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Chiral diphosphite ligand and iridium composite catalyst and preparation thereof method and application to asymmetrical hydrogenization synthesis (S)-metolachlor

A technology of chiral bisphosphine ligands and composite catalysts, applied in asymmetric synthesis, organic compound/hydride/coordination complex catalysts, organic chemistry methods, etc.

Active Publication Date: 2010-10-13
NANJING UNIV OF TECH +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, the ee value of (S)-metolachlor produced by asymmetric hydrogenation route only reaches about 80%, and there is still room and need for improvement

Method used

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  • Chiral diphosphite ligand and iridium composite catalyst and preparation thereof method and application to asymmetrical hydrogenization synthesis (S)-metolachlor
  • Chiral diphosphite ligand and iridium composite catalyst and preparation thereof method and application to asymmetrical hydrogenization synthesis (S)-metolachlor
  • Chiral diphosphite ligand and iridium composite catalyst and preparation thereof method and application to asymmetrical hydrogenization synthesis (S)-metolachlor

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Preparation of Example 1 Ligand Ia (General Structural Formula I, R=methyl)

[0033]Under the protection of nitrogen, add (R)-(S)-1-dimethylaminoethylferrocene (III, 0.1mol) and absolute tetrahydrofuran (100mL) to the reaction flask successively, and control the reaction flask with a dry ice-acetone bath. The temperature does not exceed -45~-35°C, add butyllithium n-hexane solution (0.11mol) dropwise, keep warm at -35°C for 30min, slowly rise to 40°C, keep warm for 1h, add diphenyl chloride dropwise Phosphine tetrahydrofuran solution, after the dropwise addition, keep warm for 6h. The reaction system was lowered to 0°C, and saturated aqueous sodium bicarbonate solution was added dropwise, the organic layer was separated with a separatory funnel, the aqueous layer was extracted with ether (3×30mL), the organic layers were combined, dried over anhydrous sodium sulfate, and filtered , precipitation, the obtained reddish-brown oily crude product is done column chromatograp...

Embodiment 2

[0035] Preparation of Example 2 Ligand Ib (such as general structural formula I, R=tert-butyl)

[0036] Use phosphonane IVb (IV, R = tert-butyl, 0.11mol) to replace phosphonane IVa, and (R)-N, N-dimethyl-1-[(S)-2-(diphenylphosphino) Ferrocenyl]ethylamine was prepared according to the same operation steps in Example 1 to obtain bisphosphine ligand Ib with a yield of 72% and a melting point of 50-52°C.

Embodiment 3

[0037] Preparation of Example Three Ligand Ic (such as general structural formula I, R=ethyl)

[0038] Use phosphonane IVc (IV, R = ethyl, 0.11mol) instead of phosphonane IVa, and (R)-N, N-dimethyl-1-[(S)-2-(diphenylphosphino) di Ferrocenyl]ethylamine was prepared according to the same operation steps in Example 1 to obtain bisphosphine ligand Ic with a yield of 72% and a melting point of 63-66°C.

[0039] The preparation of embodiment three composite catalysts Ia-Ir and the hydrogenation reaction of EMA-imine

[0040] Diphosphine ligand Ia (0.01mmol), [Ir(cod)Cl] 2 (0.005mmol), tetrabutylammonium iodide (0.005mmol), and glacial acetic acid (5mL) were mixed, and stirred at room temperature for 5min to obtain in-situ catalysts Ia-Ir.

[0041] Freshly distilled EMA-imine (1 mol), glacial acetic acid (80 mL) were added to a 500 mL autoclave.

[0042] Catalysts Ia-Ir were added into the reactor, and after gas exchange, the pressure was adjusted to 90 kg and the hydrogenation re...

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Abstract

The invention relates to a kind of chiral diphosphite ligands, an iridium composite catalyst thereof, a preparation method and application thereof. The ligands are obtained through using chiral (R)-(S)-1-dimethylamino ethyiferroene as raw materials to react with diphenyl phosphonium chloride under the effect of butyl lithium and then to carry out displacement reaction with diaryl phosphine alkane. The chiral diphosphite ligands respectively act with homotropilidene compositions of iridous chloride, tetrabutyl ammonium iodide and glacial acetic acid, and imine asymmetrical hydrogenization catalysts can be obtained. When the iridium-diphosphine catalysts are used for catalyzing 2-methyl-6-ethyl-N-methylene aniline (EMA-imine) hydrogenization reaction, (S)-N-(1-anisyl-2-propyl)-2-methyl-6- ethylaniline ((S)-NNA) can be obtained, and the antimer excessive value (ee) can reach 86.5 percent. The (S)-NNA and chloracetyl chloride carry out acylation reaction to obtain (S)-metolachlor with the ee value of 86 percent. Thereby, the ligands provided by the invneiton can be used for synthesizing chiral herbicidal chemicals of (S)-metolachlor.

Description

technical field [0001] The invention belongs to the technical field of chiral pesticide production. Chiral bisphosphine ligand provided by the invention and iridium-cyclooctadiene complex ([IrCl(cod)] 2 ), tetrabutylammonium iodide and glacial acetic acid, the chiral bisphosphine ligand and iridium composite catalyst can be applied to the asymmetric hydrogenation reaction of imine, and then can be used for chiral herbicide (S-) isopropyl Production of alachlor. technical background [0002] Metolachlor (trade name: Dual) is a broad-spectrum herbicide developed by the former Ciba-Geigy Company. It is low-toxic to humans and animals and can be used to control annual grass weeds and other crops in corn and other dry fields. Broadleaf weeds. Studies have found that metolachlor has four stereoisomers, one chiral axis and one chiral center, and 95% of the herbicidal activity exists in the (1'S)-diastereomer, and its three-dimensional structural formula is as follows: [0003] ...

Claims

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Application Information

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IPC IPC(8): C07F19/00C07F17/02B01J31/24C07C233/88C07C231/02C07B53/00
Inventor 朱红军李玉峰于国权吕良忠楚庆岩杜刚王凯施璐黄仁均
Owner NANJING UNIV OF TECH
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