Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/52—Two oxygen atoms
  • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
  • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D211/80—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
  • C07D211/84—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen directly attached to ring carbon atoms
  • C07D211/86—Oxygen atoms
  • C07D211/88—Oxygen atoms attached in positions 2 and 6, e.g. glutarimide
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D231/16—Halogen atoms or nitro radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
  • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D249/12—Oxygen or sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
  • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D257/04—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
  • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
  • C07D513/04—Ortho-condensed systems

Definitions

• This invention relates to certain aryl sulfonamides, their N-oxides, agriculturally suitable salts and compositions, and methods of their use for controlling undesirable vegetation.
• the control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, corn (maize), potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of undesired vegetation in noncrop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.
• U.S. 4,818,275 discloses herbicidal acyclic sulfonamides of the formula
• X and Y are Br, Cl or F;
• R is alkyl, haloalkyl or dialkylamino
• R 1 is H, ⁇ a, lower alkyl or SO 2 R;
• R 2 is alkyl, haloalkyl or lower alkoxy; and R 3 is halogen, alkyl or haloalkyl.
• This invention is directed to compounds of Formula I including all geometric and stereoisomers, TV-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use for controlling undesirable vegetation:
• X is H, F or Cl
• Y is F, Cl, Br, cyano, nitro, C*-C 3 haloalkyl, C r C 3 alkoxy, C ⁇ -C 3 haloalkoxy or C(S)NH 2 ;
• R 1 is H, C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C3-C6 haloalkynyl, C 2 -C 6 alkoxyalkyl, C -C 6 haloalkoxyalkyl, formyl, C 2 -C 6 alkylcarbonyl, C4-C7 cycloalkylcarbonyl, C -C 6 haloalkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C3-C6 alkoxyalkylcarbonyl, C 2 -C6 haloalkoxycarbonyl, C3-C6 cycloalkyl, C3-C 6 halocycloalkyl, C4-C7 cycloalkylalkyl, C 4 -C 7 halocycloalkylalkyl
• R 3 is H, C1-C3 alkyl or C r C3 haloalkyl; or R 3 is phenyl optionally substituted with
• R 4 is H, C1-C3 alkyl or C1-C3 haloalkyl; or R 4 is phenyl optionally substituted with C1-C3 alkyl, 1-3 halogen, 4-5 fluorine, 1-2 nitro, C1-C3 alkoxy or CF 3 ;
• R 5 is C j -C 3 alkyl or C - -C 3 haloalkyl; or
• R 4 and R 5 are taken together as -CH-CH 2 -, -CH 2 CH 2 CH 2 -,
• Z is CR6R7, O, S, S(O), S(O) 2 , N(C r C 4
• R 6 is H, C C 6 alkyl, halogen, hydroxy, Cj-Cg alkoxy, C'-C ⁇ haloalkyl, C r C 6 haloalkoxy, C 2 -Cg alkylcarbonyloxy or C 2 -Cg haloalkylcarbonyloxy;
• R 7 is H, C Cg alkyl, hydroxy or halogen; or when R 6 and R 7 are bonded to adjacent carbon atoms they can be taken together with
• CH 2 A the carbons to which they are attached to form optionally substituted with at least one member selected from 1-2 halogen and 1-2 C1-C3 alkyl;
• R 8 is C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
• R 9 is H, halogen, cyano, alkyl, C1-C3 alkoxy or C--C3 haloalkoxy;
• R 1 1 is C r C 6 alkyl, C,-C 6 alkylthio, C r C 6 haloalkyl or N(CH 3 ) 2 ;
• R 12 is H, halogen, C r C 6 alkyl, C r C 6 haloalkyl or C r C 6 alkoxy;
• R 13 and R 14 are each independently H, C r C 6 alkyl or C r C 6 haloalkyl;
• R 15 is H, C r C 6 alkyl or C r C 6 haloalkyl; each R 16 is independently H, C r C 6 alkyl, C ⁇ -C 6 haloalkyl, C 3 -C 6 alkenyl or C 2 -C 6 alkoxyalkyl; R 17 is C r C 6 alkyl, C r C 6 haloalkyl other than CF 3 , C 2 -C 6 alkoxyalkyl, C 2 -C 6 haloalkoxyalkyl, C 2 -C6 cyanoalkyl, C*-C 6 nitroalkyl, C2-C 6 alkylthioalkyl,
• each Q is independently O or S.
• alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, rt-propyl, -propyl, or the different butyl, pentyl or hexyl isomers.
• 1-2 alkyl indicates that one or two of the available positions for that substituent may be alkyl which are independently selected.
• Alkenyl includes straight-chain or branched alkenes such as ethenyl, 1 -propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl” includes straight-chain or branched alkynes such as ethynyl, 1 -propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
• Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
• Alkoxy includes, for example, methoxy, ethoxy, «-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
• Alkoxyalkyl denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
• Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
• Alkylthioalkyl denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 .
• Alkylthioalkoxy denotes alkylthio substitution on alkoxy.
• Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group. Examples of
• alkylsulfmyl include CH 3 S(O), CH 3 CH 2 S(O), CH 3 CH 2 CH 2 S(O), (CH 3 ) 2 CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers.
• alkylsulfonyl include CH 3 S(O) 2 , CH 3 CH 2 S(O) 2 , CH 3 CH 2 CH 2 S(O) 2 , (CH 3 ) 2 CHS(O) 2 and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers.
• Cyanoalkyl denotes an alkyl group substituted with one cyano group.
• Examples of “cyanoalkyl” include NCCH 2 , NCCH 2 CH 2 and CH 3 CH(CN)CH 2 .
• Alkylamino dialkylamino
• alkenylthio alkenylsulfinyl
• alkenylsulfonyl alkynylthio
• alkynylsulfinyl alkynylsulfonyl
• alkynylsulfonyl and the like, are defined analogously to the above examples.
• Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
• Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.
• Examples of “cycloalkylalkoxy” include cyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moieties bonded to straight-chain or branched alkoxy groups.
• Alkylcycloalkyl denotes alkyl substitution on a cycloalkyl moiety.
• Examples include 4-methylcyclohexyl and 3-ethylcyclopentyl.
• Cyanocycloalkyl denotes a cycloalkyl group substituted with one cyano group.
• Examples of “cyanocycloalkyl” include 4-cyanocyclohexyl and 3-cyanocyclopentyl.
• nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides.
• nitrogen containing heterocycles which can form N-oxides.
• tertiary amines can form N-oxides.
• Synthetic methods for the preparation of /V-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxirane.
• MCPBA peroxy acids
• alkyl hydroperoxides such as t-butyl hydroperoxide
• sodium perborate sodium perborate
• dioxiranes such as dimethydioxirane.
• halogen either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine.
• 1-2 halogen indicates that one or two of the available positions for that substituent may be halogen which are independently selected. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
• haloalkynyl examples include HC ⁇ CCHCl, CF 3 C ⁇ C, CC1 3 C ⁇ C and FCH 2 G ⁇ CCH 2 .
• haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
• haloalkylthio examples include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
• haloalkylsulfinyl examples include CF 3 S(O), CCl 3 S(O), CF 3 CH 2 S(O) and CF 3 CF 2 S(O).
• haloalkylsulfonyl examples include CF 3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 and CF 3 CF 2 S(O) 2 .
• haloalkoxyalkoxy examples include CF 3 OCH 2 O, ClCH 2 CH 2 OCH 2 CH 2 O, Cl 3 CCH 2 OCH 2 O as well as branched alkyl derivatives.
• C C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
• C 2 alkoxyalkyl designates CH 3 OCH 2
• C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
• C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
• alkylcarbonyl examples include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
• substituents When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1 , said substituents (when they exceed 1 ) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)i_j, then the number of substituents may be selected from the integers between i and j inclusive.
• Stereoisomers of this invention can exist as one or more stereoisomers.
• the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
• one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s).
• the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
• the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof.
• the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
• the salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
• inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
• the salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol.
