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Патент USA US2134642

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Patented Oct. 25, 1938
2,134,642
UNITED STATES PATENT oFFicE
2,134,642
AZO .DYEST‘UFF AND PROCESS FOR THE
MANUFACTURE. THEREOF
'
Pierre Petitcolas, Rouen, and Robert Frédéric
Michel Sureau, Mont St~Aignan, France, as
signors toQCompagnie Nationale de Matieres
C'olorantes et Manufactures‘ de Produits Ghi
, miques du N ord Réunies, Etablissements Kuhl
mann, Paris, France, a corporation of France
No Drawing. Application July 28, 1937, Serial
No. 156,178. In France August 12, 1936
10 Claims.
(01. 260—-193)
This invention relates to azo dyestuffs and
process for the manufacture thereof.
,
After cooling to about 100? 0., there are intro
duced in small portions 90 grams of o-nitroben
' g
It has been found according to the present in
vention that there are easily obtained‘the aryl
zene-sulfonyl chloride. The temperature should
tion products of the general formula:
not exceed 130-140° C. The reaction is practicale
ly instantaneous. After a few‘ moments stirring =
the 'whole is poured with good agitation into
‘
grams of caustic soda‘per litre, After ?ltration
esters of orthosulphanilic acid or of its substitu
3000 ‘cos. of an alkaline‘solutionr containing 30
NEH
OSOzOaryl
of the crystallized product and puri?cation in al
cohol the phenyl ester offo-nitro-benzene sul
(in which the benzene nucleus substituted by the
NI-Iz-group and also the other aryl nucleus may
phonic ‘acid of the following formula:
contain other substituents whichdo not impart
V
solubility in water, substituents such as alkyl or
alkoxy groups or halogen atoms), by reducing by
any customary process the condensation prod
ucts of ortho-‘nitro-benzene sulfonyl chloride or
its substitution products with alkali-phenolates
or their'nuclear substitution products such for
example as the alkali salts of the 0-, m- and
p-cresols, the o-, m-, p-‘chlorophenols, the di- and
NCIM
’
is produced in the form of white needles (M. P.
57°). .By reduction by means of the customary
processes there is obtained the phenyl-ester of
o-sulphanilic acid (M. P. 71° after puri?cation
in alcohol).
Ewample 2
'20
By working as in Example 1 but replacing the
tri-chlorophenols, the mono-alkyl derivatives of
o-nitro-benzene-sulfonyl chloride by 1-chloro—3
nitro-¢l-benzene-sulfonyl-chloride there is ob
hydroquinone'or resorcinol or the like.
These condensations are ‘carried out in the ab
sence of water and either in the presence of ex
cess of phenol or better‘ in a neutral solvent such
as benzene, toluene, chlorobenzene or the like.
The bases of the above general formula can
be used as diazo constituents and constitute par
tained a condensation product, the phenyl-ester
of 1-chloro-3-nitro-benzene-sulphonic acid‘ (M; 25
P. 82° after puri?cation in‘ alcohol), which, by re
duction, ‘gives the corresponding base .(M. P. 103°)
of formula:
ticularly'valuable starting materials for the pro-z .
duction of‘azo dyestuffs, ‘in particular for‘. the .
V
‘
N111:
30
production on the ?bre and in substance of azo
dyestuffs insoluble in ‘water by. coupling with
coupling components'of substantive character,
such as the arylides of o-hydroxy-carboxylic
acids, acyl-acetic acids and others.
'
The ‘dyestuffs obtained possess good fastness
‘properties to chlorine, boiling, and above all re
markable fastness to light.
-
19 grams of this phenyl-ester are ?nely‘po'w
dered and stirred for several hours at ordinary
temperature into a mixture of 100 cos. of hydro 35
chloric acid of 20° Bé. and 20 cos. of ‘Water.
There is added a distinct excess of a 50% solution
of sodium nitrite and the whole is stirred briskly
for half an hour. ‘ The diazo solution is ?ltered
The production of these dyestu?s on the ?bre and subjected to the addition of a concentrated 40
can be carried out as regards the'dyeing of cot~ . solution of sodium ?uo borate. The diazonium
ton, viscose vor other natural or arti?cial ?bres ?uoborate crystallizes instantaneously in beauti
by means of known processes with or without
ful white plates which are centrifuged and can
intermediate formation of nitros amines, diazo
be dried at 50° C. For use it is ground with a
amino compounds,‘ diazo-sulphonates, Schiff 'mixture of naphthalene-2.7-disulphonic acid and 45
bases and soon.
_
The dyestuffs produced in substance can be
used for ‘the dyeing of lacquers, varnishes, or
ganic solvents, plastic masses, rubber and so on.
' The following examples’ illustrate the inven
tion;
"
.
..
_
aluminium sulphate in such a manner as to bring
the content of the powder to 20% of free base.
