The Reaction of Propylene Oxide With Organomagnesium Bromides

Huston, Ralph C.; Bostwick, Charles O.

doi:10.1021/jo01161a002

Cited by 16 publications

(12 citation statements)

References 4 publications

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“…The reaction mixtures were purified by column chromatography over silica gel (60-240 mesh). (R)-Pulegol (5a), 22 exo-borneol (5c), 23 cis-myrtanol (5f), 24 endo-camphanol (5g), 24,25 (-)-isopinocampheol (5h), 24 (R)-1mesitylpropan-2-ol (5j), 26 (S)-2-mesityl-1-phenylethanol (5k), 26,27 methyl methylphenylphosphinate, 12a o-anisylphenylphosphine oxide, 28 o-tolylphenylphosphine oxide, 29 1-naphthylphenylphosphine oxide, 30 benzylphenylphosphine oxide, 31 and tert-butylphenylphosphinic chloride (9e) 32 were prepared according to the literature procedures or were available from other research projects running in our laboratories. The preparation of compounds 7 and 8, and details of the reaction of racemic 3 with chiral alcohols (Table 2) are provided in the Supporting Information.…”

Section: Paper Syn Thesismentioning

confidence: 99%

Dynamic Kinetic Resolution of Phosphinic Acid Derivatives via Nucleophilic Substitution at Phosphorus Center

et al. 2018

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Reaction of racemic phosphinic acid derivatives with chiral alcohols proceeds with predominant formation of one diastereomer. The highest level of enrichment has been obtained for transesterfication of racemic methyl benzylphenylphosphinate (64% de). The outcome of the reaction depends on both the structure of chiral alcohol and the starting organophosphorus compound. The results strongly suggest that the nature of the observed phenomena is not a classical equilibration of intermediates found in dynamic kinetic resolution process but is a result of a different reactivity of both enantiomers of racemic substrate towards the same chiral nucleophile.

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Section: Paper Syn Thesismentioning

confidence: 99%

Dynamic Kinetic Resolution of Phosphinic Acid Derivatives via Nucleophilic Substitution at Phosphorus Center

et al. 2018

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“…7) are to be expected. Although propylene oxide reacts more slowly with magnesium diethyl (to yield magnesium diethyldiisopropoxide) than magnesium dibromide (to give magnesium dibromodiisopropoxide) 17), diethyl magnesium polymerises propylene oxide about 2.5 times faster than does magnesium dibromide. It is therefore considered that the loss of the bromide component of the GRIGNARD reagent is not the cause of the fall off in polymerisation rate in stage (i).…”

Section: Huston and B O S T W I C K~~) Found T H A T The Addition Of mentioning

confidence: 99%

The polymerisation of propylene oxide by organomagnesium compounds

Stafford

1971

Makromol. Chem.

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Diethyl magnesium as a diethyl etherate-dioxanate complex polymerises propylene oxide in a diethyl ether solution to very high molecular weight crystalline polymer. Magnesium dibromide diethyl etherate polymerises propylene oxide in diethyl ether to low polymer. Ethyl magnesium bromide diethyl etherate polymerises propylene oxide in diethyl ether in four distinct kinetic stages. In the first two kinetic stages, polymer similar to that produced by diethyl magnesium is obtained in very low yield. Polymer of RV w , 10,000to 15,000 in yields up to 50% is produced in the next two stages. Above a certain catalyst concentration, the second stage is characterised by gel formation and precipitation. The third kinetic stage, during which most of the eventual polymer yield is produced, occurs with breakdown of the gel and redissolution of the precipitate, a similarity with polymerisation of propylene oxide by magnesium dibromide. With the ethyl magnesium bromide polymerisation, above the aforementioned catalyst concentration, change of catalyst concentration or solvent affects only the initial polymerisation stage kinetically. ZUSAMMENFASSUNG:Propylenoxid wird durch den Diathylmagnesium/Diathylatherat/Dioxanat-Komplex in Diathylither zu hochmolekularen, kristallinen Polymeren polymerisiert, durch Magne-siumbromidlDiathylatherat in Diathylather dagegen zu niedermolekularen Produkten. Bei der Polymerisation von Propylenoxid mit &hylmagnesiumbromid/Diathylatherat in Diathylather treten vier kinetisch unterscheidbare Bereiche auf. I n den beiden ersten entsteht in geringer Ausbeute ein Polymeres, das dem durch Diathylmagnesium hergestellten ahnlich ist. I n den beiden letzten Bereichen werden Polymere mit Molekulargewichten M, M 10000-15000 in Ausbeuten bis zu 50% gebildet. I m zweiten kinetischen Bereich tritt oberhalb einer bestimmten (kritischen) Katalysatorkonzentration Gelbildung und Fallung auf. Der dritte kinetische Bereich (in dem der grol3te Teil des Polymeren gebildet wird) ist durch ein Verschwinden des Gels und ein Wiederauflosen der Fallung gekennzeichnet, ahnlich wie bei der Polymerisation von Propylenoxid mit Magnesiumdibromid. Bei der Verwendung von hhylenmagnesiumbromid als Katalysator beeinfluat jedoch die Katalysatorkonzentration oder die Natur des Losungsmittels nur den ersten kinetischen Bereich, sofern oberhalb der kritischen Katalysatorkonzentration gearbeitet wird. -*) New address: Sandoz AG (Bau 94/E 12), Postfach, CH-4002 Basel, Switzerland.

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“…Their work, along with later systematic studies by chemists in America, notably Cottle,3589 3 5 9 , 6 5 6 , 1 6 2 2 Huston,5099 [844][845][846][847][848][849] and others, has been exhaustively reviewed by Kharasch and Reinmuth,Q27 as well as by Gaylord and Becker.625 These encyclopedic articles should be consulted for a more complete treatment than can be given here.…”

Section: E Organometallic Reagentsmentioning

confidence: 99%

“…Phenylmagnesium bromide, a representative example of several aromatic Grignard reagents recorded in the literature in connexion with propylene oxide, also gives normal products (Eq. 826), as does the even bulkier reagent mesitylmagnesium bromide.5099 845 The reason for the singular behavior of tert-butylmagnesium chloride is therefore probably not merely a steric one. …”

Section: Tert-chmgclmentioning

confidence: 99%

Ethylene Oxides

Rosowsky¹

1964

Chemistry of Heterocyclic Compounds: A Series of Monographs

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The Reaction of Propylene Oxide With Organomagnesium Bromides

Cited by 16 publications

References 4 publications

Dynamic Kinetic Resolution of Phosphinic Acid Derivatives via Nucleophilic Substitution at Phosphorus Center

Dynamic Kinetic Resolution of Phosphinic Acid Derivatives via Nucleophilic Substitution at Phosphorus Center

The polymerisation of propylene oxide by organomagnesium compounds

Ethylene Oxides

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The Reaction of Propylene Oxide With Organomagnesium Bromides

Cited by 16 publications

References 4 publications

Dynamic Kinetic Resolution of Phosphinic Acid Derivatives via Nucleophilic­ Substitution at Phosphorus Center

Dynamic Kinetic Resolution of Phosphinic Acid Derivatives via Nucleophilic­ Substitution at Phosphorus Center

The polymerisation of propylene oxide by organomagnesium compounds

Ethylene Oxides

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Dynamic Kinetic Resolution of Phosphinic Acid Derivatives via Nucleophilic Substitution at Phosphorus Center

Dynamic Kinetic Resolution of Phosphinic Acid Derivatives via Nucleophilic Substitution at Phosphorus Center