IM- PROVEMENTS IN THE PRODUCTION OF DYES FROM NAPHTHALINE AND ITS DERIVATIVES
Year: 1875

page_text: LETTERS PATENT to Justus Wolff, of Wyke, near Bradford, Con-
sulting and Engineering Chemist, and Ralph Betley, of Wigan,
Analytical and Consulting Chemist, for the Invention of "IM-
PROVEMENTS IN THE PRODUCTION OF DYES FROM NAPHTHALINE AND ITS
DERIVATIVES."
Scaled the 23rd December 1875, and dated the 7th July 1875.
PROVISIONAL SPECIFICATION left by the said Justus Wolff and
Ralph Betley at the Office of the Commissioners of Patents, with
their Petition, on the 7th July 1875.
We, JUSTUS WOLFF, of Wyke, near Bradford, Consulting and
Engineering Chemist, and RALPH BETLEY, of Wigan, Analytical and
Consulting Chemist, do hereby declare the nature of our said Inven-
tion for "IMPROVEMENTS IN THE PRODUCTION OF DYES FROM NAPHTHALINE AND
ITS DERIVATIVES," to be as follows:-
This Invention relates to the production of dyes obtained from the
products which are yielded by substitution of one hydrogen atom in
napthaline or its derivatives by one molecule of benzol or its derivatives,
1

page_text: or the homologues of benzol or their derivatives, and by means of
energetic oxidation either with chromic acid or permanganic acid, or
chloric acid, or sulphuric acid, or other suitable oxidizing agent with the
treatment of the so formed sulpho-acid with caustic soda or potash, and
finally oxidation by forming sulpho-acids or substitutions of the before-
mentioned compounds with chlorine, bromine, iodine, nitrous acid,
cyanogen, etc., and subsequently treating with caustic soda or potash.
For the purpose of carrying out this Invention we take for example
one equivalent of napthaline mixed with 1 equivalent of dichlor benzol
and 2 equivalents of zinc powder, and heat this mixture in strong closed
vessels at a temperature of about 220° Celsius for about 12 hours. The
mass thus obtained we treat with about 3 times its weight of acetic acid
(glacial acetic acid being preferred) in order to dissolvo it, and add
whilst warm and with slight and cautious agitation and in small
quantities at a time chromic acid until no further reaction takes place,
then we add to this mixture about 3 to 4 times its weight of cold water,
the mass is then filtered off and the residuum on the filter well washed,
dried, and dissolved in about 3 or 4 times its weight of fuming sulphuric
acid at a heat 220 degrees to 230 degrees Celcius until it is ascertained
by a drawn sample that it completely dissolves in water (with the
exception of carbonised matters), which will be usually accomplished in
about 2 hours time. The resulting substance we treat with water,
neutralise with quicklime, boil it, filter if necessary, evaporate and
treat the evaporated solution with caustic soda in solution equal to about
3 times the weight of the substance which has been dissolved in
sulphuric acid for about 4 to 6 hours at 170 degrees to 200 degrees
Celsius, until it is ascertained by a sample treated with excess of acid
that the mass does not show any increase of precipitate created by the
acid; then we dissolve the resulting mass in water, neutralise it with
hydrochloric acid, filter and wash; the material so obtained is ready for
dycing and printing purposes.
Another example is as follows:-We take one equivalent phthalic
acid (produced from napthaline by energetic oxidation with permanganic
acid, chloric acid, or nitric acid) and mix it with 1 equivalent of dichlor
benzol and 2 equivalents of zinc, in powder preferred, and heat this
mixture in strong closed vessels for about 12 hours at about 220 degrees
Celsius, the resulting mass is then dissolved in acetic acid (glacial acetic
acid being preferred), and strongly oxidised in this solution either with

page_text: chromic acid, permanganic acid, chloric acid, or any other suitable
oxidising agent; after the reaction ceases we mix the material so
obtained with water, filter, wash out, dry, and dissolve in fuming
sulphuric acid at 220 degrees to 230 degrees Celsius for about 2 to
4 hours until all the colour producing matter is soluble in water, then
dilute with water, neutralise with lime, precipitate with soda or caustic
soda, boil and filter, and evaporate with caustic soda in excess for several
hours at 170 degrees Celsius, until it is ascertained by a sample treated
with excess of acid that the mass does not show any increase of pre-
cipitate created by the acid; then we dissolve in water, neutralise with
hydrochloric acid and wash, the material so obtained being then ready
for dyeing and printing purposes.
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Justus Wolff and Ralph Betley in the Great Seal
Patent Office on the 5th January 1876.
TO ALL TO WHOM THESE PRESENTS SHALL COME, we, JUSTUS
WOLFF, of Wyke, near Bradford, Consulting and Engineering Chemist,
and RALPH BETLEY, of Wigan, Analytical and Consulting Chemist, send
greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Seventh day of July, in the year of
our Lord One thousand eight hundred and seventy-five, in the thirty-
ninth year of Her reign, did, for Herself, Her heirs and successors,
give and grant unto us, the said Justus Wolff and Ralph Betley, Her
special license that we, the said Justus Wolff and Ralph Betley, our
executors, administrators, and assigns, or such others as we, the said
Justus Wolff and Ralph Betley, our executors, administrators, or
assigns, should at any time agree with, and no others, from time to
time and at all times thereafter during the term therein expressed,
should and lawfully might make, use, exercise, and vend, within the
United Kingdom of Great Britain and Ireland, the Channel Islands,
and Isle of Man, an Invention for "IMPROVEMENTS IN THE PRODUCTION OF
DYES FROM NAPHTHALINE AND ITS DERIVATIVES," upon the condition (amongst
others) that we, the said Justus Wolff and Ralph Betley, our executors

