Catalytic production of 1,2,5,6-hexanetetrol from levoglucosenone

Abstract

A method of making of 1,2,5,6-hexanetetrol (“tetrol”). The method includes the steps of contacting a reaction solution containing water as well as levoglucosenone, dihydrolevoglucosenone, and/or levoglucosanol, with a catalyst containing metal and acid functionalities, at temperature of from about 100° C. to about 175° C., and a hydrogen partial pressure of from about 1 bar to about 50 bar (about 0.1 MPa to about 5 MPa), and for a time wherein at least a portion of the reactant is converted into 1,2,5,6-hexanetetrol.

Claims

1. A method of making of 1,2,5,6-hexanetetrol, the method comprising: contacting a solution comprising levoglucosenone, dihydrolevoglucosenone, or levoglucosanol, or mixtures thereof and water, with a catalyst containing metal sites and acid sites, at temperature of from about 100° C. to about 175° C., and a hydrogen partial pressure of from about 1 bar to about 50 bar (about 0.1 MPa to about 5 MPa), and for a time wherein at least a portion of the levoglucosenone, dihydrolevoglucosenone, or levoglucosanol, or mixtures thereof is converted into 1,2,5,6-hexanetetrol.

2. The method of claim 1, wherein the catalyst comprises a metal selected from the group consisting of Ru, Rh, Pd, Os, Jr, Pt, Au, Ag, Cu, Co, Fe, and Ni.

3. The method of claim 1, wherein the catalyst comprises a noble metal selected from the group consisting of Ru, Rh, Pd, and Pt.

4. The method of claim 1, wherein the catalyst comprises a noble metal that is platinum.

5. The method of any one of claims 1 to 4, wherein the pressure is from about 20 to about 45 bar.

6. The method of claim 5, wherein the pressure is from about 30 to about 40 bar.

7. The method of claim 1, wherein the acid catalyst comprises a mineral acid selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, and solid acidic supports selected from the group consisting of alumina, zirconia, titania, hafnia, silica, zirconia-phosphate, titania-phosphate, zirconia-tungsten, titania-tungsten, zeolites, and mixtures of these.

8. The method of claim 1, wherein the catalyst comprises aluminum and silicon.

9. The method of claim 1, wherein the catalyst comprises platinum deposited on a support.

10. The method of claim 1, wherein the solution comprises levoglucosanol having a threo-to-erythro ratio of about 1.

11. The method of claim 1, wherein the solution comprises levoglucosanol having a threo-to-erythro ratio of less than 1.

12. The method of claim 1, wherein the solution comprises levoglucosanol having a threo-to-erythro ratio of greater than 1.

13. The method of claim 1, wherein the method is conducted batch-wise or continuously.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a quantitative .sup.13C NMR spectrum of the product yielded by the disclosed process. The reaction, Lgol to tetrol, was 100%. Batch reaction of 10 mL of 0.9 wt % levoglucosanol in water using Pt/SiAl catalyst, 150° C., 500 psi H.sub.2, 3 h reaction time, 100 mg 1% Pt/SiAl.

(2) FIG. 2 is graph depicting the concentrations of reactant and products over time in a batch reactor with dip-tube sampling. Batch reaction of 60 mL of 0.9 wt % levoglucosanol in water using Pt/SiAl catalyst, 150° C., 500 psi H.sub.2, 360 mg 1% Pt/SiAl.

DETAILED DESCRIPTION

(3) Abbreviations and Definitions:

(4) The “noble metals” are defined herein as ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg).

(5) LGO=levoglucosenone. LGOL=levoglucosanol.

(6) As used herein, catalyst “support” refers to a solid material having a substantially stable surface area at the stated reaction conditions. That is, the support has a surface area that is not substantially altered by the reaction conditions or altered in any way physically or chemically that affects the reaction. The catalyst support generally comprises one or more solid acid materials. Exemplary solid acids which can be utilized include, but are not limited to, heteropoly acids, acid resin-type catalysts, meso-porous silicas, acid clays, sulfated zirconia, molecular sieve materials, zeolites, and acidic material on a thermo-stable support. Where an acidic material is provided on a thermo-stable support, the thermo-stable support can include for example, one or more of alumina, zirconia, titania, hafnia, silica, tin oxide, niobia, carbon, and the like, zeolites, and mixtures of these. In preferred versions of the method, the support comprises aluminum and silicon, with platinum, palladium, rhodium, and/or rhenium deposited on the support. The oxides themselves (e.g., ZrO.sub.2, SnO.sub.2, TiO.sub.2, etc.) which may optionally be doped with additional acid groups such as sulfonates may also be used as solid acid catalysts.

(7) Further examples of suitable solid acid supports include strongly acidic ion exchangers such as cross-linked polystyrene containing sulfonic acid groups. For example, the Amberlyst®-brand resins are functionalized styrene-divinylbenzene copolymers with different surface properties and porosities. The functional group is generally of the sulphuric acid type. The Amberlyst®-brand resins are supplied as gellular or macro-reticular spherical beads. (Amberlyst® is a registered trademark of the Dow Chemical Co.) Similarly, Nafion®-brand resins are sulfonated tetrafluoroethylene-based fluoropolymer-copolymers which are solid acid catalysts. Nafion® is a registered trademark of E.I. du Pont de Nemours & Co.)

(8) Preferred supports are refractory oxides having acid sites, such as (but not limited to) alumina, zirconia, titania, hafnia, phosphates, silica; and mixtures of these. The catalyst support material can be or can include rare earth-modified refractory metal oxides, where the rare earth may be any rare earth metal, for example, lanthanum or yttrium; and/or alkali earth metal-modified refractory oxides. Zeolites can also be used as supports. H-type zeolites are generally preferred, for example zeolites in the mordenite group or fine-pored zeolites such as zeolites X, Y and L, e.g., mordenite, erionite, chabazite, or faujasite. The supported catalysts disclosed herein can be in any shape or form now known or developed in the future, such as, but not limited to, granules, powder, beads, pills, pellets, flakes, cylinders, spheres, or other shapes.

(9) Tetrol=1,2,5,6-hexanetetrol.

(10) THFDM=tetrahydrofurandimethanol.

(11) Numerical ranges as used herein are intended to include every number and subset of numbers contained within that range, whether specifically disclosed or not. Further, these numerical ranges should be construed as providing support for a claim directed to any number or subset of numbers in that range. For example, a disclosure of from 1 to 10 should be construed as supporting a range of from 2 to 8, from 3 to 7, from 1 to 9, from 3.6 to 4.6, from 3.5 to 9.9, and so forth.

(12) All references to singular characteristics or limitations of the present invention shall include the corresponding plural characteristic or limitation, and vice-versa, unless otherwise specified or clearly implied to the contrary by the context in which the reference is made. The indefinite articles “a” and “an” mean “one or more,” unless explicitly stated to the contrary. Unless expressly stated to the contrary, “or” refers to an inclusive “or.” That is, a condition “A or B” is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

(13) All combinations of method or process steps as used herein can be performed in any order, unless otherwise specified or clearly implied to the contrary by the context in which the referenced combination is made.

(14) The methods of the present invention can comprise, consist of, or consist essentially of the essential elements and limitations of the method described herein, as well as any additional or optional ingredients, components, or limitations described herein or otherwise useful in synthetic organic chemistry. The terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains” or “containing,” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, a mixture, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus.

(15) As used herein, the term “about” modifying the quantity of an ingredient or reactant, or the value of a variable, refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or carry out the methods; through the limitations of the equipment used to measure variables such as time, temperature, and pressure, and the like. The term “about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term “about”, the claims include equivalents to the quantities. The term “about” may mean within 10% of the reported numerical value, preferably within 5% of the reported numerical value.

(16) Overview:

(17) As shown in Scheme 1, polysaccharides (or cellulose) can be converted into levoglucosenone (LGO) via acid-catalyzed dehydration. LGO can then be catalytically reduced into the corresponding alcohol, levoglucosanol (LGOL). At the heart of the current method is a means to catalytically convert LGOL into 1,2,5,6-hexanetetrol (“tetrol”), without over-reacting the LGOL into downstream products such as tetrahydrofurandimethanol (THFDM) or 1,6-hexanediol.

(18) ##STR00001##

(19) The crux of the method is thus shown in Scheme 2. An aqueous reaction solution comprising levoglucosanol is contacted with a heterogeneous catalyst comprising a noble metal deposited on a support having acid sites in the presence of hydrogen (H.sub.2). As noted earlier, the preferred reaction temperature is about 100° C. to about 175° C., and the preferred hydrogen partial pressure of from about 1 bar to about 50 bar (about 0.1 MPa to about 5 MPa).

(20) ##STR00002##

(21) High yields of tetrol have been achieved using both dilute (0.9 wt %) and concentrated (22.5 wt %) Lgol solutions in water. See Table 1.

(22) TABLE-US-00001 TABLE 1 Selectivity versus LGOL concentration Lgol Time Lgol Selectivities (%) Cat. wt % (h) Conversion Tetrol THFDM Total 1% Pt/SiAl 0.90 3  90% 94% 3% 97% 5% Pt/SiAl 22.5 17 100% 86% 7% 93%
Conditions: 150 C, 500 psi H.sub.2, 100 mg catalyst, 10 mL Lgol in water solvent.

(23) Levoglucosenone can also be directly upgraded in one pot to tetrol. In batch reactions using 0.9 wt % LGO in water over 1% Pt/SiAl, 500 psi H.sub.2 (34 bar) at 150° C. shows 90% tetrol yield, with THFDM as a side-product. See Scheme 3.

