103110-88-9Relevant articles and documents
Oxidation Chemistry of Propene in the Autoignition Region: Arrhenius Parameters for the Allyl + O2 Reaction Pathways and Kinetic Data for Initiation Reactions
Stothard, Nigel D.,Walker, Raymond W.
, p. 2621 - 2630 (1992)
The oxidation of propene has been studied at a total pressure of 60 Torr between 400 and 520 deg C, and a detailed product analysis made in the initial stages of reaction over a wide range of mixture composition.Mechanisms for the formation of the products are discussed.The initial rates of formation of hexa-1,5-diene (HDE) and carbon monoxide are used to obtain A8 = 109.66 +/- 0.35 dm3 mol-1 s-1 and E8 = 78.6 +/- 4.5 kJ mol-1, the former giving from the known value of k1 CH2=CHCH2* + CH2=CHCH2* -> CH2=CHCH2CH2CH=CH2 (1).CH2=CHCH2* + O2 -> CO + products.Arrhenius parameters are also given for alternative pathways of the allyl + O2 reaction.All involve high energy barriers.From measurements of the accelerating effect of small amounts of additives CH3CHO, HCHO, HDE and propene oxide, rate constants at 480 deg C are obtained (for the first three) for the initiation reaction (21) RH + O2 -> R + HO2.Very few independent data for this type of reaction are available.The accelerating effect of propene oxide is ascribed to an exothermic isomerisation product which is not thermally stabilised at 60 Torr and undergoes homolysis to radical fragments.HDE is shown to have a spectacular accelerating effect on propene oxidation and values of k21n/k10 = 1050 +/- 200 at 480 deg C is obtained.C3H6 + O2 -> CH2=CHCH2* + H2O.HDE + O2 -> *CH2CH=CHCH2CH=CH2 + H2O.
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Gerdil
, p. 1859,1861 (1973)
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Oxygenation with Molecular Oxygen. Thermal and Photochemical Epoxidation of Propylene in the Presence of Sulfur Dioxide in Acetonitrile at Ambient Temperature
Sasaki, Tadahiro
, p. 3882 - 3886 (1981)
Irradiation of a mixture of propylene and sulfur dioxide in acetonitrile at ice-cold temperature causes absorption of molecular oxygen and gives propylene oxide as the sole volatile product.Also, in the absence of light, the addition of nitrile or nitrate salts to a mixture of sulfur dioxide and propylene in acetonitrile under oxygen at room temperature leads to the smooth formation of propylene oxide as the only volatile product.Both reactions show quite similar solvent dependence and are retarded by the additives with ionization potentials lower than ca. 9.5 eV.The main byproduct is poly(propylenesulfonate).The mechanisms of the epoxidation reactions are discussed.
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Krassuski
, (1907)
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Seeley,Mc Elwee
, p. 1691 (1973)
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Stopped-Flow Studies of the Mechanisms of Ozone-Alkene Reactions in the Gas Phase: trans-2-Butene
Martinez, Richard I.,Herron, John T.
, p. 4644 - 4648 (1988)
The reaction of ozone with trans-2-butene has been studied in the gas phase at 294 K and 530 Pa (4 Torr) by using a stopped-flow reactor coupled to a photoionization mass spectrometer.The concentrations of reactants and products were determined as a function of reaction time.A mechanism is proposed to account for the observed products: CH3CHO, H2CO, CO2, CH4, CF3C(O)C(H)(OH)CH3, H2C=C=O, H2O, 2-butanone, 2,3-epoxybutane, CH3C(O)C(O)CH3, and HC(O)C(O)H.This work again indicates that simple "hot" ester hypothesis needs to be critically reconsidered for gas-phase ozonolysis.
Reactions Involving Hot O(3P) Atoms and Isomeric 2-Butene
Ferrieri, Richard A.,Wolf, Alfred P.
, p. 4747 - 4752 (1992)
The low-pressure gas-phase investigation is reported on the reactions involving high-energy O(3P) atoms with cis- and trans-butene.Gas chromatographic analysis of stable hydrocarbon end products revealed a complex spectrum of compounds containing carbonyl, epoxide, and alcohol groups.The large distribution of alcohol products was a distinct feature in these hot atom systems, indicating that OH radical formation was important.These analyses revealed differences in the internal energy levels of the reaction intermediates formed through the greater pressure dependence exhibited by the degree of stereospecific addition of oxygen atoms to trans-butene then reaction with cis-butene and through the greater degree of internal rearrangement and carbon-carbon bond scission exhibited by the trans intermediate.Direct measurements using on-line mass spectrometry also revealed that CO product signals were 14.6 times higher from reactions with cis-butene than with trans-butene, indicating greater reactivity of the cis ?-bond toward oxygen atom attack.Similarly, these direct analyses revealed that OH product signals were 1.7 times higher from reactions with cis-butene, suggesting that in addition to direct H abstraction an indirect pathway involving mutual interaction with the substrate's ?-bond may have contributed, in part, to those OH products observed in these studies.Kinetic energy moderator studies supported this hypothesis through the different moderator dependencies exhibited by the OH product signals seen to arise from high-energy oxygen atom reactions with the two stereoisomers.
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Carlock,J.T.,Mack,M.P.
, p. 5153 - 5156 (1978)
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A method for preparing epoxy butane
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Paragraph 0019; 0020, (2017/03/08)
The invention relates to a method for preparing epoxy butane, which comprises the following step: in an isopropyl benzene solution containing 25 wt% of cumene hydroperoxide solute, preparing epoxy butane from butylene oxide by using the cumene hydroperoxide solute as an oxidizer and a titanium-silicon molecular sieve with three-dimensional pore canal structure as a catalyst, wherein the fixed bed reaction conditions are as follows: the mole ratio of butylene to the cumene hydroperoxide solute is (5.0-12.0):1, the weight hourly space velocity of the cumene hydroperoxide is 1.0-5.0 h, the reaction pressure is 1.0-6.0 MPa, and the temperature is 60.0-120.0 DEG C. The catalyst is the titanium-silicon molecular sieve with three-dimensional pore canal structure; the molecular sieve has hysteresis loop on the low-temperature nitrogen adsorption and desorption isotherm; the average pore size is 2.0-8.0nm, and the specific area is 650.0-1100.0 m/g; and the catalyst has the advantages of favorable activity and high epoxy butane selectivity, and can be widely popularized and applied to industrial production of epoxy butane by butylene epoxidation.
