CA1134386A - Substituted-4-alkylthioalkanesulfonanilides and derivatives thereof - Google Patents

Abstract

Abstract of the Disclosure Alkane- and monohaloalkane-sulfonanilides sub-stututed in the para position by alkylthio, alkysulfinyl and alkylsulfonyl groups and additionally substituted by halogen and optionally by trifluoromethyl and agriculturally acceptable salts thereof are useful herbicides.

Description

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SULFONANILIDES AND DERIVATIVES THEREOF
This invention relates to halo-subs~ituted methane-and chloromethane-sulonanilides substituted in the para po-sition by alkylthio, a]kylsulfinyl or alkylsulfonyl groups S and optionally substituted by trifluoromethyl and ~o agri-culturally acceptable salts thereof. ~he compounds of the invention are active herbicidal agents and plant growth modi-fying agents. The invention also relates to herbicidal for- ;
mulations containing said compounds and to the use of the com-pounds to regulate and control the growth of higher plants.
More particularly, the invention relates to com~
pounds of the formula HNSO R

A ~ 2 B

S () wherein R is an alkyl group containing from 1 to 4 (preferably 1 to 2) carbon atoms or monohalomethyl ~chloromethyl, bromo-methyl, iodomethyl or fluoromethyl), R' is an alkyl group containing from 1 to 4 carbon atoms, A is halogen or CF3, B
is hydrogen or halogen and n is 0-2, provided that when A is CF3, B is halogen, and agriculturally acceptable salts there-o, to compositions for killing and modifying the growth ofhigher plants consisting essentially of a compound of the in-vention dispersed in an extending medium, to the use of the compounds o the invention to modify the growth of higher : -,, ~

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2 -plants and to kill higher plan~s and to processes for the preparation of the compounds of the invention. The invention is particularly useful in the selective herbici~e area to con-trol particular weed species in the presence of specific S crops (with little or no damage to the crops), for example to control such weeds a~ rhizomatous Johnsongrass, annual grasses, yellow nutsedge and/or purple nutsedge in such crops as cotton or soybeans.
The compounds of formula I wherein R is ~CH2Cl and A is chlorine or bromine form a preferred class, and those compounds of formula I wherein R is -CH3 and A is chlorine or bromine constitute a second preferred class, due in both cases to their highly useful activity.
The compounds of formula I above can form salts, i.e. compounds of the above formula wherein H is replaced by an agriculturally acceptable cation. These are generally metal, ammonium and organic amine salts and can be prepared by treating the acid-form compound with an appropriate base under mild conditions. Among the metal salts of the invention are alkali metal (e.g. lithium~ sodium and potassium), alka-]ine earth metal (e.g. barium, calcium and magnesium) and i'~
heavy metal (e.g. 7inc and iron) salts as well as other metal salts such as aluminum. Appropriate bases for use in pre-paring the metal salts include metal oxides, hydroxides, car-bonates; bicarbonates and alkoxides. Some salts are alsoprepared by cation exchange reaction (by reacting a salt of 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, . . i: . , ; .. .. ,. P
. :,: ~ ... ... ,.:.:: . . :

as well as those having a mixture of these types of struc-tures. The amines useful in preparing the salts of the in-vention can be primary, s~condary or tertiary and preferably contain not more than 20 carbon atorns. Such amines include, for example, morpholine, methyl cyclohexylamine, glucosamine, amines derived from fatty acids, etc~ The amine and ammoni-wm salts can be prepared by reacting the acid form with the appropriate organic base or ammonium hydroxide. Any of the salts of the types set out above are agriculturally accept-able, the one chosen depending upon the partlcular use andupon the economics of the situation. Of particular utility are the alkali metal, alkaline earth, ammonium and amine salts.
The salts of the invention are frequently formed by reacting the precursors in aqueous solution. This solution can be evaporated to obtain the salt of the compound, u~ual-ly as a dry powder. In some cases, it may be more convenient to use a non-aqueous solvent such as alcohols, acetone, etc.
The resulting solution is then treated to remove the solvent, for example, by evaporation under reduced pressure.
The compounds of the invention can be prepared ac-cording to the reaction sequence outlined below.

