5576 5580.output

* GB785984 (A)
Description: GB785984 (A) ? 1957-11-06
Improvements in or relating to the manufacture of metal ingots and castings
Description of GB785984 (A)
AMENDED SPECIFICATION
Reprinted as amended in accordance with the decision of the
Superintending Examiner, acting for the Comptroller-General, dated the
fourteenth day of January, 1960, under Section 33, of the Patents Act,
1949.
PATENT SPECIFICATION
DRAWINGS ATTACHED In'ventor: KOSSY STRAUSS 785,984 Date of filing
Complete Specification: Feb 24, 1956.
Application Date: March 7, 1955 No 6667/55.
Complete Specification Published: Nov 6, 1957.
Index at acceptance: Classes 82 ( 1), W; and 83 ( 1), F 11 (S: W).
International Classification:-B 22 c C 22 d.
COMPLETE SPECIFICATION
Improvementsi in or relating to the Manufacture of Metal Ingots and
Casftings We, FOUNDRY SERVIC Es LIMITED, of Long Acre, Nechells,
Birmingham 7, a British Company, do hereby declare the invention, for
which we pray that a patent may be granted to us, and the method by
which it is to be performed, to be particularly described in and by
the following statement: -
The present invention relates to the manufacture of metal ingots and
castings and is more particularly concerned with the casting of steel
and other metals in ingot form.
In producing metal ingots, it is customary practice, in order to avoid
the adverse effects of uneven cooling of molten metal when poured into
an ingot mould, to employ refractory tiles having low thermal
conductivity to provide heat insulation, either by lining the top
portion of the ingot mould or by fitting the tiles into a separate
ingot head box which is located on top of the mould It has been known
for a considerable time that both the yield and soundness of ingots

produced in such moulds are increased if the refractory tiles are
pre-heated prior to pouring the ingot.
It is also known to employ, instead of tiles which only have heat
insulating properties, tiles or other moulded ishapes such as sleeves
made of exothermic: material, which set up a heat-producing reaction
in contact with the molten metal and thereby delay cooling of the
adjacent part of the poured ingot Exothermic mixtures which can be
used in this manner are aluminium-containing mixtures such as are
described in Specification No.
627,678.
Although such a technique has been utilised lPrice 3 s Razz, I 1, on a
production scale, its application is limited, particularly for ingots
of the inherently cheap metals, since the cost of the exothermic
materials can outweigh the advantages of increased ingot yield,
increased soundness of ingot and, possibly, increase in the number of
ingots produced per ladle of metal Also, and this is of great
importance, the efficiency of the exothermic compounds is reduced,
since the fabricated exothermic tiles and similar shapes come into
contact with the highly thermally-conducting metal of the ingot mould
or head box This results in much of the heat evolved from the
exothermic material being wasted instead of being utilised for
superheating the tile or similar shape and delaying the solidification
of the ingot head metal Proposals have been made for applying a lining
of exothermic material to a sand or similar layer already present in
the mould or in a hot top.
The object of the present invention is to increase the efficiency of
mouldable exothermic materials when employed for the feeding of ingots
and also of castings, by reducing the loss of evolved heat to
materials other than the ingot or casting head metal.
According to the present invention, a shaped fabricated laminar,
separately vendible article for use with an ingot mould or other metal
casting mould is provided, having an outer layer, namely that which
does not contact the molten metal, constituted by a heat insulating
material, and an inner layer, which contacts the molten metal,
constituted by a mouldable aluminium-containing exothermic material,
and a layer of mildly exothermic material there between the layers
being firmly bonded together.
Preferably, the mouldable exothermic material used is as described in
Specification
No 627,678.
Shapes composed of exothermic material for superheating the tiles or
other shaped articles and for delaying the solidification of the
feeder head metal, and a good insulator for minimizing the loss of
heat from the exothermic material itself enable a more efficient

application of exothermic materials for feeda) Lining of insulating
materi, b) Lining of exothermic materi c) Duplex lining (half inch v
exothermic material surroun a half inch wall of insi material) These
results clearly indicate that exothermic linings are more efficient
than purely insulating ones, but that the efficiency of exothermic
linings is very considerably improved by separating the exothermic
material from the metal mould by means of a layer of insulating
material.
Other experiments made in a steel works producing 4 " square ingots in
high speed steel confirmed that tiles consisting of an inner layer of
exothertnic material and an outer layer of insulating material are
considerably more efficient than tiles made entirely of exothermic
material or insulating material In these experiments, the billet to
ingot yield was 72 % when an insulating liner was used, 78 % when an
exothermic liner was used and 8283 ' when a duplex liner was employed.
It will be appreciated that the thicknesses of the individual layers
in the tile or other shaped article may be varied so as to suit the
size of the particular ingot or casting to be produced The shaped
articles of the present invention consist of three individual layers
which comprise an inner layer of strongly exothermic material, such as
described in the afore-mentioned Specification No 627,678, an
intermediate layer of mildly exothermic material, such as a
carbonaceous material, and an outer, heat-insulating layer the
articles being in the form of tiles, sleeves or the like.
As the heat-insulating layer, there may be used any refractory,
heat-insulating materials, such as sand or aliuminous grog.
In order that the invention may be readily understood, reference is
made to the following description of the accompanying drawing, in
which a preferred shaped article is illustrated and also to the
subsequent specific Example; the drawing shows a perspective view of a
cylindrical sleeve consisting of a layer of insulating material and
layers of two different exothermic materials It consists of an outer
layer 14 of insulating and inert material, an ing purposes and also
markedly reduce the cost of the tiles, so that they may be used to
considerable economic advantage, even on ingots of inherently cheap
metals.
In experiments to determine the efficiency of various liners, the rate
of cooling of molten copper filling a cylindrical cavity 8 " deep x 6
" diameter in a metal mould lined with an inch thick wall of the
lining materials was investigated under laboratory conditions Copper
poured at 13000 C took the following times to solidify:
al 28 minutes.
al 36 Vall of ded by flating 48 minutes.
intermediate layer 15 of mildly exothermic material and an inner layer

16 of strongly exothermic material This sleeve can be used to line
cylindrical passage-ways in ingot moulds, such as risers and feeder
heads.
EXAMPLE.
Suitable com-positions of heat-insulating and inert material are as
follows:
Grog, sand, crushed firebrick or any other granular refractory
material 80-90 % Binder (such as sodium silicate, dextrine gum or
sulphite lye) 6-10 % Clay or fireclay 4-10 %' A heat insulating
material as aforesaid is moulded into a sleeve by moistening with
water and ramming into a pattern or core box, usually of cylindrical
shape To the inner surface of this is applied a lining of a mildly
exothermic material for the following composition:
Carbonaceous material such as charcoal or coke 60-65 % Grog or sand
10-15 %O Dextrine or sulphite lye 15-20 % Iron millscale O 5 % To the
inner surface of the mildly exothermic layer is applied a layer of
strongly exothermic material of the following composition:
Aluminium particles 15-35 % Sodium nitrate 5-10 ' Iron oxide O 5 %
Core gum 1-5 % Cryolite, sodium fluoride or sodium silicofluoride 1 5
% Sand 40-60 % The sleeves thus formed has the structure shown in the
drawing and can be used as mentioned in connection therewith The
bonding agent in the insulating and exothermic materials is usually a
water-soluble organic gum or sodium silicate which requires drying,
but for this purpose many self-setting cements 785,984 in which the
mouldable exothermic material used is as described in Specification
No.
627,678.
3 A shaped article as claimed in claim 1 or 2 in which the heat
insulating material comprises a layer of aluminous grog, sand or
mixtures thereof.
4 A shaped article as claimed in any of
* Sitemap
* Accessibility
* Legal notice
* Terms of use
* Last updated: 08.04.2015
* Worldwide Database
* 5.8.23.4; 93p
* GB785985 (A)

Description: GB785985 (A) ? 1957-11-06
Improvements in the carbonylation of olefinic compounds
Improvements in the Carbonylation of Olefinic Compounds
We, Esso RESEARCH AND ENGINEERING
COMPANY, a corporation duly organized and existing under the laws of
the State of
Delaware, United States of America, having an office at Elizabeth, New
Jersey, United
States of America, do hereby declare the invention, for which we pray
that a patent may be granted to us, and the method by which it is to
be performed, to be particularly described in and by the following
statement :
The present invention relates to a carbonylation process, that is a
process that involves the preparation of oxygenated organic compounds
by the reaction of carbon monoxide and hydrogen with carbon compounds
containing olefinic linkages in the presence of a carbonylation
catalyst.
It is now well known in the art that oxygenated organic compounds may
be synthesized from organic compounds containing olefinic linkages by
a reaction with carbon monoxide and hydrogen in the presence of a
catalyst containing metals of the iron group, such as cobalt or iron,
preferably the former, in an essentially three-stage process. In the
first stage, the olefinic material, catalyst and the proper
proportions of CO and H2 are reacted to give a product consisting
predominantly of aldehydes whose molecules contain one carbon atom
more than the molecules of the reacted olefin. This oxygenated organic
mixture, in which are dissolved salts and the carbonyls and molecular
complexes of the metal catalyst, is treated in a second stage to cause
removal of soluble metal compounds from the organic material in a
catalyst removal zone. The catalyst-free material is then generally
hydrogenated to the corresponding alcohols, or may be oxidized to the
corresponding acid.
This carbonylation reaction provides a particularly attractive method
for preparing valuable primary alcohols which find large markets,
particularly as intermediates for plasticizers, detergents and
solvents. Amenable to the reaction are long-chained and short-chained

olefinic compounds, depending upon the type of alcohols desired. Not
only olefins, but most organic compounds possessing at least one
non-aromatic carbon-carbon double bond may be reacted by this method.
Thus straight-chained and branchxhained olefins and diolefins, such as
propylene, butylene, pentene, hexene, heptene, butadiene, pentadiene,
and styrene, olefin polymers, such as di- and tri-isobutylene, hexene
and heptene dimers, and polypropylene, olefinic fractions from the
hydrocarbon synthesis process and thermal and catalytic cracking
operations, and other sources of hydrocarbon fractions containing
olefins may be used as starting material, depending upon the nature of
the final product desired.
The catalyst in the first stage of the prior process is usually added
in the form of salts of the catalytically active metal with fatty
acids of high molecular weight, such as stearic, oleic, palmitic, and
naphthenic acids.
Thus, suitable catalysts are, for example, cobalt oleate or
naphthenate. These salts are soluble in the liquid olefin feed and may
be supplied to the first stage as hydrocarbon solution or dissolved in
the olefin feed.
The synthesis gas mixture fed to the first stage may consist of any
ratio of H2 to CO, but preferably these gases are present in about
equal volumes. The conditions for reacting olefins. with H2 and CO
vary somewhat in accordance with the nature of the olefin feed, but
the reaction is generally conducted at pressures in the range of about
1500 to 4500 p. & i.g., and at temperatures in the range of about
150"--450" F. The ratio of synthesis gas to olefin feed may vary
widely; in general, about 2500 to 15,at)0 cubic feet of H2 + CO per
barrel of olefin feed are employed.
At the end of the first stage, when the desired conversion of olefins
to oxygenated compounds has been effected, the product and unreacted
material are generally withdrawn to a catalyst-removal zone where
dissolved catalyst is removed from the mixture by thermal treatment in
the presence of an inert gas, a vapor, hot water, or dilute acid.
Thereafter, the aldehydic reaction product is generally hydrogenated
to the corresponding alcohoL
It has been recognized that substantially all forms of cobalt catalyse
this reaction, for the active catalytic agent is cobalt hydrocarbonyl
in all probability; this compound is synthesized in situ from the
cobalt compound or metal originally introduced. However, it has been
preferred to employ the compounds of cobalt that are oil-soluble, such
as high molecular weight salts of cobalt, e.g. cobalt oleate or
naphthenate. These materials form a homogeneous reaction mixture and
have a reactivity or reaction rate, substantially higher than that of
cobalt metal or oxide, or aqueous solutions of cobalt salts, such as

