TW299330B - 5-hydroxypyrazol-4-ylcarbonyl-substituted saccharin derivatives, herbicidal compositions containing them - Google Patents

Abstract

5-Hydroxypyrazol-4-ylcarbonyl-substituted saccharin derivatives of the formula I (see claim I) where the substituents have the following meanings: L and M are hydrogen, C1-C4-alkyl, or chlorine; Z is hydrogen, C1-C4-alkyl, C3-C6-alkenyl, C3-C5-alkynyl or phenyl; Q is a radical CO-J, J is a 4-linked 5-hydroxypyrazole ring of the formula II (see claim II) where R1 is C1-C4-alkyl and R2 is hydrogen or methyl, and agriculturally customary salts of the compounds I are described.

Description

V. Description of the invention (A7 B7 The present invention is based on a 5-hydroxypyrazol-4-ylcarbonyl-substituted saccharin derivative of formula I Q ^ s〇? 0 where the substituent has the following meanings: L and Μ is hydrogen, Ci-C4 alkyl, Ci-C4 alkoxy, Ci-alkylthio Z is a group, chlorine, cyano, mesylate, nitro or trifluoromethyl; hydrogen 'Ci-"alkyl 'C3-Ce cycloalkyl' C3-Ce alkenyl, C3-C5 alkynyl, Ci-C * acetyl, benzyl or phenyl, where the stupid ring may be unsubstituted or halogen or (^-C4 alkyl Substitute CO-J radical; formula 4-linked 5-hydroxypyrazole ring R2 --- j .--.--- ^ --- (please read the precautions on the back before filling this page) Economy Printed by the Ministry of Central Standards Bureau employee consumer cooperative

HO I R1

II where "is Ci-c4 alkyl, and R2 is hydrogen or methyl, this paper uses the Chinese National Standard (CNS) A4 specification (210 X 297 mm)> A7 B7 5. Description of invention (2) and formula I Commonly used salts of compounds. The present invention further relates to the herbicidal compound containing the compound of formula I, and the method of controlling the growth of the saccharin by the saccharin derivative of formula M. The prior art cannot infer the herbicidal effect of saccharin derivatives. It has long been known that unsubstituted saccharin (o-sulfobenzylidene amide, ie, L, ", 01, and 2 in formula I is ^ 1) is an artificial sweetener. In addition, 4-hydroxysaccharin is also known as sweet Agent (German Patent No. 3 607 343). Saccharin derivatives are also known for the control of harmful organisms, such as JP Publication No. 72/00419, 73/35457 (Fungicide), which is used for pharmaceutical purposes It is also known, such as EP-A 59 4257 and the documents mentioned therein. Heterocyclic compounds with a sulfonamide ring are disclosed as herbicides, and their typical representatives are bentazone ---: --r --- ^ ^-(Please read the precautions on the back before filling out this page) Order 1

Η Printed by the Beigong Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs Ο The purpose of the present invention is to provide novel herbicides. Prior to this, its basic structure can be used for this purpose is unknown. It has now been found that the objects of the present invention can be achieved by the compounds of formula I as defined herein. The compound of formula I is prepared by the chloroform of M formula IV of 5-hydroxypyrazole of formula I and the pyrazole ester formed by Chongjie to obtain the saccharin derivative of formula 1.1. The paper scale is based on the Chinese National Standard (CNS) Α4 specification (210Χ297mm) Α7 Β7 5. Description of the invention (3

----: —: --- ^^ — (Please read the precautions on the back before filling in this page) In the above formula, L, Μ and Z have the definitions described in this article. The first step of the reaction is salination, which is carried out in a known manner, for example, in the presence of proribine, adding chloroform of formula IV to a solution or suspension of 5-hydroxypyrazole of formula I. In this case, it is advantageous to use reactants and auxiliary bases that are approximately equal in moles. In some cases, it may be advantageous to use a small excess (1.2 to 1.5 molar equivalents of the base compound of formula I as the basis). Suitable auxiliary rib bases are tertiary alkylamines, pyridine or alkali metal carbonates, and solvents that can be used are, for example, methylene chloride, diethyl ether, toluene or ethyl acetate. When adding chloroform, it is preferred to cool the reaction mixture to 0 to 101C, and then stir at a higher temperature, such as 25 to 50 ° C, until the reaction is complete.

Purification and separation are carried out in accordance with conventional methods, for example, the reaction mixture is poured into water and extracted with dichloromethane, for example. After drying the organic phase and removing the solvent, the crude 5-hydroxypyrazole ester can be subjected to heavy purification without further purification. For the preparation example of 5-hydroxy% azole benzoate, please refer to, for example, EP-Α 282 944 or US -6-This paper scale is applicable to China National Standard (CNS) Α4 specification (210X297 mm). Printed by the quasi-authorized shellfish consumer cooperative

A7 B7 5. Description of the invention (4) 4,643,757. (Please read the precautions on the back before filling in this page) It is convenient to reconstitute 5-hydroxypyrazolate into 20 to 40 it, in the presence of prosthetic base, in a solvent, with the aid of a cyano compound II agent The compound of formula I.1. The solvent used may be, for example, acetonitrile, dichloromethane, 1,2-dichloroethane, ethyl acetate, or methylbenzene. The preferred solvent is acetonitrile. Suitable auxiliary bases are tertiary alkylamines, pyridines or alkali metal carbonates, which can be used in excess of four times. The preferred auxiliary base is twice triethylamine. Suitable catalysts are, for example, potassium cyanide or 2-methyl-2-hydroxypropionitrile, e.g. K5-hydroxypyrazolate, in an amount of 1 to 50 mol%, especially 5 to 20 mol%. The amount of 2-methyl-2-hydroxypropionitrile added is preferably, for example, 10 mol%. Examples of heavy sisters of 5-hydroxypyrazole benzoate can be referred to EP-Α 282 944 or US 4,643,757, but only potassium carbonate or sodium carbonate in dioxane is used as a catalyst. It is known to use potassium cyanide or 2-methyl-2-hydroxypropionitrile (US 4,695, 673) in similar cyclohexane-1,3-dienol enol esters, but there are no examples in the literature showing cyanide It is especially suitable for Fries recombination reaction of 5-hydroxypyrazole 0-acyl derivatives. The printing of the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs is purified and separated according to known methods. For example, M dilute mineral acid (such as 5SS hydrochloric acid or sulfuric acid) acidifies the decanted mixture and extracts it, such as M dichloromethane or ethyl acetate Ester extraction. During purification, the extract is extracted with a cold 5 to 10¾ strong alkali gold tartrate carbonate solution to bring the final product into the aqueous phase. The aqueous solution is acidified or extracted with dichloromethane to obtain a precipitate of the compound of formula I, dried and the solvent is removed. The 5-hydroxypyrazole of Formula I as the starting material is known, and can be prepared by known methods (please refer to EP-A 240 001 and J. Prakt. Chem. 2JJ5_ This paper size uses Chinese national standards (CNS) M specifications (210X297mm) A7 B7 V. Description of the invention ((1973), 382). 1,3-Dimethyl-5-hydroxypyrazole is a commercially available compound. May M Known method to make formula M saccharin carboxylic acid

