EP0775137A1

EP0775137A1 - Saccharine derivatives

Info

Publication number: EP0775137A1
Application number: EP95927735A
Authority: EP
Inventors: Peter Plath; Wolfgang Von Deyn; Stefan Engel; Uwe Kardorff; Hartmann König; Harald Rang; Matthias Gerber; Helmut Walter; Karl-Otto Westphalen
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1994-08-08
Filing date: 1995-07-27
Publication date: 1997-05-28
Also published as: TW300891B; US5716906A; JPH10505589A; DE4427998A1; ZA956578B; CA2197119A1; WO1996005198A1; AU3166795A

Abstract

The invention concerns saccharine derivatives of formula (I) in which the substituents are defined as follows: L, M hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, chlorine, cyano, methylsulphonyl, nitro or trifluoromethyl; Z hydrogen, C1-C4 alkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, C3-C5 alkinyl, C1-C4 acyl, benzyl or phenyl, wherein any of the phenyl rings may be substituted by halogen or C1-C4 alkyl; Q a T-J group, T being a carbonyl (CO) group or the -CHY group, J being an isoxazole ring of formula (II) bonded at the 4-position and in which R1 is hydrogen or C¿1?-C4 alkyl, R?2 is C¿1-C4 alkyl, cyclopropyl, 1-methylcyclopropyl or 1-methylthiocyclopropyl, Y is an OH-group, a hydroxy group acylated with C2-C4 acyl, or a chlorine atom. The invention also concerns salts of such compounds usually used in agriculture.

Description

SACCHAR DERIVATIVES WITH HERBICIDAL EFFECT

description

The present application relates to saccharin derivatives of the formula I.

in which the substituents have the following meaning:

L, M is hydrogen, -CC alkyl, -CC alkoxy, -C ₄ alkylthio, chlorine, cyano, methylsulfonyl, nitro or trifluoromethyl;

Z is hydrogen, -CC ₄ alkyl, C -C ₈ cycloal] <yl, C ₃ -C ₆ alkenyl, C ₃ -C ₅ alkynyl, C ~ C ₄ -acyl, benzyl or phenyl, the phenyl rings are each optionally substituted by halogen or -CC ₄ alkyl;

Q is a residue T-J, where

T stands for a carbonyl radical CO or for the radical -CHY, where

J is an isoxazole ring of the formula II linked in the 4-position,

R ₂

means in which

R ¹ for hydrogen or -CC ₄ alkyl and

R ^{2 represents} -C-alkyl, cyclopropyl, 1-methylcyclopropyl or 1-methylthiocyclopropyl;

Y represents an OH group, a hydroxyl group optionally acylated with C ₂ -C ₄ -acyl or a chlorine atom;

as well as agriculturally customary salts of the compounds I. The invention furthermore relates to herbicidal compositions comprising the compounds I and processes for controlling unwanted vegetation with the saccharin derivatives I. In addition, the present invention also comprises intermediates for the preparation of the end products I according to the invention and production processes for the products I under Use of the new intermediate products of formulas B2 and IV

Saccharin derivatives with herbicidal activity cannot be found in the prior art. In contrast, unsubstituted saccharin (o-sulfobenzoimide, i.e.L, M, Q and Z in formula I = H) has long been known as a synthetic sweetener. 4-Hydroxy-saccharin (DE-OS 3 607 343) is also known as a sweetener. It is also known to use saccharin derivatives in pest control, e.g. JP publication 72/00419, 73/35457 (fungicides) and in pharmacy, e.g. EP-A 594 257 and patents mentioned therein.

Heterocyclic compounds with a ring containing a sulfonamide group have become known as herbicides, and bentazone is a typical representative here

H

to call. The object of the invention was to provide new herbicides with a basic structure hitherto unknown for this indication. Accordingly, the compounds I defined at the outset and the intermediates B2 were found.

Compounds of the formula I with R ¹ = H are obtained by the known β-keto esters of the formula AI [Y. Oikawa et al., JOC AI, 2087 (1978) 1 acylated with an acid chloride of the formula III to give an ester of the formula B1, which is converted into a 1,3-diketone of the formula Cl by reaction with p-toluenesulfonic acid in toluene, then the 1,3-Diketone Cl either converted to an enol ether Dl with orthoformic acid triethyl ester or with dimethylformamide-dimethylacetal into an enamine D2 and reacting Dl or D2 with hydroxylamine to give the saccharin derivative of the formula 1.1. The reaction sequence is summarized in the following formula:

D1: X = 0C ₂ H ₅

D2: X = N (CH ₃ ) ₂

The ß-keto esters of the formula AI used as starting material are known and can, for. B. by reaction of Meldrum's acid with acid chlorides of the formula R ² -C0C1 and subsequent reaction with tert. Butanol can be obtained.

The reaction of β-keto esters of the formula AI with benzoic acid chlorides and the subsequent acid-catalyzed decomposition to 1,3-diketones is known: e.g. from EP-A 527 037, EP-A 560 483. Both the condensation of 1,3-diketones with triethyl orthoformate and the reaction of the resulting enol ether D1 with hydroxylamine to form isoxazoles are known, e.g. from EP-A 527 036, EP-A 560483. The reaction of 1,3-diketones with orthoamides such as dimethylformamide dimethylacetal and the subsequent reaction of the resulting enamines D2 with hydroxylamine to isoxazoles is described by Menozzi in J. Het. Chem. _Z, 645 (1983).

