2154-50-9

Upstream product

• 60-29-7 diethyl ether 
• 109-95-5 ethyl nitrite 
• 383-63-1 ethyl trifluoroacetate, 
• 62268-73-9 diphenylcarbene 
• 74586-02-0 phenylnitrene anion radical 
• 2143-58-0 methylperoxy radical 
• 3170-61-4 ethylperoxy radical 
• 2143-59-1 Cyclohexylperoxy radical 
• 27974-64-7 neopentylperoxy radical 
• 4599-48-8 allylperoxyl radical 
• 107247-59-6 (ethoxy)oxo(5,10,15,20-(tetra-4-methylphenyl)porphinato)molybdenum(V) 

Downstream Products

• 60-29-7 diethyl ether 
• 625-58-1 ethyl nitrate 
• 109-95-5 ethyl nitrite 
• 75-07-0 acetaldehyde 

Relevant academic research and scientific papers

Photochemical Epoxidation of Olefins with Molecular Oxygen Activated by Oxo(tetra-p-tolylporphinato)molybdenum(V)

Photochemical epoxidation of olefins was catalyzed by a molybdenum porphyrin in benzene under aerobic conditions.The catalytic reaction rate was somewhat lower than that observed for the similar reactions catalyzed by the corresponding niobium complex.A reaction mechanism, involving cooperative interaction of an olefin and dioxygen with the molybdenum(V) species, was postulated.

Kinetics of the Reaction between Ethylperoxy Radicals and Nitric Oxide

The kinetic of the C2H5O2 + NO -> C2O5O + NO2 reaction is examined by two real-time techniques.NO consumption and NO2 formation are measured using transient diode laser absorption, whereas ethylperoxy loss and ethylnitrite formation are monitored by time-resolved UV spectrometry.Simultaneous fits of the NO and NO2 concentration versus time profiles yield rate constants consistent with the results of the C2H5O2 and C2H5ONO measurements.The combined data yield a rate constant of k5 = (3.1-1.0+1.5)E-12 e (330+/-11)/T cm3 s-1 over the 220-355 K temperature range.The small negative temperature dependence is consistent with the accepted mechanism of the reaction proceeding through a C2H5O2NO adduct.

Kinetics of the cross reactions of CH3O2 and C2H5O2 radicals with selected peroxy radicals

The kinetics of the reactions of selected peroxy radicals (RO2) with CH3O2 and with C2H5O2 have been investigated using two techniques: excimer-laser photolysis and conventional flash photolysis, both coupled with UV absorption spectrometry. Radicals were generated either by photolysis of molecular chlorine in the presence of suitable hydrocarbons or by photolysis of the appropriate alkyl chloride. All such cross-reaction kinetics were investigated at 760 Torr total pressure and room temperature except for the reaction of the allylperoxy radical with CH3O2, for which the rate constant was determined between 291 and 423 K, resulting in the following rate expression: k15 = (2.8 ± 0.7) × 10-13 exp[(515 ± 75)/T] cm3 molecule-1 s-1. Values of (2.0 ± 0.5) × 10-13, (1.5 ± 0.5) × 10-12, (9.0 ± 0.15) × 10-14, -12, (2.5 ± 0.5) × 10-12, and (8.2 ± 0.6) × 10-12 (units of cm3 molecule-1 s-1) have been obtained for the reactions of CH3O2 radicals with C2H5O2, neo-C5H11O2, c-C6H11O2, C6H5CH2O2, CH2ClO2, and CH3C(O)O2, respectively, and (1.0 ± 0.3) × 10-12, (5.6 ± 0.8) × 10-13, (4.0 ± 0.2) × 10-14, and (1.0 ± 0.3) × 10-11 (units of cm3 molecule-1 s-1) for the reactions of C2H5O2 with CH2=CHCH2O2, neo-C5H11O2, c-C6H11O2, and CH3C(O)O2 radicals, respectively. These rate constants were obtained by numerical simulations of the complete reaction mechanisms, which were deduced from the known mechanisms of the corresponding peroxy radical self-reactions. A systematic analysis of propagation of errors was carried out for each reaction to quantify the sensitivity of the cross-reaction rate constant to the parameters used in kinetic simulations. The rate constant for a given cross reaction is generally found to be between the rate constants for the self-reactions of RO2 and CH3O2 (or C2H5O2). However, when the RO2 self-reaction is fast, the cross reaction with CH3O2 (or C2H5O2) is also fast, with similar rate constants for both reactions, suggesting that these particular peroxy radical cross reactions can play a significant role in the chemistry of hydrocarbon oxidation processes in the troposphere and in low-temperature combustion. Relationships between cross-reaction and self-reaction rate constants are suggested.

