JPS5948462A - N-substituted hydrazine derivative and herbicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The N-substituted hydrazine derivative of formula I (R1 is H or halogen; R2 is halogen; R3 is H or 1-8C straight or branched-chain alkyl which may be substituted with lower alkoxy; R4 is lower alkyl; X is O or S; n is 3-6). EXAMPLE:1, 2-Trimethylene-1-ethoxycarbonyl-2-( 2-fluoro-4-chloro-5-ethoxy-carbonylphenylcarbamoyl)-hydrazine. USE:Useful as a herbicide effective at a low dose against the annual weeds such as Deccan grass and broad-leaved weeds, etc. and perennial weeds such as flatstage in paddy field, and broad-leaved weeds of Amaranthaceae family, Chenopodiaceae family etc. in the plowed land. It has no phytotoxicity to rice plant, wheat, soybean, etc. PROCESS:The compound of formula I can be prepared, e.g. by reacting the N<1>, N<2>-alkylene-N<1>-alkoxycarbonylhydrazine compound of formula II with the compound of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION In the present invention, in the formula C, 1 mo represents a hydrogen atom or a halogen atom.
2 is a halogen atom, IT3 is a straight-chain branched alkyl group of (,)I~(zu8), which may be substituted with a hydrogen atom or a lower alkoxy group, and I-(,).

represents a lower alkyl group; Removal characterized by: 1
"

Some N-substituted human ranane derivatives have herbicidal activity.
It is known that there are substances that For example, Tokukai II+'
351 38425 publication, 52-83552 publication,
53-/10785 is published.

As a result of various studies on N-substituted phenyl derivatives, the present inventors surprisingly found that a derivative having a halogen atom at the rose position and a carboxyl group or its ester group at the rose position, as shown in Narita. It was discovered that this herbicide exhibits extremely strong herbicidal activity, has little phytotoxicity to crops, and can be used as a practical herbicide, leading to the completion of the present invention.

The compound of the present invention not only exhibits low medicinal use and excellent herbicidal efficacy against annual weeds such as water level 1 barnyard grasses and broad-leaved 4f grasses, but also against perennial weeds such as water holly, bulrush, black eye, pine cabbage, and turmeric. In addition, it showed strong herbicidal efficacy in upland fields as well, in the -M- Tit against broadleaf pitcher
It was discovered that it has excellent herbicidal efficacy when used in a pot.On the other hand, it has little phytotoxicity against rice, wheat, oats, corn, soybeans, etc., and is useful as a practical herbicide.

The novel N-substituted hydrazine derivative represented by the formula (1) is, for example, as shown below, where 1 mo in the formula (2) c and 1] are the same as in the formula (1).N+, N2 −(2
+ (31 (1) alkylene ~ Nl-alkoxyt)) levonylhytoranes and formula (3) (in the formula
Same as in 1), X represents an oxygen atom or a sulfur atom.The substituted phenyl isocyanate represented by 9 can be obtained by reacting substituted phenyl thiocyanates with KG. This reaction 61 can be carried out by dissolving IX, but it is generally preferable to use 4 parts and 1 part of solvent, and the reaction temperature is generally 0'C~], 0
0 tZ', preferably from 5C to 50C for 20 minutes;
Do this for about 3 hours.

The shortened equation (4) C IT is the same as equation (2))
Shiru (4) (3) YCO (Monday also 4 (6) (1) N I, N 2-alkylene hydrazines and humans (3
) is reacted with the compound represented by the formula (
5) (in the formula J(, □, ■(2, H.3, X is the formula (
After obtaining a compound represented by the formula (same as 3), this and the formula (
6) In formula C, 1 mo 4 is the same as in formula (1), Y represents a
A compound represented by formula (1) can also be obtained by setting l',1.