L 0 HOOC-+-II I / ΝZO M S ° 2

III (please read the precautions on the back before filling this page) to prepare the starting reactant of formula IV by reacting with sulfenyl atmosphere. Some saccharin carboxylic acids of formula II are known (4-C00H are disclosed in:

Zincke, Liebigs Ann. U992) 231; 5-C00H was revealed in Jacobsen, Chem. Ber. L2_ (1880), 1554; 6-C00H was revealed in. Weber, Chem. Ber. 2l5_ (1982), 1740). In addition, 4-chlorosaccharin-5-carboxylic acid is disclosed in German Patent 36 07 343. The corresponding bromine- or iodine-substituted saccharin derivative A1 of formula A1 can also be used where L, M and Z are as defined above, or when Z is not Η, the paper formula of the compound of formula A2 can be applied to the Chinese National Standard (CNS ) Α4 specifications (210X297 mm) Order · Printed by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

Br, I

S02 V. Description of the invention (6) L u

A7 B7 reacts with carbon monoxide and water or Ci-Ce fermentation under high pressure in the presence of palladium, nickel, cobalt or a transition metal catalyst and alkali to produce saccharin carboxylic acid. Iodosaccharin is known in the literature: 6-iodosaccharin is shown in De Roode, Ainer. Chem. Journal 11 (1981), 231. It is prepared by oxidizing 2-toluenesulfonamide substituted by iodine through manganese compound oxidation, or by reacting amino saccharin through Sandmeyer reaction. Amino saccharin is prepared by embedding the original nitrosaccharin according to known methods. Nitrosaccharin is known (Kastle, Amer. Chem. Journal LL (1889), 184 or DRP 551423 (1930)), or it can be It is prepared from the appropriate nitrobenzene derivative (Liebigs Ann. (1963), 85) or nitrobenzenesulfonamide according to the method disclosed in the literature. For example, when L is methyl and M and Z are hydrogen, the following reaction can be performed: g: ---- r ——: --- ^ > water ----- 1T (please read the back first (Please fill out this page again) Printed by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

HOOC. Co / h2o / N—η catalyst S02 catalyst nickel, cobalt, rhodium and especially palladium may be a metal type or a common salt type of known valence, for example, in the form of a halide, such as pd (: L2, -9-ch3

ch3

This paper wave scale is applicable to the Chinese National Liang Zhun (CNS) A4 specification (210X2_97). 5. Description of the invention (7) A7 B7

RhCU. H2〇; acetate, for example, Pd (OAc) 2; cyanide, etc. May also contain tertiary phosphine complex compounds, metal alkylcarbonyl, metal carbonyl groups, such as C02 (C0) s, Ni (C0) 4, and tertiary phosphine complex compounds, such as (PPh3) 2Ni (C0) 2, or the transition gold complex salt of trisphosphonium. When palladium is used as the catalyst, the transition phosphonium salt complex of tertiary phosphine is the best. The nature of phosphine ligands in this article varies greatly. For example, it may indicate the following: Ρ R1 R2 R3

