Preparation method of Cis-ruthenium-salen N-heterocyclic carbene

A technology of nitrogen heterocyclic carbene and nitrogen protection, which is applied in the direction of chemical instruments and methods, ruthenium organic compounds, compounds containing elements of group 8/9/10/18 of the periodic table, etc., and can solve the problem of low yield and synthetic method Complicated problems, to achieve the effect of increasing productivity

Active Publication Date: 2021-02-02
JIANGSU OPEN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] The technical problem solved: for above-mentioned existing need 300W incandescent lamp carries out photolysis decarbonylation to cis-ruthenium-salen biscarbonyl compound, then reacts with carbene source to obtain cis-ruthenium-salen carbene, this synthetic method is comparatively complicated, and yield is low High technical problem, in order to solve this problem, the present invention has developed a kind of novel method for synthesizing cis-ruthenium-salen nitrogen heterocyclic carbene

Method used

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  • Preparation method of Cis-ruthenium-salen N-heterocyclic carbene

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Embodiment 1

[0034] A kind of preparation method of Cis-ruthenium-salen nitrogen heterocyclic carbene, the synthetic steps are as follows:

[0035] (1) Synthesis of Precursor A

[0036] Precursor A was synthesized according to the method disclosed in J.Am.Chem.Soc.2009, 131, 4405-4417, and the yield was 35%.

[0037]

[0038] (2) Synthesis of cis-ruthenium-salen azacyclic carbene Ru-1

[0039] Under nitrogen protection, add cis-ruthenium-salen biscarbonyl complex precursor A (1mmol, 702mg), silver oxide (4mmol, 920mg), 1,3-dimethyl-1H-benzo Imidazolium-3-onium iodide (2mmol, 546mg), 100ml dehydrated tetrahydrofuran, after the addition of reactants, react at 50°C for 8h, then cool down to room temperature, remove the solvent by rotary evaporation, and separate and purify through silica gel chromatography to obtain an orange powder compound Ru-1, the yield was 79%.

[0040]

[0041] Ru-1: 1 H NMR (CDCl 3 ,300Hz)δ8.30(s,1H),7.78(s,1H),7.36(d,J=2.7Hz,1H),7.11(br,4H),7.02(d,J=2.6Hz,1...

Embodiment 2

[0043] The synthesis steps of the cis-ruthenium-salen azacyclic carbene Ru-4 of the present embodiment are as follows:

[0044] (1) Synthesis of Precursor B

[0045] Precursor B was synthesized according to the method disclosed in J.Am.Chem.Soc.2009, 131, 4405-4417, and the yield was 41%.

[0046]

[0047] B: 1 H NMR (CDCl 3 ,400Hz)δ8.08(s,1H),7.52(s,1H),7.39-7.34(m,3H),7.27-7.24(m,1H),7.16-7.15(m,2H),7.11(d, J=2.6Hz, 1H), 6.88(d, J=7.7Hz, 1H), 6.85(d, J=2.7Hz, 1H), 6.77-6.75(m, 1H), 2.15(s, 3H), 1.92( s,3H);IR 2065,1992cm -1 (υ(CO)); FAB-MSm / z 713[M] +

[0048] (2) Synthesis of cis-ruthenium-salen azacyclic carbene Ru-4

[0049]Under nitrogen protection, add the precursor Bcis-ruthenium-salen biscarbonyl complex (1mmol, 713mg), silver oxide (4mmol, 920mg), 1-ethyl-3-methylimidazolium iodide into a 100mL three-necked flask (2mmol, 476mg), 100ml dehydrated tetrahydrofuran, after the addition of the reactants is completed, react at 50°C for 8h, then cool down to room ...

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Abstract

The invention discloses a preparation method of Cis-ruthenium-salen N-heterocyclic carbene. The preparation method comprises the following steps: adding 1 mmol of dodecacarbonyl triruthenium, 1 mmol of salen ligand and 10 ml of 1, 2, 4-trichlorobenzene into a reaction flask under the protection of nitrogen, heating to 185 DEG C, reacting for 6 hours, cooling to room temperature, and separating andpurifying by a silica gel chromatographic column to obtain a cis-ruthenium-salen dicarbonyl complex; the method comprises the following steps: adding 1 mmol of a cis-ruthenium-salen dicarbonyl complex, 4 mmol of silver oxide, 2 mmol of an N-heterocyclic carbene precursor and 100 ml of dehydrated tetrahydrofuran into a reaction flask under the protection of nitrogen, reacting at 50 DEG C for 8 h after the reactants are added, cooling to room temperature, and separating and purifying by a silica gel chromatographic column to obtain the cis-ruthenium-salen N-heterocyclic carbene complex. The preparation method is performed under mild conditions without light, and a series of novel cis-ruthenium-salen N-heterocyclic carbenes are obtained at an excellent reaction yield of 61%-79%.

Description

technical field [0001] The invention belongs to the field of organic chemical synthesis, and in particular relates to a preparation method of Cis-ruthenium-salen nitrogen heterocyclic carbene. Background technique [0002] In recent years, cis-ruthenium-salen biscarbonyl compounds have shown excellent performance in the field of asymmetric catalysis. The carbene complexes of cis-ruthenium-salen are widely considered as intermediates of such catalytic reactions, and the synthesis of such intermediates is of great significance for deepening people's understanding of such catalytic reactions and further designing and optimizing catalysts. [0003] At present, the literature reports of this kind of cis-ruthenium-salen carbene compound are very rare. The only synthesis case is to use a 300W incandescent lamp to decarbonylate the cis-ruthenium-salen biscarbonyl compound, and then react with the carbene source to obtain cis-ruthenium-salen salen carbene, this synthetic method is r...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00
CPCC07F15/0046
Inventor 陈大庆
Owner JIANGSU OPEN UNIV
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