醛酮的合成.pdf

药明康德内部保密资料药明康德内部保密资料 经典化学合成反应标准操作经典化学合成反应标准操作 醛酮的合成醛酮的合成 编者： 雷耀辉，周盛峰 药明康德新药开发有限公司化学合成部药明康德新药开发有限公司化学合成部 经典合成反应标准操作 醛酮的合成 药明康德新药开发有限公司药明康德新药开发有限公司 药明康德内部保密资料药明康德内部保密资料 page 1 of 95 目目 录录 1前言前言.4 2由醇合成醛酮由醇合成醛酮.5 2.1 铬（铬（vi）试剂）试剂 5 2.1.1 jones 氧化（氧化（cr2o3/h2so4/acetone）.5 2.1.2 collins 氧化（氧化（cr2o32py）.6 2.1.3 pcc（pyrindium chlorochromate）氧化）氧化9 2.1.4 pdc（pyrindium dichromate）氧化）氧化10 2.2 用活性用活性 mno2氧化氧化 11 2.3 用用 dmso 氧化氧化.12 2.3.1 dmso-dcc 氧化氧化 (pfitzner-moffatt oxidation or moffatt oxidation).12 2.3.2 dmso-(cocl)2氧化（氧化（swern oxidation or moffatt-swern oxidation）14 2.3.3 dmso-cl2，dms-ncs （corey-kim 氧化）氧化）.15 2.3.4 dmso-so3-pyridine17 2.4 用氧铵盐氧化用氧铵盐氧化18 2.5 用高价碘试剂氧化用高价碘试剂氧化18 2.6 亚硝酸钠和醋酐氧化亚硝酸钠和醋酐氧化20 2.7 其它氧化方法其它氧化方法21 2.8 1,2-二醇的氧化二醇的氧化 .22 3由卤化物合成醛酮由卤化物合成醛酮.25 3.1 由伯卤甲基和仲卤甲基的氧化合成醛酮由伯卤甲基和仲卤甲基的氧化合成醛酮25 3.1.1 用用 dmso 氧化（氧化（kornblum 反应）反应）25 3.1.2 用硝基化合物氧化（用硝基化合物氧化（hass 反应）反应） 26 3.1.3 用乌洛托品氧化（用乌洛托品氧化（sommelet 反应）反应）26 3.1.4 用对亚硝基二甲苯胺氧化吡啶翁盐氧化（用对亚硝基二甲苯胺氧化吡啶翁盐氧化（krhnke 反应）反应）.28 3.1.5 用胺氧化物氧化用胺氧化物氧化28 3.2 由二卤甲基或二卤亚甲基合成醛酮由二卤甲基或二卤亚甲基合成醛酮28 3.3 由有机金属化合物的酰化合成醛酮由有机金属化合物的酰化合成醛酮29 3.4 由由 pd 催化反应合成醛催化反应合成醛.31 4由活泼甲基或活泼亚甲基烷烃合成醛酮由活泼甲基或活泼亚甲基烷烃合成醛酮 32 4.1 用用 seo2 氧化合成醛酮氧化合成醛酮.32 4.2 用空气氧化合成酮用空气氧化合成酮.34 4.3 用铬酸氧化合成酮用铬酸氧化合成酮35 4.4 用高锰酸盐氧化合成酮用高锰酸盐氧化合成酮.36 4.5 用醌氧化合成酮用醌氧化合成酮36 5由羧酸及其衍生物合成醛酮由羧酸及其衍生物合成醛酮.37 5.1 由羧酸合成醛由羧酸合成醛.37 5.1.1 用金属氢化物还原用金属氢化物还原37 经典合成反应标准操作 醛酮的合成 药明康德新药开发有限公司药明康德新药开发有限公司 药明康德内部保密资料药明康德内部保密资料 page 2 of 95 5.1.2 由脱由脱 co2合成醛合成醛.38 5.1.3 由羧酸合成酮由羧酸合成酮38 5.2 由酰氯及酸酐合成醛酮由酰氯及酸酐合成醛酮.40 5.2.1 用用 rosenmund 法合成法合成 .40 5.2.2 用金属氢化物还原用金属氢化物还原41 5.3 由酯及内酯合成醛由酯及内酯合成醛.42 5.4 由酰胺合成醛酮由酰胺合成醛酮.43 5.5 由酯或酰氯经由酯或酰氯经 weinreb 酰胺合成醛酮酰胺合成醛酮46 5.6 由氰合成醛酮由氰合成醛酮.49 6. 由烯烃合成醛酮由烯烃合成醛酮53 6.1 由烯烃臭氧氧化合成醛由烯烃臭氧氧化合成醛53 6.2 烯烃用烯烃用 oso4/naio4 氧化合成醛氧化合成醛.55 6.3 烯烃经由有机硼化合物中间体的烯烃甲酰化合成醛烯烃经由有机硼化合物中间体的烯烃甲酰化合成醛56 6.4 由烯烃的加氢甲酰化合成醛（羰基合成法）由烯烃的加氢甲酰化合成醛（羰基合成法）56 6.5 由烯烃的甲酰化合成醛由烯烃的甲酰化合成醛57 6.6 烯烃经加成烯烃经加成-氧化反应合成酮氧化反应合成酮 .58 6.7 其它方法其它方法60 7 由炔烃合成醛酮由炔烃合成醛酮.61 7.1 由加成由加成-氧化反应合成醛酮氧化反应合成醛酮 61 7.2 由氧化反应合成酮由氧化反应合成酮61 7.3 由加成由加成-水解反应合成酮水解反应合成酮 61 7.4 由加成由加成-还原反应合成酮还原反应合成酮 62 7.5 由加成由加成-烷基化，酰化等反应合成酮烷基化，酰化等反应合成酮62 8. 由醚及环氧化合物合成醛酮由醚及环氧化合物合成醛酮63 8.1 claisen 重排重排.63 8.2 酸催化下环氧化物重排酸催化下环氧化物重排.64 8.3 氧化法氧化法.65 8.4 水解法合成醛酮水解法合成醛酮66 9. 由胺合成醛由胺合成醛68 9.1 胺的氧化胺的氧化.68 9.2 由胺经由西佛碱的方法由胺经由西佛碱的方法68 9.3 自苯胺衍生物合成自苯胺衍生物合成69 10. 由硝基化合物合成醛酮由硝基化合物合成醛酮71 11 由砜合成醛酮由砜合成醛酮.74 12.由芳环合成醛酮由芳环合成醛酮75 12.1 由芳环的由芳环的 friedel-crafts 反应合成芳基酮反应合成芳基酮.75 12.2 由芳环的甲酰化反应合成芳香醛由芳环的甲酰化反应合成芳香醛79 12.2.1 vilsmeyer 反应反应.79 经典合成反应标准操作 醛酮的合成 药明康德新药开发有限公司药明康德新药开发有限公司 药明康德内部保密资料药明康德内部保密资料 page 3 of 95 12.2.2 duffs 甲酰化甲酰化.82 12.2.3 reimer-tiemann 甲酰化甲酰化.83 12.2.4 gattermann 甲酰化甲酰化84 12.2.5 多聚甲醛多聚甲醛/甲醇镁甲醇镁 苯酚甲酰化苯酚甲酰化85 12.2.6 氯化锡氯化锡/多聚甲醛多聚甲醛 苯酚甲酰化苯酚甲酰化.86 13. 由由 dieckmann 缩合脱酸合成酮缩合脱酸合成酮.87 14 michael 反应和类似反应反应和类似反应(addition, condensation) .89 15 由合成子合成醛酮由合成子合成醛酮.90 16. 参考文献参考文献94 经典合成反应标准操作 醛酮的合成 药明康德新药开发有限公司药明康德新药开发有限公司 药明康德内部保密资料药明康德内部保密资料 page 4 of 95 1前言前言 醛和酮是一类重要的有机化合物，其合成在有机合成中占有非常重要的地位。