JPS6016964A - Carbazinic acid derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:The 3-chloroacetyl carbazinic acid derivative of formula I [R1- R3 are H, Cl, CH3, C2H5, or -O-C3H7-i; R4 is 1-5C alkyl, benzyl, phenyl or -C2H4-O-R5 (R5 is CH3 or C2H5); Z is O or S]. EXAMPLE:Methyl 3-chloroacetyl-3-(2,6-dimethylphenyl)carbazate. USE:Herbicide effective to a wide variety of weeds such as dicotyledonous weeds (e.g. white-bird's eye, white goose-foot, smartweed, etc.), gramineous weeds, cyperaceous weeds, etc. PREPARATION:The compound of formula I is prepared by reacting the compound of formula II with the compound of formula III at <=10 deg.C in the presence of a base such as pyridine, triethylamine, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a 3-chloroacetylcarbanonic acid derivative represented by the following general formula and a herbicide containing the compound as an active ingredient.

R3 [In the formula, R+ + R2r R3 may be the same or different, and each represents H, CL, CH3, C2H
5゜-0-C3H7-i, R4 is
It represents an alkyl group having 1 to 5 carbon atoms, a benzyl group, a phenyl group, or a -C2H4-C)-R5 group.

R5 represents CH3 or C2H5, and 2 represents an oxygen atom or a sulfur atom. ] The 3-chloroacetylcarbazic acid derivative of the present invention represented by the above general formula is a new compound that has not been published in literature, patents, etc., and as a result of synthesizing it and carrying out various studies, it has been found that it has excellent effects as a herbicide. It was recognized that the

That is, the compound of the present invention exhibits strong herbicidal activity against a wide range of weeds, and when the active ingredient is applied to the weeds just before they germinate or at an early stage of their growth, approximately 1. Within a period of ~2 weeks, a wide range of weeds as described below can be killed.

In addition, by limiting the amount of this compound applied or applying an appropriate application method, specific crops such as corn, potato, sugarcane, peanuts, soybeans, sunflowers, barley, wheat, turgid, paddy rice, cotton, and fruit trees can be treated. It is possible to selectively eliminate weeds in the cultivation field.

Typical examples of the compounds of the present invention include those shown in Table 1.

In addition, the compound is indicated by the symbol in the above general formula.

Table 1 (5) (6) (9) The compound of the present invention can be synthesized, for example, according to the following formula.

Reaction 1 Reaction 2 As the base, tertiary amines such as pyridine and triethylamine, and alkalis are suitable.

It is preferable to use an inert solvent such as solvent habenzene, toluene, chloroform, dichloromethane, dioxane, ethyl ether, or tetrahydrofuran, or a tertiary amine used as a base.

The reaction temperature may be 10° C. or lower for reaction 1, and room temperature for reaction 2.

(10) Typical synthesis examples will be shown below and will be explained in more detail.

Synthesis Example 1 Methyl 3-chloroacetyl 3-(2
,6-dimethylphenyl)carbazate (compound number 12) 2. Triethylamine 22
．． 9 is added and the solution is cooled with ice water. While stirring, 195 g of methyl chloroformate was slowly added dropwise while ensuring that the reaction temperature did not exceed 10°C, and after the addition was completed, it was left to stand overnight. The resulting triethylamine hydrochloride was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain an oil. Adding a small amount of cyclohexane to this and leaving it to stand, methyl 3' (2,
6-dimethylphenyl)carpase 1-33g precipitates as 1 crystal.

NMR (CDCA3) 2.37ppm (s, 6H)
3.67ppm (s, 3H) 5.75pprn (b, ]
, H) 6.65pprn (b, IH) 6.85-7.
10 ppm (m, 3H) methyl 3- (2
, 6-dimethylphenyl)carhalase) 3.99 Dissolve in 1Qme of cyclomethane, and add 2.5 g of chloroacetyl chloride. The resulting crystals were collected by filtration and dried to obtain 38 g of a white powder (compound A12) with a melting point of 165°.

Synthesis Example 2 Ethyl 3-chloroacetyl-3-(p-chlorophenyl)carpazate (compound number 36) 19.2 g of p-chlorophenylhydrazine sulfate was suspended in 300 ml of water, and 400 ml of benzene was added. 8 parts caustic soda aqueous solution under cold water cooling 1.50
ml is added dropwise to obtain a benzene solution of p-chlorophenylhydrazine. Add 9g of pyridine to the benzene solution,
Methyl chlorocarbonate under water cooling 9.5. ! 9 was added dropwise in 30 minutes. Wash with 5 oome of 1% hydrochloric acid water, and wash with water 300111/
! After washing with water, remove the benzene layer and dry with sodium sulfate. This solution was concentrated under reduced pressure to bring the total volume to about 50 CC, and by standing, diethyl (p-chlorophenyl) was produced.
11 g of carbazate was obtained as white crystals.

