CA1330439C - 5-methanesulfonyl-2, 4-diphenylpyrimidine derivatives - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A compound of the formula:

Description

1 330~3q 5-METHANESULFONYL-2, 4-DIPHENYLPYRIMIDINE DERIVA~IVES

This application is a divisional of our co-pending Canadian Patent Application No. 607,839 filed August 9, 1989.
The present invention relates to 5-substituted-2,4-diphenylpyrimidine derivatives, their production and use. More particularly, it relates to novel 5-substituted-2,4-diphenylpyrimidine derivatives, a process for producing them, and their use as herbicides.
There have been used a number of herbicides.
However, since they are insufficient for herbicidal effects, and also poor in the selectivity between crops and weeds, they do not always satisfy.
The present inventors have made extensive and intensive studies to develop excellent herbicides, and consequently found that the following compound is good in the herbicidal activity as well as in the selectivity between crops and weeds. The present invention is based on this finding.
Namely, the compound of the present invention has the following structural formula; ~

~: :

. ;~ R30 N ::`
~`
' ~^

n ~ ~

1 33043q 1 wherein R1 represents a hydrogen atom, or a halogen atom, a (C1 to C3)-alkyl group, a halo-(Cl to C~)-alkyl group, a (C1 to C6)-alkoxy group which may contain an un-saturated bond, a (Cl to C2)-alkylthio group, a halo-(C1 to C6)-alkoxy group which may contain an unsaturated bond, a halo-(Cl to C2)-alkylthio group, a phenoxy group, a (Cl to C3)-alkylcarboxy group, a halo-(C1 to C3)- ~-alkylcarboxy group, a (C1 to C2)-alkoxy-(Cl to C2)-alkoxy group, a (C1 to C3)-alkylsulfonyloxy group, a halo-(Cl to C3)-alkylsulfonyloxy group, a cyano group, a (Cl to C3)-alkoxycarbonyl group, a hydroxycarbonyl group, an aminomethyl group or a hydroxymethyl group at the ortho or meta position; R2 represents a hydrogen atom, a halogen atom, a (C1 to C2)-alkyl group, a halo-(Cl to C2j-alkyl group, a (Cl to C2)-alkoxy group, a nitro ~ group, a (C1 to C2)-alkylthio group, a halo-tC1 to C2)-;~ alkylthio group or a halo-(Cl to C2)-alkoxy group; and R3 represents a (C1 to C2)-alkyl group, provided that both R1 and R2 are not a hydrogen atom at the same time.

In another aspect, the present invention provides .~ ; S-methanesulfonyl-2, 4-diphenylpyrimidine derivatives having ~:~ the following structural formu~:
,~ ;
~, J ''~

J .
~:~

~ R~ 2 ~ CH3S2 wherein Rl represents a hydrogen atom, or a halogen atom, a (Cl to C3)-alkyl group, a halo-(CI to C3)-alkyl group, a (Cl to C6)-alkoxy group which may contain an ~ unsaturated bond, a (Cl to C2)-alkylthio group, a halo-i (Cl to C6)-alkoxy group which may contain an unsaturated 10 bond, a halo-~Cl to C2)-alkylthio group, a phenoxy group, a (Cl to C3)-alkylcarboxy group, a halo-~Cl to C3)-alkyl-carboxy group, a (Cl to C2)-alkoxy-(Cl to C2)-alkoxy ~ group, a ~Cl to C3)-alkylsulfonyloxy group, a halo-lCl to ~.:
f C3)-alkylsulfonyloxy group, a cyano group, a (Cl to C3)-15 alkoxycarbonyl group, a hydroxycarbonyl group, an aminomethyl group or a hydroxymethyl group at the ortho ~:i ~:~ or meta position; and R~represents a hydrogen atom, a ~ halogen atom, a (Cl to C2)-alkyl group, a halo-(Cl to `~ C2)-alkyl group, a ~Cl to C2)-alkoxy group, a nitro 20 group, a (Cl to C2)-alkylthio group, a halo-~Cl to C2)~
alkylthio group or a halo-(Cl to C2)-alkoxy group;
provided thatboth Rl and R~ are not a hydrogen atom at th~ ~ame tl~e.

2a -~ /'~
., ~ 1 33043~

Hitherto, J. Heterocyclic Chem., 23, 77 (1986) discloses 2,4-diphenyl-5-methanesulfonylpyrimidine, etc.
similar to the compound of the present invention.
However, in this paper, no mention is made of the biological activity of the compounds. Further, the paper does not disclose at all the chemical structure ~:
:
, ~

;;

: :~
. .' v ..
" ' ' ' ' ' :
' :` `' ::

,~

- 2b -:
:

:
1 and biological activity of 5-substitu~ed-2,4-diphenyl-pyrimidine derivatives of the present ir.vention.
The compound of the present invention has an excellent herbicidal activity, and ~s good in the ~ 5 selectivity between crops and weeds. Namely, the ; compound of the present invention has a good herbicidal activity on a number of undesired weeds whi~h will cause a problem to the foliar treatment as well as the soil treatment in up land fields. Examples of these weeds , 10 include broad-leaved weeds such as common chickweed (Stellaria media), radish (Raphanus sativus), wild mustard (sinaPis arvensis), velvetleaf (Abutilon theophrasti), prickly sida (Sida spincsa), field pansy (Viola arvensisj, catchweed bedstraw (Galium aParine), ivyleaf morningglory (Ipomoea hederacea), tall morningglory (Pharbitis purpurea), black nightshade (Solanum niqrum), and persian speedwell ~Veronica persica); and graminaceous weeds such as Japanese millet (Echinochloa frumentacea), barnyardgrass (Echinochloa crus-qalli), green foxtail ~Setaria viridis), large crabgrass (Diqitaria sanquinalis), oats (Avena sativa), and wild oats (Avena fatua). In addition, the compound of the present invention does not exert undesired phytotoxicity to main crops such as wheat, barley, rice plant, soybean, cotton, and corn.
~ ' ' .
~ 3 , .,~,.'.f~

` 1 330439 ., , 1 Further, the compound of the present invention ; has a herbicidal activity on a variety of weeds in paddy fields, for example, graminaceous weeds such as barnyardgrass (Echinochloa oryzoides), and does not exert undesired phytotoxicity on rice piant.
In the compound of the present invention, it is preferable that Rl is a hydrogen atom, or a halogen . atom, a tCl to C3)-alkyl group, a halo-(Cl to C3)-alkyl group, a (Cl to C6)-alkoxy group which may contain an unsaturated bond, a (Cl to C2)-alkylthio group, a halo-(Cl to C6)-alkoxy group which may contain an unsaturated bond, a halo-(Cl to C2)-alkylthio group, a phenoxy group, a (Cl to C3)-alkylcarboxy group, a halo-(Cl to C3)-alkyl-ca.boxy group, a (Cl to C2)-alkoxy-(Cl to C2)-alkoxy group, a (Cl to C3)-alkylsulfonyloxy group, a halo-(Cl to C3)-alkylsulfonyloxy group or a cyano group at the meta position; and R2 is a hydrogen atom, or a halogen atom, a (Cl to C2)-alkyl group, a halo-(Cl to C2)-alkyl group or a (Cl to C2)-alkoxy group at the meta or para position. More preferably, Rl is a hydrogen atom, or a halogen atom, a trifluoromethyl group or a trifluoro-methoxy group at the meta position; R2 is a hydrogen atom, or a halogen atom or a trifluoromethyl group at ~` the para position; and R3 is a methyl group. Most preferably, Rl is a trifluoromethyl group or a 1 33043q 1 trifluoromethoxy group at the meta position; R2 is a fluorine atom, a chlorine atom or 2 trifluoromethyl I group at the para position; and R3 is a methyl group.
3 The particularly preferred ccmpounds of the present invention include 2-(4-fluorG?henyl)-4-(3-tri-fluoromethylphenyl)-5-methoxypyrimidi..e; 2-t4-tri-fluoromethylphenyl)-4-(3-trifluoromethoxyphenyl)-5-meth-oxypyrimidine; and 2-(4-fluorophenyl)-4-(3-trifluoro-methoxyphenyl)-5-methoxypyrimidine.
. 10 The compound (I) of the presen' invention can be produced by the following procedures:
Procedure (A):
The compound (I) is prepared by reacting a ,.-compound of the formula:

lS

:
" ~ ' ;

[wherein Rl and R2 are each as defined above] with a compound of the formula:

, ~

~ .

