Iron-catalyzed transfer hydrogenation of esters to alcohols

一种催化剂、预催化剂的技术，应用在有机化学领域，能够解决昂贵、高氢气压力等问题

Active Publication Date: 2020-04-17
EASTMAN CHEM CO
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, such efforts face one or more disadvantages, such as requiring the use of expensive noble metal catalysts, high temperatures, and / or high hydrogen pressures

Method used

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  • Iron-catalyzed transfer hydrogenation of esters to alcohols
  • Iron-catalyzed transfer hydrogenation of esters to alcohols
  • Iron-catalyzed transfer hydrogenation of esters to alcohols

Examples

Experimental program
Comparison scheme
Effect test

example

[0114] General experiment information

[0115] Unless otherwise stated, all organometallic compounds were prepared and handled under a nitrogen atmosphere using standard Schlenk and glove box techniques. Anhydrous EtOH (200 proof alcohol) and toluene were purchased from Sigma Aldrich and used Molecular sieve preservation. Both EtOH and toluene were freshly distilled before use. Dimethyl 1,4-cyclohexanedicarboxylate (DMCD, mixture of cis and trans isomers, >90% purity) was purchased from Alfa Aesar and used without further purification. Compounds 1a-c have been previously reported in the literature. They were synthesized according to procedures slightly modified from literature procedures.

example 1

[0117] 1a[( iPr Synthesis of PNHP)Fe(H)(CO)(Br)]

[0118]

[0119] In a glove box, under a nitrogen atmosphere, a 200-mL oven-dried Schlenk flask was charged with the complex [ iPr PNHP]FeBr 2 (CO) (850mg, 1.545mmol), NaBH 4 (60 mg, 1.545 mmol, 98% purity) and 100 mL of dry EtOH. The resulting yellow solution was stirred at room temperature for 18 hours and filtered through Celite. The filtrate was evaporated to dryness to afford pure 1a (86% isolated yield). 1a 1 H and 31 P{ 1 H} NMR spectra are in good agreement with reported values ​​(see S. Chakraborty et al., J. Am. Chem. Soc. 2014, 136, 7869).

example 2

[0121] 1b[( iPr PNHP)Fe(H)(CO)(HBH 3 )] improved synthesis of

[0122]

[0123] In a glove box, under a nitrogen atmosphere, a 200-mL oven-dried Schlenk flask was charged with the complex [ iPr PNHP]FeBr 2 (CO) (850mg, 1.545mmol), NaBH 4 (131 mg, 3.399 mmol, 98% purity) and 100 mL of dry EtOH. The resulting yellow solution was stirred at room temperature for 18 hours and filtered through Celite. The filtrate was evaporated to dryness to afford pure 1b (isolated yield 84%). 1b 1 H and 31 P{ 1 H} NMR spectra are in good agreement with reported values ​​(see S. Chakraborty et al., J. Am. Chem. Soc. 2014, 136, 7869).

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Abstract

Iron-based homogeneous catalysts, supported by pincer ligands, are employed in the transfer hydrogenation of esters using C2-C12 alcohols as sacrificial hydrogen donors to produce corresponding alcohols from the esters. No external H2 pressure is required. The reaction can be carried out under ambient pressure.

Description

technical field [0001] The present invention relates generally to the field of organic chemistry. It is particularly concerned with the catalytic transfer of hydrogen from alcohols to esters to form the corresponding alcohols from the esters. Background technique [0002] Hydrogenation of esters is an important process. It is commonly used to manufacture alcohols on an industrial scale for a variety of applications, including plasticizers and polyester synthesis. Industrially, ester hydrogenation is usually carried out under very harsh reaction conditions (250-300 ° C and 2000-5000 psig H 2 pressure), with a heterogeneous catalyst (such as copper chromite). These harsh conditions often result in lower selectivity to the desired alcohol product due to the formation of various by-products. From the perspective of energy cost and safety, there is an urgent need to develop a homogeneous catalytic system for ester hydrogenation, which may be effective under milder conditions ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/147C07C31/27B01J31/18B01J31/20
CPCB01J31/189B01J31/20C07C29/147C07C2601/14B01J2231/641B01J2531/842B01J2231/643B01J2531/0258B01J31/121C07C31/276B01J31/0202B01J31/24C07C29/1285C07F15/025
Inventor 苏米特·查克拉博蒂维卡姆·塞沙德里史蒂文·J·亚当斯罗伯特·托马斯·赫姆瑞斯科特·唐纳德·巴尼克
Owner EASTMAN CHEM CO
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