EP0457802A1 - Ethers d'oxabicyclononane herbicides - Google Patents

Ethers d'oxabicyclononane herbicides

Info

Publication number
EP0457802A1
EP0457802A1 EP90902899A EP90902899A EP0457802A1 EP 0457802 A1 EP0457802 A1 EP 0457802A1 EP 90902899 A EP90902899 A EP 90902899A EP 90902899 A EP90902899 A EP 90902899A EP 0457802 A1 EP0457802 A1 EP 0457802A1
Authority
EP
European Patent Office
Prior art keywords
chch
och
alkyl
compounds
rice
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP90902899A
Other languages
German (de)
English (en)
Inventor
Matthew Fred Schlecht
Joseph Edward Semple
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0457802A1 publication Critical patent/EP0457802A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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 oxabicyclononane 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 in soybeans, cotton, sugar beets, rape, corn, wheat, barley and particularly in rice.
  • DE 2937645 generically discloses ethers as herbicides including oxabicyclo [3.3.1] nonane ethers
  • U.S. 4,388,104 discloses ethers as herbicides including dioxabicyclo [3.2.1] nonane ethhrs.
  • EP-A 302,599 discloses [3.3.1] dioxabicyclononane ethers.
  • This invention pertains to compounds of
  • R 1 is H or a C 1 -C 4 straight chain alkyl group
  • R 2 is H, C 1 -C 6 alkyl, CN, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, phenyl, CH 2 Ph or C 1 -C 3 alkyl substituted with OH, CN, C 1 -C 3 alkoxy, OPh,
  • R 3 is H, F, Cl, Br, I, OH, PhSe, C 1 -C 3 alkoxy, OSO 2 Ph optionally substituted with 1-3 CH 3 , PhSO n optionally substituted with 1-3 CH 3 ,
  • R 3 and R 4 may be taken together to form a 5
  • membered ring acetonide optionally
  • substituted with 1-2 CH 3 or R 3 and R 4 when on the same carbon may be taken together to form a ketone or R 3 may be taken together with an adjacent carbon to form a double bond with the proviso said double bond is not at a bridgehead carbon or the OCH 2 W carbon.
  • R 3 and R 4 on adjacent carbons may be taken
  • R 4 OH and R 3 and R 4 are on the same carbon, then R 3 cannot be OH, F, Cl, Br, I, PhSe, CH 3 Se, alkoxy or amino;
  • W is phenyl optionally substituted with 1-3 substituents selected from F, Cl, Br, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, OH, CN, C 1 -C 3 haloalkyl, C 1 -C 3 haloalkoxy, C 1 -C 3 alkylthio, C 2 -C 4 alkenyl or C 2 -C 4 alkynyl, or W is a 4, 5, 6 or 7-membered heterocyclic ring containing at least one from among 0-3 nitrogen, 0-2 oxygen or 0-2 sulfur, each ring optionally
  • heterocycles includes but is not limited to oxetane, furan, dioxane, oxepane, dioxolane, oxadiazole, thiadiazole, triazole, thiophene, tetrahydropyran, tetrahydrofuran, isoxazole, oxazole, pyrazole, imidazole, thiazole, pyridine and pyrazines; provided that the total number of heteroatoms is 3 or less; and n is 0, 1 or 2.
  • Preferred embodiments are:
  • R 5 is H or CH 3 ;
  • R 6 is H, or CH 3 .
  • R 1 is C 1 -C 3 alkyl
  • R 2 is C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 2 -C 3
  • alkynyl phenyl, CH 2 Ph or C 1 -C 2 alkyl substituted by OCH 3 , CN, SO 2 CH 3 or C 1 -C 3 alkoxycarbonyl.
  • W is phenyl optionally substituted by 1-2
  • R 3 is H, F, Br or Cl
  • R 4 is H. 4.
  • W is phenyl optionally substituted by 1-2
  • the compounds of Formula I exhibit geometrical and optical isomerism and may be prepared in
  • Formula V is treated with a base such as sodium hydride in N,N-dimethylacetamide and the appropriate alkylating agent represented as WCH 2 X where W
  • alkylating agents WCH 2 X are prepared from the alcohols WCH 2 OH in the conventional manners known to those skilled in the art.
  • Formula lb can be hydroxylated with the catalytic osmylation described earlier in Scheme 2, to give the diol of Formula XVIII.
  • This diol of Formula XVIII can be reacted with 2,2-dimethoxypro ⁇ ane in the presence of acid to provide the acetonide of
  • Tertiary alcohols of Formula If could be prepared by the addition of a suitable Grignard reagent, or hydrogen cyanide, to the ketone of Formula Ic.
  • the epoxides of Formula Ig can be prepared by epoxidation of the alkenes lb with a reagent such as meta-chloroperoxybenzoic acid in methylene chloride.
  • the alcohols of Formula Ih can be prepared as shown in Scheme 6.
  • the phenylselenides of Formula XIX are prepared as in Scheme 2 from the giycol monoether of Formula VIII with phenylselenenyl chloride.
  • the selenides may be subjected to
  • reaction mixture was cooled and then diluted with 250 mL of ether, and then water was added dropwise to hydrolyze the aluminum complex.
  • This solution was filtered and cooled to 0oC under nitrogen, and was charged with a solution of p-toluenesulfonic acid (0.46 g, 0.0024 mole) in 10 mL of DME. The ice bath was removed and the mixture was stirred at room temperature for 23 h. The reaction mixture was extracted sequentially with 2 ⁇ 100 mL of a 5% aqueous solution of sodium carbonate, 2 ⁇ 100 mL of water, 100 mL of brine, and the solution was dried over magnesium sulfate.
