1,2-Addition of Methylmagnesium Iodide to Mesityl Ketones

Fuson, Reynold C.; Armstrong, Marvin D.; Wallace, Wm. E.; Kneisley, J. Wayne

doi:10.1021/ja01233a005

Cited by 7 publications

(3 citation statements)

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“…One of these was 1 -duryl-1 -phenylethylene (II), the olefin which would be formed by dehydration of the carbinol produced by 1,2 addition. This result is similar to those obtained with benzoylmesitylene, benzoylisodurene, and p-toluylmesitylene (1). The 1-duryl-l-phenylethylene (II) was converted by the action of ozone to a mixture of henzoyldurene and durylphenylacetic acid.…”

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confidence: 85%

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The Addition of Methylmagnesium Iodide to Benzoyldurene

Fuson¹,

McKusick²,

Mills³

1946

J. Org. Chem.

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In earlier studies embracing benzoylmesitylene (1), benzoylisodurene (1), benzoyldurene (2), the mesitoylnaphthalenes (3), and similar diaryl ketones, it has been demonstrated that addition of Grignard reagents occurs in spite of the excessive crowding about the carbonyl group. The addition may be 1,2, 1,4, or 1,6, depending on the nature of the ketone and of the Grignard reagent which is used. Recently Young and Roberts (4) made the surprising discovery that 1,2 addition occurs when benzyl and s-butenyl Grignard reagents are condensed with acetomesitylene. These and methylmagnesium iodide are the only Grignard reagents which have been found to combine with mesityl ketones in this manner.In most cases addition takes place in the 1,4 manner.There is evidence, however, that even 1,4 addition is limited to reagents having small alkyl or aryl groups. In fact, in two instances 1,6 addition has been observed; benzyl-and -butylmagnesium chloride react in this manner with benzoyldurene (2).

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confidence: 85%

“…of water, and the Calc'd: C, 83.67; H, 10.14 Found: C, 83.70; H, 10.32 °All the ketones listed in this table were prepared by the Friedel-Crafts method. 1 This compound was made by the Friedel-Crafts method and also by the Grignard method.…”

mentioning

confidence: 99%

The Addition of Methylmagnesium Iodide to Benzoyldurene

Fuson¹,

McKusick²,

Mills³

1946

J. Org. Chem.

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“…(5 H, m, phenyl CH), 6.68 (2 H, s, aryl CH), 2.18 (3 H, s, aryl CH;i), 2.10 (6 H, s, aryl CH3), 1.88 (3 H, s, CH3CO), and 1.68 (1 H, s, OH, exchanged with D20); mass spectrum m/e (rel intensity) 240 (M+, <1), 223 (13), 222 (58), 208 (18), 207 (100), 206 (18), 192 (45), 191 (12), and 96 (11).…”

Section: Experimental Section18mentioning

confidence: 99%

Reactions involving electron transfer. 11. Reaction of lithium dimethylcuprate with diaryl ketones

House¹,

Chu²

1976

J. Org. Chem.

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Protonenresonanz‐Untersuchungen zur inneren Rotation, VIII. Konformationsanalyse α.α.o.o′‐tetrasubstituierter Toluole mittels magnetischer Kernresonanz und halbempirischer Energieberechnung

Mannschreck

Ernst

1971

Chem. Ber.

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Proton Magnetic Resonance Studies of Internal Rotation, VIII') Conformational Analysis of a.a.o.0'-tetrasubstituted Toluenes by Means of Nuclear Magnetic Resonance and Semi-empirical Energy CalculationsIH n.m.r. spectra and semi-empirical calculations of strain energies have shown that the ground state of the toluene derivative 3 is represented by conformation a (R -CH3), the cr-methine proton of which eclipses one of the o-methyl groups. Accordingly, the existence of two rotamers, e.g. 15E and 15Z, was demonstrated in the case of the toluenes 15,16,17,18, and 19 synthesized with two unequal 0-or m-substituents. The measured equilibrium ratios of rotamers (Table 2) are in good agreement with the results of the calculations for 15 and 16.-The free enthalpies of activation AG: for rotation about the C, -aryl bond vary from 7.5 to 15 kcal/mole (Table\ 1 and 2). Barriers of this kind were reproduced with sufficient accuracy by calculations for 3, 15, and 16 if the C, aryl bond length and the bond angles were assumed to be flexible, i.e., if they were optimized for each rotational arrangement. The transition state turned out to be a conformation of type d, the C,-H bond of which 1971Protonenresonanz-Untersuchungen zur inneren Rotation (VIII.) 229 is arranged perpendicular to the benzene ring; potential energy curves for C:,-aryl rotation are given in Fig. 3 and 4. Calculations presupposing a rigid molecular geometry erroneously result in conformation c as the transition state and yield barriers which are much higher than the measured ones.Die bei der Rotation urn sp? sp3-oder spz-sp2-Rindungen ghnstigen Konformationen wurden in experimenteller und theoretischer Hinsicht weit ausfiihrlicher untersucht als die Verhaltnisse an sp2 -sp3-Valenzen2). Derartige Konformationen weisen bei Verbindungen des Typus 1 und 2 eine besonders hohe Lebensdauer auf und sind deshalb NMR-spektroskopisch erfaRbar, was sich erstmals fur 9-Mesityl-fluoren3), das man als substituiertes Toluol 1 auffassen kann, und filr N.N-Dibenzyl-anilinium-Ionen4) 2 7eigen lie13. An einfacheren Toluolen. die in den ortho-Stellungen symmetrisch substituiert Find (1, RI --RZ -CH3), sollte nun der unbekaiinte relative Energieinhalt der ausgezeichneten Konformationen a, b, c und d ermittelt, d. h. die vollstandige Potentialkurve fur die sp2--sp3-Rotdtion aufgestellt werden, wobei besonders die Struktur des Grund-und des ubergangszustandes interessierte. Im AnschluR daran sollten sich die analogen Fragen auch fur unsymmetrisch substituierte Derivate (1, R1 += R2) bedntworten lassen.Protonenresonanz-Ergebnisse fur Toluole mit zwei gleichen o-Substituenten 3 zeigt bei -60" fur die beiden o-Methylgruppen zwei Signale (Abbild. l), die durch ihre Koaleszenz bei T, --35" (Aceton-ds) unter Ausbildung rines Singuletts leicht von der p-Methyl-Absorption zu unterscheiden sind. Das r-Methyl-Dublett ( J ~ 7 HI) ist dagegen bei -60' weder in CS2 noch in Aceton-ds als Losungsmittel weiter aufgespalten oder verbreitert. Diese Befunde lassen sich nicht mit der Konformation d (R...

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1,2-Addition of Methylmagnesium Iodide to Mesityl Ketones

Cited by 7 publications

References 0 publications

The Addition of Methylmagnesium Iodide to Benzoyldurene

The Addition of Methylmagnesium Iodide to Benzoyldurene

Reactions involving electron transfer. 11. Reaction of lithium dimethylcuprate with diaryl ketones

Protonenresonanz‐Untersuchungen zur inneren Rotation, VIII. Konformationsanalyse α.α.o.o′‐tetrasubstituierter Toluole mittels magnetischer Kernresonanz und halbempirischer Energieberechnung

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