DE3002880A1 - SUBSTITUTED 4-ALKYLTHIOALKANESULPHONE ANILIDE - Google Patents

Description

PATENT LAWYERS

WUESTHOFF - ν. PECHMANN - BEHRENS - GOETZ

professional representatives before the european patent office agrees pres l'office europeen des brevets

PR.-I) · '. Γ ΚΑΝΪ ^ ^- UESTHOFF

LR. I HIL. PREDA TUESTHOPF (1927-19J6) riPL.-ING. GERHARD PULS (1952-1971)

D1PL.-CHEM. DR. E. BARBER OF PECHMANN DR.-ING. DIETER BEHRENS DIPL.-ING .; DirL.-VIRTSCH.-JNG. RUPERT GOETZ

1A-53 221
Minnesota Mining

D-8000 MUNICH 90

SCHWEIGERSTRASSE 2

te le fon: (089) 66 10 5 i telegram: frotectpatent telex: j 24 070

patent applica-making

Applicant: MINNESOTA MINING AND MANUFACTURING COMPANY 3M Center, Saint Paul
Minnesota 55 101, USA

Title:

Substituted 4-alkylthioalkanesulfonanilides

030032/0728

PATENT LAWYERS

WUESTHOFF - ν. PECHMANN - BEHRENS - GOhTZ

PROFESSIONAL REPRESENTATIVES BEFOKE THE ZUKOPEAN PATENT OFPICE MANDATAIKES AGREES PKES l'OFFICE EUROPEEN DES BKEVBTS

DR.-ING. FRANZ VUESTHOFF T) K. PHII FREDA IPUESTHOFF (1527-I9J6) DI.'L.-ING. GERHARD PULS (τ $$ 1-1 $ γΐ) DIPL.-CHEM.DK. E. BARON OF PECHMANN DK.-ING. DIETEK BEHRENS DIPL-ING .; DIPL.-iriRTSCH.-ING. KUPEKT COETZ description

D-8000 MUNICH SCHWEIGERSTRASSE

phone: (089) 66 20 yi

TELEGRAM: PKOTECTPATENT

telex: j 14070

1A-53 221

The invention relates to halogen-substituted methane and chloromethanesulfonanilides, which are in the p-position by alkylthio, Alkyl sulfinyl or alkyl sulfonyl groups and optionally also substituted by trifluoromethyl and their Salts compatible with agriculture. The compounds according to the invention are effective herbicides and plant growth regulators. The invention also relates to herbicides containing the compounds and their use to regulate the growth of higher plants.

The invention specifically relates to compounds of the formula:

HNSO ₂ R

S (O) _n R ¹

in which E is an alkyl group with 1 to 4 carbon atoms (preferably 1 to 2 carbon atoms) or a monohalomethyl group (chloromethyl, bromomethyl) iodomethyl or fluoromethyl group, E ^{1 is} an alkyl group with 1 to 4 carbon atoms, A is a halogen atom or a trifluoromethyl group, B denotes a hydrogen or a halogen atom and η denotes 0 to 2,

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provided that when A is trifluoromethyl is, B is a halogen atom and their agriculturally acceptable salts. The invention relates to also means for killing or modifying the growth of higher plants which, as an active ingredient, contain a compound according to the invention, optionally dispersed in a carrier, and the use of the compounds according to the invention for modification the growth of higher plants and for the killing of higher plants and a process for the preparation of the compounds. The compounds according to the invention are particularly suitable for use in the field of selective herbicides Control of special plant species in the presence of special crops (with little or no destruction of useful plants occurs), e.g. to control weeds such as rhizomatous Johnsongrass, annual grasses, yellow Sedge and / or purple sedge in crops such as cotton or soybeans.

The compounds of the formula I in which E is the -GHpCl group and A is a chlorine or bromine atom represent a preferred group of compounds and those compounds of the formula I in which R is -CflEU and A is a chlorine or bromine atom represent a second preferred group, in both cases because of their high potency.

The compounds of the formula I can form salts, that is to say Compounds of the formula given above in which H has been replaced by an agriculturally suitable cation.

