WO1993018016A1 - Oxazolidinones fongicides - Google Patents

Oxazolidinones fongicides Download PDF

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Publication number
WO1993018016A1
WO1993018016A1 PCT/US1993/002164 US9302164W WO9318016A1 WO 1993018016 A1 WO1993018016 A1 WO 1993018016A1 US 9302164 W US9302164 W US 9302164W WO 9318016 A1 WO9318016 A1 WO 9318016A1
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Prior art keywords
optionally substituted
alkyl
phenyl
substituted
pyridyl
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PCT/US1993/002164
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English (en)
Inventor
Carlton Lane Campbell
Charlene Marie Gross
Jeffrey Arthur Sternberg
King-Mo Sun
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E.I. Du Pont De Nemours And Company
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Priority to AU38006/93A priority Critical patent/AU3800693A/en
Priority to EP93907384A priority patent/EP0630370A1/fr
Publication of WO1993018016A1 publication Critical patent/WO1993018016A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole 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
    • C07D263/44—Two oxygen 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
    • A01N43/72—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
    • A01N43/74—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 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole 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
    • C07D263/46—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole 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
    • C07D263/48—Nitrogen atoms not forming part of a nitro radical
    • 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

Definitions

  • the present invention relates to substituted oxazolidinone compounds, fungicidal compositions containing such compounds, and method of use of the compounds and compositions as fungicides.
  • New compounds effective for controlling the growth of undesired fungi are in constant demand. In the most common situation, such compounds are sought to
  • WO90/12791 teaches the use of fungicidal compounds of Formula i
  • A is O or NR 4 ;
  • W is O or S.
  • WO90/12791 also relates to processes for the preparation of these compounds and to certain novel compounds.
  • the compounds of WO90/12791 differ from those of the present invention in the nature of R 2 .
  • the above reference does not disclose the compounds of the present invention.
  • the present invention comprises compounds of
  • Formula I including all geometric and stereoisomers, agricultural compositions containing them and use of the compounds and compositions as fungicides.
  • the variation in Formula I occurs primarily in substituent R 2 .
  • Formula I comprises:
  • R 1 is H; C 1 -C 4 alkyl; C 1 -C 4 haloalkyl; C 3 -C 6
  • R 2 is C 7 -C 20 alkyl; C 7 -C 20 haloalkyl; C 4 -C 17 alkyl substituted with C 3 -C 6 cycloalkyl; C 4 -C 17 alkyl substituted with phenyl optionally substituted with R 31 on the phenyl ring; C 3 -C 14 alkyl substituted with phenoxy or phenylthio each optionally substituted with R 31 ; C 1 -C 20 alkyl substituted with R 19 ; C 2 -C 6 alkoxyalkyl substituted with R 21 ; C 7 -C 20 alkoxyalkyl
  • R 21 optionally substituted with R 21 ; C 7 -C 20 alkenyl;
  • R 3 is phenyl, pyridyl, pyrimidinyl or pyridazyl
  • R 4 is H, methyl, or a ⁇ etyl
  • R 5 , R 7 , R 11 , R 14 , R 23 , R 24 , R 3 °, R 39 , R 43 , and R 55 are each independently H or C 1 -C 4 alkyl;
  • R 6 , R 29 , R 34 , R 38 , R 42 , R 44 , and R 56 are each
  • R 8 is C 1 -C 19 alkyl; C 2 -C 19 alkylcarbonyl; C 2 -C 19
  • R 9 is C 1 -C 18 alkyl; or phenyl optionally
  • R 10 , R 27 , and R 45 are each independently 1-2
  • R 12 is H; C 1 -C 8 alkyl optionally substituted with
