The Manufacture and Production of Condensation Products from Phenols and Alloxan.
Year: 1899

page_text: Date of Application, 20th June, 1899*
Complete Specification Left, 19th Mar., 1900-Accepted, 19th May, 1900
The Manufacture and Production of Condensation Products from
Phenols and Alloxan.
I, GEORGE WILLIAM JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Patent Agent, do hereby declare the nature of this invention (which has been com-
municated to me from abroad by C. F. Boehringer & Soehne of Waldhof, near
Mannheim, in the German Empire) to be as follows:-
The present invention has for its object the manufacture and production of
condensation products from phenols and alloxan. According to this invention it has
been found that these compounds, when brought together under suitable conditions,
will unite and form well-defined condensation products; this condensation taking
place, in some cases when the component bodies are merely brought together in
solution but the best results are obtained when they are combined in the presence of
condensing agents. Hydrochloric acid is particularly suitable as a condensing agent,
but the condensation may be carried out also by the aid of, and in the presence of,
sulphuric acid, zinc-chloride and other similarly acting compounds. In the course of
the reaction the phenol and alloxan unite, molecule for molecule, and the reaction
probably takes place in such a way that the ketone-carbon atom of the alloxan-
molecule and the benzyl nucleus are bound together, while at the same time the
liberated atom of hydrogen is bound to the ketone oxygen of the alloxan.
The process according to this invention is applicable both to univalent and multi-
valent phenols the resulting compounds corresponding to the type denoted by the
hydrogen.
The compounds of this new class of bodies, so far as they have been investigated,
are distinguished by ready crystallization. The derivatives of the benzene-series are
readily soluble in warm water and tolerably soluble in cold water. They are readily
taken up by alcohol. Alloxan-alpha-naphthol is somewhat less soluble.
The alloxan-phenols are useful as medicines and lend themselves readily to such
use because of their solubility in water and their being tasteless. They are moreover
useful as initial products in the preparation of other products useful in the
arts.
Condensation products for example can be prepared from the following in accordance

page_text: 1. From alloxan and phenol proper, the formula of the new compound being-
C₁HN₂O+H₂O;
5°
2. From alloxan and meta-cresol. The formula of the new compound is C₁₁₂O.
This body crystallizes from water in the shape of colourless needles. On heating
to 230° Centigrade, it becomes coloured, and at 270° it is decomposed with evolution
of gas.
3. From alloxan and para-cresol. These unite and form a compound having the
formula CHN₂O. It crystallizes from an aqueous solution in the form of coarse
needles. It decomposes at a temperature of from 228° to 230° Centigrade.
10
4. From alloxan and guaiacol. The formula of the new compound formed by these
is C₁HNO+H₂O. It crystallizes from water in coarse colourless crystals and
melts at 150° Centigrade, with decomposition and evolution of gas.
11
5. From alloxan and benzocatechin. The compound from these has the
formula CoHN20. It crystallizes from water in the form of coarse prisms. On
heating to over 200° Centigrade it decomposes.
6. From alloxan and resorcin. The formula of the condensation product
is CoHN₂O. From acetic ether it crystallizes in the form of fine colourless
crystals and is gradually decomposed on heating to over 200° Centigrade.
7. The compound from alloxan and hydroquinone crystallizes from water in the
form of prisms. It becomes of a darker colour on heating to 170° Centigrade, and is
completely decomposed when heated to from 205° to 207° Centigrade.
8. The compound from alloxan and pyrogallol has the formula C₁HN₂O+H₂O.
It crystallizes from water in the form of coarse needles which decompose at about
230° Centigrade.
14 10'
9. The compound from alloxan and alpha-naphthol has the formula C₁H0N205.
It is rather difficult of solution even in hot water. On cooling such a solution the
compound crystallizes either in the form of acicular, or shining foliated, crystals. On
heating it gradually decomposes.
I give in detail a number of examples but I do not limit myself to the details
TW CONDENSATION
21.4 kilograms of alloxan are dissolved in 70 litres of water and 9.4 kilograms of
phenol are added to the solution and the whole is mixed by agitating. By this action
the phenol becomes suspended in the alloxan solution. A strong current or jet of
hydrochloric acid in the form of a gas, or in aqueous solution is then introduced into
the suspended mixture taking care that the mixture does not become too highly
heated by this action which can be done by cooling by water circulating around, or
through, the mixture. As a result of this treatment the phenol gradually. goes into
solution. When a clear solution has been attained the introduction of hydrochloric
acid is discontinued and the whole is allowed to stand, until it congeals, or solidifies,
in the form of a thick pasty mass of crystals which are then separated from the
mother liquor and purified by recrystallizing from water. In this way the new
condensation compound is obtained in the form of beautiful colourless large crystals
whose composition corresponds to the formula:
These crystals become yellow when heated to over 200° Centigrade, and they melt
with violent evolution of gases and consequent decomposition at from 255° to 257°
Centigrade.
The operation is successful when a solution of alloxan in hydrochloric acid, or an
alloxan solution very strongly acidulated with HCl, is employed, instead of the
aforesaid aqueous solution of the alloxan. Under these conditions the separate
introduction of the HCl current may be entirely, or partly, dispensed with.

