JPS59199686A - Pyrazolesulfonylurea derivative, its preparation and herbicide containing the same - Google Patents

Abstract

NEW MATERIAL:A compound of formual I [R is H, COOR' (R' is lower alkyl); Me is methyl; X, Y are H, lower alkyl, lower alkoxy, halogen; X is N=CR<2>- (R<2> is H, halogenated alkyl or may be form an O-containing 5-membered ring together with Y)]. EXAMPLE:N-[( 4, 6-Dimethoxypyrimidin-2-yl )aminocarbonyl]-4-ethoxycarbonyl-1- methylpyrazole-3-sulfonamide. USE:Herbicide: it shows high herbicidal activity with a much less dose than in the conventional. PREPARATIONThe reaction between a pyrazolesulfonyl isocyanate of formula IIand an aminopyrimidine or aminotriazine of formula III is carried out in a sufficiently dried inert solvent such as dioxane to give the compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel pyrazole sulfonyluronide derivatives,
The present invention relates to a method for producing the compound and a herbicide containing the compound as an active ingredient.

JP-A-55-102577 and JP-A-56-139
Publication No. 7166 f'13 describes that pyridine sulfonylurea derivatives are useful as herbicides, and JP-A-56-169688 describes that pyrrolesulfonylurea derivatives are useful as herbicides.

On the other hand, conventional pyrazole derivatives are described, for example, in Japanese Patent Publication Nos. 54-36648, 41872-1972, 2276-1976, 58670-1987, and 133265-1980. It is known that compounds such as ``#'' are useful as herbal agents.

It is essential to use herbicides to protect important crops such as rice, wheat, corn, and rice from weed damage and increase yields. Especially from the viewpoint of preventing environmental pollution and reducing economic costs during transportation and spraying. Since then, research has been ongoing for many years to find compounds that have a high herbicidal effect at as low a dose as possible.Some compounds with these properties are currently used as herbicides, but these properties have not been There is also a need for new compounds with .

Although the above-mentioned pyridine sulfonylurea derivatives and pyrrolesulfonylurea derivatives have excellent herbicidal effects at low doses, they are not always satisfactory, and some of the conventionally known pyrazole derivatives Shows selectivity for rice, but requires relatively high doses;
This also cannot necessarily be said to have satisfactory characteristics.

In order to develop useful herbicides, the present inventors have continued to research over many years and have studied the herbicidal properties of many compounds in order to produce compounds with higher herbicidal power.

As a result, the compound of the present invention represented by the general formula N) was compared with known pyridine sulfonylurea derivatives, pyrrolesulfonylurea derivatives, and pyrazole derivatives against many weeds in soil treatment and foliage treatment. The present invention was completed based on the discovery that it has a significantly stronger herbicidal power even if The compound of the present invention exhibits a high herbicidal activity with a very low level of 1 compared to conventional herbicides, so it is useful as a herbicide for not only υ1 land but also other prefectural orchards and non-arable land.

The compound of the present invention represented by the general formula (+) is a new compound, and can be easily manufactured by selecting one of the following Reaction Formulas 1 to 3.

(1) [In the formula, R, Me, X, Y and Z have the same meanings as above. ] That is, the birazole sulfonyl sardine-1 derivative is generally reacted promptly by adding a sufficiently dried pyrimidine or triazine derivative represented by dioxane or acetonitrile and stirring every 7 times, and the main reaction is completed in Reactions 1 to 1. Invention compound (I) is obtained. If the reaction is difficult to proceed, the reaction can be facilitated by adding a suitable base such as triethylamine, l-lyethylenediamine, pyridine, sodium alkoxide, sodium hydroxide, or the like.

[In the formula, R, X, Y and Z have the same meanings as above. R
3 represents an alkyl group or a phenyl group. ] In other words,
Pyrazole sulfonamide derivative (TV) is reacted with chloroformate or carbonate in a solvent such as acetone or methyl ethyl ketone in the presence of a base such as potassium carbonate, and after the reaction, compound (Vl) is prepared by treating with an acidic substance such as hydrochloric acid. obtain. The compound (1) of the present invention is then heated with the compound (I[) in a solvent such as toluene.
can be IH.