  • R 11 and R 58 can be taken together as -CH 2 (CH 2 ) 2 CH 2 -, -CH 2 (CH 2 ) 3 CH 2 -, -CH 2 (CH 2 ) 4 CH 2 -, -CH 2 CH 2 OCH 2 CH 2 -, -CH 2 CH 2 SCH 2 CH 2 -, -CH 2 CH 2 N(R 5 )CH 2 CH 2 - or
  • R 13 is C 1 -C 6 alkyl; C 3 -C 6 cycloalkyl; phenyl
  • R 15 is C 1 -C 12 alkyl; C 2 -C 12 alkylcarbonyl; benzoyl optionally substituted with R 16 on the phenyl ring; C 2 -C 12 alkoxycarbonyl; C 2 -C 12 alkylaminocarbonyl substituted with R 55 on nitrogen;
  • phenoxycarbonyl optionally substituted with R 46 on the phenyl ring; or phenylaminocarbonyl optionally substituted with R 46 on the phenyl ring and with R 55 on nitrogen;
  • R 16 is 3 halogen; cyano; C 5 -C 8 alkyl; C 2 -C 8
  • R 17 , R 18 , R 32 , R 35 , R 47 , and R 53 are each
  • R 19 is cyano; nitro; C 1 -C 19 alkylthio; C 1 -C 19
  • alkylsulfinyl C 1 -C 19 haloalkoxy; C 5 -C 6
  • phenylsulfonyl phenyl-sulfinyl, pyridyl or pyridyloxy each optionally substituted with R 31 ; thienyl, pyrimidinyl, furanyl,
  • naphthalenyl naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R 38 ;
  • R 20 is cyano; nitro; C 1 -C 17 alkylthio; C 1 -C 17
  • alkylsulfinyl C 1 -C 17 haloalkoxy; C 5 -C 6
  • R 21 is cyano; nitro; C 1 -C 17 alkylthio; C 1 -C 17
  • alkylsulfinyl C 1 -C 17 haloalkoxy; C 5 -C 6
  • alkynyloxy C 1 -C 17 alkylsulfonyl; C 2 -C 17 alkoxycarbonyl; hydroxyl; hydroxycarbonyl;
  • naphthalenyl naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R 38 ;
  • R 22 is C 1 -C 16 alkyl; phenyl optionally substituted with R 36 ; or pyridyl optionally substituted with R 36 ;
  • R 25 is H; C 1 -C 6 alkyl; or phenyl optionally
  • R 26 is C 1 -C 6 alkyl; C 1 -C 6 alkoxy; phenoxy
  • R 28 is phenyl, pyridyl or pyrimidyl each optionally substituted with R 37 ; or thienyl, furanyl, isoxazolyl, oxazolyl or pyrazolyl each
  • R 31 , R 36 , R 37 , R 41 , R 46 are independently 1-2
  • R 33 is C 1 -C 6 alkyl; or phenyl optionally
  • R 40 is pyridyl or pyrimidyl each optionally
  • R 48 is cyano; nitro; C 1 -C 17 alkylthio; C 1 -C 17
  • alkylsulfinyl C 1 -C 17 haloalkoxy; C 5 -C 6
  • phenylsulfonyl phenylsulfinyl, pyridyl or pyridyloxy each optionally substituted with R 31 ; thienyl, pyrimidinyl, furanyl,
  • naphthalenyl naphthalenyl, pyrimidinyloxy, naphthalenyloxy each optionally substituted with R 38 ;
  • R 49 is C 5 -C 12 alkyl; C 2 -C 12 haloalkyl; C 5 -C 12
  • R 50 is C 1 -C 6 alkyl; C 1 -C 6 haloalkyl; C 1 -C 6 alkoxy;
  • R 51 is phenyl substituted with R 52 ; pyridyl or pyrimidyl each optionally substituted with R 37 ; or thienyl, furanyl, isoxazolyl, oxazolyl, or pyrazo
  • R 54 is phenyl substituted with R 37 ; pyridyl or
  • R 57 is C 1 -C 12 alkyl; C 3 -C 6 cycloalkyl; C 1 -C 12
  • haloalkyl C 3 -C 12 alkenyl; C 3 -C 12 haloalkenyl; C 3 -C 12 alkynyl; C 3 -C 12 haloalkynyl; phenyl, naphthalenyl or pyridyl each optionally substituted with R 41 ; or furanyl or thienyl each optionally substituted with R 42 ;
  • R 59 is phenyl optionally substituted with R 38 ;
  • A is O, NR 25 , or a direct bond
  • E and V are independently O or S;
  • J is O or N-A-L
  • n 1-4;
  • n 3-4;
  • Q is O, NR 11 , or a direct bond
  • T is phenyl optionally substituted with 1-2
  • W is O, S, or N-Q-R 58 ;
  • R 2 is an optionally substituted phenyl or heterocyclic ring, only H or F can be
  • the phenyl group is not attached to the alkyl carbon attached to the oxazolidinone ring.
  • This invention further comprises a fungicidal composition
  • a fungicidal composition comprising an effective amount of a compound of Formula I as defined above and at least one of (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent.
  • the invention further comprises a method of
  • controlling fungal diseases in plants comprising treating the locus to be protected with an effective amount of a compound of Formula I, as defined above.