These salts are generally metal, ammonium and organic amine salts and can be prepared by treatment a compound in the acid form with a corresponding one

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Base under mild conditions. The metal salts according to the invention include the alkali salts and alkaline earth salts (e.g. barium, calcium and magnesium salts) as well as the heavy stable salts (e.g. zinc and iron salts) as well as other metal salts such as aluminum salts. Suitable bases for preparation of the metal salts according to the invention are the metal oxides, -hydroxides, carbonates, bicarbonates and alkoxides (alcoholates). Some salts can also be prepared by ion exchange (by reacting a salt according to the invention with an organic or inorganic salt in a 'cation exchange reaction' The organic amine salts include the salts of aliphatic (e.g. alkyl), aromatic and heterocyclic amines, as well as those with mixed structures of this type. For the preparation of the salts according to the invention Amines used can be primary, secondary or tertiary and preferably contain no more than 20 carbon atoms. Such amines are, for example, morpholine, methylcyclohexylamine, glucosamine, amines which are derived from fatty acids etc. The amine and ammonium salts can be prepared by reacting the acidic form with an appropriate one organic base or ammonium hydroxide. The salts given above are tolerable and special for agriculture The salt chosen will depend on the specific intended use and economic considerations. The alkali, alkaline earth, ammonium and amine salts are particularly suitable.

*) (e.g. lithium, sodium and potassium salts)

The salts according to the invention are frequently formed by converting the precursors or intermediates in aqueous solution Solution. This solution can be evaporated to obtain the salt of the corresponding compound, usually to a dry powder. In some cases it may be more beneficial to use a non-aqueous solvent such as alcohols, acetone, etc. to use. The resulting solution is then treated to remove the solvent, for example under reduced pressure evaporated.

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The compounds according to the invention can be prepared according to the following Reaction scheme can be prepared:

NHSO ₂ R

(D

(5)

(O) _n R-

SCN

NHSO ₂ R

(2)

(4)

N (SO ₂ R) ₂

The reaction step (1) comprises the formation of the substituted 4-üChiocyanoaniline from the appropriately substituted Aniliiei (the compounds are known, or processes for their Manufacture are known) by generally customary processes.

Reaction step (2) involves the formation of the substituted 4-alkylthioanilines directly from the corresponding 4-ihiocyanoanilines. This reaction can be achieved with the help of various common

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rather procedures are carried out. For example, the hiocyano group be alkylated in alcoholic sodium cyanide solution. Preferably the alcohol has the same hydrocarbon radical as the desired alkyl group. Optionally, initially a sodium mercaptide formed from the thiocyano group and this can then be alkylated using an alkylating agent such as an alkyl halide (methyl iodide).

Step (2) can also be carried out by first converting the sodium mercaptide into the free mercaptan by acidification convicted. The mercaptan is then treated with an alkylating agent such as an alkyl halide (methyl iodide) in the presence of a organic base implemented. Suitable organic bases are tertiary amines, such as triethylamine, dimethylcyclohexylamine, Pyridine et al. The reaction is usually preferred when the alkyl halide is a tert-butyl halide (tert-butyl bromide) is.

The reaction of step (3) is the methanesulfonylation or Ohlormethansulfonylierung the product of step (2) with two or more equivalents of methanesulfonyl chloride or chloromethanesulfonyl chloride in the presence of a base. If 1 to 2 equivalents of the sulfonyl chloride are employed, a mixture can be used of the mono- and bi- (sulfonylated) product obtained which can be used in step (4-). If two or more equivalents of the chloride are reacted it will bi '(sulfonylated) product preferred. Suitable bases for the Implementation of stage (3) are organic and inorganic bases, such as pyridine, üfriäthylamin, Ν, Η-dimethylaniline and substituted Pyridine et al. Excess liquid bases can be used in place of a solvent. Stronger bases favor the Formation of the bi (sulfonylated) product compared to the mono- (sulfonylated) Product.

Step (4-) is a partial hydrolysis of the intermediate bis-compounds. This basic. Hydrolysis runs with it

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- ir-

high yield using a strong base, like potassium hydroxide in methanol. Optionally, the starting compound of stage (3) directly into the product of stage (4) be converted with the help of a mono (sulfonylation) reaction using one or more equivalents of the base. This reaction is favored by a base that is weaker than pyridine, such as 3-bromopyridine.

