CN108927219A - 绿色高效合成金属卟啉共轭聚合物并催化氧化环酮类制备内酯化合物 - Google Patents
绿色高效合成金属卟啉共轭聚合物并催化氧化环酮类制备内酯化合物 Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 16
- 230000003647 oxidation Effects 0.000 title claims abstract description 15
- -1 lactone compound Chemical class 0.000 title claims abstract description 6
- 150000003997 cyclic ketones Chemical class 0.000 title abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title description 3
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- 238000003786 synthesis reaction Methods 0.000 title description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001413 amino acids Chemical class 0.000 claims abstract description 7
- 150000002596 lactones Chemical class 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000002904 solvent Substances 0.000 claims abstract 2
- 239000000758 substrate Substances 0.000 claims abstract 2
- 150000004032 porphyrins Chemical class 0.000 claims description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
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- 239000000126 substance Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 108700003601 dimethylglycine Proteins 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims 2
- NCAJWYASAWUEBY-UHFFFAOYSA-N 3-[20-(2-carboxyethyl)-9,14-diethyl-5,10,15,19-tetramethyl-21,22,23,24-tetraazapentacyclo[16.2.1.1^{3,6}.1^{8,11}.1^{13,16}]tetracosa-1(21),2,4,6(24),7,9,11,13,15,17,19-undecaen-4-yl]propanoic acid Chemical compound N1C2=C(C)C(CC)=C1C=C(N1)C(C)=C(CC)C1=CC(C(C)=C1CCC(O)=O)=NC1=CC(C(CCC(O)=O)=C1C)=NC1=C2 NCAJWYASAWUEBY-UHFFFAOYSA-N 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
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- 239000004471 Glycine Substances 0.000 claims 1
- 108010077895 Sarcosine Proteins 0.000 claims 1
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- 150000001555 benzenes Chemical class 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
