CN108299138B - 一种可见光催化氧化胺类化合物合成亚胺类化合物的方法 - Google Patents
一种可见光催化氧化胺类化合物合成亚胺类化合物的方法 Download PDFInfo
- Publication number
- CN108299138B CN108299138B CN201810136237.0A CN201810136237A CN108299138B CN 108299138 B CN108299138 B CN 108299138B CN 201810136237 A CN201810136237 A CN 201810136237A CN 108299138 B CN108299138 B CN 108299138B
- Authority
- CN
- China
- Prior art keywords
- visible light
- under
- hmdtn
- imine
- porphyrin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 36
- 230000003647 oxidation Effects 0.000 title claims abstract description 34
- 150000002466 imines Chemical class 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 28
- -1 amine compound Chemical class 0.000 title claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- AKAIWNDBVZJOAJ-UHFFFAOYSA-N 1,4-dithiine Chemical compound S1C=CSC=C1 AKAIWNDBVZJOAJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 238000005286 illumination Methods 0.000 claims description 18
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- 230000009471 action Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 68
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000002474 experimental method Methods 0.000 description 17
- 150000001412 amines Chemical class 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000013067 intermediate product Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001254 matrix assisted laser desorption--ionisation time-of-flight mass spectrum Methods 0.000 description 6
- COCAUCFPFHUGAA-MGNBDDOMSA-N n-[3-[(1s,7s)-5-amino-4-thia-6-azabicyclo[5.1.0]oct-5-en-7-yl]-4-fluorophenyl]-5-chloropyridine-2-carboxamide Chemical compound C=1C=C(F)C([C@@]23N=C(SCC[C@@H]2C3)N)=CC=1NC(=O)C1=CC=C(Cl)C=N1 COCAUCFPFHUGAA-MGNBDDOMSA-N 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- OENHQHLEOONYIE-UKMVMLAPSA-N all-trans beta-carotene Natural products CC=1CCCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C OENHQHLEOONYIE-UKMVMLAPSA-N 0.000 description 4
- TUPZEYHYWIEDIH-WAIFQNFQSA-N beta-carotene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2=CCCCC2(C)C TUPZEYHYWIEDIH-WAIFQNFQSA-N 0.000 description 4
