5696 5700.output

* GB786104 (A)
Description: GB786104 (A) ? 1957-11-13
Preparation of unsaturated polyene compounds
Description of GB786104 (A)
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CH336063 (A) DE1001258 (B) FR1211308 (A)
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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.
COMPLETE SPECIFICATION
Preparation of Unsaturated Polyene Compounds
We, EASTMAN Konnx COMPANY, a Company, organized under the Laws of the
State of New Jersey, United States of America, of 343, State Street,
Rochester, New York,
United States of America (Assignee of
CHARLES DONALD ROBESON), 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 preparation of conjugated polyenes, and
is particularly concerned with the preparation of vitamin A active
compounds and their intermediates.
More specifically, the invention is concerned with the preparation of
such compounds by forming double bonds in certain carboxylic acid
compounds having a conjugated structure.

A preferred method for forming double bonds in organic compounds has
been to dehydrate carbinols with such dehydrating agents as mineral
acids, organic acids, acid salts and similar acidic dehydrating
agents. However, when conjugated carbinols are dehydrated with the
above acid dehydrating agents, isomeric mixtures are formed which are
difficult to separate. Such isomeric mixtures are unavoidable as the
acids that are used to effect the dehydration also catalyze the
isomerization of the dehydrated product.
As the resulting isomers often have similar chemical and physical
properties, they are difficult to separate.
The formation of isomeric mixtures is undesirable in synthetic
processes as additional purification steps are thereby required.
Further, low yields of the desired isomer may make the process
economically unfeasible. It is therefore highly desirable to have a
means by which a double bond can be specifically inserted in an
unsaturated organic compound having a conjugated structure without any
substantial isomerization accompanying such insertion.
It is accordingly an object of this invention to provide a new and
improved method for preparing conjugated polyenes without
isomerization.
It is a further object of this invention to prepare a biologically
active hydrocarbon with the formula of
<img class="EMIRef" id="026415663-00010001" />
COMPOUND 1.
These objects are accomplished by treating a conjugated beta-hydroxy
carboxylic acid with an acid anhydride, under substantially anhydrous
conditions, so as to decarboxylate and dehydrate the beta-hydroxy acid
and introduce a double bond between the carbon atoms alpha and beta to
the original carboxylic group to form a hydrocarbon having conjugated
unsaturation.
The invention is applicable to beta-hydroxy carboxylic acids having
the general formula
COMPOUND 2.
Where R is a conjugated polyene radical, each of radicals RI and
R"'-is a hydrogen atom or a lower alkyl radical and Rlll is a lower
alkyl radical, a conjugated polyene radical or a hydrogen atom, in
order to produce unsaturated polyene compounds of the formula
The term lower alkyl radical means an alkyl radical having from 1 to 7
carbon atoms. R and Ru are preferably conjugated polyenes in which the
conjugation is arranged so as to be in conjugation with the double
bond to be inserted between the alpha and beta carbon atoms of
Compound 2. Other conjugated polyenes can be employed however. A

preferred substituent of the radical R of Compound 2 is a conjugated
radical terminating in a beta-ionone ring.
In Compound 2, if the carbinol radical were attached to a carbon atom
other than the beta-carbon atom, or if the carboxyl radical were
esterified, substantially no decarboxylation would result when acid
anhydrides or other acidic dehydrating agents are employed.
Accordingly the herein described process is specific for a
simultaneous dehydration and decarboxylation of beta-hydroxy
carboxylic acids.
A typical beta-hydroxy carboxylic acid that can be dehydrated and
decarboxylated to form a conjugated hydrocarbon is 1- (2, 6,
6-trimethyl-1-cyclohexen-1-yl)-3, 7-dimethyl-7-hydroxy-8-carboxyl-1,
3, 5nonatriene having the formula
COMPOUND 3.
Other beta-hydroxy carboxylic acids that can be employed with similar
results include : 1- (2, 6, 6-trimethyl-1-cyclohexen-1-yl)3,
7-dimethyl-7-hydroxy-8-carboxy- 1, 3, 5-octatriene ; 1- (2, 6,
6-trimethyl1-cyclohexen-1-yl)-3-methyl-3-hydroxy4-carboxy-1-pentene ;
1-(2, 6, 6-trimethyl-1- cyclohexen-1-yl)-3 = methyl-3-hydroxy-
4-carboxy-1-butene ; 1- (2, 6, 6-trimethyl-1- cyclohexen-1-yl)-3, 7,
10-trimethyl-9hydroxy-10-carboxy-1, 3, 5, 7-decatetraene ; 1-2, 6,
6-trimethyl-1-cyclohexen-1-yl)3, 7-dimethyl-9-hydroxy-10-carboxy- 1,
3, 5, 7, 11-dedecapentaene ; 1- (2, 6,
6-trimethyl-1-cyclohexen-1-yl}-3, 7, 11trimethyl-9-hydroxy-10-carboxy-
1, 3, 5, 7, 11-dodecapentaene ; 1- (2, 6,
6-trimethyl-1-cyclohexen-1-yl)-3, 7-dimethyl-9-butyl-9-hydroxy-10-
carboxy-1, 3, 5, 7-decatetraene ; 1- (2, 6,
6trimethyl-1-cyclohexen-1-yl)-3, 7, 10trimethyl-9-hydroxy-10-carboxy-
1, 3, 5, 7-dodecatetraene ; 1- (2, 6,
6-trimethyl-1-cyclohexen-1-yl)-3, 7, 10trimethyl-9-hydroxy-10-carboxy-
1, 3, 5, 7-tridecatetraene ; and 6-hydroxy-7- carboxy-2, 4-heptadiene.
Beta-hydroxy carboxylic acids, as employed in this process can be
prepared by well-known methods.
Such beta-hydroxy carboxylic acids, however, are preferably prepared
with the well-known Reformatzky reaction by reacting alphahalogen
esters with a compound containing a carbonyl group and thereafter
saponifying the ester, acidifying and separating the betahydroxy acid
prepared by condensing vitamin
A aldehyde with alpha-bromo-propionate in the presence of zinc and
thereby forming a beta-hydroxy ester which can be readily converted
into the beta-hydroxy acid, 1- (2, 6, 6trimethyl-1-cyclohexen-1-yl)-3,
7, 10trimethyl-9-hydroxy-10-carboxy- 1, 3, 5, 7-decatetraene.
Any of the well-known acid anhydrides can be suitably employed such as

