US3804896A - N,n'-disubstituted sulfamides - Google Patents

N,n'-disubstituted sulfamides Download PDF

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US3804896A
US3804896A US00075680A US7568070A US3804896A US 3804896 A US3804896 A US 3804896A US 00075680 A US00075680 A US 00075680A US 7568070 A US7568070 A US 7568070A US 3804896 A US3804896 A US 3804896A
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ethylidene
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diethylamino
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C Tincher
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Monsanto Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/195—Radicals derived from nitrogen analogues of carboxylic acids

Definitions

  • sisting of halogen, alkyl of a maximum of 6 carbon R is hydrogen, alkyl of a maximum of 12 carbon atoms, atoms halqalkyl of a maxlmum of 6 carbon haloalkyl of a maximum of 12 carbon atoms and a and a maxlmum of 3 halogens alkoxy of a manmaximum of 3 halogens, cycloalkyl of 3 through 8 2O mum of 6 carobn atoms phenoxy and carbon atoms, aryl of a maximum of 10 carbon atoms, and phenyl substituted by a maximum of five of the group con- 0 sisting of halogen, alkyl of a maximum of 6 carbon -NHi J-Rs atoms, haloalkyl of a maximum of 6 carbon atoms and a maximum of 3 halogens, alkoxy of a maximum of 6 carbon atom
  • Z is oxygen or sulfur
  • E R and R are each independently selected from alkyl of a maximum of 12 carbon atoms, haloalkyl of a maximum of 12 carbon atoms with a maximum of 3 haloh gens, alkenyl of a maximum of 12 carbon atoms, cycloz i z IS an alkyl of a maxlmum of 6 carbon alkyl of 3 through 8 carbon atoms, alkylene linked Zis oxygen Sulfur through a hetero oxygen atom (i.e.
  • R and R are each independently selected from alkyl of a phohno moiety) aryl a maximum of 10 carbon maximum of 12 carbon atoms, haloalkyl of a maximum atoms alkaryl a maxlmum of 18 carbon atoms aryl of 12 carbon atoms with a maximum of 3 halogens, aikyl of a maximum of 18 carbon atoms; alkenyl of a maximum of 12 carbon atoms, cycloalkyl R415 an aryl of a maxlmun ⁇ of 10 carbon atoms and phen' of 3 through 8 carbon atoms, alkylene linked through 40 s.ubstltuted by a maximum of of the group cona hetero Oxygen atom (ie To form a morpholino slsting of halogen, alkyl of a maximum of 6 carbon moiety) aryl of a maximuhl' of 10 carbon atoms atoms, haloal
  • Y is Where R is an alkyl of a maximum of 6 carbon atoms; NH--. When n is 0 then preferably R is haloalkyl. Y is oxygen or an -NH- group; When n is 1 then preferably Z is oxygen. Most preferred n is an integer of 0 or 1 with the provisions that when R; in each of the foregoing cases are where any phenyl is hydrogen or haloalkyl then It is 0.
  • the alkyls represented by R R and R can be methyl, ethyl, propyl, sec. propyl, tert. butyl, hexyl and dodecyl.
  • Haloalkyls represented by R R and R can be chlo romethyl, trifluorornethyl, l-bromopropyl, 1,1-dichlorobutyl, 1,1,2-trichlorohexyl, and l-iodododecyl.
  • Alkenyls represented by R R and R can be 1- propenyl, allyl, isobutenyl, methallyl, 2-hexeny1, l-octenyl and 2-dodecenyl.
  • the cycloalkyls represented by R R and R can be cyclopropyl, cyclohexyl and cyclooctyl.
  • Aryls of up to 10 carbon atoms represented by R R R and R can be phenyl and naphthyl.
  • Aralkyls represented by R, and R can be benzyl, phenethyl and 12-phenyldodecyl.
  • Alkaryls represented by R; and R can be Z-methylphenyl, 3-ethylphenyl, 6-isopropylphenyl, p-tert.butylphenyl, 4-hexylphenyl, 4-dodecylphenyl, 2,4-dimethylphenyl, 2-methyl-4-hexylphenyl and 2,4,6-trimethylphenyl.
  • Substituted phenyls represented by R and R; can be p-chlorophenyl, 4-bromophenyl, 2,4,6-trichlorophenyl, any of the alkaryls aforementioned, 2-chloromethylphenyl, 4-iodomethylphenyl, 3-trifluoromethylphenyl, 2,6- di( 1-chloroethyl)phenyl, 4-( 1, 1-dibromobuty1)phenyl, 4- (6,6,6-trichlorohexyl)phenyl, 2-methoxyphenyl, 3-propoxyphenyl, 4-hexoxyphenyl, 2-nitrophenyl, 2,4-dinitrophenyl, 3-(acetamido)phenyl, 4-(butyramido)phenyl, 4- (caproamido)phenyl, 2-chloro-4-methyl-phenyl, 2-methoxy-4-methylphenyl, 2-methoxy-4-bromophenyl, 2,
  • dichlorophenoxy)ethylidene1sulfamate 1 1 2,4-dichlorophenyl N-[ 1- (morpholino) -2- (phenoxy) ethylidene] sulfamate 12) p- (Z-methylpropionamido) phenyl N- 1- (dimethylamino) -2- (p-nitrophenoxy) ethylidene] sulfamate 13 p-nitrophenyl N-[ l-(diethylamino) -2- (O-nitrophenoxy) ethylidene1snlfamate (l4) p-chloro-O-toylyl N-[ 1-( diethylamino -2- p-nitrophenoxy) ethylidene] sulfamate 15 p-nitro-m-tolyl N-[ 1-( diethylamino -2- p-nitrophenoxy)ethy1idene]sulf
  • the general procedure involves reacting in a first step, the necessary amide with the chlorosulfonyl isocyanate to form a sulfonyl acetamidine. This is followed by the reaction of the sulfonyl acetamidine in a second step with the necessary aniline or phenol.
  • EXAMPLE 1 In a three-neck flask (500 ml.) fitted with a mechanical stirrer, dropping funnel and a drying tube were placed 4 g. or 0.025 mol of N,N-diethyl-a-ethoxy acetamide and milliliters of anhydrous methylene chloride. The solution was cooled in a Dry Ice-isopropanol bath and 3.52 g. or 0.025 mol of chlorosulfonyl isocyanate was added in one portion. The reaction was allowed to stir overnight at room temperature. (At that time an LR.
  • EXAMPLE 2 In a three neck rflask (500 ml.) fitted with a mechanical stirrer, dropping funnel and a drying tube were placed g. or 0.045 mol of N,N-diethyl-wphenylthioacetamide and 100 milliliters of anhydrous methylene chloride. The solution was cooled in a Dry Ice-isopropanol bath and 6.5 g. or 0.045 mol of chlorosulfonyl isocyanate was added dropwise. The reaction was stirred about hours at room temperature, then 6.9 g. or 0.05 mol of p-nitrophenol dissolved in acetone and methylene chloride and 10.1 g. of triethylamine were added to the solution.
  • Nuclear magnetic resonance analysis confirmed the expected structure p-nitrophenyl N-[1-(diethylamino)-2- (phenylthio ethylidene] sulf am ate.
  • EXAMPLE 3 In a three-neck flask (500 ml.) fitted with a mechanical stirrer, dropping funnel and a drying tube were placed 10 g. or 0.05 mol of N-methyl-N-(2-methyl-6-tert.-butylphenyl)formamide in anhydrous methylene chloride. The solution was cooled in a Dry Ice-isopropanol bath and 6.35 g. or 0.045 mol of chlorosulfonyl isocyanate was added. The reaction was allowed to stir until the NMR showed no isocyanate present. Then 12.2 g.
  • EXAMPLE 4 In a three-neck flask (500 ml.) fitted with a mechanical stirrer, dropping funnel and a drying tube were placed 40 g. or 0.55 mol of dimethylfor-mamide dissolved in ether. The solution was cooled to 0 C. and 70.7 g. or 0.5 mol of chlorosulfonyl isocyanate was added and the reaction was allowed to stir about 3 to 4 hours. First, 50.5 g. of triethylamine was added, then 90 g. of 3-(isopropylcarboxamido)phenol was added and the reaction mixture was allowed to stir for one-half to one hour. The resulting solution was washed with water, the organic phase dried over magnesium sulfate and the solvent was stripped off. Recrystallization of the resulting material from ethanol yielded a white solid having a melting point of 126- 127 C.
  • herbicide as used herein and in the appended claims means materials which (1) effectively control all plants in a given locus or (2) selectively control the growth of one or more plant species in the presence of other plants. In like manner, herbicidal is used to identify the overall and selective control activity of the compositions of this invention.
  • plant as used herein and in the appended claims is inclusive of dormant seeds, germinant seeds, ger-minative seeds, emerging seedlings and established woody and herbaceous vegetation including the roots and above-ground portions.
  • control as used herein and in the appended claims is inclusive of the actions of (l) killing, (2) inhibiting growth, reproduction or proliferation, and (3) removing, destroying or otherwise diminishing the occurrence and activity of plants and is applicable to any of the stated actions, or any combination thereof.
