Crown ether carbene and method of use

Abstract

The present invention provides a material comprising (i) a crown ether of formula (I), (ii) a crown ether of formula (II), and / or (iii) a crown ether of formula (III), or a salt thereof, wherein each m is independently an integer from 1 to 8, p is an integer from 1 to 1000, each "(F)" represents an optional bond and / or structure, each X is an optional substituent, and each * independently represent -H, =O, or a bond to the remainder of the substance, provided that at least one * is the bond to the remainder of the material, and the remainder of the material is attached via an sp3-sp3 carbon-carbon bond, methods of making the material, and methods of using the material are provided. [Formula 1] JPEG2025535965000092.jpg69149

Description

Background of the Invention

[0001]

[0001] Crown ethers are cyclic organic molecules containing oxygen-based repeating units and carbon-based repeating units. Crown ethers are known to strongly bond to certain cations to form complexes. In this respect, the oxygen atoms are oriented to coordinate with metal cations located on the inside of the ring, while the outside of the ring remains hydrophobic due to the repeating carbon units. As a result, complexes containing crown ethers and cations can be soluble in nonpolar solvents. For this reason, crown ethers can be useful in phase transfer catalysts.

[0002]

[0002] Due to the high utility of crown ether-based compounds, there remains a need for the development of substances containing crown ether-based compounds and for new and efficient methods for preparing such substances. The present invention provides such substances and methods for their preparation. Further advantages and aspects of the present invention will be readily apparent from the disclosures provided herein. Brief Summary of the Invention

[0003]

[0003] The present invention is (i) Formula (I): [ka] Crown ether, (ii) Formula (II): [ka] The crown ether, and / or (iii) formula (III): [ka] A substance containing a crown ether or a salt thereof, wherein each m is an integer from 1 to 8, and each p is an integer from 1 to 1000. [ka] " represents an optionally present bond and / or structure, each X is an optionally present substituent, each * represents -H, =O, or a bond to the remainder of the substance independently, provided that at least one * is a bond to the remainder of the substance, and the remainder of the substance is bonded via an sp3-sp3 carbon-carbon bond, to provide a substance.

[0004]

[0004] The present invention also provides a substance of formula (IV):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0005]

[0005] The present invention provides a method for preparing the substances described herein, comprising (i) reacting a hydrazide or hydrazine with a compound of formula (VII):

Chemical formula

[0006]

[0006] The present invention further provides a method for removing one or more metal ions from a solution, comprising the step of passing the solution through a substance described herein. [Brief explanation of the drawing]

[0007] [Figure 1] This bar graph shows the metal removal efficiency (MRE) percentages for lithium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, and lead, as represented by the crown ether carbene-coated nylon described in Example 7. Detailed description of the invention

[0008]

[0008] The present invention is (i) Formula (I): [ka] Crown ether, (ii) Formula (II): [ka] The crown ether, and / or (iii) formula (III): [ka] A substance comprising a crown ether of or a salt thereof, wherein each m is an integer from 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8), and p is an integer from 1 to 1000 (e.g., 1 to 500, 1 to 100, 10 to 50, or 1 to 10), and each " [ka] " indicates a bond and / or structure that is optionally present, where each X is an optionally present substituent, and each * However, each independently represents a bond to -H, =O, or the remainder of the substance, provided that at least one * However, this provides a substance in which the bond is to the remainder of the substance, and the remainder of the substance is bonded via sp3-sp3 carbon-carbon bonds.

[0009]

[0009] In some embodiments, the substance is of formula (I): [ka] The formula contains the crown ether of or a salt thereof, where each m is an integer from 1 to 8 independently, and each " [ka] " indicates an optional bond and / or structure, where each X is an optional substituent. * The symbol represents a bond to the remainder of the substance, which is bonded via sp3-sp3 carbon-carbon bonds.

[0010]

[0010] In some embodiments, the substance is of formula (II): [ka] The formula contains the crown ether of or a salt thereof, where each m is an integer from 1 to 8 independently, and each "

Chem.

[0011]

[0011] In certain embodiments, the substance is of formula (III):

Chem.

[0012] In any embodiment of the substance described herein, each m is independently an integer from 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8). Generally, each m is selected from an integer from 1 to 8 to form a crown ether selected from 12-crown-4, 15-crown-5, 18-crown-6, 21-crown-7, 24-crown-8, 27-crown-9, or 30-crown-10. For example, each m may be 2 to form 12-crown-4, each m may be 3 to form 18-crown-6, each m may be 4 to form 24-crown-8, or each m may be 5 to form 30-crown-10. Alternatively, or additionally, each m may differ to form 12-crown-4, 15-crown-5, 18-crown-6, 21-crown-7, 24-crown-8, 27-crown-9, or 30-crown-10. In some embodiments, each m is independently an integer between 1 and 4. In certain embodiments, each m is independently an integer selected from 1 or 2. In other embodiments, each m is 2.

[0013]

[0013] In any embodiment of the substance described herein, each X is an optionally present substituent. If present, X may be an electron-withdrawing substituent, an electron-donating substituent, or a neutral substituent. For example, each X can be independently selected from -OR, -OH, -NO2, -NR2, -NHR, -NH2, -COOH, -F, -Cl, -Br, -I, -COOR, -CN, -R, where R is C 1~6 The substituent is alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl). In some embodiments, the substituent "X" is absent.