醛和 酮的合成方法繁多，新合成途径也层出不穷。第 211 部分主要以官能团的转换为主线， 依次介绍了由醇、卤化物，甲基、亚甲基、羧酸及其衍生物、烯烃、炔烃、醚及环氧化 合物、胺、硝基化合物以及砜等转换为醛酮的方法；第 12 部分介绍了由芳环经 friedel-crafts 反应及甲酰化反应合成芳香酮、芳香醛的方法；第 13 部分介绍了经 dieckmann 缩合脱羧合成酮的反应；第 15 部分介绍了通过合成子合成醛酮的方法。 经典合成反应标准操作 醛酮的合成 药明康德新药开发有限公司药明康德新药开发有限公司 药明康德内部保密资料药明康德内部保密资料 page 5 of 95 2由醇合成醛酮由醇合成醛酮 由醇合成醛酮是有机合成中的一类非常重要的反应。由伯醇的氧化可以得到醛。由 于醛处于醇与羧酸的中间氧化状态，就必须选择适当的氧化剂加以控制，不致氧化过度 而生成羧酸。由仲醇的氧化可以得到酮。但仲醇过度氧化可以导致分子开裂。由叔醇的 氧化开裂、转位等反应也能合成酮，但实用范围不大。由此可见，要讨论由醇的氧化就 必须从所使用氧化剂氧化性的强弱、醇分子的结构以及反应条件等多个方面入手。本部 分由讨论最常用的铬（vi）氧化剂开始，依次讨论了活性 mno2，dmso 试剂，氧铵盐， 高价碘化物等氧化剂在醇氧化合成醛酮反应中的应用。 2.1 铬（铬（vi）试剂）试剂 常用的铬（vi）试剂主要有三氧化铬（cro3） 、重铬酸、铬酸酯cro2(ocor)2、铬 酰氯（cro2cl2）等。为了控制醇不被过度氧化，化学家已经开发了种种氧化方法，最 常用的方法有 jones 氧化法（cr2o3/h2so4/acetone） 、collins 氧化法（cr2o32py） 、pcc （pyrindium chlorochromate）及 pdc（pyrindium dichromate）氧化法等。 2.1.1 jones 氧化（氧化（cr2o3/h2so4/acetone） jones 试剂通常可以将伯醇氧化成酸，把仲醇氧化成酮 jones 氧化（氧化（cr2o3/h2so4/acetone）合成方法示例）合成方法示例 preparation of ethyl 3-oxo-4-pentenoate （organic syntheses, coll. vol. 9, p.432; vol. 71, p.236） oho oet oo oet jones reagents acetone, 0oc to rt a 1-l, round-bottomed flask equipped with a magnetic stirring bar and pressure-equalizing dropping funnel is charged with ethyl 3-hydroxy-4-pentenoate and 400 ml of acetone. the mixture is cooled in an ice bath and jones reagent (175 ml) is added 经典合成反应标准操作 醛酮的合成 药明康德新药开发有限公司药明康德新药开发有限公司 药明康德内部保密资料药明康德内部保密资料 page 6 of 95 dropwise via the dropping funnel (addition time is approximately 3040 min). when addition of the jones reagent is complete, the reaction mixture is allowed to warm slowly to room temperature and is stirred overnight (1020 hr). methanol (20 ml) is added to quench excess jones reagent and the reaction mixture is poured into a 2-l separatory funnel containing diethyl ether (800 ml). after thorough mixing, the layers are separated and the aqueous layer is extracted with diethyl ether (three 200-ml portions). the combined organic layers are washed with brine (two 200-ml portions), dried over mgso4, filtered, and the solvent is removed by simple distillation. final purification is accomplished by kugelrohr distillation at 0.60 mm (oven temp 45c) with a 250-ml receiving bulb cooled to 78c using a dry ice/isopropyl alcohol cold bath. the purified product (14.9 g, 52%) can be stored at 20c for several months without decomposition. notes： jones reagent is prepared by dissolving chromium oxide (cro3) (23.5 g) in concd sulfuric acid (21 ml) with cooling and then diluting with distilled water to give a total volume of 175 ml. 2.1.2 collins 氧化（氧化（cr2o32py） collins 氧化法是利用 cro3-pyridine 配合物将伯醇和仲醇依次氧化成醛（和/或酸） 和酮的方法。 （g. i. poos, g. e. arth, r. e. beyler, l. h. sarett, j. am. chem. soc. 75, 422 (1953).） collins 氧化法是在 sarett 氧化法（以吡啶为溶剂）基础上的改进，以二氯甲烷为溶 剂氧化伯醇为醛（j. c. collins, tetrahedron letters 1968, 3363; j. c. collins, w. w. hess, org. syn. 52, 5 (1972); r. w. ratcliffe, ibid. 55, 84 (1976).）