Photodissociation of Alkyl Nitrites in a Molecular Beam. Primary and Secondary Reactions

The translational energy distributions P(ET) for the 248-nm photodissociation products (NO + RO) of isopropyl nitrite and tert-butyl nitrite have been measured with a molecular beam time-of-flight (TOF) apparatus.Previous experiments with methyl nitrite and ethyl nitrite have been repeated with higher resolution.The average photofragment translation energies of these four alkyl nitrites are in good agreement with those predicted by an impulsive model that treats the NO as a rigid fragment and the alkoxy radical as a soft fragment.Hence, and in contrast to the vibrational predissociation on the S1 potential energy surface, S2 dissociation is direct and involves no significant "vibrational-translational" coupling between the reaction coordinate rO-N and the rN=O coordinate.The width of the experimental P(ET) distributions decreases with increasing size of the alkoxy substituent.This result is discussed in terms of an anticorrelation between the internal energies of a fragment pair.Furthermore, the spontaneous secondary dissociation of isopropoxy and tert-butoxy photofragments was observed which yields CH3 radicals and acetaldehyde or acetone, respectively.The unimolecular decay of these alkoxy radicals confirms their relatively high internal energy as deduced from the primary P(ET) and it is shown that this decay occurs on a submicrosecond time scale.

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 Nucleophilic Reactivities of Phenylnitrene (PhN-*) and Sulfur Anion Radicals (S-/.) at sp3 and Carbonyl Carbon

The reactions of PhN-/. with a series of carbonyl-containing molecules (aldehydes, ketones, and esters) were shown to proceed via an addition/fragmentation mechanism, PhN-* + R2C=O -> -)R2> -> PhN=C(O-)R + *R, producing various acyl anilide anion products.In several cases, the tetrahedral intermediate anion radicals were observed as minor ions.The intrinsic reactivity of the carbonyl-containing molecules was aldehydes > ketones > esters, where similar R groups were involved.The overall exothermicities of these reactions did not appear to play the major role in determining the relative rates (krelC=O) for these reactions.From the reaction of PhN-* with cyclobutanone, a new type of anion radical, PhN=C(O-)CH2* (m/z 133) (+ C2H4) was produced; the loss of C2H4 was considered due to the ring strain in the ketone.With cyclopentanone, cyclohexanone, and cycloheptanone, the anion radicals PhN=C(O-)(CH2)n* (n = 4-6) were the exclusive product ions.PhN-* was shown to be a poor nucleophile in SN2 displacement reactions with CH3X molecules (X = Cl, Br, O2CCF3).S-* was shown to exhibit modest SN2 nucleophilicity with CH3Cl and CH3Br.The reactions of S-* with CF3CO2R proceed via both SN2 displacement and carbonyl addition/fragmentation mechanisms: with R = CH3, the anion products were 65percent CF3CO2- and 35percent CF3COS-; from R = C2H5, the product ions were 4percent CF3CO2- and 96percent CF3COS-.These data yield the ratio kCH3/kC2H5 = 16 for SN2 displacement by S-* at these alkyl groups.The reactions of PhN-* with CO2, COS, CS2, and O2 are also reported.The reaction of PhN-* with CS2 to produce S-* as a major channel was used as the source of this atomic anion radical.In several reactions occuring at nearly the collison limit, selectivity was observed for (a) which of two reaction centers were attacked to give products and (b) which of two mechanisms would be dominant in the overall reaction.

Energy Partitioning to Product Translation in the Infrared Multiphoton Dissociation of Diethyl Ether

The infrared multiphoton decomposition of diethyl ether (DEE) has been investigated by the cross laser-molecular beam technique.The center-of-mass product translation energy distributions (P(E')) were measured for the two dissociation channels: (1) DEE -> C2H5O + C2H5 and (2) DEE -> C2H5OH + C2H4.The shape of the P(E') measured for radical channel 1 is in agreement with the predictions of statistical unimolecular rate theory.The translational energy released in concerted reaction 2 peaks at 24 kcal/mol; this exceedingly high translational energy release with a relatively narrow distribution results from the recoil of the products from each other down the exit barrier.Applying statistical unimolecular rate theory, we estimate the average energy levels from which DEE dissociates to products using the measured P(E') for radical channel 1.