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Dearomatization-based novel 1,4 addition type Ugi reaction

A dearomatization and reaction technology, applied in the field of Ugi reaction, can solve problems such as poor substrate applicability, and achieve the effect of good substrate applicability

Inactive Publication Date: 2019-05-31
TIANJIN UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This makes the reaction less suitable for substrates

Method used

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  • Dearomatization-based novel 1,4 addition type Ugi reaction
  • Dearomatization-based novel 1,4 addition type Ugi reaction
  • Dearomatization-based novel 1,4 addition type Ugi reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046]

[0047] First take a 50mL round bottom flask, add 10.0mL methanol at room temperature, add the pure compound 4-methyl-N-phenylaniline (1.0mmol) under stirring, cool to -40°C, add 320mg (1.0mmol) iodobenzene diacetic acid, stirred for 30 min, transferred the reaction solution to room temperature, stirred for 10 min, and monitored the progress of the reaction with TLC until the reactant disappeared, and the reaction was completed.

[0048] After the reaction finishes, transfer the reaction solution to a 50ml separatory funnel with ethyl acetate, extract three times with ethyl acetate, combine the organic phases, wash three times with saturated aqueous sodium chloride solution, dry the organic phase with anhydrous sodium sulfate to remove water, The filtered filtrate was rotary evaporated to dryness under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography, and the eluent was V 石油醚 :V 乙酸乙酯 =30:1, the product ...

Embodiment 2

[0053]

[0054] First, take a 15ml pressure-resistant reaction tube, add 2 mL of trifluoroethanol, then add imine 2a (1.0 mmol), benzoic acid (2.0 mmol), and tert-butylisonitrile (2.0 mmol) into the pressure-resistant reaction tube in sequence, and tighten The stopper was stirred for 10 minutes, and the reaction bottle was moved into a 60° C. oil bath, and the progress of the reaction was monitored with a TLC (thin layer chromatography) 5×2 cm silica gel plate until the end of the reaction.

[0055] After the reaction was completed, the reaction solution was transferred to a 50 mL round-bottomed flask with methanol solvent, and evaporated to dryness under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography, and the eluent was V 石油醚 :V 乙酸乙酯 =20:1-5:1, the pure product 5a was obtained, and the yield was calculated.

[0056] 1 H NMR (400MHz, CDCl 3 )δ13.56(s,1H),7.45-7.33(m,7H),7.22(d,J=8.0Hz,1H),7.15(d,J=8.0Hz,2H)...

Embodiment 3

[0060]

[0061] Take a 50ml reaction eggplant-shaped bottle, carry out anhydrous and oxygen-free operation, at room temperature, under the protection of argon, add 192mg (2mmol, 2equiv) of sodium tert-butoxide, 91.5mg (0.05mmol) of tris(dibenzylideneacetone) dipalladium , 0.05equiv), 4ml of anhydrous toluene was added under stirring, and then 93.8ul of tri-tert-butylphosphine (0.2mmol, 0.2equiv) was added and stirred for 2 minutes. Add 4-bromoethylbenzene (1.2 mmol, 1.2 equiv) and aniline 1.0 mmol, 1 equiv) for the last time, and then transfer the reaction system to a 50° C. oil bath for 1 h. TLC monitoring until the end of the reaction. Slowly add water to quench, add ethyl acetate (10mL×3) for extraction, combine the organic phases, wash with saturated sodium chloride (30mL×3), dry over anhydrous sodium sulfate and spin dry to obtain a crude product. The crude product was purified by silica gel column chromatography, and the eluent was V 石油醚 :V 乙酸乙酯 =50:1, the pure com...

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Abstract

The invention relates to a dearomatization-based novel 1,4 addition type Ugi reaction. The reaction includes steps: taking a 15ml pressure-resistant reaction tube, adding 2mL of trifluoroethanol, sequentially adding imine, acid and t-butylisonitrile into the pressure-resistant reaction tube, tightly plugging, stirring for 10min, transferring the reaction tube into an oil bath at 60 DEG C, and monitoring an extent of reaction by a thin layer chromatography silicon rubber plate until reaction is finished. Aniline is oxidized into imine by iodobenzene diacetate, then imine is subjected to reaction with carboxylic acid and t-butylisonitrile, and trifluoroethanol serves as a solvent.

Description

technical field [0001] The present invention studies imines, acids, and isonitriles as substrates based on dearomatization-based 1,4-addition Ugi reactions. Background technique [0002] 1,4 addition (Michael addition) is a very classic organic reaction. According to the hard and soft acid-base theory, soft nucleophiles are more likely to undergo 1,4 addition reactions than hard nucleophiles. As a carbon atom-based nucleophile, isonitrile is a soft nucleophile, so theoretically it should be easier to perform 1,4 addition to α,β-unsaturated imines. Through literature research, we found that as early as 1963, Ugi himself reported that bromides of N-alkyl substituted quinolines participated in the Ugi reaction ( Figure 1-9 ), although isonitrile can perform 1,2 addition or 1,4 addition to N-alkyl substituted quinolinium cations, only 1,4 addition products can be seen from the results of the reaction. This is the first and, to our knowledge, the only example of a 1,4 addition...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C231/10C07C237/24C07C253/30C07C255/58
Inventor 芦逵张壮陈志浩孙园园雷玲玉王栋郁彭
Owner TIANJIN UNIV OF SCI & TECH
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