The Manufacture or Production of Chemical Compounds from Halogenphtalimides.
Year: 1899

page_text: [Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH BAYER
& Co., of Elberfeld, Germany, Manufacturers.]
The Manufacture or Production of Chemical Compounds from
Halogenphtalimides.
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 to be as follows:-
My foreign correspondents discovered some time since the production of new
halogen derivatives of phtalimide having the general formula:
CO
CH₁
NX
CO
(X meaning in this formula an halogen atom, such as chlorine bromine or the
like.)
My foreign correspondents have now found that the said halogenphthalimides can
be used as starting materials for the production of valuable chemical compounds
inasmuch as they yield by a suitable treatment the following ortho disubstituted
products of the benzene series, viz. dialkylesters of the carboxyanthranilic acid,
anthranilic acid, carboxyalkylanthranilic acids and isatoic acid.
producing these bodies proceeds in, the following manner.
The process for
alcoholic solutions of alkaline alcoholates the halogenphthalimides are transformned
By the action of dilute
into the hitherto unknown dialkylesters of the carboxyanthranilic acid which have
the formula.

page_text: if they are treated with acetyl chloride or acetic anhydride.
In order to illustrate the production of the above mentioned compounds more fully
the following examples are given the parts being by weight.
EXAMPLE A.
PRODUCTION OF CARBOXYANTHRANILIC ACID DIMETHYLESTER.
To a solution of 4 parts of metallic sodium in 200 parts of absolute methylalcohol
(free from acetone) which solution has been cooled down to zero 40 parts of bromnyl-
phthalimide are added. The bromine compound dissolves slowly whilst the tempera-
ture rises a little and the solution assumes a slightly yellowish red color. After
having allowed the reaction mass to stand for several hours it is heated on a water
bath for about one hour. Subsequently the mixture is cooled then it is neutralized
by means of diluted hydrochloric acid and finally rendered slightly acid by the
addition of acetic acid. On distilling off the alcohol with the aid of a water bath a
red brown oil remains which solidifies on cooling. In order to purify the product
thus produced it is triturated with diluted caustic soda lye filtered off, washed with
water and dried. Subsequently it is distilled in vacuo. It distills over in the shape
of a colourless oil which on cooling changes into a crystalline mass.
The pure
neutral dimethylester of the carboxyanthranilic acid thus obtained is readily soluble
in ether, ligroin and alcohol. It crystallizes from ligroin in the shape of small
needles melting at from 60° to 61° Centigrade. According to analytical researches
it has the formula.

page_text: and a saturated watery solution of crystallized baryum hydrate [B a (OH)2] is heated
to boiling. After a short while the reaction sets in according to the following
equation.

page_text: instead of acetylchloride or if in place of carboxymethylanthranilic acid other
carboxyalkylanthranilic acids are employed.
My foreign correspondents do not intend to confine themselves to the particulars
given in the above examples as these are merely. typical and can be varied within
wide limits.
The Manufacture or Production of Chemical Compounds from
Halogenphtalimides.
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 correspondent's produced, some time since, new halogen derivatives
of phthalimide, having the general formula
CH
NX
(X meaning, in this formula, an halogen atom, such as cholorine. bromine, or
the like).
My foreign correspondents have now found that the said halogen phthalimides
can be used as starting materials for the production of valuable chemical com-
pounds, inasmuch as they yield, by a suitable treatment, the following
orthodisubstituted products of the benzene. series, viz., dialkylesters of the
carboxyanthranilic acid, anthranitic acid, carboxy-alkylanthranilic acids, and
isatoic acid. The process for producing these bodies proceeds in the following
manner :-
By the action of dilute alcoholic solutions of alkaline alcoholates, the halogen
phthalimides are transformed into the hitherto unknown dialkylesters of the
carboxy-anthranilic acid, which have the formula-

page_text: is produced, whilst, when the said dialkyl esters are treated with alcoholic solutions of
alkalies, carboxyalkylanthranilic acids of the general formula
when treated with acetyl chloride.
\N CO.OH
In order to illustrate the production of the above-mentioned compounds more
fully, the following examples are given, the parts being by weight.
EXAMPLE A.
PRODUCTION OF CARBOXYANTHRANILIC ACID DIMETHYLESTER.
To a solution of 4 parts of metallic sodium in 200 parts of absolute methyl alcohól
(free from acetone), which solution has been cooled down to zero, 40 parts of
bromylphthalimide are added. The bromine compound dissolves slowly, whilst the
temperature rises a little, and the solution assumes a slightly yellowish-red color.
After allowing the reaction mass to stand for several hours, it is heated on a water-
hath for about one hour. Subsequently, the mixture is cooled ; then it is neutralized
by means of dilute hydrochloric acid, and finally rendered slightly acid by the addition
of acetic acid. On distilling off the alcohol with the aid of a water-bath, a reddish-
brown oil remains, which solidifies on cooling. In order to purify the product thus
produced, it is triturated with dilute caustic soda-lye, filtered off, washed with water,
and dried. Subsequently, it is distilled in vacuo. It distils over in the shape of n
colorless oil, which, on cooling, changes into a crystalline mass. The pure neutral
dimethylester of the carboxyanthranilic acid thus obtained is readily soluble in ether,
ligroine, and alcohol. It crystallises from ligroine in the shape of small needles
melting at from 60° to 61° Centigrade.
According to analytical researches, it has the formula

