
Very
13
5-methyl-4-methoxy-2-amino-2’-4’-
methoxy-‘y-mtroazobenzene
methyl-4’-nitroazobenzene.
methyl-4’-nitroazobenzene.
dinitroazobenzene.
5
brown.
Deep brown.
benzenev
.
7
brown.
Do.
azobenzene
Do.
- Y e 1 l o w i s h
wn.
reddish“
brown.
yellowish
brown.
Deep
olive
brown.
14
5- methyl - 4 - ethoxy - 2 - amino - 2’-
15
4, 5-dunethyl-2-anunol4’-mtroazobenzene. .....do ..................... _. Red-brown.
ch19:o-4'-nitroaqobenzene.
Deep brown.
:40
4;
:I I I1) I 9,100,910
, g
,1
.'
' o
Coupled with the following
Diazo compound from:
‘
5
'
.
erylide oi
_
a-hydmxy- ,
: Shade
naphthoic ac d:
97 t-llritro-emethoxy-zamino-2’-chloroazo- iParo-anisididenni... ..... _- Brown-rod.
enzene.
98
.
5-methyl—4-methoxy-2-amino-2’,4’-dibromoazobenzene.
99
100
-
'
Anilide ............. ... .... ._
-
'
'
Ortho-anisidide ..... .-‘, .... --
5-methyl-4-methoxy-2-amino-iGphenoxy4'-nitro-5’-methylazobenzone.
‘
Anilide
_
............ __.
' ..... ..'
_
'
'
_
.
-
Red-brown. i
'
5-methy1-4-methoxy-2-omino-2’-ethoxy<
azobenzene.
10 101
‘
v
Yellowlsh brown
'
Do.
.
''
‘
__
10
4,5-dunethyl-Z-am1no-2’-chlcro-4’-mtro- _-...do .............. ...- _____ ._ Black-brown;
azobenzene.
'
‘
i
102
5-methyl-4-methoxy-2~amino~4’-N-
103
5-methyl-4-methoxy-2-amino-2‘Joarbor' Anilide .................... -. Brown-red.
methyl-ethanesuliamide-ezobenzsno.
Ortho-amsidido ........... __
I
‘
ylic acid-methyl-ester-azdbenzene.
104
'
‘
I
-
5-methyl-4»?methoxy-2-amino-2'-phonyl- .__._do ..................... ._
sulfonyI-4’-nitroazobenzene.
>
15
V
Red-brown. I
Diazo compound from
Brown.
Coupled with
Shade I
105 5-methyl-4-methoxy-2-aminoy2’ehloro-y- l-(3’-hydroxy-7’.,8’-bonzocar- Blue-gray.
nitroezcbenzene.
a
20 106
'
-
hazole-2’-carbonylamino)-
I
5-methyl-4-methoxy-2-amino-2’-methyi-
1-(3'-hydroxy-7’,8'-benm-
5’-chloroazobenzene.
‘
ino)-2-methyl-4-methoxy
I
*
benzene.
107 5-methyl-4-methoxy-2-amino12’-
-
-
1-(2'-hydroxycarbazola-3'- Yellow~brown.
methoxy-5’-nitroazobenzene.
'
20
Khaki-olive.v i
carbozolo-2’-carbonylam_
*
'
z-mothyl-i-mothoxyben'
zone.
gzrbonylaminm-i-chloto-
l
-
-
mane.
j
,
25 108 E-methyl-4-methoxy-2-amino-2’-nitro-4’- 1-(2’-hydroxyanthraosne-3'- ‘Olive.
methoxy-azobenzene.
I
>
'
'
'
25
carbonylamino)-2-methyl- ‘
.
benzene.
.
109
4,5-dimethoxy-2-amino-2'-chloro4’-nitro- -.__.do .................... __ Black-groom;
110
5-methy1-4-methoxy-2-amin0-2#ch1or0' ...-.do ..................... -- Olivmgraen.
azobenzene.
'
4’—methylazobenzene.
_
-
'
I
'
'
~
g
so 111 5-methyl-4~methoxy-2-ammo-2’-mtro-4'-
i
l-(3’-hydroxy-7’,8’-benzo- Mole-brown;
chloroazobenzone.
60
; .carbazole-2’ ~carbonylam
‘
I ino)+methoxybenzene.
yielding, when produced on the ?ber, a deep
yellowish-brown dyeing of very good fastness to
washing and to chlorine and of very good (115- 35
Since, an object of the present invention is to
provide dyestu?s of good fastness properties
35 which dyestuffs are insoluble in water and alka
li'es, it is to be understood that the aromatic nu
chargeability. '
clei of the general formulae appearing in the ap
pended claims do not contain any substituents
3- The water-insoluble ortho-disazo dyestu?‘
of the following formula:
which are known to render organic compounds
o
0 soluble'in water or alkalies and to tend to de
I
01
CH:
‘
preciate the fastness of the dyestuffs to alkalies.
Substituents of'this' kind are, for instance, the
sulfonic acid and the carboxylic acid group.
' 40
O|N-
N=N
0 CH:
We claim:
‘:45
1. The water-insoluble ortho-disazo dyestu?
of the following formula:
,
;
1
Cl
0
'
l
‘CH:
OQNON=N
:50
.
.
-45
'
CH:
com
-
'50
'
yielding,~ when produced on the ?ber, a dark
N_
olive-brown dyeing of very good fastness to
washing andto' chlorine and of very good dis
.
70H ‘
‘ '
£55
chargeability.‘
4. The water-insoluble ortho-disazo dyestuffs "55
I of the following‘ general formula:
.
,
'
I
I
x
yielding, when produced on the ?ber; a deep
‘ .
brown dyeing of. very good fastness to washing
<IRr_‘_N___N
'60 and to chlorine and of very good dischargeability.
I
'
_
'
'7“
I
I
.‘
‘
‘
X01
_
.
N
'
CHI‘
.
K
OH
V
/
‘65
0GB. I I
I
‘
E
‘70
u
l
‘
’
MON:
,
- I
s60
N
2. The water-insoluble ortho-disazo Idyestuft
of the following formula:
Y
-,
,
'
l
.
v
_
\C0-—NH-—-R:
wherein R: means a member of the group con
‘
,
I sisting'of radicals of the benzene and naphthalene ‘. 70
' ‘series, B: stands for a radical of the group con
- , sisting
of
halogen-phenyl,
dihalogen-phenyl,
halogen-methyl-phenyl, nitro-phenyl, dinitrc
} phenyl,v nitro-halogen-phenyl, nitro-dihalogen
" phenyl,
nitro-methyl-phenyl,
nitro- dimethyl-i 7 5
' 2,105,919
phenyl,
phenyl,
nitro-alkoxy-phenyl,
nitro-dialkoxy-
nitro - tri?uoro-methyl-phenyl,
nitro-
arylsulfonyl - phenyl and nitro-alkoxy-methylphenyl, X stands for a member of the group consisting of hydrogen, alkoxy, methyl, halogen and
nitro and Y for a member of the group consisting of a methyl and alkoxy, yielding, when produced on the ?ber, brown dyeings of good fastness
properties, particularly of very good fastness to
l0 washing and to chlorine.
5
5. Fiber dyed with the ortho-disazo dyestu?
as claimed in claim 1.
6. Fiber dyed with the ortho-disazo dyestu?’ as
claimed in claim 2.
'7. Fiber dyed with the ortho-disazo dyestuff as 5
claimed in claim 3.
8- Fiber dyed with the ortho-disazo dyestu?‘s as
claimed in claim 4.
ERWIN HOFFA.
HANS HEYNA.
10
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