  • insect and insecticide are used herein in their broad common usage to include spiders, mites, ticks, and like pests which are not in the strict biological sense classed as insects.
  • the usage herein conforms to the definitions provided by Congress in Public Law 104, the Federal Insecticide, Fungicide, and Rodenticide Act of 1947, section 2, subsection b, wherein the term insect is used to refer not only to those small invertebrate animals belonging mostly to the class Insecta, comprising six-legged, usually winged forms, as beetles, bugs, bees, flies, and so forth, but also to other allied classes of anthropods whose members are Wingless and usually have more than six legs, as spiders, mites, ticks, centipedes, and wood lice.
  • herbicidal or insecticidal composition as used herein means a novel compound of this invention in combination with an adjuvant to be defined hereinbelow.
  • EXAMPLE 5 The pre-emergent herbicidal activity of the active ingredients of this invention is demonstrated as follows: A good grade of top soil is placed in aluminum pans and compacted to a depth of to /2" from the top of each pan. A predetermined number of seeds of the test plant species are placed on top of the soil in the pans. The seeds are covered with a /8 layer of soil and the pan leveled. The active ingredient is applied by spraying the surface of the top layer of soil with a herbicidal formulation containing a suflicient amount of active ingredient to obtain the desired rate of active ingredient per acre. For soil incor poration, the chemical is sprayed on and mixed into the soil used to cover the seeds.
  • the seed-containing pans are placed on a wet sand bench and maintained under ordinary conditions of sunlight and watering. The plants are observed at the end of approximately 14 days and the results recorded.
  • the herbicidal activity index is based on the average percent control of each seed lot. The herbicidal activity index is converted to a relative numerical scale for the sake of brevity and simplicity in the table.
  • the pre-emergent herbicidal activity index used is defined as follows:
  • Average percent control Numerical scale 0 to 25 0 26 to 50 l 51 to 2 76 to 3 TAB LE I Dosage, Barnlbs. Morning Wild Rye Sugar yard Crab Pig- Cpd. acre Koohla glory oat Brorne grass Radish beet Cotton Corn Foxtall grass grass weed Cana- Wild dian Vel- Soy- Buck- To- Sor- Smart- Cockle- Lambsthis- Coflce Nutvet Quack- Johnson Bro'mua Cpd.
  • EXAMPLE 6 Thereafter is added 0.1 ml. of an acetone solution of In a post-emergent herbicidal test, the active ingrediknow? Foncelitratlon in percent by weight of a compound ents in each case is applied in spray form to 21 day old O.th1s mvemlon ex amp 16 an of by specimens of the plants (species indicated hereinafter). welght.acetofne sohmon prov] es 52
  • the herbicidal sprays are acetone-Water solutions con- S o w 3 of an 0 taining surface active agents and varying amounts of the Y Welg t aceton? so of the Sald compound active ingredient.
  • the solutions are applied to the plants a Concentratlon of thereof) In the troug in different pans at rates equal to the desired rate of ac- 40 oft e pouch formed by the paper i thereof are placed tive ingredient on a per acre basis.
  • the treated plants are i i com (Zea mays glybnd g about placed in a greenhouse and the effects are observed and ⁇ 1p g d sereupon to t troug an g e recorded after approximately 14 days see s is a e to 12 ready-to-hatch eggs of t e sout ern corn rootworm (Diabrotica undecimpunctata howardi)
  • the Post emfirgent herblcldal actmty Index used m thls which eggs were washed (with distilled water) free of the example is defined as follows: N I 1 H b, d l ,t SO11 1n wh1ch they were incubated at room temperature umema sea
  • the so-charged growth pouch is then placed in an 1 Sl1ghtphytotox1c1ty. h b o d 2 Moderate phytotoxicity.
  • p ig t position m an lncu ator malntamed at 80 F. an 3 Severe phytotoxicity 70% relative humidity for 14 days.
  • the growth pouches are removed and the extent of In Table H below the dosage rate method of app1ica kill in percent of the particular species of corn rootworm tion, the spectrum of plant seeds treated, and the results larvae observed. The results were as follows:
  • EXAMPLE 7 g gg The act1v1ty of these compounds agamst the southern 5 com rootworm (Diabrotica undecimpunctata howardi) is N01E.
  • K is rn-(isopropylcarboxamido)phenyl dimethylamin demonstrated by the follow.mg' methylenesuliamate
  • L is 2,4-dichl0r0phenyl N-[l-(diethylamlno)-2 To a growth Pouch (dlSPO SEed'Pak growth Pouch, (p-nitrophenoxy)-ethylidene]sulfamate;Misp-nitrophenylN-[l-(diethyl- Catalogue No.
  • N 2,3,4,5,6-pcntachlorophenyl N-[l-(morpholmo)-2-(phenoxy)-ethylidene]sulfemate
  • O p- Amenca Hospital Supply Corporation, Evanston, Ill.) 1n chloro-O-tolyl N-[l-(diethylamino)-2-(p-nitrophenoxy)-ethylidene]sulfaan upright position is added 20 ml. of distilled water.
  • EXAMPLE 8 The compounds of the present invention are also effective against the western corn rootworm (Diabrotica virgifera). To illustrate this activity an aqueous acetone solution of p-nitrophenyl N [1 (diethylamino) 2 (phenylthio)ethylidene]-sulfamate at a concentration of 5 p.p.m. was prepared. About 1 ml. of this solution was used to moisten a sheet of filter paper positioned in a petri dish. Two one-inch sections of corn roots were deposited on the filter paper and the paper was then infested with 5 western corn rootworm larvae. After being maintained for 24 hours at 25 C. and 70% relative humidity, the mortality rate was observed. Under these conditions, 60% of the larvae were killed.
  • EXAMPLE 9 To illustrate the activity of the compounds of this invention with respect to control of mosquito larvae, tests were carried out employing a standard evaluation procedure on 3-day old early instar yellow fever mosquito larvae (Aedes aegypti) and the results were as follows:
  • the active ingredients hereindefined are suitable for both pre-emergent and post-emergent plant application. That is, they are effective in controlling the growth of germinant seeds, emerging seedlings, and established vegetation by exposing the seeds, emerging seedlings, the roots, the leaves or other above-ground portions to the action of an eifctive amount of one or more of these herbicidally active compounds; however, the best results are usually obtained in a pre-emergent application. Such constitutes a preferred embodiment of the method of controlling plants.
  • the active ingredients are applied in amounts from about 0.1 to about 50 or more pounds per acre, preferably about 0.1 to 15 pounds per acre in foliar treatments. In soil applications, it is desirable that the active ingredients be distributed to a depth of at least 0.2 inch. In pre-emergence herbicidal applications the active ingredients are usually applied in amounts from about 0.1 to 25 pounds per acre but preferably from about 0.2 to 10 pounds per acre. It is believed that one skilled in the art can readily determine from the teachings of this specification, including, examples, the procedure for any particular desired application.
  • the active ingredient is usually employed at a rate of 0.01 to 50 pounds per acre. Preferably, they are employed in about 0.1 to 25 pounds per acre.
  • the active ingredients can be used alone or in combination with an appropriate material referred to in the art as an adjuvant in liquid or solid form.
  • adjuvants are prepared by admixing the active ingredient with one or more adjuvants which includes diluents, extenders, carriers and conditioning agents to provide compositions in the form of finely-divided particulate solids or dusts, granules, pellets, solutions, dispersions or emulsions.
  • the active ingredient can be used with an adjuvant such as a finely-divided particulate solid, a liquid of organic origin, water, a wetting agent, dispersing agent, an emulsifying agent or any suitable combination of these.
  • Suitable adjuvants of the foregoing types are not here defined in detail as to composition, particle size, relative amounts, etc., since they are well known in the art.
  • the active ingredients may be formulated with the active ingredient in minor or major proportions in accordance with the table below:

