1,879,424
Patented Sept. 27, 1932
UNITED STATES PATENT OFFICE
WILHELM NEELMEIER AND EUGEN GLIETENBERG, OF LEVERKUSEN, NEAR COLOGNE,
GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS INC., OF NEW YORK, N. Y., A
CORPORATION OF DELAWARE
WATERSOLUBLE DIAZO COMPOUND
No Drawing. Application‘?led March 28, 1929, Serial No. 350,801, and in Germany April 14, 1928.
The present invention relates to a process obtained if an excess of the coupling com
of preparing water-soluble condensation ponent is present.
The starting compounds of the general
products from diazotized aromatic amines
and secondary amines and to new products ob formula
5 tainable thereby, more particularly it relates
to compounds of the probable general for
mula
R1 R2
50
nr'r. dnosozn
are obtainable by causing ammonia, primary
aliphatic or hydroaromatic amines to react
upon the bisul?te compounds of aldehydes.
55
wherein R stands for an aromatic nucleus One of the coupling compounds falling with
in the scope of the general formula is de
which may be substituted, for example by scribed
in German Patent 216,072.
halogen, nitro—, alliyl— sulfuric acid——, ~ Our new
in some cases partial
or carboxylic acid-groups, R1 stands for hy ly separate compounds
during
the
and the sep
15 drogen, alkyl, a hydrogenated benzene nu aration is completed byreaction
addition of salts 60
cleus, or for the residue of an aldehyde-sul for example sodium or the
potassium chloride.
furous acid, said residue of an aldehyde-sul They are obtained in a crystalline
and
furous acid may be represented by the for are in the dry state very stable, form
generally
mula
.
20
R’
-dH.o.so,H
yellowish colored substances which are
en
erally soluble in water and which by the ad
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dition of a mineral acid or an acid salt of a
wherein R’ means hydrogen, alkyl— or a mineral acid such as sodium bisulfate or
phenyl group, and R2 stands for hydrogen, strong organic acids to their aqueous solution
or an ,alkyl——, or a phenyl group.
25
Our new compounds are obtainable by in
are split up into the two components, that 70
means into the diazo compound and a com
troducing a diazo-solution which is prepared pound of the general formula
in the usual manner by diazotization of an
aromatic amine with hydrochloric acid and
sodium nitrite, into an aqueous solution of
75
30 an alkali metal salt of a compound of the wherein R1 and R2 mean the same as above
general formula
described.
The new products are valuable
products in the manufacture of azo dyestuffs.
The invention is illustrated by the follow
ing examples but is not restricted thereto.
Example 1
above mentioned R1 and R2, in the presence
of an acid binding agent, for instance, caustic
Into an aqueous solution of 114 mol of
alkalies, alkali-metal carbonates, sodium ace methyl-imino-methyl-sulfurous acid (sodium
tate, pyridine. The process is favorably 'car
40 ried out at temperatures not higher than salt) to which an excess of the sodium salt
about 20° C.; the quantities of the two com of acetic acid has been added, there is slow
35 wherein R1 and R2 mean the same as the
ponents which are caused to react upon each ly introduced at a temperature of about 0°
other may be varied within the widest limits, to 10° C. a diazo solution prepared in the
but generally we take care that molecular usual manner from 4-chloro-2-toluidine
45 quantities are present, the best results being (NH2=1). The reaction is soon complete.
85
2
1,879,424
2. The process which comprises reacting
After ?ltration, the condensation product is
precipitated by the addition of potassium upon a compound of the general formula:
chloride. In its free state it has the follow
ing formula
CH3
wherein R1 stands for hydrogen, alkyl, a
hydrogenated benzene nucleus or the residue
70
of an aldehyde-sulfurous-acid, with about an
The sodium salt of the methyl-imino
methyl~sulfurous acid can be obtained by re
acting upon methyl-amine in aqueous solu
tion with an equivalent quantity of formalde
hyde sodium bisul?te and precipitating the
equivalent quantity of a diazo compound of
an aromatic amine in aqueous solution in the 75
presence of an acid binding agent.
3. The process which comprises reacting
upon a compound of the general formula:
sodium salt with alcohol.
