HU195722B - Herbicide compositions containing delta-2-1,2,4-triazolin-5-one derivatives as active component and process for producing delta-2-1,2,4-triazolin-5-one derivatives - Google Patents

Abstract

DELTA <2>-1,2,4-Triazolin-5-one derivatives represented by the general formula, <IMAGE> (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 hydroxycarbonylalkyl group; and 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). The DELTA <2>,1 ,2,4-triazolin-5-one derivatives are useful as herbicides.

Description

The present invention relates to δ ² -1,2-4-triazolin-5-one derivatives. herbicidal compositions and the preparation of A ² -1,2,4-triazolin-5-one derivatives.

Formula ² ú -l forming compositions of the invention comprise (I), wherein 2-4-triazolin-5-one-permissible nature (I)

R is hydrogen; an alkali metal; C 1-6 alkyl optionally substituted with halo; C 3-6 cycloalkyl optionally monosubstituted with halogen; C3-C6 alkenyl; C 3-6 alkynyl, (C 1-4 alkoxy) (C 1-4 alkyl), (C 1-4 alkyl) thio (C 1-4 alkyl), (C 1-4 alkyl) ) -Sulphinyl (C1-C4) alkyl, (C1-C4) alkylsulfonyl (C1-C4) alkyl, (C1-C4) alkoxy (C1-C4) alkoxy) (C 1 -C 4) alkyl, or on the phenyl moiety one or two halogens or one

Benzyl optionally substituted with C 1-4 alkyl or C 1-4 alkoxy.

The N-triazolin-5 derivatives of formula I are new compounds and have not yet been described in the literature.

Sho-57-108079 (1982) and Sho-57-181069 (1982). The active herbicidal composition of Japanese Patent Publication (Kokai) similar in structure to formula I of the invention (I) is ² l, 2,4-triazolin-5-ones.

It has now been found that formulations containing the compounds of formula (I) according to the invention have potent herbicidal activity and are suitable for agricultural use.

It has also been found that formulations containing the compounds of formula (I) according to the invention exhibit particularly excellent herbicidal activity at relatively low doses and lower phytotoxicity than herbicidal active ingredients in the above-mentioned published descriptions.

The present invention relates to ² l, from 0.1 to 50% by weight of the herbicidal compositions comprising 2-4-triazolin-5-derivatives as an active ingredient.

The present invention also relates to a process for the preparation of a compound of formula I wherein:

R is hydrogen; C 1-6 alkyl optionally substituted with halogen; C 3-6 cycloalkyl optionally monosubstituted with halogen; C3-C6 alkenyl; C 3-6 alkynyl; (C1-C4) alkoxy (C1-C4) alkyl; (C 1 -C 4 alkyl) thio (C 1 -C 4 alkyl); (C 1 -C 4 alkyl) sulfinyl (C 1 -C 4 alkyl); (C1-C4 alkyl) sulfonyl (C1-C4 alkyl); (C 1 -C 4 alkoxy) - (C 1 -C 1 alkoxy) - (C 1 -C 4 alkoxy) - (C 1 -C 1 alkoxy) cat-carbonyl (C 1-4 alkyl) a) benzyl optionally substituted on the phenyl moiety with 1 or 2 halogen atoms or with 1 or 2 C 1 -C 4 alkoxy groups or a nitro group, (C 1 -C 4 alkoxycarbonyl group, phenoxy group or C 1 -C 4 alkyl group); -csrport or 'phenethyl group.

These compounds of formula (I) may be prepared by methods A, B, or C, as described below. Method A / is outlined in Scheme 1, Method B / in Scheme 2, and Method C / in Scheme 3. In Scheme 1, R is as defined above, Z ¹ is chloro, bromo or iodo. In Scheme 2, R is as defined above, Z ² is halogen. In Scheme 3, R is as defined above, X is halogen or hydroxy.

The formula ^z l, 2,4-triazole-5-one derivatives according to tilálmány (I) according to process a) (II) and a compound (III), b) a method according to (IV) A compound of formula (V) and a compound of formula (V), while process (c) may be prepared by reacting a syrup of formula (VI) and a compound of formula (VII) in an inert solvent in the presence or absence of a basic compound.

Suitable inert solvents for the above reactions are any inert solvent which does not adversely affect the reaction, such as aromatic hydrocarbons (benzene, toluene, xylene and the like), aliphatic hydrocarbons (n-hexane, cyclohexane and the like), alcohols (methanol, ethanol, propanol). , ethylene glycol and the like), ketones (methyl diethyl ketone, cyclohexanone and the like), lower aliphatic carboxylic acid esters (ethyl acetate or the like), ethers (tetr & hydrofuran, dioxane and the like), lower fatty acid amides (dimethylformamide) , dimethylacetamide and the like), water, dimethyl sulfoxide or the like can be mentioned by way of example. The above solvents may be used alone or in admixture with one another.

In process c), when an alcohol is used as a solvent, an alcohol of formula VI is preferably used.

In the above-mentioned reactions, inorganic basic compounds such as alkali metal hydrides (sodium hydride and the like), alkali metal hydroxides (sodium hydroxide, potassium hydroxide and the like), alkali metal carbonates are the basic agents.

G (sodium carbonate, potassium carbonate, and the like), alkali metal hydrogencarbonates (e.g., sodium bicarbonate, potassium hydrogen carbonate and the like), alkali metal alcoholates (sodium methylate and the like), or organic basic compounds, such as pyridine , trimethylamine, triethylamine, diethylaniline, 1,8-dlazabicyclo (5,4,0) -7-undecene.

The above reactions may be carried out at temperatures between 0 and 150 ° C.

The reactions are equimolar reactions and it is preferred that one of the reactants be used in a small excess relative to the other.

The reaction time may vary from 0.5 to 48 hours.

After the reaction is complete, the target product can be recovered by treating the reaction mixture in a known manner.

The compound of formula (II) which can be used as starting material in process (a) can be prepared according to Scheme 4. The figure R is as defined above, R ¹ and R ² is lower alkyl, A is oxygen or sulfur.

In Scheme 4, compounds of formula (II) may be prepared by reacting a compound of formula (VIII) with a compound of formula (IX) under heating in an inert solvent and subjecting the resulting compound of formula (X) to a ring closure reaction. using a basic compound. The ring closure reaction may also be carried out by recovering the compound of formula (X) from the reaction mixture, or it may be carried out without isolating the compound of formula (X).

The starting compound of formula (IV) used as starting material in process (b) is the

Scheme 5 may be prepared as described in Scheme 5. In Figure ^R1 is as defined above.

In the above reaction, hydrogen iodide or an alkyl thioate may be used instead of hydrogen bromide.

Table 1 lists some representative copies of the Δ ² -1,2,4-thiazolin-5-one derivatives of formula I and their physical constants.

