摘要：联萘酚是一类具有C2轴不对称芳香族化合物，具有一定的刚性和立体选择性，光学活性联萘酚及其衍生物是有效的手性催化剂，广泛应用于生物医药、合成等领域。本文对联萘酚及其衍生物的合成及发展做了详细叙述。实验以光活性1,1'-联-2-萘酚（2,2'-dihydroxy-1,1'-binaphthalene，BINOL，简称联萘酚）、纯液溴、氯甲醚等为主要原料，设计实验方案，合成了3,3'-Br-1,1'-联-2-萘酚，其主要步骤简述为下：通过对拆分的联萘酚（R-型，S-型），用氯甲醚进行羟基保护，然后进行卤化（即用溴取代3,3'位上的氢），最后脱保护得到3,3'-Br-1,1'-联-2-萘酚，利用1H NMR对中间体和目标产物进行了结构表征。并采用单因素法优化了反应的工艺条件，得到了收率和纯度较为理想的目标化合物。24148
毕业论文关键词：BINOL；衍生物；合成；手性
The synthesis of3, 3'- Br - 1，1'-bi-2-naphthanol
Abstract：Binaphthol was a class of aromatic compounds having an asymmetric axis C2, with a certain rigidity and stereoselectivity, and the optically active binaphthol derivative was effective chiral catalysts,were widely used in biomedicine, and other fields. This paper coupleted naphthol and its derivatives synthesis and development of a detailed narrative.The main raw material of the synthesis of3, 3 '- Br - 1，1'-bi-2-naphthanol were2,2'-dihydroxy-1,1'-binaphthalene (BINOL), pure liquid bromine, and chloromethyl methyl ether. Then design the experiment plan. The experiment steps were as follows. Through the split of R- BINOL and S- BINOL on hydroxyl protection, and then to halide the product (fluorine substitution at the 3,3' positions of 2,2'-dihydroxy-1,1'-binaphthalene (BINOL).Finally to take off protection for 3, 3 '- Br - 1，1'-bi-2-naphthanol, then carry on the purification, and characterized the product of 2, 2 '- Br - 1，1'-bi-2-naphthanol. Results expressed: hydroxyl protecting the product easier to get high yields, bromo was the rate controlling step of the experiment, a lower yield. NMR spectra showed that the resulting product was realy the desired product.The use of 1H NMR for intermediates and target products were characterized. And the use of single-factor method to optimize the reaction conditions, the yield and purity has been the ideal target compound.
Keywords: BINOL；Derivatives; Synthesis; Chirality
目录
第一章 绪论 1
1.1联萘酚的介绍 1
1.2联萘酚的发展进程 1
1.2.1 消旋体联萘酚的发展 1
1.2.2 光活性联萘酚的发展 2
1.2.3 联萘酚配合物的发展 3
1.3联萘酚及其衍生物的研究意义 5
1.4核磁共振仪的原理 6
第二章 联萘酚(BINOL)的合成方法 8
2.1 外消旋体BINOL的合成 8
2.1.1 三氯化铁作为氧化剂 8
2.1.2 铜(Ⅱ)作为氧化剂 9
2.1.3 O2作为氧化剂 9
2.2外消旋体BINOL的拆分 10
2.2.1 化学拆分 10
2.2.2 色谱拆分 10
2.2.3 酶拆分 11
2.3 不对称氧化偶联合成法 11
2.3.1 手性铜胺配合物作为氧化剂 11
2.3.2 钒配合物作为氧化剂 11
2.3.3 手性环境中三氯化铁作为氧化剂 12
2.3.4 手性环境中光催化氧化 12
2.3.5 其他 12
第三章 3,3'-Br-1,1'-联-2-萘酚的合成与表征 13
3.1 引言 13
3.2 实验部分 13
3.2.1 主要仪器 13 3,3'-Br-1,1'-联-2-萘酚的合成与表征:http://www.751com.cn/huaxue/lunwen_17512.html