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Патент USA US3097207

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United States Patent 0
3,097,197
"P
1C6.
lgatented July 9, 1963
2
1
According to a further feature of the invention there is
3,097,197
provided a process for the manufacture of the new azo
1-(DIHALUGEN-TRIAZINYLAMINOPHENYD-Ai-(,8—
NAPHTHYLAZO)PYRAZOLONE DYESTUFFS.
dyestutfs, as hereinbefore de?ned, which comprises react~
ing cyanuric chloride or cyanuric bromide with an azo
Colin George Tilley and Frederick Andrew Waite, Man
chester, England, assignors to Imperial Chemical In
dustries Limited, London, England, a corporation of
compound, which in the form of its free acid, is repre
sented by the formula:
Great Britain
SOaH
No Drawing. Filed Nov. 6, 1959, Ser. No. 851,223
Claims priority, application Great Britain Nov. 14, 1958
.
,
1 Claim.
(Cl. 260—153)
10
This invention relates to new azo dyestuffs and more
particularly it relates to new azo dyestuifs which are valu
able for colouring cellulose textile materials.
According to the invention there are provided the new
dyestuffs which, in the form of the free acids, are repre 15
sented by the formula: ..
SOaH
Z
wherein A and n have the meanings stated above, one Z
20 represents a hydrogen atom or a sulphonic acid group and
.the other Z represents an ——NHR group, wherein R has
the meaning stated above, and the benzene nucleus may
be substituted by atoms or groups other than hydroxy,
amino or substituted amino groups.
25
Y
This process of the invention may be conveniently car~
ried out by adding an aqueous solution of the sodium salt
of the azo compound to a suspension of the cyanuric chlo
ride or cyanuric bromide in water or in a mixture of water
and a water-miscible organic liquid, for example acetone,
ical or a carboxylic acid, carboxylic acid ester, carbamyl 30 adding sodium carbonate to maintain the pH of the mix
wherein n represents \0, 1 or 2, A represents an alkyl rad
,or substituted carbamyl group, one Y represents a hydro
gen atom or a sulphonic acid group and the other Y
represents a group of the formula:
ture at 7 and ‘?ltering off the azo dyestuff which is pre
cipitated. ‘If desired sodium chloride can be added to
ensure complete precipitation of all the azo dyestuff.
The azo compounds used in this process of the.inven—
35 tion may be obtained by diazotising an amine of the
formula:
sloaH
NH:
40
(30311)»
wherein R represents a hydrogen atom or an alkyl rad
ical, X represents a chlorine or a bromine atom, and the
benzene nucleus may be substituted by atoms or groups
Formula I
other than hydroxy, amino and substituted amino groups.
wherein n has the meaning stated above, and coupling
As examples of the alkyl radicals represented by A 45 .the diazo compound so obtained with a pyrazolone of the
there may be mentioned lower alkyl radicals such as
formula:
methyl and ethyl radicals. As examples of the carboxylic
CHz-—~C—A
acid ester groups represented by A there may be men
tioned carbo lower alkoxy groups such as carbomethoxy,
2A
carbethoxy, carbopropoxy and carbobutoxy groups and 50
carb'oaryloxy groups for example carbo monocyclic aryl
oxy groups such as carbophenoxy.
N
As examples of the
substituted carbamyl groups represented by A there may
be mentioned N-methylcarbamyl, NzN-dimethylcarbamyl,
‘N-ethylcarbamyl, NzN-diethylcarbamyl, N-phenylcar
bamyl, N-methyl-N-phenylcarbamyl, N-?-hydroxyethyl
carbamyl and NzN-di-(B-hydroxyethyl)carbamyl.
z
55
2
Formula II
It is preferred that A represents a carboxylic acid “
‘groups or a lower alkyl radical, preferably a methyl radi
cal.
wherein A and Z have the meanings stated above, and the
60 benzene nucleus may be substituted by atoms or groups
other than hydroxy, amino and substituted amino groups.
