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2,115,030
Patented Apr. 26, 1938
‘ UNITED STATES
PATENT OFFICE
2,115,030 p
'
AZO COMPOUNDS m'rnoonss'ron
comamc 'rnrnnwrrn
James G. McNally and Joseph B. Dickey, Roches-
’
ter, N. Y., as‘signors to Eastman Kodak Com
pany, Rochester, N. Y., a corporation of New I
Jersey
,
No Drawing. Application June 4, 1937,
I
Serial No. 146,524‘
19 Claims.
This invention relates to aryl azo com
pounds. More particularly it relates to aryl azo
derivatives of malonylmalonamide and the appli
cation of the nuclear non-sulfonated aryl azo
5 derivatives of malonylmalonamide for the colora
tion of organic derivatives of cellulose. The in
ventionincludes the azo compounds, the process
for their preparation, the process of coloring with
themv and materials colored with the azo co
10
pounds of the invention.
a
-
'
H Organic derivatives of cellulose are character
ized by an indi?erent ailinity for the usual cotton
or wool dyes, especially the ordinary water soluble
dyes. Typical organic derivatives of cellulose in
15 clude thehydrolyzed as well as the unhydrolyzed
cellulose organic acid esters, such as cellulose
acetate, cellulose formate, cellulose propionate or
cellulose butyrate, and the hydrolyzed ascwell as
the unhydrolyzed mixed organic acid esters of
20 cellulose, such as cellulose acetate-propionate,
cellulose acetate-butyrate, and the cellulose
ethers, such as methyl cellulose, ethyl cellulose
or benzyl cellulose.
-
The azo compounds of our invention are repre
25 sented by the following formulae:
Formula 1
I '
(Cl. 8-5)
general Formula 2, when one molecular weight of
malonylmalonamide is caused to couple with an
equivalent molecular Weight of, a diazotized aryl
amine. As indicated above, the coupling is selec-.
tive in that the combining power of one of the I
reactivemethylene groups of the malonylmalon
amide is fully used up before appreciable cou
pling occurs at the second reactive methylene
group. To form compounds having the general
Formula 2, wherein R and R1 are the same, pref- 10
erably, the malonylmalonamlde and diazotized
arylamine should be present in the proportions
of about one mole of malonylmalonamide to about
two moles of the diazotized arylamine and the
coupling reaction should be continued until com- 1‘
pleted. In any event coupling should be. con
tinued until formation of the disazocompound
takes place where compounds of the general‘For
mula 2 are desired.
To form compounds of the general Formula 2 20
wherein R and R1 are different aryl nuclei‘ a
mono' azo'aryl compound of malonylmalonamide
is ?rst formed following which it is coupled with
a diazotized arylamine di?erent from that em
ployed to form the mono azo compound.
1-amino-2-methoxy-4-nitrobenzene
. ’ ,25
and _
1- .
1 amino-2-nitro-4-chlorobenzene, o-anisidine and
1-amino-2-‘nitro-4-chlorobenzene and o-chloro
aniline and p-nitroaniline, for example, are repre
sentative of the combination of amines that may 30.
be employed in this connection.
h
The nuclear non-sulfonated azo compounds of
‘our invention constitute a valuable class of dyes
suitable for the dyeing or coloration of material
made of or containing an organic derivative of 35
cellulose. By means of the non-sulfonated azo
compounds, dyeings may be produced which are
of good fastness to light and washing and which
range in shade from'lgreen-yellow to red.
wherein R and R1 represent the same or dif
ferent aryl nuclei. Advantageouly R and R1
represent aryl nuclei of the benzene ‘series.
. The azo compounds of our invention can be
45 prepared by diazotizing an arylamine and cou
pling the diazonium compound formed with
malonylmalonamide in an alkaline medium.
Malonylmalonamide may be'prepared as de
scribed in Journal of the Chemical Society,
50 volume 99, page 615. (i911).
