2-(2,6-disubstituted phenyl)-4-aryl-5-alkyl-1,3-oxazoline...

Details 2-(2,6-disubstituted phenyl)-4-aryl-5-alkyl-1,3-oxazoline... 2-(2,6-disubstituted phenyl)-4-aryl-5-alkyl-1,3-oxazoline...

2002-06-21

2003-06-03

Chang, Ceila (Department: 1626)

Drug, bio-affecting and body treating compositions

Designated organic active ingredient containing

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

C546S271400, C548S237000

Reexamination Certificate

active

06573286

ABSTRACT:

BACKGROUND OF THE INVENTION
This invention concerns new oxazolines that are useful as insecticides and acaricides. More particularly, the present invention concerns 2-(2,6-disubstituted phenyl)-4-aryl-5-alkyl-1,3-oxazoline compounds and their stereoisomers. This invention also includes new synthetic procedures and intermediates for preparing the compounds, pesticide compositions containing the compounds, and methods of controlling insects and mites using the compounds.
There is an acute need for new insecticides and acaricides. Insects and mites are developing resistance to the insecticides and acaricides in current use. At least 400 species of arthropods are resistant to one or more insecticides. The development of resistance to some of the older insecticides, such as DDT, the carbamates, and the organophosphates, is well known. But resistance has even developed to some of the newer pyrethroid insecticides and acaricides. Therefore a need exists for new insecticides and acaricides, and particularly for compounds that have new or atypical modes of action.
2-(Substituted-phenyl)-1,3-oxazolines with insecticidal activity are disclosed in JP 4-89484, EP 0345775-A1, EP 0432661-A2, EP 0553623-A1, WO 99/01443, WO 99/23081 and WO 98/47881. 2-Aryl- and 2-heteroaryl-1,3-oxazolines with acaricidal and insecticidal activity are disclosed in JP 6-145169 and WO 99/65901. Arthropocidal 2-(substituted-phenyl)-1,3-oxazolines are disclosed in WO 93/24470. To the applicants' knowledge, only one oxazoline product, etoxazole, has been developed as a commercial acaricide. It would be highly desirable to discover related compounds of this mode of action that are more potent, more selective or of broader spectrum in their activity and/or that have improved toxicological and environmental properties.
SUMMARY OF THE INVENTION
This invention provides novel 2-(2,6-disubstituted phenyl)-4-aryl-5-alkyl-1,3-oxazoline derivatives especially useful for the control of insects and mites.
More specifically, the invention provides novel insecticidally active compounds of the formula (I)
wherein
R
1
is (C
1
-C
3
) alkyl or (C
1
-C
3
) haloalkyl;
R
2
and R
3
are independently H, halogen, (C
1
-C
3
) alkyl, (C
1
-C
3
) haloalkyl, (C
1
-C
3
) alkoxy or (C
1
-C
3
) haloalkoxy;
Q is a group selected from
R
4
is H, halogen, hydroxy, (C
1
-C
6
) alkyl, (C
1
-C
6
) alkoxy, (C
1
-C
6
) haloalkyl, (C
1
-C
6
) haloalkoxy, (C
1
-C
6
) alkoxyalkyl, (C
1
-C
6
) alkoxyalkoxy, (C
2
-C
6
) alkenyl, (C
2
-C
6
) haloalkenyl, CN, NO
2
, CO
2
R
6
, CON(R
6
)
2
, S(O)
m
R
6
, SCN, —CH
2
OR
6
, —CH
2
SR
6
, —CH
2
NR
6
R
6
, —OCH
2
R
6
, —SCH
2
R
6
, —NR
6
CH
2
R
6
,
R
5
represents
R
6
is H, (C
1
-C
6
) alkyl, (C
1
-C
6
) haloalkyl, (C
2
-C
6
) alkenyl, (C
2
-C
6
) alkynyl, phenyl, or substituted phenyl;
R
7
and R
8
are independently H, halo, (C
1
-C
6
) alkyl, (C
1
-C
6
) haloalkyl, (C
1
-C
6
) alkoxy or (C
1
-C
6
) haloalkoxy;
X and Y are independently Cl, F, methyl, halomethyl, methoxy, or halomethoxy;
m is 0, 1, or 2; and
Z is a direct bond, CH
2
, CH
2
CH
2
, O or S
or a phytologically acceptable acid addition salt or N-oxide thereof.
Preferred compounds of formula (I) include the following classes:
(1) Compounds of formula (I) wherein X and Y are both halogen.
(2) Compounds of class (1) wherein X and Y are both F.
(3) Compounds of formula (I) wherein R
2
and R
3
are H.
(4) Compounds of formula (I) wherein R
4
is H, halogen, (C
1
-C
6
) alkyl, (C
1
-C
6
) haloalkyl, (C
1
-C
6
) alkoxy or (C
1
-C
6
) haloalkoxy.
(5) Compounds of formula (I) wherein Q is
(6) Compounds of class (5) wherein R
5
is
(7) Compounds of formula (I), and particularly compounds of class (6) as defined above, wherein Z is a direct bond.
(8) Compounds of formula (I) wherein R
1
is methyl.
It will be appreciated by those skilled in the art that the most preferred compounds are generally those which are comprised of various combinations of the above preferred classes.
Particularly preferred compounds are of formula (Ia)
The invention also provides new processes and intermediates for preparing compounds of formula (I) as well as new compositions and methods of use, which will be described in detail hereinafter.
DETAILED DESCRIPTION OF THE INVENTION
Throughout this document, all temperatures are given in degrees Celsius, and all percentages are weight percentages unless otherwise stated.
Unless specifically limited otherwise, the terms “alkyl”, “alkenyl” and “alkynyl”, as well as derivative terms such as “alkoxy” and “alkanoyl”, as used herein, include within their scope straight chain, branched chain and cyclic moieties. The terms “alkenyl” and “alkynyl” are intended to include one or more unsaturated bonds.
Unless specifically limited otherwise, the term “halogen”, as well as derivative terms such as “halo”, as used herein, refer to fluorine, chlorine, bromine, and iodine. Preferred halogens are fluorine and chlorine.
The terms “halomethyl”, “haloalkyl”, and “haloalkenyl” refer to methyl, alkyl, and alkenyl groups substituted with from one up to the maximum possible number of halo atoms. The terms “halomethoxy” and “haloalkoxy” refer to methoxy and alkoxy groups substituted with from one up to the maximum possible number of halo atoms.
The terms “substituted pyridyl,” “substituted isoxazolyl,” “substituted thienyl,” and “substituted thiazolyl” refer to the ring system substituted with one or more groups independently selected from halo, (C
1
-C
4
) alkyl, (C
1
-C
4
) haloalkyl, CN, NO
2
, phenyl, (C
1
-C
4
) alkoxy, or (C
1
-C
4
) haloalkoxy.
The term “substituted phenyl” refers to a phenyl group substituted with one or more groups independently selected from halo, (C
1
-C
10
) alkyl, (C
1
-C
7
) haloalkyl, (C
1
-C
7
) hydroxyalkyl, (C
1
-C
7
) alkoxy, (C
1
-C
7
) haloalkoxy, phenoxy, phenyl, NO
2
, OH, CN, (C
1
-C
4
) alkanoyl, benzoyl, (C
1
-C
4
) alkanoyloxy, (C
1
-C
4
) alkoxycarbonyl, phenoxycarbonyl, or benzoyloxy.
Unless otherwise indicated, when it is stated that a group may be substituted with one or more substituents selected from an identified class, it is intended that the substituents may be independently selected from the class, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied.
Relative to the oxazoline ring, the compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include geometric isomers, diastereomers and enantiomers. Thus the compounds of the present invention include racemic mixtures, individual stereoisomers and optically active mixtures. For example, for compounds of the formula (Ia)
the following stereoisomers are possible:
It will be appreciated by those skilled in the art that one stereoisomer may be more active than the others. Individual stereoisomers and optically active mixtures may be obtained by selective synthetic procedures, by conventional synthetic procedures using resolved starting materials or by conventional resolution procedures.
Synthesis
Compounds of formula (I), in particular diastereomers Syn (I) and Anti (I) can be prepared by the method illustrated in Scheme A:
wherein R
1
, Q, X and Y are as defined in formula (I).
In step a of Scheme A, the compound of formula (A) is reacted with an aminoalcohol (D) to afford a compound of formula (C). 1,2-Dichloroethane is the preferred solvent, however other polar aprotic solvents such as pyridine or THF can also be used.
In step b of Scheme A the N-amidealcohol of formula (C) can be reacted with either (diethylamino)sulfur trifluoride (DAST) or with thionyl chloride to provide the products of formula Syn (I) and Anti (I) which can be separated using chromatographic techniques. The DAST reaction is carried out in dichloromethane or 1,2-dichloroethane at a temperature in the range from −78° C. to ambient temperature. The thionyl chloride reaction is carried out in dichloromethane or 1,2-dichloroethane at a temperature in the range from 0° C. to ambient temperature.
Alternatively, when Q represents
compounds of formula (I), in particula

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