Methods and compositions for the proudction of amides from sugar lactones

Abstract

A method comprising contacting an amine reactant with a lactone under conditions suitable for the formation of an amide, wherein the lactone comprises glucono-delta lactone (GDL), D-glucaric acid 1,4,6,3 dilactone (GAdL), substituted lactones or combinations thereof. A method of preparing a biobased amide comprising contacting an amine with a sugar-derived lactone under conditions suitable for the formation of an amide.

Description

METHODS AND COMPOSITIONS FOR THE PROUDCTION OF AMIDES FROM SUGAR LACTONESCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application Serial No. 63 / 518,052 filed August 7, 2023 and entitled “METHODS AND COMPOSITIONS FOR THE PRODUCTION OF AMIDES FROM SUGAR LACTONES,” which is hereby incorporated herein by reference in its entirety for all purposes.STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0002] Not applicable.FIELD

[0003] The present disclosure relates generally to platform chemicals. More particularly, the present disclosure relates to the production of amides from biobased chemicals.BACKGROUND

[0004] Over the last 150 years, the synthesis of inexpensive chemicals from fossilized forms of carbon (e.g. oil, coal, natural gas) has dramatically altered society through their broad applications, ranging from cosmetics to plastics. This petroleum-based carbon feedstock generates a small collection of platform chemicals from which highly efficient chemical conversions lead to the manufacture of a large variety of chemical products. However, the current approach to producing these carbon-based chemicals is inherently non-sustainable as feedstocks that required millions of years to form are being depleted. The creation of a truly sustainable chemical industry will only occur when the timescale of the feedstock formation matches the timescale of its utilization to make chemicals.

[0005] Amide bond synthesis is ranked as the second most important challenge in key green chemistry research areas identified by the ACS Green Chemistry Institute. Amides are molecules that contain a nitrogen atom which is connected to the carbon atom of a carbonyl group and are typically formed by the reaction of an amine and carboxylic acid with the concomitant elimination of water molecules. Generating amides by chemical synthesis typically relies on toxic chemicals, the use of organic solvents, and stoichiometric amounts of coupling reagents, which is associated with genemolar ration of considerable amounts of waste.

[0006] Amides have a wide array of industrial uses. For example, unsubstituted aliphatic carboxylic acid amides are used, for example, as intermediates, stabilizers, release agents for plastics, films, surfactants, and soldering fluxes. Substituted amides such as dimethylformamide and dimethylacetamide have powerful solvent properties. Some unsaturated aliphatic amides, such as acrylamide, are reactive monomers used in polymer synthesis. Acrylamide can be employed in a variety of applications such as in the synthesis of dyes, adhesives, paper and textile sizing, permanent press fabrics, and sewage and waste treatment. In the metal industry amides are used in applications such as ore processing, and in civil engineering for the construction of dam foundations and tunnels. Polyacrylamides find extensive utility as flocculants in water and sewage treatment, and as strengthening agents during paper manufacture in the paper and pulp industry. An ongoing need exists for amides obtained from renewable resources.SUMMARY

[0007] Disclosed herein is a method comprising contacting an amine reactant with a lactone under conditions suitable for the formation of an amide, wherein the lactone comprises glucono-delta lactone (GDL), D-glucaric acid 1 ,4, 6, 3 dilactone (GAdL), substituted GDL, substituted D-glucaric acid 1 ,4, 6, 3 dilactone, or combinations thereof.

[0008] Also disclosed herein is a method of preparing a biobased amide comprising contacting an amine with a sugar-derived lactone under conditions suitable for the formation of an amide.BRIEF DESCRIPTION OF THE DRAWINGS

[0009] For a detailed description of various exemplary aspects, reference will now be made to the accompanying drawings in which:

[0010] Figure 1 A is a schematic depiction of the double dehydration of glucaric acid to form glucaric acid 1 ,4:6, 3 dilactone (GAdL).

[0011] Figure 1 B depicts the structure of glucaric acid 1 ,4:6,3 dilactone.

[0012] Figure 1 C depicts the structure of glucono-delta lactone.

[0013] Figure 2 depicts the structure of monoamines.

[0014] Figure 3 depicts the structure of diamines, triamines and polyamines.

[0015] Figure 4 depicts the reaction of a primary monoamine with glucaric acid 1 ,4:6,3 dilactone in stochiometric amounts and the formation of the mono amide salt.

[0016] Figure 5 depicts the reaction of a primary monoamine with glucaric acid 1 ,4:6,3 dilactone with an excess of monoamine.

[0017] Figure 6A depicts the stoichiometric reaction of a stoichiometric ratio of a primary diamine with glucaric acid 1 ,4:6,3 dilactone.

[0018] Figure 6B depicts the stoichiometric reaction of a primary diamine with glucaric acid 1 ,4:6,3 dilactone with the dilactone in excess to form a diamide dilactone of glucaric acid, which can then be reacted with an acid to form a straight chain diamide or monolactone diamide.

[0019] Figure 6C depicts the stoichiometric reaction of a primary diamine with glucaric acid 1 ,4:6,3 dilactone and a crosslinking agent to form a crosslinked polymer.

[0020] Figure 7A depicts the reaction of glucaric acid 1 ,4:6, 3 dilactone with an excess of a primary diamine to make a primary amine terminated diamide, followed by the reaction with a dicarboxylic acid or diesters or diacyl halides.

[0021] Figure 7B depicts the chemical structures of dicarboxylic acids or diesters or diacyl halides for use in the present disclosure.

[0022] Figure 7C depicts the acid catalyzed polymerization of an amide to form a polyether.

[0023] Figure 7D depicts the acid catalyzed polymerization of an amide with a carboxylic acid to form a polyester.

[0024] Figure 8 depicts the reaction of glucono-delta lactone with a monoamine.

[0025] Figure 9A depicts the reaction of glucono-delta lactone with an excess of diamine.

[0026] Figure 9B depicts the reaction of excess glucono-delta lactone with a monoamine.

[0027] Figure 9C depicts the reaction of glucono-delta lactone with an excess of amine alcohol.

