30922-78-2

Upstream product

• 768-32-1 trimethylphenylsilane 
• 62268-73-9 diphenylcarbene 
• 117750-38-6 C₁₁H₁₅^(1-) 
• 177552-58-8 quadricyclane anion 
• 177552-59-9 2-quadricyclanide anion 
• 71-43-2 benzene 
• 28760-98-7 C₁₂⁽¹³⁾CH₁₁^(1-) 
• 18802-87-4 diphenylmethanide 
• 108-86-1 bromobenzene 

Downstream Products

• 109662-36-4 (1-Cyclohexylidene-2,2,3,3,3-pentafluoro-propyl)-benzene 
• 109662-32-0 (2-Methyl-1-pentafluoroethyl-propenyl)-benzene 
• 109662-33-1 (2,2,3,3,4,4,4-Heptafluoro-1-isopropylidene-butyl)-benzene 
• 71-43-2 benzene 
• 13133-62-5 thiophenolate 
• 35542-25-7 thiobenzoate anion 
• 201230-82-2 carbon monoxide 
• 78944-74-8 Benzoyl radical 
• 177552-58-8 quadricyclane anion 
• 177552-59-9 2-quadricyclanide anion 
• 109662-35-3 (1-Cyclohexylidene-2,2,2-trifluoro-ethyl)-benzene 
• 125254-29-7 naphthalene anion radical 

Relevant academic research and scientific papers

Relative Acidities of Water and Methanol and the Stabilities of the Dimer Anions

The difference between ΔH0acid of H2O and CH3OH was directly measured to be 9.6 +/- 0.2 kcal/mol at 600 K by variable-temperature pulsed high pressure mass spectrometry.This result defines ΔH0acid(CH3OH) at 300 K as 381.6 +/- 0.7 kcal/mol and also confirms published values of EA(CH3O) and ΔH0D(CH3O-H), H2O was also used as a reference to measure ΔH0acid(C6H6) as 400.7 +/- 0.8 kcal/mol at 600 K.The dissociation energies of the hydrogen-bonded dimers OH-*H2O (26.8 kcal/mol), CH3O-*H2O (23.9 kcal/mol), and CH3O-*CH3OH (28.8 kcal/mol) were also measured.The former two are found to be in very good agreement with pu blished ab initio results.

Reactivity and thermochemistry of quadricyclane in the gas phase

The gas-phase acidity of quadricyclane C7H8 has been determined using a flowing after-glow selected ion flow tube at room temperature. Measurements of forward and reserve rate constants for the proton transfer reaction B- + C7H8 ? C7H7- + BH where BH = NH3, CH3NH2 and C6H6 give ΔacidG300(C7H8) = 394.7±0.8 kcal/mol and ΔacidH300(C7H8) = 403.0±1.1 kcal/mol. Combining this value with the electron affinity, 0.868±0.006 eV, of the quadricyclyl radical, gives 109.4±1.3 kcal/mol for the C-H bond dissociation energy of quadricyclane at Cl. Reactions of quadricyclane ion with various reagents have been studied, and branching ratios of product channels have been determined. These results along with ab initio calculations and a companion photoelectron spectroscopy study, indicate that there are two isomers of quadricyclane ion which have similar energies. The gas-phase acidity of quadricyclane, C7H8, has been determined using a flowing afterglow-selected ion flow tube at room temperature. Measurements of forward and reverse rate constants for the proton transfer reactions B- + C7H8 ? C7H7- + BH where BH = NH3, CH3NH2, and C6H6 give Δ(acid)G300(C7H8) = 394.7 ± 0.8 kcal/mol and Δ(acid)H300(C7H8) = 403.0 ± 1.1 kcal/mol. Combining this value with the electron affinity, 0.868 ± 0.006 eV, of the quadricyclyl radical, gives 109.4 ± 1.3 kcal/mol for the C-H bond dissociation energy of quadricyclane at C1. Reactions of quadricyclanide ion with various reagents have been studied, and branching ratios of product channels have been determined. These results, along with ab initio calculations and a companion photoelectron spectroscopy study, indicate that there are two isomers of quadricyclanide ion which have similar energies.

Collision-induced Dissociations of Substituted Benzyl Negative Ions in the Gas Phase. The Elimination of C4H4

The major collision-induced dissociation of PhEt2 involve the losses of H, H2, and CH4.Loss of H occurs from the phenyl ring, H2 is eliminated principally by the process while methane is lost by the stepwise process in which t

Generation, Thermodynamics, and Chemistry of the Diphenylcarbene Anion Radical (Ph2C.-)

Dissociative electron attachment with Ph2C=N produced Ph2C.- (m/z 166).The reactions of Ph2C.- with potential proton donors of known gas-phase acidity were used to bracket PA(Ph2C.-) = 380 +/- 2 kcal mol-1 from which ΔHf0(Ph2C.-) = 81.8 +/- 2 kcal mol-1 was calculated.The reactions of Ph2C.- with CH3OH and C2H5OH proceeded with major and minor amounts, respectively, of a H2.+-transfer channel, forming Ph2CH2, RCHO, and an electron.The kinetic nucleophilicity of Ph2C.- in SN2 displacement reactions with CH3X and C2H5X molecules was shown to be medium, which requires a significant intrinsic barrier in these reaction.The reactions of Ph2C.- with various aldehydes, ketones, and esters were fast and established two principal product-forming channels: (1) H+ transfer if the neutral reactant contains activated C-H bonds and (2) carbonyl addition followed by radical β-fragmentation of one of the groups originally attached to the carbonyl carbon.The order for the ease of radical β-fragmentation in the tetrahedral intermediates was RO > alkyl >> H, and CO2CH3 > CH3.Since the reactions of Ph2C.- with the simple esters HCO2CH3 and CH3CO2CH3 were fast, it should now be possible to examine the reactions of carbonyl-containing organic molecules, which are expected to react slower than these esters and obtain their relative reactivities.

Gas-Phase Reactions of Anions with Substituted Silanes

The gas-phase reactions of fluoride, amide, hydroxide, and methoxide ions with a variety of substituted silanes have been studied by the flowing afterglow technique.Fluoride reacts readily with trimethylsilyl derivatives to displace benzyl, alkenyl, and alkynyl anions.These reactions have also been used to generate specific structural isomers (CH3CC- and CH2C=C=CH-).Anions more basic than phenide ion cannot be produced in this manner, and their parent trimethylsilanes interact with fluoride by more complex mechanisms.Amide, hydroxide, and methoxide ions react with substituted trimethylsilanes by both displacement and proton abstraction whenever an acidic hydrogen is present; in the absence of displaceable groups and acidic hydrogen, the reactions of amide, hydroxide, and methoxide parallel those of fluoride ion.