close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2122424

код для вставки
2,122,424
Patented July 5, 1938
UNITED STATES PATENT OFFICE
2,122,424
DIAZOAMINO‘ COMPOUNDS AND THEIR
MANUFACTURE
Jean G. Kern, Hamburg, N. Y., assignor to Na
tional Aniline and Chemical Company, Inc.,
New York, N. Y., a corporation of New York
No Drawing. Application August 16, 1934,
Serial N0. 740,179
22 Claims.
This invention relates to a new type of diazo
amino compounds and to compositions of matter
containing them. The diazoamino compounds of
V
the present invention are especially suitable for
5 use in the art of dyeing textile ?bers of any
origin, for instance in the dyeing or printing of
cellulose, either natural ?bers or regenerated cel
lulose, cellulose esters or others, silk, wool, or
(Cl. 260-459)
substituents, e. g. halogen, nitro, alkyl, aryl,
aralkyl, alkylaryl, . alkoxy, . aryloxy, azo, primary,
secondary, or tertiary amino, sulfo, sul?te, hy
droxy, and carboxy substituents.
The diazoamino compounds of especial im- \
portance and which constitute one of the pre
ferred embodiments of my invention may be rep
resented by the formula:
hair ?bers or fabrics. The diazoamino com
10 pounds of the present invention also are useful as
germicides, bactericides, and insecticides.
The diazoamino compounds of the present in
vention may be represented by the general for
mula
(1)
112
wherein Ar represents an aromatic radical, which
may be further substituted; R1 represents a sat
v20 urated aliphatic or cycloaliphatic group, R2 rep
resents hydrogen, a saturated aliphatic or cyclo
aliphatic group, or an aromatic group, or R1 and
R2 together represent a polymethylene chain, and
the groups R1 and R2 are joined to the —-N—- of
25 the formula by a carbon of the R1 and R2 except
in the case where R2 represents H, and R1 is
joined to the ester group of the formula by a
‘carbon of the R1 group and R1 and R2 may con
tain as substituents alkyl, hydroxy, alkoxy,
aryloxy, sulfo, sulfato groups, halogen or a poly
,methylene chain, and R2 may contain an ester
group of the type shown joined to R1 in the for
mula;
Acyl represents the residue of sulfuric acid,
35 phosphoric acid, or a polybasic acid of the ben
zene or aliphatic series; i. e., Acyl represents the
radical formed by subtracting the acid OH
groups from the organic or inorganic acid, thus
from H2804 two OH groups are subtracted leav
40 ing S02 as the Acyl group corresponding to this
acid and from phthalic acid CsH4(COOH)2 two
OH groups are subtracted leaving C6H4(CO)2 as
the Acyl group corresponding to this acid;
Me represents hydrogen or'a metal;
45
n2 represents a positive integer;
:0 represents the number of esteri?ed hydroxyl
groups of the acid; and
1/ represents the number of unesteri?ed hy
droxyl groups of the acid. '
It should be noted in connection with the above
formula that one, two, or more amino-diazo
groups, -—N=NR1(R2)—OAcyl(-—OMe)y may be
joined to Ar; that is, the compounds may include
not only diazo nuclei but tetrazo nuclei and so
Further,‘ Ar may contain one or. more other
-55 011..
10
wherein, Ar has the value previously ascribed
but is free from groups conferring solubility in
water, sulfonate and carboxylate groups in par
ticular; R1 represents a hydrocarbon group, R2 15
represents hydrogen or a hydrocarbon group, or
R1 and R2 together represent a hydrocarbon
group [i. e. hydrocarbon groups of the classes
assigned in connection with Formula »(1) l;
Acyl has the value previously ascribed but 20
preferably represents S02;
vMe represents hydrogen, sodium, or potassium.
The compounds of my invention are especially
applicable to the dyeing of textile ?bers and may
be used for this purpose in a manner similar to 25
diazo or nitrosamine compositions. The diazo
amino compounds of this invention are stable in
the presence of coupling components and hence
may be used for the preparation of stable dye
compositions comprising one or'more of the di— 30
azoamino compounds and a suitable coupling
component or components.
Coupling of the diazoamino compounds of this
invention with the coupling components normally
employed with the corresponding diazo com
pounds may be eifected by treatment with acid,
as by introducing an acid into the bath contain
ing a solution of the diazoamino compound and
the coupling component, or by subjecting ?bers
containing a coupling component to the'raction 40
of an acidi?ed bath of the diazoamino compound
or by subjecting fibers impregnated with a solu
tion or paste of the diazoamino compound and a
coupling component to the action of an acid bath
or acid vapors. In the case of the diazoamino 1,45
.compound of the present invention coupling is
much more energetic and more complete than
with the diazoamino compounds formerly em
ployed, and dyeings of greater depth and bril
liance are therefore obtained.
The reason for 50
the improved results in these respects appears
to lie in the fact that cleavage of the diazoamino
linkage is accompanied by breakage of the link
binding the organic residue R1 above to the poly
basic acid radical.
Thus one acid radical is set 5.5
2
2,122,424
free and the action of this free acid radical mate
containing a coupling component or developer
rially promotes further cleavage of the diazo
amino linkage. The cleavage is most complete
and a diazoamino compound of one of the fol
in the case ofdiazoamino compounds formed'ioy
5 the cgupling ef a diazo compound with the par
tial ester of a hydroxy organic primary or sec
ondary amine and an inorganic polybasic acid
logging types:
i
(6)
and
AFN=N_N_ _R,__o_Acy1(~oMe),
ganic
of thepolybasic
class previously
acid. ; The
mentioned
double cleavage
or a strong
which
or-
takes place using the diazoamino compounds of
a
I: i.
'3’
"1
(7)
,
wherein A; represents an aryl group, e. g. phenyl, 10
this inventicen may be demonstrated by the fol-
naphthyl, :diphenyl, anthranyl, anthraquinonyl,
lowing equation;
orgcarbazole, which may contain as substituents
‘
'
i
CHz-CHg-CH;
one
or more of the following: chlorine, bromine,
r
Ar-—N=N—2
. i i
nitro, alkyl, aryl, aralkyl, alkylaryl, alkoxy, aryl
AFN? ;-N
I,
CH’TCHHJE
EH OHz—Ol5([)r?1g.SOaNa—>+HN
(3)
2.