• organic bases e.g., pyridine, ammonia, or triethylamine
• inorganic bases e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium
• Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I above, and N-oxides and agriculturally suitable salts thereof, wherein
• R 1 is H, C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 2 -C 6 alkoxyalkyl, C -C 6 haloalkoxyalkyl, C 2 -Cg alkylcarbonyl, C4-C7 cycloalkylcarbonyl, C 2 -C6 haloalkylcarbonyl, C 2 -Cg alkoxycarbonyl, C 3 -C 6 alkoxyalkylcarbonyl, S(O) 2 R 17 , C(O)NR R5 or benzoyl.
• J is J-1, J-2, J-3 or J-6.
• Preferred 4 Compounds of Preferred 3 wherein Z is CR 6 R 7 , O or S; R 6 is H, halogen, C Cg alkoxy or C 2 -C6 alkylcarbonyloxy;
• R 7 is H or halogen; m and n are each independently 1 or 2, provided that m + n is 2 or 3; R 8 is C r C 6 alkyl, C r C 6 haloalkyl or C 3 -C 6 alkenyl; R 9 is halogen, Cj-Cg alkyl, Cj-C 3 alkoxy or C ⁇ -C 3 haloalkoxy; R 10 is C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl or NH 2 ; and
• Rl 1 is C r C 6 alkyl or C r C 6 haloalkyl.
• R 1 is H, C -C 3 alkylcarbonyl or C 2 -C 3 alkoxycarbonyl; and R 2 is C r C 2 haloalkyl.
• J is J-2.
• Preferred 8 Compounds of Preferred 5 wherein J is J-3.
• Preferred 9 Compounds of Preferred 5 wherein J is J-6. Most preferred are compounds of Preferred 5 selected from the group:
• This invention also relates to herbicidal compositions comprising herbicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent.
• This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the compounds of the invention (e.g., as a composition described herein).
• the preferred methods of use are those involving the above preferred compounds.
• the compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-6.
• the definitions of X, Y, R ⁇ -R 17 , J, Q, m, and n in the compounds of Formulae 1-25 below are as defined above in the Summary of the Invention.
• Compounds of Formulae la-If are various subsets of the compounds of Formula I, and all substituents for Formulae la-If are as defined above for Formula I.
• Reaction of the compounds of Formula 4 with diamines of Formula 5 in an inert solvent such as tetrahydrofuran or toluene in the presence of a suitable base such as potassium carbonate, sodium carbonate or pyridine yields the urea intermediates; these urea intermediates are treated with phosgene or a phosgene equivalent to give the compounds of Formula 6.
• Reduction of the nitro group with either tin chloride or iron in acetic acid gives the compounds of Formula 7.
• Condensation of the compounds of Formula 7 with a suitable sulfonyl chloride provides the compounds of Formula la wherein R 1 is H.
• Compounds of Formula la wherein R 1 is other than H can be prepared by treatment of the ⁇ H compound with an alkyl halide, alkyl carbonyl chloride or alkyl sulfonyl chloride to give the corresponding capped compounds of Formula la.
• Diamines of Formula 5 are either commercially available or can be prepared by methods known in the art; see, for instance, EP 075,267 and EP 457, 151.
• Scheme 1
• Scheme 2 illustrates the preparation of compounds of Formula lb.
• Anilines of Formula 3 are treated with sodium nitrite and reduced with tin chloride or iron in acetic acid to give the corresponding hydrazines of Formula 8.
• the hydrazines of Formula 8 are converted to triazolines of Formula 9 by reaction with an appropriate aldehyde, followed by potassium cyanate and bleach; these methods are known in the art: see, for example, Temple Jr., C. The Chemistry of Heterocyclic Compounds (1981), 37, 365-403; Lyga, J. W. Synthetic Communications (1986), 163; Ray, P. S. et al. Heterocyclic Chemistry (1990), 27, 2017; Theodoridis, G. et al. U.S.
• Patent 4,980,480 Alkylation of compounds of Formula 9 with an alkyl halide in the presence of a suitable base gives the compounds of Formula 10.
