Note: Descriptions are shown in the official language in which they were submitted.
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; ~
~: :
3 R2
. ;~ 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~:
,~ ;
~,
2 -
J ''~
J .
~:~
1 330439
~ 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 330439
:
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
- 4 -
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
CH3S02 N
:
" ~ ' ;
[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:
R2
R30 N
..
[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 330439
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 330439
.
~ 1 etc., and if necessary, purlfied by chromatography,
j distillation, recrystalli2ation, etc.
Procedure (C):
A compound of the formula:
~ ~ (I-2)
R30 N
[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 330439
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 330439
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.
- 12 -
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 330439
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.
~ :
: .
- 14 -
- .
: :`
1 33043
;~
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 330439
¦ 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 3 3 0 4 3 9
,~ .
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
- 22 -
1 330439
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~
:? ~' '. ` ;.','. '.` . '
1 330439
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 330439
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)
R2 NH
[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 -
~ .
1 330439
~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~)
- 30 -
:
`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 -
1 330439
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
2 -
~,, " ", .", ,,.. ,,,,. ,,, ;;". ., .,-- -
` - 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,
129-141
CDC13~DMSO-d6: Compounds 113, 117, 128, 142, 143
DMSO-d6: other compounds
v ~` ~ ' " '
~ _ 33 _
,'~ .
. ~
) ~
1 330439
~ .
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
:
..
- 34 -
~ :
1 330439
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.
: ~'
~ .
~ . ` , !
::
: :
': ~
' ~ '
- 35 -
:: 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:
'~
, .
,~
.
.~
- 36 -
1 33043q
o ~ ~ ~ R2 (I-S)
R3O N
[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
::-
,,.
- 38 -
:~:
`
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,
' ':~'
- 39 -
: ':
:
1 330439
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 330439
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
:: :
- 41 -
:~
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
:~
- 42 -
~ - ~ 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
8 2000 10 10
12 2000 10 -
16 2000 10 10
17 2000 10 9
500 10 _
18 2000 9 10
500 - 10
19 8000 10 lG
21 2000 10 10
31 2000 10 10
500 10 ~
32 2000 10 10
34 2000 10 9
00 10 -
58 2000 10
61 2000 9
2000 10
A 8000 6 6
2000 2 2
~ .. ... .
~ 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
6 2000 10 10 10
500 9 - -
7 2000 10 10 10
500 9 9
8 2000 10 10 10
500 10 9 10
9 500 10 10 10
125 8 - 10
500 9 9 10
9 9 9
32 9 ~ 9
- 46 -
~ ~ .
1 330439
Table 7_(cont'd)
Herbicidal Activity
Compound Velvet- Tall
No. Dosaqe Radish leaf Morninqqlory
(g/ha)
11 500 - 9 9
12 500 10 10 10
125 9 9 10
32 - 8 10
14 2000 9 10 9
16 125 10 8 10
.17 500 8 9 10
125 - 9 lC
18 500 10 10 10
125 10 10 10
32 10 9 9
19 2000 9 9 10
5C0 9 9 10
500 10 9 10
125 9 9 9
32 9 8 9
21 500 10 9 9
12S 10 9 9
32 10 9 9
23 500 10 8 10
125 9 8 9
31 500~ 10 10 9
. 125 10 9 9
32 10 9 9
~: 32 500 10 9 10
125 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)
34 500 10 9 10
125 9 9 10
47 2000 10 10 10
500 9 19 10
125 9 10 9
48 2000 10 9 10
500 10 9 10
125 10 9 10
4g 2000 10 10 10
500 10 9 10
125 10 9 10
52 2000 9 - 9
58 2000 10 9 10
500 9 9 10
2000 9 9
500 9 g -
61 500 10 9 10
125 9 9 10
32 9 8 10 ~-
: 62 500 9 9 10 ~ ::
125 9 9 9
63 500 9 8 10
125 9 8 9
32 9 8 9
64 2000 9 9 9
500 9 9 9
; 65 500 10 9 10
125 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) -
66 500 9 9 10
125 9 9 10
32 9 9 9
B 8000 9 0 0
2C00 ~ 0 0
D 2000 3 2
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 )
2 4000 10
4 4000 lU
6 4000 10
7 4000 10
8 4000 10
9 4000 10
4000 10
11 4000 10
12 4000 10
~: 13 4000 10
: ~ 14 4000 10
4000 10
16 4000 10
17 4000 10
18 4000 10
' ~ 19 4000 10
; 20 4000 10
21 4000 10
23 4000 10
31 4000 10
32 4000 10
:~ ~ 34 4000 10
: :
1 1 33043q
Table 8 (cont'd)
Compound ~erbicidal Activity
No. ~ gQBanYa~dqrass
47 4000 lO
48 4000 10
49 4000 lO
52 4000 lO
58 40~0 lO
61 4000 lG
62 4000 lO
64 4000 lO ;~
4000 10
66 4000 10
D 4000 0
:~ :~
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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