Processes for Converting Substitution Derivatives of Amidobenzoyl- benzoic Acids and Substitution Derivatives of Oxyamidobenzoyl- benzoic Acids into Corresponding Anthracene Derivatives.
Year: 1898

page_text: Processes for Converting Substitution Derivatives of Amidobenzoyl-
benzoic Acids and Substitution Derivatives of Oxyamidobenzoyl-
benzoic Acids into Corresponding Anthracene Derivatives.
I, JOHN IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, in the County
of London, Consulting Engineer and Chartered Patent Agent, do hereby declare the
nature of this invention (as communicated to me from abroad by La Société
Anonyme des Matieres Colorantes et Produits Chimiques de St. Denis, of 105, Rue
Lafayette, Paris, Albin Haller and Alfred Guyot, of Nancy, France) to be as
follows:-
This invention relates to the conversion of substitution derivatives of amido-
benzoylbenzoic acids and of oxyamidobenzoylbenzoic acids into anthracene
derivatives.
The amidobenzoylbenzoic acids in question are prepared by the method described
by my foreign correspondents (Comptes Rendus de l'Academie des Sciences, Vol. 119,
page 205). Their conversion into anthracene derivatives of the form
CH
CH,NR, or CH
CH₂
ND
II. This second method presents the same general characteristic as the first and
yields finally the same products; but it is distinguished by the fact that the
anthracene condensation is effected through benzyl derivatives which are obtained by
the reduction of the parent benzoyl derivatives,
Example. When dimethylamidobenzoylbenzoic acid is reduced by zine or by
sodium amalgam the following change occurs :-

page_text: This reduction occurs in two phases and there can be isolated a monophenyl-
phthalide
In either case, whether the two phases are separated or combined, the product
when heated with strong sulphuric acid undergoes the anthracene condensation,
yielding products which have all the characters of anthranols.
at to the fukewarm surp
acid solution of the antirano produces a reddisn
violet colouration, probably due to the formation of the oxyanthranol; and if this
solution be heated to from 50° to 60° C. the red needles of dimethylamido-anthra-
quinone, the last of the reaction may be observed.
The same substance can be directly obtained by starting from the corresponding
anthranol; a current of air passing through an alkaline solution of the anthranol
determines an abundant precipitation of red flocks of dimethylamidoanthraquinone.
EXAMPLE I.
A pot of about ten litres capacity, not enamelled, is charged with 7 litres of
water, 350 grams of caustic soda and 200 grams of dimethylamido-benzoyl-benzoic
acid. The mixture is heated to its boiling point and 400 grams of zinc powder are
thrown in in small portions during 24 hours. When the reduction is completed the
excess of zinc is separated by filtration, and the filtered solution is so far neutralised
that it has only a feebly alkaline reaction. The temperature is again raised to the
boiling point and the boiling liquid is precipitated by adding acetic acid until the
liquid is decidedly acid. The benzylated acid is thus precipitated in the form of
small dirty white spangles melting at 173° C. The ebullition is continued for some
moments, the whole is allowed to cool and settle and the precipitate is washed and
dried; it can be used as such for the preparation of the anthracene product, for which
purpose a solution of one part of it in 10 parts of strong sulphuric acid is heated at
80° C; at the end of from 25 to 30 minutes the greenish solution thus obtained is
poured into 15 parts of water, 700 cubic centimetres of ferric chloride solution
(13 specific gravity) are added per kilo. of acid and the whole is boiled for several
hours. This ebullition renders more crystalline the red precipitate formed in the
first instance. When the liquid has cooled it is allowed to settle and the solid matter
is washed on the filter; the product is very pure from the first and is in the form of
red needles which melt at 181° C.
In this example one may substitute for the dimethylamidobenzoylbenzoic
acid :—
(1) 220 grams of diethylamidobenzoylbenzoic acid; the corresponding derivative
melts at 108° C and the diethylamidoanthraquinone is in the form of red needles
which melt at 162° C.
(2) 256 grams of methylbenzylamidobenzoylbenzoic acid, or
266 grams of
ethylbenzylamidobenzoylbenzoic acid; in these two cases the benzylated derivatives
and the anthraquinone derivatives are obtained in the form of pasty masses,

page_text: This second method is well applicable to dialkylated amidometaoxybenzoylbenzoic
acids or to sulphonic acids of dialkylated amidobenzoylbenzoic acids; the benzylated
derivative is first made, then by means of sulphuric acid containing 30 per cent. of
anhydride the oxidation to anthraquinone can be realized at the same time as the
anthracene condensation; sulphonation occurs and there is an evolution of sulphur
dioxide. There will be used, for example, 7 litres of water, 350 grams of soda, and
221 grams of diethylamidometaoxybenzoyl-benzoic acid prepared by the methods
described in the German Specifications Nos. 85,931 and 87,068, and reduction is
effected by 400 grams of zinc powder; the corresponding benzylated hydroxyl
derivative is crystalline and melts at 196°-200° C. When treated with sulphuric
acid containing 30 per cent. of anhydride it yields the corresponding
anthraquinone sulphonic acid.
In this case there may be substituted for the diethylamidometaoxybenzoylbenzoic
acid the dimethyl-acid or the diethylamidobenzoylbenzoic acid described by
Haller and Guyot (Bulletin de la Société Chimique de Paris, 1896). The benzylated
derivative crystallises from water in the form of white needles and is converted into
an anthraquinone sulphonic acid in the manner previously described.
Dated this 5th day of May 1898
ABEL & IMRAY,
Agents for the Applicant.
Processes for Converting Substitution Derivatives of Amidobenzoyl-
benzoic Acids and Substitution Derivatives of Oxyamidobenzoyl-
benzoic Acids into Corresponding Anthracene Derivatives.
I, JOHN IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, in the
County of London, Consulting Engineer and Chartered Patent Agent, do hereby
declare the nature of this invention (as communicated to me from abroad by La
Société Anonyme des Matieres Colorantes et Produits Chimiques de St. Denis, of
105, Rue Lafayette, Paris, Albin Haller and Alfred Guyot, of Nancy, France) and in
what manner the same is to be perforined, to be particularly described and ascer-
tained in and by the following statement :-
This invention relates to the conversion of substitution derivatives of amidobenzoyl-
benzoic acids and of oxyamidobenzoylbenzoic acids into anthracene derivatives.
The amidobenzoylbenzoic acids in question are prepared by the method described
by my foreign correspondents (Comptes Rendus de l'Academie des Sciences, Vol. 119,
page 205).
Their conversion into anthracene derivatives of the form
CO.
CO
VR₁
CH₁
>CH,NR₂
or C₂H₁
C₂H₂
NR