Reaction formula l (IX) [In the formula, R and Me have the same meanings as above. E and F represent a halogen atom, R represents a lower alkyl group, and G represents a nitrogen atom or a CH- group. ] Unexamined Japanese Patent Publication No. 5 6-1
5 4. 4. 7 Referring to Publication No. 1, synthesize the compound (■) which is a part of the compounds of the present invention by reacting the pyrazole sulfonamide derivative (■) with pyrimidine or triazine isocyanate (■), and then synthesize the compound (■) which is a part of the compound of the present invention. Compound (IX), which is also a part of the compounds of the present invention, can also be synthesized by reacting with lard. Pyrazole sulfonyl isocyanate, the raw material used in Reaction Formula 1, is synthesized from pyrazole sulfonamide by the method described below, and further by the method described in JP-A-55-1.
It can be synthesized by referring to the method described in Japanese Patent No. 3266. Although the intermediate pyrazole sulfonamide is also a new compound, it can be synthesized using the synthetic route described below.

1i (1■) [j(width R-Me-X-Yt; +!-HiZ has the same taste as above.] One synthesis example of the intermediate pyrazole sulfanoamide used in the present invention is shown below. The following is described as a reference example.

Reference Example-1 Synthesis of 1-methylpyrazole-3-sulfonamide 1-methyJ(/v-aminopyrasol 32g, concentrated hydrochloric acid 1
20 ml, and parts: 40 ml of acid 1 γ volume 1 night Sodium 11ate 3/1.1 g/1 ζ 1/10
It was added at ゛°C to 0°C. The solution was stirred at -5°C for 30 minutes and then added in small portions to 6.7% chloride. , sulfite scum saturation ffi! : r(i l'r':
440 ml of liquid was added dropwise at 10 to 5'C.

After dropping, stir at 0-5°C for 4 hours with a 4-trowel.
, was poured into ice water and extracted with ether. The extract was thoroughly washed with water and saturated hydrogen carbonate, 1-liu,/- aqueous 1-iso, and dried. Now, I added the sulbonyl chloride that was added to my stomach to 50%
m1 to 18 I'lf, and at a temperature below IO'C, add 150 m of 28% ammonia water! was added under water cooling. After 3 hours of stirring at room temperature, the mixture was concentrated under reduced pressure, and the blue solid was filtered, washed with water and hexane, and dried to give 142 g of the desired product. , melting point 156-15ε('
C Side A Tally 3- 4- Metokey/Punorponyl-1-Methyl Beansole-3-Sugetsuyumi J/7 Synthesis of Mito 3-Ae Rou]-Methyl 1 Pyrazole-4 Carbon 醇Methyl) Mili Reference Return to Example I (7 O: 2 melting point 1
91-1971'C Reference example 1 4-ethoxycarbonyl-1-methylpyrazole-3-
Synthesis of sulfonamide Synthesis was carried out using ethyl 3-amino-1-methylpyrazole-4-carboxylate.

Melting point 1.19-15]°C Reference Example 1~;
The synthesis example will be explained below.
'', j11-j Determination 11. There is no lomo.

Examples・xical-nyl-1-methylpyrazole-,
'3-Sulfonamide 7' 8 g + 'l,j Δ・＞1. ; i Q/, potassium, no, n-butyl sardine in a mixture of 6.90 g and 70 ml of acetone.
1-4, add 1g at room temperature, add and reflux, 31ij.

The mixture was stirred for a while (the reaction was viscous). Acetone was distilled off under reduced pressure (7), ice water was added to the residue, and insoluble matter was filtered. The filtrate was precipitated with hydrochloric acid, and the precipitated crystals were separated by filtration, washed with water, dried, and washed with N -(Summer) Phylcarbamoyl-1-methylpyrazole-3-nurponami F'
ltl. Dry 7g (12, 1~125℃9), dry 1?V: 12Oml of l-luene, add Bofgen 9611 under the flow, and then After 15 hours of drying;
- I was disappointed. Phase nulfonylisocyanate-11.0. 400mg of 2-amino-4,6-simethoxypyrycin
20 mL of dry acetate nitrile was added to Cε, and the mixture was stirred at room temperature. The resulting crystals were filtered, washed, and dried to yield a product of 1.0.