[0028] Figure 10 depicts the reaction of diglucaric acid amide lactone with a diamine.

[0029] Figure 11 depicts the reaction of diglucaric acid amide lactone with a monoamine.

[0030] Figure 12A depicts the polymerization of gluconic acid amide lactone with an acid catalyst to form a polyether.

[0031] Figure 12B depicts the polymerization of gluconic acid amide lactone and carboxylic acid and an acid catalyst to form a polyester.

[0032] Figure 12C depicts the chemical structures of amino alcohols.DETAILED DESCRIPTION

[0033] The following discussion is directed to various exemplary aspects. However, one of ordinary skill in the art will understand that the examples disclosed herein have broad application, and that the discussion of any aspect is meant only to be exemplary of that aspect, and not intended to suggest that the scope of the disclosure, including the claims, is limited to that aspect.

[0034] The figures are not necessarily to scale. Certain features and components herein may be shown exaggerated in scale or in somewhat schematic form and some details of conventional elements may not be shown in interest of clarity and conciseness.

[0035] In the following discussion and in the claims, the terms “including” and “comprising” are used in an open-ended fashion, and thus should be interpreted to mean “including, but not limited to... .” As used herein, the terms “approximately,” “about,” “substantially,” and the like mean within 10% (i.e., plus or minus 10%) of the recited value. Thus, for example, a recited angle of “about 80 degrees” refers to an angle ranging from 72 degrees to 88 degrees.

[0036] Unless the context dictates the contrary, all ranges set forth herein should be interpreted as being inclusive of their endpoints, and open-ended ranges should be interpreted to include only commercially practical values. Similarly, all lists of values should be considered as inclusive of intermediate values unless the context indicates the contrary.

[0037] Disclosed herein are methods and compositions for the production of one or more amides from a sugar-derived molecule. In one or more aspects, the sugar-derived molecule is a sugar oxidation product, additionally or alternatively, the sugar-derived molecules are lactones.

[0038] In one or more aspects, a method of the present disclosure comprises reacting one or more sugar oxidation products under conditions suitable for the formation of one or more amides. For example, a dilactone can be produced by double dehydration of glucaric acid in the presence of methyl isobutyl ketone. This exemplary reaction is depicted in Figure 1A.

[0039] In one or more aspects, a reagent to produce one or more amides comprises a lactone obtained from a renewable resource. Nonlimiting examples of lactones derived from a renewable resource include glucono-delta lactone (GDL), glucaric acid 1 ,4:6,3 dilactone (GAdL), derivatives thereof or combinations thereof. The structures of GDL and GAdL are presented in Figures 1 B and 1C, respectively. In one or more aspects, the lactones GDL, GAdL may be unsubstituted. In alternative aspects, the GDL, GAdLor both contain one or more substituents, nonlimiting examples of which are disclosed herein. For example, GDL, GAdL or both may have hydoxyl group substituents at one or more of any of the available positions on these molecules. Hereinafter the disclosure will refer to the use of GDL or GAdL but it contemplated that substituted compounds of GDL or GAdL may be also be reacted in place of or in addition to the unsubstituted lactones. Nonlimiting examples of alternative lactones are depicted in Structures I or Structure II below, where each Z is independently acetate, methyl oxide, trityl or disopropylidine.Structure I Structure II

[0040] In an aspect, a method of the present disclosure comprises reacting an amine with a lactone under conditions suitable for the formation of an amide product. In one or more aspects, the lactones disclosed herein react readily with amines to form an amide product examples of which include monolactone-monoamides and catalytically formed polyamides.

[0041] In an aspect, an amine reactant suitable for use in the present disclosure is an aliphatic compound. Herein the term aliphatic refers to an acyclic or cyclic, saturated or unsaturated amine. In various aspects, the amine reactant may comprise a monoamine, a diamine, triamine, polyamine, or combinations thereof.

[0042] In an aspect, the amine reactant is a monoamine. Nonlimiting examples of monoamines for use in the present disclosure include ethanolamine (EtA); propylamine; butylamine (BuA); sec-butylamine; N,N-diethyl-1 ,3-diaminopropane; isopropylamine; 2- ethylhexylamine; pentylamine (AML); 2-ethyl-hexylamine; hexylamine (HexA); octylamine (OctA); dodecylamine (DodA); oleylamine (Oam); phenethylamine (PHEA); 1-adamanantamine (ADA); cyclohexylamine (cHexA); tert-butylamine (tBuA);2- (aminomethyl)phenol; 2-(aminomethyl)benzyl alcohol; 2-aminophenol; 2-aminobenzyl alcohol; 2-(aminomethyl)benzyl alcohol; 3-(aminomethyl)phenol; 3-(aminomethyl)benzyl alcohol; 4-(aminomethyl)phenol; 4-(aminomethyl)benzyl alcohol; 4-aminophenol; 3-aminophenol; 3-(aminomethyl)benzyl alcohol; 4- (aminomethyl)phenol; 4-(aminomethyl)benzyl alcohol; 4-aminophenol; 3-aminophenol; 3-aminobenzyl alcohol; 4-aminobenzyl alcohol; 2-vinylbenzylamine; 4-vinylaniline; 2- vinylaniline; 3-vinylbenzylamine; 3-vinylaniline; 4-vinylbenzylamine; aminoalkyl acrylamide; aminoalkyl methacrylamide; and combinations thereof. The structures of these monoamines are depicted in Figure 2.

[0043] In an aspect, the amine reactant is a diamine. Nonlimiting examples of diamines for use in the present disclosure include ethylenediamine (EtDA); diaminopropane (DAP); 1 ,2-diaminopropane; 2,2-dimethyl-1 ,3-propanediamine; putrescine (BDA); cadaverine (PDA); 2-methyl-1 ,5-pentanediamine (MPMD); hexamethylenediamine (HMDA); dodecylenediamine (DodDA); 4,4’-diaminodicyclohexylmethane; 2,2- (ethylenedioxy)diethylamine; 2-[2-[2-[2-aminoethoxy]ethoxy]ethoxy]ethylamine; 1 ,3- bis(2-aminoethyl)urea; glucarodiamine (DIG); L-lysine (LYS); isophorone diamine (IPDA); m-xylylene diamine (mXDA); 1 ,5-diaminonapthalene (1 ,5DAN) and combinations thereof.

