New or Improved Manufacture of Periodides of Phenols and Salicylic Acid.
Year: 1889

page_text: Date of Application, 23rd Mar., 1889
Complete Specification Left, 10th Jan., 1890-Accepted, 22nd Feb., 1890
PROVISIONAL SPECIFICATION.
New or Improved Manufacture of Periodides of Phenols and
Salicylic Acid.
I, BENJAMIN WILLCOX, of 47 Lincoln's Inn Fields, in the County of Middlesex,
Patent Agent, do hereby declare the nature of this invention (which has been com-
municated to me from abroad by the Farbenfabriken vormals Friedrich Bayer & Co.
of Elberfeld in the Empire of Germany) to be as follows:-
By treating phenol with iodine there results only such substitution products in
which hydrogen atoms of the neucleus are alone replaced by iodine.
Salicylic acid also (in like manner to phenol) -produces this kind of iodine
substitution products.
By means of the process hereinafter described my foreign correspondents have
succeeded in producing new iodine substitution products or per iodides of phenol
and of salicylic acid such as the tri-iodophenol, iodide, iodo-thymol-iodide, iodo-thymol
(thymol iodide), beta-naphthol-iodide, and tri-iodo-salicylic acid iodide. This process
consists essentially in causing a solution of iodine in alkaline iodide (iodine alkalies)
to act on a watery alkaline solution of a phenol or salicylic acid. According to the
nature of the phenol or acid employed the products of the reaction vary, the lower
members of the phenols of the benzene series produce with the employment of
small quantity of iodine, disubstitution products and with a large excess of iodine
tetra iodine substitution products; the bigher members such as thymol produce
disubstitution products; the mono substituted salicylic acid of the naphthalene' series
produces a tetra substituted body.
In all cases however, the hydrogen atom of the hydroxyl group enters in reaction
and is replaced by iodine.
The product obtained by causing four atoms of iodine to react upon one molecule
of phenol is disagreeably smelling oil but a well defined almost odourless solid brown
red body is obtained by the action of eight atoms of iodine upon one molecule
of phenol.
The higher phenols such as thymol and beta naphthol can be quantitatively converted
into new solid iodine compounds by the action of four or two atoms of iodine. These
compounds are almost completely odourless and easily liberate even when simply
warm the atom of iodine associated with the oxygen with formation of mono iodo-
thymol or reformation of beta naphthol.
Salicylic acid yields when acted on by eight atoms of iodine a brown red colourless
body which likewise readily parts with the one atom of iodine with the formation of
triiodo salicylic acid.
The process for the production of the new iodine compound or combination of
phenol utilises the whole of the iodine employed.
The reaction in the case of thymol for example is represented by the following
equation-

page_text: utilised in practice by mixing the mother liquors of the filtered iodo thymol iodide
with a suitable alkaline solution of thymol and liberating the bound iodine by means
of an oxidising or liberating agent, such as chloride of: lime chlorine or alkaline
subchlorites (subchlorous acid salts of the alkalies). A. fresh quantity of thymol is
thus converted into the desired iodo thymol iodide according to the following
equation―
The following examples are given to enable the method of carrying out the
invention to be readily, understood.
Process for the production of iodo thymol iodide.
15 kilos of thymol are dissolved in 10 litres of water with the addition of 0.8 kilos
of caustic soda and to the clear liquid à solution of 5.08 kilos of iodine in 6.5 kilos
of an alkaline iodide is added whilst stirring without heating. A' dark red voluminous
amorphous deposit or precipitate is immediately formed which consists of iodo thymol
iodide. This product is immediately separated by filtration and the iodide collected
is carefully washed with clean water and' dried at the ordinary or atmospheric
temperature.
The new product thus obtained is chemically pure and forms an amorphous odourless
powder of a brown red colour. It is insoluble in cold or hot water being soluble in
alcohol and more readily soluble in ether and crystallises. In capillary tubes it melts
at from 101 to 102 degrees Centigrade the melting point of mono-iodo thymol.
Owing to the one atom of iodine associated with the oxygen the product is an
extremely unstaple body and readily changes into a colourless and hitherto unknown
mono iodo thymol. Mere exposure to the air is sufficient to cause a gradual conver-
sion of this di iodo derivative of thymol into a mono iodo, thymol. This process is
considerably accelerated by heat and moisture: When boiled with water or with a
solution of ether, or preferably alcoliol the product completely loses its colour on the
addition of sodium hyposulphite.
Conversion of iodo thymol iodide into thymol iodide (iodo thymol). Iodo thymo!
iodide is dissolved in water or alcohol' and treated or boiled with an alkali or a
solution of a subsulphurous acid salt (subsulphite of soda). A complete loss of colour
gradually takes place on continuous agitation and slightly heating. On pouring into
water or diluting with water the mono iodo thymol (thymol iodide) separates in the
form of white amorphous flakes. This product melts at from 101 to 102 degrees
Centigrade and is odourless and tasteless being insoluble in cold or hot water slightly
soluble in alcohol but dissolving readily in ether.
When phenol is substituted for the thymol in the foregoing example and eight
atoms of iodine are caused to react thereon as hereinbefore described a brown red
odourless substance is obtained-which readily parts with one atom of iodine: On
being boiled with soda lye this product is completely deprived of colour and then
forms triiodo phenol when treated with acid.
Salicylic acid produces in the same way as phenol when one molecule is acted on
by eight atoms of iodine a red brown odourless body which readily parts with one
atom of iodine with formation of tri iodo salicylic acid.

