CN113559904B - 氮碳材料锚定的铁单原子催化剂在催化醇的氨氧化制腈反应中的应用 - Google Patents

氮碳材料锚定的铁单原子催化剂在催化醇的氨氧化制腈反应中的应用 Download PDF

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CN113559904B
CN113559904B CN202110805525.2A CN202110805525A CN113559904B CN 113559904 B CN113559904 B CN 113559904B CN 202110805525 A CN202110805525 A CN 202110805525A CN 113559904 B CN113559904 B CN 113559904B
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陆国平
易文斌
王博仁
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Nanjing University of Science and Technology
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Abstract

本发明公开了一种氮碳材料锚定的铁单原子催化剂在催化醇的氨氧化制腈反应中的应用，属于醇的氨氧化制腈反应技术领域。所述氮碳材料锚定的铁单原子催化剂在催化醇的氨氧化制腈反应中的应用，具体步骤如下：将醇、氮碳材料锚定的铁单原子催化剂、氨水和水依次加入到反应容器中，于一定温度下反应一段时间，反应结束后，去除催化剂，对反应溶液进行后处理，即得腈化合物。本发明以氮碳材料锚定的铁单原子材料为催化剂，高效催化醇氨氧化制腈反应，反应条件温和、选择性和底物耐受性好，催化剂廉价低毒且可以回收利用，因此易于实现腈类化合物的放大生产制备。