Table 1

Number of compound R Physical property 1 H nD ²⁴ · ⁵ 1.5192 2 So- op .: 186.1 ° C 3 K op .: 119.2 ° C 8 CH3 from ^23rd 1.5142 9 C2H5- n ¹⁰ D 1.5112 10 BOW-C3H7- na ²³ · » 1.5051 11 iso-Cilh- at ²³ · ⁰ 1.5051 12 iv Céis- _no 29.O 1.5031 13 FZO-CtHa- _ni) 29.0 1.5011 14 Éerc-CíHs- nD ²⁶ · ⁰ 1.5009 15 n CsHxi- of ²⁷ · ⁵ 1.4984 16 FZO-CsHn- nD ²⁶ · ⁰ 1.5002 17 n C6Hn- nD ^28.5 1.4992 18 C1CH2CH2- nD ²⁶ · ⁵ 1.5204 19 BrCH2CH2- _not 19.5 1.5291 20 CI3CCH2- op .: 106.5 ° C 21 F3CCH2- _nD 19.5 1.4826 22 CICH2CH2CH2- op .: 87.7 ° C 23 BrCH2CH2CH2- op .: 83.8 ° C 24 CICH2CH- | op .: 68.7 ^a C CH3 25 C1CH2CHCH2- j op .: 95.0 ° C 1 cl 26 C1CI [2 _X CH-C1CH2 ^Z η ¹⁴ - ⁵ η 1.5091 27 BrCH2 _{x CH} - BrCHz op .: 104.2 ° C 28 FsC _x CH _n i9.5 _D 1.4573 FAC '' 29 CICH2CH2CH2CH2- op .: 95.3 ° C 30 cyclopentyl nu ² ® · ⁰ 1.5130

195

Table 1

Physical property

cyclohexyl- nu ²⁷ · ⁸ 1.5140 2-cyclohexyl n "n.5 1.5171 CHz CHCHz- of ²⁸ · ⁵ 1.5156 CH CCH2 _nD 28.5 1.5192 CH CC2CHz- _nI) 17.5 1.5209 CH ₃ O (CH 2) 2- _nt) 26.0 1.5088 C2H5 (CH2) 2 from ²⁶ · ⁰ 1.5022 JZO-C3H70 (CH2) 2 n _D 26.o 1.4989 n-C4Hs> O (CH2) 2 from ^26-0 1.4878 CH3OCHCH2CH2- I of ²⁷ · ⁸ 1.5009 I CH3 CH3SCH2- _nu 18.0 1.5279 CH ₃ S (CH 2) 2- _ni) 26.5 1.5306 C2HsS (CH) 2- _nD 19.5 1.5274 I-C3H7S (CH2) 2 from ^19.8 1.5233 JZO-C4H9S (CH2) 2 from ¹⁹ · ⁸ 1.5212 No. <? k-C4H9S (CH2) 2 _nD 19.5 1.5219 ier <CiH9S ^ (CH2) 2 _nD 22.5 1.5179 CH3 S (CH2) 3 _nD 19.5 1.5299 C ₂ H ₅ S (CH 2) 3- from ¹⁹ · ⁵ 1.5203 1zo-C3H7S (CH2) 3- from ¹⁹ · ⁸ 1.5204 n-C 4 H 9 S (CH 2) ₃ - m> " 1.5216 I-C4H9S (CH2) 3- _nD MS. 1.5209 te'c-C4H9S (CH2) ₃ - from ¹⁸ · ⁸ 1.5172 CHSs (CH2) 2 Ψ Melting point: 104.5 ° C 0 CH ₃ S (CH 2) 2- Ovadáspont: 99.8 ° C CH ₃ O (CH 2) 2 O (CH 2) 2 - _n 26.0 _D 1.5052 CH3OC-CHII 1 Melting point: 108.1 ° C II 1 0 ch ₃ benzyl- Melting point: 82.4 ° C 2-chlorobenzyl Melting point: 117.5 ° C 3-chlorobenzyl Melting point: 72.6 ° C 4-chlorobenzyl Melting point: 73.0 ° C 2-fluorobenzyl Melting point: 115.7 ° C 4-fluorobenzyl Melting point: 80.0 ° C 4-methylbenzyl Melting point: 102.8 ° C 4-methoxybenzyl Melting point: 89.4 ° C 4-nitrobenzyl Melting point: 126.5 ° C 4- (ethoxycarbonyl) benzyl Melting point: 135.3 ° C 3-phenoxybenzyl η ²⁶ ·% 1.5588 2,4-dichlorobenzyl Melting point: 163.0 ° C 2,6-dichlorobenzyl Melting point: 114.7 ° C 3.4-methoxybenzyl Melting point: 96.5 ° C 1-phenyl-et-l-yl- Oily substance phenylethyl Oily substance

The following table lists the NMR data for oily substances:

Table 2

Compound Number NMR (ppm)

1:15 (t, 9H), 1.64 (D, 3H) 2:41 (s, 3H), 2.19 (Q. 6H) 4:53 (q, 1H), 7.03 (T, IH) 7:04 (d, 1H), 7; 22 (D, IH) 1.32-1.77 l (m, 6H), 2.30 (S, 3H) 4.60 (q, 1H), 5.76 (Q. IH) 6.86 (t, 1H), 6.76-7.31 (M, 7H) 1:56 (d, 3H), 2.35 (S, 3H) 2.84 (t, 2H), 4.28 (T, 2 H) 4:59 6.85- (q, 1H), 6.91 -7.32 (m, 7H) (T, IH)

The invention is illustrated by the following examples, but the invention is not limited to the following examples.

Example 1 1- [4-Chloro-2-fluoro-5- (1-ethoxycarbonyl / ethoxy) -phenyl] -4- (difluoromethyl) -3-methyl-1 H-1,2-triazoline Preparation of ε-one (Compound 9)

13.27 g (0.045 mol) of the compound of the formula IV, 9.06 g (0.0498 mol) of ethyl olibromopropionate and 13.27 g (0.0962 mol) of potassium carbonate in 200 ml of acetone are added for 3 hours. over reflux. The reaction mixture was then cooled to room temperature and insoluble materials were removed by filtration. The filtrate was evaporated and the oily material was dissolved in diethyl ether and washed with cold water. The diethyl ether solution was dried and the solvent was evaporated to give an oily product. (The oily material was clear but further purified by silica gel dry column chromatography.) Yield: 14.7 g (83.1 µ) · η “· 1.5112.

Example 2 l- [4-chloro-2-fluoro-5- / l- (hydroxycarbonyl) ethoxy / phenyl] -4- (difluoromethyl) ^-3-methyl-2 -l 2, Preparation of 4-triazolin-5-one (Compound No. 1)

1.4 g (0.00356 mol) of 1- [4-chloro-2-fluoro-5- [1- (ethoxycarbonyl, ethoxyphenyl) -4- (difluoromethyl-S-methyl-z] N, N-Triazolin-5-one was dissolved in ethanol (50 ml), then potassium hydroxide (1.2 g) in water (20% w / v) was added to the solution, and the whole was stirred at room temperature for 3.5 hours. After completion of the reaction, the reaction mixture was poured into ice water, acidified with hydrochloric acid, and the desired product was extracted with ethyl acetate, washed with water, dried over anhydrous magnesium sulfate and the solvent evaporated to give 1.1 g of the title compound as an oil.

84% · γ «· ⁵ β = 1.5192.