page_text: Production of beta naphthol iodide.
14 kilos of beta naphthol are dissolved in 0.8 kilos of caustic soda and to the
filtered liquid a solution of 24 kilos of iodine in 4.5 kilos of alkalino iodide is added.
The product of the reaction beta naphthol iodide immediately separates in the form
of an amorphous greenish yellow precipitate. It is filtered, thoroughly washed and
carefully dried indoors. The. beta naphthol iodide thus obtained is insoluble in cold
or hot water but may be dissolved by ether solvents and readily changes into beta
naphthol with separation of iodine.
Dated 01 L
M
1000
New or Improved Manufacture of Periodides of Phenols and
Salicylic Acid.
I BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this Invention (which has been com-
municated to me from abroad by the Farbenfabriken vormals Friedr. Bayer & Co.
of Elberfeld 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:
By treating phenols with iodine in an alkaline, alcoholic or watery solution with or
without the employment of means which bind the, hydriodic acid as heretofore
described, substitution products, result in which hydrogen atoms of the nucleus are
alone displaced by iodine (Beilstein II. pages 436-7. Willgerodt Journal, für pr.
Chemie 37, pages 446-48).
Phenolcarboxy acids (salicylic acid) and cresolcarboxy acids also afford this -kind
of iodine substitution products.
By means of the process, hereinafter described my foreign correspondents, have
succeeded in producing new iodine substitution products or periodides of phenol,
cresol, resorcin, thymol beta naphthol and of phenol. carboxy acids, (salicylic acid)
and cresolcarboxy acids in which the hydrogen atoms of the hydroxyl groups are
displaced by iodine. This process consists essentially, in causing a solution.of.iodine
in an alkaline iodide to act on a-watery, alkaline: solution of a phenol, or carboxy acids
thereof or their homologues.
According to the nature of the phenol or phenolcarboxy acid employed, t.the
products of the re-action vary, containing more.or less iodine, corresponding to the
quantity of iodine employed.
In all cases however the hydrogen atom of the hydroxyl group enters into reaction
and is displaced by iodine.
The reaction in the case of thymol for example is represented by the following
equation.
One half of the iodine is apparently lost in this process, but in fact the whole is
utilised in practice by mixing the inother liquors of the filtered iodo-thymol iodide
5 with a suitable alkaline solution of thymol, and liberating the bound iodine by means
of an oxidising or liberating agent such as chloride of lime, chlorine or alkaline,
hypochlorites (hypochlorous acid salts of the alkalies). A fresh quantity of

page_text: thymol is thus converted into the desired iodo thymol-iodide according to the
following equation.
reatify
Process for the production of iodo thymol iodide
15 kilos of thymol are dissolved in 10 litres of water with the addition of 0.8 kilos
of caustic soda and to the clear liquid a solution of 5.08 kilos of iodine in 6.5 kilos of
an alkaline iodide is added, the liquid being stirred without heating. A dark red
voluminous amorphous deposit or precipitate is immediately formed which consists of
iodo-thymol-iodide. This product is immediately separated by filtration and the
collected iodide is carefully washed with clear water and dried at the ordinary or
- atmospheric temperature.
The new product thus obtained is pure, and forms an amorphous odourless powder of
a brown red color. It is insoluble in cold or hot water, but is soluble in alcohol and
more readily soluble in ether and oil.
In capillary tubes it melts at about 110 degrees Centigrade but undergoes decom-
position. Owing to the one atom of iodine being associated with the oxygen, the
product is an extremely unstable body and readily changes into a colourless and
hitherto unknown mono-iodo-thymol. Mere exposure to the air is sufficient to cause
a gradual conversion of the di-iodo-derivative of thymol into a mono-iodo thymol.
This process is considerably accelerated by heating. When boiled with water or
with a solution of ether or preferably alcohol, the product completely loses its red
color on the addition of sodium hyposulphite.
When phenol, ortho meta or para cresol or resorcine are substituted for the thymol
in the foregoing example and an excess of iodine is caused to act thereon as herein-
before described new iodine substituted odourless substances are obtained.
In the case of phenol a brown red odourless product is produced which is insoluble
in water in dilute acids and alkalies, but soluble in alcohol, ether or benzene. It
scarcely undergoes change when boiled with water.
In the case of resorcin the potassium salt of Iodoresorcin iodide results in the
form of a chocolate brown powder possessing qualities similar to those of the other
phenol iodides.
Similar results are obtained with-the cresols which produce iodo-cresoliodides. With
salicylic acid and cresolcarboxy acids iodide new iodine substitution products are
likewise obtained which are odourless and insoluble in alkalies.
Production of beta naphthol iodide.
14 kilos of beta naphthol are dissolved in 0.8 kilos of caustic soda, and to the
filtered liquid a solution 2.4 kilos of iodine in 45 kilos of alkaline iodide is added.
The product of the reaction beta-napthol iodide immediately separates in the form
of an amorphous greenish yellow precipitate. It is filtered off thoroughly washed
and carefully dried.

page_text: The beta naphthol iodide thus obtained is insoluble in cold or hot water but may be
dissolved by ether. On treatment with alkalies or hyposulphites it is readily
reconverted into beta naphthol with separation of iodine.
Having now particularly described and ascertained the nature of the said invention
and in what manner the same is to be performed I declare that what I claim is :-
1. The process for the manufacture of new iodine substitution products of phenol,
cresol, resorcine, thymol beta naphthol, phenofcarboxy-acids viz.: salicylic acid and
cresol carboxy acids, which contain iodine in place of the hydrogen of the hydroxyl
group
(a) by treating these bodies in an alkaline solution with a watery solution of iodine
in alkaline iodides.
(b) by treating these bodies in an alkaline solution in the presence of iodine with
agents which liberate the bound iodine viz.: chloride of lime, chlorine or
alkaline bypochlorites.
2. The new iodine substitution products such as can be manufactured by the
processes hereinbefore described and claimed.
Dadth 10th
1000
J. H. JOHNSON & Co.,
Agents.