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Abstract

THE NEW COMPOUNDS OF THE FORMULA

R1-(Z-CH2)N-C(-N(-R2)-R3)=N-SO2-Y-R4

WHERE: R1 IS HYDROGEN, ALKYL OF A MAXIMUM OF 12 CARBON ATOMS, HALOALKYL OF A MAXIMUM OF 12 CARBON ATOMS AND A MAXIMUM OF 3 HALOGENS, CYCLOALKYL OF 3 THROUGH 8 CARBON ATOMS, ARYL OF A MAXIMUM OF 10 CARBON ATOMS AND PHENYL SUBSTITUTED BY A MAXIMUM OF FIVE OF THE GROUP CONSISTING OF HALOGEN, ALKYL OF A MAXIMUM OF 6 CARBON ATOMS, HALOALKYL OF A MAXIMUM OF 6 CARBON ATOMS AND A MAXIMUM OF 3 HALOGENS, ALKOXY OF A MAXIMUM OF 6 CARBON ATOMS, PHENOXY, NO2, AND

-NH-CO-R5

WHERE R5 IS AN ALKYL OF A MAXIMUM OF 6 CARBON ATOMS; Z IS OXYGEN OR SULFUR; R2 AND R3 ARE EACH INDEPENDENTLY SELECTED FROM ALKYL OF A MAXIMUM OF 12 CARBON ATOMS, HALOALKYL OF A MAXIMU, OF 12 CARBON ATOMS WITH A MAXIMUM OF 3 HALOGENS, ALKENYL OF A MAXIMUM OF 12 CARBON ATOMS, CYCLOALKYL OF 3 THROUGH 8 CARBON ATOMS, ALKYLENE LINKED THROUGH A HETERO OXYGEN ATOM (I.E TO FORM A MORPHOLINO MOIETY), ARYL OF A MAXIMUM OF 10 CARBON ATOMS, ALKARYL OF A MAXIMUM OF 18 CARBON ATOMS; MAXIMUM OF 18 CARBON ATOMS; R4 IS ARYL OF A MAXIMUM OF 10 CARBON ATOMS, AND PHENYL SUBSITUTED BY A MAXIUM OF FIVE OF THE GROUP CONSISTING OF HALOGEN, ALKYL OF A MAXIMUM OF 6 CARBON ATOMS, HALOALKYL OF A MAXIMUM OF 6 CARBON ATOMS AND A MAXIMUM OF 3 HALOGENS, ALKOXY OF A MAXIMUM OF 6 CARBON ATOMS, PHENOXY, NO2, AND

-NH-CO-R5

WHERE R5 IS AN ALKYL OF A MAXIMUM OF 6 CARBON ATOMS; IS OXYGEN OR AN-NH-GROUP; N IS AN INTEGER OF 0 OR 1 WITH THE PROVISIONS THAT WHEN R1 IS HYDROGEN OR HALOALKYL THEN N IS 0. THESE COMPOUNDS ARE USEFUL AS HERBICIDES AND AS INSECTICIDES.

