Page 234 - 《精细化工》2023年第4期

す 40 ࢤす 4 ᱌ ㇫ ㏳ ࡃ ጒ Vol.40, No.4
20 23 Ꭱ 4 ᰵ FINE CHEMICALS Apr. 2023

㇫㏳ࡃጒ͚䬡Ҁ
CuI ϸᄩ Reformatsky ࣺᏁ倅᩵व᜽

ȕ-㓌ധ䚜ㆨࡃव➖

*
䧌⦉㏏喑ᑍࢍͶ喑⼻㏏▢喑҆ᴠ䲆喑ॡᄼՖ喑㒄Ꭱࡻ
喍䊐ࢄࡨ႓䮏 㢜႓䮏喑↌㺬 䊐ጋ 341000喎

ᦅ㺮喟㔰ᄌγ㠜⩟䛈হ 2-ⷅΆ䚥Ά䚜व᜽ 3-㓌ധ-3-㠜ധ͆䚥Ά䚜喍1喎⮱ࣺᏁ᲎Уᄦϔ➖ϔ⢴⮱ᒞ৺喑ᓄݝ⮱
ᰭхࣺᏁ᲎Уͧ喟В 1.0 mmol 㠜⩟䛈হ 1.5 mmol 2-ⷅΆ䚥Ά䚜ͧ࣌᫆Ƞ0.2 mmol CuI ͧϸᄩȠ3.0 mmol 䨹ㆶͧ
יࡃݯȠ0.2 mmol CF 3 CO 2 H ͧ⌨ߍݯȠ2 mL V(Ά㙵)ńV(ࣨ⻨ၽⅡ)=1ń1 ⮱⌤व⋟ͧ⏣ݯ喑ბ⍖̸ࣺᏁȡౕ䄒
13
1
ࣺᏁ᲎У̸喑व᜽γ 32 ͗ϔ⢴ౕ 82%~95%͸䬡⮱ ȕ-㓌ധ䚜ㆨࡃव➖ 1~32喑ϔ➖㐀Ჱ㏼ HNMRȠ CNMR হ
MS ⶛䃮喑Ꭳ᣽ܧγज㘪⮱ࣺᏁᱧ⤳ȡᐭࣾγ̭⻺⩞ CuI ϸᄩ⮱キᭀȠ倅᩵⮱ Reformatsky יࡃҀ㈨喑჋⣝γ䨹
ㆶ倅᩵יࡃ 2-ⷅΆ䚥Ά䚜̻̺ह㟠䛈/㟠䚛⮱ Reformatsky ࣺᏁ喑䄒יࡃҀ㈨ᩫ๔㜠ٸ㏔喑В 92%⮱倅ϔ⢴㣤ᓄ
ࡃव➖ 1ȡ
ڠ䩛䃺喟CuI喠䨹喠Reformatsky ࣺᏁ喠ȕ-㓌ധ䚜喠2-ⷅΆ䚥Ά䚜喠㇫㏳ࡃጒ͚䬡Ҁ
͚ఫܳㆨत喟TQ243.4喠O625.3 ᪴⡛ᴴ䃳⴮喟A ᪴」㑃त喟1003-5214 (2023) 04-0920-09

CuI mediated Reformatsky reaction: Efficient synthesis of ȕ-hydroxy esters

ZHONG Yuhong, ZHANG Zhanyi, SHUI Hongling,
*
YU Liujing, WU Xiaoqian, LUO Nianhua
喍School of Pharmacy, Gannan Medical University, Ganzhou 341000, Jiangxi, China喎

Abstract: The effects of reaction conditions on the yield of 3-hydroxy-3-phenylpropionate ethyl (1)
synthesized from benzaldehyde and ethyl 2-iodoacetate were investigated. The optimal reaction conditions
were obtained. The reaction was performed at room temperature with 1.0 mmol benzaldehyde and 1.5 mmol
2-ethyl iodoacetate used as raw materials, 0.2 mmol CuI as mediator, 3.0 mmol zinc powder as catalyst,
0.2 mmol CF 3CO 2H as additive, and 2 mL of V(acetonitrile)ńV(deionized water)=1ń1 mixture as solvent.
Thirty-two ȕ-hydroxyl esters (1~32) with yields ranging 82%~95% were then synthesized under the
above-mentioned reaction conditions from different araldehydes/different arketones, and characterized via
1 13
HNMR, CNMR and MS, followed by exploration on the possible reaction mechanism. Herein, a simple
and efficient Reformatsky catalytic system mediated by CuI was developed for efficient catalysis of the
Reformatsky reaction between ethyl 2-iodoacetate and different araldehydes/arketones with zinc powder as
catalyst. This catalytic system was scaled up to gram level and compound 1 was successfully synthesized with a
high yield of 92%.
Key words: CuI; Zn; Reformatsky reaction; ȕ-hydroxy esters; ethyl 2-iodoacetate; fine chemical intermediates

ȕ-㓌ധ㓝ധ俕᳣᭜̭ㆨ䛺㺮⮱㢜᩵ധఏহᰶФ 㵺⩌➖᭫ᓄ䲋፥䛺㺮 [3-4] ȡڣ͚喑Reformatsky ࣺᏁ
[5]
թ⮱व᜽ၽ [1-2] 喑Ꭼ∈ႅౕλ⩌➖≨ᕔܳၽȠ㢜➖ܳ जВᰶ᩵ౝव᜽ ȕ-㓌ധ䚜ࣷڣ㵺⩌➖ 喑Ꭳ⩕λ⩌
ၽহ๖♣ϔ➖͚ȡ఍ₑ喑ຯ҂倅᩵व᜽ ȕ-㓌ധ㓝ധ ➖ࡨ㢜͚䬡ҀȠ⩌➖≨ᕔܳၽぶ⮱व᜽ȡ

ᩣ⽬ᬒ᱌喟2022-07-07; Ⴧ⩕ᬒ᱌喟2022-09-07; DOI: 10.13550/j.jxhg.20220628
ധ䛾䶦Ⱋ喟↌㺬Ⱞ⻾ឭࢲ䶦Ⱋ喍20224BAB203009喎喠↌㺬Ⱞ᪆㗟ࢲ䉱ߖ䶦Ⱋ喍GJJ211541喑GJJ180801喎喠2022 Ꭱ↌㺬Ⱞ๔႓⩌݈᫝݈
͇䃚㏰䃎ܿ䶦Ⱋ喍S202210413034喎
҉㔲キϸ喟䧌⦉㏏喍1989ÿ喎喑ຠ喑ߖ⤳჋侹ጵ喑E-mail喟754877574@qq.comȡ㖁㈨ϧ喟㒄Ꭱࡻ喍1982ÿ喎喑⩤喑ࢇธ喑ޜ᪆ᢵ喑E-mail喟
luoxiaoge102@163.comȡ