  • a compound of Formula I as defined above.
  • the preferred compounds for use in the method of the present invention are defined as below for the
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” denotes straight chain or branched alkyl; e.g., methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl, hexyl, etc. isomers.
  • Me denotes methyl.
  • Cycloalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • cycloalkyloxy denotes the same groups linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy.
  • Cycloalkenyl denotes groups such as cyclopentenyl, cyclohexenyl, and cycloheptenyl.
  • Alkenyl denotes straight chain or branched alkenes; e.g., 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl , pentenyl, hexenyl, etc.
  • Alkenyl also denotes polyenes such as
  • Alkynyl denotes straight chain or branched alkynes; e.g., ethynyl, 1-propynyl, 3-propynyl and the different butynyl, pentynyl, hexynyl, etc. isomers.
  • Alkynyl can also denote moieties comprised of multiple triple bonds; e.g., 2,7-octadiyne and
  • Alkoxy denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy, hexyloxy, etc. isomers.
  • alkoxyalkoxyalkoxy examples include
  • Alkynyloxy denotes straight or branched
  • alkynyloxy moieties examples include HC ⁇ CCH 2 O,
  • Alkylthio denotes methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylsulfinyl denotes both enantiomers of an alkylsulfinyl group. For example, CH 3 SO, CH 3 CH 2 SO, CH 3 CH 2 CH 2 SO, (CH 3 ) 2 CHSO and the different butylsulfinyl, pentylsulfinyl and hexylsufinyl isomers.
  • alkylsulfonyl examples include CH 3 SO 2 ,
  • halogen either alone or in compound words such as “haloalkyl”, denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CF 2 .
  • haloalkynyl include HC ⁇ CCHCl, CF 3 C ⁇ C, CCl 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy include CF 3 O, CCl 3 CH 2 O, CF 2 HCH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CCT 3 S, CF 3 S,
  • haloalkylsulfonyl examples include CF 3 SO 2 , CCl 3 SO 2 , CF 3 CH 2 SO 2 and
  • haloalkoxyalkoxy include CF 3 OCH 2 O, ClCH 2 CH 2 OCH 2 CH 2 O, Cl 3 CCH 2 OCH 2 O as well as branched alkyl derivatives.
  • C i -C j The total number of carbon atoms in a substituent group is indicated by the "C i -C j " prefix where i and j are numbers from 1 to 20. For example, C 1 -C 3
  • alkylsulfonyl designates methylsulfonyl
  • C 2 alkoxyalkoxy designates CH 3 OCH 2 O
  • C 3 alkoxyalkoxy designates, for example, CH 3 OCH 2 CH 2 O or CH 3 CH 2 OCH 2 O
  • C 4 alkoxyalkoxy designates the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 O, and CH 3 CH 2 OCH 2 CH 2 O.
  • alkoxyalkyl include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Formula I is comprised of one or more pyridyl
  • Preferred for greatest fungicidal activity and/or ease of synthesis are the compounds of Preferred 1 that are the compounds of Formula I wherein: Preferred 1 :
  • R 1 is H; C 1 -C 2 alkyl; or vinyl;
  • R 2 is C 7 -C 20 alkyl; C 7 -C 20 haloalkyl; C 3 -C 8 alkyl substituted with phenoxy or phenylthio each optionally substituted with R 31 ; C 1 -C 16 alkyl substituted with R 19 ; C 2 -C 6 alkoxyalkyl substituted with R 21 ; C 7 -C 16 alkoxyalkyl optionally substituted with R 21 ; C 7 -C 20 alkenyl; C 2 -C 16 alkenyl substituted with R 20 ; pyridyl substituted with one substituent selected from R 49 , or one group from R 50 and one from R 18 ; or -T-Z;
  • R 3 is phenyl optionally substituted with C 1 -C 2
  • R 4 is H or methyl
  • R 12 is C 1 -C 8 alkyl; phenylmethyl; or phenyl;
  • R 28 is phenyl or pyridyl each optionally
  • R 40 is pyridyl or pyrimidyl each optionally
