WO1996015116A1 - Pyrazoles herbicides - Google Patents

Pyrazoles herbicides Download PDF

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Publication number
WO1996015116A1
WO1996015116A1 PCT/GB1995/002459 GB9502459W WO9615116A1 WO 1996015116 A1 WO1996015116 A1 WO 1996015116A1 GB 9502459 W GB9502459 W GB 9502459W WO 9615116 A1 WO9615116 A1 WO 9615116A1
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WO
WIPO (PCT)
Prior art keywords
compounds
reaction
formula
general formula
compound
Prior art date
Application number
PCT/GB1995/002459
Other languages
English (en)
Inventor
Ewan James Turner Chrystal
Susan Patricia Barnett
Original Assignee
Zeneca Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zeneca Limited filed Critical Zeneca Limited
Priority to AU36468/95A priority Critical patent/AU3646895A/en
Publication of WO1996015116A1 publication Critical patent/WO1996015116A1/fr

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Classifications

    • 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
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • 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

Definitions

  • cycloalkenyl refers to a hydrocarbon ring having from three to eight ring carbon atoms and containing at least one double bond. Examples of such groups include cyclohexenyl.
  • Suitable halogenating agents include chlorinating agents such as chlorine, phosphorus, trichloride, phosphorus pentachloride and sulphuryl chloride, as well as other halogenating agents such as bromine and iodine.
  • the compound of general formula (XXVT) is reacted with powdered solid carbon dioxide and then the reaction mixture is neutralised with an acid solution.
  • Suitable acid solutions include aqueous solutions of mineral acids, for example dilute hydrochloric acid, or, alternatively, aqueous solutions of salts of weak bases, for example aqueous ammonium chloride.
  • the reaction may be conducted at a temperature of from -80°C to 50°C, typically -10°C to 30°C.
  • a nucleophilic catalyst may also be present and the reaction should preferably be conducted in a dry inert atmosphere and in a solvent such as a halogenated solvent, for example dichloromethane; an ether, for example tetrahydroruran; a nitrile, for example acetonitrile; an aromatic solvent, for example dichlorobenzene; or a heterocyclic solvent, for example pyridine.
  • a solvent such as a halogenated solvent, for example dichloromethane; an ether, for example tetrahydroruran; a nitrile, for example acetonitrile; an aromatic solvent, for example dichlorobenzene; or a heterocyclic solvent, for example pyridine.
  • a base may also be present and suitable bases are inorganic bases such as alkali and alkaline earth metal hydroxides or carbonates, typically potassium carbonate. Alternatively, an organic base may be used and suitable examples include tertiary amines such as triethy
  • phase transfer catalyst may also be used.
  • Suitable phase transfer catalysts include quaternary ammonium salts, for example tetrabutylammonium iodide, quaternary phosphoniu salts, such as tetrabutyl phosphonium bromide, and crown ethers, for example 18-crown-6.
  • R 1 , R 4 , X, Y and n are as defined in relation to formula (I) by reaction with compounds of formula (R C Z), where R e is R 3 (except when R 3 is H), and Z is a leaving group, in the presence of a base as described in the art.
  • suitable leaving groups include chlorine.
  • a particularly preferred compound of formula (R C Z) is chlorodifluoromethane.
  • the reaction is suitably effected in the presence of a solvent or mixtures of solvents, in the presence or absence of a base and optionally in the presence of a catalyst at a temperature between -10 and 100°C.
  • R 4 is SOpR 3
  • Suitable oxidising agents for this conversion include peracids such as n-chloroperbenzoic acid, dioxiranes such as dimethyldioxirane, periodate salts, such as potassium periodate, and salts of transition metals in higher oxidation states, including potassium permanganate.
  • An alternative synthesis for compounds of general formula (In) is the reaction of compounds of (D) with compounds of formula (XX) in the presence of a dehydrating agent such as a carbod ⁇ mide, typically N,N-dicyclohexylcarbodiimide, or a di-substituted carbonyl derivative of formula COQQ' where Q and Q' are leaving groups such as in 1,1-carbonylimidazole.
  • a dehydrating agent such as a carbod ⁇ mide, typically N,N-dicyclohexylcarbodiimide, or a di-substituted carbonyl derivative of formula COQQ' where Q and Q' are leaving groups such as in 1,1-carbonylimidazole.
  • R 1 , R 2 , R 3 and Y are as defined in general formula I and R l is an alkyl, preferably a tertiary alkyl, group with an amine of general formula (XXII).
  • the reaction may be carried out in the presence ofa nucleophilic catalyst in an inert atmosphere at a temperature of -20°C to 200°C, more typically from 0°C to 100°C.
  • R 1 is an alkyl, typically a tertiary alkyl, group for example tertiary butyl.
  • inorganic bases include alkali or alkaline earth metal hydrides, hydroxides or carbonates typically sodium hydroxide.
  • organic bases are alkali metal alkoxides, particularly sodium ethoxide, and tertiary amines such as diazobicycloundecane.
  • the reaction temperature will typically be -30°C to 200°C , more probably from 0°C to 50°C.
  • the synthesis of compounds of general formula (XI) has already been described above. The synthesis of compounds (lo), (Ip), (lib), (Ho) and (up) is summarised in Reaction Scheme DI.
  • miscellaneous herbicides including ethofumesate, cinmethylin, difenzoquat and salts thereof such as the methyl sulphate salt, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, flurochloridone, quinchlorac, mefanacet, and triketone herbicides such as sulcotrione; BB.
  • useful contact herbicides include: bipvridylium herbicides such as those in which the active entity is paraquat and those in which the active entity is diquat;
  • Step f Preparation of 4-chloro-3-(5-difluoromethoxy-2-fluorophenyI)-5- difluoromethoxy-1-methylpyrazole, Compound 1 of Table 1).

