GB2194233A

GB2194233A - Herbicidal triazolinone derivatives compounds of formula

Info

Publication number: GB2194233A
Application number: GB08717055A
Authority: GB
Inventors: Mitsuru Kajioka; Atsushi Tsushima; Yoichi Hachitani; Kenichi Ikeda
Original assignee: Nihon Nohyaku Co Ltd
Current assignee: Nihon Nohyaku Co Ltd
Priority date: 1984-05-31
Filing date: 1987-07-20
Publication date: 1988-03-02
Also published as: SE8502073L; DK190985D0; DK157191C; HU195722B; GB2162511B; IL75034A0; CS248742B2; DK157191B; HUT38219A; GB8717055D0; GB8510455D0; DE3514057C2; IT1215156B; AU552540B2; CH664364A5; BE902306A; NL8501217A; SE452882B; DK190985A; AU4146285A

Description

GB2194233A 1 SPECIFICATION &2-1,2,4-Triazolin-5-one derivatives and

herbicidal compositions containing the same

FIELD OF THE INVENTION 5

The present invention relates to &2-1,2,4-triazolin-5-one derivatives and herbicidal compositions containing the same as the active ingredient.

A2-1,2,4-Triazolin-5-one derivatives according to the present invention are represented by the general formula (1), 10 F 0 Cl- - N j N-CHF 2 0 N 11 CH 15 ROCCHO 1 CH 3 (wherein R is a hydrogen atom; an alkali metal atom; a quaternary ammonium salt; an unsubsti- 20 tuted-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 alkylsuifinylaikyl group; a lower alkylsulfonylalkyl group; a lower alkoxyalkoxyalkyl group; a lower alkoxycarbonylalkyl group; a hydroxycarbonylalkyl group; an 25 unsubstituted-benzyl group; a substituted-benzy] 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; a-methy] benzy] group or a phenethyl group).

30 DESCRIPTION OF THE PRIOR ART

A2-1,2,4-Triazolin-5-one derivatives represented by the general formula (1) 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 A2-1,2,4triazolin-5-one derivative represented by the general formula (1) are disclosed as the active ingredient in herbicidal compo- 35 sitions in Japanese Patent Kokai (Laid-open) No. Sho 57-108079 (1982) and Sho 57-181069 (1982).

The present inventors have found that compounds represented by the general formula (1) possess effective herbicidal activities, thus they are useful as agricultural herbicides.

Additionally, the present inventors have found the facts that compounds represented by the 40 general formula (1) show surprisingly excellent herbicidal activities in relatively lower dosage and with lower phytotoxicities as compared with activities shown by compounds disclosed in the above-mentioned prior art references.

SUMMARY OF THE INVENTION 45

An object of the present invention is to provide novel A2-1,2,4-triazolin5-one derivatives.

Another object of the present invention is to provide herbicidal compositions containing the &2-1,2,4-triazolin-B-one as the active ingredient.

Yet further object of the present invention is to provide processes for preparing A2-1,2,4 triazolin-5-one derivatives. 50 Compounds represented by the general formula (1) can be prepared by for example, processes method-A, method-B and method-C as follows:

Method-A F 0 CEP 2Z 1 p 0 55 cl N k NH (11i) 1k k =C- c N N-CHF 0 N Base 2 11 0 N - ROCCHO CH 3 11 CE i ROCCHO 3 60 t;L'3 1 Lon 3 (wherein R is the same as defined above; Z1 is a chlorine atom, a bromine atom or an iodine atom). 65 2 GB2194233A 2 Method-13 F 0 0 F 0 11 2 A 5 d, N N-CHF2 RO% Z cl- N CHF2 _N. 1 6 4 0 HO CH (y) 3 Base ROCCHO CH 3 1 L;h 3 (1) 10 (wherein R is the same as defined above; Z2 is a halogen atom).

Method-C F 0 F 0 15 ROH M) 2 C1 - N N-CHF2 - C1 CHF 2 \ N_=0 0 11 0 4 11 CH 3 ROCCHO CH 3 20 XCCHO I I %.n 3 Un3 (VII) (wherein R is the same as defined above; X is a halogen atom or a hydroxyl group).

Thus, the objective A2-1,2,4-triazolin-5-one derivative represented by the general formula (1) 25 can be prepared, in method-A, by reacting a compound represented by the general formula (11) with a compound represented by the general formula (111); in method-13, by reacting a 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 30 presence or absence of a basic compound.

As to the inert solvent used in these reactions, any inert solvent which does not give any adverse effect to the reactions may be employed, for example 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, 35 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 fied; lower fatty acid amides such as dimethylformamide, dimethylacetoamide or the like can be exemplified; and water, dimethyl sulfoxide or the like can be exemplified. The above-mentioned 40 solvents may be employed in singly or in a mixture thereof.

Further, in method-C, when an alcohol is used as the solvent, an alcohol corresponding to a compound represented by the general formula (VI) may preferably be used.

As to the basic compound used in the above-mentioned reactions, inorganic basic compounds, for example alkali metal hydrides such as sodium hydride or the like; alkali metal hydroxides such 45 as sodium hydroxide, potassium hydroxide 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 like; and organic basic compounds such as pyridine, trimethylamine, triethylamine, diethylaniline, 1,8-diazabicyclo-[5,4,01-7-undecene or the like can be exemplified. 50 Reactions of the present invention can be carried out, for example at a temperature in the range of from 0' to 150'C 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. 55 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 (11) used as the starting material in method-A may be synthesized by the reaction steps as follows:

3 GB2194233A 3 C=XCOOR2 Cl_'C'L 41n4H2 R'-A- I 0 L;n 3 (IX) IZOCCHO Heat 5 1 CH 3 (Vill) F 10 C NHNHC=NCOOR 2 Basic compound 0 Un 3 11 'OCCIHO 15 L;n 3 F 0 20 cl -N NR 0 N ROCCHO CH3 1 25 t-4 3 (wherein R is the same as defined above; RI and R2 are each a lower alkyl group; A is an oxygen atom or a sulfur atom). 30 Thus, a compound represented by the general formula (11) 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 formula (X) is treated under a ring-closing reaction, with a basic compound, with or without being separated from the reaction product. 35 Furthermore, a compound represented by the general formula (IV) used as the starting material in method-13 may be synthesized by the reaction step as follows:

F 0 F 0 C N), N_C"V2 HBr:!_ C1_ N N-CHF2 40 R10 CH 3 HO CH3 (xi) (IV) 45 (wherein R1 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 A 2-1 2,4-triazolin-5-one derivatives represented by the general formula (1) 50 are shown in the following Table 1.

0 cl-C N') N-CHF 55 0 N= 2 11 XX ROCCHO I CH3 CH 3 4 GB2194233A 4 Table 1

Compound No. R - Physical properties 5 1 H- n 24.5 1.5192 D 2 Na- Melting point 186.10C 10 3 K- Melting point 119.20C 4 %H 4- Metling point 92.70C 15 iso-C H %H - Melting point 157.31C 3 7 3 6 (C 2 H 5).('qH- Oily substance 20 7 (n-C H)('qH - Melting point 126.50C 4 9 2 2 8 CH - n 23 1.5142 3 D ' 10 25 9 c H - 1.5112 2 5 n D 11-C H - n 23.0 1.5051 3 7 D 11 iso-C H - n 23.0 1.5051 30 3 7 D 12 R-C H - n 29.0 1.5031 4 9 D 13 iso-C H - n 29.0 1.5011 35 4 9 D 14 tert-C H - n 26.0 1.5009 4 9 D 15 n-C H - n 27.5 1.4984 40 11 D 16 iso-C H n 26.0 1.5002 ll- D 17 n-C H - n 28.5 1.4992 45 6 13 D 18 C1CH CH n 26.5 1.5204 2 2 D 19 BrCH CH n 19.5 1.5291 2 2 D 50 cl 3 CCH 2- Melting point 1b6.50C 21 F CCH - n19.5 1.4826 3 2 D 55 22 C1CH2 CH 2 CH 2- Melting point 87.71C 23 BrCH 2 CH 2 CH 2- Melting point 83.80C 24 C1CH2CH- Melting point 68.71C 60 1 CH 3 - Contld GB2194233A 5 Table 1 (Cont'd) 25 C1CH CHCH - Melting point 95.VC 5 21 2 cl 26 C1CH n 14.5 1.5091 10 2' D CH- C1CH 2 27 BrCH 2'- Melting point 104.20C CH- 15 1 BrCH 2 28 F C n 19.5 1.4573 3 D CH- 20 3 29 C1CH 2 CH 2 CH 2 CH 2- Melting point 95.3'C 25 E- n 26.0 1.5130 D 31 n 27.5 1.5140 30 D 32 n 17.5 1.5174 'Cl D 35 33 CH =CHCH n 28.5 1.5156 2 2 34 CH=-CCH n 28.5 1.5192 40 2 D CH=-CCH CH n 17.5 1.5209 2 2 D 36 CH O(CH) - n 26.0 1.5088 45 3 2 2 D 37 C H O(CH n 26.0 1.5022 2 5 2 D 38 iso-C H O(CH n 26.0 1.4989 50 3 7 2 2 D 39 n-C 4 H 9 O(CH 2) 2 26.0 1.4878 n D 40 CH OCHCH CH - n27.5 1.5009 55 3 1 2 2 D CH 3 41 CH SCH - n 18.0 1.5279 60 3 2 D 42 CH S(CH n 26.5 1.5306 3 2 2 D - Cont'd - 65 6 GB2194233A 6 Table 1 (Cont d) 43 C H S (CH) - n19.5 1.5274 5 2 5 2 2 D 44 iso-C H S(CH) - n 19.5 1.5233 3 7 2 2 D iso-C H S(CH) - n 19.5 1.5212 10 4 9 2 2 D 46 sec-C H S(CH) - n 19.5 1.5219 4 9 2 2 D 47 tert-C 4 H 9 S(CH 2)2_ 22.5 n D 1.5179 48 CH S(CH) - n 19.5 1.5299 15 3 2 3 D 49 C H S(CH n 19.5 1.5203 50 iso-C H S(CH n 19.5 1.5204 20 3 7 2 3 D 51 n-C H S(CH) - n 14.5 1.5216 4 9 2 3 D 52 iso-C H S(CH n 14.5 1.5209 25 4 9 2 3 D 53 tert-C H S(CH n 16.5 1.5172 4 9 2 3 D 54 CH 3 S(CH 2)2_ Melting point 104.50C 30 55 CH S(CH) - Melting point 99.80C 35 3 2 2 y 0 0 56 CH O(CH) O(CH n 26.0 1.5052 40 3 2 2 2 2 D 57 CH 3 OC-CH- Melting-point 108.10C 3 45 58 CH - Melting point 82.46C 2 cl 50 59 CH 2- Melting point 117.50C 55. cl 55 CH 2- Melting point 72.60C 61 Cl CH2- Melting point 73.OOC 60 - Cont ' d - 65 7 GB2194233A 7 Table 1 (Cont d) F 5 62 CH 2- Melting point 115.70C 63 F CH 2- Melting point 80.01C 10 64 H C CH - Melting point 102.81C 15 3 2 65 H CO Melting point 89.40C 20 3 CH2- 66 0 2 N CH 2- Melting point 126.5'C 25 67 C 2 H 5 OC --a- CH 2Melting point 135.31C 30 11 0 26.0 1.5588 35 68 - CH n 2 D cp,", 40 0 cl 1 69 cl C112- Melting point 163.0C 45 cl 50 CH 2- Melting pbint 114.7C cl 55 CH 3 0 71 CH 3 0 CH 2- Melting point 96.50C 60 - Cont'd - 8 GB2194233A 8 Table 1 (Cont ' d) 72 H- Oily substance 0-CI 1 - CH 3 10 73 -CH CH - Oily substance 2 2 15 Next, NMR spectrum data for the compound having physical properties indicated as oily substance are shown in Table 2 below.

Table 2 20

Compound NMR CC1 4 (ppm) No. TMS 25 6 1.15 (t, 9H), 1.64 (d, M), 2.41 (s, M), 2.19 (q, 6H), 4.53 (q, 1H), 7.03 (t, 1H), 30 7.04 (d, 1H), 7.22 (d, 1H) 35 72 1.32-1.77 (m, 6H), 2.30 (s, 3H), 4.60 (q, 1H), 5.76 (q, 1W, 686 (t, 1H) 40 6.76-7.31 (m, 7H) 73 1.56 (d, M), 2.35 (s, M), 2.84 (t, 2H), 45 4.28 (t, 2H), 4.59 (q, 1H), 6.91 (t, 1H)r 6.85-7.32 (m, 7H) 50 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.

