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Патент USA US2136135

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2,136,135
UNITED STATES PATENT OFFICE
Patented Nov. 8, 1938
2,136,135
PSEUDO-AZllVlIDO-BENZENE-AMINO - ACYL
,
OAG‘ETIG ACID‘ EST‘ERS
‘Hans Johner ‘and Gerald Bonhote, Basel, Swit
zerland, assignors to the ?rm Society of Chem
ical Industry in Basle, Basel, Switzerland
No Drawing. Application July 12, 1937, Serial
No. 153,279.
1
.
In Switzerland July 14, 1936
8 Claims.
(Cl. 260-308’)
The present invention relates to new arylides
of Ji-ketone-carboxylic acids which are valuable
intermediate products for the manufacture of
dyestuffs.
It comprises the new arylides, the
‘ 5 process of producing the same as well as their
application for the manufacture of dyestuffs.
It has been found that valuable arylides of pi
ketone-carboxylic acids may be obtained if amino
compounds of the general'formula
'10
"15 in which R. stands for an aryl radical of the ben
zene or naphthalene series such as the 5-amino
2~phenyl-pseudo-azimidobenzene, the 5 -'ain'ino 6-methyl-2-phenyl-pseudo - azimidobenzene, the
5-amino-2-(4'-methoxy) -phenyl-p'seudo - azimi
2 O dobenzene, the 5-amino-2—(4’- ethoxy) - phenyl
pseudo-azimidobenzene, the 5-ami'no-6-methy1
2- (4'-methoxy) -phenyl-pseudo - azimidobenzene,
the 5-amino-6-methyl - 2 -"(4'- ethox‘y) -p-henyl
pseudo-azimidobenzene, the 5-amino-6-methoxy
25 2- (4' -methoxy) -- phenyl-pseudo-azimidobenzene,
the 5-amino-6-methoxy-2- (4’ - ethoxy) - phenyl
pseudo - azimidobenzene, the 5 - amino - 2 -(1') -
naphthyl-pseudo-azimidobenzene, the E-amino
2- (4’-c-‘methoxy-oxyethyl) - phenyl - pseudo-azi
3 O midobenzene, are condensed with esters of B
ketone-carboxylic acids, such as ethyl acetoace
tate, benzoyl acetic ester, or terephthaloyl acetic
ester,
These arylides thus correspond to the general
formula
O
40
\N
~11
in which R stands for a member of the group
consisting of aryl nuclei of the benzene and naph
thalene series, R1 stands for a member of the
45 group consisting of methyl and phenyl, and y
stands for a member of the group consisting of
H, CH3 and O-alkyl. Among such products those
are valuable in which R‘ represents a nucleus
of the benzene series because they lead to par
ticularly valuable dyestuffs. Among such prod
ucts those are again particularly valuable which
correspond to the general formula
in which y has the signi?cation already indicated
4.60 above and :1,‘ stands for a member of the group
consisting of H, CH3 and O-alkyl.
All these
products are light colored powders insoluble in
water but soluble in aqueous caustic alkalies.