acetic anhydride, n-butyric anhydride, n-propionic anhydride,
n-caproic anhydride, phthalic anhydride and succinic anhydride. Other
well-known dehydrating agents such as mineral acids, organic acids and
acid salts do not simultaneously dehydrate and decarboxylate
beta-hydroxy carboxylic acids and thus can not be employed in lieu of
the acid anhydrides in the herein described process.
The acid anhydride dehydration and decarboxylation process is
conducted under substantially anhydrous conditions, preferably in an
organic solvent substantially inert to the acid anhydride such as
benzene, petroleum ether, and ethyl ether, although the present
reaction can be effected without the use of such solvents. The
reaction can be effected at room temperature although the application
of heat to the reaction mixture can be used to increase the rate of
reaction.
The dehydration and decarboxylation results in the introduction of a
double bond between the carbon atoms which were alpha and beta to the
original carboxyl radical. Accordingly, the product is not in mixture
with isomers because of this specificity of double bond introductions.
Further, decarboxylation of the beta-hydroxy acid is likewise specific
as well as being substantially complete. Thus, the preparation of
specific unsaturated compounds can be more easily effected in high
yields by this invention.
The invention is employed in the dehydration of conjugated carbinols
such as carbinols of vitamin A intermediates and similar conjugated
compounds. The usual method for dehydrating carbinols to the
corresponding unsaturated compound is to use acidic catalysts such as
hydrochloric acid, p-toluene sulphonic acid, phosphorous pentoxide,
and thionyl chloride. However, these acidic dehydrating agents produce
isomeric mixtures from which it is difficult to separate the desired
isomers. For example, in the acid catalyzed dehydration of a typical
conjugated carbinol such as a vitamin A intermediate having the
formula
COMPOUND 4.
An isomeric mixture results which contains a compound having the
formula
COMPOUND 5.
Together with the corresponding retroisomer having the formula
COMPOUND 6.
Thus, the above-described prior art dehydration process for the
insertion of a double bond in such a conjugated system is undesirable
because of the resulting isomerism.

Rowever, Compound 5 can be easily prepared substantially free of the
corresponding retro- isomer, Compound 6, by dehydrating a betahydroxy
carboxylic acid having the formula
COMPOUND 7,
With an acid anhydride under substantially anhydrous conditions.
Accordingly, in the dehydration of such a beta-hydroxy carboxylic acid
as Compound 7 with an acid anhydride, a double bond is specifically
inserted between the atoms alpha and beta to the original carboxyl
radical with substantially no reversion to the retro-isomer, Compound
6.
The present acid anhydride dehydration process not only dehydrates
beta-hydroxy carboxylic acids and specifically inserts double bonds
therein, with substantially no isomerization, but it also
decarboxylates betahydroxy carboxylic acids to form hydrocarbons. Thus
the process provides a simple and efficient means for preparing
hydrocarbons.
The herein disclosed acid anhydride dehydration and decarboxylation
process is particularly useful in preparing such hydrocarbons as
vitamin A hydrocarbon. Vitamin A hydrocarbon, Compound 1, is of
interest as it has about one-fourth the biological activity of vitamin
A alcohol. The dehydration of the corresponding beta-hydroxy
carboxylic acid,
Compound 3, with an acid anhydride to form vitamin A hydrocarbon can
be effected without the formation of isomers having less biological
activity such as the retro-isomer of vitamin A hydrocarbon. The
retro-isomer of vitamin A hydrocarbon has very low biological activity
and accordingly decreases the biological utility of vitamin A
hydrocarbon if admixed therewith. Many metnods of dehydrating
carbinols xesult in the formation of such undesirable isomers as the
retro-isomer and are thus unsatisfactory. However, vitamin
A hydrocarbon can be most easily prepared, with substantially no
isomerization, by the herein disclosed acid anhydride dehydration and
decarboxylation method.
The preparation of useful hydrocarbons of the formula
COMPOUND 8.
Wherein R is a conjugated polyene radical in conjugation with the
vitamin A moiety, the vitamin A moiety being the bracketed portion of
Compound 8, can also be readily effected by dehydrating and
decarboxylating the corresponding beta-hydroxy acid. Such betahydroxy
acids can be prepared by condensing vitamin A aldehyde with
alpha-halogen esters in accordance with the Reformatzky reaction.
Typical of the substituents for radical R* of

