The Manufacture and Production of a New Crystallized Compound of Anhydro-ortho-sulphamine Benzoic Acid.
Year: 1894

page_text: Date of Application, 23rd Nov., 1894
Complete Specification Left, 6th Dec., 1894-Accepted, 12th Jan., 1895
PROVISIONAL SPECIFICATION.
The Manufacture and Production of a New Crystallized Compound
of Anhydro-ortho-sulphamine Benzoic Acid.
1, JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of
London Gentleman do hereby declare the nature of this invention (which has
been communicated to me from Dr. F. von Heyden Nachfolger of Radebeul near
Dresden in the Empire of Germany) to be as follows:-
In the course of a series of experiments or trial, made by Professor Remsen
Johns Hopkins, University Baltimore in conjunction with his pupils on the
oxydation of the sulphonic acids and the sulphamides of toluene, xylene and the
like the results of which investigations have become known by chemical literature
Professor Remsen (in this part of his investigations assisted by Fahlberg)
discovered the anhydro-orthosulphamine benzoic acid.
This anhydro-ortho-sulphamine benzoic acid and its sodium salt is as is well
known the substance which imparts the sweet taste to saccharine which latter was
introduced into commerce by Fahlberg.
The commercial products sold under the name of saccharine are very seldom
pure anhydio-orthosulphamine-benzoic acid or pure anhydro-orthosulphamine-
benzoate of sodium.
The known commercial saccharine and also the so-called refined saccharine
nearly always contain admixtures which have no sweet taste and reduce the value
of the product.
The most frequent impurity is the parasulphamine benzoic acid which has an
acid or sour taste and forms up to 40% of that product which is known in
commerce under the name of saccharine purum. (See "Hefelmann" on Saccharine
of commerce and destination of its value. Pharmac. Centralhalle 1894 No. 87.)
This mixture of anhydro-orthosulphamine benzoic acid of 40% of parasulph-
amine benzoic acid and of other impurities forms the product named saccharine
which is described in the British Patent No. 6626 A.D. 1886.
In the trade the saccharine is sometimes furthermore diluted and adulterated by
admixing powdered substances which have the noncharacteristic appearance of the
initial product of commerce saccharine such for example as powdered sugar which
is 500 times cheaper than the pure sweet substance anhydro-orthosulphamine
benzoic acid.
The purchase of saccharine is therefore entirely in the hands of the manufacturer
or the trader; the consumer is entirely unable to ascertain whether the purchased
saccharine is free of any inferior or worthless admixtures and what percentage of
such admixtures the article purchased contains.
In order to determine such adulterations a complicated chemical analysis is
necessary.
The reason why the consumer cannot at once recognise whether the saccharine
purchased by him is a pure anhydro-orthosulphamine benzoic acid (or.the sodium
salt of it) and the reason why the commercial product saccharine is so frequently
adulterated, is that the product hitherto in commerce as saccharine has no
characteristic appearance but possesses the form of white or dirty white powder or
grain so that it is very easy to dilute or adulterate the saccharine by admixing
with it a soluble cheap powder of identical appearance which adulteration it is
impossible to recognise merely by the eye.
There is according to this invention provided a new product which enables

page_text: adulterations to be detected by the eye alone. The new product is the sodium salt
of anhydro-orthosulphamine benzoic acid in the new forms of crystals. It is to be
called Crystallose.
The crystal form gives a guarantee against every adulteration by worthless
mixtures as the purchaser can at once recognise merely by the eye whether the
substance offered to him in commerce contains besides the crystals of the crystallose
any foreign admixtures.
Between the hitherto powdered or grainy product of commerce-saccharine and
the new crystallized product of commerce-crystallose there exists a similar
relation or distinction as that which exists between calcined soda in its powdery
form and the crystal soda.
The calcined soda or soda-ash is in consequence of its powdery form subject to
adulteration and in fact it very seldom is purchasable by the smaller consumers in
a non-adulterated form. Admixtures of up to 40% of common salt sulphate of
sodium and so on are frequently met with in the soda of commerce.
On account of these frequent adulterations which are beyond control of the
ordinary purchaser the soda is preferred in the form of crystals instead of the
powdered calcined soda as the crystal form of the soda offers a guarantee at least
against too large an adulteration by the admixture of other salts.
With the crystallose the crystal form offers nearly a complete guarantee against
every adulteration by the admixture of foreign substances.
The crystallose has the chemical formula:

