Aromatic Series.
Year: 1899

page_text: Aromatic Series.
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 have discovered that, by causing the so-called halogen-
methylic alcohols, having the formula CH2. Cl. OH, CH. Br. OH, CH,I. OH. (that is
to say, the reaction products from formic aldehyde, or substances which are capable
of yielding formic aldehyde, and from haloid acids, such as hydrochloric acid, hydro-
bromic acid, hydriodic acid, or the like), to act, in the presence of suitable condensing
agents, such as strong mineral acids, or the like, on aromatic oxy compounds con-
taining electro negative substituents, (such as aromatic oxy-carbonic acids, aromatic
oxy-aldehydes, derivatives of the said bodies, or the like substances), valuable new
derivatives of these compounds are obtained which are characterized by the facts
that they contain the group-CH₁X (X meaning a halogen atom), and that the
halogen atom contained therein can easily be replaced by various groups and radicles,
- valuable derivatives of the new halogen-containing compounds being thus pro-
In order to illustrate the production of the said new halogen-containing com-
duced.
T
ivan the kilos being by weight
1.38 kilos. of salicylic acid are stirred into a solution of 0.665 kilos. of chloro-
methylic alcohol in 5 litres of highly concentrated hydrochloric acid; the mixture is
After this
heated up to 20-40 degrees, and then allowed to stand for 12 hours.
time, a white pasty mass results, which is separated from the liquid by filtering and
washing with concentrated hydrochloric acid. The product is then dried at low
temperatures, and purified by crystallization from benzene. Thus it is obtained in
the shape of brilliant leaves, which melt at 160° Centigrade, and are easily soluble in
ether, acetone, acetic acid, acetic ether, benzene, and chloroform.

page_text: From:
Chloromethylic alcohol and paraoxy benzoic acid
"
"
a body is obtained which
melts at:-
204° Centigrade
"
"
"
"
"
دو
metaoxy-benzoic acid
betaoxynaphthoic acid
metacresotinic acid
196°
"
200°
"
192°
"
paracresotinic acid
169°
"
anisic acid CH
"
"
CH
10.CH,
173°
"
\CO. OH/
وو
99
23
"
"
"
"
"
"
"
ester
-
وو
">
anisic acid ethyl ester
gaultheria oil
salicylic acid ethyl ester-
paraoxybenzoic acid me-
thyl ester
metacresotinic acid ethyl
2.3 oxynaphthoic acid
78°
"
98°
"
96°
"
-
-
139°
"
169°
"
"
"
ethyl ester
salicylic aldehyde
116°
"
88°
"
OH
"
"
vanilline CH
-CHO 127°
""
\O.CH
187°
"
22
106°
"
184°
99
"
"
salicylic aldehyde
879
دو
Bromomethylic alcohol and salicylic acid
salicylic aldehyde
Iodomethylic alcohol and salicylic acid-
It may be remarked that, in order to obtain the new product, it is (according t
e researches of my foreign correspondents) not necessary to operate with the fre
logen methylic alcohols. The same results are obtained on using the latter in th
-called statu nascendi, by employing, for instance, instead of chloromethylic alcoho
solution of this body which has been obtained by dissolving formic aldehyde in
ncentrated hydrochloric acid, and saturating the resulting solution with gaseou
drochloric acid.
According to the investigations of my foreign correspondents, the new haloger
ethylic derivatives exhibit the following characteristic properties.
When they are subjected to the action of hot water, the halogen atom of the group-
2 X is replaced by the hydroxy group, bodies containing the group-ČH₂ O
ing produced; when they are subjected to the action of alcohol, bodies substitute
the group CH. O. R (R meaning an alkyl radicle) are formed, an haloid aci
ch as hydrochloric acid or the like, being set free during these two reactions. O