- 235000013734 beta-carotene Nutrition 0.000 description 4
- 239000011648 beta-carotene Substances 0.000 description 4
- 229960002747 betacarotene Drugs 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000003642 reactive oxygen metabolite Substances 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000004435 EPR spectroscopy Methods 0.000 description 3
- 238000004847 absorption spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 3
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QWLULCKKOHDCIE-UHFFFAOYSA-N 2,3-dimethyl-1-oxidopyridin-1-ium Chemical compound CC1=CC=C[N+]([O-])=C1C QWLULCKKOHDCIE-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000003939 benzylamines Chemical class 0.000 description 1
- 125000001409 beta-carotene group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/22—Magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种可见光催化氧化胺类化合物合成亚胺类化合物的方法，所述方法以四羟甲基四(1，4‑二噻英)四氮杂钴卟啉为催化剂，以分子氧为氧化剂，在λ≥420 nm的可见光照射下实现胺类化合物氧化为相应的亚胺类化合物；本发明与现有的亚胺类化合物合成方法不同，在以含硫氮杂钴卟啉作为光催化剂的催化体系中，可以在以太阳光为能源、分子氧为氧化剂的条件下实施胺类化合物的光催化选择性氧化，高效、节能地生产亚胺类化合物。
Description
技术领域
本发明属于化工和制药技术领域，具体涉及一种可见光催化氧化胺类化合物合成亚胺类化合物的方法。
背景技术
亚胺类化合物是一种非常重要的有机合成中间体，已广泛应用于精细化工、农药合成和医药合成等领域。开发高效、节能的亚胺类化合物合成方法具有重要意义和应用价值。
光催化技术可以将可再生的太阳能引入到有机化合物的合成领域，以环境友好和廉价的氧气作为氧化剂，在温和的条件下实现有机化合物的选择性氧化，获得目标产物，该技术具有绿色和节能的优势，作为一种绿色有机合成途径受到了广泛的关注。太阳光中大部分为可见光，为提高太阳能的利用率，需要开发高效的可见光响应型光催化剂。含硫氮杂金属卟啉在可见光区具有强的摩尔吸光系数，可以作为可见光催化剂有效地利用太阳能。利用含硫氮杂金属卟啉在温和的条件下可见光活化分子氧氧化有机物，通过优化反应条件获得高产率的目标产物，可以为绿色有机合成提供一种新的途径。
发明内容
本发明的目的在于克服现有技术的不足，提供一种可见光催化氧化胺类化合物合成亚胺类化合物的方法，该方法利用可见光催化剂四羟甲基四(1，4-二噻英)四氮杂钴卟啉对分子氧进行活化，能够高选择性地氧化胺类化合物合成亚胺类化合物。
为解决上述问题，本发明采用的技术方案为：
一种可见光催化氧化胺类化合物合成亚胺类化合物的方法，所述方法以四羟甲基四(1，4-二噻英)四氮杂金属卟啉为可见光催化剂，以分子氧为氧化剂，在λ≥420nm的可见光照射下实现胺类化合物氧化为相应的亚胺类化合物。
优选的，以四羟甲基四(1，4-二噻英)四氮杂钴卟啉(简写为CoPz(hmdtn)4)为可见光催化剂。
其中，所述CoPz(hmdtn)4的分子结构式为：
所述方法的具体步骤为：在石英夹套光反应瓶中加入一定量的CoPz(hmdtn)4和溶剂，在搅拌的作用下使CoPz(hmdtn)4在溶剂中完全溶解，再向体系中加入胺类化合物，并在无光照的条件下继续搅拌2-4h；然后在1-4atm氧气和λ≥420nm的可见光光照的条件下反应一定时间即可。
优选的，所述溶剂为乙腈或二甲基亚砜。
优选的，所述胺类化合物包括伯胺或仲胺。
另外，本发明还要求保护CoPz(hmdtn)4在催化氧化胺类化合物合成亚胺类化合物中的应用，其中，所述催化氧化反应是以分子氧为氧化剂，在λ≥420nm的可见光照射下进行。
与现有技术相比，本发明的优点和有益技术效果为：
