PROCESS FOR PRODUCING A TETRAHYDROFURAN COMPOUND COMPRISING AT LEAST TWO AMINE FUNCTIONAL GROUPS

Abstract

The present invention concerns a process for preparing a tetrahydrofuran compound comprising at least two amine functional groups by reacting a furan compound comprising at least two nitrogen-containing functional groups with hydrogen in the presence of a hydrogenation catalyst.

Claims

1. A process for preparing a tetrahydrofuran compound comprising at least two amine functional groups by reacting a furan compound comprising at least two nitrogen-containing functional groups with hydrogen in the presence of a hydrogenation catalyst, wherein the hydrogenation catalyst comprises: at least one noble metal element in elemental form and/or at least one noble metal compound of at least one noble metal element, or at least one metal element in elemental form and/or at least one metal compound of at least one metal element and a dopant, wherein the metal element is selected from the group consisting of (i) elements of group IA, IIA, IIIA, IVA, VA, VIA and VIIA of the Periodic Table, (ii) elements of groups IB, IIB, IIIB, IVB, VB, VIB, VIM and VIIIB of the Periodic Table, (iii) lanthanides, (iv) actinides, and (v) any combination thereof.

2. The process according to claim 1, wherein the noble metal element is selected from the group consisting of ruthenium, rhodium, palladium, silver, osmium, iridium, platinum and gold.

3. (canceled)

4. The process according to claim 1, wherein the hydrogenation catalyst is selected from the group consisting of Pd/C, Pt/C, Rh/C, Ru/C, Au/C, Pd/CeO.sub.2, Pd/Al.sub.2O.sub.3, Pt/Al.sub.2O.sub.3, Rh/Al.sub.2O.sub.3, Ru/Al.sub.2O.sub.3 and Au/Al.sub.2O.sub.3.

5. The process according to claim 1, wherein the hydrogenation catalyst comprises one and only one metal element in elemental form and a dopant, wherein the only one metal element in elemental form is selected from the group consisting of elements of groups IB, IIB and VIIIB of the Periodic Table.

6. The process according to claim 1, wherein the hydrogenation catalyst comprises a mixture comprising at least two metal elements in elemental form and a dopant.

7. The process according to claim 1, wherein the hydrogenation catalyst comprises a metal alloy comprising at least two metal elements in elemental form and a dopant.

8. The process according to claim 6, wherein the two metal elements are selected from the group consisting of Pt, Pd, Rh, Ru, Au, Ag, Ni, Co, Fe, Cu, Sn, B, Al, Si, Sb, Bi and Ge.

9. The process according to claim 7, wherein the metal alloy is selected from the group consisting of PtAu, PtPd, PtSn, PtBi, PtFe, RhAg, RhAu and Raney nickel alloys.

10. The process according to claim 9, wherein the hydrogenation catalyst is a doped NiAl Raney nickel alloy and the total aluminum content is comprised from 1% to 10% by weight with respect to the total weight of NiAl Raney nickel alloy.

11. The process according to claim 1, wherein the dopant is selected from the group consisting of elements of groups IVB, VB, VIB, VIIB and VIIIB of the Periodic Table.

12. The process according to 1, wherein the dopant is selected from the group consisting of Zn, Fe, Ti, Mo, V, Cr, Co, Mn, and combinations thereof.

13. The process according to claim 1, wherein hydrogenation catalyst is NiAl Raney nickel comprising metallic dopant elements iron and chromium.

14. The process according to claim 7, wherein the metal alloy is a Raney cobalt alloy.

15. The process according to claim 14, wherein the Raney cobalt alloy is a doped CoAl Raney cobalt alloy and the total aluminum content is comprised from 1% to 10% by weight with respect to the total weight of the CoAl Raney cobalt alloy.

16. The process according to claim 1, wherein the hydrogenation catalyst is a CoAl Raney cobalt alloy comprising metallic dopant elements nickel and chromium.