cobalt formate or acetate. However, the use of high-molecular-weight
cobalt carboxylates has certain disadvantages. They are expensive to
prepare, requiring a variety of processing steps, and also contaminate
the final reaction product with the acid or ester corresponding to the
carboxylate employed. Furthermore, though the reactivity and reaction
rates are high, leading ro high olefinic conversions, the aldehyde and
alcohol selectivity resulting from use of these catalysts is not
always satisfactory, and may be somewhat low.
An alternative system is the use of metallic cobalt or a slurry of
cobalt oxide. These catalytic agents, although they have no residues
to contaminate the aldehyde or alcohol product, and although they give
a higher alcohol selectivity than the oil-soluble cobalt soap, have a
very slow reaction rate. This is a very serious defect in continuous
operation, since the reactants must pass through very slowly.
A third alternative has been the use of aqueous solutions of
water-soluble salts, such as cobalt acetate solutions. Here, also, the
contamination problem is substantially less than in the case of
oil-soluble salts, and alcohol selectivities at a given olefin
conversion level are higher than for an equivalent amount of a
high-molecular-weight cobalt salt. As in the case of the cobalt metal
and oxide, the cobalt acetate is also substantially cheaper than the
oil-soluble salt, such as the oleate. Thus, the conversion-selectivity
relationship for cobalt oleate and cobalt acetate catalysts may be
illustrated as follows for equivalent amounts of catalyst. The
selectivity values are adjusted to an olefin conversion in the Oxo
stage of 75%.
Percentage
selectivity
Catalyst Addition technique to alcohol
Cobalt oleate In olefin solution 7879%
Cobalt acetate In aqueous solution 87%
Cobalt acetate Solid acetate tetrahydrate 81%
In the foregoing discussion, the terms"alcohol selectivity" and
"olefin conversion" are defined as follows:
(volume of alcohol recovered)
alcohol selectivity per cent= x 100
(volume of feed converted)
(Volume of feed) -(volume of feed recovered)
conversion per cent=-x 100
(volume of feed)
The percentage yield of alcohol (based on feed) is then equal to
(conversion %) x (alcohol selectivity %)
100 since (volume of feed) = (volume of feed converted) + (volume of
feed recovered).

Other phases of these data would appear to suggest considerable
advantages of cobalt acetate catalyst over cobalt oleate, besides its
50% greater cheapness. However, though alcohol selectivities are
higher, reaction rates of aqueous solutions of cobalt acetate are
considerably slower than those of the oil-soluble cobalt salts. In
order to add an amount of cobalt acetate equivalent to cobalt oleate
to provide the desired cobalt concentration of about 0. 3 weight %,
about 54 volume % of water (based on olefin) must be added to the
olefin feed. It was found, however, that such a system, i.e., olefin
plus aqueous cobalt acetate, did not function efficiently, and gave a
more unfavourable feed-rate-times-percentageefin-conversion
relationship than cobalt oleate catalyst at equivalent cobalt
concentration. This is illustrated in the following example, where a
heptene fraction from a propylenebutylene polymerization unit was
continuously carbonylated with 0.3 wt. % of cobalt catalyst at
340--350" F.
Liquid Feed Conversion Catalyst System Rate V/V/Hr. Mol %
Cobalt Oleate in Olefin Solution 0.6 80
Cobalt Oleate in Olefin Solution 1.2 74
Cobalt Acetate in Aqueous Solution 0.6 72
1.2 54
Thus with the aqueous cobalt acetate catalyst, it is necessary to
decrease the olefin feed rate by about 50% to achieve a conversion
level equivalent to cobalt oleate. In batch operations in autoclaves,
these differences are not at once apparent or recognized unless
conditions are especially provided to measure reaction rates.
It has now been found that solid cobalt acetate, and specifically
Co(CH3O2)2AH2O, gives high aldehyde and alcohol selectivities and a
high percentage olefin conversion, and is thus peculiarly adapted to
use in a continuous carbonylation operation. Accordingly the invention
provides a carbonylation process in which an olefinic compound is
reacted with hydrogen and carbon monoxide at an elevated temperature
and pressure, characterized ia that the catalyst in the carbonylation
reaction is solid cobalt acetate.
Although it is known that beneficial effects, including an increase in
alcohol selectivity, are obtained ia certain instances by adding water
to the reaction system in the carbonylation reactor, it has now been
found that when cobalt acetate is used as a carbonylation catalyst the
presence of water substantially decreases the olefin conversion with
only slight increase in percentage alcohol selectivity.
The property of producing high alcohol selectivities at high
percentage olefin conversions is apparently unique with cobalt
acetate. As will be shown below, this property is not shared by cobalt
solids as such, or even by low molecular cobalt salts or carboxylates

as such.
In accordance with the present invention, therefore, solid cobalt
acetate, such as the tetrahydrate, is added as a slurry either in the
olefia feed or ia the product; preferably, however, in the feed. The
slurry may be injected into the Oxo reactor by any conventional method
of adding a slurry or paste to a system under pressure. Such methods
include slurry pumps, paste injectors, surge systems, etc.
One embodiment of a system suitable for carrying out the present
invention is shown diagrammatically in the accompanying drawing.
Turning now to the drawing, solid cobalt acetate tetrahydrate of
suitable particle size is introduced into mixing chamber 2 through
hopper 4.
Olefin feed or Oxo product is added to the mixing chamber through line
3 such that the slurry contains from 2 to 10% solids. By means-of the
circulation pump 6, the slurry is circulated through lines 8, .10 and
15 to both the top and bottom of the mixing chamber.
By means of a suitable surge pump liquid olefin or Oxo product is
introduced through lines 14 and 16 into surge vessel 18. The system is
so designed that except under positive action from the surge pump, the
pressure in the surge vessel is sufficiently low to allow slurry to
pass through the lower check valves in line 12. Under positive action
from the surge pump, the slurry is forced through the upper check
valves ia line 20.
The slurry of cobalt acetate dispersed in the olefin feed or other
organic medium, such as recycle aldehyde product or even alcohol
distillation bottoms is thus continuously injected into carbonylation
reactor 24 through line ; 22. The slurry which consists of about 0.5
to 3% by weight of cobalt acetate tetrahydrate calculated as cobalt,
may be injected at the rate of about 5 to 200 pounds per barrel of
olefin, at pressures preferably equal to or slightly higher than those
prevailing in reactor 24.
A gas mixture comprising H2 and CO in approximately equal volumes,
though from 0.5 to 2 volumes of H2 to 1 volume of CO may be used, is
supplied through line 26 and flows concurrently with preheated liquid
olefin feed admitted through line 28, and with the catalyst slurry.
Reactor 24 is preferably operated at pressures of about 2500-3500 p.
s. i. g. and temperatures of 300-375 F., depending upon the olefin
feed and other reaction conditions.
Liquid feed rates of 0.2 to 2.0 V/V/hour may be employed, which are
substantially greater than when aqueous solutions of cobalt acetate,
or even anhydrous or water-:ontain- ing slurries of cobalt metal,
cobalt oxide, or cobalt carbonate are employed.
Liquid oxygenated reaction products consisting mainly of aldehydes,
containing cobalt carbonyl in solution, as well as unreacted synthesis

gases, are withdrawn overhead through line 30 from higher pressure
reactor 24 and thereafter reacted in a manner now well knows in the
art,, and not forming a part per se of the present invention. Thus,
the cobalt-contaminated aldehyde product may be freed of cobalt by
heating it in the presence of water or dilute acid, in particular
dilute acetic acid, and thereafter hydrogenated to the corresponding
alcohol. Dilute acetic acid provides a particularly advantageous
method for recovering the catalyst as cobalt acetate directly. It is
desirable to degas the aldehyde product before treatment with acetic
acid if it is desired to recover cobalt as cobalt acetate solution.
The latter is thereafter evaporated to recover the cobalt salt as the
solid tetrahydrate.
The advantages of the present invention may be further illustrated by
the following experiments :
EXPERIMENT L
This experiment describes the technique employed in studying the
reaction rates.
The : olefin feed and catalyst, either as a solid or in solution, are
charged to a stainless steel shaker autoclave. The charge is adjusted
to the size of the autodave such that there will always be a
substantial excess of synthesis gas and that temperature can be
controlled.
In general, the liquid charge and catalyst occupy 1530% of the volume
of the vessel
The vessel is sealed, purged several times with synthesis gas, and
tested for pressure tightness at a pressure near the desired operating
value. After reducing pressure to a low level, about 200 p.s.i.g., the
contents of the vessel are brought to the desired temperature and the
synthesis gas pressure is then increased to the maximum operating
value, generally 2500 3500 p.ai.g. Depending upon the nature of the
feed and catalyst, an induction period ranging from a very few minutes
to several hours may be observed.
There is little or no gas consumption as indicated by pressure drop
during the induction period. Once reaction starts, a steady decrease
in pressure takes place and the pressure is allowed to decrease from
its original value to not less than 1700 p.s.i.g. The reaction is
relatively insensitive to pressure in the range of 1700-3500 p.s.i.g.
It is preferable to choose catalyst concentrations such that the
reaction takes place under essentially constant temperature. The
reaction is allowed to proceed until sufficient gas is absor'oed to
convert at least 5060% of the olefin, repressuring, if necessary. It
is preferable to obtain a pressure-time chart from a continuous
pressure recorder. From this record, several points on an
olefin-conversion reaction-time correlation can be calculated from the