Examples of inert solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; n-hexano,
1]-Aliphatic hydrocarbons such as hebutane and petroleum ether; alicyclic hydrocarbons such as cyclohexane; chloroform and carbon tetrachloride; halogenated hydrocarbons such as percrene; ketones such as acetone and methyl ethyl ketone Class;
Ethers such as ethyl ether, tetrahydrofuran and dioxane; alcohols such as methanol and ethanol; esters such as ethyl acetate; and amides such as dimethylformamide.

The compound represented by formula (2), which is a raw material, can be obtained by a known method (Japanese Unexamined Patent Publication No. 51-65757). Further, the compound represented by formula (3) is the compound represented by formula (7) (where l
, In2, 2, 1, and 3 are the same as in formula (1)).
9) Substituted anilines and phosgene' represented by formula (8) (in the formula, X represents an oxygen atom or a sulfur atom, and Y represents a halogen atom). ! i:, f is thiophoscene or formula (9
) can be obtained by reacting with trichloromethylchloroforme-1. Although the reaction can be carried out without a solvent, it is preferable to use an inert solvent.
Generally carried out between -20C and the boiling point of the mixture,
Preferably, the temperature is between 0 and 120C. Furthermore, although the reaction is preferably carried out under normal pressure, it is also possible to carry out the reaction using a pressurizing agent or under reduced pressure.

Examples of halogen atoms include chlorine, bromine, fluorine, and the like. Examples of lower alkoxy groups include groups such as methyl and oxy.

Examples of 01-C8 straight-chain or branched alkyl groups include methyl, ethyl, 11-propyl, i-propyl, 1]-butyl, S-butyl, 1-butyl, +1-pentyl, l]- Mention may be made of the following groups: hexyl, 11-heptyl, 1]-octyl, 2-ethylhexyl, ], ]3-dimethylbutyl.

■The lower alkyl group represented by Mo4 is 01-(co,
can include straight-chain or branched alkyl groups,
Examples include methyl, ethyl, 1-copropyl, 1-
Examples include groups such as propyl, n-butyl, and S-butyl.

Examples of the compound represented by formula (2) include ethyl it 2-trimethylenehydrazine-1-carboxylate, 1.2
-methyl tetramethylenehydrazine-1-carboxylate,
(2) 2-Pentamethylenehydrazine Next, specific examples thereof will be shown.

Synthesis Example 1゜1.2-t1) Methylene-1-ethquincarbonyl-nofluponylphenyl-rubamoyl)-hydrazine (compound NL2)], 2-)linothylenehydrazine-1-ethyl carboxylate 2.4 6 FC Dissolve 0.017 mol) in 30 ml of toluene.
．． Add 1/Ip (0.017 mol) and stir at room temperature for 1 hour.

After washing with water and anhydrous sulfuric acid), the crystals obtained by concentrating and drying with IJum were purified by column chromatography using silica gel (developing solvent: hexane to ethyl acetate) to obtain the desired product, 4.29F- (yield: 65 %) has a melting point of 82-83tZ
Obtained as white crystals.

Elemental analysis value C, 6H,, F CI N3 (-9.

Calculated value C: 49.55 11: 4.93 N: IO. 8
3 fruit 4111 value C19.75 11:
4.971 N: 10.91 Note that ], ]2-trimethylenehydrazine-1 Instead of ethyl carboxylate,
The desired product can be obtained in the same manner by using the ll@acid salt and the motriethylamine.

Synthesis example 2.

], 2-trimethylene-1-carboethoquino-2-(4
-Bromo-3-secandabutoxycarbonylphenylthiocarbamoyl)hydrazine (compound 7) 1,, 2-)! J Methylenehydranone-1-
Ethyl nonorboxylate 1.4/11 (0.01 mol) was dissolved in benzene: 30 ml: K fW L , /l-phyromo-3-sepnonodalibutoxylponylinisothiocyanate) 3.1 g'co, Add 9 oi moles and stir at room temperature for 1 hour.

Thereafter, the crystals obtained by concentration were recrystallized from hexane-toluene to obtain the target product 391 (yield 85%), melting point Ll.
Obtained as white crystals with a molecular weight of 9 to 120.50.