By replacing in this example the phenol by p
cresol it is possible to prepare the p-cresyl-ester
of p-chloro-o-nitrobenzene-sulphonic acid (M. P. 50
97-99°) of the formula:
Example» 1
A mixture of 200 grams of phenol and 25 grams
1 of pure caustic potash is’ heated to 190-200° C. to
55 the complete elimination of the water formed.‘
65
2
2,134,642
which, when reduced, gives the p-cresyl-ester of
104°) (the corresponding nitro-derivative melts
p-chloro-o-sulphanilic acid (M. P. 114° C.) of
the formula:
at 59° 0.).
NHi
(c) the 2'.5'-dichlorophenyl-ester of p-chloro-o
sulphanilic acid (M. P. 123°) of formula:
Cl
U!
This latter can be diazotized in the same manner
as above.
10
With p-chloro-phenol under the same condi
10
tions there is isolated the p-chloro-phenyl-ester
of p-chloro-o-nitrobenzene-sulphonic acid (M. P.
90°) then the p-chloro-phenyl-ester of p-chloro
o-sulphanilic acid (M. P. 115°) of the formula:
15
NH:
I
(the corresponding nitro-derivative melts at
130° C.).
(d) the 2’.4'6’-trichlorophenyl-ester of p~chloro
o-sulphanilic acid (M. P. 138°) of formula:
C1
I
20
Example 3
25 grams of phenol and 12 grams of pure caus-V
NHz
C1
tic potash are dissolved in 100 cos. of ethyl alcohol.
This solution of potassium phenate is poured into
(the. corresponding nitro derivative melts at
500 ccs. of chloro-benzene and the mixture
128° C.).
25 brought to boiling point with distillation of the
water and the alcohol then of the chloro-benzene
to the complete elimination of the water. After
cooling to about 50° C. there are introduced 45
grams
of
1-methyl-3-nitro-4-benzene-sulfonyl
30 chloride. The reaction is rapid and causes a con
siderable increase of temperature. The whole is
brought to boiling for some minutes and then the
solvent driven oil with steam. The phenyl ester
of o-nitro-p-toluene sulphonic acid crystallizes
35 easily.
Puri?ed from alcohol it is produced in
the form of white needles (M. P. 101°).
By reduction there is obtained the phenyl-ester
of p-methyl-o-sulphanilic acid (M. P. 94°) of the
formula:
Example 4
25
2 grams of naphthylamide of 2.3-hydroxy
naphthoic acid are pasted with 3 ccs. of denatured
alcohol and 0.8 cc. of caustic soda of 34° Bé.; di
lution is effected with 2 ccs. of cold water and 30
there is obtained a clear solution to which is
added 1 cc. of 33% formaldehyde. After standing
for 5 minutes this solution is poured into 1 litre of
cold water to which have previously been added
5.2 cos. of caustic soda of 34° Bé. and 5 ccs. of 35
sodium sulpho-ricinoleate 50%. 50 grams of cot.
ton yarn are handled for half an hour at 25-30°
C. in this impregnating bath then it is squeezed
and developed immediately in a bath constituted
by 1 litre of water in which have been dissolved 40
13 grams of the diazo-derivative such as is ob
tained in Example 2 starting from the phenyl
ester of 1-amino-5-chloro-benzene-2-sulphonic
45
acid and containing 20% of free base.
Under analogous conditions it is possible to
The duration of the development is half an 46
produce
hour in the cold; the skein is rinsed, acidi?ed,
(a) the o-chlorophenyl-ester of p-chloro-o-sul
phanilic acid (M. P. 111°) of formula:
rinsed, soaped for half an hour at the boil in a
bath containing 3 grams of Marseilles soap per
litre, rinsed again and dried. A scarlet shade is
obtained.
50
The table below indicates the shades obtained
with different phenyl esters of o-sulphanilic acid
or their derivatives on one hand and different
coupling components on the other hand.
(17) the o-cresyl-ester of o-sulphanilic acid (M. P.
55
Diazotization component
Coupling component
Shade on cotton
Anilide of 2.3-hydroxynaphthoic acid ________________ _.
m-Nitranilide of 2.3-hydroxynaphthoic acid _________ __
?-Naphthylamide of 2.3-hydroxynaphthoic acid_ . __5-chloro-2-toluidide of 2.3-hydroxynaphthoic acid ____ __
60
Reddish orange.
Orange.
Scarlet.
Orange.
Palral-anésédidfe 20g 2E3-(iilydl‘OXYIl?1FélthOi0 gcid ......... _. graddish brown.
.
o-
o ui
i
e o
.
-
y
roxynap
oic aci
_ _ _ _ _ __ _
_ __
1315113113955“?
or 16ammo'5'chlm'o'benzene' o-Anisidide
a-Naphthylamide
of 2.3-hydroxynaphthoic acid
5“ p Omc ac‘ '
0f 2.3—hydroxynaphthoic acid ____ __
right orange.
Reddish
brown.
Orange.
p-Ohloro-o-anisidide of 2.3 hydroxynaphthoic acid
Do.
2.3 - hydroxynaphthoyl - 2.4 - dimethoxy - 5 - chloro -l -
65
Diacetoacetyl-o-tolidine _____________________________ __
(Anilide of 2.3-hydroxynaphthoic acid ...... _.
p-Cresyl-ester of l-amino-S-chloro-benzene2-sulphonic acid.
