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A kind of calixarene derivative and its metal complex as well as their preparation method and application

A technology of metal complexes and derivatives, which is applied in the preparation of organic compounds, preparation of aminohydroxyl compounds, organic compound/hydride/coordination complex catalysts, etc., can solve the problem that aromatics have not been found and reported, and achieve high conversion rate , mild reaction conditions, simple operation

Active Publication Date: 2011-12-14
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0014] However, quaternary ammonium calix[4]arenes have not been reported

Method used

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  • A kind of calixarene derivative and its metal complex as well as their preparation method and application
  • A kind of calixarene derivative and its metal complex as well as their preparation method and application
  • A kind of calixarene derivative and its metal complex as well as their preparation method and application

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0047] Embodiment one: preparation [H 4 L](PF 6 ) 4 (where H 4 L=5,11,17,23-tetrakis (trimethylquaternary ammonium salt) calix [4] arene) method comprises the following steps:

[0048] [1] Preparation of p-benzoic acid diazonium chloride salt solution:

[0049] Dissolve 1.37g (10mmol) of p-aminobenzoic acid in 10mL of 5% (mass fraction) sodium hydroxide solution, add 0.69g (10mmol) of sodium nitrite after cooling to room temperature, and continue stirring for 30 minutes, then put the above solution in Slowly add dropwise to the mixture of 3.67mL concentrated hydrochloric acid and 2.5mL distilled water while stirring, keep the temperature at 0-5°C, stir for 30 minutes after the dropwise addition is completed, a large amount of white precipitate is found, dissolve after adding 4mL distilled water .

[0050] [2] Preparation of calix[4]arenes

[0051] Calix[4]arene Reference Synthesis: Gutsche, C.D.; Levine, J.A.; Sujeeth, P.K. J. Org. Chem .1985, 50 ,5802.

[0052] [3] ...

Embodiment 2

[0073] [1] see image 3 , to prepare the calix[4]arene Mn(III) superoxide complex [Mn(III)L(O 2 )(H 2 O)](PF 6 ) 2

[0074] 2mlMn(OAc) 2 4H 2 O (98mg, 0.4mmol) methanol solution was slowly added dropwise to 6ml [H 4 L](PF 6 ) 4 (where H 4 L = 5,11,17,23-tetra(trimethylquaternary ammonium salt) calix[4]arene) (123mg, 0.1mmol) in acetonitrile solution, the mixed solution was stirred in an open air system for 3 hours, filtered, Diethyl ether was added to the filtrate to diffuse at room temperature for 1 week, and dark purple rhombic crystals appeared, filtered, washed with ether, and dried to obtain the target product [Mn(III)L(O 2 )(H 2 O)](PF 6 ) 2 , the quaternary ammonium-containing calix [4] arene metal complex [Mn (III) L (O 2 )(H 2 O)](PF 6 ) 2 The schematic diagram of the cation structure is attached Figure 4 shown.

[0075] [2] The product was characterized by infrared and X-ray single crystal diffraction.

[0076] The specific results are as follows:...

Embodiment 3

[0083] At 20°C, olefin (0.88 mmol), isobutyraldehyde (1.76 mmol), catalyst [Mn(III)L(O 2 )(H 2 O)](PF 6 ) 2 (1.76 × 10 -3 mmol) of 2 mL MeCN solution was added to a 10 mL round bottom flask. After the mixture was stirred for 5 hours under the condition of bubbling oxygen, the bubbling of oxygen was stopped and filtered. Various components in the mixed solution were analyzed by gas chromatography-mass chromatography (GC-MS) test and internal standard comparison. The epoxidized products were further identified by gas chromatography (GC) retention times and internal standards.

[0084] The selection of the olefins is shown in the substrate column in the table below, and the products obtained and the corresponding selectivity are shown in the table below:

[0085]

[0086] As can be seen from the above table: it can be seen that the calix [4] arene Mn (III) superoxide complex [Mn (III) L (O 2 )(H 2 O)](PF 6 ) 2 It can be used to catalyze the epoxidation reaction of o...

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Abstract

The invention relates to a calixarene derivative and a metal complex thereof, and a preparation method and application of the calixarene derivative and the metal complex thereof. The calixarene derivative is quaternary ammonium salt calix [4] arene [H4L](PF6)4, wherein H4L is 5,11,17,23-tetra(trimethyl quaternary ammonium salt) calix [4] arene; and the metal complex containing the quaternary ammonium salt calix [4] arene is [Mn(III)L(O2)(H2O)](PF6)2. The calixarene derivative [H4L](PF6)4 disclosed by the invention not only can be used for separation, phase-transfer catalysis, molecule exchange and the like of neutral organic matters but also can be used for reacting with metal salts to generate the metal complex so that the calixarene derivative is applied more widely. The Calix [4] arene Mn(III) super-oxygen complex [Mn(III)L(O2)(H2O)](PF6)2 can be used for epoxidation for catalyzing olefin. The reaction condition is moderate. The conversion rate is higher; furthermore, the selectivity is exclusive.

Description

technical field [0001] The invention relates to a calixarene derivative and a metal complex thereof, a preparation method and an application thereof, in particular to 5,11,17,23-tetra(trimethylquaternary ammonium salt) calix[4]arene and its combination with hexafluorophosphoric acid Complexes of metal manganese, and their preparation and catalytic applications. Background technique [0002] In recent years, due to the unique "cavity" structure of calixarene, it has attracted widespread attention, and a large number of calixarene derivatives have been synthesized successively. Therefore, calixarene derivatives are widely used in molecular recognition, biological enzyme simulation, material recognition and Separation aspects as well as functionalized materials show broad application potential. [0003] In the prior art, reports about calixarene include: [0004] (1) The Chinese invention with the patent number 200510134614.X discloses a novel compound that can be used as a f...

Claims

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Application Information

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IPC IPC(8): C07C215/90C07C213/00C07F13/00B01J31/22C07D303/04C07D301/06
Inventor 郎建平刘雷雷万黎敏任志刚王会芳丁红叶
Owner SUZHOU UNIV
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