Urea derivatives and highly selective herbicidal compositions containing the same

This invention relates to a urea derivative of the formula ##STR2## wherein X is a halogen, an alkyl or trifluoromethyl, n is an integer of from 0 to 3, provided that when n is 2 or 3, X may be different to each other; A is ##STR3## or --C.tbd.C--, wherein ##STR4## is in trans form; and R is methyl or methoxy. This invention also relates to a process for preparing the urea derivative defined above, and to a herbicidal composition containing the same.
The inventors had studied in order to develop a herbicidal composition having highly selective herbicidal activity, namely, having low phytotoxicity to useful plants such as crops, and high toxicity to weeds, and found a group of compounds represented by the formula (I) above. The inventors confirmed that the compounds exhibit high selectivity between the useful plants and weeds and have very low toxicity for humans, animals, especially livestocks, fish, shellfish and the like, and finally completed this invention.
Various urea series herbicidal compounds which contain in the molecule, the same moiety as that of the compounds of this invention are known. However, it is also known that such conventional urea herbicidal compounds have relatively poor selectivity between the useful plants and weeds. Although many attempts have been made, no significant improvement has been obtained.
Examples of the commercially available urea series compounds are N'-N-chlorophenyl-N,N-dimethylurea (monuron), N'-3,4-dichlorophenyl-N,N'-dimethylurea (diuron), and N'-3,4-dichlorophenyl-N-methoxy-N-methylurea (linuron). Although these types of compounds have high herbicidal activity against weeds, they exhibit at the same time, high phytotoxicity to useful plants. Therefore, in practical application, the conditions for application and particular useful plants and weeds must be carefully selected, and the use thereof is limited to a certain extent.
On the other hand, various compounds of triazine series are known for use as a herbicidal agent. However, it is generally recognized that the triazine compounds, like the urea compounds described hereinbefore, have low selectivity. For example, 2,4-bis(ethylamino)-6-methylthio-1,3,5-triazine (simetryne) is taken through roots of plants at a relatively slow rate in comparison with other types of triazine compounds, and it has been broadly used in order to control broadleaf weeds. However, the practical application of the compound is limited, especially when it is applied to paddy field, as the rice plant is often injured under water flooded conditions and at an elevated temperature. So, the compound must be used carefully on paddy fields.
In contrast, the compounds represented by the formula (I) of this invention exhibit, as shown in Experiments hereinbelow, no or slight phytotoxicity to useful plants, and a very strong herbicidal activity against harmful weeds, regardless of the particular application conditions and particular plants and weeds to be treated. The compounds of this invention have very high selectivity between crops and weeds.
The compounds of this invention represented by the formula (I) are novel and can be prepared by the various processes described hereunder.
(1) The compounds represented by the formula (I) are prepared by reacting a compound of the formula (II) ##STR5## wherein X, A and n are as defined above and Y is a halogen, with a urea derivative represented by the formula (III) ##STR6## wherein R is as defined above. The reaction is carried out in an appropriate solvent with aid of a proper acid acceptor to give the object compound in a high yield.
The solvents useful in this reaction include hydrocarbons such as benzene, toluene and the like; ethers such as diethyl ether, tetrahydrofuran, dioxane and the like; alcohols such as methanol, ethanol and the like; hydrocarbon halides such as chloroform; esters such as ethyl acetate; and other organic solvents such as dimethylformamide and the like; and mixture thereof. If desired, water or an aqueous mixture of one or more organic solvents can be used.
The acid acceptors useful in this reaction include, for example, organic compounds such as pyridine, triethylamine and the like; and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydride and the like.
The reaction is usually carried out at room temperature, but may be carried out under cooling or under heating depending on the particular reactants, solvents or acid acceptors used. The reaction is completed usually within 1-8 hours. After completion of the reaction, the product is recovered from the reaction mixture by the conventional isolation and/or purification technique.
The compounds of the formula (I) can also be prepared by the following process (2).
(2) The compounds are prepared by reacting a phenol derivative represented by the formula (IV) ##STR7## wherein X and n are as defined above, with a urea derivative represented by the formula (V) ##STR8## wherein Y, A and R are as defined above. The reaction is carried out in a solvent and with aid of an acid acceptor to give the object compound in a high yield.
The solvents and acid acceptors useful in the reaction (2) include those which can be used in the reaction (1). Although the reaction proceeds at room temperature, it may be carried out under cooling or under heating, depending on the particular reactants, solvents or acid acceptors to be used. The reaction is completed within 1-8 hours under suitable reaction conditions. Upon completion of the reaction, the product is separated and purified in any suitable conventional way.
(3) The compounds of the formula (I) can also be prepared with a high yield by reacting an aniline derivative represented by the formula (VI) ##STR9## wherein X, A and n are as defined above, with a carbomoyl chloride derivative of the formula (VII) ##STR10## wherein Y and R are as defined above.
The reaction is carried out in a solvent with aid of an acid acceptor. The solvents and acid acceptors useful in this reaction are those specified for the reaction (1).
Although the reaction proceeds at room temperature, it may be carried out under cooling or under heating, depending on the particular reactants, solvents and acid acceptors to be used. The reaction is completed within 1-8 hours under suitable conditions. The product is separated and purified in any suitable way.
(4) Further, the compounds of the formula (I) can be prepared with a high yield by reacting a phenylisocyanate derivative of the formula (VIII) ##STR11## wherein A, X and n are as defined above, with an amine derivative of the formula (IX) ##STR12## wherein R is as defined above.
This reaction is carried out using an inert solvent and an acid acceptor such as those exemplified in the explanation for the reaction (1).
Although the reaction proceeds at room temperature, good results may be given by cooling or heating the reaction system, depending on particular reactants and solvent to be used. The reaction is usually completed within 1-8 hours, although the reaction time varies broadly, depending on particular conditions applied. The product is separated and purified by any suitable conventional technique.
(5) The compounds of this invention represented by the formula (I) wherein R is methoxy can be prepared with a high yield of methylating a urea derivative represented by the formula (X) ##STR13## wherein X, A and n are as defined above.
Examples of the methylating agent useful in this invention are dimethylsulfate, methyl iodide, diazomethane and the like.
The reaction conditions such as reaction temperature, time and the like vary broadly, depending on the particular solvents, reaction promoters, methylating agents, etc., but satisfactory results are obtained by applying the conventional methylating technique to this reaction.
The preparation of various compounds of this invention is further illustrated by the following Preparations.