Step (5) is carried out using conventional oxidation processes, e.g. with hydrogen peroxide in acetic acid, sodium metaperiodate among others carried out. The sulfoxide compound (n = 1) is formed when equimolar amounts of the oxidizing agent and the Reaction partner are applied, while the sulfone (n = 2) directly when using two moles (or a small excess) of the oxidizing agent are formed per mole of reactants.

The herbicidal activity of the compounds according to the invention was determined by tests on greenhouse plants. Both pre-emergence and post-emergence activity was measured Emergence determined in a direct investigation against a selected group of weeds and grasses. the The following weeds are examples of these attempts were applied.

Grasses:

Giant foxtail (Setaria faberij chicken millet (Echinochloa crus-galli) Cinquefoil (Digitaria ischaemum) common couch grass (Agropyron repens) yellow cypergrass (Cyperus esculentus)

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broad-leaved plants:

curved back foxtail (Amaranthus retroflexus) purslane (Portulaca oleracea) wild mustard (Brassica kaber)
Bindweed (Convolvulus arvensis)

The compounds to be tested were dissolved in a small amount of acetone or another suitable solvent and then diluted with water to a concentration of 2000 ppm. Equal proportions of this were diluted to a final concentration of 500 ppm. SDmI of this solution were added to a 15 cm pot containing the weed seeds, corresponding to a concentration of 22.4 kg / ha. The use of 20 ml of solution corresponding to a concentration of 5 _f 6 kg / ha. All subsequent irrigation was done from the ground. Two pots were used per treatment. Two to three weeks after the treatment, the values were determined and recorded as the percentage death of the species in question before emergence, compared with untreated control plants.

To determine post-emergence activity, the same weed mixtures grow up to the two to three weeks Grasses about 2.5 to 7.6 cm high and broadleaf weeds about 2.5 to 3.8 cm high had achieved. They were about -10s. or until the leaf surface is well wetted with the above 2000 ppm containing solution sprayed.

The values were determined two to three weeks after the treatment and as a percentage of those concerned Species, compared with untreated control plants, noted.

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The compounds according to the invention are herbicides with a broad spectrum of activity. The mechanism by which this herbicidal effectiveness is brought about has not yet been fully clarified. The compounds according to the invention However, they also show various effects of modifying plant growth. A modification of the Plant growth as indicated here consists in all deviations from natural development, e.g. B. defoliation, stimulation, development inhibition, delay, Dehydration, appearance of giant or. Dwarf growth, Control, etc. Plant growth control activity is generally observed when the Compounds according to the invention interact with certain processes within the plant. If those Processes are essential, the plant will die if it is treated with a sufficient amount of the compound. However, the way in which plant growth is modified varies with different plants.

For application to the plants, the compounds can be finely divided and suspended in any conventional aqueous medium will. Furthermore, agents to facilitate spreading, wetting agents, tackifiers and other auxiliaries can be added. Dry powders can be used as such or diluted with inert substances such as diatomaceous earth can be used as a dusting agent.

The agents according to the invention are applied to the plants or the ground is covered with it if pre-emergence control is desired. The application is with Using conventional spray devices, dust devices and the like carried out. The amount applied is generally However, 0.56 to 22.4 kg / ha can also be higher or lower depending on the particular application.

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The compounds according to the invention can advantageously be used together with other known herbicides in order to expand the spectrum of those weeds _/ which are controlled by the herbicides according to the invention or for better control of a weed which is not adequately controlled by specific individual compounds according to the invention. Known herbicides include phenoxy herbicides e.g. B. 2,4-D, 2,4,5-T, Silvex and the like, carbamatherbicides, thiocarbamate and dithiocarbamate herbicides, substituted ureas such as diuron, monuron and the like, triazines, for example, simazine and atrazine, chloroacetamide and chlorinated aliphatic acids, chlorinated benzoic acid and phenylacetic acid, paraquat, nitraline and the like, In addition, herbicidal agents containing compounds according to the invention, additionally nematicides, fungicides, insecticides, fertilizers, trace elements, agents for improving the soil and other plant growth regulators and the like can contain.

-ΪΟ- 030032/0728

The invention is illustrated by the following examples. Unless otherwise stated, parts are always to be understood as parts by weight.

