Improvement in the Manufacture of Amidophenols.
Year: 1889

page_text: Date of Application 16th May, 1889
Complete Specification Left, 15th Mar., 1890-Accepted, 26th Apr., 1890
PROVISIONAL SPECIFICATION.
[Communicated from abroad by Messrs. WIRTH & Co., of Frankfort-on-the-Main,
acting as Agents of A. Leonhardt & Co., of Mulheim-on-the-Main, both in the
Empire of Germany.]
Improvement in the Manufacture of Amidophenols.
I, HENRY HARRIS LAKE, of the firm of Haseltine, Lake & Co., Patent Agents,
Southampton Buildings, in the County of Middlesex, do hereby declare the nature of
this invention to be as follows:-
If resorcine is heated with ammonia or salts of ammonia in an autoclave for a
certain length of time and at a high temperature, there is formed metamidophenol.
If instead of aminonia or its salts, substituted amines of the olefines or their salts
are used there are formed the corresponding substituted metamidophenols.
This chemical reaction also takes place if aromatic amines are employed, but it is
essential that salts of such amines be present; in this case the reaction however can
already be carried out in an open vessel without pressure.
The treatment of the product of the reaction takes place in a manner well known
to chemists; if aminonia or amines of the olefines are employed, the product of
reaction is acidulated and the resorcine which escaped the reaction is extracted with
ether etc. the amidophenols formed are isolated from the aqueous inother-lye after
saturation with soda by crystallization or extraction etc.
If aromatic amines are employed the substituted amidophenols formed can be
separated by simply pouring the product of reaction into acidulated water.
*Dated this 16th day of Nov 1880
HASELTINE, LAKE & Co.,
45 Southampton Buildings, London, Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvement in the Manufacture of Amidophenols.
I, HENRY HARRIS LAKE, of the firmn of Haseltine, Lake & Co., Patent Agents,
Southampton Buildings, in the County of Middlesex, do hereby declare the nature of
this invention and in what manner the saine is to be performed, to be particularly
described and ascertained in and by the following statement :-
If resorcine is heated with ammonia in the presence of or without a suitable salt of
ammonia (such as the hydrochloride or the like) at a high temperature and for a
certain length of time, metaamidophenol is formed.
If instead of ammonia or its salts, substituted amines of the fatty series or their
salts are used, substituted metaamidophenols are obtained.
Ammonia or those fatty amines which are gaseous at the ordinary temperature, are,
for the sake of facility preferably employed. in watery solutions; dietliylamine, how-
ever, being liquid at the ordinary temperature, I prefer to employ in a rather
concentrated state, free from water or nearly so.
The following examples show the manner in which this invention can be carried
out.
After
1st. 10 kilos. of resorcine are heated in an autoclave with 20 kilos. of ordinary
liquid ammonia of about 15 per cent. during 12 hours at about 220° Cent.
cooling down, the whole mass is acidulated with hydrochloride, or sulphuric, or other
suitable acid, the unaltered resorcine is extracted with ether, amylic, alcohol or the
like, and the remaining water solution is made slightly alkaline preferably by means
After concentrating the liquid and cooling down, the greater part of the
of soda.

page_text: metaamidophenol crystallizes out of the solution (especially when small quantities of
crystallized metaamidophenol are added to the fluid); the rest can be extracted with
ether or the like.
2nd. 10 kilos. of resorcine are heated in a autoclave with 6 kilos. of muriate
of ammonia and 20 kilos. of liquid ammonia (of about 10 per cent.) during, say,
12 hours at about 200° C. After cooling down to the ordinary temperature, the
whole mass is treated in the same manner as above stated.
3rd. 11 kilos. of resorcine are heated with 18 litres of a watery solution of
methylamine, containing 6 kilos. of methylamine, during about 12 hours at a
temperature of 200-220° Cent. After cooling, the whole mass is acidulated with
hydrochloric or other suitable acid, and resorcine which escaped the reaction, is
extracted with ether. The watery solution is then made slightly alkaline preferably
with soda, and filtered if necessary, and the monomethylmetaamidophenol obtained
is extracted with ether. It can be purified by distilling. The boiling point is at
about 280° Cent.
4th. 11 kilos. of resorcine are heated with 42 litres of a watery solution of
dimethylamine, containing 12 kilos. of dimethylamine, and 4 litres of hydrochloric
acid (of about 30 per cent.) during 10 hours at about 190-210° Cent. After cooling
and acidulating, the unaltered resorcine is extracted in the usual way, and the
watery solution is fractionally precipitated with soda. The first precipitates contain
resinous matters which are removed by filtration; the following precipitates yield
dimethyl metaamidophenol which can be purified by distilling or crystallizing out of
benzol and ligroine.
Dimethylmetaanidophenol can also be obtained by heating, say, 10 kilos. of
resorcine with a strong watery solution of about 10 kilos. of trimethylamine at
about 210° C. for 12 hours, and then operating further in the same manner as
above stated.
5th, 11 kilos. of resorcine are heated with 15 litres of diethylamine during
about 10 hours at about 190-210° Cent. After cooling down, the unaltered
resorcine and the formed diethylamidophenol are isolated in the same way as
indicated under 4th.
Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed as communicated to me by my
foreign Correspondents I declare that what I claim is :--
First. The production of metaamidophenol by heating resorcine with ammonia in
the presence of or without a suitable salt of ammonia, at a high temperature and for
a certain length of time, substantially as above described.
Second. The production of substituted metaamidophenols, such as methylmeta-
amidophenol, or dimethylmetaamidophenol, or diethylmetaamidophenol, by heating
resorcine with methylamine, dimethylamine, trimethylamine, diethylamine or any
other fatty amine which will give a similar or like result, in presence of or without
a suitable salt of such amine, at a high temperature and for a certain length of time,
substantially as above described.
Third. Metaamidophenol or substituted metaamidophenols produced by heating
resorcine with ammonia or fatty amines, substantially as hereinbefore described.
1000
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, Agents for the Applicant.