DK157191B - DELTA2-1,2,4-TRIAZOLIN-5-ON DERIVATIVES AND HERBICIDES CONTAINING SUCH DERIVATIVES - Google Patents

Description

DK 157191 B

The invention relates to 2-1,2,4-triazolin-5-one derivatives and herbicidal agents containing them as the active ingredient.

ISLAND

The β-1,2,4-triazolin-5-one derivatives according to the invention are characterized by the characterizing part of claim 1.

p1 -1,2,4-triazolin-5-one derivatives represented by the general formula (I) of the invention are novel compounds and have not been described in the literature.

Some similar compounds related to the above-mentioned 2-1,2,4-triazolin-5-one derivatives represented by the general formula (I) are described as the active component of herbicidal agents in Japanese Patent Kokai (published) No. Sho 57-108079 (1982) and Sho 57-181069 (1982).

The inventors have found that compounds represented fairly by the general formula (I) exhibit an effective herbicidal activity and that they are thus useful as agricultural herbicides.

Furthermore, the inventors have found that the compounds represented by the general formula (I) surprisingly exhibit excellent herbicidal activities at relatively lower doses and with lower phytotoxicities compared to activities exhibited by compounds described in the references cited which illustrate the prior art.

It is the object of the invention to provide novel -1,2,4-triazolin-5-one derivatives and to provide herbicidal mixtures containing the -1,2,4-triazolin-5-one as the active ingredient.

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Compounds represented by the general formula (I) may e.g. is made by using Method A, Method B and Method C in the following manner:

Method A

/ S F Q

ci - / "" V,> 'iiH (III) rf ~ \ A

10 / \ / -2 = - * ..Cl-V Vn n-chf- \\ / N \ BaSS O / "ROCCHO CH3 jj / NCH3

I - ROCCHO

ch3 | (XI) CH3 · (where R is the same soin defined above; is a chlorine atom, a bromine atom or an iodine atom).

Method B

F ° ~ 'F

/ ISLAND ISLAND

/ ΓΛ A ”2 A

ci-f Vn n-chf2 rocch-z ^ ci- ^ Vn n-chf2

r H k i r H

HO CH- -ROCCHO CH-

Hase j J

(XV) CH3 (I) 21 (where R is the same as fer defined; Z is a halogen atom).

Method C

FO FO

or K; / '' Λ jl / Cï3 ROCCHO CH3

XCCHO I

f ch3 CH-3

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(where R is the same healthy father defined; X is a halogen atom or a hydroxyl group).

Thus, the L, -1,4,4-triazolin-5-one derivative represented by the general formula (I) may be prepared in connection with Method A by reacting a compound represented by the general formula ( III), in connection with method B by reacting a compound of general formula (IV) with a compound represented by the general formula (V), and in connection with method C by reacting a compound 10 represented by the general formula ( VII) with a compound represented by the general formula (VI), in an inert solvent, in the presence or absence of a basic compound.

The inert solvent used in these reactions may be any inert solvent which does not produce any adverse effects in the reactions, e.g. aromatic hydrocarbons, such as benzene, toluene, xylene or similar aliphatic hydrocarbons, such as n-hexane, cyclohexane or the like; alcohols, such as methanol, ethanol, propanol, ethylene glycol or the like; ketones, such as acetone, methyl ethyl ketone, cyclohexanone or the like; lower aliphatic, acidic esters, such as ethyl acetate or the like; ether, such as tetrahydrofuran, dioxane or the like; lower fatty acid amides, such as dimethylformamide, dimethyl sulfoxide or the like. The solvents indicated may be used singly or in admixture.

Further, when using an alcohol as the solvent of Method C, one may preferably use an alcohol corresponding to a compound represented by the general formula (VI).

The basic compound which can be used in the reactions indicated can be exemplified by inorganic basic compounds, e.g. alkali metal hydrides, such as sodium hydride 4

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or similar; alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide or the like; alkali metal carbonates, such as sodium carbonate, potassium carbonate or the like; alkali metal bicarbonate, such as sodium bicarbonate, potassium bicarbonate or the like; alkali metal alcoholate, such as sodium pyridine, trimethylamine, triethylamine, diethylanilirv, 1,8-diazabicyclo '[5,4,0] -7-undecene or the like.

Reactions of the invention may e.g. is carried out at a temperature of between 0 ° C and 150 ° C to a predetermined temperature.

The reactions in each step are equimolar reactions, and in carrying out these reactions a small excess amount of one reactant can be used for the amount of another reactant.

The reaction time can be selected in the range of 0.5 to 48 hours.

After the reaction is complete, the product in question can be obtained by treating the reaction product in a conventional manner. 1

The compound represented by the general formula (II) used as starting material in Method A can be synthesized using the following reaction steps:

DK 157191 B

-

Cl -V 7— NHNH, R1-A-C = NCOOR2 Λ = / 2 | CH3 (X) ROCCHO I Heat CH3 (VIII)

F

Cl - $ y - NHNHC = NCOOR2 / J Basic compound O / CH-, -

Il / 3 -

ROCCHO

CH3 (X) FO.

¢ 1 - (/ 7 — N NH

\ - / \ / î / N1 ROCCHO CH- in 3 CH3 (II) 19 (where R is the same as father defined; R and R are each a lower alkyl group; A is an oxygen atom or a sulfur atom ).

Thus, a compound represented by the general formula (II) can be prepared by reacting a compound represented by the general formula (VIII) with a compound represented by the general formula (IX) in an inert solvent under heating conditions. wherein the compound thus obtained represented by the general formula (X) is treated during an annealing reaction but a basic compound, with or without separation from the reaction product.