5-cl1loro-2-toluidide of 2.3-hydroxynaphthoic acid.
Do.
Reddish orange.
__. Orange.
Para-anisidide of 2.3-hydroxynaphthoic acid _________ .. Brownish orange.
70
o-Toluidide of 2.3-hydroxynaphthoic acid _ _ _
4
Do _____________________________ _-
Yellow.
Orange.
rn-Nitranilide of 2.3-hydroxynaphthoic acid .
B-Naphthylemide of 2.3-hydroxynaphthoic acid
-
___
_ __
Orange.
u-Naphthylamide of 2.3-hydroxynaphthoie a
Reddish orange.
o-Anisidide oi 2.3-hydroxynaphthoic acid.___
Orange.
p-Chloro-o-anisidide of 2.3~hydroxynaphthoic a
2.3-hydroxynaphthoyl-2.4-dimethoxy-5-chloro-l-aminobenzene.
Diecetoacetyl-o-tolidine _____________________________ __
.75
Brown.
aminobenzene.
Do.
Brown.
-
Yellow. '
76
2,134,642
Diazotization component
3
Coupling component
Shade on cotton
Anilide of 2.3-hydroxynaphthoic acid _____ __
Orange:
m-Nitranilide of 2.3-hydroxynaphthoic acid
-_ Reddish orange.
B-Naphthylamide of 2.3-hydroxynaphthoic acid _ __
__
Do.
5<cl1loro-2-to1uidide of 2.3-hydroxynaphtho_ic acid ____ __ Orange.
Para-anisidide of 2.3-hydroxynaphthoic acld _________ __
Phenyl-ester of o-sulphanilic acid _______ ._
O-TOlllldlde of 2.3-hydroxynaphthcic acid__
a-naphthylamide of 2.3-hydroxynaphthoic a
Brownish orange.
Orange.
Orange.
Reddish orange.
o-anisidide of 2.3-hydroxynaphthoic acid"-..
p ohloro o anisidide of 2l3-hydroxynaphthoic a
-.
Do.
10
2.tghydroxynaphthoyl-Z.4-dimethoxy-S-chloro-l-amino- Brown.
enzenc.
'
Diacetoacetyl-o-tolidine _____________________________ __
What we claim is:
15
Greenish yellow.
4. Process for the manufacture of azo dye
1. Process for the manufacture of azo dye
stuffs consisting in coupling the diazo-deriva
stuffs consisting in coupling thevdiazo-deriva
tives of aromatic amines of the general formula:
tives of aromatic amines of the general formula:
15
NHa
/
co
’
20
with a member of the group consisting of phenyl
amides of 2-3-hydroxynaphthoic acid, naphthyl
amide of 2-3 hydroxynaphthoic acid and the di
25
acetoacetyl-o-tolidine.
'
2. Process for the manufacture of azo dye
stu?s consisting in coupling the diazo-deriva
' tives of aromatic amines of the general formula:
30
NHI
/
in which the benzene nucleus contains at least
one member of the group consisting of halogen,
alkyl and alcoxy groups with a member of the
group consisting of phenylamides of 2-3-hy
droxynaphthoic acid, naphthylamides of 2-3 hy
droxynaphthoic acid and the diacetoacetyl-o
tolidine;
‘
5. Process for the manufacture of azo dye
stuffs consisting in coupling the diazo-derivatives
of aromatic amines of the general formula:
/
in which the benzene nucleus contains at least
one member of the group consisting of halogen,
35 alkyl and alcoxy groups with a member of the
group consisting of phenylamides of 2-3-hy
droxynaphthoic acid, naphthylamides of 2-3 hy
droxynaphthoic acid and the diacetoacetyl-o
tolidine.
40" 3. Process for the manufacture of azo dye
stuffs consisting of coupling the diazo-deriva
tives of aromatic amines of the general formula:
NH:
/
45
in which the benzene nucleus‘contains at least
one member of the group consisting of halogen,
alkyl and alcoxy groups with a member of the
group consisting of phenylamides of 2-3-hy
droxynaphthoic acid, naphthylamides of 2-3 hy
droxynaphthoic acid and the diacetoacetyl-o
tolidine.
25
30
NH:
in which the benzene nucleus contains at least 35
one member of the group consisting of halogen,
alkyl and alcoxy groups with a member of the
group consisting of phenylamides of 2-3-hy
droxynaphthoic acid, naphthylamides of 2-3 hy
droxynaphthoic acid and the diacetoacetyl-o-tol
idine.
40
‘
6. Azo dyestuffs obtained by the process ac
cording to claim 1.7
_
'7. A20 dyestuffs obtained by
cording to claim 2.
8. Azo dyestuffs obtained by
cording to claim 3.
9. Azo dyestuffs obtained by
cording to claim 4.
10. Azo dyestu?s obtained by
cording to claim 5.
the process ac
45
the process ac
the process ac
the process ac
PIERRE PETITCOLA‘S.
ROBERT FRnDE'RIc MICHEL SUREAU.
50
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