close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2130358

код для вставки
' In;
Patented Sept. 20, 1938
2,130,358 ‘
UNITED STATES PATENT OFFICE.
'
2,130,358
AZO COMPOUNDS AND PROCESS FOR
COLORING THERE-WITH
James G. McNally and Joseph B. Dickey, Roches
ter, N. Y., assignors to Eastman Kodak Com
pany, Rochester, N. Y., a corporation of New
Jersey
-
Application April '7, 1937,
No Drawings.erial No. 135,556
' ‘14 Claims.
This invention relates .to aryl azo compounds.
/
More particularly it relates to nuclear non-v
sulfonated aryl azo compounds suitable for the
coloration of organic derivatives of cellulose.
5 The invention includes the azo compounds, the
process for their preparation, the process of col
oring with them and materials colored with the
azo compounds of the invention.
Organic derivatives of cellulose are charac
terized by an indi?‘erent a?inity for the usual
cotton or wool dyes, especially the ordinary water
soluble dyes. Typical organic derivatives of cel
lulose include the hydrolyzed as well as the un
15
hydrolyzed cellulose organic acid esters, such as
cellulose acetate, cellulose formate, cellulose pro
pionate or cellulose butyrate, and the hydrolyzed
as well as the unhydrolyzed mixed organic acid
esters of cellulose, such as cellulose acetate-pro
pionate, cellulose acetate-butyrate, and the cel
lulose ethers, such as methyl cellulose, ethyl cel
lulose or benzyl cellulose.
We have discovered that the aryl azo deriva
tives of compounds having the general formula:
)
.
Formula I
CHa-Gé3
1
Bios 2c=N-x
4
3|
0:, ——-NH
-
wherein X represents hydrogen, an alkyl group,
an aryl group or an alkaryl group, constitute a
3O
valuable class of compounds. These compounds,
which make up the compounds of our invention,
have the following general formula:
CH3—-C-_=N
1!
R—N=N— $6{i5 §C=N~X
0: ——-NH
wherein X has the meaning previously assigned
(Cl. 8-5)
pounds of our invention may be employed for
the dyeing‘ or coloring of organic derivatives of
cellulose. By the employment of these nuclear
non-sulfonated aryl azo compounds dyeings of
good fastness' to light and washing ranging in
shade from yellow to red can be produced on
organic' derivatives of cellulose.
The nuclear
sulfonated aryl. azo compounds (that is, com
pounds in which the aryl portion of the azo com
pound contains a nuclear sulfonic acid group)
have little or no applicability'for the coloration
of organic derivatives of cellulose but may be
employed for the coloration of other textile ma
terials, such as wool and cotton, by customary
methods of application.
/
15
The aryl azo compounds of our invention can
be prepared by diazotizing an arylamine and
coupling the diazonium salt formed with a‘ com
pound designated by'the general Formula I.
The following examples illustrate the method
20
of preparation of the azo compounds of our in
vention:
I
Example 1
13.7 grams of o-phenetidine are dissolved in 200
cc. of water containing 30 cc. of 36%v hydro
chloric acid. The resulting solution is cooled to
a temperature approximating 0-5“ C. by the ad-v
dition of ice, for example, and diazotized by add
ing with stirring ‘6.9 grams of sodium nitrite
dissolved in water. In accordance with custom
ary procedure the diazotization reaction is car:
ried out while maintaining a temperature ap
proximating 0—10° C.
‘
11 grams of 2-imino-6-methyl uracil are dis 35
solved in 200 cc. of water containing 30 grams
of sodium carbonate. The resulting solution is
cooled and the diazo solution prepared as de
to it and R is an aryl nucleus. Advantageously scribed above is gradually added with stirring. 40
Upon completion of the coupling reaction which
40 R is an aryl nucleus of the benzene series.
- takes place, the mixture is made acid to litmus
The term “alkyl group” as used above is iu-r .
with acetic'acid. The dye compound formed is
recovered
by ?ltration, washed with water and
such as a methyl group, an ethyl group or a
'
propyl group, as well as substituted allwl ‘dried.
