IE47637B1 - Sulphonanilides useful as pesticides and plantgrowth regulants - Google Patents

Abstract

Controlling pests and regulating plant growth comprises treatment with a sulphonamide of formula (I) or its salt. In (I) R1 is cycloalkyl, NR7R8 or opt. substd. alkyl, aralkyl, aryl or heterocyclyl; R7 and R8 are H or opt. substd. alkyl, aralkyl or aryl; R is alkylene or alkenylene; A is COOH, CSSH, CEGR9, CENR10 R11, COO.N=CR7R9, CN or COR12 opt. as carbonyl deriv. or addn. cpd. E and G are O or S; R9 is opt. substd. alkyl, aralkyl or aryl; R10 and R11 are as R7, or together complete opt. substd. heterocyclyl; or R10 is H and R11 is -N=CR7R9 or HNR13; R13 is H or COOR9; R12 is H, cycloalkyl or opt. substd. alkyl, aralkyl, aryl or C -bound heterocyclyl. Alternatively RA is the gp. (II); R14 is H, alkyl or aryl; (I) are variously useful as growth regulators, herbicides (total or selective), fungicides, insecticides and antibacterials.

Description

This invent inn I'chitrs In new compound·; jin.l tlirir prodm I inn and to methods anil compos itions for combating posts and for regulating the growth of a plant.

Accordingly, the invention provides a method of combating 5 pests at a locus infested or liable to be infested with them or of regulating the growth of a plant at a locus at which the plant is growing or is to grat, which method comprises applying to the locus a pest-combating or plant growth regulant amount of a compound which is a sulphonanilide of fomula or salt thereof, wherein R1 represents alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, a heterocyclic group, n7 a substituted heterocyclic group, or a group of formula θ 8 R where R and R are the same or different and each represents a hydrogen atom, alkyl, substituted alkyl, aralkyl, substituted aralkyl, aryl or substituted aryl; R represents alkylene or alkenylene; A represents -COOH; -CSSH; -CEGR9; -CENR^R11; -B-O-N=C<Rq ; .

-Qi; -COO cycloalkyl; or -COS. or a carbonyl derivative or addition ccnpound 25 thereof; vjhere E and G are the same or different and each represents an oxygen. or sulphur iitorri; !I represents alkyl, subsl i tule.I alky!, aralkyl, ID substituted aralkyl, aryl or substituted aryl; II1” and !l’* are the sail»· or different and each represents a group as defined for R ; or Rll) and R11 together with the nitrogen atom to which they are 5 attached form a heterocyclic group or a substituted heterocyclic group; or R1^ represents a hydrogen atom while R11 represents a group of formula -N=C<^ g or -N^ 13 where P. represents a hydrogen atom 9 12 R or -COOR ; and R represents a hydrogen atom, alkyl, substituted alkyl, cycioalkyl, aralkyl, substituted aralkyl, aryl, substituted aryl, a heterocyclic group linked via a carbon atom in the group or such a heterocyclic group which is substituted; or R-A represents a group of formula >®2k /RU CH, C< .. I L R1S Ϊ wherein R11 represents a hydrogen atom, alkyl or aryl, B represents I TC TC an oxygen atom or -NR , R represents a hydrogen atom or alkyl, and n represents 0, 1 or 2; and R2, r\ R4, R8 and R6 are the same or different and each represents a hydrogen atom; alkyl; substituted alkyl; hydroxy; alkoxy; -SCN; nitro; halogen; amino; substituted amino; mercapto; a group of formula -SR16, -SOR16, -SO2R16 or -OSO,R16 where R16 represents alkyl, aryl or aralkyl; -SO^NR^R8; or -COOR12 Tins Invention pruvlilea nltio n peel leiilul inplant growth regulant composition containing the compound, especially such a composition comprising the compound together with at least one material selected from carriers, surface active agents, other pesticides, other plant growth regulants, antidotes and fertilizers.

The compounds are novel, and the invention provides them per se.

The invention also provides a process for 10 preparing the compounds, which process comprises: (a) reacting a sulphonamide of formula: 47037 oi- salt thereof·, with a halo derivative of formula X -It Λ, wherein X represents a halogen atom nnd Λ, It, It’, It^, It'\ 1’\ Π’*’ and l'fl are as defined above; (b) acylating an arylamino derivative of formula or salt thereof, with an acylating agent of formula R^SO^Z or 12 (R SO^O where Z represents a halogen atom and A, R, R , R , •r λ r c.

R , R4, R3 and R° are as defined above; (c) where A represents -COOH, hydrolysing a sulphonanilide of g 10 11 formula I or salt thereof in which A represents -COOR , -CONR R , 15 -$-O-N=C<^ or -CN where R7, R9, R10 and R11 are as defined above; Q (d) where A represents -COOR , esterifying a sulphonanilide of formula I or salt thereof in which A represents -COOH with an alcohol of formula R9OH; Q (e) where A represents -CEGR , reacting an acyl halide of formula with an alcohol or mercaptan of formula R GH, where Y represents a hitloi'.en atom anil li, G, R, I?, K2, ll\ ll'’, li’, lih and l{Q .ire ar. delined above; (f) where A represents , reacting the acyl halide of formula IV where E represents an oxygen atom with an amino derivative of formula HNr’OrU, where R^ and are as defined above; (g) where A represents -fi-O-N=CZRQ, reacting the acyl halide of \Ry formula IV where E represents an oxygen atom with a hydroxylamine 7 9 derivative of formula HON=cCg where R and R are as defined above; (h) where A represents -CDRiSxcept where R^2 represents a hydrogen atan) or a carbonyl derivative or addition canpound thereof, decarboxylating a carboxylic acid, of formula (i) where A represents a carbonyl derivative of -COR , reacting the corresponding conpound in which A represents -OOR with a material of formula HMH to eliminate a molecule of water between them wliere M represents a divalent radical such that the material of formula 12 HMH reacts with the ccsipound in which A represents -COR to form a carbonyl derivative thereof; (j) where A represents .Oalkyl '12 Oalkyl reacting the corresponding compound in which Λ represents -(X)R^ with an orthoformate of formula CH(Oalkyl) · 1? (k) where Λ represents an oxime carbamate of -C-R ', reacting the corresponding oxime with an isocyanate, or a carbamoyl chloride, or with phosgene and then an amine; fl 12 (l) where A represents an addition compound of -C-R , reacting the corresponding compound in which A represents -COR with the compound with which it is required to make up the addition compound; (m) to produce a salt of the sulphonanilide,salifying the sulphonanilide; or (n) to produce the sulphonanilide, desalifying a salt of the sulphonanilide.

Some of the intermediates in the production of the present compounds are novel, including: 2' ,6'-dimethyl-l-propanesulphonanilide, 2',6’-dichloro-methanesulphonanilide, 2'-chloro-6’-methyl-methanesulphonanilide, 2',6'-dimethyl-l-butanesulphonanilide, 2',6'-dimethyl-ethanesulphonanilide, 21-ethyl-methanesulphonanilide, 3’,4'-dichloro-2-thiophenesulphonanilide, 3'-chloro-4'-fluoro-methanesulphonanilide, 3’-chloro-4’-methyl-methanesulphonanilide, 21-methanesulphonyloxy-methanesulphonanilide, 2' ,6' -diisopropyl-methanesulphonanilide, 2’-methanesulphonyloxy-S1-nitro-methanesulphonanilide, 21,6’-dimethyl-dimethylaminosulphonanilido, 21-chloro-61-methyl-dimethylaminosulphonanilide, 21,3'-dichloro-methanesulphonanilide, . 3' ,4'-dimethyl-methanesulphonanilide, 21,6'-dimethyl-2-propanesulphonanilide, 31,4'-dichloro-ethoxycarbonylmethanesulphonanilide, 3',5'-dichloro-methanesulphonanilide, 2' ,6'-dimethyl-4-morpholinesulphonaniiide, 3',4’-dichloro-4-morpholxnesulphonanilide, and their salts.

The novel intermediates wnich are sulphonamides of formula II, or salts thereof, may be prepared hy acylating an aniline of formula or salt thereof with an acylating agent of formula pJsOgZ or 3 The sulphonanilide of formula I may form salts.. When R, R , R^, R5 or R.6 represents -COOH, or A represents -COOH or -CSSH, a salt may be formed with a base, e.g. sodium hydroxide. Such salts include metal, particularly alkali metal, especially sodium or potassium, salts and amine salts, e.g. methylamine or ethanolamine 7637 salts. The salts may be formed from the non-salt form (i.e. the non-salt form may be salified) in ways conventional for other salts, and may be converted to the non-salt form (i.e. desalified) in ways conventional for other salts. Thus, a salt may be formed by reaction of the non-salt form with a base, e.g. sodium hydroxide, and a salt with a base may be converted to the non-salt form by reaction with an acid, e.g. hydrochloric acid.

The sulphonamides of formula II may form salts. Salts may be formed from the non-salt form in ways conventional for other salts, IQ and may be converted to the non-salt form in ways conventional for other salts. Thus salts may be formed by reaction of the non-salt form ivith a strong base, and may be converted to the non-salt form by reaction with an acid, e.g. hydrochloric acid. Salts include for exanple potassium salts.

When R12 in -$-R12 represents a hydrogen atom, tlie present . fi 12 sulphonanilides are aldehydes; when R in -C-R represents other than a hydrogen atom, the present sulphonanilides are ketones. In both cases, carbonyl derivatives are formed. The derivatives can be considered as being derived from the carbonyl group of A by reaction 2o with elimination of a molecule of water. The derivatives include: ketals, where A represents e.g. or -CH, CH, I··—QL SQL thioketals, where A represents e.g. — C—SQL· I or Cl’ oximes, where A represents e.g.

-% I^S-QL· ®3 n oxime esters, where A represents e.g. -C—CHg NOOOCHj oxime ethers, where A represents e.g.

V3 KOCHg oxime carbamates, where A represents e.g. -C-t-Bu N-O-gNHCH3 hydrazones, where A represents e.g. substituted hydrazones, for instance methylhydrazones, where A represents e.g. q_q, or II 3 WKH, phenylliydrazones, where Λ represents e.g. -C—Cll^ NNtiPh and setnicarbazanes (including thiosanicarbazanes ),where A represents e.g, -CH—CH« 3 NNHCSNI^ Carbonyl derivatives are well known in themselves. lhe addition compounds include those with cyanide ion, bisulphite ion or ammonia. The ions may be for instance ammonium, sodium or potassium ions. Addition compounds of aldehydes and ketones are well known in themselves.

The present compounds are preferably prepared by reacting the sulphonamide of formula II or salt thereof with the halo derivative of formula X-R-A. X represents a halogen (ie. fluorine, chlorine, bromine or iodine) atom, preferably a chlorine or bromine atom, lhe reaction is usually conducted in the presence of an acid acceptor, e.g potassium carbonate. lhe present conpounds may be prepared by acylating the arylamino derivative of formula III or salt thereof with an 1 1 acylating agent of formula (R or Pre^era’’ly SO2Z. Z usually represents a chlorine atom.

The present conpounds in which A represents -COOH may be □ prepared by hydrolysing the conpound in which A represents -COOR , -CONR^R11, -?-0-N=Cr^o or -CN. The hydrolysis is usually conducted xRy in the presence of acid (e.g. sulphuric acid) or base (e.g. sodium hydroxide).

Q The present compounds in which A represents -COOR may be prepared by esterifying the conpound in which A represents -COOH.

The esterification is usually conducted in the presence of acid (e.g. sulphuric acid). q The present compounds in which A represents -CEGR may be 9 prepared by acylating the alcohol or mercaptan of formula R GH with the acyl halide of formula IV. Y in formula IV represents a halogen, usually a chlorine, atom.

The present conpounds in which A represents -COHR^R11 may be prepared by acylating the amino derivative of formula HNR.10r11 with the acyl halide of formula IV where E represents an oxygen atom. Again Y usually represents a chlorine atom.

The conpounds in which A represents -COR may be prepared by decarboxylating a carboxylic acid of formula V. Decarboxylation may be brought about for exanple by heating. The carboxylic acid is preferably prepared in situ, for exanple by hydrolysis of its ester e.g. its ethyl ester.

. The conpounds in which A represents a carbonyl derivative of -COR may be prepared by reacting the corresponding conpound in 12 which A represents -COR with a material of formula ΗΉ to eliminate a molecule of water between them. For instance, a conpound in which A represents -COCHj may be reacted with ethylene glycol in the presence of acid to form the corresponding conpound in which A /°-?!2 represents Ihe compounds in which A represents may be prepared by reacting the corresponding conpound in which A 12 represents -COR with an orthoformate of formula CH(0alkyl)3, usually 10 in the presence of for exanple an acid such as 4-toluenesulphonic acid or hydrogen chloride, or ammonium chloride or ferric chloride.

The sulphonamide of formula II or salt thereof may be prepared by acylating an aniline of formula VI or salt thereof xvith the acylating agent of formula (R^SO^IgO or preferably R^SOgZ. Again Z usually represents a chlorine atom.

The acyl halide of formula IV may be prepared by reacting a sulphonanilide of formula I in which A represents -COOH or -CSSH or salt thereof with thionyl halide, phosphoryl halide, phosphorus pentahalide or oxalyl halide, particularly the chlorides and especially thionyl chloride.

The present processes are usually conducted in the presence of a solvent, and usually are carried out at 0-200 e.g. 0-150°C. Ihe solvent may be for exanple water or an ether, ketone, hydrocarbon, amide or alcohol. Ihe pressure may be for instance 0.5 to 10 atmospheres, conveniently ambient pressure. tiny substituted alkyl group in the present compounds preferably has as the substituent(s) one or more of halogen, alkoxy, furyl, phthalimido, -SCN, amino, substituted amino (e.g. amino mono- or di-substituted by alkyl or acyl), alkoxycarbonyl, carboxy, -^-NR^R11, benzoyloxy, alkanoyloxy, alkylsulphonyloxy, nitrile and hydroxy. In 2 S 4 5 6 the case of R , R , Ry R3 and R , a preferred such substituted alkyl group is “CFj.

Any acyl group is preferably alkanoyl.

Any substituted aryl group is preferably aryl substituted by 10 one or more of halogen, alkyl, alkoxy, alkylsulphonyloxy, nitro, —SCN and trifluoromethyl.

Any substituted aralkyl group is preferably substituted on the aryl nucleus. Ihe substituent (s) are preferably selected from halogen, alkyl, alkoxy, nitro, -SCN, alkylsulphonyloxy and trifluoromethyl.

When any of the present symbols represents a substituted or unsubstituted group, it is preferably unsubstituted. When it is substituted by more than one substituent, the substituents are usually the same, e.g. all chlorine or all methyl.

Any alkyl group involved in the present symbols is preferably of 1-15, e.g. 1-8, especially 1-6, carbon atoms, for exanple methyl, ethyl, propyl, isopropyl, butyl or hexyl. Any cycloalkyl group is preferably of 3-7 carbon atoms, especially eyclohexyl or cyclopentyl. Any aryl group is preferably phenyl. Any aralkyl group is preferably phenylalkyl, e.g. of 7-10 carbon atoms, especially benzyl. Any halogen is preferably fluorine, chlorine or bromine especially chlorine, Any alkoxy is prolcriiblv of 1-6 i.-irlion atom'., '·.(>. ncthoxy. Any alkanoyl group is preferably of 2-7 carlton atoms, lhe alkylene or alkenylene group which R represents may be branched or straight chain. Usually it contains 1-6, preferably 1-3, carbon atoms. Especially preferred when A represents 12 -COR or a carbonyl derivative or addition conpound thereof is R representing methylene; when A represents^gther values, it is especially preferred that R represents where represents alkyl of 1-5, preferably 1 or 2, carbon atoms.

Hie heterocyclic or substituted heterocyclic group which R1- may represent may be linked via a ring carbon or ring hetero atom.

Any heterocyclic group involved in the present symbols is usually a single hetero ring containing 3 to 7 ring atoms of which 1-3, e.g. or 2, are hetero atoms, each hetero atom being nitrogen, sulphur or oxygen, to which hetero ring a benzene ring is optionally fused. The heterocyclic group may be for exanple furyl, thienyl, piperidyl, pyrrolyl, piperazinyl, morpholinyl or benzofuranyl. Any substituent on a heterocyclic group may be for instance alkyl e.g. methyl, oxo, nitro, or halogen e.g. chlorine.

Preferably, the heterocyclic group which -NR^°R^^ may represent is a single hetero ring containing 5-7, e.g. 5 or 6,ring atoms of which besides the nitrogen atom there may be 1 or 2 further hetero atoms, each hetero atom being oxygen, sulphur or nitrogen, to which hetero ring a benzene ring is optionally fused. The heterocyclic group is preferably piperazino, pyrrolidino, piperidino or morpholino. Any substituent may be for instance alkyl, e.g. methyl, oxo, nitro, or halogen, e.g. chlorine.

