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A series of tetraaryl spiro compound and its preparation method and application
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A spiro compound, a series of technologies, applied in the field of organic chemical synthesis
Active Publication Date: 2021-12-21
TIANJIN NORMAL UNIVERSITY
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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.)
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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 (0.2 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 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)
[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 O40 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 O [M+...
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 tolanil, Pd(OAc) 2 4.5 mg (0.02 mmol), Cu(OAc) 2 . h 2 O40 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)
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Abstract
The invention discloses a series of tetraaryl spiro ring compounds and their preparation method and application, and relates to a series of tetraaryl spiro rings synthesized by direct cycloaddition reaction between aromatic tertiary amine and diaryl acetylene under the catalysis of palladium acetate compound method. The preparation method of the present invention is as follows: palladium acetate and corresponding aromatic tertiary amine, diaryl acetylene, copper acetate monohydrate, o-phenanthroline, and silver tetrafluoroborate according to the ratio of 0.2:2:2:2:0.25:0.3 The molar ratio is mixed, solvent methanol is added, the reaction system is filled with argon, and the reaction temperature is controlled at 100‑120 o C. After 24 hours, the reaction system was pumped to dry the solvent, and separated by silica gel column chromatography to obtain the corresponding product. In this reaction, two molecules of diaryl acetylene are inserted into the para-position C-H bond of the tertiary amino group to generate a spiro compound. The method has the advantages of simple operation, good substrate applicability, simple and easy-to-obtain substrate structure and the 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...
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