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Патент USA US2118088

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Patented May 24, 1938
2,118,088?
UNITED STATES PATENT OFFICE
2,118,088
MONOAZO DYESTUFFS AND THEIR
PRODUCTION
Arthur Howard Knight and Henry Alfred Piggott,
Blackley, Manchester, England, assignors to
Imperial Chemical Industries Limited, a cor
poration of Great Britain
No Drawing. Application February 21, 1935, Se
rial No. 7,659. In Great Britain February 23,
1934
13 Claims. (Cl. 260-96)
The present invention relates to the manufac
ably by virtue of the multiplicity of polyethenoxy
ture of new monoazo dyestu?s.
groups they contain, have characteristic prop
According to the invention we make thesaid erties.
new dyestuffs by coupling a diazotized para-nitro
The new dyestuffs can be converted into dis
5 amine of the benzene or naphthalene series, hav
persible dyestuff powders by milling the dyestuff 5
ing no sulphonic or carboxylic acid groups, with pastes with known dispersing agents, e. g. those
the compounds (or mixture of compounds) ob
described in British speci?cation 224,077, fol
tained by N-substituting with polyethenoxy lowed by drying and grinding operations. These
radicles, to the extent de?ned below, those amines dispersable powders are superior to those ob
10 of the benzene series adapted to couple in the tained by similarly treating the known dyestuffs 10
para position to the .amino group.
The compounds used as second components ac
cording to the invention have the general
formula:
15
A,
where Ar is an aryl group of the benzene series
20 free from carboxylic and sulphonic acid groups
and having an unsubstituted position para to the
N, R is methyl, ethyl, ?-hydroxethyl or
25 n and n’ being integers greater than zero, such
that n+n' does not exceed 10 and preferably does
not exceed 4.
A
In selecting a suitable diazo component to cou
ple with an amine of the formula given, atten
30 tion must be paid to the necessity of being able
to separate the obtained dyestu? in a solid form.
‘When the sum of n and n’ is 6 or more, and the
diazotized amine used for coupling is 4-nitro
aniline, the dyestuff may be a jelly-like mass
35 whereas when the sum of n and n’ is 3 or 4 the
dyestuffs can be readily isolated in solid form.
Suitable coupling components may be made by
reacting in presence of a small quantity of caustic
soda, suitable amines such as e. g. N-hydroxy
40
ethyl-m-toluidine.
N-n-butyl-3-amino-4-meth
oxytoluene, N-ethylam'line or aniline with a quan
tity of ethylene oxide calculated. to supply the
necessary number of polyethenoxy residues (see
formula above). Alternatively, a mixture of
45 ethylene chlorhydrin and caustic soda may be
used in place of ethylene oxide.
Suitable diazo- components are diazotized 4
nitroaniline, 5-nitro-2-anisidine, 2-chlor-4-nitro
aniline, 2,6-dichloro-4-nitroaniline, 2,6-dibromo
e-nitroaniline, 2,4-dinitroaniline, 6-chloro-2,4
dinitroaniline, 2,4-dinitro-l-naphthylamine.
Monoazo dyestuffs from N-mono-p-hydroxy
ethyl-, N-alkyl-p-hydroxyethyh, and N-p,/3’
dihydroxyethylamines are known.
The dye
55 stuffs of the present invention, however, prob
mentioned above as regards the ease and ef?ciency
with which they disperse in water, the disper
sions obtained having the appearance of true
solutions. To this property are due the excellent
results obtained in using the new dyestuffs in the 16
printing of acetate arti?cial silk. The‘prints ob
tained are levelaeven in weak shades.
Further, the new dyestuffs have other advan
tages as compared to the known dyestuffs. The
speed of dyeing at low temperatures is higher,
the change in speed of dyeing with rise of tem
perature is more regular, and quick dyeing is less
dependent on high temperatures. Hence, pene
tration and the production of level shades on
heavy, closely knitted or woven, acetate arti?cial 25
silk fabrics, as for example, crepes, is facilitated. ‘
These properties, however, do not prevent the
new dyestuffs from being employed satisfactorily
in mixtures with other insoluble .azo or anthra
quinone dyestuffs for the purpose of coloring ar 30
ti?cial silk.
The invention is illustrated but not limited by
the following examples, in which the parts are by
weight.
