5561 5565.output

* GB785969 (A)
Description: GB785969 (A) ? 1957-11-06
Process of producing solid chloro-paraffins
Description of GB785969 (A)
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and information originating from other authorities than the EPO; in
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up-to-date or fit for specific purposes.
PATENT SPECIFICATION
785,969 l M| A d Date of Application and filing Complete Specification
May 3, 1956.
No 13748/56.
Application made in Germany on May 13, 1955.
Complete Specification Published Nov 6, 1957.
Index at acceptance: -Class 2 ( 3), CIGI(A 2: D), C 1 G 6 A 1.
International Classification: -CO 7 c.
COMPLETE SPECIFICATION
Process of Producing Solid Chloro-Paraffins' We, IMHAUSEN W Ea Rca G M
B HS, of Witten-Ruhr, Germany, a Body Corporate organised under the
Laws of Germany, 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 a process of producing solid
chloro-paraffins.
It is known that paraffinic hydrocarbons can be chlorinated and that
the products are liquid or solid according to their molecular weights
and their chlorine content.
The production of solid chloro-paraffins with high melting points
presents fairly substantial technical difficulties.

By introducing large quantities of chlorine into low molecular
paraffinic hydrocarbons, solid products can be obtained but the
chloroparaffins thus produced all have relatively low melting points
Higher molecular and more particularly solid paraffinic hydrocarbons
by themselves are difficult to chlorinate to high chlorine contents
because they become increasingly viscous as their chlorine content
increases and they strongly tend to effervesce.
Moreover, the temperature cannot be arbitarily raised to reduce their
viscosity during chlorination because the compounds then dissociate
and darken.
It has therefore been proposed to chlorinate these higher molecular
paraffins in a solvent, more particularly carbon, tetrachloride
However these methods also suffer from grave disadvantages The
relative volatility of the solvent necessitates comparatively low
chlorination temperatures and these entail prolonged reaction times In
view of the high viscosity of chloro-paraffins at these low
temperatures, large quantities of solvent are needed and their
recovery calls for special apparatus, quite apart from the fact that
they are most difficult to separate completely from the chlorinated
product.
It has now been found that solid chloroparaffins with relatively high
melting points can be prepared in a simple manner by chlorinating high
molecular paraffinic hydrocarbons, more particularly solid paraffins,
such as commercial paraffin melting at 52 C, or crude paraffin wax,
together with relatively low molecular paraffinic hydrocarbons such as
fractions boiling between 150 and 2500 C, or their chlorination
products The low molecular hydrocarbons and their chlorination
products apparently serve as solvents for the higher molecular
hydrocarbons and permit chlorination at higher temperatures so that
viscosity is reduced, the utilisation of the chlorine improved and
more stable compounds are produced The lower molecular chlorination
products need not be removed when chlorination has been completed.
Based on the foregoing discovery, the present invention provides a
process for the production of solid chloro-paraffins, which comprises
subjecting a mixture of high molecular paraffin hydrocarbons
containing more than 20 carbon atoms in the molecule and especially
solid paraffins, with comparatively low molecular paraffin
hydrocarbons containing between 5 and 20 carbon atoms, and preferably
between 10 and 16 carbon atoms in the molecule (especially fractions
boiling between and 2500 C) or their chlorination products, to
chlorination in a manner known per se, at temperatures of between 50
and 180 C, and preferably between 80 and 1400 C.
According to the proportions in which the lower and higher
hydrocarbons are present, hard resins melting at more or less elevated

temperatures are obtained.
It is an advantage to add inorganic and/or organic nitrogen compounds
such as ammonium chloride, urea or amines, before and/or during
chlorination, in order to prevent the product from darkening, as this
easily happens at elevated temperatures, when chlorination is
interrupted or when the dissolved chlorine and hydrogen chlorides are
being driven out with a current of gas after chlorination is complete.
Chlorination is conveniently effected at' 785,969 increasing
temperatures with the final temperature as high as may be compatible
with the preservation of colour, because the chloroparaffins produced
at high temperatures are more stable than those produced at lower
temperatures.
The invention will be illustrated by the following examples, in which
the parts referred to are parts by weight:EXAMPLE 1 parts of paraffin,
m p 520 C, and 18 parts of a paraffinic hydrocarbon boiling between
about 180 and 225 C, are chlorinated together at a temperature of
about 100 C, whilst exposed to light, until the chlorine content has
risen to about 65 % The temperature is then raised gradually to 160 C.
When the chlorine content is 71 7 % the product obtained has a melting
point of 690 C If chlorination proceeds to 75 % chlorine a light
yellow product results which fuses at 1080 C.
EXAMPLE 2 parts of paraffin, m p 520 C, and 60 parts of a
chloro-hydrocarbon with a chlorine content of 71 % prepared from a
paraffinic hydrocarbon boiling between 180 and 2250 C., are
chlorinated together at a temperature of 1800 C Chlorine contents
equal to those mentioned in Example 1 produce the same chlorination
products.
EXAMPLE 3 parts of crude paraffin wax from the hydrogenation of carbon
monoxide, and 21 parts of a synthetic paraffinic hydrocarbon boiling
between 160 and 2100 C, are chlorinated together as described in
Example 1.
When the chlorine content is 72 6 % the product is a brittle light
resin which fuses at 750 C.
On the other hand, if a fraction between and 225 is chlorinated by
itself the product at 73 % C 12 is already considerably viscous at 400
C Moreover, a paraffin melting at 520 C cannot be chlorinated at 1000
C.
in a reasonable time without the use of a solvent, to more than 62 to
65 % Cl 2 as it otherwise becomes too viscous and effervesces
considerably At higher temperatures the product becomes very dark.
If darkening should occur in the course of chlorination a pronounced
lightening in colour can be achieved in the course of further
chlorination by the admixture of 03-0 5 % of ammonium chloride or
urea.

