Plant protecting and regulating compositions – Plant growth regulating compositions – Organic active compound containing
Reexamination Certificate
2000-10-06
2001-05-29
Lambkin, Deborah C. (Department: 1626)
Plant protecting and regulating compositions
Plant growth regulating compositions
Organic active compound containing
C514S378000, C548S240000
Reexamination Certificate
active
06239076
ABSTRACT:
This application is a 371 of PCT/KR00/00152 Feb. 24, 2000.
FIELD OF THE INVENTION
The present invention relates to novel 2-(5-isoxazolinylmethyloxyphenyl)-4,5,6,7-tetrahydro-2H-indazole derivatives of the following formula 1, their preparation method and their use as herbicides.
In the foregoing formula 1,
X represents a chlorine atom or a hydroxy group;
R represents an alkyl group of C
1
-C
5
, a substituted or unsubstituted phenyl group, a cyano group, a carboxyl group, a carboxyl ester group, or a substituted or unsubstituted heterocyclic ring; and
in case of a phenyl group or a heterocyclic ring being substituted, the phenyl group or the heterocyclic ring is optionally substituted by one or more identical or different substituents selected from the group consisting of alkyl groups of C
1
-C
3
, alkoxy groups of C
1
-C
3
, halogen atoms, cyano groups, nitro groups, carboxyl groups and carboxyl ester groups.
The compounds of the formula 1 have chiral centers and they can exist as enantiomers. All these separate individual isomers and their racemic mixtures are in the scope of the present invention.
DESCRIPTION OF THE RELATED ART
Some compounds containing an indazole group have been known to be useful for herbicides in the art. For example, U.S. Pat. No. 4,059,434, U.S. Pat. No. 4,124,374 and GB Pat. No. 2,127,410 A disclose 3-chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole, 3-chloro-2-(2,4-dichloro-5-methoxyphenyl)-4,5,6,7-tetrahydro-2H-indazole, 3-methyl-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole, 3-chloro-2-(4-chloro-5-propargyloxy-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole, etc. However, there has been a need for development in the herbicidal activity and selectivity.
We, the inventors of the present invention, have investigated the optimum structures of indazole derivatives in order to develop the herbicides for inhibiting growth of undesirable plants selectively in an established crop, and have synthesized the compounds of the formula 1 which has not been ever developed as a herbicide and have the improved herbicidal activity and selectivity.
SUMMARY OF THE INVENTION
The objective of the present invention is to provide novel 2-(5-isoxazolinylmethyloxyphenyl)-4,5,6,7-tetrahydro-2H-indazole derivatives of the formula 1.
Another objective of the present invention is to provide a preparation method of the said 2-(5-isoxazolinylmethyloxyphenyl)-4,5,6,7-tetrahydro-2H-indazole derivatives.
The further objective of the present invention is to provide herbicidal compositions comprising the said 2-(5-isoxazolinylmethyloxyphenyl)-4,5,6,7-tetrahydro-2H-indazole derivatives as an active ingredient.
The herbicidal compositions according to the present invention have a strong herbicidal activity against paddy weeds comprising ECHOR (
Echinochloa crus
-
galli
var. oryzicola; common name is barnyardgrass), SCPJU (
Scirpus juncoides
ROXB.; common name is bulrush), MOOVA (
Monochoria vaginalis
PRESL.; common name is monochoria), CYPSE (
Cyperus serotinus
ROTTB.; common name is flat-sedge), and SAGPY (
Sagittaria pygmaea
MIQ.; common name is arrow head) in rice.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to 2-(5-isoxazolinylmethyloxyphenyl)-4,5,6,7-tetrahydro-2H-indazole derivatives of the following formula 1.
In the foregoing formula 1,
X represents a chlorine atom or a hydroxy group;
R represents an alkyl group of C
1
-C
5
, a substituted or unsubstituted phenyl group, a cyano group, a carboxyl group, a carboxyl ester group, or a substituted or unsubstituted heterocyclic ring; and
in case of a phenyl group or a heterocyclic ring being substituted, the phenyl group or the heterocyclic ring is optionally substituted by one or more identical or different substituents selected from the group consisting of alkyl groups of C
1
-C
3
, alkoxy groups of C
1
-C
3
, halogen atoms, cyano groups, nitro groups, carboxyl groups and carboxyl ester groups.
The compounds of the formula 1 have chiral centers and they can be exist enantiomers. All these separate individual isomers and their racemic mixtures are in the scope of the present invention.
In the formula 1, preferably X is a chlorine atom. And R is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic ring or a cyano group.
The representative compounds of the present invention of the formula 1 are as followings:
1) 3-chloro-2-[4-chloro-5-(3-phenyl-5-methylisoxazolin-5-yl)methyloxy-2-fluorophenyl]-4,5,6,7-tetrahydro-2H-indazole (compound No. 1);
2) 3-chloro-2-[4-chloro-5-(3-(4-cyanophenyl)-5-methylisoxazolin-5-yl)methyloxy-2-fluorophenyl]-4,5,6,7-tetrahydro-2H-indazole (compound No. 2);
3) 3-chloro-2-[4-chloro-5-(3-(4-methylphenyl)-5-methylisoxazolin-5-yl)methyloxy-2-fluorophenyl]-4,5,6,7-tetrahydro-2H-indazole (compound No. 3);
4) 3-chloro-2-[4-chloro-5-(3-(2-fluorophenyl)-5-methylisoxazolin-5-yl)methyloxy-2-fluorophenyl]-4,5,6,7-tetrahydro-2H-indazole (compound No. 4);
5) 3-chloro-2-[4-chloro-5-(3-(2,4-dichlorophenyl)-5-methylisoxazolin-5-yl)methyloxy-2-fluorophenyl]-4,5,6,7-tetrahydro-2H-indazole (compound No. 5);
6) 3-chloro-2-[4-chloro-5-(3-(2-nitrophenyl)-5-methylisoxazolin-5-yl)methyloxy-2-fluorophenyl]-4,5,6,7-tetrahydro-2H-indazole (compound No. 6);
7) 3-chloro-2-[4-chloro-5-(3-(4-chloro-3-nitrophenyl)-5-methylisoxazolin-5-yl)methyloxy-2-fluorophenyl]-4,5,6,7-tetrahydro-2H-indazole (compound No. 7);
8) 3-chloro-2-[4-chloro-5-(3-cyano-5-methylisoxazolin-5-yl)methyloxy-2-fluorophenyl]-4,5,6,7-tetrahydro-2H-indazole (compound No. 8);
9) 3-chloro-2-[4-chloro-5-(3-(4-trifluoromethylphenyl)-5-methylisoxazolin-5-yl)methyloxy-2-fluorophenyl]-4,5,6,7-tetrahydro-2H-indazole (compound No. 9);
10) 3-chloro-2-[4-chloro-5-(3-(4-bromophenyl)-5-methylisoxazolin-5-yl)methyloxy-2-fluorophenyl]-4,5,6,7-tetrahydro-2H-indazole (compound No. 10);
11) 3-chloro-2-[4-chloro-5-(3-(4-methoxyphenyl)-5-methylisoxazolin-5-yl)methyloxy-2-fluorophenyl]-4,5,6,7-tetrahydro-2H-indazole (compound No. 11); and
12) 3-chloro-2-[4-chloro-5-(3-(2-chlorophenyl)-5-methylisoxazolin-5-yl)methyloxy-2-fluorophenyl]-4,5,6,7-tetrahydro-2H-indazole (compound No. 12).
In addition, the present invention provides a preparation method of 2-(5-isoxazolinylmethyloxy-phenyl)-4,5,6,7-tetrahydro-2H-indazole derivatives of the formula 1.
The preferred process is described hereinafter in detail.
2-(5-Isoxazolinylmethyloxyphenyl)-4,5,6,7-tetrahydro-2H-indazole derivatives of the formula 1 can be prepared by reacting the compound of formula (II) and nitrile oxide (or a precursor of nitrile oxide) by the 1,3-dipolar cycloaddition reaction (see Scheme 1).
Wherein, X and R are defined as the formula 1.
At this time, a variety of solvents may be used including dichloromethane, tetrahydrofuran, benzene, diethvl ether, alcohol of C
1
-C
4
, etc. Preferably anhydrous solvent may be used.
The compound of formula (II) can be prepared by reacting the compound of formula (III) and methallyl chloride or methallyl bromide in the presence of a base by the substitution reaction (see Scheme 2)
Wherein, X is defined as the formula 1 and Y is a halogen atom.
At this time, the base may be preferably used including sodium hydride, potassium carbonate, etc. A variety of solvents may be used including N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, acetone, etc. depending on the base.
The compound of formula (III) can be prepared by the method disclosed by GB Pat. No. 2,127,410 A, but should not be considered to be limited thereto. The compound of formula (III) can be synthesized by other methods.
The preparation method of compounds according to the present invention can be abstracted into the following steps:
1) reacting the compound of formula (III) and methallyl chloride or methallyl bromide in the presence of a base to give a compound of formula (II) by the substitution reaction (step 1); and
2) reacting the compound of formula (II) prepared in the step 1 and nitrile ox
Cho Kwang Yun
Jeon Dong Ju
Kim Hyoung Rae
Kim Kyoung Mahn
Lee Jung No
Bachman & LaPointe P.C.
D'Souza Andrea M.
Korea Research Institute of Chemical Technology
Lambkin Deborah C.
LandOfFree
Herbicidal 2-(5-isoxazolinyl... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Herbicidal 2-(5-isoxazolinyl..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Herbicidal 2-(5-isoxazolinyl... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2550492