  • the still hot reaction mixture was charged with 800 mL of 20% NaHSO 3 (aq), and a distillation head was attached and the reaction vessel was heated. When 2250 mL of distillate had been obtained, the temperature began to rise and the heating was stopped and the mixture was allowed to stand overnight to cool.
  • reaction mixture was extracted successively with three 100 mL portions of ether and with 100 mL of methylene chloride.
  • the combined organics were extracted with a mixture of 100 mL of ice and 350 mL of 10% H 2 SO 4 (aq), and then with 250 mL of brine.
  • dimethylacetamide was charged with a solution of (1R,S; 2 S,R)1,5-dimethyl-9-oxabicyclo[3.3.1]nonan-2-ol (0.57 g, 3.35 mmol) in 10 mL of dimethylacetamide under nitrogen. The reaction mixture was stirred at room temperature for 30 min and then was heated to
  • reaction temperature rose to 33oC. After 14 h at room temperature, the reaction mixture was heated to 90oC for 1.5 h. The solution was cooled, diluted with 50 mL of water and was extracted with 4 ⁇ 50 mL of ether. The combined ether layers were extracted with 3 ⁇ 50 mL of water, 50 mL of brine and were dried over magnesium sulfate. Concentration in vacuo gave 0.95 g of crude product which was purified by
  • the first fraction was 583 mg (56% yield) of 1 R, S; 2 S,R)-exo-1,5-dimethyl-2[(2',6'-difluorophenyl)methoxy]-9-oxabicyclo[3.3.1]nonane.
  • Tables 1 through 14 may be prepared.
  • H H CH C(CH 3 ) 2
  • H H CH C(CH 3 ) 2
  • H H CH C(CH 3 ) 2
  • H H CH C(CH 3 ) 2
  • H H CH C(CH 3 ) 2
  • H H CH C(CH 3 ) 2
  • Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable
  • Sprayable formulations can be
  • compositions are primarily- used as intermediates for further formulation.
  • the formulations broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of
  • Active ingredient plus at least one of a Surfactant or a Diluent equals 100 weight percent.
  • Emulsifiers Annual MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.
  • compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent
  • Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering.
  • the active ingredient is first sprayed onto the amorphous silica, then the ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.
  • the active ingredient is first sprayed onto the diatomaceous earth then the ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in
  • the product is reblended before packaging.
  • a slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.
  • the active ingredient and Atlox emulsifiers are dissolved in the solvent, filtered and packaged.
  • Atlox 3403F and 3404F are blends of anionic and ionic emulsifiers from ICI Americas, Inc. Example 9
  • the active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.
  • the ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized
  • the compound is added directly to the water with stirring to produce the solution, which may then be packaged for use.
  • the active ingredient is sprayed onto the attapulgite and then passed through a hammer-mill to produce particles substantially all below 200
  • preemergence herbicides Many compounds in this invention are useful for the control of selected grass and broadleaf weeds with tolerance to important agronomic crops such as barley (Hordeum vuloare), corn (Zea mays), cotton (Gossypiur ⁇
  • rape (Brassica napug)
  • rice Oryza
  • Grass weed species controlled include, but are not limited to, barnyardgrass (Echinochloa crus-galli). crabgrass (Dicitaria spp.), and foxtail (Setaria spp.). Broadleaf weed species controlled include, but are not limited to, duck salad
  • These compounds also have utility for weed control of selected vegetation in specified areas such as around storage tanks, parking lots, highways, and railways, and in fallow crop, citrus, and
  • Rates of application for compounds of this invention are determined by a number of factors.
  • the subject compounds should be applied at rates from 0.008 to 20 kg/ha with a preferred rate range of
  • Compounds of this invention may be used alone or in combination with other commercial herbicides, insecticides, or fungicides.
  • the following list exemplifies some of the herbicides suitable for use in mixtures.
  • herbicides may be particularly useful for weed
  • fluoroglycarboxymethyl 5-[2-chloro-4-(tricofen fluoromethyl)phenoxy]-2-nitrobenzoate fluridone 1-methyl-3-phenyl-5-[3-(trifluoromethyl)phenyl]-4(1H)-pyridinone fomesafen 5-[2-chloro-4-(trifluoromethyl)phenoxy]- N-(methylsulfonyl)-2-nitrobenzamide fosamine ethyl hydrogen (aminocarbonyl)- phosphate Common Name Chemical Name glyphosate N-( ⁇ hosphonomethyl)glycine
  • paraquat 1,1'-dimethyl-4,4'-dipyridinium ion pebulate S-propyl butylethylcarbamothioate pendimethalin N-(1-ethylpropyl)-3,4-dimethyl-2,6- dinitrobenzenamine
  • PPG-1013 5-[2-chloro-4-(trifluoromethyl)- phenoxy]-2-nitroacetophenone
  • barnyardgrass Echinochloa crus-galli
  • cheatgrass Bromus secalinus
  • cocklebur Xanthium
  • pensylvanicum corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Di ⁇ itaria spp.), giant foxtail (Setaria faberi), morningglory (Ipomoea spp.), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean
  • Morningglory 0 0 0 0 0 0 0

