The Manufacture or Production of Chemical Compounds and Dye-stuffs Derived from Phenolic Bodies.
Year: 1895

page_text: Date of Application, 30th July, 1895
Complete Specification Left, 28 h Apr., 1896-Accepted, 20th June, 1896
PROVISIONAL SPECIFICATION.
[Communicated from abroad by The Farbenfabriken, vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture or Production of Chemical Compounds and
Dye-stuffs Derived from Phenolic Bodies.
1, HENRY EDWARD NEWTON, of The Office for Patents, 6 Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
:-
Some time since my foreign correspondents found that on condensing phenols,
naphthols, or the like, that is to say, in general, bodies containing hydroxylic groups,
with secondary amines of the fatty series, in the presence of formaldehyde, or the
Alkyl
like, new products are obtained which contain the group-O-CH,N
Alkyl,
in place of the hydroxylic group, and, chemically, are phenol amino alkylic ethers.
For example, on condensing phenol with dimethyl amine in the presence of
formaldehyde omegadimethylamidoanisol (or dimethylexoamido-methyl phenol
ether)-CH,O.CH₂N(CH₂), is obtained. Similar compounds have also been
produced by condensing phenolic bodies with halogen derivatives of secondary
amines.
My foreign correspondents have now discovered that the said compounds
containing the group O.CH,N
Alkyl
Alkyl
are readily changed, under the influence
of chemical or physical agents, into isomeric bodies, which, by reason of their pro-
perties and of their formation, are to be considered as hydroxybenzylalkylamine
Alkyl
compounds. In this process, the group OCH,N
of the original body is
Alkyl
Alkyl
being substituted
probably changed into a hydroxylic group, the group CH,N
Alkyl
at the same time for a hydrogen atom of the nucleus, according to the following
equation [if, for example, omega dimethylamidoanisol (or dimethylexoamidoanisol)
OH
be used]-C,H,OCH,N(CH₁), = CH
4.
N(CH3)2.
An
be used]-C,H,OCH,N(CH₂), = C₂H¸
N(CH)
My foreign corespondents effect the transformation of phenolaminoalkylicethers
into hydroxybenzylalkylamine bodies, for instance, by heating the said amino-
alkylic ethers, or salts thereof, in or without the presence of solvents or diluents.
The reaction may be profitably supported by the addition of a small quantity of
[D. 071
^

page_text: an alkali or acid, or of certain salts. The greater part of the amino alkylic ethers
is transformed with readiness, for example, by gently heating on the water bath,
whilst the remainder is changed with greater difficulty into the isomeric products.
The new products thus obtained are, as above mentioned, hydroxybenzyl-
alkylamines, & the respective homologues or analogues thereof. They dissolve in
acids as well as in alkalies. They can be used in the production of dyestuffs, or
of pharmaceutical products or the like.
My foreign correspondents give the following examples, in order to illustrate
the process of transforming phenolaminoalkylethers into hydroxybenzylalkylamine
bodies. The parts are by weight.
TRANSFORMATION OF DIMETHYLEXOAMIDOANISOL (OMEGA-DIMETHYLAMIDO-
ANISOL) INTO HYDROXYBENZYLDIMETHYLAMINE.
20 parts of dimethylexoamidoanisol-C₂H₂OCH₂N(CH,),—are boiled with about
30 parts of water during several hours, until a sample of the liquid dissolves
completely in dilute caustic soda lye. At this stage, the liquid is allowed to cool.
The hydroxybenzyldimethylamine thus produced forms a colourless oil, which
separates from the liquid. The mixture is extracted with ether, & the ether
solution thus obtained is evaporated.
The new product thus obtained dissolves with readiness in dilute acids, or in
alkalies; also readily in alcohol, ether, & the other, usual solvents, but with
difficulty in water.
It boils at about 200 degrees Centigrade with partial decomposition.
It has the formula
-
LANAVETAMIDUDIME LAVARIDUMMALL
INTO ACETAMIDOHYDROXYDIMETHYLBENZYLAMINE.
An alcoholic solution of 2.1 parts of paracetamidodimethylexoamidomethyl-
CH,CONH
phenolether―
40
(CH3)2NCH₂O
CH, (prepared by the interaction of 1.5 parts of 3
paracetamidophenol with 0.8 parts of a formaldehyde solution, containing
per cent. formaldehyde and 0.9 parts of a 50 per cent. solution of dimethylamine)
is heated on the water bath until a sample of the liquid dissolves in caustic
soda lye.
The so-formed acetamidohydroxydimethylbenzylamine is isolated in any suitable 3
It melts at 110 degrees Centigrade, & has the formula-
manner.