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* 5.8.23.4; 93p
* GB785970 (A)
Description: GB785970 (A) ? 1957-11-06
Inhibitor for lubricating oil compositions
Date of Application and filing Complete Specification: May 8, 1956.
No 14253156.
Application made in United States of America on May 25, 1955.
Complete Specification Published: Nov 6, 1957.
Index at acceptance:-Classes 2 ( 3), B 4 E, C 2 C( 2: 6 C: 7 A 2: 7 A
3: 8); and 91, F( 1: 2).
International Classification:-CO 7 d Cl Om.
Inhibitor for Lubricating Oil Compositions; We, Esso RESEARCHAND
ENGINEERING COMPANY, a Corporation duly organised and existing under
the laws of the State of Delaware, United States of America, of
Elizabeth, New Jersey, State of 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: -
This invention relates to lubricants and more particularly relates to
improved lubricant compositions containing a new class of products as
corrosion and oxidation inhibitors, to the novel products themselves
and to the method of their preparation The novel products of this
invention, which are oil soluble, are prepared by reacting a metal
polysulfide with diphenylamine or an alkyl derivative thereof.
The successful lubrication of internal combustion engines is
complicated by the deterioration of the lubricating oil during use
Oxidation of the oil, for example, causes the formation of sludge and
lacquers that deposit on parts of the engine and interfere with
circulation of the oil Also, certain deterioration products are acidic
in nature and corrode bearing metals and other metal parts The
difficulties encountered in regard to corrosion have become aggravated
in recent years because of the increasing utilization of bearings made
of alloys such as cadmium-nickel, copper-lead, cadmium-silver, etc,
and also because of the increased severity of engine operation.
Although the discovery of certain lubricant additives has alleviated
this problem to a certain extent, there is a continuing need for still
further improved lubricating compositions which are resistant to
oxidation.
In accordance with the present invention, it has been found that a
product prepared by reacting an alkali or alkaline earth metal
polysulfide with diphenylamine, or certain alkyl derivatives thereof,
imparts improved antioxidant and anti-corrosion properties to a
lubricant More specifically, the products of this invention are
prepared by reacting an lPrice 3 s 62; f 3 >CC El 4 alkali or alkaline
earth metal polysulfide with a compound having the formula where each
R is hydrogen or an alkyl radical containing 1 to 16 carbon atoms,
preferably 1 to 10 carbon atoms The reaction is carried out at an
elevated temperature and for a period of time sufficient to produce an
oil-soluble reaction product which contains a ratio of sulfur atoms to
nitrogen atoms in the range of from 0 4 to 1 5, preferably from 0 5 to
1.0 The proportions of the reactants are selected so that the amount
of the metal polysulfide employed in the reaction is such as to
provide sufficient reactive sulfur atoms to produce an oil-soluble
reaction product containing the aforementioned sulfur to nitrogen
ratio The reaction mixture (resulting from the reaction of the metal
polysulfide and the diphenylamine compound) will generally contain a
small amount of oil-insoluble material and this is removed by
filtration or decantation from oil solution (e g hexane) to yield the
oilsoluble product of this invention.
The metal polysulfides of this invention preferably have the following

general formula:
Ma Sb where M is an alkali metal or an alkaline earth metal, a is an
integer of 2 in the case of alkali metals and 1 in the case of
alkaline earth metals and b is 2, 3, 4 or 5 The preferred metals are
calcium, barium, magnesium, lithium, sodium, and potassium The
alkaline earth metals are particularly preferred The preferred metal
polysulfides are calcium polysulfides It has been found that metal
monosulfides alone are inoperative in the present invention The metal
polysulfides utilized in this invention may be r 85,970 prepared by
any conventional methods such as by heating 1 mole of the metal
monosulfide with about 1 to 4 moles, particularly about 3 moles, of
elemental sulfur Such reaction may be conveniently carried out at a
temperature in the range of about 2000 to 300 F for a period of time
of about 0 5-2 hours In this type of preparation it is desirable to
carry out the reaction in water which serves as a vehicle or carrier
for the reactants The products produced by reacting metal monosulfides
with elemental sulfur are predominantly metal polysulfides, and the
total product may be employed in this invention if desired The
reaction of the metal polysulfide and the phenylamine compound is
carried out at an elevated temperature so that the reactants are
maintained in a molten state Temperatures in the range of about 175 F
to 570 F may be employed to carry out the reaction At temperatures
below about 1750 F the reactants will not readily react whereas at
temperatures in excess of about 5700 F difficulty is encountered due
to the vaporization of the diphenylamine compound Preferably the
reaction temperature is maintained in the range of about 200 to 300 F.
The proportion of the metal polysulfide employed in the reaction is
such as to provide sufficient reactive sulfur atoms to produce an
oil-soluble reaction product containing a ratio of sulfur atoms to
nitrogen atoms in the range of about 0 4 to 1 5, preferably 0 5 to 1
0.
Because the higher sulfur content polysulfides contain a greater
number of reactive sulfur atoms per molecule, it is therefore possible
to utilize a smaller proportion of them in the reaction than in the
case of the lower sulfur content polysulfides such as the disulfides.
The term "reactive sulfur atoms" refers to those atoms of sulfur which
are combined with the metal in excess of one sulfur atom per molecule
Thus the metal polysulfides may be expressed as MSSY where y is an
integer of 1 to 4 and S, designates the "reactive sulfur atoms " The
reaction is carried out for an extended period of time until an
oil-soluble reaction product is obtained which contains the desired
ratio of sulfur atoms to nitrogen atoms, which ratio, as previously
stated, is in the range of about 0 4 to 1 5, preferably about 0 5 to 1
0.