The new arylides, which represent valuable
intermediate products for the manufacture of
dyestuffs, dissolve in aqueous caustic alkalies
owing to the presence of the ~CO—CH2—CO-—
group. In such solutions the alkali salts of the
new arylides possess a marked affinity for the
Vegetable ?ber, which is entirely surprising, since 10
the similar arylides from the isomeric amino-azi
mides do not possess such an a?inity for the vege
table ?ber. Since they combine with diazo com
pounds to‘ azo-dyestuffs they are inter alia very
suitable for the production of azo-dyestuffs on 15
the vegetable ?ber (cotton, ram-ie, ?ax, jute and
the like) as well as on regenerated cellulose (vis
cose or cuprammonium silk), and also on animal
?bers such as wool, natural silk or loaded silk,
according to the methods usual in dyeing with ice 20
colours. Such methods are, for example, padding
the ?ber in an alkaline solution of the new
arylide and developing with a diazo compound,
preferably one containing no hydroxy-, carb'oxy
or sulfo-groups. Such diazo-compounds are, for 25
instance, those derived from aniline, ethers or
esters of amino-phenols, for ‘example ortho- or
para-anisidine, 4-chloro—Z-amino-diphenylether,
4:4'-dichloro-2-aminodiphenylether; those de
rived from monoacylated products from 2:5-di
aminohydro-quinone-diethyl- or -dimethy1ether
and benzoylchlorider or phenoxy-acetic-acid
chloride; aminoazoedyestuffs, for instance, 4
amino-5-methoxyazobenzene,
methoxyazobenzene,
Ll-amin'o - 2:5 - di
ortho-amino-azo - toluene;
further those derived from chlorotoluidines, for
instance tl-chloro-2-methyl-l-aminobenzene, 4
chloro-1-methyl-2-aminobenzene; those from ni-'
tranalines such as ortho-nitraniline, 1-amino-2 40
methylA-nitrobenzene, l-amino-2-n'itro-4-chlo
robenzene, 1-amino~2-nitro-4-1nethyl- or -meth
oxybenzene, or 4-nitro-2-methoxy-1-aminoben—
zene; those derived from ortho- or meta-chloran
iline, 2:5-dich1oraniline, u- or ,cenaphthylamine
and the like.
For the purpose of producing fast tints on the
?ber preparations or printing colors containing
them may also be prepared which contain an
alkali salt of'the new derivatives and a stabilized
diam-compound in the form of a nitrosamine or
of a diazoamino-compound. vThese preparations
may be printed on the fiber and then developed
to dyestuifs by suitable treatment, for example ,
by passage through an acid. It is also possible
to print mixtures of the free diazotizing com
ponents or the corresponding N—nitramines and
alkali salts of the new coupling components on
the ?ber and to convert such mixture into dye
2
2,136,135
stu?s by development with nitrous acid, and,
if desired, subsequent treatment in alkali.
are added gradually 15 parts of ethylacetoacetate.
Condensation is continued for 2 hours, during
'
The condensation products of the general for
which time the alcohol formed and some chloro
benzene are distilled. When condensation is
complete, the mass is cooled, the chlorobenzene
is distilled in steam and the condensation prod
not left behind is ?ltered; it is dissolved in dilute
caustic alkali lye and, after ?ltration from some
mula
impurities, the solution is treated with dilute
hydrochloric acid to reprecipitate the condensa 10
tion product.
10 in which R, R1 and y have the signi?cation in
dicated above, coupled in substance with the
same non-sulfonated compounds with which they
are used for the production of fast tints on the
?ber, yield pigments which are useful as such
or in coloring lacquers, varnishes or the like.
It is a white powder freely soluble in dilute
alkalies and melting after recrystallization from
alcohol at 152° C.
The process is similar with the other pseudo
With sulfonated diazo-compounds wool dye
15
azimides and ?-ketone-carboxylic acid esters
cited in the introductory paragraphs. The fol
stuffs are in particular obtained. Especially valu
able are the dyestuffs which are derived from
lowing table shows the melting point of some of
such condensation products:—
ortho-hydroxylated or ortho-carboxylated diazo
20
B-ketone-carboxylic-acid-ester
Azimide
Melting point from—
Ethyl acetoacetate ____________ __
+5-ami_n0-2-(4’-methoxy)-phenyl-pseudo-azimidobenzene.;
Do _______________________ __
+5-am1_no-2-(4’-ethoxy)-phenyl-pseudo-azimidobenzene____
Alcohol 191° 0.
Do _______________________ ._
Do _______________________ _.
+5-am1no-6*methyl-2-phenyl-pseudo-azimidobenzene____ __
Alcohol 205° 0.
Do _______________________ __
+5-an_11no~6-methoxy-2-(4’-methoxy)-phenyl-pseudo-azi-
Do _______________________ _.
+5-ammo-6-methoxy-2-(4’-ethoxy)-phenyl-pseudo-azimi~
+5 -_a!I_1m0 - 6 - methyl - 2 - (4’ - methoxy) - phenyl - pseudoaz1midobenzene.
,
'
Chlorobenzene 222° 0.
25
‘
midobenzene.
dobenzene.
Alcohol 163° 0.
