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Method for synthesizing levorotatory citronellol by asymmetric hydrosilation of citral

A technology of citral and citronellol, which is applied in the direction of organic chemical methods, chemical instruments and methods, and the preparation of organic compounds, can solve the problems of high cost, long reaction time, and large energy consumption, and achieve reduced dosage and yield And the effect of high enantioselectivity and simple reaction operation

Active Publication Date: 2020-04-07
WANHUA CHEM GRP CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

It solves the disadvantages of high energy consumption, high cost and long reaction time in the preparation of L-optical citronellol in the prior art, and can achieve high yield, high enantioselectivity and low raw material by simple operation and mild reaction conditions. Synthesis of L-optical citronellol at low cost

Method used

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  • Method for synthesizing levorotatory citronellol by asymmetric hydrosilation of citral
  • Method for synthesizing levorotatory citronellol by asymmetric hydrosilation of citral
  • Method for synthesizing levorotatory citronellol by asymmetric hydrosilation of citral

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Experimental program
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Embodiment 1

[0050] Embodiment 1: In the glove box, [Ru(COD)Cl 2 ] (2.8mg, 0.01mmol), L1-BINAP (7.6mg, 0.012mmol) and toluene (230.65g) were added to a single-necked bottle equipped with a magnetic stirrer, and the stirring was started, and the metal precursor and the ligand were dissolved and coordinated After 30 minutes, the light yellow catalyst solution was obtained. The one-mouth bottle was sealed, and the glove box was taken out. Under the protection of nitrogen, it was pumped into a 2L reaction kettle with an advection pump. The reaction kettle was replaced with nitrogen in advance, and the substrate citral (76.88 g, 0.5mol), triphenylsilane (289.33g, 1.1mol) and NbCl 5 (27.29 g, 0.1 mol). After the addition of the catalyst solution, the reactor was turned on for stirring and heat tracing. When the inner temperature of the reactor reached 40° C., the timing was started and the reaction was kept for 3 hours. The reaction kettle is cooled to room temperature, the reaction kettle is ...

Embodiment 23

[0055] In the glove box, the [Ru(COD)Cl 2 ] (1.4mg, 0.005mmol), L5 (4.6mg, 0.006mmol) and dichloromethane (230.65g) were added to a single-necked bottle equipped with a magnetic stirrer, and the stirring was started, and the metal precursor and the ligand were dissolved and coordinated After 30 minutes, the light yellow catalyst solution was obtained, the one-mouth bottle was sealed, and the glove box was taken out, and under the protection of nitrogen, it was squeezed into a 2L reaction kettle with an advection pump, and the reaction kettle was replaced with nitrogen in advance, and the substrate citral (orange Flower aldehyde and geranial ratio=46:54, 76.88g, 0.5mol), triphenylsilane (289.33g, 1.1mol) and NbCl 5 (6.82 g, 0.025 mol). After the addition of the catalyst solution was complete, the reaction kettle was started to stir, and the reaction was kept at 20° C. for 6 hours. Open the reactor, remove the solvent dichloromethane by distillation under reduced pressure, the...

Embodiment 24

[0057] In the glove box, the [Ru(COD)Cl 2 ] (1.4mg, 0.005mmol), L5 (8.4mg, 0.011mmol) and tetrahydrofuran (153.76g) were added to a single-necked bottle equipped with a magnetic stirrer, and the stirring was started, and the metal precursor and ligand were dissolved and coordinated for 30 minutes Finally, the light yellow catalyst solution is obtained, the one-mouth bottle is sealed, and the glove box is taken out, and under the protection of nitrogen, it is squeezed into a 2L reactor with an advection pump, and the reactor has been replaced with nitrogen in advance, and the substrate citral (neral and geranial ratio=81:19, 153.76g, 1.0mol), triphenylsilane (578.69g, 2.2mol) and NbCl 5 (136.45 g, 0.5 mol). After the addition of the catalyst solution was complete, the reaction kettle was started to stir, and the reaction was kept at 20° C. for 4 hours. Open the reaction kettle, remove the solvent tetrahydrofuran by distillation under reduced pressure, and then rectify under r...

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Abstract

The invention provides a method for synthesizing levorotatory citronellol from citral through asymmetric hydrosilation. The method comprises following steps: under the catalytic action of a chiral ruthenium complex, monohydrosilane is used as a hydrosilylation reagent, a Lewis acid is used as an auxiliary agent, and citral is subjected to asymmetric hydrosilylation to obtain levorotatory citronellol. According to the method, the ruthenium complex which is relatively low in price is used as the catalyst, meanwhile, the use amount of the ruthenium complex is effectively reduced, the maximum molar ratio of the chiral ruthenium complex to citral can reach 1: 30000, and the cost of the catalyst is remarkably reduced.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a method for preparing L-optical citronellol. Background technique [0002] Citronellol is a very important monoterpene fragrance, which has an odor similar to that of roses. It is often used in rose fragrance, citrus fragrance and many fragrances containing citronellol esters. [0003] There are asymmetric atoms in the molecule of citronellol, which are optically active, and usually exist in the form of a mixture of left-handed and right-handed. The aroma of the left-handed citronellol is more elegant than that of the right-handed. The citronellol present in geranium oil and citronella oil is mainly dextrorotary, and the citronellol present in rose oil and essential oil of geranium is mainly levorotatory. Among them, L-citronellol can be used to synthesize relatively expensive L-rose ether. [0004] Asymmetric hydrogenation of citral to prepare optically active cit...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/17C07C33/025
CPCC07C29/175C07F7/1804C07F7/188C07B2200/07C07C33/025
Inventor 沈稳黄文学王中华谢硕张永振黎源苏黎明
Owner WANHUA CHEM GRP CO LTD