page_text: subjecting the new compounds to the action of aromatic oxy compounds, or of amines,
a haloid acid is likewise set free, valuable new condensation products being thereby
obtained. In order to illustrate the two last mentioned reactions more fully, the
following Examples B and C are given, the parts being by weight.
C.H,
-OH
CHĘCI
in 500 parts of glacial acetic acid, is mixed with a concentrated solution of 144 parts
of beta naphtol in the same solvent. The mixture is heated at about from 100 to
120 degrees Centigrade until the development of hydrochloric acid which takes place
during the reaction, has ceased. After cooling, a crystalline mass will have separated,
which is filtered off, and recrystallised from glacial acetic acid. Thus it is obtained
in the shape of white leaves, which melt at 198° Centigrade. They are easily dis-
solved by alcohol and ether; are insoluble in water, but are capable of forming
soluble alkaline salts.
On adding a solution of ferric chloride (Fe, Cl₂) to a solution of the new body in
alcohol, a dark-blue precipitate is obtained.
In analogous manner, the condensation products from other aromatic oxy com-
pounds, or other of the above-defined halogenmethylic compounds, are obtained, if,
for instance, in the foregoing example, instead of betanaphthol, alphanaphthol is
employed, a body is obtained which melts at 258 degrees Centigrade; from chloro-
methyl salicylic acid and phenol, a body melting at 159° Centigrade is obtained;
from chloro-methyl salicylic acid and thymol, a compound melting at 250°; from
chloromethyl salicylic acid and isobutylorthocresol, a body melting at 177° is
obtained; from chloromethylic salicylic acid and resorcinol, likewise a valuable con-
densation product can be obtained.
The new compounds exhibit, in a high degree, bactericide properties, and represent
valuable antiseptic remedies for internal or external use. They can be applied for
these purposes either by themselves or in the form of their alkaline salts.
It is isolated by filtration, washed with water, and recrystallized from alcohol.
Thus it is obtained in the shape of small yellowish needles melting at 161 degrees
Centigrade.
My foreign correspondents proceed in an analogous manner in order to produce the
condensation products from other of the above defined halogen-methylic compounds,
or from other amines.

page_text: It may be pointed out that my foreign correspondents do not intend to confine
themselves to the particulars given in the above Specification, as the examples con-
tained therein are merely typical, and can be varied within wide limits without
altering thereby the nature of the present invention.
Dated this and dose of At 1000
NEWTON & SON,
Agents for the Applicant.
The Manufacture or Production of Chemical Compounds of the
Aromatic Series.
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 correspondents have discovered that, by causing the so-called halogen
methylic alcohols, having the formulae CH, Cl. OH, CH,Br OH, CH, IOH (that is
to say, the reaction products from formic aldehyde, or substances which are
capable of yielding formic aldehyde, and from haloid acids, such as hydrochloric acid,
hydro-bromic acid, hydro-iodic acid, or the like), to act in the presence of suitable
condensing agents, such as strong mineral acids, phosphorus oxychloride, phosphorus
pentoxide, zinc chloride, or the like, on aromatic oxy compounds containing electro-
negative substituents (such as aromatic oxy-carbonic-acids, aromatic oxy aldehydes,
derivatives of the said bodies, or the like substances), valuable new derivatives of
these compounds are obtained, which are characterized by the facts, that they contain
the group-CH, X (X meaning a halogen atom), and that the halogen atom con-
tained therein can easily be replaced by various groups and radicles, valuable deriva-
tives of the new halogen-containing compounds being thus produced.
.
In order to illustrate the production of the said new halogen-containing compounds,
the following typical Example A is given, the parts being by weight.
EXAMPLE A.
1.38 kilos. of salicylic acid are stirred into a solution of 0.665 kilos. of chloro
methylic alcohol in 5 litres of highly concentrated hydrochloric acid; the mixture is
heated up to 20-40 degrees Centigrade, and then allowed to stand for 12 hours. After
this time, a white pasty mass results, which is separated from the liquid by filtering
and washing with concentrated hydrochloric acid. The product is then dried at low
temperatures, and purified by crystallisation from benzene.
It has the appearance of
brilliant leaves, which melt at 163 degrees Centigrade, and are easily soluble in ether,
acetone, acetic acid, acetic ether, benzene, and chloroform.
The new product has most probably the formula

page_text: From:
Chloromethylic alcohol and paraoxy benzoic acid
"
66
"
"
"
"
"
"
metaoxybenzoic,
betaoxynaphthoic,,
metacresotinic
paracresotinic
وو
ments at―
204° Centigrade
196°
"
200°
192°
"
169°
"
"
OCH
anisic acid
H
173°
وو
"
"
COOH
"
"
"
"
"
2 2 2 5
د,
دو
ethyl-ester
78°
22
"
"
"
gaultheria oil
salicylic acid ethyl ester-
paraoxybenzoic acid me-
"
thyl-ester
metacresotinic acid
ethyl ester
-
989
969
"
***
-
-
139°
"
169°
"
"
"
2.3 oxynaphthoic acid-
ethyl ester
116°
"9
"
"
salicylic aldehyde -
88°
"
OH
"
"
vanilline CH,
-CHO
127°
"
OCH₂
"
iodomethylic alcohol
""
"
Bromomethylic alcohol and salicylic acid
"
187°
وو
"
22
"
aldehyde
acid
aldehyde
106°
"
184°
"
87°
""
It may be remarked that, in order to obtain the new products, it is (according to
the researches of my foreign correspondents) not necessary to operate with the free
halogen methylic alcohols. The same results are obtained on using the latter in the
so-called statu nascendi, by employing, for instance, instead of chloromethylic alcohol,
a solution of this body which has been obtained by dissolving formic aldehyde in a
concentrated hydrochloric acid, and saturating the resulting solution with gaseous
hydrochloric acid.
According to the investigations of my foreign correspondents, the new halogen-
methylic derivatives exhibit the following characteristic properties:
When they are subjected to the action of hot water, the halogen atom of the group
CH, X is replaced by the hydroxy-group, bodies containing the group CH, OH being
produced. When they are subjected to the action of alcohol, bodies substituted by
the group CH₂OR (R meaning an alkyl radicle) are formed, an haloid acid, such as
hydrochloric acid or the like, being set free during these two reactions. On subjecting
the new compounds to the action of aromatic oxy-compounds or salts thereof, or of
amines, haloid acid is likewise set free, valuable new condensation products being
thereby obtained. In order to illustrate the two last mentioned reactions more fully,
the following Examples B and C are given, the parts being by weight :-
EXAMPLE B.

