A herbicidal composition for foliar treatment is described, which contains as active ingredients, (a) a compound of general formula [1] wherein R is alkyl, cycloalkyl, alkenyl, dimethylamino, or diethylamino; and (b) a compound selected from the group consisting of atrazine, dicamba, clopyralid, 2,4-D, and bromoxynil. The herbicidal composition is useful for effective control of a wide variety of weeds in upland fields, particularly in corn fields. Also described are a weeding method by foliar treatment of weeds with the above herbicidal composition; and use as a herbicide for foliar treatment, of a mixture of the above active ingredients. ##STR1##

TECHNICAL FIELD 
The present invention relates to a herbicidal composition, and more 
particularly, it relates to a herbicidal composition for foliar treatment 
and a weeding method by foliar treatment of weeds therewith. 
BACKGROUND ART 
At the present time, numerous herbicides are commercially available and 
they are widely used. There are, however, many species of weeds to be 
controlled and their growth extends over a long time. For this reason, 
requested are herbicides with higher herbicidal activity, wide herbicidal 
spectrum, and safety to crops. 
DISCLOSURE OF INVENTION 
The present inventor has intensively studied to find out excellent 
herbicides. As a result, he has found that various weeds growing in crop 
lands or non-crop lands can be effectively controlled by foliar treatment 
of these weeds with a herbicidal composition containing as active 
ingredients, 
(a) a compound of the general formula: 
##STR2## 
wherein R is C.sub.1 -C.sub.7 alkyl, C.sub.5 -C.sub.6 cycloalkyl, C.sub.2 
-C.sub.6 alkenyl, dimethylamino, or diethylamino; and 
(b) a compound selected from the group consisting of 6-chloro-N.sup.2 
-ethyl-N.sup.4 -isopropyl-1,3,5-triazine-2,4-diamine (common name, 
atrazine; hereinafter referred to as atrazine), 
3,6-dichloro-2-methoxybenzoic acid (common name, dicamba; hereinafter 
referred to as dicamba), 3,6-dichloropicolinic acid (common name, 
clopyralid; hereinafter referred to as clopyralid), 
2,4-dichlorophenoxyacetic acid (common name, 2,4-D; hereinafter referred 
to as 2,4-D), and 3,5-dibromo-4-hydroxybenzonitrile (common name, 
bromoxynil; hereinafter referred to as bromoxynil). He has further found 
that the herbicidal activity is synergistically increased as compared with 
the cases where the active ingredients are independently used, and the 
herbicidal composition can, therefore, be applied at a lower amount; and 
that the herbicidal spectrum is expanded and a wide variety of weeds can 
be selectively controlled, particularly in corn fields, thereby completing 
the present invention. 
Thus, the present invention provides a herbicidal composition for foliar 
treatment comprising as active ingredients, (a) a compound of general 
formula [1] as depicted above, and (b) a compound selected from the group 
consisting of atrazine, dicamba, clopyralid, 2,4-D, and bromoxynil 
(hereinafter referred to as the present composition); and a weeding method 
by foliar treatment of weeds therewith.

MODE FOR CARRYING OUT THE INVENTION 
Compound [1], one of the active ingredients of the present composition, can 
be produced by the methods as described in the following production 
examples. 
Production Example 1 
To a solution of 5.3 g (53.3 mmol) of sodium acetate mixed with about 100 
ml of water was added under ice cooling 6.6 g (24.3 mmol) 
of1,1-dibromo-3,3,3-trifluoro-acetone, and the mixture was stirred at 
70.degree. C. for 20 minutes. The reaction mixture was cooled to room 
temperature, to which a solution of 5.8 g (21.5 mmol) of 
2-fluoro-4-chloro-5-isopropoxyphenylhydrazine dissolved in about 20 ml of 
diethyl ether was added, and the mixture was stirred at room temperature 
for 1 hour. The ether layer was separated and then concentrated. About 60 
ml of tetrahydrofuran (hereinafter referred to as THF) was added to the 
residue, to which 8.3 g (23.0 mmol) of 
(carbethoxyethylidene)triphenylphosphorane was added, and the mixture was 
heated under reflux for 2 hours. The THF was distilled out under reduced 
pressure, and the residue was subjected to silica gel column 
chromatography, which afforded 3.8 g (10.5 mmol) of 
2-[2-fluoro-4-chloro-5-isopropoxyphenyl]-4-methyl-5-trifluoromethyl-pyrida 
zin-3-one. 