Compound 8 are = CH-CI,
= CH-CH = CH-CH = CH2,
and related conjugated polyenes. By adding to the conjugation of the
vitamin A moiety, compounds more highly coloured than vitamin A can be
prepared, with vitamin A active compounds exhibiting such colours as
yellow- orange and orange being readily prepared. The resulting
hydrocarbons thus have the biologically active vitamin A moiety in
addition to the chromatic-lending conjugated polyene radical.
Accordingly, these biologically active and highly coloured compounds
are particularly suited for fortifying and colouring numerus food
products and margarine in particular.
The invention includes an orange-yellow compound exhibiting vitamin A
activity and having the formula :-
EXAMPLE 1.
To a 1. 2 g. sample of 1- (2, 6, 6-trimethyl-1- cydohexen-'1-yl)-3,
7-dimethyl-7- hydroxy-8-carboxy-1,3,5-octatriene dissolved in 3 cc. of
benzene was added 1.2 g. of phthalic anhydride. After the mixture was
allowed to stand at about 25 C. for 24 hours, the mixture was admixed
with 100 cc. of Nl2 aqueous potassium hydroxide and thereafter
extracted with ethyl ether. The ether extract was washed again with
N/2 potassium hydroxide and thereafter further washed with water. The
remaining fraction was dried and chromatographed on a column of sodium
aluminium silicate. The non-adsorbed fraction, contaiing the product,
was further purified by crystallization from petroleum ether and
yielded yellow crystals of desmethyl vitamin
A hydrocarbon, 1- (2, 6, 6-trimethyl-1- cyclohexen - 1 - yl) - 3,7 -
dimethyl - 1,3,5,7octatetraene, melting at 61-62~ C. and E1%1cm.
(319 mIL) =1815. Infrared adsorption curves showed an absence of bonds
characteristic of hydroxyl or carboxyl groups, while showing curves
characteristic of a terminal methylene group.
EXAMPLE 2.
Desmethyl vitamin A hydrocarbon was pre-pared as in Example 1 except
that acetic anhydride was used instead of phthalic anhydride as the
dehydrating and decarboxylating agent.
EXAMPLE 3.
Desmethyl vitamin A hydrocarbon was prepared as in Example 1 except
that succinic anhydride was used instead of phthalic anhydride as the
EXAMPLE 4.
Desmethyl vitamin A hydrocarbon was prepared as in Example 1 except
that caproic anhydride was used instead of phthalic anhydride as the

EXAMPLE 5.
To a 6. 8 g. sample of 1-(2, 6, 6-trimethyl-l- cyclohexen 1-yl)-3,
7-dimethyl-7hydroxy-8-carboxy-1, 3, 5-nonatriene dissolved in 10 cc.
of benzene was added 6 cc. of acetic anhydride. The reaction and
subsequent purification were carried out as in Example 1.
The crude product from the reaction weighed 4. 65 g. for a
corresponding yield of about 84%. Yellow crystals of vitamin A
hydrocarbon, 1- (2, 6, 6-trimethyl-1-cyclohexen-1-yl)- 3,
7-dimethyl-1, 3, 5, 7-nonatetraene, resulted, having a m.p. 71-72~ C.
and E1%1cm.(323 m/t) =l800. Infrared analysis showed no remaining
hydroxyl or carboxyl groups.
EXAMPLE 6.
To a 5 g. sample of the beta-hydroxy acid 1- (2, 6,
6-trimethyl-1-cyclohexen-1- yl)-3-methyl-3-hydroxy-4-carboxy-
1-butene, ElC/ n (234 m} =185, was added 5
lcm. cc. of acetic anhydride. The reaction and subsequent purification
were carried out as in
Example 1. The resulting product, 1- (2, 6,
6trimethyl-1-cyclohexen-1-yl)-3- methyl-1, 3-butadiene, was a nearly
colourless, limpid oil weighing 1. 8 g. and having E 1c/m
lcm.
(228, 262 mu) =633, 611. The infrared adsorption curves of the product
showed bands characteristic of a terminal methylene group and an
absence of bands characteristic of hydroxyl or carboxyl groups.
EXAMPLE 7.
To a 5. 0 g. sample of the beta-hydroxy acid
1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3methyl - 3 - hydroxy - 4 -
carboxy - 1pentaene, having Ell' (234 m?) =166, dissolved in 7 cc. of
benzene was added 7 cc. of acetic anhydride. The solution was worked
up as described in Example 1. The purified hydrocarbon product, 1- (2,
6, 6-trimethyl-1- cyclohexen-1-yl)-3-methyl-1, 3 ~ penta- diene, was a
nearly colourless oil weighing-2. 2 g. and having E 1c/m (257 m) =679.
An infrared analysis of the product showed an absence of hydroxyl and
carboxyl groups.
EXAMPLE 8.
To a 6 g. sample of the beta-hydroxy acid, 1- (2, 6,
6-trimethyl-1-cyclohexen-1- yl)-3, 7,
10-trimethyl-9-hydroxy-10carboxy-1, 3, 5, 7-decatetraene, dissolved in
10 cc. of benzene, was added 6 cc. of acetic anhydride. The reaction
and subsequent purifiction were carried out in accordance with the
procedure described in Example 1. The purified hydrocarbon, 1- (2, 6,
6-trimethyl-1- cyclohexen-1-yl)-3, 7,
10-trimethyl1,3,5,7,9-decapentaene, was an orange-yellow
Vitamin A active material having E1 % 1cm.(356 m) =2040. Infrared