55 Example 1

Preparation of 1-14-chloro-2-fluoro-5-[1-(ethoxycarbonyi)ethoxylphenyll-4difiuoromethy]-3-m e- thyi-A2-1,2,4-triazolin-5-one (Compound No. 9) 9 GB2194233A 9 CH 0 C141 N N-CHE 2 ""' I 'n' 3 H C N j N-CHF :\_ \ N - 2 S. i 1 2 HO ", CH 0 N 5 3 CH3 (IV) 13-27 Grams (0.045 mole) of compound (IV), 9.06 g (0.0498 mole) of ethyl a-bromopropion- 10 ate and 13.27 g (0.0962 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 temperature, and the insoluble matters were removed by filtration. Next, the filtrate was concentrated, and the oily substance thus obtained was dissolved in diethyl ether, and washed with cold water, then the 15 diethyl ether solution was dried, the solvent was removed by evaporation to yield an oily substance. (This oily substance was indeed clear state as it was, and was purified by means of a dry column chromatography by using a silica gel.) Yield: 14.7 g (83.1%) Refractive index n19.0 D 1.5112.

20 Example 2

Preparation of 1-14-chloro-2-fluoro-5-[l-(hydroxycarbonyl)ethoxy]phenyll4-difuoromethyl-3-m e- thyl-A2-1,2,4-triazolin-5-one (Compound No. 1) F 0 F 0 25 cl- - N 'K N-CHF 2 C1 -N j N-CHF _J 2 0 N \ 0 N- C CH 11 CH C2 H5 OC I 110 3 HOCCHO 3 30 t_zi 1 3 CH 3 1.4 Grams (0.00356 mole) of 1-14-chloro-2-fluoro-5-[l- (ethoxycarbonyl)ethoxy]phenyll-4-difluoromethyl-3-methyl-A2-1,2,4-triazolin-5-one was dissolved in 50 ml of ethanol, then to this solu- 35 tion was added 1.2 g of 20%-potassium hydroxide aqueous solution, and the whole mixture was stirred at a room temperature for 3.5 hours. After the reaction was completed, the reaction 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 of oily sub- 40 stance as the objective product. Refractive index n24.5 1.5192. Yield 84%.

D Example 3

Preparation of sodium 2-[2-chloro-5-(4-difluoromethyl-3-methyl-5-oXo-A2-1, 2,4-triazolin-l-yl)-4- fluorophenoxy]propionate (Compound No. 2) 45 F 0 F 0 C' - N N-CHF 2 ci- N), N-CHF 2 o N=' N 50 EOCCHO CH 3 CH 3 1 NaOCCHO CH 3 1 55 0.5 Gram (0.00136 mole) of 1-14-chloro-2-fluoro-5-[l(hydroxycarbonyl)ethoxy]phenyll-4-difluoromethyl-3-methyl-A2-1,2,4-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 tetrahydro furan was removed by evaporation under a reduced pressure, the residue thus obtained was 60 washed with n-hexane to yield 0.37 g of the objective product. Melting point 186.10C. Yield 76.4%.

Example 4

Preparation of dibutylammonium 2-[2-chloro-5-(4-difluoromethyl-3-methyt-5oXo-A2-1,2,4-triazo- 65 GB2194233A 10 lin-l-yi)-4-fluorophenyloxy]propionate (Compound No. 7) F 0 F 0 cl N N-CHF c N 1k N-CHF J_ 2 5 2 N N 0 n-C H 0 11 / CH 3 4 9\ Ge 11 CH 3 NH 2 OCCHO n-C H cl 3 4 9 CH 3 10 0.5 Gram (0.00136 mole) of 1-14-chloro-2-fluoro-5-[1- (Hydroxycarbonyi)ethoxylphenyll-4-difluoro-methyi-3-A2-1,2,4-triazolin-5-one was dissolved in 20 mi of benzene, then to solution was added 1.0 9 (0,0139 mole) of dibutylamine, then under an ice-cooling condition, the reaction was carried out. The crystals fromed in the reaction mixture was collected by filtration, and 15 washed with benzene to yield 0.51 g of the objective compound. Melting point 126.WC. Yield 79.4%, Example 5

Preparation of 1-14-chloro-2-fluoro-5-[1(propargyloxycarbonyi)ethoxy]phenyll-4-difluoromet hy1-3methyl-A2-1,2,4-triazolin-5-one (Compound No. 34) F 0 F 0' cl N N-CHF Cl-N), N-CHF 25 N 2 > \ N-i 2 0 0 / 11 CH3 9 CH3 C1CCHO CH 3 30 F 0 cl -N), N-CHF 2 35 6 \ 0 M I CH ECECCH 2 OCCHO 3 1 40 CH 3 A mixed solution of 20 mi of thionyl chloride containing 2.7 9 of 1-14chloro-2-fluoro-5-[1 (hydroxycarbonyl)ethoxylphenyll-4-difluoromethy]-3-methyl-A2-1,2,4triazolin -5-one was refluxed under heating for 2 hours. After the reaction was completed, the excessive thionyl chloride was 45 removed by evaporation, and obtained 2.8 g of 1-14-chloro-2-fluoro-5-[1(chiorocarbonyi)ethoxy]phenyll-4-difluoromethyl-3-methyi-A2-1,2,4-triazolin-5-one quantitatively. Then 0.5 9 (0.0013 mole) of this compound was dissolved in 20 mi 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 com- 50 pleted, 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 carbo nate, 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 9 of the objective product. Refractive index n M. 5 1.5192. Yield 66.6%. 55 D Example 6

Preparation of 1-15-[1-(tert-butoxycarbonyi)-ethoxy]-4-chloro-2fluorophenyll-4-difluoromet hy1-3- methyl-A2-1,2,4-triazolin-5-one (Compound No. 14) GB2194233A 11 F 0 F 0 c N N-CHF J 2 cl- -N N-CHF 2 c) N.5 CH 3 CH 3 CH 3 10 0.58 Gram (0.00151 mole) of 1-{4-chloro-2-fluoro-5-[1- z(chlorocarbonyl)ethoxy]phenyll-4-difluoro-methyl-3methyi-A2-1,2,4-triazolin-5-one was added in a mixed solution of 0.25 g (0.00338 mole) of tert-butyl alcohol, 0.14 9 (60% in oil, 0.0035 mole) of sodium hydride, and 20 mi 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 15 D.5 described in Example 5, to yield 0.13 9 of the desired product. Refractive index n26' 0 1 009.

Yield 18.8%.

