NZ239269A - 3-substituted phenyl-5-substituted sulphonyl pyrazole derivatives; herbicidal compositions, methods of preparation and for combating undesirable plants - Google Patents

3-substituted phenyl-5-substituted sulphonyl pyrazole derivatives; herbicidal compositions, methods of preparation and for combating undesirable plants

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Publication number
NZ239269A
NZ239269A NZ239269A NZ23926991A NZ239269A NZ 239269 A NZ239269 A NZ 239269A NZ 239269 A NZ239269 A NZ 239269A NZ 23926991 A NZ23926991 A NZ 23926991A NZ 239269 A NZ239269 A NZ 239269A
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chloro
methyl
methylsulfonyl
fluoro
members
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NZ239269A
Inventor
Deborah Aileen Mischke
Bruce Cameron Hamper
Scott Santford Woodard
Kurt Moedritzer
Michael David Rogers
Gerard Anthony Dutra
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Monsanto Co
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Publication of NZ239269A publication Critical patent/NZ239269A/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • 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
    • C07D231/18—One oxygen or sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Description

New Zealand Paient Spedficaiion for Paient Number £39269 239 269 Priority Dato!.:-}: ^ W I k »]V« w Iv C-MOaSjll,?,: , jQP.lPfHll&ir,:... cc>i pmTlJpv/ • Cf?T\ 0ihoZ>1&t; .C QlPU&i ^>2,' Publication Dat;: ..? .5.MAY.
P.O. Journal, f io: .... .... .[f.....
NEW ZEALAND v\ .<$ Xs_eiV No.: Date: PATENTS ACT, 1953 COMPLETE SPECIFICATION HERBICIDAL SUBSTITUTED ARYL ALKYLSULFONYL PYRAZOLES /Tfwe, MONSANTO COMPANY, a corporation organized and exisiting under the laws of the State of Delaware, United States of America, of 800 North Lindbergh Boulevard, St. Louis, Missouri 63167, United States of America hereby declare the invention for which^i// we pray that a patent may be granted to XP&fus, and the method by which it is to be performed, to be particularly described in and by the following statement: - I (followed by page la) 239 2 6 -lej— 41-21(3046) A HERBICIDAL SUBSTITUTED ARYL ALKYLSULFONYL PYRAZOLES FIELD OF THE INVENTION The field of the invention contemplated herein pertains to herbicidal compounds generically defined by 5 the above title, to compositions containing same and processes for preparing said compounds.
BACKGROUND OF THE INVENTION Various substituted 3- and 5-arylpyrazole-type compounds are known in the literature. Such 10 compounds have various utilities, e.g., as chemical intermediates, pharmaceuticals and herbicides.
Among the substituted-arylpyrazole compounds in the prior art are those having a variety of substi-tuent radicals on the aryl and/or pyrazole moieties of 15 the compound. For example, compounds of this type are known wherein the aryl moeity is a substituted or unsubstituted phenyl radical, in which the substituent radicals are alkyl, cycloalkyl, alkaryl, halogen, trifluoromethyl, heterocyclic or substituted hetero-20 cyclic, e.g., thienyl or alkyl-substituted furanyl, pyridyl, pyrimidinylurea, etc. and the pyrazolyl radical is substituted in various positions on the N or carbon atoms with alkyl, halogen, alkoxy, heterocycles, S(0)nR members, wherein n is 0-2 and R may be a variety of 25 radicals such as those substituted on the aryl or pyrazole moieties.
Prior compounds of the above type having utility as herbicides, typically require application rates as high as five or ten or more kilograms per 30 hectare to achieve adequate weed control. Accordingly, it is an object of this invention to provide a novel class of arylpyrazole-type compounds having uniquely high phytotoxic unit activity against a spectrum of weeds, including narrowleaf and broadleaf weeds yet 35 maintain a high degree of safety in a plurality of crops, especially small grains and/or row crops such as wheat, barley, corn, soybeans, peanuts, etc. 239269 -2- 41*21(3046)A SUMMARY <?f THE INVENTION This invention relates to herbicidally-active compounds, compositions containing these compounds, processes for making them and herbicidal methods of 5 using same. *3 I R, R,-^ SO*"** r6-\u; I-., I R* *7 wherein R, is hydrogen, Ct_s alkyl optionally substituted with an R^ member; Cj.s cycloalkyl or cycloalkenyl optionally substituted with CM alkyl; R, is C,.j alkyl optionally substituted with, an Rs i * member; > ■i _ 'lOQ^ rr' ! Rj is hydrogen or halogen; , > jj Rj is halogen and f VV R^ and R7 are C14 alkyl, haloalkyl, alkylthio, cilkoxy- alkyl or polyalkoxyalkyl, cycloalkyl, cycloalkenyl, cycloal-25 kylalkyl or cycloalkenylalkyl; C^, alkenyl or alkynyl; carbamyl, halogen, amino, nitro, cyano, hydroxy, C ^ jq heterocycle containing 1-4 °/ S(O)m and/or N hetero atoms, aryl, aralkyl or alkaryl, 3q -CXYR,, —CXR9, -CH?OCOR10, -YRU, -NR12R13, or any two Rj-Rt members may be combined through a saturated and/or unsaturated carbon, X II -C- and/or hetero atom linkage to form a heterocyclic ring having 35 up to 9 ring members, which may be substituted with any of said R5-R7 members said Rs-R7 or Rs.,3 members followed by page 2a 23 9 2 69 - 2a - (.f-bllaoo^ ^ substituted with any of said R5-R7 members; provided that when said two Rj-R7 members are combined through a -hetero atom 0 II . . . . -c-N- linkage, said heterocyclic ring has at least six ring members; X is 0, S(0)o, NRW or CRlSR16; Y is O or S (0) m or NRt7; Rj—Rj? are one of said R5-R7 members and m is 0-2 ; provided that when R^ and R2 are methyl, R3 is bromo or chloro, R5 is fluoro, R6 is chloro, R7 is -CH2C02-i-C3H7, -CH2CH2C02C2H5 or YRU wherein Y is O, S or -NR12R13 and 15 Ru-R13 areas defined above. 23 9 2 6 9 41 21(3040)A A preferred subgenus of substituted-arylpyra-zolyl compounds in this•invention are those according to 5 Formula II *5 II AN' (S02)-R2 wherein Rv R2 and R3 are as defined for Formula I; R^ is independently one of said R3 members and R6 and R7 are independently one of said R4 members or are combined to form a heterocyclic ring having up to 9 members and containing 0, N and/or S atoms, which ring may be substituted with alkyl, haloalkyl, alkoxy, alkenyl or alkynyl radicals each having up to 4 carbon atoms; provided that when said two R6 and R7 members are combined through a -hetero atom ?! -C-N- linkage, said heterocyclic ring has at least six ring members.
Particularly preferred compounds of this invention are those according to Formula III j5 III (O (S02)-R2 N wherein fluoro; t'i R1 and Rj are ci-5 alkyl; R3 and Rj are hydrogen, bromo, chloro or " r FtO i93<t .j o ? a -4- 41-21(3(HG)A Rj is an R, member or nitro; R7 is an R4 member or R6 and R7 are combined through an -0CH2(C=0)-N-(R4)- linkage to form a fused six-membered ring. 5 Still more preferred compounds according to Formula III are those wherein R, and R2 are methyl; r3 is hydrogen, bromo or chloro; Rs is chloro or fluoro; R6 is chloro, fluoro or nitro; R7 is a YRn member as defined in Formula I or R6 and Rr are combined through an -0CH2(C=0)-N-(propynyl)-linkage to form a fused six-membered ring.
Preferred species according to this invention include the following: 4-Chloro-3- (2-f luoro-4-chloro-5— (2-propynyloxy) phenyl) - l-methyl-5- (methylsulfonyl) -lH-pyrazole 4-Bromo-3-(2-fluoro-4-chloro-5-(2-propynyloxy)phenyl) -20 l-methyl-5-(methylsulfonyl) -lH-pyrazole 4-Chloro-3-(2-f luoro-4-chloro-5- (2 -methoxy ethoxy) - phenyl) -l-methyl-5- (methylsulfonyl) -lH-pyrazole 4-Bromo-3-(2-fluoro-4-chloro-5-(2-methoxyethoxy) - phenyl) -l-methyl-5- (methylsulfonyl) -lH-pyrazole 25 6- (4-Chloro-l-methyl-5-(methylsulfonyl) -lH-pyrazol-3-y1)-7-fluoro-4-(2-propynyl)-2H-1,4-benzoxaz in-3-(4H)-one (5 - (4-Br omo-1-methy 1 - 5 - (methy lsu 1 f ony 1) - lH-py r a z o 1 - 3-yl)-2-chloro-4-fluorophenoxy) acetic acid, 1-30 methylethyl ester (5-(4-Chloro-l-methy 1-5-(methylsulfonyl) -lH-pyrazol-3-yl)-2-chloro-4-fluorophenoxy) acetic acid, 1-methylethyl ester 3- (5- (4-Bromo-l-methyl-5- (methylsulfonyl) -lH-pyrazol-3-35 yl)-2-chloro-4-fluorophenoxy)propanoic acid, ethyl ester and r~ . ji .-1 1 * ■ ! i FS3 1334 ~7 269 -5- 41-21(3040)A 3- (5- (4-Chloro-l-methyl-5- (methylsulfonyl) -lH-pyrazol-3-yl)-2-chloro-4-fluorophenoxy)propanoic acid, ethyl ester.
Another aspect of this invention relates to 5 processes for preparing the compounds according to Formulae I-III and their precursors and intermediates starting materials. These process aspects will be discussed in more detail below.
Other aspects of this invention relate to 10 herbicidal compositions containing the compounds of Formulae I-III and to herbicidal methods of using those compositions to control undesirable weeds.
It is further within the purview of this invention that the substituted-arylpyrazole compounds of 15 Formulae I-III be formulated in compositions containing other herbicidal compounds as co-herbicides, e.g., acetanilides, thiocarbamates, ureas, sulfonylureas, imidazolinones, benzoic acids and their derivatives, diphenyl ethers, salts of glyphosate, etc. 20 Other additaments may be included in such herbicidal formulations as desired and appropriate, e.g., antidotes (safeners) for the herbicide(s), plant disease control agents, such as fungicides, insecticides, nematicides and other pesticides. 25 As used herein, the terms "alkyl", "alkenyl", alkynyl" when used either alone or in compound form, e.g., haloalkyl, haloalkenyl, alkoxy, alkoxyalkyl, etc., are intended to embrace linear or branched-chain members. Preferred alkyl members are the lower alkyls 30 having from 1 to 4 carbon atoms and preferred alkenyl and alkynyl members are those having from 2 to 4 carbon atoms.
The term "haloalkyl" is intended to mean alkyl radicals substituted with one or more halogen (chloro, 35 bromo, iodo or fluoro) atoms; preferred members of this class are those having from 1 to 4 carbon atoms, r ■ especially the halomethyl radicals, e.g., trifluoro- 1 ■) Fl: 1334 239 2 6 9 -6- 41-21(3046)A methyl. In polyhaloalkyl members, the halogens can all be the same or mixed halogens.
Representative, non-limiting alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl and 5 cycloalkenylalkyl members include the following: Methyl, ethyl, the isomeric propyls, butyls, pentyls, hexyls, heptyls, octyls, nonyls, decyls, etc.; vinyl, allyl, crotyl, methallyl, the isomeric butenyls, pentyls, hexenyls, heptenyls, octenyls; ethynyl, the 10 isomeric propynyls, butynyls, pentynyls, hexynyls, etc.; the alkoxy, polyalkoxy, alkoxyalkyl and polyalkoxyalkyl analogs of the foregoing alkyl groups, e.g., methoxy, ethoxy, propoxys, butoxys, pentoxys and hexoxys and corresponding polyalkoxys and alkoxyalkyls, e.g., 15 methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxy-ethoxy, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, propoxymethyl, isopropoxymethyl, butoxy-methyl, isobutoxymethyl, tertbutoxymethyl, pentoxy-methyl, hexoxymethyl, etc., cyclopropyl, cyclobutyl, 20 cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, etc.; the isomeric cyclopentenes, cyclohexenes and cycloheptenes having mono-or di-unsaturation; representative aryl, aralkyl and alkaryl groups include phenyl, the isomeric tolyls 25 and xylyls, benzyl, naphthyl, etc.
Representative mon-, di- and tri- haloalkyl members include: chloromethyl, chloroethyl, bromo-methyl, bromoethyl, iodomethyl, iodoethyl, chloropropyl, bromopropyl, iodopropyl, 1, l-dichloromethyl, 1,1-di-30 bromomethyl, l, 1-dichloropropyl, 1,2-dibromopropyl, 2,3-dibromopropyl, l-chloro-2-bromoethyl, 2-chloro-3-bromopropyl, trifluoromethyl, trichloromethyl, etc.
Representative heterocyclic members include: alkylthiodiazolyl; piper idyl; piperidylalkyl; dioxo-35 lanylalkyl, thiazolyl; alkylthiazolyl; benzothiazolyl; halobenzothiazolyl; furyl; alkyl-substituted furyl; furylalkyl; pyridyl; alkylpyridyl; alkyloxazolyl; tetrahydrofurylalkyl; 3-cyanothienyl; thienylalkyl; 239 2 6 9 -7- 41-21(3046)A alkyl-substituted thienyl; 4,5-polyalkylene-thienyl; piperidinyl; alkylpiperidinyl; pyridyl; di- or tetrahydropyridinyl; alky ltetrahydromorpholyl; alkylmorpholyl; azabicyclononyl; diazacycloalkanyl, 5 benzoalkylpyrrolidinyl; oxazolidinyl; perhydro-oxazolidinyl; alkyloxazolidyl; furyloxazolidinyl, thienyloxazolidinyl, pyridyloxazolidinyl, pyrimi-dinyloxazolidinyl, benzooxazolidinyl, C3.7 spiro-cycloalkyloxazolidinyl, alkylaminoalkenyl; alkyl-10 ideneimino; pyrrolidinyl; piperidonyl; perhydroazepinyl; perhydroazocinyl; pyrazolyl; dihydropyrazolyl; pipera-zinyl; perhydro-l,4-diazepinyl; quinolinyl, isoquino-linyl; di-, tetra- and perhydroquinolyl - or - iso-quinolyl; indolyl and di- and perhydroindolyl and said 15 heterocyclic members substituted with radicals such as the members defined in Formula I.
As used herein, the term "agriculturally-acceptable salts" (of the compounds defined by the above formulae) is meant a salt or salts which readily ionize 20 in aqueous media to form a cation or anion of said compounds and the corresponding salt anion or cation, which salts have no deleterious effect on the herbicidal properties of a given herbicide and which permit formulation of the herbicide composition without undue 25 problems of mixing, suspension, stability, applicator equipment use, packaging, etc.
By "herbicidally-effeetive" is meant the amount of herbicide required to effect a meaningful injury or destruction to a significant portion of 30 affected undesirable plants or weeds. Although of no hard and fast rule, it is desirable from a commercial viewpoint that 80-85% or more of the weeds be destroyed, although commercially significant suppression of weed growth can occur at much lower levels, particularly with 35 some very noxious, herbicide-resistant plants. 8 41 DETAILED DESCRIPTION OF THE INVENTION The compounds according to this invention are suitably prepared by a variety of processes as will be described below. for preparing the compounds of Formulae I-III is best viewed in the separate process steps required to get the necessary intermediates, immediate precursors and end products of the above formulae. Viewed from this per-10 spective, there are at least thirteen main process steps involved and these will be described below. The products according to Formulae I-III are prepared by the general "Processes I-XIII" scheme described below; it being expressly understood that various modification 15 obvious to those skilled in the art are contemplated. Specific embodiments are described in Examples 1-27 below. below, the various symbols defining radical substi-20 tuents, e.g., R,-R17, X, Y, etc. have the same meanings as defined for the compounds of Formulae I-III, unless otherwise qualified or limited.
PROCESS I important intermediate compounds, which are useful in the overall process scheme for producing compounds of Formulae I-III. Such intermediate compounds of Formula B below in which R3 is H are prepared by this process step.
In broad aspect, the preferred overall process In the sequence of process steps described This process describes the preparation of 1) dithiokctal 2) cyclization R A B 239 2 -9- 41-21(3046)A The process for the preparation of compounds according to Formula B suitably proceeds from (un)substituted acetophenones of Formula A which are known in the art. The process can be carried out in any anhy-5 drous solvent or mixture of such solvents; the preferred solvents are dimethylsulfoxide, toluene, benzene, etc. The (un) substituted acetophenones are treated with a strong base such as an alkali hydride or alkali alkoxide with alkali alkoxides such as potassium t-butoxide being 10 preferred. The basic mixture is treated with carbon disulfide. Reaction temperature is in the range of -100'C to 100*C, preferably -78'C to 50*C. After addition of the carbon disulfide is complete, the reaction may be treated with an alkylhalide, 15 alkyldihalide, alkylsulfate, dialkylsulfonate or other suitable alkylating agent with the preferred reagent being methyl iodide. The reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction tempera-20 ture, etc. After completion of the reaction the intermediate 1 - (subst i tuted) - 3,3 -b i s (a Iky 1 th i o) - 2 -propen-l-one is isolated by diluting the reaction mixture with water and the product is isolated by a method such as crystallization or solvent extraction. 25 If necessary, the product is purified by standard methods. The cyclization of this intermediate to give compounds of Formula B can be carried out in any suitable solvent by treatment with hydrazine or substituted hydrazines with alkylhydrazines being 30 preferred. Reaction temperature is in the range of -78*C to 150*C, preferably 10'C to 100'C. The reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc. The product is isolated 3 5 after completion of the reaction by filtration and/or concentration of the reaction mixture. If necessary, the product is purified by standard methods such as extraction, crystallization, column chromatography, etc. 239 2. 69 -10- 41-21(3046)A In the case of the addition of hydrazine to the intermediate l-(substituted)-3,3-bis(alkylthio)-2-propen-l-one, the resultant pyrazole nay be treated with an alkyl halide, alkyl sulfonate or other suitable 5 alkylating agent to obtain compounds of Formula B. In this case, products of Formula B can be obtained by treatment of the above compound with an alkylating agent such as methyl iodide, benzyl bromide, allyl bromide, dimethyl sulfate, etc. The preferred solvents are 10 dimethylsulfoxide, acetone, dimethylformamide, dioxane, etc. Reaction temperature is in the range of -78*C to 150*C, preferably 10'C to 100*C. The reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction 15 temperature, etc. The product is isolated after completion of the reaction by filtration and/or concentration of the reaction mixture. If necessary, the product is purified by standard methods such as extraction, crystallization, column chromatography, etc. 20 The 2-fluoro-4-chloro-5-methoxyacetophenone, used to prepare compound Nos. 4, 9, 10 and 11 in Table 1 by the above process, was prepared from 2-chloro-4-fluoroanisole, which can be obtained from 2-chloro-4-fluoro-phenol by methods known in the art (C. A. Buehler 25 and D. E. Pearson, Survey of Organic Synthesis, pp. 285-382, Wiley-Interscience, New York, 1970). Treatment of 2-chloro-4-fluoroanisole with titanium tetrachloride and dichloromethylmethylether at room temperature gives 2-fluoro-4-chloro-5-methoxybenzaldehyde. The 2-fluoro-30 4-chloro-5-methoxybenzaldehyde is converted to 2-fluoro-4-chloro-5-methoxyacetophenone by treatment with methyl Grignard followed by oxidation using standard methods known in the art.