45
Example 2
tended to include non-substituted alkyl groups,
45 groups, except as otherwise indicated, such as
13.5 grams of p-aminoacetophenone are dis
solved in 200 cc. of water containing 25 cc. of
for example.
The nuclear non-sulfonated aryl azo com
36% hydrochloric acid. The resulting ‘solution
is cooled to a temperature approximating 0~5° C. 50
2
,
2,130,368
and diazotized in the usual manner by the addi
are added to 200 cc. of water containing 40 cc. of
tion of an aqueous solution of 6.9 grams of so
36% hydrochloric acid and diazotized while
dium nitrite.
maintaining a temperature of 10-15° C. by the
addition of 6.9 grams of sodium nitrite dissolved
11 grams of 2-imino-6-methyl uracil are dis
solved in 200 grams of water and ice containing
10 grams of sodium hydroxide and the diazo so
in water.
lution prepared above is added with stirring.
Upon completion of the coupling reaction, the
uracil are dissolved in 200 cc. of water containing
30 grams of sodium carbonate. The resulting so
lution is cooled and the diazo solution prepared
above is slowly added with stirring. Upon com 10
mixture is made acid to Congo red paper by the
10 addition ‘of a mineral acid such as hydrochloric
acid. The dye compoundv formed is recovered by
?ltration, washed with water and dried.
E:rample 3
15
16.8 grams of 1-amino-2-methoxy-4-nitro-~
pletion of the coupling reaction, the mixture is
made acid to litmus with acetic acid and the dye
compound formed is recovered by ?ltration,
washed with water and dried.
20
11 grams of 2-imino-6-methyl uracil are dis
solved in 200 grams of water and ice containing
10 grams of sodium "hydroxide and the diazo
disclosed hereinafter.
Preparation of Z-imino-G-methyl uracil '
CHrC8=iN
11.554 azc-Nn
paper with a mineral acid, hydrochloric acid for
example, and the dye compound formed is re
.
covered by ?ltration, washed with water and
may be prepared as described in Liebig's Annalen,
dried.
gravity 1.84) and after the addition the solution is
warmed to not over 70° C. following which it is
.
-
B. 18.3 grams of l-amino-2,4-dinitrobenzene
are dissolved in 231 grams of hot glacial acetic
acid and the resulting solution is rapidly cooled
to room temperature.
40
The mixture prepared in B is added to the solu
tion prepared in A over a period of 30-45 minutes.
This addition is effected with stirring and while
maintaining a temperature of 10-15° C. The- so
lution resulting is stirred for an additional 30 min
utes and one gram of .urea is. added to remove excess nitrous acid.
‘
11 grams of 2-imino-6-methyl uracilare dis
solved in 400 cc. of water containing su?icient
sodium hydroxide to neutralize the acids present
50 in the diazo solution prepared as described above.
This diazo solution is slowly added with stirring.
Upon completion of the coupling reaction, which
takes place, the mixture is made acid to Congo
red paper with'hydrochloric acid and the dye
55
compound formed is recovered by ?ltration,
washed with water and dried.
Example 5
13.7 grams of o-phenetidine are diazotized as
described in Example 1 and coupled with 15 grams
of 2-ethylimino-6-methyl uracil dissolved in 200
cc, of water containing 30 grams of sodium car
bonate. When coupling is complete, the mixture
is made acid to litmus with acetic acid and ‘the
dye compound formed is recovered by ?ltration,
washed with water and dried.
Equivalent molecular weights of 2-?-hydroxy
uracil, 2-benzylimino-6
70 methyl uracil and 2-phenylimino-6-methyl uracil,
for example, may be substituted for the 2-ethyl
imino-6-methyl uracil employed above.
