72089-90-8

Upstream product

• 86423-34-9 <1,1-(2)H2>octyl bromide 
• 1449563-33-0 1-methyl-d₃-heptyl phenyl ether 

Relevant academic research and scientific papers

Hydrogen elimination in the thermal decomposition of iridium-n-alkyl complexes

Iridium complexes L2Ir(CO)X (L = PPh3, P(p-FC6H5)3, CO; X = Cl, I) and L2Ir(CO)X3 (L = PPh3, P(p-FC6H5)3; X = Cl, I) were allowed to react with CH3(CH2)6CD2Li and CH3(CH2)5CD2CH2Li to form the respective n-octyliridium complexes.Thermal decomposition of these complexes yielded solely D2C=CH(CH2)5CH3 and CHD2(CH2)6CH3 from the 1,1-dideuteriooctyliridium complexes and H2C=CD(CH2)5CH3 and CDH2CD2(CH2)5CH3 from the 2,2-dideuteriooctyliridium complexes.Thus, productive decomposition of the n-alkyliridium complexes occurred exclusively by a β-hydrogen elimination mechanism.This is in accord with the previously reported reaction of (PPh3)2Ir(CO)Cl with CH3(CH2)5CD2CH2Li and demonstrates that changing the steric and electronic nature of the donor ligands on the iridium is insufficient to induce productive decomposition by α-hydrogen elimination.Keywords: Iridium; Alkyls; Elimination reactions

Reaction pathways and energetics of etheric C-O bond cleavage catalyzed by lanthanide triflates

Efficient and selective cleavage of etheric C-O bonds is crucial for converting biomass into platform chemicals and liquid transportation fuels. In this contribution, computational methods at the DFT B3LYP level of theory are employed to understand the efficacy of lanthanide triflate catalysts (Ln(OTf)3, Ln = La, Ce, Sm, Gd, Yb, and Lu) in cleaving etheric C-O bonds. In agreement with experiment, the calculations indicate that the reaction pathway for C-O cleavage occurs via a C-H → O-H proton transfer in concert with weakening of the C-O bond of the coordinated ether substrate to ultimately yield a coordinated alkenol. The activation energy for this process falls as the lanthanide ionic radius decreases, reflecting enhanced metal ion electrophilicity. Details of the reaction mechanism for Yb(OTf) 3-catalyzed ring opening are explored in depth, and for 1-methyl-d3-butyl phenyl ether, the computed primary kinetic isotope effect of 2.4 is in excellent agreement with experiment (2.7), confirming that etheric ring-opening pathway involves proton transfer from the methyl group alpha to the etheric oxygen atom, which is activated by the electrophilic lanthanide ion. Calculations of the catalytic pathway using eight different ether substrates indicate that the more rapid cleavage of acyclic versus cyclic ethers is largely due to entropic effects, with the former C-O bond scission processes increasing the degrees of freedom/particles as the transition state is approached.

Thermal decomposition of palladium-n-alkyl complexes by hydrogen elimination

1,1-Dideuterio-1-octyllithium and 2,2-dideuterio-1-octyllithium were allowed to react with palladium complexes of the type L2PdCl2 and L2PdCl4 (L = PPh3, py; L2 = bpy, dppe) to form the respective straight-chain alkylpalladate complexes.These complexes were then allowed to decompose thermally and the resulting 1-octene was analyzed.The 1,1-dilabeled alkyl ligand produced 1,1-dideuterio-1-octene, while the 2,2-dilabeled ligand formed 2-deuterio-1-octene.These products indicate that α-hydrogen removal, rather than ?-hydrogen removal, is the productive decomposition mode for these n-alkylpalladate complexes. Keywords: Palladium; Alkyl; Mechanism; Decomposition; Alkylpalladate; Beta-elimination

Photochemistry of alkyl halides. 12. Bromides vs Iodides

Conditions have been developed for optimizing ionic photobehavior material balances from alkyl bromides. Hydroxide ion as an efficient for the byproduct HBr while giving minimal competing photoreduction via electron transfer to the alkyl bomide. The photobehavior of bromides 1, 11, 25, and 40 has examined and with that of the corresponding iodides 2, 12, 26, 41 under conditions. In each case, the bromide higher yields of products derived from out of cage radical intermidiates than the corresponding iodide. However, with the 2-norbornyl bromides 11 and iodides 12 showed that, of products not formed from the out of cage 2-norbornyl radical 13, the bromides 11 gave a higher percentage of products from the ionic intermediates 15 and 16 than did the iodides. Thus, electron transfer within the radical pair 14 is apparently more rapid for bromides than iodides, as expected on the of the relative electronegativities of bromine iodine. It is that the substantially higher yields of out of radical products from alkyl bromides may be due in to formation of the radical pair with greater excess energy, which results in more rapid escape from the cage. The epimeric 2-norbornyl bromides 11x and 11n underwent no detectable interconversion and afforded somewhat different product ratios. The more hindered epimer 11n underwent conversion to products at a slower than 11x. By contrast, 12x and 12n underwent substantial interconversion via out of transfer of an iodine atom from iodide 12 to radical 13. Epimerization was significantly attenuated in the more viscous solvent tert-butyl alcohol.