Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reexamination Certificate
1999-10-22
2001-07-17
Morris, Patricia L. (Department: 1625)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
C548S267200, C548S267400, C548S267600, C548S267800, C548S268600, C548S269400
Reexamination Certificate
active
06262099
ABSTRACT:
FIELD OF THE INVENTION
This invention provides new compounds that are useful as insecticides and acaricides, new synthetic procedures and intermediates for preparing the compounds, pesticide compositions containing the compounds, and methods of controlling insects and mites using the compounds.
BACKGROUND OF THE INVENTION
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.
A number of 3,5-diphenyl-1H-1,2,4-triazole derivatives have been described in the literature as having acaricidal activity. U.S. Pat. No. 5,482,951; JP 8092224, EP572142, JP 08283261. To applicants knowledge, however, none of these compounds has become a commercial product. Nitro furanyl triazoles are described by L. E. Benjamin and H. R. Snyder as antimicrobials (
J. Heterocyclic Chem.
1976, 13, 1115) and by others as antibacterials (
J. Med. Chem.
1973, 16(4), 312-319;
J. Med. Chem.
1974, 17(7), 756-758). The present invention provides novel compounds with commercial level activity against mites and insects.
SUMMARY OF THE INVENTION
This invention provides novel compounds especially useful for the control of insects and mites.
More specifically, the invention provides novel insecticidally active compounds of the formula (1)
wherein
Ar is a group of the formula
wherein R
7
and R
8
are independently H, Cl, F, methyl, halomethyl, methoxy, or halomethoxy;
R
1
is lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, or benzyl;
R
2
is H, Cl, Br, lower alkyl, lower alkenyl, lower alkynyl, alkoxyalkyl;
R
3
is selected from H, halo, lower alkyl, (C
7
-C
21
) straight chain alkyl, hydroxy, lower alkoxy, haloalkyl, haloalkoxy, alkoxyalkyl, alkoxyalkoxy, lower alkenyl, haloalkenyl, CN, NO
2
, CON(R
6
)
2
, (C
3
-C
6
) cycloalkyl, S(O)
m
R
6
, SCN, pyridyl, substituted pyridyl, isoxazolyl, substituted isoxazolyl, naphthyl, substituted naphthyl, phenyl, substituted phenyl, —(CH
2
)
n
R
6
, —CH═CHR
6
, —C≡CR
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
,
provided one of R
2
and R
3
is other than H;
R
4
, R
5
, and R
5
′ are independently H, halo, lower alkyl, lower alkoxy, haloalkyl, haloalkoxy, CN, CO
2
R
6
, CON(R
6
)
2
, or S(O)
m
alkyl, or
R
4
and R
5
, or R
2
and R
5
form a 5 or 6 member saturated or unsaturated carbocyclic ring which may be substituted by 1 or 2 halo, lower alkyl, lower alkoxy or haloalkyl groups; or
R
6
is H, lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, phenyl, or substituted phenyl;
m is 0, 1, or 2; and
n is 1 or 2;
p is an integer from 2 to 6;
or a phytologically acceptable acid addition salt thereof.
Preferred compounds of formula (1) include the following classes:
(1) Compounds of formula (1) wherein R
7
and R
8
are independently F or Cl.
(2) Compounds of formula (1) wherein R
7
and R
8
are both F.
(3) Compounds of formula (1) wherein R
7
and R
8
are both Cl.
(4) Compounds of formula (1) wherein R
7
is F and R
8
is Cl.
(5) Compounds of formula (1), and particularly compounds of class (1), (2), (3), or (4) as defined above, wherein R
2
is H, CH
3
, Br, or substituted phenyl.
(6) Compounds of class (5) wherein R
2
is CH
3
.
(7) Compounds of formula (1), and particularly compounds of any one of classes (1) through (6) defined above, wherein R
3
, R
4
, and R
5
are independently selected from H, halo, methyl, and methoxy.
(8) Compounds of formula (1), and particularly compounds of any one of classes (1) through (7) as defined above, wherein R
5
and R
5
′ are both H.
(9) Compounds of formula (1) wherein R
2
is CH
3
, R
3
and R
4
are Cl, and R
5
and R
5
′ are H.
The invention also provides new processes and intermediates for preparing compounds of formula (1) 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.
The term “lower alkyl” refers to (C
1
-C
6
) straight hydrocarbon chains and (C
3
-C
6
) branched and cyclic hydrocarbon groups.
The terms “lower alkenyl” and “lower alkynyl” refer to (C
2
-C
6
) straight hydrocarbon chains and (C
3
-C
6
) branched hydrocarbon groups containing at least one double or triple bond, respectively.
The term “lower alkoxy” refers to -O-lower alkyl.
The terms “halomethyl”, “haloalkyl”, and “haloalkenyl” refer to methyl, lower alkyl, and lower alkenyl groups substituted with one or more halo atoms.
The terms “halomethoxy” and “haloalkoxy” refer to methoxy and lower alkoxy groups substituted with one or more halo atoms.
The term “alkoxyalkyl” refers to a lower alkyl group substituted with a lower alkoxy group.
The term “alkoxyalkoxy” refers to a lower alkoxy group substituted with a lower alkoxy group.
The terms “substituted naphthyl”, “substituted thienyl,” “substituted pyrimidyl,” “substituted pyrazolyl,” “substituted pyridyl,” and “substituted isoxaxolyl” refer to the ring system substituted with one or more groups independently selected from halo, halo (C
1
-C
4
) alkyl, CN, NO
2
, (C
1
-C
4
) alkyl, (C
3
-C
4
) branched alkyl, phenyl, (C
1
-C
4
) alkoxy, or halo (C
1
-C
4
) alkoxy.
The term “substituted phenyl” refers to a phenyl group substituted with one or more groups independently selected from halo, (C
1
-C
10
) alkyl, branched (C
3
-C
6
) alkyl, halo (C
1
-C
7
) alkyl, hydroxy (C
1
-C
7
) alkyl, (C
1
-C
7
) alkoxy, halo (C
1
-C
7
) alkoxy, 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.
Synthesis
Compounds of formula (1) can be prepared by the method illustrated in Scheme I:
wherein Ar and R
1
through R
5
′ are as defined in formula (1) above. The sequence shown in Scheme 1 involves the coupling of cyclopropyl acid chlorides of formula (2) with the amidrazone of formula (3). Preparation 1, hereinafter, illustrates preparation of an amidrazone of formula (3). The base used in the coupling could be any organic or inorganic base. Cyclopropyl acid chlorides of formula (2) are prepared from corresponding cyclopropyl carboxylic acids of formula (5)
which are either commercially available or are readily made through known procedures. A good general method is the dihalocarbene insertion into activated olefins as outlined in Acta.
Chem. Scandinavica
B31, (1977) 823-825 and
Chem. Ber.
109, 2351-2369 1976. Conversion of carboxylic acids of formula (5) to the corresponding acid chlorides of formula (2) is carried out by conventional methods, as illustrated hereinafter in Preparation 3. Intermediates of formula (4) can be isolated or not and the entire sequence can be done in one pot as seen in Example 1, hereinafter.
Preparation 1
The following steps illustrate preparation of the amidrazone of formula (3a)
A. 2,6-difluorobenzenethioamide
Into a 3 L three necked round bottom flask equipped with a mechanical stirrer, dry ice condenser, dropping funnel, and outlet to a trap filled with bleach was added pyridine (550 mL), 2,6-difluorobenzonitrile (208 g, 1.50 mol), triethylamine (202 g, 279 mL, 2.0 mol), and sodium sulfide hydrate (521 g, 2.17 mol) broken into pieces small enough to fit into the flask. The temperature of the stirred mixture was lowered to approximately 5° C. and to t
Ash Mary L.
DeVries Donald H.
Dintenfass Leonard P.
Gifford James M.
Martin Timothy P.
Dow AgroSciences LLC
Mixan Craig E.
Morris Patricia L.
Stuart Donald R.
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