Insecticidal dihydrooxadiazine compounds

Details Insecticidal dihydrooxadiazine compounds Insecticidal dihydrooxadiazine compounds

1999-01-11

2001-03-06

Shah, Mukund J. (Department: 1624)

Drug, bio-affecting and body treating compositions

Designated organic active ingredient containing

Heterocyclic carbon compounds containing a hetero ring...

C514S230500, C514S222500, C514S222800, C514S242000, C514S243000, C544S066000, C544S008000, C544S010000, C544S182000, C544S183000

Reexamination Certificate

active

06197766

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to insecticidal substituted dihydrooxadiazine compounds, insecticidal compositions containing the dihydrooxadiazine compounds, and methods for their use.
BACKGROUND OF THE INVENTION
Certain oxadiazine compounds have been described as useful as pesticides and as pharmaceutical agents. For example, U.S. Pat. No. 5,536,720 describes substituted 2-phenyl-1,3,4-oxadiazine-4-carbamide compounds useful as insecticides and acaricides. Trepanier et al, J. Med. Chem 9: 753-758 (1966) describe certain 2-substituted 4H-1,3,4-oxadiazines useful as anticonvulsants in mice. U.S. Pat. No. 3,420,826 describes certain 2,4,6-substituted 4H-1,3,4-oxadiazines, useful as sedatives, anticonvulsants, and as pesticides against nematodes, plants, and fungi. U.S. Pat. No. 3,420,825 describes methods for producing certain 2,4,6-substituted 4H-1,3,4-oxadiazines.
It is a purpose of this invention to provide novel dihydrooxadiazine derivatives useful as insecticides.
SUMMARY OF THE INVENTION
The present invention relates to a compound having the formula:
wherein
X is O, N or S;
R is phenyl, unsubstituted or mono-, di-, or tri-substituted with halogen, C
1
-C
4
haloalkyl, C
1
-C
4
haloalkoxy, or C
1
-C
4
haloalkyl thio; or R is a C
4
-C
5
heterocyclic group containing one nitrogen, sulfur, or oxygen atom, unsubstituted or mono-, di-, or tri-substituted with halogen, C
1
-C
4
haloalkyl, or C
1
-C
4
haloalkoxy;
R
1
is halogen, C
1
-C
4
haloalkyl, C
1
-C
4
haloalkoxy, C
1
-C
6
haloalkyl sulfonyl, or C
1
-C
4
haloalkyl sulfinyl;
R
2
, R
3
, R
4
, and R
5
are one of the following:
a) R
2
, R
3
, and R
4
are, independently, hydrogen, C
1
-C
6
alkyl, C
1
-C
6
alkoxy, or furanyl; and R
5
is nitro, cyano, C
1
-C
6
alkyl, di(C
1
-C
6
)alkylamino, C
1
-C
6
alkylthio, C
1
-C
6
alkoxy, C
1
-C
6
haloalkoxy, phenoxy, phenylthio, or (C
1
-C
6
alkoxy)carbonyl, wherein R
3
and R
5
together can form a ring; or
b) R
3
, R
4
, and R
5
are hydrogen; and R
2
is C
1
-C
6
alkylthio, C
1
-C
6
alkylsulfinyl, Cl-C
6
alkylsulfonyl, nitro(C
1
-C
6
alkoxy), hydroxy, di-(C
1
-C
4
alkoxy)-phosphinyl, cyano, C
2
-C
6
acyloxy, C
1
-C
6
alkoxy, C
1
-C
6
haloalkoxy, C
4
-C
6
cycloalkyl, or C
3
-C
6
alkenyl; or R
2
is phenyl, phenylthio, phenylsulfinyl, phenylsulfonyl, pyrazolyl, furanyl, thienyl, phenyl(C
1
-C
6
alkoxy), or benzoyloxy, unsubstituted or mono-, di-, or tri-substituted with halogen, C
1
-C
4
alkyl, or C
1
-C
4
alkoxy;
R
6
is hydrogen, C
1
-C
6
alkyl, C
1
-C
4
alkylthio, (C
1
-C
4
alkoxy)C
1
-C
4
alkyl, C
2
-C
8
acyl, benzyl, or (C
1
-C
6
alkoxy)carbonyl.
These compounds, or physiologically acceptable salts thereof, are useful as insecticides.
The insecticidal compositions of this invention comprise: (a) an effective amount of one or more compounds of formula I, and (b) a suitable carrier.
DETAILED DESCRIPTION OF THE INVENTION
Preferably, the compound of this invention has the formula:
wherein
R is phenyl, unsubstituted or mono-, di-, or tri-substituted with halogen, C
1
-C
4
haloalkyl, C
1
-C
4
haloalkoxy, C
1
-C
4
haloalkyl thio, C
1
-C
4
haloalkyl sulfinyl, or C
1
-C
4
haloalkyl sulfonyl; or R is a C
4
-C
5
heterocyclic group containing one nitrogen, sulfur, or oxygen atom, unsubstituted or mono-, di-, or tri-substituted with halogen, C
1
-C
4
haloalkyl, or C
1
-C
4
haloalkoxy;
R
1
is halogen, C
1
-C
4
haloalkyl, C
1
-C
4
haloalkoxy, C
1
-C
4
haloalkyl thio, C
1
-C
6
haloalkyl sulfinyl, C
1
-C
6
haloalkyl sulfonyl;
R
2
is C
1
-C
6
alkylthio, C
1
-C
6
alkylsulfinyl, C
1
-C
6
alkylsulfonyl, nitro(C
1
-C
6
alkoxy), hydroxy, di-(C
1
-C
4
alkoxy)-phosphinyl, cyano, C
2
-C
6
acyloxy, C
1
-C
6
alkoxy, C
1
-C
6
haloalkoxy, C
4
-C
6
cycloalkyl, or C
3
-C
6
alkenyl; or R
2
is phenyl, phenylthio, phenylsulfinyl, phenylsulfonyl, pyrazolyl, furanyl, thienyl, phenyl(C
1
-C
6
alkoxy), or benzoyloxy, unsubstituted or mono-, di-, or tri-substituted with halogen, C
1
-C
4
alkyl, or C
1
-C
4
alkoxy; and
R
6
is hydrogen, C
1
-C
6
alkyl, (C
1
-C
4
alkoxy)C
1
-C
4
alkyl, C
2
-C
6
haloacyl, C
2
-C
8
acyl, or (C
1
-C
6
alkoxy)carbonyl.
R is more preferably phenyl, optionally mono-, di- or tri-substituted by bromo, chloro, trihaloalkyl, or trihaloalkoxy, more preferably, one bromo, one chloro, one trihalomethyl, one trihaloethyl, one trihalomethoxy, or one trihaloethoxy. Particularly preferred is the compound of formula IA wherein R is phenyl substituted by bromo, chloro, methyl, trifluoromethyl, or trifluoromethoxy.
Preferably, R
1
is C
1
-C
4
trihaloalkyl or C
1
-C
4
trihaloalkoxy, more preferably, trihalomethyl or trihalomethoxy; R
2
is C
1
-C
6
alkylthio, C
1
-C
6
alkylsulfinyl, C
1
-C
6
alkylsulfonyl, nitro(C
1
-C
4
alkoxy), hydroxy, di-(C
1
-C
4
alkoxy)-phosphinyl, cyano, C
2
-C
6
acyloxy, C
1
-C
6
alkoxy, C
1
-C
6
haloalkoxy, C
4
-C
6
cycloalkyl, or C
3
-C
6
alkenyl, phenyl, phenylthio, phenylsulfinyl, phenylsulfonyl, pyrazolyl, mono- or di-(C
1
-C
4
alkyl)-pyrazolyl, furanyl, (C
1
-C
4
alkyl)furanyl, thienyl, phenyl(C
1
-C
4
alkoxy), or benzoyloxy; and R
6
is hydrogen, C
1
-C
4
alkyl, C
1
-C
4
alkylthio, (C
1
-C
4
alkoxy)methyl or C
2
-C
8
acyl, more preferably, hydrogen, methyl, methylthio, methoxymethyl or acetyl.
The compounds and compositions of this invention are useful as plant protecting agents against insects and are particularly effective against coleopterous insects and lepidopterous insects, such as tobacco budworm.
The compounds of the instant invention can be prepared by reacting an oxadiazine of formula A below, wherein R, R
2
, R
3
, R
4
, R
5
, and X are as described above, with an isocyanate of formula B below, wherein R
1
is as described above, and a catalytic amount of triethylamine in a suitable solvent such as acetonitrile or toluene, to produce the compound of formula IB (the compounds of formula I in which R
6
is hydrogen).
The compounds of formula I in which R
6
is C
1
-C
6
alkyl, C
1
-C
4
alkylthio, (C
1
-C
4
alkoxy)C
1
-C
4
alkyl, C
2
-C
8
acyl, or benzyl, can be prepared by reacting the compound of formula IB with R
6
Y wherein Y is halogen and R
6
is C
1
-C
6
alkyl, C
1
-C
4
alkylthio, (C
1
-C
4
alkoxy)C
1
-C
4
alkyl, C
2
-C
8
acyl, or benzyl, with a suitable base such as triethylamine or sodium hydride.
Compounds of formula A above can be prepared by the cyclization of an azo compound (RCXN═NCO
2
C
2
H
5
) with an alkene of the formula:
wherein R, R
2
, R
3
, R
4
, R
5
, and X are as described above, followed by hydrolysis of the resultant intermediate.
The compounds of formula IA in which R
3
, R
4
, and R
5
are hydrogen; and R
2
is C
1
-C
6
alkylthio, C
1
-C
6
alkylsulfinyl, C
1
-C
6
alkylsulfonyl, nitro(C
1
-C
6
alkoxy), hydroxy, di-(C
1
-C
4
alkoxy)-phosphinyl, cyano, C
2
-C
6
acyloxy, C
1
-C
6
alkoxy, C
1
-C
6
haloalkoxy, C
4
-C
6
cycloalkyl, or C
3
-C
6
alkenyl; or R
2
is phenyl, phenylthio, phenylsulfinyl, phenylsulfonyl, pyrazolyl, furanyl, thienyl, phenyl(C
1
-C
6
alkoxy), or benzoyloxy, unsubstituted or mono-, di-, or tri-substituted with halogen, C
1
-C
4
alkyl, or C
1
-C
4
alkoxy, can be prepared by reacting an oxadiazine of formula C below, wherein R, R
1
, and R
6
are as described above, with a nucleophile R
2
H, wherein R
2
is as described above, and a Lewis acid such as boron trifluoride etherate in a suitable solvent such as dichloromethane or tetrahydrofuran to produce the compound of formula IA.
Compounds of formula (C) above can be prepared by the following scheme in which an oxadiazinone of formula (II) is reacted with an isocyanate of formula (III) and a catalytic amount of tributyltin diacetate in a solvent such as acetonitrile to give the intermediate (IV) which is further reacted with a reducing agent sodium borohydride to give the intermediate alcohol (V) which is further reacted with an acid chloride such as acetyl chloride to give the intermediate (C). The compounds of formula IA in which R
2
is hydroxy or acyloxy or aroyloxy are made at the intermediate stages shown in the scheme:
Some of the com

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