Example 3

2- [2-Chloro-5- (4- (difluoromethyl) -3-methyl-5-oxo- ² -1,2,4-triazolin-1-yl) -4- (fluorophenoxy)] preparation of sodium propionate (Compound # 2)

0.5 g (0.00136 mol) of 1- [4-chloro-2-fluoro-5- [1- (hydroxycarbonyl) ethoxy] phenyl] -4- (difluoromethyl) -3-methyl N, N-Triazolin-8-one was dissolved in tetrahydrofuran (20 mL), treated with sodium hydride (0.05 g, 0.00125 mol) and the whole was stirred at room temperature for 10 minutes. After the reaction was complete, tetrahydrofuran was distilled off under reduced pressure and the resulting residue was washed with n-hexane. 0.37 g of the title product are obtained. Mp: 186.1 ° C. Yield: 76.4%.

i. example

Oibutil araraónium-2- [2-chloro-5- (4- / difluoromethyl / ^{-3-methyl-5-oxo-2} -l, 2,4-triazole: yn-l-yl) -4- (fluorophenoxy) propionate (Compound 7)

0.5 g (0.00136 mol) of 1- [4-chloro-2-fluoro-5- (1-hydroxycarbonyl-ethoxy) -phenyl] -4- (difluoromethyl) -3-A ² -1,2,4-Triazolin-5-one was dissolved in benzene (20 ml), added to dibutylamine (1.0 g, 0.0138 mole) and the reaction was carried out under ice-cooling. The crystals formed in the reaction mixture were removed by filtration and washed with benzene to give 0.51 g of the title compound. Yield: 79.4%. Mp: 126.5 ° C.

Γ>. EXAMPLE l- [l-chloro-2-fluoro-5-l- / propargyl oxi1 arbonil / -ethoxy) -phenyl] -4- (difluoromethyl thiomethyl) -3-methyl-4 ² -l, 2,4-triazole ! in-5-on (no. 34)

Preparation of Compound (II) in ml of thionyl chloride with stirring 2.7 g of 1- (4-chloro-2-fluoro-5- (1-hydroxycarbonyl-ethoxy) -phenyl) -4- (difluoromethyl) -S-methyl The ² -1,2,4-triazolin-5-one was dissolved and the solution was refluxed for 2 hours with stirring.

-511 was complete, the excess thionyl chloride was distilled off, giving 2.8 g of 1- [4-chloro-2-fluoro-5- [1- (chlorocarbonyl) ethoxy] phenyl] -4- (difluoromethyl) 0.5 g of this compound (0.0013 mol) was dissolved in 20 ml of tetrahydrofuran and 0.2 g (0.00357) of this compound were obtained. propargyl alcohol (0.2 mole) and triethylamine (0.2 g, 0.00198 mole) were added and the whole was allowed to react at room temperature for 2 hours.After completion of the reaction, the reaction mixture was poured into ice water and extracted with ethyl acetate. The acetate layer was extracted with 10% aqueous potassium carbonate solution, then water, dried over anhydrous magnesium sulfate and the solvent was distilled off to give 0.35 g of the title compound (66.6%). . n28- ⁵ D = l, 5,192th

Example 6 1- [5- [1- (tert-Butoxycarbonyl) ethoxy] -4-chloro-2-fluorophenyl] -4- (difluoromethyl) -3-methyl-N, 4'-triazoline-6-one. -on (Compound 14)

0.58 g (0.00151 mol) of 1- [4-chloro-2-fluoro-5- (1- (chlorocarbonyl) ethoxy] phenyl] -4- (difluoromethyl) -5-methyl-A N, N-Triazolin-5-one (0.25 g, 0.00338 mol) tert-butyl alcohol, 0.14 g (60% oil, 0.0035 mol) sodium hybrid and 20 ml tetrahydrofuran They were added the whole was heated under reflux for 6 hours After the reaction was completed, the reaction mixture was treated in a similar manner to that described in Example 5 to give 0.13 g of desired product Yield:..... 18.8% n ° i ^2? > = 1,5009.

Example 7 1- [4-Chloro-2-fluoro-5- (1 - ((1-methoxycarbonyl) ethoxycarbonyl) ethoxyphenyl] -4-difluoromethyl) -3-methyl Preparation of ² -1,2,4-triazolin-5-one (Compound 57)

0.5 g (0.00136 mol) of 1- [4-chloro-2-fluoro-5- (1-hydroxycarbonyl) ethoxy-phenyl] -4- (difluoromethyl) -3-methyl -A ² -1,2,4-triazolin-5-one,

0.28 g (0.00136 mol) of N, N'-dicyclohexylcarbodiimide, 0.02 g (0.000164 g) of 4- (dimethylamino) pyridine, 0.14 g (0.00136 mol) of α A solution of methyl hydroxypropionic acid and 10 ml of diethyl ether was stirred at room temperature for 6 hours. After the reaction was complete, the insoluble material was filtered off, the filtrate was evaporated and the residue was purified by dry column chromatography. 0.41 g of the title product is obtained. Mp .: 108.1 "C. Yield: 64.3%.

Example 8

1- [4-chloro-2-fluoro-5- / l- (ethoxycarbonyl) ethoxy / phenyl] -4- (difluoromethyl) -3-metilδ ² -1,2,4-tr iazolin-5 —Life (Compound # 9)

0.04 g (0.00134 mole) of sodium hydride was suspended in 10 ml of anhydrous Ν, Ν-dimethylformamide, and 0.4 g (0.00122 mole) of 1- [4-chloro-2] was added dropwise to this suspension. solution of -fluoro-5- [1- (ethoxycarbonyl) ethoxy] phenyl] -3-methyl-Δ ² -1,2,4-triazolin-5-one at room temperature. After the dropwise addition was complete, the whole mixture was stirred for 30 minutes and then at 130 ° C for 5 hours, gas was bubbled into monochlorodifluoromethane. After the reaction was complete, the reaction mixture was cooled to room temperature and poured into ice water. The resulting oily material was extracted with diethyl ether and the extract was dried over anhydrous magnesium sulfate. The solvent was evaporated to give an oily substance. This oily material was purified by dry column chromatography to give 0.15 g of the title compound. Yield: 32.6% ¹⁹ = 1.5121.

Example 9 1- [1-Chloro-2-fluoro-5- [1- (methylthiomethoxycarbonyl) ethoxy] phenyl] -4- (difluoromethyl) 3-irethyl-A ² -1,2 , 4-Triazolin-5-one (Compound 41)

0.5 g (0.00137 mol) of 1- [4-chloro-2-fluoro-5- [1- (hydroxycarbonyl) ethoxy] phenyl] -4- (difluoromethyl) -3-inethyl - ² -1,2,4-triazolin-5-one,

1.76 g (0.00128 mole) of t-butyl bromide, 1.15 g (0.00137 mole) of sodium bicarbonate and 10 ml of anhydrous dimethylsulfoxide were mixed and allowed to stand at room temperature with constant stirring for 32 hours. . After the reaction was complete, the reaction product was treated as in Example 8. 0.4 g of the expected product is obtained.η ¹⁸ · ο = 1.5279; yield 68.7%.

