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Linked disulfide group substituted deuteroporphyrin, metal complexes, preparation method and uses thereof

A metal complex and hypoporphyrin technology is applied in the preparation and application of metallohypoporphyrin compounds, and can solve the problems of few studies on metallohypoporphyrin derivatives, poor catalyst selectivity, and low cyclohexane conversion rate. , to achieve the effect of short oxidation reaction time, less catalyst dosage, and improved selectivity of alcohols and ketones

Inactive Publication Date: 2009-11-25
NANJING UNIV OF SCI & TECH
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  • Abstract
  • Description
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Problems solved by technology

The above-mentioned methods utilize different metalloporphyrins and derivatives thereof as catalysts, the reaction time is longer (>10h), the catalyst selectivity is poor, and the conversion rate of cyclohexane is lower (the highest value is 12%), which easily leads to the formation of deep Oxidation product, difficult to industrialize
[0004] However, most of the metalloporphyrin compounds currently used to study the catalytic performance of cyclohexane oxidation are based on artificially synthesized metallotetraphenylporphyrins, while semi-synthetic metallohypoporphyrin derivatives based on hemin very little research

Method used

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  • Linked disulfide group substituted deuteroporphyrin, metal complexes, preparation method and uses thereof
  • Linked disulfide group substituted deuteroporphyrin, metal complexes, preparation method and uses thereof
  • Linked disulfide group substituted deuteroporphyrin, metal complexes, preparation method and uses thereof

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preparation example Construction

[0028] combine figure 1 , the preparation method of dithio-substituted hypoporphyrin of the present invention, comprises the following steps:

[0029] In the first step, slowly add thionyl chloride dropwise to a reactor containing anhydrous methanol under ice-bath conditions, and then add cystine powder in batches to the reactor. After the addition, react overnight at room temperature, distill off methanol and excess thionyl chloride to obtain a white cystine hydrochloride solid. Wherein, the molar ratio of thionyl chloride to cystine is 3:1-8:1.

[0030] In the second step, add hypoporphyrin, cystine methyl ester hydrochloride, dicyclohexylcarbodiimide (DCC), N, N-dimethylformamide (DMF) in the reactor, and then drop pyridine As a catalyst, stir the reaction at room temperature, the reaction time is 8 ~ 24h. After completion, 200 mL of saturated NaCl aqueous solution was added, and the aqueous layer was extracted with dichloromethane; after drying and recrystallization, a ...

Embodiment 1

[0035]Example 1: In the first step, 5 mL of thionyl chloride was slowly added dropwise to a three-necked flask containing 100 mL of anhydrous methanol under ice-bath conditions, and then 2.0 g of cystine powder was added in batches to the three-necked flask. After the addition, react overnight at room temperature, distill methanol and excess thionyl chloride to obtain 2.48g of white cystine hydrochloride solid with a yield of 98%; in the second step, add 0.3g of cystine hydrochloride to a three-necked flask Hypoporphyrin, 0.18g cystine methyl ester hydrochloride, 0.34g dicyclohexylcarbodiimide (DCC), 80mL N, N-dimethylformamide (DMF), then dropwise added 1.5mL pyridine as a catalyst, The reaction was stirred at room temperature for 8.0 h. After completion, 200 mL of saturated NaCl aqueous solution was added, and the aqueous layer was extracted with dichloromethane. After drying and recrystallization, 0.16 g of reddish-brown powdery dithio-substituted hypoporphyrin solid was ob...

Embodiment 2

[0036] Embodiment 2: The other steps are the same as in Example 1. In the first step, under ice bath conditions, slowly add 5 mL of thionyl chloride dropwise to a three-necked flask with 100 mL of anhydrous methanol, and then add in batches to the three-necked flask Cystine powder 3.5g. After the addition, react overnight at room temperature, distill off methanol and excess thionyl chloride to obtain 4.3 g of white cystine hydrochloride solid with a yield of 97%.

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Abstract

The present invention discloses a linked disulfide group substituted deuteroporphyrin, metal complexes, preparation method and uses thereof, wherein linked disulfide group substituted deuteroporphyrin and metal complexes thereof, first using thionyl chloride and cystineto prepare cystine methyl ester hydrochloride solid; then using deuteroporphyrin, cystine methyl ester hydrochloride, dicyclohexylcarbodiimide DCC and N, N-dimethylformamide DMF to prepare linked disulfide group substituted deuteroporphyrin in the presence of catalyst pyridine. Then dissolving the linked disulfide group substituted deuteroporphyrin solid in chloroform, adding metal salts and proceeding refluxing reaction to get the linked disulfide group substituted deuteroporphyrin metal complexes. The invention provided linked disulfide group substituted deuteroporphyrin and metal complexes thereof are novel compounds capable of improving catalyst activity and selectivity, shorting reaction time, improving cyclohexane transformation ratio and selectivity of the cyclohexanone (cyclohexanol) in products.

Description

technical field [0001] The invention belongs to the preparation and application technology of a class of metal hypoporphyrin compounds, in particular to a bidisulfide-substituted hypoporphyrin and its metal complex, preparation method and application. Background technique [0002] Porphyrin and its derivatives have many unique properties. In addition to being used in many fields such as semiconductors, superconductors, special functional polymer materials, and photosensitive anticancer drug intermediates, one of its most important uses is widely used as an analog Biological enzyme catalysts catalyze the oxidation of various hydrocarbon compounds. [0003] Using oxygen (or air) as an oxygen source to directly catalyze the oxidation of cyclohexane to synthesize cyclohexanone is the current development trend and research focus of cyclohexanone synthesis technology. In this field, metalloporphyrin is a kind of catalyst with very good effect. CN1269343, CN1405131, CN1530357 disc...

Claims

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Application Information

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IPC IPC(8): C07D513/22B01J31/22C07C49/403C07C35/08C07C27/12C07C45/33C07C29/50
Inventor 胡炳成周维友刘祖亮姚其正徐士超
Owner NANJING UNIV OF SCI & TECH
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