Elemental analysis value C, 81-1,, J3r N30. S
Calculated value C: 47.16 JI: 5.27 N: 9.16
Actually it! II Value C:47.08 11:5.
53 N: 9.26 Synthesis Example 3 1.2-teJ-ramethylene-1-ethoxyca/l/ho=2-C/I-chloro-2-fluoro-5-improfoxycarponylnenyl(rubamoyl) ~ hydrazino (Compound Nλ13) J, Dissolve 0.7 (4 (0,00/18 mol) of ethyl 2-tetramethylenehydrazine-I-carboxylate in 20 ml of benzene, and dissolve 2-fluoro-4-chloro-5-isopropoxysilane Rubonylphenyl isocyanate 1.
2. Add IP (0,0048 mol) and stir at room temperature for 15 hours. After that, it was washed with water, dried over anhydrous sodium sulfate, concentrated, and the residue was purified by column chromatography using silica gel (
When purified with developing solvent: hexane-ethyl acetate), the target product was 1.98 V- (yield 992%9, refractive index n, 5152
49 as a yellow oil.

Elemental analysis value C2,, r-123CI F N305 calculated value C: 60.6511: 5.57 N: 10.11 actual
Side value C: 60.94 11. '5.61
N+10.1. d Synthesis Example 4 1.2-tetramethine-1-carbomethoxy-2-C
4-1' 00-3-methoxycarbonylphenylthio-Jyrubamoyl)-hydrazine (compound Nn19) 1. Methyl 2-tetramethylenehydrazine-1-carboxylate 1. /1.3 P (0.01 mol) in benzene 3
0m14 K Dissolution L, 4-chloro-3-methoxy force/
l/pho-ruphenylisothiothiocya-i-t2.2
FC (0.01 mol) was added and stirred at room temperature for 1 hour.

Thereafter, the crystals obtained by condensation are recrystallized from toluene-ethyl acetate and the desired product 2.57 (yield 67%) is obtained as pale yellow crystals with a melting point of 181.5-183.5 U.

Elemental analysis value C,, I-1,8CIN304 S word-1
Calculation A direct C: 4 8. ．． 15 11'
:/1.87 N:1130 fruit 611j
Value C: /18.73 H:4.93 N+1
0.95 Synthesis Example 5 1.2-tetramethylene-1-carboisobutoxy-2
-(2-Fluoro-4-chloro-5-improboxycarponylphenylthiorubamoyl)-hydrazine (compound rI & 134) 1.2-tetramethylene-1-isobutyl carboxylate/
15. Ig-(00255%) with benzea 50 m
TC, 2-fluoro-4-chloro-5-iso7
'Roboxonofluponylphinyl inthiocyanate 7
．． Add 07 (00255 mol) and stir at room temperature for 1 hour. Thereafter, it is concentrated, and the residue is purified by column chromatography using silica gel to obtain the target product 9PC (yield: 767%) as a yellow oil with a refractive index of n: 51.5448.

Elemental analysis value C2 [114□7 CI I-” N, O
4S calculated value C: 52.231-1: 5.92 N: 9.
111 actual value C: 52.51 +1: 5.89 N: 9
．． 16 Synthesis Example 6 1.2-pentamethylene-1-ethoxycarbonyl-2
-C2,4-dichloro-5-isopropoxycarbonylphenylcarbamoyl9-hydrazine (compound Na41
], 2-hentamethylenehydrazine-ethyl J-carboxylate 3.1 q c O, 0], s mol) was dissolved in benzene; Ne-1-4,
9FC0,018 mol) was added and heated at room temperature [1]
1 Stir.

Thereafter, the crystals are washed with water, dried over anhydrous sodium sulfate, and then condensed with 6'2. The resulting crystals are recrystallized from hegizan-toluene to obtain the desired product 4.85FC in a yield of 60%9 as white crystals with a melting point of 68-71C.

