Metallohematoporphyrin diether diester compound, catalyst and preparation method thereof, and cyclohexane catalytic oxidation method
A porphyrin double ether, catalytic oxidation technology, applied in the preparation of carbon-based compounds, the preparation of organic compounds, organic compounds/hydrides/coordination complex catalysts and other directions, can solve the problem of high catalytic cost, low catalytic efficiency, and catalyst dosage. Large and other problems, to achieve the effect of high catalytic efficiency, small dosage, and improved selectivity
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[0044] The third aspect of the present invention provides a kind of preparation method of above-mentioned catalyst, comprises the following steps:
[0045] After hemin and saturated hydrogen bromide glacial acetic acid solution are mixed and reacted for a predetermined period of time, an alcohol with 6 to 21 carbon atoms, preferably a straight chain or branched chain fatty alcohol, is added and reacted under ultrasonic vibration conditions to obtain the structural formula: Compound shown in formula II. The reaction temperature is preferably normal temperature, such as 20°C to 30°C, and the predetermined time is preferably 12 hours to 24 hours.
[0046]
[0047] Reacting Fe salt, Co salt and / or Ni salt with the compound represented by formula II in a solvent at a temperature of 130° C. to 150° C. to obtain the metallohaematoporphyrin diether diester compound. The reaction time may preferably be 3 to 5 hours, and the solvent may be, for example, dimethylformamide (DMF). The...
Embodiment 1
[0067] 300g of cyclohexane was added to the reactor, and then the metallohaematoporphyrin diether diester compound a (see Table 1) with a mass concentration of 1.0ppm was added, and the reactor was sealed. Feed nitrogen to replace, and when the oxygen content in the tail gas is lower than 0.5%, close the tail gas valve, continue to feed nitrogen, make the pressure in the still reach 0.2MPa, and seal the reaction kettle. Turn on the heating system and stir, heat the reaction system to 110°C, then feed air, open the tail gas valve, make the reaction system pressure reach 0.65MPa, and start timing. After reaction advances 50min, stop feeding air, cooling down, reaction system is analyzed, catalytic oxidation analysis result is as shown in table 2.
Embodiment 2-9
[0069] The difference of embodiment 2-9 and the hexanaphthene catalytic oxidation method of embodiment 1 is that the central metal atom M and alkyl R of the catalyst b-i adopted in embodiment 2-9 are different from the catalyst (a ). The catalytic oxidation analysis results of Examples 2-9 are shown in Table 2.
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