Example 7

Preparation of 1-14-chloro-2-fluoro-5-[1-[[1(methoxycarbonyi)ethoxylcarbonyllethoxyphenyll -4difluoromethyl-3-methyl-A2-1,2,4-triazolin-5-one (Compound No. 57) F 0 F 0 cl N" N-CHF!!.- Cl-:N N-CHF \N 2 0 0 N -:1 2 25 11 CH 11 11 \ CH 3 HOCCHO 3 CH 3 OCCHOCCHO CH 3 CH 3 CH 3 30 A mixed solution of 0.5 g (0.00136 mole) of 1-14-chloro-2-fluoro-5-[1- (hydroxycarbonyl)ethoxylphenyll-4-difluoromethyl-3-methyl-A2-1,2,4-triazolin-5-one, 0.28 9 (0. 00136 mole) of N,Wdicyclo hexylcarbodiimide, 0.02 g (0.000164 mole) of 4-dimethylaminopyridine and 10 mi 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 filtrate was treated by evaporation, the 35 residue obtained was purified by means of a dry column chromatography to yield 0.41 9 of the objective product. Melting point 108.1'C. Yield 64.3%.

Example 8

Preparation of 1-14-chloro-2-fluoro-5-[1-(ethoxycarbonyl)ethoxylphenyll-4difuoromethyi-3-m ethy]- 40 A2-1,2,4-triazolin-5-one (Compound No. 9) 0 F 0 cl N 101 NH C" cl N 1k N-CHF 2 45 0 0 11 CH 3 11 CH 3 c 2 H 5 OCCHO c 2 H 5 OCCH Cl H 3 50 0.046 Gram (0.00134 mole) of sodium hydride was suspended in 10 m[ of dried N,N dimethylformamide, to this suspension was added dropwise a solution prepared by dissolving 0.4 g (0.00122 mole) of 1-14-chloro-2-fluoro-5-[1- (ethoxycarbonyi)ethoxylphenyll-3-methyi-A21,2,4-triazolin-5-one at a room temperature. After the completion of dropwise addition, the whole mixture was stirred for 30 minutes, then monochlorodifluoromethane (CICI-IF2) gas was 55 introduced into the mixture at 13WC 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 z was removed by evaporation to yield an oily substance. This only substance was purified by means of a dry column chromatography to yield 60 0.15 9 of the objective product. Refractive index n" 1.5112. Yield 32.6%.

D Example 9

Preparation of 1-14-chloro-2-fluoro-5-[1(methyithiomethoxycarbonyi)ethoxy]phenyll-4-difluo rome- thyl-3-methy I-A2-1 2,4-triazolin-5-one (Compound No. 41) 65 12 GB2194233A 12 F r 0 J N N-CHF - N N-CHF 2 C 2 0 CP 'N:--0 N 11 11 5 HOCCHO CH 3 CH 3 SCH 2waw CH 3 1 1 t_n 3 Lon 3 A mixture of 0.5 g (0.00137 mole) of 1-14-chloro-2-fluoro-5-[l- (hydroxycarbonyl)ethoxy]phenyll-4-difluoromethyl-3-methyl-A2-1,2,4-triazolin-5-one, 1.76 g (0.00128 mole) of tert-butyl bro mide, 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. After the completion of the reaction, the reaction product was treated by a method similar to that described in Example 8 to yield 0.4 g of the objective product. Refractive index n18.0 1.5279. 15 D Yield 68.7%.

The A2-1,2,4-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 (Echinochloa crusgalli Beauv., an annual weed of Gramineae family grown in paddy fields and strongly injurious), monochoria (Monochoria vaginalis Presl, a strongly injuri- 20 ous annual weed of Pontederiaceae family grown in paddy fields), smallflower umbrellaplant (Cyperus difformis L., an injurious annual weed of Cyperaceae family grown in paddy fields), slender spikerush (Eleocharis acicularis R6mer 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 25 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 (Digitaraia adscendcus Henn, an annual wee of Gramineae 30 family which is a typical strongly injurious weed grown in upland fields and orchards), Gishi-gishi (Rumex japonicus Houttuyn, a perennial weed of Polygonaceae family, grown in upland fields and on roadsides), umbrella sedge (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 (Xan- 35 thium Strumarium L., an annual weed of Compositae family, strongly injurious to soybeans).

Since, A2-1,2,4-triazolin-5-one derivatives represented by the general formula (1) exhibit excel lent controlling effects against weeds of both pre- and post-emergent stages, they are useful as herbicides for soil treatment 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 40 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 fields, agricultural pathways, waterways, pasture, graveyards, parks, roads, playgrounds, unoccupied areas around buildings, reclaimed lands, railways and forests. 45 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 formu lated, according to conventional procedures for preparing agricultural compositions, into a form convenient to use. That is, derivatives of the present invention are mixed with suitable insert 50 carriers and, if necessary, further mixed with adjuvants, in a suitable ratio, and through dissolu tion, 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 55 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; synthetic polymers such as powdered synthetic resins; inorganic or mineral products such as clays (e.g., kaolin, benzonite and acid 60 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, pumice, calcined diatomaceous earth, ground brick, fly ash, sand, calcium carbonate, and calcium phos- 65 13 GB2194233A 13 phates; chemical fertilizers such as ammonium sulfate, ammonium phosphates, ammonium ni trate, 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 5 be used along or in combination with one another, are water, alcohols (e. g., methanol, ethanol, isopropanol, butanol and ethylene glycol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone), ethers (e.g., diethyl ether, dioxane, cello solves, dipropyl ether, and tetrahydrofuran), aliphatic hydrocarbons (e.g. , gasoline and mineral oils), aromatic hydrocarbons (e.g., benzene, toluene, xylene, solvent naphtha, and alkylnaphthal- 10 ene), halogenated hydrocarbons (e.g., dichloroethane, chlorinated benzenes, chloroform and car bon tetrachloride), esters (e.g., ethyl acetate, dibutyl phthalate, diisopropyl phthanate, and dioctyl phthalate), acid amides (e.g., dimethy[formamide, diethy1formamide, and dimethylacetamide), and nitriles (e.g., acetonitrile), and dimethyl sulfoxide.

As to the adjuvants, which are exemplified below, are used according to individual purposes. 15 In some cases, they are used in combination with one another. In some other cases, no adjuvant is used at all.

For the purpose of emulsification, dispersion, solubilization and/or wetting of the active ingredi- ents, there can be used surface active agents, for example polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene resinates, 20 polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooeate, alkylarylsulfonates, naphthalenesulfonic acid condensation products, ligninsulfonates, and higher alcohol sulfate est ers. 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, methylcellulose, carboxymethy1cellulose, gum arabic, polyvinyl alcohol, pine root oil, rice 25 bran oil, bentonite 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 dispersible compositions, it is also recommendable to use naphthalenesul- fonic acid condensation products and condensed phosphates. 30 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. For the preparation of powdered or granulated products, it is generally 0.5 to 20% by weight 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 35 ingredients may be used.