Elemental analysis value CI9 H□, C1□N30° Calculated value C:
51.1211:5.64N:9.4 L fruit! I
j value C: 51.32 1]: 5.80 N
:9.37 Synthesis Example 7゜1.2-pentamethylene-1-carboethoxy-2-0
2-Fluoro-4-bromo-5-isopropoxycarbonylphenylthiocarbamoyl)-hydrazine (compound ~
L/l8) ethyl 1.2-pentamethylenehydrazine-1-carboxylate], 7 P CO0.01 mol) in benzene 30
Dissolved in 2-70 ml.

Roboxyluponylphenyl isothiocyanate 3.2
! Add YCO (0.01 mol) and stir at room temperature for 1 hour. The residue obtained by concentrating the groove was purified by column chromatography using silica gel to obtain the desired product 311 (yield: 63
2%) is obtained as pale brown crystals with a melting point of 99-101'C.

Elemental analysis value CI! l H□s 13r P N3αS
Calculated value c: 4653 JI: 5.13
N: 8.56 Actual measurement value C10,441-1:
5.32 N: 8.54 Examples of compounds obtained by the above method are given in Table 1.

Table 1 Next, the synthesis of substituted phenyl isocyanate and substituted phenyl inthiocyanate represented by formula (3) will be specifically explained.

For reference]]]1. Preparation of /l-chloro2-fluoro5-ingloboxylponylphenyl isocyanate (trichloromethylchloroforme) 5.4. meC
o, (1/15 mol) was added to 30 ml of 6 M ethyl, and after cooling to OC, 13.9 mol of 4-chloro-2-fluoro-5-isoproboxinofulvonylaniline
A solution of 6 mol of yco,o) and 25 m6 of ethyl acetate is added dropwise over 15 minutes. After stirring for 1 hour at 0-LoC, keep at reflux temperature for 2 hours. After that, when concentrated, the target product 15.45PC (yield 99.9%) was obtained with a melting point of 41'-4
:', obtained as white crystals of C.

Reference example 2. Preparation of 2,4-dichloro-5-ethoxyluponylphenylthiocyanate-1.2.7I-cyclo-5-ethoxyluponylaniline23. /I'
0.1 mol of thiophosgene) was dissolved in 80 me of thiophosgene after cooling to below 1'C.
F-CO, 13 mol) was added dropwise and stirred at room temperature for 2 hours.
<+: After refluxing for 3 hours, the mixture is concentrated to obtain light brown crystals 2'#-C with a yield of 977%.

The melting point was /I5-716C.

When the compound of the present invention is used as an active ingredient of a herbicide, even if the compound of the present invention is used in one or two devices-1-
Two.

When the compound of the present invention is used as a herbicide, depending on the purpose of use, it is generally used in the field of agrochemical manufacturing, in which a pesticide adjuvant is used to enhance or stabilize the effect. Depending on the method, it can be used in the form of powders, fine granules, granules, wettable powders, flowables, emulsions, etc.

In actual use, these various preparations can be used directly or diluted with water to a desired concentration.

Examples of the agrochemical auxiliary agents herein include carrier C diluent) and other auxiliary agents such as spreading agents, emulsifiers, wetting agents, dispersing agents, fixing agents, and disintegrants.

Examples of "liquid" - q-forms include aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, buknol, and glycol, ketones such as acetone, amides such as dimethylbormamide, sulfoxides such as dimethyl sulfoxide, and methylnaphthalene. , cyclohegylene, animal and vegetable oils, fatty acids, fatty acid esters, etc.

Solid carriers include clay, kaolin, talc, diatomaceous earth,
Shiritsuno, calcium carbonate, Montmorillonai! - Bentonite, feldspar, quartz, alumina, sawdust, etc.

A surfactant is usually used as an emulsifier or dispersant = A:
For example, higher alcohol sodium sulfate 11
, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine, and other anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.

All formulations can be used not only as they are, but also in combination with fungicides, insecticides, plant growth regulators, acaricides, agricultural and horticultural fungicides, soil drinkers, soil conditioners, or nematicides. It may also be used in combination with Fertilizer 81'-1 or other herbicides.

