The Manufacture and Production of a New Compound and of Artificial Indigo from Phenyl-glycocoll, or Analogues, Compounds, or Derivatives thereof.
Year: 1890

page_text: Date of Application, 5th June, 1890
Complete Specification Left, 2nd Mar., 1891-Accepted, 9th May, 1891
PROVISIONAL SPECIFICATION.
The Manufacture and Production of a New Compound and of Artificial
Indigo from Phenyl-glycocoll, or Analogues, Compounds, or
Derivatives thereof.
I, JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of
Middlesex, Gentleman do hereby declare the nature of this invention which has
been communicated to me from abroad by the Badische Anilin and Soda Fabrik
of Ludwigshafen on Rhine in the Empire of Germany to be as follows:-
=:
The invention is based on the discovery that phenylglycocoll and analogues
thereof, their salts, ethers, anhydrides [such as di-phenyl-di-keto-piperazine or
diphenyldiacipiperacine] also amidoderivatives thereof such as phenylglycocoll-
anilide can by appropriate treatment be made to yield indigo. The reaction
generally takes place in two steps or stages. First, a body which has the general
character of a leuco compound is obtained; this stage of the reaction is accompanied
by the splitting off of water from the glycocoll body and is brought about by the
action of suitable reagents for extracting water, such as for instance caustic potash.
The second stage of the reaction consists in oxidizing the product of the first step.
Many oxidizing agents can be employed but the best and simplest appears to be the
oxygen of the air in alkaline solution.
I give the following example as typical to further illustrate the nature of the
invention, but I premise that the invention is not restricted to the employment of
phenyl-glycocoll, or to the action of caustic potash on it and its analogues, as other
bodies, as above mentioned yield similar results to phenyl-glycocoll and other
substances which in this respect act in a similar way to caustic potash can be
substituted for it. The parts are by weight.
One part of phenylglycocoll which can be obtained as is well known from
monochloracetic acid and aniline [see Berichte der deutschen chemischen Gesellschaft
Vol. 10 p. 2046] and two parts of dry caustic potash are melted together preferably
in a closed retort and the temperature gradually raised to and maintained at about
two hundred and sixty five degrees Centigrade or higher. The melt froths up owing
to the evolution of vapours and its colour changes to deep orange. The completion
of this change marks the end of the reaction or it may be ascertained by with-
drawing test portions from the melt from time to time dissolving each in water and
oxidizing by passing air through the solution; when no increase in the quantity of
indigo formed is noticed in successive tests the operation is completed. This point
being arrived at, the entire melt is when cold dissolved in water and air is passed
through the solution. The precipitate formed is filtered off washed with water,
with very dilute hydrochloric acid and finally with alcohol and the residual indigo
is then dried.
בזי
1
T
1000
J. H. JOHNSON & Co.,
Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of a New Compound and of Artificial
Indigo from Phenyl-glycocoll, or Analogues, Compounds, or
Derivatives thereof.
I JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention (which has
been communicated to me from abroad by the Badische Aniline and Soda Fabrik
[Pric

page_text: of Ludwigshafen-on-Rhine 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 :—
This invention is based on the discovery that phenyl-glycocoll, and certain
analogues thereof, (to which hereinafter more particular reference is made) their
salts, ethers, and similar derivatives, can, by appropriate treatment, be made to
yield artificial indigo; by which I mean blue to greenish dyestuff's belonging to the
indigo group and capable of application in the dyeing industry in the same ways as
vegetable indigo.
The reaction takes place in two steps, or stages;-First, I obtain, in each case,
as herein explained, what I term a new compound; that is an intimate combination
of a body having the nature of a leuko-compound, with the excess of the re-agents
employed, and with other products of the re-action. To this compound I apply the
name of artificial indigo-white. This stage of the re-action is accompanied by the
splitting off of water from the glycocoll body, and is brought about by the action
of suitable re-agents for extracting water from the bodies operated upon.
The second stage of the re-action consists in oxidizing the product of the first step.
Many oxidizing agents can be employed for this purpose, but the oxygen of the
atmosphere is, I believe, the simplest and the best.
As aforesaid, not only phenyl-glycocoll, but also analogues thereof can be used 2
as the material from which to start in carrying out this invention. Now, as is well
known, (see Berichte der deutschen chemischen Gesellschaft Vol. 10 page 2046)
phenyl-glycocoll is obtained by the interaction of aniline and mono-chloracetic acid.