As examples of the alkyl radicals represented by R there
As examples of the amines of Formula I which may be
may be mentioned lower alkyl radicals such as methyl,
used to obtain the azo compounds used in this process of
ethyl, propyl and butyl, and as examples of the substitu
the invention there may be mentioned Z-naphthylamine
ents which may be present in the benzene nucleus there
may be mentioned halogen atoms for example chlorine, 65 lzrS-disulphonic acid, Z-naphthylamine 1:5:7-trisulphonic
acid, Z-naphthylamine-l:sulphonic acid, Z-naphthylamine
alkyl radicals for example lower alkyl radicals such as
methyl, alkoxy radicals for example lower alkoxy rad
icals such as methoxy, nitro, carboxy and sulpho groups.
1:6 ~ disulphonic
sulphonic acid.
acid
and Z-naphthylamine - 1:7 - di
3,097,197
The pyrazolones of Formula 11 wherein A represents
a carboxylic acid ester group may be obtained by heating
wherein A and Y have the meanings stated above, and
the benzene nucleus may be substituted vby ‘atoms or groups
other than hydroxy, amino or substituted amino groups.
This process of the invention may be conveniently car
ried out by adding sodium nitrite to a solution or sus
pension of the amine of Formula I in a dilute aqueous
the corresponding pyrazolone wherein A represents a car
boxylic acid group with an excess of the appropriate
alcohol in the presence of sulphuric acid or hydrochloric
acid, making neutral with sodium carbonate, removing
the excess alcohol by distillation, adding water and ?lter
solution of hydrochloric acid, adding the diazo solution
ing oif the pyrazolone which is precipitated.
or suspension so obtained to an ‘aqueous solution of the
The pyrazolones of Formula II wherein A represents a
carbamyl or substituted carbamyl ‘group may be obtained
coupling component and ?ltering off the azo dyestutf
which is precipitated. If desired sodium chloride can be
added to ensure complete precipitation of all the azo dye
stuff.
by heating the corresponding pyrazolone wherein A repre-'
sents a carbethoxy group with an excess of ammonia or
the appropriate ‘amine and subsequently removing the
The coupling components used in this process of the
excess ammonia or the amine. Alternatively the pyrazo
invention may be obtained by treating a pyrazolone of
lones of Formula II wherein A represents an N-aryl sub 15 Formula II with cyanuric chloride or with cyanuric
stituted car-barnyl group and R represents ‘a hydrogen atom
bromide.
may be obtained by reacting a pyrazolone of the formula: '
As examples of coupling components which may be
used in this alternative process of the invention there may
be mentioned 1-[3'- or 4'—(4":6"-dichloro-1”:3”:5"-tri
20
azin-2"-y1amino)phenyl] -3-methyl—5-pyrazolone, 1-[3'- or
4'- (4" : 6"-‘dichloro - 1" : 3 " : 5 "~triazin-2.”-y1amino) phen
yl]~3-carboxy-5-pyrazolone, 1-[3'- or 4’-(4":6"-dichloro
1":3":5"-tniazin-2"-ylamino)-4'- or 3’-sulphophenyl]-3
methyl-S-pyrazolone, 1-[3'- or 4'-(4":6"-dichloro-l":3":
25 5" - triazin - 2" - ylamino)-4'- or 3'-sulphopheny1]-3-car
boxy-S-pyrazolone, 1-[3'- or 4’-(4”:6”~dichloro -1":3":
5"-triazin-2"-ylamino)phenyl] -3-carbomethoxy, carbeth
wherein one Z’ represents a hydrogen atom or a sulphonic
acid group ‘and the other Z’ represents a nitro group, and
oxy, carbopropoxy or carbophenoxy-S-pyrazolone, 1-[3'
or 4'-(4”:6"-dichloro - 1":3":5” - triazin - 2”-y1amino)
the benzene nucleus may be substituted by atoms or
groups other than hydroxy, amino and substituted amino 30
phenylJ-3-oarbamyl, N-methylcarbamyl, N:N-dimethyl
groups, with the appropriate iarylamine in the presence of
carbamyl, N - ethylcarbamyl, N:N - diethylcarbamyl, N
phenyl-carbamyl, N-methyl - N - phenylcarbamyl, N-?-hy
phosphorus oxychloride and subsequently converting the
droxyethylcarbamyl or NzN-di(?-hydroxye<thyl) carbam
nitro group to an amino group.
