Primary Photoproduct of 2,6-Dimethyl-4-Aminopyrimidine
Primary Photoproduct of 2,6-Dimethyl-4-Aminopyrimidine
复制标题
2,6-二甲基-4-氨基嘧啶的初级光产物
DOI：
10.1021/ja00889a048
复制
发表时间：
1963
期刊：
影响因子：
--
通讯作者：
A. R. Katritsky
中科院分区：
文献类型：
--
作者：
K. Wierzchowski;D. Shugar;A. R. Katritsky
根据Ames和Grey3的方法，用n -苄基氧胺处理樟脑酸酐，制得n -苄基樟脑酰亚胺（III）， mp80 -81；M23d+ 19.2 （CHCU）。C17H2iN03: C, 71.06；H, 7.37;4.87 N,。发现C， 70.99；H, 7.38;4.97 N。)氢解得到n -羟基亚胺(I)，产率为51%，mp 229-230,[a] 230 + 7.29。称为，对于Ci0H， 5NO3: C, 60.89；H, 7.67;7.10 N,。发现：C， 60.60；H, 7.65;N, 7.20)。n -羟基亚胺基团3的红外光谱特征在3.0、5.74和5.95µ处发生吸收。用浓盐酸重排3-硝基樟脑，得到n-羟基樟脑亚胺，收率94%，mp 229-230；[a] 23d+ 7.46 (CHC13).(a)发现：C， 60.76；H, 7.58;7.18 N。)重排法和合成法合成的n -羟基亚胺的红外光谱完全一致。与正常的Nef反应不同，Nef反应的异常过程必须受到3-硝基樟脑中羰基质子化的影响，以促进CC键的断裂，羰基碳原子带着电子迁移形成CN键，这与酸催化硝酸脱水有关。失去一个质子形成羰基。质子化作用和
Camphoric anhydride was treated with N-benzyloxyamine according to the method of Ames and Grey3 to form N-benzylcamphorimide (III), mp 80-81; M23d+ 19.2 (CHCU).(Anal. Caled, for C17H2iN03: C, 71.06; H, 7.37; N, 4.87. Found C, 70.99; H, 7.38; N, 4.97.) Hydrogenolysis of IIIgave the N-hy-droxyimide (I) in 51% yield, mp 229-230,[a] 23o+ 7.29 (Anal. Caled, for Ci0H, 5NO3: C, 60.89; H, 7.67; N, 7.10. Found: C, 60.60; H, 7.65; N, 7.20). Absorption in the infrared spectrum characteristic of the N-hydroxyimide group3 occurred at 3.0, 5.74, and 5.95 µ.The rearrangement of 3-nitrocamphor with concen-trated hydrochloric acid gave N-hydroxycamphorimide in 94% yield, mp 229-230;[a] 23d+ 7.46 (CHC13).(Anal. Found: C, 60.76; H, 7.58; N, 7.18.) The infrared spectra of the N-hydroxyimides formedby re-arrangement and by synthesis were identical. The unusual course of the Nef reaction, in contrast to the normal Nef reaction, must be effected by protonation of the carbonylgroup in 3-nitrocamphor to facili-tate the cleavage of the CC bond and the migration of the carbonyl carbon atom with the electrons to form the CN bond which occurs concertedly with the acid catalyzed dehydration of the nitronic acid. Loss of a proton forms the carbonyl group. Protonation and