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Патент USA US3090825

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United States Patent Q "ice
2
i
r
mean?
Patented May 21, 1963
on a side-chain alkyl group. Furthermore, not more than
two halogen atoms are attached to the ring. That these
3,090,817
PARTIAL DEHYDROHALOGENATIGN 0F HAM)
ALKYLHALGBKCYCLOALKENIC COMP'SUNDS
compounds undergo dehydrohalogenation is unexpected;
the very fact that the literature of the prior art now
known shows that a cyclopentadiene-vinyl chloride ad
duct cannot be dehydrochlorinated while the hexachlo
Louis Schmerling, Riverside, 111., assignor to Universal
Oil Products Company, Des Plaines, 111., a corporation
of Delaware
rocyclopentadiene-vinyl chloride adduct can be dehydro~
No Drawing. Filed July 27, 1960, Ser. No. 45,551
18 Claims. (Cl. 260-648)
This application is a continuation-in-part of my co
chlorinated would tend to lead away from the process of
the present invention inasmuch as it would appear that
10 a chlorine atom of a bicyclic chlorinated compound can
pending application Serial No. 803,587, ?led April 2,
not be removed by treatment with a dehydrochlorinat
1959, now abandoned, which was a continuation-in-part
ing agent unless one of the rings is completely chlori
of my co-pending application Serial No. 580,468, ?led
April 25, 1956, now abandoned.
nated.
It is therefore an object of this invention to prepare
The present invention relates to methods for par
a halo-substituted alkylbicyclo'alkadiene by partially de
hydrohalogenating a haloalkylhalobicycloalkene.
tially dehydrohalogenating certain haloalkylhalobicyclo
ole?nic compounds and more particularly to a method of
The term “bicycloalkadiene” as used hereinafter in
dehydrohalogenating haloalkylhalobicycloheptenes.
the speci?cation and appended claims, refers to those
Heretofore it has been indicated that bicycloalkadienes
could not be prepared by dehalogenating halobicyclo
compounds in which both double bonds are in the ring
20 and to those compounds in which one of the double
alkenes obtained by the condensation of a cycloalkadiene
with a haloole?n. For example, attempts have been
made, as disclosed in a paper by Roberts et al., Journal
bonds is in ‘the ring, the other double bond being exo
thereto. The expression “halo-substituted bicycloalka
diene” refers to bicycloalkadienes which contain halogen
of the American Chemical Society, 72, 3329 (1950),
attached to a carbon atom in the ring and/ or a side-chain.
and in Belgian Patent No. 498,176, issued to I. Hyman
Thus, both 2-chloromethyl-2,S-norbornadiene and 5
et al., to dehydrochlorinate 5—chlorobicyclo[2.2.1]-2-hep
chloromethylene-Z-norbornene are halo-substituted bi~
tene to form bicyclo[2.2.l]-2,5-heptadiene, also known
as 2,5-norbornadiene. This is illustrated by the follow
cycloalkadienes.
A further object of this invention is to ?rst prepare
a haloalkylhalobicycloalkene and then to partially de
ing equation:
hydrohalogenate the same to form a halo-substituted bi
01
+H¢C=CHC1 —->
C
cycloalkadiene.
KOH
One embodiment of this invention is found in a proc
ess for the preparation of a halo-substituted bicycloalka
No reaction
diene which comprises condensing a conjugated cyclo
On the other hand, partial dehalogenation of the con 35 alkadiene with a haloole?n having the general formula:
densation product of a halogenated cycloalkadiene,
namely, hexachlorocyclopentadiene and vinyl chloride may
be carried out as shown by the following equations:
40
in which R is a haloalkyl radical, Q and Q’ are radicals
selected from the group consisting of hydrogen and halo
gen radicals, only one of said Q and Q’ radicals being’
halogen, and R’ is a radical selected from the group
45
consisting of hydrogen, alkyl, halogen, haloalkyl, cyclo
alkyl and aryl radicals, thereby forming a haloalkylhalo
bicycloalkene, and partially dehydrohalogeiiating said
alkene in the presence of a dehydrohalogenating agent
selected from the group consisting of alkali metal hy
droxides, alkaline earth metal hydroxides, alkali metal
Cl
However, this dehydrochlorination reaction occurs be
alkoxides and amines at a temperature in the range of
from about 50° to about 250° C. to form a ‘halo-substi
cause of the presence of the six chlorine atoms on one
ring of the molecule, said chlorine atoms serving to
activate the chlorine atom on the second ring. As here
inbefore stated it has been shown that the reaction prod
tuted bicycloalkadiene.
A further embodiment of the invention is found in a
uct of a conjugated cycloalkadiene such as an unhaloge 55 process for the preparation of a halo-substituted bicyclo
heptadiene which comprises condensing cyclopentadiene
nated cyclopentadiene and a monohaloole?n will not
with a haloole?n having the general formula:
undergo dehydrohalogenation when subjected to the op
erating conditions of prior processes, the single halogen
atom being too inert to undergo reaction with the de
hydrohalogenating agent.
