Product‐determining factors in the grignard reactions of benzophenones. The role of the structure of alkyl groups in grignard reagents

The mechanism of the Grignard reactions of substituted benzophenones with two kinds of alkyl Grignard reagent, n-C 3 H 7 MgBr and i-C 3 H 7 MgBr, was investigated. In these reactions, both addition and reduction products were also generated. Based on the results of product analysis and stopped-flow, ESR and association measurements, it was confirmed that the product distribution was governed by several factors: the oxidizing ability of benzophenones, the association ability of Grignard reagents and the structure of alkyl groups of Grignard reagents. In particular, the strength of C-Mg and β-C-H bonds of Grignard reagents could strongly affect the product distribution

[1]  H. Yamataka,et al.  Rate-determining step of the reactions of benzophenone with various Grignard reagents , 1989 .

[2]  E. C. Ashby.  Single-electron transfer, a major reaction pathway in organic chemistry. An answer to recent criticisms , 1988 .

[3]  C. Walling.  A fresh look at electron transfer in the reactions of Grignard reagents , 1988 .

[4]  K. Maruyama,et al.  Structure of radical intermediates appearing in the grignard reaction of monoketones , 1988 .

[5]  K. Maruyama,et al.  Mechanism of the Grignard reaction. Reaction of benzil , 1986 .

[6]  E. C. Ashby,et al.  New methodology in determining evidence for single electron transfer in the reaction of Grignard reagents with ketones , 1985 .

[7]  T. Holm.  Electron transfer from alkylmagnesium compounds to organic substrates , 1984 .

[8]  E. C. Ashby,et al.  Direct evidence supporting a single electron transfer pathway in the reduction of ketones by primary, secondary, and tertiary Grignard reagents , 1981 .

[9]  E. C. Ashby,et al.  Organometallic reaction mechanisms. 17. Nature of alkyl transfer in reactions of Grignard reagents with ketones. Evidence for radical intermediates in the formation of 1,2-addition product involving tertiary and primary Grignard reagents , 1981 .

[10]  T. Holm.  Thermochemical bond dissociation energies of carbon–magnesium bonds , 1981 .

[11]  E. C. Ashby.  A detailed description of the mechanism of reaction of Grignard reagents with ketones , 1980 .

[12]  N. Yanaihara,et al.  MECHANISMS OF THE REACTIONS OF GRIGNARD REAGENTS. XIII. SINGLE ELECTRON TRANSFER IN THE REDUCTION OF AZOBENZENE AND BENZOPHENONE , 1980 .

[13]  M. Ōkubo.  Ketyl Radicals Formed in Grignard Reaction. IV. Sterically Hindered Ketyl Radicals in Nuclear Replacement and Conjugate Addition , 1977 .

[14]  M. Ōkubo.  Abnormal Grignard Reaction of 2,4,6-Trimethylbenzophenone: An Electron-transfer Mechanism , 1975 .

[15]  E. C. Ashby,et al.  Mechanisms of Grignard reagent addition to ketones , 1974 .

[16]  B. Mannervik,et al.  Mechanism of the Grignard Addition Reaction. XI. Electrode Kinetics and Chemical Reactivity of Grignard Reagents. , 1974 .

[17]  C. Swahn,et al.  MECHANISM OF THE GRIGNARD ADDITION REACTION PART 10, KINETICS AND DEUTERIUM ISOTOPE EFFECTS IN THE REACTION OF ISOBUTYLMAGNESIUM BROMIDE WITH BENZOPHENONE , 1973 .

[18]  J. D. Morrison,et al.  Mechanism of benzophenone reduction with the 2-norbornyl Grignard reagent , 1972 .

[19]  E. C. Ashby,et al.  Direct evidence for the reactive species, and their reaction orders, in the addition reaction of methylmagnesium bromide Grignard to 2-methylbenzophenone , 1971 .

[20]  T. Holm.  The reaction of benzophenone with Grignard reagents: separation of the rate and product determining steps , 1971 .

[21]  L. Ehrenberg,et al.  Mechanism of the Grignard Addition Reaction. VIII. Reaction Rates and Product Distribution for the Reactions of t-Butylmagnesium Chloride and Methylmagnesium Bromide with Substituted Benzophenones. , 1971 .

[22]  F. Bickelhaupt,et al.  Radical formation during reactions of Grignard reagents with quinones , 1970 .

[23]  H. Mosher,et al.  Reaction of the Grignard reagent from neopentyl chloride with benzophenone. Nuclear magnetic resonance study. , 1969 .

[24]  E. C. Ashby,et al.  Composition of Grignard compounds. VI. Nature of association in tetrahydrofuran and diethyl ether solutions , 1969 .

[25]  B. Eistert,et al.  Das verschiedene Verhalten einiger o‐Chinone und des Benzils gegen Dimethyl‐ und Diäthylzink; Analogie zum Verhalten gegen Diazomethan und ‐äthan , 1968 .

[26]  E. Müller,et al.  Anwendung und Grenzen magnetischer Methoden in der Radikalchemie , 1966 .

[27]  Rudolph A. Marcus,et al.  Chemical and Electrochemical Electron-Transfer Theory , 1964 .

[28]  A. Rieker.  Monovalente Reaktionen an Metallorganylen , 1964 .

[29]  K. Maruyama.  The Appearance of Free Radicals during Grignard Reactions , 1964 .

[30]  E. Janzen,et al.  Electron-Transfer Processes. I. The Scope of the Reaction between Carbanions or Nitranions and Unsaturated Electron Acceptors , 1964 .

[31]  H. Mosher,et al.  Relative Rates of Grignard Addition and Reduction Reactions1-3 , 1961 .

[32]  Rudolph A. Marcus,et al.  On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I , 1956 .

[33]  O. Pierce,et al.  The Reducing Action of Grignard Reagents on Fluorinated Carbonyl Compounds1,2 , 1952 .

[34]  C. G. Swain,et al.  The Mechanism of Addition of Grignard Reagents to Ketones , 1951 .

[35]  H. Mosher,et al.  Asymmetric Reductions. II. The Action of (+)-3-Methylpentylmagnesium Chloride on Methyl t-Butyl Ketone , 1950 .

[36]  R. C. Fuson,et al.  THE ADDITION OF METHYLMAGNESIUM IODIDE TO BENZOYLDURENE , 1946 .

[37]  W. V. Evans,et al.  The Electrolysis of n-Propylmagnesium Bromide and Isopropylmagnesium Bromide in Ethyl Ether , 1939 .

[38]  W. V. Evans,et al.  Electrolysis of Methylmagnesium Halides in Ether Solutions , 1936 .

[39]  W. V. Evans,et al.  Electrolysis of Ether Solutions of the Grignard Compound. Isolation, Identification and Quantitative Determination of Anodic Products , 1934 .

[40]  F. Blicke,et al.  THE REDUCING ACTION OF ALIPHATIC GRIGNARD REAGENTS , 1929 .

[41]  E. Zoellner,et al.  THE YIELDS OF SOME GRIGNARD REAGENTS. ALTERNATING PROPERTIES OF NORMAL ALKYL BROMIDES , 1929 .