page_text: and a saturated watery solution prepared from 47.3 parts of crystallized barium
hydrate (Ba(OH)2 corresponding to 15 molecules) is heated to boiling. After a short
time, the reaction sets in according to the following equation :-
hours, the reaction will be finished, the mixture being meanwhile transformed into a
thick mass. Subsequently, the barium carbonate is removed therefrom by filtration.
Into the hot liquid thus obtained, carbonic acid anhydride is introduced, in order to
remove the excess of barium hydrate possibly still contained therein. The liquid is
then again filtered, and evaporated to dryness. Thus, the barium sait of anthranilic
acid is obtained. The free acid can be produced therefrom in the usual manner.
The process proceeds in an analogous manner, if, instead of barium hydroxide,
watery solutions of other earthy alkalies, such as lime-water or the like, are employed,
or if, in place of the diethylester, other neutral esters or carboxyanthanilic acid are
used.
EXAMPLE C.
PRODUCTION OF CARBOXYMETHYLANTHRANILIC ACID FROM CARBOXYANTHRANILIC
ACID DIMETHYLESTER.
To a solution of 10 kilos. of the neutral dimethylester of carboxyanthranilic acid in
20 litres of absolute methylalcohol, 12 litres of a solution of caustic potash in methyl-
alcohol (which solution contains in each litre 340 grammes of caustic potash) are
added. A white precipitate is thus separated, which dissolves on heating the mixture
on a water-bath. Subsequently the liquid is boiled for several hours, and the alcohol
is then distilled off. The residue thus obtained is dissolved in water. On acidulat-
ing the resulting solution with dilute sulphuric acid, the carboxymethyl anthranilic
acid is precipitated as a white mass, which is further purified by a crystallization
from hot water or benzene. It crystallizes in the shape of small leaves, melting at
176° Centigrade. The acid thus obtained exhibits the properties indicated by
G. Schmidt (see "Journal für pract. Chemie," Vol. 36, p. 375).
It is almost insoluble in ligroin, readily soluble in acetic ether, in methyla!cohol,
and in ethyl alcohol. ⚫
The process proceeds in a similar manner, if the carboxyethylanthranilic acid
(melting at 126° Centigrade) is to be produced from the neutral diethylester of
carboxyanthranilic acid.
EXAMPLE D.
PRODUCTION OF THE ISATOIC ACID.
A mixture prepared from 10 kilos. of carboxyethylanthranilic acid and 30 kilos. of
acetylchloride is heated for several hours on a water-bath. Subsequently, the excess
of acetylchloride is distilled off. The isatoic acid thus obtained is finally purified in
the known manner. It exhibits the known properties (see "Berichte der deutschen
chemischen Gesellschaft," Vol. 22, p.p. 1673 and 1674).
The reaction takes place in an analogous manner, if, in place of carboxy-
methylanthranilic acid, other carboxyanthranilic acids are employed.

page_text: My foreign correspondents do not intend to confine themselves to the par-
ticulars given in the above examples, as these are merely typical, and can be varied
within wide limits.
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 process for the production of the neutral esters of carboxyanthranilic acid,
which process consists in treating the halogen phthalimides with dilute alcoholic
solutions of alkaline alcoholates, substantially as herein before described.
2. The process for the production of anthranilic acid, which process consists in
treating the above mentioned neutral esters of carboxyanthranilic acid with
hydroxides of earthy alkalies, substantially as herein before described.
"
3. The process for the production of carboxyalkylanthranilic acids, which process
consists in treating the hereinbefore defined neutral esters of carboxyanthranilic
acid with alcoholic solutions of alkalies, substantially as herein before described.
4. The process for the production of isatoic acid, which process consists in
treating the above-named carboxyanthranilic acids with acetyl chloride, substantially
as hereinbefore described.
5. As new articles of manufacture, the products obtainable by the processes
herein before described and claimed.