The above mentioned 2-fluoro-4-chloro-5-35 methoxyacetophenone and its analogous precursor, 2- fluoro-4-chloro-5-methoxybenzaldehyde and processes for preparing them are the discovery of other inventors 239269 -11- 41-21(3046)A (Bruce C. Hamper and Kindrick L. Leschinsky) employed by the assignee herein.
Table 1 shows typical examples of compounds prepared by Process I.
TAMrE 1 physical data for 3 - aryl- 5 -meth ylthi op yra z oles r5 h W Compound ^ No.
R5 R? physical data mp (°Q or nD(25°C 1 ch3 f h f light yellow oil 2 ch3 f a CH3 90.0 3 ch3 f a h 44.0-45.0 4 ch3 ch3 f h a H OCH3 cf3 50.0-51.0 nD 1.5533 (25°Q 6 ch3 f och3 H nD 1.6036 (25°C) 7 ch3 a a h 90.0 8 h f h f 88.0 9 H f a OCH3 133-135 CH(CH3)2 f a och3 66-67 11 et f • a och3 nD 1.5989 (25°C) 12 ch3 f f H nD 1.5820 Compounds such as those Formula B species shown in Table I are useful as starting materials to prepare various other compounds which, in turn, are 35 useful as intermediates in the preparation of compounds according to Formula II. For example, the compounds in Table I may be halogenated at the pyrazole 3-position to -12- 41-2&3§6& 2 6 9 prepare novel compounds typified by those shown in Table ii. table ii PHYSICAL DATA FOR 3 - ARYL-4-HALO-5-METHYT,TH10P YRAZOLES Compound No. Ri R5 R7 physical data mp (°C) or nD(250Q 14 CH3 f h f nD 1.5791 ch3 f nh2 f 123.0-124.0 16 ch3 f nh2 och3 nD 1.6212 17 ch3 f a f nD 1.5937 18 ch3 f a och3 87.0-88.0 19 ch3 f a ch3 83.0 ch3 f och3 h nD 1.5943 21 H f a OCH3 151.0-152.5 239269 -13- 41-21(3046)A oxidation OW This process describes an important step involving oxidation of compounds according to Formula B 10 to prepare compounds according to Formula I. The important feature of this process step is the conversion of sulfide derivatives of Formula B to obtain the S,S-dioxide derivatives of Formula I compounds. Accordingly, it will be understood that the oxidation system 15 described below is merely representative, but conceptually any suitable means of accomplishing the intended conversion of sulfide derivatives of Formula B to S,S-dioxide derivatives of Formula I is contemplated herein.
Oxidation of substituted thiopyrazoles of 20 Formula B can give the corresponding sulfonylpyrazoles of Formula I. Any inert solvent may be used in this reaction that does not markedly hinder the reaction from proceeding. Such solvents include, but are not limited to, organic acids, inorganic acids, hydrocarbons, 25 halogenated hydrocarbons, aromatic hydrocarbons, ethers or sulfones. Suitable oxidants include, but are not limited to molecular oxygen, organic and inorganic peroxides, organic peracids, inorganic oxides; the preferred reagents being hydrogen peroxide, perbenzoic 30 acids, alkali periodates, alkali permanganates, etc. Reaction temperature is in the range of -78 *C to 150'C, preferably 10*C to 100'C. The reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction 35 temperature, etc. After completion of the reaction the product is isolated by diluting the reaction mixture with water and the product is isolated by a method such 239 2 6 9 -14- 41-21(3046)A as crystallization or solvent extraction, if necessary, the product is purified by standard methods. process iii In this process description, one class of 5 products according to Formula D vherein R3 is halogen is prepared by the halogenation of the corresponding Formula C compound wherein Rj is hydrogen and p is 0 or 2.
H Ro V^_^S{0)pR2 halogenation Lv_^S(0)pR2 N\ (RJi Any inert solvent may be used in this reaction that does not markedly hinder the reaction from proceeding. Such solvents include, but are not limited to, organic acids, inorganic acids, hydrocarbons, halo-genated hydrocarbons, aromatic hydrocarbons, ethers and 20 sulfides, sulfoxides or sulfones. Halogenating agents suitable for the above reaction include bromine, chlorine, N-bromosuccinimide, N-chlorosuccinimide, sul-furyl chloride, 1,3-dichloro-5,5-dimethylhydantoin, etc. With some halogenating agents it is preferable to use an 25 organic peroxide or light as a catalyst. The amount of halogenating agent can range from equivalent molar amounts to an excess. Reaction temperature is in the range of -100'C to 150'C, preferably 10'C to 100'C. The reaction period may be chosen from the range of a few 30 minutes to several weeks or longer depending on the amounts of reagents, reaction temperature, etc. After completion of the reaction the product is isolated by diluting the reaction mixture with water and the product is isolated by a method such as crystallization or 35 solvent extraction. If necessary, the product is purified by standard methods. 239 2 6 9 -15- 41-21(3046)A PROCESS IV This section describes a process for the preparation of compounds according to Formula I in which one of the R4 residues is a nitro group (Formula E) starting with compounds according to Formula I.
R, J>-<r NO, R3 nitration Sl (W '—' N* (Rj Nitrating agents such as concentrated nitric acid, fuming nitric acid, mixtures of nitric acid with 15 concentrated sulfuric acid, alkyl nitrates and acetyl nitrate are suitable for this reaction. Solvents such as mineral acids, organic solvents such as acetic anhydride or methylene chloride, and water or mixtures of these solvents may be used. The nitrating agent may 20 be used in equimolar amounts or in excess. Reaction temperature is in the range of -100*C to 150'C, preferably -10'C to 100'C. The reaction period may be chosen from the range of a few minutes to several days depending on the amounts of reagents, reaction temper-25 ature, etc. After completion of the reaction the product is isolated by diluting the reaction mixture with water and the product is isolated by a method such as crystallization or solvent extraction. If necessary, the product is purified by standard methods.
PROCESS V In this process description, one class of products according to Formula G (one species of Formula II compounds) is prepared by displacement of the Z radical of the corresponding compound of Formula F, 3 5 wherein Z is any suitable leaving group of the previously defined R4 members. i 239 2 6 9 -16- 41-21(3046)A . Rj _ _ R« Rj no/**- " >Hi NO,' Formation of products of Formula G can be carried out by treatment of compounds of Formula F with 10 an alkoxide, thioalkoxide, amine, etc., or an alcohol, mercaptan, amine, etc. in the presence of a base in any suitable solvent. The preferred solvents are dimethyl-sulfoxide, acetone, dimethylformamide, dioxane, water, etc. The base may be an organic base (such as a trial-15 kylamine or another organic amine) or an inorganic base (an alkali carbonate such as potassium carbonate or sodium carbonate). Reaction temperature is in the range of -100'C to 150'C, 'preferably -10'C to 100'C. The reaction period may be chosen from the range of a few 20 minutes to several weeks depending on the amounts of reagents, reaction temperature, etc. The product is isolated after completion of the reaction by filtration and/or concentration of the reaction mixture. If necessary, the product is purified by standard methods 25 such as extraction, crystallization, column chromatography, etc.
PROCESS VI In this process description, a variety of compounds of Formula I (exemplified by Formula J below 30 are prepared from compounds of Formula H (Formula I compounds in which one of the R; members is a nitro residue).
R* SOjRJ (fwr ^ NV (RJ H 239 2 6 9 -17- 41—21(3046)A A. In the first step of this tvo step process, compounds according to Formula H are reduced to give an amine derivative according to Formula J wherein one of the R4 radicals is an amine group. Reducing agents 5 suitable in an acidic medium include, but are not limited to, metals such as iron, zinc or tin. The reaction solvent can include either organic or inorganic acids, such as acetic acid or hydrochloric acid, and may be used as concentrated acid solutions or dilute aqueous 10 solutions. Reaction temperature is in the range of 0*C to 150*C, preferably 10*C to 100*C. The reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
After completion of the reaction the product is isolated by diluting the reaction mixture with water and the product is isolated by a method such as crystallization or solvent extraction. If necessary, the product is purified by standard methods. 20 Alternatively, compounds of Formula H may be reduced by catalytic hydrogenation. For catalytic hydrogenation, which may be carried out at normal or elevated pressures, suitable catalysts include Raney nickel, palladium-carbon, palladium black, palladium on 25 any suitable support, palladium oxide, platinum, platinum black, etc. Solvents include any inert solvent which does not markedly hinder the reaction including alcohols, ethers, etc. The product is isolated after completion of the reaction by filtration and concen-30 tration of the reaction mixture. If necessary, the product is purified by standard methods such as extraction, crystallization, column chromatography, etc.
B. The amine radical of the product of step A can be 35 converted to a variety of functional groups, e.g., a halogen (preferred), cyano, hydroxyl, etc., radical by the following step in the process. In this reaction any suitable solvent may be employed, although, anhydrous 239 2 6 9 -18- 41*21(3046)A solvents such as anhydrous acetonltrile are preferred. A solution or slurry of the product of step A is treated with copper salts including cupric halides, cuprous halides, mixtures of cupric and cuprous halides or other 5 copper salts and their mixtures and with an alkyl nitrite or other organic nitrites, such as t-butyl-nitrite. Reaction temperature is in the range of O'C to 150'C, preferably 10'C to 100'C. The reaction period may be chosen from the range of a few minutes to several 10 weeks depending on the amounts of reagents, reaction tempera- ture, etc. The product is isolated after completion of the reaction by filtration and/or concentration of the reaction mixture. If necessary, the product is purified by standard methods such as 15 extraction, crystallization, column chromatography, etc.
Alternative process operations for converting the amine radical to various functional groups, including those mentioned in the preceding paragraph include use of various conventional procedures, e.g., 20 the Sandmeyer, Meerwein, etc., reactions which employ diazonium salts as intermediates. process vii In this process description, compounds « according to Formula I, wherein one of the R4 members is 25 YH, are prepared from compounds according to Formula I wherein one of the R4 members is YRn and R„ is not hydrogen.
The reaction can be carried out as a solution or suspension in any suitable solvent or neat. A Lewis 30 acid such as, but not limited to, BBr3, A1C13, etc. or inorganic acids such as concentrated or aqueous hydrochloric acid, sulfuric acid, hydrobromic acid, etc. can be employed. Reaction temperature is in the range of O'C to 150*C, preferably 10*C to 100'C. The reaction 35 period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc. The product is isolated after completion of the reaction by filtration and/or 239269 -19- 41-21(3046)A concentration of the reaction mixture. If necessary, the product is purified by standard methods such as extraction, crystallization, column chromatography, etc. PROCESS VIII In this process description, compounds according to Formula I, wherein one of the R4 members is YR^ and Rn is not hydrogen, are prepared from compounds according to Formula I wherein one of the R4 members is YH.
In representative embodiments of this process, formation of products defined above can be carried out by treatment of the starting material with an alkylating agent such as an alkyl halide or alkyl sulfonate, e.g., methyl iodide, allyl bromide, propargyl bromide, methyl 15 phenylsulfonate, etc., or an acylating agent. The reaction may be carried out in any suitable solvent or mixture of solvents, with or without a catalyst, in the presence or absence of a base. The preferred solvents are dimethylsulfoxide, acetone, dimethylformamide, 20 dioxane, etc. The base may be an organic base (such as a trialkylamine or another organic amine) or an inorganic base (an alkali carbonate such as potassium carbonate or sodium carbonate). Reaction temperature is in the range of O'C to 150'C. preferably 10'C to 100'C. 25 The reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc. the product is isolated after completion of the reaction by filtration and/or concentration of the reaction mixture. If 30 necessary, the product is purified by standard methods such as extraction, crystallization, column chromatography, etc.
PROCESS IX This process describes the preparation of 35 compounds of Formula M (Formula II compounds wherein R7 is YCH2.n(R18)nC0YRM) from the corresponding compounds of Formula K. The radicals R18.2o are as previously defined for the said R^ members. 41-212,0$ 269 Rs Rs y r, ~ o={ Rl8>" yr,ft ,"5 % ,"5 R,3 SOaRj M SO^ A. In the first step of this two step process, compounds of Formula K are converted to compounds of Formula L by hydrolysis of the YR19 radical. The 25 reaction can be carried out in any suitable solvent or mixture of solvents, with or without a catalyst, in the presence of a base or acid. The preferred solvents are water, alcohols, dioxane, dimethylsulfoxide, acetone, dimethylformamide, etc. In the case of base hydrolysis, 30 inorganic bases such as alkali hydroxides are preferred. For acid hydrolysis, inorganic acids such as concentrated hydrochloric acid or sulfuric acid, organic acids or mixtures of such acids may be employed. Reaction temperature is in the range of O'C to 150*C, preferably 35 10'C to 100'C. The reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
After completion of the reaction the product is isolated 239 2 69 -21- 41-21(3046)A by diluting the reaction mixture with water and/or treating the solution with acid (in the case of base hydrolysis) and the product is isolated by a method such as crystallization or solvent extraction. If necessary 5 the product is purified by standard methods.
B. The product of step A is converted to compounds of Formula M by ester if ication or an amide-forming reaction. This may be accomplished directly from compound L 10 or via an alkali metal salt of compound L. The esterification can be carried out by using an excess of the alcohol corresponding to the objective ester in the presence of a mineral acid (e.g., sulfuric acid). The amide derivatives can be prepared by treating compound L 15 with the desired amine either neat or in a suitable solvent. The esterification or amide-forming reactions can also be carried out in the presence of an inert solvent and a dehydrating agent.
Alternatively, the product of step A can be 20 converted to an acid halide or anhydride and treated with an alcohol or amine. Preparation of the acid halide is carried out in the presence of a halogenating agent such as, but not limited to, thionyl chloride, phosporus pentachloride, oxalyl chloride, etc., with or 25 without an inert solvent. Any inert solvent which does not interfere with the reaction may be employed. A catalytic amount of an amine base such as triethylamine, pyridine or dimethylformamide or the like may be added for the purpose of promoting this reaction. The reac-30 tion temperature is in the range of -20*C to the boiling point of the solvent used, the reaction period ranges from several minutes to 48 hours depending upon the amounts of reactants used and the reaction temperature.
After completion of the reaction, the excess halogen-35 ating reagent and solvent(s) are removed from the reaction product by evaporation or distillation. The resultant acid halide may be subjected to an amine or alcohol directly or purified by the usual means. 2 3 9 2 6 9 -22- 41-21(3046) A The ^cid halide is treated with an alcohol or amine to give a compound of Formula M. Any inert solvent may be employed and a catalytic amount of an amine base such as triethylamine, pyridine or dimethyl-5 formamide or the like may be added for the purpose of promoting this reaction. The reaction temperature is in the range of -20 *c to the boiling point of the solvent used. The reaction period ranges from several minutes to 48 hours depending upon the amounts of reactants used 10 and the reaction temperature. The product is isolated after completion of the reaction by filtration and/or concentration of the reaction mixture. If necessary, the product is purified by standard methods such as extraction, crystallization, column chromatography, etc. 15 PROCESS X This process describes the preparation of compounds of Formulae 0, P, Q, R, S or T (Formula II compounds in which the R7 substituent is alkyl, substituted alkyl, haloalkyl, carboxaldehyde, carboxylic 20 acid or a carboxylic acid derivative such as the previously defined CXYR^ or CXR^) from compounds of Formula N. The radicals R21 and R22 are as previously defined for the R4 members and X, and X2 are halogens.
Process schematics are shown below. 239269 -23- 41-21(3046)A ft ^ SOjRs halogenatioa N'n> Ri 239 2 6 9 -24- 41—21(3046) A In the first step of this process, compounds of Formulae N are converted to either compounds of Formula 0 or Q or a mixture of these products. Any inert solvent may be used in this reaction that does not 5 markedly hinder the reaction from proceeding. Such solvents include, but are not limited to, organic acids, inorganic acids, hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, ethers and sulfides, sulfoxides or sulfones. Halogenating agents suitable for the above 10 reaction include bromine, chlorine, N-bromosuccinimide, N-chlorosuccinimide, sulfuryl chloride, etc. With some halogenating agents it is preferable to use an organic peroxide or light as a catalyst. The amount of halogenating agent can range from an equal molar amount to 15 an excess. Reaction temperature is in the range of -100'C to 150'C, preferably 10*C to 100'C. The reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc. After completion of the 20 reaction the product or products are isolated by diluting the reaction nix- ture with water and the product(s) are isolated by a method such as crystallization or solvent extraction. If necessary the product(s) are purified by standard methods. 25 Compounds of Formula 0 can be converted to compounds of Formula P by displacement of the halogen radical Xt by a suitable nucleophile. Formation of products of Formula P can be carried out by treatment of compounds of Formula O with an alkoxide, thioalkoxide, 30 amine, alkyl or aryl anion, etc., or an alcohol, mer-captan, amine, etc. in the presence of a base in any suitable solvent. The preferred solvents are dimethyl-sulfoxide, acetone, dimethylformamide, dioxane, etc. The base may be an organic base (such as a trialkylamine 35 or another organic amine) or an inorganic base (an alkali carbonate such as potassium carbonate or sodium carbonate). Reaction temperature is in the range of O'C to 150'C, preferably 10*C to 100'C. The reaction period 2 6 9 -25- 41 may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc. The product is isolated after completion of the reaction by filtration and/or concen-5 tration of the reaction mixture. If necessary, the product is purified by standard methods such as extraction, crystallization, column chromatography, etc.
Formation of products of Formula R can be carried out by acid hydrolysis of compounds of Formula 10 Q. To effect acid hydrolysis, compounds of Formula Q are subjected to an excess of a mineral acid such as hydrochloric acid or sulfuric acid, with a large excess of sulfuric acid being preferred. Reaction temperature is in the range of O'C to the boiling point of the inert 15 solvent, preferably 10'C to 100'C. The reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc. After completion of the reaction the product or products are isolated by diluting the reac-20 tion mixture with water and the product(s) are isolated by a method such as crystallization or solvent extraction. If necessary, the product(s) are purified by standard methods.
Compounds of Formula S are obtained by 25 oxidation of Formula R compounds. Any suitable inert solvent may be employed in this reaction including hydrocarbons, aromatic hydrocarbons, pyridine and its derivatives, water, etc. Oxidizing agents employed include but are not liaited to peroxides such as 30 potassium permanganate or potassium dichromate.
Reaction temperature is in the range of O'C to the boiling point of the inert solvent, preferably 10'C to 100'C. The reaction period may be chosen from the range of a few minutes to several weeks depending on the 35 amounts of reagents, reaction temperature, etc. After completion of the reaction the product or products are isolated by diluting the reaction mixture with water and the product(s) are isolated by a method such as crys- O TO 9 -26- 41-M(TO4S)XI" tallization or solvent extraction. If necessary, the product(s) are purified by standard methods.
The last step of this process is meant to include the transformation of compounds of Formula S to 5 compounds of Formula T by any of the variety of standard techniques for preparation of derivatives of carboxylic acids. This process step is an esterif ication or an amide-forming reaction. This may be accomplished directly from a compound S or via an alkali metal salt 10 of a compound S. The esterif ication can be carried out by using an excess of the alcohol corresponding to the objective ester in the presence of a mineral acid (e.g., sulfuric acid). The amide derivatives can be prepared by treating a compound S with the desired amine either 15 neat or in a suitable solvent. The esterif ication or amide-forming reactions can also be carried out in the presence of an inert solvent and a dehydrating agent.