'
As apparent from Formula 2, one mole of
malonylmalonamide is capable of coupling with
two moles of a diazotized arylamine. A compound
having the general Formula 1' is formed, to the
55 substantial exclusion of a compound having the
The nuclear sulfonated compounds of our in- 40
vention possess little or no practical utility for
the dyeing of organic derivatives of cellulose but
may be employed for the dyeing of other mate
rials such as cotton and wool, for example, being
applied thereto by the customary methods of ap- ' 45
plication' Again, it'should be noted that when
the compounds of our invention are to be em
ployed for the coloration of organic derivatives
of cellulose, it is generally advantageous that they 50
contain no carboxylic acid group as this group
generally affects the stability of the dyeing ad
versely. It should be noted that while nuclear
non-sulfonated azo compounds of the general
Formula 1 or the general Formula 2 may be, em- 55
2,115,030
2
stirring. Upon completion of the coupling 1'8
action which takes place, the ‘mixture is made
cellulose, those compounds having the general acid
to litmus by‘ the addition of acetic acid and
Formula 1‘ have been found to be of greater utility _ the dye compound formed is recovered by ?ltra
for this purpose.
and dried. The dye has
The following examples illustrate the method tion, washed with water
the
formula:
of preparation of the axe compounds of our in
ployed for the dyeing of organic derivatives of
vention:
-
Example 1
,
10
13.7 grams of o-phenetidine are dissolved in
10 200 cc; of water containing 25 cc. of 36% hydro
15
chloric acid. The resulting solution is cooled to
a temperature of 0-.5° C. and diazotized ‘by the
- addition, with stirring, of 6.9 grams of sodium
nitrite dissolved in water.
sod?!
It colors wool yellow.
17 grams-of malonylmalonamide are dissolved,
'
in 300 cc...of water containing 31.8 grams of
sodium carbonate. The resulting solution is
‘cooled to a temperature approximating 040° C.
and the diazo solution prepared above is added
'20 withv stirring. Upon completion of the coupling
reaction which takes place, the mixture is made
acid to litmus by the addition of acetic acid and
the dye compound formed is recovered by ?ltra
tion, washed, with water and dried. The dye has
25
13.6 grams of p-aminodimethylaniline are dis
solved in 200 cc. of water containing" 40 cc. of
36% hydrochloric acid. The resulting solution
is cooled, by the addition of ice, to a temperature
approximating 0-5" C. and diazotized by the ad
dition, with stirring, of 6.9 grams of sodium ni
trite
35
i
‘
dium carbonate. The resulting solution is cooled
to a temperature approximating 0-10° C. and the
diazo solution prepared above is added with stir
ring. Upon completion of the coupling reaction 80'
which takes place, the mixture is made acid to
litmus by the addition of acetic acid and the dye
compound formed is recovered by ?ltration,
washed with water and dried. The dye has the
and colors cellulose acetate silk green-yellow
-
Example 2
_
in 300 cc. of water containing 31.8 grams of so
=0
from a water suspension.
in water.
17 grams of malonylmalonamide are dissolved
the formula:
30
18
_
Example 4
‘
formula:
16.3 'gramsof 1-amino-2-methoxy-4-nitroben
zone are added to 200 cc. oi water containing 30
cc. of 36% hydrochloric acid. The resulting so
lution is cooled to a temperature approximating
0-5° C. by the addition of ice and diazotizedin the
o= —-N-— =0
-
usual manner by the addition, with stirring,‘ of
6.9 gramsbt sodium nitrite dissolved in water.
17 grams of malonylmalonamide are dissolved
aqueous suspension.
Example 5
in 300 cc. oi'water containing 31.8 grams of so
16.7 grams of
dium carbonate. The resulting solution is cooled
to a temperature approximating 0-10° C‘. and
the diazo solution prepared above is added with
stirring. Upon completion of the coupling re
action which takes place, the mixture is made
50 acid to litmus by the addition of acetic acid and
the dye compound formed is recovered by ?ltra
tion, washed with water and dried. The dye has
the formula:
>
H
and colors cellulose acetate silk red from an
,
Gm
\ocmioom
are diazotized in the usual manner.