[0014]

[0014] In any embodiment of the substance described herein, p is an integer between 1 and 1000 (e.g., 1 to 500, 1 to 100, 10 to 50, or 1 to 10). In some embodiments, p is an integer between 1 and 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).

[0015]

[0015] In any of the embodiments of the substance described herein, each [ka] The dashed line indicates a bond and / or structure that is of optional nature. In other words, the bond to variable X is of optional nature depending on whether substituent X is present, and the bond to variable Y can be a single or double bond depending on whether Y is -H, =O, or MS, so that one of the bonds is of optional nature, and the phenyl ring indicated by the dashed line is of optional nature.

[0016]

[0016] In any of the embodiments of the substance described herein, each * Each represents independently of a bond to -H, =O, or the remainder of the substance, provided that at least one * This is a bond to the remainder of the substance, which is bonded via sp3-sp3 carbon-carbon bonds. While we do not wish to be bound to any particular theory, it is thought that the hydrazones used to prepare the substances described herein can (i) not form from the outset, thus leaving a ketone, (ii) be hydrolyzed and / or decomposed by a polymeric support without CH insertion, thus leaving hydrogen or a ketone, or (iii) undergo CH insertion by a polymeric support to form at least one CC bond. In some embodiments, substances containing the crown ether of formula (I-III) have more than one CC bond with the remainder of the substance.

[0017]

[0017] The crown ether of formulas (I) to (III) is in formulas (I) to (III) *The crown ethers of formulas (I) to (III) can be incorporated into any suitable substance (e.g., a chemical compound or medium) insofar as they are bonded to the remainder of the substance via at least one carbon specified in the formula, the remainder of the substance being bonded via sp3-sp3 carbon-carbon bonds. The object of this application is to incorporate the crown ethers of formulas (I) to (III) into a substance via CH insertion using carbene chemistry. It will be readily apparent to those skilled in the art that the crown ethers of formulas (I) to (III) can be incorporated into a substance at any number of positions and any number of times. Thus, the substance can be any suitable substance (e.g., a chemical compound or medium) containing aliphatic CH bonds available for CH insertion. In some embodiments, the substance is porous, and therefore a liquid or fluid can pass through it.

[0018]

[0018] In some embodiments, the remainder of the substance to which the crown ethers of formulas (I) to (III) are bonded is bonded to a polymer support selected from membranes (e.g., porous membranes or permeable membranes), fiber media, polymer coatings (e.g., laminates or sealants such as polyurethane coatings, epoxy coatings, acrylic coatings, etc.) or substances (e.g., gelatin, alginate, starch, polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide, polyimide, polyester, cellulose, polystyrene, etc.), metal-organic structures, monolithic supports (e.g., catalyst supports), beads (e.g., polymer beads), filters, or resins (e.g., chromatography resins). In some embodiments, the polymer support includes gelatin, alginate, starch, polyethylene (e.g., high-density polyethylene), polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide (e.g., nylon), polyimide, polyester, cellulose, polystyrene, or a combination thereof. In certain embodiments, the polymer support includes polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, cellulose, or a combination thereof.

[0019]

[0019] Therefore, in some embodiments, the substance is of formula (IV): [ka] , formula (V): [ka] , or formula (VI): [ka] It is a substance or a salt thereof, where each m is an integer from 1 to 8 independently, and p is an integer from 1 to 1000, and each " [ka] " indicates optionally present bonds and / or structures, where each X is an optionally present substituent, and each Y is hydrogen, oxygen, or MS, provided that at least one Y is MS, and each MS is independently a polymeric support selected from membranes, fiber media, polymer coatings or materials, metal-organic structures, monolithic supports, beads, filters, or resins, where the MS are bonded via sp3-sp3 carbon-carbon bonds. All other definitions and embodiments relating to the variables m, p and X and polymeric supports are as described herein with respect to the materials of the present invention.

[0020]

[0020] In any embodiment of the substances described herein, each Y is hydrogen, oxygen, or MS, wherein at least one Y is MS, and the MS are bonded via sp3-sp3 carbon-carbon bonds. While we do not wish to be bound to any particular theory, it is thought that the hydrazones used to prepare the substances described herein can (i) not form from the outset, thus leaving a ketone, (ii) be hydrolyzed and / or decomposed by a polymeric support without CH insertion, thus leaving hydrogen or a ketone, or (iii) be CH inserted by a polymeric support to form at least one C-MS bond via sp3-sp3 carbon-carbon bonds. In some embodiments, the substances of formula (IV-VI) have more than one C-MS bond.

[0021]

[0021] In some embodiments, the substance is of formula (IV): [ka] It is a substance or a salt thereof, where each m is an integer from 1 to 8 independently, and each " [ka] " indicates optionally present bonds and / or structures, where each X is an optionally present substituent, and MS is a polymeric support selected from films, fiber media, polymer coatings or materials, metal-organic structures, monolithic supports, beads, filters, or resins, and MS is bonded via sp3-sp3 carbon-carbon bonds. All other definitions and embodiments relating to the variables m and X and the polymeric support are as described herein with respect to the materials of the present invention.