page_text: Such acidulated alloxan solutions may be obtained directly by oxidizing uric acid
with hydrochloric acid and chlorate of potash. It is of considerable advantage to
hasten the solution of the phenol to add a quantity of alcohol. For example, the
process may be carried out as follows:-
To a warm solution of 21.4 kilograms of alloxan in an equal quantity of water,, are
added 9.4 kilograms of phenol and 10.litres of alcohol. To the clear solution thus
obtained 20 litres of fuming hydrochloric acid of specific gravity 1.19 are added and
the whole is gently warmed on the water bath. After a short time the alloxan-phenol
begins to separate, the quantity being considerably increased on cooling.
21.4 kilograms of alloxan are dissolved in an equal quantity of hot water
and 9.4 kilograms of phenol are then added. 9 kilograms of zinc-chloride are
then added to the mixture and the whole is stirred. A clear solution thus results
which. is then gently warmed on the water bath. On cooling the alloxan-phenol
separates out and it may be purified by recrystallization from water.
150 grams of alpha-naphthol in 160 grams of alcohol are added to a hot solution of
220 grams of alloxan in 220. grams of water. An oil substance separates. When
this takes place the whole is heated on the water bath and 350 grams of fuming
hydrochloric acid are added. A clear solution forms which stiffens to a crystalline
mass, the crystals being composed of the new compound; alloxan-alpha-naphthol
having the formula C₁₁₂О. The reaction is indicated by the equation.
10
PREPARATION OF ALLOXAN-GUAIACOL.
520 grams of alloxan are dissolved in an equal quantity by weight of hot water.
To this solution are added 700 grams of fuming hydrochloric acid and a solution of
300 grams of guaiacol in 400 grams of alcohol. Into the clear liquid obtained at, or
about ordinary or room temperature hydrochloric acid is introduced until the solution
begins to give off fumes. After a time the condensation product separates and is
removed by siphoning or decanting, and recrystallized from water, when it is obtained
in the form of coarse crystals containing one molecular proportion of water of
crystallization. The said crystals melt-with evolution of gas at 150° Centigrade.
The new compound has the formula C₁₁₂O+ H2O and the reaction which
takes place in its formation is expressed in the equation:
130 grams of pyrogallol are added to a warm solution of 220 grams of alloxan in
an equal weight of water, and the whole is heated on the water bath until solution
takes place. On cooling the new condensation product separates in the form of
coarse needles, or prisms having the formula C₁HN,O,+2H₂O. On heating to about
230° Centigrade they are decomposed.