~
80
Instead of formaldehyde there may be
used any other aldehyde.
wherein R1 stands for hydrogen, alkyl, a
Ewample 2
hydrogenated benzene nucleus or the residue
In an analogous manner as described in of an aldehyde-sulfurous-acid, and R2 stands 85
Example 1, there is obtained from the diazo for hydrogen, an alkyl-, or a phenyl-group
compound prepared from 5—nitro-2-tolui< with about an equivalent quantity of a diazo
dine, coupled in the presence of sodium bi— compound of an aromatic amine in aqueous
carbonate as acid binding agent, in a well solution in the presence of an acid binding
crystallized form the compound of the for agent at a temperature of ‘at most about so
20° C.
mula
CH3
4. The process which comprises reacting
upon a compound of the general formula: '
wherein R1‘ stands for hydrogen, 'alkyl, a
The, condensation of the diazo compound hydrogenated benzene nucleus or the residue
from 5-chloro-2-toluidine and amino of an aldehyde-sulfurous-acid, with about an IOU
methyl-sulfurous acid (Berichte der deutsch equivalent quantity of a diazo compound of
en Chemischen Gesellschaft Vol. 38, p. an aromatic amine in aqueous'solution in the
1073) proceeds in the same manner as de
presence of an acid binding agent at a tem
scribed in Example 1, in the presence of soda. perature of at most about 20° C.
5. The process which comprises reacting
The condensation product is obtainable in the
form of its potassium salt in a crystalline upon a compound of the general formula:
form.
Example 4
If instead of amino—methyl-sulfurous acid wherein RI stands for an alkyl group with
11.163
of Example 3, there is used the imino-di about
equivalent quantity of a diazo com
methyl-sulfurous acid of the formula: pound an
aromatic amine in aqueous so~
H802.O.CH2.NH.CH2.O.SO2H (compare lution inoftheanpresence
of an acid binding agent
German Patent 216,072), the condensation
proceeds in the same manner as described in
Example 3.
We claim:
at a temperature of at most about 20° C.
6. The process which comprises reacting
upon a methyl-iinino-methyl-sulfurous acid
with about an equivalent quantity of a diazo
1. The process which comprises reacting compound of the benzene series, wherein the
benzene nucleus may be substituted by
upon a compound of the general formula:
halogen, the alkyl, nitro, sulfonic acid or
carboxylic acid groups in aqueous solution
in the presence of an acid binding agent at a
wherein R1 stands for hydrogen, alkyl, a temperature of at most about 20° C‘.
hydrogenated benzene nucleus or the residue
of an aldehyde-sulfurous-acid, and R2 stands
for hydrogen, an alkyl—, or a phenyl-group
with about an equivalent quantity of a diazo
compound of an aromatic amine in aqueous
7. The process which comprises reacting
upon 1% mols of methyl-imino-methyl-sul
furous acid with 1 mol of the diazo-com
pound from ét-ohloro-Q-toluidine, in aqueous
solution, in the presence of the sodium salt of‘
solution in the presence of an acid binding acetié acid at a temperature from (1° C. to
agent.
10°
.
1,879,424
8. As new products compounds of the
probable general formula:
wherein R stands for an aromatic nucleus
which may be substituted by halogen, the
alkyl, nitro, sulfonic acid or carboxylic acid
groups, R1 stands for hydrogen alkyl, a hy
10
drogenated benzene nucleus or the residue of
an aldehyde-sulfurous acid, and R2 stands
for hydrogen, an alkyl——, or a phenyl-group,
being in their dry form stable, generally yel
20
lowish colored substances, soluble in water,
being split up in aqueous solution into the
two starting components by the addition of
a mineral acid, and being Valuable substances
in the manufacture of dyestuffs.
9. As new products compounds of the prob
able general formula:
25
may be substituted by halogen, the alkyl, ni
15
wherein R stands for a benzene nucleus Which
tro, sulfonic acid or carboxylic acid groups,
and R1 stands for an alkyl group, being in
their dry form stable, generally yellowish
colored substances, soluble in water, being
80
split up in aqueous solution into the two
85
probable general formula:
starting components by the addition of a
mineral acid, and being valuable substances
in the manufacture of dyestuffs.
10. As a new product the compound of the
CH1
40
CH3
being a yellowish colored powder, soluble in
water and being split up by the addition of
a mineral acid to its aqueous solution into
the diazo compound of 4-chloro-2-toluidine
and methyl-imino~methyl-sulfurous acid.
In testimony whereof We have hereunto set
our hands.
WILHELM NEELMEIER.
EUGEN GLIETENBERG.
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