Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
FIELD OF THE INVENTION
The present invention relates to ~ -1,2,4-
triazolin-5-one derivatives and herbicidal compositions
containing the same as the active ingredient.
~2-1,2,4-Triazolin-5-one derivatives according
to the present invention are represented by the general
formula (I),
F
Cl ~ N N-CHF2 ( I )
o r N ='~ CH
ROCfHO 3
CH3
(wherein R is a hydrogen atom; an alkali metal atom;
a ~uaternary ammonlum salt; an unsubstituted-alkyl group
having 1 to 6 carbon atoms; a substituted-alkyl group hav-
ing halogen atoms as the substituents; an unsubstituted-
cycloalkyl group; a substituted-cycloalkyl group having
halogen atoms as the substituents; an alkenyl group; an
alkynyl group; a lower alkoxyalkyl group; a lower
alkylthioalkyl group; a lower alkylsulfinylalkyl group;
a lower alkylsulfonylalkyl group; a lower alkoxy-
alkoxyalkyl group, a lower alkoxycarbonylalkyl group;
a hydroxycarbonylalkyl group; an unsubstituted-benzyl
.~ i ,i~
3~
1 group; a su~stituted-benzyl group having 1 to 2 substituents
selected rom the group consisting of a halogen atom,
a lower alkyl group, a lower alkoxy group, a nitro group,
a lower alkoxycarbonyl group, a hydroxycarbonyl group and
a phenoxy group; ~-methylbenzyl group or a phenethyl group).
DESCRIPTION OF THE PRIOR ART
Q -1,2,4-Triazolin-5-one derivatives represented
by the general formula (I) according to the present
invention are novel compounds and have not been known in
any literature.
Some of similar compounds related to the above-
mentioned ~ -1,2,4-triazolin-5-one derivative represented
by the general formula tI) are disclosed as the active
ingredient in herbicidal compositions in Japanese Patent
Kokai (Laid open) No. Sho 57-10~079 (1982) and Sho 57-
181069 11982).
The present inventors have found that compounds
represented by the general formula (I) possess effective
herbicidal activities, thus they are useful as agricultural
herbicides.
Additionally, the present inventors have found
the Eacts that compounds represented by the general
formula (I) show surprisingly excellent herbicidal
activities in relatively lower dosage and with lower
phytotoxicities as compared with act.ivities shown hy
compounds disclosed in the above-mentioned prior art
references.
SUMMARY OF THE INVENTION
An object of the present invention is to provide
novel ~ -1,2,4-triazolin-5-one derivatives.
Another object of the present invention is to
provide herbicidal compositions containing the ~2-1,2,4-
triazolin-5-one as the active ingredient.
Yet further object of the present invention is
to provide processes for preparing ~2-1,2,4-triazolin-
5-one derivatives.
Compounds represented by the general formula
(I) can be prepared by for example, processes method-A,
method-B and method-C as follows:
Method-A
~ ~ CHF2 zl F O
O ~ N ~ Base ~ N N-CHF 2
ROCCHO CH3 11 / CH3
CH3 ROCCHO
~II) CH3 (I)
(wherein R is the same as defined above; zl is a
chlorine atom, a bromine atom or an iodine atom).
3~
1 Method-B
Cl- ~ ~ N N-CHF2 ROCCH-Z Cl ~ ~ N -CHF2
N ~ (V) I N ~
~o CH3 Base 3- ROCCHO C~I3
(IV) CH3 (I~
(wherein R is the same as defined above; z2 is a halogen
atom).
Method-C
F o F O
~ ~ ROH (VI) ~ ~
C1 ~ -N N-CHF2 - ~- Cl ~ N~ ~ -CHF2
li CH3 ROCCHO C~I3
XCCHO
1H CH3
3 (VII) ( I)
S (wherein R is the same as defined above; X is a halogen
atom or a hdyroxyl group).
Thus, the objective ~2-1,2,4-triazoline-5-one
derivative represented by the general formula (I) can be
prepared, in method-A, by reacting a compound represented
by the general formula (II~ with a compound represented
by the general formula (III); in method-B, by reacting a
~ t~3 ~
1 compound represented by the general formula (IV) with a
compound represented by the general formula (V); and in
method-C, by reacting a compound represented by the general
formula (VII) with a compound represented by the general
formula (VI), respectively in an inert solvent, in the
presence or absence of a basic compound.
As to the inert solvent used ln these reactions,
any inert solvent which does not give any adverse effect
to the reactions may be employed, for ex~mple aromatic
hydrocarbons such as benzene, toluene, xylene or the like
can be exemplified; aliphatic hydrocarbons such as n-
hexane, cyclohexane or the like can be exemplified;
alcohols such as methanol, ethanol, propanol, ethylene
glycol or the like can be exemplified; ketones such as
acetone, methyl ethyl ketone, cyclohexanone or the like
can be exemplified; lower aliphatic acid esters such as
ethyl acetate or the like can be exemplified; ethers
such as tetrahydrofuran, dioxane or the like can be
exempli~ied; lower fatty acid amides such as dimethyl-
formamide, dimethylacetoamide or the like can be exempli-
fied; and water, dimethyl sulfoxide or the like can be
ex,emplified. The above-mentloned solvents may be employed
in singly or in a mixture thexeof.
Further, in method-C, when an alcohol is used as
the solvent, an alcohol corresponding to a compound repre-
sented by t~e general formula ~VI) may preferably be used.
As to the basic compound used in the above-
mentioned reactions, inorganic basic compounds, for
3~
l example alkali metal hydrides such as sodium hydride or the
like; alkali metal hydroxides such as sodium hydroxide,
potassium hydrcxide or the like; alkali metal carbonates
such as sodium carbonate, potassium carbonate or the like;
alkali metal hydrogen carbonate such as sodium hydrogen
carbonate, potassium hydrogen carbonate or the like;
alkali metal alcoholate such as sodium methylate or the
li~e; and organlc basic compounds such as pyridine, tri-
methylamine, triethylamine, diethylaniline, 1,8-diazabi-
cyclo-[5,4,0]-7-undecene or the like can be exemplified.
Reactions of the present invention can be carried
out, for example at a temperature in the range of from 0
to 150C to a predetermined temperature.
The reactions in each step therein are equimolar
reactions, and in carrying out these reactions, slightly
excess amount of one reactant to the amount of another
reactant may be employed.
The reaction time may be selected from in the
range of from 0.5 to 48 hours.
After the reaction is completed, the objective
product can be obtained by treating the reaction product
under a conventional manner.
