CA1242730A - .delta..SUP.2-1,2,4-TRIAZOLIN-5-ONE DERIVATIVES AND HERBICIDAL COMPOSITIONS CONTAINING THE SAME - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
.DELTA.2-1,2,4-Triazolin-5-one derivatives represented by the general formula, (wherein R is a hydrogen atom; an alkali metal atom;
a quaternary ammonium salt; an unsubstituted-alkyl group having 1 to 6 carbon atoms; a substituted-alkyl group having halogen atoms as the substituents; an unsubstituted-cycloalkyl group; a substituted-cycloalkyl group having halogen atoms as the substituents; an alkenyl group; an alkynyl group; a lower alkoxyalkyl group; a lower alkylthioalkyl group; a lower alkylsulfinylalkyl group;
a lower alkylsulfonylalkyl group; a lower alkoxyalkoxyalkyl group; a lower alkoxycarbonylalkyl group; a hydroxy-carbonylalkyl group; an unsubstituted-benzyl group; a substituten-benzyl group having 1 to 2 substituents selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, a lower alkoxycarbonyl group, a hydroxycarbonyl group and a phenoxy group; .alpha.-methylbenzyl group or a phenethyl group).
The .DELTA.2-1,2,4-triazolin-5-one derivatives are useful as herbicides.

Description

FIELD OF THE INVENTION
The present invention relates to ~ -1,2,4-triazolin-5-one derivatives and herbicidal compositions containing the same as the active ingredient.
~2-1,2,4-Triazolin-5-one derivatives according to the present invention are represented by the general formula (I), F
Cl ~ N N-CHF2 ( I ) o r N ='~ CH
ROCfHO 3 (wherein R is a hydrogen atom; an alkali metal atom;
a ~uaternary ammonlum salt; an unsubstituted-alkyl group having 1 to 6 carbon atoms; a substituted-alkyl group hav-ing halogen atoms as the substituents; an unsubstituted-cycloalkyl group; a substituted-cycloalkyl group having halogen atoms as the substituents; an alkenyl group; an alkynyl group; a lower alkoxyalkyl group; a lower alkylthioalkyl group; a lower alkylsulfinylalkyl group;
a lower alkylsulfonylalkyl group; a lower alkoxy-alkoxyalkyl group, a lower alkoxycarbonylalkyl group;
a hydroxycarbonylalkyl group; an unsubstituted-benzyl .~ i ,i~

3~

1 group; a su~stituted-benzyl group having 1 to 2 substituents selected rom the group consisting of a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, a lower alkoxycarbonyl group, a hydroxycarbonyl group and a phenoxy group; ~-methylbenzyl group or a phenethyl group).

DESCRIPTION OF THE PRIOR ART
Q -1,2,4-Triazolin-5-one derivatives represented by the general formula (I) according to the present invention are novel compounds and have not been known in any literature.
Some of similar compounds related to the above-mentioned ~ -1,2,4-triazolin-5-one derivative represented by the general formula tI) are disclosed as the active ingredient in herbicidal compositions in Japanese Patent Kokai (Laid open) No. Sho 57-10~079 (1982) and Sho 57-181069 11982).
The present inventors have found that compounds represented by the general formula (I) possess effective herbicidal activities, thus they are useful as agricultural herbicides.
Additionally, the present inventors have found the Eacts that compounds represented by the general formula (I) show surprisingly excellent herbicidal activities in relatively lower dosage and with lower phytotoxicities as compared with act.ivities shown hy compounds disclosed in the above-mentioned prior art references.

SUMMARY OF THE INVENTION
An object of the present invention is to provide novel ~ -1,2,4-triazolin-5-one derivatives.
Another object of the present invention is to provide herbicidal compositions containing the ~2-1,2,4-triazolin-5-one as the active ingredient.
Yet further object of the present invention is to provide processes for preparing ~2-1,2,4-triazolin-5-one derivatives.
Compounds represented by the general formula (I) can be prepared by for example, processes method-A, method-B and method-C as follows:

Method-A

~ ~ CHF2 zl F O

O ~ N ~ Base ~ N N-CHF 2 ~II) CH3 (I) (wherein R is the same as defined above; zl is a chlorine atom, a bromine atom or an iodine atom).

3~

1 Method-B

Cl- ~ ~ N N-CHF2 ROCCH-Z Cl ~ ~ N -CHF2 N ~ (V) I N ~
~o CH3 Base 3- ROCCHO C~I3 (IV) CH3 (I~

(wherein R is the same as defined above; z2 is a halogen atom).

Method-C

F o F O
~ ~ ROH (VI) ~ ~
C1 ~ -N N-CHF2 - ~- Cl ~ N~ ~ -CHF2 li CH3 ROCCHO C~I3 XCCHO

3 (VII) ( I) S (wherein R is the same as defined above; X is a halogen atom or a hdyroxyl group).
Thus, the objective ~2-1,2,4-triazoline-5-one derivative represented by the general formula (I) can be prepared, in method-A, by reacting a compound represented by the general formula (II~ with a compound represented by the general formula (III); in method-B, by reacting a ~ t~3 ~

