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Cyclic phosphamide derivative with biaryl skeleton and synthesis method and application thereof

A cyclic phosphoramide and a synthesis method technology, applied in the field of synthesis, cyclic phosphoramide derivatives, can solve the problems of increasing economic cost, waste of resources and manpower, harsh reaction conditions, etc., to avoid waste, less pollution, and reaction cycle. short effect

Pending Publication Date: 2022-01-28
NANYANG NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the reported methods have very obvious defects: the use of transition metals requires cumbersome steps in the follow-up impurity removal process on the one hand, resulting in waste of resources and manpower; on the other hand, the reaction conditions are harsh (high temperature, long reaction time), and the environment It is more harmful; the use of equivalent oxidant produces a large amount of waste, resulting in unnecessary waste of raw materials and increasing economic costs

Method used

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  • Cyclic phosphamide derivative with biaryl skeleton and synthesis method and application thereof
  • Cyclic phosphamide derivative with biaryl skeleton and synthesis method and application thereof
  • Cyclic phosphamide derivative with biaryl skeleton and synthesis method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] A kind of synthetic method of 6-phenyl-5 benzyl-5H-dibenzo[c,e][1,2]-6-oxaphosphonamide (2a), comprising the following steps: adding Phosphoramide 0.2mmol (77mg), n-butylammonium bromide (0.5mmol), 5mL acetonitrile / methanol mixed solution, put graphite electrodes and platinum electrodes into the reaction device, connect the power supply and feed 10mA constant current, and react at room temperature After 6 hours, it was concentrated under reduced pressure and subjected to column chromatography to obtain 72 mg of a white solid with a yield of 93% and a purity of 99.9%. 1 H NMR (400MHz, CDCl 3)δ8.20–7.97(m,2H),7.84-7.75(m,1H),7.74-7.60(m,3H),7.51-7.40(m,2H),7.39–7.30(m,2H),7.31– 7.11(m,6H),7.10–7.03(m,1H),7.02–6.96(m,1H),5.18(dd,J=16.8,6.8Hz,1H),4.72(dd,J=16.8,7.5Hz, 1H); 13 C{ 1 H}NMR (100MHz, CDCl 3 )δ139.7, 137.1 (d, J = 5.5Hz), 136.7 (d, J = 3.3Hz), 132.5 (d, J = 2.1Hz), 132.1 (d, J = 2.4Hz), 131.7, 131.6, 131.0 (d ,J=10.3Hz),129.8,128.6,128.5,128.5,127.6,127.5,12...

Embodiment 2

[0030] A method for synthesizing 4-methyl-6-phenyl-5-benzyl-5H-dibenzo[c,e][1,2]-6-oxaphosphonamide (2b), comprising the following steps:

[0031] Add phosphoramide 0.2mmol (81mg), n-butylammonium bromide (0.5mmol), 5mL acetonitrile / methanol mixed solution into the reaction vessel at one time, insert graphite electrode and platinum sheet electrode into the reaction device, connect the power supply and feed 10mA constant current, reaction at room temperature for 6h, concentration under reduced pressure, and column chromatography (200-300 mesh silica gel, petroleum ether / ethyl acetate = 2 / 1-5 / 1) to obtain 74 mg of white solid with a yield of 91%. 99.9% pure. 1 H NMR (400MHz, CDCl 3 )δ8.00–7.89(m,1H),7.88-7.78(m,1H),7.77–7.65(m,1H),7.65–7.47(m,3H),7.40–7.22(m,4H),7.23– 7.16(m,2H),7.13–7.03(m,3H),6.87–6.59(m,2H),5.09(dd,J=16.7,7.2Hz,1H),4.62(dd,J=16.8,7.4Hz, 1H), 2.14(s,3H); 13 C NMR (100MHz, CDCl 3 )δ156.31, 155.08, 142.44, 131.70, 130.23, 129.71, 128.25, 127.86, 127.27, 126...

Embodiment 3

[0034] A method for synthesizing 4,6-diphenyl-5-benzyl-5H-dibenzo[c,e][1,2]-6-oxaphosphonamide (2c), comprising the following steps:

[0035] Add phosphoramide 0.2mmol (78mg), n-butylammonium bromide (0.5mmol), 5mL acetonitrile / methanol mixed solution into the reaction vessel at one time, insert graphite electrode and platinum sheet electrode into the reaction device, connect the power supply and feed 10mA constant current, reaction at room temperature for 6h, concentration under reduced pressure, and column chromatography (200-300 mesh silica gel, petroleum ether / ethyl acetate = 2 / 1-5 / 1) to obtain 65 mg of white solid, yield 83%, purity 99.9%. White solid in 83% yield; 1 H NMR (400MHz, CDCl 3 )δ8.08–7.90(m, 2H),7.79–7.69(m,1H),7.68–7.55(m,3H),7.43–7.33(m,2H),7.33–7.20(m,10H),7.19– 7.15(m,3H),7.14–7.01(m,1H),5.17(dd,J=16.6,6.7Hz,1H),4.67(dd,J=16.6,7.1Hz,1H); 13 C NMR (101MHz, CDCl 3 )δ142.35, 140.31, 139.90(d, J=0.8Hz), 136.86, 132.51(d, J=2.0Hz), 132.14(d, J=2.7Hz), 131....

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Abstract

The invention relates to a cyclic phosphamide derivative with a biaryl skeleton and a synthesis method and application thereof, belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing the cyclic phosphamide derivative with the biaryl skeleton by utilizing an electrochemical catalysis intramolecular phosphine amination reaction. The method has good applicability to mono-substituted or di-substituted electron withdrawing groups and electron donating groups on ortho, meta and para positions on a ring A and a ring B in a biaryl phosphamide compound structure, and a substituent R can be an electron donating alkyl group or an electron withdrawing group, so that the method has small influence on the yield of the corresponding product. Compared with the prior art, on one hand, the method has wide substrate universality, good reaction selectivity and high molecular conversion rate and yield; on the other hand, reaction conditions are mild, a catalytic mode is green and efficient, and operation steps are simple. The cyclic phosphamide derivative with the biaryl skeleton prepared by the method can be used for preparing various organic PN ligands and organic photoelectric materials through chemical conversion.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a cyclic phosphoramide derivative with a biaryl skeleton, a synthesis method and an application. Background technique [0002] Cyclophosphamide derivatives with biaryl skeletons have unique optical properties and are used as organic optoelectronic materials in OLEDs. In addition, various chiral PN-type ligands prepared by chemical transformation of cyclophosphamide derivatives with biaryl skeleton exhibit high catalytic activity in various organic catalytic reactions. In view of this, how to efficiently prepare cyclophosphamide derivatives with biaryl skeleton has become a research hotspot. However, due to the unique structure of the target compound, there are few synthetic methods at present. The common synthetic methods include: transition metal-catalyzed intramolecular C-N coupling reaction, oxidative dehydrogenation C-N bond coupling reaction, in which t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/6584C25B3/09C25B3/07C25B3/05C25B3/29
CPCC07F9/65842C25B3/05C25B3/07C25B3/09C25B3/29
Inventor 高文超赵强程新峰罗保民桑志培孔伟光李文广
Owner NANYANG NORMAL UNIV
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