IR data 3450m-1, 3650m-1, (NH
)1700α-1(co)IMR(CDCt3) 3.
60ppm (s, 3H) 5.8ppm (b, IH) 6
．． 7ppm (b, IH) 6.57-7.3ppm (m,
4H) Ethyl 3-(p-chlorophenyl) obtained above
107 g of carbazate is suspended in a mixture of 8 mg of dichloroethane and 5 ml of tetrasalt carbon, and 8.0 g of chloroacetyl chloride is added at room temperature. It immediately generates heat and melts, producing hydrogen chloride. After the generation of hydrogen chloride has finished, the crystals formed are collected by filtration and washed with 5 Qml of carbon tetrachloride to obtain ethyl 3-chloroacetyl-3-(p-chlorophenyl)carbaze)14. Obtained OJ9.

IR data 3490crn-' (N)l)1670
m'', 1745t1n-'' (C=O) The active compound according to the invention can be formulated into dosage forms such as emulsions, aqueous preparations, pastes, flowable powders, granules, etc. by applying conventional formulation methods. can.

Furthermore, the compounds of the present invention can be mixed with other herbicides. In order to expand the scope of its action, (13) it can be used in combination with agricultural chemicals other than herbicides, such as insecticides and fungicides.

Next, examples of typical dosage forms will be given. "Department" in the description
indicates parts by weight.

Example 1 50 parts of the compounds shown in Table 1 as active ingredients for a wettable powder, 10 parts of diatoms, 35 parts of clay, 3 parts of sodium polyoxyethylene alkyl allyl ether sulfonate, and 2 parts of sodium alkylnaphthalene sulfonate were mixed. It is pulverized to obtain an aquarium containing 50% of the active ingredient compound.

When using, dilute with water to the specified concentration and spray.

Example 2 Granules 10 parts of the compound shown in Table 1, 20 parts of bentonite, 68 parts of clay
1 part and 2 parts of sodium dodecylbenzenesulfonate are mixed together, about 20 parts of water is added, and the mixture is kneaded with a mixer, then granulated through a granulator, and then dried and sized to produce granules containing 10 parts of the active ingredient. get the agent.

(14) Example 3 15 parts of the compounds shown in Table 1 as emulsion active ingredients, 40 parts of dimethylformamide, 40 parts of Xyref and 5 parts of polyoxyethylene argyl allyl ether were mixed to make a homogeneous solution, and the active ingredients were mixed. An emulsion containing Column 15 is obtained. When using, dilute with water to the specified concentration and spray.

Since the novel carbazic acid derivatives of general formula I have excellent herbicidal activity, they are suitable for controlling weeds growing in rice fields, fields, orchards, non-agricultural lands, etc.

When this active compound is applied to the soil surface or mixed into the soil, it can significantly inhibit the growth of weeds and cause them to die. Weeds can also be controlled by spraying the main agent on the stems and leaves of growing weeds.

The dosage of this compound is regulated and the application rate is 1 per hectare.
When the amount is selected to be 10 kg, it can be used as a selective herbicide in cultivated fields such as paddy rice, corn, wheat, barley, sugar cane, soybean, peanuts, sunflower, potato, cotton, or fruit trees. Increasing trench application rates allows for non-selective herbicide applications.

The compounds of the invention can be used to control weeds, for example in the following ways: That is, dicotyledonous plants, such as chickweed (5tel lariamedja), whiteweed (
Chenopodium), Coacaza (Chonop)
odiumficifolium), Japanese knotweed (P
oligonum nodosum), Portulaca: '-
(Portulace oleracea), shepherd's purse (Capsella bursapastoris),
Porippa 1ndica 2, Cardamine Hexuosa,
Marupa morning glory (Ipomoea purpurea)
, Ipologia (5enecio vulgaris),
Aster 5onchus asper, Aster 5ubulatus, Lamium amplexicavle, Oxalis cornicolate, Amaranthus retrofiexus )
, Vicia 5ativa, Galium spurium, Solanum nigrum, Daturastramonjum, Monochoria vaginalis, etc. Plants, such as Poaannus
), Alopeculus ae
Qualis)
sendens), Eleusine 1
ndica), foxglove (5etariavir)
idis), Golden millet (Echinochlor c.
rusgalli), Agropyron
tsukushiensis ), Hosomugi (Lol
ium nerenne), dog wheat (Bromusc)
atharticos), oat (Avena
tatua), toadfish (Polypogon H
lgegaweri), Panicum
dichotomiflorom), Cyperaceae weeds, e.g.
oiria), Cyperus 1
ria), Eleocharis acic
The compounds of the present invention have excellent herbicidal efficacy against a wide range of weeds such as those mentioned above, and are particularly effective when applied to the surface of fields or the foliage of plants immediately before or after the weeds germinate. When sprayed in flooded areas, extremely high pest control effects can be obtained.