Example i

2-chloro-6-trifluoromethylnitrobenzene

A mixture of 25 g (0.12 mol) of 3-chloro-2-nitrobenzoic acid and 42.1 g (0.389 mole) of sulfur tetrafluoride was heated in a Hastelloy B-reaction vessel for 16 h at 130 ⁰ C. That
unreacted sulfur tetrafluoride was removed u ^ cl the residue in a solution of 6.2 g of sodium fluoride and
Poured 200 ml of water. Sodium carbonate was added to pH 8 and the basic mixture was extracted with ether. The combined ether extracts were washed with water and dried. After removal of the drying agent and the ether, a product was obtained which, by chromatography over silica gel with petroleum ether (boiling point 30 to 60 ° C.) / ether, was obtained
Eluent has been purified.

Analysis: _ % C% H % N

Ber. for C _n H _x / 3

Found:

The following compound was made using the same general procedure:
5-chloro-2-trifluoromethylnitrobenzene (liquid)

Example 2

37 , 37 1 , 34 6th , 21 36 ,8th 1 , 2 5 , 9

5-chloro-2-trifluoromethylaniline

Aqueous ammonium sulfide (60 g, 52 to 60%) was added with stirring to a 75 ° C ethanolic solution of 22.6 g (0.1 mol) 5-chloro-2-trifluoromethylnitrobenzene was added dropwise and the resulting The mixture was heated for 4 h at a bath temperature of 97 ° C. and then cooled to room temperature. The reaction mixture was poured into water and the organic product with diethyl ether

030032/07 2 8

BATH ORIGINAL

extracted. To. Washing and drying of the ether solution, the ether was evaporated to give the desired product. The following connection was made in the same way:
2-chloro-6-trifluoromethylaniline.

Example 3

2-bromo-4-thiocyanoaniline

To a cold (0 to 5 ° C) solution of 20.6 g (0.12 mol) o-bromoaniline and 29.2 g (0.36 mol) sodium thiocyanate in 300 ml of methanol was stirred into a solution of 19.5 S (0.122 mol) of bromine in 75 ml of methanol, which was mixed with sodium bromide was saturated, added dropwise. The solution was stirred 1 h after the addition of the bromine and then poured into 2 l of water and neutralized with sodium carbonate. The resulting plague * was filtered off, washed with water and dried, Ip 74 Ms 79 ° O.

The following compounds were made using the same general procedure:

2-chloro-4-thiocyanoaniline, Ep 63 to 65 ° G 2-fluorine-4-thiocyanoaniline, Ip 34-t> is 35 ° C 2,5-dichloro-4-thiocyanoaniline, I ¹ P 111 to 115 ° 0 2 , 3-DiChIOr-I - thiocyanoaniline, Ep 132 to 137 ° C 2-iodo-4-thiocyanoaniline, Ip 92 to 93 ° O

Example 4

2-bromo-4-methylthioaniline

A solution of 11.5 S (0.05 moles) of 2-bromo-4-thiocyanoaniline and 1.23 g (0.025 mol) of sodium cyanide in 100 ml of methanol was stirred overnight at room temperature. Then it became 0.025 Mol sodium cyanide was added and the reaction mixture was heated

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and held at reflux temp era door for 2 h and then cooled ^{to 0 to 5 0 O.} Methyl iodide was added and stirring continued. Thin layer chromatography showed a product point. The product was isolated by extraction with methylene chloride. 8.4 g were obtained.

The following additional compounds were made using the same general procedure:

2-C8ilor-4-methylthioaniline (oil)
2,3-dichloro-4-methylthioaniline (solid)

Example 5

2-chloro-4-ethylthioaniline

A solution of 40 g (0.22 mol) of 2-chloro-4-thiocyanoaniline in 250 ml of ethanol was added with stirring to a solution of 5% S (Oj22 mol) of sodium sulfide nonahydrate in 110 ml of water, and the mixture was heated to 50 ° for 45 minutes warmed up. Then 36.6 g (0.22 mol) of ethyl iodide were added and the mixture was stirred for a further 2 hours at 50 ° C. and then overnight at room temperature. The reaction mixture was poured into 3 l of water and the product extracted with ether. The combined organic extracts washed with water and dried over CaSO ^. After removal of the drying agent and solvent, 2-chloro was obtained

4-ethylthioaniline as an oil.

