CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the priority benefit of U.S. Provisional Application No.

62/142,808, filed April 3, 2015, which is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

[0002] The present invention relates to N-substituted glycinium (fluorosulfonyl)(tri- fluoromethylsulfonyl)imide compounds and methods for producing and using the same.

BACKGROUND OF THE INVENTION

[0003] Ionic liquids have a wide variety of applications in various fields including, but not limited to, batteries (in particular lithium batteries), removal of metal ions, electrodeposition of metals, and synthesis of nanoparticles. Unfortunately, the solubility of ionic inorganic compounds, e.g., metal salts, are very low in most conventional ionic liquids. This low solubility of metal salts is a serious drawback for possible applications of ionic liquids that require high concentrations of dissolved metal salts, e.g., in lithium batteries, electrodepositions, and synthesis of nanoparticles.

[0004] It has been found, however, that ionic liquids comprising a carboxyl group moiety

(i.e., -C0 ₂ H), on its cationic moiety portion can increase solubility of metal salts dramatically. See, for example, J. Phys. Chem. B., 2006, 110, 20978-20992 and Inorg. Chem., 2008, 47, 9987- 9999. Ionic liquids in these cited references have bis(trifluoromethyl-sulfonyl)imide, i.e., N[(S0 ₂ CF ₃ )] ₂ "TFSr or "Tf ₂ N", as the anionic moiety.

[0005] Because of their utility in ability to dissolve or form a complex with inorganic salts, there is a need for other ionic liquids having a carboxyl moiety in its cationic moiety portion. SUMMARY OF THE INVENTION

[0006] One aspect of the present invention provides an N-substituted gly

(fluorosulfonyl)(trifluoromethylsulfonyl)imide compound of the formula:

I

where each of R ¹ , R ² and R ³ is independently selected from the group consisting of alkyl, aryl, aralkyl, cycloalkyl, (cycloalkyl)alkyl, heteroaryl, (heteroaryl)alkyl, heterocyclyl, and

(heterocyclyl)alkyl; or R ¹ and R ² together with the nitrogen atom to which they are attached to form a nitrogen-heterocyclyl, or a nitrogen-heteroaryl.

[0007] Another aspect of the invention provides a method for producing N-substituted glycinium (fluorosulfonyl)(trifluoro-methylsulfonyl)imide compound of Formula I. One particular method comprises contacting an N-substituted glycinium compound of the formula:

II

with (fluorosulfonyl)(trifluoromethylsulfonyl)imide ("HFTFSI") under conditions sufficient to produce said N-substituted glycinium (fluorosulfonyl)(trifluoromethylsulfonyl)-imide compound of Formula I, where R ¹ , R ² and R ³ are those defined herein. The reaction can be conducted in the presence of or in the absence of a solvent.

[0008] Another embodiment of a method for producing N-substituted glycinium

(fluorosulfonyl)(trifluoro-methylsulfonyl)imide compound of Formula I comprises contacting an N-substituted glycinium salt of the formula:

III

with a salt of (fluorosulfonyl)(trifluoromethylsulfonyl)imide under conditions sufficient to produce said N-substituted glycinium (fluorosulfonyl)(trifluoromethyl-sulfonyl)imide compound of Formula I, where R ¹ , R ² and R ³ are those defined herein. The reaction can be conducted in the presence of or in the absence of a solvent.

[0009] Still another aspect of the invention provides a method for extracting a metal oxide and/or a metal salt from a sample using a compound of the invention. Typically, the sample comprises a metal oxide, a metal salt or a combination thereof. The method involves contacting the sample with a compound of the invention under conditions sufficient to separate a metal oxide or a metal salt from the sample. Exemplary metal oxides that can be extracted using the method of the invention include, but are not limited to, uranium(VI) oxide, zinc(II) oxide, cadmium(II) oxide, mercury(II) oxide, nickel(II) oxide, copper(II) oxide, palladium(II) oxide, lead(II) oxide, silver(I) oxide, rare earth oxides or a combination thereof.

[0010] The compound of invention and the sample are admixed at temperature between

0 °C and 150 °C for extracting the metal oxide and/or the metal salt.

