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Патент USA US3066165

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3,066,152
Patented Nov. 27, 1962
1
3,066,152
CYCLOALKENIC DERIVATIVES OF
EPOXYCYCLQl-EXANES
_
John P. Luvisi, Park Ridge, Ill., assignor to Universal Oil
Products Company, Des Plaines, lll., a corporation of
Delaware
No Drawing. Filed Dec. 22, 1961, Ser. No. 161,356
34 Claims. (Cl. 260-348)
in which the R’s are selected from the group consisting.
of hydrogen and alkyl radicals and the R"s are selected '
This application is a continuation-in-part of my co 10 from the group consisting of -R .and cyclo radicals hav- -
ing the generic formulae:
pending application Serial No. 808,868, ?led April 27,
1959, now abandoned, which was a copending applica
tion of Serial No. 675,006, ?led July 30, 1957, now aban
_ CECE)“
doned, and my copending application Serial No. 808,869,
?led April 27, 1959, now abandoned, which was a co
15
pending application of Serial No. 675,007, ?led July 30,
1957, now abandoned.
This invention relates to new compositions of matter
and to a method for the preparation thereof, and par
ticularly to a method for the preparation of cycloalkenic 20
derivatives of epoxycyclohexanes.
An object of this invention is to prepare derivatives of
epoxycyclohexanes by condensing unsaturated compounds
with said cyclohexanes.
.
Taken in its broadest aspect one embodiment of this
invention resides in a process which comprises condensing
l,2-epoxycyclohexane containing, as the sole additional
functional group, an ole?nic side chain of from 2 to
about 7 carbon atoms attached to a carbon atom of the
cyclohexane ring, said group consisting of carbon and 30 in which the X’s are selected from the group consisting of '1.
hydrogen and halo radicals, the R"’s are selected from the
hydrogen atoms, with an unsaturated compound selected
group consisting of hydrogen and alkyl radicals, and n!
from the group consisting of conjugated butadienes, cyclo
pentadienes, cyclohexadienes, halogenated conjugated
butadienes, halogenated cyclopentadienes, and halogen
is an integer of from 0 to about 5, at least one R’ being
selected from the cyclo radicals.
ated cyclohexadienes, said halogen being selected from
the groupconsisting of chlorine, bromine, and iodine, at
‘
A speci?c embodiment of this invention resides in a -
a temperature in the range of from about atmospheric to
about 300° C. and at a pressure in the range of from
process which comprises condensing dipentene monoxide "
with cyclopentadiene at a temperature in the range of"
from .about atmospheric to about 300° C. and at a pres-v
about atmospheric to about 100 atmospheres.
sure in the range of from about 1 to about 100 atmospheres ’
ane containing, as the sole additional functional group,
an ole?nic side chain of from 2 to 7 carbon atoms at
in a process for the preparation of 1,2,3,5-tetrachloro-4- >
A further embodiment of this invention is found in a 40 to form 5-methyl-5-(4-methyl-3,4-epoxycyclohexyl)-2-nor
bornene.
process which comprises condensing 1,2-epoxycyclohex
Another speci?c embodiment of this invention resides
tached to a carbon atom of the cyclohexane ring, said 45 methyl-4 - (4-methyl - 3,4 - epoxycyclohexyl)cyclohexene
which comprises condensing dipentene monoxide with
group consisting of carbon and hydrogen atoms, with a
halogenated unsaturated compound selected from the
1,2,3,4-tetrachloro-1,3-butadiene at a temperature in the '
range of from about atmospheric to about 300° C. and
group consisting of halogenated conjugated butadiene,
cyclopentadiene and cyclohexadiene, said halogenated
unsaturated compound consisting of carbon, hydrogen
and halogen atoms, the halogen being selected from the
group consisting of chlorine, bromine and iodine, at a
temperature in the range of from about atmospheric to
about 300° C. and at a pressure in the range of from
about atmospheric to about 100 atmospheres.
Yet another embodiment of this invention resides in a
process which comprises condensing 1,2-epoxycyclohex
at a pressure in the range of from about 1 to about 100 '
50
atmospheres.
_ Yet_another speci?c embodiment of this invention re- '
sldes 1n 1,2,3,4,7,7-heXachloro-5-methyl-5-(4-methy1-3,4- "
epoxycyclohexyl)-2-norbornene.
Other objects and embodiments referring to alternative
55 epoxy-cyclohexanes having an ole?nic side chain, as the
' sole additional functional group and to alternative unsatu- _
rated compounds, will be found in the following further
detailed description of this invention.
ane containing, as the sole additional functional group,
ole?nic side chain of from 2 to 7. carbon atoms attached
As hereinbefore set forth cycloalkenic derivatives of
to a carbon atom of the cyclohexane ring, said group 60 epoxycyclohexanes may be prepared by condensing an
consisting of carbon and hydrogen atoms, with a con
epoxycyclohexane containing an ole?nic side chain, as the
jugated halo-cyclopentadiene consisting of carbon, hy
drogen and halogen atoms, the halogen being selected
sole additional functional group, said group containing
only carbon and hydrogen atoms, with an unsaturated con
from the group consisting of chlorine, bromine and iodine,
jugated compound such as alkadienes, cycloalkadienes,
at a temperature in the range of from about atmospheric
to about 300° C. and at a pressure in the range of from
halo substituted alkadienes, or halo cycloalkadienes, to _
about atmospheric to about 100 atmospheres.
Still another embodiment of this invention is found in
a compound having the generic formula:
uses in the chemical ?eld.
form condensation products which ?nd a wide variety of
For purposes of this inven- ,
tion the term “cycloalkenic" as used hereinafter in the ._
speci?cation and appended claims will refer ‘to both cyclo
3,066,152
alkenic and bicycloalkenic derivatives of epoxycyclohex
alkyl, haloalkyl, halogen and‘hydrogen radicals, or poly
anes, and in addition it is contemplated within the scope
halo-cycloalkadienes having the general formula:
of this invention that the aforementioned term will em
brace both unsubstituted and halo substituted cycloalkenic
derivatives. Furthermore, the term “halo substituted”
will refer to both mono- and polyhalo substituted com—
pounds.
