84224-52-2

Upstream product

• 611-70-1 phenyl isopropyl ketone 
• 32770-78-8 2-methyl-1-phenylpropan-1-one hydrazone 
• 84224-54-4 (Z)-2,5-dimethyl-3,4-diphenyl-3-hexene 

Relevant academic research and scientific papers

A heterobimetallic complex featuring a Ti-Co multiple bond and its application to the reductive coupling of ketones to alkenes

To explore metal-metal multiple bonds between first row transition metals, Ti/Co complexes supported by two phosphinoamide ligands have been synthesized and characterized. The Ti metalloligand Cl2Ti(XylNPiPr2)2 (1) was treated with CoI2 under reducing conditions, permitting isolation of the Ti/Co complex [(μ-Cl)Ti(XylNPiPr2)2CoI]2 (2). One electron reduction of complex 2 affords ClTi(XylNPiPr2)2CoPMe3 (3), which features a metal-metal triple bond and an unprecedentedly short Ti-Co distance of 2.0236(9) ?. This complex is shown to promote the McMurry coupling reaction of aryl ketones into alkenes, with concomitant formation of the tetranuclear complex [Ti(μ3-O)(NXylPiPr2)2CoI]2 (4). A cooperative mechanism involving bimetallic C=O bond activation and a cobalt carbene intermediate is proposed.

Reaction of ketone hydrazones with diselenium dihalides: Simple synthesis of Δ3-1,3,4-selenadiazolines and 2,5-diarylselenophenes

Sterically congested cis- and trans-Δ3-1,3,4- selenadiazolines were isolated by one-pot reactions of ketone hydrazones with diselenium dibromide, which suggested the in situ formation of selone and diazoalkane intermediates. The thermolysis of these compounds gave symmetrical olefins, whereas oxidation afforded the corresponding azines. The reaction of acetophenone hydrazones with diselenium dibromide afforded 2,5- diarylselenophenes in moderate yields. The reaction proceeded through selone intermediates.

Pinacol reduction-cum-rearrangement. A re-examination of the reduction of aryl alkyl ketones by zinc-aluminum chloride

Reduction of alkyl phenyl ketones by zinc and aluminum chloride in acetonitrile results in pinacol condensation followed by rearrangement. The phenyl group migrates in every instance.

Radical-Stabilization-Energy - the MMEVBH Force Field

Making use of the VB method of Malrieu et al. a force field has been developed, which allows to calculate heats of formation of hydrocarbons (conjugated and non-conjugated olefins, radicals and diradicals) with high accuracy.With this method radical stabilization energies (RSE) for a great number of delocalized radicals are calculated and compared with experimental values, derived from shock-tube measurements of dissociation energies or from rotational barriers of substituted olefins.A detailed analysis of the RSE with respect to structure, substituents, strain, and aromaticity is presented. - Key Words: Resonance energy / Heats of formation / Single pulse shock tube / Intrisic rotational barrier

Stereochemistry and Side Products in Reductive Coupling of Alkyl Aryl Ketones to 1,2-Dialkyl-1,2-diarylethylenes

The reductive coupling of alkyl aryl ketones 1 - 3 and 7 - 9 by low valent titanium salts yields predominantly the (Z)-isomers of 11 - 13 and 17 - 19.Evidence is given by 1H NMR spectroscopy.This behavior can be explained by ?-complex formation of phenyl rings with Ti0.Severe steric hindrance, however, favors the (E)-isomers ( -> 14 and 15).Donor groups in p-position, particularly, give increasing amounts of pinacols, 23 - 27, which undergo rearrangement to the ketones 28 and 29.

HYDROGENATION AND OTHER SIDE-REACTIONS DURING THE REDUCTIVE COUPLING OF KETONES WITH LOW-VALENT TITANIUM (McMurry Synthesis).

Active titanium slurries, effective in the McMurry coupling reaction of ketones to olefins, are also hydrogenation agents.Sometimes they also promote isomerisation of the originally formed olefin as well as aldol type and pinacol type condensations under special reaction conditions. The most prominent factors promoting hydrogenation are the use of high ratios LiAlH4 : TiCl3 and low temperatures in the formation of the low-valent titanium species.