(1)本发明以CoPz(hmdtn)4为可见光催化剂，可以直接高效催化氧化胺类化合物为亚胺类化合物，且产物亚胺类化合物具有高的选择性；
(2)本发明在可见光的作用下，通过CoPz(hmdtn)4活化O2产生活性氧物种1O2和O2 ·-，这两种活性氧物种能够氧化胺生成关键的中间产物NH-亚胺，然后NH-亚胺与胺可以很容易通过缩合反应生成目标产物亚胺，从而在可见光和分子氧的条件下可以高效率、高选择性氧化胺类化合物为亚胺类化合物，即本发明是在CoPz(hmdtn)4、可见光和O2三者综合作用下实现胺类化合物的高选择性氧化生成亚胺类化合物；
(3)本发明与现有的亚胺类化合物合成方法不同，在以CoPz(hmdtn)4作为可见光催化剂的催化体系中，可以在以太阳光为能源、分子氧为氧化剂的条件下实现胺类化合物的光催化选择性氧化，高效、节能地生产亚胺类化合物。
附图说明
图1为本发明实施例2中TMP-1O2的ESR信号图；
图2为本发明实施例2中DMPO-O2 ·-的ESR信号图；
图3为本发明实施例2中中间产物NH-亚胺的GC谱图；
图4为本发明实施例2中中间产物NH-亚胺的MS谱图；
图5为本发明实施例2中光谱DPD法测定光催化氧化苄胺过程中生成H2O2的紫外-可见吸收光谱图；
图6为本发明原料四羟甲基四(1，4-二噻英)四氮杂钴卟啉在DMF溶剂中的紫外-可见吸收光谱图；
图7为本发明原料四羟甲基四(1，4-二噻英)四氮杂钴卟啉的MALDI-TOF MS谱图；
图8为本发明原料四羟甲基四(1，4-二噻英)四氮杂镁卟啉在DMF溶剂中的紫外-可见吸收光谱图；
图9为本发明原料四羟甲基四(1，4-二噻英)四氮杂镁卟啉的MALDI-TOF MS谱图；
图10为本发明原料四羟甲基四(1，4-二噻英)四氮杂锌卟啉在DMF溶剂中的紫外-可见吸收光谱图；
图11为本发明原料四羟甲基四(1，4-二噻英)四氮杂锌卟啉的MALDI-TOF MS谱图。
具体实施方式
下面结合实施例对本发明的技术方案做进一步的阐述：
原料：
(1)CoPz(hmdtn)4的合成参考文献Journal of Molecular Catalysis A:Chemical(2013,372:114-120)，将文献中的原料醋酸亚铁替换为等摩尔量的四水合乙酸钴。利用紫外-可见吸收光谱和MALDI-TOF MS对CoPz(hmdtn)4进行了结构表征，其紫外-可见吸收光谱和MALDI-TOF MS谱图分别如图6和图7所示。
(2)四羟甲基四(1,4-二噻英)四氮杂镁卟啉(简写为MgPz(hmdtn)4)的合成参考文献Journal of Molecular Catalysis A:Chemical(2013,372:114-120)。利用紫外-可见吸收光谱和MALDI-TOF MS对MgPz(hmdtn)4进行结构表征，其紫外-可见吸收光谱和MALDI-TOFMS谱图分别如图8和图9所示。
(3)四羟甲基四(1，4-二噻英)四氮杂锌卟啉(简写为ZnPz(hmdtn)4)的合成参考文献Journal of Molecular Catalysis A:Chemical(2013,372:114-120)，将文献中的原料醋酸亚铁替换为等摩尔量的醋酸锌。利用紫外-可见吸收光谱和MALDI-TOF MS对ZnPz(hmdtn)4进行结构表征，其紫外-可见吸收光谱和MALDI-TOF MS谱图分别如图10和图11所示。
实施例1：
四羟甲基四(1，4-二噻英)四氮杂钴卟啉可见光催化氧化苄胺的活性测定
其步骤如下：在石英夹套光反应瓶中加入3mg CoPz(hmdtn)4和25mL乙腈(简写为CH3CN)，在搅拌的作用下使CoPz(hmdtn)4在乙腈中完全溶解，再向体系中加入1mmol苄胺，并在无光照的条件下继续搅拌2h。然后在1atm氧气和λ≥420nm的可见光(采用氙灯作为光源，并用420nm滤光片滤掉波长小于420nm的光，以下实施例同)光照的条件下反应3h，可见光的光强为0.747W·cm-2。利用GC-MS对反应产物进行定性分析，并通过GC对反应产物进行定量分析，本组为可见光光照条件下的实验，记为Entry 1；取消λ≥420nm的可见光光照，则为无光照条件下的实验，本组记为Entry 2。
按照同样的操作步骤，还进行了其他四组实验作为对照：在1atm氩气气氛和可见光光照的条件下，考察CoPz(hmdtn)4的光催化活性，本组记为Entry 3；不加CoPz(hmdtn)4，仅在可见光光照和氧气存在的条件下，考察苄胺的氧化，本组记为Entry 4；在1atm氧气和可见光光照的条件下，考察常见的四苯基钴卟啉(简写为CoTPP，其用量和CoPz(hmdtn)4相同)可见光催化氧化苄胺的活性，本组记为Entry 5；在1atm氧气和可见光光照的条件下，考察常见的间-四羟乙基(4-甲氧苯基)钴卟啉(简写为CoTPPOMe，其用量和CoPz(hmdtn)4相同)可见光催化氧化苄胺的活性，本组记为Entry 6。
表1.苄胺在不同条件下的氧化.