PREPARATION 1
4-(4-Chloro-2-methylphenoxy)-2-trans-butenyl chloride (2.3 g) was added to a solution of potassium hydroxide (0.78 g) and N'-4-hydroxyphenyl-N,N-dimethylurea (1.8 g) in ethanol (30 ml), and the mixture was stirred at 50.degree.-60.degree. C. for 4 hours and then diluted with water and extracted with ethyl acetate. The solvent was evaporated from the extract under reduced pressure and the residue was recrystallized from ethanol to give 3.1 g of N'-4-[4-(4-chloro-2-methylphenoxy)-2-trans-butenyloxy]-phenyl-N-methyl-N-methoxyurea. (m.p.: 122.degree.-123.degree. C.) (Compound No. 32)
Analysis: Calcd. for C.sub.20 H.sub.23 ClN.sub.2 O.sub.3 (molecular weight: 374.87): C, 64.08; H, 6.18; N, 7.47 (%). Found: C, 64.29; H, 6.23; N, 7.49 (%)
PREPARATION 2
4-(2,6-Dimethylphenoxy)-2-trans-butenyl chloride (2.1 g) was added to a solution of potassium hydroxide (0.78 g) and N'-3-hydroxyphenyl-N-methyl-N-methoxyurea (2.0 g) in ethanol (40 ml) and the mixture was subjected to reaction by heating it at 60.degree.-70.degree. C. for 5 hours while stirring. After completion of the reaction, the reaction mixture was diluted with water and extracted with ethyl acetate. The solvent was evaporated under reduced pressure. The residual oily product was chromatographed using a column filled with silica gel and chloroform as an eluent to isolate the product. The fractions containing the product were combined and the solvent was evaporated to give as an oily substance 3.0 g of N'-3-[4-(2,6-dimethylphenoxy)-2-trans-butenyloxy]-phenyl-N-methyl-N-methoxyurea. (Compound No. 106)
Analysis: Calcd. for C.sub.21 H.sub.26 N.sub.2 O.sub.4 (molecular weight: 370.45): C, 68.09; H, 7.07; N, 7.56 (%). Found: C, 68.33; H, 7.15; N, 7.40 (%)
PREPARATION 3
N'-3-(4-Chloro-2-trans-butenyloxy)-phenyl-N-methyl-N-methoxyurea (2.9 g) was added to a solution of sodium hydroxide (0.6 g) and 2,4-dichlorophenol (1.4 g) in methanol (50 ml) and the mixture was reacted by heating it at 50.degree. C. for 4 hours while stirring. After completion of the reaction, the reaction mixture was diluted with water and extracted with ethyl acetate. The solvent was evaporated from the extract under reduced pressure and the resulting residue was recrystallized from ethyl acetate/n-hexane to give 3.2 g of N'-3-[4-(2,4-dichlorophenoxy)-2-trans-butenyloxy]-pehnyl-N-methyl-N-methoxyurea. (m.p.: 91.degree.-92.degree. C.) (Compound No. 98)
Analysis: Calcd. for C.sub.19 H.sub.20 Cl.sub.2 N.sub.2 O.sub.4 (molecular weight: 411.28): C, 55.49; H, 4.90; N, 6.81 (%). Found: C, 55.53; H, 4.90; N, 6.70 (%)
PREPARATION 4
A solution of 4-[4-(4-chlorophenoxy)-2-trans-butenyloxy]-aniline (2.7 g) and triethylamine (1.2 g) in tetrahydrofuran (30 ml) was cooled with ice, and to the solution was added slowly dimethyl-carbamoly chloride (1.3 g). After completion of the addition, the mixture was stirred under cooling with ice for 30 minutes, and then at room temperature for 2 hours. The resulting triethylamine hydrochloride was removed by filtration, and the solvent was evaporated from the filtrate under reduced pressure. The resulting risidue was recrystallized from diethyl ether to give 3.0 g of N'-4-[4-(4-chlorophenoxy)-2-trans-butenyloxy]-phenyl-N,N-dimethylurea. (m.p.: 144.degree.-145.degree. C.) (Compound No. 4)
Analysis: Calcd. for C.sub.19 H.sub.21 ClN.sub.2 O.sub.3 (molecular weight: 360.84): C, 63.24; H, 5.88; N, 7.76 (%). Found: C, 63.18; H, 5.92; N, 7.88 (%)
PREPARATION 5
3-[4-(4-Chloro-2-methylphenoxy)-2-trans-butenyloxy]phenyl-isocyanate (3.3 g) was dissolved in tetrahydrofuran (30 ml) and a 50% dimethylamine aqueous solution (1 g) was added dropwise to the solution while stirring and cooling with ice. After completion of the addition, the mixture was stirred for 30 minutes while stirring under cooling with ice, and then stirred at room temperature for an additional 2 hours. The solvent was evaporated under reduced pressure and the resulting residue was recrystallized from ethyl acetate/n-hexane to give 2.9 g of N'-3-[4-(4-chloro-2-methylphnoxy)-2-transbutenyloxy]-phenyl-N,N-dimethylurea. (m.p.: 116.degree.-118.degree. C.) (Compound No. 80)
Analysis: Calcd. for C.sub.20 H.sub.23 ClN.sub.2 O.sub.3 (molecular weight: 374.87): C, 64.08; H, 6.18; N, 7.47 (%). Found: C, 63.97; H, 6.21; N, 7.51 (%)
PREPARATION 6
A solution of 3-[4-(2,4-dimethylphenoxy)2-transbutenyloxy]-phenylisocyanate (3.1 g) in methylene chloride (10 ml) was added dropwise to an aqueous solution of hydroxylamine hydrochloride (0.5 g) and sodium hydroxide (0.5 g) while stirring and cooling with ice. After completion of the addition, the stirring was continued for an additional 30 minutes under the same condition, and then at room temperature for 2 hours. The reaction mixture was then diluted with water and the precipitate was recovered by filtration and dried. The product was dissolved in benzene methanol (1:1) (50 ml), and 1.0 N aqueous sodium hydroxide (1 ml) and dimethylsulfate (1.3 g) were added dropwise to the solution while stirring and cooling with ice. After completion of the addition, the mixture was stirred for an additional 30 minutes under the same conditions, and then at room temperature for 2 hours. The reaction mixture was diluted with water and extracted with benzene, and the solvent was evaporated. The resulting residue was recrystallized from ethyl acetate/n-hexane to give 2.6 g of N'-3-[4-(2,4-dimethylphenoxy)-2-trans-butenyloxy]phenyl-N-methyl-N-methoxyurea. (m.p.: 84.5.degree.-85.degree. C.) (Compound No. 104)
Analysis: Calcd. for C.sub.21 H.sub.26 N.sub.2 O.sub.4 (molecular weight: 370.45): C, 68.09; H, 7.07; N, 7.56 (%). Found: C, 68.33; H, 7.15; N, 7.40 (%)
Preparation 7
4-(3-Methyl-4-chlorophenoxy)-2-butynyl chloride (2.29 g) was added to a solution of N'-4-hydroxyphenyl-N-methyl-N-methoxyurea (1.96 g) and potassium hydroxide (0.65 g) in ethanol (30 ml), and the mixture was stirred at 60.degree. C. for 5 hours to react the reactants. After completion of the reaction, the ethanol was evaporated under reduced pressure, and the resulting residue was diluted with water and extracted with benzene. The benzene layer was washed with 5% aqueous sodium hydroxide and then with water, and dried over sodium sulfate. After removing the sodium sulfate by filtration, the benzene was evaporated under reduced pressure to give an oily product. Recrystallization of the oily product from benzene/n-hexane gave 2.4 g of N'-4-[4-(3-methyl-4-chlorophenoxy)-2-butynyloxy]-phenyl-N-methyl-N-methoxyurea. (m.p.: 79.5.degree.-80.degree. C.) (Compound No. 166)
Analysis: Calcd. for C.sub.20 H.sub.21 ClN.sub.2 O.sub.4 (molecular weight: 388.84): C, 61.77; H, 5.44; N, 7.20 (%). Found: C, 61.55; H, 5.32; N, 7.19 (%)
PREPARATION 8
3,4-Dichlorophenol (1.9 g) was added to a solution of sodium hydride (0.29 g) in dimethylformamide (20 ml), and then N'-4-(4-chloro-2-butynyloxy)-phenyl-N,N-dimethylurea (2.67 g) was added to the mixture followed by stirring it at 50.degree. C. for 5 hours. After completion of the reaction, the reaction mixture was poured into water (50 ml) and the separated oily phase was extracted with benzene. The benzene layer extract was washed with 5% aqueous sodium hydroxide and then with water, and dried over sodium sulfate. After removing the sodium sulfate by filtration, the benzene was evaporated under reduced pressure. The residue was recrystallized from ethyl acetate/n-hexane to give 2.36 g of N'-4-[4-(3,4-dichlorophenoxy)-2-butynyloxy]-phenyl-N,N-dimethylurea. (m.p.: 113.degree.-114.degree. C.) (Compound No. 131)
Analysis: Calcd. for C.sub.19 H.sub.18 Cl.sub.2 N.sub.2 O.sub.3 (molecular weight: 393.26): C, 58.02; H, 4.61; N, 7.12 (%). Found: C, 58.15; H, 4.70; N, 7.07 (%)
PREPARATION 9
4-[4-(3,5-Dimethylphenoxy)-2-butynyloxy]aniline (2.81 g) and triethylamine (1.4 ml) were dissolved in tetrahydrofuran (30 ml). To the solution was added dropwise a solution of N,N-dimethylcarbamoly chloride (1.07 g) in tetrahydrofuran (15 ml) while stirring and cooling with ice-water. After completion of the addition, the mixture was stirred under cooling for 30 minutes, and at room temperature for 2 hours to complete the intended reaction. After completion of the reaction, the tetrahydrofuran was evaporated under reduced pressure and water was added to the residue to give crystals which were recovered by filtration and dried. The crystals were recrystallized from ethyl acetate/n-hexane to give 2.95 g of N'-4-[4-(3,5-dimethylphenoxy)-2-butynyloxy]-phenyl-N,N-dimethylurea. (m.p.: 145.degree.-146.degree. C.) (Compound No. 138)
Analysis: Calcd. for C.sub.21 H.sub.24 N.sub.2 O.sub.3 (molecular weight: 352.42): C, 71.56; H, 6.86; N, 7.94 (%). Found: C, 71.38; H, 6.87; N, 7.99 (%)
PREPARATION 10
O,N-Dimethylhydroxylamine hydrochloride (1.17 g) and triethylamine (1.68 g) were dissolved in chloroform (50 ml). To this solution another solution of 3-[4-(3,4-dimethylphenoxy)-2-butynyloxy]phenylisocyanate (3 g) in chloroform (20 ml) was added dropwise while stirring and cooling with ice water. After completion of the addition, the stirring was continued under cooling for 30 minutes, and then at room temperature for 5 hours to complete the intended reaction. After addition of water, the reaction mixture was extracted with chloroform. The chloroform layer was separated, dried over sodium sulfate, and, after removing the sodium sulfate, evaporated under reduced pressure to remove the chloroform. The residue was recrystallized from benzene/n-hexane to give 2.65 g of N'-3-[4-(3,4-dimethylphenoxy)-2-butynyloxy]phenyl-N-methyl-N-methoxyurea. (m.p.: 93.5.degree.-94.5.degree. C.) (Compound No. 201)
Analysis: Calcd. for C.sub.21 H.sub.24 N.sub.2 O.sub.4 (molecular weight: 368.42): C, 68.45; H, 6.56; N, 7.60 (%). Found: C, 68.44; H, 6.66; N, 7.53 (%)
PREPARATION 11
A solution of 3-[4-(3,4-dimethylphenoxy)-2-butynyloxy]phenyl-isocyanate (3 g) in methylene chloride (10 ml) was added dropwise, while stirring and cooling with ice, to a solution of hydroxylamine hydrochloride (0.8 g) and sodium hydroxide (0.5 g) in water (10 ml). After completion of the addition, the reaction mixture was stirred under cooling for 30 minutes, and then at room temperature for 2 hours to complete the intended reaction. Then, water was added to the reaction mixture to form a precipitate which was recovered by filtration and dried.