8.5 grams of malonyhnalonamide are dissolved _.
in one liter of water containing 30 grams of so.
dium carbonate. Ice is added and the diazo so
lution prepared above is slowly added with stir
'
ring. When coupling is complete, the mixture 1
_ is made acid to litmus with hydrochloric acid and
55
the precipitated dye compound formed is recov
ered by ?ltration, washed with water and dried. '
and colors cellulose acetate silk golden ‘yellow
- The dye has the formula:
,
.
'
from its suspension in water..
Example 3
34.7 grams of disodium-Z-aminonaphthalene
4,8-disulfonate are dissolved in 200 cc. of water,
the resulting solution is well iced and then 50
cc. 01 36% hydrochloric acid are added with
vigorous stirring. A concentrated solution of
6.9 grams of sodium nitrite is then gradually
added with stirring and the mixture is stirred
until diazotization is complete.
.
'
1'7 grams of malonylmalonamide are dissolved‘
in 300 cc. of water containing 31.8 grams of so
dium carbonate. The resulting solution is cooled
to a temperature approximatingv 0-l0° C. and
75 the diazo solution prepared above is added with _
H
CiH4-OCH:
0CzH4—-OCHI
.,
and colors cellulose acetate silk yellow from an
aqueous suspension.
Example 6
16.3 grams of 1-amino-2-nitro-4-chloroben
zene are diazotized in the usual manner.
8.5 grams of malonylmalonamide are dissolved
in one liter of water containing 30 grams of so
dium carbonate. Ice is added and the diazo so-‘
lution prepared above is slowly added, with stir 75
2,115,030
ring. When coupling is complete, the mixture is
made acid to litmus with hydrochloric acid and
the precipitated dye compound formed is re
covered by ?ltration, washed with water and
dried. The dye has the formula:
10
3
disazo compounds can be prepared by coupling
one mole of malonylmalonamide with one mole
of a diazotized amine and completing the cou
pling reaction with a'mole of a second diazotized
amine. The diazotization and coupling reac
tions may, for example, be carried out following
the general procedure described in Examples 1
to 8 inclusive. The colors given in the tabulation
arethose for the monoazo derivatives of malonyl
malonamide but the disazo compounds produce
and 'colors cellulose acetate silk a yellow shade’ generally similar colors. .
from an aqueous suspension.
15
Example 7
27.1 grams of o-methoxybenzeneazocresidine
are suspended in 400 cc. of water containing 40
cc. of 36% hydrochloric acid and diazotized at a
temperature approximating 20° C. by the addi
tion, with stirring, of 6.9 grams of sodium ni
20 trite dissolved in water.
17 grams of malonylmalonamide are dissolved
in 300 cc. of water containing 31.8 grams of
Aminc
Color on cellu
Coupling component
lose nilolgtate
s
o-Anisidine _______________ _. Malonylmalonamide
p-Anisidine__..
15
Yellow.
__-do ____________ -_
Do.
o-Ohloroamlmep~Chloroaniline___
Do.
Do.
p-Aminoaoetophenone-
_
Do.
p-Nitroaniline; ___________ __
Golden yellow.
1-amino-2-nitr0-4'chl0toben-
Do.
zene.
a-naphthylamine ______________ -_do ____________ ._
Yellow.
sodium carbonate. The resulting solution is
cooled to a temperature approximating 0-10” C.
and the diazo solution prepared above is added
p-Aminodimethylaniline_.'._ _-___do ____________ __
Bed.
with stirring. Upon completion of the coupling
of our invention may be clearly understood, their
reaction which takes place, the mixture is made
acid to litmus by the addition of acetic acid and
the
dye compound formed is recovered by ?ltrar
30
tion, washed with water and dried. The dye
compound has the formula:v
20
.
In order that the application of the compounds
application for the direct dyeing er coloration of
materials made of or containing an organic de
rivative of cellulose, and more particularly cellu
lose acetate silk, is described hereinafter.