[0044] In an aspect, the amine reactant is a triamine. Nonlimiting examples of triamines for use in the present disclosure include diethylenetriamine (DETA); tetraethylenepentamine; 2-aminoethyl ether; triethylene tetramine;melamine (MEL); tris(2-aminoethyl)amine (TREN) and a combination thereof.

[0045] In an aspect, the amine reactant is a polyamine. Nonlimiting examples of polyamines for use in the present disclosure include polyethylenimine (PEI); amino polypropylene acrylamide; amino polyethylene acrylamide and combinations thereof. The structures of these diamines, triamines and polyamines are depicted in Figure 3.

[0046] In one or more aspects, the amine reactant (e.g., monoamine, polyamine) may contain one or more additional functional groups. Nonlimiting examples of additional functional groups that may be present in the amine reactant include other amines (- NH2), alcohols (-OH), alkenes (-C=C-), ketones (-RCOR-), acrylates (-C=COOR-), carboxylic acids (-COOH), aldehyde (R-CHO), acyl halides (R-(CO)-X), carboxylates (R-COO), esters (R-(CO)-O-R’), ethers (R-O-R’), imides, ((RCO^N-R’) isocyanates (R- NCO), or combinations thereof.

[0047] In some aspects, reaction of the amine reactant and a lactone both of the type disclosed herein produces a first product, Product A, which can be used as formed. Inadditional or alternative aspects, Product A is further reacted to produce a second product, Product B.

[0048] In one or more aspects, a primary monoamine of the type disclosed herein is reacted with GAdL under conditions suitable for the formation of a straight chain glucaric amide. Herein the term “primary” has the IUPAC definition referring to when one of three hydrogen atoms in ammonia is replaced by an organic substituent. Similarly, secondary amines have two of the three hydrogen atoms replaced with organic substituents and tertiary amines have all three of the hydrogens of the amine replaced with organic substituents.

[0049] In one or more aspects, formation of the glucaric amide is carried out by contacting the primary monoamine and GAdL and subjecting the contacted materials to one or more of the following reaction conditions: a temperature of from about 20 °C to about 150 °C, or about 20 °C to about 40 °C or about 60 °C to about 80 °C; a time period of from about 6 hours to about 72 hours, or about 12 hours to about 48 hours or about 12 hours to about 24 hours. This set of conditions will henceforth be called the ‘standard reaction conditions’. The reaction may be carried out within a polar aprotic solvent such as tetrahydrofuran, acetone, dimethylformamide, acetonitrile, dimethylsulfoxide or combinations thereof.The reaction of a primary monoamine and GAdL at a molar ratio of 1 :1 (primary monomaine:GAdL) results in the formation of monoamide glucaric lactone as depicted in Figure 4. The reaction of a primary monoamine and GAdL at a molar ratio where the amount of primary amine exceeds the amount of GAdL, for example, a molar ratio of at least 1.1 :1 (primary monomaine:GAdL) or a molar ratio of 2:1 (primary monomaine:GAdL) results in the formation of straight chain glucaric diamide as depicted in Figure 5. In one or more aspects, the monoamide glucaric lactone is converted to a salt by contacting with a metal hydroxide, YOH, where Y can be any suitable monocation such as potassium or sodium as depicted in Figure 4.

[0050] In one or more aspects, GAdL is contacted with a primary diamine under conditions suitable for the formation of a polyamide glucaric acid. In one or more aspects, the molar ratio of GAdL to primary diamine is about 1 :1 or is 1 :1 . The mixture of GAdL and primary diamine may be subjected to the standard reaction conditions. The reaction may be carried out within a polar aprotic solvent such as tetrahydrofuran, acetone, dimethylformamide, acetonitrile and dimethylsulfoxide. In some aspects, thereaction includes an acid catalyst such as sodium hypophosphite or phenylphosphonic acid. The stochiometric reaction of GAdL with a primary diamine is depicted schematically in Figure 6A.

[0051] In one or more aspects, GAdL is contacted with a primary diamine under conditions suitable for the formation of a dilactone diamide. In one or more aspects, the molar ratio of GAdL to primary diamine is from about 2.1 :1 to about 2.5:1 , or greater than or equal to about 2:1 or about 3:1 , or about 4:1 or about 5:1. The mixture of GAdL and primary diamine may be subjected to the standard reaction conditions. The reaction may be carried out in a polar aprotic solvent such as tetra hydrofuran, acetone, dimethylformamide, acetonitrile and dimethylsulfoxide. The dilactone diamide may be fully protonated to form a straight chain di-GA diamide, partially protonated, or reacted with a metal hydroxide to form the corresponding salt. The reaction of GAdL with an excess of primary diamine is depicted schematically in the first reaction step of Figure 6B.

[0052] In one or more aspects, GAdL is contacted with a primary diamine under conditions suitable for the formation of a primary amine terminated diamide. In one or more aspects, the molar ratio of GAdL to primary diamine is from about 1 :2.1 to about 1 :2.5, or greater than or equal to about 1 :2 or about 1 :3, or about 1 :4 or about 1 :5:1. The mixture of GAdL and primary diamine may be subjected to the standard reaction conditions. The reaction may be carried out within a polar aprotic solvent such as tetrahydrofuran, acetone, dimethylformamide, acetonitrile and dimethylsulfoxide. The reaction of GAdL with an excess of primary diamine is depicted schematically in the first reaction step of Figure 7A.

[0053] In one or more aspects, GAdL is reacted with a primary diamine and a crosslinking agent under conditions suitable for the formation of a crosslinked polymer. In an aspect, the crosslinking agent is a polyamine such as a triamine. In such aspects, the reaction is carried out at a molar ratio of GAdL:diamine:crosslinker of about 1 : 1 :0.05 or is 1 :1 :0.1. The mixture of GAdL, primary diamine and crosslinker may be subjected to the standard reaction conditions. The reaction may be carried out within a polar aprotic solvent such as tetra hydrofuran, acetone, dimethylformamide, acetonitrile and dimethylsulfoxide. In some aspects, the reaction includes an acid catalyst such as sodium hypophosphite or phenylphosphonic acid. The reaction of GAdL with a primary diamine and crosslinking agent is depicted schematically in Figure 6C.

