Plant protecting and regulating compositions – Plant growth regulating compositions – Organic active compound containing
Reexamination Certificate
2001-02-20
2002-11-26
Solola, T. A. (Department: 1626)
Plant protecting and regulating compositions
Plant growth regulating compositions
Organic active compound containing
C548S221000
Reexamination Certificate
active
06486098
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel herbicidal phenoxypropionic acid N-alkyl-N-2-fluorophenyl amide compounds represented in the following formula (1), a method for preparing thereof, their use to control barnyard grass produced from rice and composition as suitable herbicides.
wherein,
R is methyl or ethyl group;
X is hydrogen, halogen, cyano, C
1
~C
6
alkyl, C
1
~C
6
alkoxy, C
1
~C
3
haloalkyl substituted with 1 to 3 of halogen atom(s), C
1
~C
3
haloalkoxy substituted with 1 to 3 of halogen atom(s), C
2
~C
4
alkoxyalkoxy, phenoxy, benzyloxy, C
2
~C
6
alkenyl, C
2
~C
6
alkinyl, C
2
~C
6
alkenyloxy, C
2
~C
6
alkinyloxy, or phenyl group;
Y is hydrogen or fluoro;
n is an integer of 1 or 2 and when n is 2, X can be in a combination of other substituents.
2. Description of the Prior Art
U.S. Pat. No. 4,130,413 discloses the compound containing the following formula (2).
wherein, (R
1
)
m
is hydrogen, halogen, CF
3
, NO
2
, CN or alkyl group; A is O, S or NH; R
2
is hydrogen or alkyl group; Z is
where R
3
and R
4
, that are the same or different, are hydrogen, C
1
~C
6
alkyl, C
3
~C
6
hydroxyalkyl, C
3
~C
6
cycloalkyl, C
1
~C
4
alkoxy, or phenyl substituted where 1 to 3 substituents are selected from C
1
~C
4
alkyl group, C
1
~C
6
alkoxy group, halogen and CF
3
U.S. Pat. No. 4,531,969 discloses the compounds containing the following formula (3).
wherein, R
5
is
where R
6
is hydrogen or halogen atom, R
7
is hydrogen or alkyl group); Z is the same as defined above.
U.S. Pat. No. 5,254,527 discloses the compounds containing the following formula (4).
wherein, R
5
and Z are the same as defined above.
None of the patents teaches the synthesis of the compound represented in the above formula (1) and have tested the same for herbicidal activity.
JP Patent publication 2-11580 discloses the compound represented in the following formula (5).
wherein, L is lower alkyl, halogen, methoxy, methoxyphenoxy, methylthio or methylvinyl group; n is an integer of 0 to 2.
JP Patent publication sho 53-40767 and sho 54-112828 also disclose that phenoxypropionic acid amide derivatives have herbicidal activity.
However, none of reports including the patents mentioned above has taught a method for preparing the compounds in the above formula (1) and tested the same against herbicidal activity. And also 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 to one who is in the field of agriculture. After transplanting young rice, 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 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, they completed this invention to find a novel phenoxypropionic acid N-alkyl-N-2-fluorophenyl amide 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 N-alkyl-N-2-fluorophenyl amide represented in the following formula (1) with an excellent herbicidal activity as well as selectively stable toward rice.
wherein, R, X, Y and n are the same as previously defined.
The compounds of the formula (1) according to the present invention may be specified as the following Table 1.
TABLE 1
(1)
R
Y
X
CH
3
H
H
CH
2
CH
3
H
H
CH
3
H
4-CN
CH
3
H
4-F
CH
3
H
3-F
CH
3
H
5-F
CH
3
H
4-Cl
CH
3
H
4,5-F
2
CH
3
H
4-Br
CH
3
H
4-phenyl
CH
3
H
4-CH
3
CH
3
H
3-Br
CH
3
H
4-CH
2
CH
3
CH
3
H
4-propyl
CH
3
H
4-isopropyl
CH
3
H
4-cyclopropyl
CH
3
H
4-butyl
CH
3
H
4-isobutyl
CH
3
H
3-CN
CH
3
H
4-OCH
3
CH
3
H
4-O-phenyl
CH
3
H
4-OEt
CH
3
H
4-O-isopropyl
CH
3
H
4-O-allyl
CH
3
H
4-O-propyl
CH
3
F
H
CH
3
F
3-F
CH
3
F
4-F
CH
2
CH
3
F
4-F
CH
3
F
4-Cl
CH
3
F
4-Br
CH
3
F
4-CH
3
CH
3
F
4-CH
2
CH
3
CH
3
F
4-propyl
CH
3
F
4-isopropyl
CH
3
F
4-cyclopropyl
CH
3
F
4-butyl
CH
3
F
4-isobutyl
CH
3
F
4-OCH
3
CH
3
F
4-OEt
CH
3
F
4-O-isopropyl
CH
3
F
4-O-propyl
CH
3
H
3,5-F
2
CH
3
H
5-F
CH
3
H
5-Cl
CH
3
H
5-Br
CH
3
H
5-CN
CH
3
H
5-CH
3
CH
3
H
5-CH
2
CH
3
CH
3
H
5-phenyl
CH
3
H
5-propyl
CH
3
H
5-isopropyl
CH
3
H
5-cyclopropyl
CH
3
H
5-butyl
CH
3
H
5-isobutyl
CH
3
H
5-OCH
3
CH
3
H
5-OEt
CH
3
H
5-O-isopropyl
CH
3
H
5-O-propyl
CH
3
H
5-O-phenyl
CH
3
H
5-O-allyl
CH
3
F
5-H
CH
3
F
5-F
CH
3
F
5-Cl
CH
3
F
5-Br
CH
3
F
5-CH
3
CH
3
F
5-CH
2
CH
3
CH
3
F
5-propyl
CH
3
F
5-isopropyl
CH
3
F
5-cyclopropyl
CH
3
F
5-n-butyl
CH
3
F
5-isobutyl
CH
3
F
5-OCH
3
CH
3
F
5-OEt
CH
3
F
5-O-isopropyl
CH
3
F
5-O-propyl
The compounds of formula (1) according to this invention can be synthesized by a conventional method represented in the following scheme 1, reacting a compound of the formula (6) with a compound of the formula (7).
wherein, X′ is OH, Cl, Br or phenoxy group; R, X, Y and n are the same as previously defined.
In the method according to scheme 1, it is prefer to use a binder such as triphenylphosphine and an organic base such as triethylamine or pyridine by keeping temperature at 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, and to purify the crude product by column chromatography.
Another method for preparing the compounds (1) represented in the following scheme 2 is an alkylation of a compound of the formula (8) to compounds of the formula (9).
wherein, X″, which is a leaving group, is Cl, Br, I, benzenesulfonyloxy, toluenesulfonyloxy, methanesulfonyloxy or lower alkyl sulfate group; R, X, Y 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 amide, 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 reaction of a compound of the formula (10) with a compound of the formula (11) in the presence of a base.
wherein, Y′ is halogen, alkylsulfonyloxy, haloalkylsulfonyloxy, benzenesulfonyloxy or toluenesulfonyloxy group; R, X, Y, and n are the same as previously defined.
In Scheme 3, it is prefer to use inorganic bases such as alkali metal hydroxides like sodium hydroxide or potassium hydroxide, alkali metal carbonates like sodium carbonate or potassium carbonate, alkali metal hydrogencarbonates like sodium hydrogencarbonate or potassium hydrogencarbonate or organic bases like 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 or chlorobenzene; aliphatic hydrocarbons
Chang Hae Sung
Kim Dae Whang
Kim Jin Seog
Ko Young Kwan
Koo Dong Wan
Dongbu Hannong Chemical Co. Ltd.
Lowe Hauptman & Gilman & Berner LLP
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