5696 5700.output

* GB786104 (A)

Description: GB786104 (A) ? 1957-11-13

Preparation of unsaturated polyene compounds

Description of GB786104 (A)

A high quality text as facsimile in your desired language may be available

amongst the following family members:

CH336063 (A) DE1001258 (B) FR1211308 (A)

CH336063 (A) DE1001258 (B) FR1211308 (A) less

Translate this text into Tooltip

[82][(1)__Select language]

Translate this text into

The EPO does not accept any responsibility for the accuracy of data

and information originating from other authorities than the EPO; in

particular, the EPO does not guarantee that they are complete,

up-to-date or fit for specific purposes.

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 :-

* Sitemap

* Accessibility

* Legal notice

* Terms of use

* Last updated: 08.04.2015

* Worldwide Database

* 5.8.23.4; 93p

* 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.

* Sitemap

* Accessibility

* Legal notice

* Terms of use



* 5.8.23.4; 93p

* GB786106 (A)

Description: GB786106 (A) ? 1957-11-13

Improvements in and relating to the production of phenols


Translate this text into Tooltip

[75][(1)__Select language]

Translate this text into

The EPO does not accept any responsibility for the accuracy of data

and information originating from other authorities than the EPO; in

particular, the EPO does not guarantee that they are complete,

up-to-date or fit for specific purposes.


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.

* Sitemap

* Accessibility

* Legal notice

* Terms of use



* 5.8.23.4; 93p

* 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.

* Sitemap

* Accessibility

* Legal notice

* Terms of use



* 5.8.23.4; 93p

* 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.

* Sitemap

* Accessibility

* Legal notice

* Terms of use



* 5.8.23.4; 93p

5696 5700.output

Healthcare