page_text: or administrators, by an instrument in writing under our hands and
seals, or under the hand and scal of one of us, should particularly
describe and ascertain the nature of the said Invention, and in
what manner the same was to be performed, and cause the same
to be filed in the Great Seal Patent Office within six calendar months
next and immediately after the date of the said Letters Patent.
NOW KNOW YE, that we, the said Justus Wolff and Ralph Betley,
do hereby declare the nature of our said Invention, and in what manner
the same is to be performed, to be particularly described and ascertained
in and by the following statement, that is to say :—
This Invention relates to the production of dyes obtained from the
products which are yielded by substitution of one hydrogen atom in
naphthaline or in its suitable derivatives by one molecule of benzole or of
any of its suitablo derivatives, or of any of the suitable homologues of
benzole, or of any of their suitable derivatives, and by means of energetic
oxydation either with chromic acid, or permanganic acid, or chloric acid,
or sulphuric acid (followed by treatment with caustic alkali) or other
suitable oxidizing agent, and finally oxydation by forming sulpho-acids.
or substitutions of the before-mentioned compounds with chlorine,
bromine, iodine, nitrous acid, cyanogen, etc., and subsequently treating
with caustic soda or potash.
For the purpose of carrying out this Invention we take for example 1
equivalent of naphthaline mixed with one equivalent of dichlor benzol
and 2 equivalents of zinc powder, and heat this mixture in strong closed
vessels at a temperature of about 220° Celsius for about 12 hours. The
mass thus obtained we treat with about 3 times its weight of acetic acid
(glacial acetic acid being preferred) in order to dissolve it, and add
whilst warm, and with slight and cautious agitation, and in small
quantities at a time chromic acid until no further reaction takes place;
then we add to this mixture about 3 to 4 times its weight of cold water,
the mass is then filtered off and the residuum on the filter well washed,
dried, and dissolved in about 3 or 4 times its weight of fuming sulphuric
acid at a heat of from about 220 to about 230° Celsius, until it is ascer-
tained by a drawn sample that it completely dissolves in water (with the
exception of carbonized matters) which will be usually accomplished in
about 2 hours time. The resulting substance we treat with water,

page_text: neutralize with quicklime, boil it, filter if necessary, evaporate and treat
the evaporated solution with caustic soda (in solution) equal to about
3 times the weight of the substance which has been dissolved in
sulphuric acid for about 4 to 6 hours at 170 to 200° Celsius, until it is
ascertained by a sample treated with excess of acid that the mass does
not show any increase of precipitate created by the acid; then we
dissolve the resulting mass in water, neutralize it with hydrochloric
acid, filter, and wash; the material so obtained is ready for dyeing and
printing purposes.
Another example is as follows:-We take one equivalent phthalic acid
(produced from naphthaline by energetic oxydation with permanganic
acid, chloric acid, or nitric acid), and mix it with one equivalent of dichlor
benzol and two equivalents of zinc, in powder preferred, and heat this
mixture in strong closed vessels for about 12 hours at about 220° Celsius,
the resulting mass is then dissolved in acetic acid glacial acetic acid
being preferred) and strongly oxydised in this solution either with chromic
acid, permanganic acid, chloric acid, or any other suitable oxydising
agent; after the reaction ceases we mix the material so obtained with
water, filter, wash out, dry, and dissolve in fuming sulphuric acid
at 220° to 230° Celsius for about 2 to 4 hours, until all the color
producing matter is soluble in water, then dilute with water, neutralise
with lime, precipitate with soda ash, soda crystals, or caustic soda, boil
and filter, and evaporate with caustic soda in excess for several hours
at about 170° Celsius until it is ascertained by a sample treated with
excess of acid that the mass does not shew any increase of precipitate
created by the acid; then we dissolve in water, neutralize with hydro-
chloric acid and wash, the material so obtained being then ready for
dyeing and printing purposes.
Having now described and particularly ascertained the nature of our
said Invention, and the manner in which the same is, or may be used,
or carried into effect, we would observe in conclusion that what we
consider to be novel and original, and therefore claim as the Invention
secured to us by the herein-before in part recited Letters Patent is, the
production of dyes from naphthaline and also from the derivatives there-
from, in which one atom of the hydrogen contained therein is substituted
by one molecule of benzol or its derivatives, or the homologues of
benzol or their derivatives, by firstly submitting the same to an oxydizing

page_text: process, and after separating the products of oxidation submitting such
products to a second oxidizing process, and finally to the action of an
alkali, substantially in the manner herein-before described.
In witness whereof, we, the said Justus Wolff and Ralph Betley,
have to this our Specification set our hands and seals, the Third
day of January, One thousand eight hundred and seventy-
six.