Compound represented by the general formula (II)
used as the starting material in method-A may be synthesiz-
ed by the reaction steps as follows:
-- 6
3~
\ ~2 Rl-A-f=NcooR
O CH3 (IX)
Il ~
ROCCHO Heat
CH3 (VIII)
Cl ~ ~ NHNHC=NCOOR
~ H3 Basic compound
ROCfHO
CH3 (X)
F O
C1- ~ N NH
O ~ N ~
ROCCHO CH3
CH3
1 (wherein R is the same as defined above; Rl and R2 are
each a lower alkyl group, A is an oxygen atom or a
sulfur atom).
Thus, a compound represented by the gene.ral
formula (II) can be prepared by reacting a compound
represented by the general formula (VIII) with a
compound represented by the general formula ~IX) in an
inert solvent under a heating condition, -then the
thus obtained compound represented by the general
- 7 --
2~
1 formula (X) is trea-ted under a ring-closing reaction,
with a basic compound, with or without being separated
from the xeaction product.
Furthermore, a compound represented by the
general formula (IV) used as the starting material in
method-B may be synthesized by the reaction step as
follows:
F O F O
Cl ~ N -CHF2 ~3 Cl ~ N N-CHF2
R10 CH3 HO CH3
(XI~ (IV)
(wherein Rl is the same as defined above).
In the above-mentioned reaction, in place of
using hydrobromic acid, there may be used hydroiodic acid
or an alkyl thiolate.
Typical examples of ~2-1,2,4-triazolin-5-one
derivatives represented by the general formula (I) are shown
in the following Table 1.
F O
Cl ~ N N-CHF
O ~ \N ~ 2
ROCfHO C~3
CH3 (I)
Table 1
Compound
No. R Physical properties
1 H- nD 1.5192
2 Na- Melting point 186.1C
3 K- Melting point 119.2C
4 ~ H4- Metling point 92.7C
lso C3H7~ H3 Melting point 157.3C
6 (C2H5) ~ H- Oily substance
7 (n-C4H9)2~ H2- Melting point 126.5C
8 CH3- n23 1.5142
C2H5 nl 1.5112
n~C3H7~ n23'0 1 5051
11 iso-C3H7- n23 0 1 5051
12 n C4Hg n29 0 1.5031
13 iso-C4Hg- n29 0 1.5011
14 tert-C H - nD 1.5009
5 11 nD 1O4984
16 lSO-C H - nD 1.5002
17 _ C6H13 nD '5 1.4992
18 ClCH2CH2 nD6-5 1.5204
19 BrCH2CH2 nl9 5 1.5291
C13CCH2- Melting point 106.5C
21 F3CCH2- nl9 5 1.4826
22 ClCH2CH2CH2- Melting point 87.7C
23 BrCH2CH2CH2- Melting point 83.8C
24 ClCH2fH- Melting point 58.7C
CH3 - Cont'd -
3~
Table 1 (Cont'd)
ClCH2CHCH2- Melting point 95.0C
Cl
26 ClCH2 \ CH nD 5 1.5091
ClCH2 /
27 BrCH2 \ CH- Melting point 104.2C
BrCH2/
28 3C > CH- nl9 5 1.4573
F3C
29 ClcH2cH2cH2cH2 Melting point 95.3C
~ n26 0 1 5130
31 ~ n27-5 1 5140
32 Cl nl7 5 1 5174
33 CH2-CHCH2- n28.5 1 5156
34 CFI_CCH2 n28-5 1.5192
CH_CCH2CH~- nl7 5 1.5209
36 CH30(CH2)2 n26 0 1 5088
37 C2H5O~CH2)~- n26 0 1 5022
38 iso-C3H7O(cH2)2 nD6 0 1.4989
_ 4 9 (C 2)2 n26.0 1 4878
CH OCH~H CH - n~7-5 1.5009
41 CH3SCH2- nl~ 1.5279
42 CH3S[CH2)2- n26-5 1.5306
- Cont'd -
-- 10 --
Table 1 (Cont'd)
43 C2H5S(CH2)2- nl9'5 1.5274
44 1so-c3H7s(cH2)2 nl9 5 1.5233
1so-C4HgS(CH2)2- nl9 5 1.5212
46 seC-c4H9s~cH2)2 nl9'5 1.5219
47 tert-C4HgS~CH2)2- n22-5 1 5179
48 CH3S(CH2)3- nD9 5 1.5299
49 C2H5S(CH2)3- nl9 5 1.5203
1so-c3H7s(cH2)3- nl9 5 1.5204
51 n-C4HgS(CH2)3- nl4 5 1 5216
52 1SO-C4Hgs(cH2)3- nD 5 1.5209
53 tert-C4HgS(CH2)3- nl6 5 1 5172
54 CH3S(CH2~2- Melting point 104.5C
~ Melting point 99.8C
O O
56 CH30(CH2~2O(cH2)2 nD6 0 1.5052
57 CH OC-CH- Melting point 108.1C
3 il l
O CH3
58 ~ CH2- Melting point 82.4C
__ "-Cl
Cl CH2- Melting point 117,5C
~ CH2- Melting point 72.6C
61 C1 - ~ CH2- Melting point 73.0C
- Cont'd -
,
7~
Table 1 (Cont'd)
62 ~ CH~- Melting point 115.7C
63 F ~ CH~- Melting poin-t 80.0C
64 H3C- ~ CH2- Melting point 102.8C
H3C0 ~ - CH2- Melting point 89.4C
66 02N ~ CH2- Melting point 126.5C
67 C2H5C ~ - CH2- Melting point ].35.3C
68 ~ CH2- n26-0 l 5588
C 1
69 Cl ~ CH2- Melting point 163.0C
C1 Melting point 114.7C
CH3 \
71 CH30 ~ CH2- Melting point 96.5C
- Cont'd -
- 12 -
L?~
Table 1 (Cont'd)
72 ~ -CH- Oily substance
73 ~ CH2CH2- Oily substance
1 Next, NMR spectrum data for the compound
having physical properties indicated as oily substance
are shown in Table 2 below.
Table 2
No. NMR TC14 (ppm)
6 1.15 (t, 9H), 1.64 (d, 3H3~ 2.41 (s, 3H),
2.19 (q, 6M), 4O53 (q, lH3, 7.03 (t, lH),
7.Q4 (d, lH), 7.22 (d, lH)
72 1.32-1.77 (m, 6H), 2.30 ~s, 3H), 4.60
(q, lH), 5.76 (q, lH), 686 (t, lH),
6.76 7.31 (m, 7H)
73 1.56 (d, 3H)~ 2.35 (s, 3H), 2.84 (t, 2H),
4.28 (t, 2H), 4.59 (q, lH), 6.91 (t, lH),
6.85-7.32 (m, 7H~
1 The present invention will be illustrated more
specifically by way of showing the following examples.
However, the present invention will not be restricted only
to these examples.
Example 1
Preparation of 1-{4-chloro-2-fluoro-5-[1-(ethoxy-
carbonyl~ethoxy]phenyl}-4-difluoromethyl-3-methyl-~2-
1,2,4-triazolin-5-one (Compound No. 9)
F O F O
Cl ~ -N I N-CHF2 BrCHCOOC2H5 Cl ~ -N ~ -CHF2
~O O ¦ CH3
~5C2OCIHO
(IV) C~I3
13.27 Grams (0.045 mole) of compound (IV),
9.06 g (0.0498 mole) of ethyl ~-bromopropionate and
13.27 g (0.0~62 mole) of potassium carbonate were
refluxed in 200 ml of acetone with stirring for 3 hours.
Then, the reaction mixture was cooled to a room tempera-
ture, and the insoluble matters were removed by filtra-
tion. Next, the filtrate was concentrated, and the oilysubstance thus obtained was dissolved in diethyl ether,
and washed with cold water, then the diethyl ether solu-
tion was dried, the solvent was removed by evaporation
to yield an oily substance. (This oily substanc~ was
indeed clear state as it was, and was purified by means
- 14 -
)3~
1 of a dry column chromatography by using a sllica gel.)
Yield: 14.7 g (83.1%) Refractive index nD 1.5112.
Example 2
Preparation of 1-{4-chloro-2-fluoro-5-[1-
(hydroxycarbonyl)ethoxy]phenyl}-4-difluoromethyl-3-
methyl-~ ~1,2,4-triazolin-5-one (Compound No. 1)
F O F O
Cl ~ N ~ N-CHF2 Cl ~ N N-CHF2
HO CH3 HOCCHO CH3
CH3 CH3
1.4 Grams ~0.00356 mole) of 1~{4-chloro-2~
fluoro-5-[1-~ethoxycarbonyl)ethoxy]phenyl}-4-difluoro-
methyl-3-methyl-~-1,2,4-triazolin-5-one was dissolved
in 50 ml of ethanol, then to this solution was added
1.2 g of 20~-potassium hydroxide aqueous solution, and
the whole mixture was stirxed at a room temperature for
3.5 hours. After the reaction was completed, the reac-
tion mixture was poured in an ice-water, acidified with
hydrochloric acid, then the desired product was
extracted with ethyl acetate. The extract was washed
with water, and dried with anhydrous magnesium sulfate,
then the solvent was removed by evaporation to yield
1.1 g ol oily substance as the ob]ective product.
Refractive index n24 5 1.5192. Yield 84~.
- 15 -
~ Z L~ 7 3V
1 Example 3
Preparation of sodium 2-[2-chloro-5-(4-difluoro-
methyl-3-methyl-5-oxo-~ -1,2~4-triazolin-1-yl)-4-fluoro-
phenoxy]propionate (Compound No~ 2~
F O F O
Cl ~ N ~ N-CHF2 ~ ~ Cl ~ N M-CHF2
HOCfH i N ~ c~3 ~ N
c~3 CH3
0.5 Gram (0.00136 mole) of 1-{4-chloro-2-
fluoro-5-[1-~hydroxycarbonyl)ethoxy]phenyl}-4-difluoro-
methyl-3-methyl-~ -1,2,4-triazolin~5-one was dissolved
in 20 ml of tetrahydrofuran, then to this solution
was added 0.05 g (0.00125 mole) of sodium hydride,
and the whole mixture was stirred at a room temperature
for 10 minutes. After the reaction was completed, the
tetrahydrofuran was removed by evaporation under a reduced
pressure, the residue thus obtained was washed with n-
hexane to yield 0.37 g of the objective product.
Meltlng point 186.1C. Yield 76.4%.
16 -
7~
1 Example 4
Preparation of dibutylammonium 2-[2-chloro-5-
(4-difluoromethyl-3-methyl-5-oxo-Q2-1,2,4-triazolin-1-
yl)-4-fluorophenyloxy]propionate (Compound No. 7)
F O F O
Cl ~ \ ~ F2 - =a_ Cl ~ N N-CHF2
CH3 n-C4~Ig \ 6~3 ll ¦ CH3
HOCCHO NH2 OCCHO
IH3 n C4Hg CH3
0.5 Gram (0.00136 mole~ of 1-{4-chloro-2-
fluoro-5-[1-(hydroxycarbonyl)ethoxy]phenyl}-4-difluoro-
methyl-3-Q -1,2,4-triazolin-5-one was dissolved in
20 ml of benzene, then to solution was added 1.0 g (0.0139
mole) of dibutylamine, then under an ice-cooling condition,
the reaction was carri.ed out. The crystals fromed in the
reaction mixture was collected by filtration, and washed
with benzene to yield 0.51 g of the objective compound.
Melting point 126.5C. Yield 79.4~.
- 17 ~
3~
1 Example 5
Preparation of 1-{4-chloro-2-fluoro-5-[1~
(propargyloxycarbonyl)ethoxy]phenyl}-4-difluoromethyl-
3-methyl-Q2 1,2,4-triazolin-5-one (Compound No. 34)
F O F O
HOCCHO 3 C1CCHO CH3
CH3 CH3
F O
Cl- ~ N N-CHF
N ~
Il CH3
HC-CCH2OCfHO
CH3
A mixed solution of 20 ml of thionyl chloride
containing 2.7 g of 1-{4-chloro-2-fluoro-5-[1-Ihydroxy-
carbonyl)ethoxy]phenyl}-4-difluoromethyl-3-methyl-Q2-
1,2,4-triazolin-5-one was refluxed under heating for
2 hours. After the reaction was completed, the
excessive thionyl chloride was removed by evaporation,
and obtained 2.8 g of 1-~4-chloro-2-fluoro-5-~ chloro-
carbonyl)ethoxyJ-phenyl}-4-difluoromethyl-3-methyl-Q2_
1,2,4-triazolin-5-one quantitatively. Then 0.5 g
- 18 -
1 (0.0013 mole) of this compound was dissolved in 20 ml of
tetrahydrofuran, to this solution was added 0.2 g
(0.00357 mole) of propargyl alcohol and 0.2 g (0.00198
mole) of triethylamine, then the whole mixture was
reacted at a room temperature for 2 hours. After the
reaction was completed, the reaction mixture was poured
in an ice-water, and extracted with ethyl acetate. The
ethyl acetate layer was washed with an aqueous solution
containing 10~ of potassium carbonate, then with water,
dried with anhydrous magnesium sulfate, and the solvent
was removed by evaporation. Thus obtained residue was
purified by means of a dry column chromatography to
yield 0~35 g of the objective product.