:
:
T
l
7
oxy, azo, amino, sulfo, hydroxy, and carboxy
groups; R1 represents a hydrocarbon group, R2
represents hydrogen or a hydrocarbon group, or
R1 and Ratogether represent a hydrocarbon group
[i. e. hydzocarbon groups of the classes assigned
The products of the present invention are suit
20 able for the preparation of either water soluble
or water insoluble azo dyes.
They are especially
suited for the production of azo dyes of the irisol
uble type and the invention in its preferred as
pects is directed to the diazoamine compounds
25 or compositions derived frompdiaze compounds
free from sulfonate or carhoxylate groups and,
in the case of compositions containing a coupling component,
components free from such
groups,
1
The diazi'oamino compounds of this invention,
30
especially those in which the amino ester group
comprises an —OS,OzOMe radical, wherein Me
20
in
:5 1;Me
connection
represents
represents
with
a hydrogen
positive
Formula
integer,
or(1)
a l;
metal,
preferably 1 or
2, m
andor 112 represents a whole number, in par
ticular l, 2, or 3.
5
in
water or aqueous alkaline solutions and hence
are especially valuable for" use where rapid and
25
The diezoemihe Compounds of the type repre
Sehted- by Formula 6 may be Prepared by 0011
Fling anilroma?e 1110110- '01‘ poly-diazonium Salt
with an 'amino partial ester.
The coupling may
be represented by the following equation;
30
Ar(—N=N—z)"fl-n1[H—III—~R1_b_AOy1(é_.OMe),]
'
R2
represents H, Na, or K, possess notable solubility
35
p-a Cll
.
(8)
A‘ ‘N:N_IIT—R‘*O?AW1(—OM®']+”‘(H_z)
'iRz
n, ,
35
Preparation er the diazoamino compounds
complete solution is desirable; this property con
stitutes a marked?advanta'ge of the compounds represented by Formula 7 is effected in a similar:
of the present invention whether they are em
"mannerrand may be represented by the following
ployed as
40
etc.
,
40
'
The diazoamino compounds of the present in
vention may be prepared by coupling anj aro-
matic diaz'onium salt of the general formula:
Ar—-(N=;\T—z)n1
(4)
5
.
1
~
.
W
.
wherein Ar represents an aromatic radical as pre
.
L
'iously set forth,
.7
example 51’ and‘
50
, .
C
55
'
.
.e r7153
i
.q
1 y
of’ 'a ’ m?é'r' or
;
J,
[<HIII_,>R‘_O_JACYI(_OMQ'
R”
I‘
In either case
is advantageous to add an alka
line rea cut to bind the
45
acid liberated duri '7
represents a“ positive integer ’ added either during coupling or after as desired.
of
to di
p
y
lsg?ida‘ry ammo'partml Qster of tlhe general for‘
'*
i
represents an acid group, for V the wuiling. ‘*The alkaline reagent’ may 1%:
?lele Stoi £10m t .1811’ uan?;
*
R’
[Ar_N:N“jT_]_R‘?0_A°y1(_OMe)“ma-‘1) (9)
LB’ ':
1
“B
I
azoamino compound 1n the compositions of my 50
invention may vary widely. Preferably, however,
I mix the two constituents in about stoichio
metrical
(5)
1
wherein R1, R2, Acyl, Me, a: and 1/ have the values;
previously ascribed in the discussion of Formula;
i and ‘n2 represents a positive integer indicating
the number ofgprimary or secondary’ amino
60 groups joined toethe organic rae'iical R1, prefer-
quantities.
The
compositions
may
comprise the constituents in, dry form or in solu
tion. :The dry composition may be prepared by 65
mechanical admixture of the two constituents
in solid phase or by evaporating a solution of the
two constituents.
While the present invention is of general ap
plicability to the class of compounds indicated 60
ably 1, 2, or 3.
,
7
above, especially those of Formulae (6) and (7),
The reaction to form the diazoamino com- . I have foundlithat the best results may be ob
pound proceeds at low temperatures. The cou- tained when the .diazoamino compounds are pre
pling of the diagonium salt with the amino‘ par65 tial ester is advantageously effected by bringing
togethei" aqueous solutions of the individual I'G-E
"actants’in the presence of an alkaline; medium
iwhich serves to bind the acid liberated by the
coupling. The diazoamino compound may be re70 covered by crystallization, including salting out,’
or by drying the solution containing it in vacuum
or in other suitable manner, for instance with
the aid of an inert gas or on a rotary drum drier.
In its preferred aspects my invention compre-
(75 hendsifthe preparation of dyestu? compositions
pared by the reaction, of an aromatic diazoni'im
salt with a sulfuric acid partial ester of hy 05
droxylated aliphatic amines; either ?l‘imal'y 01'
secondary. As previously indicated,‘ such com
P01111915, Which eontain'atleeiet One —-—0S020Me
radical, possess properties rendering, them es
pecially suitable for the purposes of this inven 70
tion. WhenZthe esters are those of polyhydroxy
aliphatic amines, one or more of the hydroxy
grOliQPS may be esteri?ei The products Prepeél‘ed
as first indicated are diazoamino-aliphatic eul
furic acid partial esters, including b'pth the free 75
,
.
.
_
V
U
_
2,122,421‘
acids" and their meta ,s'altspthe alkali-metal
salts and particularly the sodium salts beingthe,
preferred form of these compounds for’, use inad
mixture with the various known coupling compo
nents.
,
7
~
'
The compositions containing a diazoamino
' compound of the present invention and a cou
pling component, may, be applied to textile ?bers
in the usual manner. , They are particularly
10
suitable for the dyeing‘, of fabrics by the printing
process. A printing paste is prepai'e‘d‘by mixing
together about stoichiometrical quantities of a
diazoamino compound ‘of the type-‘previously de
?ned and a coupling component, adding to the
15 mixture sodium hydroxide solution in quantity
suf?cient todissolvethe components and making
up the mixture to a. printing paste in the usual
manner by, adding thereto a thickening agent
such as starch or gum tragacanth and the neces-_
20 sary quantity of water. .If desired, Turkey red
oil or other assistants or solvents may beadded.
