4481 4485.output

* GB784888 (A)
Description: GB784888 (A) ? 1957-10-16
Improvements in or relating to apparatus for the catalytic cracking of
hydrocarbon oils
Description of GB784888 (A)
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The EPO does not accept any responsibility for the accuracy of data
and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
PATENT SPECIFICATION
7849888 Date of Application and filing Complete Specification June 22,
1955.
No 18107/55.
a x e S Application made in United States of America on June 24, 1954.
Complete Specification Published Oct 16, 1957.
Index at Acceptance: -Classes 1 ( 1), A 3 (A 1 A: B 2 A); and 32, El.
International Classification: -B Olj Cl Og.
COMPLETE SPECIFICATION
Improvements in or relating to Apparatus for the Catalytic Cracking of
Hydrocarbon Oils We, N V DE BATAAFSCHE PETROLEUM MAATSC Fi APPIJ, a
company organised under the laws of The Netherlands, of 30 Carel van
Bylandtlaan, The Hague, The Netherlands, 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 new and improved apparatus for the
catalytic cracking of hydrocarbon oils using a fluidised catalyst, the
apparatus having both a novel flow arrangement and a novel arrangement
of its essential component parts which is adapted to a specific type
of catalytic cracking process allowing substantially increased
optimum-conversion levels, substantially increased gasoline yields and
product values, and substantially decreased coke production.
In the specification of our Patent Application
No 16616/55 (Serial No 784,546) there is described a process for the
catalytic cracking of hydrocarbon oils, called " controlled catalytic
cracking ", which affords substantially increased optimum conversion
levels, substantially increased gasoline yields and product-values,
and substantially reduced coke production This type of cracking
operation cannot be carried out in the conventional catalytic cracking
apparatus A catalytic cracking apparatus according to the present
invention, allows such a process to be carried out both practically
and economically with a low capital expenditure and low operating
cost.
According to the present invention there is provided apparatus for the
catalytic cracking of hydrocarbon oils comprising in combination a
fluidized catalyst regenerator vessel, a catalyst separator-hopper
vessel, a catalyst stripper vessel, and a fluidized catalyst reactor
vessel, each disposed substantially vertically and the four being
arranged in plan roughly in a circle, the catalyst separator-hopper
vessel being at the highest elevation and being provided with a
standpipe opening into the fluidized catalyst reactor vessel near the
lPice 3 s 6 d l bottom thereof, the fluidized catalyst reactor vessel
being situated at a lower level and being provided with an inclined
standpipe communicating with a substantially vertical riser line
opening into the stripper vessel above the normal catalyst bed level
therein, the stripper vessel being provided with an inclined standpipe
communicating with a substantially vertical riser line opening into
the regenerator vessel above the normal catalyst bed level therein,
and the regenerator vessel being provided with an inclined standpipe
communicating with a substantially vertical riser line opening into
the catalyst separator-hopper vessel.
In apparatus for use in a catalytic cracking process such as that
described in the specification of Patent Application No 16616/55
(Serial No 781,916) the said riser line opening into the catalyst
separator-hopper vessel is a riser reactor into which the oil vapour
to be subjected to first stage catalytic cracking is injected at the
bottom, the oil vapour injected into said reactor vessel being that to
be subjected to second stage catalytic cracking.

In a modification of apparatus according to the present invention, the
separator-hopper vessel is arranged wholly or partly within the upper
part of the reactor vessel, and the fluidised catalyst regenerator
vessel, the catalyst stripper vessel and the fluidised catalyst
reactor vessel are arranged roughly in a circle.
An apparatus according to the present invention will now be described
with reference to the accompanying drawing, in which Figure I shows
the arrangement of the main vessels and lines of the plant in oblique
projection, and Figure II shows a plan of the arrangement.
Referring to Figure II, the apparatus is arranged so that the catalyst
circulates (counter-clockwise as the apparatus is shown in Figure II)
through four vessels which are arranged in plan roughly in a circle In
circulating, the catalyst undergoes a number of changes in elevation
In each case the raising of the catalyst to a higher elevation is
effected in a confined vertical conduit, the catalyst being 784,888
transported in the form of a dilute suspension and horizontal movement
around the circuit shown in the plan view is, in each case, effected
by movement of the catalyst by gravity in an inclined confined path in
the form of a dense (pseudo-liquid) phase.
Referring now also to Figure I, the apparatus comprises a
substantially vertical riser reactor 11, forming a first stage
catalytic cracking reactor and four vertically disposed essentially
cylindrical vessels which are a fluid catalyst regenerator vessel 1, a
catalyst separator-hopper vessel 2, a second stage fluid catalyst
reactor vessel 3 and a fluid catalyst stripper vessel 4 The
separator-hopper vessel 2 is the most elevated of the vessels, being
approximately level with the top of the regenerator vessel.
The reactor vessel 3 is at a lower position and the stripper vessel 4
is preferably located at a still lower elevation Each of these vessels
1-4 is provided, preferably substantially at the bottom, with an
inclined standpipe 5 6, 7, or 8 respectively, which standpipes 5-8 are
straight and preferably inclined to the vertical at an acute angle
lying in the range from about 200 to about 450.
Starting at the elevated separator-hopper vessel 2, the catalyst
descends under gravity as a dense (pseudo-liquid) stream through the
standpipe 6 which opens into the bottom of the reactor vessel 3, into
which the oil fraction to be subjected to second stage cracking is
introduced at A, the catalyst thereby traversing one section of the
horizontal path of travel.
From the reactor 3 the catalyst again descends under gravity as a
dense (pseudo-liquid) stream, this time through the standpipe 7 to a
position which in plan is directly under the stripper vessel 4,
thereby traversing a second leg of the horizontal path of travel It is
then raised into the stripper vessel 4 through a vertical line 9, for