[0022]

[0022] In other embodiments, the substance is of formula (V): [ka] It is a substance or a salt thereof, where each m is an integer from 1 to 8 independently, and each " [ka] " indicates a bond that is optionally present, each X is an optionally present substituent, each Y is hydrogen, oxygen, or MS, wherein at least one Y is MS, and each MS is independently a polymer support selected from membranes, fiber media, polymer coatings or materials, metal-organic structures, monolithic supports, beads, filters, or resins, and the MS are bonded via sp3-sp3 carbon-carbon bonds. All other definitions and embodiments relating to the variables m, X and Y and polymer supports are as described herein with respect to the materials of the present invention.

[0023]

[0023] In a particular embodiment, the substance is of formula (VI): [ka] It is a substance or a salt thereof, where each m is an integer from 1 to 8 independently, and p is an integer from 1 to 1000, and each " [ka] " indicates optionally present bonds and / or structures, where each Y is hydrogen, oxygen, or MS, provided that at least one Y is MS, and each MS is independently a polymeric support selected from membranes, fibrous media, polymer coatings or materials, metal-organic structures, monolithic supports, beads, filters, or resins, where the MS are bonded via sp3-sp3 carbon-carbon bonds. All other definitions and embodiments relating to the variables m, p and Y and polymeric supports are as described herein with respect to the materials of the present invention.

[0024]

[0024] The object of this application is to incorporate the crown ethers of formulas (I) to (III) into a substance via CH insertion using carbene chemistry. Accordingly, the present invention relates to a method for producing the described substances, (i) Hydrazide or hydrazine, formula (VII): [ka] , formula (VIII): [ka] , or formula (IX): [ka] The steps include reacting it with a crown ether to form a hydrazone-containing compound, (ii) A step of reacting a hydrazone-containing compound with a polymer support selected from a film, fiber medium, polymer coating or substance, metal-organic structure, monolithic support, beads, filter, or resin to form at least one CC bond. Methods including the above are also provided. All other definitions and embodiments relating to the variables m, p and X and the polymer support are as described herein with respect to the substance of the present invention.

[0025]

[0025] This method includes the step of reacting a hydrazide or hydrazine with a crown ether of formula (VII) to (VIII). For example, the hydrazide or hydrazine can be brought into contact with (e.g., brought into contact with), mixed (e.g., shaken, stirred, etc.), heated, refluxed, or a combination thereof, for any period of time, as long as the desired hydrazone-containing compound is formed.

[0026]

[0026] The hydrazide or hydrazine may be any suitable hydrazide or hydrazine known to those skilled in the art, insofar as the hydrazide or hydrazine can decompose to form a reactive carbene when it is in the form of a hydrazone-containing compound. For example, the hydrazide or hydrazine may be p-toluenesulfonyl hydrazide (i.e., tosyl hydrazide), benzenesulfonyl hydrazide, 2,4,6-triisopropylbenzenesulfonyl hydrazide, etc. In some embodiments, the hydrazide or hydrazine is p-toluenesulfonyl hydrazide.

[0027]

[0027] Hydrazide or hydrazine can be used in any suitable amount. Generally, hydrazide or hydrazine is added in a slightly excess amount relative to the desired number of hydrazone portions (e.g., about 1 molar equivalent, about 1.05 molar equivalent, about 1.1 molar equivalent, about 1.15 molar equivalent, or about 1.2 molar equivalent). Thus, in some embodiments, hydrazide or hydrazine is added in an amount of at least 1, at least 1.05, at least 1.1, at least 1.15, or at least 1.2 molar equivalents relative to the desired number of hydrazone portions.

[0028]

[0028] In some embodiments, the formation of the hydrazone-containing compound takes place in a solvent. Thus, the reaction between a hydrazide or hydrazine and the crown ether of formulas (VII) to (VIII) can be carried out in any suitable solvent. In some embodiments, the solvent is a high-boiling point solvent (i.e., above 100°C), such as toluene. However, the formation of the hydrazone-containing compound can also take place in a low-boiling point solvent (i.e., below 100°C), such as ethanol or methanol, if accelerated by an acid accelerator.

[0029]

[0029] In some embodiments, the formation of the hydrazone-containing compound is accelerated by an acid accelerator and / or heat. The acid accelerator may be any suitable Brønsted acid or Lewis acid. For example, the formation of the hydrazone-containing compound can be accelerated by p-toluenesulfonic acid, acetic acid, or formic acid. The reaction may be heated to any suitable temperature. Since the objective is to eliminate water, in some embodiments, the reaction between the hydrazide or hydrazine and the crown ether of formulas (VII) to (VIII) is heated to a temperature above 100°C, for example, by using a Dean-Stark apparatus.

[0030]

[0030] This method further includes the step of reacting a hydrazone-containing compound with a polymer support selected from a membrane, fiber medium, polymer coating or substance, metal-organic structure, monolithic support, beads, filter, or resin to form at least one CC bond. For example, the hydrazone-containing compound can be combined with the polymer support (e.g., in contact), mixed (e.g., shaken, stirred, etc.), heated, refluxed, or a combination thereof, for any period of time as long as the desired CC bond is formed.