For example, the condensation product of cyclopenta
diene and dipentene monoxide (1-methyl-1,2-epoxy-4
in which the X’s have the same meaning as above and n
isopropenylcyclohexane), namely, 5-methyl-5-(4-methyl
10 is 1 or 2. Examples of these compounds include halo
3,4-epoxycyclohexyl)-2-norbornene may be used as an
alkadienes such as
intermediate in the preparation of an insecticide, the ?nal
1-chloro-1,3-butadiene,
1,3-dichloro-1,3-butadiene,
product which will possess insecticidal activity being pre
pared by halogenating, and particularly chlorinating, the
aforesaid intermediate by any means known in the art 15
such as treatment with chlorine, anhydrous hydrogen
chloride, etc., at appropriate temperatures and pressures,
1,1,3-trichloro-1,B-butadiene,
said chlorinated product being especially e?ective against
house?ies. It is also contemplated that the reaction prod
uct may be further condensed with hexachlorocyclopenta
diene to prepare products which are useful per se as in
secticides. In addition, if the unsaturated compound is
halo substituted, and particularly polyhalo substituted to
begin with, the Diels-Alder adduct may be useful as an
insecticide without further treatment such as further
halogenation.
For example, the Diels-Alder condensa
tion product of hexachlorocyclopentadiene and dipentene
monoxide, namely, 1,2,3,4,7,7-hexachloro-5-methyl-5-(4
methyl-3,4-epoxycyclohexyl)-norbornene may be used per
se as an insecticide, especially against house?ies. In addi
tion, the Diels~Alder adduct of this invention may also be
used as oxidation inhibitors or as intermediates in the
preparation of resins, pharmaceuticals, plastics, etc.
The process of this invention in which the unsaturated
compound comprising a conjugated diole?n such as an
1-bromo-l,3-butadiene,
1,3-dibromo-1,3-butadiene,
1,3-diiodo-1,3-butadiene,
l,1,3-tribron1o-1,3-butadiene,
l —iodo- l ,3-butadiene,
20 1
,Z-diiodo- 1,3-butadiene,
1 ,l,3-triiodo-1,3-butadiene,
1 ,1,2-trichloro-l,B-butadiene,
l ,1,2-tribromo-l,3-butadiene,
l
25 ,1,2-triiodo-1,3-butadiene,
1 ,l,4-trichloro-1,3-butadiene,
1 ,1,4-tribromo-l ,3-butadiene,
1 ,1,4-triiodo-1,3 -butadiene,
l ,1,4,4,-tetrachloro-l ,3-butadiene,
l
30 ,1,4,4-tetrabromo-1,3-butadiene,
1 ,1,4,4-tetraiodo-1,3-butadiene,
l ,1,2,3-tetrachloro-l ,3-butadiene,
l ,1,2,3-tetrabromo-1,3-butadiene,
1 ,1,2,3-tetraiodo-l,S-butadiene,
1
,1,2,3,4-pentachloro-1,3-butadiene,
35
alkadiene, cycloalkadiene, halogenated alkadiene, or halo
genated cycloalkadiene is condensed with the epoxycyclo
hexane containing an ole?nic side chain as the sole addi
tional functional group will be effected at a temperature
in the range of from about atmospheric to about 300° C. 40
or more and often preferably at a temperature in the
range of from about 100° to about 250° C., the tempera
ture depending upon the reactants which are to be con
densed. Generally, the reaction will take place at atmos
pheric pressure; however, if higher temperatures are used 45
when condensing a lower boiling diene with the epoxy
cyclohexane, superatmospheric pressures ranging from
about 2 to about 100 atmospheres will be used, the amount
of pressure being necessary to maintain at least a portion
1,1,2,3,4-pentabromo-1,3-butadiene,
1,1,2,3,4-pentaiodo-1,3-butadiene,
hexachloro—l,3-butadiene,
heXabrom0-1,3-butadiene,
hexaiodo-1,3-butadiene,
1,3-dichloro-2-methyl-1,3-butadiene,
1,4-dichloro-2-methyl-1,3-butadiene,
1,1,4,4-tetrachloro-2-rnethyl-1,3-butadiene,
l,4-dichloro-2-chlorornethyl-1,3-butadiene,
l ,4-dichloro-2-dichloromethyl-1,3-butadiene,
l ,1,4-trichloro-2-methyl-1,3-butadiene,
1 ,1,4,4-tetrachloro-2-methyl-1,3-butadiene,
l ,1,4,4-tetrachloro-2-chloromethyl-1,3-butadiene,
1 ,3-dibromo-2-methyl-1,3-butadiene,
l ,4-dibromo-2-rnethyl-1,3-butadiene,
of the reactants in the liquid phase. In addition, if so 50 l,l,4,4-tetrabrorno-2-methyl-1,3-butadiene,
desired, the reaction will take place in the presence of
1,4 dibrOmo-Z-bromomethyl-l ,3-buta diene,
inert organic solvents including aromatic solvents such
1 ,4-dibromo-2-dibromomethyl-1,B-butadiene,
as benzene, toluene, 0-, m- and p-xylene, ethyl benzene,
1,1,4-tribromo-2-methyl-l,3-butadiene,
etc.; alcohols such as methyl alcohol, ethyl alcohol, propyl
l,1,4,4-tetrabromo-Z-methyl-1,3-butadiene,
alcohol, etc.; ethers such as dimethyl ether, diethyl ether, 55 1 , 1,4,4-tetrabromo~2-bromomethyl-l ,3-butadiene,
dipropyl ether, etc.; saturated aliphatic hydrocarbons
1,3-diiodo-2-methyl-1,3-butadiene,
1,4-diiodo-2-methyl-1,3-butadiene,
1,1,4,4-tetraiodo-2-methyl-1,3~butadiene,
such as pentane, hexane, heptane, etc.; or acetone, acetic
acid, etc.