example by means of steam introduced at B The catalyst then flows
under gravity and as a dense phase through the standpipe 8 to a
position which in plan is under the regenerator vessel 1, thereby
traversing a third leg of the horizontal path of travel.
After being raised into the regenerator vessel 1 through the vertical
line 10 by means of air and/or steam introduced at C, the catalyst
again flows under gravity as a dense phase through the standpipe 5 to
a point from which it is raised to the separator-hopper vessel 2
through the first stage catalytic cracking reactor 11 by means of the
vaporised oil feed which is to be subjected to first stage cracking in
the reactor 11 and is introduced at D The reactor 11 is vertical
except for the bend at its top which is necessary to enable the
catalyst to enter the separator-hopper vessel 2 tangentially Thus, the
catalyst flows under gravity and as a dense phase through the
standpipes 5-8 to complete the horizontal displacement of the
circulation path and at intermediate points is raised through the
vertical lines 9 and and the reactor 11.
The lines 9 and 10 extend up into the stripper vessel 4 and
regenerator vesel 1 respectively, to a height above the normal levels
of 70 the fluidized catalyst beds in them, as indicated at levels X
and Y respectively, and, therefore, they open into the upper, or
disengaging, space of these vessels 1 and 4 These lines 9 and 10 and
also the reactor 11, which are 75 constructed to be as straight as
possible and substantially vertical, are of such diameter that at the
flow rate for which the plant is designed the linear velocity therein
is well above the critical velocity, the latter being the superficial
80 velocity above which a so-called dense or pseudo-liquid catalyst
phase cannot separate.
The standpipes 5, 6, 7 and 8 operate with the catalyst always flowing
under gravity as a dense or pseudo-liquid phase 85 In order to obtain
a Proper pressure balance, so that the circulation of the catalyst may
be effected, it is necessary that the standpipe 6 should open into the
reactor vessel 3 near the bottom substantially as shown in Fix I Flow
90 control valves 12 and 13 are provided only on the standpipes 5 and
8 respectively through which the catalyst flows from the regenerator 1
and the stripper 4 The other standpipes 6 and 7 require no such valve
A back-pressure 95 control valve 14 is provided in the vapour effluent
line 15 which leads from the stripper vessel 4 and opens into the
reactor vessel 3 near the top At the top of both the separatorhopper
vessel 2 and the reactor vessel 3 there 100 is provided an outlet-pipe
16 or 17 respectively, through which the vapour effluents flow to
separate fractionating columns In these fractionating columns
separation is effected into a gas-gasoline overhead fraction and a bot
105 tom fraction which, from one or both columns, serves as the feed

for the second stage reactor 3 into which it is introduced at A
Regeneration gases issuing from the regenerator vessel 1 are led
through a line 18 to the flue 110 Only the important lines and
features of the anparatus are shown in the drawing Actually, all four
of the vessels 1-4 are provided near the top with cyclone separators
of conventional design having depending dip-legs Also, there 115 are
vapour distributors, e g perforated pipe distributors, at the bottom
of the cylindrical parts of the regenerator vessel 1 and the stripper
vessel 4 for the distribution of air, introduced at E, and stripping
steam, es' 120 For the sake of clarity and simplicity these and other
conventional features are not shown in the drawving It is to be
understood however that these feautres, as well as various minor
valves, aeration lines, control instruments, 125 and the like
auxiliary equipment will normally be included in the apparatus.
The arrangement of all the four vessels 1-4 in plan roughly in a
circle as shown is the preferred arrangement, but in a modifica 130
784,888 tion of apparatus according to the present invention it is
possible to construct the separator-hopper vessel 2 wholly or partly
within the upper part of the reactor vessel 3 the three vessels 1, 3
and 4 then being arranged roughly in a circle with the
separator-hopper vessel 2 within the vessel 3 directly above the
reaction zone In this arrangement it is essential, as in the case
described, that there be no communication between the two vessels,
except through the catalyst line 6 opening into the reactor vessel 3
near the bottom.
The apparatus described with reference to the drawing is applicable
and may be used with advantage for the controlled catalytic cracking
of hydrocarbon oils by the process described in the aforesaid
co-pending application, to which reference should be made for details
as to the process conditions It will be appreciated however that other
catalytic cracking processes may be carried out in apparatus according
to the present invention Whilst it is particularly suitable for a
two-stage process, it may also be used for a single stage process, the
vapour introduced at D then being steam or the like, and the oil feed
being introduced into the reactor 3 at A.
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* GB784889 (A)
Description: GB784889 (A) ? 1957-10-16
Improvements in or relating to energy regulating services
FR1111623 (A)
FR1111623 (A) less
784,889 / g Date of Application and filing Complete Specification Aug
4, 1955.
No 22477/55.
Application maidne in France on Sept 17,1954.
Complete Specification Publised Oct 16, 1957.
Index at Acceptance:-Class 38 ( 5), Bl S( 1 B 10), B 2 C( 6 C 2: 8 A).
International Classification:-Ho 2 c.
Improvements in or relating to energy regulating services We, SCINTEX,
a Body Corporate duly organized according to the French laws, of 42 to
50, rue de l'Industrie, Courbevoie, (Seine), France, 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 invention relates to
a device for regulating energy supplied to an electric load.
Some electric generators, as for instance the magnetic flywheels used

on vehicles of the motor-cycle type give a voltage which varies
according to the speed of rotation of the flywheel and also according
to the number of loads placed in operation At high speeds and if a
single load of low power rating is placed in service, the voltage may
become excessive and cause damage to or even the destruction of this
load.
The object of the present invention is to obviate this drawback by
regulating the energy supplied to the load at a critical level.
The invention consists in a device for regulating energy supplied to
an electric load, comprising a source of current, a fixed contact
connected to this source, a resiliently mounted metallic blade in
series with the load, a movable contact carried at one extremity of
this blade, a conducting resistance wire connected to a fixed point
and to the said extremity of the blade so as to urge the movable
contact against the fixed contact, the resistance wire being in
parallel with the blade and the load, so that when the voltage of the
source exceeds a critical voltage the resistance wire expands and cuts
off the supply of the load, such interruptions being short but more
and more frequent as the voltage rises, whereby the mean value of the
energy supplied to the load is regulated.
The features of the invention will appear in a more precise manner
from the description which will be given hereinafter with lPrice 3 s 6
d l reference to the drawing which shows in diagrammatic form a device
embodying the invention.
In the drawing, a rigid blade 1 is mounted on a flat spring 2 secured
to a terminal 3 50 which is connected to one end of a load, the other
end thereof being earthed The blade 1 carries a contact 4 at its free
end A conducting resistance wire 5 is stretched between the contact 4
and a fixed point 6 The 55 contact 4 is placed opposite another
contact 8 carried by an elastic blade 9 supported at The lower end of
wire 5 is earthed with or without an interposition of an adjusting
resistance 7 and the contact 4 is pulled to 60 ward the contact 8
against the action of the flat spring 2 by the tension of the wire 5 A
cut-off switch 11 controls the supply of current from the positive
pole of a source having the negative pole earthed and a screw 12 65
makes it possible to adjust the location of the contact 8 If the
applied voltage is lower than a critical voltage, the current passes
through 10, 9, 8, 4, 1, 2 and 3 into the load in a continuous manner,
the slight heating of 70 the wire 5 being made up by the heat losses
to the surrounding medium.
When the voltage increases to above the critical voltage, the wire 5
expands and, allows the blade to move under the action 75 of the flat
spring 2 to open the circuit.
The wire 5, to which power is now no longer supplied, cools down, the

contacts 4 and 8 engage each other and the cycle is repeated The
current is thus interrupted, 80 at a frequency which increases with
the voltage.
By operation of the screw 12 and possibly by alteration of the
resistance 7, it is possible to adjust the system at will and in
particular 85 to adapt it according to the ambient temperature,
variations of which affect the cooling time for the wire 5 and
consequently the duration of the current interruption.
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* GB784890 (A)
Description: GB784890 (A) ? 1957-10-16
Improvements in or relating to fuel elements for nuclear reactors
BE550544 (A) DE1029495 (B) ES230518 (A1) FR1156074 (A)
BE550544 (A) DE1029495 (B) ES230518 (A1) FR1156074 (A) less

fnventor: KENNETH HENRY DENT
Date of filing Complete Specification Aug 16, 1956.
Application Date Aug 25, 1955.
Complete Specification Published Oct 16, 1957.
784890 No 24513/55.
Index at Acceptance: -Class 39 ( 4), P 3 C.
International Classification: -G 21.
Improvements in or relating to Fuel Elements for Nuclear Reactors We,
UNITED KINGDOM ATOMIC ENERGY AUTHORITY, London, a British Authority,
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 perfomed, to be
particularly described in and by the following statement: -
This invention relates to fuel elements for nuclear reactors and the
invention is concerned with a form of fuel element suitable for use as
one of a column of similar elements in a vertically orientated nuclear
reactor, that is, a nuclear reactor comprising a moderator structure
having vertical fuel element channels.
The operating temperature of a nuclear reactor designed as a part of a
steam/electricity generating plant should be as high as possible for
the efficient production of electricity and accordingly it can be said
that the factors in the reactor design limiting its maximum safe
operating temperature also limit the efficiency of electricity
generation At the present time the (principal of these factors is the
creep strength of the material used to enclose the nuclear fuel (the
material commonly referred to as the canning material) and any design
which may be directed to the removal of loads, and hence creep
deformities, from the canning material has merit, especially in view
of the fact that the elements will be expected to reside in the
reactor for a long time to achieve a high degree of burn up ( 3000
megawatt days per tonne) In one proposal to this end it has been
suggested that, in a vertically orientated reactor, the fuel elements
should be individually supported so that the stresses should never
exceed those due to a single element In yet another proposal it has
been suggested that the stressed parts of the canning material should
be preferentially cooled.
According to the present invention a fuel element for use in a
vertically orientated nuclear reactor comprises a nuclear fuel member
enclosed by a protective sheath of canning material and an end
supporting means for the lPrice 3 s W 1 e 4 6 O _ - <; fuel element
comprising a load carrying member having a creep strength superior to
that of the protective sheath material penetrating and sealed to the
protective sheath, and adapted to be fixed to the nuclear fuel member

so that 50 stresses due to the weight of the nuclear fuel member are
carried directly by the load-carrying member.
The load carrying member may be at either end of the fuel element to
provide either for 55 a suspended element which is in tension and thus
free from bowing or a supported element which behaves as a strut in
compression and is liable to bowing but is more easily dischargeable
from the reactor The elements 60 may be individually supported, or
supported one upon or from the other in strings by providing load
carrying members at both ends of the fuel elements which can be
associated with one another in adjacent elements to take the 65
compression or tension in the strings.
The load carrying member is preferably made of a material having a low
neutron absorption (e g beryllium or zirconium alloy) as there will be
many of these members inside 70 a charged reactor core Other
considerations may however prevent the use of low neutron absorbing
materials and it then becomes important that the volume of the load
carrying member should be as small as possible A 75 screwed pin having
one end screwed into the nuclear fuel member and the other end
available to connect with an external part to support the fuel element
provides a simple low volume device 80 The arrangement of individually
suspended fuel elements according to the invention is of particular
interest as it offers not only satisfactory operating conditions
without bowing tendencies, but also safer discharging from the 85
reactor as the discharging operation need not involve stressing the
canning material.
An individually supported fuel element according to the invention is
now described with reference to the drawing accompanying 90 784,890
the provisional specification in which Fig 1 is a sectional elevation
and Fig 2 is a plan view of Fig 1.
In the drawings a fuel element comprises a vertical fuel member 10
enclosed by a sheath 11 made from a tube 12 having circumferential
fins 13, a lower end cap 14, and an upper enid cap 15 An end
supporting means in the form of a stainless steel stud 16 penetrates
the end cap 15 part of the sheath 11 and is screwed into the fuel
member 10 at a thread 17 The stud 16 is bonded to the cap 15 along the
surface 18, so as to be sealed to the sheath in passage therethrough.
The stud 16 has screwed to it a lifting and support member 19 which
comprises a boss 20 with three fixed lifting legs 21 and three
springloaded pivoted legs 22 The legs 22 pivot on pins 23 and the
spring loading is provided by springs 24 in a sense to move the legs
22 outwards.
Each leg 22 has a rising part 25 which offers a face 26 which can be
depressed to move the legs 22 inwards against the spring loading
(during charging and discharging of the fuel element) to the position

shown dotted.
The fuel element is shown lodged in a graphite moderator structure 27
which isshaped to provide a coolant channel 28, a ledge 29 in which
the legs 22 rest so as to support the fuel element, and a conical
cut-away part 30.
A heat insulating disc 31 of aluminium oxide is provided between the
fuel member 10 and the end cap 14 to reduce heat transfer to the end
cap 14.
In the assembly of the fuel element the finned tube 12 is closed at
its lower end by inserting the end cap 14 supporting the disc 31 and
welding along the rim 32 The fuel member 10 is then inserted and the
assembly of cap 15 with bonded stud 16 is screwed into place with a
tool which enters holes 33 This brings flanges 34, 35 into contact,
which are then sealed with an edge weld 36 The lifting and support
member 19 is then attached.
In the charging of the fuel element into the reactor the element is
supported in a grab by the legs 21 and a plunger in the grab acting on
faces 26 keeps the legs 22 to the inward positioni At a suitable point
(the tolerance of which may be liberally taken) in the insertion of
the element, the force of the plunger is withdrawn and the legs 22
move outwards under the loading of springs 24 to touch the 55 walls of
the channels 28 and to follow the conical part 30 to reach the ledge
29 when the element becomes self-suspended.
In discharging the fuel element a grab is lowered which has a sk irt
of larger radius than 60 that of the legs 21 and is arranged to be
located angularly by the legs 22 thereby to locate a lifting part of
the grab under the legs 21.
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* GB784891 (A)
Description: GB784891 (A) ? 1957-10-16

Novel unsaturated ketones and a process for the manufacture thereof
FR1130887 (A)
FR1130887 (A) less
Novel Unsaturated Ketones and a process for the Manufacture
thereof
We, F. HOFFMANN-LA ROCHE & CO., A1CTIENGESELLSCHAFT, a Swiss Company,
of 124-184 Grenzacherstrasse, Basle, Switzer- land, 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 is concerned with novel unsaturated ketones and
with a process for the manufacture thereof.
The unsaturated ketones provided by the invention are substances which
may be represented by the general formula:
<img class="EMIRef" id="026598905-00010001" />
in which R stands for a 6-alkyl-2,6-dimethylcyclohexen-(l)-yl or
6-alkyl-2,6 - dimethylcyclohexen-(2)-yl radical wherein the ailcyl
group contains from 2 to 4 carbon atoms.
These ketones possess new scent nuances and may be used in the
preparation of odoriferous compositions and perfumes.
According to the process provided by the present invention, the
unsaturated ketones aforesaid are manufactured by treating a ketone
having the general formula:
wherein 1S1 represents an alkyl radical having from 2 to 4 carbon
atons, with substantially water-free sulphuric acid below 0 C. or with
phosphoric acid at ca. 20"--35"C. according to whether compounds

having a double bond in the 11,2l- or 21,31-poskions respectively are
required.
The ketones which may be used as starting materials include, for
example, 6,10-dimethyldodecatrien-(3,5,9) - one - (2) and
6,10,12-trimethyl tridodecatrien- (3,5,9)-one-(2). The 6,
10-dirnethyl-dodecatrien-(3,5,9)-one-(2) may be obtained, for example,
as follows:
600 g. of 3-methyl-penten-(1)-ol-(3) were cooled to + 15 C. with an
ice bath, then 1,800 ml. of concentrated aqueous hydrochloric acid
(37%) were poured into the reaction vessel. The mixture was stirred
for 30 minutes. The oil, comprising essentially
1chloro-3-methyl-pentene-(2) was separated, washed three times with
500 ml. of water and dried over calcium chloride. 4 litres of benzene,
1,040 g. of ethyl aceto-acetate and 378 g. of sodium methylate were
stirred into a 12 litre flask. 696 g. of 1-chloro-3-methyl-pentene-(2)
were added from a separatory funnel in 2 hours at 60"C. The stirring
was then continued at 60"C. for 16 hours. The mixture was diluted with
4 litres of water. The oil was separated and the benzene was distilled
off under vacuum. The thick residue,
3-carbethoxy-6-methyl-octen-(5)-one-(2), was placed in a 5-litre flask
with 2 litres of ethyl alcohol, 1 litre of water and 500 g. of
potassium hydroxide. This was stirred for 2 hours, then allowed to
stand for 16 hours, thereby forming the potassium salt of
3-carboxy-6-methylocten-(5)-one-(2). Concentrated hydrochloric acid
was added to the stirred reaction mixture from a separating funnel
until the mixture became strongly acid. The oil layer was removed, and
the aqueous portion was extracted with 1 litre of benzene. The
combined oils were water washed and fractionated to yield
6-methyl-octen-(5)-one-(2), distilling at 65" C./10 mm., nn25=1.4412.
84 g. of metallic sodium was dissolved in 3 litres of liquid ammonia.
Acetylene was bubbled into the stirred solution until its colour
changed from blue to a white. 420 g. of 6-methyl-octen (5)-one-(2) was
dissolved in 500 ml. of diethyl ether and dropped into the stirred
reaction mixture in 1 hour. Stirring was then con tinued for 3 hours
while a slow stream of acetylene was bubbled in. The addition of
acetylene was then stopped, but the stirring was continued for about
15 hours. The ammonia was then distilled off and the residue in the
reaction vessel was washed with 2 litres of 5% aqueous sulphuric acid.
The product was then water-washed, dried over anhydrous calcium
sulphate and fractionated to yield
3,7-dimethyl-nonen-(6)-yn-(1)-ol-(3), distilling at 89Cj10 mm. n-5
1.4612. 300 g. of 3,7-dimethyl-nonen-(6)-yn-(1)-ol-(3), 30 g. of 5 %
lead/palladium/calcium- carbonate catalyst [LINDLA1R, Helvetica
Chimica Acta 1952, 35, 446] and 300 ml. of petroleum ether were placed

in a flask provided with a stirrer and hydrogenated at 25 c30 C. at
one atmosphere hydrogen pressure until 1.9 mols. of hydrogen were
consumed. Fractionation of the product gave
3,7-dimethyl-nonadiene-(1,6)-ol(3) distilling at 132 C./86 mm., nD25 =
4603.
In a flask fined with a stirrer, thermometer, dropping funnel, and a
cold water bath, were placed 1,500 ml. of water, 250 g. of sodium
dichromate, 125 ml. of glacial acetic acid, 200 ml. of benzene, and
125 g. of 3,7-dini-ethyl- nonadien-(1,6)-ol-(3). To the stirred
reaction mixture was added a solution of 125 ml. of concentrated
sulphuric acid in 400 ml. of water over a period of 2 hours. During
the addition, the temperature was controlled at 40 C. The stirring was
continued for an additional hour; then 1 litre of water was added.
The oil layer was removed with a separating funnel, and the aqueous
layer was extracted with 400 ml. of benzene. The oil and benzene
extracts were combined and washed until neutral. The oil was distilled
through a column under vacuum. The product,
3,7-dimethyl-nonadien-(2,6)-al-(1), distilled at 135 -1370C./25 mm.,
nD25=1.4830. The semicarbazone derivative melted at 159"C. 45 g.
of 3,7-dimethyl-nonadien-(2,6)-al-(1), 50 g. of aluminum isopropylate,
600 ml. of acetone and 600 ml. of benzene were placed in a 2-litre
flask and stirred at reflux temperature for 24 hours. The cooled
reaction mixture was washed first with dilute hydrochloric acid and
finally with water until neutral. The benzene was distilled off, and
the product was fractionated under high vacuum, the desired product
6,10dimethyl-dodecatrien-(3,5,9)-one-(2) being obtained in a fraction
distilling at 102 103 C.
/0.2 mm., nD23 =1.5223. The 2,4-dinitro- phenyl hydrazone derivative
melted at 117 C.
The other starting ketones may be obtained similarly: for example, by
using 3,5-dimethyl- hexen-(1)-ol-(3) instead of 3-methyl-penten
(1)-ol-(3).
Depending on the acid agent used for effecting the cyclisation, there
are obtained cyclic ketones having structures analogous to -ionone or
of -ionone. Thus, as indicated hereinbefore, final ketones having
structures analogous to that of ss-ionone are obtained if the ketones
used as starting materials are treated with substantially water-free
sulphuric acid at below 0 C. and final ketones having structures
analogous to that of Sionone are obtained if the ketones used as
starting materials are treated with syrupy phosphoric acid at ca
200-350C. When using sulphuric acid to effect the cyclisation it is
advantageous to carry out the reaction in the presence of acetic acid
as the formation of by products due to polymerisation is lessened
thereby.

