Page 215 - 《精细化工》2020年第5期

第 37 卷第 5 期 精 细 化 工 Vol.37, No.5
202 0 年 5 月 FINE CHEMICALS May 2020

精细化工中间体
光学纯 1,1′-(4,6-二苯并呋喃二基)

双乙基-1-醇/胺的合成探索

刘启宾

（大连联化化学有限公司，辽宁 大连 116620）

摘要：二苯并呋喃（Ⅱ）与仲丁基锂（s-BuLi）、四甲基乙二胺（TMEDA）、乙醛（CH 3 CHO）反应，得到 1,1′-(4,6-
二苯并呋喃二基)双乙基-1-醇（Ⅲa），然后在氯铬酸吡啶 盐（PCC）中经过氧化反应得到 1,1′-(4,6-二苯并呋喃
二基)双乙基-1-酮（Ⅳa），随后在(S)-2-甲基-CBS-唑硼烷{(S)-MeCBS}催化下采用硼烷-二甲硫醚（BH 3 -Me 2 S）
还原，重结晶后得到(1R,1′R)-1,1′-(4,6-二苯并呋喃二基)双乙基-1-醇（Ⅰ）。最佳反应条件为 n(Ⅱ)∶n(s-BuLi)∶
n(TMEDA) ∶ n(CH 3 CHO)=1.0 ∶ 3.0 ∶ 3.3 ∶ 2.2 ， n( Ⅲ a) ∶ n(PCC)=1.0 ∶ 4.0 ， n( Ⅳ a):n[(S)-MeCBS] ∶
n(BH 3 -Me 2 S)=1.0∶0.6∶3.0，3 步反应总收率为 32%。化合物 I 中存在分子内氢键，其影响了羟基进一步衍生。
化合物Ⅲa 经过氯化亚砜氯代、叠氮化钠取代和钯碳氢化还原，得到消旋 1,1′-(4,6-二苯并呋喃二基)双乙基-1-胺
（Ⅶ），加入常见手性酸利用成盐拆分的方法未能得到光学纯 1,1′-(4,6-二苯并呋喃二基)双乙基-1-胺（Ⅷ）。
关键词：二苯并呋喃；(S)-MeCBS；(1R,1′R)-1,1′-(4,6-二苯并呋喃二基)双乙基-1-醇；分子内氢键；成盐拆分；精
细化工中间体
中图分类号：O621.3 文献标识码：A 文章编号：1003-5214 (2020) 05-1065-06

Synthetic exploration of optically pure 1,1′-(dibenzo[b,d]

furan-4,6-diyl)bis(ethan-1-ol/amine)

LIU Qibin
（Dalian Allychem Company Limited, Dalian 116620, Liaoning, China）

Abstract: 1,1′-(Dibenzo[b,d]furan-4,6-diyl)bis(ethan-1-ol) (Ⅲa) was prepared by reaction of dibenzofuran
(Ⅱ) with sec-butyllithium (s-BuLi), tetramethyl ethylene diamine (TMEDA) and acetaldehyde (CH 3CHO),
which was oxidized with pyridinium chlorochromate (PCC) to yield 1,1′-(dibenzo[b,d]furan-4,6-diyl)
bis(ethan-1-one) ( Ⅳ a). Subsequently, intermediate Ⅳ a was reduced with borane-dimethyl sulfide
(BH 3-Me 2S) in the presence of a catalytic amount of (S)-2-methyl-CBS-oxazo borane{(S)-MeCBS} and
recrystallization gave optically pure (1R,1′R)-1,1′-(dibenzo[b,d]furan-4,6-diyl)bis(ethan-1-ol) (Ⅰ). The
optimal reaction conditions for the synthesis of compound Ⅰ were as follows: n(Ⅱ)∶n(s-BuLi)∶
n(TMEDA)∶n(CH 3CHO)=1.0∶3.0∶3.3∶2.2, n(Ⅲa)∶n(PCC)=1.0∶4.0, n(Ⅳa)∶n[(S)-MeCBS]∶
n(BH 3-Me 2S)=1.0∶0.6∶3.0. Under these conditions, the overall yield of the three-step reaction was 32%.
There are certain intramolecular hydrogen bonds in compound Ⅰ, which affect further diversifications of its
hydroxyl groups to some extent. Chlorination with thionyl chloride of Ⅲa, azidination with sodium azide and
Pd/C-catalyzed hydrogenation afforded racemic 1,1′-(dibenzo[b,d]furan-4,6-diyl)bis(ethan-1-amine) (Ⅶ).
However, optically pure 1,1′-(dibenzo[b,d]furan-4,6-diyl)bis(ethan-1-amine) (Ⅷ) was not successfully
obtained by the resolution of Ⅶ with commonly used chiral carboxylic acids.
Key words: dibenzofurans; (S)-MeCBS; (1R,1′R)-1,1′-(dibenzo[b,d]furan-4,6-diyl)bis(ethan-1-ol); intra
molecular hydrogen bonds; salt resolution; fine chemical intermediates

收稿日期：2019-09-04; 定用日期：2019-11-01; DOI: 10.13550/j.jxhg.20190841
作者简介：刘启宾（1979—），男，博士，高级工程师，E-mail：qliu@allychem.com。