The content of the active ingredient compound in the herbicide of the present invention varies depending on the formulation form, method of application, and other conditions, and in some cases may contain only the active ingredient compound, but usually 05 to 95% (weight). ranges from 2 to 50% (by weight).

When the herbicide of the present invention is used to kill weeds, the amount of use thereof varies depending on the compound used and the place of application, and usually the active ingredient compound per area is 1 to 10 (+7, preferably 3 to 75 V). Be used.

Next, formulation examples of the present invention will be explained in more detail.
The types and mixing ratios of additives are not limited to these, and can be used in a wide range. Note that parts do not refer to parts by weight.

Formulation Example 1 To 50 parts of emulsion compound No. 1:3, 35 parts of a mixture of xylene and medylnafucrene (C1:1) was added and dissolved, and then a mixture of polyoxyethylene alkylphenyl ether and alkylbenzene sulfone decalcification (8°2) was added and dissolved. 15
An emulsion is obtained by mixing 1 part with 1 part.

Formulation Example 2 Powder A powder is obtained by adding 95 parts of clay to 5 parts of Compound No. 24, mixing and pulverizing.

Formulation Example 3 Wettable powder Compound No. 45 (50 parts) was mixed with a carrier consisting of 10 parts of diatom, 2 parts of kaolin, and further added with lauryl sulfate, triuno 2.
! 12. 8 parts of a mixture of 2'-naphthylmethanesulfonic acid triurine was mixed evenly and then ground to obtain a finely powdered water concentrator.

Formulation Example 4 Granules 5 parts of fine powder of Compound No. 6 were mixed with silica grains (16-32 mesh) by using a suitable mixer. ．． A methanol solution of 0.5 parts of polyvinyl acetate is used as a binder and spread on 5 parts of polyvinyl acetate to obtain granules.

The excellent herbicidal activity of the herbicidal compound of the present invention will be explained below using an experimental example.

All experiments were conducted in duplicate, and the results are shown as the average value of each.

Experimental example 1. Water D] Immediately 175.00 before weed emergence
A certain amount of paddy soil is packed in a 0 are Wagner Ponot and used as a planting stock, and the rice fields are planted with Japanese cabbage, Japanese cabbage, Japanese azalea, azalea, azalea, etc.
A certain amount of r-seeds were sown. Furthermore, 3 tubers of Urikawa per pot were buried at a depth of 1 cm below the soil surface layer, and after flooding to a depth of 1.3 cm, 6 tubers of the active ingredient compound of the present invention were added per pot.
The dissection solution adjusted to 251 to 25 g was subjected to MJ treatment in swamp water. After chemical treatment: 30 days The removal effect was investigated on the 4th day.The investigation was conducted according to the following criteria and the results shown in Table 2 were obtained.

*Herbicidal effectiveness index 5: Complete weeding II: Approximately 80% weeding 3: 60% 240% 1:20% 0: No effect Table 2 Experimental example 1 Submergence treatment before weed emergence ・Notes
(1) Broad-leafed: Japanese cypress, azalea, azalea, chickweed (2) Japanese cypress: Tamagayanri 1 Experimental example 2. Paddy field growing season Flooding treatment A fixed amount of paddy soil was packed in a 115,000 are Wagner Ponot to make it into a vegetated state, and a fixed amount of seeds of Japanese millet, Japanese cabbage, woodweed, azalea, Japanese chickweed, and Japanese cypress were sown. Furthermore, three Urikawa tubers were buried in the soil surface layer per bot at a depth of J:sl Ca1l, and three rice fungi (Nihonbare) at the 25-leaf stage were transplanted. The active ingredient compound of the present invention was removed when # was grown at the 2-3 leaf stage. /□The diluted solution was dropped into the submerged water.

30 days after chemical treatment, herbicidal effects and fpy were observed.

were investigated and the results shown in Table 3 were obtained. In addition, the base of the survey was the same as Experimental Example J in terms of herbicidal effect, and the next base in terms of chemical damage was 11.

