5591 5595.output

* GB785999 (A)
Description: GB785999 (A) ? 1957-11-06
Process for bleaching waxes, fatty oils and fats
Description of GB785999 (A)
PATENT SPECIFICATION
Inventors: ROBERT SCHIRMER, HEINRICH VOIT and HANS HOYER -:
7859999 Date of Application and filing Complete Specification Sept I,
1955.
No 25194/55.
Complete Specification Published Nov 6,1957.
Index at acceptance: -Class 91, C 2 A( 1: 2), W 4.
International Classification: -Cilb.
COMPLETE SPECIFICATION
Process for heachiing Waxes, Fatty O Iii Rs aind Fats We, FARBWERME
T-OECHST Al T'IENGESELLSCHAFT vorinals Meister Lucius & Brining, a
Body Corporate recognised under German Law, of Frankfurt (M)-Hoechst,
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 for bleaching waxes, fatty oils
and fats.
It is known to bleach wax by mixing it with an oxidising agent
(bleaching agent) for example chromosulphuric acid, in a vessel
provided with a stirrer In this vessel the material to be bleached is
mixed with the bleaching agent and there are also carried out the
chemical part of the bleaching process and the separation of the
bleached material from the bleaching agent It is also known to carry
out the bleaching in stages, the chemical part of the bleaching
process being divided into two or perhaps more stages When a
relatively large number of stages is employed, however, the above
process is no longer economical.
According to another known process, the oxidising agent flows
continuously through a vessel of the type above mentioned and is then

conducted in a cycle for regeneration and returned to the vessel It
has also been proposed to carry out the bleaching in such a vessel by
pre-oxidising the material to be bleached and then causing it and the
bleaching agent to flow together through the apparatus in a continuous
manner but in counter-current to one another This process is very
difficult to carry out in practice since increased formation of foam
either greatly impedes the counter-current when the latter is
conducted vertically, or requires an apparatus of excessively large
base when the counter-current movement takes place horizontally Apart
from this process, the known method of bleaching wax is, as far as the
material to be bleached is concerned, a discontinuous one.
lPric Furthermore, the known methods involve the following
drawbacks:It is impossible or only possible to a very restricted
extent to maintain the most favourable conditions in different stages
of the bleaching process, for example certain values of reaction
temperature and a certain concentration of bleaching agent Especially
in the first stage of the bleaching process, before the material to be
bleached and the bleaching agent separate from one another
automatically due to difference in density, in which stage, howvever,
uhe major part of the chemical reactions takes place, it is impossible
to control the reaction in a desired manner since, for example, the
concentration of the bleaching agent cannot be varied in any desired
manner.
In the first stage some of the particles of the material to be
bleached are already attacked by the bleaching agent while others have
not yet been attacked; the most favourable concentration of bleaching
agent for each particular particle depends upon the degree to which
this particle is attacked; since, however, the bleaching agent can
only be present in the reaction mixture in a uniform concentration it
cannot be avoided that the concentration, while it is most
advantageous for bleaching some of the particles, is little favourable
for other ones.
Conscquently, it is Impossible specifically to adjust the reaction
conditions to every particle.
Furthermore, the gases and vapours which are formed during the
bleaching process, especially carbon dioxide and water vapour, give
rise to an increased formation of foam, The vessel equipped with a
stirrer must therefore be very large as compared with the quantity of
the wax to be bleached.
Moreover, the time required for charging, discharging and cleaning the
vessel and also for separating the bleached material from the
bleaching agent, is relatively long compared with that required for
the bleaching itself.
Furthermore, towards the end of the ( 6 so bleaching process the

material to be bleached and the bleaching agent scarcely mix with one
another without great expenditure ol mechanical energy, so that the
last phase of bleaching requires a very long time.
-the present invention is based on the observation that the above
mentioned drawbacks can be avoided and waxes, ratty oils and tats can
be bleached with chromosulphuric acid in a simple and suitable manner
by subdividing the total bleaching process into several separate
stages, separating the material being bleached and the bleaching agent
from one another, after each stage, agam mixing tihe separated
material, to be further bleached in a later stage, with a bleaching
agent, which may be fresh or already used in the present process, and
continuously conducting the material to be bleached and the bleaching
agent in co-current in each individual stage.
It is sufficient to carry out the said separations according to such
methods as are usual in industry.
When waxes are bleached with aqueous oxidising media, the following
chemical reactions primarily take place:1) Impurities, such as resins
and acids containing hydroxyl groups, are oxidised to a large extent
and mainly decomposed to carbon dioxide and water.
2) The esters which constitute the main fraction of the material to be
bleached, are saponified to the corresponding fatty acids and alcohols
with consumption of water.
3) The alcohols which have been formed as described under 2) are
oxidised to the corresponding fatty acids with simultaneous formation
of water.
4) The fatty acids which have been formed as described under 2) and 3)
are partly decomposed by the bleaching agent with formation of fatty
acids having shorter hydrocarbon chains; this process is undesirable
and should be avoided as tar as possible.
Although the sequence is as set forth above, the individual processes
in part overlap one another in the total bleaching process When in the
case of the partial process of one of the above four stages, the mass
of the substance d S formed per unit of time (S=mass of the substance
formed, t=time) is plotted as ordinate and the time as abscissa, the
curve obtained always first rises from the origin, reaches a maximum
value-unless the process is stopped prematurely-and falls again to
zero The curves of the partial processes of the individual stages are
related one to another and also depend upon the composition of the
mixture of the material to be bleached and the bleaching agent and
upon external influences such as temperature and pressure The nature
of each of the curves can be separately changed when the material to
be bleached and the bleaching agent are conducted continuously in the
same direction according to 65 this invention.
The process according to the present invention is carried out in at

least two, advantageously in 3 reaction stages It is, however, also
possible to provide more stages, for 70 Lxampie 6, aithough too large
a number oi stages renders the process more complicate.
The external factors influencing the progress of the reaction such as
temperature and pressure, can thus be adjusted as required at each 75
part of the apparatus By the application of superatmospheric pressure
it is even possible to raise the reaction temperature in certain parts
of the apparatus above the boiling point at normal atmospheric
pressure of the mixture So of the material to be bleached and the
bleaching agent In order to be able to vary the composition of the
mixture of tne bleaching agent and the material to be bleached, the
total bleaching process must be divided up into 85 stages
corresponding to separate partial processes, each stage comprising a
process of mixing, a process of reaction and a process of separating
the material to be bleached from the bleaching agent 90 In carrying
out the process of the invention, the various stages are each
conducted in an allotted section of the apparatus, the material to be
bleached and the bleaching agent always being conducted in the same
direction It is 95 also possible to modify one or more stages by
adding bleaching agents at different places in the sections
corresponding to the individual stages it is obviously not always
possible to arrange for the whole of a particular reaction 100 to take
place in any particular section but one reaction may commence at a
point in one section, proceed through the whole of the next section
and perhaps be completed in a third section Each process of separation
is advan 105 tageously carried out at the same place in the apparatus
so that the used bleaching agent can be replaced by a fresh one for
use in the next section In this manner, the composition of the
bleaching agent, the quantitative propor 110 tion between the material
to be bleached and the bleaching agent and therefore the composition
of the material being bleached can be varied.
An apparatus suitable for use in carrying 115 out the process of this
invention is illustrated diagrammatically by way of example in the
accompanying drawings.
Referring to the drawings, a section comprises a mixing device 1, a
reactor 2 and a 120 separating device 3 (see Fig I) The bleaching
agent is introduced at 4, the material to be bleached at 5; the latter
can be removed at 6 and the former at 7 Reactor 2 may, for example,
consist of a tube system; if desired, 125 the pipe connecting the
mixing device with the separating device may itself serve as reactor
because of the short reaction times which can 785,999 of the reactor
15 and the inlet of the mixing device 16 o O this particular section
of the apparatus so that the mixture of the material to De oteacned
and the bleaching agent can be recycled several times through this

section.
When the mixture of the material to be oleacned and the bleaching
agent does not separate automatically, the composition of the said
mixture can also be varied by separating the materiai to be bleached
and the bleaching agent by mechanical means using an additional
device, ror example a separator or centrifuge.
When such additional device is used, a return pipe is not necessary
tor the particular section out may in some circumstances be of
advantage at least a part of one reactant, i e of time material to be
bleached or the bleaching agent, or both the reactants together, can
be returned, either completely or partially, to the mixing device of
the stage concerned even aiter they have been separated.
As stated above, within each stage the material to De bleached and the
bleaching agent flow in the same direction Through the individual
stages, however, the material to be bleached and the bleaching agent
can pass in any predetermined succession whereby the quality of the
final product can be influenced to a certain degree Fig 3 shows, by
way of example, the arrangement of apparatus in the case of 3 stages
Conduits for the bleaching agent are indicated at 17, conduits for the
material to be bleached at 18 conduits for the mixture of the
bleaching agent and the material to be bleached at 19 and conduits for
the mixtures of the bleaching agent and the material to be bleached
and/or for the bleaching agent and/or for the material to be bleached
at 20.
The method of conducting the material to be bleached and the bleaching
agent in the same direction involves the further particular advantage
that the process can take place in a flow apparatus in which a high
degree of turbulence can be attained with little expenditure of energy
Accordingly the material to be bleached and the bleaching agent can be
mixed with one another very intensively The time of reaction is
relatively short; it can be further reduced by utilization of a
relatively high concentration of the bleaching agent When the total
bleaching process is not interrupted, the concentration of the
bleaching agent decreases exponentially with time The resulting curve
can be divided into a branch representing a vigorous reaction and a
branch representing only a very slow reaction Advantageously a stage
should correspond only to the former branch, while the latter branch
should be avoided as far as possible by separation of the material to
be bleached from the bleaching agent When chromosulphuric acid is
used, which can be regenerated in an electrolytic cell equipped with a
diaphragm, a residual concentration of the chromosulphuric acid in any
be obtained by the present process In general, a part of the reaction
already takes place in the mixing device before entry into the said
pipe With a predetermined number oi stages the most favourable

conditions can be applied, for example, in order to obtain the
shortest possible time of reaction or final products o O an especially
high quality It is of advantage to provide for the possiblity of
varying the following factors:a) Temperature of the material to be
bleached flowing to the mixing device concerned; b) Temperature of the
bleaching agent flowing to the mixing device concerned; c) Temperature
in the reactor concerned; d) Composition of the bleaching agent
flowing to the mixing device concerned; e) Ratio of the quantity of
the material to be bleached to the quantity of the bleaching agent
iowing per unit of time into the mixing device concerned; t) Pressures
in the mixing device, the reactor and the separating device concerned.
By the process of this invention waxes, fatty oils and fats can be
obtained having the specific properties required in each particular
case for their intended use The above mentioned most favourable
conditions depend on the desired properties of the products and can be
determined and applied in each particular case in the practice of the
process of the present invention.
Mixing device l, reactor 2 and separating device 3, shown
diagrammatically in Fig 1, are represented in more detail in Fig 2 In
this case a vessel 3 serves as separating device in which the
individual components separate owing to their different specific
gravities.
The bleaching agent is shown at 8, the material to be bleached at 10
and the mixture of the bleaching agent and the material to be bleached
at 9 Valves are represented at 11, a pump at 12 and a device for
sucking in the mixture 9 at 13.
If no particular importance is attached to being able to control the
composition of the mixture of the bleaching agent and the material to
be bleached before the material to be bleached and the bleaching agent
are separated from one another automatically due to their difference
in density, it is sufficient to provide vessels 3 through which the
bleaching agent and the material to be bleached pass in streamline
flow (see Fig 2) When in this case the consequential time of dwell of
the mixture of the bleaching agent and the material to be bleached in
the reactor of a particular stage is not sufficient for producing the
automatic separation of the material to be bleached and the bleaching
agent after the mixture has passed through the reactor once, this
particular section of the apparatus must be provided with a rettun
pipe 14 The latter is an additional connection between the outlet
785,999 785,9 g 9 particular stage involves no disadvantage, since it
has been found that between chromosulphuric acid of low concentration
and crude wax or slightly bleached wax so strong a reaction takes
place that in a desired stage the concentration of the chromosulphuric
acid can be reduced to 0 by employing an appropriate proportion of the