Example 10 1- [1-Chloro-2-fluoro-5- [1- (n-butoxycarbonyl-ethoxy) -phenyl] -4- (difluoromethyl) -3-methyl-δ ² -1, Preparation of 2,4-Triazolin-5-one (Chemical No. 12) (Scheme 6)

13.27 g (0.045 mol) of the compound of formula IV, 9.0 g (0.0498 mol) of n-butyl α-bromopropionic acid and 13.27 g (0.0962 mol) of potassium carbonate 200 of acetone (reflux) with stirring for 3 hours, cool to room temperature and insoluble matter

-613 filtered. The filtrate was evaporated and the resulting oil was dissolved in diethyl ether. The resulting solution was washed with cold water, dried and the solvent was evaporated. The purity of the resulting oily material is satisfactory for practical purposes, however, it is subjected to dry column chromatography on silica gel. Yield: 80%. n ^Z9 B = 1.5031.

Example 11

1- [4-Chloro-2-fluoro-5- [1 - [(3-chloropropoxy) carbonyl) ethoxy] phenyl] -4- (difluoromethyl) -S-methyl-α 1 -N- Preparation of Triazolin-S-one (Compound 22) (Scheme 7)

To a suspension of 0.52 g (0.0037 mol) of potassium carbonate in 50 ml of anhydrous Ν, Ν-dimethylformamide is added 1.0 g (0.0034 mol) of IV and the resulting mixture is stirred at room temperature for 30 minutes. 0.85 g (0.0034 mol) of α-bromopropionic acid 3-chloropropyl ester are added. The resulting reaction mixture was heated at 50 ° C for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and poured into ice water. The resulting aqueous mixture was extracted with diethyl ether, and the extract was washed, dried and evaporated. The product is finally recrystallized from a mixture of diethyl ether and n-hexane. This gave 1.1 g of the title compound. Mp = 87.7 ° C.

Example 12 l- [4-chloro-2-fluoro-5- / l- (methoxycarbonyl) ethoxy / phenyl] -4- (difluoromethyl) ^-3-methyl-2 -l, 2,4 Preparation of -triazolin-5-one (Compound 8) (Scheme 8)

To a suspension of sodium hydroxide (0.2 g, 0.0051 mol) in methanol (30 ml) was added compound (IV) (1.5 g, 0.005 mol), and the resulting mixture was stirred for 30 minutes and 0.85 g (0.0051 mol) was added. mole) of methyl α-bromopropionic acid is added. The reaction mixture was refluxed for 3 hours, after which the reaction mixture was cooled to room temperature and poured into ice water. The aqueous mixture was extracted with diethyl ether and the extract was dried and evaporated. The residue was purified by dry column chromatography. 1.2 g of product are obtained. Yield: 62.2% of ^{z3 0} = 1. 5142.

Example 13 1- (4-Chloro-2-fluoro-5- [1- (2-methylthio) ethoxycarbonyl) ethoxy] phenyl] -4-difluoromethyl-5-methyl-α 1 H - Triazolin-8-one (42.

s. (Scheme 9)

To a suspension of sodium hydride (0.15 g, 0.0037 mol) in tetrahydrofuran (30 ml) was added 1.0 g of compound (IV), and the resulting mixture was stirred for 30 minutes and 0.84 g (0.0037 mol) was added x bromo-propionic acid (2-methylthio) ethyl ester.

The resulting reaction mixture was refluxed for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and worked up as described in Example 12. 0.8 g of product is obtained. Yield: 53.7% -n ^26-5 d = 5306th

Example 14 1- [4-Chloro-2-fluoro-5- / 1 - ((3-l: chloroporopropoxy) carbonyl) -ethoxy] -phenyl] -4- (difluoromethyl) -S- Preparation of methyl N, N-, N-triazolin-5-one (Compound 22) (Scheme 10)

To a solution of the compound (IV) (1.5 g, 0.0051 mol) in anhydrous dimethyl sulfoxide (40 mL) was added 0.3 g of potassium hydroxide in powder form. The resulting mixture was stirred for 30 minutes at room temperature and then 1.0 g (0.0053 mol) of 3-chloropropyl ester of ecchloropropionic acid was added. The resulting reaction mixture was heated at 80 ° C for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and worked up as described in Example 11. 0.9 g of product is obtained. Yield: 40.0%. Mp 87.7 ° C.

Example 15 l- [(N-4-chloro-benzyloxy) -4-chloro-2-fluoro-5- / l -ethoxy / phenyl] -4- (difluoromethyl) ^-3-methyl-Z - Preparation of 1,2,4-triazolin-5-one (Compound 61) (Scheme 11)

1.5 g (0.0051 mol) of the compound of formula IV, 9.06 g (0.0498 mol) of α-bromopropionic acid 4-chlorobenzyl ester and 1.27 g (0.0056 mol) Potassium carbonate (50 mL) in diethyl ethyl ketone (50 mL) was heated at reflux for 5 hours with stirring, then cooled to room temperature and the insoluble material was filtered off. The filtrate was evaporated and the residue was purified by dry column chromatography. 1.6 g of product are obtained. Yield: 66.7%. Mp = 73.0 ° C.

-715

1G

Example 16 1- [4-Chloro-2-fluoro-5- [1- (2- (2-methoxyethoxy) ethoxycarbonyl) ethoxy] phenyl] -4- (difluoromethyl) -3 Preparation of -methyl- ² -1,2,4-triazolin-5-one (Compound 56) (Scheme 12)

2.93 g (0.01 mol) of compound of formula IV, 9.06 g (0.0498 mol) of 2-chloropropionic acid 2- (2-methoxyethoxy) ethyl ester and 1.66 g A suspension of potassium carbonate in 50 mL of acetonitrile was heated at reflux for 8 hours at 70 ° C with stirring, then cooled to room temperature and the insoluble material was filtered off. The filtrate was evaporated and ethyl acetate was added. The ethyl acetate layer was washed with water, dried and evaporated. The resulting oily material was purified by dry column chromatography. 4.2 g of product are obtained. Yield: 89%. η ^2β · ° Β = 1.5052.

The N, N-triazolin-8-one derivatives which are active ingredients of the compositions of the present invention are useful for controlling annual and perennial weeds in cotton, rice, orchards and marshes. Examples of herbicides we can control are Cockroach (Echinochloa crus-galli Beauv., A very dangerous weed on the rice field, belonging to the Gramineae family), Monochoria (Monochoria vaginalis Presl, Aching on the rice field, Pontederea). canopy (Cyperus difformis L., an annual weed of the Cyperaceae family in the rice fields), slender spear (Eleocharis acicularis Römer et Schultes, a typical perennial weed of the Cyperaceae family in the rice fields) pygmaea iq., a characteristic, perennial weed of the Alismataceae family of rice fields, marshes and ditches, Scots (Scirpus juncoides Roxb. var. Hotarui Ohwi, annual weeds of the Cyperaceae family) princeps Pamp., his works and inactive f perennial weeds of the Compositae family (Digitaraia adscendcus Henr., a typical, very dangerous, Gramineae weed of cotton lands and orchards); perennial weeds), perennial weeds (Cyperus iria L., perennial weeds of the Cyperaceae family growing on cotton fields and highways), porcupine (Amaranthus varidis L, perennial weeds growing on cotton fields, abandoned lands and highways), Amaranth and weevil (a very dangerous weed of the soybean of the Compositae family).