1 33043q .,~.

. .

1 R30M (III) [wherein M is a metal atom, and R3 is as defined above].
The reaction is usually carriec out in an inert solvent at a temperature of about 20 to 100C for a period of about 0.5 to 5 hours.
~¦ Normally, the compound (III) is used in an ! amount of about 1 to 10 equivalents to one equivalent of the compound (II).
The solvent includes aliphatic hydrocarbons (e.g., hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g., benzene, toluene, xylene), ethers (e.g., diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), alcohols (e.g., methanol, ethanol, isopropanol, t-butanol), esters (e.g., ethyl acetate, butyl acetate), acid amides (e.g., N,N-dimethylformar~ide, acetamide), sulfur compounds (e.g., dimethyl sulfoxide), and mixtures thereof.
The compound (III) includes alkali metal alkoxides (e.g., sodium methoxide, sodium ethoxide).
After completion of the reaction, the reaction mixture is subjected to the usual after-treatment such as extraction with organic solvents, concentration, etc., to obtain the compound (I) of the present 1 33043q 1 invention, and if necessary, purified b~ chromatography, distillation, recrystallization, etc.
Procedure (B):
A compound of the formula:

..

[wherein R4 is a (C2 to C6)-alkoxy group or a halo-~C2 to C6)-alkoxy group at the ortho or meta position; and R~
and R3 are each as defined above~ is prepared by reacting a compound of the formula:
'.

~2 . . R30 N

[wherein R2 and R3 are each as defined above; and the hydroxyl group of the phenol moiety bonded to the _ 7 _ 1 pyrimidine ring is positioned at t~.e ortho or meta position] with a (C2 to C6)-olefi. which may be substituted with halogen.
The reaction i5 usually car-ied out in the presence of a base in an inert solvent at a temperature of 30 to 150C for a period of about 1 o 100 hours.
Normally, the olefin and the base are used respectively in amounts of about 5 to 30 equivalents and of about 1 to 10 equivalents to one equivalent of the compound (IV).
The solvent includes aliphG~ic hydrocarbons (e.g., hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g., benzene, toluene, xylene), halogenated hydrocarbons (e.g., chlorojenzene, dichloro-benzene), ethers (e.g., diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diet;-ylene glycol di-methyl ether), nitriles (e.g., aceton trile, isobutyro-nitrile), acid amides (e.g., N,N-cimethylformamide, acetamide), water, and mixtures thereo_.
iThe base includes inorganic b2ses (e.g., sodium hydroxide, potassium hydroxide, scdium carbonate, potassium carbonate, sodium hydride), etc.
After completion of the reaction, the reaction mixture is subjected to the usual a'er-treatment such as extraction with organic solvents, concentration, ~ - 8 -::

.
~ 1 etc., and if necessary, purlfied by chromatography, j distillation, recrystalli2ation, etc.
Procedure (C):
A compound of the formula:

~ ~ (I-2) [wherein R5 is a (Cl to C3)-alkylsulfor.yloxy group or a halo-(Cl to C3)-alkylsulfonyloxy group at the ortho or meta position; and R2 and R3 are each as defined above]
is prepared by reacting a compound of the formula:
R6-Cl (V) [wherein R~ is a (Cl to C3)-alkylsulfonyl group which may : be substituted with halogen] with the co~pound (IV).
1~ The reaction is usually carried out with or ~;~
without an inert solvent and in the presence of a base : at a temperature of about 0 to 50C for a period of about 0.5 to 5 hours.

~` 9_ 1 Normally, the compound (V) and the base are used respectively in amounts of about 1 to 2 equivalents and of about 1 to 5 equivalents to one e~uivalent of the compound (IV).
The solvent includes alipha.ic hydrocarbons (e.g., hexane, heptane, ligroin, p~troleum ether), aromatic hydrocarbons (e.g., benzene, 'oluene, xylene), halogenated hydrocarbons (e.g., chloroform, carbon tetrachloride, dichloroethane, chlorob-nzene, dichloro-benzene), ethers (e.g., diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), ketones (e.g., aceto-.e, methyl ethyl ketone, methyl isobutyl ketone, is3phorone, cyclo-hexanone), esters (e.g., ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate), pyridine, acid amides (e.g., N,N-dimethylformamide, acetamide), water, and mixtures thereof.
The base includes organic bases (e.g., pyridine), etc.
After completion of the reaction, the reaction ; mixture is subjected to the usual after-treatment such as extraction with organic solvents, concentration, etc., and if necessary, purified by chromatography, distillation, recrystallization, etc.

1 33043q .
1 Procedure ~D):
A compound of the formula:
~, '' ~ ~ ~I-3) R30 :;:
,. .
~wherein R7 is a (Cl to C6)-alkoxy group which may contain an unsaturated bond, at tr.e ortho or meta position; and R2 and R3 are each as defined above] is prepared by reacting a compound of the formula: .:~
. . :
R8-x (VI) ~wherein R8 is a (Cl to C6)-alkyl group, a (C2 to C6)-alkenyl group or a (C2 to C6)-alkynyl group; and X is a halo~en atom] with the compound (IV).
The reaction is usually carried out in the .
presence.of a base jin an inert solvent at a temperature :~
of 20 to 150C for a period of about 0.5 to 50 hours. :
,: ~
~;~ Normally, the compound (VI) and the base are ~ ~
":~
`~: used respectively in amounts of about 1 to 20 ~ ~ :
`~::

1 equivalents and of about 1 to 20 equivalents to one equivalent of the compound (IV).
The solvent includes aliphatic hydrocarbons ~e.~., hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g., benzene, toluene, xylene), ethers (e.g., diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), ¦ ketones (e.g., acetone, methyl ethyl ketone, methyl sobutyl ketone, isophorone, cyclohexanone), esters (e.g., ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate), nitriles (e.g., acetonitrile, iso-butyronitrile), acid amides (e.g., N,N-dimethylform-amide, acetamide), and water.
The base includes inorganic bases (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride), etc.
After completion of the reaction, the reaction mixture is subjected to the usual after-treatment such as extraction with organic solvents, concentration, etc., and if necfssary, purified by chromatography, distillation, recrysta11ization, etc.

3 = :

1 33043q 1 Procedure (E)~
A compound of the formula:
4) :~ R30 ~3 ~! [wherein R9 is a (Cl to C3)-acyl group; and R2 and R3 are each a~ defined above] is prepared by reacting a compound of the formula:

R9-O-R9 (VII) ~ -~' 10[wherein R9 is as defined above] with the compound (IV).
:
The reaction is usually carried out with or without an inert solvent and in the presence of an acid catalyst at a temperature of about 0 to 100C for a ~
period of about 0.5 to 30 hours. ~;
15Normally, the compound (VII) is used in an amount of about 1 to 3 equivalents to one equivalent of the compound (IV).
The solvent includes aliphatic hydrocarbons e.g., hexane, heptane, ligroin, petroleum ether), 20aromatic hydrocarbons (e.g., benzene, toluene, xylene), halogenated hydrocarbons (e.g., chloroform, carbon ~ ;

1 tetrachloride, dichloroethane, chlorobenzene, dichloro-., benzene), ethers (e.g., diethyl ether, dilsopropyl ether, dioxane, tetrahydrofuran, diethylene glycol di-methyl ether), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclo-hexanone), acid amides (e.g., N,N-dimethylformamide, , ~;
acetamide), water, and mixtures thereof.
The acid catalyst includes organic acids (e.g., acetic acid), inorganic acids (e.g., hydrochloric acid, sulfuric acid), etc.
After completion of the reaction, the reaction mixture is subjected to the usual after-treatment such as extraction with organic solvents, concentration, etc., and if necessary, purified by chromatography, distillation, recrystallization, etc.
Table 1 illustrates examples of the compound (I) of the present invention which can be produced by the above procedures.

~ :

: .

- .

: :`

;~
Table 1 Rl ~
R30 N ~:
; ~.. .
Rl R2 H p-Cl CH3 p-Br CH3 H p-CF3 3 ~ P-N02 CH3 m-F H CH3 m-F p-CH3 CH3 m-F p-F CH3 m-F p-CF3 CH3 m-F p-Cl CH
m-F p-Br CH3 m-F p-F
m-Cl p-F CH3 m-Cl H f CH3 m-Cl p-C1 CH3 m-Cl p-CF3 CH3 m-Br H CH3 .

~:~ - 15 -:~

1 33043q Table 1 (cont'd) Rl R2 m-Br p-Cl CH
m-Br p-Br CH
m-Br p-CF3 CH3 m-Br P-N02 CH3 m-Br p-F C2~5 -i o-Br p-CF3 CH3 :
m-I p-CF3 CH3 m-I p-F CH3 m-I p-F C2H5 m-CH3 p-F ~:

~:~ m-CH3 p-CF3 CH3 :~
; o-CH3 p-CF3 CH3 m-CF3 H CH3 m-CF3 p-CH3 : : m-CF3 p-F CH3 :
m-CF3 p-Cl CH
m-CF3 p-Br CH3 m-CF3 ~ ' ' p-CF3 CH3 ~; m-CF3 p-CH30 m-cF3 . m-CH30 CH3 m-CF3 m-F CH3 .`~
~ :

~ - 16 -. ~. '..;, ?, , :~ ` . "'~

1 33043~

' Table 1 (cont'd) .1 R1 R2 R3 CF3 o-F CH3 m-CF3 p-F C2H
m-CF3 p-CF3 C2H
m-CF3 p-Cl C2H
. m-cF3 p-CH3 C2H

m-CF3 . H C2H
o-CF3 p-CF3 CH3 o-CF3 o-F CH3 m-CH30 p-F ~H3 m-CH30 p-CF3 3 m-C2H5 p-F CH3 m C2H5 p-CF3 CH
m-(i)C3H70 p-F CH3 m-(seC)c4H9 p-F
m-(sec)C4HgO p-CF3 CH3 m-CH2=CHCH20 p-F c~3 m-CH2=CHCH20 p-CF3 m-CBaCCH20 . p-F CH3 m-CH-CCH20 p-CF3 CH3 m-CH3S p-F CH3 m-CH3S p-CF3 CH3 m-CF30 p-CF3 CH3 J,, .
- 17 - :
:::

133043q ~ ~

Table 1 (cont'd) l R2 R3 m-CF30 p-F CH3 m-CF30 p-Cl CH3 ~, m-CF30 p-F C2H5 m-CC130 p-F CH3 m-CC130 p-CF3 CH3 m-CF2HO p-F CH3 m-CF2HO p-CF3 ~ -m-CF2C10 p-F CH3 m-CF2C10 p-CF3 CH3 m-CF3CF2 p-F C~3 m CF3CF20 p-CF3 CH3 m-CF2HCF20 p-F CH3 m-CF2HCF20 p-CF3 m-CC12~1CF2 p-F CH3 m-CC12HCF20 p-CF3 CH3 m-CF3S p-F CH
m-CF3S p-CF3 CH3 ~.
m-C6H50 . . p-F j CH3 m C6H5 p-CF3 CH3 ~: m-CH3C02 p-F CH3 m-CH3C2 p-CF3 CH3 m-CClFHCF20 p-F CH3 ~ :
i - 18 -: .

1 33043q Table 1 (cont'd) l R2 R3 ,1 _ m-CClFHCF20 p-CF3 CH3 m-CClFHCClF0 p-F CH3 m-CClFHCClF0 p-CF3 CH3 m-CF3C02 p-F
m-C~30C~20 p-F CH3 m-CH30CH20 p-CF3 CH3 m-CH3S03 p-F CH3 m-CH3S3 p-CF3 m-CH3CH2S03 p-F CH3 m-CH3CH2S03 p-CF3 CH3 m-CF3S3 p-F CH3 m-CF3S03 p-CF3 CH3 m-CF3CF2S3 p-F CH3 m-CF3CF2S03 p-CF3 CH3 m-rF30 p-CF30 CH3 m-CF3 p-CF30 CH3 m-CH2NH2 p-CF3 CH3 m-CH2NH2 . p-F CH3 m-CH20H p-CF3 CH3 m-CH20H p-F CH3 m-CF30 p-SCH3 CH3 m-CF3 p-SCH3 CH3 ~ -~ ~ .
:;~
~ ~ - 1 9 ~ 1 330439 ,, ~ 1 Table 1 ~cont'd) 3 Rl R2 R3 _ :
m-CN p-CF3 CH
m-CN p-F CH3 m-COOH p-CF3 CH3 m-COOH p-F CH3 m-COOCH3 p-CF3 CH3 m-COOCH3 p-F
m-CClF=C~O p-F CH3 m-CF30 p-SCF3 CH3 m-CF3 p-SCF3 CH
~ ~:
The present invention will be illustrated in more detail by the following examples, but the present invention is not construed as being limited thereto.
First, Production Examples of the present invention are shown below.
Production Example 1 ~
2 9 of 2-(4-fluorophenyll-4-(3-trifluoromethyl- ~-phenyl)-5-methanesulfonylypyrimidine and 0.3 g of sodium methoxide were added to 20 ml of ethylene glycol dimethyl ether, and the resulting mixture was heated under reflux for 5 hours. The solvent was distilled away under reduced pressure. The residue was washed ,~ ~.
,~

~ - 20 - ~

¦ 1 with water, and then dried to obtair. 1.5 9 of 2-(4-fluorophenyl)-4-t3-trifluoromethylph~nyl)-5-methoxy-pyrimidine (Compound 18).
Production Example 2 1.5 g of 2-(4-fluorophenyl)-4-'3-hydroxyphenyl)-5-methoxypyrimidine and 0.25 9 of soc-um hydride were added to 15 ml of N,N-dimethyifor=~mide, and the resulting mixture was heated to 70C. After adding 6.6 g of 1,1-dichloro-2,2-difluoroethyle P thereto, the mixture was heated under reflux for 3 days. After completion of the reaction, ice-cold ~-'er was added to the mixture. Subsequently the mixt~.e was extracted with ethyl acetate. The solvent we, evaporated off, and the residue was purified by column chromatography on silica gel, thereby obtaining 1.0 of 2-(4-fluoro-phenyl)-4-[3-(1',1''-difluoro 2',2'-cichloroethoxy)-phenyl]-5-methoxypyrimidine (Compound 53).
Production Example 3 1.2 9 of 2-(4-fluorophenyl)-4-~3-hydroxyphenyl)-5-methoxypyrimidine and 0.57 9 of methanesulfonyl chloride were added to 10 ml of ~;ridine, and the resulting mixture was stirred for 3 hours at room , temperature. After completion of the -eaction, ice-cold water was added to the mixture. Subsequently the mixture was extracted with ethy~ acetate. The ~ - 21 -.

r` , . ~

,~ .
1 solvent was evaporated off, and the res.due was purified by column chromatography on silica gel, thereby obtain-ing 1.0 9 of 2-(4-fluorophenyl)-4-(3-me~hanesulfonyloxy-phenyl)-5-methoxypyrimidine (Compound 5Ç).
Production Example 4 ~ 1.2 9 of 2-(4-fluorophenyl)-4-(3-hydroxyphenyl)--~ 5-methoxypyrimidine, 5.5 g of potassiu-. carbonate, a~d 5.5 g of 2-bromobutane were added to 200 ml of acetone, and the resulting mixture was heated u,ider reflux for 2 days. The solvent was distilled away under reduced pressure. The residue was washed with water, and then purified by column chromatography on silica gel, thereby obtaining 1.0 9 of 2-(4-fluorophenyl)-4-~3-sec-butoxyphenyl)-5-methoxypyrimidine (Compound S0).
Production ~xample 5 One drop of 96% sulfuric acid was added to a mixture of 1.2 g of 2-(4-fluorophenyl)-4-(3-hydroxy-phenyl)-5-methoxypyrimidine and 0.5 9 of acetic anhydride, and the resulting mixture was stirred for 20 hours a'c room temperature. After completion of the reaction, ice-cold water was added to the mixture.
Subsequently the mixture was extracted with ethyl acetate. The solvent was evaporated off, and the residue was purified by column chromatography on silica 3 1 gel, thereby obtaining 1.0 g of 2-(4-f:uorophenyl)-4-(3-i acetoxyphenyl)-5-methoxypyrimidine (Com?ound 55).
Table 2 illustrates part of th~ compounds of the I present invention produced accordir.~ to the above i~
Production Examples.
. Table 2 ~1~
. R30 N

10Compound Melting No. - Rl R2 R3 - Point ( ~c) 1 m-Cl p-F CH3126.0 2 H p-Cl CH3105.5 : 3 H p-Br CH3155.4 4 H p-CF3 CH384.4 . :
H P-N02 CH3163.5 6 m-Cl H CH397.0 7 m-Cl p-Cl CH3143.0 m-Cl p-CF3 CH397.0 9 m-Br H C~3103.2 m-Br p-Cl CH3153.3 : ~:
: .

1 33043q Table 2 (cont'd) Compound Melting No. Rl R2 R3- Point ( C ) 11 m-Br p-Br CH3158.9 12 m-Br p-CF3 C~312g.5 13 m-Br p-No2 CH3152.1~dec) 14 o-Br p-CF3 CH3119.0 o-CH3 p-CF3 CH3103.4 16 m-cF3 H CH392.6 17 m-cF3 p-CH3 CH395.8 18 m-cF3 p-F c~398.9 . 19 m-cF3 p-Cl c~3127.4 m-cF3 p-Br CH3130.5 21 m-CF3 p-CF3 CH3108.3 22 m-CF3 p-CH30 CH3104.3 23 m-I p-CF3 CH3131.4 24 m-F H CH383.5 m-F p-CH3 CH372.5 26 m-F p-F CH398.3 27 m-F p-CF3 CH3101.3 28 m-F p-Cl CH3104.5 29 m-F p-Br CH3131.2 o-CF3 p-CF3 CH3142.5 31 m-CF3O p-CF3 CH394.6 : .

` ~
`~ - 24 -:e ~ S ~ ~s~ `s~

:? ~' '. ` ;.','. '.` . ' Table 2 (cont'd) Compound Melting , No. Rl _R2 - R3Point ( .~ 32 m-CF3O p-F CH373.9 33 m-I p-F CH3111.5 m-CF3 p-F C2H590 6 m-CF3 p-CF3 C2H5101.4 36 m-cF3 p-Cl C2~5103.0 37 m-CF3 p-CH3 C2H598.4 38 m-cF3 H C2H5104.1 39 m-~r p-F C2~5110.0 m-F p-F C2H5111.9 41 m-I p-F C2H5122.5 42 m-CF3O p-F C2H566.6 43 m-CH3 p-F CH3106.7 44 m-C2H5O p-F CH386.1 m-CH3OCH2O p-F CH393~4 46 m-CH3O p-F CH390.2 47 m-li)C3H7O p-F CH378.2 48 . m-CF3O p-Cl CH395.3 49 m-CF2HCF2O p-F CH379.2 m-(seC)c4Hg p-F CH3 86.0 Sl m-C6H5 p F c~3150.4 52 m-cF3 o-F c~367.8 :

1 33043~
, .

Table 2 (cont'd) ~3 Compound Melting i No. Rl R2 2.3Point (C) 53 m-CC12HCF2O p-F C-3 75~5 54 m-CH3SO3 P-P C 3 121.4 m-CH3CO2 p-F c~3 113.6 56 m-CF3CO2 p-F c~3 147.4 57 m-CF3 m-CH3Oc~3 83.1 58 m-cF3 m-F c~3 60.0 59 m-CF3SO3 p-F c~3 127.5 m-CH3O p-CF3C~3 98.2 61 m C2H5o p-CF3C~3 86.4 62 m-CH3OCH2O p-CF3 CH3 79 3 : :
63 m C6H5 p-CF3c~3 132.2 64 m-CF3 m-CF3c~3 98~2 m-CF3O m-F c~3 51.6 66 m-CF3O m-cF3C~3 55 7 : 67 m-CH2=CHCH2O p-F C~3 1.6180 (n25) 68 m-cF3 m-Cl c~3 78.8 69 m-CF2~HO p-CF3CH3 , 93 4 ~;
~ 70 m-CF3O m-Cl CH3 77.8 ~;
~ 71 m-CF3 p-SCH3 CH3 121.1 ;~ 72 m-CN p-CF3 CH3 131.7 73 m-CF2HO p-F CH3 88.5 .~ ~
~ . ` - 26 -:~: ~
.' ~'''.''''','.1`"'`"'.',''"'''~''',','"' '"'' ';"' "

1 The compound (II), which is a s~arting material ~ for the compound of the present invent on, is prepared 3 by reacting a compound of the formula:

N(cH3)2 1 ~ S2CH3 (VIII) R O -[wherein Rl is as defined above] with a compound of the . formula:
:~
~ NH2 (IX) [wherein R2 is as defined above].
The reaction is usually carried out in a solvent at a temperature of about 20 to 100C for a period of about 0.~5 to 5 hours.
: 15 Normally, the compound (IX) is used in an amount of about 1.1 to 1.2 equivalents to one equivalent of the compound ~VIII).

: ~
: - 27 -. 1 33043q I

1 The solvent includes aliphatic hydrocarbons (e.g., hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g., benzene, toluene, xylene), halogenated hydrocarbons (e.g., chlorobenzene, dichloro-S benzene), ethers (e.g., diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), alcohols (e.g., methanol, ethanol, isopropanol) acid amides (e.g., N,N-dimethylformamide, ace~amide), sulfur compounds (e.g., dimethyl sulfoxide, sulfolane), and mixtures thereof.
In the above reaction, the compound (IX) is normally used in the form of adducts of acids (e.g., a salt of hydrochloric acid). In this case, inorganic bases le.g., potassium carbonate) or alkali metal alkoxides (e.g., sodium methoxide, sodium ethoxide) are ~ .
used.
After completion of the reaction, the reaction mixture is subjected to the usual afte:-treatment such as extraction with organic solvents, concentration, etc., and if necessary, purified by chromatography, r. , , ~ .
recrystailization, etc.
` Production ExamPle 6 6 9 of 1-~3-trifluoromethylbenzoyl)-1-methane-sulfonyl-2-~N,N-dimethylamino)ethene and 4 9 of 4-fluorobenzamidine hydrochloride were dissolved in 30 ml ~ , ,~' ' - 28 - ~
:

1 33043q ,.
1 of me.nanol at room tem.pe.a.ure. ~ te- addir.g 1.2 g o~
sodium methoxide thereto, the mlxture ~as hezted under reflux ~or 1 hou~. The solven' W25 di_ illed a~2y under reduced pressure. The residue was ~c~hed with water, and then dried to obtain 6 g of 2-(4-f:uorophenyl)-4-(3-trifluoromethylphenyl)-5-methanesui onylpyrimidine (Compound 112).
Table 3 illustrates examples of the compound ~II) produced according to the above F-oduction Example 6.
Table 3 Rl ~/~

Compound ; 15 No. Rl R2 lH-NMR (~ value)*

101 H p-CF3 9.55 ~s, 1~), 8.72-8.6(d, 2H), 8.05-7.5 (m, 7H),3.15 (s, 3H) 102 H p-NO2 9.45 (s,lY,), 8.8-8.3 (q, 4H), 7.7 (b;s, 5H), 3.2 (s, 103 m-Cl H 9.45 (s, 1~), 8.65-8.45 (m, 2H), 7.8-7.45 (m, 7H), 2.8 - (s, 3H) ~' '.
.~

`; - 29 -~ .

~i `1, :
Table 3 (cont'd) No. Rl R2 lH-NMR (j value)*
104 m-Cl p-CF32H), 7.85-7)2 (8m7 86H)5 (d~
(s, 3H) 105 m-Br H 9.25 (s, :~), 8.55-7.3 (m, 9H), 3.15 (s, 3H) 106 m-Br p-Cl 9 45 (s, _~), 8.55-7.5 (m, 107 m-Br p-Br 9.5 (s, 1~), 8.5-8.35 (d, 2H), 7.95-7.4 (m, 6H), 3,2 (s, 3H) 1~
108 m-Br p CF 9 45 (sO _lH4)~(m 6Hjf 3.2 (s, 3H) o-Br p-CF 9 55 (s, iH), 8.65-8.5 ~d, ; 109 3 2H), 7.95-7.35 (m, 6H), 3.2 (s, 3H) 110 m-CF3 H 9.5 (s, 1~), 8.65-7.4 (m, 9H), 2.8 (s, 3H) 111 m-CF3 p-CH3 9.45 (s, ;~), 8.5-8.35 (d, 2H), 8.05-7.85 (m, 4H), 7.45-7.3 Id, 2H), 3.15 (s, 3H), 2.4 (s, 3H) 112 m-cF3 p-F 9.45 (s, lH), 8.7-7.0 (m, 8H), 3.0 (s, 3H) 113m_~F3 p-Cl 9 4 (s~ 1~45 (m 6H;, 3-0 (s, 3H) 114 m-CF3 p-Br 9.45 (s, lH), 8.5-7.6 (m, 8H), 3.05 (s, 3H) 115 3 6H), 2.8 (s, 3~) :

`i 1 33043q J
i `~ Table 3 (cont'd) Compound Rl R2l~-NMR (~5 value)*
116 m-cF3 P-No29 6 (s, 1~), 8.8-7.7 (m, 117 m-CF3 p-CH309.4 (s, lh), 8.6-8.4 (d, 2H), 8.1-7.7 (m, 4H), 7.1-6.95 (d, 2~), 3.9 (s, 3H), 3.0 (s, 3H) 118 m-I p-CF3 9.5 (s, lr), 8.75-8.6 (d, 2H), 8.15-7.2 (m, 6H), 3.22 (s, lH) 119 m-F H 9.45 (s, 1~), 8.55-8.35 (m, 2H), 7.75-7.55 (m, 7H), 3.1 (s, 3H) 120 m-F p-CH3 9 35 (s, 1~), 8.4-8.25 (d, 2H), 7.6-7.3 (m, 6H), 3.2 (s, 3H), 2.45 (s, 3H) 121 m-F p-F 9.4 (s, 1~), 8.65-8.4 (m, 2H), 7.75-7.0 (m, 6H), 2.8 (s, 3H) 122 m-F p-Cl 9.35 (s, 1~), 8.5-8.35 (d, 2H), 7.7-7.5 (m, 6H), 3.2 (s, 3H) 123 m-F p-Br 9.35 (s, 1~), 8.4-8.25 (d, 2H), 7.75-7.4 (m, 6H), 3.15 (s, 3H) 124 m-I p-F 9.35 (s, lH), 8.6-8.3 (m, 2H), 8.0-7.15 (m, 6H), 3.05 (s, 3H) 125 m-CF3 p-CF3 9 45 (s, lH), 8.7-8.55 (d, 2H), 7.8-7.45 (m, 6H), 2.8 (s, 3H) 126 m CF30 p-F 9.45 (s, lH), 8.7-8.45 (m, 2H), 7.75-7.0 (m, 6H), 2.8 (s, 3H~
:~ :
~ - 31 -Table 3 (co.~t'~) Co~ound ~o . ~1 R2 1~ Y2~ue ~ *

127 o-C~3 p-C~3 9.~5 (s, 1~-), 8.7-8.55 ~
2~), 7.8-7.65 (m, 6H), 2.8 (s, 3~) 128 m-cH3 p-F 9.30 (s, lH), 8.6-6.9 (m, 8H), 2.65 (s, 3H), 2.4 ~s, 3H) 129 m-C2~5 p-F 9.40 (s, 1~), 8.70-8.40 (m, 2H), 7.50-6.95 (m, 6H), 4.30-3.95 (q, 2H), 2.75 (s, 3H), 1.60-1.35 (t, 3H) 130 m-CH3OCH2O p-F 9.35 (s, 1~), 8.60-8.35 (m, 2H), 7.45-6.95 (m, 6H), 5.20 (s, 2-~), 3.45 (s, 3H), 2.75 (s, 3~
131 m-cF3 o-F 9.50 (s, lH), 8.30-7.0 (m, 8H), 2.80 ~s, 3H) 132 m-C6HSO p-F 9.35 (s, 1~) 1 8.60-8.35 (m, 2H), 7.5-6.95 (m, llH), 2.80 (s, 3~) 133 o-cF3 o-F 9.5 (s, 1~), 8.20-7.0 (m, 8H), 2.80 ls, 3H) 134 ~ m-Cl o-F 9. 50 (s, lH), 8.35-7.0 (m, 8H), 2.80 (s, 3H) 135 m-CF3 m-CH3O 9.40 (s, lH), 8.20-6.95 (m, 8H), 3.85 (s, 3H), 2.75 (s, 3H) 136 m-cF3 m-F 9.45 (s, 1~), 8.40-7.05 (m, 8H), 2.80 (s, 3H) 137 m-cF3 m-cF3 9 45 (5~ lH), 8.85-8~60 (m, 2H), 8.10-7.40 (m, 6H), 2.75 ( s, 3 ~,, " ", .", ,,.. ,,,,. ,,, ;;". ., .,-- -` - 1 330439 Table 3 (cont'd~
Compound No. Rl ~ lH-NMR (~ value)*
138 m-CF3O m-CF3 9.30 (s, 1-), 8.70-8.50 (m, 2H), 7.80-7.20 (m, 6H), 2.90 (s, 3-) 139 m-CH3OCH2O p-CF3 9.50 (s, -), 8.80-8.50 (m, 2H), 7.85-7.20 (m, 6H), 5.25 (s, 2--), 3.50 (s, 3H), 2.80 (s, 3-) 140 m-CF3O m-Cl 9.40 (s, 1~), 8.60-8.35 (m, 2H), 7.90-7.25 (m, 6H), 2.75 (s, 3 141 m-cF3 p-SCH3 9.30 (s, 1_), 8.45-7.15 (m, 8H), 2.75 (s, 3H), 2.50 (s, 3H) 142 m-CH3C~2O p-CF3 9.35 (s, 1-), 8.6 n -8.45 (m, 2H), 7.7C-6.95 (m, 6H), 4.25-3.90 lq, 2H), 2.75 (s, 3H), 1.55-1.30 (t, 3H) 143 m-CN p-CF3 9 40 (s, H), 8.75-7.6 (m, i 8H), 3.0 (s, 3H) *Solvent ;~ CDC13: Compounds 104, 110, 112, 121, 125, 126, 127, CDC13~DMSO-d6: Compounds 113, 117, 128, 142, 143 DMSO-d6: other compounds v ~` ~ ' " ' ~ _ 33 _ ,'~ .
. ~
) ~

~ .
1 The compound represented by the formula (VIII) is prepared by reacting a compound of the formula:

F~l ~ so2c}~3 ( X ) ~1 5 [wherein Rl is as defined above] with `;,N-dimethylform-amide dimethylacetal. The reaction i5 usually carried out with or without a solvent at a tem?erature of 20 to 150C for a period of about 0.5 to 10 h~rs.
Normally, N,N-dimethylformamide dimethylacetal is used in an amount of 1.0 to 1.5 equivalents to one e~uivalent of the compound (X).
The solvent includes aliphatic hydrocarbons (e.g. ! hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g., benzene, ~oluene, xylene), halogenated hydrocarbons (e.g., chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichloro-,, ~ , benzenej, ethers (e.g., diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), alcohols (e.g., methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol, methyl-cellosolve, diethylene qlycol, glycerin), acid amides :
..

~ :

1 (e.g., N,N-dimethylformamide), sulfur compounds (e.g., dimethyl sulfoxide, sulfolane), and mixtures thereof.
Production Example 7 2.5 g of m-trifluoromethyl-~-methanesulfonyl-acetophenone and 1.4 9 of N,N-dimethylformamide di-methylacetal were dissolved in 40 ml o' toluene, and the resulting mixture was heated under reflux for 2 hours.
The solvent was distilled away under reduced pressure.
The residue was treated with column chromatography on silica gel, thereby obtaining 3 g o' 1-(3-trifluoro-methylbenzoyl)-l-methanesulfonyl-2-(N,`.;-dimethylamino)-ethene (Compound 205).
Table 4 illustrates examples of the compound (VIII) produced according to the above Production Example 7.

: ~' ~ .
~ . ` , !
::

: :
': ~
' ~ ' :: 1 33043q ~ Table 4 ,~
~ ~ N(CH3)2 ~-Rl S02CH3 Compound No. _ R lH-NMR (~ value, CDCl~ solvent) 201 m-F 7.8 (s, lH), 7.7-7.2 (m, 4H), 3.2 (s, 3H), 2.8 (brs, 6H) 202 m-Cl 7.7-7.1 (m, 5H), 3.05 (s, 3H), 2.7 ; (brs, 6H) 203 m-Br 7.9-7.~5 (m, 5H), 3.15 (s, 3H), 2.75 (brs, 6H) 204 m-I 8.15-7.1 (m, 5H), 3.2 (s, 3H), 2.8 (brs, 6H) 205 m-CF3 8.0-7.5 (m, 5H), 3.15 ~s, 3H), 2.8 ~
(brs, 6H) ~ -206 o-Br 7.85-7.25 (m, 5H), 3.0 (brs, 9H) 207 m-CF3O 7.80-7.40 (m, 5H), 3.15 (s, 3H), ; 2.75 (brs, 6H) 208 m-CH3OCH2O 7.70 (s, lH), 7.40-7.10 (m, 4H), 5.15;(s, 2H), 3.40 (s, 3H), 3.15 (s, 3H), 2.7 (brs, 6H) .~, :
The compound represented by the formula (IV) is ~ prepared by reacting a compound of the ~ormula:
'~
, .
,~
.
.~

1 33043q o ~ ~ ~ R2 (I-S) [wherein R10 is a methoxymethoxy group at the ortho or meta position; and R2 and R3 are each as defined above]
with an acid. The reaction is usually carried out with a solvent at a tempera.ure of 20 to 100C for a period `~
of 1 to 5 hours.
Normally, the acid is used in a3 amount of 1 to 10 equivalents to one equivalent of the eompound (I-5).
The solvent includes aliphatic hydrocarbons (é.g., hexane, heptane, ligroin, pe.roleum ether), ~
aromatic hydrocarbons (e.g., benzene, toluene, xylene), ~;
halogenated hydrocarbons (e.g., chlorobenzene, dichloro-benzene), ethers (e.g., diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclo-hexanone), alcohols (e.g., methanol, ethanol, isopropanol, t-butanol), water, and mixtures thereof.
..

~ _ 37 _ ~
:~ .

f~

:. 1 33043q ;'~

1 The acid includes organic acics (e.g., acetic acid), inorganic acids (e.g., hyd-ochloric acid, sulfuric acid), and Lewis acids (e.c., fluoroborane ether complex).
After completion of the reactl.~, the reaction mixture is subjected to the usual after-treatment such as extraction with organic solvents, concentration, etc., and if necessary, purified by chromatography, recrystallization, etc. to obtain the de~ired compound.
Production Example 8 8 g of 2-(4-fluorophenyl)-4-(~-methoxymethoxy-phenyl)-S-methoxypyrimidine was added o a mixture of 150 ml of tetrahydrofuran and 150 r.l of isopropyl alcohol. After adding 10 ml of 12 N r.ydrochloric acid thereto, the mixture was stirred for 3 hours at 60C.
The solvent was distilled away under .educed pressure.
The residue was washed with water, ar.d then dried to obtain 7 g of 2-(4-fluorophenyl)-4-(3-~.ydroxyphenyl)-5-methoxypyrimidine.
For the practical use of the co ~ound (I), it is usually formulated with conventional solid or liquid carriers or diluents as well as surface active agents or auxiliary agents into conventional preparation forms ,, ,:
such as emulsifiable concnetrates, ~2ttable powders, suspensions and granules. The content of the compound ::-,,.

:~:

`
33043q .

1 (I) as the active ingredient in such preparation forms is normally within a range of about 1 to 80% by weight, preferably of about 2 to 70% by weight. Examples of the ~¦ solid carrier or diluent are fine powde.s or granules of S kaolin clay, attapulgite clay, bentonite, terra alba, pyrophyllite, talc, diatomaceous earth, calcite, walnut shell powders, urea, a~monium sulfate and synthetic hydrous silicate, etc. As the liquid carrier or diluent, there may be exemplified aro~atic hydrocarbons (e.g., xylene, methylnaphthalene), alcohols (e.g., iso-propanol, ethylene glycol, cellosolve), ketones (e.g., i, acetone, cyclohexanone, isophorone), soybean oil, cotton seed oil, dimethyl sulfoxidé, N,N-dimethylformamide, acetonitrile, water, etc.

i 15 The surface active agent used for emulsifica-tion, dispersion or spreading may be of any type, for instance, either anionic or non-ionic. Examples of the surface active agent include alkylsulfates, alkyl-sulfonates, a]kylarylsulfonates, dialkylsulfosuccinates, phosphates of polyoxyethylenealkylaryl ethers, polyoxy-ethylene alkyl ethers, polyoxyethylene alkylaryl ethers, ;~ polyoxyethylene-polyoxypropylene block copolymer, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. Examples of the auxiliary agents include ligninsulfonates, sodium alginate, ' ':~' : ':
:

1 polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phospha-e), etc.
ractical embodiments of the h~-bicidal composi-tion according to the present invent .n are illustra-tively shown in the following Form-lation Examples wherein parts are by weight. The compc nd number of the active ingredient corresponds to the onC in Table 2.
Formulation Example 1 Seventy parts of Compound 8 o- 17, 3 parts of calcium ligninsulfonate, 2 parts of soc-um laurylsulfate and 25 par.s of synthetic hydrous s licate are well mixed while being powdered to obtain a ~-ettable powder.
Formulation Example 2 Ten parts of Compound 10, 18, c- 20, 14 parts of lS polyoxyethylene styrylphenyl ether, 6 ?arts of calcium dodecylbenzenesulfonate, 70 parts of xylene are well mixed to obtain an emulsifiable concent:ate.
Formulation Example 3 Two parts of Compound 12 or 23, 1 part of synthetic hydrous silicate, 2 pa-ts of calcium ligninsulfonate, 30 parts of bentonite and 65 parts of kaolin clay are well mixed while beir.~ powdered. The mixture is then kneaded with water, gr~nulated and dried to obtain granules.
~ 25 :~

~ _ 40 -1 Formulation Example 4 Twenty-five parts of Compound 20 is mixed with 3 parts of polyoxyethylene sorbitan monoo~eate, 3 parts of carboxymethyl cellulose and 69 parts of water and pulverized until the particle size of the mix.ure becomes less than 5 microns to obtain a suspension.
¦ The compound (I) thus formulated in any suitable preparation form is useful for pre-e~ergence or post-emergence control of undesired weeds by soil or foliar treatment as well as flood following .reatment. These treatments include application to the soil surface prior to or after transplanting, incorporation into the soil, etc. The foliar treatment may be effected by spraying the herbicidal composition containing the compound (I) over the top of plants. It may also be applied directly to the weeds if care is taken to keep the chemical off the crop foliage.
The compound (I) may be used together with any other herbicide to improve its activity as a herbicide, and in some cases, a synergistic effect can be expected.
Further, it may be applied in combination with an insecticide, an acaricide, a nematocide, a fungicide, a plant growth regulator, a fertilizer, a soil improver, etc. Furthermore, it may be used as a herbicide applicable to agricultural plowed fields as well as :: :

:~

1 33043q 1 paddy fields. It is also useful as 2 herbicide to be employed for orchards, pasture lands, lawns, forests, non-agricultural fields, etc.
The dosage of the compouna (I) may vary 1 5 depending on the prevailing weather conditions, the ! formulation used, the prevailing seas~n, the mode of application, the soil involved, the crop and weed specides, etc. Generally, however, t;se dosage of the active ingredient is from about 1 to 8000 grams, preferably from about 5 to 2000 grams per hectare.
The herbicidal composition G' the invention formulated in the form of an emulsifiable concentrate, a wettable powder or a suspension may ordinarily be employed by diluting it with water at a volume of about 100 to 1000 liters per hectare, if necessary, with addition of an auxiliary agent such as a spreading agent. Examples of the spreading 2gent include, in addition to the surface active agents as noted above, polyoxyethylene resin acid (ester), ligninsulfonate, abietylenic acid salt, dinaphthylmethanedisulfonate, parafin, etc. The composition formulated in the form of granules may be normally applied as such without dilution.
The biological data of the compound (I) as herbicides will be illustratively shown in the following :~

~ - ~ 33043q .i .

1 Test Examples wherein the phytotoxici.~ to crop plants and the herbicidal activity on wee~; were observed ~ visually as to the degree of germinati_n as well as the i growth inhibition and rated with an lnc~x 0, 1, 2, 3, 4,5, 6, 7, 8, 9, or 10, the numeral ~" indicating no material difference as seen in co~._arison with the . untreated plants and the numeral "1~" indicating the complete inhibition or death of the tes plants.
The compounds as shown in Tabl- 5 were used for comparison.
Table 5 Compound -~
Code Structural Formula Remarks N~N~cE~3 ~Cor-ercial herbicide) '' ' B ¦¦ /ONa DSM~.
CH3-As\ (Co~ercial herbicide) . , C ~ Benthiocarb ..
Cl ~ CH25llN(C2H5)2 (Coh~ercial herbicide) :

~::

~ 1 330439 S, 1 Table 5 (cont'd) Compound Code Structural Formula Remarks D ~ ~ Described in J~ ~ J J. Heterocyclic Chem., ~, ~N ~ ~, 23, 77 ~1986) CH3SO2 ~ N

. :
Test ExamPle 1 Cylindrical plastic pots (diameter, 10 cm;
height, 10 cm) were filled with upland field soil, and the seeds of tall morningglory and velvetleaf were sowed therein and covered with soil. A designated amount of 10the test compound formulated in a wettable powder as in Formulation Example 1 was diluted with water, and the dilution was sprayed onto the soil surface by means of a small hand sprayer at a spray volume of 1000 liters per hectare. The test plants were grown in a greenhouse for 1520 days, and the herbicidal activity was examined. The results are shown~in Table 6.

~; ~ 44 ~

1 33~439 Table 6 ~erbiciaal Activity Compound Tall No. E~ MorninqqlorYVelvetleaf 500 10 _ 19 8000 10 lG

500 10 ~

~ .. ... .
~ D 2000 0 0 :~:Test ExamPle 2 ~Cylindrical plastic pots (diameter, 10 cm;
: height, ld cm) were filled with upland field soil, and ~: :
~ ~, _ 45 -. ~,.,,,,~,",................................

1 3'0439 ~, 1 the seeds of tall morningglory, radish and velvetleaf were sowed therein and cultivated in a greenhouse for 10 days. A designated amount of the test compound formulated in an emulsifiable cor.centrate as in Formulation Example 2 was diluted with water containing a spreading agent, and the dilution was sprayed over the foliage of the test plant by means of a small hand sprayer at a spray volume of 1000 liters per hectare.
The test plants were further grown in a greenhouse Eor 20 days, and the herbicidal activity W25 examined. The results are shown in Table 7.
Table 7 Herbicidal ActivitY
Compound Velvet- Tall No. ~ Radish leaf Morninqalory lS 2 500 8 8 9 32 9 ~ 9 ~ ~ .

Table 7_(cont'd) Herbicidal Activity Compound Velvet- Tall No. Dosaqe Radish leaf Morninqqlory (g/ha) .17 500 8 9 10 125 - 9 lC

31 500~ 10 10 9 . 125 10 9 9 ~: 32 500 10 9 10 :: 32 10 9 9 i~
;:~ ~
:: :
:
: 47 :

~ 330439 Table 7 ( cont ' d ) ~erbicic- Activity Co~pound Velve .- Tall ~ No. Dosa~e Radish le~Morninqqlory j (g/ha) 4g 2000 10 10 10 500 9 g -32 9 8 10 ~-: 62 500 9 9 10 ~ ::

; 65 500 10 9 10 32 ' 10 9 10 "~ '.

~: .

~; : - 48 -~ 1 330439 o 1 Table 7 (cont'd) Herbicida: Activity Compound Velvet- Tall No. Dosaqe Radish leaf Morninqqlory (g/ha) -2C00 ~ 0 0 Test Example 3 Cylindrical plastic pots (c.ameter, 8 cm;
height, 12 cm) were filled with paddy field soil, and the seeds of barnyardgrass (Echinochloa orYzicola) were sowed in 1 to 2 cm depth, and water was poured therein , to make a flooded condition.
Five days (at that time ~eeds began to germinate) thereafter, a designated ams~nt of the test compound formulated in an emulsifiable concentrate as in Formulation Example 2 and diluted with water (5 ml) was applied to the pots by perfusion. The test plants were grown for an additional 20 days in a greenhouse, and the herbicidal activity was examined. The results are shown ln Table 8.

1 33043q ~ .

Table 8 Compound Herbicid21 Activit~
No. DosaqeBanyc dqrass :
~, - ( g/ha ) 4 4000 lU

~: 13 4000 10 : ~ 14 4000 10 ' ~ 19 4000 10 ; 20 4000 10 :~ ~ 34 4000 10 : :

1 1 33043q Table 8 (cont'd) Compound ~erbicidal Activity No. ~ gQBanYa~dqrass 47 4000 lO

49 4000 lO
52 4000 lO
58 40~0 lO
61 4000 lG
62 4000 lO
64 4000 lO ;~

:~ :~
Test Example 4 Wagner's pots (l/5000 are) were filled with paddy field sQil, and the seeds of barnyardgrass (Echinochloa orYzicola~, broad-leaved weeds (i.e., common alsepimpernel,~indian toothcup, waterwort), and hardstem bulrush were sowed in l to 2 cm depth. Water was poured therein to make a flooded condition, and rice seedlings of 3-leaf stage and tubers of water nutgrass were transplanted therein, and the test plants were grown in a greenhouse. Five days (at that time 1 33043q .

1 barnyardgrass began to germinate) thereafter, a designated amount of the test compound 'ormulated in an emulsifiable concentrate as in Formulat,on Example 2 and diluted with water (10 ml) was appliec to the pOLS by perfusion. The test plants were grown Cor an additional 20 days in the greenhouse, and the he~b-lcidal activity was examined. The results are shown in Table 9. At the time of the treatment, the depth of w2ter in the pots was kept at 4 cm and following two da;s, water was let leak a volume corresponding to a 3 cm de?th per day.

.

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330~3q h ~
~ c o o o a~ o o o o 3 ~ .

~ ~ ,_1 o o a~c~ oo oo .~ ~ m ;

o o o ~ ~ O O , .~ ~3 :r: m , ~u~
: r cr o o ~ ~ ~ ~ ~ o ~ ~
- C~ ~q ~

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~ o a ~o ~o ~o oo . I
,~ P .'~
'~ .

:~ C ~ ::
.~: 1 ~ ~, '~ 1 ,',~ l_ :

: :

, . .

Claims (4)

1. A compound of the formula:
wherein R1 represents a hydrogen atom, or a halogen atom, a (C1 to C3)-alkyl group, a halo-(C1 to C3)-alkyl group, a (C1 to C6)-alkoxy group which may contain an unsaturated bond, a (C1 to C2)-alkylthio group, a halo-(C1 to C6)-alkoxy group which may contain an unsaturated bond, a halo-(C1 to C2)-alkylthio group, a phenoxy group, a (C1 to C3)-alkylcarboxy group, a halo-(C1 to C3)-alkyl-carboxy group, a (C1 to C2)-alkoxy-(C1 to C2)-alkoxy group, a (C1 to C3)-alkylsulfonyloxy group, a halo-(C1 to C3)-alkylsulfonyloxy group, a cyano group, a (C1 to C3)-alkoxycarbonyl group, a hydroxycarbonyl group, an aminomethyl group or a hydroxymethyl group at the ortho or meta position; and R2 represents a hydrogen atom, a halogen atom, a (C1 to C2)-alkyl group, a halo-(C1 to C2)-alkyl group, a (C1 to C2)-alkoxy group, a nitro group, a (C1 to C2)-alkylthio group, a halo-(C1 to C2)-alkylthio group or a halo-(C1 to C2)-alkoxy group;
provided that both R1 and R2 are not a hydrogen atom at the same time.

2. A compound according to claim 1, wherein R1 represents a hydrogen atom, or a halogen atom, a (C1 to C3)-alkyl group, a halo-(C1 to C3)-alkyl group, a (C1 to C6)-alkoxy group which may contain an unsaturated bond, a (C1 to C2)-alkylthio group, a halo-(C1 to C6)-alkoxy group which may contain an unsaturated bond, a halo-(C1 to C2)-alkylthio group, a phenoxy group, a (C1 to C3)-alkylcarboxy group, a halo-(C1 to C3)-alkylcarboxy group, a (C1 to C2)-alkoxy-(C1 to C2)-alkoxy group, a (C1 to C3)-alkylsulfonyloxy group, a halo-(C1 to C3)-alkyl-sulfonyloxy group or a cyano group at the meta position;
and R2 represents a hydrogen atom, or a halogen atom, a (C1 to C2)-alkyl group, a halo-(C1 to C2)-alkyl group or a (C1 to C2)-alkoxy group at the meta or para position.

3. A compound according to claim 1, wherein R1 represents a hydrogen atom, or a halogen atom, a tri-fluoromethyl group or a trifluoromethoxy group at the meta position; and R2 represents a hydrogen atom, or a halogen atom or a trifluoromethyl group at the para position.

4. A compound according to claim 1, wherein R1 represents a trifluoromethyl group or a trifluoromethoxy group at the meta position; and R2represents a fluorine atom, a chlorine atom or a trifluoromethyl group at the para position.