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Further, a compound represented by the general formula (IV) used as starting material in Method B can be synthesized by the following reaction steps:

FO FO

Cl - (^ Vn ^ N-CHF, _ Cl- / ~ ^ -n '^' n-CHFo yw - ^ aV Xch3 ho ch3 (XI) (IV) 5 (where R "1 is the same as father defined) .

In the reaction indicated, instead of using hydrobromic acid, iohydric acid or an alkyl thiolate can be used.

2

Typical examples of β-1,2,4-triazolin-5-one derivatives represented by the general formula (I) are shown in the following Table 1.

F O

A 1 01 - (/ \) - nxn ~ chf9 ο w li / \. "ROCCHO CH- CH3 (I) TABLE 1

Compound No. Physical Properties 94 ζ 1 "H-nD '1» 5192

Z mp 186.1 ° C

3 K mp 119.2 ° C

4 NH2 melting point 92.7 ° C

5 iso-C-H-, ® NH, - mp 157.3 ° C

s // - v 6 (C 2 H 2) ^ NH-oily substance 7

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Compound No. ü Physical Properties 7 (n-C4Hg) 2% H2 melting point 126.5 ° C.

8 CH3- n33 1,5142 9 C2H5- n30 1,5112 5 10 n "C3H7“ nD3, ° M051 11 iso-C3H7- n23'0 ^ 5051 12 n-C4H9- n1 2> ° 1.5031 13 iso-C4Hg - n2'0 1.5011 14 tert-C4Hg- n26'0 1.5009 .10 15 n_C5Hll "n3715 1.4984 16 iso-C5H1] L- n26> ° 1,5002 17 nrc6Hl3-nD8, S ^ 4992 18 C1CH2CH2 - n36 f5 1.5204 19 BrCH2CH2- n * 9'5 1.5291

Melting point 106.5 ° C

21 F3CCH2 “n39'5 1” 4826

22 C1CH2CH2CH2 melting point 87.7 ° C

23 BrCH2CH2CH2 - melting point 83.8 ° C

24 ClCH-CH melting point 68.7 ° C- in CH3

ClchOCHCH «- melting point 95.0 ° C

Z j Z

Cl 26 C1CH9 ^ n £ 4'5 1.5091 / CH-cich2 ^ 2η BrCH melting point 104 ^ 2 ° C.

2 "= CH-

BrCH2 / F, C-. nj9'5 1.4573 2 0 CH— 8

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Compound No. R_ Physical Properties 29 C1CH2CH2CH2CH2 melting point 95.3 ° C '30 0- n * 6'0 1.5130 · 31 (h) - n "' 5 1.5140 5 '32 (ÊV-nj7 · 3, 1,5174

XI

33 CH2 = CHCH2- η28Γ5 ^ 5156 34 CH = CCE2 nD8î5 1 »5192 35 CHECCH2CH2- Hq7 r 5 1,5209 36 CH30 (CH2) 2- nD6T ° 1i5088 10 37 C2H50 (CH2) 2- nD6l ° 15022 38 iso-C3H70 (CH2) 2- η £ 6ι ° 1.4989 39 n-C4HgO (CH2) 2- η26τ ° 1.4878 40 CH3OCHCH2CH2- nD? T5 1 ^ 5009 ch3 41 CH3SCH2- nD8r ° ^ 5279 15 42 CH3S (CH2) 2 - nD6 ^ 5 1r5306 43 C2H5S (CH2) 2- nJ9, S 1? 5274 19 5 44 iso-C3H7S (CH2) 2- nD? 1.5233 1 2 5 45 iso-C4H9S (CH2) 2- 1.5212 46 sec-C4H9S (CH2) 2- nj9'5 tert-C4HgS (CH2) 2- nj ^ 2? 1,5179 48 "CH3S (CE2) 3- nD9'5 ir5299 49 C2H5S (CH2) 3- η09; 5I5203 19 5 50 iso-C3H7S (CH2) 3- nD 'lr5204 9

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Compound No. «Physical Properties 51 n-C4H9S (CH2) 3- n * 4'5 1.5216 '.52 iso-C4HgS (CH2) 3- n * 4'5 ^ 5209 53 tert-C4H9SÎCH2) 3- n * 6'5 1i5172

54 CH 3 S (CH 2) 2 mp 104.5 ° C

0

55 CH₂S (CH₂) mp 99.8 ° C

y \ 2 2 0 0 56 CH30 (CH2) 20 {CH2) 2- n ^ 6 r 0 1.5052

57 CH, 0C-CH mp 108.1 ° C

3 il I

O CH3

58 ch 2 melting point: 82.4 ° C

r - < 'C1

59 ° V - CH 2 melting point -117.5 ° C

Cl 60 Ν ^ Γ ~ ^ - CH2 ~ mp 72, -6. .C; 61 C1-C12-2 melting point, 0.1 ° C;

P

52 'CH 2' mp 115.7 ° C

g3 p - CH2 melting point 80.8 ° C

64 h3C - <[> - CH2 melting point 102.8 ° C: 65 H3CO4 O-CH2 ~ melting point 89.4 ° C: 10

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Connect. Physical Properties

652N - CH2 melting point 126 * 5 ° C

67 C2H5OC-CH2 melting point 135.3 ° C

ISLAND

68 <0> ~ CH2 "nD6f ° 1 r5588 °

Cl

69 Cl - CH2 melting point 163.0 ° C

»^ / Cl

70 V-V "-CH2 melting point 114.7 ° C

Cl CH3 ° \

71 CH₂O-CH₂ melting point = 96.5 ° C

72 -CH- oily suturing L3 73 CH2CH2- oily substance 11

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Next, data in relation to the NMR spectrum of the compounds whose physical properties are characterized as oily substances are shown in the following Table 2.