SCN SR ' ~3~1 NHS02R NHS02R N (S02R) 2 B ~J -- t~J ( 4 ) B~
S(O)nR' SR' . , - , ~ .

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4 -The reaction of step (1) involves the formation of the substituted 4-thiocyanoanilines from the corresponding substituted anilines (which are known or for which the methods of preparation are well known) generally by conventional means.
~he reaction of step (2) involves the formation of the substituted 4-alkylthioanilines directly from the corres~
ponding 4-thiocyanoanilin0s. This reactio~ can be carried out utilizing various conventional techniques. For example, the thiocyano moiety can be alkylated in an alcoholic sodium cyanide solution. Pre~erably the alcohol has the same hydro-carbon residue as the desired al~yl group. Alternatively, a sodium mercaptide can be first formed from the thiocyano moiety and it can then be alkylated utilizing an alkylating agent such as an alkyl halide (methyl iodide).
Step (2) can also be carried out by first converting the sodium mercaptide to the free mercaptan by acidification.
The mercaptan is then reacted with an alkylating agent such as an alkyl halide (methyl iodide~ in the presence of an or-ganic base. Suitable organic bases are tertiary amines such as triethylamine~ dimethylcyclohexyl amine, pyridines and the like~ This reaation is ordinarily preferred when the alkyl halide is a tert-butyl halide (tert-butyl bromide).
The reaction of step (3) is the methanesulfonylation or chloromethanesulfonylation of the product of step (2) with 25 two or more equivalents of methanesulfonyl chloride or chloro-methanesulfonyl chloride in the presence of a base. If one to two equivalents of the sulfonyl chloride are used, a mix-ture of mono- and bis-(sulfonylated) product can be obtained ~' which may be used in step (4). If two or more equivalents ;~

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of the chloride are reacted, the bis(sulfonylated) product is favored. Suitable bases for the reaction of step (3) are organic or inorganic bases such as pyridine, triethylamine, N,N-dimethylaniline and substituted pyridine, and the like.
Liquid bases in excess can be used to eliminate the need for solvent. Stronger bases promote the formation of bis-(sulfonylated) product over the mono(sulfonylated) product.
Step t4) is the partial hydrolysis of the inter-mediate bis compounds. This is a high yield base hydrolysis reaction using a strong base such as potassium hydroxide in methanol. Alternatively, the precursor of step (3) can be conve~ted directly to the product of step (~) by means of a mono(sulfonylation) reaction using one or more equivalents of base. This reaction is favored by a base weaker than pyri-dine, such as 3-bromopyridine.
Step (5) is carried out using conventional oxida-tion methods such as hydrogen peroxide in acetic acid, sodium metaperiodate and the like. The sulfoxide compound (n=l~ is produced when equimolar amounts of the oxidizing agent and the reactant are utilized, whereas the sulfone (n=2) is pre-pared directly utilizing 2 moles (or a slight excess) of the oxidizing agent per mole of the reactant.
The herbicidal activity of the compounds of the in-vention has been determined using screening tests against greenhouse plantings. Both pre- and post-emergence activity are determined in a direct screen against selected weed species~ The following weeds are examples of weeds which are used for these tests.

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- 6 - ~ ~343 Grasses:
Giant foxtail fSeta~ie ~aheri) Barnyardgrass fEchinoch~oa cru~-gaZZi) Crabgrass (Digita~ia isahaemum) Quackgrass (Agropyron repens) Yellow nutsedge (Cyperu~ es~u~entu~) Broadleaves:
Pigweed fAmaranthus retro~Ze~us) Purslane (Por~u~aca oleracea) Wild mustard fBra~sica kaber) Field bindweed (ConvoZvu~s arvensis) The test chemicals are dissolved in a small amount of acetone or other suitable solvent and then diluted with water to give a concentration of 2000 ppm. From this concen-tration aliquots are diluted to give a final concentration of 500 ppm. Eighty ml. of this solution are added to a 6-inch pot containing the weed seeds to give a concentration equiv-alent to 20 lb/acre. Use of 20 ml. of said solution gives a concentration equal to 5 lb/acre. All subsequent waterings are made from the bottom. Two pots are used per treatment.
Data are taken 2 to 3 weeks after treatment and recorded as percent pre-emergence kill for each species compared to the untreated controls.
To assess post-emergence activity, the same weed mixtures are allowed to grow from two to three weeks until the grasses are approximately l to 3 inches and the broad-leaves l to l-l/2 inches tall. They are sprayed for approxi-mately 10 seconds or until good wetting of the leaf surfaces ' occurs with a 2000 ppm solution as described above.