• the nitro group can then be reduced by the methods described in Scheme 1 to yield the compounds of Formula 1 1 , which are treated with an appropriate sulfonyl chloride to provide the compounds of Formula lb wherein R 1 is H.
• Further functionalization can be accomplished by treatment with an alkyl halide, alkyl carbonyl chloride or alkyl sulfonyl chloride to give the corresponding capped compounds of Formula lb wherein R l is other than H.
• G is halide or sulfonate
• R la is Rl excluding H lb (R- is other than H)
• Compounds of Formula Ic can be prepared by the methods shown in Scheme 3. Anilines of Formula 3 are converted the the corresponding isocyanates of Formula 12 by treatment with phosgene or a phosgene equivalent. The isocyanates of Formula 12 are then condensed with the appropriate substituted alkylcrotonates of Formula 13 in the presence of a base such as sodium hydride, followed by acidification with dilute HC1 to afford the compounds of Formula 14; this method is known in the art: see, for example, Satow, J. et al. EP 408,382-A2.
• R la is R- excluding H
• Compounds of Formula Id can be prepared by the methods shown in Scheme 4.
• the isocyanates of Formula 12 are treated with trimethylsilyl azide and water to afford the tetrazolinones of Formula 17; this method is known in the art: see, for example, Theodoridis, G. Pesticide Science (1990), 30, 259.
• Alkylation using a suitable alkyl halide and reduction with tin chloride or iron in acetic acid gives the compounds of Formula 19.
• the anilines of Formula 19 are then treated with an appropriate sulfonyl chloride to provide the compounds of Formula Id wherein R 1 is H.
• Further functionalization can be accomplished by treatment with an alkyl halide, alkyl carbonyl chloride or alkyl sulfonyl chloride to give the corresponding capped compounds of Formula Id wherein R 1 is other than H.
• Step A The crude product was triturated in diisopropyl ether (1.5 L), isolated by filtration, and dried under reduced pressure to afford the title compound of Step A (196.2 g, 87.6%) melting at 145-146 °C. -H NMR (Me 2 SO- ⁇ f 6 ) ⁇ 10.3-10.2 (s, 1H), 8.9 (d, 1H), 7.9-7.8 (d, 1H), 2.2-2.1 (s, 3H).
• Step B Preparation of 4-chloro-2-fluoro-5-nitrobenzenamine 0
• a solution of title compound of Step A (50 g, 0.214 mol) in 6NHC1 (200 mL) was heated at reflux for 6h.
• Step D Preparation of 3- (4-chloro-2-fluoro-5-nitrophenv ⁇ imino1tetrahydro-lH H- f 1 ,3,41thiadiazolor3,4-a.1pyridazin- 1 -one
• Step F Preparation of 1 -chloro-N-r2-chloro-4-fluoro-5-[ " (tetrahydro-3-oxo- 1H.3H- ri,3,41thiadiazolo[3_,4-q1pyridazin-l- ylidene)aminolphenynmethanesulfonamide
• Step F a compound of this invention, was isolated by flash chromatography as a solid melting at 168 °C ( 1.40 g, 81%).
• Step A Preparation of N-r2-chloro-4-fluoro-5-
• pyridine 0.5 mL
• methylene chloride 5 mL
• dimethylaminopyridine 25 mg
• isobutyryl chloride 110 mg
• Step B Preparation of 3-(4-chloro-2-fluoro-5-nitrophenyl)-6-(trifluoromethyl)-
• Step B The reaction mixture was extracted with ethyl acetate and the solvent was removed under reduced pressure to yield the title compound of Step B which was purified by flash chromatography to give a white solid (5.2 g, 74%).
• Step E Preparation of 1 -chloro-N-r2-chloro-5-f 3 ,6-dihydro-3-methyl-2 ⁇ 6-dioxo-4- (trifluoromethyl (2H)-pyrimidinyl)-4-fluorophenyl1methanesulfonamide
• Step A Preparation of N- f2 -chloro-5 - 3 ,6-dih vdro-3 -methyl-2 ,6-dioxo-4-

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  • 1998-04-20 CN CN 98804408 patent/CN1252803A/zh active Pending
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