One-pot synthesis method of conjugate eneyne thioether

The technology of an enyne sulfide and a synthesis method is applied in the field of preparation of conjugated enyne sulfide compounds, can solve the problems of high price, limited application and the like, and achieves the effects of simple operation, good versatility, easy separation and purification

Active Publication Date: 2014-03-05
HUNAN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

This method requires the use of expensive alkyne compounds as raw materials, which greatly limits its application

Method used

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  • One-pot synthesis method of conjugate eneyne thioether
  • One-pot synthesis method of conjugate eneyne thioether
  • One-pot synthesis method of conjugate eneyne thioether

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] R=CH 3 ;Ar=Ph

[0032] At room temperature, add sodium methyl mercaptide (420 mg, CH 3 SNa content 50%) and methanol (15mL), then slowly add 1-bromo-4-phenyl-3-buten-2-one (560mg, 2.5mmol) to the reaction system, after adding, TLC follows the reaction , the reaction was completed in about 15 minutes, 100 mL of water was added to the reaction solution, extracted with dichloromethane (30 mL × 3), the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered and evaporated to remove the solvent under reduced pressure, and the residue was passed through Silica gel column chromatography separation [V (petroleum ether): V (CH 2 Cl 2 )=5:1] to obtain 2a 293mg, yield 61%.

[0033] 2a Pale yellow oil

[0034] 1 H NMR (400MHz, CDCl 3 ): δ=2.09(s, 3H), 3.39(s, 2H), 6.97(d, J=16.00Hz, 1H), 7.38~7.41(m, 3H), 7.56~7.59(m, 2H), 7.68( d, J=16.00Hz, 1H).

[0035] MS (EI) m / z (%): 192 (M + , 75).

Embodiment 2

[0037] R=CH 3 ;Ar=Ph

[0038] LiHMDS (1.0 mol / L THF solution, 1.6 mL) was added dropwise to substrate 2a (307 mg, 1.6 mmol) in THF (15 mL) at -78°C under nitrogen protection, and stirred for about 30 minutes. ClP(O)(OEt) 2 (0.3mL, 1.9mmol) into the above reaction system. After the dropwise addition, the cooling device was removed, and the mixture was naturally raised to room temperature and stirred for 30 minutes. The reaction system was cooled to -78°C again, and then LiHMDS (4.0 mL of tetrahydrofuran solution with a concentration of 1.0 mol / L) was added dropwise to the above reaction system, and stirring was continued at this temperature for 1 hour. The reaction was quenched with saturated ammonium chloride solution, the mixed solution was poured into water, extracted with ethyl acetate (30mL×3), the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered and evaporated to remove the solvent under reduced pressure, the residue The pro...

Embodiment 3

[0045] Step is with embodiment 1. Substrate 2b was prepared starting from 1-bromo-4-(4-methoxy)phenyl-3-buten-2-one (R=CH 3 ; Ar=4-CH 3 OC 6 h 4 ), yield 65%.

[0046] 1b Light yellow solid, melting point: 50~52℃

[0047] 1 H NMR (400MHz, CDCl 3 ): δ=2.10(s, 3H), 3.83(s, 2H), 3.85(s, 3H), 6.85(d, J=16.00Hz, 1H), 7.92(d, J=8.80Hz, 2H), 7.54 (d, J=8.80Hz, 2H), 7.64 (d, J=16.00Hz, 1H).

[0048] MS (EI) m / z (%): 222 (M + , 85).

[0049] Step is with embodiment 2. The substrate is 2b (R=CH 3 ; Ar=4-CH 3 OC 6 h 4 ), the product is 1b, and the yield is 70%.

[0050] 1b yellow solid, melting point: 32~34℃

[0051] 1 H NMR (400MHz, CDCl 3 ): δ=2.44(s, 3H), 3.81(s, 3H), 6.08(d, J=16.00Hz, 1H), 6.83~6.88(m, 3H), 7.30(d, J=8.00Hz, 2H) .

[0052] 13 C NMR (100MHz, CDCl 3 ): δ=19.52 (SCH 3 ), 55.28 (OCH 3 ), 82.06(C≡), 91.75(C≡), 105.72(CH), 114.11(CH), 127.49(CH), 129.07(C), 140.33(CH), 160.00(C).

[0053] FT-IR (KBr): 2926, 2134 (C≡C), 1604, 1511, 1308, 1249, 1175...

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Abstract

The invention provides a one-pot synthesis method of conjugate eneyne thioether based on 1-hydrocarbon sulfenyl-4-aryl-butene-2-ketone substrate. The method includes feeding Lithium Hexamethyldisilazide (LiHMDS) to a tetrahydrofuran (THF) solution of 1-hydrocarbon sulfenyl-4-aryl-butene-2-ketone under protection of low-temperature nitrogen; stirring; adding [C1P(O) (OEt)2] dropwisely to the reaction system, increasing the temperature to a room temperature after the addition and continuing to stir; after the reaction system cools again to a low temperature, dripping the LiHMDS to the reaction system and stirring for reaction under the temperature; and obtaining the conjugate eneyne thioether from the reaction mixture after normal aftertreatment and column chromatographic separation. The method is a convenient and economical processing method for the conjugate eneyne thioether.

Description

【Technical field】 [0001] The present invention relates to a preparation method of conjugated enyne sulfide compounds, specifically a conjugated enyne sulfide based on 1-hydrocarbylthio-4-aryl-3-buten-2-one A new method for the one-pot synthesis of . 【Background technique】 [0002] Conjugated enynes are a class of compounds that contain two mutually conjugated double bonds and triple bonds in the molecule. This kind of enyne compound contains the basic structure of alkenes and alkynes, and has the basic properties of these two types of compounds. It is an extremely important class of organic synthesis intermediates. It is widely used in the synthesis of biologically active compounds and the preparation of macrocyclic molecules (Trost et al., Angew.Chem.Iht.Ed., 34(3): 259-281, 1995; Nicolaou et al., Science, 256 (6): 1172-1178, 1992). However, the preparation of conjugated enyne sulfides is very rare, and the only report comes from Japanese researchers. Mitsunobu et al. u...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C319/20C07C321/20C07C321/28C07C323/16C07C323/07
Inventor 安德烈苏琼梅洪峰刘元甫谢德逊石磊蔡青云
Owner HUNAN UNIV
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