1487-43-0Relevant academic research and scientific papers
Study of the Reaction Cl + Ethyl Formate at 700-950 Torr and 297 to 435 K: Product Distribution and the Kinetics of the Reaction C2H5OC(=O) → CO2 + C2H5
Kaiser
, p. 3414 - 3423 (2016/07/06)
The kinetics and mechanism of the reaction of atomic chlorine with ethyl formate [Cl + CH3CH2O(C=O)H, reaction 1] have been examined. These experiments were performed at pressures of 760-950 Torr and temperatures from 297 to 435 K. Reactants and products were quantified by gas chromatography-flame ionization detector (GC/FID) analysis. The initial mixture contained ethyl formate, Cl2, and N2. Cl atoms were generated by UV photolysis of this initial mixture at 360 nm, which dissociates Cl2. The rate constant of reaction 1 was measured at 297 K relative to that of the reaction Cl + C2H5Cl (reaction 2), yielding the rate constant ratio k1/k2 = 1.09 ± 0.05. The final products formed from reaction 1 are ethyl chloroformate, 1-chloroethyl formate, and 2-chloroethyl formate. These products result from the reactions with Cl2 of the three free radicals formed by H atom abstraction from ethylformate in reaction 1. Based on the molar yields of these three chlorinated products, the yields of the three radicals formed from reaction 1 at 297 K are (25 ± 3) mole percent of CH3CH2O(C=O); (67 ± 5) mole percent of CH3CHO(C=O)H; and (8 ± 2) mole percent of CH2CH2O(C=O)H. A second phase of this experiment measured the rate constant of the decarboxylation of the ethoxy carbonyl radical [CH3CH2O(C=O) → CO2 + C2H5, reaction 4] relative to the rate constant of its reaction with Cl2 [CH3CH2O(C=O) + Cl2 → CH3CH2O(C=O)Cl + Cl, reaction 3a]. Over the temperature range 297 to 404 K at 1 atm total pressure, this ratio can be expressed by k4/k3a = 1023.56±0.22 e-(12700±375)/RT molecules cm-3. Estimating the value of k3a (which has not been measured) based on similar reactions, the expression k4 = 5.8 × 1012 e-(12700)/RT s-1 is obtained. The estimated error of this rate constant is ± a factor of 2 over the experimental temperature range. This rate expression is compared with recent ab initio calculations of the decarboxylation of the analogous methoxy carbonyl radical.
A systematic study on the activation of simple polyethers by MoCl 5 and WCl6
Dolci, Sara,Marchetti, Fabio,Pampaloni, Guido,Zacchini, Stefano
experimental part, p. 5367 - 5376 (2010/08/04)
MoCl5, 1a, and WCl6, 1b, activate 1,3-dioxolane at room temperature in chlorinated solvents: the compound [MoOCl 3{OC(H)OCH2CH2Cl}]2, 2, has been isolated from MoCl5/dioxolane. The mixed oxo-chloro species WOCl 4, 1c, reacts with 1,3-dioxolane, selectively giving the coordination adduct WOCl4(κ1-C3H6O 2), 3. Dimethoxymethane, CH2(OMe)2, undergoes activation including C-H bond cleavage when reacted with 1a to give the molybdenum complexes [MoOCl3{OC(H)OMe}]2, 4, and Mo 2Cl5(OMe)5, 5. The reactions of 1b with CH 2(OR)2 (R = Me, Et) proceed via O-abstraction with formation of the oxo-derivatives WOCl4[O(R)CH2Cl] (R = Me, 6a; R = Et, 6b) in admixture with equimolar amounts of RCl. The reactions of 1a,b with CMe2(OMe)2 lead to mesityl oxide, MeC(O)CHC(Me)2. A series of simple diethers of general formula ROCH2(CHR′)OR′′ are activated by 1a,b in CDCl 3, usually via cleavage of C-O bonds at high temperature. The complex WCl5(OCH2CH2OMe), 7, has been detected in solution as an intermediate species in the course of the degradation of 1,2-dimethoxyethane (dme) by 1b. The activation of CH(OMe)3 by 1 is limited to C-O bonds and selectively gives methyl chloride and methylformate, which has been found coordinated in WOCl4[OC(H)OMe], 8. The organic fragments produced in the reactions have been detected by GC-MS and NMR analyses, upon hydrolysis of the reaction mixtures. Compounds 2 and 5, which have had their molecular structures ascertained by X-ray diffraction, represent rare examples of crystallographically-characterized dinuclear Mo(v) species containing both halides and oxygen ligands.
FREE-RADICAL CHLORINATION OF ACETALS AND ORTHO ESTERS
Rol'nik, L. Z.,Pastushenko, E. V.,Zlot-skii, S. S.,Rakhmankulov, D. L.
, p. 1498 - 1500 (2007/10/02)
The chlorination of 1,3-dioxolane and ortho esters (trihexyloxymethane and 2-hexyloxy-1,3-dioxolane) in the presence of azobisisobutyronitrile was studied. 2-Chloroethyl formate is formed in the case of dioxolane and 2-chloroethyl formate, ethylene carbonate, and hexyl chloride are formed in the case of 2-hexyloxy-1,3-dioxolane.
FREE-RADICAL TRANSFORMATIONS OF 2-ALKOXY-1,3-DIOXOLANES IN POLYHALOGENOALKANES
Rol'nik, L. Z.,Kalashnikov, S. M.,Pastushenko, E. V.,Zlot-skii, S. S.,Rakhmankulov, D. L.
, p. 1296 - 1299 (2007/10/02)
The free-radical transformations of 2-ethoxy-1,3-dioxolane and 2-hexyloxy-1,3-dioxolane in bromoform and chloroform were investigated.The products from these transformations are alkyl 2-halogenoalkyl carbonates, 2-halogenoethyl formates, the corresponding cyclic and linear carbonates, aldehydes, and halogenoalkanes.A scheme of homolytic transormations is proposed for 2-alkoxy-1,3-dioxolanes in polyhalogenoalkanes.