_
——NH
schen Chemischen Gesellschaft, vol. 19, pages 220 30
A. 7.6 grams of powdered sodium nitrite are
dissolved in 53 cc. of cold sulfuric acid (speci?c
ethylir'nino-G-methyl
°=
25'
_ vol. 262, pages 365 and 366, or Berichte der Deut
Example 4
cooled to l0-l5° C.
20
2-imino-6-methyl uracil,
solution prepared above is added with stirring.
When the coupling reaction which takes place is
25 complete, the mixture is made acid to Congo red
76
_
In order that our invention may be fully under 15
stood the preparation of a number of coupling
components which‘ may be employed in the
preparation of the compounds of the invention is
benzene are added to 200 cc. of water contain
ing 30 cc. of 36% hydrochloric acid and diazo
tized in the usual manner by the addition of 6.9
grams of sodium nitrite dissolved in water.
-
' 16.6 grams of 2-,6-hydroxyethylimino-6-methyl
' Example 6
17.3 grams of 1-amino-2-nitro-4-chlorobenzene
and 221.
Preparation of z-ethylimino-?-methyl uracil
9.4 grams of ethyliminourea carbonate (this
compound may be prepared as described in 35
Science Papers Inst. of Chemical Research
Tokyo—-16, 306-9; 24-8, 1931) are heated in 30
cc. of ethyl alcohol with'12 grams oi acetoacetic
ester for 4 hours. The resulting crystals of 2
ethylimino-?-methyl uracil are recovered by ?l 40
tration and washed with alcohol and water. If
desired, the compound may be further puri?ed by
recrystallization from hot water.
Preparation of 2-p-hydroxyethlimino-6-methyl
.
uracil
12 grams of p-hydroxyethyliminourea carbonate
(this compound may be prepared as described in
Science Papers Inst. 01.’ Chemical Research
Tokyo-16, 306-9; 24-8, 1931) are heated in 30 cc. 50
of ethyl alcohol with 12 grams of acetoacetic ester
for 4 hours. The resulting crystals are recovered
by ?ltration, and washed with alcohol and water.
If desired, the crystals of 2-p-hydroxyethylimino- I
?-methyl uracil may be further puri?ed by re
crystallization from hot water.
Preparation of Z-phenylimino-?-methyl uracil
and Z-benzylimz'no-G-methyl uracil
These compounds may be prepared in a similar
manner as that described for 2-ethylimino-6
methyl uracil by the substitution of a correspond
60
ing equivalent molecular weight of plienylim
inourea carbonate and benzyliminourea carbon
ate, respectively, for ethyliminourea carbonate.
The following tabulation further illustrates
the compounds included within the scope of our
invention together with the color they produce
on cellulose acetate silk. The compounds indi 70
cated below may be prepared by diazotizing the
amines listed under the heading "Amine” and
coupling with the compounds speci?ed in the
column entitled “Coupling component”. The di
azotization and coupling reactions may, for ex
3
2,180,858
employed, for example. These amounts are not
ample, be carried out in accordance with the
to be taken as limits as greater or lesser amounts
can be used. To illustrate, if the dye is ground to
_ general procedure disclosed in Examples 1 to 6
inclusive.
Amine
Coupling component
1-amino-2-?uorobenzene _________ _.
1-amino-3-?uornhen enn
2-imino-6-methyl uracil .... ..
colgée‘zgtgegluéosa
Yellow.
__ _____dn
'
D0.‘
1-amino-4-iluorobenzene..._
10
Do.
1-amino-2-chlorobenzone- _ _
l-amino-3-chlorobenzene- _ _
l-amino-4-chlorobenzene- _ _
1-amino-2-bromobenzene
- l—amino-3—bromobenzene
l-amino-‘i‘broxnobenzene
1-amino-2-iodobcnzene- .
15
1-amino-3-iodobenzene._
15
l-amino-4—iodobenzene _____ _._.___
o-Toluidine. .___
m-Toluidine ____________________ -_
p-Toluidine..___
1-amino~2-methexybenzene
l-amino-Ii-methoxybenzene
l-amino-‘i-methoxybenzene.__
20
20.
