1、谈谈实验室安全和实验的个人体会,导师：麻生明 研究员 汇报人：顾振华,有机所枫林论坛,往者可谏 来者可追,2,主要内容,实验室安全个人的实验 科学的信誉问题Giving Proper Credit,3,溶剂(1) 对神经系统破坏：抑制神经系统的传导冲动功能，产生麻醉，神经系统障碍或引起神经炎等。酒精、苯、氯化乙醇、二氯乙烷、汽油、甲酸戊酯、醋酸戊酯、二甲苯、三氯乙烯、丁醇、松节油、煤油、丙酮、三氯甲烷、异丙苯等。(2) 对肝脏机能损伤： 损伤肝脏机能，引起恶心、呕吐、发烧、黄疸炎及中毒性肝炎；一般氯化烃类均会引起肝脏中毒现象。四氯化碳、氯仿、三氯乙烯、四氯乙烷、苯及其衍生物等。(3) 对肾脏机
2、能破坏： 肾脏为毒物排泄器官，故最易中毒，且因血氧量减少，亦足以使肾脏受害，发生肾炎及肾病。烃类之卤化物、苯及其衍生物、二元醇及其单醚类、四氯化碳、乙醇等。(4) 对造血系统破坏：破坏骨髓造成贫血现象。苯及其衍生物(硝基苯)如甲苯、氯化苯、二元醇等。 (5) 对粘膜及皮肤刺激： 刺激粘膜，使鼻粘膜出血，喉头发炎，嗅觉丧失或因皮肤敏感产生红肿、发痒、红斑及坏疽病等。三氯甲烷、醚、苯、丙酮、甲醇、石油、氯酚、二氯乙烯、四氯化碳等。,4,控温仪毛细管温度计、温度计套管 核磁管高温高压反应,5,操作规范 整洁、有章程 （洗瓶、药品的存放(苯胺)，称量、取用(双层手套法、注射器的正确使用)、了解不同试剂
3、的性质(液氨)）过柱溶剂的转移,溶剂球的固定,防护镜不要“意气用事”试管,蒸馏“空中接力”,6,多借鉴别人的经验LiAlH4：Workup best conducted by “1,2,3-method”for 1.0 g LiAlH4 used, added 1 mL H2O (slowly)then 2 mL of 10% aqueous NaOH, then 3 mL of H2O无故乱翻书8 : 2规则,7,全合成：广度,方法学：深度,2. Corey-Bakshi-Shibata reductionCorey-Chaykovsky-epoxidation (Corey-ylide)C
4、orey-Fuchs reactionCorey-Kim oxidationCorey-Winter olefin Synthesis,3. Coupling ReactionJohn F. Hartwig,根深则叶茂,1. Phil BaranChemical & Engineering News, 2007, 85, 38 “One of the things I think Phil is really good at is having a sense of what is new, what is novel, and what needs to be discovered in o
5、ur field,“ remarks graduate student Noah Z. Burns. “Its not an easy thing to do in a mature field.“make (+)-ambiguine H in 10 steps without relying on any protecting groups (Nature 2007, 446, 404)Baran has a reputation as a wunderkind,8,The Nobel Prize in Chemistry 1913“in recognition of his work on
6、 the linkage of atoms in molecules by which he has thrown new light on earlier investigations and opened up new fields of research especially in inorganic chemistry“,Alfred Werner 1866-1919,9,Karl Ziegler Federal Republic of Germany 1898-1973,1953年他利用铝有机化合物成功地在常温常压下催化乙烯聚合,Giulio Natta Institute of T
7、echnology Milan, Italy 1903-1979,1954年在德国化学家K.Ziegler乙烯低压聚合制成聚乙烯重大发现的 基础上，发现以钛和烷基铝为催化剂，丙烯在低压下高收率地聚合， 生成分子结构高度规整的立体定向聚合物聚丙烯，具有高强度 和高熔点，开创了立体定向聚合的崭新领域。,The Nobel Prize in Chemistry 1963 “for their discoveries in the field of the chemistry and technology of high polymers“,10,Org. Syn. 2000, 77, 141,the
8、 mixture is heated to 85 oC (internal temperature) over 30 min by means of an oil bath,实验操作：胆大、心细、脸皮厚,因为了解，所以失败,11,假设,设计反应,实施,yes,no,基于呋喃酮骨架的周环反应研究,12,13,a Yields were determined by 1H NMR analysis with CH2Br2 as the internal standard. b 14% yield of 4c remained as determined by 1H NMR analysis. c P
9、dCl2 was used asthe catalyst, 67% of 4c remained as determined by 1H NMR analysis. d 30 mol% Sc(OTf)3 and 4.0 equiv of BF3Et2O were used.,14,A. K. Ghosh, J. Cappiello, D. Shin, Tetrahedron Lett. 1998, 39, 4651,15,The mechanism study,Where does the two hydrogen (in red) of 4c go?,Where does the three
10、 hydrogen (in blue) of 113c come?,Is 112c a precursor of 113c?,16,The 1H NMR (300 MHz) spectra of the mixture of 112c and 113c in CDCl3 at 25 oC. (a) 1H NMR spectrum of the mixture obtained right after isolation; (b) The 1H NMR spectrum after 4 hours; (c) The 1H NMR spectrum after 6 hours; (d) The 1
11、H NMR spectrum after 27 hours,17,18,19,20,21,22,23,24,25,26,ORTEP representation of trans-96sc,27,28,29,Conditions: (a) C2H5Br, Mg, THF, then acetylene; (b) CD3COCD3, 34%; (c) NaH, Et2O, then ClCO2Me, 71%; (d) n-BuLi, Et2O, -78 oC; then H2O, -78 oC, 38%; (d) 2-allyl-4-phenylbuta-2,3-dienoic acid, Pd
12、(OAc)2/TFP, K2CO3, DMSO, 54%, 95%D.,30,31,The plausible pathway,32,33,Giving Proper Credit,Researchers who have been directly affected by Crdovas actions . say Crdova steals research ideas at conference and then presents the ideas as his own by publishing the results of hasty and often poorly execut
13、ed parallel experiments.,Crdova,Donna G. Blackmond, a professor of chemistry at Imperial College, says Crdova stole her scientific ideas at a lecture, published them, and continues to present her development of a new model explaining nonlinear effects in organocatalysis as if it were his own.,“Its f
