杂环化合物的反应.ppt

六员杂环化合物的芳香C-H键反应一般发生在α位。 3.芳香C-H键反应 A）Chichibabin氨化 ANRORC (Add. Of Nu., Ring Opening and Ring Closure) B. VNS氨化 C. 格氏试剂反应 D. 重氮化 1. ANRORC mechanism The ANRORC mechanism in organic chemistry describes a special type of substitution reaction. ANRORC stands for Addition of the Nucleophile, Ring Opening, and Ring Closure in nucleophilic attack on ring systems and it helps to explain product formation and distribution in some nucleophilic substitutions especially in heterocyclic compounds. This reaction mechanism has been extensively studied in reactions of metal amide nucleophiles (such as sodium amide) and substituted pyrimidines (for instance 4-phenyl-6-bromopyrimidine 1) in ammonia at low temperatures. The main reaction product is 4-phenyl-6-aminopyrimidine 2 with the bromine substituent replaced by an amine. This rules out the formation of an aryne intermediate A which would also give the 5-substituted isomer. 第四节. 重排反应 2. Boulton-Katritzky rearrangement Rearrangment of 5- to 7-substituted 4-nitrobenzfuroxanes. Boulton A. J., Katritzky A. R., Rev. Chim. (Romania), 1962, 7, 691. 3. Ciamician-Dennsted rearrangement Cyclopropanation of a pyrrole with dichlorocarbene generated from CHCl3 and. NaOH. Subsequent rearrangement takes place to 4. Cornforth rearrangement Cornforth重排反应是由澳洲化学家 John Cornforth (1917－)（1975年获化学诺奖）于1949年首先报道。其是C-5为烃基取代（-R1）、C-4 为酰基取代（-C(O)R2）的恶唑环系，在加热时发生重排，生成 R1与 R2互换的产物。 C-4 用硫代酰基（-C(S)R2）取代后，重排后可得1,3-噻唑环系。 反应机理： 反应机理可能为底物发生开环，生成一个开链的二酰基腈叶立德中间体，然后再使用 -C(O)R2 的羰基经过电环化成恶唑环，得到产物。 5. Morin rearrangement 在这些杂化化合物中，一般都具有很弱的碱性,但吡咯具有弱酸性： 1. 酸碱性 第五节. 其它反应 该钾盐可以方便地转化成N-取代的衍生物： 吡啶环氮也体现弱碱性： 2. 芳香偶联反应 3. 歧化反应 4. 脱羧反应 4. The Diels-Alder Reaction Otto Diels Kurt Alder Noble Prize in 1950 5. 羰基化反应 Davoli P , Forni A , Prati F , et al . Tetrahedron , 2001 , 57 (9) :1801-1812. Coates GW , Getzler YD YL , Mahadevan V. WO 3050154 , 2003. Magnesium Derivatives Boron / Silicon / Tin Derivatives Transmetallaton Zinc Derivatives Reactio