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Data are taken two to three weeks after treatment and recorded as percent kill for each species compared to the untreated controls.
The compounds of this invention are broadly active as herbicides. The mechanism(s) by which this herbicidal ac-tivity is effected is not presently known. I-lowever, the com-pounds of this invention also show various types of plant growth modifying activity. Plant growth modification as de- ;
fined herein consists of all deviations from natural develop-ment, for example, defoliation, stimulation, stunting, re-tardation, desiccation, tillering, dwarfing, regulation and the like. This plant growth modifying activity is generally observed as the compounds of the invention begin to interfere with certain processes within the plant. If these processes are essential, the plant will die if treated with a suffi-cient dose of the compound. However, the type of growth modi-fying activity observed varies among types of plants.
For application to plants, the compounds can be finely divided and suspended in any of the usual aqueous media. In addition, spreading agents, wetting agentst stick-ing agents or other adjuvants can be added as desired. ~ry powders, as such or diluted with inert materials such as di-atomaceous earth, can likewise be used as dusts for this pur-pose. The preparations are coated on the plants or the ground is covered when pre-emergence control is desired. Ap-plication rates are at 0.5 to 20 lbs/acre in general, but may be increased or reduced according to individual circumstances of use '`''P

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The compounds of the invention may be advantageous-ly combined with other known herbicides to broaden or maxi-mize the weed spectrum controlled by herbicidal compositions of this invention or to better control a weed not well con-trolled by specific compounds of the invention. Amony theseother known herbicides are phenoxy herbicides, e.g. 2,~-D, 2,4,5 T, silvex and the like, carbamate herbicides, thiocar-bamate and dithiocarbamate herhicides, substituted urea herbicides, e.g. diuron, monuron and the like, triazine herbicides, e.g. simazine and atrazine, chloroacetamide and chlorlnated aliphatic acid herhicides, chlorinated benzoic and phenylacetic acid herbicides such as chloramben and o$her herbicides such as trifluralin, paraquat, nitralin and the like. Furthermore, herbicidal compositions containing com-pounds of the invention may contain, in addition, nematicides,fungicides, insecticides, fertilizers~ trace metals, soil con-ditioners, other plant growth regulators and the like. Such combinations are clearly envisioned in this invention.
The following examples are given for the purpose of further illustrating the present invention but are not intend-ed, in any way, to be limiting on the scope thereof. All parts are given by weight unless otherwise specifically noted.
Example 1 2-Chloro-6-trifluorometh~ nitrobenzene.
A mixture of 3-chloro-2-nitrobenzoic acid ~25 g., 0.12 mole) and sulfur tetrafluoride (42~1 g., 0.389 mole) is heated at 130 C. in a Hastelloy B reaction vessel for 16 hours. The unreacted sulfur tetrafluoride is vented through k - -, ~ ~ ~3~3~
_ 9 a scrubber, and the residual ma-terial is poured into a solu-tion of sodium fluoride (6.2 g.) and water (200 ml.). Sodium carbonate is added to pH 8 ! and the basic mixture is ex-tracted with ether. The combined ether extracts are washed with water and dried. Removal of the drying agent and ether gives product that is purified by chromatography on silica gel with a petroleum ether tb.p. 30-60 C.)~ether eluant.
Analysis: %C %~I %N
Calculated for C7H3ClF3NO~: 37.37; 1.34; 6.21 10 Found: 36.8; 1.2; 5.9.
The following compound is made using the same general method:

5-chloro-2-trifluoromethylnitrobenzene, a liquid.
Example 2 5-Chloro-2 trifluorometh laniline Aqueous ammonium sulfide (60 g., 52-60~) is added dropwise to a warm (75 C.), stirred ethanol solution of 5-chloro-2 trifluoromethylnitrobenzene (22.6 g., 0.1 mole) and the resulting mixture is heated for four hours at a heating bath temperature of 97 C. and then allowed to cool to room temperature. The reaction mixture is poured into water, and the organic product is extracted with diethyl ether. After washing and drying the ether solution, the ether is removed by evaporation to give the desired product.
The following compollnd can be made in the same general way:
2-chloro-6-trifluoromethylaniline.

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2-Bromo-4-thiocyanoaniline ... . _ To a cold (0-5 C.), stirred solu-tion o~ o-bromo aniline (20~6 g., 0.12 mole) and sodium thiocyanate ~29.2 g., 0.36 mole) in methanol (300 ml.) is added dropwise a solution of bromine (19.5 g., Q.122 mole) in methanol (75 ml.) satu-rated with sodium bromide. The solution is stirred for 1 hour following the addition of the bromine and then poured into water (2 liters) and neutralized with sodium carbonate.
The resulting solid is ~iollected, washed with water and dried, m.p~ 74-79 C.
The following compounds are prepared using the same general method: ;
2-chloro-4-thiocyanoaniline, m.p. 63-65 C~
2 fluoro-4-thiocyanoaniline, m.p. 34-35 C.
2,5-dichloro-4-thiocyanoaniline, m.p~ 111-115 C.
2,3-dichloro-4-thiocyanoaniline, m.p. 132-137 C.
2-iodo-4-thiocyanoaniline, m.p. 92-93 C.

Exam~le 4 2-Bromo-4-methylthioaniline .
A solution of 2-bromo-4-thiocyanoaniline (11.5 g., 0.05 mole) and sodium cyanide (1.23 g., 0.025 mole) in meth-anol ~100 ml.) is stirred at room temperature overnight. So-dium cyanide (0.025 mole) is then added and the reaction heated at reflux 2 hours and then cooled (0-5 C.). Methyl iodide is added and stirring continued. Thin layer chroma-tography shows one prcduct spot. Product is recovered by ex-traction with methylene chloride, 8-.4 ~.

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~3~ 6 The following additional compounds are p~epared utilizing the same general method:
2-chloro-4-methylthioaniline, an oil.
2,3-dichloro-4-methylthioaniline, a solid.
Example 5 2-Chloro-4-ethylthioan line.
, A solution of 2-chloro-4-thiocyanoaniline (40 g., 0.22 mole) in ethanol (250 ml.) is added to a stirred solu-tion oE sodium sulfiae nonahydrate (58.5 g., 0.22 mole) in water (110 ml.) and the mixture is warmed (50 C.) for 45 minutes. Ethyl iodide (36.6 gJ, 0.22 mole) is added and stirring is continued for 2 hours at 50 C. and then at room temperature overnight. The reaction is poured into water (3 liters) and the product extracted with ether. The combined extracts are washed with water and dried (CaSO4). Removal of the drying agent and solvent gives 2-chlo ~ -4-ethylthloaniline, an oil.
The following additional compounds are prepared utilizing the same general method:
2-bromo-4-ethylthioaniline, an oil.
2 fluoro-40ethylthioaniline, an oil.
2-chloro-4-isopropylthioaniline, an oil.
2,5-dichloro-4-ethylthioaniline, an oil.
2,3-dichloro-4-methylthioaniline, an oil.
2~iodo-4-ethylthioaniline, an oil.
Exam~le 6 _Chloro-4-tert-but~lthioaniline.
A solution of 2~chloro-4-thiocyanoaniline (36.9 g~

