DIAMIDUAZOBENZIDINES AND COLORAD Exam
Year: 1887

page_text: Date of Application, 11th June, 1887
Complete Left, 9th Mar., 1888
Complete Accepted, 27th Apr., 1888
A. DIAMIDUAZOBENZIDINES AND COLORAD
Example 1. 10 lb. Metadiamidodiphen-acid are diazotised as usual and mixed with
the solution of 13,2 lb. chlorhydrate of Alpha or Beta Naphtylamine in 30 lb. water.
After a rest of 12 hours, the precipitate is filtered, washed, stirred up in 50 gallons
water and boiled with addition of Ammonia sufficient to give alcaline reaction. The
Ammonia-salt, thus formed, is precipitated by common salt and filtered.
If 6,6 lb. chlorhydrate of Alpha-Naphtylamine are substituted for the 13,2 lb.
chlorhydrate of Naphtylamine a precipate is formed with a free diazogroup which may
be combined with a second molecule, of an Amine or Phenole..

page_text: or the equivalent quantities of the sulfoacids of these bodies, under addition of a
quantity of acetate of soda equivalent to 3 to 4 molecules of hydrochloric acid. The
resulting bodies-as far as they are not obtained from the Sulfoacids of Aniline,
Toluidine, Xylidine and Cumidine-are difficult of solution in water and spirit, but
may be easily diazotised.
Example 6. The Diamidoazocompound resulting from 10 lb. Benzidine and 14,2 lb.
Aniline salt, while still moist, is stirred up in 25 gallons water and 30 lb. hydrochloric
acid. After cooling 7,6 lb. Nitrite of Soda-in aqueous solution-are cautiously added
and the mixture left to rest for 12 hours.
:
The new tetrazo compound thus obtained is poured into an aqueous solution of one

page_text: The coloring matters resulting from
filtered and, if necessary, re-dissolved.
a, blue. b, violet. red.
these 3 cases are separated by common sal
They dye cotton in alcaline bath :
ADIVE
7,9 lb. chlorhydrate of Toluidine
or 10,2
"
"
"
Xylidine
or 11
Cumidine
وو
"
"
combinations result which may be combined in the same way with the same quanti-
ties of Naphtoldisulfoacids and Naphtolmonosulfoacids and Naphtionates, as is said in
Example 10; analogous colors resulting. The coloring matters obtained in
Example 10 and 11 derived from the naphtylaminesulfoacids may be transformed into
coloring matters containing the Alpha or Betanaphtolsulfoacids, by diazotising and
boiling.
Example 12. In substituting the 10 lb. Diamidoazobenzidine of Examples 7 and 8
by the equivalent quantities of one of the Monoamidoazobenzidines of Example 10
and 11, similar bodies result, dyeing cotton with a more bluish shade.
Example 13. In substituting the 10 lb. Benzidine of Example 10 by the equivalent
quantities of
1, Metadiamidodiphen acid or its ethers
2, Tolidine or Dixylyldiamine
3, The ethers of Diamidodiphenol
4, Diamidofluoren or Diamidostilben or their sulfoacids
similar bodies to the Monoamidoazobenzidine result, which may be also diazotised and
combined with the equivalent quantities of R salt of Betanaphtoldisulfoacid, soda salt
of Alpha or Beta naphtolmonosulfoacid, Alpha or Betanaphtylamine sulfoacids,
· Resorcine; and furnish blue; violet and red coloring matters which dye cotton in
alcaline bath.
The Monoamidoazobenzidines, described in the preceding Examples may be
combined with a second molecule of Aniline or its homologues or their sulfoacids,
and furnish thus the same combinations which result from combining one molecule of
the tetrazocompounds known, direct with 2 molecules of the respective Amines, as it
is mentioned in Examples 1 to 9.
Example 14. The monoamidoazobenzidine, resulting from Example 10 is stirred up
in water with 6 lb. acetate of Soda, and mixed with an aqueous solution of
7,1 lb. Aniline salt. After 12 hours rest-sooner by agitating and heating-the red
precipitate is transformed into a yellow one of the composition:
In the same way the combinations resulting from Example 13 may be combined
with another molecule of Aniline, Tolüidiné, Xylidine, Cumidine or their sulfoacids.
C. TRANSFORMATION OF THE MONOAMIDOAZOBENZIDINES INTO HYDROXYL-COMBINA-
TIONS BY BOILING WITH WATER, DIAZOTISING THE THUS OBTAINED HYDROXYL-
COMBINATIONS AND THEIR COMBINATION WITH PHENOLES OR AMINES.
In combination the known tetrazocompounds mentioned, with one Molecule Alpha
or Betanaphtol, Alpha, or Betanaphtylamine, Aniline; Toluidine, Xylidine, Cumidine,
Resorcine, or the sulfoacids of all these bodies, combinations result which contain still
a free diazogroup; this diazogroup may be completely transformed into the hydroxyl-
group (HO) by boiling with acidulated water, and in this manner the compounds not

