CN109320514B - 一种固载多功能化合物及其制备和应用 - Google Patents

一种固载多功能化合物及其制备和应用 Download PDF

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CN109320514B
CN109320514B CN201811379052.9A CN201811379052A CN109320514B CN 109320514 B CN109320514 B CN 109320514B CN 201811379052 A CN201811379052 A CN 201811379052A CN 109320514 B CN109320514 B CN 109320514B
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史兰香
张宝华
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Hebei Jing Zhong Biological Technology Co.,Ltd.
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Abstract

本发明公开了一种固载多功能化合物及其制备和应用。本发明以1，10‑菲罗啉‑2，9‑二醛为原料，分别与4‑氨基‑2，2，6，6‑四甲基哌啶和氨微球缩合、再经还原、氧化制备了固载多功能化合物(式I)。本发明的化合物兼具配体、碱和助氧化剂功能，能与Cu盐形成一种高选择性的分子氧氧化各种醇制备醛/酮的反应体系。式I易与反应体系分离，循环使用。

Description

一种固载多功能化合物及其制备和应用
技术领域
本发明涉及有机化学合成领域，具体地说是一种固载多功能化合物及其制备和应用。
背景技术
高效选择性氧化醇类化合物制备醛酮，是一类重要的官能团转化反应，应用广泛。传统的醇氧化方法常采用铬(Ⅵ)酸盐，锰酸盐，高价碘的化合物，钌(Ⅷ)氧化物和二甲基亚砜等为氧化剂，这些氧化剂存在用量大，产生大量的副产物等缺点，在工业生产中受到很大的局限。
近年来，均相金属络合物与TEMPO的复合催化体系在非常温和的条件下，能高效选择催化分子氧对醇的氧化，产物收率接近定量，引起了化学界的注意。在这些反应体系中，联吡啶、菲罗林、氮杂卡宾以及它们的类似物等作为配体能促进反应顺利进行，但它们的结构比较复杂，制备过程繁琐，价格昂贵，若不能回收循环利用，会导致生产成本太高。助氧化剂TEMPO也存在同样的问题。另外，为了促进醇氧化反应高选择性进行，这类反应体系中，通常需要加入适量的有机碱或无机碱，以便更好的夺取醇羟基上的质子，促进中间体金属醇盐的形成。同时，有机碱还可以与铜进行配位，降低铜的氧化还原电势，提高其催化性能。但碱的加入对环境造成污染。为解决目前这些研究中存在的问题，本发明将起配体作用的菲罗啉结构、TEMPO结构和起碱作用的胺结构进行拼合和负载，制备了一种固载多功能化合物，该化合物易与反应体系分离，能回收循环利用，氧化选择性高，环境友好。
发明内容
本发明的目的是提供一种固载多功能化合物，其特征在于，其结构如式I所示：
Figure 206933DEST_PATH_IMAGE001
式中，
Figure 850404DEST_PATH_IMAGE003
为氨微球
本发明的另一目的是提供一种固载多功能化合物的制备方法，其特征在于，具体步骤如下：
（1）1，10-菲罗啉-2，9-二醛先与等摩尔量的4-氨基-2，2，6，6-四甲基哌啶在THF中室温反应12h，再与预先在THF中溶胀好的氨微球（含氨1.4mmol/g）反应12h，过滤，THF反复洗涤，真空干燥，制得氨微球固载的二亚胺化合物（Ⅱ)；
（2）将氨微球固载的二亚胺化合物加入THF中溶胀，冷至0℃，分批加入NaBH4，反应12h，慢慢滴入饱和NH4Cl溶液至无气泡产生，过滤，THF与甲醇洗涤，制得氨微球固载的胺化合物（Ⅲ)；
（3）将氨微球固载的胺化合物加入甲醇与Mg(OH)2混合物中，回流状态下，慢慢滴入30%的H2O2,反应6h，冷至室温，过滤，甲醇和正己烷洗涤，真空干燥，制得式I。
反应式如下：
Figure 100002_DEST_PATH_IMAGE004
式中，
Figure 716729DEST_PATH_IMAGE003
为氨微球
本发明所述的一种固载多功能化合物，其同时具有配体、助氧化剂和碱的功能。
本发明所述的一种固载多功能化合物，其能与Cu盐和氧分子形成一种高效氧化体系，这种氧化体系能高选择性的氧化各种醇制备醛/酮。
本发明所述的高效氧化体系，其Cu盐选自CuI, CuCl, CuBr, CuCN, 三氟甲磺酸亚铜, 醋酸亚铜，硫氰酸亚铜，硫酸亚铜。
本发明所述的一种固载多功能化合物，其易与反应体系分离，能回收循环利用。
具体实施方式
以下的实施例在于详细说明本发明，而非限制本发明。
实施例1
氨微球固载的二亚胺化合物（Ⅱ)的制备
在100mL三口瓶中，加入236mg(1mmol)1，10-菲罗啉-2，9-二醛和5mLTHF，再加入156mg(1mmol)4-氨基-2，2，6，6-四甲基哌啶，室温反应12h，再加入0.71g(1mmol，1.4mmol/g)用10mLTHF溶胀好的氨微球，反应12h，过滤，THF反复洗涤，真空干燥，制得氨微球固载的二亚胺化合物（Ⅱ)。
实施例2
氨微球固载的胺化合物（Ⅲ)的制备
将0.97g(1mmol)氨微球固载的二亚胺化合物（Ⅱ）加入15mLTHF溶胀，冷至0℃，分批加入83.6mg(2.2mmol)NaBH4，反应12h，慢慢滴入10mL饱和NH4Cl溶液至无气泡产生，过滤，THF与甲醇洗涤，制得氨微球固载的胺化合物（Ⅲ).
实施例3
固载多功能化合物式I的制备
将0.9g氨微球固载的胺化合物（Ⅲ)加入15mL甲醇中，再加入2mg Mg(OH)2，回流状态下，慢慢滴入0.25mL30%的H2O2,保温反应6h，冷至室温，过滤，甲醇和正己烷洗涤，真空干燥，制得式I。
实施例4
脂肪伯醇氧化成醛
在装有磁子的25mLSchlenk圆底烧瓶中加入230mg(1.25mmol)碘化亚铜, 0.89g(1.25mmol)化合物式I和10mL乙腈。混合物敞口搅拌1min,然后加入3.25g(25mmol)1-辛醇。反应液在室温和空气氛围(气球压力)下搅拌6h。反应结束后, 过滤，正己烷洗涤，回收化合物式I与Cu（I）的配合物，循环利用。滤液合并，浓缩，硅胶柱层析纯化，制得辛醛，收率95%。
实施例5
芳香伯醇氧化成醛
在装有磁子的25mLSchlenk圆底烧瓶中加入230mg(1.25mmol)碘化亚铜, 0.89g(1.25mmol)化合物式I和10mL乙腈。混合物敞口搅拌1min,然后加入2.70g(25mmol)苄醇。反应液在室温和空气氛围(气球压力)下搅拌6h。反应结束后, 过滤，乙腈、正己烷洗涤，化合物式I回收，循环利用。滤液合并，浓缩，硅胶柱层析纯化，制得苯甲醛，收率97%。
实施例6
芳香基伯醇氧化成醛
在装有磁子的25mLSchlenk圆底烧瓶中加入0.89g实施例5回收的化合物式I、265mg(1.25mmol)三氟甲磺酸亚铜和10mL乙腈。混合物敞口搅拌1min,然后加入2.45g(25mmol)糠醇。反应液在室温和空气氛围(气球压力)下搅拌6h。反应结束后, 过滤，乙腈、正己烷洗涤，化合物式I回收，循环利用。滤液合并，浓缩，硅胶柱层析纯化，制得2-呋喃甲醛，收率96%。
实施例7
用新鲜制备的化合物式I代替回收的化合物式I，其它操作同实施例6，2-呋喃甲醛的收率96%。
实施例8
仲醇氧化成酮
在装有磁子的25mLSchlenk圆底烧瓶中加入0.89g(1.25mmol)化合物式I、122mg(1.25mmol)氯化亚铜和10mL乙腈。混合物敞口搅拌1min,然后加入3.05g(25mmol)1-苯基乙醇。反应液在室温和空气氛围(气球压力)下搅拌7h。反应结束后, 过滤，乙腈、正己烷洗涤，化合物（I）回收，循环利用。滤液合并，浓缩，硅胶柱层析纯化，制得苯乙酮，收率94%。