constituents of the mixture, which proportion can be easily determined
by simple test As indicated above, in the bleaching of crude wax with
chromosulphuric acid, gases and vapours, particularly carbon dioxide
and water vapour, are forin-d, especially in the first phase of the
reaction When the material to be bleached and the bleaching agent are
mixed thoroughly, the above mentioned gases are formed almost
throughout the mixture The specific properties of this mixture of wax
and chromosulphuric acid at reaction temperature, however, prevent an
enlargement and the combination of small bubbles and also an escape of
the gases and give rise to an increase in the number of bubbles per
unit of volume, i e to foam formation In order Lo avoid the formation
of too much foam, the reaction has hitherto in most cases been
purposely checked, for example by adjusting to a temperature which
does not promote the reaction to any great extent, by a relatively low
29 degree of mixing or by a delayed bringing together of the material
to be bleached and the bleaching agent On the other hand, relatively
large reaction vessels have been used to avoid foaming over.
The pellicle of the individual bubbles consists partially of a wax
layer and partially of a chromosulphuric acid layer The space between
the bubbles is mainly filled with thromosulphuric acid In the state of
foam crude wax and chromosulphuric acid have a large surface of
contact due to the vesicular structure They are, however, divided into
a large number of small volumes This state is maintained until the
reaction becomes weaker or subsides When this mixture is in the state
of foam-i e primarily in the first phase of the bleaching process in
which the chemical reaction would be expected to be most vigorous-the
reaction can only continue slowly since the surface at which reactants
are in contact with one another is constant, that is, it is not
enlarged or diminished in the course of time even if their position in
the foam is changed by turbulence.
Reaction-promoting diffusion through the boundary surfaces is
furthermore impeded by interfacial tensions.
It has further been found that these influences of the foam which
retard the course of the reaction can be overcome or reduced without
preventing the initial formation of the foam, but by destroying it,
advantageously by varying the pressure, at least at one place in the
complete apparatus, suitably after the reaction mixture has left a
particular stage This is a dilferent procedure from the known
processes In processes of wax oxidation according to the continuous
flow principle, this can be done with the aid of any appropriate
mechanical foam destroying means in an early stage 70 of the total
bleaching process In this manner the yield of bleached wax per unit of
time can be still further increased.
It is of advantage to divide the reactor 2, as shown in Fig 4, into

two or more smaller 75 partial reactors, for example 21 and 22, and to
arrange between them one or more mechanical foam destroyers, for
example 23 and 24, in which, if desired, a part of the reaction may be
allowed to take place In this manner, the 80 mixture oi the material
to be bleached and the bleaching agent enters each partial reactor
after having had the foam destroyed The separating device has itself a
foam destroying action but the separation effect can, however, 85 be
enhanced by arranging a foam destroying device in front of the
separator In the above mentioned process according to which vessels 3
(Pig 2) are used, appropriate foam, removal is also of advantage It is
however, of par 90 ticular advantage to enhance the effect of each
such vessel, which replaces an ordinary separator, by passing the
reaction mixture through a foam destroyer before it enters the
separator Fig 5 shows, by way of example, 95 such an arrangement A
foam destroyer 23 may suitably comprise a vessel 25 in which
fluctuation of pressure is produced, for example, by an oscillating
membrane (diaphragrn) 26 which is operated at 27 either 100
mechanically or electrically or by means of a valve control-mechanism
with the aid of reaction gas, air or other inert gas The mixture (if
the material to be bleached and the bleaching agent enters the foam
destroyer 23 at 28 105 and leaves at 29 after having had the foam
removed The waste gas is led off at 30 by way of a non-return valve 31
The lower part of Fig 5 is the same as the right hand part of Fig 2
110 For destroying the foam, devices can be used in which the mixture
of the material to be bleached and the bleaching agent is subjected to
rapidly varying pressures Rotary pumps, centrifugal mixing devices,
separating 115 devices or centrifuges have, for example, a destroying
action on foam.
By the above process there can be bleached solid or liquid waxes, for
example montan wax, candelilla wax, ouricouri wax, beeswax, 120
spermaceti, wool wax, carnauba wax, synthetic waxes obtained, for
example, by esterification of palmitic or stearic acid with cetyl or
octodecyl alcohol, fatty oils and fats such as palm kernel oil,
coconut oil, olive oil, cottonseed oil, 125 sesame oil, poppyseed oil,
soy bean oil, peanut oil, whale oil or hog fat The process of this
invention is especially suitable when the said fats art intended for
technical purposes.
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* 5.8.23.4; 93p
* GB786000 (A)
Description: GB786000 (A) ? 1957-11-06
Odour inhibited polyethylene
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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.
PATENT SPECIFICATION
786000 Date of Application and filing Complete Specification: Oct 19,
1955.
No 29801155.
Application made in United States of America on Oct 21, 1954.
Complete Specification Published: Nov 6, 1957.
Index at acceptance:-Class 2 ( 6), P 7 C( 8 B: 10: 20 B), P 7 (D 1 A:
52).
International Classification:-CO 8 f.
Odour Inhibited Polyethylene We, UNION CARBIDE CORPORATION(formerly
Union Carbide and Carbon Corporation), of 30, East 42nd Street, New
York, State of New York, United States of America, a Corporation
organised under the laws of the State of New York, United States of
America (assignee of JAMES HARDING), 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 inhibiting odor
development in polyethylene or polyethylene compositions More
particularly, the invention relates to the stabilization of
polyethylene against objectionable odor development by incorporating
in the polyethylene a minor amount of certain monohydric phenols as
odor inhibitors.
Normally solid polymers of ethylene are well known and widely used in
the production of thermoplastic products such as film, sheeting, and
molded articles Virgin polyethylene as obtained from the polymerizing
equipment is generally practically odorless, but upon extended
storage, and especially at elevated temperatures, e g 35 o C -90 ' C,
or when subjected to heat required for processing as in extrusion or
molding, the polyethylene develops a rancid-like odor The odor
intensity, which is somewhat similar in its sharpness to butyric acid,
varies according to the exposure conditions, thus it is more intense
in closed atmospheres as for example the interior of sealed
polyethylene bottles or jars than is the case with polyethylene
sheeting used as external wrapping or packaging material However, odor
can be readily detected on polyethylene sheeting stored for some time
in a closed package Apparently, while polyethylene is regarded as one
of the more stable polymers, it nevertheless under conditions of
normal usage or heat-processing suffers some slight decomposition
sufficient to be detected olfactorily Such odor development has caused
consumers to object to articles manufactured (Trice 3 s 6 d l from
polyethylene, such as cosmetic jars, bottles, filn or sheeting,
particularly when polyethylene comes in contact with foodstuffs.
It has now been found that objectionable odor development in
polyethylene can be substantially suppressed by incorporating in the
polyethylene relatively small amounts of a trialkyl substituted
monohydric phenol in which the two ortho positions and the para
position contain an allkyl substituent, for example, methyl, ethyl,
butyl, amyl, octyl, nonyl, and dodecyl, and free from any substituents
other than hydrogen on the two meta positions.
Such phenols are represented by the formula:
o H R 3 O R, R 2 wherein R 1, R 2, and R, are each the same or a
different allyl radical The alkyl radicals may contain from 1 to 12
carbon atoms.
Somewhat higher efficiencies in suppressing odor has been observed
when R 1 and R, are tertiary alkyl groups instead of normal or
secondary alkyl groups and hence such phenols are preferred.
Specific phenols within the scope of the above formula and useful in
the practice of this invention are the following:

2,4,6-trimethyl phenol 2,4,6-triisopropyl phenol 2,4,6-triethyl phenol
2,4,6-tritertiary butyl phenol 2,4,6-tritertiary amyl phenol
2-tertiary butyl-4,6-dimethyl phenol 2,6-diethyl-4-methyl phenol
2,6-ditertiary butyl-4-methyl phenol 2,6-dipropyl-4-methyl phenol
2,6-diethyl-4-tertiary butyl phenol 2,6-ditertiary butyl-4-tertiary
amyl phenol 2,6-dimethyl-4-dodecyl phenol 2,6-ditertiary butyl-4-nonyl
phenol PW u 25 p I1 r, E 7 , The discovery that trialkyl substituted
phenols of the aforedescribed type are effective in suppressing odor
development in polyethylene is considered most surprising in view S of
the fact that, while these phenols when freshly prepared are generally
characterized by a mild unobjectionable odor, they have been reported
as tending to develop an objectionable odor upon storage Thus it has
been suggested that alkyl phenols be stabilized against deterioration
in odor by treating the phenol with from about 0 01 per cent to 5 per
cent by weight of organic polybasic carboxylic acids or salts thereof.
For the purposes of the present invention, it is not essential to
stabilize the alkyl substituted phenol as suggested; however, if
desired, such stabilized phenols can be employed for incorporation in
polyethylene.
Incorporation in polyethylene of amounts as little as 0 005 per cent
by weight of a 2,4,6-trialkyl substituted phenol has been found
effective in suppressing or minimizing odor development in
polyethylene Preferably, there are employed amounts of trialkyl
substituted phenol between 0 001 per cent to 0 02 per cent by weight
of the polyethylene, since within this range satisfactory inhibition
of the odor normally developed in uninhibited polyethylene is
prevented over extended periods of time without at the same time
imparting to the polyethylene a phenolic odor perceptible to the
average person The threshold concentration of trialkxyl substituted
phenol in polyethylene at which a phenolic odor in polyethylene may be
observed is about 0 2 per cent to 0 5 per cent depending of course on
the particular phenol used Where a phenolic odor is unobjectionable or
preferable over the rancid type odor developed in unstabilized
polyethylene, amounts up to about 2 per cent to 4 per cent may be used
without marked impairment of the normal physical properties of
polyethylene such as tensile strength and solvent resistance.
Incorporation and satisfactory dispersion of the phenol into the
polyethylene can be by way of fluxing the polyethylene with the phenol
on heating on heated open rolls, at which time fillers and/or coloring
agents such as pigments or dyes may be added if desired.
Other suitable mixing procedures include the use of Banbury mixers and
of heated extruders of the single or double screw type.
The use of a trialkyl substituted phenol to suppress odor is effective
not only with clear polyethylene compositions, but also with