1-ainino-3-nitrobenzene __________ __
imminM-nitrobenzene- _________ ._
D
D0.
1-amino-2-iluor o-i-nitro‘r
l-amino-Z-methoxy—4-nitrobenzene
25
Do.
\'
Do.
1-amino—2-chloro-4-nitrobenzene_ _
D0.
l-ainino-2-bromo-4-nitrobenzene._
D0.
l-amino-2-iodo¢4-nitrobenzene____ _
Do.
l-amino-2-nitro-4-?uorobenzene_ - _
l-amino-2-nitro4-chlorobenzene _ _
Do.
Do.
1-amino-2-nitro-4-bromobenzene
Do.
1-amino-2-nitro-4-iodobenmne_ _
Do.
l-amino-li-acetobenmne ______ . .
Yellow.
l-amino-‘kchloroA-acetobenzene..
Orange yellow.
l-amino-2-broxno-4-aeetobenzene- _
' m-Aminoacetanilide . . _
Do.
Do.
Yellow.
p-Aminoacetanilide
Do.
o~AminophenoL
m-Aniinopheuol
D0.
Do.
p-Aminophenol ____ __
D0.
l-amino-Z, 4-dichlorobenzene. .
35
30
Do.
l-amiuo-2~iodo-4-aoetobenzene___. _
1-amino-2-nitro-4-acetobenzene
30
25
35
Orange yellow.
1-amino-2, S-dichlorobenzene ____ ..
Do.
l-amino-2-methoxy-5-methyl-ben-
Yellow.
zene.
.,
.
1-11 m i n o-2-methoxy-5-chloro-ben-
D0.
zene.
l-am in o72-me thoxy-5-bromo-ben
.
40
Z8119.
Lamina-2, 4-dinitrobenzene _____ _.
1-amino~2. 4, ?-trinitro-ben zene _ _ _
learn in 0-2, 4-dinitro-6~?uoroben-¢
zone.
1-1: m in o- 2, 4dinitro~6-chloroben
zene.
1-11 m i 11 0-2, 4»dinitro’6~bromoben
45
zene.
Ami
p-Amino dimethyl aniline_______ _;___do _____________________ -. Red
p-Amino dimethyl aniline ____ __
z-ethyliminoe?emethylumcil- ~
1-amino-2-chloro~4-nitrobenzene___ .4____do__~ ____ _-'_ ............ -.
0.
,
0181180170110“?
In employing the aryl azo derivatives of our
50 invention as dyes, they will ordinarily be applied
to the material in the form of an aqueous suspen
a vsuifliciently ?ne powder dyeing can be satis
factorily carried out without the aid of a dis-_
50
persing agent. Generally speaking, however, the
sion which can be prepared by grinding the dye
use of a dispersing agent is desirable.
to a paste in the presence of a sulfonated oil,
soap, or other suitable dispersing agent and dis
stantially neutral dyebath.
Advantageously, dyeing is carried out in a sub- _
Perhaps, more ac
curately, it should be stated that dyeing should
persing the resulting paste in water. Dyeing not be carried out in an alkaline dyebath, that is,
operations can, :rith advantage, be conducted at _one having any substantial alkalinity, since the
a temperature of 80-85°_ 0., but any suitable tem
presence of free alkali appears to affect the dye
perature may be used. In accordance with the ing adversely. Dyeing in an acid dyebath is not
usual dyeing practice, the material to be dyed recommended because of the tendency of acids to
60 will ordinarily be added to the aqueous dye bath
affect the material undergoing dyeing adversely.
at a temperature lower than that at which the Because of these considerations when a dispers
main portion of the dyeing
to be e?fected, a ing agent is to be employed preferably it is neutral
temperature approximating 45-55“ C., for ex
substantially neutral.
