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Method for preparing halogenated benzo [alfa] fluorenol

A technology of halogenated benzene and fluorenol, applied in the field of preparation of halogenated benzo[a]fluorenol, can solve the problems of poor functional group compatibility of reactants, harsh conditions, difficult separation, etc., and achieves excellent chemical selectivity and reaction operation. The effect of simplicity and high product yield

Inactive Publication Date: 2012-09-12
JIANGXI NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

These methods require the reactants to be heated to a relatively high temperature for conversion to occur. The conditions are relatively harsh, and the compatibility of the functional groups of the reactants is relatively poor. The resulting products are often a mixture of several isomers, which are difficult to separate.

Method used

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  • Method for preparing halogenated benzo [alfa] fluorenol
  • Method for preparing halogenated benzo [alfa] fluorenol
  • Method for preparing halogenated benzo [alfa] fluorenol

Examples

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Effect test

example 1

[0022]

[0023] Under the protection of nitrogen, N-iodosuccinimide (NIS, 0.36mmol) and catalyst AgOTf (0.015mmol) were dissolved in the organic solvent dichloromethane, and added dropwise to 3-phenyl-1 -(2-(2-Phenylethynyl)phenyl)propargyl-2-ol (0.30mmol) in dichloromethane solution, stirred at 10°C for 10-15 hours, TLC detected complete reaction. After the reaction was completed, the solvent was spin-dried, and the crude product was directly subjected to silica gel column chromatography to obtain the pure product 6-iodo-11-phenyl-11H-benzo[a]fluorenol 2a. Yield: 71%; 1 H NMR (400MHz, CDCl 3 ): δ8.81-8.79(d, J=8.00Hz, 1H), 8.49(s, 1H), 7.85-7.83(d, J=8.00Hz, 1H), 7.74-7.72(d, J=8.00Hz, 1H), 7.42-7.39(m, 4H), 7.37-7.32(m, 2H), 7.28-7.19(m, 5H), 2.54(s, 1H); 13 C NMR (100MHz, CDCl 3 ): δ152.3, 147.1, 142.6, 141.8, 139.2, 137.8, 135.1, 128.6, 128.5, 128.4, 128.1, 127.4, 127.2, 127.1, 126.5, 125.2, 124.9, 124.1, 122.5, 85.0 calcd for C 23 h 15 IO(M) + : 434.0168, found...

example 2

[0025]

[0026] Under the protection of nitrogen, N-bromosuccinimide (NBS, 0.36mmol) and catalyst AgOTf (0.015mmol) were dissolved in the organic solvent dichloromethane, and added dropwise to 3-phenyl-1 -(2-(2-Phenylethynyl)phenyl)propargyl-2-ol (0.30mmol) in dichloromethane solution, stirred at 10°C for 10-15 hours, TLC detected complete reaction. After the reaction was completed, the solvent was spin-dried, and the crude product was directly subjected to silica gel column chromatography to obtain the pure product 6-bromo-11-phenyl-11H-benzo[a]fluorenol 2b. Yield: 54%; 1 H NMR (400MHz, CDCl 3 ): δ8.59-8.57(d, J=8.00Hz, 1H), 8.14(s, 1H), 7.84-7.82(d, J=8.00Hz, 1H), 7.76-7.74(d, J=8.00Hz, 1H, 7.39-7.36(m, 3H), 7.33-7.29(m, 2H), 7.24-7.18(m, 4H), 2.56(s, 1H); 13 C NMR (100MHz, CDCl 3 ): δ152.2, 147.3, 142.5, 138.6, 135.9, 134.7, 134.0, 128.7, 128.5, 128.4, 127.6, 127.2, 126.9, 126.6, 125.1, 124.9, 124.1, 123.8, 114.7, 83.9). 23 h 15 BrO(M) + : 386.0306, found: 386.032...

example 3

[0028]

[0029] Under the protection of nitrogen, N-iodosuccinimide (NIS, 0.36mmol) and catalyst AgOTf (0.015mmol) were dissolved in the organic solvent dichloromethane, and added dropwise to 3-phenyl-1 -(2-(2-phenylethynyl-5-fluoro)phenyl)propargyl-2-ol (0.30mmol) in dichloromethane solution, stirred at 10°C for 10-15 hours, TLC detected to complete reaction. After the reaction was completed, the solvent was spin-dried, and the crude product was directly subjected to silica gel column chromatography to obtain the pure product 3-fluoro-6-iodo-11-phenyl-11H-benzo[a]fluorenol 2c. Yield: 56%; 1 H NMR (400MHz, CDCl 3 ): δ8.80-8.78(d, J=8.00Hz, 1H), 8.45(s, 1H), 7.72-7.69(m, 1H), 7.51-7.43(m, 2H), 7.20-7.14(m, 2H ), 7.36-7.34(m, 1H), 7.29-7.21(m, 3H), 7.16-7.12(t, J=8.00Hz, 1H), 2.53(s, 1H); 13 C NMR (100MHz, CDCl 3 ): δ167.7, 161.9, 159.5, 152.4, 146.68, 146.61, 141.9, 141.6, 138.8, 138.6, 132.2, 132.0, 130.8, 129.9, 129.8, 129.4, 129.3, 128.9, 128.8, 127.38, 128.5, 2 124...

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Abstract

The invention provides a method for preparing halogenated benzo [alfa] fluorenol. The method comprises the following step of performing series electrophilic cyclization reaction on 3-aryl-1-(2-(2-aryl ethinyl) phenyl) propargyl-2-alcohol serving as a reaction substrate and various electrophilic reagents such as halogenated succinimide (NXS, X=I, Br and Cl) or simple substance iodine (I2), simple substance bromine (Br2) or iodine chloride (ICl) at the temperature of 0 and 15 DEG C for 10 and 15 hours under the catalysis of AgOTf, and is a 'one-pot method' for efficiently preparing the Halogenated benzo [alfa] fluorenol. The method has the advantages of mild reaction conditions, low cost, less side reaction, high product purity, is easy to operate and can be applied to mass production of the halogenated benzo [alfa] fluorenol; and moreover, separation and purification can be conveniently realized.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry, and in particular relates to a preparation method of a halogenated benzo[a]fluorenol. Background technique [0002] Compounds with fluoreno ring structures often have very good photoelectric functional properties due to their relatively large π-conjugated systems ((a) Shimizu, A.; Tobe, Y.Angew.Chem.Int.Ed.2011, 50 , 6906. (b) Liu, T.; Xing, C.; Hu, Q. Angew. Chem. Int. Ed. 2010, 49, 2909. (c) Allard, S.; Forster, M.; .; Thiem, H.; Scherf, U.Angew.Chem.Int.Ed.2008, 47, 4070.), and are widely used in the field of optoelectronic functional materials. In addition, current research has also found that polycyclic aromatic compounds with benzofluorene structure are also the core structural units of many natural products or drugs. For example, the natural product 5-diazobenzo[b ] fluorene, which is also one of the main components of the antibiotic kanamycin ((a) Gould, S.J.; Tamayo, N.; Melv...

Claims

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Application Information

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IPC IPC(8): C07C29/62C07C35/52C07C41/32C07C43/23C07C35/44C07C29/34
Inventor 陈知远曾梦静杨琴彭以元
Owner JIANGXI NORMAL UNIV
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