  • R 37 substituted with R 37 ; or thienyl or furanyl each optionally substituted with R 38 ; 2-tetrahydropyranyl; or 2-tetrahydrofuranyl;
  • R 51 is phenyl substituted with R 52 ; pyridyl
  • R 57 is C 1 -C 12 alkyl; C 3 -C 6 cycloalkyl; C 1 -C 12
  • haloalkyl phenyl, naphthalenyl or pyridyl each optionally substituted with R 41 ; or furanyl or thienyl each optionally substituted with R 42 ;
  • R 58 is R 12 ;
  • A is O or NR 25 ;
  • G is -OR 51 or -SR 51 ;
  • L is H; C 1 -C 8 alkyl; phenylmethyl optionally
  • Q is OH, NH, or a direct bond
  • Y is -OR 28 or -SR 28 ;
  • R 1 is methyl
  • R 2 is C 7 -C 20 alkyl; C 7 -C 20 haloalkyl; C 3 -C 8 alkyl substituted with phenoxy or phenylthio each optionally substituted with R 31 ; C 1 -C 16 alkyl substituted with R 19 ; C 2 -C 6 alkoxyalkyl substituted with R 21 ; C 7 -C 16 alkoxyalkyl optionally substituted with R 21 ; C 7 -C 20 alkenyl; C 2 -C 16 alkenyl substituted with R 20 ; pyridyl substituted with one substituent selected from R 49 , or one group from R 50 and one from R 18 ; or -T-Z;
  • R 3 is phenyl optionally substituted with F, Cl, or methyl
  • R 4 is H
  • R 16 is 3 halogen; C 5 -C 8 alkyl; C 2 -C 8 haloalkyl;
  • R 22 is C 1 -C 16 alkyl; or phenyl optionally
  • R 28 is phenyl or pyridyl each optionally
  • R 29 , R 38 , R 42 , and R 44 are independently 1-2 halogen selected from the group consisting of F and
  • R 31 , R 36 , R 37 , and R 41 are independently trifluoromethyl; 1-2 halogen; cyano; C 1 -C 4 alkyl; C 1 -C 4 alkoxy; or phenoxy substituted with R 44 ;
  • R 40 is pyridyl substituted with R 37 ; or thienyl
  • R 49 is C 5 -C 8 alkyl; C2-C 8 haloalkyl; C 5 -C 8 alkoxy;
  • R 50 is C 1 -C 6 alkyl; C 1 -C 6 haloalkyl; C 1 -C 6 alkoxy;
  • R 57 is C 1 -C 12 alkyl; phenyl or pyridyl optionally substituted with R4 1 ; or thienyl optionally substituted with R 42 ;
  • A is O or NH
  • L is C 1 -C 8 alkyl; phenylmethyl; or phenyl;
  • T is phenyl optionally substituted with 1-2
  • halogen selected from the group consisting of
  • W is O or S
  • Z is phenoxy optionally substituted with R 16 ;
  • R 2 is C 7 -C 12 alkyl; C 7 -C 12 haloalkyl comprised of fewer than 7 halogens from the group
  • R 18 is F, Cl, Br, or methoxy
  • R 19 is C 1 -C 12 alkylthio; C 5 -C 6 cycloalkyloxy;
  • R 20 is C 1 -C 12 alkylthio; C 5 -C 6 cycloalkyloxy; C 1 -C 12 alkoxy; 1-3 halogen; phenyl or phenoxy each optionally substituted with R 31 ;
  • R 31 , R 37 , and R 41 are 1-2 halogen selected from the group consisting of F and Cl; cyano, C 1 -C 4 alkyl, or C 1 -C 4 alkoxy; or phenoxy;
  • R 38 is 1-2 halogen selected from the group
  • R 49 is C 5 -C 8 alkyl; C 2 -C 8 haloalkyl; C 5 -C 8 alkoxy; or C 2 -C 8 alkylthio;
  • R 50 is C j ⁇ -Cg alkyl; C 1 -C 6 haloalkyl; C ⁇ Cg alkoxy;
  • L is C 1 -C 8 alkyl or phenylmethyl when A is O;
  • T is phenyl optionally substituted with fluorine or methyl
  • compounds of Preferred 4 that are the compounds of Preferred 3 wherein:
  • R 2 is C 7 -C 12 alkyl; C 7 -C 12 haloalkyl; C 4 -C 6 alkyl substituted with phenoxy optionally
  • R 31 substituted with R 31 ; C 1 -C 12 alkyl substituted with R 19 ; C 7 -C 12 alkoxyalkyl; C 7 -C 12 alkenyl; pyridyl substituted with one group from R 50 and one halogen from the group consisting of F and Cl; or -T-Z;
  • R 19 is C 1 -C 19 alkylthio; C 5 -C 6 cycloalkyloxy; or
  • R 50 is C 1 -C 6 alkyl; trifluoromethyl; C 1 -C 6 alkoxy; or phenoxy optionally substituted with R 37 ; and R 57 is C 1 -C 8 alkyl; or phenyl optionally
  • 2-Thioxo-4-oxazolidinones la can be prepared by one or both of the Methods illustrated in Equation 1.