The analogues which I find may be used with advantage may be obtained similarly
by the inter-action of mono-chloracetic acid, and certain of the next higher 2
homologues, or alkyl substitution compounds, of aniline namely:
tolyl-glycocoll, from ortho-toluidine.
xylyl-glycocoll, from meta-xylidine.
methyl-phenyl-glycocoll, from mono-methyl-aniline.
ethyl-phenyl-glycocoll, from mono-ethyl-aniline.
amyl-phenyl-glycocoll, from mono-amyl-aniline.
:-
ethyl-tolyl-glycocoll, from mono-ethyl-ortho- or para-toluidine.
amyl-tolyl-glycocoll, from mono-amyl-ortho-toluidine.
•
I give examples of the manner in which it is preferred to prepare the phenyl-
glycocoll analogues for the purpose of this invention, although I do not limit myself 3
to any particular way in which they are made. Phenyl-glycocoll, ortho-tolyl-
glycocoll and meta-xylyl-glycocoll I prefer to prepare at a temperature of about
100° Centigrade in the presence of water thus:-Mix two molecular proportions of
aniline (or ortho-toluidine, or meta-xylidine, as the case may be) and one molecular
proportion of mono-chlor-acetic acid with twice the whole quantity of water and 4
boil for from about four to six hours. On cooling, the glycocoll compound, as is
well known, will separate out, and when dry it is pure enough for use in the
new process.
Ethyl-phenyl-glycocoll, methyl-phenyl-glycocoll, ethyl-tolyl-glycocoll and the
other phenyl-glycocoll analogues derived from alkyl-substitution compounds of 4
aniline, or its homologues, are preferably prepared without the addition of water,
and at a rather higher temperature.
Heat together one molecular proportion of mono-chlor-acetic acid, and two
molecular proportions of mono-ethyl-aniline (or corresponding base) for about three
hours at about 100° Centigrade, and then, for about four hours more, at about 110° 5
to 115° Centigrade; introduce the whole mass when cold into water, and add an
excess of alkali, separate off the mono-ethyl-aniline (or corresponding base) and
acidify the solution with acetic acid. If too much water has not been used a portion
of the phenyl-glycocoll analogue will separate. In any case extract the whole with
fusel oil, or ether, and isolate the phenyl-glycocoll analogue by distilling off the 5
solvert.

page_text: In some cases the nature of the artificial indigo, as shewn by the colour it imparts
to fibre, varies according to the conditions of manufacture. Thus for instance:
if ethyl-phenyl-glycocoll be treated in the alkali melt, at a temperature of, say
about two hundred and seventy degrees Centigrade, until successive test samples,
dissolved in water, shew, on oxidation, no increase in the quantity of dyestuff formed.
then the artificial indigo obtained after oxidation is a bluer dyestuff than is that
obtained by treating the same glycocoll with a caustic alkali, at a temperature of
about three hundred and fifty degrees Centigrade, until the orange colour of the
melt no longer increases in intensity and subsequently oxidizing in aqueous solution.
The dyestuff obtained through melting at the higher temperature gives a greener
shade to fibre.
In preparing artificial indigo, by means of an alkali melt, it is, in all cases,
possible to use caustic soda, instead of caustic potash; or a mixture of these two
alkalies with one another may be used. The oxides and hydrates of the metals of
the alkaline earths, such, for instance, as lime, (quick or slaked) may also be added
to the alkali with good results.
I give an example of the production of artificial indigo from ethyl-phenyl-
glycocoll at the lower temperature, which also illustrates the use of mixtures of the
alkalies.
PRODUCTION OF ARTIFICIAL
EXAMPLE 3.
INDIGO FROM
ETHYL-PHENYL-GLYCOCOLL BY
MEANS OF AN ALKALI MELT.
Heat rapidly one part of the ethyl-phenyl-glycocoll (obtained as hereinbefore
described or in any other way,) with four and a half parts of a mixture of equal
quantities of caustic soda, and caustic potash, and one part of quicklime to about
two hundred and eighty degrees Centigrade and then, within ten minutes raise the
temperature to three hundred and twenty degrees Centigrade. Allow the melt, or
artificial indigo, when thus obtained, to cool, and, when cold, dissolve it in water
and filter off the undissolved lime, keeping the liquid as far as possible from
exposure to the air; pass air through the solution, till no more blue précipitate
forms, filter, wash with water, then with hydrochloric acid, and then with alcohol,
and dry the artificial indigo obtained.