[0054] In one or more aspects, a diamine of the type disclosed herein is reacted with GAdL under conditions suitable for the formation of a diamine diamide. Conditions suitable for formation of the diamine diamide include contacting the diamine and GAdL at a molar ratio of diamine to GAdL is about 2:1 or is 2:1 and subjecting the contacted materials to the standard reaction conditions. The reaction may be carried out within a polar aprotic solvent such as tetra hydrofuran, acetone, dimethylformamide, acetonitrile, dimethylsulfoxide or combinations thereof. The resulting diamine diamide product is characterized by the presence of terminal amine groups.

[0055] In one or more aspects, the diamine diamide is further reacted with a dicarboxylic acid under conditions suitable for the formation of a block polymer with alternating hydroxylated and non-substituted acid units. In one or more aspects, the block polymer comprises n monomeric units where n ranges from about 3 to about 50,000 or from about 50,000 to about 100,000. Nonlimiting examples of diacids that may be reacted with the diamine diacid include 2,5-furandicarboxylic acid (FDCA), 2,5- thiophenedicarboxylic acid (TFDCA), adipic acid, maleic acid, succinic acid, fumaric acid, itaconic acid, sebacic acid, terephthalic acid or combinations thereof. The reaction of GAdL with a diamide diamine and subsequently with a dicarboxylic acid is depicted in Figure 7A. The structures of dicarboxylic acids suitable for use in the present disclosure are depicted in Figure 7B

[0056] In one or more aspects, a gluconamide alcohol is prepared by reaction of GdL with an amine alcohol characterized by the general formula OH-R-NH2 wherein R can be alkyl (C1 to C20) or aryl. The structures of nonlimiting examples of amine alcohols suitable for use in the present disclosure are depicted in Figure 12C. GdL and the amine alcohol may be contacted under one or more of the following reaction conditions: a temperature of from about 20 °C to about 160 °C, or about 60 °C to about 90 °C or about 100 °C to about 110 °C a time period of from about 6 hours to about 72 hours, or about 12 hours to about 48 hours or about 12 hours to about 24 hours. The reaction may be carried out within a polar aprotic solvent such as tetrahydrofuran, acetone, dimethylformamide, acetonitrile, dimethylsulfoxide or combinations thereof. The resulting material may be characterized by Structure III where R is an C1-C20 alkyl group or a C1-C20 aryl group. In one or more aspects, R is ethyl.Structure IIIThese polymerization reactions are depicted in Figure 7C and Figure 7D.

[0057] In one or more aspects, GDL is reacted with a monoamine under conditions suitable for the formation of a gluconamide product. In such aspects, the reaction is carried out at a molar ratio of GDL: monoamine of equal to or greater than about 1 : 1 , or about 1 :2, 1 :3 or 1 :4. The mixture of GDL and monoamine may be subjected to one or more of the following reaction conditions: a temperature of from about 20 °C to about 160 °C, or about 40 °C to about 60 °C or about 80 °C to about 100 °C; a time period of from about 6 hours to about 72 hours, or about 12 hours to about 48 hours or about 12 hours to about 24 hours. The reaction may be carried out within a polar solvent such methanol, ethanol, dimethylformamide, water, dimethylacetamide, sulfolane or combinations thereof. The reaction of GDL with a monoamine is depicted schematically in Figure 8.

[0058] In one or more aspects, GDL is reacted with excess diamine under conditions suitable for the formation of a GDL amide amine product. In such aspects, the reaction is carried out at a molar ratio of GDL: diamine of at least about 1 :2, 1 :3, 1 :4, 1 :5 or 1 :6. The mixture of GDL and diamine may be subjected to one or more of the following reaction conditions: a temperature of from about 20 °C to about 160 °C, or about 40 °C to about 60 °C or about 80 °C to about 100 °C; a time period of from about 6 hours to about 72 hours, or about 12 hours to about 48 hours or about 12 hours to about 24 hours. The reaction may be carried out within a polar solvent such as methanol, ethanol, dimethylformamide, water, dimethylacetamide, sulfolane or combinations thereof. The reaction of GDL with a diamine in excess of GDL to form a glucodiamide product with a terminal amine end and terminal hydroxyl group end is depicted schematically in Figure 9A.

[0059] In one or more aspects, excess GDL is reacted with a diamine under conditions suitable for the formation of a GDL amide amine product having both ends terminated with hydroxyl groups. In such aspects, the reaction is carried out using excess GDL sufficient to provide a GDL: diamine molar ratio of at least about 2:1 , 3:1 , 4:1 , 5:1 or 6:1.The mixture of GDL and diamine may be subjected to one or more of the following reaction conditions: a temperature of from about 20 °C to about 150 °C, or about 40 °C to about 70 °C or about 90 °C to about 110 °C; a time period of from about 6 hours to about 72 hours, or about 12 hours to about 48 hours or about 12 hours to about 24 hours. The reaction may be carried out within a polar solvent such as methanol, ethanol, dimethylformamide, water, dimethylacetamide, sulfolane or combinations thereof. The reaction of excess GDL with a diamine in excess to form a glucodiamide product is depicted schematically in Figure 9B.

[0060] The amide products produced by reaction of GAdL or GDL may be used as produced or may serve as reagents in the production of other useful chemicals.

[0061] In one or more aspects, a glucaric acid amide lactone (GAAL) is reacted with a primary monoamine to form a tetraamide. In such aspects, the glucaric acid amide lactone is reacted with a monoamine to provide a molar ratio of GAAL:monoamine of equal to or greater than about 1 :2, or equal to or greater than 1 :3 or equal to or greater than 1 :4. In some aspects, the molar ratio of GAALmonoamine provides about 10% excess monoamine or about 20% excess monoamine. The mixture of GAAL and monoamine may be subjected to standard reaction conditions. The reaction may be carried out within a polar aprotic solvent such as tetrahydrofuran, acetone, dimethylformamide, acetonitrile and dimethylsulfoxide. The reaction of a GAAL and monoamine is depicted schematically in Figure 11.

[0062] In one or more aspects, a glucaric acid amide lactone (GAAL) is reacted with a primary diamine to form a tetraamide diamine. In such aspects, the glucaric acid amide lactone is reacted with a diamine to provide a molar ratio of GAAL:diamine of equal to or greater than about 1 :2, or equal to or greater than 1 :3 or equal to or greater than 1 :4. In some aspects, the molar ratio of GAAL:diamine provides about 10% excess diamine or about 20% excess diamine. The mixture of GAAL and diamine may be subjected to the standard reaction conditions. The reaction may be carried out within a polar aprotic solvent such as tetrahydrofuran, acetone, dimethylformamide, acetonitrile and dimethylsulfoxide. The reaction of a GAAL and diamine is depicted schematically in Figure 10.

[0063] In one or more aspects, the amine reactant is contacted with an acrylate or acrylate ester under conditions suitable for the formation of an amine-acrylate polymer. In one or more aspects, conditions suitable for the formation of an amine-acrylate polymer include radical polymerization conditions.

[0064] Amine reactants suitable for use include any primary or secondary amine, monoamines or polyamines, all of which have been disclosed herein. In one or more aspects, the amine reactants comprise at least one reactive hydrogen atom attached to the amine nitrogen atom.

[0065] For example, the amine reactant can comprise methylamine, ethylamine, isopropylamine, n-butylamine, hexylamine, neoheptylamine, 2-ethylhexylamine, ethylenediamine, diethylenetriamine, xylene diamine, hexamethylenetetramine, 1 ,2- diaminopropane, 1 ,3-diaminopropane, or combinations thereof.

[0066] Acrylate esters suitable for use in this disclosure include butyl acrylate, dimethylaminoethyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, 1 ,6-hexanediol diacrylate, methyl acrylate, pentaerythritol and tetraacrylate.

[0067] The amount of an acrylate ester can vary from about 1 mole to about 3 moles or molarratios of about 10:1 , 8:1 , 6:1 , 5:1 , 2:1 , 1 :1 , 2:1 , 3:1 , 5:1 or 10:1 per amino hydrogen atom equivalent in the amino compound. The reaction can be carried out in the absence of a solvent or in the presence of an inert solvent such acetone, benzene, toluene, xylene, hexane, octane, and the like.

[0068] A hydroxyl group terminated amide of the type disclosed herein may reacted in the presence of a suitable catalyst acid catalyst to form a polymer characterized by Structure IV, where R is a C1-C20 alkyl group ora C1-C20 aryl group and n ranges from about 5 to about 1000.Structure IVThis hydroxyl group terminated amide may be prepared by reaction of a lactone of the type disclosed herein (e.g., GadL, GDL) with an amine alcohol. The polymerization reaction of a hydroxyl group terminated amide is depicted schematically in Figure 12A.

[0069] In some aspects, the hydroxyl group terminated amide of the type disclosed herein is reacted with a dicarboxylic acid under conditions suitable for the formation of a polymer characterized by Structure V, where R is and n ranges from about to about1000. The polymerization reaction of a hydroxyl group terminated amide and dicarboxylic acid is depicted schematically in Figure 12B.Structure V

[0070] Nonlimiting examples of end products that may be prepared using the methodologies disclosed herein include diamine-diamideGA for use as Nylon additives or in the synthesis of Nylon 6,6. Nonlimiting examples of product A include: mono lactone monoamideGA which can be further reacted with other amines to produce unsymmetrical products (Product B); diol terminated-diamideGA or diol-amideGO inserted in polyethers or polyesters; and monolactone monoamide GA ring open to form a product salt.

[0071] Disclosed herein are methodologies for the preparation of functionalized molecules (e.g., having NH- and OH- functional groups) which are characterized as having highly tunable reactivity in a wide range of environments.

[0072] This presently disclosed methods provide a versatile platform for synthesizing multi-functional amides from sugar lactones. Specifically, the present disclosure provides for synthesis of new amide products from GAdL and GDL and improved ways of synthesizing amides. These molecules are derived from sugar, a renewable resource. The synthetic processes described herein advantageously are versatile as they utilize very few raw materials and hence are easy to scale.

[0073] D-glucaro-1 ,4:6,3-dilactone can be synthesized via a double ratio of D-glucaric acid. Those lactones, GDL from gluconic acid and GAdL from glucaricacid, react readily with amines to form amides products ranging from monolactone-monoamides to catalytically formed polyamides.

[0074] The amides produced can have several applications such as additives, surfactants, polymers, copolymers and crosslinkers. Surfactants are amphiphilic molecules. In the molecules described in this disclosure, the sugar-based component will be the hydrophilic region and a hydrophobic component (e.g., long chain fatty acid or ester), can be attached to the hydrophilic component via amide linkages. Such surfactants derived from bio-sources can be used in a wide range of applications, including laundry and dish detergents.

[0075] The amines used can be aliphatic, or carrying additional functional groups such as other amines, alcohols, alkenes, ketones, acrylates, and carboxylic acids. With those functionalities, the product can be further transformed, by radical polymerization with acrylates, by addition to a poly acrylate / methacrylate. The use of diamines (1 : 1 ) will yield a polyamides, and the use of a polyamines (three or more functionalities) will yield crosslinked materials.

[0076] The use of diamines in the right stoichiometry with GAdL leads to polyamides (from 3 to 50,000 units) or diGA amide lactones or di-amine of GAdiamides. The products generated can be further reacted for example, diamine-diamideGA as NYLON additives or in a NYLON 6,6 synthesis, mono actone monoamideGA further reacted with other amines (unsymmetrical products), diol-diamideGA or diol-amideGO inserted in polyethers or polyesters, mono lactone monoamideGA ring open to form salt.

