Improvements in the Manufacture of Antiseptic and Disinfectant Materials for Sanitary Purposes.
Year: 1893

page_text: Date of Application, 7th Mar., 1893
Complete Specification Left, 7th Dec., 1893-Accepted, 27th Jan., 1894
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Antiseptic and Disinfectant
Materials for Sanitary Purposes.
I CHARLES ROMLEY ALDER. WRIGHT D.Sc. F.R.S. of 3 Castellain Real,
Maida Vale, in the County of Middlesex, do hereby declare the nature of th
invention to be as follows:-
S:
This invention relates to the employment as antiseptic germicide and disinfectant,
materials of chloronaphthalene, broinonaphthalene and analogous more highly
chlorinated and brominated derivatives of naphthalene to an improved process for
preparing certain of these derivatives; and to the manufacture of novel commercial
products applicable for sanitary, purposes, and containing such derivatives as active
constituents.
1.
It is known to scientific chemists that by various laboratory operations of more
or less complex character, the hydrogen in naphthalene CH, may be replaced
by chlorine or bromine, giving rise successively to various isomeric modifications
of chloro naphthalene G, H,Cl, dichloronaphthalene CHCl, trichloronaphtha-
lene C10 HCl, &c..; or to the corresponding bromine derivatives. I have found
that these substances, some of which are liquid and some solid at the ordinary
temperature are, as a class possessed of marked germicide and antiseptic
characters. bogistgo
+ 1
By this invention I am enabled to manufacture "certain of these compounds at
such a price that they can be used for the above purpose at moderate cost, and 'f
also in some cases, provide for their convenient use in the powdered or liquid form.
by admixing or combining them with other substances as hereinafter described. I
generally prefer to employ the less highly chlorinated or brominated derivatives,
because of their liquid nature and greater degree of volatility; and for the sake of
cheapness of production, I prefer those substances that are formed by the direct
action of chlorine, or bromine, on, naphthalene rather than those produced by more
complex processes.
When it is required to obtain a liquid product consisting chiefly of chloronaphtha-
lene or bromonaphthalene, and containing as little as possible of dichloronaphthalene
or dibromonaphthalene or of more highly chlorinated or brominated substances, I find
that it is necessary to operate in a particular way whilst treating naphthalene with
chlorine or bromine. The materials must be cooled to prevent the temperature from
rising too high, which otherwise is apt to take place in consequence of the chemical
action, and the chlorine or bromine must not be used in sufficiently large quantity to
act upon the whole of the naphthalene present, so that at the end of the operation a
portion of the naphthalene remains unaltered, at least one-fourth or one-fifth.
This unaltered naphthalene is removed from the product and regained for use over
again, by blowing wet steam through the mass, as long, as the condensed matter
volatilized by the steam solidifies on dropping into cold water; or the mass 'is.
When on the other
distilled, when the unaltered naphthalene passes over first.
hand it is required to obtain a product containing larger quantities of dichloro
naphthalene or dibromo-naphthalene or more highly chlorinated or brominated
case of the
derivatives, it is unnecessary to cool the materials, excepting in,
temperature rising so high as to risk charring them; whilst the chlorine, or bromine
is used in much larger quantity, so that at the end of the operation. little or no
naphthalene remains unaltered.
b
As an example of the process I employ for obtaining a product consisting chiefly
of chloronaphthalene or bromo-naphthalene with but little admixture of mote
w of fold ads b
yas

page_text: highly chlorinated or brominated derivatives. I proceed as follows:-I suspend
naphthalene in water in a suitable vessel provided with a cooling jacket, and an
efficient agitator, and pass in a current of chlorine gas, keeping up vigorous
agitation, whereby the gas is rapidly absorbed; any small quantity escaping
absorption may be recovered by passing the escaping gases into a receptacle or
scrubber, containing lumps of solid naphthalene. When 55 to 60 parts of chlorine
have been used per 100 of naphthalene, the operation is stopped; the resulting
liquid or semi solid mass is treated with a current of wet steam blown through
until the unaltered naphthalene originally present is all volatilised. The heat of
the steam decomposes the liquid compound of chlorine and naphthalene (naphtha-
lene dichloride, CHCl₂) which is the principal product of the action when
carried out as above described, the effect of the decomposition being to form hydro-
chloric acid and chloro-naphthalene in accordance with the equation--

