DD143199A5 - CROPPING AGENT OR PLANT GROWTH REGULATOR - Google Patents

Description

Pesticides or plant growth regulants

Field of application of the invention

The present invention relates to a process for the preparation of novel compounds and to compositions for. Controlling pests and regulating plant growth.

Characteristic of the known technical solutions

Pesticidal and plant growth regulating compounds, methods and compositions are known.

Object of the invention

The aim of the present invention is the preparation of improved compounds, processes and compositions for this application,

Explanation of the essence of the invention

The object of the invention is to provide new pesticides or plant growth regulators. "

Accordingly, the invention relates to a method for controlling

9. 4. 1979 54- 760 18

of pests in a place infested or liable to be attacked by them, or for regulating plant growth in a place where the plants are to grow or grow, '' a pest-controlling or growth-regulating amount of a compound being applied to the site concerned ' namely a sulfonanilide of the formula

SO ₂ R

IT-H-A

(D

or a salt Ke-rvon is applied, in which formula

R is alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, aryl, substituted aryl, heterocyclic group, substituted heterocyclic group or a group of formula -H * "* g wherein R 'and R are the same or different and each R5 is hydrogen, alkyl, substituted alkyl, aralkyl, substituted aralkyl, aryl or substituted aryl; R is alkylene or alkenylene;

ß .7

C-

C-O-C = C

-R '

12 · ^X R ⁹

COR 'or a carbonyl derivative or an Addi »

A-COOH; -CSSH; -CBGR

-CN or

compound of which is B and G are the same or different and each is oxygen or sulfur; R is alkyl, substituted alkyl, aralkyl, substituted

- 1b -

9. 4. 1979 760 18

substituted aralkyl, aryl or substituted aryl; 10 11

R and R ¹ 'are the same or different and each one'

7 10 11

Mean group defined for R '; or R and S "together with the nitrogen atom to which they are attached form a heterocyclic group or a substituted heteroaryl group.

Form 10 cyclic groups; or R water

means, while R is a group of the formula

^ ^ * 13

-N = CC "or -N- ^ ₁ _, where R is water

Represents substance or COOR; and R represents hydrogen, alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, aryl, substituted aryl, a heterocyclic group connected via a carbon atom in the group, or such a substituted heterocyclic group; or R-A is a group of the formula

.14

14, wherein R is hydrogen, alkyl or aryl, B is oxygen

¹ 15 15

• or -NR, R is hydrogen or alkyl and η is 0, 1 or 2; and

R, R, R, R and R are the same or different and each is hydrogen, alkyl, substituted alkyl, hydroxy, alkoxy, -SCN, nitro, halogen, amino, substituted amino, mercapto, a group of the formula -SR, -SOR, -SO R or

• 4 / ~CL "V ß

OSO ₉ R, where R is alkyl, aryl or aralkyl, is -SO-NR R or -COOR, with the proviso that R, R, R ⁴ , R and R are not each hydrogen when R is alkylene,

R is phenyl or substituted phenyl and A is COOH or

9 9

COOR, where R is alkyl.

The invention furthermore relates to a pest control agent or a plant growth regulator which contains the abovementioned compound, in particular to an agent which comprises the abovementioned compound together with at least one material from the group of carriers, surface-active agents, other pesticides, other plant growth regulators, antidotes and fertilizers.

10121

Almost all compounds are new and their preparation is thus the subject of the present invention

The invention relates to the preparation of the compounds defined except that the above proviso by the

234 5

Is replaced by the proviso that R, R, R and R are not each hydrogen when R is hydrogen, methoxycarbonyl or ethoxy carbonylmethyl, R is alkylene, R is phenyl or .substituted phenyl

9 9

and A is benzoyl, COOH or COOR, where R is alkyl.

The invention therefore also relates to a process for the preparation of the novel compounds, which is characterized in that a) a sulfonamide of the formula

N-H

-R '

-R-

(H)

or a salt thereof with a halogen derivative of the formula

X-R-A,

in which formulas X is halogen and A, R, R, R, R, R, R and R have the abovementioned meaning,

b) an arylamino derivative of the formula

N-R-A

(III)

or a salt thereof with an acylating agent of the formula

R ^{1 is} SO ₂ Z or (R ¹ SO ₂ ) ₂ 0,

in which formulas Z is a halogen and A, R, R, R, R, R ⁴ , R ' and R have the abovementioned meaning, acylates /

c) when A is -COOH, a sulfonanilide of the formula (I) il :, 7

or a salt thereof, wherein A is -COOR, -CONR R,

-C-O-N = C

or -CN, wherein R ⁷ , R ⁹ , R ¹⁰ and R ¹¹

have the abovementioned meaning, hydrolyzed,

9 ·. '

d) when A is -COOR, a sulfonanilide of the formula (I)

or a salt thereof, wherein A is -COOH, with an alcohol

9 of the formula R OH esterifies,

e) when A is -CEGR, an acyl halide of the formula

N-R-CEY

(IV)

with an alcohol or mercaptan of the formula R GH, in which

ili, 9

Y is halogen and E, G, R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R have the abovementioned meaning,

f) when A is -CONR "R, the acyl halide of For (IV), wherein E is oxygen, with an amino derivative of

Formula HNR R, where R and R are as defined above,

implements, "

g) when A is -C-O-N = C

-. TT

means the acyl halide of

Formula (IV), wherein E is oxygen, with a hydroxyl

• R ⁷

7 9 arainderivat of the formula HON = CC _q , wherein R and R are the above

Have meaning, implements,

h) when A is -COR ¹ or a carbonyl derivative or an addition compound thereof, a carboxylic acid of the formula

N-R-CD (COOH)

12 in which DH _{9 is} R, decarboxylated,

12

i) when A is a carbonyl derivative of -COR, the corresponding

12

A compound wherein A is -COR is reacted with a compound of the formula HMH to remove a water molecule between them,. ,

j) if A.

O-alkyl

1 ^ Oalkyl

12, the corresponding compound in which A is -COR, with an orthoformate of the formula CH (OAlkyl) ^,

fi 12

k) when A is an oxime carbamate of -C-R which reacts correspondingly with oxime with an isocyanate or a carbamyl chloride or with phosgene and then with an amine,

M 12

1) when A is an addition compound of -C-R, the

12

corresponding compound wherein A is -COR with the compound with which the addition compound is prepared

should,

(m) for the preparation of a salt of sulfonanilide, the sulfone

anilide salted or

n) to prepare the sulfonanilide a salt of sulfonanilide

desalted.

Some intermediates in the preparation of the compounds of the invention are novel and the invention also relates to their preparation.

The invention provides: 2 ', 6'-dimethyl-1-propanesulfonanilide; 2 ', 6'-Dichlormethansulfonanilid; 2'-chloro-6'-methylmethanesulfonanilide, 2, 6'-dimethyl-1-butanesulfonanilide; 2 ', 6' dimethylethanesulfonanilide; 2'-Äthylmethansulfonanilid; 3 ', 4'-dichloro-2-thiophensulfonanilid; 3'-chloro-4'-fluoromethanesulfonanilide; 3'-chloro-4'-methylmethansulfonanilid; 2'-Methansulfonyloxymethansulfonanilid; 2 ', 6'-Diisopropylmethansulfonanilid; 2'-methanesulfonyloxy-5'-nitromethansulfonanilid; 2 ', 6'-Dimethyidirnethylaminosulf onanilide; 2'-chloro-6'-methyldimethyiami.no-

-S

sulfonanilide, 2 ', 3'-dichloromethanesulfonanilide; 3 ', 4'-Dimethylmethansulfonanilid; 2 ', 6'-dimethyl-2-propansulfonanilid; 3 ', 4'dichloroethoxycarbonylmethanesulfonanilide; 3 ', 5'-dichloromethanesulfonanilide; 2 ¹ , 6'-Dimethy1-4-morpholinesulfonanilide; 3 ', 4' dichloro-4-morpholinesulfonanilide and their salts.

The invention thus also relates to a process for the preparation of the novel intermediates, namely sulphonamides of the formula (II) and their salts, which consists in reacting an aniline of the formula. ·

(VI)

: I R-

or a salt thereof with an acylating agent of the formula R ¹ SO ₂ Z or (R ¹ SO ₂ J ₂ O acylated.

The sulfonanilide of the formula (I) can form salts. When R ² , R ³ / R ⁴ , R ⁵ or R ^{6 is} -COOH or A is -COOH or -CSSH, a salt can be formed with a base, eg, sodium hydroxide. Such salts are metal salts, in particular alkali metal salts, such as sodium or potassium salts, and amine salts, for example methylamine or ethanolamine salts. The salts may be formed from the non-salt form (ie, the non-salt form may be salified) by methods common to other salts and converted to the non-salt form (ie, desalted). · Methods that are common for other salts are transferred. Thus, a salt can be formed by reacting the non- salt form with a base, eg, sodium hydroxide; a salt with a base can be converted to the non-salt form by reaction with an acid, eg hydrochloric acid.

The sulfonamides of. Formula (II) know form salts. Salts can be formed from the non-salt form by conventional methods for other salts? they can be converted into the non-salt form by methods customary for other salts. Thus, salts can be made by reacting the non-salt form with a strong one

Base formed by reacting with a strong acid, e.g. Hydrochloric acid, are converted into the non-salt form. Salts are, for example, potassium salts.

12 H 12

When R in C-R is hydrogen, the invention are

12 corresponding sulfonanilides aldehydes; if R in

Il I ₂ -CR has a meaning other than hydrogen, the sulfonanilides according to the invention are ketones. In both cases, carbonyl derivatives are formed. The derivatives may be considered to be derived from the carbonyl group of A by reaction with removal of a water molecule. The derivatives include:

OCH ,. 0 - CH ₀

, 3/2

Ketals, where A is, for example, C-OCH ₃ or -C ^ | is

CH ^ ₁ (C ~ ^CH 2

SCH ₃ S- ^CH 2

Thioketals in which A is, for example, -C - SCH _n or -C,

W-

_{3 2}

^CH 3

Oximes, where A is, for example, -C - CH _n ,

Il ³

NOH

Oxime esters wherein A is e.g. -C- CIU is,

NOCOCH ₃

Oxime ethers, wherein A is, for example, -C - CH _n ,.

H 3

NOCK ₃

Oxime carbamates wherein A is e.g. -C - tert.Bu,

Il

NO-CNHCH ₀ Ii ³

.0

Hydrazones, where A is e.g. -C-CH., Is,

NNH "substituted hydrazones, e.g. Methylhydrazones, wherein A is e.g.

-C - CH-, or Il ³

NNHCH

- ΊΟ -

Phenylhydrazones, wherein A is e.g. -C - CH_ is, and

NNHPh

Semicarbazones, where A is, for example, -C - CH ₃ .

NNHCSNH ₂

Carbonyl derivatives are well known in the art.

The addition compounds include those with cyanide ion, bisulfite ion or ammonia. The ions may e.g. Ammonium, sodium or potassium ions. Addition compounds of aldehydes and ketones are well known in the art.

The compounds of the invention are preferably prepared by reacting the sulfonamide of formula (II) or a salt thereof with the halogenated derivative of formula X-R-A. X is halogen (i.e., fluorine, chlorine, bromine or iodine), preferably chlorine or bromine. The reaction is usually carried out in the presence of an acid acceptor, e.g. potassium carbonate.

The compounds of this invention may be prepared by acylating the aryl amino derivative of formula (III) or a salt thereof with an acylating agent of formula (R SO ₉ ) "O, or preferably. R SO "Z are produced. Z is usually chlorine.

The compounds of the invention wherein A

-COOH can be obtained by hydrolysis of the compound in which

J.

A is -COOR ⁹ , -CONR ¹⁰ R ¹¹ , -CON = CC or -CN. The hydrolysis is usually carried out in the presence of an acid (eg sulfuric acid) or a base (eg sodium hydroxide).

g The compounds of the invention wherein A is -COOP.

may be prepared by esterifying the compound wherein A is -COOH. The esterification is usually carried out in the presence of an acid (e.g., sulfuric acid),

The compounds according to the invention in which A is -CEGR '

may be by acylating the alcohol or mercaptan

of formula R "GH with the acyl halide of formula (IV) In formula (IV), Y is halogen, usually chloro.

! β 1

The compounds of the invention wherein A

-CONR R can be prepared by acylating the amino derivative of formula HNR R with the acyl halide of formula (IV) wherein E is oxygen. Again it is

Υ usually chlorine.

12

The compounds in which A is -COR can by

Decarboxylating a carboxylic acid of formula (V) are prepared. The decarboxylation can be effected, for example, by heating. The carboxylic acid is preferably prepared in situ, e.g. by hydrolysis of the ester, e.g. of the ethyl ester.

The compounds wherein A is a carbonyl derivative of

12 -COR, can be achieved by implementing the appropriate

12 bond, wherein A is -COR, with a material of formula HMH to remove a molecule of water therebetween. For example, a compound, wherein A is -COCH 2, may be reacted with ethylene glycol in the presence of an acid to form the corresponding compound wherein A is

^ 0-CH ₀

<: I

-O CH ₉

H ₃

J C

is to be implemented.

means .12

The compounds wherein AC -., - ,, ₁ ^ ι-OAlkyl

Century 2

by reacting the corresponding compound wherein A is -COR with an orthoformate of the formula CH (Oalkyl) _, usually in the presence of, for example, an acid such as 4-toluenesulfonic acid or hydrogen chloride, or ammonium chloride. or ferric chloride.

The sulfonamide of formula (II) or a salt thereof can be prepared by acylating an aniline of formula (VI) or a salt thereof with the acylating agent of formula (R SO ₀ J ₀ O or preferably R SO ₀ Z. Again Z usually chlorine. ·

The acyl halide of formula (IV) may be prepared by reacting a sulfonanilide of formula (I) wherein A is -COOH or -CSSH

--Jl-

or a salt thereof with thionyl halide, phosphoryl halide, phosphorus pentahalide or oxalic halide, especially chloride, preferably thionyl chloride.

The inventive method is usually in the presence of a solvent usually at 0 to 20.0 ⁰ C, eg 0 to 150 ⁰ C is performed. The solvent may be, for example, water or an ether, a ketone, a hydrocarbon, an amide or an alcohol. The pressure may be, for example, about 0.5 to 10 bar, suitably ambient pressure.

Each substituted alkyl group in the compounds according to the invention has as substituent (s) one or more of the group halogen, alkoxy, furyl, phthalimido, -SCN, amino, substituted amino (eg amino, mono- or disubstituted by alkyl or acyl), alkoxycarbonyl , Carboxy,

Il 1 0 1 \

-C-NR R j benzoyloxy, alkanoyloxy, alkylsulfonyloxy, nitrile and hydroxy. In the case of R, R, R, R and R, a preferred such substituted alkyl group is -CF ^.

The acyl group is preferably alkanoyl.

The substituted aryl group is preferably aryl substituted by one or more of the following groups: halo, alkyl, alkoxy, alkylsulfonyloxy, nitro, -SCN and trifluoromethyl.

The substituted aralkyl group is preferably substituted on the aryl nucleus. The substituent (s) is (are) preferably halogen, alkyl, alkoxy, nitro, -SCN, alkylsulfonyloxy and trifluoromethyl.

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

An alkyl group in the symbols used preferably has 1 to 15, e.g. 1 to 8,. in particular 1 to 6 C-atoms, e.g. Methyl, ethyl, propyl, isopropyl, butyl or hexyl. Each cycloalkyl group preferably has 3 to 7 C atoms

on, e.g. Cyclohexyl or cyclopentyl. Each aryl group is preferably phenyl. Each aralkyl group is preferably phenylalkyl, e.g. with 7 to 10 carbon atoms, in particular benzyl. Each halogen atom is preferably fluorine, chlorine or bromine, but especially chlorine. Each alkoxy group preferably has 1 to 6 C atoms, e.g. Methoxy. Each alkanoyl group preferably has 2 to 7 carbon atoms. The alkylene or alkenylene group for R may be straight or branched chain. Usually it contains 1 to

1 2 6, preferably 1 to 3 C-atoms. When A is -COR or a carbonyl derivative or an addition compound thereof, R is more preferably methylene; if A has another meaning,

_R 18

• 18

R is more preferably -CH, where R is alkyl with

1 to 5, preferably 1 or 2 C atoms.

The heterocyclic or substituted heterocyclic group for R may be linked via a ring carbon or ring heteroatom. Each heterocyclic group in the present symbols is usually a single hetero ring having from 3 to 7 ring atoms, of which from 1 to 3, e.g. 1 or 2, are heteroatoms wherein each heteroatom is nitrogen, sulfur or oxygen to which hetero ring optionally a benzene ring is fused. The heterocyclic group may be, for example, furyl, thienyl, piperidyl, pyrrolyl, piperazinyl, morpholinyl or benzofuranyl. Any substituent on a heterocyclic group can be, for example, alkyl, such as methyl, oxo, nitro or halogen, such as chlorine.

Preferably, the heterocyclic group for -NR R is a single hetero ring of 5 to 7, e.g. 5 or 6 ring atoms, of which, in addition to the nitrogen atom, 1 or 2 may be further heteroatoms, wherein each heteroatom is oxygen, sulfur or nitrogen, to which hetero ring optionally a benzene ring is fused. The heterocyclic group is preferably piperazines, pyrrolidino, piperidino or morpholines. For example, each substituent may be alkyl, e.g. Methyl, oxo, nitro or halogen, such as chlorine.

Thus, in a preferred embodiment:

R is alkyl having 1 to 15 carbon atoms; Alkyl having 1 to 15 carbon atoms, mono- or polysubstituted by halogen, alkoxy with

1 to 6 C atoms, alkoxycarbonyl having 2 to 7 C atoms, carboxy, 0

Il η 11

-CNR R, phthalimido, -SCN, benzoyloxy, alkanoyloxy of 2 to 7 carbon atoms, alkylsulfonyloxy of 1 to 6 carbon atoms, furyl, nitrile, hydroxy, amino and amino, mono- or disubstituted by alkyl of 1 to 15 C Atoms or alkanoyl having 2 to 7 C atoms; Cycloalkyl having 3 to 7 C atoms; Phenylalkyl having 7 to 10 carbon atoms, optionally mono- or polysubstituted by halogen on the phenyl ring, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, nitro, -SCN, .- alkylsulf onyloxy with 1 to 6 C atoms and trifluoromethyl; phenyl; Phenyl, monosubstituted or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, alkylsulfonyloxy having 1 to 6 C atoms, nitro, -SCN and trifluoromethyl; a heterocyclic group which is a single hetero ring having 3 to 7 ring atoms, of which 1 to 3 are heteroatoms, each heteroatom being nitrogen, sulfur or oxygen to which hetero ring a benzene ring is optionally fused; such a heterocyclic group, mono- or polysubstituted by alkyl having 1 to 6 C atoms, oxo, nitro

p7 "7

and halogen; or a group of the formula -N ^ 8, where R and

8 R are the same or different and each is hydrogen;

Alkyl having 1 to 15 carbon atoms; Alkyl having 1 to 15 carbon atoms, monosubstituted or polysubstituted by halogen, alkoxy having 1 to 6 carbon atoms, alkoxycarbonyl having 2 to 7 carbon atoms, carboxy,

"1 0 1 1 -CNR R, phthalimido, -SCN, benzoyloxy, alkanoyloxy of 2 to 7 carbon atoms, alkylsulfonyloxy of 1 to 6 carbon atoms, furyl, nitrile, hydroxy, amino and amino, mono- or disubstituted by alkyl with 1 to 15 C atoms and alkanoyl having 2 to 7 C atoms, phenylalkyl having 7 to 10 C atoms, phenylalkyl having 7 to 10 C atoms, monosubstituted or polysubstituted by halogen on the phenyl ring, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro, -SCN, alkylsulfonyloxy having 1 to 6 C atoms and trifluoromethyl, phenyl or phenyl, mono- or polysubstituted by halogen, alkyl having 1 to 6 C atoms , Alkoxy having 1 to 6 C atoms, alkylsulfonyloxy having 1 to 6 C atoms, nitro,

.810 120

~ AS "

-SCN and trifluoromethyl;

R is alkylene or alkenylene having 1 to 6 C atoms;

9 10 11 "s R A -COOH; -CSSH; -CEGR; -CENR R; -CON = C _q;

12 ·

-CN or COR or a carbonyl derivative or an addition compound thereof; where E and G are the same or different

9 and each represents oxygen or sulfur, R is alkyl with ·

1 to 15 C atoms / alkyl having 1 to 15 C atoms, monosubstituted or polysubstituted by halogen, alkoxy having 1 to 6 C atoms,

Alkoxycarbonyl having 2 to 7 C atoms, carboxy,

0,.