Description

Patented Apr. 16, 1974 I 3,804,896 growth of plants and insects therewith. The new com- 'DISUBSTITUTED SULFAMIDES pounds of this invention are of the formula Cline A. Tincher, Olivette, M0., assignor to Monsanto Company, St. Louis, M0. N Drawing- (sr p if s 1 7/060Ser. No. 75,680 RKZCHDAIENSOHR US. Cl. 260--556 N 1 Claim ]I z R1 ABSTRACT OF TIE DISCLOSURE where:
The new compounds of the formula 10 R is hydrogen, alkyl of a maximum of 12 carbon atoms, haloalkyl of a maximum of 12 carbon atoms and a R (zCHl),,C=NsO2YR4 maximum of 3 halogens, cycloalkyl of 3 through 8 carbon atoms, aryl of a maximum of 10 carbon atoms,
and phenyl 15 substituted by a maximum of five of the group conwhere: sisting of halogen, alkyl of a maximum of 6 carbon R is hydrogen, alkyl of a maximum of 12 carbon atoms, atoms halqalkyl of a maxlmum of 6 carbon haloalkyl of a maximum of 12 carbon atoms and a and a maxlmum of 3 halogens alkoxy of a manmaximum of 3 halogens, cycloalkyl of 3 through 8 2O mum of 6 carobn atoms phenoxy and carbon atoms, aryl of a maximum of 10 carbon atoms, and phenyl substituted by a maximum of five of the group con- 0 sisting of halogen, alkyl of a maximum of 6 carbon -NHi J-Rs atoms, haloalkyl of a maximum of 6 carbon atoms and a maximum of 3 halogens, alkoxy of a maximum of 6 carbon atoms, phenoxy, N0 and where R is an alkyl of a maximum of 6 carbon atoms;
Z is oxygen or sulfur;
E R and R are each independently selected from alkyl of a maximum of 12 carbon atoms, haloalkyl of a maximum of 12 carbon atoms with a maximum of 3 haloh gens, alkenyl of a maximum of 12 carbon atoms, cycloz i z IS an alkyl of a maxlmum of 6 carbon alkyl of 3 through 8 carbon atoms, alkylene linked Zis oxygen Sulfur through a hetero oxygen atom (i.e. to form a mor- R and R are each independently selected from alkyl of a phohno moiety) aryl a maximum of 10 carbon maximum of 12 carbon atoms, haloalkyl of a maximum atoms alkaryl a maxlmum of 18 carbon atoms aryl of 12 carbon atoms with a maximum of 3 halogens, aikyl of a maximum of 18 carbon atoms; alkenyl of a maximum of 12 carbon atoms, cycloalkyl R415 an aryl of a maxlmun} of 10 carbon atoms and phen' of 3 through 8 carbon atoms, alkylene linked through 40 s.ubstltuted by a maximum of of the group cona hetero Oxygen atom (ie To form a morpholino slsting of halogen, alkyl of a maximum of 6 carbon moiety) aryl of a maximuhl' of 10 carbon atoms atoms, haloalkyl of a maximum of 6 carbon atoms and i a aryl of a maximum of 18 carbon atoms, arylalkyl of a a nlljaxlmum of halogensbalkogy of a maximum of 6 maximum of 18 carbon atoms; car on atoms p enoxy N an R is aryl of a maximum of 10 carbon atoms, and phenyl substituted by a maximum of five of the group consisting of halogen, alkyl of a maximum of 6 carbon atoms,
haloalkyl of a maximum of 6 carbon atoms and a maxi- NEG-R5 mum of 3 halogens, alkoxy of a maximum of 6 carbon atoms phenoxy and 'where R is an alkyl of a maximum of 6 carbon atoms;
Y is oxygen or an NH group; 0 n is an integer of 0 or 1 with the provision that when R NH -R is hydrogen or haloalkyl then It is 0.
Preferred compounds of the foregoing are where Y is Where R is an alkyl of a maximum of 6 carbon atoms; NH--. When n is 0 then preferably R is haloalkyl. Y is oxygen or an -NH- group; When n is 1 then preferably Z is oxygen. Most preferred n is an integer of 0 or 1 with the provisions that when R; in each of the foregoing cases are where any phenyl is hydrogen or haloalkyl then It is 0. moiety present is substituted by a maximum of three of These compounds are useful as herbicides and as the recited substiiuents a maxium of l insecticides The halogens included within the scope of this mvention are the whole group consisting of chlorine, bromine, iodine and fluorine. This invention relates to new compounds, the method Examples of the various other substituents included in of their preparation and to the method of controlling the this invention are as follows:
The alkyls represented by R R and R can be methyl, ethyl, propyl, sec. propyl, tert. butyl, hexyl and dodecyl.
Haloalkyls represented by R R and R can be chlo romethyl, trifluorornethyl, l-bromopropyl, 1,1-dichlorobutyl, 1,1,2-trichlorohexyl, and l-iodododecyl.
Alkenyls represented by R R and R can be 1- propenyl, allyl, isobutenyl, methallyl, 2-hexeny1, l-octenyl and 2-dodecenyl.
The cycloalkyls represented by R R and R, can be cyclopropyl, cyclohexyl and cyclooctyl.
Aryls of up to 10 carbon atoms represented by R R R and R; can be phenyl and naphthyl.
Aralkyls represented by R, and R can be benzyl, phenethyl and 12-phenyldodecyl.
Alkaryls represented by R; and R can be Z-methylphenyl, 3-ethylphenyl, 6-isopropylphenyl, p-tert.butylphenyl, 4-hexylphenyl, 4-dodecylphenyl, 2,4-dimethylphenyl, 2-methyl-4-hexylphenyl and 2,4,6-trimethylphenyl.
Substituted phenyls represented by R and R; can be p-chlorophenyl, 4-bromophenyl, 2,4,6-trichlorophenyl, any of the alkaryls aforementioned, 2-chloromethylphenyl, 4-iodomethylphenyl, 3-trifluoromethylphenyl, 2,6- di( 1-chloroethyl)phenyl, 4-( 1, 1-dibromobuty1)phenyl, 4- (6,6,6-trichlorohexyl)phenyl, 2-methoxyphenyl, 3-propoxyphenyl, 4-hexoxyphenyl, 2-nitrophenyl, 2,4-dinitrophenyl, 3-(acetamido)phenyl, 4-(butyramido)phenyl, 4- (caproamido)phenyl, 2-chloro-4-methyl-phenyl, 2-methoxy-4-methylphenyl, 2-methoxy-4-bromophenyl, 2,6-dichloro-4-propylphenyl, 2-chloro-4-propionamidophenyl, 2-ethyl-4-acetamidophenyl, 2-chloro-4-acetamido-6-methoxyphenyl, 3-propyl-4-nitrophenyl, and the like.