However, I have now discovered that the products of
the Diels-Alder condensation of cycloalkadienes with a
60
in which R is a haloalkyl radical, Q and Q' are radicals
particular class of polyhaloole?ns contain active halo
selected from the group consisting of hydrogen and halo
gens and, contrary to the teaching of the prior art, may 65 gen radicals, only one of said Q and Q’ radicals being
be partially dehydrohalogenated to introduce an ole?nic
halogen, and R’ is ‘a radical selected from the group
bond into a compound having the bicycloheptane ring
consisting of hydrogen, alkyl, halogen, haloalkyl, cyclo
system which previously was regarded as not susceptible
alkyl and aryl radicals, thereby forming a haloalkylhalo
to dehydrohalogenation, thus forming the desired halo
bicycloheptene, and partially dehydrohalogenating said
substituted bicycloalkenes. The compounds which I sub 70 heptene in the presence of a dehydrohalogenating agent
ject to dehydrohalogenation are characterized by the
comprising an alkali metal hydroxide and an organic
presence of halogen on only one of the rings and
solvent at a temperature in the range of from about 50°
3,090,817
3
This reaction is illustrated ‘by the following equation:
to about 250° C. to form a halo-substituted bicyclohepta
diene.
Yet another embodiment of the invention resides in a
01
G
01
halogenated 5-alkylidene-2~norbornene.
HgOl
A speci?c embodiment of the invention resides in a 5
process for the preparation of a halo-substituted bicyclo
heptadiene which comprises condensing cyclopentadiene
with 2,3-dichloro-1-propene, thereby forming S-chloro-S
chloromethyl-2-norbornene, and partially dehydrohalo
O
This compound was tested as an insecticide and found to
genating said heptene in the presence of potassium hy 10 be 100% effective against house?ies when using a 1%
droxide and ethanol at a temperature in the range of from
about 7 5° to about 200° C. to form S-chloromethylene
concentration and to be 64% effective against house?ies
when using a 0.1% concentration. - It was also 100%
Z-norbornene and 2-chloromethyl-2,S-norbornadiene.
effective against mites (both red spider mites and 2-spotted
. Yet another speci?c embodiment of the invention is
mites) in an 0.5% concentration.
found in 5-chloromethylene-2-norbornene.
Other objects and embodiments referring to alternative
diene with 5-chloromethylene-Z-norbornene yields 1,2,3,4,
reactants utilizable as charging stock in the present process
10,10 - hexachloro-6-chloromethylene - 1,4,4a,5,6,7,8,'8a
and to alternative dehydrohalogenating agents within the
scope of this invention will be referred to in greater detail
in‘ the following ‘further detailed description of the in 20
vention.
'
Similarly, the condensation of hexachlorocyclopenta
'
As hereinbefore set forth it has now been discovered
that halo-substituted bicycloalkadienes having the follow
ing formula:
octahydro-1,4,5,18~dimethanonaphthalene, which is also an
excellent insecticide. This reaction is illustrated by the
following equation:
01 /o1
c1 +I oIWzGHCl
01 /
\/I _ono1
_
-—>
I c1001 o
01
25
Cl
01
01
or
.
I
I/
O1
. The reaction between the conjugated cycloalkadiene
30 such as cyclopentadiene and a polyhaloole?n such as a 2,3
.
7
RI!
dihalo-l-propene will proceed according to the following
RII
equation:
in which R represents a haloalkyl radical, X represents a
> hydrogen, halogen, alkyl or haloalkyl radical, y is an in
'
teger from 1 to 4, preferably 1 or 2, R" is independently
selected from the group consisting of hydrogen and alkyl 35
radicals and R’” is afhydrogen, halogen, alkyl or halo
alkyl radicals, may be synthesized ‘by condensing, in a
The polyhaloalkylbicycloalkene will then be partially de-,
Diels-Alder condensation reaction, a conjugated cyclo
hydrohalogenated in the presence of a dehydrohalogenat
alkadiene with a polyhaloole?n having the general for 40 ing agent such as an alkali metal hydroxide and an organic
mula:
i
solvent according to the following equation: I
Q
MOH
VCHaX
I\—__OHX
| iI\"CHsX
X —»
and I C I
ROH LG I
Q’
I
in which R is a haloalkyl radical, R’ is ‘a radical selected 45
from the group consisting of hydrogen, alkyl, halogen,
haloalkyl, cycloalkyl and aryl radicals, Q and Q’ are hy
drogen or halogen radicals, only one of said Q and Q’
I/
to prepare the desired halo-substituted bicycloalkadiene.
In the above equations X represents a halogen, MOI-I is
an ‘alkali metal hydroxide and ROI-I is an alcohol.
radicals being halogen, to ‘form a haloalkylhalobicyclo
alkene, ‘and dehydrohalogenating the resultant compound
,
Another, more speci?c, example of the above method
50 of preparing a halo-substituted bicycloalkadiene is ‘found .
in the'following equations in which cyclopentadiene is re
in the presence of a dehydrohalogenating agent, thus yield
ing new compositions of matter comprising the desired
acted with 1,3-dichloro-l-propene and the resulting com
pound comprising 6-chloro-5~chloromethyl-Z-norbornene
halosubstituted bicycloalkadienes.
is dehydrohalogenated in the presence of potassium hy
droxide and ethanol to form the desired 2-chloromethyl
. The reaction between the conjugated cycloalkadiene and
the polyhaloole?n is a thermal condensation of the Diels
2,5-norbornadiene and 6~chloro-5-met'hylene-2-norborn
Alder type and occurs in the absence of any added cata
lyst. The condensation usually takes place at a tempera
. ene.
