In the chemical reaction process, reaction time, type of solvent, can easily affect the result of the reaction, thereby determining the yield and properties of the reaction product. An updated downstream synthesis route of 4117-09-3 as follows. Computed Properties of C7H13Br
A clean, dry, 1 L 3-neck flask equipped with a stir bar and nitrogen inlet was charged with magnesium turnings (10.31 g, 0.4241 mol, 1.5 equiv.) and ?0.1 mg of iodine, and the flask was purged with nitrogen for 5 minutes. 750 mL of anhydrous THF [15 mL/g of 7-bromohept-1-ene (3)] was charged and stirring was initiated. 7-Bromohept-1-ene (3, 50.02 g, 0.2824 mol, 1.0 equiv.) was slowly added drop wise over 10-15 minutes under nitrogen. During this period, the pink color of iodine disappeared during initial stages, the reaction was found to be slightly exothermic, and the temperature of the contents was raised from an initial ambient (20-23 C.) to about 31 C. After the addition was complete, the resulting pale gray color solution was cooled to room temp (23 C.) and stirring was continued for an additional 2.5 h under nitrogen to form the Grignard reagent (7-hept-1-ene magnesium bromide). Into a separate 2 L dry three neck RB flask equipped with a mechanical stirrer, thermocouple and an addition funnel with nitrogen inlet, diethyl oxalate (4, 82.61 g 0.5642 mol, 2.0 equiv.) and 750 mL of anhydrous THF [15 mL/g of 7-bromo-1-pentene (3)] were charged under nitrogen. The mixture was cooled to below -20 C. temperature (Jacket temperature: -23 C.) with stirring. The Grignard reagent (7-hept-1-ene magnesium bromide), which was prepared as described above, was transferred using a cannula into a side-arm addition funnel set on top of the 2 L RB flask. The reagent was added drop wise slowly into diethyl oxalate-THF solution over 1 h 50 min, while maintaining the jacket temperature below -23 C. During the addition of the Grignard reagent, the reaction was found to be exothermic and the internal temperature was raised to maximum of -18 C. After the addition was complete, the mixture was warmed to -15 C., and the progress of the reaction was monitored by HPLC. After 3 h at -15 C., the reaction mixture was warmed to -10 C., quenched with 3N hydrochloric acid solution and the final pH was adjusted to 1.4-1.6 by drop wise addition. During the quench, the internal temperature rose to -6.7 C. due to an exotherm while, the jacket temperature was maintained at -12 C. The mixture was stirred for an additional 10 min and the pH was re-checked and confirmed to be approximately, 1.7-1.8. The mixture was warmed to 22 C., and the pH was again re-checked (pH=2.8) and re-adjusted to pH=1.2 with 3N hydrochloric acid solution. A total of 81 mL of 3N hydrochloric acid solution was used for quench and pH adjustment. Agitation was stopped and the layers allowed to settle. The organic phase was separated, and the bottom aqueous layer was back-extracted with dichloromethane (1*100 mL). The combined organic phases were concentrated on a rotary evaporator (Bath temperature: 45 C./Vacuum) to give the crude product as a yellow oil. The crude product was dissolved in 200 mL of dichloromethane (some solids/salts were present) and 200 mL water. The bottom aqueous phase was separated and back-extracted with dichloromethane (2*200 mL). The combined organic phases were dried over anhydrous magnesium sulfate (25 g), filtered and concentrated on a rotary evaporator (bath temperature: 45 C., under vacuum), to afford a pale yellow viscous as oil. The crude product was purified by flash chromatography in four equal portions, with each portion dissolved in about 25 mL of dichloromethane for loading onto a silica gel column and eluted using 5-10% ethyl acetate in hexanes. The selected fractions were combined and concentrated on a rotary evaporator (bath temperature: 45 C., under vacuum), and further dried under vacuum (<5 mm/Hg) at ambient temperature for 4 h to afford 36.49 g of ethyl 2-oxonon-8-enoate (5) in 65.2% yield as colorless oil.
According to the analysis of related databases, 4117-09-3, the application of this compound in the production field has become more and more popular.
Reference:
Patent; AbbVie Inc.; Abrahamson, Michael J.; Pruyne, Julie J.; Kielbus, Angelica B.; Lallaman, John E.; Reddy, Rajarathnam E.; Chemburkar, Sanjay R.; (29 pag.)US10059969; (2018); B1;,
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