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- 239000002131 composite material Substances 0.000 claims 1
- 239000012141 concentrate Substances 0.000 claims 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims 1
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- ZIXLDMFVRPABBX-UHFFFAOYSA-N 2-methylcyclopentan-1-one Chemical compound CC1CCCC1=O ZIXLDMFVRPABBX-UHFFFAOYSA-N 0.000 description 4
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- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 description 1
- BFMCCQBOSWKYPC-UHFFFAOYSA-N 2-(2-oxopropyl)cyclopentan-1-one Chemical compound CC(=O)CC1CCCC1=O BFMCCQBOSWKYPC-UHFFFAOYSA-N 0.000 description 1
- MOMFXATYAINJML-UHFFFAOYSA-N 2-Acetylthiazole Chemical group CC(=O)C1=NC=CS1 MOMFXATYAINJML-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- XJJWWOUJWDTXJC-UHFFFAOYSA-N [Mn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Mn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 XJJWWOUJWDTXJC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- MMFBJNOBEXDRLM-UHFFFAOYSA-N c1cc2cc3ccc(cc4ccc(cc5ccc(cc1n2)[nH]5)n4)[nH]3.c1ccc(cc1)[Fe](c1ccccc1)(c1ccccc1)c1ccccc1 Chemical compound c1cc2cc3ccc(cc4ccc(cc5ccc(cc1n2)[nH]5)n4)[nH]3.c1ccc(cc1)[Fe](c1ccccc1)(c1ccccc1)c1ccccc1 MMFBJNOBEXDRLM-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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Abstract
本发明公开了一种以廉价、高效的催化体系(铜盐/氨基酸)催化合成的四氨基苯基桥联的金属卟啉共轭多孔聚合物为催化剂，催化氧化环戊酮、环己酮及其衍生物生成内酯的方法，其特征在于在通入l‑50atm的空气或氧气，聚合金属卟啉(I)的投放量为被氧化底物的5×10‑4～4×10‑3wt％，苯甲醛为催化助剂，1,2‑二氯乙烷为溶剂，反应温度50℃‑110℃的条件下对环酮类化合物进行催化氧化，环酮类化合物转化率可达99％以上，对应的内酯产物的选择性达96％以上，并且催化剂用量少，催化效果好，多次重复利用仍能保持很高的催化活性。
Description
技术领域
本发明涉及一种高效环保的催化体系催化合成金属锰卟啉共轭聚合物，并用于催化氧化环酮类生成内酯的方法。
背景技术
金属卟啉是一大类具有四吡咯环核心结构的化合物，具有独特的物理化学特性，在材料、化工、物理、化学等领域引起广泛关注。金属卟啉多被用于仿生催化研究，例如，催化活化C-H；在温和条件下选择性催化环酮类、醇类。如专利CN102391238B[P].2013使用简单的四苯基铁卟啉催化氧化环己酮生成己内酯，表现出较好的催化效果。然而，单体金属卟啉催化体系极不稳定，在反应过程中容易受搅拌、高温等外界条件影响而失活，并且随着反应进行容易分解和自我氧化，不能重复使用。因此研究出一种能够重复使用、高催化活性、适用于环酮类氧化的新型功能催化剂，显得很有必要。