[0011] One particular aspects of the invention provides a method for dissolving a metal oxide, a metal hydroxide, a metal salt or a combination thereof from a sample. Such a method comprises contacting a sample that includes a metal hydroxide, a metal salt or a combination thereof with a compound of the invention under conditions sufficient to dissolve a metal oxide, a metal hydroxide, a metal salt or a combination thereof from said sample to produce a solution of dissolved metal comprising said compound of the invention and a processed sample. In this manner, one can decontaminate soil, polish a metal surface, extract precious metal from an ore, etc.

[0012] Compounds of the invention are ionic liquids, and therefore can be used in various applications where ionic liquids are used. Such uses are well known to one skilled in the art. Exemplary uses include, but are not limited to, (1) solubilizing organic or inorganic compounds, such as of metal oxides, metal hydroxides or metal salts; (2) extracting processes, e.g., for extracting metal ions from metallurgical slags or from pulverized mixtures of metal oxides with silicate or aluminosilicate rocks; (3) decontamination of soils that are contaminated by heavy metals (especially with copper, nickel, zinc, cadmium, mercury or lead); (4) in catalytic reactions where the compound of the invention serves as a solvent, co-solvent or as a catalyst; (5) electrodeposition of metal ions, e.g., by using the compound of the invention a solvent for the metal precursors; (6) as a medium for electropolishing or for the cleaning of metal surfaces, e.g., by removing metal oxide from its surface; (7) in electrodeposition of (thin) metal layers on conductive surfaces, e.g., by dissolving metal ions and then using electrolysis to deposit the metal layer; (8) processing of spent nuclear fuel elements, e.g., for removing lanthanide or actinide oxides from nuclear fuel elements; (9) as electrolytes in batteries, fuel cells, photovoltaic devices and electrochromic devices; and (10) recycling metals from used catalysts and electronic circuits.

DESCRIPTION OF THE INVENTION

[0013] Definitions:

[0014] The term "alkyl" refers to a saturated linear monovalent hydrocarbon moiety of one to twenty, typically one to twelve, and often one to six carbon atoms or a saturated branched monovalent hydrocarbon moiety of three to twenty, typically three to twelve and often three to six carbon atoms. Alkyl groups can optionally be substituted with an alkoxide (i.e., -OR ^a , where R ^a is alkyl) and/or other functional group(s) that are either protected or non-reactive under a given reaction condition. In addition, one or more hydrogen atoms of the alkyl group may be replaced by same or different halo atoms. Exemplary alkyl groups include, but are not limited to, methyl, ethyl, w-propyl, 2-propyl, ferf-butyl, pentyl, -CH ₂ C1, -CF ₃ , -CH ₂ CF ₃ , -CH ₂ CC1 , and the like.

[0015] The term "cycloalkyl" refers to a non-aromatic, saturated, monovalent mono- or bicyclic hydrocarbon moiety of three to ten ring carbons. The cycloalkyl can be optionally substituted with one or more, for example, one, two or three, substituents within the ring structure that are either protected or unreactive under a given reaction condition. In addition, one or more hydrogen atoms of the cycloalkyl group may be replaced by same or different halogen atoms. [0016] The terms "halo," "halogen" and "halide" are used interchangeably herein and refer to fluoro, chloro, bromo, or iodo.

[0017] The terms "heterocyclyl" and "heterocycloalkyl" are used interchangeably herein and refer to a non-aromatic mono-, bi- or tricyclic moiety of three to twenty, typically three to twelve and often three to eight ring atoms in which one or two ring atoms are heteroatoms selected from N, O, or S(0) _n (where n is an integer from 0 to 2), the remaining ring atoms being C, where one or two C atoms can optionally be a carbonyl group. The heterocyclyl ring can be optionally substituted independently with one or more, preferably one, two, or three,

substituents. When two or more substituents are present in a heterocyclyl group, each substituent is independently selected. In addition, one or more hydrogen atoms of the heterocycloalkyl may be replaced by the same or different halogen atoms. Exemplary heterocycloalkyls include, but is not limited to, tetrahydropyranyl, piperidino, piperazino, morpholino and thiomorpholino, thiomorpholino-1 -oxide, thiomorpholino- 1, 1 -dioxide, and the like.

