The Reaction of Ethylene Oxide With Grignard's Reagent

Huston, R. C.; Agett, A. H.

doi:10.1021/jo01201a012

Cited by 37 publications

(20 citation statements)

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“…The isolation of these fragments at the alcohol oxidation level was at first sight surprising. In mammalian steroid biosynthesis (22R)-22-hydroxycholesterol ' M e (10) and (20R,22R)-20,22-dihydroxycholesterol have been identified l6 as key intermediates whilst the side chain fragment was obtained as the aldehyde. The sterol side chain is labelled from the 2-position of mevalonate at C-22 and C-26 and consequently two centres in the alcohols ( 6) and ( 7) should be labelled.…”

mentioning

confidence: 99%

Studies of terpenoid biosynthesis. Part 29. The cleavage of the sterol side chain in the biosynthesis of demethoxyviridin

Hanson¹,

O’Leary²,

Wadsworth³

1983

J. Chem. Soc., Perkin Trans. 1

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The structures of a group of C6 and C7 alcohols obtained from Nodulisporium hinnuleum have been elucidated. When biosynthesized from [2-14C]me~alonic acid they have been shown to have a specific activity consistent with a common origin with their co-metabolite, demethoxyviridin. The number of [2-2H2] mevalonoid hydrogen atoms which were incorporated suggests that they were formed initially at the aldehyde oxidation level.

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confidence: 99%

Studies of terpenoid biosynthesis. Part 29. The cleavage of the sterol side chain in the biosynthesis of demethoxyviridin

Hanson¹,

O’Leary²,

Wadsworth³

1983

J. Chem. Soc., Perkin Trans. 1

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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%

“…849 and methyl-to n-butylmagnesium iodide.847 In addition, several branched-chain primary alkylmagnesium bromides, chlorides, and iodides have been examined. 844 Most effective among the three types of alkylmagnesium halides are apparently the bromides,8449 845 chlorides and iodides exhibiting a greater tendency to form halohydrins at the expense of desired Grignard adducts.8441847 Chain length seems to have little or no effect on yield and product composition. Reactant ratio, however, and to an even greater extent temperature and reaction time, play profound roles in determining the composition of product mixtures.…”

Section: R = Ch3 Cahsmentioning

confidence: 99%

“…817) are isopropylmagnesium halides, sec-butylmagnesium halides, and several others. 844,847,848 Tertiary alkyl Grignard reagents are extremely unreactive toward ethylene oxide, giving rise exclusively to ethylene halohydrins under conditions normally suitable for reactions with primary or secondary Grignard reagents.800.8449 8473 848 In other words, in terms of the Schlenk equilibrium concept set forth above, the magnesium halide component of tertiary alkyl Grignard reagents causes halohydrin formation faster than the dialkylmagnesium component can add. Special conditions have, however, been found, which permit addition of tert-butylmagnesium chloride to ethylene oxide (Eq.…”

Section: R = Ch3 Cahsmentioning

confidence: 99%

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Ethylene Oxides

Rosowsky¹

1964

Chemistry of Heterocyclic Compounds: A Series of Monographs

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“…When the initially formed complex of the Grignard reagent with oxirane is treated with water without preliminary heating the resulting product is a halohydrin. The yield of the latter decreases with growing temperature of the treatment before decomposition of the complex (boiling in the ethyl ether [43] or replacement of the ether by a higher boiling solvent [44,45]). However a better method preventing nearly completely the halohydrin formation consists in distilling off the ether before the treatment of the reaction mixture [46], or in precipitation of MgX 2 by adding dioxane [45].…”

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confidence: 99%

Vinyl Ethers Containing an Epoxy Group: XXIII. Reactions of Alkynylmagnesium Bromides with Glycidol Ethers: Synthesis and Thermal Transformations of 1-[2-( Vinyloxy)ethoxy]- and 1-(Allyloxy)-5-hexyn-2-ols, -5-phenyl-4-pentyn-2-ols, and -3-bromo-2-propanols

et al. 2005

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Reaction of 2-[2-(vinyloxy)ethoxy]methyl-and 2-(allyloxymethyl)oxiranes with 2-propynyl-and phenylethynylmagnesium bromides (1055°C, 0.54 h) resulted in new representatives of the series of 1-organyloxy-5-hexyn-2-ols, -5-phenyl-4-pentyn-2-ols, and -3-bromo-2-propanols in 5099% yields. During distillation the 1-[2-(vinyloxy)ethoxy]-5-phenyl-4-pentyn-2-ol and -3-bromo-2-propanol transform respectively into 2-methyl-4-(3-phenyl-2-propynyl)-and 2-methyl-4-(bromomethyl)-1,3,6-trioxocanes via intramolecular cyclization involving the hydroxy and vinyloxy groups.The reaction of organomagnesium compounds (Grignard [2, 3] and Iotsich reagents [3,4]) with oxiranes is a classical building up method of alcohol synthesis (with formation of a CC bond) [3, 511], also used for acetylene and allene alcohols [611]. The best studied reaction is that of the Grignard reagents with the simplest epoxides: unsubstituted oxirane, methyl-, phenyl-, 2,2-dimethyl-, and 2,3-dimethyloxiranes, although other examples of this process are also described (with naturally occurring epoxides, epoxyalcohols, epoxyketones, epoxyesters, diepoxides etc.) [511]. The reaction finds an industrial application in production of various technically important alcohols, in particular, those used in fragrance industry: 2-phenyl-1-ethanol (rose oil) [12], 3-phenyl-1-propanol (with the hyacinth fragrance) [13], 3,7-dimethyl-6-octen-1-ol (rhodinol) with a rose scent [14], alcohols with the properties of sex attractants and plant growth regulators. [15].The preparation was reported of chiral homoallyl alcohols in reaction of vinylmagnesium halides with glycidol derivatives containing as protection functions benzyl, methoxtphenylmethyl, tert-butyldimethylsilyl, and tertbutyldiphenylsilyl groups [16]. (R)-1-(Benzyloxy)-5-hexen-2-ol, the key intermediate in the stereoselective synthesis of trans-2,5-dioxymethylpyrrolidone derivatives possessing C 2 -symmetry, was obtained by treating with allylmagnesium chloride the optically active (S)-2-[(benzyloxy)methyl]oxirane [17]; reactions were performed of 2-(methoxymethyl)-and 2-(phenoxymethyl)-oxiranes with ethyl-and phenylmagnesium bromides [18]. Alkynols and allenols originate from both reactions of alkynylmagnesium halides with oxiranes [610] and of 2-ethynyloxiranes with Grignard reagents 11]. The alkynols combining the properties of the three most important classes of organic compounds (alcohols [19], acetylenes [20], and CH-acids when the compounds contained fragments CºCH and/or CH 2 CºC [21,22]) are valuable intermediates in preparation of a lot of synthetically and commercially significant products (chemicals for agriculture, drugs, and fragrant substances [9,23]). They are widely used in the synthesis of functionalized acetylene alcohols and diols [1, 24], heterocycles, including derivatives of furan [25], pyran [26], pyrrole [27], indole [28], pyrazole [29], 2,3-dihydropyridine, pyridine [30], benzazepine-1,5-dione [31], thiophene [32], various allene systems [20, 23, 24, 33], in particular, allenols that ar...

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The Reaction of Ethylene Oxide With Grignard's Reagent

Cited by 37 publications

References 1 publication

Studies of terpenoid biosynthesis. Part 29. The cleavage of the sterol side chain in the biosynthesis of demethoxyviridin

Studies of terpenoid biosynthesis. Part 29. The cleavage of the sterol side chain in the biosynthesis of demethoxyviridin

Ethylene Oxides

Vinyl Ethers Containing an Epoxy Group: XXIII. Reactions of Alkynylmagnesium Bromides with Glycidol Ethers: Synthesis and Thermal Transformations of 1-[2-( Vinyloxy)ethoxy]- and 1-(Allyloxy)-5-hexyn-2-ols, -5-phenyl-4-pentyn-2-ols, and -3-bromo-2-propanols

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