gas laws and the free volume of the reactor. Calculations should never
go beyond 70% conversion of olefin.
The data thus obtained are found to represent a first-order reaction
and a plot of the logarithm of a function of the unconverted olefin
concentration against time is linear.
From the slope of the line, the conventional first order reaction rate
constant may be calculated. These rate calculations are quite
reproducible at constant temperature and catalyst concentration.
EXPERIMENT II.
In the example below, the reaction rate constants kx 104 were
determined, in the manner described in the foregoing experiment for a
series of cobalt-containing solids and solutions. The reaction rate
constants were determined at 0.2% cobalt equivalent with a heptene
fraction prepared by copolymerizing propylene and butylenes on a
P2O-kieselguhr catalyst.
Reaction
Rate
Induction Catalyst
Temperature Period Min.
Catalyst "F. Minutes kx102
Cobalt Oleate 300 81 2.1
Cobalt Carbonyl 300 None 2.0
Aqueous Cobalt Acetate Solution (7% water 300 > 60 0.2
based on olefin)
Solid Cobalt Acetate Tetrahydrate - 300 10 1.7
Cobalt Oleate 340 30 6.5
Solid Cobalt Acetate Tetrahydrate - 340 10 3.2
Aqueous Cobalt Acetate Solution (4% water 340 20 1.4
based on olefin)
Solid Cobalt Carbonate 350 5 0.4
Solid Cobalt Oxalate 5 350 5 0.5
Solid basic Cobalt Formate 350 5 0.5
Cobalt Oxide 350 4--5 0.7
Cobalt Metal 350 4-7 0.3
Solid Cobalt Sulfate Heptahydrate 350 < 5 0.7
These data show clearly that the reaction rates obtainable with the
solid cobalt acetate are closer to the rates obtainable with cobalt
oleate or cobalt carbonyl, the best known catalysts in activity, than
the rates obtainable with aqueous cobalt acetate solution. The data
further show that this property is not shared by other cobaltiferous
solids by the simple exclusion of water. Neither do other anhydrous
cobalt salts of low molecular weight show these high reaction rates.
The low reaction rates of the cobalt oxalate, carbonate, basic
formate, oxide and metal are a direct result of the low rate of

conversion of these solids to active catalyst, i.e. cobalt
hydrocarbonyl. This low rate of conversion is apparently not caused by
reaction inhibitors, for the induction periods are not greater than
those experienced with cobalt oleate or acetate catalysts at
equivalent conditions. It appears, thus, that solid cobalt acetate and
in particular hydrated cobalt acetate, preferably the tetrahydrate, is
unique in its ease of conversion to active catalyst
The process of the invention admits of numerous modifications apparent
to those skilled in the art. Thus, it may be desirable under certain
circumstances to incorporate the solid cobalt salt into a paste with a
hydrocarbon material such as liquid petrolatum or wax. Also, the
catalyst slurry may be prepared in batch as well as continuous
operation.
What we claim is:
1. A carbonylation process in which an olefinic compound is reacted
with hydrogen and carbon monoxide at an elevated temperature and
pressure, characterized in that the catalyst in the carbonylation
reaction is solid cobalt acetate.
* Sitemap
* Accessibility
* Legal notice
* Terms of use
* 5.8.23.4; 93p
* GB785986 (A)
Description: GB785986 (A) ? 1957-11-06
Transistor circuits
A high quality text as facsimile in your desired language may be available
amongst the following family members:
US2809304 (A)
US2809304 (A) less

Translate this text into Tooltip
[79][(1)__Select language]
Translate this text into
The EPO does not accept any responsibility for the accuracy of data
and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
785,986 Date of Application and filing Complete Specification: April
12, 1955.
No 10441/55.
Application made in United States of America on April 15, 1954
Index at acceptance:-Class 40 ( 6), G( 1 M: 2 U), T.
International Classification:-HO 3 f, k.
Transistor Circuits We, INTERNATIONAL BUSINESS MACHINES CORPORATION, a
corporation organized and existing under the laws of the State of New
York, United States of America, of 590 Madison Avenue, New York 22,
New York, United States of America, do hereby declare the invention,
for which we pray that a patent may be granted to us, and the method
by which it is to be performed, ito be particularly described in and
by the following statement: This invention relates to transistor
citcuits, and particularly to trigger circuits embodying transistors
The circuits of the present invention resemble in certain respects
those of our copending application No 722,516.
A switching circuit may be defined as a circuit having an output which
shifts suddenly between separated values of electrical quantities If a
switching circuit has two stable output states, in either of which it
will remain indefinitely once it is established there, it is known as
a bistable circuit The term "trigger circuit" is sometimes used
synonymously with "bistable circuit" More frequently, the term
"trigger circuit" is used to identify a bistable circuit having a
single set of input terminals, which is switched back and forth
between its two output states by means of successive signals received
at those input terminals When the term "trigger circuit" is used in
this manner, it is to be distinguished from a latch circuit, which is
a bistable circuit having two sets of input terminals, and which is
switched from one stable set to the other by a single impulse at one
terminal and switched back from the other state to the one state by a
signal at the opposite set of input terminals.

Where a trigger circuit is switched from one set to the other and back
again in response to two successive signal impulses of the same
polarity applied at the same set of input terminals, it is spoken of
as a scaling trigger circuit or sometimes as a binary trigger circuit.
The present invention relates particularly to such scaling trigger
circuits.
lPrice 3 s 6 d l There are disclosed in our specification No.
722,516 certain trigger circuits which employ both a transistor and a
vacuum tube connected in series with the transistor base In such
circuits, the emitter current is the sum of the base current and the
collector current The collector can receive current only through the
emitter, because of the presence of the asymmetrically conductive tube
in series with the base, which prevents current flow through the base
toward the collector In the circuits disclosed in the said copending
application, a feedback is provided between a load resistor in series
with the collector and the grid of the tube, so that an increase in
the collector current tends to increase the base current and a
decrease in the collector current tends to decrease the base current
The variation in the base current produces a corresponding variation
in the emitter current, with a following variation in the collector
current Consequently, the circuit operates in one of two stable states
In one such state, referred to as the OFF state, the tube is cut off,
and the emitter current equals the collector current, which is very
low In the other state referred to as the ON state, the emitter is
conducting current at substantially its maxiknum capacity, and the
tube and the collector are also conducting in their maximum current
The system is switched back and forth between these two ON and OFF
states by means of a series of input signal pulses of the same
polarity, which are fed simultaneously into two points in the circuit
One of these points is the grid of the tube and the other is the base
of the transistor The signal supplied to the transistor base is
effective when the circuit is in its OFF condition to start an
increase in the emitter current with a following increase in the
collector current and hence in the tube current so as to switch the
circuit to its ON condition.
The signal transmitted to the grid of the tube is ineffective When the
tube is cut off After the tube circuit is transferred to its ON
condition, the next input signal pulse is ineffective -I f ( at the
transistor base, since the emitter is already carrying substantially
its maximum current The signal supplied to the grid of the tube is
then effective to initiate a decrease in the tube current with
following decreases in the emitter and collector current, thereby
starting a cumulative process which is effective to switch the circuit
back to its OFF condition.

Transistor characteristics vary considerably from one transistor to
another, and the characteristics of a given transistor vary with time
It is therefore an ever present problem in connection with transistors
to provide circuits which will not be sensitive to such variations in
characteristics While the circuits of the prior application are not,
as transistor circuits go, particularly sensitive to such variations,
it is nevertheless highly desirable to inprove the circuits further
from that standpoint.
The circuits of our prior application have a continuous small value of
current flow, even in the OFF state This small current flow produces
an undesirable power loss and also limits the output signals
available, i e, it limits the difference obtainable between the
maximum and lminimum output conditions.
It is an object of the present invention to provide an improved
transistor circuit Another object is to provide an improved scaling
trigger circuit.
According to the invention, we provide an electronic trigger circuit
comprising a tran3 sistor, first and second sources of unidirecttional
electrical energy connected in series, means connecting the emitter to
the joined terminals of said sources, variable impedance means
connected between the base of the transistor and the other terminal of
one source, positive feedback means connecting a collector load
impedance and said variable impedance means, a voltage divider
connected across the other source, and a means connecting an
intermediate point on the voltage divider to said base, the other
source and the voltage divider being arranged to cooperate when the
impedance of the variable impedance means is high to bias the
transistor OFF while said first source is arranged to be effective
when the impedance of the variable impedance means is low to send a
current through a portion of the voltage divider and thereby to bias
the base in a sense to turn the transistor ON.
In a preferred form, the biasing circuit includes a biasing battery
'having two voltage dividing resistors connected in series across its
terminals The negative terminal of the biasing battery is connected to
the positive terminal of the battery which supplies current to the
emitter The mid-point of the voltage divider is connected to the base
of the transistor.
When the tube is in its OFF condition, the voltage divider circuit is
effective to bias the base substantially with respect to the emitter
in a sense to inhibit the injection of current carriers from the
emitter, thereby reducing the emitter current substantially to zero
When the tube is conducting a current, part of the current of the tube
flows from one terminal 7 ( of the emitter current supplying battery
through one resistor of the voltage divider, in a direction to reduce

the potential of the midpoint of the voltage divider below that of
said one terminal of the emitter current supplying 7.
battery, thereby biasing the base in a sense to promote the injection
of current carriers by the emitter.
The biasing circuit is thereby effective to reduce the output current
in the OFF state, 8 ( and to increase to some extent the output
current in, the ON state An increased differential between the output
electrical conditions in the ON and OFF states is thereby provided.
The power consumption in the OFF state is 85 practically eliminated,
and the resulting circuit is muchi less sensitive to variations in the
transistor characteristics This is particularly true insofar as such
variations may effect the current flow in the OFF state of the circuit
9 C Other objects and advantages of our invention will become apparent
from a consideration of the following specification taken together
with the accompanying claims and drawing.
In the drawing: 95 Fig 1 is a wiring diagram of one form cf transistor
circuit employing the invention, anl Fig 2 is a wiring diagram of a
modified forin of transistor circuit embodying the invention, 101
There are only slight differences between the circuits of Figs 1 and
2, and the same reference numerals have been used to indicate
corresponding parts in both circuits.
Referring to Fig 1, there is shown a tran 10 l sistor 1 having an
emitter electrode le, a collector electrode lc and a base electrode
lb.
It is assumed that the transistor 1 has a body of n-type
semi-conductive material, although it will be readily understood that
the inven 11 ( tion is equally applicable to transistors having bodies
of p-type material, with appropriate changes in polarities, etc An
electric discharge device 2, shown as a triode including an anode 3, a
control electrode 4 and a cathode 5 has 11 ' its anode 3 connected
directly to the base lb through a conductor 6 Cathode 5 is connected
through a resistor 7 and a parallel capacitor 8 to a grounded
conductor 9.
Current for the emitter le is supplied by a 12 ( battery 10 having its
negative terminal connected to the grounded conductor 9 and its
positive terminal connected to emitter le through wire 11.
Because of the presence of the asymmetrically 12.
conductive triode 2, current may flow through the base electrode lb
only in the direction toward the grounded wire 9 Because of the
asynnmretrically conductive nature and the bias of emitter le, current
may flow through it 13 785,986 common terminal is connected through
wire to base lb, so that the base lb is biased positively with respect
to emitter le If the body of transistor 1 is of n-type semi-conductive
material, as has been assumed, then this 70 positive potential on base

