古代服饰名称.pdf

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1、实验十六氯霉素（Chloramphenicol）的合成一、目的要求1.熟悉溴化、Delepine反应、乙酰化、羟甲基化、Meerwein-Ponndorf-Verley羰基还原、水解、拆分、二氯乙酰化等反应的原理。2.掌握各步反应的基本操作和终点的控制。3.熟悉氯霉素及其中间体的立体化学。4.了解播种结晶法拆分外消旋体的原理，熟悉操作过程。5.掌握利用旋光仪测定光学异构体质量的方法。二、实验原理氯霉素的化学名为1R，2-（-）-1-对硝基苯基-2-二氯乙酰胺基-1，3-丙二醇，（1R，2R）-（-）-p-nitropHenyl-2-dichloroacetamido-1，3-propanedi

2、ol。氯霉素分子中有两个手性碳原子，有四个旋光异构体。化学结构式为：NO2CHOHCCH2OHHCl2CHCOHNNO2CHOHCCH2OHHNHCOCHCl21R,2R(-)1S,2S(+)NO2CHOHCCH2OHCl2CHCOHNHNO2COHHCCH2OHNHCOCHCl2H1S,2R(-)1R,2S(+)上面四个异构体中仅1R，2R（-）或 D（-）苏阿糖型有抗菌活性，为临床使用的氯霉素。氯霉 素 为 白色 或微 黄色 的针 状、长片 状结晶 或 结晶 性 粉末，味 苦。mp.149153。易溶于甲醇、乙醇、丙酮或丙二醇中，微溶于水。比旋度25-25.5（乙酸乙酯）；D25+18.5

3、21.5（无水乙醇）。合成路线如下：O2NCOCH3Br2,C6H5ClO2NCOCH2Br(CH2)6N4,C6H5ClO2NCOCH2Br(CH2)6N4C2H5OHHCl,H2OO2NCOCH2NH2.HCl(CH3CO)2OCH3COONaO2NCOCH2NHCOCH3HCHOC2H5OHO2NCOCHCH2OHNHCOCH3AlOCH(CH3)23CH3CH(OH)CH3O2NCHOHCCH2OHHNHCOCH3O2NCHOHCCH2OHHNH2.HClHCl,H2ONaOHO2NCHOHCCH2OHHNH2O2NCHOHCCH2OHHNHCOCH3CHCl2COOCH3,CH3OH

4、O2NCHOHCCH2OHHNHCOCHCl215%拆分三、实验方法（一）对硝基-溴代苯乙酮的制备在装有搅拌器、温度计、冷凝管、滴液漏斗的250 mL 四颈瓶中，加入对硝基苯乙酮 10 g，氯苯 75 mL，于 2528搅拌使溶解。从滴液漏斗中滴加溴9.7 g。首先滴加溴 23 滴，反应液即呈棕红色，10 min内褪成橙色表示反应开始；继续滴加剩余的溴，约11.5 h加完，继续搅拌1.5 h，反应温度保持在2528。反应完毕，水泵减压抽去溴化氢约30 min，得对硝基-溴代苯乙酮氯苯溶液，备用。注释：1.制备氯霉素的二、实验原理除以对硝基苯乙酮为原料的二、实验原理（对酮法）外，还有成肟法、苯乙

5、烯法、肉桂醇法、溴苯乙烯法以及苯丝氨酸法等。2.冷凝管口上端装有气体吸收装置，吸收反应中生成的溴化氢。3.所用仪器应干燥，试剂均需无水。少量水分将使反应诱导期延长，较多水分甚至导致反应不能进行。4.若滴加溴后较长时间不反应，可适当提高温度，但不能超过50，当反应开始后要立即降低到规定温度。5.滴加溴的速度不宜太快，滴加速度太快及反应温度过高，不仅使溴积聚易逸出，而且还导致二溴化合物的生成。6.溴化氢应尽可能除去，以免下步消耗六亚甲基四胺。文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T

6、5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文

7、档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ

8、9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10

9、N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 H

10、K2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B

11、3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3

12、ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5思考题：1.溴化反应开始时有一段诱导期，使用溴化反应机理说明原因？操作上如何缩短诱导期？2.本溴化反应不能遇铁，铁的存在对反应有何影响？（二）对硝基-溴化苯乙酮六亚甲基四胺盐的制备在装有搅拌器、温度计的250 mL 三颈瓶中，依次加入上步制备好的对硝基-溴代苯乙酮和氯苯20 mL，冷却至 15以下，在搅拌下加入六亚甲基四胺（

