AU639708B2 - Butyric acid derivatives - Google Patents

Butyric acid derivatives Download PDF

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Publication number
AU639708B2
AU639708B2 AU61097/90A AU6109790A AU639708B2 AU 639708 B2 AU639708 B2 AU 639708B2 AU 61097/90 A AU61097/90 A AU 61097/90A AU 6109790 A AU6109790 A AU 6109790A AU 639708 B2 AU639708 B2 AU 639708B2
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AU
Australia
Prior art keywords
chloro
acid
hydrogen
difluorobutyric
difluorobutyric acid
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AU61097/90A
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AU6109790A (en
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Manfred Boger
Peter Maienfisch
Eginhard Steiner
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Novartis AG
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Ciba Geigy AG
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
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Abstract

Novel 4-chloro-4,4-difluorobutyric acid derivatives of the formula I <IMAGE> in which R1 and R2 independently of one another are hydrogen, C1-C4-alkyl or C1-C4-haloalkyl, R3 is hydrogen or an organic radical and X is oxygen or -NR4-, where R4 represents hydrogen or C1-C6-alkyl, can be employed as pesticides. Insects and arachnids can preferably be controlled.

Description

6397 08 S F Ref: 137325 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE: Class Int Class Complete Specification Lodged: Accepted: Published: Priority: Related Art: 1 Name and Address of Applicant: Address for Service: Ciba-Geigy AG Klybeckstrasse 141 4002 Basel
SWITZERLAND
Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Males, 2000, Australia Complete Specification for the invention entitled: Butyric Acid Derivatives The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/3 PS/5-17701/1+2/+ Butyric acid derivatives Abstract Novel 4-chloro-4,4-difluorobutyric acid derivatives of formula I ClF 2 C-cjH-tfH-- -X-R3 R, R 2 0 00. wherein and R 2 independently of one another are hydrogen, Cl-C4alkyl or Cl-C 4 haloalkyl, 008 3 is hydrogen or an organic radical and X is oxygen or -NR 4 s o a in which R 4 is hydrogen or Cl-C 6 alkyl, may be used as pesticides. Especially insects and arachnids can be controlled.
goof 00 o0 so 0 so 0.6000.
lA- PS/5-17701/1+2/+ Butyrc acid derivatives The present invention relates to novel derivatives of 4-chloro, 4,4-difluorobutyric acids, to processes and intermediates for their preparation, to pesticidal compositions that contain those compounds, and to their use in pest control.
The 4-chloro-4,4-difluorobutyric acid derivatives according to the invention correspond to formula I ~ClF 2 C-c H--c H- -X-R 3
(I
R R 2 0 ::wherein RI and R 2 independently of one another are hydrogen, Cj-C4alkyi or Cl-C4haloalkyl, R~z is hydrogen or an organir radical and X is oxygen or -Rin which R 4 is hydrogen or Cl-C 6 alkyl.
In the literature, the class of polyhalogenated butyric acid chlorides as intermediates for pyrethroidai haloketones is known from Helv. Chim. Acta L3, p. 1947-1957 (1980).
The organic radical mentioned in the definition of R 3 is any organic radical that can be bonded in the form of an alcohol or of an amine. to the carbonyl group of 4-chloro-4,4-difluorobutyric acid. Preferably, the alcohol or amino function of that organic radical is Sbonded to a carbon atom. Accordingly, the radical R3 is preferably bonded via a carbon atom to the -CO-X group. For example, R(3 is C 1
-C
20 alkyl, C3-C 7 cycloalkyl,
C
3 -C2 0 aikenyl, C 3 -C20ailkynyl, benzyl or aryl, each of which is substituted or unsubstituted. Within the, scope of the present invw:ntion, R3 is preferably Cl-C2 0 alkyl, C3-C7cyciOalkyl, C 3 -C20alkenyl, C 3 -C20alkynyl, aryl, C 3
-C
2 0 haloalkenyl, C 3
-C
20 haloalkynyl; C3-C7cycloalkyl substituted by halogen or by CI-C4alkyl; aryl substituted by halogen, C 11 -C4alk 4, Cl-C4haloalkyl, Cl-Cl~alkoxy, Cl-C naloalk xy, Cl-C4alkylthio, nitro, cyano, benzoyl, halobenzoyl, phenoxy, halophenoxy, Cl-C4alkylphenoxy, -2- Cl-C 4 haloalkylphenoxy, tri-Cl-C4alkylsilyl, N-pyrrolidinyl, N-piperidinyl, N-pyrrolidin-2-onyl, N-piperidin-2-onyl, C 1
-C
4 alkylamino, di-C 1 -C4alkylamino, anilino,
N-C
1 -C4alkylanilino, N-formylanilino, N-C 1 -C~alkylcarbonylanilino, phenylthio or by halophenylthio; phenyl substituted by an unsubstituted or substituted, aromatic or non-aromatic, monocyclic or bicyclic heterocycle that is bonded via oxygen or sulfur, in which both the heterocycle and the phenyl ring may each be substituted by halogen, C l-C4alkyl, nitro, Ci-C 4 haloalkyl, Cl-C4haloalkoxy, Cl-C4alkoxy, Cl-C 4 alkylthio or by cyclopropyl; or Cl-C20alcyl substituted by hydroxy, halogen, di-Cl-C4allcylamino, C 1
-C
4 alkoxy, C 1 -C4haloalkoxy, C2-$2~alkoxcyalkoxy, Cl-C4haloalkylthio, Cl-C 4 alkylthio, Cl-C4alkylsulfinyl, Cl-C 4 a~kylsu,!fonyl, Cl-C4alkylsulfonyloxy, Cl-C 4 alkylcarbonyl, Cl-C4alkoxycarbonyl, C1-C6alkyl~carbonyloxy, C3-C7cycloalkyl, aryl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, arylsulfonyloxy, arylcarbonyl or by pyridyl, in which the aryl and pyridyl groups may each be substituted by halogen, Cl-C 4 alky1, Cl-C 4 ::haloalkyl, Cl-C4alkoxy, Cl-C 4 haloalkoxy, C 1 -C4alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or by halophenylthio.
In the definition of formula I according to the invention, the individual generic terms should be understood as having the following meanings: Halogen atoms that come into consideration as substituents are fluorine and chlorine and sea also bromine and iodine, with fluorine, chlorine and bromine being preferred. Halogen is here toq be undr -stood as being an indepenC:Vnt substituent or part of a' substituent, such as :in haloalkyL, haloalkylthio, haloaikoxy, halophen-ylthio or ha,'ophenoxy.
Alkyl, alkylthio, alkoxyalkoxy and alkoxy radicals that come into consideration as substituents may be straight-chained or branched. Examples of such alkyl radicals are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl or pentyl, hexyl, octyl, decyl, dodecyl and their isomers. Suitable alkoxy radicals are inter alia: methoxy, ethoxy, propoxy, isopropoxy or butoxy and their isomers. Alkylthio is, for example, methylthio, ethylthio, isopropylthio, propylthio or the isomers of butylthio.
If the alkyl, alkoxy, alkenyl, alkynyl or aryl groups that come into consideration as substituents are substituted by halogen, they may be only partially halogenated or also perhalogenated. The definitions given above apply here for halogen, alkyl and alkoxy.
Examples of the alkyl elements of those groups are methyl substituted from one to three times by fluorine, chlorine and/or by bromnine, for example CHF 2 or CF 3 ethyl -3substituted from one to five times by fluorine, chlorine and/or by bromine, for example CH2CF3, CF 2
CF
3
CF
2 CC1 3
CF
2 CHC12, CF 2
CHF
2
CF
2 CFC12, CF 2 CHBr 2
CF
2 CHC1F, CF 2 CHBrF or CCIFCHCIF; propyl or isopropyl substituted from one to seven times by fluorine, chlorine and/or by bromine, for example CH 2 CHBrCH 2 Br,
CF
2
CHFCF
3
CH
2
CF
2
CF
3 or CH(CF 3 2 butyl or one of its isomers substituted from one to nine times by fluorine, chlorine and/or by bromine, for example CF(CF 3
)CHFCF
3 or
CH
2
(CF
2 2 CF3.
If the alkyl, cycloalkyl or aryl groups defined under R3 are substituted by other substituents, they may be mono- or poly-substituted by identical or different substituents selected from those listed. Preferably, the substituted groups contain one or two further substituents.
es.
The cycloalkyl radicals that come into consideration as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Alkenyl and alkynyl groups contain one or more, preferably not more than three, unsaturated carbon-carbon bonds. The double or triple bonds are separated from the point of linkage to the bridge X by at least one saturated carbon atom. Typical examples are allyl, methallyl, 2-butenyl, 3-butenyl, propargyl, 2-butynyl or 3-butynyl.
Aryl is an aromatic hydrocarbon radical. Preferably, aryl is understood as being phenyl or naphthyl.
Examples of alkoxyalkoxy radicals are methoxymethoxy, methoxyethoxy, ethoxyethoxy, ethoxymethoxy, propoxymethoxy, propoxyethoxy, methoxypropoxy, butoxymethoxy and propoxyethoxy.
Examples of alkoxycarbonyl radicals are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl and butoxycarbonyl. Alkylcarbonyl is, for example, acetyl, propionyl, b-tyryl or valeryl, as well as isomers thereof.
Alkylcarbonyloxy is, for example, acetoxy, propionyloxy or butyryloxy.
Examples of aromatic and non-aromatic, monocyclic or bicyclic heterocycles that are bonded via. an oxygen or sulfur atom to phenyl nuclei defined under R3 are the following cyclic basic structures: pyridine, pyrazine, pyridazine, pyrimidine, pyrrolidine, thiazoli, thiadiazole, oxazole, benzothiazole, triazine, oxadiazole, quinoline, quinoxaline, quinazoline, isoquinoline, phthalazine, naphthyridine, cinnoline, pteridine, triazole, piperidine Gr benzoxazole. These heterocycles are preferably bonded via an oxygen or sulfur bridge to the 4-position of the phenyl nucleus. The oxygen or sulfur bridge itself is carried by a carbon atom of the heterocycle. Both the phenyl nucleus and the heterocycle may carry further substituents, for example they may each carry up to three radicals from the group halogen, alkyl, haloalkyl and alkoxy or one or two substituents from the group nitro, haloalkoxy, alkylthio and cycloalkyl. In general, the total number of substituents at the phenyl ring and at the heterocycle together is not more than four. Preferably, those two groups together carry not more than 3 further substituents from the group chlorine, bromine, methyl, ethyl and trifluoromethyl, and are bonded to one another via an oxygen atom.
:Of those compounds, special mention should be made of those wherein R 3 is phenyl substituted in the 4-position by an aromatic monocyclic or bicyclic heterocycle bonded via oxygen and selected from the group pyridine, pyrimidine and benzothiazole, in which both aromatic rings are unsubstituted or together carry not more than three further substituents from the group chlorine, bromine, methyl, ethyl and trifluoromethyl.
Especially, the phenyl radicals that are substituted by a heterocycle via, oxygen or sulfur se* under the definition of R 3 may have, for example, the following individual meanings: o: -4-(3-methylthiadiazol-5$yloxy)-phenyi, -4-(4-bromothiazol-2-yloxy)-phenyl, -4-(5-trifluoromelhylpyrid-2-yloxy)-phenyl, -4-(3,5-dichloropyrid-2-yloxy)-phenyl, -4-(3-chloro-5-trifluorornethiylpyrid-2-yloxy)-phenyl, *00 -3-(5-trifluoromethylpyrid-2-yloxy)-phenyl, S: -2,6-dimethyl-4-(4-trifluoromethylphenoxy)-phenyl, -2,6-diisopropyl-4-(N-formylaiuilino)-phenyl, -2,6-diisopropyl-4-(N-methylanilino)-phenyl, -4-phenylthiophenyl, -4-(2-cyclopropyl-4-trifluoromethylpyrimidin-6-yloxy)-phenyl, -4-(2-tert.-butyl-4-trifluoromethylpyrimidin-6-yloxy)-phenyl, -4-(2-methylthio-4-methylpyrimidin-6-yloxy)-phcnyl, -4-(2-methyl-4-triflujoromethylpyrimidin-C&y'ioxy)-phenyl, -4-(6-trifluoromethoxybenzothiazol-2-yloxy)-phenyl, -4-(6-chlorobenzothiazol-2-yloxy)-phenyl, -4-(6-nitrobenzothiazol-2-yloxy)-phenyl, -4-(6-methoxybenzothiazol-2-yloxy)-phenyl, -4-(5-trifluoromethylbenzothiazol-2-yloxy)-phenyl, -3,5-dichloro-4-(3-chloro-5-trifluoromethylpyrid-2-yloxy)-phenyl, -2,6-dimethyl-4-(3-chloro-5-trifluoromethylpyrid-2-yloxy)-phenyl, -4-chloro-3-(3,5-bis-trifluoromethylpyrid-2-yloxy)-phenyl, -4-chloro-3-(5-chloro-3-fluoropyrid-2-yloxy)-phenyl, -2,6-dimethyl-4- [3-chloro-5-(2,2-dichloro- 1, 1,2-trifluoroethyl)-pyrid-2-yloxy]-phenyl, -4-[3-chloro-5-(2,2-dichloro- 1,1 ,2-trifluoroethyl)-pyrid-2-yloxy]-phenyl, -4-(N-acetylpyrid-3-ylamino)-phenyl, S.4dclr--3cloo5tilooehlprd2yoy-hnl ,*-4-dhocro-3-(3-chloro-5-trifluoromethylpyrid-2-yloxy)-phenyl, -4-ethycaboi--(3-chloro-5-trifuoromethylpyrid-2-yloxy)-pheny -3,-ehl-3chloro-5-trifluoromethylpyrid.-2-yloxy)-phenyl, *-3,-di-chloro-4--trifluoromethylpyrid-2-yloxy)-phenyl, -4-(6m3(-chloro- ifluoromethylpyrid-2-'oxy)-phenyl, -3-(5-trifluoromethylpyrid-2-yloxy)-phenyl, -2,6-dimethyl-4-(3,5-dichloropyrid-2-ylthio)-phenyl, -2,6-dimethyl-4-(2-chloropyridazin-6-yloxy)-phenyl, -2,6-dimethiyl-4-(pyrimidin-2-yloxy)-phenyl, K: -2,6-dimethyl-4-(pyrazin-2-yloxy)-phenyl, 0 l 2,6-dimethyl-4-(6-chloroquinoxalin-2-yloxy)-phenyl, c -2,6-dimethyl-4-(6-trifluoromethylquinoxalin-2-yloxy)-phenyl, -2,6-dimethyl-4-(quinolin-2-yloxy) -phenyl, -4-chloro-2-fluoro-5-(3-methyl- 1 ,2,4-thiadiazol-5-yloxy)-phenyl, -2,6-dimethyl-4-(4-bromothiazol-2-ylb,, y)-phenyl or 6:40 -4,-methyl-3-(3-chloro-5-trifluoromethylpyrid-2-yloxy)-phenyl.