If, on the other hand, R ^{1 is} C 1 -C 4 -alkyl, the compounds of the formula I are obtained by reacting saccharin carboxylic acid chlorides of the formula IV with alkynylstannanes of the formula A2 to give benzoylalkynes of the formula B2 and then using nitrile oxides of the Formula C2 subjects a cycloaddition to the isoxazoles of formula 1.2:

In the above formulas, M has the meaning given above and Z represents hydrogen, C 1 -C ₄ -alkyl,

C ₃ -C ₈ cycloalkyl, C ₃ -C ₆ alkenyl, C ₃ -Cs alkynyl, C ₁ -C ₈ -acyl or for benzyl or phenyl which is optionally substituted by halogen or C 1 -C ₄ alkyl.

Alkynylstannanes of the formula A2 can be obtained in a known manner from trialkyltin chloride and lithium acetylidene. Aroylalkynes are prepared in a manner known per se from alkynylstannanes and benzoic acid chlorides in the presence of palladium catalysts such as bis (triphenylphosphine) palladium (II) chloride, such as e.g. by Crisp in Synth. Comm. 1_, 1745 (1989).

Nitrile oxides of the formula C2 are obtained in a known manner from hydroxamic acid chlorides and tertiary amines such as triethylamine. The cycloaddition of aroylalkynes with nitrile oxides to isoxazoles is e.g. known from EP-A 487 357.

The starting materials of the formula IV are prepared in a manner known per se by reacting the saccharin carboxylic acid derivatives III

made with thionyl chloride.

Saccharin carboxylic acids III are known in some cases (4-COOH: Zincke, Liebigs Ann. 427, 231 (1922), 5-C00H: Jacobsen, Chem. Ber. H, 1554 (1880), 6-COOH: Weber, Chem. Ber. 21, 1740 (1892)). DE-OS 3 607343 also describes the preparation of 4-chlorosaccharin-5-carboxylic acid.

Saccharin carboxylic acids can also be obtained by corresponding bromo or iodo substituted saccharin derivatives of formula II

in which L, M and Z have the meaning given above, or in the case of Z ≠ H compounds of the formula III

in the presence of a palladium, nickel, cobalt or rhodium transition metal catalyst and a base with carbon monoxide and water or a Ci-C _ß alcohol under increased pressure.

For example, if L is methyl and M and Z are hydrogen, the reaction sequence can be represented as follows:

The catalysts nickel, cobalt, rhodium and in particular palladium can be metallic or in the form of conventional salts such as in the form of halogen compounds, for example PdCl ₂ , RhCl • H ₂ O, acetates, for example Pd (0AC) ₂ , cyanides etc. in the known valence levels . Furthermore, metal complexes with tertiary phosphines, metal alkylcarbonyls, metal carbonyls, for example Co ₂ (CO) ₈ , Ni (C0) ₄ , metal carbonyl complexes with ter-phosphines, for example (PPh ₃ ) ₂ Ni (CO) ₂ or complexed with tertiary phosphines Transition metal salts are present. The latter embodiment is particularly preferred in the case of palladium as a catalyst. The type of phosphine ligand is widely variable. For example, they can be represented by the following formulas:

R ⁷ Rl ^ Ri2 R ⁸ or P (CH ₂ ) _n R ¹³ R ⁹ where n is the numbers 1, 2, 3 or 4 and the radicals R ⁷ to R ¹³ for low molecular weight alkyl, for example Ci-Cβ-alkyl, aryl , Ci-C ₄ alkylaryl, for example benzyl, phenethyl or aryloxy. Aryl is, for example, naphthyl, anthryl and preferably optionally substituted phenyl, the substituents only having to be considered for their inertness to the carboxylation reaction, otherwise they can be varied widely and include all inert C-organic radicals such as Ci-Cε -Alkyl radicals, for example methyl, carboxyl radicals such as COOH, COOM (M is, for example, an alkali metal, alkaline earth metal or ammonium salt), or C-organic radicals bonded via oxygen, such as -CC ₆ alkoxy radicals.

The phosphine complexes can be prepared in a manner known per se, for example as described in the documents mentioned at the outset. For example, one starts from customary commercially available metal salts such as PdCl ₂ or Pd (0C0CH ₃ ) ₂ and adds the phosphine, for example P (C ₆ H ₅ ) ₃ , P (nC ₄ H ₉ ) ₃ , PCH (C ₆ H ₅ ) ₂ , 1,2-bis (diphenylphosphino) ethane.

The amount of phosphine, based on the transition metal, is usually 0 to 20, in particular 0.1 to 10 mol equivalents, particularly preferably 1 to 5 mol equivalents.

The amount of transition metal is not critical. Of course, for reasons of cost, rather a small amount, for example from 0.1 to 10 mol%, in particular 1 to 5 mol%, based on the starting material II or III will be used. β

To prepare saccharin carboxylic acids III, the reaction is carried out with carbon onoxide and at least equimolar amounts of water, based on the starting materials A2 and A4. The reaction partner water or Ci-Cε-alkyl-OH can also serve as a solvent, i.e. the maximum amount is not critical.

