Improvements in Preparing Coloring Matters of the Oxyketone Group, suitable for Dyeing and Printing with the Aid of Mordants.
Year: 1889

page_text: Date of Application, 20th May, 1889
Complete Specification Left, 17th Feb., 1890-Accepted, 22nd Mar., 1890
PROVISIONAL SPECIFICATION.
Improvements in Preparing Coloring Matters of the Oxyketone
Group, suitable for Dyeing and Printing with the Aid of
Mordants.
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 communi-
cated to me from abroad by the Badische Anilin and Soda Fabrik, of Ludwigshafen
on the Rhine, Germany) to be as follows:-
This Invention relates to the production of coloring matters, which according to
their chemical constitution are oxygenated derivatives of either acetophenone or of
benzophenone or of homologues and substitution compounds of the said ketones.
The property, which these oxyketones possess of dyeing with the aid of mordants,
principally depends upon the presence of at least two hydroxyl groups in their
aromatic residue and moreover upon the juxta-position of at least two of these
hydroxyl groups.
Oxygenated derivatives of the above named ketones are already known. The
known compounds do not however contain any hydroxyl groups in juxta-position in
their aromatic residues, with the exception of the oxyketones termed gallacetophenone
(Journ. Pract. Chemie XXIII, 147, 538) benzopyrocatechine (Ann. Chem. CCX, 262)
and anhydropyrogallol-ketone.
Neither of the bodies belonging to the oxyketone group, as above defined, has as
yet been known to be endowed with coloring properties.
My foreign correspondents produce their colouring matters according to this
Invention by either of the following two methods, viz. :-
I by the condensation of pyrogallol with carboxyl-derivatives (or with substitution
compounds thereof) of the fatty and aromatic series.
II by the condensation of gallic acid or of pyrogallol-carbonic acid with other
phenolic bodies.
The condensation is assisted by the agency of sulphuric acid, or of chloride of
zinc or of tetrachloride of tin or of similar so-called condensing agents.
The following oxyketones have so far yielded practical results, viz. :-
I. Trioxybenzophenone produced by heating about equal parts by weight of
pyrogallol and of benzoic acid at about 145 degrees Centigrade whilst gradually
adding, under constant stirring, about three times the weight of chloride of zinc.
The reaction is finished after about three hours, or when a sample of the melt thus
produced upon being dissolved in hot water and then allowed to get cool, no longer
separates out any laminae of benzoic acid but fine light yellow needles of the desired
compound. This point being arrived at, the result of the operation is dissolved in
much boiling water, by preference with the addition of animal charcoal, filtered and
allowed to cool down. The crystallised oxyketone thus obtained is soluble with
difficulty in cold water and easily soluble in alcohol, ether, acetone, and glacial
acetic acid. It dissolves both in alkaline liquors and in concentrated sulphuric acid
with an intense yellow colour. The solutions in caustic potash or soda liquor (these
solvents being employed in excess) rapidly attract oxygen from the air forming a
green oxidation-product. This colouring matter dyes a golden yellow colour upon
cotton which has received an alumina mordant. The chrome lake is brownish-yellow
and iron mordants produce an olive colour. A very bright yellow colour is produced
by printing a mixture of the oxyketone with acetate of alumina and tin crystals (or
citrate of tin).

