Plant protecting and regulating compositions – Plant growth regulating compositions – Organic active compound containing
Reexamination Certificate
2002-01-29
2002-12-03
Ramsuer, Robert W. (Department: 1626)
Plant protecting and regulating compositions
Plant growth regulating compositions
Organic active compound containing
C548S221000
Reexamination Certificate
active
06489268
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to high selective herbicidal phenoxypropionic acid alkoxycarbonyl anilid compounds represented in formula 1, method of preparing thereof, their use to control barnyard grass produced from rice, and a composition as suitable herbicides,
wherein
R is a hydrogen atom, methyl or ethyl group;
R
1
is a hydrogen atom, C
1
-C
6
alkyl, C
1
-C
6
alkyl substituted with 1 to 3 of the group consisting of hydroxy, carboxyl, and a halogen atom, C
3
-C
6
cycloalkyl, C
3
-C
4
alkenyl, C
3
-C
4
alkinyl, or C
2
-C
4
alkoxyalkyl group;
n is an integer of 1 or 2 and when n is 2, R
1
can be a combination of other substituents.
2. Description of the Prior Art
U.S. Pat. No. 4,130,413 disclosed the compound represented in the following formula 2,
wherein
(R
1
)
m
is a hydrogen atom, a halogen atom, CF
3
, NO
2
, CN or alkyl group;
A is O, S or NH;
R
2
is a hydrogen atom or alkyl group; and
Z is
(wherein R
3
and R
4
, that are the same or different, are a hydrogen atom, C
1
~C
6
alkyl, C
1
~C
6
hydroxyalkyl, C
3
~C
6
cycloalkyl, C
1
~C
4
alkoxy, or phenyl substituted with 1 to 3 substituents selected from the group consisting of C
1
~C
4
alkyl group, C
1
~C
6
alkoxy group, a halogen atom and CF
3
.
U.S. Pat. No. 4,531,969 disclosed the compounds represented in the following formula 3,
wherein R
5
is
(where R
6
is a hydrogen or a halogen atom, R
7
is a hydrogen atom or alkyl group); Z is the same as defined above.
U.S. Pat. No. 5,254,527 disclosed the compounds represented in the following formula 4,
wherein, R
5
and Z are the same as defined above.
Japanese Patent publication 2-11580 disclosed the compounds represented in the following formula 5,
wherein L is lower alkyl group, a halogen atom, methoxy, methoxyphenoxy, benzyloxy, methylthio, methylvinyl group; and n is an integer of 0 to 3.
U.S. Pat. No. 4,968,343 disclosed the compounds represented in the following formula 6.
Japanese Patent publication 53-40767 and 54-112828 also disclosed that phenoxypropionic acid amide derivatives show herbicidal activities.
However, none of the patents teaches the synthesis of the compound represented in the above formula 1 and has tested the same for herbicidal activity. Furthermore, it has not been reported that the compounds have superior herbicidal activity and selectivity toward rice and control barnyard grass produced from rice.
SUMMARY OF THE INVENTION
Even though many of herbicides for rice have been recently developed and used, barnyard grass among weeds is the biggest problem in rice paddy.
Development of herbicides to control barnyard grass is an urgent request to one who is in the field of agriculture. After transplanting young rice, conventional herbicides, developed until now, cannot effectively control the production of barnyard grass so that it causes a huge damage to harvest. It has been reported that when barnyard grass is produced for one week in 1 m
2
, amount of harvest decreases by 2%, for 5 weeks by about 10%, for 10 weeks by 19% and for 20 weeks by 35%.
Many herbicides have been used for the purpose of controlling barnyard grass that damages in huge amount of harvest of rice. However, the herbicide with a broader herbicidal activity, environmentally-friendly property and cost-effectiveness is still in demand.
The inventors have intensively studied to prepare herbicides to effectively control barnyard grass. As a result, we completed this invention to find a novel phenoxypropionic acid alkoxycarbonyl anilid and its derivatives that are stable to rice and selectively control barnyard grass. This superior effectiveness is distinguished from the conventional inventions.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is characterized by novel phenoxypropionic acid alkoxy-carbonyl anilid and its derivatives represented in formula 1 with an excellent herbicidal activity as well as selectively stable toward rice.
wherein, R, R
1
, and n are the same as previously defined.
The compounds of formula 1 according to the present invention may be specified as the following Table 1.
TABLE 1
(1)
Substituted
R
n
position of CO
2
R
1
R
1
H
1
3
H
H
1
3
CH
3
H
1
3
CH
2
CH
2
Cl
H
1
3
CH
2
CH
3
H
1
3
CH
2
CH
2
CH
3
H
1
3
CH(CH
3
)
2
H
1
3
(CH
2
)
3
CH
3
H
1
4
H
H
1
4
CH
3
H
1
4
CH
2
CH
3
H
1
4
CH
2
CH
2
Cl
H
1
4
CH
2
CH
2
CH
3
H
1
4
CH(CH
3
)
2
H
1
4
(CH
2
)
3
CH
3
H
1
2
H
H
1
2
CH
3
H
1
2
CH
2
CH
3
H
1
2
CH
2
CH
2
Cl
H
1
2
CH
2
CH
2
CH
3
H
1
2
CH(CH
3
)
2
H
1
2
(CH
2
)
3
CH
3
H
2
3, 4
CH
3
H
2
3, 4
CH
2
CH
3
H
2
2, 3
CH
3
CH
3
1
2
H
CH
3
1
2
CH
3
CH
3
1
3
H
CH
3
1
3
CH
3
CH
3
1
3
CH
2
CH
3
CH
3
1
3
CH
2
CH
2
Cl
CH
3
1
3
CH
2
CH
2
CH
3
CH
3
1
3
CH(CH
3
)
2
CH
3
1
3
(CH
2
)
3
CH
3
CH
2
CH
3
1
3
CH(CH
3
)
2
CH
3
1
4
H
CH
3
1
4
CH
3
CH
3
1
4
CH
2
CH
3
CH
3
1
4
CH
2
CH
2
CH
3
CH
3
1
4
(CH
2
)
3
CH
3
CH
3
1
4
CH(CH
3
)
2
CH
3
2
2, 3
CH
3
CH
3
2
2, 3
CH
2
CH
3
CH
3
2
3, 4
CH
3
CH
3
2
3, 4
CH
2
CH
3
H
1
3
cyclopropyl
H
1
4
cyclopropyl
H
1
3
cyclopropylmethyl
H
1
4
cyclopropylmethyl
H
1
3
cyclohexyl
H
1
3
CH
2
CH═CH
2
H
1
3
CH
2
—C≡CH
H
1
4
CH
2
CH═CH
2
H
1
4
CH
2
C≡CH
H
1
3
CH
2
CH
2
OCH
3
H
1
4
CH
2
CH
2
OCH
3
H
1
3
CH2CH
2
OH
H
1
4
CH2CH
2
OH
H
1
3
CH
2
CO
2
H
H
1
3
CH
2
CO
2
CH
3
H
1
4
CH
2
CO
2
H
H
1
4
CH
2
CO
2
CH
3
H
1
3
CH
2
CO
2
Et
H
1
4
CH
2
CO
2
Et
The compounds of formula 1 according to the present invention can be synthesized by a conventional method represented in the following scheme 1, reacting a compound of formula 7 with a compound of formula 8.
wherein X
1
, which is a leaving group, is OH, Cl, Br or phenoxy group; R, R
1
and n are the same as previously defined.
In the method according to scheme 1, condensation reaction can be performed by using binder such as triphenylphosphine or 1,3-cyclocarbodiimide and an organic base such as triethylamine or pyridine. It is prefer to carry this reaction at the temperature of 0-100° C. in an inert solvent such as ethers like tetrahydrofuran, ethyethyl acetate, acetonitrile, toluene, xylene, hexane, methylene chloride, carbon tetrachloride, dichloroethane or the like. The product is obtained by evaporating a solvent and performing column chromatograph.
Another method for preparing the compounds (1) represented in the following scheme 2 is an alkylation of a compound of formula 9 with compounds of formula 10.
wherein, X″, which is a leaving group, is Cl, Br, I, benzenesulfonyloxy, toluenesulfonyloxy, methanesulfonyloxy or lower alkyl sulfate group; R, R
1
and n are the same as previously defined.
In scheme 2, it is prefer to use a strong base which is enough to pull out a hydrogen from anilide, NH. The strong base used in this invention is NaOH, KOH, LiOH, NaH, n-BuLi or LDA. It is prefer to carry this reaction at the temperature of −78-50° C. in an inert solvent such as ethers like ethylether, dioxane or tetrahydrofuran or hydrocarbons like hexane.
Another method for preparing the compounds (1) represented in the following scheme 3 is a condensation reaction of a compound of formula 11 with a compound of formula 12 in the presence of a base.
wherein, Y′ is a halogen atom, alkylsulfonyloxy, haloalkylsulfonyloxy, benzenesulfonyloxy or toluenesulfonyloxy group; R, R
1
and n are the same as previously defined.
In Scheme 3, it is prefer to use alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate or potassium carbonate, alkali metal hydrogencarbonates such as sodium hydrogencarbonate or potassium hydrogencarbonzate or organic bases such as triethylamine, N,N-dimethylaniline, pyridine or 1,8-diazabicyclo[5,4,0]undec-7-ene.
A phase transition catalyst such as tetra-n-butylammonium bromide or 18-crown-6-[1,4,7,10,13,16-hexaoctacyclooctadecane] can be added to complete a reaction rapidly, if necessary. And also one or more than two solvents can be combined and used, if deemed necessary. It is prefer to use an inert organic solvent; for example; ketones such as acetone; aromatic hydrocarbons such as toluene, xylene
Chang Hae Sung
Kim Dae Whang
Kim Tae-Joon
Ko Young Kwan
Koo Dong Wan
Dongbu Hannong Chemical Co. Ltd.
Ramsuer Robert W.
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