However, depending on the type of starting materials and the catalysts used, it may also be advantageous to use a different inert solvent or the base used for the carboxylation as the solvent instead of the reaction partner.

Suitable inert solvents for carboxylation reactions are conventional solvents such as hydrocarbons, for example toluene, xylene, hexane, pentane, cyclohexane, ethers, for example methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted amides such as dimethylformamide, per-substituted ureas such as tetra-Cι -C ₄ alkylureas or nitriles such as benzonitrile or acetonitrile.

In a preferred embodiment of the process, one of the reactants, in particular the base, is used in excess, so that no additional solvent is required.

Bases suitable for the process are all inert bases which are able to bind the hydrogen iodide or hydrogen bromide released during the reaction. For example, tertiary amines such as triethylamine, cyclic amines such as N-methylpiperidine or N, N-dimethylpiperazine, pyridine, amides such as N-methyl or N, N-dimethylformnamide, alkali or alkaline earth metal hydroxides,

carbonates, or bicarbonates or tetraalkyl-substituted urea derivatives such as tetra-C 1 -C ₄ -alkylurea, for example tetra-methylurea.

The amount of base is not critical, usually 1 to 10, in particular 1 to 5, moles are used. If the base is simultaneously used as solvent, the amount is generally such that the reactants are dissolved, unnecessarily high excesses being avoided for reasons of practicality; to save costs, to be able to use small reaction vessels and to ensure maximum contact for the reaction partners.

During the reaction, the carbon monoxide pressure is adjusted so that there is always an excess of CO, based on A3 or A4. The carbon monoxide pressure at room temperature is preferably 1 to 250 bar, in particular 5 to 150 bar CO. The carbonylation is generally carried out continuously or batchwise at temperatures from 20 to 250 ° C., in particular at 30 to 150 ° C. In the case of discontinuous operation, carbon monoxide is expediently pressed continuously onto the reaction mixture in order to maintain a constant pressure.

From the resulting reaction mixture, the products can be prepared in the usual way, e.g. isolated by distillation.

The starting materials A3 or A4 required for the reaction are known or can be prepared in a manner known per se. They can either be obtained by permanganate oxidation of iodine-substituted 2-methylbenzenesulfonamides or by Sandmeyer reaction from aminosaccharides. Aminosaccharins are obtained by known methods by reduction of nitrosaccharides, which in turn are either known (Kastle, Amer. Chem. Journal H, 184 (1889) or DRP 551423 (1930) or in a manner known from the literature from suitable nitrobenzene derivatives (Liebigs Ann 669, 85 (1963)) or benzene sulfonamides.

In addition, they can be obtained analogously to the preparation instructions from Examples 1 to 12.

The compounds I with T = -CHY can be obtained from the compounds of the formula 1.2 with T = CO by reducing them with sodium borohydride to carbinols of the formula 1.3 and reacting them either with methanesulfonyl chloride to chlorides of the formula 1.4 or with C ₂ -C carboxylic anhydrides acylated to esters of the formula 1.5.

CH ₃ S0 ₂ C1

1.5

With regard to the intended use, saccharin derivatives of the formula I are preferred in which the radicals L and M are hydrogen, methyl, methoxy, methylthio, chlorine, cyano, methylsulfonyl, nitro or trifluoromethyl. Furthermore, one of the radicals L or M is hydrogen and the other radical is one of the radicals mentioned above.

In formula I, Q particularly preferably denotes the radical CO-J. The radical R ¹ is preferably hydrogen and R ^{5 is} preferably cyclopropyl or tert. Butyl.

The radical Z particularly preferably represents one of the C-organic radicals mentioned, in particular methyl, ethyl, acetyl, phenyl or propargyl.

Particularly preferred active ingredients can be found in Table 1. The groups listed in Table 1 for a substituent also represent themselves - regardless of the specific combination with other substituents in which they are mentioned - represent a particularly preferred definition of the substituent in question.

The compounds I can be in the form of their agriculturally useful salts, the type of salt generally not being important. Usually the salts of such bases will be considered which do not adversely affect the herbicidal activity of I.

Particularly suitable as basic salts are those of the alkali metals, preferably the sodium and potassium salts, those of the alkaline earth metals, preferably calcium, magnesium and barium salts and those of the transition metals, preferably manganese, copper, zinc and iron salts as well as the ammonium salts, which can carry one to three C 1 -C ₄ alkyl, hydroxy C 1 -C ₄ alkyls and / or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium and trimeth 1 - (2-Hydroxyethyl) ammonium salts, the phosphonium salts, the sulfonium salts, preferably tri- (C 1 -C ₄ ) alkylsulfonium salts, and the sulfoxonium salts, preferably tri- (C 1 -C 4) alkylsulfoxonium salts.

The compounds I or the herbicidal compositions comprising them and their environmentally compatible salts of, for example, alkali metals, alkaline earth metals or ammonia and amines, or the herbicidal compositions comprising them, can weeds and harmful grasses very well in crops such as wheat, rice, corn, soybeans and cotton fight without significantly damaging the crops. This effect occurs especially at low application rates.