TABLE 2 PP1 5 Compound NMR (ppm) Part No. 6 1.15 (t, 9H), 1.64 (d, 3H), 2.41 (s, 3H), 2.29 (q, 6H), 4.53 (q, 1H), 7.03 (t, 1H), 7.04 (d, 1H), 7.22 (d, 1H) 72 1.32-1.77 (m, 6H), 2 , 30 (s, 3H), 4.60 (q, 1H), 5.76 (q, 1H), 686 (t, 1H), 6.76-7.31 (m, 7H) ~ ... .......... 73 1.56 (d, 3H), 2.35 (s, 3H), 2.84 (t, 2H), 4.28 (t, 2H), 4, 59 (q, 1H), 6.91 (t, 1H), 6.85-7.32 (m, 7H) The invention will be illustrated more specifically with reference to the following examples. However, the invention is not limited to these.

EXAMPLE 1

Preparation of 1- [4-chloro-2-fluoro-5- [1- (ethoxycarbonyl) o-ethoxy] phenyl] -4-difluoromethyl-3-methyl-1, 1,2,4-triazolin-5-one ( compound # 9) 12

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FO FO

_y h çh3 _ / ji

Cl- ^ y-K / XN ~ CHF2 BrCHCOOC2H5 Cl- ^ V-N ^ SN-CHF2

H f M

CH-li 1 CH-,

J HcC_OCCHO

52 I

(IV) CH 3 13.27 g (0.045 mole) of compound (IV), 9.06 g (0.0498 mole) of ethyl a-bromopropionate and 13.27 (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 room temperature and the undissolved materials were removed by filtration. The filtrate was concentrated and the oily substance thus obtained was dissolved in diethyl ether and washed with cold water, then the diethyl ether solution was dried and the solvent was removed by evaporation to form an oily substance (in reality this oily substance was available). in a clear state, and it was purified by chromatography in a ter sail using a silica gel). Yield: 14.7 g (83.1¾). Refractive index n 15 1.5112.

EXAMPLE 2

Preparation of 1- [4-chloro-2-fluoro-5- [1- (hydroxycarbonyl) -ethoxy] phenyl] -4-difluoromethyl-3-methyl-1, 1,2,4-triazolin-5-one (Compound no. 1) FO FO - / ri λ ^ 20 CI-f VN N-CHF- Cl-V y — N N-CHF -! / H —- ï / "Λ C H OCCHO CH3 hqccHD CH3 • I!

CH3 CH

13

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1.4 g (0.00356 mol) of 1- [4-chloro-2-fluoro-5- [1-ethoxycarbonyl) -ethoxy] phenyl] -4-difluoromethyl-3-methyl-1, 1,2,4-triazulinoline 5-one was dissolved in 50 ml of ethanol, to this solution was added 1.2 g of 20¾ aqueous potassium hydroxide solution, 5 and the whole mixture was stirred at room temperature for 3.5 hours. After the reaction was complete, the reaction mixture was poured into ice water acidified with hydrochloric acid and then the desired product was extracted with ethyl acetate. The extract was washed with water and triturated with anhydrous magnesium sulfate, and then the solvent was removed by evaporation to give 1.1 g of oily substance as the product concerned. Refractive index 1.5192. Yield 84¾.

EXAMPLE 3

Preparation of sodium 2- [2-chloro-5- (4-difluoromethyl-3-methyl-5-oxo- [1,2,4-triazolin-1-yl) -4-fluorophenoxy] propionate (compound # 2)

FO FO

ci - ^ _ ^ - n '/ ^ sn-chf2 - £ = »ci - / ^ - n ^ n-chf2 s Y H o r« V “3

I I

CH3 CH3 0.5 g (0.00136 mol) 1- [4-chloro-2-fluoro-5- [1- (hydroxycarbonyl) ethoxy] phenyl -4-difluoromethyl-3-methyl- / -1 , 2,4-Triazolin-5-one was dissolved in 20 ml of tetrahydrofuran, to this solution was added 0.05 g (0.00125 mole) of sodium hydride and the whole mixture was stirred at room temperature for 10 minutes. . After the reaction was complete, the tetrahydrofuran was removed by evaporation under reduced pressure, and the residue thus obtained was washed with hexane to give 0.37 g of the product concerned. Melting point 186.1 ° C. Yield 76.4¾.

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EXAMPLE 4

Preparation of dibutylammonium 2- [2-chloro-5- (4-difluoro-methyl-3-methyl-5-oxo- [1,2,4-triazolin-1-yl) -4-fluoro-phenyloxy] propionate (Compound # 7)

FO FO

r ~ (X. il 5 Cl-V y- H H-CHF, - s— 01—4 V- N '^ N-CHF.

V = r / \ / 2 \ - / \ / 2 / N ^ \ / N - = \ 0 / \ n-Γ K? / \

Il / CH n C4H9 \ 00 || / W

HOCCHO ** XNH "OCCHO 3

I X -2 I

0.5 g (0.00136 mol) of 1- [4-chloro-2-fluoro-5- [1- (hydroxycarbonyl) ethoxylphenyl] -4-difluoromethyl-3- 4-Triazolin-5-one was dissolved in 20 ml of benzene, to the solution was added 1.0 g (0.0139 mole) of dibutylamine and the reaction was carried out under ice-cooling conditions. was formed during the reaction, collected by filtration and washed with benzene to give 0.51 g of the title compound Melting point 126.5 ° C Yield 79.4% ....