ture in the range of ‘from about 50° to about 250° C.,
and preferably in the range of from about 100° to about
200° C. In'addition, the reactants are preferably present 60
If“
in a molar ratio range of ‘from about 0.5 :1 to about 0.9:1
moles of cycloalkadiene to polyhaloole?n. The excess of
polyhaloole?n is preferred in order to insure the produc
tion of a bicyclic compound instead of a tetracyclic 'com
pound which may occur if the cycloalkadiene is in excess. 65
7 The halo-substituted bicycloalkadienes comprising new
compositions of matter which are the desired products of
the present invention are usefulas intermediates in the
. I CITOHQCI ——>
KOH I CI I ~ 011201
I/_01
ethanol I
and I OI
_on,
I/_C1
_ As hereinbefore stated one component of the feed stock
is selected from the group of compounds consisting of con
For example, the condensation of a haloalkyl 70 jugated cycloalkadienes, such compounds including 1,3- '
preparation of insecticides, pharmaceuticals, resins and
plastics.
bicycloalkadiene such as 2-chloromethyl-2,S-norbornadi
ene prepared according to the process of this invention,
cyclopentadiene (herein referred to as cyclopentadiene),
with,hexachlorocyclopentadiene yields l,2,3,4,10,10-hex
ene, etc., alkyl substituted cyclopentadienes such as 1
1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3»cyclooctadi
methylcyclopentadiene, 2-methylcyclopentadiene, 5-meth-'
achloro-6-chloromethyl-1,4,4a,5,8,8a-hexahydro -- 1,4,5 ,8- _
dimethanonaphthalene;
75
ylcyclopentadiene, S-ethylcyclopéntadiene, 5,5-dimethyl
3,090,817
5
cyclopentadiene, 1,2-dimethylcyclopentadiene, etc., 1
1 ,Z-dibrorno-Z-butene,
1 ,Z-di?uoIO-Z-butene,
1,2-dimethyl-1,3-cyclohexadiene, 1,3-dimethyl-1,3—cyclo
l ,2-diiodo-2-butene,
1 ,1, 3-trichloro-2-butene,
hexadiene, 1,Z-diethyl-1,3-cyclohexadiene, etc. Cyclopen
l ,1,3-tribromo-2-butene,
tadiene and alkyl substituted cyclopentadienes are pre
1 , l ,3-tri?uoro-2-butene,
‘ferred reactants in this process due to their relatively
1 ,1,3-triiodo-2-butene,
greater availability. It is also contemplated within the
1 , 1,2-trichloro-2-butene,
scope of this invention that dicycloalkadienes which dis
l , 1,2-tribro1no-2-butene,
associate and ‘become monocycloalkadienes at conditions
under which the reaction of this invention proceeds may 10 1 ,1,2-tri?uoro-2-butene,
l , 1 ,Z-triiodo-Z-butene,
also be used. Examples of these dicycloalkadienes in
1 ,1,1,S-tetrachloro-Z-butene,
clude dicyclopentadiene, dicyclohexadiene, etc.
l ,l,1,3-tetrabromo-2-butene,
The polyhaloole?n compound which as hereinbefore set
l , 1,1 ,3-tetrafluoro~2~butene,
forth has the general formula:
15 1 ,l,1,3-tetraiodo-2-butene,
1 , 1, l,2-tetrachloro-2Jbutene,
1 , 1, l ,2~tetrabromo-2-butene,
l , l , 1,2-tetra?uoro-2-butene,
rnethyl-1,3-cyclohexadiene, 1 - ethyl-1,3-cyclohexadiene,
1,l,1,2-tetraiodo-2-butene,
in which R, R’, Q and Q’ represent radicals previously set
20 l-cyclopentyl-Z, 3-dichloro- l-propene,
forth, may include
l~cyclopentyl-2,3-dibromo- l-propene
1-cyclopentyl-2,3-di?uoro-l-propene,
1,3-dichloro-1-propene,
1, 3-dibromo-l-propene,
1,3-dilluoro-l-propene,
1,3-diiodo-l-propene,
2,3-dichloro-1-propene,
2,3-dibromo-1-propene,
2,3-diiiuoro-1-propene,
2,3-diiodo- l-propene,
1,3,3-trichloro-1-propene,
1,3,3-tribromo-l-propene,
,1,3-trichloro-l-propene,
1-cyclopentyl-2,3-diiodo-1 -propene,
1-cycloheXyl-2,3-dichloro- l-propene,
25
,3 ,3-trichloro'l -propene,
1-phenyl-2, 3 ~dichlor0-1-propene,
1-phenyl-2,3-dibrorno- l-propene,
30 l-phenyl-2,3-di?uoro- 1 ~propene,
1-phenyl-2,3-diiodo-l-propene,
1-cyclopentyl-2,4-dichloro-1=butene,
1—cyclopentyl-2,4-dibrom0- 1 -butene,
35
,3,3-tribron1o-1-propene,
,3,3-tritluoro-1-propene,
,3,3-triiodo-1-propene,
,3 ,3,3-tetrachloro- l -propene,
,3,3 ,S-tetrabromo- l-propene,
,3 ,3,3-tetra?uoro- l-propene,
,3,3,3~tet-raiodo-1-propene,
,3,3 ,3-tetrachloro- l-propene,
,3 , 3 ,3-tetrabromo-l-propene,
,3,3,3-tetra?uoro- l-propene,
and also due to the fact that they will result in the forma
tion of the preferred final products. It is to be understood
that the above enumerated conjugated cycloalkadienes
and polyhaloole?ns of the aforesaid general formula are
only representatives of the compounds which may be used,
and that this invention is not necessarily limited thereto.