compositions pigmented with organic or inorganic compounds of chromium
or manganese which when uninhibited often develop an odor more quickly
than a clear polyethylene composition.
Chromium and manganese compounds as for example hydrated chromic
oxide, manganese dioxide, manganese ammonium pyrophosphate (Nurnberg
Violet), employed as pigments in polyethylene compositions have been
observed to accelerate odor development whereas other pigments, as for
example titanium dioxide, are comparatively inert either in inhibiting
or promoting odor development in polyethylene.
The process and resultant products of the invention are further
exemplified in the following examples:
EXAMPLE 1
A six-pound batch of polyethylene having 75 an average molecular
weight of 21,000 was compounded with 0 5 per cent by weight of
2,6-ditertiary butyl-4-methyl phenol in a Banbury mixer for 15 minutes
at 135 C 1405 C to form a relatively concentrated 80 master batch
dispersion of the phenol suitable for mixing with additional
uninhibited polyethylene The hot master batch was transferred from the
Banbury to mixing rolls having a roll surface temperature of 50 ' C to
sheet 85 the batch The resultant sheets were cooled and then
granulated One pound of this granulated composition was dry blended
with 24 pounds of granulated uninhibited polyethylene (average
molecular weight 21,000) by tumbling 90 for 30 minutes, producing a
mixture containing 0.02 per cent by weight of the trialkyl phenol.
The tumbled mix was fluxed at 150 ' C in an extruder, and the extruded
product was pelletized One sample of these pellets was placed 95 in a
clean glass jar which was then sealed to retain therein any odors
which might be given off by the sample during storage at room
temperature Another sample of the same pellets was extruded once more
to determine the 100 effect an odor from this additional exposure to
heat and this twice extruded product was also placed in a clean glass
jar After storage for two weeks at room temperature, the jars
containing the two phenol inhibited samples 105 together with a jar
containing virgin polyethylene which had been subjected to the thermal
abuse of only one extrusion operation were opened and compared as to
odor content Both phenol inhibited polyethylene 110 samples were so
essentially free of odor as determined by a staff of five experienced
testers that the product could be used as molded containers or
wrapping for such odor sensitive materials as foods, condiments, and
115 cosmetics The -jar containing virgin polyethylene sample when
opened had a sharp xancid odor and was judged unsatisfactory for the
aforementioned uses.
EXAMPLE 2
An odor stabilized polyethylene composition pigmented with an organic

manganese compound and suitable for injection molding was prepared by
fluxing in a Banbury mixer at C the following components:
Parts by weight Polyethylene 100 0 Pigment Rubine 3 G" 1 0
2,4,6-tritertiary butyl phenol 0 2 786,000 a very strong, rancid and
acidic odor developed after two months' storage at 40 C in sealed
glass jars containing the granulated polyethylene.
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* 5.8.23.4; 93p
* GB786001 (A)
Description: GB786001 (A) ? 1957-11-06
Improvements in fuel supply systems for thermal power plants
P At TENT SPECFICATION
__A 786,001
Date of Application and filing Complete Specification:
Oct 21, 1955 No 30185155.
Application made in United States of America on Oct 25, 1954.
Complete Specification Published: Nov 6, 1957.
Index at Acceptance:-Classes 110 ( 3), G 10 (A: B): and 135, P( 1 C l
E:1 F: 8: 24 E 5: 24 KX).
International Classification:-FO 2 c.
COMPLETE SPECIFICATION.
Improvements in Fuel Supply Systems for Thermal Power Plants.
We, GENERAL ELECTRIC COMPANY, a Corporation of the State of New York,
United States of America, Schenectady 5, State of New York, United
States of America, do hereby declare the invention, for which we pray
that a patent may be granted to us, and the method by which it is to
be performed, to be particularly described in and by the following

statement:-
This invention relates to fuel systems for thermal power plants and
more particularly to dual fuel supply system for gas turbine power
plant.
The gas turbine normally runs on one fuel during any given period
However, when the gas turbine is operated on gas received from a
supplier there is to be considered the possibility that the available
gas supply may not be sufficient for the turbine's needs.
To meet this contingency the gas turbine is set up to receive a
liquid-fuel to supplement a possible inadequate gas supply The gas and
liquid fuel lines are fed into a dual fuel nozzle and then to the
combustion chamber where the fuels are mixed in the desired
proportions.
The present invention has for its object to provide an improved dual
fluid supply system for a thermal power plant having a combustion
chamber.
According to the present invention a dual fluid supply system for a
thermal power plant comprises separate fuel supply lines for supplying
two different fuels to the combustion chamber, separate controls for
the respective fuels in the respective fuel lines, said controls being
of the type which control fuel flow in response to an imposed
pressure, means to produce a pressure signal responsive to the
operating conditions of the power plant and a pressure divider by
which the pressure signal is divided to operate the said lPrice 3 s 61
1 separate pressure controls, said divider comprising a housing with a
central bore, a pressure fluid inlet port communicating with an
intermediate portion of the bore and to which the aforesaid signal is
transmitted, and first and second drain ports axially spaced on either
side of the inlet port, a flow control member comprising an axially
slidable stem member with three axially spaced lands disposed in said
bore in cooperative relation with the inlet and drain ports, the said
lands including a central land having an axial length less than the
axial extent of the inlet port, a first drain land spaced axially from
the central land and defining therewith in the bore a first fluid
outlet chamber having a first pressure outlet port, the said first
drain land also cooperating with its drain port to define a first
drain orifice communicating with the first outlet chamber, when the
flow control member is in neutral position, and a second drain land
spaced axially from the said central land, the second drain land
co-operating with the central land to define in the bore a
second-fluid pressure outlet chamber having a second fluid pressure
outlet port, the second drain land also co-operating with its drain
port to define a second drain orifice equal in effective area to said
first drain orifice when the flow control member is in its neutral

position, the two outlet ports being connected respectively to the
aforesaid controls and means for positioning said flow control member
axially so that the pressure signal can be so divided that the two
fuels are supplied in the desired proportions.
The invention will be better understood from the following description
taken in connection with the accompanying drawings, in which: Fig 1 is
a schematic view of the dual fuel system; 9 7 g 6,co 1 Fig 2 is a
modified form of the dual fuel system; and Fig 3 is a sectional view
of the pressure divider.
Referring now more particularly to Fig.
1, the dual fuel system is shown applied to a gas turbine I containing
a combustion chamber 2 to which fuel is supplied through a nozzle
arrangement 3 The nozzle 3 is connected up to receive either gas or a
liquid fuel, or both through conduits 4, 5 The flows of the fuels
through the conduits 4, 5 are regulated by a gas control valve 6 and a
fuel oil pump 7 respectively The fuel oil pump is controlled by
pressure responsive means and the gas control valve is pressure
responsive so that the pump and valve regulate the flow of fuel in
accordance with an imposed control pressure The sum total of the fuel
flowing through the fuel pump and gas control valve is regulated by a
servo mechanism having speed, temperature and pressure responsive
components A servo mechanism of this type is indicated diagram2,
matically at 8 in the drawing and is arranged to regulate the
hydraulic pressure in conduit 9 The regulator is supplied with oil
pressure from a source through the conduit 9 a The regulator 8
produces an outlet pressure in conduit 9 which is determined by the
operating condition of the turbine This signal pressure in conduit 9
determines the amount of fuel required to operate the gas turbine at
the operating condition thereof.
The pressure in conduit 9 will be referred to as the VCO (Variable
Control Oil) pressure The VCO pressure is thus the pressure which
determines the amount of fuel flowing into the gas turbine The VCO
pressure enters the pressure divider assembly where it is split into
two pressures P P 2.
The sum of pressures P 1, P 2 is equal to the VCO pressure plus a
desired constant which is determined by a back pressure arrangement to
be discussed later in detail The two pressures P 1, P 2 are then
transmitted to the gas control valve and fuel pump control
respectively where they control the flow of gas and liquid fuel to the
turbine.
The gas control valve and fuel pump control are so designed that in
response to an equivalent VCO pressure the total load available is
substantially constant for a given VCO pressure regardless of the
ratio of the pressures imposed on the gas control valve and fuel pump

control The pressure divider assembly 10, for example, may be set so
that the entire signal pressure is transmitted to the gas control
valve in which case the gas turbine will be run entirely on gas.
On the other hand, the VCO pressure may be divided up so that both gas
and liquid fuel will be supplied to the nozzle 3 In the latter case,
the sum of the fuels flows to the combustion chamber will produce the
required output load of the turbine.
The pressure divider assembly may be manually regulated by the handle
11 to change the ratio of the signal pressure flowing to the fuel pump
control and gas control 70 valve This manual change can be made at any
time during the operation of the turbine without requiring the turbine
to be shut down.
In the modification shown in Fig 2, the 75 pressure divider assembly,
is regulated by an electric motor 69 acting through a gear 72.
Located in tie line between the electric source and the motor 69 is a
pressure responsive switch 70 The switch is respon Si sive to the
pressure in conduit 4 a which is transmitted through conduit 71 The
switch is set so that if the pressure in conduit 4 a drops below a
predetermined amount the motor circuit will be closed to energize the
85 motor and actuate the pressure divider assembly to divert more of
the signal pressure to the fuel pump control so as to provide more
liquid fuel to compensate for the reduced amount of gas available 90
Any suitable means is provided to stop the motor when the required
adjustment has been made and to reverse the motor when the pressure in
conduit 4 a rises above the predetermined pressure 93 With this
arrangement the gas turbine can be set to operate on only gas within
the range of its availability and to automatically cut in the second
fuel only if the gas pressure should drop below a predetermined 100
value.
This is done by first setting the pressure divider so that the entire
signal pressure will be sent to the gas control valve If the
requirements of the turbine are such as to 105 require more gas than
is available the reduced gas pressure will be reflected in conduit 71
The pressure switch will then be closed to actuate the motor to divert
some of the signal pressure to the fuel pump con 110 trol to reduce
the amount taken from the gas line When the gas pressure is again
normal the switch 70 will open to shut off the motor.
The minimum pressure to be maintained in the line 4 a is usually set
by the gas sup 115 plier This is done so that the turbine will not
deprive other users of the gas by consuming too much of the available
amount.
Referring to Fig 3, there is illustrated in section, the VCO pressure
divider 10 The 120 pressure divider comprises a piston valve assembly
for dividing up the VCO pressure, a manually operated arrangement for

regulating the division of the VCO pressure, and a "constant adder"
arrangement in the drain 125 line of the piston valve so that the
pressure available for operating the fuel pump control and gas control
valve never falls below a predetermined minimum provided the necessary
control pressure in line 9 a is available 130 7 a 6,001 The piston
valve assembly is located in a bore 16 defined by the housing 17 The
valve assembly consists of a piston valve 18 slidably disposed in a
valve sleeve 19 The S valve assembly is guided in the bore 16 by a
tubular member 20.
The valve sleeve 19 and tubular member define aligned axially spaced
ports 21, 22, 23, 24 and 25 Ports 21 and 25 are drain ports and are in
communication with passageway 26 defined by the housing for returning
the drained oil to the reservoir 15 through conduit 14 (see Fig 1) The
VCO, pressure is supplied to the valve assembly through conduit 9 and
port 23 Ports 22, 24 are in communication with conduits 12 and 13
respectively for supplying the portion of the VCO pressure allotted to
it to the fuel pump control and gas control valve 2 ' respectively.
The piston valve 18 has axially spaced lands 28, 29, and 30 which
regulate the flaw through inlet port 23 and drain ports 21 and
respectively Uuper and lower chambers 2.5 33, 34 are formed between
the land 28 and lands 30 and 29 respectively The land 28 is slightly
smaller than port 23 and when centrally located relative to port 23
equal orifice openings 31, 32 are defined leading from inlet port 23
to outlet valve chambers 33 and 34 respectively With the land 28 in
the central or neutral position, the lands 29 and 30 are so located as
to form orifice openings 35, 36 between the valve chambers 33, 34 and
the drain ports 25, 21 respectively These orifices 35, 36 are exactly
equal to-orifices 31, 32.
A back pressure is set up in the drain ports 21, 25 and drain line 26
by a relief valve 65 or other suitable constant adder means which can
be set at any desired pressure.
By way of example only, consider a VCO pressure in port 23 of 200 p s
i and the back pressure in the drain ports 21, 25 and drain line 26 as
being 40 p s i When the VCO pressure flows into the pressure divider
assembly 10 the drain line 26 fills up developing a 40 p s i back
pressure The difference between the VCO pressure and the back pressure
in drain line 26 is the maximum drop that can occur across any flow
path between the inlet and drain line 26 in the pressure divider
assembly This relief valve arrangement prevents the pressure in valve
chambers 33, 34 and conduits 12, 13 from falling below 40 p s i
provided the necessary pressure in line 9 a is available.
The minimum pressure in chambers 33, 34 provides for better operating
characteristics of the fuel pump control and gas control valve, since
they are spring loaded and are designed to operate accurately on a