Of the compounds of formula I, special mention should be made of those sub-groups in which either
R
1 and R 2 independently of one another are hydrog,-en or Cl-C4alkyl, or b) X is oxygen, -NCH3- or -NC 2
H
5 or c) R 3 is hydrogen, Cl-C 20 alkyl, C3-C 7 cycloalkyl, C3-C2Oalkenyl, C3-C2Oalkynyl, phenyl, naphthyl, C 3 -C2Ohaloalkenyl, C 3
-C
2 ohaloalkynyl; C 3
-C
7 cycloalkyl substituted by fluorine, chlorine, bromine or by Cl-C3alkyl; phenyl or naphthyl substituted by fluorine, chlorirn,, bromine or Cl-C 3 alkyI, Cl-C 3 haloalkyl, Cl-C3alkoxy, Cl-C 3 haloalkoxy, Ci-C 3 alkylthio, nitro, cyano, phenoxy, halophenoxy, Cl-C4alkylphenoxy, Cl-C 4 haloalkylphenoxy, tri-Cl-C4alkylsilyl, N-pyrrolidinyl, N-piperidinyl, N-pyrrolidin-2-onyl, N-piperidin-2-onyl, Cl-C4alkylamino, di-Cl-C4alkylarnino, anilino, N-Cl-C 4 alkylanilino, N-formylanhlino, N-Cl-C6alkylcarbonylanilino, phenyithio or by halophenylthio, or
C
1 -C2 0 alkyl substituted by hydroxy, fluorine, chlorine, bromine, di-Cl-C4alkylamino, C 1 -C~alkoxy, Cl-C 4 haloalkoxy, C2-C~alkoxyalkoxy, Cl-C 4 haloalkylthio, Cl-C 4 alkylthio, C j-C4alkylsulfinyl, Cl-C4alkylsulfonyl, Cl-C 4 alkylsulfonyloxy, Cl-C 4 alkylcarbonyl, C1 -C4alkoxycarbonyl, Cl-C~alkylcarbonyloxy, C3-C7cycloalkyl, phenyl, phenoxy, phenylthio, phenylsulfonyloxy or by pyridyl, in which the phenyl and pyridyl groups may each be substituted by fluorine, chlorine, a 4, bromine, Cl-C 3 alky1, C l-C3haloalkyl, Cl-C3alkoxy, Cl-C 3 haloalkoxy, %ease Cl-C~alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or by halophenyl- 0:000: thio, or too d) R 3 is phenyl substituted in the 4-position by an aromatic monocyclic or bicyclic heterocycle bonded via oxygen and selected from the group pyridine, pyrimidine and benzothiazole, in which both aromatic rings are unsubstituted or together carry not more than three further substituents from the group chlorine, bromine, methyl, ethyl and trifluoromethyj Of the compournds of sub-group those are preferred wherein Rl and R2 are hydrogen.
Of the compounds of sub-group those are preferred wherein X is oxygen or -NH-.
Special mention should be made of the group of compounds of formula I wherein Rl and SR2 independently of one another are hydrogen or C I-C4alkyl, X is oxygen or -NRg- and R4 is hydrogen, methyl or ethyl. Very especially preferred compounds of formula I are those wherein R1 and R2 are hydrogen.
Of the compounds of formula I of sub-group special mention should be made on the one hand of those compounds wherein R3 is phenyl, benzyl, naphthyl or 3-pyridylmethyl or phenyl, benzyl, naphthyl or 3-pyridylmethyl each of which is substituted by fluorine, chlorine, bromine, Cl-C 3 alkyl, C 1
-C
3 haloalkyl, Cl-C3alkoxy, C 1 -C3h1aloalkoxy, -7-
C
1
-C
3 alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or by halophenylthio. Of those compounds, preference is given in turn to those wherein R 1 and R2 independently of one another are hydrogen or C 1
-C
4 alkyl, X is oxygen or -NR 4 and R4 is hydrogen, methyl or ethyl.
On the other hand, special mention should be made also of those compounds of formula I of sub-group c) wherein R 3 is C 1
-C
1 2 alkyl or C 1 -C12alkyl substituted by hydroxy, fluorine, chlorine, bromine, dimethylamino, methoxy, ethoxy, methoxyethoxy, ethoxyethoxy, methylthio, ethylthio, cyclopropyl, cyclopentyl, cyclohexyl, phenyl or by phenoxy, in which the phenyl or phenoxy radical may be substituted by fluorine, chlorine, bromine, phenoxy, halophenoxy or by phenylthio. Of that group of compounds, preference is given to those wherein R 1 and R 2 independently of one another are hydrogen or C 1 -C4alkyl, X is oxygen or -NR 4 and R4 is hydrogen or C1-C 4 alkyl. More Sespecially, in preferred forms Ri and R 2 are both hydrogen.
S A very interesting group of compounds of formula I of sub-group c) comprises compounds wherein R 3 is C 3 -C12alkenyl, C 3
-C
1 2 alkynyl or C 3 -C1 2 alkenyl or C3-C12alkynyl each of which is substituted by fluorine, chlorine or by bromine. Of that group, preference is given to those compounds wherein R 1 and R2 independently of one another are hydrogen or C 1 -C4alkyl, X is oxygen or -NR4- and R4 is hydrogen or C1-C4alkyl. The meaning of hydrogen for RI and R 2 is especially preferred.
The following may be mentioned as preferred individual compounds of formula 1: 4-chloro-4,4-difluorobutyric acid methyl ester, 4-chloro-4,4-difluorobutyric acid ethyl ester, 4-chloro-4,4-difluorobutyric acid isopropyl ester, 4-chloro-4,4-difluorobutyric acid tert.-butyl ester, 4-chloro-4,4-difluorobutyric acid n-butyl ester, 4-chloro-4,4-difluorobutyric acid (2,2-dimethylpropyl) ester, 4-chloro-4,4-difluorobutyric acid benzyl ester, 4-chloro-4,4-difluorobutyric acid phenyl ester, 4-chloro-4,4-difluorobutyric acid [2-(4-phenoxyphenoxy)-ethyl] ester, 4-chloro-4,4-difluorobutyric acid cyclohexyl ester, 4-chloro-4,4-difluorobutyric acid cyclohexylmethyl ester, 4-chloro-4,4-difluorobutyric acid cyclopropylmethyl ester, 4-chloro-4,4-difluoro-2-trifluoromethylbutyric acid ethyl ester, 4-chloro-4,4-difluorobutyric acid N-methylamnide, 4-chloro-4,4-difluorobutyric acid N,N-dimethylamide, 4-chloro-4,4-difluorobutyric acid N,N-dihexylamide, 4-chloro-4,4-difluorobutyric acid N-ethylamide, 4-chloro-4,4-difluorobutyric acid N-isopropylamide, 4-chloro-4,4-difluorobutyric acid N-butylamide, 4-chloro-4,4-difluorobutyric acid N -tert.-butylamide, 4-chloro-4,4-difluorobutyric acid N-benzylamide, 4-chloro-4,,4-difluorobutyric acid anilide, 4-chloro-4,4-difluorobutyric acid N-methyl-N-pyrid-3-yl methylamide, 4-chloro-4,4-difluorobutyric acid N-pyrid-3-ylmethylamide, 4-chloro-4,4-difluorobuiyric acid (4-chioroanilide), 4-hoo44diloouyi acd(4peoxail) 000,4-chloro-4,4-difluorobutyric acid (2-chiooanilide), 4-hoo44diloouy0 acd(-ehoynld) b:.:4-chloro-4,4-difluorobutyric acid (4-mhlanilide), 4-hoo44dfuoouyi cd(4mtoynld) Woo*o&,-iloobtrcacd(-ehymratonld) 4-chloro-4,4-difluorobutyric acid (4-fluoroanilide), 4-chloro-4,4-difluorobutyrc acid (4-chlrntoanilide), 4-chloro-4,4-difluorobutyric acid (4-pheoxenyld)etr S4-chloro-4,4-difluorobutyric acid [(4-hlorophnioaniy),ey]etr :::4-chloro-4,4-difluorobutyric acid [(-fluoropenoy)peoth ester, 4-chloro-4,4-difluorobutyric acid (4-nitlrophen )-hnl ester, 4-chloro-4,4-difluorobutyric acid [4-(3,-fluorophenoxy)-phenytyl ester, 4-chloro-4,4-difluorobutyric acid [4-(5truormethnyrd2ylx)hnl ester, 4-chloro-4,4-difluorobutyric acid and *64-chloro-4,4-difluorobutyric acid amide.
The compounds of formula I according to the invention can be prepared analogously to known processes. For example, the compound of formula I is obtained by either a) reacting a 4-chIbro-4,4-difluorobutyric acid halide of formula II C2.F 2 C-TH- H- c-Hal I) RI R 2 0 -rein R 1 and R 2 are as defined under formula I and Hal is halogen, preferably chlorine or bromine, with a compound of formula III
H-X-R
3 (III), wherein X and R 3 are as defined under formula I, in the presence of a base, or b) reacting 4-chloro-4,4-difluorobutyric acid of formula Ic C1F 2 C-CH-CH- -OH (Ic),
R
1
R
2 0 wherein R 1 and R 2 are as defined under formula I, with a compound of formula III in the presence of water-removing igent, .J The reaction of process a) (nI+II 1) is preferably carried out in an inert solvent that is free of hydroxy groups in the presence of an organic base, for example pyridine, 4-dimethylaminopyridine, lutidine, collidine, a trialkylamine or N,N-dialkylaniline, or bicyclic, non-nucleqphilic bases, such as 1,4-diazabicyclo[2.2,2]octane (DAB CO), 1,5-diazabicyclo[4,3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5,4.0]undec-7-ene (1.5-5) (DBU). The reaction is generally carried out at temperatures of from -30° to preferably from -100 to +50°C. The reaction is advantageously carried out in the presence of an inert solvent or solvent mixture. Suitable solvents are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert.-butyl methyl ether, etc.), anole, dioxane, tetrahydrofien; nitriles, such as acetonitrile, propionitrile; esters, such a as ethyl auetate, propyl acetate or butyl acetate; ketones, such as acetone, diethyl ketone, nethyl ethyl ketone, cotndA stc~ as dimethyl sulfoxide (DMSO), dimethylformainide (DMF), and mixtures of such solvents with one another. However, the reaction may also be carried out in an excess of one of the above-mentioned bases or, if the compound of formula III is an amine (X NR4), a second equivalent or even a relatively large excess of the compound of formula III may be used instead of the base.
In process variant b) (Ic IF the reaction is advantageously carried out in the presence of water-removing agents customarily used in esterification reactions, for example in the presence of a carbodiimide [dicyclohexylcarbodiimide (DCC)] or of a 1-alkyl-2-halopyridinium salt, such as 1-methyl *2-chloropyridinium iodide. The reaction is advantageously carried out in the presence of an inert solvent or solvent mixture at temperatures of from -30 0 C to +70 0 C, preferably from -10 0 C to +50 0 C. The reaction is preferably carried out in the presence of a base, for example in the presence of an organic amine, such as a trialkylamine (trimethylamine, triethylamine, tripropylamine or diisopropylethylaniine), a pyridine (pyridine itself, 4-dimethylaminopyridine or 4-pyrrolidinopyidine), a morpholine (N-methylmorpholine) or an N,N-dialkylaniline (N,N-dimethylaniline or N-methyl-N-ethylaniline). Suitable solvents are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert.-butyl methyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles, such as acetonitrile, propionitrile; esters, such as ethyl acetate, propyl acetate or butyl acetate; and mixtures of such solvents S with one another.
If the compound of formula III is an alcohol (X process variant b) may also be carried out in the presence of an acid catalyst, for example H 2
SO
4 HCI or a sulfonic acid, such as methanesulfonic acid or p-toluenesulfonic acid. In that case, the reaction is advantageously carried out with an excess of the alcohol of formula III. In this process, water that is liberated can be removed continuously from the reaction mixture. A customary method is the removal of the water of reaction by distilling off an azeotropic mixture of the solvent with water. Suitable solvents are benzene, toluene, xylene, methylene chloride or chloroform.
In principle, the various derivatives of formula I are also obtainable from the readily available lower alkyl esters of 4-chloro-4,4-difluorobutyric acid by transesterification or amidation.
For example, the derivatives of formula I of the ester type (X 0) can be obtained by base- or acid-catalysed transesterification of the lower alkyl esters of form la -11- ClF2C- H- H-C-O-C1-C4-Alkyl (la)
R
1 R2 O with the alcohols of formula ma
H-O-R
3 (nIa) wherein R 3 is ar, defined under formula I, with the exception of C 1
-C
4 alkyl. Especially suitable acid catalysts are HC1, H 2 S0 4 or a sulfonic acid. In the case of base-catalysed transesterification there is preferably used as the base the sodium or potassium alcoholate of the alcohol of formula mIa, which are obtainable from IIIa, for example, by the addition of sodium or potassium hydride. The transesterification reaction is preferably carried out at temperatures of from -20°C to +120 0 C, especially from 0 C to +100 0 C. The alcohol component IIIa is advantageously used in excess. Suitable solvents are ethers, such as diethyl ether, diisopropyl ether, dioxane or tetrahydrofuran, halogenated hydrocarbons or Saliphatic or aromatic hydrocarbons.
0 Derivatives of formula I of the amid- type (X NR 4 are obtained from the lower alkyl esters of formula Ia by reacting those esters with amines of formula IIIb
R
3 H- 3 (Ib) oR 4
R
wherein R 3 and R 4 are as defined under formula I. The amidation reactions are carried out at temperatures of from 0 C to +120 0 C. Advantageously, the reactants are reacted in an inert solvent or mixture of solvents. Suitable solvents are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles, such as acetonitrile, propionitrile; alcohols, such as methanol, ethanol, propanol, isopropanol; or water. The amine component IIIb is advantageously used in excess.
The compounds of formula III are known and some of them are commercially available, or they can be prepared analogously to known preparation processes.
I I -12- The acid halides of formula II can be obtained in customary manner from the 4-chloro-4,4-difluorobutyric acids of formula Ic by reaction with halogenating agents.
Suitable halogenating agents are especially SOCl 2 oxalyl chloride, PC1 3 POC1 3 or PC1 5 The reaction is generally carried out at temperatures of from -20 0 C to +120 0 C, preferably from 0°C to +100 0 C. The reaction ,an be carried out without solvents or in admixture with an inert solvent. Suitable solvents are, for example, aromatic hydrocarbons, such as benzene or toluene, or halogenated hydrocarbons, such as methylene chloride, chloroform or chlorobenzene. The reaction is frequently carried out with the addition of a catalytic amount of DMF.
The intermediates of formula II are novel. They have been developed specifically for the synthesis of the compounds of formula I. The present invention therefore relates also to those intermediates.
o The 4-chloro-4,4-difluorobutyric acids of formula Ic can be obtained from compounds of formula Ia by acid or basic hydrolysis. The reaction is generally carried it at temperatures of from -20 0 C to +120 0 C, preferably from +10 0 C to +100 0 C. In the case of acid hydrolysis it is preferable to use HC1 or H 2 S04 and in the case of basic hydrolysis NaOH or KOH. The reaction is advantageously carried out in water or in a solvent mixture of water and an organic solvent. Especially suitable organic solvents are alcohols, such as methanol or ethanol; ethers, such as dioxane or tetrahydrofuran; dimethyl sulfoxide; or dimethylformamide.
The compounds of formula la, which form a sub-group of compounds of formula I and at the same time may be used as intermediates for the preparation of the various ester and amide types of formula I, are obtainable in accordance with the following process: The compounds of formula Ia can be obtained by catalytically dehalogenating in the o-position an a-halo-4-chloro-4,4-difluorobutyric acid ester of formula IV C1F2C- -0-C 1
-C
4 -Alkyl (IV), RI R 2 Y 0 wherein R 1 and R 2 are as defined under formula I and Y is chlorine or bromine, with hydrogen.
-13- The compounds of the more limited sub-formula Ib C 1F2C-H-CH2-C-0-Ci-C4-Alkyl (Ib), RI 0 wherein R 1 is as defined under formula I, can be obtained from the a,a-dihalo- 4-chloro-4,4-difluorobutyric acid esters of formula V CIF2C-CH -0-C1-C4-Alkyl
R
1 Y 0 wherein R 1 is as defined under formula I and Y and Z independently of one another are chlorine or bromine, by catalytic a(-dehalogenation with hydrogen.
By a suitable selection of the catalyst and the reaction conditions it is also possible to replace the ac-halo atoms Y and Z stepwise with hydrogen. In this manner, the compounds of formula IV wherein R 2 is hydrogen can be prepared from the compounds of formula V •t by mono-a-dehalogenation.
The catalytic dehalogenating processes using hydrogen (IV la, V Ib and V IV) are carried out with hydrogen in the presence of a noble metal catalyst or Raney nickel, optionally in the presence of a hydrogen halide acceptor and of a solvent, at a temperature of from 0°C to +150 0 C and under normal pressure or under a pressure of up to 150 bar.
S The solvent is preferably selected from the group of the hydrocarbons, halogenated a hydrocarbons, ethers, ketones, alcohols, carboxylic acid esters, sulfones, N,N-dialkylcarboxylic acid amides, N-alkyl lactams and lactones. Some examples are petroleum ether, pentane, hexane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, S chlorobenzene, methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, S dioxane, acetone, methyl isobutyl ketone, methyl or ethyl acetate, tetramethylenesulfone, dimethylformamide, N-methylpyrrolidone, y-valerolactone, butyrolactone, methanol, ethanol or isopropanol. Preferably, the solvent is polar. Especially preferred solvents are ethyl acetate, tetrahydrofuran or alcohols. The amount of solvent can vary within wide limits. Advantageously, the amount of solvent used is equal to or up to ten times the amount of compound of formula IV or V. Hydrogen halide acceptors are generally known. They may be tertiary nitrogen bases having preferably a total of from 3 to 14especially from 3 to 12, carbon atoms, alkali metal or alkaline earth metal salts of organic acids or of carbonic acid, or alkali metal or alkaline earth metal oxides or hydroxides.
Some examples are sodium carbonate, sodium or calcium hydrogen carbonate, sodium acetate, NaOH, KOH, MgO and CaO; or aromatic, aliphatic or cyclic tertiary nitrogen bases, such as trimethyl-, triethyl-, tripropyl-, tributyl-, triethanol- or butyldimethyl-amine, pyridine, 2,6-dimethylpyridine, N-methylpyrroline and N-methylmorpholine. Preferred hydrogen halide acceptors are tertiary nitrogen bases and MgO. 2,6-dimethylpyridine is especially preferred. The hydrogen halide acceptor may be used in a slightly lesser amount or slight excess relative to the amount o? compound of formula IV or V. Equimolar amounts are preferably used. Suitable noble metal catalysts are, for example, iridium, rhodium, platinum, ruthenium and palladium. The use of palladium is especially preferred.
The noble metal is preferably used as the catalyst on a carrier. Examples of carriers are BaS04, SiO 2 A1 2 0 3 and, especially, active carbon. In addition to the carrier, the catalyst used generally contains from 0.1 to 20 by weight of the noble metal. Sulfided catalysts S may also be used. The amount employed may be from 0.1 to 20 by weight, relative to the amount of compounds of formula IV or V. It may be advantageous to add catalyst that is regenerated or not used up during the reaction. The reaction temperature is preferably from 0 C to +80 0 C, especially from 0°C to +30 0 C. The pressure is preferably up to bar. Preferably, the reaction is carried out under normal pressure.
The compounds of formula V are known from EP-A-2206 or they can be obtained analogously to the process described therein. The intermediates of formula IV can be prepared by adding 1,1-difluoroethylene of formula VII
F
2
C=CH
2
(VII)
to a chloroacetic acid ester of formula VI Cl -0-C 1
-C
4 -Alkyl (VI), Y R 2 0 wherein R 2 is as defined under formula I and Y is chlorine or bromine, in the presence of a Cu(I) catalyst. Where Y chlorine, this process is described in Helv. Chim. Acta 63, p.
1947-1957 (198U).
The catalysts that may be used contain as essential element copper in oxidation stage 1.
Examples thereof are copper(I) chloride and copper(I) bromide (CuCl, CuBr) and cuprous cyanide (CuCN). CuCI and CuBr and mixtures thereof are preferred. The catalysts are generally used in amounts of approximately from 0.01 to 10 mol%, preferably from 0.1 to mol%, relative to the compound of formula VII. The reaction is carried out in an organic solvent. Suitable organic solvents are those in which the catalysts are sufficiently soluble or which are able to form complexes with the catalysts but are inert towards the starting compounds of formulae VI and VII. Examples of such solvents are alkylnitriles, especially those having from 2 to 5 carbon atoms, such as acetonitrile, propionitrile and butyronitrile; 3-alkoxypropionitriles having 1 or 2 carbon atoms in the alkoxy moiety, such as 3-methoxypropionitrile and 3-ethoxypropionitrile; aromatic nitriles, especially benzonitrile; aliphatic ketones having preferably a total of from 3 to 8 carbon atoms, such as acetone, diethyl ketone, methyl isopropyl ketone, diisopropyl ketone, methyl tert.-butyl S ketone; alkyl and alkoxyalkyl esters of aliphatic monocarboxylic acids having a total of S from 2 to 6 carbon atoms, such as formic acid methyl and ethyl esters, acetic acid methyl, Sethyl, n-butyl and isobutyl esters, as well as 1-acetoxy-2-methoxyachane; cyclic ethers, S such as tetrahydrofuran, tetrahydropyran and dioxane; dialkyi ethers having from 1 to 4 o carbon atoms in each alkyl moiety, such as diethyl ether, di-n-propyl ether and diisopropyl ether; N,N-dialkylamides of aliphatic monocarboxylic acids having from 1 to 3 carbon atoms in the acid moiety, such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide and N,N-dimethylmethoxyacetamide; ethylene glycol and diethylene glycol dialkyl ethers having from 1 to 4 carbon atoms in each alkyl moiety, such as ethylene glycol dimethyl, diethyl and di-n-butyl ether, diethylene glycol diethyl and di-n-butyl ether or hexamethylphosphoric acid triamide. Preferred solvents are alkylnitriles having from 2 to 6 carbon atoms and 3-alkoxypropionitriles having 1 or 2 carbon atoms in the alkoxy moiety, especially acetonitrile and 3-methoxypropionitrile.
The reaction temperature is generally not critical and can vary within wide limits. The reaction temperatures are preferably from approximately +60 0 C to +200°C, especially S from approximately +80 0 C to +170 0 C. The reaction may be carried out under pressure or without pressure.
The compounds of the more limited formula Id ClF2C-CH-H- -X-R (Id), Ri R2 O0 -16wherein R 1
R
2 and X are as defined under formula I and R is hydrogen or C1-C6alkyl, can be obtained from the 4-chloro-4,4-difluorocrotonic acid derivatives of formula VIII C1F 2 C-C=C- C-X-R (VI), I II
R
1
R
2 0 wherein R1, R 2 and X are as defined under formula I and R is hydrogen or C1-C6alkyl, by catalytic hydrogenation with hydrogen.
The resulting products of the more liriited sub-formulae Ia, Ib, Ic and Id can be converted into the other derivatives of formula I by customary derivatising reactions, such as hydrolysis, transesterification or transamidation.
The catalytic hydrogenation of the crotonic acids of formula VIII is carried out under conditions that are customary for that type of reaction. For example, the reaction is carried out in the presence of a noble metal catalyst or of Raney nickel, preferably in an inert solvent, under a hydrogen atmosphere, under a pressure of from 1 to 150 bar.
Suitable noble metal catalysts are, for example, iridium, rhodium, platinum, ruthenium and palladium. The use of palladium is especially preferred. The noble metal is preferably used as the catalyst on a carrier. Examples of carriers are BaSO 4 SiO 2 A1 2 0 3 and, especially, active carbon. In addition to the carrier, the catalyst used generally S contains from 0.1 to 20 by weight of the noble metal. Sulfided catalysts may also be used. The amount employed may be from 0.1 to 20 by weight, relative to the amount of compounds of formula VIII. It may be advantageous to add catalyst that is regenerated or not used up during the reaction. The reaction temperature is preferably from 0°C to S +80 0 C, especially from 0 C to +30 0 C. The pressure is preferably up to 20 bar. In particular, the reaction is preferably carried out under normal pressure. The solvent is S preferably selected from the group of the hydrocarbons, halogenated hydrocarbons, ethers, ketones, carboxylic acid esters, sulfones, N,N-dialkylcarboxylic acid amides, N-alkyl lactams and lactro s. Some examples are petroleum ether, pentane, hexane, cyclohexane, methylcyclohr benzene, toluene, xylene, chlorobenzene, methylene chloride, chloroform, 1,2-di ,oroethane, 1,1,2,2-tetrachloroethane, diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, acetone, methyl isobutyl ketone, methyl or ethyl acetate, tetramethylenesulfone, dimethylformamide, N-methylpyrrolidone, -17y-valerolactone, butyrolactone and methanol. Preferably, the solvent is polar. Especially preferred solvents are ethyl acetate and tetrahydrofuran. The amount of solvent can vary within wide limits. Advantageously, the amount of solvent used is equal to or up to ten times the amount of compound of formula VIII.
The compounds of formula VIII, with the exception of 4-chloro-4,4-difluorocrotonic acid, are novel. They have been developed as intermediates specifically for the synthesis of the compounds of formula I. The present invention relates also to those compounds. The novel compounds of formula VIII can be obtained analogously to the preparation process described for the free acid (Izvestiya Akademii Nauk SSSR, Ser. Khim, No. 2 (1965), 300-307) or can be prepared from those products by customary derivatising reactions, such as esterification, transesterification or amidation.
Compounds of formula VIII wherein R 1 and R 2 are hydrogen can also be obtained from o. compounds of formula IX i CIF 2
C-CH-CH
2 -C-X-R
(IX)
I I! O-A O wherein A is hydrogen or an acyl group, by p-elimination in accordance with known methods, for example Houben Weyl 6/lb 939 (1984).
S Compounds of formula IX can be prepared from compounds of formula X S*
CIF
2
C-C--CH
2 C-X-R
(X)
II II 0 0 S by reduction, for example catalytic reduction with hydrogen in accordance with the method described by Reuben G. Jones in J. Amer. Chem. Soc., 70 (1948) 144.
Some of the compounds of formula X are known, or they can be prepared by known methods, for example Claisen condensation (Huang Weiynan et al.; Huaxne Xuebao 1983, 41(8) 723; C.A. 1C, (1984) 22308s).
Compounds of formula X are further obtained by reacting chlorodifluoroacetyl chloride C1F 2 C-CO-Cl with ketene H 2 C=C=0 and hydrolysing the resulting 18 4-chloro-4,4-difluoroacetic acid chloride of formula XI ClF 2
C-C-CH
2 -C-Cl (XI) 11 11 0 0 to form the free acid, which is con-vexted into the esters or amides of formula X by reaction with the appropriate alcohols or aminmes. Adv.antageously, those. esters and amides can also be obtained directly by reacting the acid chloride of formrala XI with an alcohol or amine.
For example, for compounds of formula I wherein R 1 and R 2 are hydrogen, X is oxygen and R 3 is alkyl, synthesis in accordance with scheme I below is to be regarded as advantageous: 0 6 0 6 Schema 1: 0
II
CIF
2 C-C-CH--COOAIkyl e.g. with Ha/Rh/AI 2 0 3
OH
I
CIFC-CH-CH--COOAIky N. acylatlon e.g. with (H 3
C-CO)
2 0
H
2 0 X
O-CO-CH,
e.g. with P20, I
CIF
2 C-CH-CH--COOAlkyl 4
CIF
2 C-CH=CH-COOAIkyl reduction e.g. with H2Rh/A 2 0 3
CIF
2
C-CH
2 -CHy-COOAIky There is also provided according to the invention a pesticidal composition, which contains as active ingredient at least one compound of formula 1 together with a pesticidally 5 acceptable carrier, adjuvant and/or diluent.
There is further provided according to the invention a method of controlling insects and/or arachnids that are harmful to animals and plants, which comprises treating the insects and/or arachnids or the locus thereof with an insectically and/or arachnicidally effective 10 amount of a compound of formula I or a composition according to the invention.
0 0 0 0 The compounds of formula I according to the invention are valuable active ingredients in pest control while being well tolerated by warm-blooded animals, fish and plants. The compounds according to the invention can be used especially against insects and arachnids S 15 which occur on useful plants and ornamentals in agriculture, especially in cotton, vegetable and fruit crops, in forestry, in the protection of stored goods and material stocks, and also in the hygiene sector, especially on domestic animals and productive livestock. They are effective against all or individual development stages of normally sensitive and also resistant species. Their action may manifest itself immediately in the death of the pests or only at a later date, for example at shedding, or in reduced oviposition and/or a reduced hatching rate. The above-mentioned pests include: of the order Lepidoptera, for example, 4 H-X-R 3
(III),
lUbW00287:EAR Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra. cautella, Carposina nipponensis, Chilo spp., Choristoneura sr.; Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora pp., Crocidolomia binotalis, Cryptophiebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia. botrana,, Lymantria spp., Lyonetia spp., Malacosoma. spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis', Pammene spp., Pandemnis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesa mia spp., Sparganothis spp., Spodoptera. spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.; '.of the ordor Coleoptera, for example, too* Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curcuio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa deceinlineata, Lissorhoptrus spp., Melolontha, spp., Orycaephilus spp., CO* Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.; of the order Orthoptera, for example, Blatta spp., Blattella spp., 9. Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; of the order Isoptera, for example, 00 Reticulitermes spp.; of the order Psocoptera, for example, Liposcelis spp.; of the order Anoplura, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; of the order Mallophaga, for example, Damalinea spp. and 0 Trichodectes spp.; of the order Thysanoptera, for example, 0 Franklniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and Scirtothrips aurantli; of the order Heteroptera, for example, Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Saibergella singularis, Scotinophara spp. and Triatoma spp.; of the order Homoptera, for example, -21- Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemnisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Emnpoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecaniumn corni, Lepidosaphes spp., Macroiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aetlilopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri; of the order Hymenoptera, for example, Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp.
w, and Vespa spp.; of the order DiOtera, for example, Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis wo* spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, SFannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyamni, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; of the order Siphonaptera, for example, see 0 Ceratophyllus spp,, Xenopsylla cheopis, 4 of the order Acarina, for example, Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Nxodes spp., Olygonychuas pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta ole.ivora, V* Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.; and of the order Thysanura, for example, Lepisma saccharina.
The good pesticidal activity of the compounds of formula I according to the invention corresponds to a mortality of at least 50-60 of the mentioned pests.
The activity of the compounds of the invention and of the compositions containing them -22can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticides and/or acaricides. Examples of suitable additives include representatives of the following classes of compounds: organophosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.
The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation, and can therefore be formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in polymer substances. As with the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are S chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) of formula I, or combinations of those compounds with other insecticides or acaricides, and, where appropriate, a solid or liquid adjuvant, 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: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phtLalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.
S
The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acids or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of granulated 23materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of formula I to be formulated, or uf the combinations of those compounds with other insecticides or acaricides, suitable surface-active compoun are non-ionic, cationic and/or anionic surfactants having good emuls "ying, dispersing i ad wetting properties. The zetr "surfactants" will also be understood as comprising mixtures of surfactants.
Both so-called water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants.
S Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or S substituted ammonium salts of higher fatty acids (C10-C 2 2 eg. the sodium or potassium salts of oleic or stearie acid, or of natural fatty acid mixtures which can 'c obtained e.g.
from coconut oil or tall oil. Mention may also be made of fatty acid methyltaurin salts and modified and unmodified phospholipids as surfactants.
St P More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
S* The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and generally contain a Cg-C22rlkyl 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 sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing approximately 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said -24derivatives 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 ie alkylphenols. Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 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. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, castor oil thioxilate, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene S sorbitan trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C8-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g.
stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of formulation are described, for example, in the following publications: "1985 International McCutcheon's Emulsifiers Detergents", Glen Ruck, NJ, USA, 1985, H. Stache, "Tensid-Taschenbuch", 2nd edition, C. Hanser Verlag, Munich, Vienna, 1981, S M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-II, Chemical Publishing Co., New York, 1980-1981.
The pesticidal compositions usually contain 0.1 to 99 preferably 0.1 to 95 of a compound of formula I or combinations of that compound with other insecticides or acaricides, 1 to 99.9 of a solid or liquid adjuvant, and 0 to 25 preferably 0.1 to 20 of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations containing considerably lower active ingredient concentrations. Typical application concentrations are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm. The rates of application per hectare are generally from 1 to 1000 g of active ingredient per hectare, preferably from 25 to 500 g/ha.
Preferred formulations have especially the following compositions percent by weight): Emulsifiable concentrates: active ingredient: surface-active agent: liquid carrier: Dusts: active ingredient: solid carrier: Suspension concentrates: active ingredient: S water: surface-active agent: 0 Wettable powders: active ingredient: surface-active agent: solid carrier: 1 to 20 preferably 5 to 10 5 to 30 preferably 10 to 20 50 to 94 preferably 70 to 85 0.1 to 10 preferably 0.1 to 1 99.9 to 90 preferably 99.9 to 99 5 to 75 preferably 10 to 50 94 to 24 preferably 88 to 30 1 to 40 preferably 2 to 30 0.5 to 90 preferably 1 to 80 0.5 to 20 preferably 1 to 15 5 to 95 preferably 15 to 90 0.5 to 30 preferably 3 to 15 99.5 to 70 preferably 97 to 85 *a Granulates: active ingredient: solid carrier: The compositions may also contain further auxiliaries such as stabilisers, antifoams, preservatives, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for obtaining special effects.
-26- The following Examples serve to illustrate the invention. They do not limit the invention.
Preparation Examples Example P1: 4-Chloro-4,4-difluoro-2-trifluoromethylbutvric acid ethyl ester C1F 2
C-CH
2
-CH-COOC
2
H
CF
3 a) 2,4-Dichloro-4,4-difluoro-2-trifluoromethylbutyric acid ethyl ester.
22.5 g of 2,2-dichloro-3,3,3-trifluoropropionic acid ethyl ester are placed with 0.5 g of Cu(I) chloride and 100 ml of acetonitrile in an autoclave. After the introduction of 16.0 g of 1,1-difluoroethylene under pressure, the mixture is heated at +160 0 C for 8 hours. After cooling, the reaction mixture is freed of solvent and the oil that remains is rectified in vacuo. 7.4 g of 2,4-dichloro-4,4-difluoro-2-trifluoromethylbutyric acid ethyl ester are obtained in the form of a colourless oil having a boiling point of 54-56 0 C/11 mbar.
Analysis: C7H 7 C1 2
F
5 0 2 (289.03) calc.: C 29.09% H 2.44% Cl 24.53 F 32.87 found: C29.2 H2.4 Cl 24.4 F 32.9 b) 28.9 g of 2,4-dichloro-4,4-difluoro-2-trifluoromethylbutyric acid ethyl ester in 200 ml of ethanol are treated with hydrogen gas in the presence of 2 g of 5 platinum/carbon catalyst, under normal pressure and at room temperature, until 1 equivalent of hydrogen has been absorbed. After the catalyst has been filtered off, the solvent is distilled off under normal pressure and the residue is rectified. 15 g of 4-chloro-4,4-difluoro-2-trifluoromethylbutyric acid ethyl ester are obtained in the form of a colourless oil having a boiling point of 41-43 0 C/16 mbar.
Analysis: C7H 8 ClF 5 0 2 (254.58) calc.: C 33.03 H 3.17 C1 13.92 F 37.31 found: C 33.2 H13.1 Cl 14.1 F 37.0 27 Example P2: 4-Chloro-4,4-difluorobutvric acid ethyl ester C1F 2
C-CH
2
-CH
2
-COOC
2
H
22.1 g of 2,4-dichloro-4,4-difluorobutyric acid ethyl ester are dissolved in 200 ml of absolute ethanol. After the addition of 8.2 g of anhydrous sodium acetate and 2.0 g of 5 platinum/carbon catalyst, hydrogen gas is introduced under normal pressure until the amount of hydrogen absorbed is 100 of the theoretical amount. After the catalyst has been filtered off and the ethanol has been distilled off, the oil that remains is poured onto water and the organic phase is separated off, dried with sodium sulfate, filtered and rectified under normal pressure. 14.0 g of 4-chloro-4,4-difluorobutyric acid ethyl ester are obtained in the form of a colourless oil having a boiling point of 154-156 0
C.
Analysis: C 6 HgCF 2 02 (186.59) calc.: C 38.62 H 4.86 Cl 19.00 F 20.36 found: C 38.6 H4.8 Cl 19.1 F 19.9 Example P3: 4-Chloro-4,4-difluorobutyric acid ethyl ester C1F 2
C-CH
2
-CH
2
-COOC
2
H
22.1 g of 2,4-dichloro-4,4-difluorobutyric acid ethyl ester are dissolved in 100 ml of absolute tetrahydrofuran. After the addition of 10.7 g of 2,6-dimethylpyridine and 2.0 g of palladium/carbon catalyst, hydrogen gas is introduced under normal pressure until the amount of hydrogen absorbed is 100 of the theoretical amount. After the catalyst has been filtered off and the tetrahydrofuran has been distilled off, the oil that remains is S poured onto water and the organic phase is separated off, dried with sodium sulfate, filtered and rectified under normal pressure. 14.0 g of 4-chloro-4,4-difluorobutyric acid ethyl ester are obtained in the form of a colourless oil having a boiling point of 154-156 0
C.
Analysis: C 6
H
9 C1F 2 0 2 (186.59) calc.: C 38.62 H 4.86 Cl 19.00 F 20.36 found: C38.6 H4.8 C1 19.1 F 19.9 -28- Example P4: 4-Chloro-4,4-difluorobutyric acid ethyl ester C1F 2
C-CH
2
-CH
2
-COOC
2
H
25.5 g of 2,2,4-trichloro-4,4-difluorobutyric acid ethyl ester are dissolved in 200 ml of absolute ethanol. After the addition -f 16.4 g of anhydrous sodium acetate and 2.0 g of platinum/carbon catalyst, hydrogen gas is introduced under normal pressure until the amount of hydrogen absorbed is 2 equivalents. After the catalyst has been filtered off and the ethanol has been distilled off, the oil that remains is poured onto water and the organic phase is separated off, washed with sodium sulfate, filtered and rectified under normal pressure. 14.0 g of 4-chloro-4,4-difluorobutyric acid ethyl ester are obtained in the form of a colourless oil having a boiling point of 154-156 0
C.
Analysis: C 6
H
9 C1F 2 0 2 (186.59) calc.: C 38.62 H 4.86 Cl 19.00 F 20.36% found: C38.6 H4.8 Cl19.1 F 19.9
S
Example P5: 4-Chloro-4,4-difluorobutyric acid N-methylamide C1F 2
C-CH
2
-CH
2 -CO-NH-CH3 S 2.0 g of 4-chloro-4,4-difluorobutyric acid ethyl ester are dissolved at 0 C in 10 ml of a 33 solution of methylamine in ethanol. The resulting reaction mixture is stirred at room temperature for 3 days and then concentrated by evaporation. The resulting residue is recrystallised from hexane. 1.5 g of 4-chloro-4,4-difluorobutyric acid N-methylamide having a melting point of 61-63°C are obtained.
Example P6: 4-Chloro-4,4-dcfluorobuvric acid benzvl ester C1F 2
C-CH
2
-CH
2 -COO-CH2 a) 4-Chloro-4,4-difluorobutyric acid.
18.6 g of 4-chloro-4,4-difluorobutyric acid ethyl ester are stirred with 100 ml of 2N NaOH at room temperature until a homogeneous solution has formed. The solution is then poured onto 150 ml of 2N HC1. The separated organic phc-e is taken up in diethyl ether, dried with sodium sulfate and, after the ether has been distilled off, -29rectified in vacuo. 12.6 g of 4-chloro-4,4-difluorobutyric acid are obtained in the form of a colourless oil having a boiling point of 88-90 0 C/11 mbar.
Analysis: C 4
H
5 C1F 2 0 2 (158.53) calc.: C 30.31 H 3.18 Cl 22.36 F 23.97 found: C30.3 H3.2 C122.4 F24.2 b) 4-Chloro-4,4-difluorobutyric acid chloride.
15.8 g of 4-chloro-4,4-difluorobutyric acid are mixed with 50 ml of thionyl chloride and 0.2 ml of dimethylformamide and the mixture is heated to +70 0 C within a period of 2 hours and then kept at +70C for a further 30 minutes. The reaction mixture is rectified in vacuo and the liquid that distils over at a boiling point of 35-37 0 C/21 mbar is collected. 10.5 g of 4-chloro-4,4-difluorobutyric acid chloride are obtained in the form of a clear, colourless liquid.
.lysis C 4
H
4
CI
2
F
2 0 (176.98) calc.: C 27.15 H 2.28 Cl 40.06 F 21.47 found: C27.3 H2.3 C140.1 F21.4 c) A solution of 1.84 g of benzyl alcohol and 3.74 g of pyridine in 6 ml of methylene chloride is added at 0°C within a period of 30 minut.s to a solution of 3.35 g of 4-chloro-4,4-difluorobutyric acid chloride in 15 ml of benzene. The resulting reaction mixture is stirred at 0°C for 16 hours and then poured onto 50 ml of 1N HCI solution and extracted with 150 ml of diethyl ether. The organic phase is washed with 50 ml of saturated NaHCO 3 solution and 50 ml of saturated NaCI solution, dried with magnesium sulfate and concentrated by evaporation. The resulting crude product is distilled in a bulb tube at 190-210°C/120 mbar. 3.65 g of 4-chloro-4,4-difluorobutyric acid benzyl ester are obtained.
MS: m/e: 248 (M CllHllClF20 2 S Example P7: 4-Chloro-4,4-difluorobutyric acid N-isopropylamide C1F 2 C-CH2-CH 2
-CO-NH-C
3
H
7 -i A solution of 3.35 g of isopropylamine in 5 ml of methylene chloride is added at 0 C to a solution of 3.35 g of 4-chloro-4,4-difluorobutyric acid chloride in 15 ml of toluene. The resulting reaction mixture is stirred at 0 C for 16 hours and then poured onto 50 ml of saturated NaHC0 3 solution and extracted with 150 ml of diethyl ether. The organic phase is washed with 50 ml of saturated NaCI solution, dried with magnesium sulfate and concentrated by evaporation. 3.18 g of 4-chloro-4,4-difluorobutyric acid N-isopropylamide are obtained, 84-85 0
C.
Example P8: 2,4-Dichloro-4,4-difluorobutyric acid methyl ester
CIF
2
C-CH
2 -CHCl-COOCH 3 A solution of 2.4 g of 2,2,4-trichloro-4,4-difluorohutyric acid methyl ester in 20 ml of absolute ethanol is hydrogenated at room temperature, with the addition of 0.2 g of 5 platinum/carbon catalyst, until one equivalent of hydrogen has been absorbed (about one S hour). After the catalyst has been filtered off, the resulting crude product is distilled in a bulb tube at +70 0 C/20 mbar. 1.5 g of 2,4-dichloro-4,4-difluorobutyric acid methyl ester are obtained in the form of a colourless oil.
Example P9: 4-Chloro-4,4-difluorobutyric acid C1F 2
C-CH
2
-CH
2
-COOH
15.6 g of 4-chloro-4,4-difluorocrotonic acid are dissolved in 160 ml of tetrahydrofuran S and, after the addition of 0.8 g of 5 Pd/BaSO 4 catalyst, treated with hydrogen gas at room temperature and under normal pressure until the amount of hydrogen absorbed is 100 of the theoretical amount. After the catalyst has been filtered off and the solvent has been distilled off, the oil that remains is rectified in vacuo. There are obtained 12 g of a colourless oil which has a boiling point of 88-90 0 C/11 mbar and is identical to the 4chloro-4,4-difluorobutyric acid prepared in accordance with Example P6a.
S..
Example P10: 4-Chloro-4,4-difluoro-3-hydroxybutyric acid ethyl ester C1F 2
OH
20.0 g of 4-chloro-4,4-difluoroacetoacetic acid ethyl ester are dissolved in 200 ml of tetrahydrofuran and, after the addition of 2.0 g of a 5 rhodium/A1203 catalyst, hydrogenated with hydrogen gas under normal pressure and at room temperature until the -31theoretical amount of hydrogen has been absorbed. It may be necessary to add additional fresh catalyst during the hydrogenation. The catalyst is then filtered off and the solvent is evaporated off under a water-jet vacuum. Rectification of the crude product yields 18.0 g of pure 4-chlorc *4,4-difluoro-3-hydroxybutyric acid ethyl ester in the form of an oil that boils at 93-95 0 C and 17 mbar and solidifies to form long needles.
Analysis: C 6
H
9 ClF 2 0 3 (202.6) cal C 35.6 H 4.5 Cl 17.5 F 18.8 found: C 35.5 H 4.5 Cl 17.1 F 18.7 Example P11: 4-Chloro-4,4-difluoro-3-acetoxvbutyric acid ethyl ester
CIF
2 C-CH-tL 2
-COOC
2
I
O-CO-CH
3 20.2 g of 4-chloro-4,4-difluoro-3-hydroxybutyric acid ethyl ester and 0.1 g of anhydrous S sodium acetate are dissolved in 50 ml of acetic acid anhydride at +100 0 C and stirred at that temperature for one hour. After the reaction mixture has been poured onto 150 ml of water, the product is taken up in diethyl ether. The ethereal phase is dried with sodium sulfate and the ether is then evaporated off in vacuo. Rectification of the crude product yields 20.1 g of 4-chloro-4,4-difluoro-3-acetoxybutyric acid ethyl ester in the form of a colourless oil that boils at 95-97 0 C and 17 mbar.
Analysis: C8H 1 1 C1F20 4 (244.6) calc.: C 39.3 H 4.5 Cl 14.5 F 15.5 S found: C 39.2 H 4.6 C1 14.4 F 15.5 Example P12: 4-Chloro-4,4-difluorocrotonic acid ethyl ester 0 oo0 SCJ
CIF-C-CH-=CH-COOC
2
H
24, g of 4-chloro-4,4-difluort-3-acetoxybutyric acid ethyl ester and 40 ml of quinoline are mixed together and heated in a distilling apparatus. At a bath temperature of approximately 200 0 C, a colourless pungent oil having a boiling point of 140-145 0 C distils off.
The crude produt is taken up in diethyl ether and washed with hydrochloric acid and with water. After the ether phase has been dried with sodium sulfite and the ether has been distilled off, 14.0 g of 4-chloro-4,4-difluorocrotonic acid ethyl ester are obtained in -32the form of a colourless oil that boils at 41-43 0 C and 12 mbar.
Analysis: C 6
H
7 C1F 2 0 2 (184.6) calc.: C 39.0 H 3.8 Cl 19.2 F 20.6 found: C 39.3 H 3.8 Cl 19.0 F 20.4 The same product is obtained if 4-chloro-4,4-difluoro-3-hydroxybutyric acid ethyl ester is treated with phosphorus pentoxide in accordance with the method given by McBee et al.
in J. Amer. Chem. Soc. 76 (1954) 3722 for 4,4,4-trifluoro-3-hydroxybutyric acid ethyl ester.
Example P13: 4-Chloro-4,4-difluorobutyric acid ethyl ester
CF
2
CCH-CH-CH
2
-COOC
2
H
18.4 g of 4-chloro-4,4-difluorocrotonic acid ethyl ester are dissolved in 200 ml of ethyl acetate and, after the addition of 2.0 g of a 5 palladium/barium sulfate catalyst, treated S with hydrogen gas under normal pressure and at room temperature. The hydrogenation is complete after a short time. After the catalyst has been filtered off, the solvent is evaporated off in vacuo and the residue is rectified. The product that distils at 154-156 0
C
is identical to the 4-chloro-4,4-difluorobutyric acid ethyl ester prepared in accordance with Examples P2, P3 and P4.
The compounds mentioned in the following Tables are also prepared analogously to the above-described procedures.
C C 33 Table 1: ClF 2 C-cjH-TH-CO-O-R 3 R, R 2 Comp.
No.
1.01 Rl R2 R~3 H H CH 3 1.02 H H C 2
H
5 1.03 H 1.04 H
C
3
H
7 -n
C
3
H
7 -i
C
4 H9-t I, 906 660g o es 6S S 9 009099 5 *s 00 0 504
SOS
S
0590 00 6* 0 1.05 .1.06 H H H H C 4
H
9 -n Ehys. data
C
5
H
7 C1F 2 0 2 nWe: 172 MS C 6 HqC1F 2 0 2 nile: 186
C
7
H
1 1 C1F 2 0 2 nile: 200 15,C 7
H
1 1 C1F 2 0 2 nile: 199 MS:(M+1, C 8
H
1 4C1F 2 0 2 nile: 215 MS C., 0
H
17 C1F 2 0 2 nile: 242
C
14 1- 2 5CIF 2
O
2 nile: 298 33-35TC CqH 15 C1F 2 0 2 nile: 228
C
6
H
9 C1F 2 0 3 m/le: 202 1.07 H H C 6 C1 3 -n 1.08 H H C 10 6H 2 1 -n 1.09 1.10
C
2 0 H4 1 -n
CH
2
C(CH
3 3 1.hJl H H1 CH 2
CH
2
OH
1.12 1.13 1.14 1.16 116 1.17 1.18 1.19 1.20 1.21 1.22
CH
2
CH
2
O-COCH
3
CH
2
CH
2
O-COOCH
3
CH-
2
CH
2
OCONHC
6
H
CH
2
CH
2
OC
2
H
CH
2
CH
2
OCH
2
CH
2
OCH
3
CH
2 CC1 3
CH
2 CBr 3
CH
2
CH
2
SCH
3
CH
2
CH
2
OCH
2
CH
2
CH
2
CI
CH
2
C
6 H-1 MS CgH 1 5 C1F 2 04) nile: 260 n.o 2 3 1.5050 CiiHi 1C1F202) nile: 248 34- .Table 1 (continued) Comp.
No.
1.23 1.24 1.25 1.26 1.27 1.28 1.29 1.30 1.31 HH R H H H H H H H H H H H H H H H H Phys. data CH(CH3)C6H5 CH(CH3)C6H5 (R)
CH(CH
3
)C
6
H
5
(S)
CH.C6H4-N0 2
CH
2
-C
6 H4-N0 2
CH
2
-C
6
H
4 -Cl-(2)
CH
2 -C6H5-F- (4)
CH
2 -C6H4-O-C6HS-(3) 9s *9* 0@W* S S 5. 0 0
S
*055sq 5 59 5 5 S. 5*0 Set'S ~t 5* 95 9 Sib
S.
S
5**
S
S
1.32 H H -C 6
H
4 -O-C6H5-(4) 1.33 H H -C6H 4 -NO2-(4) 1.34 H H -C 6
PH
4 1.35 H H Q C 0 2
N
1.36 H H -CH 2
CH
2 O 0 1.37 El! -CH 2
CH
2 O-Q0 QF 1.38 H H -CH 2 CHi 2 0 0.- Ca
F
1.39 H H
-CH
2
CH
2 0 -0\ nD 23 1.5270 MS C 10
H
9 C1F 2 0 2 m/e: 234 -D3 1.530 m.p. 81-82TC -D3 1.5109 MS;(M+ C 18
H
17 C1F 2 0 4 m/e: 370 m.p. 62-63*C nD 2 0 =1.5380 nD 10=j.5047 1.40 H H C6HI 1 -cycl.
1.41 H H C 5
H
9 -cycl.
MS (M+-35,C 0 H 1 5
F
2 0 2 m/e: 205 35 Table 1 (continued) No. R1!R2 R3 H H C 3
H
5 -CYCl.
1.43 H H -CU 2 KI0 1.44 H H -CU 2 1.45 H H -CH 2 1.46 H CF 3
-C
2
H
5 1.47 H H -CH 2
CH
2
O-(
1.48 H H Phys. data to* *0 0000 00 we,* 0 00 MS: C 8
H
1 1-7202) m/e: 177 MS:(Me, C 7 HgC1F 5
O
2 ra/e: 254 n23= 1.5150 b.p. 88-90O/l 1 mbar 1.49 1.50 1.51 1.52 -Cl 6
H
3 3 n
-CH(CH
2
CH
2
CH
2
CH
3 2
-CH
2
-(CH
2 4
CH
2
CI
1.53 H H -CH 2 -C (CU 3 2 C2 OC2H 1.54 H H -CH 2 C (CU 3 2-0 /C Cl 1.55 H H -CH 2
CH
2
CH
2
CH
2
-C
6
H
1.56 H H -CH 2
CH
2
C
1.57 1.58 1.59 1.60
-CH
2
-CH=CH
2
-CH
2
CH=C(CH
3
)CH
2
CH
2
CH=C(CH
3 2
-CH
2
CH=C(CH
3
)CH
2
CH
2
CH=C(CH
3
)-CH
2
CH
2
CH=C(CH
3 2
-CH
2 7CH=-CH -36- Table 1 (continued) Comp.
No.
1.61 1.62 1.63 1.64 1.65 1.6 1.66 1.69 RI 92 Phys. data H H -CH 2
CH
2
-C-=C-(CH
2 4 CHi 3 H H -CH 2
CH
2
O-SO
2
CH
3 H H -CH 2
CH
2 O-S0 2 \a Cf1 3 H H -CH 2
CH
2
O-COC
6
H
"H H CH 3 HU H CH3 HH H H H~
CH
3 H H
-CH
2 C F F 1.70 H H -CH 2 F F
_OCH
3 o 1,71 H H -C 2 1 37 Thblel1 (continued~) Comp.
NO. Ii RZ R~3 Phys. data
CF
3 1.72 14 H
-CH
2
CF
3 1.73 H H -CHV.C 6
H
4 -Br-(4) Br 1,74 H H -CH 2 1,75 H H -CH 2 C2H2H *4 Us 1.76 IH H -CH 2 C3, 1.77 H- H -"CH 2 1.78 H H -CH 2 -C6H 4 -CI-(3) to~ 1.79 H H -CH- 2 -CjI 4 -C1-(4) V, 1.80 H -CH Cl 1.81 H H -CH 2 cl 1.82 H H -CH(CH 3
C
C'
38 Table 1 (continued) Comp.
No. R 1
R
2
R
3 Phys. data Cl 1,93 H H -CH 2 Cl
OCH
3 1.84 H H -CH 2
OCH
3 46.:1.85 H H -CH 2 CH2 3 1.86 H H -CH/-C6HCHFCH 3 1.87 H H -CH 2
-C
6
H
4 2 H-(4) S 1.88 H H -CH 2
-C
6
H
4 :1.92 H H- -CH 2
-C
6
H
4 -OH-(4) 1.93 H H -CH 2
-C
6
H
4 1.91 H H -CH 2 \-6H 1.92 H H -CH 2
-C
6
H
4 0C 3 1.96 H H, -CI-1 2
-C
6
H
4
-CF
3
OH
3 1.97 HE HC OCH3 39 Table 1 (continued) Comp.
No.
91 R2 R3 Phys. data 1.98 H H
CH
3
-CH
2
CH
3
CH
3 1.99 HI H -CH 2 H &*of a*e1.101 H ~O(CH 2 3
CH
3 y:1.102 H H
(CH
3 3 1.103 H H C17- 3 1.104 1.105 1.106
-C
6
H
4 -CI-(2)
C
6
H
4 -CI-(3) -CAH-C1-(4)
IC(CH
3 3
OS
46 .6 *0 66 I*6 a 1. 107 H H
(CH
3 3 Cl1 1.108 H H
C]-
1.109 H H Q Cl Cl Table 1 (continued)
COMP.
NO. Rl 9 2
R
3 Phys. data 1.11OH H
F
CH
3 1.111 H
H
CH
3 1.112 H H /\OC 2
H
Goo* S.Cl Cl 1.113 H H F' x *F F 1.114 H H \0 -41- Table 1 (continued) Comp.
No. R- 1.117 H R2 R~3 Phys. data e.g
SC
0* C
S~~S
C
COOS
C
SCSSC
S
S.
S S C.f~C 1.118 H 1.119 H
CH
3
OH
3
CH
3 1.120 1.121 1.122 1.123
CH
3
CH
3
C
2
H
5
C
2
H
5 -n 55 S S 5*
S.
S
S.C
C
555CC 0 1. 124 CH 3 1.125 CH(CH 3 2 H -C 6
H
H -C 6
H
H -C 6
H
H -CH 2
CH
2
O
H -CH 2 CHi 2 O 0 /\F H -CH 2
C
6
H
H H
CF
3
-CH
2
CH
2
O
1.126 1.127
CH
3
C
3
H
7 -n 1.128 H -42- Table 1 (continued) Comp.
No. !Ri 1. 129 H R2 R3
H
Phys. data 1.130 H *0 0e egg 0000 *0 0* 0
OOOS
0 0000 0 *00*00 0 1.131 H @000 000S 0009 1.132 H *0 0 0 0g 0* 1.133 H 0 0,0000 0
CI
CI
H N~
CH
3
H//
N
1.134 H -43 Table 1 (continued) Comp.
No. BRi 1.135 H 1.136 H 0 *SI 1.137 H 1.138 C 3
H
7 -n R2 93 H 0 \CF 3
CI
H a- \C
CI
H 0F H CAH
HN
0 \CF 3 H -CH 2
-CI-
2 -0 0 f
S-N
Phys. data rn.p. 1.139 H
S
*5 S. S S *S S S 5* 55
S
S..
aSSes.
S
1. 140 H -44 Table 2: ClF2C-ffH-fH- CO-N-R 4 Rl R 2 A comp.
No.
2.01 2.02 91lR2 Hi H H H R4
H
CH
3 93
-CH
3
-CH
3 Phys. data rn.p. 61-63'C
C
6
H
10 C1F 2
NO)
mle: 185 2.03 2.04 *00 two 2.06 2.07 pots:: 2.08 2.09 2.10 Voss. 2.11 2.12 2.13 2.14 as a 2.16 2.17 to* 2.18 2.19 2.20 0 22 2.21 2.22 2.23 2.24 2.27 2.28 2.29
H
CF
3
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
C
6 Hl 3 -n
H
H
H
H
H
H
H
H
H-
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
-C
6
H
1 3 -n
-CH
3
-C
3
H
7 -i -C3H 9 -n
-C
4
H
9 -n
-C
6 Hl 3 -n -ClOH2 i-n
-C
2 0H 4 1i-n
-CH
2
C(CH
3 3
-CH
2
CH
2
OH
-CH
2 CH2O-COC 6
-CH
2 CH2O-COOCH 3
-CH
2
CH
2
O-CONHC
6
HI
-CH
2
CH
2
OC
2
H
-CH
2 CFq
-CH
2 CC1 3
-CH(CH
3
)C
6
H
5
-CH(CH
3
)C
6
H
5
(R)
-CH(CH
3
)C
6
H
5
(S)
-CH
2
-C
6
H
5
-CH
2 -C6H 4 -N0 2
-CH
2
-C
6
H
4 -CH2--C 6
H
4 -Cl- (2)
-C
6
H
5 -C6H- 4 -N0 2 -(4d) m.p. 50-51'C m.p. 84-85'C imp. rn.p. 97-98'C m.p. 40-41'C m.p. 55-56'C m.p. 60-61'C m.p. 74-75'C m.p. 121-122'C Table 2 (continued) Comp.
No.
2.30 R2 14 H H 2.31 H H H 2.32 H H H 00 4 0 **so too* 2.33 H H CH3
-C
6 H4-F-(4)
C'
NO
2 -CH2~
-CH
2 Cl
-C
6
H
4 -CN-(4)
-C
6
H
4
-CF
3
-C
6
H
4
-C
6
H
5
-C
6
H
4
-CF
3 0 M.P. 122-1231C
MS:(M+,C
1 iHl 3
CIF
2
N
2
O)
Phys. data rn.p. 96-97'C M.P. 110-lilac m/e: 262 2.34 CH 3 2.35 H H H 2.36 :2.37 2.38 *.gS2.39 5 S S 2.40 H H H 2.41 H H H m.P. 47-49'C m.P. 122-123'C M.p. 106-107'C m.p. 186-187'C m.p. 77-79'C m.p. 143-144'C m.p. 120-121'C m.p. 105-106'C m.p. 150-151'C m.P. 93-94*C m.p. 113-114'C m.p. 120-121'C 2.42 2.43 2.44 2.45 2.46
-C
6
H
4 -Cl-(2)
-C
6
H
4 -Cl-(4)
-C
6
H
4 -CI-(3)
-C
6
H
4
-OCH
3
-C
6
H
4
-CH
3 46 Table 2 (continued) Comp.
No.
2.47 2.48 2.49 2.50 2.51 2.52 2.53 2.54 2.55 2.56 2.57
-C
6
H
4
-SCH
3 Phys. data Imp. 88-89'C m.p. 92-93'C m.p. 71-72'C -Cl 2
H
25 -n
-CH
2
(CH
3
)-CH
2
CH
2
CH
3
-CH
2
CH
2
CH
2
CH
2
OH
-CH
2
CH
2
CH
2
CH
2
OCH
3
S.
hO @0 ib~ 0 see.
S
0000
S
*5
C
9**S H H H 2.58 H H H 2.59 H H H -CH2H2CHCH2-SO2--a CH 3
-CH
2
CH
2
CH
2
CH
2 0-SO 2
CH
3
-CH
2
CH
2 O-CO- a l
-CH
2
CH
2
O-CH
2
CF
3
-CH
2
CH
2
N(CH
3 2
-CH
2
(CH
3
)-CH
2
CH
2
CH
2
-N(CH
2
CH
3 2
-CH
2
CH
2 a OCH 3 2.60 2.61 2.62
SS
S S S
S.
2.63 HI-H H 2.64 H H H
S.
S
S..
0006Se C S 2.65 2.66 2.67
-CH
2
CH
2
OCH
3
-CH
2
(CH
3
)-C(CH
3 3
-CH
2 CHi(OCH 2
CH
3 2
-CH
2
-CO-C
6
H
-CH
2 -4 2.68 H H H 47 Table 2 (continued) Comlp.
No.
Rl R 2 R4 P~hys. data 2.69 H H H 0 0 0 to
S
to.
2.70 2.71 2.72 2.73 2.74 2.75 2.76 2.77 2.79 2.80 2.80 2.81 2.82 2.83 2.84 2.85
H
H
H
CH
3
OH
3 Cl' 3
H
H
H
H
H
H
H
H
H
H
-CH
2
(CH
3
)-CH
2 0CH 3
-CH
2
CH
2
-CH(CH
3 2
-CH
2
(CH
2 7
CH=CH-(CH
2 7
CH
3 -Cl 8
H
37 -n
-C
3
H
7 -n
-CH
2
CH
2
-C
6
H
-CH
2
-C
6
H
4
-OCH
3
M.P.]
-CH
2
-C
6
H
4
-CH-
2
-C
6
H
3
-F
2 -Cl- 2
-C
6
H
3
-F
2
-CH
2
-C
6
H
3
-F
2
-CH
2
-C
6
H
4 Mn.P.
CH
2
-C
6
H
3 -C1 2
-CH
2
-C
6
H
4
-CF
3 -CHz-c 6
H
4
-NO
2
-CH('C
6
HS)
2 -CH2 0 106-108 0
C
102-1030C 2.86 H H H @0
S
*55 C S 2.87 H H -OH 2
(CH
3
-CH
2 2.88 H H H -48 Table 2 (continued) Comp.
No.
RI R2 R~4 Phys. data 2.89 H H H 2.90 H H H 2.94 2.91 2.95 2.96 H H H H H H H H H H H H H H H
CH
3
CAH
C
3
H
7 -i
C
4
-H
9 -n
H
H
-CH2 -CH2 9
-CE
2
N
-CH
2
-C
6
H
-CH
2
-C
6
H
-CH
2
-C
6
H
-CH
2
-C
6
H
-C
6
H
1 1 -cyclo
-C
3
H
5 -cyclo
HH
CE
3
-CH
2
-C-=CH
-CH
2
-C-=CH
-CH
2
-CHMCH
2
-C
6
H
4
-COCH
3
-C
6
H
4
-CONH
2
-C
6
H
4 -CN-(3) H H H H H H V. 2.100 H H 2.101 H H *V 2.102 H H 2.103 H H 2,104 H H 2.105 H H
H
CH
3
H
H
H
H
-49 Table 2 (continued) Comp.
2.106 H H H.
2.107 H H 2.10 2. 108 H H H too's ~2.10 H H H
-C
6
H
4 -Br-(4)
-,;D-CH
3 Br Br
CH
3 Br Cl
CH
3 \Br
CH
3
CR
3 N0 2 Phys. data
S
0000 6e*~
CS
0O B
S.
CS C 0* 2.111 H H H 2.112 H H H 2.113 H H I 50 Table 2 (continued) Comp.
No.
91 92 94 PhXs. data 2.114 H H H 2.115 H H H 4.b~ 0 2.116 H H H sa 10*00 *2.117 H H H 2.118 H H H to \C1 \C1 /C1 Cl CH 3
F
2.119 H H H be 0*a, 0 0* eO *0 V 0 2.120 H H H
OCH
3
OCH
3 CH 3
CH
3 -O
CH-
2
CH
3 2.121 H H H -51- Table 2 (continued) Comp.
No.
91 R2 94 Phys. data 2.122 HH H 2.123 1-1 H H
~-CH
3 99.
4 2.1241H1 H H
CH
3
CH
3
-C
6 1 4 -OH-(4) 46 a 6*S a I9.00*4 0 S 2.127 H H H 2.128 HR H 2.129 H H H
\/O-SO
2 -a CH 3
OH
2
CF
3 52 Table 2 (continued) Comp.
No.
2.130 2.131 2.132 2.133 2.134 2.135 2.136 2.137 2.138 2.139 Hl
H
H
H
CH
3
CH
3
C
2 H3
C
4
H
9 -ni
H
CH
3
C
2 H3
H
H
H
H
H
Hil
CH
3 _3 Phys. data
CAH
C6H 4
-NO
2
C
6 H-C1-(4)
-C
6
H
-C
2
H
-CH
2
-C
6
H
-CH
2
-C
6
H
-CH
2
-C
6
H
-CH
2
-C
6
H
-C
6
H
H
3 0 0 CF M.P. 145-147TC
H
3
C
4090 le to 2.140 H H H 00 *4 0 0 of 100 2.141 H H
H
5
C
2 SI(CH 3 3 rn.p. 207-208TC m.p. 94-95TC 2.142 H H H 2.143 H H H
OCJOH
21 -n m~.91-93oC NC.P 2-4 2.144 H H H H H 53 Table 2 (continued) Comp.
NO.
91 R2 94 R Phys. data 2.145 H H H No~r~ m.p. 179-181TC 0* 0 2.146 H 0 0 2.147 H H H O-CF 2
.CF
2
H
CI
m.p. 114-115'C H H H H H H
H
3 C
O-CF
2
-CF
2 H m.p. 114-115Tc 4/ B r m.p. 149-151TC
-C(CH
3 2
CI
m.p. 131-133'C imp. 88-90*C H H /\ocF 3 2.151 H H H 2.151 H H H m.p. 130-133 0 C m.p. 130-133T -54- Table 2 (continued Comp.
No. Rl R12 94 R13 Phys. data H H0 N
CF
3 2.152 H M.P. 127-128TC 2.153 H *00 H H
N
CF
3
,SCH
3
N
H H 0 N
CH
3 0
CH
3 2.155 H H H 0 NCF 2.156 H H H 0-KI~1. m p s
OCF
3 2.157 H H C1 2.158 H H H S '<NO 2.159 H H H
NCH
.88-1 89 0
C
Vo a:0 0 55 Table 2 (continued) No.
91 2 94 R Phys. data 2.160 H 2.161 H *se 2.6 2.162 H a to N~ DCF 3 H H0 Cl Cl H H 0 'CF 3 m.p. 149-150 0
C
CI
H
3 C CI H H
CF
3 m.P. 205-207JC
H
3
C
H H H H Q CI
CF
3 o
\CF
3
C
m.p. 107-109TC m.p. 137-139'C 2.165 H 2.166 H
CH
3 H H 0 'JCF 2
CFC
2 M.P. 130-132 0
C
OH
3 Cl H H 0 /\CF 2
CFCI
2 M.P. 122-124 0
C
CI
-56- Table 2 (continued) Comp.
No.
Ri 2 94 9 Phys. data 2.167 H 2.168 H 2.6 Hs H H H H H H
CCH
3
CI
'0
F
3
CI
/\COOC
2
H
-N
CI
2.170 H 2.171 H
CH
3
N
H H0 3
CI
H H *es *.eS C.
C S 2.172 H H H
CI
N
&2CF 3
CI
CI
N
CF
3
N
0 3 Cl 2.173 H H H, 57 Table 2 (continued; comp.
No. Rl 2.174 H 2.175 H 2.7 HO es ::2.176 H S952.177 H
I
ii 12 R~4 R Phys. data ~I H -Q
N
0 C\
H
3
C
H H-
H
3 C
C
H
5
C
2 H H
H
5
C
2 a H H Njj 0
H
3
C
N-N
H H 0 ci
H
3
C
H
3
C
N
H H 0-<3
H
3
C
-58- Table 2 (continued) Comp.
No.
1 2R 4 R Phys. data 2.181 H 2.182 H 2.8 H .:goo* 2.184.
H H H H
H
3
C
H
3
C
CI
-CF
3
H
3
C
H H0 H,
C
F
H HN 1 CH3 m.p. 131-133TC
S-N
S 5H 3 C NfBr 2.185 H H H 1
H
3
C
2.186 H H H -CH 2
CH
2 C1 m.p. 43-441C 2.187 H H H -CH 2
-C
6
H
4
-N(CH
3 2 m.p. 124-125'C 2.8 H H.H-CH-(CS3S) S.12-21 2.188 H H H -CH 2
-C
6
H
4
-CH
3 m.p. 14-15 0
C
2.190 H H H -CH(C 2
H
5 /0\o 0 imp. 97-98'C 2.191 H H H -CH(C 2
H
5 /0 0 F m.p. 135'C 59 Table 2 (continued) Comp.
No. Rl R2 R4 R~3 Phys. data 2.192 H H H 2.193 H H H m.p. 135-136TC
C.H
00 0 2.194 H H H CN3mp 39' $00 C. C H 3
C
N
2.195 H H H 0 CI~ m.p. 163-165 0
C
H
3
CF
2.196 H H H -CH 2
-C(CH
3 2
\OCH
3 Formulation Examples (throughout, percentages are by weight) Example Fl: Emulsifiable concentrates a) b) c) compound no. 1.01 or 1,02 25% 40% calcium dodecylbenzenesulfonate 5 9 6 castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5 tributyiphenol polyethylene glycol ether (30 mcies of ethylene oxide) -12% 4% cyclohexanone 15% xylene mixture 65% 25% Emulsions of any desired concentration can be produced from such concentrates by dilution with water.
Example F2: Solutions compound no. 1.04 ethylene glycol monomethyl ether polyethylene glycol (mol. wt. 400) N-methyl-2-pyrrolidone epoxidised coconut oil ligroin (boiling range 160-190 0
C)
a) 80% b) 10% c) 5% d)
S.
S
6*e ue55e 0Ir 0* 4 us..
94% The solutions are suitable for application in the form of micro-drops.
Example F3: Granulates compound no. 2.02 kaolin highly dispersed silicic acid attapulgite a) b) 5% 94 1% The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
0 Example F4: Dusts compound no. 1.45 highly dispersed silicic acid talcum kaolin a) b) 2% 1% 97% Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient.
-61- Example F5: Wettable powders compound no. 2.09 sodium lignosulfonate sodium laurylsulfate sodium diisobutylnaphthalenesulfonate octylphenolpolyethylene glycol ether (7-8 moles of ethylene oxide) highly dispersed silicic acid kaolin a) 25% 5% 3% b) 50% c) 6% 5% 62% 2% 10% 27% -a
U.
#ea.
*J 4 me
I
.me.
The active ingredient is mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.
Example F6: Emulsifiable concentrate compound no. 2.01 octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) *o calcium dodecylbenzenesulfonate castor oil polyglycol ether a' (36 moles of ethylene oxide) cyclohexanone xylene mixture 3% 3% 4% :0.
SA
64* a Emulsions of any desired concentration can be obtained from this concentrate by dilution with water.
Example F7: Dusts compound no. 2.24 talcum kaolin a) b) 5% 8% 95 92% Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and -62grinding the mixture in a suitable mill.
Example F8: Extruder granulate compound no. 2.08 10 sodium lignosulfonate 2% carboxymethylcellulose 1% kaolin 87 The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded, granulated and then dried in a stream of air.
Example F9: Coated granulate *b compound no. 2.33 3% polyethylene glycol (mol. wt. 200) 3% a kaolin 94% The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
Example F10: Suspension concentrate compound no. 2.07 40 ethylene glycol 10 nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 sodium lignosulfonate 10 carboxymethylcellulose 1% 37 aqueous formaldehyde solution 0.2 silicone oil in the form of a 75 aqueous emulsion 0.8 water 32 The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can' r obtained by dilution with water.
-63- Biological Examples Example B 1: Action against Boophilus microplus Adult female ticks which are replete with blood are affixed to a PVC plate and covered with a cotton wool swab. For treatment, 10 ml of an aqueous test solution containing 125 ppm of the test compound are poured over the test insects. The cotton wool swab is then removed and the ticks are incubated for 4 weeks until oviposition has taken place.
The action against Boophilus microplus manifests itself either as mortality or sterility of the females or as ovicidal action in the eggs.
In this test, compounds of Tables 1 and 2 exhibit good activity against Boophilus microplus. In particular, compounds 1.01, 1.04, 1.05, 1.06, 1.10, 1.18, 1.21, 1.22, 1.30, 1.31, 1.33, 1.35, 1,36, 1.37, 1.38, 1.39, 1.40, 1.45, 1,46, 2.01, 2.02, 2.05, 2.07, 2.08, 2.09, 2.24, 2.28, 2.30, 2.31, 2.32, 2.33 and 2.35 are more than 80 effective.
0 S Example B2: Ovicidal action against Heliothis virescens Egg deposits of Heliothis virescens on filter paper are immersed for a short time in an aqueous acetone solution of the test compound having a concentration of 400 ppm. After the test solution has dried, the eggs are incubated in petri dishes. After 6 days, the percentage of eggs which have hatched is evaluated in comparison with untreated controls reduction in the hatching rate).
Compounds of Tables 1 and 2 exhibit good activity against Heliothis virescens in this test.
In particular, compounds 1.01, 1.02, 1.04, 1.06, 1.10, 1.22, 1.31, 1.36, 1.40, 1.45, 1.46, 2.01, 2.02, 2.05, 2.07, 2.08, 2.24 and 2.28 are more than 80 effective.
Example B3: Action against Aonidiella aurantii Potato tubers are populated with crawlers of Aonidiella aurantii (red citrus scale). After about 2 weeks, the potatoes are immersed in an aqueous emulsion or suspension containing the test compound in a concentration of 400 ppm. After the treated potato tubers have dried, they are incubated in a plastics container. Evaluation is made 10-12 weeks later by comparing the survival rate of the crawlers of the first subsequent generation of the treated scale population with that of untreated controls.
Compounds of Tables 1 and 2 exhibit good activity against Aonidiella aurantii in this test.
-64 In particular, compounds 1.18, 1.21, 1.22, 1.30, 1.31, 1.32, 1.33, 1.35, 1.37, 1.38, 1.39, 1.48, 1.49, 2.01, 2.05, 2.07, 2.08, 2.30, 2.37, 2.42, 2.43, 2.44, 2.45, 2.46 and 2.48 are more than 80 effective.
Example B4: Action against Nilaparvata lugens Rice plants are sprayed with an aqueous emulsion containing 400 ppm of test compound.
After the spray coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stages. Evaluation is made 21 days later. The percentage reduction in the population activity) is determined by comparing the number of surviving cicadas on the treated plants with that on untreated plants.
Compounds of Tables 1 and 2 exhibit good activity against Nilaparvata lugens in this test.
In particular, compounds 1.10, 1.22, 1.30, 1.31, 1.33, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.45, 1.48, 1.49, 2.05, 2.07, 2.08, 2.24, 2.28, 2.30, 2.31, 2.32, 2.33, 2.35, 2.36, 2.39, 2.41, 2.42, 2.43, 2.45, 2.46 and 2.47 are more than 80 effective.
S Example B5: Action against Tetranychus urticae Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed one day later with an aqueous emulsion containing 400 ppm of the test compound.
The plants are then incubated for 6 days at 25°C and then evaluated. The percentage reduction in the population activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on untreated plants.
S Compounds of Tables 1 and 2 exhibit good activity against Tetranychus urticae in this test. In particu'lr, compounds 1.30, 1.33, 1.35, 1.36, 1.38, 1.39, 2.28, 2.39, 2.41, 2.43 and 2.44 are more than 80 effective.
Example B6: Action against Anthonomus grandis adults Young cotton plants are sprayed with an aqueous emulsion containing 400 ppm of the test compound. After the spray coating has dried, the cotton plants are populated with adults of Anthonomus grandis and placed in a plastics container. Evaluation is made 3 days later. The percentage reduction in the population or the percentage reduction in feeding damage activity) is determined by comparing the number of dead beetles and the feeding damage on the treated plants with that on untreaLtd plants.
Compounds of Tables 1 and 2 exhibit good activity against Anthonomus grandis in this test. In particular, compounds 1.22, 1.36, 1.37, 1.49, 2,28, 2.32, 2.38 and 2.39 a-e more than 80 effective.
Example B7: Action against Aphis craccivora Pea seedlings are infested with Aphis craccivora and then sprayed with a spray mixture containing 400 ppm of the test compound, and incubated at 20 0 C. Evaluation is made 3 and 6 days later, The percentage reduction in the population activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants, Compounds of Tables 1 and 2 exhibit good activity against Aphis craccivora in this test.
In particular, compounds 2.05, 2.07, 2.08, 2.24, 2.28, 2.35 and 2.39 are more than 80 effective.
e S Example B8: Systemic action against Myzus persicae Pea seedlings are infested with Myzus persicae and then placed with their roots in 'a spray mixture containing. 400 ppm of the test compound and incubated at 20°C. Evaluation is made 3 and 6 days later. The percentage reduction in the population activity) is determined by comparing the number of dead aphid on the treated plants with that on untreated plants.
Compounds of Tables 1 and 2 exhibit good activity against Myzus persicae in t .est. Ix S particular, compounds 2.05, 2.24 and 2.28 are more than 80 effective.
0 S Example B9: Systemic action against Nilaparvata lugens 8 Pots containing rice plants are placed in an aqueous emulsion solution containing 400 ppm of the ttet compound, The rice plants are then populated with larvae in the 2nd and 3rd stage. Evaluation is made 6 days later. The percentage reduction in e population activity) is determined by comparing the number of cicadas on the treated plants with that on untreated plants.
Coorpunds of Tables 1 and 2 exhibit good activity against Nilaparvata lugens in this test.
In particular, compounds 1.01, 1.02, 1t.04, 105, 1.06, 1.10, 1.18, 1.21, 1.22, 1.30, 1.31, 1.33, 1.35, 1.36, 1.37, 1.38, 1.39, 1.4, 1.45, 1.46, 1.48, 1.49, 2.01, 2.05,2.07, 2.08, 2.09, 2.24, 2.28, 2.30, 2.31, 2.32, 2.33, 2.35, 2.36, 2.37, 2.38, 2.39, 2.40, 2.41, 2.42, 2.43, 2.44, 2.45, 2.46, 2.47 and 2.48 are still more than 80 effective at 12.5 ppm.
P
66- Example BG(: Ovicidal action against Adoxophyes reticulana Egg deposits of Adoxophyes reticulana on filter paper are immersed for a short time in an aqueous acetone solution of the test compound having a concentration of 400 ppm. After the test solution has dried, the eggs are incubated in petri disb'h. After 6 days, the percentage of eggs which have hatched is evaluated in comp-ison with untreated controls reduction in the hatching rate), Compounds of Tables 1 and 2 exhibit good activity against Adoxophyes reticulana in this test. In particular, compounds 1.02, 1.22, 1.31, 1.36, 2.05, 2.07, 2.08 and 2.35 are more than 80 effective.
Example B 11: O-icidal/larvicidal action against Heliothis virescens Egg deposits of Heliothis virescens on cotton are sprayed with an aqueous emulsion o containing 400 ppm of the test compound. 8 days later, the percentage of eggs which have hatched and the survival rate of the caterpillars are evaluated in comparison with untreated controls reduction in the population).
Compounds of Tt bles 1 and 2 exhibit good activity against Heliothis virescens in this test.
I particular, compounds 1.01, 1.02, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.18, 1.21, 1.22, 1.30, 1.31, 1.32, 1.33, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.45, 1.46, 1.48, 1.49, 2.01, 2.02, 2.05, 2.07,2.08, 2.09, 2.24, 2.28, 2.30,2.31, 2.32, 2.33, 2.35, 2.36, 2.37, 2.38, 2.39, 2.40, 2.41, 2.42, 2.43, 2.44, 2.45, 2.46, 2.47 and 2.48 are more than 80 effective.
0* S Example B12: Action against Dermanyssus gallinae 2 to 3 ml of a solution containing 10 ppm of test compound, and approximately 200 mites at various stages of development, are placed in a glass container that is open at the top.
S The container is then closed with a cotton wool plug, shaken for 10 minutes until the mites are completely wetted, and then inverted for a short time so that the remaining test solution can be absorbed by the cotton wool. After 3 days, the mortality of the raites is determined.
Compounds of Tables 1 and 2 exhibit good activity against Dermanyssus gallinae in this test. In particular, compounds 1.04, 1.06, 1.10, 1.22, 1.31, 1.36, 1.40, 1.45, 2.01 and 2.02 are more than 80 effective.
-67- Example B13: Action against Heliothis virescens caterpillars Young soybean plants are sprayed with an aqueous emulsion containing 400 ppm of the test compound. After the spray coating has dried, the soybean plants are populated with Heliothis virescens caterpillars in the first stage and placed in a plastics container.
Evaluation is made 6 days later. The percentage reduction in the population or the percentage reduction in feeding damage activity) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
Compounds of Tables 1 and 2 exhibit good activity against Heliothis virescens in this test.
In particular, compounds 2.01, 2.07, 2.24 and 2.33 are more than 80 effective.
C
Example B14: Ovicidal action against Cydia pomonella Egg deposits of Cydia pomonella on filter paper are immersed for a short time in an aqueous acetone solution of the test compound having a concentration of 400 ppm. After the test solution has dried, the eggs are incubated in petri dishes. After 6 days, the percentage of eggs which have hatched is evaluated, in comparison with untreated controls reduction in the hatching rate).
Compounds of Tables 1 and 2 exhibit good activity against Cydia pomonella in this test.
Example B 15: Action against Nephotettix cincticeps Rice plants are sprayed with an aqueous emulsion containing 400 ppm of the test compound. After the spray coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stages. Evaluation is made 21 days later. The percentage reduction in the population activity) is determined by comparing the number of surviving cicadas on the treated plants with that on untreated plants.
Compounds of Tables 1 and 2 exhibit good activity against Nephotettix cincticeps in this test. In particular, compounds 1.33, 1.37, 1.38, 1.49 and 2.48 are more than 80 effective.
Example B 16: Action against Ctenocephalides felis to 25 flea eggs are placed in a horizontal 50 ml cell culture bottle into which 15 g of flea larvae nutrient medium containing 100 ppm of the test compound have been -68introduced beforehand. The test bottles are incubated in an incubator at 26-27 0 C and 60-70 humidity. After 21 days, the bottles are checked for the presence of adult fleas, unhatched pupae and larvae.
Compounds of Tables 1 and 2 exhibit good activity against Ctenocephalides felis in this test.
Example B 17: Action against Diabrotica balteata eggs to 50 egg deposits of D. balteata on cloth filters are placed in a petri dish and sprayed with an aqueous emulsion containing 400 ppm of the test compound. The petri dishes are incubated at 24 0 C. After 7 days, the percentage of eggs which have hatched is evaluated in comparison with untreated controls reduction in the hatching rate).
Compounds of Tables 1 and 2 exhibit good activity against Diabrotica balteata in this test.
In particular, compounds 2.05, 2.08 and 2.24 are more than 80 effective.
Example B 18: Action against Bemisia tabaci eggs e Dwarf bean plants are placed in gauze cages and populated with adults of Bemisia tabaci (whitefly). When oviposition has taken place, all the adults are removed and 2 days later the plants and the nymphs located thereon are sprayed with an aqueous emulsion of the test compounds (concentration 400 ppm), Evaluation is made 10 days after application of S the test compound by determining the hatching rate in comparison with untreated S controls.
Compounds of Tables 1 and 2 exhibit good activity against Bemisia tabaci in this test.
*ogo

Claims (21)

1. 4-Chloro-4,4-difluorobutyric acid derivatives of formula I C1 2 C-cjH-TH-fj-X-R 3 (I R, R 2 0 wherein R 1 and R2 independently of one another are hydrogen, CI-C 4 alkyl or Cl-C4haloalkyl, R 3 is hydrogen or an organic radical and X is oxygen or -NR 4 in which R 4 is hydrogen or Cl-C~alkyl. Compounds according to claim 1, wherein R 3 is hydrogen or Cl.-C 2 Galkyl, ses C 3 -C 7 cycloalkyl, C 3 -C2Oalkenyl, C3-C20alkynyl, benzyl or aryl, each of which is substituted or unsubstituted. c3. Compounds according to claim 1, wherein R 3 is hydrogen, C1-C2Oalkyl, C 3 -C 7 cycloalkyl, C 3 -C20alkenyl, C3-C20alkynyl, aryl, C 3 -C 2 Ohaloalkenyl, C 3 -C 2 Ohalo- alkynyl; C 3 -C 7 cycloalkyl substituted by halogen or by Cl.-C 4 alkyl; aryl substituted by halogen), C l-C 4 alkyl, Cl-C 4 haloalkyl, Cl-C 1 2alkoxy, C1 -C 4 haloalkoxy, Cl-C 4 alkylthio, **o1 nitro, cyano, benzoyl, halobenzoyl, phenoxy, halophenoxy, Cl-C4alkylphenoxy, C 1 -C 4 haloalkylphenoxy, tri-Ci -C4alkylsilyl, N-pyrrolidinyl, N-piperidinyl, N-pyrrolidin-2-onyl, N-piperidin-2-onyl, Cl-C4alkylamino, di-Ci -C4alkylamino, anilino, 00 c*c N-Cl-C4alkylanilino, N-formylanilino, N-Cl-C~alkylcarbonylanilino, phenylthio or by halophenylthio; phenyl substituted by an unsubstituted or substituted, aromatic or non-aromatic, monocyclic or bicyclic heterocycle that is bonded via oxygen or sulfur, in which both the heterocycle and the phenyl ring may each be substituted by halogen, C 1 -C 4 alkyl, nitro, Cl-C4haloalkyl, Cl-C 4 haloalkoxy, ClI-C 4 alkoxy, C 1 -C4alkylthio or by cyclopropyl; or Cl-C2Qalkyl substituted by hydroxy, halogen, di-Cl-C 4 alkylamino, CI-C 4 alkoxy, Cl-C 4 haloalkoxy, C2-C~alkoxyalkoxy, C 1 -C 4 haloalkylthio, CI-C 4 alkylthio, Cl-C4alkylsulfinyl, C 1 -C4alkylsulfonyl, Cl-C4alkylsulfonyloxy, Cj-C 4 alkyl- carbonyl, Cl-C4alkoxycarbonyl, Cl-C~alkylcarbonyloxy, C 3 -C 7 cycloalkyl, aryl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, arylsulfonyloxy, arylcarbonyl or by pyridyl, in which th.- aryl and pyrr yl groups may each be substituted by halogen, C -C4alkyl, Cl-C4- haloalkyl, Cl-C4alkoxy, Cl-C4haloalkoxy, Cl-C4alkylthio, nitro, cyano, phenoxy, 70 halophenoxy, phenylthio or by halophenylthio.
4. Compounds according to claim 1, wherein Rl and R 2 independently of one another are hydrogen or Cl-C4alkyl, but preferably hydrogen. Cozmpounds according to claim 1, wherein X is oxygen, -NCH 3 or -NC 2 H 5 but preferably oxygen or -Nil-.
6. Compounds according to claim 3, wherein R 3 is phenyl substituted in the 4-position by an aromatic monocyclic or bicyclic heterocycle bonded via oxygen and selected from the group pyridine, pyrinidine and benzothiazole, in which both aromatic rings are unsubstituted or together carry not more than three further substituents from the group :..chlorine, bromine, methyl, ethyl and trifluoromethyl.
7. Compounds according to claim 3, wherein R 1 and R 2 independently of one another, ae 0 hydrogen or Cl-C4alkyl, X is oxygen or -NR 4 and R 4 is hydrogen, methyl or ethyl and *:e:R 3 is hydrogen, C-C 0 alkyl, C3-C 7 cyloalkyl, C3-C2alkenyl, C3-C2alkynyl, phenyl, 00 naphthyl, C3-C20haloalkenyl, C3-C20haloalkynyl, C3-C7cycloalkyl substituted by fluorine, chlorine, bromine or by C 1 -C 3 alkyl, phenyl or naphthyl substituted by fluorine, chlorine, bromine or CI-C3alkyl, C 1 -C3haloalkyl, Cl-C3alkoxy, Cl-C3haloalkoxy, Cl-C 3 alkylthio, nitro, cyano, phenoxy, halophenoxy, Cl-C4alkylphenoxy, C 1 -C4haloalkylphenoxy, tri-Cl-C 4 alkylsilyl, N-pyrrolidinyl, N-piperidinyl, ses N-pyrrolidin-2-onyl, N-piperidin-2-onyl, Cl-C4alkylamino, di-C 1 -C4alkylamino, anilino, N-Cl-C4alkylanilino, N-formylanilino, N-Cl-C~alkylcarbonylanilino, phenylthio or by halophenylthio, or Cl-C 2 0 alkyl substituted by hydroxy, fluorine, chlorine, bromine, di-Cl-C4alkylamino, Cj-C4alkoxy, Cl-C4haloalkoxy, C2-C~alkoxyalkoxy, C 1 -C4- haloalkylthio, Cl-C 4 alkylthio, Cl-C4alkylsulfinyl, Cl-C4alkylsulfonyl, Cl-C4alkyl- sulfonyloxy, Cl-C4alkylcarbonyl, Cl-C4alkoxycarbonyl, Cl-C~alkylcarbonyloxy, C3-C 7 cycloalkyl, phenyl, phenoxy, phenylthio, phenylsulfonyloxy or by pyridyl, in which the phenyl and pyridyl groups may each be substituted by fluorine, chlorine, bromiAne, C 1-C3alkyl, Cl-C3haloallcyl, C 1 -C3alkoxy, C1 -C3haloalkoxy, Cl-C3alkylthio, nitro, cyano, phenoxy, haiophenoxy, phenylthio or by halophenylthio.
8. Compounds according to claim 1, wherein RI and R 2 independently of one another are hydrogen or Cl-C4alkyl, X is oxygen or -NR 4 R 4 is hydrogen, methyl or ethyl, R 3 is phenyl, benzyl, naphthyl or 3-pyridylmethyl or phenyl, benzyl, naphthyl or -71- 3-pyridylmethyl each of which is substituted by fluorine, chlorine, bromine, Cl-C 3 alky1, Cl-C 3 haloalkyl, Ci-C 3 alkoxy, Cl-C 3 haloalkoxy, Cl-C 3 alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or by halophenylthio. 9, Compounds according to claim 1, wherein R 1 and R 2 independently of one another are hydrogen or Cj-C4allcyl, X is oxygen or -NR 4 R4 is hydrogen or C 1 -C4alkyl, R 3 is Cl-Cl 2 alkyl or Cl-Cl2alkyl substituted by hydroxy, fluorine, chlorine, bromine, dimethylamino, methoxy, ethoxy, methoxyethoxy, ethoxyethoxy, methylthio, ethylthio, cyclopropyl, cyclopentyl, cyclohexyl, phenyl or by phenoxy, in which the phenyl or phenoxy radical may be substituted by fluorine, chlorine, bromine, phenoxy, halophenoxy or by phenylthio.
10. Compounds according to claim 1, wherein R 1 and R 2 independently of one another are hydrogen or Cl-C 4 alkyl, X is oxygen or -NR4-, R 4 is hydrogen or C1-C4alkyl, R 3 is 3-Cl 2 alkenyl or C3-Cl~alkynyl Or C3-Cl~alkenyl or C--Cl~alkynyl each of which is substituted by fluorine, chlorine or by bromine.
11. Compounds according to claim 3, wherein R 1 and R 2 are hydrogen and X is oxygen, -NCH 3 or -NC 2 Et 5
12. Compounds according to claim 1, selected from the group 4-chloro-4,4-difluorobutyric acid methyl ester, 4-chloro-4,4-difluorobutyric acid ethyl ester, 4-chloro-4,4-difluorobutyric acid isopropyl ester, 4-(;hloro-4,4-difluorobutyric acid tert.-butyl ester, 4-chloro-4,4-difluorobutyric acid n-butyl ester, 4-zhloro-4,4-difluorobutyric acid (2,2-dimethylpropyl) ester, A a i e z l e t r :':4-chloro-4 A -difluorobutyric, acid benyl ester, 4-chloro-4,4-difluorobutyric acid [-4poxypyloy-ehl ester, 4-chloro-4,4-difluorobutyric acid [2-(4-hexyhes oytyrstr 4-chloro-4,4-difluorobutyric acid cyclohexymtyl ester, 4-chloro-4,4-difluorobutyric acid cyclohexpylmethyl ester, 4-chloro-4,4-difluoro-2-trifluoromethylbutyric acid ethyl ester, 4-chloro-4,4-difluorobutyric acid N-methylamide, 72 4-chloro-4,4-difluorobutyric acid N,N-dimethylamide, 4-chloro-4,4-difluorobutyric acid N,N-dihexylamide, 4-chloro-4,4-difluorobutyric acid N-ethylamide, 4-chloro-4,4-difluorobutyvric acid N-isopropylamide, 4-chloro-4,4-difluorobutyric acid N-butylamide, 4-chloro-4,4-difluorobutyric acid N-tert.-butylamide, 4-chloro-4,4-difluorobutyric acid N-benzylamide, 4-chloro-4,4-difluorobutyric acid anilide, 4-Lliloro-4,4-difluorobutyric acid N-methyl-N-pyrid-3-ylmethylamide., 4-chluro-4,4-difluorobutyric acid N-pyrid-3-ylmethylamide, 4-chloro-4,4-difluorobutyric acid (4-chioroanilide), 4-chloro-4,4-difluorobutyric acid (4-phenoxyanilide), 4 h o o 4 4 d f u r b t r i c d h o o n l d :..4-chloro-4,4-difluorobutyric acid (2-chooanilide), *eye. 4-chloro-4,4-difluorobutyric acid (4-methoyanilide), *a:.4-chloro-4,4-difluorobutyric acid (4-methylmanide),e) 4-chloro-4,4-difluorobutyric acid (3-melrcaptoanlide) 2 "4-chloro-4,4-difluorobutyric acid (4-floroa2nide),de *S 4-chloro-4,4-difluorobutyric acid (4-chloo--itroalideser, 4-chloro-4,4-difluorobutyric acid [(-frphenoxyyi)l ester, 4-chloro-4,4-difluorobutyric acid [4-(4-fluorophenoxy)-phenoy l ester, 4-chloro-4,4-clifluorobutyrc acid (4-nitrophenyl) ester, .:4-chloro-4,4-difluorobutyric acid [4-(3,5-difluorophenoxy)-phenyl] ester, V. 4-chloro-4,4-difluorobutyric acid [4-(5-trifluoromethylpyrid-2-yloxy)-phenyl] ester, 4-chloro-4,4-difluorobutyric acid and 4-chloro-4,4-difluorobutyri,', acid amide. OS 13. A process for the preparation of the compounds of formula I according to claim 1, which comprises either a) reacting a 4-chloro-4,4-difluorobutyric acid halide of formula H R 1 R 2 0 wherein RI and R 2 are as defined under formula I and Hal is halogen, preferably chlorine or bromine, with a compound of formula I 73 H-X-R 3 wherein X and R 3 are as defined under formula I, in the presence of a base, or b) reacting 4-chloro-4,4-difluorobutyric acid of formula Ic CIF 2 C-CH-CH-C-OH I I II R, R 2 0 (Ic), wherein R 1 and R 2 are as defined under formula I, with a compound of formula III in the presence of water-removing agent.
14. A pesticidal composition, which contains as active ingredient at least one compound according to any one of claims 1 to 12 together with a pesticidally acceptable carrier, adjuvant and/or diluent.
15. A method of controlling insects and/or arachnids that are harmful to animals and plants, which comprises treating the insects and/or arachnids or the locus thereof with an insectically and/or arachnicidally effective amount of a compound of formula I according to any one of claims 1 to 12 or a composition according to claim 14.
16. 4-Chloro-4,4-difluorobutyric acid halides of formula II CIF 2 C-CH-CH-C-Hal I I II R 1 R 2 O (11), wherein R 1 and R 2 independently of one another are hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl, and Hal is halogen, preferably chlorine or bromine.
17. 4-Chloro-4,4-difluorocrotonic acid derivatives of formula VIII C IF 2 C-C=C- C-X-R i I 1I .R R 2 0 (VIII), wherein R is C 1 -C 6 alkyl, R 1 and R 2 independently of one another are hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl, X is oxygen or -NR 4 in which R4 is hydrogen or Cl-C6alkyl. IJ\WPUSSR\UBFF100022:EAR 74
18. A process for the preparation of the compounds of formula I, which comprises hydrogenating a 4-chloro-4,4-difluorocrotonic acid derivative of formula VIII CIF 2 C-C=C- C-X-R (VIII), I I II R, R 2 O wherein R is hydrogen or C 1 -C 6 alkyl, R 1 and R 2 independently of one another are hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl, R 3 is hydrogen or an organic radical and X is oxygen or -NR 4 in whi"' R 4 is hydrogen or C 1 -C 6 alkyl, with hydrogen in the presence of a catalyst and converting the resulting compounds of formula Id CIF 2 C-CH-CH-C-X-R (Id), I I II R R2 0 Swherein R 1 R 2 X and R are as defined above, into the other compounds of formula i Saccording to claim 1 by hydrolysis, transesterification or transamidation.
19. The product of the process of claim 13 or claim 18. A 4-Chloro-4,4-difluorobutyric acid derivative substantially as hereinbefore described with reference to any one of Examples P1 to P11, P13 or any one of compound 20 numbers 1.01 to 1.140, 2.01 to 2.196.
21. A 4-Chloro-4,4-difluorobutyric acid halide substantially as hereinbefore described with reference to Example P6(b).
22. A 4-Chloro-4,4-difluorocrotonic acid derivative substantially as hereinbefore described with reference to Example P12.
23. A process for the preparation of a 4-chloro-4,4-difluorobutyric acid derivative, which process is substantially as hereinbefore described with reference to any one of Examples P1 to P11, P13 or any one of compound numbers 1.01 to 1.140, 2.01 to 2.196.
24. A process for the preparation of a 4-chloro-4,4-difluorobutyric acid halide, which Sprocess is substantially as hereinbefore described with reference to Example P6(b). IUbW\0027:EAR 3 of 4 A process for the preparation of a 4-chlo.to-4,4-difluorocrotonic acid derivative, which process is substantially as hereinbefore described with reference to Example P12.
26. A pesticidal composition substantially as hereinbefore described with reference to any one of Examples Fl to
27. A pesticidal composition comprising a compound of claim 20 together with a pesticidally acceptable carrier, adjuvant and/or diluent.
28. A method of controlling insects and/or arachnids that are harmful to animals and plants, which method comprises treating the insects and/or arachnids or the locus thereof with an insecticidally and/or arachnicidally effective amount of a compound of claim 19 or 20 or a composition of claim 26 or claim 27. Dated 21 April, 1993 Ciba-Geigy AG Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON 0 0 0 *5 0u 00000 0, S S *Q S .J. S 055 o S IUbWi\O0267,EAR
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IL102676A0 (en) * 1991-08-07 1993-01-14 Ciba Geigy Ag Butyric acid amides
ES2106162T3 (en) * 1991-11-01 1997-11-01 Ciba Geigy Ag DERIVATIVES OF THE BUTIRIC ACID, PROCEDURE FOR ITS PREPARATION AND ITS USE AS PESTICIDES.
ATE149482T1 (en) * 1993-11-11 1997-03-15 Basf Ag P-HYDROXYANILINE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING HARMFUL FUNGALS OR PESTS
ATE163639T1 (en) * 1993-11-11 1998-03-15 Basf Ag P-HYDROXYANILINE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING HARMFUL FUNGALS OR PESTS
JP2006223647A (en) * 2005-02-18 2006-08-31 Hiroyasu Yamamoto Training machine for enhancing running speed
JP2007143748A (en) * 2005-11-25 2007-06-14 Sharp Corp Image recognition device, fitness aid device, fitness aid system, fitness aid method, control program and readable recording medium
US20110297883A1 (en) * 2009-02-19 2011-12-08 Solvay Fluor Gmbh Compositions of esters of fluorosubstituted alcanoic acids
KR101904510B1 (en) * 2014-03-17 2018-10-05 닛산 가가쿠 가부시키가이샤 Oligoaniline derivative, charge-transporting varnish, and organic electroluminescent element

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HRP940499A2 (en) 1997-06-30
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AU6109790A (en) 1991-02-21
EP0413666A1 (en) 1991-02-20
TR25930A (en) 1993-11-01
IE63504B1 (en) 1995-05-03
EG19084A (en) 1994-09-29
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IL95346A0 (en) 1991-06-30
MY106449A (en) 1995-05-30
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YU157190A (en) 1993-05-28
CA2023464A1 (en) 1991-02-19
KR910004530A (en) 1991-03-28
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