Note: Descriptions are shown in the official language in which they were submitted.
PP 29295/ A
This application is a divis:ion oE Serial No. 2g5,309
filed January 19, 1978.
This invention relates to novel cyclopropane derivatives
use~ul as insecticides, to processes for their preparation,
to compositions comprising them and to methods of combating
insec-t and similar invertebrate pests using them.
Certain naturally occurring esters of cyclopropane
carboxylic acids have long been known to possess insecticidal
properties, but these compounds have been too easlly degraded
by ultra violet light to be of much use in agrlculture.
Several groups of synthetlc compounds based on cyclopropane
carboxylic acids (for example those disclosed in British
patent specifications nos 1,243,8S8 and 1,413,491) have been
evaluated ln an attempt to discover compounds of sufficient
light stability for use as general agricultural insecticides.
We have now discovered that compounds according to the
~ 15 general formula:-
: O
~ RlR2C=CH-CH_cH_c_R
C
CH CH
3 3
wherein Rl and R2 are both haloalkyl gro~ps containing 1 or
2 carbon atoms or in which one of Rl and R2 is such ~ halo-
; ~ alkyl group and the other is a halogen atom or a methyl
~ group, and in which R is a phenoxybenzyloxy group optionally
:,~
~ - 2 -
.
.. .: . :
:: : ~ , ., ........... "'
: . . .
. ;. ~ .
: :~ ~ " .. -' :
substituted in the a-position by a cyano or ethynyl group
have very good insecticidal properties combined with good
resistance to light degradation, and that similar compounds
wherein R is a hydroxy group or an alkoxy group containing
up to 6 carbon atoms, or a halogen atom are useful as
intermediates for the preparation of insecticides. Where R
is a phenoxybenzyloxy or a-substituted phenoxybenzyloxy
group it is preferably a 3-phenoxybenzyloxy or a-substituted
3-phenoxybenzyloxy group.
In one aspect.therefore the present invention provides
compounds according to the general formula:-
o
RlR2C=CH-CH-CH-C-O-CH (R3)~,oC6H5
: CH3 CH3 (I)
l 2
wherein one of R and R represents a group of formula:-
' '
: ~ W- (CF2)m-
where W represents an atom of hydrogen, fluorine or chlorine
and m has the value one or two, and the other of Rl and R2
represents an atom o fluorine, chlorine or bromine or a
group of formula:-
.
- 3 -
~: ~ , ... . .
:' - - - : . ' ' :
.: - :.
. ~ .
r ~L266~8
s
Y
i~ i
X--C--
., I
i¢ whexe each of X, Y and Z independently represents an atom
~¢ of hydrogen, fluorlne or chlorine, and R3 represents an
a,~om of hydrogen or the cyano or ethynyl group.
One preferred group o compounds within the invention
1 5 are those according to the general formula I given above
, in which one of Rl and R2 represents a group of formula:-
WCF2 ~
~ `
where W represents an atom of hydrogen, fluorine or chlorine,
and the other of Rl and R2 represents a group of formula:-
~ ~,
~ v
X--C--
.~ ~ z
where X, Y and Z are as defined above, and R3 represents
an atom of hydrogen or the cyano group. Withln this
~; prefexred group o compounds those which are particularly
~; ~ : preferred are those wherein Rl and R2 are both trifluoro-
~;~ methyl groups.
,
. ':
~ 4 -
:~:
.
~,
~: , , : .:
:
: ~ : . . ;,, ,
.
.. :.. .. , . . : ..
7!3
Another pre~erred group of compounds within the invention
are those according to the general formula I given above in
which one o R and R2 represents a group of formula:-
WCF2 -
where W represents an atom of hydrogen, fluorine or chlorine,
and the other of R1 and R2 represents a fluorine, chlorine,
or bromine atom, and R3 represents an atom of hydrogen or
the cyano group. Especially preferred compounds within this
group are those wherein one of Rl and R2 represents the
trifluoromethyl group and the other represents a chlorine or
bromine atom.
It will be appreciated by those skilled in the art that
the compounds represented by formula I are capable of
existing in various geometrical and stereoisomeric forms.
Thus there may be cis and trans isomers arising from the
substitution pattern of the cyclopropane ring, and E- and Z-
isomers arising from the substituted vinyl group when Rl is
not the same as R2. In addition two of the three carbon
atoms of the cyclopropane are capable of existing in either
:,
R- or S-configurations since they are asymmetrically sub-
stituted, and when R3 is not hydrogen the carbon atom to
which it i5 attached is also capable of existing in either
the R- or S- configuration.
~: :
,~ ~
.....
~6~
Thus for a compound according to formula I where Rl and
R2 are the same and R3 is hydrogen, there are four isomeric
possibilities, arising from the cyclopropane ring substit-
ution. These may be named by reference to their absolute
configuration as tl~,3R), ~lR,3S), (lS,3S) and (lS,3R).
When R is not hydrogen there are eight possible isomers
since each of the four possible cyclopropane ring config-
urations must exist in two forms, one corresponding to the
S-configuration and one to the R-configuration of the carbon
atom bearing the R3 group. Alternatively if R3 is hydrogen,
and Rl is not the same as R2 there are again eight isomeric
possibilities since each of the four possible cyclopropane
ring configurations must exist in two forms, one corresponding
to the Z-configuration and one to the E-configuration of the
vinyl group.
Finally when Rl is not the same as R , and R is not
hydrogen, each compound may exist in sixteen isomeric forms.
In Table I there are listed compounds according to the
:
invention. Each of the compounds listed is a racemic mixture
of (~) and ~-) isomers, although a distinction is made
between cis and trans substitution on the cyclopropane ring
~: and E- and Z-substitution in the vinyl group where this is
~`~ present.
: The compounds of Table I all conform to the following
formula:-
6 -
.
; - , ,
~:
: - . :~ ;:.. .... .
, . ~ : : : :: . , :,. . : , , . , :
~ .' ': :
R ~ ,H ll
~ ~ OC6H5
~.'( /
/
: :~ /
__ _ _ ~ __ _
-:
~:
7 -
- ~
O H
O 1~
H Z ~ U~ 3 u~ 3 u~ 3 u~ 3 u~ 3 u~ 3
~ 11~ H ~ h r~
1-1 0 E-~
., ~
O ~ ~
~ .
__ . .. .- _ ___ _ _ r _ . _ . _ _ _
~P; Z Z ~ ~ ~C Z ~ Z Z
__
~`3
C~; C) ~ C~ U C~ U
_ -- -- ._.. ____ _ _.__ _ _ _
-
~ ~ ~ ~ r~
:~. ~ ~
__ _~ ... _ . ,_ ,,
~0 ~ O ~ ~
V . ~:
__ ~ _ _ ~ ,_ _ ,
:
~ .
:~ .
a-
~ ;
~ . .
. .
. . ~ ,: ..
:: .,.. -.: . .
.
~.2~i6~
. _ . ,.
O H
Z
H Z E~ U~
E-( ~ Z 1~
ul ~~ tn 0
~ O ~
H O E~ U OC~ t) ~ ~ U U -IJ ~ O t)
1~
æ ~ ~
Cl ~ .
_ . ..
~ ~ O ~J Z Z Z Z Z Z; Z Z
Z ~ U C~
o . __ _ _
, ~ ~ ~ ~ r~
. ~ ~. ~ ~ ~ ~ ~ ~ ~ ~: ~ $ ~ X
~3 ~ o U ~ '' '' " ''
. . .~
:: ___ ~ __ _ _ _ _
,';'`: : O O ~ ~ Ln u:~ I~ oo ~ O ~ ~ ~ ~r
` .` ~ Z~ ~ ~1 ~ .
O ..... ___ . .. __
'''' ~
: ~ ~
. ~ .
: ~ ,
:
:
~ _ 9 _ .
: `
:
.
` - ' ,` ~. '`~ , - ... .
~: ~
; , :` - :
~L~66~
... ...
O H
Z~
O ~U~
H Z E~ u~
. O ~) h h ~ h ~ ,1 h h
~ ~ ~ ~) t) V ~J ~, O U ~) ~ t) C)
H O E~
1~
Z t~ a:
O
O ~ ~
_ .. . ....
z ~ 5~ , Z Z æ z
z .~ _
o ~ ~ C.~ ~4~ ~ ~.~ ~ ~ .
~~ ~ ~ ~ ~ ~C ~ ~ ~ ~ ~ ~
E~ ~; O C~
~ ~1 ~ ~1
~ ~ (r~ ~ ~ U ~ C~ (`~
,~ . ~
"~ ~
., . Z
~ O O ~D 1~ CO O~ O ~1 ~ ~ ~ Ln ~.D
8 ~ N t~
:
:,j
` .,
! ~
' ,~'`.`:
~;J ~
10 -
:: :
;~ ` ` ~ , '
' ; . ~ '
,
'~ ~ ,~''' ',
`~ '`'
~ , ., ., ~ ,
: `' ~ . ,
67~
. .. ~ ~
o~
~ Z E~ u~
O ~ ~ h
H O E~
E~
0
C~
: ~ . __
z ~ ta ~ æ Z Z Z Z
~ ~ U~ ,~ U~
H _ U ~ U C)
_
~ ~ U~ ~ ~
,:.o P~ C~ U U ~ U U ~ U
: ~
`'. ~: ~ OO I` co a~ o
~ Z ~ ~ ~ ~ ~ ~ . ~ ~
:: o : --~
: ~ :
: : : :
:: ~ ` : : : : : ` ::` : :
L2~6678
~ _ . _
oZ
o ~ tn
~ Z E~ u~
~ ~ Z U~
O ~ ~rl h ~ l Ll ~ rl h ~ rl h h
C~ ~4 H C~ ~ t) ~ ~ C) O ~ ~ t) t) ~ JJ
H O E~
O
O U
... ..... ~
Z ~ ~: ~ U U Z Z U Z Z ~
~` ~. Z . __ . . -_ .
O ~`I ~~ h~
~i ~ ~ 1:4 U C ) U a~ u ~q t ) u o o u
, ~: ~ .. _, .__ _ - - .. _ . ... _
::
~1
E~ C~ U ~ ~ ~ ~ r~
. ~ ~ U ~
1:~; ;:4 ~ 1:4 EL~ ~ V ~ C~ Ç~ O U U
~` .C~ C.) C) C) ~
O U U
Z
~' C~ O ~ O ~I ~ ~ ~ U~ O
O ._~
~"
;
' :
~ - 12 -
: " ' ` , ~ ~ '
::: -:'
~ ~ . ` ' ,.~ " -
: :: :
Particularly useful compounds of formula I according
to the invention include:
(+)-a-cyano-3-phenoxybenzyl ~+)-cls/~rans-3-(2-chloro-
3,3,3-~rifluoroprop-1-en l-yl)-2,2-dimethylcyclopropane
car~oxylate,
(+)-a-cyano-3-phenoxybenzyl (+)-cis/trans-3-(3,3,3-trifluoro-
2~trifluoromethylprop-l-en-l-yl)-2,2-dimethylcyclopropane
carboxylate,
(+)~a-cyano-3~phenoxybenzyl (+)-cis/trans-3-(3-chloro-
2,3,3-trifluoroprop-l-en-1-yl)-2,2-dimethylcyclopropane
carboxylate,
~:: (+)-a-cyano-3-phenoxybenzyl (~-cls/trans-3-(3-bromo-
3,3,3-trifluoroprop-1-en~l-yl)-2,2-dimethylcyclopropane
carboxylate,
~: 15 3-phenoxybenzyl (+)-cls/trans-3-(2-chloro-3,3,3-trifluoro-
prop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate~ and
-~ 3-phenoxybenzyl (+)-cis/trans-3-(3,3,3-trifluoro-2-trifluoro-
methylprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate.
:~
:~
: = 13 -
, .
.,, ~ . .
~2~ 8
The compounds of the invention according to Formula
I are esters and may be prepared by conventional esteri-
fication processes, of which the following are examples.
: . (a) An acid of formula:-
o
RlR2C=CH-CH--CH-C-OH
\ /
C
C 3 CH3
where Rl and R2 have any of the meanings given hereinabove,
may be reacted directly with an alcohol of formula:-
Ho-CH(R3) ~ 6 5
where R represents the hydrogen atom, or the cyano or
:~ ethynyl group, the reaction preferably taking place in the
~: presence of an acld catalyst, for example, dry 'nydrogen
::
. 10 chloride.
~` (b) An acld halide of formula:-
: O
; RlR2C=CH-CH~CH C-Q
/ \
CH3 ~H3
. ~
~ - 14 -
~ . , ;.~ .
,
6~3
where Q represents a haloyen atom, preferabLy a chlorine
atom, and Rl and R2 have any of the meanings given herein-
above, may be reacted with an alcohol of ormula:-
HocH(R3) ~ C6H5
ll ~J
wherein R3 represents the hydrogen atom or the cyano or
ethynyl group, the reaction preferably taking place in the
presence of a base, for example, pyridine, alkali metal
hydroxide or carbonate, or alkali metal alkoxide. As an
alternative when R3 is to be the cyano group, a mixture of
alkali metal cyanide and 3-phenoxybenzaldehyde may be
employed in place of a-cyano-3-phenoxybenzyl aLcohol.
(c) An acid of formula:-
~" O
~ RlR2C=CH-CH CH-C-OH
\C/
: ~ : / \
:~ ~ CH3 CH3
or, preferably, an alkali metal salt thereof, may be reacted
with a halide of formula:-
~:~ : Q'-CH(R3) ~ C6H5
- 15 -
',
"~
,
.: , , . . . -
where Q' represents a ha:Logen atom, preferably the chlorine
atom, and R represents the hydrogen atom, or the cyano or
ethynyl group, or with the quaternary ammonium salts derived
rrom such halides with tertiary amines, for example pyridine,
or trialkyl amines such as triethylamine.
(d) A lower alkyl ester of formula:-
o
RlR2c=cH-cH-cH-c-oR
C
/ \
; CH3 CH3
where R represents ~ lower alkyl group containing up to six
carbon atoms, preferably the methyl or ethyl group, and Rl
;; and R2 hava any of the meanings given hereinabove, is heated
with an alcohol of formula:-
HO-CH(R ) ~ C6H5
,~ ~
to effect a transesterification reaction. Preferably the
process is performed in the presence o~ a suitable catalyst,
for example, an alkali metal alkoxide, such as sodium
methoxide, or an alkylated titanium derivative, such as
~` 15 tetramethyl titanate.
:`
~ - 16 -
'~
-
..,
~*~6~7~
All of these conventional processes for the preparation
of esters may be carried out using solvents and diluents for
the various reactants where appropriate, and may be accelerated
or lead to higher yields o product when performed at
S elevated temperatures or in the presence of appropriate
catalysts, for example phase-trans~er catalysts.
The preparation of individual isomers may be carried
out in the same manner but commencing from the corresponding
individual isomers of compounds of formula II. These may
be obtained by conventional isomer separation techniques
from mixtures of isomers. Thus cis and trans isomers may
be separated by fractional crystallisation of the carboxylic
acids or salts thereof, whilst the various optically active
species may be obtained by fractional crystallisakion of
salts o~ the acids with optically active amines, followed
by regeneration of the optically pure acid.
The op~ically pure isomexic form of the acid (or its
equivalent acid chloride or ester) may then be reacted with
3-phenoxybenzyl alcohol to produce the compounds of formula
I in the orm of an individually pure isomer thereof. In
the case of a-cyano~3-phenoxybenzyl alcohol the product will'
be a mixture of two isomers since it is not possible to
react optically pure a-cyano-3-phenoxybenzyl alcohol with
the acid or its equivalent without racemisation of the
alcohol occurring. Typical products of this procedure
-~ include:
, ~
~ 17
:
. ~ , . . . ...
I ,.. . ~ .
:
.
~:6~
(+)~~-cyano-3-phenoxybenzyl (lR,3R)~3-(3,3,3-trifluoro-2-
trifluoromethylprop-len-1-yl)-2,2~dimethylcyclopropane
carboxylate, and
(+)-a-cyano-3-phenoxybenzyl (lR,3S)-3-(2-chloro-3,3,3-
trifluoroprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate~
These compounds are believed to be especially useful as
insecticides.
The preparation of single isomers of these compounds
may be achieved by preparing the optically pure acid chloride
and reacting it with (~)-3~phenoxymandelamide to give the
corresponding (+)~a~carboxamido ester. The two isomeric
esters may be separated by fractional crystallisation, and
individually subjected to dehydration to the corresponding
~ .
~-cyano-3-phenoxybenzyl ester. In this way the following
single lsomers may be obtained.
(S)-a cyano-3-phenoxybenzyl (lR,3R)-3-(3,3,3-trlfluoro-2-
trifluoromethylprop-l-en-l-yl)~2,2-dimethylcyclopropane
carboxylate, and
(S)-~-cyano-3-phenoxybenzyl (lR,3S)-3-(2-chloro-3,3,3-
trifluoroprop-l-en-1-yl)-2,2-dimethylcyclopropane carboxylate.
~; which are believed to be the insecticidally most effective
isomers of those particular compounds.
,
:,
~ 18 -
,~
:
'~
78
The various cyclopropane compounds referred to herein-
above as being useful as intermediates in the processes by
which the invention compounds of Formula I may be prepared
are themselves novel compounds.
In further aspect therefore the present invention
provides compounds according to the general formula:-
RlR2C=CH-CH_CE~_c_Q
C
CH / \CH ~II)
wherein one of Rl and R2 represents a group of formula:-
.
W (CF2 ) m_
where W represents an atom of hydrogen, fluorine or chlorine
and m has the value one or ~wo, and the other of Rl and R~
represents an atom of fluorine, chlorine or bromine or a
group of formula:-
:. Y
~ I
: ~ ~ X-C-
Z
19
. ~
~26~ 7~3
where each of X, Y and Z independently represents an atom of
hydrogen, fluorine or chlorine, and Q represents the hydroxy
group, a lower alkoxy group containing up to six carbon
atoms, or the chlorine or bromine atom.
One preferred group of intermediates within the invention
are those according to the general formula II given above in
which one of Rl and R2 represents a group of formula:-
WCF2 -
where W represents an atom of hydrogen, fluorine or chlorine,
~ and the other of Rl and .R2 represents a group of formula:-
:~: "' Y
X--C--
Z
~,
where X, Y and Z are as defined above, and Q represents the
:~ hydroxy group, a lower alkoxy yroup containing from one to~:: three carbon atoms, or the chlorine or bromine atom. Within
this preferred group of compounds those which are particularly
preferred are those wherein Rl and R2 are both trifluoro-
methyl groups.
Another preferred group of intermediales within the
:: in~ention are those according to the general ~ormula II
- 20 -
.
:
.
~ . .-
..
given above in which one of R1 and R2 represents a group of
formula:-
WCF2 -
.
where W represents an atom of hydrogen, 1uorine or chlorine,
and the other of Rl and R2 represents a fluorine, chlorine,
or bromine atom, and Q represents the hydroxy group, a lower
alkoxy group containing from one to three carbon atoms, or
the chlorine or bromine atom. Especially preferred compounds
within this group are those wherein one of Rl and R2
represents the trifluoromethyl group and the other represents
a chlorine or bromine atom.
The compounds represented by formula II are also
capable of existing in various geometrical and stereoisomeric
forms in the same way as the compounds of formula I. Thus
there may be cis and trans isomers arising from the sub-
stitutlon pa~tern of the cyclopropane ring, and E- and Z-
~ isomers arising from the substituted vinyl group when Rl is
;~ not the same as R2. In addltion two of the three carbon
.
atoms af the cyclopropane are capable of existing in either
R-;or S-conigurations since they are asymmetrically sub-
20~ stituted.
Examples o~ specific intermediate compounds according
. ~
; to the invention include those represented by the following
general formula:
21 -
"~
~. . . . - , ...
~ ~ - ,. ' :
~6~
Rl H O
' \ / 11
C=C \ C-Q
R2 C-C
/\1\
H C H
CH3 CH3
wherein Rl and R2 have the specific meanings given in Table
I hereinabove for the corresponding compounds of formula I
and wherein Q represents a chlorine atom, a hydroxy group or
an ethoxy group.
The compounds of formula II wherein Q i5 hydroxy may be
obtained by~hydrolysis of the compounds of formiula II
wherein Q is lower alkoxy, and may be converted to the
compounds of formula II wherein Q is chloro or bromo by
:,
reaction with for example thionyl chloride or thionyl
bromide respectively~ All of the compounds of formula II
may be used either directly or indirectly to prepare the
~`~ insecticidally active esters of formula I, as described
hereinabove.
~Y'
The compounds of formula II wherei~ Q is lower alkoxy
lS may be prepared by a variety of processes. One method
~ :,
~ invol~es reacting a diene of ormula:-
.
.
~,,
~"
:;
~ 22 -
~ .
~ ~ .
~:; . :
: ~ -: . . : .
:::; ~
~6~ 7~
Rl /CH3
C=CH-CH=C
R2/ \ CH3 (V)
with a lower alkyl ester of diazoacetic acid. This gives
rise to the required compound of formula II directly. The
process is conveniently conducted using an excess of the
diene as a solvent for the alkyl diazoacetate in the presence
of a metallic catalyst, for example powdered copper or
copper bronze.
In a variation of the above process a compound of
formula III may be obtained by the reaction of the unsatur-
ated alcohol of formula IV with a lower alkyl diazoacetate,
and may be converted to a compound of formula II where Q is
lower alkoxy by dehydration with a chemical dehydrating
agent, for example, phosphorus pentoxide.
~ OH o
'~ R R21-CX2-CH-5H_C_Q
: C
'~,, ~ / \
~ ~ CX3 CH3 (III)
~: :
~: ,
~ 23 -
~: :
. - . .
7~3
OH CH3
1 2
R R C-CH2-CH-C
CH3 (IV)
This variant of~ the diazoacetate process is not applicable
; to the preparation of compounds wherein one of Rl and R2
is a halogen atom, but is very useful for the preparation
of compounds where Rl and R2 are both trifluoromethyl
groups, or wherein one of Rl and R2 is trifluoromethyl
and the other is difluoromethyl.
. In a.yet further aspect the invention provides
:~ compounds of formula.-
' 1
R \ CH3
C-CH-CH=C
2/
~: R CH3 (V)
~"
wherein Rl and R2 are as defined hereinabove for the
compounds o formula I, and compounds of formula:
~ i
R \ OH
C CH
:~ 2
- R CH2-CH=C
: CH3 ~IV)
wherein Rl is tri1uoromethyl, and R2 is ~rifluoromethyl
~: or difluoromethyl.
- 24 -
:, - : , ,
~ ~ :
.
7~
The compounds of formula IV may be obtained by reacting
a ketone of formula:-
o
1 11 2
R -C-R (VI)
with 3-methylbut-l~ene~ prefera~ly under pressure. The
corresponding compounds of ormula V may be obtained by
dehydration, with e.g. phosphorus pentoxide, of the compounds
of formula IV.
The compounds of formula V wherein Rl and R2 are both
haloalkyl groups or wherein one of Rl and R2 is a haloalkyl
; group and the other is a methyl group may also be obtained
by reacting the corresponding ketone of formula:
O
-C-R
~: "
~`; with the ylld obtained by treating a 3,3-dimethylallyl
triphenylphosphonium halide, preferably the chloride or
;
bromide, with a suitable dehydrohalogena~ing agent, for
example an alkyllithium compound such as n-butyllithium.
The phosphonium halide may be obtained by reacting triphenyl
: phosphine with a 3,3-dimethylallyl halide. Dienes which may
~ -:
: be obtained by this process include those of formula V
:! 1 2
wherein R and R are as defined in the following table:
:
~:
: : 25
- _
~:
~,,,, ~ , '
:- ,,
:
::.,
:::
Ill R2
CF3 CF3 .
CHF2 CHF2
CF3 CHF2
CF3 CH3
CF2Cl CF2Cl
CHF2 .
;'
Examples of compounds of formula IV are 5-hydroxy-
:~ 2-methyl-6,6,6-trifluoro-5-trifluoromethylhex-2-ene and
5-hydroxy-2-methyl-6,6-dlfluoro-5-trifluoromethylhex-2- .
ene, and these may be dehydrated to 2-methyl-6,6,6-trifluoro-
5-trifluoromethylhexa-2,4-diene and 2-methyl-6,6-difluoro-
~: 5-trlfluoromethylhexa-2,4 diene as examples o compounds
: of formula V.
Another method of preparing the compounds of formula II
where Q is alkoxy involves the base induced ring closure of
: 10 a:compound of formula:-
W' CH3 O
Rl-C-CH2-CH--C-CH -C-Q
2 ~ l l 2
R ~ W~ ~ CH3 (VII)
:: :
wherein R and~R have any of the meanings given above, Q is
, . - : :
~ alkoxy, and W' and W " are each either fluorin2, chlorine or
. ~ ~
- 26 -
' ~
bromine, provided tha-t W' is bromine when R2 is bromine.
Suitable ~ases for carrying out the process include
tertiary amines, for example pyridine, triethylamine,
diethylaniline and N~methylpiperidine, and also alkali metal
lower alkoxides, that is those containing up to six carbon
atoms, for example sodium methoxide, sodium ethoxide, and
sodium and potassium t-butoxide. The step is conveniently
carried out in a diluent or solvent for the reactant and the
base. A particularly convenient manner of conducting this
process is to treat a solution of the compound of formula
III in an alcohol corresponding to the alkali metal alkoxide
being used for a period of from 0.5 to 20 hours.
At least two moles of base are required to convert the
compounds of formula VII to the compounds of formula II
where R is alkoxy, and this involves two separate stages,
cyclisation and ~-elimination of hydrogen halide, but it is
not clear in what order these two stages proceed or if they
~;~ proceed simultaneously.
When the process i5 conducted using only one molar
equivalent of base three different products are obtained
corresponding ~o the following formulae:
R CH 0
3 ll
C=CH-CH - C-CH -C-Q
2/ 1 1 2
~ RW'' CH3 (A)
; '
~ - 27 -
~'
'
~$~
W' CH O
1 1 1 3 1l
R -C-CH=CH-C-CH2C-Q
12
R CH3 (B)
W' O
1 1 11
R -C-CH -CH-CH-C-Q
R C
CH3 CH3 (C)
Each of these species on treatment with a further molar
equivalent of base gives the compound of ormula III, and
in a further aspect therefore the invention provides a
process for preparing the compounds of formula II where Q
is alkoxy by treating a compound of ormula A, B or C with
~;~ at least one molar equivalent of a base.
Although the process may be used for the preparation of
all of the compounds of formula II where Q is alkoxy it is
particularly useful for the preparation of compounds wherein
one o Rl and R2 is a halogen atom.
~- The compounds of formula VII useful as intermediates in
~ : the preparation of the compounds of formula II may be
::~ prepared by reacting a compound o formula:-
o
~- : CH2=CH-C(CH3)2-CH2-C-Q (VIII)
~"~:
~ 28 -
:~: ., .
:~ , : ' .
6~i6~3
wherein Q is alkoxy, with a compound of formula:-
Rl-C-W' '
W' (IX)
wherein Rl, R2, W' and W'' have any o the meanings given
hereinbefore, in the presence of a free radical initiator.
This may be a physical initiator such as irradiation wi-th a
suitable e.g. ultra violet, light source, or a conventional
chemical free radical catalyst, such as e.g. benzoyl peroxide
~: or azobisisobutyronitrile. The process may conveniently be
carried out by using an excess o~ the compound of formula V
. as a diluent, at temperatures in the range 50C to 150C,
preferably 80 to 120C for periods of from 1 to 20 hours,
~:: optionally in a sealed system and under the autogenic
pressure of the reaction.
; ~ A particularly useful compound of formula VIII is ethyl
-; ~ 3,3-dimethylpent-4-enoate, although other lower alkyl esters
lS may al~o be used.
The ester o~3,3-dimethylpent-4-enoic acid represented
by formula VIII may be replaced by other compounds in which
the carboxylate function is replaced by an equivalent
: :.
function, by which we mean a functional group which does not
~;
- 29 -
,, ~ - : , .
:
~ .
interfere with the process set out hereinahove but which may
subsequently be chemically modified by oxidation or hydrolysis
to give the carboxylic acid, for example the nitrile, acetyl,
or formyl group. Alternatively the compound of formula VIII
may be replaced by a compound of formula:
Q''
CH2=cH-c(cH3)2-cH-Ql
where Q' is selected from alkoxycarbonyl, cyano and acetyl
; and Q'' is cyano or alkoxycarbonyl.
A yet further process by which the compounds of formula
II wherein Q is alkoxy may be prepared involved the reaction
of a diene of formula V with an alkyl malonate in the presenc0
of a reducible copper salt, and optionally in the presence
~ of another salt selected from halldes of Group I and Group II
.~
metals such as lithium chloride or calcium chloride. The
initial product which has the formula:
Q'' O
RlR2C=CH-CH-C - C-Q
~;:~ \ I
:~ C
~; / \
CH3 CH3
4~
~ - 30 -
i
~,
- , ' '
:: , .. .
,:
~6~
wherein R , R2, and Q " have the meanings given above and Q
is alkoxy, may be converted to the required products of
formula II by conventional hydrolytic and esterification
procedures.
Examples of compounds of formula IX useful in the above
processes include hexafluoroethane, chloropentafluoroethane,
l,l-dichlorotetrafluoroethane, 1,2-dichlorotetrafluoroethane,
l,l,l-trichlorotrifluoroethane, l,1,2-trichlorotrifluoro
ethane, l,l,l-tribromotrifluoroethane, l,1,1,3-tetrachloro-
tetrafluoropropane and 1,1,3-trichloropentafluoropropane.
When the various processes for the preparation of the
intermediates of ormula II are carried out the products are
usually mixtures of the various geometrical isomers. Thus
the processes may lead to a mixture of cis and trans
isomers, often with one form predominating, and, in the
cases where Rl is not the same as R2, 2- and E~isomers of
both cis and trans forms, again oten with one form pre-
.~.
~ dominating.
- Unless these forms are separated by some physical
process, e.g. fractional crystallisation of the carboxylic
acids, the final products of formula I will also consist of
mixtures of the various isomers, containing more than one of
the compounds of Table 1. Typical examples of insec~i-
cldally active products, most of which are mix~ures of more
than one compound, which have been obtalned include those
~`.' .
:
~,
- 31 -
. . . ~ . .
.~ .
.
~6~6~7~
set out hereinbelow.
Product no 1 : A mixture of 1 part of compound no 1 with
4 parts of compound no 2.
Product no 2 : A mixture of 1 part of compound no 1 with
1 part of compound no 2.
Product no 3 : Compound no 2 alone.
Product no 4 : Compound no 1 alone.
Product no 5 : A mixture of 19 parts of compound no 31
with 1 part of compound no 32.
Product no 6 : A mixture of 19 parts of compound no 31,
1 part of compound no 32, 19 parts of
compound no 33, and 1 part of compound
no 34.
Product no 7 : A mixture of 11 parts of compound no 3
with 14 parts of compound no 4.
Product no 8 : A mixture of compounds nos 15, 16, 17 and
18 (composition undetermined).
Product no 9 : A mixture of 1 part of compound no 39 with
1 part of compound no 41.
Product no 10 : A mixture of 19 parts of compound no 43,
1 part of compound no 44, 19 parts of
; compound no 45 and 1 part of compound no
46.
Product no 11 : A mixture~of 19 parts of compound no 43
with 1 part of compound no 44.
: :~
~;
- 32 -
: .,
~: , ' ~ " ,
' ' ' ,' ::
':
7~
Product no 12 : A mixture of 19 parts of compound no 39
with 1 part of compound no 40.
Product no 13 : A mixture of 1 part of compound no 19,
9 parts of compound no 20, 1 part of
compound no 21 and 9 parts of compound
no 22.
Product no 14 : A mixture of 1 part of compound no 23,
9 parts of compound no 24, 1 part of
compound no 25 and 9 parts of compound
no 26.
Product no 15 : A mixture o 1 part of compound no 47
~; with 1 part of compound no 48.
Product no 16 : Compound no 47.
~: Product no 17 : A mixture of 1 part of compound no 49 with
1 part of compound no 50.
Product no 18 : A mixture of 1 part of compound no 1 with
with 2 parts of compound no 2.
Product no 19 : A mixture o 3 parts of compound no S with
~: 2 parts of compound no 6.
~ 20 Product no 20 : A mixture of 3 parts of compound no 7 with
;~ 2 parts of compound no 8.
Product no 21 : A mixture of 9 parts of compound no 35,
~: 1 part of compound no 36, 6 parts of
` ; compound no 37 t and 4 parts of compound
no 38.
33 -
'''
~; . ~, ~ . i . :
:, ~
: ~ , . . .
.
Product no 22 : A mix-ture of 9 parts of compound no 51
with one part of compound no 52.
Product no 23 : Compound no 53 alone.
Product no 24 : A mixture of 7 par-ts of compound no 9 with
13 parts of compound no 10.
Product no 25 : A mixture of 7 parts of compound no 11
with 13 parts of compound no 12.
Product no 26 : A mixture undetermined compositions
containing compounds 27, 28, 29 and 30.
Product no 27 : A mixture of 10 parts of compound no 54,
1 part of compound no 55, 10 parts of
compound no 56 and 1 part of compound
no 57.
Product no 28 : A mixture of 10 parts of compound no 58,
: lS 1 part o~ compound no 59, 10 parts of
; compound no 60 and 1 part of compound
no 61.
~ Product no 29 : A mixture of 2 parts of compound no 13
: with 3 parts of compound no 14.
~ The compounds of formula I may be used to combat and
: ~ control infestations of insect pests and also other inver~ebrate
pests, for example, acarine pests. The insect and acarine
~` pests which may be combated and controlled by the use of
the invention compounds include those pests associated with
:;
34 -
.
.~.~ - .
~: `
: , : ' ::
i6~3
agriculture (which term includes the growing of crops for
food and fibre products, horticulture and animal husbandry),
forestry, the storage of products of vegetable origin, such
as fruit, grain and timber, and also those pests associated
S with the transmission of diseases of man and animals.
In order to apply the compounds to the locus of the
pests they are usually formulated into compositions which
include in addition to the insecticidally active ingredient
or ingredients of formula I suitable inert diluent or
carrier materials, and/or surface active agents. The
compositions may also comprise another pesticidal material,
for example another insecticide or acaricide, or a fungicide,
or may also comprise a insecticide synergist, such as for
example dodecyl imidazole, safroxan, or piperonyl butoxide.
The compositions may be in the form of dusting powders
wherein the active ingredient is mixed with a solid diluent
or carrier, for example kaolin, bentonite, kieselguhr, or
talc, or they may be in the form of granules, wherein the
active ingredient is absorbed in a porous granular material
for example pumice.
Alternatively the compositions may be in the form of
liquid preparations to be used as dips or sprays, which are
generally aqueous dispersions or emulsions of the active
ingredient in the presence of one or more known wetting
agents, dispersing agents or emulsifying agents (surface
active agents)-.
- 35 -
,:
:, . . .
: . .~ .. : .. ...... . .
~6~
Wetting agents, dispersing agents and emulsifying
agents may be of the cationic, anionic or non-ionic type.
Suitable agents of the cationic type include, for example,
quaternary ammonium compounds, for example, cetyltrimethyl
ammonium bromide. 5uitable agents oE the anionlc type
include, ~or example, soaps, salt~ o aliphatic monoesters
or sulphuric acid, for example sodium lauryl sulphate, salts
of sulphonated aromatic compounds, for example sodium
dodecylbenzenesulphonate, sodium, calcium or ammonium
1~ lignosulphonate, butylnaphthalene sulphonate, and a mixture
of the sodium salts of diisopropyl- and triisopropylnaph-
thalene sulphonates. Sui~able agents of the non-ionic type
include, for example, the condensation products of ethylene
oxide with fatty alcohols such as oleyl alcohol or cetyl
aIcohol, or with alkyl phenols such as octyl phenol, nonyl
phenol and octyl cresol. Other non-ionic agents are the
~ partial esters derived from long chain fatty acids and
; hexitol anhydrides, the condensation products of the said~ partial esters with ethylene oxide, and the lecithins.
; 20 The compositions may be prepared by dissolving the
-~ active ingredient in a suitable solvent, for example, a
ketonic solvent such as diacetone alcohol, or an aromatic
solvent such as trimethylbenzene and addlng the mixture so
obtained to water which may contain one or more known wetting,
dispersing or emulsifying
- 36 -
, :
~: ' " ' ` `
~, . . . ~
agents. Other suitable organic solvents are dimethvl
formamide, ethylene dichloride, isopropvl alcohol, propylene
glycol and other glycols, diacetone alcohol, toluene,
kerosene, white oil, methylnaphthalene, xylenes and trichloro-
ethylene, N-methyl-2 ~yrrolidone and tetrahydro furfuryl
alcohol (THFA)
The compositions to be used as sprays may also be in
the form of aerosols wherein the formulation is held in a
container under pressure in the presence of a propellant
such as fluorotrichloromethane or dichlorodifluoromethane.
The composltions which are to be used in the form of aqueous
dispersions or emulsions are generally supplied in the form
of a concentrate containing a high proportion of the active
ingredient or ingredients, the said concentrate to be
diluted with water before use. These concentrates are often
required to withstand storage for prolonged periods and
~ after such storage~ to be capable of dilution with water to
;; form aqueous preparations which remain homogeneous for a
sufficient time to enable them to be applied by conventional
spray equipment. The concentrates may contain 10-85% by
~ weight of the active ingredient or ingredients. When diluted
- to form aqueous preparations, such preparations may contain
; varying amounts of the active ingredient dependir.g upon the
~ purpose for which they are ~o be used.
~,
~ - 37 -
-
: :
~6~
For agricultural or horticultural purposes, an aqueous
preparation containing between 0.000].~ and 0.1~ by weight of
the active ingredient is particularly useful.
In use the compositions are applied to the pests, to
the locus of the pests, to the habitat of the pests, or to
growing plants liable to infestation ~y the pests, by any of
the known means of applying pesticidal compositions, for
example, by dusting or spraying.
The compositions of the invention are very toxic to
wide varieties of insect and other invertebrate pests,
including, for example, the Eollowing:-
; phis fabae (aphids)
Me~oura viceae (aphids)
Aedes aegypti (mosquitoes)
Dysdercus fasclatus (capsids)
Musca domestica (house~lies)
.
Pieris brassicae ~white butterfly, larvae)
Plutella maculipennis (diamond back moth, larvae)
Phaedon cochleariae (mustard beetle)
::
Telarius cinnabarinus (caxmlne spider mite)
Aonidiella spp. (scale insects)
~: Trialeuroides spp. (white flies)
: Blattella germanica (cockroaches)
:
2~ littoralis (cotton leaf worm)
Chortiocetes terminifera (locusts)
:
: `
.:~
- 38 -
': ~
.. , ~
~ ~ ,
.: -
The compounds of formula I and compositions comprising
them have shown themselves to be paxticularly useful in
controlling lepidopteran pests of cotton, for example
Spodoptera spp. and Heliothis spp. They are also very
useful in combating insect and acarine pests which infest
domestic animals, such as Lucilia sericata, and ixodid
ticks such as Boophilus spp., Ixodes spp., ~mblyomma spp.,
Rhi~icephalus spp., and Dermaceutor spp. They are effective
in comba~ing both susceptible and resistant strains of
these pests in their adult, larval and intermediate stages
of growth, and may be applied to the infested host animal
by topical, oral or paxenteral administration.
The following Examples illustrate the various aspects
of the invention.
~ , .
:~ '
~ .
,
''
:~ .
~:
:~.
~ - 39 -
,
~: -
,
-, . . .:
EXAMPLE 1
This Example illustrates the preparation of l-chloro-
1,1-difluoro-2-chlorodifluoromethyl-5-methylhexa-2,4-diene,
of formula:-
CH3\ / F2Cl
C=CH-CH=C
CH3 CF2Cl
(a) Preparation of 3,3-dimethylallyl triphenylphosphonium
~; s bromide.
A mixture of 3,3-dimethylallyl bromide (50.0 g),
triphenylphosphine (88.0 g) and dry toluene (S00 ml) was
stirred and heated at the reflux temperature for one hour,
and then kept at the ambient temperature for la hours.
The white precipitate of 3,3-dimethylallyl triphenyl-
phosphonium bromide ~m.p. 242C) was collected by filtration,
washed with diethyl ether and dried.
(b) Preparation of l-chloro-l,l-difluoro-2-chlorodirluoro-
methyl-5-methylhexa-2,4-diene.
lS~ n-Butyl lithium (65.0 ml of a 15% w/w solution in
hexane) was slowly added to a vigorously stirred suspension
. ~
~ o~ 3,3~dimethylallyl triphenylphosphonium bromide (65.0 g)
::~
~ in dry petroleum ether (boiling range 30-40C, 500 ml) at
..
..,'~
-;
- 40 -
~: .- .. .
.
:~2~i6~
0C under a nitrogen atmosphere, after which the mixture was
kept at the ambient temperature for 18 hours. The mixture
was then cooled to 0C, and 1,3-dichlorotetrafluoroacetone
(31.44 g) was added. The mixture was then permitted to
attain the ambient temperature over a period of two hours,
~` and the precipitate removed by filtration. The filtrate was
concentrated by evaporation, until the volume was about 70
ml, an~ passed through a short alumina column, after which
the remaining solvent was evaporated at atmospheric pressure
at a temperature of 69C. The residual liquid was subjected
to fractional distillation, and the fraction boiling at 79-
80C/20 mm Hg collected and identified by infra red and
nuclear magnetic resonance spectroscopy as l-chloro-l,l-
difluoro-2~chlorodifluoromethyl-5-methylhexa-2,4~diene.
; 15 N.m.r. tCC14) p.p.m. 1.88-1.94 (m,6H); 6.3 (d,lH); 7.08
(d,l~).
.
'
:: :
;~ ~ 41 -
,,~
~ : .
.
.
~ ' ~ ~ ' ' ,: - ,
, - ~ . :: ~ .
,7~3
EXA~LE 2
By similar procedures to that illuskrated in Example
1 other dienes were prepared from the appropriate ketones,
as ~ollows:-
(i) 2-Methyl-5-trifluoromethylhexa-2,4-diene was
prepared from l,l,l-trifluoroacetone.
N.m.r. (CC14) p.p.m. 1.76~1.82 ~m,9H); 5.85-
6.00 (m,lH); 6.62-6.78 (m,lH).
(ii) 1,1-Difluoro-2-chlorodifluoxomethyl-5-methylhexa-
2,4-diene was prepared from 1-chloro-1,1,2,2-
tetrafluoroacetone.
Infra red (liquid film) - 3000, 1650, 1265 cm 1.
(iii) 1,1-Difluoro-2~di f luoromethyl-5-methylhexa-2,4-
diene was prepared f rom 1,1,3,3-tetrafluoro-
; acetone.
N.m.r. (CC143 p.p.m. 1.90-2.02 (m,6H); 5.65-
7.10 (m,4H).
:
, ~:
.:.;.:
.
~,
42 -
,.
.: : ~ : , . .:.
- ~, ,.
, ,
EXAMPLE 3
This Example illustrates the preparation of 5-hydroxy-
2-methyl 6,6,6-trifluoro~5-trifluoromethylhex-2-ene.
A stirred mixture of hexafluoroacetone (235 g) and
3-methylbut-1-ene (100 g) was heated at 125C under a
pressure of 17 atmospheres for a period of 20 hours.
Distillation of the product mixture under reduced pressure
yielded 5 hydroxy-2-methyl-6,6,6-trifluoro-5-triEluoro-
methylhex-2-ene as a mobile colourless liquid, b.p. 43C/
15 mm Hg.
N.m.r. (CC14) p.p.m. 1.77 (d,6H); 2.58-3.00 (m,3H); 5.0-
5 4 (m,lH).
EX~MPLE 4
By the use of a procedure similar to-that illustrated
in Example 3 5-hydroxy-2-methyl-6,6-dlfluoro-5-trifluoro-
methylhex-2-ene was prepared from pentafluoroacetone.
~ W.m.r. (CCl~) p.p.m. 1.78 (d,6H); 2.5-2075 (m,3H); 5.18
`::
(m,lH); 5.80 (t,lH).
, ~
.~
~ 3 -
,,
: , , :. :: . :
:~ ~ . ' . ' : '
,
: '' ~ ~ ,
~66~8
EXAMPLE 5
This Example illustrates the preparation of ethyl
(+) cis/trans-3-(2-hydroxy-3,3,3-trifluoro-2-tri~luoro-
methylprop-l-yl)~2,2-dimethylcyclopropane carboxylate.
A solution of ethyl diazoacetate (9.12 g) in dichloro-
methane (400 ml) was added dropwi~e over a period of 48
hours to 5-hydroxy-2-methyl-6,6,6-trifluoro-5-trifluoro-
methylhex-2-ene (18.9 g) in the presence of a catalytic
amount of anhydrous copper (II) sulphate at 110-120C.
The resultant mixture was washed with water, dried
over anhydrous magnesium.sulphate, and distilled to yield
several fractions within the range 68-90C at 0.15 mm.
N.m.r., infra red and mass spectral analysis indicated that
these fractions consisted principally of the (~)-cis and
(~)-trans-isomers of ethyl 3-(2-hydroxy-3,3,3-trifluoro-2-
trifluoromethylprop-1-yl)-2,2-dimethylcyclopropane carboxy-
late in different proportions.
N.m.r. (CDC13) p.p.m. 1.04-1.40 (m,9H); 1.55-2.43 (m,4H);
4000-4.37 (m,2H).
:
~:
~'
,, ~ .
- 44
': ~
:
, '
i7~
EXAMPLE 6
By the use o a procedure similar to that illustrated
in Example 5 S-hydxoxy-2-methyl-6 r 6-difluoro-5-trifluoro-
methylhex-2-ene was converted to ethyl (+)-cis/trans-3-(2-
hydroxy-3,3-difluoro-2-trifluoromethylprop-1-yl)-2,2-dimethyl-
cyclopropane carboxylate.
N.m.r. (CCl~) p.p.m. 1.3-2.4 (m,13H); 4.0-4.35(m,2H); 4.6-
4.8 (m,lH); 5.2-6.4 (m,lH).
EXAMPLE 7
This Example illustrates the preparation of ethyl (~)-
cis/trans-3(3,3,3-trifluoro 2-trifluoromethylprop-1-en-1-
; 10 yl)-2,2-dimethylcyclopropane carboxylate.
A mixture of ethyl (+)-cis/trans-3-(2-hydroxy-3,3,3-
trifluoro-2-trifluoromethylprop-1-yl)-2,2-dimethylcyclopropane
carboxylate (4.62 g), phosphorus oxychloride (2.2 g), and
dry pyridine (5.3 ml) was heated at 110C or a period of
65 hours, after which it was poured into iced water and
stirred for 5 hours. The mixture thus obtained was extracted
with diethyl ether, and the extracts washed with water and
dried over anhydrous sodium sulphate. After ramoval of the
ether by evaporatlon under reduced pressure the residual
;20 oil was distillad under reduced pres~ure, and ethyl (+)-
45 -
,
.
A ~ ,
i6Gi~
cis/trans-3-(3,3,3-trifluoro-2-trifluoromethylprop-1-en-
l-yl)-2,2-dimethylcyclopropane carboxylate was obtained
as a colourless oil, b.p. 60-65/0.5 mm Hg.
N.m.r. (CDC13) p.p.m. 1.15-1.39 (m,9H); 1.75-2.60 (m,2H);
4.02-4.34 (m,2H); 6.36 and 7.36 (dd,lH).
EXAMPLE 8
By the use of a procedure similar to that illustrated
in Example 7 ethyl (+)-cis/trans-3-(3,3-difluoro-2-trifluoro-
- methylprop-l en-l-yl)-2,2-dimethylcyclopropane carboxylate
was obtained from the product of Example 6.
N.m.r. (CC14) p~p.m. 1.2-1.4 (m,9H); 1.6-2.6 (m,2H);
4.0-4.4 (m,2H); 5.4-7.2 (m,2H).
ExAMæLE 9
By the use of similar procedures to that illustrated
in Example 5 the following ethyl esters of formula II
were obtained from the stated dienes by reaction with
ethyl diazoacetate.
(i) Ethyl (~)-cis/trans-3-(3,3-di~luoro-2-difluoro-
methylprop-l-en-l-yl)-2,2-dimethylcyclopropane
carboxylate, from 1,1-difluoro-2-difluoromethyl-
5-methylhexa~2,4~diene.
- 46 -
.'.: .
, ~ . .. .
:: `
``'
~l~6~i7~3
N.m.r. (CC14) p.p.m. 1.25-1.44 (rn,9H); 1.60-2.40
(m,2H); 4.0 4.30 (m,2H); 5.58-7.34 (complex, 3H).
(ii) Ethyl (+)-cis/trans-3-(E/Z 2-trifluoromethylprop-
l-en-l-yl)-2,2-dimethylcyclopropane carboxylate,
from 2-trifluoromethyl-5-methylhexa-2,4-diene.
N.m~r. (CC14) p.p.m. 1.10-1.40 (m,9H); 1.50-2.10
(m,SH); 4.0-4.38 (m,2H); 5.24-6.46 (m,lH).
(iil) Ethyl (~)-cls/trans-3-(3-chloro-3,3-difluoro-2-
chlorodifluoromethylprop-l-en-l-yl)-2,2-dimethyl-
cyclopropane carboxylate, from l-chloro-l,l-
di1uoro-2-chlorodifluoromethyl-5-methylhexa-2,4-
diene.
N.m.r. (CC14) p.p.m. 1,28-1.42 (m,9H); 1.78~2.60
(m,2H); 4.08 4.26 (m,2H); 6.20 and 7.16 (dd, lH).
~; 15 (iv) Ethyl (~)-cis/trans-3-(E/Z~3,3-difluoro-2-chloro-
difluoromethylprop-l-en-l-yl)-2,2-dimethylcyclo~
propane carboxylate, from 1,1-difluoro-2-chloro-
~; difluoromethyl-5~methylhexa-2,4-diene.
~ N.m.r. (CC14) p.p.m. 1.24-1.52 (m,9H); 1.64-2.50
;`: 20 (m,2H); 3.90-4.30 (m,2H); 5.50-7.04 (m,2H).
~ ~ .
~ 47 -
; ~ :: , : .; .
. ~
;
:,. :~
~2~
EXAMPLE 10
This Example illustrates the preparation of ethyl
3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluoroheptanoate,
of formula:-
CF3CC~2C~2CHClC(CH3)2CH2C02C2H5
A mixture of ethyl 3,3-dimethylpent-4~enoate (7.0 g),
1,1,1-trichloro-2,2,2-trifluoroethane (20.0 g) and benzoyl
:
pexoxide (0.1 g) was heated in a sealed glass tube for 5
hours at 100C. The mix:ture obtained was carefully distilled
and ethyl 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluoro-
heptanoate was collected as a fraction boiling at 112-114C/
2 mm Hg, and its identity confirmed by infra red and nuclear
: magnetic spectroscopic analysis.
:'
:
.~`~',
. ~
; ~ :
~ :
~ - 48 -
;' ~
: , : . ~ ,
- . .
.
: .~ . . . .~: .
,
~6~i7~3
EXAMPLE 11
By the use of procedures similar to that set out in
Example 10 certain other halogenated esters were prepared
by reacti~g haloalkanes with ethyl 3,3-dimethylpent-4-
enoate as follows:-
(i) Ethyl 3,3-dimethyl-7,7-difluoro-4,6,6,7-tetra-
chlorohepkanoate from l,l-difluorotetrachloro-
ethane~
N.m.r. (CDC13) p.p.m. 1.10-1.35 (m,9H); 2.10-
3.00 (m,4H); 4.12 (q,2H); 4.52 ~dd,lH).
(ii) Ethyl 3,3-dimethyl-6,7,7-trifluoro-4,6,7-trichloro-
heptanoate from 1,1,2-trifluorotrichloroethane.
The boiling point of the product was 75-76C/
0.05 mm Hg.
(iii) Ethyl 3,3-dimethyl-4,6,6-tribromo-7,7,7-tri~luoro-
15~ heptanoate from l,l,l-tribromotrifluoroethane.
N.m.r. (CDC13) p.p.m. 1.16-1.44 (m,9H); 2.50
(q,2H), 3.04 (q,2H); 4 18 (q,2H); 4.60-4.74
(m,lH).
(iv) Ethyl 3,3-dimethyl-7,7,8,8,8-pentafluoro-4,6,6-
trlchlorooctanoate from l,l,l-trichloropPntafluoro-
propane.
:
N.m.r. (CCl~) p.p.m. 1.13-1.40 (m,9H); 2.14-2.92
(m,4~1); 3.96-4.25 (q,2H); 4.5-4.62 (m,lH).
- 49 -
., ~ ,
..;
. ~ : : - . : : - - -
: - . -
.
7~
(v) Ethyl 3,3-dimethyl-7,7,8,8-tetrafluoro-4,6,6,8-
tetrachlorooctanoate from 1,1,1,3-tetrachloro-
tetrafluoropropane.
EXAMPLE 12
. , .
This example illustrates the preparakion of ethyl (+)-
cls/trans-3-(E/Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-
dimethylcyclopropane carboxylate.
~ The ethyl 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluoro-
;~ heptanoate obtained in Example 10 was dissolved in dry
tetrahydrofuran (30 ml) and the solution added dropwise to a
suspension of sodium t-butoxide (2.75 g, prepared in situ
: from sodium hydride and t-butyl alcohol) in dry tetrahydro-
:~ furan (120 ml) at 0C. When the addition was complete the
~ mixture was stirred for a period of 2 hours at 0C and then
acidified with ethanolic hydrogen chloride. After diluting
the mixture with diethyl ether it was washed with water,
dried over anhydrous magnesium sulphate and concentrated by
evaporation of the solvents under reduced pressure. The
:
: residuaI yellow oil was carefully distilled under reduced
pressure ~o yield e~hyl (~ cis/trans-3-(2-chloro-3,3,3
tri~luoroprop-1-en-1-yl)-2,2-dimethylcyclopropane carboxylate,
`
b . p . 70C/0.5 mm Hg. Nuclear magnetic resonance analysis
indicated that the product consisted of a mixtur~ of about
: 60% of the cis isomers and about 40% of the trans-isomers
;,
- 50 -
:: ::: . : '~ ` ,.
9~
(across the cyclopropane ring), there being in each case
about 90-95~ o~ the isomer in which the trifluoromethyl
group is trans to the cyclopropane ring on the double bond
(the Z-isomer), and about 5-10% of the isomer in which it
is cis (the E-isomer).
EXAMPLE 13
By the use of procedures similar to that illustrated
in Example 12 other ethyl esters of formula II were prepared
as follows:-
(i) Ethyl (~)-cls/trans-3-(E/Z-2,3-dichloro-3,3-
difluoroprop-1-en-1-yl)-2,2~dimethylcyclopropane
carboxylate, from ethyl 3,3-dimethyl-7,7-difluoro-
4,6,6,7-tetrachloroheptanoate.
N.m.r. (CDC13) p.p.m. 1.15-1.55 (m,9H); 1.55-2.50
(m,2H); 4.00-4.33 (m,2H); 6.13 and 6.95 (dd,lH).
lS (ii) Ethyl (+)-cis/trans-3-(E/Z-3-chloro-2,3,3 trifluoro-
prop~l-en-l-yl)-2,2-dimethylcyclopropane car~oxy-
late, from ethyl 3,3-dimethyl-6,7,7-trifluoro-4,6,7-
trichloroheptanoate.
N.m.r. (CC14) p.p.m. 1.20-1.58 (m,9H); 1.58-2.33
(m,2H); 4.15 (q,2H); S.10, 5.41, 5.gl and 6.2;
~ .
: (4d,1H).
`:
- 51 -
::
..,, ~:
(iii) Ethyl (~)-cis~trans-3-(2-bromo-3,3,3-trifluoroprop-
l-en-l-yl)-2,2-dimethylcyclopropane carboxylate~
from ethyl 3,3-dimethyl-4,6,6 tribromo-7,7,7-
trifluoroheptanoate.
S N.m.r. (~C14) p.p.m. 1.10-1.40 (m,9H~; 1.60-2.44
(m,2H); 3.96-4.28 (m,2H); 5.96-7.26 (m,lH).
(~v) E~hyl (+~-cis/trans-3-(2-chloro-3,3,4,4,4-penta-
fluorobut-l-en-l-yl)-2,2-dimethylcyclopropane
carboxylate from ethyl 3,3-dimethyl-7,7,8,8,8-
pentafluoro-4,6,6-trichlorooctanoate.
N.m.r. (CC14) p.p.m. 1.15-2.53 (complex,llH);
3.92-4.30 (m,2H); 6.12 and 6.92 ~dd,lH).
(v) Ethyl (+)-cis/trans-3-(2,4-dichloro-3,3,4,4-
tetrachlorohut l-en-l-yl)-2,2-dimethylcyclopropane
carboxylate, from ethyl 3,3-dimethyl-7,7,8,8-
tetrafluoro-4,6,6,8-tetrachlorooctanoate.
'
E~AMPLE 14
This Example illustrates the preparation of (+)-cis/
tr~ns-3-(3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl)
-2,2-dimethylcyclopropane carboxylic acid.
A mlxture of ethyl (~)-cis/trans-3-(3,3,3-trifluoro-2-
trifluoromethylprop-l-en-l-yl)-2,2-dimethylcyclopropane
carboxylate (0.52 g), glacial acetic acid (2.52 ml), hydro-
: ,~
~ ~ - 52 -
'~ ~
`~: ;
;~
~,: : - ~ , ~ . , . -
, .
~ . , , , : .
~`::: . . :
; ",,~
.
:~6~7~3
bromic acid (48~ w/v; 3.36 ml), and water (1.12 ml) was
heated at the reflu~ temperature for a period of 10 hours.
After cooling the mixture it was diluted with water (50 ml)
and extracted several times with diethyl ether. The extracts
were combined, washed with water, dried over anhydrous sodium
sulphate, and concentrated by evaporation of the ether under
reduced pressure. The residual oil was shown by spectroscopic
analysis to consist principally of (~)-cis/trans-3-(3,3,3-
trifluoro-2-trifluoromethylprop-1-en-l-yl~-2,2-dimethylcyclo-
propane carboxylic acid.
~ E~AMPLE 15
:
This Example illustrates the conversion of (+)-c /trans-
3-(3,3,3-trifluoro~2-trifluoromethylprop-1-en-l-yl)-2,2-
dimethylcyclopropane carboxylic acid to its acid chloride.
A mixture of (~)-cis/trans-3-(3,3,3-trifluoro-2-tri-
_. _
lS fluoromethyl-prop-l-en-1-yl)-2,2-dimethylcyclopropane
carboxylic acid (0.4 g) and thionyl chloride (5.0 ml) was
heated at the reflux temperature for a period o 2 hours,
after whi~h the excess thionyl chloride was removed by
distillation under reduced pressure, leaving (+)-ci ! trans-
l-chlorocarbonyl-3-(3,3,3-trifluoro-2-trifluoromethyl-prop-
l-en-l-yl)-2,2-dimethylcyclopropane.
:'
` :~
~ - 53 ~
~ ~ .
~ , ,' .
-
:
~l~G66'78
EXAMPLE 16
This Example illustrates the preparation of (+)-~-
cyano-3-phenoxybenzyl (+)-cis/trans-3-(3,3,3-trifluoro-2-
trifluoromethylprop-l-en-l-yl)-2,2-dimethyl cyclopropane
carboxylate, herein referrad to as Product no 1.
To the residue of (~)-cis/trans-L-chlorocarbonyl-3-
(3,3,3-tri1uoro-2-trifluoromethylprop-1-en-1-yl)-2,2-
dimethylcyclopropane (obtained in Example lS) was added a
mixture of pyridine (0.12 g) and (~)-a-cyano-3-phenoxybenzyl
alcohol (0~33 g) and the mixture thus obtained was stirred
for a period of 16 hours at the ambient temperature. Water
(20 ml) was added and the mixture extracted with diethyl
ether (3 x 10 ml). The combined extracts were washed with
; water, saturated sodium bicarbonate solution, and water and
dried over anhydrous sodium sulphate. After removal of the
lS ether by evaporation under reduced pressure the residual oil
was subjected to preparative thick-layer chromatography,
using 2 mm ~hick silica on glass with chloroform as eluent,
to yield (+)-~-cyano-3-phenoxybenzyl (+)-cis/trans-3-(3,3,3-
trifluoro-2-trifluoromethylprop-1-en-1-yl)-2,2-dimethylcyclo-
propane carboxylate (Rf 0.53), containing about 20~ of the
cis-isomer and about 80~ of the trans-isomer. Spactral
data: infra red, 1755, 1680, 1600, 1490, 1300, 1160; n.m.r.,
0.9-2.5~ , 6.0-6.15l , 6.35-7.2~ ; mass spectrum, ~ 483(275,
259, 231, 209, 208, 181).
54 -
~ , "
.: . -
,, : ~
, . .. . . .
~ ' " ;`
~.~6~6~3
EXAMPLE 17
This Example illustrates the preparation of (+)-c
trans-3-(2-chloro--3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethyl-
cyclopropane carboxylic acid.
A mixture of ekhyl (+)-cis/trans-3-(2-chloro-3,3,3-
trifluoro-prop-1-en-1-yl)-2,2-dimethylcyclopropane carboxylate
(0.52 g), glacial acetic acid (2.52 ml), hydrobromic acid
(48~ w/v; 3.36 ml), and water (1.12 ml) was heated at the
reflux temperature for a period of 10 hours. After cooling
the mixture it was diluted with water (50 ml) and extracted
several times with diethyl ether. The extracts were combined,
washed with water, dried over anhydrous sodium sulphate, and
concentrated by evaporation o the ether under refuced
pressure. The residual oil was shown by spectroscopic
analysis to consist principally of (+)-cis/trans-3-(2~
chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane
carboxylic acid.
EXAMPLE 18
Th1s Example illustrates the conversion of (+)-cls/trans-
3~(2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethyl-
cyclopropane carboxylic acid to its acid chloride.
55 -
' :
:
:: :: :
A mixture of (+)-cis/trans-3-(2-chloro-3,3,3-trifluoro-
prop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylic acid
(0.4 g) and thionyl chloride (5.0 ml) was heated at the
reflux temperature for a period of 2 hours, after which the
excess thionyl chloride was removed by distillation under
reduced pressure, leaviny (+)-cis/trans-l-chlorocarbonyl~3-
. .
(2-chloro-3,3,3-trifluoroprop-l-en-1-yl)-2,2-dlmethylcyclo
propane.
ExAMæLE l9
This Example illustrates the preparation of (+)-a-
cyano-3-phenoxybenzyl (+)-cls/tra-hs-3-(2-chloro-3r3~3-
tri1uoroprop-l-en-l-yl)-2,2-dimethyl cyclopropane carboxy-
late, herein referred to as product no 6.
To the residue of (+)-cis/trans l-chlorocarbonyl-3-(2-
chloro-3,3,3-trifluoroprop-l-an-l-yl)-2,2~dimethylcyclo-
propane (obtained i.n Example 18) was added a mixture of
pyridine (0.12 g) and (~)-a-cyano-~-phenox~benzyl alcohol
(0.33 g~ and the mixture thus obtained was stirred for a
period of 16 hours at the ambient temperature. Water
(20 ml) was added and the mixture extracted with diethyl
ether (3 x 10 ml). The combined extracts were washed with
water, saturated sodium bicarbonate solution, and water and
dried over anhydrous sodium sulphate. After removal of the
: - 56 -
.
;, '
' ` . .';
'~
~X6G6~8
ether by evaporation under reduced pressure the residual oil
was subjected to preparative thick-layer chromatography,
using 2 mm thick silica on glass with chloroform as eluent,
to yield (+)-a-cy~no-3-phenoxybenzyl (-~)-cis-3-(2-chloro-
3,3,3 trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane
carboxylate (Rf 0.52), and the corresponding trans isomers
(Rf 0.42), each containing about 90-95% of the Z-isomer.
Spectral data : infra red (CHC13) 1740, 1660, 1590, 1480,
1460 cm 1; n.m.r. (CC14) : 6.90-7.50 ~, 1.60-2.70 Z, 1.50-
1.00 ~, and specific peaks at 6.3 ~ (benzylic H), 6.85,
6.50~ 6.11 and 5.84 ~ (vinylic H) tentatively assigned to
the Z-cis, E-cis, Z-trans and E-trans isomers respectively.
' '
E~AMPLE 20
By the use of procedures similar to those illustrated
in Example 14 and Example 17 the ollowing carboxylic acids
were prepared from the corresponding ethyl esters.
(i) (+)-cis/trans-3-(3,3-difluoro-2-trifluoromethyl-
~ . ~
; prop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylic
acid.
Infra red (liquid film) 3500-2400, 1700, 1665 cm 1.
(ii) (+)~cis/trans-3-(3~3-difluoro-2-difluoromethyl-
prop 1-3n-1-yl)~2,2-dimethylcyclopropane carboxylic
~;~ acid.
'
- 57 -
.
: :
.-.
~X6~i67~3
N.m.r. (CC14) p.p.m. 1.30-1.50 (m,6H); 1.70-2.60
(complex, 2H); 5.70-7.13 (complex, 3H).
(iii) (+)-cis/trans-3-tE/Z~2-trifluoromethylprop-1-en-
l-yl)-2,2-dimethylcyclopropane carboxylic acid.
N.m.r. (CC14) p.p.m. 1.22-1.44 (m,6H); 1.6-2.3
(m,5H); 5.36-6.6 (m,lH); 11.9 (s,lH).
(iv) (f)-cis/trans-3-(3-chloro-3,3-difluoro-2-chloro-
difluoromethylprop-l-en-l-yl)-2,2-dimethylcyclo-
propane carboxylic acid.
N.m.r. (CC14) p.p.m. 1.24-1.42 (m,6H); 1.80-2.68
(~,2~); 6.16 and 7.L2 (dd,lH); 11.6 (s,lH).
(v) (~)-cis/trans-3-(E/Z-3,3-difluoro-2-chlorodifluoro-
methylprop-l-en l~yl)-2,2-dimethylcyclopropane
carboxylic acid.
Infra red (CHC13) 3450-2500, 1705, 1675 cm 1.
(vi) (+) cis/ rans-3-(2-bromo-3,3,3-trifluoroprop-1-en-
;~ l-yl)-2,2-dime~hylcyclopropane carboxylic acid.
In~ra red (CHC13) 3400-2450, 1700, 1650, 1275,
1140 cm
(vii) (~)-cis/trans-3-(3-chloro-2,3,3-trifluoroprop-1-
en l-yl)-2,2-dimethylcyclopropane carboxylic acid.
~; Infra red (oil film) 3400-2200, 1700, 1450, 1140,
1070 cm 1.
, ~
. ~
, ~
~ 58 -
.
~:
~,i,.,,," ~,. .
-~ - . - . - ,
. . .
. ~ .:, -, : ~ . . : .
' ~ ,. ' ~'
6~
(viii) (~)-cis/trans-3-(2,3-dichloro-3,3-difluoroprop-1-
en~l-yl)-2,2-dimethylcyclopropane carboxylic acid.
Infra red (CHC13) 3400-2200, 1700 cm 1.
(ix) Pure (+)-cis-3-(2,3-dichloro-3,3-difluoroprop-1-
en-1-yl~~2,2-dimethylcyclopropane carboxylic acid
was precipitated on cooli~g from a concentrated
solution of the mixed cis and trans acids in
hexane.
N.m.r. (CDC13) p.p.m. 1.25 (s,6H); 1.80-2.25
(m,2H); 6.73 (d,lH).
(x) (+)-cis/trans-3-(2-chloro-3,3,4,4,4-pentafluorobut-
l-en-l-yl)-2,2~dimethylcyclopropane carboxylic
acid.
N.m.r. (CDC13) p.p.m. 1.10-1.50 (m,6H); 1.68-2.58
(m,2H); 6.14 and 6.85 (dd,lH).
(xi) (~ cis/trans 3-(2,4-dichloro-3,3,4,4-tetrafluoro-
but-l-en-l-yl)-2,2-dimethylcyclopropane carboxylic
acid.
EXAMPLE 21
The various carboxylic acids of Example 20 were converted
to the lnsecticidal ester products according to formula I by
reacting the acid chlorides with 3-phenoxyben2yl alcohol,
(+)-a-cyano-3-phenoxybenz~l alcohol or (+)-~-ethynyl~3-
'
' ~:
59 -
':
~ ~ :
7~
phenoxybenzyl alcohol. The products of the~e reactions
(herein designated Product nos 2 to 5 and 7 to 29) are for
the most part mixtures of more than one of the compounds of
Table I, as se~ out hereinbelow.
Product no 2 ~ a-cyano-3-phenoxybenzyl (~)-cis/
trans-3 (3,3,3-trifluoro-2-trifluoro-
me~hylprop-l-en-l-yl)-2,2-dimethyl
cyclopropane carboxylate, is a mixture
of 1 part of compound no 1 with 1 part
of compound no 2.
N.m.r. (CC14) p.p.m. 1.20-1.40 (m,6H);
1.80~2 30 (m,2H); 6.17-6.37 and 6.85-
7.42 (mm,llH).
Product no 3 : (+)-~-cyano-3-phenoxybenzyl (+)-trans-
lS 3-(3,3,3-tri~luoro-2-trifluoromethylprop-
l-en-l-yl)-2,2-dimethylcyclopropane
carboxylate, is compound no 2 alone.
~; Product no 4 : (+)-~-cyano-3-phenoxybenzyl (+)-cis-
3-(3,3,3-trifluoromethylprop-1-en-1-yl)-
2,2-dimethylcyclopropane carboxylate,
is compound no 1 alone.
Product no 5 ~ a-cyano-3-phenoxybenzyl (+)-Ci5-
~` 3-(2 chloro-3,3,3-trifluoroprop-1-en-
l-yl)~2,2-dimethylcyclopropane carboxylate,
is a mixture of 19 parts of compound no
;~ ; 31 with 1 part of compound no 32.
`~
- 60 -
: - . .
:
. .
- ' :. .-
~.
.: ~ ' '
: ' ' .
i6~
Product no 7 : 3-phenoxybenzyl (~)-cis/trans-3-(3,3,3-
trifluoro-2-trifluoromethylprop-1-e~
yl)~2,2-dimethylcyclopropane carboxylate,
is a mixture of 11 parts of compound no
3 with 14 parts of compound no 4.
N.m.r. (CC14) p.p.m. 1.18-1.40 (m,6H);
1.75-2.55 (m,2H); 5.15 (s,2H); 6.30 and
6.70-7.40 (dm,lOH).
Product no 8 : (~)-a~cyano-3-phenoxybenzyl (~)-cis/
trans-3-(3,3-difluoro-2-trifluoromethyl-
prop-l-en-l-yl)-2,2-dimethylcyclopropane
carboxylate, is a mixture of compounds
nos 15, 16, 17 and 18 (composition
undetermined).
Infra red (liquid film) 1745, 1665, 1595
cm
Product no 9 : 3-phenoxybenzyl (~)-cis/trans-3-(Z-
2,3-dichloro-3,3-difluoroprop-1-en-1-
yl)-2,2-dimethylcyclopropane carboxylate
~ ~ 20 is a mixture of 1 part of compound no
; 39 wlth 1 part of compound no 41.
: .
N.m.r. (CDC13~ p.p.m. 1.20-1.37 (m,6H);
1.73-2.50 (m,2H); 5.10 (d,2H); 6.12 and
`~ 6.88-7.48 (dm,lOH).
- 61 -
~":~: :
.: :
7l3
Produc~ no 10 ~ a-cyano~3~phenoxybenzyl (~)-cis/
trans-3-(Z/E-2,3 dichloro-3,3-di,luoro-
prop-l-en-l~yl)-2 t 2-dimethylcyclopropan~
carbox~late is a mixtur2 o 19 pa~ts of
S compound no 43, 1 pa-t of compound no
44, 19 parts o~ compt~und no 45 and 1
par~ of compaund n~ 46.
N.m.r.. (CCl4) p.~.m~ l.L8-1.45 ~m,6~);
1.73-2.50 (~,2E); 6.32 ~m,l~); 6.08 a~d
~10 6.8i (dd,l~; 6.9~-7.~4 (m,9E).
Product nc 11 : (+)-~-cyano-3-phe~cxy~enzyl (~)-c~
3-(Z/E~2,3-dichloro-3,3-difluoro~ro~-
l-en-l-yl)-2,2-dimethylcyclopropane
car~oxylate is a ml~ture of 19 p~rts o r
compound no ~3 wi~h 1 part o~ compaund
~: no 4~.
N.m.r. (CC14) ~.p..n. l~L~-1.40 (m,5~);
: ~ l.g2-2.32 (m,2~); 6.31 ~d,l~): 6.~l-
(djl~); 6.9a-~.4s (m,g~).
Product no 12 : 3-phQnoxyhenzyl (+) ~ s -3~ 2, 3-
: : dlc~lor~-3,3~dl.1uoro~rop-L-en-l-yl)-
2,2-dimethylc~clo~~o~ane car~oxyl~ e, 1_,
lxture O 1~ ~a_~s o com~o~-~ no 39
th i ~ar~ ~ com~o~ no 40.
,m.r. ~CCl,) ~.p.mm. 1.0~-1.'3 (~,o.~);
1.84-2.33 (~ .02 (s,2:~); 5.?2-7.';
o 2
~,
j
:
78
Product no 13 ~ (+)-~-cyano-3-phenoxybenzyl (+)-cis/
trans-3-(Z/E-2-tri1uoromethylprop-1-
en-l-yl)-2,2-dimethylcyclopropane
carboxylate is a mixture of 1 part
of compound no 19, 9 parts of compound
no 20, 1 part of compound no 21 and
9 parts of compound no 22.
N.m.r. (CC14) p.p.m. 1.22-1.40 (m,6H);
1.60-2.30 (m,5H~; 5.2-6.45 (mlH).
10Product no 14 : 3-phenoxybenzyl (+)-cis/trans-3-(Z/E-
2-trifluoromethylprop-1-en-1-yl)-2,2-
- ' dimethylcyclopropane carboxylate is amixture of 1 part of compound no 23,
9 parts of compound no 24, 1 part of
compound no 25 and 9 parts of compound
no 26.
N.m.r. (CCl~) p.p.m. 1.22-1.40 (m,6H);
1.58-2.2 (m,5H); 5.02 (s,2H); 5.2-6.45
(m,lH); 6.85-7.42 (m,9H).
20Product no 15 : (+)-a-cyano-3-phenoxybenzyl (+)-cis/
trans-3~(Z-3-chloro-2,3,3-trifluoro-
prop-l-an-l-yl)-2,2-dimethyl cyclopropane
carboxylate, is a mixture of 1 part of
compound no 47 with 1 par~ of compound
no 48.
63 -
. .: . -
" ' '
- .
. ' ', ' '' ~, .
N~m.r. (CC14) p.p.m. 1.15-1.40 (m,6H);
1.65-2.40 (m,2H); 5.08, 5.39, 5.80 and
6.12 (4d,lEI); 6.35 (m,lH); 6.92-7.50
(m,9H).
Product no 16 : (+)-a-cyano-3-phenoxybenzyl (+)--cis-
3-(Z-3-chloro-2,3,3-trifluoroprop-1-
en-l-yl)-2,2-dimethylcyclopropane
carboxylate, ls compound-no 47.
N.m.r. (CC14) p.p.m. 1.18-1.40 (m,6H);
1.85-2.33 (m,2H); 5.80 and 6.11 (dd,lH);
6.35 (d,lH); 6.95-7.60 (m,9H).
Product no 17 : 3-phenoxybenzyl (+) cis/trans-3-(Z-
; 3-cnloro-2,3,3-trifluoroprop-1-en-1-
yl)-2,2-dimethylcyclopropane carboxylate,
is a mlxture of 1 part o~ compound no
49 with 1 part of compound no 50.
N.m.r. (CC14) p.p.m. 1.15-1.30 (m,6H):
1.65-2.40 (m,2H); S.10, 5.40, 5.92 and
6.23 (m,3d,3H); 6.90-7.45 (m,9H).
~20 Product no 18 : (~ -cyano-3-phenoxybenzyl (+)-cis/
trans-3~(3,3,3-tri~luoro-2-trifluoro-
methylprop-l-en-l-yl)-2,2-dimethyl-
cyclopropane carboxylate, is a mixture
~:
:
of 1 part of compound no 1 with 2
parts of compound no 2.
- 64 -
. .
` , ' .
.
~X6i66713
Product no 19 : 3-phenox~benz~fl (~)-cls/trans-3-(3,3--
difluoro-2-difluororn2thylprop-l-en-l~
yl)-2,2-dimethylcyclopropane carboxylate
is a mixture of 3 parts of compound no 5
with 2 parts of compound no 6.
N.m.r. (CCl4) p.p.m. 1.18-1.37 (m,6H);
l.60-2.45 (m,2H); 5.03-S.l (m,2H); 5.13-
7.47 (complex, 12H).
Product no 20 : (+)-~-cyano 3-phenoxybenzyl (+)-cls/
trans-3-(3,3-difluoro-2-difluorome-thyl-
__
prop-l-en-l-yl) 2,2-dimethylcyclopropane
carboxylate is a mixture of 3 par-~s of
compo~md no 7 with 2 parts o compound
no 8.
1.5 N.m.r. (CC14) p.p.m. 1.~0-1.40 (m,6H);
; 1.80-2.47 ~m,2H); 6.17-6.37 and 6.85
-7.43 ~mm,l3EI).
;~ Product no 21 ; 3~phenoxybenzyl (~)-cis/trans-3-(Z/E-
2-chloro-3,3,3-trifluoroprop-l-en-l-
~ 20 yl)-2,2-dimethylcyclopropane carboxylate,
- ~ ; is a mixture of 9 parts of compound no
35, l part of compound no 36, 6 parts
`~ o~ compound no 37, and 4 parts of compound
no 38
~:
, :
,~. ,
~ - 65 -
. ,
i ~ :
;
. .
~: ' ~ ' ~`' -
6~'7~
Product no 22 ~ a-cyano 3-phenoxybenzyl (+)-c
trans-3~(Z-2,4-dichloro-3,3,4,4-tetra-
fluorobut~l-en-l~yl)-2,2 dimethylcyclo-
propane carboxylate, is a mixture of 9
parts of compound no 51 with one part of
compound no 52.
Product no 23 : (+)--cyano-3-phenoxybenzyl (+)-trans-
3-(Z-2-chloro-3,3,4,4,4-pentafluorobut-
; l-en-l-yl)-2,2-dimethylcyclopropane
carboxylate is compound no 53.
N.m.r. (CC14) p.p.m. 1.16-1.42 (m,6H);
; 1.74-2.60 (m,2H); 5.98-6.40 and 6.77-
7.55 (mm,llH).
~: "
Product no 24 : 3-phenoxybenzyl ~)-cis/trans-3-(3-
chloro-3,3-difluoro-2-chlorodifluoro-
methylprop-l-en-l~yl)-2,2-dimethylcyclo-
propane carboxylate, is a mixture of 7
parts of compound no 9 with 13 parts of
compound no 10.
~.
~ 20 N.m r. (CCl~) p.p.m. 1.24-1.42 ~m,6H);
,,
1.76-2.60 (m,2H); 5.02 (s,2H); 6.16 and
7.12 (dd,lH); 6.76-7.40 (m,9H).
, , ~
'`,~:::~ :
~ - 66 -
-,~, .,, . ... ~ . ,
~, . ::.
~ .
:~ :
3 ~ 7~
~ Product no 25 : (+)-a-cyano-3-phenoxybenzyl (+)-cis/
i~
trans~3(3-chloro-3,3-difluoro-2-chloro-
difluoromethylprop l-en-l-yl)-2,2-
dimethylcyclopropane carboxylate, is a
mixture of 7 parts of compound no 11
~ with 13 parts of compound no 12.
¦ N.m.r. (CCl~) p.p.m. 1.24-1.42 (m,6H);
1.84-2.70 (m,2H); 6.16 and 7.12 (dd,lH);
6.36 (ss,lH); 6.90-7.50 (m,9H).
Product no 26 : (+)-a-cyano-3-phenoxybenzyl (+)-cis/
trans-3-(Z/E-3,3-difluoro-2-chloro-
difluoromethylprop-l-en-l-yl)-2,2-
dimethylcyclopropane carboxylate, is a
mixture of undetermined composition
containing compounds 27, 28, 29 and 30.
N.m.r. (CC14~ p.p.m. 1.24-1.52 (m,6H);
1.76-2.70 (m,2H~; 5.6-7.6 (m,12H).
Produc~ no 27 : (+)-a-cyano-3-phenoxybenzyl (~)-cis/trans-3-
(Z/E-2-bromo-3,3,3-trifluoroprop-l-en-1-
: ~
yl~-2,2-dimethylcyclopropane carboxylate,
is a mixture of 10 ~arts of compound no
54, 1 part of compound no S5, lO parts
;~ of compound no 56 and 1 part of compound
: ~ :
;~ no 57.
::
~ 25 N.m.r. (CC14) p.p.m. 1.24-1.50 (m,6H);
. ~
:
1.75-2.55 (m,2H); 5.96-7.26 (m,lH);
6.36-6.56 (m,lH); 7.0-7.6 (m,9H).
- 67 -
1 ~:: .. .. ,.~ : ,
.
. :
~;; , . - :
; ~ ' , - ~ -
1;~66~78
Product no 28 : (+)-~-ethynyl-3-phenoxybenzyl t+)-cis/
trans-3-(Z/E-2-chloro-3,3,3-trifluoro-
prop-1-en-1-yl)-2,2-dimethylcyclopropane
caxboxylate, is a mixture of 10 par~s of
compound no 58, 1 part of compound no 59,
10 parts of compound no 60 and 1 part of
compound no 61.
N.m.r. (CC14) p.p.m. 1.16-1.44 (m,6H);
1.64-2.56 (m,3H); 5.7-7.0 (m,lH); 6.28-
6.40 (m,lH); 6.70-7.40 (m,9H).
Product no 29 : (+)-a-ethynyl-3-phenoxybenzyl (+)-cis/
trans-3-(3,3,3-trifluoro-2-trifluoro-
methylprop-l-en-1-yl)-2,2-dimethylcyclo-
propane carboxylate, is a mixture of 2
parts of compound no 13 with 3 parts of
compound no 14.
N.m.r. (CC14) p.p.m. 1.16-1.44 (m,6H);
1.76-2.56 (m,3H); 6.12-7.04 (m,lH);
6.24-6.40 (m,l~); 6.76-7.36 (m,9H).
EXAMPLE 22
This Example illustrates the insecticidal properties
of (+)-a-cyano-3-phenoxybenzyl (+)-cis/trans-3-(2-chloro-
3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl)-2,2-dimethyl-
cyclopropane carboxylate (containin~ 60% cis-isomer) (Product
- 68 -
.
lZ666'7B
.,
no 6) and (+)-~-cyano-3-phenoxybenzyl (+)~cls/trans-3-
(3,3,3-trifluoro-2-trifluoromethylprop~l-en-l-yl)-2,2-
dimethylcyclopropane carboxylate (containing 20% cis-
isomer) ~Product no 1) as representative examples of esters
~ 5 according to the invention.
¦ The activity of the products was tested against a
variety of insect and other invertebrate pests. Each
product was used in the form of liquid preparations, containing
in the case of product no 1 1000, 5QO, 125 and 62.5 p.p.m.
and in the case of product no 6, 50, 25, 12.5 and 6.25 p.p.m.
by weight of the product. The preparations were made by
dissolving the compound.in a mixture of solvents consisting
of 4 parts by volume of acetone and l part by volume of
~ diacetone alcohol. The solutions were then diluted with
; 15 water containing 0.01~ by weight of a wetting agent sold
under the trade name "LISSAPOL" NX untill the liquid
preparations contained the required concentration of the
compound. "Lissapol" is a Trade Mark.
The test procedure adopted with regard to each pest was
basically the same and comprised supporting a number of the
pests on a medium which was usually a host plant or a
foodstuff on which the pests feed, and treating either or
both the pests and the medium with ~he preparations.
~; The mortality of the pests was then assessed at periods
~; 25 usually varying from one to three days after the treatment.
,~ .
, '
'
~ 69 -
~ ' .
. .
:~
:~L;~
The results of the tests are given below in Tables II
and III. In these tables the first column indicates the
name of the pest specles. Each of the subsequent columns
indicates the host plant or medium on which it was supported,
the number of days which were allowed to elapse after the
treatment before assessing the mortality of th~ pests,
and the results obtained fox each of the concentrations
given above. The assessment is expressed in integers which
range from 0 3.
0 represents less than 30% kill
1 represents 30-49~ kill
2 represents 50-90~ kill
3 represents over 90% kill
:
A dash (-) indicates that no test was carried out.
lS "Contact test" indicates that both the pests and the medium
~' were treated and "residual test" indicates that the medium
~ was treated before infestation with the pests.
-~ The results for Product no 1 are in Table II and for
Product no 6 in Table III.
- 70 -
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-- 72 -
:
:
: `
EX~MPLE 23
This Example illustrates the insecticidal properties of
the products of Example 21. The tests were conducted under
the same conditions as those in Example 22. The results are
given in Table IV as the p~rcentage mortality of the pests
at one rate of application only for each product.
The symbols used in Table IV have the following meanings.
"P no" indicates "Product no" as defined in Example 21.
"Rate" indicates the concentration expressed in parts
per million of the active ingredient in the preparations
used in the test.
"A" to "M" indicate the pest species used in the tests,
which are as follows:
"A" - Tetranychus elarius (red spider mites - adults)
"Bl' - Tetranychus ~elar1us (red spider mites - eggs)
"C" ~ fabae (black aphids)
"D" - Me~oura viceae (green aphids)
"E" - Aedes aegypti (mosquitoes)
"F" - Musca domestica (houseflies) - contact activity
-
.
i'G" - Musca domestica (houseilies) - residual activity
"H" - Plutella xylostella - residual activity (3 days)
"I" - Plutella xylostella - residual activity (10 days)
"J" - Phaedon cochleariae (mustard beetle~
; ~ "R" - Calandra ~ (grain beetle)
:
.
~; ~ 73 -
:~
: :: . . :: . '
. : ,, :. ,
': : - `'
- ~ ~
-. . .. .
~24i~
"L" - Tribolium castaneum (flour beetle)
~M~ - ~ littoralis (cotton leaf worm)
An asterisk (*) in the table indicates that in addition
to the stated mortality the remaining living insects were
all severely affected and would ha~e been expected to die if
the duration of the text had been extended.
. .
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Ei6t78
EXAMPLE 24
This Example illustrates the ixodicidal activity of
product no 2 and product no 6 against cattle ticks (Bo_philus
~) .
A suspension of each of the products was prepared by
ball milling 10 parts of the product with 985 parts of water
and S parts of "Teric" N9 ("Teric" is a Registered Trade
Mark and "Teric" N9 is a nonionic surfactant obtained by
condensing nonylphenol with ethylene oxide in a molar ratio
of 1:9) to give a composition containing 1.0~ active ingredient.
A portion of each of the above suspension was then dlluted
with water to give compositions containing 0.1% and 0.01
active ingredient.
:~ The efficacy of each o the products against engorged
adult female ticks of the "Yeerongpilly" strain was tested
15 ~ by applying a microdrop of the appropriate concentration
~:~ suspension to each of about twenty of the ticks. After 14
days the mortality count o~ the adult ticks was assessed by
counting the eggs laid by them and the percen~age of those
eggs which had hatched. The results are given in Table V~
~: ~: 20: The eficacy of each o~ the products against larval
ticks o~ the "Yeerongpilly" strain was tested as ollows: A
sheet of filter paper was soaked in the appropriate
.
.~
~ 77 -
:~ ~
-, :
,
: . ,
: ' : " : ~-' '~
,. :. .
:: ~
concentration suspension and then allowed to dry. The
treated paper was converted to the form of an envelope and
approximately 100 larval ticks of the "Yeerongpilly" strain
were enclosed therein. A mortality count was done on the
larval ticks 48 hours after they had been placed in the
envelope and the kill rated on a 0-5 scale wherein
0 represents 0-20% kill
1 represents 20-50% kill
2 represents 50-80% kill
3 rapresents 80 95% kill
4 represents 95-99% kill
5 represents 100~ kill
:
The results are given in Table V.
In a further test an emulsion of each of the products
was prepared by mixing 25 parts of the compound with 75
parts of cyclohexanone and 25 parts of "Teric" N9 and
dlluting the mixture with water to provide 10,000 parts by
volume of an emulsion. Each of the emulsions so obtained
was sprayed, to drip point, onto calves heavily infested
20 ~ wlth various stages of the resi~tant "Biarra" strain of
cattle tick. The ef~icacy of each of the products was
assessed as follows:
(i) All adult female ticks which were fully engorged at the
; tlme of spraying were collected soon after spraying the
~ 25 calves. They were then placed in a Petri dish in an
,: ~
8 -
... ..
., ,' ~ '- ' ~ ' '
:
.
-~
incubator for assessment of mortality based on capaci-ty
to lay eggs, and if eg~s were laid, the viability of
the eggs as shown by hatch of vlable larvae. Engorged
adults, if any, were also collected at 24 hours and 48
hours after spraying and the same assessment of mortality
was made. Th:is assessment is referred to as "Mortality -
Engorged Adul~s" and the results are given in Table VI.
(ii) At daily intervals predetermined sampling areas on each
calf were inspected for the effect of the active
ingredient on the immature adults and nymphs. This
assessment was rated on the 0-5 scale defined in
Example 3 and is referred to as "Mortality - Immature
Adults" and "Mortality - Nymphs". The results are
given in Table VI.
; 15 The symbol "-" is used to indlcate that no engorged adults
were present.
; In these tests permethrln (3-phenoxybenzyl (+)~cis/
trans-3(2,2-dichloro~inyl)-2,2-dimethylcyclopropane carboxy-
late) was used as a standard.
' :
: :
- 79 -
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