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WO1992003440A1 - Ethers herbicides - Google Patents

Ethers herbicides Download PDF

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Publication number
WO1992003440A1
WO1992003440A1 PCT/US1991/005438 US9105438W WO9203440A1 WO 1992003440 A1 WO1992003440 A1 WO 1992003440A1 US 9105438 W US9105438 W US 9105438W WO 9203440 A1 WO9203440 A1 WO 9203440A1
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WO
WIPO (PCT)
Prior art keywords
compound
och
formula
growth
controlling
Prior art date
Application number
PCT/US1991/005438
Other languages
English (en)
Inventor
Matthew Fred Schlecht
Original Assignee
E.I. Du Pont De Nemours And Company
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 E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Publication of WO1992003440A1 publication Critical patent/WO1992003440A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems

Definitions

  • the present invention relates to novel oxabicycloalkane ether derivative compounds, to compositions containing these ether derivative compounds, and to methods of using these compounds or compositions to control the growth of undesired vegetation particularly in rice.
  • U.S. 4,388,104 discloses ethers as herbicides including
  • This invention pertains to compounds of Formulas I, II, III, IV and V including stereoisomers, suitable agricultural compositions containing them and their use as broad spectrum preemergent and postemergent herbicides:
  • X is OR 5 , SR 5 , C 1 -C 6 acyloxy, benzoyloxy, halogen, N(R 6 )R 7 ,
  • R 1 is H or straight chain C 1 -C 3 alkyl optionally substituted with 1 or more deuteriums;
  • R 2 is H or C 1 -C 4 alkyl
  • R 3 is H, C 1 -C 3 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 3 alkyl substituted with OCH 3 or OCH 2 CH 3 , or may be taken together with R 2 to form a 5 or 6-membered spiro or fused ring;
  • R 4 is H, C 1 -C 3 alkyl, C 2 -C 4 alkenyl, C 1 -C 6 acyl or benzoyl;
  • R 5 is H, C 1 -C 3 alkyl optionally substituted with 1 or more
  • R 6 and R 7 are independently H, C 1 -C 3 alkyl or may be taken
  • a 5- or 6-membered saturated or unsaturated heterocyclic ring containing 1-4 nitrogens, 0-1 oxygen or 0-1 sulfur, each ring optionally substituted with 1-2 substituents selected from halogen, CH 3 or OCH 3 , such as but not limited to pyrrole, pyrazole, imidazole, tetrazole, triazole, pyrrolidine, piperidine, morpholine, piperazine, thiazolidine, isoxazolidine, oxazolidine or tetrahydrooxazine;
  • Q is -CH 2 W or
  • R 8 is H, halogen, C 1 -C 3 alkyl, OR 9 , SR 9 or CN;
  • R 9 is C 1 -C 3 alkyl or C 1 -C 3 haloalkyl
  • J is CH 2 , NR 10 , O, S or may be taken to form a double bond with an adjacent carbon;
  • R 10 is H or C 1 -C 3 alkyl
  • q 1 is 0-2;
  • W is phenyl optionally substituted with 1-3 substituents selected from halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxyl, OH, CN, C 1 -C 3 haloalkyl, C 1 -C 3 haloalkoxyl, C 1 -C 3 alkylthio, C 2 -C 4 alkenyl or C 2 -C 4 alkynyl, or W is a 5-, 6- or 7-membered heterocyclic ring containing 0-2 nitrogens, 0-2 oxygens or 0-2 sulfurs, each ring optionally substituted with 1-2 substituents selected from halogen, CH 3 or OCH 3 ; a representative exemplification of such heterocycles includes but is not limited to pyrrole, furan, thiophene, tetrahydrofuran, tetrahydropyran, isoxazole, oxazole, pyrazole, imidazole, thiazole,
  • halogen either alone or in compound words such as “haloalkyl”, denotes fluorine, chlorine or bromine. 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 examples include CH 2 CH 2 F, CF 2 CF 3 and CH 2 CHFCI.
  • 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 or isopropyl.
  • W is phenyl optionally substituted by 1-2 substituents selected from halogen, CH 3 or OCH 3 ; or W is
  • R 1 is straight chain C 1 -C 3 alkyl optionally substituted with
  • R 3 is H, C 1 -C 3 alkyl or may be taken with R 2 to form a 5- or
  • R 4 is C1-C3 alkyl, C 1 -C 6 acyl or benzoyl;
  • R 8 is H, CH 3 , halogen, OCH 3 or SCH 3 .