page_text: The yellow colours as obtained are as fast as alizarine-dyes. In a similar manner
the following oxyketones are produced, and therefore only their chemical names and
the names of their constituents need be mentioned.
II. Trioxymonochlor-benzophenone produced from pyrogallol and para-chlor-
benzoic acid. Fine needles fusing at 154-155° (. Dyes similarly to the preceding
one.
III. Tetraoxy-benzophenone from pyrogallol and salicylic acid. Greenish-yellow
laminae, fusing at 102° C. Dyes a reddish yellow. upon alumina mordants.
IV. Tetraoxy-benzophenone from pyrogallol and metaoxybenzoic acid. Yellow
needles, fusing point 133° C., dyes like I.
V. Tetraoxy-benzophenone from pyrogallol and para-oxybenzoic acid. Yellowish
needles, not fusing at 200° C. Dyes like I.
VI. Tetraoxyphenyl tolylketone from pyrogallol and meta-cresotinic acid.
Yellow needles fusing at 118-120° C. Dyes like III.
VII. Pentaoxy-benzophenone from pyrogallol and beta-resorcylic acid. Yellowish
needles fusing at 168-170° C. Dyes like I.
VIII. Penta-oxy-benzophenone from gallic acid and resorcine.
Brownish needles fusing above 200° C. Dyes a greenish-yellow shade upon
alumina mordant.
IX. Hexa oxybenzophenone from pyrogallol and gallic acid. Long, silky, pale-
yellow needles, not_fusing at 270° C. Dyes upon alumina mordants a somewhat.]
greener shade than I.
✗. Hexaoxybenzophenone from pyrogallol and pyrogallol-carbonic acid.
Long yellow needles fusing at 238° C. Dyes similarly to IX.
The solution of this colouring matter in caustic soda liquor retains its yellow
colour in contact with atmospheric air.
XI. Trioxy ethyl phenyl ketone from pyrogallol and propionic acid.
This oxyketone crystallises in yellowish needles which, when first dried at 75° C.,
fuse at 127° C. It dyes a greenish-yellow upon alumina mordants.
XII. Trioxy-propyl-phenyl-ketone from pyrogallol and normal butyric acid.
Yellow needles, dyes like XI, fuses at 100° C., after being dehydrated, the air-.
dried crystals losing water at 70° and commencing fusion at 76° 80° C.
XIII. Trioxy-butyl phenyl ketone from pyrogallol and valerianic acid. Yellow
needles, fusing at 108 C., dyes like XI.
The above named coloring matters, containing a fatty residue (XI, XII, XIII) dye.
much less intense colours than do the preceeding ones.
Dated this 20th day of Mo 1880
COMPLETE SPECIFICATION.
Improvements in Preparing Coloring Matters of the Oxyketone
Group, suitable for Dyeing and Printing with the Aid of
Mordants.
.
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 communi-
cated to me from abroad by the Badische Anilin and Soda Fabrik of Ludwigshafen-
on-the-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 relates to the production of colouring matters which according to
their chemical constitution are oxygenated derivatives of either acetophenone or
benzophenone or of certain analogous and substitution compounds of the said ketones.
These analogous and substitution compounds are phenyltolylketone, ethylphenyl-
ketone, propylphenylketone, butylphenylketone and monochlor-benzophenone. The

page_text: property of dyeing with the aid of mordants which characterizes these oxyketones,
depends principally upon the presence of at least two hydroxyl groups in their aromatic
residue and moreover upon the juxtaposition of at least two of these bydroxyl
groups.
Oxygenated derivatives of the above named ketones are already known. The known
compounds however, with the exception of the oxyketones termed gallacetophenone
(Journal für Practische Chemie vol. 23 p.p. 147, 538) benzopyrocatechin (Annalen der
Chemie vol. 210, p. 262) and anhydropyrogallol-ketone, do not contain hydroxyl
groups in juxtaposition in their aromatic residue. Neither of the bodies belonging to
the oxyketone group, as above defined, has prior to this Invention been known to be
endowed with colouring properties.
According to this Invention the new colouring matters are produced by either of
the following two methods, viz. :-
I. By the condensation of pyrogallol with certain carboxyl-derivatives of the fatty
and aromatic series, or with their substitution compounds, viz.: benzoic acid, para-
chlorobenzoic acid, salicylic acid, meta hydroxybenzoic acid, para-hydroxybenzoic
acid, meta cresotinic acid, betaresorcylic acid, propionic acid, normal butyric acid
and valerianic acid.
II. By the condensation of gallic acid or of pyrogallol-carboxylic-acid, with certain
phenolic bodies, viz.: resorcinol and pyrogallol.
The condensation is assisted by the agency of sulphuric acid or of chloride of zinc,
or of tetrachloride of tin or of similar so-called condensing agents.
I give the following as the best means with which I am acquainted for the
preparation according to this Invention of those oxyketones which have so far yielded
practical results.
I. Trioxybenzophenone is produced by heating about one part by weight of
pyrogallol and one part by weight of benzoic acid at about 140 degrees Centigrade
and adding, whilst continuously stirring about three parts by weight of chloride of
zinc. The reaction is finished after about three hours, or the completion of the re-action
may be ascertained by dissolving a sample of the melt thus produced in hot water
when if, on cooling, no laminæ of benzoic acid separate out but only fine light yellow
needles of the desired compound, then this re-action is completed.
This point being arrived at, the melt is dissolved in a large quantity of boiling
water, with preferably a little animal charcoal added thereto. "The liquor is filtered
off and allowed to cool down, when the crystallized oxyketone separates out and is
filtered, pressed and dried.'
The oxyketone thus obtained is very slightly soluble in cold water but is readily
soluble in alcohol, ether, acetone, and glacial acetic acid. It dissolves both in alkaline
liquors and in concentrated sulphuric acid with an intense yellow colour. If dissolved
in an excess of caustic potash or soda liquor the solutions rapidly attract oxygen from
the air and a green oxidation product is formed.
This oxyketone dyes cotton which has received an alumina mordant a golden-
yellow colour. The chrome lake is brownish yellow and with iron-mordants an olive
colour is obtained. A very bright yellow colour is produced with this dye by
printing it with a mixture of acetate of alumina and tin crystals or citrate
of tin.
The yellow colours thus obtained are as fast as the alizarine dyes.
As the operations by means of which the following oxyketones are produced are
perfectly analogous to those above described it is only necessary to mention their
chemical names and the names of their constituents.
II. Trioxymonochlor-benzophenone produced from pyrogallol and parachlorobenzoic
acid.-Fine needles fusing at about 154 to 155 degrees Centigrade.-Dyes similarly
to the preceding one.
III. Tetraoxybenzophenone from pyrogallol and salicylic acid. Greenish yellow
laminæ fusing at about 112 degrees Centigrade. Dyes a more reddish yellow upon
alumina mordants.