Abstract

L'invention porte sur des composés de la formule (I). Dans cette formule, R1 représente hydrogène, alkyle, alcényle, alcynyle, n'importe lequel d'entre eux pouvant éventuellement être substitué; R2 représente alkyle, alcényle ou alcynyle, n'importe lequel d'entre eux pouvant éventuellement être substitué, ou OR5 ou SO¿mR?5; R3 représente hydrogène, halogène, cyano, alkyle éventuellement substitué, alcényle ou alcynyle ou OR5 ou CO¿2R?5; R4 représente hydrogène, alkyle, alcényle ou alcynyle, n'importe lequel d'entre eux pouvant éventuellement être substitué, halogène, cyano, nitro, CO¿2?R?5, OR5, NR5R6, NR5SO¿2R6, OSO2R5 ou OmSR?5R6R7; R5, R6 et R7¿ sont chacun indépendamment hydrogène, alkyle, alcényle ou alcynyle, n'importe lequel pouvant éventuellement être substitué; chaque X est indépendamment halogène, cyano, nitro, hydroxy, alkyle, alkoxy, alkyltio, alkoxyalkyle, SO¿m?alkyle, CONR?8R9¿ ou hétérocyclyle ou selon un autre mode de réalisation, deux groupes X ensemble ou un seul groupe X avec R4 peuvent former un autre cycle, m étant égal à 0, 1 ou 2 et n à 0, 1 ou 2; R8 et R9 sont indépendamment hydrogène ou alkyle inférieur. Les composés de la formule (I) sont actifs en tant qu'herbicides.
PCT/GB1995/002459 1994-11-10 1995-10-18 Pyrazoles herbicides WO1996015116A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU36468/95A AU3646895A (en) 1994-11-10 1995-10-18 Herbicidal pyrazoles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9422708A GB9422708D0 (en) 1994-11-10 1994-11-10 Herbicides
GB9422708.9 1994-11-10

Publications (1)

Publication Number Publication Date
WO1996015116A1 true WO1996015116A1 (fr) 1996-05-23

Family

ID=10764184

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1995/002459 WO1996015116A1 (fr) 1994-11-10 1995-10-18 Pyrazoles herbicides

Country Status (5)

