席夫碱的制备(甲苯制备但己烷与二氯甲烷重结晶).pdfVIP

Organic Syntheses, Coll. Vol. 8, p.586 (1993); Vol. 65, p.108 (1987). AMBIENT-TEMPERATURE ULLMAN REACTION: 4,5,4,5- TETRAMETHOXY-1,1-BIPHENYL-2,2-DICARBOXALDEHYDE [1,1-Biphenyl]-2,2-dicarboxaldehyde, 4,4,5,5-tetramethoxy-] Submitted by F. E. Ziegler, K. W. Fowler, W. B. Rodgers, and R. T. Wester1. Checked by Tetsuji Oshima and Ryoji Noyori. 1. Procedure Caution! Aqueous sodium cyanide is used in this procedure. All operations should be conducted in a well-ventilated hood and rubber gloves should be worn. A. 6-Bromo-3,4-dimethoxybenzaldehyde cyclohexylimine (1). A 2-L, three-necked flask is equipped with a Dean–Stark trap, a reflux condenser, a magnetic stirrer, and a nitrogen inlet. The vessel is purged with nitrogen and charged with 40.0 g (0.16 mol) of 6-bromo-3,4-dimethoxybenzaldehyde (6- bromoveratraldehyde) (Note 1). 22.4 mL (0.20 mol) of cyclohexylamine (Note 2), and 800 mL of toluene. The mixture is refluxed for 16 hr (Note 3). The solution is cooled to room temperature and the solvent is removed on a rotary evaporator. The residual crystalline mass is recrystallized from a 3 : 1 hexane–methylene chloride mixture (1.5 L) to provide 48.4–51.4 g of the imine 1 as white crystals in two crops (mp 172–172.5°C)2 (Note 4). B. Cuprous iodide-triethyl phosphite complex ( ). (Note 5). A 1-L, round-bottomed flask equipped 2 with a magnetic stirrer and reflux condenser is flame-dried under nitrogen. The vessel is charged with 38.2 g (0.20mol) of cuprous iodide, 33.4 mL (0.20 mol) of triethyl phosphite (Note 6) and 400 mL of dry toluene (distilled from CaH2). The mixture is stirred at 80°C for 8 hr, cooled to room temperature, and filtered under reduced pressure on a pad of Celite. The solvent is removed from t