Benzamide derivatives and herbicidal composition containing the same

A herbicidal composition comprises a novel compound of benzamide derivative having the formula ##STR1## wherein R represents a C.sub.1 -C.sub.8 alkyl group; X represents oxygen or sulfur atom and n is an integer of 1 or 2.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to novel benzamide derivatives and herbicidal 
compositions containing the benzamide derivative. 
2. Description of the Prior Arts 
Recently, many herbicides have been proposed and practically used to 
contribute for elimination of agricultural labour works. 
Thus, various problems on herbicidal effects and safety of the herbicides 
have been found in the practical applications. 
It has been required to find improved herbicides which have no adverse 
effect to the object plants and effective to noxious weeds in a small dose 
of the active ingredient and significantly safe without any environmental 
pollution. 
The inventors have synthesized various benzamides so as to find 
satisfactory herbicides and have studied herbicidal effects thereof, and 
the present invention has been attained. 
SUMMARY OF THE INVENTION 
It is an object of the present invention to provide specific benzamide 
derivatives and herbicidal compositions containing the same as an active 
ingredient. 
The foregoing and other objects of the present invention have been attained 
by providing novel benzamide derivatives having the formula 
##STR2## 
wherein R represents a C.sub.1 -C.sub.8 alkyl group, X represents oxygen 
or sulfur atom; n is an integer of 1 or 2. 
The herbicidal composition of the present invention comprises the novel 
benzamide derivative as an active ingredient and an adjuvant. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The typical novel benzamide derivatives of the present invention include as 
follows. 
TABLE 1 
______________________________________ 
Comp. Melting point 
No. (.degree.C.) 
______________________________________ 
1 4-Methoxymethoxy-N--(2,3-dichloro- 
109-111 
phenyl)-benzamide 
2 4-Ethoxymethoxy-N--(2,3-dichloro- 
87-88.5 
phenyl)-benzamide 
3 4-n-Propoxymethoxy-N--(2,3-dichloro- 
68.5-70.5 
phenyl)-benzamide 
4 4-n-Butoxymethoxy-N--(2,3-dichloro- 
70-71 
phenyl)-benzamide 
5 4-(2-Methoxyethoxy)-N--(2,3-dichloro- 
122-125 
phenyl)-benzamide 
6 4-(2-Ethoxyethoxy)-N--(2,3-dichloro- 
121.2-122 
phenyl)-benzamide 
7 4-(2-n-Propoxyethoxy)-N--(2,3-dichloro- 
98-100 
phenyl)-benzamide 
8 4-(2-n-Butoxyethoxy)-N--(2,3-dichloro- 
70-72 
phenyl)-benzamide 
9 4-Methylthiomethoxy-N--(2,3-dichloro- 
113-115 
phenyl)-benzamide 
10 4-Ethylthiomethoxy-N--(2,3-dichloro- 
89.5-91 
phenyl)-benzamide 
11 4-n-Butylthiomethoxy-N--(2,3-dichloro- 
58.5-60.5 
phenyl)-benzamide 
12 4-(2-Methylthioethoxy)-N--(2,3-dichloro- 
121.5-122.5 
phenyl)-benzamide 
13 4-(2-Ethylthioethoxy)-N--(2,3-dichloro- 
111-112 
phenyl)-benzamide 
______________________________________ 
The benzamide derivatives of the present invention can be produced by the 
following process. 
The benzamide derivatives can be produced by reacting 2,3-dichloroaniline 
with the corresponding benzoyl chloride derivative or benzoic acid ester 
derivative 
##STR3## 
(R' represents a moiety of the ester) in the presence of a base in an 
organic solvent. 
When the benzoyl chloride derivative is used, an organic or inorganic base 
such as alkali metal hydroxides and carbonates and pyridine and 
triethylamine can be used. The solvent can be any inert solvent such as 
acetone, toluene and dioxane. When the benzoic acid ester derivative is 
used, a special base such as sodium hydride or sodium methoxide is 
preferably used. 
The solvent is preferably a polar solvent such as dimethylsulfoxide. 
