Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-04-13
2002-07-09
McKane, Joseph K. (Department: 1626)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Heterocyclic carbon compounds containing a hetero ring...
C548S266200, C548S110000, C514S340000, C514S383000, C546S272400, C544S112000
Reexamination Certificate
active
06417187
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). 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;
J Med. Chem.
1974, 17(7), 756). The present invention provides novel compounds with broad spectrum 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 phenyl, substituted phenyl, pyridyl, substituted pyridyl, or lower alkyl;
R
1
is lower alkyl, cycloalkyl, phenyl, or substituted phenyl;
Q is thienyl, substituted thienyl, phenyl, substituted phenyl, pyridyl, or substituted pyridyl;
R
2
is selected from H, lower alkyl, lower alkenyl, pyridyl, substituted pyridyl, pyrimidyl, substituted pyrimidyl, isoxazolyl, substituted isoxazolyl, naphthyl, substituted naphthyl, phenyl, substituted phenyl, thienyl, substituted thienyl, —(CH
2
)
m
R
3
, —CH═CHR
3
, —C≡CR
3
, —CH
2
OR
3
, —CH
2
SR
3
, —CH
2
NR
3
R
3
, —OCH
2
R
3
, —SCH
2
R
3
,—
R
3
is H, lower alkyl, haloalkyl, lower alkenyl, lower alkynyl, phenyl, or substituted phenyl;
m is 1 or2;
n 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 Ar is a group of the formula
wherein R
4
and R
5
are independently H, Cl, F, methyl, halomethyl, methoxy, or halomethoxy.
(2) Compounds of formula (1) wherein Ar is a group of the formula
wherein R
4
and R
5
are independently H, Cl, F, methyl, halomethyl, methoxy, or halomethoxy.
(3) Compounds of class (1) and (2) wherein R
4
and R
5
are independently F or Cl.
(4) Compounds of class (1) and (2) wherein R
4
and R
5
are both F.
(5) Compounds of class (1) and (2) wherein R
4
and R
5
are both Cl.
(6) Compounds of class (1) and (2) wherein R
4
is F and R
5
is Cl.
(7) Compounds of formula (1), and particularly compounds of class (1), (2), (3), (4), (5) or (6) as defined above, wherein Q is a substituted thiophene.
(8) Compounds of formula (1), and particularly compounds of class (1), (2), (3), (4), (5) or (6) as defined above, wherein Q is a substituted phenyl.
(9) Compounds of formula (1), and particularly compounds of any one of classes (1) through (8) as defined above, wherein R
2
is methyl.
(10) Compounds of formula (1), and particularly compounds of any one of classes (1) through (9) as defined above, wherein R
2
is a phenyl or substituted phenyl.
(11) Compounds of formula (1), and particularly compounds of any one of classes (1) through (9) as defined above, wherein R
2
is a thiophene or substituted thiophene.
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 isoxazolyl” 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 methods illustrated in Scheme 1:
wherein Ar is phenyl or substituted phenyl, Q, and R
2
are defined as in formula (1) above. The sequence shown in Scheme 1 involves the coupling of 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. Acid chlorides of formula (2) are prepared from corresponding carboxylic acids of formula (11)
which are either commercially available or are readily made through known procedures. Examples 1 and 2, hereinafter, illustrate the coupling and cyclization utilizing the amidrazone of formula (3) to produce a triazole product of formula (1).
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 the slurry was added dropwise concentrated hydrochloric acid (143 g, 288 mL, 3.99 mol). An exotherm was noted and the rate of addition of the hydrochloric acid was such that the temperature of the reaction mixture did not exceed 25° C. for a total addition time of 75 min. The cooling bath was removed and the slurry was allowed to warm to RT and to stir over night. The mixture was poured into water (2 L) and was extracted with ether (3×500 mL). The ether layer was washed with dilute sulfuric acid, water, brine, dried (MgSO
4
), and the solvent removed in vacuo to give 232 gram
Bis Scott Jerome
Hamilton Christopher Thomas
Hegde Vidyadhar Babu
Heo Emilie Chassat
Johnson Peter Lee
Corvin Carl D.
McKane Joseph K.
Saeed Kamal
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