The fabric is printed with this printing paste
in the usual manner; then, either with or with
out drying and steaming it is treated for a short
25 time, say around 20 seconds, in a bath containing
an acid, for example 3% to 10% of formic acid,
acetic acid, or oxalic acid at a temperature be‘
tween 50° and 90° C. The bath may also contain
30
I 2,5édichlor-l-amino-benzene,
l-amino-anthraquinone,
1-amino-4-benzoylamino-anthraquinone,
anilin-li-sulfonic acid,
2,5_-dichlor-aniline-?l-sulfonic acid,
2-amino-diphenyl-sulfone,
_ 2-amino-4'-methyl - diphenyl -- sulfone-4-su1
fonicacid,
2-amino-4’-hydroxy - diphenyl-sulfone-3'-car
boxy-‘l-sulfonic acid,
2-amino-4-methyl-5—nitro-benzoic acid,
1-amino-anthraquinone-2~sulfonic acid,
2-amino-l-carboxy-benzene-4-sulfonic acid,
2-amino-4-methoxy -5- phenylamino-l-chloro is
benzene,
4,6-_dichloro-2-amino-l-methyl-benzene,
ZA-dimethyl-aniline,
3-amino-4-methoxy -6- nitro ~l- methyl - ben
zene,
3-amino-4-methoxy-6-benzoylamino-1-methy1—
benzene,
V3-benzoy1amino-4,6-dimethoxy-aniline,
4,4'-cliamino-3,3’-dimethoxy-azobenzene,
2,6-dimethoxy-4-benzoylamino-aniline,
2,5-dimethoxy-4-benzoylamino-aniline,
2-methoxy-4-benzoylamino-5-ethoxy-aniline,
4-methyl-4'-amino -2- methoxy-S-methyl-azo
or sodium chloride (NaCl), or sodium acetate
benzene,
4-chloro-4'-amino-2',5’-diethoxy-azobenzene.
1 through an acid vapor ager containing, for, ex
35 ample, steam and vapors of acetic or formic acid
or both. After development of the print in any
of the above manners, it may be rinsed, washed,
and dried in the customary manner.
1 '
,
As mentioned earlier in this application, the
40 diazoamino, compound of the present invention
may ,be prepared‘ from diazotized aromatic
amines and primary or secondary amines con
taining a partial ester group. The partial ester
group may be introduced into the amine by melt
45
ing andrfusing together and/or by'condensing in
appropriate solvents, and/or in the presence of
catalysts, the free polybasic acids or their an
hydrides or acid chlorides or mixtures thereof
and an hydroxylated amine in its free state or in
its combined N—- salt, state. .
,
,
Since the esteri?cation of hydroxyrcompound's
is well known, the description of the ‘prepara
tion of the compounds and ‘compositions of the
present invention will be described in the ex
., 55
diazo compounds to produce the diazoamino com
pounds of the present invention:
met-hyl-amino-butyl-sulfuric acid,
ethyl-amino-butyl-sulfuric acid,
hydroxy-ethyl-amino-ethyl-sulfuric acid,
amino-diethyl-disulfuric acid,
cyclohexylamino-ethyl sulfuric acid,
lfi- (beta-ethyl-hexyl) -amino-ethyl s u l i u r i c
aci
,
N-(beta - ethyl-cyclohexyl) -amino - ethyl sul- -.
715
furic acid,
hydroxy-ethyl-amino-ethyl-phthalic acid,
_ the sulfonic ester from ethanolamine and 4
sulfo-benzoic acid,
methyl-amino-ethyl-dichlor-phthalic acid,
sulfo-ethyl-aminoebutyl-sulfuric acid,
zene-p-disulfonic acid,
the disulfonic ester from dipropanol amine and
ll-sulfo-benzoic acid,
N-n-butyl-amino-ethyl-sulfuric acid,
isohexylamine-beta-sulfuric acid,
of its general applicability and not by way of
limitation. Thus the invention may be applied
tetrahydro-naphthylamine-ethyl-su1furic acid,
S-chlor-aniline,
,
,
4-chlor-2-arnino-1-methyl benzene,
4-chlor-2-amino-1-methoxy-benzene,
4-nitro-2-amino-l-methyl-benzene,
' 5-nitro-y2-amino-l-methylfbenzene,
3-nitro—4-amino-l-methyl-benzene,
5-chlor-2-amino-l-methyl-benzene,
,3-chlor-2-amino-l-methylfbenzene, '
6,-chlor-2-arnino-l-methyl-bénziane,
3-chlor-4-amino-l-methyl-benzene,
4,5-dichlor-2-amino-l-methyl-benzene,
2,5-dichlor-4-amino-l-methyl-benzene,
, G-benzoylamino 4- chlor-3-amino-1-methoxy
benzene,
a
the mono, (methylamino-ethyl-ester) of ben
mono- (methyl-amino-ethyl) -maleic acid ester,
'
. '75
The following partial esters illustrate the wide
tial esters. The'invention is of a broad scope
and the examples are inserted as a demonstration
the ‘following aromatic amines:
so
variety of compounds which may be coupled with ,‘ ~
amples commencing With'theamino organic par
to diazo compounds obtained by diazotization of
(6 O
is
4-nitro-4’-amino-2’,5'-dimethoxy-azobenzene,
3-nitro-4’-amino-2',5’-dimethoxy-azobenzene,
other assistants, penetrants, etc., for example
around 10% of Glauber’s salt ‘(Na2SO410I-I2O),
(CH3COONa). Instead of developing the dye in
an acid bath, it may be developed by passing it
110'
-2-amino-5-chlor-l-benzoic acid methyl ester,
the disulfonic ester from diethanolamine and 3
sulfo-benzoic acid,
piperidine-beta-sulfuric acid,
cyclo-hexyl-amine-B-sulfuric acid,
pyrrolidine-alpha-methyl-sulfuric acid,
the sulfonic ester from methyl-ethanolamine
‘and li-sulfo-benzoic acid,
methylamino-ethyl-acid-succinate,
methylamino-ethyl-acid-chlor-maleate,
ethylamino-ethyl-phthalic acid,
methylamino-propyl-sulfuric acid,
methyl-amino-ethyl-phosphoric acid ester,
2,5-dichloro-phenyl-amino-butyl-sulfuric acid,
4-methoxy-phenyl-amino-ethyl-sulfuric acid,
60
1 65
a
flémethoxy - phenyl - amino - diethyl - sulfuric
aci
,
.