1,4-dichloro-1-butene,
1 ,4?dibromo-l-butene,
l ,4,4-tribromo-l—butene,
1,4,4-tri?uoro-1-butene,
1,4,4—triiodo-1~butene,
1,4,4,4'tetrachloro-l -butene,
1,4,4,4-tetrabromo- l-butene,
1,4,4,4-tetra?uoro- l-butene,
1,4,4,4-tetraiodo- l-butene,
2,4,4-trichloro- l -butene,
2,4,4-tribromo-1-butene,
2,4,4~tri?uoro-1-butene,
2,4,4~triiodo-1-butene,
2,4,4,4-tetrachl0ro-14butene,
2,4,4,4-tetrabromo-l-butene,
2,4,4,4-tetra?uoro-l-butene,
2,4,4,4-tetraiodo- l-butene,
l,3~dichloro-2-butene,
1 ,3-dibromo-2~butene,
1,3-di?uoro-2-butene,
1,3-diiodo-2-butene,
1,2-dichloro-2-butene,
1-cyclopentjl-2,4-di?uoro-l-butene,
1-cyclopentyl-2,4-diiodo-1-butene,
1-cyclohexyl-2,4-dichloro-1#butene,
1~cyclohexyl-2,4-dibromo- l-butene,
l-cyclohexyl-2,4-di?uoro- l-butene,
1~cycloheXyl-2,4-diiodo- l-butene,
1-phenyl-2,4-dichloro- l-butene,
1-phenyl-2,4-dibromo-1-butene,
1-phenyl-2,4-di?uo ro- l-butene,
1-phenyl-2,4-diiodo-1~butene, etc.
The dichloropropenes ‘are the preferred polyhaloole?ns
45 due to their relatively greater availability and lower cost,
2,3 ,3,3-tetraiodo-l -propene,
1,4-di?uoro-1-butene,
1,4-diiodo-l -butene,
2,4rdichloro-1-butene,
2,4-dibromo-1-butene,
2,4-difluoro-1-butene,
2,4-diiodo~ l-butene,
1,4,4-trichloro- Lbutene,
1 -cycloheXyl-2, 3 ~dibromo-1-propene,
1-cycloheXyl-2,3—di?uoro~1-propene,
1~cycloheXyl-2,3-diiodo-1 -propene,
, 1,3-tribromo-l-propene,
1,3-tri?uoro-1-propene,
,1,3-triiodo-1-propene,
a
The partial dehydrohalogenation of the polyhaloalkyl
bicycloalkenes resulting from the reaction between the
55
conjugated cycloalkadiene and the polyhaloole?n is ef
fected by treating said compounds with a dehydrohalo
genating agent which includes the hydroxides of the al
kali metals and alkaline earth metals such as the hydrox
ides of lithium, sodium, potassium, rubidium, cesium,
calcium, barium, and strontium; amines such as trimethyl
‘amine, pyridine, quinoline, etc.; alkali metal alkoxides
such as sodium methoxide, potassium ethoxide, etc.; and
other basic substances such as potassium carbonate, po
tassium phenoxide, etc.
The hydroxides of the alkali
metals and alkaline earth metals may be used as such
65 (fused or powdered) or they may be dissolved in a suitable
organic solvent, preferably an alcohol.
The particular
alcohol which is used as the organic solvent in the dehy
drohalogenating reaction will depend largely upon the
temperature at which the reaction occurs. Alcohols which
are utilizable in this reaction include ‘methyl, ethyl, n
propyl, isopropyl, n-butyl, isobutyl, amyl, etc.
The operating conditions under which the process of
the present invention is conducted will, to some extent,
depend upon the particular compounds employed in the
75 reaction.
The temperature for the reaction between the
particular conjugated cycloalkadiene and the polyhalo
ole?n in which a haloalkylhalobicycloalkene is formed
will range from about atmospheric to about 250° C. or
more, the preferred range being from about 100° to about
200° C. Likewise, the partial dehydrohalogenation step
or more, the preferred range being from about 60° to
about 200° C. In addition, the reaction may be effected
in any suitable manner, either a batch or a continuous
type operation similar to that hereinbefore described with
reference to the reaction between the cycloalkadiene and
the polyhaloole?n. in the batch type operation the re
actants comprising .the hexachlorocyclopentadiene and
of this process will also occur at temperatures depending
upon the particular reactants and the solvent which is
the halosubstituted .bicycloalkadiene are placed in a re
used as a medium for the reaction. Suitable temperatures
will usually lie in the range of from about 50° to about . actor provided with heating and mixing devices. This
250° C., the preferred range being from 75° to about 10 reactor is heated and maintained at the desired temper
ature until the reaction is completed after which the re
200° C. In addition, the reaction will usually take place
actor is cooled to room temperature and the desired re
at atmospheric pressure, however, when the reaction tem
action product withdrawn, separated and puri?ed by con
perature is in a higher range than the boiling point of
ventional means such as fractional distillation, crystal
the solvent, superatmospheric pressures may be employed.
The process of this invention may be effected in any 15 lization, etc.
When a continuous type operation is used the reactants
suitable manner and may comprise eitherv a batch or a
may be introduced into a reactor through lines provided
continuous type operation. When a batch type operation
therefor, said reactor being equipped with heating and
is used, a quantity of the reactants comprising the con
mixing means and maintained at the desired operating
jugated cycloalkadiene and the polyhaloole?n is placed
in a reactor provided with a mixing and heating device. 20 conditions of temperature and pressure. The desired
product is withdrawn and puri?ed while the unconverted
The reactor is heated to the desired temperature while
thoroughly admixing the contents thereof. After a suit
able period of time has elapsed, the reactor and its con
tents are cooled to room temperature, after which the
material may be recycled and used as part of the feed
stock, or mixed with fresh starting materials. It is also
contemplated within the scope of this invention, that this
desired product is recovered by suitable means, for ex 25 latter reaction may take place in the presence of inert
diluents, e.g. liquid aromatic hydrocarbons such as ben
ample, by fractional distillation or other means known
zene, toluene, etc.
in the art, while the unreacted feed stock may be re
The physical properties of the insecticides which are
charged to form a portion of the starting material of the
_ prepared by reacting the products of this invention with
next batch. The desired product is then placed in a
second reactor, or if so desired, returned to the same re
actor and the dehydrohalogenating agent and organic
solvent added thereto.