The following examples are illustrative of the present invention:
EXAMPLE 1.
A solution of 350 g. of concentrated sulphuric acid and 75 g. of
glacial acetic acid was cooled to - 30 C. 100 g. of
6,10-dimethyl-dodeca.rien-(3,5,9)-one-(2) were added dropwise in 45
minutes, keeping the temperature at -20" to -30 C. The stiff reddish
coloured mixture was warmed up to 0 C. and stirred for 10 minutes.
This was then poured on to 1,500 g. of crushed ice. The product was
extracted with toluene, washed with water, then with 20% aqueous
sodium hydroxide solution, and finally with a saturated sodium
chloride solution containing a few drops of acetic acid. On
fractionation, 4-[6l-ethyl-2l,6l- dimethyl-cyclohexen-(1)-yl] -
buten-(3)-one (2) was obtained in a fraction distilling at
86.50-870C./0.3 mm., nD25= 1.5165. This compound has an odour
reminiscent of violets, but with cedar notes. The 2,4-dinitro-phenyl
hydrazone derivative melted at 126"C.
EXAMPLE 2.
51.4 g. of 6,10-dimethyl-dodecatrien-(3,5,9)one-(2) were added drop by
drop to 3S6 g. of 85% aqueous phosphoric acid with vigorous stirring.
The addition was made in 30 minutes while the temperature was kept at
30"--35"C.
The reaction product was poured into 1,500 ml. of cold water. The
product was extracted with benzene and the extract was subjected to
steam distillation. The distillate was benzene extracted, and the
extract was fractionated.
4-[61-ethyl - 21,6l - dimethyl-cyclohexen-(21) yl] buten-(3)-one-(2)
was obtained as a fraction distilling at 73 C./0.10 mm., nD2= 1.497.
The 2,4-dinitro-phenyl hydrazone derivative melted at 1600C.
4-[6l-ethyl-2l,6l- dimethyl-cyclohexen-(21)-yl] -buten-(3)-one-(2) has
a pleasant fragrance reminiscent of that of orris root.
EXAMPLE 3.
94.6 g. of refractionated
6,10,12-trimethyltridecatrien-(3,5,9)-one-(2), b.p. 10-+ C./0.1 mm.,
nD=1.515 were added to 580 ml.
syrupy aqueous phosphoric acid (85% by weight phosphoric acid) during
30 minutes at a temperature maintained between 24 C. and 30 C. The
stirring was continued 5 minutes longer at 30 C. The mixture was then
poured into 2.2 litres of ice water. The upper layer was separated,
and the aqueous layer was extracted novice, each time with 500 ml. of
benzene. The benzene solution was water washed until neutral. The-
crude reaction product was distilled with steam, the upper (organic)
layer of the distillate was separated and the aqueous (lower) layer
was extracted with 100 ml. of benzene. The organic layer and the
benzene extract were combined and the benzene was removed under

reduced pressure. The residue was fractionated under high vacuum. The
fraction distilling at 94"- 97"C./0.2 mm., nD25 = 1.4958= 1.4963 was
4[614sobutyl-21,6' - dimethyl - cyclohexen-(21)yl]-buten-(3)-one-(2).
This product has a penetrating woody odour reminiscent of cedarwood
and sandalwood and is useful as an odorant in the preparation of
perfumes.
ExAMPLE 4.
A solution of 700 g. of concentrated sulphuric acid and 150 g. of
glacial acetic acid was cooled to -30 C. Then 234 g. of refractionated
6,10,12 - trimethyl - tridecatrien (3,5,9)-one-(2), b.p. 104 C./0.1
mm., nD25= 1.515, was added during 45 minutes, the temperature being
kept between - 30 C. and
- 20 C. An efficient powerful stirrer was needed as the solution
became very thick.
The mixture was warmed up to 0 C. and stirred for 10 minutes at that
temperature. It was then poured on to 3,000 g. of crushed ice and
allowed to stand until the ice melted. The organic layer was
separated, and the aqueous layer was extracted with toluene. The
organic layer and the toluene extract were combined and washed with
500 ml. of water, 500 ml. of 20% aqueous sodium hydroxide solution and
finally with 500 ml. of a saturated aqueous sodium chloride solution
containing a little acetic acid. The oil was dried over anhydrous
calcium sulphate, the solvent was removed and the residue was
fractionated. The fraction distilling at 92"C./0.3 mm., nn25 =
1.505-1.507, comprised essentially 4[6i - isobutyl - 21,61
dimethyl-cyclohexen-(11)-yl] - buten - (3)-one (2). This compound has
an odour similar to that of 4-[61-isobutyl-2l,6l-dimethyl-cyclo-
hexen-(21)-yl] -buten-(3)-one-(2), but distinguishable from the odour
of the latter in being not quite so woody and in having leafy accents.
The compound is useful as an odorant in the preparation of scented
compositions.
What we claim is: -
1) Substances of the general formula:
in which R stands for a 6-allcyl-2,6-dimethyl- cyclohexen-(l)-yl or
6-alkyl-2,6 - dimethylcyclohexen-(2)-yl radical wherein the alkyl
group contains from 2 to 4 carbon atoms.
2) 4- [61-ethyl-21,61 - dimethyl - cyclohexen(ll)-yl]
-buten-(3)-one-(2).
3) 4-[6l-ethyl-2l,6l- dimethyl- cyclohexen- (21)-yl]
-buten-(3)-one-(2).
4) 4- [61-isobutyl-2l,6l-dimethyl-cyclohexen- (21)-yl] -buten-(3
)-one-(2).
5) 4- [614sobutyl-21,61-dimethyl-cyclohexen- (ll)-yl]