  • Z C 1 -C 4 alkyl, C 3 -C 4 alkenyl, C 3 -C 12 cycloalkyl, C 6 -C 7 cycloalkylalkyl, C 2 -C 4 alkoxyalkyl, PhCH 2
  • Formula 4 can be alkyl (C 1 -C 4 ), alkenyl (C 3 -C 4 ),
  • cycloalkyl (C 3 -C 12 ), cycloalkylalkyl (C 6 -C 7 ),
  • esters in which Z is C 1 -C 4 alkyl are preferred for ease of synthesis and lower expense.
  • the 2-hydroxycarboxylic acid esters of Formula 4 can be prepared by a number of methods known in the literature.
  • 2-hydroxycarboxylic acids by esterification as is well known in the literature.
  • the 2-hydroxycarboxylic acids can be prepared from ketones or aldehydes by formation of cyanohydrins, then hydrolysis, as is also known.
  • Org. Syntheses . Coll. Vol. 4, 58 (1968) teaches the preparation of atrolactic acid from
  • esters can also be synthesized from aldehyde and ketone cyanohydrins by treatment with alcohols in the presence of HC1 to afford the iminoether
  • a third method known for preparing 2-hydroxycarboxylic acids and esters involves treating 2-ketoacids or 2-keto-esters with nucleophilic-organometallic reagents such as Grignard reagents, and alkyl- and aryl-lithium reagents.
  • nucleophilic-organometallic reagents such as Grignard reagents, and alkyl- and aryl-lithium reagents.
  • R. G. Salomon et al. teach the preparation of some esters of Formula 4 by the addition of aryl-Grignard reagents to pyruvate esters ( J. Org. Chem . 1982, 47, 4692).
  • Carbonyl compounds known to undergo this reaction include pyruvate esters and acids, glyoxylate esters and acids, and diesters of oxomalonates.
  • the acids used in the acylation reaction can either be protic in nature, for example, a mixture of acetic and sulfuric acid, or a Lewis acid such as aluminum chloride, tin tetrachloride, titanium tetrachloride, or other Lewis acid known to effect Friedel-Crafts-type reactions.
  • the acid can be used either catalytically or in excess. In some cases, the acid may react destructively with the carbonyl substrate and excess carbonyl compound must be used.
  • the acylation can be conducted neat or in a solvent known by one skilled in the art to be suitable for Friedel-Crafts reactions, for example, methylene chloride, carbon disulfide, and nitrobenzene.
  • the reaction may be conducted from -50°C to 100°C.
  • the specific choice of acid, solvent, temperature, and reaction time will depend on the carbonyl and aromatic substrates to be reacted.
  • WO 90/12791 discloses the preparation of Ib by treating 2b with a substituted hydrazine 3 as illustrated in Equation 1. The preparation of the starting dioxazinediones 2b is also described therein.
  • WO 90/12791 also describes the desulfurization of
  • desulfurizing agents include aqueous OXONE ® (KHSO 5 ) and aqueous silver nitrate. Equation 2
  • compounds of Formula Ib can be prepared by the methods outlined in Equation 3. These procedures involve treatment of a 2-hydroxycarboxylic acid ester 4 with a carbonylating agent 6 to produce compounds of Formula 5, followed by conversion of 5 to Ib by treatment with a substituted hydrazine 3.
  • Equation 3 U can be chlorine, 1-imidazolyl, or other suitable leaving group, and the ester group containing Z is as described above for the 2-hydroxycarboxylic esters 4 in Equation 2.
  • the compounds of Formula 5 can be prepared by the method illustrated in Step 1, Equation 3.
  • the alcohols of Formula 4 are dissolved in an inert solvent such as methylene chloride or 1-chlorobutane, and treated with a tertiary-amine base such as
  • 1-imidazolyl can be prepared using 1,1'-carbonyldiimidazole (CDI, 6b) as described below.
  • the alcohols of Formula 4 are dissolved in an inert solvent in which the CDI has sufficient solubility at the reaction temperature.
  • Methylene chloride, 1-chlorobutane and toluene are three of many suitable inert solvents.
  • the CDI is added as a solid or as a solution in an inert solvent at temperatures from 0°C to 100°C.