Because the δ ² -1,2,4-triazolin-5-one derivatives of formula I are excellent for controlling weeds, either pre- or post-emergence, they can be used as herbicides before or after sowing to treat soil, during the growing season, to treat the soil, to spray before sowing or to spray, for example, soybeans, cotton, maize and similar crops during the growing season of the crop.

In addition, these derivatives are suitable for weed control in the early and middle stages of rice growing on paddy fields, and can also be used for general weed control in, for example, rice field furrows, farm roads, gully, pastures, tombs, parks, roads, playgrounds, farmland in cultivated areas, between rails and in forests. The most effective treatment is when the weeds have not yet emerged, but it is not necessary to apply the compounds before the weeds emerge.

The formulations of the present invention are prepared in conventional manner and advantageous forms are prepared.

The active compounds of the invention are admixed with suitable inert carriers and, if desired, adjuvants in a suitable weight ratio, and after reconstitution, dispersion, suspension, mechanical mixing, impregnation, adsorption or adhesion, suitable formulations such as suspensions, emulsifiable concentrates, solutions, wettable powders, or tablets.

Solid carriers or liquid carriers may be used as carriers in agricultural compositions. Examples of suitable solid carriers are powders of plant origin, such as soybean flour, cereal flour, wood flour, sawdust, bark flour, powdered tobacco stalks, powdered hazelnuts, bran, powdered cellulose, extracts of plants; fibrous materials such as paper, corrugated paper waste materials; synthetic polymers such as powdered synthetic resins; inorganic or mineral products such as clays (e.g. kaolin, bentonite and acid clays), talc (e.g. talc and pyrophyllite), silicon-containing materials (e.g. diatomaceous earth, sand, mica and white carbon (highly dispersed silica, finely powdered) also known as dioxide or hydrated silica and some other commercial products containing calcium silicate as the main component), activated carbon, powdered sulfur, foam, calcined diatone earth, ground bricks, ash, sand,

-817 calcium carbonate and calcium phosphates; artificial fertilizers such as ammonium sulfate, ammonium phosphates, ammonium nitrate, urea and ammonium chloride; and stable manure. The above solid supports may be used alone or in combination with other carriers.

Suitable liquid carriers are, for example, those which are soluble in the active ingredient or which do not dissolve it, but which are capable of dispersing the active ingredients in the presence of excipients. Liquid carriers may also be used alone or in combination. Examples of liquid carriers are alcohols (e.g., methanol, ethanol, isopropanol, butanol and ethylene glycol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone), ethers (e.g., diethyl ether). , dioxane, cellosolve, dipropyl ether and tetrahydrofuran), aliphatic hydrocarbons (e.g. gasoline and mineral oils), aromatic hydrocarbons (e.g. benzene, toluene, xylene, naphtha solvent and alkylnaphthalene), halogenated hydrocarbons (e.g. dichloroethane, chloro), such as chloroform and carbon tetrachloride), esters (e.g. ethyl acetate, dibutyl phthalate, diisopropyl phthalate and dioctyl phthalate), acid amides (e.g. dimethylformamide, diethylformamide, dimethylacetamide) and nitriles (e.g. acetonitrile). ) and dimethylsulfoxide.

The excipients listed below can be used for a variety of purposes. In some cases they are used in combination with each other, while in other cases no excipients are used at all.

Surfactants such as polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene high carbon fatty acid esters for emulsifying, dispersing, solubilizing and / or wetting the active ingredient. , polyoxyethylene resinates resins, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkylarylsulfonates, naphthalenesulfonic acid condensation products, lignin sulfonates and higher carbon atoms alcohol sulfate esters may be used.

For example, casein, gelatin, starch, alginic acid, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, pine oil, bentonite and lignin sulfonates may be used to stabilize the dispersion or agglomerate the active ingredient.

It is recommended to use resins, stearates or alkyl phosphates to improve the flow properties of the solid compositions.

It is recommended to use condensation products of naphthalenesulfonic acids and condensed phosphates as dispersants in dispersible compositions.

Antifoam agents such as silicone oil may also be added to the compositions.

The amount of active ingredient present in the formulations will depend on the route of administration. In the case of powdered or granulated products, it is generally possible to use from 0.5 to 20% by weight of the active ingredient, whereas for emulsifiable concentrates or wettable powders, the active ingredient content is usually from 0.1 to 50% by weight.

For controlling various weeds, preventing their growth or protecting the crop from weeds, the herbicidal composition according to the invention is applied in an amount which suppresses the weed or inhibits its growth. The composition may be applied alone, but dissolved or suspended in a suitable solvent, to the soil or foliage of the weeds on land where the emergence or growth of the weeds is undesirable.

The amount of the herbicidal composition according to the invention will depend on various factors such as the purpose of application, the species of weed to be controlled, the emergence or maturity of the crop and weeds, the tendency of the weeds to hatch, the weather conditions, the the type of area to be treated, the time of treatment, etc.

When used as a selective herbicide, the herbicidal composition of the present invention per se is generally applied at a dose of 10-5000 g / ha. When used in combination with other herbicides, the optimum dosage is often lower than when used alone.

The herbicidal compositions of the present invention are particularly suitable for treatment of pre-emergence or initial emergence of highland weeds or in the early or mid-growth stage of rice field weeds. The herbicidal compositions of the present invention may be used in combination with other herbicides to increase the amount of weeds to be controlled, to extend the treatment period or to reduce the dose.

For example, the herbicidal compositions of the invention may be used in combination with one or the other of the following herbicides.

Phenoxy-S2 acid-type herbicides, for example

2,4-D: Ethyl (2,4, dichlorophenoxyl acetate)

MCP: Ethyl (2-methyl-4-chlorophenoxy) acetate, (2-methyl-4- (chlorophenoxy) -acetic acid, sodium salt and allyl-2- (2-nylyl-4- / chlorocefadroxil phenoxy / l acetate

MCBP: c t. N-2-methyl-4 - (chlorophenoxy) - butyrate

-919 dichlof op-methyl: methyl 2- [4- (2,4-dichlorophenoxy) phenoxy] propinate

Diphenyl ether herbicides such as NIP: (2,4-dichlorophenyl) - (4-nitrophenyl) ether chloronitrophen: (2,4,6-trichlorophenyl) - (4-nitro) o-Phenyl ether Clomethoxynil: (2,4-dichlorophenyl) - (3-methoxy-4-nitrophenyl) ether acifluorfen: 5- (-chloro-α, K, x-trifluoro- p- tolyloxy) -2-nitrobenzoic acid and its salts fluazifop-butyl: butyl (±) -2- {4 - [(5- (trifluoromethyl / -2-pyridyl) oxy] phenoxy} propinate

Triazine herbicides such as simazine: -2-chloro-4,6-bis (ethylamino) -striazine promethrin: 2- (methylthio) -4,6-bis (isopropylamino) -triazine trin: 2- (methylthio) -4,6-bis (ethylamino) -s-triazine metribuzin:

4-amino-6-t-butyl-3- (methylthio) -l, 2,4-triazin-5 (H) -one

Carbamate-type herbicides such as molinate: B-ethylhexahydro-1H-azepine-1-carbothionate swep: methyl-N- (3,4- (dichlorophenyl) -carbamate chlorpropham: isopropyl-N- (3-chloro) -phenyl) -carbamate bentiocarb: s- (4-chlorobenzyl) -diethylthiocarbamate

Toluidine-type herbicides such as trifluralin: (i, N, K-trifluoro-2,6-dinitro-N,

N-Dipropyl-p-toluidine Penimethyl: N- (1-ethyl-propyl) -2,6-dinitro-3,4-xylidine

Saeamide-type herbicides such as p-propanil: 3,4-dichloropropionanilide butachlor: N- (butoxymethyl) -2-chloro-2,6-diethylacetanilide alachlor: 2-chloro-2,6-diethyl-N - (methoxymethyl) acetanilide metolachlor: 2-chloro-N- (2-ethyl-6-methylphenyl) -N- (2-methoxy-1-methylethyl) acetamide antilachlor: 2-chloro-2 , 6-diethyl-N- (2-propoxyethyl) acetanilide

Other types of herbicides, such as diuron: 3- (3,4-dichlorophenyl) -1,1-dimethylurea beutazole: 3-isopropyl- (H) -2,1,3-benzothiaziti-4- (. III) -cn-2,2-dioxide pyrazolate: 4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-8-yl p-toluenesulfonate pyrazoxifene: 1,3-dimethyl-4- ( 2,4-dichlorobenzoyl) -5- (phenacyloxy) pyrazole and

M1 -71: 4- (2,4-Dichloro-3-ethyl-benzoyl) -1,3-di-ethyl-pyrazol-5-yl-p-toluenesulfonate.

The herbicidal activity of the compositions of the present invention is illustrated by the following examples, which are not intended to limit the invention.

Experimental Example 1

Pre-emergence weed control of Rirsland

To imitate the rice soil, pots (0.01 m) were filled with earth, and then planted with cocksfoot, monochoria, umbrella, sedge and arrowroot gurus. Most of the above plants are very dangerous weeds grown in rice fields. Seeds or seeds. the pots were kept under conditions to allow the seeds to enter the pre-emergent stage.

The soil in the pot was sprayed with the appropriate dilution of the emulsifiable concentrates prepared from the active compounds listed in Table 1 and formulated as described in Formulation Example 4.

days later, herbicidal activity was calculated from the percentage of herbicidal activity compared to untreated control, and

Table 2: Evaluated as indicated.

2. ^ elsa Liza

Criteria for the magnitude of the herbic id effect

The herbicidal effect The weed is'% Ground disinfestation s 1 100 90-99 3 80-89 2 70-79 1 less than. 70

The exams! results in Table 3: za.

-1 021

Λ chem. number The amount of active substance is g / 100 m ² Table 3 effect Kakasláb- grass The pre-en Mono Chorin : rgensing treatment Eagle Grass arrow 1 30 5 5 5 5 5 3 5 5 5 5 5 9 30 5 5 5 5 5 3 5 5 5 5 5 8 30 5 5 5 5 5 3 5 5 5 5 5 9 30 5 5 5 5 5 3 5 5 5 5 5 11 30 5 5 5 5 5 3 5 5 5 5 5 13 30 5 5 5 5 5 3 5 5 5 5 5 17 30 5 5 5 5 5 3 5 5 5 5 5 18 30 5 5 5 5 5 3 5 5 5 5 5 19 30 5 5 5 5 5 3 5 5 5 5 5 21 30 5 5 5 5 5 3 5 5 5 5 5 22 30 5 5 5 5 5 3 5 5 5 5 5 26 30 5 5 5 5 5 3 5 5 5 5 5 31 30 5 5 5 5 5 3 5 5 5 5 5 32 30 5 5 5 5 5 3 5 5 5 5 5 33 30 5 5 5 5 5 3 5 5 5 5 5 34 30 5 5 5 5 5 3 5 5 5 5 5 35 30 5 5 5 5 5 3 5 5 5 5 5 36 30 5 5 5 5 5 3 5 5 5 5 5 38 30 5 5 5 5 5 3 5 5 5 5 5 42 30 5 5 5 5 5 3 5 5 5 5 5 45 30 5 5 5 5 5 3 5 5 5 5 5 48 30 5 5 5 5 5 3 5 5 5 5 5 49 30 5 5 5 5 5 3 5 5 r _t 5 5 53 30 5 5 5 5 5 3 5 5 5 5 5 54 30 5 5 5 5 5 3 5 5 5 5 5 55 30 5 5 5 5 5 3 5 5 5 5 5 56 30 5 5 5 5 5 3 5 5 □ 5 5 58 30 5 5 5 5 5 3 5 5 5 5 5 61 30 5 5 5 5 5 3 5 5 0 δ 5

-1 123

1

Table 3

The chemical. number The amount of active substance is g / 100 m ² Kakasláb- grass Effect of pre-emergent treatment Mono- Chorin Umbrella- Sed plant Grass arrow 64 30 5 5 5 5 5 3 5 5 5 5 5 65 30 5 5 5 5 5 3 5 5 5 5 5 69 30 5 5 5 5 5 Reference compound 3 5 5 5 5 5 THE 3 3 4 4 3 3 B 3 3 4 4 3 3 The reference Compound No. 1 Compound L = - (2,4-Dichloro-5-isopropoxyphenyl) -4- (difluoromethyl) · -3-methyl- -? - 1 -? -? - triazolin-8-one (az 57.108079. s. Japanese KOKAI Mon? -in compound) Reference B Compound 7: . s. Compound A = 2,4-dichloro-l- {f • - [(N-l) ethoxy] phenyl} -4- (di- fluoromethyl) -3 · -methyl-Δ ² -!, 2,4- triazolin-5-one (57-181,089. £ z. KOKAI Compound)

Experimental Example 2

Post-emergence eradication of weeds in rice fields

Pots (0.01 m ² ) were filled with earth to simulate rice field conditions, and the following harmful weeds were grown there to the degree of development shown below. In addition, 2.5 leaf Nihonbare rice seedlings were planted in pots the day before spraying as described in Experimental Example 1. After 21 days, herbicidal activity and crop damage were evaluated by comparing with plants in control pots.

The weeds tested

barnyardgrass

Monochoria

Plant shade

Eagle

Grass arrow

Water Walnut

Maturity of weeds (number of leaves)

2-3

1-2

2-3

1-2

The crop damage was evaluated as follows:

H = inert (including atrophy)

M = medium L = low N = nin: s damage

The herbicidal activity was evaluated according to Table 2. The results of the tests are shown in Table 4.