The reactor is then heated to the
30 other organic compounds such as hexachlorocyclopenta,
diene, the illustrative reactions of said reactions being
hereinbefore set forth, and the effects they have on ento
mological forms of life make them particularly desir
which the halo-substituted bicycloalkadiene is separated 35 able as insecticides and insect repellents, the compounds
having many of the'features desired of materials for this
by suitable means hereinbefore set forth while the’ or
desired temperature until the reaction is completed, after
ganic solvent and dehydrohalogenating agent are re-_
, covered for further use in subsequent batches.
purpose. They are, for example, toxic to insects which '
are destructive of plant life and materials normally sub
ject to insect infestation, their toxic effects being manig
Another method of operation of the present process is
'
of the continuous type. In this operation the reactants 40 tested by contact of the poison with the insect. The in
secticides comprising the present componds are thus ef
comprising the conjugated cycloalkadiene and the poly
fective against chewing as well as sucking types of insects.
haloole?n are continuously charged to a reactor provided
The compounds are su?iciently volatile so that when ap
with heating and mixing means. The reactor may com
plied to plant life intended for subsequent human con
prise an unpacked vessel or coil or may be lined with
sumption, the plants when harvested and after allowing
an adsorbent packing material such as dehydrated bauxite,
a reasonable time ‘for evaporation of the applied insecti
alumina and the like, said reactor being maintained at
cide therefrom, retain none of the toxicant to prevent
suitable operating conditions of temperature and pressure.
the use of the plant for consumption as food. On the
The desired reaction product comprising a haloalkylhalo
hand, the compounds are of su?iciently limited
bicycloalkene is continuously withdrawn from this vessel ' other
volatility to'be retained on the insect for the time re
by suitable means and charged into a second reactor also 50 quired to accomplish the toxic effect of the compounds.
maintained at suitable operating conditions, while the
The volatility and retentive capacity of the compounds
unreacted feed stock from the ?rst reactor may be with
may be varied at will by combining them with suitable
drawn and recycled for use as a part of the fresh feed
?xing agents which reduce or promote their volatilization,
stock. The dehydrohalogenating agent, comprising, for
example, an alkali or alkaline earth hydroxide, either in
solid or ?uidized form or dissolved in the solvent which
acts as a medium in which the partial dehydrohalogena
tion takes place are also charged to the aforesaid second
reactor by suitable means. The partially dehydrohalo
1 as desired. Thus, the compounds may be ‘dissolved in a
suitable high boiling solvent, such as a mineral or vege
table oil, petroleum, etc.; a wax, such as para?in wax,
beeswax, etc.; a high molecular weight alcohol or ether
such as myricyl alcohol, dibutyl ether, etc.; or they may
be emulsi?ed with water by the addition of an emulsify
genated compound, comprising a halo-substituted bicyclo 60 ing agent, such as a surface active agent, to the mixture ‘
alkadiene, is continuously withdrawn from this second
of components. The latter solvents and dispersants may
reactor and puri?ed by conventional means hereinbefore
also be employed for the speci?c purpose of reducing the
set forth, while the unreacted material may be recycled
concentration of insecticide to the desired level in a
to form a portion of the feed stock.
speci?c insecticidal formulation. The particular formu
As hereinbefore set forth, the halo-substituted bicyclo
lation of active components in combination with the sol
alkadiene prepared in the above manner may be reacted
vent or dispersant will depend upon its application.
with a polyhalocycloalkadiene such as hexachyorocyclo
Compositions containing as high as 20% of active com;
pentadiene to form polyhaloalkyl tetracyclic compounds
ponent may be preferred, in some instances where deep
which are useful as insecticides. The condensation of
penetration of the insecticide is desired, as in the treat;
the halo-substituted bicycloalkadiene and the hexachloro 70 ment of ?brous material, such as wood, for extinction of
cyclopentadiene is carried out in a similar manner to the
a particular infestation, for example, wood termites.
reaction between the conjugated cycloalkadiene and the
For other purposes the required concentration of active
polyhaloole?n as hereinbefore described. The temper
components in the formulation may be as low as 0.1%,
ature at which the reaction is to be carried out will be
as for example, in the treatment of fabrics for destroying,
in the range of from about atmospheric to about 250° C. ' moth larvae.
3,090,817
10
In utilizing the present insecticidal compounds against
The cut boiling at 69—72° . (at 19 mm. pressure) or
174—175° C. (at 760 mm.) was separated out.