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des composés dérivés d'éther d'oxabicyclononane de formule (I), des compositions contenant ces composés de dérivés d'éther, ainsi que des procédés d'utilisation desdits composés ou desdites compositions afin de réguler la croissance de végétations indésirables dans le soja, le coton, les betteraves à sucre, le colza, les céréales, le blé, l'orge et particulièrement le riz.
EP90902899A 1989-02-10 1990-02-06 Ethers d'oxabicyclononane herbicides Pending EP0457802A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US30977189A 1989-02-10 1989-02-10
US309771 1989-02-10

Publications (1)

Publication Number Publication Date
EP0457802A1 true EP0457802A1 (fr) 1991-11-27

Family

ID=23199619

Family Applications (2)

Application Number Title Priority Date Filing Date
EP90902899A Pending EP0457802A1 (fr) 1989-02-10 1990-02-06 Ethers d'oxabicyclononane herbicides
EP90301210A Withdrawn EP0383469A1 (fr) 1989-02-10 1990-02-06 Ethers d'oxabicyclononane comme herbicides

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP90301210A Withdrawn EP0383469A1 (fr) 1989-02-10 1990-02-06 Ethers d'oxabicyclononane comme herbicides

Country Status (9)

Country Link
EP (2) EP0457802A1 (fr)
KR (1) KR920701210A (fr)
CN (1) CN1044818A (fr)
AU (1) AU5040890A (fr)
BR (1) BR9007064A (fr)
CA (1) CA2045676A1 (fr)
PE (1) PE33390A1 (fr)
PT (1) PT93107A (fr)
WO (1) WO1990009383A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0593433A1 (fr) * 1989-09-11 1994-04-27 E.I. Du Pont De Nemours And Company Ethers oxabicyclo herbicides
US5234900A (en) * 1989-09-11 1993-08-10 E. I. Du Pont De Nemours And Company Herbicidal oxabicyclo ethers
WO1992003440A1 (fr) * 1990-08-16 1992-03-05 E.I. Du Pont De Nemours And Company Ethers herbicides
BR9205717A (pt) * 1991-01-30 1994-05-17 Du Pont Éteres biciclicos herbicidas

Family Cites Families (2)

* 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
US4670041A (en) * 1981-12-16 1987-06-02 E. I. Du Pont De Nemours And Company Oxabicycloalkane herbicides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9009383A1 *

Also Published As

Publication number Publication date
WO1990009383A1 (fr) 1990-08-23
CN1044818A (zh) 1990-08-22
PE33390A1 (es) 1991-01-10
AU5040890A (en) 1990-09-05
BR9007064A (pt) 1992-01-28
KR920701210A (ko) 1992-08-11
EP0383469A1 (fr) 1990-08-22
PT93107A (pt) 1990-08-31
CA2045676A1 (fr) 1990-08-11

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