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Synthesis method for preparing Salen ligand in chiral or not chiral binuclear

A synthetic method and achiral technology, applied in the field of binuclear Salen ligands, can solve problems such as troublesome product purification, and achieve the effect of reducing by-products

Inactive Publication Date: 2005-10-26
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, we have found in experiments that the products prepared by the methods provided in the literature still contain a large amount of by-products, which brings great trouble to the purification of the products.

Method used

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  • Synthesis method for preparing Salen ligand in chiral or not chiral binuclear
  • Synthesis method for preparing Salen ligand in chiral or not chiral binuclear

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0015] Add (R, R)-1,2-diaminocyclohexane mono(+) tartrate 2.77g in a single-necked flask of 50ml, anhydrous K 2 CO 3 2.9g, under the protection of nitrogen, add 15ml of distilled water, 6ml of ethanol, reflux for 3h. with 30mlCH 2 Cl 2 The released cyclohexanediamine, CH 2 Cl 2 layer anhydrous Na 2 SO 4 dry. Dried CH 2 Cl 2 layer to filter out Na 2 SO 4 After that, it was added to a 100ml single-necked flask, cooled to 0°C in an ice bath, and 23ml CH 2 Cl 2 The solution was dripped in 1 hour, and kept in an ice bath for 24 hours. Then, add dropwise 1.74 g of 5,5′-methylene bis-tert-butyl salicylaldehyde in 17 ml of CH 2 Cl 2 solution. After stirring the reaction at room temperature for 12 h, the reaction was detected by TLC, and there was no product point.

Embodiment 2

[0017] The conditions are the same as in Example 1, except that the order of addition of 3,5-di-tert-butyl salicylaldehyde and 5,5'-methylene bis-tert-butyl salicylaldehyde is changed, that is, 5,5'-methylene bis After tert-butyl salicylaldehyde was reacted for 24 hours, 3,5-di-tert-butyl salicylaldehyde was added. After the reaction was completed, TLC detection showed only a small amount of product.

[0018] As can be seen from the above two examples, the method for extracting cyclohexanediamine is not easy to obtain dinuclear ligands. Therefore, we adopt the method of not extracting cyclohexanediamine, that is, directly add 3,5-di-tert-butyl salicylaldehyde or 5,5'-methylene bis-tert-butyl after cyclohexanediamine is freed from its salt For the salicylaldehyde reaction, the following examples are the one-pot method for synthesizing the dinuclear Salen ligand without extracting cyclohexanediamine.

Embodiment 3

[0020] Add (R, R)-1,2-diaminocyclohexane mono(+) tartrate 1.901g in a 100ml single-necked flask, anhydrous K 2 CO 3 2.0g, under the protection of nitrogen, add 6ml of distilled water and stir at room temperature for 10min to dissolve the solid. Add 50ml CH 2 Cl 2 , add 12g K in two times 2 CO 3 Absorbs water inside. Cool down to 0°C in an ice bath, and start to add dropwise 5,5'-methylenebis-tert-butylsalicylaldehyde 1.104g in 20ml of CH 2 Cl 2 The solution was dripped in 1 hour, and kept in an ice bath for 24 hours. Then, add dropwise 2.527 g of 3,5-di-tert-butyl salicylaldehyde in 10 ml CH 2 Cl 2 solution. After the dropwise addition, the solid was filtered, and 80 ml of absolute ethanol was added to the solution. Reflux for 9 hours, TLC detects the reaction, and the chromatographic yield of the product is 70%. First, 80ml of solvent was evaporated, and a solid precipitated after standing still, which may be a mixture of trinuclear and dinuclear catalyst ligands....

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Abstract

The present invention provides a synthesis method for preparing chiral or achiral binuclear Salen ligand by utilizing chiral or achiral diamine and derivative of monosalicylal and disalicylal. Said method adopts the following steps: firstly, making derivative of disalicylal be reacted with excess diamine, then adding excess derivative of monosalicylal to produce synthesis reaction to prepare the invented product. The described diamine can be chiral or achiral diamine and its ammonium salt.

Description

Technical field [0001] The invention relates to a synthesis method for preparing chiral or non-chiral dinuclear Salen ligands by using chiral or non-chiral diamine, monosalicylaldehyde and disalicylaldehyde derivatives, and belongs to the field of chemical synthesis. Background technique [0002] Salen [from N, N'-bis (salicylaldehyde ethylenediamine)] is one of the most important ligands in chiral synthesis in recent years. The properties of Salen's metal complexes as catalysts are gradually being recognized, which can be called Salen-metal catalysts. Salen-metal catalysts are widely used in asymmetric catalysis and are multifunctional catalysts that can catalyze many reactions. Among them, Salen-metal catalysts can obtain nearly pure photoactive epoxy compounds and diols in the hydrolytic kinetic resolution of epoxy compounds. [0003] For the hydrolytic kinetic resolution of epoxy compounds, the Salen-Co catalyst is mainly used, and the effect is very good. For industr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C251/24
Inventor 周智明李连友余从煊
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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