Taking into account the versatility of the application methods, the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants, for example the following crops are suitable:

Allium cepa, pineapple comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spp. altissima, Beta vulgaris spp. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea libericaus), Cucumodison , Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoealumisisumisum , Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus aviu, Prunus persica, Pyrus communisis, Ribes sylvest , Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (see vulgar), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum dunim, Vicia faba, Vitis vinifera, Zea mays.

In addition, the compounds I can also be used in crops which have been made largely resistant to the action of I or other herbicides by breeding and / or by means of genetic engineering methods.

The herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active substances are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not struck wherever possible, while the active compounds grow more rapidly on the leaves underneath unwanted plants or the uncovered floor area (post-directed, lay-by).

The compounds I or the herbicidal compositions comprising them can be sprayed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents or granules , Atomizing, dusting, scattering or pouring can be used. The application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

The following are essentially suitable as inert auxiliaries for the production of directly sprayable solutions, emulsions, pastes or oil dispersions: mineral oil fractions from medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons , for example paraffins, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, for example amines such as N-methylpyrrolidone, or Water. Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the 5 substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.

The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as from

15 fatty acids, alkyl and alkyl aryl sulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols as well as fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of nphthaline and 0 Naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated polyethyleneglycol alcohol 5% Sorbitol esters, lignin sulfite waste liquors or methyl cellulose can be considered.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers.

35 places. Solid carriers are mineral soils such as silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate, Ammonium phosphate, ammonium nitrate, urinary

40 substances and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

The formulations generally contain between 0.01 and 45 95% by weight, preferably between 0.5 and 90% by weight, of active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum). The compounds I according to the invention can be formulated, for example, as follows:

I. 20 parts by weight of compound 1.05 are dissolved in a mixture which is alkylated from 80 parts by weight

Benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanol amide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By

Pouring out and finely distributing the solution in 100,000 parts by weight of water gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.

II. 20 parts by weight of compound 1.05 are in one

Dissolved mixture, which consists of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the additive of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

III. 20 parts by weight of the active ingredient 1.05 are in one

Dissolved mixture, which consists of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring and finely distributing the solution in

100,000 parts by weight of water give an aqueous dispersion which contains 0.02% by weight of the active ingredient.

IV. 20 parts by weight of the active ingredient 1.05 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. A fine mixture of the mixture in 20,000 parts by weight of water gives a spray liquor which contains 0.1% by weight of the active ingredient. V. 3 parts by weight of active ingredient 1.05 are mixed with 97 parts by weight of finely divided kaolin. In this way, a dusting agent is obtained which contains 3% by weight of the active ingredient.

VI. 20 parts by weight of active ingredient 1.05 are mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid,

8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic

Mineral oil mixed intimately. A stable oily dispersion is obtained.

In order to broaden the spectrum of activity and to achieve synergistic effects, the saccharin carboxylic acid derivatives I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied together. For example, diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenyl carbamates, thiol carbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1, come as mixing partners. 3-dione derivatives, e.g. in the 2-position carry a carboxy or carbimino group, quinoline carboxylic acid derivatives, imidazolinones, sulfonamides, sulfonylureas, aryloxy, heteroaryloxyphenoxypropionic acids and their salts, esters and amides and others.

It may also be useful to apply the compounds I alone or in combination with other herbicides, mixed with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.

Depending on the control target, the season, the target plants and the growth stage, the active compound application rates are from 0.01 to 3.0, preferably from 0.01 to 1.0, kg / ha of active substance (a.S.).

Preparation Examples:

1. Acylation of Meldrum's acid with cyclopropanecarboxylic acid chloride

To a solution of 20 g (0.14 mol) cooled to 5 ° C

2,2-Dimethyl-l, 3-dioxan-4, 6-dione (Meldrum's acid) in 100 ml of methylene chloride, 22 g (0.28 mol) of pyridine are added. A solution of 16 g (0.15 mol) of cyclopropanecarboxylic acid chloride in 50 ml of methylene chloride is then added dropwise at 0-3 ° C. After two hours of stirring at 25 ° C, the reaction mixture with 100 ml of 5 percent. HC1 added and stirred briefly. The organic phase is then separated off, washed with water and dried over sodium sulfate. After the solvent has been stripped off in vacuo, my 27.7 g of an oil (84% of theory) are obtained, which according to NMR is the enol of the formula

is present.

2. tert-butyl 3-oxo-3-cyclopropyl-propionate

25 g (0.338 mol) of tert are added. Butanol to a solution of 23.9 g (0.113 mol) of the compound obtained in 1. in 100 ml of toluene and heated to boiling. After 4 hours, the mixture is allowed to cool, the reaction mixture is washed with ice water and the organic phase is dried over sodium sulfate. After the solvent has been stripped off, 20 g (82% of theory) of an oil of the above structure remain.

