CN109111392B - 一种环丁烷衍生物的合成方法 - Google Patents

一种环丁烷衍生物的合成方法 Download PDF

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CN109111392B
CN109111392B CN201810838128.3A CN201810838128A CN109111392B CN 109111392 B CN109111392 B CN 109111392B CN 201810838128 A CN201810838128 A CN 201810838128A CN 109111392 B CN109111392 B CN 109111392B
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韩英锋
马莉莉
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Abstract

本发明公开了一种新型环丁烷衍生物的合成方法，其以新型金卡宾化合物为起始原料，发展了一种通过金卡宾模板效应一步法构筑分离环丁烷衍生物的方法。本发明提供的合成方法与传统方法相比，具有明显优势：无辅助物，转化高效；产物单一；易分离等系列优点。

Description

一种环丁烷衍生物的合成方法
技术领域
本发明涉及一种合成新型环丁烷衍生物的方法，属于合成化学技术领域。
背景技术
光化学反应又称光化作用，即物质在可见光或紫外光下发生化学反应。在合成化学中，相对于传统合成方法，光化学反应作为一种新型的合成方法表现出无可替代的优势。近年来，环丁烷衍生物在生物活性、气体吸附以及电化学等领域都有非常广泛的应用前景。根据Schmidt 规则，发生[2+2]光化学环加成反应需满足两个C=C双键按平行方式排列并且之间的距离须小于4.2 Å。在没有约束的条件下分子进行无序运动，两个分子之间的距离很难满足光化学反应要求，因此，自由分子直接进行[2+2]光化学环加成反应并构筑环丁烷衍生物相对较难。通过不断探索和努力，研究者们发现利用环糊精、葫芦脲、一些特殊的 MOFs骨架等可作为模板剂，将反应物约束在一个有限的空间内进行光化学反应；另外利用分子间作用力,如配位键、氢键、金属-金属作用等也可以达到类似的效果。
近年来随着配位化学的快速发展，研究者利用配位基团与含有C=C烯烃配体组装成配位聚合物或者金属有机框架材料可获得具有合适的预排列的结构，将有助于[2+2]环加成反应的发生。
发明内容
本发明的目的是提供一种通过金卡宾模板效应，在温和条件下一步法构筑分离环丁烷衍生物的方法。
为实现上述目的，本发明公开了如下技术方案：
一种环丁烷衍生物的合成方法，包括以下步骤：
（1）以CH2Cl2为溶剂，双核金卡宾配合物(I)和含有C=C烯烃配体2a-2u为原料制备矩形金卡宾化合物[3a-3u] (OTf)4；
Figure 100002_DEST_PATH_IMAGE001
其中，R为:
Figure 100002_DEST_PATH_IMAGE002
（2）以化合物[3a-3u] (OTf)4为原料，通过模板效应实现[2+2]光化学环加成反应，制备环丁烷衍生物4a-4u；
Figure 100002_DEST_PATH_IMAGE003
。
上述步骤（1）中，化合物（I）和配体2a-2u的物质的量比为1:1~1:1.5，优选为1:1。
上述步骤（1）中，化合物1与配体2a-2u的反应时间为1~72小时，优选为24小时。
上述步骤（2）中，使用365 nm紫外光照射，光照时间为1~72小时，优选为24小时。
上述合成方法中的模板分子[3a-3u](OTf)4在[2+2]光化学反应中的应用。
本发明的优点：金属卡宾模板反应具有反应条件温和、反应时间短、产率高、操作简单；合成环丁烷衍生物具有转化高效（无辅助物）、产物单一、易分离、普适性广等一系列优点。
附图说明
图1为合成环丁烷衍生物4a-4u机理示意图。
具体实施方式
下面通过实施例进一步具体描述本发明，本发明并不局限于下述实施例。
如图1所示，本发明利用金属卡宾模板效应，在365 nm紫外光照射下，被限域的烯烃进行[2+2] 光化学环加成反应裂解形成环丁烷衍生物。此反应利用环丁烷衍生物张力，导致金属与N之间形成的化学键断裂，此过程无需借助其他外界条件，即可形成环丁烷衍生物。
实施例1：矩形金卡宾化合物[3a] (OTf)4的制备
无水无氧操作条件下，将化合物（I） (100 mg, 0.12 mmol), 含C=C烯烃配体2a(22 mg, 0.12 mmol)溶于15 mL CH2Cl2中，然后向溶液中加入AgOTf (61 mg, 0.24 mmol)，避光条件下室温搅拌反应12 h。反应结束后，用二氯甲烷洗涤，过滤收集固体，将固体置于100 mL烧杯中，加入乙腈，过滤收集滤液，旋干得到淡黄色固体106.2 mg,产率76%。1H NMR(400 MHz, DMSO-d 6): δ= 8.60 (d, J = 6.5 Hz, 8H), 8.07 (d, J = 1.9 Hz, 4H),7.79 (d, J = 1.9 Hz, 4H), 7.67 (d, J = 6.5 Hz, 8H), 7.58 (s, 4H), 7.27 and6.49 (s, 4H), 4.33 (d, J = 29.9 Hz, 8H), 1.82 (m, 8H), 1.28 (m, 8H), 0.90 ppm(t, J = 7.4 Hz, 12H). HRMS (ESI, positive ions): m/z = 418.1093 (calcd for[3a]4+ 418.1083)。
实施例2：矩形金卡宾化合物[3b] (OTf)4的制备
无水无氧操作条件下，将化合物1 (351 mg, 0.43 mmol)，含C=C烯烃配体2b (150mg, 0.48 mmol)溶于20 mL CH2Cl2中，然后向溶液中加入AgOTf (250 mg, 0.97 mmol)，避光条件下室温搅拌反应12 h。反应结束后，用二氯甲烷洗涤，过滤收集固体，将固体置于100mL烧杯中，加入乙腈，过滤收集滤液，旋干得到固体450 mg，产率82%。1H NMR (400 MHz,DMSO-d 6): δ= 9.93 (s, 4H), 8.68 (s, 4H), 8.02 (s, 4H), 7.80 (s, 4H), 7.46 (d,J = 8.4 Hz, 8H), 7.29 (d, J = 8.5 Hz, 8H), 6.80 (s, 4H), 6.77 (s, 4H), 4.29(t, J = 6.5 Hz, 8H), 1.82 (m, 8H), 1.26 (m, 8H), 0.89 ppm (t, J = 7.3 Hz,12H). HRMS (ESI, positive ions): m/z = 1117.2256 (calcd for {[3b](OTf)2 }2+1117.2127), 484.1290 (calcd for [3b]4+484.1300)。