Alternatively, compounds of Formula S can be converted to an acid halide or anhydride and treated 20 with an alcohol or amine. Preparation of the acid halide is carried out in the presence of a halogenating agent such as, but not limited to, thionyl chloride, phosphorus pentachloride, oxalyl chloride, etc., with or without an inert solvent. Any inert solvent which does 25 not interfere with the reaction may be employed. A catalytic amount of an amine base such as triethylamine, pyridine or dimethylformamide or the like may be added for the purpose of promoting this reaction. The reaction temperature is in the range of -20'C to the boiling 30 point of the solvent used. The reaction period ranges from several minutes to 48 hours depending upon the amounts of reactants used and the reaction temperature. After completion of the reaction, the excess halogenating reagent and solvent(s) are removed from the reac-35 tion product by evaporation or distillation. The resultant acid halide may be subjected to an amine or alcohol directly and purified by the usual means. -»&&& 2 6 9 -27- 41 The acid halide is treated with an alcohol or amine to give a compound or Formula T. Any inert solvent may be employed and a catalytic amount of an amine base such as triethylamine, pyridine or 5 dimethylformamide or the' like may be added for the purpose of promoting this reaction. The reaction temperature is in the range of -20 *C to the boiling point of the solvent used. The reaction period ranges from several minutes to 48 hours depending upon the 10 amounts of reactants used and the reaction temperature. The product is isolated after completion of the reaction by filtration and/or concentration of the reaction mixture. If necessary, the product is purified by standard methods such as extraction, crystallization, 15 column chromatography, etc.
PROCESS XI This section describes a process for the preparation of compounds according to Formula I in which one of the R4 residues is a thiol group (Formula U) 20 starting with compounds according to Formula I.
SH SO2R2 cjs, JV^VSOjRJ mO-vJ" "1 u In this process, the desired compounds are obtained by preparation of a halosulfonyl intermediate 30 followed by reduction to give compounds of Formula U. Any solvent may be employed that does not hinder the progress of the reaction such as halogenated hydrocarbons, ethers, alkylnitriles, mineral acids, etc. An excess of chlorosulfonic acid is preferred as both the 35 reagent and solvent for the formation of chlorosulfonyl intermediates. The reaction temperature is in the range of 25*C to the boiling point of the solvent employed. The reaction period may be chosen from the range of a 41-21 few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc. After completion of the reaction the product or products are isolated by diluting the reaction mixture with water and the pro-5 duct(s) are isolated by a method such as crystallization or solvent extraction. If necessary, the product(s) are purified by standard methods. be carried out in inert solvents including either 10 organic or inorganic acids, such as acetic acid or hydrochloric acid, and may be used as concentrated acid solutions or dilute aqueous solutions. Reducing agents suitable in an acidic medium include, but are not limited to, metals such as iron, zinc or tin. The 15 reaction solvent can include Reaction temperature is in the range of O'C to 150'C, preferably 10'C to 100'C. The reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
After completion of the reaction the product is isolated by diluting the reaction mixture with water and the product is isolated by a method such as crystallization or solvent extraction. If necessary, the product is purified by standard methods.
PROCESS XII In this process step, compounds of Formula V (Formula I compounds in which R2 is CH^^ where Ra is one of the previously defined R4 members) are prepared from compounds of Formula I where Rz is methyl.
Reduction of the halosulfonyl intermediate can R I V • -29- 41-21(3 Any suitable solvent may be eaployed provided that it is anhydrous, does not react with water, and does not interfere with the course of the reaction. Preferably, anhydrous ethers such as tetrahydrofuran, 5 diethyl ether or polyethers are employed. The reaction temperature is usually -100'C to the boiling point of the solvent employed with -78*C to 25*C being preferred. Initially, the compound of Formula I is treated with a strong base such as an alkyl metal, metal hydride, metal amide, etc., followed by treatment with an alkylating agent such as an alkyl halide, an alkyl sulfonate, etc. The reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
After completion of the reaction the product is isolated by diluting the reaction mixture with water and the product is isolated by a method such as crystallization or solvent extraction. If necessary, the product is purified by standard methods.
PROCESS XIII This process step describes the conversion of compounds of Formula W to either compounds of Formulae X or Y. The radical R24 is as previously defined for one of the R4 members and n is an integer of 0 or 1.
U9 2 6 9 °: ^ °24 w 239269 -30- 41-21(3046)A In this process step, the nitro radical of compounds according to Formula W is reduced to give an amine derivative which can either be isolated or allowed to cyclize directly to give products of Formulae X or Y 5 depending on the nature of the R24 radical. In some cases, it may be necessary to carry out the above reactions at elevated temperatures in order to facilitate cyclization of the amine intermediate. Reducing agents suitable in an acidic medium include, but are not 10 limited to, metals such as iron, zinc or tin. The reaction solvent can include either organic or inorganic acids, such as acetic acid or hydrochloric acid, and may be used as concentrated acid solutions or dilute aqueous solutions. Reaction temperature is in the range of O'C 15 to 150'C, preferably 10'C to 100'C. The reaction period may be chosen from the range of a few minutes to several weeks depending on the amounts of reagents, reaction temperature, etc.
After completion of the reaction the product 20 is isolated by diluting the reaction mixture with water and the product is isolated by a method such as crystallization or solvent extraction. If necessary, the product is purified by standard methods.
Alternatively, compounds of Formula W may be 25 reduced by catalytic hydrogenation. For catalytic hydrogenation, which may be carried out at normal or elevated pressures, suitable catalysts include Raney nickel, palladium-carbon, palladium black, palladium on any suitable support, palladium oxide, platinum, plati-30 num black, etc. Solvents include any inert solvent which does not markedly hinder the reaction including alcohols, ethers, etc. The product is isolated after completion of the reaction by filtration and concentration of the reaction mixture. If necessary, the product 35 is purified by standard methods such as extraction, crystallization, column chromatography, etc. 239269 41-21 (7t>45) A The following Examples 1-27 describe specific working embodiments for the preparation of representative compounds according to this invention. In the examples which follow, where chromatographic purifi-5 cations were done the adsorbent material was silica.
Examples 1-3 describe specific working embodiments of Process I, used to prepare intermediate compounds for preparing the final products of this invention.
Example 1 (A.) All equipment was flame dried under Nz. To a slurry of 5.4 g (0.18 mole) 80* oil dispersion NaH in 150 mL dry DMSO was added 14.04 g (0.09 mole) 2,5-di-fluoroacetophenone (commercially available) over 10 min. 15 A gas evolution was noted. The reaction was cooled to 15* and 5.4 mL (0.09 mole) CS2 were added over 15 min. keeping the temperature at 15*C and the gas evolution under control, ll.l mL (0.018 mole) methyl iodide was added immediately after the completion of the CS2 20 addition at 20*C. The reaction was stirred for 2 hr. at room temperature. The reaction mixture was poured into 500 mL ice and stirred for 1 hr. The solid was filtered, washed with water and air dried. The residue was purified chromatographically using 20% ethyl acetate 25 in hexane as the eluent to give 19.8 g (85%) of l-(2,5-difluorophenyl)-3,3-bis(methylthio)-2-propen-l-one as a yellow solid, mp 105.5*C; Alternatively, for the procedure described in step (A.) a mixture of anhydrous solvents can also be 30 used, e.g., a mixture of DMSO and THP.
Anal. Calc. for C^H^FjO^: C,50.75; H,3.87; S,24.63.
Found: C,50.85; H,3.86; S,24.75.
(B.) To a slurry of 4.0 g (0.0154 mole) of the product of step (A.) in 50 mL acetonitrile was added 1.65 mL 35 (0.031 mole) methylhydrazine over 15 min. at 24*C. The solution was refluxed for 6 hr. The solution was stripped in vacuo. The residue was purified chromato- 2 -32- 41-21(3046)A graphically using 10% ethyl acetate in hexane as the eluent to give 3.05 g (82%) of 3-(2,5-difluorophenyl)-l-methyl-5-(methylthio)-lH-pyrazole as a light yellow oil; Anal. Calc. for C^H^FjNjS, : C, 54.99; H,4.20; N,11.66; S,13.34.
Found: C,55.03; H,4.26; N,11.55; S,13.38.
Example 2 This example describes the preparation of an isomeric mixture of 3-(2,5-difluorophenyl)-l-methyl-5-methylthio-lH-pyrazole and 5-(2,5-difluorophenyl)-1-methyl-3-methylthio-lH-pyrazole.
A. To a solution of 5.2 g 1-(2,5-difluorophenyl)-3,3-15 bis(methylthio)-2-propen-l-one in 50 mL acetonitrile at 24*C was added 1.3 mL of anhydrous hydrazine over a period of 3 minutes. The reaction was heated to 95*C for 1 hour. The reaction was concentrated in vacuo. The residue was taken up in diethyl ether and washed 20 with water, dried over anhydrous MgS04, and concentrated in vacuo. The residue was recrystallized from hexane to give 4.14 g (94%) of 3-(2,5-difluorophenyl)-5-(methylthio) -lH-pyrazole as a white solid, mp 88*C.
Anal. Calc. for C^F^S,: C,53.09; H,3.56; N,12.38; 25 S,14.17.
Found: C,53.12; H,3.55; N,12.40; S,14.15.
B. A slurry of 3.44 g of the product of Step A, 2.2 g K2C03, and 1.0 mL methyl iodide in 75 mL acetone was stirred overnight at 25 *C. The solution was diluted with 300 mL cold water and extracted three times with ethyl acetate. The ethyl acetate extracts were washed with brine, dried over anhydrous MgS04, and concentrated in vacuo. The residue was purified chromatographically 35 using 10% ethyl acetate in hexane as the eluent to give 2.97 g (85%) of 3-(2,5-difluorophenyl)-l-methyl-5-methylthio-lH-pyrazole (analysis given in Example 1) and 0.35 g (10%) of 5-(2,5-difulorophenyl)-l-methyl-3- 23! -33- 41-21(3046)A (methylthio)-lH-pyrazole as a light yellow oil, nf5 1.5731.
Anal. Calc. for C11H10F2N2S1: C, 54.99; H,4.20; N,11.66.
Found: C,54.83; H,4.19; N,11.85.
Example 3 This example describes the preparation of 3-(2,4-difluorophenyl)-l-methyl-5-(methylthio)-1H-pyrazole.
All glassware was flame dryed. To a mechanically 10 stirred solution of potassium t-butoxide (43g 0.38mol) in anhydrous tetrahydrofuran (600ml) was added 2,4-di-fluoroacetophenone (30g, 0.192mol). The solution exothermed to 40*C and was stirred at that temperature for 30 minutes. The solution was then cooled to O'C and 15 a solution of carbon disulfide (11.6 ml, 0.192 mol) was added at such a rate that the temperature of the reaction never exceeded 1*C. After the addition was complete, the reaction was stirred for 15 minutes at O'C, followed by the addition of methyl iodide (2 3.6g, 20 0.38 mol) never letting the solution temperature rise above 1*C. The solution was stirred using no cooling until it reached 10*C, at which time the reaction solution was poured onto 1L of ice water. Two crops of a filterable yellow solid were collected to give a total 25 yield of 48.lg (96% yield) of the dithioketal. The dithioketal (47g, 0.180 mol) was dissolved in acetonitrile (500 ml) and methyl hydrazine (21g, 0.45 mol) was added all in one portion. The solution was brought to reflux for 24 hours and then most of the acetonitrile 30 was stripped off under vacuum. The remaining liquid was poured onto ice water and extracted into diethyl ether. The organics were washed with brine three times and dried over anhydrous magnesium sulfate, and stripped of all volatiles to give 37.77g (87% yield) of 3-(2,4-35 difluorophenyl)-l-methyl-5-(methylthio)-lH-pyrazole as an amber oil. 'HNMR (CDC13) ppm: 7.82 (q, J=6.6, 1H), 6.78 (m, 2H), 6.55 (d, J=3.6, 1H), 3.83 (s, 3H), 2.34 (s, 3H). 239 2 6 9 -34- 41-21(3046)A Anal. calc. for C^H^F^S,: C, 54.99; H,4.20; N,11.66 Found: C,55.06; H,4.23; N,11.60. Examples 4, 5 and 6 describe specific working embodiments of Process II. 5 Example 4 This example describes the preparation of 3-(2,5-dif luorophenyl) -l-methyl-5-(methylsulfonyl) -1H-pyrazole.
A solution of 2.66 g (0.011 mole) of the product of step 10 (B) , Example 1, in 50 mL methylene chloride was cooled to -5'C. A solution of 7.6 g (0.022 mole) 50-60* m-chloro-perbenzoic acid in 100 mL methylene chloride was added to the reaction mixture and allowed to stir overnight at room temperature. The solution was washed with 15 a saturated sodium bicarbonate solution containing 5* sodium thiosulfate, followed by a water wash, dried over anhydrous MgS04, and concentrated in vacuo. The residue was recrystallized from methylcyclohexane to give 2.8 g (93*) of 3-(2,5-dif luorophenyl) -l-methyl-5-(methyl-2 0 sulfonyl)-lH-pyrazole as a white solid, mp 126-127*C; Anal. Calc. for C11H10F2O2S1: C,48.53; H,3.70; N,10.29; S,11.78.
Found: C,48.61; H,3.70; N,10.26; S,11.71.
Example 5 This example describes the preparation of 5-(4-chloro-2-f luor o- 5 -methoxypheny 1) - 3 - (methy 1 su 1 f ony 1) -lH-pyrazole.
To a solution of 1.12 g of 5-(4-chloro-2-30 fluoro-5-methoxyphenyl)-3-(methylthio)-lH-pyrazole in a mixture of 30 mL of glacial acetic acid and 15 mL of ethanol was added 3.2 g of Oxone*. The heterogeneous mixture was heated to 85 *C and after 2 hours was poured into ice water. The resultant mixture was extracted 35 three times with methylene chloride and the organic extracts concentrated to afford an oily residue. Solution of the oily residue in 10* aqueous NaOH followed by neutralization with concentrated HC1 239 2 69 -35- 41-21(3046)A afforded a solid precipitate which was collected and washed with water to afford 0.60 g (48%) of 5-(4-chloro-2-f luoro-5-methoxyphenyl) -3- (methylsulfonyl) -1H-pyrazole. An analytical sample was obtained by 5 recrystallization from methanol/water to give a yellow, crystalline solid; mp 213-216 (dec.)* Anal. Calc. for C^H^OjF,: C,43.36; H,3.31; N,9.19; S, 10.52.
Found: C,43.51; H,3.33; N,9.10; 10 S,10.44.
Example 6 This example describes the preparation of 4-chloro-3-(2-f luoro-4-methoxyphenyl) -l-methyl-5-(methylsulfonyl)-1H-pyrazole.
To a O'C solution of 4-chloro-3-(2-fluoro-4- methoxyphenyl) -l-methyl-5- (methylthio) -lH-pyrazole (3.5g, 0.0122 mol) in methylene chloride (150 mL) was added m-chlorobenzoic acid in small portions. The reaction was stirred for 20 hours at room temperature, then the organics were extracted twice with a 50% solution of saturated sodium bicarbonate in saturated sodium thiosulfate solution. The organics were dried over anhydrous magnesium sulfate and the volatiles removed under vacuum to give a yellow solid with mp = 75'C.
Anal. Calc. for C^^F^jOjS^l,: C,45.22; H,3.79; N,8.79.
Found: C,45.49; H,3.77; N, 8.69.
Examples 7 and 8 describe specific working embodiments of Process III.
Example 7 This example describes the preparation of 4-chloro-3- (2,5-dif luorophenyl) -l-methyl-5- (methylsul-35 fonyl)-lH-pyrazole.
At 25*C, 2.25 g (8.2 mmole) of the product of Example 4 was dissolved in 40 mL glacial acetic acid and 1.1 g (16.4 mmole) chlorine gas was bubbled in over a 239 2 6 9 -36- 41-21(3046)A period of 50 minutes. The reaction vas allowed to stir for 45 minutes. The reaction solution vas poured into 300 mL ice water, and extracted with diethyl ether. The ether was washed with a saturated sodium bicarbonate 5 solution, dried over anhydrous MgS04, and concentrated in vacuo. The residue was purified chromatographically using 30% ethyl acetate in hexane as the eluent to give 1.35 g (84%) of 4-chloro-3-(2,5-dif luorophenyl) 1-methyl-5-(methylsulfonyl) lH-pyrazole as a white solid, mp 77*C; 10 Anal. Calc. for C^HfC^FjN^S,: C,43.08; H,2.96; N,9.13; S,10.45; CI,11.56.
Found: C,43.16;H,2.97 ;N, 9.12; S,10.39; CI,11.49.
Example 9 This example describes the preparation of 4- chloro-3 - ( 2-f luoro-4 -methoxypheny 1) -l-methyl-5- (methylthio) -lH-pyrazole.
To a O'C solution of 3-(2-fluoro-4-methoxy-phenyl)-l-methyl-5-(methylthio)-lH-pyrazole (4g, 0.015 20 mol) in diethyl ether (30 ml) and l drop of glacial acetic acid was added l,3-dichloro-5,5-dimethylhydantoin (1.77 g, 0.009 mol). The reaction was stirred for one hour at room temperature and then poured onto ice. The organics were extracted into diethyl ether, washed with 25 brine, dried over anhydrous magnesium sulfate and stripped in vacuo to give a yellow oil, n^ = 1.5943 at 25'C.
Anal. Calc. for C^^NjO^Cl,: C,50.26; H,4.22; N,9.77.
Found: C,49.84; H,4.13; N,9.61.
Examples 9 and 10 describe specific working embodiments of Process IV.
Example 9 This example describes the preparation of 4-chloro-3- (2,5-dif luoro-4-nitrophenyl) -l-methyl-5-35 (methylsulfonyl)-lH-pyrazole. 2 3 9 2 6 0 -37- 41-21(3046)A At 24 *C, 1.5 g (4.9 mmolej' 4-chloro-3-(2,5-d if luorophenyl) -l-methyl-5-(methylsulfonyl) -lH-pyrazole, was slowly added to 25 mL of fuming nitric acid. The reaction was stirred at' 30 *C for 30 minutes. The 5 reaction was poured into 300 mL of ice. The slurry was filtered and the cake washed well with water and air dried. The solid was recrystallized from methylcyclo-hexane to give 1.13 g (66%) of 4-chloro-3-(2,5-difluoro-4-nitrophenyl) -l-methyl-5- (methylsulfonyl) -lH-pyrazole 10 as a beige solid, mp 147*C; Anal. Calc. for C^HgCl^jNjO^: C,37.56; H,2.29; N, 11.95; S,9.12.
Found: C,37.60; H/2.29;N,11.98; S,9.10.
Example 10 This example describes the preparation of 4-chloro-3 - (4 -chloro-2 -f luoro-5-nitropheny 1) -1 -methy1-5-(methylsulfonyl)-lH-pyrazole.
To a solution of 3g (0.0093 mol) of 4-chloro-20 3-(4-chloro-2-fluorophenyl)-l -methy 1-5- (methy1su1fony1) -lH-pyrazole in 3 mL of concentrated sulfuric acid was added a mixture of 1 mL of concentrated nitric acid in 3 mL concentrated sulfuric acid, dropwise. This mixture was then stirred at 25'C for 2 hours. The reaction 25 mixture was then poured into ice-water and extracted with ether. The organic extracts were then washed three times with 100 mL of aqueous NaCl, dried (MgSOJ, filtered and concentrated to afford 2.3g (67%) of 4-chloro-3-(4-chloro-2-fluoro-5-nitrophenyl) -l-methyl-5-30 (methylsulfonyl)-lH-pyrazole as a yellow solid.
Chromatography (10% EtOAc/CH2Cl2) afforded an analytical sample, mp 111-115*C.
Anal. Calc. for C11H8N304C12F1S1 + 1/4 EtOAc: C,36.45; H,2.60; N,10.85.
Found: C,36.39; H,2.26; N,10.91.
Examples 11 and 12 describe specific working embodiments of Process V. 239 2 6 9 -38- 41-21(3046)A Example 11 This example describes the preparation of 4-chloro-3-(2-f luoro-5-methoxy-4-nitrophenyl) -l-methyl-5-(methylsulfonyl)-lH-pyrazole.
A mixture of 4.8 g (0.0137 mole) of the product of Example 9, 1.9 g (0.014 mole) K2C03, and 5 mL methanol vas slurried in 50 mL DMSO at 25*C. The reaction vas stirred at 45*C for 8 hours. The reaction vas cooled, diluted vith 100 mL cold vater, and 10 extracted four times vith ethyl acetate. The ethyl acetate extracts were vashed vith brine, dried over anhydrous MgS04, and stripped in vacuo. The residue was recrystallized from ethyl acetate/hexane to give 4.21 g (84%) of 4-chloro-3-(2-fluoro-5-methoxy-4-nitrophenyl) -15 l-methyl-5-(methylsulfonyl)-lH-pyrazole as a yellow solid, mp 178.5-180*C; Anal. Calc. for C12H11C11F1N305S1: C,39.62; H,3.05; N,11.55; S,8.81.
Found: C,39.58; H,2.98; 20 N,ll.54; S,8.59.
Example 12 This example describes the preparation of 5-[ 4-chloro-l-methyl-5- (methy lsu If onyl) -lH-pyrazol-3-yl] -4-f luoro-N- (1-methylethyl) -2-nitrobenzenamine. 25 To a solution of 4-chloro-3-(2,5-difluoro-4- nitrophenyl) -l-methyl-5- (methylsulfonyl) -lH-pyrazole (7.6g, 0.0218 mol) in n-methyl pyrrolidinone (50 ml) vas added isopropyl amine (1.94g, 0.0328 mol), potassium carbonate (4.5g, 0.0328 mol) and a catalytic amount of 30 copper (II) fluoride. The reaction vas heated to 60*C for two hours and determined complete by TLC. The reaction was diluted into ethyl acetate and the organics were vashed three times with brine, dried over anhydrous magnesium sulfate and the volatiles removed under vacuum 35 to give 8.4g (98%) of 5-[4-chloro-l-methyl-5-(methylsulfonyl) -lH-pyrazol-3-yl] -4-f luoro-N- (1-methylethyl) -2-nitrobenzenamine as an orange solid after recrys-talization from ethanol/methyl cyclohexane, mp 152*C. 239 2 69 -39- 41-21(3046)A Anal. Calc. for ^H^Cl^N^S,: C,43.03; H,4.13; N, 14.34.
Found: C,43.09; H,4.09; N,14.36.
Example 13 This example describes the preparation of 4-5 chloro-3-(4-chloro-2-fluoro-5-methoxyphenyl) -1-methy1-5-(methylsulfonyl)-lH-pyrazole is a specific embodiment of Process VI.
(A.) A slurry of 3.3 g (9.1 mmole) of 4-chloro-3-(2-f luoro-5-methoxy-4-nitrophenyl) -l-methyl-5- (methyl-10 sulfonyl)-lH-pyrazole in 100 mL of acetic acid was heated to 80*C under nitrogen and treated portionwise with 1.5 g (27 mmole) of iron powder. After 20 minutes at 85'C, the mixture was allowed to cool and filtered through celite*. The resultant solution was diluted 15 with 250 mL of water and extracted three times with ethyl acetate. The organic extracts were washed with water, saturated aq. NaHCOj, water, dried with MgS0; and concentrated to afford 3.1 g of a tan solid. (B.) A solution of 3.0 g (9.0 mmole) of the product of 20 step (A.) in 70 mL dry acetonitrile at 25*C was treated with 0.9 g (9.0 mmole) CuCl and 1.8 g (13.1 mmole) CuCl2. A solution of 2.4 mL (18 mmole) 90% t-butyl nitrite was added to the reaction mixture over 5 minutes. After 1 hour at 28 *C the reaction mixture was concentrated in 25 vacuo. The reaction residue was taken up in ethyl acetate and vashed three times with a 10% HCl solution, two times with brine, dried over anhydrous MgS04, and concentrated in vacuo. The residue was purified chromatographically using 50% ethyl acetate in hexane as 30 the eluent to give 2.64 g (83%) of 4-chloro-3-(4-chloro-2-f luoro-5-methoxyphenyl) -l-methyl-5- (methylsulfonyl) -lH-pyrazole as a white solid, mp 127.5*C.
Anal. Calc. for C^^CljF^OjS,: C,40.81; H,3.14; N,7.93; S,9.08; Cl,10.08. 35 Found: C,40.94; H,3.14; N,7.88; S,8.97; CI,19.95.
Examples 14-16 describe specific working embodiments of Process VII. 2,3 9 l -40- 41^rif3046)A n R Q Example 14 This example describes the preparation of 2-chloro-5-[4-chloro-l-methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl]-4-fluoro-N-2-propenylbenzenamine. 5 A solution of 1 g (0.0023 mol) of N-[2-chloro- -[4-chloro-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-yl]-4-fluorophenyl]-2,2,2-trifluoroacetamide, 0.97 g (0.007 mol) of potassium carbonate, 25 mL of anhydrous DMF and 0.85g (0.007 mol) of allyl bromide was allowed 10 to stir at 70*C for 24 hours. This solution was diluted with EtOAc, washed with three times 100 mL of 5* HCl, dried (MgSOJ , filtered and concentrated to afford 0.9g of a red oil. This oil was dissolved in 20 mL of methanol and 3 mL of 10% NaOH was added. This mixture 15 was stirred at 25*C for 8 hours. The reaction mixture was diluted with EtOAc, washed with three times 100 mL of aqueous NaCl, dried (MgSOJ, filtered and concentrated to afford 0.8g of a red oil. Chromatography (CH2C12) afforded 0.6g (69%) of 2-chloro-5-[4-chloro-l-methyl-5-20 (methylsulfonyl) -lH-pyrazol-3-yl]-4-f luoro-N-2-propenyl-benzenamine as a yellow oil, n^5 = 1.5956.
Anal. Calc. for CMHUN302C12F,S,: C,44.46; H,3.73; N,ll.li.
Found: C,44.66; H,3.68; N,10.85.
Example 15 This example describes the preparation of N- [2-chloro-5-[4-chloro-l-methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl]-4-fluorophenyl]-methanesulfonamide.
To a solution of 0.5g (0.001 mol) of N-[2-chloro-5-[4-chloro-l-methyl-5-(methylsulfonyl)-1H-3 0 pyrazol-3-yl]-4-fluorophenyl]-N-(methylsulfonyl)- methanesulfonamide in 20 mL of methanol was added 2 mL of 10% NaOH. This mixture was stirred at 25*C for 4 hours. The reaction mixture was diluted with EtOAc, washed with three times 100 mL of 5% HCl, dried (MgS04), 35 filtered and concentrated to afford 0.2g (48%) of N-[2-chloro-5-[4-chloro-l-methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl]-4-fluorophenyl]methanesulfonamide as a 239 2 6 9 -41- 41-21(3046)A yellow-tan solid. Chromatography (EtOAc) afforded an analytical sample, mp 165-166*C.
Anal. Calc. for C^^NjO^Cl^Sj + 1/4 EtOAc: C,35.18; H,3.24; N,9.65. 5 Found: C,35.09; H,2.97; N,9.90.
Example 16 This example describes the preparation of 4-chloro-3-(4-chloro-2-f luoro-5-hydroxyphenyl)-l-methyl-5-(methylsulfonyl)-lH-pyrazole.
A solution of 1.15 g (3.25 mmole) 4-chloro-3- (4-chloro-2-f luoro-5-methoxyphenyl) -l-methyl-5- (methylsulfonyl)-lH-pyrazole in 30 mL methylene chloride was chilled to O'C and treated with 4 mL of a 1M methylene chloride solution of BBr3 (4.0 mmole) vas added slowly 15 over 5 minutes. The solution was allowed to stir overnight at room temperature. The solution was vashed two times with water, dried over anhydrous MgS04, and concentrated in vacuo. The residue was recrystallized from hexane to give 1.1 g (100%) of 4-chloro-3-(4-20 chloro-2-f luoro-5-hydroxyphenyl) -l-methyl-5- (methylsulfonyl)-lH-pyrazole as a beige solid, mp 190.5*C; Anal. Calc. for C^CljF^OjS,: C.38.95; H,2.67, N,8.26.
Found: C,38.93; H,2.67; N,8.43.
Examples 17, 18, 19 and 20 describe specific 25 working embodiments of Process VIII.
Example 17 This example describes the preparation of 2-chloro-5-[4-chloro-l-methyl-5- (methylsulfonyl) -1H-pyrazol-3-yl]-4-f luoro-N-(1-methylethyl) -benzeneamine. 30 A solution of 0.5g (0.0015 mol) of 2-chloro- -[4-chloro-l-methyl-5-(methylsulfonyl) -lH-pyrazol-3-yl]-4-f luorobenzenamine and 2 mL of 2-iodopropane in 5 mL of anhydrous DMF was stirred at 75'C for 6 hours, then at 25*C for 2-1/2 days. The reaction mixture was 35 diluted with EtOAc, washed with two times 50 mL of 5% HCl, dried (MgS04), filtered and concentrated to afford 0.5g red oil. Chromatography (methylene chloride) afforded 0.25g (44%) of 2-chloro-5-[4-chloro-l-methyl 239 2 6 9 -42- 41-21(3046)A -(methylsulfonyl) -lH-pyrazol-3-yl]-4-f luoro-N- (1-methylethyl)-benzeneamine as a red solid, mp 118'C-121*C.
Anal. Calc. for C^^NjOjdjF^, + 1/2 HzO: 5 C,43.20; H,4.40; N,10.79.
Found: C,42.88; H/4.02; N, 10.70.
Example 18 This example describes the preparation of N-[2-chloro-5-[4-chloro-l-methyl-5-(methylsulfonyl) -1H-10 pyrazol-3-yl]-4-fluorophenyl]-alanine, ethyl ester.
A solution of alanine, N-[2-chloro-5-[4-chloro-2-methyl-5-(methylsulfonyl) -lH-pyrazol-3-yl]-4-fluorophenyl]- in ethanol with a catalytic amount of acetyl chloride was allowed to stir at 25*C for 18 15 hours. This solution was diluted with EtOAc, washed with water, two times with 100 mL of aqueous potassium carbonate, dried (MgSOJ , filtered and concentrated to afford 0.5g of a yellow oil. Chromatography (CH2C12) afforded 0.17g (20*) of N-[2-chloro-5-[4-chloro-l-20 methyl-5- (methylsulfonyl) -lH-pyrazol-3-yl] -4-f luorophenyl] -alanine, ethyl ester as a yellow oil. 1HNMR (400 MHz, CDClj) d 1.2 (5, 3H), 1.48 (d, 3H) , 3.23 (s, 3H) , 3.8 (q, 1H) , 4.15 (q, 2H) , 4.18 (s, 3H) , 4.7 (bs, 1H) , 6.6 (d, 1H), 7.1 (d, 1H) ppm: ; 19FNMR( 360MHz, CDC13 d -25 128 (s, IF) ppm.
Anal. Calc. for C16H18N304C12F1S1: C,43.85; H,4.14; N,9.59.
Found: C,43.90; H,4.11; N,9.52.
Example 19 This example describes the preparation of N-30 [2-chloro-5-[4-chloro-l-methyl-5-(methylsulfonyl) -1H- pyr azol-3-yl]-4-f luor opheny 1 ] -N - (methy lsulfonyl) me thane-sulfonamide.
To a solution of 0.5g (0.0015 mol) of 2-chloro-5-[4-chloro-l-methyl-5- (methylsulfonyl) -1H-35 pyrazol-3-yl]-4-fluorobenzeneamine in 20 mL of methylene chloride was added 0.33g (0.0033 mol) of triethylamine followed by 0.37g (0.0033 mol) of methanesulfonyl chloride. This mixture vas stirred at 25*C for 18 239 2 6 9 -43- 41-21(3046) A hours. The reaction mixture vas diluted vith EtOAc, vashed vith three times 100 mL of 5% HCl, dried (MgS04), filtered and concentrated to afford 0.7g (94%) of N-[2-chloro-5-[4-chloro-l-methyl-5-(methylsulfonyl)-1H-5 pyra2ol-3-yl]-4-fluoropheny 1 ]-N-(methy 1su1f ony1)-methanesulfonamide as an off-white solid. Chromatography (EtOAc) afforded an analytical sample, mp 234-237*C.
Anal. Calc. for C13H14N306C12F1Sj + 1/4 EtOAc: 10 C,32.17; H,3.14; N,8.18.
Found: C,32.05; H,2.86; N,8.48.
Example 20 This example describes the preparation of 4-chloro-3-(4~chloro-2-fluoro-5- (2-propynyloxy) -15 phenyl) -l-methyl-5- (methylsulfonyl) -lH-pyrazole A mixture of 0.87 g (2.5 mmole) of 4-chloro-3- (4-chloro-2-f luoro-5-hydroxyphenyl) -l-methyl-5-(methylsulfonyl)-lH-pyrazole, 0.4 g (3.0 mmole) K2C03, and 0.3 mL (3.0 mmole) propargyl bromide vere slurried 20 in 10 mL DMSO at 25'C. The reaction vas stirred at 45*c for 16 hours. The reaction vas cooled, diluted with 100 mL cold water, and extracted four times with ethyl acetate. The ethyl acetate extracts vere vashed vith brine, dried over anhydrous MgS04, and stripped in vacuo. 25 The residue vas purified chromatographically using 50% ethyl acetate in hexane as the eluent to give 0.93 g (96%) of 4-chloro-3-(4-chloro-2-f luoro-5-(2-propynyloxy) phenyl) -l-methyl-5-(methylsulfonyl) -1H-pyrazole as a tan solid, mp 135*C. Anal. Calc. for 30 C^H^CljF^jOjS,: C, 44 .58 ; H,2.94, N,7.43.
Found: C,44.75; H,3.08;N,7.36 Examples 21 and 22 describe specific vorking embodiments of Process IX.
Example 21 This example describes the preparation of 2- (2-chloro-5-(4-chloro-l-methyl-5- (methylsulfonyl) -1H-pyrazol-3-yl) -4-fluorophenoxy) -propanoic acid. 239 2 -44- 41-21(3046)A To a slurry of 3.77 g (8.6 mmole) 2-(2-chloro-5-(4-chloro-l-methy1-5-(methylsulfonyl)-lH-pyrazol-3-yl)-4-fluorophenoxy)-propanoic acid, ethyl ester in 20 mL water and 20 mL 1,4-dioxane vas added 3.5 mL (8.6 mmole) 10% aqueous NaOH. The reaction became clear after 30 min. and a TLC indicated that the reaction was complete. The solution was cooled and the pH adjusted to 3 with concentrated HCl. The reaction vas extracted with ethyl acetate. The extracts vere vashed vith water, dried over anhydrous MgS04, and concentrated in vacuo. The residue was recrystallized from hexane to give 2.9g (83%) of 2-(2-chloro-5-(4-chloro-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-yl)-4-fluorophenoxy)-propanoic acid as a white solid, mp 56*C.
Anal. Calc. for CKH13C12F1N2°5S1: c,40.80; h,3.19; n,6.81.
Found: C,40.87; H,3.24; N,6.69.
Example 22 This example describes the preparation of 2-(2-chloro-5-(4-chloro-l-methyl-5-(methylsulfonyl)-l-pyrazol-3-yl)-4-fluorophenoxy)-N-methylpropanamide.
To a solution of 1.17g (5.9 mmole) 2-(2-chloro-5-(4-chloro-l-methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)-propanoic acid in 10 mL methylene chloride vas added 0.8 mL (9.6 mmole) oxalyl chloride over 3 minutes, causing the evolution of gas. When this evolution ceased, one drop of DMF vas added and the solution stirred until the gas evolution ceased. The solution vas stripped to dryness in vacuo. The residue vas dissolved in 5 mL THF and at O'C added to 10 mL of a 40% aqueous solution of methyl amine over 5 minutes. The reaction mixture vas alloved to stir for 30 minutes at room temperature. The solution vas poured into 150 mL cold vater and extracted vith ethyl acetate. The ethyl acetate extracts vere vashed times vith brine, dried over anhydrous MgS04, and stripped in vacuo. The solid vas recrystallized from methylcyclohexane/ethyl acetate to give 0.96g (80%) of 2-(2-chloro-5-(4-chloro- 23 9 2 6 9 -45- 41-21(3046)A l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-yl)-4-fluorophenoxy) -N-methylpropanamide as a white solid, mp 178'C; 1HNKR (CDClj) ppn: 1.55 (d, 3H), 2.81 (d, 3H) , 3.23 (s, 3H), 4.17 (s, 3H), 4.64 (q, 3H), 6.65 (br, 1H), 6.97 (d, 5 1H), 7.22 (d, 1H) .
Anal. Calc. for C^H^Cl^NjO^S,: C,42.46; H,3.80; N,9.90.
Found: C,42.60; H,3.68; N,9.86.
Examples 23 and 24 describe specific working embodiments of Process X.
Example 23 This example describes the preparation of (((2-chloro-5-(4-chloro-l-methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl)-4-fluorophenyl)methyl)thio)acetic acid, ethyl ester.
At 25*C, 1.25g (3.0 mmole) 3-(5-(bromomethyl)- 4-chloro-2-fluorophenyl)-4-chloro-l-methyl-5-(methylsulfonyl) -lH-pyrazole, 0.5g (3.3 mmole) K2C03, and 0.4 mL (3.3 mmole) ethyl bromoacetate were slurried in 15 mL acetone. The reaction was stirred at 20*C for 8 hours.
The reaction was poured into 150 mL water, filtered and air dired. The solid was recrystallized from methyl-cyclohexane to give 1.2g (93%) of (((2-chloro-5-(4-chloro-l-methyl-5- (methylsulfonyl) -lH-pyrazol-3-yl) -4-fluorophenyl)methyl) thio) acetic acid, ethyl ester as a 25 white solid, mp 110*C.
Anal. Calc. for C^H^ljF^O^Sj: C,42.20; H,3.76; N,6.15.
Found: C,42.25; H,3.72; N,6.18.
Example 24 This example describes the preparation of 2-30 chloro-5- (4-chloro-l-methyl-5- (methylsulfonyl) -1H-pyrazol-3-yl)-4-fluoro-N-methylbenzamide.
To a solution of 1.34g (3.7 mmole) 2-chloro- -(4-chloro-l-methyl-5-(methylsulfonyl) -lH-pyrazol-3-yl)-4-fluorobenzoic acid in 25 mL methylene chloride was added 1.0 mL (11.1 mmole) oxalyl chloride over 3 minutes, causing the evolution of gas. When this evolution ceased, one drop of DMF was added and the solution stirred until the gas evolution ceased. The 41-n (2>^)jQ 2 6 9 solution was stripped to dryness in vacuo. The residue was dissolved in 5 mL THF and at O'C added to 10 mL of a 40% aqueous solution of methyl amine over 5 minutes.
The reaction mixture was allowed to stir for 30 minutes 5 at room temperature. The solution was poured into 150 mL cold water, filtered, and air dried. The solid was recrystallized from methylcyclohexane/ethyl acetate to give 0.95g (69%) of 2-chloro-5-(4-chloro-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-yl)-4-fluoro-N-methyl-10 benzamide as a white solid, mp 187'C.