Then, 3.5 g (9.7 mmol) of 
2-[2-fluoro-4-chloro-5-isopropoxyphenyl]-4-methyl-5-trifluoromethylpyridaz 
in-3-one was dissolved in about 10 ml of concentrated sulfuric acid under 
ice cooling, and the solution was warmed to room temperature. After ten 
minutes, about 100 ml of water was added to the reaction mixture. The 
deposited crystals were collected by filtration, and then washed twice 
with 20 ml of water and once with 10 ml of hexane in this order. The 
crystals thus obtained were recrystallized from isopropanol, which 
afforded 3.2 g (9.9 mmol) of 
2-[2-fluoro-4-chloro-5-hydroxy-phenyl]-4-methyl-5-trifluoromethylpyridazin 
-3-one. 
Then, 3.2 g (9.9 mmol) of 
2-[2-fluoro-4-chloro-5-hydroxyphenyl]-4-methyl-5-trifluoromethylpyridazin- 
3-one was dissolved in about 50 ml of N,N-dimethyl-formamide, to which 0.44 
g (11 mmol) of sodium hydride (60 wt % oil dispersion) was added at room 
temperature. The mixture was left stand at room temperature for 30 minutes 
and then cooled with ice, to which 1.8 g (11 mmol) of ethyl bromoacetate 
was added. The mixture was stirred at room temperature for 1 hour, to 
which diethyl ether and water were added in this order to make an 
extraction. The organic layer was washed with 10% aqueous hydrochloric 
acid solution, saturated aqueous sodium hydrogencarbonate solution, and 
saturated aqueous sodium chloride solution in this order, and then dried 
over anhydrous magnesium sulfate. The solvent was distilled out under 
reduced pressure, and the residue was subjected to silica gel column 
chromato-graphy, which afforded 2.4 g (5.5 mmol) of ethyl 
2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxy 
acetate (compound [1] wherein R is ethyl; hereinafter referred to as 
compound A), m.p., 102.0.degree. C. 
Production Example 2 
The same procedure as described in Production Example 1 is repeated, except 
that the following reaction reagents are substituted for ethyl 
bromoacetate. Thus, the desired ester derivatives of 
2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyrida-zinon-2-yl)phenox 
yacetic acid can be obtained. 
TABLE 1 
______________________________________ 
Ester Compound Physical 
Reaction reagent* 
produced* symbol property (m.p.) 
______________________________________ 
Methyl bromoacetate 
Methyl ester 
B 80.4.degree. C. 
Propyl bromoacetate 
Propyl ester 
C 82.9.degree. C. 
Butyl bromoacetate 
Butyl ester 
D 75.6.degree. C. 
Pentyl chloroacetate 
Pentyl ester 
E 
Hexyl bromoacetate 
Hexyl ester 
F 
Heptyl bromoacetate 
Heptyl ester 
G 63.2.degree. C. 
i-Propyl bromoacetate 
i-Propyl ester 
H 
i-Butyl bromoacetate 
i-Butyl ester 
I 
t-Butyl bromoacetate 
t-Butyl ester 
J 
c-Pentyl bromoacetate 
c-Pentyl ester 
K 
c-Hexyl bromoacetate 
c-Hexyl ester 
L 
Allyl bromoacetate 
Allyl ester 
M 
Vinyl chloroacetate 
Vinyl ester 
N 
______________________________________ 
*: "i", "t", and "c" mean iso, tertiary, and cyclo, respectively. 
