One-pot synthesis method of methylthio aryl alkynye

A technique for diacetylenic sulfides and synthesis methods, which is applied in the fields of thioether preparation and organic chemistry, and can solve the problems of obtaining aryldiyne sulfides, which have not been found in literature reports, etc., and achieve simple operation, good versatility, and easy separation and the effect of purification

Inactive Publication Date: 2014-01-01
HUNAN UNIV
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  • Abstract
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Problems solved by technology

However, it is very difficult to obtain arylene diacetylene sulfide (Ar-≡-≡-SR) terminal building blocks, and no related literature reports have been found so far

Method used

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  • One-pot synthesis method of methylthio aryl alkynye
  • One-pot synthesis method of methylthio aryl alkynye
  • One-pot synthesis method of methylthio aryl alkynye

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] R=CH 3 ;Ar=Ph

[0031] At room temperature, add sodium methyl mercaptide (421 mg, CH 3 SNa content 50%) and methanol (15mL), then slowly add 4-bromo-1-phenyl-1,3-butanedione (603mg, 2.5mmol) in the reaction system, after adding, TLC tracking reaction, The reaction was completed in about 15 minutes, and 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 the solvent was evaporated 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 364 mg of substrate 2a with a yield of 70%.

[0032] 2a Pale yellow oil

[0033] (keto form: enol form = 0.08: 1.00) (enol form) 1 H NMR (400MHz, CDCl 3 ): δ=2.19(s, 3H), 3.30(s, 2H), 6.40(s, 1H), 7.46(t, J=7.60Hz, 2H), 7.54(t, J=7.60Hz, 1H), 7.90 (d, J=7.60Hz, 2H), 15.77(s, 1H). (keto form)1 ...

Embodiment 2

[0036] R=CH 3 ;Ar=Ph

[0037] Under nitrogen protection at -78°C, LiHMDS (1.0 mol / L THF solution, 2.8 mL) was added dropwise to substrate 2a (300 mg, 1.4 mmol) in THF (15 mL), and stirred for 30 minutes. ClP(O)(OEt) 2 (0.4mL, 2.9mmol) was added dropwise to the above reaction system. 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 system was cooled to -78°C again, and then LiHMDS (7.0 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 reaction mixture was poured into water, extracted with ethyl acetate (30 mL×3), the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressu...

Embodiment 3

[0044] Step is with embodiment 1. Substrate 2b was prepared starting from 4-bromo-1-(4-methyl)phenyl-1,3-butanedione (R=CH 3 ; Ar=4-CH 3 C 6 h 4 ), yield 63%.

[0045] 2b Light yellow solid, melting point: 51~55℃

[0046] (keto form: enol form = 0.10: 1.00) (enol form) 1 H NMR (400MHz, CDCl 3 ): δ=2.19(s, 3H), 2.42(s, 3H), 3.29(s, 2H), 6.37(s, 1H), 7.26(d, J=8.40Hz, 2H), 7.80(d, J= 8.00Hz, 2H), 15.86(s, 1H). (keto form) 1 H NMR (400MHz, CDCl 3 ): δ=2.07(s, 3H), 2.42(s, 3H), 3.36(s, 2H), 4.30(s, 2H).

[0047] MS (EI) m / z (%): 222 (M + , 100).

[0048] Step is with embodiment 2. The substrate is 2b (R=CH 3 ; Ar=4-CH 3 C 6 h 4 ), the product is 1b, and the yield is 59%.

[0049] 1b yellow oil

[0050] 1 H NMR (400MHz, CDCl 3 ): δ=2.34(s, 3H), 2.44(s, 3H), 7.11(d, J=8.00Hz, 2H), 7.36(d, J=8.40Hz, 2H).

[0051] 13 C NMR (100MHz, CDCl 3 ): δ=18.99 (SCH 3 ), 21.55 (CH 3 ), 73.69(C≡), 75.00(C≡), 77.96(C≡), 79.40(C≡), 118.50(C), 129.14(CH), 132.43(CH), 139.49(C...

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Abstract

The invention provides a new method of the one-pot synthesis of methylthio aryl alkynye 1 based on 4-sulfenyl-1-aryl-1,3-butanedione substrates. lithium hexamethyldisilazide (LiHMDS) is added in tetrahydro furan (THF) solution containing 4-sulfenyl-1-aryl-1, 3-diacetyl under the protection of low temperature nitrogen, and the stirring is carried out; in addition, diethyl chlorophosphate [ClP(O)(OEt)2] is dripped into the above-mentioned reaction system, the temperature rises to reach the room temperature naturally after the dripping is finished, and stirring is carried out continuously. The reaction system is cooled down to get low temperature again, then LiHMDS is dripped into the reaction system, and stirring is carried out continuously for reaction under the temperature. Reaction mixtures are processed through conventional post-processing and column chromatography separation, and then methylthio aryl alkynye is obtained. The new method is simple, convenient and economical to prepare methylthio aryl alkynye.

Description

【Technical field】 [0001] The invention relates to a preparation method of aryndiacetylene sulfide compounds. 【Background technique】 [0002] The development and application of self-assembled new functional materials is an attractive research hotspot in the fields of chemistry, medicine, materials and life sciences. Due to the great application value of sulfur-containing compounds in self-assembled monolayers (SAMs) and the self-assembly research of noble metal nanoclusters, developed countries such as Europe, America and Japan have been actively carrying out research on such materials, and have made great efforts to discover Apply for patent protection for self-assembly materials. At present, many sulfur-containing compounds, such as mercaptans (including polythiols) (Li et al., Langmuir, 18 (8): 3392-3395, 2002), thiophenols (Hutchison et al., J.Am.Chem.Soc., 127( 49): 17421-17426, 2005; Pemberton et al., Langmuir, 8(3): 753-756, 1992), thioethers (Zhong et al., J.Am.Chem...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C319/20C07C321/20C07C321/28C07C323/07
Inventor 安德烈苏琼杨盛查长军谢德逊石磊蔡青云
Owner HUNAN UNIV
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