University of California

The Wellcome Foundation Limited

Roussel Uclaf

Other

John P Larkin

Ian H Smith

John E Casida

Christopher J Palmer

John B Weston

John A Wyatt

David A Pulman

Malcolm H Black

Deborah J Hawkes

The present invention provides a class of substituted bicyclooctanes of formula ##STR1## wherein R is a C.sub.2-10 non-aromatic hydrocarbyl optionally substituted by cyano, halo, C.sub.1-4 alkoxy, C.sub.1-4 haloalkoxy or S(O).sub.m R.sup.3 ; R.sup.1 and r.sup.2 are independently hydrogen, halo, a C.sub.1-3 aliphatic group optionally substituted, S(O).sub.m,R.sup.4, or R.sup.1 and R.sup.2 and the carbon atoms to which they are attached form a C.sub.5-7 carbocyclic ring optionally substituted by halo, or a C.sub.1-3 aliphatic or alkoxy group;

Heterobicycloalkanes as pesticidal compounds

Bicyclo-[2,2,1]-heptanes, bicyclo-[2,2,2,]-octanes and bicyclo-[2,2,3]-nonanes having 2 or 3 ring hetero atoms selected from O, S and N, substituted at the 1-position by a 4-alkynylphenyl group and at the 4-position and optionally at the 3 and/or 5-position are valuable pesticides, particularly insecticides and acaracides. The compounds may be prepared by reacting an alkyne with the corresponding 4-iodophenyl substituted compound or by debromination of the corresponding 4-dibromomethylphenyl substituted compound.

Trithiabicyclo[2,2,2]octanes

The present invention provides compounds of the formula (I): ##STR1## wherein R is a phenyl group, substituted fluorine atoms formulations containing them and their use in controlling pest infestation.

Pesticidal compounds

Bicyclo-[2,2,1]-heptanes, bicyclo-[2,2,2]-octanes and bicyclo-[2,2,3]-nonanes having 2 or 3 ring hetero atoms selected from O, S and N, substituted at the 1-position by a 4-alkynylphenyl group and at the 4-position and optionally at the 3 and/or 5-position are valuable pesticides, particularly insecticides and acaracides. The compounds may be prepared by reacting an alkyne with the corresponding 4-iodophenyl substituted compound or by debromination of the corresponding 4-dibromomethylphenyl substituted compound.

The present invention provides a class of novel substituted bicyclooctanes which have pesticidal activity, particularly against arthropod pests. Pesticidal formulations containing the compounds of the formula (I), their use in the control of pests and methods for their preparation are also disclosed.

A compound of the formula (I): ##STR1## wherein R is C.sub.2-10 alkyl, alkenyl or alkynyl, each optionally subsituted by or methyl substituted by cyano, C.sub.3-4 cycloalkyl, halo, C.sub.1-4 alkoxy or a group S(O)mR.sup.4 where R.sup.4 is C.sub.1-4 alkyl and m is O, 1 or 2, or R is C.sub.3-10 cycloalkyl, C.sub.4-10 cycloalkenyl or phenyl, each optionally substituted by C.sub.1-4 alkoxy, C.sub.1-3 alkyl, C.sub.2-4 alkynyl, halo, cyano or a group S(O)mR.sup.4 as defined hereinbefore; R.sup.1 is halo, C.sub.1-3 alkyl, C.sub.2-3 alkenyl or alkynyl each optionally substituted by halo, cyano, C.sub.1-4 alkoxy, alkyl carbalkoxy containing up to 6 carbon atoms, a group S(O)mR.sup.4 as defined hereinbefore or alkynyl substituted by tri-C.sub.1-4 alkylsilyl, or R.sup.1 is cyano, spiro-cyclopropyl, gem dimethyl, oxo or methylene optionally substituted by cyano or C.sub.1-3 alkyl optionally substituted by fluorine, or R.sup.1 and R and the carbon atoms to which they are attached form a C.sub.5-7 carbocyclic ring optionally substituted by halo, C.sub.1-3 alkyl or alkoxy or C.sub. 2-3 alkenyl, R.sup.2 is phenyl, C.sub.5-10 cycloalkyl or cycloalkenyl each optionally substituted other than phenyl substituted by C.sub.2-3 alkynyl and R.sup.3 is hydrogen, C.sub.1-3 alkyl, C.sub.2-3 alkenyl or alkynyl each optionally substituted by cyano, C.sub.1-4 alkylthio, C.sub.1-4 alkoxy or halo, or R.sup.3 is cyano, its use in medicine, pharmaceutical compositions containing it and processes for its preparation.

Pesticidally-active alkynylphenyl-substituted 1,3-oxathianes and related substituted compounds of the formula: ##STR1## and their use in controlling pests such as arthropods and helminths are described.

Alkynylphenyl-substituted 1,3-oxathione compounds with pesticidal

Pesticidal bicyclo-octanes are of the formula ##STR1## where R is a substituted or unsubstituted aliphatic or aromatic group, R' and R.sup.3 are H or a substituted or unsubstituted aliphatic or aromatic group, R.sup.2 is a substituted or unsubstituted heterocyclic group containing at least one ring nitrogen and is preferably a 3- or 4- pyridyl group, Z is CH.sub.2 CH.sub.2, CH.sub.2 O--CH.sub.2 S or COCH.sub.2 or CH(OR.sup.5)CH.sub.2 where R.sup.5 is H, alkyl, acyl or carbamoyl at Y and Y' are O or S(O).sub.m where m is 0, 1 or 2. Various methods for their preparation are described.

1-heterocyclic bicyclo-octanes

Bicyclo-[2,2,1]-heptanes, bicyclo-[2,2,2]-octanes and bicyclo[2,2,3]-nonanes having 2 or 3 ring hetero atoms selected from O, S and N, substituted at the 1-position by a 4-alkynylphenyl group and at the 4-position and optionally at the 3 and/or 5-position are valuable pesticides, particularly insecticides and acaracides. The compounds may be prepared by reacting an alkyne with the corresponding 4-iodophenyl substituted compound or by debromination of the corresponding 4-dibromomethylphenyl substituted compound.

The present invention provides compounds of the formula (I): ##STR1## wherein R is a C.sub.2-10 non-aromatic hydrocarbyl group, a C.sub.2-10 non-aromatic hydrocarbyl group substituted by, or methyl substituted by cyano, halo, C.sub.1-4 alkoxy, C.sub.1-4 alkoxy substituted by halo, or a group S(O).sub.m R.sup.4 where R.sup.4 is C.sub.1-4 alkyl optionally substituted by halo and m is 0, 1 or 2, or R is phenyl or phenyl substituted by C.sub.1-4 alkoxy, C.sub.1-3 alkyl, C.sub.2-4 alkynyl, halo, C.sub.1-4 haloalkyl, cyano or a group S(O).sub.m R.sup.4 as defined hereinbefore; R.sup.1 and R.sup.2 may be the same or different, and each is hydrogen, or a C.sub.1-3 aliphatic group, or a C.sub.1-3 aliphatic group substituted by halo; R.sup.3 contains between 3 and 18 carbon atoms and is a group R.sup.5 wherein R.sup.5 is a C.sub.1-13 non-aromatic hydrocarbyl group, a C.sub.1-3 non-aromatic hydrocarbyl group substituted by a C.sub.2-4 carbalkoxy or cyano group and/or by one or two hydroxy groups and/or by one to five halo atoms which are the same or different and/or by one to three groups R.sup.6 which are the same or different and each contains one to four hetero atoms, which are the same or different and are chosen from oxygen, sulphur, nitrogen and silicon, 1 to 10 carbon atoms and 0 to 6 fluoro or chloro atoms or R.sup.3 is a 6-membered aromatic ring substituted by cyano and/or by one to three groups R.sup.6 and/or by a group --C.tbd.CH, --C.tbd.C--R.sup.5 or C.tbd.C-halo and/or by one to five halo atoms and/or by one to three C.sub.1-4 haloalkyl groups wherein R.sup.5 and R.sup.6 are as hereinbefore defined; and Y is selected from methylene, oxygen and S(O).sub.t', Y' is selected from oxygen and S(O).sub.t' where t' and t' are each selected from 0, 1 or 2; and t is 1 or 2, processes for their preparation, formulations containing them and their use in the control of pest infestation.

Bicyclo-[2,2,1]-heptanes, bicyclo-[2,2,2]-octanes and bicyclo-[2,2,3]-nonanes, having 2 or 3 ring hetero atoms selected from O, S and N substituted at the 1-position by a carbocyclic group other than an alkynylphenyl group, and substituted at the 4-position and optionally substituted at the 3 and/or 5 position, are valuable pesticides, particularly insecticides and acaricides. Various cyclization processes are disclosed to form the various bicyclo ring systems.

Bicyclo-[2,2,1]-heptanes, bicyclo-[2,2,2]-octanes and bicyclo-[2,2,3]-nonanes, having 2 or 3 ring hetero atoms selected from O, S and N, substituted at the 1-position by a 4-alkynylphenyl group and at the 4-position and optionally at the 3 and/or 5-position are valuable pesticides, particularly insecticides and acaracides. The compounds may be prepared by reacting an alkyne with the corresponding 4-iodophenyl substituted compounds or by debromination of the corresponding 4-dibromomethylphenyl substituted compound.

The present invention relates to a compound of the formula (I): ##STR1## wherein R is C.sub.2-10 alkyl, alkenyl or alkynyl, each optionally substituted by or methyl substituted by cyano, C.sub.3-4 cycloalkyl, halo, C.sub.1-4 alkoxy or a group S(O)m R.sup.4 where R.sup.4 is C.sub.1-4 alkyl and m is 0, 1 or 2, or Ris C.sub.3-10 cycloalkyl, C.sub.4-10 cycloalkenyl or phenyl, each optionally substituted by C.sub.1-4 alkoxy, C.sub.1-3 alkyl, C.sub.2-4 alkynyl, halo, cyano or a group S(O)m R.sup.4 as defined hereinbefore; R.sup.1 is halo, C.sub.1-3 alkyl, C.sub.2-3 alkenyl or alkynyl each optionally substituted by halo, cyano, C.sub.1-4 alkoxy, alkyl carbalkoxy containing up to 6 carbon atoms, a group S(O)m R.sup.4 as defined hereinbefore or alkynyl substituted by tri-C.sub.1-4 alkylsilyl, or R.sup.1 is cyano, spiro-cyclopropyl, gem dimethyl, gem dicyano, gem diethynyl, oxo or methylene optionally substituted by cyano of C.sub.1-3 alkyl optionally substituted by fluorine, or R.sup.1 and R and the carbon atoms to which they are attached form a C.sub.5-7 carbocyclic ring optionally substituted by halo, C.sub.1-3 alkyl or alkoxy or C.sub.2-3 alkenyl, R.sup.2 is phenyl substituted by an C.sub.2-3 alkynyl group or by a tri-C.sub.1-4 alkylsilylalkynyl group and R.sup.3 is hydrogen, C.sub.1-3 alkyl, C.sub.2-3 alkenyl or alkynyl each optionally substituted by cyano, C.sub.1-4 alkylthio, C.sub.1-4 alkoxy or halo, or R.sup.3 is cyano or halo, its use in medicine, pharmaceutical compositions containing it and its preparation.

Growing community of inventors

Leighton Buzzard, United Kingdom

John P Larkin