实验结果如表1所示，对比实验表明，在无催化剂CoPz(hmdtn)4存在(Entry 4)，无可见光光照(Entry 2)以及氩气气氛(Entry 3)的条件下，苄胺都基本不发生转化；而苄胺在催化剂CoPz(hmdtn)4存在、可见光光照以及氧气存在的条件下，可以发生有效转化，光反应3h，苄胺的转化率达到90％，而其氧化产物N-苄烯丁胺的选择性达到99％以上(Entry1)。表明在可见光的条件下CoPz(hmdtn)4可以高效地活化分子氧直接催化氧化苄胺为相应的亚胺，该反应是一个光催化氧化反应。同时，常见的CoTPP和CoTPPOMe催化剂也可以光催化氧化苄胺为N-苄烯丁胺，光反应3h苄胺的转化率分别为11％(Entry 5)和43％(Entry6)，通过比较可知，苄胺在CoPz(hmdtn)4催化体系中的转化率是CoTPP催化体系中的8.2倍、CoTPPOMe催化体系中的2.1倍，表明与常见的金属卟啉相比，含硫氮杂钴卟啉具有高的光催化活性。
实施例2：
四羟甲基四(1，4-二噻英)四氮杂钴卟啉可见光催化氧化苄胺的机理研究
(一)活性氧物种的检测
其步骤如下：在石英试管中加入3mg CoPz(hmdtn)4和1mL CH3CN，在搅拌的作用下使CoPz(hmdtn)4在CH3CN中完全溶解。然后加入10μL 2,2,6,6-四甲基哌啶(简写为TMP)或20μL二甲基吡啶N-氧化物(简写为DMPO)。在λ≥420nm的可见光光照的条件下，持续鼓入氧气4min，然后取少量反应液进行电子自旋共振(简写为ESR)检测。TMP为单线态氧(简写为1O2)的捕获剂，DMPO为超氧阴离子自由基(简写为O2 ·-)的捕获剂。
实验结果如图1和图2所示。实验结果表明，在可见光的照射下，CoPz(hmdtn)4可以活化O2通过能量转移产生活性氧物种1O2(图1)和电子转移产生活性氧物种O2 ·-(图2)。
(二)淬灭实验
进一步实施了淬灭实验，考察活性氧物种对光催化氧化苄胺的影响。其步骤如下：
在石英夹套光反应瓶中加入3mg CoPz(hmdtn)4和25mL CH3CN，在搅拌的作用下使CoPz(hmdtn)4在CH3CN中完全溶解，再向体系中加入1mmol苄胺，并在无光照的条件下继续搅拌2h。然后加入1mmolβ-胡萝卜素(简写为β-Carotene)或1mmol 2,2,6,6-四甲基哌啶氮氧化物(简写为TEMPO)，在1atm氧气和λ≥420nm的可见光光照的条件下反应3h，可见光的光强为0.747W·cm-2。并通过GC对反应产物进行定量分析，加入淬灭剂β-Carotene为检测活性氧物种1O2对光催化氧化苄胺的影响，本组记为Entry 1；加入淬灭剂TEMPO为检测活性氧物种O2 ·-对光催化氧化苄胺的影响，本组记为Entry 2；不加入淬灭剂的组记为Entry 3。
实验结果如表2所示。对比实验表明，加入1O2的淬灭剂β-Carotene时，苄胺的转化率从90％降低到了1％；当加入O2 ·-的淬灭剂TEMPO时，苄胺的转化率从90％降低到了7％，表明1O2和O2 ·-是此光催化过程中的活性氧物种，与ESR测试的结果相一致。
表2.淬灭剂对光催化氧化苄胺的影响.
