Petroleum residues apparatus

The experimental details for mono-M-propylanillne are as follows. Reflux a mixture of 230 g. of aniline and 123 g. of n-propyl bromide for 8-10 hours. Allow to cool, render the mixture alkafine, and add a solution of 150 g. of zinc chloride in 150 g. of water. Cool the mixture and stir after 12 hours, filter at the pump and drain well. Extract the thick paste several times with boiling light petroleum, b.p. 60-80° (it is best to use a Soxhlet apparatus), wash the combined extracts successively with water and dilute ammonia solution, and then dry over anhydrous potassium carbonate or anhydrous magnesium sulphate. Remove the solvent on a water bath, and distil the residue from a Claisen flask with fractionating side arm (well lagged). Collect the n-propyl-aniline at 218-220° the yield is 80 g. Treat the pasty solid zincichloride with an excess of. sodium hydroxide solution and steam distil 130 g. of pure aniline are recovered. 

To the cooled reaction mixture, 200 ml. of water is added carefully with stirring. Potassium carbonate is added with continued stirring until the water layer is saturated the mixture is now transferred to a separatory funnel and extracted three times with 60-ml. portions of ether. The combined ether extracts are dried over solid sodium hydroxide and are then transferred to a simple distillation apparatus. Distillation is commenced with a steam bath as source of heat when most of the ether has been removed, the steam bath is replaced by a flame. Distillation is continued until most of the piperidine (b.p. 106°) has been removed. The cooled residue in the distillation flask is recrystallized from petroleum ether (boiling range 30-60°) with the use of charcoal. There is obtained 30.0 g. (71%) of N-/3-naphthyl-piperidine as tan crystals, m.p. 52-56°. An additional recrystallization from the same solvent gives crystals, m.p. 56-58°, with about 10% loss in weight (Note 6). 

Acetic anhydride (75 ml) and pulverized calcium carbide (15 g) are refluxed for 60 minutes in an apparatus as described above. Sufficient benzene is then added to reduce the boiling temperature to 110-112°. After cooling, 14.4 g of pinacol is introduced, and the mixture is refluxed with stirring for 30 hours. The cooled mixture is then stirred into ice, extracted into ether and washed with sodium carbonate solution. The solution is dried, then filtered, and theether is evaporated. The residue is clarified with Norit and recrystallized from benzene-petroleum ether or methanol, mp 67-68°. 

Extraction. Each dried plant part was Soxhlet-extracted with petroleum ether. The solvent was evaporated vacuo to give a residue labeled Fraction A (Scheme I). The marc was air-dried and extracted with ethanol in a Soxhlet apparatus. Evaporation of the solvent vacuo yielded Fraction B. The aqueous phase was removed by freeze-drying and the water-soluble residue was labeled Fraction C. 

The receiver can be disconnected from the apparatus under a positive pressure of nitrogen from both nitrogen inlets and the neck is closed with a stopcock. The fuming reactive residues in the reaction flask may be destroyed by dilution with petroleum ether (bp 60-80°), followed by slow addition of pentanol or hexanol while cooling in ice-salt. After all reaction has ceased this mixture may be poured into a large volume of ice for disposal. 

In a distillation apparatus fitted with mechanical stirrer, thermometer, and provisions for adding solids, to an agitated mixture of 26.7 gm (0.187 mole) erf 2-naphthylamine (CAUTION carcinogenic material) and 20 gm (0.163 mole) of nitrobenzene maintained at 180°C is added slowly 17 gm of powdered sodium hydroxide over a 20 min period. After completion of the addition, heating is continued for 10 min. After cooling, the reaction mixture is treated repeatedly with dilute hydrochloric acid. The excess nitrobenzene is then separated by steam distillation. The residue from the steam distillation is treated with ethanol at 70°C to precipitate insoluble impurities which are removed by filtration. On cooling the filtrate, product cyrstals separate which, after filtration, are taken up in petroleum ether, leaving petroleum ether-insoluble impurities behind. The petroleum ether extract is evaporated to dryness and the residue is recrystallized from ethanol at 75°C yield 17 gm (41 %), m.p. 84°C. 