Illustrative examples of compounds of this invention are:
( l m- (isopropylcarboxamido) phenyl dimethylaminomethylenesulfamate (2) p-chlorophenyl dimethylaminomethylenesulfamate (3 p-butoxyphenyl N- 1- (N'-methyl-N'-dodecyl amino methylene] sulfamate (4) m-nitrophenyl dimethylaminomethylenesulfamate (5) 2,3,4,5,6-pentachlorophenyl N-[1-(diethylamino)- 2- (ethoxy) ethylidene] sulfamate (6) p-methoxyphenyl N-[ l-(diethylamino)-2-dodecy1- oxy) ethylidene1sulfamate (7) p-chloromethylphenyl N-[ 1-(diethylamino)-1-phenoxy) methylidene] sulfamate (8) 3,4-dichlorophenyl N-[ 1-(diethylamino)-2- (2,4-dichlorophenoxy) ethylidene] sulfamate (9) m-(Z-methylpropionamido phenyl N-[ l- (diethylamino -2- (2,4-dichlorophenoxy) ethylidene] sulfamate (10) m-propionamidophenyl N-[ 1-( diethylamino -2-(2,4-
dichlorophenoxy)ethylidene1sulfamate 1 1 2,4-dichlorophenyl N-[ 1- (morpholino) -2- (phenoxy) ethylidene] sulfamate 12) p- (Z-methylpropionamido) phenyl N- 1- (dimethylamino) -2- (p-nitrophenoxy) ethylidene] sulfamate 13 p-nitrophenyl N-[ l-(diethylamino) -2- (O-nitrophenoxy) ethylidene1snlfamate (l4) p-chloro-O-toylyl N-[ 1-( diethylamino -2- p-nitrophenoxy) ethylidene] sulfamate 15 p-nitro-m-tolyl N-[ 1-( diethylamino -2- p-nitrophenoxy)ethy1idene]sulfamate 16) p-phenoxyphenyl N 1- (diethylamino) -2- (phenoxy ethylidene] sulfamate 17) p-chloro-O-tolyl N- l-(diethylamino) -2- (phenoxy) ethylidene] sulfamate 18) p-nitro-O-tolyl N-[ l-(diethylamino -2- (phenoxy) ethylidene1sulfamate 19 p-phenoxyphenyl N-[ l-(morpholino) -2- (phenoxy) ethylidene] sulfamate (20) p-chlorophenyl N-[1-(diallylamino)-2-(phenoxy)- ethylidene] sulfamate (21 p-nitrophenyl N-[ 1- (diethylamino -2- (phenylthio) ethylidene] sulfamate (22) 2,4-dichlorophenyl N-[1-(diethylamino)-2-(phenylthio ethylidene] sulfamate (23) 2,3,4,5,6-pentachlorophenyl N- 1- (diethylamino 2- (phenylthio ethylidene] sulfamate (24) n-[a-(2 tert.butyl N,6 dimethylanilino)methylidene] -N'- (2,6-xyly sulfamide (25) N-[2chloro-1-(N-isopropylanilino)ethylidene]-N'- a,a,a-trifluoro-m-tolyl-sulfamide (26) 4'-nitro-N-[2-chloro-1-(N-isopropylanilino) -ethylidene] sulfanilide (27) N-[Z-chloro 1 (diisobutylamino)ethylidene]-2,6-
xylysulfamide (28) N- [2-chloro-1-(N-isopropylanilino)ethylidene] 2,6-
xylysulfamide (29) m-(Z-methylpropionamido)phenyl N-[ l-diethylamino-2- (2,4,5 -trichlorophenoxy) ethylidene] sulfamate (30) m-propionamidophenyl N-[1-(dimethylamino)-2- 2,4,5 -trichlorophenoxy ethylidene] sulfamate (31) p-nitrophenyl N-[1-(dimethylamino)-2-(2,4,5-trichlorophenoxy ethylidene] sulfam ate (32) 4'-chloro-N-[l-butoxy-l-(N diethylamino)methylidene]su1fanilide (33 4-methoxy-N-[l-phenyl-l-(N-diethy1amino)- methylidene] sulfanilide (34) N-[2-(2,4,5-trichlorophenyl)-l-(N-diethylamino ethylidene] sulfanilide (35 N[2- (4-methylphenyl) -1-(N-ethyl-N-1-chloroethylamino)ethylidene]sulfanilide (36) 4-methylphenyl N-[1-(methyl-2',6'-dimethylphenylamino -2- (dodecylthio ethylidene] sulfamate (37) 4 chlorophenyl N-[ l-(diethylamino)-2-(4-chlorophenylthio)ethylidene]sulfamate (3 8) N-[ 1- N-ethyl-N-Z-methylphenylamino -2- (propylthio)ethylidene]sulfanilide (39) N [1 (N ethyl N phenylamino)-2-(4-chloromethylphenylthio)ethylidene] -4-chlorosulfani1ide (40) N- 1-(N,N-diethylamino) -2-(pheny1thio)ethylidene]-4-nitrosulfanilide (41) N-[1-(N,N-diethylamino)-2-(2-chlorophenylthio ethylidene] -2-methylsu1fanilide (42) N-[1-(N,N--didodecen-2-ylamino)-2-(4-chlorophenylthio) ethylidene] sulfanilide (43) 2,3,4,5,6-pentachlorophenyl N-[1-(morpholino)- 2- (phenoxy)ethylidene]sulfamate The compounds can all be prepared by the same general procedure. The general procedure involves reacting in a first step, the necessary amide with the chlorosulfonyl isocyanate to form a sulfonyl acetamidine. This is followed by the reaction of the sulfonyl acetamidine in a second step with the necessary aniline or phenol. Illustrative detailed, examples of this invention will now be set forth.
EXAMPLE 1 In a three-neck flask (500 ml.) fitted with a mechanical stirrer, dropping funnel and a drying tube were placed 4 g. or 0.025 mol of N,N-diethyl-a-ethoxy acetamide and milliliters of anhydrous methylene chloride. The solution was cooled in a Dry Ice-isopropanol bath and 3.52 g. or 0.025 mol of chlorosulfonyl isocyanate was added in one portion. The reaction was allowed to stir overnight at room temperature. (At that time an LR. spectrum showed the disappearance of the isocyanate (NCO) band at 4.5,u.) Then the theoretical amount (i.e., 6.75 g.) of 2,3,4,5,6-pentachlorophenol accompanied by a theoretical amount of (i.e., 2.5 g.) triethylamine was added dropwise to the solution, which was cooled in an ice-salt bath and the reaction mixture was allowed to stir overnight. The resulting solution was washed with water, the organic phase dried over magnesium sulfate and the solvent was stripped off on a rotary evaporator. Recrystallization of the resulting material from ethanol yielded a white solid having a melting point of 121.5122.5 C.
Elemental analysis and other data follows:
C14H1'ZC15N204S1 MW=486. 66. Calcd. (percent): C, 34.55; H, 3.52; CI, 36.43; N, 5.76; 0, 13.15; S, 6.59. Found (percent): C, 34.80; H, 3.44; Cl, N, 5.99; O, S,
Both nuclear magnetic resonance (NMR) and infrared spectral analysis confirmed the expected structure 2,3,4,5,6-pentachlorophenyl N-[ 1- (diethylamino) 2- (ethoxy)ethylidene]sulfamate.
EXAMPLE 2 In a three neck rflask (500 ml.) fitted with a mechanical stirrer, dropping funnel and a drying tube were placed g. or 0.045 mol of N,N-diethyl-wphenylthioacetamide and 100 milliliters of anhydrous methylene chloride. The solution was cooled in a Dry Ice-isopropanol bath and 6.5 g. or 0.045 mol of chlorosulfonyl isocyanate was added dropwise. The reaction was stirred about hours at room temperature, then 6.9 g. or 0.05 mol of p-nitrophenol dissolved in acetone and methylene chloride and 10.1 g. of triethylamine were added to the solution. The flask and contents was cooled in an ice-salt bath and the reaction mixture was allowed to stir several hours. The resulting solution was washed with water, the organic phase dried over magnesium sulfate and the solvent was stripped off. Recrystallization of the resulting material from ethanol yielded a yellow solid having a melting point of 86.9-88.1 C.
Nuclear magnetic resonance analysis confirmed the expected structure p-nitrophenyl N-[1-(diethylamino)-2- (phenylthio ethylidene] sulf am ate.
EXAMPLE 3 In a three-neck flask (500 ml.) fitted with a mechanical stirrer, dropping funnel and a drying tube were placed 10 g. or 0.05 mol of N-methyl-N-(2-methyl-6-tert.-butylphenyl)formamide in anhydrous methylene chloride. The solution was cooled in a Dry Ice-isopropanol bath and 6.35 g. or 0.045 mol of chlorosulfonyl isocyanate was added. The reaction was allowed to stir until the NMR showed no isocyanate present. Then 12.2 g. or about 0.1 mol of 2,6-dimethylaniline and approximately a theoretical amount of triethylamine was added to the solution, which was cooled in an ice-salt bath and the reaction mixture was allowed to stir several hours. The resulting solution was washed with Water, the organic phase dried over magnesium sulfate and the solvent was stripped 01f. Recrystallization of the resulting material from ethanol yielded a white solid having a melting point of 173- 174 C.
Both nuclear magnetic resonance and infra-red spectral analysis confirmed the expected structure N-[ot-(2-tert.- butyl-N,6-dimethylanolino)methylidene]-N'-(2,6 xylyl)- sulfamide.
EXAMPLE 4 In a three-neck flask (500 ml.) fitted with a mechanical stirrer, dropping funnel and a drying tube were placed 40 g. or 0.55 mol of dimethylfor-mamide dissolved in ether. The solution was cooled to 0 C. and 70.7 g. or 0.5 mol of chlorosulfonyl isocyanate was added and the reaction was allowed to stir about 3 to 4 hours. First, 50.5 g. of triethylamine was added, then 90 g. of 3-(isopropylcarboxamido)phenol was added and the reaction mixture was allowed to stir for one-half to one hour. The resulting solution was washed with water, the organic phase dried over magnesium sulfate and the solvent was stripped off. Recrystallization of the resulting material from ethanol yielded a white solid having a melting point of 126- 127 C.
Both nuclear magnetic resonance (NMR) and infra-red spectral analysis confirmed the expected structure m-(isopropylcarboxamido)phenyl dimethylaminomethylidenesulfamate.
The utility of the compounds of this invention, that is, the related herbicidal and insecticidal methods, will now be discussed.
The term herbicide as used herein and in the appended claims means materials which (1) effectively control all plants in a given locus or (2) selectively control the growth of one or more plant species in the presence of other plants. In like manner, herbicidal is used to identify the overall and selective control activity of the compositions of this invention.
The term plant as used herein and in the appended claims is inclusive of dormant seeds, germinant seeds, ger-minative seeds, emerging seedlings and established woody and herbaceous vegetation including the roots and above-ground portions.
The term control as used herein and in the appended claims is inclusive of the actions of (l) killing, (2) inhibiting growth, reproduction or proliferation, and (3) removing, destroying or otherwise diminishing the occurrence and activity of plants and is applicable to any of the stated actions, or any combination thereof.
The terms insect and insecticide are used herein in their broad common usage to include spiders, mites, ticks, and like pests which are not in the strict biological sense classed as insects. Thus, the usage herein conforms to the definitions provided by Congress in Public Law 104, the Federal Insecticide, Fungicide, and Rodenticide Act of 1947, section 2, subsection b, wherein the term insect is used to refer not only to those small invertebrate animals belonging mostly to the class Insecta, comprising six-legged, usually winged forms, as beetles, bugs, bees, flies, and so forth, but also to other allied classes of anthropods whose members are Wingless and usually have more than six legs, as spiders, mites, ticks, centipedes, and wood lice.
The term herbicidal or insecticidal composition as used herein means a novel compound of this invention in combination with an adjuvant to be defined hereinbelow.