3ichloro4tolyl-aminoébutyl-sulfuric acid,
a
.4
2,122,424
The illustrative partial esters have been, set
forth above in terms of the free acids. Normally
it is advantageous to employ these partial esters
in the form of a salt.
Hence they may be em
ployed in the form wherein the hydrogen or hy
drogens of the acid groups are substituted by a
metal, e. g. sodium or potassium.
,
of the partial ester salt. The product may be
recovered from solution in the same manner as in
Example 1 or the aqueous solutionmay be» evap
orated to dryness in a Vacuum or on a double drum
drier under reduced pressure.
The product is a
yellow powder readily soluble in water, having
the probable formula:
Any of the coupling components in use for cou
CH3
pling with diazo compounds may be employed
tholates, 2,3-hydroxy naphthoic acid arylides,
alkyl phenyl-pyrazolones, aceto-acetic acid aryl
ides, 2-hydroxy-carbazole-o-carbonic arylides,
15 and the ZA-dihydroxy-quinolines.
Speci?c ex
amples of these coupling components are given in
connection with the following examples and in
the table of dyestuif compositions which is a part
hereof.
20
The following examples will serve to further
illustrate the present invention.
'
Example 1.—l00 parts by weight of 3-chlor
aniline are diazotized in the customary manner
by means of hydrochloric acid and sodium ni
25 trite to yield an aqueous solution of 3-chlor
phenyl-diazonium chloride. This solution is
gradually run into an aqueous solution of the
sodium salt of N-methyl-amino-butyl-sulfuric
acid. The ester solution comprises about 150
30 parts of the ester, about 400 parts of sodium ace
During the
addition of the diazonium chloride, the aqueous
' tate, and about 1000 parts of water.
ester solution is stirred and cooled so as to main
tain the temperature at 0° to 5° C. The dia
35 zonium chloride addition is regulated to avoid
any substantial rise in temperature.
After the
'
|
10 with the diazoamino compounds of the present
invention, for instance the naphthols and naph- v
CH3
10
Cl
In a similar manner diazoamino compounds
may be prepared from the other chlor- and nitro 15
substituted anilines previously mentioned and
methylamino-butyl-sulfuric acid or alkali-metal
salts thereof; The products thus formed are
yellow to orange powders, readily soluble in water.
They are stable towards alkalis but are decom
action of acid reagents thereon.
Example 3.—'10 parts by weight of sulfanilic
acid (NI-I2—C6H4——p—SO3I-I-I-I2O) are diazotized 25
in the usual manner with sodium nitrite and hy
drochloric acid, and the resultant solution of the
diazonium chloride is introduced into an aqueous
solution of N-(beta-ethyl-cyclo-hexyl) -amino
ethyl-sulfuric acid, the solution comprising about 30
14 parts of the partial ester, 30 parts of sodium
acetate, and 200 parts of water. The cooling,
stirring, and addition of the diazonium chloride
are regulated as in Example 1 so that the tem
perature ‘does not exceed plus- 5° C.
The solution 35
The diazoamino compound
is then rendered slightly alkaline by addition of "
addition of the diazonium chloride is completed,
sodium carbonate.
the’ solution is made alkaline with soda ash in
which forms is salted out by the addition of sodium
chloride to the cold liquid, is ?ltered off and dried
slight excess and agitated at 0° C. for from one to
40 two hours or until no- free diazonium chloride can
be detected. The diazoamino ester salt which
forms has the following formula:
20
posed into the corresponding diazonium salts,
methylamino-butanol, and sulfuric acid by the
at a low temperature. The dry product is a
yellowish powder very soluble in water. It may be 40
represented by the following structural formula:
CH3
(13)
45
CH
45
CH,
The diazoamino sodium sulfate is then salted out
from the solution by adding thereto 200 parts of
50 sodium chloride. The crystallized ester is sepa
rated by ?ltration or centrifuging and is dried.
The product is a yellow powder readily soluble inv
water.
The isolation of the diazoamino compound may
55 be eifected in a number of ways. Normally it is
desirable to add a neutralizing agent to the solu
tion during coupling of the diazonium salt with
the amine or after the coupling is complete.
Instead of sodium carbonate any other suitable
60 alkaline neutralizing agent, either organic or in
organic, may be‘ employed, for example sodium
hydroxide, magnesia, magnesium carbonate, bar
ium carbonate, calcium carbonate, pyridine and
its homologues, and triethanolamine.
65
Example 2.—100 parts by weight of 2-methyl-5
chlor-aniline,
.
70
(In
Q-m
(11)
|
CH3
are diazotized and the diazonium salt solution is
added to an aqueous solution of methylamino
75 butyl-sodium-sulfate containing about 150 parts
In a similar manner diazoamino compounds 50
‘may be prepared from any of the carboxy- or . '
sulfo-substituted anilines previously mentioned.
Water-soluble azo dyestuffs may be prepared from
any of the resultant diazoamino compounds by
dissolving the diazoamino compound in water and 55
adding thereto a coupling component in aqueous '
solution and thereafter acidifying the solution
with a strong organic acid, for example formic
acid, acetic acid, or oxalic acid until an acid solu
tion of 3% to 10% strength is obtained.
Prefer
ably a small amount- of sodium acetate is added
prior to acidi?cation. The formation of the azo
60
dye can be accelerated by the application of heat
and proceeds rapidly at a temperature of from
50° to 60° C.
The coupling can be effected even 65
more rapidly by using a mineral acid for acidi?ca- .
tion, for example hydrochloric acid, or an acid
salt such as sodium bisulfate. The preparation
of soluble azo dyestuffs of the above type also may
be effected by introducing an» aqueous solution of 70
a coupling component into an aqueous solution of
the diazoamino compound to which an acid pre
viously has been added.