3. 2-methyl-6-acetaminobenzoic acid

90.6 g (0.6 mol) of 6-methylanthranilic acid are added to a solution of 24.8 g (0.62 mol) of NaOH in 500 ml of water, and 63.4 g (0.62 mol) of acetic anhydride are then added dropwise. After one hour of stirring with conc. HC1 acidified to pH 3, the precipitate is filtered off, washed with water and at 50 ° C i. Vak. dried.

Yield: 107 g (0.55 mol) = 92% of theory, mp: 189-190 ° C

4. 2-methyl-3-nitro-6-acetaminobenzoic acid

271 ml of 98 percent are added. Nitric acid at - 5 ° C and carries in portions 106 g (0.55 mol) of the 2-methyl-6-acetaminobenzoic acid prepared under 1. After one hour After stirring at 10 ° C, the reaction mixture is poured into a mixture of 540 g of ice and 270 ml of water. The precipitate is filtered off, washed with water and i at 50 ° C. Vac. dried. Yield. 75.6 g (0.317 mol) = 58% of theory. Th., M.p .: 190-191 ° C

After a long period of standing, the filtrate separates into

3-position nitrided isomers.

Yield: 21.3 g (0.089 mol) = 16% of theory. Th., M.p .: 180-182 ° C

2-methyl-3-nitro-6-aminobenzoic acid

450 ml of 2-N NaOH are introduced and 75.6 g (0.317 mol) of 2-methyl-3-nitro-6-acetaminobenzoic acid are added. The reaction mixture is then heated to 95 ° C. and left to stir at this temperature for one hour. After cooling to 10 ° C., the mixture is acidified by adding 425 ml of 2-N HC1. The precipitate is filtered off, washed with water and dried at 50 ° C i. Vak .. yield. 50.7 g (0.258 mol) = 82% of theory Th., M.p .: 183-184 ° C

6. 2-methyl-3-nitro-6-aminobenzoic acid methyl ester

49.7 g (0.253 mol) of 2-methyl-3-nitro-6-aminobenzoic acid are dissolved in 380 ml of acetone and 43 g (0.51 mol) of sodium hydrogen carbonate are added. The mixture is then heated to boiling until the C0 ₂ evolution is complete. 35.3 g (0.28 mol) of dimethyl sulfate are then added dropwise to the suspension of the sodium salt of 2-methyl-3-nitro-6-aminobenzoic acid obtained at the boiling point of the acetone over the course of two hours, then refluxed for a further three hours and then let cool. After pouring the reaction mixture into 1.8 l of water, it is extracted with methylene chloride. After the organic phase has dried, the mixture is concentrated. The solid obtained is sufficiently pure for the subsequent reaction (NMR). Yield: 50 g (0.238 mol) = 94% of theory. Th., Mp: 92-94 ° C

2-methoxycarbonyl-3-methyl-4-nitro-benzenesulfonic acid chloride

58.5 g (0.278 mol) of methyl 2-methyl-3-nitro-6-amino-benzoate are dissolved in 280 ml of glacial acetic acid with heating and this solution is poured at 85 ° F. into 85 ml of conc. HC1. A solution of 19.3 g (0.28 mol) of sodium nitrite in 60 ml of water is then added dropwise at 5-10 ° C. and the mixture is stirred at 5 ° C. for 30 minutes. Then you drop this diazonium salt solution into a solution of 374 g S0 ₂ in 750 ml glacial acetic acid, containing 14 g CuCl2 (dissolved in 30 ml water). After the nitrogen evolution has ended, the mixture is stirred for a further 15 min and then poured into 1.4 l of ice water. The sulfonic acid chloride is separated off by extraction with 1.2 l of methylene chloride. After drying and concentrating the organic phase, 73 g (0.25 mol) (= 90% of theory) of an oil are obtained which, according to NMR (in CDC1 ₃ ), is pure 2-methoxycarbonyl-3-methyl-4-nitro-benzenesul- is fonic acid chloride.

8. 4-methyl-5-nitrosaccharin

104 ml of 25 percent is added. Ammonia solution, adds 100 ml of water and then drops in a solution of 48.7 g (0.166 mol) of 2-methoxycarbonyl-3-methyl-4-nitro-benzenesulfonic acid chloride in 70 ml of tetrahydrofuran at 10 ° C. . After stirring for three hours at 25 ° C., the mixture is concentrated on a rotary evaporator to remove water and THF. The remaining residue is stirred with ethyl acetate, suction filtered and washed with ethyl acetate. After drying i. Vak. 34 g (0.131 mol) = 79% of theory are obtained. Th. Of a white solid with mp: 312 ° C (dec.)

9. 2,4-dimethyl-5-nitrosaccharin

This substance can be prepared by subsequent methylation of the saccharin obtained under 8. with dimethyl sulfate in the presence of NaOH.