The thus obtained solid hydroxyurea derivative was dissolved in benzene/methanol (1:1) (50 ml), and to the solution were added 10 N aqueous sodium hydroxide (1 ml) and dimethyl sulfate (1.3 g) while stirring and cooling with ice. After completion of the addition, the mixture was stirred under cooling for 30 minutes and then at room temperature for 2 hours to complete the reaction. The, water was added to the reaction mixture and the resulting precipitate was extracted with benzene. The benzene layer was separated and evaporated to remove benzene. The residue was recrystallized from benzene/n-hexane to give 1.8 g of N'-3-[4-(3,4-dimethylphenoxy)-2-butynyloxy]-phenyl-N-methyl-N-methoxyurea. (m.p.: 93.degree.-94.degree. C.) (Compound No. 201)
When the compound was subjected to mixed examination with the product of Preparation 10, no drop in the mixed melting point was observed.
Typical compounds represented by the formula (I) of this invention which were prepared in the same way as in the previous Examples are listed in the following Table 1. It should be understood that the compounds in Table 1 are shown for illustrative purpose, not for limitation.
In Table 1, figures of from 2 to 6 in the column for "Substituent X" represent the position on benzene nucleus, and "m" and "p" in the column entitled "Binding Position" represent meta- and para- positions on the other benzene nucleus with respect to the substituent ##STR14##
The NMR spectra of the products given as oily substances by conventional isolation and purification technique are shown in Table 2.
Further, Et, Pr, Bu and Am in Table 1 represent --C.sub.2 H.sub.5, --C.sub.3 H.sub.7, --C.sub.4 H.sub.9 and --C.sub.5 H.sub.11, respectively.
The compound number assigned in the previous Preparations and in Tables below will be used in Examples and Experiments hereunder.
TABLE 1__________________________________________________________________________ Bond-Com- Substituents ing Meltingpound X posi- pointNo. 2 3 4 5 6 R A tion (.degree.C.)__________________________________________________________________________1 -- -- -- -- -- CH.sub.3 ##STR15## p 138-1392 Cl -- -- -- -- CH.sub.3 ##STR16## p 125-1273 -- Cl -- -- -- CH.sub.3 ##STR17## p 129.5-131.54 -- -- Cl -- -- CH.sub.3 ##STR18## p 144-1455 -- -- Br -- -- CH.sub.3 ##STR19## p 154-1566 F -- -- -- -- CH.sub.3 ##STR20## p 113.5-114.57 -- F -- -- -- CH.sub.3 ##STR21## p 146-146.58 -- -- F -- -- CH.sub.3 ##STR22## p 139-139.59 CH.sub.3 -- -- -- -- CH.sub.3 ##STR23## p 129-130.510 -- CH.sub.3 -- -- -- CH.sub.3 ##STR24## p 124-126.511 -- -- CH.sub.3 -- -- CH.sub.3 ##STR25## p 156-15712 -- -- Et -- -- CH.sub.3 ##STR26## p 144-14513 -- -- n-Pr -- -- CH.sub.3 ##STR27## p 134-13514 -- -- i-Pr -- -- CH.sub.3 ##STR28## p 142-143.5 sec-15 -- -- Bu -- -- CH.sub.3 ##STR29## p 109-11016 -- -- t-Bu -- -- CH.sub.3 ##STR30## p 158-159 sec-17 -- -- Am -- -- CH.sub.3 ##STR31## p 93-9518 -- -- t-Am -- -- CH.sub.3 ##STR32## p 102-10319 -- CF.sub.3 -- -- -- CH.sub.3 ##STR33## p 127-12820 Cl Cl -- -- -- CH.sub.3 ##STR34## p 125.5-127.521 Cl -- Cl -- -- CH.sub.3 ##STR35## p 121-122.522 Cl -- -- Cl -- CH.sub.3 ##STR36## p 115-11623 Cl -- -- -- Cl CH.sub.3 ##STR37## p 116-117.524 -- Cl Cl -- -- CH.sub.3 ##STR38## p 157-15925 -- Cl -- Cl -- CH.sub.3 ##STR39## p 142-14326 CH.sub.3 CH.sub.3 -- -- -- CH.sub.3 ##STR40## p 135-13727 CH.sub.3 -- CH.sub.3 -- -- CH.sub.3 ##STR41## p 133-13428 CH.sub.3 -- -- CH.sub.3 -- CH.sub.3 ##STR42## p 137-13929 CH.sub.3 -- -- -- CH.sub.3 CH.sub.3 ##STR43## p 137-13930 -- CH.sub.3 CH.sub.3 -- -- CH.sub.3 ##STR44## p 14631 -- CH.sub.3 -- CH.sub.3 -- CH.sub.3 ##STR45## p 126-12832 CH.sub.3 -- Cl -- -- CH.sub.3 ##STR46## p 122-12333 Cl -- -- -- CH.sub.3 CH.sub.3 ##STR47## p 121-12234 -- CH.sub.3 Cl -- -- CH.sub.3 ##STR48## p 13835 Cl -- t-Bu -- -- CH.sub.3 ##STR49## p 124-12536 Cl -- Cl Cl -- CH.sub.3 ##STR50## p 141-14237 Cl -- Cl -- Cl CH.sub.3 ##STR51## p 128-12938 CH.sub.3 -- CH.sub.3 -- CH.sub.3 CH.sub.3 ##STR52## p 110-11139 Cl -- Cl -- CH.sub.3 CH.sub.3 ##STR53## p 133-13440 -- CH.sub.3 Cl CH.sub.3 -- CH.sub.3 ##STR54## p 153.5-154.541 -- -- -- -- -- OCH.sub.3 ##STR55## p 90-9142 Cl -- -- -- -- OCH.sub.3 ##STR56## p 114-11543 -- Cl -- -- -- OCH.sub.3 ##STR57## p 78-8044 -- -- Cl -- -- OCH.sub.3 ##STR58## p 122-122.545 -- -- Br -- -- OCH.sub.3 ##STR59## p 122.5-126.546 -- -- F -- -- OCH.sub.3 ##STR60## p 111-11247 -- CH.sub.3 -- -- -- OCH.sub.3 ##STR61## p 74-7648 -- -- CH.sub.3 -- -- OCH.sub.3 ##STR62## p 114-115.549 -- CF.sub.3 -- -- -- OCH.sub.3 ##STR63## p 91.5-9350 Cl Cl -- -- -- OCH.sub.3 ##STR64## p 102-10351 Cl -- Cl -- -- OCH.sub.3 ##STR65## p 123.5-124.552 Cl -- -- Cl -- OCH.sub.3 ##STR66## p 85-90.553 Cl -- -- -- Cl OCH.sub.3 ##STR67## p 126-12754 -- Cl Cl -- -- OCH.sub.3 ##STR68## p 126- 12855 -- Cl -- Cl -- OCH.sub.3 ##STR69## p 91-9256 CH.sub.3 -- -- CH.sub.3 -- OCH.sub.3 ##STR70## p 98-9957 CH.sub.3 -- -- -- CH.sub.3 OCH.sub.3 ##STR71## p 118.5-119.558 CH.sub.3 -- Cl -- -- OCH.sub.3 ##STR72## p 112-113.559 -- CH.sub.3 Cl -- -- OCH.sub.3 ##STR73## p 107-10860 Cl -- -- -- CH.sub.3 OCH.sub.3 ##STR74## p 115-116.561 Cl -- Cl Cl -- OCH.sub.3 ##STR75## p 130-13162 CH.sub.3 -- CH.sub.3 -- CH.sub.3 OCH.sub.3 ##STR76## p 114-11663 -- -- -- -- -- CH.sub.3 ##STR77## m 102-10464 Cl -- -- -- -- CH.sub.3 ##STR78## m 132-132.565 -- Cl -- -- -- CH.sub.3 ##STR79## m 126.5-127.566 -- -- Cl -- -- CH.sub.3 ##STR80## m 140.5-141.567 -- -- Br -- -- CH.sub.3 ##STR81## m 134.5-135.568 -- -- F -- -- CH.sub.3 ##STR82## m 132.5-13469 -- CH.sub.3 -- -- -- CH.sub.3 ##STR83## m 128-12970 -- -- CH.sub.3 -- -- CH.sub.3 ##STR84## m 145-145.571 -- CF.sub.3 -- -- -- CH.sub.3 ##STR85## m 134-13572 Cl Cl -- -- -- CH.sub.3 ##STR86## m 142-143.573 Cl -- Cl -- -- CH.sub.3 ##STR87## m 136-13874 Cl -- -- Cl -- CH.sub.3 ##STR88## m 147-14875 Cl -- -- -- Cl CH.sub.3 ##STR89## m 95-9676 -- Cl Cl -- -- CH.sub.3 ##STR90## m 126-12777 -- Cl -- Cl -- CH.sub.3 ##STR91## m 117.5-119.578 CH.sub.3 -- -- CH.sub.3 -- CH.sub.3 ##STR92## m 165-16679 CH.sub.3 -- -- -- CH.sub.3 CH.sub.3 ##STR93## m 8880 CH.sub.3 -- Cl -- -- CH.sub.3 ##STR94## m 116-11881 -- CH.sub.3 Cl -- -- CH.sub.3 ##STR95## m 119-12082 Cl -- -- -- CH.sub.3 CH.sub.3 ##STR96## m 98-9983 Cl -- Cl Cl -- CH.sub.3 ##STR97## m 173.5-174.584 CH.sub.3 -- CH.sub.3 -- CH.sub.3 CH.sub.3 ##STR98## m 111.5-11385 -- -- -- -- -- OCH.sub.3 ##STR99## m 86-8786 Cl -- -- -- -- OCH.sub.3 ##STR100## m 72-7487 -- Cl -- -- -- OCH.sub.3 ##STR101## m 61-6388 -- -- Cl -- -- OCH.sub.3 ##STR102## m 113.5-11589 -- -- Br -- -- OCH.sub.3 ##STR103## m 99-10090 F -- -- -- -- OCH.sub.3 ##STR104## m 0.191 -- F -- -- -- OCH.sub.3 ##STR105## m oil92 -- -- F -- -- OCH.sub.3 ##STR106## m 101-102.593 CH.sub.3 -- -- -- -- OCH.sub.3 ##STR107## m oil94 -- CH.sub.3 -- -- -- OCH.sub.3 ##STR108## m oil95 -- -- CH.sub.3 -- -- OCH.sub.3 ##STR109## m 131-13296 -- CF.sub.3 -- -- -- OCH.sub.3 ##STR110## m oil97 Cl Cl -- -- -- OCH.sub.3 ##STR111## m oil98 Cl -- Cl -- -- OCH.sub.3 ##STR112## m 91-9299 Cl -- -- Cl -- OCH.sub.3 ##STR113## m oil100 Cl -- -- -- Cl OCH.sub.3 ##STR114## m oil101 -- Cl Cl -- -- OCH.sub.3 ##STR115## m oil102 -- Cl -- Cl -- OCH.sub.3 ##STR116## m oil103 CH.sub.3 CH.sub.3 -- -- -- OCH.sub.3 ##STR117## m oil104 CH.sub.3 -- CH.sub.3 -- -- OCH.sub.3 ##STR118## m 84.5-85105 CH.sub.3 -- -- CH.sub.3 -- OCH.sub.3 ##STR119## m oil106 CH.sub.3 -- -- -- CH.sub.3 OCH.sub.3 ##STR120## m oil107 -- CH.sub.3 CH.sub.3 -- -- OCH.sub.3 ##STR121## m 109.5-110108 -- CH.sub.3 -- CH.sub.3 -- OCH.sub.3 ##STR122## m oil109 CH.sub.3 -- Cl -- -- OCH.sub.3 ##STR123## m 81-82110 -- CH.sub.3 Cl -- -- OCH.sub.3 ##STR124## m 88-90111 Cl -- -- -- CH.sub.3 OCH.sub.3 ##STR125## m oil112 Cl -- Cl Cl -- OCH.sub.3 ##STR126## m oil113 Cl -- Cl -- Cl OCH.sub.3 ##STR127## m oil114 CH.sub.3 -- CH.sub.3 -- CH.sub.3 OCH.sub.3 ##STR128## m oil115 -- -- -- -- -- CH.sub.3 CC p 91-92116 Cl -- -- -- -- CH.sub.3 CC p 102.5-103.5117 -- Cl -- -- -- CH.sub.3 CC p 106.5-107.5118 -- -- Cl -- -- CH.sub.3 CC p 118119 -- -- Br -- -- CH.sub.3 C C p 115-115.5120 F -- -- -- -- CH.sub.3 CC p 110-110.5121 -- F -- -- -- CH.sub.3 CC p 95-96122 -- -- F -- -- CH.sub.3 CC p 96-97123 CH.sub.3 -- -- -- -- CH.sub.3 CC p 86124 -- CH.sub.3 -- -- -- CH.sub.3 CC p 94.5-95125 -- -- CH.sub.3 -- -- CH.sub.3 CC p 106-197126 -- -- Et -- -- CH.sub.3 C C p 81.5-82127 Cl Cl -- -- -- CH.sub.3 CC p 124.5-125128 Cl -- Cl -- -- CH.sub.3 CC p 95.5-96129 Cl -- -- Cl -- CH.sub.3 CC p 92.5-93.5130 Cl -- -- -- Cl CH.sub.3 CC p 114.5-115.5131 -- Cl Cl -- -- CH.sub.3 CC p 113-114132 -- Cl -- Cl -- CH.sub.3 CC p 118.5-119.5133 CH.sub.3 CH.sub.3 -- -- -- CH.sub.3 CC p 145.5-146134 CH.sub.3 -- CH.sub.3 -- -- CH.sub.3 CC p 108-109135 CH.sub.3 -- -- CH.sub.3 -- CH.sub.3 CC p 124.5-125.5136 CH.sub.3 -- -- -- CH.sub.3 CH.sub.3 CC p 125137 -- CH.sub.3 CH.sub.3 -- -- CH.sub.3 CC p 137.5-138138 -- CH.sub.3 -- CH.sub.3 -- CH.sub.3 CC p 145-146139 CH.sub.3 -- Cl -- -- CH.sub.3 CC p 120-121140 -- CH.sub.3 Cl -- -- CH.sub.3 CC p 113.5-115141 Cl -- -- -- CH.sub.3 CH.sub.3 CC p 107.5-108142 Cl -- Cl Cl -- CH.sub.3 CC p 140-141143 -- CH.sub.3 Cl CH.sub.3 -- CH.sub.3 CC p 139-140144 -- -- -- -- -- OCH.sub.3 CC p 86.5-87.5145 Cl -- -- -- -- OCH.sub.3 CC p 66.5-67.5146 -- Cl -- -- -- OCH.sub.3 CC p oil147 -- -- Cl -- -- OCH.sub.3 CC p 97.5-98148 -- F -- -- -- OCH.sub.3 CC p 68-68.5149 -- -- F -- -- OCH.sub.3 CC p 76-76.5150 CH.sub.3 -- -- -- -- ICG.sub.3 CC p 70151 -- CH.sub.3 -- -- -- OCH.sub.3 CC p oil152 -- -- CH.sub.3 -- -- OCH.sub.3 CC p 77.5-78153 Cl Cl -- -- -- OCH.sub.3 CC p 128.5-130.5154 Cl -- Cl -- -- OCH.sub.3 CC p 87-88155 Cl -- -- Cl -- OCH.sub.3 C C p 57-58156 Cl -- -- -- Cl OCH.sub.3 CC p 116-117157 -- Cl Cl -- -- OCH.sub.3 CC p 86-87158 -- Cl -- Cl -- OCH.sub.3 CC p 75.5-76159 CH.sub.3 CH.sub.3 -- -- -- OCH.sub.3 CC p 93.5-94.5160 CH.sub.3 -- CH.sub.3 -- -- OCH.sub.3 CC p 78.5-79.5161 CH.sub.3 -- -- CH.sub.3 -- OCH.sub.3 CC p 98-98.5162 CH.sub.3 -- -- -- CH.sub.3 OCH.sub.3 C C p 93-93.5163 -- CH.sub.3 CH.sub.3 -- -- OCH.sub.3 CC p 101-102164 -- CH.sub.3 -- CH.sub.3 -- OCH.sub.3 CC p 84165 CH.sub.3 -- Cl -- -- OCH.sub.3 CC p 91.5-92166 -- CH.sub.3 Cl -- -- OCH.sub.3 CC p 79.5-80167 Cl -- -- -- CH.sub.3 OCH.sub.3 CC p 99-100168 -- -- -- -- -- OCH.sub.3 CC m 123-124169 -- Cl -- -- -- CH.sub.3 C C m 102.5-103.5170 -- -- Cl -- -- CH.sub.3 CC m 151.5-152.5171 -- -- F -- -- CH.sub.3 CC m 149.5-150172 -- -- CH.sub.3 -- -- CH.sub.3 CC m 119.5-120.5173 i-pr -- -- -- -- CH.sub.3 CC m 88174 Cl -- Cl -- -- CH.sub.3 CC m 121.5-122.5175 Cl -- -- Cl -- CH.sub.3 CC m 94.5-95.5176 Cl -- -- -- Cl CH.sub.3 CC m 124.5- 125.5177 -- Cl Cl -- -- CH.sub.3 CC m 129-130178 -- Cl -- Cl -- CH.sub.3 CC m 114.5-115.5179 CH.sub.3 -- -- -- CH.sub.3 CH.sub.3 CC m 128-129180 -- CH.sub.3 CH.sub.3 -- -- CH.sub.3 CC m 120.5-122.5181 CH.sub.3 -- Cl -- -- CH.sub.3 CC m 119-120.5182 -- CH.sub.3 Cl -- -- CH.sub.3 CC m 98-99183 Cl -- -- -- CH.sub.3 CH.sub.3 CC m 122.5-123.5184 Cl -- Cl Cl -- CH.sub.3 CC m 134-135185 -- -- -- -- -- OCH.sub.3 CC m 74.5-75.5186 -- Cl -- -- -- OCH.sub.3 CC m oil187 -- -- Cl -- -- OCH.sub.3 CC m 90-91188 -- F -- -- -- OCH.sub.3 CC m 45-46189 -- CH.sub.3 -- -- -- OCH.sub.3 CC m oil190 i-pr -- -- -- -- OCH.sub.3 CC m 71-73191 -- CF.sub.3 -- -- -- OCH.sub.3 CC m 57.5-58.5192 Cl Cl -- -- -- OCH.sub.3 CC m 96-97193 Cl -- Cl -- -- OCH.sub.3 CC m 100-101194 Cl -- -- Cl -- OCH.sub.3 CC m 75-76195 Cl -- -- -- Cl OCH.sub.3 CC m 69-70196 -- Cl Cl -- -- OCH.sub.3 CC m 72-73197 -- Cl -- Cl -- OCH.sub.3 CC m 87-88198 CH.sub.3 -- CH.sub.3 -- -- OCH.sub.3 C C m 74.5-75199 CH.sub.3 -- -- CH.sub.3 -- OCH.sub.3 CC m 84.5-85.5200 CH.sub.3 -- -- -- CH.sub.3 OCH.sub.3 CC m oil201 -- CH.sub.3 CH.sub.3 -- -- OCH.sub.3 CC m 93.5-94.5202 -- CH.sub.3 -- CH.sub.3 -- OCH.sub.3 CC m 96-97203 CH.sub.3 -- Cl -- -- OCH.sub.3 CC m 95.5-96.5204 -- CH.sub.3 Cl -- -- OCH.sub.3 CC m 78-79205 Cl -- -- -- CH.sub.3 OCH.sub.3 C C m 76-78206 Cl -- Cl Cl -- OCH.sub.3 CC m 79.5-80.5__________________________________________________________________________
TABLE 2______________________________________CompoundNo. NMR spectra (.delta.)(CDCl.sub.3)______________________________________ 90 3.15(3H,s), 3.73(3H,s), 4.55(4H,m), 6.03(2H,m), 6.48-7.30(8H), 7.67(1H,bs) 91 3.15(3H,s), 3.72(3H,s), 4.54(4H,m), 6.00(2H,m), 6.47-7.30(8H), 7.68(1H,bs) 93 2.23(3H,s), 3.16(3H,s), 3.73(3H,s), 4.55(4H,m), 6.05(2H,m), 6.52-7.30(8H), 7.69(1H,bs) 94 2.32(3H,s), 3.16(3H,s), 3.74(3H,s), 4.55(4H,m), 6.05(2H,m), 6.50-7.30(8H), 7.70(1H,bs) 96 3.16(3H,s), 3.72(3H,s), 4.54(4H,m), 6.03(2H,m), 6.50-7.37(8H), 7.65(1H,bs) 97 3.15(3H,s), 3.71(3H,s), 4.56(4H,m), 6.06(2H,m), 6.45-7.30(7H), 7.66(1H,bs) 99 3.15(3H,s), 3.72(3H,s), 4.55(4H,m), 6.02(2H,m), 6.49-7.32(7H), 7.70(1H,bs)100 3.16(3H,s), 3.73(3H,s), 4.55(4H,m), 6.07(2H,m), 6.52-7.35(7H), 7.67(1H,bs)101 3.15(3H,s), 3.72(3H,s), 4.50(4H,m), 5.98(2H,m), 6.48-7.35(7H), 7.69(1H,bs)102 3.15(3H,s), 3.73(3H,s), 4.51(4H,m), 6.00(2H,m), 6.50-7.30(7H), 7.68(1H,bs)103 2.15(3H,s), 2.25(3H,s), 3.16(3H,s), 3.72(3H,s), 4.54(4H,m), 6.06(2H,m), 6.50-7.30(7H), 7.67(1H,m)105 2.19(3H,s), 2.29(3H,s), 3.15(3H,s), 3.71(3H,s), 4.51(4H,m), 6.03(2H,m), 6.49-7.30(7H), 7.67(1H,m)106 2.24(6H,s), 3.14(3H,s), 3.71(3H,s), 4.30(2H,m), 4.53(2H,m), 6.05(2H,m), 6.48-7.31(7H), 7.65(1H,m)108 2.26(6H,s), 3.15(3H,s), 3.72(3H,s), 4.51 (4H,m), 6.03(2H,m), 6.47-7.31(7H), 7.70(1H,bs)111 2.27(3H,s), 3.15(3H,s), 3.73(3H,s), 4.51(4H,m), 6.10(2H,m), 6.50-7.31(7H), 7.67(1H,bs)112 3.14(3H,s), 3.71(3H,s), 4.52(4H,m), 5.98 (2H,m), 6.49-7.40(6H), 7.67(1H,bs)113 3.16(3H,s), 3.72(3H,s), 4.55(4H,m), 6.07(2H,m), 6.50-7.30(6H), 7.69(1H,bs)114 2.20(9H,s), 3.14(3H,s), 3.71(3H,s), 4.27(2H,m), 4.54(2H,m), 6.06(2H,m), 6.52-7.30(6H), 7.64(1H,bs)______________________________________
In practice, one or more compounds of this invention are usually applied to the field at a rate between 50 and 2000 g per 10 ares, preferably 100 and 1000 g per 10 ares, although the application rate may vary depending upon the conditions such as particular species and infestation level of weeds, particular herbicidal compound to be used.
