Improvements in and relating to the Manufacture of Dyestuffs.
Year: 1897

page_text: PROVISIONAL SPECIFICATION.
Improvements in and relating to the Manufacture of Dyestuffs.
A communication from abroad by LA SOCIÉTÉ CHIMIQUE DES USINES DU RHÔNE,
ANCIENNEMENT GILLIARD P. MONNET ET CARTIER, of Lyons, France,
Manufacturers.
I, GEORGE BELOE ELLIS, of the Firm of J. C. Mewburn & Ellis, of 55 and 56,
Chancery Lane, in the County of London, Chartered Patent Agents, do hereby
declare the nature of this invention to be as follows:-
This invention relates to improvements in and relating to the manufacture of
dyestuffs obtained by the condensation of saccharin with meta-amido-phenol and
its derivatives, and to the manufacture of new dyestuffs.
By the condensation of saccharin with meta-amido-phenol or alkylated
meta-amido-phenol, dyestuffs are obtained to which the name saccharo-rhodamines
has been given; these dyes do not resist alkalies.
According to the present invention these saccharo-rhodamines may be converted
into dyes capable of resisting alkalies by treatment with acids, acid anhydrides or
acid chlorides. After treatment of the saccharo-rhodamine with 70 per cent.
sulphuric acid at a temperature between 120° and 130°C., the color of the acid
solution of the new dye which is formed is scarcely affected by alkali, but
the new product is precipitated as base by alkali from concentrated solutions.
The change is probably brought about in this instance by the conversion
of the sulphamide group into a sulphonic group in the sense of the following
equation:-
H
NR R
C.H. NR,R.

page_text: hydrochloric acid and to heat under pressure to a temperature not exceeding
130° C. At a higher temperature a violet-red dye is formed.
A further series of new dyes, also very resistant to alkalies, may be produced by
heating the saccharo-rhodamines with acetic anhydride. In this instance it appears
that the acetyl group enters the sulphamine group. Thus by the treatment of the 5
saccharo-rhodamine derived from diethyl-meta-amido-phenol a bluish-red fluorescent
dye, very resistant to alkali is obtained, the analysis of which agrees with the
formula
The base of this dyestuff melts about 232°C. In a similar manner other acid 10
radicles may
be introduced. Further, with phosphorus oxychloride a substitution
product is formed of the probable formula
CH
-N (C₂Hб)₂
CH
-N (C₂Hб)₂
CH
NPOCI,
The following are examples of the manner in which this invention may be
carried out.
EXAMPLE 1.
Five parts diethyl-meta-amido-phenol-saccharein is suspended in thirty parts
70 per cent. sulphuric acid and heated for 12 hours at 125°-130°C. The product
of the reaction is poured into fifty parts of water. The sulphate of the new dye
crystallizes out in beautiful greenish crystals.
EXAMPLE 2.
15
20

page_text: Instead of the tetra alkylated rhodamine in the above examples, the sacchareins
of all the other meta-amido-phenols, either wholly or partially substituted, may be
employed with more or less success.
Improvements in and relating to the Manufacture of Dye-stuffs.
A communication from abroad by LA SOCIÉTÉ CHIMIQUE DES USINES DU RHÔNE,
anciennement GILLIARD P. MONNET ET CARTIER, of Lyons, France, Manu-
facturers.
I, GEORGE BELOE ELLIS of the Firm of J. C. Mewburn and Ellis, of 55 and 56,
Chancery Lane, in the County of London, Chartered Patent Agents, do hereby
declare the nature of this invention and in what manner the same is to be per-
formed, to be particularly described and ascertained in and by the following state-
ment:-
This invention relates to improvements in and relating to the manufacture of
dyestuffs obtained by the condensation of saccharin with meta-amido-phenol and its
derivatives, and to the manufacture of new dyestuffs.
By the condensation of saccharin with meta-amido-phenol or its alkylated deriva-
tives, dyestuffs are obtained to which the name saccharo-rhodamines has been given;
these dyes do not resist alkalies.
According to the present invention these saccharo-rhodamines are converted into
dyes capable of resisting alkalies by treatment with mineral acids, acid anhydrides
or acid chlorides. After treatment of the saccharo-rhodamine with 70 per cent.
sulphuric acid at a temperature between 120° and 130°C., the color of the acid
solution of the new dye which is formed is scarcely affected by alkali, but the new
product is precipitated as base by alkali from concentrated solutions.
The change is probably brought about in this instance by the conversion of the
sulphamide group into a sulphonic group in the sense of the following equation :-

page_text: that the acetyl group enters the sulphamine group. Thus by the treatment of the
saccharo-rhodamine derived from diethyl-meta-amido-phenol a bluish-red fluorescent
dye, very resistant to alkali is obtained, the analysis of which agrees with the
formula
The base of this dyestuff melts about 232° C. In a similar manner other acid
radicles may be introduced. Further, with phosphorus oxychloride a substitution
product is formed of the probable formula
CH
CH
-N(C₂H₂)₂
0
-C₂H₂
-N(C₂H)2
NPOCIĄ
SO₂
The following are examples of the manner in which this invention may be carried 10
out.
EXAMPLE I.
Five parts diethyl-meta-amido-phenol-saccharein is suspended in thirty parts
70 per cent. sulphuric acid and heated for 12 hours at 125°-130° C. The product
of the reaction is poured into fifty parts of water. The sulphate of the new dye 15
crystallizes out in beautiful greenish crystals. Complete precipitation of the new
dyestuff may be effected by the addition of salt to the aqueous solution in the usual
manner.
EXAMPLE 3.
Five parts diethyl-meta-amido-phenol-saccharein is heated to boiling with an 2
excess of phosphorus oxychloride for two hours. The excess of phosphorus oxy-
chloride is then distilled off in vacuum and the residue recrystallised from water or
alcohol.
Instead of the tetra alkylated rhodamine in the above examples, the sacchareins
of all the other meta-amido-phenols, either wholly or partially substituted, may be 3
employed with more or less success.

page_text: Having now particularly described and ascertained the nature of the said
invention as communicated to me, and in what manner the same is to be per-
formed I declare that what I claim is :-
1. The manufacture of alkali resisting dyestuffs by treating the condensation
products of meta-amido-phenol or its derivatives and saccharin with mineral acids,
substantially as described.
2. The manufacture of, alkali resisting dyestuffs by treating the condensation
products of meta-amido-phenol or its derivatives and saccharin with acid
anhydrides substantially as described.
3. The manufacture of alkali resisting dyestuffs by treating condensation
products of meta-amido-phenol or its derivatives and saccharin with acid chlorides
substantially as described.
4. The manufacture of alkali resisting dyestuffs by treating a saccharo-rhoda-
mine with sulphuric acid substantially as herein before described under Example 1.
5. The manufacture of alkali resisting dyestuffs by treating a saccharo-rhoda-
mine with acetic anhydride substantially as herein before described under
Example 2.
6. The manufacture of alkali resisting dyestuffs by treating a saccharo-rhoda-
mine with phosphorus oxychloride substantially as herein before described under
Example 3.
7. As new products the alkali resisting dyestuffs herein before described such for
example as can be obtained by treating saccharo-rhodamine with mineral acids,
acid anhydrides or acid chlorides.
Darth VHS way
J. C. MEWBURN & ELLIS,
55 and 56, Chancery Lane, London, Chartered Patent Agents.