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0.20 mole) in ethanol (100-200 ml.) is added to a stirred so-lution of sodium sulflde nonahydrate (48.04 g.~ 0.20 mole) in water (100 ml.) and the mixture warmed (50 C.) for 90 minutes. The cool reaction mixture is poured into water (1 liter) and dilute hydrochloric acid added to bring the pH up to 6.0-6.5. The product is extracted with ether, the ether washed with water and then dried. Removal of the drying agent and ether leaves 2~chloro-4-mercaptoaniline as a yellow oil.
Dimethylcyclohexylamine (22.86 g., 0.18 mole) in methylene chloride (125 ml.) is added dropwise to a stirred solution of 2-ch1oro-4-mercaptoaniline (27.0 g., 0.17 mole) and tert-butyl bromide (22.86 g., 0.18 mole) in methylene chloride ~125 ml.) and the mixture is allowed to stir at room temperature for about 68 hours. An additional quantity of dimethylcyclohexylamine (2.3 g.) and tert-butyl bromide (2.5 g., 0O018 mole) is added and stirring is continued over-night. The reaction is poured into water, and the product is extracted with methylene chloride. The combined extracts are washed with dilute hydrochloric acid, water and dried. Re-moval of the drying agent and methylene chloride gives impure 2-chloro-4-tert-butylthioaniline as a beige solid.
Example 7 2-Bromo-4-methylthiochloromethanesulfonanilide.
Chloromethanesulfonyl chloride (0.03 mole) is added dropwise to a cold (0.5 C.) stirred solution o- 2-bromo-4-methylthioaniline (6.2 g., 0.028 mole) in pyridine ~20 ml.).
The solution is stirred at room temperature ove~night, poured ~3~

into ice water and 12 N hydrochloric acid with stirring to give 2-bromo-4-methylthiochloromethanesulfonanilide as an oil. A methylene chloride solution of the oil is washed with water and dried. Removal of the drying agent and methylene chloride gives a red oil. Crystallization from methylene chloride-hexane gives a red-tan solid, m.p. 72-85 C.
Analysis: %C ~H ~N
Calculated for C8HgBrClNO2S2: 29.0; 2.7; 4.2 Found: 29.6; 2.8; 4.3.
The following compounds are made using the same general method:
2-chloro-4-methylthiochloromethanesulfonanilide, m.p.
79-8~ C.
2 chloro-4-methylthiomethanesulfonanilide, mOp. 128-133 C.
2,3-dichloro-4-methylthiochloromethanesulfonanilide, m.p.
119-123 C.
2,3-dichloro-4-methylthiomethanesulfonanilide, m.p. 165-170 C.
4-methylthiomethanesulfonanilide, m.p. 107.5-I10 C.
Example 8 2-Bromo-4-meth~ thiomethanesulfonanilide.
To a stirred mixture of 4-methylthiomethanesulfon-anilide (7.6 g., 0.035 mole), iron filings (0.35 g.) and glacial acetic acid ~50 ml.) is added bromine (5.6 g., 0.035 mole~ dropwise. The reaction mixture is then heated at 110 C. for two hours, cooled and poured into water (300 ml.).
The oil product is extracted with methylene chloride, the combined extracts washed with water and dried, Removal of .:' , ; :``, , ~ ' :: ': : ' ` ' ' .:
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the drying agent and solvent gives product as an oil. The oil is crystallized from hexane, and the tan solid recrys-tallized from hexane-methylene chloride t:o gi~re a brown solid, m.p. 100-110 C.
5 Analysis: %C %H %N
Calculated for C8HlOBrNO2S2: 32.4; 3.4; 4.7 Found: 33.1; 3.4; 4.7.
Exam;?le 9 2-Chloro-4-eth~lthiochloromethanesul~onanilide.
Chloromethanesulfonyl chloride (4.0 g., 0.027 mole) is added dropwise to a stirred solution of 2-chloro-4-ethyl-thioaniline (5.0 g., 0.027 mole) in 3-bromopyridine (6.4 g., 0.041 mole) t and the mixture is stirred overnight at room temperature. The reaction mixture is taken up in methylene 15 chloride ~200 ml.) and dilute hydrochloric acid (20%, 200 ml.), the layers are separated, and the methylene chloride solution is washed with dllute hydrochloric acid (10%, 200 ml.) three times and then dried (CaSO4~. Removal of the drying agent and solvent glves product as a reddish oil. This oil is taken 20 up in hexane and cooled to give the product, 2-chloro-4-ethyl-thiochloromethanesulfonanilide, m.p. 70-72 C.
Analysis: %C %H %N
Calculated or C~H11C12NO2S2: 36.0; 3.7; 4-7 ~ Found: 36.3; 3.5; 4.7.
Additional compounds prepared utilizing the same general method are as follows~
2-bromo-4-ethylthiochloromethanesulfonanilide, m.p. 63-65 C. ~ ;

