Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
  • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
  • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
  • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
• • 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
  • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
  • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
  • C07D307/81—Radicals substituted by nitrogen atoms not forming part of a nitro radical
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
  • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
  • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
  • C07D317/58—Radicals substituted by nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
  • C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
  • C07D319/16—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems condensed with one six-membered ring
  • C07D319/18—Ethylenedioxybenzenes, not substituted on the hetero ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
  • C07D321/02—Seven-membered rings
  • C07D321/10—Seven-membered rings condensed with carbocyclic rings or ring systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
  • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
  • C07D333/58—Radicals substituted by nitrogen atoms

Definitions

• This invention relates to a process for the conversion of mixtures of E and Z isomers of certain ketoximes to 98% or greater pure E isomer.
• This invention provides a process for producing 98% or greater pure E isomer of an aryl alkyl ketoxime having the formula: wherein Ar is phenyl; phenyl substituted in the 2- to 6- position with 1-5 halogen (Cl, Br, F, I), C 1 - C 4 alkyl, C l - C 4 alkoxy, C l - C 4 alkylthio, methylenedioxy, ethylenedioxy, isopropylenedioxy, trifluoromethyl, C l -C 4 haloalkyl, C 1 - C 4 alkylthioalkyl, C 2 - C 4 alkenyl, C 2 - C 4 alkynyl, cyano, C 2 - C 4 cyanoalkyl, C 2 - C 4 carboalkoxy, C 1 - C 4 alkylsulfonyl, C 2 - C 8 alkoxyalkyl, C 2 - C 4 haloalkenyl,
• aryl alkyl ketoximes treated in accordance with this invention include:
• mixtures of E and Z isomers of the aryl alkyl ketoximes are precipitated as the E isomer immonium complex by treating a solution of the mixture in an anhydrous solvent with anhydrous protic or Lewis-acids. It has been found that, unexpectedly, the E isomer in the mixture is preciptated as an immonium salt and the Z isomer isomerizes to the E isomer. Upon neutralization about 98% of the original mixture of isomers is recovered in the form of E isomer.
• the organic solvent used can be any of the well known solvents used in organic synthesis operations, so long as the solvent is anhydrous.
• Typical utilizable anhydrous organic solvents include hydrocarbons, such as hexane, cyclohexane, toluene, and xylene; chlorinated hydrocarbons, such as chloroform and carbon tetrachloride; ethers, such as diethyl ether, tetrahydrofuran and dioxane; and ketones, such as acetone and 2-butanone.
• the amount of solvent used is not a critical factor, as it simply serves as a medium for the acid treatment. In general, between about one part and about 10 parts solvent per part aryl alkyl ketoxime can be used.
• the acid used to precipitate the immonium salt of the aryl alkyl ketoxime will be an anhydrous organic or inorganic protic or Lewis acid.
• Typical acids include Lewis acids, such as boron trifluoride and aluminum chloride; mineral acids, such as sulfuric acid, orthophosphoric acid and polyphosphoric acids; hydrogen halide acids, such as hydrobromic acid and hydrochloric acid.
• HC1 and BF 3 are preferred because they are gases and easily handled. At least a stoichiometric amount of .the acid must be used, although an excess over the stoichiometric up to the point of saturation of the ketoxime solution is not detrimental.
• the reaction of the aryl alkyl ketoxime with the acid to form the immonium complex or salt can be carried out at temperatures between about -20°C. and about 150°C., although temperatures between about 10°C. and about 40 o C. are preferred. The reaction is carried out until precipitation is complete, usually within one hour.
• the solid immonium complex is isolated, as by filtration, and washed with solvent, preferably the same as used in the initial solution. Then, the E ketoxime isomer immonium complex is neutralized to obtain the free E ketoxime. Neutralization is readily carried out using dilute aqueous solutions of alkali metal salts, particularly Na and K, of weakly ionized organic acids, such as carbonic acid and oxalic acid, e.g., sodium carbonate, potassium carbonate, sodium bicarbonate, sodium oxalate, and potassium oxalate. In general, the concentration of the aqueous solution can be between 10 weight per cent and 15 weight per cent and usually 10 weight per cent. A large excess of the aqueous solution is used, in the order of 3 parts per part immonium complex.
• alkali metal salts particularly Na and K
• weakly ionized organic acids such as carbonic acid and oxalic acid
• the concentration of the aqueous solution can be between 10 weight per cent and
• the aryl alkyl ketoximes are prepared from aryl alkyl ketones and excess hydroxylamine hydrochloride in the presence of a base, in a manner familiar to those skilled in the art. In practice, the aryl alkyl ketoximes usually are obtained as a mixture of E and Z isomers.
• the ketoximes are precursors for preparing active insecticides by converting them to ketoximinoethers for example, by reacting the sodium ketoximate with substituted alkyl bromides, such as m-phenoxybenzylbromide.
• ketoxime ratios are ascertained using two corroborative methods: (1) comparison of the E/Z isomer ratio of the thermally stable trimethyl silyl derivative of the oxime before and after acid (HC1) treatment, by gas chromatograph analysis and (2) comparison of the relative integration in the H 1 HMR of the separate resonances for the E and Z isopropyl methine protons, before and after the acid (HC1) treatment.
• the E stereochemistry was concluded from both H l and C13 chemical shift data. References: J. Am. Chem. Soc. 86, 4373 (1964); Tet. 23, 1079-1095 (1967); J. Am. Chem. Soc. 94, 4897 (1972); J.O.C. 39(8), 1017 (1974).
• a 60:40 E/Z isomeric mixture of p-chloro- isobutyrophenone oxime (151g., 0.76m) was dissolved in 50.0 ml of anhydrous diethyl ether. The solution was saturated with anhydrous HC1, whereupon a voluminous amount of pure E oxime hydrochloride precipitated. The solid was filtered and washed well with dry ether. The dried hydrochloride salt was then added in portions to a vigorously stirring solution of 2500 ml. of 10% Na 2 C0 3 . The free oxime was filtered; washed with H 2 0 until washings were neutral,, and dried, under reduced pressure to yield 145g. of 98% E p-chlorophenyl isopropyl ketoxime.
• Example 6 is a typical illustration of a sterospecific synthesis of an insecticidally active ketoximinoether using the E oxime of Example 1.

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• 1978
  • 1978-08-16 US US05/934,142 patent/US4158015A/en not_active Expired - Lifetime
• 1979
  • 1979-07-31 EP EP79301528A patent/EP0009865A1/de not_active Withdrawn
  • 1979-08-06 IL IL57990A patent/IL57990A0/xx unknown
  • 1979-08-15 DK DK341779A patent/DK341779A/da unknown
  • 1979-08-15 JP JP10321279A patent/JPS5551049A/ja active Pending
  • 1979-08-16 ZA ZA00794299A patent/ZA794299B/xx unknown
  • 1979-08-16 DD DD79215024A patent/DD146592A5/de unknown

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