lb effectively blocks all current from the emitter le Some current
will flow through collector lc because of this positive potential on
the base, but it will be small in value, since it will be flowing in
the 75 high impedance direction through collector 1 c.
The setting of tap 25 on resistor 13 is adjusted so that triode 3 is
biased to cutoff.
With the foregoing OFF state established, assume that a signal pulse
is received at the 80 input terminals 16 and 17 When the trailing edge
of this pulse is transmitted through condenser 22 and resistor 23 to
grid 4, it appears there as a negative pulse, which lhas substantially
no effect on the conductivity of triode 2, 85 since that triode is
already biased to cut-off by the current flow through resistor 13.
When this input signal passes through capacitor 21 to wire 6 is biases
base lb negatively, and thereby produces a flow of emitter current 90
from battery 10 through wire 6 and capacitor 21 This flow of emitter
current produces an increased collector current, thereby increasing
the potential drop through resistor 13, and raising the potential of
tap 25, which is coin 95 municated through wire 24 and resistor 23, to
control electrode 40 so as to make the triode 2 conductive When triode
2 becomes conductive, it produces a further increase in emitter
current flow, with a consequent further 100 increase in collector
current flow and a following further increase in the potential of
lcontrol electrode 4 This cumulative process continues until the
circuit shifts to its ON state.
As the signal pulse passes through capatcitor 105 21 and as the tube
becomes conductive, a portion of the current necessary to supply the
condenser 21 and the tube 2 comes from battery 10 through resistor 34
and wire 35.
This current flowing through resistor 34 tends 110 to make wire 35
negative with respect to junction 36 and hence negative with respect
to emitter le This negative potential is applied to the base electrode
lb and therefore biases the base with a polarity tending to increase
115 the flow of emitter current, thereby producing a further
cumulative effect and further increasing the final value of collector
current While some of the current through the tube 2 is supplied by
battery 32 through resistor 33, 120 this has no substantial effect on
the potential of base lb, the latter being determined particularly by
the flow of current from battery through resistor 34.
The capacitor 26 is provided to hold the 125 cut-off biasing potential
on the control electrode 4 against the tendency of the input signal
pulse through condenser 22 to lower that potential further when the
tube 2 is already cut off In other words, the condenser 130 only in
the direction toward the body of the transistor Consequently, the
current through emitter le is the sum of the base and collector

currents The base current flows through a circuit which may be traced
from the positive terminal of battery 10 through wire 11, emitter le,
base lb, wire 6, anode 3, cathode 5, resistor 7 and wire 9 back to the
negative terminal of battery 10 The collector current flows through a
circuit which may be traced from the positive terminal of battery 10
through wire 11,-emitter le, collector lc, a wire 12, a load resistor
13, a wire 14, and a battery 15, to the negative terminal of battery
10.
Input signal pulses of the square wave or step type are supplied
through input terminals 16 and 17 Input terminal 17 is connected to
grounded wire 9 The polarity of the input pulses is such that during
an input signal pulse terminal 16 is positive with respect to terminal
17, as indicated by the legend in the drawing.
These input pulses are impressed across a capacitor 18 in series with
a resistor 19 and a parallel diode 20 These elements cooperate to
differentiate the pulses in a well-known.
manner and to shunt the spike due to the leading edge of the pulses,
so that only the spike due to the trailing edges are transmitted to
the trigger circuit These spikes due to the trailing edges are
transmitted through a capacitor 21 to the wire 6, and base lb ano 4
through a capacitor 22 and a resistor 23 to the control electrode 4 of
triode 2 Control electrode 4 is also connected through resistor 23 and
a wire 24 to a movable tap, 25 on the load resistor 13 A capacitor 26
is connected between wire 24 and collector lc.
Output pulses may be taken from output terminal 27 connected to
grounded wire 9 and either an output terminal 28 connected through a
wire 29 to the cathode 5 or an output terminal 30 connected through a
wire 31 to wire 6.
The circuit as thus far described is substantially the same as that
shown in the copending application, previously mentioned, except for
the addition of the resistor 23 which functions as an oscillation
suppressing resistance in a manner well known in the art.
The present invention is concerned with a novel biasing circuit for
the transistor 1, which includes a battery 32 having connected across
its terminals a voltage divider including two resistors 33 and 34 in
series The common terminal of the resistors 33 and 34 is connected
through a wire 35 to base lb The negative terminal of battery 32 is
connected to the positive terminal of battery 10 at junction 36.
When the circuit (Fig 1) is in its OFF condition, no current is
flowing through triode 2 The only current flowing through resistors 33
and 34 is that supplied by battery 32 so that the common terminal of
those resistors is then positive with respect to junction 36 and
henrce with respect to emitter le This 785,986 26 is effective when
the circuit is in its OFF state to prevent the signal pulse

transmitted through capacitor 22 from holding the circuit in its OFF
state.
After the circuit has become established in its ON state, let it be
assumed that another input signal of the same wave shape and polarity
is transmitted through input terminals 16 and 17 The trailing edge of
this signal is transmitted through capacitors 21 and 22 to base lb and
control electrode 4, respectively, where it appears as a negative
pulse Under present conditions, the pulse transmitted through
capacitor 21 is not effective to increase is substantially the emitter
current, since the emitter is already substantially saturated The
pulse transmitted through condenser 22 becomes effective to lower the
potential of control electrode 4, thereby reducing the base current
through transistor 1 and consequently the emitter current This
reduction in the emitter current produces a consequent reduction in
the collector current which is effective through resistor 13 and wire
24 to bias the control electrode 4 more negatively, thereby further
reducing the base current A cumulative process is again set up, which
continues until the tube 2 is cut off and the circuit is again
established in its OFF state The biasing battery 32 and resistors 33
and 34 contribute to this cumulative process by swinging the potential
of base lb in a positive direction, thereby decreasing the current
flow through transistor 1.
The capacitor 8 is effective during the transfer from the ON to the
OFF condition to hold the cathode 5 at the potential vwhich it had
during the ON condition, thereby making the reduction in the potential
of control electrode 4 more rapidly effective to cut off the flow of
current through the tube 2.
It should be apparent from the foregoing that in the OFF state of the
transistor, the emitter current is substantially zero Consequently,
the power consumption of the circuit is lower than in the previous
circuits, and the available output is greater Furthermore, the circuit
shown is considerably less sensitive to variation in the
characteristics of the transistor, since its base potential is
controlled at all times by impedances which are independent of the
transistor impedance.
The tube in the circuit just described functions as a variable
impedance means to control the flow of current through the transistor.
There are many advantages in the use of a tube for this variable
impedance means, especially with regard to the stability of the
characteristics of currently commercially available tubes However, it
is within the broader aspects of the invention to use some other
electric translating device having similar variable impedance
characteristics in place of tube 2 For example, such an alternative
translating device might be another transistor.

The circuit in Fig 2 is the same as that of Fig 1 except that an
additional resistor 37 is connected in series with the emitter
electrode le Resistor 37 is effective in the ON condition of the
circuit to increase the resistance in the anode load circuit of the
tube Consequently, the anode potential drops to a lower value when the
tube is conducting The output signal, when taken across terminals 27
and 30, may be increased by approximately 30 %,, in the circuit of Fig
2 as compared to the circuit of Fig 1 Furthermore, it is possible in
the circuit of Fig 2 to take the output signal from grounded terminal
27 and a terminal 38 connected through a wire 39 to emitter electrode
le, providing an even greater output potential than when the output
signal is taken across the terminals 27 and 30.
The following table shows, by way of example, a particular set of
values for the potentials of the various batteries and for the
impedances of the various resistors, in a circuit which has been
operated successfully It will be understood that these values are set
forth by way of example only and that the invention is not limited to
these values or any of them No values are given for the asymmetric
impedance elements, which may be considered to have substantially zero
impedance in there forward direction and substantially infinite
impedance in their reverse direction.
785,986 785,986 TABLE I.
Transistor 1 Triode 2 Resistor 7 Capacitor 8 Battery 10 Resistor 13
Battery 15 Capacitor 18 Diode 20 Capacitor 21 Capacitor 22 Resistor 23
Capacitor 26 Battery 32 Resistor 33 Resistors 34 and 19 Resistor 37
* Sitemap
* Accessibility
* Legal notice
* Terms of use
* 5.8.23.4; 93p
* GB785987 (A)
Description: GB785987 (A) ? 1957-11-06
Improvements in or relating to oestrogenic substances

Inventor: GERALD SEATON POPE Date of filing Complete Specification
March 26, 1956.
Application Date April 14, 1955.
785,987 No 10796/55.
Complete Specification Published Nov 6, 1957.
Index at Acceptance:-Classes 2 ( 3), C 3 A 11; and 81 ( 1), B 12 B.
International Classification: -A 61 k, C 07 g.
Improvements in or relating to Oestrogenic Substances We, NATIONAL
RESEAR Cii DEVELOPMENT CORPORATION, a British Corporation, of 1,
Tilney Street, London, W 1, do hereby declare the invention, for which
we pray that a patent may be granted to us, and the method by which it
is to be performed, to be particularly described in and by the
following statement: -
This invention relates to the isolation of naturally-occurring
oestogenic substances and is particularly concerned with the isolation
of an oestrogen from a Siamese plant which was formerly incorporated
in a Siamese rejuvenating drug.
This drug, which was reported in 1932 and 1933 to have been used in
Siam, consisted of the tuberous roots of a plant, powdered and mixed
with honey and myrobalans It was reported to have brought on
menstruation in old women, to have enabled an impotent old man to
become the father of new offspring and also in some cases to have been
toxic The tuberous root which had these effects was thought to be that
of Butea superba, Roxb.
Schering-Kahlbaum obtained supplies of the roots and in Specifications
Nos 437,051 and
453,583 they describe extraction methods using water, acetone,
chloroform and methanol All the extracts were highly oestrogenic in
the rat but that prepared with water was the most potent The
specification also described various ways of separating the oestrogen
from inactive matter as follows:(a) The roots were extracted with hot

