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Method for synthesizing 5-aryl methylene-2-cyclohexenone derivates

A technology of aryl methylene and cyclohexenone, applied in the field of synthesizing cis-α-acyl-β, achieving the effect of product separation and purification, high regio and stereoselectivity, and simple operation

Inactive Publication Date: 2010-07-28
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The general synthesis methods are based on the original six-membered ring skeleton, so the limitations are relatively large, and the introduction of optical activity is also relatively difficult. Therefore, the development of a highly efficient synthetic optically active 2-cyclohexenone derivative has become a research hotspot.

Method used

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  • Method for synthesizing 5-aryl methylene-2-cyclohexenone derivates
  • Method for synthesizing 5-aryl methylene-2-cyclohexenone derivates

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Under nitrogen, ethyl 2-methyl-4-phenyl-2,3-butadienoate (0.0836 g, 0.4 mmol) and toluene (5 mL) were added to the reaction tube, and diethyl was added dropwise to the system. Zinc hexane solution (1.4 mL, 0.88 M, 3 equivalents, 1.2 mmol). After the addition was completed, after 2 hours of reaction, saturated ammonium chloride solution was added dropwise to quench the reaction. Add water, extract with ether, wash with 1% hydrochloric acid, saturated sodium bicarbonate, saturated brine, dry with anhydrous sodium sulfate, filter, concentrate, and flash column chromatography to obtain 2,6-dimethyl-3-ethyl Benzyl-4-phenyl-5(Z)-(phenylmethylene)-6-ethoxycarbonyl-2-cyclohexenone 0.0520 g, the yield was 65%. The product is a colorless solid. Melting point: 125-126°C (n-hexane).

[0023] 1 H NMR(300MHz, CDCl 3 ): δ7.35-7.17 (m, 8H), 7.17-7.09 (m, 2H), 6.86 (s, 1H), 4.47 (s, 1H), 3.60-3.47 (m, 1H), 3.30-3.15 (m , 1H), 2.70-2.50 (m, 1H), 2.22-2.10 (m, 1H), 2.00 (s, 3H), 1.20-1.1...

Embodiment 2

[0029] According to the method described in Example 1, the difference is that the substrate and reagent used are: 2-methyl-4-phenyl-2,3-butadienoic acid methyl ester (0.0765 g, 0.4 mmol), and 2 ,6-Dimethyl-3-ethyl-4-phenyl-5(Z)-(phenylmethylene)-6-methoxycarbonyl-2-cyclohexenone 0.0575g, the yield was 79% . The product is a colorless solid. Melting point: 161-162°C (n-hexane).

[0030] 1 H NMR(300MHz, CDCl 3 ): δ7.36-7.17(m, 8H), 7.11(d, J=7.2Hz, 2H), 6.70(s, 1H), 4.48(s, 1H), 2.96(s, 3H), 2.67-2.53( m, 1H), 2.23-2.10 (m, 1H), 2.00 (s, 3H), 1.20 (s, 3H), 1.16 (t, J=7.7 Hz, 3H);

[0031] 13 C NMR(CDCl 3 , 75MHz): δ197.1, 171.0, 158.3, 141.5, 141.3, 135.8, 131.3, 129.0, 128.7, 127.8, 127.7, 127.21, 127.15, 58.5, 54.2, 51.8, 27.5, 24.6, 11.9, 11.6;

[0032] MS(m / z): 374(M + , 62.84), 285(100);

[0033] IR(neat, cm -1 ): 2948, 1746, 1657, 1630, 1598, 1450, 1229, 1094.

[0034] Elemental analysis calcd for C 25 H 26 O 3 : C, 80.18; H, 7.00; Found: C, 80.25; H, 6.96.

Embodiment 3

[0036] According to the method described in Example 1, the difference is that the substrate and reagent used are: ethyl 2-methyl-4-(4'-bromophenyl)-2,3-butadienoate (0.1109 g, 0.4 Millimoles) to give 2,6-dimethyl-3-ethyl-4-(4'-bromophenyl)-5(Z)-((4'-bromophenyl)methylene)-6- The ethoxycarbonyl-2-cyclohexenone was 0.0674 g, and the yield was 63%. The product is a colorless solid. Melting point: 137-138°C (n-hexane).

[0037] 1 H NMR(300MHz, CDCl 3 ): δ7.43 (d, J=8.4Hz, 2H), 7.38 (d, J=8.4Hz, 2H), 7.10 (d, J=8.4Hz, 2H), 6.97 (d, J=8.4Hz, 2H) ), 6.72(s, 1H), 4.39(s, 1H), 3.65-3.53(m, 1H), 3.37-3.23(m, 1H), 2.65-2.50(m, 1H), 2.20-2.05(m, 1H) ), 1.98(s, 3H), 1.17(s, 3H), 1.13(t, J=7.8Hz, 3H), 0.93(t, J=7.1Hz, 3H);

[0038] 13 C NMR(CDCl 3 , 75MHz): δ196.8, 170.2, 156.7, 141.9, 140.4, 134.6, 131.8, 131.7, 130.9, 130.7, 129.6, 127.8, 121.4, 121.3, 61.1, 58.5, 53.7, 27.3, 24.2, 13.4, 11.9, 11.7;

[0039] MS(m / z): 548(M + (2× 81 Br), 18.01), 546(M + ( 79 Br and 81 Br), 35.82), 544(M + (2...

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Abstract

The invention relates to derivatives of 5-aryl methylene-2-cyclohexenone and a synthesis method thereof. Under room temperature, dialkyl zincon and two equivalents of 2, 3-allenic acid ester react to generate a series of derivatives of the 5-aryl methylene-2-cyclohexenone. The R<3> group of the dialkyl zincon is introduced onto the intermediate carbon of the first equivalent of allenes and ring closure reaction is carried out between the generated intermediate and the second equivalent of allenes; as the obtained product, 5 sites of double bonds are of single formation and two carbon atoms of4 sites and 6 sites have high diastereoselective. Chiral holding and optically active products can be prepared when optically active allenic acid ester is applied as a substrate to carry out reaction. The method of the invention is easy to be operated, adopts raw materials and solvents which are easy to get, has very high reaction regioselectivity and stereoselectivity, generates products which are easy to be separated and purified and is suitable for the synthesis of various substituted 5-aryl methylene-2-cyclohexenone derivatives.

Description

technical field [0001] The invention relates to a method for synthesizing cis-alpha-acyl-beta, gamma unsaturated carboxylic acid esters. At room temperature, a dialkyl zinc reagent reacts with two molecules of 2,3-alkenoate to generate a series of 5-arylmethylene-2-cyclohexenone derivatives. Background technique [0002] 5-arylmethylene-2-cyclohexenone derivatives are one of the most important intermediates in organic synthesis and one of the most common structural units in natural products. In the field of technology, medicine and pesticides have great development and utilization value (a) C.Gey, S.Kyrylenko, L.Hennig, L.-N.Nguyen, A.Bütter, H.D.Pham, A.Giannis, Angew.Chem .2007, 119, 5311; Angew.Chem.Int.Ed.2007, 46, 5219; b) K.C.Nicolaou, G.Vassikogiannakis, K.B.Simonsen, P.S.Baran, Y.-L.Zhong, V.P.Vidali, E.N.Pitsinos, E.A. Couladouros, J.Am.Chem.Soc.2000, 122, 3071; c) K.C.Nicolaou, K.B.Simonsen, G.Vassilikogiannakis, P.S.Baran, V.P.Vidali, E.N.Pitsinos, E.A.Couladou...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C67/30C07C69/757
Inventor 麻生明陆展柴国璧
Owner ZHEJIANG UNIV