1 compound represented by the general formula (IV) with a compound represented by the general formula (V); and in method-C, by reacting a compound represented by the general formula (VII) with a compound represented by the general formula (VI), respectively in an inert solvent, in the presence or absence of a basic compound.
As to the inert solvent used ln these reactions, any inert solvent which does not give any adverse effect to the reactions may be employed, for ex~mple aromatic hydrocarbons such as benzene, toluene, xylene or the like can be exemplified; aliphatic hydrocarbons such as n-hexane, cyclohexane or the like can be exemplified;
alcohols such as methanol, ethanol, propanol, ethylene glycol or the like can be exemplified; ketones such as acetone, methyl ethyl ketone, cyclohexanone or the like can be exemplified; lower aliphatic acid esters such as ethyl acetate or the like can be exemplified; ethers such as tetrahydrofuran, dioxane or the like can be exempli~ied; lower fatty acid amides such as dimethyl-formamide, dimethylacetoamide or the like can be exempli-fied; and water, dimethyl sulfoxide or the like can be ex,emplified. The above-mentloned solvents may be employed in singly or in a mixture thexeof.
Further, in method-C, when an alcohol is used as the solvent, an alcohol corresponding to a compound repre-sented by t~e general formula ~VI) may preferably be used.
As to the basic compound used in the above-mentioned reactions, inorganic basic compounds, for 3~
l example alkali metal hydrides such as sodium hydride or the like; alkali metal hydroxides such as sodium hydroxide, potassium hydrcxide or the like; alkali metal carbonates such as sodium carbonate, potassium carbonate or the like;
alkali metal hydrogen carbonate such as sodium hydrogen carbonate, potassium hydrogen carbonate or the like;
alkali metal alcoholate such as sodium methylate or the li~e; and organlc basic compounds such as pyridine, tri-methylamine, triethylamine, diethylaniline, 1,8-diazabi-cyclo-[5,4,0]-7-undecene or the like can be exemplified.
Reactions of the present invention can be carried out, for example at a temperature in the range of from 0 to 150C to a predetermined temperature.
The reactions in each step therein are equimolar reactions, and in carrying out these reactions, slightly excess amount of one reactant to the amount of another reactant may be employed.
The reaction time may be selected from in the range of from 0.5 to 48 hours.
After the reaction is completed, the objective product can be obtained by treating the reaction product under a conventional manner.
Compound represented by the general formula (II) used as the starting material in method-A may be synthesiz-ed by the reaction steps as follows:

3~

\ ~2 Rl-A-f=NcooR

O CH3 (IX) Il ~
ROCCHO Heat CH3 (VIII) Cl ~ ~ NHNHC=NCOOR
~ H3 Basic compound ROCfHO
CH3 (X) F O

C1- ~ N NH
O ~ N ~

1 (wherein R is the same as defined above; Rl and R2 are each a lower alkyl group, A is an oxygen atom or a sulfur atom).

Thus, a compound represented by the gene.ral formula (II) can be prepared by reacting a compound represented by the general formula (VIII) with a compound represented by the general formula ~IX) in an inert solvent under a heating condition, -then the thus obtained compound represented by the general

2~

1 formula (X) is trea-ted under a ring-closing reaction, with a basic compound, with or without being separated from the xeaction product.
Furthermore, a compound represented by the general formula (IV) used as the starting material in method-B may be synthesized by the reaction step as follows:

F O F O

Cl ~ N -CHF2 ~3 Cl ~ N N-CHF2 (XI~ (IV) (wherein Rl is the same as defined above).
In the above-mentioned reaction, in place of using hydrobromic acid, there may be used hydroiodic acid or an alkyl thiolate.
Typical examples of ~2-1,2,4-triazolin-5-one derivatives represented by the general formula (I) are shown in the following Table 1.

F O

Cl ~ N N-CHF
O ~ \N ~ 2 ROCfHO C~3 CH3 (I) Table 1 Compound No. R Physical properties 1 H- nD 1.5192 2 Na- Melting point 186.1C

3 K- Melting point 119.2C

4 ~ H4- Metling point 92.7C
lso C3H7~ H3 Melting point 157.3C
6 (C2H5) ~ H- Oily substance 7 (n-C4H9)2~ H2- Melting point 126.5C
8 CH3- n23 1.5142 C2H5 nl 1.5112 n~C3H7~ n23'0 1 5051 11 iso-C3H7- n23 0 1 5051 12 n C4Hg n29 0 1.5031 13 iso-C4Hg- n29 0 1.5011 14 tert-C H - nD 1.5009

5 11 nD 1O4984 16 lSO-C H - nD 1.5002 17 _ C6H13 nD '5 1.4992 18 ClCH2CH2 nD6-5 1.5204 19 BrCH2CH2 nl9 5 1.5291 C13CCH2- Melting point 106.5C
21 F3CCH2- nl9 5 1.4826 22 ClCH2CH2CH2- Melting point 87.7C
23 BrCH2CH2CH2- Melting point 83.8C
24 ClCH2fH- Melting point 58.7C

CH3 - Cont'd -3~

Table 1 (Cont'd) ClCH2CHCH2- Melting point 95.0C
Cl 26 ClCH2 \ CH nD 5 1.5091 ClCH2 /
27 BrCH2 \ CH- Melting point 104.2C
BrCH2/
28 3C > CH- nl9 5 1.4573 29 ClcH2cH2cH2cH2 Melting point 95.3C

~ n26 0 1 5130 31 ~ n27-5 1 5140 32 Cl nl7 5 1 5174 33 CH2-CHCH2- n28.5 1 5156 34 CFI_CCH2 n28-5 1.5192 CH_CCH2CH~- nl7 5 1.5209 36 CH30(CH2)2 n26 0 1 5088 37 C2H5O~CH2)~- n26 0 1 5022 38 iso-C3H7O(cH2)2 nD6 0 1.4989 _ 4 9 (C 2)2 n26.0 1 4878 CH OCH~H CH - n~7-5 1.5009 41 CH3SCH2- nl~ 1.5279 42 CH3S[CH2)2- n26-5 1.5306 - Cont'd -Table 1 (Cont'd) 43 C2H5S(CH2)2- nl9'5 1.5274 44 1so-c3H7s(cH2)2 nl9 5 1.5233 1so-C4HgS(CH2)2- nl9 5 1.5212 46 seC-c4H9s~cH2)2 nl9'5 1.5219 47 tert-C4HgS~CH2)2- n22-5 1 5179 48 CH3S(CH2)3- nD9 5 1.5299 49 C2H5S(CH2)3- nl9 5 1.5203 1so-c3H7s(cH2)3- nl9 5 1.5204 51 n-C4HgS(CH2)3- nl4 5 1 5216 52 1SO-C4Hgs(cH2)3- nD 5 1.5209 53 tert-C4HgS(CH2)3- nl6 5 1 5172 54 CH3S(CH2~2- Melting point 104.5C