page_text: soluble in alkali and showing few symptoms of a color nature before are transformed
into such, soluble in alkali and dyeing wool.
Example 15. 10 lb. Benzidine are diazotised as usual and combined
a. under addition of 7.2 lb. acetate of Soda, with
1.
7,1 lb. chlorhydrate of Aniline or
2. 7,9
Toluidine or
"
. "
"
3. 10,2
"
"
"
Xylidine or
4. 11
Cumidine or
"
"
""
5. 9,8, Alpha or Beta Naphtylamine or
6. 13,3,, Alpha or Beta Naphtionate of Soda, or
Metasulfanilacid.
7. 9,3,
After some rest, the mixtures are heated to boiling and the boiling continued until
emission of Azote has ceased.
Those coloring matters resulting, which are not soluble in water, may be made
soluble by sulfonation.
The coloring matters obtained dye cotton yellow to red in alcaline bath.
b, under addition of 34,5 lb. Ammonia, with
8. 7,8 lb. Alpha or Betanaphtol
9. 18,8,, Soda Salts of Betanaphtoldisulfoacids.
10. 13,2,, Soda salts of Alpha or Betanaphtolmonosulfoacids; voluminous, dark
colored precipitates are formed, which are completely decomposed by boiling.
The colors resulting from Naphtoles are made soluble in water by sulphonation.
Example 16. The coloring matters, containing the Naphtolsulfoacids also result by
diazotising the precipitates from the naphtylaminesulfoacids, and decomposing them
by boiling with water. Boiling is however not necessary.
The precipitate, for instance, from naphtionates in Example 15 is mixed with
24 lb. hydrochloric acid, 3,7 lb. Nitrite of Soda and left to rest 12 hours. Then
boiled, and the product treated as is said above in Example 15. Also the other
Amines, combined with the known or the new tetrazocompounds may be further
diazotised and combined anew with Phenoles or Amines,
Dated this 11th day of June 1887
HERBERT & Co.,
Agents to Applicant.

page_text: 2x4,8 lb. chlorhydrate of Aniline
or 2 x 5,3
Toluidine
"
"
"
or 2 × 6,9
"
"
"
or 2 × 7,4
Xylidine
Cumidine
"
"
"
and an excess of Ammonia cautiously added to an alcaline reaction.
If the tetrazocompound had been filtered it is stirred up with some water, the
solution of the chlorhydrate of the Amine is added with a quantity (equivalent to
3 to 4 molecules hydrochloric acid) of acetate of Soda.
In both cases yellow precipitates are formed which are filtered and washed.
All these colours are weak colouring matters for cotton.
Example 4. The moist precipitate resulting from example 3 by the combination of
1. molecule Tetrazodiphenyldicarbonacid and for instance 2 mol. Aniline is stirred up
in 25 gallons water, 18 lb. hydrochloric acid added and boiled.
After filtering and cooling the solution is diazotised by 5,2 lb. Nitrite of Soda. After
some rest the solution which has turned into a brownish yellow is poured into an
acqueous solution formed by
a. 18,2 lb. Naphtionate of Soda and the same weight of acetate of Soda which after a
rest of 24 hours is filtered and poured into Ammonia.
The colouring matter formed, dyes cotton red from alcaline bath.
This colouring matter may be yet again diazotised wholly or partly by wholly
diazotising for instance scarlet colouring matters for wool are obtained.
or 6 26,2 lb. R salt of Betanaphtoldisulfoacid, the mixture to be kept alcaline. A
red colouring matter results.
or c. 18,3 lb. Soda salt of the Alpha or Betanaphtolmonosulfoacid red orange dyeing
colours resulting.
Example 5. 10 lb. Benzidine are diazotised in 25 gallons water with 26,5 lb. hydro-
chloric acid (30%) and 7,6, lb. Nitrite of Soda. The solution of Tetrazodiphenyl thus
formed is poured into an acqueous solution of :-
2x 9,8 lb. chlorhydrate of Alpha or Betanaphtlylamine
or 2 × 7,1
"
"
"
or 2 × 7,9
"
"
"
"
وو
Aniline
Toluidine
Xylidine
Cumidine
"
"
or 2 × 10,2,,,
or 2 x 11
"
or the equivalent quantities of the sulfoacids of these bodies under addition of a
quantity of acetate of soda equivalent to 3 to 4 molecules of hydrochloric acid.
The resulting bodies as far as they are not obtained from the sulfoacids of Aniline,
Toluidine, Xylidine and Cumidine are difficult of solution in water and spirit but may
be easily diazotised.
Example 6. The Diamidoazocompound resulting from 10 lb. Benzidine and 14,2 lb.
Aniline salt, while still moist is stirred up in 25 gallons water and 30 lb. hydrochloric
acid. After cooling, 7,6 lb. Nitrite of Soda in acqueous solution, are cautiously added
and the mixture left to rest for 12 hours.
The new tetrazocompound thus obtained is poured into an acqueous solution of one
of the following bodies
a. 26,6 lb. Naphtionate of Soda
or b. 37,8 R Salt of Betanaphtoldisulfoacid
"
or c. 26,7,
From a, a red, from
bath results.
soda salt of Alpha or Betanaphtolmonosulfoacid.
a blue, from e, a violet colouring matter for cotton in alcaline