Al
30
though the remarks are more particularly di
rected to the dyeing or coloring of the above
.I mentioned materials those pertaining to tem
perature, the dispersing agents and the amounts
of dispersing agent and dye which may be em
ployed, for example, are of general applicability
where the dye is to be applied directly to the ?ber
and colors cellulose acetate silk orange yellow
from an aqueous suspension.
Example 8
18.6 grams of 1-sulfonic-2-amino-5-nitroben
zene are dissolved in 150 cc. of water containing
45 6 grams of sodium carbonate and diazotized in
the usual manner. 8.5 grams ‘of malonylmalon
amide are dissolved in 100 cc. of water containing
15 grams of sodium carbonate. The resulting
solution is cooled and the diazo solution prepared
above is slowly added with stirring. When cou
50 pling is complete, the reaction mixture is made
acid to litmus by the addition of hydrochloric
acid. The dye compound formed is precipitated
out by the addition of sodium chloride after
55 which it is recovered by ?ltration, washed with
water and dried. The dye has the formula:
from an aqueous suspension. ' The general meth
ods by which the dye compounds may be applied
to the coloration of other materials are well
known in the art and need not be described here.
In employing the aromatic azo ‘derivatives of
our invention as dyes, they will ordinarily be ap
plied to the material in the form of anaqueous
suspension which can be prepared by grinding the 45
dye to a paste in the presence of a sulfonated oil,
soap, or other suitable dispersing agent and dis
persing the resulting paste in water. Dyeing op
erations can, with advantage, be conducted at a
temperature of 80-85" 0., but any suitable tem 50
perature may be used. In accordance with the
usual dyeing practice, the material to be dyed
will ordinarily be added to the aqueous dye bath
at a temperature lower than that at which the
main portion of the dyeing is to be effected, a
temperature approximating 45-55“ C., for exam
55
ple, following which the temperature of the dye
bath will be raised to that selected forca'rrying
out the dyeing operation. The temperature at
60
0|N8_
H
S0;Na
and colors silk and wool orange-yellow shades
from an aqueous solution of the dye which may
contain salt.
65
.
'
The following tabulation further illustrates the
compounds included within the scope of our in
vention together with the color they produce on
cellulose acetate silk. Monoazo compounds may
be prepared by diazotizing one mole of an amine
70 listed under the heading “Amine” and coupling
with one mole of malonylmalonamide which is
listed in the column entitled “Coupling compo
nent”. Disazo compounds may be prepared by
diazotizing two moles of an amine and coupling
75 with one mole of malonylmalonamide. Similarly
which the dyeing is conducted will vary some
what, depending, for example, on the particular,
material or materials undergoing coloration.
The amount of dispersing agent employed may
be varied over wide limits.
Amounts approxi- ,
mating 10 to 200% by weight. on the dye may be 65
employed, for example.
These amounts are not -
to be taken as limits as greater or lesser amounts
can be used. To illustrate, if the dye is ground
to a sufficiently ?ne powder, dyeing can be satis
factorily carried out without the aid of a dis 70
persing agent. Generally speaking, however, the
use of a dispersing agent is desirable. _
Advantageously, dyeing is carried out in a s'ub- '
stantially neutral dyebath. Perhaps, more ac
curately, it should be stated that dyeing should 75
2,115,030
4
" not be carried out in an alkaline dyebath, that
I is, one having any substantial alkalinity, since the
presence of freealkali appears to affect the dye
ing adversely. Dyeing in an acid dyebath is not
recommended because of the tendency of acids
to affect the material'undergoing dyeing adverse
ly. Because of these‘considerations when a dis
persing agent is to be employed preferably it is
neutral or substantially neutral.
the temperature is gradually raised to 80-85° C.
and the silk worked for several hours at this latter
temperature. Sodium chloride may be added as
desired during the dyeing operation to promote
exhaustion of the dyebath. Upon completion of
the dyeing operation the cellulose acetate silk is
removed, washed with soap, rinsed and dried. The
cellulose acetate silk is colored a yellow shade of
~
It will be understood that the azo compounds of
our invention may be applied to the material to
be colored in any suitable manner. Coloration
may be effected, for example, by dyeing, printing,
or stenciling. Dispersing or solubilizing agents
that can be employed for preparing suspensions
of the dye include soap, sulphoricinoleic acid,
salts of sulphoricinoleic acid, a water soluble salt
of cellulose phthalate, cellulose succinate or cellu- '
[lose mono-acetate diphthalate, for example, the
sodium, potassium or ammonium salts, and sul
fonated oleic, stearic or palmitic acid, or salts
‘thereof, such, for example, as the sodium or am
monium salts.