Thus, in a preferred embodiment, R1 represents alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, alkoxycarbonyl of 2-7 carbon atoms, carboxy, -CNR10Rl;1·, phthalimido, -SCN, benzoyloxy, alkanoyloxy of 2-7 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, furyl, nitrile, hydroxy, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; cycloaikyl of 3-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro, -SON, alkylsulphonyloxy of 1-6 carbon atoms and trifluoromethyl; a heterocyclic group which is a single hetero ring containing 3 to 7 ring atoms of which 1-3 are hetero atoms, each hetero atom being nitrogen, sulphur or oxygen, to which hetero ring a benzene ring is optionally fused; such a heterocyclic group substituted by one or more of alkyl of 1-6 carbon atoms, oxo, nitro and halogen; or a group of formula 8 where R and R are the same or different and each represents a hydrogen atom; alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms. alkoxycarbonyl of 2-7 carbon atoms, carboxy, plitlialimido, -SCN, benzoyloxy, alkanoyloxy of 2-7 carbon atoms, alkylsulphonyloxy of l-(> carbon atone, furyl, nitrile, hydroxy, amino and amino mono10 or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro, -SCN, alkylsulphonyloxy of 1-6 carbon atoms and trifluoromethyl; phenyl; or phenyl substituted by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, nitro, -SCN and trifluoromethyl; R represents alkylene or alkenylene of 1-6 carbon atoms; A represents -COOH; -CSSH; -CEGR9; -CENR^R11; -C-O-N=C<^g ; -CH; cycloalkyloxycarbcxiyl of 4-3 carbon atans; or-COR^2 or a carbonyl derivative or additicn canpound thereof; where E and G are the same or different and each represents g an oxygen or sulphur atom, R represents alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, alkoxycarbonyl of 2-7 carbon atoms, carboxy, -StfR^R11, phthalimido, -SCN, benzoyloxy, alkanoyloxy of 2-7 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, furyl, nitrile, hydroxy, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro, -SCN, alkylsulphonyloxy of 1-6 carbon atoms and trifluoromethyl; phenyl; or phenyl substituted by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, nitro, -SCN and trifluoromethyl; r’0 and R7’’ are the same or different and each represents a group as defined for R7 immediately above; or and R^ together with the nitrogen atom to which they are attached form a heterocyclic group which is a single hetero ring containing 5-7 ring atoms of which besides the nitrogen atom there may be 1 or 2 further hetero atoms, each hetero atom being oxygen, sulphur or nitrogen, to which hetero i ring a benzene ring is optionally fused; such a heterocyclic group substituted by one or more of alkyl of 1-6 carbon atoms, oxo, nitro and halogen; or R^ represents a hydrogen atom while r’’’’ represents n7 13 a group of formula -N=C7^ g or -N< 13 where R represents a hydrogen 9 12 ” ” atom or -COOR ; and R represents a hydrogen atom, alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, alkoxycarhonyl of 2-7 carbon atoms, carboxy, -^JR^R11, phthalimido, -SCN, benzoyloxy, alkanoyloxy of 2-7 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, furyl, nitrile, hydroxy, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; cycloalkyl of 3-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, allyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro, -SCN, alkylsulphonyloxy of 1-6 carbon atoms and tri fluornmothyl; phenyl; phenyl substi tub'd hy one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, nitro, -SCN and trifluoromethyl; a heterocyclic group linked via a carbon atom in the group, which group is a single hetero ring containing 3 to 7 ring atoms of which 1-3 are hetero atoms, each hetero atom being nitrogen, sulphur or oxygen, to which hetero ring a benzene ring is optionally fused; or such a heterocyclic group substituted by one or more of alkyl of 1-6 caibon atoms, oxo, nitro and halogen; or R-A represents a group of formula wherein R14 represents a hydrogen atom, alkyl of 1-6 carbon atoms or phenyl, B represents an oxygen atom or -l^iR15, R15 represents a hydrogen atom or alkyl of 1-6 carbon atoms, and n represents 0, 1 or 2; R2, R8, R4, R5 and R6 are the same or different and each represents a hydrogen atom; alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, alkoxycarbonyi of 2-7 carbon atoms, carboxy, -^NR^R11, phthalimido, -SCN, benzoyloxy, alkanoyloxy of 2-7 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, furyl, nitrile, . 47637 hydroxy, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; hydroxy; alkoxy of 1-6 carbon atoms; -SCN; nitro; mercapto; a halogen atom; amino; amino mono5 or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; a group of formula -SR16, -SOR16, “SO2R16 or -OSO2R16 where R16 represents alkyl of 1-6 carbon atoms, phenyl or phenyl7 8 7 8 alkyl of 7-10 carbon atoms; -SOjNRR where R and R are 12 defined immediately above; or -COOR is as defined immediately above. Within this embodiment, preferably 3 or 4 of R2, R2, R^, R6 and R6 each represents a hydrogen atom.

In a particular embodiment of the present compounds, R1 represents alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, or a group of 1)7 , q formula -N·^'o where R and R are the same or different and each \R8 represents a hydrogen atom, alkyl, substituted alkyl, aralkyl, substituted aralkyl, aryl or substituted aryl; R represents alkylene; IS A represents -COOH, -CSSH, -CEGR9, -CENR10RU, -C-O-N=C^Rg or -CN; where E and G are the same or different and each represents □ an oxygen or sulphur atom; R represents alkyl, substituted alkyl, aralkyl, substituted aralkyl, aryl or substituted aryl; R10 and R11 are the same or different and each represents a group as defined for R?; or R*° and R^ together with the nitrogen atom to which they are attached form a heterocyclic group; or represents a -J hydrogen atom while R represents a group of formula □ or /H ,, g R -N^r13 where R represents a hydrogen atom or -COOR (in which R9 represents particularly ethyl); and R2, R3, R4, R5 and R6 are the same or different and each represents a hydrogen atom, alkyl, substituted alkyl, alkoxy, -SCN, nitro, mercapto, alkylmercapto, amino or a halogen atom Preferably, within this embodiment, R represents alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more o£ halogen, alkoxy of 1-6 carbon atoms, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; cycloaikyl of 3-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carhon atoms, alkoxy of atoms 1-6 carbon/, nitro and trifluoromethyl; · or a group of fcrmula urf 7 R -NC o where R and R are the same or different and each represents R8 a hydrogen atom; alkyl of 1-15 carbon atoms; allyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carhon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carhon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atons, alkoxy of 1-6 carbon atoms, nitro and trifluoromethyl; phenyl; or phenyl substituted by one or more of halogen, alkyl of 1-6 carhon atoms, alkoxy of 1-6 carbon atoms, nitro and trifluoromethyl; 2o R represents alkylene of 1-6 carbon atoms; A represents -OOOH, -CSSH, -CEGR9, -CENR^R11, or -CN; where E and G are the same or different and each represents Q an oxygen or sulphur atom; R represents alkyl of 1-15 carbon rfcms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of l-ΰ carbon atoms, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro and trifluoromethyl; phenyl; or phenyl substituted by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro and trifluoromethyl; R10 and R11 are the same or different and each represents a group as defined for R7 immediately above; or R1® and R11 together with the nitrogen atom to which they are attached fom a monocyclic heterocyclic group containing 5 or 6 ring atoms of which besides the nitrogen atom there may be a further hetero atom, which hetero atom is oxygen or nitrogen; or represents a hydrogen atom while R11 fy rt » r £ R , R , R , R and R are the same or different and each represents a hydrogen atom; alkyl of 1-15 carbon atoms; alkyl of 1- 15 carbon atoms substituted by one or more of halogen, alkoxy 20 of 1-6 carbon atoms, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of . 2- 7 carbon atoms; alkoxy of 1-6 carbon atoms; -SCN; nitro; mercapto; alkylmercapto of 1-6 carbon atoms; amino or a halogen atom In another particular embodiment, R1 represents alkyl, substituted allyl, cycloalkyl, aralkyl, substituted aralkyl, a heterocyclic group, a substituted heterocyclic group, or a group of formula -Νζ^ g 7 8 where R and R are the same or different and each represents a hydrogen atom, alkyl, substituted alkyl, aralkyl, substituted aralkyl, aryl or substituted aryl; R represents alkylene or alkenylene; A represents -COR or a carbonyl derivative or addition conpound 12 thereof, where R represents a hydrogen atom, alkyl, substituted allyl, cycloalkyl, aralkyl, substituted aralkyl, aiyl, substituted aryl, a heterocyclic group linked via a carbon atom in the group or such a heterocyclic group which is substituted; and Ο 'ϊ A C (s R , R , R*, R and R are the same or different and each represents a hydrogen atqm; alkyl; substituted alkyl; alkoxy; -SCN; nitro; halogen; amino; substituted amino; mercapto; a group of fomula -SR16, -SOR16 or -SO2R16 where R16 represents 7 β 7 8 alkyl, aryl or aralkyl; -SO^NR R where R and R are as defined 12 12 immediately above; or -COOR where R is as defined immediately above.

Within this embodiment, preferably, R1 represents alkyl of 1-15 caibon atoms; allyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; eycloalkyl of 3-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon, nitro and trifluoromethyl; a heterocyclic group which is a single hetero ring containing 3 to 7 ring atoms of which 1 or 2 are hetero atoms, each hetero atom being nitrogen, sulphur or oxygen, to which hetero ring a benzene ring is optionally fused; such a heterocyclic group substituted by one or more alkyl of 1-6 carbon atoms, nitro and halogen; or a group of formula fi where R and R are the same or different and each represents a hydrogen atom; alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms, phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro and trifluoromethyl; phenyl; or phenyl substituted by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, nitro and trifluoromethyl; R represents alley lene or alkenylene of 1-6 carbon atoms; A represents -COR or a carbonyl derivative or addition 12 conpound thereof, where R represents a hydrogen atom, alkyl of S 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; eycloalkyl of 3-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro and trifluoromethyl; phenyl; phenyl substituted by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, nitro and trifluoromethyl; IS a heterocyclic group linked via a carbon atom in the group, which group is a single hetero ring containing 3 to 7 ring atoms of which 1 or 2 are hetero atoms, each hetero atom being nitrogen, sulphur or oxygen, to which hetero ring a benzene ring is optionally fused; or such a heterocyclic group substituted by one or more of alkyl of 1-6 carbon atoms, nitro and halogen; and RZ, R3, r\ R5 and R6 are the same or different and each represents a hydrogen atom; alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, amino and amino mono- or di-substituted by grotps selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon fitoin·;; alkoxy oF 1-6 carbon aionis; nitro; morraito; a halogen atom; amino; amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; a group of formula -SR16, -SOR16 or -SO2R16 where R16 represents alkyl of 1-6 carbon atoms, phenyl or phenylalkyl of 7-10 12 carbon atoms; or -COOR where R is as defined immediately above. Particularly preferred conpounds are those wherein, R1 represents alkyl of 1-4 carbon atoms, 2-phthalimidoethyl, ethoxycarbonylmethyl, morpholino, thienyl or dialkylamino of 2-8 carbon atoms; R represents alkylene of 1-3 carbon atoms or alkenylene of 3 carbon atoms; A represents -COOH; -CENH2; -CN; -CONHPh; cycloalkyloxycarbony1 of 4-8 carbon atoms; irorpholinocarbonyl; -CONHNH2; -CONFIG^ COOalkyl of 1-4 carbon atoms; -CONHNHCOO alkyl of 1-4 carbon atoms; -COOR17 or -CON(R17)2 where R17 represents alkyl of 1-5 carbon CHj atoms; -COCH^; -03GL,0H; ‘3 ’ °®3 OCH. ‘3 '0-CH.

COOEt !20H •SCN ; -COC —H 'COOEt NOH II 3 0 R-Λ represents ; and or 4 of R2, R3, P4, P,5 and R6 each represents a hydrogen atom and the remainder are the same or different and each represents alkyl of 1-3 carbon atoms, halogen, hydroxy, phenylmercapto, -SCN, nitro, alkoxy of 1-6 carbon atoms, trifluoromethyl, phenylsulphonyl, or methylsulphonyloxy.

In a particularly preferred group, 3 or 4 of R2, R3, R4, anj 12 R° each representsa hydrogen atom. When A represents -COR or a carbonyl derivative or addition compound thereof, it is particularly preferred that R3, R4 and R5 or R2, R3, R3 and R6 each represent a hydrogen atom.

In a particularly preferred group, R1 represents alkyl of 1-4 carbon atoms or thienyl, R represents methylene, s_ A represents -COCH^, <7 OCH, -OCH, -C—CH, or -COCCCHj)^, or 4 of R2, R3, R4, R3 and R6 each represents a hydrogen atom and the remainder are the same or different and each represents alkyl of 1-3 carbon atoms, halogen or alkoxy of 1-6 carbon atoms.

In another particularly preferred group, represents alkyl of 1-4 carbon atoms; „18 R represents -CH- in which r’’® represents methyl or ethyl; A represents -COOH, -OOOR17, -CENH^, -CQN(R17)2, -CM or -CONHPh 17 where R represents alkyl of 1-8 carbon atoms; and or 4 of RZ, R3, r\ R5 and each represents a hydrogen atom and the remainder are the same or different and each represents 10 alkyl of 1-3 carbon atoms, halogen, alkoxy of 1-6 carbon atoms or trifluoromethyl.

Specific conpounds are specified in the Examples.

Preferred specific conpounds, particularly as herbicides, are N-cyanomethyl-3',4'-dichloro-methanesulphonanilide; N- (l-£je thoxycarbonylZ7ethvl)-2',6'-dimethyl-l-propanesulphonanilide; and N-(l-/jethoxycarbonylZ7ethyl)-2',6'-dine thyl-ethanesulphonanilide.

Another preferred specific conpound, particularly as a fungicide, e.g. for use on vines or potatoes, is N-(1-(methoxycarbonyl)ethyl)-2’,6'-dimethyl-methanesulphonanilide. 6 37 Another preferred specific compound, particularly as a fungicide, is N-2-oxopropyl-2',6,-dimethyl-inethanesulphonanilide.

The present compounds are pesticides and plant growth regulants.

Hie conpounds, especially those wherein A represents -COOH, -CSSH, -CEGR9, -CENrIOrU, -S-O-N^C^^q , -COO cycloaikyl or-GN, are particularly ^-R active on plant physiology, affecting the growth of plants so that the conpounds may be used as herbicides or plant growth regulants. The 12 present compounds, especially those wherein A represents -COR or a carbonyl derivative or addition conpound thereof, are also particularly useful as fungicides. The present conpounds, especially those wherein A represents an oxime carbamate, are also particularly useful as insecticides. The present conpounds are also anti-bacterial agents. The present conpounds are outstandingly useful for combating fungus or weeds in crops. lhe conpounds may be enployed to combat for instance chickweed (Stellaria media), fathen (Chenopodium album), wild oat (Avena fatua), blackgrass (Alopecurus nyosuroides), barnyardgrass (Echinochloa cruss-galli) or crabgrass (Digitaria sanguinalis).

The conpounds may be enployed to conibat weeds in for exanple food crops such as potatoes, vines, carrots or cereals, e.g. rice, wheat, barley or maize, ornamental crops, or plantation crops such as cotton.

For use as fungicides, the conpounds are preferably enployed to conibat fungal diseases of plants, particularly of a crop specified above.

The compounds can be used to confcat various fungal genera, e.g. f’ythium, Phytophthora, Plasmopora, or Pyricularia.

Die present conpounds are normally employed in tiie form of compositions, which can be prepared by admixing the ingredients. Usually the compositions are initially produced in the form of concentrates, e.g. containing 0.5-85¾ of the present conpound, and these are diluted with water or hydrocarbon, usually water, for application, generally such that the concentration of the compound is 0.05-5¾. though in ultra low volume application the concentration may be higher, e.g. tp to 20¾. Percentages and parts in this specification are by weight unless otherwise indicated.

The conpositions normally contain a surface active agent and/or a carrier.

The carrier may be a liquid, e.g. water (e.g. water used to dilute a concentrate for application). If water is employed as carrier in a concentrate, an organic solvent may also be present as carrier, though this is not usually employed. A surface active agent may advantageously be present.

The carrier may be a liquid other than water, for example an organic solvent, such as a water immiscible solvent, e.g. a hydrocarbon which boils within the range 130-270°C, in which the conpound is dissolved or suspended. A concentrate containing a water iraisciblo solvent suitably also contains a surface-active agent so that the concentrate acts as a self-emulsifiable oil on admixture with water. Ihe liquid may be a water-misciblc solvent e.g. 2-methoxyethanol, methanol, propylene glycol, diethylsne glycol, diethylene glycol monoethyl ether, formamide or methylformamide.

The carrier may be a solid, which may be finely divided.

Examples of suitable solids are limestone, clays, sand, mica, chalk, attapulgite, diatomite, perlite, sepiolite, silicas, silicates, lignosulphonates, peat and solid fertilizers. The carrier can be of natural or synthetic origin or can be a modified natural material.

Wettable powders soluble or dispersable in water may be formed by admixing the conpound in particulate form with a particulate carrier or spraying molten conpound on to the particulate carrier, admixing a wetting agent and a dispersing agent and finely grinding the whole powder mixture.

An aerosol composition may be formed by admixing the conpound with a propellant e.g. a polyhalogenated alkane such as dichlorodifluoromethane, and suitably also with a solvent.

A flowable suspension concentrate may be formed if the conpound has a low water solubility by grinding the conpound with water, a wetting agent and a suspending agent.

A flowable suspension concentrate wherein the carrier is a hydrocarbon which boils within the range 13O-27O°C rather than water may be formed.

Thus the present composition can. for example be solid (e.g. dust or granules) and contain a solid carrier, or liquid (e.g. an emulsifiable concentrate) and contain a liquid carrier which is a hydrocarbon which boils within the range 130-270°C.

The term 'surface-active agent' is used in the broad sense to include materials variously called emulsifying agents, dispersing agents and wetting agents. Such agents are w;ell known in the art.

Ihe surface active agents used may comprise anionic surface active agents, for example soaps, mono- or di-esters of phosphoric acid with fatty alcohol ethoxylates or salts of such esters, fatty alcohol sulphates such as sodium dodecyl sulphate, sodium octadecyl sulphate or sodium cetyl sulphate, ethoxylated fatty alcohol sulphates, ethoxylated alkylphenol sulphates, lignin sulphonates, petroleum sulphonates, alkyl-aryl sulphonates sucli as alkyl-benzene sulphonates or lower alkylnaphthalene sulphonates, e.g. butyl-naphthalene sulphonate, salts of sulphonated naphthaleneformaldehyde condensates, salts of sulphonated phenol-formaldehyde condensates, or more complex sulphonates such as the amide sulphonates e.g. the sulphonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulphosuccinates e.g. the sodium sulphonate of dioctyl succinate.