Anal. Calc. for C13H12C12F1Nj03S1: C,41.07; H,3.18; N,11.05.
Found: C,41.12; H,3.13; N,11.03.
Example 25 This example describes the preparation of 2-15 chloro-5-(4-chloro-l-methyl-5-(methylsulfonyl)-1H-pyrazol-3-yl)-4-fluorobenzenethiol and is a specific working embodiment of Process XI.
A slurry of 9.3g (0.022 mole) 2-chloro-5-(4-chloro-l-methyl-5- (methylsulfonyl) -lH-pyrazol-3-yl) -4-20 fluorobenzenesulfonyl chloride and 29g (0.44 mole) zinc powder in 125 mL glacial acetic acid was stirred at 90 *C for 4 hours. The slurry was cooled and filtered through Celite®. The filtrate was poured into 1 liter water and the slurry filtered and air dried. The solid was 25 recrystallized from ethanol/water to give 5.8g (74%) of 2-chloro-5-(4-chloro-l-methyl-5-(methylsulfonyl) -1H-pyrazol-3-yl)-4-fluorobenzenethiol as a white solid, mp lll'C.
Anal. Calc. for CnH9Cl2F1N202S2: C,37.19; H,2.55; N,7.86; 30 S, 18.05.
Found: C,37.29; H,2.44; N,7.86; S,17.95.
This example describes the preparation of 4-3 5 chloro-3-(4-chloro-2-fluoro-5-methoxyphenyl) -1-methyl-5-(ethylsulfonyl)-lH-pyrazole and is a specific working embodiment of Process XII. -223^^2 ( , -47- 41 All equipment was flame dried under nitrogen. To a solution of 4-chloro-3-(4-chloro-2-fluoro-5-methoxyphenyl) -l-methyl-5- (methylsulfonyl) -lH-pyrazole (1.25g, 3.5 mmol) in 50 ml dry tetrahydrofuran at -78*c 5 was added a 1M solution of n-butyl lithium (3.5 ml, 3.5 mmol) never letting the temperature rise above -60'C. The reaction was stirred for 30 minutes at -78*C and then methyl iodide (0.49g, 3.5 mmol) was added to the reaction. The reaction was warmed to room temperature 10 and then poured onto ice and extracted into ethyl acetate. The organics were washed twice with brine, dried over anhydrous magnesium sulfate, and concentrated in vacuo. The residue was purified chromatographically in 1:1 hexane to ethyl acetate solvent system to give 15 0.5g (39% Yield) of a yellow solid, mp 65*C.
Anal. Calc. for C^H^NjOjS^ljt C,42.52; H,3.57; N,7.63.
Found: C,42.53; H,3.80; N,7.71.
Example 27 This example describes the preparation of 7-20 [4-chloro-l-methy 1-5-(methylsulfonyl) -lH-pyrazol-3-yl]-6-fluoro-2H-l,4-benzothiazin-4(3H)-one and is a specific working embodiment of Process XIII.
A solution of ((5-(4-chloro-l-methyl-5-(methylsulf onyl) -lH-pyrazol-3-yl) -4-f luoro-2-nitro-25 phenyl)thio)acetic acid, ethyl ester (3.0g, 6.6 mmol) in glacial acetic acid (150 ml) was heated to 80*C and iron (1.5g, 0.0268 mol) was added all in one portion. The solution was heated between 80*C-100*C for one hour and then cooled, filtered through Celite* and washed with 30 water until a solid falls out of solution. The solid was filtered off to give 1.7g (68%) of the compound named in the first paragraph of this example as a white solid, mp 245*C; fHNMR (CDC1,) ppm: 7.28 (d, J - 7.2, 1H), 6.79 (d, J = 10.8, 1H), 4.1 (s, 3H), 3.27 (s, 2H), 35 3.22 (s, 3H).
Anal. Calc. for C13H11C11F1N303S1: C,41.55; H,2.95; N, 11.18.
Found: C,41.72; H,3.09; N,10.81.
Tables 3 and 4 show examples of conpounds prepared by Processes II-XIII and/or any combination of these processes as exemplified in Examples 1-27.
Table3. Pkyaical Data for l-Mclhyl-3-aryl-5-methyliulfony)pyraxolet.
Compound No. R3 Rj R( R7 22 Br F a OCH2CH2OCH3 23 Br F C! 0CH2002CH2CH3 24 a a a 11 23 a a a Nl<2 26 a a a N02 27 a a a N(S02CII3)2 2» a a CI NHSO2CU2CH3 29 a a a N(S02CH2CH3)2 a a a NHSO2CH3 31 a F a CH2Br 32 a F a CH2OCH2CH2CXM3 33 a F a CH2OCH2CHJ physical dau mpCQornD<25*C) 106.0 113.0 • «a 117.0 | 135.0 190.0 >230 177.0 213.0 176.0 14I.0-H3.O nD I.S629 I H> 76 0 77.0 w o x po o\ > CO ro o> T«M«* (coa'l) Cmponad No. Rj Rj 34 a F 33 a F 36 a F 37 a F 31 a F 39 a F 40 a F 41 a F 42 a F 43 a F 44 a F 43 a F 46 a F 47 a F 41 a F 49 a F a F R« R? a CH2OCOCH3 a ClljOII a CH2SCH2CO2CH2CH3 a CH3 a CHBrj a CHO a C02CH2CH3 a C0JCH2002CH2CH3 a COjH a CONHCH3 a F a II a N<Cll2C02CH2C»«3)C0CF3 a N(CH2C*CH)COCF3 a N(Cll3>2 a N(S02C»l3>2 a 4-imrphoUnc physical dau mp (*C) or nD(15*0 137.0 127.0 110.0 141.0 - 144.0-146.0 1 Ul - 130.0-132.0 0 . 1 117.0 79 0 194.0-1960 187.0 137.0 104.0-107.0 I—* 146.0-149.0 1 to 149.0-131.0 W 116.0-122.0 O J* 234-237 181.0 CM CO ro CD CO Table 3. (coa'l) Coopomd No. R3 Rj R< 31 a F a 32 a F a 33 a F a 34 a F a 33 a P a 36 a F a 37 a P a 31 a F a 59 a P a 60 a F a 61 a F a 62 a F a 63 a F a 64 a P a 65 a F a 66 a F a 67 a F a physical data mp(*C)ornD(25*C) NH2 135137 NHCH(CH3)2 118-121 N1IC!!(CH3)C02CH2CH3 yellow oil NI1CH2CH-CH2 nD 1.3956 NHCH2CO2CH3 99.0-100.0 NIICH2OCH 155-158 NHCOCF3 109.0-113.0 NHSO2CH3 165-166 NO2 111-113 mOC(-CHCH3XX>2CH3 138.0 <0Cll2CH2>30CI«3 nD 1.5465 OCH(Cll3)2 126.0 OCH(C«3)C02CH2CH3 nD 1.5429 0CH(CH3)C02H 56.0 0CII(CH3)C0NHCH2C02CH3 130.0 OCH(CH3)CX>NHCH3 178.0 OCH(Cll3)C«CH 29.0-30.0 Table 1. (cart) Compound No. R3 Rj R* 68 a F a 69 a p a 70 a F a 71 a p a 72 a F a 73 a F a 74 a P a 75 a F a 76 a P a 77 a F a 71 a P a 79 a F a a F a tl a P a 12 a F a >3 a F a 84 a F a R 7 physical data mp (*C) or nD(23*C) OCH2CH2F 141.0 0CH2C112OCHJ 69.0 OCH2CH2SCH3 96.0 OCH2CH3 102.0 OCH2CX)2C(CH3)3 138.0 1 OCH2CO2CH2CH2CH3 104.0 Ul to 1 0CH2C02CH(CH3)2 147.5-148.5 0CH2C02CH2CH3 116.0 0CH2C02CH3 I0S.0 0CII2C02H 152.0 OCll2O0N<CH3>2 124.0 OCH2CONHCH3 115.0-186.0 Oai2COSCH(CH3)2 159.0 M 1 IO »-• OCH2OCH 133.0 OCII2ON 133.0 U» octij 127.5 0 4k o\ OOIF2 83.0 > ro CM CO ro O) CO Table 3. (coal) Compouwl No. R 3 Rj R« •5 a F a 16 a F a 17 a F a II a F a 19 a F a 90 a F a 91 a F a 92 a F a 93 a F a 94 a P a 93 a F a 96 a F 11 97 a F NH2 91 a F N«2 99 a F N112 100 a P N112 101 a F N112 Rt physical data mp(°C)ornD(25*C) OH 190.5 SCH(CH3>2 99.0 SCII(CH3)C02Cll2CIl3 yellow oil SCH(CH3)C02CH3 yellow ail SCH2CH-CH2 94.0 SCH2C02CH(CH3)2 145.0 SCH2CO2CH2CH3 95.0 SCH2OCH 119.0 SH 111.0 S02CH(CH3)2 136.0 SOai(Cll3)2 65.0 F 77.0 OOI2CII3 94.0 CWI2CH2F 189.0-190.0 Oai(CH3)2 103.0 OCH3 139.0 4-mnphoUnc 175.0 1 ui Ui I I N> GJ O .U 0\ > ro o*i r\D o> <0 Table 3. (ow'l) Compound No. R 3 R j R4 102 a p NO2 103 a F N02 104 a F NO2 105 a F NO2 106 a P NO2 107 a F NO2 I0« a F NO2 109 a F NO2 110 a F NO2 111 a F N(>2 112 a F NO2 113 a F NO2 114 a F NO2 US a F NO2 116 a F NO2 117 a F 0013 III a F 0013 R7 physical data mp (*C) or nD(25*0 F 147.0 N(CH(CH3)2)COCF3 145.0 N(CH3)OCH3 116.0 4-morpholine 175.0 NHCH(CH3)2 152.0 (OCH2CH2)30CH3 nD 1.5507 OOI(C»l3)2 157.0 OCH2CH2F 124.0-125.0 OO I^O 120013 117.0-118.0 OCII2CII2SCII3 90.0 OCII2CH3 155.0 0013 178.3-180.0 SCII(Ol3)2 164.0 SCH(CH3)C02CH2CH3 nD 1.5846 SCH2CO2CH2CH3 155.0 If 75.0 NO2 144.0 I ui 4b I l fo M U> Il\> >04 CO PO c?> CO T»bk3. (oon't) Compelled No. R3 Rj 119 a F 120 H F 121 H F 122 H F 123 H F 124 Br F 123 Br F 126 Br F 127 Br F 121 Br F 129 Br F 130 Br F 131 Br F 132 Br F 133 a F 134 a F 133 ci F R« R7 physical data mp ("Q or nD(23*Q OH N02 130.0 II F 126.0-127.0 a CH3 149.0 a 11 157.0-159.0 a OCII3 169.0 N02 F 148.0 N112 F 151.0 NH2 OCH3 141.0 11 F 97.0 a OCH3 150.0 a OH 210.0 a OCH2OCH 130.0 a 0CI12002CH(CH3)2 169.0 a 0CH(CH3)C02CH2CH3 114.0 a cif-0C(-CHCH3)CO2H 194.0 a OCH(CHICH3)CX>2CH3 64.0 a OCIIjCONHi 170.0 SO? jO>l > CO ro C£> Tahiti. (CM*!) Cotnponad No. Rj Rj R« 136 a F a 137 a F F 131 a F F 139 a F NOz 140 a F NOi 141 a F a 142 a F N02 143 a F a physical dau mp (*C) or nDCZ5*C) OCH2CH2SOCH} 153.0 H 79.0 NO2 144.0 NHCH2CH-CH2 113.0 I NHCH2CO2CH3 142.0 0\ OCHtf-pynlyl) 1660 1 N(COCF])CH2CH-CH2 121.0 OGH(*-pentyl)OCH nD 1.5803 1 lv» 2 04 > CO ro o> Table 4. Physical Data for 3-Aiyl-5-alkyUulfonylpynzoks.
Compound No. Structure 144 145 146 147 148 y—f n'n CH,0 CH.
Physical Data (mp, -C) 107.0 129.0 93.0 65.0 04 CO ro o> CO i U1 ^1 I 123.0-124.0 I N> Ut O a\ Table 4. Physical Data for ^Ajyl-S-alkylsulfonylpyiaxofes.
Compound No. Structure CHjO F H Q ru CH,0 / <? c rfw;; oh/^ch, H _/ 1 V^ •» 'h-^VhTY>> <hQ-^VV Physical Data (■P. *C) 165.0-166.0 I en 213.0-216.0 I 192.0 245.0 I N) OJ o ro o\ CaI > CO ro o> Table 4. Physical Data for 3-Afyl-5-alky)Mlfoaylpyruoles.
Compound No. Structure 0»CH, / CI 0% ch, 153 154 155 156 Physical Data (■P. *C) 128.0 138.0 l m vo I 219.0 H 94.0 1 K> u o o\ > ro CM ro o> Tabk 4. Phytic*! Dau for 3-Afyl-S-alkylsulfonylpyfmzoles.
Compound No. Structure 157 151 159 O _ F 01 Q <Vi Physical Data (■P. *c> 196.0 I o\ o 141.0 170.0 I R> u o at ro Cj4 CO ro to 239 2 69 -61- 41-21(3046) A PRE-EMERGENCE HERBICIDE TESTS As noted above, the compounds of this invention have been found to be surprisingly effective as herbicides.
The tests for pre-emergence herbicide activity are conducted as follows: Topsoil is placed in an aluminum pan and compacted to a depth of 0.95 to 1.27 cm from the top of the pan. On the top of the soil is placed a 10 predetermined number of seeds of each of several monocotyledonous and dicotyledonous annual plant species and/or vegetative propagules of various perennial plant species. A known amount of the active ingredient dissolved or suspended in an organic solvent, e.g., 15 acetone, or water as a carrier is then applied directly to the seed bed, which is then covered with a layer of untreated topsoil to level fill the pan. After treatment, the pans are moved to a greenhouse bench where they are watered from below as needed to give adequate 20 moisture for germination and growth.
Approximately 10/14 days (usually 11 days) after seeding and treating, the pans are observed and the results (% inhibition) are recorded.
Table 5 below summarizes the results of the 25 pre-emergence herbicidal activity tests of compounds of this invention against weeds. The herbicidal rating shown in Table 5 is the percent inhibition of each plant species.
The plant species usually regarded as weeds 30 which are utilized in one set of tests, the data for which are shown in Table 5, are identified by letter headings above the columns in accordnace with the following legend: 239 2 69 -62- 41-21(3046)A Yens- Yellow nutsedge Anbg - Annual bluegrass Sejg - Seedling johnsongrass Dobr - Downy Brome Bygr - Barnyardgrass Mogl - Morningglory Cobu - CocXlebur Vele - Velvetleaf Innu - Indian mustard Wibw - Wild buc)cwheat Where noted in the tables below, the symbol "C" represents 100% control and the symbol "N" indicates that the species was planted, but no data obtained for one reason or another.
Cpd.
No. 22 23 24 26 27 28 29 31 32 33 34 36 37 38 39 TABU 5 PREEMERGENCE TESTS % PLANT INHIBITION YASDBKCVIW anaoyooani Rata nbjbggblab kg/ha sggrrluauv I.12 80 CCC CC70CCC I.12 30 20 80 30 20 C 80 90 90 C 11.21 70 C 90 70 C 90 70 C C C 11.21 0 80 80 70 80 70 30 C C 90 11.21 0 0 00 00 0 80 10 0 11.21 0 0 50 20 20 30 40 90 70 10 11.21 CC 70 80 CCCCCC 11.21 20 C 80 40 C C 0 C C 90 I.12 80 40 40 10 80 C C C C C II.21 40 10 70 0 C 80 80 80 80 80 11.21 CCCCCCCCCC II.21 90 C 90 C C C 70 C C C 11.21 90 C 90 60 C C 70 C C C 11.21 90 C C 50 C C 60 C C C 11.21 30 30 60 C 90 60 60 C C C II.21 60 80 90 30 C C C C C C 11.21 80 80 80 50 C 90 70 90 C C 11.21 90 C 90 80 C C C C C C 1.12 70 C 70 40 80 C 60 C C 90 1.12 70 50 30 10 80 C 20 C C C 11.21 80 80 90 80 C C C C C C 1.12 70 C C 50 90 C C C C C 239269 41-21(3046)A Cpd.
NO. 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 239 2 6 9 -64- 41-21(3046)A TABU 5 (cant Inuad \ PRggMEBCENCT TgSTS % PLANT INHIBITION YASDBKCVIW • n-«oyoo«ni Rat* nbjbggblmb kg/ha aggrr 1 u • u w 11.21 90 CCCC C90CCC 11.21 CCCCCCCCCC 1.12 0 0 30 10 0 10 20 70 70 C 1.12 0 60 80 10 70 80 10 90 C C 1.12 0 30 60 20 C 40 20 80 90 C I.12 0 90 90 10 90 90 30 C C C 11.21 20 80 70 60 90 C 20 C 90 C 11.21 50 C C 80 C 80 C 90 C C 1.12 10 C C 90 90 80 60 C C C 1.12 0 10 0 90 40 90 50 C C 60 1.12 40 10 30 20 0 70 30 C 90 90 1.12 10 0 0 20 20 C 90 90 C C 1.12 10 90 80 60 70 90 70 C C C 1.12 10 0 0 0 0 30 20 70 80 70 1.12 70 40 70 10 C 90 C C C C II.21 50 C C 80 C 90 90 C C C 1.12 30 70 C 90 80 60 40 C 70 C 1.12 50 90 60 SO 90 C 40 C C C 1.12 0 C 80 70 80 90 C 80 C 80 1.12 40 50 90 90 C 80 C C C C 1.12 30 20 30 80 C 70 C 90 C 90 1.12 40 80 70 SO C C 60 C C C Cpd No. 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 2392 6 9 41-21(3046)A TABLE 5 (continued! PREEMERGENCE TESTS % PLANT INHIBITION Y A S D B M C V I w a n • o y 0 O e n i Rate n b j b 9 9 b 1 m b kg/h* ■ 9 9 r r 1 u • u w 1.12 60 C 90 40 c C 70 c C c 1.12 0 C 70 80 c c 80 c c C 1.12 90 60 90 90 70 c c 90 1.12 60 C 90 50 90 C c c c 1.12 C 90 40 C C c c c 1.12 C 90 40 C 80 c c 90 1.12 60 60 80 c C 90 90 90 1.12 50 60 50 90 80 80 90 80 1.12 40 0 80 90 60 80 90 80 1.12 70 70 0 80 C C C c c 1.12 50 0 70 80 C 40 C 90 c 1.12 60 70 C 90 90 90 80 1.12 0 80 C 70 C 80 80 1.12 60 C 90 50 C C C C C C 1.12 90 C 70 90 C C c c c 1.12 60 70 C 60 90 90 90 1.12 60 c C 90 C 90 80 c c C 1.12 50 50 80 90 C 90 c c 90 CM H • r-t 70 c C C C c 60 c c C 1.12 0 80 70 80 80 c 80 c c c LI.21 90 90 90 90 90 90 C c c c 1.12 0 40 40 80 90 Cpd.