~ Melting point 99.8C
O O
56 CH30(CH2~2O(cH2)2 nD6 0 1.5052 57 CH OC-CH- Melting point 108.1C
3 il l 58 ~ CH2- Melting point 82.4C
__ "-Cl Cl CH2- Melting point 117,5C
~ CH2- Melting point 72.6C

61 C1 - ~ CH2- Melting point 73.0C

- Cont'd -, 7~

Table 1 (Cont'd) 62 ~ CH~- Melting point 115.7C

63 F ~ CH~- Melting poin-t 80.0C

64 H3C- ~ CH2- Melting point 102.8C

H3C0 ~ - CH2- Melting point 89.4C

66 02N ~ CH2- Melting point 126.5C

67 C2H5C ~ - CH2- Melting point ].35.3C

68 ~ CH2- n26-0 l 5588 69 Cl ~ CH2- Melting point 163.0C

C1 Melting point 114.7C

CH3 \
71 CH30 ~ CH2- Melting point 96.5C

- Cont'd -L?~

Table 1 (Cont'd) 72 ~ -CH- Oily substance 73 ~ CH2CH2- Oily substance 1 Next, NMR spectrum data for the compound having physical properties indicated as oily substance are shown in Table 2 below.

Table 2 No. NMR TC14 (ppm)

6 1.15 (t, 9H), 1.64 (d, 3H3~ 2.41 (s, 3H), 2.19 (q, 6M), 4O53 (q, lH3, 7.03 (t, lH),

7.Q4 (d, lH), 7.22 (d, lH) 72 1.32-1.77 (m, 6H), 2.30 ~s, 3H), 4.60 (q, lH), 5.76 (q, lH), 686 (t, lH), 6.76 7.31 (m, 7H) 73 1.56 (d, 3H)~ 2.35 (s, 3H), 2.84 (t, 2H), 4.28 (t, 2H), 4.59 (q, lH), 6.91 (t, lH), 6.85-7.32 (m, 7H~

1 The present invention will be illustrated more specifically by way of showing the following examples.
However, the present invention will not be restricted only to these examples.

Example 1 Preparation of 1-{4-chloro-2-fluoro-5-[1-(ethoxy-carbonyl~ethoxy]phenyl}-4-difluoromethyl-3-methyl-~2-1,2,4-triazolin-5-one (Compound No. 9) F O F O

Cl ~ -N I N-CHF2 BrCHCOOC2H5 Cl ~ -N ~ -CHF2 ~O O ¦ CH3 ~5C2OCIHO

(IV) C~I3 13.27 Grams (0.045 mole) of compound (IV), 9.06 g (0.0498 mole) of ethyl ~-bromopropionate and 13.27 g (0.0~62 mole) of potassium carbonate were refluxed in 200 ml of acetone with stirring for 3 hours.
Then, the reaction mixture was cooled to a room tempera-ture, and the insoluble matters were removed by filtra-tion. Next, the filtrate was concentrated, and the oilysubstance thus obtained was dissolved in diethyl ether, and washed with cold water, then the diethyl ether solu-tion was dried, the solvent was removed by evaporation to yield an oily substance. (This oily substanc~ was indeed clear state as it was, and was purified by means )3~

1 of a dry column chromatography by using a sllica gel.) Yield: 14.7 g (83.1%) Refractive index nD 1.5112.

Example 2 Preparation of 1-{4-chloro-2-fluoro-5-[1-(hydroxycarbonyl)ethoxy]phenyl}-4-difluoromethyl-3-methyl-~ ~1,2,4-triazolin-5-one (Compound No. 1) F O F O

Cl ~ N ~ N-CHF2 Cl ~ N N-CHF2 1.4 Grams ~0.00356 mole) of 1~{4-chloro-2~
fluoro-5-[1-~ethoxycarbonyl)ethoxy]phenyl}-4-difluoro-methyl-3-methyl-~-1,2,4-triazolin-5-one was dissolved in 50 ml of ethanol, then to this solution was added 1.2 g of 20~-potassium hydroxide aqueous solution, and the whole mixture was stirxed at a room temperature for 3.5 hours. After the reaction was completed, the reac-tion mixture was poured in an ice-water, acidified with hydrochloric acid, then the desired product was extracted with ethyl acetate. The extract was washed with water, and dried with anhydrous magnesium sulfate, then the solvent was removed by evaporation to yield 1.1 g ol oily substance as the ob]ective product.
Refractive index n24 5 1.5192. Yield 84~.

~ Z L~ 7 3V

1 Example 3 Preparation of sodium 2-[2-chloro-5-(4-difluoro-methyl-3-methyl-5-oxo-~ -1,2~4-triazolin-1-yl)-4-fluoro-phenoxy]propionate (Compound No~ 2~

F O F O

Cl ~ N ~ N-CHF2 ~ ~ Cl ~ N M-CHF2 HOCfH i N ~ c~3 ~ N

c~3 CH3 0.5 Gram (0.00136 mole) of 1-{4-chloro-2-fluoro-5-[1-~hydroxycarbonyl)ethoxy]phenyl}-4-difluoro-methyl-3-methyl-~ -1,2,4-triazolin~5-one was dissolved in 20 ml of tetrahydrofuran, then to this solution was added 0.05 g (0.00125 mole) of sodium hydride, and the whole mixture was stirred at a room temperature for 10 minutes. After the reaction was completed, the tetrahydrofuran was removed by evaporation under a reduced pressure, the residue thus obtained was washed with n-hexane to yield 0.37 g of the objective product.
Meltlng point 186.1C. Yield 76.4%.