-CNR R, phthalimido, -SCN, benzoyloxy, alkanoyloxy with

2 to 7 carbon atoms, alkylsulfonyloxy having 1 to 6 carbon atoms, furyl, nitrile, hydroxy, amino and amino, mono- or disubstituted with alkyl having 1 to 15 carbon atoms and alkanoyl having 2 to 7 carbon atoms; Phenylalkyl of 7 to 10 carbon atoms; Phenylalkyl having 7 to 10 C atoms, monosubstituted or polysubstituted by halogen on the phenyl ring, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro, -SCN, alkylsulfonyloxy having 1 to 6 C atoms and trifluoromethyl; phenyl; or phenyl _; mono- or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, alkylsulfonyloxy having 1 to 6 C atoms, nitro, -SCN and trifluoromethyl; R and R are the same or different and each represents a group as defined immediately above for R; or R and R together with the nitrogen atom to which they are attached form a heterocyclic group which is a single hetero ring having from 5 to 7 ring atoms, of which, in addition to the nitrogen atom, 1 or 2 may be further heteroatoms, each heteroatom being oxygen, sulfur or Nitrogen is to which hetero ring optionally a benzene ring is fused; such a heterocyclic group, mono- or polysubstituted by alkyl having 1 to 6 C atoms, oxo, nitro and halogen; or R ^{1 is} hydrogen, while R '

• R ⁷ / ^{ll is} a group of the formula -N = C _q or -N _in , where

^X R ^N R

1-2

R ^{13 is} hydrogen or -COOR ⁹ ; and R ^{12 is} hydrogen, alkyl with. .1 to 15 carbon atoms; Alkyl having 1 to 15 carbon atoms, monosubstituted or polysubstituted by halogen, alkoxy having 1 to 6 carbon atoms, alkoxycarbonyl having 2 to 7 carbon atoms, carboxy,

ο ..

-CNR R, phthalimido, -SCN, benzoyloxy, Alkanöyloxy with 2 to 7 carbon atoms, alkylsulfonyloxy having 1 to 6 carbon atoms, furyl, nitrile, hydroxy, amino and amino, mono- or disubstituted by alkyl with 1 to 15 C atoms and alkanoyl having 2 to 7 carbon atoms; Cycloalkyl having 3 to 7 C atoms; Phenylalkyl of 7 to 10 carbon atoms; Phenylalkyl having 7 to 10 C atoms, on the phenyl ring once or more than once by halogen, alkyl having 1 to 6 C atoms, alkoxy having T to 6 C atoms, nitro, -SCN, alkylsulfonyloxy having 1 to 6 C atoms and Trifluoromethyl substituted; phenyl; Phenyl, mono- or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, alkylsulfonyloxy having 1 to 6 C atoms, nitro, -SCN and trifluoromethyl; a heterocyclic group linked via a carbon atom in the group, which group is a single hetero ring having 3 to 7 ring atoms, of which 1 to 3 are heteroatoms, each heteroatom being nitrogen, sulfur or oxygen to which hetero ring optionally anneals a benzene ring is; or such a heterocyclic group, mono- or polysubstituted by alkyl having 1 to 6 C atoms, oxo, nitro and halogen; or

R-A is a group of the formula

Wherein R is hydrogen, alkyl of 1 to 6 carbon atoms

ι ^ Cr Ik

or phenyl, B is oxygen or -NR '', R is hydrogen or alkyl having 1 to 6 C atoms and η is 0, 1 or 2;

Ii y

R, R, R, R and R are the same or different and each is hydrogen; Alkyl having 1 to 15 carbon atoms; Alkyl having 1 to 15 carbon atoms, mono- or polysubstituted by halogen alkoxy having 1 to 6 carbon atoms, alkoxycarbonyl having 2 to 7 carbon atoms

"10 11 carboxy, -CNR R, phthalimido, -SCN, benzoyloxy, alkanoyloxy having 2 to 7 carbon atoms, alkylsulfonyloxy having 1 to 6 carbon atoms, furyl, nitrile, hydroxy, amino and amino, mono- or disubstituted by alkyl with 1 to 15 C atoms and alkanoyl with 2 to 7 C atoms; hydroxy; alkoxy with 1 to 6 C atoms; -SCN; nitro; mercapto; halogen; amino; amino, mono- or di-substituted by alkyl with 1 to 15 C atoms and alkanoyl with 2 to 7 C atoms;

a group of the formula -SR ¹⁶ , -SOR ¹⁶ , -SO ₀ R ¹⁶ or -OSO ₀ R ¹⁶ ,

16 wherein R is alkyl having 1 to 6 carbon atoms, phenyl or phenylalkyl

1 R "7 R

with 7 to 10 carbon atoms; -SO ₉ NR R, where R and R are the

12

have the meaning given immediately above; or -COOR,

.wherein R has the meaning immediately above,

with the proviso that R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} not each hydrogen, when R is alkylene having 1 to 6 carbon atoms, R is phenyl or phenyl, mono- or polysubstituted by halogen, alkyl with 1 to 6 carbon atoms ,. Alkoxy having 1 to C atoms, alkylsulfonyloxy having 1 to 6 C atoms, nitro, -SCN

9 9

and trifluoromethyl and A COOH or COOR. where R is alkyl of 1 to 15 carbon atoms. Within this embodiment, there are two preferred aspects. In one aspect, R has another meaning a phenyl or substituted phenyl. In the other aspect, three or four of the groups R, R, R, R and R are each hydrogen.

According to a particular embodiment, the substituents in the compounds according to the invention have the following meaning:

R is alkyl, substituted alkyl, cycloalkyl, aralkyl,

substituted aralkyl, aryl, substituted aryl or a

"7

^ 7 8

Group of formula -N _R , where R and R are the same or different

each is hydrogen, alkyl, substituted alkyl, aralkyl, substituted aralkyl, aryl or substituted aryl;

R is alkylene;

A is -COOH, -CSSH, -CEGR ^, -CENR ¹ R '', -CON = C

⁰ R ⁷ 9 10 11 " ^

or -CN, wherein E and G are the same or different and each

9 is oxygen or sulfur, R is alkyl, substituted

Alkyl, alkyl, substituted aralkyl, aryl or substituted aryl; R. and R are the same or different and each represents a group as defined for R; or R _{un (} 3 r 1 1 together with the nitrogen atom to which they are attached form a heterocyclic group, or R is hydrogen, while R is a group of the formula

^ ^R? / ^H '13

-N = C _q or -N ₁ -. where R is hydrogen or

^X R ^{y X} R ^J

9 9

-COOR means (where R is in particular ethyl); and

R, R, R, R and R are the same or different

and each is hydrogen, alkyl, substituted alkyl, alkoxy, -SCN, nitro, mercapto, alkylmercapto, amino or halogen;

with the proviso that R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} not

each represents hydrogen when R is phenyl or substituted

9 9

Phenyl and A is -COOH or -COOR (wherein R is alkyl).

Preferably, within this embodiment, R is alkyl of 1 to 15 carbon atoms; Alkyl having 1 to 15 C atoms, mono- or polysubstituted by halogen, alkoxy having 1 to 6 C atoms, amino and amino, mono- or disubstituted by alkyl 'having 1 to 15 C atoms and alkanoyl having 2 to 7 carbon atoms; Cycloalkyl having 3 to 7 C atoms; Phenylalkyl with 7 to 10 carbon atoms? Phenylalkyl having 7 to 10 C atoms, monosubstituted or polysubstituted by halogen on the phenyl ring, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro and trifluoromethyl; Phenyl or phenyl, monosubstituted or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro and trifluoromethyl; or a group of the formula

/ 7 8

-N-. ~. where R. and R are the same or different and each

because hydrogen, alkyl having 1 to 15 carbon atoms, alkyl with 1 to

- -is -

15 C atoms, mono- or polysubstituted by halogen, alkoxy having 1 to 6 C atoms, amino and .Amino, mono- or disubstituted by alkyl having 1 to 15 carbon atoms and alkanoyl having 2 to 7 carbon atoms; Phenylalkyl of 7 to 10 carbon atoms; Phenylalkyl having 7 to 10 C atoms, monosubstituted or polysubstituted by halogen on the phenyl ring, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro and trifluoromethyl; Phenyl or phenyl, monosubstituted or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms. Nitro and trifluoromethyl; R alkylene having 1 to 6 carbon atoms;

OR ⁷

A-COOH, -CSSH, -CEGR ⁹ , -CENR ¹⁰ R ¹¹ , -CON = C ^ _q

Λ R

or -CN, wherein E and G are the same or different and each

Mean oxygen or sulfur; R is alkyl having 1 to 15 C atoms, alkyl having 1 to 15 C atoms, mono- or polysubstituted by halogen, alkoxy having 1 to 6 C atoms, amino and amino, mono- or disubstituted by alkyl having 1 to 15 C Atoms and alkanoyl having 2 to 7 C atoms; Phenylalkyl of 7 to 10 carbon atoms; Phenylalkyl having 7 to 10 C atoms, monosubstituted or polysubstituted by halogen on the phenyl ring, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro and trifluoromethyl; Phenyl or phenyl, mono- or polysubstituted by halogens, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro and trifluoromethyl; R and R are the same or different and each represents a group as defined immediately above for R; or R and R together with the nitrogen atom to which they are attached form a monocyclic heterocyclic group having 5 or 6 ring atoms, of which, in addition to the nitrogen atom, another heteroatom may be present, which heteroatom is oxygen or nitrogen; or R is hydrogen, while R is a group of the formula

R ⁷ H

-N = C "^ . Or -N ^ .._, where R ^{l3 is} hydrogen or -COOR ⁹

"R ^y ^ R ^lJ represents; and

R, R " ¹ , R, R and R are the same or different and each is hydrogen, alkyl having 1 to 15 C atoms, alkyl having 1 to 15 C atoms, mono- or polysubstituted by halo

Alkoxy having 1 to 6 C atoms, amino and amino, mono- or disubstituted by alkyl having 1 to 15 C atoms and alkanoyl having 2 to 7 C atoms; Alkoxy having 1 to 6 C atoms; SCN; nitro; mercapto; Alkylmercapto having 1 to 6 C atoms; Amino or halogen; with the proviso that R, R, R, R and R are not each hydrogen when R is phenyl or phenyl, mono- or polysubstituted by halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms , Nitro and trifluoromethyl, and A: -COOH or

9 9

COOR, where R is alkyl of 1 to 15 carbon atoms.

According to a further particular embodiment, R is alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, aryl, substituted aryl, a heterocyclic group, a substituted heterocyclic group or

/ ^ 7 8

a group of the formula -N _ft , where R and R are the same or

are different and each represents hydrogen, alkyl, substituted alkyl, aralkyl, substituted aralkyl, aryl or substituted aryl;

R is alkylene or alkenylene;

1 ? A -COR or a carbonyl derivative or an addition

Compound of which R is hydrogen, alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, aryl, substituted aryl, a heterocyclic group connected via a carbon atom in the group, or such a substituted heterocyclic group; and

R, R, R, R and R are the same or different and each is hydrogen; alkyl; substituted alkyl; alkoxy; SCN; nitro; Halogen; amino; substituted amino; mercapto; a group of the formula -SR, -SOR or -SO R, where R is alkyl,

"7 Q I ft

Aryl or aralkyl; -SQ ₉ NR R, where R and R are as directly

1 7 12 bar are defined above; or -COOR _'r wherein R is as immediately

is defined above.

Within this embodiment, R ¹ is preferably alkyl having 1 to 1 * 5 carbon atoms; Alkyl having 1 to 15 carbon atoms, mono- or polysubstituted by halogen, alkoxy having 1 to 6 carbon atoms, amino and amino, mono- or disubstituted.

by alkyl having 1 to 15 C atoms and alkanoyl having 2 to 7 C atoms; Cycloalkyl having 3 to .7 C atoms; Phenylalkyl of 7 to 10 carbon atoms; Phenylalkyl having 7 to 10 C atoms, monosubstituted or polysubstituted by halogen on the phenyl ring, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro and trifluoromethyl; phenyl; Phenyl, monosubstituted or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, alkylsulfonyloxy having 1 to 6 C atoms, nitro and trifluoromethyl; a heterocyclic group which is a single hetero ring having 3 to 7 ring atoms of which 1 or 2 are heteroatoms, each heteroatom being nitrogen, sulfur or oxygen to which hetero ring optionally a benzene ring is attached; such a heterocyclic group, mono- or polysubstituted by alkyl having 1 to 6 C atoms, nitro and halogen;

.R 7 8

or a group -Ng, where R and R are identical or different

are separated and each hydrogen; Alkyl having 1 to 15 carbon atoms; Alkyl having 1 to 15 carbon atoms, mono- or polysubstituted by halogen, alkoxy having 1 to 6 carbon atoms, amino and amino, mono- or disubstituted by alkyl having 1 to 15 carbon atoms and alkanoyl having 2 to 7 C. -atoms; Phenylalkyl of 7 to 10 carbon atoms; Phenylalkyl having 7 to 10 C atoms, monosubstituted or polysubstituted by halogen on the phenyl ring, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro and trifluoromethyl; phenyl; or phenyl, monosubstituted or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, alkylsulfonyloxy having 1 to 6 C atoms, nitro and trifluoromethyl;

R is alkylene or alkenylene having 1 to 6 C atoms;

1 2 A -COR or a carbonyl derivative or an addition

1 2 compound thereof, wherein R is hydrogen, alkyl having 1 to 15 carbon atoms; Alkyl having 1 to 15 carbon atoms, mono- or polysubstituted by halogen, alkoxy having 1 to 6 carbon atoms, amino and amino, mono- or disubstituted by alkyl having 1 to 15 carbon atoms and alkanoyl having 2 to 7 C. -atoms; Cycloalkyl having 3 to 7 C atoms; Phenylalkyl of 7 to 10 carbon atoms; phenylalkyl

with 7 to 10 C atoms, monosubstituted or polysubstituted by halogen on the phenyl ring, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro and trifluoromethyl; phenyl; Phenyl, monosubstituted or polysubstituted by halogen, alkyl having 1 to C atoms, alkoxy having 1 to 6 C atoms, alkylsulfonyloxy having up to 6 C atoms, nitro and trifluoromethyl; a heterocyclic group connected via a carbon atom in the group, which group is a single hetero ring having 3 to 7 ring atoms, of which. 1 or 2 are heteroatoms, wherein each heteroatom is nitrogen, sulfur or oxygen to which hetero ring optionally a benzene ring is fused; or such a heterocyclic group which is mono- or polysubstituted by alkyl

1 to 6 C atoms, nitro and halogen is substituted; and

R, R, R, R and R are the same or different and each is hydrogen, alkyl having 1 to 15 C atoms; Alkyl having 1 to 15 carbon atoms, mono- or polysubstituted by halogen, alkoxy having 1 to 6 carbon atoms; Amino and amino, mono- or di-substituted by alkyl having 1 to 15 carbon atoms and alkanoyl with

2 to 7 C atoms; Alkoxy having 1 to 6 C atoms; SCN; nitro; mercapto; Halogen; amino; Amino, mono- or disubstituted by alkyl having 1 to 15 carbon atoms and alkanoyl having 2 to 7 carbon atoms; a group of the formula -SR, -SOR or -SO R,

1 fi where R is alkyl having 1 to 6 C atoms, phenyl or phenylalkyl

1 ? 12

with 7 to 10 carbon atoms; or -COOR, where R has the meaning immediately above.

Particularly preferred compounds are those wherein R is alkyl of 1 to 4 carbon atoms, 2-phthalimidoethyl, ethoxycarbonylmethyl, nitrophenyl, morpholino, thienyl or dialkylamino of 2 to 8 carbon atoms; R alkylene having 1 to 3 carbon atoms or alkenylene with

Represents 3 C atoms; ,

A-COOH; -CENH ₂ ; -CN; -CONHPh; Cycloalkyloxycarbonyl having 4 to 8 C atoms; morpholinocarbonyl; -CONHNH ₂ ; -CONHCH ₂ . COOalkyl having 1 to 4 C atoms; -CONHNHCOOalkyl with 1 to 4 C

atoms; -C-N_j; -COOR ¹⁷ or -CON (R ^{1 7} K, where R ¹⁷

-33-

Is alkyl of 1 to 5 C atoms; -COCH; -COCH ₂ OH;

S - CH.

I; COOCH,

FX

CH ₃ ^S - ^CH 2

OCH ₃ ; -C -OCH ₃ ; -C

^Cl 3 Cl

O - CH.

O - CH,

; -COCH ₂ OCOCH ₃ ; CONH

COOA't SCN; -COC - H;

CH ₂ OH

-C - CH ,; -COC (CH ₀ ) ,; -C - CH ₀ ; -C - CH_ or -C - CH

H 3

NOH

3'3

11

STILL.

Il

NOCCH

H 3

NOCNHCH.

Il

or

means; and

° three or four of the groups R, R, R, R and R are each Vihydrogen and the others are the same or different and each alkyl having 1 to 3 carbon atoms, halogen, hydroxy, phenylmercapto, -SCN, nitro, alkoxy with 1 to 6 C atoms, trifluoromethyl, phenylsulfonyl or methylsulfonyl.

According to a particularly preferred group are three

[he .12

or four of the groups R, R, R, R and R are each hydrogen.

When A is -COR or a carbonyl derivative or an addition compound

When this is the case, it is particularly preferred that R, R

and R. or R, R, R and R- are each hydrogen. In a particularly preferred group R are alkyl having 1 to 4 C atoms or thienyl,

S - CH

R methylene,

A -COCH, -C

J S-CH

CH,

₂ OCH ₃

, -C - OCH ₀

I ^J CH,

0 - CH

-C

CH.

Ό - CIL

O - CH.

- CH ϋ ι NOH , CH "OH

CH ₃ or -COC (CH ₃ ) - and

three or four of the groups R, R, R, R and R are each hydrogen and the others the same or different and each alkyl having 1 to 3 carbon atoms, halogen or alkoxy having 1 to 6 carbon atoms.

In another particularly preferred group are

R is alkyl having 1 to 4 C atoms;

R is -CH-, where R ^{18 is} methyl or ethyl;

A is -COOH, -COOR ¹⁷ , -CENH ₂ , -CON (R ¹⁷ J ₂ , -CN or -CONHPh, wherein R ^{17 is} alkyl of 1 to 8 carbon atoms, and three or four of the groups R, R, R , R and R

in each case hydrogen and the others the same or different and in each case alkyl having 1 to 3 C atoms, halogen, alkoxy having 1 to 6 C atoms or trifluoromethyl.

Specific compounds are given in the examples.

Preferred specific compounds, especially as herbicides, are: N-cyanomethyl-3 ', 4'-dichloromethanesulfonanilide; N- [1- (ethoxycarbonyl) ethyl] -2 ', 6'-dimethyl-1-propanesulfonanilide and N- [1- (ethoxycarbonyl) ethyl] -2', 6'-dimethylethanesulfonanilide.

Another preferred specific compound, especially as a fungicide, for example for use on wine or potatoes, is N- [1- (methoxycarbonyl) ethyl] -2 ', 6'-dimethylmethanesulfonanilide.

Finally, another preferred specific compound, especially for use as a fungicide, is N-2-oxopropyl-2 ', 6'-dimethylmethanesulfonanilide.