For destroying various weeds, inhibiting their growth, or protectinuseful 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 other suitable medium, to the soil or the foliage of weeds in the area where the emergence or growth of weeds is 40 undesirable.

The amount of the heribicial 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 composition, the mode of application, the type 45 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 1 to 500 g per 10 ares. On the other hand, in 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 50 lower than the above, when it is used in combination with 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 of weeds in paddy fields. In order to expand both range of controllable weed species and the period of time when effective applications are possible or to reduce the 55 dosage, the herbicidal composition of the present invention can be used in combination with other herbicides, and this usage is within the scope of the present invention.

For example, herbicidal composition of the present invention can be used in combination with one or more of the following herbicides.

Phenoxy fatty acid type herbicides: for example, 2,4-D: e.g. ethyl (2,4dichlorophenoxy)acetate 60 MCP: e.g., ethyl (2-methyl-4-chlorophenoxy)acetate, sodium (2-methyl-4chlorophenoxy)acetate, and allyl 2-(2-methyl-4-chlorophenoxy)acetate MCBP: e.g., ethyl (2-methyl-4-chlorophenoxy)butyrate Diclofop-methyl: methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propanoate Diphenyl ether type herbicides: for example, 65 14 GB2194233A 14 Nitrogen: 2,4-dichlorophenyl 4-nitrophenyl ether Chlornitrofen: 2,4,6-trichlorophenyl 4-nitrophenyl ether Chlornethoxynil: 2,4-dichlorophenyl 3-methoxy-4-nitrophenyl ether Acifluorfen: 5-(2-chloro-a,a,ct-trifluoro-p-tolyoxy)-2-nitrobenzoic acid and its salts Fluazifop-butyl: butyl ( )-2-[4-[[5-(trifluoromethyl)-2pyridyi]oxylphenoxy]propionate 5 Triazine type herbicides: for example, Simazine: 2-chloro-4,6-bis(ethylamino)-s-triaz!ne Prometryne: 2-methylthio-4,6-bis(!sopropylamino)-s-triazine Simetryne: 2-methyithio-4,6-bis(ethylamino)-s-triazine, and Metribuzin: 4-amino-6-tert-butyi-3-methyithio-1,2,4-triazin-5(H)-one 10 Carbamate type herbicides: for example, Molinate: s-ethyl hexahydro-1H-azepine-l-cabothioate Swep: methyl N-(3,4-dichlorophenyi)carbamate Chloropropham: isopropyl W(3-chlorophenyl)carbarnate and Benthiocarb: s-(4-chlorobenzyi)diethyitriocarbamate 15 Toluidine type herbicides: for example, Trifluraline: (a,a,a-trifluoro-2,6-dinitro-N,N-dipropyi-p-toluidine and Pendimethaline: W(1 -ethyl propyi)-2,6-dinitro-3,4-xylidine Acid amide type herbicides: for example, Propanil: 3,4-dichloropropionanilide 20 Butachlor: N-(Butoxymethyi)-2-chloro-2,6-diethylacetanifide Alachlor: 2-chloro-2,6-diethyl-N-(methoxymethyi)acetanilide Metolachlor: 2-chloro-N-(2-ethy]-6-methylphenyi)-N-(2-methoxy-1- methylethyi)acetamide and Pretilachlor: 2-chloro-2,6-diethyi-N-(2-propoxyethyl)acetanilide Other types of herbicides: for example, 25 Duron: 3-(3,4-d ichloro phenyl)- 1, 1 -dimethylurea Bentazon: 3-isopropyi-(H)-2,1,3-benzothiazin-4-(3H)-one 2,2-dioxide Pyrazolate: 4-(2,4-dichlorobenzoyi)-1,3-dimethylpyrazole-5-yi-p- toluenesuifonate Pyrazoxyfen: 1,3-dimethy]-4-(2,4-dichlorobenzoyi)-5-phenacyloxypyrazol and MY-71: 4-(2,4-dichloro-3-methylbenzoyi)-1,3-dimethylpyrazol-5-yl-,ptoluenesuifonat e 30 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.

Herbicidal test example-1 Controlling effect on paddy field weeds of pre-emergence stage 35

Pots (l/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, respec tively, which are all injurious weeds grown in paddy fields, were conditioned so as to be in pre- emergence stage. 40 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.

Table 2 45

Criterion for determining herbicidal activity Degree of Percent control of herbicidal weed growth activity (%) 50 100 4 90-99 3 80-89 2 70-79 55 1 Less than 70 The test results were summarized in Table 3.

Table 3

Amount of Effect of pre-emergence treatment active Compound ingredient Barnyard Mono- Umbrella- No. Ware) grass choria plant Bulrush Arrowhead 1 30 5 5 5 5 5 3 5 5 5 5 5 2 30 5 5 5 5 5 3 5 5 5 5 5 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 is 30 5 5 5 5 5 3 5 5 5 5 5 G) 19 30 5 5 5 5 5 3 5 5 5 5 5 (To be continued) > CM Table 3 (Continued) 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 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 G) 42 30 5 5 5 5 5 3 5 5 5 5 5 (To be continued) Table 3 (Continued) 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 5 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 30 5 5 5 5 5 3 5 5 5 5 5 56 30 5 5 5 5 5 3 5 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 5 5 5 64 30 5 5 5 5 5 G) 3 5 5 5 5 m N 30 5 5 5 5 5 3 5 5 5 5 5 (To be continued) > OD Table 3 (Continued) 69 30 5 5 5 5 5 3 5 5 5 5 5 Reference Compound A 3 3 4 4 3 3 B 3 3 4 4 3 3 Reference compound A: Compound No. 1 = 1-(2,4-Dichloro-5isopropoxyphenyl)-4- difluoromethyl-3-methyl-A 2 -1,2,4-triazolin-5-one as disclosed in Japanese Patent Kokai No. 57-108079 (1982) Reference compound B: Compound No. 7 = 1-(2,4-Dichloro-5-1[1- ethoxycarbonyllethoxy]phenyl)-4-difluoromethyl-3-methyl-A 2_1 2,4-triazolin-5-one as disclosed in Japanese Patent Kokai No. 57-181069 (1982) G) W CO 19 GB2194233A 19 Herbicidal test example-2 Controlling effect on paddy field weeds of post-emergence stage