17. The process according to claim 1, wherein the furan compound comprising at least two nitrogen-containing functional groups is selected from the group consisting of 2,5-bis(azidomethyl)furan, furan-2,5-dicarbaldehyde dioxime, 2,5-bis(hydrazonomethyl)furan, 2,5-bis(aminomethyl)furan, 3-((5-(aminomethyl)furan-2-yl)methoxy)propan-1-amine, 3,3-((furan-2,5-diylbis(methylene))bis(oxy))bis(propan-1-amine), 3,3-((furan-2,5-diylbis(methylene))bis(oxy))dipropanenitrile, ((oxybis(methylene))bis(furan-5,2-diyl))dimethanamine and 3,3-((((oxybis(methylene))bis(furan-5,2-diyl))bis(methylene))bis(oxy))dipropanenitrile.

18. The process according to claim 1, wherein the tetrahydrofuran compound comprising at least two amine functional groups is selected from the group consisting of 2,5-bis(aminomethyl)tetrahydrofuran, 3-((5-(aminomethyl)tetrahydrofuran-2-yl)methoxy)propan-1-amine, 3,3-(((tetrahydrofuran-2,5-diyl)bis(methylene))bis(oxy))bis(propan-1-amine), ((oxybis(methylene))bis(tetrahydrofuran-5,2-diyl))dimethanamine and 3,3-((((oxybis(methylene))bis(tetrahydrofuran-5,2-diyl))bis(methylene))bis(oxy))bis(propan-1-amine).

19. The process according to claim 1, wherein the hydrogen has a gas pressure which is comprised from 5 to 80 bars.

20. The process according to claim 1, wherein the conversion of furan compound comprising at least two nitrogen-containing functional groups is comprised from 40% to 100%.

21. The process according to claim 1, wherein the selectivity of tetrahydrofuran compound comprising at least two amine functional groups is comprised from 60% to 100%.

Description

EXPERIMENTAL PART

Example 1

[0081] Raw materials furan-2,5-dicarbaldehyde dioxime, 2,5-bis(azidomethyl)furan and 2,5-bis(amino-methyl)furan used in these experiments were prepared from biomass derived platform chemical 5-hydromethylfurfural. Furan-2,5-dicarbaldehyde dioxime was prepared following the recipe of the prior arts (Hajj et. al. B. Soc. Chim. Fr., 1987, pp 855-860) and the others were prepared as follows.

[0082] To a 5 L round-bottomed flask equipped with a magnetic stir bar was added 2,5-bis(hydroxymethyl)furan (257 g, 2.0 mol) and a solution of diphenyl phosphoryl azide (1.2 kg, 4.4 mol) in toluene (3 L). Under stirring, DBU (732.7 g, 4.8 mol) was added drop-wise to the reaction mixture at 0 C., then warmed up to ambient temperature and stirred for 20 h. The reaction mixture was washed with water (24000 ml), HCl aqueous solution (5%, 4000 ml), and then brine (4000 ml). The organic layer was concentrated and 288 g (81% yield) of 2,5-bis(azidomethyl)furan as brown oil was obtained by distillation under vacuum (90 C./100 Pa).

[0083] Triethylamine (163.2 g, 1.6 mol) and hydrazine hydrate (564.5 g, 1.13 mol) were added to the solution of the diazide obtained above in methanol (6000 ml). Raney Ni (57.6 g) was added and the reaction mixture was stirred at 0 C. for 24 h. The catalyst was removed by filtration and the filtrate was concentrated under vacuum to give 170 g of 2,5-bis(aminomethyl)furan (pale yellow oil, 84% yield).

Example 2

[0084] Into a 100 ml parr pressure reactor, 2,5-bis(azidomethyl)furan (1.50 g, 8.4 mmol) and 10% Pd/C (0.30 g) from Zhejiang Metallurgical Research Institute Co., Ltd were added and dissolved in methanol (50 ml). The mixture was stirred at 30 C. under 10 atms H.sub.2 atmosphere for 18 h and was then filtered through celite after completion of the reaction. The filtrate was concentrated in vacuo to give 1.05 g of pale brown oil (90% isolated yield). .sup.1HNMR showed that 2,5-bis(aminomethyl) tetrahydrofuran was obtained in the ratio between cis and trans isomers of about 65:35.