minimum pressure of 40 p s i to avoid losses due to hysteresis.
:rom the above it can be seen that there are two flow paths formed
between the inlet port 23 and the drain line 26 The upper flow path is
formed by port 23, orifice 31, valve chamber 33, orifice 35, port 25
and 70 drain line 26 The lower flow path is formed by port 23, orifice
32, valve chamber 34, orifice 36, port 21 and drain line 26 The total
pressure drop in each of these flow paths will be 203 p s i (the
assumed VCQ 75 pressure) minios the 40 p s i back pressure set up by
the relief valve 65 There is no pressure drop through ports 22, 24
since they are part of a closed system leading only to the fuel pump
control and gas control 80 valve for determining the amount of fuel
flowing therethrough.
It can be appreciated by one skilled in the art of fluid mechanics
that with the land 28 in the neutral position relative to port 23 85
the drop across the equal orifice openings 31, 35 are identical
Therefore, the total drop across orifices 31, 35 is equal to 200 p.s i
(assumed VCO pressure) minus 40 p.s i (the back pressure set up by
relief 90 valve 65) or 160 p s i The drop across each of tile orifices
31, 35 is one-half the total drop or 80 p s i Since the drop across
orifice 31 is 80 p s i the pressure in chamber 33 and the pressure in
conduit 13 for con 95 trolling the gas control valve is the VCO
pfrssure ( 200 p s i) minus the pressure drop across orifice 31 ( 80 p
s i) or 120 p s i.
Now in considering the lower flow path through orifice 32, valve
chamber 34, etc, 100 and the land 28 in the neutral position, the same
flow principles can be applied The total drop across the lower flow
path and the drop across each of the orifice openings 32, 36 is equal
to the drop across the upper 105 flow path and the drop across each of
orifices 31, 35 respectively The pressure in chamber 34 and in conduit
12 for controlling the fuel pump is therefore also 120 p s i.
The sum of the pressures in conduits 12, 110 13 is 240 p s i or in
other words is equal to the VCO pressure ( 200 p s i) plus the back
pressure ( 40 p s i) fixed by the relief valve 65.
If it is desired to run the turbine on, for 115 example, only oil, the
piston valve is moved upward to close off orifice opening 31.
When orifice 31 is closed off, orifice 36 is also blocked off due to
the aforesaid relationship between the piston valve 18 and 120 the
ports in sleeve 19 Therefore, the pressure in conduit 12 is equal to
the VCO pressure At the same time it can be appreciated that since
there is no pressure being supplied to valve chamber 33 and it is open
125 to drain line 25, the pressure in conduit 13 will become 40 p s i
as determined by the relief valve 65 The total is still 240 p s i, or
the VCO pressure plus the back pressure determined by relief valve 65
In this ex 1 ( O 7 $G,00 Q 1 treme position, it can be seen that the

turbine will be operated only on oil In the other extreme position, it
will be operated on the other fuel.
Now let us consider the piston valve in a position between the neutral
and extreme positions In the neutral positions, orifices 31, 32, 35,
36 are all equal The lands 29, are so located that upon movement of
the piston valve 18 in a downward direction the orifice 36 is opened
by the amount orifice is closed At the same time the orifice 31
becomes larger by the amount 32 shrinks.
Thus, when the piston valve is moved downwardly the total pressure
drop across each of the flow paths remains the same but the drops
across each of the orifices are changed.
In the new position orifices 31 and 36 are equal and orifices 32 and
35 are equal.
When the piston valve 18 is moved in a downward direction, the
orifices 31, 36 are enlarged by the amount orifices 32, 35 are reduced
The drop across the pairs of equal orifices are then correspondingly
changed.
That is, the drops across the smaller orifices are increased by the
amount the drops across the larger orifices are decreased The pressure
drops across orifices 31 and 36 are equal and the pressure drops
across 32 and 35 are equal.
The pressure in chamber 33 equals the VCO pressure minus the pressure
drop across orifice 31 and the pressure in chamber 34 equals the VCO
pressure minus the pressure drop across orifice 32 Therefore, assuming
the pressure drop across orifice 31 to be 50 p s i the pressure in
chamber 33 is 200 p s i (assumed VCO pressure) minus 50 p s i or 150 p
s i The drop across the upper flow path is 200 p s i (VCO pressure)
minus 40 p s i (relief valve back pressure) or 160 p s i The drop
across orifice 35 therefore equals the pressure in chamber 33 ( 150 p
s i) minus the back pressure ( 40 p s i) or 110 p s i.
Since the pressure drop across orifices 32 and 35 is equal, the
pressure in chamber 34 is 200 p s i minus 110 p s i (drop across
orifices 35) or 90 p s i The sum of the pressure in chambers 33, 34
equals 150 + 90 p.s i and again equals the sum of the VCO pressure (
200 p s i) plus the back pressure ( 40 p s i) determined by relief
valve 65.
Thus it can be seen that whatever position the piston valve is in, the
sum of the pressures in conduits 12, 13 is equal to the VCO pressure
plus a constant predetermined back pressure.
The piston valve 18 is adapted to be moved downward to various
positions by a manually operated handwheel 37 and is urged upwardly by
a spring means 38.
The arrangement for manuallv operating the piston valve includes a
shaft 39 The shaft 39 extends through a chamber 66 defined by the

upper portion of the housing 17 and its ends are journaled in cap
members 42, 43 The cap members are located in openings 40 41 defined
by the housing and they are secured to the housing by bolts 44 T) The
chamber 66 is closed off by a cover 67 which is secured to the casing
by bolts 68.
The shaft is rotated by a handle 11 secured to one end thereof Located
on the shaft 39 is a cam member 45 which is adapted to 5 be in contact
with a rod 46 Rod 46 extends through hole 47 defined by the cover
member 48 which closes the chamber containing the valve assembly from
the upper housing chamber 66 At its lower end the 50 rod contacts a
bracket 49 secured to the piston valve 18 Thus it can be seen that
upon rotation of the shaft 39 the cam 45 through the rod 46 and
bracket 49 is capable of moving the piston valve 18 in a down 8.
ward direction.
Fastened to the lower end of piston valve 18 is a spring abutment
member 50 The compression spring 38 is located between the spring
abutment member 50 and a spring 91guide member 52 in the bottom of
bore 16.
The spring 38 urges the piston valve in an upward direction so that
bracket 49 is maintained in contact with rod 46 and the rod in contact
with cam 45 95 It can be appreciated that the location of the piston
valve is positively determined by the operation of the handle 11 since
the spring means 38 makes the bearing connection between the cam 45
and rod 46 the 1 (O( equivalent of a rigid connection.
The relief valve 65 located in drain line 26 serves to set up a back
pressure in the drain line This back pressure limits the pressure drop
between the inlet port 23 and 105 the drain line 26 The setting of the
relief valve determines the minimum pressure in the valve chambers 33,
34 provided there is the necessary control pressure in line 9 a.
The relief valve is disposed in a bore 60 11 O in housing 17 and
comprises a seat member 53 having an inlet opening 54 The seat member
is retained in the housing 17 by a plate member 55 and bolts 56 A
valve disk 57 is biased by a spring 58 to close lie inlet 54 The
spring 58 abuts at its other end against an abutment member 59 which
may be adjusted to give whatever spring force desired The member 59 is
disposed in a cover plate 61 which is secured to hous _ 120 ing 17 by
bolts 62 The end of the abutment member 59 is secured against
tampering by a cap member 63 which is secured to the cover plate 61 by
bolts 64.
Thus it will be seen that the invention 125 provides for a dual fuel
system which can be automatically regulated to provide a desired
proportion of each of the fuels without requiring shutdown of the
turbine The total amount of fuel required by the turbine 130 786,001
mitted, and first and second drain ports axially spaced on either side

of the inlet Po't, a flow control member compriginlg an axially
slidable stern member with three 6,5 axially spaced lands disposed in
said bore in co-operative relation with the inlet and drain ports, the
said lands including a central land having an axial length less than
the axial extent of the inlet port, a first 70 drain land spaced
axially from the central land and defining therewith in the bore a
first fluid outlet chamber having a first pressure outlet port, the
said first drain land also co-operating with its drain port to 75
define a first drain orifice communicating with the first outlet
chamber, when the flow control member is in neutral position, and a
second drain land spaced axially from the said central drain land, the
second drain 80 land co-operating with the central land to define in
the bore a second-fluid pressure outlet chamber having a second-fluid
pressure outlet port, the second drain land also co-operating with its
drain port to define 85 a second drain orifice equal in effective area
to said first drain orifice when the flow control member is in its
neutral position, the two outlet ports being connected respectively to
the aforesaid controls and means for posi 90 tioning said flow control
member axially so that the pressure signal can be so divided that the
two fuels are supplied in the desired proportions.
2 A dual fuel supply system as claimed 95
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* GB786002 (A)
Description: GB786002 (A) ? 1957-11-06
Improvements in jacks
I, Au GUSTF F Av RE, of 406 Rue Paradis,

Marseille, France, of French nationality, do hereby declare the
invention, for which I pray that a patent may be granted to me, and
the method by which it is to be performed, to be particularly
described in and by
the following statement:-
The present invention relates to jacks, its object being to provide an
improved construction primarily for use in docks for ship building and
repair.
According to the present invention, a shiftable jack for use in
shipyards, comprises a rail track for positioning in the path along
which the jack is to be shifted, a rigid frame positioned over said
track, roller means journalled in the frame and positioned on said
track for supporting the frame thereon, a cylinder of a hydraulically
operable piston and cylinder lifting device mounted on the frame with
its axis normal to the track, a piston slidable in said cylinder and
extending from an end thereof for seating against a load to be
supported, a cylinder of a hydraulically operable piston and cylinder
shifting device coupled to the track, and a piston slidable in said
shifting cylinder and coupled to the frame, whereby the frame is
movable to a selected position along the track by application of fluid
under pressure to the shifting device.
Preferably the journals for the roller means are resiliently coupled
to the frame such that the rollers support part of the weight of the
frame.
The jack may include a chamber in the lower part for hydraulic liquid,
a non-return inlet valve in the base of the lifting cylinder, a
conduit opening at one end to said inlet valve and at the other end in
the liquid chamber of the frame, means for supplying compressed fluid
to the chamber to force liquid therefrom into the lifting cylinder and
lPrice 3 s 6 d l lift the piston therein, and an outlet valve on the
lifting cylinder for releasing liquid from said cylinder when the
piston is to be lowered This enables the lifting device to be brought
rapidly up to the load, whereafter rigid support is given by the
liquid which has entered through the non-return valve.
A resilient sole plate may be provided on the piston of the lifting
device for more readily contacting the load in an even manner.
An embodiment of the invention is hereinafter particularly described
with reference to the accompanying drawing, wherein:Figure 1 shows in
longitudinal vertical section, a jack for use in dry docks.
Fig 2 shows means for lateral movement of the jack.
The apparatus consists of a frame 1 comprising at its lower part 2,
which forms the base, a reservoir 3 containing a liquid 4.
The air space 5 of this reservoir has an inlet orifice 6 for the entry
of air under pressure.

