Note: Descriptions are shown in the official language in which they were submitted.
This application is a divisional. of Application No. 3X~,263 which
was filed on August 20, 1981.
The present invention relates to intermecliates usefu] for preparing
cyclopropanecarboxylic acid ~-allenyl-3-phenoxybenzyl esters, which find use
in pest control. The cyclopropanecarboxylic acid ~-allenyl-3-phenoxyben~yl
esters have the formula
CH=C3CH2
Xl C CH-C~-C l-COOCH~ ~ (I),
CH3CH3 1 2
wherein Xl i5 halogen and each of Yl and Y2 is hydrogen or halogen.
Halogen in the above defi.nition denotes fluorine, chlorine, bromine
or lodine, with fluorine, chlorine or bromine being preferred.
Preferred compounds are those of the formula I, wherei.n Xl is
fluorine or chlorine9 Yl is hydrogen and Y2 is hydrogen, fluorine, ch].orine
or bromine.
The most preferred compounds are those of the formula I, wherei.n X
is chlorine, Yl is hydrogen and Y2 is hydrogen, fluorine or chlorine.
These compounds are described and claimed in Application ~o. 38~,2~3.
The compounds of the formula I are obtained by methods which are
known per se, e.g. as follows:
1) X
1 C=CH-CH-CH-COX CH=C=CH acid acceptor or
3 3 + OH-CH ~ ~ o ~ hydrophilic ~ I
(II) (III) 1 2
2) Xl C=C~I~C}~-CH-COOR C~l=C=CH2
Xl / Cll3 C~l~ + HO-C~ 0 ~ -R03
(IV) (Il-L) 1 2
In Eormlllae Il to IV abo~7e, ~1~ Yl and Y2 are as defined for
formula I,
In formulae II ~' is a halogen atom, especially chlorine or bromine,
and R in formula IV is Cl-C~I alkyl, preferably methyl or ethyl.
Suitable acid acceptors are in particular tertiary amines, such as
trialkylamines and pyridine, and also hydroxides, oxides, carbonates and
bicarbonates of alkali metals and alkaline earth metals, and in addition alkali
metal alcoholates, for example potassium tert-butylate and sodium methylate,
As hydrophilic agent it is possible to use e.g. dicyclohexylcarbodiimide.
Processes 1 and 2 are carried out at a reaction temperature between -10 and
120 C, usually between 20 and 80 C, under normal or elevated pressure and
preferably in an inert solvent or diluent. Examples of suitable solvents or
diluents are: ether and ethereal compounds, for example diethyl ether,
dipropyl ether, dioxane, dimethoxyethane and tetrahydrofurane; amides, such
as N,N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydro-
carbons, especially benzene, toluene, xylene, chloroform and chloroben~ene;
nitriles, such as acetonitrile; dimethyl sulfoxide; and ketones, such as
acetone and methyl ethyl ketone.
The starting materials of the fonmllae II and IV are known or they
can be obtained by methods analogous to known ones. Tile compounds of the
formula III are novel.
Thus this invention provides an ~-allenyl-3-phenoxyben~yl compound
of the formula III
Cl~=C=C~I
~y ~ Y
in which Yl and Y2 each separately represent hydrogen or halogen.
These compounds may be prepared by reacting an ~-e-~hynyl-3-
phenoxybenzyl alcohol of the formula
C - CH
~ O - ~ CH-OH
Y2 Yl
with paraformaldehyde and diisopropylamine, in the presence of copper
bromide as a catalyst.
The present invention, together with that of applicants
aforementioned copending application number 384,263 will now be further
described.
- 2a -
The compounds of the formula I exist in the form of a mixture of
di:Eferent optically active isomers if inhomogeneous optically
active starting materials are used in the reaction~ The different
mix-tures of isomers can be separated into the individual isomers
by known methods. A compound of the formula I will be understood
to comprise both the individual isomers and -the mixtures -thereof.
Tile compounds of the formula I are suitable Eor con-
trolling a variety of pests of animals and plants. In particular,
the compounds of the formula I are suitable for con-trolling
insects, phytopathogenic mi-tes and ticks, for example of -the
orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera,
Acarina, Thysanoptera, Or-thoptera, Anoplura, Siphonaptera,
Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera.
In particular, the compounds of the formula I are
suitable for con-trolling plant-destructive insects, especially
plant- destructive feeding insects, in ornamen-tals and crops oE
useful plants, especially in cotton and rice plantations (e.g.
Spodoptera littoralis, Heliothis virescens, Chilo suppressalis
and Laodelphax) and in crops of vegetables and fruit (for example
Leptinotarsa decemlineata, Myzus persicae, Laspeyresia pomonella
and Adoxophyes re-ticulana).
The compounds of -the Eormula I are also very effec-tive
against flies, for exarnple Musca domestica and mosquito larvae.
The acaricadal and/or insecticidal action can be sub-
stantially broadened and adapted to prevailing circumstances by
addition of other insecticides and/or acaricides. Examples of
suitable additives include organophosphorus compounds, nitro-
phenols and derivatives thereof, formamidines, ureas, pyrethroids,
carbamates, and chlori.nated hydrocarbons.
Compounds of the formula I are also combined with
particular advantage wi-th substances which exert a synergis-tic or
potentiating ef:Eect on pyrethroids. Examples of such compounds in-
clude: piperonyl butoxide, propynyl ethers, propynyl oximes,
propynyl carbamates and propynyl phosphates, 2-(3,4-methylene-
dioxyphenoxy)-3,6,9-trioxaundecane (Sexamex or Sesoxane), S,S,S-
tributylphosphorotri-thioate, 1,2-methylenedioxy-4(2-(oc-tyl-
sulfinyl)-propyl)-benzene.
The compounds of the formula I are used in unmodified
form or, preferably, together with the adjuvan-ts conventionally
employed in the art of formulation, and are therefore formulated
in known manner to emulsifiable concentrates, directly sprayable
or dilutable solutions, dilute emulsions, we-t-table powders,
soluble powders, dusts, granula-tes, and also encapsulations in
e.g. polymer s-ubs-tances. The methods of application, such as
spraying, atomising, dusting, scattering or pouring, are chosen
in accordance wi.th the intended objectives and the prevailing
circumstances, just li~e -the nature of -the composltions.
The formulations, i.e. the composi-tions or preparations
containing the compound (active ingredien-t) of the formula I and,
where appropriate, a solld or liquid adjuvan-t, are prepared in
known manner, e.g. by homogeneously mixing and/or grinding the
active ingredients with extenders, e.g. solvents, solid carriers
and, where appropriate, surface-active compounds (surfactants).
Suitable solvents are: aroma-tic hydrocarbons, pre-
ferably the fractions containing 8 to 12 carbon atoms, e.g.
xylene mixtures or substituted naphthalenes, ph-thalates such as
--4--
rjg~, ?~~
dibu-tyl ph-thalate or dioctyl phthala-te, aliphatic hydrocarbons
such as cyclohexane or paraffins, alcohols and glycols and their
e-thers and es-ters, such as ethanol, ethylene glycol, ethylene
~lycol monomethyl or monoe~hyl ether, ketones such as cyclo-
hexanone~ strongly polar solvents such as N-methyl~2-pyrrolidone,
dimethyl sulEoxide or dimethyl formamide, as well as epoxidised
veyetable oils such as epoxidised coconu-t oil or soybean oil; or
water.
The solid carriers used e.g. Eor dusts and dispersible
powders, are normally natural mineral fillers, such as calci-te,
talcum, kaolin, montmorillonite or attapulgi-te. In order -to
improve the physical properties it is also possible to add highly
dispersed silicic acid or highly dispersed absorbent polymers.
Suitable granulated adsorptive carriers are porous types, for
example pumice, broken brick, sepiolite or bentoni-te; and suitable
nonsorbent carriers are materials such as calcite or sand. In
addition, a great number of pre~ranulated materials of inorganic
or organic nature can be used, e.g. especially dolomite or
pulverised plant residues.
2Q Depend:ing on the nature of the compound of -the formula I
to be formulated, suitable surface-active compounds are nonionic,
cationic and/or anionic surfac-tan-ts having good emulsifying,
dispersing and wetting properties. The -term "surfactants" will
also be understood as comprising mixtures of surfactants.
Suitable anionic surfactan-ts can be both water-soluble
soaps and water-soluble syn1-hetic surface-active compounds.
Sui-table soaps are the alkall metal sal-ts~ alkaline
earth salts or unsubsti-tuted or substituted ammonium salts of
higher Eatty acids (C10-C22)~ e.g. the sodium or potassium salts
of oleic or s-tearic acid, or of natural fatty acid mixtures which
can be obtained e.g. from coconut oil or tallow oil. Mention may
also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants
are used, especially fatty sulfonates, fatty sulfates, sulfonated
benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form
of alkali metal salts, alkaline earth metal salts or unsubstitu-
ted or subs-tituted ammonium salts and contain a C8-C22alkyl
radical which also includes the alkyl moiety of acyl radicals, e.g.
the sodium or calcium salt of lignosulfonic acid, of dodecyl-
sulfate or of a mixture of fatty alcohol sulfa-tes obtained from
natural fatty acids. These compounds also comprise the salts oE
sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene
oxide adducts. The sulfonated benzimidazole deriva-tives pre-
ferably con-tain 2 sulfonic acid groups and one fatty acid radical
containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates
are the sodium, calcium or triethanolamine sal-ts of dodecyl-
benzenesu]fonic acid, dibutylnaphthalenesulfonic acid, or of a
napthalenesulfonic acid/formaldehyde condensation produc-t. Also
suitable are corresponding phosphates, e.g. salts of -the
phosphoric acid ester of an adduct of p-nonylphenol wi-th 4 to
14 moles of ethylene oxide.
Non-ionic surfactants are preferably po:Lyglycol ether
derivatives of aliphatic or cycloaliphatic alcohols, or saturated
--6--
or unsatura-ted fat-ty acids and alkylphenols, said derivatives
containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms
in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in
the alkyl moiety of the alkylphenols~
Further suitable non-ionic surfactants are the water-
soluble adducts of polyethyler.e oxide with polyproplene glycol,
ethylenediamine propylene glycol and alkylpolypropylene glycol
con-taining 1 to 10 carbon atoms in -the alkyl chain, which adducts
contain 20 to 250 ethylene glycol ether groups and 10 -to 100
propylene glycol ether groups. Thesecom~ounds usually con-tain
1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are
nonylphenolpolyethoxyethanols, castor oil polyglycol ethers,
polypropylene/polyoxyethylene adducts, tributylphenoxypolye-thoxy-
ethanol, polyethylene glycol and octylphenoxyethoxye-thanol.
Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene
sorbitan trioleate are also suitable non-ionic surfactan-ts.
Cationic surfactants are preferably quaternary ammonium
salts which contain, as N-substituent, at least one C8-C22alkyl
radical and, as further substituen-ts, lower unsubstituted or
halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The
salts are preferably in the form oE ha:Lides, methylsulfates or
ethylsulfates, e.y. stearyltrimethylammonium chloride or benzyldi-
(2-chloroethyl)ethylammonium bromide.
The surfac-tants customarily employed in the ar-t of
formulation are described e.g. in "McCutcheon's Detergents and
Emulsifiers Annual", MC Publishing corp., Rinywood, New Jersey,
1979.
' ? ~L
The pesticidal formula-tions usually contain 0.1 to
99%, preferably 0.1 to 95%, of a compound of the formula I, l
to 99.9% of a solid or liquid adjuvant, and O to 25%, preferably
0.1 to 25%, of a surfac-tant.
~ Ihereas commercial products are preferably formulated
as concentrates, the end user will normally employ dilute
formulations.
The formula-tions can also contain further additives
such as stabilisers, antifoams, viscosi-ty regulators, binders,
adhesives, as well as fertilisers, in order to produce special
effects.
~ ~3'~
Formulation Examples
. _
Formulat.ion Examples :Eor liquld activ~ i gredients of the formul I
(-throughou-t, percentages are by weigh-t)
1) Emulsifiable concentrates a) b) c)
active ingredien-t 20% 40% 50%
calcium dodecylbenzenesulfona-te 5% 8%5.8%
cas-tor oil polyethylene glycol ether
(36 moles of ethylene oxide) 5% - -
tributulphenol polyethylene glycol e-ther
(30 moles of e-thylene oxide) - 12%4.2%
cyclohexanone - 15% 20%
xylene mixture 70% 25% 20%
Emulsions of any required concentration can be produced from
such concentrates by dilution with water.
2) Solu-tions a) b) c) d)
active ingredient 80% 10% 5% 95%
ethylene glycol monomethyl e-ther 20% - - -
polyethylene glycol ~00 - 70%
N-me-thyl-2-pyrrolidone - 20%
epoxidised coconut oil - - 1% 5%
petroleum diOtillOte (boiling
range 160 -190 ) - - 94%
These solutions are sui-table for application in the form of
microdrops.
3) Granul_ es a) b)
active ingredient 5% 10%
kaolin 94%
highly dispexsed silicic acid1%
attapu]yite ~ 90%
The active ingredient is dissolved in methylene
chloride, -the solution is sprayed onto the carrier~ and the
solvent i.s subse~uently evaporated off in vacuoO
4) Dusts a) b)
active ingredient 2% 5%
highly dispersed silicic acid1% 5%
talcum 97%
kaolin ~ 90%
Ready-fox-use dusts are obtained by intimately mixi.ng
the carriers with the active i.ngredient.
Formulation examples for solid active ingredients of the formulaI
.. . . . _ . . . . _ . .. .. ~
(throughout, percentages are by weigh-t)
5) Wettable powders a) b)
active ingredient 20% 60%
sodium lignosulfonate 5% 5%
sodium laurylsulfate 3%
sodium diisobutylnaphthalenesulfonate - 6%
octylphenol polyethylene glycol ether
(7-8 moles of ethylene oxide~ - 2%
highly dispersed silicic acid 5% 27%
kaolin 67%
--10--
The ac-tive ingredient is -thoroughly mixed with the
adjuvants and the mixture is thoroughly ground in a suitable
mill, affording wet-table powders which can be dilu-ted with
water -to give suspensions of the desired concentration.
6) Emulsifiable concentrate
.. , .__
active ingredient 10%
octylphenol polyethylene glycol e-ther
(4-5 moles of e-thylene oxide) 3%
calcium dodecylbenzenesulfona-te 3%
castor oil polyglycol ether
(36 moles of e-thylene oxide) 4%
cyclohexanone 30%
xylene mixture 50%
Emulsions of any required concentration can be obtained
from this concentrate by dilution with water.
7) Dusts a) b)
active ingredient 5~ 8%
talcum 95%
kaolin - 92%
Dusts which are ready for use are obtained by mixing
the active lngredient with the carriers, and grinding the mixture
in a suitable mill.
3) Extruder granulate
active ingredient 10%
sodium lignosulfonate 2%
carboxymethylcellulose 1%
kaolin 87%
~ c3~
The ac-tive ingredient is mixed and ground with the
adjuvantsr and the mixture is subsequently mois-tened with water.
The mixture is ex-truded and then dried in a stream of air.
9) Coated granulate
_ _
active ingredient 3%
polyethylene glycol 200 3%
kaolin 94%
The finely ground ac-tive ingredient is uniformly
applied, in a mixer, to the kaolin moistened with polyethylene
10 glycol. Non-dusty coated granulates are obtained in this manner.
10) Suspension concentrate
active ingredierLt 40%
ethylene glycol 10%
nonylphenol polyethylene glycol ether
(15 moles of ethylene oxide) 6%
sodium lignosulfonate 10%
carboxymethylcellulose 1%
37% aqueous formaldehyde solution0.2%
silicone oil in the form of a 75%
aqueous emulsion 0.8%
water 32%
The Einely ground active ingredient is intimately
mixed with the adjuvants, giving a suspension concentrate from
which suspensions of any desired concentra-tion can be obtained by
dilution wi-th wa-ter.
Example 1:
A) Prepaxation__f ~-al ~ 3-phenoxbenzyl alcohol
10 g oE ~-ethynyl-3-phenoxybenzyl alcohol, 2.1 g of
paraformaldehydel 5.3 of diisopropylamine, 0.215g of Cu:Br and
50 ml of dioxane are refluxed for 2 hours. The reaction mixture
is cooled to 20C, poured into a solution of 2N HCl and extracted
with ether. The organic phase is washed with 10% potassium car-
bonate and satura-ted sodium chloride solution, dried over magnesium
sulfate and concentrated. The residue is chromatographed over
silica gel wi~h a 7:3 mixture of hexane/e-ther as eluant,
affording the compound of the formula
-13-
. , CH=C=C~H~
li i-- 1 Il-CH-OH
with a refractive index of nD = 1.5942.
The following compounds are prepared in analogous manner:
CH=C=CH~
i~ li-~ -CH-OH ~ = 1.5765
F~
CH=C=CH
Cl- i~ 1i i~ 1i ' ~
C'~=C=C~2
li--i~ -CE~-OH nD a 1- 5893
B) Preparation of ~~allenyl-3-phenoxybenzyl-~,2-dimethyl-3-(2,2-di-
chlorovinyl)cyclopropane-l-cdrboxylate
A solution of 5 g of ~-allenyl-3-phenoxybenzyl alcohol in 20 ml of
toluene is added dropwise at 0C to a mixture of 4.8 g of 2,2-dimethyl-
3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid chloride, 2.2 ml of
pyridine and 20 ml of toluene. The reaction mixture is stirred for
18 hours at 20C, poured into 2N hydrochloric acid and extracted with
toluene. The organic phase is washed with 10~ potassium carbonate and
saturated sodium chloride solution, dried over magnesiurrl sulfate and
concentrated. The crude product is chromatographed over silica gel with
a 1:10 mixture of ether/hexane as eluant, affording the compound of
the formula
CH=C=CH
C=CH- ~ OClH-i~ Ii-~
20
with a refractive inde~ of nD ~ 1.5757.
The following co~pounds are prepared in analogous ~anner:
CH=C=CH
C=CH-CH - CH-coolH-i li--~ - 1 5563
C~3 CH3
CHaC=CH
C-CH-CH - CH~C~IH~i~ li-~i~ li nD = 1.5748
C~3 CH3
CH=C=CH
C=CH-CH - c3;COOCH-i li--i ll nD = 1.5568
CH=C=CH
C=CH-Cd - ~rl COOCH-i ~ --I~ ~ nD =1. 5938
i~
- 1~ -
C'~l=C=C'~
/C=CH-CH - CH-~OO(IH-i~ l--~ nD = l.a719
Cl \~C\
3 3
1 R - cis, ~ RS
CX-C=C~
C=CH-CH - CH-C00~ l--i~ li nD = 1.5627
C~3 CH3
lR - cis, a ~S
C~=C=C~.
\C=CH-CH - CH-COOCH-- i li-- i li
Cl \ ¢ .
3 ~3
Biological Examples
_
Example 2: Insectlcidal stomach poison action a~ainst Spodoptera
littoralis and Heliothis virescens
Cotton plants are sprayed ~ith a solution containing 50, lO0, 2C0 or
400 ppm of the compound to be tested. After the coating has dried, the
plants are populated with larvae of the species Spodoptera littoralis
(L3-stage) or Heliothis virescens (~3-stage). Two plants are used for
each test compound and ~est species. A mortality count is made after
2, 4, 24 and 48 hours. The test is carried out at 28C and 60~ relatiie
hun~idity.
Within the above concentration liL~its, the compounds of Example 1 are
effective against larvae of the species Spodoptera littoralis and
~leliothis virescens (vide Table).
~ S~
Ecample ,: ~c~?r~cidal action
Twe~ve hours before the test for acaricidal action, Phaseolus vulgaris
plents are infected with an infested piece of leaf from a mass culture
of Tetranychus urticae. The mobile stages which have migrated to the
plants are sprayed from a chromatography atomiser with a solution
containing 50, 100, 200, 400 and 800 ppm of the compound to be tested,
such that the spray mixture does not run off. A count of living and
dead organisms is made under astereoscopic microscope after 7 days and
expressed in percentage values. During the test run the plants are
stood in greenhouse compartments at 25C.
~ithin the above concentration limits, the compounds
of Example 1 are effective against adults, larvae and eggs of Tetra-
nychus urticae (vide Table).
Example 4: Feedin _and depth action aga_nst_Adoxophves_retic-llana
(L3 larvae)
Two small apple trees (20 cm high) are each infected with 5 to 8 L3
larvae of Adoxophyes reticulana. Over 3 days these larvae are afforded
the opportunity to roll themselves up into a leaf. Before the treatment,
the leaves are first examined for rolled up larvae. Any larvae not or
insufficiently rolled up are removed. Three days after infestation each
of the apple trees is sprayed with 25 ml of a solution containing 50
or 100 ppm of the compound to be tested. A count of living and dead
larvae is made 3 days after the treatment. Within the above indicated
concentration limits, compounds according to Example 1 are effective
against L3 larvae of Adoxophes reticulana (vide Table).
Biological test results
... . _ .
Test results based on the preceding Exampl2s are reported in the
following table, using the following rating to indicate the percentage
kill of the pests:
.~: 70-100% ~ill at a concentration of 50 p~"m
B: 70-100~ '~ill at a concentration of 100 ppm
C: 70-].00% ~ill at a concentration of ~00 ppm
D 70-100~ I;ill at a concentration of 400 ppm
Iq
C~3
~ ) ~
ChJi ~
Cl~ ~
Cl
O O
~ ~ ~a
V~
~, \\.
C)~ ---
o ~ ~ ~ ~ 3
~ ,~ X~