实施例3：矩形金卡宾化合物[3c] (OTf)4的制备
无水无氧操作条件下，将化合物1 (150 mg, 0.18 mmol)，含C=C烯烃配体2c (76mg, 0.18 mmol)溶于20 mL CH2Cl2中，然后向溶液中加入AgOTf (104 mg, 0.41 mmol)，避光条件下室温搅拌反应12 h。反应结束后，用二氯甲烷洗涤，过滤收集固体，将固体置于100mL烧杯中，加入乙腈，过滤收集滤液，旋干得到固体200 mg, 产率79%。1H NMR (400 MHz,DMSO-d 6): δ= 9.21 (s, 4H), 8.13 (d, J = 1.8 Hz, 4H), 7.83 (d, J = 1.8 Hz,4H), 7.78 (d, J = 8.2 Hz, 4H), 7.59 (d, J = 8.5 Hz, 8H), 7.56 (d, J = 8.5 Hz,4H), 7.35 (d, J = 8.3 Hz, 8H), 7.28 (s, 4H), 7.23 (t, 4H), 7.17 (t, 4H), 6.90(s, 4H), 4.35 (t, 8H), 1.87 (m, 8H), 1.31 (m, 8H), 0.89 ppm (t, J = 7.4 Hz).HRMS (ESI, positive ions): m/z = 1215.2471 (calcd for {[3c](OTf)2}2+1215.2535), 760.5198 (calcd for {[3c](OTf)}3+760.5181) , 533.1572 (calcd for{[3c]}4+533.1505)。
实施例4：矩形金卡宾化合物[3d] (OTf)4的制备
无水无氧操作条件下，将化合物1 (50 mg, 0.061 mmol)，含C=C烯烃配体2d (29mg, 0.061 mmol)溶于15 mL CH2Cl2中，然后向溶液中加入AgOTf (31 mg, 0.12 mmol)，避光条件下室温搅拌反应12 h。反应结束后，用二氯甲烷洗涤，过滤收集固体。1H NMR (400MHz, DMSO-d 6): δ= 9.05 (s, 4H), 8.14 (d, J = 1.8 Hz, 4H), 7.89 (d, J = 5.1Hz, 4H), 7.84 (d, J = 1.9 Hz, 4H), 7.55 (d, J = 8.6 Hz, 8H), 7.51 (s, 4H),7.34 (d, J = 9.3 Hz, 8H), 7.26 (s, 4H), 4.34 (t, 8H), 2.23 (d, J = 13.2 Hz24H), 1.88 (m, 8H), 1.31 (m, 8H), 0.90 ppm (t, J = 7.4 Hz, 12H).HRMS (ESI,positive ions): m/z = 561.1865 (calcd for {[3d]}4+561.1818)。
实施例5：环丁烷衍生物4a的制备
将化合物[3a] (OTf)4 7 mg置于核磁管中，加入0.6 mL DMSO-d 6，将核磁管置于365 nm氙灯下，室温光照5 h，此时反应转化率为100%。随后将光照后的溶液倒入100 mL的茄型瓶中，加入30 mL乙醚，超声，收集白色固体，抽干，将固体溶于乙腈，采用乙醚扩散的方法重结晶，2天之后，除去白色晶体，收集淡黄色固体。1H NMR (400 MHz, CD3OD):δ= 8.72(d, J = 6.6 Hz), 8.09 (d, J = 6.5 Hz), 5.45 ppm (s, 2H)。
实施例6：环丁烷衍生物4b的制备
将化合物[3b] (OTf)4 10 mg置于核磁管中，加入0.6 mL DMSO-d 6，将核磁管置于365 nm氙灯下，室温光照11 h，此时反应转化率为100%。随后将光照后的溶液倒入100 mL的茄型瓶中，加入40 mL乙醚，超声，收集固体，抽干，用甲醇洗涤固体，收集固体，抽干。1H NMR(400 MHz, DMSO-d 6):δ= 9.20 (s, 4H), 8.17 (s, 4H), 7.69 (d, J = 8.5 Hz), 7.46(d, J = 7.9 Hz), 4.72 ppm (s, 4H).
实施例7：环丁烷衍生物4c的制备
将化合物[3c] (OTf)4 10 mg置于核磁管中，加入0.6 mL DMSO-d 6，将核磁管置于365 nm氙灯下，室温光照14 h，此时反应转化率为100%。随后将光照后的溶液倒入100 mL的茄型瓶中，加入50 mL乙醚，超声，收集固体，抽干，用甲醇洗涤固体，收集固体，抽干。1H NMR(400 MHz, DMSO-d 6):δ= 8.52 (s, 4H), 7.76 (d, J = 8.6 Hz, 4H), 7.50-7.65 (m,16H), 7.44 (d, J = 7.8 Hz, 4H), 7.29 (t, 4H), 7.19 (t, 4H), 4.88 ppm (s, 4H).
实施例8：环丁烷衍生物4d的制备
将化合物[3d] (OTf)4 10 mg置于核磁管中，加入0.6 mL DMSO-d 6，将核磁管置于365 nm氙灯下，室温光照24 h，此时反应转化率为100%。随后将光照后的溶液倒入100 mL的茄型瓶中，加入50 mL乙醚，超声，收集固体，抽干，用氯仿提取，旋干。1H NMR (400 MHz,CDCl3):δ= 7.96 (s, 4H), 7.60 (s, 4H), 7.41 (s, 4H), 7.15 (s, 4H), 4.74 (s,4H), 2.36 (s, 12H), 2.23 ppm (s, 12H)。
实施例9：发明人参照实施例1-8的方法，使用含不同C=C烯烃矩形金卡宾化合物制备得到环丁烷衍生物。
Figure DEST_PATH_IMAGE004
Figure DEST_PATH_IMAGE005
Figure DEST_PATH_IMAGE006
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Figure DEST_PATH_IMAGE008
Figure DEST_PATH_IMAGE009
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Figure DEST_PATH_IMAGE012
Figure DEST_PATH_IMAGE013
Figure DEST_PATH_IMAGE014
Figure DEST_PATH_IMAGE015
Figure DEST_PATH_IMAGE016
以上所述仅是本发明的优选实施方式，应当指出，对于本领域的普通技术人员，在不脱离本发明的前提下，还可以对本发明做出的若干改进和补充，这些改进和补充，也应视为本发明的保护范围。

