CN102688777A - 一种锰配合物的用途 - Google Patents

一种锰配合物的用途 Download PDF

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CN102688777A
CN102688777A CN2012101861511A CN201210186151A CN102688777A CN 102688777 A CN102688777 A CN 102688777A CN 2012101861511 A CN2012101861511 A CN 2012101861511A CN 201210186151 A CN201210186151 A CN 201210186151A CN 102688777 A CN102688777 A CN 102688777A
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罗梅
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Abstract

一种锰配合物的用途是二氯化二DMF合锰（Ⅱ）配合物在芳醛与腈化物的腈硅化反应制备目标产物时作为催化剂，所取的芳醛包括苯甲醛或取代苯甲醛，如4-甲基苯甲醛、4-甲氧基苯甲醛、4-氟苯甲醛，4-溴苯甲醛、4-氯苯甲醛、2-甲氧基苯甲醛、2-氟苯甲醛和1-萘醛。

Description

一种锰配合物的用途
一、技术领域
本发明涉及一种金属有机配位化合物（配合物）的用途，特别涉及含氧的金属有机配合物的用途，确切地说是一种锰氧配合物的用途。
二、背景技术
金属锰配合物因其在生物功能和分子磁体、荧光材料、有机化学及电化学等方面的潜在应用价值已引起人们的广泛关注。参考文献：【1-3】
1. Nonprecious Metal Catalysts for Fuel Cell Applications: Electrochemical Dioxygen Activation by a Series of First Row Transition Metal Tris(2-pyridylmethyl)amine Complexes, Ward, Ashleigh L.; Elbaz, Lior; Kerr, John B.; Arnold, John , Inorganic Chemistry (Washington, DC, United States), 2012, 51(8), 4694-4706. 2. Direct polymerization of 2-bromothiophenes based on direct arylation reaction, Takita, R.; Wang, Q.; Kikuzaki, Y.; Nakamura, Y.; Wakioka, M.; Ozawa, F. Pacifichem 2010, International Chemical Congress of Pacific Basin Societies, Honolulu, HI, United States, December 15-20, 2010, PagesORGN-943， Conference; Meeting Abstract.
3. Highly active dimeric Mn(salen) catalysts entrapped within nanocages of periodic mesoporous organosilica for epoxidation of alkenes, Hu, Jianglei; Wu, Qingyin; Li, Kexin; Li, Wei; Ma, Fengyan; Zhang, Shengqu; Su, Fang; Guo, Yihang; Wang, Yonghui, Catalysis Communications, 2010, 12(3),238-242.
三、发明内容
本发明旨在为芳醛与氰化物或腈化物的加成反应制备目标产物，所要解决的技术问题是提供高效催化剂。
本发明所称的锰氧配合物是一种以二价锰为中心离子、以N,N-二甲基甲酰胺（DMF）为配体的由以下化学式所示的锰-氧配合物：
Figure 2012101861511100002DEST_PATH_IMAGE001
化学名称：二氯化二DMF合锰（Ⅱ），简称锰配合物。
本锰配合物的合成方法首先以邻苯二胺为配体合成锰-氮配合物，然后进行配体交换得到以DMF为配体的锰-氧配合物。反应过程如下：
首先用摩尔比近2:1的邻苯二胺和与四水合氯化锰在无水四氢呋喃溶剂中回流反应24小时，反应结束后热过滤，得到白色的滤渣。然后将滤渣置于用DMF（溶质）和无水乙醚（溶剂）配成的饱和溶液中密闭静置，一天后底部有无色晶体析出并分离。该无色晶体经红外和元素分析及X-衍射鉴定确认为上式所示的锰-氧配合物。
在本发明中称芳醛与氰化物或腈化物的加成反应为腈硅化反应。当芳醛与氰化物加成时得到芳基羟腈；当芳醛与腈化物为三甲基硅腈（TMSCN）加成时得到芳基氰醇硅醚，如下式所示:
Figure 648785DEST_PATH_IMAGE002
本发明所称的锰配合物的用途是在邻、对位取代的芳香族醛类腈硅化反应中的用途，所述的芳醛包括苯甲醛或取代苯甲醛，如4-甲基苯甲醛、4-甲氧基苯甲醛、4-氟苯甲醛，4-溴苯甲醛，2-甲基苯甲醛、2-甲氧基苯甲醛、2-氟苯甲醛，1-萘醛。
二、附图说明
图1是配合物（Ⅰ）的单晶衍射图。
三、具体实施方式
1、锰配合物的合成
称取1.1186g(10mmol)邻苯二胺放入100mL圆底烧瓶中，加入30mL四氢呋喃，搅拌使其溶解；将0.9768g(5mmol) MnCl2·4H2O加入上述溶液，加热回流24h；反应后热过滤，得到白色的滤渣。对滤渣用DMF和无水乙醚配成饱和溶液后密封，一天后底部有无色晶体出现，产率：66.82%，红外数据(KBr 压片)：2923,2810,1658,1576,1496,1434,1388,1250,1105,677. 元素分析：C6H14 N2O2MnCl2理论值：C：26.49%； H：5.19%； N：10.30% ；理论值：C：26.49% H：5.19% N：10.30 % ；实测值：C：26.42%；H：5.49%；N：9.96%。
2. α-(三甲基硅氧基)-苯乙腈的制备
0.15mmol 催化剂I (1mmol), 苯甲醛0.1mL, TMSCN 0.3 ml (3.3mmol) 相继在20~30˚C下加入，并溶解于2mL 甲苯, 8h 后， 加入水淬灭经柱层后（石油醚/二氯甲烷：5/1），得无色油状液体。转化率：96%，1H NMR (500MHz, CDCl3) 7.56–7.59 (m, 0.9 Hz, 2H), 7.31–7.34 (m, 3H), 5.43 (s, 1H),0.16 (s, 9H). 13C NMR (75 MHz, CDCl3) 136.1, 128.8(x2), 126.2(x2), 119.1, 63.5, -0.39(x3).，Conv.%:62%
3. α-(三甲基硅氧基)-2-氟苯乙腈的制备
0.15mmol 催化剂I (0.15mmol), 2-氟苯甲醛1mmol, TMSCN 0.3 mL (3.3mmol) 相继在20~30˚C下加入，并溶解于2mL 甲苯, 反应8h 后，经柱层后（石油醚/二氯甲烷：5/1），得无色油状液体。转化率：91 %，1H NMR (500MHz, CDCl3)7.56–7.59 (m, 0.9 Hz, 2H), 7.31–7.34 (m, 3H), 5.43 (s, 1H),0.16 (s, 9H). 13C NMR (75 MHz, CDCl3) 136.1, 128.8(x2), 126.2(x2), 119.1, 63.5, -0.39(x3).
3. α-(三甲基硅氧基)-2-甲氧基苯乙腈的制备
0.15mmol 催化剂I (0.15mmol), 2-甲氧基苯甲醛1mmol、, TMSCN 0.3 mL (3.3mmol) 相继在20~30˚C下加入，72h 后，经柱层后（石油醚/二氯甲烷：5/1），得无色油状液体。转化率：85 %，1H NMR (500MHz, CDCl3)1H NMR (300MHz, CDCl3) 7.52–7.54 (d, J=7.5Hz, 1H), 7.20-7.30(m,3H), 5.57(s, 1H), 2.44 (s, 3H), 0.22 (s,9H)。
4. α-(三甲基硅氧基)-4-甲基苯乙腈的制备
0.15mmol 催化剂I (0.15mmol), 4-甲基苯甲醛0.1mL, TMSCN 0.3 mL (3.3mmol) 相继在20~30˚C下加入，并溶解于2mL 二氯甲烷, 反应 8h 后，经柱层析后（石油醚/二氯甲烷：5/1），得无色油状液体, 转化率：73 %，1H NMR (500MHz, CDCl3) 7.37-7.39 (m, 2H), 7.21-7.24 (m, 2H), 5.48(s, 1H), 2.38(s,3H), 0.24(s, 9H). 13C NMR (75 MHz, CDCl3) 139.3,133.5,129.6,126.4,63.6, 31.6, 22.6, 21.2, 14.1, -0.23(x3)。
5. α-(三甲基硅氧基)-4-甲氧基苯乙腈的制备
0.15mmol 催化剂I (0.15mmol), 4-甲氧基苯甲醛1mmol, TMSCN 0.3 mL (3.3mmol) 相继在20~30˚C下加入，并溶解于2mL 甲苯, 反应 8h 后，经柱层后（石油醚/二氯甲烷：5/1），得无色油状液体。转化率：24%，1H NMR (500MHz, CDCl3) 7.61–7.63 (m, 1H), 7.37-7.40(m,1H), 7.04–7.07 (m, 1H), 6.92–6.94 (m, 1H), 5.82(s, 1H), 3.91 (s, 3H), 0.25 (s, 9H)。
6.α-(三甲基硅氧基)-4-氟苯乙腈的制备
0.15mmol 催化剂2b (0.15mmol), 4-氟苯甲醛1mmol, TMSCN 0.3 mL (3.3mmol) 相继在20~30˚C下加入, 并溶解于2mL 甲苯, 反应 8h 后, 经柱层后（石油醚/二氯甲烷：5/1），得无色油状液体转化率：46 %，1H NMR (500MHz, CDCl3) 7.40-7.41 (m, 4H), 5.46 (s, 1H), 0.24 (s, 9H)。
7. α-(三甲基硅氧基)-4-溴苯乙腈的制备
0.15mmol 催化剂I (0.15mmol), 4-溴苯甲醛1mmol, TMSCN 0.3 mL (3.3mmol) 相继在20~30˚C下加入，并溶解于2mL 甲苯, 反应 8h 后，经柱层后（石油醚/二氯甲烷：5/1），得无色油状液体。转化率: >99%，1H NMR (500MHz, CDCl3) 1H NMR(300 MHz, CDCl3) 7.53–7.56 (m, 2H), 7.33–7.36(m, 2H), 5.45 (s, 1H), 0.23 (s, 9H)。
8. α-(三甲基硅氧基)-4-氯苯乙腈的制备
0.15mmol 催化剂I (0.15mmol), 4-溴苯甲醛1mmol, TMSCN 0.3 mL (3.3mmol) 相继在20~30˚C下加入，并溶解于2mL 甲苯, 反应 8h 后，经柱层后（石油醚/二氯甲烷：5/1），得无色油状液体。转化率: 45 %，1H NMR (500MHz, CDCl3) 1H NMR(300 MHz, CDCl3) 7.53–7.56 (m, 2H), 7.33–7.36(m, 2H), 5.45 (s, 1H), 0.23 (s, 9H)。
9.α-(三甲基硅氧基)-萘乙腈的制备
0.15mmol 催化剂I (0.15mmol), 1-萘甲醛1mmol, TMSCN 0.3 mL (3.3mmol) 相继在20~30˚C下加入，并溶解于2mL 甲苯, 反应 8h 后，经柱层后（石油醚/二氯甲烷：5/1），得无色油状液体。转化率: 75%, 1HNMR (300MHz, CDCl3) 8.16-8.18(m, 1H), 7.88-7.91 (m,2H), 7.69-7.71(m,1H), 7.25-7.61(m,4H)。

Claims (9)

1.一种锰配合物的用途，其特征是在芳醛的腈硅化反应制备目标产物时作为催化剂。
2. 根据权利要求1所述的用途，其特征是在2-甲氧基苯甲醛的腈硅化反应制备目标产物时作为手性催化剂。
3.根据权利要求1所述的用途，其特征是在2-氟苯甲醛的腈硅化反应制备目标产物时作为手性催化剂。
4.根据权利要求1所述的用途，其特征是在4-氟苯甲醛的腈硅化反应制备目标产物时作为手性催化剂。
5.根据权利要求1所述的用途，其特征是在4-甲基苯甲醛的腈硅化反应制备目标产物时作为催化剂。
6.根据权利要求1所述的用途，其特征是在4-甲氧基苯甲醛的腈硅化反应制备目标产物时作为催化剂。
7. 根据权利要求1所述的用途，其特征是在4-溴苯甲醛的腈硅化反应制备目标产物时作为催化剂。
8.根据权利要求1所述的用途，其特征是在4-氯苯甲醛的腈硅化反应制备目标产物时作为催化剂。
9.根据权利要求1所述的用途，其特征是在1-萘苯甲醛的腈硅化反应制备目标产物时作为催化剂。
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102304151A (zh) * 2011-05-25 2012-01-04 合肥工业大学 一种锰配合物及其合成方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102304151A (zh) * 2011-05-25 2012-01-04 合肥工业大学 一种锰配合物及其合成方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
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汪海明等: "手性自负载催化剂研究新进展", 《化学进展》 *

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Application publication date: 20120926