The benzamide derivatives can be produced by reacting 
4-hydroxy-N-(2,3-dichlorophenyl)-benzamide 
##STR4## 
with the corresponding alkoxyalkyl halide or alkylthioalkyl halide 
EQU RX(CH.sub.2).sub.n Hal 
(Hal represents a halogen atom) in the presence of a base in an organic 
solvent. 
An alkali metal salt of 4-hydroxy-N-(2,3-dichlorophenyl)benzamide can be 
used without using a base since it is the reaction product of the base. 
Potassium salt of 4-hydroxy-N-(2,3-dichlorophenyl)-benzamide is preferably 
used in the latter case. 
The base can be inorganic and organic bases such as alkali metal hydroxides 
and carbonates and pyridine and triethylamine. 
The solvent can be inert organic solvents such as acetone toluene, dioxane 
and N,N-dimethylformamide. 
A molar ratio of the corresponding benzoyl chloride derivative or benzoic 
acid ester derivative to 2,3-dichloroaniline is usually in a range of 1 to 
4 preferably 1 to 2. 
The reaction temperature can be in a range of room temperature to a 
refluxing temperature. 
The solvent can be aromatic hydrocarbons such as benzene, toluene and 
xylene and halohydrocarbons such as methylenechloride, chloroform and 
carbon tetrachloride, ketones such as acetone and ethers such as 
tetrahydrofuran and dioxane and polar solvents such as 
N,N-dimethylformamide and dimethylsulfoxide. An amount of the solvent is 
preferably in a range of 1 to 10 times by weight and preferably 2 to 5 
times by weight of the total reactants. 
A molar ratio of the corresponding benzoyl chloride derivative or benzoic 
acid ester derivative to the base is usually in a range of 1 to 6 
preferably 1 to 2. 
A molar ratio of the corresponding alkoxyalkyl halide or alkylthioalkyl 
halide to 4-hydroxy-N-(2,3-dichlorophenyl)-benzamide is usually in a range 
of 1 to 4 preferably 1 to 2. 
The reaction temperature can be in a range of 0.degree. C. to a refluxing 
temperature. 
The solvent can be aromatic hydrocarbons such as benzene, toluene and 
xylene and halohydrocarbons such as methylenechloride, chloroform and 
carbon tetrachloride, ketones such as acetone and ethers such as 
tetrahydrofuran and dioxane and polar solvents such as 
N,N-dimethylformamide and dimethylsulfoxide. An amount of the solvent is 
preferably in a range of 1 to 10 times by weight and preferably 2 to 5 
times by weight of the total reactants. 
A molar ratio of the corresponding alkoxyalkyl halide or alkylthioalkyl 
halide to the base is usually in a range of 1 to 6 preferably 1 to 3.

Typical examples for preparations of the compounds will be illustrated. 
Preparation 1: (Compound No. 6) 
A mixture of 7.2 g. of p-ethoxyethoxy benzoic acid, 50 ml. of dioxane and 
12.2 g. of thionyl chloride was refluxed at 70.degree. to 80.degree. C. 
for 2 hours. After the reaction, excess of thionyl chloride and the 
solvent were recovered by a rotary evaporator to obtain a crude 
p-ethoxyethoxybenzoic chloride as a residue. The crude 
p-ethoxyethoxybenzoic acid chloride was dissolved in 70 ml. of acetone and 
then, a mixture of 6.6 g. of 2,3-dichloroaniline and 4.1 g. of 
triethylamine was added dropwise with stirring at room temperature during 
30 minutes. After the addition, the mixture was stirred at the same 
temperature for 2 hours. After the reaction, the reaction mixture was 
poured into 300 ml. of 2% hydrochloric acid and the resulting precipitate 
was separated by a filtration. The resulting crude product was 
recrystallized from toluene to obtain 9.0 g. of 
4-(2-ethoxyethoxy)-N-(2,3-dichlorophenyl)-benzamide. The yield was 74.4 g. 
The compound had a melting point of 121.2.degree. to 122.degree. C. 