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2-chloro-4-isopropylthiochloromethanesulfonanilide, m.p.
50 53 C.
2-fluoro-4-ethylthiochloromethanesulfonanilide, m.p.
78-81 C.
2-chloro-4-ethylthiomethanesulfonanilid~, m.p. 101-103 C.
2-chloro-4-isopropylthiomethanesulfonanilide, m.p. 78-2-chloro-4-ethylthio~thanesulfonanilide, m.p. 64-66 C.
2-chloro-4-isopropylthioethanesulfonanilide, m.p. 52-53 C.
2-bromo-4-ethylthiomethanesulfonanilide, m.p. 83-85 C.
2-fluoro-4-ethylthiomethanesulfonanilide, m.p. 89-91 C.
2,5-dichloro-4-ethylthiomethanesulfonanilide, m.p. 143-144 C.
2-fluoro-4-ethylthioethanesulfonanilide, m.p. 77-79 C.
2-fluoro-4-methylthioethanesulfonanilide, m.p. 69-71 C.
2-fluoro-4-methylthiomethanesulfonanilide, m.p. 133-13~ C
2-fluoro-4-methylthiochloromethanesulfonanilide, m.p.
88-90 C.
2-bromo-4-isopropylthiomethanesulfonanilide, m.p. 82-84 C.
2-bromo-4-isopropylthioethanesulfonanilide, m.p. 62-64 C.
2-bromo-4-ethylthioethanesulfonanilide, m.p. 77.5-79.5 C.
2-fluoro-4-isopropylthiochloromethanesulfonanilide, an oil.
2-bromo-4-tert-butylthiochloromethanesulfonanilide, m.p.
100-102 C.
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2-iodo-4-ethylthiochloromethanesu-fonanilide, m.p. 74-76 c.
2,5-dichloro-4-ethylthiochloromethanesulfonanilide, m.p.
132.5-1~4 C.
2,5-dibromo-4-ethylthiochloromethanesulEonanilide, m.p~
189-195 C.
2j5-dibromo-4-isopropylthiochloromethanesulfonanilida~ ;
m.p~ 132-133 C~
2,3-dichloro-4 ethylthiochloromethanesulfonanilide, m.p~
92-94 C.
2-bromo-4-isopropylthiochloromethanesulfonanilide, m.p.
56-59 C.
Example 10 N-Chloromethylsulfonyl-2-chloro 4-ethylthiochloromethanesul-fonani lide . _ ,,, , ,. . . .... ~ ... - -Chloromethanesulfonyl chloride (60 g., 0.4 mole) is added dropwise to a cold (0-5 C.) stirred solution of 2-chloro-4-ethy1thioaniline (15.1 g., 0.081 mole) in pyridine (104 ml.). The solution is stirred at room temperature and poured into ice water and 12 N hydrochloric acid with stir-ring. The product is extracted into CH2C12, washed with water and dried. Removal of the drying agent and solvent gives crude product. Chromatography on silica gel with methy-lene chloride eluant gives pure product as an oil.
Example 11 2-Chloro-4-ethylthiochloromethanesulfonanilide.
, A solution of N~chlorome~hylsulfonyl-2-chloro-4-ethylthiochloromethanesulfonanilide (7.2 g., 0.017 mole) and - 85 percent potassium hydroxide (2.9 g.~ in methanol is stirred ' ' . ' - ' . . '' '., '' ' :, ' :~ . ' ` : ' 3~3~