Pots (l/10,000-are) were filled with soil to simulate a paddy field and grown with each of injurious weeds of the following lead age. In addition, young seedings of rice plant (cultivar:

"Nihonbare") of the 2.5 lead age were transplanted to the soil on the day before the treatment 5 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 10 Barnyard grass 1 Monochoria 2-3 Umbrella plant 1-2 Bulrush 2-3 Arrowhead 3 15 Water nutgrass 1-2 The criterion for judging the degree of crop injury are as follows:

H: High (including withering) 20 M: Medium L: Low N: None The criterion for judging the herbicidal activity is in accordane with that used in herbicidal test example-1. The results were summarized inTable 4. 25 Table 4

Amount of Effect of post-emergence treatment Crop active injury Compound ingredient Barnyard Mono- Umbrella- Water No. (q/are) grass choria plant Bulrush Arrowhead nutgrass Rice 1 30 5 5 5 5 5 5 L 3 5 5 5 5 4 5 L 2 30 5 5 5 5 5 5 L 3 5 5 5 5 5 4 L 8 30 5 5 5 5 5 5 L 3 4 5 5 5 5 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 5 4 L 13 30 5 5 5 5 5 5 L 5 5 5 5 5 5 L 17 30 5 5 5 5 5 5 L 3 5 5 5 5 4 4 L 18 30 5 5 5 5 5 5 L 3 5 5 5 5 4 5 L G) CC] 19 30 5 5 5 5 5 5 L 3 5 5 5 5 5 5 L CO -p.

(To be continued) rli OW, Table 4 (Continued) 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 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 G) 42 30 5 5 5 5 5 5 L 3 5 5 5 5 5 5 L (To be continued) '>" N) Table 4 (Continued) 30 5 5 5 5 5 5 L 3 5 5 5 5 5 5 L 48 30 5 5 5 5 5 5 L 3 5 5 5 4 5 5 L 49 30 5 5 5 5 5 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 5 5 L 3 5 5 5 4 4 4 L 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 L 3 5 5 5 5 5 4 L G) 30 5 5 5 5 5 5 L 3 5 5 5 5 5 5 L (To be continued) Table 4 (Continued).

69 30 5 5 5 5 5 5 L 3 5 5 5 4 4 4 L Reference compound A 3 2 4 4 2 3 2 L B 3 2 4 4 2 3 2 L Reference compounds A and B are the same as mentioned in Table 3.

G) 24 GB2194233A 24 Herbicidal test example-3 Controlling effect on upland field weeds of pre-emergence stage

Polyethylene vats, having 1Ox2Ox5 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. 5 The soil was treated with each of the present herbicides formulated to a given concentration of liquid, by spraying. After 21 days, the herbicidal effect 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.

t, I Table 5

Amount of Effect of pre-emergency treatment active Compound ingredient Barnyard Large Redroot Gishi- Umbrella No. (q/are)_ Oats grass crabgrass pigweed Mugwort gishi sedge Cocklebur 1 30 5 5 5 5 5 5 5 5 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 5 5 5 8 30 5 5 5 5 5 5 5 5 3 4 4 5 5 5 5 5 5 9 30 5 5 5 5 5 5 5 5 3 4 4 5 5 5 5 5 5 11 30 5 5 5 5 5 5 5 5 3 4 4 5 5 5 5 5 5 13 30 5 5 5 5 5 5 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 5 18 30 5 5 5 5 5 5 5 5 3 4 5 5 5 5 5 - 5 5 G) 19 30 5 5 5 5 5 5 5 5 co 3 4 5 5 5 5 5 5 5 CD (To be continued) CF) Table 5 (Continued) 21 30 5 5 5 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 26 30 5 5 5 5 5 5 5 5 3 4 5 5 5 5 5 5 5 31 30 5 5 5 5 5 5 5 5 3 4 4 5 5 5 5 5 5 32 30 5 5 5 5 5 5 5 5 3 4 5 5 5 5 5 5 5 33 30 5 5 5 5 5 5 5 5 3 4 5 5 5 5 5 5 5 34 30 5 5 5 5 5 5 5 5 3 4 5 5 5 5 5 5 5 30 5 5 5 5 5 5 5 5 3 5 5 5 5 5 5 5 5 36 30 5 5 5 5 5 5 5 5 3 4 5 5 5 5 5 5 5 38 30 5 5 5 5 5 5 5 5 3 4 5 5 5 5 5 5 5 42 30 5 5 5 5 5 5 5 5 3 4 5 5 5 5 5 5 5 C.) (To be continued) W > Table. 5 (Continued) 30 5 5 5 5 5 5 5 5 3 4 5 5 5 5 5 5 5 48 30 5 5 5 5 5 5 5 5 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 5 53 30 5 5 5 5 5 5 5 5 3 4 4 5 5 5 5 5 5 54 30 5 5 5 5 5 5 5 5 3 4 5 5 5 5 5 5 5 30 5 5 5 5 5 5 5 5 3 3 4 5 5 5 5 5 5 56 30 5 5 5 5 5 5 5 5 3 3 4 5 5 5 5 5 5 58 30 5 5 5 5 5 5 5 5 3 5 5 5 5 5 5 5 5 61 30 5 5 5 5 5 5 5 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 a) 30 5 5 5 5 5 5 5 5 -P.

3 4 4 5 5 5 5 5 5 P13 (To be continued) N) 00 Table 5 (Continued) 69 30 5 5 5 5 5 5 5 5 3 4 5 5 5 5 5 5 5 Reference compound A 3 2 3 3 5 4 3 4 1 B 3 1 2 3 5 4 3 4 2 G) m NJ W W CO 29 GB2194233A 29 Herbicidal test example-4 Controlling effect on upland field weeds of post-emergence stage

Polyethylene vats, having 10x20x5 cm (depth) size, were filled with soil and seeded with the weeds shown below and soybean seeds, respectiely, and the seeds were covered with soil. The weeds and soybean were cultivated respectively to the following leaf ages and then treated with 5 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 10 Oats 2 Large crabgrass 2 Redroot pigweed 1 Mugwort 1 15 Gishi-gishi 2 Umbrella sedge 1 Cocklebur 1 Soybean iirst trifoliate age 20 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.

