64198-20-5

Upstream product

• 4786-20-3 but-2-enenitrile 
• 626-62-0 Cyclohexyl iodide 
• 76-63-1 allytriphenyltin 
• 41320-40-5 <<(methylthio)thiocarbonyl>oxy>cyclohexane 
• 1190-76-7 (Z)-2-butenenitrile 
• 24371-94-6 cyclohexylmercury chloride 
• 4786-20-3 crotononitrile 
• 108-85-0 1-bromocyclohexane 
• 119-61-9 benzophenone 
• 110-82-7 cyclohexane 

Relevant academic research and scientific papers

Hydrocarbon activation. Synthesis of β-cycloalkyl (Di)nitriles through photosensitized conjugate radical addition

Photoinduced hydrogen abstraction from aliphatic cyclic hydrocarbons (C5 to C7, C12, as well as adamantane) by triplet aromatic ketones in the presence of α,β-unsaturated (di)nitriles offers a straightforward entry to the corresponding alkylated (di)nitriles via the alkyl radicals. Yields are moderate to good depending on the olefins structure (substitution in β slows down the addition to mononitriles, but with α,α-dinitriles electronic activation allows efficient alkylation also of β,β-disubstituted substrates). A tandem alkylation - cyclization process has been obtained with (1-methylpent-4-enylidene)malononitrile.

A New Coupling Reaction of Alkyl Iodides with Electron Deficient Alkenes Nickel Boride (cat.) - Borohydride Exchange Resin in Methanol

The radical addition reaction of alkyl iodides with α,β-unsaturated esters, nitriles, and ketones proceeds in moderate to excellent yields (50-95%) using Ni(OAc)2 (0.05-0.2 equiv) - BER (3-5 equiv) in methanol in 1-9 h at room temperature or at 65°C. Nickel boride on borohydride exchange resin (BER) is a good alternative reagent to tributyltin hydride for the coupling of alkyl iodides with the electron deficient alkenes in methanol. Compared with tributyltin hydride method, this method has an advantage of simple workup, since nickel boride - BER can be removed readily by filtration.

BIS(TRI-n-BUTYLSTANNYL)BENZOPINACOLATE: PREPARATION AND USE AS A MEDIATOR OF INTERMOLECULAR FREE RADICAL REACTIONS

Bis(tri-n-butylstannyl)benzopinacolinate (2) serves as a thermal source of tri-n-butylstannyl radicals and mediates intermolecular coupling of selected alkyl halides to O-benzylformaldoxime and electron deficient olefins.A free radical non-chain mechanism is proposed for these reactions.

Dimeric Metal Complexes as Mediator for Radical C-C Bond-Forming Reactions

Irradiation of dicarbonyl(η5-cyclopentadienyl)iron dimer 1 or decacarbonyldimanganese (2) in the presence of alkyl halides leads to C-centered radicals which can be trapped by alkenes and yields saturated and/or unsaturated addition products.Carbon radicals are generated via halogen abstraction by the initially formed metal-centered radicals resulting from homolysis of the metal-metal bond of dimeric mediators 1 and 2.No reaction occurs using octacarbonyl dicobalt (3).

Approximate rate constants for the addition of alkyl radicals to allylstannanes

Rate constants for the addition of alkyl radicals to allylstannanes lie in the range of 104-105 M-1 s-1 at 50-80°C.

TRIS(TRIMETHYLSILYL)SILANE AS MEDIATOR IN ORGANIC SYNTHESIS VIA RADICALS

Silane 3 is an effective mediator in organic synthesis via radicals.Reactions with this silane give smaller amounts of unwanted reduction products than reactions with toxic stannanes.

Selectivity of prim., sec. and tert. Alkyl Radicals in Addition Reactions

In reductions of alkylmercuric salts 4 and 5 with NaBH4 alkyl radicals 1 are formed as intermediates.The selectivity of prim., sec. and tert. radicals in addition reactions with alkenes 6-12 can be measured by this "mercury-method", because adduct radicals 13-19 form products 20-26 quantitatively.Dimerization, disproportionation, polymerization, trapping of oxygen and β-bond cleavage don't compete with the hydrogen transfer to 13-19.The measurements show, that alkyl radicals 1 are nucleophiles and that their selectivity increases in going from prim. to sec. and tert. radicals (Table 1).As long as steric effects are not important, reactivities and selectivities can be described by frontier molecular orbital theory.As a consequence of this theory selectivity increases with increasing reactivity.