Table 4

Compound number The amount of active ingredient is 100 m ² Effect of post-emergent treatment Plant- damage Kakasláb- grass Mono- Chorin Ernyősnö- receipt Eagle Grass arrow Aquatic diófü Rice 1 30 5 5 5 5 5 5 L ' 3 5 5 5 5 • 1 5 L 2 30 5 5 5 5 r 5 L 3 5 5 5 5 r ₍ 4 L 8 30 5 5 5 5 5 L 3 4 5 5 5 0 4 L 9 30 5 5 5 5 5 5 L 3 4 5 5 5 5 5 L 11 30 5 5 5 5 5 5 L 3 4 5 5 5 δ 4 L

25 195 722 26 Table 4 Compound The active- The post-emergent treatment effect Plant- number material damage g / 100m ² Kakasláb- Mono- Ernyösnö- Eagle Grass arrow Aquatic Rice grass Chorin receipt nut grass 13 30 5 5 5 5 5 5 L 5 5 5 5 5 5 5 L 17 30 5 5 5 5 5 5 L 3 5 5 5 5 4 4 t 18 30 5 5 5 5 5 5 L 3 5 5 5 5 4 5 L 19 30 5 5 5 5 5 5 L 3 5 5 5 5 5 5 L 21 30 5 5 5 5 5 5 L 3 5 5 5 5 5 5 L 22 30 5 5 5 5 5 5 L 3 5 5 5 5 5 5 L 26 30 5 5 5 5 5 5 L 3 4 5 5 5 5 5 L 31 30 5 5 5 5 5 5 L 3 5 5 5 5 4 5 L 32 30 5 5 5 5 5 5 L 3 5 5 5 5 5 5 L 33 30 5 5 5 5 5 5 L 3 5 5 5 5 4 4 L 34 30 5 5 5 5 5 5 L 3 5 5 5 5 4 4 L 35 30 5 5 5 5 5 5 L 3 5 5 5 5 5 5 L 36 30 5 5 5 5 5 5 L 3 5 5 5 5 4 4 L 38 30 5 5 5 5 5 5 L 3 5 5 5 5 4 4 L 42 30 5 5 5 5 5 5 L 3 5 5 5 5 5 5 L 45 30 5 5 5 5 5 5 I 3 5 5 5 5 5 5 L 48 30 5 5 5 5 0 5 L 3 5 5 5 4 5 5 L 49 30 5 5 5 5 She 5 L 3 5 5 5 4 4 4 L 53 30 5 5 5 5 5 5 L 3 5 5 5 5 4 5 L 54 30 5 5 5 5 Γ, 5 L 3 5 5 5 4 4 4 L 55 30 5 5 5 5 5 5 L 3 5 5 5 4 4 5 L 56 30 5 5 5 5 5 5 L 3 5 5 5 5 4 4 L 58 30 5 5 5 5 5 5 L 3 5 5 5 5 5 5 L 61 30 5 5 5 5 5 5 L 3 5 5 5 5 5 5 L 64 30 5 5 5 5, 5 5 h 3 5 5 5 5 5 4 L 65 30 5 5 5 5 5 5 L 3 5 5 5 5 ϋ 5 L 69 30 5 5 5 5 5 5 L 3 5 5 5 4 4 4 L

Reference-

compound THE 3 2 4 4 2 3 2 L B 3 2 4 4 2 3 2 L

Reference compounds are as given in Table 3.

-13195722

Experimental Example 3

Pre-emergence weed control of native weeds

10 x 20 x 5 cm polyethylene pots were filled with two of your heads and seeded with oats, cocksfoot, big toad, pork shoots, black wormwood, gishi-gishi, parasol and wormwood.

The main was sprayed as described in Experimental Example 1. After 21 days, the herbicidal activity was determined relative to the untreated control. The herbicidal activity was determined according to Experimental Example 1. The results are shown in Table 5.

Table 5

Compound The active- The fish of pre-emergent treatment The amount oat Rooster- Ujjas- Pig- Black Gi.shi- Ernyős- Serbian- g / 100m ² foot grass mallow the grass on ürör.i -gislii plant thorn 1 30 5 5 5 5 5 5 δ 3 3 4 4 5 5 5 5 5 5 2 30 5 5 5 5 5 5 5 5 3 4 4 5 5 5 δ 5 5 8 30 5 5 5 5 5 δ 5 5 3 4 4 5 5 5 5 δ 5 9 30 5 δ 5 5 5 5 5 δ 3 4 4 5 δ δ 5 5 Γ 11 30 5 5 5 5 5 δ 5 5 3 4 4 5 5 5 5 5 5 13 30 5 5 5 5 5 δ 5 5 3 4 4 5 5 5 5 5 5 17 30 5 5 5 5 5 5 5 5 3 4 4 5 5 5 5 5 δ 18 30 5 5 5 5 5 5 5 5 3 4 5 5 5 5 5 5 5 19 30 5 5 5 5 5 5 5 δ 3 4 5 5 5 δ 3 5 5 21 30 5 5 δ 5 5 5 5 5 3 4 5 5 5 5 5 5 5 22 30 5 5 5 5 5 5 5 5 3 4 5 5 5 .5 5 5 5 20 30 5 5 5 5 δ □ 5 5 3 4 5 5 5 5 5 5 5 31 30 5 5 5 5 5 5 δ δ 3 4 4 5 5 5 5 5 5 32 30 5 5 5 5 5 5 5 5 3 4 5 5 3 5 5 5 5 33 30 5 5 5 5 5 5 5 δ 3 4 5 5 5 δ 5 5 5 34 30 5 5 5 5 5 δ 5 3 3 4 5 5 5 5 5 5 5 35 30 5 5 5 5 5 5 5 δ 3 5 5 5 5 δ 5 δ 3 30 30 5 5 5 5 5 0 5 Γ 3 4 5 5 5 3 5 5 5 38 30 5 5 5 5 5 5 δ 3 3 4 5 5 5 3 5 5 5. -12 30 5 5 5 5 5 3 5 5 3 4 5 5 5 5 δ 5 3 45 30 5 δ 5 5 5 5 5 3 3 4 5 5 5 5 5 5 • 5 18 30 5 5 δ δ 5 5 δ 3 3 3 4 5 5 5 5 5 5 49 30 5 5 5 5 5 5 5 5 3 4 5 5 5 5 5 5 δ 53 30 5 5 5 5 5 5 5 Γ, 3 4 1 5 5 5 5 5 5

-1 423

Table 5

Compound number The active- Effect of pre-emergent treatment The amount of cxiiljcxe is g / 100m ² oat Rooster- foot grass I was swimming Pig- the grass on Black wormwood Gishi- -gishi Ernyós- plant Serbian- thorn 54 30 5 5 5 5 b 5 b 3 4 5 5 5 5 5 5 b bb 30 5 5 5 5 5 5 b b 3 3 4 5 5 5 5 5 5 bG 30 5 5 5 5 b 5 b b 3 3 4 5 5 5 r 5 5 58 30 5 5 5 b 5 5 b 5 3 5 5 5 5 5 5 5 b 61 30 5 5 5 5 5 5 f) 5 3 4 5 5 5 5 5 5 5 64 30 5 5 5 5 5 5 5 5 3 4 5 5 5 5 5 5 5 65 30 5 5 5 5 5 5 5 5 3 4 4 5 5 5 5 5 5 69 30 5 5 5 5 5 5 5 5 3 4 5th 5 5 5 5 5 5

Reference-

compound THE 3 2 3 3 5 4 3 4 1 B 3 1 2 3 5 4 3 4 2

Experimental Example 4

Post-emergence weed control of native weeds

Polyethylene pots (10x20x5 cm) were filled with earth, then the weeds and soybeans listed below were seeded and the seeds covered with earth. Weeds and soybeans were grown to the following stage of development and sprayed as described in Experimental Example 1.

day after day, weed effects on weeds and crop damage were determined by comparison with untreated controls.

Experimental weeds

Degree of development (how many leaf states)

oat

Big toad

pigweed

Black wormwood

GISH Gishi

Umbrella sedge

cocklebur

Soy-bean

First triple leaf condition

Herbicidal activity and crop damage were evaluated similarly to Experimental Examples 1 and 2. The results are

Table 5 contains.

Table 6

Compound A - Effect of Post-emergent Treatment Number of Plants Material Damage Quantity --- (g / 100m ² ) Oat Rooster - Pig - Black Gishi - Umbrella - Serbian - Soya Bean Foot Grass - Gishi Salt Thorn

5 • 1 4

5

4

5

4

5 ti

First

L

I

I

First

First

I

-1 531

Table 6

Effect- Effect of post-emergent treatment Quantity of plant material damage - (g / 100m ² ) Oat Rooster - Pig - Black Gish - Umbrella - Serbian - Soya bean footworm wormwood - Gishi moss

4

5

4

5

5

5

4

5

5

5

5

5

5

5

5

5

5

5

5

5

5

5

4

5

4

5

5

5

5

5

5

5

5

5

5

5

5

5

4

5

4

5

5

5

5

5

5

5

5

5

5

5

4

5

4

5

4

She

Li

L

L

L

L

L

L

L

L

L

L

L

L

L

I

L

L

L

L

I,

I,

L

L

L

L

L

I

L

L

I

First

I

I

L

I

L

L

L

L

L

i.

L

First

First

I

L

1 ·.

I

I

L

First

L

L

L

L

L

L

L

-1 633

3-1

Compound A Effect - Effect of Post-emergent Treatment Female Sex Material Exposure Amount-- ^; ---------------------------------- (g / 100m ^z , Zab Rooster- Pig- Black Gabi- Cute- Serbian- Soybean foot pariah wormwood -gishi cheese thorn

Reference compound

B 3

Formulation example 1

Formulation example 5

Wettable powder composition by grinding the following components:

No. 3 Compound (40 parts by weight) and white carbon (5 parts by weight) were prepared by mixing

An emulsifiable concentrate was prepared by blending a homogeneous blend of the following components with polyoxyethylene-nonyl20 containing moles of ethylene oxide:

No. 56 compound SP-3005X dimethylformamide xylene

Formulation example 6

23.0 parts by 10.0 parts by 20.0 parts by 37.0 parts by weight

part by weight of phenyl ether

Formulation example 2

A granular preparation was prepared by mixing the following components homogeneously, grinding, adding water and then granulating the mixture:

Compound No. 25 A mixture of 5 parts by weight bentonite (30 parts by weight) and clay (60 parts by weight) 90 parts by weight calcium lime sulphonate 5 parts by weight

Granular formulations were prepared by mixing, grinding, adding water, kneading, extruding and drying the following components:

1% active ingredient A particulate preparation containing 0.1% active ingredient

Formulation example 3

An emulsifiable concentrate was prepared by mixing the following components homogeneously:

• 10

No. 22 Bentonite / Clay Mixture of Compound Calcium Lignin Sulfonate

0.1 parts by weight (31 parts by weight bentonite and 63 parts by weight clay,

94.9 parts by weight (31.6 parts by weight bentonite and 63.3 parts by weight clay, parts by weight

No. 50 Compound xylene Polyoxyethylene Nonylphenyl Ethylene · (8 parts by weight) and calcium alkylbenzene sulphonate (2 parts by weight) 40 parts by weight

Claims (4)

PATENT CLAIMS Formulation example 4 An emulsifiable concentrate was prepared by mixing the following components homogeneously: No. 22 compound 11.5 parts by weight 8 parts by weight of 2 parts by weight of 2 parts of xylene in a mixture of SP-3005X / 10 moles of ethylene oxide with a polyoxyethylene styrylphenyl ether and an alkylaryl sulfonate; manufactured by Toho Kagakukogyo Kabushiki Kaisha Tokyo Japanese company dimethylsulfoxide methylnaphthalene 10.0 parts by weight 10.0 parts by weight 68.5 parts by weight CLAIMS 1. A herbicidal composition comprising 0.1 to 50% by weight of the ² -1,2,4-triazolinone compound of the formula I as an active ingredient, wherein R is hydrogen; an alkali metal; C 1-6 alkyl optionally substituted with halogen; C 3-6 cycloalkyl optionally monosubstituted with halogen; C3-C6 alkenyl; C 3-6 alkynyl, (C 1-4 alkoxy) - (C 1-4 alkyl), (C 1-4 alkyl) thio (C 1-4 alkyl), (C 1-1 alkyl) ) sulfinyl (C1-C4 alkyl), (C1-C4 alkyl) sulfonyl (C1-C4 alkyl 1), (C1-C4 alkoxy) - (C1-C4 alkoxy) - (1) Or a C4 alkyl group, or one or two halogens on the phenyl moiety -1735 195722 benzyl, optionally substituted with C 1 -C 4 alkyl or C 1 -C 4 alkoxy, containing by weight 100% or more of a solid or liquid inorganic substance of organic or inorganic origin, whether natural or synthetic preferably clay, bentonite, white carbon, xylene, methylnaphthalene, dimethylsulfoxide or dimethylformamide, and a nonionic or anionic surfactant, preferably a dispersant or emulsifier, preferably a calcium salt of lignin sulfonic acid, alkyl benzyl, arylsulfonate, polyoxyethylene-nonyl-15-phenyl ether or polyoxyethylene-styrylphenyl ether. (Priority: March 3, 1985) 2. A composition according to claim 1, wherein the active ingredient is a _2-1,2,4 -triazolin-5-one derivative of formula (I): R is C 1-6 alkyl. (First Edition: 5/31/1984) 3. A method wherein the ^two new -l, 2,4-triazolin-5 derivatives which (I). 25 R is hydrogen; C 1-6 alkyl optionally substituted with halogen; C 3-6 cycloalkyl optionally monosubstituted with halogen; C3-C6 alkenyl; C 3-6 alkynyl; (C1-C4) alkoxy (C1-C4) alkyl; (C1-C4 alkyl) thio (C1-C4 alkyl)); (C 1 -C 4 alkyl) sulfinyl (13C) -4-carbon) Union alkyl); (C 1 -C 4 alkyl) sulphoryl (C 1 -C 4 alkyl); (C 1 -C 4 alkoxy) - (C 1 -C 4 alkoxy) - (C 1 -C 4 alkyl); (C 1 -C 4 alkoxy); ) -carbonyl (C 1 -C 4) alkyl; the phenyl portion has 1 or 2 halogens or 1 or 2 (C 1 -C 4) alkoxy groups or a nitro group (C 1 -C 4 alkoxy) carbonyl group; a benzyl group optionally substituted with phenoxy or C1-C4 alkyl, α-methylbenzyl or phenethyl, characterized in that a) reacting a compound of formula II and III wherein R is as defined above, Z ¹ is chlorine, bromine or iodine; b) reacting a compound of formula (IV) and burn (V) wherein R is as defined above, Z ² is halogen, or c) reacting a compound of formula (VI) and a compound of formula (VII) wherein R is as defined above, X is halogen and hydroxy, in the presence of a basic compound and inert solvent (s). (Priority: March 3, 1985) 4. A process according to claim 3 for the preparation of compounds of formula I wherein R is C 1-6 alkyl. (Priority: 1984.