*became

The following other compounds were made after the same general procedure made:

2_Bromo-4-ethylthioaniline (oil)
2-fluoro-4-ethylthioaniline (oil)
2-chloro-4-isopropylthioaniline (oil) 2,5-dichloro-4-ethylthioaniline (oil) 2,3-dichloro-4-methylthioaniline (oil) 2-iodo-4-ethylthioaniline (oil)

Ö3OO32 / D728

BATH ORIGINAL

Example 6

2-chloro-4-tert-butylthioaniline

A solution of 36.9 S (0.120 mol) of 2-chloro-4-thiocyanoaniline in 100 to 200 ml of ethanol was added with stirring to a solution of 48.04 g (0.20 mol) of sodium sulfide nonahydrate in 100 ml of water, and the mixture Heated to 50 ^° C. for 90 min.

The cooled reaction mixture was poured into 1 l of water and dilute hydrochloric acid was added to a pH of 6.0 to 6.5. The product was extracted with ether which Ether washed with water and then dried. After removing the drying agent and ether, 2-chloro-4-mercaptoaniline was obtained as yellow oil.

22.86 g (0.18 mol) of dimethylcyclohexylamine in 125 ml of methylene, chloride were added with stirring to a solution of 27.0 g (0.17 mol) of 2-0hlbr-4-mercaptoaniline and 22.86 g (0.18 mol) of tert-butyl bromide added dropwise in 125 ml of methylene chloride and the mixture Stirred for about 68 hours at room temperature. Then a further 2.3 g of dimethylcyclohexylamine and 2.5 g (0.018 mol) of tert-butyl bromide were added added and stirred further overnight. The reaction mixture was poured into water and the product with methylene chloride extracted. The combined extracts were washed with dilute hydrochloric acid and water and dried. To Removal of the drying agent and methylene chloride gave impure 2-chloro-4-tert.-butylaniline as a beige solid.

Example 7

2-Bromo-4-methylthiochloromethanesulfonanilide

0.03 moles of chloromethanesulfonyl chloride were added to one with stirring cold (0-5 ° 0) solution of 6.2 g (0.028 mol) of o-2-bromo-4-methylthioaniline in 20 ml of pyridine was added dropwise. The solution was over Stirred overnight at room temperature, poured into ice water and poured in 12N hydrochloric acid with stirring, with 2-bromo-4-methylthiochloromethanesulfonanilide emerged as oil. A methylene

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30Q2880

The chloride solution of the oil was washed with water and dried. After removing the drying agent and the methylene chloride, a red oil was obtained. Crystallization from methylene chloride-hexane gave a red-tan-colored solid, mp 72 to 85 ^° C.

Analysis:% C% H% N

Ber. for OgH ₀ BrClNO ₂ S ₂ : 29.0 2.7 4.2

Found: '29.6 2.8 4.3

The following compounds were made using the same general procedure:

2-chloro-4-methyithiochloromethanesulphonanilide, m.p. 79 to 82 ⁰ C 2-chloro-4-methylthiomethanesulphonanilide, m.p. 128 to 133 ° G 2,3-dichloro-4-methylthiochloromethanesulphonanilide, m.p.

2,3-dichloro-4-methylthiomethanesulfonanilide, m.p. 165-170 ° C 4-methylthiomethanesulfonanilide, m.p. 107.5-110 ° 0.

Example 8

2-Bromo-4-methylthiomethanesulfonanilide

To a mixture of 7.6 g (0.035 mol) of 4-methylthiomethanesulfonanilide, 0.35 S iron filings and 50 ml of glacial acetic acid were added dropwise with stirring 5> 6 g (0.035 mol) of bromine. The reaction mixture was heated to 110 ° 0 for 2 h, cooled and poured into 300 ml of water. The oily product was extracted with methylene chloride, the combined extracts washed with water and dried. After removing the drying agent and the solvent the product was obtained as an oil. The product crystallized from hexane and the tan solid became from hexane-methylene chloride recrystallized to give a brown solid, mp 100 to 110 ° 0. ·

