Improvements in the Manufacture or Production of Salols and Analogous Compounds.
Year: 1890

page_text: Date of Application, 23th Oct., 1890
Complete Specification Left, 20th July, 1891-Accepted, 28th Oct., 1891
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture or Production of Salols and
Analogous Compounds.
1, Dr. CARL KOLBE, of Radebeul, near Dresden, Saxony, in the Empire of
Germany, do hereby declare the nature of this invention to be as follows:-
In the Specification of Letters Patent No. 8018, dated 16 June 1886; granted
to Marcel von Nenchi and myself, and in the Specifications of Letters Patents
No. 10260 dated 22nd July 1887, and No. 13169 dated 12th September 1888
granted to me, various methods are described for the manufacture or production of
salols. In the further practice of the reactions described in these Specifications it
has been discovered that cinnamic acid could be employed in place of the various
acids therein referred to, and also that glycerine could be employed in place of
phenol.
In this manner the following new bodies are produced according to this
nvention.
Cinnamate of guajacol.
Cinnamate of creosol.
Salicylate of glycerine (di-salicylate and tri-salicylate).
o-Cresotinate of glycerine (di-cresotinate and tri-cresotinate).
in-Cresotinate of glycerine (di-cresotinate and tri-cresotinate).
p-Cresotinate of glycerine (di-cresotinate and tri-cresotinate).
Cinnamate of glycerine (di-cynnamate and tri-cynnamate).
It has also been found in this case that in the production of the said glycerine
salols or esters, the condensation or dehydrating agents such as PCI, PC,, &c.,
nentioned in the said former Specifications, can be entirely dispensed with by simply
eating in a continuous manner to a temperature of from about 150° to about 200° C.,
a mixture of glycerine with, for example, salicylic acid, suitable proportions being
molecule of glycerine to 2 molecules of salicylic acid for producing the
li-salicylate, and 1 molecule of glycerine with 4 to 6 molecules of salicylic acid
or producing the tri-salicylate.
It is advantageous to effect the heating at a pressure less than that of the
tmosphere in order that the water, phenol, &c., formed, may distil off rapidly.
When instead of the above mentioned condensation or dehydrating agents,
ydrochloric acid is employed, by continuously conducting this gas into, for
example, a hot mixture of glycerine and salicylic acid, then one molecule of
ydroxyl in the glycerine is replaced by an acid ester for example by OCOCH OH;
nd the other two molecules of hydroxyl are replaced by chlorine. Thus a salicylate
f di-chlorhydrine is produced according to the following equation :-
CH₂OH
COOH
+ CH(OH)3 + 2 HCl = CH₂OСОС¸н¸OH + 3 H₂O
Cl₂
In the same manner by substituting o- m- p-cresotinic acid for salicylic acid,
o-, m-, and p-cresotinate of di-chlorhydrine CHOCOCH₂CH¸ can be obtained;
Cl₂
OH
3
and by.substituting cinnamic acid for the salicylic acid, cinnamate of di-chlorhydrine

page_text: di-chlorhydrino he heated with salicylate of sodium, there will be produced the
tri-salicylate according to the following equation:-
-
tri-salicylate according to the following equation:-
Cl₂
2 C. HCOONa
OH
-
2 NaCl + C₂H(ОCOC₂H₂OH)3
The resulting product is washed with water, and re-crystallized from alcohol.
All the substances above mentioned are colourless and often remain liquid though
the same may have been cooled to a temperature low enough to be changed into a
solid state. They are insoluble or with difficulty soluble in water, but are soluble
in alcohol from which they can be separated by re-crystallization. They dissolve
without decomposition in a cold dilute solution of soda. When this solution is
heated saponification ensues.
The new salols or products herein before referred to can be employed as healing
agents.
CARL KOLBE,
Per L. W.
COMPLETE SPECIFICATION.
Improvements in the Manufacture or Production of Salols and
Analogous Compounds.
1, Dr. CARL KOLBE of Radebeul near Dresden, in the Kingdom of Saxony, 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 :-
In the Specification of Letters Patent No. 8018, dated 16 June 1886, granted to
Marcel von Nencki and myself, and in the Specifications of Letters Patent
No. 10260 dated 22nd July 1887, and No. 13169 dated 12th September 1888
granted to me, various methods are described for the manufacture or production
of salols. In the further practice of the reactions described in these Specifications
it has been discovered that cinnamic acid could be employed in place of the
various acids therein referred to, and also that glycerine could be employed in place
of phenol.
In this manner the following new bodies are produced according to this
invention.
Cinnamate of guajacol.
Cinnamate of creosol (i.e. methylguajacol).
Cinnamate of eugenol (i.e. allylguajacol).
Salicylate-of glycerine (di-salicylate and tri-salicylate).
o-Cresotinate of glycerine (di-cresotiuate and tri-cresotinate).
m-Cresotinate of glycerine (di-cresotinate and tri-cresotinate).
p-Cresotinate of glycerine (di-cresotinate and tri-cresotinate).
Cinnamate of glycerine (di-cinnamate and tri-cinnamate).
Of the acid or poly-acid sulphates of the alkalies as mentioned in my said former
Specification No. 10260 of 1887, there can be employed with advantage the pyro-
sulphates of the alkalies, for instance pyro-sulphate of potassium K.SO.SO,
or K,S,O,.
It has also been found in this case that in the production of the said glycerine
salols or esters, the condensation or dehydrating agents such as PCI, PCI, &c.,
mentioned in the said former Specifications, can be entirely dispensed with by
simply heating in a continuous manner to a temperature of from about 150° to
about 200° C., a mixture of glycerine with, for example, salicylic acid, suitable
proportions being 1 molecule of glycerine to 2 molecules of salicylic acid for
producing the di-salicylate, and I molecule of glycerine with 4 to 6 molecules of
salicylic acid for producing the tri-salicylate.

page_text: It is advantageous to effect the heating at a pressure less than that of the atmo-
sphere in order that the water, phenol, &c., formed, may distil off rapidly.
When instead of the above mentioned condensation or dehydrating agents,
hydrochloric acid is employed, by continuously conducting this gas into, for
example, a hot mixture of glycerine and salicylic acid, then one molecule of
hydroxyl in the glycerine is replaced by an acid ester for example by OCOCHOH;
and the other two molecules of hydroxyl are replaced by chlorine. Thus a
salicylate of di-chlorhydrine is produced according to the following equation
:-

page_text: Glycerine cinnamate.
By heating glycerine with the respective aromatic acids to a temperature of from
about 150 to 200° C. without the addition of condensation or dehydrating agents as
set forth.
3. The manufacture or production of:
Salicylate of dichlorhydrine or
o-Cresotinate of dichlorhydrine or
m-Cresotinate of dichlorhydrine or
p-Cresotinate of dichlorhydrine
Cinnamate of dichlorhydrine.
By conducting hydrochloric acid gas into a hot mixture of glycerine and the
respective acid, the resulting dichlorhydrine compounds being converted, if
desired, into tri-esters of glycerine by heating with a salt the respective acid.
Dated this 20th day of July 1891.
C. KOLBE,
By L. W., per F. B.