Example 1
35
183 parts of 2,6l-dinitroaniline are diazotized
in concentrated sulphuric acid solution by the
aid of nitrosyl sulphuric acid in the known way.
The aqueous solution of the diazo compound ob
tained by pouring the sulphuric acid solution into 40
ice and Water and ?ltering is added slowly to a
solution in 4000 parts of water at 0°-5° C. of 283
parts of the product obtained by condensing 151
parts of N-ls-hydroxyethyl-m-toluidine with .45
three equivalents (132 parts) of ethylene oxide.
Simultaneously keeping the temperature below
5° C. there is added a 40% solution of aqueous
caustic soda, at such a rate that the coupling
medium is always faintly acid to Congo red,50
paper. When combination is complete the dye?
stu? suspension is rendered just alkaline with
caustic soda and the dyestuff is ?ltered off,
washed with water, and preserved as paste or
dried in any suitable way.
..55
2,118,088
2
The dyestuffr is conveniently applied to acetate
Example 4
arti?cial silk by the method described in British 7
> 138 parts of. p-nitroaniline are diazotized in
the usual way and to the aqueous'solution of the
speci?cation No. 224,077.
A reddish-violet dyeing of good fastness prop
erties and dischargeability is obtained.
'
The coupling component used in the example
diazo compound are added 297 parts of the prod
uct obtained by condensing’ 121 parts of N-ethyl
aniline with 4 equivalents (176 parts) of ethylene
.
oxide. Aqueous sodium acetate is added during
A mixture of 151 parts of N-B-hydroxyethyl-m
half an hour'to facilitate coupling by removing
toluidine, 132 parts of ethylene oxide and 0.5 the mineral acidity of the coupling medium (ap 10
part
"of 10% aqueous caustic soda is heated at. proximate1y‘3270 parts of sodium acetate are used).
10
140° C. in a sealed vessel until the internal pres
'When combination is complete the dyestuff suse
sure falls to zero. ' A pale yellow liquid, which is
pension is rendered alkaline and the dyestuff ?l
soluble in hot water is obtained. The yield is tered o?, washed with water, and preserved as
265 parts; this corresponds to an absorption of . paste or dried in any suitable way.
15
about2.5 molecular equivalents of ethylene oxide.
The dyestuff dyes acetate arti?cial silk in scar
If in the above example the coupling compo
let-red shades of good fastness to light and is
nent is replaced by the product made by con
much superior to the corresponding dyestuif from
densing 107 parts of m~toluidine with 220 parts N-ethyl-N-p-hydroxyethylaniline in ease of dis
of ethylene oxide a dyestuif of similar shade but
. The coupling component used in theexample is
20 with somewhat superior properties as regards dis
obtained by reacting the above stated amounts
persion in water is‘obtained.
.
>
of amine and ethylene oxide under. the condi
Example 2
is made in the following Way:—
persion.
V
-
_
.
'
'
tions described in Example 1.
i 267 parts of 6-bromo-2,4-dinitroaniline are di
Example 5
azotized as in Example 1,’ and the cooled diazo
solution added'slowly to a solution in 4000 parts
oirwater at'0° C.’ and 370 parts of 10% hydro
chloric acid of 239 parts of the product obtained
by condensing 151 parts of N-e-hydroxyethyl-m
toluidine with two equivalents (88 parts) of
ethylene oxide. Ice is added from time to time
to keep the temperature of the coupling medium
at 0° C. Coupling occurs rapidly and when com
7 plete the dyestuff is ?ltered off, washed thorcugh~
1y with water to remove sulphuric acid, and pre
served as paste or dried in any suitable way.
It dyes acetate arti?cial silk .Iin bluish-violet
shades of good fastness properties and discharge
ability when applied in the manner described
in Example 1.
The coupling component used in this example
is obtained by reacting the above stated amounts
of amineand ethylene oxide under the conditions
described in Example .1.
is
25
V
i 138 parts of p~nitroani1ine are diazotized in the
usual way and to the aqueous solution of the diazo '
' compound are added 313 parts of the product ob- ‘
tained by condensing 93 parts of aniline with
5 equivalents (220 parts) of ethylene oxide.