I got it. tl''; point 150-152°C, then ζ >114, and the 111 property of the synthesized compound was determined by the length. ) is combined with the compound synthesized in the example below.
1 (,: The compound of the present invention (111.L) is not shown.

Bottom margin- Table 1 (I) Me: Methyl group Pl: Ethyl group.

- Edges and lower margins 1 When applying the compound of the present invention as a herbicide, it is generally necessary to use a suitable carrier, such as a solid carrier such as clay, talc, bentonite, diatomaceous earth, water, alcohols (methanol, ethanol, etc.), aromatic Hydrocarbonized water Z class (Hensen, toluene, xylene, etc.), chlorinated hydrocarbons,
Ethers, ketones, esters (ethyl acetate, etc.),
It can be applied in combination with a liquid carrier such as acid amides (dimethylformamide, etc.), and if desired, emulsifiers, dispersants, suspending agents, penetrating agents, spreading agents, stabilizers, etc. can be added.
It can be put to practical use in any dosage form such as a liquid, emulsion, wettable powder, powder, or granule.

Next, examples of formulations of herbicides containing the compound of the present invention as an active ingredient will be shown, but the invention is not limited thereto.

In addition, in the following formulation examples, "parts" mean parts by weight.

K gold box 1 Wettable powder Compound of the present invention No. 2
---50 parts Sieglite A ---------
-1.--46 parts (kaolin clay: di-
Kurite Kogyo (+ surface-increasing product name) Tsurupol 5039 -1--2 parts (mixture of nonionic surfactant and anionic surfactant: Toho Kagakusho) product name) Carplex (hardware) Anti-caking agent) ------- 2 parts (White Carphone: Shionogi & Co., Ltd. trade name) or more are mixed and ground to make a wettable powder.When using, add 50 to 50% of the above wettable powder It is diluted 0.000 times and sprayed so that the amount of active ingredient is 0.005 kg to 10 kg per hectare.

1 go] Da J-2 - Hydrating agent Compound of the present invention No. 3 ----------
75 parts Seacrite A --------------
-------- 19 parts (kaolin clay: Zikrite Industries Co., Ltd. product name) Tsurupol 5039 --- 1 ---
--- 2 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Co., Ltd. trade name) Carplex (anti-caking agent) --- 1 --- 4 parts Why 1 - Carbon: Shionogi &Co.'s product name) The above is mixed and pulverized uniformly to make a wettable powder.

Arrangement I Row J - Hydrating agent Compound of the present invention No. 17-----1・----
-50 parts Thetalight A -------------
---4, 6 parts (kaolin clay: Sieglite Kogyo @ Kiku product name) Tsurupol 5039 - ---
−−−−−−−−−2 parts (mixture of nonionic surfactant and anionic surfactant ↑− agent: Toho Chemical (■Product name) Carplex (anticaking agent) −−−− -2 parts (white carbon: Shionogi & Co., Ltd. trade name) or more are uniformly mixed and pulverized to make a wettable powder.

Skin hydration agent Compound of the present invention No. 18-----・--------
---25th part Sea Cry I-A ・-------1-
・−−−1−−−−・−71 parts (Kaolin clay: Sieglite Kogyo η trade name) Tsurupol 5039 --
−−−−−1−−−−−−2 parts (Mixture of nonionic surfactant and anionic surfactant: Toho Chemical 0 trade name) Carplex (anti-caking agent) -2 parts (White Carbon: Shionogi & Co. +l?) Trade name) The above is mixed and ground uniformly to make a wettable powder.