14、air to say that Crdova has a pretty bad reputation in the community, and it seems he is resubmitting things he has heard about in lectures,“ says Benjamin List. List says that after he spoke a conference in Italy, Crdova submitted similar work that was published in Tetrahedron Letters. He says he bl
15、ames himself for talking about the work, but he adds, “People know whats going on.“,Sweden, Stockholm University,34,In 2001, Crdova submitted a research paper to the Journal of the American Chemical Society and later to Tetrahedron Letters without Barbas consent. The paper was rejected by JACS, and
16、Barbas was able to retract it after he learned that it had been submitted and accepted for publication in Tetrahedron Letters. Crdova had by then been fired from the Barbas lab for reasons that Barbas wont specify. In April 2003, Barbas wrote to Stockholm University, saying he feared Crdova would at
17、tempt to submit the paper again.“Indeed, Crdova submitted the manuscript to Synlett on May 21, 2003, and it was published in Crdovas name (as sole author) in 2003,“ Sterner and Frejd write in their report of the investigation.,Crdova sticks to his argument that he has not behaved differently, in ter
18、ms of his publication practices, Than other people in the field. “When more senior people do it, its okay. I thought I was following the norms of the field“ he says.,A graduate student in the Crdova lab, Ismail Ibrahem, claims that other, larger groups envy their Productivity “People dont reference
19、our work, but they use our methods,“ he claims. He says he enjoys working with his mentor and that the Crdova lab is a productive and happy environment. He points out that many papers in organocatalysis “appear at the same time with the same chemistry. Theres a lot of competition.“,35,Researcher Wit
20、hdraws JACS Papers,Dalibor SamesProfessor of chemistry, Columbia UniversityBeng SezenSames was not able to speak with C&EN because the matter is under investigation by Columbia. Sezen could not be reached by C&EN press time.,Chemical & Engineering NewsMarch 15, 2006March 23, 2006June 16, 2006,36,Sam
21、es retracted the JACS papers He says other scientists could not reproduce the results reported by Sezen.Sezen : The reactions described in these publications were performedindependently by my colleagues in my absence before the submission of papers; thus these retractions came as a surprise to me. I
22、 strongly protest that the retractions were made without my knowledge.Sezen: “During the past week, I have tried to contact professor Sames about the retraction of papers without any success. I have reserved copies of experimental data, which support the original claims of these publications, but wa
23、s not given a chance to present these data. I am also prepared to perform the reactions under the supervision of professor Sames if I am given a chance.“Columbia University has forbidden Sames to speak to the media about Sezen or the universitys investigation. The scientists Sezen identified as bein
24、g able to reproduce her work are both members of the Sames group. They declined to verify her assertions or otherwise speak with C&EN.,37,Four more papers are being retracted by Columbia University Professor of Chemistry, Dalibor Sames.Sezen has cried foul over the retractions, maintaining that she
25、has never been properly notified or consulted. Whats more, she claims not only that her work can be reproduced but that it has been reproduced by other members of the Sames group (C&EN, March 23). Her assertions cannot be verified because no one in the Sames group has been willing to speak with C&EN
26、.Sezen now also claims that Sames did not use the proper catalysts when trying to reproduce her work.,38,小结,安全实验,讲究效率,科学信誉,要善于保护好自己,39,定风波莫听穿林打叶声苏轼 三月七日沙湖道中遇雨。雨具先去，同行皆狼狈，余独不觉。已而遂晴，故作此。 莫听穿林打叶声，何妨吟啸且徐行。竹杖芒鞋轻胜马，谁怕？一蓑烟雨任平生。料峭春风吹酒醒，微冷，山头斜照却相迎。回首向来萧瑟处，归去，也无风雨也无晴。,40,Many Thanks For Your Kindly Attention!,