P Ρ R3 R4 I-: ----- ^-(please read the notes on the back before filling in this page) or where η is 2 3 groups, such as Ci-Ce alkyl, Ministry of Economic Affairs Central Standards Bureau The industrial and consumer cooperatives printed the ethyl or aryl sulfonate, which can be replaced, such as methyl metal or ammonium group. For example, the gold halide salt is C 4 Η β) 3, and the M transition is 0.1 oxy. Arylphenyl. Only need to change, including, the number of groups, such as or 4, and R1 to R4 is a low molecular weight alkylaryl or Ci-C * alkylaryl group, such as benzyl, stupid can be naphthyl, 葸Group, preferably unsubstituted or considering the sentiment of the substituent to the carboxylation reaction, otherwise all inert C-organic groups, such as [^-(^ alkyl COOH. C00M (Μ is for example, alkali gold, alkaline earth >, or oxygen-bonded C-organic groups, such as Ci-Ce alkoxide known method, can be used as a commercial starting material, and PCH3 (CeHs) metal as a reference to 10, especially good phosphine complex, for example Addition of phosphines such as PdCU or Pd (0C0CH3) 2, etc., as mentioned in the literature mentioned in this article, such as P (CeH5) 3, P (n-2 or 1,2-bis (diphenylphosphino) ethyl ether Color, the amount of phosphine used is 0 to 20 mil equivalent, especially 1 to 5. 10 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). · A7 B7 Employee of the Central Sample Bureau of the Ministry of Economic Affairs Printed by the consumer cooperative V. Description of the invention (8) The amount of transitional gold is not important. Of course, due to cost, the starting material of formula A1 or A2 is used as the benchmark. It is used in very small amounts, for example 0.1 to 10 mol% , Especially 1 to 5 mol%. The reaction of water with carbon monoxide and at least equal to mol (based on the starting material of formula A1 or A2) is to prepare formula M saccharin carboxylic acid with K. The reaction water can also be used simultaneously As a solvent, that is, the maximum amount is not important. However, depending on the nature of the starting material and catalyst used, another inert solvent may be used, or the base used for the carboxylation reaction as the solvent, rather than Μ is the reaction part. The appropriate inert solvent for the carboxylation reaction is a conventional solvent, such as hydrocarbons, such as toluene, xylene, hexane, pentane, cyclohexane, ether, such as methyl tert-butyl Ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted acetamide, such as dimethylformamide, super-substituted gland, such as tetra-Ci-CU alkylurea, or nitrile, such as benzonitrile Or acetonitrile. The preferred embodiment of the preparation method is to use one reaction component in excess, especially the base, so no additional solvent is needed. The bases suitable for this preparation method are all the hydrogen iodide or bromine that can be released in the reaction Inert bases combined with hydrogen hydride. Examples of them are tertiary amines, such as triethylammonium, cyclized amines , Such as N-methyl hexahydropyridine or Ν, Ν'-dimethyl hexahydropyridine, pyridine, alkali alkane or alkaline earth alkaloid hydroxide, carbonate or bicarbonate, or tetraalkyl substituted urea derivative Substances, such as tetra-C4 alkyl urea, such as tetramethyl urea. The amount of base is not important, the usual amount is 1 to 10 moles, especially 1 to 5 moles. When the base is used as a solvent at the same time, The amount according to the rule to dissolve the reaction sister part -11-(please read the precautions on the back before filling in this page) ^-. Order-This paper size is applicable to the Chinese National Standard (CMS) A4 specification (210X297mm) Description of the invention (9) Α7 Β7 The volume of printing printed by the Employee Consumer Cooperative of the Central Ministry of Economic Affairs of the Ministry of Economics has increased. Due to cost savings, the use of small reaction tanks and the practical consideration of ensuring maximum contact with the reaction components, excessive excess should be avoided . During the reaction, the pressure of carbon monoxide is adjusted so that C0 is kept in excess of the compound of formula A1 or A2. Preferably, the pressure of carbon monoxide at room temperature is 1 to 250 bar, especially 5 to 150 bar. The carboxylation reaction is routinely performed in batches or batches at 20 to 250 1C, especially 30 to 150 1C. As the batch proceeds, it is preferred that carbon monoxide is continuously injected into the reaction mixture to maintain a constant pressure. The product is isolated from the resulting reaction mixture by conventional methods, such as distillation. The starting materials of formulas A1 and A2 required for reaction are known, or can be prepared according to known methods. In addition, it can also be prepared in a similar manner as shown in Examples 1 to 12. When used, the preferred saccharin derivatives of formula I in which L and M are hydrogen, methyl, methoxy, methylthio, chlorine, cyano, Mesylate, nitro or trifluoromethyl. In addition, L and M are preferably hydrogen, Ci-C * alkyl and chlorine. More preferably, in the compound of formula I, L and M are hydrogen, or one of L and M is hydrogen and the other is methyl or chlorine. In formula I, R1 is preferably methyl, and R2 is preferably hydrogen or methyl. Z special is one of the organic groups mentioned, especially methyl, ethyl, propargyl, ethyl or phenyl. The compounds shown in Table 1 are shown in Table 1. Table 1 shows the particularly good definitions of the substituents related to the groups (whether or not they are combined with other substituents). The compounds of formula I can be used in the form of agriculturally available salts. In general, the nature of the salt is not important. In general, the applicable ones are non-negative compounds of formula I (please read the precautions on the back before filling in this page)-· Order_ This paper size is used in accordance with the Chinese National Standard (CNS) Α4 specification (210Χ297mm) A7 — 299396-— V. Description of the invention (10) Alkaline salts with herbicidal activity. Appropriate alkaline salts are especially alkaline gold salts, preferably sodium and potassium salts, alkaline earth metal salts, preferably calcium, magnesium and barium salts, and transition gold salts, preferably manganese, zinc, and iron Salts, and ammonium salts, which may contain one to three L-C4 alkyl or hydroxy Ci-C 4 alkyl substituents, and / or phenyl or benzyl substituents, preferably diisopropylammonium, tetramethyl Ammonium ammonium, tetrabutylammonium, trimethylbenzylammonium, and trimethyl- (2-hydroxyethyl) ammonium salts, oxonium salts, sulfonium salts, preferably tri (Ci-C4) alkyl hoops , And oxybromide salts, preferably tri- (Ci-Cd alkyl oxidized salts. Compounds of formula I, herbicidal compositions containing them and their environmentally tolerant salts, such as alkali gold elk, alkaline earth gold or ammonium Salt, and amines or other herbicidal compounds can control broad-leaved and grassy weeds in crops such as wheat, rice, corn, rice, and cotton, without causing visible damage to the crop. The effect is especially at low application rates. The variability of the application method of Kaulu, the compound of formula I and the composition containing them can also be used to eradicate weeds in another crop. The applicable crops are as follows: Onion (Allium cepa), Fengli (Ananas coinosus), Luohua I ----; --- ^ '^-(please read the precautions on the back before filling in this page) Order-Ministry of Economic Affairs Central Standard Falcon Bureau negative Printed by the industrial and consumer cooperative Γ is Acs • 1 · 1Λ (ft of ofal • 1 _1 s (ss Π ss et ^ aan έ Γ Γ i ^ BB sc arar caas ani B cci ο P yh 荀 0 0 (Beet stems sweet high Jing, Wucaitou Big Wood £ Red