page_text: I. This very simple method consists in heating a solution in strong sulphuric acid
of the substance to be converted, for some minutes at 175° C.
Example. Starting with dimethylamidobenzoylbenzoic acid, dimethylamidoanthra-
quinone is obtained.
Dimethylamidobenzoylbenzoic acid.
Dimethylamido-anthra-quonine.
II. This second method presents the same general characteristic as the first and
yields finally the same products; but it is distinguished by the fact that the
anthracene condensation is effected through benzyl derivatives which are obtained by
the reduction of the parent benzoyl derivatives.
Example. When dimethylamidobenzoylbenzoic acid is reduced by zinc or by
sodium amalgam the following change occurs:—
Oxidising agents convert the anthranols into corresponding anthraquinones. With
ferric chloride, for example, this oxidation occurs in two phases. Addition of ferric
chloride to the lukewarm sulphuric acid solution of the anthranol produces a reddish
violet coloration, probably due to the formation of the oxyanthranol; and if this
solution be heated to from 500 to 60° C. the red needles of dimethylamido-anthra-
quinone, the last stage of the reaction may be observed.
'
The same substance can be directly obtained by starting from the corresponding
anthranol; a current of air passing through an alkaline solution of the anthrano!
determines an abundant precipitation of red flocks of dimethylamido-anthra-
quinone

page_text: When the reduction is completed the excess of zinc is separated by filtration, and
the filtered solution is so far neutralised that it has only a feebly alkaline
reaction.
The temperature is again raised to the boiling point and the boiling liquid is
precipitated by adding acetic acid until the liquid is decidedly acid. The benzylated
acid is thus precipitated in the form of small dirty white spangles melting at
173° C.
The ebullition is continued for some moments, the whole is allowed to cool and
settle and the precipitate is washed and dried; it can be used as such for the
preparation of the anthracene product, for which purpose a solution of one part of it
in 10 parts of strong sulphuric acid is heated at 80° C.; at the end of from 25 to
30 minutes the greenish solution thus obtained is poured into 15 parts of water,
700 cubic centimetres of ferric chloride solution (1-3 specific gravity) are added per
kilo of acid and the whole is boiled for several hours. This ebullition renders more
crystalline the red precipitate formed in the first instance. When the liquid has
cooled it is allowed to settle and the solid matter is washed on the filter; the product
is very pure from the first and is in the form of red needles which inelt at
181° C.
In this example one may substitute for the dimethylamidobenzoylbenzoic
acid-
(1) 220 grams of diethylamidobenzoylbenzoic acid; the corresponding derivative
melts at 108° C. and the diethylamidoanthraquinone is in the form of red needles
which melt at 162° C.
(2) 256 grams of methylbenzylamidobenzoylbenzoic acid, or 266 grams of
ethylbenzylamidobenzoylbenzoic acid; in these two cases the benzylated derivatives
and the anthraquinone derivatives are obtained in the form of pasty masses.
This second method is well applicable to dialkylated amidometa oxybenzoylbenzoic
acids or to sulphonic acids of dialkylated amidobenzoylbenzoic acids; the
benzylated derivative is first made, then by means of sulphuric acid containing
30 per cent. of anhydride the oxidation to anthraquinone can be realised at the same
time as the anthracene condensation; sulphonation occurs and there is an evolution
of sulphur dioxide. There will be used, for example, 7 litres of water, 350 grams of
soda, and 291 grams of diethylamidometaoxybenzoylbenzoic acid prepared by the
methods described in the German Specifications Nos. 85,931 and 87,068, and
reduction is effected by 400 grams of zinc powder; the corresponding benzylated
When treated with
hydroxyl derivative is crystalline and melts at 196° to 200° C.
sulphuric acid containing 30 per cent. of anhydride it yields the corresponding
anthraquinone sulphonic acid.
In this case there may be substituted for the diethylamidometaoxybenzoylbenzoic
acid the dimethyl-acid or the diethylamidobenzoylbenzoic acid described by Haller
and Guyot (Bulletin de la Société Chimique de Paris, 1896). The benzylated
derivative crystallises from water in the form of white needles and is converted into
an anthraquinone sulphonic acid in the manner previously described.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
--
1. A process for converting substituted amido-derivatives substituted oxy-amido-
derivatives and sulphonic acids of substituted amido-derivatives of benzoylbenzoic
acid into anthracene derivatives by heating for some minutes at a temperature about
175° C a solution of the compound to be converted in strong sulphuric acid
substantially as described.

page_text: 2. A process for effecting the conversion referred to in Claim 1 by reducing the
compound to be converted so as to form an intermediate benzylated derivative and
subsequently oxidising this derivative, substantially as described.
3. The intermediate derivatives obtained as set forth in Claim 2.
4. The anthracene derivatives obtained as set forth in Claims 1 and 2.
ABEL & IMRAY,
Agents for the Applicant.