Chiral dinaphtholsiloxane derivatives and preparation method thereof

A technology for binaphthol siloxane and derivatives, which is applied in the field of chiral binaphthol siloxane derivatives and their preparation, can solve the problems of weak bond and force between metals and ligands, poor catalytic reactivity and selectivity, and load The problem of small specific surface area of ​​the catalyst, to achieve the effect of easy to obtain and simple steps

Inactive Publication Date: 2008-02-13
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Another example is the document {Hesemann P., Moreau J.J.E. Acta Chemometrica (France) 2003, 6, 199-207}, after the phenolic hydroxyl group in binaphthol directly reacts with isocyanate group triethoxysilane, the chiral binaphthyl obtained Phenol siloxane derivatives, cyclooctadienyl rhodium(I) chloride dimer, tetraethoxys

Method used

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  • Chiral dinaphtholsiloxane derivatives and preparation method thereof
  • Chiral dinaphtholsiloxane derivatives and preparation method thereof

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Embodiment 1

[0016] The general structural formula is (III), wherein, R is selected from -CH 2 OCH 3 Preparation of chiral binaphthol siloxane derivative 6,6'-bis(triethoxysilylpropylamino ester)methyl-2,2'-dimethoxymethoxybinaphthyl.

[0017] Compound (R)-6,6'-dimethylol-2,2'-dimethoxymethoxybinaphthyl 0.70g (1.60mmol), isocyanatopropyltriethoxysilane 1.58mL (6.40 mmol), triethylamine 0.91mL (6.40mmol) was dissolved in 15mL toluene, stirred under the protection of nitrogen, heated to reflux for 24 hours, cooled, filtered to remove insoluble matter, the filtrate was distilled under reduced pressure to remove toluene, and used petroleum ether: ethyl acetate = 2:1 as the eluent, separated by flash column chromatography to obtain 1.11 g of the target product as a white solid, with a yield of 74.5%. It was proved by NMR and elemental analysis that it was indeed the target compound:

[0018] 1 H NMR (CDCl 3 )δ: 8.06 (s, 2H), 7.83-7.85 (d, 2H), 7.40-7.44 (d, 2H), 7.32-7.34 (d, 2H), 7.20-7.2...

Embodiment 2

[0020] The general structural formula is (III), wherein, R is selected from -CH 3 Preparation of chiral binaphthol siloxane derivative 6,6'-bis(triethoxysilylpropylamino ester)methyl-2,2'-dimethoxybinaphthyl.

[0021] Compound (R)-6,6'-dimethylol-2,2'-dimethoxybinaphthyl 0.60g (1.60mmol), isocyanatopropyltriethoxysilane 1.58mL (6.40mmol), Triethylamine 0.91mL (6.40mmol) was dissolved in 15mL toluene, stirred under nitrogen protection, heated to reflux for 26 hours, cooled, filtered to remove insoluble matter, and the filtrate was distilled under reduced pressure to remove toluene, using petroleum ether: ethyl acetate = 5: 1 was used as the eluent to separate by flash column chromatography to obtain 1.09 g of the target product as a white solid, with a yield of 78.5%. It was proved by NMR and elemental analysis that it was indeed the target compound:

[0022] 1 HNMR (CDCl 3 )δ: 8.02 (s, 2H), 7.80-7.82 (d, 2H), 7.40-7.44 (d, 2H), 7.31-7.33 (d, 2H), 7.19-7.22 (d, 2H), 6.13-6....

Embodiment 3

[0024] The general structural formula is (III), wherein, R is selected from-C 12 h 25 Preparation of chiral binaphthol siloxane derivative 6,6'-bis(triethoxysilylpropylamino ester)methyl-2,2'-bis(dodecyloxy)binaphthyl.

[0025]Compound (R)-6,6'-dimethylol 2,2'-bis(dodecyloxy)binaphthyl 0.82g (1.20mmol), isocyanatopropyl triethoxysilane 1.48mL (6.00 mmol), triethylamine 0.85mL (6.00mmol) was dissolved in 15mL toluene, stirred under the protection of nitrogen, heated to reflux for 30 hours, cooled, filtered to remove insoluble matter, the filtrate was distilled under reduced pressure to remove toluene, and used petroleum ether: ethyl acetate =3:1 as the eluent, separated by flash column chromatography to obtain 0.95 g of the target product as a colorless oil, with a yield of 66.3%. It was proved by NMR and elemental analysis that it was indeed the target compound:

[0026] 1 HNMR (CDCl 3 )δ: 8.04 (s, 2H), 7.82-7.84 (d, 2H), 7.41-7.45 (d, 2H), 7.33-7.35 (d, 2H), 7.21-7.24 (d...

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Abstract

The invention relates to a chiral linking naphthol siloxane derivative connected by the 6, 6-propylamine amide methyl and the preparation method. The invention is characterized in the structural formula; therein, R is chosen from the - CH2OCH3,-CH3, -C12H25 or - C16H33. After the later graft or copolycondensation to be loaded on the mesoporous silicon dioxide, the chiral linking naphthol siloxane derivative provided in the invention can be used in a plurality of catalytic reactions, such as the asymmetric synthetic reaction of the diethyl zinc and the benzaldehyde, the asymmetric Baylis-Hillman reaction, and so on. Therein, the linking naphthol siloxane derivative protected by the methoxy methyl can be used to prepare the mesoporous material after the copolycondensation or the later graft to protect the easy doffing of the base groups, and can be directly used in the catalytic reaction; the linking naphthol siloxane derivative protected by the long-chain alkyl can be used as the siloxane modifying reagent and the surfactant at the same time to prepare the complex mesoporous material. In the synthesis method of the chiral linking naphthol siloxane derivative, the raw materials are easy to access; the synthesis process is simple and easy.

Description

technical field [0001] The invention relates to a chiral binaphthol siloxane derivative connected with a propylamino ester group methyl group at the 6,6' position and a preparation method thereof. Background technique [0002] have C 2 The chiral 1,1'-bi-2-naphthol and its derivatives of the symmetry axis have been widely used in asymmetric synthesis and molecular recognition {Pu, L. Chemical Review (USA) 1998, 98, 2405.; Chen Y.; Yekta S.; Yudin A.K. Chemical Reviews (USA) 2003, 103, 3155.}. In recent years, the loading of chiral ligands on mesoporous silica for asymmetric catalysis has received great attention {Dirk E.D.; Dams M.; Sels B.F.; Jacobs P.A. Chemical Reviews (USA) 2002, 102, 3615 .}. The main loading methods are co-polycondensation and post-grafting modification, and the siloxane derivatives of chiral ligands can be co-condensed with tetraalkoxy silicon or post-grafted with blank mesoporous silica. grafting reaction to complete the loading of chiral ligands...

Claims

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Application Information

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IPC IPC(8): C07F7/18
Inventor 王晓梅高连勋姬相玲邱雪鹏
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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