The surface active agents may also comprise non-ionic agents, for example condensation products, of fatty acid esters, fatty alcohols, fatty acid amides or fatty-, alkyl- or alkenylsubstituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers e.g. sorbitan fatty acid esters, condensation products of such esters with ethylene oxide e.g. polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol, or ethoxylated acetylenic glycols.

The surface active agents may also comprise cationic agents, for exanple allyl- and/or aryl-substituted quaternary ammonium conpounds such as cetyl trimethylammonium bromide or ethoxylated tertiary fatty amines.

Preferred surface active agents include ethoxylated fatty alcohol sulphates, lignin sulphonates, alkyl-aryl sulphonates, salts of sulphonated naphthalene-formaldehyde condensates, salts of sulphonated phenol-formaldehyde condensates, dialkyl sulphosuccinates, alkyl phenol ethoxylates, and fatty alkyl ethoxylates.

Non-ionic surface active agents are preferred. lhe present active conpound may be admixed with another pesticide, e.g. herbicide,fungicide, insecticide or anti-bacterial agent, or with another plant growth regulant. The invention provides a one pack presentation, in which the present conpound is already mixed with other pesticide or plant growth regulant, and also a single package designed to hold the present conpound and other pesticide or plant growth regulant in separate containers, for mixing, e.g. in a spray tank, for application. Particular advantages are obtained with mixtures with another herbicide or fungicide. The present compound may be used sequentially with another pesticide or plant growth regulant particularly with another herbicide or fungicide, e.g. one herbicide applied before planting or before emergence of a crop and the other herbicide applied after emergence of the crop.

The other herbicide may be for example one or more of a phenoxyaliphatic acid, substituted urea, triazine, phenol, nitrile, bipyridylium compound, substituted benzoic acid, halogenated aliphatic acid, carbamate, thiocarbamate, chloroacetamide, diazine or arsenic herbicide. In respect of selective herbicidal compositions for post-emergence use, the present compound may be used in admixture with for example a substituted phenoxyaliphatic acid; in respect of selective herbicidal compositions for pre-emergence use, the present conpound may be used in admixture with for example a substituted urea or triazine; in respect of sequential selective herbicidal use, one may apply for exanple before emergence of the crop S-2,3-dichloroallyl di-isopropylthiocarbamate or S-2,3,3-trichloroallyl di-isopropylthiocarbamate and the present compound after emergence of the crop.

The phenoxyaliphatic acid generally comprises alkyl and/or halogen substituted phenoxyaliphatic acids, and their salts, for example alkali metal, amine and alkanolamine salts, and functional derivatives, for example esters and amides. These compounds may be of activity such that they are recognised as commercial herbicides, or may be of only slight herbicidal activity. .17 0 3 7 Examples of the substituted phenoxyaliphatic acids which may be mentioned include 2,4-dichlorophenoxyacetic acid, 2-(2,4-dichlorophenoxy)propionic acid, 2-methyl-4-chlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, gamma-2,4-dichlorophenoxybutyric S acid, ganma-2-methyl-4-chloro-phenoxybutyric acid, alpha-2-methyl4-chlorophenoxypropionic acid, 2-(4-/22,4-dichlorophenoxy_Vphenoxy) propionic acid and 2-(4-Z~4-chlorophenoxy27phenoxy)propionic acid.

The substituted urea generally conrorises a tri- or tetrasubstituted urea such as N'-(3-chloro-4-methoxyphenyl)-N,N10 dimethylurea, N'-(3-chloro-4-methylphenyl)-N,N-dimethylurea, N' -parachlorophenyl-N.N-dimethylurea, N-butyl-N' - (3,4-dichlorophenyl) -N'-methylurea, N'-parachlorophenyl-0,N,N-trimsthylisourea, N'-p-chlorophenyl-N-methoxy-N-methylurea, N,N-dimethyl-N'-pheny1-urea, 3-(4-bromophenyl)-l-methoxy-l-rnethylurea, l-(2-benzothiazolyl) 3-methylurea, N,N-dimethyl-N'-(4-/Zl-methylethylZ7phenyl)urea, N'-(3,4-dichlorophenyl)-N-methoxy-N-methylurea or N,N-dimethyl-N'~ /Z3-(tii£luoromethyl)phenylZZurea.

The triazine herbicide generally comprises 2-chloro-4-(1cyano-l-methylamino)-6-ethylamino-l,3,5-triazine or 2-isopropyl20 amino-4-(3-methoxypropylamino)-6-nrothylthio-1,3,5-triazine or a compound of the formula:- Y where X is a halogen atom, alkoxy or alkylthio, and ' are the same or different and are hydrogen or alkyl and R ’ and R*' are the same or different alkyl groups, such as 2-chloro-4,6bisethylamino-1,3,5-triazine, 2-chloro-4-ethylamino-6-diethyl5 amino-1,3,5-triazine, 2-chloro-6-ethylamino-4-isopropylamino-l,3,5triazine or 2,4-bis(isopropylamino)-6-methylthio-1,3,5-triazine.

The phenol herbicide generally comprises 4,6-dinitro-ocresol,4,6-dinitro-2-sec-butylphenol or pentachlorophenol. The nitrile herbicide generally comprises 3,5-diiodo-4-hydroxy10 benzonitrile, 3,5-dibromo-4-hydroxybenzonitrile or 2,6-dichlorobenzonitrile. The bipyridylium herbicide generally comprises l,l'-dimethyl-4,4'-bipyridylium dichloride or 1,1'-ethylene-2,2'bipyridylium dibromide. The substituted benzoic acid herbicide generally comprises 2,3,6-trichlorobenzoic acid, 2-msthoxy-3,615 dichlorohenzoic acid or N-(l,1-dimethylpropyny1)-3,5-dichlorobenzamide. The halogenated aliphatic acid herbicide generally comprises trichloroacetic acid or 2,2-dichloropropionic acid.

The carbamate herbicide generally comprises isopropyl N-(3-chlorophenyl) carbamate, 4-chloro-2-butynyl N-(3-chlorophenyl)carbamate, methyl 3-(m-tolylcarbamoyloxy)phenylcarbamate or D-N-ethyl-2(phenylcarbamoyloxyjpropionamide. The thiocarbaroate herbicide generally comprises S-ethyl Ν,Ν-dipropylthiocarbamate, S-ethyl Ν,Ν-diisobutylthiocarbamate, S-(2,3-dichloroallyl) N,N-diisopropylthiocarbamate, S-ethyl N-ethyl-N-cyclohexylthiocarbamate, S-propyl butylethylthiocarbamate or S-(2,3,3-trichloroallyl) N,N-diisopropyl47637 thiocarbamate. The chloroacetanids herbicide generally comprises N,N-diallyl-2-chloroacetamide or N-isopropyl-2-chloroacetanilide. Hie diazine herbicide generally comprises 5-bromo-6-insthyl-3sec-butyluracil, 3-cyclohexyl-5,6-trimethyleneuracil, 5-amino-45 chloro-2-phenyl-3-pyridazinone or l,2-dihydropyridazine-3,6-dione. The arsenic herbicide generally comprises a salt of methane arsonic acid or cacodylic acid. Other herbicides which may be used as the second herbicide include l,2-dimethyl-3,5-diphenylpyrazolium ion, ethyl N-benzoyl-N-(3,4-dichlorophenyl)alanine, N-isobutyl-2-oxo-l-imidazolidine-carboxamide, aminotriazole,2,3dichloro-l,4-naphthoquinone, 4-amino-3,5,6-trichloropicolinic acid, N,N-dimethyl-2,2-diphenylacetamide, 2,6-dinitro-N,Ndipropyl-4-trifluoronBthylaniline, N-butyl-N-ethyl-2,6-dinitro4-trifluoromethylaniline, S,S,S-tributyl phosphorotrithioate, IS 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-henzofuranyl methylsulphonate, 4-chloro-2-oxohenzothiazolin-3-yl acetic acid, 3-isopropyl-2,l,3benzothiadiazinon-(4)-2,2-dioxide, 3,5-dibromo-4-hydroxybanzaldehyde 2,4-dinitrophenyloxime, methyl 2-chloro-3-(4-chlorophenyl) propionate, 2-chloroethyltrimethylammonium chloride, isopropyl 220 (N-benzoyl-3-chloro-4-fluoroanilino)propionate, nethyl 2-(N-benzoyl 3-chloro-4-fluoroanilino)propionate, 2-chloro-N-(l,3-dioxolan-2ylnethyl)-21,6’-dimethylacetanilide, 2-chloro-l-(3-ethoxy-4-nitrophenoxy)-4-trifluoromethylbenzene, methyl 2-(4-£/2*,4*-dichloropb.eno?yi7phenoxy)propionate or isobutyl 2-(4-Z3,-chlorophenoxy27~ phenoxy) propionate.

Hie other herbicide may particularly be another herbicide which combats wild oats in cereal crops.

The particular embodiments, the present compound and particularly one specified above as being preferred for use as a herbicide, e.g. N-cyano-methyl-3,4-dichloro-methanesulphonanilids, is used (a) in admixture with 4-chloro-2-butynyl 3-chlorophenylcarbamate, 1,2-dimethyl-3,5-diphenylpyrazolium ion, alpha-2-raethyl-4-chlorophenojypropionic acid, N-(3-chloro-4-methoxypbenyl)-Ν,Ν-dimethylurea, N'-(3-chloro~4-methylphenyl)-N,N-dimethylurea or ethyl N-benzoyl-N-(3,4-dichlorophenyl)alanine, or (b) after emergence of the crop following use before emergence of the crop of S-2,3dichloroallyl di-isopropylthiocarbamate or S-2,3,3-trichloroallyl di-isopropylthiocarbanate.

The present conpound may be used in admixture or sequence with another fungicide, particularly another cereal fungicide.

The other fungicide may be for instance one or more of maneb (polymeric manganese ethylenebisdithiocarbamate), zineb (zinc ethylenebisdithiocarbamate), mancozeb (which can be regarded as a mixture of maneb and zineb), thiram (tetramethylthiuram disulphide), ditalimfos (0,0-diethyl phthalimidophosphonothioate), tridemorph (2,6-dimethyl-4-tridecylmorpholine), fluotrimazole (l-£/Jiphenyl(3-trifluoromethylphenyl)methylZ7-l>2,4-triazole), ethirimol (5-butyl-2-ethylamino-4-hydroxy-6-methylpyrimidine), triforine (1,4-di/32,2,2-trichloro-l-formamidoethyl27piperazine), pyracarbolid (3,4-dihydro-6-methylpyran-S-carboxanilide), zineb-ethylene thiurandisulphide adduct, carbendazim (methyl benzimidazol-2ylcarbamate), captafol f5a.4.7.7a-tetrahvdro-N-/~I,1.2.2-tetra5 chloroethanesulphenyl~7phthalimide), thiophanate (l,2-di/j5-ethoxycarbonyl-2-thioureidoZ7benzene), propineb (polymeric zinc propylenebisdithiocarbamate), oxycarboxin (2,3-dihydro-6-m3thyl-5phenylcarbamoyl-l,4-oxathiin 4,4-dioxide), quintozene (pentachloronitrobenzene), benomyl (methyl l-ZZbutylcarbamoy£7 benzimidazol-2-ylcarbamate), benadanil (2-iodobenzanilide), dichlofluanid (N-dichlorofluoromsthanesulphenyl-N' ,N'dimethyl-N-phenylsulphamide), sulphur, copper compounds, iprodione (3-0,5-dichlorophenyl27 -l-/~Tl-methylethyl)aminocarbonyl~7 imidazolidine-2,4-dione, ziram (zinc dimethyldithiocarbamate), nabam (disodium ethylenebisdithiocafbamate), and triadimefon (1-(4-chlorophenoxy)-3,3-dimethy1-1-(1,2,4-triazol-l-yl)-2butanone).

In a particular embodiment, the present compound, e.g. N-2-oxopropyl-2',6’-dimethyl-methanesulphonanilide, is used in admixture with thiram.

The present conpound may be used in admixture or sequence with an insecticide, particularly a cereal insecticide, lhe insecticide may be for instance one or more of demeton-S-msthyl (S-2-ethylthioethvl 0,0-dimethyl nhosphorothioate), dimethoate (0,0-dimethyl S-methylcarbamoylmethyl phosphorodithioate), forraothion (S-/ N41 fon.iyl-M-i’K!tliylc;irbainoylinothyl27 θ,O-dimethyl phosphorodithioatc), oxydemeton-wethyl (S-2-ethylsulphinylethyl 0,0-dinethyl phosphorothioate), pirimicarb (Z-cUmethylamino-5,6-dimethylpyrimidin-4-yl dimethylcarbamate), thiometon (S-2-ethylthioethyl 0,0-di5 methyl phosphorodithioate), EKC (benzene hexachloride), aldrin (1,2,3,4,10,lC-hexachloro-1,4a,5,8,8a-hexahydro-exo-l,4-enio-S,8dimethanonaphthalene), fenitrothion (0,0-dimethyl 0-4-nitro-mtolyl phosphorotliioate), omethoate (0,0-dimethyl S-methylcarbamoyImethyl phosphorothioate), pirimiphos-methyl (0-2-diethylamino10 6-methyl-pyrimidin-4-yl 0,0-dimethyl phosphorothioate) and DDT (l,l,l-trichloro-2,2-di£chloraphenylI7ethane (COT is a trade Mark).

Ihe ratio of the present conpound to the other pesticide or plant growth regulant may vary over a wide range according to the particular conpounds involved and the intended use. In general, the ratio of present conpound to other pesticide or plant growth regulant lies in tlie range 1:0.1 to 1:15.

The present conpounds may be in admixture with non-phytotoxic oils, e.g. Agri-Oil Plus, Sun Oil HE or Fyzol 11E (Sun oil is a trade mark) The conpounds may be in admixture with an antidote (a 20 substance having the property of inproving the selectivity of herbicides), e.g. N,N-diallyl-2,2-dichloroacetamide or 1,8naphthalic anhydride.

The conpounds may be in admixture with fertilizers.

In the us·* of the present compounds as total herbicides, high rates of application, for exanple at least 10 kg per hectare, such as 10-2S kg per hectare, of the compounds are usually required, unless they are mixed with other herbicides, in which case the rate can be reduced.

In the use of tlie present compounds as selective herbicides, the rate of application is usually much lower and may be for example 0.5-10, e.g. 0.5-8, kg per hectare, such as 1-4 kg per hectare.

In the use of the compounds as plant growth regulants, low rates of application are usually required such as 0.1-4, eg 0.5-1, kg per hectare.

For use as fungicides, insecticides or anti-bacterial agents, the compounds are generally applied at a rate of 0.3-10, e.g. 1-6, kg per hectare. For use as fungicides, the compounds can be incorporated into a plant growing medium, particularly a peat based plant growing medium, in which plants are to grow, e.g. at a rate of 10-1000, preferably 50-500,gof conpound per cubic metre.

Ihe compounds can be employed as seed dressings, 'seeds' being used in its wider sense as including tubers and bulbs; for this use, the compounds can he employed at a rate for example of 0.1~lg per kg of seed and are preferably used in admixture with a carrier to facilitate admixture with the seed; the carrier can be a liquid, e.g. a hydrocarbon, or a solid, e.g. a clay or Fullers earth.

The present compounds may be applied to plants (including seeds), the soil (including compost), land or aquatic areas, or to inanimate or stored materials, e.g. textiles, paper, leather or wood, susceptible to fungal attack. They are preferably used as herbicides, particularly selective herbicides, or fungicides, especially for application to a locus at which a crop e.g. a food crop and especially a cereal crop such as wheat, barley or maize is growing or, less preferably, is to grow. Thus, the compounds may be applied pre- or post-planting of the crop. They may be employed for pre-emergence use or post-emergence use. The compounds may be used to protect plants from weeds and fungus.

The invention is illustrated by the following Examples, in which tenperatures are in degrees C. 4763? Example 1 Λ solution of 1-propanesulphonyl chloride (25 ml) in toluene (50 ml) was added during 15 minutes to a stirred solution of 2,6-dimethylani.line (55 ml) in toluene (400 ml). The mixture was stirred and boiled under reflux for 20 hours, then cooled and filtered. Ihe toluene solution was washed with, dilute hydrochloric acid (3 times) and water, then extracted (3 times) with dilute sodium hydroxide solution. The aqueous alkaline solution was acidified with dilute hydrochloric acid, and the product collected by filtration, washed with water and dried. Crystallisation from toluene/60-80° petrol gave 2',6'-dimethyl-l-propanesulphonanilide as buff coloured crystals (28.Og, 55$), melting point 72°.

Example 2 A mixture of the sulphonanilide of Exanple 1 (28.Og), anhydrous IS potassium carbonate (9.4g), ethyl 2-bromopropionate (17.6 ml) and 1,2-dimethoxyethane (200 ml) was stirred and boiled under reflux for 20 hours, then cooled and filtered, and the filtrate evaporated. A solution of the residual oil in ether was washed ivith dilute sodium hydroxide solution. The alkaline solution was acidified ivith dilute hydrochloric acid and the precipitated solid was collected by filtration This material (13.3g) was identified as unreacted sulphonanilide. Ihe ethereal solution was evaporated and a solution of the residual oil in ethanol/10% sodium hydroxide solution (100 ml, 1:1) was heated at 50° for 2 hours. The ethanol was evaporated, leaving an aqueous solution of the sodium salt of N-(2,6-dimethylphenyl)-N-(l-propanesulphonyl)47637 alanine. The solution was acidified with dilute hydrochloric acid. The product acid was extracted with chloroform, the chloroform solution was dried and evaporated, and the residue crystallised from toluene/60-80° petrol to give buff coloured crystals of N-(2,6-dimethylphenyl)-N-(l-propanesulphonyl)alanine (14.lg) (73¾ yield based on unrecovered sulphonanilide).