page_text: CH. (OH)+CH₂N₂O₁=C₁H¸¸.
a
This invention broadly considered consists in the manufacture and production of
new series of compounds by adding alloxan to a phenol either without a condensing
agent, or in the presence of a condensing agent, such as hydrochloric acid, sul-
phuric acid, zinc chloride, or the equivalents, the hydrochloric acid being
deemed particularly desirable. The condensation products prepared in accordance
with this invention are distinguished by their solubility in alcohol and with the
exception of the alpha-naphthol product by their solubility in hot water and tolerable
solubility in cold water, by their ready crystallizability, and many of them by their
tendency to decompose at an elevated temperature.
Dated this 20th day of June 1800
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of Condensation Products from
Phenols and Alloxan.
I, GEORGE WILLIAM JOHNSON, of 47, Lincoln's Inn Fields, in the County of
London, Patent Agent, do hereby declare the nature of this invention (which has been
communicated to me from abroad by G. F. Boehringer & Solhne, of Waldhof, near
Mannheim, in the German Empire) and in what manner the same is to be
performed to be particularly described and ascertained in and by the following
statement
The present invention has for its object the manufacture and production of con-
densation products from phenols and alloxan. According to this invention it has
been found that these compounds, when brought together under suitable conditions
will unite and form well defined condensation products; this condensation taking
place, in some cases when the component bodies are merely brought together in
solution but the best results are obtained when they are combined in the presence of
condensing agents. Hydrochloric acid is particularly suitable as a condensing agent,
but the condensation may be carried out also by the aid of, and in the presence of
sulphuric acid, zinc-chloride and other similarly acting compounds. In the course of
the reaction the phenols and alloxan unite, and the reaction probably takes place in
such a way that the ketone-carbon atom of the alloxan-molecule and the benzene
nucleus are bound together, while at the same time the liberated atom of hydrogen
is bound to the ketone oxygen of the alloxan.
The process according to this invention is applicable both to univalent and multi-
valent phenols the resulting compounds corresponding to the type denoted by the

page_text: On treating a multivalent phenol with alloxan it is also possible to obtain conden-
sation products containing more than one molecular proportion of alloxan for one
molecular proportion of the phenol vir. the phloroglucin-trialloxan having the
formula
The compounds of this new class of bodies so far as they have been investigated
are distinguished by ready crystallization. The derivatives of the benzene series are
readily soluble in warm water and tolerably soluble in cold water. They are readily
taken up by alcohol. Alloxan-alpha-naphthol is somewhat less soluble.
The alloxan-phenols are useful as medicines and lend themselves readily to such use
because of their solubility in water and their being tasteless. They are moreover
useful as initial products in the preparation of other products useful in the arts.
Condensation products for example can be prepared from the following in accordance
with this invention.
1. From alloxan and phenol proper, the formula of the new compound being
CHH₂O + H₁₂O.
10
2. From alloxan and meta cresol. The formula of the new compound is C₁H₁N,O..
This body crystallizes from water in the shape of colourless needles. On heating to
230° Centigrade it becomes coloured and at 270° it is decomposed with evolution of
gas.
3. From alloxan and para-cresol. These unite and form a compound having the
formula C₁₁₂O. It crystallizes from an aqueous solution in the form of coarse
needles. It decomposes at a temperature of from 228° to 230° Centigrade.
10'
4. From alloxan and guaiacol. The formula of the new compound formed by these is
C₁HNO + H₂O. It crystallizes from water in coarse colourless crystals and melts
at 150° Centigrade with decomposition and evolution of gas.
5. From alloxan and brenzocatechin. The compound from these has the formula
C₁0HN₂O It crystallizes from water in the form of coarse prisms. On heating
to over 200° Centigrade it decomposes.
6. From alloxan and resorcin. The formula of the condensation product
is CoHN2O From acetic ether it crystallizes in the form of fine colourless
crystals and is gradually decomposed on heating to over 200° Centigrade.
7. The compound from alloxan and hydroquinone crystallizes from water in the '
form of prisms. It becomes of a darker colour on heating to 170° Centigrade and is
completely decomposed when heated to from 205° to 207 Centigrade.
8. The compound from alloxan and pyrogallol has the formula CHNO, + H₂O.
It crystallizes from water in the form of coarse needles which decompose at about
230° Centigrade.
25°
9. The compound from alloxan and alphanaphthol has the formula C₁HËN₂О¸.
It is rather difficult of solution even in hot water. On cooling such a solution the
compound crystallizes either in the form of acicular or shining foliated crystals. On
heating it gradually decomposes.
10. The compound from two molecular proportions of alloxan and one molecular
proportion of resorcin has the formula C₁HNO10 + H2O. It crystallizes from water
in the form of compact colourless crystals which decompose when heated at above
200° Centigrade.
:
11. The compound from three molecular proportions of alloxan and one molecular

