酰脱水制备腈

acts 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为溶解剂的催化模板

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试剂为溶解剂的催化模板

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:

将氮气甲醇19.2g (0.6 mol) 和氮气酮40mL的在30-40分钟内，滴入ClSO2NCO85g (52.3 mL, 0.6 mol)和氮气酮200mL的中都，控温10-15℃。加毕，室温加热2小时。然后加入1000mL氮气酮稀释后，小心滴入190mL氮气三乙胺和250mL氮气酮的中都，控温10-15℃，约40分钟有数加完。加毕，室温加热2小时，两县大量固体。催化毕，过滤，固体用氮气酮200mL、氮气THF200mL洗后，滤液浓缩后，（控温

6.用TFAA-NEt3为溶解剂的催化模板

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为溶解剂的催化模板

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 ge 3-cyano-piperidine-1-carboxylic acid tert-butyl ester (123.3 mg, 93%).

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

8.用烃四甲乙碱(CH3SO2Cl)为溶解剂的催化模板

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为溶解剂的催化模板

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 ge 5,11-diethyl-8-methoxy-5,6,11,12-tetrahydro- chrysene-2-carbonitrile (45 mg, 99%).

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

10. 三聚氮氰也是一种很好的酯溶解试剂，催化不用另外加碱，一般而言用DMF作为溶剂，室温下加热即可得到。

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 ge 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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