Example 3 A solution of the alanine derivative of Example 2 (6.5g) in toluene (100 ml) was treated with thionyl chloride (10 ml), boiled under reflux for 1 hour, then evaporated. The residual oil was re-evaporated with toluene to remove traces of thionyl chloride, and the residue was then boiled in 2-propanol for 1 hour and evaporated. A solution of this oily residue in ether was washed with sodium bicarbonate solution, dried and evaporated to a brown oil which was percolated through a column of silica gel with chloroform. Evaporation of the eluate gave the isopropyl ester so2ch2chzch3 CH.

CH.

CH. as a clear yellow oil; Analysis: Found: S9.451C, 7.9ΠΗ, 3.77W C17H27NO4S requires: 59.791C, 7.97ΪΗ, 4.101N Examples 4-33 Following an analogous procedure to that of the previous Acids Exanple R1 A Sub Melting Point 4 Me Me COOH 3,4-di Cl 131° 5 Me Me COOH 2-Et 212° 6 Me Me COOH 2-C1-6 Me 98° 7 Me Me COOH 2,6-di Me 118° 8 Me Me COOH 2-OCH- 131° 9 Et Me COOT 2,6-di Me 122° 10 Me Me COOH 2,6-di Et 118° 11 Me Me COOT 2,6-di Cl 128° Esters <«t Tt ‘Λ’* ** ** Ο tn Tt Tt cn cn tn cm •3Si I xt xt xt xt vo \o rs r* in xt Tt *t tn xt t^-r* tn xt +j I tn •rt & in 0) -si tn co cm tn CM CM C cm 00 rrt vo t>. m tn vo r*» ’d- Tt Tt *e Tt Tt in m s: oo Tt Tt Ο Ό cn tn rrt CM Tt w Tt W xt £ pH cj CM rrt cj tn tn Pm O x* tn rrt U Pm Tt CM rrt υ Em »—I U CM Kxr g ti 3.3 rrt O “ Pm g £ rrt CJ Ih rH CJ •rl £ •rt CU •h tn tn TJ o rtf P4 P* I in \O \O CJ 1 CJ 1 Tt •rt 1 Tt* CM CM tn tn tn CM tn CJ I xt CJ I Tt <Η04 l-l CM 'd’d' •d· ^4* *d· tO *t vo vo b»b* into b. b* co b* •d* *± M· στ κ in O Ob Mb* • · · · Ο o b* b* CM CM Cft ri co cn in to 00 in cn cn cm Q Q m co ri 00 CM VO Ori co «d- »t r* \o h* Ο Ό co CO CM ri 00 co b* b* b. b. cn cn ’d* «d· cn co *t *d· in in in in d* tt in tn in in m tn m m co *± CM ω ί υ co nF* tO ri U CO IS) O 2S ΐ γ-I a ω cT CM X O ι—I w ί % rM I to CM B b* CM co £ o nF* to co tt § m nT o rM U Melting Point o rM ri ri ri O ri O rM rM •Η ”Μ ·Μ 1 ’J3 Ο ·Μ CO ·Μ ·Η Ο Ο Ο Ο b* Ο Ο Ο Ο ’d rM Sub β> fl) 0 fl) ri fl) Ρ - « § 3 S Μ § g * tc Π3 Π3 *d Ό *0 P ri G 1 ri 1 1 1 1 ι CU cj Ο Ό ΟΙΟΌΌΌΌ I I ι «ν 1 r r ·* * *· CM CM CM CM CM CM CM CM CM CM < p P p p p p p p fl) P « B S3 S3 Η Η Η K S K 8 8 8 8 8 8 8 8 8 8 Ο ο ο O OuuuoQ co g g g ί 'ed i i % Ϊ % S I i i £ c c Example ri cm tn tt in vo tb co cn O CM CM CM CM CM CM CM CM CM tn 4J U W *n w o w £ § fc § tn •rt tn «4- K> «3· KJ KJ cl O *e*j· rCM tE rw «cf δ K) KJ ¾ CM CJ •3 c frt +J ·Η •rt •rt •rt «rt Ο Ο Ο Ο ft 2 ο ο ο s s TJ *ΰ £ Ό \£5 Ό KJ δ KJ l/J δ.

Pi £ Example 34 A solution of N-(2,6-dimethylphenyl)-N-methanesulphonyl alanine (5g) in chloroform (50 ml) was treated with thionyl chloride (5 ml), and the solution was boiled under reflux for 5 1 hour then evaporated. The residue was re-evaporated with toluene to remove traces of thionyl chloride. A chloroform solution of the residue was treated with a saturated solution of ammonia in chloroform, the mixture was allowed to stand at room temperature for 4 hours, then water was added and the organic 10 solvent evaporated. The suspended solid was removed by filtration, washed with water and dried. Reerystallisation from ethanol gave the amide IS as colourless crystals, melting point 158°.

Examples 35-43 Following an analogous procedure to that of Example 34, the following compounds were prepared: SO^1 I Ris N—Cff—A -44-Sub Example R1 CC Tbs A Sub Melting Point 35 Me H CONEt2 4-C1 76° 36 Me H CONEt2 2,6-diMe 76° 37 Me H C0NEt2 2-isoPr 108° 38 Me H C0NEt2 3-CF3 54° 39 Me H CONEt2 3,4-diCl 90° 4» Me Me CONHPh 2-Et 156° 41 Me Me (Βθ 2-Et 120° 42 Me Me CONH2 2,6-diEt 134° 43 Me Me conh2 2-Cl,6-Me 158° Example 44 A mixture of 3,4-dichloro-methanesulphonanilide (7.0g), anhydrous potassium carbonate (2.4g), chloroacetonitrile (2.2 ml) and 1,2-dimethoxyethane (100 ml) was stirred and boiled under reflux for 6 hours. The dark coloured reaction mixture was cooled, filtered and evaporated. A solution of the residual oil in chloroform was washed well with water, dried, and evaporated to give a black oil which was percolated through a column of silica gel with chloroform. Evaporation of the eluate gave an oil, a solution of which in ethanol deposited a cream coloured solid identified as N-cyanomethyl-3,4-dichloro-methanesulphon~ anilide (3.8g), melting point 83°, S0,CH, I N-CH2CN Cl Examples 45-48 Cl Following an analogous procedure to that of Example 44, the following compounds were prepared: Example R1r18 A Sub Melting Point 45 Me H CN 4-Cl 102° 46 Me H CN 2,6-diMe 84° 47 Me H CN 2-isoPr 99° 48 Me H CN 3-CF3 61° Examples 49-55 Seeds of the plant species listed below were sown in anodised aluminium pans, 19 an long x 9.5 cm wide x 5 cm deep, containing John Innes I potting compost. They were then watered and placed in a controlled environment room (22°C; 65-85¾ relative humidity; 14 hours per day artificial illumination at 13000 lux). Fourteen S days after sowing, the seedlings received a foliar spray of a compound listed below, formulated as a solution in 1:1 by volume aqueous acetone. The concentration of active ingredient and volume of application were adjusted so as to be equivalent to a rate of 11.2 kg/ha in 450 litres per hectare. After seven days growth in the controlled environment room, the plants were visually assessed for any herbicidal or growth regulant response. All differences from the untreated control were scored according to an index where 0 = no effect and 100 = complete kill. The results are shown in the following table: m tn c*. Ol 11.2 tn 100 o O* 20 O cn ο 1 tn 03 in 00 1 o n Γ) n I rt \O • o cn rt in Ol rH «—| rH tn in Ol m o O o n n I in Ol .-3 CO Ol tn 03 rH Ol n o n m o o Q Ol rt • Ol o cn o cn tn o tn Ol i—i i-H rH tn 03 in O O «η O in o m rH cn tn rH Cn 00 rH o 03 03 in O 30 tn O in O tn 03 co 00 09 rH cn 03 tn O O O O tn O rt ^H rH σι cn pH cn o· 0 1 i-H .a s fl 1? O' m 0 3 tf) o ti •3 •ri μ *ϋ s to Ζ—Y ri 0 z-v co 0 /—v ω 3 0 •rH fi to Oi H & Q bo 3 ri •y fi •ri ri ri Oi S ri 0 μ > cd t'· tn O •rH 3 •P μ ri Q g 4J •rH 0 bi p ω w u fi ri tf) P ph ri _y tf) tf) 3 tf) rH fi P O ei p fi 3 0 3 ri e 2 •rl ri fi tf) to c rH P o <2 •rH •H •a O 0 > •fi CU ω u U w < cu o 1 o 1 Sm* I 1 1 1 ! tf) 0 •fi tf) ’ri 'ri to 0 0 μ 0 ri •p rfi ri 0 μ υ υ tf) P bi ri ci 0 ri V) fi 0 ω P 0 Pi 0 K ri ri ,μ CO cu 2 >4 Cd w O tu Examples 56-60 The compounds listed below were each formulated as an attaclay/sand dust and incorporated into John Innes I potting compost at a rate equivalent to 26 parts per million weight/ volume of active ingredient to soil and placed in anodised aluminium pans, 19 cm long x 9.5 cm wide x 5.0 cm deep. This rate is approximately equivalent to a soil surface application of 11.2 kg active ingredient/hectare cultivated to a depth of 5 cm. Seeds of the species listed below were sown in the treated soil, watered and placed in a controlled environment room (22°C; 65-851 relative humidity; 14 hours per day artificial illumination at 13000 lux) for 21 days. The plants were then visually assessed for any growth regulatory or herbicidal effects. All differences from an untreated control were scored on a scale fron 0 - 100, where 0 signifies no effect and 100 signifies complete kill. The results are shorn in the following table: Example 56 57 58 59 60 Compound of Example 15 44 22 3 24 Species Dosage rate (prm) 26 26 26 26 26 Peas - (Pisum sativum) 0 0 0 0 0 Mustard - (Sinapis alba) 100 40 100 90 100 Linseed - (Linum usitatissimum) 70 20 100 20 100 Maize - (Zea mays) 50 5 so 20 60 Oats - (Avena sativa) 20 60 so 20 60 Ryegrass - (Lolium nerenne) 100 5 DO 90 im Examples 61-65 Seeds of the plant species listed below were sown in John Innes I potting compost in aluminium pans, 19 cm long x 9.5 cm wide x 5.0 cm high, one species per pan. The soil surface was then sprayed with a compound listed below, formulated as a solution in 1:1 by volume aqueous acetone except for the compound of Example 44 which was formulated as an aqueous suspension containing 1000 parts per million of the wetting agent Lissapol NX (lissapol is a trade mark) (nonylphenol/ethylene oxide condensate). Each caipound was applied at a rate of 2.8 kg of active ingredient per hectare in 450 litres of spray liquid per hectare. The pans were then watered, and placed in a controlled environment room (22°C, relative humidity 65-85s, 14 hours per day artificial illumination at Γ7000 lux) for 21 days. The plants were then visually assessed for any growth regulatory or herbicidal effects. All differences from an untreated control were scored on a scale from 0 - 100, where 0 signifies no effect and 100 signifies complete kill. The results are shown in the following table: Example Compound of Example 61 62 63 64 65 15 44 22 3 24 Species Dosage rate kg/ka 2.8 2.8 2.8 2.8 2.8 Chickweed - (Stellaria media) 30 - 50 - - Mustard - (Sinapis alba) 10 - 90 - - Cotton - (Gossypium sp.) 0 - 0 - - Tomato - (Lycopersicon esculentum) 20 - 40 - - Fathen - (Chenopodium album) 100 - 100 - - Carrot - (Daucus carota) 0 0 — Wheat - (Triticum aestivum) 0 0 0 0 10 Barley - (Hordeum vulgare) 0 0 0 0 30 Wild Oat - (Avena fatua) 5 0 0 80 100 Blackgrass - (Alopecurus myosuroides) 20 0 40 90 100 Barnyardgrass - (Echinochloa crus-galli) 40 80 0 60 80 Crabgrass - (Digitaria sanguinalis) 100 0 90 90 100 Rice - (Orysae sotiva) - 0 - - - IS Example 66 Seeds of the monocotyledon species listed below were sown in anodised aluminium pans, 19 cm long x 9.S cm wide x 5.0 cm deep, containing John Innes I potting compost. They were then watered and placed in a controlled environment room (22°C; 65-85¾ relative humidity; 14 hours per day artificial illumination at 17000 lux). 14 days after sowing, the seedlings were given a foliar spray of the compound of Example 44, formulated as an aqueous suspension together with 2000 ppn of the wetting agent Lissapol NX. The dosage rate was adjusted to be 2.8 kg active ingredient in 450 litres per hectare. After a further 14 days in the controlled environment room, the plants were visually assessed for any growth regulatory or herbicidal effect. All differences from an untreated control were scored on a scale from 0-100 where 0 signifies no effect and 100 signifies complete kill. The results are shown in the following table: Species Dosage rate kg/ha 2.8 Wheat - (Triticum aestivum) Barley - (Hordeunt vulgare) Barnyardgrass - (Echinochloa crus-galli) 100 Examples 67-83 The compounds listed below were tested according to the procedure of Examples 56-60 but at 130 parts per million weight/ volume of active ingredient to soil. This rate is approximately equivalent to a soil surface application of 56 kg active ingredient per hectare cultivated to a depth of 5 cm.

The results are shown below: IS to 00 co •rt , 50 8 μ 8 Iri 1 ί 90 08 j ο •rt 82 r·'· •rt o μ | 08 8 μ ο LO 30 σ iri μ oo Ό M- O CM 00 o cn Ο co Ο Γ>- Ο tn r-4 j 08 LO •rt o CM 00 O cn Ο co Ο Γ“- 30 μ CD o n 100 n Ο ο Ο r*. tn CM •rt CM CM CM 00 LO o OOT O Ο Ο Ο tn CM •rt CM CM CM >· r-» r- CM © CM 00 co 00 00 00 μ μ μ μ μ Ό \O CM 00 00 00 00 00 8 μ μ μ μ μ rri m to CM LO 100 os Ο 20 40 00 O ο o Π Ο Ο Γ**· μ rt co to tn KJ t·. Ci Γ) o Ο ο Ο r* tri •rt ’rt cn CM a 00 O cn ο tn ο CM 40 μ . CM o η o ιη ιη Ο r*. r-i •rt r-. co O cn o Ο O ο ο 8 t. tn Γ*» co (Μ cn f* o Ο O Ο ο Ο Ό CM r- LO tn tn co LO o Ο o Ο 30 ο ο tO L0 r·. <Μ tn r* Tf n Ο Ci Ο Ο ο o Γ*- cn •rt r* Φ i—l U4 7J Ζ~-\ Ο § Ψι o 'ΐτΓ •ri P ζ—\ d -d s o > υ .5 0) μ +j RJ (0 RJ ΙΛ •ri 3 a sat: £ £ •ri & Β RJ1 g u 5 i Rj c £ •ri μ c ο dj ri a. w • ri 3 % ¢) t'J 1 •sri 1 1 1 1 (Λ 2 nJ ω V) 3 •ri υ Peas Rj •H ω fe & w ft) N JcL , A μ JL ----. -1 Example 84 Aqueous acetone suspensions containing 2000 mg of the compound of Example 15 per litre and 125 mg of the wetting agent Lissapol NX (nonylphenol/ethylene oxide condensate) per litre were applied to 5 the soil surrounding the roots and leaves of cucumber plants with two fully expanded leaves. The treated plants, together with controls treated with wetting agent alone, were inoculated 24 hours after the chemical application with spores of the disease organism known as cucumber powdery mildew Erysiphe cichoracearum. The plants 10 were then placed in a controlled environment room (18°C and 80-90' relative humidity) until disease incidence was measured after fourteen days, when, it was found that the treatment with active compound had given 82? fungus control, in comparison with less than 5? on the controls.

IS Example 85 A slow stream of hydrogen sulphide gas was bubbled through a stirred solution of N-cyanomethyl-3,4-dichloromethanesulphonanilide (6.0g) in pyridine (75 ml) containing triethylamine (11.0 ml). Reaction was carried out at room temperature for 4 hours, and the 20 mixture was then poured into ice/water (1500 ml). The precipitated buff coloured solid was collected by filtration, washed with water, and dried. The product was identified as N-(thiocarbamoylmethyl)-3, 4-dichloromethanesulphonanilide (6.0g, 89? yield), melting point 178°.