3 1X This paper scale is applicable to China National Standard (CNS) A4 (210X297mm) Cha Shan Nuo (d blue 1! Igan e, A7 ____B7 V. Invention description (11) Employee consumption cooperation of the Central Standard Falcon Bureau of the Ministry of Economic Affairs Printed walnuts (Carya illioninensis), sticks (Citrus limon), sweet dials (Citrus sinensis), small fruit coffee (Coffea arabica) [Coffea canephora], big fruit coffee (Coffea liberica)], cucumber (Cucumis sativus), Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, soybean (Glycine max), Gossypium hirsutum, [tree Cotton (Gossypium arboreum), grass cotton (G ossypium herbaceum), Portuguese leaf cotton (G 〇ssy P iu in vitifoliuni)], Xiangri Cai (Helianthus annuus), oak hazel (Hevea brasiliensis), barley (Hordeuffl vulgare), hops (Humulus lupulus), bat curtains (batatas), walnuts (Juglans regia), pawn * 3 (Lens culinaris), flax (Linum usitatissimum), Fan 55 (L ycopersic ο n 1 ycopersicum), Xiancai (M a 1 usspp ·), cassava (Manihot esculenta), alfalfa (Medicago sativa), plantain (Musa spp.), tobacco (Nicotiana tabacum) [Yellow Tobacco (N · rustica)], Oil olive (〇lea europaea), rice (0 "yza sativa), golden armor & (Phaseolus lunatus), kidney bean (Phaseolus vulgaris), European spruce (P iceaabies), pine (P inusspp.), Pea (P isum sativum), European sweet cherry (Prunus aviuro), peach (Prunus persica), pear (Pyrus communis), red currant (Ribes sylvestre), grate (Ricinus Communis), Gan M -14-(please read the back first Please pay attention to this page and then fill out this page) * The size of the paper for clothes binding is applicable to the Chinese National Standard (CNS) A4 (210X297mm) 29933〇 V. Description of the invention (12) (S accharum 0 ffi C inarium), rye (seca 1 e C erea 1 e), horse antelope (Solanum tuberosum), sorghum (Sorghum bicolor) [(S. vulgare)], cocoa (Theobroma cacao), red cargrass (Trifolium pratense), wheat (Triticum aestiv um), durum wheat (Triticum durum), S bean (▽ icia faba), grape (Vitis vinifera), and jade shu committee (Z ea mays) ° Furthermore, breeding and / or borrowing genetic engineering methods This compound is used on crops that have developed severe resistance to compounds of formula I. The herbicide compound or active compound can be applied before germination or after gourd germination. If the specific crop is poorly tolerant to the active compound, the application technique of spraying the herbicidal compound with the aid of spray equipment can be used so that the leaves of sensitive crops are not affected as much as possible while the active compound touches the growth at the same time Leaves of weeds under the crop or covering the surface of the soil (post-contact or retention method). Printed by the consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). The compound may contain them The herbicidal composition can be sprayed directly with aqueous solutions, powders, moisturizers, or even high-concentration aqueous, oily or other moisturizers or dispersions, emulsions, oil dispersions, vinegars, spreading compositions, and dispersions. Spray, atomize, spread, disperse or add water in the form of the composition or granules. The form of application depends on the intended use; if possible, the active compound of the present invention should be dispersed as evenly as possible. The auxiliary agents suitable for direct spraying of solutions, emulsions, agents or oily dispersions for the preparation of food are mainly: mineral oils with medium to high boiling points, such as kerosene or diesel oil, and coal tar, and vegetable or animal oils, aliphatic, Annular and aromatic-15-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of the invention (13) Employee consumption cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs to print printed hydrocarbons, such as stone lanthanum , Tetrahydronaphthalene, alkylated naphthalene or its derivatives, alkylated benzene and its derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, Si, such as cyclohexanone, or strong polar solvents, Such as amines, such as N-methylpyrrolidone, or water. Water can be added to prepare aqueous application forms from emulsions, shrinkage liquids, suspensions, agents, wettable powders or water-dispersible granules. To prepare emulsions, ointments or oily dispersions, the material can be homogenized in water, so that it can be dissolved in oil or solvent by means of a wetting agent, adhesive, dispersant or emulsifier. However, it is possible to prepare concentrates suitable for dilution with M water containing active ingredients, wetting agents, adhesives, dispersants or emulsifiers and possible solvents or oils. Suitable surfactants are aromatic sulfonic acid alkali gold, alkaline earth alkane or ammonium salts, such as twenty-four sulfonic acid, phenol sulfonic acid, naphthalene sulfonic acid, and dibutyl naphthalene sulfonate, and fatty acids, alkyl and Alkyl sulfonate, alkyl, dodecyl ether and fatty alcohol sulfate, can also be the salt of sulfonated sixteen seventeen and eighteen alcohol, and fatty alcohol glycol ether, sulfonated naphthalene and their derivatives Condensate of compounds and formaldehyde, Condensate of naphthalene or naphthalenesulfonic acid and phenol and formaldehyde, Polyoxyethyl octyl phenol ether, Ethoxylated isooctyl, octyl or nonyl phenol, alkylphenyl Or tributylphenyl polyglycol ether, alkyl aryl polyether yeast, isotridecyl alcohol, fatty alcohol-ethylene oxide condensate, ethoxylated grate oil, polyoxyethylene alkyl ether or poly Oxypropylene alkyl ether, dodecanol polyglycol ether acetate, sorbitan ester, lignin-sulfite wastewater or methyl vitrin. Powders, dispersing and distributing compositions can be prepared by mixing or combining active compounds with solid carriers. Granules can be prepared by combining active compounds and solid carriers, such as coating, -16-This paper i is applicable to China National Standard (CNS) Α4 specification (210X297mm) '' (please read the notes on the back before filling in This page). Shi Yiding A7 __B7 5. Description of the invention (14) Impregnated or homogeneous granules. The solid carrier is mineral earth, such as silicic acid, silicate, talc, kaolin, limestone, lime, chalk, bole, loess, clay 'dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, synthetic substances & Fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and vegetable products such as yin flour, bark powder, wood chips, and rice hulls, wrapped vitamin powder or other solid carriers. In general, the formulation contains 0.01 to 95% by weight of active compound, preferably 0.5 to 90% by weight. The purity of the active compound used is 90 to 100¾. Preferably 95 to 100 «(based on NMR spectrum). The compound of formula I of the present invention can be formulated according to the following method: I 20 parts by weight of the compound of formula I are dissolved in 80 parts by weight of alkylated benzene, 10 parts by weight of from 8 to 10 moles of ethylene oxide and 1 mole of oleic acid N -In a mixture of an addition product formed from monoethanolamide, 