1973
DOI: 10.1021/jo00941a054
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Chromyl chloride in acetone. .alpha.-Chloro ketones and ketones directly from olefins

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Cited by 43 publications
(12 citation statements)
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“…For instance, the role of the solvent (in acetone a-chloro carbonyl compounds become mayor products) [33] remains unclear and more importantly the present investigations do not explain why diols are absent as products in the reactions between CrO 2 Cl 2 and olefins, whereas the corresponding reactions between OsO 4 and olefins generate exclusively diols with little epoxide as a product. [9] To answer this question one would have to consider the diolates formed from the [23] addition of ethylene to CrO 2 Cl 2 and OsO 4 , respectively, and compare their rate of hydroxylation with water to their rate of rearrangements to epoxides.…”
Section: Discussionmentioning
confidence: 75%
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“…For instance, the role of the solvent (in acetone a-chloro carbonyl compounds become mayor products) [33] remains unclear and more importantly the present investigations do not explain why diols are absent as products in the reactions between CrO 2 Cl 2 and olefins, whereas the corresponding reactions between OsO 4 and olefins generate exclusively diols with little epoxide as a product. [9] To answer this question one would have to consider the diolates formed from the [23] addition of ethylene to CrO 2 Cl 2 and OsO 4 , respectively, and compare their rate of hydroxylation with water to their rate of rearrangements to epoxides.…”
Section: Discussionmentioning
confidence: 75%
“…In addition to the aforementioned products carbonyl compounds were often obtained, too, but these were considered as secondary rather than primary products and proposed to follow from subsequent reactions of the epoxides or chlorohydrins during workup. [32,33] However, recently a hint to the relevance of intermediate chromium complexes also for the formation of the carbonyl products was provided: H. Schwarz, D. Schröder et al showed that the CrO 2 ionÐthat is a Cr V oxideÐreacts with ethylene in the gas phase to yield OCr ´´´O CH-CH 3 [34a] and (more relevant to the present problem as a d 0 system is considered) VO 2 oxidizes ethylene to form OV ´´´O CHCH 3 . [34b] In an attempt to investigate the ethylene oxidation by CrO 2 Cl 2 at an early stage at very low temperatures and to thereby obtain direct information about occurring primary and secondary intermediates we have successfully employed matrix isolation techniques: if the activation energy necessary to trigger the reaction in argon at 10 K is provided by means of irradiation, the species OCrCl 2´´´O CHCH 3 (1) and OCrCl 2´´´O CH 2 CH 2 (2) [Eq.…”
Section: Discussionmentioning
confidence: 99%
“…Since other olefins are quantitatively oxidized to carbonyl compounds by CrO 2 Cl 2 in thermal reactions, [3] intermediates analogous to 1 could play a more important role in these cases, although, of course, other mechanisms for the formation of carbonyl compounds are imaginable. [5] The isolation of an intermediate in an olefin oxidation by CrO 2 Cl 2 was achieved for the first time. The presence of this intermediate could explain the occurrence of carbonyl compounds in the product spectrum of such reactions.…”
mentioning
confidence: 99%
“…B. Chromaoxetane, Chromalkoxide und Epoxidkomplexe), von denen allerdings bis heute keines nachgewiesen werden konnte, erklären sollten. [3,4] Das Auftreten von Carbonylverbindungen im Produktspektrum wurde teilweise mit Umlagerungsreaktionen bestimmter Endprodukte bei der Aufarbeitung erklärt, [3,5] während jüngere Arbeiten die Bedeutung intermediärer Chromkomplexe dieser Carbonylverbindungen unterstreichen. So entsteht bei der Reaktion des CrO 2 -Ions mit Ethylen im Massenspektrometer nachweislich OCr ´´´O CHCH 3 .…”
unclassified
“…[12] hergestellt und gereinigt; AsF 5 wurde aus den Elementen hergestellt und durch fraktionierende Kondensation gereinigt; SbF 5 wurde fraktionierend destilliert und HF mit Fluor getrocknet. [13] In einem KEL-F-Reaktor wurden 3 mmol MF 5 [9] ). Durch Untersuchung der Konzentrationsabhängigkeit konnte weiterhin gezeigt werden, daû nur ein Ethylen-¾quivalent an der Reaktion beteiligt ist, so daû das organische Produkt eine Carbonylverbindung mit einer C 2 -Einheit sein muû (O CH 2 kann als Produkt ausgeschlossen werden [10] [11] zur Synthese des 18 O-Isotopomers von 1, verschieben sich lediglich drei Banden signifikant: die n(CO)-(Dn Ä 29 cm À1 ) und die n(CrO)-Bande (43 cm À1 ) sowie eine weitere Bande bei 852 cm À1 (26 cm À1 ), der nach diesem Experiment hauptsächlich ein d(CCO)-Charakter zugeordnet werden kann.…”
unclassified