Examples 86-89 By following procedures analogous to that of Example 85, ths following compounds were prepared: Example R1 R18 A Sub Melting Point 86 Me H -^nh7 2-isopropyl 136° 87 Me H 4-chloro 186° 88 Me H -!nh7 3-CF3 136° 89 Me H § -OT2 2,6-dimethyl 160° Examples 90-92 Following an analogous procedure to that of Bxap)e 2, the following conpounds were prepared: SO.R1 R18 N-CH-A J I Sub Example R1 R18 A Sub Melting Point 90 Me Et COOH 2,6-diMe 164° 91 n-Bu Me COOH 2,6-diMe 112° 92 n-Pr Ms OOOH 2,6-diMe 143° Examples 93-122 Following an analogous procedure to that of Example 3, the I following conpounds of the formula given in Examples 90-92 were prepared: 2S Analysis where Product is an Oil z: σ» bO c +2 •rt C P «rt rd O O ft co 'ft o o oo »—i K) Tf rtN ON ο σ» cn cm t-* c* Tf in ON O CT) \O Tf rd LO Tf Tf t^· Γ* \O O O «“I cm Tf \O cn γ-* sf *t cm cn σι kj \O oo O oo Ο Γ Γ- rd tn Tf C» CM Ο σι O N. t- Ν- CM CM o tn Tf Tf tn tn Tf Tf W *3· s Naf w Tf NJ CO rd O KJ tn co tn tn tn tn co co Νί Ό cn n. tn in r* a CM Z CM U CO •rt O rd o CM CO I o CM w •rt »X3 o CM \O u I CM •rt Ό \o d •rt TJ Tf A KJ $ CM § I Tf w θ’* CM »«· CM ΰ % £ γ X '-3 Tf k£> Ο Λ Λ ·» tn CM CM Ji a Ji ^£. rA >d.

P ft •SJ tn Tf tn cn cn cn •X) cn r* cn σι cn •w .Sc p;.S rrt O 0 pH IS ts. oo r** oo tn tn m Ό mm m O O cm CO o* CM co d* CM rrt C) v£> CJ I CM m m oo o rs r·.

CM CO t*» § cn sf* tn cT o co O o Tt \O CJ I CM CM a o I CM •rt T3 I o fl) S (rt Μ ΓΌ a* S s S 8 co o* SsT4 CM ΐ tn U* ffi CM 4' CO § Analysis where Product is an Oil z: ef» »Trt o o hh r» \O rs tn CO CO 00 -it to lH oo r- \o rs co Tf to r- O co to •e· un \o S’ Tt «± un O Ch t· r·- 1» rd es es to es cn O r·* es cn Ο Ό Ch co in Ch oo to to ’tt’ -cf m m -rt 00 rd \D rd CO pH t>. r- mo m in in tn W O* cs W C?* rs rH CS tT tf aT Ό fH O o rs Ch W r to CS X S3 rH rH a rd •8 m r-1 rd I—I Example 121 Following an analogous procedure to that of Exanple 2 but enploying bromolactone starting material, the lactone melting point 127°, was prepared.

Examples 122-125 Following an analogous procedure to that of Exanple 34, the following conpounds of fornula given in Examples 90-92 were prepared: Μ •S3 fi ο gq, fi . pi Ν a •8 ο c ΐ fi υ «· a in a Examples 126-146 Following an analogous procedure to that of Exanple 44, the following compounds of formula given in Exanples 90-92 were prepared: Exanple R1 CO 'ftS A Sub Melting Point 126 Me H OJ 2-Cl,6Me 63° 127 Me Me OI 2,6-diMs 80-82° 128 Me H OJ 2-C1 65° 129 Me H CN 3-Cl,4Me 88° 130 nPr H CN 3,4-diCl 80° 131 Ms H OJ 2,5-diCl 112° 132 Me H CN 3-Cl,4-F 110° 133 Me H CN 2,6-diCl 82° 134 Ms H CN 2-050^ 98-99° 135 Et H CN 3,4-diCl 79-81° 136 NMe2 H OJ 3,4-diCl 85° 137 Me H CN 2,3-diCl 86° 138 Me H CN 3-C1 64° 139 Me H CN 4-SCN 118° 140 Me H CN 3-N02,4-Cl 114-116° 141 Me H CN 2,4-diCl 88° 142 NMe2 H CN 4-C1 52° 143 Me H CN 3,4-diMe 102° 144 Me H -(ch2),cn 2,6-diMe 51° 145 Me H 3,4-diCl 78° 146 Me H -(ffl2)2CN 3,4-diMe 88° Examples 147-158 Following an analogous procedure to that of Exanple 85, the following conpounds of formula given in Examples 90-92 were prepared: Exanple R1 oo A Sub Melting Point 147 Me H csnh2 2-Cl,6Me 152° 148 Me H CSNi^ 3-01,4½ 202° 149 Me H CSNF^ 2-C1 172° 150 Mb H CSN^ 2,6-diCl 180° 151 Me H CSNH^ 2,5-diCl 196° 152 Me H CSNI^ 3-C1 184° 153 nPr H csnh2 3,4-diCl 168-170° 154 Et H csnh2 3,4-diCl 162-164° 155 Me H CSN^ 2,3-diCl 178° 156 Me H CSNi^ 3-Cl,4-F 182° 157 Me H CSi®^ 2,4-diCl 160° 158 Me H csnh2 2-OSO2Me 180° MbS02C1 Pyridine SO,Me I 2 NC^COOEt .1 solution of N-phenylglycine ethyl ester (10.Og) in pyridine 25 (50 mL) was treated with methane sulphonyl chloride (4.3ml). The exothermic reaction was allowed to proceed unchecked, then the mixture was boiled under reflux for 25 hours, cooled and poured into a rapidly stirred mixture of ice/water/hydrochloric acid.

Hie precipitated, buff coloured, solid was collected by filtration, washed with water and dried. Yield 7.Og (49¾). Reerystallisation from ethyl acetate/6O-8O° petrol gave colourless crystals of melting point 66°. Λ mixture of 2',6'-dimethylethanesulphonanilide (6.0g), anhydrous potassium carbonate (2.1g), ethyl 2-bromopropionate (3.65 ml) and dimethylformamide (EMF) (90 ml) was stirred and heated at 90° for 7) hours. The mixture was cooled, filtered, the residue washed on the filter with hot EMF, and the filtrate evaporated. The resulting yellow oil was dissolved in ether and the solution washed successively with 10¾ sodium hydroxide solution go and water, then dried (MgSO^) and evaporated. The solid residue was slurried with a little ethanol and the crystals collected by filtration. Yield of N-l-carboethoxyethyl-21,6'-dimethyl-ethanesulphonanilide was 5.7g (65¾). Melting point 70°.

Example 161 A mixture of 2',6'-dimethylethanesulphonanilide (68.5g), , 47637 anhydrous potassium carbonate (24.5g), ethyl 2-bromopropionate (58.Og) and 1,2-di-methoxyethane (400 ml) was stirred and boiled under reflux for 66 hours, then cooled, filtered and the filtrate evaporated.

A solution of the oily residue in ether was washed 3 times with 10¾ sodium hydroxide solution (100 ml), washed with water, dried (MgSO4) and evaporated to give N-(l-carboethoxyethyl)-2',6'dimethylethanesulphonanilide as a pale yellow oil having purity greater than 99¾ (by gas-liquid chromatography).

Analysis · Empirical Formula <=15H23 N o4 S Theory, ? 57.48 7.40 4.47 20.42 10.23 Found, % 57.19 7.71 4.81 The aqueous alkali washes were combined, and acidified with dilute HCl. The precipitated solid (9.9g) was filtered off, washed with water, dried and identified as recovered unreacted sulphonanilide.

Total yield of the ester was 84.5g (98¾ yield based on sulphonanilide not recovered).

Example 162 Λ solution of the N-/3-(2-ethoxycarbonyl)hydrazinocarhonyl) ethylZ7-2' ,6'-dimethylmethane sulphonanilide (5.6g) in ethanol (75 ml) plus 101 NaOH solution (75 ml) was heated on a steam bath for 2j hours and then cooled, and the ethanol evaporated.

The resultant aqueous solution was acidified, heated on the steam bath for 1 hour, and then filtered, lhe filtrate was just neutralised with dilute NaOH, saturated with sodium chloride, and extracted with chloroform. The chloroform solution was dried and evaporated. The residue gave almost colourless crystals of N-(l-hydrazinocarbonyl)ethyl)-21,6'-dimethylmethanesulphonanilide from a solution in toluene/60-80° petrol. Yield 2.6g (581). Melting point 115-118°.

Example 163 In a standard test indicative of insecticidal activity, 301 inhibition of acetylcholinesterase was exhibited by the compound N-Ο (methyl carbarnoyloxyimino)propyr7-2' ,6' -dimethyl-methanesulphonanilide at a 100 micromolar concentration of conpound.

Example 164 A 11 suspension/solution of the product of Exanple 155 in polyethylene glycol (Carbowax 400) was added to a dextrose nutrient broth to give a concentration of 1,000 parts per million (ppm) weight/volume of medium. Dilution in test tubes was then carried out to give a concentration of 200 ppm weight/volume of medium.

To 8 ml quantities of broth was added 0.2 ml of a dense broth culture of the bacterium causing black arm of cotton, Xanthoimnas malvacearum.

After 8 days incubation at 25°C, all the broth specimens were examined for signs of bacterial growth. No growth occurred, indicating that the compound is highly bacteriostatic to this organism.

Examples '165-167 A one week old maize meal/sand culture of the damping-off disease organism Pythium ultimum was thoroughly mixed by hand with clean sterile John limes No 1 potting compost in the ratio of 3 kg culture to 12 litres of soil. Ihe infected soil was then left for approximately 18 hours before use. Each of the conpounds listed below was ground together with a wetting agent, Tkeen 20 (1¾ of final volume), until a solution or fine suspension was produced which was then diluted with distilled water to give 16Cknl of solution containing 1500, 500, 150 or 50 ppm active ingredient. ml aliquots of this solution were added to 75g portions of the soil infected with Pythium ultimum which were contained in small plastic cartons, 60 mm diameter x 55 mm high. Fifteen cabbage seeds, variety Flower of Spring, were placed in a circular depression in the treated infected soil, recovered, and the whole sealed with a plastic cap. The cartons were then placed in a constant temperature room at 25°C + 1°C. Four replications per treatment were made with one additional treatment where seeds were sown in soil which was chemically treated only, i.e. there was no infection. Ihis latter treatment was included to measure the direct effect of the chemical on the germination of the seed. After six days the cartons were '·· 476 37 removed from the controlled tenperature chamber and assessed for degree of fungal growth on the soil surface and percentage of seedling emergence. The results of both these assessments are expressed in a 0-8 scale as follows: 0 = <201 inhibition = 20-34¾ inhibition » 35-44¾ inhibition 45-54¾ inhibition » 55-64¾ inhibition “ 65-74¾ inhibition - 75-84¾ inhibition = 85-94¾ inhibition = >94% inhibition and are given in the following table: Exanple Conpound Product of Exanple No Dose rate, ppm Mycelial Control Score Germination Score 165 9 300 0 5 100 0 5 30 0 1 166 24 100 0 5 30 0 1 167 26 300 0 4 100 0 4 30 0 3 Untreated - - 0 0 637 Examples 168-176 Aqueous acetone solutions or suspensions containing 2000 or 500 mg of the compound listed below per litre, together with 125 mg of a wetting agent per litre, were applied to: (A) the soil surrounding the roots and leaves of rice plants having two fully expanded leaves; (B) the leaves of vine plants having five fully expanded leaves; (C) the soil surrounding the roots of potato plants having seven fully expanded leaves; (D) the leaves of potato plants having seven fully expanded leaves; (E) the soil surrounding the roots and leaves of barley plants having one fully expanded leaf; or (F) the soil surrounding the roots and leaves of cucumber plants with two fully expanded leaves.

The treated plants, together with controls treated with wetting agent alone, were inoculated 24 hours after the chemical application: in the case of (A) with an aqueous suspension of spores of the disease organism rice blast Pyricularia oryzae; in the case of (B) with an aqueous suspension of sporangia of the disease organism vine downy mildew Plasmopara viticola; in the case of (C) and (D) by spraying with an aqueous suspension of sporangia of the disease organism potato blight Phytophthora infestans; in the case of (E) by shaking with spores of the disease organism barley powdery mildew Erysiphe graminis; or in the case of (F) by shaking with spores of the disease organism cucumber powdery mildew Erysiphe cichoracearum.

The plants then: in the case of (A) were placed in an atmosphere of 80-100¾ humidity at 28°C until the disease incidence was measured seven days later; in the case of (B) were placed in an atomosphere of 80-100¾ humidity at 14-18°C until the disease incidence was measured twelve days later; in the case of (C) and (D) were placed in an atmosphere of 100¾ humidity for 24 hours and then transferred to a controlled environment room (18°C and 80-90¾ relative humidity) until disease incidence was measured after 5 days; in the case of (E) were transferred to a controlled environment room (18°C and 80-90¾ relative humidity) until disease incidence was measured after 10 days; or in the case of (F) were transferred to a controlled environment room (18°C and 80-90¾ relative humidity) until disease incidence was measured after fourteen days.

It was found that in comparison with less than 5¾ on the controls, the chemical treatments gave the percent control shown in the following table: Exanple Conpound Product of Exanple No Rate, ppm Disease % Control 168 139 2000 rice blast 84 169 29 2000 vine downy mildew 98 rr 500 ii r ι 11 90 170 41 2000 potato blight 93 171 130 2000 II II 76 11 500 11 It 59 172 146 2000 barley powdery mildew 89 173 145 2000 II II II 96 174 146 2000 II II It 92 175 144 2000 II II II 95 176 121 2000 cucumber powdery mildew 92 Example 177 .

The product of Exanple 95 was tested according to the procedure of Examples 49-55. It gave the following results: Species Effect Peas 15 Mustard 100 Linseed 25 Ryegrass IS Sugarbeet 100 Oat 20 French beans 100 Examples 178-182 The conpounds listed below were tested according to the procedure o£ Exanple 66 but including rice (Oryza sativa) as an additional test species. The results were as follows: Exanple Compound Product of Exanple Wheat Barley Barnyard Grass Rice 178 85 0 0 90 0 179 129 5 10 90 0 180 135 0 0 80 0 181 148 0 0 80 0 132 154 0 0 90 0 Example 183 The.product of Exanple 95 was tested according to the procedure of Examples 56-60 but at 130 and 26 parts per million weight/volume.

The results were as follows: Species Dosage Rs 130 te, ppm 26 Peas 30 20 Mustard 100 90 Linseed 80 0 Maize 100 50 Oats 100 0 Ryegrass 100 90 Examples 184-189 Each of the conpounds listed below was formulated as: (I) an attaclay/sand dust and incorporated in John Innes 1 potting conpost at a rate equivalent to 6.5 and 3.25 parts per million weight/volume of active ingredient to soil and placed in anodised aluminium pans, 19 cm long x 9.5 cm wide x 5.0 cm high.

This is approximately equivalent to a surface application of 2.8 and 1.4 kg active ingredient per hectare cultivated to a depth of 5 cm. Seeds of the species listed below were sown in the treated soil, one species per pan, watered and placed in a controlled environment room (22°C; 65-85% relative humidity and 14 hours artificial illumination at 17000 lux) for 21 days.

(II) An aqueous suspension together with 1000 ppm of the wetting agent Lissapol NX. The surfaces of an additional set of pans with seeds already sown were then sprayed with 2.8 or 1.4 kg/ha in 450 litres/hectare, and the pans kept in the controlled environment room for 21 days.

The plants were then visually assessed for any growth regulatory or herbicidal effects. All differences from an untreated control were scored on a scale from 0-100, where 0 signifies no effect and 100 signifies conplete suppression.

The results are shown in the following table where I stands for soil incorporation and II for surface spray.

Species Dosage Rate, ppm Conpound Product of Exanple 95 I II 165 148 135 I 'II 129 I TI 85 I II I II I II Cotton 6.5 0 0 0 0 0 0 0 ' 0 0 0 5 - 3.25 0 0 0 0 0 0 0 o 0 0 - - Tomato 6.5 0 0 0 0 0 0 00 0 0 90 - 3.25 0 0 0 0 0 0 0 1 0 0 0 - - Wheat 6.5 0 0 0 0 0 0 0 0 0 0 - - 3.25 0 0 0 0 0 0 0 0 0 0 - Barley 6.5 0 0 0 0 0 0 0 0 0 0 3.25 0 0 0 θ 0 0 ojo 0 0 - - Barnyard Grass 6.5 90 100 60 70 90 100 70:80 90 100 1 - - 3.25 70 80 60 so 90 90 SO j60 90 90 - - Rice 6.5 0 0 0 0 0 0 0 0 0 0 - - 3.25 0 0 0 0 0 0 0 0 0 0 - - Carrot 6.5 - - - - 0 0 0 0 0 0 0 3.25 - - - 0 θ 0 0 0 0 - - Chickweed 6.5 90 - Mustard , 6.5 50 - Fathen ‘ 1 6.5 100 - Example 190 2',61-dimethyl-ethanesulphonanilide Ethanesiilphonyl chloride (114,4g) was added slowly (during minutes) to a stirred solution of 2,6-dimethylaniline (LIO ml) in pyridine (500 ml). The exothermic reaction was allowed to proceed, unchecked (the temperature rose to 60°), then the reaction mixture was boiled under reflux for 3 hours, cooled and poured into a rapidly stirred mixture (5 litres) of water, ice and hydrochloric acid. The precipitated, brown, granular, solid was collected by filtration, washed well with water and dried under vacuum at 50°. The yield of crude 2',6'-dimethyl-ethanesulphonanilide was 152.Og (80¾). Its melting point was 90°.

The total crude product was dissolved in 40¾ sodium hydroxide solution (100 ml), the solution was diluted to approximately 2 litres, warmed with charcoal for 30 minutes, then filtered. The clear, pale yellow, filtrate was cooled, then added slowly to a rapidly stirred mixture of ice, water and hydrochloric acid. The precipitated, white, solid was collected by filtration, washed with water, and dried under vacuum at 50°. The yield of purified material, melting point 92°, was 114.7g (60¾).