5 parts by weight of calcium dodecanesulfonate, and 5 parts by weight of an addition product formed of 40 moles of ethylene oxide and 1 mole of sesame oil. The solution was poured into and evenly dispersed in 100,000 parts by weight of water to obtain an aqueous dispersion containing 0.02% by weight of active compound. I Dissolve 20 parts by weight of the compound of formula I in 40 parts by weight of cyclohexyl copper, printed by the Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs (please read the precautions on the back and fill in this f) 30 parts by weight of isobutanol, In a mixture of 20 parts by weight of an addition product of 7 moles of ethylene oxide and 1 mole of isooctylphenol and 10 parts by weight of an addition product of 40 moles of ethylene oxide and 1 mole of sesame oil. The solution was poured into and evenly dispersed in 100,000 parts by weight of water to obtain an aqueous dispersion containing 0.02% by weight of active compound. I Dissolve 20 parts by weight of the active compound of formula I in 25 parts by weight of cyclohexanone-17-This paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm). Today, A7 B7_V. Description of the invention (15 ) The Ministry of Economic Affairs, Central Bureau of Standards and Labor under the cooperation of du printing, 65 parts by weight of mineral oil with a boiling point of 210 to 280 C and 10 parts by weight of the addition product formed from 40 mole ethylene oxide and 1 mole grate sesame oil In the mixture. Pour the solution and disperse it evenly in 100,000 parts by weight of water to obtain an aqueous dispersion containing 0.02% by weight of active compound. IV Mix 20 parts by weight of active compound of formula I with 3 parts by weight of diisobutylnaphthalene-α- Sodium sulfonate, 17 parts by weight of sodium sulfonate from sulfurous acid wastewater and 60 parts by weight of powdered aerogel were developed in a hammer mill. The mixture was evenly dispersed in 20,000 parts by weight of water to obtain a spray composition containing 0.1% by weight of active compound. V Mix 3 parts by weight of the active compound of formula I with 97 parts by weight of finely cut kaolin. In this way, a bubu sister compound containing 3% by weight of the active compound is obtained. VI is thoroughly mixed with 20 parts by weight of the active compound of formula I and 2 parts by weight of calcium dodecanesulfonate, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight Parts sodium salt of phenol-urea-formaldehyde condensate and 68 parts by weight of stone oil. Get a stable oily dispersion. The saccharin derivative can be mixed with a variety of other representative herbicidal or growth-regulating active compounds and applied together to increase the scope of action and achieve synergistic effects. For example, the applicable basic components are dioxan, 4bu3, bobenzoxo Derivatives, benzothiadianthone, 2,6-dinitroaniline, N-phenylcarbamate, thiocarbamate, halogenated carboxylic acid, tricropping, amine, gland, biphenyl Bond, tri- 11-keto, ureidimidine, benzofuran derivatives, cyclohexane-1,3-dione derivatives containing alkynyl or carbodiimide at the 2_ position, oxoline carboxylic acid derivatives, thiazole Lin Si, -18 ~ This paper scale is applicable to China National Standards (CNS) M specifications (210X297mm) ---------- ^ Shiyi ------ order --- ^ --- -ί i〆 --- {Please read the precautions on the back before filling out this page). A7 B7 Printed by the Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs V. Invention Instructions (16) Sulfadiamide, sulfonylurea, aromatic Oxy- or aryloxyphenoxypropionic acid and its salts, esters and benzoin and others. In addition, the compound of formula I itself or its sister with other herbicides may be additionally mixed with other crop protection agents and applied, for example, in combination with preparations for controlling harmful organisms or phytopathogenic fungi and bacteria. It is also interesting to mix with mineral salt solution for nutrient loss and trace element deficiency. Non-phytotoxic oils and oil concentrates can also be added. Depending on the purpose of control, the age of pickling, the plants and the growth stage vary, the application amount of active compound is between 0.001 and 3.0 kg of active compound per mu (a.s.), preferably between 0.01 and 1.0. Preparation Example ⑴ 2-Methyl-6-acetamidobenzoic acid 90.6 g (0.6 mol) 6-methyl o-aminobenzoic acid was added to a solution of 24.8 g (0.62 mol) NaOH in 500 ml of water Then, 63.4 g (0.62 mol) of acetic anhydride was added dropwise. After stirring for one hour, the pH of the mixture was acidified with concentrated HC1 to 3 during cooling, and the deposited precipitate was pumped through, washed with M water, and dried under reduced pressure at 501C. Yield: 107 g (0.55 mol), 92¾ of theoretical value, melting point: 189-190 C. ⑵ 2-Methyl-3-nitro-6-acetamidobenzoic acid Take 271 ml of 98¾ nitric acid of 51C, partly add 106 g (0.55 mol) of 2-methyl prepared in ⑴ -6-Acetylaminobenzoic acid. After stirring at 10 ° C for one hour, the reaction mixture was poured into a mixture of 540 g of ice and 270 ml of water. Pumping through the sediment of sediment, with water -19-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm): .--- ^ Ά ------ book --- ^ ---- i i- (Please read the precautions on the back before filling this page) A7 B7 printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Invention Instructions (17) Rinse and dry under reduced pressure at 50 t . Yield: 75.6 g (0.317 mol), which is 58¾ of theoretical value, melting point: 190-1911C. After standing for a long time, the filtrate precipitated the 3-position nitrated isomer yield · 21.3 g (0.089 mole), which is 16% of the theoretical value, melting point: 1 80- 1 82 1 ° ⑶ 2-A 4-Nitro-3-nitro-6-aminobenzoic acid Take 450 ml of 2N NaOH and add 75.6 g (0.317 mol) of 2-methyl-3-nitro-6-acetamidobenzoic acid. The reaction mixture was heated to 95 ° C and stirred at this temperature for one hour. After cooling to 10 ° C, add 425 ml of 2N HC1 to acidify it, suction and filter the deposited precipitate, rinse with K water, and dry it under reduced pressure at 501C. Yield: 50.7 g (0.258 mol), 82¾ of theoretical value, melting point: 183-1 8410. ⑷ Methyl 2-methyl-3-nitro-6-aminobenzanoate Dissolve 49.7 g (0.253 mol) of 2-methyl-3-nitro-6-aminobenzoic acid in 380 ml of acetone, Add 43 grams (0.51 mole) of sodium bicarbonate. Then the mixture was heated to boiling until (: 02 was completely released. Then, at the boiling point of acetone, 35.3 g (0.28 mol) of dimethyl sulfate was added to the produced 2-methyl-3 in two hours -Nitro-6-aminobenzoic acid sodium salt floating solution, followed by refluxing the mixture for three hours, and then cooling it. The mixture was poured into 1.8 liters of water, extracted with M dichloromethane. After drying, the organic was concentrated Layer. The purity of the resulting solid is sufficient -20-This paper scale is applicable to China National Standard (CNS) A4 specification (210X297mm) ---: -------- ^^ ------ order --- „- --- ^ " '· I (please read the precautions on the back before filling in this page) A7 B7 printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (18) for the next NMR (NMR ). Yield: 50 g (0.238 mole), the theoretical value of 94! K, melting point: 92-9 generation ° ⑸ 2-methoxycarbonyl-3-methyl-4-nitrobenzenesulfonate atmosphere temperature Dissolve 58.5 g (0.278 mol) of 2-methyl-3-nitro-6-aminobenzoic acid methyl ester in 280 ml of glacial acetic acid under heat, and pour the solution into 85 ml of concentrated HC1 at 15 to 20 t Medium. Then from 5 to A solution of 19.3 g (0.28 mol) of sodium nitrite in 60 ml of water was added dropwise at 10¾, and the mixture was stirred for 30 minutes at 51 C. The diazonium salt solution was then added dropwise to 374 g of S〇2 containing 14 g of CuCU (Dissolved in 30 ml of water) in a solution of 7 50 ml of glacial acetic acid. After the nitrogen is completely released, the mixture is stirred for 15 minutes and poured into 1.4 liters of ice-water. Ml. 2 liters of dichloromethane is extracted into the sulfonamide. The organic layer was dried and concentrated to obtain 73 g (0.25 mol, 90¾ of theoretical value) of oil, which was determined to be purified by NMR (CDCU) 2-methylcarbonyl-3-methyl-4-nitro Benzenesulfonyl chloride. ⑹ 4-methyl-5-nitrosaccharin extract 104 ml of 253L ammonia solution, add 100 ml of water, then add 48.7 g (0.166 mol) of 2-methoxy at 10 ° C dropwise A solution of carbonyl-3-methyl-4-nitrobenzenesulfonate in 70 ml of tetrahydrofuran. After stirring at 25 C for three hours, the mixture was concentrated on a rotary evaporating dish, M was removed of water and THF, and ethyl acetate was used The residue was stirred, filtered with suction and rinsed with ethyl acetate. It was dried under reduced pressure to obtain 34 g (0.131 mole, theoretical value of 79¾) white solid, melting point: 312 ° C (decomposition). ⑺ 2, 4-Dimethyl-5-nitrosaccharin-21-The paper size is suitable for Chinese National Standard (〇 奶) 8 4 specifications (210 father 297 mm) (please read the back Please pay attention to this page and then fill out this page) Find A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs i, Invention Instructions (19) In the presence of NaOH, dimethyl sulfate can be used to methylate the saccharin obtained in ⑹ preparation. (8) 3-Methyl-4-nitro-2- (N'_methyl) carboxamide-N-methylbenzylsulfonamide Pour 50 ml of water into 50 ml of 40¾ methylamine solution, and then A solution of 24.3 grams (83 millimoles) of 2-methoxycarbonyl-3-methyl-4-nitrosulfonic acid in 35 liters of THF was added dropwise at 10 ° C. After stirring at 25¾ for one hour, remove all volatile components on a rotary evaporating dish. The residue was extracted with K ethyl acetate, and the organic layer was washed with M water, dried and concentrated. After standing for a long time, the residue remained crystalline. Yield: 10.3 g (40 millimoles, 48% of theory), melting point: 125-126 ^: melting point after recrystallization of ethyl acetate: 144-145. ⑼ 4-Methyl-5-aminosaccharin Dissolve 33.6g (0.13mol) 4-methyl-5-nitrosaccharin in 1.2L of water heated to 45 ° C, add 5g of Pd / C (in activated carbon On 10: «). Hydrogen gas (pressureless hydrogenation) was added with vigorous stirring. Absorb 9 liters of hydrogen in 4.5 hours. After cooling to 25P, the catalyst was filtered, and the filtrate was concentrated to 200 ml of 稹, and then acidified to pH 1. The accumulated precipitate was filtered by suction, rinsed with M water, and dried under reduced pressure at 50C. This gave 23.4 g (0.11 mol, 85¾ of theory) as a white solid, melting point: 272-27 3 1C. ⑽ 4-Methyl-5-iodose extract, a mixture of 205 liters of glacial acetic acid, 160 liters of water and 40 ml of concentrated HC1, add 23.4 g (0.11 mol) of 4-A-22-this between 15-20¾ stirring The paper standard is in accordance with the Chinese standard (CNS> A4 specification (210X297mm) (please read the precautions on the back before filling in this page). Order A7 B7 Printed by the Employee Consumer Cooperative of the Central Provincial Bureau of the Ministry of Economic Affairs 20) Amino-5-aminosaccharin. 7.9g (0.115mol) of nitrite was added dropwise to the resulting suspension at 5-10C and stirred at 51C for 30 minutes. The diazo contained in the suspension The salt is partially added dropwise to a solution of 19.1 g (0.115 ng) of potassium iodide heated to 50 "in 170 ml of water to form nitrogen gas. After cooling to room temperature, the deposited product is separated by suction filtration and M water Rinse and dry under reduced pressure at 5010. Obtained 32.5 g (0.1 mol, 91¾ of theoretical value) solid, melting point: 257 -258 ¾ ° Combustion analysis revealed that its iodine content was 38.5¾ (39.3 of theoretical value). The purity of this product is sufficient for the next reaction. Α1) 4-methyl saccharin-5-carboxylic acid will be 6.4 g (0.002 mol) 4- Yl-5-iodosaccharin was dissolved in 70 ml of tetramethylurea and 30 ml of water, and reacted with 0.7 g of bis (triphenylphosphine) palladium chloride, heated to 1001 in a 300 l autoclave at 100 bar Stir for 36 hours under the pressure of carbon monoxide. «After the mixture, the water and tetramethyl urea are removed by high vacuum distillation, purified and separated. The residue of M third butyl ether methyl ester (MTBE) is sucked and extracted with M NaHCO 3 solution, After acidification of MHCI, extraction with MMTBE. After concentration, 2.8 g (theoretical value of 58304-methyl saccharin-5-carboxylic acid. ^ NMR (DMS0, 400.1 MHz): 2.85 (3H, s); 8.05 (1H, d) ; 8.2 (1H, d); 13C NMR (DMSO, 100.6 MHz): 167.4 (CO); 161,3 (CO); 141.6 (four-level C); 139,7 (four-level carbon); 138.7 (four-level carbon) ); 135.6 ((: 11); 125.4 (four-grade carbon); 118.5 ((: 10; 15.4 (CH3). -23-'This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210Χ297 mm)' (Please read the precautions on the back before filling in this page) Order V. Invention description (21 A7 B7 Printed 2,4-dimethyl saccharin-5-carboxylic acid by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, 7.3 g (0.02 Mohr) 3 -Methyl-4-iodo-2-(^-methyl) carboxamide-N-tosylamide, together with 0.69 g of bis (tribenzylphosphine) palladium chloride, 30¾ liter of water and 70 ml of tetramethylurea Place in a 300 ml autoclave, heat the mixture to 100T, and stir for 36 hours at 100 bar carbon monoxide pressure. After purification and isolation according to the method described in 02), 4.1 g of the target compound (0.014 mol, 72X of theoretical value) was obtained. XW NMR (DMS0, 400.1 MHz): 2.9 (3H, s); 3.15 (3H, s); 8.2 (2H, 2d); 14.0 (1H, s) 13C NMR (DMSO, 100.6 MHz); 167.3 (CO): 158.6 (CO); 139.7 (level C); 139.1 (level C); 138.9 (level C); 135.5 (CH); 124.6 (level C); 119.0 (CH); 22.9 (CH3); 15.6 ( CH3). 4-Amino-3-methyl-2- (N'-methyl) carboxamido-H-methyl-benzylsulfonamide is similar to the method of ⑼, the pressureless hydrogenation ⑻ obtained 3- Yl-4-nitro-2- (N'-methyl) carboxamide-H-methyl-benzenesulfonamide. The resulting stupid amine derivative has the formula h2n