[0018] The term "aryl" refers to a monovalent mono-, bi- or tricyclic aromatic hydrocarbon moiety of six to twenty, typically six to twelve and often six to ten ring atoms which is substituted independently with one or more substituents. Exemplary aryl includes, but is not limited to, phenyl, 1-naphthyl, and 2-naphthyl, anthracenyl, and the like.

[0019] The term "heteroaryl" means a monovalent mono-, bi- or tricyclic aromatic moiety of 5 to 20, typically 5 to 12 and often 5 to 10 ring atoms containing one, two, or three ring heteroatoms selected from N, O, or S, the remaining ring atoms being C. Exemplary heteroaryls include, but is not limited to, pyridyl, furanyl, thiophenyl, thiazolyl, isothiazolyl, triazolyl, imidazolyl, isoxazolyl, pyrrolyl, pyrazolyl, pyrimidinyl, benzofuranyl, isobenzofuranyl, benzothiazolyl, benzoisothiazolyl, benzotriazolyl, indolyl, isoindolyl, benzoxazolyl, quinolyl, isoquinolyl, benzimidazolyl, benzisoxazolyl, benzothiophenyl, dibenzofuran, benzodiazepin-2- one-5-yl, and the like.

[0020] The terms "(cycloalkyl)alkyl", "(heterocycloalkyl)alkyl", "aralkyl",

"(heteroaryl)alkyl" refers to a moiety of the formula -R ^a R ^b , where R ^a is alkenyl and R ^b is cycloalkkyl, heterocycloalkyl, aryl, and heteroaryl, respectively. [0021] The term "alkenyl" refers to alkyl group as defined herein which is divalent, i.e., having two attaching bonds.

[0022] The term "ionic liquid" refers to a salt having a melting point of about 100 °C or less, typically about 80 °C or less, often 50 °C or less, and most often about 25 °C or less.

[0023] As used herein, the terms "treating", "contacting" and "reacting" refer to adding or mixing two or more reagents under appropriate conditions to produce the indicated and/or the desired product. It should be appreciated that the reaction which produces the indicated and/or the desired product may not necessarily result directly from the combination of two reagents which were initially added, i.e., there may be one or more intermediates which are produced in the mixture which ultimately leads to the formation of the indicated and/or the desired product.

[0024] The term "absence of any solvent" means no solvent is added. While some solvent may be present inadvertently, the total amount of solvent is about 5 % or less, typically about 3 % or less, often about 1% or less, and most often about 0.5% or less of the total weight of the mixture.

[0025] Compounds of the Invention and Synthesis thereof

[0026] One aspect of the present invention provides an N-substituted glycinium

(fluorosulfonyl)(trifluoromethylsulfonyl)imide compound of the formula:

I

wherein each of R ¹ , R ² and R ³ is independently selected from the group consisting of alkyl, haloalkyl, aryl, aralkyl, cycloalkyl, (cycloalkyl)alkyl, heteroaryl, (heteroaryl)alkyl, heterocyclyl, and (heterocyclyl)alkyl; or R ¹ and R ² together with the nitrogen atom to which they are attached to form a nitrogen-heterocyclyl, or a nitrogen-heteroaryl. Compounds of Formula I are ionic liquids. [0027] In some embodiments, each of R ¹ , R ² and R ³ is independently alkyl. In one particular embodiment, R ¹ , R ² and R ³ are methyl. In other embodiments, at least one of R ¹ , R ² and R ³ is methyl. Still in other embodiments, at least two of R ¹ , R ² and R ³ are methyl.

[0028] Still in another embodiment, R ¹ and R ² together with the nitrogen atom to which they are attached to form a nitrogen-heterocyclyl or a nitrogen-heteroaryl. In one particular embodiment, R ¹ and R ² together with the nitrogen atom to which they are attached to form a nitrogen-heterocyclyl or a nitrogen-heteroaryl selected from the group consisting of 3,4-dihydro- 2H-pyrrolidinium, 2,3,4,5-tetrahydropyridinium, imidazolium, pyridinium, pyrrolidinium, piperidinium, and morpholinium.

[0029] Compound of Formula I can be produced by contacting an N-substituted glycinium compound of the formula:

R2

1 +

R— N— R ³

^CO~2

II

with (fluorosulfonyl)(trifluoromethylsulfonyl)imide ("HFTFSI") under conditions sufficient to produce said N-substituted glycinium (fluorosulfonyl)(trifluoromethylsulfonyl)imide compound of Formula I. (Fluorosulfonyl)(trifluoromethylsulfonyl)imide, i.e., HFTFSI, has the following chemical formula:

_/ S0 ₂ F

HN

\

S0 ₂ CF ₃

and can be readily produced using a process known to one skilled in the art, such as those disclosed in a commonly assigned U.S. Patent Application No. 14/071,597, filed November 4, 2013, which is incorporated herein by reference in its entirety.

[0030] The reaction can be conducted in the presence or in the absence of a solvent. If solvent is used, typically water or an alcoholic solvent, such as ethanol, propanol, isopropanol, butanol, etc. or a mixture thereof, is used. [0031] The reaction can be carried out by adding N-substituted glycinium compound of

Formula II to FIFTFSI or by adding FIFTFSI to N-substituted glycinium compound of Formula II. Typically, FIFTFSI is added to N-substituted glycinium compound of Formula II slowly to maintain the reaction temperature below a certain temperature, e.g., at or below 70 °C, typically at or below 65 °C, and often at or below 60 °C.

[0032] Once the addition is completed, the reaction temperature may be increased to expedite the reaction. The reaction temperature can vary widely and can depend on a variety of factors including, but not limited to, whether a solvent is used or not, the amount of HFTFSI added, the concentration of the reagents, the reaction time, etc. Typically, when no solvent is used the reaction temperature is increased to at least about 65 °C and often to at least about 70 °C. In some embodiments, after complete addition of HFTFSI, the reaction temperature is increased to about 70 °C. When a solvent, e.g., water, is used for the reaction the reaction temperature of about 50 °C or less and often about 40 °C or less is used.

[0033] The reaction time can also vary widely depending on various factors including, but not limited to, whether a solvent is used or not, the amount of HFTFSI added, the

concentration of the reagents, temperature of the reaction, etc. In general, however the reaction time is about 2 hours or less, typically about an hour or less, and often about 0.5 h.

[0034] In another embodiment, N-substituted glycinium (fluorosulfonyl)(trifluoromethyl- sulfonyl) compound of Formula I can be produced by contacting an N-substituted glycinium salt of the formula:

R2

1+

R— N— R ³ · X ^"

^C0 ₂ H

III

with an alkaline salt, alkaline-earth salt or a transition metal salt of (fluorosulfonyl)(trifluoro- methylsulfonyl)imide, i.e., "MFTFSI", where M represents alkaline metal, alkaline-earth metal, or a transition metal, under conditions sufficient to produce said N-substituted glycinium

(fluorosulfonyl)(trifluoromethyl-sulfonyl) compound of Formula I. R ¹ , R ² and R ³ of compound of Formulas II and III are those defined herein. In N-substituted glycinium salt of Formula III, X ^~ can be any counter ion of a strong acid such as, but not limited to, chloride, bromide, iodide, phosphonate, sulfonate, and the like. A "strong acid" refers to a compound whose pKa is sufficiently low enough to protonate N-substituted glycinium compound of Formula II.

Typically, a strong acid has pKa of about 5 or less, often pKa of about 3 or less, often pKa of about 1 or less. The term "about" refers to ± 20%, typically ± 10%, and often ± 5% of the numeric value.

[0035] Reaction conditions are typically similar to that described above.

[0036] Utility

[0037] Compounds of the invention have a wide variety of applications that are known to one skilled in the art of ionic liquids. Exemplary application of compounds of the invention includes, but is not limited to, extracting a metal oxide or salt from a sample comprising a metal oxide or salt. Other uses of ionic compounds of the invention include as a solvent in

electrochemical applications, e.g., as electrolytes in batteries, in photovoltaic devices, as a medium for electrodeposition, electropolishing of metals, as a solvent for nanoparticle synthesis, and other applications known to one skilled in the art. In addition, since ionic liquids have low vapor pressure and/or high ignition points, they do not generate dangerous air-vapor mixtures. Therefore, they can are particularly useful solvents for chemical reactions, including catalytic reactions.

[0038] With regards to extracting a metal oxide or a metal salt using a compound of the invention, such a method typically includes contacting a sample with a compound of Formula I under conditions sufficient to separate a metal oxide from the sample. Exemplary metal oxides that can be extracted using compounds of the invention include, but are not limited to, uranium (VI) oxide, zinc (II) oxide, cadmium (II) oxide, mercury (II) oxide, nickel (II) oxide, copper (II) oxide, palladium (II) oxide, lead (II) oxide, silver (I) oxide, rare earth oxides, or a combination thereof. Exemplary metal salts that can be extracted include CuCl ₂ *2H ₂ 0 or EuCl ₃ *6H ₂ 0. Often the sample and the compound of Formula I are combined in a solution, typically an aqueous and/or an alcoholic solution. [0039] Extraction of metal oxides or salts can be conducted under a wide range of temperature including, but not limited to, from about 0 °C to about 100 °C. Typically, it is conducted at room temperature.

[0040] Compounds of the invention have a relatively low melting point compared to other similar ionic liquids, e.g., other N-substituted glycinium ionic liquids such as betaine- bis(trifluoromethylsulfonyl)imide, i.e., "[Hbet][TFSI]". Typically, the melting point of compounds of the invention is about 100 °C or less, often 80 °C or less, more often 60 °C or less, and most often 50 °C or less.

[0041] The viscosity of compounds of the invention also is relatively low compared to other N-substituted glycinium ionic liquids. Typically, the viscosity of compounds of the invention is at least 5% lower, often at least 10% lower and more often at least 20% lower than the viscosity of other known N-substituted glycinium ionic liquids, such as [Hbet][TFSI]. Low viscosity is advantageous, as it allows increased mass transfer and more rapid metals extraction.

[0042] As stated above, compounds of the invention can be used in a variety of application. In one particular embodiment, compounds of the invention are used to solubilize metal substrates. Exemplary metal substrates that can be solubilized by compounds of the invention include, but are not limited to, metal oxides, metal hydroxides, metal salts, etc.

[0043] Compounds of the invention can be used to dissolve metal oxides such as: SC2O3,

Y2O3, U2O3, Pr ₆ On, Nd ₂ 0 ₃ , Sm ₂ 0 ₃ , Eu ₂ 0 ₃ , Gd ₂ 0 ₃ , Tb ₄ 0 ₇ , Dy ₂ 0 ₃ , Ho ₂ 0 ₃ , Er ₂ 0 ₃ , Tm ₂ 0 ₃ , Yb ₂ 0 ₃ , Lu ₂ 0 ₃ , UO ₃ , PbO, ZnO, CdO, HgO, CuO, Ag ₂ 0, NiO, PdO and MnO. Similarly, compounds of the invention can also be used to dissolve hydroxides of these metal oxides. In this manner, compounds of the invention can be used in chemical reaction where use of a non-protic solvent is desired or required. In some cases, water can be used to facilitate the dissolution of the metal oxide or metal hydroxide, after which water can be removed. Metal salts can also be dissolved by compounds of the invention in a similar manner with or without the aid of water. Exemplary metal salts that can be dissolved include, but are not limited to, CuCl ₂ *2H ₂ 0 and EuCl3*OH ₂ 0.

[0044] The dissolution process can be facilitated by using moderate to high pressure conditions. [0045] The metals that are dissolved using compounds of the invention can be recovered or removed by extracting the ionic liquid of the invention with an acidified aqueous solution such as a dilute hydrochloric acid or nitric acid solution. Such extraction transfers the metals to the aqueous phase and the compound of the invention is regenerated. In this manner, a sample (e.g., soil, or other material) can be decontaminated using compounds of the invention. A metal surface can also be cleaned using a similar process to remove the metal oxide coating from its surface. Thus, one particular use of compounds of the invention include recycling precious metals, e.g., platinum, from catalysts and the electrodeposition process.

[0046] Compounds of the invention can also be used in ore processing. In particular, extracting precious metals from ores. Due to its selective solubility of metal oxides, compounds of the invention have advantage for the extraction for metals from ores. For example, precious or valuable metals can be extracted from ores whereas other non-metal materials, such as the quartz, silicates, aluminosilicates, aluminum oxides and iron oxides are unaffected and can be readily separated.

[0047] Compounds of the invention can also be used in metal processing. For example, by dissolving metals (e.g., from metal salts), one can electrodeposits metals on to other surfaces using electrolysis. Compounds of the invention can also be used in electroplating using a similar process. Metal surfaces can also be polished by removing metal oxide coating from the surface using compounds of the invention.

[0048] Because compounds of invention are ionic liquids, they can also be used in electrolytes for batteries, fuel cells and photovoltaic cells. As such, compounds of the invention are particularly useful in lithium batteries.

[0049] Selective dissolving of lanthanide and actinide series of metals also allows compounds of the invention to be used in processing spent nuclear fuel elements. In addition, selective dissolving properties of heavy metals allow compounds of the invention to be used in cleaning or decontamination of soils as well as in recovery of various metals such as copper, zinc and lead from a wide variety of samples.

[0050] Additional objects, advantages, and novel features of this invention will become apparent to those skilled in the art upon examination of the following examples thereof, which are not intended to be limiting. In the Examples, procedures that are constructively reduced to practice are described in the present tense, and procedures that have been carried out in the laboratory are set forth in the past tense.

EXAMPLES

[0051] Unless otherwise stated, all the chemicals used were of reagent grades.

(Fluorosulfonyl)(trifluoromethylsulfonyl)imide ("HFTFSI") was prepared as described in a commonly assigned U.S. Patent Application No. 14/071,597.

[0052] EXAMPLE 1 : This example illustrates a process for producing protonated trimethylglycinium (fluorosulfonyl)(trifluoromethylsulfonyl)imide, i.e., betaine

(fluorosulfonyl)(trifluoromethylsulfonyl)imide or "hbet-FTFSI".

[0053] In a 100 ml dry flask equipped with stirring device, (fluorosulfonyl)(trifluoro- methylsulfonyl)imide, i.e., HFTFSI, (11.5g, 0.05mol) was mixed with betaine powder (5.85g, 0.05mol) at room temperature under Argon atmosphere. After complete addition of betaine, the resulting reaction mixture was heated to about 70 °C for 0.5 h. The reaction mixture was then stirred at 50 °C/<100 mtorr for 1 h and cooled to room temperature to obtain a colorless clear liquid. Yield: 17.3 g, 99.5%.

[0054] EXAMPLE 2: This example illustrates a process for producing protonated betaine (fluorosulfonyl)(trifluoromethylsulfonyl)imide ("hbet-FTFSI") in water.

[0055] In a 250 ml flask equipped with stirring device, betaine (11.7g, 0. lmol) was dissolved in 35 g of water. (Fluorosulfonyl)(trifluoromethylsulfonyl)imide (23. lg, O. lmol) was added drop wise into the stirring betaine solution. After complete addition of HFTFSI, the resulting reaction mixture was stirred for additional 0.5 h. Water was removed using a rotary evaporator and the resulting mixture was further stirred at 50 °C/<100 mtorr for 2 h and then cooled to room temperature to obtain a colorless liquid. Yield: 34.45 g, 99%.

[0056] The foregoing discussion of the invention has been presented for purposes of illustration and description. The foregoing is not intended to limit the invention to the form or forms disclosed herein. Although the description of the invention has included description of one or more embodiments and certain variations and modifications, other variations and modifications are within the scope of the invention, e.g., as may be within the skill and knowledge of those in the art, after understanding the present disclosure. It is intended to obtain rights which include alternative embodiments to the extent permitted, including alternate, interchangeable and/or equivalent structures, functions, ranges or steps to those claimed, whether or not such alternate, interchangeable and/or equivalent structures, functions, ranges or steps are disclosed herein, and without intending to publicly dedicate any patentable subject matter. All references cited herein are incorporated by reference in their entirety.