Examples 191-206 Following procedures analogous to that of Exanple 1, the following sulphonamides were prepared: ^R1 NH Λ Sub 4763? Example R1 Suh '’elting Point, 191 methyl 2,3-dichloro 102 192 methyl 3,4-dimethyl 92 193 isopropyl 2,6-dimethyl 102 194 -CH2COOEt 3,4-dichloro 104 195 methyl 2,6-dichloro - 196 methyl 2-chloro-6-methyl 94 197 n-butyl 2,6-dimethyl - 198 methyl 2-ethyl 40 199 2-thienyl 3,4-dichloro 138 200 methyl 3-chloro-4-fluoro 116 201 methyl 3-chloro-4-methyl 83 202 methyl 2-methanesulphonyloxy 121-123 203 methyl 2,6-diisopropyl 93 204 methyl 2-methanesulphonyloxy-5-nitro 178 205 dimethylamino 2,6-dimethyl - 206 dimethylamino 2-chloro-6-nethyl - The NMR spectra of the conpounds for whom no melting point is 20 given in the above table have the following tau values: Compound of Example Tau (CDClj) 195 2.5-3.0, 3H, multiplet, (aromatic); 3.5, IH, broad singlet, (N-H); 6.7, 3H, singlet, (CH3). 197 2.95, 3H, singlet, (aromatic); 4.2, IH, broad singlet, (N-H); 6.8-7.0, 2H, multiplet, (S-CH2); 7.65, 6H, singlet, (2,6-diCHj); 7.9-8.7, 4H, multiplet, (O^O^CH-jCHj); 9.1, 3H, triplet, (Q^O^CJ^CHj). 205 2.95, 3H, singlet, (aromatic); 3.95, IH, broad singlet, (N-H); 7.15, 6H, singlet, (N/ 0¾ /2); 7.6, 6H, singlet, (2,6-diCH3). 206 2.75-3.0, 3H, multiplet, (aromatic); 3.8, IH, broad singlet, (N-H); 7.2, 6H, singlet, (N/ 0¾ /2); 7.55, 3H, singlet, (CHj). Example 207 N-2-oxopropyl-4’- chloro-methanesulphonanilide - Λ mixture of 4'-chloro-methanesulphonanilide (10.Og), anhydrous potassium carbonate (4.0g), chloroacetone (4.8 ml), and 1,2-dimethoxy 7637 ethane was stirred and boiled under reflux for 24 hours, and then filtered, and the filtrate was evaporated. The oily residue was dissolved in ether, and the solution was washed with water, dried (MgSO^) and evaporated. The residue gave almost colourless crystals from acetone/40-60° petrol. Melting point 108°. Yield 4.1g. Examples 208-219 In a similar way to Exanple 207,the following were prepared: N-2-oxopropyl-2'-chloro-61-methyl-methanesulphonanilide, melting point 96°; N-2-oxopropyl-21,6' -dime thy 1-irethanesulphonanilide, melting point 56°; N-2-oxo-3,3-dimethylbutyl-2',6'-dimethyl-ethanesulphonanilide, analysis: Found: C 61.75, H 8.26, N 4.62 C^I^jNOjS requires: C 61.70, H 8.09, N 4.50; N-2-oxopropyl-2’,6’-dime thy 1-ethanesulphonanilide, melting point 68°; N-2-oxopropyl-2' ,6'-dimethyl-l-propanesulphonanilide, melting point 104°; N-2-oxopropyl-2',6*-dimethyl-2-thiophenesulphonanilide, melting point 127-128°; N-2-oxopropyl-2', 6'-diethyl-methanesulphonanilide, melting point 46°; N-2-oxopropyl-2',6'-dimethyl-l-butanesulphonanilide, melting point 69°; N-2-oxopropyl-3',4'-dichloro-methanesulphonanilide, melting point 92°; N-2-oxopropyl-3',4'-diisopropyl-methanesulphonanilide, melting point 134°; N-2-oxopropyl-2'-nethoxy-methanesulphonanilide, melting point 126°; and N-2-oxopropyl-2',5’-dichloro-methanesulphonanilide, melting point 134°.

Example 220 N- (2,2-dimethoxypropyl) -21 -chloro-61 -nethyl-methanesulphonanilide To a solution of N-(2-oxopropyl)-2'-chloro-6’-methy1-methanesulphonanilide (5.7g) in methanol (80 ml) was added 4-toluenesulphonic acid (0.2g), followed by trimethyl orthoformate (6.65 ml), lhe mixture was stirred at room tenperature for 24 hours, then allowed to stand for 6 days. The solution was poured into dilute sodium bicarbonate solution, and the precipitated solid was collected by filtration, washed with water, and dried to give an off-white coloured solid of melting point 84°. Yield 6.0g.

Examples 221 and 222 In a similar way to Exanple 220, the following were prepared: N-(2,2-dimethoxypropyl)-4’-chloro-nethanesulphonanilide, melting point 85°; and N-(2,2-dimethoxypropyl)-2',6'-dimethyl-methanesulphonanilide, melting point 82°.

Example 223 4' -chloro-N-£~ (2-methyl-l ,3- dithiolan -2-yl )methy]/7-roethanesulphonanilide A solution of 4'-chloro-N-(2,2-dimethoxypropyl)-methanesulphon5 anilide (3.2g) in acetic acid (SO ml) was treated with ethanedithiol (0.96 ml) and the mixture was slowly distilled, using a short Vigreux column, for 30 minutes, and the distillate discarded. The remaining acetic acid solution was evaporated, and the residue was re-evaporated with toluene to remove traces of acetic acid.

A solution of the residue in ether deposited pink coloured crystals on standing. Recrystallisation from ethyl acetate/ether gave the product as nearly white crystals of melting point 114-117°.

Exanples 224 and 225 In a similar way to Exanple 223, the following were prepared: · N-/T’(2-reethyl-l,3-dithiolan-2-yl )methyl27-2',6'-dimethylmethanesulphonanilide, melting point 108°; and N-jC(2-methyl-l,3- dithiolan-2-yl )methy£72 '-chloro-6'-methylnethanesulphonanilide, melting point 140°.

Example 226 N-/7(2-methyl-l,3-dioxolan-2-yl)methyl27-4,-chloro-methanesulphonanilide A mixture of N- (2-oxopropy$-4'-chloromethanesulphonanilide (6.0g), ethane-1,2-diol (10 ml), 4-toluenesulphonic acid (O.lg) and toluene (75 ml) was stirred and boiled under reflux with water separation by means of a Dean and Stark receiver. After 3 hours the reaction mixture was cooled, and poured into water (about 200 ml) containing a few drops of sodium hydroxide solution. Ihe organic layer was separated, washed with water, dried (MgSO^) and evaporated to a brown oil, which gave fawn coloured crystals from a solution S in toluene/80-100° petrol. Yield 6.0g (86%). Melting point 84-85°. Examples 227-229 In a similar way to Example 226, the following were prepared: N-/7 (2-methyl-4-hydroxymethyl-1,3-dioxolan-2-yl)rae thy 127-4’chloro-methanesulphonanilide, melting point 118°; N-/22(2-methyl-l,3-dioxolan-2-yl)methyl27-2’-chloro-6’-methy1methanesulphonanilide, melting point 84°; and N-£7(2“methyl-l,3-dioxolan-2-yl)methyl7-2 ’ ,6'-dimethylmethanesulphonanilide, melting point 58°.

Example 230 N-2-hydroxyiminopropyl-2’,g-dimethyl-methanesulphonanilide A solution of N-(2-oxopropyl)-2,,6,-dimethyl-methanesulphonanilide (3.0g) in ethanol (50 ml) was added to a solution of hydroxylamine hydrochloride (0.9g) and sodium acetate (l.lg) dissolved in the minimum volume of water. The solution was boiled under reflux for 3 hours, and then cooled and evaporated. A solution of the residue in ether was washed with, water, dried (MgSQ^) and evaporated. Ihe residue was re-evaporated with toluene to remove acetic acid, then the product was crystallised from an ethyl acetate solution.

Melting point 122-124°.

Examples 231 and 232 One week old maize meal/sand culture of the damping-off disease organism Pythium ultimum was thoroughly mixed by hand with clean sterile John Innes No 1 potting conpost in the ratio of 3 kg culture to 12 litres of soil. This infected soil was then left for approximately 18 hours before use. The conpounds listed in the Table below were each ground with the wetting agent Tween 20 (1% of final volume) (Tween ia a trade mark), until a solution or fine suspension was produced, wiiich was then diluted with distilled water to give 160 ml of solution containing 1500 or 500 parts per million (ppm) active ingredient. 15 ml aliquots of this solution were added to 75g portions of the soil infected with Pythium ultimum which were contained in small plastic cartons, 60 m diameter x 55 mm high.

Fifteen cabbage seeds, variety Flower of Spring, were placed in a circular depression in the treated infected soil, recovered, and the whole sealed with a plastic cap. The cartons were then placed in a constant tenperature room at 25°C + 1°C. Four replications per treatment were made, with one additional treatment where seeds were sown in soil which was chemically treated only, i.e. there was no infection. This latter treatment was included to measure the direct effect of the chemical on the germination of the seed.

After six days, the cartons were removed from the controlled tenperature chamber and assessed for degree of fungal growth on the soil surface and percentage of seedling emergence. The results of both these assessments are expressed in a 0 - 8 scale as follows: = <2Oo inhibition = 20 - 34¾ inhibition = 35 - 44¾ inhibition = 45 - 54¾ inhibition = 55 - 64¾ inhibition = 65 - 74¾ inhibition = 75 - 84¾ inhibition = 85 - 94¾ inhibition = >94?o inhibition and are given in the following table. Any phytotoxicity induced by the chemical alone is deduced from the chemical only soil treatment.

Compound Dose, ppm Mycelial Control Score Germination Score Phytotoxicity Score N-/7(2-methyl-l,3dioxolan-2-yl)methyl2?41-chloro-methanesulphonanilide 300 8 0 N- (2,2-dimethoxypropyl)-2'-chloro6' -methyl-methanesulphonanilide 300 4 1 0 100 3 1 0 Untreated 0 0 0 Example 233 & 234 Aqueous acetone solutions of each of the compounds listed in the Table below, containing 2000 parts per million (ppm), together with 125 ppm of a suitable wetting agent, were applied to the soil surrounding the roots and leaves of vine plants having five fully expanded leaves.

The treated plants, together with controls treated with wetting agent alone, were inoculated 24 hours after the chemical application with an aqueous suspension of sporangia of the disease organism known as vine downy mildew, Plasmopara viticola.

Ihe plants were then placed in an atmosphere of 100$ humidity/80$ humidity, at 14-18°C until the disease incidence was measured twelve days later, when it was found that the treatments had given the following fungal control in comparison with less than 5$ era the controls.

Conpound $ Control Vine Downing Mildew N- (2,2-dime thoxypropyl)-2'-chloro-6'-methylmethanesulphonanilide N-/7(2-methyl-l, 3-dioxolan-2-yl)methyl7 2'-chloro-6'-methyl-methanesulphonanilide 94 80 Examples 235-237 Aqueous acetone solutions of each of the compounds listed below, containing 2,000, 500 or 125 per million (ppm) weight/volume together with 125 ppm of a suitable wetting agent, were applied to the soil surrounding the roots and leaves of potato plants having seven fully expanded leaves.

The treated plants, together with controls treated with wetting agent alone, were inoculated 24 hours after the chemical application with an aqueous suspension of sporangia of the disease organism known as potato blight, Phytophthora infestans.

The plants were then placed in an atmosphere of 100$ humiditjj/ 80s humidity for 24 hours, and then transferred to a controlled environment room (18°C and 80-90¾ relative humidity) until disease incidence was measured after five days.

It was found that the treatments had given the degree of fungal S control shown in the following Table, compared with less than 5Ϊ on the controls.

Compound Dose, ppm % Control Potato Blight N-2-oxopropyl-2',6'-dimethyl-methanesulphonanilide 2,000 99 500 94 125 90 N- (2,2-dimethoxypropyl)-2',6'-dimethylmethanesulphonanilide 2,000 98 500 55 Ν-£Γ (2-me thyl-1,3-dioxolan-2-yl)methyr72' ,6 '-dimethyl-methanesulphananilide 2,000 98 Example 238Aqueous acetone solutions of N-2-oxo-3,3-dimethylbutyl-2',6’dimethyl-ethanesulphonanilide, containing 2,000 parts per million (ppm) weight/volume together with 125 ppm of a suitable wetting agent were applied to the soil surrounding the roots and leaves of rice plants having two fully expanded leaves.

The treated plants, together with controls treated with wetting agent alone, were inoculated 24 hours after the chemical application with an aqueous suspension of spores of the disease organism known as rice blast, Pyricularia oryzae.

The plants were then placed in an atomosphere of 100$ humidity/ 80$ humidity, at 28°C, until the disease incidence was measured seven days later, when it was found that the treatment had given 80$ fungal control in comparison with less than 5$ on the controls. t Example 239 N- (Z-oxopropyS -21 -chloro-6' -methyl-methanesulphonanilide, formulated as an attaclay/sand dust, was incorporated in John Innes I potting compost at a rate equivalent to 130 parts per million weight/volume of active ingredient to soil and placed in anodised aluminium pans, 19 cm long x 9.5 cm wide x 5.0 cm deep. These rates are approximately equivalent to a soil surface application of 56 kg active ingredient per hectare cultivated to a depth of 5 cm. Seeds IS of Peas, Mustard, Linseed, Maize, Oats and Ryegrass were sown in the treated soil, watered and placed in a controlled environment room (22°C; 65-85$ relative humidity; 14 hours artificial illumination at 13000 lux) for 21 days.

The plants were then visually assessed for any growth regulatory or herbicidal effects. All differences from an untreated control were scored on a scale from 0 - 100, where 0 signifies no effect and 100 signifies complete suppression.

The results are shown in the follcwing table: Species Dosage rate (ppm) 130 Peas - (Pisum sativum) 30 Mustard - (Sinapis alba) 100 Linseed - (Linum usitatissimum) 80 Maize - (Zea mays) 5 Oats - (Avena sativa) 60 Ryegrass - (Lolium perenne) 70 Example 240 A 30¾ solution of sulphuric acid (27.5 ml) is added dropwise to a stirred mixture of N-(2-oxopropyl)-2',6'-dimethyl-methanesulphon anilide (0.1 mole), potassium cyanide (6.2g) and water (20 ml). The tenperature is kept at 15°. The reaction mixture is stirred for 15 minutes and the cyanohydrin of the sulphonanilide is isolated.

IS Example 241 A mixture of N-/73)3-di(ethoxycarbonyl)-2-oxo-l-methylpropyl27Z1,6'-dimethyl-methane sulphonanilide (0.5 mole), sodium hydroxide (1.5 mole), ethanol (500 ml) and water (500 ml) is heated for 2J hours, cooled and the ethanol evaporated. The resulting aqueous solution is acidified v.ith hydrochloric acid and heated for 1 hour, and then the product is isolated.

Example 242 A mixture of 2,6-dimethylmethanesulphonanilide (12.5g), 21-chloro-4-thiocyanoacetanilide (14.2g), potassium carbonate (4.3g) and dimethylformamide (75ml) was stirred and heated to 70-80° for 3 hours, then poured into ice/water. The precipitated viscous semi-solid material was extracted into chloroform. The chloroform solution was washed with 5¾ sodium hydroxide solution, washed with water, then dried (MgSO^) and evaporated to a brown oil. A solution of this oil in chloroform was percolated through a short column of silica gel. Evaporation of the eluate gave a brown oil whicii deposited almost colourless crystals of Μ-/ΓΖΓ(4thiocyanophenyl) carbamoyljjme thyLZ7-2' ,6' -dimethylmethanesulphonanilide from a solution in ethylacetate. Melting point 152°. Example 24-3 A solution of N-(3-hydroxy-2-oxopropyl)-2’,6'-dimethylmethanesulphonanilide (2.8g) in pyridine (5 ml) and acetic anhydride (5 ml) was allowed to stand at room tenperature for 20 hours. Water was added to decompose excess anhydride, and the oily product was extracted into ether. The ether solution was washed successively with dilute hydrochloric acid and sodium bicarbonate solution, dried C-IgSOp, and evaporated to give a yellow oil. A solution of this oil in chloroform was percolated through a short column of silica gel. Evaporation of the eluate gave the product, N-(3-acetoxy-2oxopropyl)-2',6'-dimethylmethanesulphonanilide, as a pale yellow oil.

Yield 2.5g (77¾).

Analysis: C, 53.20; H, 6.57; N, 4.30¾ C14H19NO5S recluires c> 53.66; H, 6.11; N, 4.47¾ Example 244 A solution of N-/3_(2-(ethoxycarbonyl)hydrazinocarbonyl)ethyl272',6'-dimetbylmBtbanesulphonanilide (5.6g) in ethanol (75 ml) and 10¾ sodium hydroxide solution (75 ml) was heated on a steam bath for 2I hours, and then the ethanol was evaporated off. The aqueous solution remainingwas acidified with dilute hydrochloric acid, heated on a steam bath for 1 hour, and then filtered. The filtrate was just neutralised with dilute sodium hydroxide solution, saturated with sodium chloride and extracted with chloroform, lhe chloroform solution was dried and evaporated, and the residue gave colourless crystals of N-ZT--(hydrazinocarbonyl)ethylZ7-2',6,-dimethylmsthanesulphonanilide from a solution in toluene/60-80° petrol. Yield 2.6g (58¾). Melting point 115-118°.

Example 245 A solution of the hydrochloride salt of N-ZT--(hydrazinocarbonyl)ethyQ^'jd'-dimethylrosthanesulphonanilide (3.2g) and acetylacetone (1.0 ml) in ethanol (2S ml) was heated to boiling, and then allowed to cool to room temperature during 2 hours, lhe precipitated solid was collected by filtration and recrystallised from ethanol to give N-ZZ2-(3,5-dirosthyl-l-pyrazolyl)-l-miethyl-2-oxo-ethy£721,6'dimethylmethanesulphonanilide. Yield l.Sg (43¾). Melting point 168°.