yl-S-pyrazolone, 1-(2’-methyl-5' - (4":6"-dichloro-1:3:5
As examples of pyrazolones of Formula II which may
be used to obtain the azo compounds used in this process
triazin-2-ylamino)pheny1] - 3 - methyl or 3-carboxy-5-py.
of the invention there may be mentioned 1-(3'-amino
razolone, 1-[2’-chloro-5’ - (4":6"-dich1orotriazin-2"-yla_
phenyl) - 3 - methyl-S-pyrazolone, 1-(3'-aminopheny1)-3
carboxy - 5 - pyrazolone, 1-(4'-a.rninophenyl)~3-methyl-5
mino)-phenyl] - 3 - methyl- or 3-carboxy-5-pyrazolone, 1
[4'-(4":6"-dichloro - 1":3”:5"-triazin - 2"-ylamino)-2'
pyrazolone, 1 - (3'-aminophenyl) -3-carbethoxy-5-pyrazo 40 carboxyphenyl]-3-methyl- or 3-carboxy-5-pyrazolone, 1
lone, 1 - (3' - amino~4'-su'lphophenyl)~3-methyl-5-pyrazo
[4’—(4":6”~dichloro - 1":3”:5”-triazin - 2”-ylamino)-2'
lone, l-(3'-aminopheny1)-3-carbamyl, N-methylcarbamyl,
N:N-dimethylcarbamyl, N-ethylcarbamyl, N:N-diethyl
carbamyl, N-phenylcanbamyl, NJmethyl-N-phenylcar
methoxyphenyl1-3-methy1 or B-carboxy-S-pyrazolone, 1
no)phenyl] -3-carboxy - 5 - pyrazolone and 1-[3'-(4”:6”
barnyLN-IS-hydrOXyethyIcarbamyl or N:N-di(?—hydroxy
ethyl)carbamyl~5-pyrazolone, 1 - (4'-aminopheny1)-3-car 45
boxy-S-pyrazolone.
[4’- (4" : 6"—dichloro-1” : 3 " : 5"-triazin - 2"-y1-methylami
dibromo - 1”:3":5"-triazin - 2"-ylamino)phenyl]-3-car
bomethoxy, carbethoxy, carbopropoxy or carbophenoxy
It is generally preferred to isolate the new azo dyestuffs,
5~pyrazolone, l-(4-aminophenyl)-3-carbamyl, N-methyl
as hereinbefore ‘de?ned, from the medium in which they
have been formed at a pH from 6 to 8 and it has been
carbamyl, N:N-dimethylcanbamyl, N-ethylcanbamyl, N
phenylcarbamyl, N-methyl-N-phenylcarbamyl or N-B-h - 50 found that the loss of halogen atoms from the triazine ring
droxyethylcarbamyl-S-pyrazolone, 1-(2'-methyl-5'-amino
present in the dyestuifs can be reduced considerably by
the addition of certain buffering agents which give a pH
value between 6 ‘and 8 and in particular by those which
give a pH of about 6.5. The buffering agents may be
razolone, 1 - (4'-amino-2’-carboxyphenyl) -3-methy1 or 55 added at any stage during the manufacture of the dye
stuif but it is preferred to add the buffering agent just
-carboxy-5-pyrazolone, 1 - (4’-amino-3'—sulphopheny1)-3
before the dyestulf is isolated and to subsequently dry
methyl or -carboxy-5-pyrazolone, 1-(4'-annino-3’-sulpho-‘
‘the dyestuff in the presence of such a bu?ering agent. As
phenyl)-3-methyl or -canboxy-5—pyrazolone, 1-(4'-arnino~
examples of suitable buffering agents which can be used
2'-methoxyphenyl)-3-methyl or -carboXy-5-pyrazolone
and 1-(4'—methylaminopl1eny1)-3-carboxy-5-pyrazolone. 60 there may be mentioned mixtures of disodium hydrogen
phosphate and sodium dihydrogen phosphate or potassium
According to a further feature of the invention there
phenyl)-3-methyl or -carboxy-5qpyrazolone, 1-(2'-ch1oro
5'-aminopheny1)-3-methyl or -canboxy-5~pyrazolone, 1
(3’-amino-4'-su1phophenyl)~3-methyl or -carboxy-5-py
is described an alternative process for the manufacture
of the new azo dyestuffs, ‘as hereinbefore de?ned, which
comprises diazotising an amine of Formula I, as herein
dlhydrogen phosphate and mixtures of sodium diethyl
metanilate and sodium hydrogen sulphate.