page_text: These crystals become yellow when heated to over 200° Centigrade, and they melt
with violent evolution of gases and consequent decomposition at from 255° to.
257° Centigrade.
The operation is successful when a solution of alloxan in hydrochloric acid, or an
alloxan solution very strongly acidulated with HCl is employed instead of the afore-
said aqueous solution of the alloxan. Under these conditions the separate intro-
duction of the HCl current may be entirely or partly, dispensed with.
Such acidulated alloxan solutions may be obtained directly by oxidizing uric acid
with hydrochloric acid and chlorate of potash. It is of considerable advantage to
hasten the solution of the phenol to add a quantity of alcohol. For example, the
process may be carried out as follows:-
To a warm solution of 21.4 kilograms of alloxan in an equal quantity of water,
are added 9.4 kilograms of phenol, and 10 litres of alcohol. To the clear solution
thus obtained 20 litres of fuming hydrochloric acid of specific gravity 1.19 are added
and the whole is gently warmed on the water bath. After a short time the alloxan-
phenol begins to separate, the quantity being considerably increased on cooling.
150 grams of alpha-naphthol in 160 grams of alcohol are added to a hot solution
of 220 grams of alloxan in 220 grams of water. An oily substance separates. When
this takes place the whole is heated on the water bath and 350 grams of fuming
hydrochloric acid are added. A clear solution forms which stiffens to a crystalline

page_text: mass the crystals being composed of the new compound alloxan-alpha-naphthol
having the formula C₁₁₂O5. The reaction is indicated by the equation:
10
де поп сотрои
TII Hot water. 10 crystalizes ertner
in needles, or in shining foliated crystals. It gradually decomposes on heating.
EXAMPLE 3.
PREPARATION OF ALLOXAN-GUAIACOL.
520 grams of alloxan are dissolved in an equal quantity by weight of hot water.
To this solution are added 700 grams of fuming hydrochloric acid and a solution of
300 grams of guaiacol in 400 grams of alcohol. Into the clear liquid obtained at, or
about, ordinary or room temperature hydrochloric acid is introduced until the solution
begins to give off fumes. After a time the condensation product separates and is
removed by siphoning or decanting, and recrystallized from water, when it is obtained
in the form of coarse crystals containing one molecular proportion of water of
crystallization. The said crystals melt with evolution of gas at 150° Centigrade.
The new compound has the formula C₁HN2O + H2O and the reaction which
takes place in its formation is expressed in the equation:
10
6
520 grams of alloxan are dissolved in an equal quantity by weight of hot water.
To this solution are added 700 grams of fuming hydrochloric acid and a solution of
300 grams of guaiacol in 400 grams of alcohol. Into the clear liquid obtained at, or
about, ordinary or room temperature hydrochloric acid is introduced until the solution
begins to give off fumes. After a time the condensation product separates and is
removed by siphoning or decanting, and recrystallized from water, when it is obtained
in the form of coarse crystals containing one molecular proportion of water of
crystallization. The said crystals melt with evolution of gas at 150° Centigrade.
The new compound has the formula C₁HNO + H2O and the reaction which
takes place in its formation is expressed in the equation:
130 grams of pyrogallol are added to a warm solution of 220 grams of alloxan in
an equal weight of water, and the whole is heated on the water bath until solution
takes place. On cooling the new condensation product separates in the form of coarse
needles, or prisms, having the formula C₁HN₂O + 2 H₂O. On heating to about
230° Centigrade they are decomposed.
The reaction proceeds according to the equation:
220 grams of alloxan are dissolved in 200 grams of hot water and 55 grams of
resorcin are added thereto. A clear solution is obtained, which on cooling forms a
crystalline mass. After about 15 hours the crystals are siphoned and purified by re-
crystallization from a small quantity of water. Compact colourless crystals are so
obtained decomposing when heated to above 200° Centigrade.
This invention broadly considered, consists in the manufacture and production of a
new series of compounds by adding alloxan to a phenol either without a condensing
agent, or in the presence of a condensing agent, such as hydrochloric acid, sulphuric
acid, zinc chloride, or the equivalents the hydrochloric acid being deemed particularly
desirable. The condensation products prepared in accordance with this invention are
distinguished by their solubility in alcohol and with the exception of the alpha-
naphthol product by their solubility in hot water and tolerable solubility in cold
water, by their ready crystallizability and many of them by their tendency to decom-
pose at an elevated temperature.
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:

page_text: 1. The manufacture of condensation products of a phenol and alloxan by treating
univalent, or multivalent phenol with alloxan solution in the presence or not of a
condensing agent in the manner herein before described.
2. As new articles of manufacture the condensation products of a phenol and
alloxan having the formula and the properties hereinbefore set forth.
Dated this 19th day of March 1900.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents..