Production of New Derivatives of Alkyl-hydroxy-para- amidobenzenes.
Year: 1897

page_text: Production of New Derivatives of Alkyl-hydroxy-para-
amidobenzenes.
WILLIAM HENRY CLAUS & ALFRED REE, Chemical Manufacturers, both of Clayton,
Manchester, and LEON MARCHLEWSKI, Chemist, of 25, Wellington Street, Higher
Broughton, Manchester, do hereby declare the nature of this invention to be as
follows:-
The invention relates to the production of condensation products of certain
carbohydrates with para-phenetidine or para-anisidine. We use those carbohydrates,
which according to the views of some writers (Fittig comp. Zertschirft für Chemie,
1869 p. 266; Fischer Berichte der Deutschen Chem. Gesellschaft, 1895 p. 1145)
contain an aldehyde group, or which according to others (Tollens Berichte di
Deutschen Chem. Gesellschaft 16 p. 933; Marchlewski Journal of the Chemical
Society London 1893 p. 1041) contain a group capable of being transformed under
certain circumstances into an aldehyde group.
The condensation takes place readily in alcoholic solution and can be formulated in
the case of glucose or another monose of the given description and paraphenetidine
being used as follows:-
given:
10 parts of glucose are heated with 150 parts of alcohol and 40 parts of
paraphenetidine on a waterbath for 3-6 hours. The glucose goes gradually into
solution.
When all is dissolved the solution is further heated for 1 hour and one half of the
alcohol used distilled off. The residue is cooled down and mixed with a large excess
of ether, when the condensation product, glucophenetidid, will separate out as a white
Price Rdl

page_text: powder which is filtered off, washed with ether and finally crystallised from
alcohol.
The glucose of the foregoing example may be substituted amongst others by
d-fructose, d-gallactose, milk sugar and mattose; the paraphenetidine may be replaced
by para-anisidine.
WILLIAM HENRY CLAUS,
ALFRED RÉE,
LEON MARCHLEWSKI.
Production of New Derivatives of Alkyl-hydroxy-para-
amidobenzenes.
WILLIAM HENRY CLAUS and ALFRED RÉE, both Chemical Manufacturers, of Clayton,
Manchester, and LEON MARCHLEWSKI, Chemist, of 25, Wellington Street, Higher
Broughton, Manchester, 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 :-
The invention relates to the production of condensation products of certain carbo-
hydrates with para-phenetidine and para-anisidine.
We use those carbohydrates which, according to the views of some writers (Fittig
comp. Z. fur Chem. 1869, p. 266, Fischer Berichte 1894, p. 1,145) contain an alde-
hyde group;
or which, according to others (Tollens Berichte 1883, p. 921,
Marchlewski, Journal of the Chemical Soc., London, 1893, p. 1,137), contain a group
capable of being transformed, under certain circumstances, into an aldehyde group.
The condensation takes place readily in alcoholic solution, and can be, in case
glucose and p-phenetidine are used, formulated as follows:
CHgO + CH.NH,.OC H = HgO + C,H,O,.N.CH,0C,H.
12
The constitution of the condensation compound in case of glucose being used,
may be formulated thus:
CH₂.OH
(CH.OH).
H-C=N.CH..OCH
CH,.OH
(CH.OH),
ог
CH
CH.NH.C HỌC, H.
In order to illustrate the working of our invention, the following examples may be
3

page_text: then distilled off. On cooling of the solution, the condensation product separates
out in the form of a crystalline mass; next ether is added and the mass filtered off,
washed with ether, and finally crystallised from alcohol.
The gluco-p-phenetidide so obtained represents white crystals soluble in hot water
and alcohol; insoluble in ether. By the action of mineral acids, it is decomposed
into glucose and p-phenetidine. Its aqueous solution gives with ferric chloride
a brown coloration, and reduces readily silver salts. Its melting point is 160° C
D-GALACTO-P-PHENETIDide.
10 parts of galactose and about 40 parts of p-phenetidine are heated with 150
parts of alcohol on the water bath for several hours. The condensation product
separates out on cooling of the solution, and may be purified by crystallisation from
alcohol. Its properties are very similar to those of gluco-p-phenetidide. Its melting
point is 165° C.
The proportions of the ingredients as above given may be, of course, varied, but it
is advisable to apply an excess of the amine, especially in case expensive carbo-
hydrates are to be used.
The condensation of the carbohydrate with the amine can also be accomplished
by heating the two substances without the aid of a solvent, to higher temperatures--
for instance, 150°-230° C.
The p-phenetidine in the above examples may be substituted by p-anisidine, when
gluco-p-anisidide and galacto-p-anisidide will be obtained. The described compounds
are intended for medicinal use.
Having now particularly described and ascertained the nature of our said
invention, and in what manner the same has to be carried out, we declare that what
we claim is:—
1. The preparation or manufacture of gluco-p-phenetidide; gluco-p-anisidide;
galacto-p-phenetidide; galacto-p-anisidide by heating glucose or galactose with
p-phenetidine or p-anisidine in alcoholic solution; or by heating glucose or galactose
with p-phenetidine or p-anisidine without the aid of a solvent, substantially as
described.
2 As new products of manufacture the new compounds ·