[0031]

[0031] In some embodiments, the CC bond is formed in the solvent. Therefore, the reaction between the hydrazone-containing compound and the polymer support can be carried out in any suitable solvent (e.g., an organic solvent). For example, the reaction between the hydrazone-containing compound and the polymer support can be carried out in ethanol, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, methanol, isopropyl alcohol, tetrahydrofuran, acetonitrile, or a combination thereof.

[0032]

[0032] In some embodiments, the reaction between the hydrazone-containing compound and the polymer support is facilitated by a base accelerator. In other words, the formation of the carbene can be facilitated by a base accelerator. The base accelerator can be any suitable Brønsted base or Lewis base. For example, the base accelerator can be sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, potassium tert-butoxide, or a combination thereof. In certain embodiments, the reaction between the hydrazone-containing compound and the polymer support is carried out in ethanol and / or N-methyl-2-pyrrolidone in the presence of sodium hydroxide.

[0033]

[0033] The base accelerator can be used in any appropriate amount. Generally, the base accelerator is added in excess of the number of hydrazone moieties present in the hydrazone-containing molecule to be reacted (for example, at least about 1 molar equivalent, at least about 2 molar equivalents, at least about 5 molar equivalents, or at least about 10 molar equivalents). Therefore, in some embodiments, the base accelerator is added in an amount of at least 1, at least 2, at least 5, or at least 10 times the number of hydrazone moieties present in the hydrazone-containing molecule to be reacted.

[0034]

[0034] In some embodiments, the formation of the carbene is further facilitated by a metal catalyst. Suitable metal catalysts for the formation and / or stabilization of the carbene moiety are known in the art. For example, the formation of the carbene can be facilitated by a copper catalyst, a rhodium catalyst, an iron catalyst, a ruthenium catalyst, a molybdenum catalyst, or a combination thereof. In certain embodiments, the reaction between the hydrazone-containing compound and the polymer support does not involve a metal catalyst.

[0035]

[0035] The reaction between the hydrazone-containing compound and the polymer support can be heated and / or exposed to ultraviolet (UV) light. While we do not wish to be bound by any particular theory, it is thought that the formation of CC bonds (e.g., via CH insertion) can be accelerated by increasing the temperature (e.g., above 50°C or above 75°C) and / or UV light. In certain embodiments, the reaction between the hydrazone-containing compound and the polymer support is cured using patterned selective functionalization by UV light exposure.

[0036]

[0036] The substances described herein can be used for any suitable purpose in any suitable industrial application. For example, the substances described herein can be used in water purification, wastewater treatment, mining, electronic (e.g., microelectronics), papermaking, pharmaceutical, biomedical, energy (e.g., as separators in fuel cells or batteries), or metallurgical applications. Generally, the substances described herein are used to selectively remove one or more metal ions from a fluid (i.e., a solution). The fluid can be any suitable liquid containing a solvent (e.g., water, alcohol, sulfoxide, sulfide, acetate, ether, amide, nitrile, or a combination thereof) and one or more metal ions. In certain embodiments, the fluid (i.e., the solution) is an aqueous solution.

[0037]

[0037] In some embodiments, the substances described herein can be used in a method for removing one or more metal ions from a solution, comprising the step of passing the solution through the substance. For example, the substance can be used as a filter, porous medium, chromatographic resin, membrane, etc., through which a solution passes to remove one or more metal ions. Thus, the present invention relates to a method for removing one or more metal ions from a solution, comprising passing the solution through (i) Formula (I): [ka] Crown ether, (ii) Formula (II): [ka] The crown ether, and / or (iii) formula (III): [ka] A substance containing the crown ether of or a salt thereof, where each m is an integer from 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8), and p is an integer from 1 to 1000 (e.g., 1 to 500, 1 to 100, 10 to 50, or 1 to 10), and each " [ka] " indicates a bond and / or structure that is optionally present, where each X is an optionally present substituent, and each * However, each independently represents a bond to -H, =O, or the remainder of the substance, provided that at least one * The present invention further provides a method comprising the step of passing a substance through which the substance is bonded to the remainder of the substance, the remainder of the substance being bonded via sp3-sp3 carbon-carbon bonds. All other definitions and embodiments relating to the variables m, p, X, and Y, as well as the polymer support, are as described herein with respect to the substance of the present invention.

[0038]

[0038] This method can be used to remove any suitable ions. Alternatively, or additionally, this method can be used to allow any suitable ions to pass through a substance. For example, this method can be used to selectively remove one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof. Alternatively, or additionally, this method can be used to selectively allow one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof to pass through a substance. In certain embodiments, this method selectively allows lithium to pass through a material and removes one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof.

[0039]

[0039] This method can remove any appropriate amount of one or more metal ions from a solution. For example, this method can remove at least 40% of one or more metal ions from a solution, at least 50% of one or more metal ions from a solution, at least 60% of one or more metal ions from a solution, at least 70% of one or more metal ions from a solution, at least 80% of one or more metal ions from a solution, or at least 90% of one or more metal ions from a solution. In some embodiments, this method removes at least 50% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof. In a particular embodiment, this method removes at least 60% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof. In a preferred embodiment, this method removes at least 70% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof.