EXAMPLE 5

Preparation of 1- [4-chloro-2-fluoro-5- [1- (propargyloxycarbonyl) ethoxy] phenyl] -4-difluoromethyl-3-methyl-η [-1,2,4-triazoline -5-on (Compound No. 34) 15

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FO Fi u

. _ / ïï / X

ÇX — Û 7 — N N-CHF- ^ OX — sf y-N N-CHF2 yw 0 y h H / CH ® / CH-, V / Cil3 C1CCH0 - - 3 HOCCHO | In CH, CH3. . 3

F O

_ Cl-Z ^^ - N ^ N-CHE, - »

Il / ch3

HC = CCHnOCCHO

2 I

CH3

A mixed solution of 20 ml of thionyl chloride containing 2.7 g of 1- [4-chloro-2-fluoro-5- [1- (hydroxycarbonyl) ethoxy] phenyl] -4-difluoromethyl-3-methyl- ^ -1,2,4-Triazolin-5-one was refluxed under heating for 2 hours. After completion of the reaction, the excess thionyl chloride was removed by evaporation and 2.8 g of 1- [4-chloro-2-fluoc-5- [1- (chlorocarbonyl) ethoxy] phenyl] -4- difluoromethyl-10 3-methyl-1, 1,2,4-triazolin-5-one in quantitative yield.

Then 0.5 g (0.0013 mole) of this compound was dissolved in 20 ml of tetrahydrofuran, to this solution was added 0.2 g (0.00357 mole) of propargyl alcohol and 0.2 g (0.00198 mole) of triethylamine. and then the whole mixture was reacted at room temperature for 2 hours. After the reaction was complete, the reaction mixture was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with an aqueous solution containing 10? Potassium carbonate, then with water, and dried over anhydrous magnesium sulfate, and the solvent was removed by evaporation. The residue thus obtained was purified by dry soybean chromatography to give 0.35 g of 16

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28 5 the product concerned. Refractive index '1.5192. Yield 66.6%.

EXAMPLE 6

Preparation of 1- [5- [1- (tert-Butoxycarbonyl) ethoxy] -4-2-chloro-2-fluorophenyl] -4-difluoromethyl-3-methyl-J / J -1,2,4-triazoline 5-on (compound # 14)

FO FO

/ r <JL / r (k .. y h .h lt / CH3 h I ch,

ClCCHO J (CH3) - COCCHQ. J

i -5 J | CH 3 CH 3 0.58 g (0.00151 mol) 1- [4-chloro-2-fluoro-5- [1- (chlorocarbonyl) ethoxy] phenyl] -4-difluoromethyl-3-methyl-yl 2,4-Triazolin-10 5-one was added in a mixed solution of 0.25 g (0.00338 mol) of tert.-butyl alcohol, 0.14 g (60% in oil, 0.0035 mol) trihydride and 20 ml of tetrahydrofuran. The whole mixture was heated under reflux for 6 hours. After the reaction was complete, the reaction mixture was treated under conditions similar to those described in Example 5 to give 0.13 g of the desired product. Refractive index n ^ * 1.5009. (Yield yield 18.8%.

EKSEHP & - 7

Free positioning of 1- [4-chloro-2-fluoro-5- [1- [C1- (methoxycarbonyl) ethoxy] carbonyl] ethoxyphenyl] -4-difluoromethyl-3-methyl-2 4-Triazolin-5-one (Compound No. 57) 17

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FO * F O

_ / iï .— / Il

Cl-T V-n'n-chf, —-s * Cl-τ '\> _ N 1J-CHF, γ = * w 2 ο o y ^ \ À

i / \ H I II '^ CH

«Oc» 3 CH3OCÇHOCCHO ch3 CH, CHj CH3

A mixed solution of 0.5 g (0.00136 mole) of 1- [4-chloro-2-fluoro-5- [1- (hydroxycarbonyl) ethoxy] phenyl] -4-difluoromethyl-3-methyl- [beta] -1 , 2,4-triazolin-5-one, 0.28 g (0.00136 mol) N, N'-5 dicyclohexylcarbodiimide, 0.02 g (0.000164 mol) 4-dimethylaminopyridine and 10 ml diethyl ether were reacted at room temperature for 6 hours. After completion of the reaction, the insoluble components were removed by filtration and the filtrate was treated by evaporation and the resulting residue 10 was purified by a terrail column chromatography to give 0.41 g of the product in question. Melting point 108.1 ° C. Yield 64.3¾.

EXAMPLE 8

Preparation of 1- [4-chloro-2-fluoro-5- [1- (ethoxycarbonyl) -2-ethoxy] phenyl] -4-difluoromethyl-3-methyl-1, 1,2,4-triazolin-5-one (compound # 9) FO _ ** g αι_ / ΓΛ_Ν ^ ΝΗ -ci- / y-if n-chf,

or H O f ^ H

Il 'CH il / CH o C2H5OCÎfHO 3 ~ C2H5OCCHÔ

CH, J

3 CH 3 0.046 g (0.00134 mole) of sodium hydride was suspended in 10 ml of dried N, N-dimethylformamide, to this suspension was added a solution prepared by dissolving 0.4 g (0.00122 mole) of 1- [4 -chloro-2-fluop-5- [1- (ethoxycarbonyl) etho-2 18

DK 157191 B

xy Iphenyl 1-3-methyl-1, 1,2,4-triazolin-5-one at room temperature. After completion of the dropwise addition, the whole mixture was stirred for 30 minutes and then gaseous monochlorodifluoromethane (CICHF2) was introduced into the mixture at 5 130 ° C for 5 hours. After the reaction was complete, the reaction mixture was cooled to room temperature and the reaction mixture was poured into ice water. The oily material formed was extracted with diethyl ether and the extract was triturated with anhydrous magnesium sulfate. The solvent was removed by evaporation to give an oily material.

This oily material was purified by terrain chromatography to give 0.15 g of the product in question. Refractive index n ^ 1,5112. Yield 32.6%.

EXAMPLE 9 Preparation of 1- [4-chloro-2-fluoro-5- [1- (methylthiomethoxy-v. Carbonyl) ethoxy] phenyl] -4-difluoromethyl-3-methyl-2 \ -1,2, 4-Triazolin-5-one (Compound No. 41)

FO FO

yr (A _ / rA

0.1 - (/ VN N-CHF- _5 = 3 ^ Cl-V VN N-CHF- \ = J \ / 2 \ = / \ / 2 O / N = i O / N = (ii / Λ ii / Λ HOCCHO CH- CH-SCH-OCCHO CH-

| S Ο Δ j J

CHg. CH3

A mixture of 0.5 g (0.00137 mol) of 1- [4-chloro-2-fluoro-5- [1-20 (hydroxycarbonyl) ethoxy] phenyl] -4-difluoromethyl-3-methyl -1,2,4-triazolin-5-one, 1.76 g (0.00128 mol) of tert, butyl bromide, 1.15 g (0.00137 mol) of sodium bicarbonate and 10 ml of terraced dimethyl sulfoxide was reacted without stirring at room temperature for 32 hours. After completion of the reaction, the reaction product was treated using a method similar to Example 8 to give 0.4 g of 18 0 of the product in question. Refractive index n ^ '1.5279. Yield tea 68.7%.

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The ο-1,2,4-triazolin-5-one derivatives of the invention are capable of controlling annual and perennial weed species that grow in rice fields, highland fields, orchards and marshes, e.g. male spore (Echino-chloa crusgalli Beauv., 5 a year-old weed species from the Gramineae family, growing in rice fields and highly injurious), monochoria (Monochoria vagi-nalis Presl, a highly injurious weed species of the Pontede-riaceae family, growing in rice fields ), small-flowered nile grass (Cyperus difformis L., a pernicious. annual weed species of the Cyperaceae family growing in rice fields), spiny marsh (Eleocharis acicularis Romer et Schultes, a typical perennial weed species of the Cyperaceae family growing and also in swamps and waterways), willow leaf (Sagittaria pygmaea Mig., a perennial weed species of the Alismataceae family, growing in rice fields, swamps and grafts), cow lakes (Scirpus juncoides Roxb. was Hotarui Ohwi, a one-year-old weed Cyperaceae family, growing in rice fields, swamps and ditches), wild oats (Avena fatua L., an annual weed species of the Gramineae family, growing on 20 plains, fallow fields and fields on shark), gray birch (A rertmisia princeps Pamp., a perennial weed species of the Compositae family, growing in cultivated and uncultivated fields), large finger axis (Digitaraia adscendcus Henr., an annual weed species of the Gramineae family, a typically highly injurious weed plant growing in fields on moorland and in orchards), Gishi-gishi (Rumex japonicus Houttuyn, a perennial species of the Polygonaceae family, growing in fields on highland and on roadsides), parasol semi-grass (Cyperus iria L., an annual weed plant) Cyper-30 aceae family, growing in fields on meadows and on roadsides), root-rooted quinoa (Amaranthus varidis L., an annual weed plant of the Amaranthaceae family growing on meadows, fallow fields and roadsides) and brood (Xanthium strumarium L. , a one-year weed species of the Compositae family, 35 highly injurious to soybeans).

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reputation

Since the -1,2,4-triazolin-5-one derivatives represented by the general formula (I) exhibit excellent controlling effects on weeds both before and after germination, they are useful as herbicides for soil treatment for 5 and after sowing (planting), for soil treatment during the growing season, for leaf treatment for sowing (planting), for leaf treatment during the growing period of useful crops on hay ridge, such as soybeans, cotton, maize and the like. Furthermore, these derivatives are useful as herbicides applied during the initial and intermediate stages of rice growth in rice fields, and are also useful as herbicides for controlling common weeds, e.g. grows on elevations between rice fields, agricultural paths, waterways, meadows, burial grounds, parks, roads, playgrounds 15, unoccupied areas around buildings, reclaimed land, railways and forests. Herbicidal treatments of such areas are carried out most efficiently and economically when the weed species are not sprouted, but they do not necessarily have to be performed for the sprouting of the weed species.

For the purpose of applying the derivatives of the invention as herbicides, they are generally formulated according to conventional methods of preparing agricultural mixtures and in a form suitable for application. That is, the derivatives of the invention are blended with suitably inert carriers and, if necessary, further blended with adjuvants, in a suitable ratio, and that the mixture is dissolved, dispersed, suspended, mechanical blended, impregnated, adsorbed or adhered. is converted to an appropriate state, e.g. suspensions, emulsifiable concentrates, solutions, wettable powders, dust, granules or tablets.