This
most insects, a composition containing from about 0.1%
cut, comprising 5-chloromethylene-2-norbornene and 2
to about 5% by weight of the active component is highly
chloromethyl-Z,S-norbornadiene, having a refractive index
effective. The choice of the most desirable solvent or
of 1.5183 was subjected to analysis. The results of this
dispersant further depends upon the method utilized to
analysis are set forth below.
apply the insecticidal composition to the infested arti
Analysis-Calculated for C3H9Cl: C, 68.33; H, 6.45;
cle, for example, a low molecular weight, normally
gaseous carrying agent. The active insecticidal com
C], 25.22. Found: C, 67.64; H, 6.65; Cl, 25.66.
ponent, such as propane, vbutane, the Freons, etc., may
Example III
be compressed and lique?ed into a small bomb containing 10
A
mixture
of
102
g.
of dicyclopentadiene and 200 g. of
the insecticide. Upon release of pressure from the bomb,
1,3-dichloro-l-propene was heated at a temperature in the
the lique?ed carrier vaporizes and suspends a quantity
range of from about 180° to about 200° C. in a glass liner
of the active components therein, thus providing a con
of a rotating autoclave under 30 atmospheres of initial
venient spraying method of applying the insecticide. The
active component may also ‘be dissolved in a liquid car 15 nitrogen pressure for a period of about 4.5 hours. At the
end of this time the liner and contents thereof were cooled
rier, such as kerosene, an alcohol, ester, ketone, etc., and
to room temperature, the nitrogen was vented and the re
the resulting solution atomized by a suitable spraying de
action product comprising 6-chloro-5-chloromethyl-2-nor
vice.
bornene was separated.
The present invention is further illustrated with respect
to speci?c embodiments thereof in the following ex
amples which, however, are not intended to limit the
generally broad scope of the present invention in strict
accordance therewith.
Example I
A solution of 40 g. of the 6-chloro-5-chloromethyl-2
norbornene and 15 g. of potassium hydroxide in 150 g. of
n-propyl alcohol was heated under re?ux at 95-98° C. for
9 hours. The potassium chloride which had precipitated
(8 g.) ‘was ?ltered oif and the ?ltrate ‘was distilled to re
25 move about 150 cc. of overhead at 87-96° C. The tem
A mixture of 102 g. of dicyclopentadiene and 200 g.
perature of the solution rose to 100° ‘C. at which tempera
ture it was re?uxed for an additional 11 hours. The
product was permitted to cool and was then ?ltered yield
ing 4.0 g. additional potassium chloride. The ?ltrate was
rotating autoclave under 30 atmospheres of initial nitro
gen pressure for a period of about 4.5 hours. At the end 30 combined with the overhead, about 1 liter of Water was
added and the product was extracted with pentane. The
of this time the liner and contents thereof were cooled
pentane extract was washed with water, dried and distilled
to room temperature, the nitrogen vented and the reac
from potassium carbonate. There was obtained 11.5 g.
tion product was separated from unreacted starting ma
of a fraction boiling from 90° C. at 60 mm. to 88° C. at
terials. The reaction product was subjected to fractional
distillation at reduced pressure and the cut boiling at 35 38 mm., converted boiling point: (l69—l79° C. at 760
mm.); refractive index, 11132", 15116-15130. Infra-red
75—77° C. (at 4 mm. pressure) or 221-223° C. (at 760
inspection of the product showed that it consisted chie?y
mm.) was separated. The cut amounted to 118 g. of 5
of a mixture of 6-chloro-5~methylene-2-norbornene and
chloro-S-chloromethyl-Z-norbornene having a refractive
2~chlorornethyl-2,5-n0rbornadiene.
index in the range of from 1.5185 to 1.5205.
The 5-chloro-5-chloromethyl-2-norbornene was par 40
Example IV
of 2,3-dichloro-1-propene was heated at a temperature in
the range of from 180° to 200° C. in a glass liner of a
tially dehydrochlorinated by re?uxing 43 g. of product
prepared as above described with a solution of 15 g. of
A mixture of cyclopentadiene and 2,4-dichloro-1-butene
potassium hydroxide in n-propyl alcohol at 95° C. for 9
hours. Filtration yielded 9.3 g. of potassium chloride.
is heated at approximately 200° C. in a glass liner of a ro
hours, after which it was cooled and the precipitated
potassium chloride (1.2 g.) was ?ltered oif. Water
tion under reduced pressure. The cut, comprising 5
chloro-S-(Z-chloroethyl)-2-norbornene is separated out.
(about 800 cc.) was added to the ?ltrate as well as to
the above-mentioned distillate and the product was ex—
tracted with pentane. The pentane extract, which was
?ux with an ethyl alcohol solution of potassium hydroxide
tating autoclave under 30 atmospheres under initial nitro
The ?ltrate was then distilled, about 120 cc. of overhead 45 gen pressure for a period of time of about 5 hours. At
the end of this time, the liner and contents thereof are
boiling at 87-97° C. being obtained, while the tempera
cooled to room temperature. The nitrogen gas is vented
ture of the alcoholic solution rose to 102° C. The solu
and the reaction product is subjected to fractional distilla
tion was re?uxed at 102° C. for an additional twelve
water washed to remove any dissolved alcohol, was then
dried over potassium carbonate and fractionally distilled
from potassium carbonate. There was obtained 10 g.
‘of liquid boiling vfrom 89° C. at 52 mm. to 79° C. at 29
mm., converted boiling point: (172-176° C. at 760 mm.);
refractive index, r1132", 1.51157-1.5166. The infrared
spectrum of this ‘material indicated that it contained both 60
the cis-ethylenic double bond such as is found in 2-nor
bornene and a trisubstituted ethylenic double bond exo
to the ring. It was apparent that the product consisted
chie?y of 5-chloromethylene-2-norbornene mixed with a
smaller amount of 2-chloromethyl-2,5-norbornadiene.
The above mentioned norbornene is heated under re
at a temperature of approximately 80° C. for about 16
hours. At the end of this time the reflux vessel and the
contents thereof are cooled to room temperature and the
reaction product subjected to fractional distillation under
reduced pressure. The cut, comprising 5-(2-chloroeth
ylidene)-2-norbornene and 2-(2-chloroethyl)-2,5-nor
bornadiene is separated and puri?ed by conventional
means.
