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Phase-transferring catalyst containing dinaphthalene chiral double-spiral quaternary ammonium and its production

A technology of phase transfer catalysts and double spiro rings, which can be used in organic chemistry methods, chemical instruments and methods, physical/chemical process catalysts, etc., and can solve problems such as inability to obtain ideal results from substrates

Inactive Publication Date: 2007-11-21
TIANJIN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Chiral quaternary ammonium salt compounds are used as phase transfer catalysts to catalyze asymmetric reactions. Although people have done a lot of research work, the use of existing chiral quaternary ammonium salt phase transfer catalysts can only show high sensitivity to specific substrates. activity and enantioselectivity, not ideal for all substrates

Method used

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  • Phase-transferring catalyst containing dinaphthalene chiral double-spiral quaternary ammonium and its production
  • Phase-transferring catalyst containing dinaphthalene chiral double-spiral quaternary ammonium and its production
  • Phase-transferring catalyst containing dinaphthalene chiral double-spiral quaternary ammonium and its production

Examples

Experimental program
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Effect test

example 1

[0016] Example 1: Preparation of catalyst: (R, R)-bis(1,1'-binaphthyl-2,2'-methyleneamine)-4,4'-bipiperazine alkyl ammonium bromide

[0017]

[0018] (R, R)-1,1'-binaphthyl-2,2'-dimethyl bromide 660mg, (1.4mmol), 4,4'-bipiperazine 169mg (0.7mmol), potassium carbonate 580mg, ( 4.2mmol) into a 100mL round-bottomed flask, and 15mL of acetonitrile was added, the mouth of the round-bottomed flask was connected to a spherical condenser with a drying tube, heated to reflux at 80°C for 24 hours, and the reaction was detected by thin-layer chromatography. The reaction solution was poured into a beaker filled with 40 mL of water, and stirred for 10 minutes. Transfer to a separatory funnel and extract three times with 120 mL of dichloromethane. The organic phases were combined and dried over anhydrous magnesium sulfate. Filtration, evaporation of the solvent, quick silica gel column separation (dichloromethane / methanol=50 / 1 as the eluent), to obtain the target (R, R)-bis(1,1'-binaph...

example 2

[0020] Example 2: Preparation of catalyst: (S, S)-bis(1,1'-binaphthyl-2,2'-methyleneamine)-4,4'-bipiperazine ammonium bromide

[0021]

[0022] In a method similar to Example 1, using (S, S)-1,1-binaphthalene-2,2'-dimethyl bromide as a raw material, using tetrahydrofuran as a solvent, and a reaction temperature of 0°C, synthesize (S, S) -Bis(1,1'-binaphthyl-2,2'-methyleneamine)-4,4'-bipiperazine ammonium bromide, yield 91.2%. 1 H NMR (500MHz, CDCl 3 ), δppm: 1.72-1.77 (m, 2XCH, 2H), 1.81-1.88 (m, 2XCH, 2H), 2.10-2.22 (m, 2XCH, 2H), 2.29-2.33 (m, 2XCH, 2H), 2.35- 2.37(m, 2XCH, 2H), 3.37-3.42(m, 2XCH, 2H), 3.52-3.55(m, 2XCH, 2H), 3.63-3.74(m, 6XCH, 6H), 3.96(d, J=13.0Hz , 2H), 4.50(d, J=13.0Hz, 2H), 5.09(d, J=13.0Hz, 2H), 7.38-7.48(m, Ar-H, 8H), 7.62-7.65(m, Ar-H , 4H), 7.83-7.91 (m, Ar-H, 4H), 8.12-8.13 (m, Ar-H, 4H), 8.22-8.25 (m, Ar-H, 4H).

[0023] The catalyst is used to catalyze the conjugated addition reaction of nitroisopropane to α, β-unsaturated carbonyl compoun...

example 3

[0024] Example 3: Preparation of catalyst: (R, R)-bis(1,1'-binaphthyl-2,2'-methyleneamine)-4,4'-bispiperazine methane ammonium bromide

[0025]

[0026] In a similar manner to Example 1, using 4,4'-bispiperazine methane as a starting material, reacting at 25 ° C, using 1.4 mmol sodium carbonate as a base, and using chloroform as a solvent, synthesize (R, R)-bis(1 , 1'-binaphthyl-2,2'-methyleneamine)-4,4'-bispiperazine methane ammonium bromide, the yield was 88.3%. 1 H NMR (500MHz, CDCl 3 ), δppm: 1.19-1.22 (m, CH 2, 2H), 1.72-1.77(m, 2XCH, 2H), 1.81-1.88(m, 2XCH, 2H), 2.10-2.22(m, 2XCH, 2H), 2.29-2.33(m, 2XCH, 2H), 2.35- 2.37(m, 2XCH, 2H), 3.37-3.42(m, 2XCH, 2H), 3.52-3.55(m, 2XCH, 2H), 3.63-3.74(m, 6XCH, 6H), 3.96(d, J=13.0Hz , 2H), 4.50(d, J=13.0Hz, 2H), 5.09(d, J=13.0Hz, 2H), 7.38-7.48(m, Ar-H, 8H), 7.62-7.65(m, Ar-H , 4H), 7.83-7.91 (m, Ar-H, 4H), 8.12-8.13 (m, Ar-H, 4H), 8.22-8.25 (m, Ar-H, 4H).

[0027] The catalyst is used to catalyze the conjugated addition rea...

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Abstract

The invention is concerned with chiral bis-spironaphthoxazine ammonium salt phase-transfer activator and its produce method. The 3, 3'-disubstitute-2, 2'-bihalogenated methyl-1, 1' binaphthalene react with 4, 4'-bipiperazine alkane in organic solvent with alkali at 0 to 120 degree to get the aimed chiral bis-spironaphthoxazine ammonium salt phase-transfer activator after washing, extraction and separation. The mol ratio of 3, 3'-disubstitute-2, 2'-bihalogenated methyl-1, 1' binaphthalene, 4, 4'-bipiperazine alkane and alkali is 2:1:2 to 8. This activator can be used to catalyse the conjugate addition reaction of nitroparaffin and alpha, beta-unsubstituted carbonyl compounds with 90 to 99 percent of productivity and the the ee value of reflection selectivity is 60 to 97 percent.

Description

technical field [0001] The invention relates to a novel chiral double-spiro ring quaternary ammonium salt phase transfer catalyst, and specifically discloses a class of binaphthyl axis-containing chiral double-spiro ring quaternary ammonium salt phase transfer catalyst and a preparation method thereof. Background technique [0002] Chiral quaternary ammonium salts are an important class of organic small molecule phase transfer catalysts, which exhibit very high chiral induction ability in many catalytic asymmetric reactions (O'Donnell, M.J.In Catalytic Asymmetric Synthesis, 2nd ed.; Ojima, I., Ed.; WILEY-VCH: New York, 2000; Chapter 10.(b) Shioiri, T. In Handbook of Phase-Transfer Catalysis; Sasson, Y., Neumann, R., Eds.; Blackie Academic & Professional: London, 1997; Chapter 14. (c) O'Donnell, M.J. Phases-The Sachem Phase Transfer Catalysis Review; 1998; Issue 4, p 5. (d) O'Donnell, M.J. Phases-The Sachem Phase Transfer Catalysis Review; 1999 ...

Claims

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Application Information

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IPC IPC(8): B01J31/02C07B53/00C07D487/10
Inventor 马军安华明清王琏聂晶
Owner TIANJIN UNIV
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