Description

氮碳材料锚定的铁单原子催化剂在催化醇的氨氧化制腈反应 中的应用
技术领域
本发明属于醇的氨氧化制腈反应技术领域，具体涉及一种氮碳材料锚定的铁单原子催化剂在催化醇的氨氧化制腈反应中的应用。
背景技术
腈类化合物是一类十分重要的化学中间体，其在医药、农药、染料、添加剂、纺织助剂以及聚合物的合成中都有广泛的应用，同时其本身也是许多具有生物活性化合物的合成结构，如非布司他和比卡鲁胺等。探索有效绿色的合成腈类化合物的方法具有十分重要的实用价值。
在过去的几十年中，研究者已经报道了许多合成腈的合成方法，包括醛肟或酰胺的脱水（ACS Catal. 2013, 3, 1652），Sandmeyer 反应（Chem. Rev. 1947, 40, 251），Rosenmund von Braun 反应（Tetrahedron, 1984, 40, 1433），芳基卤化物的氰化（Chem.Soc. Rev. 2011, 40, 5049.），以及胺的氧化（Green Chem. 2019, 21, 5386）。这些方法通常采用化学计量的剧毒 HCN 或金属基氰化物，如 KCN、NaCN 或 K4[Fe(CN)6] 作为起始材料。此外，由于形成仲胺和叔胺副产物，胺氧化为腈的选择性较差。
以分子氧（或空气）作为唯一氧化剂，同时利用多相催化剂催化醇的氨氧化是获得腈的优选途径。近十年来，研究者开发了一系列过渡金属多相催化剂（Org. Chem. Front.2021 Doi：10.1039/D1QO00275A）。然而，其中贵金属催化具有高成本、高毒性的缺点，而非贵金属催化剂的催化条件比较苛刻，且回收使用效果不好。
氮碳材料锚定的铁单原子催化剂由于其特殊的结构而呈现出显著不同于常规纳米催化剂的活性、选择性和稳定性，但是如何将其成功且高效地用于腈类化合物的制备中，已成为本领域技术人员亟待解决的技术问题。
发明内容
本发明的目的是为了解决现有技术的不足，而提供一种氮碳材料锚定的铁单原子催化剂在催化醇的氨氧化制腈反应中的应用，所述反应的反应条件温和、选择性和底物耐受性好、三废少且催化剂廉价低毒易回收，易于推广应用。
为实现上述目的，本发明采用的技术方案如下：
氮碳材料锚定的铁单原子催化剂在催化醇的氨氧化制腈反应中的应用，步骤如下：将醇、氮碳材料锚定的铁单原子催化剂、氨水和水依次加入到反应容器中，于一定温度下反应一段时间，反应结束后，去除催化剂，对反应溶液进行后处理，即得腈化合物。
进一步地，所述醇、氮碳材料锚定的铁单原子催化剂、氨的摩尔比为：1:0.02~0.08:4~8；醇的摩尔用量与水的体积比为0.2：1mmol/mL。
更进一步地，所述氨水为25 wt.%的氨水溶液。
进一步地，反应时的温度为25~130℃，反应时间为12~24 h，反应时的空气压力为0.1~2 MPa。
进一步地，所述醇为取代苄醇、杂环基甲醇、取代烯丙基醇或脂肪醇中的一种。
更进一步地，所述取代苄醇为苄醇、对甲基苄醇、对甲氧基苄醇、间甲基苄醇、间甲氧基苄醇、邻甲氧基苄醇、3,4-二甲氧基苄醇、3,4-二甲基苄醇、对氯苄醇、对溴苄醇、对硝基苄醇、3,4,5-三甲氧基苄醇、3,4,5-三氟苄醇、对异丙基苄醇、对三氟甲基苄醇、2-萘甲醇、胡椒醇、苯并二氧六环-6-甲醇、对苯甲氧基苄醇、2-溴-3,4-二甲氧基苄醇或对苯基苄醇中的一种。
更进一步地，所述杂环基甲醇为喹啉-6-基甲醇、噻吩-2-基甲醇、吡啶-2-基甲醇或3-喹啉基甲醇中的一种。
更进一步地，所述取代烯丙基醇为肉桂醇、E-3-(吡啶-3-基)丙烯醇、E-2-甲基-3-苯基丙烯醇、E-3-(4-硝基苯基)丙烯醇、紫苏醇、桃金娘烯醇或香叶醇中的一种；所述脂肪醇为2-(4-甲氧基苯基)乙醇、3-环己烯-1-甲醇、环己基甲醇、正己醇、正辛醇或香茅醇中的一种。
进一步地，所述反应结束后，离心分离催化剂；所述后处理具体为：加入乙酸乙酯萃取，收集有机相，经干燥、旋蒸除去乙酸乙酯，可得粗产品，粗产品通过重结晶或硅胶柱层析提纯得到腈化合物。
进一步地，所述氮碳材料锚定的铁单原子催化剂的制备方法为：将七水硫酸铁、六水硝酸锌加入到水中配制溶液1；将2-甲基咪唑和苯胺加入另外的水中，剧烈搅拌至混合均匀，得溶液2；将溶液1倒入正在搅拌的溶液2中，所得悬浊液继续搅拌一段时间，搅拌结束后，离心分离得到固体，将所得固体经水洗、干燥后，于氮气氛围下进行煅烧，即得氮碳材料锚定的铁单原子催化剂。
本发明与现有技术相比，其有益效果为：
（1）本发明以氮碳材料锚定的铁单原子材料为催化剂，具有类酶的FeN4结构，其对于分子氧表现出了优异的活化性能，因此可以高效催化醇的氨氧化反应。
（2）本发明的应用方法反应条件温和，选择性和底物耐受性好且催化剂廉价低毒。
（3）催化剂中的铁以单原子的形式锚定在氮碳材料上，具有良好的稳定性和利用率，因此催化可以实现高效回收利用且铁用量较低。
（4）本发明易于实现腈类化合物的放大生产制备，有利于大范围推广。
（5）相比于现有技术，本发明将氮碳材料锚定的铁单原子催化剂应用在催化醇的氨氧化制腈反应中，具有明显的价格、活性和环保优势（具体见表1）。
附图说明
图1为本发明胡椒腈3r的氢谱；1H NMR (500 MHz, DMSO-d6) δ 7.41 – 7.36 (m,2H), 7.09 (d, J = 8.0 Hz, 1H), 6.16 (s, 2H).
图2为本发明3-(3-吡啶基)-2-丙烯腈3ab的氢谱；1H NMR (500 MHz, DMSO-d6) δ8.81 (d, J = 2.3 Hz, 1H), 8.62 (dd, J = 4.8, 1.6 Hz, 1H), 8.10 (dt, J = 8.0,2.0 Hz, 1H), 7.71 (d, J = 16.7 Hz, 1H), 7.48 (dd, J = 8.0, 4.8 Hz, 1H), 6.63(d, J = 16.8 Hz, 1H)。
具体实施方式
下面结合实施例对本发明作进一步的详细描述。
本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限定本发明的范围。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过购买获得的常规产品。
氮碳材料锚定的铁单原子材料的制备方法如下：
七水硫酸铁0.1 mmol，六水硝酸锌2.0 mmol加入到20 mL水中配成溶液（溶液1）。2-甲基咪唑8 mmol和苯胺8 mmol，加入另外水中，剧烈搅拌10 min，直到混合物搅拌均匀（溶液2）。将溶液1倒入正在搅拌的溶液2中，所得悬浊液继续搅拌一段时间。搅拌结束后，通过离心分离所得固体，水洗2次，并在60 oC下干燥12 h。所得固体在管式炉中氮气氛围下900 oC煅烧2 h，升温速率为5 ℃/min，得到最终的氮碳材料锚定的铁单原子催化剂，记为Fe1@NC。
本发明取代苄醇的氨氧化反应的反应式如下：
本发明取代苄醇的氨氧化反应对应的目标产物及对应的产率如下：
本发明杂环基甲醇、取代烯基醇和脂肪醇的氨氧化反应的反应式、对应的目标产物及对应的产率如下：
实施例1：苄醇的氨氧化反应
将0.2 mmol苄醇，20 mg Fe1@NC，150 mg 25 wt.%氨水溶液，1 mL水加入到反应容器内，常压空气条件下35 oC反应24 h。反应结束降温后，离心分离催化剂和反应液。加入乙酸乙酯（1 mL×3）萃取收集有机相，干燥、旋蒸得粗产品，其可以通过硅胶柱层析提纯得到目标产物苯甲腈3a 20.4 mg，产率99%，纯度93%。
腈类化合物3b-3j、3l-3s、3v-3z、3aa-3ad的合成步骤与实施例1相同，只需将相同摩尔量的苄醇换成其他对应的醇即可。
实施例2：对硝基苄醇的氨氧化反应
将0.2 mmol对硝基苄醇，20 mg Fe1@NC，150 mg 25 wt.%氨水溶液，1 mL水加入到反应容器内，常压空气条件下50 oC反应24 h。反应结束降温后，离心分离催化剂和反应液，通过气相检测确定反应产率和选择性。加入乙酸乙酯（1 mL×3）萃取收集有机相，干燥、旋蒸得粗产品，其可以通过硅胶柱层析提纯得到目标产物3k 26.6 mg，产率90%，纯度97%。
腈类化合物3t、3u的合成步骤与实施例2相同，只需将相同摩尔量的对硝基苄醇换成其他对应的醇即可。
实施例3：香茅醇的氨氧化反应
将0.2 mmol香茅醇，20 mg Fe1@NC，150 mg 25 wt.%氨水溶液，1 mL水加入到反应容器内，2 Mpa空气条件下130 oC反应24 h。反应结束降温后，离心分离催化剂和反应液，通过气相检测确定反应产率和选择性。加入乙酸乙酯（1 mL×3）萃取收集有机相，干燥、旋蒸得粗产品，其可以通过硅胶柱层析提纯得到目标产物3ak 20.8 mg，69%，纯度95%。
腈类化合物3ae-3aj、3al的合成步骤与实施例3相同，只需将相同摩尔量的香茅醇换成其他对应的醇即可。
实施例4：苄醇的氨氧化反应
将0.2 mmol苄醇，20 mg FeCl2，150 mg 25 wt.%氨水溶液，1 mL水加入到反应容器内，常压空气条件下35 oC反应24 h。反应结束降温后，离心分离催化剂和反应液，经气相检测没有发现有目标产物3a生成。
实施例5：苄醇的氨氧化反应
将0.2 mmol苄醇，20 mg 纳米Fe2O3，150 mg 25 wt.%氨水溶液，1 mL水加入到反应容器内，常压空气条件下35 oC反应24 h。反应结束降温后，离心分离催化剂和反应液，经气相检测没有发现有目标产物3a生成。
表1 现有技术中其他催化剂在催化醇的氨氧化制腈反应中的应用
[1]T. Oishi, K. Yamaguchi, N. Mizuno, Angew. Chem. Int. Ed.2009, 48,6286-6288.
[2]Y. Preger, T. W. Root, S. S. Stahl, ACS Omega2018, 3, 6091-6096.
[3]A. N. Hashemi, H. Eshghi, K. Lamei, Appl. Organomet. Chem.2019, 33, e4835.
[4]H. Wang, D. Xu, E. Guan, L. Wang, J. Zhang, C. Wang, S. Wang, H.Xu, X. Meng, B. Yang, B. C. Gates, F.-S. Xiao, ACS Catal.2020, 10, 6299-6308.
[5]R. V. Jagadeesh, H. Junge, M. Beller, Nat. Commun.2014, 5, 4123.
[6]S. Shang, L. Wang, W. Dai, B. Chen, Y. Lv, S. Gao, Catal. Sci. Technol.2016, 6, 5746-5753
[7]S. Shang, W. Dai, L. Wang, Y. Lv, S. Gao, Chem. Commun.2017, 53,1048-1051.
[8]K.-k. Sun, J.-l. Sun, G.-P. Lu, C. Cai, Green Chem.2019, 21, 4334-4340.
[9]T. Yasukawa, X. Yang, S. Kobayashi, J. Org. Chem.2020, 85, 7543-7548.
上表1中所涉及的催化剂催化醇的氨氧化制腈反应的反应式如下：
上述实施例对本发明的实施方式作了详细说明，但是本发明并不限于上述实施方式，在本领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下做出各种变化。以上所述仅为本发明较佳可行的实施例而已，并非因此局限本发明的权利范围，凡运用本发明说明书内容所作的等效结构变化，均包含于本发明的权利范围之内。