13、乌洛托品）粉末 8.5 g，温度控制在 28以下，加毕，加热至3536，保温反应 1 h，测定终点。如反应已到终点，继续在3536反应 20 min，即得对硝基-溴代苯乙酮六亚甲基四胺盐（简称成盐物），然后冷至 1618，备用。注释：1.此反应需无水条件，所用仪器及原料需经干燥，若有水分带入，易导致产物分解，生成胶状物。2.反应终点测定：取反应液少许，过滤，取滤液1 mL，加入等量 4%六亚甲基四胺氯仿溶液，温热片刻，如不呈混浊，表示反应已经完全。3.对硝基-溴代苯乙酮六亚甲基四胺盐在空气中及干燥时极易分解，因此制成的复盐应立即进行下步反应，不宜超过12 h。4.复盐成品：mp.118120（

14、分解）。思考题：1.对硝基-溴代苯乙酮与六亚甲基四胺生成的复盐性质如何？2.成盐反应终点如何控制？根据是什么？（三）对硝基-氨基苯乙酮盐酸盐的制备在上步制备的成盐物氯苯溶液中加入精制食盐3 g，浓盐酸 17.2 mL，冷至612，搅拌 35 min，使成盐物呈颗粒状，待氯苯溶液澄清分层，分出氯苯。立即加入乙醇 37.7 mL，搅拌，加热，0.5 h 后升温到 3235，保温反应 5 h。冷至 5以下，过滤，滤饼转移到烧杯中加水19 mL，在 3236搅拌 30 min，再冷至-2，过滤，用预冷到 23的 6 mL 乙醇洗涤，抽干，得对硝基-氨基苯乙酮盐酸盐（简称水解物），mp.250（分解），

15、备用。注释：1.对硝基-溴代苯乙酮与六亚甲基四胺（乌洛托品）反应生成季铵盐，然后在酸性条件下水解成对硝基-氨基苯乙酮盐酸盐。该反应称Delepine 反应。2.加入精盐在于减小对硝基-氨基苯乙酮盐酸盐的溶解度。文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P

16、8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV

17、1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S

18、8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编

19、码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U

20、6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1

21、C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2

22、C10B3P8G3 ZV1A8T5S8R53.成盐物水解要保持足够的酸度，所以与盐酸的摩尔比应在3 以上。用量不仅导致生成醛等副反应（Sommolet 反应），而且对硝基-氨基苯乙酮游离碱本身亦不稳定，可发生双分子缩合，然后在空气中氧化成紫红色吡嗪化合物。此外，为保持水解液有足够酸度，应先加盐酸后加乙醇，以免生成醛等副反应。4.温度过高也易发生副反应，增加醛等副产物的生成。思考题：1.本实验中 Delepine 反应水解时为什么一定要先加盐酸后加乙醇，如果次序颠倒，结果会怎样？2.对硝基-氨基苯乙酮盐酸盐是强酸弱碱生成的盐，反应需保持足够的酸度，如果酸度不足对反应有何影响？(四)对硝基-乙酰胺

23、基苯乙酮的制备在装有搅拌器、回流冷凝器、温度计和滴液漏斗的250 mL 四颈瓶中，放入上步制得的水解物及水20 mL，搅拌均匀后冷至 05。在搅拌下加入醋酐9 mL。另取 40%的醋酸钠溶液 29 mL，用滴液漏斗在30 min 内滴入反应液中，滴加时反应温度不超过15。滴毕，升温到1415，搅拌 1 h（反应液始终保持在pH 3.54.5），再补加醋酐 1mL，搅拌 10 min，测定终点。如反应已完全，立即过滤，滤饼用冰水搅成糊状，过滤，用饱和碳酸氢钠溶液中和至 pH 7.27.5，抽滤，再用冰水洗至中性，抽干，得淡黄色结晶（简称乙酰化物）,mp.161163。注释：1.该反应需在酸性条件

24、下（pH 3.54.5）进行，因此必须先加醋酐，后加醋酸钠溶液，次序不能颠倒。2.反应终点测定：取反应液少许，加入 NaHCO3中和至碱性，于 4045温热 30 min，不应呈红色。若反应未达终点，可补加适量的醋酐和醋酸钠继续酰化。3.乙酰化物遇光易变红色，应避光保存。思考题：1.乙酰化反应为什么要先加醋酐后加醋酸钠溶液，次序不能颠倒？2.乙酰化反应终点怎样控制，根据是什么？(五)对硝基-乙酰胺基-羟基苯丙酮的制备在装有搅拌器、回流冷凝管、温度计的250 mL 三颈瓶中，投入乙酰化物及乙醇 15 mL，甲醛 4.3 mL，搅拌均匀后用少量NaHCO3饱和溶液调 pH 7.27.5。搅拌下缓慢

25、升温，大约40 min 达到 3235，再继续升温至 3637，直到反应文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I1

26、0N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5

27、HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10

28、B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3

29、 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8

30、T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5

31、文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5完全。迅速冷却至0，过滤，用 25 mL 冰水分次洗涤，抽滤，干燥得对硝基-乙酰胺基-羟基苯丙酮

32、（简称缩合物），mp.166167。注释：1.本反应碱性催化的pH 值不宜太高，pH 7.27.5 较适宜。pH 过低反应不易进行，pH 大于 7.8 时有可能与两分子甲醛形成双缩合物。甲醛的用量对反应也有一定影响，如甲醛过量太多，亦有利于双缩合物的形成；用量过少，可导致一分子甲醛与两分子乙酰化物缩合。O2NCOCH2NHCOCH3O2NCOCNHCOCH3CH2OHCH2OHO2NCOCH2NHCOCH3O2NCOCHNHCOCH3CH2O2NCOCHNHCOCH3+2 HCHO+HCHO为了减少上述副反应，甲醛用量控制在过量40%左右（摩尔比约为 1：1.4）为宜。2.反应温度过高也有双缩

33、合物生成，甚至导致产物脱水形成烯烃。3.反应终点测定：用玻棒蘸取少许反应液于载玻片上，加水1 滴稀释后置显微镜下观察，如仅有羟甲基化合物的方晶而找不到乙酰化物的针晶，即为反应终点（约需 3 h）。思考题：1.影响羟甲基化反应的因素有那些？如何控制？2.羟甲基化反应为何选用NaHCO3作为碱催化剂？能否用NaOH，为什么？3.羟甲基化反应终点如何控制？（六）异丙醇铝的制备在装有搅拌器、回流冷凝管、温度计的三颈瓶中依次投入剪碎的铝片2.7 g，无水异丙醇 63 mL 和无水三氯化铝0.3 g。在油浴上回流加热至铝片全部溶解，冷却到室温，备用。注释：1.所用仪器、试剂均应干燥无水。2.回流开始要密切

34、注意反应情况，如反应太剧烈，需撤去油浴，必要时采取适当降温措施。3.如果无水异丙醇、无水三氯化铝质量好，铝片剪得较细，反应很快进行，文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10

35、B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3

36、 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8

37、T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5

38、文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:C

39、J9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I1

40、0N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5约需 1-2 h，即可完成。(七)D

41、L-苏阿糖型-1-对硝基苯基-2-氨基-1，3-丙二醇的制备在上步制备异丙醇铝的三颈瓶中加入无水三氯化铝1.35 g，加热到 4446，搅拌 30 min。降温到 30，加入缩合物 10 g。然后缓慢加热，约30 min 内升温到 5860，继续反应 4 h。冷却到 10以下，滴加浓盐酸70 mL。滴毕，加热到 7075，水解 2 h（最后 0.5 h加入活性炭脱色），趁热过滤，滤液冷至 5以下，放置 1 h。过滤析出的固体，用少量20%盐酸（预冷至 5以下）8 mL 洗涤。然后将固体溶于 12 mL水中，加热到 45，滴加 15%NaOH溶液到 pH 6.57.6。过滤，滤液再用 15%Na

42、OH 调节到 pH 8.49.3，冷却至 5以下，放置 1 h。抽滤，用少量冰水洗涤，干燥，得DL-苏阿糖型-1-对硝基苯基-2-氨基-1，3-丙二醇（DL-氨基物），mp.143145。注释：1.滴加浓盐酸时温度迅速上升，注意控制温度不超过50。滴加浓盐酸促使乙酰化物水解，脱乙酰基，生成DL-氨基物盐酸盐，反应液中盐酸浓度大致在20%以上，此时 AL(OH)3形成了可溶性的 AlCl3-HCl 复合物，而 DL-氨基物盐酸盐在 50以下溶解度小，过滤除去铝盐。2.用 20%盐酸洗涤的目的是除去附着在沉淀上的铝盐。3.用 15%NaOH 溶液调节反应液到pH 6.57.6，可以使残留的铝盐转变

43、成AL(OH)3絮状沉淀过滤除去。4.还原后所得产物除DL-苏阿糖型异构体外，尚有少量 DL-赤藓糖型异构体存在。由于后者的碱性较前者强，且含量少，在pH 8.49.3时，DL-苏阿糖型异构体游离析出，而DL-赤藓糖型异构体仍留在母液中而分离。思考题：1.制备异丙醇铝的关键有哪些？2.Meerwein-Ponndorf-Verley还原反应中加入少量AlCl3有何用？3.试解释异丙醇铝异丙醇还原DL-对硝基-乙酰胺基-羟基苯丙酮主要生成 DL-苏阿糖型氨基物的理由。4.还原产物1-对硝基苯基-2-乙酰氨基-1，3-丙二醇水解脱乙酰基，为什么用 HCl 而不用 NaOH 水解？水解后产物为什么用

44、20%盐酸洗涤？5.“氨基醇”盐酸盐碱化时为什么要二次碱化？(八)D-（-）-1-对硝基苯基-氨基-1，3-丙二醇的制备1.拆分文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3

45、P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 Z

46、V1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5

47、S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档

48、编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9

49、U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N

50、1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5文档编码:CJ9U6I10N1C5 HK2C10B3P8G3 ZV1A8T5S8R5在装有搅拌器、温度计的250 mL 三颈