water; the extract filtered and the filtrate evaporated to a syrup,
which was then diluted with a large excess of methanol and filtered
The filtrate possessed oestrogenic activity Repetition of this process
concentrated the active matter further.
(b) The active matter from (a) obtained by evaporating the filtrate to
dryness was re-dissolved in water and precipitated with ammonium
sulphate Oestrogenic activity was found in the precipitate.
(c) Dried powdered roots were extracted lPrice 3 s 6 d l with methanol
The methanol solution was evaporated; the residue dissolved in water
and precipitated with ammonium sulphate The precipitate was
partitioned between benzene 50 and 70 % ethanol and the oestrogenic
activity was then found mainly in the lower layer.
(d) The precipitated matter from (b) possessing activity was
re-dissolved in methanol and ether added to precipitate impurities;
this 55 being repeated twice, the oestrogen remaining largely in
solution.
(e) The active matter from (d) obtained by evaporating the solution to
dryness was dissolved in ethanol and water added until the 60 solution
contained 70 % of ethanol This was then extracted with benzene The
oestrogen remained in the aqueous ethanol.
Schoeller, Dohrn and Hohlweg (United States Specification No
2,112,712) again 65 found the roots to be rich in oestrogen (highly
active orally as well as subcutaneously) They extracted the dried,
powdered roots with ethanol and then filtered and evaporated the
solution They note the isolation of an oestro 70 gen of the empirical
formula GIH 22,0.
Later these workers published their work in short form
(Naturwissenschaften 28, 532 ( 1940)) They described the acquisition
of the oestrogenic roots from Siam, which they call 75 butea superba,
but they noted that the oestrogenic plant appeared to be different
from the butea superba growing in botanical gardens in Ceylon They
estimated the oestrogenic activity of the roots to be 180,000 Rat
Units 80 per kilogram or equivalent to 150 mg of oestrone per kg They
prepared highly oestrogenic concentrates from which Butenandt and
Jacobi at Danzig, first isolated the oestrogen and the gave the
empirical formula C 1,l H,0 06 85 (Butenandt, Naturwissenschaften 28,
533 ( 1940)) Butenandt found that the compound reduced Fehiing's
solution, was destroyed by alkali, gave an anhydro derivative CJH 1
OO, with HC 1 and gave a monomethyl ether 90 Schoeller, Dohrn and
Hohlweg (Naturwissenschaften 28, 532 ( 1940)) also described 785,987
the various physiological effects on the rat of the new compound These
are typical of stimulation by oestrogen The new substance lay between
oestradiol and oestrone in activity when assayed by the subcutaneous
route in the Ailen-Doisy test; it was much more active orally than

either oestradiol or oestrone.
It was finally established that the plant producing the tuberous roots
containing the oestrogen is of a new species which is named pueraria
miriica, Airy Shaw et Suvatabandhu (Kew Bulletin ( 1952, 549)).
It is an object of this invention to provide an improved process for
the isolation of the aforesaid oestrogen to which we have ascribed the
empirical formula C 20 H 2206, but which is presumably identical with
that described by Butenandt to which he gave the empirical formula G
10 H 20 G O This compound will hereinafter be referred to as
"miroestrol " Particulars of the ultra-violet and infra-red absorption
spectra are given below in Example 1.
According to the process of the present invention for the production
of miroestrol, a methanol or ethanol extract of tuberous root of
pueraria mirifica is subjected to partition chromatography.
Two methods were used for assaying the various extracts and fractions
for oestrogen content; bioassay by the mouse uterine weight assay as
used by Pope & Roy (Biochem J 53, 427 ( 1953)) and paper
chromatographic assay.
Bioassay which can estimate the total oestrogenic activity of a crude
extract was used during the development of the isolation process but
once miroestrol had been concentrated sufficiently it was possible and
convenient to estimate it by paper chramatography.
According to a preferred embodiment of the invention powdered tuberous
roots of pueraria mirifica are extracted with aqueous methanol or
ethanol and then with pure methanol or ethanol and the solutions
separated, for example by filtration, combined together and evaporated
to dryness The residue from this is fractionated by solution in
methanol and ether added to precipitate impurities Most of the
oestrogen remains in solution and is further purified by partition in
a solvent system containing water, methanol, ethyl acetate and benzene
The active material remains in the lower phase and is next subjected
to partition chromatography.
Preferably the partition chromatography is carried out on a column of
kieselguhr and preferably also the mobile phase is a mixture of
benzene and ethyl acetate and the stationary phase is aqueous
methanol.
The following examples illustrate the invention:1 The initial material
is tuberous roots of pueraria mirifica sliced, sun-dried and powdered
to a fine powder in a hammer-mill and having a dry matter content of
approximately 87 %.
kg of powder was boiled and stirred for 0.5 hour with a mixture of 11
litres of methanol and 1 litre of water in a 20 litre flask, provided
with a reflux condenser and a stirrer consisting of a stainless steel
shaft and six 70 small vanes set at an angle of 450 to the shaft.

The stirrer was driven by a 0 08 H P electric motor at 1350 r p m by
direct coupling with rubber tubing The solution was separated by
filtration through an 8-inch Buchner funnel 75 having a tin-plate,
cylindrical extension piece to increase its capacity, the filtrate
passing directly into a 20 litre distillation flask The plant residue
was then similarly extracted a second time with 10 litres of methanol
and a 80 third time also with 10 litres of methanol The combined
filtrates were evaporated to dryness under reduced pressure, the
residue shaken with 3 litres of methanol and left to stand for 18
hours after which the granular precipitate 85 was filtered off and the
filtrate evaporated to dryness at reduced pressure The residue was
then dissolved in 1 liitre of methanol and 4 litres of ether added On
leaving overnight a gummy precipitate formed from which the 90
supernatant solution was decanted This solution was then evaporated to
dryness and the residue dissolvel in 1 litre of methanol and 4 litres
of ether added Again after allowing to stand the clear supernatant
solution was 95 decanted off, the precipitate being redissolved in 500
ml of methanol and re-precipitated with 2 litres of ether The combined
supernatant solutions were then evaported to dryness at reduced
pressure This residue was shaken 100 with 2 5 litres of ethyl acetate
at room temperature and the solution left to clarify The filtrate was
evaporated to dryness and partitioned between: Benzene 2500 ml 1 ^ 5
Ethyl acetate 250 ml Methanol 1250 nl Water 1250 ml The lower phase
was separated off and the upper phase washed with 1250 ml of 50 % 110
aqueous methanol The combined lower phases were evaporated to dryness
at reduced pressure and the residue chromatographed on a large column
using the partition method The solvent system used was: 115 Benzene
8000 ml Ethyl acetate 3000 ml Methanol 5000 ml Water 5000 ml The
column consisted of a 6 ft length of 120 glass pipeline of 4 inches
internal diameter with a suitable reduction piece and stop-cock at its
lower end It was packed with kieselguhr (Celite 545, supplied by
Johns-Manville Co, Ltd, London, the word " Celite " being a 125
registered Trade Mark) by the method of Martin (Biochem Soc Symposia
No 3, p 11, 1949) The kieselguhr was slurried with solvent by
mechanical stirring in a flask and the slurry transferred by pressure
into the top of 130 -785,987 the column Packing was done with a
stainless steel ramrod having a perforated head ( 8 inch diameter
holes) and a sectional shaft The height of the kieselguhr was then 28
inches.
The residue to be chromatographed was added in the minimum quantities
of a mixture of stationary and mobile phases necessary to effect
solution The partition column was operated in the usual manner and
suitable aliquots of the various fractions examined by paper
chromatography The chromatograms were sprayed with a suitable

visualising agent such as diazotised p-aminophenyl-2-diethylaminoethyl
sulphone, methanolic potassium hydroxide or periodic acid.
The fractions from the 4-inch diameter column containing miroestrol
were then rechromatographed on a 2-inch diameter kieselguhr column
using the same solvent system.
2 C The fractions containing miroestrol were again identified by paper
chromatography and were collected together and run similarly on a
second 2-inch column The fractions from this column which contained
miroesterol crystallised partially and were washed with ethyl acetate
yielding crystals ( 140 mg) Recrystallisation from methanol gave pure
miroestrol ( 120 mg), m.p (with decomposition) 2700 C, optical
rotation lOlC'7 D = + 3010.
The ultra-violet absorption of miroesterol in ethanol solution was as
follows: ethanol A max.
ethanol A 220 my; 287 my e= 3480 max.
The infra-red absorption spectrum of miroesterol (crystalline state;
as paraffin paste) showed absorption peaks at: 3334 cm -', 2865 cm -',
1712 cm -', 1664 cm.', 1621 cm ', 1597 cm -', 1508-1504 cm.1,
1460-1453 cm -', 1401 cm ', 1362 cm?, 1325 cm -1, 1282 cm -',
1245-1242 cm, 12,24-1218 cm -', 1183 cm -', 1176 cm.?', 1170 cm -',
1160 cm -, 1155 cm -'.
The oestrogenic activity of miroestrol was about 1 3 times that of
oestradiol-17/3 in the mouse uterine weight test and about one-fourth
that of oestradiol-17/ in the rat vaginal smear test (Allen & Doisy,
Amer J Physiol 69, 577 ( 1924)).
It was estimated by mouse bioassay methods that the overall recovery
of miroestrol from the plant source was greater than 50 %.
2 Example 1 was repeated using an equal volume of ethanol instead of
methanol for the two extractions of the plant.
* Sitemap
* Accessibility
* Legal notice
* Terms of use
* 5.8.23.4; 93p
* GB785988 (A)
Description: GB785988 (A) ? 1957-11-06

Basic monoazo dyes of the benzene-azo-benzene series
785,988 o Date of Application and filing Complete Specification: May
2, 1955.
SS 'l S S Hi L No12638155.
Application made in United States of America on May 3, 1954.
Application made in United States of America on April 12, 1955.
Index at acceptance: -Classes 2 ( 3), C 1 FI(AI: A 3: C 6: D 2: E),
CIF 2 (A 2: A 3: C 6: D 2: E), C 2 84 (A 2: C: D: F: G 2: G 4: G 8), C
22 89, C 2 B 37 (A 2: A 3: l: J: L); and 2 ( 4), Pl(A 1 B 2: D 1: Fl:
F 2), P 9 A 3 A 2.
International Classification:-CO 7 c C 09 b.
Basic Monoazo Dyes of the Benzene-Azo-Benzene Series We, E I Du PONT
DE NEMOURS AND COMPANY, a corporation organized and existing under the
laws of the State of Delaware, located at Wilmington, State of
Delaware, United States of America, do hereby declare the invention,
for which we pray that a patent may be granted to us, and the method
by which it is to be performed, to be particularly described in and by
the following statement: -
This invention relates to novel dyes and more particularly to new
basic monoazo dyes suitable for dyeing the polyacrylic fiber known
under the Registered Trade Mark as " Orlon " which is predominantly
polyacrylonitrile and is hereinafter referred to as polyacrylic fibre.
Recently, there has been a growing emphasis on the use of basic dyes
for polyacrylic fiber or such fiber in mixture with other fibers such
as wool or cellulosic fibers The problem which is presented is to
provide such a basic dye which is suitable for rapid dyeing and which
will also be stable, wash and light-fast Several monoazo dyes have