Refractive index n28-5 1.5192. Yield 66.6%.
Example 6
Preparation of 1-{5-[1-(tert-butoxycarbonyl)-
ethoxy]-4-chloro 2-fluorophenyl}-4-difluromethyl-3-
methyl-~ -1,2,4-triazolin-5-one (Compound No. 14)
F O F O
C ~ N ~ N-C~F2 ~ C ~ \N ~
ll CH3 ll CH3
ClCf HO (CH3)3-COCIC~IO
CH3 CH3
0.58 Gram ~0.00151 mole) of 1-{4-chloro-2-
fluoro-5-[1-(chlorocarbonyl)ethoxy]phenyl}-4-difluoro-
.
'7~{3
1 methyl-3-methyl-Q2-1,2,4-triazolln-S-one was added in a
mixed solution of 0.25 g (0.00338 mole) of tert-butyl
alcohol, 0.14 g (60~ in oil, 0.0035 mole) of sodium
hydride, and 20 ml of tetrahydrofuran. The whole mixture
was heated under refluxing condition for 6 hours. After
the reaction was completed, the reaction mixture was
treated under a condition similar to that described in
Example 5, to yield 0.13 g of the desired product.
Refractive index n26 0 1.5009. Yield 18.8%.
Example 7
Preparation of 1-{4-chloro-2-fluoro-5-[1-
[[l-(methoxycarbonyl)ethoxy]carbonyl]ethoxyphenyl}-4-
difluoromethyl-3-methyl-~2-1,2,4-triazolin-5-one
(Compound No. 57)
F o F O
Cl ~ ~N ~ 2 ~ ~ Cl ~ N N-C~F2
HOCfHO CH3 CH30CCHOCCHO C~I3
CH3 CH3 CH3
A mixed solution of 0.5 g l0.00136 mole) of
1-~4-chloro-2-1uoro-5-[1-(hydroxycarbonyl)ethoxy]phenyl}-
4-difluoromethyl-3-methyl-~2-1,2,4-triazolin-5-one, 0.28 g
(0.00136 mole) of N,N'-dicyclohexylcarbodiimide, 0.02 g
(0.000164 mole) of 4-dimethylaminopyridine and 10 ml of
diethyl ether was reacted at a room temperature for
6 hours. After the completion of the reaction, the
insoluble matters were removed by filtration, and the
- 20 -
73l~
1 filtrate was txeated by evaporation, the residue obtained
was purified by means of a dry column chromatography to
yield 0.41 g of the objective product. Melting point
108.1C. Yield 64.3~.
Example 8
Preparation of 1 {4-chloro-2-1uoro-5-[1-
(ethoxycarbonyl)ethoxy]phenyl}-4-difluoromethyl-3-methyl-
-1,2,4-triazolin-5-one (Compound No. 9)
F O F O
Cl ~ N NH 3~ Cl ~ N N-CHF2
C2~5OCCHO CH3 C2H5OCCHO CH3
CH3 IH3
0.046 Gram (0.00134 mole) of sodium hydride
was suspended in 10 ml of dried N,N-dimethylformamide, to
this suspension was added dropwise a solution prepared by
dissolving 0.4 g (0.00122 mole) of 1-{4-chloro-2-fluoro-
5-[1-(ethoxycarbonyl)ethoxy~phenyl}-3-methyl-~2-1,2,4-
triazolin-5-one at a room temperature. After the comple-
tion of dropwise addition, the whole mixture was stirredfor 30 minutes, then monochlorodifluoromethane (ClCHF2)
gas was introduced into the mixture at 130C for 5 hours.
After the reaction was completed, the reaction mixture was
cooled to a room temperature, and the reaction mixture was
poured in an ice-water. The oily substance formed was
extracted with diethyl ether, and the extract was dried
with anhydrous magnesium sulfate. The solvent was removed
- 21
Z'7~6~
1 by evaporation to yleld an oily substance. This oily
substance was purified by means of a dry column chromato-
graphy to yield 0.15 g of the objective product. Refrac-
tive index n19 1.51120 Yield 32.6%.
Example 9
Preparation of 1-{4-chloro-2-fluoro-5-[1-
(methylthiomethoxycarbonyl)ethoxy]phenyl}-4-difluoro-
methyl-3-methyl-~2-1,2,4-triazolin-5-one (Compound No. 41)
F ~ F O
C ~ N -CHF2 ~=~ C ~ \ ~ 2
HOCfHO CH3 CH3SCH2OCfHO CH3
CH3 CH3
A mixture of 0.5 g (0.00137 mole~ of 1-{4-chloro-
2-fluoro-5-[1-~hydroxycarbonyl)ethoxy}phenyl}-4-difluoro-
methyl-3-methyl-~2-1,2,4-triazolin-5-one, 1.76 g (0.00128
mole) of tert-butyl bromide, 1.15 g (0.00137 mole) of
sodium hydrogen carbonate and 10 ml of dried dimethyl
sulfoxide was reacted under stirring condition at a
room temperature for 32 hours. ~fter the completion of
the reaction, the xeaction product was treated by a
method similar to that described in Example 8 to yield
0.4 g of the objectiv~ product. Refractive index nl8 0
1.5279. Yield 68.7%~
- 22 -
~ 3~
l The ~2-1,2,4-triazolin-5-one derivatives of the
present invention are capable of controlling annual and
perennial weeds grown in paddy fields, upland fields,
orchards and swamps, for example barnyard grass (Echino-
chloa crusgalli Beauv., an annual weed of Gramineae family
grown in paddy fields and strongly injurious), monochoria
(Monochoria vaginalis Presl, a strongly injurious annual
weed of Pontederiaceae family grown in paddy fields),
smallflower umbrellaplant (Cyperus difformis L., an inju-
rious annual weed of Cyperaceae family grown in paddyfields), slender spikerush (Eleocharis acicularis Romer
et Schultes, a typical injurious perennial weed of
Cyperaceae family grown in paddy fields, and also grown
in swamps and waterways), arrowhead (Sagittaria pygmaea
Miq., an injurious perennial weed of Alismataceae family,
grown in paddy fields, swamps and ditches), bulrush
(Scirpus juncoides Roxb. var. Hotarui Ohwi, an annual
weed of Cyperaceae family, grown~ in paddy fields, swamps
and ditches), wild oats (Avena fatua L., an annual weed
of Gramineae family, grown in plains, waste lands and
upland fields~, mugwort (Artemisia princeps Pamp., a
perennial weed of Compositae family, grown in cultivated
and uncultivated fields), large crabgrass (Digltaraia
adscendcus Henr., an annual wee of Gramineae family which
is a typical strongly injurious weed grown in upland
fields and orchards), Gi hi-gishi (Rumex ~aponicus
Houttuyn, a perennial weed of Polygonaceae family, grown
; in upland fields and on roadsides), umbrella sedge
- 23 -
:
.:- '' ' , :
;
... .
.
.. " . ,......
3~
1 (Cyperus iria L., an annual weed of Cyperaceae family,
grown in upland fields and on roadsides), redroot pigweed
~Amaranthus varidis L., an annual weed of Amaranthaceae
family grown in upland fields, vacant lands and roadsides),
and cocklebur (Xanthium Strumarium L., an annual weed of
Compositae family, strongly injurious to soybeans).
Since, ~2-1,2,4-triazolin-5-one derivatives
represented by the general formula ~I) exhibit excellent
controlling effects against weeds of both pre- and post-
emergent stages, they are useful as herbicides for soiltreatment before and after seeding (planting), for soil
treatment in the growth period, for foliar treatment
before seeding (planting), for foliar treatment in the
growth period of useful upland crops such as soybeans,
cotton, corns and the like. Furthermore, these derivatives
are useful as herbicides applying at the initial stage
and the middle stage of rice grown in paddy fields,
moreover, they are useful as herbicides to control general
weeds grown in for example/ ridges between paddy ~ields,
agricultural pathways, waterways, pasture, graveyards,
parks, roads, playgrounds, unoccupied areas around build-
ings, reclaimed lands, railways and forests. Herbicidal
treatments of such areas are carried out most effectively
and economically when weeds are not emergence but not
necessarily be done prior to the emergence of weeds.
For applying the derivatives of the present
invention as herbicides, they are generally formulated,
according to conventional procedures for pxeparing
- 24 ~
1 agricultural compositions, into a ~orm convenient to use.
That is, derivatives of the present invention are mixed
with suitable insert carriers and, if necessary, further
mixed with adjuvants, in a suitable ratio, and through
dissolution, dispersion, suspension, mechanical mixing,
impregnation, adsorption or adhesion, to make the mixture
into a suitable form of composition, e.g., suspensions,
emulsifiable concentrates, solutions, wettable powders,
dusts, granules or tablets.
As to the carriers to be used in the agricultural
compositions may be either solid carriers or liquid
carriers. Examples of acceptable solid carriers may be
cited vegetable powders such as soybean flour, cereal
flour, wood flour, bark flour, saw dust, powdered tobaco
stalks, powdered walnut shell, bran, powdered cellulose,
and extraction residues of vegetables; fibrous materials
such as paper, corrugated paperboard, and waste cloths;
synthe~ic polymers such a.s powdered synthetic resins~
inorganic or mineral products such as clays (e.g., kaolin,
bentonite and acid clay), talc products ~e.g., talc and
pyrophyllite~, silica products ~e.g., diatomaceous earth,
silica sand, mica and white carbon ~a highly dispersed
synthetic silicic acid, also called as finely pulverized
hydrated silica or hydrated silicic acid, and some of
commercially available products contain calcium silicate
as the major component~], activated carbon, powdered
sulfur~ p~ice, calcined dia~omaceous earth, yround brick,
fly ash, sand, calcium carbonate, and calcium phosphates;
- 25 -
3i~
1 chemical fertilizers such as ~mmonium sulfate, ammonium
phosphates, ammonium nitrate, urea, and ammonium chloride;
and farmyard manures. These solid carriers may be used
alone or in combination with one another. As to the
acceptable liquid carriers are selected from those which
are solvents for the active ingredients and those which
are non-solvent but can disperse the active ingredients
with the aid of adjuvants. Examples of these liquid
carriers may be used alone or in combination with one
another, are water, alcohols (e.g., methanol, ethanol,
isopropanol, butanol, and ethylene glycol), ketones
te.g., acetone, methyl ethyl ketone, methyl isobutyl
ketone, diisobutyl ketone, and cyclohexanone), ethers
(e.g., diethyl ether, dioxane, cellosolves, dipropyl
ether, and tetrahydrofuran), aliphatic hydrocarbons (e.g.,
gasoline and mineral oils), aromatic hydrocarbons (e.g.,
benzene, toluene, xylene, solvent naphtha, and alkyl-
naphthalene), halogenated hydrocarbones (e.g.,
dichloroethane, chlorinated henzenes, chloroform and
carbon tetrachloride), esters (e.g., ethyl acetate, dibutyl
phthalate, diisopropyl phthanate, and dioctyl phthalate),
acid amides (e.g., dimethylformamide, diethylformamide,
and dimethylacetamide), and nitriles (e.g., acetonitrile),
and dimethyl sulfoxide.
As to the adjuvants, which are exemplified
below, are used according to individual purposes. In
some cases, they are used in combination ~.~ith one another.
In some other cases, no adjuvant is used at all.
'7~31~
1 For the purpose of emulsification, dispersion,
solubilization and/or wetting of the active ingredients,
there can be used surface active agents, for example
polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl
ethers, polyoxyethylene higher fatty acid esters,
polyoxyethylene resinates, polyoxyethylene sorbitan
monolaurate r polyoxyethylene sorbitan monooeate, alkyl-
arylsulfonates, naphthalenesulfonic acid condensation
products, ligninsulfonates, and higher alcohol sulfate
esters. For the purpose of stabilizing the dispersion,
tackification and/or agglomeration of the active
ingredients, the following materials may be used, for
example, casein, gelatin, starch, alginic acid, methyl-
cellulose, carboxymethylcellulose, gum arabic, polyvinyl
alcohol, pine root oil, rice bran oil, bentoni-te and
ligninsulfonates.
For the purpose of improving the flow property
of the solid compositions, it is recommendable to use
waxes, stearates, or alkyl phosphates.
As to peptizers for dispersi~ie compositions,
it is also recommendable to use naphthalenesulfonic acid
condensation products and condensed phosphates.
It is also possible to add anti-foaming agents
such as for example, a silicone oil.
The content of the active ingredients in the
herbicidal composition may be adjusted depend on the
applications. ~or the preparation of powdered or
granulated products, it is generally 0.5 to 20% by weight
- 27 -
l of the active ingredients may be used, and for the
preparation of emulsifiable concentrates or wettable
powder products, it is generally 0.1 to 50% by weight
of the active ingredients may be used.
For destroying various weeds, inhibiting their
growth, or protecting useful plants from the injury
caused by these weeds, the herbicidal composition of the
present invention is used in a weed-destroying dosage or
a weed growth inhibiting dosage as such or after properly
diluted with or suspended in water or in other suitable
medium, to the soil or the foliage of weeds in the area
where the emergence or growth of weeds is undesirable.
The amount of the herbicidal composition of
the present invention to be used depends on various
factors such as, for example, the purpose of application,
the objective weeds, the emergence or growth state of
weeds and crops, the emergence tendency of weeds, weather,
environmental conditions, the form of herbicidal composi-
tion, the mode of application, the type of the field to
be treated, and the time of application and others.
In applying the present herbicidal composition
alone as a selective herbicide, it is suitable to select
the dosage of l to 500 g per 10 ares. On the other hand,
ill applying the present herbicidal composition in the
combined use of herbicides, the optimum dosage thereof
is often lower than that in the single use, the present
herbicidal composition may be used in an amount lower
than the above, when it is used in combination with
- 28 -
2~7~3~
1 another type of herbicide.
Herbicidal composition of the present invention
is especially valuable for the pre-emergence treatment
and initial emergence stage treatment of upland fields
and for the early stage and middle stage control o~ weeds
in paddy ~ields. In order to expand both range of
controllable weed species and the period of time when
effective applications are possible or to reduce the
dosage, the herbicidal composition of the present inven-
tion can be used in combination with other herbicides,and this usage is within the scope of the present
invention.
For example, herbicidal compositio~ of the
present invention can be used in combination with one
or more of the following herbicides.
Phenoxy fatty acid type herbicides: ~or example,
2,4-D: e.g., ethyl (2,4-dichlorophenoxy)-
acetate
MCP: e.g., ethyl (2-methyl-~-chlorophenoxy)-
acetate, sodium (2-methyl-4-chlorophenoxy~acetate, and
allyl 2-(2~methyl-4-chlorophenoxy)acetate
~ IC~P: e.g., ethyl ~2-methyl-4-chlorophenoxy)-
butyrate
Diclofop-methyl: me~hyl 2-[4-(2,4-
dichlorophenoxy)phenoxy]propanoate
Diphenyl ether type herbicides: ~or example,
Nitrogen: 2,4-dichlorophenyl 4-nitrophenyl
ether
- 29 -
'7;3~3
1 Chlornitrofen: 2,4,6-trichlorophenyl
4-nitrophenyl ether
Chlomethoxynil- 2,4-dichlorophenyl
3-methoxy-4-nitrophenyl ether
Acifluorfen: 5-(2-chloro~ -trifluoro-p-
tolyoxy)-2-nitrobenzoic acid and its salts
Fluazifop-butyl: butyl (+)-2-[4-[~5-
(trifluoromethyl)-2-pyridyl]oxy]phenoxy]propionate
Triazine type herbicides: ~cr example,
Simazine: 2-chloro-4,6-bi~(ethylamino)-s-
trlazlne
Prometryne: 2-methylthio-4,6-bis(iso-
propylamino)-s-triazine
Simetryne: 2-methylthio-4,6-bis(ethylamino)-
s-triazine, and
Metribuzino 4-amino-6-tert~butyl-3-methylthio-
1,2,4-triazin-5~H)-one
Carbamate type herbicides: for example,
Molinate: s-ethyl hexahydro-l~-azepine-l-
cabothioate
Swep: methyl N-(3,4-dichlorophenyl3carbamate
.Chloropropham: isopropyl N~(3-chlorophenyl)-
carbamate and
Benthiocarb: s-(4-chlorobenzyl)diethyl-
triocarbamate
Toluidine type herbicides: ~or exa~lple,
Trifluraline: (~,u,~-tri~luoro-2,6-dinitro-N,
N-dipropyl-p-toluidine and
- 30 -
, ~
~2~7~¢;7
1 Pendimethali.ne: N~ ethylpropyl)-2,6-
dinitro-3,4-xylidine
Acid amide type herbicides. for example,
Propanil: 3,4-dichloropropionanilide
Butachlor: N-(Butoxymethyl)-2-Chloro-2,6-
diethylacetanilide
Alachlor: 2-chlor--2,6-diethyl-N~
(methoxymethyl)acetanilide
Metolachlor: 2-chloro-N-(2-ethyl-6-
methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide and
PretilachlorO 2-chloro-2,6-diethyl-N-
~2-propoxyethyl)acetanilide
Other types of herbicides: for example,
Duron: 3-(3,4-dichlorophenyl)-1,1-
dimethylurea
Bentazon: 3-isopropyl-(H)-2,1,3-
- benzothiazin-4-(3H) one 2,2-dioxide
Pyraæolate: 4-(2,4-dichlorobenzoyl)-1,3-
dimethylpyrazol-5-yl-p~toluenesulfonate
Pyrazoxyfen: 1,3-dimethyl-4-(2,4-
dichlorobenzoyl)-5-phenacyloxypyrazol and
MY-71: 4-(2J4-dichloro-3~methylbenzoyl)-
1,3-dimethylpyraæol-5-yl-p-toluenesulfonate
The following examples illustrate the herbicidal
effects, and the herbicidal compositions of the present
invention. However, the present invention will not be
restricted only to these examples~
1 Herbicidal test example - 1
Controlling effect on paddy field weeds of
pre-emergence stage
Pots (1/10,000 - are) were filed with soil to
simulate a paddy field, and planted with seeds of barnyard
grass, monochoria, umbrella plant, and bulrush, and with
tubers of arrowhead, respectively, which are all injurious
weeds grown in paddy fields, were conditioned so as to
be in pre-emergence stage.
The soil in the pot was treated with each of
the present compounds (listed in Table 1) formulated to
given concentration of liquid, by spraying. After 21
days, the percent control of weed growth compared with
that on the untreated plot was observed and the herbicidal
activity was determined according to the criterion as
shown in the following Table 2.
- 32 -
X~3~
Table 2
Criterion for determining herbicidal
activity
Degree of Percent control of
herbicidal weed growth
activity (%)
100
4 90 - 99
3 80 - 89
2 70 - 79
1 Less than 70
The test results were summarized in Table 3.
- 33 -
~.
~ .~
a) ~
3 Ln Ln Ln Ln Ln Ln n Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln o
O
S~
s~ a)
a) o
a
5~ u~
5~ Ln Ln Ln Ln Ln Ln Ln Ln U~ Ln Ln Ln u~ Ln Ln Ln Ln Ln
a) ~
~ m
s~
a
~ l
a
s~
~ a~ ~ Ln Ln Ln Ln Ln Ln Ln Ln Ln ~n Ln In Ln Ln Ln Ln Ln Ln
Q
O D
a
~ I ~1
E~ O h Ln Ln Ln In Ln Ln Ln Ln Ln Ln Ln Ln Ln In In Ln Ln Ln
~: O
n~ Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln 11'1 Ln Ln Ln In
~u ~
o a) _
rl
o ~ o ~ o ~ o ~ o ~ o ~ o ~ o ~ o
0
O O ~ ~ co c~ ~ ~ 1-- co
~Z
O
O
-- 34 --
In ~ ~ r) u~ ~ Ln n ~ Ln Ln Lr Lr) Ln r~ In Lr Ln n Ln Lr)
o
E~
n Ln n Ln Ln Ln Ln Ln Ln Ln ~n In n Ln In Ln Ln Ln Ln Ln Ln L-~
n Ln Lr~ n u~ n Ln Lr) n Ln Ln Ln Ln n Ln L~ Ln Ln ~ n
,~
o
In Ln Ln U Ln Ln L~ Ln Ln Lr~ Ln Ln U~ Ln Lf~ n Ln Ln Ln Ln Ln
a~
E~
~ O Lr~ Ln In Ln Ln n n Ln L~ Ln n Ln Ln Ln LO In L~ Ln Ln Ln
C:~ ~ O t'') O ~ O ~) O ~7 0 ~ O ~ O ~ O ~ O ~) O 1~)
n ~ co
-- 35 --
a
E~
.~
o
R
E~
Or'~Or~or~or~or~or~)or~or~10t~O~Or~
r~7 r~ ~ r~
36
~d ~ u~
a) :~ (~
U~ X
o o a)
~ O
I ~ ~1 1 ~o
O ~ --
O h N a~
O C) rl O
~7 ~ X U~
O I Cl~ O I
O rl
-I -- O N u~
Q~ O
O N ~ ,~
u~ td 1-- ~ I
.,1 ,1 o ~ ~ Z
~1 0 I G
L~l ~ O Ll~ I rl
I ~1 1 ~1
O ~P I O
o ~ U~ o
~ I O
~1 ~ Z ~rl ~ a
O
V ~ S O
~ _ ~ X --
a~
,1 ~ ~ ~ O
11 0
~, :4 'u
o ~ a) o ~ ,1
Z ~3 a~ ~ I ~
3 0 ~ ~ ~-1 0
O ~ ~ O ~ ~
O r l 1~ 0 S 'ra
O ~ ~ ~ ~ ~
O O
~3 ~o3
a) ~ ~
t~ rd t) C~
a) ~ ~ a
5~ 0 ~ ~ S~
~D ~ ~ ~ ~
W ~ ~ W
o a) a
C) ~;
-- 37
3~
1 Herbicidal test example - 2
Controlling effect on paddy field weeds of
post-emergence stage
Pots (1/10,000 - are~ were filled with soil
to simulate a paddy field and grown with each of injurious
-weeds of the followiny lead age. In addition, young
seedings of rice plant (cultivar: "Nihonbarei') of the
2.5 lead age were transplanted to the soil on the day
before the treatment with each of the present herbicides.
After 21 days, the herbicidal effect and the degree of
crop injury were evaluated by comparing the results with
those on the untreated plot.
Species of weed tested Leaf age of the weed
Barnyard grass
Monochoria 2 - 3
Umbrella plant 1 - 2
Bulrush 2 - 3
Arrowhead 3
Water nutgrass 1 - 2
The criterion for judging the degree of crop
injury are as follows:
H: High ~including withering)
M: Medium
L: I.ow
N: None
The criterion for judging the herbicidal
~ 38 -
'73~3
1 activity is in accordance with that used in herbicidal
test example - 1. The results were summarized in Table
4.
- 3g -
~Z~ 3~3
O -r O ~::
~ .~ g
h ~ ¦ O
~ ,IJ
3 ~
a~ o
S~
S~
a~
U~
Ei ~
a~
U~
O 1~
~r ~ ,1
~1 0 ~
Q ~S
E~ ~ ~ ~
I .,1
~:: O
~ I
h td
h
~Q
O ~,_
,1
1 O ~1 0 ~ O ~ o ~ o ~ o ~ o ~ o ~ o r~
~ rl
0~ t~
O O , t ~ cc ~ , 1 ~ 1~ a) c~
C) r l r~ r~ r~ r~
-- 40 --
3`~3
o
Q
o
a~
~1
O
E~
o ~ o ~ o ~ o ~7 o ~ o ~ o ~ o ~ o ~ o ~ o
-- 41 --
7~
o
Q
E~
~r
o ~ o ~ o ~ o ~ o ~ o ~ o r~ o ~ o ~ o ~ o
-- 42 ~
Lr
E~
~1
~ o
~ u~
R
h
a:
In 1~7 N
U~
O ~ ,~ , O
E~
o
a
O
~1
a
a~ ~ O
Q) O
- 43
3~
1 Herbicidal test example - 3
Controlling effect on upland field weeds of
pre-emergence stage
Polyethylene vats, having 10 x 20 x 5 cm (depth)
size, were filled with soil and seeded with oats, barnyard
grass, large crabgrass, redroot pigweed, mugwort,
Gishi-gishi, umbrella sedge and cocklebur, respectively,
and seeds were covered with soil.
The soil was treated with each of the present
herbicides formulated to a given concentration of liquid,
by spraying. After 21 days, the herb.icidal e~fect was
evaluated by comparing the results with those on the
untreated plot. The criterion for judging the herbicidal
activity is the same as shown in test example - 1. The
results were summarized in Table 5.
- 4~ -
3~
O Ln Ln Ir) Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln
~, ~
tl~ Q
h ~) Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Lt~ Ln
O D ul
~/
.,1 .,_1
~ ~C ~ Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln ~n Ln Ln Lr~ Ln Ln Ln Ln
c) ~ u~
~ t~ ~
s~ ~
E3 3 Ln Ln Ln Ln Lr~ Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln n Ln Ln
~D :1
s~
L~
o o ~
~1 3 Ln L~) Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Lrl Ln Ln
C~
Ln ~ P~ Q
4J
a) ~ u~
u~
Q t~
S~
E~ ~ ~ Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln
t~ ~1
S~
U~
~ ~n Ln ~r Ln ~;r Ln ~ Ln ~ Ln ~ Ln ~r Ln ~ Ln Ln Ln Ln
5~ 1~
~5 h
:q
~ ¦ Ln ~ Ln ~ Ln ~r Ln ~r Ln ~ Ln ~r Ln ~ Ln ~r Ln ~
o
o ~
~ o ~ o ~ o ~ o ~ o ~ o ~ o ~ o ~ o ~
O ~ ~ tJ'
o o ~ ~ co ~ ~ ~ l`
~Z ~ ~ ~ ~1 ~
o
- ~1 5
3~3
Ln n Ln u~ Ln Ln Ln Ln n Ln Ln Ln n Ln Ln Ln Ln n Ln Ln Ln n
D
n Ln In In In Ln In Ln u~ In Ln In In In Ln In Ln Ln Lr, Ln Ln n ~-
n Ln Ln ~ Ln Ln Ln In In ~n Ln n Ln In Ln In n Ln Ln In n n
n n n Ln n Ln n Ln n n Ln Ln n n Ln Ln n Ln n Ln Ln n
a)
n n n Ln Ln In Ln In n n n n n Ln n n ~n n n Ln Ln n
~1
o
-
Ln n Ln Ln Ln Ln Ln Ln n Ln In In In In In In In Ln Ln Ln Ln Ln Ln
a)
Ln u~ In In In Ln Ln ~r In In Ln Ln Ln Ln In In Ln n In In n Ln
Ln ~r In ~ m ~ r In ~r Ln ~ In ~r In In Ln d In ~ Ln ~r
~ o ~ o ~ o ~ o ~ o ~ o ~ o ~ ~
,~ ~ ~ ,~ ~ ~ ~ Ln
_ a~6 --
.
r~
Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln s::
o
E~
Ln Ln Ln n Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln n Ln Ln Ll-) --
Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ll") Ln Ln Ln Ln
Ln Ln Ln Ln Ln Ln Ln Ln n Ln Ln Ln Lt') Ln Ln Ln Ln Ln Ln Ln Ln Ln
Ln Ln Ln Ln Ln Ltl Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ll~ Ln Ln
o
Ln Ln Ln Ln Ln Ln LO Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln
E~
Ln Ln Ln ~r Ln Ln Ln ~ Ln Ln Ln ~ Ln ~ Ln Ll~ ~n Ln Ln Ln Ln
Ln ~ Ln ~ Ln ~ Ln ~ Ln ~ Ln ~ Ln ~ Ln Ln Ln ~ r Ln e:r
o ~ o ~ o ~ o ~ o ~7 o ~7 o ~ o ~ ~ ~ o ~ o
Ln a~ r Ln ~ co ,~ ~ Ln
~r ~r ';Y Ln Ln Ln Ln L~ ~D ~D L~:)
-- 47 --
, .
In ln ~r
u~ In ~r
-
o
c~
E~
~n ~r ~ ,1
o ~ ~ ~
m
~;
-- 48 --
1 Herbicidal test example - 4
Controlling effect on upland field weeds of
post-emergence stage
Polyethylene vats, having 10 x 20 x 5 cm
(depth) size, were filled with soil and seeded with the
weeds shown below and soybean seeds, respectively, and
the seeds were covered with soil. The weeds and soybean
were cultivated respect.ively to the following leaf ages
and then treated with each of the present active compounds
at a given dosage.
After 21 days, the herbicidal effect on the
weeds and the degree of corp injury to the soybean were
evaluated by comparing the results with those on the
untreated plot.
Species of test plant Leaf age
Oats 2
Large crabgrass 2
Redroot pigweed
Mugwort
Gishi-gishi 2
Umbrella sedge
Cocklebur
Soybean First tri~oliate age
The criteria for judging the herbicidal
activity and crop injury were in accordance with those
used in herbicidal test examples -1 and -2, respectively.
The results were summarized in Table 5.
- 44 _
o r Q ~1 ~ ~ ~ ~1
U~
Q
n Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln ~
t,
O
U
Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ltl Ln Ln Ln Ln
a
~
~ :: ~ Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln
~ C~
a~
~ ~ 3o Ln LO Ln Ln Ln n Ln Ln Ln Ln Ln Ln Ln Ln Ln U~ Ln Ln Ln Ln
a~ ~ :~
E~ O O ~
~ 0 3 Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Ln Lo Ln Ln Ln Ln Ln Lo Ln Ln
L,L~ ~ ~
O P:; Q
C~ u~
~Q
L,L~
LL~ h ~ Ln ~;r Ln ~r Ln ~r Ln ~r Ln ~r L~ Ln Lo ~ Ln Ln ~n Ln Ln Lo
,a h
~ ¦ Ln ~r Ln ~ Ln ~r Ln ~r Ln ~r Ln ~r Ln ~ Ln ~r Ln ~r Ln ~r
ol
L~
O Q~_
rl (I)
O~Ot~Ot~Ot~70~Ot~Ot~Ot~Ot~Ot~
~ ~ ~J td t~ tr) tr) tr) t~) t~ t~) t~) t~ t~7
O
a-~
O O ~1 ~I t~o ~ ,I t~ tx~
~ Z ~ ~ ~ ~ ~ t~l
o
C~
- 50
~2~Z'7~3~
~,
E~
c
C~
Q
O ~ O t'') O ~) O ~ O ~ O ~) Q ~) O t~) O ~ O ~ O
-- 51 --
3¢~
o
a)
R
Lll m u~ ~ ~ In In L~ In m L~ m m ~n u~ m In ~n m ~
m Lr ~ In In In ~ In In ~ u~ In m In ~ In Ln In In m m u~
~ u~ m In In In Ll~ ~ ~ In m u~ n Ln In In In m In ~ Lo
a) .
m ~ Ln Lt~ m ~ In m m u~ m m m u~ m ~) Lr m m m
o
-
Ll~ m u~ m In u~ m !n ~ In m m Lr u~ m In m m m
E~
Ln m In ~ ~ ~ In ul In m m In m m u~ r m ~ m ~r
r m er u~ r In ~ In ~ m
O ~ 0 ~7 0 ~ O ~ O ~ o ~ o ~ o ~ o r~ o ~ o
~;r If) Lf~ ~ m m
- 52 -
73~
.,,
o
-
~D
~r
E~
a~
~,
o
~ o
P~ t,
~ 53 -
'7~3~
1 Example of herbicidal composition - 1
A wettable powder composition was prepared by
mixing uniformly and grinding the following ingredients:
Compound No. 3 50 Parts
Mixture of clay with white 45 Parts
carbon (in which clay
is contained as the major
component~
Polyoxyethylene nonylphenyl 5 Parts
ether
Example of herbicidal composition - 2
A granular composition was prepared by mixing
uniformly and grinding the following ingredients,
kneading the mixture with a suitable amount of water,
and granulating the kneaded mixture:
- Compound No. 25 S Parts
Mixture of bentonite90 Parts
with clay
Calcium ligninsulfonate 5 Parts
- 54 -
1 Example of herbicidal composition - 3
An emulsifiable concentrate was prepared by
mixing uniformly the following ingredients:
Compound No. 50 50 Parts
Xylene 40 Parts
Mixture of polyoxyethylene 10 Parts
nonylphenyl ether with
calcium alkylbenzenesulfonate
- 55 -
.~
