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(12) United States Patent (10) Patent No.: US 8,350,056 B2 FOO Et Al

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(12) United States Patent (10) Patent No.: US 8,350,056 B2 FOO Et Al USOO835.0056B2 (12) United States Patent (10) Patent No.: US 8,350,056 B2 FOO et al. (45) Date of Patent: *Jan. 8, 2013 (54) FUNCTIONALIZED N-SUBSTITUTED 2010, 0140166 A1* 6, 2010 Erdner-Tindall et al. ..... 210,603 2010.0143992 A1* 6, 2010 Erdner-Tindall et al. ..... 435,160 PYRROLIDONIUM IONIC LIOUIDS 2010.0143993 A1* 6, 2010 Erdner-Tindall et al. ..... 435,160 2010.0143994 A1* 6, 2010 Erdner-Tindall et al. ..... 435,160 (75) Inventors: Thomas Foo, Wilmington, DE (US); 2010.0143995 A1 6, 2010 Erdner-Tindall et al. ..... 435,160 Mark Andrew Harmer, Landenberg, 2010.0143999 A1* 6, 2010 Erdner-Tindall et al. ..... 435,161 2010/0.144000 A1* 6, 2010 Erdner-Tindall et al. ..... 435,161 PA (US); Keith W. Hutchenson, Lincoln 2010, 0145073 A1 6, 2010 Foo University, PA (US); Christopher P. 2010, O152465 A1 6, 2010 Davis Junk, Wilmington, DE (US); Berlyn R. Mellein, Wilmington, DE (US); Aaron FOREIGN PATENT DOCUMENTS Minter, Wilmington, DE (US) WO O3O48078 A2 6, 2003 WO 201OO65816 6, 2010 WO 201OO65841 6, 2010 (73) Assignee: E I du Pont de Nemours and WO 2010.065873 6, 2010 Company, Wilmington, DE (US) WO WO 2010.065606 A2 * 6, 2010 (*) Notice: Subject to any disclaimer, the term of this OTHER PUBLICATIONS patent is extended or adjusted under 35 Cardoso et al., Synthesis, Characterization, and Thermal and Dielec U.S.C. 154(b) by 136 days. tric Properties of Three Different Methacrylate Polymers With Zwit terionic Pendant Groups, J. Polymer Sci., Part B: Polymer Physics, This patent is Subject to a terminal dis 1997, vol. 35:479-488. claimer. Lermit et al., Some Dichloroamine Derivatives, J. of the Chem. Soc., 1947, pp. 530-533. (21) Appl. No.: 12/792,079 Kosharet al., Preparation of B-H-Perfluoro Alkanesulfonic Acids, J. Am. Chem. Soc., 1953, vol. 75:4595-4596. (22) Filed: Jun. 2, 2010 Wasswescheid et al., Feedstock/Product Phase, Angew. Chem. Int. Ed., 2000, vol. 39:3772-3789. Prior Publication Data R. Sheldon, Catalytic Reactions in Ionic Liquids, The Royal Society (65) of Chemistry, 2001, pp. 2399-2407. US 2011 FO137048A1 Jun. 9, 2011 International Search Report, PCT/US2009/066739, Dated Apr. 3, 2012. International Search Report, PCT/US2009/066751, Dated Feb. 5, Related U.S. Application Data 2010. (63) Continuation-in-part of application No. 12/328,078, International Search Report, PCT/US2009/066712, Dated Feb. 10, 2010. filed on Dec. 4, 2008, now Pat. No. 8,119,818. Van Rantwijk and Sheldon, Delft University of Technology, Biocatalysts in Ionic Liquids, Chem. Rev. 2007, 107, 2757-2785, (51) Int. C. American Chemical Society, New York. C07D 207/12 (2006.01) Ranke, Stolte, Stomann, Arning and Jastorff, Universitat Bremen, (52) U.S. Cl. ........................................ 548/550; 252/364 Design of Sustainable Chemical Products—the Example of Ionic (58) Field of Classification Search .................. 548/550; Liquids, Chem. Rev. 2007, 107, 2183-2206, Americhan Chemical 252/364 Society, New York. Corma, Iborra and Velty, Universidad Politecnica De Valencia, See application file for complete search history. Chemical Routes for the Transformation of Biomass Into Chemicals, Chem. Rev. 2007, 107,2411-2502, American Chemical Society, New (56) References Cited York. Horvath and Anastas, Innovations and Green Chemistry, Chem. Rev. 2007, 107,2169-2173, American Chemical Society, New U.S. PATENT DOCUMENTS York. 2.913,496 11, 1959 Fuller Yokozeki. Sheflett, Junk, Grieco and Foo, Physical and Chemical 4,820,672 4, 1989 Mehta Absorptions of Carbon Dioxide in Room Temperature Ionic Liquids, 5,608, 105 3/1997 Fitzpatrick J. Phys. Chem. B 2008, 112, 16654-16663, American Chemical 5,859,263 1/1999 Ghorpade et al. Society, New York. 6,054,611 4/2000 Farone et al. Letter August 9, 2010, From Reggie Taylor, University of South 6,136,586 10/2000 Budowsky Alabama, to P. Michael Walker. 6,579.343 B2 6, 2003 Brennecke Marsh et al., Fluid Phase Equilibria, 2004, 219, pp. 93-98. 6,818,593 B2 11/2004 Manzer Dorwald, F. Zaragoza, Side Reactions in Organic Synthesis: a Guide 6,900,337 B2 5, 2005 Manzer et al. to Successful Synthesis Design, Weihheim: Wiley-VCH Verlag 7,153,996 B2 12/2006 Fagan et al. Gmbh & Co. KGAA, 2005, Preface. 7,157,588 B2 1/2007 Harmer et al. 7,208,605 B2 4/2007 Davis * cited by examiner 7,314,962 B2 1/2008 Harmer 7,544,813 B2 6, 2009 Harmer Primary Examiner — Rebecca Anderson 7.625,941 B2 12/2009 Harmer 7,744,838 B2 6, 2010 Davis Assistant Examiner — Matthew Coughlin 7,765,823 B2 8, 2010 Shifett 2004.0035293 A1 2/2004 Davis (57) ABSTRACT 2004/O133058 A1 7, 2004 Art 2006/O197053 A1 9, 2006 Shiflett et al. This invention relates to compounds useful as ionic liquids 2006/0235230 A1 10, 2006 Harmer et al. that are based on an N-substituted pyrrolidinone and incor 2006/0276670 A1 12, 2006 Junket al. porate a pendant ammonium cation that is spaced from the 2006/0276671 A1 12/2006 Harmer et al. pyrrolidone ring by a variable length linker. 2008/0028777 A1 2/2008 Boesmann 2010/013.9154 A1* 6, 2010 Erdner-Tindall et al. ....... 44/451 25 Claims, No Drawings US 8,350,056 B2 1. 2 FUNCTIONALIZED N-SUBSTITUTED include an anion, and a cation in which there is a pendant PYRROLIDONIUM IONIC LIOUIDS ammonium cation spaced from a pyrrolidone ring by a vari able length linker. This linker is denominated Zin the descrip This application is a continuation-in-part of and claims the tion of Formula I as set forth herein. These compounds are benefit of, U.S. application Ser. No. 12/328,078, filed Dec. 4, 2008, which is by this reference incorporated in its entirety as useful as ionic liquids, and can be used for example as a a part hereof for all purposes. Solvent, as a catalyst for various kinds of reactions (such as an alkylation reaction), and as an absorbent for various gases TECHNICAL FIELD (such as CO). These compounds also have the advantage that the cationic portion, and some of the associated anions, may This invention relates to N-substituted pyrrolidonium com 10 be readily prepared from levulinic acid, or levulinic acid pounds that are useful as ionic liquids. derivatives, which may be obtained from the hydrolysis of inexpensive renewable biomass feedstocks. BACKGROUND In the description of the compositions hereof, the following definitional structure is provided for certain terminology as Ionic liquids are liquids composed of ions that are fluid at 15 or below about 100°C. Ionic liquids exhibit negligible vapor employed variously in the specification: pressure, and with increasing regulatory pressure to limit the An “alkyl group is a monovalent (i.e. having a Valence of use of traditional industrial solvents due to environmental one) group having the general Formula CH2. considerations such as Volatile emissions and aquifer and “Biomass” refers to any cellulosic or lignocellulosic mate drinking water contamination, much research has been rial, and includes materials containing cellulose, and option devoted to designing ionic liquids that could function as ally further includes hemicellulose, lignin, starch, oligosac replacements for conventional solvents. charides and/or monosaccharides. Biomass may also include Ionic liquids typically consist of a salt of an organic cation additional components such as proteins and/or lipids. Biom such as the N-alkylpyridinium, 1,3-dialkylimidazolium, tet ass suitable for use herein may be derived from a single raalkylammonium, tetraalkylphosphonium or trialkylsulfo Source, or may be a mixture derived from more than one nium cation. U.S. Pat. No. 7,157.588 describes, for example, 25 Source. Such sources include without limitation bioenergy ionic liquids based on N-substituted pyrrolidones, which crops, agricultural residues, municipal Solid waste, industrial have a pendant ammonium cation that is spaced from the Solid waste, sludge from paper manufacture, yard waste, pyrrolidone ring by a variable length linker. A need remains, wood and forestry waste. Examples of biomass include with however, for other ionic liquids that may be designed for use out limitation corn grain, corn cobs, crop residues such as in selected applications, particularly those that may be pre 30 cornhusks, corn Stover, grasses, wheat, wheat Straw, hay, rice pared at least in part from renewable resources. Straw, Switchgrass, waste paper, Sugar cane bagasse, Sor ghum, Soy, residue from the milling of grain, trees, branches, SUMMARY roots, leaves, wood chips, sawdust, shrubs and bushes, Veg This invention provides a compound represented by the 35 etables, fruits, flowers and animal manure. A “catalyst” is a substance that affects the rate of a reaction structure of the following Formula 1: but not the reaction equilibrium, and emerges from the reac tion chemically unchanged. Formula 1 “Conversion” refers to the weight percent of a particular reactant that is converted in a reaction to product. 40 A "hydrocarbyl group is a monovalent group containing only carbon and hydrogen. An “ionic liquid is an organic salts that is fluid at or below about 100° C. 45 A “levulinate” ion is an anion represented by the structure CH3 of the following formula: wherein (a) Z is —(CH), , wherein n is an integer from 2 to 12: (b) R are Rare each independently H or a C to C. 50 straight-chain or branched alkyl group; (c) R' is -(CH2) X -(CH2), Y-R wherein X and Y are each independently O, Nor NR, r and pare each independently an integer from 1 to 4, q is an integer from 0 to 8, and each R is independently Hora C to C straight-chain e O or branched alkyl group; and 55 (d) A is an anion selected from the group consisting of levulinate, BFI.
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