Example 4.—386 parts of the diazoamino com
pound obtained from 2-nitro-44methyl-phenyl
75
5
- 2,122,424
diazonium . chloride and .methylaminobutyl-so
. diumr-sulfate and having vthe probable formula:
CH3
(14)
N02
are dissolved in an/aqueous solution comprising
1500 parts of water and about 100‘parts of sodium
10 acetate. To the resultant solution an aqueous
alkaline solution comprising 220_parts of aceto
to 5ngrams of the amide, about 1 to about 10 cc.
of 34° Bé. (28%) NaOH and about 1 to about
10 cc. of Turkey red oil of 50% strength.
The impregnated cotton is introduced into the
bath containing the acidi?ed diazoamino com 5
pound and the bath is slowly heated to about
50° to 60° C. The formation of the azo dyestuif
on the ?ber occurs very readily. -' It has the
, probable formula:
NaOI-I is added.
10
01
I
‘acetanilide, 2000 parts’of water,_and 45 parts of
To this solution acetic acid is
gradually added to accomplish neutralization,
whereupon coupling proceeds progressively as
more acetic acid is added. The rate of coupling
may be accelerated by raising the temperature as
in Example 3. Upon completion of the reaction
a yellow dyestu? of the probable formula:
20
0.0—CH3
(15)
(19)
.
CH3
OH O
15
When the diazo compound can no longer be de
tected in the bath, the cotton is removed there
from, -is rinsed, soaped at boiling temperature,
rinsed again, and dried. A brilliant red of ex
20
cellent fastness is thus obtained.
Example 7.—The sodium salt of the diazoamino
compound obtainable from 2-methoxy-5-chlor
phenyl-diazonium chloride and N-methyl-amino
butyl-sulfuric acid _ and having the probable
25
formula
1
'
CH3
CH3
Cl
separates. This product maybe ?ltered off,
(20)
.30 washed and dried in any suitable manner.
Example 5.—An aqueous solution of the diazo
amino compound formed by coupling 2-,nitro
,4-methoxy-phenyl-diazonium chloride and cyclo
hexyl-amino-ethyl sulfuric acid, of the formula:
35
02114-0 scion
is treated with an alkaline‘ aqueous aceto-acetic
acid-2-toluidide solution containing an equimolar
with 2-hydroxy-3-naphthoic-acid-2’—anisidide in
an aqueous solution containing an equimolecular
quantity of NaOH.- The mixture is evaporated to
35
dryness at a low temperature in vacuum.
70 parts by weight of the dry product are made
up to 1000 parts with 50 parts Turkey red oil,
50 parts urea, 600 parts starch-tragacanth
thickener, and the remainder’ water. The re
sultantrprinting paste may be printed on a tex 40
tile fabric in the usual manner. The printed
fabric is passed through an acid vapor ager at a
temperature of 100° to 102° C., the ager being
supplied with steam containing between say .05%
. quantity of the aceto-acetic-toluidide, in the man
ner set forth in Example {1.7 {in orange yellow
azo dyezof the probable formula: '
130
in aqueous solution, is mixed in equimolar ratio
.
and 1% of acetic and .05% and 1/2% of formic 45
acid vapors to form the azo dye having the
probable formula:
‘
'7
’
QOCH:
CH
N=N—(|JH
l
V50
l
_,
N=N—
17
OzN
( )
g H
0 H
OCH:
|
I
(21)
1 £50
OOHs.
CH;
After a short period of contact of the printed
fabric with the acid vapors in the ager, say 2'
s55
.
0-—-CH3
is thus obtained.
minutes, the material is rinsed, soaped, and dried.
’ _
Example 6.--To 1000 parts by weight _‘ of an
.90 aqueous solution containing 4.6 parts by Weight
of the diazoamino compound obtained from 2
methylq'5-chlor-phenyl-diazonium-jchloride and
amingo-diethyl-disodium-disulfate, and having the
probable
formula:
'
.
A very bright scarlet print is thus obtained.
Example 8.-—A'paste made in the same man
ner as in Example‘ '7, but containing the diazo
amino compound from 2,5-dichlorphenyl-diazo
nium chloride and methylaminobutyl-sulfuric
acid together with Z-hydroxy-B-naphthoic acid
'2",5'-dimethoxy-anilide as a coupling component
instead of the diazoamino compound and cou
pling component of the previous example, yields a 65
-
(18)
CH3
.10 there is‘ added 20 parts of acetic acid,~5 parts of
alum, and 5 parts of sodium acetate. ’
Cotton fabric is impregnated in the customary
manner .with. 2-hydroxy-3-naphthoic acid-2'
naphthylamide; for instance 50 grams of cotton
may be ‘impregnated with a liquor containingl/z -
fast brown azo print on cotton, theazo com
pound having the probable formula:
6
‘2,122,424
Example 9.--About 31/2 parts of the diaaoamino Any of the usualmethods of developing
azo dye
stuffs by coupling diazoamino compounds and
coupling components may be employed with the
diazoamino compounds of the present invention.