Unsaturated conjugated diole?nic compounds contain
ing at least one halogen substituent which may be reacted
60
with the epoxycyclohexane containing the ole?nic side
chain as the sole additional functional group, said group
1 ,4-diiodo-2-iodomethyl-1,3-butadiene,
1,1,4-triiodo-2-methyl-1,3-butadiene,
1,1,4,4-tetraiodo-2~rnethyl-1,3-butadiene,
1,1,4,4-tetraiodo~2-iodomethyl-l,3 -butadiene, etc.;
containing only carbon, hydrogen and halogen atoms, in
halocycloalkadienes such as halogenated 1,3-cyclopenta
the process of the present invention include straight-chain 65
dienes which for purposes of this invention will be desig
diole?ns having the general formula:
nated as halogenated cyclopentadienes including
in which the X’s are independently selected from the
group consisting of hydrogen or halogen radicals having
an atomic weight of from 35 to 127 (Le. chlorine, bro
mine or iodine), at least 1 of the X’s being halogen and Y
is independently selected from the group consisting of
70
l-chlorocyclopentadiene,
1,Z-dichlorocyclopentadiene,
1,2,3-trichlorocyclopentadiene,
1,2,3,4-tetrachlorocyclopentadiene,
1,2,3,4,5~pentachlorocyclopentadiene,
hexachlorocyclopentadiene,
l-bromocyclopentadiene,
l,2-dibromocyclopentadiene,
5,066,15é
5
1,2,3-tribroniocyclopentadiene,
2-ethyl-l,3-hexadiene,
3-ethyl-1,3-hexadiene,
2,3-diethyl-1,3-hexadiene,
2,4-heptadiene,
3-methyl-2,4-heptadiene,
4-methyl-2,4-heptadiene,
3,4-dimethyl-2,4-heptadiene,
1,2,3,4-tetrabromocyclopentadiene,
1,2,3,4,5-pentabromocyclopentadiene,
hexabromocyclopentadiene,
l-iodocyclopentadiene,
1,Z-diiodocyclopentadiene,
1,2,3-triiodocyclopentadiene,
1,2,3,4-tetraiodocyclopentadiene,
1,2,3 ,4,5-pentaiodocyclopentadiene,
3 -ethyl-2,4-heptadiene,
hexaiodocyclopentadiene, etc.
10
It is also contemplated within the scope of this inven
tion that polyhalo substituted conjugated cyclohexadienes
such as 1,Z-dichloro-1,3-cyclohexadiene, 1,2,3-trichloro
1,3-cyclohexadiene, octachloro-1,3-cyclohexadiene, etc.,
1,Z-dibromo-1,3-cyclohexadiene, 1,2,3-tribromo-1,3-cyclo
hexadiene, octabromo-1,3-cyclohexadiene, 1,2-diiodo-1,3
15
4-ethyl-2,4-heptadiene,
3,4-diethyl-2,4-heptadiene,
1,3-heptadiene,
2-methyl-1,3-heptadiene,
3-methyl-1,3-heptadiene,
2,3-dimethyl-1,3-heptadiene,
2-ethy1-1,3-heptadiene,
3-ethyl-l,3-heptadiene,
2,3-diethyl-1,3-heptadiene, etc.;
cyclohexadiene, 1,2,3~triiodo - 1,3 - cyclohexadiene, octa
iodo-1,3-cyclohexadiene, etc., may also be used. In addi
cycloalkadienes and alkyl substituted cycloalkadienes such ’
tion, it is also contemplated that polyhaloalkadienes and
as 1,3-cyclopentadienes which for purposes of this inven
tion will be designated as cyclopentadienes and include
polyhalocycloalkadienes which are used in this process
may contain more than one species of halo substituents,
such as, for example,
1,1-dichloro-3-bromo-l,3-butadiene,
1-chlor0-3-bromo-l,3~butadiene,
25
1-iod0-3-chloro-1,3-butadiene,
2-bromo-3-chloro-l ,3-butadiene,
1,4-dichloro-2-bromomethyl-1,3-butadiene,
1,4-dichloro-2-iodomethyl~1,3-butadiene,
1-chloro-Z-bromocyclopentadiene,
1.,2-dichloro-3-bromocyclopentadiene,
cyclopentadiene,
l-methylcyclopentadiene,
2-methylcyclopentadiene,
S-methylcyclopentadiene,
1,2-dimethylcyclopentadiene,
1,3-dimethylcyclopentadiene,
5 ,5 -dimethylcyclopentadiene,
l ,2, 3 -trimethylcyclopentadiene,
1,2,3,4-tetramethylcyclopentadiene,
v30 hexamethylcyclopentadiene,
1,Z-dichloro-5,5-dibromocyclopentadiene, etc.,
may be used although not necessarily with equivalent re
sults.
Diole?nic conjugated hydrocarons containing only car
35
bon and hydrogen atoms which may be reacted with the
epoxycyclohexane containing an ole?nic side chain as the
sole additional functional group in the process of the
present invention include straight-chain conjugated di
ole?ns having the general formula:
l-ethylcyclopentadiene,
2-ethylcyclopentadiene,
5~ethylcyclopentadiene,
1,2-diethylcyclopentadiene,
1,3-diethylcyclopentadiene,
5,5-diethylcyclopentadiene,
1,2,3-triethylcyclopentadiene,
1,2,3 ,4-tetraethylcyclopentadiene,
40 hexaethylcyclopentadiene, etc.
it is also contemplated within the scope of this‘invention ’
that conjugated cyclohexenes such as
1,3 -cyclohexadiene,
in which the R’s are independently selected from the
l-methyl-1,3-cyclohexadiene,
group consisting of alkyl or hydrogen radicals, at least 45 Z-methyl-1,3-cyclohexadiene,
one R of each of the doubly bonded carbon atoms being
5-methyl-1,3 -cyclohexadiene,
hydrogen; or conjugated cycloalkadienes having the gen
eral formula:
R
50
meg
/
R
1,5,6-trirnethyl-l,3-cyclohexadiene, etc.,
in which the R’s are independently selected from the group
consisting of hydrogen or alkyl radicals.
may also be used although not necessarily with equivalent
results.
