Preparation of caprolactone, caprolactam, 2,5-etrahydrofuran-dimethanol, 1,6-hexanediol or 1,2,6-hexanetriol from 5-hydroxymethyl-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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AI-Extracted 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 le...

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.

Application Domain

Lactams preparationPreparation by oxygen reduction

Technology Topic

MethanolDiol +9

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Examples

Experimental program(11)

Example Embodiment

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

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

Example

[0098] Examples 2-15 Hydrogenation of 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 1000 rpm, and after three vacuum/nitrogen cycles, bring the autoclave at 5 MPa H 2 Pressurize and increase the temperature to 75°C. After 1.5 hours, the hydrogen pressure was increased to 9 MPa, and the temperature was increased to 200°C. The autoclave was kept stirring under these conditions for an additional 14 hours. After cooling to room temperature, the pressure was released and GC analysis of the contents of the autoclave indicated the presence of 30% THFDM.

[0100] In the same way, 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/C(ALD)5% 30 3 Ru/C(JM)5% 46 4 Ru/C(JM)0.5% 12 5 Pd/C 10% 38 6 G-69B(Sud) 55 7 Ra-Ni 79 8 CuCr(ALD) 9 9 CuCr(AC) 11 10 CuCr-Pd/C 62

[0103] Providers in parentheses: ALD=Aldrich; JM=Johnson Matthey; Sud=sudchemie; AC=Across

[0104] a 100% conversion of the starting material was observed in all cases.

[0105] It is clear from these results that Raney nickel (Ra-Ni) is a very good catalyst for this transformation.

[0106] Examples 11-15 (summarized in Table 2) show the effect of temperature on hydrogenation of HMF using Raney nickel in methanol at 9 MPa.

[0107] Table 2: Hydrogenation of HMF using Ra-Ni at different temperatures a

[0108] Example temperature Yield of 2,5-THF-dimethanol 11 250 50 12 200 79 13 150 88 14 100 99 15 75 91

[0109] a 100% conversion of the starting material was observed in all cases.

[0110] It is clear from these results that 100 °C is the optimal temperature for hydrogenation from HMF to THFDM using Ra-Ni, and that Ra-Ni is a suitable catalyst.

Example

[0111] Examples 16-22: Hydrogenation of 1,6-Hexanediol from THFDM

[0112] In a 100 ml autoclave under stirring, 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 1000 rpm, and after three vacuum/nitrogen cycles, bring the autoclave at 10 MPa H 2 Pressurize and increase the temperature to 260°C. The autoclave was kept under stirring for an additional 6 hours under these conditions. After cooling to room temperature, the pressure was released and GC analysis of the contents of the autoclave indicated 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％ 2.0％ 19 CuZn(Sud T-2 130 28％ 2.2％ 1.1％

[0115] In Examples 20 to 22, the effect of temperature and time on the hydrogenation of THFDM using CuCr in the same experiments as in Example 16 was investigated.

[0116] Table 4: Hydrogenation of THFDM using CuCr

[0117] Example time temperature 1,6-Hexanediol 1,2,6-Hexanetriol 20 6h 260℃ 17％ 4％ 21 15h 260℃ 22％ 1％ 22 6h 320℃ 15％ 0％

[0118] Preparation of Rh/Re catalysts used in Examples 23-32

[0119] Unless otherwise mentioned, the silica was pre-calcined at 773K for 3 hours prior to impregnation. 2g silica with 176mg RhCl 3 The aqueous solution was stirred together for 2 hours. Then, the water was filtered off and the residual solid was dried at 383K for 13-14 hours. Next, after filtration and drying, the solid was immersed in 113 mg of NH 4 ReO 4 , followed by a final step of calcination at 773 K in air for 3 h.

[0120] The catalyst was tested to have a Rh content of 4 wt% and a Re content of 2 wt%.

[0121] It is also possible to use two solutions in one impregnation step. The catalyst thus prepared was tested in Example 24.

[0122] Support materials other than silica, such as alumina or cerium oxide, can also be used.

[0123] For comparison, catalysts impregnated with Rh (tested in Example 25) or Re (tested in Example 26) only were also prepared according to the above procedure. Results for all four types of catalysts can be found in Table 5.

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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

AI-Extracted Technical Summary

Problems solved by technology

Abstract

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Examples

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Description & Claims & Application Information