10. 3-methyl-4-nitro-2- (N'-methyl) carboxamido-N-methylbenzenesulfonamide

Pour 50 ml of water in 50 ml of 40 percent. Methylamine solution and dropwise at 10 ° C a solution of 24.3 g (83 mmol) of 2-methoxycarbonyl-3-methyl-4-nitro-benzenesulfonic acid chloride in 35 ml of THF. After stirring for one hour at 25 ° C., all volatile constituents are stripped off on a rotary evaporator, the residue is extracted with ethyl acetate, the organic phase is washed with water, dried and concentrated. The remaining residue crystallizes after standing for a long time. Yield: 10.3 g (40 mmol = 48% of theory), mp: 125-126 ° C, after recrystallization from ethyl acetate, mp: 144-145 ° C. According to NMR, the product is not a saccharine derivative but a carboxamide with an additional sulfonamide group. 11. 4-methyl-5-amino-saccharin

33.6 g (0.13 mol) of 4-methyl-5-nitro-saccharin are dissolved in 1.2 l of water with heating to 45 ° C. and 5 g of Pd / C 5 (10% on activated carbon) are added. Hydrogen gas is then passed in with vigorous stirring (pressureless hydrogenation). 9 1 H _{2 are} absorbed over the course of 4.5 hours. After cooling to 25 ° C., the catalyst is filtered off, concentrated to a volume of 200 ml on a Rotavapor and then acidified to pH 1. 10 The precipitate is filtered off, washed with water and at 50 ° C i. Vac. dried. 23.4 g (0.11 mol = 85% of theory) of a white solid with mp: 272-273 ° C. are obtained

15 12. 4-Methyl-5-iodo-saccharin

A mixture of 205 ml of glacial acetic acid, 160 ml of water and 40 ml of conc. HC1 before and enters with stirring 23.4 g (0.11 mol) of 4-methyl-5-amino-saccharin at 15 - 20 ° C. To the originated

20 drops of suspension are added dropwise at 5-10 ° C. 7.9 g (0.115 mol) of sodium nitrite and left for 30 min. Stir at 5 ° C. The diazonium salt, which is in suspension, is then added dropwise in portions to a solution of 19.1 g (0.115 mol) of potassium iodide in 170 ml of water heated to 50 ° C., nitrogen being removed.

25 stands. After cooling to room temperature, the precipitated product is isolated by suction, washed with water and i. Vak. dried. 32.5 g (0.1 mol = 91% of theory) of a solid with mp: 257-258 ° C. are obtained.

30 A combustion analysis shows an iodine content of 38.5% (theory 39.3%).

The product is sufficiently pure for the subsequent implementations.

35 13. 4-methyl-saccharin-5-carboxylic acid

6.4 g (0.002 mol) of 4-methyl-5-iodo-saccharin are dissolved in 70 ml of tetramethyl urea and 30 ml of water 0.7 g, mixed with bis (triphenylphosphine) palladium chloride and the mixture in a 300 ml autoclave heated to 100 ° C and stirred for 36 h at a pressure of 100 bar carbon monoxide.

For working up, the mixture is filtered and water and tetramethylurea are removed by distillation in a high vacuum. The residue is taken up in methyl tert-butyl ether (MTBE) 45, with NaHC0 ₃ solution. extracted and after acidification with HCl again with MTBE extracted. After concentration, 2.8 g of 4-methyl-1-saccharin-5-carboxylic acid (58% of theory) are obtained.

iH NMR (DMSO, 400.1 MHz): 2.85 (3H, s); 8.05 (1H, d); 8.2 5 (1H, d);

¹³ C NMR (DMSO, 100, 6 MHz): 167.4 (CO); 161.3 (CO); 141.6 (quart. C); 139.7 (quart. C); 138.7 (quart. C); 135.6 (CH); 125.4 (quart. C); 118.5 (CH); 15.4 (CH ₃ ). 10

14. 4, N-Dimethyl-saccharin-5-carboxylic acid

7.3 g (0.02 mol) of 3-methyl-4-iodo-2- (N'-methyl) carboxamido-N-methylbenzenesulfonamide together with 0.69 g of bis (tri-15 phenylphosphine) palladium chloride, 30 ml of water and 70 ml

Tetramethylurea placed in a 300 ml autoclave, the mixture heated to 100 ° C and stirred for 36 h at a pressure of 100 bar carbon monoxide.

After working up as described in Example 12, 4.1 g of the title compound are obtained (0.014 mol = 72% of theory).

* H NMR (DMSO, 400.1 MHz): 2.9 (3H, s); 3.15 (3H, s); 8.2 (2H, 2d); 14.0 (1H, S) 25

¹³ C NMR (DMSO, 100.6 MHz): 167.3 (CO); 158.6 (CO); 139.7 (quart. C); 139.1 (quart. C); 138.9 (quart. C); 135.5 (CH); 124.6 (quart. C); 119.0 (CH); 22.9 (CH3); 15.6 (CH ₃ ).

30 15. 4-Amino-3-methyl-2- (N'-methyl) carboxamido-N-methylbenzenesulfonamide

Analogously to the procedure described in item 11, the 3-methyl-4-nitro-2- (N'-methyl) carboxamido-35 N-methyl-benzenesulfonamide obtained in item 10 was hydrogenated without pressure. The aniline derivative of the structure shown opposite was obtained in 93% yield, mp: 217-218 ° C.