page_text: raw toluene sulphonamide is obtained. The first precipitation contains nearly the
entire quantity of orthotoluene sulphonamide whereas the second precipitation
contains but little ortho and considerable para amide.
The first precipitant with the main bulk of ortho-amide is now dissolved in a
second vessel in hot water with the addition of alkaline earth for example lime.
This solution contains the toluene sulphonamide as a salt of calcium.
To this solution which is of an highly alkaline reactive character permanganate
of potassium is added while the contents of the vessel are subjected to constant
stirring.
The solution at first will acquire the fine colour of the permanganate of potassium,
but will afterwards quickly discolour, because the permanganate of potassium will
decompose into oxygen, manganese and alkali. The oxygen will oxydise the
tolnene-sulphon amide. Further quantities of permanganate of potassium are
added as long as the solution coloured by it will readily discolour.
When this discolouring commences very slowly, the oxydation of the toluene
sulphon amide is completed.
The strongly alkaline solution is then freed from the suspended manganese by
filtration or still better by centrifugal action and hydrochloric acid is added to the
filtered fluid until the latter reacts neutrally.
This neutralised solution is concentrated by evaporisation in a vessel provided
with a steam jacket tall a sample taken from the concentrated fluid will it cooled
down, deposit crystals. The solution so concentrated is then run down from the
evaporating pan into a crystallizing vessel. If the solution cools down, mainly the
chloride of potassium and the para sulphamine-benzoate of potassium will
crystallise and the anhydro-ortho-sulphamin-benzoate of potassium which is more
easily soluble will remain in the mother lye. The concentrated solution is allowed
to crystallise in the crystallizing vessel for a period, such that the analysis of a
sample of the mother lye will shew that it contains but little parasulphamine
benzoic acid. Then the contents of the crystallizing pan are filtered through bags.
or by any known or suitable filtering device.
The mother lye resulting from this filtering process is treated in a vessel with
hydrochloric acid.
The resulting precipitate, consisting of pure or nearly pure anhydro-ortho
sulphamine benzoic acid, is then filtered and by washing it with water in a
centrifugal machine is freed from acid mother lye; the precipitate is afterwards
dissolved in hot water or diluted alcohol by the addition of soda up to neutral
reaction.
This dissolving process is effected by means of steam in an open vessel or if
alcohol be used, the employment of a closed vessel, provided with a cooler is
preferred.
For the complete discolouring of the boiling solution animal charcoal can be
added to it, the fluid being separated from said charcoal by filtration.
If the solution has properly cooled down, the pure product which is called
crystallose will crystallise in well formed crystals.
The crystals are freed from any adhering liquid and dried. The mother lye
after repeated concentration and cooling, will again yield crystals of crystallose.
2ND PROCESS.
Pure or nearly pure anhydro-orthosulphamine benzoic acid is dissolved in an open
1
111 to noutral reaction

page_text: Mixtures of anhydro orthosulphamine benzoic acid with parasulphaminebenzoic
acid, as such mixtures are for instance known as saccharinum purum in the trade,
are dissolved in hot water, in a vessel provided with a steam jacket, neutralizing
the solution with soda or potash. Afterwards the solution is concentrated, not up
to dryness, as in the production of the known soluble saccharine, but up to such a
point that a sample taken will crystallise in cooling down...
The so far concentrated solution is caused to run into a crystallising vessel and
left to crystallise until an analysis of the mother lye shews that it is free or almost
free from para sulphamine benzoic acid salts.
The contents of the crystallization vessel are then filtered.
The crystals will then contain all or nearly all paraacid salts, while the mother
lye will contain the anhydro-orthosulphamine benzoate of sodium or potassium.
If at first soda be used for neutralization, the resulting mother lyc-if necessary
after discolouring by animal charcoal-may be at once concentrated by further
evaporation. In the cooling down, crystals of the crystallose are obtained.
If Lowever at first potash has been used for neutralization the mother lye,
which contains the anhydro-orthosulphamine benzoate of potassium, is treated
with hydrochloric acid, until all anhydro-orthosulphamine benzoic acid has been
precipitated.
The latter is afterwards subjected to filtration and is converted into crystallose
according to the second process.
Dated this 23rd day of November 1894.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of a New Crystallised Compound
of Anhydro-ortho-sulphamine Benzoic Acid.
I, JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of London
Gentleman do hereby declare the nature of this invention (which has been
communicated to me from abroad by Dr. F. von Heyden Nachfolger of Radebeul
near Dresden in the Empire of Germany) and in what manner the same is to be
performed to be particularly described and ascertained in and by the following
statement :-
In the course of a series of experiments or trials made by Professor Remsen,
Johns Hopkins University Baltimore in conjunction with his pupils on the
oxydation of the sulphonic acids and the sulphamides of toluene, xylene and the like,
the results of which investigations have become known by chemical literature,
Professor Remsen (in this part of his investigations assisted by Fahlberg) discovered
the anhydro-orthosulphamine-benzoic acid.
This anhydro-ortho-sulphamine benzoic acid and its sodium salt is-as is well
known the substance which imparts the sweet taste to saccharine which latter was
introduced into commerce by Fahlberg.
The commercial products sold under the name of saccharine are very seldom
pure anhydro-orthosulphamine benzoic acid or pure auhydro-orthosulphamine-
benzoate of sodium.
The known commercial saccharine and also the so called refined saccharine,