ample, following which the temperature of the orIt
will be understood that the azo compounds
dye
bath
will
be
raised
to
that
selected
for
65
of our invention may be applied to the material to
carrying out the dyeing operation. The tem
colored in any suitable manner. Coloration
perature at which the dyeing is conducted will be
may be effected, for example, by dyeing, printing
vary somewhat, depending, for example, on the or stenciling. Dispersing or solubilizing agents
particular material or materials undergoing that can 'be employed for preparing suspensions
70 coloration. Sodium chloride may be added, if of the dye include soap, sulphoricinoleic acid,
desired, during the dyeing operation to promote salts of sulphoricinoleic acid, a water soluble salt
exhaustion of the dyebath..
_
cellulose phthalate, cellulose succinate or cel
The amount of dispersing agent employed may of
lulose mono-acetate diphthalate, for example,
be varied over wide limits. Amounts approxi
the sodium, potassium or ammonium salts, and
75 mating 10 to 200% by weight on the dye may be
55
60
65
70
75
4
2,130,858
sulfonated oleic, stearic or palmitic acid, or salts
thereof, such, for example, as the sodium or
ammonium salts.
'
While it is preferred to effect coloration by
applying the dye compound from an aqueous dye
bath directly to the material to be colored, the
azo compounds 01' our invention may be applied
employingthe methods applicable to the so-called
vice colors. Brie?y, in accordance with this
10 method of dyeing, the amine is absorbed and
diazotized on the ?ber, after which the dye is
formed in situ by developing with a coupling com
ponent such as 2-imino-6-methyl uracil or
and a benzyl nucleus and R represents an aryl
nucleus of the benzene series.
2. An azo compound having the general for
wherein R represents an aryl nucleus of the hen
Zene series.
3. An azo
formed in situ by coupling with an aryl diazonium
invention.
general
R——N=N—~(:JH o=N—x
O=C——-NH
wherein X represents an alkyl group and R
represents an aryl nucleus of the benzene series.
4. An
azo_ compound
having the general
formula:
CH3-—C=N
Example A
R—N=N—-CH
2.5 parts of the compound formed by coupling
25 2-imino-6-methyl uracil with diazotized l-amino
_2-nitro-4-chlorobenzene in an alkaline medium
are ?nely ground with soap and dispersed in
1000 parts of water. The dispersion thus pre
pared is heated to a temperature approximating
30 45-55" C. and 100 parts of cellulose acetate silk
in the form of ta?eta or threads, for example,
are added to the dye bath after which the tem
perature is gradually raised to 80-85“ C. and the
cellulose acetate silk worked for several hours at
35 this latter temperature. Upon completion of the
dyeing operation, the cellulose acetate silk is re
moved, washed with soap, rinsed and dried. The
cellulose acetate silk is dyed an orange-yellow
shade.
C=N—X
O=C———NH
wherein X represents a hydroxyalkyl group and
R represents an aryl nucleus'of the benzene
series.
5. An
7
azo
compund
having
the
general
formula:
OKs-(3:1?
R—N=N—C|1H
(Il=N—X
O=C——NH
30
wherein X represents a phenyl nucleus and R
represents an aryl nucleus of the benzene series.
6. The process of coloring an organic derivative
of cellulose which comprises applying thereto a
dye selected from the class of azo compounds
having the general formula:
Example B
40
the
CH3—C=N
2-ethylimino-6-methyl uracil, for example.‘ Con
, salt. The following examples illustrate how dye
v20 ing may be carried out in accordance with our
having
,
16 versely the material undergoing dyeing or color
ation may ?rst be treated to ‘absorb one of said
coupling components and the dye subsequently
10
compound
formula:
40
2.5 parts of the compound formed by coupling
2-imino-6-methyl uracil with diazotized l-amino
2-methoxybenzene are ?nely ground with soap
wherein X represents a member selected from the
and ‘dispersed in 1000 parts of water. The disper
sion thus prepared is heated to a temperature group consisting of hydrogen, an alkyl group, a
phenyl nucleus and a benzyl nucleus and R
approximating 45-55° C. and 100 parts of cellu
represents a nuclear non-sulfonated aryl nucleus
, lose acetate silk in the form of taffeta or threads,
for example, are added to the'dye bath after of the benzene series. ’
7. The process of coloring an organic acid ester
which the temperature is gradually raised to
50 80—85° C. and the cellulose acetate silk worked
of cellulose which comprises applying thereto a ,
for several hours at this latter temperature. dye selected from the class of azo compounds
Upon completion of the dyeing operation, the having the general formula:
cellulose acetate silk is removed, washed with
soap, rinsed and dried. The cellulose acetate silk
45
55 is dyed a‘yellow shade.