Aqueous sodium acetate is added during half an
hour to facilitate coupling by removing mineral‘
acidity (approximately 270 parts of 7 sodium
acetate are used). When combination is com
plete the dyestu? is ?ltered off, washed with
water, and the'dyestuff paste preserved as such
at
or dried in any suitable way.
The dyestu? dyes acetate arti?cial silk in yel
lowish-red shades of good fastness properties and
dischargeability, and is superior to the corre "40
sponding dyestuff from N-?,/3'-dihydroxydiethyl
aniline in ease of dispersion.
The coupling component used in this example
is obtained by reacting the above stated amounts . .
of amine and ethylene oxide under the conditions
described in Example 1.
Example 3
7 A suspension of 172.5 parts of 2-chloro-4-nitro
aniline in 8000 parts of water and 1110 parts of
Example 6
10% hydrochloric acid-is diazotized by the addi
r 69 parts of sodium nitrite are added to 1480
tion-of 69 parts ofsodium nitrite. The solution
of the zdiazo compound is added to a solution'ob
parts of 100% sulphuric acid and stirred until no .50
solid remains, then 222'parts of 6-chloro-2A-di
' tained by dissolvingin'4000 parts of water and
nitroaniline are added to this with stirring dur
370 parts of 10% hydrochloric acid the'product ing 2 hours. After stirring for a further hour
obtained by condensing 121 parts of N-ethylani . ‘the solution is'heated to 50° 0.. kept at that tem
line with 88 parts (two equivalents) of ethylene perature for two hours, and then cooled to 20° C.
oxide. Coupling is facilitated by the addition of
approximately 408 parts of sodium acetate.
When coupling is complete the dyestu? suspen
sion is rendered alkaline and the dyestuff ?ltered
off, washed thoroughly with water, and preserved
60
as paste or dried in any suitable way.
7
The dyestuff 'dycs V acetate arti?cial silk in
bluish-red shades of good fastness to light and
is superior to the corresponding dyestufi from
iN-ethyl-N-,8-hydroxyethylaniline in easegof dis
persion and in penetration of crepe materials
It is then added slowly to a cold (0° C.) well agi
tated solution in 4000 parts of water and 7370.
parts of 710% hydrochloric acid of 327 parts of.
the product obtained by condensing 151 parts of
N-p-hydroxyethyl-m-toluidine. with 4 equivalents 60
(176 parts) of ethylene oxide. Ice is added from
time to time to keep the temperature of the cou
pling medium at 0° C. Coupling is rapid and
when complete the dyestu?’ is ?ltered off, washed . .
thoroughly with acid to remove sulphuric acid,
and preserved as paste or dried in any suitable
consisting of or containing acetate arti?cial silki 7 way.
When applied in‘ the manner described in Ex- _
If the coupling component in the above exam
ple is replaced by the product obtained by con
densing 121 parts of N-ethylanilin-e, with 176
parts of ethylene oxide under the conditions de
scribedrin Example 1, a bluish-red dyestuff is ob
tained which disperses more readily in water
than that obtained by the use of 88 parts of
ethylene oxide.
7
,
,
ample 1 it dyes acetate arti?cial silk in bluish
violet shades ofgood fastness properties and dis 70
,chargeability, and penetrates crepe materials of
acetate arti?cial silk better’ than the correspond
ing dyestu? from N-Mi’—dihydroxydiethyl~m
toluidine.
'
'
Ifthe coupling'cornponent in the above example 75
3
2,118,088
is replaced by the product obtained by condensing
in which X is one of a group consisting of
107 parts of m-toluidine with 220 parts of
ethylene oxide under the conditions described in
Example 1 a bluish-violet dyestuff of similar
properties is obtained.
Example 7
methyl, ethyl, beta-hydroxyethyl and
69 parts of sodium nitrite added to 1480 parts
of sulphuric acid monohydrate until no solid
10 remains, then 238 parts of 2,4-dinitro-1-naph
thylamine are added to this with stirring during
two hours. After stirring for a further hour the
solution obtained is heated to 45° C. and kept at
that temperature for two hours and then cooled
15 to 20° C. It is then added slowly to a cold (0° C.)
well agitated solution in 4000 parts of water and
370 parts of 10% hydrochloric acid of 342 parts
of the product obtained by condensing 107 parts
of m-toluidine with 235 parts of ethylene oxide,
20 ice being added from time to time to keep the
temperature at 0° C. When coupling is com
plete the dyestuff is ?ltered off, washed with
water, resuspended in 6000 parts of water, the
resulting suspension rendered alkaline with so
25 dium carbonate, and the dyestu? ?ltered off and
preserved as paste or dried in any suitable way.