目前，通过C-N键的偶联使四氨基苯基金属卟啉聚合形成微孔结构的聚合材料是一种新兴的研究方向，近几年，钯催化体系催化C-N键的偶联成为卟啉聚合的热点，但是钯金属不但有很强的毒性，而且非常昂贵，不适合用于大规模的工业生产。马大伟等人通过Cu盐/氨基酸催化体系催化了小分子间的C-N键的偶联(J.Org.Chem.2006,71,5268-5273)，然而，铜盐催化体系完成卟啉C-N键偶联聚合的合成方法还未见报道。M.B.Ansari等人将单卟啉分散于介孔结构的有机硅中形成PMOs材料完成对环己酮的催化氧化(ACS Catalysis.1(2011)855-863)，而直接将卟啉聚合形成微孔结构的聚合物并催化氧化环酮类的技术更是未见报道。
发明内容
本发明提供了一种环保的，低价的，高效的催化体系(铜盐/氨基酸)催化合成四氨基苯基金属卟啉共轭聚物并用于催化氧化环酮类的方法。四氨基苯基卟啉聚合物有很大的比表面积，并且具有1.0-4.0nm左右的微介孔结构，在氧气存在、60℃的温和条件下能够催化氧化环酮类，氧化产物为对应的己内酯，选择性高达96％以上。并且聚合卟啉在反应过程中不发生分解和自我氧化，可多次重复利用。该催化氧化反应方程式如下：
本发明提供的方法中，用于催化氧化环酮类的四氨基苯基卟啉聚合物是以高效、环保、廉价的铜盐/氨基酸催化体系催化聚合。金属卟啉聚合物催化剂的化学结构如(I)所示：结构式(I)中的金属原子M选自Mn、Zn、Co、Fe和Ni；苯环上取代基R1，R2选自氢，甲基，乙基，硝基，甲氧基，卤素等；X为乙酸，乙酰丙酮，卤素等。
该催化剂结构特征在于金属卟啉单体四臂上亚氨基活性基团和对二溴苯之间发生C-N偶联，单卟啉被亚苯基所链接，每个单臂桥连接的亚苯基单体个数为m＝1-3，卟啉高聚物大分子中重复单元为n＝1-3000，该聚合物不被有机溶剂溶解，表现很好的3D刚性多孔结构，且具有优异的催化性能，在催化过程中表现出很好的结构稳定性和化学稳定性，能够循环多次利用，比表面积高达60-2500m2/g，主要孔径集中在1.0-4.0nm。
本发明所制备的聚合物材料，耐高温性能较好，催化氧化环酮类过程中能够稳定存在，能够多次回收重复利用，是催化氧化环酮类的一种新型催化材料。
具体实施方式
下面对本发明方案进行举例说明，但本发明包括但不限于如下的实施例：
实施例1
向干燥后装有冷凝装置和温度计的50ml三口烧瓶中，加入76.2mg四氨基苯基铁卟啉，58.97mg对溴苯，20.6mgN,N-二甲基甘氨酸，19mgCuI，280mgK2CO3，10ml1,4-二氧六环充分搅拌混合，控制温度为90℃，搅拌反应24小时，合成了具有结构(I)的金属卟啉聚合物，其中R1＝R2＝H，m＝1，M＝Fe，n＝638，比表面积为364m2/g，收率为87.6％。
实施例2
向干燥后装有冷凝装置和温度计的50ml三口烧瓶中，加入78.6mg四氨基苯基钴卟啉，130.68mg对溴联苯，20.6mgN,N-二甲基甘氨酸，14mgCuBr，280mgK2CO3，10ml1,4-二氧六环充分搅拌混合，控制温度为110℃，搅拌反应24小时，合成了具有结构(I)的金属卟啉聚合物，其中R1＝R2＝甲基，m＝2，M＝Mn，n＝581，比表面积为478m2/g，收率为83.6％。
实施例3
将10mg具有结构式(I)的金属卟啉聚合物，R1＝R2＝H，m＝1，n＝628，M＝Mn，比表面积为362m2/g，平均孔径为1.6nm，加入到0.15mmol环戊酮中，加热到60℃，控制空气流速为120ml/min，持续搅拌反应5h，环戊酮的转化率为99％，选择性为98.3％。
实施例4
将10mg具有结构式(I)的金属卟啉聚合物，R1＝R2＝Br，m＝2，n＝547，M＝Mn，比表面积为580m2/g，平均孔径为2.1nm，加入到0.15mmol 2-甲基环戊酮中，加热到60℃，控制空气流速为120ml/min，持续搅拌反应5h，2-甲基环戊酮的转化率为98.8％，选择性为97.6％。
实施例5
将10mg具有结构式(I)的金属卟啉聚合物，R1＝CH3，R2＝Br，m＝3，n＝370，M＝Mn，比表面积为678m2/g，平均孔径为3.40nm，加入到0.15mmol环己酮中，加热到60℃，控制空气流速为120ml/min，持续搅拌反应5h，环己酮的转化率为99.2％，选择性为98.7％。
实施例6
将10mg具有结构式(I)的金属卟啉聚合物，R1＝CH3，R2＝Cl，m＝2，n＝481，M＝Co，比表面积为610m2/g，平均孔径为2.28nm，加入到0.15mmol 2-乙基环己酮中，加热到60℃，控制空气流速为120ml/min，持续搅拌反应5h，2-乙基环己酮的转化率为99.4％，选择性为96.7％。