been proposed for use on polyacrylic fiber; however, it has been found
that these dyes are inferior in light-fastness or build-up properties.
This invention has an object to provide novel basic monoazo dyes A
further object is to provide basic monoazo dyes for rapid and direct
dyeing of polyacrylic fiber A still further object is to provide
stable, wash and lightfast basic monoazo dyes suitable for the rapid
dyeing of union fabrics containing polyacrylic fiber Other objects
will appear hereinafter.
These objects are accomplished by the following invention of the novel
basic monoazo dyes which are obtained by coupling a diazotized
aminophenacylammonium salt with an aromatic amine These dyes are
yellow-orange to red-violet in shade and they exhibit excellent
light-fastness on polyacrylic fiber The novel dyes of the present
invention are represented by the following general formula:
I Pru X x xi y yv RI A / RK + (Ie N = NN R 2 -N-Z-C R 5 R 3 wherein R
1 is lower alkyl; R 2 is a radical selected from the group consisting
of lower alkyl and hydroxyalkyl; R, is a radical selected from the
group consisting of lower alkyl, hydroxyalkyl and monocyclic aralkyl
and wherein R,, R and R, together with the contiguous nitrogen atom
may represent a monocyclic heterocyclic group; R 4 is a radical
selected from the group consisting of hydrogen, lower alkyl,
hydroxyalkyl, acetylalkyl, cyanoalkyl, chloroalkyl and monocyclic
aryl; R, is a radical selected from the group consisting of hydrogen,
lower alkyl and hydroxyalkyl and cyanoalkyl; X is a radical selected
from the group consisting of hydrogen, lower alkyl, halogen and
alkoxyl; X' is a radical selected from the group consisting of
hydrogen, lower alkyl and halogen; Y is a radical selected from the
group consisting of hydrogen, lower alkyl, halogen and allcoxyl; Y' is
a radical selected from the group consisting of hydrogen and lower
alkyl; with the proviso that when R, R^, R,, R, and R are all methyl
radicals at least one of X, X 1, Y or Y 1 is lower alkyl, alkoxyl or
halogen; Z is a radical selected from the group consisting of normal
and branched alkylene groups having 1 to 3 carbons; A is an anion
taken from the group consisting of organic and inorganic anions which
renders the dye soluble in water and wherein the RI AR 2 N Z-CO h 2
785,988 grouping is in meta or para position to the azo linkage, the
lower alkyl radical being an alkyl radical having from 1 to 4 carbon
atoms.
The following examples will better illustrate the nature of the
present invention, however, the invention is not intended to be
limited to these examples.
EXAMPLE I.
1500 ml of an aqueous solution containing 219 grams of
p-aminophenacyl-trimethyl ammonium chloride and 500 ml of 36 %,'

aqueous hydrochloric acid is cooled to 0-5 C by the addition of ice,
and the amine is diazotized by the addition of 66 3 grams of sodium
nitrite (as a 34 5 % aqueous solution).
An excess of nitrous acid is maintained in the solution for 30 min
(potassium iodide-starch test paper) and is then removed by the
addition of a small amount of sulfamic acid To the solution then is
added 176 grams nm-chloroN,N-diethylaniline, followed by 100 grams
sodium acetate trihydrate The mixture is stirred at 0-10 C while 400
ml of 30 % aqueous sodium hydroxide are added slowly over a period of
2 5 hours The mixture is stirred an additional 2 5 hours at 0-10 C,
and then for 16 hours, without cooling The p H of the mixture is
adjusted to 5 5 by the addition of aqueous sodium hydroxide, and the
product is isolated by filtration The filter cake is reslurried with
1000 ml of water, heated to 900 C., and filtered hot The filtrate is
stirred and allowed to cool to room temperature 100 grams of sodium
chloride are added, stirring is continued for 1 hour, and the product
is isolated by filtration and dried in a vacuum oven at C The product
is a red-brown powder which dissolves readily in warm water to give a
red-orange solution Polyacrylic fiber is dyed a red-orange shade from
a neutral dye bath at the boil The dye obtained has the formula 0 cl
(CH 3)3 N -CH 2 C0-N = N N S 2 Cl C 2 H 5 EXAMPLE II.
A solution of 74 grams of p-acetaminophenacyl-trimethyl ammonium
chloride in 400 ml water and 200 ml of 36 % aqueous hydrochloric acid
is heated at the boil for 0 5 hour to effect hydrolysis of the acetyl
group The resulting solution is stirred and cooled with ice to 0-5 C,
and the amine is diazotized by the addition of 19 grams of sodium
nitrite (as a 34 5 % aqueous solution) Excess nitrous acid is
maintained in the solution at 0-10 C for 0.5 hour and is then removed
by the addition of sulfamic acid To the solution is added,
successively, 44 grams of NN-diethyl-miitoluidine and 200 grams of
sodium acetate trihydrate Stirring is continued for 1 hour at 0-10 C
and an additional 60 grams of sodium acetate trihydrate are added
Stirring is continued for 8 hours at room temperature, and the mixture
is filtered The product, after drying, is a dark brown powder which
dissolves readily in warm water to give a red solution.
Polyacrylic fiber is dyed in red shades from a neutral dye bath at the
boil.
EXAMPLE III.
A solution of 12 grams of p-acetaminophenacyl-pyridinium chloride in
100 ml of water and 50 ml 36 aqueous hydrochloric acid is heated at
the boil for 0 5 hour to effect hydrolysis of the acetyl group Ice is
added to give a total volume of 500 ml, and the amine is diazotized by
the addition of 2 9 grams sodium nitrite (as a 34 5 %, aqueous
solution).

After stirring for 0 5 hour at 0-10 C, excess nitrous acid is
destroyed by the addition of sulfamic acid, and 8 4 grams of
NN-diethylm-toluidine and 60 grams of sodium acetate are added
successively The mixture is stirred at 0-10 C for 3 hours, and at the
ambient temperature for 8 hours, then filtered and the residue is
dried The product is a dark brown powder which gives dyeings on
polyacrylic fiber with shade and fastness properties comparable to
those shown by the product of Example II.
EXAMPLE IV.
ml of an aqueous solution containing 22.8 grams of
p-aminophenacyl-trimethyl ammonium chloride and 52 ml of 36 %.
aqueous hydrochloric acid is cooled to 0-5 C by the addition of ice,
and the amine is diazotized by the addition of 6 9 grams of sodium
nitrite (as 34 5 % aqueous solution) An excess of nitrous acid is
maintained in the mixture for 0 5 hour, and is then destroyed by the
addition of a small amount of sulfamic acid To the solution is added,
successively, 12.2 grams 2,5-dimethyl-aniline and 80 grams sodium
acetate trihydrate Stirring is continued at 0-10 C for 3 hours,
followed by 8 hours without cooling The mixture is rendered alkaline
(positive reaction to Brilliant Yellow paper) by the addition of
sodium hydroxide, heated to 60 C, and filtered The filtrate is
neutralized with acetic acid, and salted with % by weight of sodium
chloride The product is isolated by filtration and dried at 50-60 C to
yield a brown powder which dissolves in water to give an orange
solution The product dyes polyacrylic fiber in orange shades.
EXAMPLE V.
An aqueous solution of 13 8 grams of pacetamino
phenacylbenzyldimethylammonium chloride in 100 ml water and 50 ml of
36 %,' hydrochloric acid is heated at the boil for 0 5 hour, iced to O
C, and diazotized by the addition of 2 76 grams of sodium nitrite (as
a 34.5 % aqueous solution) An excess of nitrous acid is maintained in
the mixture for 20 min, and is then destroyed by the addition of a
small amount of sulfamic acid To the solution at C is added 7 4 grams
of mi-chloro-N,Ndlethylaniline, followed by 140 grams sodium acetate
trihydrate The mixture is stirred 2 785,988 similar to those obtained
with the product of Example I.
When the m-chloro-NN-diethylaniline is replaced with 6 6 grams of
NN-diethyl-mtoluidine a product is obtained which dyes polyacrylic
fiber from a neutral aqueous dye bath in red shades, similar to those
obtained with the product of Example II.
EXAMPLE VII.
ml of an aqueous solution containing 6.4 grams of p
aminophenacyltrimethyl ammonium chloride and 6 0 ml of 10 N.
aqueous hydrochloric acid are mixed and cooled to 0-50 C The amine is

diazotized by the addition of 2 2 grams of sodium nitrite (as a 5 N
aqueous solution), and an excess of nitrous acid is maintained in the
mixture for 30 minutes, and is then destroyed by the addition of a
small amount of sulfamic acid.
To the solution at 0-5 C, is added 6 0 grams of
NN-di(beta-cyanoethyl)-m-toluidine in 41 mol of 36 % aqueous
hydrochloric acid solution during a 15 minute period The solution is
stirred for 16 hours during which time it is allowed to warm to room
temperature Then 74 grams of sodium acetate are added and stirring is
continued for an additional 2 hours The product is removed by
filtration and dried at 50-60 C to yield an orange powder which
dissolves readily in warm water to give an orange solution It dyes
polyacrylic fiber in orange shades from a neutral dye bath at the
boil.
EXAMPLE VIII.
In a similar manner, the following cationic dyes were prepared.
hours at 0-10 C, then 16 hours at the ambient temperature The product
is removed by filtration and is dried at 50-60 C to a brown powder
which dissolves in water to give a red-orange solution This product
dyes polyacrylic fiber from a neutral aqueous dye bath to give
red-orange dyeings similar to those obtained with the product of
Example I.
When the m-chloro-NN-diethylaniline of this example is replaced with 6
6 grams of N,N-diethyl-m-toluidine, a red dye is obtained which when
applied to polyacrylic fiber produces dyeings of comparable shade and
fastness properties to the product of Example II.
EXAMPLE VI.
A solution of 12 grams of p-acetaminophenacyl-dimethyl
(beta-hydroxyethyl)ammonium chloride in 100 ml of water and 50 ml of
36 % hydrochloric acid is heated at the boil for 0 5 hour, iced to O
C, and diazotized by the addition of 2 76 grams of sodium nitrite (as
a 34 5 % aqueous solution) An excess of nitrous acid is maintained in
the mixture for 20 minutes, and is then destroyed by the addition of a
small amount of sulfamic acid To the solution at 100 C is added 7 4
grams of m-chloro-NN-diethylaniline, followed by 140 grams of sodium
acetate trihydrate The mixture is stirred for 2 hours at 0-10 C, then
for 16 hours without cooling.
The product is isolated by filtration and dried to give a brown powder
which dissolves in water to give a red-orange 'solution When applied
to polyacrylic fibre from a neutral aqueous dye bath orange shades are
obtained Diazo Component (a) p-aminophenacyltrimethyl ammonium
chloride (b),, c)) (d) j (e),, (f)) (h),, (i), (i) is (k),,1 ( 1) (m)
(n) (o) Coupling Component m-toluidine 2,6-dimethylaniline
3-5-dimethylaniline 2-methoxy-5-methylaniline 5-chloro-o-toluidine