When applied in the manner of Example 1 it
dyes acetate arti?cial silk in violet shades.
The coupling component used above is obtained
30 by reacting the above stated amounts of amine
and ethylene oxide under the conditions described
in Example 1.
We claim:
1. The method of making a dyestu? which
35 comprises diazotizing and coupling a para ni
troarylamine from the group consisting of the
benzene and naphthalene nitroarylamines to a
position para to the amino group of an N-substi
tuted ethylene oxide derivative of aniline in
40 which there are combined between two and ten
not greater than 10.
7. A dyestuif being the product of coupling a
diazotized para-nitroamine from the group con 10
sisting of the benzene and naphthalene nitro
amines with a compound having the formula
15
CHz—CHz—(0CHz—-CH2)..—OH
in which Ar is an aryl group of the benzene series
free from water-solubilizing groups, X is one of a
group consisting of methyl, ethyl, beta-hydroxy
ethyl and CH2—-CH2—(OCH2—CH2) 1u-—~0H, n 20
and n’ are integers and the sum of n and 'n' is not
more than 10'.
8. A dyestu? being the product of coupling a
diazotized para-nitroamine from the group con
sisting of the benzene or naphthalene nitro
amines with a compound having the formula
25
X
Ar—N
CHr-CHz—-(OOH:—CH:)»—OH
30
in which Ar is an aryl. group of the benzene
series free from water-solubilizing groups, X is
one of a group consisting of methyl, ethyl, beta
hydroxyethyl and
35
n and n’ are integers and the sum of n and n’
is not more than 4.
2. The method of making a dyestu? which
comprises diazotizing and coupling a para nitro
9. The method of making monoazo dyestuffs
which comprises diazotizing and coupling a p 40
nitraniline with an aniline having the position
para to its amino group unoccupied and wherein
said amino group is combined with three to ten
arylamine from the group‘consisting of the ben
equivalents of ethylene oxide.
ethylene oxide groups.
45 zene and naphthalene nitroarylamines to a posi
tion para to the amino group of an N-substituted
ethylene oxide derivative of aniline in which
there are combined between four‘ and ten ethyl
ene oxide groups.
50
11, and n’ are integers and the sum of n and n’ is
3. The method of making a dyestuff which
comprises diazotizing and coupling a para ni
troarylamine from the group consisting of the
benzene or naphthalene nitroarylamines to a po
sition para to the amino group of an N-substi
55 tuted ethylene oxide derivative of aniline in which
there are combined about four ethylene oxide
groups.
4. A compound formed by coupling diazotized
6-chloro-2:4-dinitroaniline to the condensation
60 product of meta-toluidine and three equivalents
of ethylene oxide.
5. The compound being the product of coupling
10. The method of making monoazo dyestuffs 45
which comprises diazotizing and coupling 1
amino~2-chlor-4-nitrobenzene with the product
obtained by condensing N-ethylaniline with two
to four equivalents of ethylene oxide.
11. The monoazo dyestuffs having the general 50
formula
x
R—N=N—-R’—N
/
cinmoomonmon
wherein R is the radical of a p-nitraniline, X 55
represents C2H4(OCH2CH2)n'OH, n’ being zero
or a whole number, and n is a whole number, the
sum of n and n’ being no more than ten.
12. The monoazo dyestuffs having the general
formula
C:H4(OCH:CH2)»’OH
6 - chloro - 2 : 4 - dinitroaniline to the compound
formed by condensing N-n-butyl-cresidine with
65 two equivalents of ethylene oxide.
6. A dyestuff being the product which results
from coupling a diazotized para-nitroamine from
the group consisting of the benzene and naphtha
65
wherein R is a radical of a diazotized p-nitrani
line, n’ is zero or 1 and n has the value 2-n'.
13. The azo dyestuff having the formula
lene nitroamines which does not contain a water
70 solubilizing substituent with a substituted amine
70
having the formula
/
Phenyl-N\Y
ARTHUR HOWARD KNIGHT.
HENRY ALFRED PIGGO'IT.
75
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