实施例7
将10mg具有结构式(I)的金属卟啉聚合物，R1＝OCH3，R2＝Cl，m＝1，n＝610，M＝Zn，比表面积为390m2/g，平均孔径为1.29nm，加入到0.15mmol 2-硝基环己酮中，加热到60℃，控制空气流速为120ml/min，持续搅拌反应5h，2-硝基环己酮的转化率为99.2％，选择性为97.4％。
实施例8
将10mg具有结构式(I)的金属卟啉聚合物，R1＝OCH3，R2＝Br，m＝2，n＝538，M＝Zn，比表面积为560m2/g，平均孔径为2.56nm，加入到0.15mmol 2-硝基环戊酮中，加热到60℃，控制空气流速为120ml/min，持续搅拌反应5h，2-硝基环戊酮的转化率为98.7％，选择性为98.8％。
实施例9
将10mg具有结构式(I)的金属卟啉聚合物，R1＝Br，R2＝Br，m＝3，n＝376，M＝Ni，比表面积为762m2/g，平均孔径为3.10nm，加入到0.15mmol 2-溴-环戊酮中，加热到60℃，控制空气流速为120ml/min，持续搅拌反应5h，2-溴-环戊酮的转化率为99.5％，选择性为96.8％。
实施例10
将10mg具有结构式(I)的金属卟啉聚合物，R1＝OCH3，R2＝OCH3，m＝1，n＝662，M＝Co，比表面积为395m2/g，平均孔径为1.75nm，加入到0.15mmol 2-乙酰丙酮基-环戊酮中，加热到60℃，控制空气流速为120ml/min，持续搅拌反应5h，2-乙酰丙酮基-环戊酮的转化率为99.3％，选择性为97.7％。
实施例11
将10mg具有结构式(I)的金属卟啉聚合物，R1＝Cl，R2＝Cl，m＝2，n＝474，M＝Co，比表面积为580m2/g，平均孔径为2.70nm，加入到0.15mmol 2-乙酰丙酮基-环己酮中，加热到60℃，控制空气流速为120ml/min，持续搅拌反应5h，2-乙酰丙酮基-环己酮的转化率为99％，选择性为98.5％。
实施例12
将10mg具有结构式(I)的金属卟啉聚合物，R1＝OCH3，R2＝H，m＝3，n＝368，M＝Ni，比表面积为736m2/g，平均孔径为3.61nm，加入到0.15mmol环己酮中，加热到60℃，控制空气流速为120ml/min，持续搅拌反应5h，环己酮的转化率为99.3％，选择性为96.9％。
实施例13
将10mg具有结构式(I)的金属卟啉聚合物，R1＝OCH3，R2＝OCH3，m＝1，n＝762，M＝Co，比表面积为395m2/g，平均孔径为1.75nm，加入到0.15mmol 2-乙酰丙酮基-环戊酮中，加热到60℃，控制空气流速为120ml/min，持续搅拌反应5h，回收循环利用该催化剂，重复利用四次后，2-乙酰丙酮基-环戊酮的转化率为98.7％，选择性为97.3％。
Claims (3)
1.一种基于化学结构式如(I)所示的金属卟啉高聚物，温和条件下催化空气或氧气氧化环己酮、环戊酮及其衍生物生成对应的内酯，所用催化剂(I)的基本结构特征：结构式(I)中的金属原子M选自Mn、Zn、Co、Fe和Ni；苯环上取代基R1，R2选自氢，甲基，乙基，硝基，甲氧基，卤素等；X为乙酸，乙酰丙酮，卤素等；催化氧化条件为：通入l-50atm的空气或氧气，聚合金属卟啉(I)的投放量为被氧化底物的5×10-4～4×10-3wt％，苯甲醛为催化助剂，1,2-二氯乙烷为溶剂，反应温度50℃-110℃，对应的内酯产物的选择性达96％以上；
金属卟啉高聚物催化剂(I)结构单元
催化氧化反应方程式示例如下：
。
2.基于权利要求1所阐述的方法，金属卟啉高聚物(I)是由相应的四氨基苯基金属卟啉与对溴多苯化合物为原料，在60-120℃下,以低价、环保、高效的铜盐/氨基酸为复合催化剂催化合成得到；铜盐是指含有亚铜离子的盐类，可以是普通的CuI、CuBr、CuCl、Cu2O等含有亚铜离子的无机盐；氨基酸是指甘氨酸、N,N-二甲基甘氨酸、N-甲基甘氨酸等系列氨基酸。
3.根据权利要求1所阐述的方法，该金属卟啉高聚物(I)的结构特征在于金属卟啉单体四臂上亚氨基活性基团和对溴苯之间发生C-N偶联，单卟啉被亚苯基所链接，每个单臂桥连接的亚苯基单体个数为m＝1-3，高聚物大分子中卟啉单体的重复单元数为n＝1-3000，该聚合物不被有机溶剂溶解，表现出很好的3D刚性多孔结构，且在催化过程中表现出很好的结构稳定性和化学稳定性，能够循环多次利用，比表面积高达60-2500m2/g，主要孔径集中在1.0-4.0nm。
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