\-
The new azo dyestuffs, as hereinbefore de?ned, are
before de?ned, and coupling the diazo compound so ob 65 valuable for colouring cellulose textile materials, for
tained with a coupling component of the formula:
example cotton, viscose rayon and linen textile materials.
For colouring the cellulose textile materials the new azo
dyestu?s, either singly or in the form of mixtures, may
be applied by either a dyeing or a printing method, pref
70 erably in conjunction with a treatment with an acid
‘binding agent, for example by the methods disclosed in
British Patent No. 797,946. When so applied to cellulose
textile materials the new 'azo dyestuifs, as hereinbefore
de?ned, yield greenish-yellow to orange shades possessing
75 excellent fastness to wet treatments and to light.
l
i
l
3,097,197
5
'6
parts of the disodium salt of ‘the azo compound WhiCh'iS
‘Belgian Patent No. 558,957 describes and claims inter
alia azo dyestuffs of the formula:
obtained by coupling diazotised 2~naphthylamine-1:5-di
sulphonic acid with 1-(3’-aminophenyl)~3-methyl-5-py
razolone.
On analysis the dyestu?f composition so obtained is
found to contain 2.14 atoms of organically bound chlorine
for each molecule of dyestu? present.
When applied to cellulose textile materials in conjunc
tion with a treatment with an acid-binding agent the dye
10
stu?? yields golden yellow shades possessing excellent fast
ness to light and to washing.
Example 3
In place of the 599 parts of the trisodium salt of the
wherein R1 represents a naphthalene nucleus containing 15 azo compound used in Example 1 there are used 64.9
parts of the trisodium salt of the azo compound which is
at least one sulphonic acid group, R3 represents a methyl,
obtained by coupling diazotised Z-naphthylamine 1:5:7
trisulphonic acid with 1-(3'-aminophenyl)-3-methyl-5-py
carboxy or modi?ed carboxy group and n is a positive
Whole number, which are obtained by condensing a cy
anu-ric halide with azo compounds which are themselves
obtained by coupling diazotised naphthylamine sulphonic 20
acids with py-nazolones of the formula:
razolone.
On analysis the dyestu?f composition so obtained is
found to contain 1.86 atoms of organically bound chlorine
for each molecule of dyestu? present. When applied to
cellulose textile materials in conjunction with a treatment
with an acid-binding agent the dyestu? yields golden yel
25 low shades possessing excellent fastness to light and to
washing.
The following table gives further examples of the new
dyestu?s of the invention which are obtained by replacing
the 59.9 parts of the trisodium salt of the azo compound
30 used in Example 1 by an equivalent ‘amount of the sodi
um salt of the azo compound which is obtained by diazo
tising the naphthylamine sulphonic ‘acid listed in the sec
ond column of the table and coupling the diazo compound
wherein R3 ‘and n have the meanings stated above.
None of the dyestu?fs of the present application are de
scribed in Belgian Patent No. 558,957 and there is no dis
so obtained with the pyrazolone listed in the third column
35 of the table. The fourth column of the table indicates the
shades obtained when the dyestuffs are applied to cellulose
textile materials in conjunction with a treatment with
closure in this Belgian patent of the use of Z-naphthyl
amine l-sulphonic acid or of 2-naphthylamine l-sulphonic
an acid-binding agent.
acid containing additional sulphonic acid groups as the
diazo components. When compared with comparable 40
dyestuffs of Belgian Patent No. 558,957 the dyestuffs of
the present application give dyeings on cellulose textile
Example
Naphthylamine
Pyrazolone
Shade
sulphonicacid
materials which have superior light fastness.
