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

page_text: Date of Application, 6th May, 1895
Complete Specification Left, 5th Feb, 1896-Accepted, 7th Mar 1896
PROVISIONAL SPECIFICATION
[Communicate from abroad by THE FARBENFABRIKLY, vormals FRIEDRICH
BAYER & Co, of Elberfeld Germany ]
The Manufacture or Production of Chemical Compounds and
Dye stuffs Derived from Phenolic Bodies
I PHILIP ARTHUR NEWTON of The Office for Patents, 6 Breams Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows
-
My foreign correspondents have found that chemical compounds containing
bydroxlic groups in the aromatic nucleus, are generally capable of being condensed
with primary or secondary amines of the fatty series, in the presence of form
aldehyde or the like It makes no difference whether the process is allowed to take
place at ordinary temperature, or at somewhat higher temperature, no what kind
of solvent or diluent is used, nor if the action is carried out without adding solvents
or diluents
This new process applies not only to phenols, naphthols, and analogous bodies,
or derivatives thereof, but also to every substance, especially to dye-stuffs
containing one or several hydroxylic groups in the aromatic nucleus
A series of new products is thus obtained which can be used as materials for the
manufacture of coloring matters, or which are by themselves dye-stuffs
If, for example, phenol formaldehyde, and dimethylamine be employed, the
eaction proceeds in accordance with the following equation
This equation is typical of the action which takes place when other phenolic
bodies, fitty aldehyde, and primary or secondary fatty amines, are used
The products thus obtained from phenols naphthols, or the like, are chemically
alkylic ethers of phenols, naphthols, or the like, in which a hydrogen atom of the
alkyl radicle is substituted by an alkyl amido radicle, which becomes evident from
the preceding equation
The proces is illustrated by the following example, which is merely typical
PRODUCTION OF "OMEGA DIMETHYLAMIDO ANISOLE, OR DIMETHYL EXO-
AMIDOMETHYLPHENOLETHER FROM EQUIMOLECULAR PROPORTIONS OF
PHENOL, DIMETHYLAMINE, AND FORMALDEHYDE
75 parts of a solution of formalhyde (containing 40 per cent of CH₂O) are
added to a liquid prepared by mixing a solution of 94 parts of phenol in about
50 litres (in case the parts are kilos by weight) of alcohol, with a watery solution
of 13 5 parts of dimethylamine containing 33 per cent of dimethylamine

page_text: Under spontaneous heating, the formation of the new basic compound is
completed after a short time After distilling off the alcohol, and diluting the
residue with hydrochloric acid, the so formed solution is filtered off, and the
resulting filtrate is mixed with concentrated caustic soda lye The new basic
compound is separated from the solution as a colorless oily body, which pouses es
the formula
PRODUCTION
ETHER,
OF OMEGA AMIDOI HENETOI, OR
EXOAMIDO LTHYIIHENOL
FROM J QUAL MOI ECULAR PROPORTIONS OF PIENOI AND
BROMEIHYLAMINE
94 parts (1 molecular proportion) of phenol are dissolved in 04 litres (in case
the parts are kilos by weight) of alcohol After adding 2 24 parts (2 molecular
proportions) of caustic potassa lye, containing 5) per cent of KOTI, 205 parts
(= 1 molecului proportion) of biomethylaminehydrobromide (CH,B,CH,NH,
HBr (Be d d chem G, XXI 566) are introduced
The resulting mixture is heated during about 24 hours by means of a waterbath
in a vessel provided with a reflux condenser When the action is completed, the
alcohol is di tilled off, and the residue is dissolved in hydrochloric acid
The new
basic compound, which chemically is omega amidophenetol, or exoamidoethylphenol-
ether, is precipitated by the addition of concentrated caustic sodalye It separates
as an oily body
The process takes place according to the following equation
-
C¸H₂OH + 2 KOH + BrC₂H NH₂ HBr = C¸H¸ O CH NH2 + 2 KBr + H₂O
Naturally, the process illustrated by the foregoing second example not only
applies to the substance employed in this example, but also to all similar or
analogous compounds, that is to say, the phenol can be replaced by equivalent

page_text: quantities of other aromatic bodies which contain hydroxylic groups, and instead
of the hydro bromide of bromethylamine, the free bromethylamine, or other salts
of this compound, or other halogen derivatives of primary or secondary or tertiary
alkylamines, or the hydro chlorides, hydrobromides, or other salts of such
halogenated alkylamido compounds, can be used with the same or a similar result
The caustic potassa lye used in the example can be replaced by caustic soda lye,
or the like, and stead of alcohol other suitable solvents or diluents can be
employed, or the process may carried out without adding any solvent or diluent
My foreign cori espondents have found that amongst the compounds obtainable
by means of one of the two methods herein before defined, those are of special
value which contain fiee amido groups
According to the researches of my foren correspondents, these compounds
containing amido groups can be used a initial material for preparing new valuable
basic azo dye-stuffs
The last named compounds containing amido groups are most profitably prepared
by condensing nitro phenolic bodies, either with alkylamines in the piesence of
formaldehyde or the like, or with halogen derivatives of alkylamines, and
subsequently reducing the so-formed nitio products Thus, for instance, para-
nitrophenol, when acted on with formaldehyde and methylamine according to the
process illustrated by the above first example, is converted into paranitro phenol
exoamido ethylether, which process can be illustrated by the following equation
NO, C.H.OH + CH₂O + CH₂ NH,
=
NO, C.H, 0 CH, CH, NH, + H,O
NO₂ C.H OH + KOH + BrCH₂CH, NH, NO, CHOCH,CH,
=
Ng+ ADI + ngu
The nitrocompounds obtainable by either method are subsequently reduced in
the known manner, the corresponding amido compounas being thus produced
Of the compounds herembefore defiued, in which the nydiogen atom of the
hydroxylic group is replaced by an imido alkyl indicle, some are described in
chemical literature, uz _" betaaminoethylphenylethei CH,O CII,CH,NH,
(Ber dd ch G, XXII, 3256), "gamma aminopropylphenylether' CH,OCH,
CH,CH,NH, (Be d d ch G XXIV, 2643) "delta aminobutylphenylether
CHO CH₂CH,CH,CH,NH, (Ber d d 'ch G, XXIV, 3232) "amino methyl-
phenoxylepeutan C,H,O CH₂CH₂CH CH
VCH,
CH₂
NH2 (Ber d d ch G,
XXVI, 2572), and the so called " paraamidophenol-omega amidoethylether
(NH, CHI, OCH2CH2NH2) which has been produced by condensating para
nitrophenol buta-brometly lether with ammonia, and subsequently reducing the
so foimed nitro product (Journ ẞ Prakt Ch 1881, 248)
The processes that have been employed for producing the last-named compounds
are, however, less profitable than the two methods illustrated by the foregoing two
examples
In order to obtain dyestuffs from the said products containing amido groups,
these products are diazotised in the known manner, and the resulting diazo
compounds are allowed to act on dye stuff components in a suitable manner
The coloring matters thus obtained possess basic nature, which is caused by

page_text: the fact that they coutain amido groups in the alkyl radicles, which are in place of
the hydrogen of the hydioxy group of the phenolic bodies used as initial materials
Ihese dye-stuffs are therefore capable of dycing cotton moidanted with tannic
acid on the like, and can be briefly termed as "basic azo dye-stuffs'
Of basic azo coloring matters, only such have been prepared hitherto, which
yield yellow or orange shades, whereas my foreign coirespor dents have now
succeeded in preparing out only yellow and orange dye-stuffs, but also such as
produce on cotton prepared with tannic acid or the like scarlet shades, which could
not be obtained hitherto in dyeing cotton mordanted with tannic acid
This process for producing the said new basic azo dye-stuffs is illustrated by the
following examples I he puts are by weight
N
1 94 parts of metamidophenol omega diethyl amidomethylether NH, CHO CH,
C₂HS
\C₂H₂
are diazotised by means of 07 parts of nitrite of sodium in the presence
of hydrochloric acid The resulting diazo solution is then allowed to flow into
an aqueous solution of 179 parts of the hydrochloride of ẞ naphthylamine l he
formation of the dye-stuff is hastened by the addition of sodium acetate The
finished dye-stuff is precip tated by meins of common salt, and isolated in a