[0040]

[0040] In some embodiments, the solution through which the substance has passed is the desired product of the method described herein. Thus, in such embodiments, the method may further include the step of recovering the solution through which the substance has passed (e.g., an aqueous solution). While we do not wish to be bound by any particular theory, if smaller metal ions such as lithium and / or sodium are desired, it is thought that the recovered solution will be the desired product because smaller metal ions such as lithium and / or sodium pass through the substance described herein more readily.

[0041]

[0041] In other embodiments, one or more metal ions removed from the solution are desired products of the method described herein. Thus, in these embodiments, the method may further include recovering one or more metal ions removed from the solution. One or more metal ions can be recovered by any suitable means. For example, a substance containing one or more metal ions can be washed with the recovery solution. While we do not wish to be bound by any particular theory, if larger metal ions such as magnesium, aluminum, potassium, calcium, manganese, iron, and barium are desired, it is assumed that these desired metal ions will remain in the substance because larger metal ions are less likely to pass through the substance described herein.

[0042]

[0042] The aspects of the invention described herein, including embodiments, may be useful individually or in combination with one or more other aspects or embodiments. Without limiting the foregoing description, certain non-limiting embodiments of this disclosure, numbered 1 to 22, are described below. As will be apparent to those skilled in the art upon reading this disclosure, each individually numbered embodiment may be used or combined with any of the preceding or succeeding individually numbered embodiments. This is intended to cover all such combinations of embodiments and is not limited to the combinations of embodiments expressly described below: Embodiments

[0043]

[0043] (1) In embodiment (1), (i) formula (I): [ka] Crown ether, (ii) Formula (II): [ka] The crown ether, and / or (iii) formula (III): [ka] A substance containing a crown ether or a salt thereof, wherein each m is an integer from 1 to 8, and each p is an integer from 1 to 1000. [ka] " indicates a bond and / or structure that is optionally present, where each X is an optionally present substituent, and each * However, each independently represents a bond to -H, =O, or the remainder of the substance, provided that at least one * However, the substance is presented in which the bond is to the remainder of the substance, and the remainder of the substance is bonded via sp3-sp3 carbon-carbon bonds.

[0044]

[0044] (2) In embodiment (2), the substance is of formula (I): [ka] The formula contains the crown ether of or a salt thereof, where each m is an integer from 1 to 8 independently, and each " [ka] " indicates a bond and / or structure that is optionally present, where each X is an optionally present substituent. * However, the substance of embodiment (1) is presented, which represents bonding to the remainder of the substance, and the remainder of the substance is bonded via sp3-sp3 carbon-carbon bonds.

[0045]

[0045] (3) In embodiment (3), the substance is of formula (II): [ka] The formula contains the crown ether of or a salt thereof, where each m is an integer from 1 to 8 independently, and each " [ka] " indicates a bond that exists by choice, and each X is a substituent that exists by choice, and each * However, each independently represents a bond to -H, =O, or the remainder of the substance, provided that at least one * However, the bond is to the remainder of the substance, and the remainder of the substance is bonded via sp3-sp3 carbon-carbon bonds, as presented in Embodiment (1).

[0046]

[0046] (4) In embodiment (4), the substance is of formula (III): [ka] The formula comprises the crown ether of or a salt thereof, where each m is an integer from 1 to 8 independently, and p is an integer from 1 to 1000, and each * However, each independently represents a bond to -H, =O, or the remainder of the substance, provided that at least one * However, the bond is to the remainder of the substance, and the remainder of the substance is bonded via sp3-sp3 carbon-carbon bonds, as presented in Embodiment (1).

[0047]

[0047] (5) Embodiment (5) presents the substances of Embodiments (1) to (4), in which each m is an integer from 1 to 4 independently.

[0048]

[0048] (6) Embodiment (6) presents one of the substances from Embodiments (1) to (5), in which each m is an integer independently selected from 1 or 2.

[0049]

[0049] (7) Embodiment (7) presents one of the substances from Embodiments (1) to (6), where each m is 2.

[0050]

[0050] (8) In embodiment (8), the substance is of formula (IV): [ka] , formula (V): [ka] , or formula (VI): [ka] It is a substance or a salt thereof, where each m is an integer from 1 to 8 independently, and p is an integer from 1 to 1000, and each " [ka] A substance of Embodiment (1) is presented, wherein "" represents optionally present bonds and / or structures, each X is an optionally present substituent, each Y is hydrogen, oxygen, or MS, provided that at least one Y is MS, and each MS is independently a polymer support selected from films, fiber media, polymer coatings or materials, metal-organic structures, monolithic supports, beads, filters, or resins, and the MS are bonded via sp3-sp3 carbon-carbon bonds.

[0051]

[0051] (9) In embodiment (9), the substance is of formula (IV): [ka] It is a substance or a salt thereof, where each m is an integer from 1 to 8 independently, and each " [ka] A substance of Embodiment (8) is presented, wherein "" indicates optionally present bonds and / or structures, each X is an optionally present substituent, MS is a polymer support selected from films, fiber media, polymer coatings or materials, metal-organic structures, monolithic supports, beads, filters, or resins, and MS is bonded via sp3-sp3 carbon-carbon bonds.