The properties of the artificial indigo so obtained closely resemble those of the
indigo obtained from phenyl-glycocoll in the manner hereinbefore described.
The extraction of water from phenyl-glycocoll, and its analogues, to yield an
artificial indigo-white can be effected in certain cases by means of sulphuric
acid. Now, just as fuming sulphuric acid readily converts vegetable indigo and the
artificial indigo hereinbefore described into the form of sulpho-acid soluble in
water, so, in this process, the fuming sulphuric acid used, not only attacks the
glycocoll compound to extract the water, but sulphonates the indigo compounds
during their formation, so that the ultimate product is artificial indigo in the form
soluble in water.
The following example illustrates this way of carrying this invention into
effect:-
EXAMPLE 4.
PREPARATION OF ARTIFICIAL INDIGO, IN THE FORM SOLUBLE IN WATER, BY
THE ACTION OF FUMING SULPHURIC ACID UPON PHENYL-GLYCOCOLL.
PREPARATION OF ARTIFICIAL INDIGO, IN THE FORM SOLUBLE IN WATER, BY
THE ACTION OF FUMING SULPHURIC ACID UPON PHENYL-GLYCOCOLL.
Add about fifty parts of phenyl-glycocoll, gradually, to about four hundred
parts of fuming sulphuric acid, containing about thirty per cent. of free anhydride
[SO], stir carefully, and keep the mixture cool, so that, at no time, does the
temperature exceed about forty degrees Centigrade. As soon as the glycocoll
compound is completely dissolved, pass a stream of moist air through the solution
until no more fumes are given off; keep the solution cool during this operation, and

page_text: subsequently continue to pass air through the solution until the colour no longer
increases in intensity. Pour the whole into ten times the quantity of water and
precipitate the sulphonated artificial indigo with common salt (previously
neutralizing part of the acid with soda, if necessary) filter, press, and dry.
This sulphonated artificial indigo can be used like sulphonated vegetable indigo
(indigo-carmine) for dyeing animal fibre from the acid bath.
This process can be applied to certain analogues of phenyl-glycocoll; that is to
say, methyl-phenyl-glycocoll and ethyl-phenyl-glycocoll and with these, sulphonated
artificial indigo is obtained which imparts greener shades to fibre than sulphonated
vegetable indigo (indigo-carmine).
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The manufacture of what I have termed artificial indigo-white by treating
phenyl-glycocoll (or its analogues, compounds, or derivatives as herein before
mentioned) with a body that effects the extraction of water, substantially as herein-
before described.
2. The manufacture of what I have termed artificial indigo by treating phenyl-
glycocoll (or its analogues, compounds, or derivatives, as herein before mentioned,)
with a body that effects the extraction of water, and with an oxidizing-agent,
substantially as hereinbefore described.
3. The manufacture of what I have termed a body having the nature of an
indigo leuko-compound, by treating phenyl-glycocoll, ortho-tolyl-glycocoll, meta-
xylyl-glycocoll, ethyl-phenyl-glycocoll, or ethyl-tolyl-glycocoll, at a high
temperature with caustic potash, or with caustic soda, or with a mixture of caustic
potash and caustic soda, in each case either with, or without, the addition of an
oxide, or a hydrate of a metal of the alkaline earths, all substantially as herein-
before described.
4. The manufacture of what I have termed artificial indigo by treating phenyl-
glycocoll, ortho-tolyl-glycocoll, meta-xylyl-glycocoll, ethyl-phenyl-glycocoll, or
ethyl-tolyl-glycocoll, at a high temperature with caustic potash, or with caustic
soda, or with a mixture of caustic potash and caustic soda, in each case either with,
or without, the addition of an oxide or hydrate of a metal of the alkaline earths, and
subsequently oxidizing the melt dissolved in water by means of the oxygen of the air,
or equivalent oxidizing agent, all substantially as herein before described.
5. The manufacture of what I have termed artificial indigo in the soluble form
of a sulpho-acid by treating phenyl-glycocoll, methyl-phenyl-glycocoll, or ethyl-
phenyl-glycocoll, with fuming sulphuric acid and subsequently oxidizing the
solution obtained, substantially as hereinbefore described.
6. The products obtained by proceeding according to any of the processes which
are claimed in the above claiming clauses.
Dated this 2nd day of March 1891.
J. H. JOHNSON & Co.,
Agents.