Epoxycyclohexanes containing an ole?nic side chain
Examples of
these compounds include conjugated alkadienes such as
1,3-butadiene,
2-methyl-1,3-butadiene (isoprene),
2,3-dimethyl-1,3-butadiene,
1,3-pentadiene,
2-methyl-1,3-pentadiene,
3-methyl-1,3-pentadiene,
2,3-dimethyl-1,3-pentadiene,
2-ethyl-1,3-pentadiene,
3-ethyl-l,3-pentadiene,
2,4-hexadiene,
3-methyl-2,4-hexadiene,
3 ,4-dimethyl-2,4-hexadiene,
of from 2 to about 7 carbon atoms as the sole additional
60 functional group, said group containing only carbon and
hydrogen atoms, which may be used in the process of
this invention include
65
70
3-ethyl-2,4-hexadiene,
3,4-diethyl-2,4-hexadiene,
1,3-heXadiene,
2-methyl-3,4-hexadiene,
3 -methyl-1,3-hexadiene,
1,2-dimethy1-1 ,3-cyclohexadiene,
1,3-dimethyl-1,3-cyclohexadiene,
1,4-dimethyl-1,3-cyclohexadiene,
5,6-dimethyl-1,3-cyclohexadiene,
1,2,3-trimethyl-l,3~cyclohexadiene,
1,2,4-trirnethyl-1,3-cyc1ohexadiene,
1,4,5-trimethyl-1,3-cyclohexadiene,
75
1,2-epoXy-3-vinylcyclohexane,
l,2-epoxy-4~vinyl-cyclohexane,
1,2-epoxy-3-allycyclohexane,
1,2-epoxy-4-allylcyclohexane,
1,2-epoxy-3-methallylcyclohexane,
1,2-epoXy-4-metha1lylcyclohexane,
1,2,-epoxy-3-crotonylcyclohexane,
1,2-epoxy-4-crotonylcyclohexane,
1,2-epoxy-3-pentenylcylohexane,
1,2-epoxy-4-pentenylcyclohexanel.
1,2-epoxy-3-( 1-rnethyl-3-pentenyl) cyclohexane,
1,2-epoxy-4-( 1-methyl-4-pentenyl) cyclohexane,
‘13,066,152
1S
l,2-epoxy-3 -propyl-4-vinylcyclohexane,
1,2-epoxy-1-methyl-4-crotonylcyclohexane,
'
subject to insect infestation, their toxic effects being mani
fested by contact of the poison with the insect. The
insecticides comprising the present compound are thus
1,2-epoxy- l-ethyl-4-crotonylcyclohexane,
1,2-epoxy-3-methyl-4-crotonylcyclohexane,
1,2-epoxy-3-ethyl-4-crotonylcyclohexane,
1,2-epoxy-3,5-dimethyl-4-vinylcyclohexane,
1,2-ep oxy-3 ,5 -dimethyl-4-allylcyclohexane,
1,Z-epoxy-3,6-dimethyl-4-vinylcyclohexane,
effective against chewing as well as sucking types of in
sects. The compounds are sufficiently volatile so that
when applied to plant life intended for subsequent hu
man consumption, the plants when harvested and after
allowing a reasonable time for evaporation of the applied
1,2-epoxy3,6-diethyl-4-a1lylcyclohexane, etc.
It is to be understood that the aforementioned conjugated
alkadienes, cycloalkadienes, halo substituted alkadienes
and cycloalkadienes, and the epoxycyclohexanes contain
ing an ole?nic side chain as the sole additional functional
group are only representatives of the class of compounds
which may be used and that this invention is not neces
insecticide therefrom retain none of the toxicant to pre
vent use of the plant for consumption as food. On the
other hand, the compounds are of su?iciently limited
volatility to be retained on the insect for the time re
quired to accomplish the toxic effects of the compounds.
The volatility and retentive capacity of the compounds
15 may be varied at will by combining them with suitable
?xing agents which reduce or promote their volatilization,
as desired. Thus, the compounds may be dissolved in a
sarily limited thereto.
One example of the condensation reaction of the pres
ent process may be illustrated by the following equations
in which dipentene monoxide is reacted with l,3-dichloro—
1,3-butadiene and hexachlorocyclopentadiene respectively:
suitable high boiling solvent, such as a mineral or vege
table oil, petroleum, etc.; a wax, such as para?in wax,
20 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 emulsifying
agent, such as surface active agent, to the mixture of
components. The latter solvents and dispersements may
25 also be employed for the speci?c purpose of reducing
the concentration of insecticide to the desired level in av
speci?c insecticide formulation, the particular formula
H30
01
1__O
E20
Cl
/
/
1_0
or
or
+ l t
01
/
~——»
__
01
/o\
H3
tion of active components in combination with the sol
vent or dispersant Will depend upon its application. Com
30 positions containing as high as 20% of active component
may be preferred, in some instances where deep pene
tration of the insecticide is desired, as in the treat
ment of ?brous material, such as wood, for extinc
tion of a particular infestation, for example, Wood ter
35 mites. For other purposes, the required concentration
01
mo /\ 01
C \CH2
ClOCl
i
of active components in the formulation may be as low‘
as 0.1%, as for example in the treatment of fabrics for
destroying moth larvae. in utilizing the present insecti-.
Cl
cidal compounds against most insects, a composition con
Cl
40 taining from about 0.1% to about 5% by weight of the
active component is highly effective. The choice of
Another example of the condensation reaction of the
the most desirable solvent or dispersant further depends
present process may be illustrated by the following equa
upon the method utilized to apply the insecticidal com
tions in which 1,2-epoxy-4-vinyl-cyclohexane is reacted
position to the infested article. 'For example, a low
with 2-methyl—1,3-butadiene (isoprene) and cyclopenta
diene respectively:
45
'
molecular weight, normally gaseous carrying agent for
the active insecticidal component, such as propane, bu
tane, the Freons, etc., may be compressed and lique?ed
into a small bomb containing the insecticide. Upon re
lease of pressure from the bomb, the lique?ed carrier va
50 porizes and suspends a quantity of the active component
therein, thus providing a convenient spraying method of
applying the insecticide. The active component may also
HO
//
be dissolved in a liquid carrier, such as kerosene, an al
CH2
cohol, ester, ketone, etc., and the resulting solution at
omized by a suitable spraying device.
The process of the present invention may be effected
in any suitable manner and may comprise either a batch
0
/
O
or continuous type operation.
For example, when a
batch type operation is used, a quantity of the starting
materials comprising the epoxycyclohexane containing
an ole?nic side chain as the sole additional functional
OH:
I
to yield 1-methyl-4-(3,4-epoxycyclohexyl)—il-cyclohexene
and 5-(3,4-epoxycyclohexyl)-2-norbornene respectively.
The physical properties of the present halocycloalkenic
group, said group containing only carbon and hydro
gen atoms, and, if so desired, an inert organic solvent
is placed in a condensation apparatus provided with heat
ing and mixing means. The apparatus is then adjusted
to the desired temperature and the conjugated ole?n
such as alkadiene or cycloalkadiene containing only car
bon and hydrogen atoms or a haloalkadiene or halo
cycloalkadiene containing only hydrogen, carbon, and
derivatives of epoxycyclohexanes and the effects they have 70 halogen atoms is added thereto at a predetermined rate,
the temperature of the ?ash being maintained at the de
on entomological forms of life make them particularly
desirable as insecticides and insect repellents, the com
sired level for a predetermined residence time.