[0077] Molecules with -NH and -OH groups provide multifunctionality in paints and coatings, in which the ability to interact with multiple ingredients is highly desirable. Such multifunctional molecules can be used as dispersants, rheology modifiers, surfactants, and neutralizing agents.

[0078] In adhesives, paints, and coatings, molecules with -NH and -OH groups can function as cross-linkers. These multi-functional molecules can be used as additives in polymers and plastics, as plasticizers and lubricants. These molecules can be polymerized or copolymerized to create plastics and hydrogels with applications in cosmetic formulations (e.g., emulsifier stabilization), agriculture (e.g., controlled release systems), and binders for aqueous coatings.ADDITIONAL DISCLOSURE

[0079] A first aspect which is a method comprising contacting an amine reactant with a lactone under conditions suitable for the formation of an amide, wherein the lactone comprises glucono-delta lactone (GDL), D-glucaric acid 1 ,4, 6, 3 dilactone (GAdL), substituted GDL, substituted D-glucaric acid 1 ,4, 6, 3 dilactone, or combinations thereof.

[0080] A second aspect which is the method of the first aspect wherein the substituted lactones are generally characterized by Structure I or Structure IIwhere each Z is independently acetate, methyl oxide, trityl or disopropylidine.

[0081] A third aspect which is the method of any of the first through second aspects wherein the amine reactant is an aliphatic compound.

[0082] A fourth aspect which is the method of any of the first through third aspects wherein the amine reactant is a monoamine.

[0083] A fifth aspect which is the method of the fourth aspect wherein the monoamine comprises ethanolamine (EtA); propylamine; butylamine (BuA); sec-butylamine; N,N- diethyl-1 ,3-diaminopropane; isopropylamine; 2-ethylhexylamine; pentylamine (AML); 2- ethyl-hexylamine; hexylamine (HexA); octylamine (OctA); dodecylamine (DodA); oleylamine (Oam); phenethylamine (PHEA); 1-adamanantamine (ADA); cyclohexylamine (cHexA); tert-butylamine (tBuA);2-(aminomethyl)phenol; 2- (aminomethyl)benzyl alcohol; 2-aminophenol; 2-aminobenzyl alcohol; 2- (aminomethyl)benzyl alcohol; 3-(aminomethyl)phenol; 3-(aminomethyl)benzyl alcohol; 4-(aminomethyl)phenol; 4-(aminomethyl)benzyl alcohol; 4-aminophenol; 3- aminophenol; 3-(aminomethyl)benzyl alcohol; 4-(aminomethyl)phenol; 4- (aminomethyl)benzyl alcohol; 4-aminophenol; 3-aminophenol; 3-aminobenzyl alcohol; 4-aminobenzyl alcohol; 2-vinylbenzylamine; 4-vinylaniline; 2-vinylaniline; 3- vinylbenzylamine; 3-vinylaniline; 4-vinylbenzylamine; aminoalkyl acrylamide; aminoalkyl methacrylamide; or combinations thereof.

[0084] A sixth aspect which is the method of any of the first through third aspects wherein the amine reactant is a diamine.

[0085] A seventh aspect which is the method of the sixth aspect wherein the diamine comprises ethylenediamine (EtDA); diaminopropane (DAP); 1 ,2-diaminopropane; 2,2- dimethyl-1 ,3-propanediamine; putrescine (BDA); cadaverine (PDA); 2-methyl-1 ,5- pentanediamine (MPMD); hexamethylenediamine (HMDA); dodecylenediamine (DodDA); 4,4’-diaminodicyclohexylmethane; 2,2-(ethylenedioxy)diethylamine; 2-[2-[2- [2-aminoethoxy]ethoxy]ethoxy]ethylamine; 1 ,3-bis(2-aminoethyl)urea; glucarodiamine (DIG); L-lysine (LYS); isophorone diamine (IPDA); m-xylylene diamine (mXDA); 1 ,5- diaminonapthalene (1 ,5DAN) or combinations thereof.

[0086] A sixth aspect which is the method of any of the first through third aspects wherein the amine reactant is a diamine.

[0087] A seventh aspect which is the method of the sixth aspect wherein the diamine comprises ethylenediamine (EtDA); diaminopropane (DAP); 1 ,2-diaminopropane; 2,2- dimethyl-1 ,3-propanediamine; putrescine (BDA); cadaverine (PDA); 2-methyl-1 ,5- pentanediamine (MPMD); hexamethylenediamine (HMDA); dodecylenediamine(DodDA); 4,4’-diaminodicyclohexylmethane; 2,2-(ethylenedioxy)diethylamine; 2-[2-[2- [2-aminoethoxy]ethoxy]ethoxy]ethylamine; 1 ,3-bis(2-aminoethyl)urea; glucarodiamine (DIG); L-lysine (LYS); isophorone diamine (IPDA); m-xylylene diamine (mXDA); 1 ,5- diaminonapthalene (1 ,5DAN) or combinations thereof.

[0088] An eighth aspect which is the method of any of the first through seventh aspects wherein the amine reactant is a triamine, polyamine or combinations thereof.

[0089] A ninth aspect which is the method of the eighth aspect wherein the triamine or polyamine comprises diethylenetriamine (DETA); tetraethylenepentamine; 2- aminoethyl ether; triethylene tetramine;melamine (MEL); tris(2-aminoethyl)amine (TREN), polyethylenimine (PEI); amino polypropylene acrylamide; amino polyethylene acrylamide or combinations thereof.

[0090] A tenth aspect which is the method of any of the first through ninth aspects wherein a monoamine is reacted with GAdL at a ratio of monoamine to GDAdL of about 1 :1 under conditions suitable for the formation of a monoamide glucaric lactone.

[0091] An eleventh aspect which is method of any of the first through ninth aspects wherein a monoamine is reacted with GAdL at a ratio of monoamine to GDAdL of about 2:1 under conditions suitable for the formation of a diamide glucaric lactone.

[0092] A twelfth aspect which is the method of any of the first through ninth aspects wherein a diamine is reacted with GAdL at a ratio of diamine to GDAdL of about 1 :1 under conditions suitable for the formation of a glucaric polyamide.