Rin Sen 15 Emulsion Compound of the Invention No. 18
Part 2 -------
−−−−−−−78 parts dimethylborumamide 2−−
−−−−−−15 part crane pole 2680 −−−−−
----~- 5 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Okiku brand name) The above ingredients are mixed uniformly to form an emulsion. In use, the above emulsion is diluted 10 to 10,000 times and sprayed to give an amount of active ingredient of 0.005 kg to 1° kHz per kilogram.

Ki1fi3u-flowable compound of the present invention ll! 0. 3------25 parts Ageliseal S-710 song-10 parts (Nonionic surfactant: Kao Atlas (■Product name) Runonox 1000C---0.5 parts (Anionic surfactant: Toho Chemical fee (trade name) 1% Rhodobol water -------20 parts (thickener: Lone Boulin product name) Water ---1----
−−−−−−−−−−−−−−−・−・−−−−−−−
4, 4, 5 or more parts are uniformly mixed to form a flowable agent.

31 cases - 7 - Granules Compound of the present invention No. 12 ----------
−−− 0, ] part bentonite −−−−−
−−−−−−55,0 parts talc −−−
−−−−−−−−−−After uniformly mixing and pulverizing 44.9 parts or more, adding a small amount of water, stirring and kneading, enlarging the granules with an extrusion type granulator, and drying them into granules. Make it into a drug.

Father Plan - Granules Compound of the Invention No. 13
− 0.5 part bentonite −−−−−−−−
-------55,0 parts talc ---
−−−−・−−−−−After uniformly mixing and pulverizing 44.5 parts or more, adding a small amount of water, stirring and kneading, enlarging the granules with an extrusion type granulator, and drying them into granules. Make it into a drug.

Furthermore, the compound of the present invention may be mixed with other herbicides, various insecticides, fungicides, synergists, etc. at the time of molding or spraying, if necessary.

Other types of herbicides mentioned above include, for example, Farm Chemicals, Handbook (Farm (:chemical)).
s1+andbook) 68th edition (19B 2).

The compound of the present invention can be applied to control various weeds in agricultural and horticultural areas such as fields, paddy fields, and orchards, as well as in non-agricultural areas such as playgrounds, vacant lots, and railway edges, and the amount of the applied drug depends on the application situation. There are differences depending on the application period, application method, target grass species, cultivated crops, etc., but in general, the appropriate amount of active ingredient is about 0.005 to 100 kg per hectare.

Next, the usefulness of the compounds of the present invention as herbicides will be specifically explained in the following test examples.

Some of the compounds of the invention have selectivity for certain crop species.

■Kunji ↓ Testing the weeding effect of soil treatment A plastic box measuring 15cm long, 22cm wide, and 6cm deep (into which the diluvial soil was mailed was placed, and rice, Japanese grass, Japanese grass, Cyperus cyperus, Koakaza, Purslane, Cucophyllacea japonica, and Dogweed) were placed in the box. Mixed seeding, approx. 1.5cmτ°, '1+, f,'!,
, so that the force component increases by a predetermined percentage (this 1-1'
i () 11 cloths were applied uniformly to the fence-11).

11. The drug Noida (4, j' + ii) was diluted with water and sprayed on the entire surface with a small spray.゛11 The herbicidal effect on weeds was investigated according to the following criteria.

Ikiyoshitsuki 3 '11.1 Table 2 (shown here).

'1 sword, J old ((t・5 weeds killed) T 90% or more (almost completely dead) 4-
Weed killing rate 7D ~ 90% 3 I9; q' 4 () ~ 70%
2 - Grass killing 4 20-40 %1 -
Z: Bank immersion ↑-2 5-20 %O weed killing rate
Less than 5% (hardly effective)
! ! l) The above-ground growth V weight of the treated area was measured and determined from the number 2 below. .

Honey ] 5 cm, width 22 cm, depth 6 cm plastic) y,! Put the sterilized i,)I:Mi soil in the box, and spot the weight of rice, 1J kaya, 17 kaza, hakida, nogiku, doggarashi, t--′f: lofushi, daisu, kono, and gi. (Ko-seed Shime 1)
．． 5C4±.