Preparation 2: (Compound No. 4) 
Into 20 ml. of toluene, 2.38 g. of methyl p-n-butoxymethoxybenzoate and 
1.64 g. of 2,3-dichloroaniline were dissolved and 1.62 g. of sodium 
methoxide was added to the solution. The mixture was stirred at 
105.degree. to 115.degree. C. for 4 hours. After the reaction, the 
reaction mixture was cooled to room temperature and the reaction mixture 
was washed for two times with 20 ml. of water and then was dehydrated over 
anhydrous sodium sulfate and then, toluene was recovered by a rotary 
evaporator to obtain an oily product. The oily product was crystallized 
from methanol to obtain 1.36 g. of 
4-n-butoxymethoxy-N-(2,3-dichlorophenyl)-benzamide as the object product. 
The yield was 36.8% and a melting point of the product was in a range of 
70.0.degree. to 71.0.degree. C. 
Preparation No. 3: (Compound No. 12) 
Into 30 ml. of N,N-dimethylformamide, 5.64 g. of 
4-hydroxy-N-(2,3-dichlorophenyl)-benzamide, 3.32 g. of 2-chloroethyl 
methylsulfide and 8.29 g. of potassium carbonate were dispersed and the 
mixture was stirred at 100.degree. to 110.degree. C. during 6 hours. After 
the reaction, the reaction mixture was poured into 300 ml. of 2% 
hydrochloric acid. The resulting precipitate was separated by a filtration 
and the resulting crude product was recrystallized from ethanol to obtain 
5.05 g. of 4-(2-methylthioethoxy)-N-(2,3-dichlorophenyl)-benzamide as the 
object product. The yield was 70.9% and the melting point of the product 
was 121.5.degree. to 122.5.degree. C. 
Preparation No. 4: (Compound No. 5) 
In accordance with the process of Preparation 3, except using 4.17 g. of 
2-bromoethyl methyl ether instead of 2-chloroethyl methylsulfide, a 
reaction was carried out to obtain 4.45 g. of 
4-(2-methoxyethoxy)-N-(2,3-dichlorophenyl)-benzamide having a melting 
point of 122.degree. to 125.degree. C. as the object product. The yield 
was 65.4%. 
Preparation No. 5: (Compound No. 7) 
In accordance with the process of Preparation 3, except using 5.01 g. of 
2-bromoethyl n-propyl ether instead of 2-chloroethyl methylsufide, a 
reaction was carried out to obtain 5.16 g. of 
4-(2-n-propoxyethoxy)-N-(2,3-dichlorophenyl)-benzamide having a melting 
point of 98.degree. to 100.degree. C. as the object product. The yield was 
70.1%. 
Preparation No. 6: (Compound No. 8) 
In accordance with the process of Preparation 3, except using 5.43 g. of 
2-bromoethyl n-butyl ether instead of 2-chloroethyl methylsulfide, a 
reaction was carried out to obtain 3.71 g. of 
4-(2-n-butoxyethoxy)-N-(2-3,-dichlorophenyl)-benzamide having a melting 
point of 70.degree. to 72.degree. C. as the object product. The yield was 
48.6%. 
Preparation No. 7: (Compound No. 13) 
In accordance with the process of Preparation 3, except using 5.07 g. of 
2-bromoethyl ethylsulfide instead of 2-chloroethyl methylsulfide, a 
reaction was carried out to obtain 5.85 g. of 
4-(2-ethylthioethoxy)-N-(2,3-dichlorophenyl)-benzamide having a melting 
point of 111.degree. to 112.degree. C. as the object product. The yield 
was 79.0%. 
Preparation No. 8: (Compound No. 2) 
Into 50 ml. of N,N-dimethylformamide, 6.4 g. of potassium 
4-hydroxy-N-(2,3-dichlorophenyl)-benzamide was dispersed and then, 3.8 g. 
of chloromethyl ethyl ether was added dropwise at 0.degree. C. during 30 
minutes. After the addition at the same temperature during 30 minutes, the 
mixture was stirred at room temperature for 30 minutes. After the 
reaction, the solvent was recovered by a rotary evaporator. The resulting 
residue was dissolved into 100 ml. of toluene and the solution was washed 
for 2 times with 100 ml. of water and dehydrated over anhydrous sodium 
sulfate and toluene was recovered by a rotary evaporator to obtain an oily 
product. The oily product was crystallized from methanol to obtain 4.2 g. 
of 4-ethoxymethoxy-N-(2,3-dichlorophenyl)-benzamide as the object product. 