‘
While our invention has been illustrated in
‘connection with the dyeingof cellulose acetate
silk it will be understood that dyeing operations
60 can be carried out in a manner similar to that
wherein X represents a member selected from the
group consisting of hydrogen, an alkyl group, a
phenyl nucleus and a benzyl nucleus and R repre
sents a nuclear non-sulfonated aryl nucleus of 60
the benzene series.
8. The process of coloring a cellulose acetate
65 substitution of both the material being dyed and
from. the class of azo compounds having the gen
described above by the substitution of another
organic derivative of cellulose material for cellu
lose acetate silk or by employing dye compounds
other than those employed in the examples, or by
which comprises applying thereto a dye selected
the dye compounds of the examples.
We
65
claim:
1. An
azo
I
compound
formula:
.
\
having
the
_
general
'
CH3—C=N
|
R—N=N—CH
I
.
l
C=N—X
l
O=C—-——NH
wherein X represents a member selected from the
75 group consisting of hydrogen, a phenyl nucleus
wherein X represents a member selected from the 70
group consisting of hydrogen, an alkyl group, a
phenyl nucleus and a benzyl nucleus and R
represents a nuclear non-sulfonated aryl nucleus
of the benzene series.
9. The process of coloring a cellulose acetate
5
2,130,858
which comprises applying thereto a dye selected
from the class of azo compounds having the
general formula:
'
12. A' cellulose acetate colored with a dye se
lected from the class of azo compounds having
the general formula:
.
CH:—C=N
R—-N=N—‘—CH
_
C=N—H
O=C-—-—NH
wherein R represents a. nuclear non-sulfonated
wherein X represents a member selected from
aryl nucleus of the benzene series.
10. Material containing an organic derivative
10
represents a nuclear non-sulfonated aryl nucleus
of cellulose colored with a dye selected from the
class of azo compounds having the general form
ula:
the group consisting of hydrogen, an alkyl group,
a phenyl nucleus and a benzyl nucleus and R 10
of the benzene series.
-
13. A cellulose acetate colored with a dye se
lected from the class of azo compounds having
15
wherein X represents a. member selected from the
group consisting of hydrogen, an alkyl group, a
phenyl nucleus and a benzyl nucleus and R rep - wherein R represents a nuclear non-sulfonated 20
20
resents a. nuclear non-sulfonated aryl nucleus aryl nucleus of the benzene series.
m
14. A process of preparing azo compounds
of the benzene series.
11. Material containing an organic acid ester which comprises coupling a diazotized arylamine
of cellulose colored with a dye selected from the of the benzene series with a compound having
25
25
class of azo compounds having the'general form
ula:
CHr-C=N
R-—N=N—CH
.
C=N—X
O=C—-———NH 3
30 wherein X represents a member selected from
the group consisting of hydrogen, an alkyl group,
a phenyl nucleus and a benzyl nucleus and R rep
resents a nuclear non-sulfonated aryl» nucleus of -
the benzene series.
wherein X represents a member selected from
the groupv consisting of hydrogen, an alkyl group,
a phenyl nucleus and a benzyl nucleus.
JAMES G. McNAIl-Y.
JOSEPH B. DICKEY;
30
Документ
Категория
Без категории
Просмотров
0
Размер файла
593 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа