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Патент USA US2131894

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2,1313%
Patented Oct. 4, 1938
‘UNITED, STATES PATENT OFFICE v
2,131,894
‘ ‘
AZO DYEISTUFFS‘ AND THEI‘B. raonUcTIoN'
Arthur vHoward Knight, Blackley, Manchester,
England, assign'or to Imperial Chemical ‘In
dustries Limited,a corporation of Great Britain
No Drawing‘.- Application November 30, 1934, See.
rial No. 755,505. V In Great Britain DecemberB,
-
1933
1
‘
>
In U. S. Patent No. 1,483,084 there‘is described acetate arti?cial ‘ silk, ‘dyeing _;.that material ‘from
the manufacture of azo dyestuffs which "dye wool 'anacid, neutral or alkaline bath in orange-brown:
and silk from an acid bathiand‘which owe their to red-brown shades ‘of good iastness properties
solubility and acid character tothe presence in and good dischargeability. They are also emié
. their structure of ‘the alcoholic sulphuric acid: nently suitable for the direct‘printing of acetate
group -‘—C2I-I4SO4H attached to nitrogenm Dyes arti?cial silk.‘ Moreover they are valuable for
containing this -—C2H4SO4H group - (including ' dyeing wool, natural ‘silk, and tin-weighted silk
soluble salts thereof) have been called “sulphato”.
dyes.
10
>
1
- In British vspeci?cation No. 237,739‘ there is
described a process" of dyeing acetate‘ arti?cial
silk by applying certain sulphato monoazo ‘dyes,v
and in particular the sulphato compounds of ni
trated monoazo dyes, in'a neutral, acid, or‘alka
ii
-
v =
weight.
‘
>
r
w
,
.7
-
Example 1
Sixty-nine (69) parts’ of sodium nitrite are
»'
nitrobenzeneazo-p—N-sulphatoethyl - aniline, 2,6?‘
di-bromo~4-nitrobenzeneazo-p-N -sulphatoethyl¢
aniline, 2-chlor-G-broinA-nitrobenzeneaZo- pT-N
sulphatoethyl-aniline, 2,6-‘di-chloro-4 --nitroben
zeneazo - p - N esulphaltopropyl - aniline, 2,6 - di
bromo-é-nitrobenzeneazo-p - N ‘- sulphatopropyle
aniline, 2-chlor-6-brom-ll-nitrobenzeneaZo-p- N
sulphatopropyl-aniline, 2,6-cli-chlord-4-nitroben
zeneazo-p-N-alkyl- N -sulphatoethyl—aniline, “2,6
di-bromo-4-nitrobenzeneazo-p'- N-alkyl ‘- N - su1-"
phatoethyl-aniline, ‘2-ch1or-6-brom- 4 - nitroben;
zeneazo-p'éN - alkyl-N-sulphatoethyl-aniline, ' 2,6-.
di-chloro-4-initrobenzeneazo-p-N -'alkyl ‘- N = sul-'>
phatopropyl-aniline, 2,64 di~bromo - 4 - nitroben
zeneazo-p-N-alkyl- N -sulphatopropyl-ani1ine, 24
chlor-6-brom—4;nitrobenzeneazo-p- N. -alkyl - N -
sulphatopropyl-aniline, in the coloring of acetate
arti?cial silk, silk, tin-weighted silk, leather, and
2,6 -, dichloro; 4 - nitroaniline
(10%
excess
of
theory), vareadded to this with stirring during
two hours and stirring continued for a short time
longer if necessary, until no solid matter remains. 20
The resulting liquid is then poured into 4000
parts of ice and 1000 parts of water with good '
agitation.
After stirring for half‘ an hour the
solution of the diazotized 2,6-dichloro-4-nitroani
line is ?ltered from undiazotized base and added
slowly to a cooled solution of 245 parts of N-ethyl 25v
N-sulphatoethylaniline in ‘4000 parts of water
containing 40 parts ofcaustic soda. Ice is added
from time to time to keep the temperature of the
coupling medium at 0°-5° C. and 40% aqueous 30
caustic soda is‘ also added gradually at such a
rate that the coupling medium is ‘at no time dur
ing coupling more than slightly acid to Congo Red
paper or slightly‘ alkaline to Clayton Yellow
paper. _ When coupling is complete the dyestuff 35
suspension is made alkaline by the addition of
wool.
Also I
according
T‘
to thep invention, I‘ manufacture
l l
caustic soda and; the dyestuff is then ?ltered o?,
new mono-azo dyestu?s by coupling ,diazotized
washed‘ with 5% brine and preserved as paste or
dried in any suitable way. It is soluble in water‘
and dyesiacetate arti?cial silk from a neutral 40
2,6-dichloro-4-nitro-aniline or 2,6 - dibromo - 4 -
nitroaniline or 2-chloro-6-bromo- 4 e nitroaniline
with an N-sulphatoethyl (or propyl), or an N
alkyl-N-sulphato-ethyl (orpropyl) derivative of
an amine of the benzene series adaptedtodimplev
in the para position to the aminoygroupi,
45
the followingexamples in which the parts are by 10
‘ added to MSG-parts of ‘100%. sulphuric acid, and 15
According to the present invention I apply new stirred until no ‘solid, remains, then 277.7 parts of
line dye-bath.
sulfato-monoazo dyes, namely, 2,6-di-chloro-4
20
and leatherin orange-brown to red-brown shades. ,
a The invention is illustrated but not limited by
, . 1
‘Also according to the, invention 1 manufacture
the new dyestu?s by treating the dry water in
soluble dyestuffs obtained by combining diazo
tized 2,6-dichloro- or 2,6-dibromo- or 2-chloro
6-bromo-4-nitroaniline with an N - 13 - hydroxy
50 ethyl- or hydroxy-propyl- or an N-alkyl-N-p-hy
droxyethyl- or hydroxy-propyl derivative of an
amine of‘the benzene series adapted to couple in
the para position to the‘amino group with‘ an
'55.
agent adapted to give the sulphuric esters.
The new dyestuffs have very good a?inity for
bath containing 3%‘ salt, giving orange-brown
shades of good fastness properties and good dis
chargeability.
-
>
-
'
-,
It can also be employed for the production of
orange-brown prints on acetate arti?cial silk.
45
The dyestuff when applied from an acid bath, _
possesses good‘af?nityfor wool, natural silk, and
tin-weighted silk, dyeing these materials in
orange-brown shades. ‘
‘
When applied to leather by the method usually 50
employed for‘acid‘ dyestuffs it produces orange
brown shades of good fastness properties,
. ,,
,,.If instead‘of using 227.’? parts of ‘2,6-dichloro
ll-nitro-aniline there are used 325.6 parts of 2,6
dibromo-lienitroanili'ne or "277.7. parts ‘of 2 - 55
2
2,131,894
chloro-6-bromo-4-nitroaniline, dyestu?s produc
with good agitation. After stirring for half an
ing similar orange brown'shades are obtained.
Slightly yellower shades are obtained by the dye,
stu?’s made by using 247 parts of N-methyl-N
sulphatopropyl aniline in place of 259 parts of N
ethyl-N-sulphatopropylaniline.
N-ethyl-N -sulphatopropy1 aniline is obtained
in the form of an aqueous solution of its sodium
10
salt by reacting one molecular proportion of N
ethyl-N-y-hydroxypropyl aniline with one molec
ular proportion of chlorosulphonic acid in ethyl
ene dichloride solution, adding dilute aqueous
caustic soda until permanent alkalinity to Bril
liant Yellow paper is obtained, and separating
the aqueous extract from the ethylene dichloride.
Example 2
Sixty-nine (69) parts of sodium nitrite are
added to 1480 parts of 100% sulphuric acid and
20 stirred until no solid remains, then 227.7 parts
of 2,6-dichloro~4-nitroaniline (10% excess of
theory) are added to this with stirring during
two hours and stirring continued for a short
time longer if necessary, until no solid matter
The resulting liquid is then poured
into 4000 parts of ice and 1000 parts of water
with good agitation. After stirring for half an
hour the solution of the diazotized 2,6-dichloro
4-nitroaniline is ?ltered from undiazotized base
and added slowly to a cooled solution of 261
> _
remains.
parts of N - sulphatoethyl - m - amino - p - cresol
and added slowly to a cooled solution of 231
parts of N -methyl-N-sulphatoethylaniline in 4000
parts of water containing 40 parts of caustic
soda. The temperature of the coupling medium
is kept at 0°-5° C. by the periodical addition
of ice, and 40% aqueous caustic soda solution is
also added gradually at such a rate that the 10
coupling medium is at no time during coupling
more than just acid to Congo Red paper or
slightly alkaline to Clayton Yellow paper. When
coupling is complete the dyestuff suspension is
rendered alkaline with caustic soda, the dyestu? 15
?ltered off, Washed with 5% brine and preserved
as paste or dried in any suitable way. It is solu
ble in water and dyes acetate arti?cial silk from
a neutral bath containing 3% salt, giving orange
brown shades of good fastness properties and 20
good dischargeability. The vdyestui’l" can also be
applied for the direct printing of acetate arti
?cial
silk.
.
.
'
The dyestuff, when applied from an acid bath,
possesses good affinity for W001, natural silk and 25
tin-weighted silk, dyeing these ,materials in
orange-brown shades.
Example 4
The insoluble dyestuff. obtained bydiazotizing
251.5 parts of 2-chloro-6-bromo-4-nitroaniline
methyl ether in 4000 partsof Water containing
and combining the diazo solution so obtained with
40 parts of caustic soda. Ice is added from time
to time to keep the temperature of the coupling
medium at 0°-5° C. and 40% aqueous caustic
207 parts of N-n-butyl-N-B-hydroxyethyl-m
soda solution is added at such a rate that the
coupling medium is kept only just acid to Congo
Red paper during the addition of the diazo solu
tion. When all the diazo solution has been added
the dyestu? is ?ltered from the acid medium,
washed with water, and the dyestuff paste ground
with sufficient sodium carbonate to neutralize
any remaining free acidity and to convert the
dyestuff into its sodium salt. The dyestu? can
I then be preserved as paste or dried in any suit
able way.
It dyes acetate’ arti?cial silk from a neutral
bath containing 3% salt in red-brown shades of
good fastness properties and dischargeability.» It
is also suitable for the direct printing of acetate
arti?cial silk.
N-sulphatoethyl-m-amino-p-cresol m e t h yl
ether is obtained by treating one molecular pro
portion of N-p-hydroxyethyl-m-amino-p-cresol
methyl ether in tetrachloroethane with one mo
lecular proportion of chlorosulphonic acid, re
moving the tetrachloroethane and crystallizing
the crude sulphate compound from alcohol.
has m. p. 192° C.
toluidine is dried and ground to a powder and
the powder so obtained is added during about two
hours to a solution of 1480 parts of 100% sul
phuric acid with good stirring. Stirring is con
tinued for a further 12-18 hours and the sul
phuric acid solution then poured into 4000 parts
of ice and 1000 parts of water. The sulphate 40
compound of the dyestuff separates from solu
tion and is ?ltered off, Washed thoroughly with
water, and the dyestu? paste so obtained treated
with su?icient sodium carbonate to neutralize
any remaining sulphuric acid and to form the
sodium salt of the sulphato dyestu?. The prod 45
uct so obtained is then preserved as paste or
dried in any suitable way. It dyes acetate arti
?cial silk in brown shades when applied from a
neutral bath containing 3% salt.
N-n-butyl-N-B-hydroxyethyl-m-toluidine is ob
with n-butyl chloride.
It has b. p. 177°-178°
C./12 mm.
-
I claim:
.