The invention is illustrated but not limited by the
1-(3’-amino-4’su1pho~
Greenish
following examples in which the parts and percentages 45 4 _______ _- 2-naphthy1arnine-1z5disulphomc acid.
phenyD-3-methyl-5yellow.
pyrazolone.
are by weight:
5 ____________ “do _______________ __ 1-(4’-aminophenyl)-3Golden
Example 1
methy1-5-pyrazoyellow.
lone.
A solution of 59.9 parts of trisodiurn salt of the azo
compound which is obtained by coupling \diazotised 2
naphthylamine-l:5edisulphonic acid with l-(3’-‘arnino
6 ____________ __do _______________ __
50
of sodium carbonate are then added.
22.5 parts of so
dium \diethylmetanilate, 1.5 parts of sodium hydrogen
paste so obtained is mixed with 11.25 parts of sodium
Do.
7 _______ __ 2-naphthylamine-1-
1-(3’-amin0-4’-sulpho-
Reddish
8 _______ __ Z-naphthylamine-
1-(3’-arninopheny1)-3-
Yellow.
sulphonic acid.
1: 5: 7-trisulphonic
acid.
9 _______ __
phenyi)-3-carboxy~
5-pyrazolone.
yellow.
carbethoxy-5
pyrazolone.
Z-naphthylamiue-lzti-
1-(3’-aminophenyl)-3-
disulphonic acid.
carboxy-?-pyrazo
Do.
no.
10 ______ __ 2-naphthy1amine~
1 -. 5: 7-tr1sulphonic
acid.
1-(3’an1inophenyD-31~(3’-arninophenyl)-3-
12 ______ __ 2~naphthy1amine-1:5-
1-(4-N~methylamino-
disulphonic acid.
Do.
carb amyl-?epyrazo
lone.
11 ___________ __do _______________ __
sulphate and 75 parts of sodium chloride are then added
and the precipitated dyestu? is ?ltered off. The dyestuff 60
caIboxy-5-pyrazo
lone.
phenyl)-5-pynazolone-3-carboxylic acid in 600 parts of
water is added with stirring to :a suspension of 18.8 pants
of cyanuric chloride in a mixture of 140‘ parts of acetone,
400 parts of ice and 400 parts of water, the temperature
being maintained ‘between 0° and 3° C. The mixture is 55
stirred for 1 hour and 50 parts of a 10% ‘aqueous solution
1-(4’-a.min0pheny1)-3-
N-methylcarbamyl
5>pyrazolone.
phenyD-B-carboxy
?-pyrazolone.
Do.
Do.
diethylmetanilate and 0.75 part of sodium hydrogen sul
phate and ‘dried at 20° C.
On analysis the dyestutf composition so obtained is 65
The 1 - (3’-aminophenyl)-3-carbethoxy - 5 - pyrazolone
found to contain 1.89 atoms of organically bound chlo
used in Example 8 may be obtained in the formv of its salt
rine for each molecule of dyestu? present. When applied
to cellulose textile materials in conjunction with a treat
with hydrogen chloride by ‘heating l-(3’-aminophenyl)-3
carboxy-S-pyrazolone with ethanol which has been satu
ment with an acid-binding agent the dyestuif yields golden
yellow shades possessing excellent fastness to light and to 70 rated with hydrogen chloride gas and subsequently remov
ing the excess ethanol ‘by distillation when the hydro
washing.
Example 2
In place of the 59.9 parts of the trisodium salt of the
azo compound used in Example 1 there are used 54.7
chloride of 1-(3'-aminophenyl) - 3 - carbethoxy - 5 - pyra
zolone (which melts at 210° C.) separates out and is
?ltered 0E and dried.
