Reaction of Chromyl Chloride With Some Olefins: Part I. The Products From Cyclohexene, Cyclopentene, 1-Hexene, and 2-Methyl-1-Pentene

Stairs, Robert A.; Diaper, D. G. M.; Gatzke, A. L.

doi:10.1139/v63-151

Cited by 28 publications

(5 citation statements)

References 6 publications

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“…It could be excluded that they were generated in the matrix by isomerization of epoxide complexes and on permethylation of the olefinic bond (i.e., employment of TME) their formation route was completely suppressed. Moreover, first representatives for OCrCl 2 ···epoxide complexes, often proposed as intermediates in the literature, − ,,, have been isolated and characterized. Both types of complexes should be considered as respectable intermediates also under thermal conditions.…”

Section: Discussionmentioning

confidence: 99%

“…For quite some time the olefin oxidation with chromyl chloride (CrO 2 Cl 2 ) seemed to proceed completely unspecifically, and reports with the most different product palettes accumulated. − The first selective oxidation was reported in 1969 by F. Freeman et al claiming that reductive workup of the reaction mixtures in the presence of zinc enables the isolation of carbonyl compounds in good yields . However, mainly disubstituted, electron-rich olefins had been employed in this investigation. − In 1973 K. B. Sharpless et al found that chloroketones are formed selectively if the reactions are carried out in acetone at −78 °C, and they related the findings made on reductive workup 7-11 to the reduction of these oxychlorides by zinc.…”

Section: Introductionmentioning

confidence: 93%

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Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl₂−Epoxide Complexes

Limberg

Köppe

1999

Inorg. Chem.

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After photolytic induction (411 nm) of the reaction between chromyl chloride and olefins in low-temperature matrixes, for the first time primary products of this system have been isolated and identified: the reaction of propylene yields O=CrCl(2).O=CHCH(2)CH(3) and while in the case of trans- and cis-2-butylene, OCrCl(2).O=C(CH(3))(CH(2)CH(3)) as well as OCrCl(2).(trans-2,3-butylene oxide) and OCrCl(2).(cis-2,3-butylene oxide) are obtained, respectively. Epoxide formation proceeds under complete retention of stereochemistry, and the regioselective reaction route leading to the carbonyl products can be suppressed if all hydrogen atoms at the olefinic bond are substituted: tetramethylethylene is selectively oxidized to tetramethylethylene oxide, which forms a complex with OCrCl(2). All products were characterized by IR spectroscopy, which was further supported by DFT calculations in certain cases. The mechanism leading to the formation of these products, their electronic states, and the implications of the matrix results on the thermal reactions of chromyl chloride are discussed.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 93%

Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl₂−Epoxide Complexes

Limberg

Köppe

1999

Inorg. Chem.

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“…Transition metal oxides and halides are applied extensively as oxidants in processes where oxygen or halogen is inserted into a C−H linkage or added to an olefin double bond. − Oxidation carried out in this way is often relatively gentle and remarkably specific compared to the direct application of elemental oxygen or halogen. Many of the oxidation processes have been subject to mechanistic studies. − …”

Section: Introductionmentioning

confidence: 99%

A Density Functional Study of [2+3] versus [2+2] Addition of Ethylene to Chromium−Oxygen Bonds in Chromyl Chloride

1998

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Density functional theory (DFT) calculations have been carried out on the [2+2] and [2+3] addition of ethylene to Cr=O bonds in CrO(2)Cl(2). The [2+3] addition was found to be more favorable with an electronic reaction enthalpy of -9.6 kcal/mol and an activation barrier of 15.8 kcal/mol. The corresponding values for the [2+2] addition were 15.4 and 27.9 kcal/mol, respectively. It was concluded that epoxides formed in the reaction between CrO(2)Cl(2) and olefins are unlikely to originate from a [2+2] addition path to a Cr=O bond as previously suggested. The two addition reactions were analyzed by the intrinsic reaction coordinate method, and comparisons were made to a previous study of [2+2] and [2+3] addition by ethylene to OsO(4). Qualitative considerations were used to rationalize why the addition of ethylene to metal-oxygen bonds in tetrahedral d(0) oxo complexes seems more prone to proceed by a [2+3] mechanism.

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“…The nature of these products speaks strongly against the proposals of Stairs et a/. (10) and Nenitzescu and coworkers (1 1) both of whom proposed that the a$-unsaturated carbonyl compounds formed in chromyl chloride oxidations of olefins could arise from the elimination of HCl from an a-chloroketone. This rather unlikely process would yield a$-unsaturated derivatives of pinocamphone (2) but none of these products are found.…”

Section: Traduit Par Le Journal]mentioning

confidence: 91%

The Chromyl Chloride Oxidation of α-Pinene

Bachelor¹,

Cheriyan²

1972

Can. J. Chem.

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The oxidation of α-pinene with chromyl chloride has been investigated and 11 compounds amounting to 81% of the total reaction have been isolated and identified. Besides a small amount of recovered α-pinene these compounds have been found to be products of acid-catalyzed rearrangement (bornyl chloride, borneol, and limonene); products of allylic oxidation (myrtenal, myrtenol, and verbenone); and products of oxidative addition–rearrangement (pinocamphone, pinocarveol, campholenaldehyde, and pinol). In addition, p-cymene was isolated which may arise from several oxidation sequences. The isolation of optically active pinol suggests that at least part of the oxidation of α-pinene is initiated by attack of the chromyl chloride on the same side of the double bond as the dimethyl substituted bridge. An attack by a positive chromium atom on the double bond is ruled out by a deuteration study.

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Reaction of Chromyl Chloride With Some Olefins: Part I. The Products From Cyclohexene, Cyclopentene, 1-Hexene, and 2-Methyl-1-Pentene

Cited by 28 publications

References 6 publications

Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl₂−Epoxide Complexes

Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl₂−Epoxide Complexes

A Density Functional Study of [2+3] versus [2+2] Addition of Ethylene to Chromium−Oxygen Bonds in Chromyl Chloride

The Chromyl Chloride Oxidation of α-Pinene

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Reaction of Chromyl Chloride With Some Olefins: Part I. The Products From Cyclohexene, Cyclopentene, 1-Hexene, and 2-Methyl-1-Pentene

Cited by 28 publications

References 6 publications

Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl2−Epoxide Complexes

Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl2−Epoxide Complexes

A Density Functional Study of [2+3] versus [2+2] Addition of Ethylene to Chromium−Oxygen Bonds in Chromyl Chloride

The Chromyl Chloride Oxidation of α-Pinene

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Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl₂−Epoxide Complexes

Reactive Intermediates in Olefin Oxidations with Chromyl Chloride. IR-Spectroscopic Proof for OCrCl₂−Epoxide Complexes