Claims (2)

1.氮碳材料锚定的铁单原子催化剂在催化醇的氨氧化制腈反应中的应用，其特征在于，步骤如下：将醇、氮碳材料锚定的铁单原子催化剂、氨水和水依次加入到反应容器中，于一定温度下反应一段时间，反应结束后，去除催化剂，对反应溶液进行后处理，即得腈化合物；
所述醇、氮碳材料锚定的铁单原子催化剂、氨的摩尔比为：1:0.02~0.08:4~8；醇的摩尔用量与水的体积比为0.2：1mmol/mL；
所述氨水为25 wt.%的氨水溶液；
反应时的温度为25~130℃，反应时间为12~24 h，反应时的空气压力为0.1~2 MPa；
所述醇为取代苄醇、杂环基甲醇、取代烯丙基醇或脂肪醇中的一种；
所述杂环基甲醇为喹啉-6-基甲醇、噻吩-2-基甲醇、吡啶-2-基甲醇或3-喹啉基甲醇中的一种；
所述取代苄醇为间甲基苄醇、间甲氧基苄醇、邻甲氧基苄醇、3,4-二甲氧基苄醇、3,4-二甲基苄醇、对溴苄醇、对硝基苄醇、3,4,5-三甲氧基苄醇、3,4,5-三氟苄醇、对三氟甲基苄醇、2-萘甲醇、胡椒醇、苯并二氧六环-6-甲醇、对苯甲氧基苄醇、2-溴-3,4-二甲氧基苄醇或对苯基苄醇中的一种；
所述取代烯丙基醇为E-3-(吡啶-3-基)丙烯醇、E-2-甲基-3-苯基丙烯醇、E-3-(4-硝基苯基)丙烯醇、紫苏醇、桃金娘烯醇或香叶醇中的一种；所述脂肪醇为3-环己烯-1-甲醇、环己基甲醇、正己醇、正辛醇或香茅醇中的一种；
所述氮碳材料锚定的铁单原子催化剂的制备方法为：将七水硫酸铁、六水硝酸锌加入到水中配制溶液1；将2-甲基咪唑和苯胺加入另外的水中，剧烈搅拌至混合均匀，得溶液2；将溶液1倒入正在搅拌的溶液2中，所得悬浊液继续搅拌一段时间，搅拌结束后，离心分离得到固体，将所得固体经水洗、干燥后，于氮气氛围下进行煅烧，即得氮碳材料锚定的铁单原子催化剂。
2.根据权利要求1所述的氮碳材料锚定的铁单原子催化剂在催化醇的氨氧化制腈反应中的应用，其特征在于，所述反应结束后，离心分离催化剂；所述后处理具体为：加入乙酸乙酯萃取，收集有机相，经干燥、旋蒸除去乙酸乙酯，可得粗产品，粗产品通过重结晶或硅胶柱层析提纯得到腈化合物。
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