page_text: in 500 parts of glacial acetic acid, is mixed with a concentrated solution of 144 parts
of beta naphthol in the same solvent. The mixture is heated at about from 100 to 120
degrees Centigrade, until the development of hydrochloric acid, which takes place
during the reaction, has ceased. After cooling, a crystalline mass will have separated,
which is filtered off, and recrystallized from glacial acetic acid. It will have the
appearance of white leaves, which melt at 198 degrees Centigrade. They are easily
dissolved by alcohol and ether, are insoluble in water, but are capable of forming
soluble alkaline salts.
On adding a solution of ferric chloride (Fe,Cl) to a solution of the new body in
alcohol, a dark-blue precipitate is obtained.
In an analogous manner, the condensation products from other aromatic oxy com-
pounds, or other of the above defined halogen methylic compounds, are obtained; if,
for instance, in the foregoing example, instead of betanaphthol, alphanaphthol is em-
ployed, a hody is obtained which melts at 258 degrees Centigrade. From chloro-
methylic salicylic acid and phenol, a body melting at 159 degrees Centigrade is
obtained. Chloromethylic salicylic acid and thymol produce a compound melting
at 250 degrees Centigrade. From chloromethylic salicylic acid and isobutyl-ortho-
cresol, a body melting at 177 degrees Centigrade is obtained; from chloromethylic
salicylic acid and resorcin, likewise a valuable condensation product can be obtained,
whilst the chloro-methyl salicylic aldehyde combines as well with one as with two
molecules of resorcin, two different condensation products being obtained.
The new compounds exhibit, in a high degree, bactericide properties, and represent
valuable antiseptic remedies for internal or external use. They can be applied for
these purposes either by themselves or in the form of their alkaline salts.
.
It is isolated by filtration, washed with water, and recrystallized from alcohol. Thus
it is obtained in the shape of small yellowish needles melting at 161 degrees
Centigrade.
My foreign correspondents proceed in an analogous manner in order to produce the
condensation products from other of the above defined halogen methylic compounds,
or from other amines.
It may be pointed out that my foreign correspondents do not intend to confine
themselves to the particulars given in the above specification, as the examples
contained therein are merely typical, and can be varied within wide limits, without
altering thereby the nature of the present invention.
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 claim is :-
1. The process for producing new aromatic compounds containing the group-
CH2X (X meaning a halogen atom), which process consists in treating aromatic
oxy carboxylic acids, or aromatic oxy aldehydes, or derivatives thereof, with halogen,
methylic alcohols having the formulae CH,CI OH, CH, - Br - OH, CH, - 1 - OH,
in the presence of suitable condensing agents, such as strong mineral acids, zinc
1

page_text: chloride, phosphorus oxychloride-phosphorus pentoxide, or the like, substantially as
herein before described.
2. The process for producing new aromatic compounds containing the group-
CH, X (X meaning a halogen atom), which process consists in treating a mixture
prepared from aromatic oxy-carboxylic acids, or aromatic oxy-aldehydes, or derivatives
thereof, and formic aldehyde, with concentrated haloid acids, substantially as herein-
before described.
3. The process for producing aromatic compounds containing the group-CH, OH,
which process consists in treating with water the bodies obtainable by the processes
claimed under Claims 1 and 2, substantially as herein before described.
4. The process for producing aromatic compounds, containing the group CH₂OR
(R meaning an alkyl radicle such as methyl, ethyl, or the like), which process consists
in treating with alcohols the compounds obtainable by the processes claimed under
Claims 1 and 2, substantially as herein before described.
5. The process for producing new condensation products derived from the above
described compounds obtainable by the processes claimed under Claims 1 and 2, which
process consists in treating these bodies with aromatic oxy compounds, or salts
thereof, substantially as herein before described.
6. The process for producing new condensation products derived from the above
described compounds obtainable by the processes claimed under Claims 1 and 2,
which process consists in treating these bodies with amines, substantially as herein-
before described.
7. As new articles of manufacture, the bodies obtainable by the processes herein-
before described and claimed.