Propylene-argon

Gas Calibration Blends, 1 to 10 mg/kg COS in either nitrogen, argon, propylene or a propylene/argon mixture. They can be obtained from any commercial supplier or prepared as shown in Appendix XI or Test Method D 4468. 

A suspension of 37.3 g (0.1 mol) of 7/3-amino-3-methoxy-3-cephem-4-carboxylic acid hydrochloride dioxanate in 500 ml methylene chloride is stirred for 15 minutes at room temperature under an argon atmosphere and treated with 57.2 ml (0.23 mol) of bis-(trimethylsilyl)-acetamide. After 45 minutes the faintly yellow slightly turbid solution is cooled to 0°C and treated within 10 minutes with 31.2 g (0.15 mol) of D-Ct-amino-Ct-d, 4-cyclohexadienyl (acetyl chloride hydrochloride. Thirty minutes thereafter 15 ml (about 0.21 mol) of propylene oxide is added and the mixture is further stirred for 1 hour at 0°C. A cooled mixture of 20 ml of absolute methanol in 200 ml of methylene chloride is added within 30 minutes, after another 30 minutes the precipitate is filtered off under exclusion of moisture, washed with methylene chloride and dried under reduced pressure at room temperature. The obtained hygroscopic crystals of the hydrochloride of 7j3-[D-a-(1,4-cyclohexadienyl)acetylamino] -... 

Table III presents the relative rates of H2 transfer reactions from cyclo-C5H10 and C5H12 to propylene, ethylene, acetylene, and cyclopropane. These values were obtained by irradiating pentane-CwDm-02 mixtures with gamma rays, or with the argon resonance lines at 1048-1067 A. The results obtained by the two irradiation techniques are in fair agreement.

Perfluoroallyl radical, C3F5, was obtained by vacuum pyrolysis (850-950°C, 10 Torr) of 1,5-perfluorohexadiene or of 3-iodopentafluoro-propylene (14) and was studied by pyrolytic mass spectrometry (Kagrama-nov et al., 1983b) and by IR spectroscopy in an argon matrix (Mal tsev et al., 1986). 

Matrix IR spectra of various silenes are important analytical features and allow detection of these intermediates in very complex reaction mixtures. Thus, the vibrational frequencies of Me2Si=CH2 were used in the study of the pyrolysis mechanism of allyltrimethylsilane [120] (Mal tsev et al., 1983). It was found that two pathways occur simultaneously for this reaction (Scheme 6). On the one hand, thermal destruction of the silane [120] results in formation of propylene and silene [117] (retroene reaction) on the other hand, homolytic cleavage of the Si—C bond leads to the generation of free allyl and trimethylsilyl radicals. While both the silene [117] and allyl radical [115] were stabilized and detected in the argon matrix, the radical SiMc3 was unstable under the pyrolysis conditions and decomposed to form low-molecular products. 

Pyrolytic carbon was inserted into the pores of these silica matrices by chemical vapor infiltration (CVI). The silica template was contacted with a flow of propylene Pr, (2.5 vol%) diluted in argon at 750°C during 15 hours. A quite uniform pore filling can be obtained by CVI. At the end, the carbon represents about 50 wt% of the C/Si02 material. Since the deposition... 

The first fixed-bed application of a supported ionic liquid-phase catalyst was hydroformylation of propylene, with the reactants concentrated in the gas phase (265). The catalyst was a rhodium-sulfoxantphos complex in two ionic liquids on a silica support. The supported ionic liquid phase catalysts were conveniently prepared by impregnation of a silica gel with Rh(acac)(CO) and ligands in a mixture of methanol and ionic liquids, [BMIMJPFg and [BMIM][h-C8Hi70S03], under an argon atmosphere. 

A 300 mL dried round-bottomed flask with a magnetic stirrer bar, and a 3-way tap with argon balloon was charged with (a5,R)-6,6 -[(propylene)dioxy]biphe-nyl-2,2 -diol (5) (600 mg, 2.4 mmol), potassium carbonate (720 mg, 5.52 mmol) and A,A -dimethylformamide (150 mL). The mixture was heated to 80 °C. To the mixture was slowly added 2-bromoethyl ether (553 pL, 4.8 mmol) in N,N -dimethylformamide (4mL) over 4 h, and this was stirred for 5 h at the same... 