page_text: Resorcine disulfonate of soda a blackish red solution arises from which a colouring
matter which dyes a more bluish red shade than that derived from resorcine, is preci-
pitated by common salt and filtered.
Example 9. If for the tetrazodiphenyl is substituted the equivalent quantities of
a. Tetrazodiphenyldicarbon acid and its ethers
b. Tetrazoditolyl and Tetrazodixylyl
c. Tetracompounds of the ethers of Diamidodiphenol
d. Tetrazofluoren and Tetrazostilben
and treated in the same way as is said in Examples 1 to 8 analagons colouring matters
are formed.
B. MONOAMIDOAZOBENZIDINES AND COLOURS DERIVED FROM THEM.
if one molecule of one of the known tetrazocompounds is combined with only one
molecule of Aniline, Toluidine, Xylidine or Cumidine or their sulfoacids, Mono-
amidoazobenzidines result which may be again diazotised and combined either with
two molecules of the same or of different Amines or Phenoles or with one molecule
of an Amine or Phenole.
Example 10. 10 lb. Benzidine are diazotised in the usual way, mixed with an
acqueous solution of 7,2 lb. acetate of Soda andja solution of 7,1 lb. Aniline salt & 6 lb.
acetate of Soda in 6,5 gallons water added. A red precipitate is at once formed and
may be filtered after a rest of one hour.
This precipitate is stirred up in 15 gallons water with 24 lb. hydrochloric acid and
diazotised with 3,7 lb. Nitrite of Soda.
After a rest of some hours the tetrazocompound thus obtained is poured into an
acqueous solution of one of the following bodies.
a. 37,5 lb. R salt of Betanaphtoldisulfoacid, or
b. 26,3 lb. soda salt of alpha or Betanaphtolmonosulfoacid (in both cases the mixture
is to be kept alcaline) or
c. 26,3 lb. Naphtionate of Soda and 36 lb. acetate of Soda.
The colouring matters resulting from these three cases are separated by common
salt, filtered and if necessary redissolved. They dye cotton in alcaline bath.
a blue. b, violet. c, red.
1,3 10. CHornyurate of ordi
or 10,2
"
"
"
11
Xylidine
Cumidine
"
"
"
"
combinations result which may be combined in the same way with the same quantities
of Naphtoldisulfoacids and Naphtolmonosulfoacids and Naphtionates as is said in
Example 10 analagous colours resulting.
The colouring matters obtained in Examples 10 and 11 derived from the naphtyl-
aminesulfoacids may be transformed into colouring matters containing the Alpha-or
Betanaphtolsulfoacids by diazotising and boiling.
Example 12. In substituting for the 10 lb. Diamidoazobenzidine of Examples 7 & 8
the equivalent quantities of one of the Monoamidoazobenzidines of Examples 10 and 11
similar bodies result dyeing cotton with a more bluish shade.
Example 13. In substituting for the 10 lb. Benzidine of Example 10 the equivalent

