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Synthesis method of benzo[b]phospholes

A technology of heterocyclopentadiene and synthesis method, which is applied in the field of organic chemical synthesis and achieves the effect of good application prospect and good tolerance

Inactive Publication Date: 2017-06-13
ZHENGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] Aiming at the present technical situation, the purpose of the present invention is to provide a novel green and environment-friendly synthetic method of benzophosphole compounds

Method used

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  • Synthesis method of benzo[b]phospholes
  • Synthesis method of benzo[b]phospholes
  • Synthesis method of benzo[b]phospholes

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Embodiment 1 I-a to I-g, I-j, I-k, the synthetic method of I-m, the steps are as follows:

[0022] Take 10mmol of the raw material of the compound of formula A in 100mL schlenk, vacuumize and change nitrogen three times, add 50mL of anhydrous ether, then warm the system to -75°C, add n-BuLi 10mmol dropwise, return the system to room temperature and react for 1h (system 1 ). Take another 100mL schlenk and change the nitrogen for three times, add 20mL of anhydrous ether, and then add PhPCl 2 11 mmol, and cooled to -78°C (system 2). Inject the turbid solution in System 1 into System 2 with a syringe, keep warm for 10 minutes after completion, and the reaction will return to room temperature by itself, and react for 1 hour. After the reaction was completed, 5 mL of water was slowly added to the reaction system in an open state, and the reaction was continued for 10 minutes. After the reaction was completed, it was extracted with ethyl acetate and water, the organic phas...

Embodiment 2I-h

[0030] Embodiment 2I-h, I-i, the synthetic method of I-l:

[0031] Take 10mmol of the raw material of the compound of formula A in 100mL schlenk, evacuate and change the nitrogen three times, add 50mL of anhydrous diethyl ether (THF was used for the synthesis of I-1), then cool the system down to -75°C, add 10mmol of n-BuLi dropwise, and keep it warm Reaction 1h (system 1). Take another 100mL schlenk and change the nitrogen for three times, add 20mL of anhydrous ether, and then add PhPCl 2 11 mmol, and cooled to -78°C (system 2). Inject the turbid solution in system 1 into system 2 with a syringe at -75°C, keep warm for 10 minutes after completion, and the reaction will return to room temperature by itself, and react for 1 hour. After the reaction is over, add 5 mL of water to the reaction system in an open state, and react for 10 minutes. The post-treatment method is the same as before.

[0032] I-i yield: 39%, pale yellow solid, 1 H NMR (300MHz, CDCl 3 )δ=7.26-7.55(m,9...

Embodiment 4II-a to II

[0034] Synthesis of Example 4II-a to II-m

[0035] The above annotation a Compounds were synthesized using toluene solvent, marked b Compounds were synthesized using DMF solvent. Take 1 mmol of the raw material of the target object I in a 30mL schlenk tube with a cock, add a rubber stopper in the ventilation, then vacuumize and change the nitrogen three times, then under the protection of nitrogen, add 5mL of anhydrous oxygen-free toluene or DMF5mL, and put Replace the rubber stopper with a Teflon sealing stopper. The system is sealed. React at 110°C-120°C. After the reaction was completed, the reaction solvent was distilled off under reduced pressure, and separated by column with dichloromethane:ethyl acetate=5:1.

[0036] II-a yield: 82%, 1 H NMR (300MHz, CDCl 3 )δ=7.28-7.53 (m, 10H), 7.59-7.79 (5H); 13 C NMR (75MHz, CDCl 3 )δ=124.68(d, J CP =9.5Hz,CH),126.60(d,J CP =6.4Hz,2CH),128.93(d,J CP =12.2,2CH),128.94(d,J CP =10.9Hz, 2CH), 128.94(s, 2CH), 129.19(d, J CP...

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Abstract

The invention belongs to the organic chemical synthesis field and in particular relates to a synthesis method of benzo[b]phospholes. The synthesis method comprises the following steps: taking 1-substitued-2-bromoaryl-acetylene as a raw material, adding a dichlorophenylphosphine synthesis intermediate, and then generating a target compound through trace air catalysis. The synthesis method provided by the invention has the advantages that an oxidant, a catalyst and an additive do not need to be additionally added, and tolerance on different functional groups is good, so that the synthesis method is an environment-friendly synthesis method for a benzo[b]phospholes compound; the yield reaches more than 40%, so that the synthesis method has a good application prospect.

Description

technical field [0001] The invention belongs to the field of organic chemical synthesis, and in particular relates to a method for synthesizing benzophospholene which has application value in terms of materials. Background technique [0002] Benzophosphole in photoelectric materials (Chem.Soc.Rev.2016,45,5296), biological imaging, fluorescent probes (Angew.Chem.Int.Ed.2015,54,4539; Chem.Commun. 2015, 51, 11880), photochromic molecular switches (Chem.Sci.2017, 8, 1309) and other aspects have a wide range of applications. [0003] The reported synthesis methods of benzophospole mainly include: I) the formation of phenylacetylene with ortho-phosphorus group by intramolecular ring formation; II) the intermolecular free radical reaction between the phosphorus-containing compound and another compound Formation; III) The key step is transition metal-catalyzed "one-pot" multi-component multi-step reaction generation (Org. Biomol. Chem. 2016, 14, 5402; Org. Lett. 2016, 18, 5436). S...

Claims

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Application Information

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IPC IPC(8): C07F9/6568C09K11/06H01L51/54
CPCC09K11/06C07F9/65686C09K2211/1096H10K85/657
Inventor 段征周洋王越王文彪
Owner ZHENGZHOU UNIV
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