analysis showed an absence of hydroxyl and carboxyl groups.
Thus, by means of this invention a double bond can be specifically
introduced into a conjugated organic compound with the simultaneous
removal of a hydroxyl and a carboxyl group to form a hydrocarbon. The
disadvantages attendant upon other methods of dehydration are not
present, as there is substantially no isomerization of the product.
What we claim is :-
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* GB786105 (A)
Description: GB786105 (A) ? 1957-11-13
Improvements in or relating to internal combustion engines
PATENT SPECIFICATION
786,105 Date of Application and filing Complete Specification: July 6,
1955.
Application made in Brazil on July 23, 1954.
Complete Specification Published: Nov 13, 1957.
No 19474/55.
Index at acceptance:-Classes 7 ( 3), B 2 J 2; and 7 ( 6), B 2 Q( 1 C:5
B:5 D:9:15).
International Classification:-FO 2 f.
Improvements in or relating to Internal Combustion Engines I, A Nroxio
SBAIS, an Italian Citizen, of Via Conservatorio, 30, Milan, Italy, do
hereby declare the invention, for which I pray that a patent may be
granted to me, and the method bv which it is to be performed, to be
particularly described in and by the following statement:-

This invention relates to internal combustion engines and is more
particularly concerned with valve mechanism thereof, the principal
object of the invention being to provide a novel construction of
rotary or oscillating valve for admission of fuel, air, or fuel-air
mixture to and exhausting of gases from the cylinder which is more
efficient thanhitherto proposed forms.
According to this invention an internal combustion engine comprises a
cylinder head having a valve chamber, aligned inlet and exhaust
passages communicating with said chamber and disposed transversely of
the cylinder, a part-spherical rotary or oscillating valve mounted in
the valve chamber on a hollow shaft which is disposed transversely of
the cylinder and at right angles to the inlet and exhaust passages,
said valve being hollow and having one or more depressions providing
surface cavities for selectively connecting the passages with the
cylinder, and means for circulating cooling fluid through the shaft to
the valve in the direction of the axis of rotation thereof.
The invention will be described further, by way of example, with
reference to the accompanying drawings, in which:Fig 1 is a side
elevation, partly in crosssection of a single-cylinder petrol engine,
constructed in accordance with the invention, Fig 2 is an end
elevation, partly in cross-section, of the engine shown in Fig 1, Fig
3 is a cross-sectional detail of part of the engine aforesaid, lPrice
3/6 l Fig 4 is a cross-sectional view of an engine similar to that of
Figs 1 to 3, but having a fuel injection system, the section being
taken on the line A-A of Fig 5, Fig 5 is a horizontal section
correspond 50 ing to Fig 4, and Figs 6, 7, 8 and 9 are diagrams
illustrating various stages in the cycle of the engine.
Throughout the drawings, similar 55 reference numerals designate
similar parts.
In the drawings, an internal combustion engine comprises a cylinder 4
having a combustion chamber 2 above which is mounted a cylinder head
11 providing a 60 valve chamber for a rotary valve 1 An inlet passage
6 and an exhaust passage 7 extend transversely of the cylinder 4 and
communicate with the valve chamber, and these passages are in
alignment with one 65 another, having a common centre line 5.
In this connection, it is to be noted that these passages can be of a
diameter which is considerably larger than has hitherto been possible,
even of greater diameter 70 than the cylinder 4, with consequent
increase in efficiency of the engine.
The axis 3 (see Fig 2) of the rotary valve 1 passes through the
intersection of the centre line 5 of the inlet and exhaust 75 passages
6 and 7, and the centre line 8 of the cylinder 4, and this axis 3 is
disposed transversely of the cylinder at right angles to the centre
line 5 of the passages 6 and 7 80 In the embodiment illustrated in