*Pharmaceutical damage index -, ZuIIr: Treasure, slight damage, slight damage] 11: Medium damage: Ren damage, <: + Urami Table 3 Experimental example 2 Paddy field weed growth period Submergence treatment 3rd table
Experimental Example 2 Paddy field weed growth period, ', g; water treatment Table 3 Experimental row 2 Paddy field weed growth period flooded treatment As seen in the results of Experimental Examples 1 and 2, the compound of the present invention Issued for major annual and perennial weeds. It showed excellent herbicidal efficacy in both pre- and post-treatment and growing-season treatments. Moreover, it was found to be highly safe for paddy rice.

Next, we will show an example of an experiment conducted in a field.

Experimental example: 3 Into a circular plastic case with a diameter of 8C7717〒x8cm　rn, a certain amount of seeds of tlll-(: yam), tlll-(: yam), T. l. The soil surface was covered with soil at a depth of 0.5 to 8 degrees Lcm. After treatment, the plants were grown in a greenhouse and the weeding effect was investigated on the 20th day.The experiment was conducted in duplicate, and the average value for each was determined.The investigation criteria were This was the same as in Experimental Examples 1 and 2, and the results shown in Table 1 were obtained.

Table 4 Experimental example: Experimental example 4 on soil treatment before weed germination A circular plastic case with a diameter of 8 cm and 8 squares (filled with a certain amount of soil in field C) was sown with a certain amount of seeds of crabgrass and chinensis, respectively. 25I, 25g, and 50
The solution diluted to 7-10% was sprayed on the plants.

Actually 1j thrift is 2 consecutive? It was carried out in 1 ill. Yakugekai Jurir
The 20th bite of wheat was investigated using the same investigation criteria as in Experimental Example 1, and the results shown in Table 5 were obtained.

Table 5 Experimental Example 4 Weed Growth Period Treatment Experimental Example 5 Fill a plastic bat measuring 23 cm long, 45 crn wide, and 12.5 cm deep with a certain amount of field soil, and use it to grow cotton, corn, wheat, sunflower, and rice. Spread the core at a constant rate, and make a key with a knee of about 3 cm.
Did.

Immediately, 20 ml of a diluted solution containing the active ingredient compound/product of the present invention adjusted to a concentration of 25 to 507 active ingredients per vat was applied to the surface of the vat using a small sprayer. After treatment, growth is managed in a greenhouse and 2
At around day 0, the extent to which each crop was treated with the filtrate was investigated. The experiment was carried out in duplicate with 1 jll, and the average value of each was determined.

The investigation criteria are the same as in Experimental Example 1, and the results in Table 6 are 14).

Table 6 Experimental Example 5 As is clear from the results of Experimental Examples 3 and 4, the compound of the present invention exhibits an extremely superior herbicidal effect on major weeds in upland fields by pre-emergence treatment and growth treatment. I understand. As is clear from the results of Experimental Example 5 of Katsuda Mi, it does not cause any phytotoxicity to crops and is suitable as a herbicide for upland fields.

Patent applicant: Honkayaku Co., Ltd. 489

Claims (1)

[Claims] (1) Formula (where I (・1 is hydrogen atom or hydrogen atom)・Rogen atom,
I(, 2 is a halogen atom, t3 is C1-C which may be substituted with a hydrogen atom or a lower alkoxy group)
Three linear or branched alkyl groups of 8, ■ (, 4 is a lower alkyl group, N-substituted hydrazine derivative represented by (in the formula, 1 (, 1 is a hydrogen atom or a hydrogen atom),
■Mo2 is...a rogen atom, 1(・3 may be substituted with a hydrogen atom or a lower alkoxy group) C□～
C8 straight chain or branched alkyl group, 1 mo4 represents a lower alkyl group, X represents an oxygen atom or a sulfur atom, and the truncated 1] represents an integer from 3 to 6.N- A herbicide containing a substituted hydrazine derivative as an active ingredient.