7~

1 Example 4 Preparation of dibutylammonium 2-[2-chloro-5-(4-difluoromethyl-3-methyl-5-oxo-Q2-1,2,4-triazolin-1-yl)-4-fluorophenyloxy]propionate (Compound No. 7) F O F O

Cl ~ \ ~ F2 - =a_ Cl ~ N N-CHF2 CH3 n-C4~Ig \ 6~3 ll ¦ CH3 IH3 n C4Hg CH3 0.5 Gram (0.00136 mole~ of 1-{4-chloro-2-fluoro-5-[1-(hydroxycarbonyl)ethoxy]phenyl}-4-difluoro-methyl-3-Q -1,2,4-triazolin-5-one was dissolved in 20 ml of benzene, then to solution was added 1.0 g (0.0139 mole) of dibutylamine, then under an ice-cooling condition, the reaction was carri.ed out. The crystals fromed in the reaction mixture was collected by filtration, and washed with benzene to yield 0.51 g of the objective compound.
Melting point 126.5C. Yield 79.4~.

- 17 ~

3~
1 Example 5 Preparation of 1-{4-chloro-2-fluoro-5-[1~
(propargyloxycarbonyl)ethoxy]phenyl}-4-difluoromethyl-3-methyl-Q2 1,2,4-triazolin-5-one (Compound No. 34) F O F O

F O

Cl- ~ N N-CHF
N ~

Il CH3 HC-CCH2OCfHO

A mixed solution of 20 ml of thionyl chloride containing 2.7 g of 1-{4-chloro-2-fluoro-5-[1-Ihydroxy-carbonyl)ethoxy]phenyl}-4-difluoromethyl-3-methyl-Q2-1,2,4-triazolin-5-one was refluxed under heating for 2 hours. After the reaction was completed, the excessive thionyl chloride was removed by evaporation, and obtained 2.8 g of 1-~4-chloro-2-fluoro-5-~ chloro-carbonyl)ethoxyJ-phenyl}-4-difluoromethyl-3-methyl-Q2_ 1,2,4-triazolin-5-one quantitatively. Then 0.5 g 1 (0.0013 mole) of this compound was dissolved in 20 ml of tetrahydrofuran, to this solution was added 0.2 g (0.00357 mole) of propargyl alcohol and 0.2 g (0.00198 mole) of triethylamine, then the whole mixture was reacted at a room temperature for 2 hours. After the reaction was completed, the reaction mixture was poured in an ice-water, and extracted with ethyl acetate. The ethyl acetate layer was washed with an aqueous solution containing 10~ of potassium carbonate, then with water, dried with anhydrous magnesium sulfate, and the solvent was removed by evaporation. Thus obtained residue was purified by means of a dry column chromatography to yield 0~35 g of the objective product.
Refractive index n28-5 1.5192. Yield 66.6%.

Example 6 Preparation of 1-{5-[1-(tert-butoxycarbonyl)-ethoxy]-4-chloro 2-fluorophenyl}-4-difluromethyl-3-methyl-~ -1,2,4-triazolin-5-one (Compound No. 14) F O F O

C ~ N ~ N-C~F2 ~ C ~ \N ~

ll CH3 ll CH3 ClCf HO (CH3)3-COCIC~IO

0.58 Gram ~0.00151 mole) of 1-{4-chloro-2-fluoro-5-[1-(chlorocarbonyl)ethoxy]phenyl}-4-difluoro-.

'7~{3 1 methyl-3-methyl-Q2-1,2,4-triazolln-S-one was added in a mixed solution of 0.25 g (0.00338 mole) of tert-butyl alcohol, 0.14 g (60~ in oil, 0.0035 mole) of sodium hydride, and 20 ml of tetrahydrofuran. The whole mixture was heated under refluxing condition for 6 hours. After the reaction was completed, the reaction mixture was treated under a condition similar to that described in Example 5, to yield 0.13 g of the desired product.
Refractive index n26 0 1.5009. Yield 18.8%.

Example 7 Preparation of 1-{4-chloro-2-fluoro-5-[1-[[l-(methoxycarbonyl)ethoxy]carbonyl]ethoxyphenyl}-4-difluoromethyl-3-methyl-~2-1,2,4-triazolin-5-one (Compound No. 57) F o F O
Cl ~ ~N ~ 2 ~ ~ Cl ~ N N-C~F2 HOCfHO CH3 CH30CCHOCCHO C~I3 A mixed solution of 0.5 g l0.00136 mole) of 1-~4-chloro-2-1uoro-5-[1-(hydroxycarbonyl)ethoxy]phenyl}-4-difluoromethyl-3-methyl-~2-1,2,4-triazolin-5-one, 0.28 g (0.00136 mole) of N,N'-dicyclohexylcarbodiimide, 0.02 g (0.000164 mole) of 4-dimethylaminopyridine and 10 ml of diethyl ether was reacted at a room temperature for 6 hours. After the completion of the reaction, the insoluble matters were removed by filtration, and the 73l~

1 filtrate was txeated by evaporation, the residue obtained was purified by means of a dry column chromatography to yield 0.41 g of the objective product. Melting point 108.1C. Yield 64.3~.

