Methyl acetate from petroleum oils

The 4b-methyl-ip-(2-formylethyl)-2p-formyl-2-(2-cyanoethyl)-4p,7a-dihydroxyperhydrophenanthrene ip-methyl acetal 2p,4p-lactol methyl ether 7a-acetate (360 mg) was stirred in 3 ml of ether. Upon the addition of 9 ml of 70% aqueous acetic acid the crystals dissolved immediately. The solution was allowed to stand at room temperature for 16 h and was then extracted with ether. The extract was washed thoroughly with water and aqueous sodium bicarbonate, dried over magnesium sulfate and concentrated to dryness under reduced pressure, yielding 337 mg of oil. On trituration with ether there was obtained 305 mg of crystals of 4b-methyl-ip-(2-formylethyl)-2p-formyl-2-(2-cyanoethyl)-4p,7a-dihydroxyperhydrophenanthrene 2p,4p-lactol methyl ether 7a-acetate as platelets, melting point 85°-105°C after recrystallizations from benzene-petroleum ether. 

This is the solid residue left when turpentine is distilled for the preparation of oil of turpentine. It consists essentially of resin acids and their oxidation products and forms brittle, translucent masses with a peculiar resinous odour and a colour varying from pale yellow to dark brown D = 1 05-1 085. It is readily soluble in alcohol (1 part in 10 parts of 70% alcohol) and dissolves also in methyl or amyl alcohol, ether, acetone, benzene, chloroform, carbon disulphide or oil of turpentine in petroleum ether it is not completely soluble. It is easily and completely saponified by caustic soda solution. Addition of a drop of concentrated sulphuric add to a solution of a small quantity of colophony in acetic anhydride produces an intense violet-red or purple coloration, soon changing to yellowish-brown. Different types or grades of colophony are sold, distinguished mainly by the colour and origin. 

Methyl 2-(3 -Phenyl-2 -propen-r-oyl)phenyl Tellurium3 A stirred mixture of 12 g (46 mmol) of 2-acetylphenyl methyl tellurium, 17.6 m/(18.4 g, 170 mmol) of benzaldehyde, 88 mlof acetic acid, and 35 ml of piperidine is heated under reflux for 6 h. The mixture is then steam-distilled to remove unreacted benzaldehyde. The resultant red oil is separated by extraction with chloroform, the extract is evaporated, and the residue is fractionally distilled under vacuum. The fraction boiling above 200°/0.1 torr is collected and redistilled to give a condensate that should solidify. This solid is recrystallized several times from a mixture of petroleum ether and benzene yield 3.2 g (20%) m.p. 102-104° (from heptane/benzenc). 

Treat 12 g (111) at room temperature for 24 hours with acetic anhydride then hydrolyze and extract to get 11.5 g residue which is ground in petroleum ether and recrystallized from cyclohexane (can chromatograph on alumina and elute with petroleum ether to wash out an oil, then with benzene containing 5% ethyl acetate to elute the produce) to give methyl-a(l-acetyl-5-bromo-2,3-dihydro-3-ind-olyl)-6-methylnicotinate (IV). Heat 5 g (IV), 12.5 ml acetone, 12.5 ml methanol and 1.8 ml methyl iodide for 18 hours in a Carius tube at 70-80°. Cool, filter, wash with acetone and recrystallize from methanol to get methyl-a(l-acetyl-2,3-dihydro-5-bromo-3-indolyl)-l,6-dimethylnicotinate iodide (V). To 9.4 g (V) in 250 ml water and 250 ml methanol at 35° add over 5 minutes 2.9 g KBH and stir 10 minutes. Add 2.9 g more KBH and stir 30 minutes. Evaporate in vacuum and extract the residue with methylene chloride to get 6.2 g oily mixture containing about 2 g of the d isomer (can separate by chromatography if desired) of methyl- o (1 -acetyl-2,3-dihydro-5-bromo-3-indolyl)-6-methyl-l,2,5,6-tetrahydro-nicotinate (VI),... 

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