Country Link
AU (1) AU3646895A (fr)
GB (1) GB9422708D0 (fr)
IL (1) IL115711A0 (fr)
WO (1) WO1996015116A1 (fr)
ZA (1) ZA959002B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998027090A2 (fr) * 1996-12-16 1998-06-25 Basf Aktiengesellschaft Pyrazol-3-ylbenzazoles substitues
WO1999055702A1 (fr) * 1998-04-29 1999-11-04 Basf Aktiengesellschaft (4-brompyrazol-3-yl)benzazoles substitues

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0019760A1 (fr) * 1979-05-23 1980-12-10 BASF Aktiengesellschaft Esters de l'acide 3-aryl-5-méthyl-pyrazole-4-carboxyliques, herbicides les contenant, procédé pour leur production et leur utilisation
EP0074749A2 (fr) * 1981-08-31 1983-03-23 Uniroyal, Inc. Pyrazoles substitués comme herbicides
EP0230110A1 (fr) * 1985-11-30 1987-07-29 FISONS plc Dérivés du pyrrole et du pyrazole doués d'une activité pharmacologique
JPH02300173A (ja) * 1988-09-07 1990-12-12 Nippon Nohyaku Co Ltd ３又は５−フェニルピラゾール類又はその塩及び除草剤
JPH0347180A (ja) * 1989-04-21 1991-02-28 Nippon Nohyaku Co Ltd ３―置換フェニルピラゾール誘導体又はその塩類及びその製造方法並びに除草剤
JPH0393774A (ja) * 1989-09-07 1991-04-18 Nippon Nohyaku Co Ltd ３又は５―フェニルピラゾール類又はその塩及び除草剤
WO1992002509A1 (fr) * 1990-08-06 1992-02-20 Monsanto Company Arylpyrazols d'akylsulfonil herbicides a substitutions
WO1992006962A1 (fr) * 1990-10-18 1992-04-30 Monsanto Company Composes herbicides d'haloalkylpyrazoles aryle substitue
DE4126543A1 (de) * 1991-08-10 1993-02-11 Chem & Pharm Patent Hold Ltd 3(5)-(hydroxyaryl)-pyrazole und ihre verwendung als wirkstoffe in arzneimittel
JPH06157469A (ja) * 1992-11-13 1994-06-03 Ube Ind Ltd ピラゾールカルボニルウレア誘導体、その製法及び有害生物防除剤
JPH06199806A (ja) * 1992-09-29 1994-07-19 Nippon Nohyaku Co Ltd ジフルオロメトキシピラゾール誘導体及びその製造方法
DE4341749A1 (de) * 1993-12-08 1995-06-14 Kali Chemie Pharma Gmbh 3-(Phenylalkylaminoalkyloxy)-5-phenylpyrazol- Verbindungen sowie Verfahren und Zwischenprodukte zu ihrer Herstellung und diese Verbindungen enthaltende Arzneimittel

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0019760A1 (fr) * 1979-05-23 1980-12-10 BASF Aktiengesellschaft Esters de l'acide 3-aryl-5-méthyl-pyrazole-4-carboxyliques, herbicides les contenant, procédé pour leur production et leur utilisation
EP0074749A2 (fr) * 1981-08-31 1983-03-23 Uniroyal, Inc. Pyrazoles substitués comme herbicides
EP0230110A1 (fr) * 1985-11-30 1987-07-29 FISONS plc Dérivés du pyrrole et du pyrazole doués d'une activité pharmacologique
JPH02300173A (ja) * 1988-09-07 1990-12-12 Nippon Nohyaku Co Ltd ３又は５−フェニルピラゾール類又はその塩及び除草剤
JPH0347180A (ja) * 1989-04-21 1991-02-28 Nippon Nohyaku Co Ltd ３―置換フェニルピラゾール誘導体又はその塩類及びその製造方法並びに除草剤
JPH0393774A (ja) * 1989-09-07 1991-04-18 Nippon Nohyaku Co Ltd ３又は５―フェニルピラゾール類又はその塩及び除草剤
WO1992002509A1 (fr) * 1990-08-06 1992-02-20 Monsanto Company Arylpyrazols d'akylsulfonil herbicides a substitutions
WO1992006962A1 (fr) * 1990-10-18 1992-04-30 Monsanto Company Composes herbicides d'haloalkylpyrazoles aryle substitue
DE4126543A1 (de) * 1991-08-10 1993-02-11 Chem & Pharm Patent Hold Ltd 3(5)-(hydroxyaryl)-pyrazole und ihre verwendung als wirkstoffe in arzneimittel
JPH06199806A (ja) * 1992-09-29 1994-07-19 Nippon Nohyaku Co Ltd ジフルオロメトキシピラゾール誘導体及びその製造方法
JPH06157469A (ja) * 1992-11-13 1994-06-03 Ube Ind Ltd ピラゾールカルボニルウレア誘導体、その製法及び有害生物防除剤
DE4341749A1 (de) * 1993-12-08 1995-06-14 Kali Chemie Pharma Gmbh 3-(Phenylalkylaminoalkyloxy)-5-phenylpyrazol- Verbindungen sowie Verfahren und Zwischenprodukte zu ihrer Herstellung und diese Verbindungen enthaltende Arzneimittel