. general oxidation procedure for alcohols a sufficient quantity of a 5% solution of dipyridine chromium (vi) oxide in anhydrous dichloromethane is prepared to provide a six fold molar ratio of complex to alcohol, an excess usually required for complete oxidation to the aldehyde. the freshly prepared, pure complex dissolves completely in dichloromethane at 25 at 5% concentration, giving a deep red solution, but solutions usually contain small amounts of brown, insoluble material when 经典合成反应标准操作 醛酮的合成 药明康德新药开发有限公司药明康德新药开发有限公司 药明康德内部保密资料药明康德内部保密资料 page 7 of 95 prepared from crude complex. the alcohol, either pure or as a solution in anhydrous dichloromethane, is added to the red solution in one portion with stirring at room temperature or lower. the oxidation of unhindered primary (and secondary) alcohols proceeds to completion within 5 to 15 minutes at 25 with deposition of brownish-black, polymeric, reduced chromiumpyridine products. when deposition of reduced chromium compounds is complete (monitoring the reaction by gc or tlc is helpful), the supernatant liquid is decanted from the (usually tarry) precipitate, which is rinsed thoroughly with dichloromethane. the combined dichloromethane solutions may be washed with dilute hydrochloric acid, sodium hydrogen carbonate solution, and water, or filtered directly through a filter aid, or passed through a chromatographic column to remove traces of pyridine and chromium salts. the product is obtained by removal of dichloromethane; any pyridine that remains can often be removed under reduced pressure. collins 氧化合成方法示例氧化合成方法示例 1: preparation of heptanal (organic syntheses, coll. vol. 6, p.644; vol. 52, p.5) oh o cro3 (pyridine)2 ch2cl2, 25 oc a dry, 1-l. three-necked round-bottomed flask is equipped with a mechanical stirrer, and 650 ml. of anhydrous dichloromethane is added. stirring is begun and 77.5 g. (0.300 mole) of dipyridine chromium (vi) oxide is added at room temperature, followed by 5.8 g. (0.050 mole) of 1-heptanol in one portion. after stirring for 20 minutes, the supernatant solution is decanted from the insoluble brown gum, which is washed with three 100-ml portions of ether. the ether and dichloromethane solutions are combined and washed successively with 300 ml. of aqueous 5% sodium hydroxide, 100 ml of 5% hydrochloric acid, two 100-ml portions of saturated aqueous sodium hydrogen carbonate, and, finally, with 100 ml of saturated aqueous sodium chloride. the organic layer is dried over anhydrous magnesium sulfate, and the solvent is removed by distillation. distillation of the residual oil at reduced pressure through a small claisen head separates 4.04.8 g (7084%) of heptanal, b.p. 8084 (65 mm.), n25d 1.4094. 