NZ209062A - Nitroarylalkylsulphone derivatives - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £09062 90 fa II If li lH Under the -provisions • of Regtf^ lat'ton 2i (i) the ^ Specification -has been ante-dsned: to /sm.u~ 4oltM {'"V; O^'i,! V IJ-'i; t6 t 0u,,k ...&7kr.?.'.

Complete Specification Fs;ed; Class: Publication Date: P.O. Journsl, No: 80 AUG 1985 I'iViT Patents Form No. 5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION NITROARYLALKYLSULFONE DERIVATIVES WE, CIBA-GEIGY AG, a Swiss Corporation of Klybeckstrasse 141, 4002 Basle, Switzerland, hereby declare the invention, for which ZVwe pray that a patent may be granted to jutf/us, and the method by which it is to be performed, to be particularly described in and by the following statement (followed by page 1 A.) # Ml - IA- /.. v.- > w //_ Nitroarylalkylsulfone derivatives The present invention relates to new nitroarylalkylsulfone derivatives and their production and their use in ganetocidal ccnpositions.

The present invention provides compounds having the formula I: wherein is C-^-Cg alkyl, R2 and Reach independently of the other, are hydrogen, C^-Cg alkyl, C-^-Cg alkoxy, C^-Cg haloalkyl, halogen, cyano, nitro or amino or, both together in the ortho-position to each other as a -(CH=CH)2~ group, complete a naphthalene ring, and is a hydrazinum or ammonium ion.

Alkyl by itself or as moiety of another substituent comprises e.g. the following groups: methyl, ethyl, propyl, butyl, pentyl and hexyl, and the isomers thereof e.g. iso-propyl, isobutyl, tert-butyl and isopentyl. Haloalkyl is a mono- to perhalogenated alkyl substituent e.g. CHC^r Ct^Cl, CCl^f CF^ or CH2CH2CI. Halogen denotes fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred.

Examples of suitable ammonium ions are: NH^> NH(alkyl)^, NH2(alkyl)2 and NH3(alkyl), such as NH(CH-j)NH.(C2Htj)3> NH2(CH3)2, Ml2(C3H7-n)2, NR3CR3, NH^Hg-n, or quaternary ammonium ions such as tetraethylarcmonium, tetrapropylaramonium, tetrabutylammonium, tetrapentylammonium, tetrahexylamcnonium, tetraheptylammonium, tetraoctylammonium, tetranonylaramonium, tetradecylammonium, methyltributyl-ammonium, dimethyldibutylammonium, trimethylbutylammonium, methyltrioctylammoniura, benzyltrimethylammonium, benzyltriethylammonium, benzyltripropylammonium, benzyl-tributylammonium, benzyldimethylhexadecylamraoniuin, benzyl- 209062 diethylhexadecylamraonium, diisobutylcresoxyethyldimethyl-benzylammonium, trimethylphenylammonium, diphenyldiraethyl-amrnonium, butyltripropylammonium, tributylphenylammoniuin or tricaprylraethylammonium. Suitable hydrazinium ions are unsubstituted or substituted hydrazinium ions, such as NH2NH3, NH2N(alkyl)3, NH2"NH(alkyl)2, NH2NH2(alkyl) etc.

In addition to NH/ , preferred ammonium cations comprise, in particular, those of the type NH^_a^ (lower alkyl)a, in which a = 1, 2, 3, or 4, and among these, in particular + + tetraalkylammoniura ions such as N(CH3)^, N(C2H^)^, N(C4H9-n)4' N(CH3)2(C2H5)+, N(C3H7_n)+, NCC-jH^)* etc.

The compounds of formula I are oils, resins or mainly solids which are stable at room temperature and have very valuable microbicidal and plant growth regulating properties. They may therefore preferably be used in agriculture or related fields for selectively influencing flower formation in plants and are also suitable for controlling phytopathogenic microorganisms.

New Zealand Patent Specification No. 2002 82 describes and claims a method of stimulating flower formation and a method of obtaining hybrid seeds by use of inter alia compounds of formula I. Specification No. 200282 is herein incorporated by reference as if fully set fort* The present invention also provides a process for producing compounds of formula I comprising neutralising a free phenol of formula II: °2N II 209062 wherein R^, R2 and R^ have their previous significance, in the temperature range from 0° to 180°C, and in the presence of an inert solvent, with an aqueous hydrazinium or ammonium hydroxide derivative, and isolating the resultant salt in conventional manner.

In addition, the invention relates to agrochemical, particularly gametocidal, compositions, comprising as active ingredient a compound of the formula I with a carrier.

The compounds of formula I in the form of compositions can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds.

These compounds can be both fertilisers or micronutrient donors or other preparations that influence plant growth.

They can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, mullusicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application-promoting adjuvants customarily employed in the art of formulation. Suitable carriers and adjuvants can be solid or liquid and correspond to the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, binders or fertilisers.

The compositions of the invention contain adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances.

\ ZQ906Z The formulations, i.e. the compositions or preparations containing the compound (active ingredient) of the formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalates or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, as well as epoxidised vegetable oils such as epoxidised coconut oil or soybean oilj or water.

The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepolite or bentonitej and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues. 2090 62 Depending on the nature of the compound of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (Ci0~^22^' e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyl taurin salts.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a Cg-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples 2 090 62 of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalene-sulfonic acid/formaldehyde condensation product. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamine propylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributyl-phenoxypolyethoxyethanol, polyethylene glycol and octyl-phenoxyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants. 209062 Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one Cg-C22_ alkyl radical and, as further substituents, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxy-alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyl-trimethylammonium chloride or benzyldi(2-chloroethyl)-ethylammonium bromide.

The surfactants customarily employed in the art of formulation are described e.g. in "McCutcheon*s Detergents and Emulsifiers Annual", MC Publishing Corp. Ringwood, New Jersey, 1979, and Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc.

New York, 1980.

The agrochemical composition usually contain 0.1 to 99%, preferably 0.1 to 95%, of a compound of the formula I, 1 to 99.9% of a solid or liquid adjuvant, and 0 to 25%, of a surfactant.

Whereas commercial products are preferably formulated as concentrates, the end user will normally employ dilute formulations.

The compositions may also contain further ingredients, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.

Such agrochemical compositions also constitute an object of the present invention.

The invention is further illustrated by the following Examples Parts and percentages are by weight. 2©f 0 -6 Example 1 a) Preparation of °2\„.

HO—^ /*"S02CH3 ^ 4-Hydroxy-3-nitrophenvlmethylsulfone .6 kg of 4-chloro-3-nitrophenylmethylsulfone are stirred slowly into 4 kg of 30 % aqueous sodium hydroxide and the mixture is diluted continuously with water to a volume of o about 50 litres. The reaction mixture is heated to 90 C and then a further 29 kg of 30 % aqueous sodium hydroxide are added, with stirring, over 3 to 4 hours. The mixture is then heated for 90 minutes to 103°C. After it has cooled to about 60°C, the solution is adjusted with 16 % sulfuric acid to a pH value of about 1.5, whereupon the product precipitates. The precipitate is isolated by filtration, washed and recrystallised from ethanol.

Yield: 24 kg of colourless crystals with a melting point of 166°-168°C. b) Preparation of i > 02\_.

C-0—^ S02CH3 (1-14) 4- r.v cl npropyl carbonyloxy- 3-ni trophenylmethyl sul f one 32.6 g of 4-hydroxy-3-nitrophenylmethylsulfone are suspended in 250 ml of tetrahydrofurane and to this suspension are added 21 ml of triethylamine. With stirring, 15.7 g of cryclopropanecarboxylic acid chloride are added dropwise to the resultant solution. After the 2090 62 weakly exothermic reaction has subsided, stirring is continued for 3 hours at room temperature and the filtrate is concentrated, affording 42 g of a viscous oil which is digested with petroleum ether. Yield: 40.5 g of pale yellow crystalline product with a melting point of 114°-116°C. c) Preparation of °2\ /y 0- '/ > \ )"S02CH3 0 N(C4H9-a)4 (2.20) 4-Hydroxy-3-nitrophenylmethylsulfone tetra- (n-butyl) ammonium salt To a solution of 13.5 g of 4-hydroxy-3-nitrophenylmethyl-sulfone in 100 ml of ethanol are added 41 g of a 40 % aqueous tetrabutylammonium hydroxide solution. The resultant deep yellow solution is evaporated in a rotovap to give 28 g of yellow crystal product with a melting point of 98°-100°C.

Examples 2 to 8 The compounds listed in the following Table can be prepared using procedures similar to those described in Example 1. -10 _ 209062 Table Compounds of Che formula I °2\..

R*°A.A"S02R1 lI) R3 2 R1 R2 R3 R4 Physical data (°C) 2.

CH3 H H n(ch3)4" m.p. 151-153° 3. ch3 H H »<C4H9n)* m.p. 98-100° 4.

CH3 H H N(C,H.). 2 5 4 m.p. 130-137° . ch3 H H N(CH3)3ch2C6H5+ orange-ye1low-res in 6.

CH3 H H N(ch3)3C12H25 orange resin 7.

CH3 H H N(ch3J2N(CH3)3 orange resin 8.

CH3 H H nh2nh3 209062 Formulation Examples for liquid active ingredients of the formula I (throughout, percentages are by weight) 1. Emulsifiable concentrates a) b) c) Compound of Table 1 25 % 40 °L 50 % calcium dodecylbenzenesulfonate 5 % 8 7« 5.8 castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5 % - tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) - 12 % 4.2 % cyclohexane - 15 7„ 20 "L xylene mixture 65 % 25 % 20 % Emulsions of any required concentration can be produced from such concentrates by dilution with water. 2. Solutions a) b) c) d) Compound of Table 1 80 % 10 °L 5 % 95 0/0 ethylene glycol monomethyl ether 20 "L polyethylene glycol 400 - 70 % - N-methyl-2-pyrrolidone - 20 % epoxidised coconut oil - - 17. 5 7. ligroin (boiling range 160-190°) - - 94 % - These solutions are suitable for application in the form of microdrops. 209062 3. Granulates a) b) Compound of Table 1 5 % 10 "U kaolin 94 % highly dispersed silicic acid 1 % attapulgite - 90 % The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo. 4. Dusts a) b) Compound of Table 1 2 % 5 % highly dispersed silicic acid 1 % 5 % talcum 97 % kaolin - 90 % Ready for use dusts are obtained by intimately mixing the carriers with the active ingredient.

Formulation examples for solid active ingredients of the formula I (throughout, percentages are by weight) Wettable powders Compound of Table 1 sodium lignosulfonate sodium laurylsulfate sodium diisobutylnaphthalene- sulfonate octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) highly dispersed silicic acid kaolin a) % 5 % 3 °L % 67 % b) 50 % 5 % 2 % 10 % 27 % c) 75 7o % 6 % 10 70 7c 209062 The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration. 6. Emulsifiable concentrate Compound of Table 1 10 % octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3 % calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (36 moles of ethylene oxide) 4 "L cyclohexanone 20 % xylene mixture 50 % coconut oil 10 7o.

Emulsions of any required concentration can be obtained from this concentrate by dilution with water. 7. Dusts a) b) c) Ready for use dusts are obtained by mixing the active ingredient with the carriers, and grinding the mixture in a suitable mill. 8. Extruder granulate Compound of Table 1 talcum kaolin 7o 95 7o 8 7o 6 7o 44 7o 92 7o 50 7o Compound of Table 1 sodium lignosulfonate carboxymethylcellulose kaolin 7c 2 7c 17. /i • ' ' 87 7o. /; £1 ■/ f-

Claims (7)

- 14 - 209062 The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air. 9. Coated granulate a) b) Compound of Table 1 3 7. 5 % polyethylene gylcol 200 3 7. 3 Z kaolin 94 °L 92 % The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner. 10. Suspension concentrate Compound of Table 1 40 % ethylene glycol 10 % nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 % sodium lignosulfonate 10 % carboxymethylcellulose 1 % 37 7o aqueous formaldehyde solution 0.2 % silicone oil in the form of a 75 % aqueous emulsion 0,8 7, water 32 %. The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water. Formulation ingredients which enhance the adhesion of the active ingredient to the plant, e.g. mineral or vegetable oils, are very effective in foliar application. ffv r 209062 - 15 - ^6, Csk' i'S What is- ciralmuQ ic>:

1. Compounds having the formula: wherein is C^rCg alkyl, R2 and R^, each independently of the other, are hydrogen, C^-Cg alkyl, C-^-Cg alkoxy, C^-Cg haloalkyl, halogen, cyano, nitro or amino or, both together in the ortho-position to each other as a -(CH=CH)2~ group, complete a naphthalene ring, and R^ is a hydrazinium or ammonium ion.

2. Compounds of formula I substantially as described with reference to any of the Examples.

3. Process for producing compounds of formula I as defined in claim 1 comprising neutralising a free phenol of formula II: o2n HO -(/ v^SO^ II A-—X r3 r: wherein R1, R2 and R^ have their previous significance, in the temperature range from 0° to 180°C, and in the presence of an inert solvent, with an aqueous hydrazinium or ammonium hydroxide derivative, and isolating the resultant salt in conventional manner.

4. Process according to claim 3 substantially as described with reference to any of the Examples. - 16 - 2Q306Z

5. Compounds of formula I when produced by a process claimed in claim 3 or 4.

6. An agrochemical composition containing a compound as claimed in claim 1 or claim 2 together with a suitable carrier.

7. A gametocidal composition containing a compound as claimed in claim 1 or claim 2 together with a suitable carrier. CIBA-GEIGY AG By their Attorneys