compound from 3-chlor-phenyl-diazonium-chlo
ride and ethylaminobutyl sodium sulfate
'
Diazoamino compounds from diacid esters of
dialkylolamines and cycloalkyldiol amines as well
as those from esters of 'mono-alkylolamines and
cycloalkyl mon-olamines constitute an important
group among the products of the present inven-_
02115
‘on
'
r
'
'
/
>—N=N——N
"
‘ (23)
\
i (OH2)4OSQ2ONa
V
and about 2% parts of Z-hydroxy-3-naphthoic
tion. The di-ester diazoamino compounds of
greateriimportance may be represented by the
1O acid-2’-toluidide were made up to a paste with
hot water with the addition of 3 parts of the
mono-ethyl ether of glycol. To this paste 3 parts
general ' formula
by weight of 36° Bé. NaOH (30%), 60 parts by e
_,
(25)
weight of neutral starch tragacanth thickener
wherein Ar represents an aromatic radical, R5 15
parts by weight with vwater. This printing paste represents an alkyl preferably with 4 carbon
is applied to cotton fabric in the'iusual manner. atoms or cycloalkyl group, Acyl represents a
The print is then steamed for around 5 minutes 'polybasic acid igroup asdescribed in connection
15 are added, and the product is made up to 100
v
(or as an alternative is hung inv contact with the 'with Formula {1) and Me represents hydrogen, v
20 atmosphere for about 21‘ hours). The cotton is sodium, or potassium. The sulfuric acid esters 20
then introduced for a short‘ time into an aqueous of the'following general formula possess especial
advantages in that they are highly soluble in
bath maintained at about'80° to 90° C. and con
vtaining 50 grams ‘acetic acid and 50 gramsisodium water and alkaline aqueous solutions:
' '
sulfate per liter. eBy this’treatm ent the azo dye’
25 of the probable formula:
. A1‘—N=N—N §,—R50—SO2OM€) 2
5
wherein Ar represents an aromatic radical, R5
represents an' alkyl preferably with 47 carbon
atoms’ or cycloalkyl group, and Me representscH
(24)
H
p
or Na;
' The following table further illustrates the
nature of compositions of dyes that may be ob
'HO
tained bythe application of
iis developed on'the'?ber yieldin g a print of a
30
invention. In this
table are shown the shades of dyeings obtain
able with the diazoamino compounds and the
very brilliant orange shade of excellent fastness.
35 ,A similar result is" obtained by developing the
print in an acid bath containing formic acid, 0;;
"alic acid, ‘or another strong‘ organic acid instead
'of the acetic acid mixture. ‘Likewise develop
coupling componentsset forth. It will be under 35
stood that such'dyeings may be obtained by sub
stantive preparation, or by printing a textile ?ber
witli'ia printing paste'containing the diazoamino
" ment
a vapor lager cantaining a volatile acid
compound and coupling componenteand subse
quently developing, or by impregnating the tex 40
40 7, such as’ acetic acid produces similar results.
' > It will be obvious from the above examples that . tile ?ber with one of the components and subse
?'the procedure involved in the preparation and ‘quently'developing the'dye by bringing the im
' use of‘ my new diazoamino
or compo
_
‘ compounds
V
’ pregnated ?ber into contact with the other com
7 45 sitions is capable of, almost lirnitless variation.
ponent ‘under conditions favoring ‘azo coupling._
45
No.
Base
1
Stabilizer 1 '
2.5- dichloro -"l -
Hydroxy ethyl amino
aminobenzene.
5-0
s
,
.
2.5 - dichloro Q l #
v
‘
1'
7
/
,w/ '
s
‘
s
"
p
',
,
_,
;zene.
.
mine
>
and
EN
mic is hylethanola
_
v
Do.
l-aceto-acetylamino
i
benzene.
,7
\.
*
:
EN
1' I
Sulffonic ester E'from:
ylbenzene.
,
CHz?CHz—OOO--i@aH4—'COQH
.7
_ amino-l-meth-
,
"CH3
benzoic acid.
4.5 - dichloro - 2-
Yellow.
‘f
J
2.5 - dichloro - 4 - nitro-
‘
V
V
.. 4
Diacetoacetyl - o -:toli-
CHr-OHrOSOzH
7
4~sulfo
Shade
r
OHr-QHr-OH
7
Coupling component
dide.
_
"
3 4-Vchloro-2-amino- ‘Sulfonic ester from
1-1nethylbenmethyl ethanola~
7'
EN’
ethyl phthalic acid.
"'
s
'
7
Hydroxy ethyl amino
aminobenzene.
'
7
QHr-CHz-OH
ethyl sulfuric acid.
_
j
2
FOI'IIliIJa
..
,
..
Diacetoacetyl-o-tolia
dide
,
.
Do.
.
V
CHrCHrO-SOT“
60
___-.do
Do.
a»
be.
mine and 4-sulfo
65
65
a
gi-chloro-Z-azhinon .
" 1 - methoxy
I
Methyl-amino-ethylbenzoic acid.
. CH3 '
dichlorphthalic acid.
benzene. ’
-
»
175
f’
e,7
.
GOOH
"
.
OH2'—'CH2—0O0—®—C1
V
2.5-dichloro -1_-
r.
HN\
7270
6
.
‘I
Q
N gethane - sulfonic -‘
methyl-4-am1-
amino-butyl sulfuric
nobenzene.
acid.
onronrsoan'
'7
HN
V
01
r
‘
‘
l;
‘
"
'
e
OHT-OHrOHiLQHFQSOaH '
70
p
,
_-___do _______________ __
.
-
>
Do.
'
75
2,122,424
N0
Base
Stabilizer
44
6-amino-3-ben-
Ethyl-amino-butyl-
zoylamino-lA-
dimethoxybenzene.
45
4-chloro-2-aminol-methylben-
phosphoric acid.
9
Formula
/
C2115
EN
\
Coupling component
Shade
Sodium compound of
Do.
2-hydroxy-naphtha
0 OH
|| /
lene-3-carboxylic
acid O-toluidide.
Methyl-amino—propylsulfuric acid ester.
Sodium compound of
Z-hydroxy-carba
zene.
Brown.
10
zole - o - carboxylic
acid 2’-toluidide.
46
i-nitro - 4’ - ami -
Acid ester from meth-
no-2’5’-din1ethoxyazo - ben -
yl - ethanol - amine
and benzene-disul-
zene.
15
47
3-nitro-4’-ami-
no-2’5’-dimeth-
48
20
ionic acid.
no-Z-methoxy-
4-chlor0-4’-amino - 2'5’ - die-
ethyl-sulfuric acid.
Do.
Sodium compound of
amino-butyl-sulfu-
2-hydroxy-naphtha
ric acid.
Do.
lene-3-carboxy1io
.
acid o~toluidide.
Hydroxy-ethyl-amino-
Sodium compound of
butyl-sulfuric acid.
Do.
2-hydroxy-naphtha~
lene-3—carboxylic
zene.
acid alpha-naphthyl
amide.
25
4. As a new compound a diazoamino ester of
the following general formula
following general formula
30
wherein Ar .represents an aromatic radical, R1
represents a. saturated aliphatic or cycloaliphatic
35 group, R2 represents hydrogen, a saturated ali
wherein Ar represents an aromatic radical, R1
represents a saturated aliphatic or cycloaliphatic
group, R2 represents hydrogen, a saturated ali
phatic or cycloaliphatic group, or an aromatic 35
phatic or cycyloaliphatic group, or an aromatic
group, or R1 and R2 together represent a poly
group, or R1 and R2 together represent a poly
methylene chain forming a heterocyclic ring with
the —N—,Acyl representsthe residue of sulphuric
acid, phosphoric acid, or a polybasic acid of the
benzene or aliphatic series, Me represents hydro
methylene chain forming a heterocyclic ring with
gen or a metal, 712 represents a positive integer,
and x and 1/ each represents a positive integer.
2. As a new compound a diazoamino ester of the
the —N-—, Me represents hydrogen or a mono
valent metal, Acyl represents the residue of sul
furic acid, phosphoric acid, or a polybasic acid
of the benzene or aliphatic series, and a: and 1/
represent positive integers.
5. As a new compound a diazoamino ester of the
following general formula
I, following general formula
wherein Ar represents an aromatic radical, R1
represents a saturated aliphatic or cycloaliphatic
group, R2 represents hydrogen, a saturated ali
phatic or cyclo-aliphatic group, or an aromatic
group, or R1 and R2 together represent a poly
methylene chain forming a heterocyclic ring with
the --N—-,Merepresents hydrogen or amonovalent
metal, Acyl represents the residue of sulfuric acid,
phosphoric acid, or a polybasic acid of the ben
zene 'or aliphatic series, 1/ represents a positive
integer, and n1 represents an integer less‘ than 4.
60
15
2-hydroxy-naphtha
N-ethane-sulfonic
I claim:
1. As a new compound a diazoamino ester of the
1%
Sodium compound of
acid alpha-naphthyl
amide.
thoxy~azo~ben~
30
acid o-toluidide.
Hydroxy-ethyl-amino-
zene,
4-methyl-4’-ami-
Black.
2-hydroxy-naphtha1
lene-3-carboxylic
lene-3-carboxylic
benzene.
25
Sodium compound of
oxyazo - ben -
5-methylazo49
___
3. As a new compound a diazoamino ester of
the following general formula
45
wherein Ar represents an aromatic radical free
from sulfonate and carboxylate groups, R1 repre
sents a saturated aliphatic or cycloaliphatic
group, R2 represents hydrogen, a saturated ali
phatic or cycloaliphatic group, or an aromatic
group, or R1 and R2 together represent a poly
methylene chain forming a heterocyclic ring with
the -—N—, Me represents hydrogen or a mono
55
valent metal, Acyl represents the residue of sul
furic acid, phosphoric acid, or a polybasic acid of
the benzene or aliphatic series, and 1/ represents
a positive integer.
6. As a new compound a diazoamino ester of the 60
following general formula
Ar—N= N-—N(—R1—OAcyl—OMe) 2
represents a saturated aliphatic or cycloaliphatic
group,‘R2 represents hydrogen, a saturated ali
wherein Ar represents an aromatic radical, R1
represents a saturated aliphatic or cycloaliphatic 65
group, and Me represents hydrogen or a mono
valent metal.
phatic or cycloaliphatic group, or an aromatic
group, or R1 and R2 together represent a poly
amino-aliphatic sulfuric acid partial ester.
65 wherein Ar represents an aromatic radical, ‘R1
70 methylene chain forming a heterocyclic ring with
the —N--, Me represents hydrogen or a monova
lent metal, Acyl represents the residue of sulfuric
acid, phosphoric acid, or a polybasic acid of the
benzene or aliphatic series, 1/ represents a positive
75 integer, and 122 represents an integer less than 4.
7. As a new compound, an aromatic diazo
8. As a new compound a diazoamino ester of 70
the following general formula
I
Ar —N=N—I|\l—-R1—O-SO2——0Me]
I
R2
'Il1
wherein Ar represents an aromatic radical free
2,125,424
10
from sulfonate and carboxylate groups, Rr‘repre- represents an acid group, and n1'1'represents an
integer less than 4, with an amino partial ester
sents asaturatedaliphatic or cycioaliphatic hy
of the general formula
'
drocarbon group, R2 represents hydrogen, a satu
Hi7N—-R1——O-—Acyl(-—O'Me),,
rated aliphatic or cycloaliphatic group, or an aro
matic group, Me represents hydrogen or a mono
valent metal, and m represents an integer less
than 4.
‘
'
9. As a new compound a diazoamino ester of
the
f, following
Ar-—N=N—N——
general formula
R1-—O—SO2——-OMe
> [
20
I!“
2i
wherein R1 represents a saturated aliphatic or
cycloaliphatic group, R2 represents hydrogen, a
saturated aliphatic or cycloaliphatic group, or
an aromatic group, or R1 and R2 together repre
sent a polymethylene': chain forming a hetero
'
1'12 722
10
cyclic ring with the —N—, Acyl represents the
wherein Ar represents an aromatic radical, R1
represents a saturated aliphatic or cycloaliphatic
15 hydrocarbon group, R2 represents hydrogen, a
saturated aliphatic or cycloaliphatic group, or
an aromatic vgroup, Me represents hydrogen or a,
monovalent metal, and 112 represents an integer
less than 4.
..
"
residue of suifuric acid, phosphoric acid, or a
polybasic acid'of the ‘benzene or aliphatic series,
Me represents hydrogen or a monovalent metal, 15
and 1;: represents a positive integer.
17. The method of producing a diazoamino
compound of the type set forth in claim 3, which
comprises coupling in ‘an alkaline medium an
1
10. As a new compound a diazoamino ester of
aromatic diazonium salt of the general formula
the following general formula
wherein Ar represents an aromatic radical and 2
represents an acid group, With an amino partial
wherein Ar rep-resents an aromatic radical free
ester of the general formula
25 from siilfonate and carboxylate groups, R1 rep
resents a saturated aliphatic or cycloaliphatic
hydrocarbon group, R2 represents hydrogen, a
saturated aliphatic or cycloaliphatic group, or
an aromatic group, and‘Me represents hydrogen
or a monovalent metal.
11. As a new compound a diazoamino ester of
the following general formula 7
1
saturated aliphatic ;or cycloaliphatic group, or
an aromaticngroup, or R1 and R2 together repre
sent a'polyinethylene chain forming a hetero
cyclic ring with the —N—, Acyl represents'athe
gen or a monovalent metal,
less than 4.
,
amino-aliphatic sulfuric acid partial ester in the
form of an alkali-metal salt.
13. As a new compound an aromatic diazo
aminobutyl sulfuric acid partial ester in the form
of a sodium salt.
I
e
14. As a new compound an aromatic diazo
amin0-di(butyl sulphuric acid) partial ester.
15. The method of producing a diazoamino
compound of the type set forth in claim 1, which
comprises coupling a; diazonium salt of the gen
50
j,
represents a saturated aliphatic or cycloaliphatic
hydrocarbon group, and Me represents hydro
12. As a new compound, an aromatic diazo
45
[ . 1'12 1112
eral formula
'
Ar-—(N:N—z) 111
wherein Ar represents an aromatic radical, 2
represents an acid group and n1 represents a
positive integer, with an amino partial ester of
55 the general formula
H——N— —R1—~O— gey1<—oMe),
wherein R1 represeiits a saturated aliphatic or
60 cycloaliphatic group, R2 represents hydrogen, a
saturated aliphatic or cycloaliphatic group, or
angaromatic group, or R1 and R2 together rep
resent a polymethylene chain forming a hetero
cyclic ring with the —N—, Acyl represents the
residue of sulfuric acid,- phosphoric acid, or a
polybasic acid of the benzene or aliphatic series,
Me represents hydrogen or':a metal, n2 represents
a positive integer, and :1: and g each represents
a positive integer.
‘
16. The method of producing a diazoamino
compound of the typeset forth in claim 2, which
comprises coupling in an alkaline medium an
aromatic diazonium salt of the general formula
_
Ar(—N=N--—z)n1
@
wherein Ar represents an aromatic radical, 2
25
wherein R1 rep-resents asaturated aliphatic. or
cycloaliphatic group, R2 represents hydrogen, a
residue of sulfuric acid, phosphoric acid, or a
polybasic acid of the benzene or aliphatic series,
Me represents hydrogen or a monovalent metal,
1; represents a positive integer, and 112 an integer
35 wherein Ar represents an aromatic radical, R1
40
'
R—N— R1—o-Aey1(-0Me),
18. The
compound
comprises
diazonium
7;;
'
method ;;of producing a diazoamino
of the type set forth in claim 4, which 40
icoupling in an alkaline solution a
salt of the general formula
;
Ar—N=N—z
~
wherein Ar represents an aromatic radical and 2
45
represents an acid group, with an amino partial
ester of the general formula
( R2
)z
wherein 94* represents an aromatic radical, R1
represents a saturated aliphatic or cycloaliphatic
group, R2 represents hydrogen, a saturated ali
phatic or clycloaliphatic group, or an aromatic
group, or R1 and R2 together represent a poly
methylene chain forming
heterocyclic ring with
the —N——~, Me represents hydrogen or a mono
valent metal, Acyl represents the residue of sul
furic acid, phosphoric acid, or a polybasic acid
of the benzene or aliphatic series, and a: and y
00
represent positive integers.
19. The method of producing a diazoamino
compound of the type set forth in claim 5, which
comprises coupling a diazonium salt of the gen
eral formula
65
wherein Ar represents an aromatic radical free
from suli‘onate and carboxylate groups and 2 rep
resents
acid group, with an amino ester of the
general formula
H—l|\l'——R1——O—Acyl(—0Me)g
R2
70
'
wherein R1 represents a saturated aliphatic or
cycloaliphatic group, R2 represents hydrogen, a
saturated aliphatic or cycloaliphatic group, or
w
11
2,122,424
an aromatic group, or R1 and R2 together rep
resent a polymethylene chain forming a hetero
wherein Ar represents an aromatic radical and
2 represents an acid group, with an amino partial
cyclic ring with the —N—, Me represents hy
ester of the general formula
drogen or a monovalent metal, Acyl represents
the residue of sulfuric acid, phosphoric acid, or
a polybasic acid of the benzene or aliphatic series,
and 1] represents a positive integer.
20. The method of producing a diazoamino
compound of the type set forth in claim 8, which
wherein R1 represents a saturated aliphatic or
[ l. m
cycloaliphatic hydrocarbon group, R2 represents
hydrogen, a saturated aliphatic or cycloaliphatic
comprisescoupling in an alkaline medium an aro
group, or an aromatic group, Me represents hy
matic diazonium salt of the general formula
drogen or a monovalent metal, and n2 represents
an integer less than 4.
22. The method of producing a diazoamino
compound of the type set forth in claim 10, which
comprises coupling in an alkaline medium a 15
diazonium salt of the general formula
wherein Ar represents an aromatic radical free
15 from sulfonate and carboxylate groups, 2: repre
sents an acid group, and n1 represents an integer
1O
less than v4:, with an amino partial ester of the
general formula
20
wherein R1 represents a saturated aliphatic or
wherein Ar represents an aromatic radical free
from sulfonate and carboxylate groups and 2 rep
resents an acid group, with an amino partial ester
of the general formula
cycloaliphatic hydrocarbon group, R2 represents
hydrogen, a saturated aliphatic or cycloaliphatic ‘
25 group, or an aromatic group, and Me represents
hydrogen or a monovalent metal.
21. The method of producing a diazoamino
compound of the type set forth in claim 9, which
comprises coupling in an alkaline medium an aro
30 matic diazom'um salt of the general formula
wherein R1 represents a saturated aliphatic or
cycloaliphatic hydrocarbon group, R2 represents
hydrogen, a saturated aliphatic or cycloaliphatic
group, or an aromatic group, and Me represents
hydrogen or a monovalent metal.
JEAN G. KERN.
25
Документ
Категория
Без категории
Просмотров
0
Размер файла
1 398 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа