Manufacture and Production of Aromatic Para-amido Aldehydes and their Derivatives of Substitution.
Year: 1898

page_text: Manufacture and Production of Aromatic Para-amido Aldehydes
and their Derivatives of Substitution.
I, THOMAS RICHARD SHILLITO, of 15, Tooks Court, London, E.C., Engineer and
Patent Agent, do hereby declare the nature of this invention, a communication to me
from abroad by Messieurs John Rudolph Geigy & Co., of Basle, Switzerland, Colour
Manufacturers, to be as follows:-
This invention relates to a new process of very general application by which it is
possible to introduce the aldehyde group-C in any aromatic primary,
H
secondary, or tertiary amine having an unhindered para position, or of sulphonic acids
of those amines. The new reaction, upon which the process of this invention is
based, depends upon the simultaneous reaction of formaldehyde and an aromatic
derivative of a hydroxylamine or its sulphonic acids with an aromatic.amine or its
sulphonic acid, whereby directly the aldehyde corresponding to the amine, or to its
sulphonic acid is formed together with an amine or its sulphonic acid corresponding
to the hydroxylamine.
For instance-dimethylaniline formaldehyde and m-sulpho-p-tolylhydroxylamine
furnish the anhydrous compound of the dimethyl-p-amidobenzaldehyde with
paratoluidine-sulphonic acid :

page_text: or another example:-diphenylaminesulphonic acid, formaldehyde and phenylhy-
droxylamine furnish the anhydro compound of the aldehydo-diphenylaminesulphonic
acid together with aniline:
These anhydro compounds are then decomposed by heating their solution with
alkalies or acids and on the one hand there is obtained the corresponding
amidoaldehyde or its sulphonic acid, on the other hand an amido sulphonic acid or
an amine. By employing phenyl- or orthotolylhydroxylamine the separation of the
pure aldehyde is rendered somewhat difficult by the simultaneous formation of bye
products as paraamidophenol, etcetera, out of the hydroxylamine in presence of acids,
but this does not happen when starting from a sulphonic acid of an aromatic
hydroxylamine which at the same time distinguish themselves by a much better
power of reaction.
In practice very favourable results have been obtained in employing the hydroxy-
lamine sulphonic acids obtained by reduction of the generally known sulphonic acids
of the nitrobenzene, of the ortho- and paranitrotoluene according to the process
described in the German Patent Specifications Nos. 84138 and 89978 with powder of
zine in neutral aqueous solution in presence of certain salts as chloride of ammonia,
chloride of calcium, etcetera. Likewise the hydroxylamines deriving from other
nitro compounds as paranitrotoluene, m-nitrobenzoic acid, m-nitro-o-chlorbenzene
sulphonic acid are fit to this reaction, without any advantage however.
The process for the production of aldehydes may be modified in the way that the
hydroxylamine sulphonic acids enter into reaction in statu nascendi with the amine.
in presence of formaldehyde. This may be accomplished by reduction of a mixture
of nitrobenzene or nitrotoluene sulphonic acid, amine and formaldehyde in acid
solution, either by introduction of a reducing agent, for instance, powder of zinc,.
powder of aluminium, iron filings, etceteru, or by the reaction of electrolytically
generated hydrogen. In both cases the aldehydes separate in combination with
toluidine sulphonic acid or metanilic acid as benzylidene compounds, which may be
decomposed into their components in the above described manner.
The following examples are given to illustrate the general method of carrying
out the invention but my correspondents do not limit themselves to the precise
details.
I. PRODUCTION OF THE HYDROXYLAMINE SULPHONIC ACIDS.
METASULPHOPARATOLYLHYDROXYLAMINE.
In an iron drum provided with a lying stirrer and a safety valve, the exterior of
which drum may be cooled by cold water 100 kilos. of technically pure sodium
paranitrotoluene sulphonate (obtained by sulphonation of paranitrotoluene, precipita-
tion with salt water, filtration, and drying) and 15. kilos. of chloride of aminonia are
dissolved in 400 litres of boiling water. The acid solution is exactly neutralised by
ammonia and cooled while stirring. To the thick pap of crystals are now added,
while constantly stirring, and as quickly as-the considerable heating, brought down
by exterior cooling allows it, 80 kilos. of powder of zinc, in avoiding the entrance of
air as much as possible. In a very short time the reaction is finished, which may be

page_text: easily seen by a rapid diminution of the temperature. When the contents of the
drum are quite cold they are quickly passed through a filter press and the cakes of
oxide of zinc coming out of the same are washed out with 250 liters of water. The
whole filtrate acidulated with 20 kilos. of hydrochloric acid can at once be employed
for the production of the aldehyde.
The reduction of other nitro compounds as for instance nitrobenzene sulphonic
acid, nitrobenzoic acid, etcetera, to the corresponding hydroxylamine derivatives is
accomplished in exactly the same way. A characteristic of all these sulphonic acids
of aromatic hydroxylamines is their extreme solubility which makes their separation,
for instance, by addition of common salt, quite impossible.
Small colourless leaves; melting point 114° C., sparingly soluble in water, easily in
benzene, alcohol, and diluted acids.

page_text: Thick yellow prisms; melting point 63° C., readily soluble in alcohol, ether, and
benzene, sparingly soluble in petrolether. Its solution in concentrated muriatic acid
disassociates completely when diluted with water.
Semi fluid yellow resin, crystallising after some time; easily soluble in alcohol,
ether, and benzene, sparingly in petrolether; insoluble in diluted acids.
Yellow non crystallising resin; solubility like the preceding aldehyde.
11. PHENYL-P-AMIDOBENZALDEHYDE.
To the cold (5° C.) solution of 50 kilos. diphenylamine in 400 liters alcohol are
added 22.5 kilos. formaldehyde of 40 per cent., then there is introduced rapidly the
solution of tolylhydroxylamine sulphonic acid (600 liters) acidulated with 40 kilos.
(instead of 20 kilos.) muriatic acid and likewise cooled to 5° C., care being taken to
constantly stir the liquid while adding the hydroxylamine. The diphenylamine,
separating in thin leaves by dilution of the alcohol and thus transforming the liquid
into a thick paste, dissolves very soon. At the same time the liquid gets a deep
orange and afterwards a brown red colour and separates again a brown red precipitate,
After 8 hours, is added so much of a warm solution of carbonate of soda until the
whole mass dissolves with a bright yellow shade whereupon the alcohol is driven away
by means of steam. The remaining solution, when containing small quantities of by
products, while still hot has common salt added to it until it becomes quite clear, and
is filtered when cold. The anhydrous compound of phenyl-p-amidobenzaldehyde with
toluidine sulphuric acid contained in the yellow filtrate as sodium salt cannot be com-
pletely decomposed by treating with alkalies like the anhydrous compounds of the
preceding examples. A splitting off of toluidine sulphonic acid takes place but the
separating products which contain the aldehyde are still soluble in alkali because they
are mixtures with toluidine sulphonic acids. In order to accomplish a complete
decomposition, the above mentioned filtrate is diluted with water up to 4000 liters,
then acidulated with acetic acid and boiled up. When the turbidity taking place by
heating does not increase any more, neutralisation is effected with soda lye and pre-
cipitation with common salt. The filtered precipitate consisting of a mixture of free
aldehyde and still undecomposed anhydrous compound is treated with ether in order
to dissolve the aldehyde.
Phenyl-p-amidobenzaldehyde forms a yellow glassy mass like colophony, brittle and
pulverisable when cold and getting soft when warm, and forming at 70° C. a thick oil.
It dissolves readily in ether and benzene, less in alcohol, scarcely in cold and boiling
water. It shews a very characteristic behaviour against paraphenylendiamine. All
the preceding aldehydes furnish with this diamine cinnabar red to blueish red pre-
oipitates, but when a piece of filtering paper impregnated with an acoholic or etheric
solution of phenyl-p-amido-benzaldehyde is touched with a solution of the chlorhydrate
of paraphenylendiamine, it takes first a brownish red shade which very soon passes
over into a deep voolet black.

page_text: 12-13. METHYL- AND ETHYLPHENYL-P-AMIDOBENZALDEHYDES.
Resemble very much the above mentioned aldehydes, they only remain resinous
when cold and furnish with paraphenylendiamine on paper not violet black but deep
violet brown shades with metallic lustre.
By decomposition of the yellow anhydrous compounds very soluble in diluted
alkalies of the above named aldehyde with toluidine sulphonic acid or metanilic
acid, only a brownish brittle amorphous mass is obtained, consisting probably of a
mixture of polymeric products or products of condensation, or perhaps of quinoid
forms of the aldehyde. It dissolves easily in benzene, less in alcohol or ether,
scarcely in muriatic acid; is coloured reddish brown by the latter.
18. ALDEHYDODIPHENYLAMINESULPHONIC ACID.
A solution of 80 kilos. of sodium diphenylamine sulphonate in 300 litres water,
acidulated by 'addition of 10 kilos. muriatic acid, has added to it 22.5 kilos.
formaldehyde and the acidulated solution of sulphotolylhydroxylamine. Immediately
afterwards the solution turns to yellow; after two days the orange precipitate is
brought into solution by addition of hot water and then is added as much of a solution
of chlorhydrate of aniline or rather paratoluidine as the precipitate is increasing.
It is filtered off, washed, dissolved with carbonate of soda and all the aniline or
paratoluidine driven away by means of a current of steam. The solution is now
completely saturated with common salt at 40° to 50° C., whereby the sodium salt
of the aldehydodiphenylamine sulphonic acid separates in half solid soft lumps.
Separated from the mother lye and dried, it forms a bright yellow powder very
soluble in water. Its solution turns to brown red with muriatic acid without the
formation of a precipitate. With the chlorhydrate of aniline it furnishes an orange
red, with paraphenylenediamine a deep brown red precipitate.

page_text: Production like that of 18. The sodium salts dissolve extremely well in water and
well in hot alcohol. When acidulated there is no precipitation. The first gives with
para-phenylenediamine a very bright cinnabar red, the second a blueish red precipitate
with metallic green lustre. Their hydrazones, which are obtained by heating with 5
phenylhydrazine in acetic acid solution as crystalline precipitates, are colourless.
21-22. ALDEHYDOBENZYLANILINE- AND BENZYLORTHOTOLUIDINE SULPHONIC ACIDS.

page_text: Insoluble in diluted acids, sparingly soluble in concentrated muriatic acid; better
soluble in alcohol, ether and benzene.
THOMAS R. SHILLITO,
15, Tooks Court, London, E.C.
Manufacture and Production of Aromatic Para-amido Aldehydes
and their Derivatives of Substitution.
I, THOMAS RICHARD SHILLITO, of 15, Tooks Court, London, E.C., Engineer and
Patent Agent, do hereby declare the nature of this invention and in what manner
the same is to be performed, a communication to me from abroad by Messieurs John
Rudolph Geigy & Co., of Basle, Switzerland, Colour Manufacturers, to be particularly
described and ascertained in and by the following statement:—
This invention relates to a new process of very general application by which it is
possible to introduce the aldehyde group-C
in any aromatic primary, secondary
or tertiary amine having an unhindered para position, or of sulphonic acids of those
amines. The new reaction upon which the process of this invention is based depends
upon the simultaneous reaction of formaldehyde and an aromatic derivative of a
hydroxylamine or its sulphonic acids with an aromatic amine or its sulphonic acid,
whereby directly the aldehyde corresponding to the amine, or to its sulphonic
acid is formed together with an amine or its sulphonic acid corresponding to the
hydroxylamine.
For instance :-dimethylaniline, formaldehyde and m-sulpho-p-tolylhydroxylamine
furnishes the anhydrous compound of the dimethyl-p-amidobenzaldehyde with para-
toluidinesulphonic acid :-

page_text: or another example:-diphenylaminesulphonic acid, formaldehyde and phenyl-
hydroxylamine furnish the anhydrous compound of the aldehydodiphenylamine-
sulphonic acid together with aniline :-
:―
These anhydrous compounds are then decomposed by heating their solution with
alkalies or acids and obtaining on the one hand the corresponding amidoaldehyde or
its sulphonic acid, on the other hand an amidosulphonic acid or an amine. By
employing phenyl- or orthotolylbydroxylamine the separation of the pure aldehyde is
rendered somewhat difficult by the simultaneous formation of bye products as pará-
amidophenol, etcetera, out of the hydroxylamine in presence of acids, but this does
not happen when starting from a sulphonic acid of an aroinatic hydroxylamine which
distinguish themselves at the same time by a much better power of reaction.
My correspondents have had very favourable results in employing the hydroxyl-
aminesulphonic acids obtained by reduction of the generally known sulphonic acids
of the nitrobenzene, of the ortho and paranitrotoluene according to the process
described in the German Patent Specifications 84138 and 89978 with powder of zinc
in neutral aqueous solution in presence of certain salts as chloride of ammonia,
chloride of calcium, etcetera. Likewise the hydroxylamines deriving from other
nitro compounds as paranitrotoluene, m-nitrobenzoic acid, m-nitro-o-chlorbenzene
sulphonic acid are fit to this reaction, without any advantage however.
The process of the invention for the production of aldehydes may be modified in
the way that the hydroxylamine sulphonic acids enter into reaction in statu hascendi
with the amine in presence of formaldehyde. This may be accomplished by reduction
of a mixture of nitrobenzene or nitrotoluene sulphonic acid, amine, and formaldehydê;
in acid solution, either by introduction of a reducing agent, for instance, powder of
zine, powder of aluminium, iron filings, etcetera, or by the reaction of electrolytically
generated hydrogen. In both cases the aldehydes separate in combination with
toluidine sulphonic acid or metanilic acid as benzylidene compounds which may be
decomposed into their components in the above described manner.
The following examples are given to illustrate the general method of carrying
out the invention but my correspondents do not limit themselves to the precise
METASULPHOPARATOLYLHYDROXYLAMINE.
In an iron drum provided with a horizontal stirrer and a safety valve and the
exterior of which drum may be cooled by cold water, 100 kilos. of commercially
pure sodium paranitrotoluene sulphonate (obtained by sulphonation of paranitro-
toluene; precipitation with salt water, filtration, and drying) and 15 kilos. of chloride
of ammonia are dissolved in 400 liters of boiling water. The acid solution is
exactly neutralised by ammonia and cooled while stirring. To the thick pap of
crystals are now added, while constantly stirring and as quickly as the consider-
able heating brought down by exterior cooling allows it, 80 kilos. of powder of
R

page_text: zinc, in avoiding the entrance of air as much as possible. In a very short time
the reaction is finished, which may be easily seen by a rapid diminution of the
temperature. When the contents of the drum are completely cold, they are
quickly passed through a filter press and the cakes of oxide of zinc coming out
of the press are washed out with 250 liters of water. The whole filtrate acidulated 5
with 20 kilos. of hydrochloric acid can at once be employed for production of the
aldehyde.
The reduction of other nitro compounds, as for instance, nitrobenzene sulphonic
acid, nitrobenzoic acid, etcetera, to the corresponding hydroxylamine derivates, is
accomplished in exactly the same way. A characteristic of all these sulphonic acids
of aromatic hydroxylamines is their enormous solubility which makes their separation,
for instance, by addition of common salt, quite impossible.
II. PRODUCTION OF AROMATIC PARAAMIDOALDEHYDES.
1. DIMETHYL-P-AMIDOBENZALDEHYDE.
To the cold solution of 36 kilos. of dimethylaniline in 45 kilos. muriatic acid 1
of 21° Bé. are added 22.5 kilos. formaldehyde of 40 per cent. and at once the acidulated
solution of metasulphoparatolylhydroxylamine obtained after I (about 600 liters).
The mixture very soon gets a deep orange colour and the separation of the anhydrous
compound in form of yellow crystalline precipitate begins. After 48 hours the latter
is filtered off, washed, dissolved in ammonia, and boiled up, whereupon the 2
aldehyde separates in oily drops crystallising when cold. Filtered off and crystallised
again from water, it has already the exact melting point of 73° C., as well as all the
other properties of the known dimethyl-p-amidobenzaldehyde.
2. ORTHOCHLORODIMETHYL-P-AMIDOBENZALDEHYDE.
To a solution of 25 kilos. of sodium nitrobenzene sulphonate and 10 kilos. of 2
metachlordimethylaniline in 90 kilos. muriatic acid and 300 liters of water are
introduced, while constantly stirring, at 40° C., 5 kilos. of formaldehyde of
40 per cent. and 15 kilos. of iron filings. After a short time the solution takes a deep
yellow shade and the benzylidene compound begins to separate in reddish yellow
crystals. The precipitate not increasing any more, it is filtered, dissolved in a solution 3
of carbonate of soda and again filtered in order to remove the iron; the already known
aldehyde may be obtained by heating up with caustic soda.
In the same way my correspondents have prepared the following hitherto unknown
aldehydes :-
From monomethyl-o-toluidine. Small colourless leaves; melting point 114° C.,
sparingly soluble in water, easily in benzene, alcohol, and diluted acids.
From monoethyl-o-toluidine. Long thin needles; melting point 70° C.

page_text: 7. METHYLBENZYL-P-AMIDOBENZALDEHYDE.
From methylbenzylaniline. Thick yellow prisms; melting point 63° C., readily
soluble in alchol, ether, and benzene, sparingly soluble in petrolether. Its solution
in concentrated muriatic acid dissociates completely when diluted with water.
From benzylaniline. Semi fluid yellow resin, crystallising after some time; easily
soluble in alcohol, ether, and benzene, sparingly in petrolether; insoluble in diluted
acids.
From benzyl-o-toluidine. I ellow non crystallising resin; solubility like the
preceding aldehyde.
11. PHENYL-P-AMIDOBENZALDEHYDE.
To the cold (5° C.) solution of 50 kilos. diphenyl-amine in 400 liters alcohol are
added 22.5 kilos. formaldehyde of 40 per cent., then is rapidly introduced the
solution of tolylhydroxylamine sulphonic acids (600 liters) acidulated with 40 kilos.
(instead of 20 kilos.) muriatic acid and likewise cooled to 5° C., care being taken to
constantly stir the liquid while adding the hydroxylamine. The diphenylamine
separating in thin leaves by dilution of the alcohol and thus transforming the
liquid into a thick paste dissolves very soon, at the same time the liquid gets a
deep orange colour and afterwards a brown red colour and separates again a brown
red precipitate. After 8 hours there is added as much of a warm solution of
carbonate of soda till the whole mass dissolves with a bright yellow shade whereupon
the alcohol is driven away by means of steam. The remaining solution, when
troubled by small quantities of bye products and being still hot has cominon
salt added to it until it becomes quite clear, and is filtered when cold. The
anhydrous compound of phenyl-p-amidobenzaldehyde with toluidine sulphuric acid
contained in the yellow filtrate as sodium salt cannot be completely decomposed
by treating with alkalies like the anhydrous compounds of the preceding examples.
A splitting off of toluidine sulphonic acid takes place, Lut the separating products
which contain the aldehyde are still soluble in alkali because they are mixtures
with toluidine sulphonic acids. In order to accomplish a complete decomposition,
the above mentioned filtrate is diluted with water up to 4000 liters, then
acidulated with acetic acid and boiled up. When the turpidity taking place by
heating does not increase any more, neutralisation is effected with soda lye and
precipitation with common salt. The filtered precipitate consisting of a mixture of
free aldehyde and still undecomposed anhydrous compound is treated with ether in
order to dissolve the aldehyde.
Phenyl-p-amidobenzaldehyde forms a yellow glassy mass like colophony, brittle
and pulverisable when cold and getting soft when warm and forming at 70° C. a
thick oil. It dissolves readily in ether and benzene, less in alcohol, scarcely in cold
and boiling water. It shews a very characteristic behaviour against para-
phenylendiamine. All the preceding aldehydes furnish with this diamine cinnabar
red to blueish red precipitates, but when a piece of filtering paper impregnated with
an alcoholic or etheric solution of phenyl-p-amidobenzaldehyde is touched with a
solution of the chlorhydrate of paraphenylendiamine, it takes first a brownish red
shade, which passes very soon over in a deep violet black.

page_text: 12-13. METHYL, AND ETHYLPHENYL-P-AMIDOBENZALDEHYDES.
From methyl and ethyldiphenylamine. Resemble very much the above
mentioned aldehydes, they only remain resinous when cold and furnish with
paraphenylendiamine on paper not violet black but deep violet brown. shades with
metallic lustre.
A solution of m-sulpho-p-tolylhydroxylamine prepared according to I is mixed with
22.5 kilos. of formaldehyde of 40 per cent. and then introduced into a lukewarm.
solution of 40 kilos. of a naphtalamine in 50 kilos. muriatic acid and 2000 liters of
water. The yellow precipitate. immediately formed becomes deep reddish brown
after 24 hours; it is filtered, washed and decomposed. in the, described manner.
This aldehyde is obtained probably in polymeric form as an amorphous yellowish
brown powder insoluble in water, sparingly soluble in alcohol, better in ether and
benzenė.
17. ALDEHYDODIPHENYLAMINESULPHONIC ACID.
A solution of 80 kilos. of sodium diphenylamine sulphonate in 300 liters of water,
acidulated by addition of 10 kilos. muriatic acid has added to it 22.5 kilos. of formal-
dehyde and the acidulated solution of sulpho-tolylhydroxylamine. Immediately
afterwards the solution turns to yellow; after two days the orange precipitate is
brought into solution by addition of hot water and then is added a solution of
chlorhydrate of aniline or rather paratoluidine as long as a precipitate is forming. It
is filtered off, washed, dissolved with, carbonate of soda and all the aniline or para-
toluidine driven away by means of a current of steam. The solution is now com-
pletely saturated with common salt at 40°-50° C., whereby the sodium salt of the
aldehydodiphenylamine sulphonic acid separates in half solid soft lumps. Separated
from the mother lye and dried, it forms a bright yellow powder very soluble in water...
its solution turns to brown red with muriatic acid without the formation of a pre-..
cipitate. With the chlorhydrate of aniline it furnishes an orange red, with para-
phenylenediamine a deep brown red precipitate. Aldehydomethyl- and ethyl-
diphenylamine sulphonic acids can be prepared in the same way from. methyl- and
ethyldiphenylamine sulphonic acids.
18-19. ALDEHYDOMETHYL- AND ETHYLBENZYLANILINE SULPHONIC ACIDS.
From methyl and ethylbenzylaniline sulphonic acids. Production like, that of 17.
The sodium salts dissolve extremely well in water and well in hot alcohol. When.
acidulated there is no precipitation. The first gives with a paraphenylenediamine a
very bright cinnabar red, the second, a blueish red precipitate with metallic green-
lustre. Their hydrazones which are obtained by heating with phenylhydrazine in
acetic acid solution as crystalline precipitates, are colourless.
20-21. ALDEHYDOBENZYLANILINE- AND BENZYLORTHOTOLUIDINE SULPHONIC ACIDS.

page_text: From
27. ORTHOCHLORMONOETHYL-P-AMIDO-M-TOLUYLALDEHYDE.
metachlor-monoethyl-o-toluidine. Thin yellowish needles; melting
point 78° 79° C. Very soluble in alcohol and ether, less in benzene. The muriatic
solution dissociates by addition of water.

page_text: From diethylaniline. Needles. Melting point 41° C.
Having now particularly described and ascertained the nature of 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 :-
1. The manufacture and production of aromatic paraamido aldehydes belonging to
the benzene as well as to the naphtaline series and their alkylated phenylated,
alphylated, benzylated and sulphonic derivates, which consists in the simultaneous
or gradual reaction of formaldehyde and an aromatic hydroxylamine derivative or its
sulpho acid in acid or neutral solution upon primary, secondary, or tertiary aromatic
amines having an unhindered para position and being substituted in the benzene ring
or in the amido group or not and in the further decomposition of the thus obtained
anhydrous compounds of aldehyde and amine or its sulpho acid by heating with
aqueous alkalies or diluted acids, substantially as described.
2. Modification of the above process for the production of aromatic paraamido
aldehydes, which consists in the reaction of aromatic hydroxylamine compounds in
statu nascendi upon the amine and the formaldehyde by reducing a mixture of a
nitro compound, of an amine and of formaldehyde in presence of an acid either by
introduction of a reducing agent such as powder of zinc, powder of aluminium, iron
filings, or by the reaction of electrolytically generated hydrogen, substantially as
described.
meta-
monomethyl-
3. The manufacture and production of the following aldehydes :-paraamidobenz-
raldehyde, paraamidometatoluylaldehyde, orthochloroparaamidobenzaldehyde, ortho-
chloroparaamidometatoluylaldehyde, metamethoxyparaamidobenzaldehyde,
ethoxyparaanidobenzaldehyde, inonomethylparaamidobenzaldehyde,
paraamidometatoluylaldehyde, orthochloromonomethylparaamidometatoluylaldehyde,
monoethylparaamidobenzaldehyde, orthochloromonoethylparaamidobenzaldehyde,
monoethylparaamidometatoluylaldehyde, orthochloromonoethylparaamidometatoluyl-
aldehyde, dimethylparaamidobenzaldehyde, orthochlorodimethylparaamidobenzalde-
hyde, diethylparaamidobenzaldehyde, orthochlorodiethylparaamidobenzaldehyde,
monobenzylparaamidobenzaldehyde, monobenzylparaamidometatoluylaldehyde, ortho-
chloromonobenzylparaamidobenzaldehyde, orthochloromonobenzylparaamidometato-
luylaldehyde, methylbenzylparaamidobenzaldehyde, orthochloromethylbenzylpara-
amidobenzaldehyde, ethylbenzyl paraamidobenzaldehyde, orthochloroethylbenzyl para-
amidobenzaldehyde, phenylparaamidobenzaldehyde, methylphenylparaamidobenzalde-
hyde, ethylphenylparaamidobenzaldehyde, orthooxydimethylparaamidobenzaldehyde,
orthooxydiethylparaamidobenzaldehyde, dimethylparaamidoorthotoluylaldehyde, ortho-
orthodichloroparaamidobenzaldehyde, orthoorthodichlorodimethylparaamidobenzalde-
hyde, orthometadichlorodimethylparaamidobenzaldehyde, a 1-amido-a 2-naphtaldehyde,
paraaldehydodiphenylamine sulphonic acid, paraaldehydomethyldiphenylamine sul-
phonic acid, paraaldehydoet byldiphenylamine sulphonic acid, paraaldehydobenzyl-
aniline sulphonic acid, paraaldehydobenzylorthotoluidine sulphonic acid, paraalde-
hydomethylbenzylaniline sulphonic acid, paraaldehydoethylbenzylaniline sulphonic
acid, paraaldehydodibenzylaniline monosulphonic acid, paraaldehydodibenzylaniline
disulphonic acid (in all the abovenamed benzylated derivation the sulpho group being
in the benzyl rest) a 1 aldehydo- a 2 naphtylamine ẞ 2 sulphonic acid, obtained by the
reaction of formaldehyde and one of the following hydroxylamine compounds :-
paratolylhydroxylamine, metasulphophenylhydroxylamine, metasulphoparatolyl-
hydroxylamine, metasulphoorthotolylhydroxylamine, metasulphoparachlorophenyl-
hydroxylamine, metahydroxylaminebenzoic acid, upon the following amines:-aniline,
orthotoluidine, metachloraniline, metachlororthotoluidine, orthoanisidine, orthophene-

page_text: tidine, monomethylaniline, monomethylorthotoluidine, metachlormonomethylortho-
toluidine, monoethylaniline, metachlormonoethylaniline, monoethylorthotoluidine,
metachlormonoethylorthotoluidine, dimethylaniline, metachlordimethylaniline, die-
thylaniline, metachlorodiethylaniline, monobenzylaniline, monobenzylorthotoluidine,
metachloromonobenzylaniline, metachloromonobenzylort hotoluidine, methylbenzyl-
aniline, metachloromethylbenzylaniline, ethylbenzylaniline, netachlorethylbenzylanil-
ine, diphenylamine, methyldiphenylamine, ethyldiphenylamine, dimethylmetaamido-
phenol, diethylmetaamidophenol, dimethylmetatoluidine, metametadichloraniline,
metametadichlorodimethylaniline, orthometàdichlorodimethylaniline, a naphtylamine,
paradiphenylamine monosulphonic acid, paramethyldiphenylamine monosulphonic
acid, paraethyldiphenylamine monosulphonic acid, benzylaniline monosulphonic acid,
benzylorthotoluidinemonosulphonic acid, methylbenzylanilinemonosulphonic acid,
ethylbenzylanilinemonosulphonic acid, dibenzylanilinemonosulphonic acid, dibenzyl-
anilinedisulphonic acid, a 1-naphtylamine-ẞ 1-monosulphonic acid, substantially as
described.
4. As new products the aldehydes such as are obtained by the processes claimed
in the preceding first, second and third claims, substantially as described.
THOMAS R. SHILLITO,
15, Tooks Court, London, E.C.