A reaction time in the range of about 0 5 to 4.0 hours is generally
sufficient to produce an oil-soluble reaction product containing a
ratio of sulfur atoms to nitrogen atoms in the range of 0 4 to 1 5,
providing, of course, that a sufficient quantity of the metal
polysulfide is employed Preferred reaction times are in the range of
about 1 to 2 hours Upon completion of the reaction, the compounds of
this invention may be dissolved in a suitable solvent such as hexane,
heptane, petroleum ether, ligroin, etc, and then filtered to separate
therefrom any insoluble inorganic material such as metal monosulfides,
metal oxides and other unreactive products Thereafter the compounds of
this invention may be recrystallized from the solvent The crystallized
product contains no detectable amount of metal, 70 which is removed by
filtration as described above It has not been possible to date to
identify the molecular structures of the products of this invention.
The following examples are intended to 75 illustrate in greater detail
but it will be understood that it is not intended that the invention
be limited thereto.
EXAMPLE 1
A calcium polysulfide product was prepared 80 by placing 72 grams of
calcium monosulfide, 96 grams of sulfur, and 400 grams of water in a
one-liter glass flask which was equipped with a condenser, stirrer,
and thermometer.
The contents of the flask were heated for about 85 one hour at about
2150 F, with the water being refluxed during the reaction The reaction
produced a red jolored upper liquid layer and a small lower layer of
unreacted solid materials The red colored liquid was 90 separated and
was then evaporated to dryness to recover a yellow powder which
contained 22 ' calcium and 57 5 % sulfur Although the calcium
polysulfide product in this example was prepared as described above in
the labora 95 tory, it will be understood that any polysulfide of
alkali or alkaline earth metals may be used in the reaction described
below.
34 grams of the powder prepared above were then blended with 84 grams
of diphenyl 100 amine and the mixture was placed in a oneliter glass
flask equipped with a condenser, stirrer, and thermometer The contents
of the flask were heated together for two hours at C After cooling,
the contents of the 105 flask were blended with about 250 cc of hexane
and the solution was filtered through a Buchner funnel A small amount
of insoluble material was collected on the filter.
This insoluble material consisted primarily of 110 calcium monosulfide
and other unreactive calcium and sulfur containing products Thereafter
the oil-soluble product of this invention vas recrystallized from the
hhexane and dried to produce a crystalline product which con 115
tained 12 32 % sulfur, 6 47 %' nitrogen and no detectable amount of

calcium The product was readily soluble in mineral oil and will
hereinafter be termed Product A The ratio of sulfur atoms to nitrogen
atoms in Product 120 A was 0 84.
A similar reaction was carried out utilizing diphenylaimine and
calcium monosulfide but no reaction took place, thus indicating the
necessity of utilizing a polysulfide in the 125 reaction with
diphenylamine.
EXAMPLE 2
About 34 grams of the dried powder prepared in Example 1 were blended
with 98 2 grams of pp'-dioctyl diphenylamine and the 130 785,970
EXAMPLE 3
In order to determine the storage stability of the oil-soluble
reaction products of this invention in mineral lubricating oils,
various concentrations of Product A and B were added to a mineral
lubricating oil base stock (hereinafter termed Base Stock I) and were
tested for stability under the following conditions:
( 1) in the sunlight at room temperature and ( 2) in a refrigerator at
350 F The storage stability of the blends was determined by noting the
period of time that they remained clear without any evidence of
turbidity, suspended sediment or solids precipitation An anti-oxidant
additive of the prior art, namely phenothiazine, was also subjected to
these storage stability tests for comparison purposes.
mixture was placed in a one-liter glass flask equipped with a
condenser, stirrer, and thermometer The contents of the flask were
heated for one hour at 1400 C, after which the contents were cooled
and then added to about 250 cc of hexane The resultant solution was
filtered through a Buchner funnel and a small amount of oil-insoluble
material was collected on the filter The oil-soluble product of this
invention was then recrystallized from the filtrate and dried An
oilsoluble crystalline product was obtained which contained 4 02 %
sulfur, 3 37 % nitrogen and no detectable amount of calcium This
product will hereinafter be termed Product B. The ratio of sulfur
atoms to nitrogen atoms in Product B was 0 53.
TABLE I
Storage 'Stability Test Additive in Base Stock 1 Storage Stability,
Days Sunlight Refrigerator Type Conc, Wt;% Room Temp 350 F.
Product A , , Product B h h Ph enothi azin e 0.5 2.0 3.0 5.0 3.0 5.0
0.5 + + < 10 + + + 2 l + 7 < 2 Base Stock I was a solvent refined
Mid-Continent mineral oil base stock (SAE-20 grade) having the
following inspections:
Gravity, O A Pl = 29 4 SUS viscosity @ 1000 F = 522 6 Pu t, @ 2100 F =
66 2 Pour Pt,, F = -'10 EXAMPLE 4
The effectiveness of Product A as an oxidation inhibitor was then
determined in a test which was carried out as follows: A 500 cc.

sample of the test lubricant was charged to a "Pyrex" tube in a salt
bath held at 3250 F.
("Pyrex" is a Registered Trade Mark) A shaft holding two halves of a
copper-lead bearing was rotated in the test lubricant at 400 to 650 r
p m while 2 cu ft /hour of air was bubbled through the lubricant The
test was run for 4-hour periods, and at the end of each, the bearings
were cleaned and 65 weighed to measure weight loss The test was
continued 'in repeated 4-hour cycles until a cumulative bearing weight
loss of 100 mgms.
was obtained.
For comparison purposes, phenothiazine 70 was similarly tested and the
following results were determined:
TABLE II
Oxidation-Corrosion Test Additive in Base Stock I Conc, Type Wt % None
Product A Phenothiazine Hours to Lose mgms.
12 34 0.5 0.5 785,970 The results of the tests shown in Examples 3 and
4 clearly indicate that products made in accordance with this
invention are outstanding additives for lubricating oil compositions
on account of ( 1) their excellent solubility in lubricating oil base
stocks and ( 2) their effectiveness in reducing oxidation and
corrosion.
EXAMPLE 5
The products of this invention are not a mere mixture of diphenylamine
(or its alkyl derivatives) and phenothiazine (or its alkyl
derivatives), which can be formed by reacting diphenylamine (or its
alkyl derivatives) with elemental sulfur This is shown by the
following laboratory treatment of the product of this invention A
benzene solution of Product A was washed with a 10 % solution of
hydrochloric acid and the water phase separated.
If free diphenylamine had been present, it would have formed the
diphenylamine hydrochloride salt which is water soluble The water
layer was neutralized with sodium hydroxide to liberate free
diphenylamine, which being water insoluble would precipitate.
Since no precipitate was formed, it can be concluded that the product
of the invention contains no free diphenylamine.
Product A of this invention as well as diphenylamine, phenothiazine
and mixtures of diphenylamine and phenothiazine were evaluated as
additives in a mineral lubricating oil in the Oxidation-Corrosion Test
described in Example 4 The mineral lubricating oil (hereinafter termed
Base Stock II) was a solvent refined Mid-Continent mineral oil base
stock of SAE-30 grade The results of these tests are shown below:
TABLE III
Oxidation-Corrosion Test Additive, Wt % in Base Stock II None
Phenothiazine 0 5 % Product A 0.5 % Hours to Lose mgms.