Example 8 Preparation of 1 {4-chloro-2-1uoro-5-[1-(ethoxycarbonyl)ethoxy]phenyl}-4-difluoromethyl-3-methyl--1,2,4-triazolin-5-one (Compound No. 9) F O F O
Cl ~ N NH 3~ Cl ~ N N-CHF2 C2~5OCCHO CH3 C2H5OCCHO CH3 0.046 Gram (0.00134 mole) of sodium hydride was suspended in 10 ml of dried N,N-dimethylformamide, to this suspension was added dropwise a solution prepared by dissolving 0.4 g (0.00122 mole) of 1-{4-chloro-2-fluoro-5-[1-(ethoxycarbonyl)ethoxy~phenyl}-3-methyl-~2-1,2,4-triazolin-5-one at a room temperature. After the comple-tion of dropwise addition, the whole mixture was stirredfor 30 minutes, then monochlorodifluoromethane (ClCHF2) gas was introduced into the mixture at 130C for 5 hours.
After the reaction was completed, the reaction mixture was cooled to a room temperature, and the reaction mixture was poured in an ice-water. The oily substance formed was extracted with diethyl ether, and the extract was dried with anhydrous magnesium sulfate. The solvent was removed Z'7~6~

1 by evaporation to yleld an oily substance. This oily substance was purified by means of a dry column chromato-graphy to yield 0.15 g of the objective product. Refrac-tive index n19 1.51120 Yield 32.6%.

Example 9 Preparation of 1-{4-chloro-2-fluoro-5-[1-(methylthiomethoxycarbonyl)ethoxy]phenyl}-4-difluoro-methyl-3-methyl-~2-1,2,4-triazolin-5-one (Compound No. 41) F ~ F O

C ~ N -CHF2 ~=~ C ~ \ ~ 2 HOCfHO CH3 CH3SCH2OCfHO CH3 A mixture of 0.5 g (0.00137 mole~ of 1-{4-chloro-2-fluoro-5-[1-~hydroxycarbonyl)ethoxy}phenyl}-4-difluoro-methyl-3-methyl-~2-1,2,4-triazolin-5-one, 1.76 g (0.00128 mole) of tert-butyl bromide, 1.15 g (0.00137 mole) of sodium hydrogen carbonate and 10 ml of dried dimethyl sulfoxide was reacted under stirring condition at a room temperature for 32 hours. ~fter the completion of the reaction, the xeaction product was treated by a method similar to that described in Example 8 to yield 0.4 g of the objectiv~ product. Refractive index nl8 0 1.5279. Yield 68.7%~

~ 3~

l The ~2-1,2,4-triazolin-5-one derivatives of the present invention are capable of controlling annual and perennial weeds grown in paddy fields, upland fields, orchards and swamps, for example barnyard grass (Echino-chloa crusgalli Beauv., an annual weed of Gramineae family grown in paddy fields and strongly injurious), monochoria (Monochoria vaginalis Presl, a strongly injurious annual weed of Pontederiaceae family grown in paddy fields), smallflower umbrellaplant (Cyperus difformis L., an inju-rious annual weed of Cyperaceae family grown in paddyfields), slender spikerush (Eleocharis acicularis Romer et Schultes, a typical injurious perennial weed of Cyperaceae family grown in paddy fields, and also grown in swamps and waterways), arrowhead (Sagittaria pygmaea Miq., an injurious perennial weed of Alismataceae family, grown in paddy fields, swamps and ditches), bulrush (Scirpus juncoides Roxb. var. Hotarui Ohwi, an annual weed of Cyperaceae family, grown~ in paddy fields, swamps and ditches), wild oats (Avena fatua L., an annual weed of Gramineae family, grown in plains, waste lands and upland fields~, mugwort (Artemisia princeps Pamp., a perennial weed of Compositae family, grown in cultivated and uncultivated fields), large crabgrass (Digltaraia adscendcus Henr., an annual wee of Gramineae family which is a typical strongly injurious weed grown in upland fields and orchards), Gi hi-gishi (Rumex ~aponicus Houttuyn, a perennial weed of Polygonaceae family, grown ; in upland fields and on roadsides), umbrella sedge :

.:- '' ' , :
;

... .
.
.. " . ,......

3~

1 (Cyperus iria L., an annual weed of Cyperaceae family, grown in upland fields and on roadsides), redroot pigweed ~Amaranthus varidis L., an annual weed of Amaranthaceae family grown in upland fields, vacant lands and roadsides), and cocklebur (Xanthium Strumarium L., an annual weed of Compositae family, strongly injurious to soybeans).
Since, ~2-1,2,4-triazolin-5-one derivatives represented by the general formula ~I) exhibit excellent controlling effects against weeds of both pre- and post-emergent stages, they are useful as herbicides for soiltreatment before and after seeding (planting), for soil treatment in the growth period, for foliar treatment before seeding (planting), for foliar treatment in the growth period of useful upland crops such as soybeans, cotton, corns and the like. Furthermore, these derivatives are useful as herbicides applying at the initial stage and the middle stage of rice grown in paddy fields, moreover, they are useful as herbicides to control general weeds grown in for example/ ridges between paddy ~ields, agricultural pathways, waterways, pasture, graveyards, parks, roads, playgrounds, unoccupied areas around build-ings, reclaimed lands, railways and forests. Herbicidal treatments of such areas are carried out most effectively and economically when weeds are not emergence but not necessarily be done prior to the emergence of weeds.
For applying the derivatives of the present invention as herbicides, they are generally formulated, according to conventional procedures for pxeparing - 24 ~

1 agricultural compositions, into a ~orm convenient to use.
That is, derivatives of the present invention are mixed with suitable insert carriers and, if necessary, further mixed with adjuvants, in a suitable ratio, and through dissolution, dispersion, suspension, mechanical mixing, impregnation, adsorption or adhesion, to make the mixture into a suitable form of composition, e.g., suspensions, emulsifiable concentrates, solutions, wettable powders, dusts, granules or tablets.
As to the carriers to be used in the agricultural compositions may be either solid carriers or liquid carriers. Examples of acceptable solid carriers may be cited vegetable powders such as soybean flour, cereal flour, wood flour, bark flour, saw dust, powdered tobaco stalks, powdered walnut shell, bran, powdered cellulose, and extraction residues of vegetables; fibrous materials such as paper, corrugated paperboard, and waste cloths;
synthe~ic polymers such a.s powdered synthetic resins~
inorganic or mineral products such as clays (e.g., kaolin, bentonite and acid clay), talc products ~e.g., talc and pyrophyllite~, silica products ~e.g., diatomaceous earth, silica sand, mica and white carbon ~a highly dispersed synthetic silicic acid, also called as finely pulverized hydrated silica or hydrated silicic acid, and some of commercially available products contain calcium silicate as the major component~], activated carbon, powdered sulfur~ p~ice, calcined dia~omaceous earth, yround brick, fly ash, sand, calcium carbonate, and calcium phosphates;

3i~
1 chemical fertilizers such as ~mmonium sulfate, ammonium phosphates, ammonium nitrate, urea, and ammonium chloride;
and farmyard manures. These solid carriers may be used alone or in combination with one another. As to the acceptable liquid carriers are selected from those which are solvents for the active ingredients and those which are non-solvent but can disperse the active ingredients with the aid of adjuvants. Examples of these liquid carriers may be used alone or in combination with one another, are water, alcohols (e.g., methanol, ethanol, isopropanol, butanol, and ethylene glycol), ketones te.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone), ethers (e.g., diethyl ether, dioxane, cellosolves, dipropyl ether, and tetrahydrofuran), aliphatic hydrocarbons (e.g., gasoline and mineral oils), aromatic hydrocarbons (e.g., benzene, toluene, xylene, solvent naphtha, and alkyl-naphthalene), halogenated hydrocarbones (e.g., dichloroethane, chlorinated henzenes, chloroform and carbon tetrachloride), esters (e.g., ethyl acetate, dibutyl phthalate, diisopropyl phthanate, and dioctyl phthalate), acid amides (e.g., dimethylformamide, diethylformamide, and dimethylacetamide), and nitriles (e.g., acetonitrile), and dimethyl sulfoxide.
As to the adjuvants, which are exemplified below, are used according to individual purposes. In some cases, they are used in combination ~.~ith one another.
In some other cases, no adjuvant is used at all.

'7~31~

1 For the purpose of emulsification, dispersion, solubilization and/or wetting of the active ingredients, there can be used surface active agents, for example polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene resinates, polyoxyethylene sorbitan monolaurate r polyoxyethylene sorbitan monooeate, alkyl-arylsulfonates, naphthalenesulfonic acid condensation products, ligninsulfonates, and higher alcohol sulfate esters. For the purpose of stabilizing the dispersion, tackification and/or agglomeration of the active ingredients, the following materials may be used, for example, casein, gelatin, starch, alginic acid, methyl-cellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, pine root oil, rice bran oil, bentoni-te and ligninsulfonates.
For the purpose of improving the flow property of the solid compositions, it is recommendable to use waxes, stearates, or alkyl phosphates.
As to peptizers for dispersi~ie compositions, it is also recommendable to use naphthalenesulfonic acid condensation products and condensed phosphates.
It is also possible to add anti-foaming agents such as for example, a silicone oil.
The content of the active ingredients in the herbicidal composition may be adjusted depend on the applications. ~or the preparation of powdered or granulated products, it is generally 0.5 to 20% by weight l of the active ingredients may be used, and for the preparation of emulsifiable concentrates or wettable powder products, it is generally 0.1 to 50% by weight of the active ingredients may be used.
For destroying various weeds, inhibiting their growth, or protecting useful plants from the injury caused by these weeds, the herbicidal composition of the present invention is used in a weed-destroying dosage or a weed growth inhibiting dosage as such or after properly diluted with or suspended in water or in other suitable medium, to the soil or the foliage of weeds in the area where the emergence or growth of weeds is undesirable.
The amount of the herbicidal composition of the present invention to be used depends on various factors such as, for example, the purpose of application, the objective weeds, the emergence or growth state of weeds and crops, the emergence tendency of weeds, weather, environmental conditions, the form of herbicidal composi-tion, the mode of application, the type of the field to be treated, and the time of application and others.
In applying the present herbicidal composition alone as a selective herbicide, it is suitable to select the dosage of l to 500 g per 10 ares. On the other hand, ill applying the present herbicidal composition in the combined use of herbicides, the optimum dosage thereof is often lower than that in the single use, the present herbicidal composition may be used in an amount lower than the above, when it is used in combination with 2~7~3~