N-ethyl-o-toluidine N-beta-cyanoethylaniline
N-beta-cyanoethyl-otoluidine N-beta-cyanoethyl-mtoluidine
N-methyldiphenylamine NN-di(beta-hydroxyethyl) aniline
N,N-di(beta-hydroxyethyl)rn-toluidine N-beta-cyanoethyl-Nmethylaniline
N-beta-cyanoethyl-Nethylaniline
N-beta-cyanoethyl-N-betahydroxyethyl-aniline Color on poly Acrylic
Fiber orange yellow-orange yellow-brown , yellow red-orange orange
orange red-orange red-orange orange red orange orange orange 785,988
785,958 Diazo Component (p) p-aminophenacyltrimethyl ammonium chloride
(q),, (r),, (s) ( 3-amino-4-methylphenacyl) trimethylammonium chloride
(t) ( 3-amino-4-methylphenacyl) trimethylammonium chloride (u) (v) (
3-amino-4-methoxyphenacyl) trimethylammonium chloride (x) (
4-amino-3-bromophenacyl) trimethylammonium chloride (Y) 2) (aa) (bb) (
4-amino-3,5-dibromophenacyl) trimethyl ammonium chloride (cc) (dd),,
(ee),, (Hf) ( 4-amino-2-chlorophenacyl) tri-methyl ammonium chloride
(hh) ( 4-amino-2,5-dimethylphenacyl) trimethyl ammonium chloride
Coupling Component N,N-di(beta-cyanoethyl) aniline
N-beta-cyanoethyl-N-betahydroxyethyl-m-toluidine
N-beta-chloroethyl-Nethyl-aniline N,N-dime^thylaniline
iii-chloro-N,N-dimethylaniline N,N-diethyl-iii-toluidine
N,N-dimethylaniline ii-chloro-N,N-dimethylaniline
ii-chloro-N,N-dimetlhylaniline m-clhloro-N,N-diethylaniline
N,N-diethyl-m-toluidine N,N-dimethylaniline
iii-chloro-N,N-dimethylaniline mz-chloro-N,N-diethvlaniline
N,N-diethyl-mii-toluidine N,N-dimethylaniline
m-chloro-N,N-diethylaniline N,N-diethyl-m-toluidine
N,N-dimethylaniline Color on poly Acrylic Fiber orange red orange
orange orange yellow brown orange red orange red red red-violet red
red red red-violet red red-orange red red-orange The phenacyl
intermediates employed in the above examples were prepared in the
following manner.
PREPARATION OF INTERMEDIATES.
(a) Preparation of p-acetaminophenacyl chloride.
A mixture of 180 grams of acetanilide, 269 grams of chloroacetyl
chloride and 1250 grams sym -tetra chloroethane is stirred at
temperatures below 60 C while 630 grams anhydrous aluminum chloride
are added in small portions over a 2-hour period The mixture is heated
at 58-62 C for 2 hours and is drowned on sufficient crushed ice to
insure the presence of floating ice in the final mixture The mixture
is filtered and washed with cold water until the filter cake is
essentially free of sym-tetrachloroethane and the washings give a
negative acid test with Congo red test paper The product may be dried
in air at room temperature or in a vacuum oven at 30-50 C The yield is
essentially quantitative.

(b) Preparation of p-aminophenacyl-trimethyl-ammonium chloride.
A mixture of 249 grams of p-acetaminophenacyl chloride and 650 ml of
an aqueous solution containing 65 grams of trimethylamine is stirred
for 16 hours at room temperature and then at 60-65 C for 2 hours A
small amount of insoluble material is removed by filtration The
filtrate is combined with onehalf its volume of concentrated
hydrochloric acid ( 36 % by weight) and the resulting solution is
heated at the boil for O 5 hour The aqueous solution of
p-amino-phenacyltrimethylammonium chloride is used as such in grams of
35 % hydrochloric acid at the boil for 0 5 hour.
(k) Preparation of ( 4-amino-3,5-dibromophenacyl) trimethylammonium
chloride.
This preparation is carried out utilizing a 70 modification of the
procedure for the preparation of 4-amino-3,5-dibromoacetophenone
described by Fuchs, Monatsh 36, 122 ( 1915) A solution of 53 grams of
p-acetaminophenacyltrimethylammonium chloride in 450 ml of 75 14.6 %
aqueous hydrochloric acid is heated at the boil for 0 5 hour to
hydrolyze the acetyl group The solution then is cooled to 250 C.
and a solution of 103 grams of bromine and 52.4 grams of glacial
acetic acid is added 80 slowly over a period of 2 hours The color of
the bromine disappears, and the solution is used as such in the
preparation of dyes.
EXAMPLE IX.
ml of an aqueous solution containing 85 5.2 grams of p
aminophenacyltrimethyl ammonium chloride and 9 0 ml of 10 N aqueous
hydrochloric acid is cooled to 0-5 C., and the amine is diazotized by
the addition of 2 0 grams of sodium nitrite (as a 5 N 90 aqueous
solution) An excess of nitrous acid is maintained in the mixture for
30 min, and is then destroyed by the addition of a small amount of
sulfamic acid To the solution at 0-55 C is added 4 4 grams of
o-chloro-N 95 beta-cyanoethylaniline in 40 ml of l ON aqueous
hydrochloric acid during a 5 minute period The solution is stirred for
one hour at 0-5 C and then for 16 hours at 20-25 C.
To this mixture is added 94 grams of sodium 100 acetate and stirring
is continued for 30 minutes.
The product is removed by filtration and dried at 60-65 C to yield an
orange powder which dissolves readily in warm water to give an orange
solution It dyes polyacrylic fiber in 105 orange shades from a neutral
dye bath at the boil.
the preparation of dyes The concentration of aromatic amine in the
solution can be determined easily by measuring nitrous acid
absorption.
Alternatively, the p acetaminophenacyl chloride can be dissolved in a
suitable solvent, such as acetone, and treated with gaseous

trimethylamine to effect quaternization The hydrolysis is effected in
1: 2 concentrated hydrochloric acid-water, as described above.
(c) In a similar manner, ( 3-amino-4-methylphenacyl)-trimethylammonium
chloride is prepared starting from o-acetotoluide.
(d) In a similar manner, ( 4-amino-2-chlorophenacyl)-trimethylammonium
chloride is prepared starting from m-chloroacetanilide.
(e) In a similar manner (
4-amino-2,5-dimethyl-phenacyl)-trimethylammonium chloride is prepared
starting from 2,5-dimethylacetanilide.
(f) In a similar manner ( 3-amino-4-methoxyphenacyl)-trimethylammonium
chloride is prepared starting from o-acetaniside.
(g) Preparation of p-acetaminophenacylpyridinium chloride.
To a solution of 25 grams of p-acetaminophenacyl chloride in 400 ml of
acetone is added 20 ml of pyridine The mixture is stirred for 16 hours
at the room temperature and is then stirred 3 hours at a gentle
reflux.
The white crystalline precipitate is isolated by filtration and dried.
(h) Replacement of the pyridine in (g) by ml of
beta-dimethylaminoethanol yields (pacetaminophenacyl) dimethyl
(beta-hydroxyethyl)ammonium chloride as a white crystalline material.
(i) Replacement of the pyridine in (g) by 27 grams of
benzyldimethylamine yields (p-acetaminophenacyl) benzyldimethyl
ammonium chloride as a white crystalline material.
(j) Preparation of ( 4 amino-3-bromophenacyl) trimethyl-ammonium
chloride.
To a well-stirred mixture of 62 grams of pacetaminophenacyl chloride,
734 grams of glacial acetic acid and 400 grams of water is added a
solution of 81 grams of bromine in 315 grams of glacial acetic acid
The addition is carried out over a period of 2-4 hours.
Solution is complete at the end of the addition, but the product
precipitates gradually as stirring is continued for 16 hours The
mixture is diluted with a solution of 3 grams of sodium bisulfite in
2500 ml of water, stirred a few minutes, and filtered The yield of
product, after drying at room temperature, is 86 grams.
The product is dissolved in 1600 grams of acetone, and the solution is
filtered The filtrate is stirred and saturated with trimethylamine.
The precipitate, after isolation by filtration and drying at the room
temperature, is a tan microcrystalline material, melting at 2152160 C
The yield is 63 grams Hydrolysis is effected by heating 28 grams of
the quaternary ammonium salt with 200 ml of water and 177 EXAMPLE X.
(a) Preparation of l 2-(p-aminobenzoyl)ethyll trimethyl-ammonium
chloride.
H 2 N-O-CO' Cc C Hjc H 2 N(CH 2), CIA mixture of 113 grams of
anhydrous aluminum chloride and 214 grams of sym tetrachloroethane is

stirred at temperatures below 350 C while 31 grams of acetanilide are
115 added in small portions To this mixture 48 grams of
beta-chloropropionyl chloride are added below 400 C The resulting
mixture is heated gradually to 600 C and stirred at 60 -65 C for two
hours The reaction mass is 120 drowned in 1700 grams of ice and water
keeping the temperature below 200 C The product is filtered off and
washed with cold water until essentially free of sym
-tetrachloroethane and the washings are no longer acid to Congo Red
125 test paper The washed filter cake is mixed 785,988 with 50 ml
water and 58 grams of an aqueous solution containing 19 3 grams of
trimethylamine The mixture is heated to 600 C in one hour and held at
60-65 C for 2 hours.
66 ml of concentrated hydrochloric acid ( 36 % by weight) are added
and the resulting solution heated to 1030 to 1070 C for hour,
distilling out a small amount of tetrachloroethane to attain this
temperature The resulting solution of l 2 (p
aminobenzoyl)ethylltrimethylammonium chloride is used as such in the
preparation of dyes, the concentration of aromatic amine being
determined by nitrite absorption.
(b) Preparation of the Azo Dye.
125 ml of an aqueous solution containing 9.6 grams of l
2-(p-aminobenzoyl)ethylltrimethyl-ammnonium chloride and 10 ml of
concentrated hydrochloric acid is cooled by ice to 0-5 ' C and the
amine is diazotized by adding 2 75 grams of sodium nitrite (as a 34.5
% aqueous solution) An excess of nitrous acid is maintained for 30
minutes and is then removed by the addition of a small amount of
sulfamic acid To the diazo solution is added 6 5 grams
NN-diethyl-iii-toluidine and the mixture is stirred at 0-10 C for 4
hours 5 grams of sodium acetate trihydrate are added and the mixture
is stirred without cooling for 16 hours The color is then precipitated
by adding 10 grams of sodium acetate trihydrate as a 25 % aqueous
solution The color is filtered off, washed with 10 % salt solution and
dried at 750 C The product is obtained as a brittle mass which gives a
brownish powder on grinding It dyes polyacrylic fiber in red shades.
(c) The replacement of the l 2-(p-aminobenzoyl)ethylltrimethylammonium
chloride of Ex XIV (b) with 13 grams of l
3-(p-aminobenzoyl)propylltriethylammonium bromide gives a dye for
polyacrylic fibre of similar shade Said ammonium bromide compound is
represented by the formula Br H 2 N-(/)-COCH 2 CH 2 CH 2-N (C 2 H 5)3
This intermediate is prepared by the method disclosed by W H Linnell
and S V Vora, The Journal of Pharmacy and Pharmacology, Volume 4, No
1, pages 62-64, 1952.
(d) When the NN,-diethyl-rn-toluidine of part (b) of this example is
replaced with 6 4 grams N-( 2-cyano-ethyl)-N-methylaniline a product