  • X is OR 5 , SR 5 , C 1 -C 6 acyloxy, benzoyloxy or
  • R 5 is H; C 1 -C 3 alkyl optionally containing 1 or more
  • deuteriums or C 1 -C 3 alkoxyls or phenyl optionally substituted with 1-2 substituents selected from halogen, CH 3 or OCH 3 .
  • Preferred 10 are the compound of Preferred 10 which are: 5-(methoxy-d3)-1-methyl-2-(phenylmethoxy)-9- oxabicyclo[3.3.1]nonane, exo-:
  • compositions for controlling the growth of undesired vegetation according to the invention comprise an effective amount of the compounds recited herein and at least one of the following: surfactant, solid diluent or liquid diluent.
  • Methods for controlling the growth of undesired vegetation according to the invention comprise applying to the locus to be protected an effective amount of the
  • the compounds of Formula I, II, IH, IV and V exhibit geometrical and optical isomerism and can be prepared in geometrically or optically pure or mixed forms.
  • the various individual optical and geometrical forms and various combinations thereof of the materials of the invention usually have some difference in herbicidal properties. Generally preferred for herbicidal activity are those geometrical isomers of
  • the present invention contemplates all herbicidally active forms resulting from synthesis and from deliberately created mixtures, including those from among the synthetic intermediates and precursors which demonstrate herbicidal activity.
  • the enone of Formula 2 can be acetalized by the following treatment: heating, in the presence of an acid such as 2-naphthalenesulfonic acid, under conditions of water removal from the reaction system such as with a Dean-Stark trap, with an alcoholic reagent of the form AOH where the A group can be C 1 -C 4 alkyl or two A can be taken together to form a C 2 -C 6 diol such as ethylene glycol (for acetaHzations, see F. A. J. Meskens, Synthesis 501 (1981).
  • the intermediate acetal can be converted to the acetal diol of Formula 3 by treatment with catalytic osmium tetroxide in the presence of a stoichiometric oxidant such as N-methylmorpholine-N-oxide or trimethylamine oxide, in a suitable solvent system such as water/tert-butyl alcohol/pyridine (see for example R. Ray & D. S. Matteson,
  • This oxidation of the intermediate acetal to the acetal diol of Formula 3 can also be effected with potassium permanganate or other similar oxidative reagents.
  • the acetal diol of Formula 3 can be selectively coupled with an alkylating agent QY, where Y is a leaving group, in the presence of a base such as sodium hydride in a solvent such as a mixture of tetrahydrofuran and dimethylacetamide, to yield the acetal glycol monoether of Formula 4
  • Typical leaving groups are exemplified by but not limited to Cl, Br, I, and GSO 3 , where the group G of the organosulfonate moiety is exemplified by but not limited to CH 3 , CF 3 , phenyl and p-methylphenyl. It is well known in the art that a selective ether coupling is possible at a secondary hydroxyl in preference to a tertiary hydroxyl.
  • the acetal glycol monoether of Formula 4 can undergo internal acetal exchange in the presence of a catalytic quantity of an anhydrous acid such as 2-naphthalenesulfonic acid to yield the substituted
  • cyclohexan-1,4-dione of Formula 5 can be reacted with an organometallic reagent of the type R 1 M where the metallic group M is exemplified by but not limited to Ii, MgBr, 1/2 Mg, MgCl, Mgl, ZnBr, 1/2 Zn, ZnCl and Znl.
  • the product of this reaction can be represented by the 4-substituted-l-hydroxyoxabicyclo[2.2.1]heptane of Formula 6, and this can be subjected to a dehydration reaction in the presence of an acid such as 2-naphthalenesulfonic acid under conditions of water removal, such as with a Dean-Stark trap, to furnish the enone of Formula 2.
  • an acid such as 2-naphthalenesulfonic acid under conditions of water removal, such as with a Dean-Stark trap
  • halogen agents are exemplified by but not limited to thionyl bromide, phosphorus trichloride, phosphorus