The yield was 61.7%. The compound had a melting point of 87.0.degree. to 
88.5.degree. C. 
Preparation No. 9: (Compound No. 1) 
In accordance with the process of Preparation 8, except using 3.22 g. of 
chloromethyl methyl ether instead of chloromethyl ethyl ether, a reaction 
was carried out to obtain 3.32 g. of 
4-methoxy-methoxy-N-(2,3-dichlorophenyl)-benzamide having a melting point 
of 109.degree. to 111.degree. C. as the object product. The yield was 
50.8%. 
Preparation No. 10: (Compound No. 3) 
In accordance with the process of Preparation 8, except using 4.38 g. of 
chloromethyl n-propyl ether instead of chloromethyl ethyl ether, a 
reaction was carried out to obtain 4.19 g. of 
4-n-propoxymethoxy-N-(2,3-dichlorophenyl)-benzamide having a melting point 
of 68.5.degree. to 70.5.degree. C. as the object product. The yield was 
59.2%. 
Preparation No. 11: (Compound No. 9) 
In accordance with the process of Preparation 8, except using 3.86 g. of 
chloromethyl methylsulfide instead of chloromethyl ethyl ether, a reaction 
was carried out to obtain 3.80 g. of 
4-methylthiomethoxy-N-(2,3-dichlorophenyl)-benzamide having a melting 
point of 113.degree. to 115.degree. C. as the object product. The yield 
was 55.5%. 
Preparation No. 12: (Compound No. 10) 
In accordance with the process of Preparation 8, except using 3.32 g. of 
chloromethyl ethylsulfide instead of chloromethyl ethyl ether, a reaction 
was carried out to obtain 4.85 g. of 
4-ethylthiomethoxy-N-(2,3-dichlorophenyl)-benzamide having a melting point 
of 89.5.degree. to 91.0.degree. C. as the object product. The yield was 
68.1%. 
Preparation No. 13: (Compound No. 11) 
In accordance with the process of Preparation 8, except using 4.16 g. of 
n-butyl chloromethylsulfide instead of chloromethyl ethyl ether, a 
reaction was carried out to obtain 5.90 g. of 
4-n-butylthiomethoxy-N-(2,3-dichlorophenyl)-benzamide having a melting 
point of 58.5.degree. to 60.5.degree. C. as the object product. The yield 
was 76.8%. 
Preparation No. 14: (Compound No. 5) 
In accordance with the process of Preparation 8, except using 5.56 g. of 
2-bromoethyl methyl ether instead of chloromethyl ethyl ether, a reaction 
was carried out to obtain 4.89 g. of the object compound of 
4-(2-methoxyethoxy)-N-(2,3-dichlorophenyl)-benzamide. The yield was 71.9%. 
The herbicidal compositions of the present invention can be obtained by 
admixing the active ingredient with a desired adjuvant so as to form a 
wettable powder, an emulsifiable concentrate, a dust, a granule etc. 
The liquid adjuvant is usually an organic solvent and the solid adjuvant is 
usually mineral fine powder. In order to impart emulsifiable property, 
dispersable property and spreadable property, a desired surface active 
ingredient is added. The active ingredient can be used by admixing with an 
agricultural chemical such as a fertilizer, a herbicide, an insecticide 
and a germicide. 
The active ingredient of the compound of the present invention is applied 
depending upon a weather condition, a soil condition, a form of the 
composition, a season of the application and a method of the application 
and kinds of crop plants and kinds of weeds. The active ingredient is 
usually applied in a range of 1 to 2,000 g. preferably 1 to 1,000 g., 
especially 100 to 500 g. per 10 are in the treatment. The active 
ingredient is usually used in the form of a wettable powder, an 
emulsifiable concentrate or, a dust or a granule which comprises 0.1 to 50 
wt.% of the active ingredient. The active ingredient is usually applied in 
a concentration of 10 to 10,000 ppm preferably 100 to 5,000 ppm. 
especially 250 to 3,000 ppm. of the active ingredient. 
In the preparation of the emulsifiable concentrate, the active ingredient 
is dissolved in an agricultural acceptable organic solvent and a solvent 
soluble emulsifier is added. Suitable solvent is not usually miscible to 
water and include organic solvents such as hydrocarbons, chlorinated 
hydrocarbons, ketones, esters, alcohols and amides. Suitable solvents 
include toluene, xylene, naphtha, perchloroethylene, cyclohexanone, 
isophorone, dimethylformamide and mixtures thereof. The optimum solvents 
include aromatic hydrocarbons and ketones. A mixture of solvents is 
usually used. The surfactants used as the emulsifier is incorporated at a 
ratio of 0.5 to 20 wt.% based on the emulsifiable concentrate. The 
surfactants can be anionic, cationic or nonionic surfactants. Suitable 
anionic surfactants include higher alcholsulfates or sulfonates, 
alkylarylsulfonates or sulfosuccinates, such as calcium 
dodecylbenzenesulfonate and sodium dioctylsulfosuccinate etc. Suitable 
cationic surfactants include aliphatic alkylamines and aliphatic acid 
alkyl quaternary salts such as laurylamine hydrochloride and 
lauryldimethylbenzylammonium chloride. Suitable nonionic surfactants 
include ethylene oxide adducts of alkylphenol, aliphatic alcohol, 
mercaptane or aliphatic acid such as polyethyleneglycol ester of stearic 
acid or polyethyleneglycol ethers of palmityl alcohol or octylphenol. 
The concentration of the active ingredient is in a range of 0.5 to 80 wt.% 
especially 5 to 40 wt.%. 
The wettable powder is prepared by incorporating the active ingredient in 
an inert fine powder and a surfactant. The active ingredient is usually 
incorporated at a ratio of 1 to 50 wt.% and the surfactant is incorporated 
at a ratio of 0.5 to 20 wt.%. The solid carriers usually used with the 
active ingredient include natural products of clay, silicates, silica, 
lime and carbonates and organic carriers. Suitable carriers include 
kaolin, jeeklite, fuller's earth talc, diatomaceous earth, magnesium lime, 
dolomite, and walnut shell powder. 
The emulsifiers and wetting agents used in the wettable powder include 
polyoxyethylene-alkylphenols, aliphatic alcohols or aliphatic acids and 
alkylamines, alkylarylsulfonates, and dialkylsulfosuccinates. Suitable 
spreaders include glycerin mannitol laurate and condensates of oleic acid 
and polyglycerin modified with phthalic anhydride. Suitable dispersing 
agents include condensates of maleic anhydride and olefin such as sodium 
salt of copolymer of diisobutylene and maleic acid; sodium 
ligninsulfonate; and sodium formaldehydenaphthalenesulfonate, etc. The 
dust is prepared by incorporating the active ingredient in an inert 
carrier used for dusts such as talc, fine clay, agalmatolite, diatomaceous 
earth, magnesium carbonate or wheat powder. 
A concentrated dust containing the active ingredient of 10 to 80 wt.% is 
usually prepared. In the application as a herbicide, it is diluted with a 
solid carrier at a concentration of about 1 to 20 wt.%. 
The granule is prepared by incorporating the active ingredient in a 
granular or pelletized agricultural acceptable carrier such as bentonite, 
kaolin clay, diatomaceous earth and talc having particle size of 8 to 60 
mesh. The granule contains 1 to 50 wt.% of the active ingredient. 
The amounts of the active ingredients, adjuvants and additives in the 
herbicidal compositions of the present invention will be further 
illustrated. 
Emulsifiable concentrate: 
Active ingredient: 0.5 to 80 wt.% preferably 5 to 40 wt.% 
Surfactant: 1 to 40 wt.% preferably 5 to 20 wt.% 
Liquid carrier: 5 to 95 wt.% preferably 50 to 90 wt.% 
Wettable powder: 
Active ingredient: 1 to 50 wt.% preferably 5 to 30 wt.% 
Surfactant: 0.5 to 20 wt.% preferably 1 to 10 wt.% 
Solid carrier: 5 to 99 wt.% preferably 50 to 95 wt.% 
Granule: 
Active ingredient: 0.5 to 50 wt.% preferably 1 to 20 wt.% 
Solid carrier: 50 to 98.5 wt.% preferably 70 to 90 wt.% 
Surfactant: 1 to 10 wt.% preferably 2 to 5 wt.% 
Dust: 
Active ingredient: 0.5 to 10 wt.% preferably 1 to 5 wt.% 
Solid carrier: 90 to 99.5 wt.% preferably 95 to 99 wt.% 
The herbicidal compositions of the present invention mainly suppress 
seadling and growth of weeds. The herbicidal compositions impart excellent 
herbicidal effect for gramineous weeds of barnyard grass, marsh grass, 
sprangletop and monochoria by a soil treatment in a flooded condition. 
Moreover, the herbicidal compositions impart growth control effect to 
broad leaf weeds such as long stemmed waterwort and toothcup. No 
phytotoxicity to transplanted rice seedling is not found. Thus, the 
herbicidal composition has high selectivity. 
The herbicidal compositions of the present invention will be illustrated by 
certain examples. 
EXAMPLE 1: (Wettable Powder) 
Jeeklite: 97 wt. parts 
Neopelex powder (Kao-Atlas Co.): 1.5 wt. parts 
Sorpol 800 A (Toho Kagaku Kogyo): 1.5 wt. parts 
These components were uniformly pulverized and mixed to prepare a carrier 
for wettable powder. 
The resulting carrier for wettable powder (90 wt. parts) and Active 
ingredient (Compound No. 2) (10 wt. parts) were uniformly pulverized and 
mixed to obtain a wettable powder. 
EXAMPLE 2: (Emulsifiable concentrate) 
Active ingredient (Compound No. 4): 10 wt. parts 
Cyclohexanone: 40 wt. parts 
Xylene: 40 wt. parts 
Sorpol 800 A (Toho Kagaku Kogyo): 10 wt. parts 
The components were uniformly mixed to obtain an emulsifiable concentrated. 
EXAMPLE 3: (Granule) 
Active ingredient (Compound No. 10): 7 wt. parts 
Bentonite: 44 wt. parts 
Kaolin clay: 44 wt. parts 
Sodium ligninsulfonate: 5 wt. parts 
The components were uniformly mixed and water was added and the mixture was 
kneaded, granulated and dried to obtain a granule. 
EXAMPLE 4: (Wettable powder) 
Active ingredient (Compound No. 2): 50 wt. parts 
Kaolin clay: 45 wt. parts 
Sorpol 5039 (Toho Kagaku Kogyo): 5 wt. parts 
These components were uniformly mixed to obtain a wettable powder. 
EXAMPLE 5: (Emulsifiable concentrate) 
Active ingredient (Compound No. 4): 25 wt. parts 
Xylene: 35 wt. parts 
Cyclohexanone: 30 wt. parts 
Sorpol 800 A (Toho Kagaku Kogyo): 10 wt. parts 
These components were uniformly mixed to obtain an emulsifiable 
concentrate. 
Test 1: 
Each porcelain pot of 1/15,500 are was filled with paddy soil and seeds of 
barnyard grass, marsh grass, sprangletop were uniformly sown on the 
surface layer, and flooded in a depth of 2 cm. Two seedlings of rice 
(species: Nihon bare) at two leaf stage were transplanted. At the time of 
germination of the weeds, each diluted solution of a wettable powder 
containing each active ingredient was poured into water at each dose of 
the active ingredient. Twenty days after the treatment with the active 
ingredient, the herbicidal effect to barnyard grass, marsh grass, 
sprangletop and the phytotoxicity to the transplanted rice seedlings were 
observed. The test results are shown by the following ratings. 
______________________________________ 
Phytotoxicity to transplanted 
Herbicidal effect rice seedling 
______________________________________ 
0: none -: none phytotoxicity 
1: growth suppression of 20-30% 
.+-.: substantial none- 
phytotoxicity 
2: growth suppression of 40-50% 
+: slight damage 
3: growth suppression of 60-70% 
++: damage 
4: growth suppression of 80-90% 
+++: remarkable damage 
5: complete growth suppression 
______________________________________ 
The test results are shown in Table 2. 
As shown in Table 2, the compounds of the present invention had remarkably 
high herbicidal effect to remarkably high herbicidal effect to the 
gramineous weeds of barnyard grass, marsh grass and sprangletop without 
any phytotoxicity to the transplanted rice plant as the gramineous crop 
plant. 
TABLE 2 
______________________________________ 
Phyto- 
toxicity 
Herbicidal effect 
Comp. Dose of rice Barnyard 
Marsh Sprangle- 
No. g./10 are seedling grass grass top 
______________________________________ 
1 1000 - 5 5 5 
500 - 5 5 5 
250 - 4.5 4.5 4.5 
125 - 4 4 4 
62.5 - 2 1 1 
2 1000 - 5 5 5 
500 - 5 5 5 
250 - 5 5 5 
125 - 5 5 5 
62.5 - 5 5 5 
3 1000 - 5 5 5 
500 - 5 5 5 
250 - 5 4.5 5 
125 - 4.5 4 4.5 
62.5 - 4.5 4 4 
4 1000 - 5 5 5 
500 - 5 5 5 
250 - 5 5 5 
125 - 5 5 5 
62.5 - 5 5 5 
5 1000 - 5 5 5 
500 - 5 5 5 
250 - 5 5 5 
125 - 5 5 5 
62.5 - 2 3 2 
6 1000 .+-. 5 5 5 
500 - 5 5 5 
250 - 5 5 5 
125 - 5 5 5 
62.5 - 3 2 3 
7 1000 - 5 5 5 
500 - 5 5 5 
250 - 5 5 5 
125 - 5 5 5 
62.5 - 1 1 2 
8 1000 - 5 5 5 
500 - 5 5 5 
250 - 5 5 5 
125 - 5 5 5 
62.5 - 1 1 1 
9 1000 - 5 5 5 
500 - 5 5 5 
250 - 5 5 5 
125 - 5 5 5 
62.5 - 4 3 4 
10 1000 - 5 5 5 
500 - 5 5 5 
250 - 5 5 5 
125 - 5 5 5 
62.5 - 5 4.5 4.5 
11 1000 - 5 5 5 
500 - 5 5 5 
250 - 5 5 5 
125 - 5 5 5 
62.5 - 4 4 4 
12 1000 - 5 5 5 
500 - 5 5 5 
250 - 5 5 5 
125 - 5 5 5 
62.5 - 4 4 4.5 
13 1000 - 5 5 5 
500 - 5 5 5 
250 - 5 5 5 
125 - 5 5 5 
62.5 - 4 4.5 4 
______________________________________ 
Test 2: 
Each porcelain pot of 1/15,500 are was filled with paddy soil and seeds of 
barnyard grass and sprangletop were uniformly sown on the surface layer, 
and flooded in a depth of 2 cm. Two seedlings of rice (species: Nihon 
bare) at two leaf stage were transplanted. Five days or ten days after the 
transplantation, each diluted solution of each emulsifiable concentrate 
was added dropwise by a pipet at a specific dose of the active ingredient. 
Twenty days after the treatment with the active ingredient, the herbicidal 
effect and the phytotoxicity to the transplanted rice seedlings were 
observed. The test results are shown in Table 3. 
The rating is the same as that of Test 1. 
As shown in Table 3, the compounds of the present invention in the 
emulsifiable concentrate had remarkably high herbicidal effect to the 
gramineous weeds of barnyard grass and sprangletop without any 
phytotoxicity to the transplanted rice plant as the gramineous crop plant. 