Figs.
1 and 2, the rotary valve 1 is driven from the mainshaft 18 of the
engine by a chain 19 passing round a sprocket 9 on the mainshaft and a
sprocket 10 mounted on a 85 rotary shaft 3 ' to which the valve 3 is
secured Bearings 12 for the shaft 3 ' are provided in the cylinder
head The diameter of the sprocket 10 is twice that of the sprocket 9,
so that rotary valve 1 is 90 sce 25 p 786,105 driven at half the
engine speed This, of course, is applicable to four-stroke engines,
but for two-stroke engines the valve 1 will, accordingly, be driven at
the same speed as the mainshaft 18.
Alternative means may be provided for driving the valve, and such may,
if desired, be such as to impart an oscillatory movement thereof
instead of a Continuous rotation.
The valve 1 shown is substantially spherical in outline, but has one
or more surface cavities 14 which, according to the radial position
thereof, selectively connect either the exhaust passage 7 or the inlet
passage 6 with the combustion chamber 2, in one position the cylinder
being completely closed Sealing between the valve and the cylinder is
achieved by providing a close contact between the co-operating
surfaces thereof To this end, there are provided one or more rings 13,
These may be in the form of gaskets which may be rigid or flexible,
solid or in segmental form, or split, and of suitable shape and
material Tightness between the rings 13:
and the valve man be ensured by thermal expansion of the rings or by
means such as springs, resiliently arging the rings upwards towards
the valve Su Lich meanis man be mounted in the cyvlinder head or the
cylinder of the engine.
The valve 1 is hollow, as also is the shaft.
3 ', the latter having a chamber 20 extending through to-the valve,
whereby cooling finid, supplied through pipes 21, may be passed
therethrouoh In this way, the rotary valve is cooled, not only by the
usual thermal contact with the cooled walls of the cylinder head or
the cylinder, buit also by forced circulation of water, oil or other
cooling fluiid, within the valve itself Further cooling is provided
for the engine by circulating coolinlp fluid in ajacket 22 surrounding
the cylinder, via pipes 23 and 23 ' In addition, the bearings 12 are
provided with fittings 24 permitting lubricant to be fed thereto.
The further parts of the engine illusso trated are the conventional
carburettor 25 which is connected to the inlet passage 5 and the
sparking plug 26 vwiich is con 1nected by a lead 28 to a magneto 27
which is driven from the mainshaft 18 by a chain 29 and sprockets 30,
31 or other conventional means.
Referring now to Figs 6 to 9, the positions of the valve at various
stages of the four strokes of the cycle are illustrated.

As the piston passes its top-dead-centre position at the end of the
exhaust stroke, the valve is in the position shown in Fig 6 wherein
both the inlet and outlet passages are open to the cylinder As the
piston commences its induction stroke, a very small portion of the
intake stream passing through the inlet passage serves to scavenge the
cylinder and complete the discharge of the exhaust gases Rotation of
the valve then closes the exhaust passage 70 as the piston continues
its induction stroke as is illustrated in Fif 7, at the end of the
stroke the valve having closed both passages and the combustion
chamber as shown in Fig S 75 With the passages and combustion chamber
so closed, the piston performs its compression stroke and comnbustion
stroke at the end of which the valve has moved towards the position of
Fig 9 wherehil the 80 exhaust passage is open and the piston is
performing its final exhaust stroke of the crcle.
As is shown in Figs 4 and S of the drawings, the invention is
applicable to 85 engines embodyilng fuel injection means which
operates in conjunction with the valve and dispenses with the
conventional carburettor Such arraftigement permits efficient
atomisation of the fuel as it is fed go to the comibustion chamler and
permits the fuel to b 3 e supplied in correct proportion The injection
means comprises essentially a pump, a distribution chamber (not showni
and an injector proper 95 The device operates in the following wla:The
pump, wbiol is a reciprocating pump sclks the fuel from its tank and
feeds it to the Distribution echamber which 100 is a pressure
container havin h-pass valves which serve to feed excess fuel pumped
to the chamber back to the tank.
so that a substantially constant pressure is maintained in the
eontainer From the 105 distribution chamber, the fuel is fed to the
injector 15 This injector, whiell is suitably disposed in the cylinder
4 is fitted with a jet or nozzle of desired size an d this feeds fuel
to the coilbustion chamber 110 intermittently, in accordance with
engine cycle, With the air admitted to the cylinider throntgh the
inlet passag e by the valve 1.
Such intermittent feeling may be controlled by means of a small valve
aetuated 115 by any s-sitable mechanism driven by the engine, to admit
the ftiel at the desired period of the induction stroke of the engine
In the illustrated embodiment, the rotary valve itself serves to
control the 120 injection The injector 15 communicates with a passage
16 provided in the ring 1, which seals the valve to the cylinder 4
anal a complementary perforation 17 which aligns with the passage 16
at the desirel 125 instant of injection is provided in the valve 1.
The advantages of the engine emplon a rotary valve inl ac ordanice
with the invention are many: 130 786,105 1 The conventional
spring-actuated valves are dispensed with and consequently the danger