page_text: In order to prepare bromonaphthalene and other more highly brominated
derivatives of naphthalene, I proceed as above described, substituting bromine for
chlorine, that is passing bromine vapour into naphthalene suspended in water or
dropping in liquid bromine or solution of bromine, and employing 80 parts by
weight of bromine instead of 35 parts of chlorine.
In certain cases I employ chlorine and bromine simultaneously, or first one
and then the other, so as to produce mixed chlorinated and brominated substances.
The chloro-naphthalene and bromo-naphthalene products obtained as above
described are sufficiently volatile to evaporate readily at ordinary temperatures
when freely exposed to the air in thin films, as for example, when poured over
spongy or porous materials, or when intermixed with suitable powdered solid
substances. By impregnating the atmosphere with their vapours in this way, or by
converting them into spray, or by heating with water and allowing the vapours to
escape into the air, any germs present in the atmosphere may be sterilised, and the
air disinfected and purified.
Disinfectant powders for use in this way are readily prepared by intermixing the
unchlorinated or brominated products with suitable solid absorbents, such as
plaster of paris, carbonate of lime or sawdust, in the way usually employed in the
manufacture of sanitary powders containing other active ingredients.
Disinfectant soaps are prepared by "crutching" the chlorinated or brominated
products into melted soaps just before cooling to set and solidify; or by adding
them to the stock soap and other materials ground up together in the manufacture
of "nilled" soaps.
Watery and other solutions of the chlorinated or brominated products are
prepared by dissolving them, with or without the aid of heat, either in aqueous
liquors containing in solution the alkali salts of suitable organic acids, and more
particularly the soda salts of the weak acids contained in rosin; or in other suitable
fluids, such as rosin oil containing saponaceous matters in solution, so as to produce
liquids, which on dilution with water will furnish milky emulsions permanent for
considerable periods of time, and possessing great activity on account of the
extremely finely divided state of the active ingredients thus produced.
Instead of employing the chlorinated or brominated products alone for the above
purposes, they may in many cases be advantageously used in combination with other
substances of antiseptic character and more especially with certain natural essential
oils or balsams, or analogous artificial substances.
Thus fluids well adapted for household use, as air-sterilising disinfectants on
account of their comparatively fragrant odour and active properties, are obtained
by admixing with the chlorinated or brominated products, smaller quantities of
essential oils of antiseptic character, such as oil. of cloves, oil of thyme, oil of
rosemary, oil of cinnamon, eucalyptus oil, camphor oil, &c.; or by similarly
employing the active constituents of such oils extracted for the purpose, or
analogous substances of artificial origin, such as menthol, thymol eugenol, camphor,
phenol, naphthol &c.
Dated this 6th day of March 1893.
CHARLES R. ALDER WRIGHT.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Antiseptic and Disinfectant
Materials for Sanitary Purposes.
I, CHARLES ROMLEY ALDER WRIGHT, D.Sc., F.R.S., of 3 Castellain Road,
Maida Vale, in the County of Middlesex, 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 :-
13
This invention relates to the employment as antiseptic germicide and disinfectant

page_text: :
materials of chloronaphthalene, bromonaphthalene and analogous more highly
chlorinated and brominated derivates of naphthalene; to an improved process for
preparing certain of these derivatives; and to the manufacture of novel
commercial products applicable for sanitary purposes, and containing such derivatives
as active constituents.
:
It is known to scientific chemists that by various laboratory operations of more
or less complex character, the hydrogen in naphthalene C₁H may be replaced
by chlorine or bromine giving rise successively to various isomeric modifications
of chloro naphthalene CH,Cl, dichloronaphthalene C₁HCl, trichloronaphtha-
lene CHCI, &c.; or to the corresponding bromine derivatives. I have found
that these substances some of which are liquid and some solid at the ordinary
Lemperature are, as a class, possessed of marked germicide and antiseptic
characters.
By this invention I am enabled to manufacture certain of these compounds at
such a price that they can be used for the above purpose at moderate cost, and I
also in some cases, provide for their convenient use in the powdered or liquid form
by admixing or combining them with other substances as hereinafter described.
I generally prefer to employ the less highly chlorinated or brominated derivatives
because of their liquid nature and greater degree of volatility; and for the sake of
cheapness of production, I prefer those substances that are formed by the direct
action of chlorine or bromine on naphthalene, rather than those produced by more
complex processes.
When it is required to obtain a liquid product consisting chiefly of chloronaph-
thalene or bromonaphthalene, and containing as little as possible of dichloronaph-
thalene or dibromonaphthalene or of more highly chlorinated or brominated
substances, I find that it is necessary to operate in a particular way whilst treating
naphthalene with chlorine or bromine. The materials must be cooled to prevent
the temperature from rising too high, which otherwise is apt to take place in
consequence of the chemical action, and the chlorine or bromine, must not be used
in sufficiently large quantity to act upon the whole of the naphthalene present, so
that at the end of the operation a portion of the naphthalene remains unaltered, at
least one-fourth or one-fifth. This unaltered naphthalene is removed from the
product and regained for use over again, by blowing wet steam through the mass,
as long as the condensed matter volatilized by the steam solidifies on dropping into
cold water; or the mass is distilled, when the unaltered naphthalene passes over
first. When on the other hand it is required to obtain a product containing larger
quantities of dichloronaphthalene or dibromonaphthalene or more highly chlorinated
or brominated, derivates, it is unnecessary to cool the materials, excepting in case
of the temperature rising so high as to risk charring them, whilst the chlorine or
bromine is used in much larger quantity, so that at the end of the operation little or
no naphthalene remains unaltered.
As an example of the process I employ for obtaining a product consisting chiefly
of chloronaphthalene with but little admixture of more highly chlorinated
- derivatives I proceed as follows:-I suspend naphthalene in water in a suitable
vessel provided with a reflux condenser to condense steam and other vapours
emitted when the materials get heated up by the chemical action, and with a cooling
jacket, and an efficient agitator; and pass in a current of chlorine gas, keeping up
vigorous agitation, whereby the gas is rapidly absorbed; any small quantity
escaping absorption may be recovered by passing the cooled gases escaping from
the condensing arrangement into a receptacle or scrubber, containing lumps of solid
naphthalene. When 55. to.60 parts chlorine have been used per 100 of naphthalene
the operation is stopped; the resulting liquid or semi-solid mass is treated with a
current of wet steam blown through until the unaltered naphthalene originally
present is all volatilised.....
By operating in this way the temperature during the chlorination stage i
prevented from rising above 100 C.; under these circumstances the principa
action of the chlorine is to combine directly with the naphthalene, forming

