Nitrogen removal from petroleum products

Methoxy-cis-19-norpregna-l,3,5(10),17(20)-tetraene A solution of 31 g (109 mmolesi of estrone methyl ether in 600 ml of benzene is added rapidly to a solution of 469 mmoles of ethylidenetriphenylphosphorane in 1.2 liters of DMSO. After heating under nitrogen at 60° overnight, the reaction is cooled, poured into ice water, and extracted with three portions of hexane, backwashed with three portions of water and the hexane removed. The crude product, dissolved in petroleum ether (bp, 30-60°), is filtered through 225 g of alumina (activity I). The residue from the eluate consists of 95 % cis- and 5 % tran5-isomers, as determined by vpc analysis. After recrystallization from ether-methanol, 26.3 g (82%) of cw-isomer is obtained mp 76.5-77.5° [a]o 60°. 

A solution of 3.7 g (12 mmol) of the pure (l R)-diastereomer 6 is stirred under nitrogen in 15 mL of iodomethane and 5 mL of dry DMSO for 36 h. The excess iodomethanc is evaporated leaving a viscous red oil which is heated under reflux in 25 mL of 2N KOI for 5 h. After cooling, the amino alcohol is removed from the aqueous phase by extraction with Et20. The alkaline aqueous layer is acidified with 12 N HC1 and extracted with Ei,0. The crude product is recrystallized from benzene/petroleum ether to give enantiomer-ically pure (R)-2-hydroxy-2-phenylpropanoic acid [(-)-(R)-atrolaclic acid] (7) yield 1.4 g (71%) mp U5-116X [x]25 - 38.4 (< = 2.5, EtOH). 

The cooling bath is removed, and the mixture is left to reach room temperature with an air bath and stirred for 30 min. The solvent is removed under vacuum to afford a brown solid and then 30 mL of petroleum ether (40-60°C), freshly distilled from Na/benzophenone under nitrogen, is added to the flask. The dark yellow suspension is filtered to remove the lithium acetylacetonate, and the solid is washed twice with 7 mL of petroleum ether. The solvent is removed from the filtrate under vacuum to yield a dark yellow solid (1.95 g), which is sublimed at 50-60°C (10 3torr). The product is a yellow crystalline solid. Yield 1.84 g (86%). ... 

Typically, liquids derived from coal are lower in hydrogen content and contain more impurities than do petroleum products. These impurities consist of atoms other than hydrogen and carbon, that is, nitrogen, sulfur, oxygen, and inorganic materials. Upgrading of coal liquids to make specification fuels typically involves both hydrogen addition and removal of impurities. 

Phenylazo)phenyl Tellurium Acetate1 A solution of 0.082 g (1 mmol) of sodium acetate in 20 ml dry methanol is added under an atmosphere of nitrogen to a stirred solution of 2-(phenylazo)phenyl tellurium chloride (0.344 g, 1 mmol) in 25 ml dichloromcthanc at 20°. The mixture is stirred for 20 min and the solvents removed on a rotary evaporator. 100 ml dichloromethane are added to the residue. The mixture is stirred vigorously and then filtered to remove insoluble sodium chloride The solvent is removed from the filtrate on a rotary evaporator. 5 ml methanol are added to the residue, the mixture is stirred well, and then filtered to collect the product. The crude material is dissolved in petroleum ether (60-80°). Slow evaporation of the solvent caused golden-orange crystals to form yield 75% ,fn.p. 121-122° (dec.). 

Two grams (0.007 mol) of triphenylphosphine is dissolved in 100 ml. of dioxane or tetrahydrofuran. One gram (0.0020 mol) of triiron dodecacarbonyl (synthesis 46) is added, and the mixture is stirred in an atmosphere of nitrogen at a temperature of about 70° for 45 minutes, or until the green color of the solution completely disappears. The mixture is then cooled to room temperature, filtered, and the browm residue washed with dioxane or tetrahydrofuran. The solvent is removed from the filtrate and washings by distillation vmder vacuum and the residue treated with 50 ml. of methanol or ethanol and cooled. A yellow crystalline product is obtained. The crystals are filtered, washed with two 10-ml. portions of petroleum ether, and sublimed under vacuum at 180°. The sublimate consists of [Fe (CO) 4- (C6Hs)3P ], which melts at 201 to 203° with decomposition. The residue from the sublimation is dissolved in a minimum amount of benzene, and the solution is filtered. The fil-... 

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