Alkali metal adducts of benzophenone azine. I. The sodium and potassium adducts

1970 ◽  
Vol 48 (12) ◽  
pp. 1904-1914 ◽  
Author(s):  
E. J. MacPherson ◽  
James G. Smith
Keyword(s):  
Electron Transfer ◽  
Alkali Metal ◽  
Methyl Iodide ◽  
Chemical Reactions ◽  
Methyl Benzoate ◽  
Ethyl Chloroformate ◽  
Methylene Iodide ◽  
Benzylic Carbon ◽  
Metal Adducts ◽  
Sodium And Potassium

Contrary to previous reports, the reaction between benzophenone azine and sodium or potassium produces an adduct containing 2 g-atoms of alkali metal per mole of azine. The chemical reactions of this dianion have been examined and a 1,2-dianionic structure is most consistent with its chemical behavior.Treatment of the adduct with methyl iodide, 1,3-dibromopropane, or 1,4-dibromobutane results in alkylation on the benzylic carbon and adjacent nitrogen. However, regeneration of benzophenone azine occurred with methylene iodide, 1,2-dibromoethane, and benzyl chloride.With ethyl chloroformate, reaction occurred at the carbanionic center to form an intermediate unstable anion. This anion could be protonated or alkylated but if allowed to stand, decomposed to diphenyldiazomethane and the anion of ethyl diphenylacetate.Reaction of the benzophenone azine dianion with methyl benzoate is quite complicated and leads to substantial amounts of benzophenone azine being regenerated by electron transfer. That portion of the dianion which is not converted to azine reacts with methyl benzoate to produce the anion of α-benzamido- α,α-diphenylacetophenone.The possibility that an adduct of N-benzoyl benzophenone imine is an intermediate in this last reaction is examined and rejected.

scholarly journals THE REDUCTIVE DIMERIZATION OF N-BENZYLIDENE ANILINE

1966 ◽  
Vol 44 (21) ◽  
pp. 2497-2502 ◽  
Author(s):  
James G. Smith ◽  
C. Doreen Veach
Keyword(s):  
Alkali Metal ◽  
Lithium Metal ◽  
Reaction Products ◽  
Polar Solvents ◽  
Reductive Dimerization ◽  
Nonpolar Solvents ◽  
Diastereomeric Mixture ◽  
Metal Adducts ◽  
Sodium And Potassium

The formation of alkali metal adducts of N-benzylidene aniline in several inert solvents is studied by protonolysis of the adducts and analysis of the reaction products, the diastereomeric N,N′,1,2-tetraphenylethylenediamines. With sodium and potassium metal in polar solvents, the product is predominantly the dd,ll diamine. With lithium metal or with solvents of low polarity, the product contains approximately equal quantities of the two diastereomers.It is demonstrated that the initially formed diastereomeric mixture generally contains appreciable amounts of the meso isomer. In polar solvents with sodium, isomerization to the stable dd,ll diastereomer occurs. However, with lithium or with sodium in nonpolar solvents, the isomerization does not occur. The reasons for the preponderance of the dd,ll-disodio compound in the equilibrating systems are discussed.

Electron transfer reactions from alkali metal surfaces to (±) and (S)-(−)-1,3-dimethoxy-1,1-diphenylbutane. Studies on 1,3-elimination

1984 ◽  
Vol 62 (11) ◽  
pp. 2464-2470 ◽  
Author(s):  
Harry M. Walborsky ◽  
Martha Pass Murari
Keyword(s):  
Electron Transfer ◽  
Alkali Metal ◽  
Charge Radius ◽  
Alkali Metals ◽  
Transfer Reactions ◽  
Lithium Metal ◽  
Sodium Metal ◽  
Pure Product ◽  
Optically Pure ◽  
Sodium And Potassium

The 1,3-elimination of methoxide by carbanions generated from the reaction of (±)-1,3-dimethoxy-1,1-diphenylbutane with the alkali metals, lithium, sodium, and potassium, in various solvents was studied to determine the significance of cation–methoxyl coordination due to decreasing charge/radius ratio of the cations and also the cation complexing ability of the solvent. The stereochemistry of cyclization in the reaction of (S)-(−)-1,3-dimethoxy-1,1-diphenylbutane with lithium metal in tetrahydrofuran and with sodium metal in methylcyclohexane to yield 1-methyl-2,2-diphenylcyclopropane was determined. The reaction proceeded by an intramolecular SN2-type displacement to yield optically pure product of inverted configuration.

