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问题：关于丙二酸二乙酯的氯化和溴化
类型：求助 (悬赏分:3分)
提问：puyun86
等级：▲
版块：有机化学问题(jimuwei,fpcwin1211,netpanda,yjgzfl,Ftian,)
信誉：0%
回复：24
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时间：2008-11-25 22:16:19  编辑    加入/取消收藏    订制/取消短消息    举报该贴    

如何将丙二酸二乙酯氯化和溴化？二氯代、二溴代是不是比一氯代、一溴代困难？谢谢专家指教！！！
回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 10:26:57   编辑 1楼
这个根本不困难，凡是学过有机化学的 都应该知道，别说是高等有机化学，就是 基础有机化学书上都有


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 10:27:37   编辑 2楼
第14章说的清清楚楚，明明白白，有机合成就是要记得机理，希望你以后多看书 。。


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 10:29:42   编辑 3楼
知道 CLAISEN加成吗？

知道 CLAISEN缩合吗？


远离是一样的 ，就是 2个 羰基之间的 亚甲基 电负性 ，H被基团取代~~~~

记得 乙酰乙酸乙酯吗？那个原理是一样的 。酰用醇钠和原料反应。。生成碳负离子，然后再上取代基就OK了


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 10:30:59   编辑 4楼
丙二酸二乙酯的亚甲基受两个羰基的影响，活性较高。它与乙醇钠作用生成钠盐，继而与卤代烃反应，生成一元或二元烃基取代的丙二酸二乙酯。


回复人：xiaoyaolcl,★★★★★ (由于爱好,所以从事) 时间：2008-11-26 12:04:43   编辑 5楼
楼主要的是上氯,可以用磺酰氯氯代,要控制好,尽量减少二氯代.反应过程中肯定有二氯代的出现,然后精馏分离.我们做过的


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:21:13   编辑 6楼
所有文献如下：


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:20:27   编辑 7楼
除了溴化和氯化，其实还有上氟。。。用三氟乙酸即可


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:22:29   编辑 8楼
Bibliographic Information

Rapid and catalyst-free .alpha.-halogenation of ketones using N-halosuccinimides in DMSO. Sreedhar, B.; Reddy, P. Surendra; Madhavi, M. Indian Institute of Chemical Technology, Hyderabad, India. Synthetic Communications (2007), 37(23), 4149-4156. Publisher: Taylor & Francis, Inc., CODEN: SYNCAV ISSN: 0039-7911. Journal written in English. CAN 148:238534 AN 2007:1416651 CAPLUS

Abstract

.alpha.-Halogenation of various carbonyl compds. such as .beta.-keto-esters, cyclic ketones, and lactams with N-halosuccinimides (NBS, NCS, NIS) in the presence of DMSO proceeded very smoothly to give the corresponding .alpha.-monohalogenated products in good to excellent yields with high selectivity under catalyst-free conditions.


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:23:40   编辑 9楼
Bibliographic Information

Rapid and catalyst-free .alpha.-halogenation of ketones using N-halosuccinimides in DMSO. Sreedhar, B.; Reddy, P. Surendra; Madhavi, M. Indian Institute of Chemical Technology, Hyderabad, India. Synthetic Communications (2007), 37(23), 4149-4156. Publisher: Taylor & Francis, Inc., CODEN: SYNCAV ISSN: 0039-7911. Journal written in English. CAN 148:238534 AN 2007:1416651 CAPLUS

Abstract

.alpha.-Halogenation of various carbonyl compds. such as .beta.-keto-esters, cyclic ketones, and lactams with N-halosuccinimides (NBS, NCS, NIS) in the presence of DMSO proceeded very smoothly to give the corresponding .alpha.-monohalogenated products in good to excellent yields with high selectivity under catalyst-free conditions.


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:24:00   编辑 10楼
8楼发错了。。图不对，不过文献可以看的


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:25:08   编辑 11楼
Bibliographic Information

High selective method for chlorinating carbonyl compounds in jet loop reactors. Kutschera, Dirk; Riener, Franz-Xaver; Schlueter, Michael. (Wacker Chemie AG, Germany). Ger. Offen. (2008), 16pp. CODEN: GWXXBX DE 102006053380 A1 20080515 Patent written in German. Application: DE 2006-102006053380 20061113. Priority: . CAN 148:540354 AN 2008:588566 CAPLUS
Abstract

A high selective, continuous or semicontinuous method for full or partial chlorinating carbonyl compds. comprises reacting carbonyl compds. with chlorinating agents at ratios (1:1) - (4,000:1) in a jet loop reactor at -20 - 160. Thus, continuous chlorination monochloroacetone to 1,1,3-trichloroacetone (I) at Cl2 stream 4 - 5 Nm3/h takes place at 40 and normal pressure during 10 h with selectivity I formation 35%.


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:26:30   编辑 12楼
Bibliographic Information

Eco-friendly and versatile brominating reagent prepared from a liquid bromine precursor. Adimurthy, Subbarayappa; Ramachandraiah, Gadde; Bedekar, Ashutosh V.; Ghosh, Sudip; Ranu, Brindaban C.; Ghosh, Pushpito K. Central Salt and Marine Chemicals Research Institute, Bhavnagar, India. Green Chemistry (2006), 8(10), 916-922. Publisher: Royal Society of Chemistry, CODEN: GRCHFJ ISSN: 1463-9262. Journal written in English. CAN 147:277198 AN 2006:1041947 CAPLUS

Abstract

Facile bromination of various org. substrates has been demonstrated with a 2 : 1 bromide:bromate reagent prepd. from the alk. intermediate of the conventional bromine recovery process. The reagent is acidified in situ to generate HOBr as the reactive species, which effects bromination. Arom. substrates that have been successfully brominated under ambient conditions without use of any catalyst include phenols, anilines, arom. ethers and even benzene. Non-arom. compds. bearing active methylene group were monobrominated selectively with the present reagent and olefinic compds. were converted into the corresponding bromohydrins in moderate yields. By obtaining the present reagent from the liq. bromine precursor, the twin advantages of avoiding liq. bromine and producing the reagent in a cost-effective manner are realized. When coupled with the addnl. advantage of high bromine atom efficiency, the present protocol becomes attractive all the way from "cradle to grave".