[0052]

[0052] (10) In embodiment (10), the substance is of formula (V): [ka] It is a substance or a salt thereof, where each m is an integer from 1 to 8 independently, and each " [ka] A material of Embodiment (8) is presented, in which "" indicates a bond that is optionally present, each X is an optionally present substituent, each Y is hydrogen, oxygen, or MS, wherein at least one Y is MS, and each MS is independently a polymer support selected from a film, fiber medium, polymer coating or substance, metal-organic structure, monolithic support, beads, filter, or resin, and the MS are bonded via sp3-sp3 carbon-carbon bonds.

[0053]

[0053] (11) In embodiment (11), the substance is of formula (VI): [ka] It is a substance or a salt thereof, where each m is an integer from 1 to 8 independently, and p is an integer from 1 to 1000, and each " [ka] A material of Embodiment (8) is presented, in which "" indicates optionally present bonds and / or structures, where each Y is hydrogen, oxygen, or MS, provided that at least one Y is MS, and each MS is independently a polymeric support selected from films, fiber media, polymer coatings or materials, metal-organic structures, monolithic supports, beads, filters, or resins, and the MS are bonded via sp3-sp3 carbon-carbon bonds.

[0054]

[0054] (12) Embodiment (12) presents one of the substances from Embodiments (8) to (11), in which each m is an integer from 1 to 4 independently.

[0055]

[0055] (13) Embodiment (13) presents one of the substances from Embodiments (8) to (12), in which each m is an integer independently selected from 1 or 2.

[0056]

[0056] (14) Embodiment (14) presents one of the substances from Embodiments (8) to (13), where each m is 2.

[0057]

[0057] (15) Embodiment (15) presents any one of the materials from Embodiments (8) to (14) in which the polymer support is gelatin, alginate, starch, polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide, polyimide, polyester, cellulose, polystyrene, or a combination thereof.

[0058]

[0058] (16) Embodiment (16) is a method for producing any one of the substances of Embodiments (8) to (15), (i) Hydrazide or hydrazine, formula (VII): [ka] , formula (VIII): [ka] , or formula (IX): [ka] The steps include reacting it with a crown ether to form a hydrazone-containing compound, (ii) A step of reacting a hydrazone-containing compound with a polymer support selected from a film, fiber medium, polymer coating or substance, metal-organic structure, monolithic support, beads, filter, or resin to form at least one CC bond. Methods including this are presented.

[0059]

[0059] (17) Embodiment (17) presents the method of Embodiment (16) in which the hydrazide or hydrazine is p-toluenesulfonyl hydrazide.

[0060]

[0060] (18) Embodiment (18) presents a method for removing one or more metal ions from a solution, comprising the step of passing the solution through one of the substances or a salt thereof of Embodiments (1) to (15).

[0061]

[0061] (19) Embodiment (19) presents the method of Embodiment (18) in which the solution is an aqueous solution.

[0062]

[0062] (20) Embodiment (20) presents the method of Embodiment (18) or Embodiment (19) for removing at least 50% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof.

[0063]

[0063] (21) Embodiment (22) presents the method of Embodiment (18) or Embodiment (19) which removes at least 60% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof.

[0064]

[0064] (22) Embodiment (22) presents the method of Embodiment (18) or Embodiment (19) for removing at least 70% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof. [Examples]

[0065]

[0065] These following embodiments further illustrate the present invention, but should not be construed as limiting its scope.

[0066] Example 1

[0066] This embodiment provides an exemplary experimental procedure for preparing the crown ether of formula (VII) described herein, which is summarized in Scheme 1. [ka]

[0067]

[0067] Benzocrown ether 1 (5 g, 18.6 mmol, 1 equivalent) was dissolved in Eaton's reagent (35 g) at 50°C. Once completely dissolved, 4-aminobenzoic acid 2 (2.8 g, 20.5 mmol, 1.1 equivalents) was added, and the reaction was heated at 50°C for 16 hours. The resulting mixture was poured onto ice, filtered, and washed with water. After drying the resulting solid product through a filter, the product was recrystallized from ethanol to produce 2.23 g (31%) of aminobenzocrown ether 3.

[0068] Example 2

[0068] This embodiment provides an exemplary experimental procedure for preparing the crown ether of formula (VII) described herein, which is summarized in Scheme 2. [ka]

[0069]

[0069] Dibenzocrown ether 4 (24.0 g, 66.5 mmol) was dissolved in Eaton's reagent (110 mL) at 50°C. Once completely dissolved, 4-(methylamino)benzoic acid 5 (10.0 g, 66.5 mmol, 1 equivalent) was added, and the reaction was heated at 50°C for 4 hours. The resulting mixture was poured onto ice, filtered, and washed with water. After drying the resulting solid product through a filter, crude aminodibenzocrown ether 6 (30 g) was recovered. Nuclear magnetic resonance (NMR) spectroscopy showed that the crude product was more than 85% of the desired product 6, and that the mass balance was a mixture of the starting material 4 and the doubling product.