Analysis:% C% H% N

Ber. for CgH ₁₀ BrNO ₂ S ₂ : 32.4 3.4 4.7

Found: 33.1 3.4 4.7

-3fr-

- 41-

Example ° j

2-chloro-4-ethylthiochloromethanesulfonanilide

4.0 g (0.027 mol) of chloromethanesulfonyl chloride were added dropwise with stirring to a solution of 5.0 g (0.027 mol) of 2-chloro-4-ethylthioaniline in 6.4 g (0.041 mol) of 3-bromopyridine, and the mixture was added overnight Room temperature stirred. The reaction mixture was taken up in 200 ml of methylene chloride and 200 ml of 20% dilute hydrochloric acid were added, the layers were separated and the methylene chloride solution was washed three times with 200 ml of 10% dilute hydrochloric acid and then dried over OaSO ^. After removing the drying agent and the solvent, the product was obtained as a reddish oil. This was taken up in hexane and cooled. Mp 70 was obtained 2-0hlor-4-äthylthiochlormethansulfonanilid, to 72 ⁰ G.

Analysis; Ber. for Og Gef .:

Other compounds made using the same general procedure are:

2-Bromo-4-ethylthiochloromethanesulfonanilide, Pp 63 to 65 0 2-chloro-4-isopropylthiochloromethanesulfonanilide, Ep 50 to 53 2-fluoro-4-ethylthiochloromethanesulfonanilide, mp 78 to 81 ° 0 2-chloro-4-ethanesulfonanilide, 101-ethylthiomide 103 ° C 2-chloro-4-isopropylthiomethanesulfonanilide, mp 78 to 80 ° 0 2-chloro-4-ethylthioethanesulfonanilide, mp 64 to 66 ⁰ O 2-chloro-4-isopropylthioethanesulfonanilide, mp 52 to 53 ° O 2-bromo-4 -äthylthiomethansulfonanilid, mp 83 to 85 ° C 2-fluoro-4-äthylthiomethansulfonanilid, mp 89 to 91 ° C 2,5-dichloro-4-äthylthiomethansulfonanilid, mp 143-144 ° 0 2-fluoro-4-äthylthioäthansulfonanilid, mp 77 to 79 ° O 2-fluoro-4-methylthioethanesulfonanilide, m.p. 69 to 71 ° 0 2-fluoro-4-methylthiomethanesulfonanilide, m.p. 133 to 135 ° C

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G Ά. Ξ S. 36 , 0 3, 7th 4th 36 , 3 3, 5 4, Ä , 7 , 7

3Q0288Q

- TG "-

- 4S-

2-Pluor- ^z l ~ meth.yltliiochlormetliaiisulfonaiilid, Pp 88 to 90 ⁰ G 2-Bromo-4-isopropylthiomethansulfonanilid, Ip 82 to 84 0 2-Bromo-4-isopropylthioäthan sulfonanilid, Mp 62 to 64 ⁰ G 2-Brom- 4-ethylthioethanesulfonaiilide, I ¹ P 77.5 to 79.5 ° C 2-ITuor-4-isopropylthiochlo: methanesulfonanilide (oil) 2-bromo-4-tert.-butyl thiochloromethanesulfonanilide, Pp 100 bis

2-iodo-4-ethylthiochloromet] aaiisulforLanilid, Ip 74 to 76 ⁰ G 2,5-dichloro-4-ethylthiochlo: methanesulfonanilide, Ip 132,5 bis

2,5-dibromo-4-ethylthiochloromethanesulfonanilide, Ip 189 bis

2,5-dibromo-4-isopropylthiochloromethanesulfonanilide, Ip 132 bis

2,3-Oichlor-4-äthylthiochlormethansulfonanilid, Ip 92 to 94 ⁰ C 2-bromo-4-isopropylthiochlormethansulfonanilid, Ip 56 to 59 ° C.

Example 10

N-chloromethylsulfonyl-2-chloro-4-ethylthiochloromethanesulfonanilide

60 g (0.4 mol) of chloromethanesulfonyl chloride were added dropwise with stirring to a cold (0 to 5 ° 0) solution of 15.1 g (0.081 mol) of 2-chloro-4-ethylthioaniline in 104 ml of pyridine stirred at room temperature and poured with stirring into ice-water and 12 η hydrochloric acid. the product was extracted into GHpOl _2, washed with water and dried. After removal of the drying agent and solvent gave the crude product. when Ghromatographieren over silica gel with methylene chloride as eluent to give the pure product as an oil.

