论文总字数：11690字

摘 要

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

第一章 综述.........................................................1

1.1前言............................................................1

1.2丙硫菌唑及其中间体的合成综述....................................1

1.2.1丙硫菌唑的合成............................................2

第二章 实验部分.....................................................6

2.1试剂与仪器......................................................6

2.2实验方法........................................................6

第三章 实验结果与讨论...............................................8

3.11-乙酰基-1氯环丙烷（N-3）的合成..................................8

3.1.1催化剂对产物的影响............................................8

3.1.1.1氢氧化钠的浓度对反应收率的影响..........................8

3.1.1.2氢氧化钠的用量对反应收率的影响..........................9

3.1.1.3反应温度对反应收率的影响...............................10

第四章 结论与展望..................................................12

4．1结论...................................................12

4．2展望...................................................12

参考文献...........................................................13

致谢...............................................................15

1-乙酰基-1氯环丙烷的合成

摘要

丙硫菌唑是一种三唑硫酮类的杀菌剂，具有杀菌效率高、毒性低、持效期长等优点。与其它三唑类杀菌剂相比，丙硫菌唑具有更广谱的杀菌活性，是目前全球最畅销的十大杀菌剂之一。本文主要研究丙硫菌唑的合成方法，开发可行的生产工艺，以将其应用到工业生产中。

以α-乙酰基-γ-丁内酯为起始原料，经磺酰氯氯代得到α-氯-α-乙酰基-γ-丁内酯(N-1)；经盐酸开环得到3,5-二氯-2-戊酮(N-2)；碱性条件下关环得到1-乙酰基-1-氯环丙烷(N-3)；再通过磺酰氯氯代得到重要中间体2-氯-1-(1-氯环丙基)乙酮(N-4)。

邻氯氯苄与镁反应生成的格氏试剂与N-4加成，得到2-(1-氯环丙基)-2-(2-氯苄基)环氧乙烷(N-5a)和1-氯-2-(1-氯环丙基)-3-(2-氯苯基)-2-丙醇(N-5b)的混合产物；经肼解得到2-(1-氯环丙基)-3-(2-氯苯基)-2-羟基-1-肼盐酸盐(N-6)；再与丙酮、硫氰酸钾在酸性条件下关环得到2-(1-氯环丙基)-1-(2-氯苯基)-3-(3，3-二甲基-1，2，4-三唑烷-5-硫逐-1-基)-2-丙醇(N-7)；最后与甲酸反应制得目标产物丙硫菌唑(N-8)。

产物及关键中间体以核磁共振进行表征。对反应的物料配比、试剂浓度、加料方式、时间、温度等条件进行了探讨，丙硫菌唑总收率达到27%。关键词：丙硫菌唑 合成 1-乙酰基-1氯环丙烷

ABSTRACT

Prothioconazole is a kind of triazole fungicides, which has high fungicidal efficiency, low toxicity, and long duration. Compared with other triazole fungicides, prothioconazole has wider bactericidal activity and it is one of top ten currently best-selling fungicides. Herein, we mainly studied the preparation of prothioconazole to establish its feasible production in industrial scale.

With α-acetyl-γ-butyrrolactone used as a starting material, α-chloro-α-acetyl-γ-butyrolactone(N-1) was prepared by sulfonyl chloride chlorination. Ring-openning of N-1 by hydrochloric acid smoothly afforded 3,5-dichloro-2-pentanone(N-2). 1-Acetyl-1-chlorocyclopropane(N-3) was obtained by cyclization of N-2 in basic conditions. One of the important intermediates, 2-chloro-1-(1-chlorocyclopropyl)ethyl ketone(N-4) was prepared by sulfonyl chloride chlorination of N-3.

The addition reaction between N-4 with the Grignard reagent derived from o-chlorobenzyl chloride, gave a mixture of 2-(1-chlorocyclopropyl)-2-(2-chloroethyl)epoxy ethane(N-5a) and 1-chloro-2-(1-cyclopropyl)-3-(2-chlorophenyl)-2-propanol(N-5b). 2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxyl-1-hydrazine dihydrochloride(N-6) was obtained by hydrazinolysis of of the above mixture. The cyclization of N-6 with acetone and potassium thiocyanate under acidic conditions gave 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(3,3-dimethyl-1,2,4-triazole-5-thionic-1-yl)-2-propanol(N-7). Finally the product prothioconazole(N-8) was prepared by the treatment of N-7 with formic acid.

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