page_text: similar bodies to the Monoamidoazobenzidine result which may be also diazotised and
combined with the equivalent quantities of R salt of Betanaphtoldisulfoacid, soda salt
of Alpha or Betanaphtolmonosulphoacid, Alpha or Betanaphtylaminesulfoacids
Resorcine, and furnish blue, violet and red colouring matters, which dye cotton
in alcaline bath.
The Monoamidoazobenzidines described in the preceding Examples may be com-
bined with a second molecule of Aniline or its homologues or their sulfoacids and
furnish thus the same combinations which result from combining one molecule of tho
tetrazocompounds, known, direct with two molecules of the respective Amines as is
mentioned in Examples 1 to 9.
Example 14. The monoamidoazobenzidine resulting from Example 10 is stirred up
in water with 6 lb. acetate of Soda and mixed with an acqueous solution of 7,1 lb.
Aniline salt. After 12 hours rest, sooner by agitating and heating-the red
precipitate is transformed into a yellow one of the composition.
In the same way the combinations resulting from Example 13 may be combined with
another molecule of Aniline, Toluidine, Xylidine, Cumidine or their sulfoacids.
.
C. TRANSFORMATION OF THE MONOAMIDOAZOBENZIDINES INTO HYDROXYL COMBINA-
TIONS BY BOILING WITH WATER, DIAZOTISING THE THUS OBTAINED HYDROXYL
COMBINATIONS AND THEIR COMBINATIONS WITH PHENOLES OR AMINES.
In combining the known tetrazocompounds mentioned with one Molecule Alpha or
Betanaphtol, Alpha or Betanaphtylamine, Aniline Toluidine, Xylidine, Cumidine
Resorcine, or the sulfoacids of all these bodies, combinations result which contain still
a free diazogroup, this diazogroup may be completely transformed into tho hydroxyl
group (HO) by boiling with acidulated water and in this manner the compounds not
soluble in alkali and showing few previous symptoms of a colour nature are transformed
into such, soluble in alkali, and capable of dyeing wool.
Example 15. 10 lb. Benzidine are diazotised as usual and combined (a.) under
addition of 7,2 lb. acetate of Soda with-
Voluminous, dark coloured precipitates are formed which are completely decomposed

page_text: diazotising the precipitates from the naphtylamine sulfoacids and decomposing them
by boiling with water. Boiling is however not essential.
The precipitate for instance from naphtionates in Example 15 is mixed with 24 lb.
hydrochloric acid 3,7 lb. Nitrite of Soda and left to rest 12 hours. Then boiled and
the product treated, as is said above in Example 15. Also the other amines combined
with the known or the new tetrazocompounds may be further diazotised and combined
anew with Phenoles or Amines.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim is
In the manufacture of dyes.
1. Combination of the following tetrazocompounds
a Tetrazodiphenyl, Tetrazoditolyl, Tetrazoxylyl
.b Tetrazodiphenyldicarbonacid and its ethers
c Tetrazocompounds of the ethers of Diamidodiphenol or
d. Tetrazofluoren or Tetrazostilben
or the sulfoacids of these bodies with two molecules of Aniline, Toluidine, Xylidine
or Cumidine or their sulfoacids.
2. The transformation of the bodies resulting from the combination of tetrazo-
compounds heretofore known with two equal or different molecules of Alpha or
Betanaphtylamine or their sulfoacids, Aniline, Toluidine, Cumidine Xylidine or their
sulfoacids into novel tetrazocompounds.
3. The decomposition of those the said novel tetrazocompounds resulting from claim
No. 2. which contain Amines or their sulfoacids into compounds containing the
corresponding Phenoles or Naphtoles or their sulfoacids by boiling with water.
4. The combination of the said novel tetrazocompounds resulting from claim No. 2
with Alpha or Beta Naphtol, or Alpha or Beta Naphtylamine or their sulfoacids.
5. The combination of one molecule of the known tetrazocompounds mentioned in
claim No. 1. with one molecule Aniline, Toluidine Xylidine or Cumidine or their
Sulfoacids.
6. The transformation of the Monoaniidoazocompounds resulting from claim No. 5
into Diazocompounds and their combination with Alpha or Beta Naphtol or their
sulfoacids or Alpha or Beta Naphtylamine or their sulfoacids.
7. The Diazotisation of the Diamidoazocompounds resulting from claim No. 1 and
of the Monoamidoazocompounds resulting from claim No. 5 and combination thereof
with Resorcine or its sulfoacids.
8. The transformation of the intermediate products resulting from the combination
of one molecule of the known tetrazocompounds mentioned in claim No. 1 with one
molecule Aniline, Toluidine, Xylidine, Cuinidine Alpha or Betanaphtylamine, Alpha
or Beta Naphtol, Resorcine or the sulfoacids of all these bodies into bodies which
contain the Hydroxyl group (HO) instead of the free diazogroup by boiling with
water.
9. The transformation of the compounds resulting from claim No. 8 which contain
Naphtylamine sulfoacids into colours containing the Alpha or Betanaphtolsulfoacids
by diazotising and boiling with water.