page_text: nearly always contain admixtures which have no sweet taste and reduce the value
of the product.
The most frequent impurity is the para-sulphamine benzoic acid, which has an
acid or sour taste and forms up to 40% of that product which is known in commerce
under the name of saccharine purum. (See "Hefelmann " on Saccharine of
commerce and determination of its value. Pharmac. Centralhalle 1894 No. 8.)
This mixture of anhydroorthosulphamine benzoic acid, of 40% of parasulphamine
benzoic acid and of other impurities forms the product named saccharine which is
described in the Specification of the British Patent No. 6626, A.D. 1886.
In the trade saccharine is sometimes furthermore diluted and adulterated by
admixing powdered substances which are not distinguishable by the eye from the
initial product commercial saccharine, such for example as powdered sugar, which
is 500 times cheaper than the pure sweet substance anhydroorthosulphamine benzoic
acid.
The purchaser of saccharine is therefore entirely in the hands of the manufacturer
or the trader as the purchaser is quite unable to ascertain whether the saccharine
is free from any inferior or worthless admixtures or what percentage of such
admixtures the saccharine contains.
In order to determine such adulterations a complicated chemical analysis is
necessary.
The reason why the consumer cannot at once recognise whether the saccharine
purchased by him. is a pure auhydro-ortho-sulphamine benzoic acid (or the sodium
salt of it) and the reason why the commercial product saccharine is so frequently
a lulterated, is that the commercial product known as saccharine has no
characteristic appearance, but is in the form of white or dirty white powder or
grain, so that it is very easy, to dilute or adulterate the saccharine by admixing
with it a soluble cheap powder of identical appearance, which adulteration it is
impossible to recognise by the eye.
There is according to this invention provided a new product, which enables
adulterations to be detected by the eye alone. The new product is the sodium salt
of anhydroorthosulphamine benzoic acid in the new forms of crystals, and my
foreign correspondent has named it "Crystallose." The crystal form gives a
guarantee against every adulteration by worthless admixtures as the purchaser
can at once recognise merely by the eye, whether the substance offered to him in
commerce contains besides the crystals of the crystallose any foreign admixtures.
Between the hitherto powdered or grainy product commercial saccharine-and
the new crystallised product crystallose-there exists a similar relation or
distinction as that which exists between calcined soda in its powdery form and the
crystal soda.
The calcined soda or soda ash is in consequence of its powdery form-subject to
adulteration and in fact it very seldom is purchasable by the smaller consumers in
a non-adulterated form. Admixtures of up to 40% of common salt, sulphate of
sodium and so on are frequently met with in the soda of commerce.
On account of these trequent adulterations, which are beyond control of the
ordinary purchaser, the soda is preferred in the form of crystals, instead of the
powdered calcined soda, as the crystal form of the soda offers a guarantee at least
against too large an adulteration by the admixture of other salts."
With the crystallose the crystal form affords a complete or nearly complete
guarantee against every adulteration by the admixture of foreign substances.
The crystallose has the chemical formula :-