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:27:23   编辑 13楼
Bibliographic Information

Conversion of nucleophilic halides to electrophilic halides: efficient and selective halogenation of azinones, amides, and carbonyl compounds using metal halide/lead tetraacetate. Kim, Jeum-Jong; Kweon, Deok-Heon; Cho, Su-Dong; Kim, Ho-Kyun; Lee, Sang-Gyeong; Yoon, Yong-Jin. Department of Chemistry & Environmental Biotechnology National Core Research Center, Gyeongsang National University, Jinju, S. Korea. Synlett (2006), (2), 194-200. Publisher: Georg Thieme Verlag, CODEN: SYNLES ISSN: 0936-5214. Journal written in English. CAN 144:450258 AN 2006:242292 CAPLUS

Abstract

AlCl3/Pb(OAc)4 and ZnBr2/Pb(OAc)4 are efficient electrophilic N- and .alpha.-C-halogenating agents. A variety of azinones, amides, and carbonyl compds. were chemoselectively and regioselectively N- or .alpha.-C-halogenated in good to excellent yield using AlCl3/Pb(OAc)4 or ZnBr2/Pb(OAc)4 in acetonitrile.


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:27:55   编辑 14楼
Bibliographic Information

New synthesis of polyfluoroalkyl racemic .alpha.-amino acids. Delon, L.; Laurent, P.; Blancou, H. Laboratoire Organisation Moleculaire, Evolution et Materiaux Fluores, UMR CNRS 5073, CC17, Universite Montpellier II, Montpellier, Fr. Journal of Fluorine Chemistry (2005), 126(11-12), 1487-1492. Publisher: Elsevier B.V., CODEN: JFLCAR ISSN: 0022-1139. Journal written in English. CAN 145:314485 AN 2005:1241454 CAPLUS

Abstract

New synthesis of racemic .alpha.-amino acids contg. polyfluorinated aliph. long chain RF(CH2)3Y (RF = C2F5, C6F13, C8F17) (Y = CH(NH2)COOH) based on Soerensen's method is described. The radical addn. of perfluoroalkyl iodides RFI (RF = C2F5, C6F13, C8F17) at room temp. to ethyl-2-carbethoxy-2-phthalimido-pent-4-enoate was first initiated by Et3B/O2. Then, the redn. of adducts using Et3B/O2/Bu3SnH leads to ethyl-2-carbethoxy-2-phthalimido-5-perfluoroalkyl-pentanoate under mild conditions. Exptl. conditions for optimization of the iodoperfluoroalkylation step using Et3B/O2 were studied. Finally, deprotection of the later gave the desired products in good yields.


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:29:12   编辑 15楼
Bibliographic Information

The synthetic versatility of alkoxycarbonyl- and hydroxymethyl-piperazine-2,5-diones. Chai, Christina L. L.; Elix, John A.; Huleatt, Paul B. Department of Chemistry, The Faculties, Australian National University, Canberra, Australia. Tetrahedron (2005), 61(36), 8722-8739. Publisher: Elsevier B.V., CODEN: TETRAB ISSN: 0040-4020. Journal written in English. CAN 143:347134 AN 2005:708384 CAPLUS

Abstract

[(Alkoxy)carbonyl]-2,5-piperazinedione derivs. are versatile precursors for the .alpha.-functionalization of piperazinedione derivs. The alkoxycarbonyl group activates the .alpha.-carbon position to alkylation reactions and this provides a mild and selective method for the extension of the carbon framework of piperazine-2,5-diones. In addn., the alkoxycarbonyl group can be converted to the carboxy group, which in turn can be deleted' or manipulated for the installation of carbon and/or heteroatom substituents where desired, the latter via N-acyliminium chem. It was demonstrated that (hydroxymethyl)-2,5-piperazinedione derivs. complement carboxy-piperazinedione derivs. as precursors for the generation of N-acyliminium ions.


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:30:01   编辑 16楼



回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:30:31   编辑 17楼



回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:31:11   编辑 18楼



回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:32:17   编辑 19楼
二代的文献也来啦2，接招：
文献如下：


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:32:57   编辑 20楼



回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:33:42   编辑 21楼
比较困难，如果你要收率高的二溴，必须要过量的溴素


回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:34:12   编辑 22楼



回复人：claymore,★★★★★ (C-H活化，kumada,suzuki,stille,negishi.cross-coupling.) 时间：2008-11-26 12:34:46   编辑 23楼
这些文献喜欢哪个自己说，发帖秒回。祝您学习进步，天天向上~


回复人：puyun86,▲ (氟化工) 时间：2008-12-02 01:50:40   编辑 24楼
不是理论问题，也不是哪章节就能简单解决具有实际工业价值的工艺。一溴代是很容易进行的，二溴代就不是那么容易了。5楼能传授一下磺酰氯氯代的具体工艺条件吗？我要的是尽可能多的二卤产品得率。谢谢大家。我的电邮puyun86@163.com。



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