  • the resulting mixture is poured into a water-immiscible solvent and washed successively with dilute mineral acid, water, and brine. The organic liquid phase of this mixture is separated, dried, and evaporated to isolate the product.
  • isolation of compounds of Formula 5 is not necessary.
  • the compounds can be treated in situ with a hydrazine of Formula 3 as described below for Step 2.
  • CDI can be first prepared, for example by treatment of a solution of imidazole in an inert solvent with phosgene as described by Staab and Wendel (Org. Syntheses. Coll. Vol. 5, 201, (1973)), and then treated in situ with alcohols 4 to afford 5b.
  • compounds of Formula 5 can be dissolved in an inert solvent such as methylene chloride, 1-chlorobutane, or THF and treated with a hydrazine of Formula 3 at a temperature from 0°C to 80°C.
  • an inert solvent such as methylene chloride, 1-chlorobutane, or THF
  • a hydrazine of Formula 3 at a temperature from 0°C to 80°C.
  • a tertiary-amine base such as triethylamine, N, N-diethylaniline, N, N-diisopropylethylamine, or a second equivalent of a hydrazine 3
  • Suitable carboxylic acids include acetic acid, pivalic acid, and benzoic acid.
  • the product of Formula Ib can be isolated by evaporation of the aforementioned inert solvent, and purified by dissolving the residue in a water-immiscible solvent such as ether or methylene chloride, washing with mineral acid, aqueous base, and water, drying, and evaporating the extraction solvent. Crystallization or chromatography can be utilized for additional
  • Acid salts of the hydrazine, hydroxylamine or amine such as dimethylhydrazine hydrochloride and hydroxylamine hydrochloride may also be used, and in these cases an equivalent of additional base is
  • Triethylamine, N, N-diisopropylethylamine and other tertiary amine bases are preferred.
  • the products lc can be isolated by evaporation of the solvent and dissolving the residue in a water- immiscible solvent such as ether. This solution may then be washed with mineral acid, water, and brine, and dried. Evaporation of the solvent followed by
  • hydroxylamines like 7 can also be accomplished by methods known in the art. See, for example, Castellino, A. J., et al. J. Org. Chem . 1984, 49, 1348; Murray, R. W., et al. Synthetic Comm . 1989, 19, 3509 and references cited therein; and
  • the group X in the compounds of Formula 8 may be a halogen, acetate, or other moiety known to be a leaving group in acylation reactions.
  • Chlorine is the most commonly used leaving group X.
  • the compound of Formula 8 is an acid chloride, chloroformate, or carbamoyl chloride
  • the iminooxazolidinones of Formula Ie are dissolved in an inert solvent such as methylene chloride,
  • THF tetrahydrofuran
  • benzene and treated with 8 and a base at a temperature from 0°C to 100°C.
  • Triethylamine, N, N-diisopropylethylamine, and other tertiary amine bases are preferred.
  • the products of Formula Id can be isolated by evaporation of the solvent and dissolving the residue in a water-immiscible solvent such as ether. This solution may be washed with a dilute aqueous mineral acid, water, and brine, and dried. Evaporation of the solvent followed by crystallization or chromatography affords the purified products.
  • Oxazolidinones of Formula If can be synthesized by reacting a compound of Formula Ie with an isocyanate as described in Equation 6 below.
  • the iminooxazolidinones of Formula Ie are dissolved in an inert solvent such as toluene, THF, acetonitrile, or 1,2-dichloroethane and treated with an isocyanate at temperatures from 0°C to 50°C.
  • the products of Formula If can be isolated by evaporation of the solvent, and dissolving the residue in a water-immiscible solvent such as methylene chloride. This solution may be washed with dilute aqueous mineral acid, water, brine, and dried. Evaporation of the solvent followed by crystallization or chromatography affords the products of Formula If.
  • alkyl, alkenyl, and alkynyl radicals are the normal isomers.
  • reaction solution was stirred at room temperature overnight and was then added to water (20 mL).
  • the aqueous layer was extracted with EtOAc (3 ⁇ 50 mL). The combined organic layers were washed with water
  • R 1 -R 59 and A, E, V, G, J, L, m, n, Q, T, W, Y, and Z are as defined in Formula I in the Summary of the Invention. Additional variables are used in the compounds and Tables and are:
  • R 60 which is a structural component of some R 19 groups, is R 22 , R 22 O, or R 22 R 43 N;
  • R 52 or R 37 is R 52 or R 37 ;
  • p which designates the size of a portion of some substituted R 2 alkyl groups, is 1-18;
  • q which designates the size of a portion of other substituted R 2 alkyl groups, is 1-19; and r and t designate the length of some alkoxyalkyl R 2 groups. The sum of r and t is 2-20.