(三)中间产物分析
其步骤如下：在石英夹套光反应瓶中加入3mg CoPz(hmdtn)4和25mL CH3CN，在搅拌的作用下使CoPz(hmdtn)4在CH3CN中完全溶解，再向体系中加入1mmol苄胺，并在无光照的条件下继续搅拌2h。然后在1atm氧气和λ≥420nm的可见光光照的条件下反应2h，可见光的光强为0.747W·cm-2。利用GC-MS对中间产物NH-亚胺进行检测。
实验结果如图3和图4所示。实验结果表明，在光催化氧化苄胺为N-苄烯丁胺的过程中有中间产物NH-亚胺的生成。
进一步通过光谱DPD法测定了苄胺转化为N-苄烯丁胺的过程中的中间产物H2O2。其步骤如下：在石英夹套光反应瓶中加入3mg CoPz(hmdtn)4和25mL CH3CN，在搅拌的作用下使CoPz(hmdtn)4在CH3CN中完全溶解，再向体系中加入1mmol苄胺，并在无光照的条件下继续搅拌2h。然后在1atm氧气和λ≥420nm可见光光照的条件下反应，可见光的光强为0.747W·cm-2。然后每隔一定时间用光谱DPD法测定此光催化氧化过程中生成的H2O2。
实验结果如图5所示。实验结果表明，在光催化氧化苄胺过程中有H2O2的生成，而且随着光照时间的延长，H2O2的生成量逐渐增大。
通过ESR检测和淬灭实验，1O2和O2 ·-是苄胺的光催化氧化过程中的活性氧物种。同时，通过中间产物的检测分析，此光催化过程中有中间产物NH-亚胺的生成，而NH-亚胺是关键中间产物，因为NH-亚胺与苄胺可以很容易通过缩合反应生成目标产物N-苄烯丁胺。CoPz(hmdtn)4在可见光的作用下，活化O2产生活性氧物种1O2和O2 ·-，这两种活性氧物种能够氧化苄胺生成关键的中间产物NH-亚胺，中间产物H2O2的生成进一步证实了这步反应的发生；然后NH-亚胺与苄胺可以很容易通过缩合反应生成目标产物N-苄烯丁胺，这可能就是CoPz(hmdtn)4在可见光和分子氧条件下可以高效率、高选择性氧化胺类化合物为亚胺类化合物的原因。
实施例3：
考察中心金属对催化活性的影响
按照实施例1的操作步骤，分别在催化剂为CoPz(hmdtn)4、MgPz(hmdtn)4和ZnPz(hmdtn)4的条件下进行苄胺的光催化氧化实验，考察中心金属对含硫氮杂金属卟啉的催化活性的影响。催化剂为CoPz(hmdtn)4记为Entry 1；催化剂为MgPz(hmdtn)4记为Entry 2；催化剂为ZnPz(hmdtn)4记为Entry 3。
实验结果如表3示。对比实验表明，在相同的条件下，苄胺在ZnPz(hmdtn)4光催化体系中光反应3h，其转化率为45％，氧化产物N-苄烯丁胺的选择性为86％；苄胺在MgPz(hmdtn)4光催化体系中光反应3h，其转化率为59％，氧化产物N-苄烯丁胺的选择性为89％；而苄胺在CoPz(hmdtn)4光催化体系中的转化率达到了90％，显著高于在MgPz(hmdtn)4和ZnPz(hmdtn)4光催化体系中的转化率，同时，与MgPz(hmdtn)4和ZnPz(hmdtn)4光催化体系相比，氧化产物N-苄烯丁胺在CoPz(hmdtn)4光催化体系中的选择性也提高了10％左右。
表3.中心金属对催化活性的影响.