The compounds of the invention are pesticides and plant growth regulators. The connection

9, especially those in which A is -COOH, -CSSH, -CEGR,

OR. '

-CENR ¹⁰ R ¹¹ , - (JON = C ^ ₉ or -CN means are on the

Plant physiology particularly effective by affecting the growth of the plants, so that the compounds are used as herbicides or plant growth regulators

can. The compounds according to the invention, in particular those

wherein A represents -COR or a carbonyl derivative or an addition compound thereof are also particularly useful as fungicides. The compounds of the invention, especially those wherein A is an oxime carbamate, are also particularly useful as insecticides. The compounds of the invention are also antibacterial agents. They are excellent for controlling fungi or weeds in crops.

The compounds can be used, for example, for combating starwort (Stellaria media), white goosefoot (Chenopodium album), wild oat (Avena fatua), bulrush (Alopecurus myosuroides), millet (Echinochloa crus-galli) or fingergrass (Digitaria sanguinalis).

The compounds may be used to control weeds in, for example, food crops such as potatoes, wine, carrots or cereals such as rice, wheat, barley or corn, ornamental fruits or crops such as cotton.

For use as fungicides, the compounds are preferably used for combating fungal diseases of plants, in particular one of the species listed above.

The compounds may be used to control various species of fungi, e.g. Phythium, Phytophthora, Plasmopora or Pyricula ria.

The compounds of this invention are usually used in the form of compositions / which can be prepared by mixing the ingredients. Usually, the compositions are first prepared in the form of concentrates, e.g. 0.5-85% of the compound of the invention, and these are diluted with water or a hydrocarbon, usually water, for use, generally such that the concentration of the compound is 0.05-5%, although when used in extremely low volumes the concentration can be higher, for example up to 20%. Percentages and parts in this specification are by weight unless otherwise specified.

The compositions usually contain a surfactant and / or a carrier.

The carrier can be a liquid. e.g. Water (such as the water used to dilute a concentrate for application). When water is used as a carrier in a concentrate, an organic solvent may also be present as the carrier, though such is not normally used. Advantageously, a surfactant may be present.

The carrier may be a liquid other than water, for example an organic solvent such as a water immiscible solvent, eg a hydrocarbon which boils within the range of 130 to 27O ⁰ C, in which the compound is dissolved or suspended. A concentrate containing a water-immiscible solvent suitably also contains a surfactant so that the concentrate acts as a self-emulsifiable oil when mixed with water. The liquid may be a water-miscible solvent, for example 2-methoxyethanol, methanol, propylene glycol, diethylene glycol, Diäthylenglykomonoäthylather, 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, lignosulfonates, peat and solid fertilizers. The carrier can be of natural or synthetic origin or a modified natural material

Wettable powders which are soluble or dispersible in water may be obtained by mixing the compound in particulate form with a particulate carrier or spraying the molten compound onto the particulate carrier, admixing a wetting and dispersing agent, and finely grinding the entire powder mixture.

An aerosol composition may be prepared by mixing the compound with a propellant, e.g. a polyhalogenated alkane, such as dichlorodifluoromethane, and expediently also with a solvent.

A flowable suspension concentrate, when the compound has a low solubility in water, can be formed by milling the compound with water, a wetting agent and a suspending agent.

A flowable suspension concentration wherein the carrier is a hydrocarbon having a boiling range of 130 to 270 C instead of water may be formed.

For example, the composition of the present invention may be solid (eg, a dust or granules) and may contain a solid carrier, or it may be a liquid (eg, an emulsifiable concentrate) and a liquid carrier, namely, a hydrocarbon having a boiling range of 130 to 270 ,

The term "surfactant" is used broadly and includes materials such as emulsifiers, dispersants and wetting agents. Such agents are well known. ,

The surfactants used may include anionic surfactants, e.g. Soaps, mono- or diesters of phosphoric acid with fatty alcohol ethoxylates or salts such! esters, fatty alcohol sulfates such as sodium dodecyl sulfate, sodium octadecyl sulfate or sodium cetyl sulfate, ethoxylated fatty alcohol sulfates, ethoxylated alkylphenol sulfates, lignosulfonates, petroleum sulfonates, alkylarylsulfonates such as alkylbenzenesulfonates or lower alkylnaphthalenesulfonates, e.g. Butyl naphthalene sulfonate, salts of sulfonated naphthalene-formaldehyde condensates, salts of sulfonated phenol-formaldehyde condensates, or more complex sulfonates such as the amide sulfonates, e.g. the sulfonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulfosuccinates, e.g. the sodium sulfonate of dioctylsulfate.

The surfactants may also be non-ionic agents, for example condensation products of Fettsäureestern, fatty alcohols, fatty acid or fat, or alkyl phenols alkenylsubstituiertei with ethylene oxide, fatty esters of polyhydric Alkonoläthern,?,. B

 Sorbitan fatty acid esters, condensation products of such esters with etylene oxide, e.g. Polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide. Acetylene glycols, such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol, or ethoxylated acetylene glycols.

The surfactants may also include cationic agents

 be, e.g. alkyl- and / or aryl-substituted cuuatemäre Armvoniumverbindungei such as cetyltrimethylanimonium bromide, or ethoxylated tert. Fatty amines.

Preferred surface-active agents are ethoxylated fatty alcohol sulfates, lignosulfonates, alkylarylsulfonates, salts of sulfonated naphthalene-formaldehyde condensates, salts of sulfonated phenol-formaldehyde condensates, dialkylsulfosuccinates, alkylphenol ethoxylates and fatty alkyl ethoxylates.

Nonionic surfactants are preferred.

The active compound of the invention may be combined with another pest control agent, e.g. Herbicide, fungicide, insecticide or antibacterial agent or with another plant growth regulating agent:

be mixed. The invention provides a Einpackungspräsentation before, in the present compound is already mixed with another pesticide or plant growth ^regulator,: and also a single package which is designed to retain the compound of the invention and another pesticide or other plant growth regulator in separate containers, which are then mixed in a spray container for use, for example. Particular advantages are achieved with mixtures with another herbicide or fungicide. The compound of the present invention may be sequentially used with another pesticide or plant growth regulator, particularly with another herbicide or fungicide / eg, one herbicide is applied before planting or before emergence of one fruit and the other after emergence.

The other herbicide may, for example, be one or more of the following: phenoxyaliphatic acid, substituted urea, triazine, phenol, nitrile, bipyridylium compound, substituted benzoic acid, halogenated aliphatic acid, carbamate, thiocarbamate, chloroacetamide, oxazine or arsenic compounds. With respect to the selective post-emergent herbicidal compositions, the compound of the present invention may be used in admixture with, for example, a substituted phenoxyaliphatic acid with respect to selective herbicidal compositions for pre-expending use in admixture with, for example, a substituted urea or triazine; in the successive selective herbicidal use

You can, for example, before the emergence of crops

S-2, B-dichloroyl-diisopropylthiocarbaraat or S-2,3,3-trichloro allyl diisopropylthiocarbamat and apply after emergence of the compound of the invention.

The phenoxyaliphatic acid is generally an alkyl- and / or halogen-substituted phenoxyaliphatic acid or a salt thereof, e.g. an alkali metal, amine and alkanol amine salt, or a functional derivative thereof, e.g. an ester or amide. These compounds may have such activity that they are recognized as commercial herbicides or have only weak herbicidal activity. Examples of noteworthy substituted phenoxyaliphatic acids include 2,4-dichlorophenoxyacetic acid, 2- (2,4-dichlorophenoxy) -propic acid, 2-methyl-4-chlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, gamma-2,4-dichlorophenoxybutyric acid , Y ~ 2-methyl-4-chloro phenoxybutanoic acid, α-2-methyl-4-chlorophenoxypropionic acid, 2- [4 - '(2, 4-dichlorophenoxy) -phenoxy] -propionic acid and 2- [4- (4-chlorophenoxy ) phenoxy] propionic acid.

The substituted urea is generally a tritiated tetrasubstituted urea, such as N '- (3-chloro-4-methoxyphenyl) Ν, Ν-dimethylurea, N' - (3-chloro-4-methylphenyl) -N, N-dimethyl urea, N ^L p -chlorophenyl-N, N-dimethylurea, N-butyl-N ¹ -

(3,4-dichlorophenyl) -N-methylurea, N'-p-chlorophenyl-Ο, Ν, N-trimethylisourea, N'-p-chlorophenyl-N-methoxy-N-methylurea, N, N-dimethyl-N ' -phenylurea, 3- {4-bromophenyl) -1-methoxy-1-methylurea, 1- (2-benzothiazolyl) -3-methylharnsto N, N-dimethyl-N '- [4- (1-methylethyl) -phenyl] urea, N'- (3,4-dichlorophenyl) -N-methoxy-N-methylurea or N, N-dimethyl-N '

[3- (trifluoromethyl) phenyl] urea.

The triazine herbicide is generally 2-chloro-4- (1-cyano-1-methylamino) -6-ethylamino-1,3,5-triazine or 2-isopropylamino-4 (3-methoxypropylamino) -6-methylthio-1,3 , 5-triazine or an Ver

binding of the formula

W N

N - C

- 50-.

wherein X is halogen, alkoxy or alkylthio, R ¹ and R "are the same or different and each is hydrogen or alkyl and R" ¹ and R "" are identical or different and are alkyl, such as 2-chloro-4,6-bisethylamino-1,3 , 5-triazine, 2-chloro-6-ethylamino-4-isopropylami.no-1, 3,5-triazine, 2-chloro-4-ethylamino-6-diethylamino-1,3,5-triazine or 2,4 bis (isopropylamino) -6-methylthio-1,3,5-triazine.

The phenolic herbicide is generally 4,6-dinitro-o-cresol-4,6-dinitro-2-sec-butylphenol or pentachlorophenol. The nitrile herbicide is generally 3,5-diiodo-4-hydroxybenzonitrile, 3,5-dibromo-4-hydroxybenzonitrile or 2,6-dichlorobenzonitrile. The bipyridylium herbicide is generally 1,1'-dimethyl-4,4'-bipyridylium dichloride or 1,1'-ethylene-2,2'-bipyridylium dibromide. The substituted benzoic acid herbicide is generally 2,3,6-trichlorobenzoic acid, 2-methoxy-3,6-dichlorobenzoic acid or N- (1, 1-dimethylpropynyl) -3,5-dichlorobenzamide. The halogenated aliphatic acid herbicide is generally trichloroacetic acid or 2,2-dichloropropionic acid. The carbamate herbicide is generally isopropyl N- (3-chlorophenyl) carbamate, 4-chloro-2-butynyl-N- (3-chlorophenyl) carbamate, methyl 3- (m -tolylcarbamoyloxy) -phenylcarbamate or DN-Ä 'thyl-2- (phenylcarbamoyloxy) -propionantide. The thiocarbamate herbicide is generally S-ethyl-N, N-dipropylthiocarbamate, S-A'-ethyl-N, N-diisobutylthiocarbamate, S- (2, 3-dichloroallyl) -Ν, Ν-diisopropylthiocarbamate, S-ethyl-N-ethyl N-cyclohexylthiocarbamate, S-Propylbutyläthylthiocarbamat or S- (2,3,3-trichloroallyl) -Ν, Ν-diisopropylthiocarbamat. The chloroacetamide herbicide is generally N, N-diallyl-2-chloroacetamide or N-isopropyl-2-chloroacetanilide. The diazine herbicide is generally 5-bromo-6-methyl-3-sec-butyluracil, 3-cyclohexyl-5,6-trimethyleneuracil, 5-amino-4-chloro-2-phenyl-3-pyridazinone or 1,2- dihydropyridazin-3,6-dione. The arsenic herbicide is generally a salt of methanarsonic acid or cacodylic acid. Other herbicides which can be used as the second herbicide are 1,2-dimethyl-3,5-diphenylpyrazolium ion, ethyl-N-benzoyl-N- (3,4-dichlorophenyl) alanine, N-isobutyl-2-oxo 1-imidazolidinecarboxamide, aminotriazole-2, 3-dichloro-1, 4-naphthoquinone, 4-arniino-3,5,3-trichloro-picolinic acid, N, N-dimethyl-2,2-diphenylacetairiide, 2,6-dinitro ~ N, N-dipropyl-4-trifluoromethylaniline, H-butyl-N ~ ethyl-2,6-dinitro-4-trifluoromethylaniline, S, S _{f S-Tributylphosphortrithioat;} 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranylniethylsulfonate, 4-chloro

-51-

2-oxobenzothiazolin-3-ylacetic acid, 3-isopropyl-2, 1, 3-benzothiadiazinon- (4) -2,2-dioxyd, 3, S-dibromo-M-hydroxybenzaldehyde - 2,4-dinitrophenyloxime, methyl 2-chloro-3- (4-chlorophenyl) propionate, S-chloroethyltrimethylammonium chloride, isopropyl 2- (N-benzoyl-3-chloro-4-fluoroanilino) -propionate, methyl 2- (N-benzoyl-3-chloro 4-fluoroanilino) propionate, 2-chloro-N- (1,3-dioxolan-2-ylmethyl) -2 ', 6'-dimethylacetanilide, 2-chloro-1- (3-ethoxy-4-nitrophenoxy) - 4-trifluoromethylbenzene, methyl 2- [4- (2 ', 4'-dichlorophenoxy) -phenoxy] -propionate or isobutyl-2- [4- (4'-chlorophenoxy) -phenoxy] -propionate.

In particular, the other herbicide may be one which combats wild oats in cereal crops.

According to preferred embodiments, the compound according to the invention, in particular as has been mentioned above as being preferred for use as a herbicide, e.g. N-cyanomethyl-3,4-dichloromethanesulfonanilide, a) in. Mixture with 4-chloro-2-butynyl-3-chlorophenylcarbamate ,. 1,2-Dimethyl-3,5-diphenyipyrazolium ion, α-2-methyl-4-chlorophenoxypropionic acid, N '- (3-chloro-4-methoxyphenyl) -N, N-dimethylurea, N' - {3-chloro-4 -methylphenyl) -NjN-dimethylhydrogen or ethyl-N-benzoyl-K- (3,4-dichlorophenyl) -alanine or b) after emergence of the crop after using S-2,3-dichloroallyl-diisopropylthiocarbamate or S-2,3,3-trichloroallyl-diisopropylthiocarbamate used before emergence of the crop.

The compound of the invention may be used in admixture or sequentially with another fungicide, especially another cereal fungicide. The other

For example, fungicide can

one or more of the following: maneb (polymeric manganese ethylenebisdithiocarbamate), zineb (zinc ethylenebisdithiocarbamate), mancozeb (which may be considered a mixture of maneb and zineb), thiram (tetramethylthiuram disulphide), ditalimfos (0,0-diethylphthalimidophosphonothioate), tridemorph. (2, 6-dimethyl-4-tridecylmorpholine), fluotrimazole {1- [diphenyl- (3-trifluoromethylphenyl) -methyl] -i , 2,4-triazole), ethirimol (5-butyl-2-ethylamino-4-) hydroxy-6-methylpyr-imidine), triforin (1,4-di- [2,2-trichloro-1-formamidoethyl] -piperazine), pyracarbolide (3,4-dihydro-6-methyl-pyran-5-carboxanilide) , Benzenethiuram disulfide adduct,

Carbendazim (methylbenzimidazol-2-ylcarbamate), captafol (3a, 4,7,7a-tetrahydro-N- [1,1,2,2-tetrachloroethanesulfenyl] phthalimide), thiophanate (1,2-di- [3-ethoxycarbonyl -2-thioureido] benzene), propineb (polymeric zinc propylene bisdithiocarbamate), oxycarboxine (2,3-dihydro-6-methyl-5-phenylcarbamoyl-1,4-oxathiin-4,4-dioxide), quintozene (pentachloronitrobenzene), benomyl (Methyl-1- [butylcarbamoyl] -benzimidazol-2-ylcarbamate), benadanil (2-iodobenzanilide), dichlorofluanide (N-dichlorofluoromethanesulfenyl-N ', N'-dimethyl-N-phenylsulfamide), sulfur and copper compounds, iprodione (3 - [3,5-dichlorophenyl] -T - [(1-methylethyl) -aminocarbonyl] -imidazolidine-2,4-dione, ziram (zinc dimethyldithiocarbamate), nabarn (disodium ethylenebisdithiocarbamate) and triadimefon (1 - [4-chlorophenoxy] -3 , 3-dimethyl-1- [1,2,4-triazol-1-yl] -2-butanone).

According to a particular embodiment, the

Compound of the invention, e.g. N-2-oxopropyl-2 ', 6'-dimethylmethanesulfonanilide, used in mixture with thiram.

The compound of the invention may be used in admixture or sequential with an insecticide, especially a cereal insecticide. The insecticide may, for example, one or more of the group demeton S-methyl- (S-2- 'ethylthioethyl-ÖjO-dimethylphosphorthioat), dimethoate (0,0-dimethyl-S-methylcarbamoylmethylphosphordithioat), formothion (S- [N-formyl -N-methylcarbamoylmethyl] -0,0-dimethylphosphorodithioate), oxydemetonemethyl (S-2-ethylsulfinylethyl-CO-dimethylphosphorothioate), pirimicarb (2-dimethylamino-5,6-dimethylpyrimidin-4-yl dimethylcarbamate), thiometone (S-2-ethylthioethyl) -0,0-dimethylphosphorodithioate), BHC (benzene hexachloride), aldrin (1,2,3,4,10,1-O-hexachloro-1,4a, 5,8,8a-hexahydro-exo-1,4-endo-5 , 8-dimethannaphthalene), fenitrothion (O, O-dimethyl-O-4-ηitromolactyl phosphorothioate), omethoate (O-2-dimethyl-S-methylcarbamoylmethyl phosphorothioate), pirimiphosmethyl (O-2-diethylamino-6-methylpyrimidine-4- yl-0,0-dimethyl phosphorothioate) and DDT (1,1,1-trichloro-2,2-di [chlorophenyl] ethane).

The ratio of the compound of the invention to the other pesticide or plant growth regulator may vary over a wide range depending on the particular compounds employed and the intended use.

ff O 120

In general, the ratio of the compound according to the invention to the other pest control agent or plant growth regulator is 1: 0.1 to 1:15.

The compounds of the invention may be mixed with non-phytotoxic oils, e.g. Agri-Oil Plus, Sun Oil 11E or Fyzol 11E. ,

The compounds may be mixed with an antidote (a compound having a property of improving the selectivity of herbicides), ζ.B. N, N-diallyl-2,2-dichloroacetamide or 1,8-naphthalic anhydride.

The compounds may be in admixture with fertilizers. ,

When using the compounds of the invention as total herbicides, usually high application rates, e.g. at least 10 kg per ha, such as 10 to 25 kg per ha, of the compounds required if they are not mixed with other herbicides, in which case the rate can be reduced.

When using the compounds of the invention as selective herbicides, the rate of application is usually much slower and may be, for example, from 0.5 to 10, e.g. 0.5 to 8 kg per ha, such as 1 to 4 kg per ha.

When using the compounds as plant growth regulators, low application rates are usually required, such as 0.1 to 4, e.g. 0.5 to 1 kg per ha.

For use as fungicides, insecticides or antibacterial agents, the compounds will generally be used in an amount of from 0.3 to 10, e.g. 1 to 6 kg per ha applied. For use as fungicides, the compounds may be incorporated into a plant growth medium, in particular a peat-based medium in which plants are to grow, for example in an amount of 10 to 1000, preferably 50 to 500 g compound / cm. The compounds can be used as seed fertilizers, the term "seed" being used broadly to include tubers and onions; for this use, the compounds may be used in an amount of, for example, 0.1 to 1 g per kg of seed; preferably they are used in admixture with a carrier to effect mixing with the seeds.

9. 4. 1979 760 18

The carrier may contain a liquid, e.g. a hydrocarbon or a solid, e.g. a sound or Fuller-Brede, his «

The compounds of the invention may be applied to plants (including seeds), the soil (including compost), land or water surfaces, or to lifeless or stored materials, e.g. Preferably, they are used as herbicides, in particular selective herbicides, or fungicides, in particular for use in a place where a crop, in particular a barley fruit, such as wheat, Barley or corn, grows, or, less preferably, grows, applied. Thus, the compounds can be applied before or after planting the fruit. They can be used for pre-emergence or casserole use. The compounds can be used to protect plants from weeds and fungi.