[0093] A thirteenth aspect which is the method of any of the first ninth aspects wherein a diamine is reacted with GAdL at a ratio of diamine to GDAdL of about equal to or greater than about 1 :2.1 under conditions suitable for the formation of a straight chain polyamide.

[0094] A fourteenth aspect which is the method of any of the first through ninth aspects wherein a diamine is reacted with GAdL, excess diamine and a crosslinker under conditions suitable for the formation of a crosslinked glucaric polymer.

[0095] A fifteenth aspect which is the method of the fourteenth aspect wherein the crosslinker is a triamine.

[0096] A sixteenth aspect which is the method of any of the first through fifteenth aspects wherein a diamine is reacted with GAdL, diamine and a dicarboxylic acid under conditions suitable for the formation of a glucaric acid polymer.

[0097] A seventeenth aspect which is the method of any of the first through sixteenth aspects wherein a monoamine is reacted with GDL at a molar ratio of monoamine toGDL of equal to or greater than about 1 :2.1 under conditions suitable for the formation a glucoramide product.

[0098] An eighteenth aspect which is the method of any of the first through seventeenth aspects wherein a diamine is reacted with GDL at a molar ratio of monoamine to GDL of equal to or greater than about 1 :1 under conditions suitable for the formation a glucodiamide product.

[0099] A nineteenth aspect which is a method of preparing a biobased amide comprising contacting an amine with a sugar-derived lactone under conditions suitable for the formation of an amide.[001 oo] A twentieth aspect which is the method of the nineteenth aspect wherein the amide is further reacted to form a polymide.

[0101] A twenty-first aspect which is the method of any of the nineteenth through twentieth aspects wherein the amine is a monoamine selected from the group consisting essentially of ethylenediamine (EtDA); diaminopropane (DAP); 1 ,2-diaminopropane; 2,2-dimethyl-1 ,3-propanediamine; putrescine (BDA); cadaverine (PDA); 2-methyl-1 ,5- pentanediamine (MPMD); hexamethylenediamine (HMDA); dodecylenediamine (DodDA); 4,4’-diaminodicyclohexylmethane; 2,2-(ethylenedioxy)diethylamine; 2-[2-[2- [2-aminoethoxy]ethoxy]ethoxy]ethylamine; 1 ,3-bis(2-aminoethyl)urea; glucarodiamine (DIG); L-lysine (LYS); isophorone diamine (IPDA); m-xylylene diamine (mXDA); 1 ,5- diaminonapthalene (1 ,5DAN) and combinations thereof.

[0102] A twenty-second aspect which is the method of any of the nineteenth through twenty-first aspects wherein the lactone comprises glucono-delta lactone (GDL), D- glucaric acid 1 ,4, 6, 3 dilactone (GAdL), substituted lactones or combinations thereof.EXAMPLES

[0103] The aspects having been generally described, the following reaction conditions examples are given as particular aspects of the disclosure and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification or the claims in any manner. The following examples are prophetic.EXAMPLE 1[OO1O4]A primary monoamine (e.g., butylamine or other previously listed primary monoamine) can be reacted in a 2:1 molar ratio with D-glucaric acid 1 ,4:6,3-dilactone, henceforth GAdL, to form a straight-chain diamide product. The ratio of primary amine to GAdL can exceed 2:1 but for full conversion is at minimum 2:1. This reaction isconducted by dissolving GAdL in 40-50 molar equivalents of a polar aprotic solvent. The primary monoamine is then dissolved or, in the case of a liquid primary amine, diluted in a minimum amount of solvent and added dropwise to the GAdL reaction mixture. The reaction is conducted for 24 hours at ambient conditions with constant stirring. Alternatively, the reaction may be conducted at slightly elevated temperatures of 25 °C -50 °C. After 24 hours have elapsed the reaction is terminated by dropwise addition of the reaction mixture to an excess of a suitable non-polar antisolvent (e.g., hexanes). The resultant precipitate or gel is then washed with antisolvents several times and collected via centrifugation. The solid or gel product is then dried under vacuum to afford the dried desired diamide product. The resultant diamide product is a straight-chain glucaric acid derivative terminated on both sides by secondary amides corresponding to the respective primary amine derivative as listed above. The reaction is depicted schematically in Figure 5.EXAMPLE 2[OO1O5]A primary monoamine (e.g., butylamine or other previously listed primary monoamine) can be reacted in a 1 :1 molar ratio with GAdL to form a monolactonemonoamide product. This reaction is conducted by dissolving GAdL in 40-50 molar equivalents of a polar aprotic solvent. The primary monoamine is then dissolved or, in the case of a liquid primary amine, diluted in a minimum amount of solvent and added dropwise to the GAdL reaction mixture. The reaction is conducted for 24 hours at ambient conditions with constant stirring. After 24 hours have elapsed the reaction is terminated by dropwise addition of the reaction mixture to an excess of a suitable nonpolar antisolvent, (e.g. hexanes). The resultant precipitate or gel is then washed with antisolvents several times and collected via centrifugation. The solid or gel product is then dried under vacuum to afford the dried desired monoamide-monolactone product. The resultant product is a y-lactone functionalized with a branched secondary amide corresponding to the respective primary amine derivative as listed above. The reaction is depicted schematically in Figure 4.EXAMPLE 3

