One-pot synthesis method of alkyne thioether

A technology of arylalkyne sulfide and synthesis method, which is applied in sulfide preparation, organic chemistry and other directions, can solve the problems of long synthetic route separation of intermediates, limited application, high price, etc., and achieves easy separation and purification, good versatility, Easy to use effect

Inactive Publication Date: 2012-08-01
HUNAN UNIV
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Problems solved by technology

[0008] Some of the above methods have long synthetic routes and need to separate and purify the intermediates; some have difficulty in derivatizing the substrates, so they can only be limited to the preparation of several simple aryne sulfides, and the methods do not have universality; Although the method can synthesize aryne sulfides of various substituents, the yield is not high (30-60%); some methods require the use of sulfur reagents with certain special structures as substrates
It is worth mentioning that most of the currently known methods require the use of toxic and expensive aryne compounds as raw materials, which greatly limits the application of these methods

Method used

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  • One-pot synthesis method of alkyne thioether
  • One-pot synthesis method of alkyne thioether
  • One-pot synthesis method of alkyne thioether

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] R=CH 3 ;Ar=Ph

[0035] At room temperature, sodium methyl mercaptide (1.05 g, CH 3 SNa content 20%) and methanol (15mL), then slowly add α-bromoacetophenone (498mg, 2.5mmol) in the reaction system, after adding, TLC tracks the reaction, and about 15min has reacted and is added to the reaction solution Add 100mL of water, extract with dichloromethane (30mL×3), wash the organic phase with saturated brine, dry over anhydrous sodium sulfate, filter and evaporate the solvent under reduced pressure, and the residue is separated by silica gel column chromatography [V (petroleum ether ): V(CH 2 Cl 2 )=5:1] to obtain 316 mg of substrate 2a with a yield of 76%.

[0036] 2a colorless oil

[0037] 1 H NMR (400MHz, CDCl 3 ): δ=2.14(s, 3H), 3.77(s, 2H), 7.47(t, J=7.60Hz, 2H), 7.58(t, J=7.60Hz, 1H), 7.98(d, J=7.60Hz , 2H).

[0038] MS (EI) m / z (%): 166 (M + , 77).

Embodiment 2

[0040] R=CH 3 ;Ar=Ph

[0041] Under the protection of nitrogen at -78°C, LiHMDS (1.8 mL of 1.0 mol / L THF solution) was added dropwise to a THF (15 mL) solution of substrate 2a (300 mg, 1.8 mmol) and stirred for 30 minutes. ClP(O)(OEt) 2 (0.3mL, 2.2mmol) was added dropwise into the above reaction system liquid. After the dropwise addition was completed, the cooling device was removed, and the mixture was naturally raised to room temperature and stirred for 30 minutes. The reaction was cooled to -78°C again, and LiHMDS (4.5 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 reaction mixture 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 the solvent was evaporated under r...

Embodiment 3

[0048] Step is with embodiment 1. Substrate 2b was prepared from α-bromo-4-methoxyacetophenone (R=CH 3 ; Ar=4-CH 3 OC 6 h 4 ), yield 64%.

[0049] 2b colorless oil

[0050] 1 H NMR (400MHz, CDCl 3 ): δ=2.15(s, 3H), 3.73(s, 2H), 3.88(s, 3H), 6.95(d, J=8.80Hz, 2H), 7.97(d, J=8.80Hz, 2H).

[0051] MS (EI) m / z (%): 196 (M + , 88).

[0052] 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 69%.

[0053] 1b colorless oil

[0054] 1 H NMR (400MHz, CDCl 3 ): δ=2.46(s, 3H), 3.81(s, 3H), 6.82(d, J=8.40Hz, 2H), 7.37(d, J=8.80Hz, 2H).

[0055] 13 C NMR (100MHz, CDCl 3 ): δ=19.50 (SCH 3 ), 55.28 (OCH 3 ), 78.94(C≡), 91.62(C≡), 113.91(CH), 115.50(C), 133.39(CH), 159.63(C).

[0056] FT-IR (KBr): 2927, 2837, 2167 (C≡C), 1605, 1569, 1506, 1463, 1441, 1374, 1290, 1248, 1172, 1106, 1032, 977, 832, 777, 956, 832, 777, 644, 588, 537cm -1 .

[0057] MS (EI) m / z (%): 178 (M + , 85).

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Abstract

The invention provides a one-pot synthesis method of alkyne thioether 1 based on 2-hydrocarbon sulfenyl-1- aryl ethanone substrate. The method includes feeding Lithium Hexamethyldisilazide (LiHMDS) to tetrahydrofuran (THF) solution of the 2-hydrocarbon sulfenyl-1- aryl ethanone and stirring for reaction under protection of low-temperature nitrogen; adding [C1P(O) (OEt)2] dropwisely to the reaction system, increasing temperature to a room temperature and continuing to stir for reaction; after the reaction system cools to a low temperature again, adding the lithium hexamethyldisilazide (LiHMDS) dropwisely to the reaction system and keeping stirring for 1-3 hours under the temperature; and obtaining the arylethynes from the reaction mixture after normal aftertreatment and column chromatographic separation. The method is a convenient and economical processing method for the alkyne thioether.

Description

【Technical field】 [0001] The invention relates to a preparation method of aryne sulfide compounds. 【Background technique】 [0002] Since the construction of medical nanomaterials, micro-molecular devices, and efficient metal cluster catalysts all involve self-assembly, the development and application of new self-assembled functional materials has become an attractive research hotspot in the fields of chemistry, medicine, materials, and life sciences. . Although many sulfur-containing compounds have been used in the study of self-assembled monolayers (SAMs) and nanocluster assembly, the vast majority of self-assembled materials currently used are aliphatic sulfur-containing compounds with flexible frameworks. [0003] Arynylsulfide Molecule Ar-(≡-SR) with Rigid Structure n With good spatial orientation, it is easy to control the size or shape of the assembly during the self-assembly process of nanoclusters. Arynyl sulfide (Ar-≡-SR) is the key building block to construct mu...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C321/20C07C323/16C07C323/07C07C319/20C07D317/56
Inventor 安德烈苏琼许锋张凯谢德逊石磊
Owner HUNAN UNIV
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