-buten-(3)-one-(2).
6) A process for the manufacture of those substances of the general
formula given in claim 1 in which R stands for a
6-alkyl-2,6dimethyl-cyclohexen-( 1)-yl radical wherein the alkyl group
contains from 2 to 4 carbon atoms, which process comprises treating a
ketone of the general formula:
wherein R1 represents an alkyl radical having from 2 to 4 carbon
atoms, with substantially water-free sulphuric acid at below 0 C.
7) A process in accordance with claim 6, wherein the cyclisation is
carried out in the presence of acetic acid.
8) A process for the manufacture of those substances of the general
formula given in claim 1 in which R stands for a
6-alkyl-2,6dimethyl-cyclohexen-(2)-yl radical wherein the alkyl group
contains from 2 to 4 carbon atoms, which process comprises treating a
ketone of the general formula given in claim 6 herein with phosphoric
acid at ca. 20"--35"C.
9) A process for the manufacture of the substances claimed in claim 1
hereof, substantially as described with reference to the examples
given.
* GB784892 (A)
Description: GB784892 (A) ? 1957-10-16
Piperidine derivatives and process for their manufacture

784,892 Date of Application and filing Complete Specification: Sept
23, 1955.
No 26449/55.
Application made in Switzerland on Sept 28, 1954.
Application made in Switzerland on May 3, 1955.
Application made in Switzerland on Aug 24 1955.
Complete Specification Published: Oct 16, 1957.
Index at acceptance:-Class 2 ( 3), C 1 (A 10: B 2), C 1 F 2 (A 2 A 3:
C 4: D 3), C 2 A( 3: 5: 9), C 2 B 3 (A 4:
B: Gi: G 4), C 2 R 17.
International Classification:-CO 7 d.
Piperidine Derivatives and process for their Manufacture We, SAN Doz
LTD, Basle, Switzerland, a Body Corporate organised according to the
laws of Switzerland, do hereby declare the invention, for which we
pray that a patent may be granted us, and the method by which it is to
be performed, to be particularly described in and by the following
statement: -
The invention relates to new piperidine derivatives and salts thereof,
a process for preparing them, and therapeutic compositions containing
them.
The invention provides piperidine derivatives having the formula ja
e,,a tt 8 Ik RS I wherein R,, R 2, R 3 and R 4 are like or different
and represent hydrogen, methyl, chlorine, bromine, or methoxy, and R,
is hydrogen or an alkyl radical; and acid addition salts of such
piperidine derivatives.
The invention also provides a process for the preparation of a
piperidine derivative or an acid addition salt thereof comprising
reacting a secondary amine of the formula 43 KR II wherein R, R,, R 3
and R, are like or different and represent hydrogen, methyl, chlorine,
bromine, or methoxy, with a substituted piperidine of the formula el N
et c H-la ct I CH /Co-CI CJ-lx R 5 III wherein R, represents hydrogen
or alkyl and X represents chlorine or bromine.
In carrying out the process of the invention particularly useful
compounds are obtained by choosing secondary amines as starting
materials in which:
R 1 and R 2 are both hydrogen atoms, and/or R, is hydrogen, and R, is
chlorine, bromine, methyl or methoxy, or R, and R, are both chlorine
or bromine, or R 2 and( R 4 are both hydrogen, or in which one or both
substituents R 1 and R, are in the rm-position to the N-atom, and in
which R 5 in the piperidine derivative is hydrogen or methyl or ethyl,
with consequent formation of the corresponding compounds of the
Formula I.
The process may for example be carried out by dissolving a secondary

amine of Formula II in a solvent, such as for example benzene,
toluene, or xylene, and reacting it with a halogenated piperidine
derivative of Formula III at room temperature or at increased
temperature, for example at the boiling temperature of the reaction
mixture, with good stirring and the addition of a hydrogen
halide-binding or halogen-binding condensation agent, for example an
alkali metal hydroxide, alkali metal amide, alkali metal carbonate or
copper powder After completion of the reaction, the reaction product
is recovered by means of suitable working up of the reaction mixture
and distillation in vacuum The further purification can be effected by
conversion into a suitable salt and subsequent regeneratiorn of the
free base, lPrice 3 s 6 d l 2 784,892 The hitherto unknown compounds
prepared according to the present process are oily or crystalline at
room temperature and form stable solid salts with acids They are
active spasmolytically and should find use in therapeutics as
spasmolytics Furthermore they serve as intermediates for the synthesis
of therapeutically-active compounds Thus, for example, by treatment
with elementary sulphur in the presence or in the absence of a
catalyst, for example iodine, or by treatment with sulphur dihalides,
they lead to phenothiazine derivatives with valuable therapeutic
properties, as for example the raising to a higher power of the effect
of narcotically, hypnotically and analgesically acting pharmaceutics
These phenothiazine derivatives are therefore therapeutically suitable
for use in preparation for narcosis; they can however also be used in
the treatment of allergic illnesses, and as spasmolytics or as
neuroplegics.
The following Examples illustrate the invention without limiting it;
temperatures are given in degrees Centigrade.
EXAMPLE 1.
N lin-chloro-phenyll-N-l 2-(piperidyl2 ')-ethyl-1 l-aniline.
g N-(m-chloro-phenyl)-aniline (B p = /11 mm Hg), prepared according to
F.
Ullman, Ann 355, 338 ( 1907), are dissolved in 800 cc of absolute
xylene, treated with 25 3 g of finely-powdered sodamide, and the
mixture is held at the boiling point under reflux during 2 hours with
stirring using a bath ternperature of 180 Then, without interrupting
the heating, 104 5 g of 2-(piperidyl-2 ')-1chloro-ethane (B p 84 /12
mm Hg, Beilstein 4 Aufl 20, 105), dissolved in 100 cc of absolute
xylene, is added dropwise within 2 hours and the mixture is heated
with stirring during a further 2 hours It is then cooled and the
excess sodamide destroyed by the addition of g of ammonium chloride
After addition of 200 cc of xylene the reaction solution is extracted
3 times, each time with 300 cc of water The xylene layer is then
extracted, once with 400 cc, and then 3 times with 100 cc of dilute

