Herbicidal benzoyloxy carboxylates and carboxamides

Details Herbicidal benzoyloxy carboxylates and carboxamides Herbicidal benzoyloxy carboxylates and carboxamides

2000-04-18

2001-06-26

Raymond, Richard L. (Department: 1624)

Plant protecting and regulating compositions

Plant growth regulating compositions

Organic active compound containing

C504S227000, C504S229000, C504S238000, C504S246000, C504S248000, C504S265000, C504S270000, C504S273000, C504S280000, C504S282000, C504S286000, C504S304000, C504S315000, C544S182000, C544S223000, C544S235000, C544S236000, C544S239000, C544S314000, C546S119000, C546S121000, C546S220000, C548S144000, C548S226000, C548S263200, C548S370100, C548S375100, C548S376100, C548S476000

Reexamination Certificate

active

06251829

ABSTRACT:

This invention relates to herbicidal alpha-benzoyloxy-alpha-beta-, and/or beta-gamma-unsaturated-carboxylates and their derivatives, to compositions which contain these compounds, and to methods of use of these compounds.
The presence of unwanted plant species causes substantial damage to useful crops. Prevention or minimizing the loss of a portion of such valuable crops by killing or inhibiting the growth of unwanted weeds is one way of improving this efficiency. Though many herbicides are available, the need still exists for more effective herbicides.
Alpha-beta- and beta-gamma-unsaturated carboxylic acids and their derivatives are known as agricultural herbicides (see U.S. Pat. No. 4,902,334). We have discovered that certain alpha-(2,4,5-trisubstituted)- and alpha-(2, 5-disubstituted)-benzoyloxy-alpha-beta- and/or beta-gamma-unsaturated carboxylic acids and their derivatives provide superior efficacy as herbicides compared to compounds disclosed in U.S. Pat. No. 4,902,334.
The present invention, therefore, relates to such alpha-(2,4,5-trisubstituted)- and alpha-(2,5-disubstituted)-benzoyloxy-alpha-beta- and/or beta-gamma-unsaturated-carboxylates, their isomers, and agronomically acceptable salts.
We have discovered that compounds represented by formulae I and II, and their agronomically acceptable salts, are surprisingly effective as pre-emergent and post-emergent herbicides:
wherein
R
1
, R
2
, R
3
, R
4
, and R
5
are independently hydrogen,(C
1
-C
12
)alkyl, (C
1
-C
12
)haloalkyl, (C
3
-C
8
)cycloalkyl, (C
2
-C
8
)alkenyl, (C
3
-C
10
)alkynyl, (C
1
-C
4
)alkoxyalkyl, (C
3
-C
8
)cycloalkoxy(C
1
-C
4
)alkyl, (C
2
-C
8
)alkenyloxy(C
1
-C
4
)alkyl, (C
3
-C
10
)alkynyloxy(C
1
-C
4
)alkyl, (C
1
-C
12
)alkylcarbonyl, (C
1
-C
4
)alkoxycarbonyl, (C
2
-C
8
)alkenyloxycarbonyl, cyano, (C
1
-C
10
)alkoxy, (C
3
-C
8
)cycloalkoxy, (C
2
-C
8
)alkenyloxy, (C
3
-C
10
)alkynyloxy, dialkylamino, (C
1
-C
12
)alkylsulfonyl, or substituted or unsubstituted phenyl, wherein the substituents are from one to three independently selected from the group consisting of halogen, cyano, nitro, trihalomethyl, and methyl. Preferably, R
1
, R
2
, R
3
, R
4
, and R
5
are independently selected from hydrogen, (C
1
-C
6
)alkyl, (C
1
-C
4
)haloalkyl, (C
4
-C
5
) cyclalkyl, (C
2
-C
5
)alkenyl, (C
3
-C
6
)alkynyl, (C
1
-C
3
)alkoxy(C
1
-C
2
)alkyl, (C
4
-C6)cycloalkoxy(C
1
-C
2
)alkyl, (C
2
-C
5
)alkenyloxy(C
1
-C
2
)alkyl, (C
3
-C
6
)alkynyloxy(C
1
-C
2
)alkyl, (C
1
-C
6
)alkylcarbonyl, (C
1
-C
4
)alkoxycarbonyl, (C
2
-C
5
)alkenyloxycarbonyl, cyano, (C
1
-C
6
)alkoxy, (C
4
-C
6
)cycloalkoxy, (C
2
-C
5
)alkenyloxy, (C
3
-C
6
)alkynyloxy, dialkylamino, (C
1
-C
6
)alkylsulfonyl or substituted or unsubstituted phenyl. More preferably, R
1
, R
2
, R
3
, R
4
, and R5 are independently selected from hydrogen, methyl, and substituted or unsubstituted phenyl, wherein the substituents are independently halogen, trihalomethyl, or methyl;
R
6
is OR
7
or NR
8
R
9
, in which R
7
is (C
1
-C
12
)alkyl, (C
2
-C
12
)alkenyl, (C
3
-C
12
)alkynyl or aryl and R
8
and R
9
are the same or different and are hydrogen, (C
1
-C
12
)alkyl or aryl; Preferably, R
6
is OEt or O-allyl.
X
1
is halo, or nitro. Preferably X
1
is chlorine, fluorine, or nitro.
X
2
is hydrogen, halo, halo(C
1
-C
6
)alkyl, cyano, or nitro. Preferably X
2
is fluorine, chlorine, trifluoromethyl, or cyano.
X
3
is halo, (C
1
-C
12
)alkyl, halo(C
1
-C
12
)alkyl, (C
1
-C
10
)alkoxy, (C
3
-C
8
)cycloalkoxy, (C
2
-C
8
)alkenyloxy, (C
3
-C
10
)alkynyloxy, (C
1
-C
4
)alkoxycarbonyl, (C
2
-C
8
)alkenyloxycarbonyl, (C
3
-C
10
)alkynyloxycarbonyl, (C
1
-C
12
)alkylsulfonylamino, (C
1
-C
12
)alkylsulfonylalkylamino, (C
1
-C
4
)alkoxycarbonylmethoxy, (C
1
-C
4
)alkoxycarbonylethoxy, aryloxy, or Q, wherein Q is:
wherein W is O or S. Preferably, X
3
is cyclopentyloxy, 2-propynyloxy, methylsulfonylamino, methylsulfonylmethylamino, 2,4-dichlorophenoxy, 2-chloro-4-trifluromethylphenoxy, 4-trifluromethyl-2-pyridinyloxy, Q
1
, or Q
13
. R
10
is NH
2
, OH, (C
1
-C
10
)alkyl or substituted alkyl. Preferably, R
10
is NH
2
, OH, or methyl.
The term “alkyl” includes both branched and straight chain alkyl groups such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, isooctyl, nonyl, decyl, undecyl, and dodecyl. The term “cycloalkyl” refers to a cyclic aliphatic ring structure such as, for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. The term “haloalkyl” refers to an alkyl group substituted with one or more halo groups. The term “halo” refers to fluoro, chloro, bromo or iodo.
The term “alkylsulfonylalkyl” refers to an alkyl group substituted with an alkylsulfonyl (alkyl-SO
2
) group such as, for example, methylsulfonylmethyl. The term “alkylsulfinylalkyl” refers to an alkyl group substituted with an alkylsulfinyl (alkyl-SO) group such as, for example, methylsulfinylmethyl.
The term “alkenyl” refers to an ethylenically unsaturated hydrocarbon group, straight or branched, having 1 or 2 ethylenic bonds. The term “haloalkenyl” refers to an alkenyl group substituted with one or more halo groups. The term “alkynyl” refers to an unsaturated hydrocarbon group, straight or branched, having 1 or 2 acetylenic bonds.
The term “alkoxy” includes both branched and straight chain alkyl groups attached to a terminal oxygen atom. Typical alkoxy groups include, for example, methoxy, ethoxy, n-propoxy, isopropoxy, and tert-butoxy. The term “haloalkoxy” refers to an alkoxy group substituted with one or more halo groups.
The term “alkylthio” includes both branched and straight chain alkyl groups attached to a terminal sulfur atom. The term “haloalkylthio” refers to an alkylthio group substituted with one or more halo groups.
The term “aryloxy” includes phenoxy and pyridinyloxy, which may be substituted with up to three substituents selected from the group consisting of halogen, cyano, nitro, trihalomethyl, and methyl. Typical aryloxy includes, for example, 4-chlorophenoxy, 2-chlorophenoxy, 3,5-dichlorophenoxy, 2,6-dichlorophenoxy, 4-trifluoromethylphenoxy, 2-chloro-4-trifluoromethylphenoxy, 2,4,6-trichlorophenoxy, 4-trifluoromethyl-2-pyridinyloxy.
For purposes of this invention, unless otherwise specified, all percentages, parts, and ratios are by weight and all ranges are inclusive and combinable.
Agronomically acceptable salts may be formed by complexation of the compounds of the current invention with metal salts such as zinc chloride or iron chloride.
Compounds of Formula I may be prepared by reacting a compound of Formula III and a compound of Formula IV in the presence of a base in a suitable solvent at a temperature between 0 to 100° C. for 0.5 to 48 hours.
Compounds of Formula III are commercially available or can be readily prepared from benzoic acids which are commercially available or can be prepared by using known methods. Compounds of Formula IV may be prepared according to known methods (such as that in
J. Chem. Soc., Perkin Trans
. 1, (7), 1249 (1998) and
Tetrahedron Letters
, 38(34), 5917 (1997)).
Compounds of Formula II can be prepared by treating compounds of Formula I with an catalysis, such as p-toluenesulfonic acid, in a suitable solvent as depicted in the following scheme:
Alternatively, compounds of Formula II may be directly prepared from a benzoic acid chloride of Formula III by treating with compounds of Formula V in the presence of a base in a suitable solvent as depicted in the following scheme:
Compounds of Formula V are either commercially available or can be prepared according to known methods.
Certain compounds of Formula I may be prepared from other compounds of Formula I. For example, when X
3
is NO
2
(Formula VI), those compounds can be converted to compounds of Formula I in which X
3
is NH
2
(Formula VII) by using a reducing agent.
In a similar manner, certain compounds of Formula II may be prepared by the chemical reaction from compounds of Formula II to other compounds of Formula II.
Occasionally, certain compounds of

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