page_text: IV. Tetraoxybenzophenone from pyrogallol and metahydroxybenzoic acid-Yellow
needles; fusing point about 133 degrees Centigrade-Dyes like the product of
Example No. I.
V. Tetraoxybenzophenone from pyrogallol and parahydroxybenzoic acid. Yellowish
needles not fusing at 200 degrees Centigrade-Dyes like the product of Example
No. I.
VI. Tetraoxyphenyltolylketone from pyrogallol and metacresotinic acid. Yellow
needles fusing at about from 118 to 120 degrees Centigrade-Dyes like the product
of Example No. III.
VII. Pentaoxybenzophenone from pyrogallol and betaresorcylic acid-Yellowish
needles fusing at about 168 to 170 degrees Centigrade-Dyes like the product of
Example No. I.
VIII. Pentaoxybenzophenone from gallic acid and resorcin. Brownish needles
fusing above 200 degrees Centigrade. Dyes a greenish yellow shade upon alumina
mordants.
IX. Hexaoxybenzophenone from pyrogallol and gallic acid-Long, silky, pale-
yellow needles not fusing at about 270 degrees Centigrade-Dyes upon alumina
mordants a somewhat greener shade than that produced according to the Example
No.. I.
X. Hexaoxybenzophenone from pyrogallol and pyrogallol carboxylic acid-Long,
yellow needles fusing at about 238° Centigrade-Dyes similarly to the product of
the Example No. IX. The solution of this colouring matter in caustic soda liquor
retains its yellow colour in contact with atmospheric air.
XI. Trioxyethylphenylketone from pyrogallol and propionic acid-This oxyketone
crystallizes in yellowish needles which after drying at about 75° Centigrade fuse at
about 127° Centigrade-It dyes a greenish yellow upon alumina mordants.
XII. Trioxypropyl-phenylketone from pyrogallol and normal butyric acid. Yellow
needles, which when dehydrated fuse at about 100 degrees Centigrade. The air dry
crystals lose water at about 70 degrees Centigrade and begin to fuse at about 76 to 80
degrees Centigrade-Dyes like the product of Example No. XI.
XIII. Trioxybutylphenylketone from pyrogallol and valerianic acid-Yellow needles
melting at 108 degrees Centigrade; dyes like the product of Example No. XI.
The colouring matters produced according to Examples XI, XII and XIII, which
contain a fatty residue, dye much less intense colours than the preceeding ones.
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 :-
A. As new articles of manufacture the herein before described colouring matters
of the oxyketone group which dye various shades of yellow on an alumina mordant,
viz. :
1. Trioxybenzophenone.
2. Trioxymonochlorbenzophenone.
Three isomeric Tetraoxybenzophenones, namely:
3. Tetraoxybenzophenone from pyrogallol and salicylic acid.
4. Tetraoxybenzophenone from pyrogallol and metaoxybenzoic acid.
5. Tetraoxybenzophenone from pyrogallol and paraoxybenzoic acid.
6. Tetraoxyphenyltolylketone.
Two isomeric Pentaoxybenzophenones, namely :-
:-
7. Pentaoxybenzophenone from pyrogallol and beta-resoŕcylic acid.
8. Pentaoxybenzophenone from gallic acid and resorcin.
Two isomeric Hexaoxybenzophenones namely:-
9. Hexaoxybenzophenone from pyrogallol and gallic acid.
10. Hexaoxybenzophenone from pyrogallol and pyrogallol-carboxylic acid.
11 Triorvaths
hanellintona

page_text: 13. Trioxybutylphenylketone.
B. The processes of preparing the hereinbefore described and claimed oxyketones,
substantially as hereinbefore described.
Dated thie 17th day of Februar 1800
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.Ċ., Agents.