45 16. 3-Methyl-4-iodo-2- (N'-methyl) carboxamido-N-methylbenzenesulfonamide

Following the procedure described in point 12, the preceding compound was diazotized and converted to the structure shown opposite by reaction with KI to give the iodobenzene derivative. Yield: 95%, mp: 60-62 ° C

15

17. 2,4-Dimethyl-saccharin-5-carboxylic acid chloride

3.8 g (14.9 mmol) of the 2,4-dimethyl-saccharin-5-carboxylic acid are suspended in 100 ml of toluene, heated to 80 ° C. and 20 drops of 3.5 g (29.8 mmol) of thionyl chloride to. After two hours of refluxing, the mixture is decanted hot and the reaction mixture is concentrated. The product obtained (3 g, 74% of theory) has an mp .: 149-150 ° C.

25 18. General procedure for the preparation of the compounds of formula 1.1

18.lAcylation to the intermediate of formula B1

30 60 g (0.33 mol) of tert-butyl 3-oxo-3-cyclopropyl-propionate are added to a suspension of 8.4 g (0.345 mol) of magnesium shavings in 700 ml of methanol, and the mixture is added with cooling to 20 - 28 ° C 8 ml carbon tetrachloride. After 4 hours of stirring, the formed

35 magnesium enolate 700 ml of acetonitrile and then added dropwise at 20-26 ° C a solution of 0.32 mol of the respective saccharin carboxylic acid chloride IV in 100 ml of acetonitrile. The mixture is then left to stir at 25 ° C. for 16 hours, then heated to 40 ° C. for a further hour and removed

40 then the acetonitrile and methanol by rotating in a vacuum. The residue is taken up in ethyl acetate, washed with 2N HCl, the organic phase is then washed with water, dried over sodium sulfate and concentrated. The remaining viscous mass (yield: 80-90

45%) is used as the raw product B1 without further purification. 18.2 Cleavage of the tert-butyloxycarbonyl radical to give the β-diketone

Cl

0.274 mol of the product B1 obtained under 18.1 is suspended in 900 ml of toluene, 11 g of p-toluenesulfonic acid are added and the mixture is heated to boiling for seven hours. After cooling, the reaction mixture with 5 percent. NaOH neutralized, the aqueous phase separated, with conc. Acidified HC1 to pH 1 and shaken with methylene chloride. After washing with water and drying the organic phase, part of the diketone Cl is isolated from this solution. The remaining amount of Cl is obtained from the initially separated toluene solution by washing it with water, drying and i. Vak. constricts. The yield is 77% of theory, the crude product is processed directly in step 18.3.

18.3 Implementation of the diketones Cl to the enol ether Dl

36 mmol of the respective diketone Cl are mixed with 6.3 g (42 mmol) of acetic anhydride and 5.5 g (54 mmol) of triethyl orthoformate and heated for three hours to boiling (110 ° C.). Then all volatile constituents i. Vak. , leaving a crystalline residue. The yield is over 95% of theory. Th ..

The crude product is reacted with hydroxylamine in step 18.4 without further purification.

18.4 Ring closure to the isoxazole derivative

10 mmol of the respective enol ether Dl are placed in 50 ml of methylene chloride, 11 mmol of hydroxylamine hydrochloride are added, and a solution of 5.5 mmol of sodium carbonate in 2.5 ml of water is added dropwise at 10-15 ° C. After four hours of stirring at 25 ° C., the reaction mixture is poured, washed with water and the organic phase is separated off. After drying and stripping off the solvent, the saccharin derivative of the formula 1.1 remains as a viscous oil, which is purified by chromatography on silica gel (mobile phase: toluene / ethyl acetate = 9: 1). The isolated yield is between 50 and 60% of theory. Th.

19. General preparation instructions for the cycloaddition of Aroy¬ alkynes with nitrile oxides to saccharin derivatives of the formula 1.2 19.1 Aroylalkynes from tributyltin alkynes

0.39 g (0.56 mmol) of bis (triphenylphosphine) palladium (II) chloride is added to a solution of 11.1 mmol of the respective saccharinic acid chloride of the formula IV in 100 ml of methylene chloride and the mixture is added at 20-25 ° C a solution of 4.9 g (14 mmol) of tributyltin propyne in 20 ml of methylene chloride. After 16 hours of stirring at 25 ° C the methylene chloride i. Vak. withdrawn and the residue obtained purified by chromatography on silica gel (mobile phase: toluene / ethyl acetate = 9: 1). The isolated yield is between 50 and 65% of theory. Th .. Intermediates of formula B2 prepared in this way are summarized in Table 2.

19.2 Cycloaddition

0.6 g (7 mmol) of isobutyraldoxime are added to the solution of 6.6 mmol of the respective aroylalkyne from step 19.1 in 30 ml of methylene chloride and then dropwise with 9.6 g (16 mmol) of a 12 percent strength. NaOCl solution added. After 16 hours of stirring at 25 ° C., the reaction mixture is shaken out with water, the org. Phase dried and concentrated. After chromatography (silica gel, toluene-cyclohexane = 8: 2), the saccharin derivative of the formula 1.2 is obtained in a yield between 20 and 40%.