A vertical conduit 7 depends below the surface of the liquid and has
its upper end opening into the base of a cylinder 8 At the bottom end
of the cylinder is an opening closable by a non-return valve 9 which
permits introduction of the liquid beneath the lower face 10 of a
piston 11 slidable in the cylinder and carrying a head or top plate
12.
A pipe 13 with cock 14 is disposed at the lower part of the cylinder 8
and allows of its being put into communication through the branch pipe
15 with the reservoir 3.
The base 2 comprises a traction arm 16 joined by a pivot 17 to a
piston rod 18 which has a travel of several metres The cylinder 19 and
the rod 18 (see Fig 2) are lodged in a trough so as not to obstruct
the runway 24.
Centrally at its base the jack is provided 7865002 PATENT
SPECIFICATION
Date of Application and filing Complete Specification:
Dec 13, 1955 No 35727/55.
Application made in France on Dec 20, 1954.
Application made in France on Nov 29, 1955.
Complete Speci cation Published: Nov 6, 1957.
Index at Acceptance -Class 78 ( 3), C( 1: 7 8:13: 15).
International Caasifieation:-B 66 f.
COMPLETE SPECIFICATION.
Improvements in Jacks.
65, 786,002 with rolling members 20 mounted on resilient bearings
consisting of a cushion 21 and a sole plate 22, the whole being
assembled together by straps and fitted in a housing 23 in such a
manner as to be able to roll along the runways 24 A resilient sole
plate 25 is secured to the movable platform 12.
It is well-known that hydraulic mechanisms in general are relatively
efficient for the transmission of high power at low speeds.
Nevertheless, the power absorbed unladen whilst bringing a hydraulic
jack up to contact with the load is nearly as great as that required
to effect lifting, so that the overall efficiency is thereby greatly
reduced and such jacks become costly to operate when considerable
distances have to be covered.
By utilising a combination of pneumatic and hydraulic operation, these
drawbacks are eliminated.
When the apparatus is used as a hydraulic jack for putting vessels
into dry dock, the jacks are disposed suitably along the keel and when
the vessel tends to heel over during emptying of the dock, the
operator, who is on land, opens a valve which allows compressed air to
pass to the reservoir 3 through the orifice 6 This air under pressure
drives out the water through the conduit 7 into cylinder 8 past the

valve 9, whereby the piston I rises in the cylinder and forces the
head 12 with its sole plate '25 against the ship to support it.
When the piston ceases to rise, the valve 9 closes and the return of
the liquid is prevented (the cock 14 also being closed).
The piston 11 then is supported solely by liquid and not by air, and
thereby gives a firm pressure capable of supporting very high loads, e
g as much as 300 tons.
In the special case where it is desirable that the vessel should not
be supported at strong pressure but should rest on a resilient
support, the cock 14 is left open and the jack exerts resilient air
pressure.
Where it is desired thereafter, with the vessel in dry dock, to the
vessel, it is only necessary to connect the cylinder S with a portable
pump.
Where the jack has been set beneath an inclined part of the vessel,
there can be placed beforehand on the top plate of the piston a
resilient or inclinable wedge, or the jack may be constructed with two
pistons o 5 instead of one, each piston acting on an extremity of the
top plate which, under pressure, will assume the inclination of the
side of the vessel.
It is possible to move the jack and place it in a desired position
during or before the entry of the vessel into dry dock This operation
is effected by remote control from land The shifting jack 19 may be
pneumatic or hydraulic and of either single or double action 65 The
jack can be pushed or pulled to the required position, e g the desired
lateral separation from the keel support in a dry dock.
The resilient bearings 21, 22 for the wheels 70 are adjustable by
tightening screws (not showe) in such a manner as to permit carrying
from 213 to 314 of the submerged weight of the jack The jack remains
permanently on its runway, and the bearing 75 of a major portion of
its weight by the wheel 20 facilitates rolling and sliding on the
paths 24.
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* GB786003 (A)

Description: GB786003 (A) ? 1957-11-06
Novel dehydro-betacarotene and the manufacture and conversion thereof
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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.
Novel Dehydro-BetaCarotene and the Manufacture and Conversion
thereof
We, F. HOFFMANN-LA ROCHE & Co.,
AKTIENGESELLSCHAFT, a Swiss Company, of 124-184, Grenzacherstrasse,
Basle, Switzerland, do hereby declare the invention, for which we pray
that a patent may be granted to us, and the method by which it is to
be performed, to be particularly described in and by the following
statement:-
The present invention relates to novel dehydro-betacarotenes and a
process for the manufacture thereof and to the conversion thereof into
all-trans 3,4;31,41-bisdehydro- betacarotene.
The novel dehydro-betacarotenes provided by the invention are
3,4;31,41;15,151-trisdehydro-betacarotene and 15,151-monocis 3,4;
31,41 - bisdehydro - betacarotene. They can readily be converted into
all-trans 3,4;31,41 bisdehydro-bctacarotene which is useful as a
colouring material for foodstuffs (e.g. butter, margarine and cheese)
and for animal feeds.
As it possesses biological activity characteristic of vitamin-A it
imparts this activity as well a its orange-red colour to the nutrient
materials in which it is incorporated.
The process provided by the invention essentially comprises condensing
acetylene with 8-[21,61,61-trimethyl-cyclohexadien-(11, 31) - yl -
(11(1 - 2,6 - dimethyl - octatrien- (2,4,6)-al-(1) or
8-[21,61,61-trimethyl-cyclohexen - (21) - ylidene - (11)] - 2,6 -
dimethyl- octatrien-(2,4,6)-al(1) in a metal-organic reaction,

subjecting the resulting
1,18-di-[21,61,61trimethyl-cyclohexadien-(11,31)-yl-(11)]-3,7,12, 16 -
tetramethyl - 8,11 - dihydroxy -
octadecahexaen-(294,6912,14,16)-ine-(9) or 1,18-di-[21,
61,61-trimethyl-cyclohexen-(21)-ylidene-(11)]-3, 7,12,16 - tetramethyl
- 8.11- dihydroxy - ecta- decahexaen-(2,4,6,12,14,16)-ine-(9) to
bilateral allyl rearrangement and dehydration and if desired,
partially hydrogenating the 3,4;31,41; 15,151-trisdehydro-betacarotene
at the triple bond to obtain 15,151-monocis 3,4;31,41-bis-
dehydro-betacarotene. The last named sub stance can be converted in
accordance with the invention into all-trans
3,4;31;41-bisdehdyro-betacarotene by isomerisation.
One embodiment of the invention which includes the conversion step
comprises condensing acetylene with approximately two molar
proportions of 8-[21,61,61-trimethyl- cyclohexadien - (11,31) - yl -
(11)] - 2,6 - dimethyl-octatrien-(2,4,6)-al-(1) or
8-[21,61,61trimethyl - cyclohexen - (21) - ylidene -
(11)]2,6-dimethyl-octatrien-(2,4,6)-al-(1) to give 1, 18-di
[21,61,61-trimethyl-cyclohexadien-(11,31)yl - (11]) - 3,7,12,16 -
tetramethyl - 8,11dihydroxy - octadecahexaen - (2,4,6,12,14,16)-
ine-(9) or 1,18-di
[21,61,61-trimethyl-cyclohexen-(21)-ylidene-(11)]-3,7,12,16-tetramethy
l8,11 - dihydroxy - octadecahexaen - (2,4,6,12, 14,16)-ine-(9)
respectively [either in a single operation, wherein one mol of
aldehyde is condensed with each of the reactive hydrogen atoms in
acetylene by means of a bilateral metal-organic reaction or, stepwise,
wherein one mole of the aldehyde is condensed with one mol of
acetylene by a metal-organic reaction thereby producing the
intermediate condensation product 10 - [2l,6l,6l - trimethyl -
cyclohexadien - (113l) - yl - (11)] - 4,8 -
dimethyldecatrien-(4,6,8)-irl-(1) < 1-(3) or 10-[21,6l,6l-
trimethyl-cyclohexen-(21)-ylidene-(11)]-4,8-dimethyl-decatrien-(4,6,8)
-in-(1)-ol-(3) respectively and condensing this product with a second
mol of the aldehyde by means of a metal-organic reaction], subjecting
said dihydroxy compound to dehydration with concomitant allyl
rearrangement to give 3,4;31, 41;15,151-trisdehydro-betacarotene, if
desired hydrogenating the last named substance with about one molar
proportion of hydrogen in the presence of a hydrogenation catalyst
which selectively catalyzes the hydrogenation of an acetylenic linkage
to an olefinic linkage to give 15,1 51-monocis
3,4;31,4l-bisdehydro-betacarotene and, if further desired,
isomerizing the latter to give all-trans
3,4;31,41-bisdehydrobetacarotene.
In the first stage wherein acetylene is condensed bilaterally with

either aldehyde in a metal-oraganic reaction, an appropriate
embodiment comprises condensing acetylene di-(magnesium halide) trith
about two molar proportions of either aldehyde in a Grignard reaction.
The acetylene di-(magnesium halide) can be prepared in a Imown manner
by the action of acetylene on a solution of lower-alkyl magnesium
halide in an inert solvent; preferably, an ethereal solution of
lower-alkyl magnesium halide is stirred or shaken in an acetylene
atmosphere for several hours. Suitable lower-alkyl magnesium halides
are, for example, ethyl, butyl and r-hexyl magnesium bromides and
chlorides. In this reaction the acetylene di-(magnesium halide)
produced separates as a heavy oil or as a solid. It is then
appropriate to add about two molar proportions of either aldehyde
dissolved in an inert solvent (preferably diethyl ether) to the well
stirred suspension of the acetylene di-(magnesium halide) and to Stir
the mixture for several hours at ci 200 G or at the boiling point of
the solvent. Upon hydrolysis of the reaction product there is obtained
the corresponding dihydroxy compound aforesaid as a very viscous
material.
In the first stage wherein acetylene is stepwise condensed, an
appropriate embodiment comprises condensing approximately one molar
proportion of either aldehyde in liquid ammonia with one molar
proportion of an alkali-metal or an alkaline-earth-metal acetylide and
reacting the product obtained (advantageously after hydrolysis) in a
metal-organic reaction with a second approximately molar proportion of
the aldehyde. The condensation in liquid amroonaa can be executed
either at elevated pressures and room temperature (i.e. ca 200 C.) or
under normal pressures and at the boiling temperature of the ammonia.
Preferably, lithium acetylide is employed in the condensation. The
aldehyde can be added in solution in an inert solvent, for example,
diethyl ether. The condensation product can best be hydrolysed by
addition of an ammonium salt before removal of the ammonia or by
addition of an acid after removal of the ammonium. Condensation of the
resulting 10-[21,61,61-trimethyl-cyclohexadien(1i,3l) - yl - (I)] -
4,8 - dimethyl - decatrien(4,6,8)-in-(1)-ol-(3) or
10-[21,61,61-trimethylcyclohexen - (21) - ylidene - (11)] - 4,8 - di-
methyl-decatrien-(4,6,8)-in-(1)-ol-(3) as the case may be with a
second approximately molar proportion of the aldehyde is effected by
means of a meta] erganic reaction. The preferred mode of execution
comprises reacting either monohydroxy compound with approximately two
molar proportions of a lower-alkyl magnesium halide in diethyl ether.
The first molar proportion of the lower-alkyl magnesium halide reacts
with the hydroxyl group whereas the second molar proportion reacts
with the acetylene hydrogen and renders the terminal carbon atom of
the compound reactive in the subsequent step of the condensation. The