-
1. The compound represented by the formula:
Example 3
55
halogen
It
Sixty-nine (69) parts of sodium nitrite are
added to 1480 parts of 100% sulphuric acid and
stirred until no solid remains, then 325.6 parts
70 of 2,6-dibromo-4-nitroaniline (10% excess of
theory) are added to ‘this with stirring during
two hours and stirring continued for a short
time longer if necessary, until no solid matter
remains. The resulting liquid is then poured
75 into .4000 parts of ice and 1000 parts of water
50
tained by treating N-,hydroxyethyl-m-toluidine
sulphatoalkyl
'
If in place of 325.6 parts of 2,6-dibromo-4
nitroaniline, there are used 227.7 parts of 2,6
dichloro-4-nitroanillne or 277.7 parts of 2-chloro
6-bromo-4-nitroaniline, there are obtained dye
stuffs producing similar red-brown shades.
65
hour the solution of the diazotized 2,6-dibromo
4-nitroaniline is ?ltered from undiazotized base
V
halogen
Y
DIIm
in which X is methyl, Z is methoxy, each m is
one of the group consisting of 0,1, and 2, the sum
of m+m is not greater than 2, and Y is one of
the group consisting of hydrogen and alkyl.
65
2. An azo dyestuff represented by the formula
of claim 1 wherein the halogen is of atomic
weight exceeding 30 but less‘than 90.
3. The compound represented by the formula:
halogen
halogen
’
Xm"
I
r
76
2,181,894
7
p
in which X is oneof the group consisting of
methyl and methoxy, m is one of the group con
halogen
sisting of 0, I, and 2, and Y is one of the group
consisting of hydrogen and alkyl.
5
4. The compound represented by the formula:
halogen
'
3
droxyalkyl-arylamine and in another step cou- '
pling a diazotized arylamine of the formula: '
0=N
N=N-c1
5
halogen
snlphetopropyl
to a compound of the formula
10
halogen
10
Y
1km
in which X, m, and Y have the meaning set forth
in claim 3 and in which halogen is of atomic
weight between 30 and 90.
15
5. An azo dyestuff havingthe formula:
01
‘ om
20
.
in which Y is one of a group consisting of hy
drogen and alkyl, Z is one of a group consisting 15
of hydroxyalkyl and 'sulphatoalkyl, X is one of a
group consisting of methyl and methoxy, and m
is one of a group consisting of 0, 1, and 2, where
by to form a compound represented by the 2
CHi-CH:
=N<:>'N< one-om-o-s 05-11
1
formula:
' ’
6. An azo dyestuif having the formula:
' t
01
'
OgN
N=
1
" 30
l
H
/
-
XIn
'
25
consisting of hydrogen and alkyl.
CHgCHaCHnCHs
Br
/sulphatoalkyl
in which X is one of the group consisting of
methyl and methoxy, m is one of the group con
sisting of 0, 1, and :2, and Y is one of the group
10. Process according to claim 9 in which the
‘ '7. An azo dyestu? having the formula: V
~
0
N=N—®—N
|
\Y‘
halogen‘
'
N\ ’
CHn‘—CHr-0—- S Call
H;
.
OzN
0-013:
25
‘
halogen
N-sulphatoalkyl-N-Y derivative is an N-sulphato
_
ethyl derivative.
'
11. Process according to claim 9 in which the
N-sulphatoalkyl-N-Y derivative‘ is an N-sulphato
35
‘
CHzCHzr-O-SOaH
O1 7
CH:
7
8. A process for the manufacture of azo dyes,
which comprises coupling diazotized 2,6-di
halogeno-4-nitroaniline with an N-sul‘phato
‘10 alkyl derivative of an arylamine of the benzene
series carrying at least one of the substituent
group consisting of methyl and methoxy and ca
pable of coupling para to the amino group.
9. The process which comprises in one step
45 sulphating the N-hydroxyalkyl group of an N-hy
propyl derivative.
‘
‘
35
12. The process for the manufacture of azo
dyes which comprises coupling diazotized 2,6-di
halogeno-ll-nitroaniline with an N-hydroxy
propyl-N-X derivative of a para-coupling aryl
amine of the benzene series, in which X is one
of the group of compounds consisting of halogen
and a short chain saturated alkyl group, and
subsequently converting the hydroxypropyl into
sulphatopropyl by treatment with sulphuric acid.
ARTHUR HOWARD KNIGHT.
‘45
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