At the
end of this time the apparatus and contents thereof are
pounds having many of the features desired of materials
allowed to cool to room temperature and the desired re
of this purpose. They are, for example, toxic to insects
which are destructive to plant life and materials normally 75 action product is separated from unreacted starting ma
speenee
12
11
terials by conventional means such as, for example, frac
1,2-dibromo-5-methyl-5- ( 4-methyl-3,4-ep oxycyclohexyl) -
tional distillation, crystallization, etc.
2-norb ornene,
1,3-dibromo-5 -methyl-5-( 4-methyl-3,4-epoxycyclohexyl) -
Alternatively,
the reactants and solvent, if any, may be ?rst admixed
and then heated to the desired reaction temperature.
2-norbornene,
Another method of effecting the condensation reaction
of the present invention is by a continuous type opera
tion. In this type of operation the starting materials com—
prising the epoxycyclohexane containing an ole?nic side
1,4-dibromo-5-methyl-5- (4-methyl-3,4-epoxycyclohexyl) -
chain as the sole additional functional group and the
alkadiene, cycloalkadiene, haloalkadiene or halocyclo 10
alkadiene are continuously charged to a reactor which
2-norbornene,
1,2,3 -tribromo-5-methyl-5-( 4-methyl-3,4-epoxycyclo
hexyl ) -2-norbornene,
1,2,3 ,4-tetrabromo-5-methyl-5—( 4-rnethyl-3 ,4-epoxycyclo
hexyl ) -2-norbornene,
1,2,3 ,4,7,7-hexabromo-S-rnethyl-S-(4-rnethyl-3 ,4-epoxy
cyclohexyl) -2-norb ornene,
is maintained at the proper operating conditions of tem
perature and pressure. The reactor may comprise an
unpacked vessel or coil or may be lined vwith an adsorbent
1,2-diiodo-5-metl1yl-5- (4-methyl-3 ,4-epoxycyclohexyl ) -
packing material such as ?re brick, alumina, dehydrated 15
'1,3-diiodo-5-methyl-5-(4-methyl-3,4»epoxycyclohexyD-2
bauxite, or the like. If so desired, inert organic solvents
of the type hereinbefore set forth may be added through
norbornene,
1,4-diiodo-5-methyl-5- ( 4-methyl-3,4-epoxycyclohexyl) -2
nor'oorne,
2-norb ornene,
a separate line or admixed with one or the other of the
starting materials prior to entry into said reactor and
1,2,3 ~diiodo-5-n1eth31l-S- ( 4-n1ethyl-3 ,4-epoxycyclohexyl) charged thereto in a single line. The reaction product is 20
2-norbornene,
l,2,3,4-diioclo-5-methyl-5- ( 4-methyl-3,4-epoxycyclo
continuously withdrawn from the reactor e?luent, and
puri?ed by conventional means hereinbefore set forth,
hexyl ) ~2-norbornene,
while the reaction starting materials are separated and
1,2,3 ,4,7,7-‘1exaiodo_-5-methyl-5-(4-methyl-3,4-epoxycy
recharged to the reactor as a portion of the feed stock.
clohexyl) -2-norb ornene,,
Examples of reaction products which are prepared ac 25 1,2-dichloro-4-methyl-4- ( 4-methyl-3 ,4-epoxycyclohexyl ) cording to the present process comprise compounds hav
l-cyclohexene,
ing the generic formula:
3 ,6~dichloro-4-methyl~4- ( 4-methyl-3,4-epoxycyclohexyl ) -
l-cyclohexene,
2,3-dichloro-4-methyl-4-(4-methyl-3,4-epoxycyclohexyl) -
30
2/
BAR,
R,
35
l-cyclohexene,
1,2,3 -trichloro-4-rnethyl-4- (4-methyl-3,4-epoxycyclo
hexyl ) -1-cyclohexene,
1,2,3,3-tetrachloro-4-methyl-4- (4-methyl-3,4-epoxycyclo
hexyl) -1-cyclohexene,
1,2,3,3,6,6-hexachloro-4-methyl-4-(4-methyl-3 ,4-epoxy
in which the R’s are selected from the group consisting
of hydrogen and alkyl radicals and the R"s are selected
1,3-dibromo-4-methyl-4- ( 4-methyl-3 ,4-epoxycyclohexyl) ~
from the group consisting of R and cyclo radicals having
the generic formulae:
3 ,6-dibrorno-4~methyl-4- ( 4-methy1—3,4-epoxycyclohexyl ) -
cyclohexyl ) - l -cyclohexene,
l-cyclohexene,
40
l-cyclohexene,
2,3 -dibrorno-4-methyl-4- ( 4-methyl-3 ,4-epoxycyclohexyl ) -
1—cyclohexene,
1,2,3 -tribromo-4-methyl-4-( 4-rnethyl-3,4-epoxycyclo
hexyl) -1-cyclohexene,
1,2,3,3-tetrabrorno-4-methyl-4-(4-methyl-3,4-epoxycyclo
hexyl) -1-cyclohexene,
1,2,3 ,3 ,6,6-hexabrorno-4-methy1-4- ( 4-methyl-3,4-epoxy
cyclohexyl) -1-cyclohexene,
1,3 -diiodo-4-methyl-4-(4-methyl-3,4-epoxycyclohexyl) ~1
and
cyclohexene,
3,6-diiodo-4-n1ethyl-4-(4-methyl-3,4-epoxycyclohexyl) -1
cyclohexene,
2,3-diiodo—4-methyl-4—(4-methyl-3,4-epoxycyclohexyl) -1
cyclohexene,
1,2,3-triiodo-4-methyl-4- (4-methyl-3,4-epoxycyclohexyl ) -
l-cyclohexene,
1,2,3 ,3-tetraiodo-4-methyl-4-( 4-methy1-3,4-epoxycyclo
hexyl) -1-cyclohexene,
in which the X’s are selected from the group consisting
of hydrogen and halo radicals, the R"’s are selected from
1,2,3,3,6,6-hexaiodo-4-methyl-4~(4-methyl-3,4-epoxycyclo
the group consisting of hydrogen and alkyl radicals, and
hexyl) -l-cyclohexene, etc.,
S-methyl-S- (4-methyl-3,4-epoxycyclohexyl) -2-norbor
n is an integer of from 0 to about 5, at least one R’ being
selected from the cyclo radicals, include
nene,
1,2-dichloro-S-methyl-5- ( 4-methyl-3,4-epoxycyclohexyl) -
2-norbornene,
1,3-dichloro-5-methyl-5- ( 4-methyl-3,4-epoxycyclohexyl ) -
2-norbornene,
(i5
5-( 4-methyl-3 ,4-epoxycyclohexyl) -2-norbornene,
5-( 4-ethyl-3,4-epoxycyclohexyl ) -2-norbornene,
5- ( 3,4-epoxycyclohexyl) -2-norbornene,
4-methyl-4-(4-methyl-3,4-epoxycyclohexyl)-1-cyclo
1,4-dich1oro-5-methyl-5- ( 4-methyl-3,4-epoxycyclohexyl) 2-norb ornene,
hexene,
4- ( 4-methyl-3 ,4-epoxycyclohexyl) -1-cyclohexene,
1,2,3 -trichloro-5~methyl-5- ( 4-methyl-3,4-epoxyclohexyl) -
4-( 4-ethyl-3 ,4-epoxycyclohexyl) - l-cyclohexene,
2-norbornene,
1,2,3,S-tetrachlorQ-S-methyI-S- ( 4~methyl-3,4-,epoxycyclo
hexyl) -2-norbornene,
4- (3,4-epoxycyclohexyl) -1-cyclohexene, etc.
The following examples are given to illustrate the
process of the present invention, which, however, are
1,2,3,4,7,7-hexachloro-5-methyl-5- (4-methyl-3,4-epoxy
cyclohexyl) -2-n0rbornene_,
not intended to limit the generally broad scope of the
present invention in strict accordance therewith.
l’i
spews
14%
13
cyclohexyl)~cyclohexane is recovered by fractional distil
Example I
A mixture of 54 g. (0.2 mole) of hexachlorocyclo
pentadiene and 25 g. (0.2 mole) of 1,2-epoxy-3-vinylcy
lation under reduced pressure.
Example VII
An insecticidal solution is prepared by dissolving 1 g.
clohexane dissolved in 50 g. of toluene was re?uxed at
a temperature of about 110° C. for a period of about 6
of 1,2,3,4,7,7 - hexachloro - 5 - methyl-5-(4-methyl-3,4
hours during which time the inert solvent, toluene, was
distilled over until the reaction temperature reached 171°
C. The reaction mixture was maintained at this tempera
epoxycyclohexyl)~2-norb0rnene in 2 cc. of benzene and
adding 100 cc. of water using Triton X——100 as an emulsi
fying agent. This solution is sprayed into a cage contain
ture for an additional 21 hours after which time the ves
ing common house?ies and causes a 100% knock-down.
sel and contents thereof were allowed to cool to room 10 Similar tests with compounds prepared according to Ex
temperature. The reaction product was recovered,
amples I and III to VI will show similar results.
washed, dried and distilled under reduced pressure. The
Example VIII
cut boiling in a range of from 183.5" to 188° C. at 0.8
mm. pressure (393 °—395° C. at 760 mm. pressure) was
A mixture of 5.4 g. (0.1 mole) of 1,3-butadiene and
separated and recovered, this product had a refractive 15 12.3 g. (0.1 mole) of 1,2-epoxy-4-vinylcyclohexane dis
solved in 50 g. of toluene is re?uxed at a temperature of
index ring‘) of 1.5673. The out which comprised 1,2,3,4,
about 100° C. for a period of about 6 hours during which
7,7-hexachloro-5-(3,4-epoxycyclohexyl) -2-norbornene was
analyzed with the following results.
Found: C, 39.34; H, 3.20; C1, 5331.
C13H12C160‘1: C,
H,
Calcd. for
C1,
time the inert solvent, toluene, is distilled over until the
reaction temperature reaches approximately 200° C. The
20 reaction mixture is maintained at this temperature for an
additional two hours after'which time the vessel and con
Example I]
tents thereof are allowed to cool to room temperature
and the reaction product is recovered, washed, dried and
A mixture of 27 g. (0.1 mole) of hexachlorocyclopen
tadiene and 15 g. (0.1 mole) of dipentene monoxide (1 25 subjected to fractional distillation under reduced pressure.
The desired product, comprising 4-(3,4-epoxycyclohexyl)
methyl-1,2~epoxy-4-isopropenylcyclohexane) dissolved in
l-cyclohexeue is separated therefrom.
50 g. of toluene is re?uxed at a temperature of about 110°
C. for a period of about 6 hours during which time the
Example IX
inert solvent, toluene, is distilled over until the reaction
A
solution
of
12.3
g.
(0.1 mole) of 1,2-epoxy-4-vinyl
temperature reaches approximately 200° C. The reaction
cyclohexane and 6.5 g. (0.1 mole) of cyclopentadiene in
mixture is maintained at this temperature for an addi
50 g. of xylene is heated under re?ux for a period of about
5 hours during which time the xylene is distilled over until
the reaction temperature reaches a maximum of about
225° C. At the end of this time the ?ask and contents
tional 2 hours, after which the vessel and contents thereof
are allowed to cool to room temperature and the reaction
product is recovered, washed, dried and distilled under
reduced pressure. The desired product, comprising
thereof are allowed to cool to room temperature and the
l,2,3,4,7,7 - hexachloro - 5 - methyl - 5 - (4-methyl-3,4—
reaction product is recovered, washed, dried and subjected
epoxycyclohexyl) -2-norbornene is separated therefrom.
to fractional distillation under reduced pressure.
The
Example 111
desired product, comprising 5-(3,4-epoxycyclohexyl)-2
A solution of 15 g. (0.1 mole) of dipentene monoxide
and 32 g. (0.1 mole) of 1,3-dichloro-1,3¢butadiene in 50
norbornene is separated and recovered therefrom.
Example X
A solution of 15 g. of l-methyl-1,2-epoxy-4-isopropenyl
cyclohexane (dipentene monoxide) and 5.5 g. of 1,3
g. of xylene is heated under reflux for a period of about
5 hours during which time the xylene is distilled over
until the reaction temperature reached a maximum of
about 225° C. At the end of this time the ?ask and
butadiene in 50 g. of toluene is heated under re?ux for
about 5 hours, after which time the product is recovered
and treated as described for the products of Examples I
contents thereof are allowed to cool to room temperature
and the reaction product is recovered, washed, dried and
subjected to fractional distillation under reduced pressure.
and II above. The desired product, comprising 4-methyl
4-(4-methyl-3,4-epoxycyclohexyl)-l-cyclohexene is recov
The desired product, comprising 1,3-dichloro-4-methyl-4
(4-methyl - 3,4 - epoxycyclohexyl)-l-cyclohexene is sepa
50
rated therefrom.
'
ered therefrom.
Example XI
A solution of 15 g. of dipentene monoxide and 6.5 g.
of cyclopentadiene in 50 g. of xylene is treated as described
in Examples I to III above. The desired product, com
Example IV
A solution of 15 g. of dipentene monoxide and 15 g. of
1,3,4-trichloro-1,3-butadiene in 50 g. of toluene is heated 55 prising 5-methyl-5-(4-methyl-3,4-epoxycyclohexyl)-2-nor
under re?ux for about 5 hours, after which the product
bornene is recovered by fractional distillation under re
is recovered and treated as described for the products of
duced pressure.
Examples I and II above. The desired product, compris
Example XII
ing 1,2,5 - trichloro - 4 - methyl - 4 - (4-methy1-3,4-epoxy
cyclohexyl)-l-cyclohexene is recovered therefrom.
Example V
A solution of 15 g. of dipentene monoxide and 7 g. of
60 2-methyl-1,3-butadiene (isoprene) in 50 g. of benzene is
subjected to the same treatment as described in the above
examples. The desired product, comprising 1,4-dimethyl
A solution of 15 g. of dipentene monoxide and 14 g. of
4-(4-methyl-3,4-epoxycyclohexyl)-1-cyclohexene is recov
ered by fractional distillation under reduced pressure.
1,3-diehloro-2-methyl-1,3~butadiene (1 ,3-dichloroisoprene)
in 50 g. of xylene is treated as described in Examples I to
III above. The desired product, comprising 2,6-dichloro
1,5-dirnethyl-5~(4-methyl-3,4-epoxycyclohexyl) - 1 - cyclo
hexene is recovered by fractional distillation under re
duced pressure.
Example VI
65
Example XIII
Equimolecular proportions of the compound prepared
in Example VII above, namely, 4-(3,4-epoxycyclohexyl)
l-cyclohexene and hexachlorocyclopentadiene are con
70 densed to form the desired product. An insecticidal solu
tion is prepared by dissolving l g. of this product in 2 cc.
A solution of 15 g. (0.1 mole) of dipentene monoxide
of benzene and adding 100 cc. of water using Triton
and 18.5 g. (0.1 mole) of 1,2,3,4-tetrachloro-1,3-buta
X-100 as an emulsifying agent. This solution is sprayedv
diene in 50 g. of toluene is treated as described in Ex
into a cage containing common house?ies and causes a
amples I to-IV above. The desired product comprising
1',2,3,5-tetrachloro - 4 - methyl-4-(4-methyl - 3,4 - epoxy 75 100% knock-down. Similar tests with other compounds
3,eee,152
15
i?»
prepared according to Examples IX to X11 and thereafter
oxide with hexachlorocyclopentadiene at a temperature in
the range of from about atmospheric to about 300° C. and
chlorinated or condensed with hexachlorocyclopentadiene
will show similar results.
at a pressure in the range of from about 1 to about 100
I claim as my invention:
atmospheres.
1. A process which comprises condensing 1,2-epoxy
cyclohexane containing, as a sole additional functional
'
15. A process for the preparation of 1,3-dichloro-4
methyl-4-(4-methyl - 3,4 - epoxycyclohexyl)-1-cyclohex
group, ole?nic side chain of from 2 to 7 carbon atoms at
tached to a carbon atom of the cyclohexane ring, said
ene which comprises condensing dipentene monoxide with
of conjugated butadiene, cyclopentadiene and cyclohexa
pheres.
diene and chlorinated, brominated and iodated conjugated
butadiene, cyclopentadiene and cyclohexadiene, at a tem
perature in the range of from about atmospheric to about
methyl-4-(4-methyl - 3,4 - epoxycyclohexyl)-1-cyclohex
1,3-dichloro-1,3-butadiene at a temperature in the range
of from about atmospheric to about 300° C. and at a
group consisting of carbon and hydrogen atoms, with an
unsaturated compound selected from the group consisting 10 pressure in the range of from about 1 to’ about ‘100 atmos~
'16. A process for the preparation of 1,2,5-trichloro-4
ene which comprises condensing dipentene monoxide with
300° C. and at a pressure in the range of from about 15 1,3,4-trichloro-1,3-butadiene at a temperature in the range
atmospheric to about 100 atmospheres.
2. A process which comprises condensing 1,2-epoxy
cyclohexane containing, as the sole additional functional
of from about atmospheric to about 300° C. and at a
pressure in the ‘range of ‘from about 1 to about 100 atmos
pheres.
'
17. A process for the preparation of 2,6-dichloro-1,5
group, ole?nic side chain of from 2 to 7 carbon atoms
attached to a carbon atom of the cyclohexane ring, said
dimethyl - 5 - (4 - methyl - 3,4 L epoxycyclohexyl) - 1 - cy
group consisting of carbon and hydrogen atoms, with a
clohexene which comprises condensing dipentene monox
ide with 1,3-dich1oro-2-methyl-1,3-butadiene at a tem
chlorinated conjugated butadiene consisting of carbon,
perature in the range of from about atmospheric to about
hydrogen and chlorine atoms, at a temperature in the
range of from about atmospheric to about 300° C. and at
300° C. and. at a pressure in the range of from about 1
a pressure in the range of from about atmospheric to 25 to about 100, atmospheres.
about 100 atmospheres.
18. A process for the preparation of l,2,3,5.-tetrachloro
3. A process which comprises condensing 1,2-epoxy
4 - methyl - 4 - v(4 - methyl - 3,4 - epoxycyclohexyDcyclo
cyclohexane containing, as the sole additional functional
hexene which comprises condensing dipentene monoxide
group, ole?nic side chain of from 2 to 7 carbon atoms
attached to a carbon atom of the cyclohexane ring, said
group consisting of carbon and hydrogen atoms, with a
with 1,2,3,4-tetrachloro-l,3-butadiene at a temperature in
the range of from about-atmospheric to about 300° C.
and at a pressure in the range of from about 1_ to about
chlorinated conjugated cyclopentadiene consisting of car
bon, hydrogen and chlorine atoms, at a temperature in
the range of from about atmospheric to about 300° C.
100
atmospheres;
‘
>
'
'
'
'
i
i
19. A process which comprises condensing 1,2~epoxy
4-vinylcyclohexane with 1,3-butadiene at a temperature in
and at a pressure in the range of from about atmospheric 35 the range of from about atmospheric to about 300° C.
to about 100 atmospheres.
and at a pressure in the range of from about 1 to about
100 atmospheres, to form 4-(3,4-epoxycyclohexyl)-1-cy
4. A process which comprises condensing 1,2-epoxy
cyclohexane containing, as the sole additional functional
clohexene.
'
'
"
group, an ole?nic side chain of from 2 to 7 carbon atoms
attached to a carbon atom of the cyclohexane ring, said 40
20. A process which comprises condensing '1,2;epoxy
4-vinylcyclohexane with cyclopentadiene at a temperature
group consisting of carbon and hydrogen atoms, with a
in the range of from about atmospheric to about 300° C.
conjugated butadiene consisting of carbon and hydrogen
and at a pressure in the range of from about 1 to about
atoms at a temperature in the range of from about atmos
pheric to about 300° C. and at a pressure in the range of
bornene.
from about atmospheric to about 100 atmospheres.
5. A process Which comprises condensing 1,2-epoxy
cyclohexane containing, as the sole additional functional
21. A process 'which comprises condensing dipentene
monoxide with 1,3-butadiene at a temperature in the
range of from about atmospheric to about 300° C. and
group, an ole?nic side chain of from 2 to 7 carbon atoms
at a pressure in the range of from about 1 to about 100
attached to a carbon atom of the cyclohexane ring, said
group consisting of carbon and hydrogen atoms, with a
clohexyl) -1-cyclohexene.
100 atmospheres, to form 5-(3,4-epoxycyclohexyl)-2-nor
atmospheres, to form 4-rnethyl—4-(4-methyl-3,4-epoxycy—
conjugated cyclopentadiene consisting of carbon and hy
drogen atoms at a temperature in the range of from about
atmospheric to about 300° C. and at a pressure in the
22. A process which comprises condensing dipentene
monoxide with cyclopentadiene at a temperature in the
range of from about atmospheric to about 300° C. and
range of from about atmospheric to about 100 atmos
at a pressure in the range of from about I to about 100
6. The process of claim 1 in which said epoxycyclo
hexane is dipentene monoxide.
7. The process of claim 1 in which said unsaturated
clohexyl ) -2-norbornene.
723. _A process which comprises condensing dipentene
monoxide with 2-methyl—l,3-butadiene at a temperature
compound is hexachlorocyclopentadiene.
in the range of from about atmospheric to about 300° C.
pheres.
atmospheres to form 5—methyl-5-(4-methyl-3,4-epoxycy
and at a pressure in the range of from about 1 to about
8. The process of claim 1 in which said unsaturated
100 atmospheres, to form ‘1,4-dimethyl-4-(4-methyl-3,4
compound is 1,3-dichloro-l,3-butadiene.
epoxycyclohexyl) -1-cyclohexene.
9. The process of claim 1 in which said unsaturated
'
24. A compound of the formula:
compound is 1,3,4-trichloro-1,3-butadiene.
10. The process of claim 1 in which said unsaturated 65
compound is 1,3-dichloro-2-methyl-l,3-butadiene.
11. The process of claim 1 in which said unsaturated
compound is l,2,3,4-tetrachloro-1,3-butadiene.
12. The process of claim 1 in which said unsaturated
compound is 1,3-butadiene.
13. The process of claim 1 in which said unsaturated
70
compound is cyclopentadiene.
14. A process for the preparation of 1,2,3,4,7,7-hexa
chloro-S-methyl-S-(Al-methyl - 3,4 - epoxycyclohexyl) - 2
in which the R’s are selected from the group consisting
norbornene which comprises condensing dipentene mon 75. of hydrogen and alkyl radicals and the R”s are selected
3,066,152
17
18
form the group consisting of R and cycle radicals of the
radicals, and n is an integer of from 0 to 5, at least one
formulae:
R’ being selected from the cyclo radicals.
25. 1,2,3,4,7,7 - hexachloro - 5 - methyl - 5 - (4 - meth
yl-3,4-epoxycyclohexyl)-2-norbornene.
26. 1,3 - dichloro - 4 - methyl - 4 - (4 - methyl - 3,4
ep oxycyclohexyl ) -1-cyclohexene.
27. 1,2,5 - trichloro - 4 - methyl - 4 - (4 - methyl - 3,4
epoxycyclohexyl ) ~1-cyclohexene.
x
X
x
it
and
X
RI!
28. 2,6 - dichloro - 1,5 - dimethyl - 5 - (4 - methyl - 3,4
10
epoxycyclohexyl)-1-cyclohexene.
29. 1,2,3,5 - tetrachloro - 4 - methyl - 4 - (4 - methyl
3 ,4-epoxycyclohexyl) cyclohexene.
30. 4- ( 3,4-epoxycyclohexyl) -1-cyclohexene.
31. 5-(3,4-epoxyclohexyl)-2-norbornene.
32. 4 - methyl - 4 - (4 - methyl - 3,4 - epoxycyclohex
y1)-1-cyc1ohexene.
33. 5 - methyl - 5 - (4 - methyl - 3,4 - epoxycyclohex
yl ) -2-norb ornene.
34. 1,4 - dimethyl - 4 - (4 - methyl - 3,4 - epoxycyclo
20 hexyl ) - 1 -cyclohexene.
in which the X’s are selected from the group consisting of
hydrogen, chlorine, bromine and iodine, the R”’s are se
lected from the group consisting of hydrogen and alkyl
References Cited in the ?le of this patent
Harrer et al.: Chem. Abs., vol. 40, p. 1505 (1946).
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