acetic acid The acetic acid extract is made alkaline to
phenolphthalein with 200 cc.
of concentrated caustic soda solution, and extracted with a total of
400 cc of benzene The benzene solution, dried over potash and
filtered, is concentrated as far as possible under partial vacuum at a
bath temperature of 80 .
The residue is first freed from excess 2(piperidyl-21)-l-chloro-ethane
at 14 mm Hg.
and using a bath temperature of about 150 , and then distilled under
high vacuum The main fraction which passes over between 165 and 190 ,
under 0 01 mm Hg, is collected.
The analytically pure N-lrn-chloro-phenyllN l
2-(piperidyl-21)-ethyl-ll-aniline boils under O 01 mm Hg at 170 -175 .
For preparation of the hydrochloride 9 07 g of the base is dissolved
in 35 cc of absolute ethanol and the solution is made acid to Congo
with ethanolic hydrogen chloride, whereupon the hydrochloride
separates out The analytically pure N lmn-chloro-phenyll -N l
2-piperidyl-2 ')-ethyl-ll -aniline-hydrochloride melts at -177 .
EXAMPLE 2.
N lm-chloro-phenyll -N l 2-(N'-ethylpiperidyl-21)-ethyl-1 l -aniline.
52.8 g N-(m-chloro-phenyl)-aniline is dis 75 solved in 175 cc of
absolute xylene and kept at the boiling point with 15 6 g of
finelypowdered sodium hydroxide under reflux with stirring during 3
hours using an oil bath temperature of 180 with provision of a water
80 separator Then, without interrupting the heating, 50 g of
2-(N-ethyl-piperidyl-21)-1-chloroethane (B p 99 -103 /13 mm Hg,
Beilstein 4 Aufl 20, 105), dissolved in 50 cc of absolute xylene, are
added dropwise during 2-, hours, 85 and, without interrupting the
stirring, the mixture is heated at the boiling point during a further
2 hours It is then cooled and the reaction mixture extracted with a
total of 600 cc of water The xylene solution, dried over 90 potash, is
filtered and concentrated as far as possible under partial vacuum at
80 The residue is first freed from excess 2-(N-ethylpiperidy
I-21)-1-chloro-ethane at 11 mm Hg.
and using an oil bath temperature of about 95 , and is then distilled
under high vacuum; The main fraction which passes over under 0.01 mm
Hg between 163 and 176 is collected The analytically pure
N-llm-chlorophenyll N l 2-(N'-ethyl-piperidyl-2 ')-ethyl 100 1
l-aniline has a boiling point of 166 /0 01 mm Hg.
EXAMPLE 3.
N lm-bromo-phenyll -N l 2-(Nl-ethylpiperidyl-21 ')-ethyl-1 l -aniline
105 64.5 g of N-(m-bromo-phenyl)-aniline (B p.
/0 04 mm, prepared in an analogous manner to the
N-(m-chloro-phenyl)-aniline is dissolved in 175 cc of absolute xylene,

15.6 g of finely pulverised sodium hydroxide 110 are added, and the
mixture is kept at the boiling point for 3 hours under reflux with
stirring using an oil bath temperature of 180 with the provision of a
water separator Then, without interrupting the heating 50 g of 2-(N
115 ethyl-piperidyl-21)-l-chloro-ethane (B p 99 103 /13 mm Hg,
dissolved in 50 cc of absolute xylene, are added dropwise during 2-,
hours and the mixture is heated for a further 2 hours It is then
cooled, and the reaction 120 mixture is extracted with a total of 600
cc of water The xylene solution, dried over potash, is filtered and is
concentrated as far as possible at 80 C under partial vacuum The
residue is first freed from excess 2-(N-ethyl-piperidyl 125
21)-1-chloro-ethane at 11 mm Hg and using an oil bath temperature of
about 160 ', and then distilled under high vacuum The main fraction,
which passes over under 0 025 mm.
Hg between 183 and 188 , is collected 130 784,892 784,892 The
analytically pure N lm-bromo-phenyllN l 2-(N'-ethyl-piperidyl-2
')-ethyl-1 l aniline boils under 0 025 mm Hg at 186 .
EXAMPLE 4.
N l 2-(N-methyl-piperidyl-2)-ethyl-1 ldiphenylamine.
169 1 g of diphenylamine ( 1 mol) is dissolved in 5 to 6 times its
weight of absolute xylene, treated with 46 8 g of sodamide ( 20 %
excess) and kept at the boiling point under reflux for an hour Then,
without interrupting the heating, 177 6 g of 2-(N-methyl-piperidyl2
')-l-chloro-ethane of B p 84 /10 mm Hg.
( 10 % excess), dissolved in its own weight of absolute xylene, is
added dropwise within 1-1 hours and the mixture is heated at the
boiling point for a further 10 hours It is then cooled and the excess
sodamide destroyed by the addition of 20 g of ammonium chloride The
reaction mixture is extracted several times with a total of the same
volume of water The xylene layer is concentrated in vacuum at a bath
temperature of 70 , and the residue distilled under high vacuum, the
fraction passing over under a pressure of 0 25 mm Hg at 170 -200 being
collected.
Pure N l 2-(N'-methyl-piperidyl-2 ')-ethyl1 l-diphenylamine boils
under O 25 mm Hg at 193 .
For preparation of the hydrochloride the base is dissolved in 10 times
its weight of absolute ether and treated with etheric hydrogen
chloride until the mixture reacts acid towards Congo The precipitated
hydrochloride is filtered off and recrystallised from 7 times its
weight of acetone The salt melts at 1481500.
EXAMPLE 5.
N lm-chloro-phenyll -N l 2-(N 1-methylpiperidyl-2 ')-ethyl-1
l-aniline.
203 5 g N-(m-chloro-phenyl)-aniline ( 1 mol) is dissolved in 4 to 5

times its weight of absolute xylene, treated with 46 8 g sodamide ( 20
% excess), and held at the boiling point under reflux for 1 hour Then,
without interrupting the heating, 177 6 g of
2-(N-methylpiperidyl-21)-l-chloro-ethane of B p 84 /10 mm Hg ( 10 %
excess), dissolved in its own weight of absolute xylene, is added
dropwise within 1 hours The mixture is then cooled and the excess
sodamide is destroyed by addition of 20 g of ammonium chloride The
reaction mixture is extracted several times with a total of the same
volume of water The xylene layer is concentrated under vacuum at a
bath temperature of 70 and the residue is distilled under high vacuum
whereby the fraction passing over under a pressure of 0 08 mm Hg at
160-193 is collected.
Pure N lm chloro-phenyll-N-l 2-(N 1methyl-piperidyl-2 ')-ethyl-ll
aniline boils under 0 04 mm Hg at 1820.
For preparation of the hydrochloride the base is dissolved in 2 times
its weight of absolute ethanol and treated with ethanolic hydrogen
chloride until the mixture reacts acid towards Congo The residue is
concentrated under vacuum at 60 and dissolved in 2-1 times its weight
of boiling dioxane On cooling, the hydrochloride crystallises out
which, after addition of the same volume of ether as of dioxane used,
is filtered off and recrystallised from its own weight of acetone The
salt melts at 125127 .
EXAMPLE 6 75
N lm-bromo-phenyll -N l 2-(N 1-methylpiperidyl-21)-ethyl-1 l -aniline.
248 g N-(m-bromo-phenyl)-aniline ( 1 mol) is dissolved in 4 to 5 times
its weight of absolute xylene, treated with 46 8 g sodamide 80 ( 20 %
excess) and held at the boiling point under reflux for 1 hour Then,
without interrupting the heating, 177 6 g of 2-(N-methylpiperidyl-2
')-1-chloro-ethane of B p 84 /10 mm Hg ( 10 % excess), dissolved in
its own 85 weight of absolute xylene, is added dropwise within 15
hours The mixture is then cooled and the excess sodamide is destroyed
by addition of 20 g of ammonium chloride The reaction mixture is
extracted several times with 90 a total of the same volume of water
The xylene layer is concentrated under vacuum at a bath temperature of
70 and the residue is distilled under high vacuum, the fraction
passing over under a pressure of 0 08 mm Hg at 185 95 201 being
collected.
The analytically pure N lm-bromo-phenyll N l 2 (NI methyl-piperidy
I-21)-ethyl-llaniline boils under 0 06 mm Hg at 193 For preparation of
the hydrochloride, the 100 base is dissolved in 12 times its weight of
absolute ether and is treated with etheric hydrogen chloride until the
mixture reacts acid towards Congo The precipitated hydrochloride is
filtered off, dissolved for recrystallisation in 105 its own weight of
boiling acetone and treated with half this weight of ether M p 126128

.
EXAMPLE 7.
l 2-(N'-methyl-piperidyl-2)-ethyl-ll 110 ldi(m-chloro-phenyl)l -amine.
20.0 g di-(m-chloro-phenyl)-amine (B p.
225-230 /25 mm Hg), prepared according to L A Elson and C S Gibson (J
Chem Soc.
1931, 301), is dissolved in 90 cc of absolute 115 xylene, treated with
3 95 g of sodamide ( 20 % excess), and held at the boiling point for 1
hour under reflux using an oil bath temperature of 170 Then, without
interrupting the heating, 16 3 g of 2-(N-methyl-piperidyl-21)-1 120
chloro-ethane (B p 84 /10 mm Hg) ( 20 % excess), dissolved in 20 cc
absolute xylene, is added dropwise within 1 hour and the mixture is
heated at the boiling point for 15 hours more It is then cooled and
the excess sodamide 125 is destroyed by the addition of 1 0 g of
ammonium chloride After addition of 100 cc.
of benzene or xylene, the reaction solution is extracted 3 times with
40 cc of water The xylene-benzene layer is concentrated under 130 4
784,892 vacuum using a bath temperature of 70 and the residue is
distilled under high vacuum, the fraction passing over under a
pressure of 0 01 mm Hg at 175-195 being collected Pure l 2-(N
1-methyl-piperidyl-2 l)-ethyl-1 l ldi(m chloro-phenyl)l-amine boils
under 0 01 mm.
Hg at 180 .
The oily base readily dissolves in mineral acids or in aqueous
solutions of organic acids as for example tartaric acid, gluconic
acid, oxalic acid, malic acid, and maleic acid.
EXAMPLE 8.
l 2-(N'-methyl-piperidyl-21)-ethyl-1 l lmchloro-phenyll
lm-methoxy-phenyll -amine.
9 1 g (mt-chloro-phenyl) (nm-methoxyphenyl)-amine (B p 142-143 /0 02
mm.
Hg.), prepared by suitable modification of the process of L A Elson
and C S Gibson (J.
Chem Soc 1931, 301) is dissolved in 40 cc.
of absolute xylene, treated with 1 83 g of sodamide ( 20 % excess),
and kept at the boiling point under reflux for 1 hour using a bath
temperature of 170 Then, without interrupting the heating, 7 55 g of
2-(N-methyl-piperidyl21)-1-chloro-ethane of B p 84 /10 mm Hg.
( 20 % excess), dissolved in 7 5 cc of absolute xylene, are added
dropwise and the mixture is heated at the boiling point for 15 hours
more.
It is then cooled and the excess sodamide is destroyed by the addition
of 0 5 g of ammonium chloride After addition of 50 cc.
of benzene, the reaction mixture is extracted 3 times, each time with

25 cc of water The xylene-benzene layer is concentrated under vacuum
using a bath temperature of 70 and the residue is distilled under
vacuum, the fraction passing over under a pressure of 0.005 mm Hg at
170-192 being collected.
Pure l 2-(N 1-methyl-piperidyl-21)-ethyl-1 llin chloro-phenyll lnm
methoxy-phenyllamine boils under 0 007 mmin Hg at 180 .
For preparation of the hydrochloride, 10 15 g of the base is dissolved
in 150 cc of absolute ether and the solution is made acid to Congo
with etheric hydrogen chloride The precipitated hydrochloride is
filtered off, dissolved in cc of chloroform, and treated with 75 cc.
of benzene, the solution is then poured into 1 to 1 5 litres of
petroleum ether (ice-cold), and is then filtered The melting point of
the l 2(N 1-methyl-piperidyl-2 l)-ethyl-1 l lm-chlorophenyll lm
methoxyphenyll amine hydrochloride is 65-68 (Decomp) after
agglomerating above 50 .
EXAMPLE 9.
N lrm-Methyl-phenyll -N l 2-(N 1-methylpiperidyl-2 ')-ethyl-1 l
-aniline.
The reaction of 2-(N-methyl-piperidyl-2 ')1-chloro-ethane with
N-(m-methyl-phenyl)aniline, by the same process, yields
N-lmmethyl-phenyll -N-l 2-(N' methyl-piperidyl21)-ethyl-1 l-aniline, b
p 1610/0 007 mm Hg.
1 t EXAMPLE 10.
N lm-Methoxy-phenyll -N l 2-(N 1-methylpiperidyl-21)-ethyl-l l
-aniline.
The reaction of 2-(N-methyl-piperidyl-21)1-chloro-ethane with
N-(m-methoxy-phenyl)aniline by the same process, yields
N-lmmethoxy-phenyll-N-l 2-(N'-methyl-piperidyl21)-ethyl-1 l-aniline, b
p 174 /0 01 mm Hg.
EXAMPLE 11.
N-l ntm-Chloro-phenyll-N-l 2-(N'-methylpiperidyl-2)-ethyl-1 l
-p-anisidine.
The reaction of 2-(N-methyl-piperidyl-21)1-chloro-ethane with
N-(m-chloro-phenyl)-panisidine by the same process, yields
N-lmchloro-phenyll N l 2-(N'-methyl-piperidyl2 ')-ethyl-1
l-p-anisidine, b p 189 /0 005 mm.
Hg.
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