Gas epichlorohydrin

Hydrolytic Kinetic Resolution (HKR) of epichlorohydrin. The HKR reaction was performed by the standard procedure as reported by us earlier (17, 22). After the completion of the HKR reaction, all of the reaction products were removed by evacuation (epoxide was removed at room temperature ( 300 K) and diol was removed at a temperature of 323-329 K). The recovered catalyst was then recycled up to three times in the HKR reaction. For flow experiments, a mixture of racemic epichlorohydrin (600 mmol), water (0.7 eq., 7.56 ml) and chlorobenzene (7.2 ml) in isopropyl alcohol (600 mmol) as the co-solvent was pumped across a 12 cm long stainless steel fixed bed reactor containing SBA-15 Co-OAc salen catalyst (B) bed ( 297 mg) via syringe pump at a flow rate of 35 p,l/min. Approximately 10 cm of the reactor inlet was filled with glass beads and a 2 pm stainless steel frit was installed at the outlet of the reactor. Reaction products were analyzed by gas chromatography using ChiralDex GTA capillary column and an FID detector. 

The problems of conformational averaging and of considering solvent effects are interconnected. For instance, one of the more obvious effects when going from the gas phase to solution is the resulting change of mole fractions for solutes with multiple conformers [115, 159]. One example of this is epichlorohydrin, which is discussed elsewhere in this chapter. A conformer distribution with several thermally accessible conformers that have considerably different ORs and ECD spectra might also result in a marked temperature dependence of measured and simulated chiroptical properties. 

C3H5CIO alpha-epichlorohydrin 106-89-8 in CCI4 1.799 1 2565 C4H4N2 pyrimidine 289-95-2 gas 2.335 1... 

No polymer formation was observed in the above reaction however, some water soluble organic components were detected by gas chromatography which were presumably derived from hydrolysis of epichlorohydrin. Analysis of the aqueous residues showed that the sodium carbonate was essentially unchanged during the reaction, which lead to examination of... 

Accordingly, sodium hydroxide (17% aqueous solution) was stirred with the chlorohydrin ester masterbatch prepared above. The reaction was followed at 40 C using a molar ratio of sodium hydroxide to chlorohydrin ester of 2 1. The reaction was followed by gas chromatography. Fig. 18 shows the rates of conversion of epichlorohydrin and chlorohydrin ester during the reaction. Again, it was shown that after 6.5 hours all the sodium hydroxide had been consumed (cf. sodium hydroxide/sodium carbonate reaction at 40 C) at which time only 64% conversion to the epoxy compound was observed. Correspondingly the epichlorohydrin hydrolysis (25%) had increased in comparison to the sodium hydroxide/sodium carbonate method (15.6% at 40 C). 

Results from the data compilation of Yaws and co-workers (31,44) were selected for heat capacity of ideal gas except for epichlorohydrin (5). Correlation of data was accomplished using Equation (l-5a). Results are in favorable agreement with data. Errors are about 1-10% or less in most cases. 

The data compilation of Yaws and co-workers (31,44,45) was selected for enthalpy of formation of ideal gas for all compounds except epichlorohydrin. For epichlorohydrin, the value at 25 C (5) was extended to higher temperatures by integration of the appropriate equations (177) which involve gas heat capacities. Data for enthalpy of formation of the ideal gas is a series expansion in temperature, Equation (1-11). Results from the correlation are in favorable agreement with data. 

These pioneering studies formed the basis for the development of commercial processes for the production of allyl acetate by oxidative acetoxylation of propylene (Eq. 1). Processes are operated by Showa Denko and Daicel in Japan and Hoechst and Bayer in Europe [2,11], The reaction is usually performed in the gas phase, e. g. at 140-170 °C over Pd(OAc)2/Cu(OAc)2/KOAc/Si02 or Pd/ KOAC/S1O2 catalysts and allyl acetate is formed with > 95 % selectivity. Allyl acetate is the raw material for the production of epichlorohydrin and glycerol. 

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