Diphenylamine 1 0 % Phenothiazine O 5 % Diphenylamine 05 % 1
Phenothiazine 0 75 %} Diphenylamine 0 25 %' When additives of this
invention are employed in lubricating oils, they are usually added in
proportions in the range of about 0.01 to 10 0 % by weight and
preferably in the range of about 0 1 to 5 O % by weight, particularly
about 0 2 to 1 0 % by weight If the additives are utilized at high
concentrations, conventional solubilizers may be employed to increase
the solubility of these additives The proportions giving the best
results will vary somewhat according to the nature of the additive.
The products of the present invention may be employed not only in
ordinary hydrocarbon lubricating oils but also in the "heavy duty"
type of lubricating oils which have been compounded with such
detergent type additives as phosphosulfurized hydrocarbons, metal
soaps, metal petroleum sulfonates, metal phenates, metal alcoholates,
metal alkyl phenol sulfides, metal organo phosphates, thiophosphates,
phosphites and thiophosphites, metal salicylates, metal xanthates and
thioxanthates, metal thiocarbamates, amines and amine derivatives,
reaction products of metal phenates and sulfur, reaction productions
of metal phenates and phosphorus sulfides and metal phenol sulfonates
Thus the additives of the present invention may be used in lubricating
oils containing such other addition agents as barium tert -octylphenol
sulfide, calcium tert amylphenol sulfide, nickel oleate, barium
octadecylate, calcium phenyl stearate, zinc diisopropyl salicylate,
aluminum naphthenate, calcium cetyl phosphate, barium di-tert
-amylphenol sulfide, calcium petroleum sulfonate, zinc
methylcyclohexyl thiophosphate and calcium dichlorostearate.
The lubricating oil base stocks used in the compositions of this
invention may be mineral lubricating oils or distillates derived from
paraffinic, naphthenic, asphaltic, or mixed base crudes, or, if
desired, various blended oils may be employed as well as residuals,
particularly those from which asphaltic constituents have been
carefully removed The oils may be 785,970 alcohols, aldehydes,
halogenated or nitrated compounds, and the like may also be employed.
In addition to being employed in lubricants, the additive of this
invention may be also used in motor fuels, hydraulic fluids, torque
converter fluids, cutting oils, flushing oils, turbine oils or
transformer oils, industrial oils, process oils, gear lubricants,
greases, and generally as anti-oxidants in oleaginous products.
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* GB785971 (A)
Description: GB785971 (A) ? 1957-11-06
Improvements in or relating to the mounting of electronic circuit components
Inventors: JACK EVANS and IDWAL JOHN TAYLOR JENKINS 785,971 / il ' Air
Date of Application and filing Complete Specification: May 9, 1956.
No 14352/56 Complete Specification Published: Nov 6, 1957.
Index at acceptance:-Classes 37, T 1; and 108 ( 3), R, 56 E 2.
International Classification:-F 06 f H Oin.
Improvements in or relating to the Mounting of Electronic Circuit
Components We, STANDARD TELEPHONES AND CABLES LIMITED, a British
Company, of Connaught House, 63 Aldwych, London, W C 2, England, 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 supporting of articles in holes in
plates or sheets and more particularly to the mounting of electronic
circuit components and articles of similar shape.
The main feature of the invention consists in a compressible tubular
member of rubber or other resilient material having a cylindrical
outer wall, an external flange at one end and a bore tapering towards
the other end, and capable of acting as a grommet.
The invention will now be described with reference to the accompanying
drawings, in which:Fig 1 shows a sectional elevation and end views of
a compressible tubular member or grommet; Fig 2 is a side view of a
member inserted in a panel, and Fig 3 is a side view showing an
electrical component inserted in a member in a panel.
As seen in Fig 1, a compressible tubular member or grommet comprises a
cylinder 1, preferably of rubber or the like having at one end an

external flange 2 and having a tapering bore-hole 3 with the layer end
of the taper at the same end as the flange 2.
The diameter of the smaller end 4 of the bore-hole is arranged to be
less than the external diameter of an article to be mounted therein
Such an article may be an electronic circuit component such as 5 (Fig
3).
In order to mount the component in a plate or sheet such as 6, the
grommet is inserted into a hole in the plate 6 (Fig 2) so that the
flange 2 is on one side of the plate 6 and the end of the cylinder 1
having the lPrice 3 s 6 d l smaller end 4 of the bore-hole is
projecting from the other side of the plate, the diameter of the hole
in the plate 6 being approximately equal to the external diameter of
the cylinder 1 An article such as 5 (Fig 3) is then 50 pushed or
driven into the bore-hole from the flange end The cylinder 1, at least
towards the smaller end of the bore hole is expanded or forced into
intimate contact with the wall of the hole and that part of cylinder
which 55 projects beyond the plate 6 is expanded around the end of the
hole so that the component and the member cannot be easily removed
from the plate.
It has been found that such a member is 60 simple to manufacture as by
moulding and that such a method of mounting a component is easy and
cheap Furthermore the component is not likely to be damaged during
mounting and is held in a resilient and shock 65 proof manner.
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* GB785972 (A)
Description: GB785972 (A) ? 1957-11-06
Process for the preparation of purified concentrates with intrinsic factor
activity

