- Efficient synthesis of vinyl chlorides and/or gem-dichlorides from ketones by treatment with tungsten hexachloride
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Treatment of cyclic ketones, e.g. 4, with tungsten hexachloride (WCl 6) provided good yields of vinyl chlorides, e.g. 5, and/or gem-dichlorides. A trans-diequatorial dichloride 9 was prepared by treatment of the corresponding epoxide 8 with WCl
- Jung, Michael E.,Wasserman, Jacob I.
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- Cobalt Catalyzed Reductive Spirocyclopropanation Reactions
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Cobalt pyridine?diimine (PDI) complexes catalyze the reductive spirocyclopropanation of terminal 1,3-dienes. gem-Dichlorocycloalkanes serve as carbene precursors and Zn is used as a terminal electron source. The reaction is effective for a range of gem-di
- Werth, Jacob,Berger, Kristen,Uyeda, Christopher
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supporting information
p. 348 - 352
(2019/11/28)
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- Preparation method of heteroatom-containing cyclohexene halide
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The invention discloses a preparation method of a heteroatom-containing cyclohexene halide, belonging to the field of synthesis of fine chemical intermediates. According to the preparation method, cyclohexanone containing heteroatoms is used as a raw material, and gem-dihalide or alkenyl halide is mainly generated in a halogenating reagent; and after an additive is added into organic alkali, and hydrogen halide is removed to generate cyclohexene halide containing heteroatoms. The method is simple in process; the operation of purifying a mixture in traditional methods is avoided; and a productis fully utilized. Under close-to-elimination condition of gem-dibromide, an additive is added to overcome the problem of difficulties in gem-dichloride elimination is by adding, and the purpose of controlling regioselectivity is achieved through steric hindrance of different alkalis.
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Paragraph 0048-0050
(2019/12/25)
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- Chlorination of oximes in hydrogen fluoride: formation of gem-dihalogenoalkanes
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The action of chlorine on oximes in hydrogen fluoride as a medium gives gem-dihalogenoalkanes.The reaction proceeds through the intermediate formation of gem-chloronitrosoalkanes.The relative proportions between gem-dichloro, -difluoro and -fluorochloro compounds are dependent on the presence of a cosolvent.The use of other oxidants, such as nitric oxide, dinitrogen tetroxide or nitrosyl chloride, gives similar compounds: - Keywords: Chlorination, Oximes; Hydrogen fluoride; Dihalogenoalkanes; NMR spectroscopy, Mass spectrometry
- Tordeux, Marc,Boumizane, Khalid,Wakselman, Claude
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p. 207 - 214
(2007/10/02)
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- KINETIC ANALYSIS OF ALKANE POLYCHLORINATION WITH MOLECULAR CHLORINE. CHLORINE ATOM/MONOCHLORIDE GEMINATE PAIRS AND THE EFFECT OF REACTIVE 'CAGE WALLS' ON THE COMPETITION BETWEEN MONOCHLORIDE ROTATION AND CHLORINE ATOM ESCAPE.
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The free-radical chlorination of alkanes produces polychlorides even at low conversions. These are formed by reaction of chlorine atom/monochloride (or dichloride) geminate pairs. This process has been studied in detail in various solvent systems, and a kinetic scheme has been proposed. Deviations from this scheme have been rationalized as being due to competition between monochloride rotation and reaction of the chlorine atom with reactive molecules in the 'cage walls' surrounding the chlorine atom/chloride geminate pair. Analysis of the dichloride products supports the suggestion that monochloride rotation is not completely 'free' within the lifetime of the geminate pair.
- Raner,Lusztyk,Ingold
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p. 3519 - 3524
(2007/10/02)
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- C-Nitroso compounds. Part XXXVI. Rearrangement of 2-chloro-2-nitrosofenchane and 2-chloro-2-nitrosocamphane
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2-Chloro-2-nitrosofenchane 7 rearranges under the influence of aluminium chloride to the isomeric chloronitrones 9 and 12 (Scheme 3). 2-Chloro-2-nitrosocamphane 18 (Scheme 4) gives, under similar conditions, only one chloronitrone 19, despite the close structural relationship between the starting materials 7 and 18.The chloronitrones react with all common nucleophiles, e.g. with water, to give hydroxamic acids, which can easily be reduced to the amides 4,5 and 6.The first and last of these amides are not accessible by Beckmann rearrangement of the appropriate oximes.
- Lub, J.,Boer, Th. J. de
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p. 328 - 332
(2007/10/02)
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