page_text: chlorine; that is passing bromine vapour into naphthalene suspended-in water, or
-dropping in liquid bromine or solution of bromine, and employing 80 parts by
weight of bromine instead of 35 parts of chlorine.
In certain cases I employ chlorine and bromine simultaneously, or first one and
then the other, so as to produce mixed chlorinated and brominated substances.
The chloro-naphthalene and bromonaphthalene products obtained as above
described are sufficiently volatile to evaporate readily at ordinary temperatures
when freely exposed to the air in thin films, as for example, when poured over
spongy or porous materials, or when intermixed with suitable powdered solid
substances. By impregnating the atmosphere with their vapours in this way, or
by converting them into spray, or by heating with water and allowing the vapours
to escape into the air, any germs present in the atmosphere may be sterilised, and
the air disinfected and purified.
Disinfectant powders for use in this way are readily prepared by intermixing the
chlorinated or brominated products with suitable solid absorbents, such as plaster
of paris, carbonate of lime, or sawdust, in the way usually employed in the
manufacture of sanitary powders containing other active ingredients.
Disinfectant soaps are prepared by "crutching" the chlorinated or brominated
products into melted soaps just before cooling to set and solidify; or by adding
them to the stock soap and other materials ground up together in the manufacture
of "milled soaps.
""
Watery and other solutions of the chlorinated or brominated products are
prepared by dissolving them, with or without the aid of heat, either in aqueous
liquors containing in solution the alkali salts of suitable organic acids, and more
particularly the soda salts of the weak acids contained in rosin; or in other suitable
Huids, such as rosin oil containing saponaceous matters in solution, so as to produce
liquids, which on dilution with water will furnish milky emulsions permanent for
considerable periods of time, and possessing great activity on account of the
extremely finely divided state of the active ingredients thus produced.
Instead of employing the chlorinated or brominated products alone for the above
purposes, they may in many cases be advantageously used in combination with
other substances of antiseptic character and more especially with certain natural
essential oils or balsams, or analogous artificial substances.
Thus fluids well adapted for household use as air sterilising disinfectants, ou
account of their comparatively fragrant odour and active properties, are obtained
by admixing with the chlorinated or brominated products smaller quantities of
essential oils of antiseptic character, such as oil of cloves, oil of thyme, oil of
rosemary, oil of cinnamon, eucalyptus oil, camphor oil, &c.; or by similarly
employing the active constituents of such oils extracted for the purpose, or analogous
substances of artificial origin, such as menthol, thymol, eugenol, camphor, phenol,
naphthol, &c.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
I. The improved process for preparing chloronaphthalene and bromonaphthalene
comparatively free from more highly chlorinated or brominated naphthalene
derivatives substantially as described.
II. The use of chloronaphthalene, bromonaphthalene, and similar more highly
chlorinated or brominated naphthalene derivatives as disinfectant antiseptic and
germicide materials, either alone, or in conjunction with other substances suitable
for the preparation of solid or liquid products available for sanitary purposes.
III. The manufacture of fluids available for sanitary purposes by dissolving or
suspending the above named chlorinated or brominated naphthalene derivatives in
aqueous liquors containing in solution a soda or other alkali salt of the weak acids
contained in rosin, or in rosiu oil containing saponaceous matters in solution, or in
other suitable liquids.

page_text: IV. The manufacture of sanitary soaps by incorporating with ordinary soap of
various qualities the above named chlorinated and brominated naphthalene
derivatives.
V. The manufacture of powders for sanitary purposes by incorporating the-
above named chlorinated or brominated naphthalene derivatives with sawdust or
plaster of paris, carbonate of lime or other suitable solid absorbents so as to obtain,
ulverulent products.
Dated this First day of December 1893.
CHARLES ROMLEY ALDER WRIGHT..