Claims (8)

1.一种环丁烷衍生物的合成方法，其特征在于包括以下步骤：
（1）以CH2Cl2为溶剂，双核金卡宾配合物(I)和含有C=C烯烃配体2a-2k为原料制备矩形金卡宾化合物[3a-3k] (OTf)4；
Figure DEST_PATH_IMAGE001
其中，R为:
Figure DEST_PATH_IMAGE002
（2）以化合物[3a-3k] (OTf)4为原料，通过模板效应实现[2+2]光化学环加成反应，制备环丁烷衍生物4a-4k；
Figure DEST_PATH_IMAGE003
。
2.根据权利要求1所述环丁烷衍生物的合成方法，其特征在于：上述步骤（1）中，化合物（I）和配体2a-2k的物质的量比为1:1~1:1.5。
3.根据权利要求2所述环丁烷衍生物的合成方法，其特征在于：化合物（I）和配体2a-2k的物质的量比为1:1。
4.根据权利要求1所述环丁烷衍生物的合成方法，其特征在于：上述步骤（1）中，化合物1与配体2a-2k的反应时间为1~72小时。
5.根据权利要求4所述环丁烷衍生物的合成方法，其特征在于：上述步骤（1）中，化合物1与配体2a-2k的反应时间为24小时。
6.根据权利要求1所述环丁烷衍生物的合成方法，其特征在于：上述步骤（2）中，使用365 nm紫外光照射，光照时间为1~72小时。
7.根据权利要求6所述环丁烷衍生物的合成方法，其特征在于：上述步骤（2）中，光照时间为24小时。
8.权利要求1所述合成方法中的模板分子[3a-3k](OTf)4在[2+2]光化学反应中的应用。
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