page_text: The crystallose is in the form of brilliant crystals, which in the pure state are
colourless and transparent. It readily dissolves in water and may be recrystallised
from it.
If a slightly diluted watery solution of hydrochloric acid be added, a white
precipitate of anhydroorthosulphamine benzoic acid will be thrown down.
The production of the crystallose may be effected in various ways.
1ST PROCESS.
Raw toluene sulphonamide is dissolved in soda lye in an open vessel. The
solution is afterwards separated from its impurities by filtration and the amide is
reprecipitated from the solution by means of acid. It is preferred not to
precipitate all the toluene sulphoamide at once, but in the first instance the main
bulk only. After this main bulk has been separated by filtration, the remaining
part of the toluene sulphonamide is precipitated out of the mother lye. In this
way a partial separation of the mixture of ortho and para toluenesulphonamide
contained in the raw toluene sulphonamide is obtained. The first precipitation
contains nearly the entire quantity of ortho toluenesulphonamide whereas the
second precipitation contains but little ortho and considerable para amide.
The first precipitation with the main bulk of ortho amide is now dissolved in a
second vessel in hot water with the addition of alkaline earth, for example lime.
This solution contains the toluene sulphonamide as a salt of calcium.
To this solution (which is of an highly alkaline reactive character) per-
manganate of potassium is added while the contents of the vessel are subjected to
constant stirring.
The solution at first will acquire the fine colour of the permanganate of
potassium, but will afterwards quickly discolour, because the permanganate of
potassium will decompose into oxygen, manganese dioxide and alkali. The oxygen
will oxydise the toluene-sulphonamide. Further quantities of permanganate of
potassium are added as long as the solution coloured by it will readily discolour.
When this discolouring commences very slowly, the oxydation of the toluene-
sulphonamide is completed.
The strongly alkaline solution is then freed from the suspended manganese
dioxide by filtration or still better by centrifugal action and hydrochloric acid is
added to the filtered fluid until the latter reacts neutrally.
This neutralized solution is concentrated by evaporization in a vessel provided
with a steam jacket, till a sample taken from the concentrated fluid will if cooled
down deposit crystals. The solution so concentrated is then un down from the
evaporating pan into a crystallizing vessel. If the solution cools down, mainly
the chloride of potassium and the para sulphamine-benzoate of potassium will
crystallise, and the anhydro-ortho-sulpho-aminebenzoate of potassium, which is more

page_text: As regards the second precipitation hereinbefore referred to as containing but
little ortho, and considerable para-amide it may be put aside and when a sufficient
quantity has accumulated it can if desired be subjected to the same process of
purification.
Pure or nearly pure anhydro-ortho-sulphamine benzoic acid is dissolved in an open
vessel with a little water in a heated state, soda being added up to neutral reaction.
If necessary animal charcoal is added for discolouring, and the liquid is then
separated from the charcoal by filtration.
The solution after cooling will yield crystals of crystallose.
In case a sample of the solution yields no crystals, while cooling down, the
solution must be further concentrated by evaporation.
In the same manner the mother lye flowing off from the crystals is again
concentrated and cooled for obtaining the crystallose still remaining in the
mother lye.
3RD PROCESS.
Mixtures of anhydro-ortho-sulphamine benzoic acid with parasulphamine-benz pic
acid, as such mixtures are for instance known as saccharinum purum in the trade,
are dissolved in hot water, in a vessel provided with a steam jacket, neutralizing
the solution with soda or potash. Afterwards the solution is concentrated, not up
to dryness as in the production of the known soluble saccharine, but up to such a
point that a sample taken will crystallise in cooling down.
The so far concentrated solution is caused to run into a crystallising vessel and
left to crystallise until an analysis of the mother lye shews that it is free or
almost free from parasulphamine benzoic acid salts.
The contents of the crystallization vessel are then filtered.
The crystals will then contain all or nearly all para acid salts, while the mother
lye will contain the anhydro-ortho-sulphamine benzoate of sodium or potassium.
If at first soda be used for neutralisation, the resulting mother lye-if necessary
after discolouring by animal charcoal-may be at once concentrated by further
evaporation. In cooling down, crystals of the crystallose are obtained.
If however at first potash has been used for neutralisation, the mother-lye,
which contains the anhydro-ortho-sulphamine benzoate of potassium, is treated with

page_text: hydrochloric acid, until all anhydro-ortho-sulphamine benzoic acid has been
precipitated.
The latter is afterwards subjected to filtration and is converted into crystallose
according to the second process.
Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed I declare that what I
claim is
1. The process of manufacturing the new product herein before termed
crystallose, substantially as hereinbetore described under head 1.
2. The process of manufacturing the new product herein before termed
crystallose, substantially as hereinbefore described under head 2.
3. The process of manufacturing the new product herein before termed
crystallose substantially as hereinbefore described under head 3.
4. The new product herein before termed crystallose, which has a sweet taste, is
readily soluble in water, and consists of white or colourless crystals of the chemical
formula.
So,
CH
N Na
CO
with or without water of crystallisation (ordinarily with 1 to 2 aq.) and which
mainly differs from the product of commerce known as saccharine, in this that the
saccharine is in a powdery or grainy form, whereas crystallose has a crystalized
form for the purpose hereinbefore stated.
Dated this 6th day of December 1894.