To a dried round-bottomed flask equipped with a magnetic stirrer bar and a 3-way tap with argon balloon containing (u5, /f)-2,2-[oxybis(ethylene)dioxy]-6,6 -[(propylene)dioxy]biphenyl (6) (656 mg, 2.0 mmol) at 0°C was added the LDBB solution in THE (25 mL). The stirring was continued for 1 h (TLC hexane/ethyl acetate = 1/1, product Rf=0.3) and quenched by aqueous 1 M HCl (20 mL). 

Propylene carbonate [108-32-7] M 102.1, b 110°/0.5-lmm, 238-239°/760mm, d 1.204, n 1.423. Manufactured by reaction of 1,2-propylene oxide with CO2 in the presence of a catalyst (quaternary ammonium halide). Contaminants include propylene oxide, carbon dioxide, 1,2- and 1,3-propanediols, allyl alcohol and ethylene carbonate. It can be purified by percolation through molecular sieves (Linde 5A, dried at 350° for 14h under a stream of argon), followed by distn under vac. [Jasinski and Kirkland AC 39 163 1967], It can be stored over molecular sieves under an inert gas atmosphere. When purified in this way it contains less... 

Alkylation of the remaining secondary amine groups of 5. sample 6. Propylene oxide (0.9 g) in ahydrous ethanol (20 mL) is added drop by drop to a stirred suspension of sample 5 (lg) previously evacuated at 120°C overnight, in 20 mL of anhydrous ethanol maintained at 0°C. The stirred suspension was kept at room temperature for additional 24 h The resulting solid 6 was filtered and washed with anhydrous ethanol under argon atmosphere, then dried under vacuum. 

Catalysts Preparation. The silicoaluminophosphate (SAPO) molecular sieves employed in this study were synthesized in the laboratory of Professor Mark Davis in the Department of Chemical Engineering of the Virginia Polytechnic Institute, following the methods reported in U.S. Patent 4,440,871. The three different samples, distinguished by their microscopic structure, were the wide-pore SAPO-5, medium-pore SAPO-11, and the narrow-pore SAPO-34. Verification of their microscopic structure (through x-ray diffraction) and micropore diameters (by argon adsorption measurements) was performed at VPI. The SAPO molecular sieves were provided in the ammonium cation form. Ex situ calcination at 873 K for one hour in oxygen was performed on the SAPO samples prior to their use as catalysts for the propylene conversion. 

Photolysis carried out in the presence of added nitrogen or argon gave lower yields of hydrocarbons other than propylene than those carried out with the same pressure of the dimethyldiazirine in the absence of added gas. This is to be expected, due to the stabilization of the CHj-CH=CHa by the nitrogen or argon. Photolysis in the presence of 5% oxygen scarcely affected the yield of propylene but considerably reduced the yields of the other hydrocarbons, presumably by reaction with the radical intermediates. 

When phosphorus vapor with argon and ethylene, propylene, butene-1, propane, methane, ammonia or hydrazine was swept through a discharge tube, phosphine, PH3, was produced as the major gaseous constituent in aU cases ... 

Supply of Chemicals Monomer propylene (CP grade) was purchased from Matheson Gas Products and was used as received. Argon was obtained from Alrco Inc. The reagent bromotri-chloromethane (99%) was obtained from Aldrich Chemical Company. 

The reactor for HjO-electrolysis used in the epoxidation of alkenes is shown schematically in Figure 2. The anode was prepared from metal blacks (70 mg) mixed with Teflon powder by the hot-press method. The cathode was prepared from a mixture of Pt black, graphite and Teflon powder. Propylene was bubbled into CH Clj (40 ml used as a solvent) in the anode compartment. In the case of 1-hexene epoxidation, 10 ml of the alkene was dissolved in 30 ml of CH2CI2. Argon (98 kPa) and water vapor (4 kPa) were... 

---