EXAMPLE 5 The pre-emergent herbicidal activity of the active ingredients of this invention is demonstrated as follows: A good grade of top soil is placed in aluminum pans and compacted to a depth of to /2" from the top of each pan. A predetermined number of seeds of the test plant species are placed on top of the soil in the pans. The seeds are covered with a /8 layer of soil and the pan leveled. The active ingredient is applied by spraying the surface of the top layer of soil with a herbicidal formulation containing a suflicient amount of active ingredient to obtain the desired rate of active ingredient per acre. For soil incor poration, the chemical is sprayed on and mixed into the soil used to cover the seeds.
The seed-containing pans are placed on a wet sand bench and maintained under ordinary conditions of sunlight and watering. The plants are observed at the end of approximately 14 days and the results recorded. The herbicidal activity index is based on the average percent control of each seed lot. The herbicidal activity index is converted to a relative numerical scale for the sake of brevity and simplicity in the table.
The pre-emergent herbicidal activity index used is defined as follows:
Average percent control: Numerical scale 0 to 25 0 26 to 50 l 51 to 2 76 to 3 TAB LE I Dosage, Barnlbs. Morning Wild Rye Sugar yard Crab Pig- Cpd. acre Koohla glory oat Brorne grass Radish beet Cotton Corn Foxtall grass grass weed Cana- Wild dian Vel- Soy- Buck- To- Sor- Smart- Cockle- Lambsthis- Coflce Nutvet Quack- Johnson Bro'mua Cpd. been wheat mato ghum Rice weed bur quarter tle weed sedge leaf grass grass tedorum NOTE.-SOll incorporated all others surface application: A=p-nit rophenyl N-[l-(diethylamino)-2-(O-nitrophenoxy)ethylidenelsulfamate; B=N-l2- chloro-l-(N-isopropylanilino)ethylidenc]-2,6-xylylsulfamide; C =p-n1tro-m-tolyl N-[l-(diethylamino)-2-(p-nitrophcnoxy)cthylidenclsultamate; D=p phenoxyphenyl N-[l-(diethylamino)-2-(phenoxy)-ethylidene]sulfamate; E=N-[l-(diethylamino)-2-(2,4-dichlorophenoxy)-ethy1idenc]-2,6-xylylsu1famide; F=N-[2-chloro-l-(N-isopropy1anilino)ethylidene]-a,a a-trifluoro-m-tolyl-sulfamide; G=m-propionamidophenyl N-[l-(diethylamino)-2-(2,4-diehlorophenoxy)ethylidenelsuliamate; H=2,4-diehlorphenyl lI-[l-(diethylamino)-2-(2,4-dichloropl1enoxy)ethylidenelsuliamate.
EXAMPLE 6 Thereafter is added 0.1 ml. of an acetone solution of In a post-emergent herbicidal test, the active ingrediknow? Foncelitratlon in percent by weight of a compound ents in each case is applied in spray form to 21 day old O.th1s mvemlon ex amp 16 an of by specimens of the plants (species indicated hereinafter). welght.acetofne sohmon prov] es 52 The herbicidal sprays are acetone-Water solutions con- S o w 3 of an 0 taining surface active agents and varying amounts of the Y Welg t aceton? so of the Sald compound active ingredient. The solutions are applied to the plants a Concentratlon of thereof) In the troug in different pans at rates equal to the desired rate of ac- 40 oft e pouch formed by the paper i thereof are placed tive ingredient on a per acre basis. The treated plants are i i com (Zea mays glybnd g about placed in a greenhouse and the effects are observed and {1p g d sereupon to t troug an g e recorded after approximately 14 days see s is a e to 12 ready-to-hatch eggs of t e sout ern corn rootworm (Diabrotica undecimpunctata howardi) The Post emfirgent herblcldal actmty Index used m thls which eggs were washed (with distilled water) free of the example is defined as follows: N I 1 H b, d l ,t SO11 1n wh1ch they were incubated at room temperature umema sea er ac M y for 21 days immediately prior to their placement in the 0 9 phymtoxlclty; trough. The so-charged growth pouch is then placed in an 1 Sl1ghtphytotox1c1ty. h b o d 2 Moderate phytotoxicity. p ig t position m an lncu ator malntamed at 80 F. an 3 Severe phytotoxicity 70% relative humidity for 14 days. Immediately there- 4 Plants dead. after, the growth pouches are removed and the extent of In Table H below the dosage rate method of app1ica kill in percent of the particular species of corn rootworm tion, the spectrum of plant seeds treated, and the results larvae observed. The results were as follows:
TABLE II Morn- Wild Cone. ing Wild Rye Rad- Sugar Fox Crab Pig- Soybuck- Sor- Cpd. percent glory oat Brome grass ish beet tail grass weed bean wheat Tomato ghum H-. 0.5 2 0 0 0 2 1 o 0 1 2 1 1 1 B 0.5 0 0 0 o 0 0 0 1 4 0 0 1 0 0.5 o 0 0 o 0 1 1 3 0 0 1 0 Norm-0.5% concentration equals about 9-10 pounds per acre dosage rate. H=m-(2-methylpropionamido)phenyl N -[1-diethylamino)-2-(2 4,5-trichlorophenoxy)ethylidcne]sulfamate;B =N-[2-chloro-1:(N-isopropy1amhn0)ethylldenel-2,6-xylylsulfamide; E =N- [2chloro-1- ('N-isopropylanili no) ethylidene]-a,a, o.-trlfiuoro-m-tolyl-suliamlde.
of tests using compounds of this invention carried out D according to the above procedure are 1nd1cated.
To illustrate the insecticidal activity of the compounds (goncenration, Percent of this invention, tests were carried out on several different species of insects.
Compound p.p.1u.)