.sup.1 H-NMR (250 MHz or 300 MHz, CDCl.sub.3, TMS, .delta.(ppm)) 
Compound E 
0.88 (3H, t, J=7 Hz), 1.2-1.4 (4H, m), 1.55-1.70 (2H, m), 2.43 (3H, J=2 
Hz), 4.19 (2H, t, J=7 Hz), 4.68 (2H, s), 6.98 (1H, d, J=7 Hz), 7.33 (1H, 
d, J=8 Hz), 7.99 (1H, s) 
Compound H 
1.26 (6H, d, J=6.3 Hz), 2.43 (3H, q, J=2 Hz), 4.65 (2H, s), 5.05-5.18 (1H, 
m), 6.98 (1H, d, J=7 Hz), 7.33 (1H, d, J=8 Hz), 7.98 (1H, s) 
Compound I 
0.90 (6H, d, J=6.6 Hz), 1.85-2.03 (1H, m), 2.42 (3H, q, J=1.8 Hz), 3.98 
(2H, d, J=6.5 Hz), 4.70 (2H, s), 6.99 (1H, d, J=6.3 Hz), 7.33 (1H, d, 
J=9.1 Hz), 7,98 (1H, s) 
Compound J 
1.45-1.53 (9H, m), 2.39-2.45 (3H, m), 4.58-4.60 (2H, m), 6.96-7.00 (1H, 
m,), 7.30-7.36 (1H, m), 7.96-8.00 (1H, m) 
Compound K 
1.5-1.9 (8H, m), 2.43 (3H, q, J=2 Hz), 4.65 (2H, s), 5.2-5.4 (1H, m d, 
J=7Hz),7.33(1H, d, J=8Hz),7.98(1H, s) 
Compound M 
2.42 (3H, q, J=1.9 Hz), 4.67-4.72 (2H, m), 5.23-5.37 (2H, m), 5.84-5.9 (1H, 
m), 7.00 (1H, d, J=6.3 Hz), 7.33 (1H, d, J=9.2 Hz), 7.99 (1H, s) 
Compound N 
2.42 (3H, q, J=1.8 Hz), 4.68-4.71 (1H, m), 4.77 (2H, s), 4.94-5.01 (1H, m), 
7.03 (1H, d, J=6.3 Hz), 7.26-7.31 (1H, m), 7.34 (1H, d, J=9.0 Hz), 7.99 
(1H, s) 
Production Example 3 
First, 1.0 g of the above compound A was dissolved in 15 ml of 1,4-dioxane, 
to which 15 ml of concentrated hydrochloric acid was added. This solution 
was warmed to 60.degree. C., stirred for 6 hours, and then extracted with 
ethyl acetate. The organic layer was washed with aqueous sodium 
hydrogencarbonate solution and saturated aqueous sodium chloride solution 
in this order, and then dried over anhydrous magnesium sulfate. The 
solvent was distilled out under reduced pressure. The residue was 
dissolved in 5 g of thionyl chloride, heated under reflux for 1 hour, and 
then concentrated under reduced pressure. The residue was dissolved in 20 
ml of THF at room temperature, to which 0.65 g of N,N-diethylhydroxylamine 
was added dropwise, and the mixture was then concentrated under reduced 
pressure. The residue was subjected to silica gel column chromatography, 
which afforded 1.1 g of 
O-[2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phen 
oxyacetyl]-N,N-diethylhydroxyl-amine (compound [1] wherein R is 
diethylamino; hereinafter referred to as compound O). 
.sup.1 H-NMR (250 MHz, CDCl.sub.3, TMS, .delta.(ppm)) 1.10 (6H, t, J=7.1 
Hz), 2.42 (3H, q, J=1.9 Hz), 2.94 (4H, q, J=7.1 Hz), 4.74 (2H, s), 7.01 
(1H, d, J=6.3 Hz), 7.33 (1H d, J=9.1 Hz), 7.97 (1H, s) 
Production Example 4 
The same procedure as described in Production Example 3 is repeated, except 
that N,N-dimethylhydroxylamine is substituted for 
N,N-diethylhydroxylamine. Thus, 
O-[2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phen 
oxyacet-yl]-N,N-dimethylhydroxylamine (compound [1] wherein R is 
dimethylamino; hereinafter referred to as compound P) can be obtained. 
Atrazine, dicamba, clopyralid, 2,4-D, and bromoxynil are compounds as 
described in Farm Chemicals Handbook, 1995 (published by Meister, 
Publishing Co., 1995), pages C32, C39, C348, C111, and C61, respectively. 
Dicamba, clopyralid, and 2,4-D can also be used in the form of 
agrochemically acceptable salts, and in the context of this specification, 
"dicamba", "clopyralid", and "2,4-D" include their salts. The salts may 
include, for example, alkali metal salts; alkaline earth metal salts; 
amine salts such as isopropylamine salts, dimethylamine salts, and 
diglycolamine salts; and ammonium salts. 
The present invention provides a herbicidal composition that is effective 
for control of a wide variety of weeds with crop selectivity and for 
application to a new cultivation method such as non-tillage cultivation. 
In particular, the herbicidal composition of the present invention 
effectively controls the main weeds in corn fields, e.g., dicotyledonous 
plants such as wild buckwheat (Polygonum convolvulus), pale smartweed 
(Polygonum lapathifolium), pennsylvania smartweed (Polygonum 
pensylvanicum), common purslane (Portulaca oleracea), common lambsquarters 
(Chenopodium album), redroot pigweed (Amaranthus retroflexus), wild 
mustard (Sinapis arvensis), hemp sesbania (Sesbania exaltata), sicklepod 
(Cassia obtusifolia), velvetleaf (Abutilon theophrasti), prickly sida 
(Sida spinosa), ivyleaf morningglory (Ipomoea hederacea), tall 
morningglory (Ipomoea purpurea), entireleaf morningglory (Ipomoea 
hederacea var. integriuscula), jimsonweed (Datura stramonium), black 
nightshade (Solanum nigrum), common cocklebur (Xanthium strumarium), 
common sunflower (Helianthus annuus), field bindweed (Convolvulus 
arvensis), sun spurge (Euphorbia helioscopia), devils beggarticks (Bidens 
frondosa), and common ragweed (Ambrosia artemisiifolia); and 
monocotyledonous plants such as barnyardgrass (Echinochloa crus-galli), 
green foxtail (Setaria viridis), giant foxtail (Setaria faberi), yellow 
foxtail (Setaria glauca), southern crabgrass (Digitaria ciliaris), 
goosegrass (Eleusine indica), johnsongrass (Sorghum halepense), quackgrass 
(Agropyron repens), and shattercane (Sorghum bicolor), while it exhibits 
no significant phytotoxicity on crops such as corn, and succeeding crops 
to corn, such as soybean. 
In the present composition, the mixing ratio of component (a) to component 
(b), although it may vary with the species of weeds to be controlled, 
situation and conditions of application, and other factors, is as follows: 
The weight ratio of compound [1] to atrazine is usually in the range of 
1:5 to 500. The weight ratio of compound [1] to dicamba is usually in the 
range of 1:2 to 200. The weight ratio of compound [1] to clopyralid, 
2,4-D, or bromoxynil is usually in the range of 1:1 to 200. 
The present composition may be usually used in the form of formulations 
such as emulsifiable concentrates, wettable powders, or flowables, which 
can be prepared by mixing the composition with solid carriers, liquid 
carriers, or other bulking agents, and if necessary, adding surfactants or 
other adjuvants to this mixture. In such a formulation, component (a) and 
component (b) are usually contained at the total amount of 0.5 to 90 wt %, 
preferably 1 to 80 wt %. 
The solid carrier to be used in the formulation may include, for example, 
the following materials in fine powder or granule form: clays (e.g., 
kaolinite, diatomaceous earth, synthetic hydrated silicon oxide, Fubasami 
clay, bentonite, acid clay); talc and other inorganic minerals (e.g., 
sericite, powdered quartz, powdered sulfur, activated carbon, calcium 
carbonate); and chemical fertilizers (e.g., ammonium sulfate, ammonium 
phosphate, ammonium nitrate, ammonium chloride, urea). The liquid carrier 
may include, for example, water; alcohols (e.g., methanol, ethanol); 
ketones (e.g., acetone, methyl ethyl ketone, cyclohexanone); aromatic 
hydrocarbons (e.g., toluene, xylene, ethylbenzene, methylnaphthalene); 
non-aromatic hydrocarbons (e.g., hexane, cyclohexane, kerosine); esters 
(e.g., ethyl acetate, butyl acetate); nitrites (e.g., acetonitrile, 
isobutyronitrile); ethers (e.g., dioxane, diisopropyl ether); acid amides 
(e.g., dimethylformamide, dimethylacetamide); and halogenated hydrocarbons 
(e.g., dichloroethane, trichloroethylene). 
The surfactant may include, for example, alkylsulfate esters; 
alkylsulfonate salts; alkylarylsulfonate salts; alkyl aryl ethers and 
their polyoxyethylene derivatives; polyethylene glycol ethers; polyhydric 
alcohol esters; and sugar alcohol derivatives. 
The other adjuvants may include, for example, adhesive agents and 
dispersing agents, such as casein, gelatin, polysaccharides (e.g., 
powdered starch, gum arabic, cellulose derivatives, alginic acid), lignin 
derivatives, bentonite, and synthetic water-soluble polymers (e.g., 
polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid); and 
stabilizers such as PAP (isopropyl acid phosphate), BHT 
(2,6-di-tert-butyl-4-methylphenol), BHA 
(2-/3-tert-butyl-4-methyoxyphenol), vegetable oils, mineral oils, fatty 
acids, and fatty acid esters. 
The present composition can also be prepared by making the active 
ingredients into the respective formulations using the above formulation 
technique and then mixing these formulations. 
The present composition thus formulated may be applied to plants as such, 
or after diluted with water or other solvents. The present composition may 
also be used in admixture with other herbicides, in which case the 
herbicidal activity can be expected to be enhanced. The present 
composition can also be used together with insecticides, bactericides, 
fungicides, plant growth regulators, fertilizers, soil conditioners, or 
other agents. 
The application amount of the present composition, although it may vary 
with the mixing ratio of component (a) to component (b) as the active 
ingredient compounds, weather conditions, formulation types, application 
times, application methods, application places, weeds to be controlled, 
and crops to be protected, is usually in the range of 10 to 2000 g as the 
total amount of active ingredient compounds per hectare. In the case of 
emulsifiable concentrates, wettable powders, flowables, or other similar 
formulations, they are usually applied after diluted in their prescribed 
amounts with water at a ratio of 100 to 1000 liters per hectare. 
The following will describe formulation examples, in which parts are by 
weight. 
Formulation Example 1 
Two parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 40 
parts of atrazine, 3 parts of calcium lignin sulfonate, 2 parts of sodium 
laurylsulfate, and 53 parts of synthetic hydrated silicon oxide are well 
pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 2 
Five parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 
40 parts of atrazine, 3 parts of calcium lignin sulfonate, 2 parts of 
sodium laurylsulfate, and 50 parts of synthetic hydrated silicon oxide are 
well pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 3 
Ten parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 40 
parts of atrazine, 3 parts of calcium lignin sulfonate, 2 parts of sodium 
laurylsulfate, and 45 parts of synthetic hydrated silicon oxide are well 
pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 4 
Five parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 
40 parts of atrazine, 3 parts of polyoxyethylene sorbitan monooleate, 3 
parts of CMC (carboxymethylcellulose), and 49 parts of water are mixed and 
wet pulverized until the particle size comes to 5 microns or smaller to 
give a flowable for each compound. 
Formulation Example 5 
Two parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 40 
parts of atrazine, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts 
of CMC (carboxymethylcellulose), and 52 parts of water are mixed and wet 
pulverized until the particle size comes to 5 microns or smaller to give a 
flowable for each compound. 
Formulation Example 6 
Two parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 50 
parts of atrazine, 3 parts of calcium lignin sulfonate, 2 parts of sodium 
laurylsulfate, and 43 parts of synthetic hydrated silicon oxide are well 
pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 7 
Two parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 28 
parts of dicamba, 3 parts of calcium lignin sulfonate, 2 parts of sodium 
laurylsulfate, and 65 parts of synthetic hydrated silicon oxide are well 
pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 8 
Five parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 
70 parts of dicamba, 3 parts of calcium lignin sulfonate, 2 parts of 
sodium laurylsulfate, and 20 parts of synthetic hydrated silicon oxide are 
well pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 9 
Twenty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 
50 parts of dicamba, 3 parts of calcium lignin sulfonate, 2 parts of 
sodium laurylsulfate, and 25 parts of synthetic hydrated silicon oxide are 
well pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 10 
Twenty-five parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, 
or P, 50 parts of dicamba, 3 parts of calcium lignin sulfonate, 2 parts of 
sodium laurylsulfate, and 20 parts of synthetic hydrated silicon oxide are 
well pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 11 
Two parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 28 
parts of dicamba, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts 
of CMC (carboxymethylcellulose), and 64 parts of water are mixed and wet 
pulverized until the particle size comes to 5 microns or smaller to give a 
flowable for each compound. 
Formulation Example 12 
One part of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 14 
parts of dicamba, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts 
of CMC (carboxy-methylcellulose), and 79 parts of water are mixed and wet 
pulverized until the particle size comes to 5 microns or smaller to give a 
flowable for each compound. 
Formulation Example 13 
One part of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 30 
parts of dicamba, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts 
of CMC (carboxy-methylcellulose), and 64 parts of water are mixed and wet 
pulverized until the particle size comes to 5 microns or smaller to give a 
flowable for each compound. 
Formulation Example 14 
Two parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 28 
parts of clopyralid, 3 parts of calcium lignin sulfonate, 2 parts of 
sodium laurylsulfate, and 65 parts of synthetic hydrated silicon oxide are 
well pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 15 
Five parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 
70 parts of clopyralid, 3 parts of calcium lignin sulfonate, 2 parts of 
sodium laurylsulfate, and 20 parts of synthetic hydrated silicon oxide are 
well pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 16 
Twenty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 
50 parts of clopyralid or a salt thereof, 3 parts of calcium lignin 
sulfonate, 2 parts of sodium laurylsulfate, and 25 parts of synthetic 
hydrated silicon oxide are well pulverized and mixed to give a wettable 
powder for each compound. 
Formulation Example 17 
Twenty-five parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, 
or P, 50 parts of clopyralid, 3 parts of calcium lignin sulfonate, 2 parts 
of sodium laurylsulfate, and 20 parts of synthetic hydrated silicon oxide 
are well pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 18 
Two parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 28 
parts of clopyralid, 3 parts of polyoxyethylene sorbitan monooleate, 3 
parts of CMC (carboxymethylcellulose), and 64 parts of water are mixed and 
wet pulverized until the particle size comes to 5 microns or smaller to 
give a flowable for each compound. 
Formulation Example 19 
One part of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 14 
parts of clopyralid or a salt thereof, 3 parts of polyoxyethylene sorbitan 
monooleate, 3 parts of CMC (carboxymethylcellulose), and 79 parts of water 
are mixed and wet pulverized until the particle size comes to 5 microns or 
smaller to give a flowable for each compound. 
Formulation Example 20 
One part of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 30 
parts of clopyralid, 3 parts of polyoxyethylene sorbitan monooleate, 3 
parts of CMC (carboxymethylcellulose), and 64 parts of water are mixed and 
wet pulverized until the particle size comes to 5 microns or smaller to 
give a flowable for each compound. 
Formulation Example 21 
Two parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 28 
parts of 2,4-D, 3 parts of calcium lignin sulfonate, 2 parts of sodium 
laurylsulfate, and 65 parts of synthetic hydrated silicon oxide are well 
pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 22 
Five parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 
70 parts of 2,4-D, 3 parts of calcium lignin sulfonate, 2 parts of sodium 
laurylsulfate, and 20 parts of synthetic hydrated silicon oxide are well 
pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 23 
Twenty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 
50 parts of 2,4-D, 3 parts of calcium lignin sulfonate, 2 parts of sodium 
laurylsulfate, and 25 parts of synthetic hydrated silicon oxide are well 
pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 24 
Twenty-five parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, 
or P, 50 parts of 2,4-D, 3 parts of calcium lignin sulfonate, 2 parts of 
sodium laurylsulfate, and 20 parts of synthetic hydrated silicon oxide are 
well pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 25 
Two parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 28 
parts of 2,4-D, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of 
CMC (carboxymethylcellulose), and 64 parts of water are mixed and wet 
pulverized until the particle size comes to 5 microns or smaller to give a 
flowable for each compound. 
Formulation Example 26 
One part of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 14 
parts of 2,4-D, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of 
CMC (carboxy-methylcellulose), and 79 parts of water are mixed and wet 
pulverized until the particle size comes to 5 microns or smaller to give a 
flowable for each compound. 
Formulation Example 27 
One part of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 30 
parts of 2,4-D, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of 
CMC (carboxy-methylcellulose), and 64 parts of water are mixed and wet 
pulverized until the particle size comes to 5 microns or smaller to give a 
flowable for each compound. 
Formulation Example 28 
Two parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 28 
parts of bromoxynil, 3 parts of calcium lignin sulfonate, 2 parts of 
sodium laurylsulfate, and 65 parts of synthetic hydrated silicon oxide are 
well pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 29 
Five parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 
70 parts of bromoxynil, 3 parts of calcium lignin sulfonate, 2 parts of 
sodium laurylsulfate, and 20 parts of synthetic hydrated silicon oxide are 
well pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 30 
Twenty parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 
50 parts of bromoxynil, 3 parts of calcium lignin sulfonate, 2 parts of 
sodium laurylsulfate, and 25 parts of synthetic hydrated silicon oxide are 
well pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 31 
Twenty-five parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, 
or P, 50 parts of bromoxynil, 3 parts of calcium lignin sulfonate, 2 parts 
of sodium laurylsulfate, and 20 parts of synthetic hydrated silicon oxide 
are well pulverized and mixed to give a wettable powder for each compound. 