is obtained which dyes polyacrylic fiber in orange shades.
EXAMPLE XI.
(a) Preparation of (p-amino-alpha-methyl phenacyl) trimethylammonium
chloride.
CH 3 H 2 N-C) CO CHWN(CH 3)3 clr A mixture of 63 grams of anhydrous
aluminum chloride and 120 grams sym tetrachloroethane is stirred at
temperatures below 350 C while adding 17 2 grams of 60 acetanilide To
this mixture 30 grams of alpha-chloropropionyl chloride are added at
temperatures below 20 ' C and stirring is continued for several hours
allowing the ternperature to rise to 240 C After standing over 65
night at room temperature ( 24 C) the mixture is drowned in 750 grams
of an ice-water mixture The oily layer is separated and washed several
times with cold water and finally stirred at 21 C with 33 grams of an
70 aqueous solution containing 11 grams of trimethylamine The
temperature rises to 320 C.
The solution is heated in 1 hour to 600 C.
and maintained at 60-655 C for 1 hour.
37 ml of concentrated hydrochloric acid are 75 added and the sym
-tetrachloroethane is removed by steam distillation The clear aqueous
solution of (p-amino-alpha-methyl phenacyl)trimethylammonium chloride
which remains is diluted with water to 500 ml and is used as 80 such
in the preparation of dyes.
(b) Preparation of the Azo Dye.
ml of the aqueous solution obtained in part (a) of this example and
containing 15 3 grams of (p-amino-alpha-methylphenacyl tri 85
methylammonium chloride and 10 ml concentrated hydrochloric acid is
cooled by ice to 0-5 O C and the amine is diazotized by adding 4 35
grams sodium nitrite (as a 345,'.
aqueous solution) An excess of nitrite is main 90 tained for 30
minutes and is then removed by the addition of a small amount of
sulfamic acid To the diazo solution are added 10 3 grams of
NN-diethyl-mz-toluidine and the mixture is stirred at 0-10 C for 4
hours 95 and then is allowed to warm to room temperature ( 24 C) in 12
hours 21 grams of sodium acetate trihydrate are added as a 25 %
aqueous solution to precipitate the color The product is filtered off,
washed with 10 %' salt solution and dried at 75 C Said product is 100
obtained in the form of a brown powder and dyes polyacrylic fiber in
red shades.
(c) When the NN-diethyl-m-toluidine of part (b) of this example is
replaced with 10 1 grams of N-( 2-cyanoethyl) N-methylaniline a 105
product is obtained which dyes polyacrylic fiber in orange shades.
EXAMPLE XII.
(a) The coupling component, 4-(N-methylanilino)butanone-2, is prepared
by adding, 110 during 2 5 hours, 82 3 grams of methyl vinyl ketone (as

an 85 % aqueous solution) to 107 grams N-methylaniline preheated to
60-65 C After standing overnight at 22 C the mixture is refluxed for
30 minutes The re 115 action product after distillation in vacuo,
weighs 125 5 grams; b p range 116-120 C.
at 2 5 mm Hg.
The analyses obtained for C, H and N correspond to those required by
the formula 120 785,988 (prepared as described in U S Patent 2,206,099
by coupling diazotized amino-acetophenones to aryl amines) in an
alcoholic solution with short chain alkyl chlorides, bromides or
sulfates, or with alkyl esters of organic sulfonic acids such as the
methyl, ethyl, propyl or butyl ester of p-toluenesulfonic acid, to
effect conversion to the quaternary ammonium derivatives The
substituents R, X and Y are defined as on page 2 except R 1 and R are
radicals selected from the group consisting of lower alkyl,
hydroxyalkyl and monocyclic aralkyl; N is 1 to 3.
As evidenced by the examples, the products of the present invention
are yellow-orange to red-violet in shade when applied to polyacrylic
fiber The preferred types of dyes from the standpoint of
light-fastness are those which are represented by the para structures,
i e, 0 O-' o CH 2 C CH 3 CH 3 (b) Preparation of the Azo Dye.
ml of an aqueous solution containing 6.54 grams of p
aminophenacyltrimethylammonium chloride and 18 cc concentrated
hydrochloric acid is cooled to 0-5 C and the amine is diazotized by
adding 6 1 ml of N sodium nitrite solution An excess of nitrous acid
is maintained for 20-30 minutes and is then removed by the addition of
a small amount of sulfamic acid To the diazo solution are added 4 9
grams of 4-(N-methylanilino)butanone-2 After 15 minutes, 5 5 grams of
sodium acetate trihydrate are added and the mixture is stirred at 0-10
C for four hours Two grams of sodium acetate trihydrate are added and
the mixture is stirred without cooling for 16-18 hours Four grams
sodium acetate trihydrate are then added and the colored precipitate
is filtered off The precipitate is then washed with 10 % salt solution
and dried at 700 C The red-brown product obtained is soluble in water
with orangered coloration Said product dyes polyacrylic fiber in
orange shades.
In the above recited examples, the chloride and bromide salts of the
dyes have been disclosed; however, it is to be understood that
different anions may be obtained in these dyes, of course, either by
utilizing another phenacyl derivative (e g, p-acetaminophenacyl
bromide,etc) for the reaction with a tertiary amine, or by subjecting
the phenacyltrimethylammonium chlorides or the dyes prepared therefrom
to the usual metathetical reactions For instance, hydrolysis of the
p-acetaminophenacyltrialkylammonium chloride compounds may be carried
out by heating in acid as described above, except that the

hydrochloric acid medium is replaced by 5 to 10 parts (based on
p-acetaminophenacyl chloride) of 4 N sulfuric or phosphoric acid The
resulting solutions of the p aminophenacyltrialkylammonium sulfates or
phosphates can be treated directly with sodium nitrite to effect
diazotization of the primary aromatic amines The diazonium compounds
thus obtained can be used directly in the coupling step to provide the
final dyes in the form of their ammonium sulfates or phosphates The
nature of the anion in the dye is not critical as long as it renders
the dye soluble in water.
Alternatively, products of this invention may be prepared by treating
the dyes of the general formula X x'6 Y Y 1 RI O XIYY o N Cn-CR R 2 R
RI Cl o XX' y y R 2 N ZC N N < R 3 R 5 The following is given as a
further example of the preparation of an azo dye in accordance with
this invention in which R, and R, of the general formula are both
hydroxy alkyl 80 A mixture of 7 5 grams of p-acetamidophenacyl
chloride and 7 2 grams of N-methylN,N-di(beta-hydroxyethyl)amine in
100 ml of acetone was heated under reflux for 3 hours.
The acetone was evaporated on the steam 85 bath and the
p-acetamidophenacyl-methyl-di(beta-hydroxyethyl)-ammonium chloride was
dissolved in 150 ml of water Fifteen grams of 36 % aqueous
hydrochloric acid were added and the solution was heated under reflux
for 2 90 hours The solution was cooled to 0-5 C.
and the p aminophenacyl methyl di(betahydroxyethyl)ammonium chloride
was diazotized by the addition of 6 ml of 5 N sodium nitrite solution
The solution was kept at 0 95 C for 30 min and the excess sodium
nitrite was decomposed with sulfamic acid.
N beta cyanoethyl N methylaniline ( 4 5 grams) was added and the
mixture was stirred at 5-10 C for 2 hours A p H of 3 was 100
maintained by the periodic addition of sodium acetate The mixture was
allowed to warm up to room temperature over a 4 hour period with
stirring The product was isolated by filtration.
It was purified by trituration with acetone, 105 isolated by
filtration, and dried in a vacuum oven at 700 C The product is a
yellow powder that dissolves readily in warm water to give a
yellow-orange solution Poly acrylic fiber is dyed yellow-orange from a
neutral 110 dyebath at the boil The dye obtained has the formula:
785,988 785,988 cl H 3 (Ho CH 2 CH 2)2 N+J NN= / -/' CH 3 CH 2 CH
2 CN These dyes have an excellent light-fastness rating of from about
5 to 8 on polyacrylic fiber These light-fastness ratings are rated on
the American Association of Textile Chemists and Colorists' scale of 1
to 8, which is defined in terms of Fadeometer exposure hours before a
noticeable break, e g, No 1 being 1 25-2 5 hours, No 2 being 2 5-5
hours, No 3 being 5-10 hours and doubling with each number up to No 8
which represents a light-fastness of 160-320 hours.

When the acylammonium radical is in the meta position to the monoazo
linkage, it has is been found that the resulting dyes have good
light-fastness ratings.
The application of the cationic monoazo dyes of the present invention
to union fabrics of polyacrylic fiber and cellulosic fibers is carried
out advantageously at 212 F in a neutral or slightly alkaline (p H
7-9) dye bath at the boil As much as 1-1 2 % of these dyes (on the
weight of the said polyacrylic fiber present in the mixture) can be
applied in this fashion to the fiber with only slight or negligible
staining of the cellulosic fiber.
Application of these dyes to union fabrics of polyacrylic fiber and
wool is carried out advantageously at 2120 F in a dye bath containing
2 % glacial acetic acid, 2 % sodium acetate (on the weight of the
fiber mixture) and 2 % (on the weight of the fiber mixture) of a
non-ionic surface-active agent, such as Emulphor ON As much as 1-1 2 %
of these dyes (on the weight of the polyacrylic fiber present in the
mixture) can be applied in this fashion to the polyacrylic fiber alone
These dyes possess the properties of indicators, and when applied to
polyacrylic fiber by the above procedure may undergo a shade change,
which occurs usually when weak dyeings are prepared, i e, when the dye
represents only 0 10.4 % of the polyacrylic fiber being dyed In these
cases the shade change can be prevented by including 2-4 % (on the
weight of the fiber mixture) of a long chain quaternary ammonium salt,
such as cetyl trimethyl ammonium bromide in the dye bath.
* Sitemap
* Accessibility
* Legal notice
* Terms of use
* 5.8.23.4; 93p

5576 5580.output

Recommended

Recommended

More Related Content

What's hot

What's hot (19)

Viewers also liked

Viewers also liked (20)

Similar to 5576 5580.output

Similar to 5576 5580.output (20)

More from Иван Иванов

More from Иван Иванов (20)

Recently uploaded

Recently uploaded (20)

5576 5580.output