EXAMPLE 7 g gg The act1v1ty of these compounds agamst the southern 5 com rootworm (Diabrotica undecimpunctata howardi) is N01E.where: K is rn-(isopropylcarboxamido)phenyl dimethylamin demonstrated by the follow.mg' methylenesuliamate; L is 2,4-dichl0r0phenyl N-[l-(diethylamlno)-2 To a growth Pouch (dlSPO SEed'Pak growth Pouch, (p-nitrophenoxy)-ethylidene]sulfamate;Misp-nitrophenylN-[l-(diethyl- Catalogue No. B1220 of Scientific Prod ct Di i i f am1n0)-2-(pheny1th1o)ethyhdene] suliamate; N is 2,3,4,5,6-pcntachlorophenyl N-[l-(morpholmo)-2-(phenoxy)-ethylidene]sulfemate; O is p- Amenca Hospital Supply Corporation, Evanston, Ill.) 1n chloro-O-tolyl N-[l-(diethylamino)-2-(p-nitrophenoxy)-ethylidene]sulfaan upright position is added 20 ml. of distilled water.
9 EXAMPLE 8 The compounds of the present invention are also effective against the western corn rootworm (Diabrotica virgifera). To illustrate this activity an aqueous acetone solution of p-nitrophenyl N [1 (diethylamino) 2 (phenylthio)ethylidene]-sulfamate at a concentration of 5 p.p.m. was prepared. About 1 ml. of this solution was used to moisten a sheet of filter paper positioned in a petri dish. Two one-inch sections of corn roots were deposited on the filter paper and the paper was then infested with 5 western corn rootworm larvae. After being maintained for 24 hours at 25 C. and 70% relative humidity, the mortality rate was observed. Under these conditions, 60% of the larvae were killed.
EXAMPLE 9 To illustrate the activity of the compounds of this invention with respect to control of mosquito larvae, tests were carried out employing a standard evaluation procedure on 3-day old early instar yellow fever mosquito larvae (Aedes aegypti) and the results were as follows:
Dosage rate (concentration, Percent Compound p.p.m.) kill NOTE.--I=N-[Z-ehloro-l-(N-isopropylanillno)ethy1ldene]-N'-a,a,a-trlfluoro-m-tolylsulfamide; 2,4-diehlorophenyl N-[1-(diethy1amino)-2- (phenylthio)ethylidenelsulfamate.
The active ingredients hereindefined are suitable for both pre-emergent and post-emergent plant application. That is, they are effective in controlling the growth of germinant seeds, emerging seedlings, and established vegetation by exposing the seeds, emerging seedlings, the roots, the leaves or other above-ground portions to the action of an eifctive amount of one or more of these herbicidally active compounds; however, the best results are usually obtained in a pre-emergent application. Such constitutes a preferred embodiment of the method of controlling plants.
In foliar treatment for herbicidal effect, the active ingredients are applied in amounts from about 0.1 to about 50 or more pounds per acre, preferably about 0.1 to 15 pounds per acre in foliar treatments. In soil applications, it is desirable that the active ingredients be distributed to a depth of at least 0.2 inch. In pre-emergence herbicidal applications the active ingredients are usually applied in amounts from about 0.1 to 25 pounds per acre but preferably from about 0.2 to 10 pounds per acre. It is believed that one skilled in the art can readily determine from the teachings of this specification, including, examples, the procedure for any particular desired application.
In insecticidal applications the active ingredient is usually employed at a rate of 0.01 to 50 pounds per acre. Preferably, they are employed in about 0.1 to 25 pounds per acre.
In practicing the insecticidal and herbicidal methods of this invention, the active ingredients can be used alone or in combination with an appropriate material referred to in the art as an adjuvant in liquid or solid form. The usual purpose of adjuvants is to facilitate application of the active composition and at the desired concentration and/or dosage rate. Insecticidal and herbicidal compositions are prepared by admixing the active ingredient with one or more adjuvants which includes diluents, extenders, carriers and conditioning agents to provide compositions in the form of finely-divided particulate solids or dusts, granules, pellets, solutions, dispersions or emulsions. Thus, the active ingredient can be used with an adjuvant such as a finely-divided particulate solid, a liquid of organic origin, water, a wetting agent, dispersing agent, an emulsifying agent or any suitable combination of these.
Suitable adjuvants of the foregoing types are not here defined in detail as to composition, particle size, relative amounts, etc., since they are well known in the art.
In general, the active ingredients may be formulated with the active ingredient in minor or major proportions in accordance with the table below:
Concentration of active ingredient, percent Type of formulation Herbicidal Insecticidal l. Granules of relatively large particle size-. 5-50 0. 1-05 2. Powdery dusts 2-90 0. 1-75 3. Wettable powders 200 0. l- 4. Emulsifiable concentrates.... 5-95 0. 1-95 5. Solutions and suspensions 0.01- 0. 0001-95 6. One of the less common types of formulations depending on the desired mode of application 01-95 0 001-99 No references cited.
DONALD G. DAUS, Primary Examiner J. TOVAR, Assistant Examiner US. Cl. X.R.
260240 G, 456 A; 424-321; 7l-103, 88
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5136098A (en) * 1991-02-01 1992-08-04 Gamblin Rodger L Nitrosating and diazotizing reagents and reactions

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