  • organic sulfonyl chlorides for example p-toluenesulfonyl chloride
  • a base such as pyridine
  • a 1 can be certain of the groups within the scope of R 5 (e.g., C 1 -C 6 akyloxy, benzoyloxy) in the presence of a base such as sodium hydride.
  • the compounds of Formula II can be prepared from the
  • this selectivity could be increased by carrying out the ether coupling on an analog of the compound of Formula 10 in which the bridgehead hydroxyl is capped with a bulky group such as dimethyl-tert-butylsilyl, by methods known to the art.
  • the diol of Formula 11 can be oxidized, for example with
  • the compounds of Formula III can be prepared as shown in
  • the group E can be alkyl of the R 3 type, alkoxyl of the OR 3 type, or a salt of the O-M + type.
  • the group E in the compound of Formula 16 can be converted to the R 3 group in the compound of Formula 17 by straightforward methods known to the art.
  • the transformation of compound of Formula 17 to the intermediate compound of Formula 18 follows the two-step process used for the conversion of the compound of Formula 2 to the compound of Formula 3 in Scheme 1.
  • the various compounds of Formula III differing in the identity of X can be prepared and
  • a two-step process serves to produce the intermediate of Formula 25: firstly an oxidation of the diol of Formula 24 to a diketone intermediate using for example the dimethylsulfoxide/oxalyl chloride oxidant; secondly the addition of an organometallic R ⁇ M such as ethyl magnesium bromide.
  • the compound of Formula 25 is subjected to dehydration in the presence of acid (for example 2-naphthalenesulfonic acid) under conditions of water removal, such as using a Dean-Stark trap.
  • the intermediate produced is then subjected to acetalization conditions with a hydroxylic reagent AOH in the presence of acid under conditions of water removal, to furnish the compound of Formula 26.
  • the compound of Formula 26 is then hydroxylated to produce the diol compound of Formula 27 in an analogous fashion to the conversion of the compound of Formula 9 to the compound of Formula 10 in Scheme 4.
  • the resulting diol of Formula 27 undergoes a selective ether coupling reaction resulting in the glycol monoether compound of Formula 28, as described above for the conversion of the compound of Formula 3 to the compound of Formula 4 in Scheme 1.
  • the various compounds of Formula V differing in the identity of the group X can be prepared and interconverted as described for the
  • reaction mixture was poured into 500 mL of water, the layers were separated and the aqueous layer was extracted with twice with methylene chloride. The combined organics were extracted once with brine, dried (Na2S ⁇ 4) and concentrated to give 30.83 g of a moist orange solid.
  • Step B 5-Methyl-9-oxabicyclo[3.3.1]nonan-1-ol (after A. Streitwieser Jr. et al, J. Org. Chem. 542331 (1989))
  • Step C 5-Methylcyclooct-4-en-1-one (after A. Streitwieser Jr. et al, J. Org.
  • Step D 8-Methyl-1 ,4-dioxaspiror4.71dodec-7-ene
  • Step E cis-8-Methyl-1,4-dioxaspiro[4.7]dodeca-7.8-diol (after Matteson,
  • Step F cis-8-Methyl-7-(phenylmethoxy)-1,4-dioxaspiro-[4.7]dodecan-8-ol
  • a suspension of 2.579 g of 80% NaH (in mineral oil) (86 mmol) was suspended in 50 mL of THF and this was charged with a solution of 5.001 g of cis-8-methyl-1.4-dioxaspiro[4.7]dodeca-7,8-diol in a total of
  • Step A cis-8-Methyl-7-[(2-fluorophenyl)methoxy]-1,4-dioxaspiro[4,7]- dodecan-8-ol
  • Step B exo-2-[(2-Fluorophenyl)methoxy]-1-methyl-9-oxabicyclo[3.3.1]- nonan-5-ol
  • reaction mixture was poured into 60 mL of water, and this was extracted with three 20 mL portions of methylene chloride.
  • A C 1 -C 4 alkyl; two A can be taken together to form a diol such as HO(CH 2 ) 2 OH;
  • Y leaving group such as Cl, Br, I, GSO 3 .
  • G CH 3 , CF 3 , Ph, p-CH 3 Ph;
  • R 1 - and Q are as previously defined.
  • R 1 CH 3 ;
  • X NCH 3 OCH 3 ;
  • Q CH 2 W
  • R 1 CH 2 CH 3 ;
  • X SCH 3 ;
  • R 1 CH 2 CH 3 ;
  • X N(CH 3 ) 2 ;
  • R 1 CH 2 CH 3 ;
  • R 1 CH 2 CH 3 ;