page_text: suitable manneı
It produces on cotton piepied with tannic acid or the like,
brilliant yellow-orange shades and possesses the following formula
D
2
-N-CH,-0 CHỌN=N-CH,NH, HC}
Similar coloring matters are obtained if the metamidophenol omega diethylamido
methylether used in the last-named example is replaced by coresponding quantities
of analogous base, or if betanaphthylamine or other amines or secondary amines
of the naphthalme series, or alpha or beta uaphthol phenol, or analogous or
homologous compounds are substituted for the betanaphthylamine used in the last
example
If alkylated naphthylamines of naphthols be employed as components, azo dyes
are obtained, which dve prepared cotton tu red-orange shades
C
The diazo solution obtained from 152 parts of puramidophenol-ome i-amido-
ethylether" by means of 07 parts of nitute of sodium in the presence of
hydrochloric acid, is poured into a watery solution piepied from 18 parts of the
The base of the
sodium salt of beta naphthol, and mixed with sodium carbonate
It is filtered off, washed,
dyestuff is thus precipitated in the form of red flakes
and dis olved in hot dilute hydrochloric acid The finished dyestuff, that is to say,
the hydrochloride of this base, is precipitated by adding either common salt or an
excess of muriatic id to the above solution It produces on cotton mordanted
The new colouring
with tonnic acid or the like, brilliant fast scarlet-red shade
matter possesses the following formula
Similar dyestuffs are obtuned if the paramido-pnenol-omega-amido ethylether
is replaced by corre ponding quantities of homologous compound, such as amido-
Ciesol-omega amido-ethylether (obtained from pa mitio-meta cresol) or the like,
o deuvatives
or equivalent quantities of alphi-n phthol or other phenolic bodie
thereof are substituted for the beta naphthol used in the fourth ex imple
As above mentioned, the two processes illustrated by the foregoing Examples
One and Two apply not only to the simple phenols naphthols and the like or to
nalogous compounds and derivatives thereof, but also to all aromatic substances
in which a hydrogen atom of the nucleus is substituted by hydroxylic group
The researches of my foreign correspondents have shewn that all dye-stuffs,
even those which are insoluble in water or in dilute acids, in case they cont un free
bydroxylic groups in the aromatu nucleu, can be condensed either with
formaldehyde or the like, and piimary, and especially secondary bases of the fatty
series, according to the process illu tiated by the fist example, or with halogen
demnatives of alkylamines, according to the process illustrated by the second
example New basic dye stuffs are thu produced, which generally produce shades
the same as those produced by the onginal colouring matters, and which differ
fom the latter by new, valuable quilities
My foreign cespondents have thu succeeded in tran forming a great number
of dyestuffs, especially azo dyes, into new and very valuable colouring matters
The chemical action which tiles place during these proce e, it for example,
formaldehyde and dialkylamine be employed in the first process, and biomalkyl-

page_text: amine in the second process, may be illustrated by the following equations, it
which X indicates the radicle of hydroxy dyestuffs
All
-
All
CONVERSION OF THE DYE-STUFI FROM DI AZO BENZENE AND PHENOL INTO A
YELLOW BASIC A70 COLOURING MATTER
135 parts of an aqueous solution of dimethylamine (containing 33 per cent of
dimethylamine) and 75 parts of a formaldehyde solution (containing 40 per cent
of CH2O) are allowed to run into a solution prepared by dissolving 198 parts of
aniline izophenol in 20 litres (in case the parts are kilos by weight) of alcohol
The mixture is heated during several hours, by means of water bath, in a vessel
provided with a reflux conden cr, until the action is completea 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 silt, and isolated in a suitable
The new dye-stuff has the formula
manner
=
-
CH,NN CH, O CH₂N
HCI
ATT
THE
RLD BASIC AZO COLOURING MATTLR 1 ROM
STUFI WHICH IS OBTAINED BY COUPLING
PHINOL WITH BI TA-NAI RIHOL
BROWN INSOLL BIE DYE
DIAZOFISI D PARAMIDO
075 parts of a 40 per cent solution of formaldehyde are added to a solution
containing 2 63 parts of paramidophenol-170-beta-naphthol, about 30 litres (in case
the parts are kilos by weight) of alcohol, and 08 parts of piperidine The
resulting mixture is heated during several hours in a vessel provided with a reflux
condensei The finished dyestuff is isolated in the manner described in Lxample VI
It yields on cotton prepared with tannic acid or the like, biilliant red shades fast
to the action of alkalies Its composition is represented by the following
formula
-

page_text: The dimethylimine and piperidine used in the last two examples, can be replaced
by equivalent quantities of other secondary or of primary amines of the fattv series
and in place of formaldehyde, all those compounds can be ued which act in the
same or a similar manner As above mentioned, the new process is not limited to
azo dye-stuffs, but applies in the same manner to every colouring-matter containing
hydroxylic groups in the aromatic nucleus, as becomes evident from the following
two examples The parts are by weight
66
EXAMILE III
CONVERSION OF MUSCARINI INTO A SOLUBLE BLUE DYE STUFF FAST TO
ALKALI
326 parts of muscame (obtained from nitrosodimethylaniline and 27-dioxy-
naphthaline), are mixed with 30 parts of alcohol After adding 1 35 parts of a
33 per 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 condensei The alcohol is distilled off and the residue is dissolved in
dilute hydrochloric acid Ihe dye stuff is finally precipitated with the aid of
It is more soluble than muscarie, and yields on cotton prepared
with tannin, blue shades fast to the action of alkalies Its composition is
represented by the following formula
common silt
-
CONVERSION OF THE DYESTUFF FROM DIAZOBENZENE AND 27 DIHYDROXY-
NAPHTHALINE, INTO AN ORANGE BASIC AZO COLOURING-MATTER
The
2 62 parts of the azo dye from diazo benzene and 27-dihydroxynaphthaline are
mixed with 2 24 parts of caustic potassa-lye (50%), 205 parts of bromoethylamine
hydrobiomide, and about 20 parts of alcohol The resulting mixture is heated
during five hours, it about 120 degrees of Centigrade in a closed vessel
alcohol in excess is distilled off, and the residue is mixed with dilute caustic soda-
lye The precipitated dyestuff is filtered off and purified by redissolving in dilute
hydrochloric acid, and salting out again with common salt It produces orange
shades on cotton prepared with tannic acid
It will be obvious that not only the compounds employed in the foregoing
Examples 8 and 9, are fit for the production of such basic azodyes, but generally all
dye-stufls containing hydioxylic groups in the aromatic nucleus can be used with
the same on a similar result
My foreign correspondents have described in the above examples, some distinct
methods of practically producing some of the umido compounds and dyestuffs
hereinbefore defined Of course
the manufacture of these products is not
restricted to the particulars given in these examples, as these can be varied,
and, generally, the components used can be replaced by other analogous compounds
The complete products and dyestuffs may be isolated in any other manner
nature of this invention is not altered by such or similar variations or modifications,
as the invention in general relates to the production of basic compounds and basic
dye-stuffs derived from phenolic bodies, and containing, in place of the hydrogen
atom of the original hydroxy groups, alkylamine groups
Dated this 6th day of May 1895
The
NEWTON & SON,
Agents for the Applicant.

page_text: The Manufacture or Production of Chemical Compounds and
Dye-stuffs Derived from Phenolic Bodies
I PHILIP ARTHUR NEWTON of The Office for Patents, 6 Breams 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 have found that compounds containing hydroxy
groups in the aromatic nucleus are generally capable of being condensed with
primary or secondary amines of the fatty series, in the presence of formaldehyde
It matters not whether the process is allowed to take place at the ordinary, or at a
somewhat higher temperature, nor what kind of solvent or diluent is used, nor if
the action is carried out without adding solvents or diluents
This new process is applicable to phenols, naphthols, and analogous phenolic
compounds generally, and derivatives thereof
If, for example, betanaphthol, formaldehyde, and dimethylamine, be used, the
action is that represented by the following equation
-
C,H,OH + CH₂O + NH
-
C₁H,O CH, N
+ H₂O
IT
H
A similar action takes place when other aromatic phenols, fatty aldehydes, and
primary or secondary fatty amines, are used
The products thus obtained from phenols, naphthols, or the like, are methylic
ethers of phenols, naphthols, or the like hydroxy compounds, in which a hydrogen
atom of the methylic radicle is displaced by the alkylamido or dialkylamido 2
radicle
The process is illustrated by the following typical example The parts are by
PRODUCTION OF OMEGADIMETHYLAMIDO ANISOL, OR DIMETHYL EXOAMIDO-
METHYLPHENOLETHER FROM MOLECULAR PROPORTIONS OF PHENOL,
DIMETHYLAMINE, AND FORMALDEHYDE
75 parts of a solution of formaldehyde in water (containing 40 per cent of
pure CH,O) are added to a liquid mixture of 94 parts of phenol, about 50 litres
(in case the parts are kilos by weight) of alcohol, and an aqueous solution of
135 parts of dimethylamine (containing 33 per cent of pure dimethylamine)
Heat is spontaneously evolved, and the formation of the new basic compound is
complete within a short time After distilling off the alcohol, the residue 18
mixed with hydrochloric acid, and the solution is filtered On mixing the filtrate
with a concentrated caustic soda-lye, the new basic compound is deposited as a
colorless oily substance represented by the formula-
C,H,O CHỌN(CH3).

page_text: or substituted phenols, of the benzene and naphthalene series, are u ed, or if
corresponding quantities of other secondary amines, or primary amines, of the
fatty series (including piperidine, piperazine or the like), are substituted for the
dimethylamine used in the above example
As an illustration of the variety of products which are obtainable by this
process, the components used in producing other typical members of this series,
together with the formulæ and the properties of the new products, are indicated in
the following table
-
prismatic needles fiom
acetone, melting at 135
Centigrade,
degrees
soluble in dilute acids,
insoluble in dilute all -
lies

page_text: My foreign correspondents have also succeeded in obtaining the same or similar
compounds in another new way This process consists in condensing hydroxy
compounds of the aromatic series, such as phenol, naphthol, substituted phenols,
naphthols, or the 1 ke, or the salts of these compounds, with certain halogen
derivatives of primary or secondary or tertiary fatty alkylamines
If, for example, phenol and bromethylamine are used, the following equation
illustrates the nature of the change
PRODUCTION OF OMEGA AMIDOPHENETOL, OR EXOAMIDO ETHYLPHENOLETHER,
FROM A MOLECULAR PROPORTION OF PHENOL, AND A MOLECULAR PRO-
PORTION OF BROMETHYLAMINE
94 parts of phenol are dissolved in 04 litres (in case the parts are kilos by
weight) of alcohol After adding 2 24 parts of caustic potash lye (containing
50 per cent of KOH), 20 5 parts of bromethylamine hydrobromide (CH,BrCH,
NH,HBr (see Berichte der Deutschen Chemischen Gesellschaft, XXI, 566) are
introduced The mixture is heated during about 24 hours, by means of a water
bath, in vessel provided with a reflux condenser When the action is complete,
the alcohol is distilled off, and the residue is dissolved in hydrochloric acid The
new basic compound, omega amidophenetol, or exoamido ethylphenolether, is then

page_text: an oil
precipitated by the addition of concentrated caustic soda lye It separates as
The process described in the second example represented by the following
equation
-
2 KBr + H₂O
Instead of the phenol prescribed in this last example, equivalent quantities of other
aromatic compounds containing hydroxy groups, and instead of the hydrobromide
of bromethylamine, other salts of this compound can be used or salts of other
analogous halogen derivatives of primary or secondary or tertiary alkylamines
It is al o possible to use, instead of the salts of the said halogenated amido oi
alkylamido compounds, the free compounds, and instead of caustic potash lye,
caustic soda lye or the like, and instead of alcohol, other suitable solvents or
diluents and the process may also be carried out without adding any solvent of
diluent
When, in the last named process, nitrophenols (such as paranitrophenol or
analogous aromatic hydroxy compounds) are used, the action takes place in
similar manner Thus, for instance, the interaction of paranitrophenol and biom-
ethylamine (BrCH,CH,NH2) affords a nitro compound in the manner represented
by the following equation
NO,CH,OH + KOH + BrCH,CH,NH₂ = NO,СH¸ОCH₂CH,NH,+
This and an logous nitro compounds obtained in a similar manner are converted
into the corresponding amido compounds by a subsequent treatment with reducing
ngents
My foreign correspondents have found that these amido compounds are of special
value, as they can be used as initial materials in preparing new valuable basic azo
dye-stuffs
Several of the above defined compounds, in which an amido alkylic group, has
displaced the hydrogen of the hydroxy group, have already been obtained in a
manner different from that herein before described, viz, "betaaminoethylphenyl-
ether, CHO CH,CH,NH, (see Berichte der Deutschen Chemi chen Gesell-
schaft, XXII, 3256), gamma aminopropylphenylether,' CHO CH₂CH₂ch₂
NH, (see Berichte der Deutschen Chemischen Gesellschaft, XXIV, 2643),
"delta aminobutylphenylether, "CH₂OCH,CH,CH,CH,NH, (see Berichte dei
Deutschen Chemischen Gesellschaft, XXIV, 3232), aminomethylphenoxyl-
peut ine,' represented by the formula-
AL
(H₂O CII,CH,CH,CH,
(Berichte der Deutschen Chemischen Gesellschaft, XXVI, 2572), and paramido
phenolomega amidoethylether
The last-named
(NH,C,H,OCH,CH,NH,)
compound has been produced by condensing paranitrophenol beta bromethylether
with ammonia, and subsequently reducing the mitro compound (sec Journal fur
Praktische Chemie, 1881, page 248)
The pioce se- that have hitherto been used in producing the last named
compounds, are, however, less advantageous than the two methods illustrated by
the two examples previou.ly given
In order to obtain dye-stuffs from the products containing amido groups in the
aromatic nuclei, as hereinbefore referred to, these products are diazotised in the

