Formation and Reactions of Ring-Substituted Derivatives of (η5-Cyclopentadienyl)dicarbonylnitrosylchromium

Marvin D. Rausch, Eric A. Mintz, David W. Macomber

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Abstract

Friedel-Crafts acylation of (η5-cyclopentadienyl)dicarbonylnitrosylchromium (1) produces the corresponding ketones and esters in good yield. Hydrolysis of [η5-((methylthio)carbonyl)cyclopentadienyl]dicarbonylnitrosylchromium gives (η5-carboxycyclopentadienyl)dicarbonylnitrosylchromium (pKa = 5.1) in 50% yield. Reduction of ketone derivatives of 1 with sodium borohydride produces the corresponding secondary alcohols in high yield, whereas reduction with lithium aluminum chloride-aluminum chloride leads to products of hydrogenolysis in 55-65% yield. High yields of tertiary alcohols have been obtained by treating ketone derivatives of 1 with alkyl or aryl Grignard reagents. Dehydration of [η5-(l-hydroxy-l-methylethyl)cyclopentadienyl]dicarbonylnitrosylchromium produces (η5-isopropenylcyclopentadienyl)dicarbonylnitrosylchromium in 81 % yield. (η5-Ethynylcyclopentadienyl)dicarbonylnitrosylchromium has been prepared by reaction of (η5-acetylcyclopentadienyl) dicarbonylnitrosylchromium with phosphorus oxychloride in dimethylformamide, followed by decomposition of the resulting chloro aldehyde in refluxing basic dioxane solution.

Original languageEnglish (US)
Pages (from-to)689-695
Number of pages7
JournalJournal of Organic Chemistry
Volume45
Issue number4
DOIs
StatePublished - Jan 1 1980

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Ketones
Derivatives
Alcohols
Acylation
Dimethylformamide
Hydrogenolysis
Dehydration
Lithium
Aldehydes
Hydrolysis
Esters
Decomposition
aluminum chloride

Cite this

Formation and Reactions of Ring-Substituted Derivatives of (η5-Cyclopentadienyl)dicarbonylnitrosylchromium. / Rausch, Marvin D.; Mintz, Eric A.; Macomber, David W.

In: Journal of Organic Chemistry, Vol. 45, No. 4, 01.01.1980, p. 689-695.

Research output: Contribution to journalArticle

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abstract = "Friedel-Crafts acylation of (η5-cyclopentadienyl)dicarbonylnitrosylchromium (1) produces the corresponding ketones and esters in good yield. Hydrolysis of [η5-((methylthio)carbonyl)cyclopentadienyl]dicarbonylnitrosylchromium gives (η5-carboxycyclopentadienyl)dicarbonylnitrosylchromium (pKa = 5.1) in 50{\%} yield. Reduction of ketone derivatives of 1 with sodium borohydride produces the corresponding secondary alcohols in high yield, whereas reduction with lithium aluminum chloride-aluminum chloride leads to products of hydrogenolysis in 55-65{\%} yield. High yields of tertiary alcohols have been obtained by treating ketone derivatives of 1 with alkyl or aryl Grignard reagents. Dehydration of [η5-(l-hydroxy-l-methylethyl)cyclopentadienyl]dicarbonylnitrosylchromium produces (η5-isopropenylcyclopentadienyl)dicarbonylnitrosylchromium in 81 {\%} yield. (η5-Ethynylcyclopentadienyl)dicarbonylnitrosylchromium has been prepared by reaction of (η5-acetylcyclopentadienyl) dicarbonylnitrosylchromium with phosphorus oxychloride in dimethylformamide, followed by decomposition of the resulting chloro aldehyde in refluxing basic dioxane solution.",
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AB - Friedel-Crafts acylation of (η5-cyclopentadienyl)dicarbonylnitrosylchromium (1) produces the corresponding ketones and esters in good yield. Hydrolysis of [η5-((methylthio)carbonyl)cyclopentadienyl]dicarbonylnitrosylchromium gives (η5-carboxycyclopentadienyl)dicarbonylnitrosylchromium (pKa = 5.1) in 50% yield. Reduction of ketone derivatives of 1 with sodium borohydride produces the corresponding secondary alcohols in high yield, whereas reduction with lithium aluminum chloride-aluminum chloride leads to products of hydrogenolysis in 55-65% yield. High yields of tertiary alcohols have been obtained by treating ketone derivatives of 1 with alkyl or aryl Grignard reagents. Dehydration of [η5-(l-hydroxy-l-methylethyl)cyclopentadienyl]dicarbonylnitrosylchromium produces (η5-isopropenylcyclopentadienyl)dicarbonylnitrosylchromium in 81 % yield. (η5-Ethynylcyclopentadienyl)dicarbonylnitrosylchromium has been prepared by reaction of (η5-acetylcyclopentadienyl) dicarbonylnitrosylchromium with phosphorus oxychloride in dimethylformamide, followed by decomposition of the resulting chloro aldehyde in refluxing basic dioxane solution.

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