Alcohol 168° C.
Alcohol 155° C.
'
+5-amino-6-ch1oro-2-phenyl-psoudo-azimidobenzene _____ __ Alcohol 185° 0.
Do ___________ __
Benzoyl acetic ester.
+5-am1n0-6-methy1-2-(1’)mapllthyl-pseudo-azimidobenzene_ Ohlorobenzene 209° C.
+5-am1no-2~phenyl-pseudo-azimidobenzene _____________ __ Alcohol 180° C.
Terephthaloyl-diacetic ester
compounds as these products may be converted
in substance or on the ?ber into metalliferous
dyestuffs.
The dyestuffs which may be prepared accord
ing to the present process with aid of the new
arylides correspond therefore to the general for
mula
30
_-_..do___ 7 ______________________________________________ __ Alcohol 280° 0.
’
r
Example 2
13.87 parts of ortho-nitraniline are diazotized
as usual and the product is introduced into a
solution of 29.4 parts of the condensation‘ prod
35
uct from 5-amino-2-pheny1-pseudo-azimidoben
zene and ethylacetoacetate, 100 parts of sodium
hydroxide solution of 36° Bé., 175‘. parts sodium
acetate and 2000 parts of 'water. The yellow
dyestuff formed is precipitated immediately; it
l'
in which R, R1 and y have the signi?cation in
dicated above, and R2 stands for an aromatic
radical selected from the group consisting of
aromatic nuclei of the benzene and naphthalene
series. If these dyestuffs do not contain sulfo
groups they represent yellow to orange or brown
orange pigments which are insoluble in water.
Particularly valuable are the dyestuffs of the for
mula
~
in which R2 stands for an aromatic radical of
the benzene series, if the benzene radical R2 con
tains a Intro-group in ortho-position to the
-—N=N-group.
These dyestuffs when produced
on the ?ber dye the same yellow tints of very
'
If a sulfonic acid, for instance sulfanilic acid,
is substituted for the ortho-nitraniline, there is
obtained a dyestuif soluble in water.
Ewample 3
Cotton yarn is impregnated with a grounding
prepared by dissolving 3 parts of the condensa
tion product from 5—aminophenyl-pseudo-azi
midobenzene and ethylacetoacetate in 300 parts
of hot water with the addition of 6 parts sodium
hydroxide solution of 30 per cent. strength, 10
parts of Turkey red oil, 15 parts of sodium chlo
ride, and water to make up 1000 parts. The
goods are then wrung out and developed in a
diazo-solution which has been neutralized with 60
sodium acetate and acidi?ed with acetic acid,
and corresponds with 2 parts of 1-amino-2
methyl-‘l-nitrobenzene per 1000 parts. There is
produced a pure greenish-yellow of very good
good fastness properties, particularly excellent
properties of fastness.
fastness to light.
The following examples illustrate the inven
components,’ for instance 1-amino-2-methyl-4~
tion, the parts being by weight:
Example 1
70
21 parts of 5-amino-2-phenyl-pseudoeazimido
benzene are introduced into 200 parts of chloro
benzene, a few drops of diethylaniline are added
and the whole is heated to boiling under re?ux.
75
is ?ltered and dried.
The chlorobenzene is then distilled and. there
Similar tints are obtained with other diazo
chlorobenzene, 1-amino-2-nitro-4-chlorobenzene,
1-amino-2-nitro-4-methylbenzene. Redder tints
are obtained for instance with l-amino-Z-nitro 70
‘l-methoxybenzene or ortho-aminoa'zotoluene.
The goods may also be grounded at a raised
temperature, for instance at 80° C.; such arylides
may also be used for printing.
~
The following table comprises a number of 75
3
2,136,135
other dyeing colors which may be made by this
invention :—
DiaZo-component
for the Vegetable ?ber, and react with diazo com
pounds with formation of azo-dyestu?s.
Condensation product from ethyl-aceto-acetate with-
Ortho-nitraniline _________________ __
5-amino-2-(4’-methoxy)-phenyl-pseudo-azimidobenzene ____ _-
Color
Yellow.
l-amino-Z-nitro-4»methyl-benzene_ __ -.___do-_ _
1-amino-2-nitro-4—methoxybenzene-_
_
Do.
