论文总字数：17274字

摘 要

目前，含氟的的化合物尤其是含有三氟甲基的吡啶类化合物在医药和农药的中间体的合成中受到广泛的重视。2-羟基-6-三氟甲基烟腈作为含三氟甲基的吡啶类化合物，可用来合成6-三氟甲基烟腈衍生物还可作为医药和农药的中间体。本文建立了一种合成2-羟基-6-三氟甲基烟腈的新方法。

以三氟乙酸酐和乙烯基乙醚作为初始原料，二氯甲烷为溶剂，吡啶为催化剂经过加成消除反应合成烯醚，4-乙氧基-1,1,1-三氟-3-丁烯-2-酮，以乙烯基乙醚计，该步反应收率为75.2%。4-乙氧基-1,1,1-三氟-3-丁烯-2-酮与浓氨水发生取代反应生成烯胺，即4-氨基-1,1,1-三氟-3-丁烯-2-酮，该步反应收率为87.9%。以三乙胺为催化剂，烯胺和腈乙酰胺进行环合得到2-羟基-6-三氟甲基烟腈，该步反应收率为42.0%。经过条件优化，该方法总收率达到27.7%。

最终产物通过熔点、核磁进行结构表征，结果表明符合目标物结构。

关键字：2-羟基-6-三氟甲基烟腈，乙烯基乙醚，三氟乙酸酐，合成

Abstract

2-Hydroxy-6-trifluoromethyl nicotinonitrile, as one useful pyridine intemediate containing trifluoromethyl group, can be used to synthesize corresponding nicotinic acid and other derivatives for producing pharmaceuticals as well as pesticides. This thesis established a new method for the synthesis of 2-hydroxy-6-trifluoromethyl nicotinonitrile.

Ethyl vinyl ether was treated with trifluoroacetic anhydride by using pyridine as the base to provide 4-ethoxy-1,1,1-trifluoro-3-butene-2-one(75.2%yield, calculated from ethyl vinyl ether). 4-amino-1,1,1- trifluoro-3-butene-2-one was readily obtained by substitutive amination of 4-ethoxy-1,1,1-trifluoro-3-butene-2-one with concentrated aqueous ammonia in a yield of 87.9%.Under the catalysis of triethylamine, the annulation of the above enamine with cyanoacetamide was realized furnishing 2-hydroxy-6-trifluoromethyl nicotinonitrile in a yield of 42.0%.

The final product was characterized by melting point and NMR technique indicating structurally agreeable.

Key words: 2- hydroxy-6-trifluoromethyl nicotinonitrile, ethyl vinyl ether, trifluoroacetic anhydride,synthesis

目录

摘要.................................................................................................................................I

Abstract..........................................................................................................................II

目录..............................................................................................................................Ⅲ

1. 文献综述..........................................................................................................1

1.1引言...................................................................................................................1

1.2烟腈类物质及其衍生物的用途.......................................................................1

1.2.1烟腈........................................................................................................1

1.2.2 烟腈的主要合成方法...........................................................................1

1.2.3烟酸........................................................................................................2

1.2.4烟酰胺....................................................................................................3

1.3含三氟甲基的烟腈类化合物...........................................................................3

13.1三氟甲基烟腈类化合物的特点.............................................................3

1.3.2电子效应................................................................................................4

1.3.3伪拟效应................................................................................................4

1.3.4亲脂性....................................................................................................4

1.3.5阻碍效应................................................................................................4

1.4 2-羟基-6-三氟甲基烟腈...................................................................................5

1.4.12-羟基-6-三氟甲基烟腈的用途.............................................................5

1.4.2 2-羟基-6-三氟甲基烟腈重要衍生物的合成........................................6

1.5 引入三氟甲基的主要方法..............................................................................7

1.5.1 直接氟化法...........................................................................................7

1.5.2 含氟砌块法...........................................................................................8

1.6 本论文研究的内容及意义..............................................................................8

第二章 实验部分.........................................................................................................9

2.1 药品和仪器......................................................................................................9

2.1.1药品........................................................................................................9

2.1.2仪器........................................................................................................9

2.2 烯醚即4-乙氧基-1,1,1-三氟-3-丁烯-2-酮的合成.......................................10

2.3 烯胺即4-氨基-1,1,1-三氟-3-丁烯-2-酮的合成...........................................11

2.4 2-羟基-6-三氟甲基烟腈的合成.....................................................................11

2.5结果的讨论与分析.........................................................................................12

2.5.1 催化剂选择和投料量考察.................................................................12

2.5.2 核磁表征…………………………………………………………….13

1. 结论与展望....................................................................................................15

3.1 结论................................................................................................................14

3.2展望.................................................................................................................14

参考文献......................................................................................................................15

致谢..............................................................................................................................17

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