Example V
A mixture of cyclopentadiene and 2,3-dibromo-1-pro
pene is heated at a temperature in the range of from about
180° to about 200° C. in a glass liner of a rotating auto
clave under 30 atmospheres of initial nitrogen pressure
for a period of time of about 5 hours. At the end of
Example II
this time the liner and contents thereof are cooled to
In this experiment the, 5-chloro-S-chloromethyl-Z-nor
room temperature, the nitrogen is vented and the reaction
bornene was prepared in a manner similar to that set forth
product is subjected to ‘fractional distillation under re
in Example I above. The 5-chloro-5-chloromethyl-2 70 duced pressure, the cut comprising S-bromo-S-bromo
norbornene was heated under re?ux with an ethyl alcohol
methyl-Z-norbOrnene being separated out. The afore
solution of potassium hydroxide at 80° C. for a period
mentioned norbornene is heated under re?ux with an
of approximately 16 hours, after which time the reaction
ethanol solution of potassium hydroxide at a temperature
product was separated and subjected to fractional distil
of approximately 80° C. for a period of about 10 hours.
lation under reduced pressure.
75 At the end of this time the re?ux vessel and contents
3,090,817"
11
,
it
i
12
ence of a dehydrohalogenating agent'comprising potas
sium hydroxide and alcohol at a temperature inthe range
of from about 50? to about 250° C. to form a‘halo-sub
thereof are cooled to room temperature and the reaction
product subjected to fractional distillation, the cut com
prising S-bromomethylene-Z-norbornene and 2-bromo
methyl-2,5-norbornadiene is separated and puri?ed by
stituted
bicycloalkadiene,
’
,
‘
'
>
‘
4. A process for the preparation of a halo-substituted
conventional means.
bicycloalkadiene which comprises condensing a conju-v
gated cycloalkadiene with a halo-ole?n having the general
Example VI
In this example cyclopentadiene and 2,3,3-trichloro-1
formula
propene are condensed in a manner similar to that set
‘
forth in the above examples. The reaction product com
prising S-chloro-S-dichloromethyl-Z-norbornene is sepa 10
rated and recovered by conventional means hereinbefore
described. The aforementioned norbornene is partially
dehalogenated by heating under re?ux with a propyl alco
hol solution of potassium hydroxide at a temperaure of
about 85° C. ‘for about 10 hours. At the end of this time
the reaction product is subjected to fractional distillation
and the cut, comprising 5-dichloromethylene-2-norborn
ene and 2-dichloromethyl-2,5-norbornadiene is separated
and recovered.v
I claim as my invention:
1. A process for the preparation of a halosubstituted bi
cycloalkadiene which comprises condensing a conjugated
cycloalkadiene with a halo-ole?n having the general for
mula
R
in which R is a haloalkyl radical, Q and Q’ are selected 0
from the group consisting of hydrogen and halogen rad
icals, only one of said Q and Q’ radicals being halogen,
and R’ is a radical selected from the group consisting of
hydrogen, alkyl, halogen, haloalkyl, cycloalkyl 'and aryl
radicals, thereby forming a haloalkylhalobicycloalkene,
and partially dehydrohalogenating said alkene in the pres
20 ence of a dehydrohalogenating agent comprising potasé
sium hydroxide and ethanol at a temperature in the ‘range
of from about 50° to about 250° C. to form a halo-sub
stituted bicycloalkadiene.
' R’
'
'
‘
‘
gated cycloalkadiene with a halo-ole?n having the general
‘formula
Q
V
5. A process for the preparation of a halo-substituted
25 ibicycloalkadiene which comprises condensing - a conju
Q’
'
I
Y
'
'
in which R is a haloalkyl radical, Q and Q’ are radicals 30
selected from the group consisting of hydrogen and halo
gen radicals, only one of said Q and Q’ radicals being
halogen, and R’ is a radical selected from the group con
sisting of hydrogen, alkyl, halogen, haloalkyl, cycloalkyl
,
,
R
R’
Q
Q’
,
in which ‘R is a haloalkyl radical, Q and Q’ are selected
from the group consisting of hydrogen and halogen radi
cals, only one of said Q and Q’ radicals being halogen, and
and aryl radicals, thereby forming a haloalkylhalobicyclo
alkene, and partially dehydrohalogenating said alkene in
R’ is a radical selected from the group consisting of hydro
gen, alkyl, halogen, haloalkyl, cycloalkyl and aryl radicals,
the persence of a dehydrohalogenating agent selected
from the group consisting of alkali metal hydroxides, al
kaline earth metal hydroxides, alkali metal alkoxides and
thereby forming a haloalkylhalobicycloalkene, and par
tially dehydrohalogenating said alkenein the presence of a
amines at a temperaure in the range of from about 50° to 40 dehydrohalogena-ting agent comprising potassium hydrox
ide and a propyl alcohol at a temperature in the range of
about 250° C. to form a halo-substituted bicycloalkadiene.
from
about 50° to about 250° C. to ‘form a halo-substi
2. A process for the preparation of a halo-substituted
tuted bicycloalkadiene.