No. 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 239 2 6 9 -66- 41-21(3046)A TABU 5 t continued 1 PRIEttERGENCE TESTS % PLANT INHIBITION YASDBKCVIW • n'*oyoo*ni Rat* n b j b g g b 1 m b kg/ha aggrrlueuw I.12 0 70 80 80 60 C 80 C C C 1.12 20 40 80 80 60 C 80 C C C I.12 0 20 40 30 80 80 80 C C C 1.12 0 0 0 20 30 60 30 C C C 1.12 20 10 10 50 70 60 60 C C C I.12 0 80 40 60 50 C 60 C C 90 11.21 0 10 0 10 50 20 0 80 80 10 11.21 60 C C 70 C 90 30 C C C 11.21 70 C C 70 C C 80 C C C 11.21 70CCCCC20CCC 11.21 20 20 40 20 80 40 20 C C 80 II.21 00 20 000000 30 II.21 0000000 20 00 II.21 0000000000 11.21 0 0 70 0 80 60 20 50 70 0 11.21 40 30 60 30 80 50 0 60 C 90 11.21 20 80 80 20 80 90 70 90 80 90 11.21 40 C 80 80 90 70 80 C C C 11.21 40 80 90 70 90 80 60 C C 70 11.21 0 60 70 30 60 40 70 C 90 90 11.21 40 90 70 60 C 70 C C C 50 11.21 30 90 90 70 80 90 80 C C C Cpd.
Ho. 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 TABLE 5 /eanfcinu«dl PRggMBRCEWCT TESTS » PLAIT IEHIBITI9P YXSDBKCV • naoyoo* Rat* nbj b g g b 1 kg/ha sggrrlu* 11.21 70 C C 60 90 80 90 C 11.21 80 C 90 80 90 90 90 C 11.21 40 C 70 70 C 20 C C 11.21 80 C C 70 90 C 70 C I.12 60 80 90 50 C 30 60 90 11.21 0 0 0 20 20 70 20 30 11.21 C 40 90 80 C C C C 11.21 90 0 80 20 60 90 60 C 11.21 70 80 90 70 C 70 90 C 11.21 0000000 80 11.21 000 0000 30 11.21 00000000 11.21 0000000 20 11.21 0000000 10 11.21 40 90 90 20 90 70 40 80 11.21 50 20 40 20 70 70 20 90 11.21 0 0 0 0 0 20 0 70 II.21 30 60 40 20 80 70 20 C 11.21 80CCCCCCC 1.12 80 C 90 70 90 90 C C 11.21 40 70 60 90 80 80 C C 1.12 40 C 80 80 90 C 60 C 239 2 6 9 41-21(3046)A I w n i B b U w C C c 80 c 70 c C c 90 c C c c c c 0 0 90 90 C 50 40 40 90 80 C c c c c c c c Cpd.
Ho. 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 TABL8 5 fcontlnuadl PPBSMgWtreg TESTS » PWtf«T IWIBITI9N YASDBMCVIW • naoyooani Rata nbjbggblmb kg/ha aggrrluauw 1.12 80 20 80 20 70 C 30 C 90 C 1.12 0 30 80 C 80 80 30 C C C 1.12 10 20 90 40 10 80 30 C 80 C I.12 C C 90 90 C 90 C C C C 1.12 C 10 80 10 C C 60 C C C I.12 10 90 90 40 C C 20 C C C 11.21 90CCCCCCCCC 11.21 0 0 0 0 0 0 0 80 20 70 11.21 20 90 80 90 80 90 90 C C C 11.21 80 60 C 20 C C C C C C I.12 30 90 70 60 80 80 20 C 90 90 11.21 60 C 90 20 90 90 60 C C C I.12 0 40 20 10 20 20 80 30 80 70 11.21 0 20 0 20 0 0 0 20 20 20 11.21 0 10 10 20 30 20 30 30 20 40 II.21 60 C C C C 80 30 C C C II.21 60 C 90 70 C 80 20 C C 90 11.21 80 C C C C 90 50 C C C 11.21 0 0 0 0 0 50 20 70 60 80 11.21 0000000000 II.21 30 90 90 30 90 C 80 C C C II.21 0000000000 239269 41-21(3046)A 4K ""69'- 4i-2<3«A 2 TABLE S (continued) PREEMERGENCE TESTS % PLANT INHIBITION Y A s D B M C V I W • n • o y o O • n i Cpd.
Rat* n b •j b 9 9 b 1 in b No. kg/ha a 9 9 r r 1 u • u w 153 1.21 60 C 70 90 80 40 c c C 154 1.12 70 C 80 80 90 C C c c C 155 1.12 80 C C 60 C C C c c C 156 1.12 0 C 90 90 90 90 c c 80 157 1.12 70 C 90 C C C C c c c 158 1.12 80 40 50 40 80 159 11.21 0 0 0 0 0 0 0 0 0 0 * Wibw-THIN • A Exceeaiv* damping off # Observation ca. 4-weeks 239 2 69 -70- 41-21(3046)A POST-EMERGENCE HERBICIDE TESTS The post-emergence herbicidal activity of some of the various compounds of this invention was demon-5 strated by greenhouse testing in the following manner.
Topsoil is placed in aluminum pans having holes in the bottom and compacted to a depth of 0.95 to 1.27 cm from the top of the pan. A predetermined number of seeds of each of several dicotyledonous and monocotyledonous 10 annual plant species and/or vegetative propagules for the perennial plant species are placed on the soil and pressed into the soil surface. The seeds and/or vegetative propagules are covered vith soil and leveled. The pans are then placed on a bench in the greenhouse 15 and watered from below as needed. After the plants reach the desired age (two to three weeks) , each pan, is removed individually to a spraying chamber and sprayed by means of an atomizer, operating at a spray pressure of 170.3 kPa (10 psig) at the application rates noted. 20 In the spray solution is an amount of an emulsifying agent mixture to give a spray solution or suspension which contains about 0.4% by volume of the emulsifier. The spray solution or suspension contains a sufficient amount of the candidate chemical in order to give 25 application rates of the active ingredient corresponding to those shown in Table 2, while applying a total amount of solution or suspension equivalent to 1870 L/Ha (200 gallons/acre). The pans were returned to the greenhouse and watered as before and the injury to the plants as 30 compared to the control is observed at approximately 10-14 days (usually 11 days) and in some instances observed again at 24-28 days (usually 25 days) after spraying. The post-emergent herbicidal activity shown in Table 6 is the percent inhibition of each plant species.
Cpd No. 22 23 24 26 27 28 29 31 32 33 34 36 37 38 39 40 41 42 43 TABLE 6 POST-EMERGENCE TESTS % PLANT INHIBITION 239 269 41-21(3046)A Y A S D B M C V I W • n '• O y o o • n i Rate n b j b 9 9 b 1 m b kg/ha ■ 9 9 r r 1 u • u w 1.12 40 40 50 C C c 80 80 1.12 50 40 40 80 c c c 60 C 11.21 40 60 80 90 80 70 c 90 C 11.21 0 0 0 40 90 11.21 0 0 0 0 0 11.21 0 0 0 0 90 50 70 11.21 0 80 C c 90 C 11.21 60 0 c 70 60 1.12 0 90 90 90 80 80 11.21 0 0 80 80 c 50 60 11.21 40 90 90 c 90 C 90 c 90 C 11.21 90 C c C 90 C c C C 11.21 40 70 70 80 80 c 90 80 11.21 70 0 C C 80 c 80 70 11.21 50 40 60 60 c 70 C 11.21 80 90 90 C C C c C c 11.21 60 70 0 70 c 60 c 60 60 11.21 80 80 90 c 50 c 90 80 1.12 40 90 90 C C 90 C c 90 90 1.12 70 80 c c 60 c 90 70 11.21 60 90 90 40 80 c C c C C 1.12 0 40 90 90 c 80 70 Cpd.
No. 44 45 46 47 48 49 SO 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 239269 -72- 41-21(3046)A TABLE 6 <continued\ POST-EMERGENCE TESTS t PLANT INHIBITION YASDBMCVIW eneoyooeni Rate nbj b g g b 1 m b kg/ha aggrrlueuw 11.21 40CCCCCCCCC 11.21 30 90 C 90 C C C C C C 1.12 20 0 0 0 0 30 30 30 30 60 1.12 20 0 20 20 0 30 30 50 40 80 1.12 10 20 20 20 20 C 60 C 40 80 9 1.12 0 10 0 0 0 40 30 50 40 60 11.21 20 30 90 50 50 70 60 90 C C 9 11.21 0 20 40 20 50 90 C C 80 C 1.12 20 40 20 20 40 90 60 C 70 C 1.12 20 20 80 50 90 90 C C 80 90 1.12 0 20 40 20 10 30 40 70 60 60 1.12 30 10 40 20 80 C C C 70 C 9 1.12 20 50 20 20 0 90 90 C 70 90 1.12 0 0 0 0 0 20 20 60 50 80 9 1.12 20 10 20 0 30 C 90 C 70 C 9 11.21 20 60 80 20 80 C 90 90 80 C 1.12 20 20 60 20 60 C C C 50 80 1.12 30 60 90 C C 60 C C 80 90 1.12 20 50 80 50 50 50 80 90 70 80 1.12 30 80 C C C C C 90 90 C 1.12 30 90 C C 90 C C C C C 1.12 30 60 80 90 90 C C 90 C 90 Cpd No. 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 239 2 6 9 -73- 41-21 (3046) A TABLB 6 Icontinued! POST-EMERGENCg TESTS % PLANT INHIBITION Y A S D B M c V I W e n e o y o o e n i Rate n b j b 9 9 b 1 a b kg/ha ■ 9 9 r £ 1 u e u w 1.12 60 80 50 C 80 c 50 C 1.12 70 70 80 70 90 90 c c C 1.12 40 90 50 60 60 90 60 40 1.12 40 50 50 90 70 C C C 70 C 1.12 c c c 80 70 1.12 90 90 90 80 c c 90 60 C 1.12 0 50 50 90 80 90 60 1.12 80 C 80 90 c 50 C 1.12 70 40 60 c c c 60 c 1.12 50 0 40 c c c 50 c 1.12 80 50 70 c c 90 60 80 1.12 60 60 c c 90 50 c 1.12 50 c 80 90 60 70 1.12 0 70 0 c 90 90 60 c 1.12 70 60 c C 90 80 90 1.12 C C C C 90 c C c c 1.12 0 0 80 80 C 40 1.12 90 C c c c c 90 90 C 1.12 70 C 90 90 90 70 C 80 c 11.21 60 90 60 90 C 90 90 90 c 1.12 60 50 C 50 90 Cpd No. 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 -74- . • TABLE 6 (continued! POST-EMERGENCE TESTS % PLANT INHIBITION 239269 41-21(3046)A Y A S D B K c V I H e n e o y 0 o e n i Rate n b 'j b 9 9 b 1 m b kg /ha s 9 9 r r 1 u e u w 1.12 40 80 c c C c c 90 90 1.12 70 80 c c C c c c 80 1.12 50 60 70 40 90 90 90 90 80 1.12 0 80 90 90 90 80 c 80 80 1.12 40 90 90 90 80 C 90 90 80 1.12 40 70 70 80 c c c 90 40 11.21 0 0 70 80 80 c 90 70 11.21 0 0 0 80 70 60 40 11.21 0 0 c 90 c 11.21 90 50 90 60 c 40 C 11.21 0 0 0 0 0 60 80 11.21 0 0 0 0 0 0 0 0 11.21 0 0 0 0 0 0 0 0 0 11.21 0 0 0 0 0 11.21 0 0 0 0 0 40 11.21 0 60 11.21 0 0 0 0 0 0 0 0 0 60 11.21 0 0 0 50 50 60 11.21 40 0 40 50 60 80 70 C 11.21 60 80 80 70 C 80 C 11.21 0 0 0 0 0 40 40 50 40 80 11.21 50 80 50 60 C C c c C Cpd.
No. 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 239 2 69 -75- 41-21(3046) A TABLE 6 I continued) POST-EMERGENCE TESTS % PLANT INHIBITION YASDBMCVIW eneoyooeni Rate nbj bggblmb kg/ha aggrrluauw 11.21 30 30 60 20 30 60 50 90 50 C 11.21 30 30 40 20 40 30 30 90 SO C 11.21 30 70 80 40 SO 50 70 C 70 C 11.21 0 40 20 0 10 20 10 70 80 50 11.21 20 60 90 40 50 40 70 C 80 C I.12 0 0 10 0 10 10 10 20 0 90 11.21 0 0 0 0 0 0 30 20 0 40 11.21 30 30 C 90 90 90 C C C C 11.21 20 20 60 30 50 80 70 C 50 60 11.21 10 50 50 40 80 60 50 C 90 C 11.21 0 0 0 0 0 20 0 20 10 0 11.21 10 000000000 11.21 0000000 10 00 11.21 00000 20 20 000 11.21 0 0 0 0 0 20 0 20 0 20 11.21 0 20 0 0 0 20 50 60 20 C 11.21 0 0 0 0 0 0 0 30 20 20 11.21 0000000 20 00 II.21 0 0 0 0 0 20 20 40 20 50 11.21 10 90 90 70 C C 70 C C C 1.12 10 50 40 80 80 80 80 80 60 C 11.21 10 30 30 0 30 80 50 C 80 C Cpd.
No. 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 239 2 69 -76- 41-21(3046)A TABLE 6 (continued! POST-EMERGENCE TESTS % PLANT INHIBITION YASDBKCVIW en'eoyooeni. Rate nbjbggblmb kg/ha sggrrlueuw I.12 30 60 40 50 20 C C C C C 1.12 40 20 60 20 70 C 90 C 40 80 1.12 30 30 40 80 80 C C C 80 80 1.12 10 40 40 80 90 90 90 C 40 40 1.12 0 90 80 C C C C C 80 50 1.12 20 10 80 0 60 C 80 C 50 50 1.12 10 20 60 30 20 80 80 C 90 90 11.21 20CCCCC90CCC 11.21 0 0 20 0 0 40 30 40 20 C 11.21 10 30 80 30 20 50 40 C C C 11.21 20 10 80 10 70 60 50 C 70 70 1.12 0 90 90 80 70 80 70 C 70 70 11.21 10 20 80 20 10 40 30 80 30 70 1.12 20 90 90 C 70 C C C 90 50 11.21 0 20 0 20 0 20 20 30 20 50 9 11.21 10 0 0 0 10 20 20 40 40 20 9 11.21 10 70 80 90 90 60 60 C 80 C 11.21 0 60 80 30 80 80 70 C 90 C 11.21 10 40 40 0 20 20 30 C 90 C 9 11.21 0 0 0 0 0 10 10 10 0 40 9 11.21 00000 20 000 20 II.21 10 0 0 0 0 60 60 80 60 C I . .-11-, TABLE 6 (continued! POST-EMERGENCB TESTS % PLANT INHIBITION 2 Y A S D B M C V 1 W e n e o y o 0 e n 1 Cpd.
Rate n b j b 9 9 b 1 m b No. kg /ha s 9 9 r r 1 u e u w 152 11.21 0 0 0 0 0 0 0 0 0 0 153 11.21 0 40 80 80 c 154 1.12 C 80 80 70 70 80 C C 80 155 1.12 90 80 70 90 70 C C 90 156 1.12 80 C 50 90 40 c 90 70 157 1.12 90 90 90 90 C C c 90 80 158 1.12 70 70 60 40 C C c 70 50 159 11.21 0 0 0 0 0 0 0 6 Poor cocklebur response + Duplicate test 0 . . 239269 -78- 41-21(3046)A The herbicidal compositions of this invention, including concentrates which require dilution prior to application, may contain at least one active ingredient and an adjuvant in liquid or solid form. The 5 compositions are prepared by admixing the active ingredient with an adjuvant including diluents, extenders, carriers, and conditioning agents to provide compositions in the form of finely-divided particulate solids, granules, pellets, solutions, dispersions or 10 emulsions. Thus, it is believed that the active ingredient could be used with an adjuvant such as a finely-divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or any suitable combination of these.
Suitable wetting agents are believed to include alkyl benzene and alkyl naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid 20 esters, petroleum sulfonates, sulfonated vegetable oils, ditertiary acetylenic glycols, polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol and nonylphenol) and polyoxyethylene derivatives of the mono-higher fatty acid esters of hexitol anhydrides 25 (e.g., sorbitan). Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate, and polymethylene bisnaphthalene sulfonate. Wettable powders are water-dispersible 30 compositions containing one or more active ingredients, an inert solid extender and one or more wetting and dispersing agents. The inert solid extenders are usually of mineral origin such as the natural clays, diatomaceous earth and synthetic minerals derived from 35 silica and the like. Examples of such extenders include kaolinites, attapulgite clay and synthetic magnesium silicate. The wettable powders compositions of this invention usually contain from above 0.5 to 60 parts 239 2 6 9 -79- 41-21(3046)A (preferably from 5-20 parts) of active ingredient, from about 0.25 to 25 parts (preferably 1-15 parts) of wetting agent, from about 0.25 to 25 parts (preferably 1.0-15 parts) of dispersant and from 5 to about 95 parts 5 (preferably 5-50 parts) of inert solid extender, all parts being by weight of the total composition. Where required, from about 0.1 to 2.0 parts of the solid inert extender can be replaced by a corrosion inhibitor or anti-foaming agent or both.
Other formulations include dust concentrates comprising from 0.1 to 60% by weight of the active ingredient on a suitable extender; these dusts may be diluted for application at concentrations within the range of from about 0.1-10% by weight. 15 Aqueous suspensions or emulsions may be prepared by stirring a nonaqueous solution of a water-insoluble active ingredient and an emulsification agent with water until uniform and then homogenizing to give stable emulsion of very finely divided particles. The 20 resulting concentrated aqueous suspension is characterized by its extremely small particle size, so that when diluted and sprayed, coverage is very uniform. Suitable concentrations of these formulations contain from about 0.1-60%, preferably 5-50% by weight of active 25 ingredient, the upper limit being determined by the solubility limit of active ingredient in the solvent. Concentrates are usually solutions of active ingredient in water-immiscible or partially water-immiscible solvents together with a surface active agent. Suitable 30 solvents for the active ingredient of this invention include dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons, and water-immiscible ethers, esters, or ketones. However, other high strength liquid concentrates may be formulated by 35 dissolving the active ingredient in a solvent then diluting, e.g., with kerosene, to spray concentration. 239 2 69 -80- 41-21 (3046)A The concentrate compositions herein generally contain from about 0.1 to 95 parts (preferably 5-60 parts) active ingredient, about 0.25 to 50 parts (preferably 1-25 parts) surface active agent and where 5 required about 5 to 94 parts solvent, all parts being by weight based on the total weight of emulsifiable oil.
Granules are physically stable particulate compositions comprising active ingredient adhering to or distributed through a basic matrix of an inert, finely-10 divided particulate extender. In order to aid leaching of the active ingredient from the particulate extender, a surface active agent such as those listed hereinbefore can be present in the composition. Natural clays, pyrophyllites, illite, and vermiculite are examples of 15 operable classes of particulate mineral extenders. The preferred extenders are the porous, absorptive, preformed particles such as preformed and screened particulate attapulgite or heat expanded, particulate vermiculite and the finely-divided clays such as kaolin 20 clays, hydrated attapulgite or bentonitic clays. These extenders are sprayed or blended with the active ingredient to form the herbicidal granules.
The granular compositions of this invention may contain from about 0.1 to about 30 parts by weight 25 of active ingredient per 100 parts by weight of clay and 0 to about 5 parts by weight of surface active agent per 100 parts by weight of particulate clay.
The compositions of this invention can also contain other additaments, for example, fertilizers, 30 other herbicides, other pesticides, safeners and the like used as adjuvants or in combination with any of the above-described adjuvants. Chemicals useful in combination with the active ingredients of this invention included, for example, triazines, ureas, sulfonylureas, 35 carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiolcarbamates, triazoles, benzoic acid derivatives, nitriles, heterophenyl ethers, •23926 -81- 41-21 (3046)A nitrophenyl ethers, diphenyl ethers, pyridines and the like such as: Heterocyclic Nitrogen/Sulfur Derivatives 2-Chloro-4-ethylaraino-6-isopropylamino-£-triazine 5 2-Chloro-4,6-bis(isopropylamino)-£-triazine 2-Chloro-4,6-bis(ethylamino)-s-triazine 3-Isopropyl-lH-2,l,3-benzothiadiazin-4-(3H)-one 2,2-dioxide 3-Amino-l,2,4-triazole 10 6,7-Dihydrodipyrido(l,2-:2 *,l'-c)-pyrazidiinium salt 5-Bromo-3-isopropyl-6-methyluracil 1,1*-Dimethyl-4,4•-bypyridinium 2- (4-Isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -3- quinolinecarboxylic acid 15 Isopropylamine salt of 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid Methyl 6- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-m-toluate and methyl 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-p-toluate 20 5- (Trif luoromethyl) -4-chloro-3-(3 •-[ 1-ethoxycarbonyl]-ethoxy-41 -nitrophenoxy) -1-methylpyrazol; - (Trif luoromethyl) -4-chloro-3- (3 ' -methoxy-4 ' -nitro-phenoxy)-l-methylpyrazole; - (Trif luoromethyl) -4-chloro-3- (3 • -[ 1-butoxycarbonyl] - 2 5 ethoxy-4•-nitrophenoxy)-4-methylpyrazol; - (Trif luoromethyl) -4-chloro-3- (3 • -methylsulfamoylcar-bonyl propoxy-4' -nitrophenoxy) -4-methylpyrazol; - (Trif luoromethyl) -4-chloro-3- (3 • -propoxycarbonyl-methyloxime-4 • -nitrophenoxy) -l-methylpyrazole; (±) —2— C4—[ [5-(Trifluoromethyl)-2-pyridinyl]oxy]phenoxy]-propanoic acid (9CI).
S, S-dimethyl-2- (dif luoromethyl) -4-isobutyl-6-trif luoromethyl-3,5-pyridinedicarbothioate; 3-Pyridinecarboxylic Acid, 2-(difluoromethyl)-5-(4,5- 3 5 dihydro-2-thiazolyl) -4- (2-methylpropyl) -6- (tri- fluoromethyl)-, methyl ester; 3,5-Pyridinedicarboxylic acid, 2-(difluoromethyl)-4-(2— methylpropyl)-6-(trifluoromethyl)-, dimethyl ester; 239 2 6 9 -82- 41-21(3046)A 3,5-Pyridinedicarbothioic acid, 4-(cyclopropylmethyl)-2-(difluoromethyl)-6-(trifluoromethyl)-, s,s-dimethyl ester; Sulfoximine, N-(diethoxyphosphinyl)-S-methyl-S-phenyl- Ureas and Sulfonylureas N-(4-Chlorophenoxy) phenyl-N,N-dimethylurea N,N-dimethy1-N1-(3-chloro-4-methylphenyl) urea 3-(3,4-dichlorophenyl)-1,1-dimethylurea 10 l,3-Dimethyl-3-(2-benzothiazolyl) urea 3-(p-Chlorophenyl)-1,1-dimethylurea 1-Butyl-3-(3,4-dichlorophenyl)-1-methylurea 2-Chloro-N[(4-methoxy-6-methyl-l,3,5-triazin-2-yl) aminocarbonylj-benzenesulfonamide Methyl 2- (((((4,6-dimethyl-2-pyrimidinyl) amino) -carbonyl)amino)sulfonyl) benzoate Ethyl l-[methyl 2-(((((4,6-dimethyl-2-pyrimidinyl)- amino)carbonyl)amino)sulfonyl)] benzoate Methy1-2((4,6-dimethoxy pyrimidin-2-yl)aminocar-20 bonyl)amino sulfonyl methyl) benzoate Methyl 2-(((((4-methoxy-6-methyl-l,3,5-triazin-2-yl)- amino)carbonyl)amino)sulfonyl) benzoate N- [ 3 - (N, N-dimethy Icarbamoyl) -2-pyr idin-2 -y 1 ] sulfony1-N'-(4,6-dimethoxypyrimidin-2-yl)urea 25 N-[ (3-ethylsulfonyl)-2-pyridin-2-yl]-sulfonyl-N'-(4,6-dimethoxy-pyrimidin-2-yl) urea N- (2-methoxycarbonylphenyl sulfonyl) -N' - (4,6-bis-difluoromethoxypyrimidin-2-yl)urea Carbamates/Thiolcarbamates 3 0 2-Chloroallyl diethyldithiocarbamate S- (4 -chlorobenzy 1) N, N-diethy lthiolcarbamate Isopropyl N-(3-chlorophenyl) carbamate S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate S-N,N-dipropylthiolcarbamate 35 S-propyl N,N-dipropylthiolcarbamate S-2,3,3-trichloroallyl-N,N-diisopropylthiolcarbamate 239 2 6 -83- 41-21(3046)A Acatamldes/Acetanilides/Anilines/Afflid«>? 2-Chloro-N,N-diallylacetamide N, N-dimethyl-2,2-diphenylacetamide N- (2,4-dimethylthien-3-yl)-N-(l-methoxyprop-2-yl)-2-5 chloroacetamide N- (lH-pyrazol-l-ylmethyl-N-(2,4-dimethylthien-3-yl)-2- chloroacetamide N- (l-pyrazol-l-ylmethyl)-N- (4,6-dimethoxypyrimidin-5-yl)-2-chloroacetamide 10 N-(2,4-dimethyl-5-[[[(trifluoromethyl)sulfonyl]amino]-phenyl]acetamide N-Isopropy1-2-chloroacetani1ide N-Isopropyl-l-(3,5,5-trimethylcyclohexen-l-yl)-2-chloroacetamide 15 2 ', 6'-Diethyl-N-(butoxymethyl)-2-chloroacetanilide 2 •, 6'-Diethyl-N-(2-n-propoxyethyl)-2-chloroacetanilide 2 •, 6'-Dimethy1-N-(l-pyrazol-l-ylmethyl)-2-chloroacetanilide 2 •, 6*-Diethyl-N-methoxymethyl-2-chloroacetanilide 20 2 ,-Methyl-6'-ethyl-N-(2-methoxyprop-2-yl)-2-chloro-acetanilide 2 ' -Methy 1-6' -ethyl-N- (ethoxymethyl) -2-chloroacet-anilide a,a,a-Trifluoro-2,6-dinitro-N,N-dipropy 1-p-toluidine 25 N- (1,1-dimethylpropynyl)-3,5-dichlorobenzamide Acids/Esters/Alcohols 2,2-Dichloropropionic acid 2-Methyl-4-chlorophenoxyacetic acid 2,4-Dichlorophenoxyacetic acid Methyl-2-(4- (2,4-dichlorophenoxy)phenoxy] propionate 3-Amino-2,5-dichlorobenzoic acid 2-Methoxy-3,6-dichlorobenzoic acid 2,3,6-Trichlorophenylacetic acid N-l-naphthylphthalamic acid Sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate 4,6-Dinitro-o-sec-butylphenol N-(phosphonomethyl) glycine and its salts 2 3 9 2 -84- 41-21(3046)A Butyl (R)-2-[4-[(5-(trifluoromethyl)-2-pyridinyl)oxy]-phenoxy] propanoate Ethers 2,4-Dichlorophenol-4-ni-trophenyl ether 5 2-Chloro-$,S,5-trifluoro-p-tolyl-3-ethoxy-4-nitro-diphenyl ether 5-(2-chloro-4-trifluoromethylphenoxy)-N-methylsul- fonyl 2-nitrobenazmide 1'-(Carboethoxy) ethyl 5-[2-chloro-4-(trifluoro-10 methyl)phenoxy]-2-nitrobenzoate Miscellaneous 2, 6-Dichlorobenzonitrile Monosodium acid methanearsonate Disodium methanearsonate 15 2-(2-chloropheny1)methyl-4,4-dimethy1-3-isoxa-zolidinone 7-Oxabicyclo (2.2.1) heptane, 1-methy1-4-(1-methyl- ethyl)-2-(2-methylphenylmethoxy)-, exo-Glyphosate and salts thereof.
Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea, potash and superphosphate. Other useful additaments include materials in which plant organisms take root and grow such as compost, manure, humus, sand 25 and the like. 239 2 6 9 -85- 41-21(3046)A Herbicidal formulations of the types described above are exemplified in several illustrative embodiments below.
I. Emulsifiable Concentrates 5 Weight Percent A. Compound No. 22 4.0 Free acid of complex organic phosphate or aromatic or aliphatic hydrophobe base (e.g., GAFAC RE-610, registered 10 trademark of GAF Corp.) 3.5 Polyoxyethylene/polyoxypropylene block copolymer with butanol (e.g., Tergitol XH, registered trademark of Union Carbide Corp.) 1.5 Xylene 5.34 Monochlorobenzene 85.66 100.00 B. Compound No. 36 3.0 Free acid of complex organic phosphate of aromatic or aliphatic hydrophobe base (e.g., GAFAC RE-610) 4.0 Polyoxyethylene/polyoxypropylene block copolymer with butanol (e.g., Tergitol XH) 1.60 Xylene 4.75 Monochlorobenzene 86.65 100.00 C. Compound No. 43 2.5 Free acid of complex organic phosphate or aromatic or aliphatic hydrophobe 30 base (e.g., GAFAC RE-610, registered trademark of GAF Corp.) 4.0 Polyoxyethylene/polyoxypropylene block copolymer with butanol (e.g., Tergitol XH, registered trademark of Union Carbide 3 5 Corp.) 1.5 Cyclohexanone 5.5 Aromatic 200 86.5 100.00 # 239269 -86- 41-21(3046)A Weight Percent D. Compound of No. 52 5.0 Free acid of complex organic phosphate of aromatic or aliphatic hydrophobe base (e.g., GAFAC RE-610 3.00 Polyoxyethylene/polyoxypropylene block copolymer with butanol (e.g., Tergitol XH) 2.0 Phenol 5.0 Monochlorobenzene 85.0 100.00 E. Compound No. 53 1.50 Free acid of complex organic phosphate or aromatic or aliphatic hydrophobe base (e.g., GAFAC RE-610, registered trademark of GAF Corp.) 4.50 Po ly oxy ethy 1 ene / po ly oxypr opy lene b lock copolymer with butanol (e.g., Tergitol XH, registered trademark of Union Carbide Corp.) 1.00 Isophorone 5.34 Emerset 2301 87.66 100.00 F. Compound No. 54 4.50 Free acid of complex organic phosphate of aromatic or aliphatic hydrophobe base (e.g., GAFAC RE-610 3.00 Polyoxyethylene/polyoxypropylene block copolymer with butanol (e.g., Tergitol XH) 2.00 Cyclohexanone 4.75 7-Butyrolactone 85.75 100.00 # II. Flowables A. Compound Ho. 58 Xanthan Gum 5 Ethylene Glycol Sodium lignosulfonate Sodium N-methyl-N-oleyl taurate Water B. Compound No. 59 Xanthan Gum Magnesium Aluminum Silicate Alkyl aryl sulfonate Propylene glycol 15 Water C. Compound No. 66 Xanthan gum Propylene Glycol Sodium lignosulfonate Alkyl aryl sulfonate (e.g., Morwet D-425) Water D. Compound No. 81 Magnesium Aluminum Silicate Ethylene Glycol Alkyl aryl sulfonate EO/PO Block Copolymer (e.g., Pluronic P-104) 3 0 Water 239 2 41-21(3046)A Weight Percent 6 9 .0 0.3 10.0 3.5 1.0 60.2 100.00 45.0 0.2 0.2 3.5 7.0 44.1 100.00 23.0 0.3 10.0 3.5 2.0 61.2 100.00 45.0 0.3 7.0 3.5 1.0 43.2 100.00 239 2 6 9 III. Wettable Powders A. Compound No. 83 Sodium lignosulfonate Kaolin Amorphous silica (synthetic) B. Compound No. 85 Sodium dioctyl sulfosuccinate 10 Alkyl Aryl Sulfonate Kaolin Amorphous silica (synthetic) C. Compound No. 93 Sodium lignosulfonate Sodium N-methyl-N-oleyl-taurate Amorphous silica (synthetic) Kaolinite clay D. Compound No. 96 Sodium lignosulfonate Sodium dioctyl sulfosuccinate Attapulgite clay Amorphous silica (synthetic) E. Compoud No. 102 Sodium dioctyl sulfosuccinate Sodium lignosulfonate Kaolin Amorphous silica synthetic F. Compound No. 106 Sodium lignosulfonate Sodium N-methyl-N-oleyl-taurate 35 Amorphous silica (synthetic Kaolinite clay 41-21 (3046) A Weight Percent .0 5.0 60.0 10.0 100.0 80.0 1.5 3.5 5.0 10-0 100.0 10.0 3.0 1.0 10.0 76.0 100.0 30.0 4.0 1.0 60.0 5t<? 100.0 75.0 1.25 3.0 10.75 10-0 100.0 15.0 3.0 1.0 10.0 71tQ 100.0 # IV. Granules A. Compound No. 36 Dipropylene Glycol •" Granular attapulgite (24/48 mesh) B. Compound No. 43 Ethylene Glycol (24/48 mesh) Granular Montmorillonite C. compound No. 49 Ethylene glycol Granular Pyrophyllite (24/48 mesh) D. Compound No. 52 Dipropylene Glycol Granular Pyrophyllite (24/48 mesh) E. Compound No. 53 Granular Bentonite (24/48 mesh) F. Compound No. 54 Amorphous silica (synthetic) Granular Montmorillonite (24/48 mesh) G. Compound No. 58 Ethylene glycol Granular Montmorillonite (24/48 mesh) H. Compound No. 59 Dipropylene Glycol Granular Bentonite (30/60 mesh) 239 41-21(3046)A Weight Percent 15.0 5.0 80.0 100.0 5.0 15.0 9Q.Q 100.0 1.0 5.0 94.0 100.0 5.0 15.0 80.0 100.0 20.0 80.0 100.0 20.0 1.0 79.0 100.0 5.0 10.0 95-Q 100.0 10.0 10.0 ?P-9 100.0 239 2 69 -90- 41-21(3046)A Weight Percent V. Suspension Concentrates A. Compound No. 66 32.5 Sodium Naphthalene-Formaldehyde Condensate (Morvet D-425) 3.0 Propylene Glycol 10.0 Sodium Oiisopropyl Naphthalene Sulfonate (Morvet IP) 1.0 Xanthan Gum (Kelzan S) 0.2 Water 52.3 100.0 B. Compound No. 81 37.0 Sodium Lignin Sulfonate (Polyfon H) 5.0 EO/PO Block Copolymer (Pluronic P-105) 2.0 Propylene Glycol 10.0 Xanthan Gum 0.2 Water 45.8 100.0 C. Compound No. 83 25.0 20 Sodium Lignin Sulfonate (Polyfon H) 4.0 Sodium N-Methyl-N-oleyltaurate (Igepon T-77) 1.0 Ethylene Glycol 10.0 Xanthan Gum (Rhodopol MD50) 0.2 Magnesium Aluminum Silicate (Van Gel-B) 0.2 Water 59.6 100.0 D. Compound No. 85 30.0 Sodium naphthalene sulfonate formaldehyde condensate 5.0 Glycerine 8.0 Methyl Cellulose (Methocel A15C) 0.3 Magnesium Aluminum Silicate (Van Gel B) 0.2 Water 56.5 100.0 # E. Compound No. 93 Nonylphenol ethoxylate 9.5 mole EO Sterox NJ Sodium lignosulfonate (Reax 88B) Ethylene Glycol Xanthan Gun Water F. Compound No. 96 Sodium lignin sulfonate (Polyfon F) Ethylene Glycol Xanthan Gum Water G. Compound No. 102 Sodium Naphthalene Sulfonate formaldehyde Condensate Propylene Glycol 20 Snelling Grade Bentonite Antifoam Water VI Microcapsules 25 (Active ingredient encapsulated within polymeric shell wall) A. Compound No. 69 Polyurea shell wall Reax* 88B (dispersant) NaCl (electrolyte) Water 239 2 69 41-21(3046)A Weight Percent 33.0 1.0 4.0 10.0 0.2 51^8 100.0 34.0 10.0 10.0 0.1 45.9 100.0 30.0 .0 7.0 0.5 0.5 52.0 100.0 4.0 0.4 1.0 5.0 89t6 100.00 ♦ *»&&& 2 6 9 B. Compound No. 81 Polyurea shell wall Reax® C-21 (dispersant) NaNOj (electrolyte) Aromatic 200 (solvent) Water C. Compound No. 130 Polyurea shell wall Reax® C-21 NaCl Xylene Water D. Compound No. 63 Polyurea shell wall Reax® 88B NaCl 2 0 Kerosene E. Compound No. 74 Polyurea shell wall Reax® 88B NaNO, Solvent Water F. Compound No. 157 Polyurea shell wall Reax® C-21 NaCl Solvent Water Weight Percent 0.5 6.82 1.0 5.0 45.0 41.68 100.00 1.0 7.0 2.0 10.0 40.0 40.0 100.0 48.0 4.8 3.0 15.0 29.? 100.0 40.0 6.5 2.0 10.5 25.0 16.0 100.0 10.0 8.5 1.5 6.0 20.0 54-Q 100.0

Claims (5)

    23 9 2 6 9 -93- *r^2TTT046)A When operating in accordance vith the present invention, effective amounts of the compounds of this invention are applied to the soil containing the seeds, or vegetative propagules or may be incorporated into the 5 soil media in any convenient fashion. The application of liquid and particulate solid compositions to the soil can be carried out by conventional methods, e.g., power dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a 10 dust or a spray because of their effectiveness at lov dosages. The exact amount of active ingredient to be employed is dependent upon various factors, including the plant species and stage of development thereof, the type and condition of soil, the amount of rainfall and 15 the specific compounds employed. In selective pre- emergence, post-emergence and soil applications a dosage of from about 0.0005 kg/ha (0.5 g/ha) to about 11.2 kg/ha is usually employed. A dosage of about 0.001 kg/ha (1.0 g/ha) to about 0.50 kg/ha (500 g/ha) is 20 preferred. Lover or higher rates may be required in some instances. One skilled in the art can readily determine from this specification, including the above examples, the optimum rate to be applied in any particular case. 25 The term "soil" is employed in its broadest sense to be inclusive of all conventional "soils" as defined in Webster's Nev International Dictionary. Second Edition, Unabridged (1961). Thus, the term refers to any substance or medium in which vegetation 30 nay take root and grow, and includes not only earth but also compost, manure, muck, humus, loam, silt, mire, clay, sand, and the like, adapted to support plant WHAT^VE CLAIM iS II: 1. 2392 - 94 41-21(3046)A Compounds according to Formula R. 10 II N R-, R so*-Rz wherein Rt is hydrogen, C[.5 alkyl optionally substituted with an Rg member; Cw cycloalkyl or cycloalkenyl optionally substituted with CM alkyl; R, is Ct.s alkyl optionally substituted with an- 20 member; r3 is hydrogen or halogen; Rj is halogen and r< and r7 are C14 alkyl, haloalkyl, alkylthio, alkoxy- 25 alkyl or polyalkoxyalkyl, Cw cycloalkyl, cycloalkenyl, cycloal-kylalkyl or cycloalkenylalkyl; C,., alkenyl or alkynyl; carbamyl, halogen, amino, nitro, cyano, hydroxy, C ^ jg heterocycle containing 1-4 3Q o, s (o)m and/or n hetero atoms, cs.l2 aryl, aralkyl or alkaryl, -cxyr,, -cxr,, -ch2ocor10, -yru, -nr12r13, or any two combinable Rg and R^ members may be combined throuqh a saturated and/or unsaturated carbon, x II 35 -C- and/or hetero atom linkage to form a heterocyclic ring having up to 9 ring members, which may be substituted with any of said Ri-R7 members or said combinable R^ and R- or R,.,3 members 2H1AR394 239269 - 95 - 41-21(3046)A substituted with any of said Rs-R7 members; provided that when said two r and R members are combined through a -hetero atom 6 7 O II . . 5 -C-N- linkage, said heterocyclic ring has at least six ring members; X is 0, SfO)^, NRU or CRl5Rl6; Y is O or SfO),,, or NR17; 10 Rj~Rt7 are one said r5-r7 members and m is 0-2 ; provided that when R^ and R2 are methyl, R3 is bromo or chloro, R& is fluoro, R6 is chloro, R7 is -CH2C02-i-C3H7, -CH2CH2C02C2H5 or YRn wherein Y is O, S or -NR12R13 and 15 Rn-R13 areas defined above. 2. Compounds according to claim 1 wherein said compounds of Formula II are a subgroup of compounds according to Formula III 20 III 25 ni wherein R, and R2 are C,.s alkyl; Rj is hydrogen, bromo, chloro or fluoro; Rj is halogen; R^ is halogen or nitro; Rj is a member as defined in Claim 1 or R« and R7 are combined through an -0CH2(C=0) -N-(propynyl)-linkage to form a fused six-membered ring. 30 35 10 96 6 9 3. Compounds according to claim 2 wherein R1 and R2 are methyl; Rj is hydrogen, bromo or chloro; R, is chloro or fluoro/ R6 is chloro, fluoro, or nitro; Rr is a YRn member . or R6 and R7 are combined through an -0CH2(C=0)-N-(propynyl)-linkage to give a fused 6-membered ring. 4. Compounds according to claim 1 selected from the group consisting of 4-chloro-3-(2-fluoro-4-chloro-5-(2-propynyloxy)phenyl)-l-methyl-5-(methylsulfonyl)-lH-pyrazole; 15 4-bromo-3-(2-fluoro-4-chloro-5-(2-propynyloxy)phenyl)-l-methyl-5-(methylsulfonyl)-lH-pyrazole; 4-chloro-3-(2-fluoro-4-chloro-5-(2-methoxyethoxy)-phenyl)-l-methyl-5-(methylsulfonyl)-lH-pyrazole ; 4-bromo-3-(2-fluoro-4-chloro-5-(2 -methoxyethoxy)-20 phenyl)-l-methyl-5-(methylsulfonyl)-lH-pyrazole ; 6-(4-chloro-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-yl)-7-fluoro-4-(2-propynyl)-2H-1,4-benzoxazin-3-(4H)-one; (5-(4-bromo-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-25 yl)-2-chloro-4-fluorophenoxy)acetic acid, 1- methylethyl ester ; (5-(4-chloro-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-yl)-2-chloro-4-fluorophenoxy) acetic acid, 1-methylethyl ester ; 30 3-(5-(4-bromo-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-yl)-2-chloro-4-fluorophenoxy)propanoic acid, ethyl ester; and 3-(5-(4-chloro-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-yl) -2-chloro-4-fluorophenoxy) propanoic acid, 35 ethyl ester. 1 * FED W | •. RCCciVED 239269 - 97 - 41 21(3046)A 5. 4-Chloro-3-(2-fluoro-4-chloro-5-(2-propynyloxy)phenyl)-l-methyl-5-(methylsulfonyl)-1H-pyrazole. 6. 4-Bromo-3-(2-fluoro-4-chloro-5-(2- 5 propynyloxy)phenyl)-l-methyl-5-(methylsulfonyl)-1H-pyrazole. 7. 3-(5-(4-Chloro-l-methyl-5-(methylsulfonyl) -lH-pyrazol-3-yl) -2-chloro-4-fluorophenoxy)-propanoic acid, ethyl ester. 10 8. (5-(4-Chloro-l-methyl-5-(methylsulfonyl)- lH-pyrazol-3-yl)-2-chloro-4-fluorophenoxy)acetic acid, l-methylethyl ester. 9. Herbicidal composition comprising 15 an adjuvant and.a herbicidally effective amount of a Compound according to Formula II: 20 II so. 25 wherein Rt is hydrogen, alkyl optionally substituted with an R<s member; C3.8 cycloalkyl or cycloalkenyl 30 optionally substituted with cM alkyl; R2 is Ct.s alkyl optionally substituted with an R<s member; R3 is hydrogen or halogen; J jggjj. 35 R< is halogen and """ | h:.;v,.ive[ £D R$ and R, are Cw alkyl, haloalkyl, alkylthio, alkoxyalkyl or polyalkoxyalkyl, Cj_, cycloalkyl, cycloalkenyl, cycloalkylalky 1 or cycloalkenylalkyl; Cj., alkenyl or alkynyl; 239269 - 98 - 41-21(3046)A carbamyl, halogen, amino, nitro, cyano, hydroxy, C heterocycle containing 1-4 O, S(0)m and/or N hetero atoms, C^j aryl, aralkyl or 5 alkaryl, — CXYRj, -CXR^/ —CHjOCORjq/ YRjj, ""NRjjRjj, or any two combinable R- and R members may be combined through a saturated and/or 6 7 unsaturated carbon, X II 10 -c- and/or hetero atom linkage to form a heterocyclic ring having up to 9 ring members, which may be substituted with any of said Rj-Ry members or said icombinable R^-and or R^j members substituted with any of said Rj-R7 members; provided that when said two R and R, members are combined through a -hetero atom • o / o II -C-N- linkage, said heterocyclic ring has at least six ring members; 20 X is 0, S(0)m, NRU or CR13RI6; Y is 0 or S (0) m or NRl7; R,-Ri7 are one of said R5-R7 members and m is 0-2 ; provided that when R^ and R2 are methyl, 25 R3 is bromo or chloro, R5 is fluoro, Rs is chloro, R7 js -CH2C02-i-CjH7, -CH2CH2C02C2H5 or YRa wherein Y is O, S or -NR12R,3 and Rn-Ri3 areas defined above. 23 9 2 69 10.. - 99 - 41-21(3040)A Herbicidal compositions comprising an adjuvant and a herbicidally-effective amount of a compound according to Formula III: III so2 -r2 10 i R, 15 wherein fluoro; Rj and R2 are alkyl; R3 and Rj are hydrogen, bromo, chloro or R6 is an Rj member or nitro; R7 is a YR^j member as defined in claim 9 or R6 and R7 are combined through an -0CH2(C=0)-N- (R4)-linkage to form a fused six-membered ring. 20 25 30 35 11. Composition according to claim 10 wherein in said compound: R1 and R2 are methyl; Rj is hydrogen, bromo or chloro; R, is chloro or fluoro; R6 is chloro, fluoro or nitro; R7 is a YRn member or R6 and R7 are combined through an 0CH2(C=0)-N-(propynyl)-linkage to give a fused 6-membered ring. 12. composition according to claim 9 wherein said compound is selected from the group consisting of 4 - ch lor o-3 - (2-f luoro-4 -chloro-5- (2 -pr opyny loxy) pheny 1) - l-methyl-5-(methylsulfonyl) -lH-pyrazole; 4-bromo-3-(2-fluoro-4-chloro-5-(2-propynyloxy)phenyl) - l-methyl-5- (methylsulfonyl) -lH-pyrazole; 4-chloro-3-(2-fluoro-4-chloro-5«(2-methoxyethoxy)-phenyl)-l-methyl-5-(methylsulfonyl)-lH-pyrazole ; ■i£!l 1 4 FEB 1334 MECCiVEn V 9 ? 6 9 100 - «1 21 (304G)A ^ 4 - bromo- 3 - (2 - f luoro-4 -ch loro-5- (2 -methoxyethoxy) - phenyl)-l-methyl-5-(methylsulfonyl)-lH-pyrazole; 6-(4-chloro-l-methy1-5-(methylsulfonyl)-lH-pyrazol-3-yl)-7-fluoro-4-(2-propynyl)-2H-1,4-benzoxazin-3-5 (4H)-one ; (5-(4-bromo-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-yl)-2-chloro-4-fluorophenoxy)acetic acid, 1-methylethyl ester; (5-(4-chloro-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-10 yl)-2-chloro-4-fluorophenoxy)acetic acid, 1- methylethyl ester; 3 -(5-(4-bromo-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-yl)-2-chloro-4-fluorophenoxy)propanoic acid, ethyl ester;and 15 3 -(5-(4-chloro-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-yl)-2-chloro-4-fluorophenoxy)propanoic acid, ethyl ester. 13. Herbicidal composition comprising an adjuvant and a herbicidally-effective amount of 4- 20 chloro-3- [ 2-f luoro-4-chloro-5- (2-propynyloxy) phenyl-1-methyl-5-(methylsulfonyl) -lH-pyrazole. 14. Herbicidal composition comprising an adjuvant and a herbicidally-effective amount of 4-bromo-3-(2-f luoro-4-chloro-5-(2-propynyloxy)phenyl)-1-methyl- 25 5-(methylsulfonyl)-lH-pyrazole. 15. Herbicidal composition comprising an adjuvant and a herbicidally-effective amount of 3-(5-(4-chloro-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-yl) -2-chloro-4-fluorophenoxy)-propanoic acid, ethyl ester. 30 16. Herbicidal composition comprising an adjuvant and a herbicidally-effective amount of (5—(4— chloro-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-yl) -2-chloro-4-fluorophenoxy)acetic acid, 1 methylethyl ester. 17. Method for combating undesirable plants in 35 crops which comprises applying to the locus thereof a herbicidally effective amount of a compound according to Formula II: 1 'i FEB 1394 , HLiCLiVED II 239269 41-21(3046)A 7 so2-^ wherein R, is hydrogen, C,.5 alkyl optionally substituted with an Rg member; C3.B cycloalkyl or cycloalkenyl 10 optionally substituted with C1>4 alkyl; Rj is C1>5 alkyl optionally substituted with an Rg member; R, is hydrogen or halogen; Rj is halogen and 15 R^ and R7 are alkyl, haloalkyl, alkylthio, alkoxy-alkyl or polyalkoxyalkyl, CM cycloalkyl, cycloalkenyl, cycloal-kvlalkvl or cycloalkenylalkyl; Cj., alkenyl or alkynyl; carbamyl, halogen, amino, nitro, cyano, hydroxy, C 4_iq heterocycle 20 containing 1-4 : ■ 0/ 3(0),, and/or N hetero atoms, aryl, aralkyl or alkaryl, -cxyrt, -cxr^, -ch7ocor10, —yrn, -nr,jr13, or any two combinable Rc'and R 7 members may be combined through a saturated and/or unsaturated earbon, 25 X H -C- and/or hetero atom linkage to form a heterocyclic ring having up to 9 ring members, which may be substituted with, any of said R5-R7 member 1 or said combinable Rg and ■—-— or R,.0 members 3d substituted with any of said R5-R7 members; provided that when said two R and R members are combined through a -hetero atom 6 7 o II . . . -ON- linkage, said heterocyclic ring has at least six ring 35 members; X is 0, S(0)n, NRU or CRlsRt6; 4 . Y is 0 or 8(0). or NR17; 2 1 MAR $394 * r- R,-Rl7 are one of said Rj-R7 members and m is 0-2 ; provided that when Rj" and R2 are methyl, (followed by page - 101a -) 101a - 23 9 2 69 CWmiA bj page (07.) R3 is bromo or chloro, R5 is fluoro, Rg is chloro, R7 is -CH2C02-i-C3H7, -CH2CH2C02CjH5 or YRn wherein Y is O, S or -NR12R13 and Rii'Ria are as defined above. 18. Method of combating undesirable plants in crops which comprises applying to the locus thereof a herbicidally-effective amount of a compound according to Formula III: * iii wherein n so2 -r2 n:'. office 14 FED 1994 23 9 2 6 - 102 - '41-21 (3046)A R, and R2 are C1>5 alkyl; R3 and R5 are hydrogen, bromo, chloro or fluoro; R6 is an R5 member or nitro; R7 is an Rt member or 5 R6 and R7 are combined through an -0CH2(C=0) -N- (R4)-linkage to form a fused six-membered ring. 19. Method according to claim 18 wherein in said compound: 10 R, and Rj are methyl; Rj is hydrogen, bromo or chloro; Rj is chloro or fluoro; r6 is chloro, fluoro, or nitro; r7 is a yrn member as defined in Formula I or 15 r6 and r7 are combined through an -OCH2(C=0)- N-(propynyl)-linkage to give a fused 6-membered ring. 20. Method according to claim 17 wherein said compound is selected from the group consisting of 20 4-chloro-3-(2-fluoro-4-chloro-5-(2-propynyloxy)phenyl)-l-methyl-5-(methylsulfonyl)-lH-pyrazole; 4-bromo-3-(2-fluoro-4-chloro-5-(2-propynyloxy)phenyl)-
  1. l-methyl-5-(methylsulfonyl)-lH-pyrazole; 4-chloro-3-(2-fluoro-4-chloro-5-(2-methoxyethoxy)-25 phenyl)-l-methyl-5-(methylsulfonyl)-lH-pyrazole ; 4-bromo-3-(2-fluoro-4-chloro-5-(2-methoxyethoxy)- phenyl)-l-methyl-5-(methylsulfonyl)-lH-pyrazole; 6-(4-chloro-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-y1)-7-fluoro-4-(2-propyny1)-2H-1,4-benzoxazin-3-30 (4H) -one '» (5-(4-bromo-1-methy1-5-(methylsulfony1)-lH-pyrazol-3-yl)-2-chloro-4-fluorophenoxy)acetic acid, 1-methylethyl ester ; (5-(4-chloro-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-35 yl)-2-chloro-4-fluorophenoxy)acetic acid, 1- methylethyl ester; j npatent - _ i I 8' JAN m \ hcceived 239269 10 15 - 103 - , , 41-21(3046)A U-0U0ir>«& pa105a ^ 3 -(5-(4-bromo-l-methy1-5-(methylsulfonyl)-lH-pyrazol-3- yl)-
  2. 2-chloro-4-fluorophenoxy)propanoic acid, ethyl ester ; and
  3. 3-(5-(4-chloro-l-methyl-5-(methylsulfonyl)-lH-pyrazol-3-yl)-2-chloro-4-fluorophenoxy)propanoic acid, ethyl ester. 21. Method of combating undesirable plants in crops which comprises applying to the locus thereof a herbicidally-effective amount of 4-chloro-3-[2-fluoro-
  4. 4-chloro-
  5. 5-(2-propynyloxy)phenyl]-l-methyl-5-(methylsulfonyl) -lH-pyrazole. 22. Process for the preparation of compounds according to Formula II which comprises reacting a compound according to Formula B with an oxidizing agent according to the equation Rs R, 20 oxidation Rs R, O r? 1 V"t R, 30 wherein R, is hydrogen, C,.5 alkyl optionally substi-25 tuted with an R4 member; Cj.g cycloalkyl or cycloalkenyl optionally substituted with CV4 alkyl; Rj is C1>5 alkyl optionally substituted with an R^ member; Rj is hydrogen or halogen and Rj is halogen and R* and R7 are Cw alkyl, haloalkyl, alkylthio, alkoxy- alkyl or polyalkoxyalkyl, CM cycloalkyl, cycloalkenyl, cycloalkyl alkyl or cycloalkenylalkyl; alkenyl or alkynyl; carbamyl, halogen, amino, nitro, cyano, hydroxy, C 4_10 heterocycle containing 1-4 1 ; - O, S(0)„ and/or N hetero atoms, C^j aryl, aralkyl or alkaryl, -CXYR,, -CXR,, -CHjOCOR10, -YR„, -NRI2R13, or any two combinable 35 R, and R_ members 6 7 (followed bv page - 103a -) 2 1 flAR'394 1033 "(MM by ,239 269 may be combined through a saturated and/or unsaturated carbon, X II -C- and/or hetero atom linkage to form a heterocyclic ring having up to 9 ring members, which may be substituted with any of said Rj-R7 members or said combinable Rg and R^ r— or Bj-u members substituted with any of said Rg-Rj members; provided that when said two R and R? members are combined through a -hetero atom 6 ' 0 II . . -C-N- linkage, said heterocyclic ring has at least six ring members; X is 0, S(0)o/ NR[4 or CR,jR16; Y is 0 or S(0)o or NR17; Rj-R,7 are one of said Rj-R7 members and m is 0-2. ;■<"! .*ry-v. / ^ Q'\ :/ \ ."'2 1 MAR 1994 • - 104 - 23 4^-34r{3046)A 23. Process according to claim 22 wherein 5 said compounds according to*Formula II are those as defined for Formula III *5 10 III n IT SO, -R, 15 20 wherein fluoro; Rj and R2 are Cj.j alkyl; Rj and Rj are hydrogen, bromo, chloro or R6 is an Rj member or nitro; R7 is an R4 member or R6 and R7 are combined through an -0CH2(C=0) N-linkage to form a fused six-membered ring. 25 30 35 24. Process according to claim 23 wherein Rj and R2 are methyl; Rj is hydrogen, bromo or chloro; Rj is chloro or fluoro; R$ is chloro, fluoro or nitro and R7 is a YR1t member as defined in Formula I. 25. Process for the preparation of compounds according to Formula II wherein Rj is a halogen, which comprises reacting a Formula I compound wherein R3 is hydrogen with a halogenating agent. 26. Process according to claim 25 wherein said Formula II compounds prepared by the halogenation process are those as defined for Formula III wherein R3 is halogen. i. ;'£nt office * 8 JAN 1994 ' reived 239 2 69 -105 - 41 21(3046)A 27. Process according to claim 26 wherein R^ and R2 are methyl, *5 is chloro or fluoro and R$ is chloro, fluoro or nitro. 28. Process for the preparation of compounds according to Formula II wherein one of sai.d Rt members is -YRn and Rn is not hydrogen, which comprises reacting the corresponding compound of Formula I wherein R„ is hydrogen with an acylating or alkylating agent. 29. Process according to claim 28 wherein said compound of Formula I prior to said acylation or alkylation is a compound as defined for Formula III wherein R7 is -YH. 30. Compounds according to Formula Has defined in claim 1 substantially as herein described with reference to any example thereof. 31. Compounds according to Formula III as defined in claim 3 substantially as herein described with reference to any example thereof. 32. A herbicidal composition as defined in claim 10 substantially as herein described with reference to any example thereof. 33. A herbicidal composition as defined in claim 12 substantially as herein described with reference to any example thereof. 34. A method for combating undesirable plants in crops as defined in claim 19 when performed substantially as herein described with reference to any example thereof. defined in claim 21 when performed substantially as herein described with reference to any example thereof. 36. A process for the preparation of compounds according to Formula I as defined in claim 25 when performed substantially as herein described with reference to any example thereof. 37. A process for the preparation of compounds according to .Formula III as defined in claim 27 when performed substantially as herein described with reference to any example thereof .dated this day of A.J. PARK & SON •»io I-QR THE APPLICANTS
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AU653299B2 (en) * 1993-02-06 1994-09-22 Nihon Nohyaku Co., Ltd. A herbicidal composition having a reduced phytotoxicity
MY111038A (en) * 1993-10-12 1999-07-31 Nihon Nohyaku Co Ltd An improved pesticidal aqueous suspension concentrate and a process for production thereof.
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