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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)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

On décrit de nouveaux composés dérivés de l'éther d'oxabicycloalcane des formules (I-V), ainsi que des compositions contenant ces composés et leur méthode d'utilisation. Ces composés sont biologiquement actifs en tant qu'herbicides aussi bien avant qu'après la germination avec une sélectivité pour une variété de cultures.
PCT/US1991/005438 1990-08-16 1991-08-06 Ethers herbicides WO1992003440A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US56848790A 1990-08-16 1990-08-16
US568,487 1990-08-16

Publications (1)

Publication Number Publication Date
WO1992003440A1 true WO1992003440A1 (fr) 1992-03-05

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2937645A1 (de) * 1979-09-18 1981-04-16 Bayer Ag, 5090 Leverkusen Tetrahydropyranether-derivate, verfahren zu ihrer herstellung sowie ihre verwendung als herbizide
EP0081893A2 (fr) * 1981-12-16 1983-06-22 Shell Internationale Researchmaatschappij B.V. Herbicides oxabicycloalquiniques
EP0308170A1 (fr) * 1987-09-15 1989-03-22 E.I. Du Pont De Nemours And Company Oxabicycloalcanes sélectifs
EP0343859A1 (fr) * 1988-05-23 1989-11-29 E.I. Du Pont De Nemours And Company Oxabicycloalkane-éthers comme herbicides
EP0383469A1 (fr) * 1989-02-10 1990-08-22 E.I. Du Pont De Nemours And Company Ethers d'oxabicyclononane comme herbicides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2937645A1 (de) * 1979-09-18 1981-04-16 Bayer Ag, 5090 Leverkusen Tetrahydropyranether-derivate, verfahren zu ihrer herstellung sowie ihre verwendung als herbizide
EP0081893A2 (fr) * 1981-12-16 1983-06-22 Shell Internationale Researchmaatschappij B.V. Herbicides oxabicycloalquiniques
EP0308170A1 (fr) * 1987-09-15 1989-03-22 E.I. Du Pont De Nemours And Company Oxabicycloalcanes sélectifs
EP0343859A1 (fr) * 1988-05-23 1989-11-29 E.I. Du Pont De Nemours And Company Oxabicycloalkane-éthers comme herbicides
EP0383469A1 (fr) * 1989-02-10 1990-08-22 E.I. Du Pont De Nemours And Company Ethers d'oxabicyclononane comme herbicides

Also Published As

Publication number Publication date
AU8432391A (en) 1992-03-17

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