Alkali metal adducts of benzophenone azine. II. The lithium adduct

1970 ◽  
Vol 48 (12) ◽  
pp. 1915-1918 ◽  
Author(s):  
E. J. MacPherson ◽  
James G. Smith
Keyword(s):  
Alkali Metal ◽  
Alkali Metals ◽  
Reducing Power ◽  
The Other ◽  
Organolithium Compounds ◽  
Metal Adducts ◽  
Sodium And Potassium

The behavior of benzophenone azine towards lithium has been studied. Unlike sodium and potassium, lithium effected extensive reduction and cleavage of benzophenone azine; the reaction product being benzhydryl amine. By limiting the amount of lithium to 2 g-atoms per mole of azine, the reaction product was shown to be N-lithiobenzophenone imine on the basis of its chemical behavior.Two reasons are advanced to explain the behavior of lithium in contrast to that of sodium or potassium. One explanation relies upon the greater reducing power of lithium compared with the other two alkali metals. The other relies upon the tendency of organolithium compounds to associate via formation of multi-center bonds.

Thermally Induced Electron Transfer in a CsCoFe Prussian Blue Derivative: The Specific Role of the Alkali-Metal Ion

2004 ◽  
Vol 116 (28) ◽  
pp. 3814-3817 ◽  
Author(s):  
Anne Bleuzen ◽  
Virginie Escax ◽  
Alban Ferrier ◽  
Françoise Villain ◽  
Michel Verdaguer ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Alkali Metal ◽  
Prussian Blue ◽  
Metal Ion ◽  
Specific Role ◽  
Alkali Metal Ion ◽  
Thermally Induced

The Hot Iodine Substitution Reaction in Gaseous Methyl Iodide

1964 ◽  
Vol 2 (3) ◽  
Author(s):  
R.J. Cross ◽  
R.L. Wolfgang
Keyword(s):  
Methyl Iodide ◽  
Chemical Reactions ◽  
Substitution Reaction ◽  
Emission Process ◽  
Atomic Iodine

SummaryChemical reactions of hot atomic iodine formed by recoil from a photoneutron emission process, (γ, n) have been studied. The yield of the hot substitution,

Intracluster Electron Transfer and Reactions in Alkali Metal−Methacrylate Clusters

2001 ◽  
Vol 105 (42) ◽  
pp. 9649-9658 ◽  
Author(s):  
Hironori Tsunoyama ◽  
Keijiro Ohshimo ◽  
Fuminori Misaizu ◽  
Koichi Ohno
Keyword(s):  
Electron Transfer ◽  
Alkali Metal

scholarly journals Resonant catalysis of thermally activated chemical reactions with vibrational polaritons

2019 ◽  
Vol 10 (1) ◽  
Author(s):  
Jorge A. Campos-Gonzalez-Angulo ◽  
Raphael F. Ribeiro ◽  
Joel Yuen-Zhou
Keyword(s):  
Electron Transfer ◽  
Chemical Kinetics ◽  
Chemical Reactions ◽  
Cavity Mode ◽  
Resonant Cavity ◽  
Quantum States ◽  
Transfer Model ◽  
Dark State ◽  
Thermally Activated ◽  
Two Hybrid

Abstract Interaction between light and matter results in new quantum states whose energetics can modify chemical kinetics. In the regime of ensemble vibrational strong coupling (VSC), a macroscopic number $$N$$ N of molecular transitions couple to each resonant cavity mode, yielding two hybrid light–matter (polariton) modes and a reservoir of $$N-1$$ N − 1 dark states whose chemical dynamics are essentially those of the bare molecules. This fact is seemingly in opposition to the recently reported modification of thermally activated ground electronic state reactions under VSC. Here we provide a VSC Marcus–Levich–Jortner electron transfer model that potentially addresses this paradox: although entropy favors the transit through dark-state channels, the chemical kinetics can be dictated by a few polaritonic channels with smaller activation energies. The effects of catalytic VSC are maximal at light–matter resonance, in agreement with experimental observations.

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