Mechanism of hydride reduction of 1-alkyn-3-ols
Mechanism of hydride reduction of 1-alkyn-3-ols
复制标题
1-炔-3-醇的氢化物还原机理
DOI：
10.1021/jo00921a024
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发表时间：
1974
影响因子：
3.6
通讯作者：
C. Djerassi
中科院分区：
文献类型：
--
作者：
B. Grant;C. Djerassi
氧化14a。将化合物14a （165 mg, 0.425 mmol）溶于15 ml醋酸-氯仿（2:1）和30%过氧化氢（180 mg, 1.6 mmol）的醋酸溶液（2.8 ml）中。1-0.2 ml份，室温下。将反应混合物用水稀释，用氯仿提取。结合的氯仿层用碳酸钠和碳酸氢钠水溶液洗涤，干燥（MgSO*），浓缩成油，静置后结晶。再结晶得到112 mg (0.28 mmol, 65%), mp 149-150（水相EtOH）。该产物（67 mg）通过制备tic（硅胶，二氯甲烷）进一步纯化，再结晶后得到27 mg的14b， mp 167-168 （MeOH）。分析的。C2/H32OS: C, 80.15；7.97 H,。发现：C， 80.21；7.98 H,。三苯基溴化磺酸与氧化锂的反应。将三苯基溴化磺酸（119 mg, 0.348 mmol）和氧化锂（292 mg, 9.7 mmol）在乙醚中组成的浆液连续搅拌。在室温下放置2天后，tic（二氧化硅-氯仿）表明可能存在苯基硫化物。9天后，用稀硫酸水解，提取乙醚。将干燥的MgSOH醚提取物浓缩，得到一种几乎完全是脂肪族的油（51毫克）（核磁共振），尽管存在一个小的芳香峰（< 2%），表明存在苯基硫化物。Glc （5% SP-100在80/100 ABS上，6英尺X 2毫米，fid）给出了与苯基硫醚相同保留时间的峰。氯仿萃取水层（经钴和铋斑点试验证实）27含有一种磺化盐，在加入溴化钠（5克）后得到粗制的三苯基溴化磺酸（171毫克）。
Oxidation of 14a. Compound 14a (165 mg, 0.425 mmol) was dissolved in 15 ml of acetic acid-chloroform (2: 1) and 30% hydro-gen peroxide (180 mg, 1.6 mmol) in acetic acid solution (2.8 ml) added in0. 1-0.2-ml portions at room temperature. The reaction mixture was diluted with water and extracted with chloroform. The combined chloroform layers were washed with aqueous sodi-um carbonate and sodium bicarbonate, dried (MgSO*), and con-centrated to give an oil, which crystallized upon standing. Re-crystallization gave 112 mg (0.28 mmol, 65%), mp 149-150 (aque-ous EtOH). This product (67 mg) was further purified byprepar-ative tic (silica gel, methylene chloride) to give, after recrystalli-zation, 27 mg of 14b, mp 167-168 (MeOH). Anal. Caled for C2/H32OS: C, 80.15; H, 7.97. Found: C, 80.21; H, 7.98. Reaction of Triphenylsulfonium Bromide with Lithium Oxide. A slurry of triphenylsulfonium bromide (119 mg, 0.348 mmol) and lithium oxide (292 mg, 9.7 mmol) in ether was stirred continuously. After 2 days at room temperature, tic (silica-chloroform) indicated the possiblepresence of phenyl sulfide. After 9 days, the mixture was hydrolyzed with dilute sulfuric acid and ether extracted. The dried"(MgSOH ether extracts were concen-trated to give an oil (51 mg) which was almost totally aliphatic (nmr), although a small aromatic peak (< 2%) indicative of phe-nyl sulfide was present. Glc (5% SP-100 on 80/100 ABS, 6 ft X 2 mm, fid) gave a peak with the same retention time as phenyl sul-fide. Chloroform extraction of the water layer, which was shown by the cobalt and bismuth spot tests27 to contain a sulfonium salt, after the addition of sodium bromide (5 g) gave crude triphenylsulfonium bromide (171 mg).