about three days at room temperature. ~he solvent is re-moved by evaporation, the residue taken up in hot water, fil-tered, and the filtrate acidified with 12 N hydrochloric acid.
The product is recovered by filtration and air dried.
S xample 12 2-Chloro-4-methanesulfinylchloromethanesulfonanilide.
.
To a stirred solution of 2 chIoro-4-methylthio-chloromethanesulfonanilide (1.8 g.j 0.0061 mole) in glacial acetic acid (20 ml.) is added 30 percent hydrogen peroxide (0.0061 mole)O The solution is stirred overnight at room temperature, heated just to reflux, then treated with water.
The aqueous mixture is extracted with methylene chloride, washed with water and dried. Removal of the drying agent and solvent gives a yellow oil. Crystallization from hexane produces a white solid, m.p. 99-110 C.
Analysis: ~C %H %~
Calculated for C8HgC12NO3S2 31.8; 3.0; 4.6 Folmd: 31.3; 3.0; 4.7 The following compounds are prepared utilizing the same general method:
2-bromo 4-methanesulfinylchloromethanesulfonanilide, m.p.
108-116 C.
2-bromo-4-ethanesulfinylchloromethanesulfonanilide, m.p.
157-159 C.
2,3-dichloro-4-methanesulfinylchloromethanesulfonanilide, m.p. 153-163 C.
2-chloro-4-methanesulfinylmethanesulfonanilide, m.p.
162-165 C~

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2-chloro-4-ethanesulfinylmethanesulfonanilide, m.p. ~-121-123 C.
2-chloro-4-ethanesulfinylethanesulfonanilide, m.p. 109-112 C.
2-bromo-4-ethanesulfinylmethanesulfonanilide, m.p. 119-121 C.
2-fluoro-4-ethanesulfinylmethanesulfonanilide~ m.p. 122-124 C.
2-fluoro-4-ethanesulfinylethanesulfonanilide, m.p. 128-130 C~
2-fluoro-4~methanesulfinylethanesulonanilide, m.p 111-113 C.
2~bromo-4-isopropylsulfinylmethanesulfonanilide, m.p.
104-106 C.
2-bromo-4-isopropylsulfinylethanesulfonanilide, m.p.
118-120 C~
2-fluoro-4-methanesulfinylmethanesulfonanilide, m.p. 149-150 C.
2-bromo-4-ethanesulfinylethanesulfonanilide, m.p. 113-115 C. `
2-1uoro-4-methanesulfinylchloromethanesulfonanilide, m.p. 118-122 C.
2-fluoro-4-isopropylsulfinylchloromethanesulfonanilide, m.p. 118-121 C.
2-bromo-4-tert-butylsulfinylchloromethanesulfonanilide, m.p 112-115 C.
2-iodo-4-ethanesulfinylchloromethanesulfonanilide, m.p.
165-167 C.

,, ~3~3~6 -- 19 -- , 2,5-dichloro-4-ethanesulfinylmethanesulfonanilide, m~p.
149-150 C.
2,5-dichloro-4-ethanesulfinylchloromethanesulfonalide, m.p. 151-154 C.
5 2,3-dichloro-4-ethanesulfinylchloromethanesulfonanilide, m.p. 118~121 C.
2-chloro-4-tert-butylthiochloromethanesulfonanilide, m.p.
89-90 C.
Example 13 2-Chloro-4-methanesulfonylchloromethanesulfonanilide To a stirred solution of 2-chloro-4~methylthio-chloromethanesulfonanilide (3.0 g., 0.010-1 mole) in glacial acetic acid (30 ml.) is added 30 percent hydrogen peroxide (0.0405 mole). The solution is heated at reflux for 2.5 hours, water is added, and the mixture ls cooled. The re-sulting precipitate is collected by filtration, washed with water and dried to give a white solid, m.p. 172-180 C.
Analysis: %C %H %N
Calculated or C8HgC12NO4S2: 30.2; 2.8; 4-4 Found: 30.2; 2.8; 4.4.
Additional compounds prepared utilizing the same general method are as follows:
2-bromo-4-methanesulfonylchloromethanesulfonanilide, m.p. 156-168 C.
25 2-bromo-~-ethanesulfonylchloromethanesulfonanilide, m.p.
120-122 C.
2 chloro-4-athanesulfonylchloromethanesulfonanilide, m.p. 146-148 C.
.,, ~:

3~3~6 2-chloro~4-isopropylsulfonylchloromethanesulfonanilide, m.p. 146-149 C.
2-fluoro-4-ethanesulfonylchloromethanesulfonanilide, m.p. 143-144 C.
2-chloro-4--methanesulfonylmethanesulfonanilide, m.p.
167-169 C.
2-chloro-4-isopropylsulfonylmethanesulfonanilide, m.p.
142-144 C.
2~chloro-4-ethanesulfonylethanesulfonanilide, m.p. 92-94 C.
2-chloro-4-isopropylsulfonylethanesulfonanilide, m.p. i 11~-117 C~
2-bromo-4-methanesulfonylmethanesulfonanilide, m.p. 170-171.5 C.
2-bromo-4-ethanesulfonylmethanesulfonanilide, m.p. 122- ~
125 C. `
2-fluoro-4-ethanesulfonylmethanesulfonanilide, m.p. 165-167 C.
2,3~dichloro-4-methanesulfonylmethanesulfonanilide, m.p.
167-1~0 C~
2~bromo-4-isopropylsulfonylmethanesulfonanilide, m.p.
133-135 C.
2-bromo-4-isopropylsulfonylethanesulfonanilide, m.p.
110-112 C.
2 fluoro-4-methanesulfonylchloromethanesulfonanilide, m.p. 153-155 C.
2-fluoro-~-isopropylsulfonylchloromethanesulfonanilide, m.p. 140-142 C.

~l3~.3~

2-bromo-4-tert-butylsulfonylchloromethanesulfonanilide, m.p. 169-170 C.
2,5~dichloro-4-ethanesulfonylmethanesulfonanilide, m.p.
171-174 C.
52,5-dichloro-4-ethanesulfonylchloromethanesulfonanilide, m.p. 182-183 C.
2,3-dichlorc>-4-ethanesulfonylchloromethanesulfonanilide m.p. 164-166 C.
2-fluoro 4-methanesulfonylmethanesulfonanilide, m.p.
10181-183 C.
2-bromo-4-ethanesulfonylethanesulfonanilide, m.p. 88-91 C.
2-iodo-4-ethanesulfonylchloromethanesulfonanilide, m.p~
130~132 C.

., : ~ , :. , : : , : . ~ : : : : : :: : :: .:: . , : :

Claims (12)

CLAIMS:

1. A compound of the formula wherein R is an alkyl group containing from 1 to 4 carbon atoms or monohalomethyl, R' is an alkyl group containing from 1 to 4 carbon atoms, A is halogen or -CF3, B is hydrogen or halogen and n is 0-2, provided that when A is CF3, B is halogen, and agriculturally acceptable salts thereof.

2. A compound according to claim 1 wherein R contains one carbon atom.

3. A compound according to claim 1 wherein n is zero.

4. A compound according to claim 1 wherein n is one.

5. A compound according to claim 1 wherein n is two.

6. 2-Bromo-4-ethanesulfinylchloromethanesulfonanilide ac-cording to claim 4.

7. 2-Bromo-4-ethanesulfonylchloromethanesulfonanilide ac-cording to claim 5.

8. 2-Chloro-4-methanesulfinylchloromethanesulfonanilide ac-cording to claim 4.

9. 2-Chloro-4-methanesulfonylchloromethanesulfonanilide ac-cording to claim 5.

10. A 2-halo-4-ethanesulfinylchloromethanesulfonanilide according to claim 4.

11. 2-Chloro-4-ethanesulfonylchlorometharlesulfonanilide according to claim 5.

12. A method of modifying plant growth, which comprises applying to the plants an effective amount of a compound as defined in claim 1, 2 or 3.