The l-(3’-aminophenyl)-3-carbamyl-5-pyrazolone used
‘ 3,097,197
7
8
in Example 10 may be obtained in the form of its salt
What we claim is:
with hydrogen chloride by heating 1-(3'-aminophenyl)—3carbethoxy-S-pyrazolone with a 20% aqueous solution of
Azo dyestutfs which, in the form of the free acids, ‘are
represented by the formula:
ammonium hydroxide in an autoclave at a temperature of
80° C. cooling the mixture so obtained, adding a con- 5
centrated aqueous solution of hydrochloric acid until the
mixture is acid to Congo Red and ?ltering 01f the precipitated hydrochloride of 1-(3'-a1ninophenyl)-3-carbamyl—
SOaH
(303K)“
0 N
\ /
5-pyrazolone (which melts at 250° C.).
The 1-(3’-aminophenyl)-3-N-methylcarbamyl-5-pyraz- 10
olone used in Example 11 may be obtained in the form of
its hydrochloride by replacing the 20% aqueous solution
of ammonium hydroxide used for the preparation of 1-(3'arninophenyl)~3-oarbamyl-S-pryrazolone by a 20% aque
ous solution of methylamine.
I
—Y
15
Y
wherein:
Example 13
i
A Solution of 4_7 parts of l_(3’_amjnophenyl)_3-me?1y]5-py-razolone in a mixture of 100 parts of water and 100‘
parts of acetone is added, over 30 minutes, with stir-ring to 20
n represents one of the numbers 0, l, and 2;
A ‘represents a member selected from the group consist
111g of lower "alkyl, CaTbOXYL Garbo lower ‘alkoxy,
Carbamyl, lower alkyl carbamyl;
a suspension of 8.75 parts of cyanuric ‘bromide in a mixture of 100 parts of dioxan, 150 parts of ice and 150 parts
of water. The mixture is then stirred for 1 hour at a temperature between 5° and 10° C. whilst maintaining the pH
one Y_1'ePfe$¢11t$ ‘3 ‘member Selected from the group
conslsting of hydrogen and ~SOsH, ‘and the Oth?l‘ Y
represents a group of th? formula:
X
of the mixture between 6 and 8 by the addition of 10% 25
R
aqueous solution of sodium carbonate. 20 parts of sodi-
|
um carbonate are then added followed by an aqueous \suspension of diazotised Z-naphthylamine-l :S-disulphonic
acid (which is obtained by adding sodium nitrite to a su-s-
N_&
%
“N_C\
\
/N
N=o
I];
pension of 7 parts of 2-naphthylamine-1:S-disulphonic 3O
_
acid in a dilute aqueous solution of hydrochloric acid)
Wherem:
and the mixture so Obtained is then Stirred for 2 hours
at a temperature between 5° and 10° C. The pH of the
mixture is then raised to 7 by the addition of a concentrated aqueous solution of hydrochloric acid and 5.5 parts 35
.
R represents a member selected from the group consist
mg of hydrogen and lower 'alkyl;
X TePIFS‘f'HtS ‘3 halogen atom selefited from the group
‘conslstmg of chlonne ‘and bromme
of sodium diethylmetanilate, 0.4 part of sodium hydrogen
“
sulphate and 40 parts of ‘sodium chloride are added. The
'
.
.
.
References Clted m the ?le of thls patent
precipitated dyestu? is then ?ltered off, the dyestu? paste
UNITED STATES PATENTS
so obtained is mixed with 2.81 parts of sodium diethyl- 40
2,892,329
Stephen _____________ __ June 30, 1959
metan'llate and 018 part of sodium hydrogen sulphate and
2,951,070
Stephen et .ai __________ __ Aug 30, 1960
the 1111mm 15, then dr1ed~
2,951,071
Tilley _______________ __ Aug, 30, 1960
558,957
FOREIGN PATENTS
Belgium ______________ __ Ian. 4, 1958
200,687
Austria _____________ __ Nov. 25, 1958
_
_
_
_
When apphed to cellulose textile materials in conjunc
tion with a treatment with an acid-binding agent the dyestu? yields golden yellow shades possessing excellent fast- 4
ness to light and to washing.
5
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