Method for preparing cis-pinane by asymmetric catalytic hydrogenation of alpha-pinene

A catalytic hydrogenation and asymmetric technology, applied in the chemical industry, can solve the problems of difficult recovery of catalysts for product separation, low cis-pinane content and high requirements for reaction equipment, and achieve the effects of easy separation, high conversion rate and mild reaction conditions.

Inactive Publication Date: 2014-08-27
KUNMING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] In the currently used method for preparing cis-pinane by hydrogenating α-pinene, the catalyst is mostly a nickel catalyst. Although its production cost is relatively low, the reaction temperature and pressure are high, and the requirements for reaction equipment are high, and the operating conditions are harsh. The safety hazard is large, and the content of

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] The preparation of the catalyst described in this embodiment specifically includes the following methods:

[0027] ① In a nitrogen atmosphere, add RhCl at 0.013g / mL 3 ·3H 2 O is slowly heated and dissolved in ethanol to obtain RhCl 3 ·3H 2 A mixed solution of O, the solution is heated to 75°C to form solution A;

[0028] ②Press RhCl 3 ·3H 2 O and PPh 3 The newly recrystallized PPh in a molar ratio of 1:4 3 Dissolve in hot deoxygenated ethanol (95%) to form solution B;

[0029] ③ Add solution B to solution A according to the ratio of solution A to solution B volume ratio of 0.65:1 to generate orange-brown precipitate, further reflux, after 0.1h the precipitate turns purple, continue to reflux for 4h;

[0030] ④ Filtrate the product obtained in ③ under reduced pressure while it is hot, and wash 3 times with deoxygenated ether;

[0031] ⑤The crystals obtained in ④ were dried under vacuum conditions at 35°C for 8h to obtain the rhodium-phosphine complex RhCl(PPh 3...

Embodiment 2

[0040] The preparation of the catalyst described in this embodiment specifically includes the following methods:

[0041] ① In a nitrogen atmosphere, add RhCl at 0.029g / mL 3 ·3H 2 O is slowly heated and dissolved in ethanol to obtain RhCl 3 ·3H 2 A mixed solution of O, the solution is heated to 85°C to form solution A;

[0042] ②Press RhCl 3 ·3H 2 O and PPh 3 The newly recrystallized PPh at a molar ratio of 1:8 3 Dissolve in hot deoxygenated ethanol (95%) to form solution B;

[0043]③ Add solution B to solution A according to the ratio of solution A to solution B volume ratio of 0.33:1 to generate orange-brown precipitate, further reflux, after 0.5h the precipitate turns purple, continue to reflux for 1h;

[0044] ④ Filtrate the product obtained in ③ under reduced pressure while hot, and wash 5 times with deoxygenated ether;

[0045] ⑤The crystals obtained in ④ were dried under vacuum conditions at 25°C for 16h to obtain the rhodium-phosphine complex RhCl(PPh 3 ) 3 ...

Embodiment 3

[0054] The preparation of the catalyst described in this embodiment specifically includes the following methods:

[0055] ① In a nitrogen atmosphere, add RhCl at 0.021g / mL 3 ·3H 2 O is slowly heated and dissolved in ethanol to obtain RhCl 3 ·3H 2 A mixed solution of O, the solution is heated to 65°C to form solution A;

[0056] ②Press RhCl 3 ·3H 2 O and PPh 3 The newly recrystallized PPh at a molar ratio of 1:6 3 Dissolve in hot deoxygenated ethanol (95%) to form solution B;

[0057] ③ Add solution B to solution A at a volume ratio of 0.2:1 to solution A to form an orange-brown precipitate, which is further refluxed. After 1 hour, the precipitate turns purple, and continues to reflux for 5 hours;

[0058] ④ Filtrate the product obtained in ③ under reduced pressure while hot, and wash 5 times with deoxygenated ether;

[0059] ⑤The crystals obtained in ④ were dried under vacuum conditions at 35°C for 8h to obtain the rhodium-phosphine complex RhCl(PPh 3 ) 3 ;

[0060...

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Abstract

The invention discloses a method for preparing cis-pinane by asymmetric catalytic hydrogenation of alpha-pinene, and belongs to the chemical engineering field. The method comprises the process steps: in a nitrogen atmosphere, heating RhCl3.3H2O to dissolve in an ethanol solution, and forming a solution A; dissolving newly recrystallized PPh3 in a deoxygenated ethanol, and forming a solution B; adding the solution B into the solution A, refluxing for a certain period of time, filtering under reduced pressure while being hot, washing with deoxygenated ether, carrying out vacuum drying to obtain a rhodium phosphine complex RhCl(PPh3)3; and adding the prepared rhodium phosphine complex RhCl(PPh3)3, an ionic liquid and alpha-pinene into a high-pressure reaction kettle according to a certain proportion, putting a cover and sealing, respectively replacing with nitrogen gas and hydrogen gas, carrying out pressure maintaining and leakage detection, and carrying out a reaction under certain conditions to prepare cis-pinane. The method has the advantages of mild reaction conditions, high conversion rate of alpha-pinene and high enantioselectivity of cis-pinane; the ionic liquid catalyst system is easily separated from the product and can be recycled; and the process flow is simple, and the energy consumption is low.

Description

technical field [0001] The invention relates to a method for preparing cis-pinane by asymmetric catalytic hydrogenation of α-pinene, which belongs to the field of chemical industry. Background technique [0002] α-pinene is the main component of turpentine, α-pinene can be produced by catalytic hydrogenation of pinane, pinane is an important raw material for the perfume and pharmaceutical industry, and is used to prepare linalool, citronellol, rose ether and dihydrogen An important intermediate of fragrances such as myrcenol. There are cis- and trans-isomers of pinane, because the reactivity of cis-pinane is much higher than that of trans-pinane, so the pinane used in the perfume industry requires cis-pinane as the main one. [0003] In the currently used method for preparing cis-pinane by hydrogenation of α-pinene, the catalyst is mostly a nickel catalyst. Although its production cost is low, the reaction temperature and pressure are high, and the requirements ...

Claims

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Application Information

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IPC IPC(8): C07C5/03C07C13/40B01J31/24
Inventor 蒋丽红王亚明李丹丹贾庆明陕绍云韩欢杨晨刘坤
Owner KUNMING UNIV OF SCI & TECH
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