  • R 61 R 62 Z 5-F 3-NO 2 (2-CF 3 - - - - 2-F 2-Cl-3, 5-diF-PhO Ph) CH 2 OCH 2 O - - - 3-Cl 2,3,5-triF-PhO - - - 2-F cyclohexyloxy - - - 2-F 2-CN-PhO 3-Br 2-F (Z)-PhCH-CH - - - 2-F 4-CN-PhO - - - 2-F (4-F-Ph)CH CH - - - 3-MeO 2-(1-bromoethyl)PhO

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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)
  • Plural Heterocyclic Compounds (AREA)

Abstract

La présente invention se rapporte à de nouveaux composés de la formule (I) comprenant des compositions géométriques et stéréo-isomères, s'appliquant à l'agriculture, et à leur utilisation comme fongicides; formule dans laquelle W représente O, S ou N-Q-R?58, et R1, R2, R3 et R4¿ représentent des groupes variés.
PCT/US1993/002164 1992-03-11 1993-03-10 Oxazolidinones fongicides WO1993018016A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU38006/93A AU3800693A (en) 1992-03-11 1993-03-10 Fungicidal oxazolidinones
EP93907384A EP0630370A1 (fr) 1992-03-11 1993-03-10 Oxazolidinones fongicides

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US84956392A 1992-03-11 1992-03-11
US07/849,563 1992-03-11

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USH1401H (en) * 1993-11-15 1995-01-03 E. I. Du Pont De Nemours And Company, Inc. Fungicidal oxazolidinones
US5552554A (en) * 1992-11-13 1996-09-03 E. I. Du Pont De Nemours And Company Imidazole and triazole carboxylates, and processes for preparing 2,4-oxazolidinediones
WO1997038997A1 (fr) * 1996-04-15 1997-10-23 Zeneca Limited Oxazolidinediones substituees et leur utilisation comme fongicides
WO1997038995A1 (fr) * 1996-04-15 1997-10-23 Zeneca Limited Derives fongicides d'oxazolidinediones
JP2010509190A (ja) * 2006-07-27 2010-03-25 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 殺菌・殺カビ性アゾ環式アミド
US7767677B2 (en) 2004-09-20 2010-08-03 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as stearoyl-CoA desaturase inhibitors
US7777036B2 (en) 2004-09-20 2010-08-17 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as therapeutic agents
US7829712B2 (en) 2004-09-20 2010-11-09 Xenon Pharmaceuticals Inc. Pyridazine derivatives for inhibiting human stearoyl-CoA-desaturase
US7919496B2 (en) 2004-09-20 2011-04-05 Xenon Pharmaceuticals Inc. Heterocyclic derivatives for the treatment of diseases mediated by stearoyl-CoA desaturase enzymes
US7951805B2 (en) 2004-09-20 2011-05-31 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as mediators of stearoyl-CoA desaturase
US8026360B2 (en) 2004-09-20 2011-09-27 Xenon Pharmaceuticals Inc. Substituted pyridazines as stearoyl-CoA desaturase inhibitors
US8071603B2 (en) 2004-09-20 2011-12-06 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as stearoyl-CoA desaturase inhibitors
JP2013510896A (ja) * 2009-11-17 2013-03-28 ノバルティス アーゲー アルドステロンシンターゼ阻害剤としてのアリール−ピリジン誘導体
US8541457B2 (en) 2005-06-03 2013-09-24 Xenon Pharmaceuticals Inc. Aminothiazole derivatives as human stearoyl-CoA desaturase inhibitors
US9090604B2 (en) 2006-07-27 2015-07-28 E I Du Pont De Nemours And Company Fungicidal azocyclic amides
US9107923B2 (en) 2013-06-27 2015-08-18 Pfizer Inc. Heteroaromatic compounds and their use as dopamine D1 ligands
CN114835700A (zh) * 2022-04-20 2022-08-02 中国农业大学 一种具有高抗念珠菌活性的吡噁唑菌酮类化合物、其制备方法及作为医用抗真菌剂的应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0393911A1 (fr) * 1989-04-21 1990-10-24 E.I. Du Pont De Nemours And Company Oxazolidinones fongicides
WO1991019703A2 (fr) * 1990-06-11 1991-12-26 E.I. Du Pont De Nemours And Company Iminooxazolidinones fongicides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0393911A1 (fr) * 1989-04-21 1990-10-24 E.I. Du Pont De Nemours And Company Oxazolidinones fongicides