page_text: PARAACETAMIDOPENTAMETHYLENEBENZYLAMINE FROM PARACETAMIDOEXO-
PENTAMETHYLENAMIDOMETHYL PHENOLETHER.
An alcoholic solution of 2.5 parts of paracetamidoexopentamethylenamido-
NHCOCH,
(prepared from 1-5 parts of para-
O-CH,N(CH,),
methyl phenolether C.H
cetamidophenol by means of 0-8 parts of a 40 per cent. formaldehyde solution and
0.85 parts of piperidine) is heated on the water bath, until a sample of the liquid
dissolves in caustic soda lye. The paracetamidohydroxypentamethylenebenzyl-
amine thus produced is isolated from the alcoholic solution in the usual manner, and
may be recrystallised from dilute alcohol, or from another suitable solvent.
pure product melts at 159 degrees Centigrade. It has the formula :-
The
TRANSFORMATION OF PENTAMETHYLENEXOAMIDOMETHYLHYDROXYQUINOLIN-
ETHER INTO PENTAMETHYLENAMIDOMETHYLENEHYDROXYQUINOLINE.
An alcoholic solution of 24 parts of pentamethylenexoamidomethylhydroxyquino-
linether (prepared from 1.5 parts of hydroxyquinoline by means of formaldehyde
and piperidine) is heated on the water bath until a sample dissolves in caustic soda
lye. The so-formed pentamethylenamidomethylenehydroxyquinoline is isolated in
the usual manner, and may be recrystallised from ligroine. The pure product
melts at 117 degrees Centigrade. It has the formula
The process takes place in an analogous manner, if other compounds containing
the group 0 CH,N
-
R
R
be substituted for these used in the foregoing examples.
Likewise other solvents or diluents may be employed in the process, and the process
may be carried out in the presence of alkalies, acids, or certain salts.
According to the researches of my foreign correspondents hydroxybenzyl
alkylamido compounds, or analogues thereof, are at once obtained on acting
with formaldehyde in the presence of secondary amines on colouring matters
containing bydroxylic groups. In this case, the first formed products containing
✓ Alkyl
mundusto

page_text: those produced by the original colouring matters, and which differ from the latter
by new, valuable qualities.
My foreign correspondents have thus succeeded in transforming a great number
of dyestuffs, especially azo dyes, into new and very valuable colouring matters.
The chemical action which takes place during this process may be illustrated by
the following equations, in which X indicates the radicle of hydroxy dyestuffs.
5
OH
N
Alk
A 11-
+ H₂O.
Alk
X.OH + CH₂O + NH
====
All
CH
CONVERSION OF THE DYE-STUFF FROM DIAZO BENZENE AND PHENOL INTO
A YELLOW BASIC AZO COLOURING-MATTER.
1.35 parts of an aqueous solution of dimethylamine (containing 33 per cent. of
dimethylamine) and 0-75 parts of a formaldehyde solution (containing 40 per cent.
of CH,O) are allowed to run into a solution prepared by dissolving 1.98 parts of
aniline-azo-phenol in 20 litres (in case the parts are kilos. by weight) of alcohol.
The mixture is heated during several hours by means of a water bath, in a vessel
provided with a reflux condenser, until the action is completed. The alcohol is
then distilled off, and the residue, which contains the base of the colouring matter,
is dissolved in muriatic acid, and the thus formed hydrochloride of the base, which
is the colouring-matter, is precipitated by common salt, and isolated in a suitable
manner. The new dye-stuff has the formula :-
RED BASIC AZO COLOURING MATTER FROM THE BROWN INSOLUBLE DYE-
STUFF WHICH IS OBTAINED BY COUPLING DIAZOTISED PARAMIDO
PHENOL WITH ẞ-NAPHTHOL.
0.75 parts of a 40 per cent. solution of formaldehyde, are added to a solution
containing 2.63 parts of paramidophenol-azo-ẞ naphthol, about 30 litres (in case the
parts are kilos. by weight) of alcohol, and 0.85 parts of piperidine. The resulting
mixture is heated during several hours in a vessel provided with a reflux condenser.
The finished dye-stuff is isolated in the manner described in the foregoing
Example V. It yields on cotton prepared with tannic acid or the like, brilliant
red shades fast against the action of alkalies. Its composition is represented by
the following formula :-

page_text: In a manner similar to that described in preceding Examples V & VI, the
analogous azo dyes containing phenol, naphthol, or the like, or, generally, all dyes
substituted by hydroxylic groups in the aromatic nuclei, are converted into new
dyestuffs which are more soluble than the original dyes, and possess great value for
dyeing and printing purposes.
The dimethylamine and piperidine used in the last two examples, can be replaced
by equivalent quantities of other secondary amines of the fatty series, and in place
of formaldehyde, all those compounds can be used which act in the same or a
similar manner. As above mentioned, the new process is not limited to azo
dyestuffs, but applies in the same manner to every colouring matter containing
hydroxylic groups in the aromatic nucleus, as becomes evident from the following
example. The parts are by weight.
CONVERSION OF A MUSCARINE INTO A SOLUBLE BLUE DYE-STUFF FAST
AGAINST ALKALI.
3-26 parts of muscarine (obtained from nitrosodimethylaniline and 2.7 dioxy-
naphthaline) are mixed with 30 parts of alcohol. After adding 1-35 parts of a
33 per cent. solution of dimethylamine & 0-75 parts of a 40 per cent. solution of
formaldehyde, the mixture is heated during several hours in a vessel provided with
a reflux condenser. The alcohol is distilled off, and the residue is dissolved in
dilute hydrochloric acid. The dyestuff is finally precipitated with the acid of
common salt. It is more soluble than muscarine, & yields on cotton prepared with
tannin, blue shades fast against the action of alkalies. Its composition is represented
by the following formula :-
It will be obvious that not only the compounds employed in the foregoing
Examples 5, 6, and 7, are fit for the production of such basic azodyes, but
generally all dyestuffs containing hydroxylic groups in the aromatic nucleus can
be used with the same or a similar result.
My foreign correspondents have described in the above examples some distinct
methods of practically producing some of the hydroxybenzylakylamine compounds
& hydroxybenzylalkylamido dye-stuffs herein before defined. Of course, the manu-
facture of these products is not restricted to the particulars given in the examples,
as these can be varied, and generally the components used can be replaced by other
analogous compounds. The complete products and dye-stuffs may be isolated in
any other manner. The nature of this invention is not altered by such or similar
variations, or modifications, as the invention relates more especially to the intro-
duction of dialkylamido groups into the nucleus of aromatic compounds containing
hydroxy-groups, in order to produce hydroxybenzylalkylamido compounds &
hydroxybenzylalkylamido dye-stuffs.
Dated this 20th f T.1 1005
NEWTON & SON,
Agents for the Applicant.

page_text: The Manufacture or Production of Chemical Compounds and
Dye-stuffs Derived from Phenolic Bodies.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement :-
My foreign correspondents some time ago found that when phenols, naphthols,
or the like, were acted on by primary or secondary amines of the fatty series, in
the presence of formaldehyde or the like, as described in the Letters Patent
No. 8988, dated 6th May 1895, new products were obtained belonging to the class
of phenol-amino-alkylic ethers containing the groups-
For example, phenol is converted by the action dimethylamine, in the presence
of formaldehyde, into omega dimethyl-amido-anisol (or dimethyl-exo-amido-methyl-
phenolether) C.H.O.CH,N (CH),. Similar compounds have been produced by
acting on phenolic compounds with halogen derivatives of secondary amines.
My foreign correspondents have now discovered that the said compounds 1
containing the groups
are readily converted into isomeric substances, which apparently may be regarded
as hydroxy benzylalkylamines formed in accordance with the equation (supposing
omega-dimethyl-amido-anisol or dimethyl-exo-amido-anisol to have been used)
ATT
CHОCHN (CH₂)₂ = CH₁
ATT VATT '
My foreign correspondents effect the conversion of the phenol-amino-alkylic
ethers into hydroxy benzylalkylamines, for instance, by heating the said amino-
alkylic ethers, or salts thereof, either alone, or together with solvents or diluents.
The change may with advantage be promoted by the addition of a small quantity
of alkali or acid, or of certain salts, such as alkaline carbonates, acetates, phosphates,
cyanides, pyrosulphates, and the like. Most of the amino-alkylic-ethers readily
undergo change, when merely heated on the water-bath, but some are less easily
changed into the isomeric compounds.
The new products thus obtained are, as above mentioned, hydroxy benzylalkyl-
amines, or homologues or analogues thereof. They dissolve in acids as well as in
alkalis, and may be used in the production of dye-stuffs, or of pharmaceutical
products or the like.
My foreign correspondents give the following examples to illustrate the process

page_text: TRANSFORMATION OF
DIMETHYL-EXO-AMIDO-ANISOL (OMEGADIMETHYL-
AMIDO ANISOL) INTO HYDROXY BENZYLDIMETHYLAMINE.
2 parts of dimethylexo-amido-anisol, C.H.OCH,N (CH),, are boiled with about
30 parts of water during several hours, until a sample of the liquid affords a clear
solution, when mixed with dilute caustic soda-lye. As the liquid cools, the hydroxy
benzyldimethylamine separates as a colourless oil.
The new product thus obtained, which is represented by the formula
CONVERSION OF PARACETAMIDO-DIMETHYL-EXO-AMIDO METHYLPHENOL-
ETHER INTO ACETAMIDO HYDROXYDIMETHYLBENZYLAMINE.
An alcoholic solution of 21 parts of paracetamidodimethylexoamidomethyl-
phenolether―

page_text: HYDROXY-PARACETAMIDO-PENTAMETHYLENE BENZYLAMINE FROM PARACET-
AMIDO EXO-PENTAMETHYLENAMIDOMETHYLPHENOLETHER.
An alcoholic solution of 2-5 parts of paracetamido-exo-pentamethylenamido-
(prepared from 1-5 parts of paracetamido-phenol by means of 0.8 parts of a 40 per
cent. formaldehyde solution and 0.85 parts of piperidine) is heated on the water-
bath until a sample of the liquid dissolves in caustic soda-lye. The paracetamido-
hydroxypentamethylene benzylamine thus produced is isolated from the alcoholic
solution in the usual manner, and may be recrystallized from dilute alcohol, or
other suitable solvent. The pure product melts at 119 degrees Centigrade. It is
represented by the formula
TRANSFORMATION
OF
PENTAMETHYLENEEXOAMIDOMETHYLHYDROXY-
QUINOLINETHER INTO PENTAMETHYLENAMIDOMETHYLENEHYDROXY-
QUINOLINE.
An alcoholic solution of 24 parts of pentamethylenexoamidomethylhydroxy
quinolinether (prepared from 1-5 parts of hydroxyquinoline by means of form-
aldehyde and piperidine) is heated on the water-bath until a sample dissolves in
caustic soda-lye. The pentamethylenamid omethyleuehydroxy-quinoline which is
thus formed is isolated in the usual manner, and may be recrystallized from
ligroine. The pure product melts at 117 degrees Centigrade. It is represented
OH
-
by the formula (C,H, – N)
CH,N(CH,) 5.
The process takes place in an analogous manner, if other compounds containing
the group OCHÂN
R
are substituted for those prescribed in the examples
R
previously given. Other solvents or diluents may be used in the process, and the
process may be carried out in the presence of alkalis or acids, or of certain salts,
such as alkaline carbonates, acetates, phosphates, cyanides, pyrosulphates and
the like.
According to the researches of my foreign correspondents, hydroxybenzyl-
alkylamido compounds, or analogues thereof, are at once obtained on acting with

page_text: formaldehyde in the presence of primary or secondary amines on colouring-matters
containing hydroxyi groups. In this case, the products containing the
groups
Alkyl
H
Containing "yurvy groups. ти this case, the products containing
Alkyl
the groups
H
- OCH,N
or OCH₂N
Alkyl
which are first formed, are at once
Alkyl,
converted into the isomeric hydroxy benzyl alkylamido compounds.
New basic dye-stuffs are thus formed which generally yield shades like those
produced by the original colouring-matters, but often differ from the latter in
possessing new valuable properties.
My foreign correspondents have thus succeeded in transforming a great number
of dye stuffs, especially azo dyes, into new and very valuable colouring-matters.
The action which takes place during this process, may be illustrated by the
following equation, in which X indicates the radicle of the hydroxy dye stuff:-
X.OH + CH2O + NH
AIK
= ✗
Alk
Un
CH, N
-
AIK
+ H₂O.
CONVERSION OF THE DYE-STUFF FROM DIAZO-BENZENE AND PHENOL INTO
A YELLOW BASIC AZO COLOURING MATTER.
1.35 parts of an aqueous solution of dimethylamine (containing 33 per cent. of
pure dimethylamine) and 0-75 parts of a formaldehyde solution (containing 40 per
cent. of CH,O) are allowed to run into a solution prepared by dissolving 1-98 parts
of benzene-azophenol in 20 litres (in case the parts are kilos. by weight) of alcohol.
The mixture is heated during several hours by means of a water-bath in a vessel
provided with a reflux condenser, until the action is completed. The alcohol is
then distilled off, and the residue, containing the base of the colouring matter, is
dissolved in muriatic acid, and the hydro-chloride of the base, which is the
colouring matter, is precipitated by common salt, and isolated in a suitable manner.
The new dye-stuff is represented by the formula :
OH
CH¸N = NCH₂
CH
CH,N
.HCI.
CI
RED
BASIC AZO
COLOURING-MATTER
STUFF
WHICH
IS
FROM
THE
BROWN INSOLUBLE DYE-
OBTAINED BY
COUPLING
DIAZOTISED PARAMIDO
PHENOL WITH BETA-NAPHTHOL.
0·75 parts of a 40 per cent. solution of formaldehyde are added to a solution

page_text: containing 2-63 parts of hydroxy benzene-azo-beta-naphthol, about 30 litres (in
case the parts are kilos. by weight) of alcohol, and 0.85 parts of piperidine. The
mixture is heated during several hours in a vessel provided with a reflux condenser.
The dye-stuff is ultimately isolated in a manner described in the sixth example.
It dyes cotton prepared with tannic acid or the like brilliant red shades which
withstand the action of alkalies. Its composition is represented by the following
formula :-
:-
In a manner similar to that described in the examples V and VI, the analogous
azo dyes containing phenol, naphthol, or the like; in fact all dyes containing
hydroxyl groups in the aromatic nuclei, are converted into new dye-stuffs which
are usually more soluble than the original dyes, and in some cases are of great
value for dyeing and printing purposes.
Instead of the dimethylamine and piperidine prescribed in the last two examples,
equivalent quantities of other secondary amines of the fatty series can be used, and
in place of formaldehyde, all compounds can be used which act in the same or a
similar manner.
As above mentioned, the new process is not limited to azo dye-
stuffs, but applies equally to all colouring-matters containing the hydroxyl groups
in the aromatic nucleus, as will be rendered evident by the following example.
The parts are by weight.
CONVERSION OF "MUSCARINE
INTO A SOLUBLE BLUE DYE-STUFF WHICH
WITHSTANDS ALKALI.
3.26 parts of muscarine (obtained from nitrosodimethylaniline and 2.7 dihydroxy-
naphthaline) are mixed with 30 parts of alcohol. After adding 1.35 parts of a
33 er cent. solution of dimethylamine and 0.75 parts of a 40 per cent. solution of
formaldehyde, the mixture is heated, during several hours, in a vessel provided
with a reflux condenser. The alcohol is then distilled off, and the residue is
dissolved in dilute hydrochloric acid. The dye-stuff is finally precipitated with
the aid of common salt. It is more soluble than muscarine, and when cotton
prepared with tannin is dyed with it, blue shades are produced which withstand
the action of alkalies. Its composition can be represented by the following
formula:-
It will be obvious that not only are the compounds prescribed in the examples five,
six, and seven, previously given, fit for the production of such basic azo dyes, but
all dye-stuffs containing hydroxyl groups in the aromatic nuclei, can be used with
the same or a similar result.
In the above examples, my foreign correspondents have described several distinct
methods of practically producing some of the hydroxybenzylalkylamines and
hydroxybenzylalkylamido dye-stuffs hereinbefore defined. As a matter of course,
however, the manufacture of these products is not restricted to the particulars
given in the examples, as these can be varied, and the compounds used can be
exchanged for other analogous compounds. The final products and dye-stuffs may
also be isolated in any suitable manner. The nature of this invention is not altered
by such or similar variations or modifications, as the invention relates more especially

page_text: to the production of hydroxy benzylalkylamines and hydroxy-benzylalkylamido
dye-stuffs.
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
from abroad), I declare that what I claim is :-
1. The conversion of aromatic compounds in which a hydrogen atom of the
nucleus is displayed by the groups
(in which schemes alkyl signifies methyl, ethyl, or the like fatty radicles) into
10 hydroxybenzylalkylamines.
2. The production of hydroxybenzylalkylamines represented generally by the
constitutional formulæ :
or salts of such compounds, either alone, or together with suitable solvents or
diluents, and small quantities of alkali or acid, or certain salts, in the manner
herein before defined.
3. In the process defined by the foregoing claim two, the use of aromatic
compounds containing the group

page_text: 6. The production of colouring matters containing hydroxy groups and the
groups
in the aromatic nuclei, which process consists in acting on dye-stuffs containing
hydroxy groups with primary or secondary fatty amines in the presence of form-
aldehyde.
7. In the process defined by the foregoing claim six, on the one hand, the use of
any dye-stuff containing the hydroxy-group in the aromatic nucleus, and, on the
other hand, the use of mono- or dimethylamine, mono- or diethylamine, piperidine,
piperazine, or the like fatty primary or secondary amines.
8. As new products of manufacture,
a) the new compounds, and
6) the new colouring matters,
produced by the processes herein before
defined, or in any other way affording
the same result.
Dated this 28th day of April 1896.
NEWTON & SON,
Agents for the Applicant.
NEWTON & SON,
Agents for the Applicant.