Table 6

Amount of. Effect of post-emergence treatment Crop active injury Compound ingredient Large Redroot Gishi- Umbrella No. (g/are) Oats crabgrass pigweed Mugwort gishi sedge Cocklebur Soybean 1 30 5 5 5 5 5 5 5 L 3 4 4 5 5 5 5 5 2 30 5 5 5 5 5 5 5 L 3 4 4 5 5 5 5 5 L 8 30 5 5 5 5 5 5 5 L 3 4 4 5 5 5 5 5 L 9 30 5 5 5 5 5 5 5 L 3 4 4 5 5 5 5 5 L 11 30 5 5 5 5 5 5 5 L 3 4 4 5 5 5 5 5 L 13 30 5 5 5 5 5 5 5 L 3 4 5 5 5 5 5 5 L 17 30 5 5 5 5 5 5 5 L 3 3 4 5 5 5 5 5 L 18 30 5 5 5 5 5 5 5 L 3 4 5 5 5 5 5 5 L 19 30 5 5 5 5 5 5 5 L 3 4 5 5 5 5 5 5 L 21 30 5 5 5 5 5 5 5 L w 3 4 5 5 5 5 5 5 L w (To-be w continued) > w 0 Table 6 (Continued) 22 30 5 5 5 5 5 5 5 L 3 4 5 5 5 5 5 5 L 26 30 5 5 5 5 5 5 5 L 3 4 5 5 5 5 5 5 L 31 30 5 5 5 5 5 5 5 L 3 4 5 5 5 5 5 5 L 32 30 5 5 5 5 5 5 5 L 3 4 5 5 5 5 5 5 L 33 30 5 5 5 5 5 5 5 L 3 4 4 5 5 5 5 5 L 34 30 5 5 5 5 5 5 L 3 4 4 5 5 5 5 5 L 30 5 5 5 5 5 5 5 L 3 4 5 5 5 5 5 5 L 36 30 5 5 5 5 5 5 5 L 3 4 5 5 5 5 5 5 L 38 30 5 5 5 5 5 5 5 L 3 4 5 5 5 5 5 5 L 42 30 5 5 5 5 5 5 5 G) L 3 4 5 5 5 5 5 5 L 30 5 5 5 5 5 5 5 CO >.

L 3 4 5 5 5 5 5 5 W L > (To be continued) Table 6 (Continued) 48 30 5 5 5 5 5 5 5 L 3 4 5 5 5 5 5 5 L 49 30 5 5 5 5 5 5 5 L 3 4 4 5 5 5 5 5 L 53 30 5 5 5 - 5 5 5 5 L 3 4 4 5 5 5 5 5 L 54 30 5 5 5 5 5 5 L 3 4 5 5 5 5 5 5 L 30 5 5 5 5 5 5 5 L 3 4 5 5 5 5 5 5 L 56 30 5 5 5 5 5 5 5 L 3 4 5 5 5 5 5 5 L 58 30 5 5 5 5 5 5 5 L 3 4 5 5 5 5 5 5 L 61 30 5 5 5 5 5 5 5 L j 4 5 5 5 5 5 5 L 64 30 5 5 5 5 5 5 5 L 3 4 4 5 5 5 5 5 L 30 5 5 5 5 5 5 5 L 3 3 4 5 5 5 5 5 L 69 30 5 5 5 5 5 5 5 L G) 3 3 4 5 5 5 5 5 L Reference compound A 3 2 3 4 3 2 3 2 L B 3 2 3 4 3 3 3 2 L NJ 33 GB2194233A 33 Example of herbicidal composition-1 A wettable powder composition was prepared by mixing uniformly and grinding the following ingredients:

Compound No. 3 50 Parts 5 Mixture of clay with white 45 Parts carbon (in which clay is contained as the major component) Polyoxyethylene nonylphenyl 5 Parts 10 ether Example of herbicidal composition-2 A granular composition was prepared by mixing uniformly and grinding the following ingredi- ents, kneading the mixture with a suitable amount of water, and granulating the kneaded mixture: 15 Compound No. 25 5 Parts Mixture of bentonite 90 Parts with clay Calcium ligninsulfonate 5 Parts 20 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 25 nonylphenyl ether with calcium alkylbenzenesulfonate

Claims

1. A2-1,2,4-Triazolin-5-one derivatives represented by the general formula (1), 30 0 ) C1 N 35 CHF

2 (1) ROCCHO CH

3 1 CH 3 40 (wherein R is a hydrogen atom; an alkali meal atom; a quaternary ammonium salt; an unsubsti tuted-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 45 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; ci-methyl benzyl group or a phenethyl group). 50 2. The A2-1,2,4-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 halo gen 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 alkoxya)kyl group; a lower alkylthioalkyl group; a lower alkylsuffiny(alkyl group; a lower alkylsulfonylalkyl 55 group; a lower alkoxyalkoxyalkyl group; a lower alkoxycarbonylalkyl group; a hydroxycarbonylal kyl 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, ei-methylbenzyl group or a phenethyl group. 60 3. A herbicidal composition comprising a A2-1,2,4-triazolin-5-one derivative as claimed in Claim 1 as the active ingredient and a suitable carrier.

4. A herbicidal composition according to Claim 3, wherein the active ingredient is a A2-1,2,4- triazolin-5-one derivative as claimed in Claim 2.

5. A method of preparing a A2_1 2,4-triazolin-5-one derivative of the general formula (1), as 65 34 GB 2 194 233A 34 defined in claim 1, which comprises reacting a compound of the general formula (11) F 0 cl -N NH 5 0 -0 N CH 3 3 (11) 10 1 wherein R is as defined in claim 1, with a compound of the general formula (111) CHF2, Z1 (111) wherein Z1 is a chlorine, bromine or iodine atom. 15 6. A method of preparing a A2-1,2,4-triazolin-5-one derivative of the general formula (1), as defined in claim 1, which comprises reacting a compound of the general formula (N) F 20 Cl-N N-CHF2 Ho CH 3 25 (M with a compound of the general formula (V) 0 30 il RO -,;-n. Z2 (V) 1 CH, 35 wherein R is as defind in claim 1 and Z2 is a halogen atom.

7. A method of preparing a A2-1,2,4-triazolin-5-one derivative of the general formula (1), as defined in claim 1, which comprises reacting a compound of the general formula (V][) F 0 40 A N-CHF cl - -N 2 0 11 CH 45 XCCHO 3 1 CH 3 wherein R is as defined in claim 1 and X is a halogen atom or a hydroxyl group, with a 50 compound of the general formula (V1) ROH (V1) wherein R is as defined in claim 1. 55 8. A method according to any one of claims 5 to 7 in which the reaction is carried out in the presence of a base.

9. A method according to any one of claims 5 to 7 in which the reaction is carried out in an inert solvent.

10. A method according to claim 7 in which the compound of the general formula (V1) is 60 used as a solvent.

11. A method according to any of claims 5 to 10 in which the reaction is carried out at a temperature in the range of 0' to 150T to a predetermined temperature.

12. A method according to any of claims 5 to 11 in which the reaction has a reaction time in the range of 0.5 to 48 hours. 65 GB2194233A 35 13. A2-1,2,4-triazolin-5-one derivatives of the general formula (1), as defind in claim 1, sub stantially as hereinbefore described.

14. Herbicidal compositions substantially as hereinbefore described.

15. A method of preparing A2-1,2,4-triazolin-5-one derivatives of the general formula (1), as defined in claim 1, substantially as hereinbefore described. 5 CLAIMS Amendments to the claims have been filed, and have the following effect:

Claims 1-15 above have been deleted or textually amended New or textually amended claims have been filed as follows:- 10 1. A2-1 2,4-Triazolin-5-one derivatives represented by the general formula (1), 0 cl - N 'I. CHF 2 (1) 15 00 11 CH ROCCHO 3 3 20 (wherein R is a hydrogen atom; an alkali metal atom; a group R', NH,-,, wherein R' is an alkyl group and n is 0,1,2,3, or 4; a halogen-substituted alkyl group; an unsubstituted-cycloalkyl group; a halogen-substituted cycloalkyl group; an alkenyl group; an alkynyl group; an alkoxyalkyl group; an alkylthioalkyl group; an alkyisuifinylaikyl group; an alkylthioalkyl group; an sulfonylalkyl 25 group; an alkoxyalkoxyalkyl group; an 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 alkyl group, an alkoxy group, a nitro group, an alkoxycarbonyl group, a hydroxycarbonyl group and a phenoxy group; et- methyibenzyi group or a phenethyl group, and wherein the alkyl moieties in the groups specified above have from 1 to 6 30 carbon atoms).

2. A herbicidal composition comprising a A2-1,2,4-triazolin-5-one derivative as claimed in Claim 1 as the active ingredient and a suitable carrier.

3. A method of preparing a A2-1,2,4-triazolin-5-one derivative of the general formula (1), as defined in claim 1, which comprises reacting a compond of the general formula (11). 35 F 0 cl;o- N N9 0 N 40 11 ROCCHO CH 3 1 CH 3 45 wherein R is as defined in claim 1, with a compound of the general formula (111) CHF2. Z l (111) wherein Z1 is a chlorine, bromine or iodine atom. 50 4. A method of preparing a A2-1,2,4-triazolin-5-one derivative of the general formula (1), as defined in claim 1, which comprises reacting a compound of the general formula (IV) F 0 55 \ N)N-CHF cl \N 2 HO CE 3. - 60 (1v) with a compound of the general formula (V) 65 36 GB 2 194 233A 36 0 11 RID C CH. Z2 M 1 5 CH, wherein R is as defined in claiml and Z2 is a halogen atom.

5. A method of preparing a A2-1,2,4-triazolin-5-one derivative of the general formula (1), as defined in claim 1, which comprises reacting a compound of the general formula (VII) 10 F 0 A z C1 -N N-CHF 0 \Ii_= 15 Al 11 %-nu CH 3 1 U11 3 (VII) 20 wherein R is as defined in claim 1 and X is a halogen atom or a hydroxyl group, with a compound of the general formula (VI) ROH (VI) 25 wherein R is as defined in claim 1.

6. A method according to any one of claims 3 to 5 in which the reaction is carried out in the presence of a base.

7. A method according to any one of claims 3 to 6 in which the reaction is carried out in an inert solvent. 30

8. A method according to claim 5 which the compound of the general formula (VI) is used as a solvent.

9. A method according to any one of claims 3 to 8 in which the reaction is carried out in a - temperature in the range of 0 to 150'C.

10. A method according to any one of claims 3 to 9 in which the reaction has a reaction 35 time in the range of 0.5 to 48 hours.

11. A2-1,2,4-triazolin-5-one derivatives of the general formula (1), as defined in claim 1, substantially as hereinbefore described.

12. Herbicidal compositions according to claim 2 substantially as hereinbefore described.

13. A method of preparing A2-1,2,4-triazoli n-5 -one derivatives of the general formula (1), as 40 defined in claim 1, substantially -as hereinbefore described.

14. 1-[4-chloro-2-fluoro-5[1-(2-chloro-ethoxycarbonyl)ethoxy]phenyl]-4difluorom ethyl-3-methyl- A2-1,2,3-triazolin-5-one.

15. 1-[4-chloro-2-flLtoro-5-[l-(2-bromoethoxycarbonyl)ethoxy]phenylj-4difluorom ethyl-3-methyl- A2-1,2,4-triazolin-5-one. 45

16. 1-[4-chloro-2-fluoro-5-[l-(2,2,2trifluoroethoxycarbonyl)ethoxy]phenyl-4-dif luoromethyl-3methyl-A2-1,2,4-triazolin-5-one.

17.1[4-chloro-2-fluor-5-[1-3-chloropropoxycarbonyl)ethoxy]phenyl]-4difluoro methyl-3-methyl-A2- 1,2,4-triazolin-5-one.

18.1-[4-chloro-2-fluoro-5-[l -methoxyethoxycarbonyl)ethoxy]phenyl]-4difluoromethyl-3-methyl-A2- 50 1,2,4-triazolin-5-one.

19.1-[4-chloro-2-fluoro-5[l -(isopropoxyethoxycarbonyl)ethoxy]phenylj-4difluoromethyl-3-methyl- A2-1,2,4-triazolin-5-one.

20.1 -[4-chloro-2-fluoro-5-[l-methoxyethoxyethoxycarbonyl)ethoxy]phenyll4-difluo romethyl-3- methyl-A2- 1,2,4-triazolin-5 -one. 55

21. 1-[4-chloro-2-fluoro-5-[1-4-chloro-benzy[oxycarbonyl)ethoxy]phenyl]-4diflur omethyl-3-me- thyl-A2-1,2,4-triazolin-5-one.

22. 1-[4-chloro-2-fluoro-5-[l-(4-methylbenzyloxycarbonyl)ethoxy]phenyl]-4difluo romethyl-3me- thyl-A2-1,2,4-triazolin-5-one.

Published 1988 at The Patent Office, State House, 66/71 High Holborn, London WC 1 R 4TP. Further copies may be obtained from The Patent Office, Sales Branch, St Mary Cray, Orpington, Kent BR5 3RD. Printed by Burgess & Son (Abingdon) Ltd. Con. 1/87.