(24) ##STR00003##
Platinum is the preferred catalyst. But other noble metals may also be used, as shown in Table 2. As shown in Table 2, platinum, palladium, rhodium, and ruthenium all function with acceptable results, although platinum clearly provides superior results.

(25) See also FIG. 1, which is the quantitative .sup.13C NMR spectrum of the product yielded by the reaction batch reaction of 10 mL of 0.9 wt % levoglucosanol in water using Pt/SiAl catalyst, 150° C., 500 psi H.sub.2, 3 h reaction time, 100 mg 1% Pt/SiAl. Yield to tetrol was nearly quantitative (93%).

(26) TABLE-US-00002 TABLE 2 Conversion and Selectivity to Tetrol and THFDM with different metal catalysts Selectivities (%) Lgol Hemiketal- Cat. Conversion Tetrol ketone THFDM Total 1% Pt/SiAl 90% 94%  3% 97% 1% Pd/SiAl 93% 52% 41% 92% 1% Ru/SiAl 58% 91%  0% 91% 1% Rh/SiAl 96% 35% 54% 11% 100% 
Effect of Metal and Acid Sites (Proposed Mechanism):

(27) Without being limited to any specific reaction mechanism or underlying chemical phenomena, a putative mechanism for the reaction is provided in Scheme 4. Of particular note in proposing this mechanism is that the reaction does not occur when a metal supported on a non-acidic support is used for the catalyst. When the same reaction is carried out with a solid acid catalyst (SiAl) in the absence of a metal, .sup.13C NMR and ESI-MS showed that a hemiketal-ketone are major intermediates, with hemiacetal as a minor intermediate (see Scheme 4). Hydrogenation of the intermediates over a metal catalyst then yields tetrol as a major product (see Table 3). Thus, it is proposed that the reaction proceeds by an acid-catalyzed C—O cleavage followed by the metal-catalyzed hydrogenation of the intermediate to yield tetrol. The reaction can also be carried out over a physical mixture of metal and acid catalysts (see Table 3). LGOL+homogeneous H.sub.2SO.sub.4 also yields a hemiacetal intermediate, and hydrogenation of this intermediate shows a lower selectivity to tetrol (˜50%).

(28) As shown in FIG. 2, Lgol is converted to Tetrol via a ketone-hemiketal intermediate which is present at short reaction times. Once 100% conversion of Lgol is achieved (by 400 minutes), there is no decrease in yield of Tetrol up to 1400 minutes, indicating that Tetrol is stable (i.e., Tetrol does not undergo further reactions) under these conditions.

(29) TABLE-US-00003 TABLE 3 Conversion and selectivity for different metal-acid catalyst configurations Selectivities (%) Time Lgol Hemiketal- Cat. (h) Conversion Tetrol Ketone THFDM Total 1% Pt/SiAl 3 90% 94% 0% 3% 97% Phys mix: 3 100%  85% 0% 8% 93% 1% Pt/SiO2 & SiAl SiAl, then Pt/SiO2   3, 3 74% 58% 17%  15%  89% H2SO4, then Pt/SiO2* 0.25, 3 71% 51% 5% 56% Conditions: 150 C., 500 psi H2, 100 mg catalyst, 10 mL 0.9 wt % Lgol in water solvent. *for H.sub.2SO.sub.4 reaction, the H.sub.2SO.sub.4 concentration was 50 mM and the reaction was carried out at 130° C. for 0.25 h.

(30) ##STR00004##
Control Over Tetrol Stereochemistry:

(31) The method is also tunable to yield diastereomerically enriched tetrol by starting with diastereomerically enriched LGOL. See Scheme 5. By altering the ratio of threo to erytho isomers in the reactant, the cis/trans ratio of the product tetrol is likewise altered.

(32) The LGOL threo/erythro ratio can be varied by hydrogenating cyrene with different catalysts to yield a diastereomerically enriched reactant solution. When the threo-to-erythro ratio of the reactant LGOL is altered to something other than 1:1 (either higher or lower), the cis/trans ratio of the product tetrol is also impacted. See Table 4. The yields in these experiments were 85-91%.

(33) ##STR00005##

(34) TABLE-US-00004 TABLE 4 Effect of Lgol stereochemistry on Tetrol stereochemistry Lgol Tetrol Cat. threo/erythro cis/trans 1% Pt/SiAl 1.4 1.2 5% Pt/SiAl 4.3 2.8
The data shown in Table 4 was generated using 10 mL of 0.9 wt % LGOL/water, which was converted to tetrol in a batch reactor using 100 mg Pt/SiAl catalyst, at 150° C., 500 psi H.sub.2, and a 3 h reaction time. The tetrol cis/trans ratio was determined by 13C NMR.