nhch3 SO2-NHCH3 -24-This paper scale uses Chinese National Standard (CNS) A4 specifications (210X297mm) ---.--.--- ('' 41-- (please read the precautions on the back and fill in This page) Order V. Description of invention (22 A7 B7

Yield 9 3! K, melting point: 2 1 7-2 1 8 it. 3-Methyl-4-iodo-2- (Ν'-methyl) carboxamide aminomethyl-benzenesulfonamide according to the method shown in ⑽ the compound S shown above is nitrided and reacted with KΙ to convert it Formed into the iodine stupid derivative of the following formula. Yield: 95¾ of theoretical value, melting point: 60-62C ch3 〇

nhch3 SO2-NHCH3 (please read the precautions on the back before filling in this page). ^ Ordered by the Ministry of Economic Affairs Central Standards Bureau Beigong Consumer Cooperative to print 09 2,4-Dimethyl saccharin-5-carbochloride. Will be 3.8g (14.9 mmol) 2,4-dimethyl saccharin-5-carboxylic acid was suspended in 100 ml of toluene, the mixture was heated to 80Ό, and 3.5 g (29.8 mmol) of thionyl chloride was added dropwise. After refluxing for two hours, the solution was decanted hot and the reaction mixture was concentrated on a rotary evaporating dish. The resulting product (3 g, theoretical value 74¾), melting point: 149-150 t. Q0 General Preparation Method for Compounds of Formula I 16.1 K Saccharin Carboxylic Acid Induces 5-Control Group-1,3-Dimethylpyrazole to 1.01 g (11 mmol) triethylamine to 1.12 g (10 mmol) (Mol) 5-hydroxy-1,3-dimethylpyrazole in 70 ml of dichloromethane suspension. Then at 25 ° C, add 10 millimoles of IV chlorinated chloride at 25-the size of the paper and use the Chinese National Standard (CNS> A4 specification (210X297 mm) A7 B7 V. Invention description (23) 30 ml Solution or suspension in dichloromethane, then heat the reaction mixture to 45¾ for five hours. After cooling to 25 ° C, treat with 60 ml of water, pour into a separatory funnel, and separate the organic layer. Μ 50 ml of dichloromethane After extracting the aqueous layer, combine the organic layer and dry over sodium sulfate. After filtering and removing the dichloromethane, an oily substance remains, which is used in Chongjie without further purification. 16.2 The pyrazolate economy obtained in 16.1 Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Education (please read the precautions on the back before filling this page) Take the 5-hydroxy-1,3-dimethylpyrazole saccharin carboxylic acid 0-acyl ester obtained in 16.1 (about 10 millimoles) was placed in 80 ml of acetonitrile. First, M2.7 ml (2.2 g = 20 mmol) of triethylamine was reacted with it, and then 0.2 g (2.3 mmol) of 2-methyl-2- The hydroxypropionate reacted with it and the reaction mixture was stirred at 25C for 16 hours. Then 30 g of 5¾ HC1 was poured into the reaction The mixture was extracted with M dichloromethane. Then the organic layer was extracted with M 5¾ potassium carbonate solution, the organic layer was discarded, concentrated HC1 was added dropwise to acidify the alkaline layer to pH 1, and a sticky substance was precipitated. The following purification was carried out: Dissolve in dichloromethane, rinse the solution with M water, dry over sodium sulfate, and concentrate it. After washing with M diethyl ether / petroleum ether, the residue forms crystals. The compounds shown in Table 1 can be prepared according to the M method: -26 -This paper standard uses the Chinese National Standard (CNS) Α4 specification (210Χ 297mm)