Formulation Example 32 
Two parts of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 28 
parts of bromoxynil, 3 parts of polyoxyethylene sorbitan monooleate, 3 
parts of CMC (carboxymethylcellulose), and 64 parts of water are mixed and 
wet pulverized until the particle size comes to 5 microns or smaller to 
give a flowable for each compound. 
Formulation Example 33 
One part of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 14 
parts of bromoxynil, 3 parts of polyoxyethylene sorbitan monooleate, 3 
parts of CMC (carboxymethylcellulose), and 79 parts of water are mixed and 
wet pulverized until the particle size comes to 5 microns or smaller to 
give a flowable for each compound. 
Formulation Example 34 
One part of compound A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, 30 
parts of bromoxynil, 3 parts of polyoxyethylene sorbitan monooleate, 3 
parts of CMC (carboxymethylcellulose), and 64 parts of water are mixed and 
wet pulverized until the particle size comes to 5 microns or smaller to 
give a flowable for each compound. 
The following will describe test examples. 
Evaluation Criteria 
The herbicidal activity is evaluated at 11 levels with indices of 0 to 10, 
i.e., shown by numeral "0", "1", "2", "3", "4", "5", "6", "7", "8", "9", 
or "10" wherein "0" means that there was no or little difference in the 
degree of germination or growth between the treated plants and the 
untreated plants at the time of examination, and "10" means that the test 
plants died completely or their germination or growth was completely 
inhibited. The herbicidal activity is excellent when ranked at "7", "8", 
"9", or "10", but insufficient when ranked at "6" or lower. The 
phytotoxicity is shown by "no injury" when no significant phytotoxicity 
was observed; "low" when low phytotoxicity was observed; "moderate" when 
moderate phytotoxicity was observed; or "high" when high phytotoxicity was 
observed. 
Test Example 1 
Plastic pots each having an area of 26.5.times.19 cm.sup.2 and a depth of 7 
cm were filled with upland soil, and then seeded with corn (Zea mays), 
giant foxtail (Setaria faberi), and southern crabgrass (Digitaria 
ciliais). These test plants were grown in a greenhouse for 23 days. 
An emulsifiable concentrate of compound A, which had been obtained by well 
mixing 10 parts of compound A, 14 parts of polyoxyethylene styryl phenyl 
ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene, and 
35 parts of cyclohexa none, a formulation product of atrazine (trade name, 
AAt rex; Ciba-Geigy Ltd.), and a mixture of the emulsifiable concentrate 
of compound A and the formulation product of atrazine were independently 
diluted in their prescribed amounts with water. Each dilution was 
uniformly sprayed over the test plants with a small sprayer. The same 
procedure was repeated for compounds E and O. After the application, the 
test plants were grown in the greenhouse for 4 days, and the herbicidal 
activity and safety to corn were then examined. The results are shown in 
Table 2. 
TABLE 2 
______________________________________ 
Herbicidal activity 
Dosage southern giant Phytotoxicity 
Compound (g/ha) crabgrass 
foxtail corn 
______________________________________ 
Compound A 
20 3 4 no injury 
Compound E 
20 3 4 no injury 
Compound O 
20 3 4 no injury 
Atrazine 500 3 2 no injury 
Compound A + 
20 + 500 9 9 no injury 
atrazine 
Compound E + 
20 + 500 9 9 no injury 
atrazine 
Compound O + 
20 + 500 9 9 no injury 
atrazine 
______________________________________ 
Test Example 2 
Plastic pots each having an area of 26.5.times.19 cm.sup.2 and a depth of 7 
cm were filled with upland soil, and then seeded with corn (Zea mays), 
giant foxtail (Setaria faberi), and southern crabgrass (Digitaria 
ciliaris). These test plants were grown in a greenhouse: corn, for 16 
days; and giant foxtail and southern crabgrass, for 23 days. 
An emulsifiable concentrate of compound E, which had been obtained by well 
mixing 10 parts of compound E, 14 parts of polyoxyethylene styryl phenyl 
ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene, and 
35 parts of cyclohexanone, a formulation product of dicamba (trade name, 
Clarity; Sandoz, Ltd.), and a mixture of the emulsifiable concentrate of 
compound E and the formulation product of dicamba were independently 
diluted in their prescribed amounts with water. Each dilution was 
uniformly sprayed over the test plants with a small sprayer. The same 
procedure was repeated for compound O. After the application, the test 
plants were grown in the greenhouse for 4 days, and the herbicidal 
activity and safety to corn were then examined. The results are shown in 
Table 3. 
TABLE 3 
______________________________________ 
Herbicidal activity 
Dosage southern giant Phytotoxicity 
Compound (g/ha) crabgrass 
foxtail corn 
______________________________________ 
Compound E 
20 3 4 no injury 
Compound O 
20 3 4 no injury 
Dicamba 200 1 1 no injury 
Compound E + 
20 + 200 8 8 no injury 
dicamba 
Compound O + 
20 + 200 8 8 no injury 
dicamba 
______________________________________ 
Test Example 3 
A upland field was seeded with corn (Zea mays), and the plant was grown for 
19 days. 
A flowable of compound A, which had been obtained by mixing 10 parts of 
compound A, 2 parts of a mixture of polyoxyethylene alkylarylphosphate and 
polyoxyethylene alkyl aryl ether, and 25 parts of water, pulverizing the 
mixture by wet grinding method so that the particle size came to 5 microns 
or smaller, adding 11 parts of a thickening agent (xanthan gum and 
smectite clay) and an antifreezing agent (propylene glycol) to the 
pulverized mixture, and further adding water so that the total amount came 
to 100 parts, a formulation product of dicamba as described above, and a 
mixture of the flowable of compound A and the formulation product of 
dicamba were independently diluted in their prescribed amounts with water. 
Each dilution was uniformly sprayed over the test plants, i.e., corn (Zea 
mays) and southern crabgrass (Digitaria ciliaris) growing in the field, 
with a sprayer installed on a tractor. On the 7th day after the 
application, the herbicidal activity and safety to corn were then 
examined. The results are shown in Table 4. 
TABLE 4 
______________________________________ 
Herbicidal 
activity 
Dosage southern Phytotoxicity 
Compound (g/ha) crabgrass 
corn 
______________________________________ 
Compound A 20 5 no injury 
Dicamba 280 0 no injury 
Compound A + 
20 + 280 9 no injury 
dicamba 
______________________________________ 
Test Example 4 
Plastic pots each having an area of 26.5.times.19 cm.sup.2 and a depth of 7 
cm were filled with upland soil, and then seeded with corn (Zea mays), 
giant foxtail (Setaria faberi), southern crabgrass (Digitaria ciliaris), 
and barnyardgrass (Echinochloa crusgalli). These test plants were grown in 
a greenhouse for 23 days. 
An emulsifiable concentrate of compound A, which had been obtained by well 
mixing 10 parts of compound A, 14 parts of polyoxyethylene styryl phenyl 
ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene, and 
35 parts of cyclohexanone, a formulation product of clopyralid (trade 
name, Stinger; DowElanco), 2,4-D (trade name, 2,4-D amine salt; Nissan 
Chemical Industries, Ltd.), bromoxynil (trade name, Buctril; Rhone-Poulenc 
S.A.), a mixture of the emulsifiable concentrate of compound A and the 
formulation product of clopyralid, a mixture of the emulsifiable 
concentrate of compound A and the formulation product of 2,4-D, and a 
mixture of the emulsifiable concentrate of compound A and the formulation 
product of bromoxynil were independently diluted in their prescribed 
amounts with water. Each dilution was uniformly sprayed over the test 
plants with a small sprayer. After the application, the test plants were 
grown in the greenhouse for 5 days, and the herbicidal activity and safety 
to corn were then examined. The results are shown in Table 5. 
TABLE 5 
______________________________________ 
Herbicidal activity 
Phyto- 
Dosage giant southern 
barn- toxicity 
Compound (g/ha) foxtail crabgrass 
yardgrass 
corn 
______________________________________ 
Compound A 
20 4 4 6 no injury 
Clopyralid 
250 0 0 0 no injury 
2,4-D 250 0 0 0 no injury 
Bromoxynil 
250 2 2 2 no injury 
Compound A + 
20 + 250 7 7 8 no injury 
clopyralid 
Compound A + 
20 + 250 7 7 8 no injury 
2,4-D 
Compound A + 
20 + 250 8 8 9 no injury 
bromoxynil 
______________________________________ 
Industrial Applicability 
A wide variety of weeds in upland fields, particularly in corn fields, can 
be effectively controlled by the present composition.