The carriers used in the agricultural mixtures may be either solid carriers or liquid carriers. Examples of 21

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acceptable solid carriers may be vegetable powders, such as soybean powder, cereal flour, wood flour, bark flour, sawdust, powdered tobacco stalk, powdered walnut shells, bran, powdered cellulose and extraction remnants of vegetables, fibrosis materials, such as paper, corrugated paper and corrugated cardboard , such as powdery synthetic resins, inorganic or mineral products, such as clays (e.g., kaolin, bentonite and acid 1s), talc (e.g. talc and pyrophyllite), silica products [e.g. diatomaceous earth, silica sand, mica and white carbon (a highly dispersed synthetic silica, also obtainable as finely powdered, hydrated silica or hydrated silica, and some commercially available products containing calcium silicate as the main component)], activated carbon , powdered sulfur, pumice, calcined diatomaceous earth, ground brick, fly ash, sand, calcium carbonate and calcium phosphates; chemical fertilizers, such as ammonium sulfate, ammonium phosphates, ammonium nitrate, urea and ammonium chloride; and manure. These solid supports can be used alone or in combination with each other. The acceptable liquid carriers are selected from those solvents for the active ingredients and those which are non-solvent, but which can disperse the active ingredients by adjuvants. Examples of these liquid carriers which can be used alone or in combination are water, alcohols (e.g., methanol, ethanol, isopropanol, butanol, and ethylene glycol), ketones (e.g., acetone, methylethyl ketone, methyl isobutyl ketone , diisobutyl ketone and cyclohexanone), ethers (e.g. diethyl ether, dioxane, cellulose solvents, dipropyl ether and tetrahydrofuran), aliphatic hydrocarbons (e.g. gasoline and mineral oils), aromatic hydrocarbons (e.g. benzene, toluene, xylene, solvent naphtha and alkyl naphthalene), halogenated hydrocarbons (e.g., dichloroethane, chlorinated benzenes, chloroform and carbon tetrachloride), esters (e.g., ethyl acetate, dibutyl phthalate, diisopropyl phthalate, and dioctyl phthalate) amides (e.g.

22

DK 157191 B

dimethylformamide, diethylformamide and dimethylacetamide) and nitriles (e.g., acetonitrile) and dimethylsulfoxide.

The adjuvants exemplified hereinafter are used according to individual purposes. In some cases 5 no adjuvants are used at all.

For the purpose of emulsifying, dispersing, solubilizing and / or wetting the active ingredients, surfactants, e.g. polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene (higher fatty acid) esters, polyoxyethylene resinates, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooeate, alkylarylsulfonates, naphthalenesulfonic acid products, naphthalenesulfonic acid products shark alcohol sulfate esters. In order to stabilize the dispersion, adhesive gelling and / or agglomeration of the active ingredients, the following materials may be used, e.g. casein, gelatin, starch, alginic acid, methyl cellulose, carboxymethyl cellulose, gum arabic, polyvinyl alcohol, pine root oil, rice bran oil, bentonite and lignin sulfonates.

To improve the flow properties of the solid mixtures, it is advisable to use waxes, stearates or alkyl phosphates.

As peptidants for dispersible mixtures, it is also recommended to use naphthalene sulfonic acid condensation products and condensed phosphates.

It is also possible to add antifoaming agents, such as e.g. and silicone oil.

The content of the active ingredients in the herbicidal mixture can. set depending on the uses. For the preparation of powdered or granulated products one can 23

DK 157191 B

usually use 0.5 to 20% by weight of the active ingredients, and in the preparation of emulsifiable concentrates of wettable powder products, usually 0.1 to 50% by weight of the active ingredients can be used.

To destroy various weeds, to inhibit their growth, or to protect usable plants from the damage caused by these weeds, the herbicidal compositions of the invention are used in a weed-destroying dose or a weed growth inhibiting dose or as such. appropriate dilution with or suspension in water or other suitable medium, on the soil or leaves of the weed species in the area where the germination or growth of weed species is undesirable.

The amount of the herbicidal compositions according to the invention to be used depends on various factors such as e.g. the purpose of the application, the weeds in question, the germination or growth state of weeds and crops, the germination tendency of weeds, the weather, the environmental conditions, the form of the herbicidal mixture, the method of application, the type of field to be treated, and the application time. the point and other factors.

When applying the herbicidal mixture in question alone as selective herbicide, it is advisable to select a dose of 1 to 500 g per day. 10 years. On the other hand, when the present herbicidal mixture is applied in conjunction with a combined use of herbicides, the optimum dose thereof is often lower than in the individual application, and the present herbicidal mixture can be used in an amount lower than used above when used in combination with another type of herbicide.

Herbicidal compositions according to the invention are particularly valuable for the treatment of germination and for treating it.

DK 157191 B

Initial germination on highland fields and for early stage and intermediate control of weed species in rice fields. In order to extend both range of controllable weed species and the time within which effective application is possible or to reduce the dose, the herbicidal composition of the invention may be used in combination with other herbicides.

Herbicidal compositions according to the invention can e.g. 10 is used in combination with one or more of the following herbicides.

Phenoxy fatty acid herbicides: e.g.

2,4-D: e.g. ethyl (2,4-dichlorophenoxy) acetate MCP: e.g. ethyl (2-methyl-4-chlorophenoxy) acetate, sodium (2-methyl-4-chlorophenoxy) acetate, and allyl 2- (2-methyl-4-chlorophenoxy) acetate MCBPî e.g. ethyl (2-methyl-4-chlorophenoxy) butyrate Diclofop methyl: methyl 2- [4- (2,4-dichlorophenoxy) phenoxy] propanoate

Diphenyl ether type herbicides: e.g.

