13898-73-2

Upstream product

• 78-79-5 isoprene 
• 20549-20-6 2-Hydroxymethyl-4-isopropenyl-cyclohexen-⁽¹⁾ 
• 14296-80-1 1,2-dimethylenecyclobutane 
• 22460-53-3 4-isopropenylcyclohexanone 
• 20549-17-1 2-Isobutyloxymethylen-4-isopropenyl-cyclohexan-1-on 
• 20549-18-2 2-Formyl-4-isopropenyl-cyclohexen-⁽¹⁾ 
• 20549-16-0 2-Formyl-4-isopropenyl-cyclohexanon-1 

Downstream Products

• 17092-80-7 m-mentha-1,3(8)-diene 
• 17066-64-7 m-menth-6-ene 
• 16580-24-8 1-isopropyl 3-methyl cyclohexane 
• 99-82-1 Menthane 
• 99-87-6 4-methylisopropylbenzene 
• 54146-37-1 (+/-)-Sylvestrene nitrosochloride 
• 17092-82-9 1,6,8,9-Tetrabromo-m-menthan 

Relevant academic research and scientific papers

Application of molecular dynamics to chromatographic-spectral identification of isomeric products of organic reactions

Isomeric products of [2+4]-cycloaddition reactions can be identified by gas chromatography-mass spectrometry on the basis of their experimental retention parameters and intramolecular vibrational and rotational energies (E) calculated by molecular mechanics for all possible isomers. The Chromatographic parameters change in the opposite direction with respect to E. The proposed approach allows unambiguous identification of four products formed by each of the reactions of butadiene with cyclopentadiene, of isoprene with 2,3-dimethylbutadiene, of cyclopentadiene with isoprene, and dimerization of isoprene and two of the four products formed by the reaction of 1,3-cyclohexadiene with cyclopentadiene. Both structural and steric isomers (exo, endo) can be distinguished. 1998 MAHK "Hayka/Interperiodica".

SPECIFIC ALLYLIC-ALLYLIC COUPLING PROCEDURES EFFECTED BY LIGAND-INDUCED ELIMINATION FROM DI(ALLYLIC)PALLADIUM SPECIES

Bis(allylic)palladium complexes can be induced to undergo reductive elimination by replacement of phosphine ligands in the system with ?-acidic ligands.The product 1,5-dienes, formed in high yield, are predominantly the 'head-to-head' coupled isomers.The bis(allylic)palladium intermediates may be formed by addition of an allylic Grignard or trialkyl(allylic)tin reagent to an(η3-allyl)palladium chloride complex, or by 1,3-diene condensation.The latter process leads to cyclodimerization, 'unusual' for palladium catalysed reactions.

On the mechanism of the nickel-catalysed regioselective cyclodimerization of isoprene

A study of various Ni-ligand catalysed oligomerizations of isoprene has shown that with π-acidic P ligands the selectivity to cyclodimers amount to 97%. A new type of ligand is introduced, viz. fluoroalkyl phosphites having π-acceptor properties comparable to those of, e.g. PCl3. With tris(hexafluoroisopropyl) phosphite the main product is 1,4-dimethy1-4-vinylcyclohexene. A detailed explanation based on a two-step mechanism is given. As to the first step, for a series of ligands having similar steric properties the changes in product distribution as a function of the electronic ligand parameter are explained in terms of a gradual change in HOMO-LUMO interactions between Ni and the olefins, with strong π-acidic ligands promoting the head-to-head coupling of the isoprene molecules. The second step, involving reductive elimination of a cyclodimer from the metal, shows an increasing selectivity towards substituted cyclohexenes for the head-to-head and tail-to-tail intermediates with increasing π-acidity of the ligand. The qualitative orbital treatment presented as an explanation is also applicable to reactions found for other metallacyclopentanes.