实施例4：胺类化合物的拓展
按照实施例1的操作步骤，改变反应底物，将底物拓展到其它的伯胺和仲胺。Entry1至Entry 9为伯胺；Entry 10和Entry 11为仲胺。
实验结果如表4所示。对比实验表明，在苄胺的苯环上引入给电子基团(CH3、C(CH3)3和OCH3)和吸电子基团(F和Cl)，这类胺都具有高的转化率，且相应氧化产物亚胺也具有高的选择性(Entry 2至Entry 6)。同时，取代基的性质显著影响底物胺的转化率，实验结果表明苯环上具有给电子基团的胺具有较高的转化率(Entry 2至Entry 4)，而苯环上具有吸电子基团的胺具有较低的转化率(Entry 5和Entry 6)，说明在反应中存在电子效应。当苯环上的取代基在邻位和对位时，底物胺也具有不同的转化率，当取代基在对位时，胺具有高的转化率(Entry 6和Entry 7)；与双取代的苄胺相比，单取代的苄胺具有高的转化率，表明在反应中存在位阻效应(Entry 6至Entry 8)。除此之外，杂环胺糠胺也可以发生有效转化，具有高的转化率，但是相应氧化产物亚胺的选择性比较低(Entry 9)。
具有对称结构的仲胺也可以发生有效转化，不仅胺具有高的转化率，而且相应氧化产物亚胺也具有高的选择性(Entry 10和Entry 11)。
表4.CoPz(hmdtn)4可见光催化氧化各种胺类化合物.
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (1)
1.一种可见光催化氧化胺类化合物合成亚胺类化合物的方法，其特征在于，所述方法以四羟甲基四(1，4-二噻英)四氮杂钴卟啉为催化剂，以分子氧为氧化剂，在λ≥420nm的可见光照射下实现胺类化合物氧化为相应的亚胺类化合物；
所述四羟甲基四(1，4-二噻英)四氮杂钴卟啉的分子结构式为：
所述方法的具体步骤为：在石英夹套光反应瓶中加入一定量的四羟甲基四(1，4-二噻英)四氮杂钴卟啉和溶剂，在搅拌的作用下使四羟甲基四(1，4-二噻英)四氮杂钴卟啉在溶剂中完全溶解，再向体系中加入胺类化合物，并在无光照的条件下继续搅拌2-4h；然后在1-4atm氧气和λ≥420nm的可见光照射的条件下反应一定时间即可；
所述溶剂为乙腈或二甲亚砜；
所述胺类化合物为
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810136237.0A CN108299138B (zh) | 2018-02-09 | 2018-02-09 | 一种可见光催化氧化胺类化合物合成亚胺类化合物的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810136237.0A CN108299138B (zh) | 2018-02-09 | 2018-02-09 | 一种可见光催化氧化胺类化合物合成亚胺类化合物的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108299138A CN108299138A (zh) | 2018-07-20 |
| CN108299138B true CN108299138B (zh) | 2020-11-13 |
Family
ID=62865062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810136237.0A Active CN108299138B (zh) | 2018-02-09 | 2018-02-09 | 一种可见光催化氧化胺类化合物合成亚胺类化合物的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108299138B (zh) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106975510A (zh) * | 2017-04-21 | 2017-07-25 | 中南民族大学 | 一种高可见光活性石墨相氮化碳及其应用 |
-
2018
- 2018-02-09 CN CN201810136237.0A patent/CN108299138B/zh active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106975510A (zh) * | 2017-04-21 | 2017-07-25 | 中南民族大学 | 一种高可见光活性石墨相氮化碳及其应用 |
Non-Patent Citations (4)
| Title |
|---|
| A Robust Palladium(II)–Porphyrin Complex as Catalyst for Visible Light Induced Oxidative C-H Functionalization;Wai-Pong To等;《Chem. Eur. J.》;20130305;第19卷;第5654-5664页 * |
| Highly Efficient Oxidation of Amines to Imines by Singlet Oxygen and Its Application in Ugi-Type Reactions;Gaoxi Jiang等;《Org. Lett.》;20190921;第11卷(第20期);第4568-4571页 * |
| 四轻甲基四 1,4 -二噻英四氮杂卟啉锌的合成、表征与性能;邓克俭等;《中南民族大学学报（自然科学版）》;20100630;第29卷(第2期);第15-17,34页 * |
| 负载型金属含硫氮杂卟啉光催化氧化苄胺的性能研究;金娟娟等;《中国化学会第四届卟啉与酞菁学术研讨会》;20171231;第89页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108299138A (zh) | 2018-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Direct evidence of charge separation in a metal–organic framework: efficient and selective photocatalytic oxidative coupling of amines via charge and energy transfer | |
| Li et al. | Simultaneous oxidation of alcohols and hydrogen evolution in a hybrid system under visible light irradiation | |
| Bu et al. | Merging visible-light photoredox and micellar catalysis: arylation reactions with anilines nitrosated in situ | |
| Lang et al. | Visible‐Light‐Induced Selective Photocatalytic Aerobic Oxidation of Amines into Imines on TiO2 | |
