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Series of tetraaryl spiro compounds and preparation and application methods thereof

A spiro compound, a series of technologies, applied in the field of organic chemical synthesis

Active Publication Date: 2019-04-05
TIANJIN NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the field of transition metal-catalyzed C–H activation of tertiary anilines remains deficient, with only a few examples of ortho-para selective transformations (Mizuta Y., Obora Y., Shimizu Y., et al. para-Selective Aerobic Oxidative C–H Olefination of Aminobenzenes Catalyzed by Palladium / Molybdovanadophosphoric acid / 2,4,6-Trimethylbenzoic Acid System[J]. Chemcatchem 2012, 4 (2), 187-191.)

Method used

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  • Series of tetraaryl spiro compounds and preparation and application methods thereof
  • Series of tetraaryl spiro compounds and preparation and application methods thereof
  • Series of tetraaryl spiro compounds and preparation and application methods thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0063] Under the protection of argon, take a 50 mL Schlenk reaction tube, add 32 μL (0.2 mmol) of N,N-diethylaniline, 35.6 mg (0.2 mmol) of toluene, Pd(OAc) 2 4.5 mg (0.02 mmol), Cu(OAc) 2 . h 2 O 40 mg (0.2mmol), o-phenanthroline 4.95 mg (0.025 mmol), AgBF 4 5.9 mg (0.03 mmol), methanol (1.0 mL), oil bath 100-120 o C, stirred for 24 h. After the reaction was completed, it was purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 20:1), and the product was 37.2 mg of white solid with a yield of 83%. (1,2,3,4-Tetraphenylspiro[4.5]dec-1,3,6,9-tetraen-8-one)

[0064] Melting point: 254 o C-256 o c. 1 H NMR (400 MHz, CDCl 3 ) δ 7.19-7.01 (m, 16H), 6.90 (d, J = 6.9Hz, 4H), 6.82 (d, J = 9.9Hz, 2H) , 6.44 (d, J = 9.9Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 186.2, 147.9, 147.6, 141.2, 134.7, 134.5, 131.9, 130.0, 129.3, 128.0, 127.9, 127.5, 127.3, 66.2.

Embodiment 2

[0066] Under argon protection, take a 50 mL Schlenk reaction tube and add 35.5 μL (0.2 mmol) of N,N-diethyl-m-methylaniline, 35.6 mg (0.2 mmol) of tolanil, Pd(OAc) 2 4.5 mg (0.02 mmol), Cu(OAc) 2 . h 2 O 40 mg (0.2 mmol), o-phenanthroline 4.95 mg (0.025 mmol), AgBF 4 5.9 mg (0.03 mmol), methanol (1.0 mL), oil bath 100-120 o C, stirred for 24 h. After the reaction was completed, it was purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 20:1), and the product was 14.8 mg of white solid with a yield of 32%. (6-methyl-1,2,3,4-tetraphenylspiro[4.5]dec-1,3,6,9-tetraen-8-one)

[0067] Melting point: 185 o C-187 o c. 1 H NMR (400 MHz, CDCl 3 ) δ 7.27-6.91 (m, 20H), 6.89-6.73 (m, 1H), 6.47 (d, J = 9.6 Hz, 1H), 6.39 (d, J = 15.4 Hz, 1H), 1.95 (s,3H); 13 C NMR (100 MHz, CDCl 3 ) δ 187.0, 156.6, 148.5, 148.4, 142.1, 134.8, 134.2, 131.4, 130.9, 129.9, 129.0, 128.1, 128.0, 127.5, 127.4, 68.6, 19.0; HRMS (ESI) m / z calcd for C 35 h 26...

Embodiment 3

[0069] Under the protection of argon, take a 50 mL Schlenk reaction tube and add 35.5 μL (0.2 mmol) of N,N-diethyl-o-methylaniline, 35.6 mg (0.2 mmol) of toluene, Pd(OAc) 2 4.5 mg (0.02 mmol), Cu(OAc) 2 . h 2 O 40 mg (0.2 mmol), o-phenanthroline 4.95 mg (0.025 mmol), AgBF 4 5.9 mg (0.03 mmol), methanol (1.0 mL), oil bath 100-120 o C, stirred for 24 h. After the reaction was completed, it was purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 20:1), and the product was 13.0 mg of white solid with a yield of 28%. (7-methyl-1,2,3,4-tetraphenylspiro[4.5]dec-1,3,6,9-tetraen-8-one)

[0070] Melting point: 192 o C-195 o c. 1 H NMR (400 MHz, CDCl 3 ) δ 7.15 – 7.07 (m, 12H), 7.03(dd, J = 7.6, 1.9 Hz, 4H), 6.93 – 6.87 (m, 4H), 6.79 (dd, J = 9.7, 2.8 Hz,1H), 6.63 – 6.57 (m, 1H) 6.42 (d, J = 9.7 Hz, 1H), 1.89(s, 3H); 13 C NMR (100MHz, CDCl 3 ) δ 186.8, 147.6, 147.1, 142.6, 141.5, 138.4, 134.8, 134.7, 131.4, 130.0, 129.3, 127.9, 127.8,...

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Abstract

The invention discloses a series of tetraaryl spiro compounds and preparation and application methods thereof and relates to a method for synthesizing a series of tetraaryl spiro compounds through direct cycloaddition reaction between aromatic tertiary amines and diaryl acetylene under catalysis of palladium acetate. The preparation method comprises mixing the palladium acetate with correspondingaromatic tertiary amines, the diaryl acetylene, copper acetate monohydrate, phenanthroline and tetrafluoroboric acid at a molar ratio of 0.2:2:2:2:0.25:0.3, adding in methanol as the solvent, fillingargon into a reaction system, controlling the reaction temperature to be 100-120 DEG C, and 24 hours later, extracting the solvent from the reaction system, and performing separation through silica column chromatography to obtain corresponding products. During the reaction above, the double-molecule diaryl acetylene is interpolated into the para C-H bonds of the aromatic tertiary amines to producethe spiro compounds. The preparation method of the series of tetraaryl spiro compounds has the advantages of being high in substrate applicability, simple in substrate structure, easy to acquire andthe like.

Description

[0001] This patent application is supported by the National Natural Science Foundation of China (21102101, 21772118, 21472122). technical field [0002] The invention belongs to the technical field of organic chemical synthesis, and relates to a method for synthesizing a series of tetraaryl spiro compounds through direct cycloaddition reaction of aromatic tertiary amines and diaryl acetylene compounds under the catalysis of palladium acetate. Background technique [0003] The carbon-carbon triple bond of alkynes is one of the important functional groups in organic chemistry, and in the past few decades, acetylene chemistry has experienced a renaissance, because it is not only present in frontier molecules of organic chemistry (eg: biochemistry or materials science) , but also as a basic module or multifunctional intermediate of synthetic chemistry (Stang P. J., Diederich F. Modern acetylene chemistry [M]. VCH: 1995; p 285-319.). Alkynes are also of widespread importance i...

Claims

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Application Information

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IPC IPC(8): C07C49/67C07C49/697C07C49/755C07C49/792C07C45/00C07C65/36C07C51/373C07C69/76C07C69/757C07C67/313C07C205/45C07C201/12H01M4/60H01M10/0525
CPCH01M4/60H01M10/0525C07C45/00C07C49/67C07C49/697C07C49/755C07C49/792C07C51/373C07C65/36C07C67/313C07C69/757C07C69/76C07C201/12C07C205/45C07C2603/94Y02E60/10
Inventor 王斌张金相李春举
Owner TIANJIN NORMAL UNIVERSITY