[0070] Example 3

[0070] This embodiment provides an exemplary experimental procedure for preparing the crown ether of formula (VIII) described herein, which is summarized in Scheme 3. [ka]

[0071]

[0071] Dibenzocrown ether 4 (5.0 g, 13.8 mmol, 1 equivalent) was dissolved in Eaton's reagent (35 g) at 50°C. Once completely dissolved, 4-aminobenzoic acid 2 (4.16 g, 30.4 mmol, 2.2 equivalents) was added, and the reaction was heated at 50°C for 4 hours. The resulting mixture was poured onto ice, filtered, and washed with water. After drying the resulting solid product through a filter, the product was recrystallized from ethanol to produce 4.1 g (50%) of diaminodibenzocrown ether 7.

[0072] Example 4

[0072] This embodiment provides an exemplary experimental procedure for preparing the crown ether of formula (VIII) described herein, which is summarized in Scheme 4. [ka]

[0073]

[0073] Dibenzocrown ether 4 (5.0 g, 13.8 mmol, 1 equivalent) was dissolved in Eaton's reagent (35 g) at 50°C. Once completely dissolved, benzoic acid 8 (3.71 g, 30.4 mmol, 2.2 equivalents) was added, and the reaction was heated at 50°C for 4 hours. The resulting mixture was poured onto ice, filtered, and washed with water. After drying the resulting solid product through a filter, the product was recrystallized from ethanol to produce 7.25 g (92%) of dibenzo-18-crown-6(9) dibenzoate.

[0074] Example 5

[0074] This embodiment provides an exemplary experimental procedure for preparing the crown ether of formula (IX) described herein, which is summarized in Scheme 5. [ka]

[0075]

[0075] Dibenzocrown ether 4 (2.29 g, 13.8 mmol, 1 equivalent) is dissolved in Eaton's reagent (70 g) at 50°C. Once completely dissolved, 1,4-benzenedicarboxylic acid 10 (5.00 g, 13.8 mmol, 1 equivalent) is added, and the reaction is heated at 50°C for 4 hours. The resulting mixture is poured over ice, filtered, and washed with water, and then with methanol. After drying the resulting solid product through a filter, an approximate amount of polymer product 11 was recovered at a degree of polymerization of about 20 by nuclear magnetic resonance (NMR) spectroscopy.

[0076] Example 6

[0076] This embodiment provides an exemplary experimental procedure for preparing the substance of formula (V) described herein, the first step of this experimental procedure is summarized in Scheme 6. [ka]

[0077]

[0077] Benzo-18-crown-6(9) dibenzoate (3.52 g, 6 mmol, 1 equivalent), p-toluenesulfonyl (i.e., tosyl) hydrazide (2.23 g, 12 mmol, 2 equivalents), and p-toluenesulfonic acid (10 mg, 1 mol%) were heated under reflux in toluene (100 mL) for 16 hours using a Dean-Stark trap. The resulting mixture was cooled in a freezer and filtered to obtain a powder, which was washed with ethanol and then dried. Nuclear magnetic resonance (NMR) spectroscopy was used to confirm the desired conversion to an imine with a yield of approximately 76% crude product 12. The isolated hydrazone 12 was then bonded to nylon as shown in Scheme 7. [ka]

[0078]

[0078] A 1% by weight or 3% by weight coating solution was prepared containing 0.41 g or 1.24 g of hydrazone 12 and 6 mmol of NaOH (added as a 50% aqueous solution) in N-methyl-2-pyrrolidone (21 mL) and ethanol (21 mL). A 4.5 inch × 10 inch nylon strip was coated with the 1% by weight or 3% by weight coating solution using a benchtop dip coater with an 8 mil gap height. The coated nylon was cured in an oven at 85°C for 2 hours. The initial absorption percentage was measured, and the coated nylon was then washed by immersing it in 3% HCl for 1 hour, followed by immersing it in deionized water for 1 hour. The coated nylon was then trickle washed with deionized water for 10 minutes and dried in an oven at 85°C for 2 hours. The absorption percentage and critical weight surface tension (CWST) of the coated nylon were measured after washing. The results are shown in Table 1.

[0079] [Table 1]

[0080]

[0079] As is evident from the results shown in Table 1, higher concentrations of hydrazone solution resulted in better crown ether absorption in the coated nylon. Furthermore, Table 1 shows that as absorption increased, the critical weight surface tension (CWST) of the coated nylon decreased.

[0081] Example 7

[0080] This embodiment demonstrates the metal removal efficiency of the substance of formula (V) described herein.

[0082]

[0081] A metal removal efficiency (MRE) test was performed using a 47 mm punched disc of the nylon-coated material from Test 4 of Example 6, which had been washed with a 5% HCl solution and deionized water. 20-30 mL or 30-40 mL of a solution of propylene glycol methyl ether acetate (i.e., OK73 fluid) containing 1 ppb of each metal impurity (i.e., lithium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, and lead) was passed through the disc, and the resulting metal ion concentrations were measured by inductively coupled plasma mass spectrometry (ICP-MS). The metal removal efficiency (i.e., the percentage concentration removed) was calculated, and the results for the 20-30 mL test (left) or the 30-40 mL test (right) are plotted in the figure.