Nitrogen: 2,4-dichlorophenyl-4-nitrophenyl ether

Chlornitrofen: 2,4,6-trichlorophenyl-4-nitrophenyl ether Chlomethoxynil: 2,4-dichlorophenyl-3-methoxy-4-nitrophenyl ether

Acifluorfen î 5- (2-chloro-ol, α, α-trifluoro-p-tholyoxy) -2-nitrobenzoic acid and its salts

Fluazifop-butyl: b-utyl - (-) - 2- [4- [[5- (trifluoromethyl) -2-pyridyl] oxyphenoxy] propionate

Triazine-type herbicides: e.g.

Simazine: 2-chloro-4,6-bis (ethylamino) -s-triazine Promethrin: 2-methylthio-4,6-bis (isopropylamino) -s-triazine

Simethrin: 2-methylthio-4,6-bis (ethylamino) -s-triazine and Metribuzin: 4-amino-6-tert.-butyl-3-methylthio-1,2,4-triazin-5 (H) -on 25 '

DK 157191 B

Carbamate-type herbicides: e.g.

Molinate: s-Ethyl-hexahydro-1H-azepine-1-cabothioate S / ep: methyl N- (3,4-dichlorophenyl) carbamate Chloropropham: isopropyl-N- (3-chlorophenyl) carbamate and Benthiocarb: s- (4-chlorobenzyl) diethyl triocarbamate toluidine-type herbicides: e.g.

Trifluralin: (cn, ot, ole-trifluoro-2,6 - dinitro-N, N-dipropyl-p-toluidine and

Pendimethalin: N- (1-ethylpropyl) -2,6-dinitro-3,4-xylidine 10 Herbicides of the acid amide type e.g.

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- (2-15 methoxy-1-methylethyl) acetamide and

Pretilachlor: 2-chloro-2,6-diethyl-N- (2-propoxyethyl) acetanilide

Other types of herbicides: e.g.

Duron: 3- (3,4-dichlorophenyl) -1,1-dinethylurea Bentazone: 3-isopropyl- (H) -2,13-benzothiazine-4- (3H) -one-2,2-dioxide

Pyrazolate: 4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yl-p-toluenesulfonate

Pyrazoxyphen: 1,3-dimethyl-4- (2,4-dichlorobenzoyl) -5-phen-acyloxypyrazole and MY-71: 4- (2,4-dichloro-3-methylbenzoyl) -1,3-dimethylpyrazole-5 yl-p-toluenesulfonate

The following examples illustrate the herbicidal effects and herbicidal compositions of the invention.

30 26

DK 157191 B

Example 1 with herbicide test

Controlling effect on weed species in rice fields in the state diet causes germination.

Pots (1/10 000 years) were filled with soil to simulate 5 rice paddies and seeded from male spores, monochoria, parasol plants and cowleaks, respectively, and with willow root tubers, all of which are harmful weed species growing in paddy fields, and they were conditioned so that they lay in the state of germination.

The soil in the pot was treated with each of the available compounds (listed in Table 1) formulated for a given concentration of liquid by spraying.

After 21 days, the percent control of weed growth was compared to the percent control of the untreated 15 soils and herbicidal activity was determined according to the criterion shown in the following Table 2.

TABLE 2

Criterion for determining activity

Degree of herbicide Percentage control of 20 activity_ weed growth (%) _ 5 100 4 90-99 3 80-89 2 70-79 25 1 less than 70

The seal results are summarized in Table 3.

27

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DK 157191 B

Example 2 with herbicidal intent Controlling effect on weed species on rice fields in the post-germination stage.

Pottery (1/10 000 years) was filled with soil to simulate 5 rice paddy fields and propelled each of the weed species with the foliage age indicated below. In addition, young seedlings of rice plants were transplanted (varie -tet: "Nihonhare") with leaf age 2.5 to the ground on the day of treatment with each of the available herbicides. After 21 days, the herbicidal effect and the degree of degradation damage were evaluated by comparing the results with the results on the untreated soil.

Underseqt weed species The leaf age of the weeds

Hançppore 1 15 Monochoria 2-3

Parasol plants 1-2

Kogleaks · 2-3

Arrow leaf 3

Water cyperus 1-2 20 The criterion for inflicting the damage of the crop is as fallowî H: high (inclusive view) M: medium L: low 25 Nîingen

The criterion for assessing the herbicidal activity is consistent with that used in Herbicide Case Example No. 1. The results are summarized in Table 4.

"32 DK 157191B

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36

Example 3 with herbicide test

Controlling effect on weed species on high-altitude fields in germination stage.

Polyethylene containers of size 10 x 20 x 5 cm (depth) 5 were filled with soil and sown with oats, male spores, large finger axis, rooted quinoa, gray birch, Gishi-gishi, parasol semi-grass and hedgehogs, and the seeds were covered. with soil.

The soil was treated with each of the 10 herbicides in question 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 soil. The criterion for assessing the herbicidal activity is the same as shown in Example 15 1. The results are summarized in Table 5.

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41. '

Example 4 with herbicide formulation

Controlling effect on weed species on shark feature fields in the post-germination stage

Polyethylene containers, whose size was 10 x 20 x 5 cm 5 (depth), were filled with soil and sown with the weed species shown below and soybean seed, and the seeds were covered with soil. The weed species and soybeans were cultured separately to the declining leaf ages and then treated with each of the available active compounds at a given dosage.

After 21 days, the herbicidal effect on the weed species and the degree of degree of damage to the soybeans were evaluated by comparing the results with the results corresponding to the untreated soil.

15 Species of experimental plant Leaves

Oats 2

Large finger axis 2

Radro quinoa ° 1

Grain beet 1 20 Gishi-gishi 2

Parasol semi-grass 1

Brodfra 1

Soybean farthest trifoliate stage

The criterion for assessing the herbicidal activity and of the degree of damage was consistent with those used in Examples 1 and 2 with herbicidal tests. The results are summarized in Table 6.

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Example 1 with herbicide mixture

A wettable powder mixture was prepared by uniform mixing and grinding of falling ingredients:

Compound # 3 50 parts 5 Mixture of 1er and white carbon (wherein 1er is soin major component) 45 parts

Polyoxyethylene nonylphenyl ether 5 parts 10 Example 2 with herbicide mixture

A granular mixture was prepared by uniform mixing and grinding of falling ingredients, by kneading the mixture with an appropriate amount of water and by granulating the kneaded mixture: Compound No. 25 5 parts

Mix of bentonite and 1 part 90 parts

Calcium lignin sulfonate 5 parts

Example 3 with herbicide mixture

An emulsifiable concentrate was prepared by uniform mixing of the following ingredients:

Compound No. 50 50 parts

Xylene 40 parts

Mixture of polyoxyethylene nonylphenyl ether and calcium-alkylbenzenesulfonate 10 parts

Claims (4)

11 CH-, ROCCHO 3! ch3. a 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 substituent n an alkenyl group; an alkynyl group; a lower alkoxyalkyl group; a lower alkylthioalkyl group; a lower alkylsulfinylalkyl group; a lower alkylsulfonylalkyl groupj a lower alkoxyalkoxyalkyl group; a lower alkoxy-carbonylalkyl group; a hydroxycarbonylalkyl group; an unsubstituted benzyl group; a substituted benzyl group having 1 to 2 substituents selected from halogen atoms, lower alkyl groups, lower alkoxy groups, nitro groups, lower alkoxycarbonyl groups, hydroxycarbonyl groups and phenoxy groups; an α-methylbenzyl group or a phenethyl group. 2. A 1,2-triazolin-5-one derivative according to claim 1, characterized in that R is a hydrogen atom; an alkali metal atom; - a quaternary ammonium salt; a substituted alkyl group having halogen atoms as the substituents; an unsubstituted cycloalkyl group; a substituted cycloalkyl group having halogen atoms as the substituents; an alkenyl group; an alginyl group; a lower alkoxyalkyl group; a lower alkyl thioalkyl group; a lower alkylsulfinylalkyl group, a lower alkylsulfonylalkyl group; a lower alkoxyalkoxyalkyl group; a lower alkoxycarbonylalkyl group and a hydroxycarbonylalkyl group; an unsubstituted benzyl group; a substituted benzyl group having 1 to 2 substituents selected from halogen atoms, lower alkyl groups, lower alkoxy groups, nitro groups, lower alkoxycarbonyl groups, hydroxycarbonyl groups and phenoxy groups; the α-methylbenzyl group or a phenethyl group. 3. 1- [4-Chloro-2-fluoro-5- [2- (2-chloroethoxycarbonyl) ethoxy] phenyl} -4-difluoromethyl-3-methyl-1H-1,2,4-thiaziazoline-5 on (compound # 18). 4. 1- [4-Chloro-2-fluoro-5- [1- (2-bromethoxycarbonyl) ethoxy]? phenyl} -4-difluoromethyl-3-methyl-Λ ^ -Ι, 2,4-triazolin-5-one (Compound No. 19). 5. 1- [4-Chloro-2-fluoro-5- [1- (2,2,2-trifluoroethoxycarbonyl) ethoxy] phenyl] -4-difluoromethyl-3-methyl] -1,2,4-triazoline -5-on (compound # 21). 6. 1- [4-Chloro-2-fluoro-5- [1- (3-chloropropoxycarbonyl) ethoxy] -phenyl] -4-difluoromethyl-3-methyl-À-1,2,4-triazolin-5-one ( compound # 22). 7. 1- [4-Chloro-2-fluoro-5- [1- (methoxyethoxycarbonyl) ethoxy] phenyl] -4-difluoromethyl-3-methyl-A ^ -1,2,4-triazolin-5-one (Compound no. 36). 8. 1- [4-Chloro-2-fluoro-5 - [(isopropoxyethoxycarbonyl) ethoxy] phenyl} -4-difluoromethyl-3-methyl-Δ2] 2,4-triazolin-5-one (Compound No. 38 ). 9. 1- [4-Ethyl chloro = 2-fluoro-5- [1- (methoxyethoxyethoxycarbonyl) ethoxy] phenyl] -4-difluoromethyl-3-methyl-N, 1,2,4-triazolin-5-one (Compound no. 56). 1- 1- 4-Chloro-2-fluoro-5- [1- (4-chlorobenzyloxycarbonyl) -ethoxy] -phenyl] -4-difluoromethyl-3-methyl-N 2,2,4-tria -zolin-5-one (Compound No. 61). 11. 1- {4-Chloro-2-fluoro-5- [1- (4-methylbenzyloxycarbonyl) ethoxy] phenyl J-4-difluoromethyl-3-methyl-A-1,2,4-triazolin-5-one ( compound # 64). 12. Herbicidal composition, characterized in that it contains 1- [2,4-triazolin-5-one derivatives according to claim 1 as the active ingredient, together with suitable carriers. »S« o Herbicide composition according to claim 12, characterized in that the active ingredient of A-1? The 2,4-triazolin-5-one derivative of claim 2. · E