CA1185621A - .alpha.-ALLENYL-3-PHENOXYBENZYL ALCOHOLS AND HALIDES - Google Patents

Abstract

ABSTRACT OF THE INVENTION
This invention describes certain .alpha.-allenyl-3-phenoxybenzyl alcohols of the formula in which each of Y1 and Y2 is halogen or hydroxyl. These compounds are intermediates in the preparation of certain cyclopropanecarboxylic acid esters of the formula

Description

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), 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 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 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%

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 . , 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-~

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\

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~

Claims (6)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS;

1. A compound of the formula wherein each of Y1 and Y2 is hydrogen or halogen.

2. A process for the production of a compound of the formula wherein each of Y1 and Y2 is hydrogen or halogen, which comprises reacting an .alpha.-ethynyl-3-phenoxybenzyl alcohol of the formula with paraformaldehyde and diisopropylamine, in the presence of copper bromide as a catalyst.

3. .alpha.-allenyl-3-phenoxybenzyl alcohol.

4. .alpha.-allenyl-3-(4-fluoro-phenoxy)benzyl alcohol.

5. .alpha.-allenyl-3-(4-chlorophenoxy)benzyl alcohol.

6. .alpha.-allenyl-3-(4-bromophenoxy)benzyl alcohol.