[0083]

[0082] As is evident from the results shown in the figure, the nylon-coated material of Test 4 of Example 6 removed more than 50% of magnesium, aluminum, potassium, calcium, manganese, iron, and barium, while selectively allowing ions such as lithium and sodium to pass through. Furthermore, the nylon-coated material of Test 4 of Example 6 was particularly effective in removing magnesium and barium, exhibiting more than 90% MRE in both cases.

[0084]

[0083] All references cited herein, including publications, patent applications and patents, are incorporated herein by reference to the same extent as each reference is individually and specifically indicated as being incorporated by reference, and as if it were included herein in whole.

[0085]

[0084] In the context describing the present invention (particularly in the context of the following claims), the use of the terms “a,” “an,” “the,” and “at least one,” and similar demonstrative pronouns, should be interpreted as encompassing both singular and plural, unless otherwise specifically indicated herein or unless clearly contradicted by the context. The use of the term “at least one” following an enumeration of one or more items (e.g., “at least one A and B”) should be interpreted as meaning one item selected from the enumerated items (A or B), or any combination of two or more of the enumerated items (A and B), unless otherwise specifically indicated herein or unless clearly contradicted by the context. The terms “equip,” “have,” “include,” and “contain” should be interpreted as open-ended terms unless otherwise specifically mentioned (i.e., “include, but not limited to”). The enumeration of value ranges in this specification is intended merely as a simplified method for referring individually to each distinct value within the range, unless otherwise specifically indicated herein, and each distinct value is incorporated herein as if it were listed individually. All methods described herein may be carried out in any suitable order, unless otherwise specifically indicated herein or unless it is clearly inconsistent with the context. Any embodiments or use of exemplary language (e.g., “like”) described herein is intended merely to improve the invention and does not limit the scope of the invention unless specifically asserted otherwise. No language herein should be construed as indicating an element not claimed as essential to the practice of the invention.

[0086]

[0085] Preferred embodiments of the Invention, including the best mode known to the inventors for carrying out the Invention, are described herein. Variations of these preferred embodiments will become apparent to those skilled in the art by reading the preceding description. The inventors expect that those skilled in the art will use such variations appropriately, and the inventors intend that the Invention may be practiced in ways other than those specifically described herein. Accordingly, the Invention includes all modifications and equivalents of the subject matter listed in the claims appended herein, as permitted by applicable law. Furthermore, unless otherwise specifically indicated herein, or unless otherwise clearly inconsistent with the context, any combination of the above elements in all possible variations is incorporated into the Invention. In certain embodiments, for example, the following items are provided: (Item 1) (i) Equation (I): [ka] Crown ether, (ii) Formula (II): [ka] The crown ether, and / or (iii) formula (III): [ka] A substance containing a crown ether or a salt thereof, wherein each m is an integer from 1 to 8, and each p is an integer from 1 to 1000. [ka] " indicates a bond and / or structure that is optionally present, where each X is an optionally present substituent, and each * However, each independently represents a bond to -H, =O, or the remainder of the substance, provided that at least one * However, the bond is to the remainder of the substance, and the remainder of the substance is bonded via sp3-sp3 carbon-carbon bonds. (Item 2) The aforementioned substance is given by formula (I): [ka] The formula contains the crown ether of or a salt thereof, where each m is an integer from 1 to 8, and each " [ka] " indicates a bond and / or structure that is optionally present, where each X is an optionally present substituent. * The substance according to item 1, wherein the bond to the remainder of the substance is expressed, and the remainder of the substance is bonded via sp3-sp3 carbon-carbon bonds. (Item 3) The aforementioned substance is given by formula (II):

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Claims

1. (i) Formula (V): 【Chemistry 16】 A substance comprising a crown ether or a salt thereof, wherein each m is an integer from 1 to 8, and each " 【Chemistry 4】 " indicates a bond that is optionally present, each X is an optionally present substituent, each Y is hydrogen, oxygen, or MS, wherein at least one Y is MS, and each MS is independently a polymer support selected from a film, fiber medium, polymer coating or substance, metal-organic structure, monolithic support, beads, filter, or resin, and the MS are bonded via sp3-sp3 carbon-carbon bonds.

2. The substance according to claim 1, wherein each m is an integer from 1 to 4 independently.

3. The substance according to claim 1, wherein each m is an integer independently selected from 1 or 2.

4. The substance according to claim 1, wherein each m is 2.

5. The substance according to claim 1, wherein the polymer support comprises gelatin, alginate, starch, polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide, polyimide, polyester, cellulose, polystyrene, or a combination thereof.

6. A method for producing the substance described in claim 1, (i) Hydrazide or hydrazine, formula (VIII): 【Chemistry 21】 The steps include reacting it with a crown ether to form a hydrazone-containing compound, (ii) The step of reacting the hydrazone-containing compound with a polymer support selected from a film, fiber medium, polymer coating or substance, metal-organic structure, monolithic support, beads, filter, or resin to form at least one C-C bond. Methods that include...

7. The method according to claim 6, wherein the hydrazide or hydrazine is p-toluenesulfonyl hydrazide.

8. A method for removing one or more metal ions from a solution, comprising the step of passing the solution through a substance or salt thereof as described in claim 1.

9. The method according to claim 8, wherein the solution is an aqueous solution.

10. The method according to claim 8, wherein at least 50% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof are removed.

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