重氮甲烷的制備及反應(yīng)

1、Zeng Qinglong2013-09-03重氮甲烷的制備：de Boer, Th. J. and Backer, H. J. Org. Synth. 1963, Coll. Vol. 4, 250 Arndt, F. Org. Synth. 1943, Coll. Vol. 2, 165 Mechanism:1、吸入重氮甲烷，及皮膚或眼部接觸重氮甲烷都是有毒的。2、重氮甲烷與磨砂玻璃的接口接觸，或加熱至100 C都可能會(huì)發(fā)生爆炸，使用時(shí)必須小心。CAUTION!一、與烯烴反應(yīng)成環(huán)丙烷L(zhǎng)uithle, J. E. A.; Pietruszka, J. J. Org. Chem. 1999,

2、64, 8287.重氮甲烷的反應(yīng)：Mechanism:鈀催化劑與重氮甲烷作用形成鈀卡賓中間體后，與烯烴親電加成，再經(jīng)還原消除生成環(huán)丙烷。二、將酰氯轉(zhuǎn)化為多一個(gè)碳的羧酸、酯或酰胺。(Arndt-Eistert homologation)Mechanism:Ancliff, R. A., Russell, A. T., Sanderson, A. J. Tetrahedron: Asymmetry 1997, 8, 3379-3382.三、與醛、酮反應(yīng)生成多一個(gè)碳原子的酮 （Buchner-Curtius- Schlotterbeck反應(yīng) ）Bchner, E. and Curtius, T.,

3、Ber., 1885, 18, 2371-2373.Schlotterbeck, F., Ber., 1907, 40, 479.Schlotterbeck, F., Ber., 1907, 40, 182.Schlotterbeck, F., Ber., 1907, 40, 3000.Mechanism:The ratio of the two possible carbonyl products (I and II) obtained is determined by the relative migratory abilities of the carbonyl substituents

4、 (R1 and R2). In general, the R-group most capable of stabilizing the partial positive charge formed during the rearrangement migrates preferentially. C. D. Gutsche, Org. React., 1954, 8, 364.Wendeborn, S., Nussbaumer, H., Schaetzer, J., Winkler, T. Synlett., 2010, 13, 1966-1968.四、甲基化試劑：與羧酸反應(yīng)生成甲基酯，與酚、-二酮 及-酮酯的烯醇型生成甲基醚 Mechanism:與C-H鍵的插入反應(yīng)相比，重氮甲烷分解產(chǎn)生的卡賓可選擇性地插入到O-H鍵之間，使羧酸轉(zhuǎn)化為相應(yīng)的甲酯。Izidor S., Bojana M., Katharina A., Bogdan