bicycloalkadiene which comprises condensing a conju
gated cycloalkadiene with a halo-ole?n having the general
formula
V
,
6. A process for the preparation of a halo-substituted
bicycloalkadiene which comprises condensing a conjugated
45
cycloalkadiene with a halo-ole?n having the general
formula
V
R
R’
>C=<
in which R is a haloalkyl radical, Q and Q’ are selected
from the group consisting of hydrogen and halogen radi
cals, only one of said Q and Q’ radicals being halogen,
in which ‘R is a haloalkyl radical, Q andQ' are selected
from the group consisting of hydrogen and halogen radi
cals, only. one of said Q and Q’ radicals being halogen,
and R’ is a radical selected from the group consisting of
hydrogen, alkyl, halogen, haloalkyl, cycloalkyl and aryl
radicals, thereby forming a haloalkylhalobicycloalkene,
and partially dehydrohalogenating said'alkene in the pres
'
55
and R’ is a radical selected from the group consisting-0f
hydrogen, alkyl, halogen, haloalkyl, cycloalkyl and aryl
radicals, thereby forming a haloalkylhalobicycloalkene,
and partially dehydrohalogenating said alkene in the pres
ence of a dehydrohalogenating agent comprising an alkali
metal hydroxide and an organic solvent at a temperature
in the range of from about 50° to about 250° C. to form a
ence of a dehydrohalogenating agent comprising sodium
hydroxide and ethanol at a temperature in the range of
60 vfrom. about 50° to about 250° C. to form a halo-substi
3. A process for the preparation of a halo-substituted
halo-substituted bicycloalkadiene.
tuted bicycloalkadiene.
bicycloalkadiene which comprises condensing a conju
gated cycloalkadiene with a halo-ole?n having the general
bicycloheptadiene which comprises condensing cyclopen
formula
65
R
Q
>0 <
‘
' 7; A process for the preparation of ahalo-substituted
tadiene with a halo-ole?n having the general formula
Q.’
in which R is a haloalkyl radical, Q and Q’ are selected
from the group consisting of hydrogen and halogen radi 70 in which vR is a haloalkyl radical, Q and Q’ are radicals
selected from the group consisting of hydrogen and halo
cals, only one of said Q and Q’ radicals being halogen,
gen radicals, only one of said Q and Q’ radicals being
and R’ is a radical selected from the group consisting of
hydrogen, alkyl, halogen, haloalkyl, cycloalkyl and aryl
radicals, thereby forming a haloalkylhalobicycloalkene,
and partially dehydrohalogenating said alkene in the pres
halogen, and R’ is a radical selected from‘the group con
sisting of hydrogen, alkyl, halogen, haloalkyl, cycloalkyl
and aryl radicals, thereby forming a haloalkylhalobicyclo
3,090,817
13
14
heptene, and partially dehydrohalogenating said heptene
bicycloheptadiene which comprises condensing 2,3,3-tri
chloro-l-propene with cyclopentadiene, thereby forming
5-chloro-5-dichloromethyl-2anorbornene, and partially de
in the presence of a dehydrohalogenating agent compris
ing an alkali metal hydroxide and an organic solvent at a
temperature in the range of from about 50° to about
hydrohalogenating said norbornene with potassium hy
250° C. to form a halo-substituted bicycloheptadiene.
8. A process for the preparation of a halo-substituted
droxide and propanol at a temperature in the range of
from about 75° to about 200° C. to form S-dichloro
bicycloheptadiene which comprises condensing cyclopenta
methylene - 2 - norbornene and 2-dich1oromethyl-2,5-nor
diene with 2,3-dich1oro-1-propene, thereby forming 5
bornadiene.
12. A process for the preparation of a halo-substituted
chloro-S-chloromethyl-2-norbornene, and partially dehy
drohalogenating said heptene in the presence of potassium 10 bicycloheptadiene which comprises condensing 2,4-di
chloro-l-lbutene with cyclopentadiene, thereby forming
5-chloro-5-(2-chloroethyl)~2-norbornene, and partially
ene—2-norbornene and 2-chloromethy1-2,S-norbornadiene.
dehydrohalogenating said norbornene in the presence of
hydroxide and ethanol at a temperature in the range of
from about 75° to about 200° C. to form S-chloromethyl
potassium hydroxide and ethanol at a temperature in the
9. A process for the preparation of a halo-substituted
bicycloheptadiene which comprises condensing cyclopen 15 range of from about 75° to about 200° C. to form 5~(2
chloroethylidene-Z-norbornene and 2-(2-ch1oroethyl)-2,5
tadiene with 2,3-dibromo-1-propene, thereby forming 5
bromo-S-bromomethyl-2-norbornene, and partially dehy
norbornadiene.
drohalogenating said heptene in the presence of potassium
hydroxide and ethanol at a temperature in the range of
from about 75° to about 200° C. to form S-bromometh 20
ylene-2-norbornene and 2dbromo-2,5—norbornadiene.
10. A process 'for the preparation of a halo-substituted
bicycloheptadiene which comprises condensing cyclopen
tadiene with 1,3-dichloro-1-propene, thereby forming 5
chloro-G-chloromethyl- -norbornene, and partially dehy
drohalogenating said norbornene with potassium hydrox
25
ide and ethanol at a temperature in the range of from
about 75 ° to about 200° C. to form 6-chloro-5-methylene
2-norbornene and 2'ch1oromethy1-2,S-norbornadiene.
111. A process for the preparation of a halo-substituted 30
13.
14.
15.
16.
17.
18.
A S-haloalkylidene-Z-norbornene.
5-chloromethylene-2-norbornene.
S-bromomethyleneQ-norbornene.
6-chloro-5methylene-Z-norbornene.
5-diohloromethylene-2-norbornene.
5-(2-chloroethylidene)-2-norbornene.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,351,311
2,717,851
2,960,541
Alder et a1 ___________ __ June 13, 1944
Lidov _______________ __ Sept. 13, 1955
Elam et a1 ____________ __ Nov. 15, 1960
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