Example 246 Methyl isocyanate (1.2 ml) was added to an acetone solution of N-Z72-hydroxyiminopropyl272',6’-dimethylmethanesulphonanilide (2.7g) containing triethylamine (0.05 ml). The mixture was allowed to stand at room tenperature overnight, then evaporated to a viscous oil which slowly solidified on standing. Reerystallisation from ethylacetate/60-80° petrol gave colourless crystals of N-£2-(methylcarbamoyloxyimino)propy127-2',6'-dimethylmethanesulphonanilide.

Yield 3.0g (91$). Melting point 130-134°.

A mixture of N-Z72-hydroxyiminopropyl^7-2',6’-dimethylmethanesulphonanilide (2.7g), potassium carbonate (O.75g), iodomethane (1.3 ml) and acetone (50 ml) was stirred and boiled gently under reflux for 3 hours. Ihe reaction mixture was filtered, and the filtrate evaporated to an oil, which deposited crystals from a solution in ether/40-60° petrol. Yield 0.6g (21$). Melting point 126° Example 243 Acetyl chloride (0.9 ml) was added to a dichloromethane (20 ml) solution of N-[fl-hydroxyiminopropylZ7~2',6'-dimsthylmethane25 sulphonanilide (2.6g) and triethylamine (1.6 ml). The mixture was stirred and boiled under reflux for 3 hours, then filtered, and the filtrate evaporated to a clear yellow oil. A solution, of this oil in chloroform was percolated through a short column of silica gel, and the eluate evaporated to give analytically pure M-/72-(acetyl5 oxyimino)propyl~7-2' ,6' -dimethy lmethanesulphonanilide. Yield 1.9g (63¾).

Analysis: Found: C, 53.74; H, 6.80; N, 8.49¾ C^iyX'jO^S requires: C, 53.83; R, 6.45; N, 8.97¾ Example 249 A solution of diethyl ethoxymagnesium malonate was prepared by refluxing a mixture of magnesium (0.9g), diethyl malonate (5.6 ml), ethanol (4.3 ml) and ether (20 ml) for 3 hours, then evaporating with toluene and replacing the solvent with dry ether. To this solution was added dropwise with stirring an ethereal solution of N-(1-chlorocarbonylethyl)-21,6'-dimethyl-methane sulphonanilide (prepared from the acid (lOg) and thionyl chloride). After stirring overnight at room tenperature, the resulting complex was decomposed by wanning with dilute sulphuric acid. Organic products were extracted into ether and the solution was washed with water, dried (MgSO^), and evaporated to give a solid residue. Recrystallisation from ethyl acetate gave colourless crystals of N-£33,3-di(ethoxycarbonyl) -2-oxo-l-me thyIpropyYJ-21,6' -dimethyl-methanesulphonanilide. Melting point 125°.

Exanple 250 A solution of N-0-ethoxycarhonylethyn7-Z'-trifluoromethyl4'-phenylthio-methanesulphonanilide (7.5g) in acetic acid (50 nil) was heated to boiling with stirring, and hydrogen peroxide (6 ml of 100 vols) was added. Stirring and boiling under reflux were continued for 3 hours, then the reaction mixture was poured into ice/water and extracted with chloroform, lhe chloroform solution was dried and evaporated to a yellow oil which gave colourless crystals of N-/~l-ethoxycarbonvletliyl~7-2'-trifluoromethyl10 4'-phenylsulphonyl-methane-sulphonanilide from an ethanol solution. Yield &.6g (83¾). Mblting point 121°.

Example 251 A solution of N-carboxymethyl-2',0'-dimethyl-methanesulphonanilide (7.2g) in chloroform (50 ml) was treated with thionyl chloride (5 ml), and the mixture was boiled under reflux for 1) hours, then evaporated. The residue was re-evaporated with toluene (to remove traces of thionyl chloride), and then dissolved in dry tetrahydrofuran (10 ml). Tris-trimethylsilyloxyethylene (19.6g) was added followed by stannic chloride (3 drops). The reaction mixture was allowed to stand at room tenperature for 70 hours, then was heated on a steam bath for 2 hours, and poured into a mixture of equal volumes of dilute hydrochloric acid and tetrahydrofuran.

This solution was heated on the steam bath for ) hour, saturated with salt, and extracted with ether. Tiie combined ether solution was washed with sodium bicarbonate solution, dried (MgSO^) and 100 evaporated to give the product, N-Zr3“hydroxy-2-oxopropylZ7-2',6'dimethyl-methanesulphonanilide, as a clear yellow oil. Yield S.Og (66¾).

/Analysis: C, 57.72; H, 6.40; N, 4.91¾ C12H17NO4S requires: C, 53.12; H, 6.32; N, 5.16¾ Example.252 Following a procedure analogous to that of Example 251, N-ZZ3-hydroxy-2-oxo-l-methylpropylZ7_2',6'-dimethyl-methanesulphonanilide was prepared. Melting point 125-126°.

Examples 253 and 254 In a similar way to Examples 191-206, 2',6'-dimethy 1-4morpholinesulphonanilide, melting point 124°, and 3',4'-dichloro-4-morpholinesulphonanilide, melting point 122°, were prepared.

Examples 255-258 In a similar way to Exanple 3, the following esters of formula given in Examoles 4-33 were prepared: Sub Melting Point 20 Exanple R1 CO A 255 n-Pr Me COOCH,-#^ Z \qZ 2,6-diMe Oil 256 Ms II CH=CHCOOEt 2-Cl,6-Me 70° 257 Me Ife COOEt 3,5-diCl 92° 258 Me Me COOMe 3,5-diCl 110° 101 Tlie analysis Tor the compound of Exanple 256 is as follows: Found: 60.63¾ C, 7.00¾ K, 3.69¾ N; C19!i25VO5S recluires: 6O-14°S c> 6·64ϊ 3·695 N· Examples 259-260 In a similar way to Example 34, the following compounds of formula given in Examples 35-43 were prepared.

Example R1r18 A Sub Melting Point 259 Me H C0N^J3 2,6-diMe 109° 260 Me Me CON7/) \—/ 3,5-diCl 210° Exam-pie 261 In a similar way to Example 207, l·!-(2-oxopropyl)-3',5'-dichloromethanesulphonanilide, melting point 106°, was prepared.

Exanple 262 IS In a similar way to Exanple 44, M-(3-cyanopropyl)-3',5'dichloro-raethanesulphonanilide, melting point 82°, was prepared. Example 263 In a similar way to Exanple 121, the lactone melting point lZS*’, was prepared. 102 Example 264 In a similar way to Example 85, N-(thiocarbainoylmethyl)-3',5'dichloro-methanesulphonanilide, melting point 18S°, was prepared. Example 265 4O3g 25g A 40% weight/volume emulsifiable concentrate was prepared by making a xylene solution of the following: N-(1-(ethoxycarbonyl)ethyl)-2',6'-diroethyl-1propanesulphonanilide Arylan C4. (calcium dodecylbenzenesulphonate 10 70% in butanol) Ethylan C40AH (castor oil/ethylene oxide condensate) (Ethylan is a trade mark) Xylene (to 1 litre) Example 266 A 25% weight/volume emulsifiable concentrate was prepared by making a xylene solution of the following: N- (1-(ethoxycarbonyl)ethyl)-2',6'-dimethylethanesulphonanilide 250g Arylan CA 25g Ethylan C40AH 2Sg Xylene (to 1 litre) approx 740 ml 2Sg approx 600 ml Example 2fi7 N-(2-oxopropyl)-3',4'-dxmcthyl-metiianesulphonanilide was tested at a dose rate of 300 ppm in the test described in Examples 231 and 232. it gave a mycelial control score of 0 and a gsnaination score 103 of 3 whereas the untreated samples gave a score of 0 for both. Examples 268-270 'lhe compounds listed below were tested in the test described in Examples 168-176, with the following results: Example Compound Pate, ppm | Disease S Control 268 Product of Example 46 2000 potato blight 56 269 N~(2-oxopropyl)-3' ,4'- dimethvl-methane sulphonanilide 2000 rice blast 67 2000 barley powdery mildew 99 2000 potato li light 62 270 Product of Exanple 247 j 500 potato blight 74 500 rice blast 66 Example 271 In a similar way to Exanple 207, (2-oxopropyl)-3',4’-dimethylmethanesulphonanilide, melting point 78°, was prenared.

Claims (41)

1. A method of combating pests at a locus infested or liable to be infested with them or regulating the growth of a plant at a locus at wiiich the plant is growing or is to grow, which method comprises applying to the locus a pest-combating or plant growth regulant amount of a compound which is a sulphonanilide of formula SO/ N-R-A or salt thereof, wherein represents alkyl, substituted alkyl, eycloalkyl, aralkyl, 10 substituted aralkyl, a heterocyclic group, /R 7 a substituted, heterocyclic group, or a group of formula -N^ g 7 8 R where R and R are the same or different and each represents a hydrogen atom, allyl, substituted alkyl, aralkyl, substituted aralkyl, aryl or substituted aryl; 15 R represents alkylene or alkenylene; q M 11 9 .-R 7 A represents -COOH; -CSSH; -CEGR 3 ; -CENR AU R A1 ; -C-O-N=C Q ; 12 XR -Cfl·; -COO eycloalkyl; or -COR or a carbonyl derivative or addition compound thereof; where E and G are the same or different and each represents an oxygen or sulphur atcra,· R 9 represents alkyl, substituted alkyl, aralkyl, 20 substituted aralkyl, aryl or substituted aryl; R^° and R^ are the sane or different and each represents a group as defined 105 for R 7 ; or R 10 and R 11 together with the nitrogen atom to which they are attached form a heterocyclic group or a substituted heterocyclic group; or R 1<7 represents a hydrogen atom while R 11 represents a group of formula -N=C^ R Q or where R 13 represents a hydrogen \R y X R 13 atom or -COOR ; and R represents a hydrogen atom, alkyl, substituted alkyl, cycloaikyl, aralkyl, substituted aralkyl, aryl, substituted aryl, a heterocyclic group linked via a carbon atom in the group or such a heterocyclic group which is substituted; or R-A represents a group of formula / C % ch 2 c; -C B I X C Z R15 15 wherein R 1 ^ represents a hydrogen atom, alkyl or aryl, B I ig 15 represents an oxygen atom or -NR , R represents a hydrogen atom or alkyl, and n represents 0, 1 or 2; and R Z , R 3 , R^, R 5 and R 6 are the same or different and each represents a hydrogen atom; alkyl; substituted alkyl; hydroxy; 20 alkoxy; -SCN; nitro; halogen; amino; substituted amino; mercapto; a group of formula -SR 16 , -SC» 16 , -SO2R 16 or-0S02R 16 where R 16 represents alkyl, aryl or aralkyl; -SO 2 NR 7 R 8 ; or -COOR 12 . 106

2. A method according to claim 1 wherein R^ represents alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, alkoxycarbonyl of 2-7 carbon atoms, carboxy, -&NR 3 '°r’'’‘, phthalimido, -SCN, benzoyloxy, alkanoyloxy of 2-7 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, furyl, nitrile, hydroxy, amino and amino mono- or disubstituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; cycloalkyl of 3-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atoms, atoms alkoxy of 1-6 carbon/, nitro, -SCN, alkylsulphonyloxy of 1-6 carbon atoms and trifluoromethyl; a heterocyclic group which is a single hetero ring containing 3 to 7 ring atoms of which 1-3 are hetero atoms, each hetero atom being nitrogen, sulphur or oxygen, to which hetero ring a benzene ring is optionally fused; such a heterocyclic ring substituted by one or more of alkyl of 1-6 carbon atoms, oxo, nitro and halogen; or a group of formula R 7 ., 7 8 -N.; a where R and R are the same or different and \ R 8 each represents a hydrogen atom; alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, alkoxycarbonyl of 2-7 carbon atoms, carboxy, -^NR^R 1 · 1 ·, phthalimido, -SCN, benzoyloxy, 107 alkanoyloxy of 2-7 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, furyl, nitrile, hydroxy, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 5 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, allyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro, -SCN, alkylsulphonyloxy of 1-6 carbon atoms and trifluoromethyl; phenyl; or phenyl substituted by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, alkylsulphonyloxy of 10 1-6 carbon atoms, nitro, -SCN and trifluoromethyl; R represents alkylene or alkenylene of 1-6 carbon atoms; A represents -COOH; -CSSH; -CEGR 9 ; -CENR 10 R 11 ; -E-0-N=C^ R ; 12 ' S ' R -CN; cycloalkyloxycarbonyl of 4-8 carbon atans; or -COR or a carbonyl derivative or addition canpound thereof; where E and G are the same or different 15 and each represents an oxygen or sulphur atan; R represents allyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, alkoxycarbonyl of 2-7 carbon atoms, carboxy, phthalimido, -SCN, benzoyloxy, alkanoyloxy of 2-7 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, furyl, 20 nitrile, hydroxy, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro, -SCN, 25 alkylsulphonyloxy of 1-6 carbon atoms and trifluoromethyl; phenyl; 108 or phenyl substituted by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro, -SCN, alkylsulphonyloxy of 1-6 carbon atoms and trifluoromethyl; R 1 ^ and R 11 are the same or different and each represents a group as defined for R immediately above; or R 1 ® and R 11 together with the nitrogen atom to which they are attached form a heterocyclic group wiiich is a single hetero ring containing 5-7 ring atoms of which besides the nitrogen atom there may he 1 or 2 further hetero atoms, each hetero atom being oxygen, sulphur or nitrogen, to which hetero ring a benzene ring is optionally fused, or such a heterocyclic group substituted by one or more of alkyl of 1-6 carbon atoms, oxo, nitro and halogen; or R 1 ® represents a hydrogen atom while R 11 represents a group of formula -N=C^ R Q or where R 13 represents a hydrogen atom Χ.η·' 9 Λ 12 Λ or -COOR ; and R represents a hydrogen atom, alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted hy one or more of halogen, alkoxy of 1-6 carbon atoms, alkoxycarbonyl of 2-7 carbon atoms, carboxy, -fiNR^R 11 , phthalimido, -SCN, benzoyloxy, alkanoyloxy of 2-7 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, furyl, nitrile, hydroxy, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; cycloalkyl of 3-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro, -SCN, alkylsulphonyloxy of 1-6 carbon atoms and trifluoromethyl; phenyl; phenyl substituted 109 4763? by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, nitro, -SCN and trifluoromethyl; a heterocyclic group linked via a carbon atom in the «roup, which group is a single hetero ring containing 3 to 7 ring atoms of which 1-3 are hetero atoms, each hetero atom being nitrogen, sulphur or oxygen, to which hetero ring a benzene ring is optionally fused; or such a heterocyclic group substituted by one or more of alkyl of 1-6 carbon atoms, oxo, nitro and halogen: or R-A representsa group of formula V n 2 “ i'MI „14 wherein R represents a hydrogen atom, alkyl of 1-6 carbon I js 15 atoms or phenyl, B represents an oxygen atom or -NR , R ' represents a hydrogen atom or alkyl of 1-6 carbon atoms, and n represents 0, 1 or 2; and R 2 , R'\ R 4 , If’ and R 6 are the same or different and each represents a hydrogen atom; alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, alkoxycarbonyi of 2-7 carbon atoms, carboxy, -GstJ'V 1 , phthalimido, -SCN, benzoyloxy, alkanoyloxy of 2-7 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, furyl, nitrile, hydroxy, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; hydroxy; alkoxy of 1-6 carbon atoms; -SCN; nitro; mercapto; a halogen atom; amino; amino mono- or di-substituted by groups selected from alkyl of 1—15 carbo:: atoms and alkanoyl of 2-7 carbon atoms; a group o£ fornula -SR 16 , -SOR 16 , -SO2R 16 or -OSO2R 16 where R 16 represents alkyl of 1-6 carbon atoms, phenyl or phenylalkyl of 7-10 carbon atoms; 7 8 7 8 -SO,NR R where R and R are as defined immediately above; or 2 12 12 -COOR where R is as defined immediately above · no

3. A method according to claim 2 wherein 3 or 4 of R , R 2 , R 4 , R 3 and R 6 each represents a hydrogen atom.

4. A method according to claim 2 wherein R 1 represents alkyl of 1-4 carbon atoms, 2-phthalimidoethyl, 5. EthoxycarbonyImethyl, morpholino, thienyl or dialkylamino of 2-8 carbon atoms; R represents alkylene of 1-3 carbon atoms or alkenylene of 3 carbon atoms; 111 Λ represents -COOH; -CENH 2 ; -CN; -CONHPh; eycloalkyloxycarbonyl of 4-8 carbon atoms; morpholinocarbonyl; -C0NHNI! 2 ; -CQNHCl^COO alkyl of 1-4 carbon atoms; -CONHNHCOO alkyl of 1-4 carbon atoms; -C-N^ N \CH,; -COOR 17 or -CON(R 17 ), where R 17 represents alkyl of β v V 1-8 carbon atoms; -COCH,; -COCH,OH; CrL * .OCH, -OCH, CH, -C-CH, NOH -C /S—CH 2 |\ s CH, -¾ /0—ch 2 -c |\—CH, CH, -COOCH. -O' 0-CH / \ CH, 0 — CH CH^OH -C0C(CH 3 ) 3 ; -COCJ1,OCOCH 3 ; -CONH-OVsCN ; -C0C41 •COOEt COOEt -C-CH, . -C-CH. 3 ; or -C-CH, R-A represents JJOCii 3 NOCCHj NOCNHCH- 0 ; and 112 3 or 4 of S 2 , R 2 , R 4 , R 3 and R 6 each represents a hydrogan atom and the remainder are the same or different and each represents alkyl of 1-3 carbon atoms, halogen, hydroxy, phenylmercapto, -SCN, nitro, alkoxy of 1-6 carbon atoms, trifluoromethyl, phenylsulphonyl, or methylsulphonyloxy .

