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Preparation of caprolactone, caprolactam, 2,5-etrahydrofuran-<wbr/>dimethanol, 1,6-<wbr/>hexanediol or 1,2,6-<wbr/>hexanetriol from 5-<wbr/>hydroxymethyl-<wbr/>2-furfuraldehyde

A technology of tetrahydrofuran and hexanediol, applied in the field of preparing ε-caprolactam, can solve the problems of hindering microbial intermediates, laborious and the like

Active Publication Date: 2013-07-31
NEDERLANDSE ORG VOOR WETENSCHAPPELIJK ONDERZOEK NWO
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Additionally, the use of genetically modified organisms on an industrial scale would impede the microbial production of caprolactone or caprolactam intermediates, which may raise issues of legal or consumer acceptance
Finally, the fermentation process generates considerable waste streams (cell matter, growth medium) that can be quite laborious to dispose of in an acceptable manner

Method used

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  • Preparation of caprolactone, caprolactam, 2,5-etrahydrofuran-&lt;wbr/&gt;dimethanol, 1,6-&lt;wbr/&gt;hexanediol or 1,2,6-&lt;wbr/&gt;hexanetriol from 5-&lt;wbr/&gt;hydroxymethyl-&lt;wbr/&gt;2-furfuraldehyde
  • Preparation of caprolactone, caprolactam, 2,5-etrahydrofuran-&lt;wbr/&gt;dimethanol, 1,6-&lt;wbr/&gt;hexanediol or 1,2,6-&lt;wbr/&gt;hexanetriol from 5-&lt;wbr/&gt;hydroxymethyl-&lt;wbr/&gt;2-furfuraldehyde
  • Preparation of caprolactone, caprolactam, 2,5-etrahydrofuran-&lt;wbr/&gt;dimethanol, 1,6-&lt;wbr/&gt;hexanediol or 1,2,6-&lt;wbr/&gt;hexanetriol from 5-&lt;wbr/&gt;hydroxymethyl-&lt;wbr/&gt;2-furfuraldehyde

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0096] Example 1 Direct hydrogenation from HMF to 1,6-hexanediol

[0097] In a stirred 100 ml autoclave, 0.1 g of copper chromite and 0.06 g of Pd on carbon (10%) were added to a solution of 0.5 g of HMF in 25 ml of methanol. Close the lid of the autoclave, start stirring at 1000rpm, and after three vacuum / nitrogen cycles, bring the autoclave at 3MPa H 2 The pressure was lowered and the temperature was raised to 80°C. After 1.5 hours, the hydrogen pressure increased to 15Mpa, and the temperature increased to 270°C. The autoclave was continued under these conditions with stirring for an additional 14.5 hours. After cooling to room temperature, the pressure was released and GC analysis of the contents of the autoclave showed the presence of 4.2% 1,6-hexanediol and 2.3% 1,2,6-hexanetriol.

Embodiment 2～15

[0098] Examples 2-15 Hydrogenation from HMF to THFDM

[0099] In a stirred 100 ml autoclave, 0.05 g of 5 mol% Ru / C (Aldrich) was added to a solution of 0.5 g of HMF in 30 ml of methanol. Close the lid of the autoclave, start stirring at 1000rpm, and after three vacuum / nitrogen cycles, bring the autoclave at 5MPa H 2 The pressure was lowered and the temperature increased to 75°C. After 1.5 hours, the hydrogen pressure was raised to 9 MPa, and the temperature was raised to 200°C. The autoclave was continued under these conditions with stirring for an additional 14 hours. After cooling to room temperature, the pressure was released and GC analysis of the contents of the autoclave showed the presence of 30% THFDM.

[0100] In the same manner, several other catalysts were tested in this hydrogenation and the results are summarized in Table 1.

[0101] Table 1 Hydrogenation from HMF to 2,5-THF-dimethanol a

[0102] Example catalyst 2,5-THF-dimethanol% 2 Ru / ...

Embodiment 16～22

[0111] Examples 16-22: Hydrogenation from THFDM to 1,6-hexanediol

[0112] In a stirred 100 ml autoclave, 0.1 g copper chromite was added to a solution of 0.5 g THFDM in 30 ml n-propanol. Close the lid of the autoclave, start stirring at 1000rpm, and after three vacuum / nitrogen cycles, bring the autoclave under 10MPa H 2 The pressure was lowered and the temperature increased to 260°C. The autoclave was continued under these conditions with stirring for an additional 6 hours. After cooling to room temperature, the pressure was released and GC analysis of the contents of the autoclave showed the presence of 17.3% 1,6-hexanediol and 3.7% 1,2,6-hexanetriol. Other catalysts were tested under similar conditions (Table 3).

[0113] Table 3: Hydrogenation of THFDM

[0114] Example catalyst Conversion rate Yield of 1,6-hexanediol Yield of 1,2,6-hexanetriol 16 CuCr 70％ 17.3％ 3.7％ 17 CuZn (JM PR-A) 26％ 1.8％ 5.4％ 18 CuZn(JM PR-B) 71％ 2.1％ 2...

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Abstract

The present invention relates to a method for preparing caprolactone, comprising converting 5-hydroxymethyl-2-furfuraldehyde by hydrogenation into at least one intermediate compound selected from the group of 2,5-tetrahydrofuran-dimethanol, 1,6-hexanediol and 1,2,6-hexanetriol,and preparing caprolactone from said intermediate compound. Further, the invention relates to a method for preparing 1,2,6-hexanetriol comprising preparing 5-hydroxymethyl-2-furfaldehyde from a renewable source, converting 5- hydroxymethyl-2-furfaldehyde into 2,5-tetrahydrofuran-dimethanol and converting 2,5-tetrahydrofuran-dimethanol into 1,2,6-hexanetriol. Further, the invention relates to a method for preparing 1,6-hexanediol from 1,2,6- hexanetriol, wherein 1,2,6-hexanetriol is subjected to a ring closure reaction, thereby forming (tetrahydro-2H-pyran-2-yl)methanol, and the (tetrahydro-2H-pyran-2- yl)methanol is hydrogenated, thereby forming 1,6-hexane diol.

Description

technical field [0001] The present invention relates to a method for preparing ε-caprolactone (hereinafter referred to as caprolactone). The invention further relates to a process for preparing ε-caprolactam (hereinafter referred to as caprolactam) from caprolactone. Background technique [0002] Caprolactone is a particularly useful product for the preparation of caprolactam. It is also used as a raw material for the manufacture of polyesters and resins. Caprolactam is a relatively used monomer in the preparation of polyamides. [0003] Industrially, caprolactone and caprolactam are generally obtained from starting compounds derived from mineral oils such as benzene or toluene. In view of the need to use more robust techniques for the preparation of materials, there is a need to provide a method for the preparation of caprolactone or caprolactam from compounds obtainable from biorenewable sources. Further, there is a need to provide a process with a smaller ecological f...

Claims

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Application Information

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IPC IPC(8): C07D201/08C07D309/30C07D313/04
CPCC07C29/132C07D313/04C07D201/08Y02P20/52
Inventor 约翰尼斯·杰拉尔德斯·德弗里斯泰迪皮姆·华特·潘I·V·美利恩·卡布雷拉H·J·黑列斯
Owner NEDERLANDSE ORG VOOR WETENSCHAPPELIJK ONDERZOEK NWO
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