Fluorescent labeled organic boron/nitrogen Lewis acid and base bifunctional catalyst and preparation method thereof

A dual-functional catalyst, acid-base dual-functional technology, applied in organic chemical methods, preparation of organic compounds, organic compound/hydride/coordination complex catalysts, etc., can solve the problem of no catalytic activity, expensive raw materials, single method, etc. problem, to achieve good non-enantiomeric selectivity

Active Publication Date: 2017-06-20
HUNAN UNIV
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  • Description
  • Claims
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Problems solved by technology

Ionic organoquinoline boron compounds have high fluorescence quantum efficiency and stability, and have attracted attention in the fields of analytical chemistry and materials chemistry [Chin.J.Org.Chem.2016, 36, 987; Dalton Trans., 2012, 41, 2131; Macromolecules 2012, 45, 3078; Energy Sources, Part A, 2011, 33, 1035; Inorg.Chem.2009, 48, 10466; J.Am.Chem.Soc.2009, 131, 3476; Macromolecules.2007, 40, 6; J.Am.Chem.Soc.2004,126,7015; Macromolecules.2006,39,9041.J.Am.Chem.Soc.2004,126,7015;Appl.Phys.Lett.2001,78,2300;Chem. Mater.2000,12,79; Antimicrob.AgentsChemother.1980,17,549; Chem.Ber.1969,102,4025]. However, it has never been reported that the bifunctional catalyst based on fluorescent labeling is used in synthetic chemistry
Moreover, the method for synthesizing this type of compound is single, mainly utilizing quinoline derivatives and triphenylboron to heat and reflux reaction, but this type of method has expensive raw materials, single product structure, low yield, and no catalytic activity; making the use of ionic organic The application of quinoline boron / nitrogen fluorescent compounds as acid-base bifunctional catalysts in organic synthesis has not been reported

Method used

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  • Fluorescent labeled organic boron/nitrogen Lewis acid and base bifunctional catalyst and preparation method thereof
  • Fluorescent labeled organic boron/nitrogen Lewis acid and base bifunctional catalyst and preparation method thereof
  • Fluorescent labeled organic boron/nitrogen Lewis acid and base bifunctional catalyst and preparation method thereof

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preparation example 1

[0027] Add 0.1 mmol I (wherein R f = CF 3 ; 3 , R 4 , R 5 =H), 0.2mmol II (wherein R 1 , R 2 , R 6 = H), 0.005 mmol I 2 and 1mL toluene, under a nitrogen atmosphere, the reaction was carried out at 150°C for 12h. After the reaction was completed, it was filtered, concentrated, and separated by column chromatography to obtain III (wherein R f = CF 3 ; 1 , R 2 , R 3 , R 4 , R 5 , R 6 =H), the productive rate is 96%. Detection of catalytic activity: add 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein R f = CF 3 ; 1 , R 2 , R 3 , R 4 , R 5 , R 6 =H) and 1mL toluene, the reaction was carried out at 25°C for 12h, and TLC followed the reaction until the reaction was complete. The reaction result was: 2-anilinobenzylcyclohexanone, the productive rate was 78%, and the cis-trans selectivity was 1 / 99.

preparation example 2

[0029] Add 0.1 mmol I (wherein R f =C 2 f 5 ; 3 , R 4 , R 5 =H), 0.2mmol II (wherein R 1 = H, R 2 , R 6 = H), 0.005 mmol I 2 and 1mL toluene, under a nitrogen atmosphere, the reaction was carried out at 150°C for 12h. After the reaction was completed, it was filtered, concentrated, and separated by column chromatography to obtain III (wherein R f =C 2 f 5 ; 1 , R 2 , R 3 , R 4 , R 5 , R 6=H) yield is 73%. Detection of catalytic activity: add 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein R f = CF 3 ; 1 , R 2 , R 3 , R 4 , R 5 , R 6 =H) and 1mL toluene, the reaction was carried out at 25°C for 12h, and TLC followed the reaction until the reaction was complete. The reaction result was: 2-anilinobenzylcyclohexanone, the productive rate was 83%, and the cis-trans selectivity was 1 / 99.

preparation example 3

[0031] Add 0.1 mmol I (wherein R f = CF 3 ; 3 , R 4 , R 5 =H), 0.2mmol II (wherein R 1 , R 6 = H; R 2 =OMe), 0.005mmol I 2 and 1mL toluene, under a nitrogen atmosphere, the reaction was carried out at 150°C for 12h. After the reaction was completed, it was filtered, concentrated, and separated by column chromatography to obtain III (wherein R f = CF 3 ; 2 =OMe;R 1 , R 3 , R 4 , R 5 , R 6 =H), the productive rate is 60%. Detection of catalytic activity: add 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein R f = CF 3 ; 2 =OMe;R 1 , R 3 , R 4 , R 5 , R 6 =H) and 1mLtoluene, the reaction was carried out at 25°C for 12h, TLC followed the reaction until the reaction was complete. The reaction result was: 2-anilinobenzylcyclohexanone, the yield was 83%, and the cis-trans selectivity was 1 / 99 .

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Abstract

The invention relates to a fluorescent labeled organic boron/nitrogen Lewis acid and base bifunctional catalyst and a preparation method thereof. The catalyst is characterized by being prepared by the following step: by taking a quinoline amide compound and a cheap sodium tetraphenylborate derivative as raw materials, cheap and easily available single element iodine as a catalyst and a common organic solvent as a reaction solvent, performing a reaction for a while at a certain temperature to obtain the bifunctional organic boron/nitrogen Lewis acid and base catalyst with a high yield and high selectivity. The catalyst is good in stability and recyclable, and has very good diastereoselectivity in a Mannich reaction. The method has the advantage s of being relatively low in cost, high in yield, simple and convenient to operate, pollution-free and the like, and has certain feasibility for realizing industrial production.

Description

[0001] 【Technical field】 [0002] The invention belongs to the field of catalytic organic synthesis, and in particular relates to a novel quinoline ion organic boron nitrogen Lewis acid catalyst and a preparation method thereof. [0003] 【Background technique】 [0004] Organic Lewis acid-base bifunctional catalysts have been widely used in organic synthesis due to their high regio- and stereoselectivity due to their synergistic activation of nucleophiles and electrophiles. However, compared with metal catalysts, organic catalysts have lower catalytic activity due to their inherent physical and chemical properties similar to organic synthesis reaction products, so usually the addition amount reaches 5-10mol%, resulting in more catalyst residues, but relative to the product , how to quickly detect this low concentration of catalyst residues (<1mol%) through spectroscopy is a problem, especially for medicinal chemistry, the strict requirement that the mono-heterogeneity should ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/14C07C221/00C07C225/18C07F5/02C09K11/06
CPCB01J31/146B01J2231/4283C07B2200/07C07C221/00C07F5/02C09K11/06C09K2211/1029C07C225/18
Inventor 邱仁华曹鑫阳天宝
Owner HUNAN UNIV
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