di-(magnesium halide) compound formed is advantageously reacted in the
same solvent with the aldehyde. The condensation product is preferably
hydrolysed by conventional methods without further purification (for
example, by pouring into a mixture of ice and dilute sulphuric acid)
thereby producing the required dihydroxy compound.
In the second stage each hydroxyl group of the dihydroxy compound
obtained after the first stage, after esterification if desired,
migrates by a multiple allyl shift toward the nearer ring, and splits
out two molar proportions of water (or acid when the compound has been
esterified) by combining with a hydrogen atom and two new double bonds
are formed and simultaneously all of the multiple bonds are rearranged
into a conjugated system to give 3,4;31,41;15,151-trisde-
hydro-betacarotene. It will be appreciated that the phrase "bilateral
allyl rearrangement and dehydration " is used herein to denote the
elimination of two moles of water from, and the formation of a
conjugated system in, the product of the first step-irrespective of
whether these changes are brought about directly or via intermediate
ester formation.
The bilateral allyl rearrangement and dehydration can be effected by
various expedients. A general method comprises heating a solution of
either of the dihydroxy compounds in an inert solvent such as toluene
to a temperature of about 90 C. to about 100
C. with about two molar proportions of phosphorus oxychloride in the
presence of an organic base such as pyridine. In stead of phosphorus
exychlorde and pyridine there may be used p-toluene-sulphonic acid,
hydrochloric acid, hydrobromic acid or acetic acid (the last mentioned
in the presence of sodium acetate and a little water). A preferred
method for the treatment of 1,18-di[21,61,61triscthyl - cyclohexadien
- (11,31) - yl - (11)] - 3,7,12,1 6-tetramethyl-8, 11-dihydroxy-octa-
decahexaen-(2,4,6, 12,l4,16)-ine-(9) comprises reacting the same with
hydrogen halide at a low temperature (advantag@ously in the presence
of a loser alkanol as solvent) whereupon a
1,18-di[21,61,61-trimethyl-cyclohexadien(11.3i) - yl - (1')] - 2,17 -
dihalo - 3,7,12,16 tetraxnethyl - octadecahexaen
(3,5,7,11,13,15)in-(9) is first formed and spontaneously splits out
two mols of hydrogen halide with the formation of two additional
double bonds. The trisdehydro compound formed in this stage can be
purified by crystallisation.
In the optional third stage, the partial hydrogenation can be
accomplished according to methods kno-zm per se; e.g. by reaction with
elemental hydrogen in the presence of a selective hydrogenation
catalyst in an organic solvent. A suitable selective hydrogenation
catalyst is a palladium/calcium-carbonate catalyst which has been
partially deactivated with lead and quinoline. An especially

advantageous mode of execution of this third stage comprises effecting
the hydrogenation in a hydrocarbon medium in which the
3,4;31,41;15,151-trisdehydro-betacarotene is only partially soluble.
In this manner, the trisdehydro compound slowly goes into solution as
the hydrogenation proceeds and the hydrogenation product is
precipitated from the hydrogenation mixture as it is formed. The
15,151-monocis 3,4;31,41-bisdehydro-betacarotene so obtained has a
characteristic cis-peak" in the ultraviolet absorption spectrum.
Isolation of the hydrogenation product is not mandatory as the
subsequent stage of isomerisation can be effected directly upon the
suspension. However, if desired, the hydrogenation product can be
isolated and purified by crystallisation.
In the conversion step comprising the final stage of the comprehensive
process, the 15,151monocis 3,4;31,41-bisdehydro-betacarotene is
isomerised to the corresponding all-transcompound. This isomevisation
can be effected, for example, by treatment with iodine or by
irradiation or by heat. A particularly advantageous mode of execution
comprises heating a suspension of 15,15'monocis
3,4;3l,4l-bisdehydro-betacarotene for several hours at 80 -100 C. in a
quantity of an organic liquid vehicle insufficient for the complete
solution of th monocis material. As the isomerisation progresses, the
monocis compound goes into solution and simultaneously the all-trans
3,4;31,41-bisdehydro- betacarotene formed crystallizes out and an
almost quantitative isomerisation can thereby be attained. The product
obtained in this way can be purified by crystallization or by
partition between solvents or by chromatography. It can be stabilised,
when necessary, by the addition of antioxidants. Antioxidants can
also be employed in the other stages of the process of the invention.
As will be seen from the foregoing an important feature of the
invention resides in the preparation of all-trans 3,4;31,4l-bisde-
hydro-betacarotene by a process which comrises partially hydrogenating
3,4;31,41;15,151- trisdehydro-betacarotene at the triple bond to give
15,151-monocis 3,4;31,41-bisdehydrobetacarotene and isomerising same
to give all - trans 3,4 3194J - bisdehydro - beta carotene.
It will be understood that the numbering system employed herein for
the carotene afere- said is that set forth in Leibig's Annalen der
Chemie, 1951, 573, 3 for the carbon skeleton of carotene.
The following example is illustrative of the process and conversion
and includes the preparation of the inital materials:
EXAMPLE
PREPARATION OF THE INITIAL MATERIAL
A) 8 - [21,61,61-TRIMETHYL-CYCLOHEXADIEN
( 3I) - YL - (11)] - 2,6 - DIMETHYL-OCTA
TRIEN-(2,4,6)-AL-(1):

30 g. of 4-[21,61,61-trimethyl-cyclohexen
(11)-yl-(11)]-2-methyl-buten-(2)-al-(1) in 210 g. of methylene
chloride, together with 13.5 g. of sodium bicarbonate and 9 g. of
calcium oxide, was cooled to 0 C. while stirring.
Then 28 g. of N-bromo-succinimide was added and the temperature was
maintained for 3 hours at 5 C. to 10 C. by intermittent cooling. After
some time the mixture assumed a yellow to red colour and then slowly
became colourless again. It was filtered, 30 g. of quinoline was added
and the methylene chloride was removed in oacuo.
Again 30 g. of quinoline was added and the mixture was warmed for 2
hours under nitrogen on a steam bath. 350 g. of petroleum ether
(b.p.=300 C. to 60 C.) was added and then the mixture was poured into
250 g. of 3-N sulphuric acid and ice while stirring. The insoluble
resin was filtered off and the aqueous layer was also removed; the
residual petroleum-ether solution was washed with water, dilute sodium
bicarbonate solution and then again with water. The washed petroleum
ether solution was dried over sodium sulphate and concentrated,
yielding 29.4 g. of crude
4-[21,61,61-trimethyl-cyclohexen-(21)ylidene-(11)]-2-methyl-buten-(2)-
al-(1). This product was purified by distillation from a Hickman flask
in a high vacuum; b.p. 90 C./ 0.33 mm. Hg.
136 g. of 4-[21,61,61-trimethyl-cyclohexen- (21) - ylidene - (11)] - 2
- methyl - buten (2)-al-(1) were heated with 97 ml. of isopropenyl
acetate and 0.7 g. of p-toluene-sulphonic acid for 3 to 4 hours at 100
C. to 140
C. while passing through a slow stream of nitrogen, the acetone
released being thus continuously distilled out of the reaction
mixture.
Then the reaction mixture was allowed to cool.
The reaction mixture, containing crude 4 -[21,61,61 - trimethyl -
cyclohexadien - (11, 31) - yl - (11)] - 2 - methyl - 1 - acetoxy
butadiene-(1,3), was directly subjected to hydrolysis by adding
thereto 650 ml. of methanol, 65 ml. of water and 46 g. of sodium
bicarbonate and heating the mixture under reflux for 12 hours, while
stirring. The reaction mixture was then poured into 2000 ml. of ice
water, and the resulting mixture was made slightly acidic with dilute
sulphuric acid. The reaction product was extracted with petro leum
ether, the extract was washed with aqueous sodium bicarbonate solution
and dried over sodium sulphate. The solvent was evaporated and the
residue was distilled in a high vacuum. There were obtained 98 g. of 4
- [21,61,61 - trimethyl - cyclohexadien
(11,31)-yl-(11)]-2-methyl-buten-(2)-al-(1) b.p.= 80 C./0.05 mm. Hg.;
nD22=1.530; maxima in ultraviolet at 224 mji and 268 my; E11= 795 and
345 (in petroleum ether solution).

A solution of 82 g. of 4 - [21,61,61 - tri methyl - cyclohexadien -
(11,31) - yl - (1')] 2-methyl-buten-(2)-al-(1) in 90 ml. of ethyl
orthoformate was mixed with a solution of 1.5 ml. of orthophosphoric
acid in 15 ml. of absolute ethanol, and the mixture was allowed to
stand for 15 hours at 20 C. to 25 C. Then 10 ml. of pyridine was added
and the mixture was poured into a mixture of 100 g. of 5 O aqueous
sodium bicarbonate solution and 60 g. of ice. The reaction product was
extracted with petroleum ether, the extract was shaken with aqueous
sodium bicarbonate solution and dried over potassium carbonate.
The solution was concentrated, and the residue was freed in vacvo at
70 C. from excess ethyl orthoformate and the ethyl formate produced by
reaction. The residue, 108 g. of crude 4 - [21,61,61 - trimethyl -
cyclohexadien (11,31) - yl - (11)] - 2 - methyl - 1,1 - di
ethoxy-butene-(2), had nD25=1.487; absorption maximum in the
ultraviolet spectrum at 266 mlt (in petroleum ether solution). It was
used without further purification for the next step.
To the above 108 g. of material was added 3 ml. of a 10% by weight
solution of zinc chloride in ethyl acetate; then 29 g. of ethyl vinyl
ether and 27 ml. of the same 10% solution of zinc chloride in ethyl
acetate were added simultaneously, with stirring, at 30 to 35 C., over
a period of about 2 hours. Stirring was continued 20 hours longer at
ca 20
C. The crude 6-[21,61,61-trimethyl-cyclohexadien - (11,31) - yl -
(11)] - 4 - methyl 1,1,3-triethoxy-hexene-(4) obtained in this manner
was added to a mixture of 300 ml. of glacial acetic acid, 15 g. of
sodium acetate and 10 ml. of water, and the reaction mixture was
heated at 95 C. for 6 hours in a nitrogen atmosphere. The reaction
mixture was cooled to 30 -40 C., poured into a mixture of 200 g. of
ice and 200 ml. of water. The resulting mixture was extracted with
petroleum ether, the extract was washed with 5% aqueous sodium
bicarbonate solution and then with water and dried over sodium
sulphate. The petroleum ether solution was concentrated and the
residue was distilled 'n a high vacuum. There were thus obtained 65 g.
of 6 - [21,61,61 - trimethyl - cyclohexadien-(11, 31) - yl - (11)] - 4
- methyl - hexadien - (2,4) al-(1); b.p.=about 105 5./0.05 nun. Hg.
This material was recrystallized twice from petroleum ether at minus
70 C., yielding yellowish crystals of m.p. 18 C. to 22 C.; ultraviolet
absorption maximum at 274 m ,
E11=1380 (in petroleum ether solution).
A solution of 38.5 g. of 6 - [21,61,61 - tri methyl - cyclohexadien -
(11,31) - yl - (11)] 4-methyl-hexadien-2,4)-al-(1) in 40 ml. of ethyl
orthoformate was mixed with a solution of 0.6 ml. of orthophosphoric
acid in 9 ml. of absolute ethanol, and the reaction mixture was
allowed to stand for 15 hours at 20 C. to 25 C. Then 6 ml. of pyridine

was added, and the mixture was poured into a mixture of 50 g. of 5%
aqueous sodium bicarbonate solution and 30 g. of ice. The product was
extracted from the resulting mixture with petroleum ether, the
petroleum ether extract was shaken with aqueous sodium bicarbonate
solution and dried over potassium carbonate.
The petroleum ether solution was concentrated and the residue was
liberated in vacuo at 70
C. from excess ethyl orthoformate and from the ethyl formate produced
by the reaction, yielding 49 g. of 6 - [21,61,61 - trimethyl
cyclohexadiene - (11,31) - vl - (11)] - 4
methyl-1,1-diethoxy-hexadiene-(2,4), nD26= 1.510 ultraviolet
absorption maxima at 235 my. and 264 my (in petroleum ether solution).
This material was used for subsequent processing without further
purification.
The above 49 g. of material was mixed with 2 ml. of a 10% by weight
solution of zinc chloride in ethyl acetate. Then, 14 g. of ethyl
propenyl ether and 14 ml. of the same 10% solution of zinc chloride in
ethyl acetate were added simultaneously, with stirring, at 20 C. to 35
C, over a period of 2 hours.
The reaction mixture was stirred further for 15 hours at ci 20 C. Then
the reaction mixture was extracted with petroleum ether, the extract
was washed with dilute aqueous sodium hydroxide solution and dried
over potassium carbonate. The solvent was distilled off, yielding 55
g. of crude 8 - [21,61,61 trimethyl - cyclohexadien- (11,31) - yl -
(1l)] 2,6 - dimethyl - 1,1,3 - triethoxy - -octadiene - (4,6),
nD22=1.501, ultraviolet absorption maxima at 236 m and 262 m (in
petroleum ether solution). This material was processed without further
purification.
The, above 55 g. of material was mixed with 120 ml. of glacial acetic
acid, 10 g. of sodium acetate and 6 ml. of water. A trace of
hydroquinone was added, and the reaction mixture was heated at 95 C.
for 6 hours. The mixture was then cooled to 30 C. to 40 C. and poured
into a mixture of 100 g. of ice and 1C3 ml. of water. The reaction
product was extracted with petroleum ether, the petroleum ether
extract Tras washed with aqueous sodium bicarbonate solution and then
with water, and dried over sodium sulphate. The petroleum ether
solution was concentrated, and the residue was distilled in a high
vacuum, yielding 30 g. of 8 - [21,61,61 - trimethyl - cyclo hexadien -
(11,3l) - yl - (11] - 2,6 - dimethyl octatrien-2,4,6)-al-(1) [b.p.=138
to 143
C./0.08 mm. Hg.] which soon solidified into a crystalline mass. The
material was recrystallised twice from twice its weight of petro leum
ether at minus 70 C., yielding yellow crvstals of m.p. 64 C. to 66 C.,
ultraviolet absorption maximum at 315 m , E11=1745 (in petroleum ether

solution).
B) 8-[21,61,61-TRIMETHYL-CYCLOHEXEN-(21)
YLIDENE - (11)] - 2,6 - DIMETHYL - OCTA
TRIEN-(2,4,6)-AL-(1):
To a solution of 49.5 g. of 4 - [21,61,61 trimethyl cyclohexen - (21)
- ylidene - (11)] - 2-methyl-buten-(2)-al-(1) in 54 g. of ethyl
orthoformate was added a solution of 1 ml. of orthophosphoric acid in
9 ml. of absolute ethyl alcohol, and the mixture was set asid for 15
hours at 200 C. to 25 C. Thereupon 10 g. of pyridine was added and the
mixture was poured into a mixture of 10G g. of 5 aqueous sodium
bicarbonate solution and 6G g. of ice. The resulting mixture was
extracted with petroleum ether and the extract was shaken with aqueous
sodium bicarbonate solution and dried over potassium carbonate.
Th petroleum ether solution was concentrated and the residue was fred
in vacuo at 70 C. of excess ethyl orthoformate and of the ethyl
tormate produced by reaction, thereby yielding 70 g. of
4-[21,6l,6l-trimethyl-cyclohexen- (21) - ylidene - (11)] - 2 - methyl
- 1,1 - di ethoxy-butene)-(2); nD22=1.5155; absorption maximum in the
ultraviolet spectrum at 284.5 m (in petroleum ether solution).
The last na@ned compound, without further purification, was condensed
with ethyl vinyl ether. To this end, 3 ml. of a 10% solution of zinc-
chloride in ethyl acetate was added to the 70 g. of the compound, then
20 g. of ethyl vinyi ether and 18 ml. of a 10% solution of zinc
chloride in ethyl acetate was added simultaneously, with stirring at
30 C. to 35 C., over a period of 2 hours. The stirring was continued
20 hours longer at ca 20 C. The crude 6-[21,61,61-trimethyl-
cyclohexen - (21) - ylidene - (11] - 4 - methyl
1,1,3-triethoxy-hexene-(4) obtained in this manner was treated with a
mixture of 240 ml. of glacial acetic acid, 12 g. of sodium acetate and
6 ml. of water and heated for 6 hours in a nitrogen atmosphere at 95
C. Then it was cooled to 30 C. to 40 C. and poured into a mixture of
200 parts by weight of ice and 200 parts by volume of water. The oily
reaction product was extracted with petroleum ether, the extract was
washed with 5% aqueous sodium bicarbonate solution and with water and
dried over sodium sulphate. After concentration of the petroleum ether
solution, the residue was distilled in a high vacuum.
There were obtained 61 g. of 6-[21,61,61-trimethyl - cyclohexen - (21)
- ylidene - (11)] 4-methyl-hexadien-(2,4)-al-(1) as a mixture of
isomers, b.p. about 125 C.iO.02 mm. Hg.
By crystallization from petroleum ether at minus 70 C., there was
obtained a yellow crystalline form, m.p. 73 C.-740 C.; ultraviolet
absorption maxima at 353 na and 372 m ; E11=2360 and 2200 (in
petroleum ether solution). A residual oily isomer was converted in
part into the crystalline isomer by heating with acetic acid and

sodium acetate at 95 C. for 5 hours; by repeated treatment of the
mother liquor, practically the entire quantity was obtained in the
form of the crystalline isomer.
To a solution of 50 g. of crystalline 6 - [2l,6l,6l - trimethyl -
cyclohexen - (21) ylidene - (11)] - 4 - methyl-hexadien - (2,4) al-(1)
in 54 ml. of ethyl orthoformate was added a solution of 1 ml. of
orthophosphoric acid in 9 ml. of absolute ethyl alcohol, and the
mixture was set aside for @@ hours at 200 C. to 25 C. Then 10 ml. of
pyridine was added and the mixture was poured into a mixture of 10 g.
of 5 u,, aqueous sodium bicarbonate solution and 60 g. or ice. The
resulting mixture was extracted with petroleum ether, the extract was
shaken with aqueous sodium bicarbonate solution and dried over
potassium carbonate. Then the petroleum ether solution was
concentrated and the zesi- due was freed from excess ethyl
orthoformate and trom the ethyl formate produced oy tire reaction an
vacuo at 700</RTI
STAGE 1
1A) 16 g. of magnesium and 110 g. of n-hexyl bromide were reacted in
330 ml. of absolute diethyl ether, thereby forming an ethereal
solution of fg-hexyl magnesium bromide. This Grignard solution was
stirred for 24 hours in an atmosphere of acetylene.
Two layers were formed. The upper layer was separated eN. The lower
layer was washed once with 100 ml. of absolute diethyl ether and to
the washed material was added 200 ml. of absolute diethyl ether and
then a solution of 80 g. of 8-[21,61,61-trimethyl-cyclohexadien -
(1l,3l) - yl - (11)3 - 2,6 - dimethyloctatrien-(2,4,6)-al-(1) in 200
ml. of absolute diethyl ether was added quickly. The mixture was
heated under reflux for 3 hours, while stirring in a nitrogen
atmosphere. Then the reaction mixture was cooled, poured into a
mixture of 75 g. of ammonium chloride and 175 g. of ice-water and the
whole was stirred well for 10 minutes. The ether layer was separated,
washed thrice (each time with 209 ml. of water) and the washed
ethereal solution was dried over sodium sulphate. The ether was driven
off, yielding 87 g. of y llow, resinous, 1,18 - di[21,61,61 -
trimethyl - cyclo hexadien - (11,31) - yl - (11)] 3,7,12,16
tetramethyl - 8,11 - dihydroxy - octadeca
hexaen-(2,4,6,12,14,16)-ine-(9), having an absorption maximum in the
ultraviolet spectrum at 285 m (in petroleum ether).
2A) Dry acetene-free acetylene was introduced into a solution of 3 g.
of lithium in 1200 mI. of liquid ammonia until there was no further
reaction. Then while stirring vigorously, a solution of 100 g. of
8-[21,61,61- trimethyl - cyclohexadien - (11,31) - yl - (11)]
2,6-dimethyl-octatrien-(2,4,6)-al-(1) in 400 ml. of absolute diethyl
ether was added over a period of 20 minutes and the reaction mixture

was stirred thoroughly for 20 hours while taking precaution to exclude
moisture. Thereupon 50 g. of ammonium chloride was added in small
portions and the ammonia was permitted to evaporate. 400 ml. of water
was added and the ether layer was separated and washed with water and
then dried over sodium sulphate and concentrated. The residual reddish
oil was dried well in vacuo. There was obtained 108 g. of
10-[21,61,61-trimethyl cyclohexadien - (11,31) - yl - (11)] - 4,8 - di
methyl-decatrien-(4,6,8)-in-(1)-ol-(3) as a viscous oil, having an
absorption maximum in the ultraviolet spectrum at 284 m (in petroleum
ether). Determination of active hydrogen according to Zerewitinoff's
method showed, in the cold, one active hydrogen atom; and in the warm,
two active hydrogen atoms.
The last named compound (108 g.) was dissolved in 500 ml. cf absolute
diethyl ether and was added gradually at 15 C.-200 C., while stirring
to a Grignard solution prepared from 18 g. of magnesium 91 g. of ethyl
bromid and 300 ml. of absolute diethyl ether.
The reaction mixture was heated under reflux for one hour in a
nitrogen atmospnere and then cooled with ice-water. A solution of 92
g. of 8 - [21,61,61 - trimethyl - cyclohexa dien - (11,31) - yl -
(11)] - 2,6 - diemthyl octatrien-(2,4,6)-al-(1) in 400 ml. of absolute
diethyl ether was added at about 20 C. and the reaction mixture was
heated under reflux for 3 to 4 hours in a nitrogen atmosphere. The
reaction mixture was then poured into a mixture of 400 ml. of 3-N
sulphuric acid and 600 g. of ice, the ether layer was separated and
washed with 5 o' aqueous sodium bicarbonate solution dried over sodium
sulphate and concentrated in vacuo, yielding 200 g. of resinous 1,18 -
di[21,61161 - trimethyl - cyclo hexadien - (11,31) - yl -
(11)]-3,7,12,16 - tetra methyl - 8,11 - dihydroxy - octadecahexaen
(2,4,6,12,14,16)-ine-(9).
1B) 16 g. of magnesium and 110 g. of n-hexyl bromide were reacted in
330 ml. of absolute ether, thereby forming an ethereal solution of
n-hexyl magnesium bromide. This
Grignard solution was stirred for 24 hours in an atmosphere of
acetylene. Two layers were formed. The upper layer was separated off.
The lower layer was mashed once with 100 mi. of absolute diethyl
ether, and to the washed material was addrd 200 ml. of absolute
diethyl ether, and then a solution of 80 g. of
8-[21,61,61-trimethyl-cyclohexen-(21)ylidene - (11)] - 2,6 - diemthyl
- octatrien (2,4,6)-al-(1) in 200 ml. of absolute diethyl ether was
added quickly. The mixture was heated under reflux for 3 hours, while
stirring, in a nitrogen atmosphere. Then the reaction mixture was
cooled, Foured into a mixture of 75 g. of ammonium chloride and 175 g.
of ice-water, and the whole was stirred well for 10 minutes. The ether
layer was separated, washed thrice (each time with 200 ml. of water)

and the washed ethereal solution was dried over sodium sulphate. The
ether was driven off, yielding 87 g. of yellow, resinous 1,18 -
di[21,61,61 - trimethyl - cyclo hexen - (21) - ylidene - (11)] -
3,7,12,16 tetramethyl - 8,11 - dihydroxy - octadeca hexaen-(2,4,6,12,
14,16)-ine-(9), having an absorption maximum in the ultraviolet
spectrum at 349.5 m (in petroleum ether).
2E) Dry, acetone-free acetylene was introduced into a solution of 3 g.
of lithium in 1200 ml. of liquid ammonia, until there was no further
reaction. Then, while stirring vigorously, a solution of 100 g. of
8-[2S,6',6l- trimethyl - cyclchexen - (21) - ylidene - (11)]
2,6-dimethyl-octatrien-(2,4,6)-al-(1) in 400 ml. of absolute diethyl
ether was added over a period of 20 minutes, and the reaction mixture
was stirred thoroughly for 20 hours, with precautions to exclude
moisture. Thereupon 50 g. of ammonium chloride was added in small
portions, and the ammonia was permitted to evaporate 400 ml. of water
was added, the ether layer was separated and washed with water and
then dried over sodium sulphate and concentrated. The residual reddish
oil was dried well in vacuo. There were obtained 108 g. of
10-[21,61,61-trimethylcyclohexen - (21) - ylidene - (11)] - 4,8 - di
methyl-decatrien-(4,6,8)-in-(1)-ol-(3) as a viscous oil having an
absorption maximum in the ultraviolet spectrum at 349 mp (in petroleum
ether). Determination of active hydrogen according to the Zerewitinoff
method showed, in the cold, one active hydrogen atom and, in the warm,
two active hydrogen atoms.
The last named compound (108 g.) was dissolved in 500 ml. of absolute
diethyl ether and was added gradually, at 150 C.-200 C., while
stirring, to a Grignard solution prepared from 18 g. of magnesium, 91
g. of ethyl bromide and 300 ml. of absolute diethyl ether.
The reaction mixture was heated under reflux for one hour in a
nitrogen atmosphere and then cooled with ice-water. A solution of 92
g. of 8-[21,61,61-trimethyl-cyclohexen-(21)ylidene - (11)] - 2,6 -
dimethyl -octatrien (2,4,6)-al-(1) in 400 ml. of absolute diethyl
ether was added at about 200 C. and the reaction mixture was heated
under reflux for 3 to 4 hours in a nitrogen atmosphere. The reaction
mixture was then poured into a mixture of 400 ml. of 3-N sulphuric
acid and 600 g. of ice, the ether layer was separated and washed with
5% aqueous sodium bicarbonate solution dried over sodium sulphate and
concentrated in vacuo, yielding 200 g. of resinous 1,18 - di[21,61,61
- trimethyl - cyclohexen (21) - ylidene - (11)] - 3,7,12,16 -
tetramethyl 8,11 - dihydroxy - octadecahexaen - (2,4,6,12,
14,16)-ine-(9).
STAGE 2
1) A solution of 19 g. of 1,18-di[21,61,61- trimethyl - cyclohexadien
- (11,31) - yl (11)3 3,7,12,16 - tetramethyl - 8,11 - dihydroxy

octadacahexaen - (2,4,6,12,16) - ine - (9) in 38 ml. of toluene was
added gradually to a well stirred mixture of 6.8 ml. of phosphorus
oxychloride, 34 ml. of pyridine and 30 ml. of toluene, while cooling
with ice-water. Then the reaction mixture was heated for one hour at
95 C., quickly cooled down and poured upon 300 g. of ice. The toluene
solution was separated, washed twice with sulphuric acid (each time
with 200 ml. of 3-N sulphuric acid) and then twice with aqueous sodium
bicarbonate (each time with 200 ml. of 5% aqueous sodium bicarbonate
solution). The washed toluene solution was dried over sodium sulphate
and the solvent was removed under a water-pump vacuum. The crystalline
residue was washed with a little petrol leum ether and was
recrystallized from a mixture of methylene chloride and methanol. The
red-violet crystals of 3,4;31,41;15,151-trisdehydro-betacarotene so
obtained had a melting point 165 C.-1670 C. and ultraviolet absorption
maximum at 449 m,a (in petroleum ether solution).
2) A solution of 10 g. of 1,18-di[21,61,61trimethyl - cyclohexen -
(21) - ylidene - (11)] 3,7,12,16 - tetramethyl - 8,11 - dihydroxy
octadecahexaen - (2,4,6,12,16) - ine - (9) in 90 ml. of toluene was
added gradually to a well stirred mixture of 6 ml. of phosphorus
oxychloride, 43 ml. of pyridine and 50 ml. of toluene while cooling
with ice-water. Then the reaction mixture was heated for one hour at
95 C. and quickly cooled down and poured upon 300 g. of ice. The
toluene solution was separated washed twice with sulphuric acid (each
time with 200 ml. of 3-N sulphuric acid) and then twice with sodium
bicarbonate solution (each time with 200 ml. of 5% aqueous sodium
bicarbonate solution). The washed toluene solution was dried over
sodium sulphate and the solvent was removed under a water-pump vacuum.
The residue was extracted with petroleum ether and the petroleum ether
extract was concentrated, thereby yielding crude 3,4;
31,41;15,151-trisdehydro-betacarotene. Upon recrystallisation from a
mixture of methylene chloride and methanol, the purified material
formed redviolet crystals, m.p. 165 C.-167 C.; ultraviolet absorption
maximum at 449 m (in petroleum ether solution).
3)1 g. of 1,18-di[21,6l,6l-trimethyl-cyclohexadien - (11,31) - yi -
(11)] - 3,7,12,16 - tetramethyl - 8,11 - dihydroxy - octadeca
hexaen-(2,4,6,12,14,16)-ine-(9) was dissolved in 20 ml. of diethyl
ether, and the solution was mixed with 2 ml. of ethanolic hydrogen
chloride containing 23.7% by weight hydrogen chloride and 4 ml. of
ethanol. The mixture was allowed to stand for 2 hours at ca 20 C. and
then for an additional period of 18 hours at 0 C.-5 C. The crystals
formed were filtered off with suction, washed with methanol and with
petroleum ether and then dried. There were obtained 0.8 g. of
3,4;31,41;15,151 - trisdehydro - betacarotene, m.p. 165 C.
STAGE 3

0.75 g. of 3,4;31,41;15,151 - trisdehydro betacarotene in 20 ml. of
toluene was shaken in a hydrogen atmosphere at 20 C. in the presence
of 0.2 g. of palladium/lead/calcium- carbonate catalyst /Lindlar,
Helvetica Chimica
Acta, 1952, 35, 450/ and 0.05 ml. of quinoline until one molar
proportion of hydrogen was taken up. The catalyst was then filtered
off and the solvent was removed in a high vacuum. The residue was
crystallized from a mixture of methylene chloride and methanol,
thereby yielding 15,151-monocis 3,4;31,41 - bisdehydro - betacarotene
as dark red to violet crystals; m.p. 1900 C. (after softening and
resolidification at 1300 C.- 140 C.); ultraviolet absorption maxima at
366 m (" cis peak ") and 467 m (in petroleum ether solution).
STAGE 4
A suspension of 5 g. of 15,151-monocis
3,4;31,41-bisdehydro-betacarotene in 30 ml. of petroleum ether (b.p.
80 C.-100 C.) was heated under reflux for 22 hours in a liitro- gen
atmosphere. Then the mixture was cooled and the crystalline
precipitate was filtered off. The solid was recrystallized from a
mixture of methylene chloride and petroleum ether (alternatively, from
methylene chloride/methanol). The blue-violet crystals of all-trans
3,4;31,41-bisdehydro-betacarotene so obtained had a melting point of
190 -190 C., and showed an absorption maximum in the ultraviolet
spectrum at 471 m (in petroleum ether solution).
What we claim is:
1. 3,4;31,41;15,15 - trisdeydro - beta carotene and 15,151-monocis
3,4;31,41-bisdehydro-betacarotene,
2. A process for the manufacture of the dehydro-betacarotenes claimed
in Claim 1 whereof, which process comprises condensing acetylene with
8-[21,61,61-trimethyl-cyclohexadien - (11,31) - yl - (11)] - 2,6 -
dimethyl octatrien-(2,4,6)-al-(1) or 8-[21,61,61-trimethylcyclohexen -
(21) - ylidene - (11)] - 2,6 - di methyl-octatrien-(2,4,6)-al-(1) in a
metalorganic reaction, subjecting the resulting 1,18 di[21,6l,6l -
trimethyl - cyclohexadien - (11,31) yl - (11)] - 3,7,12,16 -
tetramethyl - 8,11 dihydroxy - octadecahexaen -
(2,4,6,12,14,16)ine-(9) or 1,18 - di[21,61,61 - trimethyl cyclohexen -
(21) - ylidene - (11)] - 3,7,12,16 tetramethyl - 8,11 - dihydroxy -
octadeca hexaen - (2,4,6,12,14,16) - ine - (9) to bilateral allyl
rearrangement and dehydration and, if desired, partially hydrogenating
the resulting 3,4;31,41;15,15 l-trisdehydro-betacarotene at the triple
bond to obtain 15,151-monocis 3,4;31,41-bisdehydro-betacarotene.
3. A process in accordance with Claim 2, wherein the said condensation
is carried out stepwise by first condensing acetylene with
approximately one molar proportion of the aldehyde initial material in
a metal-organic reaction and condensing the 1S[21,6l,6l-trimethyl -

cyclohexadien - (11,31) - yl - (11)] 4,8 - dimethyl - decatrien -
(4,6,8) - in - (1) ol - (3) or 10 -[2l,6l,6l - trimethyl - cyclo hexen
- (21) - ylidene - (11)] - 4,8 - dimethyl decatrien - (4,6,8) - in -
(1) - ol - (3) so obtained with a further approximately molar
proportion of the said material in a metalorganic reaction.
4. A process in accordance with Claim 2 or
Claim 3, wherein the bilateral allyl rearrangemcnt and dehydration is
brought about by heating the product of the first stage in an inert
solvent with about two molar proportions of phosphorus oxychloride in
the presence of an organic tertiary base or by react ing same with a
hydrogen halide at a low temperature.
5. A process in accordance with any one of the preceding process
claims, wherein the partial hydrogenation is carried out using
elemental hydrogen in the presence of a hydrogenation catalyst which
selectively catalyses the conversion of a triple to a double bond.
6. A process in accordance with any one of the preceding process
claims, which includes the further step of isomerizing the
15,151monocis 3,4;31,41-bisdehydro-betacarotene by heating or
irradiating same or treating same with iodine to produce all-trans
3,4;3,4-bisdehydro-betacarotene.
7. A process in accordance with Claim 6, wherein the isomerization is
brought about by heating a suspension of the 15,15l-monocis
3,4;31,41-bisdehydro-betacarotene in an organic liquid vehicle.
8. A process for the manufacture of the substances claimed in Claim 1
hereof and their conversion into all-trans
3,4;31,41-bisdehydrobetacarotene, substantially as described with
reference to the example.

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