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 107, no. 25, 21 December 1987, Columbus, Ohio, US; abstract no. 236702j, A.J.G. BAXTER ET AL.: "Preparation of pyrrole- and pyrazolecarboxylates as cardiotonics and calcium antagonists." page 790; column 1; *
CHEMICAL ABSTRACTS, vol. 114, no. 17, 29 April 1991, Columbus, Ohio, US; abstract no. 164226b, Y. MIURA ET AL.: "Preparation of 3- and 5-phenylpyrazole derivatives as herbicides." page 17; column 2; *
CHEMICAL ABSTRACTS, vol. 115, no. 9, 2 September 1991, Columbus, Ohio, US; abstract no. 92260d, J. MIURA ET AL.: "Preparation of 3- or 5-phenylpyrazole derivatives as herbicides." page 765; column 2; *
CHEMICAL ABSTRACTS, vol. 115, no. 9, 2 September 1991, Columbus, Ohio, US; abstract no. 92264h, K. MACHITANI ET AL.: "Preparation of 3-(benzothiazolyl, benzoxazolyl and benzimidazolyl)pyrazole derivatives as herbicides" page 766; column 1; *
CHEMICAL ABSTRACTS, vol. 119, no. 1, 5 July 1993, Columbus, Ohio, US; abstract no. 8806p, G. KAESTNER ET AL.: "Preparation and biological activity of 3(5)-(hdroxyaryl)pyrazoles." page 907; column 2; *
CHEMICAL ABSTRACTS, vol. 121, no. 25, 19 December 1994, Columbus, Ohio, US; abstract no. 300885q, I. NAKAO ET AL.: "Preparation of 3-phenyl-5-hydroxypyrazoles as herbicides." page 1014; column 2; *
CHEMICAL ABSTRACTS, vol. 121, no. 25, 19 December 1994, Columbus, Ohio, US; abstract no. 300886r, T. KODAIRA ET AL.: "Preparation of difluoromethoxypyrazoles as herbicides." page 1014; column 2; *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998027090A2 (fr) * 1996-12-16 1998-06-25 Basf Aktiengesellschaft Pyrazol-3-ylbenzazoles substitues
WO1998027090A3 (fr) * 1996-12-16 1998-09-17 Basf Ag Pyrazol-3-ylbenzazoles substitues
EA002350B1 (ru) * 1996-12-16 2002-04-25 Басф Акциенгезельшафт Замещенные пиразол-3-илбензазолы
WO1999055702A1 (fr) * 1998-04-29 1999-11-04 Basf Aktiengesellschaft (4-brompyrazol-3-yl)benzazoles substitues
US6482774B1 (en) 1998-04-29 2002-11-19 Basf Aktiengesellschaft Substituted (4-brompyrazole-3-yl) benzazoles

Also Published As

Publication number Publication date
AU3646895A (en) 1996-06-06
GB9422708D0 (en) 1995-01-04
ZA959002B (en) 1996-05-23
IL115711A0 (en) 1996-01-19

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