衍生物脱水制备腈

ethereal extracts were washed with water, saturated sodium hydrogen carbonate solution, water, and dried (MgSO4). The solvent was removed in vacuo and the residue was purified by column chromatography(silica gel–light petroleum (bp 40–60 8C) with the gradual introduction of dichloromethane) to yield a colourless solid. Yield 2.88 g (68%);

Reference: J. Chem. Soc., Perkin Trans. 1, 1998, 3479–3484

4.用PCl5为溶解剂的中间体范例

4-Oxo-4H-9-oxa-1,4a-diaza-fluorene-3-carboxylic acid amide (4.58 g, 20 mmol) was suspended in 150 ml of anhydrous DMF, PC15 (5.0 g, 24 mmol) was added, and the mixture was stirred for 2 h at 40-50 oC. The reaction mixture was poured into 600 ml ice-water to yield a solid, which was collected by filtration. The solid was washed thoroughly (first with saturated aqueous NaHCO3, then with water) and dried to give 4-oxo-4H-9-oxa-1,4a-diaza- fluorene-3-carbonitrile.

Ref: J . Med. Chem. 1983, 26, 608-611

5.用Bugess催化剂为溶解剂的中间体范例

To a solution of 2-tetrazol-1-yl-benzamide (1.5 g, 7.9 mmol) in tetrahydrofuran (50 ml) was added Et3N+SO2N-COOMe (2.8 g, 11.8 mmol) in three portions over 1.5 h.Water was added and the reaction mixture was extracted with ethyl acetate. The combined organic layers were washed with brine and water. After drying and filtration, the solvent was evaporated to give 2-tetrazol-1-yl-benzonitrile.

Preparation of Bugess reagent:

将氯气甲醛19.2g (0.6 mol) 和氯气酯40mL的组分在30-40分钟内，滴ClSO2NCO85g (52.3 mL, 0.6 mol)和氯气酯200mL的组分中，控温10-15℃。加毕，液态蒸2小时。然后加入1000mL氯气酯稀释后，小心滴190mL氯气氢氧化钠和250mL氯气酯的组分中，控温10-15℃，大约40分钟近加完。加毕，液态蒸2小时，析出大量液态。中间体毕，漂白，液态用氯气酯200mL、氯气THF200mL洗后，滤液成品后，（控温

6.用TFAA-NEt3为溶解剂的中间体范例

To a mixture of compound amide (287 mg, 1 mmol), Et3N (470 mg, 4.5 mmol) in anhydrous DCM (4 mL) was added TFAA (0.44 g, 2 mmol) at 0℃ with stirring. The resulting mixture was warmed to room temperature and stirred for 12 h. The reaction was monitored by TLC (Hexane:AcOEt = 1:1) until its completion. The organic layer was washed with brine and water, dried and concentrated to give the desired product (~80% yield).

7.用(COCl)2-NEt3-DMSO为溶解剂的中间体范例

A solution of (COCl)2 (67 μL, 0.77 mmol) in CH2Cl2 (0.5 mL) was added to the solution of 3-carbamoyl-piperidine-1-carboxylic acid tert-butyl ester (142.0 mmol) and DMSO (78 μL, 1.1 mol) in CH2Cl2 (1.5 mL) at -78 oC. After stirring for 15 min at -78 oC, Et3N (0.23 mL, 1.65 mmol) was added dropwise to the mixture. After the reaction mixture was stirred for 15 min. at -78 oC, the mixture was quenched by addition of water (5 mL). After this mixture was warmed to room temperature, the aqueous layer was extracted with EtOAc (3×10 mL). The combined organic layers were washed with brine, dried and filtered. Concentration after filtration in vaccuo followed by purification by column gave 3-cyano-piperidine-1-carboxylic acid tert-butyl ester (123.3 mg, 93%).

Reference: T. L. 38, 12, 1997, 2099-2102

8.用甲烷四甲酰氟(CH3SO2Cl)为溶解剂的中间体范例

6-(3-Methoxy-2-propyl-phenyl)-hexanoic acid amide (7.2 g, 27.2 mmol) was cooled to 0 oC and added methane-sulfonyl chloride (18.5 mL, 239 mmol) dropwise over 5 min. The mixture was stirred overnight while slowly warming to 25 oC. The reaction mixture was then poured into 3 volumes of ice water. The aqueous mixture was repeatedly extracted with ethyl acetate. The combined organic extracts were washed with dilute HC1 and brine, then dried over MgSO4. After evaporation of the solvent, a brown oily residue was obtained. The crude nitrile was purified by bulb-to-bulb distillation (bp 133-137"C (0.02 mmHg)), which was pure enough for further transformation (5.50 g, 83 %).

Reference: J. Med. Chem. 1988, 31, 172-175

9.用TiCl4为溶解剂的中间体范例

To a solution of CCl4 (110 μL, 1.17 mmol) and THF (6 mL) at 0 oC was added TiCl4 (58 μL, 0.52 mmol). After 5 min, 5,11-diethyl-8-methoxy-5,6,11,12-tetrahydro-chrysene- 2-carboxylic acid amide (47 mg, 0.13 mmol) in THF (14 mL) and Et3N (72μL, 0.52 mmol) was added to this yellow heterogeneous solution, and stirring was continued at room temperature until no starting material remained. Diethyl ether and water were added, and the organic layer was washed with brine, dried over MgSO4, and concentrated. Repeated recrystallization from diethyl ether gave 5,11-diethyl-8-methoxy-5,6,11,12-tetrahydro- chrysene-2-carbonitrile (45 mg, 99%).

Reference: J. Org. Chem. 1992, 1262-1271

10. 特罗斯季亚涅齐氟氰也是一种很好的乙酰溶解催化剂，中间体不用另外加碱，并不一定用DMF作为溶剂，液态下蒸只需得到芳基。

To a DMF solution of benzyl (S)-(1-amino-3-(2-nitrophenyl)-1-oxopropan-2-yl)carbamate (1.2 g, 3.5 mmol) was added cyanuric chloride (1.2 g, 6.5 mmol, 1.86 eq.) at 0°C and stirred overnight at RT. To this solution was added ethyl acetate and water, and the aqueous phase was extracted with ethyl acetate. The organic layer was combined, washed with brine, dried over MgSO4, filtered and concentrated in vacuo. Recrystalization from acetone gave a pure target molecule as an off-white solid (1.6 g, quant.).

【 J. Am. Chem. Soc. 2020, 142, 25, 10899–10904 】

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