Example 11_

2-chloro-4-ethylthiochloromethanesulfonanilide

A solution of 7.2 g (0.017 mol) of N-Ohlormethyisulforiyl-2-

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chlorine ^ ethylthiochloromethanesulfonanilide and 2.9 g of 85% strength Potassium hydroxide in methanol was about 3 days at room temperature touched. The solvent was evaporated, the residue taken up in hot water, filtered and the Piltrat acidified with 12 η hydrochloric acid. The product was filtered off and air dried.

Example 12

2-chloro-4-methanesulfinylchloromethanesulfonanilide

To a solution of 1.8 g (0.0061 mol) of 2-chloro-4-methylthiochloromethanesulfonanilide In 20 ml of glacial acetic acid, 0.061 mol of 30% strength hydrogen peroxide were added. The solution was over Stirred overnight at room temperature, heated immediately to reflux temperature and treated with water. That aqueous mixture was extracted with methylene chloride, washed with water and dried. After removing the desiccant and the solvent gave a yellow oil. This crystallized from hexane to a white solid, Pp 99 to 110 ° G.

Analysis: * % C % H%

C. % H 31 ₅ 8 3, O 31 ,8th . 3, O

Ber. for G ₈ HnOl ₂ NO ₃ S ₂ : 31.8 3.0 4.6

Found: - 31.8. 3.0 4.7

The following compounds were made using the same general procedure:

2-Bromo-4-methanesulfinylchloromethanesulfonanilide, Ip 108 bis

2-Bromo-4-ethanesulfinylchloromethanesulfonanilide, Jp 157

2,3-dichloro-4-methanesulfinylchloromethanesulfonanilide, Sp up to 163 ° 0

2-chloro-4-methanesulfinyl methanesulfonanilide, sp 162 to 165 ° 0

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2-chloro-4-ethanesulphinylmethanesulphonanilide, Pp 121 to 123 ° C 2-chloro-4-ethanesulphinylethanesulphonanilide, Pp 109 to 112 ° 0 2-bromo-4-ethanesulphinylmethanesulphonanilide, Jp 119 to 121 ⁰ O a-pluorine - ^ - ethanesulphinyl bhaiisulfonanilide, Pp 122 to 124 ° C 2-Pluoro-4-ethanesulfinylethanesulfonanilide, Pp 128 to ⁰ ^ -Pluor ^ -methanesulfinyläthansulfonanilid, Pp 111 to 113 ° 0 2-Bromo-4-isopropylsulfinylmethanesulfonanilid, Pp 104 to 106 ⁰ -4-isopropylsulfinylethane sulfonanilide, Pp 118 to 120 ⁰ O 2-Pluoro-4-methanesulfinylmethanesulfonanilide, Pp 149 to 2-bromo-4-ethanesulfinylethanesulfonanilide, Pp 113 to 115 ⁰ C 2-pluoro-4-methanesulfinyl chlorine thanesulfonanilide, Pp 113-115 118 to

2-fluorine-4-isopropylsulfinylchloromethanesulfonanilide, pp 118 bis

2-Bromo-4-tert-butylsulfinylchloromethanesulfonanilide, pp 112 to °

2-iodo-4-ether-sulfinylchloromethane-sulfonanilide, pp 165 to 167 ° 0 2,5-dichloro-4-ethanesulphinyl methanesulphonanilide, pp 149 to 150 ° 0 2,5-dichloro-4-ethanesulfinylchloromethanesulfonanilide, Pp I5I bis

2,3-I'icnlor-4-ethanesulfinylclllormeth.ansulί ■ onanilid, pp 118 bis

2-chloro-4-tert-butylthiochloromethanesulfonanilide, pp 89 to 90 ° 0.