WO1991019703A2 (fr) * 1990-06-11 1991-12-26 E.I. Du Pont De Nemours And Company Iminooxazolidinones fongicides

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5552554A (en) * 1992-11-13 1996-09-03 E. I. Du Pont De Nemours And Company Imidazole and triazole carboxylates, and processes for preparing 2,4-oxazolidinediones
USH1401H (en) * 1993-11-15 1995-01-03 E. I. Du Pont De Nemours And Company, Inc. Fungicidal oxazolidinones
WO1997038997A1 (fr) * 1996-04-15 1997-10-23 Zeneca Limited Oxazolidinediones substituees et leur utilisation comme fongicides
WO1997038995A1 (fr) * 1996-04-15 1997-10-23 Zeneca Limited Derives fongicides d'oxazolidinediones
US7919496B2 (en) 2004-09-20 2011-04-05 Xenon Pharmaceuticals Inc. Heterocyclic derivatives for the treatment of diseases mediated by stearoyl-CoA desaturase enzymes
US7767677B2 (en) 2004-09-20 2010-08-03 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as stearoyl-CoA desaturase inhibitors
US7777036B2 (en) 2004-09-20 2010-08-17 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as therapeutic agents
US7829712B2 (en) 2004-09-20 2010-11-09 Xenon Pharmaceuticals Inc. Pyridazine derivatives for inhibiting human stearoyl-CoA-desaturase
US7951805B2 (en) 2004-09-20 2011-05-31 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as mediators of stearoyl-CoA desaturase
US8026360B2 (en) 2004-09-20 2011-09-27 Xenon Pharmaceuticals Inc. Substituted pyridazines as stearoyl-CoA desaturase inhibitors
US8071603B2 (en) 2004-09-20 2011-12-06 Xenon Pharmaceuticals Inc. Heterocyclic derivatives and their use as stearoyl-CoA desaturase inhibitors
US8541457B2 (en) 2005-06-03 2013-09-24 Xenon Pharmaceuticals Inc. Aminothiazole derivatives as human stearoyl-CoA desaturase inhibitors
US9604962B2 (en) 2006-07-27 2017-03-28 E I Du Pont De Nemours And Company Fungicidal azocyclic amides
JP2010509190A (ja) * 2006-07-27 2010-03-25 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 殺菌・殺カビ性アゾ環式アミド
US8642634B2 (en) 2006-07-27 2014-02-04 E I Du Pont De Nemours And Company Fungicidal azocyclic amides
US9090604B2 (en) 2006-07-27 2015-07-28 E I Du Pont De Nemours And Company Fungicidal azocyclic amides
US9920030B2 (en) 2006-07-27 2018-03-20 E I Du Pont De Nemours And Company Fungicidal azocyclic amides
JP2013510896A (ja) * 2009-11-17 2013-03-28 ノバルティス アーゲー アルドステロンシンターゼ阻害剤としてのアリール−ピリジン誘導体
US9527831B2 (en) 2013-06-27 2016-12-27 Pfizer Inc. Heteroaromatic compounds and their use as dopamine D1 ligands
US9139561B2 (en) 2013-06-27 2015-09-22 Pfizer Inc. Heteroaromatic compounds and their use as dopamine D1 ligands
US9822097B2 (en) 2013-06-27 2017-11-21 Pfizer Inc. Heteroaromatic compounds and their use as dopamine D1 ligands
US9107923B2 (en) 2013-06-27 2015-08-18 Pfizer Inc. Heteroaromatic compounds and their use as dopamine D1 ligands
US10093655B2 (en) 2013-06-27 2018-10-09 Pfizer Inc. Heteroaromatic compounds and their use as dopamine D1 ligands
US10421744B2 (en) 2013-06-27 2019-09-24 Pfizer Inc. Heteroaromatic compounds and their use as dopamine D1 ligands
US10696658B2 (en) 2013-06-27 2020-06-30 Pfizer Inc. Heteroaromatic compounds and their use as dopamine D1 ligands
US11014909B2 (en) 2013-06-27 2021-05-25 Pfizer Inc. Heteroaromatic compounds and their use as dopamine D1 ligands
CN114835700A (zh) * 2022-04-20 2022-08-02 中国农业大学 一种具有高抗念珠菌活性的吡噁唑菌酮类化合物、其制备方法及作为医用抗真菌剂的应用

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