A 1-L Pyrex vessel is charged with 29.5 g (0.13 mol) of (5S)-(5-0-tert-butyldimethylsiloxymethyl)furan-2(5H)-one, 23.7 g (0.13 mol) of benzophenone (Note 10) and 800 mL of methanol. The vessel is placed in a water-cooled, immersion-irradiation apparatus (Note 11), and the solution is degassed for 1 hr in a stream of nitrogen. It is then irradiated using two 125-watt, 350-nm lamps the reaction is complete after 48 hr (Note 12). The solvent is evaporated and the residue is purified by silica chromatography [1 kg of silica, 8.5-cm x 43-cm column with a gradient elution from ethyl acetate petroleum ether (1 1) to neat ethyl acetate]. This yields 18.5 g (55%) of the title compound, 18.3 g (77%) of recovered benzophenone, 3.6 g of benzpinacol,... 

The same apparatus and procedure as in Section 5.A are used. To prepare Cd(SAr")2, 2,4,6-tri-tert-butylbenzenethiol9 (1.5 g, 5.39 mmol) is dissolved in light petroleum (20 mL). Cd[N(SiMe3)2]2 (1.08 g, 2.5 mmol) is added to the stirred solution via syringe. After a few seconds, a white solid precipitates. The reaction is warmed on a warm water bath (ca. 40°C) for 1 h. The supernatant liquid is filtered off and the residue recrystallized from toluene at 10°C to give colorless crystals (1.0 g). A second fraction is obtained from the mother liquor the combined yield is 1.2 g (72% based on cadmium). 

The greyish-green insoluble residue from the foregoing extractions, when further extracted in a Soxhlet apparatus with dry chloroform containing 5 per cent, of alcohol, yields olive-green crystals decomposing at 208° to 209° C. The product is insoluble in petroleum, carbon tetrachloride or dry chloroform, but dissolves in the last-named solvent in the presence of a little alcohol. It is decomposed by water or moist alcohol to products soluble in hot water. 

Fat.—This may be determined on the dry residue from 2, which is placed in a filter-paper thimble in an extraction apparatus, white the dish is rinsed out with anhydrous ether or light petroleum into the extraction flask. The extraction is continued for about six hours, after which the bulk of the solvent is distilled off on water-bath, while the remaining... 

The finely ground material is heated in a reflux apparatus with petroleum ether and ammonium carbonate, the mass being afterwards filtered and the petroleum extract shaken with methyl alcohol. The latter is separated and evaporated on a water-bath the presence of egg is then detectable by the odour of the residue. 

Heat under reflux for 4 hours a solution of 3 g (0.0165 mol) of undec-10-ynoic acid (Expt 5.23) in 240 ml of glacial acetic acid containing 13 ml of concentrated sulphuric acid and 1.4g of mercury(n) acetate. Dilute the dark coloured solution with 300 ml of water, filter and extract the solution with dichloromethane using a continuous extraction apparatus (Fig. 2.95) (1). Wash the dichloromethane extract carefully with distilled water until the washings are neutral, dry the extract and evaporate on a rotary evaporator. Recrystallise the solid residue from light petroleum (b.p. 60-80 °C) using a little decolourising charcoal. The yield of keto-acid, m.p. 56-57 °C, is 1.65 g (50%). 

The filtrate from the nutsch filter enters receptacle 9, and from there into vapour-heted tank 10 for distilling chlorobenzene in vacuum (chlorobenzene is sent back to synthesis). The cooled oily residue from the tank is sent into nutsch filter 13 to be separated into crystals (raw phosphonitrilechloride trimer) and oily liquid (phosphonitrilechloride oligomers). Trimer crystals are sent into collector 14 (it is also filled with light petroleum, which does not dissolve oily oligomers). The emulsion formed in the collector is sent into extractor 16. A temperature equal to the boiling point of light petroleum is maintained in this apparatus. 

Apparatus 22 is cooled with salt solution (-15 °C) to crystallise phosphonitrilechloride trimer the mixture is held for some time to let ciystals grow and precipitate. Then the ciystals are separated in centrifuge 23, and the mother solution is sent back to tank 19. The obtained crystals of phosphonitrilechloride trimer can be given additional purification, i.e. reciys-tallisation from fresh light petroleum or vacuum distillation at 127 °C and a residual pressure of 17 GPa. 

Sodium Benzenetellurolate1 This reaction must be carried out under nitrogen or argon in an apparatus suitable for work with liquid ammonia2. A filtered suspension of 0.35 g (15 mmol) of sodium in 25 ml of liquid ammonia is added to a suspension of 3.1 g (7.5 mmol) of diphenyl ditellurium in 15 ml of liquid ammonia. The blue color of the sodium/ammonia solution changes rapidly to yellow. The reaction is complete when the solid ditellurium compound has disappeared. The reaction mixture is then filtered, the ammonia is evaporated, and the grey residue is washed with petroleum ether yield 3.1 g (95%). 

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