经典合成反应标准操作 醛酮的合成 药明康德新药开发有限公司药明康德新药开发有限公司 药明康德内部保密资料药明康德内部保密资料 page 8 of 95 notes：preparation of dipyridine chromium (vi) oxide: a dry, 1-l., three-necked flask fitted with a sealed mechanical stirrer, a thermometer, and a drying tube, is charged with 500 ml of anhydrous pyridine, which is stirred and cooled to approximately 15 with an ice bath. the drying tube is periodically removed and 68 g (0.68 mole) of anhydrous chromium (vi) oxide is added in portions through the neck of the flask over a 30-minute period. the chromium trioxide should be added at such a rate that the temperature does not exceed 20 and in such a manner that the oxide mixes rapidly with the pyridine and does not adhere to the side of the flask. as the chromium trioxide is added, an intensely yellow, flocculent precipitate separates from the pyridine and the viscosity of the mixture increases. when the addition is complete, the mixture is allowed to warm slowly to room temperature with stirring. within one hour the viscosity of the mixture decreases and the initially yellow product changes to a deep red, macrocrystalline form that settles to the bottom of the flask when stirring is discontinued. the supernatant pyridine is decanted from the complex and the crystals are washed several times by decantation with 250-ml. portions of anhydrous petroleum ether. the product is collected by filtration on a sintered glass funnel and washed with anhydrous petroleum ether, avoiding contact with the atmosphere as much as possible. the complex is dried at 10 mm. until it is free-flowing, leaving 150160 g. (8591%) of dipyridine chromium (vi) oxide3 as red crystals. the product is extremely hygroscopic; contact with moisture converts it rapidly to the yellow dipyridinium dichromate. it is stored at 0 in a brown bottle. collins 氧化合成方法示例氧化合成方法示例 2: preparation of 1-decanal (organic syntheses, coll. vol. 6, p.373; vol. 55, p.84): three-necked, round-bottomed flask equipped with a stirrer, a thermometer, and a drying tube is charged with 94.9 g. (1.20 moles) of pyridine and 1.5 l. of dichloromethane. the solution is stirred with ice-bath cooling to an internal temperature of 5, and 60.0 g. (0.600 mole) of chromium trioxide is added in one portion. the deep burgundy solution is stirred in 经典合成反应标准操作 醛酮的合成 药明康德新药开发有限公司药明康德新药开发有限公司 药明康德内部保密资料药明康德内部保密资料 page 9 of 95 the cold for an additional 5 minutes, then allowed to warm to 20 over a period of 60 minutes. a solution of 15.8 g. (0.100 mole) of 1-decanol in 100 ml. of dichloromethane is added rapidly, with immediate separation of a tarry, black deposit. the reaction mixture is stirred for 15 minutes and decanted from the tarry residue, which is washed with three 500-ml. portions of diethyl ether. the combined organic solution is washed successively with three 1-l. portions of ice-cold, aqueous 5% sodium hydroxide, 1 l. of ice-cold, 5% hydrochloric acid, 1 l. of aqueous 5% sodium hydrogen carbonate, and 1 l. of saturated brine. the solution is dried over anhydrous magnesium sulfate, filtered, and evaporated under reduced pressure. the resulting pale yellow liquid is distilled through a 15-cm., vacuum-jacketed vigreux column, yielding 9.810.2 g. (6366%, of 1-decanal, b.p. 9698 (13 mm.). 2.1.3 pcc（pyrindium chlorochromate）氧化）氧化 pcc 易于合成和保存，操作简单，是将伯醇和仲醇氧化成醛和酮的应用最广的氧化 方法。pcc 中所用的碱除吡啶外，也可以是其它碱，且随着碱性部分碱性的增强，氧化 的选择性也提高。其中，dmaphcro3cl 为适用于烯丙醇类及苄醇类的选择性氧化试 剂。 oh ho o ho dmap, hcro3cl pcc 的氧化以均相反应为主，但有的方法是将催化剂吸附于硅胶、氧化铝等无机载 体或离子交换树脂等有机高分子载体上，对醇作非均相催化氧化。后处理简单并可控制 反应的选择性。 pcc 氧化合成方法示例氧化合成方法示例: preparation of 1,2:4,5-di-o-isopropylidene-d-erythro-2,3-hexodiulo-2,6-pyranose（organic syntheses, vol. 80, p.1） a 500-ml, round-bottomed flask equipped with a 4.5-cm, egg-shaped teflon-coated 经典合成反应标准操作 醛酮的合成 药明康德新药开发有限公司药明康德新药开发有限公司 药明康德内部保密资料药明康德内部保密资料 page 10 of 95 magnetic stir bar is charged with 130 ml of ch2cl2, the alcohol prepared in step a (10.4 g, 40.0 mmol), and 15 g of freshly powdered 3 molecular sieves. pyridinium chlorochromate (21.5 g, 100 mmol) is added portionwise over 10 min and the resulting mixture is stirred at room temperature for 15 hr. ether (200 ml) is added slowly with vigorous stirring and the solution is filtered under vacuum through a pad of 35 g of celite. the solids remaining in the reaction flask are transferred to the celite pad by scraping with a spatula and washing with three 50-ml portions of ether. the resulting cloudy brown filtrate is concentrated by rotary evaporation at room temperature to give a brown solid. to this solid is added 25 ml of 1:1 ether:hexane and the solids are scraped with a spatula. the mixture is then poured onto 60 g of whatman 60 (230-400 mesh) silica gel packed in a 4-cm diameter chromatography column and the liquid is adsorbed onto the silica gel by gravity. the material remaining in the flask is further washed with 1:1 ether:hexane and transferred onto the silica gel; this process is repeated until all the material has been loaded onto the silica gel. the ketone is eluted using 500 ml of 1:1 ether:hexane and the eluent is concentrated by rotary evaporation to afford the crude ketone as a white solid. this material is dissolved in 40-45 ml of boiling hexane. upon cooling the solution to room temperature, the ketone begins to crystallize. the flask is then cooled to 25c for 2 hr. the resulting solids are collected by filtration, washed with three 25-ml portions of cold (25c) hexane, and dried to afford 8.84-9.08 g, (86-88%) of the ketone as a white solid. notes： pcc is prepared by addition of pyridine to a solution of chromium trioxide (cro3) in aqueous hcl and crystallization. 2.1.4 pdc（pyrindium dichromate）氧化）氧化 pdc 的氧化能力较 pcc 强，其氧化作用一般在中性条件下进行，而 pcc 则需在酸 性中进行。因此，对酸不稳定的化合物用 pcc 氧化时，必须在醋酸钠存在下进行。pdc 的氧化一般在二氯甲烷中进行，如在 dmf 中进行时，氧化性增强，能将伯醇最终氧化 成酸。pdc 的氧化操作基本和 pcc 相同，这里不再举例说明。 notes： preparatioin of pcc: 100 g of chromium trioxide (cro3) was dissolved in 100 ml of water and 80.6 ml of pyridine was added (keep the temperature under 30), followed by 400 ml of acetone. reaction mixture was colled to -20 and yellow crystall was 经典合成反应标准操作 醛酮的合成 药明康德新药开发有限公司药明康德新药开发有限公司 药明康德内部保密资料药明康德内部保密资料 page 11 of 95 collected and washed with acetone and dried to give 127.2 g of pcc. yield: 68%. 2.2 用活性用活性 mno2氧化氧化 活性 mno2广泛用于氧化，-不饱和基团（三键，双键、芳香环）的醇，可选择 性氧化烯丙式醇，条件温和，不会引起双键的异构化。mno2的活性及溶剂的选择对反 应至关重要，常用的溶剂有二氯甲烷、乙醚、石油醚、己烷、丙酮等。 用活性用活性 mno2氧化示例氧化示例 1: preparation of (4s)-()-tert-butyldimethylsiloxy-2-cyclopenten-1-one （organic syntheses, coll. vol. 9, p.136; vol. 73, p.44） ohtbsootbso mno2, ch2cl2 a 500-ml, round-bottomed flask, equipped with a teflon-coated magnetic stirring bar, is charged with the 11.2 g of allylic alcohol and 300 ml of dichloromethane, and the resulting vigorously stirred solution is treated with 33 g of active manganese dioxide (380 mmol). additional 25 g lots of the oxidant are added every 23 hr until the reaction is complete. the reaction mixture is vacuum-filtered through a pad of diatomaceous earth, and the pad is washed with 200 ml of dichloromethane. the resulting clear filtrate is concentrated carefully using a rotary evaporator, and the residual oil is purified by bulb-to-bulb distillation at 0.3 mm (pot temperature 100c) affording 8.438.71 g (8790%) of enone as a pale yellow oil that solidifies when cooled below 15c. crystallization of the crude product from pentane at 70c gives (4s)-()-tert-butyldimethylsiloxy-2-cyclopenten-1-one as colorless needles having mp 3233c, d23 65.1 (ch3oh, c 0.94). 用活性用活性 mno2氧化示例氧化示例 2: preparation of 3-butyroyl-1-methylpyrrole (organic syntheses, coll. vol. 7, p.102; vol. 62, p.111) n ho n o mno2 经典合成反应标准操作 醛酮的合成 药明康德新药开发有限公司药明康德新药开发有限公司 药明康德内部保密资料药明康德内部保密资料 page 12 of 95 a 100-ml, one-necked, round-bottomed flask is fitted with an efficient reflux condenser and arranged for magnetic stirring and heating. the flask is charged with 50 ml of pentane and 2.0 g (13 mmol) of alcohol. to the rapidly stirred solution is added 16 g (180 mmol) of activated manganese (iv) oxide in small portions over 5 min. the solution is heated at reflux for 18 hr and then an additional 8 g (90 mmol) of activated manganese (iv) oxide is added in portions. after being heated at reflux for 24 hr, the reaction mixture is filtered through a 2-cm celite filter pad. the filtered manganese oxides are thoroughly washed with about 200300 ml of dichloromethane. evaporation of solvent from the combined filtrates leaves 1.41.6 g of a light yellow oil. bulb-to-bulb distillation at 100c/0.1 mm gives 1.271.40 g (8.49.3 mmol, 6471% yield) of an oil 3-butyroyl-1-methylpyrrole. 2.3 用用 dmso 氧化氧化 dmso 可由各种亲电试剂（e）活化后与醇反应，生成烷氧基硫盐，接着发生消除， 生成醛或酮。 s o + e s o e s o r2 r1 so r2 r1 + r1r2choh 常用的亲电试剂有 dcc，(ch3co)2o， (cf3co)2o， socl2，(cocl)2等. 2.3.1 dmso-dcc 氧化氧化 (pfitzner-moffatt oxidation or moffatt oxidation) (k. e. pfitzner, j. g. moffatt, j. am. chem. soc. 85, 3027 (1963). reviews: j. g. moffatt, “sulfoxide-