Synthesis method of 9-aryl-9H-oxo/thioxanthene compound

A synthetic method, the technology of thioxanthene, applied in the synthesis of 9-aryl-9H-oxygen/thioxanthene, in the field of organic chemistry, can solve the problem of harsh reaction conditions, non-commercialization of reaction raw materials, and the increase of production costs and products by precious metals The difficulty of purification and other issues, to achieve the effect of mild reaction conditions, high atom economy and step economy

Active Publication Date: 2021-08-31
HUAIBEI NORMAL UNIVERSITY
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AI Technical Summary

Problems solved by technology

In 2020, it was reported that using triarylmethanol derivatives as raw materials, in NaHSO 4 / SiO 2 The synthesis of 9-aryl-9H-oxanthene and 9-aryl-9H-thioxanthene has been realized under catalysis, but the reaction raw materials are not commercialized and difficult to synthesize
Another synthetic strategy employs the reaction of benzyne precursors with aldehydes or ketones, however, the atom economy is poor.
[0003] In 2012, it was reported that xanthene and aromatic hydrocarbons were used for C-H / C-H coupling, and the reaction used trifluoromethanesulfonic acid catalyst, but the reaction conditions were harsh, requiring high-pressure oxygen (10bar) and low boiling point solvent dichloromethane 100 ° C to 9- (4-methoxyphenyl)-9H-xanthene as an example, the yield is only 27%
In 2016, it was reported that the palladium / copper co-catalyzed reaction of xanthenes with arenes was carried out using 5mol% Pd(OAc) 2 and 10mol% Cu(OTf) 2 As a catalyst, the use of precious metals increases the production cost and the difficulty of product purification
However, there is no related literature report at present, so it is still very important to explore the method of constructing 9-aryl-9H-oxanthene and 9-aryl-9H-thioxanthene and analogues under no catalyst, no oxidant and mild conditions. necessary

Method used

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  • Synthesis method of 9-aryl-9H-oxo/thioxanthene compound
  • Synthesis method of 9-aryl-9H-oxo/thioxanthene compound

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Experimental program
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Embodiment 1

[0029] Optimization of reaction conditions

[0030] Add xanthene (1a, 32.2mg, 0.5mmol), electrolyte (0.4mol%), anisole (2a, 1.0814g, 10mmol), additive (2eq, 1mmol), organic solvent (5mL) into 10mL without septum in the electrolyzer. Plug the mouth of the bottle with a rubber stopper inserted into the electrode, then insert an empty balloon, connect the potentiostat to the electrode, set the current intensity, pass in the current, and react at 80°C for 12 hours. After the reaction was completed, distilled water (30 mL) was added and extracted with an organic solvent. The organic layers were combined, dried over anhydrous sodium sulfate, and evaporated under reduced pressure with a rotary evaporator to obtain a crude product, which was purified with a silica gel column (petroleum ether / ethyl acetate=30:1) to obtain product 3a. The optimized reaction results are as follows:

[0031]

[0032]

[0033] During the screening of reaction conditions, the additives (label 1-6),...

Embodiment 2

[0035] Xanthene (1a, 91.1mg, 0.5mmol), n-Bu 4 NBF 4 (131.7mg, 0.4mol%), anisole (2a, 1.0814g, 10mmol), methanesulfonic acid (2eq, 96.1mg, 1mmol), 1,2-dichloroethane (5mL) were sequentially added to 10mL without septum in the electrolyzer. Plug the mouth of the bottle with a rubber stopper inserted into the electrode (the carbon rod is used as the anode, and the 1cm×1cm platinum electrode is used as the cathode), then insert an empty balloon, connect the potentiostat to the electrode, set the current intensity to 5mA, and pass in the current. The reaction was carried out at 80° C. for 12 hours. After the reaction was completed, distilled water (30 mL) was added and extracted with ethyl acetate (3×30 mL). The organic layers were combined, dried over anhydrous sodium sulfate, and the crude product was distilled under reduced pressure with a rotary evaporator to obtain a crude product, which was purified by a silica gel column (petroleum ether / ethyl acetate=30:1) to obtain 116....

Embodiment 3

[0038] According to embodiment 2 reaction conditions, only change substrate 1 or substrate 2 structure, obtain reaction product result as follows:

[0039] 9-(3,4-dimethoxyphenyl)-9H-xanthene(3b):Pale yellow solid; 113.6 mg, 71% yield; 1 H NMR (600MHz, CDCl 3 )δ7.22-7.28(m,2H),7.13(dd,J=8.2,1.1Hz,2H),7.06(d,J=7.0Hz,2H),6.98(td,J=7.5,1.2Hz,2H ),6.79(d,J=1.0Hz,2H),6.66(s,1H),5.20(s,1H),3.84(s,3H), 3.76(s,3H). 13 C NMR (151MHz, CDCl 3 )δ151.2, 149.4, 148.0, 139.1, 129.8, 128.0, 124.7, 123.3, 120.8, 116.6, 111.7, 111.2, 56.0, 44.1. HRMS (ESI) calcd.forC 21 h 18 NaO 3 + ([M+Na] + ):341.1148,found:341.1147.

[0040] 2-methyl-4-(9H-xanthen-9-yl)phenol(3c):Pale yellow solid; 74.7mg, 52% yield; 1 H NMR (600MHz, CDCl 3 )δ7.18(t, J=7.5Hz, 2H), 7.11 (d, J=8.1Hz, 2H), 7.04(d, J=7.5Hz, 2H), 6.96(t, J=7.4Hz, 2H) , 6.91(s,1H),6.88(dd,J=8.1,1.5Hz,1H),6.64(d,J=8.1Hz,1H),5.14(s,1H),4.63(s,1H),2.15( s,3H). 13 C NMR (151MHz, CDCl 3 )δ152.6, 151.1, 139.1, 131.1, 129.8, 127.9, 127.2, 1...

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Abstract

The invention discloses a synthesis method of a 9-aryl-9H-oxo / thioxanthene compound, and belongs to the technical field of organic chemistry. According to the preparation method, oxygen / thioxanthene 1 and aromatic hydrocarbon 2 are taken as raw materials, C-H / C-H coupling is carried out under electrochemical anodic oxidation, and rapid synthesis of the 9-aryl-9H-oxygen / thioxanthene compound 3 is realized. According to the method, electrochemistry is adopted for direct coupling of C-H / C-H, high atom / step economy is achieved, meanwhile, the reaction is achieved under the condition that no catalyst or oxidizing agent exists, the method is environmentally friendly, and a new rapid, efficient, economical and green way is provided for synthesis of 9-aryl-9H-oxo / thioxanthene series products.

Description

technical field [0001] The invention relates to a synthesis method of 9-aryl-9H-oxygen / thioxanthene, which belongs to the technical field of organic chemistry. Background technique [0002] Xanthene and thioxanthene derivatives, especially 9-aryl-9H-xanthene and 9-aryl-9H-thioxanthene and their analogs, are the backbone structures of many natural products and drug molecules. In the past few years, a lot of research has been done on the synthesis of 9-aryl-9H-oxo / thioxanthene, among which the use of diarylmethanol derivatives as raw materials is the most classic, but this method requires the use of metal catalysts or complex organic molecules catalyst. In 2020, it was reported that using triarylmethanol derivatives as raw materials, in NaHSO 4 / SiO 2 The synthesis of 9-aryl-9H-xanthene and 9-aryl-9H-thioxanthene has been realized under catalysis, but the reaction raw materials are not commercialized and are difficult to synthesize. Another synthetic strategy employs the r...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C25B3/29C25B3/05C25B3/07C25B3/11
CPCC25B3/29C25B3/05C25B3/07C25B3/11
Inventor 高慧王培龙李洪基
Owner HUAIBEI NORMAL UNIVERSITY
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