of valve breakage and consequent damage to the cylinder and the piston
through falling into the combustion chamber is completely eliminated.
2 The assembly is easy and the valve can readily be run in.
3 There is no danger of fire as a result of back-firing before the end
of the c 6 mpression stroke.
4 Larger inlet and exhaust passages can be used than has hitherto been
possible, with consequent increase in the efficiency of the engine.
The size of the combustion chamber can be varied according to a
desired compression ratio without the danger of the valves engaging
the piston where only a small combustion chamber is provided, as would
be the case with conventional poppet valves in overhead valve engines.
6 The engine is less expensive than conventional engines.
The combination of the rotary valve with the fuel injector as
described with reference to Figs 4 and 5 has the advantage of
eliminating the conventional carburettor and membrane pump, the latter
being rather difficult to set Further, the provision of one or more
injectors for each cylinder eliminates engine failure due to defective
carburation This is of particular importance in aircraft engines.
In prior constructions such defective carburation can have fatal
consequences, but with the present invention in the case of failure
due, for example, to blockage of the injector, the failure is confined
only to the single cylinder associated with the injector and the
remaining cylinders will continue to operate.
The invention is not confined to the details of the foregoing
examples, and many variations may be made thereto.
Thus, whilst only a single-cylinder engine has been described,
multi-cylinder engines may similarly be constructed In the latter
instance, where "in-line" engines are concerned there may be a single
shaft o' extending longitudinally of the whole engine, a plurality of
valves 1 being provided thereon In such case the valves and shaft will
resemble a conventional engine crankshaft somewhat.
The valve 1 may, if desired, be provided with a plurality of surface
cavities 14 disposed in such a manner that the speed of rotation of
the valve, as compared with the engine speed, can be reduced The 60
cavities may be shaped as shown in the drawings, or inclined or
transverse cavities may be provided.
As previously explained, also, the valve, instead of being driven with
a continuous 65 rotary motion, may he adapted to oscillate.
Amongst the other advantages afforded by the construction according to
the invention is the fact that the amount by which the inlet passage
is opened to the cylinder 70 is in direct relation to the position of
the piston in its travel down the cylinder.
This has the effect of ensuring a smooth flow of air or air and fuel
to the cylinder on the induction stroke with the elimina 75 tion of

turbulence At the end of the exhaust stroke, as previously described
with reference to Fig 6, the air or air/fuel stream serves to scavenge
the cylinder; in so doing it helps to condense the hot com 80 bustion
gases and cools the exhaust passage.
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* GB786106 (A)
Description: GB786106 (A) ? 1957-11-13
Improvements in and relating to the production of phenols
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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.
Improvements in and relating to the Production of Phenols
We, IMPERIAL CHEMICAL INDUSTRIES
LIMITED, a British Company, of Imperial
Chemical House, Millbank, London, S.W.I, 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 production of phenols.
According to the present invention, there is provided a process for

the production of phenols having a structure :
in which X and Y are tertiary alkyl groups and R is an alkyl or
substituted alkyl group, which comprises the steps of reacting an
hydroxy-aldehyde having a structure
with hydrogen peroxide in the presence of an aqueous solution of an
alkali metal hydroxide and in the presence of a gas containing free
oxygen, to give a quinone having a structure:
reducing this quinone to give a hydroquinone having a structure :
and subsequently alkylating this hydroquinone.
Thus, by the process of the present invention, 2:
6-di-tertiary-butyl-4-methoxy-phenol may be produced from 3:
5-di-tertiary-butyl4-hydroxy-benzaldehyde. In the present application,
this process will be described in detail to illustrate preferred
operating features.
Thus, 3 : 5-di-tertiary-butyl-4-hydroxy- benzaldehyde may be dissolved
in dilute aqueous sodium hydroxide containing, for example, 5 ; % by
weight of sodium hydroxide.
This solution is maintained at a temperature of 40 to 50 in the
presence of air, and hydrogen peroxide is then added, the molar ratio
bf hydrogen peroxide: hydroxy-aldehyde being of at least the order
of 1 : 1. 2:6
Di-tertiary-butyl-parabenzoquinone is precipitated as a yellow solid.
This compound is then reduced to 2: 6-di-tertiary-butyl-hydroquinone
by treatment, for example, with zinc and acetic acid. The 2:
6-di-tertiary-butylhydroquinone is allylated to 2 : 6-di-tertiary-
butyl4-methoxy-phenol by treatment with dimethyl sulphate in the
presence of dilute aqueous sodium hydroxide.
As already stated, phenols of the type:
may be produced by the process of the present invention. The groups X
and Y are tertiary alkyl groups, and may be identical or different; in
general, however, it is preferable for X and Y to be identical, since
the starting material is then more readily accessible. The group R may
be any alkyl group or may be a substituted alkyl group such as benzyl.
In carrying out the process of the present invention, the molar ratio
of hydrogen peroxide to hydroxy-aldehyde should preferably be at least
1:1. The reaction. is conveniently carried out in the presence of air;
this may be passed through the reaction mixture, or the reaction may
merely be carried out in a vessel open to the atmosphere.
In this step, a dilute aqueous alkali is present; preferably a

stoichiometric excess is maintained over the amount of
hydroxy-aldehyde employed.
In the first step of the present process, a 2:6- di - tertiary - alkyl
- parabenzoquinone is formed. In the second step, this is reduced to a
2: 6-di-tertiary-alkyl-hydroquinone. This reduction may be effected
catalytically, for example by the use of a copper catalyst and
hydrogen, or non-catalytically, for example by the use of reagents
which liberate nascent hydrogen, such as zinc and a dilute mineral or
organic acid.
The 2: 6-di-tertiary-alkyl-hydroquinone is converted to a 2:
6-di-tertiary-alkyl-S Ikoxy- phenol in any convenient manner; for
example, it may be reacted with an alkyl halide or a dialkyl sulphate
in the presence of dilute aqueous alkali such as sodium hydroxide.
The 2: 6-di-tertiary-aLkyl-Galkoxy-phenols produced by the process of
the present invention may be employed as stabilisers for organic
compounds liable to deterioration arising from peroxide formation.
Compounds which may be stabilised in this manner are, for example,
aldehydes such as nonaldehyde, ethers, petrols, lubricating oils and
oils of animal or vegetable origin.
EXAMPLE.
57 ml. of 6% hydrogen peroxide (0.1 M) were added to a solution of
23.4 gm. (0.1 M) of 3: 5-di-tertiary-butyl-4hydroxy-benzaldehyde
dissolved in 600 ml. of 4% % aqueous sodium hydroxide maintained at 40
to 50 C.
Air was blown through the reaction mixture and a yellow precipitate of
2: 6-di-tertiarybutyl-parabenzoquinone was formed. By operating in
this way, 17.5 grams of 2: 6-di- tertiary-butyl-parabenzoquinone were
formed, corresponding to a yield of 79%.
10 gm. of the quinone produced as described above were reduced with
zinc and acetic acid.
The solution when colourless was poured on to crushed ice and the
precipitated 2: 6-di- tertiary-butyl-hydroquinone was recrystallised
from petrol. It had a melting point of 114 C.
The yield of this compound was almost theoretical.
11 gm. of 2: 6-di-tertiary-butyl-hydroquinone were dissolved in 200
ml. of 5 , 3 aqueous sodium hydroxide, maintained at 5G C. under a
nitrogen atmosphere, and 7.5 gm. dimethyl sulphate were added. A
precipitate of 2:6-di-tertiary- butyl -4- methoxy- phenol was obtained
and after stirring for 45 minutes, this compound was filtered off
under a nitrogen atmosphere, washed with water and dried. The yield
was 7.5 gm. (65%). 3). After recrystallisation from methanol this
compound melted at 103-104 C.
What we claim is : -
1. A process for the production of phenols having a structure :

in which X and Y are tertiary alkyl groups and R is an alkyl or
substituted alkyl group, which comprises the steps of reacting an
hydroxy-aldehyde having a structure :
with hydrogen peroxide in the presence of an aqueous solution of an
alkali metal hydroxide and in the presence of a gas containing free
oxygen, to give a quinone having a structure:
reducing this quinone to give a hydroquinone having a structure :
and subsequently alkylating this hydroquinone.
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* GB786107 (A)
Description: GB786107 (A) ? 1957-11-13
Improvements relating to retractable writing instruments
We, PENPARTS LIMITED, a British Com-
pany, of 26 A Cuthbert Street, Paddington, London, W 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 des-
cribed in and by the following statement:-
The present invention relates to improved retractable writing
instruments.
A known form of ball-point pen comprises a barrel housing a
replaceable writing-unit which is normally resiliently urged to a

retracted position in the barrel, the unit being manually moved to the
writing position by pushing a plunger at the rear end of the barrel,
against the resilient means, so as to cause the ball-point end of the
unit to project out of the barrel, and retraction of the unit being
effected by the resilient means when pressure is applied to a lever on
the side of the barrel.
It is an object of this invention to provide simple, effective and
cheap mechanism for writing instruments of this kind.
According to the present invention there is provided a pen comprising
a barrel formed near its upper end with a pair of longitudinally
spaced adjacent holes, a writing-unit slidably mounted in the barrel,
resilient means for urging the unit towards the upper end of the
barrel, a plunger slidable within and projecting from the upper end of
the barrel and mounted on the plunger a leafspring the free end of
which is movable into either of the holes, the arrangement being such
that when the plunger is pushed into the barrel the free end of the
leaf-spring snaps into the lower hole to retain the writing unit in
the writing position and when the free end of the leaf-spring is
pushed transversely into the hole against its spring action the said
resilient means serves to lPrice 3 s 6 d l snap the free end from the
lower into the upper hole where the writing-unit is held in the
retracted position.
A preferred form of the invention is illustrated in the diagrammatic
drawings accompanying the Provisional Specification and in
which:Figures 1 and 2 are respectively elevations of a plunger and
writing-unit; and Figure 3 is a sectional elevation of a barrel into
which the plunger and unit are fitted.
At 10 in Figure 2 is shown a conventional ball-point writing-unit
fitted with a helical spring 11 which works in compression between
lugs 12 on the unit and the inside of a barrel 13 which is shown in
Figure 3.
The barrel is formed with a pair of longitudinally spaced holes 14 and
15 in its sidewall, the upper one 14 being outwardly flanged, as shown
in Figure 3, for a purpose to be described later.
Slidably mounted in the upper end of the barrel 13 is a plunger 16
which may be formed from a cylinder of resilient plastic material It
is provided with an integral leaf-spring 17, head 18, base 19 and
locating peg 20 The spring 17 has its free end 21 outwardly turned as
shown and the body of the leaf-spring may be pushed inwardly to lie
against a reduced portion of the body of the plunger.
In use, after the writing-unit 10 has been inserted into the barrel,
the leaf-spring 17 is held against the reduced portion of the plunger
and the plunger inserted, base first, into the barrel until the free
end 21 snaps into the upper hole 14 In this position the writing-unit

is urged by its helical spring 11 into the retracted position When it
is desired to bring the pen into the writing position, the head 18 of
the plunger is pushed longitudinally into the barrel, causing the free
end 21 of 'the leaf-spring to snap 7865107 PATENT SPECIFICATION
Inventor: -JACK HILLEL SHAW.
Date of filing Complete Specification: June 26, 1956.
A plication Date: July 8, 1955 No 19877/55.
Index at Acceptance:-Class 14 T( 3), P 11 i I.
International Classification: -B 43 e.
COMPLETE SPECIFICATION.
Improvements relating to Retractable Writing Instruments.
rte CO 4 S ( t 786,107 out of the upper and into the lower hole 15,
where it then lies projecting a little from the side wall of the
barrel so as to hold the unit in the writing position.
In order to retract the unit, the free end 21 is pressed radially
inwards by the finger until, under the action of the spring 11, the
end 21 snaps out of the lower and into the upper hole.
The peg 20 serves to align the plunger in the unit.
The flange around the upper hole 14 shields the free-end 21 when it is
in this hole.
If desired the plunger may be fixed to or be made integral with the
writing-unit in which case the helical spring may be located on the
plunger and lugs, such as those shown at 12, need not be formed on the
writing unit The peg 20 or other means for aligning and fixing the
plunger to the writing unit is then superfluous.
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* GB786108 (A)
Description: GB786108 (A) ? 1957-11-13
Improvements in and relating to a mechanism for controlling reciprocated

engine elements
PATENT SPECIFICATION
786,108 Date of Application and filing Complete Specification: July
1), 1955.
Application made in Denmark on July 15, 1954.
No 20030/55.
Index at acceptance:-Class 80 ( 3), B. International
Classification:-FO 6 h.
The inventor of this invention in the sense of being the actual
deviser thereof within the meaning of Section 16 of the Patents Act,
1949, is Poul Emil Wiene, a Subject of the King of Denmark, of No 15,
Goldschmidtsvej, Copenhagen, Denmark.
Improvements in and relating to a Mechanism for Controlling
Reciprocated Engine Elements We, AKTIESELSKABET BURMEISTER & WAIN'S
MASKIN OG SKIBSBYGGERI, a Company organised under the laws of Denmark,
of 4 Strandgade, Copenhagen, Denmark, 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 mechanism for controlling reciprocated
engine elements, such as valves and pumps in power engines, of the
type, in which said elements are actuated positively in both
directions from double cam or like control members by means of two
rollers or roller sets which are actuated by a spring which serves for
causing a constant contact of both rollers with their associated cam
faces.
The invention aims at improving such mechanisms so that they will
allow for removal of the engine element controlled by the mechanism
during the operation of the engine.
The mechanism according to the invention is characterised in that the
rollers are so mutually placed that the two planes through each roller
axis and the axis of the respective cam members enclose an angle a
little less than 180, one of said rollers being journalled on a
rotatably mounted rod, the roller bearing of which is connected
through a pair of pull rods or a similar rod system to the bearing of
the other roller, and that the first mentioned roller is kept pressed
against the cam face co-operating with it by means of a spring, the
guide of which, located opposite to the roller, is secured to a

rotatably mounted rod in such a way that during the operation of the
engine one may by turning the said rod away from its normal position
release the roller from the cam face and next remove the whole engine
element actuated by the cam mechanism, e g, a fuel pump, for
examination or exchange.
The invention is illustrated merely by way of example, in the
accompanying drawing which shows partly diagrammatically an embodiment
of a mechanism according to the invention, in side elevation, partly
in sec 50 tion.
Referring to the drawing, 6 designates a control shaft carrying a
single cam plate 5, Sa and a pair of cam plates 18 mounted on either
side of the cam plate 5, 5 a, only one 55 of said cam plates 18 being
visible on the drawing The cam plate 5, 5 a coacts with a roller 4,
while the pair of cam plates 18 coact with a pair of rollers 20, which
are journalled on a rotatably mounted rod, the 60 roller bearings of
which are connected through a pair of pull-rods 26 to the bearing of
the roller 4 The last-mentioned bearing is further connected to a
pull-rod 15 which transmits the motion of the rollers effected 65 by
the cam plates to the engine element to be controlled, for instance, a
valve or a fuel pump, not shown per se Between the rod and the said
element a spring device 30 such as Belleville springs may be inserted
70 The plane through the axis of the roller 4 and the axis shaft 6 and
the plane through said axis of the shaft 6 and the axis of the rollers
20 enclose an angle a little less than The rollers 20 are pressed
against the 75 cam faces co-operating with them by means of a spring
29, the guide of which, located opposite to the rollers 20, is secured
to a rod 31 rotatably mounted on a pivot 32 When said rod 31 is turned
around the pivot 32 in 80 the direction indicated by the arrow it will
be rendered possible to lift the engine element controlled by the
mechanism, for instance, a fuel pump, and to remove it and mount a new
pump during the very opera 85 tion of the engine, which may be of
importance in case of an accident to the pump.
For controlling of pumps, e g, fuel pumps of internal combustion
engines, the spring 30 may be dispensed with and the pull rod 15 90
786,108 be connected direct with the pump plunger.
The spring 29 may be considerably smaller than the spring usually used
in a fuel pump as it shall only serve for affecting a constant contact
of both rollers with the associated cam faces and thus only perform
the small motions necessary for compensating inaccuracies originating
from manufacturing or mounting.
The rods 26 may instead of being straight rods be designed as curved
rods and the rollers 20 may in practice be placed somewhat closer to
the position diametrically opposite to the roller 4 with respect to
the shaft 6 than shown on the drawing.

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