5. A method according to claim 2 wherein R 1 represents alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, amino and amino mono- or disubstituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; cycloalkyl of 3-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atoms, atoms alkoxy of 1-6 carbon/, nitro and trifluoromethyl; or a group of formula R 7 7 8 -N.C - where R and R are the same or different and each \R 8 represents a hydrogen atom; alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more halogen, alkoxy of 1-6 carbon atoms, amino and amino mono- or disubstituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro and trifluoromethyl; phenyl; or phenyl substituted by one or more of 113 halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atons, nitro and trifluoromethyl; Ii represents alkylene of 1-6 carbon atoms; Ω 7 q in n --p/ A represents -COOH, -CSSH, -CEGR', -CENR 1 R , -C-0-N=C^ 9 3 or -CN; where E and G are the same or different and each represents Q an oxygen or sulphur atom; R represents alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms 10 and alkanoyl of 2-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro and trifluoromethyl; phenyl; or phenyl substituted by one or more of halogen, alkyl of 1-6 carbon atoms, IS alkoxy of 1-6 carbon atoms, nitro and trifluoromethyl; and R^· are the same or different and each represents a group as defined for R 7 immediately above; or R 10 and R 17 together with the nitrogen atom to which they are attached form a monocyclic heterocyclic group containing 5 or 6 ring atoms of which besides the nitrogen 20 atom there nay be a further hetero atom, which hetero atom is oxygen or nitrogen; or R' 10 represents a hydrogen atom while „7 13 represents a group of formula -N-C'' η or -Ν Ί , where R 1 represents a hydrogen atom or -COOR; and R 7 , R 3 , r\ R$ and R& are the same or different and each 2S represents a hydrogen atom; alkyl of 1-15 carbon atoms; alkyl of - 113 114 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, amino and amino mono- or disubstituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; alkoxy of 1-6 carbon 5 atoms; -SCN; nitro; mercapto; alkylmercapto of 1-6 carbon atoms; amino or a halogen atom.

6. A method according to claim 2 wherein R^ represents alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, 10 alkoxy of 1-6 carbon atoms, amino and amino mono- or disubstituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; cycloalkyl of 3-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl 15 nucleus by one or more of halogen, alkyl of 1-6 carbon atoms atoms, alkoxy of 1-6 carbon/, nitro and trifluoromethyi; a heterocyclic group which is a single hetero ring containing 3 to 7 ring atoms of which 1 or 2 are hetero atoms, each hetero atom being nitrogen, sulphur or oxygen, 115 to which hetero ring a benzene ring is optionally fused: such a heterocyclic group substituted by one or more of alkyl of 1-G carbon atoms, nitro and halogen; or a group of formula -iv \ where R and R' are the X !C sane or different and each represents a hydrogen atom; allyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, amino and amino monoor di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; phenylalkyl of 7-10 carbon atoms: phenylalkyl of 7-10 carbon atoms substituted cn the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro and trifluoromethyl; phenyl; or phenyl substituted by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, nitro and trifluoromethyl; R represents alkylene or alkenylene of 1-6 carbon atoms; n A represents -COR 1 ' or a carbonyl derivative or addition conpound 1? thereof, where R represents a hydrogen atom, alkyl of 1-15 carbon atoms; alkyl of 1-15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, amino and amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carbon atoms; cycloalkyl of 3-7 carbon atoms; phenylalkyl of 7-10 carbon atoms; phenylalkyl of 7-10 carbon atoms substituted on the phenyl nucleus by one or more of halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, nitro and trifluoromethyl; phenyl; phenyl substituted by one or more of 116 halogen, alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, alkylsulphonyloxy of 1-6 carbon atoms, nitro and trifluoromethyl; a heterocyclic group linked via a carbon atom in the group, which group is a single hetero ring containing 3 to 7 ring atoms of 5 which 1 or 2 are hetero atoms, each hetero atom being nitrogen, sulphur or oxygen, to which hetero ring a benzene ring is optionally fused; or such a heterocyclic group substituted by one or more of allyl of 1-6 carbon atoms, nitro and halogen; and R 2 , I·’ 3 , R 4 , R 3 and R 6 are the same or different and each 10 represents a hydrogen atom; allyl of 1-1S carbon atoms; alkyl of 1- 15 carbon atoms substituted by one or more of halogen, alkoxy of 1-6 carbon atoms, amino and amino mono- or di-substituted by groups selected from allyl of 1-15 carbon atoms and alkanoyl of 2- 7 carbon atoms; alkoxy of 1-6 carbon atoms; -SCN; nitro; mercapto; 15 a halogen atom; amino; amino mono- or di-substituted by groups selected from alkyl of 1-15 carbon atoms and alkanoyl of 2-7 carhon atoms: a group of formula -SR 16 , -S0R 16 or -SC^R 16 where R 16 represents alkyl of 1-6 carhon atoms, phenyl or phenylallyl of 12 12 7. -10 carbon atoms; or -COOR where R is as defined immediately 20 above.

7. A method according to claim 1 wherein the compound is one specified herein.

8. A method according to claim 1 wherein the conpound is N-cyanomethyl-3' -dichloro-methanesulphonanilide; or 117 Ν- (1-£ cthoxycarbonylZ7ethyI)-2' ,6’-dimethyl-ethanesulphonanilide.

9. A method according to claim 1 wherein the canpound is N- (1-ethoxycarbonyl) etnyl) -2 1 ,6 * -dimethyl-1-propanesulpncnanilide.

10. A method according to claim 1 wherein the canpound is N- (1- (methaxy5 carbonyl6 '-dimethyl-irethanesulphaianilide or N-2-oxopropyl-2 1 ,6'dimethyl-itethaneeulphaianilide.·

11. A method according to any cne of the preceding claims wherein the ccnpound is applied to a locus at which a crop is grcwing or is to grew.

12. Λ method according to claim 11 wherein 0.5-10 kg of the 10 compound are applied per hectare and weeds are selectively combated.

13. A method according to claim 11 wherein 1-6 kg of the compound are applied per hectare and fungus is combated.

14. A method according to claim 1 performed substantially as described herein.

15. 15. A compound which is a sulphonanilide of formula SO^ 1 N-R-A or salt thereof, wherein R·^ represents alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, a heterocyclic group, -R a substituted heterocyclic group, or a group of formula -Ν. θ 7 8 R where R and R are the same or different and each represents a hydrogen atom, alkyl, substituted alkyl, aralkyl, substituted 118 aralkyl, aryl or substituted aryl; R represents alkylene or alkenylene; 0 7 Λ represents -COOH; -CSSH; -CEGR 9 ; -CEmA 11 ; -C-O-.\ t =C^ R ; 12 Λ -CN; -COO cycloalkyl;or -COR or a carbonyl derivative or addition caipound thereof; where E and G are the same or different and each represents an oxygen or sulphur atom; R J represents alkyl, substituted alkyl, aralkyl, substituted aralkyl, aryl or substituted aryl; R 10 and R 11 are the same or different and each represents a group as defined •7 Tf) TT for R'; or R and R together with the nitrogen atom to which 10 they are attached form a heterocyclic group or a substituted heterocyclic group; or R 1<9 represents a hydrogen atom while R 11 „7 r represents a group of formula -N=C^ 0 or -N ., where R iJ represents 9 I?' R XR a hydrogen atom or -COOR ; and R represents a hydrogen atom, alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, aryl, 15 substituted aryl, a heterocyclic group linked via a carbon atom in the group or such a heterocyclic group which is substituted; or R-A represents a group of formula CH. / C,! A „14 —c. R„14 wherein R represents a hydrogen atom, alkyl or aryl, B I ic ic represents an oxygen atom or -NR , R represents a hydrogen atom or alkyl, and n represents 0, 1 or 2; and 119 2 3 4 5 6 R , R , R , R and R are the same or different and each represents a hydrogen atom; alkyl; substituted alkyl; hydroxy; alkoxy; -SCN; nitro; halogen; amino; substituted amino; mercapto; a group of formula -SR 16 , -SOR 16 , -SO 2 R 16 T fi lfi 5 or -OSO 2 R where R represents alkyl, aryl or aralkyl; -SO 2 NR 7 R 8 ; or -COOR 12 .

16. A compound as defined in Claim 2.

17. A compound defined in Claim 4.

18. A compound defined in claim 5. g 10

19. A compound defined in claim 6 wherein R represents other than hydrogen.

20. A compound according to claim 15 substantially as described herein.

21. A compound according to Claim 15 which is specified 15 herein.

22. N-cyanomethyl-3',4'-dichloro-methanesulphonanilide; or 120

23.

24. N- (l-/7cthoxycarbonyl_7ethyl) -2',6' -dimethyl-etlianesulphonanilide. Ν-(1-C ethoxycarbony!)ethyl)-2’,6'-dimethyl -1prcpanesulphonanilide. N-2-oxopropyl-2' ,6'-dimethyl-methanesulphonanilide.

25. A process for preparing a compound which is a sulphonanilide of formula S0 2 P · N-R-A or salt thereof, wherein R 1 represents alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, a heterocyclic group, a substituted heterocyclic group, or a group of formula -N n 7 8 XR where R and R are the same or different and each represents a hydrogen atom, allyl, substituted alkyl, aralkyl, substituted aralkyl, aryl or substituted aryl; R represents alkylene or alkenylene; 0 7 A represents -COOH; -CSSH; -CEGR 9 ; -CENR^R 11 ; -C-0-N=c R Q ; ^R 12 Λ -CN; -OOO cycloalkyl,· or COK or a carbonyl derivative or addition ccnpound thereof; where E and G are the same or different and each represents □ an oxygen or sulphur atom; R represents allyl, substituted allyl, aralkyl, substituted, aralkyl, aryl or substituted aryl; R 10 and R 11 121 arc the same or different and each represents a group as defined for R 7 ; or R l!1 and R 11 together with the nitrogen atom to which they are attached form a heterocyclic group or a substituted heterocyclic group; or R 1 ^ represents a hydrogen, atom while R 11 n/ /u 23 represents a group of formula -N=C^ c , or -N ,, where P. Si·' Xti-J-*·* qK 12 * represents a hydrogen atom or -COOR ; and R represents a hydrogen atom, alkyl, substituted alkyl, cycloallyl, aralkyl, substituted aralkyl, aryl, substituted aryl, a heterocyclic group linked via a carbon atom in the group or such a heterocyclic group which is substituted; or R-A represents a group of formula B wherein R represents a hydrogen atom, alkyl or aryl, B I ic κ represents an oxygen atom or -NR , R represents a hydrogen atom or alkyl, and n represents 0, 1 or 2; and R 2 , R 3 , R 4 , R 3 and R 6 are tha same or different and each represents a hydrogen atom; alkyl; substituted alkyl; hydroxy; alkoxy; -SCN; nitro; halogen; amino; substituted amino; mercapto; a group of formula -SR 16 , -SOR 16 , -SC^R 16 or -OSO^R 16 where R 16 represents alkyl, aryl or aralkyl; -SO 2 NR 7 R 8 ; or -COOR 12 ; 122 which process comprises: (a) reacting a sulphonamide of formula II or salt thereof, with a halo derivative of formula X-P-A, wherein X represents a halogen atom and A, R, r\ P 7 , R 3 , R.\ R 3 and R 3 are as defined above; (b) acylating an arylamino derivative of formula III κ 1 or salt thereof, with an acylating agent of formula R SC^Z or l 12 3 (R 93 2 ) 7 0 where Z represents a halogen atom and A, R, R , R , R , r\ r 5 and. R 6 are as defined above; (c) where A represents -COOH, hydrolysing a sulphonanilide of formula I or salt thereof in which A represents -COOR 9 , 123 .· 7 Q 10 η -0-0-,1=0 a q or -CN where R , R , R and R are as defined above; XR 9 (d) where A represents -COOR , esterifying a sulphonanilide of formula I or salt thereof in which A represents -COOH with an alcohol of formula R S 0!I; (e) where A represents -CECR 5 , reacting an acyl halide of formula so 2 R IV halogen atom and E, G, R, R 1 , R 2 , R J , R 4 , R 5 , defined above; where Y represents a R 6 and R 8 are as (f) where A represents -CONR^R 11 , reacting the acyl halide of formula IV where E represents an oxygen atom with an amino derivative of formula HNR^R 11 , where R 1 ® and R 11 are as defined above; (g) where A represents -C-O-N=C Q , reacting the acyl halide of fornula IV' where E represents an oxygen atom with a hydroxylamine 7 7 9 derivative of formula HON=C Q where R and R are as defined above; x R y 12 12 (ii) where A represents -COR except where R represents a hydrogen atcm or a carbonyl derivative or addition ccmpound thereof, decarboxylating a carboxylic acid of formula 124 (i) where A represents a carbonyl derivative of -COR , reacting the corresponding compound in which A represents -COR with a material of formula HMH to eliminate a molecule of water between them; where M represents a divalent radical such that the material of formula HMH reacts with the ccmpound in which A represents -COR to form a carbonyl derivative thereof. (j) where A represents ^Oalkyl —c ί 1Z OaUcyl reacting the corresponding compound in which A represents -COR with an orthoformate of formula CcI(Oalkyl) · Q 12 (k) where A represents an oxime carbamate of -C-R , reacting the corresponding oxime wvith an isocyanate, or a carbamoyl chloride, or with phosgene and then an amine; * 12 (1) where A represents an addition compound of -fi-R , ,12 reacting the corresponding compound in which A represents -COR ivith the compound ivith which it is required to make up the addition compound; (m) to produce a salt of the sulphonanilide, salifying the sulphonanilide; or (n) to produce the sulphonanilide, desalifving a salt of the 125 sulphonanilide. 2ΰ. A process according to claim 25 performed substantially as described herein.

26. 27. A process according to claim 25 performed substantially as described herein in any one of the Examples.

27. 28. A compound claimed in claim 15 prepared by a process claimed in any one of claims 25-27.

28. 29. A pesticidal or plant growth regulant composition comprising a compound which is a sulphonanilide of formula SOzR 1 A-r-a or salt thereof, wherein 1 R represents alkyl, substituted alkyl, cycloallyl, aralkyl, substituted aralkyl, a heterocyclic group, ^R 7 a substituted heterocyclic group, or a group of formula -N * g 7 8 R where R and R are the same or different and each represents a hydrogen atom, alkyl, substituted alkyl, aralkyl, substituted aralkyl, aryl or substituted aryl; R represents alkylene or alkenylene; „9. -R A represents -COCH; -CSSH; -CECR y ; -CEN^.^R 11 ; ; „12 -CN; -COO eycloalkyl; or -COR or a caibcnyl derivative or addition caipound thereof; where E and G are the same or different and each represents an oxygen or sulphur atom; R 9 represents alkyl, substituted alkyl, 126 10 11 aralkyl, substituted aralkyl, aryl or substituted aryl; R and R are the same or different and each represents a group as defined for Γ 7 ; or R 1 ® and R 11 together with the nitrogen atom to which they are attached form a heterocyclic group or a substituted heterocyclic group; or R lt3 represents a hydrogen atom while R 11 7 13 represents a group of formula -NO' Q or -N fZ where κ represents 9 12 a hydrogen atom or -COOR ; and R represents a hydrogen atom, alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, aryl, substituted aryl, a heterocyclic group linked, via a carbon atom in the group or such a heterocyclic group which is substituted; or R-Λ represents a group of formula CH, /R 14 -C B R 15 || wherein R represents a hydrogen atom, alkyl or aryl, B I it i: represents an oxygen atom or -NR , R represents a hydrogen atom or alkyl, and n represents 0, 1 or 2; and 20 R 2 , R 3 , R 4 , R 3 and R 6 are the same or different and each represents a hydrogen atom; allyl; substituted alkyl; hydroxy; alkoxy; -SCN; nitro; halogen; amino; substituted amino; mercapto; a group of formula -SR 16 , -SOR 16 , -SO2R 16 or -OSO2R 16 where R 16 represents alkyl, aryl or aralkyl; -SO,NR 7 R 8 ; or -COOR 12 ; 127 together with at least one material selected from other pesticides, other plant growth regulants, surface active agents, solid carriers, hydrocarbons o£ boiling point in the range 139-270¾, antidotes and fertilizers.

29. 30. A pesticidal or plant growth regulant composition comprising a compound claimed in claim 15 together with at least one material selected from carriers, surface active agents, other pesticides, other plant growth regulants, antidotes and fertilizers.

30. 31. A composition according to claim 30 wherein the compound is as claimed in claim 16.

31. 32. A composition according to claim 31 wherein the compound is as claimed in claim 17.

32. 33. A composition according to claim 31 wherein the compound is as claimed in claim 18.

33. 34. A composition according to claim 31 wherein the compound is as claimed in claim 19.

34. 35. A composition according to claim 31 wherein the compound is as claimed in claim 21

35. 36. A composition according to claim 31 wherein the compound is as claimed in claim 22.

36. 37. A composition according to claim 31 wherein the compound is as claimed in clai.: 23. 128

37. 38. A composition according to claim 31 wherein the compound is as claimed in claim 24.

38. 39. A composition according to any one of claims 29-38 which contains a surface active agent. 5

39. 40. A composition according to any one of claims 29-39 substantially as described herein.

40.

41. A composition according to any one of claims 29-39 substantially as described herein in any one of the Examples