The compounds listed in Table 1 can be obtained in an analogous manner:

Table 1:

Saccharin derivatives I with Q = CO-J

No . R ¹ R2 Q-Pos LMZ Fp (° C)

1 . 01 HC ₃ H ₅ 4 HHH

1 . 02 H C3H5 4 HH CH ₃

1 . 03 H C3H5 5 4 -CH3 HH No.R ^l R2 Q-Pos LMZ Fp (° C)

1.04 HC ₃ H ₅ 5 4-C1 H CH ₃

1.05 HC ₃ H ₅ 6 HH CH ₃ 154-156

1.06 H tC ₄ H ₉ 6 HH CH ₃

1.07 H tC ₄ H ₉ 4 HHH

1.08 CH ₃ tC ₄ H ₉ 5 4-CH ₃ H CH ₃

1.09 iC ₃ H ₇ tC ₄ H ₉ 5 4-C1 H ethyl

1.10 iC ₃ H ₇ tC ₄ H ₉ 6 HH propargyl

Table 2:

Saccharin derivatives of the formula B2

No.R2 Q-Pos L M Z Fp (° C)

2.01 cyclopropyl 4 6-CH ₃ H CH ₃

2.02 cyclopropyl 5 4-CH ₃ H C2H5

2.03 cyclopropyl 6 5-C1 H propargyl

2.04 cyclopropyl 5 4-C1 7-C1 phenyl

2.05 cyclopropyl 5 7-CH ₃ 6-CH ₃ benzyl

2.06 1-methylcyclopropyl 4 6-CH ₃ H CH ₃

2.07 1-methylcyclopropyl 5 4-CH ₃ 7-C1 C2H5

2.08 1-methylcyclopropyl 6 5-C1 H propargyl

2.09 1-methylthio-cyclo-5 4-CH ₃ 7-CH ₃ propargyl propyl

2.10 1-Methylthio-cyclo- 5 4-CH ₃ H phenyl propyl

2.11 1-methylthio-cyclo-5 4-CH ₃ 7-C1 benzyl propyl

2.12 tert-butyl 4 6-CH ₃ 7-CH ₃ CH ₃

2.13 tert, -Butyl 5 4-C1 H C2H5

2.14 tert-butyl 6 4-C1 H propargyl

Examples of use

The herbicidal activity of the saccharin derivatives of the formula I was demonstrated by greenhouse experiments: Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels. The seeds of the test plants were sown separately according to species.

In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles. The vessels were sprinkled lightly to promote germination and growth, and then covered with transparent plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was adversely affected by the active ingredients.

For the post-emergence treatment, the test plants, depending on the growth habit, were first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.

The plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species. The trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to the individual treatments was evaluated.

Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.

Claims

claims

1. Saccharin derivatives of the formula I.

in which the substituents have the following meaning:

L, M hydrogen, -CC ₄ alkyl, -C ₄ alkoxy, -C -C alkylthio, chlorine, cyano, methylsulfonyl, nitro or trifluoromethyl;

Z is hydrogen, -CC ₄ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₃ -C ₆ -alkenyl, C -C ₅ -alkynyl, -C-C ₄ -acyl, benzyl or phenyl, the phenyl rings in each case optionally by Halogen or -CC ₄ alkyl are substituted;

Q is a residue T-J, where

T stands for a carbonyl radical CO or for the radical -CHY,

J is an isoxazole ring of the formula II linked in the 4-position,

means in which

R ¹ for hydrogen or -CC ₄ alkyl and

R ^{2 represents} -C ₄ alkyl, cyclopropyl, 1-methylcyclopropyl or 1-methylthiocyclopropyl;

Y represents an OH group, a hydroxy group optionally acylated with C ₂ -C ₄ -acyl or a chlorine atom;

as well as agriculturally customary salts of the compounds I.

2. Saccharin derivatives of formula I according to claim 1, in which Q represents a group CO-J.

3. saccharin derivatives of the formula I in which one of the radicals L or M is hydrogen and the other hydrogen is C 1 -C ₄ -alkyl, C 1 -C ₄ -alkoxy, C 1 -C ₄ -alkylthio, chlorine, cyano, methylsulfonyl, nitro or Trifluoromethyl means.

4. saccharin derivatives of the formula I according to claims 1 to 3, in which the radicals L and M are hydrogen, methyl, methoxy, methylthio, chlorine, cyano, methylsulfonyl, nitro or trifluoromethyl.

5. Herbicidal composition containing at least one saccharin derivative of the formula I according to claim 1 and customary inert additives.

6. A method of combating undesirable plant growth, characterized in that a herbicidally effective amount of a saccharin derivative of the formula I according to claim 1 is allowed to act on the plants or their habitat.

7. A process for the preparation of the compounds of the formula I according to claim 1, in which Q represents a radical CO-J, characterized in that alkynylstannanes of the formula A2

(CH ₉ ) Sn Cs≡CR ² A2 with an acid chloride of the formula IV

where L, M and Z have the meaning given in claim 1, to benzoylalkynes of the formula B2

implemented and then with nitrile oxides of the formula C2

R ^l ££ == NN == O ^w C2 in which R ^{1 is} C 1 -C 4 -alkyl, a cycloaddition to the isoxazoles of the formula 1.2

submits.

8. Saccharin derivatives of the formula B2

in which L, M, Z and R ^{2 have} the meaning given in claim 1.