The compounds of this invention can be applied in various ways to achieve herbicidal action. Although they can be applied per se, they are preferably applied by formulating them into a suitable form.
They can be formulated by a conventional way into various forms, such as solution, dispersion, emulsifiable concentrate, with a suitable liquid medium and forms such as wettable powder, granule, dust and tablet with a suitable solid carrier. Upon formulation, necessary additives must be used, such as emulsifier, dispersant, spreader, penetrant, stabilizer and the like.
The active compound of this invention may be used with both solvent and non-solvent liquid mediums. Suitable liquid mediums include for example, alcohols such as methanol, ethanol, ethyleneglycol and the like; ketones such as acetone, methyl ethyl ketone and the like; ethers such as dioxane, tetrahydrofuran, cellosolves and the like; hydrocarbons such as benzene, toluene, xylene, hexane, kerosine, naphtha, methylnaphthalene and the like; esters such as ethyl acetate, butyl acetate, and the like; organic bases such as pyridine, picoline and the like; and other organic solvents such as dimethylformamide, acetonitrile and the like.
The solid carrier which is useful in this invention includes diluents and fillers, for example, mineral powder such as kaoline, bentonite, clay, acid clay, diatom earth, mica powder, alumina and the like; and vegetable powder such as soy powder, flour, wood powder, active charcoal and the like; and mixtures thereof. For the emulsifier, dispersant, penetrant or spreader, any type of surfactant can be used such as anionic, cationic, nonionic or amphoteric surfactant.
Caseine, gelatin, starch, sodium alginate may be used as an optional adjuvant for the formulation.
Although the compound of this invention can be used in any suitable proportion in the formulation, the content usually ranges from 5 to 90% by weight based on the total formulation.
The herbicidal composition of this invention may also be combined with other types of active compound, fungicidal ingredient, insecticidal ingredient, plant-growth regulator, fertilizer depending upon the particular application.

The invention is further illustrated by the following Examples and Experiments, but the described particular active compound, carriers, adjuvants and proportions are by no means intended to limit the scope of this invention.
The proportions in terms of part of percent are based on weight, unless definition is given otherwise.
Example 1: Preparation of Wettable Powder
______________________________________Compound No. 32 50 partsSodium lignin sulfonate 1 partPolyoxyethylene alkylarylether 4 partsClay 45 parts______________________________________
These components were mixed thoroughly, and pulverized to form a wettable powder herbicide.
Example 2: Preparation of Emulsifiable Concentrate
______________________________________Compound No. 102 20 partsAlkylbenzene sulfonate 3 partsPolyoxyethylene alkylarylether 10 partsXylene 67 parts______________________________________
The components were mixed thoroughly to form homogeneous emulsifiable concentrate.
Example 3: Preparation of Granules
______________________________________Compound No. 203 6 partsBentonite 30 partsSodium alkylsulfate 1.5 partsClay 62.5 parts______________________________________
The components were mixed and intimately kneaded, and processed by a conventional way to form granules.
Example 4: Preparation of Dust
______________________________________Compound No. 139 7 partsClay 93 parts______________________________________
The components were thoroughly blended to form a dust herbicide.
EXPERIMENT 1
Polyethylene post having a surface area of 1/5000 areas were filled with paddy field soil (clayish loam). The pots were seeded with barnyard grass (Echinochloa Crusgalli P. Beauv var. orizicola Ohwi), Cyperaceous weed (Cyperus difformis L.) and some broadleaf weeds in a 2-cm depth soil layer. At the same time, 2-leaf stage rice plant seedlings were transplanted in the pots at a depth of 2 cm with two seedlings together per spot. Then, the pots were submerged in water 3 cm below the water level.
When starting the germination of the weeds, the herbicidal composition formulated in Example 1 was weighed in a predetermined amount and diluted with 10 ml of water per pot and added dropwise to the water in each pot. The pots were placed in a greedhouse to allow the rice plant and the weeds to grow. Three weeks after the treatment, the levels of herbicidal activity and phytotoxicity were observed on each pot.
The results are shown in Table 3 below.
In Table 3 the level of phytotoxicity against phytotoxic level of rice plant and herbicidal activity against weeds were rated on the following scale of from 1-5.
______________________________________Scale Pytotoxicity Herbicidal Effects______________________________________5 death 100% controlled (amount of weeds 0%)4 severe injury 80% controlled (amount of weeds 20%)3 moderately 60% controlled (amount of weeds 40%) severe injury2 moderate 40% controlled (amount of weeds 60%) injury1 slight injury 20% controlled (amount of weeds 80%)0 no injury 0% controlled (amount of weeds 100%)______________________________________
TABLE 3______________________________________ Applica- Phyto-Com- tion toxicity Herbicidal Effectpound Rate to Barnyard Cyperaceous BroadleakNo. (g/10a) Rice grass weed weed______________________________________ 250 1 5 5 51 500 3 5 5 5 1000 4 5 5 5 250 1 5 5 52 500 2 5 5 5 1000 4 5 5 5 250 0 4 5 53 500 1 4.5 5 5 1000 2 5 5 5 250 0 4 5 54 500 0 4.5 5 5 1000 0 5 5 5 250 0 2 2 45 500 0 3 3 4 1000 0 3 3 4.5 250 0 5 1 56 500 0 5 2 5 1000 1 5 4 5 250 1 3 5 57 500 3 4 5 5 - 1000 4 5 5 5 250 1 4.5 5 58 500 3 5 5 5 1000 4 5 5 5 250 1 4 5 59 500 2 5 5 5 1000 3 5 5 5 250 1 5 5 510 500 2 5 5 5 1000 3 5 5 5 250 0 3 3 411 500 0 4 5 5 1000 0 4 5 5 250 0 5 1 519 500 0 5 2 5 1000 0 5 4.5 5 250 0 5 4 520 500 0 5 5 5 1000 0 5 5 5 250 0 3 5 521 500 0 4 5 5 1000 0 4.5 5 5 250 0 5 4 522 500 0 5 4.5 5 1000 0 5 5 5 250 0 5 4 523 500 0 5 4 5 1000 0 5 4.5 5 250 0 3 4 524 500 0 4 4 5 1000 0 4 4.5 5 250 0 4 3 525 500 0 4.5 4 5 1000 0 5 4 5 250 0 2 2 526 500 0 3 2 5 1000 0 3 4.5 5 250 0 3 3 527 500 0 5 4.5 5 1000 0 5 5 5 250 0 5 4.5 528 500 0 5 5 5 100 0 5 5 5 250 0 4 4.5 529 500 0 5 5 5 1000 0 5 5 5 250 0 4 4 530 500 0 4.5 4.5 5 1000 0 4.5 5 5 250 0 4.5 4 531 500 0 5 4.5 5 1000 0 5 5 5 250 0 5 5 532 500 0 5 5 5 1000 0 5 5 5 250 0 5 4 533 500 0 5 4.5 5 1000 0 5 5 5 250 0 5 2 534 500 0 5 2 5 1000 0 5 3 5 250 0 5 3 536 500 0 5 4 5 1000 0 5 4.5 5 250 0 2 1 537 500 0 3 3 5 1000 0 4 4 5 250 0 4 4.5 538 500 0 5 5 5 1000 0 5 5 5 250 0 4.5 5 541 500 1 5 5 5 1000 1.5 5 5 5 250 0 2 1 542 500 0 3 2 5 1000 0 4.5 4 5 250 0 4.5 5 543 500 0 5 5 5 1000 0 5 5 5 250 0 4 1 444 500 0 4.5 2 4.5 1000 0 5 3 5 250 0 4 1 446 500 0 4.5 1 4.5 1000 0 5 2 5 250 0 4.5 1 547 500 0 5 2 5 1000 0 5 4 5 250 0 3 1 548 500 0 4 2 5 1000 0 4.5 3 5 250 0 1 1 551 500 0 2 2 5 1000 0 3 2 5 250 0 4 1 454 500 0 4.5 2 4 1000 0 5 3 5 250 0 2 1 458 500 0 2 1 4.5 1000 0 3 2 5 250 0 4 5 563 500 0 4.5 5 5 1000 0 5 5 5 250 0 4 1 464 500 0 4.5 2 4.5 1000 0 5 3 5 250 0 4 1 565 500 0 4.5 2 5 1000 0 5 4 5 250 0 4 1 4.566 500 0 4.5 2 5 1000 0 5 2 5 250 0 4 4.5 567 500 0 4.5 5 5 1000 0 5 5 5 250 0 5 2 4.568 500 0 5 4 5 1000 0 5 5 5 250 0 5 2 569 500 0 5 2 5 1000 0 5 3 5 250 0 4 1 370 500 0 5 2 3 1000 0 5 3 4 250 0 3 4.5 571 400 0 4 5 5 1000 0 4.5 5 5 250 0 3 4 572 500 0 4 4.5 5 1000 0 4.5 5 5 250 0 5 1 473 500 0 5 2 4.5 1000 0 5 3 5 250 0 4 1 574 500 0 4.5 2 5 1000 1 5 3 5 250 0 4 5 575 500 0 4.5 5 5 1000 0 5 5 5 250 0 3 3 4.576 500 0 4 4.5 5 1000 0 4.5 5 5 250 0 4 4.5 577 500 0 4 5 5 1000 0 5 5 5 250 0 2 4 578 500 0 3 5 5 1000 0 4 5 5 250 0 5 1 480 500 0 5 2 4.5 1000 0 5 2 5 250 0 3 4.5 581 500 0 4 5 5 1000 0 4 5 5 250 0 4 5 582 500 0 4.5 5 5 1000 0 5 5 5 250 0 5 5 585 500 1 5 5 5 1000 1.5 5 5 5 250 0 5 4 586 500 0 5 5 5 1000 0 5 5 5 250 0 5 4.5 587 500 0 5 5 5 1000 0 5 5 5 250 0 4 4 588 500 0 5 4.5 5 1000 0 5 5 5 250 0 4 4 589 500 0 4.5 5 5 1000 0 5 5 5 250 0 5 5 590 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 591 500 0 5 5 5 1000 0 5 5 5 250 0 4.5 3 592 500 0 5 5 5 1000 0 5 5 5 250 0 4.5 5 593 500 0 5 5 5 1000 0 5 5 5 250 0 5 4 594 500 0 5 4.5 5 1000 0 5 5 5 250 0 5 5 596 500 0 5 5 5 1000 0 5 5 5 250 0 4.5 5 597 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 598 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 599 500 0 5 5 5 1000 0 5 5 5 250 0 4.5 5 5100 500 0 5 5 5 1000 0 5 5 5 250 0 4 1 5101 500 0 4.5 2 5 1000 0 5 3 5 250 0 5 5 5102 500 0 5 5 5 1000 0 5 5 5 250 0 4 5 5103 500 0 5 5 5 1000 0 5 5 5 250 0 4.5 5 5105 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5106 500 0 5 5 5 1000 0 5 5 5 250 0 3 4.5 5107 500 0 4 5 5 1000 0 5 5 5 250 0 5 5 5108 500 0 5 5 5 1000 0 5 5 5 250 0 5 4 5109 500 0 5 4.5 5 1000 0 5 5 5 250 0 4 4.5 5110 500 0 4 5 5 1000 0 5 5 5 250 0 5 5 5111 500 0 5 5 5 1000 0 5 5 5 250 0 4 5 5112 500 0 4.5 5 5 1000 0 5 5 5 250 0 5 5 5113 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5114 500 0 5 5 5 1000 0 5 5 5 250 0 5 3 5115 500 0 5 5 5 1000 1.5 5 5 5 250 0 5 4.5 5116 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 4.5117 500 0 5 5 4.5 1000 0 5 5 5 250 0 5 4.5 5118 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5119 500 0 5 5 5 1000 0 5 5 5 250 0 4.5 5 5120 500 1 5 5 5 1000 1 5 5 5 250 0 5 5 5121 500 0 5 5 5 1000 1 5 5 5 250 1 5 4 5122 500 2 5 5 5 1000 4 5 5 5 250 0 5 5 5123 500 1 5 5 5 1000 1 5 5 5 250 0 5 5 5124 500 1 5 5 5 1000 1 5 5 5 250 0 5 4 5125 500 1 5 4.5 5 1000 1 5 4.5 5 250 0 5 5 5126 500 0 5 5 5 1000 0 5 5 5 250 0 4 4.5 5127 500 0 4.5 5 5 1000 0 5 5 5 250 0 5 4.5 5128 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5129 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5130 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5131 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5132 500 0 5 5 5 1000 0 5 5 5 250 0 4.5 5 5133 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5134 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5135 500 0 5 5 5 1000 0.5 5 5 5 250 0 5 5 5136 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5137 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5138 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5139 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5140 500 0 5 5 5 1000 1 5 5 5 250 0 4.5 5 5141 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5142 500 0 5 5 5 1000 0 5 5 5 250 0 5 2 5144 500 0 5 3 5 1000 0 5 4 5 250 0 5 4 5145 500 0 5 5 5 1000 1 5 5 5 250 0 5 5 5146 500 1 5 5 5 1000 1 5 5 5 250 0 5 1 5147 500 1 5 2 5 1000 1 5 3 5 250 0 5 4 5149 500 1 5 4.5 5 1000 1.5 5 5 5 250 0 5 4.5 5152 500 0 5 5 5 1000 0 5 5 5 250 0 4.5 4 5154 500 0 4.5 4.5 5 1000 0 5 5 5 250 0 5 4 5157 500 0 5 5 5 1000 0 5 5 5 250 0 5 4.5 5161 500 0 5 5 5 1000 0 5 5 5 250 0 4.5 1 5165 500 0 5 3 5 1000 0 5 4 5 250 0 5 5 5166 500 0 5 5 5 1000 0 5 5 5 250 0 4.5 5 5168 500 0 5 5 5 1000 1 5 5 5 250 0 4.5 5 5169 500 0 5 5 5 1000 0 5 5 5 250 0 4 4 5170 500 0 4.5 4.5 5 1000 0 5 4.5 5 250 0 4 4.5 5171 500 0 5 4.5 5 1000 0 5 5 5 250 0 4.5 5 5172 500 0 4.5 5 5 1000 0 5 5 5 250 0 4.5 5 5174 500 0 4.5 5 5 1000 0 5 5 5 250 0 5 5 5175 500 0 5 5 5 1000 1 5 5 5 250 0 3 4.5 4.5176 500 0 4 5 5 1000 0 4.5 5 5 250 0 3 5 5177 500 0 4 5 5 1000 0 5 5 5 250 0 4 5 5178 500 0 5 5 5 1000 0 5 5 5 250 0 4.5 5 5179 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5180 500 0 5 5 5 1000 0 5 5 5 250 0 4 5 5181 500 0 4.5 5 5 1000 0 5 5 5 250 0 5 5 5182 500 0 5 5 5 1000 0 5 5 5 250 0 5 2 4.5183 500 0 5 3 4.5 1000 0 5 4 5 250 4.5 5 5184 500 0 4.5 5 5 1000 0 5 5 5 250 0 5 5 5185 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5186 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5187 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5189 500 0 5 5 5 1000 0 5 5 5 250 0 4 5 5190 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5191 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5192 500 0 5 5 5 1000 0 5 5 5 250 0 4.5 5 5193 500 0 4.5 5 5 1000 0 5 5 5 250 0 5 5 5194 500 0 5 5 5 1000 1 5 5 5 250 0 5 5 5195 500 0 5 5 5 1000 1 5 5 5 250 0 5 5 5196 500 0 5 5 5 1000 0 5 5 5 250 0 4.5 5 5197 500 0 4.5 5 5 1000 0 5 5 5 250 0 5 5 5198 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5199 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5200 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5201 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5202 500 0 5 5 5 1000 0 5 5 5 250 0 4.5 5 5203 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5204 500 0 5 5 5 1000 0 5 5 5 250 0 5 5 5205 500 0 5 5 5 1000 0 5 5 5 205 0 5 5 5206 500 0 5 5 5 1000 0 5 5 5 62.5 0.5 2 1 4Sime- 125 2 3 3 5tryne* 250 5 5 5 5Un-treated -- 0 0 0 0Area______________________________________ *Control Compound: 2,4bis(ethylamino)-6-methylthio-1,3,5-triazine
EXPERIMENT 2
Polyethylene pots having a surface area of 1/5000 ares were filled with field soil (dry clayish loam) and seeded with seeds of rice plant, wheat, barnyard grass, radish and "Aobiyu" (Amaranthus retroflexus L.), covered with the same soil at a depth of one cm and placed in a green house to allow the plants to germinate. After germination and at 2-leaf stage for rice plant, 3-leaf stage for wheat and when the first leaf (following a pair of baby leaves) came out for radish and Aobiyu, the wettable powder formulated as in Example 1 was weighed in a predetermined amount and, after diluted with 2 ml of water per pot, sprayed thoroughly on the foliage of the weed plants. Two weeks after the treatment, the herbicidal activity and phytotoxicity against the useful plants were observed.
The results are shown in Table 4. The scale in the Table is the same as that in Experiment 1.
TABLE 4______________________________________Com- Compooundpound concent- Rice BarnyardNo. ration plant Wheat grass Radish Aobiyu______________________________________ 0.25 0 0 0 5 51 0.5 2 1 2 5 5 1 3 3 5 5 5 0.25 0 0 2 5 54 0.5 0 1 2 5 5 1 1 2 3 5 5 0.25 0 0 4 5 58 0.5 1 3 4.5 5 5 1 2 4 5 5 5 0.25 0 0 2 5 510 0.5 1 2 4 5 5 1 1 3 5 5 5 0.25 0 0 4 1 119 0.5 0 0 5 3 4.5 1 0.5 0 5 5 5 0.25 0 0 1 3 424 0.5 0 0 2 4.5 5 1 0 1 3 5 5 0.25 0 0 2 5 527 0.5 0 0 5 5 5 1 0 0.5 5 5 5 0.25 0 0 2 2 334 0.5 0 0 5 4 4.5 1 0 0 5 4.5 5 0.25 0 0 1 1 136 0.5 0 0 4 3 3 1 0 0 5 5 4.5 0.25 0 0 3 3 338 0.5 0 0 4 4 4 1 1 1 4.5 5 5 0.25 0 0 4.5 5 541 0.5 2 2 5 5 5 1 4 4 5 5 5 0.25 0 0 2 5 543 0.5 1 1 3 5 5 1 2 2 5 5 5 0.25 0 0 2 4.5 446 0.5 0 0 3 5 5 1 0 0 4 5 5 0.25 0 0 4.5 5 547 0.5 0 0 5 5 5 1 0 2 5 5 5 0.25 0 0 3 4 454 0.5 0 0 5 4.5 5 1 1 1 5 5 5 0.25 0 0 5 4.5 558 0.5 0 0 5 5 5 1 1 2 5 5 5 0.25 0 0 3 4 563 0.5 0 1 4 5 5 1 1 2 5 5 5 0.25 0 0 3 1 166 0.5 0 0 4 4 3 1 0 0 5 5 5 0.25 0 0 1 4 567 0.5 0 0 3 4.5 5 1 0 1 4 5 5 0.25 0 0 4 5 568 0.5 1 1 5 5 5 1 2 2 5 5 5 0.25 0 0 4 3 369 0.5 0 0 5 4.5 4 1 1 2 5 5 5 0.25 0 0 4 5 576 0.5 0 1 5 5 5 1 1 2 5 5 5 0.25 0 0 2 4.5 578 0.5 0 1 4 5 5 1 1 1 5 5 5 0.25 0 0 4 4.5 4.580 0.5 0 1 5 5 5 1 1 2 5 5 5 0.25 2 0 3 5 585 0.5 3 1 4 5 5 1 4 2 5 5 5 0.25 0 0 5 5 586 0.5 1 2 5 5 5 1 2 3 5 5 5 0.25 0 0 3 3 489 0.5 0 1 4 3 5 1 1 2 5 5 5 0.25 0 0 3 2 592 0.5 1 1 4.5 3 5 1 1 3 5 5 5 0.25 0 0 4.5 5 594 0.5 1 2 5 5 5 1 2 3 5 5 5 0.25 0 0 4.5 5 5101 0.5 0 1 5 5 5 1 2 2 5 5 5 0.25 0 0 3 3 5106 0.5 0 1 4 4 5 1 0 3 5 5 5 0.25 0 0 4 5 5109 0.5 0 1 5 5 5 1 1 3 5 5 5 0.25 0 0 2 3 4113 0.5 0 1 4 4 5 1 1 2 5 5 5 0.25 0 0 3 3 4.5114 0.4 0 0 4.5 4.5 5 1 1 1 5 5 5 0.25 2 1 5 5 5115 0.5 3 2 5 5 5 1 4 4 5 5 5 0.25 0 0 4.5 5 5117 0.5 0 0 5 5 5 1 1 2 5 5 5 0.25 0 2 5 5 5122 0.5 1 3 5 5 5 1 3 3 5 5 5 0.25 0 0 4 5 5125 0.5 1 1 5 5 5 1 2 3 5 5 5 0.25 0 0 3 4 5126 0.5 0 1 4 4.5 5 1 1 2 5 5 5 0.25 0 0 4 5 4.5129 0.5 0 1 5 5 5 1 2 3 5 5 5 0.25 0 0 4.5 5 5135 0.5 0 0 5 5 5 1 1 2 5 5 5 0.25 0 0 4.5 5 5139 0.5 0 0 5 5 5 1 2 3 5 5 5 0.25 1 0 4.5 5 5144 0.5 2 1 5 5 5 1 4 3 5 5 5 0.25 0 0 5 5 5145 0.5 1 2 5 5 5 1 2 3 5 5 5 0.25 0 2 5 5 5149 0.5 1 2 5 5 5 1 3 4 5 5 5 0.25 0 1 4.5 5 4.5152 0.5 0 1 5 5 5 1 1 3 5 5 5 0.25 0 0 4 4 5157 0.5 1 1 5 5 5 1 2 3 5 5 5 0.25 0 0 4 4.5 5161 0.5 1 1 5 5 5 1 2 2 5 5 5 0.25 0 0 5 4.5 5165 0.5 0 1 5 5 5 1 2 3 5 5 5 0.25 1 1 4 5 4.5168 0.5 2 2 5 5 5 1 2 3 5 5 5 0.25 0 1 4.5 5 5169 0.5 1 3 5 5 5 1 2 4 5 5 5 0.25 0 0 3 1 2171 0.5 0 0 4 2 4 1 0 1 5 4 5 0.25 0 1 4 4.5 5172 0.5 1 2 4.5 5 5 1 2 2 5 5 5 0.25 0 0 4 4.5 4178 0.5 0 1 5 5 5 1 2 2 5 5 5 0.25 0 0 4.5 4.5 4180 0.5 0 2 5 5 5 1 2 3 5 5 5 0.25 0 0 4 5 5182 0.5 0 1 5 5 5 1 2 3 5 5 5 0.25 0 0 3 2 2184 0.5 0 0 4 4 4 1 1 2 5 5 5 0.25 0 0 4 4.5 4.5185 0.5 1 2 5 5 5 1 2 3 5 5 5 0.25 0 1 4 5 5186 0.5 1 2 5 5 5 1 3 4 5 5 5 0.25 2 2 5 5 5189 0.5 3 2 5 5 5 1 4 4 5 5 5 0.25 0 1 4 5 4.5193 0.5 1 2 5 5 5 1 3 4 5 5 5 0.25 0 0 5 5 4200 0.5 1 2 5 5 5 1 2 3 5 5 5 0.25 0 1 3 4.5 4.5203 0.5 1 2 4 5 5 1 3 4 5 5 5Un-treatedArea -- 0 0 0 0 0______________________________________

Number	Date	Country	Kind
55-49575	Apr 1980	JPX
55-64038	May 1980	JPX

Number	Name	Date
3903156	Teach	Sep 1975
4129436	Takemoto et al.	Dec 1978
4144049	Yoshida et al.	Mar 1979
4221817	Tenne	Sep 1980
4249938	Takemoto et al.	Feb 1981
4260411	Yoshida et al.	Apr 1981
4263219	Fujita et al.	Apr 1981
4294986	Spatz et al.	Oct 1981

Number	Date	Country
503459	Apr 1971	CHX
528861	Nov 1972	CHX
532891	Mar 1973	CHX

Urea derivatives and highly selective herbicidal compositions containing the same

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