Claims (2)

1.一种固载多功能化合物，其特征在于，结构如式（I）所示：
Figure DEST_PATH_IMAGE002
式中，
Figure DEST_PATH_IMAGE004
为氨微球。
2.如权利要求1所述的一种固载多功能化合物的制备方法，其特征在于，具体步骤如下：
（1）1，10-菲罗啉-2，9-二醛先与等摩尔量的4-氨基-2，2，6，6-四甲基哌啶在THF中室温反应12h，再与预先在THF中溶胀好的氨微球反应12h，含氨1.4mmol/g，过滤，THF反复洗涤，真空干燥，制得氨微球固载的二亚胺化合物（Ⅱ)；
（2）将氨微球固载的二亚胺化合物加入THF中溶胀，冷至0℃，分批加入NaBH4，反应12h，慢慢滴入饱和NH4Cl溶液至无气泡产生，过滤，THF与甲醇洗涤，制得氨微球固载的胺化合物（Ⅲ)；
（3）将氨微球固载的胺化合物加入甲醇与Mg(OH)2混合物中，回流状态下，慢慢滴入30%的H2O2,反应6h，冷至室温，过滤，甲醇和正己烷洗涤，真空干燥，制得式I；
Figure DEST_PATH_IMAGE006
式中，
Figure DEST_PATH_IMAGE004A
为氨微球。
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