Example 13

2-öb ■ lor-4-methanesulfonylcb ■ loΓIIlethanesulfonanilid

To a solution of 3.0 g (0.0101 mol) of 2-chloro-4-meth.ylthiochloromethanesulfonanilide in glacial acetic acid (30 ml), 0.0405 mol of 30% strength hydrogen peroxide was added with stirring. The solution was 2.5 h. heated to reflux, added water and cooled the mixture. The resulting precipitate was filtered off, washed with water and dried. A white Peststoff, Pp 172 to give to 180 ⁰ C.

Analysis: % 0 % H % _N

Ber. for O ₈ H ₉ Ol ₂ NO ₄ S ₂ : 30.2 2.8 4.4

Found: 30.2 2.8 4.4

030032/0728

Other compounds made using the same general procedure are:

2-Bromo-4-methanesulphonylchloromethanesulphonanilide, m.p. 156 to 168 ⁰ O 2-Bromo-4-ethanesulphonylchloromethanesulphonanilide, m.p. 120 to 122 ⁰ O 2-chloro-4-eethanesulphonylchloromethanesulphonanilide, m.p. 1.46 to 148 ° 0 2-chloro-4- isopropylsulfonylchlormethansulfonanilid, mp 146 to '149 C ⁰ 2-I "luor-4-äthansulfonylchlormethansulfonanilid, mp 143-144 ⁰ O 2-0hlor-4-methansulfonylmethansulfonanilid, mp 167 isopropylsulfonylmethansulfonanilid 2-0hlor-4 to 169 ° 0, mp 142 to 144 ° 0 2-chloro-4-ethanesulphonylethanesulphonanilide, m.p. 92 to 94 ⁰ O 2-chloro-4-isopi? Opylsulphonylethanesulphonanilide, m.p. 115 to 117 ° 0 2-bromo-4-methanesulphonylmethanesulphonanilide, m.p. 170 to 171.5 ° C 2 -Bromo-4-ethanesulfonylmethanesulfonanilide, m.p. isopropylsulfonylmethansulfonanilid, mp 133 to 135 ° O 2-bromo-4-isopropylsulfonyläthansulfonanilid, m.p. 110 to 112 ⁰ G ^ -fluoro ^ -methansulfonylchlormethansulf onanilid, mp 153-155 ⁰ G 2-fluoro-4-isopropylsulfonylchlo: methanesulfonanilide, m.p. 140 to 142 ⁰ O

2-bromo-4-tert-butylsulfonylchloromethanesulfonanilide ,. Mp to 17O ⁰ O 2,5-dichloro-4-ethanesulphonylmethanesulphonanilide, m.p. 171 to 174 ⁰ C 2,5-dichloro-4-ethanesulphonylchloromethanesulphonanilide, m.p. to 183 ° C 2,3-dichloro-4-ethanesulphonylchloromethanesulphonanilide, "Mp 164 to 166 ° 0 2-fluoro-4-methansulfonylmethansulfonanilid, m.p. 181 to 183 ⁰ g of 2-bromo-4-äthansulfonyläthansulfonanilid, mp 88 to 91 ⁰ O 2-iodo-4-äthansulfonylchlormethansulfonanilid, m.p. 130 to 132 ⁰ G.

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62XXIV

Claims (1)

Claims S (O) _n R ¹ » in which E is an alkyl group with Λ to 4 carbon atoms or a monohalomethyl group, R ^{1 is} an alkyl group with Λ to 4 carbon atoms ,. A is a halogen atom or a trifluoromethyl group, B is a hydrogen or halogen atom and η = O to 2, provided that when A is an irifluoromethyl group, B is a halogen atom, as well as their agriculturally suitable salts. (2) Compound according to claim 1, characterized in that R contains a carbon atom. 2-Bromo-4-ethanesulfinylchlo: n-ethanesulfonanilide (4) 2-Bromo-4-ethanesulfonylchlo; rmethanesulfonanilide 2-chloro-4-methanesulfinylchloromethanesulfonanilide (6) 2-chloro-4-methanesulfonylchloromethanesulfonanilide (7) 2-chloro-4-ethanesulfinylchloromethanesulfonanilide. 030032/0728 (8) 2-chloro-4-ethanesulfonylclilormet] iansulfonaiilid. (9) means for modifying the growth of higher plants, characterized in that it is as Active ingredient contains a compound according to claims 1 to 8, optionally together with a customary carrier and / or other Additives. 62XXIV 030032/0728