Ausg üh_run.gsbe games

The following examples are intended to illustrate the present invention in more detail, but without this being restricted thereto »

Example 1: A solution of 25 ml of 1-propanesulfonyl chloride in 50 ml of toluene was added over 15 minutes to a stirred solution of 55 ml of 2,6-dimethylaniline in 400 ml of toluene. The mixture was stirred and refluxed for 20 hours, then cooled and filtered. The toluene solution was washed three times with dilute hydrochloric acid and

- 32a -

£ 1

9. · '+. 1979 760 18

Water, then extracted three times with dilute sodium hydroxide solution. The -wäßrige alkaline solution was acidified with dilute hydrochloric acid and the product collected by filtration, washed with water and dried · Crystallization from toluene / 60-80 ⁰ petroleum ether -were 28.0 g (55%) of 2 ^f, 6'-dimethyl 1-propanesulfonanilide in the form of brown crystals, mp 72 ⁰ C ₄ ,

Example 2: A mixture of 28.0 g of the sulfonanilide of Example 1, 9.4 g of anhydrous potassium carbonate, 17.6 ml of ethyl 2-bromopropionate and 200 ml of 1,2-dimethoxyethane was stirred and refluxed for 20 hours. then cooled and filtered and the filtrate evaporated. A solution of the remaining

~ 33 ~

10 1

Oil in ether was washed with dilute sodium hydroxide solution. The alkaline solution was acidified with dilute hydrochloric acid and the precipitated solid was collected by filtration. This material (13.3 g) was identified as unreacted sulfonanilide. The ethereal solution was evaporated and a solution of the remaining oil in 100 ml ethanol / 10% sodium hydroxide solution (1: 1) heated to 50 ^° C. for 2 hours. The ethanol was evaporated to leave an aqueous solution of the sodium salt of N- (2,6-dimethylphenyl) -N- (1-propanesulfonyl) alanine. The solution was acidified with dilute hydrochloric acid. The resulting acid was extracted with chloroform, the chloroform solution was dried and evaporated and the residue crystallized from toluene / 60-80 ° C petroleum ether to give 14.1 g (73% yield based on unreacted sulfonanilide) brown crystals of N- (2 , 6-dimethylphenyl) -N- (1-propanesulfonyl) alanine.

Example 3: A solution of 6.5 g of the alanine derivative of Example 2 in 100 ml of toluene was treated with 10 ml of thionyl chloride, refluxed for 1 hour and 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 h 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 silica gel column with chloroform. Evaporation of the eluate gave the isopropyl ether

CH,

as a clear yellow oil. '.

Analysis:

Calculated for C ₁₇ H ₃₇ NO ₄ S: C 59, 79, II 7, 97, N .4, 1 T

Found: C 59.45, H 7.91, N 3.77% ..

Examples 4 to 33: In an analogous manner as described in the preceding examples, the following compounds were prepared:

Sub.

acids

At play]. R ¹ me A Sub. 131 4 me me COOH 3.4-Dicl 212 5 me me COOH 2-Aet 98 6 me me COOH 2-C1-6 Me 118 7 me me COOH 2,6-di-le 131 8th me me COOH 2-OCH 122 9 ät me COOH 2,6-diile 118 10 me me COOH 2,6-DIXT 128 11 me COOH 2,6-diCl

R- R ^ij A Sub. Mp. ° C Analysis if the product is one found % c %H oil me H COOÄt 4-Cl oil analysis calculated 45.03 4.63 45.28 4.84 example me me COOÄt 4-Cl oil C _n H ₁₄ ClNO ₄ S 46.82 5:45 IN 12 47.13 5.27 4.74 me H CCOÄt 2, 6-dia oil C ₁₂ H ₁₆ ClNO ₄ S 54.62 6:51 4.80 13 54.72 6.71 4.78 me me COOÄt 2.6 -diMe oil C ₁₃ H ₁₉ NO ₄ S 56.04 7.29 4:58 14 56.16 7:07 5.17 me me COOÄt 3-CF, oil. C ₁₄ H _n NO ₄ S 45.84 5:00 4.91 15 j 46.01 4.75 5:07 me II COOÄt 3-CF ₃ oil ^C 13 ^H 16 ^F 3 ^NO 4 ^S 44.00 4.11 4.68 15 3,4-d.iCl 44.30 4:34 4:37 me H COOÄt oil C ₁₂ H ₁₄ F ₃ NO ₄ S 40.78 3.96 4.13 17 2-Isopr 40.50 4:02 4.61 me ii COOÄt oil C _n H ₁₃ Cl ₂ NO ₄ S 55.99 7:38 4.31 IS 3,4-Dicl "56.16 7:07 4:59 me me COO ¹ At oil C ₁₄ H ₂₁ NO ₄ S 41.90 3.99 4.29 ' 19 42.36 4:44 4.96 C ₁₂ H ₁₅ Cl ₂ NO ₄ S 4.68 20 4.60 4.12

R ¹ me A Sub. Mp. ° C Analysis if the product is a ( found calculated % C %H 31 is me me COOAt 2-Aet oil analysis C ₁₄ H ₂₁ NO ₄ S 55.94 56.16 6.89 7.07 example me me COOAt 2-Cl, 6Me oil C ₁₃ H ₁₈ ClNO ₄ S 48.52 4S.82 5.43 5.67 IN 21 me me Coat 2-OCII ₃ ül C ₁₃ H ₁₉ NO ₅ S 52.19 51.81 6.36 6.36 4.88 4.68 22 n-Pr me COOAt 2.6 -diMe 44-46 C ₁₆ H ₂₅ NO ₄ S 58.28 58.69 7.77 7.70 4.33 4.38 23 me me COOJit 2-Cl oil C ₁₂ H ₁₆ ClNO ₄ S 47.05 47.14 5.60 5.27 4.84 4.65 24 iit Me Me COQAt 2.6 -diMe 70 C ₁₅ H ₂₃ NO ₄ S 57.83 57.48 7.77 7.40 4.11 4.28 25 n-Bu Me Me Me COO ^- At COOAt 2,6-diMe 2,6-diCl Oil 108 C ₁₇ H ₂₇ NO ₄ S 59.45 59.79 P.25 7.97 4.80 4.58 26 Me Me COOMe COOAt 2,6-di-2,6-diA't oil ül C ₁₃ H ₁₉ NO ₄ SC ₁₆ H ₂₅ NO ₄ S 54.69 54.72 59.00 58.69 6.69 6.71 7.35 7.70 4.33 4.42 27 28 3.83 4.10 29 30 4.46 4.91 4.59 4.28

 SSST "

example R ¹ _R lu A Sub. Mp. ° C Analysis if the product is an oil. analysis IC ^e öH ° AEN 31 me me Coon Pr 2.6 -diMe oil bereclniet 57.57 57.48 7.49 7.40  4.41 4.47 32 me me COOCCH ₉ ) ₄ CH ₃ 2.6 -diMe oil found 59.66 59.79 8.10 7.97 3.98 4.10 33 me me COOCHCH ₃ (CH ₂ ) ₅ CH ₃ 2.6 -diMe oil C ₁₃ H ₂₃ NO ₄ S 63.01 62.63 8.51 8.67 3.70 3.65 C ₁₇ H ₂₇ NO ₄ S C ₂₀ H ₃₃ NO ₄ S

-HA-

Example 34: A solution of 5 g of N- (2,6-dimethylphenyl) N-methanesulfonylalanine in 50 ml of chloroform was treated with 5 ml of thionyl chloride, and the solution was refluxed for 1 hour and then evaporated, and the residue was again washed with toluene A chloroform solution of the residue was treated with a saturated solution of ammonia in chloroform, the mixture allowed to stand at room temperature for 4 hours, then water was added and the organic solvent was evaporated. washed with water and dried, recrystallizing from ethanol to give the amide

CH,

N-CHCONH.

obtained as colorless crystals, mp 158C.

In the same way as described in example 34, the following compounds were prepared:

Sub

10 t.

example R ¹ H A. Sub 4-Cl Mp. ° C 35 me II CONAt ₂ 2,6-dLMe 76 36 me H CONAt ₂ 2-Isopr 76 37 me H CONAt ₂ 3-CF ₃ 108 38 me H CONAt ₂ 3,4-Dicl 54 39 me me CONAt ₂ 2-Aet 90 40 'Me me CQNHPh 2-Aet 156 41 me me COO 2.6 Diet 120 42 i.fe Me. CQNH ₂ 2-Cl, 6 ~ Me 134 · 43 me CONH ₂ 158

Example 44: A mixture of 7.0 g of 3,4-dichloromethanesulfonanilide, 2.4 g of anhydrous potassium carbonate, 2.2 ml of chloroacetonitrile and 100 ml of 1,2-dimethoxyethane was stirred and refluxed for 6 hours. The dark 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 yielded an oil whose solution in ethanol gave a cream-colored solid which was identified as -N-cyanomethyl-3,4-dichloromethane sulfonanilide. Yield 3.8 g, mp 83 ° C.

SO ₉ QL

N-CH ₂ CN

βίο ι

Berlin, ά.7.1.1980 54 760 18

Examples 45 to 48: In an analogous manner as described in Example 44, the following compounds were prepared:

Sub

Example E R

18

A sub

45 46 47 48

Fd. ⁰ C

Me H CN 4-Cl 102

Me H CN 2,6-diMe 84

Me H CN 2-isoPr 99

Me H CN 3-CFo 61

Examples 49-33- Seeds of the following types were sown in anodised aluminum pans , a long χ 9.5 cm wide χ 5 cm deep, containing John Innes I pot compost. They were then poured into a hem with a controlled environment (22 ⁰ C, 65 to 85% relative humidity: 14 hours per day artificial illumination at I3OOOIUX) provided. Fourteen days after sowing, the seedlings were sprayed on the leaves with one of the following compounds formulated as a solution in aqueous acetone (1: 1 by volume). The concentration of the active ingredient and the application volume corresponded to an amount of 11.2 kg / ha in 450 l / ha. After 7 days growth in the controlled environment room, the plants were visually examined for herbicidal or growth-regulating response. All differences to the untreated control were evaluated on a scale where O = no effect and 100 = complete performance.

The results are shown in the following table. '... ·· -

LO LO CM CM * I LO 8th O O CM O cn O fO I rh CM LO 8th 8th O O cn O . LO LO rh i-l CM rh CM K) • LO O O O O O I IO CM iH co CM K) CM rh CM CM C CM 8th O cn LO O cn OK) 8th LO K) rh rh rh rh CM rh CM * LO O O LO O LO O LO CM rh cn K) rh cn CO CM O LO • LO O O LO O LO σ LO 1-H rH rH co K) oo co i CM cn CQ • LO O C C O LO O •H rH rH cn cn rh cn O) PQ 'C I O>   4 cn cn i ¹ V ^ rh f Φ sin % a dui cn / -> (Λ -> th  rl C B r \ • Η U) t - ^ rh •H 3 cj • μ ρ * •H CD • 3 CO • H verb j? tiv alb ita ο GJ 5h • H V) Q) to P- - ( cj Ph P vi vi 3 Ui rh H ¹ co O isum ίΠίΙϋί I • Η γΗ O eta ν vena O O W) rt Ο- ^ ' to V- ' \ / W I I I I » 1 φ S CO • 3 ιο C id ta O Q) in M  Η cn Cr. 1) CU Λ J £ -Η -H 'Λ • m C ₁ &) α) id  3 rd W pi isi '' J I β ' O) C r ^ Ό

0 ^ ₁ - its- Berlin, d.7.1.1980 I JtA "-. ^! & ^w 54 760 18

Examples 55-60: The following compounds were each formulated as kaolin / sand dust and incorporated into John Innes 1-pot compost in an amount corresponding to 26 ppm by weight / volume of active ingredient soil and in anodized aluminum tanks, 19 cm long χ 9.5 cm wide χ 5> 0 cm deep, introduced. This amount corresponds approximately to an application to the soil surface of 11.2 kg active ingredient / ha cultured to a depth of 5 cm. Seeds of the species listed in the following were sown in the treated soil, and poured in a controlled environment room (22 ⁰ C, 65 to 85% relative humidity, 14 hours per day artificial illumination at 13ΟΟΟ lux) for 21 days kept. Then the plants were examined visually for growth regulating or herbicidal effects. All differences from the untreated controls were scored on a scale of 0 to 100, with 0 indicating no effect and 100 total extermination. The results are shown in the following table:

*-O

Example 56 57 58 59 60

Connection; from example 15 44 22 3 24

Sweetening amount (ppm) 26 26 26 26 26

Peas ~ (Fisum sativum ) 0 0 0 0 0

Mustard - (Sinapls alba) 100 40 100 90 100

Linseed - (Linum jjsitatissimum) 70 20 100 20 100

Corn - (Zea maxa) 50 5 50 20 60

Oats - ( Avena sativa) 20 60 5O 20 60

Baigras ~ (LoIi um; oer_enne) 100 5 90 90 100

Examples 61 to 65: Seeds of the species indicated below were grown in John Innes I pot compost in aluminum pans, 19 cm long χ 9 "5 cli wide χ 5" 0 cm high. u. between one species sown per Pfarmes, "The earth's surface was then planted with one of the

    .. '-46- Berlin, d.7.1.1980 I 0 1 & Ö 54 760 18

the following compounds formulated as a solution in aqueous acetone (1: 1, v / v), except for the compound of Example 44 which was formulated as an aqueous suspension containing 1000 ppm of the wetting agent Lissapol NX (nonylphenol / ethylene oxide condensate) , sprayed. Each compound was applied in an amount of 2.8 kg of active ingredient per hectare in 450 liters of spray liquid per hectare. Then the pans were cast and for 21 days in a controlled environment room (22 ⁰ C, relative humidity 65 to 85%, 14.h day artificial illumination at 17OOO lux) asked "Then the pans were visually wachstuinsregulierende or herbicidal effects examined. All differences to an untreated control were evaluated on a scale of 0 to 100, where 0 means no effect and 100 means complete destruction. The results are shown in the following table:

Example connection from example ks / ha 61 15 62 44 63 22 64 y 65 24 species Dosierunejsinenpje 2.8 2.8 2.8 2.8  2.8

Starwort - (Stellaria media) mustard - (§inajois.alba).

Cotton - (Go sypi um sp.) Tomato - (L £ COE§i £ sicon es, culentum) White Goosefoot - (Ckenpjaodj ^ JjUJbU Carrot (Daucu_s carota.) V / iron - (Triticum ae tiv_um) Barley - (Hordeum vulgare) wild oats - (Avena fatüa) bulrush - (Alopecuru's myosuroldes) barnyardgrass - (lchinochloa cimis- ^ a

Fingergrass ~ (lliililaria, sanguinalis) 100

Rice - (Orjsjae sotiva)

30 - 0 50 - 0 - 10 - 0 90 - 0 - 0 - 0 0 80 20 - .0 40 - 90 - 100 - 80 100 - 60 - 0 - 0 0 - 90 - 0 0 0 _ 10 0 0 30 5 0 100 20 40 100 ) 40 0 80 100 90 100

Berlin, d.7.1.i93O 54 760 18

Example 66: Seeds of monocotyledonous of the species indicated in the following were placed in anodised aluminum pans, 19 cm long χ _9} 5 cm wide χ 5, O.cm deep, the John Innes I potting compost contained sown. They were then poured and placed in a controlled environment room (22 ⁰ C, 65 to 85% RH, 14 hours a day artificial illumination at 17ΟΟΟ lux). Fourteen days after sowing, the seedlings were sprayed on the leaves with the compound of Example 44 which was formulated as an aqueous suspension together with 2000 ppm of the wetting agent Lissapol NX. The dosage level was adjusted to 2.8 kg of active ingredient in 45Ο 1 per ha. After a further 14 days in the controlled environment room, the plants were visually examined for growth regulating or herbicidal effects. All differences to an untreated control were evaluated on a scale of 0 to 100, where 0 means no dissolution and 100 complete annihilation. The results are shown in the following table:

Spec ies ^ . ". , Dosierunsmen ^ ek ^ / ha __JLsJ ~ L

Wheat - (Triticum aestivum) 0

Barley - (Hordeum vulgare) 0

Hiimi Millet - (Echinoehloa crus-galli) 100

Examples 67 to 83: The following compounds were tested according to the method of Examples 56 to 60, but in an amount of I30 ppm by weight / volume of the active ingredient to soil »This amount corresponds to etv / a of an earth surface application of 56 kg of active ingredient per ha, cultivated to a depth of 5 cm.

The results are below

I \ example species 67 68 69 70 71 72 73 74 75 76 77 78 79 80 sl 82 83 Connection of example Peas - (Pisum sativum) Mustard - (Sinapis alba). Linseed - (Linum usitatissimum) 4 , 5 7 9 12 14 17 18 25 26 27 35 36 4.5 46 47 48 Baigreis - (Lolium pererme) Oats - (Avcna sativa) 70 70 90 30 50 70 20 70 50 50 70 80 40 70 80 30 100 90 40 40 90 40 40 80 5 100 50 100 100 100 20 100 100 20 100 40 20 100 40 20 100 90 20 100 90 10 "80 100 50 100 100 Corn - (Zea mays) 0 20 0 20 5 30 0 30 0 100 100 20 20 80 so 50 90 40 30 30 20 5 20 0 0 20 100 ' 100 20 20 70 70 30 80 70th 30 30 30 0 40 0 30 40 100 100 20 20 30 30 10 40

Example 84: Aqueous acetone suspensions containing 2000 mg of the compound of Example 15 per liter and 125 mg of the wetting agent Lissapol NX (nonylphenol / ethylene oxide condensate) per liter were applied to the soil surrounding the roots and leaves of cucumber plants with two fully grown leaves. The treated plants as well as the controls treated with the wetting agent alone were inoculated 24 hours after the chemical treatment with spores of the organism Gu.rkenmehltau (Erysiphe cichoracearum). The plants were then placed in a controlled environment room (18 ° C, 80 to 90% relative humidity); after 14 days, the extent of the disease was measured to find that treatment with the active compound resulted in 82% fungal control, while controls showed control of less than 5%.

Example 85: A slow stream of hydrogen sulfide was passed through a stirred solution of 6.0 g of N-cyanomethyl-3,4-dichloromethane sulfonanilide in 75 ml of pyridine containing 11.0 ml of triethylamine. blown. The reaction was carried out at room temperature for 4 hours, and the mixture was poured into 1500 ml of ice / water. The precipitated brown solid was collected by filtration, washed with water and dried. The product was identified as N- (thiocarbamoylmethyl) -3,4-dichloromethane sulfonanilide, yield 6.0 g (89%), m.p. 178 ° C.

Examples 86 to 89: In an analogous manner as described in Example 85, the following compounds were prepared:

^so ? ^r i 2 _R 1. r-.

Π - Λ

_ ± Sub Sub

-so-

example R ¹ 18 R. A Sub. Mp. ° C S 86 me H -CNH ₂ 2-I.sopropyl 136 87 me H "2 4-chloro 186 88 me H -CNH ₉ 3-CF ₃ "136 89 me H -CNH ₂ 2,6-dimethyl. 160

Examples 90 to 92: In an analogous manner as described in Example 2, the following compounds were prepared:.

Sub

example R ¹ _R 18 90 ' me ät 91 n-Bu me 92 n-Pr me

A Sub - O COOH 2,6-di-ie 164 COOH 2.6 -diMe 112 COOII 2.6 -diMe 143

Examples 93 to 122: In a manner analogous to that described in Example 3, the following compounds of the formula given in Examples 90 to 92 were prepared:

R ¹ _R 1S I Λ Sub. Pp. C. Analysis, if the product is one Ilyse 7.61 7.97 oil is example ät me COUNC ₄ H ₉ 2,6diMe oil Ans found calculated 60.02 59.79 4.90 5.27 IN 95 me H COOÄt 2-Cl, 6Me oil C ₁₇ H ₂₇ NO ₄ S 46.79 47.13 7.26 7.40 3.80 4.10 94 me ät COOÄt 2,6diMe oil C ₁₂ H ₁₆ ClNO ₄ S 57.56 57.48 4.60 4.91 4.37 4.58 95 ' NSIe ₂ me COOÄt 3,4-Dicl oil C ₁₅ H ₂₃ NO ₄ S 42.70 42.28 4.66 4.47 96 me me COOÄt 4-OSO ₂ Me 101 ^C 13 ^H 18 ^C1 2 ^N 2 ° 4 ^S 7.16 7.59 97 · 'N ° 2 me ccoÄt 2.6 -diMe 164 98 S me COOÄt 3,4-Dicl 80-82 5.92 5.76 99 me COOÄt 2.6 -diMe oil 56.01 55.56 7.00 7.37 100 NMe ₂ me COOÄt 2.6 -diMe oil C ₁₇ H ₂₁ NO ₄ S ₇ 55.04 54.85 3.58 3.81 101 C ₁₅ H ₂₄ N ₂ O ₄ S P.36 p.53

, R ¹ R ¹⁸ A Sub. Mp. ⁰ C Analysis, if the product is one found calculated "-Γ ου "; oil is Roe ₂ me COOÄt 2-Cl, 6-Me oil analysis C ₁₄ H ₂₁ CLN ₂ O ₄ S 48.05 48.20 5.68 6.07 example NMe ₂ me COOMe 2-Cl, 6-Me oil VJi * r 1 l \ Ulli / - * \ J » O 46.95 46.63 5.39 5.72 w / 102 me me COOÄt 2-OSO ₇ Me oil C ₁₃ H ₁₉ NO ₇ S ₂ 42.76 42.73 5.34 5.24 7.94 8.03 103 NMe ₂ me COOMe 2.6 -diMe 71 7.91 8.37 104 me me COOAt. 4-OH 108 3.60 3.83 105 me , me COOisoPr • 2,6-diMe 64 106 me me CO3-Q 2-Cl, 6Me 76 107 me me COOisoPr 2-Cl, 6Me 78 108 H COOÄt 3,4-Dicl oil C ₁₃ H ₁₆ Q ₂ N ₂ O ₄ S 42.88 42.51 4.54 4.39 109 110 7.85 7.63

example

11.1

112

114 115 "116 117 118

,, 18 Λ Sub · F ^ ⁰ C Analysis if < found calculated "c 4H oil is me 000-Γ ~ \ 2.6 -diMe 103 ° read in product R ¹ H COOMe 3,4diCl oil analysis C _n II ₁₄ Cl ₂ N ₂ O ₄ S 39.01 38.72 4.00 4.14 IN me H COOÄt 4-Cl oil C ₃₂ H ₁₇ ClN ₂ O ₄ S 45.22 44.93 5.16 5.34 NMe ₂ me COOisoPr 2.6 -diMe .oil C ₁₆ H ₂₅ NO ₄ S 59.02 58.69 7.95 7.70 8.61 8.21 NMe ₂ me COOÄt 2-Cl, 6Me 142 - P.57 8.73 xt me COO-Q 2.6 -diMe 92 4.61. -4.28 CX T NO ₂ H-' - (CH ₂ ) ₂ COOJit 2.6 -diMe oil C ₁₅ H ₂ ^ NO ₄ S 57.14 57.48 7.16 7.40 ät H - (QI ₂ ) ₂ COOMe 2.6 -diMe oil CH ₂₁ NO ₄ S 55.81 56.16 6.94 7.07 'Me 4.33 4.47 x Me 4.50 4.68

»*

R ¹ . _R 18 A Sub. Fp.V Analysis, if the product 63.80 63.44 8.44 8.87 Oil is me H CH, - (QL) ₉ COOQr f TT 6 13 2.6 -diMe oil '..' analysis 49.72 49.87 4,53 4.19 example me me COOMe 2-CF ₃ , 4-SPh oil found. calculated 58.29 58.69 7.40 7.70 119 · ät ät COOÄt 2.6 -diMe oil CH ₅ N0 S 3.83 3.52 120 η Pr ät COOÄt 2.6 -diMe 51 ^C 18 ^H 18 ^F 3 ^NO 4 ^S 2 3.71 3.23 121 C ₁₆ H ₂₅ NO ₄ S 3.94 4.28  122 '· .. ·

Example 123: In a manner analogous to that described in Example 2 but using a bromolactone starting material, the lactone became

prepared, mp 127 ° C. ·

Examples 124 to 127: In a manner analogous to that described in Example 34, the following compounds of the formula given in Examples 90 to 92 were prepared:

example R ¹ R ¹⁸ 124 me H 125 me me 126 me me 127 me II

Sub -

Mp. ⁰ C

Analysis if the product is an oil

Analysis . found

calculated

% C

OONÄt.

CONHCH ₀ COOAt

GQNMNHOOOSt

2-Cl, 6-Me

2.6 -diMe

2.6 -diMe

2,6-diIvfe

70

178

oil

^C 17 ^H 28 ^N 2 ° 3 ^S

J59.86 59.97

8.64 8.29

8.40 8.23

Examples 128 to 148: In an analogous manner as described in Example 44, the following compounds of the formula given in Examples 90 to 92 were prepared:

I ι ·

oeispic Χ- R I me H Λ Sub. Fp. ⁰ G 128 me me me CN 2-Cl, 6Me 68 129 me TJ CN 2.6 -diMe 80-82 130 me H CN 2-Cl 65 131 me CN 3-Cl, 4ivfe ' 88 132 nPr H CN 3,4-Dicl 80 133 me H CN 2,5-DICL 112 134 me H CN 3-Cl, 4-F 110 135 me TT CN 2,6-Dicl 82 136 me TT CN 2-OSO ₂ i 98-99 137 At H CN 3,4-Dicl 79-81 138 NMe ₂ H CN 3,4-Dicl 85 ' 139 me H CN 2,3-DICL 86 140 me H CN 3-Cl 64 . 141 me H CN 4-SCN 118 142 ' me H CN 3-NO ₂ , 4-Cl 114-116 143 me H CN 2,4-DICL 88 144 NMe ₂ H Qi 4-Cl. 52 145 me CN 3.4 -diMe 102 ¹⁴⁶ H (Oy ₂ GV 2.6 -diMe sl 147 II (Oy ₂ CN 3,4-Dicl 78 148 (CH ₇ ) rCN 3.4 -diMe 88

-JS-

Step Example. le 149 to 160: In an analogous manner as described in Example 85, the following compounds of the formula given in Examples 90 to 92 were prepared:

example R ¹ R ^1S A Sub Mp. ⁰ C 149 me K CSNH ₂ 2-Cl, 6Me 152. 150 me H CSNH ₂ 3-Cl, 4Me. 202 151 me H CSNfI ₂ . 2-Cl 172 152 me H CSNH ₂ 2,6-Dicl 180 153 me H CSNH ₂ 2,5-diCi ' 196 154 me H CSNH ₂ 3-Cl 184 155 nPr H CSNH ₂ 3,4-Dicl 168-170 156 , lit H CSNH ₂ 3,4-Dicl 162-164 157 me H CSNH ₂ 2,3-DICL 178 158 me H CSiNM ₂ 3-Cl, 4-F 182 159 me H CSNH ₂ 2,4-DICL 160 160 H -CSNH ₇ 2-OSO ₂ Me 180

example

161:

MOI ₂ COOAt

MeSO ₂ C 1 pyridine

A solution of 10.0 g of N-phenylglycine ethyl ester in 50 ml of pyridine was treated with 4.3 ml of methanesulfonyl chloride. The exothermic reaction was allowed to proceed unchecked. whereupon the mixture was refluxed for 2 1/2 hours and then cooled; then it was poured onto a rapidly stirred mixture of ice / water / hydrochloric acid. The precipitated brown solid was collected by filtration, washed with water and dried. Yield 7.0 g (49%). By conversion

59-

crystallize from ethyl acetate / 60 ~ 80 ° C petroleum ether were colorless crystals with a. Mp. From 66 ⁰ C received.

example

162:

BrQtCOOAt Κ-ΟΟ, / DMF

CFL

I 3.

NCHCOOÄt

A mixture of 6.0 g of 2 ', 6'-dimethylathanesulfonanilide, 2.1 g of anhydrous potassium carbonate, 3.65 ml of ethyl 2-bromopropionate and 90 ml of dimethyl 1-formamide (DME ¹ ) was stirred and 7 1/2 9O ⁰ C heated. The mixture was cooled and filtered, and the residue on the filter was washed with hot dimethylformamide and finally the filtrate was evaporated. The resulting yellow oil was dissolved in ether and the solution was washed successively with 10% sodium hydroxide solution and water, then dried (MgSO ₄ ) and evaporated. The solid residue was slurried with a little ethanol and the crystals were collected by filtration. Yield of N-1-carboethoxyethyl 2 ', 6'-dimethylathansulfonanilide 5.7 g (65%), mp 7O ⁰ C.

Example 163: A mixture of 68.5 g of 2 ^r , 6'-dimethyl-ethanesulfonanilide, 24.5 g of anhydrous potassium carbonate, 58.0 g of ethyl 2-bromopropionate and 400 ml of 1,2-dimethoxyethane. was stirred at reflux for 66 h and boiled, then cooled and filtered, and the filtrate was evaporated.

A solution of the oily residue in ether was washed three times with 100 ml of 10% sodium hydroxide solution and then with water, dried (MgSO 4) and evaporated to give N- (1-carboethoxyethyl) -2 ', 6'-dimethyl-ananesulfonanilide as a pale yellow oil a purity of more than 99% was obtained (by gas-liquid chromatography).

Analysis:

Calculated for C ₁₅ H ₂₃ NO ₄ S: C 57.48, H 7.40, N 4.47, O 20.42, S 10.23%

found: C 57.19, H 7.71, N 4.81 I.

The aqueous alkaline washings were combined and acidified with dilute HCl. The precipitated solid (9.9 g) was filtered off, washed with water, dried and identified as unreacted sulfonanilide.

The overall yield of the ester was 84.5 g (98% based on unrecovered sulfonanilide).

example

164:

SO ₇ Me

NOICONHNHCOOEt OL

OFi

αϊ

NCHGON ¹ HNH

CH

A solution of 5.6 g of N- [1- (2-ethoxycarbonyl) -hydrazinocarbonyl) -ethyl] -2 ', 5'-dimethylethylsulfonanilide in 75 ml of ethanol plus 75 ml of 10% NaOH solution was added 2 1/2 h heated on a steam bath and then cooled; then the ethanol was evaporated. The resulting aqueous solution was acidified, heated in a steam bath for 1 hour and then filtered. The filtrate. was neutralized with dilute NaOH, saturated with sodium chloride and extracted with chloroform. The chloroform solution was dried and evaporated. The residue gave from a solution in toluene / 60-80 ° C petroleum ether 2.6 g (58%) of almost colorless crystals of N- [1- (hydrazinocarbonyl) ethyl] -2 ', 6'-dimethylmethansulfonanilid, mp up to 118 ° C

Example 165: In a standard insecticidal activity test, the compound N- [2- (methylcarbamyloxyimino) -propyl] -2 ', 6' "dimethylmethanesulfonanilide at 100 micromolar concentration exhibited a 30% inhibition of acetylcholinesterase.

  '-61-

Example 166: A 1% suspension / solution of the product of Example 157 in polyethylene glycol (Carbowax 4 00) was added to a dextrose broth at a concentration of 1000 ppm weight / volume of the medium. Then, dilution was carried out in test tubes to achieve a concentration of 200 ppm of weight / volume of the medium. To 8 ml quantities of broth was added 0.2 ml of a dense broth culture of the bacterium Xanthomonas malvacearum, which in particular infects cotton. After 8 days of incubation at 25 C, all broth samples were checked for signs of bacterial growth. There was no growth, proving that the compound is highly bacteriostatic against this organism.

Examples 167-169: A one week old cornmeal / sand culture of the Uuralium Disease Organism Pythium ultimurn was hand mixed thoroughly with pure sterile John Innes No. 1 pot compost at a 3 kg culture to 12 liter soil. The infected soil was then allowed to stand for about 18 hours before use. Each of the compounds listed below was milled together with a wetting agent, Tween 20 (1% of final volume), until a solution or fine suspension was formed, which was then diluted with distilled water to 160 ml of solution containing 15:00 To get 500, 150 or 50 ppm active ingredient. 15 ml aliquots of this solution were added to 75 g portions of the Pythium ultiinum infected soil contained in small plastic containers (60 mm diameter, 55 mm high). 15 cabbage seeds, variety Flower of Spring, were placed in a circular well in the treated infected soil, covered and sealed with a plastic lid. The containers were then placed in a constant temperature room (25 C + 1 ° C). Four replicates per treatment with an additional treatment were made, sown seeds in soil that had been chemically treated, i. no infection had been done. The latter treatment was performed to measure the direct effect of the chemical compound on germination of the seeds. Wake up 6 days, the containers were taken out of clera room

controlled temperature and examined the extent of fungal growth on the surface of the earth and the percentage of seed emergence. The results of these two studies are expressed by the following scale:

0 = <20% inhibition.

1 = 20-34% inhibition

2 = 35-44% inhibition.

3 = 45-54% inhibition.

4 = 55-64% inhibition

5 = 65-74% inhibition

6 = 75-84% inhibition

7 = 85-94% inhibition

8 => 94% inhibition

and given in the following table:

example Connecting by example Dose of tpm • mycelium control rating Germination rating 167 9 300 0 5 100 0 5 30 0 1 168 24 100 0 5 30 0 1 169 26 300 0 '4 100 0 ' 4 30 0 3 untreated - 0 0

Examples 170 to 178: Aqueous acetone solutions or suspensions containing 2,000 or 500 mg of the following compound per liter together with 125 mg of a wetting agent per liter were applied to:

(A) the soil surrounding the roots and leaves of rice plants with two fully grown leaves,

(B) the leaves of vine plants with five fully-grown leaves,

(C) the soil surrounding the roots of potato plants with seven full-grown leaves,

(D) the leaves of potato plants with seven full-grown leaves,

(E) the soil or leaves surrounding the roots and leaves of barley plants with a fully grown leaf

(F) the soil surrounding the roots and leaves of cucumber plants with two vo] full grown leaves.

The treated plants and the controls treated with the wetting agent alone were inoculated 24 hours after the chemical treatment:

in the case (A) with an aqueous spore suspension of the disease organism rice blast Pyricularia oryzae,

in the case (B) with an aqueous suspension of sporangia of the disease organism viticulture 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 (E) by shaking with spores of the disease organism Gerüstehltau Erysiphe graminis or

in case (F) by shaking with spores of the disease organism cucumber powdery mildew Erysiphe cichoracearum.

Then the plants became

iro trap (A) placed in an atmosphere with 80 to 100% humidity at 28 ° C, the onset of the disease was measured 7 days later,

in case (B) placed in an atmosphere with 80 to 100% humidity at 14 to 18 ° C, whereby the onset of the disease was measured 12 days later,

in cases (C) and (D) placed in an atmosphere of 100% humidity for 24 hours and then placed in a controlled environment room {18 C and 80 to 90% relative humidity), the occurrence of the disease being measured 5 days later .ser,

in the case of (E) placed in a controlled environment room (18 C and 80 to 90% relative humidity), the occurrence of the disease being measured after 10 days, or

in the case of (F) placed in a controlled environment room (18 C and 80 to 90 % relative humidity), with the onset of the disease being risen after 14 days.

It was found that by comparison, with less than 5% in the controls, the chemical treatments gave the percentage control shown in the following table.

example Connection of example Rate TpM Illness . % Combat 170 141 2000 rice Blast 84 171 29 2000 wine mildew 98   1 500 11 90 172 41 2000 blight ⁹³ 173 132 2000 Il 76 M 500 » 59 174 148> 2000 barley powdery mildew 89 175 147 2000 Il 96 176 146 2000 Il 92 177 123 2000 Il 95 178 123 2000 powdery mildew 92

Example 179: The product of Example 95 was tested according to the method of Examples 49-55. The following results were obtained:

species effect peas 15 mustard 100 linseed 25 ryegrass 15 sugar beets 100 oats 20 Runner beans 100

Examples 180-184: The following compounds were tested according to the procedure of Example -66 except that rice (Oryza sativa) was included as additional test species:

f Ω "1 9Ω - £ 5" - Berlin, d. 07/01/1980

ι υ ι έυ ^ _{4 76Ο 18}

Example connection from Ββΐφ iel wheat barley Hiihnerhirse rice 85 180 131 O O 90 O 181 137 5 10 90 O 182 150 O O 80 O 183 O O 80 O

184 156 OO 90-0

Example 185: The product of Example 95 was tested according to the method of Examples 59 to 60, but in an amount of 13Ο and 26 ppm by weight / volume. The results were as follows:

species Dose amount 130 26 * peas 30 20 mustard 100 90 linseed 80 0 Corn 100 50 oats 100 0 Reigris 100 90

Examples 186 to 191: Each of the compounds listed below was formulated as:

(I) incorporated kaolin / sand dust and John Innes I pot compost in an amount corresponding to 6.5 and 3.25 ppm weight / volume of the active ingredient soil and in anodized aluminum pans, 19 cm long χ 9.5 cm wide χ 5.0 cm high, introduced. This corresponds approximately to a surface coverage of 2.8 and 1.4 kg of active ingredient per ha, cultured to depth of 5 cm. Seeds of the species indicated below were sown into the treated soil, i.a. one kind per pan, poured and placed in a room with controlled

Berlin, d.7.1.1980 54 760 18

profiled area (22 ⁰ C, 65 to 85% relative humidity and 14 h.künstliche exposure at 17000 lux) provided 21 days *

(II) Sine aqueous suspension together with 1000 TpM wetting agent Lissapol HX. The surfaces of another set of pans with already sown seeds were then sprayed at 2.8 or 1.4 kg / ha at 450 l / ha and the pans held in a controlled environment for 21 days. "

Then the plants were visually examined for growth regulating or herbicidal effects. All differences to an untreated control were evaluated on a scale of 0 to 100, with 0 meaning no effect and 100 indicating complete suppression.

The results are shown in the following table, where I means incorporation into soil and II surface spray

species Dosage amount TpM £ 1 • \ 6 II ^r erb Ϊ5 I ind 0 II I mg i: I from 57 II At U I spie) 1 II 1 8 I 5 · II 9 I 5 II cotton 6.5 0 0 0 0 0 0 0 0 0 0 5 - 3.25 0 0 0 0 0 0 0 0 0 0 - - tomatoes 6.5 0 0 0 0 0 0 0 0 0 0 90 - 3.25 0 0 0 0 0 0 0 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 Ό 0 0 0 0 0 - 3.25 0 0 0 0 0 0 0 0 .0 0 - - Rühnerhirse 6.5 90 100 60 70 90 100 70 80 90 100 - - 3.25 70 80 60 50 90 90 50 60 90 90 - - rice 6.5 0 0 0 0 0 Q 0 0 0 0 - - 3.25 0 0 0 0 0 0 0 0 0 0 - - carrots 6.5. - - - - 0 O O 0 0 0 0 - ό · LJ - - - - 0 0 0 0 0 0 - - Minimize 6.5 - - - - - - - - 90 I - j mustard 6.5 - - - - - - - - 50 Goosefoot I6.5 _ ... - - - - - 1 IOD

Example 192: 2 ', 6 ' -diethylethanesulfonanilide

114.4 g of ethanesulfonyl chloride were added slowly (during 15 minutes) to a stirred solution of 110 ml of 2,6-dimethylaniline in 500 ml of pyridine. The exothermic reaction was allowed to proceed unchecked (the temperature rose to 60 ° C), after which the reaction mixture was refluxed for 3 hours, cooled and poured into a rapidly stirred mixture (5 liters) 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 ° C. The yield of crude 2 ', 6'-dimethylethanesulfonanilide was 152.0 g (80%), m.p. 90 ° C.

The entire crude product was dissolved in .100 ml of 40% sodium hydroxide solution and the solution was diluted to about 2 liters, heated with charcoal for 30 minutes and then filtered. The clear pale yellow filtrate was cooled and poured slowly into 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 ° C. The yield of purified material was 114.7 g (60%), mp 92 ° C.

Examples 193 to 208: In an analogous manner as described in Example 1, the following sulfonamides were prepared:

• Sub

S ro 120

example R ¹ Sub. Mp. ' ⁰ C 193 methyl 2,3-dichloro 102 194 methyl 3,4-dimethyl 92 19.5 isopropyl 2,6-dimethyl 102 196 -CH ₂ COOAt 3,4-dichloro 104 197 ^: . methyl 2,6-dichloro   .- · 198 methyl 2-chloro-6-methyl ' 94 199 n-butyl 2,6-dimethyl ^{: v}   -. 200 methyl 2-ethyl 40 201 2-thienyl 3,4-dichloro 138 202 methyl 3-chloro-4-fluoro 116 203 methyl 3-chloro-4-methyl 83- 204 methyl 2-MethansuIfonyloxy 121-123 205 , methyl 2, 6-diisopropyl 93 206 methyl 2-methanesulfonyl-oxy-5-nitro 178 207 dimethylamino 2, 6-dimethyl - 203 Dimethy! Amino 2-chloro-6-methyl -

The NHR spectra of the compounds for which no Fp is given in the table are as follows:

Connection of example

197

199

207

208

T (CDCl ₃ )

2.5-3.0, 3H, m, (aromatic); 3.5, 1H ₇

broad s, (NH); 6,7, 3H, s, (CH ₃ )

2.95, 3H, s, (aromatic); 4.2, 1H, wide

s, (NH); 6.8-7.0, 211, m, (S-CH ₂ ); 7.65, 6H,

s, (2 _f 6-diCH ₃ ); 7.9-8.7, 4H, m,

9.1, 3H. t, (CH ₂ CH ₂ CH ₇ CH ₃ )

2.95, 311, s, (aromatic); 3.95,

s, (NH); 7,15,6H, s, [N (CH ₃ J ₂ ]

H, wide 7.6, 6H,

s, (2,6-diCH,)

2.75-3.0, 3H, m, (aromatic); 3.8, 111, broad ε, (NH); 7.2, 6H, s, [N (CH ₃ J ₂ ], 7.55, 3H _1, s, (CH),

Example 209: N-2-oxopropyl-4'-chloromethane-sulfonanilide

A mixture of Ιϋ, Ο σ 4 '-Chlormethansulf onan.il id, A ₁ O g of anhydrous potassium carbonate, 4.8 ml of chloroacetone and

1,2-dimethoxyethane was stirred at reflux for 24 hours and boiled and then filtered; the filtrate was evaporated. The oily residue was dissolved in ether and the solution washed with water, dried (MgSO 4) and evaporated. The residue gave from acetone / 40-60 ° C petroleum ether almost colorless crystals with a mp. Of 108 ⁰ C, yield 4.1 g. ,

Examples 210 to 221: In a similar manner as described in Example 209, were prepared:

N-2-oxopropyl-2'-chloro-6'-methylmethanesulfonanilide, m.p. 96 C;

N-2-oxopropyl-2 ', 6'-dimethylmethanesulfonanilide, m.p. 56 C, N-2-CKO-3,3-dimethylbutyl-2', 6'-dimethylethanesulfonanilide, Anal. Calcd. For C ₁₆ H ₂₅ NO ₃ S : C 61.70, H 8.09, N 4.50% found: C 61.75, H 8.26, N 4.62%,

N-2-oxopropyl-2 ', 6'-dimethylethanesulfonanilide, m.p. 68 ° C, N-2-oxopropyl-2', 6'-dimethyl-1-propanesulfonanilide, m.p. 104 C, N-2-oxopropyl-2 ', 6'-dimethyl-2-thiophenesulfonanilide, mp 127-128 ° C, N-2-oxopropyl-2', 6'-diethylirethanesulfonanilide, mp 46 C, N-2-oxopropy1-2 ', 6'- dimethyl-1-butanesulfonanilide, m.p. 69 ° C, N 2 -oxypropyl S ", 4'-dichloromethane sulfonanilide, m.p. 92 C, N-2-oxopropyl-3 ', 4'-diisopropylmethanesulfonanilide, m.p. 134 C, N 2-Oxopropy1-2'-methoxymethanesulfonanilide, m.p. 126 C, and N-2-oxopropy1-2 ', S'-dichloromethanesulfonanilide, m.p.

Example 222: N- (2,2-Dimethoxypropyl) -2'-chloro-6 '

, , methylmethansulfonanilid

To a solution of 5.7 g of N- (2-oxopropyl) -2'-chloro-6'-methylmethanesulfonanilide in 80 ml of methanol were added 0.2 g of 4-toluenesulfonic acid and then 6.65 ml of trimethyl orthoformate. The mixture was stirred at room temperature for 24 hours and then allowed to stand for 6 days. The solution was poured into dilute sodium bicarbonate solution and the precipitated solid collected by filtration, washed with water and dried to give 6.0 g of an off-white solid, m.p. 84C.

Examples 223 and 224: In a similar manner as described in Example 222, the following compounds were prepared:

N- (2,2-dimethoxypropyl) -4'-chloromethanesulfonylanilide _; M.p. 85 C, and N- (2,2-dimethoxypropyl) -2 ', 6'-dimethylmethylenesulfonanilide, m.p. 82 ° C.

Example 225: 4'-Chloro-N - [(2-methyl-1,3-dithiolane

2-yl) methyl] methanesulphonanilide

A solution of 3.2 g of 4'-chloro-N- (2,2-dimethoxypropyl) methanesulfonanilide in 50 ml of acetic acid was treated with 0.96 ml of ethanedithiol and the mixture was slowly distilled using a short Vigreux column for 30 minutes and discarded the distillate. The remaining acetic acid solution was evaporated and the residue re-evaporated with toluene to remove traces of acetic acid. A solution of the residue in ether separated on standing pink crystals. By recrystallization from ethyl acetate / ether, the product was obtained in the form of almost white crystals with a mp. From 114 to 117 C.

Examples 226 and 227: In a similar manner as described in Example 225, the following compounds were prepared:

N- [(2-methyl-1,3-dithiolan-2-yl) methyl] -2 ', 6'-dimethylmethanesulfonanilide, m.p. 103 ° C, and

N - [(2-methyl-1,3-dithioan-2-yl) methyl] -2'-chloro-6'-methylmethanesulfonanilide, m.p. 140 ° C.

Example 228: N - [(2-Methyl-1,3-dioxolan-2-yl) -methyl]

4'-chlormethansulfonanilid

A mixture of 6.0 g of N- (2-oxopropyl) -4'-chloromethanesulfonanilide, 10 ml of ethane-1,2-diol, 0.1 g of 4-toluene sulfonic acid and 75 ml of toluene was added by means of a Dean-Stark apparatus stirred with water at reflux and boiled. After 3 h, the reaction mixture was cooled and poured into about 2 00 ml of water containing several drops of sodium hydroxide solution. The organic layer was separated, washed with water, dried (MgSO 4) and evaporated to e in a brown oil which gave a reddish-white crystals from a toluene / 80-100 C petroleum ether solution, yield 6.0 g (86%). , Mp 84-85 ° C.

Examples 229 to 231: In a similar manner as described in Example 228, the following compounds were prepared:. ,

N - [(2-methyl-4-hydroxymethyl-1,3-dioxolan-2-yl) -methyl] -4'-chloromethanesulfonanilide, m.p. 118 C,

N - [(2-methyl-1,3-dioxolan-2-yl) -methyl] -2'-chloro-6'-methylmethanesulfonanilide, m.p. 84 C, and

N- [(2-methyl-1,3-dioxolan-2-yl) -methyl] -2 ' , 6'-dimethyl-ethylsulfonanilide, m.p.

Example 1 232: N-2-hydroxyiminopropyl-2 ', 6'-dimethyl-

methanesulfonanilide

A solution of 3.0 g of N- (2-oxopropyl) -2 ', 6'-dimethylmethanesulfonanilide in 50 ml of ethanol was added to a solution of 0.9 g of hydroxylamine hydrochloride and 1.1 g of sodium acetate dissolved in the minimum amount of water , added. The solution was refluxed for 3 hours, then cooled and evaporated. A solution of the residue in ether was washed with water, dried (HgSO.) And evaporated. The residue was again evaporated with toluene to remove traces of acetic acid. Then, the obtained product was crystallized from an ethyl acetate solution, mp 122-124 ° C.

Examples 233 and 234: A 1 week old maize meal / sand culture of the Pythium ultimum organism was hand picked. Thoroughly mix with clean sterile John Innes No. I pot compost in the ratio of 3 kg of culture to 12 liters of soil. This infected soil was then allowed to stand for about 18 hours before use. The compounds listed in the table below were each milled with Tween 20 wetting agent (1% of final volume) until a solution or fine suspension was obtained, which was then diluted with distilled water, to 160 ml of 1500 or 500 solution To obtain TpM active ingredient. 15 ml aliquots of this solution were added to 75 g portions of Pythium ultimum infected soil contained in small plastic containers (60 mm diameter, 55 mm high).

15 cabbage seeds, variety Flower of Spring, were placed in a circular recess in the treated infected soil, covered and covered with a plastic cover! locked. Then the containers were placed in a constant temperature room (25 _ + 1 G). Four replicates were made per treatment with an additional treatment whereby seeds were seeded in soil that had only been chemically treated, i. was not infected. This latter treatment was included to measure the direct effect of the chemical compound on germination of the seeds.

After 6 days, the containers were removed from the controlled temperature room and examined for the extent of fungal growth on the surface of the soil and the percentage emergence of the seedlings. The results of these two investigations are expressed on a scale from 0 to 8:

Ό = <20% inhibition. ,

1 = 20-34% inhibition

2 = 35-44% inhibition

3 = 45-54% inhibition

4 = 55-64% inhibition

5 = 65-74% inhibition

6 = 75-84% inhibition

7 = 85-94% inhibition

8 => 94% inhibition

and in the following table. Any phytotoxicity induced by the chemical compound alone was from treatment with the chemical compound alone.

connection Dose of tpm Mycosis control rating Germination rating Phytotoxicity assessment N - [(2-methyl-1,3-dioxolan-2-yl) -methyl] -4'-chloromethanesulfonanilide N-- ( 2,2-dimethoxypropyl) -2'-chioi-6 ^! - Irethylmethansulfon- anilide untreated 30Ü 300 100 0 - 8 4 3 0 0 1 1 0 0 G

-VI-

Examples 235 and 236: Aqueous acetone solutions of each of the compounds listed in the table below containing 2000 ppm, along with 125 ppm of a suitable wetting agent, were applied to the soil surrounding the roots and leaves of grapevines having five fully grown leaves.

The treated plants and controls treated with the wetting agent alone were inoculated 24 hours after the chemical treatment with an aqueous suspension of sporangia of the disease Sorganisinus Weinmehltau, Plasmopara viticola.

Then the plants were placed in a 100% humidity / 80% humidity atmosphere at 14-18 ° C and the onset of the disease measured 12 days later to find that the treatments had the following fungal control compared to less than 5% the controls.

connection

N- (2,2-dimethoxypropyl) -2'-chloro-6'-methyImethansulfonanilid

N - [(2-methyl-1,3-dioxolan-2-yl} methyl] -2'-chloro-6'-methvlmethansulfonaniiid

% Control of downy mildew

Examples 237 to 239: Aqueous acetone solutions of each of the following compounds at a level of 2000, 500 or 125 ppm by weight / volume together with 125 ppm of a suitable wetting agent were applied to the soil surrounding the roots and leaves of pot plants containing seven fully grown leaves ,

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

The plants were then placed in an atmosphere of 100% moisture / 30% humidity for 24 hours and then placed in a controlled environment room (18 ° C and 80-90%).

-JS-

relative humidity); the onset of the disease was measured after 5 days.

It was found that compared to less than 5% of the controls, the treatments had shown the level of fungal control shown in the table below.

connection Dose of tpm % Combat potato blight N-2-oxopropyl-2 ', 6'-dimethyl-methanesulfonanilide 2000 99 500 94 125 90 N- (2,2-dimethoxypropyl) -2 ^1, 6'dimethylmethansulfonanilid 2000 98 500 55 N - [(2-methyl-1,3-dioxolan-2-yl) -methyl] -2 ', 6'-dimethyl-methanesulfonanilide 2000 98

Example 240: Aqueous acetic acid solutions of N-2-oxo-3,3-dimethylbutyl-2 ', 6'-dimethylethanesulfonanilide containing 2000 ppm by weight / volume together with 125 ppm of a suitable wetting agent were applied to the roots and leaves of rice plants applied earth surrounding two fully grown leaves.

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

Then the plants were placed in an atmosphere with 100% humidity / 80% humidity at 28 ° C; the onset of the disease was measured 7 days later. The treatment was found to provide 8% antifungal control as compared to less than 5% of the controls.

Example 241: N- (2-Oxopropyl) -2'-chloro-6'-methylmethanesulfonanilide, formulated as kaolin / sand dust, was added to soil and added to John Innes I pot compost in an amount corresponding to 130 ppm by weight / volume of the active ingredient Anodized Alurainium Pannan (19 cm long χ 9.5 cm wide

χ 5.0 cm deep). These amounts corresponded approximately to an earth surface application of 56 kg active ingredient per ha cultured to a depth of 5 cm. Seeds of peas, mustard, linseed, corn, oats and ryegrass were sown in the treated soil, watered and placed in a controlled environment room (22 ° C, 65-85% relative humidity, 14h artificial exposure at 13000 lux) 21 days long put.

Then the plants were visually .. rende or herbicidal effects examined for wachstumsregulie- '''. All differences to an untreated control were scored on a scale ^a from 0 to 100, where 0 means no effect and 100 means complete suppression.

The results are shown in the following table: Species dosage amount

(Ppm)

Peas (Pisum sativum) Mustard (Sinapis alba) Linseed (Linum usitatissimum) Corn (Zea mays) Oats (Avena sativa) Raigras (Lolium perenne)

130

30

100

80

60 70

Example 242: 27.5 ml of a 30% solution of sulfuric acid was added dropwise to a stirred mixture of 0.1 mol of N- (2-oxopropyl) -2 ', 6'-dimethylmethanesulfonanilide, 6.2 g of potassium cyanide and 20 ml of water added. The temperature was maintained at 15 ° C. The reaction mixture was stirred for 15 minutes and the cyanohydrin of the sulfonamide was isolated.

example

243:

SO ₉ Me

™ 3

N-QlCOQI

SO ₂ Me

ipy N-CHCOQi-

A mixture of 0.5 mole of N- [3,3-di (ethoxycarbonyl) -2-oxo-1-methylpropyl] -2 ', 6'-dimethylmethanesulfonanilide, 1.5 moles of sodium hydroxide, 500 ml of ethanol and 500 ml of water was heated for 2 1/2 h and then cooled and the ethanol was evaporated. The resulting aqueous solution was acidified with hydrochloric acid and heated for 1 h and then the product was isolated.

Example 244: A mixture of 12.5 g of 2,6-dimethylmethanesulfonanilide, 14.2 g of 2'-chloro-4-thiocyanoacetanilide, 4.3 g of potassium carbonate and 75 ml of dimethylformamide was stirred and heated to 70-80 ° C for 3 hours heated and finally poured onto ice / water. The precipitated viscous semi-solid material was extracted into chloroform. The chloroform solution was then washed with 5% sodium hydroxide solution and with water, dried (MgSO 4) and evaporated to a brown oil. A solution of this oil in chloroform was percolated through a short silica gel column. Upon evaporation of the eluate, a brown oil was obtained, which separated from a solution in ethyl acetate almost colorless crystals of N, ε [(4-thiocyanophenyl) carbamoyl] methyl '-2', 6'-dimethylmethanesulfonanilide, m.p.

Example 245: A solution of 2.8 g of N- (3-hydroxy-2-oxopropyl) -2 ', 6'-dimethylmethanesulfonanilide in 5 ml of pyridine and 5 ml of acetic anhydride was allowed to stand for 20 hours at room temperature The aqueous solution was extracted successively with dilute hydrochloric acid and sodium bicarbonate solution, dried (MgSO 4) and evaporated to a yellow oil. A solution of this oil in chloroform was replaced by a short one Percolation of the silica gel column, evaporation of the eluate gave the product, N- (3-acetoxy-2-oxopropyl) -2 ', 6'-dimethylmethanesulfonanilide as a pale yellow oil, yield 2.5 g (77%).

 Analysis:

Calculated for C ₄ H ₁₉ NO ₅ S: C, 53.66, H, 6.11, N, found 4.47%: C'53.20, H, 6, 57, N, 4.30%.

Example 246: A solution of 5.6 g of N-1 - [2- (ethoxycarbonyl) -hydrazinecarbonyl) -ethyl] -2 ', 6'-dimethylmethanesulfonanilide in 75 ml of ethanol and 75 ml of 10% sodium hydroxide solution became 2.1 / Heated for 2 h on a steam bath, whereupon the ethanol was evaporated. The remaining aqueous solution was acidified with dilute hydrochloric acid, heated for 1 hour on a steam bath and then filtered. The filtrate was neutralized with dilute sodium hydroxide solution, saturated with sodium chloride and extracted with chloroform. The chloroform solution was dried and evaporated and the residue from a solution in toluene / 60-80 C petroleum ether colorless crystals of N- [t-hydrazinocarbonyl) ethyl] -2 ', 6' -dimethylmethansulfonanilid in a yield of 2.6 g (58%), mp 115-118 ° C.

Example 247: A solution of 3.2 g of the hydrochloride salt of N- [1- (hydrazinocarbonyl) ethyl] -2 ', 6'-dimethylmethanesulfonanilide and 1.0 ml of acetylacetone in 25 ml of ethanol was heated to boiling and then allowed to cool to room temperature over 2 hours. The precipitated solid was collected by filtration and recrystallized from ethanol to give 1.5 g (43.%) of N- [3- (3,5-dimethyl-1-pyrazolyl) -1-methyl-2-oxoethyl] -2 '. , 6'-dimethylmethanesulfonanilide, mp 168 ° C.

Example 248: 1.2 ml of methyl isocyanate was added to an acetone solution of 2.7 g of N- (2-hydroxyiminopropyl) -2 ', 6'-dimethylmethanesulfonanilide containing 0.05 ml of triethylamine. The mixture was allowed to stand at room temperature overnight and then evaporated to a viscous oil which slowly solidified on standing. Recrystallization from ethyl acetate / 60-80 ° C petroleum ether, 3.0 g (91%) of colorless crystals of N- [2- (Methylcarbamoyloxyirnino) -propyi] 2 ', 6'-dimethylmethansulfonanilid, mp. 130 to 134 ° C. ,

Example 249:

A mixture of 2.7 g of N- (2-hydroxyiminopropyl) -2 ', 6'-dimethylmethanesulfonanilide, 0.75 g of potassium carbonate, 1.3 ml of iodomethane and 50 ml of acetone was stirred and slightly refluxed for 3 hours. The reaction mixture was filtered and the filtrate evaporated to an oil which precipitated from a solution in ether / 40-60 C petroleum ether crystals. Yield 0.6 g (21%), mp 126 ° C.

Example 250: 0.9 ml of acetyl chloride was added to a solution of 2.6 g of N- (2-hydroxyiminopropyl) -2 ', 6'-dimethylmethanesulfonanilide and 1.6 ml of triethylamine in 20 ml of dichloromethane. The mixture was stirred and refluxed 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 1.9 g of analytically pure N- [2- (acetyloxyiminepropyl] -2 ', 6'-dimethylmethanesulfonanilide (63%)).

Calculated for C ₁₄ II ₂₀ N ₂ O ₄ S: C 53.83, H 6.45, N 8.97% Found: C 53.74, H 6.80, N 8.49%.

Example 251: A solution of diethylethoxymagnesiotralona was prepared by refluxing a mixture of 0.9 g of magnesium, 5.6 ml of diethyl malonate, 4.3 ml of ethanol and 2 ml of ether for 3 hours, then evaporating with toluene and the solvent replaced by dry ether. To this solution was added dropwise with stirring an ethereal solution of N- (1-chlorocarbonylethyl) -2 ', 6'-dimethylmethanesulfonanilide. (made from 10g of acid and thionyl chloride). After stirring overnight at room temperature, the resulting complex was decomposed by heating with dilute sulfuric acid. The organics were extracted into ether and the solution washed with water, dried (MgSO ₄ ) and evaporated to give a solid residue. Recrystallization from ethyl acetate gave colorless crystals of N- [3,3-di- (ethoxycarbonyl) -2-oxo-1-methylpropyl] -2 ', 6 ^! - Diraethyirnethansulfonani lid, mp 125 C, received.

χ 5.0 cm deep). These amounts corresponded approximately to an earth surface application of 56 kg active ingredient per ha cultured to a depth of 5 cm. Seeds of peas, mustard, linseed, corn, oats and ryegrass were sown in the treated soil, watered and placed in a controlled environment room (22 ° C, 65-85% relative humidity, 14h artificial exposure at 13000 lux) 21 days long put.

Then, the plants were visually examined for growth-regulating or herbicidal effects. All differences to an untreated control were scored on a scale ^a from 0 to 100, where 0 means no effect and 100 means complete suppression.

The results are shown in the following table: Species dosage amount

(Ppm)

Peas (Pisurn sativum) Mustard (Sinapis alba)

Linseed (Linum usitatissimum)

Corn (Zea mays) oats (Avena sativa) Raigras (Lolium perenne)

130

30

100

.80

60 70

Example 242: 27.5 ml of a 30% solution of sulfuric acid was added dropwise to a stirred mixture of 0.1 mol of N- (2-oxopropyl) -2 ', 6'-dimethylmethanesulfonanilide, 6.2 g of potassium cyanide and 20 ml of water added. The temperature was maintained at 15 ° C. The reaction mixture was stirred for 15 min and the cyanohydrin of the sulfonanilide isolated.

example

243:

SO ₂ Me

1 ^ 3 ^ COOXt N-CHCOCH

^N COO t

SO ₂ Me

A mixture of 0.5 mole of N- [3,3-di (ethoxycarbonyl) -2-oxo-1-methylpropyl] -2 ', 6'-dimethylmethanesulfonanilide, 1.5 moles of sodium hydroxide, 500 ml of ethanol and 500 ml of water was heated for 2 1/2 h and then cooled and the ethanol was evaporated. The resulting aqueous solution was acidified with hydrochloric acid and heated for 1 h and then the product was isolated.

Example 244: A mixture of 12.5 g of 2,6-dimethylmethanesulfonanilide, 14.2 g of 2'-chloro-1-thiocyanoacetanilide, 4.3 g of potassium carbonate and 75 ml of dimethylformamide was stirred and heated at 70-80 ° C for 3 hours and finally poured onto ice / water. The precipitated viscous semi-solid material was extracted into chloroform. The chloroform solution was then washed with 5% sodium hydroxide solution and with water, dried (MgSO 4) and evaporated to a brown oil. Dissolution of this oil in chloroform was percolated through a short silica gel column. Evaporation of the eluate gave a brown oil which, from a solution in ethyl acetate, gave almost colorless crystals of N- [4-thiocyanophenyl) -carbamoyl] -methyl? -2 ', 6'-

l dimethylmethanesulfonanilid farewell, mp 152 C.

Example 24 5: A solution of 2.8 g of N- (3-hydroxy-2-oxopropyl) -2 ', 6'-dimethylmethanesulfonanilide in 5 ml of pyridine and 5 ml of acetic anhydride was allowed to stand at room temperature for 2 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 (HgSO 4.) And evaporated to a yellow oil. A solution of this oil in chloroform was percolated through a short silica gel column. Evaporation of the eluate gave the product, M- (3-acetoxy-2-oxopropyl) -2 ', 6'-dimethylmethanesulfonarylid as a pale yellow oil, yield 2.5 g (77%).

 Analysis:

Calculated for C ₁₄ H ₁₉ NO ₅ S: C 53.66, H 6.11, N 4.47% Found: C, 53 20; H, 6 57; N, 4.30%.

- 80 -

B ice ρ ie. 1 252: A solution of 7.5 g of N- (1-ethoxycarbonylethyl) -2'-trifluoromethyl-4'-phenylthiomethanesulfonanilide in 50 ml of acetic acid was heated to boiling with stirring and 6 ml of 100 volumes of hydrogen peroxide were added. Stirring and refluxing were continued for 3 hours whereupon the reaction mixture was poured into ice / water and extracted with chloroform. The chloroform solution was dried and evaporated to a yellow oil. which contains 6.6 g (83%) of colorless crystals of N- {1-ethoxycarbonylethyl) -2. ' trifluoromethyl-4'-phenylsulfonylmethanesulfonanilide from an ethanol solution, yield 6.6 g (83%), m.p. 121 ° C.

Example 253: A solution of 7.2 g of N-carboxymethyl-2 ', 6'-dimethylinethanesulfonanilide in 50 ml of chloroform was treated with 5 ml of thionyl chloride and the mixture was refluxed for 1 1/2 hours and then evaporated. The residue was re-evaporated with toluene (to remove traces of thionyl chloride) and then dissolved in 10 ml of dry tetrahydrofuran. 19.6 g of tris-trimethylsilyloxyethylene and then 3 drops of tin (IV) chloride were added. The reaction mixture was allowed to stand at room temperature for 70 hours, then heated in 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 a steam bath for 1/2 h, saturated with salt and extracted with ether. The combined ether solution was washed with sodium bicarbonate solution, dried (MgSO 4) and evaporated to give 5.0 g of N- (3-hydroxy-2-oxopropyl) -2 ', 6'-dimethylmethanesulfonanilide as a clear yellow oil (66%). Analysis:

Calculated for C ₁₃ H ₁₇ NO ₄ S: C 53.12, H 6.32, N 5.16% Found: C 57.72, H 6.40, N 4.91 I.

Example 254: In an analogous manner as described in Example 253, N- (3-hydroxy-2-oxo-1-methylpropyl) -2 ', 6'-dimethylmethanesulfonanilide was prepared, m.p. 125-126 ° C.

Examples 255 and 256: In a similar manner as described in Examples 193 to 203, 2 ', 6'-dimethyl-4-morpholinesulfonanilide, mp. 124 ° C, and 3', 4'-dichloro-4-morpho-

linosulfonanilide, mp 122C.

Examples 257 to 259: In a similar manner as described in Example 3, the following esters of the formula given in Examples 4 to 33 were prepared:

example R ¹ R ¹⁸ A Sub. Mp ° C 257 n-Pr me COOCH ₂ - ^ J ^ 2.6 -diMe oil 257a me H CH = CHCOOAt 2-C1,6-Me 70 258 me me COOÄt 3,5-DICL 92 259 me me COOMe 3,5-DICL 110

The analysis for the compound of Example 257 is as follows:

Calculated for C ₁₉ H ₂₅ NO ₅ S: C 60.14, H 6.64, N 3.69 I Found: C 60.63, H 7.00, N 3.69%.

Examples 260 and 261: In a similar manner as described in Example 34, the following compounds of the formula given in Examples 35 to 43 were prepared:

example rl R ¹⁸ A Sub. Mp. ⁰ C 260. 261 Me Me H me ⁰⁰ KIp corQ) 2,6-diMe 3,5-diCl 109 210

Example 262: In a similar manner as described in Example 209, N- (2-oxoprcyl) -3 ', 5'-dichloromethanesulfonanilide, m.p. 106 ° C, was prepared.

Example 263: In a similar manner as described in Example 44, N- (3-cyanopropyl) -3 ', 5'-dichloromethanesulfonanilide, m.p. 82 ° C, was prepared.

Example 264: In a similar manner as described in Example 123, the lactone became

produced, mp 128 ° C.

Example 265: In a similar manner as described in Example, N- (thiocarbamoylmethyl) -3 ', 5'-dichloromethanesulfonanilide, mp 188C, was prepared.

Example 266: A 40% w / v. Emulsifiable concentrate was prepared by preparing a xylene solution of the following ingredients:

N- [1- (A "thoxycarbonyl) -äthy1] -2 ', 6'-dimethyl-1-propane

sulfonanilide; 400 g

Arylan CA {calcium dodecylbenzenesulfonate 70% in butanol). 25 g of ethylane C40AH (castor oil / ethylene oxide condensate) 25 g

Xylene (to 11) about - 600 ml

Example 267: A 25% w / v. Emulsifiable concentrate was prepared by preparing a xylene solution of the following ingredients:

N- [T- (ethoxycarbonyl) -ethyl] -2 ', 6'-dimethylethanolananilide 250 g Arylan CA 25 g

Ethylan C40AH -. '^; , 25 g

Xylene (to 11) about 740 ml

B e is ρ ie 1 268: N- (2-oxopropyl) -3 ', 4'-dimethylmethane

Sulfonanilide was assayed at 300 ppm in the test described in Examples 233 and 234. It gave a mycelial control score of 0 and a germination score of 3, while the untreated samples gave a score of 0 for both.

Examples 269 to 271: The compounds indicated below were investigated in the test described in Examples 170 to 178. The results are as follows:

IOF

example connection Quantity TpM illness % Be fighting 269 Product of Example 46 2000 Potato blight. 56 270 N- (2-oxopropyl) -3 ', 4'-dimethylaminethanesulfonanilide 2000 rice Blast 67 Il 2000 barley powdery mildew 99 Il 2000 blight 62 271 Product of Example 249 500 blight 74 Il 500 rice Blast 66

Example 272: In a similar manner as described in Example 209, N- (2-oxopropyl) -3 ', 4'-dimethylmethanesulfonanilide, m.p. 78 ° C, was prepared.

Claims (20)

invention claim 1 2 ^ "" * ^ R -COR or a carbonyl derivative or a Addition compound thereof means wherein E and G are the same or different and each is oxygen or sulfur 1 2
compound thereof, wherein R is hydrogen, alkyl of 1 to 15 carbon atoms; Alkyl having 1 to 15 carbon atoms, mono- or polysubstituted by halogen, alkoxy having 1 to 6 carbon atoms, amino and amino, mono- or disubstituted by alkyl having 1 to 15 carbon atoms and alkanoyl having 2 to 7 C. -atoms; Cycloalkyl having 3 to 7 C atoms; Phenylalkyl of 7 to 10 carbon atoms; Phenylalkyl having 7 to 10 C atoms, monosubstituted or polysubstituted by halogen on the phenyl ring, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro and trifluoromethyl; phenyl; Phenyl, monosubstituted or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, alkylsulfonyloxy having 1 to 6 C atoms, nitro and trifluoromethyl; a heterocyclic group linked via a C atom in the group, which group is a single hetero ring having 3 to 7 ring atoms, of which 1 or 2 are heteroatoms, wherein each heteroatom is nitrogen, sulfur or oxygen, to which hetero ring optionally a benzene ring is fused; or such a heterocyclic group, one or more times / 1-3 Q where R ^{lJ is} hydrogen or -COCR; and R, R-% R, Ή / and R are the same or different and each is hydrogen; Alkyl having 1 to 15 carbon atoms; Alkyl having 1 to 15 carbon atoms, mono- or polysubstituted by halogen, alkoxy having 1 to 6 carbon atoms, amino and amino, mono- or disubstituted by alkyl having 1 to 15 carbon atoms and alkanoyl having 2 to 7 C. -atoms; Alkoxy having 1 to 6 C atoms; SCN; nitro; mercapto; Alkylmercapto having 1 to 6 C atoms; Amino or halogen; with the proviso that & R ² , R ^, R ^, R ^ and R are not each hydrogen, when R is phenyl or phenyl, mono- or polysubstituted by halogen, alkyl having 1 to 6'C-L atoms, alkoxy having 1 up to 6 C atoms, Mtro and trifluoromethyl, and A is -COOH or COOR ^9. 1 to 15 C atoms is *. Process according to item 2, characterized in that the substituents have the following meanings: '- 86 - 21 O 129 ' 55 760 18 -Ö4 - H ^{1 is} alkyl having 1 to 15 C atoms; Alkyl having 1 to 15 C atoms, monosubstituted or polysubstituted by halogen, alkoxy having 1 to 6 C atoms, alkoxycarbonyl having 2 to 7 C atoms, Carboxy, -GIIR R, phthalimido, -SQlJ, benzoyloxy, alkanoyloxy having 2 to 7 carbon atoms, alkyl sulfonyl oxy having 1 to 6 carbon atoms, furyl, nitrile, hydroxy, amino and amino, mono- or disubstituted by alkyl with 1 to 15 C atoms and alkanoyl having 2 to 7 C atoms; Cycloalkyl having 3 to 7 C atoms; Phenylalkyl of 7 to 10 carbon atoms; Phenylalkyl having 7 to 10 carbon atoms, on the phenyl ring mono- or polysubstituted by halogen, alkyl Mt 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, ITi tr-o, -SCiT, alkyl sulfonyl oxy with 1 to 6 C atoms and trifluoromethyl; a heterocyclic group which is a single hetero ring having 3 to 7 Hing atoms of which 1 to 3 heteroatoms, wherein each hetero atom is nitrogen, sulfur or oxygen "to which optionally a hetero ring B is fused nzolring _e; such a heterocyclic group, monosubstituted or polysubstituted by alkyl having 1 to 6 C atoms, Oxo, nitro and halogen: _R 7 or a group of the formula -N - ^^ »where R ' and R are the same or different and each is hydrogen; Alkyl having 1 to 15 C-Atomens alkyl having 1 to 15 carbon atoms, mono- or polysubstituted by halogen, alkoxy having 1 to 6 carbon atoms, alkoxycarbonyl with 2 to 7 C atoms, carboxy . _r O ~ cW '° B ¹¹ , phthalimido, -SCIF, 3ensoyloxy _t alkanoyloxy of 2 to 7 carbon atoms, alkylsulfonyloxy of 1 to 6  -'87 - 55 760 18 C atoms, furyl, ITitril, hydroxy, amino and amino, mono- or disubstituted by alkyl having 1 to 15 O atoms and alkanoyl having 2 to 7 C atoms; Phenylalkyl having 7 to 10 C atoms; Phenylalkyl having 7 to 10 C atoms on the phenyl ring mono- or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, Hatro _T -SCH, alkylsulfonyl-oxy having 1 to 6 C atoms and trifluoromethyl; phenyl; or phenyl, monosubstituted or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to C atoms, alkylsulfonyloxy having 1 to 6 C atoms, nitro, -SCl and trifluoromethyl » 1 to 15 C atoms / alkyl having 1 to 15 C atoms, monosubstituted or polysubstituted by halogen, alkoxy having 1 to 6 C atoms, Alkoxycarnoonyl with 2 to 7 C atoms, carboxy, 0 -CNR R ¹¹ , phthalimido, -SCN, benzoyloxy, alkanoyloxy with 1.0 1 - 88- -SCN and trifluoromethyl; ;  R Aikylen or alkenylene having 1 to 6 carbon atoms; ..-. '. ^; '. , '. o _ 1 to 6 C atoms, alkoxycarbonyl having 2 to 7 C atoms, carboxy, 0 -CNR R, phthalimides -SCN, benzoyloxy, alkanoyloxy having 2 to 7 carbon atoms, alkylsulfonyloxy having 1 to 6 carbon atoms, furyl, nitrile 'hydroxy, amino and amino, mono- or disubstituted by alkyl having 1 to 15 C- Atoms or alkanoyl having 2 to 7 C atoms; Cycloalkyl having 3 to 7 C atoms; Phenylalkyl having 7 to 10 C atoms, g <on the phenyl ring mono- or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro, -SCN, alkylsulfonyloxy having 1 to 6 C Atoms and trifluoromethyl; phenyl; Phenyl, mono- or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, alkylsulfonyloxy having 1 to 6 C atoms, nitro, -SCN and trifluoromethyl a heterocyclic group which is a single Hetero ring having 3 to 7 ring atoms, of which 1 to 3 are heteroatoms, wherein each heteroatom is nitrogen, sulfur or oxygen, to Vielehen hetero ring a benzene ring is optionally fused; such a heterocyclic group, mono- or polysubstituted by alkyl having 1 to 6 C atoms, oxo, nitro and halogen; or a group of the formula -N - ^ '8 / where R and ¹ ^ or -Έ , where R ¹ is hydrogen Represents substance or -COOR ^; and R ^{12 is} hydrogen, alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, aryl, substituted aryl, hetero-cyclic group linked via a carbon atom in the group, or such substituted heterocyclic group; or RA is a group of the formula Au. where R is hydrogen, alkyl or aryl, B is oxygen or -ITR ¹ ^, τ> ¹ 5 is hydrogen or alkyl and η is Ο, or 2; R ^ sR-, R ^ ₁ H ^ and R ° are the same or different -Λ s, i o 19h ^; '55 760 18 -SG- and in each case hydrogen, alkyl, substituted alkyl, hydroxy, alkoxy * -SOU, nitro, halogen, amino, substituted amino, mercapto, a group of the formula -SR ¹⁶ , - 30R ¹⁶ , -SO ^ R ¹⁶ or -OSO ₀ R ¹⁶ wherein R ¹⁶ is alkyl, aryl or aralkyl, -SO ^ ₀ ER R -000R ⁰ or ¹ ^, with the proviso that R, R, R, R ^ and R ^ ^e are not 3 ^e ils hydrogen when R is alkylene, R represents phenyl or substituted PJienyl and q Q A is COOH or COOR ^, where R ^{y is} alkyl · 1, a method of controlling pests in a place infested or liable to attack them, or of regulating the growth of a plant in a place where the plant is to grow or grow, characterized by being responsive to that particular one A pesticidal or plant growth regulating amount of a sulfonanilide of the formula or a salt thereof, in which formula R is alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, aryl, substituted aryl, a heterocyclic group, a substituted heterocyclic group, or a group of the formula -N ^ " "78 ° each of R and R is the same or different and each is hydrogen, alkyl, substituted alkyl, aralkyl, substituted aralkyl, aryl or substituted aryl; R represents alkylene or alkenylene; ο π A- COOH; -CSSH: -ΟΞαΐΤt -CIDER ¹ ^ R ¹ '; -CON-Co I -ίο '"SLi ^y -CH or -COR or a carbonyl derivative or an additive compound thereof, wherein E and G • ² , -COOOH ₂ - ^, -O-OCH; ; -O ^. | ^, ητχ ! * " ^w CH ₀ - WXl ^ / -trj ηττ <- ^. 0 - CH ₂ / - \ -OC J -0OCH ₀ OGOCHo; -00NH- / VsGrl; I ^^ O - CH 2 3 '\ / CH ₂ OH .coolt '-COC H; -C - CH 2; -COC (CHo) ₃ ; -0 - CH ₃ ; ϊ'τΟΗ IiOCH ₃ -C is - CHo or -C - CHo or R-A - \ ^ ^ O; Ho iTOCHHCHo ii 3 ii 3 three or four of the gods R%, R ^, R, R ^ and R are each hydrogen and are the same or different and each is alkyl of 1 to 3 C atoms, halogen, hydroxy, Phenylriercapto, -SGrT, nitro, alkoxy having 1 to 6 carbon atoms, trifluoromethyl, phenylsulfonyl or methylsulfonyl mean. 5c method according to point 2 _S distinguished by "that the substituents have the following meaning; - 87b -. , 55 760 _s 18 E ¹ alkyl having 1 to 15 C atoms ;. Alkyl having 1 to 15 carbon atoms, mono- or polysubstituted by halogen, alkoxy having 1 to 6 carbon atoms, amino and amino _r mono- or disubstituted by alkyl having 1 to 15 carbon atoms and alkanoyl having 2 to 7 carbon atoms; Cycloalkyl having 3 to 7 C atoms, j phenylalkyl having 7 to 10 C atoms; Phenylalkyl having 7 to 10 C atoms, monosubstituted or polysubstituted by halogen on phenylation, alkyl having 1 to 1 88 - - 95-- 2 to 7 carbon atoms, alkylsulfonyloxy having 1 to 6 carbon atoms, furyl, nitrile, hydroxy, amino and amino, mono- or disubstituted with alkyl having 1 to 15 carbon atoms and alkanoyl having 2 to 7 carbon atoms; Phenylalkyl of 7 to 10 carbon atoms; Phenylalkyl of 7 to 10 carbon atoms, monosubstituted or polysubstituted by halogen on the phenyl ring, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms. * Nitro, -SCN, alkylsulfonyloxy having 1 to 6C Atoms and trifluoromethyl; phenyl; or phenyl which is monosubstituted or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, alkylsulfonyloxy having 1 to 6 C atoms, nitro, -SCN and trifluoroethyl; R and R are the same or different and each represents a group as defined immediately above for R; or R and R together with the nitrogen atom to which they are attached form a heterocyclic group which is a single hetero ring containing from 5 to 7 ring atoms, of which, in addition to the nitrogen atom, 1 or 2 may be further heteroatoms, each heteroatom being oxygen, Sulfur or nitrogen is, to v.'elc.hen hetero ring optionally a benzene ring is fused; such a heterocyclic group, mono- or polysubstituted by alkyl having 1 to 6 C atoms, oxo, nitro and halogen; or R is hydrogen, while R a group of the formula -N = C "" ^ 'or -N, where - S3 -> R ^{13 is} hydrogen or -COOR ⁹ ; and R is hydrogen, alkyl of 1 to 15 carbon atoms; Alkyl having 1 to 15 carbon atoms, mono- or polysubstituted by halogen, alkoxy having 1 to 6 carbon atoms Alkoxycarbony1 with 2 to 7 C atoms, carboxy, '0 -CNR R, phthalimides, -SCN, benzoyloxy, alkanoyloxy of 2 to 7 carbon atoms, alkylsulfonyloxy of 1 to 6 carbon atoms, furyl, nitrile, hydroxy, amino and amino, mono- or disubstituted by alkyl of 1 to 15 C Atoms and alkanoyl having 2 to 7 C atoms; Cycloalkyl having 3 to 7 C atoms; Phenylalkyl of 7 to 10 carbon atoms; Phenylalkyl having 7 to 10 C atoms, on the phenyl ring once or several times by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro, -SCN, alkylsulfonyloxy having 1 to 6 C atoms and trifluoromethyl substituted; phenyl; Phenyl, mono- or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, alkylsulfonyloxy having 1 to 6 C atoms, nitro, -SCN and trifluoromethyl; a heterocyclic group linked via a carbon atom in the group, which group is a single hetero ring having 3 to 7 ring atoms, of which 1 to 3 are heteroatoms, for each heteroatom nitrogen, sulfur or oxygen to which hetero ring is optionally one Benzene ring anellie is'; or such a heterocyclic group, mono- or polysubstituted by alkyl having 1 to 6 C atoms, oxo, nitro and halogen; or R-A is a group of the formula ^(CH 2> n. 2 · Method according to item 1, characterized in that the substituents have the following meaning; - 82 - IO V - 8r - R is alkyl having 1 to 15 carbon atoms; Alkyl having 1 to 15 carbon atoms, mono- or polysubstituted by halogen, alkoxy with ^ 4 760 18 and each is hydrogen, alkyl, substituted alkyl, aralkyl, substituted aralkyl, aryl or substituted aryl;
E represents alkylene or alkenylene; 0 _o A-GOOH; -CSSH; -CEGR ^; -CENR ^ R ¹¹ ; -CON = CCT Q; -CN or -COR or a carbonyl derivative or a Addition compound thereof means wherein E and G are the same or different and each is oxygen or sulfur are; R is alkyl, substituted alkyl, aralkyl, substituted t is aralkyl, aryl or substituted aryl; R and R are the same or different and each is a group 4 · Method according to point 2, characterized by d _a that three or four of the groups H-, B? _t R ', B? and R are each hydrogen · 5 «Method according to item 2, characterized by d _a that E ¹ is alkyl of 1 to 4 carbon atoms, nitrophenyl, 2-Phthalimidoäthyl, Athoxycarbonylmethyl, morpholino, thienyl or dialkylamino having 2 to 8 C-rAtomen; R is alkylene having 1 to 3 C atoms or alkenyls having 3 C atoms; A-COOH; -CEiTH ₂ ; CIT; -COITHPh; Cycloalkyloxycarbonyl having 4 to 8 C atoms; morpholinocarbonyl; '-OONHNH ₂ ; -COMiCH ₂ . COOalkyl having 1 to 4 C atoms; -CONHHHCOiOalkyl with 1 to 4 C atoms; -C -] / Y '³; -COOR ¹⁷ or -COiI (R ¹⁷ ) _o , where R ^{17 is} alkyl of 1 to δ C atoms; -COCH ^; -COCH ₂ OH; •: · -87a- 55760 .S - CH, // ^ / ^00H 3 / O - OH, 6 C atoms, alkoxy having 1 to 6 C atoms, nitro and trifluoromethyl; phenyl; or phenyl, mono- or polysubstituted by halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, nitro and trifluoromethyl, or a group of s 7 8
Formal -N ^ _ft , where R and R are the same or different and each hydrogen; Alkyl having 1 to 15 carbon atoms; Alkyl having 1 to 15 carbon atoms, a "-, or polysubstituted by halogen, alkoxy having .1 to 6 carbon atoms, amino and amino, mono- or polysubstituted by alkyl having Ί to 15 carbon atoms and alkanoyl with 2 to 7 C atoms; Phenylalkyl of 7 to 10 carbon atoms; Phenylalkyl having 7 to 10 carbon atoms, on the phenyl ring mono- or polysubstituted by halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, nitro and trifluoro methyl; phenyl; or phenyl, mono- or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to C atoms, nitro and trifluoromethyl; R alkylene having 1 to 6 carbon atoms; O _R 7 A-COOH, -CSSH, -CEGR ⁹ , CENR ¹⁰ R ¹¹ , -CON = C " _q "* R or -CN, where E and G are the same or different 7 10 11 mean as defined for R ^f ; or R and R together with the nitrogen atom to which they are attached, a heterocyclic group or a substituted heterocyclic group 7 8 "^ R ^ tet, where R 'and H are the same or different -JOS- Berlin, d.7.1.1980 7 10 11 as defined for R 'mean; or R and R together with the nitrogen atom to which they are attached, a heterocyclic group or a substituted heterocyclic group / 7 8 -N η, where R and R are the same or different and each ^X R ⁸ because hydrogen; Alkyl having 1 to 15 carbon atoms; Alkyl having 1 to 15 carbon atoms, mono- or polysubstituted by halogen, alkoxy having 1 to 6 carbon atoms, amino and amino, mono- or disubstituted by alkyl having 1 to 15 carbon atoms and alkanoyl having 2 to 7 C. -atoms; Phenylalkyl of 7 to 10 carbon atoms; Phenylalkyl having 7 to 10 C atoms, monosubstituted or polysubstituted by halogen on the phenyl ring, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro and trifluoromethyl; phenyl; or phenyl, monosubstituted or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, alkylsulfonyloxy having 1 to 6 C atoms, nitro and trifluoromethyl; R is alkylene or alkenylene having 1 to 6 C atoms; 7. The method according to item 2, characterized in that the substituents have the following meaning; R is alkyl having 1 to 15 carbon atoms; Alkyl having 1 to 15 carbon atoms, mono- or polysubstituted by halogen, alkoxy having 1 to 6 carbon atoms, amino and amino, mono- or disubstituted by alkyl having 1 to 15 carbon atoms and alkanoyl mif 2 to 7 C. -atoms; Cycloalkyl having 3 to 7 C atoms; Phenylalkyl with 7 to 10 - 89a - 55 760 18 Carbon atoms; Phenylalkyl having 7 to 10 C atoms, monosubstituted or polysubstituted by halogen on the phenyl ring, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro and trifluoromethyl; phenyl; Phenyl, monosubstituted or polysubstituted by halogen, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, alkylsulfonyloxy having 1 to 6 C atoms, nitro and trifluoromethyl; a heterocyclic group which is a single hetero ring having 3 to 7 ring atoms, of which 1 or 2 are heteroatoms, each heteroatom being nitrogen, sulfur or - 90 -   , '-. i-58 - ·. , Oxygen is / to which hetero ring optionally a benzene ring is fused; such a heterocyclic group, mono- or polysubstituted by alkyl having 1 to 6 C atoms, nitro and halogen; or a group of the formula 8 "^ R R are identical or different and each is hydrogen, alkyl, substituted alkyl, aralkyl, substituted _s kyl, aryl or substituted aryl; R represents alkylene or alkenylene; 0 _n Q -in i / i It ^ * ~ T>' A -COOH; -CSSH; -CSGR *; -CENR ¹⁰ R ¹¹ ; -CON = CrTq; -CN or 8. »Method according to item 1, characterized in that the active compound N-cyanomethyl-3 ¹ , 4 ^f -dichloromethanesulfonanilide; N- / i "- (ethoxycarbonyl) -ethyl 7-2 ^t , 6'-dimethylethanesulfonanilide? N- / T- (1-ethoxycarbonyl) -ethyl 7-2 ^t , 6'-dimethylmethanesulfonanilide or
N-2-oxopropyl ~ 2 ', 6'-dimethylmethanesulfonanilide. Process according to item 1, characterized in that the compound is N- (1-ethoxycarbonyl) ethyl) -2'-6'-dimethyl-1-propanesulphonanilide. Berlin, d. 7.1.1980 54 760 18 8th
R are the same or different and each is hydrogen; Alkyl having 1 to 15 carbon atoms; Alkyl having 1 to 15 carbon atoms, monosubstituted or polysubstituted by halogen, alkoxy having 1 to 6 carbon atoms, alkoxycarbonyl having 2 to 7 carbon atoms, carboxy, '' 1011
-CNR R, phthalimido, -SCN, benzoyloxy, alkanoyloxy having 2 to 7 carbon atoms, - alkylsulfonyloxy having 1 to 6 carbon atoms, furyl, nitrile, hydroxy, amino and amino, mono- or disubstituted. by alkyl having 1 to 15 C atoms and alkanoyl having 2 to 7 C atoms; Phenylalkyl of 7 to 10 carbon atoms; Phenylalkyl having 7 to 10 C atoms, monosubstituted or polysubstituted by halogen on the phenyl ring, alkyl having 1 to 6 C atoms, alkoxy having 1 to 6 C atoms, nitro, -SCN, alkylsulfonyloxy having 1 to 6 C atoms and trifluoromethyl; phenyl; or phenyl which is monosubstituted or polysubstituted by halogen, alkyl having 1 to G carbon atoms, alkoxy having 1 to 6 carbon atoms, alkylsulfonyloxy having 1 to 6 carbon atoms, Ni; 9
are; R is alkyl, substituted alkyl, aralkyl, substituted · 9
in which R 1 is alkyl having 1 to 15 C atoms. 9 are each and are oxygen or sulfur; R is alkyl having 1 to 15 carbon atoms; Alkyl having 1 to 15 C atoms, monosubstituted or polysubstituted by halogen, alkoxy having 1 to 6 C atoms, amino and amino, mono- or disubstituted aryl, alkyl having 1 to 15 C atoms and alkanoyi having 2 to 7 C atoms atoms; Phenylalkyl of 7 to 10 carbon atoms; Phenyla-ikyl having 7 to 10 carbon atoms, on the phenyl ring mono- or polysubstituted by halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, nitro and trifluoromethyl; phenyl; or phenyl which is monosubstituted or polysubstituted by halo, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, nitro and trifluoromethyl; R 'and R are the same or different and are each a group immediately above defined for R; or R and R together with the nitrogen atom to which they are attached form a monocyclic heterocyclic radical having 5 or 6 ring groups; i'0-- ^: i20 55 760 18 of which, apart from the nitrogen atom, another may be a heteroatom, which heteroatom 10 atom is oxygen or nitrogen; or R is hydrogen while R is a group of the formula -N = CCq or -NLT * o cLar- JR R 9 and each oxygen or sulfur, R is alkyl with 9 '' in Ii I '^ R Ä -COOH; -CSSH; -CEGR; -CENR R; -CON = C ^ _Q ; ' -CN or COR or a carbonyl derivative or an addition compound thereof; where E and G are the same or different 9
or sulfur; R is alkyl, substituted alkyl, Aralkyl, substituted .Aralkyl, aryl or substitute 11
represents aryl; R and R are the same or different and each group is defined as for P / 10 11 Form a group; or R is hydrogen, while R a group of the formula -K = CCl Q ^oeiei1 -N_ "o is" where R ^ is hydrogen or -COOS ^: and R ^{12 is} hydrogen, alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, aryl, substituted aryl, heterocyclic group connected via a carbon atom in the group, or such substituted heterocyclic group; or RA is a group of the formula wherein R ^{14 is} hydrogen, alkyl or aryl, B is oxygen 10 11 Group form: or R means hydrogen, while R a group of the formula ^^ - R ^ -H * o -N = CCT o or -NcI ia, where R- * is water - R ^{y 1} * represents substance or -COOR ^; and R ^{12 is} hydrogen, alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, aryl, substituted aryl, heterocyclic group linked via a carbon atom in the group, or such substituted heterocyclic group; or 'RA is a group of the formula ~ -Λ0% - Berlin, d.7.1.1980 \ 0 12 © 54 760 18 Ί4. wherein E is hydrogen, alkyl or aryl, B is oxygen or -NS ^, R ¹ * is hydrogen or alkyl and η is 0, 1 or 2; and R ² , R 1, R ² , R ⁴ and R 8 are the same or different and are each hydrogen, alkyl, substituted alkyl, hydroxy, alkoxy, C 1 -C 5, nitro, halogen, amino, substituted amino, mercapto, a group of the formula SR, -SOR, -SO ₂ R ¹⁶ or -OSO ₂ R ¹⁶ , wherein R ^{16 is} alkyl, aryl or aralkyl, -SO ₂ NR ^ R or -COOR ¹² , with the proviso, ² ? ⁴ ^ , ₂ that R ² , B ?, R ⁴ and R ? are not each hydrogen, when R is alkylene, R is phenyl or substituted phenyl q o and A is COOH or COOR, wherein R ^{v is} alkyl, in addition to at least one material selected from the group of carriers, surfactants, other pesticides, other plant growth regulators, antidotes and fertilizers. Composition according to item 13 », characterized in that the active ingredient is the compound of the general formula R-r π-R ^ CD and their salts, in which R ^{1 is} alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, aryl, substituted aryl _? a heterocyclic group, a substituted heterocyclic group or a group of the formula -ΝΓ """ _Ο signify 10 tes aralkyl, aryl or substituted aryl; R and R are the same or different and each is a group 10. The method according to any one of the preceding points, characterized in that the compound is applied in one place. where a crop is supposed to grow or grow. 10 123 -S9- Berlin, d. 07/01/1980 54 760 18 substituted by alkyl having 1 to 6 C atoms, nitro and halogen: ρ 'ο h C g and R, R, H, Br and E are the same or different and each is hydrogen; Alkyl having 1 to 15 carbon atoms; Alkyl having 1 to 15 carbon atoms, one or more times substituted by halogen, alkoxy having 1 to 6 carbon atoms, amino and amino,. mono- or disubstituted by alkyl having 1 to 15 carbon atoms and alkanoyl having 2 to 7 carbon atoms; Alkoxy with 1 to. 6 C atoms: -SCK; nitro; mercapto; Halogen; amino; Amino, mono- or disubstituted by alkyl having 1 to 15 carbon atoms and alkanoyl having 2 to 7 carbon atoms: a group of the formula -SH ¹⁶ , -SOR ¹⁶ or -SO ₂ R ¹⁶ , wherein R ^{16 is} alkyl having 1 to 6 C atoms, phenyl or phenylalkyl with 7 to 10 122 12 C atoms is: or -COOR, where R is the immediately above has the meaning given 10 '11 form; or R is hydrogen, while R is a group of the IOrmel 10 11 interpret; or E and R together with the nitrogen atom to which they are attached, a heterocyclic group or a substituted heterocyclic group 10 12 « 55 760 18 -.85 are the same or different and each oxygen 11. The method according to item 10, characterized in that 0.5 to 10 kg of the compound per ha are applied and the weeds are selectively controlled, 12. The method according to item 10, characterized in that 1 to 6 kg of compound per ha are applied and fungi are combated. 12
A -COR or a carbonyl aerosol or an addition Pesticides or plant growth regulators, characterized in that they contain as active ingredient a sulphonanilide of the formula SO ₂ R ' N-R-A (D or a SaIs; thereof, - 104 Berlin, d.7.1.1980 10 12® 5 * 760 18 in which formula R is alkyl, substituted alkyl, cycloalkyl, aralkyl, substituted aralkyl, aryl, substituted aryl, a heterocyclic group, a substituted heterocyclic group or a group of the formula -N ^ o, wherein R 'and 14
wherein R is hydrogen, alkyl having 1 to 6 carbon atoms or phenyl, B is oxygen or -NR ¹⁵ , R ^{i5 is} hydrogen or alkyl having 1 to 6 C atoms and η is 0, 1 or 2; 55 760 18 R ² , R- ^ ₁ R ² * ", H ^ and H ⁶ equal to, or different and each hydrogen} alkyl having 1 to 15 G atoms j alkyl having 1 to 15 carbon atoms, mono- or polysubstituted by H _a logen, alkoxy having 1 to 6 G atoms, Alkoxycarbonyl having 2 to 7 carbon atoms, 0
Carboxy, -CKR ¹⁰ E ^11, -SCF phthalimides, B _e nzoyloxy 'alkanoyloxy of 2 to 7 carbon atoms, alkylsulfonyloxy having 1 to 6 carbon atoms, furyl, nitrile, hydroxy »amino, and amino mono- or disubstituted by Alkyl of 1 to 15 carbon atoms and alkanoyl of 2 to 7 carbon atoms; hydroxy; Alkoxy having 1 to 6 C atoms; -SClT; Nitro j Mercapto; H _a logen; amino; Amino, mono- or disubstituted by alkyl having 1 to 15 carbon atoms and alkanoyl having 2 to 7 carbon atomsj a group of Formula -SR ¹⁶ , -SOR ¹⁶ , -SO ₀ R ¹⁶ or -OSO ₀ R ¹⁶ , 15. Composition according to item 13, characterized in that the active substance is the compound according to item 3. 15 1 ^ or -NR ·, R '^ is hydrogen or alkyl and η O is ₅ 1 or 2 - 401} - Berlin, (3.7.1.1980 760 18 mean? and R, R-% jp ₉ -gp ^ _n S R ^{6 are the} same or different and each represents hydrogen, alkyl, substituted alkyl, hydroxy, alkoxy, -SON, nitro, halogen, amino, substituted amino, mercapto, a group of the formula -SR, -SOR ¹⁶ ,. -SO ₂ R ¹⁶ or -OSO ₂ R ¹⁶ . wherein R ^{16 is} alkyl, aryl or aralkyl, -SO ₂ NR ^ R or -COOR ¹² , with the proviso that R ² , Έ? ₉ R ^ and R ^ are not each hydrogen when R is hydrogen, methoxycarbonyl or ethoxycarbonylmethyl, R is alkylene, R ^{1 is} phenyl or substituted phenyl and A is benzoyl, COOH or COOr "where R ^{9 is} alkyl _o 16, agent according to item 13 », characterized in that the active substance is the compound according to item 5. 16
Wherein R is alkyl having 1 to 6 C atoms, phenyl or Phenylalkyl of 7 to 10 carbon atoms; -SO KR ^ ₀ R ^8, siobei R ^/ and R are as defined immediately above; or -COOR '^, where R has the meaning given immediately above, with the proviso that R ^2, R ^, R ^, R ^ and R ⁶ do not each represent hydrogen when R is alkylene having 1 to 6 carbon atoms, R is phenyl or phenyl mono- or poly-substituted by H _a lied , Alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, alkylsulfonyloxy of 1 to 6 carbon atoms, nitro _T- SCN and Srifluoromethyl 9 and A is COOH or COOK, where R is alkyl with 17 * Composition according to item 13 », characterized in that the active ingredient is the compound according to item 6. 18. Composition according to item 13, characterized in that the active ingredient is the compound according to item 7, wherein Ir has a meaning other than hydrogen. 19. Composition according to item 13, characterized in that the active ingredient is the compound according to item 8. 20. Composition according to item 13, characterized in that the compound N- (1- (Ithoxycarbonyl) lthyl) -2 ^s , 6 ^! -dimethy1-1 propansalfonanilide is »