Bicyclic amines and their use as insecticides

Details Bicyclic amines and their use as insecticides Bicyclic amines and their use as insecticides

2000-05-12

2001-09-25

Rotman, Alan L. (Department: 1625)

Drug, bio-affecting and body treating compositions

Designated organic active ingredient containing

Having -c-, wherein x is chalcogen, bonded directly to...

C514S299000, C514S304000, C546S018000, C546S021000, C546S112000, C424S265100

Reexamination Certificate

active

06294545

ABSTRACT:

This is a 371 of Application No. PCT/GB98/03098, filed Oct. 15, 1998.
This invention relates to bicyclic amine derivatives, to processes for preparing them, to insecticidal compositions comprising them and to methods of using them to combat and control insect pests.
Insecticidal bicyclic amines are disclosed in WO 96/37494.
The present invention provides a compound of formula (I):
wherein A is a bidentate group of formula XC═CY or XCH—CHY (wherein X and Y are independently hydrogen, hydroxy, acyloxy, alkoxy, cyano or halogen); and Ar is optionally substituted phenyl or optionally substituted heteroaryl; or an acid addition salt, quaternary ammonium salt or N-oxide derived therefrom; provided that when A is CH
2
—CH
2
then Ar is neither 5-chloropyrid-3-yl nor 5-trifluoromethylpyrid-3-yl.
It will be appreciated that the compounds of formula (I) are capable of existing in more than one isomeric form since groups may be positioned in either an exo or endo relationship, and the present invention embraces within its scope both exo and endo forms and mixtures thereof in all proportions and also any further isomeric variants arising from cis and trans substitution patterns or chiral centres.
Heteroaryl includes 5- and 6-membered rings comprising one, two or three heteroatoms selected form the group comprising nitrogen, oxygen and sulphur, said rings being optionally fused to a benzene ring. Examples of heteroaryl are pyridine, pyrazine, pyridazine, pirimidine, pyrrole, pyrazole, imidazole, 1,2,3- and 1,2,4-triazoles, furan, thiophene, oxazole, isoxazole, thiazole, isothiazole, 1,2,3- and 1,3,4-oxadiazoles, 1,2,3- and 1,3,4-thiadiazoles, benzoxazole, indole, benzofuran, benzothiophen and benzimidazole.
Halogen includes fluorine, chlorine, bromine and iodine.
Alkyl moieties preferably contain from 1 to 6, more preferably from 1 to 4, carbon atoms. They can be in the form of straight or branched chains, for example methyl, ethyl, n- or iso-propyl, or n-, sec-, iso- or tert-butyl.
Acyloxy is preferably alkylcarbonyloxy or optionally substituted phenylcarbonyloxy. Acyloxy is, for example, acetyloxy or benzoyloxy.
Phenyl and heteroaryl rings are preferably optionally substituted with: halogen, hydroxy, mercapto, C
1-4
alkyl, C
2-4
alkenyl, C
2-4
alkynyl, C
1-4
alkoxy, C
2-4
alkenyloxy, C
2-4
alkynyloxy, halo(C
1-4
)alkyl (for example CF
3
), halo(C
1-4
)alkoxy (for example OCF
3
), C
1-4
alkylthio, halo(C,
1-4
)alkylthio, hydroxy(C
1-4
)alkyl, C
1-4
alkoxy(C
1-4
)alkyl (for example CH
3
OCH
2
), C
3-6
cycloalkyl (such as cyclopentyl or cyclohexyl), C
3-6
cycloalkyl(C
1-4
)alkyl (such as cyclopentylmethyl or 1-cyclopropyleth-1-yl), phenyl, phenoxy, SF
5
, cyano, thiocyanato, nitro, —NR′R″, —NHCOR′, —CONR′R″, —COOR′, —SOR′, —SO
2
R′, —SO
2
(C
3-6
)alkenyl, —OSO
2
R′, —NHSO
2
R′, —SO
2
NR′R″, —COR′, —CR′═N″, —CR′═NOR″ or —N═CR′N″; two substituents, when they are in adjacent positions on the phenyl or heteroaryl ring can join to form a fused aliphatic ring (especially to form a fused 6-membered carbon aliphatic ring) or a fused alkylenedioxy ring (such as methylenedioxy or difluoromethylenedioxy); R′ and R″ are independently hydrogen, C
1-4
alkyl, C
1-4
alkoxy, C
1-4
alkylthio, C
3-6
cycloalkyl, C
3-6
cycloalkyl(C
1-4
)alkyl, phenyl or benzyl; the phenyl, phenoxy and benzyl groups being optionally substituted with halogen, C
1-4
alkyl, halo(C
1-4
)alkyl, C
1-4
alkoxy or C
1-4
haloalkoxy.
Alkenyl and alkynyl moieties can be in the form of straight or branched chains, and alkenyl moieties can be of either (E)- or (Z)-configuration. Examples are vinyl, allyl and propargyl.
Suitable acid addition salts include those with an inorganic acid such as hydrochloric, hydrobromic, sulfuric, nitric and phosphoric acids, or an organic carboxylic acid such as oxalic, tartaric, lactic, butyric, toluic, hexanoic and phthalic acids, or sulphonic acids such as methane, benzene and toluene sulphonic acids. Other examples of organic carboxylic acids include haloacids such as trifluoroacetic acid.
In one aspect the present invention provides a compound of formula (I) wherein A is CH
2
—CH
2
or CH═CH.
In a further aspect the present invention provides a compound of formula (I) wherein A is CH═CH.
In another aspect the present invention provides a compound of formula (I), wherein Ar is phenyl or pyrazinyl, all being optionally substituted with halogen (especially fluorine, chlorine or bromine), C
1-4
alkyl (especially methyl), C
1-4
alkoxy (especially methoxy), C
2-4
alkenyl, C
2-4
alkynyl or cyano.
In a further aspect the present invention provides a compound of formula (I) wherein Ar is pyridinyl optionally substituted with fluorine, bromine, cyano, C
1-4
alkyl, C
1-4
alkoxy or C
2-4
haloalkyl (such as 2,2,2-trifluoroethyl, 2,2-difluoroethyl or 2,2,2-trichloroethyl).
Specific compounds of formula (I) are set out in the Tables below.
TABLE 1
Compound No.
Ar
A
1
5-chloropyrid-3-yl
CH═CH
2
5-methoxypyrid-3-yl
CH
2
—CH
2
3
5-bromopyrid-3-yl
CH
2
—CH
2
4
3,5-difluorophenyl
CH
2
—CH
2
5
5-trifluoromethylpyrid-3-yl
CH═CH
6
5-methoxypyrid-3-yl
CH═CH
7
5-bromopyrid-3-yl
CH═CH
8
3,5-difluorophenyl
CH═CH
9
5-acetylenylpyrid-3-yl
CH
2
—CH
2
10
5-acetylenylpyrid-3-yl
CH═CH
11
5-cyanopyrid-3-yl
CH
2
—CH
2
12
5-cyanopyrid-3-yl
CH═CH
13
6-methoxypyrazin-2-yl
CH
2
—CH
2
14
6-methoxypyrazin-2-yl
CH═CH
15
pyrid-3-yl
CH
2
—CH
2
16
pyrid-3-yl
CH═CH
17
6-chloropyrazin-2-yl
CH
2
—CH
2
18
6-chloropyrazin-2-yl
CH═CH
19
3,5-dichlorophenyl
CH
2
—CH
2
20
3,5-dichlorophenyl
CH═CH
Compounds of formula (I) can be prepared by adapting methods described in the literature (such as WO 96/37494), by use of one or more of the following synthetic techniques described below and further illustrated in the Examples, or by combining literature methods with those methods described below. Throughout the following description R is alkyl (such as methyl) or phenylalkyl (such as benzyl).
A compound of formula (I) can be prepared by reacting a compound of formula (II) with formic acid at an elevated temperature (such as over 70° C.).
Alternatively, a compound of formula (I) can be prepared by reacting a compound of formula (II) with a suitable mixed formic anhydride (such as formic acetic anhydride).
A compound of formula (II) can be prepared by reacting a compound of formula (III) with a suitable chloroformate (such a vinyl chloroformate) and reacting the product so formed with a mineral acid (such as concentrated hydrochloric acid).
A compound of formula (III) can be prepared by treating a compound of formula (IV) first with a suitable base, such as lithium diisopropylamide (LDA) or lithium bis(trimethylsilyl)amide, and then reacting the product so formed with a compound ArHal, wherein Hal is a halogen.
A compound of formula (IV) can be prepared by reacting a compound of formula (V) with a compound of formula RL (wherein L is a suitable leaving group, such as a halide) preferably in the presence of a base.
Compounds of formula (V) can be prepared by processes analogous to those described in the art.
Compounds of formula (III) wherein A is CH═CH can be prepared by heating a compound of formula (III) wherein A is CH
2
CHZ (wherein Z is a suitable group, such as a thiono4-tolyloxy group) in a suitable solvent (such as xylene) at a suitable temperature (such as reflux).
Compounds of formula (III) wherein A is CH
2
CHZ (wherein Z is a suitable group, such as a thiono4-tolyloxy group) can be prepared by treating compounds of formula (III) wherein A is CH
2
CH(OH) with a suitable thionoformate (such as 4-tolyl chlorothiono formate) in the presence of a suitable base (such as NIN-dimethylaminopyridine).
Compounds of formula (III) wherein A is CH
2
CH(OH) can be prepared by acid hydrolysis of compounds of formula (III) wherein A is CH
2
CH(OZ′) wherein Z′ is a hydrolysable group (such as tert-butyldimethylsilyl).
A compound of formula (III) w

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