| Yan et al. | Eosin Y as a redox catalyst and photosensitizer for sequential benzylic C− H amination and oxidation | |
| Deng et al. | Visible-light-driven selective cleavage of CC bonds in lignin model substrates using carbon nitride-supported ruthenium single-atom catalyst | |
| Aresta et al. | An integrated photocatalytic/enzymatic system for the reduction of CO2 to methanol in bioglycerol–water | |
| Jin et al. | Selective oxidation of amines using O2 catalyzed by cobalt thioporphyrazine under visible light | |
| Yin et al. | A noble-metal-free photocatalytic hydrogen production system based on cobalt (III) complex and eosin Y-sensitized TiO 2 | |
| Badamali et al. | Microwave assisted oxidation of a lignin model phenolic monomer using Co (salen)/SBA-15 | |
| Hosseini-Sarvari et al. | Alizarin red S–TiO 2-catalyzed cascade C (sp 3)–H to C (sp 2)–H bond formation/cyclization reactions toward tetrahydroquinoline derivatives under visible light irradiation | |
| Melone et al. | Sunlight Induced Oxidative Photoactivation of N‐Hydroxyphthalimide Mediated by Naphthalene Imides | |
| Liu et al. | Visible-light-driven self-coupling and oxidative dehydrogenation of amines to imines via a Mn (II)-based coordination polymer | |
| Molinari et al. | Phororedox and photocatalytic processes on Fe (III)–porphyrin surface modified nanocrystalline TiO2 | |
| Hosseini-Sarvari et al. | Visible-light assisted of nano Ni/g-C3N4 with efficient photocatalytic activity and stability for selective aerobic C− H activation and epoxidation | |
| Ma et al. | Synthetic approaches for CN bonds by TiO2 photocatalysis | |
| Huang et al. | Metal-free coordination of porphyrin-based porous organic polymers for efficient photocatalytic oxidative coupling of amines under visible light | |
| Wei et al. | Highly selective photocatalytic oxidation of alcohols under the application of novel metal organic frameworks (MOFs) based catalytic system | |
| Jia et al. | Switchable ROS species regulation facilitates the selective oxidation of benzyl alcohols enabled by an organic photocatalyst | |
| Han et al. | Visible Light Induced Selective Aerobic Formation of N‐benzylidene Benzylamine over 2‐aminoterephthalic Acid Sensitized {110}‐Facetted BiOCl Nanosheets | |
| Zhou et al. | Manganese porphyrin immobilized on montmorillonite: a highly efficient and reusable catalyst for the aerobic epoxidation of olefins under ambient conditions | |
| Sabaghi et al. | Fabrication of a new heterogeneous tungstate-based on the amino-functionalized metal-organic framework as an efficient catalyst towards sonochemical oxidation of alcohols under green condition | |
| Guo et al. | Heterogeneous visible-light promoted dehydrogenative [4+ 2] annulation of benzothioamides and alkynes under aerobic conditions | |
| Feng et al. | Donor–acceptor covalent organic framework promotes visible light-induced oxidative coupling of amines to imines in air | |
| CN113546683B (zh) | 基于卟啉的共价有机框架材料在光催化氧化环化反应中的应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |