Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ he present invention relates to the spiroheptenyl
carboxylate of the formula
C~i CH
~,CH ~3~ 3 0
CH C - ~t'H C-O-CH~ O~
~ ~H2
to prooesses for produci.n~ it, and to its use for combating
pests~
The compound of the formula I is produced by methods known
per se, for example as follows: .
.
~,CH \3 / 3
1) CT- ~ ~ C \ Q acid-binding
C ~ C / CH-C-OH ~ x CEI ~ ~ agent
lII) . (III~
3 / 3
CH~ ~ ~C n acid-binding
2 ) CH C----\CH-C-X ~HO-CH ~0~
CN ~ ~ a~ent
CH3 CH
CH \ ~C~ " -H20
3 ~C'~ ~ CH - C -OH ~ H-CHl~l-~ - ~
CN ~ ~J water-bindi.ng
(II~ lV) agent
.... . . .. .. . . . .
' ' ' " , .: ,
~ . ~
7~
CH3 C~i
~,c ~ \ / o -~OH
4 ) C C ----CH-C-OR + E10--CH-~-O~
.,
(VI) ~V)
In the formulae III and IV, X represents a halogen atom
particularly chlorine or bromine, and in the formula VI, R
represents Cl-C~-alkyl, especially methyl or ethyl. Suitable
as an acid-binding agent ror the processes 1 and 2 are, in
particular, tertiary amines such as trialkylamines and pyridine,
also hydroxides, oxides, and carbonates and bicarbon2tes or
alkali metals and alkaline-earth me~als as well as alkali metal
alcoholates such as potassium-t.bu~ylate and sodium methylate.
As the water-billding agent for the process 3, it is poss~ble ~o
use, e.g., dicyclohexylcarbodiimîde. The processes 1 to 4 are
p~rformed at a reaction temperature of between -10 and 100C,
usually between 20 and 80C, at normal or elevated pressure
and preferably in an inert solvent or diluent. Suitable solvents
or diluents are, e.g.: ethers and ethereal compounds such as
diethyl ether, dipropyl ether, dioxane, dimethoxyethane and
tetrahydrofuran; amides such as N,N-dialkylated carboxylic acid
amides; aliphatic, aromatic and halogenated hydrocarbons,
especially benzene, toluene, xylene, chlo~oform and chloro-
benzene; nitriies such as acetonitrile; dimethylsulphoxide and
ketones such as acetone and methyl ethyl ketone. The process 2
can be performed also in an aqueous solutlon.
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,~
. ' ~ . , ~
7~ 3
The starting materials of the formulae III to VI are
known or can be produced by methods analogous to known methods.
A me-~hod ~or producing the novel compound of the ~ormula II
is described in Example 1.
The compound of the formula I is obtained as a mix~ure
of various op~ically active isomers, unless the s~arting
materials used to produce the said compound are homogeneous
optically act~ve materialsO The different stable isomeric
mixtures can be separated by known methods into the individual
isor.lers. It is understood that the term compound of the formula
I em~races both the separate isomers and the mixtures thereo~.
The compound of the formula I is suitable for combating
animal and plant pes~s. I~ can thus be used for combating
members of the order Acarina, such as phytopathogenic mites,
for example of the genus Tetranychus and Panonychus, and also
ticks of the f~nilies Dermanyssidae and Ixodidae. It is
particularly suitable however for combating ~nsects, for example
of the families: Tettigoniidae, Gryllidae, Gryllotalpidae,
Blattidae, ~eduviidae, PyrrhocoridaP, Cimici~ae, Delphacidae,
Aphididae, Diaspididae, Pseudococcidae, Scarabacidae, Dermes~id2e,
Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae,
Noctuidae, Lymantriidae, Pyralidae, Culicidae 3 Tipulidae,
Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae.
The compound o~ the formulà I is especially suitable ~or
. . ,: ,
combating insects whîch damage plants, particularly insects
which darnage plall~s by eatiltg~ in crops of ornamental plants
and useful plants, especially in cotton crops (e.g. against
Spodoptera littoralis and Heliothis virescens) and in crops
of vege~ables (e.g. agai.nst Leptinotarsa decemlineata and Myzus
persicae). The active substance of the formula I exhibits 2
very favourable action also against flies~ such as Musca
domes~ica, and a~ainst mosquito larvae.
The acaricidal and insecticidal action can be substantially
broadened and adap~ed to suit given circumstances b-y the
addition of other insecticides and/or acaricides~ Suitable
additives are, e.g. organic phosphorus compounds, nitrophenols
and derivatives thereof; formamidines, ureas, other pyrethrin-
like compounds, as well as carbamates and chlorinated hydro-
carbons.
The compound of the formula I ls combined particularly
advantageously also with substances which have a synergistic
or intensifying effect on pyrethroids. Examples of such compounds
are, inter alia: piperonylbutoxide, propynyl ethers, propynyl
oximes, propynyl carbamates and propynyl phosphonates, 2-
(3,4-methylened~oxyphenoxy)-3,6,9-trioxaundecane, ~Sesamex
or Sesoxane), S,S,S-tributylphosphorotrithioates, 1,2 methylene
dioxy-4-(~-octylsulphonyl)~propyl)-benzene.
:
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.. . . . . . . .
. - . . . .
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.
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The compolr-cl of the formula 1 Call be used or its o~n vr
toc,ether ~l~tll 5U~ table carriers and/or aclditives. Suitable
addi.tives can be colid or liquid and they correspond to the
subst:ances co~lr.lon in orrnulaticn practice, such as na~ural 3
regenerated substances, so].vents, dispersing agents, we~t ng
agen~s, adhesives, thickeners, binders and/or fertilisers.
The composi.ti.ons according to the invention are produced
in a manner kno~.n per se by the intimate mixing an~l/or grinding OL'
the active substance of the formula I ~7i',-h su;.taDle carrie~s,
optionally with the addition O,c dispersing agents or solvents
~hich are inert to Lhe active substances. The active substance
can be obtainecl and used in the following forms:
olici pree~ ons: d~sts, sca~tering agents, granules (coated
granules, impregnated ~ranules and
homogeneous granules);
liguid ~ arations:
) water-dispersible concen~rates of active substance:
wettable powders, pas~es or emulsions;
b~ solutions.
The content of active substance in ~he described co~positions
i~ between 0.1 and 95%; it is to be mentioned here that with
application from an aeroplane, or from other suitable devices,
concentrations of up to 99.5% or even the pure active substance
can be used~
The active substance of the formula I can be formulated
~or example as follo~s: (parts are ~y weight):
'7~3
s ~s
__
The ~ollo~i.ng substances are used to produce a) a 5% dust
and b~ a 2% dust:
a) 5 parts of active substance,
parts of ~alcum;
b) 2 ~arts of ac~ive substance,
1 part of highly dispexsed silicic acid,
97 parts o talcl~.
The active substance is mix2d and ground with the carriers.
~ranula~e
_~ .
The following ingredients are used to produce a 5V/o granula~e:
parts of active substance,
0.~5 part of epichlorohydrin,
0.25 part of cetyl polyglycol ether,
30~0 parts of polyethylene glycol,
91 par~s o kaolin (particle size 0.3 - 0.8 ~m)~
The aetive substance is mi~ed with epichlorohydrin and
dissolved wi.th 6 parts of acetone; ~he polyethylene glyccl and
ee~yl polyglycol ether are then added. The solution obtained is
sprayed onto kaol.in and the acetone i5 evaporated of in vaeuo.
Wetta~le ~owder
The following constit.uents are used to produce a) a 40%~
b) and e) a 25%, and d~ a 10% wettable powder:
a) 40 parts o active subs~ance,
parts of sodium lignin sulphonate~
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- ^ -- ~ i ' , - - ~
1 part of sod-um dibu~ naphthalene suiphonateg
~ 4 parts of silicic acid;
b) 25 par~s of active substance,
4 . 5 par~s of calcium lignin sulphonate~
1.9 parts of Champagne chalk/hydroxyethyl cellulose
mixture (1:1),
1.5 parts of sodium dibutyl-naphthalene sulphonate,
19.5 parts o~ silicic acid,
l9.S parts of Charnpagne chalk,
28.1 parts of kaolin;
c) 25 parts of active subs~ance,
2.5 parts of isooctylphenoxy-polyo~yethylene~ethanol,
1.7 par~s OI Champagne chalk/hydroxyethyl cellulose
mix~ure ~1:1), `
8.3 parts of sodi.um aluminium silicate,
16.5 pa~ts of kieselguhr,
46 parts of kaolin;
d) ~0 parts of active substance,
3 parts of a mixture of the sodium salts of
saturated fatty alcoho] sulphates,
S parts of naphthalenesulphonic acid/~ormaldehyde
condensate,
82 parts o~ kaolin.
The active substance is intimately mixed in suitable mi~ers
with the additives, and the mixt~lre is then ground in the
appropriate mills and rollers to obtain wettable powders which
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can be diluted with water to give suspensions of the desired
concentration.
Emulsifiable concentrates
_
The following substances are used to produce a) a 10%,
b) a 25%, and c) a 50% emulsifiable concentrate:
a) 10 parts of active substance,
3.4 parts of epoxidised vegetable oil,
3.4 parts of a combination emulsifier consisting of
fatty alcohol polyglycol ether and alkylaryl
sulphonate calcium salt,
40 parts of dimethylfoImamide
43.2 parts of xylene;
b) 25 parts of active substance,
2.5 parts of epoxidised vegetable oil,
lO parts of alkylarylsulphonate/fatty alcohol poly-
glycol ether mixture3
5 parts of dimethylformamide,
57.5 parts of xylene;
c) 50 parts of active substance,
4.2 parts of tributylphenol-polyglycol ether,
5.8 parts of calcium-dodecylbenzenesulphonate,
20 parts of cyclohexanone,
20 par~s of xylene.
Emulsions of the required concentration can be prepared
from these concentrates by dilution with water.
'7~;3
S p~
The folio~qing constituents are used to produce a) a 5~O
spray and b) a 95% spray:
a~ 5 parts of active substance,
1 part of epichlorohydrin,
94 parts of ligroin (boiling limits 160-190C);
b~ 95 parts of ac~ive substance,
par~s of epichlorohydrin.
The invention is further illustrated by the ollowing
Ex~mp].es.
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i :
74~
Production o ~-cyano-3-phenoxybenzyl-2',2'-dimethylspiro-
(~,4)-hept-4-~ene-carboxylate
a) Produc~ion of 2~2-dimethylspiro (2,4)-hepta-4,6-diene l-
carboxylic acid.
To a solution, cooled to ~C, of 310.5 g (1.35 moles) of
carbethoxymethyl-dimethyl-sulphonium bromide in 1075 ml of
chloroform are quickly added 1310 ml of saturated aquec,us
potassium carbonate solution and 107.5 ml of 12.5N aqueous
sodium hydroxide solution. The reaction mixture is stirred ~or
15 minutes at room temperature, filtered and the chloroform
phase is separa~ed~ The chloroform solution is dried over
potassium carbonate and heated to 40C. After the slow dropwi.se
addition of 143.7 g (1.35 moles) of 6,6-dimethylfulvene, the
reaction mixture is held at 40C for 16 hours. The chloroform
solution is washed once with saturated sodium chloride solution,
dried over sodium sulphate and distilled off. To th~ residu2,
dissolved in 900 ml of ethanol, there is added dropwise at
10C 182 g o~ potassium hydroxide in ~50 ml of water. The
reaction mixture is refluxed for 2 hours and stirred ror 14
hours at room temperature. For processing, the reaction mîxture
is concentrated under reduced pressure, poured into ice water
and extracted wlth ether. The ether phase is waqhed neu~ral
with saturated sodium chloride solution~ dried over sodium
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. ~ . .
,
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sulphate and concentrated under reduced pressure. Recrystal-
lisation of the solid residue from ethanol/water yie]ds
the compound of the formula
Cll = Cl~
~C -- CH - COOH
CH = C~l ~ C
CH3 CH3
having a melting point of 130-132C.
b) Production of 2,2-dimethylspiro-~2,4) hept-4-ene-1-
carboxylic acid:
5 g (0.031 mole) of 2~2-dimethylspiro-(2,4)-hepta-4,6-diene
in 150 ml of methanol/water = 2:1 is hydrogenated using 0.1 g
of palladium on charcoal (5%) as catalyst at normal pressure.
After fil~ration of the reaction mixture and removal of the
solvent~ the residue is taken up in etherl washed with saturated
sodium chloride solution, dried (Na2S04) and concentrated by
evaporation. Recrystallisation from petroleum ether yields the
compound of the formula
CH C~3 CH3
CH2 C ~ CHCOOH
CH2
in the form of a diastereomeric mixture having a melting
point of 88~93C.
c) Production of ~-cyano-3-phenoxybenzyl-2',2'-dimethyl-
spiro-(2,4)-hept-4-ene-1-carboxylate.
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~ '7~ ~
After the dropwise addition of 6 rnl of oxalyl chloride
to a solution of 1.9 g ~0.0114 mole~ of 2,2 dimethylspiro-
~2,4) hept-4-ene-1-carboxylic acid in 50 ml of benzene, the
reaction mixture is stirred for 4 hours at room temperature.
The reaction mixture is subsequently freed from the solvent, and
the residue is dissolved in 50 ml of benzene. To the solution,
cooled to 0C, there is added dropwise within 15 minu~s
2.47 g (0.0110 mole) of a-cyano-3-phenoxybenzyl alcohol
dissolved in 4 ml of pyridine. The reac~ion mix~ure is stirred
for 12 hours at room temperature. For processing, the mixture
is diluted with ether, washed three times with water, three
times ~lith 0.5N hydrochloric acid and twice with saturated
~odium chloride solution. The organic phase is separated, dried
over sodium sulphate and concentrated by evaporation. The
crude product is chromatographed with ether/hexane = 1:~ as
eluant through silica gel. There is obtained the compo~nd of
the formula
CH CH
~ / 3
C C - C~-C-0-CH ~ 1i-~
C~2
as a diastereoisomeric mixture having a refractive index of
nD = 1.5~78.
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Example Z
A) Insecticidal stomach-poison action
Tobacco and potato plants were sprayed with a 0.05%
aqueous active-substance emulsion ~obtained from a 10% emul-
sifiable concentrate~.
After drying of the coating, caterpillars of Spodoptera
littoralis in the L3-stage and of Heliothis virescens in the
L3-stage were placed onto the tobacco and potato plants. The
test was carried out at 24C with 60% relative humidity.
The compound according to Example 1 exhibited in the above
test a good insecticidal stomach poison action against Spodoptera
littoralis and Heliothis virescens caterpillars.
B) Insecticidal contact action
. _
One day before application of the active-substance emulsion,
broad beans (Vicia faba) grown in pots were infested with about
200 bean aphids ~Aphis fabae) per plant. The spray emulsion at a
concentration of lOOO ppm (prepared from a 25% wettable powder) was
applied by means of a compressed-air sprayer to the leaves infested
with aphids. An evaluation was made 24 hours after application.
The compound according to Example 1 exhibi~ed in the above test a
good contact ac~ion against Aphis fabae.
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