Also, when the compound of the present invention is mixed into soil, an extremely excellent weed control effect can be obtained.

In order to demonstrate the herbicidal effect of the herbicide according to the present invention, some representative test examples will be given and explained in more detail (17).

Test Example 1 Pre-emergent soil treatment (pre-emergenc
Weeding effect on plants when using volcanic ash soil in a pot with an area of 100 tyn2, and
), dogfish (Echinochloa crus-
galli), Polygonum
nodosum), Aobi j- (Amaranthu
sretroflexus), corn (Zea
mays), wheat (Triticum aesti)
vum), Phaseolusradia
tus) seeds and cover them with about 50% of soil. Immediately after that, the compounds listed in Table 1 were prepared as an irrigation agent according to Example 1, and this was diluted with water to determine its effectiveness. A dose corresponding to 10k17 of the component per hectare was applied to the soil surface of each pot. Two weeks after treatment, the herbicidal effect on plants was investigated. The herbicidal effect was visually observed and expressed in Table 2 using a 6-level index from O: no effect to 5: complete death.

Test Example 2 Foliar contact treatment (Foliar 5pray
Herbicidal effect on plants when treated (18) Fill pots with a surface area of 100 cn12 with volcanic ash soil, and add Digitaria sanguinalis
), Echinochloa crus-g
Polygonum no.
dosum), Amaranthusre
troflexus), corn (Zea ma
ys), wheat (Triticum aestivu)
m), Phaseolus radiotus
) seeds are sown, covered with soil to a depth of about 1 m, placed in a greenhouse, and when the weeds have 1 to 2 leaves, 1 dose of the hydrating agent of the compound of the present invention is applied.
I) 1000 doses equivalent to 10 kg per hectare
It was diluted with L/ha of water and sprayed using a sprayer. Ten days after the chemical spraying, the test was conducted using the same criteria as in Test Example 1, and the results were expressed using a 6-level index. The test results are shown in Table 3.

Test Example 3 Herbicidal effect on paddy field weeds and phytotoxicity test on paddy rice A pot with a surface area of 120 c/n2 was filled with paddy soil,
Monochoria vaginalis
The seeds of El
eocharis acicularis) and paddy rice weeds at the two-leaf stage were transplanted to two locations each, and the water depth was maintained at approximately 3-fold. Three days later, an aquarium containing the compound of the present invention prepared according to Example 1 was administered into the water in an amount equivalent to 10 kg per hectare.

Three weeks after chemical treatment, the herbicidal effect and chemical damage to paddy rice were investigated. The herbicidal effect and the chemical damage to crops were determined by Test Example 1.
The survey was conducted using the same criteria as the above, and was expressed using a 6-level index. The test results are shown in Table 4.

Table 4 shows that the compound group of the present invention is effective in killing weeds, which are important weeds in paddy fields, such as Japanese grasshopper, Japanese grasshopper, and Japanese grasshopper.

(22) Table 4 Flooding treatment

Claims (1)

[Claims] 1) General formula [In the formula, R1+ R2+ R3 may be the same or different, and each is H, C1, CH31C2H5゜-o
-C3H7-t, R4 is an alkyl group having 1 to 5 carbon atoms, a benzyl group, a phenyl group,
Alternatively, it represents a td -C2H4-0-R5 group. R5 represents CH3 or C2H5, and Z represents an oxygen atom or a sulfur atom. ] A 3-chloroacetylcarbazic acid derivative represented by the following. 2) General formula [In the formula, R1, R2, and R3 may be the same or different, and are H, CL, CH3, and C2Hj, respectively. -o-c3H, -i, and R4 represents an alkyl group having 1 to 5 carbon atoms, a benzyl group, a phenyl group, or a -C2H4-0-R5 group. R5 represents CH3 or C2H5, and 2 represents an oxygen atom or a sulfur atom. ] A herbicide containing a 3-chloroacetylcarbanonic acid derivative as an active ingredient.