page_text: known manner, and the diazo derivatives are allowed to act on dye-stuff components
in a suitable manner
The coloring matters thus formed are of a basic character, owing to the fact
that they contain amido or alkyl-amido groups in the alkyl radicles, which displace
the hydrogen of the aromatic hydroxy group in the phenol, used These dye-
stuffs are therefore capable of dyeing cotton mordanted with tannic acid, or the like,
and may be briefly termed "hasic azo dye-stuffs'
The basic azo coloring matters hitherto known yield yellow or orange shades,
but my foreign correspondents have now succeeded in preparing, not only yellow
and orange dye-stuffs, but al o such as will dye cotton prepared with tannic acid or
the like, scarlet shades, which could not heretofore be obtained on cotton mordanted
with tannic acid
This process for producing the said new basic azo dye-stuffs is illustrated by the
following examples The parts are by weight
1 8 parts of “paramidophenol omega dimethylamido ethylether,' NH₂CHO C,
H.N.
1 57
CH,
CH,
mitrite, and sufficient quantity of dilute hydrochloric acid A solution of
parts of
para xylidine hydrochloride, containing an excess of sodium acetate,
is then added The formation of the dye-stuff immediately begins, and is com-
pleted by gently heating the mixture The finished dye-stuff is precipitated by
means of common salt, and isolated in a suitable manner, or the base of the dye-
stuff may be first separated by means of alkali lye, and may then be filtered off,
and transformed into the hydrochloride, which is the finished dye stuff
produces brownish-yellow shades on cotton prepared with tannic acid
represented by the following formula
are diazotised in the usual manner by means of 07 parts of sodium
It
It is
vo parts of metamidophenol omega diethylamidoethylether, NH₂CH O̟ CH,
C₂H,
CH,N
C₂H
presence of hydrochloric acid The diazo solution is then allowed to flow into an
aqueous solution of 179 parts of beta naphthylamine hydio-chloride
formation of the dye-stuff is forwarded by the addition of sodium acetatu
are diazotised by means of 07 parts of sodium nitrite, in the 40
The
I he

page_text: fit ished dye-stuff is precipitated by means of common salt, and isolated in a suitable
It produces yellowish-brown shades on cotton prepared with tannic acid
or the like
This dye-stuff is represented by the following formula
manner
сн.
CH
>N-CH,H,-0C.EN=N-CHẠNH,HC1
Similar coloring matters are obtained on using, instead of the metamidophenol
omega diethylamido ethylether of the last named example, corresponding quantities
of analogous bases, or if alphanaphthylamine or other amines or secondary amines
of the naphthalene series, or alpha or betanaphthol phenol, or analogous or
homologous compounds, are substituted for the betanaphthylamine used in the last
example
If naphthols be used as components, azo dyes are obtained which dye prepared
The diazo solution obtained from 1 52 paits of "palamidophenol omega amido-
ethylether" by means of 07 parts of nitrite of sodium, in the presence of hydro-
chloric acid, is poured into an aqueous solution of 18 parts of the sodium salt of
betanaphthol, mixed with sodium carbonate The base of the dye-stuff is thrown
down as a red flocculent precipitate It is filtered off, washed, and dissolved in
hot dilute hydrochloric acid, and the finished dye stuff, that is to say, the hydro-
chloride of the base, is precipitated by adding either common salt, or an excess of
muriatic acid, to the solution It produces fast scarlet-red shades on cotton
mordanted with tannic acid or the like This new coloring matter is represented
by the following formula
-
The diazo solution obtained from 152 parts of "palamidophenol omega amido-
ethylether" by means of 07 parts of nitrite of sodium, in the presence of hydro-
chloric acid, is poured into an aqueous solution of 18 parts of the sodium salt of
betanaphthol, mixed with sodium carbonate The base of the dye-stuff is thrown
down as a red flocculent precipitate It is filtered off, washed, and dissolved in
hot dilute hydrochloric acid, and the finished dye stuff, that is to say, the hydro-
chloride of the base, is precipitated by adding either common salt, or an excess of
muriatic acid, to the solution It produces fast scarlet-red shades on cotton
mordanted with tannic acid or the like This new coloring matter is represented
by the following formula
-
HCINH,C,H,OHN = NCH,OH
HẠN
==
Similar dye-stuffs are obtained by using, instead of paramidophenol omega-
amidoethylether, corresponding quantities of homologous compounds, such as
amido ciesol omega amido ethylethci (obtained from paranitio meta cresol), or the
like, or if equivalent quantities of alpha naphthol, or other phenols, or derivatives
thereof, are substituted for the beta naphthol used in the Fourth Example
As above mentioned, the two processes illustrated by the foregoing examples one
and two, apply not only to the simple phenols, naphthols, and the like, or to
analogous compounds and derivatives thereof, but generally to aromatic substances
containing hydioxy groups in the aromatic nucleus
My foreign correspondents have described in the above examples, several distinct
method of practically producing some of the amido compounds, and some of the
dye-stuffs herein before defined Of course, the manufacture is not restricted to the
particulars given, as these can be varied As already mentioned, instead of
the components prescribed, other analogous compounds can be used, and the
complete products and dye-stuffs may be isolated in any other suitable manner
Naturally, the nature of this invention is not altered by such or similar variations or
modifications
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 phenols nauht.hols. dihydroxynaphthalenes, or the like

page_text: aromatic hydroxy compounds, or derivatives thereof, into new products containing,
in place of the hydroxy group, the monovalent groups-
олкут
-OCH,N
акут
, or
-OCH,N
ப
A111
(in which scheme, alkyl signifies methyl, ethyl, or the like fatty radicles)
2 The production of aromatic compound containing, in the aromatic nuclei, the 5
above defined groups-
- OCH₂N
or -OCH,N
TT
which process consists in allowing formaldehyde, and primary or secondary fatty
amines, to act conjointly in molecular proportions on aromatic hydroxy compounds,
such as phenols, naphthols, dihydroxy-naphthalenes, or analogues or derivative-
thereof
3 In the process defined by the foregoing Claim Two, on the one hand, the us
of phenol, cresol, thymol, alphanaphthol, betanaphthol, beta₁ beta, dihydroxy-
naphthalene, beta₁ beta, dihydroxynaphthalene, or the like aromatic hydroxy
compounds, and, on the other hand, the use of dimethylamine, diethylamine,
piperidine, piperazine, or the like secondary fatty amines
4 The production of aromatic compounds containing, in the aromatic nuclei, the
monovalent groups—
(in which formulæ n signifies the figures one, two, three, etc, and alkyl indicates
methyl, ethyl, or the like fatty radicles, the letter X signifying halogen atoms),
which process consists in allowing the said halogen compounds, or salts thereof, to
act either on aromatic hydroxy compounds in the presence of alkalies, or on the
alkaline salts of aromatic hydroxy compounds, adding alkalies, or not, as may be
desirable
5 In the process defined by the foregoing Claim 4, on the one hand, the use of
phenol, naphthols, or analogues or derivatives thereof, including nitro derivatives,
and, on the other hand, the use of bromethylamine (BrCH,CH,NH₂), or analogous
halogen derivatives of primary, secondary, or tertiary fatty amines, or salts of
these halogenated compounds
6 The conversion of the nitro products, obtainable from nitrophenols, or the
like aromatic nitro hydroxy compounds, by means of the processes defined in the
foregoing Claims Four and Five, into the corresponding amido products, which
process consists in treating the said nitro products with reducing agents
7 The production of basic azo dye-stuffs by diazotising the aromatic amido
compounds obtainable by means of the process defined in the foregoing Claim Six,
and subsequently coupling the so-formed diazo derivatives with amido-hydroxy or

page_text: lihydroxy compounds of the benzene or naphthalene series, or other suitable
lye-stuff components
8 As new products of manufacture―
(a) the new chemical
compounds, and
(b) the new coloring
matters
produced by the processes hereinbefore defined, or in
any other way affording the same result
NEWTON & SON,
Agents for the Applicant.