Ri

(Please read the precautions on the back before filling out this page), -ιτ Printed by the Ministry of Economic Affairs Central Bureau of Accreditation Consumer Cooperatives 1.16 ch3 ch3 6 HH ch3 > 200 iH-NMR {CDCI3, 200 MHz): 2,05 (s, 3H); 3,24 (s, 3H); 3,52 (s, 3H); 8,04 (d, 1H); 8,13 (m, 2H). 1.17 c2h5 H 5 4-ch3 H ch3 145-147 1.18 ch3 ch3 5 4-CH3 H i-C3H7 195-196 1.19 ch3 CH3 5 4-CH3 7-CH3 ch3 85-88 1.20 ch3 H 5 6-CH3 7-CH3 C2H5 195 1.21 ch3 ch3 5 6- CH3 7-CH3 C6H5 223 1.22 C2H5 H 5 6-CH3 7-CH3 ch3 168-170 1.23 ch3 ch3 5 6-CH3 7-CH3 ch3 188 1.24 ch3 ch3 5 6-CH3 7-CH3 i_C3H? 201 1.25 ch3 H 5 6 -CH3 7-CH3 1-C3H7 115 1.26 ch3 H 5 6-CH3 H Allyl 178 _ 27-The paper size is applicable to the Chinese National Standard (CNS) A4 said grid (210 X 297 mm) Patent Application Tea No. 84 1 08049 Amendment page of the Chinese manual (August 85) Amendment Λ 5. V. Description of the invention (/) The use example can use plastic flower pots as _ raising utensils according to the following greenhouse test display, 3 3: Humic soil. When sown separately in the pre-emergence test by species, the active compound sown and grown in water or emulsified in water, and then transparent on the cover to make the plant germinate evenly (if it is) ° After the gourd test, plant first Depends on growth morphology), and then or emulsion treatment. In this experiment, sowing and seeding in the dish can also be transferred to the culture vessel separately. Gourd kg active ingredient / mu. At 10 to 251C or 20 to 35, the inspection period is 2 to 4 times longer. During this period of rebellion. Graded from 0 to 100. In this paper, the part on the surface M is completely destroyed, the herbicidal effect of the saccharin derivative: which contains loamy soil as the substrate, with the seeds of the tested plants. Then directly disperse the floats for tube guns with fine dispersion. Lightly moisten the culture vessel to promote the plastic cover until it grows. Cover the test plants to a height of 3 to 15 cm if they are not negatively affected by the active compound (the test plants can be planted directly in the same incubator with the active compound in the water and then tested before and after the test) The application rate is 0.5 or 0.25 to maintain the species-specificity of the plant. Observe the plant and evaluate its individual treatment. 100 means that the plant has not germinated or at least at least 0 means no damage or normal growth. (Please read the notes on the back first The matter will be written on this page). Packing and ordering. Printed by the Ministry of Thread Economy, Central Bureau of Industry and Commerce, Beigong Consumer Cooperative. 28 This paper size is applicable to China National Standards (CNS) Α4 specifications (210 × 297 mm) Announcement ί 丄 9330 Application Date 84.08.02 Case No. 84108049 Category Ao / a fTll 丨 p The above descriptions are filled out by this) ^ * 1 «Vi —— A4 C4 (August 1985 Revision Page 299330 U Patent Specification

I name

English essentials do not substitute for the preparation of the control system through its carbonyl group, the 4-group method of pyrazolone pyridone prepared by the control of the other compound with sugar content and growth of the plant's cirii? D? IYiYRAZ0L'4-YLCARB0NYL -SUBSTITUTED rn £ pSi? I? NS〇RIVATIVES > HERBICIDAL C0NTAIKING THEM, METHODS OF tu2I, u ^ ING undesired PLANT GROWTH USING THEM AH0 PROCESSES FOR PRRPARTNfi THFM " Name * 1 State borrowed Des Rasemur Hamachica 6 7 8 9 Andes. Ji 05 Laa Anfkop • Multi. • Kenfin Kaman Deft. Tebivo Swuha 12 3 4 5 Gibrenjit. • Valan Finsweto European outfit

Name (name) of residence in Germany 2 3 4 5 6- 8 9 No. 24 Street No. 82¾ No. Berber Street Ϊ 1676 Dentist Street Street Lanta: 5 Handley 4 Manlebz Luke 3. Buji City Buckwheat City F City D City Jeho City Keta City Fort City Gihan Lance Schneider Tribber Bosfa Newwarman Sea Aleo China Blessed Country Blessed Country Blessed Dede Dede Dede De Lide Commercial Bardez Pigment Chemical Plant No. 3 ΊΧ 街 -Keller No.-Street 4 Line of the Ministry of Economic Affairs Central Standards Bureau Another Industrial Consumer Cooperative Printed the Applicant's Nationality Residence and Residence (Office) Representative Name No. 3, Karl-Persian Street, Safin City, Laoen, Laohe, Germany; ί | This paper uses Zhongguan Household Materials (CNS) A4 (210X297)

Claims (1)

Amendment to Bismuth 8: Ambiguity Supplementary Notice No. 84108049 Patent Application L Scope Amendment (August 1985) Application for patent range of 5-hydroxypyrazol-4-ylcarbonyl-substituted saccharin derivatives L of formula I 0 NZ where the substituents have the following meanings: L and M are hydrogen, Ci-C ^ alkyl, or chlorine; Z is hydrogen, C: -L alkyl, C3-Ce alkenyl or phenyl; Q is C0 -J group; J 'is the 4-linked 5-hydroxypyrazole ring C3-C5 alkynyl of formula E (please read the precautions on the back before writing this page). Install. IT The NI R1 R2 II HO line is printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economics. R1 is Ci-"alkyl, and 2 is hydrogen or methyl, and the industry-used salt of the compound of formula I. Gen Huan applied for a patent The saccharin derivative of formula I in the scope of item i, where L and -C4 alkyl or chloroa root are derived from the saccharin derivative of formula I in the scope of patent claims 1 or 2, of which the paper standard is applicable to China National Standard (CNS) Α4 specification (210Χ297mm) 6. LRM is hydrogen, methyl, or chlorine. A herbicidal composition comprising at least one saccharin derivative of formula I according to item 1 of the patent application scope and conventional inert additives. A method for controlling the growth of weeds, which comprises applying a herbicidally effective amount of a saccharin derivative of the formula I according to item 1 of the scope of the patent application to a plant or its growing place. A method for preparing the compound of formula I according to item 1 of the patent application scope, which includes formula I V acetyl chloride (please read the precautions on the back before filling this page) L C1C II 1 \ / ΝZO S05 0 IV Μ Printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy where L, Μ and Z are as defined in item 1 of the patent application scope, 5-hydroxypyrazole of Formula I * R2 HO • r I R1 II where R1 is a Ca-G alkyl group, R1 2 is hydrogen or methyl, and in the presence of chlorination _ heavy sister compound product, to get the formula I compound 1 2 This paper scale applies China National Standard (CNS) A4 Present grid (210X 297 mm), such as 9330 Patent Application No. 84108049 Cang! ^ Chinese Supplementary Instructions (August 1985) Table 2 Selective herbicidal activity in the greenhouse after germination post-treatment Example 1.17 Application rate (kg / ha aS) 0.125 0.0625 Test plant damage degree (%) TRZAW (winter wheat) 〇0 ZEAMX (corn) 0 0 CHEAL 90 90 POLPE 90 90 SINAL 80 70 SOLNI 95 90 Table 3 Germination in the greenhouse Selective herbicidal activity after treatment Example 1.19 Application rate (kg / ha a.S.) 0.125 0.0625 Test plant Hazard degree α) TRZAS (spring wheat) 20 10 ZEAMX (corn) 20 20 CHEAL 98 98 ECHCG 80 80 POLPE 98 98 SINAL 100 100