AP97A - Fluorobenzyl esters. - Google Patents

Fluorobenzyl esters. Download PDF

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Publication number
AP97A
AP97A APAP/P/1987/000067A AP8700067A AP97A AP 97 A AP97 A AP 97A AP 8700067 A AP8700067 A AP 8700067A AP 97 A AP97 A AP 97A
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Prior art keywords
formula
group
acid
benzyl
alcohol
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APAP/P/1987/000067A
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AP8700067A0 (en
Inventor
Alan John Whittle
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Ici Plc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/608—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a ring other than a six-membered aromatic ring in the acid moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34—Nitriles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/40—Halogenated unsaturated alcohols
    • C07C33/46—Halogenated unsaturated alcohols containing only six-membered aromatic rings as cyclic parts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/55—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing halogen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

R is selected from

Description

This invention relates to novel fluorobenzyl esters useful· as insecticides and acaricides, and to intermediates and processes useful in their preparation.
The novel fluorobenzyl esters of this invention have 5 the general formula (I):
(I) wherein R is selected from hydrogen, cyano, methyl and ethynyl, and X represents the residue of any carboxylic acid of formula X-COOH which forms an insecticidally active ester <vith a 3-phenoxybenzyl· alcohol. More particularly X represents (a) a group of formula :
APO 00 0 9 7
-CH- C - R2
wherein (i) Rl and r2 are each selected from hydrogen, halo and alkyl of up to four carbon atoms; or (ii) R^ is hydrogen and r2 represents either a group of formula :
or a group of formula :
R3 f j
- CH - C- R4
I | i J
Y Y where RJ and R*1 are each selected from methyl, halo, or haloalkyl of one or two carbon atoms containing ar least two fluorine atoms, and Y is chloro or bromo; or (iii) R^ is hydrogen and R3 represents a group of formula
AP000097 where R3 represents an alpha-branched alkyl group; or (b) X represents a group of formula :
R6
- CH- Ar where r6 represents an alkyl group of up to four carbon atoms and Ar represents a phenyl group optionally substituted with one or two halogen atoms.
Preferred compounds according to the invention are those of formula (IA) :
BAD ORIGINAL £
R1
(ΙΑ) wherein R is hydrogen, cyano or methyl, Rl and r2 are each selected from haloge'n and alkyl* of up to four carbon atoms (preferably methyl), or Rl is hydrogen and r2 is a group of formuLa :
CH.
wherein RJ and are each selected from chloro, bromo and tri fluoromethyl, or Rl is a group of formula
C(CH3b methyl, fluoro, is hydrogen and
AP000097
Particularly preferred compounds according to formula (I) are those set cut in Table I below whcrehi the meanings of rT and r2 are set out for each compound.
BAD ORIGINAL
TABLE I
Conwu nil R , RC 32
1 X ii ch3 CIb
2 H H ί -CH=C(CH3}2
3 H ’ H -ch=cci2
/* H H -CH=C3r-> 4-
5 H H -CH=CF2
6 H H i -CH=C(F)CF-
7 H H -CH=C(Ci)CF3
3 H H -CH=C(Br)CF,
9 H H -CR=C(CF3)2
19 ii C1 Cl
11 CN ch3 ch3
12 CN H -CH=C(CK3)2
13 CN H -CH=CCl2
14 CN H -CH=CBr2
15 CN H -CH=CF2
16 CN H -ch=c(f)cf3
17 CN H -CH=C(C1)CF3
18 CN H -CH=C(Br)CF3
19 CN H -CH=C(CF3)2
20 CN Cl Cl
21 ch3 CH3 C H 3
22 CH. 1 J H -CH=C(CH3)2
23 ch3 H -ch=cci2
24 Cl,3 11 -CH=CBr2
2 5 C!l3 I 11 -cii=cf2
BAD ORIGINAL ft
TABLE I (cont)
ompour.d R n
2 G Cli3 11 -CH=C(E)CF3
2 7 L-1 ΐ 3 H -CH=C(C1)CE3
28 Cll3 11 -CH=C(Gr)CE3
2 9 ch3 11 -CH=C(CK3)2
30 Ch3 Cl Cl
31 -C=CH ' H 11 — C((_rlq )
32 . -C=CH 1 H “L-H—C L 1 2
33 -C^CH H -Cll=CBr9
3 4 -C = C11 I 11 -C!b-C(Cl )CF3
3 5 -C=CH ; H -CH=C ( F )Cl-\
3 6 li . ; H /_N\
~\ /-C(CHq)q
37 CN H T-N,
AP000097 '\ /- c(ch3)
N
Many of the compounds according to the invention are capable of existinq in more than one isomeric form ovine to the presence of one or more asymmetrically substituted carbon atoms. Thus, in those compounds of formula 1 wherein R is not hydrogen, the asymmetrically substituted carbon atom to which R is attached may ό·; i si in the R-form
BAD ORIGINAL &
or the S-form. Asymmetric substitution is also exhibited at the carbon atom of the cyclopropane ring of the compounds of formula (ΙΛ) when Rx and R are not both methyl, and additionally at the Cg atom where R and R are not identical. In the latter case, four isomeric forms of the acid moiety may exist, the (lR,cis), (IS,cis), (IR,trans) and (IS,trans) forms.
Where RJ and R^. are not identical there exists the further possibility of E and Z isomers of the group R .
The scope of the invention includes each of the said isomeric forms in isolation as well as mixtures thereof, including racemic mixtures.
Especially preferred compounds according to formula (I) include the 3-benzy1-4-f1uorobenzyi, 3-benzyi- 15 cyano-4-fluorobenzyl and 3-benzyl-^ -methy1-4-fluorobenzy1 esters of the following cyclopropane acids.
2,2,3,3-tetramethylcyclopropanecarboxylic acid,
2,2-dichloro-3, 2-dimethylcyclopropanecarboxylic acid, ( IRS , ci s)-3-(2,2-dichlorovinyl )-2,2-dime thy1cyclopropane20 carboxylic acid, (IRS,trans)-3-(2-methylprop-1-en-1-yl)-2,2-dimethylcyclopropanecarboxylic acid, (lRS,cis)-3-(2,2-difluorovinyl)-2,2-dimethylcyclopropanecarboxylic acid, (IRS,cis )-3-(2, 2-dibroinov inyl )-2, 2-dime thy lcyc lop ropanecarboxylic acid,
BAD ORIGINAL ( 1 R, cis) -3-(2, 2-dibromovinyl )-2, 2-d Linet:hy Lcyclopropanecarboxylic acid, ( 1RS , cis ) - 3 - ( 7, - 2 - ch loro- 3 , 3 , 3 -1 r i f luor opr op-1 -en d imethyleye lop ropanecarboxy lie acid.
(1R,cis)-3-(2-2-chloro-3,3,3 -tr i fluoroprop-1-en-1-y1)-2,2dimethylcylcopropanecarboxyIic acid , ( IRS , cis )-3-(Z-2,3,3,'3-tetra fluoroprop- l-en-l-yl)-2,2dimethylcyclopropanecarboxylic acid, (IRS,trans-3-(2-2,3,3,3-tetra f1uoroprop-l-en-l-yl)-2,210 dimethyLcyclopropanecarboxylic acid, (IRS,cis)-3-(2-trifluorome thyl-3,3,3-t ri fluoroprop-1-en-lyl)-2,2-dimethyleyelopropanecarboxylic acid, and (IRS,trans-3-[2 - (1,1-dimethy1ethyl)pyrimidin-5-yl]-2,2dimethyIcyclopropanecarboxylic acid .
Other compounds of the invention include the 3-benxyl4-fluorobenzyl· and 3-benzyl-(X-cyano-4-fluorobenzyl esters of:
APO00097 (IRS,cis )-3-(1,2-di bromo-2,2-d i ch Loroethy i)-2,2-dimethy 1eyelopropanecarboxy1ic acid and (RS)-2-(4-chloropheny1) - 320 methylbutyric acid.
The compounds of the invention are esters and may be prepared by conventional esterification processes, of which the following are examples.
BAD ORIGINAL Ql (a) An acid of formula (II)
X- COOK (II) where X lias any of the meanings given hureinabove, may be reacted directly with a fluorobenzyl alcohol· of formula (III ) :
(III) wherein R has any of the meanings given hereinabove, the reaction preferably taking place in the presence of an acid catalyst, for example, dry hydrogen chloride, or a dehydrating agent, for example, a carbodiimide such as di cyclonexylcarbodiimide.
(b) An acid halide of formula X-COHal where Hal represents a halogen atom, preferably a chlorine atom, and X has any of the meanings given hereinabove, may be reacted with an alcohol of formula (III), the reaction preferably taking place in the presence of a base, for example, pyridine, trialkvlamine, alkali metal hydroxide or carbonate, or alkali metal alkoxide.
In a variant of this process leading to the formation of ίΧ-cyano substituted esters, an acid halide of formula XCOHal is reacted with 3-benzyl-4-fluorobenzyldehyde (V) in the presence of an alkali metal cyanide, the reaction
BAD ORIGINAL &
(1R, cis )-3-(2,2-dibromovi nyl)-2,2-dimethylcyclopropaneca rboxy lie acid, ( IRS, cis ) - 3 - (7 - 2-chloro-3,3, 3-1. r i fluoronro;»- I-en-l-yl)-2,2dimethylcyclopropanecarboxy1 ic acid, (1R,cis)-3-(2-2-chloro-3,3,3-tri fluoroprop-1-en-l-yl)-2,2dimethyIcylcopropanecarboxy1ic acid , (IRS, cis ) - 3- ( Z-2,3,3 ,’3-tetra fluoroprop- l-en-l-yl)-2,2dimethylcyclopropanecarboxylic acid, (IRS,trans-3-(Z-2,3,3,3-tetra fluoroprop-1-en-1-yl)-2,210 dimethyLcyclopropanecarboxylic acid, (IRS , cis)-3-(2-trifluoromethyl-3,3,3-tri fluoroprop-1-en-lyl)-2 , 2-dimethylcyclopropanecarboxyl ic acid, and (IRS, trans- 3 -1 2 - ( 1, 1 -d Line thy 1 ethyl)pyr imidi n-5-y1]-2,2dimethylcyclopropanecarboxy1ic acid.
Other compounds of the invention include the 3-benzy'L4-fluorobenzyl and 3-benzyl-iX-cyano-4-fluorobenzyl esters of:
(IRS,cis )-3-(1,2-dibromo-2,2-dichloroethy1)-2,2-dime thy 1cyclopropanecarboxy1ic acid and (RS)-2-(4-ch loropheny1) - 320 methylbutyric acid.
The compounds of the invention are esters and may be prepared by conventional esterification processes, of which the following are examples.
AP 0 0 0 0 9 7 bad ORIGINAL when performed at elevated temperatures or in the presence of appropriate catalysts, for example phase-transfer 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
of tile carboxylic acids or salts thereof, whilst the various optically active species may be
acids with optically active amines, followed by regeneration of the optically pure acid. The optically pure isomeric form of the acid (or its equivalent acid chloride or ester) may then be reacted with the alcohol of formula (II) to produce a compound of formula I in the form of an individually pure isomer thereof.----Esterifiable derivatives of the acids of formula (II) wherein X represents the group of formula :
CH CH
CH3 wherein represents an CX-branched alkyl group, are described in UK Patent Application No. 2,157,28SA.
The compounds of formula (III) and (IV) and 3-benzyl4-fluorobenzaldehyde have not been described previously.
In a further aspect therefore the invention provides compounds of formula (III) and (IV) and more specifically each of the following compounds :
BAD ORIGINAL
3-ben zy 1 -; - r 1 ucrobcrizy 1 Iehyde
3-benzy1-4 -f1uorobcnzy1 alcohol
\ -cyano-3-benzy1-4-fluorobenzy1 a 1coho 1
3-benzyl - 4 - 1 : ic 4 ·· ·: i 1 chloride
1) 1/ -<· v, no - 3 - ben z.v i -4 - 1 ’ i in.>ir >b<Hiz.y 1 i · h 1. .> r 1111'
X -niei.hy 1 -3 -be:i;-.';·' ’ -4 - ‘ 1 uorobenzy 1 a ! o -no !
•V -methyl -3-benzy 1-4- 11 norohenzyl ch lor ide .
3-Benzy1-4-f1uorobenzaIdehyde may be prepared by means
of the process described in Scheme I. The compounds of
P formula (ITT) and formula (TV) may be prepared from 3-
benzyl-4-fiuorobenzaldehy<le by means of the processes described in Scheme IT. further details of many of these crocus.ire yi- '-n in the Examples hereinafter.
bcneme i
APO00097
C6H5CH2 Pd(O)
H + /TUO l0J /
C6H5C1I2
SHO
BAD ORIGINAL
Scheme II ex
F —(Z -CHO
MaCN >
F —2/ \\—CH —01 c,h5ch2 c6h5ch? (III, R=CX) // V.
?HO NaBH4
C6H5CH2 /
c6h5ch2
CH-,ΟΗ (111, R=H)
CH// % ----.
r —V '?— ^nO
CH-jMgBr F
-i->
%,n — i:
C6H5CH2 c6h5ch2 (III, R = CHn)
F-^~y CHO (i) (CH3 ) 3Si-CsCH/CH3MgBr / ;
CH
III
F—C -CH —OH
/ C6H5CH2
C.-HrCIh (III) υ j zC6H5CH;
(IV, HaI=Br)
BAD ORIGINAL $
- L J -
The com pounds of formula (I) may be used to combat
and control infestations of insect and acarino pests. The
insect and i car ine pests which may be combated and
controlled by the use of the invention coapounds include
5 those pests a s so c i.i ted with agriculture (which term
includes the •jr.z’wing 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 with the
10 transmission of diseases of man and animals.
In orde: r to apply tine compounds to the locus of the
pests they a re usually formulated into compositions which
include in a. Id it ion to the insecticida1lv active
ingredient or ingredients of formula (I) suitable inert
15 diluent or e; irrier materials, and/or surface active
a gents.
The compounds of the invention may be the sole active ingredient of the composition or they may be admixed with one or more additional active ingredients such as
20 insecticides, insecticide synergists, herbicides,
fungicides o; r plant growth regulators where .appropriate.
Suit a b 1.1. i additional active ingredients for inclusion
in admixture with the compounds of the invention may be
compounds whi .ch wi.l prodder. the spectrum o: .ictivitv u::
AP000097 a tne compounos of tne invention or increase t.neir
persistence i .n the location of the pest. They may
syu e i g i s e an; : activity of the compounds of the invention or
complement tr •.e activity for example by increasing the speed
of effect, iv; go roving knockdown or overcoming repeliency.
30 Adoi t Iona 1 1 y mu j L i-ccmpoue η t mixtures of tills type may hid;··
to overcome >. >r prevent tine development of resistance to
individual cc ’•rano n e n t s .
bad original
The particular insecticide, herbicide or fungicide included in the mixture will depend upon its intended utility and the type of complementary action required. Examples of suitable insecticides include the following:
(a) Pyretf.roids such as permethrin, es fenva 1 erate, de Itamethrin, cyhalothrin, biphentnrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids for example ethofenprox, natural pyrethrin, tetramethrin, s-bioa1lethrin, fenfluthrin, prallethrin and 5-benzyl-3-furylmethy1-(E)-(1R,3S)2,2-dimethy1-3-(2-oxothiolan-3-ylidenemethy1) cyclopropane carboxylate;
(b) Organophosphates such as profenofos, sulprofos, methyl parathion, azinphos-methy1, demeton-s-methv1, heptenophos, thiometon, fenamiphos, monocrotopiios, profenophos, triazophos, methamidophos, dimethoate, p’nosphami don , malathion, chlorpyrifos , phosalone, fensulfothion, fonofos, phorate, phoxim, pyrimiphosmethyl, fenitrothion or diazinon;
(c) Carbamates (including aryl carbamates) such as pirimicarb, cloethocarb, carbofuran, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur or oxainvl;
(d) Benzoyl ureas such as triflumuron, chlorofluazuron;
(e) Organic tin compounds such as cyhexatin, fenbutatin oxide, azocyclotin;
BAD ORIGINAL
(f) MacroLiies such as averinectins or miibemycins, for example such as abamectin, avermectin, and mi 1bemyci n:
(g) Hormones such as juvenile hormone, juvabione.or e c t i y s ο n e s .
(h) Pheromones.
(i) Organoc’nlorine compounds such as benzene hexachloride, DDT, chlordane or dieldrin.
In addition to the major chemical classes of insecticide listed above, other insecticides having particular targets may be employed in the mixture if appropriate for the intended utility of the mixture. For instance selective insecticides for particular crops, for example stemborer specific insecticides for use in rice such as cartap or buprofezin, can be employed.
Alternatively insecticides specific for particular insect species/stages for example ovolarvicides such as clofentazine, flubenzimine, hexythiazox and tetradifon, motilicides such as dicofol or propargite, acaricides such as bromopropylate , chlorobenzilate, or insect growth regulators such as hydramethylon, cyromazin, methoprene, chlorofluazuron and diflubenzuron may also be included i r. the compositions.
Examples of suitable insecticide synergists for use in the compositions include piperonyl butoxide, sesamex, and dodecyl imidazole.
Suitable herbicides, fungicides and plant growth regulators for inclusion in the compositions will depend upon the intended target and the effect required. An example of a rice selective herbicide which can be included is propanil, an example of a plant growth regulator for use in cotton is Pix, and examples of
AP 0 0 0 0 9 7 bad ORIGINAL fungicides for use in rice include blasticides such as biasticidin-S . The choice of other ingredients to be used in mi x'cure with the active ingredient will often be within the normal skill of the formulate·', an·.’, will be male ‘rrom Crown u ,. tern··, t . uu, uo;.·or,U ι η> ί upon tne tο! a i e i l e c t ‘ ? be· a clue v e d .
The ratio of the compound of the invention to any other active ingredient in the composition will depend upon a number of factors including the type of insect pests to be controlled, and the effects required from the mixture. However in general, the additional active ingredient of the composition will be applied at about the rate it would usually be employed if used on its own, or at a lower rate if synergism occurs.
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).
Wetting agents, dispersing agents and emu 1sifyito 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 cety1trimethy1 ammonium bromide. Suitable agents of th.e anionic type include, for example, soaps, salts of aliphatic monoesters oi‘ sulphuric acid, for example sodium la.iryi sulphate, salts of sulphonated aromatic compounds, for example sodium dodeey1 bentenesu1phonate, sodium, calcium or ammonium 1ignosuIphonate, or butyl naphthalene sulphonate.
BAD ORIGINAL and a mixture of the sodium salts of dιisopropy1- and triisopropylnaphthalene sulphonates. Suitable agents of the non-tonic type include, for example, the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, 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.
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 adding the mixture so obtained to water which may contain one or more known wetting, dispersing or emulsifying agents.
Other suitable organic solvents are dimethyl formamide, ethylene dichloride, isopropyl alcohol, propylene glycol and other glycols, diacetone alcohol, toluene, kerosene, white oil, methylnaphthalene, xylenes and trichloroethylene, N-methy1-2-pvrroIidone and tetrahydrofurfuryl alcohol (THFA).
The compositions 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 homogenous for a sufficient time to enable chem to be applied by conventional spray equipment. The concentrates may contain 5-95'0 by weight of the active ingredient or ingredients. When diluted to form aqueous preparations such preparations may contain varying amounts of the active ingredient depending upon the purpose for which
AP000097
BAD ORIGINAL *
they are to be usee. For agricultural or horticultural purposes, an aqueous preparation containing between 0.00012 ana O.it by weight of trie active ingredient is pa r t i cu1ar1y u s e f u 1.
In use the compositions are applied to the pests, bo tiie locus of tiie pests, to the habitat of the pests, or t. growing plants liable to infestation by file nests, by any of the known means of applying pesticidal compositions, for example, by dusting or spraying.
The compositions of formula (I) and compositions comprising them are very toxic to wide varieties of insect and other invertebrate pests, including, for example, the following:
Myzu s pe rs i cae ( a ph ids)
Aphi s f abae (aphids)
Megoura viceae (aphids)
Aed.es aegypti (mosquitos) mosquitos ) (mosguitos) s ( capsids )
Anopheles spp. C u1e x spp Dvsdercus
Musca domestica (houseflies)
Pter i s brassicae (white butterfly, larvae) (diamond back moth, larvae) (mu'stard beetle)
Plutella ma cu1ipenni s Phaedon cochleariae
Aon id ie1la spp. (scale insects)
Trialcuroi.des spp- (white flies)
DIattella germanlea (cockroaches )
Periplaneta americana (cockroaches)
Blatta oriental i s (cockroaches)
Spodoptera 1 i ttora1 is (cotton leaf worm) Heliothis virescens (tobacco budworms) Chortiocetes t e nm nifera (locusts) Piabrotica spp. (rootworms)
Agrot is spp. (cutworms )
Cliilo partel 1 us (maize stem borers)
Nl1apa rvata 1ngens (plant hoppers) Nephotetlix cincti ceps (plant hoppers)
BAD ORIGINAL £
The compounds of formuLa (I) and compositions comprising them have shown themselves to he useful in . an t s, and ouo 11o and mosquitos. The compounds pests which inhabit the soil, _ __ They ma-y also be useful in and acarine pests which infest domestic controlling foliar feeding pests of health pests such as flies map' also he used to combat for example Diahrotica sop combating inse<
animals, si
c.n ls Lucilia ita, and ixodid ticks such as
Booph i lus spp. , Ixodes spp. , Amblyomma spp. , R’nipicephalus spp., and Dermaceutor spp. They are expected to be effective in combating 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 parenteral administration.
The compounds according to formula (I) and compositions comprising them also exhibit a high level of acaricidal activity, and are particularly useful in the control cf the foil;
;q acar r ne pes:
Panonychus spp., for example PanonPanonycnns citri;
s ulmi and
APO00097
Tetranychus spp., for example Tetranychus urticae and Tetranychus cinnabarinus;
Phy1locoptruta olervora;
Po1v ch a ο o t a r sο n· sop . , ano
Brevioalcus soo.
T
BAD ORIGINAL
The following Examples illustrate various aspects of tins invention. In the preparation Examples the products were usually identified and characterised by means of nuclear magnetic reasonance spectroscopy and infra red spectroscopy. In each case where a product is specifically named its spectral characLeristics are consistent with the assigned structure. Except where stated otherwise, exemplified compounds having one or more asymmetrically substituted carbon atoms were prepared in racemic form.
»
In the Examples, Gas Liquid Chromatography (GLC) retention times were determined on a Hewlett Packard 5890 Gas Chromatograph, using a Chromopak, C.P. Sil 5 C.B. column of 12.5M length and 0.2 mm internal diameter.
Unless otherwise stated, the injection temperature was 100°C, and a temperature gradient of 15°C/minute employed, up to a maximum temperature of 280°C, maintained for 4 minutes. The carrier gas was helium at a column head pressure maintained at 11 psi. Alternative injection and maximum temperatures are indicated in the Examples where app r op r i a t e.
Nuclear Magnetic Resonance (NMR) spectrometry was performed at a frequency of 270 MHz on a Jeol FX 270 NMR spectrometer, unless otherwise indicated. 90 MHz, GO MHz and 400 MHz ^H NMR spectrometry were performed using Jeol FX 90Q, Jeol PMX 60SI and Jeol GX400 spectrometers respectivelv.
^^F NMR spectrometry was performed on a Jeol FX90Q spectrometer at a frequency of 84.2ύ MHz. All NMR shift ( ςί ) values are quoted in ppm relative to a standard (TMS or CFC 1 3 > ·
Molecular Ion (M+) peaks were determined on one of three mass spectrometers : Jeol DX3O3, Kratos MS80 or Hewlett Packard UP 5992.
BAD ORIGINAL
EXAMPLE 1
This Example illustrates the stises in the preparation of 3-benzy1-4-fluoroceuzyI alcohol.
Stage 1 ·. Preparation of 3-bromo-4 - f 1 uorobenoa Idehyde .
A solution of 4 - f luoro'oenta Idehyde (49.6g) in dry 5 dichloromethane (20 cm3) was added to a cooled (0°C) suspension of powdered aluminium trichloride (90.4g) in dry dichloromethane (100 cm3). Bromine (70.4g) was added, and the mixture heated at the reflux temperature for 16 hours. After cooling, the reaction mixture was carefully poured onto ice and extracted with dichloromethane. The combined organic layers were washed with saturated sodium metabisulphite solution, water and brine, then dried ever anhydrous magnesium sulphate. Evaporation of the solvent under reduced pressure gave a dark red oil, which was purified by distillation under reduced pressure, using a 4 Vigreux column to give 3-bromo-4-fluorobenzaldehyde (45.7g) as an oil, boiling point 35-108°C at 8 mmHg.
Stage 2 : Preparation of 2-(3-bromo-4-fluorophenyl)-1,3dioxolane.
A mixture of 3-bromo-4-fluorobenzaIdehyde (45.7g), ethylene glycol (27.39g), ρ-toluenesulphonic acid (O.22 5g) and dry toluene (110 cm3) was heated at the reflux temperature under a Dean and Stark trap. After 4.5 hours, approximately 12 cm3 of water had collected in the trap, and analysis of the reaction mixture by gas liquid chromatography indicated that no starting aldehyde was
AP 0 0 0 0 9 7
BAD ORIGINAL □resent.
The cooled mixture was washed with sodium bicarbonate solution magnesium sulphate.
and brine, and dried over anhydrous Evaporation of the solvent underreduced pressure gave a yellow oil, which was purified by distillation under reduced pressure to give ( 3-broxof 1 uoropneny 1; - i , g -e. i oxo xane 10G,’C at 0.0 04 mmuo.
□οι i me
MHz 3-H NMR (CDC13) (ppm)
4.1 (4H,m); 5.8 (lH,s); 7.07.7 (3H,m).
Stage 3 : Preparation of dioxolane .
benzy 1-4 -f iuoropheny 1 ) - ] , 3 ·
This compound was prepared by a method analogous to that reported by Minato et al in Tetrahedron Letters, 21, p845, (1980).
Benzyl bromide (2.77g) was added in one addition to a suspension of activated zinc powder (2.lg) in dry tetrahydrofuran (20 cm3) under an atmosphere of nitrogen. The reaction mixture was sonicated for 2 hours, allowed to stand for 30 minutes and carefully filtered under an atmosphere of nitrogen. .The filtered solution was then added to a mixture of 2-(3-bromo-4-fluorophenyl)-1, 3dioxolane (lg) and palladium (0) tetrakis triphenylphosphine (0.05g) in dry tetrahydrofuran (10 cm3) under an atmosphere of nitrogen. The stirred mixture was heated at the reflux temperature for 40 hours, at which time analysis by gas liquid chromatography showed no trace of starting material. The reaction mixture was cooled and poured into diethyl ether. The organic layer was separated and washed with ammonium chloride solution, water and brine, then dried over anhydrous magnesium
BAD ORIGINAL ft sulphate. Evaporation of the solvent under reduced pressure gave a yellow oil which was purified by column chromatography on a silica gel support, using petroleum ether {boiling range 40-50°C) containing iiethyl ether
sec from 10¾ to 2Cs bv volume) as eluent to give 2-(3-benzy1-4-fluorophenyI)-1,3-dioxolane (0.7g). The product was used without further puri f ication.
Stage 4 : Preparation of 3-benzy1-4-fluorobenzaldehyde.
A mixture of 2-(3-benzvl-4-fluoropheny1)-1,3dioxolane (0.7g), acetone (10 cmJ ) , wafer (1 cm^) and concentrated sulphuric acid (5 drops) was stirred for 16 hours. The reaction mixture was poured into diethyl ether and the organic layer washed with sodium bicarbonate solution, water and brine, then dried over anhydrous magnesium sulphate. Evaporation of the solvents under reduced pressure gave 3-benzyl-4-fluorobenzaIdehdye (Q.59g), which was used without further purification.
7.75
AP000097
IR (liquid film) : 1700 cm 1 (C=0)
Stage 5 : Preparation of 3-benzyl-4-fluorobenzyl alcohol.
A solution of 3-benzy 1-4-f Luo robe r.za ldehyde (5g) in methanol (75 cm3) WqS cooled to 0’C. Sodium borohydri-de
BAD ORIGINAL ft ι1.34g) was added in portions, and the mixture stirred for 1 hour. The reaction tnixure was then poured cautiously into a mixture of water and diethyl ether, and the organic layer was separated, washed with water and brine, and inng.nes i um su Ipha to .
vapor aιion uried over ,i ruiy ι u o.n the solvents under reduced pressure gave a pale yellow oi; which was purified by distillation in a kugeirohr apparatus to give 3-benzyl-4-fluorobenzyl alcohol (4.Og ) .
Boiling point : 12C/C at 0.02 mmHg.
NMR (CDClg) (ppm) : 1.7 (IH,broad s); 4.0 (2H,s); 4.6 (2H,s); 7.0-7.3 (8H,m).
IR (liquid film) : 3600-3100 cn'^ (OH).
EXAMPLE 2
This Example illustrates the preparation of 3-benzyl4-f luorobenzyl (IRS, ci_s )-3-( Z-2-chloro-3 , 3 , 3-tri f iuoroprop-l-en-l-y1)-2,2-dimethyleyclopropane carboxylate ( Product I ).
A solution of dievelohexylcarbodiimide (0.4g) in dichloromethane (10 cm3) was added to a stirred mixture of (IRS , cis)-3-(Z-2-chloro,3,3,3-tri fluoroprop-1-en-1-y1)2,2-dimethylcyclopropanecarboxy1ic acid (0.54g), 3berizyi-4-f luorobenzyl alcohol (0.43g), 4-d i me thy 1 ami nopyridine (0.02·:) and dry dichloromethane (5 cm3), an-] resultant mixture stirred at the ambient temperature (ca. 20°C) for 18 hours. The reaction mixture was then heated, to the reflux temperature for 3 hours, and subsequently cooled again. The precipitate which formed was removed by filtration, <and the filtrate concentrated by evaporation of
BAD ORIGINAL S the solvent under reduced pressure. The residual oil was purified by column chromatography using a silica column eluted with a mixture of ethyl acetate (1 part by volume' and petroleum ether (boiling range 60-30 ’C, 19 parts by volume), to yield 3-benzyl-4-fluorobenzyl· (IRS, c i s ) - 3 - ( Z 2-chloro-3,3,3 -1 r i c1uoroprop-1-en-1-y1) -2,2d ime thy 1 eye lop ropaneca r’oo xy late (O.32g) .
NMR (CDC13) ppm: 1.20 (s,3H); 1.22 (s,3H); 2.0 (d,
J=7»z, 1H); 2-20 (t,J=7Hz,1H); 4.05 (s,2H); 5.03 (s,2H); 6.90-7.40 (m,9H).
NMR (ppm - relative to : -69.1(s); -113.6(m).
cfci3) ·
Infra red (liquid film)
2975, 2940, 1730, 1660, 1605, 1505,
1140, 960, 820 cm-1.
EXAMPLE 3
APO00097
This Example illustrates the preparation of (RS)- \cyano-3-benzyl-4-fluorobenzyl (IRS, cis )-3-(Z-2-chloro3,3,3-trifluoroprop-1-en-l-yl)-2,2-dime thy1eyelopropanecarboxylate (Product II).
Thionvl chloride (5 cm3) was slowly added to (IRS, cis) - 3 - ( Z-2-chloro- 3 , 3, 3-trifl uoroprop-1 - e.n-1 - v 1)-2, 2 d ime thy1 cyclopropane stirred mixture was for 30 minutes, and temperature (ca. 20° with toluene (15 cm^ carboxylic acid (lg) am Q’C. The then heated to the reflux temperature then allowed to cool to the ambient
C). The reaction mixture was diluted ), and the solvent remove ] by
BAD ORIGINAL ft evaporation under reduced pressure. This cycle was repeated twice more, until all traces of residual thionyl chloride 'sad been removed. The crude intermediate acid chloride was then immediately dissolved in 20 cm^ a mixture of diethyl ether (3 parts by volume) and petrojeum ether (boiling range 40-60eC, 1 part by volume). 33enzy1-4-f1uorobenzaidehvde (O.SGg) was then added to the solution, followed by a solution of sodium cyanide (0.20q) and tetra-n-butyl ammonium bromide (0.03g) in water (2 cm3). The two-p'nase reaction mixture was then vigorously stirred for 18 hours at the ambient temperature. After dilution with ethyl acetate, the organic layer was separated and washed with aqueous sodium bicarbonate solution and brine, and dried over magnesium sulphate.
Removal of the solvents by evaporation under reduced pressure gave an oil, which was subjected to purification by column chromatography using a silica gel column eluted with a mixture of ethyl acetate (1 part by volume) and petroleum ether (boiling range 40-60°C, 9 parts by volume) to yield (RS ) - -cyano-3-benzyl-4-fluorobenzyl ( IRS, cis)-3-(Z-2-chloro-3,3,3-trifluoroprop-l-cn-l-yl)-2,2 dimethyIcyclopropane carboxylate (0.36g 46%) as a mixture of diastereoisomers.
I ΤΗ NMR (CDC13) (ppm): 1.30 ( s , 6H ) ; 2.0 ( d , J = 7Kz , 111) ; 2.24 (t,J=7Hz,1H); 4.00 (s,2H); 6.28, 6.32 (2d,lH); 6.30 ( d , J = 7liz , 1H ) ; 7.10-7.40 (m,8H).
NMR (ppm - relative to : -69.3(s), -114.6(m).
CFCio) infra red (liquid film) : 2930, 1745, 1660, 1605, 1505, 1135, cm1 .
BAD ORIGINAL Λ zo
EXAMPLE 4
The following compounds were prepared from the appropriate starting material according to the method of E x a m o 1 e 2 or Examole 3 .
3-3enzyL- 4-f luorobenzyl (IRS, c is /1 ra.ns )-3(2,2-dr f luoroet'neny 1 )-2,2-dimethylcyclopropanecarboxvlate, cis: trans ratio of 1:9 (Product III), using the method of Example 2.
NMR (CDC13) (ppm) : 1.13 (3H,s); 1.22 (3H,s);
1.44 (lH,d); 1.90 (lH,m); 4.0 (2H,s); 4.0-41. (lH,m) 5.0 (2«.,s); 6.8-7.5 (8H,m)
GLC retention time : 8.37, 8.63 minutes (ii) 3-3e.nzyl-4-f luorobenzyl (IRS,trans)-3-(2,2dichloroethenyl)-2,2-dimethyleyelopropaneearboxylate (Product IV), using the method of Examole 2.
H NMR (CDCL3) (ppm) : 1.17 (3H,s); 1.22 (3H,s);
1.61 (lK,d); 2.24 (lH,m);
4.00 (2H,s); 5.02 (2H,s);
5.6 (ln,d); 7.0-7.4 (SH,m)
GLC retention time : 10.93 minutes.
(iii) 3-3enzyl-4-fluorobenzyl (1R,cis )-3-(Z-2-chloro3 , 3 , 3-tri fLuoroprop-l-fe:n-l-yl)-2,2-d imethy 1 eye iopropanecarboxylate (Product V), by the method of Example 2.
BAD ORIGINAL
APO00097
A
NMR (CDCIt) (ppm) : 1.25 (61!,m)
2.15 (1H,m) 5.0 (2H,s):
1.98 (12H,m): 4.0 ( 2 ri, 5 ) ;
6.8-7.4 {9H,m}.
GbC re tent ι on Lime : 9.61 ximn.eS ( RS ) - Ot-Cyano- 3-benzyl -4-f1uorobenzyI ( 1R , c i s ) - 3 (Z-2-chloro-3, 3,3-trifluoropron-1-en-1-yJ )-2,2dimethylcyclopropanecarboxylate (Product VI), by the method of Example 3.
2.24 (lH,m); 4.02 (2H,s); 6.29, 6.32 (lH,2s); 6.8 (lH,d); 7.0-7.4 (8H,m).
3-Benzyl-4-fiuorobenzyl 2,2,3,3-tetramethy1 eye 1opropanecarboxylate (Product VII) by the method of Example 2.
LH NMR (CDC13) (ppm) ; 1.17 (6H,s); 1.21 (6H,s);
4.0 (2H,s); 5.0 (2H,s);
7.0 (8H,s).
GLC retention time : 8.85 minutes.
3-Benzy.1-4-f iuorobenzyl ( IRS, c i st r a n s )-3-(2methylprop-1-en-1-yl)-2,2-dimethyIcyclopropanecarboxylate, cis:trans ratio 3:7, (Product VIII) by the method of Example 2.
BAD ORIGINAL 1H NMR (CDCI3) (ppm
1.12 (3H,s )
1.13 (3H,s) L . 4 ( 1H , d ) ; 2.05 ( 1 H , m ' 5.0 ( 2 H , s ) ; 6.8-7.4 (8
1.23 (3H,s ) 1.20 (3H,s)
1.69 (6H,m); 4.0 (2H,s);
4.9 (1H,d ; ;
GLC retention time : 9.61, 9.92 minutes.
(vii) 3-Benzyl-4-f luoro’oenzyl (1RS , trans ) - 3-( 2-t ri f lnoromethy1-3,3,3-tri fluoroprop-l-en-i-y1)-2,2-dimethy110 cyclopropanecarboxylate (Product IX), by the method of Example 2.
C- NMR (CDClj) (ppm) : 1.19, 1.21 (6h,2s): 1.82 (lH,d); 2.40 (lH,m); 3.92 (2H,s); 4.98 (2H,s); 6.24 (lH,d); 6.8-7.2 (8H,m).
GLC retention time : 8.64 minutes.
Note: this product contains less than 10% of the (1RS,cis) isomer due to the presence of (1RS,c is) material in the starting acid.
(viii) 3-Ber.zy 1-4-f iuorobenzy 1 (1 R S , c i s / tra.ns)-3-(2,2d i bromoethe ny1)-2,2-d imethy1eye 1opropanecarboxylate, cisztrans ratio 4:1, (Product X), by the method of Example 2.
ZfiOOOOdV
BAD ORIGINAL 1H NMR (CDClg) (PPm) (6K,s); 1.9 (lli,m); (2H,s); 5.01 (2H,s);
( IK,d ) ; 7.0-7.4 ί 8H,m) .
GLC retention tune
11.82 minutes .
(:x) 3-Benzy 1 -4 - f luorobenzy 1 ( 1RS , t r a n s ) - 3 - ( 2 - ( 1 ,-1 d imethy1 ethyl )pyrimidi n-5-y1Ί-2,2-dimethy1 eye 1opropanecarboxvlate (Product XI) by the method o: Example 2.
NMR (CDC13) (ppm) : 0 1
96 (3H, s ) ; 1.35 (3H,s) ;
40 ( 9H, s ) : 1 . 99 (1H,d);
56 ( IK, d ) ; 4.00 (2H,s) ;
09 (2H, s ) ; 7.2-7 .4 (8H,
7 (2 H,s) .
(x) (RS) - G<-Cyano-3-benzv1-4-f1uorobenzv1 ( IRS , trans ) 3-(2-(1,1-dimethylethy 1 )pvrimid in-5-y1]-2,2dimethylcyclopropanecarboxylate as a 3:2 mixture of enantiomer pairs (Product XII) by the method of Example 2.
Note: The preparation of ( RS ) - ii\-cyano-3-benzy 1-4-
fluorobenzyl alcohol is described in Example 6 .
1K NMR (CPC1% (ppm) : 1.0 ( 31! , 2s ) ; 1.3, 1.4
(3H,2s); 1.4 (9H,2s); 2.0
(IK,2d); 2.6 (lH,2d); 4.25
(2H, broad s ) ; 6.4
(iK,2s); 6.9-7.4 (8H, in) ;
8.45, 8.50 (2H,2s).
GLC retention time : 14.60, 15.25 minutes.
bad original
(xi) ( RS ) - 2\-Methyl-3-benzy1-4-f luorobenzyl (IRS, cis ) -3(2-2-chloro-3,3,3-trifluoroprop-l-i?n-l-yl)-2,2dimethy1cvclopropanecarboxy1 are (Product XIII) by t’ne method of Example 2.
Note: The preparation of (RS)-(\ -methy 1-3-benzy1-4fluorobenzyl alchol is described in Example 5.
400MHz i-H NMR (CDC13) (ppm) : 1.0-1.6 (9H,m); 1.95 (IH,2d); 2.L3 (IH,m); 3.99 (2H,s); 5.8 (lH,m); 6.35 (lH,m);
6.95-7.4 (8 H,m).
GLC retention time : 9.23, 9.35 minutes.
EXAMPLE 5
This Example illustrates the preparation of (RS)-0( methyl-3-benzyl-4-fluorobenzyl alcohol .
A solution of methylmagnesium bromide (0.9S9g) in dry tetrahydrofuran (2.77 cm^) was added to a stirred solution of 3-benzyl-4-fluorobenzaldehyde (0.89g) in dry tetrahydrofuran under an atmosphere of nitrogen, the temperature of the reaction mixture being kept at -35°C during the aciition by external cooling. The mixture was
AP000097 lowed to warm to the ambient emnerature and stirred for minutes. The mixture was then cautiously added to water and the products extracted into ethyl acetate. The combined organic layers were washed with water and brine, then dried over anhydrous magnesium sulphate.
of the. solvent under reduced pressure gave the title compound (Q.93g), 97% pure by GLC analysis.
Evaporation
BAD ORIGINAL
MHz 1H NMR (CDCI3) (ppm) : 1.35 (3H,d); 3.9 (2H,s);
4.7 ( 1H , q ) ; C.8-7.4 (8H,m).
dbC ru Lent ion time : 5.-51 minutes.
EXAMPLE 6
This Example illustrates the preparation of (R5)-p^5, cyano-3-benzy 1-4- f luorobenzaldehyde.
3-Benzy1-4-fluofobenzaldehyde (0.5g) was dissolved in glacial acetic acid (10 cn/ ) and the solution cooled in an ice bath. A solution of potassium cyanide (0.26g) in water (2 cm^) was added dropwise to the stirred, cooled solution and stir,ring continued for 30 minutes. The mixture was allowed to warm to the ambient temperature (ca. 20°C) and stood for lo hours, at which time analysis by thin layerchromatography showed mainly unreacted aldehyde. Further acetic acid (5 cm3) was added to redissolve the precipitate which had formed on standing and a further solution of potassium cyanide (0.26g) in water (1 cm3) was added. The mixture was allowed to stand for 1 week at the ambient temperature, and was then diluted with water. The aqueous mixture was shaken with jiiethyl ether and the ether layers separated and washed with aqueous sodium bicarbonate solution and brine, then dried over anhydrous magnesium sulphate. Evaporation of the solvent under reduced pressure gave a mixture of the starting aldehyde and the expected cyanohydrin in equal proportions (0.5g) as a yellow solid. The title compound (0.24g) was isolated as the second fraction obtained by column chromatography on silica gel, eluting with petroleum ether (boiling range 40C0°C) containing 401 by volume diethyl ether.
^H NMR (CDCl^) (ppm) : 4.05 (311,2s): 5.45 (lH,s); 7.09.0 (8 H,m).
BAD ORIGINAL &
EXAMPLE 7
This Example illustrates the biological activity of the compounds according to the invention.
The activity of the Product was determined using a variety of insect pests. The Product was used in the form of liquid preparations containing from 100 to 500 parts per million (ppm) by weight of the Product. The preparations were made by dissolving the Product in acetone and diluting the solutions with water containing 0.1% by weight of a wetting agent sold under the trade name SYNPERONIC NX until the liquid preparations contained the required concentration of the Product. SYNPERONIC is a Registered 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 the preparations. The mortality of the pests was then assessed at periods usually varying from one to seven days after the treatment.
In the case of the species Musea domestica (housefly), an additional assessment to determine the knockdown effect of the compounds was performed. Details are given in Table
II.
The results of the tests are given in Table III for each of the Products, at the race in parts per million given in the second column, as a grading of mortality designated as A, B or C wherein A indicates 80-100% mortality or knockdown, 3 indicates 50-79% mortality or knockdown and C indicates less than 50% mortality or knockdown.
In Table III the pest organism used is designated by a letter code and the pesos species, the support medium, or food, and the type and duration of test is given in Table 11 .
ZeOOOOdV
BAD ORIGINAL ft
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.^4 23 • v: .<—1 re
£ E c XJ CJ in
0 c! φ '— 4J i—4 ·»—i
c lu C-l tc Φ X
c Φ c Φ f 4-1 22 ΙΛ u>
(T T <t τ ω .-j 0 φ s: o
•C c • r*4 22 <— c~ Φ et •^4
4J CL 4-' f-' M Έ. C- M E i—4
Φ tC 0 ω >. It Φ cr· >, CJ
F F Σ) Z u- C 23
tC'
Ό
ΕΦ (0 >
u re
ft
1 4-)
ft F—.
E Φ Φ
lu 4J <t-
0 >
5 It c
i-—’ r\ t
23 r~4
£ (Z
U E
0 · — c
U 4-) c
u 0
re c 4.‘
< ? £ k.·
0 (Z o
4-) .^4 lu
c
BAD ORIGINAL
TABLE II (CONT/Γ) )
<n o
ο tn : p
V)
Ό O c cr (C <υ
Ό A
¢) P
P <z .c o P
P Ή p 5
Φ c
P C 'P <Z • p C'
E <p c c p !t C lien Cl
P £ in o r:
cr c
P p iz p c p
c P p '1 ,t <z p
UJ Z
C -e p
C
ΓΧ.
ch
CL <
BAD ORIGINAL
TABLE III
ί ji'rod.n··. E X1;n: > i <_· R,i I·· TI ’ 1 ' '- <? y; X < U - , / l‘ i J / / MI) EG liv S! Di-
i No . KD
I 2 ‘ 500 A A A A A A A A A
II 3 5 00 Λ A A - A A A A A A
III 4(i) 100 B C A - A A C A A A
IV 4 ( i i ) : 100 t C C A A A A C A A A
V 4(iii) 500 A A A A A A - A A A
VI 4(iv) ‘ 100 A c A A A A A A A A
V11 4 ( v ) 1 500 - c A - A A A A c A
VIII 4(vi) 500 c c A - A A C Λ A A
IX 4 ( v i i ) 500 A c - A A A A A A
X 4 ( v i i i ) 500 - c Ά. - A A A A A A
XI 4 ( lx ) 500 A A A - B B C A A A
XII 4 ( x) 500 A B B - A C C C C A
XIII 4 ( x i ) 500 A — A A A A A A A A
PII)/jc

Claims (3)

1. λ compound of formula :
wherein R is selected from hydrogen, cyano, methyl and ethynyl, and .
(a) X represents a group of formula
R1 i
Z60000dV wherein (r) rI and r
2 are each selected from hydrogen, halo ar —to -f our—s-ag'con—atoms-; or (ii) 7* is hydrogen arm R^ represents either a group of formula :
R3
O] a group of formula
BAD ORIGINAL ft
Y wnerein R- ar.j R^ are each selected from methyl, halo or haloalkyi of one or two carbon atoms containing at least two fluorine atoms, and Y is chloro or bromo; o (iii) Rl is hydrogen and R^ represents a group of formula :
\ / ‘
N wherein R-' represents an alpha-branehed alkyl group, or (b) X represents a group of formula :
R6
I
I — CH— Ar wherein represents an alkyl group of up to four carbon atoms and Ar represents a phenyl group optionally substituted with one or two halogen atoms.
A compound according to claim 1 wherein X represents group of formula :
BAD ORIGINAL &
(a) an acid of formula (II)
X-COOH (ID where X is as defined m claim 1, is reacted dir w:ch a fluorobenzvl alcohol of formula (III) :
F —
CH -OH C6H5CH2 (HI ) where R is as defined in claim 1, the reaction taking place in the presence of an acid catalyst or a dehydrating agent; or (b) an acid halide of formula
X-COHal where X is as defined in claim 1 and Hal represents a halogen atom, is reacted with an alcohol of formula (III), the reaction taking place in the presence of a base; or (c) a;, acid of formula (II) wherein X is as defined in claim 1, or an alkali metal salt thereof is reacted with a halide of formula (IV) ·.
AP 0 0 0 0 9 7
F
CH— Hal
IV
C6H5CH2
BAD ORIGINAL &
wherein R is as defined in claim 1 and Uni represents □ halogen atom, or with a quaternary ammonium salt derived from such a halide by reaction with a tertiary imine; or (d) a lower alkyl ester of formula X-COOQ, where X is as defined in claim: 1 and 0 represents a lower alkyl group containing up to six carbon atoms, is heated with an alcohol of formula (III), wherein R is as defined in claim 1, to effect a trans10 it» A process for preparing a compound according to claim 1 where R represents cyano, wherein an acid halide of formula X-COHal, where X is as defined in claim 1 and Hal represents a halogen atom, is reacted with 315 benzy1-4-fluorobenzaldehyde in the presence of an alkali metal cyanide.
20 6 A compound of formula
Cd - Hal
C6H5CH2
BAD ORIGINAL $
1 ·) ~r wherein R is selected from hydrogen, cyano, methyl and ethynyl, and Hal represents a halogen atom.
3-Benzyl-4-fiuorobenzaIdehyde.
. A process for the preparation of 3-benzy1-4-fluoro5 benzaldehyde which comprises the step of * (i) protection of the aldehyde group of 3-bromo-4fluorobenzaldehyde by reaction with an aldehyde protecting reagent, followed by the step of (ii) reaction of the protected 3-bromo-4-fluoro10 benzaldehyde with a benzyl halide of formula
CgHgCHnHal, wherein Hal represents a halogen atom, in the presence of zinc and a palladium (0) catalyst, followed by the step of (iii) deprotection of the 3-benzyl-4-fluoro15 benzaldehyde derivative formed in step (ii) to give 3benzy1-4-fluorobenzaldehyde .
A . A process according to claim 10 wherein the aldehyde protecting group is selected from 1,2-di'nydroxyethane and 1,3-dihydroxypropane.
20 1C
APo η n
3-Benzyl-4-fluorobenzyl alcohol .
3-Benzy1-4-fluorobenzyl chloride.
-Cyano- 3-benzyl-4-f luorobenzyl alcohol.
(/ -Cyano-3-benzy 1-4 - f 1 uorobenzy 1 chloride.
BAD ORIGINAL i
id 3X-Methyl-3-benzyl-4-f luorobenzvl alcohol.
• ':·, Os-Met hv 1 - 3 - bonzy 1 - 4 - f 1 uorobenzy 1 chloride .
An insecticidal and acaricidal composition comprising as active ingredient an insecticida1ly and
3 acaricidally effective amount of the compound of claim
1 in association with an inseeticibally and acaricidally inert diluent or carrier.
i'7 a method of combating insect and acarine pests at a locus which comprises applying to the locus the
10 insecticidal and acaricidal composition of claim 18.
APAP/P/1987/000067A 1986-07-18 1987-07-16 Fluorobenzyl esters. AP97A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB868617649A GB8617649D0 (en) 1986-07-18 1986-07-18 Fluorobenzyl esters

Publications (2)

Publication Number Publication Date
AP8700067A0 AP8700067A0 (en) 1987-05-01
AP97A true AP97A (en) 1990-09-12

Family

ID=10601338

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Application Number Title Priority Date Filing Date
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US (1) US4902814A (en)
EP (1) EP0253536A3 (en)
JP (1) JPS6330452A (en)
KR (1) KR880001571A (en)
CN (1) CN87105021A (en)
AP (1) AP97A (en)
AU (1) AU601750B2 (en)
GB (2) GB8617649D0 (en)
HU (2) HU200260B (en)
IL (1) IL83065A0 (en)
NZ (1) NZ220946A (en)
OA (1) OA08638A (en)
ZA (1) ZA874862B (en)

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Publication number Priority date Publication date Assignee Title
FR2708930B1 (en) * 1993-08-10 1995-09-08 Roussel Uclaf New esters derived from 2,2-dimethyl 3- (3,3,3-trifluoro-1-propenyl) cyclopropane carboxylic acid, their preparation process and their application as pesticides.
DE10022661A1 (en) * 2000-05-10 2001-11-15 Clariant Gmbh Ortho-substituted benzaldehydes, process for their preparation and their use
AU2002953128A0 (en) * 2002-12-05 2002-12-19 Osmose (Australia) Pty Ltd Surface treatment for wood and wood products
WO2012150206A2 (en) 2011-05-04 2012-11-08 Bayer Cropscience Ag Novel cyclopropanoic acid ester derivatives as pest control agents
WO2012150207A1 (en) 2011-05-04 2012-11-08 Bayer Cropscience Ag Use of cyclopropanecarboxylic acid ester derivatives for controlling insecticide-resistant insects

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4225533A (en) * 1979-06-01 1980-09-30 Zoecon Corporation Fluorobenzyl esters of cyclopropanecarboxylic acids
EP0060617A1 (en) * 1981-03-18 1982-09-22 Imperial Chemical Industries Plc Fluorobenzyl cyclopropane carboxylates, their preparation, compositions and use as insecticides
EP0156630A2 (en) * 1984-03-23 1985-10-02 Commonwealth Scientific And Industrial Research Organisation Arthropodicidal compounds, their manufacture and uses in compositions containing them

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4024163A (en) * 1972-05-25 1977-05-17 National Research Development Corporation Insecticides
US4457940A (en) * 1980-12-27 1984-07-03 Dainippon Jochugiku Kabushiki Kaisha Carboxylic acid ester derivatives, process for manufacturing said derivatives, insecticides and acaricides containing said derivatives, and method for killing insects and acarina by treating therewith
FR2515176A1 (en) * 1981-10-23 1983-04-29 Roussel Uclaf NOVEL ESTERS OF AROMATIC OR HETEROAROMATIC ALCOHOLS, PROCESS FOR PREPARING THEM AND THEIR APPLICATION TO THE FIGHT AGAINST PESTS
EP0162538A3 (en) * 1984-03-26 1986-10-29 Imperial Chemical Industries Plc Cyclopropane derivates
GB8520027D0 (en) * 1985-08-09 1985-09-18 Ici Plc Insecticidal ethers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4225533A (en) * 1979-06-01 1980-09-30 Zoecon Corporation Fluorobenzyl esters of cyclopropanecarboxylic acids
EP0060617A1 (en) * 1981-03-18 1982-09-22 Imperial Chemical Industries Plc Fluorobenzyl cyclopropane carboxylates, their preparation, compositions and use as insecticides
EP0156630A2 (en) * 1984-03-23 1985-10-02 Commonwealth Scientific And Industrial Research Organisation Arthropodicidal compounds, their manufacture and uses in compositions containing them

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HU200743B (en) 1990-08-28
HU896622D0 (en) 1990-03-28
OA08638A (en) 1988-11-30
AU7552587A (en) 1988-01-21
ZA874862B (en) 1988-01-18
GB8617649D0 (en) 1986-08-28
HUT44399A (en) 1988-03-28
JPS6330452A (en) 1988-02-09
HU200260B (en) 1990-05-28
GB2193959A (en) 1988-02-24
GB8715190D0 (en) 1987-08-05
KR880001571A (en) 1988-04-25
AU601750B2 (en) 1990-09-20
US4902814A (en) 1990-02-20
AP8700067A0 (en) 1987-05-01
NZ220946A (en) 1989-10-27
GB2193959B (en) 1990-10-03
EP0253536A2 (en) 1988-01-20
IL83065A0 (en) 1987-12-31
EP0253536A3 (en) 1989-02-22
CN87105021A (en) 1988-01-27

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