Example 3

[0085] Into a 30 ml autoclave, furan-2,5-dicarbaldehyde dioxime (153 mg, 1.0 mmol) and 5% Pd/C (47 mg) from Johnson Matthey were added and dissolved in methanol (5 ml). The mixture was stirred at 50 C. under 35 atms H.sub.2 atmosphere for 18 h. The reaction mixture, after completion of the reaction, was analysed by GC. It was shown 2,5-bis(aminomethyl) tetrahydrofuran was obtained in 50% yield while the bicyclic compound 8-oxa-3-azabicyclo[3.2.1]octane appeared as byproduct in 5% yield.

Example 4

[0086] Into a 30 ml autoclave, furan-2,5-dicarbaldehyde dioxime (312 mg, 2.0 mmol) and 5% Pd/Al.sub.2O.sub.3 (28 mg) from Johnson Matthey were added and dissolved in methanol (5 ml). The mixture was stirred at 100 C. under 45 atms H.sub.2 atmosphere for 18 h. The reaction mixture, after completion of the reaction, was analysed by GC. It was shown 2,5-bis(aminomethyl) tetrahydrofuran was obtained in 50% yield while the bicyclic compound 8-oxa-3-azabicyclo[3.2.1]octane appeared as byproduct in 4% yield.

Example 5

[0087] Into a 30 ml autoclave, 2,5-bis(aminomethyl)furan (134 mg, 1.06 mmol) and 5% Pd/C (50 mg) from Johnson Matthey were added and dissolved in methanol (5 ml). The mixture was stirred at 50 C. under 35 atms H.sub.2 atmosphere for 18 h. The reaction mixture, after completion of the reaction, was analysed by GC and 2,5-bis(aminomethyl) tetrahydrofuran was obtained in 97% yield.

Example 6

[0088] Into a 30 ml autoclave, 2,5-bis(aminomethyl)furan (127 mg, 1.01 mmol) and doped Raney Ni (120 mg) from Ningbo HanYi were added and dissolved in methanol (5 ml). The mixture was stirred at 60 C. under 20 atms H.sub.2 atmosphere for 12 h. The reaction mixture, after completion of the reaction, was analysed by GC and 2,5-bis(aminomethyl) tetrahydrofuran was obtained in 89% yield.

Comparative Example

[0089] Into a 30m1 autoclave, 2,5-bis(aminomethyl)furan (133 mg, 1.05 mmol) and doped Raney Ni (120 mg) from Ningbo HanYi were added and dissolved in p-xylene (5 ml). The mixture was stirred at 100 C. under 90 atms H.sub.2 atmosphere for 12 h. The reaction mixture, after completion of the reaction, was analysed by GC and 2,5-bis(aminomethyl) tetrahydrofuran was obtained in 82% yield while the bicyclic compound 8-oxa-3-azabicyclo[3.2.1] octane appeared as byproduct in 6% yield.

[0090] This comparative example used same catalyst as Example 6 but was performed by at higher temperature and higher hydrogen gas pressure than Example 6. It illustrates that by using invented process, better yield of desired product could be obtained without relying on high temperature and gas pressure.

Example 7

[0091] Into a 100 ml parr pressure reactor, furan-2,5-dicarbaldehyde dioxime (5.0 g, 32.4 mmol) and doped Raney Ni (1.0 g) from Ningbo HanYi were added and dissolved in methanol (40 ml). The mixture was stirred under 20 atms H.sub.2 atmosphere at 50 C. for 24 h and then at 80 C. for another 24 h. The reaction mixture, after completion of the reaction, was analysed by .sup.1H NMR (biphenyl as internal standard) and GC-MS. It was shown 2,5-bis(aminomethyl) tetrahydrofuran was obtained in 75% yield while 2,5-bis(aminomethyl)furan intermediate appeared as a mixture with its oligomer in ca. 12% yield.

Example 8

[0092] Into a 30 ml autoclave, 2,5-bis(aminomethyl)furan (240 mg, 1.9 mmol) and Raney Co (48 mg)(GRACE RANEY 2724) were added and dissolved in methanol (5 ml). The mixture was stirred at 100 C. under 40 atms H.sub.2 atmosphere for 12 h. The reaction mixture, after completion of the reaction, was analysed by GC and 2,5-bis(aminomethyl) tetrahydrofuran was obtained in 84% yield.