While it is preferred to effect coloration by ap
plying the dye compound from an aqueous dye
bath directly to the material to be colored, colora
tion may be e?ected by absorbing and diazotizing
good fastness to light.
While our invention has been illustrated in con 10
nection with the dyeing of cellulose acetate silk, it
will be understood that dyeing operations can be
carried out in a manner similar to that described
above by the substitution of another organic de
rivative of cellulose material for cellulose acetate 15
silk or by employing dye compounds other than
those employed in the examples, or by substitu
tion of both the material being dyed and the dye
compounds of the examples.
We claim:
'
20
1. An .azo compound selected from the class
consisting‘of azo compounds having the general
formulae:
25
an amine on the ?ber after which the dye is
formed in situ by developing with malonylmalon
amide.
The following examples illustrate how dyeing
30
may be carried out in accordance with our in
vention. Quantities are expressed in parts by
weight.
wherein R and R1 each represent a member se 35
lected from the class consisting of an aryl nucleus
of the benzene and naphthalene series.
2. An azo compound having the general for
Example A
mula:
‘
,
'40
‘ are ?nely ground with a dispersing agent such as .
soap or oleyl glyceryl sulfate and the resulting.
45
paste is dispersed in 1,000 parts of water. ,The
wherein R represents a member selected from the‘ (
ture approximating 45-55° C. and 100 parts of
and naphthalene series.
3. An ‘azo compound 'having the general for
dispersion thus prepared is heated to a tempera- _ class consisting of an aryl nucleus of the benzene _
- cellulose acetate silk, in the form of yarn or fabric,
50
for example, are added to the dyebath after which mula:
the temperature is gradually raised to 80~85° C.
and the silk worked for several hours at this
latter temperature. Sodium chloride may be
added as desired during the dyeing operation to
55
promote exhaustion of the dyebath. Upon com
pletion of the dyeing operation, the cellulose‘ wherein R represents an aryl nucleus of the ben
acetate silk is removed, washed with soap, rinsed zene series.
4. An azo compound having the general for
and dried. The cellulose acetate silk is colored a
mula:
'
yellow shade of good fastness to light.
.
2.5 parts of
Example B
'
'
65
wherein R and R1 each represent a member se
‘ ' are ?nely ground with a dispersing agent such as
soap or oleyl glyceryl sulfate and the resulting
70 paste is dispersed in 1,000 parts of water. The
dispersion thus prepared is heated to a tempera
ture approximating 45-55° ‘C.~and 100 parts of
cellulose acetate silk, in the ‘form of yarn or fabric,
for example, are added to the dyebath after which
76
lected from the class consisting of an aryl nucleus
of the benzene and naphthalene series.
5. An azo compound having the general for
mula:
-
H
‘
O_=C--N—C=O
R——N=N-- H H T-N=N-R,
()= -—;N,—- =0
‘H
.
70
2,115,030
wherein R and R1 each represent an aryl nucleus
of the benzene series.
6. A process of coloring an organic derivative
of cellulose which ‘comprises applying thereto a
dye selected from the class consisting of azo com
pounds having the general formulae:
5
from the class consisting of azow compounds hav
ing the general formulae:
~
and
1b
10
15
15
wherein R and R1 each represent a memberv se
lected from the class consisting of a nuclear
non-sulfonated aryl nucleus of the benzene and
naphthalene series.
wherein R and R1' each represent a member se
20 lected from the class consisting of a. nuclear non
11. A process of coloring a cellulose acetate '
which comprises applying thereto a dye selected‘ 20
from the class consisting of azo compounds hav
sulfonated aryl nucleus of the benzene and naph
thalene series.
'
ing the general formulae:
7. A process of coloring an organic derivative
'
of cellulose which comprises applying thereto a
25 dye selected from the class consisting of azo com
pounds having the general formulae:
and.
30
35
wherein R and R1 each represent a member se
40 lected from the class consisting of a nuclear non
sulfonated aryl nucleus of the ‘benzene series.
8. A process of coloring an organic derivative
of cellulose which comprises applying thereto a
dye selected from the class consisting of azo com
wherein R and R1 each represent a member se
lected from the class consisting of a nuclear non
sulfonated aryl nucleus of the benzene series.
.
12. A process of coloring a cellulose acetate
which comprises applying thereto a dye selected 40
from the class consisting of 9.20 compounds hav
ing the general formula:
45 pounds having the general formula:
45,
H
0=C—-N—-C=0
R——-N=N—- H
50
_
H,
o= -N- =0
R
.
50
wherein R represents a nuclear non-sulfonated
,
- aryl nucleus of the benzene series.
wherein R represents a nuclear non-sulfonated
aryl nucleus of the benzene series.
9. A process of coloring an organic acid ester
55
of cellulose which comprises applying thereto a
dye selected from the class consisting of azo com
pounds having the general formulae:
13. Material made of or containing an organic
derivative of cellulose colored with a dye selected '
from the class consisting of azo compounds hav-'
55
ing the general formulae:
I
00
wherein R and R1 each represent a member se
lected from the class consisting of a nuclear non
sulfonated aryl nucleus of the benzene series.
10. A process of coloring a cellulose acetate
which comprises applying thereto a dye selected
wherein R and R1 each represent a member se
lected from the class consisting of a nuclear non
sulfonated aryi nucleus of the benzene and naph
thalene series.
.1
14. Material made of or containing an organic .
derivative of cellulose colored with a dye selected
70'
2,115,030
.6
from the class consisting of azo compounds hav
ing the general formulae:
lected from'the class consisting of azo compounds
having the general form/ulae:
H
=C—N——C=O
I R‘Ne-N- H
Hr
5
O: --N—- ==O
>
and
E
H
=C—N-C=O
10
R—N=N-cH ~H -——N=N--R1
‘a 10
o'= —-N—- =0
H
wherein R and R1 each represent a member se
15 lected from the class consisting of a nuclear non
sulfonated aryl nucleus of the benzene series. '
20
wherein R and R1 each represent a member se- _
lected from the class consisting of a nuclear non- l5
sulfonated aryl nucleus of the benzene and naph
thalene series.
15. An organic derivative of cellulose colored
with a dye selected from the class consisting of
18. A cellulose acetate colored with a dye se
lected from the class consisting of azo compounds 2
azo compounds having the general formulae:
having the general formulae:
v
I
H
0
‘
O=?—N-C=O
R—N=N--CH
H,
O=C——N-—
=0
H
25
25
and
H
O=C—-N—C=O g
R-—N=N—-(lJH HC'—-N=N——Ri
o= —-N— =0
30.
'
30
H
wherein R and R1 each represent a member se
wherein R and R1 each represent a member se
lected from the class consisting of a nuclear non
35.
sulfonated aryl nucleus of the benzene series.
16. An organic derivative of cellulose colored
with a dye selected from the class consisting of
azo compounds having the general formula:
lected from the class consisting of a nuclear non
sulfonated aryl nucleus of the benzene series.
35
19. A' cellulose acetate colored with a dye se
lected from the class consisting of azo compounds
having the general formula:
'
H
O=(|}—-N-—C=O
Ha
R—-N=N—-GH
o=c-N—c=o
H
wherein R represents a nuclear non-sulfonated
45
wherein R represents a nuclear non-sulfonated
aryl nucleus of the benzene series.
17. A cellulose acetate colored with a dye se
aryl nucleus of the benzene series.
JAMES G, MCNALLY.
JOSEPH B. DICKEY.
1
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