TABLE 3 
__________________________________________________________________________ 
Treatment 5 days after 
Treatment 10 days after 
transplantation 
transplantation 
Herbicidal effect 
Herbicidal effect 
Barn- Phyto- 
Barn- Phyto- 
Dose yard 
Sprang- 
toxicity 
yard 
Sprang- 
toxicity 
Comp. No. 
g./10 are 
grass 
letop 
to rice 
grass 
letop 
to rice 
__________________________________________________________________________ 
1 800 5 5 - 5 5 - 
400 5 5 - 5 5 - 
200 4 4 - 4 3 - 
100 3 3 - 3 2 - 
2 800 5 5 - 5 5 - 
400 5 5 - 5 5 - 
200 5 5 - 5 5 - 
100 5 5 - 5 5 - 
3 800 5 5 - 5 5 - 
400 5 5 - 5 5 - 
200 5 5 - 5 5 - 
100 5 5 - 5 5 - 
5 800 5 5 - 5 5 - 
400 5 5 - 5 5 - 
200 5 5 - 5 5 - 
100 5 4.5 - 5 4 - 
6 800 5 5 - 5 5 - 
400 5 5 - 5 5 - 
200 5 5 - 5 5 - 
100 4.5 4.5 - 4.5 4 - 
8 800 5 5 - 5 5 - 
400 5 5 - 5 5 - 
200 5 5 - 5 5 - 
100 4 3 - 4 2 - 
10 800 5 5 - 5 5 - 
400 5 5 - 5 5 - 
200 5 5 - 5 5 - 
100 5 5 - 5 5 - 
12 800 5 5 - 5 5 - 
400 5 5 - 5 5 - 
200 5 5 - 5 5 - 
100 5 4.5 - 5 4 - 
__________________________________________________________________________ 
Test 3: 
Each wagner pot of 1/5,000 are was filled with paddy soil and a paddy soil 
containing weeds of barnyard grass and sprangletop was covered as a 
surface layer and it was treated by a manuring an irrigation and a 
puddling and it was flooded in a depth of 4 cm. Three seedlings of two 
stands rice (species: Nihon bare) at 2.5 leaf stage were transplanted. 
Three days or seven days after the transplantation, each granule of each 
active ingredient prepared by Example 3 was applied at each specific dose 
of each active ingredient. 
Twenty days after the treatment with the active ingredient, the herbicidal 
effect and the phytotoxicity to the transplanted rice seedlings were 
observed. The test results are shown in Table 4. The rating is the same as 
that of Test 1. 
As shown in Table 4, the compounds of the present invention in the granular 
form had remarkably high herbicidal effect without any phytotoxicity to 
rice seedlings. 
TABLE 4 
__________________________________________________________________________ 
Treatment 3 days after 
Treatment 7 days after 
transplantation 
transplantation 
Herbicidal effect 
Herbicidal effect 
Barn- Phyto- 
Barn- Phyto- 
Dose yard 
Sprang- 
toxicity 
yard 
Sprang- 
toxicity 
Comp. No. 
g./10 are 
grass 
letop 
to rice 
grass 
letop 
to rice 
__________________________________________________________________________ 
1 420 5 5 - 5 5 - 
280 5 5 - 5 5 - 
140 4 4 - 4 3.5 - 
2 420 5 5 - 5 5 - 
280 5 5 - 5 5 - 
140 5 5 - 5 5 - 
4 420 5 5 - 5 5 - 
280 5 5 - 5 5 - 
140 5 5 - 5 5 - 
5 420 5 5 - 5 5 - 
280 5 5 - 5 5 - 
140 5 5 - 5 5 - 
6 420 5 5 - 5 5 - 
280 5 5 - 5 5 - 
140 5 5 - 5 5 - 
8 420 5 5 - 5 5 - 
280 5 5 - 5 5 - 
140 5 5 - 4.5 5 - 
9 420 5 5 - 5 5 - 
280 5 5 - 5 5 - 
140 5 5 - 5 5 - 
10 420 5 5 - 5 5 - 
280 5 5 - 5 5 - 
140 5 5 - 5 5 - 
11 420 5 5 - 5 5 - 
280 5 5 - 5 5 - 
140 5 5 - 5 5 - 
13 420 5 5 - 5 5 - 
280 5 5 - 5 5 - 
140 5 5 - 5 5 - 
__________________________________________________________________________