When the various plants reached the 2-3 leaf stage, 77z was applied uniformly to the stems and leaves so that the amount of each component was in a predetermined ratio.

11! ! , Apply the medicine to the cloth (7j゛, dilute the hydrating agent of the above formulation example with water, apply a small spray to the entire surface of the stems and leaves of various weeds, and apply the chemical solution to the entire surface of the stems and leaves after 4 weeks.) Various j, "jJ: Test example -1 for the weeding effect against -+%
'11-Ji'E/ll: (I have made some revisions and inspections accordingly.

The results are shown in Table 3.

tari')
℃I/L Note), ``(J Compound C (Unexamined Japanese Patent Publication No. 56-1)
69688) ≧1c Control compound I! ! +I DC time 1'rn 1984-1025
No. 77 Publication) - Below margin bar 9 Shi - 1 lower 1 ゜ white 7 (3 ko 1") Continued from page 1 ■ Int, C1, 3 identification symbol Office organizer (C0
7D 4911052 39100 311100 ) 0 authors Yoshihiro Iwasawa 722-1 Tsuboi-cho, Funabashi City, Nissan Chemical Industries, Ltd. Central Research Laboratory 0 authors Toshiaki Sato 722-1 Tsuboi-cho, Funabashi City, Nissan Chemical Industries, Ltd. Central Research Laboratory 0 authors Person: Takashi Inokai, Nissan Chemical Industries, Ltd. Biochemistry Laboratory, 1470 Shiraoka-machi, Minamisaitama-gun, Saitama Prefecture 0 Author: Toshihiko Oguchi, Osaka Prefecture, Minamisaitama-gun, Minamisaitama-gun, Shiraoka-cho, Oaza Shiraoka, Nissan Chemical Industries, Ltd. Biochemistry Research Laboratory

Claims (3)

[Claims] (1) General formula (I): [In the formula, R does not represent a hydrogen atom or υC (IOR (R' does not represent lower alkyl).Met: l: represents a methyl group.X and y are each independently a hydrogen) atom,
Low N? <Indicates an alkyl group, a lower alkoxy group, a methylamino group, or a halogen atom, 3) may form a 5i ring structure containing an oxygen atom.] A vilazole sulfonylurea derivative represented by: (2) General formula N; 1 (P in the formula σ represents an atom or C00I? (R represents a lower alkyl group). 艷 represents a methyl group.) sol sulfonyl isocyanate derivative, and the following formula (II): ■ [x and Y each independently represent a hydrogen atom, IlY-class alkyl group, lower alkoxy group, dinotylamino group, or halogen atom, and 7 represents a nitrogen atom or (J,=Cl1
2- (R2 may form a hydrogen atom, a halogenated alkyl group, or a 5-membered ring structure containing an oxygen atom together with Y). ] An aminopyrimidine or amidine,
General formula (■) characterized by reacting /1 lyazine derivative 17 in an inert solvent (i): [In the formula, R is a hydrogen atom or GOOR'(R' represents a lower alkyl group.) shows. Me represents a methyl group. X and Y each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a dimethylamino group, or a halogen atom, and 2 is a nitrogen atom or -CR'(1?"
may form a five-membered ring structure containing an oxygen atom together with a hydrogen hole halogenated alkyl group or y. ) is shown. ] A method for producing a pyrazole sulfonyl derivative expressed as: (3) General formula (I): [In the formula, R is a hydrogen atom or Cool? 1 (1?' represents a lower alkyl group). The luster indicates methyl groups. X
and y each independently represent a hydrogen atom, a lower furkyl group, a lower alkoxy group, a dimethylamino group, or a halogen atom, and Z(,:l: nitrogen atom or -CR2-(
R2 may form a hydrogen atom, a halogenated alkyl group, or a 5-membered ring structure containing an oxygen atom together with Y. ) is shown. ] A herbicide characterized by containing one or more pyrazole sulfonylurea derivatives represented by the following as an active ingredient.