Process for the Preparation of Purified Concentrates with
Intrinsic Factor Activity
We, ORGANON LABORATORIES LIMITED, a
British Company, of Brettenham House, Lancaster Place, London, W.C.2,
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 statment : -
The invention relates to a process for the preparation of purified
concentrates with intrinsic factor activity, which contain a vitamin
of the B,, group.
It is generally known, that for the resorption of orally administered
vitamin B12 intrinsic factor is nncessary. This intrinsic factor
(hereinafter indicated by I.F.) which was first described by Castle
and collaborators (see Am.J.Med.Sci. 178, 748 (1929)), is a component
of normal human gastric juice and occurs therein in a sufficient
measure to place the extrinsic factor, viz. vitamin B12 or another
vitamin of the B12 group, from the food at the disposal of the
organism. In some persons the I.F. in the gastric juice is lacking so
that with those, owing to the failure of the resorption of the vitamin
B12 from the food, finally the symptoms of the pernicious an mia may
occur. It is of importance that there shall be available for such
persons and all those whose production of I.F. is partly disturbed,
I.F. preparations which can be taken simultaneously with the food, or
even more favourably of vitamin B,, containing I.F. conpentrates
because in the latter case there is the assurance that sufficient B12
is present so that they are not dependent on the B12 content of the
food.
As sources or I.F. activity are considered, in addition to normal
human gastric juice, animal organs such as the pylorus, the duodenum,
and other parts of the digestive tract and in particular the mucosa
thereof. Especially the above organs of the pig possess a great I.F.
activity.
Crude I.C. preparations may for example be obtained by drying and then

grinding the above animal organs if necessary together with one or
more vitamins of the B,, group.
It is a great objection that, in order to obtain a good, h matopoietic
effect, very large quantities of such crude preparations have to be
administered daily to patients suffering from pernicious anemia.
Attempts have therefore been made to concentrate these preparations.
From Specification No. 733,875 it is known that I.F. concentrates
which contain a vitamin of the B12 group can be purified by
precipitating them from a solution hereof by means of an alkanol or
alkanone, for example ethanol or acetone, at a temperature below oo C.
In Ptoc.Soc.Exptl.Biol.lUINed. 87, 400 (1954)
W. L. Williams and others describe how I.F. concentrates which contain
no vitamin B12 can be prepared by fractionating solutions with LF.
activity by means of alcohol. These investigators isolate the fraction
which is precipitated between 40 and 80% by volume of ethanol.
It has now been found that according to the present invention purified
LF. preparations can be prepared by treating a concentrate with
I.F. activity in the presence of a vitamin of the B12 group, in an
aqueous system which has 35-50%' by volume of an alkanol or alkanone
with not more than three carbon atoms, and separating the resulting
liquid phase which contains the active constituent. As such systems
solutions may be employed of one or more of the substances methanol,
ethanol, isopropanol, propanol, and acetone. By the treatment of the
concentrate according to the process is understood the selective
dissolving of the I.F. active constituent therefrom.
As starting products may be used a liquid or solid concentrate for
example in powder form, whether dried or not, or a somewhat purified
precipitate, such as is for example obtained according to the process
of saint patent Specification.
The process according to the invention may be applied to any
concentrate that has I.F. activity in whatever stage of purity it may
be.
If desired, aqueous solutions of I.F. concentrates may be converted
into a solid concentrate, for example by drying iez vacuo, by
lyophilizing, by spray-drying.
As vitamin B1, containing substance which is added to the I.F.
concentrate before applying the process of the invention, any
preparation that contains one or more members of the vitamin B12 group
is considered, such for example as the so-called "oral grade
solubles", crystalline vitamin B12 and other preparatlons obtainable
in trade.
It is preferable to perform the treatment in the presence of one or
several salts such for example as alkali chlorides, phosphates, etc.
This has for example as a result that after the treatment the liquid

can easily be separated from the remaining solid substance. A slight
quantity of a salt has already a very favourable action. In this
respect sodium chloride appears to have a very favourable action.
To improve the yield the treatment may be repeated once or several
times. It gives particularly favourable results if operations are
carried out at 0 C. or at lower temperature.
It is preferably carried out in a weakly acid medium for example at a
PH 6-7. The pH of the mixture can for example be adjusted to this
value by using the component parts of a buffer e.g. KH,PO4+Na,HPO4.
From several experiments it has appeared, that a very favourable
result is obtained when using 40 50% by vol. of ethanol. With this
percentage few ballast substances are extracted, as a result of which
a strong purifiction of the preparation is obtained. In a known way a
solid preparation can be prepared from the liquid phase for example by
lyophilizing, evaporating to dryness, or atomizing.
An extra purification of the preparation is effected by isolating this
from the resulting liquid by increasing the alkanone or alkanol
concentration to a value ranging from 6075% by vol. at which the I.F.
activity-containing compound precipitates, together with the bound
vitamin B,z, so that ultimately a preparation is obtained with a
strong human topoietic action in patients with pernicious an mia.
Dependent on the applied solvent, the precipitating agent used and the
nature of the tarting product, the limits of the alkanol and alkanone
concentration at which the most favourable purification takes place
may vary.
If, starting from a previously purified concentrate which shows a good
clinical activity on administration in a daily dose of +30 mg., this
concentrate is treated while making use of ethanol and the active
compound is then precipitated from the resulting solution, the
strongest I.F. active substance is obtained by increasing the ethanol
concentration of the solution to 60% by TOl. See for example,
Example 2 below in which the preparation is described of a preparation
which contains the active constituent in a concentration which is 10
times that of the starting product.
It is not necessary that the precipitation of the active compound from
the recovered liquid takes place with the same liquid which is us-.d
as solvent in the aqueous system. For the precipitation one of the
liquids commonly used for this purpose may be applied, such for
example as methanol, ethanol, acetone, or a combination of these
liquids.
The precipitate obtained from the solution by precipitation of the
active compound may be dried in a known way such for example as by
lyophilizing, drying in vacio, and passing over of warm air.
The action of the preparation may be tested by daily administering a

certain quantity hereof to patients with untreated pernicious anemia.
The preparation is preferably administered in the form of a tablet.
The action of the preparation is established on the basis of the
increase of the number of erythrocytes per cu. mm. of blood during a
certain period of treatmen. The erythrocytes content is frequently
determined a fortnight and 21 days after the beginning of the
administration of the preparation. In additicn the reticulocytes
maximum (in percentage) is frequently determined. The following
examples, in which the percentages are by volume, illustrate the
invention:
EXAMPLE 1
376 gm. of a powdered I.F. concentrate, to which during the
preparation so much cyans cobalamin has been added that the whole
binding capacity for cobalamin is saturated so that it contains about
0.28 ug. of vitamin B12 (cyanocobalamin) per mg. (in a bound form) are
used as starting product. This preparation is clinically active in a
daily dose of 38 mg. In a Waring blender the powder is moistened with
cold 45 X ethanol which solution contains 9 gin. of NaCl per 1.;
subsequently so much of this ethanolic solution is added to the
mixture that in all 4 1. thereof are used. The mixture is stirred at
50 C. for 18 hours after which it is centrifuged. The same process is
repeated twice more, each time with 45 XO ethanol which contains 9 gm.
of
NaCI per 1.
To the collected liquid phases cold 9646 ethanol is added until a
final concentration of about 75% is obtained. The temperature is kept
between 0 and 5 C. The resulting precipitate is collected and dried in
vacuo at low temperature. The final yield is 37.4 gm. of a red
coloured preparation with a vitamin B22 content of 2.3y of B12 per mg.
EXAMPLE 2
To a solution of an I.F. concentrate of which 30 mg. of dry substance
daily are clinically well active (while simultaneously administering
15pig. of B12 daily) sufficient cyanocobalamin is added to saturate
all binding capacity; subsequently, while stirring and at low
temperature 96% ethanol is added. The fraction which precipitates
between 0 and 40% ethanol concentration is intermediately removed by
centrifuging. Subsequently the ethanol concentration is raised from 40
to 75% as a result of which a precipitate is formed. This is collected
by centrifuging and serves as starting material for the extraction
according to the invention.
This starting material with a drying residue of 110 gm. and a total
vitamin B12 content of 50 mg., is suspended in 1.5 1. of cold 45%
ethanol solution which contains 17 gm. of NaC:l per 1. After stirring
at --50" C. for 24 hours the liquid is separated. The precipitate is

treated twice with 45% ethanol with 17 gm. of NaCS per 1. The
insoluble part is dried and the ethanol concentration of the collected
solutions, in all 2,880 ml., is increased in stages to gain an
impression as to the weight of the fractions which precipitate within
certain ethanol concentrations.
The precipitates are dried in vacuo.
In the following table these weights are summarised : -
Precipitated between
Fraction the alcohol limits Yield (gm.) Colour
Precipitate insoluble in 45% alcohol 45.5 white-light-brown
1 45-50 12.0 light rose
2 50-55 6.38 strongly red
3 55-60 1.87 red-yellow
4 60-70 2.99 nearly white
5 70-75 0.94 white
For determination of the clinical and microbiological activities the
fractions 1, 2 and 3 are, after termination, mixed, dissolved in
little water, and lyophilised. Microbiologically, with Lactobacillus
Leichmannii, a vitamin B12 content of 2.2 yg per mg. is found so in
all 46.6 mg. of B12 (yield more than 90%).
In the clinical assay in a daily dose of 2.9 mg. of this preparation,
completed with 5y of free cyanocobalamin already 3.30 millions of
erythrocytes per cu. mm. of blood are counted after a fortnight at an
initial value of 1.29 million, while this increase continues so that
after 21 days already 3.6 millions of erythrocytes per cu. mm. of
blood are present.
The reticulocytes maximum of 18.6% which was found in this patient
with pernicious anaemia on the eleventh day also points to the great
clinical activity of the preparation.
EXAMPLE 3
As starting product acetone is used containing the precipitate which
has been formed by adding an excess of a hydroxy cobalamin concentrate
to an aqueous solution of an I.F. concentrate so that all binding
capacity for cobalamin is saturated. The said mixture is treated with
a threefold excess of acetone in which the temperature is kept below 0
C. The precipitate is separated by centrifuging.
This starting product with a drying residue of 1,535 gm. and a
cobalamin activity which corresponds in all to 495 mg. of
cyanocobalamin, is suspended in 20.5 1. of 40% ethanol and stirred
overnight. After centrifuging the resulting residue is treated another
twice with, each time, 161. of 45% ethanol. Of the collected
solutions, in all 49 1., a sample is lyophilised in order to determine
the effect of the treatment. The content of dry substance of the
sample amounts to 5.4 mg. per ml. The collected solutions consequently

contain about 265 gm. of dry substance so that in this respect a
six-fold concentration has been reached.
To the collected solutions which have an organic solvent concentration
of about 45 /O (ethanol and a little acetone) about 19 1. of 96%
ethanol are now added to precipitate the active principle. After
drying in vacuo the precipitate has a weight of 165.5 gm. The Bl2a
content hereof, measured as cyanocobalamin activity in the
Lactobacillus Leichmannii test, amounts to 2.4y per mg. The total
quantity of vitamin B,2 in the precipitate amounts to 397 mg. I This
is a yield of 80% calculated with reference to the original, bound
quantity. This preparation is clinically active in a daily dose of 2.5
mg. (see the assay results in the following table).
Erythrocytes (million/cu. mm. of blood) Reticulocytes max.
Onthe On the
Patient Time 0 14th day 21st day Xt, day
A 1.43 1.82 2.43 23.4 9th
B 2.00 2.95 3.61 19.3 13th
EXAMPLE 4
As starting product use is made of methanol containing the precipitate
which has been prepared in the same way as described in
Example 3, however, with this difference that as a source of vitamin
B12 so-called B12 oral grade solubles have been used which, according
to the absorption spectrum, contain the vitamin in the form of
cyanocobalamin while for the precipitation 3 volumes of methanol have
been used.
The precipitate with a total wet weight of 5,638 gm. and a dry residue
of 1,643 gm. which in all contains about 500 mg. of B12 activity, is
suspended in 20 l. of 36 methanol which contains 20 gm. of NaCI per l.
Alter stirring for 17 hours the mixture is centrifuged.
A second and third treatment take place with a 40% methanol solution,
which contains 20 gm. of NaCl per 1. In all 56 1. of solution are
obtained to which 27 1. of cooled methanol are added. Here a
precipitate is formed. After drying hereof in high vacuum a final
product is obtained with 2.557 of B12 activity per mg. in a yield of
156.5 gm.
This final product is clinically very active.
Oral administration in a daily dose of 2.37 mg. to a patient with an
untreated pernicious anemia causes an increase of the erythrocytes of
1.0 million in 15 days and 1.47 million in 21 days at an initial value
of 1.17 million per cu. mm. of blood. The reticulocvtes maxlmum
amounts to 14.9% on the 9th day of the assay.
In a second patient the values found for the erythrocytes were: in the
beginning 1.82 million, after a fortnight 2.94 million and after 21
days 3.12 million.

The reticulocytes maximum on the 7th dap of the treatment amounted to
7.4%.
EXAMPLE 5
As starting product use is made of acetone containing the precipitate
which has been prepared in the same way as described in
Example 3. As a source of vitamin B,2, however, so-called B12 oral
grade solubles have been used in which the vitamin occurs in the form
of cyanocobalamin. 5.1 kg. of this starting product with a vitamin B12
activity totally corresponding to 350 mg. of B12 are treated with 15
1. of 30,' acetone and then twice with, each time, 12 1. of 35%
acetone.
Here a temperature of between5 and 0 C. is applied. During the latter
two treatments the 35% acetone always contains 15 gm. of
NaCl per 1.
To the collected solutions, in all 401., 25 1. of cold acetone are
added while stirring. After having been left to stand overnight at -
50 C the precipitate is collected and dried in vacuo
In all 80 gm. of the final product are obtained.
The vitamin B12 content is 3.67? of B12 per mg. The yield of B12
amounts to nearly 84 ' calculated with reference to the cyanocobalamin
activity.
EXAMPLE 6
Start is made from a cyanocobalamin-containing intrinsic factor
precipitate prepared according to Example 3 but the precipitation is
performed with ethanol instead of with acetone. This precipitate with
a wet weight of 2.7 kg. is suspended in 25 1. of a cooled 43% ethanol
solution which contains 20 gm. of NaCl per l., and the mixture is
stirred at -5 C. for 13 hours. Then it is centrifuged; the precipitate
is treated another twice with, each time, 20 1. of 45 % ethanol which
contains 20 gm. of NaCl per 1.
To the collected solutions, with a total drying residue of 1,40 gm.
24.8 1. of cold 96 ' ethanol are added while stirring, while the
temperature is kept at about -5 C. After the addition stirring is
continued for another hour after which the resulting precipitate is
centrifuged. The precipitate which has been formed by precipitation
between the limits of about 4S% to 60% ethanol is dried in high
vacuum. As final yield are obtained 138 gm. of a product which
contains 1.697 of B12 per mg. In a daily dose of 5.5 mg. the product
is clinically very active as appears from the following table
Erythrocytes (million/cu. mm. of blood) Reticulocytes max.
Onthe On the
Patient Time 0 14th day 21st day % day
C 0.85 1.92 2.84 44.6 8th

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* GB785973 (A)
Description: GB785973 (A) ? 1957-11-06
Manufacture of uranium tetrachloride
785,973 Date of Application and filing Complete Specification Dec I,
1944.
: ark No 24099/44.
Application made in United States of America on Dec 13, 1943.
Complete Specification Published Nov 6, 1957.
(Under Section 6 ( 1) (a) of the Patents &c (Emergency) Act, 1939 the
proviso to Section 91 ( 4) of the Patents and Designs Acts, 1907 to
1942 became operative on April 4, 1957).
Index at Acceptance:-Class 1 ( 3), A 1 (D 10: G 36 D 10).
International Classification: -C Oig.
Manufacture of Uranium Tetrachiloride We, UNITED KINGDOM ATOMIC ENERGY
AUTHORITY, of London, a British Authority, do hereby declare the
nature of this invention and in what manner the same is to be
performed, to be particularly described and ascertained in and by the
following statement: -
This invention relates to the manufacture of uranium tetrachloride by
the interaction of a uranium oxide and carbon tetrachloride at
elevated temperature.
Earlier investigators, including Camboulives, Comptes Rendu ( 1910)
150, 175-177, and Marden, U S A Patent 1,646,734 ( 1927), October 25,
mention the formation of uranium chloride by reacting uranium oxide

and carbon tetrachloride.
The present invention is concerned with a method of making uranium
tetrachloride by the above reaction, by which method there is a
considerable reduction in the tendency for some of the uranium
tetrachloride product to be lost by entrainment in the gaseous
products of the reaction.
According to the invention there is provided a process for the
manufacture of uranium tetrachloride by the interaction of carbon
tetrachloride and a uranium oxide at elevated temperature, wherein
carbon tetrachloride vapour generated from liquid carbon tetrachloride
in a first chamber is caused to flow under gravity into a second
chamber containing the uranium oxide maintained at elevated
temperature, the chambers being so interconnected that the gaseous
products of reaction pass from the second chamber upwardly into and
through the first.
The method of the invention has particular application to the
conversion to uranium tetrachloride of uranium dioxide and trioxide.
Particularly good results have been obtained using the method of the
invention for the conversion of uranium dioxide to uranium
tetrachloride at a temperature of 4250 C to 4750 C.
How the invention can be performed will now be described with
reference to the accompanying drawing, which is a diagrammatic
representation of apparatus suitable for use in the practice of the
invention Parts are given by weight throughout the written
description.
The apparatus shown in the drawing comprises a reaction vessel 3
connected to a condenser L which is in turn connected to a supply
reservoir 2 An inner gas line C extends through the condenser and into
the reaction vessel The reaction vessel is shaped somewhat like an
hourglass and comprises a first or vaporizing chamber B and a second
(" reaction ") chamber A These chambers are supported on sand bath
heaters 5 and 6, respectively The sand heater 5 is supported on a
bracket 7 and the sand heater 6 is supported on a bracket 8 Both
brackets are secured to the upright of a stand 9 which rests on the
surface 11 At the other end of the apparatus the upright of a stand 12
supports a bracket 13 which in turn supports bracket 14 which in its
turn, through a clamp 15, supports the elevated end of the condenser
at which end is vent 4 The upright of the stand 12 also supports a
bracket 16 to which is secured a clamp 17 which in turn supports the
reservoir 2.
Usually the reservoir 2 is graduated and has a gravity feed valve 18
whereby the rate at which the liquid reactant is being utilized can be
determined A container for an inert gas under pressure (not shown) is
connected at the upper end of the line C The outer jacket E of the

condenser has the usual inlet 19 and outlet 21 for a cooling fluid.
In operation the reaction chamber A is charged with uranium dioxide
and the reaction vessel 3 connected to the condenser L A gentle stream
of inert gas such as nitrogen is flowed into the reaction chamber A
through the line C to sweep out the air The flow of inert gas
continues throughout the reaction during which time it serves to sweep
out byproduct gases and excess carbon tetrachloride vapor Heat is then
applied to the reaction chamber A and a flow of carbon tetrachloride
started through the valve 18 This carbon 785,973 tetrachloride
collects in the vaporizing vessel B After a pool of the desired size
has collected, heat is applied and the addition of carbon
tetrachloride from the reservoir 2 regulated to keep the level
substantially constant.
Upon the application of heat to the vaporizing chamber B some of the
carbon tetrachloride vapors enter the condenser L and are refluxed.
Another portion of the vapor flows by gravity into the reaction
chamber where it reacts with the uranium dioxide, usually forming
carbon monoxide, carbon dioxide, phosgene and chlorine These gases are
swept up into the condenser along with some carbon tetrachloride vapor
by means of the nitrogen entering through the line C Some of the
phosgene is dissolved in the carbon tetrachloride and carried back
into the reaction chamber where it reacts with the uranium dioxide The
gases which are not condensed in the condenser are vented through the
line 4, usually into a scrubber of some sort.
Efforts to drop the carbon tetrachloride directly into the reaction
chamber have not been successful since liquid carbon tetrachloride
boils to form relatively tremendous volumes of vapor and as a result
the velocity of the gas sweeps some of the desired product out of the
reaction vessel, thereby lowering the yield In addition, uranium
pentachloride, which is volatile relative to the UC 1, is formed in
such an operation and passes into the condenser, clogging the
apparatus.
EXAMPLE I
Place a charge of 2242 parts of uranium dioxide in the reaction
chamber A of the previously described apparatus Connect the reaction
vessel 3 to condenser as shown in the drawing Introduce nitrogen in a
slow stream through the inner line C to sweep out, first, the air from
the apparatus, and then, after the reaction starts, the gaseous
reaction products.
Apply heat to the bulb containing the solid raw material and start
dropping carbon tetrachloride from the measuring container 2 into the
condenser L This liquid will collect in the vaporizing chamber B Apply
heat to the bulb containing the carbon tetrachloride and, when it
starts refluxing, maintain that condition The carbon tetrachloride

vapor at its boiling point is very much heavier than nitrogen and the
hot gases such as carbon monoxide, carbon dioxide, phosgene and
chlorine formed in the course of the reaction.
Some of the carbon tetrachloride, therefore, continuously and gently
flows downwardly into the reaction chamber When there is no reaction,
the only gas leaving the system is the small amount of nitrogen used
to maintain the slight sweeping action When the reaction mass reaches
4,50 ' C, maintain it at that temperature until the reaction is
complete In addition to carbon monoxide and carbon dioxide formed
during the reaction, some phosgene (COCL) and chlorine are produced.
At least a part of the phosgene is absorbed by he carbon tetrachloride
and returned for reaction with the uranium oxide By adjusting the flow
of carbon tetrachloride from the reservoir to keep the volume of the
pool in the vaporizing chamber B substantially constant the rate of
the reaction can be accurately followed At the completion of the
reaction 3153 parts of uranium tetrachloride will be obtained from the
reaction chamber.
EXAMPLE II
Repeat the procedure of Example I using 1056 parts of uranium trioxide
and maintain at an operating temperature of 500 C A yield of 1392
parts of uranium tetrachloride 80 will be obtained UCI, which tends to
form due to the use of UO, as charge stock is thermally unstable at
this reaction temperature, and is substantially converted into U Cl Q.
In carrying out the present process employ 85 ing uranium dioxide in
the production of uranium tetrachloride, the reaction temperature
should be maintained as near 450 C as practicable However, good
results are obtained in the range 425 to 475 C Diffi 90 culties are
encountered below 400 C and above 500 C, and these temperatures may be
considered the satisfactory operating limits.
Atmospheric pressure is preferred, although elevated pressures are not
objectionable and 95 small pressure variations do not materially
affect the yields or purity of the product.
The reaction is usually complete in less than five hours, the time
depending to some extent on the crystalline form and particle size 100
of the raw material, the temperature of the reaction, and the size of
the charge Ordinary commercial purity carbon tetrachloride is
satisfactory for the reaction The process may be carried out in glass
or metal apparatus 195 Since uranium compounds are expensive and
usually handled in small quantities it has appeared satisfactory to
illustrate Iaboratorysize apparatus With cheaper metals, which can be
handled on a much larger scale, it is 110 obvious that plant size or
large scale metal apparatus would be used.
After the uranium tetrachloride has been produced it may be poured
from the chamber.

It should be run into a dry container and 115 maintained in storage
under an environment of carbon dioxide or in vacuum.
The uranium tetrachloride produced in accordance with the present
invention has a crystal size and structure especially suitable 120 for
sublimation or vaporization in vacuum apparatus Its form allows it to
be readily out-gassed and there is little tendency for it to be
transported as a dust while being processed in a vacuum 125 Having now
particularly described and ascertained the nature of the said
invention, and in what manner the same is to be per785,973
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