.____do _ _ _ _ _ . _ _
. _ _ _ _ ._
5-amino-2-(4’-etl1oxy)~phenyl-pseudo-azimidobenzene _______ __
Ortho-nitramline ______ _
Para-mtraniline. _ _-___
10
___
.
_
_____do ____________________________________________________ __
5-smino-6-methyl-2-phenyl-pseudo-azimidobenzene ________ __
Ortho-aminoaZo-toluene_ _ -_ _.
_
l-amino-2-nitro-4-chlorbenzene ____ __
?-amino-S-methoxy-Z-(4’-metl1oxy)-phenyl~pseudo-azimidobenzene.
4:4’-dichlor~2-aminodipl1enyletl1er--_
1~amino-2-nitr0~4-chlorbenzene ____ _.
15
Ortho-nitraniline _________________ ._
Greenish-yellow.
Reddish-yellow.
10
Gold-orange.
5-%mino~6-methyl-2- (4’ -mcthoxy) ~phenyl-pseudo-azimido- Reddish-yellow.
enzene.
2:5-dichlotaniline _________________ __
Do.
D o.
Yellow.
,
_____do _ _ _ _ _ _
. _ . . _ . . -_
Greenish-yellow.
_____do ____________________________________________________ __
Reddish-yellow.
_._-_do ____________________________________________________ __
Yellow.
What we claim is:—
1. As new products the arylides of the general
15
4. As new products the arylides of the general
formula
i‘ ‘i
formula
i’
N-C-OHrC-CHB
20
in which y stands for a member of the group con
in which R stands for a member of the group con
sisting of nuclei of the benzene and naphthalene
series, R1 stands for a member, of the group con
sisting of methyl and phenyl, and 3/ stands for
a member of the group consisting of H, CH3 and
O-alkyl, which products are light colored pow
ders, dissolving in aqueous caustic alkalies, from
which solutions they possess affinity for the
35 vegetable ?ber, and react with diazo compounds
sisting of H, CH3 and O-alkyl, which products 25
are light colored powders, dissolving in aqueous
caustic alkalies, from which solutions they pos
sess af?nity for the vegetable ?ber, and react
with diazo compounds with formation of a20
30
dyestuffs.
5. As new products the arylides of the general
formula
35
with formation of azo-dyestuffs.
2. As new products the arylides of the general
formula
Ill 0
40
@Ncl,
45
,
in which R1 stands for a member of the group
consisting of methyl and phenyl, y stands for a
member of the group consisting of H, CH3 and
in which the alkyl-group contains not more than
2 carbon atoms, and in which :1] stands for a
member of the group consisting of H, CH3 and 40
O-alkyl, which products are light colored pow
ders, dissolving in aqueous caustic alkalies; from
which solutions they possess a?inity for the vege
table ?ber, and react with diazo compounds with
45
formation of azo-dyestuffs.
6. As a new product the arylide of the for
mula
O-alkyl, and it stands for a member of the group
consisting of H, CH3 and O-alkyl, which products
50 are light colored powders, dissolving in aqueous
caustic alkalies, from which solutions they possess
affinity for the vegetable ?ber, and react with
diazo compounds with formation of azo-dyestuifs.
3 As new products the arylides of the general
55
formula
]ll I
o
N-C-CHr- —OH;
60
7. As a new product the arylide of the for
mula
/N
CQHF-O-GN\Nl
H (II)
I
1l1'—C——CH2-C—-CHa
OCH:
8. As a new product the arylide of the for
mula
H 0
I ll
ll
in which :1] stands for a member of the group con
65 sisting of H, CH3 and O-alkyl, and :0 stands for
a member of the group consisting of H, CH3, 0'
alkyl and halogen, which products are light col
ored powders, dissolving in aqueous caustic alka
lies, from which solutions they possess a?inity
/N
onto-Oat |
'
\N
55
a0
—N—-C—CH2—-C—CHa
65
—CH3
HANS JOI-INER. A
GERALD BONHOTE.
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