1 another type of herbicide.
Herbicidal composition of the present invention is especially valuable for the pre-emergence treatment and initial emergence stage treatment of upland fields and for the early stage and middle stage control o~ weeds in paddy ~ields. In order to expand both range of controllable weed species and the period of time when effective applications are possible or to reduce the dosage, the herbicidal composition of the present inven-tion can be used in combination with other herbicides,and this usage is within the scope of the present invention.
For example, herbicidal compositio~ of the present invention can be used in combination with one or more of the following herbicides.
Phenoxy fatty acid type herbicides: ~or example, 2,4-D: e.g., ethyl (2,4-dichlorophenoxy)-acetate MCP: e.g., ethyl (2-methyl-~-chlorophenoxy)-acetate, sodium (2-methyl-4-chlorophenoxy~acetate, and allyl 2-(2~methyl-4-chlorophenoxy)acetate ~ IC~P: e.g., ethyl ~2-methyl-4-chlorophenoxy)-butyrate Diclofop-methyl: me~hyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propanoate Diphenyl ether type herbicides: ~or example, Nitrogen: 2,4-dichlorophenyl 4-nitrophenyl ether '7;3~3 1 Chlornitrofen: 2,4,6-trichlorophenyl 4-nitrophenyl ether Chlomethoxynil- 2,4-dichlorophenyl 3-methoxy-4-nitrophenyl ether Acifluorfen: 5-(2-chloro~ -trifluoro-p-tolyoxy)-2-nitrobenzoic acid and its salts Fluazifop-butyl: butyl (+)-2-[4-[~5-(trifluoromethyl)-2-pyridyl]oxy]phenoxy]propionate Triazine type herbicides: ~cr example, Simazine: 2-chloro-4,6-bi~(ethylamino)-s-trlazlne Prometryne: 2-methylthio-4,6-bis(iso-propylamino)-s-triazine Simetryne: 2-methylthio-4,6-bis(ethylamino)-s-triazine, and Metribuzino 4-amino-6-tert~butyl-3-methylthio-1,2,4-triazin-5~H)-one Carbamate type herbicides: for example, Molinate: s-ethyl hexahydro-l~-azepine-l-cabothioate Swep: methyl N-(3,4-dichlorophenyl3carbamate .Chloropropham: isopropyl N~(3-chlorophenyl)-carbamate and Benthiocarb: s-(4-chlorobenzyl)diethyl-triocarbamate Toluidine type herbicides: ~or exa~lple, Trifluraline: (~,u,~-tri~luoro-2,6-dinitro-N, N-dipropyl-p-toluidine and , ~

~2~7~¢;7 1 Pendimethali.ne: N~ ethylpropyl)-2,6-dinitro-3,4-xylidine Acid amide type herbicides. for example, Propanil: 3,4-dichloropropionanilide Butachlor: N-(Butoxymethyl)-2-Chloro-2,6-diethylacetanilide Alachlor: 2-chlor--2,6-diethyl-N~
(methoxymethyl)acetanilide Metolachlor: 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide and PretilachlorO 2-chloro-2,6-diethyl-N-~2-propoxyethyl)acetanilide Other types of herbicides: for example, Duron: 3-(3,4-dichlorophenyl)-1,1-dimethylurea Bentazon: 3-isopropyl-(H)-2,1,3-- benzothiazin-4-(3H) one 2,2-dioxide Pyraæolate: 4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5-yl-p~toluenesulfonate Pyrazoxyfen: 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-phenacyloxypyrazol and MY-71: 4-(2J4-dichloro-3~methylbenzoyl)-1,3-dimethylpyraæol-5-yl-p-toluenesulfonate The following examples illustrate the herbicidal effects, and the herbicidal compositions of the present invention. However, the present invention will not be restricted only to these examples~

1 Herbicidal test example - 1 Controlling effect on paddy field weeds of pre-emergence stage Pots (1/10,000 - are) were filed with soil to simulate a paddy field, and planted with seeds of barnyard grass, monochoria, umbrella plant, and bulrush, and with tubers of arrowhead, respectively, which are all injurious weeds grown in paddy fields, were conditioned so as to be in pre-emergence stage.
The soil in the pot was treated with each of the present compounds (listed in Table 1) formulated to given concentration of liquid, by spraying. After 21 days, the percent control of weed growth compared with that on the untreated plot was observed and the herbicidal activity was determined according to the criterion as shown in the following Table 2.

X~3~

Table 2 Criterion for determining herbicidal activity Degree of Percent control of herbicidal weed growth activity (%) 1 Less than 70 The test results were summarized in Table 3.

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1 Herbicidal test example - 2 Controlling effect on paddy field weeds of post-emergence stage Pots (1/10,000 - are~ were filled with soil to simulate a paddy field and grown with each of injurious -weeds of the followiny lead age. In addition, young seedings of rice plant (cultivar: "Nihonbarei') of the 2.5 lead age were transplanted to the soil on the day before the treatment with each of the present herbicides.
After 21 days, the herbicidal effect and the degree of crop injury were evaluated by comparing the results with those on the untreated plot.

Species of weed tested Leaf age of the weed Barnyard grass Monochoria 2 - 3 Umbrella plant 1 - 2 Bulrush 2 - 3 Arrowhead 3 Water nutgrass 1 - 2 The criterion for judging the degree of crop injury are as follows:
H: High ~including withering) M: Medium L: I.ow N: None The criterion for judging the herbicidal ~ 38 -'73~3 1 activity is in accordance with that used in herbicidal test example - 1. The results were summarized in Table 4.

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1 Herbicidal test example - 3 Controlling effect on upland field weeds of pre-emergence stage Polyethylene vats, having 10 x 20 x 5 cm (depth) size, were filled with soil and seeded with oats, barnyard grass, large crabgrass, redroot pigweed, mugwort, Gishi-gishi, umbrella sedge and cocklebur, respectively, and seeds were covered with soil.
The soil was treated with each of the present herbicides formulated to a given concentration of liquid, by spraying. After 21 days, the herb.icidal e~fect was evaluated by comparing the results with those on the untreated plot. The criterion for judging the herbicidal activity is the same as shown in test example - 1. The results were summarized in Table 5.

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1 Herbicidal test example - 4 Controlling effect on upland field weeds of post-emergence stage Polyethylene vats, having 10 x 20 x 5 cm (depth) size, were filled with soil and seeded with the weeds shown below and soybean seeds, respectively, and the seeds were covered with soil. The weeds and soybean were cultivated respect.ively to the following leaf ages and then treated with each of the present active compounds at a given dosage.
After 21 days, the herbicidal effect on the weeds and the degree of corp injury to the soybean were evaluated by comparing the results with those on the untreated plot.

Species of test plant Leaf age Oats 2 Large crabgrass 2 Redroot pigweed Mugwort Gishi-gishi 2 Umbrella sedge Cocklebur Soybean First tri~oliate age The criteria for judging the herbicidal activity and crop injury were in accordance with those used in herbicidal test examples -1 and -2, respectively.
The results were summarized in Table 5.

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1 Example of herbicidal composition - 1 A wettable powder composition was prepared by mixing uniformly and grinding the following ingredients:
Compound No. 3 50 Parts Mixture of clay with white 45 Parts carbon (in which clay is contained as the major component~
Polyoxyethylene nonylphenyl 5 Parts ether Example of herbicidal composition - 2 A granular composition was prepared by mixing uniformly and grinding the following ingredients, kneading the mixture with a suitable amount of water, and granulating the kneaded mixture:
- Compound No. 25 S Parts Mixture of bentonite90 Parts with clay Calcium ligninsulfonate 5 Parts 1 Example of herbicidal composition - 3 An emulsifiable concentrate was prepared by mixing uniformly the following ingredients:
Compound No. 50 50 Parts Xylene 40 Parts Mixture of polyoxyethylene 10 Parts nonylphenyl ether with calcium alkylbenzenesulfonate .~

Claims (13)

WHAT IS CLAIMED IS:

1. .DELTA.2-1,2,4-Triazolin-5-one derivatives represented by the general formula (I), (I) (wherein R is a hydrogen atom; an alkali metal atom; a quaternary ammonium salt; an unsubstituted-alkyl group having 1 to 6 carbon atoms; a substituted-alkyl group having halogen atoms as the substituents; an unsubstituted-cycloalkyl group; a substituted-cycloalkyl group having halogen atoms as the substituents; an alkenyl group; an alkynyl group; a lower alkoxyalkyl group; a lower alkylthioalkyl group; a lower alkylsulfinylalkyl group;
a lower alkylsulfonylalkyl group; a lower alkoxyalkoxyalkyl group; a lower alkoxycarbonylalkyl group; a hydroxycarbon ylalkyl group; an unsubstituted-benzyl group; a sub-stituted-benzyl group having 1 to 2 substituents selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, a lower alkoxycarbonyl group, a hydroxycarbonyl group and a phenoxy group; .alpha.-methylbenzyl group or a phenethyl group).

2. The .DELTA.2-1,2,4-triazolin-5-one derivatives according to Claim 1, wherein R is a hydrogen atom; an alkali metal atom; a quaternary ammonium salt; a substituted-alkyl group having halogen atoms as the substituents; an unsubstituted-cycloalkyl group; a substituted-cycloalkyl group having halogen atoms as the substituents; an alkenyl group; an alkynyl group; a lower alkoxyalkyl group; a lower alkylthioalkyl group; a lower alkylsulfinylalkyl group; a lower alkylsulfonylalkyl group; a lower alkoxyalkoxyalkyl group; a lower alkoxycarbonylalkyl group; a hydroxycarbonylalkyl group;
an unsubstituted-benzyl group; a substituted-benzyl group having 1 to 2 substituents selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, a lower alkoxycarbonyl group, a hydroxycarbonyl group and a phenoxy group;
.alpha.-methylbenzyl group or a phenethyl group.

3. A herbicidal composition containing .DELTA.2-1,2,4-triazolin-5-one derivatives as claimed in Claim 1 is contained as the active ingredient with suitable carriers.

4. The herbicidal composition according to Claim 3, wherein the active ingredient is .DELTA.2-1,2,A-triazolin-5-one derivative as claimed in Claim 2.

5. 1-{4-Chloro-2-fluoro-5-[1-(2-chloroethoxycarbonyl) ethoxy]phenyl}-4-difluoromethyl-3-methyl-.DELTA.2-1,2,4-triazolin-5-one.

6. 1-{4-Chloro-2-fluoro-5-[1-(2-bromoethoxycarbonyl) ethoxy]phenyl}-4-difluoromethyl-3-methyl-.DELTA.2-1,2,4-triazolin-5-one.

7. 1-{4-Chloro-2-fluoro-5-[1-(2,2,2-trifluoroethoxycarbonyl) ethoxy]phenyl}-4-difluoromethyl-3-methyl-.DELTA.2-1,2,4-triazolin-5-one.

8. 1-{4-Chloro-2-fluoro-5-[1-(3-chloropropoxycarbonyl) ethoxy]phenyl}-4-difluoromethyl-3-methyl-.DELTA.2-1,2,4-triazolin-5-one.

9. 1-{4-Chloro-2-fluoro-5-[1-(methoxyethoxycarbonyl) ethoxy]phenyl}-4-difluoromethyl-3-methyl-.DELTA.2-1,2,4-triazolin-5-one.

10. 1-{4-Chloro-2-fluoro-5 [1-(isopropoxyethoxycarbonyl) ethoxy]phenyl}-4-difluoromethyl-3-methyl-.DELTA.2-1,2,4-triazolin-5-one.

11. 1-{4-Chloro-2-fluoro-5-[1-(methoxyethoxyethoxycarbonyl) ethoxy]phenyl}-4-difluoromethyl-3-methyl-.DELTA.2-1,2,4-triazolin-5-one.

12. 1-{4-Chloro-2-fluoro-5-[1-(4-chlorobenzyloxycarbonyl) ethoxy]phenyl}-4-difluoromethyl-3-methyl-.DELTA.2-1,2,4-triazolin-5-one.

13. 1-{4-Chloro-2-fluoro-5-[1-(4-methylbenzyloxycarbonyl) ethoxy]phenyl}-4-difluoromethyl-3-methyl-.DELTA.2-1,2,4-triazolin-5-one.