17009-84-6

Upstream product

• 111-43-3 Dipropyl ether 
• 17009-83-5 protonated diethyl ether 
• 103-65-1 n-propylbenzene radical cation 
• 68706-39-8 protonated 3,3-dimethyl butanone 
• 64725-64-0 cyclopentanone; protonated form 
• 98-82-8 cumene radical cation 
• 108-88-3 toluene radical cation 
• 352-70-5 m-fluorotoluene cation radical 
• 64725-65-1 cyclohexanone; protonated form 
• 39922-13-9 1-Phenyl-ethylidene-oxonium 

Downstream Products

• 111-43-3 Dipropyl ether 
• 81971-27-9 protonated tert-butyl methyl ether 
• 18639-86-6 2,4-dimethyl-pentan-3-one; protonated form 
• 39922-13-9 1-Phenyl-ethylidene-oxonium 
• 64725-64-0 cyclopentanone; protonated form 
• 17009-85-7 Dibutyl-oxonium 
• 70058-20-7 1-Cyclopropyl-ethylidene-oxonium 
• 64725-65-1 cyclohexanone; protonated form 

Relevant academic research and scientific papers

RING SIZE EFFECTS ON THE GAS PHASE PROTONATION OF CYCLIC KETONES

Experimental proton affinities of cyclic ketones are determined showing evidence for a larger strain energy in protonated vs. neutral cyclic ketones.

Carbon-Hydrogen Bond Dissociation Energies in Alkylbenzenes. Proton Affinities of the Radicals and the Absolute Proton Affinity Scale

Rate constants (k) were measured for proton-transfer reactions from alkylbenzene ions RH+ to a series of reference bases B, i.e., RH+ + B -> BH+ + R*.For exothermic reactions (ΔH -1.For example, the reaction C6H5CH3+ + B -> BH+ + C6H5CH2* is fast (reaction efficiency = k/kcol >/= 0.5) when B = MeO-t-Bu or stronger bases, but k/kcol is significantly smaller when B is n-Pr2O or weaker bases.From the falloff curve of reaction efficiency vs.PA(B), we find PA(n-Pr2O) = PA(C6H5CH2*) + 0.8 kcal mol-1 = 200.0 kcal mol-1.Since PA(C6H5CH2*) is obtained from known thermochemical data, this relation defines the absolute PA of n-Pr2O.Through a ladder of known PA, we then obtain PA(i-C4H8) = 186.8 kcal mol-1; we also obtain the absolute PAs of other oxygen bases.Falloff curves of reaction efficiencies of 3-FC6H4CH3+, C6H5C2H5+, C6H5-n-C3H7+, and C6H5-i-C3H7+ with these reference bases give then the following PAs of R* and R-H bond dissociation energies (Do) (all in kcal mol-1) as R*, PA(R*), Do(R-H): 3-FC6H4CH2*, 197.2, 89.4; , 197.9, 86.2; , 199.1, 86.1; , 199.6, 86.1.In similar manner, rate constants for H+ transfer from C6H5NH2+ to reference pyridines and amines yield PA(C6H5NH*) = 221.5 and Do(C6H5NH-H) = 85.1 kcal mol-1 (1 kcal mol-1 = 4.18 kJ mol-1).

Oxonium Ions. Solvation by Single Acetonitrile Molecules in the Gas Phase and by Bulk Solvents

The standard free energy of formation of gaseous complexes between monoprotonic oxonium ions and acetonitrile have been obtained by using the ion cyclotron resonance equilibrium constant method for exchange of acetonitrile between the ions.The results show that the "solvation" by a single molecule of acetonitrile in the gas phase reproduces the important diverse effects of molecular structure on oxonium ion solvation by bulk water.It is estimated from the present results that the effects of solvation by bulk water are only about three times as great as the corresponding effects of "solvation" by a single water molecule in the gas phase.Internal charge delocalization from the protonic site of the oxonium ions may be reversed by differential solvation, both with single H-bonding molecules in the gas phase and with bulk solvent.Further evidence for the site of preffered protonation of esters and amides is provided.