4666 4670.output

* GB785073 (A)
Description: GB785073 (A) ? 1957-10-23
Radio frequency tuner
Description of GB785073 (A)
PATENT SPECIFICATION
785,073 Date of Application and filing Complete Specification:June I 1
1955.
No 15699/55:
Application made in United States of America on June 21, 1954.
Complete Specification Published: Oct 23, 1957 -
151 Index at Acceptance:-Class 40 ( 8), U 18 (A 2: A 5 B 3: B 4 A).
International Classification:-H 03 h.
COMPLETE SPECIFICATION
Radio Frequency Tuner.
We, ALADDIN INDUSTRIES, INCORPORATED, : a corporation organized and
operating under the laws of the State of Illinois, United States of
America, of 705, Murfreesboro Road Nashville, Tennessee, 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 radio frequency tuners, particularly those
adapted to tune over wide'tuning ranges at very high and ultrahigh
frequencies.
One principal object of the invention is to provide an improved radio
frequency tuner adapted to cover a wide frequency range, such as the
range from 54 to 890 megacycles, embracing the commercial television
bands from 54 to 216 megacycles and from 470 to 890 miegacycles.
A further object is to provide an improved tuner of the foregoing
character which affords high resonant impedance.
Another object is to provide an improved tuner especially well adapted
to be employed as a load impedance in a radio frequency amplifier
stage.
Another object is to provide a wide, range radio frequency tuner

combining the advantages of high resonant impedance and a high factor
of merit or Q.
It is a further object to provide an improved tuner which acts
generally as a variable inductance in one portion of its tuning range
and as a short-circuited quarter wave line in another portion.
Other objects and advantages of the invention will appear from the
following description, taken with the accompanying drawing in which:
Fig 1 is a longitudinal sectional view of an illustrative embodiment
of the invention in the form of a wide range radio frequency tuner,
the view being taken generally along the line 1-1 lPrice 3 s 6 d l in
Fig 2; Fig 2 is an end elevational view of the tuner shown in Fig 1;
and Vig 3 is a transverse sectional view taken generally along a line
3-3 in Fig 1 50 The illustrated tdner 1 embodies a tuning coil 2,
which, as-shown, is generally helical and cylindrical In this
instance, the coil is formed by a metallic ribbon or filmn 3 deposited
on an insulating tubular support 4 55 and formed into the desired
helical design by photographic printing or other printed circuit
techniques A thin coating 5 of low-loss dielectric material may be
applied to the coil 2 to protect and insulate the metallic film 3 60
To obtain adequate band spreading, particularly at the high frequency
end of the tuning range covered by the tuner 1, and to minimize
losses, the coil 2 is illustrated with nonuniform inductance per unit
length Merely 65 by way of example, the coil 2 is shown with end
portions 6 and 7 having relatively low turnum density and low
inductance per unit length, together with an intermediate portion 8
having high turn density and, hence, high 70 inductance per unit
length In order to minimize both the inductance and the losses in the
end portion 6, the conductive ribbon 3 is made wider than in the other
end portion 7 and the intermediate portion 8 The left 75 end portion 6
of the coil 2 is connected to a substantially continuous cylindrical
metallic extension 9.
The illustrated coil 2 is disposed in a housing 10 which may assume a
variety of forms 80 but is illustrated as an elongated cylindrical
tube closed at its left hand end by an end wall 11 In this instance,
the coil 2 is positioned axially in the tubular housing 10 The left
end of the tubular coil form 4 is mounted on 85 the end wall 11.
In order to vary the inductance of the coil 2, a tuning member 12 is
disposed between the housing 10 and the coil The illustrated tuning
member 12 is in the form of an 90 SX t s 1 i?' ', '" 785,073 annular
metallic plunger or ring having an tion, the tuner serves as the
load'impedance -external-I ylindrical surface 13 closely for the radio
frequency amplifier -tube 26.
adjacent the interior surface of the cylindrical When input voltage at
the resonant-frequency housing 10 A bore or cylindrical opening 14 of

the tuner is supplied inthe uisual way to fheis formed in the plunger
12 to receive the coil cathode 27, an output voltage is-produced at 70
2; Thus, the plunger 12 is adapted to be the anode 28: The tuner
provides high telescopically received over the coil 2 and -resonant
impedance throughout its tuning within the housing 10 It-is preferable
to range and hence maintains the gain-of the insulate the plunger from
the housing and the amplifier tube 26.
coil to provide for capacitive coupling or Energy may be transferred
from the tuner 75 energy transfer between the plunger and these in a
variety of ways In the UHF commercial elements Accordingly, a low-loss
dielectric television band, for example, energy may be sleeve 15 is
interposed between the plilger efficiently transferred from the tuner
1 by and the housing 10 This sleeve 15 may take means of a coupling
loop 35 disposed in the the form of a thin coating applied to the
housing 10 adjacent the left end portion of the 801 plunger The
insulating coatifig 5 on the coil coil 2 One end of the loop 35 is
grounded to 2 insulates 'the coil from the plunger, 12 In the 4
housing in this instance, and the other addition, an air gap 16 is
provided between end is brought out to a UHF output terminal the coil
2 and the plunger 36: " Provision is made for effecting relative In
the VHF television band, energy may be 85 axial movement between the
coil 2 and the transferred from the tuner more efficiently-by plunger
12 so as to vary the effective induct means of a lead 37 connected to
the left-end ance of the coil The plunger 12 is 'adapted portion 6 of
the coil 2 A coupling capacitor 38 to be moved relative to the -coil 2
in the may be connected between the lead 37 and a housing 10 by means
of a cam 17 mounted on -VHF output terminal 39 90 a rotatable control
shaft 18 A nnmber of By virtue of the capacitive coupling between cams
may be -mounted on the shaft in order the plunger 12-and the coil 2,
and between the that several tuners may be controlled in corn plunger
and the housing 10, the plunger 12 mon A flexible insulating rod 19 is
employed provides a low impedance path between the to connect the
plunger 12 to a -pivot 20 housing 10 and the portion of the coil 2 95
mounted on a cam follower arm 21 which within the plunger This is true
throughout carries a-roller 22 adapted to follow the cam the tuning
range of the tuner 1 Accordingly, : 17 ' A spring 23 is -provided to
bias the arm the plunger 12 acts as virtually a short circuit 21 in
one direction so as to hold the roller 22 between the housing and the
-portion of the against the cam 17 The flexible rod 19 corn coil
inside the plunger The housing 10 acts 100 pensates for any
misalignment between the as a low impedance return connection to annrm
21 and the plunger 12 A slot 24 may be ground or to some other circuit
element.
: formed longitudinally in the housing 10 to When-the plunger 12 is at

the extreme outer admit the arm 21 and permit movement of the ends of
the coil 2 and the housing 10, as arm between the full and dotted line
position shown in full lines in Fig i 1, substantially the 105 shown
in Fig 1 full'inductance of the coil 2 is in the circuit Television
channel numbers have been between the end lead 25 and the housing As
shovn on the cam 17 to indicate-the position the plunger is moved into
the housing 10ing of the cam, relative to the roller 22, -for toward
its dotted line position (Fig 1), there the various-commercial
television channels is a progressive decrease in the portion of the 11
Energy may be transferred to the left-hand coil effectively connected
between the end-lead end of the coil 2 by means of-a -lead in the 25
and the housing Accordingly, the form of a conductive ribbon 25
connected to resonant frequency of the tuner l -is progresthe metallic
cylindrical extension 9 In this sively increased It will be understood
that instance, the ribbon-lead 25 is arranged to the coil 2 is
resonated by distributed 115 receive energy from a grounded-grid-type
capacitances between its turns and between radio frequency amplifier
tube 26 having a the coil and the housing 10, together with the
cathode 2-7 an anode 28, and a grid 29, the capacitance between-the
anode 28-and ground, grid'being grounded by a lead 30 The ribbon and
other circuit capacitances.
lead 25 is connected to the anode 28 A con When the plunger reaches
its dotted line 120 nection is made to the opposite end portion 7
position, shown in Fig 1, only the cylindrical of the coil by means of
a lead 31, which is extension 9 of the coil is effectively connected
connected through a filtering resistor 32 to a between the end lead 25
and the housing 10.
terminal 33 representing a source of positive In this position the
inductance in the resonant anode voltage A feed-through-type by-pass
circuit is at a minimum As the plunger 125capacitor 34 is -connected
between the lead 31 approaches this -position, the tuner tends to and
ground The tuner '1 may be employed assume some of the characteristics
of a shortin a variety of circuits and the-illustrated radio circuited
resonant quarter wave line For this frequency amplifier circuit is
disclosed merely reason, the Q of the tuner is maintained at a by way
of example In its illustrated applica high value even at the high
frequency end of 130 of the coil.
2 A wide range radio frequency tuner in accordance with claim 1,
characterized in that said tuning member is in the form of a 40
plunger ring.
3 A wide range radio frequency tuner in accordance with claim 1 or 2,
characterized in that said tuning member or plunger ring is insulated
from said housing and from said 45 coil to provide for capacitive
energy exchange therebetween to constitute a low impedance capacitive

path.
4 A wide range radio frequency tuner in accordance with claim 1, 2 or
3, characterized 50 in that said housing is provided with an end wall
closing one end thereof and that said coil is supported thereon and
that said tuning member is movable through the opposite open end wall
of said housing and supports said 55 tubular member on the side remote
from said end wall.
A wide range radio frequency tuner in accordance with claim 1, 2, 3 or
4, characterized in that said housing, said tuning 60 member and said
coil are circular in transverse cross-section and that means are
provided at said one end of said housing for supporting a vacuum tube
thereon.
6 A wide range radio frequency tuner sub 65 stantially as herein
described and as illustrated in thelaccompanying drawings.
HERON ROGERS AND CO, Agents for Applicants, Bridge House, 181, Queen
Victoria Street, London, E C 4.
the tuning range.
In order to prevent adverse effects upon the performance of the tuner
due to spurious resonances in the inactive portion of the coil 2, an
elongated sleeve 40 is mounted on the right hand end of the plunger 12
This sleeve 40 progressively envelops the coil 2 as the plunger 12 is
moved into the housing 10.
Accordingly, the inactive portion of the coil :10 2, extending beyond
the plunger 12, is effectively short circuited or at least heavily
loaded by the sleeve 40 Any residual resonances, not completely damped
out by the loading effect of the sleeve 40, are detuned to :15
frequencies far removed from the resonant frequency determined by the
portion of the coil 2 between the plunger 12 and the end lead 25.
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* 5.8.23.4; 93p
* GB785074 (A)
Description: GB785074 (A) ? 1957-10-23

Improvements in or relating to thermal conductivity cells
Improvements in or relating to Thermal Conductivity Cells.
We, THE BRITISH PETROLEUM COMPANY
LIMITED, of Britannic House, - Finsbury
Circus, London, E.C.2, a British joint-stock
Corporation and Charles Leslie Arthur
Harbourn and Dennis Henry Desty, both of the Company's Research
Station, and both of
British nationality, 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 improved means of detecting changes- in the
thermal conductivity of a gaseous stream.
Detectors, employing thermal conductivity as a means of measuring the
composition of gases, have been described wherein a wire is heated by
an electric current, its temperature and hence its resistance varying
with the conductivity of the surrounding gas. These detectors,
employing hot wires, are of two main types. In the first type the hot
wire is tensioned axially in a cylindrical chamber, the -gas
entering-at the one end of the chamber and flowing along the wire.
This type of detector suffers from two main disadvantages.
The first disadvantage is that the part of the wire upon which the.
gaseous stream impinges first, is appreciably cooled by- the incoming
gas and thus the resistance measured will vary markedly with the rate
at which the gas flows.
The second is that to achieve a reasonable sensitivity- it is
necessary to employ at least 3 cms. of hot wire which necessitates the
use of a large chamber. This large volume hinders the resolution of
closely following changes in thermal conductivity. The second type of
hot wire detector employs - a small, heated, coiled wire - placed in a
small side chamber connected by a single orifice to a passage through
which the gas flows. This device considerably reduces the effect of
change in flow rate since the gas is not directed over the wire.
However, it is necessary for the gas to diffuse into the chamber
before the instrument will respond and as this is a'relatimely slow
process rapid changes in thermal conductivity are not easily recorded.
Compared with the first described type of hot wire detector, this

second type has the advantage that the volume of the chamber is
reduced but this is offset in that the response is much slower.
It-has been proposed to replace the hot platinum wire in detectors
hereinbefore described with - a thermistor, which is a new circuit
element, a full description of which is to be found in "Electrical
Engineering,"
Volume 65 dated November 1946, Properties and Uses of
Thermistors-Thermally Sensi- tive Resistors, and in an article by W.
T.
Gibbons, "Thermistor Production m "Electrical Communications" for
December, 1953. We have found that when using a cell containing a
thermistor in place of a cell using a hot wire, the size of the
chamber may be much reduced and in consequence the selectivity of the
detector in the cell employing a thermistor is' increased. Furthermore
it is possible, when using a thermistor, to obtain up to ten times the
output voltage compared with that obtained when employing a hot wire
type instrument under similar conditions.
However, we have found that cells constructed according. to a general
design as employed in the hot wire type cells, and wherein the hot
wire is replaced by a thermistor mounted on electrical leads, are
reduced in utility by their 'high sensitivity to changes in the flow
rate of the gas, whereby spurious variations may be introduced into
measurements of the change in thermal conductivity.
The object of this invention is to provide a cell; employing a
thermistor, for determining changes in thermal conductivity, having a
low sensitivity to changes in flow rate.
According to the-present invention there is provided: a cell for
indicating variations in the thermal conductivity of a gaseous stream,
comprising a thermistor mounted in a chamber
n having a gas inlet and a gas outlet so arranged
That a;gas~entering and leaving thereby will inflow'in ~a helical
manner around the thermistor.
By the term " thermistor " as used- throughout this specification and-
-claims, we mean a resistor, having a high temperature coefficient,
consisting of or comprising a sintered mixture of oxides.
Thermistors usually have a temperature coefficient such that their
resistance decreases about 4 per cent. per C rise in temperature, and
have specific resistances at 20 C in the range 0.1 to 109
ohm-centimetres.
Typical thermistors are (a) a mixture of manganese oxide and nickel
oxide and (b) a mixture of manganese oxide, nickel oxide and cobalt
oxide. Other oxides which may be employed.--'in.the thermistors
include iron 'oxide (we2 0,), zinc .oxide and cuprous oxide.
The preferred shape of the chamber is one having a circular cross

section, for example spherical or conical, .a convenient form being
cylindrical. Owing to the small physical dimensions df the thermistor
the volume of the chamber can be ~ reduced markedly; thus preferably
the diameter of the circular section of the chamber is not greater
than one inch whereby5 in us a high degree of resolution is obtained
in measuring rapid changes in thermal conductivity in a gas stream fed
thereto.
Preferably the inlet and outlet are arranged to provide that, in
operation, the gas is introduced tangentially at one end to the
circular cross-section and at an angle to the overall path such that
it completes approximately one revolution of the chamber before
leaving tangentially at the other end.
Conveniently, the thermistor is mounted on its electrical leads In a
cylindrical chamber these leads preferably lie'along the axis of the
chamber and are supported in a state of tension so that~the thermistor
is held in constant position.
According to a further feature of this invention there is provided an
instrument for indicating variations in thermal conductivity of a gas
comprising an electrical circuit having therein a cell as described
hereinbefore and means - of measuring the variations in the resistance
of thethermistor. This variation may be measured by incorporating a
galvanometer in the circuit or it can be measured by comparing
resistances in a bridge network.
Furthermore this invention relates to an instrument for comparing the
thermal con
ductivity of two gases by using. at least two
cells, the first cell being for the passage of
one of the gases, and the second cell being for
the passage of the other gas, the said first and
second cell being connected electrically in
adjacent sides of a'diferential bridge network.
~ ccbrding-~to a further development of this
instrument four cells are used. The four cells are employed in pairs,
each pair consisting of cells connected symmetrically and in parallel
to a single inlet tube and a single outlet tube, one pair being
provided for the'passage.of one gas and the other pair being provided
forthe passage of the other gas, the thermistors of each pair of cells
being connected electrically into non-adjacent sides of a differential
bridge network.
The term "gas" is used herein with - reference to single substances in
the gas phase and to .gaseous mixtures.
In the methods herein described for comparing gases one. of the gases
may be employed in the form of a steady stream of constant composition
to eliminate certain "fixed errors " arising from the use of the cell.

The invention-is illustrated but in no way limited with reference to
the accompanying
Figures 1-3.
Figure. 1 is a vertical section through a conductivity cell.
Figure 2 is a horizontal section through four conductivity cells used
in an instrument for comparing variations in the thermal conductivity
of two gases.
Figure 3 is the electrical circuit used in an instrument for the
comparison of variations in the thermal conductivity of two gases.
Referring to Figure 1, the chamber 1 is cylindrical in shape, having
been formed by boring a solid copper block. Inlet tube 2 enters the
chamber tangentially and at such an angle that the gas completes one
revolution of the chamber before leaving by the outlet tube 3 which is
also tangential to the chamber and situated at the other end of the
chamber to the inlet tube. Each end of the chamber is closed by a
copper plug 4 having a central orifice through which the electrical
leads 5 of the thermistor 6 leave the chamber.
The leads are supported in insulated. copper supports 7 seated on lead
washers 8.
Referring to Figure 2, the conductivity cells A1,A2, A3, A4, each
constructed as described with reference to Figure 1, are drilled from
a solid copper Ibar with a cross-section 12" x 1", and are each 3"
long and 5/16" in diameter.
The inlet tubes 9 and 10 of cells A1 and A2 are joined symmetrically
to a common inlet tube 11 and the outlet tubes.12 and 13 of cells
A1 and A, are joined symmetrically to a common outlet tube 14. Cells.
A3 and A4 are similarly joined, inlets 15 and 16 joined to common
inlet 17 and outlets 18 and 19 joined to common outlet 20. Thus the
two gases which are to be compared each pass through two conductivity
cells arranged in parallel.
Referring to Figure 3, the four conductivity cells A1, A2, A, and A4
described with reference to Figures 1 and 2 are connected electrically
into a differential bridge network, in such a manner that the two
cells havipg the same gas through them are in - non-adjacent sides of
the bridge network. 'Between cells
A2 and A, is a potentiometer 21 which is used to pre-set the balance
of the network. A recording voltmeter 22 lies across the bridge from
the balance point on the potentiometer to the junction 23 of cells A1
and A4. Current is supplied to the network at the junction 24 of cells
A, and A4 and at the junction 25 of cells A1 and A3, the circuit
supplying the current consisting of a number of voltaic cells 26 in
series, a switch 27, a variable resistance 28 in series with the
voltaic cells to regulate the flow of current through the thermistors
and an ammeter 29.

Thermal conductivity cells and instruments comprising said cells as
hereinbefore described are very suitable for determining changes in
the composition of a gaseous stream. Thus the cells are particularly
suitable for use as detectors in gas chromatography apparatus.
Thus, for example, by the use of cells as hereinbefore described a
high order of resolution has been achieved when used in conjunction
with a gas chromatographic-column of the type as described by A. T.
James and A.
J. P. Martin in Biochem. J. Vol. 50 (1952) at page 679.
Thermal conductivity cells, according to the present invention, may be
used for the control of fractional distillation columns, a continuous
sample of the overhead fraction, in vapour phase, being passed to one
or more of said cells to permit determination of cut points, in
accordance with variations in the thermal conductivity of the sample.
What we claim is:
1. A cell, for indicating variations in the thermal conductivity of a
gaseous stream, comprising a thermistor mounted in a chamber having a
gas inlet and a gas outlet so arranged that a gas entering and leaving
thereby will flow in a helical manner around the thermistor.
-2. A cell according to claim 1 wherein the chamber is circular in
cross section.
3. A cell according to claim 2 wherein the chamber is cylindrical.
4. A cell according to claim 3 wherein the diameter of the circular
section is not grea,ter than one inch.
5. A cell according to claim 4 wherein the inlet and outlet are
arranged to provide that, in operation, the gas is introduced
tangentially at one end and completes approximately one revolution of
the chamber before leaving tangentially at the other end.
6. A cell according to any of claims 1-5 wherein the thermistor is
maintained in a constant position in the chamber by means of
electrical leads held in a state of mechanical tension.
7. An instrument for indicating variation in thermal conductivity of a
gas comprising a conductivity cell according to any of the preceding
claims, means of passing a current through the thermistor and an
indicating or recording instrument for determining variations in the
resistance of the thermistor.
8. An instrument according to claim 7 wherein the conductivity cell is
connected electrically in one arm of a resistance bridge network
9. An instrument for comparing the thermal conductivity of two gases
comprising at least two conductivity cells according to any of claims
1-6, a first cell being provided for the passage of one of the gases
and a second cell being provided for the passage of the other of the
gases, said first cell and said second cell being connected
electrically in adjacent sides of a differential bridge network.

10. An instrument according to claim 9 comprising two pairs of
conductivity cells each pair consisting of cells connected
symmetrioally and in parallel, to a single inlet tube and a single
outlet tube, one pair being provided for the passage of one gas and
the other pair being provided for the passage of the other gas, the
thermistors of each pair of cells being connected electrically into
non-adjacent sides of a differential bridge network.
11. A cell for indicating variation -in the thermal conductivity of a
gaseous stream substantially as hereinbefore described with reference
to the accompanying Figure 1.
12. An instrument according to claim 10 and substantially as
hereinbefore described with reference to the accompanying Figures 2
and 3.
* GB785075 (A)
Description: GB785075 (A) ? 1957-10-23
Compounds of the octahydrophenanthrene series and synthesis of compounds of
the cyclopentanodimethylpolyhydrophenanthrene series therefrom
Compound of the Octahydrophenanthrene Series and Synthesis of
Compounds of the Cyclopentanodimethylpolyhydro-
phenanthrene Series therefrom
We, MONSANTO CHEMICAL COMPANY, a corporation organised under the laws
of the
State of Delaware, United States of America, of 1700, South Second
Street, City of St.
Louis, State of Missouri, 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 a method of producing and to novel compounds
useful in the synthesis of steroid compounds of the

cyclopentanodimethylpolyhydrophenanthrene series.
The invention relates more particularly to the synthesis of
17-formyl-cyclopentano-10. 13dimethyl-9mo ~ decahydrophenanthren-3-
one from l-(ss-carboxyethyl)-2-keto-14-methyl- A'ctahydrophemanthrma
and its alkyi esters having up to six carbon atoms in the alkyl group.
The latter are. believed to be new compounds. ~
The sequence of steps leading up to 17formyl -
cyclopentano-?4.9(11)-decahydrophenanthren-3-one is outlined
schematically in the accompanying drawing.
The initial reactant in the process outlined in the accompanying
drawing, namely-1 (hydroxy-methylene) - 2 - keto -
10-methyl1.2.5.8.9.10-hexahydronaphthalene (Compound
I) contains two asymmetric carbon atoms and consequently exists in the
form of four optically active isomers or two racemates, i. e. cis and
trans racemic mixtures-of the dextro and laevo optically active
isomers. All such forms or any mixture thereof may be employed as
starting materials in the process outlined herein. Compound I is
prepared by the formylation of the corresponding
2-keto-10methyl-1.2.5.8.9.10-hexahydronaphthalene
<img class="EMIRef" id="026415681-00010001" />
employing ethyl formate in the presence of sodium methylate. This may
be carried out in the following manner : all parts are by weight.
To a reaction vessel is charged 17. 3 parts (substantially 0. 32 mols)
of solid sodium methylate, 75 parts of anhydrous benzene and 37 parts
(substantially 0. 5 mols) of ethyl formate while maintaining the
temperature at 20-25 C. The suspension thus obtained is agitated in
the presence of an) atmosphere of nitrogen for 20-30 minutes and then
cooled to 10 C. : 16. 1 parts (substantially 0. 1 mols) of the
laevo-rotatory form of trans-2-keto-10methyl-1. 2. 5. 8. 9.
10-hexahydronaphthalene dissolved in 150 parts of benzene is added-and
the mixture agitated for 3 hours at substantially 15 C. The resulting
reaction mass ig then quenched with cold dilute sulphuric acid (20
parts-of sulphuric acid in 125 parts of water) while maintaining the
temperature at 15 C. and agitating for 5 minutes. The aqueous layer is
separated and extracted with several small portions of benzene. The
benzene extracts are combined with the original organic layer and the
whole subjected to distillation under reduced pressure to remove the
solvent.
The light tan oily residue so obtained consists essentially (951% by
weight) of the 1- (hydroxymethylene) derivative of the laevo rotatory
form of trans-2-keto-10-methyl-1. 2. 5. 8. 9. 10hexahydronaphthalene.
The oil is admixed with 105 parts of methanol and heated, with
agitation, to 50~C. 400 parts of an aqueous 5% copper acetate solution
is slowly added with constant agitation. The precipitate, namely the

copper chelate of the l- (hydroxymethylene) derivative of the
laevo-xotatory form of tYans-2-keto-10-methyl-1. 2. 5. 8. 9.
10hexahydronaphthalene, is filtered off, washed with methanol, and
then slurried with 87 parts of benzene. To the resulting slurry is
added
1800 parts of 26% sulphuric acid. The organic layer is recovered,
washed with aqueous sodiumbicarbonate, then with water and the
solventremoved under reduced pressure. The. residue is the oily
laevo-rotatory isomer of tracs-1- (hydroxy-methylene) - 2 - keto - 10
- methyl1.2.5.8.9.10-hexahydronaphthalene, b.p. 122123 ~C. at 2-3 mm,
nD25=1.5570, [?]D25=
-151. 6 (C=2, chloroform).
In like manner dl-trans-l- (hydroxy- methylene)-2-keto - 10 -
methyl-1.2.5.8.9.10hexahydronaphthalene was obtained from
dltrans-2-keto-10-methyl-1. 2. 5. 8. 9. 10-hexahydronaphthalene and
dl-cis-1-(hydroxy- methylene)-2-keto-10-methyl-1. 2. 5. 8. 9.
10hexahydronaphthalene from dl-cis-2-keto-10- methyl-1. 2. 5. 8. 9.
10-hexahydronaphthalene.
In the first step of the process shown in the accompanying drawing
Compound I is reacted with a 5-keto-6-heptenoic acid ester of the
general formula
where R is an alkyl group having up to six carbon atoms such as
methyl, ethyl, propyl or butyl, in the presence of a quaternary
ammonium alkoxide and an inert organic solvent-such as dioxane,
isopropanol, butanol, isobutanol, tertiary butanol or pentanol.
Temperatures of 0 to 60~C. can be employed but it is preferred that
the reaction temperature be about 10 to 30~C.
The first step-in the process, i. e. the production of the addition
product Compound II is illustrated by the following : all parts are by
weight.
STEP I
To a reaction vessel is added and intimately mixed 14.1 parts of the
laevo-rotatory isomer of trans-1 - (hydroxy-methylene) -
2-keto-10methyl-1. 2. 5. 8. 9. 10-hexahydronaphthalene, 14. 9 parts of
methyl 5-keto-6-heptenoate, and 15. 6 parts of tertiary butanol and
the mixture cooled to 10-15 ~C. Thereupon approximately 2.4 parts of a
29.8% by weight n-butanol solution of benzyltrimethylammonium
nbutoxide admixed with approximately four parts of tertiary butanol is
added to the agitated mixture during 15 minutes. The mix is then held
at 20-25~ C. for 16 hours, seeded with a minute amount of the final
product and then held at 20-25~C, for 48 hours.
To the resultant mass is added, with agitation, 25 parts of petroleum
ether and the mixture cooled to about 0 C. The precipitate is filtered

off,-washed with petroleum ether, then with
water and dried. The white crystalline pro
duct so obtained is the laevo-rotatory isomer
of trans-1-formyl-1-(31-keto-61-carbomethoxy
hexyl)-2-keto-10-methyl-1. 2. 5. 8. 9. 10-hexa hydronaphth'alene
(Compound n en the aocam-
panying drawing when R is methyl), m.p.
66-67~C. [?]D25=-206 (C=2, chloroform).
In like manner dl-trans-1-formyl-1-(31-keto
61-carbomethoxy-hexyl) - 2 - keto-10-methyl
1.2.5.8.9.10-hexahydronaphthalene is obtained
from dl-trans-l-(hydroxy-methylene)-2-keto-
10-methyl-1.2.5.8.9.10-hexahydronaphthalene.
In the process of Step I other quaternary
ammonium-alkoxides may be employed
although benzyltrimethyl ammonium n-but
oxide is preferred, e.g. those having the general formula
in which Ri, R2, Rg and R4 are alkyl or aralkyl groups and Rs is an
alkyl group. Suitable alkyl groups are methyl, ethyl, propyl, butyl,
amyl and octyl, and suitable aralkyl groups are benzyl and phenethyl.
The preferred quaternary ammonium alkoxides are those in which
R1, R2 and R3 are straight chain alkyl groups having 1-4 carbon atoms,
R4 is benzyl and
R5 is a branched or straight chain alkyl group having 2 to 6 carbon
atoms.
In the second step of the process shown in the accompanying drawing
the adduct (Compound II) is heated with aqueous caustic alkali, such
as sodium or potassium hydroxide, to effect ring closure followed by
acidification to form a 1-(~-carboxyethyl) - 2 -
keto-14methyl-?5.9.11(1)-octahydrophenanthrene (Compound III).
The second step in the process is illustrated by the following : all
the parts are by weight.
STEP II
In a reaction vessel there are intimately admixed 19 parts of 85, %
potassium hydroxide, 100 parts of water, and 10 parts of the
laevo-rotatory isomer of trans-1-formyl1 -
(31-keto-61-carbomethoxy-hexyl) - 2 -
keto10-methyl-1.2.5.8.9.10-hexahydronaphthalene.
This mixture is heated to substantially 70~C. and held thereat for two
hours. The aqueous solution is cooled, admixed with an equal volume of
diethyl ether and the ether layer discarded. The aqueous layer is then
acidified with hydrochloric acid and extracted with several portions
of diethyl ether. The extracts are combined, washed with water, dried

and solvent removed under reduced pressure. The solid residue is
triturated with 75 parts of a mixture of diethyl ether and petroleum
ether, filtered and dried. The crystalline product so obtained is the
laevo-rotatory isomer of antitrans-1-(~-carboxyethyl) - 2 -
keto-14-methyl ?6.9.11(1)-octahydrophenanthrene, m.p. 101 102~C.,
[?]D25=-374 (C=2, chloroform).
In a similar fashion.
dl-anti-trans-1-(~carboxyethyl)-2-keto-14-methyl-?6.9.11(1)-octahydrop
henanthrene is obtained from dl-trans1-formyl-(31 - keto -
61-carbomethoxy-hexyl)2-keto - 10 -
methyl-1.2.5.8.9.10-hexahydronaphthalene.
In the third step of the process shown in the accompanying drawing the
carboxyl group of
Compound III is esterified in an acid medium with a substantially
anhydrous alkanol having up to six carbon atoms such as methanol,
ethanol, isopropanol or butanol, to provide the ester Compound IV.
This step may be carried out as follows: all parts are-by weight.
STEP III
In a reaction vessel there are intimately admixed 100 parts of the
laevo-rotatory isomer of anti-trans-1-(~-carboxyethyl)-2-keto-14methyl
- ?6.9.11(1)-octahydrophenanthrene, 350 parts of methyl alcohol and
17.5 parts of anhydrous hydrochloric acid. The mixture is heated at
65~C. for 4 hours. The solvent is removed under reduced pressure and
the residue taken up with diethyl ether, the ethereal solution washed
with aqueous sodium carbonate, then with water and then dried.
Upon removal of the ether under reduced pressure a light yellow oily
product, identified as the methyl ester of the laevo-rotatory isomer
of
anti-trans-1-(~-carboxyethyl)-2-keto14-methyl-?6.9.11(1)-octahydrophen
anthrene, is obtained.
Similarly the methyl ester of dl-anti-transl-
(-carboxyethyl)-2-keto-14-methyl-A'- octahydrophenanthrene is obtained
from dlanti-trans-1 - (~-carboxyethyl) - 2 - keto-14methyl -
?6.9.11(1) - octahydrophenanthrene and anhydrous methyl alcohol in an
acid medium.
Other acidic esterification catalysts may be employed, for example
sulphuric acid.
In the fourth step of the process shown in the accompanying drawing
the keto-acid ester (Compound IV) is converted to the corresponding 6.
7-cis-glycol (Compound V) by treatment of the former with the silver
salt of a low molecular weight fatty acid such as acetic acid and
bromine or preferably iodine in the presence of a low molecular weight
fatty acid such as acetic acid and then hydrolysing the half esters so
produced with alcoholic alkali metal hydroxide. Any ethylcarbalkoxy

groups which are hydrolysed may be subsequently re
esterified. This step is illustrated by the following : all parts are
by weight.
STEP IV
21. 6 parts of the methyl ester of the laevorotatory isomer of
anti-trans-1-(~-carboxy
ethyl)-2-keto - 14 - methyl-?6.9.11(1)-octahydro
phenanthrene is dissolved in 794 parts of glacial acetic acid and
therewith is intimately
mixed 26. 0 parts of silver acetate and 18. 5 parts by weight of
iodine. To the mixture is added 2. 5 parts of water and the mixture
then -agitated for 1 hour at 25 C. The mixture is heated to 90-100 C.
and maintained thereat for 3 hours, then cooled, filtered, and the
filtrate subjected to distillation under reduced pressure to remoye
the bulk of the acetic acid.
The residue is taken up with 400 parts of methyl alcohol and
neutralized with potassium hydroxide. To the resulting solution is
added 209 parts of a 4.5% by weight methanol solution of potassium
hydroxide and the mixture allowed to stand for 16 hours at 25 C. under
an atmosphere of nitrogen. The solution is then neutralized with 37%
hydrochloric acid and solvent removed under reduced pressure.
The residue is taken up in chloroform, washed with three portions of a
saturated sodium chloride solution, the washed chloroform solution
dried over magnesium sulphate, then filtered and the solvent removed
from the filtrate under reduced pressure. The oily residue thus
obtained contains a small amount of the l evo-rotatory isomer of
anti-trans-1-(B- carboxyethyl) - 2 - keto - 6.7 - dihydroxy - 14
methyl-?9.11(1)-decahydrophenanthrene but is principally its methyl
ester. This residue is then taken up in anhydro ! Ua methanol and
heatedimthepresenceofasmall amount of anhydrous hydrochloric acid. The
solvent is removed therefrom under reduced pressure and the oily
residue obtained taken up with chloroform, washed with several
portions of a saturated sodium chloride solution, then with water, the
chloroform solution dried over magnesium sulphate and the solvent
removed therefrom under reduced pressure. The colourless oily residue
is the methyl ester of the laevo-rotatory isomer of anti - trans - 1 -
(~ - carboxyethyl) - 2 - keto6.7-dihydroxy - 14 -
methyl-?9.11(1)-decahydrophenanthrene (Compound V in which R is
methyl).
In a similar manner the methyl ester of dlanti-trans-1-(~ -
carboxyethyl) - 2 - keto-6.7dihydroxy-14-methyl-?9.11(1) -
decahydrophenanthrene is obtained from the methyl ester of
dl-anti-trans-1- ( -carboxyethyl)-2-keto-14-
methyl-A'--octahydrophenanthrene.

In the fifth step of the process shown in the accompanying drawing the
6. 7-glycol (Compound V) prepared as above described is reacted with a
cyclic acetal-forming ketone in the presence of a dehydrating agent.
The preferred cyclic acetals (Compound VI) so produced are those
obtained from the symmetrical ketones such-as acetone, diethyl ketone,
cyclohexanone and para-methylcyclo- thexanone. This step is
illustrated by the following : all parts are by weight.
STEP V
20.8 parts of the methyl ester of the laevorotatory isomer of
anti-trans-1- (~-carboxy
ethyl)-2-keto-6.7-dihydroxy-14-methyl-@9.11(1)-
decahydrophenanthrene prepared as described in step IV, 112 parts of
anhydrous copper
sulphate and 960 parts of dry acetone are -intimately mixed at room
temperature for
about 60 hours. The reaction mass is filtered,
the filtrate treated with anhydrous potassium
carbonate, filtered and the filtrate subjected to
distillation under reduced pressure using a
water aspirator. The residue from the distilla
tion on recrystallisation from a benzene
petroleum ether mixture yielded the white
. crystalline laevo-rotatory isomer of the
acetonide of the methyl ester of anti-trans-1 (
-carboxyethyl)-2-keto-6. 7-dihydroxy-14-
methyl9 decahydrophenanthrene, m. p.
122-124 C., MD=-242. 5 (C=2,
chloroform).
Similarly the-acetonide of the methyl ester
of dl-anti-trans-1- ( -carboxyethyl)-2-keto-
6. 7-dihydroxy--14-methy19--decahydro-
phenanthrene is obtained from the methyl ester
of dl-anti-trans-l-( -carboxyethyl)-2-keto-6. 7
dihydroxy-14-methyl-A'-decahydrophenanthrene.
In the sixth step of the process shown in the
. accompanying drawing the 9. 10-double bond
of the acetonide (Compound VI) prepared as
described-above is selectively reduced with one
molecular proportion of hydrogen in the pre
sence of palladium. The reduction is carried
out in the presence of an inert organic solvent
which, is not reduced under the conditions of
the reaction. Examples of such solvents are
benzene, toluene, xylene, ethyl benzene, cyclo

hexane, the normally liquid alkanes and the
normally liquid aliphatic alcohols. This step is
illustrated by the following : all the parts are
by weight.
STEP VI
20 parts of the laevo-rotatory isomer of the acetonide-of the methyl
ester of anti-trans-1 (~-carboxyethyl) - 2 - keto-6.7-dihydroxy-14
methyl-A''-decahydrophehantbrene pre
pared as described in step V is admixed in a reaction vessel with
approximately 160 parts of isopropanol, 0.3 parts of 10% aqueous
sodium/ hydroxide and 4 parts of a 2.% palladium-strontium carbonate
catalyst (which had been-previously reduced). While agitating,
gaseous hydrogen is passed into the mixture
at 25 ~C. and.at a pressure slightly above
atmospheric pressure. After absorption of sub
stantially one molar equivalent (approximately
0. 0535 mol) of hydrogen the catalyst is filtered
off,; the filtrate neutralized with-acetic acid and
the solvent removed under reduced pressure.
. The residue is'taKen'up with chloroform,
washed with aqueous sodium bicarbonate, then -with water, dried over
magnesium sulphate and
then evaporated to dryness. The white crystal
line product thus obtained is the laevo-rotatory
isomer of the acetonide of the methyl ester of
anti-trans-1-(~ - carboxyethyl) - 2 - keto-6.7-dihydroxy-14 -
methyl-@11(1) - dodecahydro- -phenanthrene, m.p. 106-108~C., [alpha;]D
25=
-123~(C=2, Chloroform).
In a similar manner the acetonide of the methyl ester of
dl-anti-trans-1-(~-carboxyethyl)-2-keto-6.7-dihydroxy- 14
-methyl-@11(1)-
dodecahydrophenanthrene is obtained by selec-
-tively reducing the acetonide of the methyl
ester of dl-antl-trans - 1-(~-carboxyethyl)-2
keto-6.7-dihydroxy - 14 - methyl-@ 9.11(1)-deca-
hydrophenanthrene employing palladium as the
hydrogenation catalyst.
In the seventh step of the process shown in
the accompanying drawing the acetonide
(Compound VII) prepared as described above
is hydrolyzed with an acid under such condi
tions that the acetyl group is hydrolyzed with
out substantial hydrolysis of the carbalkoxy

group to the corresponding cis-glycol (Com
pound VIII), namely an alkyl ester of 1- (. P-
carboxyethyl) - 2 - keto - 6.7 - dihydroxy-14
methyl-@11(1)-dodecahydrophenanthrene. This
glycol is'preferably not isolated but oxidized
with a lower fatty acid salt of tetravalent lead
in the presence of a lower fatty acid (the
eighth step of the process) to a dialdehyde,
namely an alkyl ester of 1- (tO-carboxyethyl)-2-
keto-5. 6-di (formylmethyl)-6-methyl-Al (9'-
dctahydronaphthalene (Compound IX). This
dialdehyde is dissolved in an inert solvent, for
example, an aromatic hydrocarbon solvent and
cyclized by heating (ninth step of the process)
in the presence of a carboxylic acid salt of an
organic nitrogen-containing base such as
piperidine acetate to provide the correspond
ing alkyl ester of 3-formyl-3a-methyl-6-( -
carboxyethyl)-7-keto-A"""-octahydro-
, pentanthrene (pound X).
The following illustrates the preparation of the alkyl ester of
3-formyl-3a-methyl-6-(~
carboxyethyl) - 7 - keto-@ 2.5a(6) -octahydro-
pentanthrene (Compound X) from the cyclic -acetal the alkyl ester of
l- (-carboxyethyl)-2- keto-6. 7-dihydroxy-14-methyI-t-dodeca-
hydrophenanthrene (Compound VIII) : all the
parts are by weight.
STEPS VII, VIII & IX
9 parts of the laevo-rotatory isomer of the acetonide of the methyl
ester of anti-trans-1( -carboxyethyl)-2-keto-6. 7-dihydroxy-14-
-methyI-A'-dodecahydrophenanthrene prepared as described in step VI is
dissolved in
approximately 60 parts of acetic acid. There
upon 60 parts of water is added, intimately mixed and the solution
heated on a steam bath
for one ho r. The solution is cooled to 0-5 ~C. and 210 parts of water
added. To the resulting
solution of the cis-glycol is added at 0-5 C.
11.25 parts of lead tetra-acetate and 210 parts
of acetic acid. The slurry so obtained is
agitated for 10 minutes and thereto is added,
with agitation, 100 parts of water. The mix
ture is extracted twice using 373 parts of chloroform each time. The
extracts are com -bined and washed successively with dilute 'aqueous

sodium bicarbonate, 200 parts of 1 N
sulphuric acid, dilute aqueous sodium bi
carbonate, and finally with water and then
dried over magnesium sulphate, filtered and
the filtrate distilled under reduced pressure to
remove solvent. The oily residue is the dialdehyde, which is taken
up in 1350 parts of anhydrous benzene and heated to 80 C.
Thereto is added, with agitation, 3 parts of acetic acid and 2 parts
of piperidine. The resulting mixture is heated at 70-80 ~C. For about
one hour while passing nitrogen thereover and slowly distilling the
water-benzene azeotrope. The reaction mixture is cooled to room
temperature, washed successively with dilute hydrochloric acid, dilute
sodium bicarbonate and water, the solution dried over anhydrous
magnesium sulphate and solvent distilled from the dried solution under
reduced pressure. Upon recrystallization of the residue so obtained
from diethyl ether, the dextro rotatory methyl ester of
anti-trans-3-formyl3a-methyl-6-(~-carboxyethyl)- 7 -keto-@ 2.5a(6)-
octahydropentanthrene, m.p. 70-72 ~C., is obtained.
Similarly the methyl ester of
dl-anti-trans-3formyl-3a-methyl-6-(~-carboxyethyl)- 7 -keto@2.5a(6)
-octahydropentanthrene obtained by the acid hydrolysis of the
acetonide of the methyl ester of dl-anti-trans-1-(~-carboxyethyl) - 2
- keto - 6.7-dihydroxy-14-methylA-dodecahydrophenanthrene, cleavage of
the glycol so obtained and ring closure of the resulting dialdehyde.
In the tenth step of the process shown in the accompanying drawing the
2. 3-double bond of the alkyl ester of
3-formyl-3a-methyl-6-(~carboxyethyl) - 7 - keto-@
2.5a(6)-octahydropentanthrene (Compound X) prepared as described
above is selectively reduced with one molecular proportion of hydrogen
in the presence of palladium to provide the alkyl ester of
3formyl-3a-methyl-6-(~-carboxyethyl)- 7
-keto@5a(6)-decahydropentanthrene (Compound XI).
The reduction is carried out in the presence of an inert organic
solvent, which is not reduced under the conditions of the reaction.
This step is illustrated by the following : all the parts are by
weight.
STEP X
35. 8 parts of the dextro-rotatory methyl ester of
anti-trans-3-formyl-3a-methyl-6-(~carboxyethyl) - 7 - keto-@2.5a(6)
-octahydropentanthrene prepared as described in steps VII,
VIII and IX, is admixed in a reaction vessel with 800 parts of
isopropanol and 15 parts of a 2% palladium-strontium carbonate
catalyst (which had been previously reduced). While agitating, gaseous
hydrogen is passed into the mixture at 25 ~C. and at a pressure

slightly above atmospheric pressure. After absorption of substantially
one molar equivalent (approximately 0. 114 mol) of hydrogen, the
catalyst is filtered off and the solvent removed under reduced
pressure. The oily residue is the dextro-rotatory methyl ester of
anti-trans-3- formyl-3a-methyl-6-(~-carboxyethyl) -
7-keto@5a(6)-decahydropentanthrene.
In a similar manner the methyl ester of
dl-anti-trans-3-formyl-3a-methyl-6- (ss-
carboxyethyl)-7-keto-A'-decahydropentanthrene is obtained from the
methyl ester of dl-anti-trans-3-formyl-3a-methyl-6-(ss-
carboxyethyl)-7-keto-A'-octahydropentanthrene employing palladium as
the reduction catalyst.
In the eleventh step of the process shown in the accompanying drawing
a cyclic ketal derived from an. alpha;~-glycol such as the
monoethylene ketal, namely, an alkyl ester of 3-[21
(11.31-dioxacyclopentanyl)] - 3a - methyl-6-(~carboxyethyl) - 7 -
keto-@5a(6)-decahydropentanthrene (Compound XII), is prepared by
heating an alkyl ester of 3-formyl-3a-methyl6- (-carboxyethyl)-
7-keto-A"''-decahydro-' pentanthrene prepared as described above with
an. ss-glycol such as ethylene glycol in the presence of an acid
condensation catalyst e. g., a toluene sulphonic acid and a
water-entraining agent. This step is illustrated by the- following :
all the parts are by weight.
STEP XI
Approximately 35 parts by weight of the dextro-rotatory isomer of the
methyl ester of anti-trans-3-formyl-3a-methyl-6-(ss-carboxy-
ethyl)-7-keto-A'-decahydropentanthrene prepared as in Step X is
dissolved in a mixture of 2500 parts of dioxan and 4500 parts of
benzene. Thereto is added and intimately mixed 7. 8 parts of ethylene
glycol and 1 part of para-toluene sulphonic acid. The reaction mass is
brought to reflux and the benzenewater-azeotrope slowly distilled off.
Thereafter the mass is subjected to distillation under reduced
pressure to remove the solvent. The residue is taken up in chloroform,
and the chloroform solution washed with aqueous potassium carbonate
followed by a water wash.
The chloroform solution is dried and the solvent removed under reduced
pressure. The residue on recrystallization from diethyl ether forms
white crystals of the dextro-rotatory 3monoethylene ketal of the
methyl ester anti trans-3-formyl-3a-methyl-6- (P-carboxy-
ethyl)-7-keto-A"''-decahydropentanthrene, m. p. 99-101 C.
In a similar manner the methyl ester of dl-anti-trans-3-
[21-(11.31-dioxacyclopentanyl)] 3a-methyl - 6 -
(~-carboxyethyl)-7-keto-@5a(6)- decahydropentanthrene is obtained by
heating ethylene glycol with the methyl ester of dlanti-trans- 3

-formyl-3a-methyl-6-(~-carboxyethyl)-7-keto-@5a(6)-decahydropentanthre
ne in the presence of an acid condensation catalyst.
In the twelfth step of the process shown in the accompanying drawing
an angular methyl group is introduced at the 6-position of the
pentanthrene nucleus by heating methyl iodide in an inert organic
solvent (or like methylating agents such as dimethyl sulphate and
methyl tosylate) with the above alkyl ester e.g. the alkyl ester of
3-[21-(11.31-dioxacyclopentanyl)]3a-methyl - 6 - ~-carboxyethyl-7-
keto-@5a(6)- decahydropentanthrene (Compound XII) under alkaline
conditions, e. g., by adding an alkali metal alkoxide. In the
introduction of the- angular methyl group an additional asymmetric
carbon atom is formed and thus mixture of stereoisomers results i. e.
the-and, ss-keto esters. This mixture is preferably not isolated or
separated into its isomeric parts, but converted directly by
hydrolysis in the presence of-water and acid (step thirteen of the
synthesis)--to-the corresponding carboxyethyl derivative (Compound
XIV). The carboxyethyl-derivative-thus obtained-is, for example, a
mixture of isomeric anti-trans-3-[21-(Il. 3l- dioxacyclopentanyl)] -
3a - 6-dimethyl-6-(~carboxyethyl) - 7 keto - @5 - decahydropent-
anthrene ; these isomers may be represented su ucturally and deEned as
follows :-
"-keto acid -keto acid
Although both of the isomeric N and uss-keto- acids may be converted
to tetracyclic ketones having the general formulas of Compounds
XV, XVI and XVII of the accompanying drawing the in-eta acid gives
rise to a tetracyclic ketone of the polyhydrocyclopentanophenanthrene
series whose angular methyl groups are on the same side of the
cyclopentanophenanthrene reference plane while the s-keto acid gives
rise to a tetracyclic ketone whose angular methyl groups are on
opposite sides.,j.
The introduction of the angular methyl group in the : 6-position of
the pentanthrene nucleus of a 3-cyclic ketal of an alkyl ester of
3-formyl - 3a.- methyl-6-(~-carboxyethyl)-7keto-@
5a(6)-decahydropentanthrene to provide a 3-cyclic ketal of an alkyl
ester of 3-formyl3a.6-dimethyl - 6 -
(~-carboxyethyl)-7-ketoA5-decahydropentantbrene (for example,
Compound-XIII) and conversion thereof to the free acid (for example,
Compound XIV) is illustrated by the following : all-the parts are by
weight.
STEPS XII & XIII
12. 22 parts of dextro-rotatory mono-ethylene ketal of the methyl
ester of anti-trans-3- formyl--3a-methyl--6- (a-carboxyethyl)-7-
Jketo-A'-decahydropentanthrene prepared as in Step XI is dissolved in

a mixture of 360 parts of benzene and 320 parts of tertiary butanol.
Thereto is added and intimately mixed 285 parts of 0.467 N potassium
tertiary butoxide in tertiary butanol. While refluxing the mixture 41
parts of methyl iodide is cautiously added. Upon completion of the
addition the reaction mass is refluxed for 5 minutes and then cooled
to room. temperature.
This-solution which contains the respective methyl-esters of the and
f3-anti-trans-keto acidsinaweight ratio of approximately 1 to 2 is
admixed with 200 parts of water in order to hydrolyze the esters. The
organic layer is separated and extracted with dilute aqueous potassium
hydroxide. The organic layer is separated and cooled to 0-3 C.,
admixed with an equal volume of diethyl ether and the mixture then
acidifie with dilute sulphuric acid. The aqueous layer is removed and
extracted with two equal volumes of diethyl ether. The ether extracts
are combined, washed with water and dried. Upon removal of the ether
under reduced pressure 11. 96 parts of an oil consisting of the < and
{S isomers of the keto-acid in a weight ratio of approximately 1 to 2
is obtained.
-The oily mixture of"-and -keto acids may be separated into its
component parts by various well-known methods, for example, by
dissolving the oil in a low molecular weight alkanol such as methanol,
admixing therewith a chemically equivalent weight of quinine, and
refluxing the reaction mass. Upon cooling to room temperature or below
the respective quinine salts may be effectively separated by
fractional crystallization. The quinine salts on treatment with an
alkaline material more basic than quinine in an aqueous medium,
followedby separation of the free quinine, and subsequently acidifying
with mineral acid yields the respective-and tq-keto acids in separated
form.
In general, however, the mixture is not separated into its component
keto-acid isomeric parts but heated (step fourteen of the process)
with an organic carboxylic acid anhydride such as acetic anhydride in
the presence of a catalytic amount of an alkali metal salt of the same
carboxylic acid, e. g. sodium acetate. By so doing an enol lactone
e.g. 3-keto-17-[21-(11.31-dioxacyclopentanyl)] cyclopentano - 10.13 -
dimethyl-@ 5.9(11) -4-oxa- decahydrophenanthrene (Compound XV), is
obtained as a mixture of isomers which correspond with those of the
acid. This reaction is preferably carried out in an atmosphere of an
inert gas.
This step is illustrated by the following : all parts are by weight.
STEP XIV
11. 96 parts of the oily mixture of keto-acids obtained in Step XIII
is dissolved in 162 parts of acetic anhydride containing 0. 1 part of
sodium acetate and renuxed for four hours under an atmosphere of

nitrogen. The reaction mass is then cooled. The acetic anhydride is
removed under reduced pressure and the residue taken upwith diethyl
ether. The solution is washed with aqueous sodium bicarbonate, then
with water and dried. Upon. removal of the ether under reduced
pressure an oil is obtained which on standing crystallises. The yield
is 9. 95 parts of a mixture of ?- and ~-enol lactones in an
approximately 1 to2.weight ratio.
In the fifteenth step of the process shown upon the accompanying
drawing the enol lactone (Compound XV) prepared as described in steps
XII and XIII is converted to the corresponding tetracyclic ketone
(Compound
XVI), e.g. to the mono-ethylene ketal of 3keto-17-formyl -
cyclopentano-10.13-dimethyl@ 4.9(11)-decahydrophenanthrene, by
reacting the former with a methyl magnesium halide at a low
temperature in diethyl ether, decomposing the addition product with
acid, and then heating the ether soluble product with an alcohol
solution of an alkali metal hydroxide. This step affords an
opportunity for conveniently separating the unwanted a-stereoisomer
from the desired ss-stereoisomer since the a-stereoisomer of the enol
lactone does not react in the manner indicated. This step is
illustrated by the following : all the parts are by weight.
STEP XV
9.95 parts of the crystalline mixture of alpha;and ~-enol lactones
prepared by Step XIV is dissolved in a mixture of 500 parts of diethyl
ether and 175 parts of benzene and cooled to below-50 C. Thereto is
added with agitation an ether solution containing 4. 25 parts of
methyl magnesium bromide while maintaining the temperature below-50 C.
Upon completion of the methyl magnesium bromide addition the mixture
is stirred at-50 to-55 C. for 90 minutes. Thereafter 50 parts of
acetone, 60 parts of water and 20 parts of acetic acid are added and
intimately mixed and the mixture permitted to rise to about 0 C. The
layers are separated and the ether extract washed with aqueous sodium
carbonate, then with water, dried and the ether removed under reduced
pressure. The oily residue is taken up in 400 parts of methyl alcohol,
72 parts of a
16. 7l% aqueous solution of potassium hydroxide added thereto and-the
mixture so obtained refluxed for 2 hours under an atmo
sphere of nitrogen. Thereupon substantially all of the methanol is
removed under reduced pressure. An equal volume of water is added to
the residue, and the resulting mixture twice extracted with equal
volumes of chloroform.
The extracts are combined, dried and distilled under reduced pressure.
6. 51 parts of an oily. residue which partially crystallizes on
standing is obtained. The residue is dissolved in methanol and set

aside to permit crystallization. White crystals of the optically
active mono-ethylene ketal of A'"'-2l-norprogester-
one, m. p. 172175 C. [a] D25=+70. 6 (C=2, chloroform), are obtained.
In a similar manner the mono-ethylene ketal of white crystalline dl-@
9(11)-21-norprogesterone is obtained by proceeding through the
processes set forth in Steps XII-XV and beginning with an alkyl ester
of dl-anti-trans3-[21-(11.31-dioxacyclopentanyl)] -
3a-methyl6-(~-carboxyethyl) - 7 - keto-@5a(6)-decahydropentanthrene.
In the sixteenth and final-sep of the pro
cess shown on the accompanying drawing the
mono-ethylene ketal (Compound XVI) pre
pared as described above is converted to the
corresponding 17-formyl-cyclopentano-10.13 dimethyl-@
4.9(11)-decahydrophenanthrene-3-one
(Compound XVII) by heating the former in
the presence of aqueous acid. This is illustrated
by the following :. all the parts are by weight.
STBP XVI
5 parts. of the mono-ethylene ketal obtained
by the process of Step XV is heated with 5000
parts of 50% aqueous acetic acid at 100 C.
for 90 minutes. The reaction mass is distilled
under reduced pressure and the residue taken up in chloroform. The
chloroform solution is
washed with aqueous sodium bicarbonate and
finally with water and dried. Upon removal of
the chloroform an oily residue is obtained
which on crystallization gives the white crystal
line dextro-rotatory isomer of A"'-21-nor-
progesterone, m.p. 127-131~C.
Similarly dl-@9(11) - 21 - norprogesterone is
obtained from the mono-ethylene ketal of dl A''-21-norprogesterone.
The compound obtained by Step XVI is
identical with that obtained by reacting one
molar equivalent of hydrogen with the dextro
rotatory isomer of @ 9(11) 16 -21-norprogesterone
(m.p. 160.5-161.5 ~C.) in the presence of
palladium.
What we claim is :-
1.1-(~-carboxyethyl) - 2 - keto-14-methyl @ 6.9(11)1
octahydrophenanthrene) and its alkyl
esters having up to six carbon atoms in the
alkyl group.
2. Anti-trans-1-(~-carboxyethyl) - 2 - keto 14-methyl-@

6.9.11(1)-octahydrophenanthrene and
its alkyl esters having up to six carbon-atoms
in the alkyl group.
3. Laevo-anti-trans- 1 -(~-carboxyethyl)-2 keto-14 -methyl -@
6.9.11(1) - octahydrophenanthrene and its alkyl esters.
4. The methyl ester of 1-(~-carboxyethyl) 2-keto- 14-methyl -
@6.9.11(1) -.octahydrophen-
anthrene.
5. The methyl ester of anti-trans-l-(, ss-carboxyethyl)- 2 -keto-14
-methyl - @ 6.9.11(1) - octa-
hydrophenanthrene.
6. The methyl ester of Zaevo-anti-trans-1- (~-carboxyethyl)
-2-keto-14-methyl- @ 6.9.11(1) -octahydrophenanthrene.
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* GB785076 (A)
Description: GB785076 (A) ? 1957-10-23
Method for packing cigarettes, cigarillos, or the like
Method for Packing Cigarettes, Cigarillos, or the Like.
I,. KuRT-KoxER, a German Citizen, of 10 Am
Pfingstberg,-Eamburg-Bergedorf, Germany, 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 has ; for its. object a method for packing
cigarettes, cigarillos or the like in a soft packing in which a

divided part of the top closure is adapted to be closed down with the
inclusion of a finger grip strip or"tearer"strip whereby this strip
can be operated only by destroying a sealing element.
The method according to the present invention is characterised in that
a finger grip strip withdrawn from a magazineorirom'a reel is folded.
around part of a cigarette block and projects to a certain extent
beyond the length thereof, these operations being performed in a
modified packing machine of known type or of desired-type before the
cigarette block is. brought against a tin foil wrapper provided with
slits or perforations at two opposed points so that the projecting end
of the strip is folded in on folding the top closure in such manner
that it is in the form of a loop enclosing a corner section of the top
closure separated-from the-rest of the top closure by means of the
slits or perforations and is arranged to lie above, the < finally
folded top cl'osure and below the sealing element subsequently to be
applied thereto and projects therefrom.
The method can be effected on a machine designed for this method or on
a normal packing'. machine with the assistance of suitable additional
devices. In carrying out the method nnger grip strips are withdrawn
from a withdrawal device, for example, a magazine, or from a reel with
an associated severing device, byr means of a-gripper,. for example a
pivota suction gripper, and these strips are laid in front of the end
face of the block of cigarettes withdrawn from a cigarette magazine
and are wrapped in U-form around the block on the further, movement
thereof.
By suitable i'mplementsjfor example cutters, the tin foil sheet
leaving a tin-foil apparatus receives slits or perforations for
limiting the part of the top which is lifted on opening the package.
The tin foil. wrapper is then applied without closing its top, and
then the liner or cover is applied whereby the finger grip strip
projects from one end-of the package. After the application of a
closure label on the wider side the closing of the top is effected at
the narrow side whereby also tlie'finger-grip strip is laid in the
form of a fold around the abutting flaps. Then the top closure is
completed, the closure label is folded and the projecting part of the
finger grip strip is laid on the end of the package. Finally the.
package is sealed by means of a sealing element.
According to further feature of the invention the closure label can be
omitted if the top closure. is effected by means of adhesive on.
theupperbroader,Bap or is effected by other suitable closure
elements."
Hereinafter the method is described on the basis of the accompanying
drawing in two examples. These show in Fig. 1 the diagram of a packing
machine with the individual sections A to H, Figs 2-. and 3 show

details of the. stations D to G ; Figs. 4 to 10 show packages in
various working stages of the head closure with a closure label, and
Figs.
11 to 16 show packages in various treatment stages. where top closure
is effected by means of adhesive.
According to Fig. 1 at the station A blocks of cigarettes are
withdrawn from, a cigarette magazine 1 and formed to a. block 18 (see
also Fig. 4) and fed towards the station B in which is located a
magazine for the finger grip strips 2, whichis pivotally arranged upon
a bearing 3, whereby the magazine may be moved towards and away from a
rotary
cross member 4 as indicated by the double cyctes & e cross member 4
withdraws the
lowermost strip from the magazine which
then moves away from the cross member as the latter rotates to
position the strip 2 over
the path of movement of the successive
blocks 18. The finger grip when brought to
this position is allowed to drop into'the path.
of movement of said blocks andas each successive block moves forward
the strip 2 is laid around the blocks 18 in the manner indicated in
Fig.. 4.. A tinfoil wrapper. feed
apparatus 5 of known kind is provided with cutters 6 which cut slits
19 or perforations in the tinfoil sheet 20 as shown in Fig. 4. Fig. 4
shows the moment at which a cigarette block
18 is pressed against the wrapper 20 with the finger grip strip 2
brought into-U form by the feed action.
The wrapping in tinfoil without top closure
and the introduction into a liner or cover 21
in the liner or-cover apparatus 7 at the station
C is effected in the usual way. Fig. 5 shows
the condition of the package after leaving this
station.
-At-the point D a normal label applying
apparatus 8 applies a closure label 12, Fig. 6,
on the wider side of the package the package
being moved on between guides by means of
the chain 17 shown in Fig. 2. The adhesion
of the closure label is to be effected laterally, i. e. on the
right-hand side of the slit 19, as
shown in Fig. 6, so that the latter is not
covered by the closure label. At the station
E a carriage 9 takes over the package. On the
latter there is effected in known manner by

means of-two folder blades of different
lengths, the formation of the top tucks on
the narrower side and at the same time part
of the finger grip strip 2 is folded reentrantly
about the inturned fiap, as shown at 2a, so
that the package shown in Fig. 6 is produced.
Thereupon the top closure is. effected by
means of a reciprocating folder blade 10 and
by a pivoted blade 11 at the station F and
simultaneously the label 12 is folded over the
end face of the package-as shown on the
Fig. 7. At the same station F-a rotary brush segment 13 folds the
label 12 completely down as shown in Fig. 8. Thereupon by means of a
plunger 22 the end part of the finger strip 2, which so. far has
projected away from the package,. is folded on to the end face of the
package as shown in Fig. 9. boy the conveyor. chain 14 the packet is
then
supplied to a sealing element apparatus at
station G which lays the sealing element 23
transversely over the finger grip strip 2 so that
both the closure label 12 as also the slits 19
of the tin foil liner are covered. The finished
package shown in Fig. 10 then passes to a
take-off device of known kind provided at
station H.
From Fig. 10 it is to be seen that the finger grip strip projects by
its grip end 2'past the sealing element so that on lifting this end
the sealing element is torn off,, an'dq the package is opened by the
corner di'vided off by the slits 19 and the cigarettes disposed in the
region of this corner are lifted cut of the package.
By the method according to the-second embodiment. the tin foil
wrapper. receives a supply of adhesive 24 at the station B as
showninFig 11. Fig 12showsthecondition after station C and Fig. 13
after passing the station E in which case of course the station
D is now omitted. shows the top closure effected by adhesive. Fig. 15
corresponds to the condition of the package after station F and Fig.
16 again shows the finished package.
Instead~of usirrg an adhesive'the folds of the top closure part to be
held closed on opening the package can also be held together by means
of interlocking folds or the like.
It will be seen that the production of the packages described can be
effected on known packing machines if the features described are
included. In particular it is convenient to construct the device
serving for applying and folding the finger grip strip as an

additional unit in order that the latter can be fitted to existing
packing machines.
What I claim is:
1. Method for packing. cigarettes, cigarillos or the like in. which a
part of the top closure, separate from the rest of said closure, is
adapted to be lifted up by means of a finger grip strip which can be
operated only by destruction of a sealing element, characterised in
that a finger grip strip withdrawn from a magazine or from a reel is
folded around part of a cigarette block and projects to a certain
extent beyond the length thereof, these operations being performed in
a modified packing machine of known type or of desired type. before
the cigarette block is brought against a tin foil wrapper provided
with slits or perforations at two opposed points so that the
projecting end of the strip is folded in on folding the top closure in
such manner that it is in the form of a loop enclosing a corner
section of the top closure separated. from the rest of the top closure
by means of the slits or perforations and is arranged to lie above the
finally folded top closure and below the sealing element sub ;
sequently to be applied thereto and projects therefrom.
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* GB785077 (A)
Description: GB785077 (A) ? 1957-10-23
Improvements in electrolytic capacitors
PATENT SPECIFICATION
Inventors: PAUL CRAWFORD LAKIN and ROY ALLEN CANTY 785,077 Date of
Application and filing Complete Specification: July 5, 1955.

No 19414/55.
Complete Specification Published: Oct 23, 1957.
Index at acceptance:-Class 37, D 3 G( 1: 2: X).
International Classification:-D Oll.
Improvements in Electrolytic Capacitors We, P R MALLORY & Co INC, a
company incorporated under the laws of the State of Delaware, United
States of America, of Indianapolis, Indiana, 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 ant by the following statement:-
This invention relates generally to electrolytic capacitors and has
specific application to such apparatus including means and methods for
providing such capacitors adapted for use with miniaturized electrical
circuits or components.
In the progress of the electrical arts, especially as relating to
communications and computers, electron tubes may be replaced by
devices wherein electrons are controlled in a solid instead of in a
vacuum, Since these devices are much smaller in physical character and
structure and require different voltages applied thereto, it is
desirable and often necessary that the components functionally
associated with such devices be fabricated and constructed in reduced
physical and electrical ratio However, the speed of development in the
construction of such miniaturized electrical components in accordance
with the pace of the development of crystal amplifiers known as
"transistors" has presentedt a great many problems.
Thus, with relation to miniaturized electric capacitors, the
cooperation' of the component parts require different modes of
assembly and construction As an example, the conventional structural
method for sealing electrolytic capacitors such as by crimping down
against a shoulder or head formed in a capacitor case, or= by crimping
the case against the side of, a rubber plug, would, in
non-miniaturized constructions, usually result in such a seal
olccupyinfig a relatively large volume of the capacitor.
Therefore; if crimping were to be used, another type of crimping
construction has to be found and used so that the physical
relation(Price 3 s 6 d l ships between the components of the capacitor
would be regulated.
The present invention meets and overcomes several of the attendant
problems lcreated by the aforesaid aspects of miniaturization and
affords a construction for the miniature electrolytic capacitor
wherein a tight seal is obtained with very low weight loss using
liquid electrolytes Moreover, the seal occupies a volume of the total
capacitor volume much, less than that previously obtainable by normal

crimping methods.
An object of the present invention is to provide a compact, efficient
electrolytic capacitor for use with printed or miniature circuits and
which is economical to fabricate and manu:
facture.
Another object of the present invention is to improve the construction
of electrolytie capacitors especially by providing means for sealing
the same so as to adapt them for utility in, small miniature type
circuits.
For illustrative purposes the invention will be described in
connection with the accompanying drawing in which:
Fig 1 is a top, plan view of the electrolytic capacitor construction
of the present invention, with portions thereof broken away so as to
more explicitly define the mode of assembly thereof; Figure 2 is a
vertical cross-sectional view of the miniature electrolytic capacitor
Iconstruction of the present invention as taken along line 2-2 thereof
and as shown in Fig.
1; and Figure 3 is an expanded view of the present invention
illustrating a miniaturized electrolytic capacitor as shown in the
above figures.
Generally speaking, the present invention provides a miniaturized
electrolytic capacitor which is operable in printed and solid type
amplifier circuits In the construction of a capacitor of such small
dimensions it is important that the sealing construction be such that
an exceedingly small portion of the entire device be used This
is-necessary inasmuch as 1 ; the overall dimensions of the electrical
capacitor is exceedingly small and the sealing means for such a device
must, in turn, be kept within rigid volumetric limits so as to enable
as much of the construction as possible to be used for the internal
portion of the device, per se In the construction of the hereinafter
described eldctrolytic capacitor, this is achieved by providing an
internal rigid construction for the capacitor which aids in effecting
the sealing of an inert electrolyte within the capacitor in such a way
that very little volume is necessary for the sealing In essence, ihe
capacitor includes a double container type of seal wherein one of the
containers is inverted and held within its companion in such a manner
that a rigid shoulder is obtained upon which a gasket may be
placed-and seated A portion of the outside container is crimped over
the gasket construction seated on the internal container so as to
provide a rigid and substantially air-tight seal.
In the Icapacitor construction, the double can construction is
fabricated individually of a thin sheet of fine silver metal
approximately 006 t thick The gasket material is fabricated of an
elastomer and may be molded to the desired configuration At the bottom

of the outside casing a headed wire structure may be spot welded
thereto so as to provide one of the terminals of the device:
Referring now to the'figures of the drawing, a miniature electrolytic
capacitor 10 is represented The capacitor comprises an outside metal
casing 11 made from a fine sheet of silver whiclh is configured in the
shape of an open ended can or cup The casing, which is adapted to act
as a cathode, has elongated, side walls 12 and 13 interconnected by a
bottom 14 A terminal post 15 is connected substantially at the centre
of the bottom wall 14 and may be welded thereto The side walls 12 and
13 are angulated, in the assembly thereof, so as to provide tapered
walls 20 and 21 which will be adapted, as hereinafter shown, to grasp
and contain a molded gasket 16 adapted to aid in the sealing of the
electrolytic device An, internal anode section 17, here shown, as
being fabricated of tantalum, is placed within the casing of the
electrolytic device.
This sectionl 17 has a terminal 23 connected substantially centrally
to the top thereof The terminal 23 is adapted to penetrate gasket 16
which includes an aperture 18 therethrough.
Placed about the anode capacitor section i 1 an insulator tube 30
having a configuration such that it will be adapted to surround the
aforesaid capacitor anode section and insulate the same from the
cathode' A second or interiial casing 31, including side Wralls 35, 36
and a tfop wall 37 having a central aperture cut therethrough, is
inverted within the first casing so that thf side walls are contiguous
to the inside surfaces 50, 501 of side walls 12 and 13 respectively
The length of the walls of the second casing is of such extent that
they terminate adjacent the bottom wall 14 of the first casing 11 It
is to be noted that the second casing 31 is open ended at the 70
bottom to form a cup-shaped structure with the top wall thereof having
a central aperture.
The gasket 16 for the electrolytic capacitor is placed between the top
portions 20, 21 of the first casing 11 and the top wall 37 of 75
second casing 31 This gasket, as stated, is made of an elastomer and
is preferably molded, having a punched hole centrally disposed
therethrough The gasket comprises a main conical section 60 having a
tapered wall 63 80 and a dependent central section 61 extending from
said main section and being integrally formed or molded thereto by
means of a shoulder portion 62 The extension 61 has a tapered wall 65
and is adapted by means of 85 the central aperture to circumscribe the
lead or conductor 23 acting as a terminal for the electrolytic
capacitor section.
In the assembly of the capacitor, insulating tube 30 is first slipped
over anode section 17 90 -and mashed down to insulate both ends
thereof Next, the anode section, 17, covered by insulating tube 30, is

inserted in the inside cup structure 31 with its lead penetrating the
small hole made in the end of the insulating 95 tube; the entire
structure being pulled up snugly therein Then, the lead attached to
the top, surface of the anode is forced through the centre of gasket
16 starting in the centre of the projection with the gasket being slid
down 100 the lead t Q approximately,s inch from the cup.
The next step is to fill the outside container 11 with an electrolyte
to a predetermined level.
Then the inside cup 31 and anode 17 is slowly inserted therein This is
done gradually so as 105 to allow the air to escape without forcing
the electrolyte out When this sub-assembly is in place, the gasket is
pushed down and the outside case is crimped.
As finally assembled, the second silver 110 casing extends all the way
to the bottom of the first casing The gasket lies in the remaining
space aboye the top wall of the second Casing and between the top
portion of the first casing with the extension fitting against 115 the
electfrolydtic capacitor section 17 so as to have the terminal extend
centrally therethrough The container is crimped at a 45 anglie until
the gasket materials are extruded or swollen out past the top portion
of the 120 first casing Thus, in this construction, the rubber will be
under the proper compression so as to take-care of expansion and
contraction of-the containir through temperature changes for still
maintaining a good seal The angle of 125 the'gasket, here determined
as being 45 , is adapfed to-allow the outside container to be crimped
-lightly before touching the rubber.
This will then keep the gasket in plaice so that it will not push out
on one side or deforan the 130 785,077 said inner casing.
2 A sealed electrolytic capacitor according
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