[0106] A diamine (e.g., hexamethylenediamine or similar) can be reacted in at least a 2:1 molar ratio with a dilactone, such as GAdL, to form a diamide product with two terminal amine groups. This can further be reacted with a dicarboxylic acid such as adipic acid to form a block polymer with alternating / random / block hydroxyl grouplatedand non-substituted acid units. Diacid can be replaced with the corresponding diester, acid anhydride, or diacyl dichloride. This is depicted schematically in Figures 7A and 7B.EXAMPLE 4[OO1O7]A primary diamine (e.g., hexamethylenediamine or other previously listed primary diamine) can be reacted in a 1 :1 molar ratio with GAdL to form a polyamide. This polymerization is conducted by dissolving GAdL in 40-50 molar equivalents of a polar aprotic solvent. Optionally, an acid catalyst such as sodium hypophosphite, or phenylphosphonic acid can be added to the reaction mixture in 0.01-0.10 molar equivalents to catalyze the polymerization reaction. The primary diamine is then dissolved or, in the case of a liquid primary diamine, diluted, into 40-50 molar equivalents of solvent. The mixtures are then combined. The addition can be a complete unrestricted transfer of dissolved diamine solution to dissolved GAdL solution or, alternatively, the dropwise addition of diamine solution to GAdL solution. The reaction is conducted for 24 hours at ambient conditions with constant stirring. Alternatively, the reaction may be conducted at slightly elevated temperatures of 25 °C -50 °C. After 24 hours have elapsed the reaction may be terminated by dropwise addition of acetic anhydride to quench any unreacted free amine. The resultant polymer precipitate or gel is then washed with antisolvents several times and collected via centrifugation or filtration. The solid or gel product is then dried under vacuum to afford the dried polyamide. This reaction is depicted schematically in Figure 6A.EXAMPLE 5[OO1O8]A primary diamine (e.g., hexamethylenediamine or other previously listed primary diamine) can be reacted in a 1 :2 molar ratio with GAdL to form a dilactone diamide. The molar ratio of diamine to GAdL is at minimum 1 :2 primary amine:GAdL, but alternatively is present in a molar ratio ranging from about 1 :2 or about 1-2.5 primary amine:GAdL. This reaction is conducted by dissolving GAdL in 40-50 molar equivalents of a polar aprotic solvent. The primary diamine is then dissolved or, in the case of a liquid primary diamine, diluted, into 40-50 molar equivalents of solvent. The mixtures are then combined via slow dropwise addition of the diamine to the GAdL reaction mixture. The reaction is conducted for 24 hours at ambient conditions with constant stirring. Alternatively, the reaction may be conducted at slightly elevated temperatures of 25 °C -50 °C. After 24 hours have elapsed the reaction may be terminated by addition of thereaction mixture to an excess of an antisolvent (e.g., hexanes). The resultant precipitate or gel is then washed with antisolvents several times and collected via centrifugation or filtration. The solid or gel product is then dried under vacuum to afford the dried product, a lactone-term inated secondary diamide. The terminal lactones may then be ring opened to afford a straight chain product in the presence of acid, or kept in lactone form if desired. Additionally, one lactone can be opened to afford a diamide terminated on one end by a lactone. This reaction is depicted schematically in Figure 6BEXAMPLE 6

[0109] A primary diamine or primary monoamine (e.g., hexamethylenediamine, hexylamine or other previously listed primary diamine or monoamine) can be reacted in a 1 :1.1 molar ratio with GadL and a crosslinking agent to form a crosslinked polyamide. This polymerization is conducted by dissolving GAdL in 40-50 molar equivalents of a polar aprotic solvent. Optionally, an acid catalyst, such as sodium hypophosphite or phenylphosphonic acid, can be added to the reaction mixture in 0.01-0.10 molar equivalents to catalyze the polymerization reaction. The addition of 0.05-0.10 molar equivalents of a polyamine or triamine mentioned previously, such as TREN, to the reaction mixture will allow for crosslinking. The crosslinking agent is dissolved or diluted into 10-15 molar equivalents of solvent and added dropwise into the GAdL reaction mixture. The primary monoamine or diamine is then dissolved or, in the case of a liquid primary amine, diluted, into 40-50 molar equivalents of solvent. The primary diamine or monoamine solution is then combined with the GAdL reaction mixture. The addition can be a complete unrestricted transfer of dissolved diamine solution to dissolved GAdL solution or the dropwise addition of primary diamine or monoamine solution to GAdL solution. The reaction is conducted for 24 hours at ambient conditions with constant stirring. After 24 hours have elapsed the reaction may be terminated by dropwise addition of acetic anhydride to quench any unreacted free amine. The resultant polymer precipitate or gel is then washed with antisolvents several times and collected via centrifugation or filtration. The solid or gel product is then dried under vacuum to afford the dried, crosslinked, polyamide. This reaction is depicted schematically in Figure 6C.EXAMPLE 7

[0110] A monoamine, or similar, can be reacted with GDL in a polar solvent to form a respective gluconamide product. In a typical reaction, a monoamine (1 .0-2.0 molar equivalents) is added to a polar solvent at room temperature, followed by addition of GDL (1 .0 molar equivalent). The resulting mixture was then stirred at room temperatureor boiled to reflux for 24-48 hours. The product can be purified by filtration or recrystallization using anti-solvents. This reaction is depicted schematically in Figure 8.EXAMPLE 8

[0111] A diamine (excess), or similar, can be reacted with GDL in a polar solvent to form a respective glucomonoamide product with a terminal amine group. The terminal amine group then can further react with other functional groups such as ester, carboxylic acid, acid anhydride or diacyl dichloride. This reaction is depicted schematically in Figure 9A.EXAMPLE 9

[0112] A diamine, or similar, can be reacted with GDL (excess) in a polar solvent to form a respective glucodiamide product. This reaction is depicted schematically in Figure 9B.EXAMPLE 10

[0113] A DiGA amide lactone product, as described in example 5, can be reacted in a 1 :2 molar molar ratio with a diamine. The molar ratio of DiGA amide lactone to diamine must be at minimum 1 :2 DiGA amide lactone to primary diamine, but the diamine may also be used in a slight excess to prevent side product formation. This reaction is conducted by dissolving the primary diamine in 40-50 molar equivalents of a polar, aprotic solvent such as, but not limited to, tetrahydrofuran, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, etc. The DiGA amide lactone is then dissolved into 40- 50 molar equivalents of solvent. The mixtures are then combined via slow dropwise addition of the DiGA amide lactone to the diamine reaction mixture. The reaction is conducted for 24 hours at ambient conditions with constant stirring. Alternatively, the reaction may be conducted at slightly elevated temperatures of 25 °C -50 °C. After 24 hours have elapsed the reaction may be terminated by addition of the reaction mixture to an excess of an antisolvent such as hexanes. The resultant precipitate or gel is then washed with antisolvents several times and collected via centrifugation or filtration. The solid or gel product is then dried under vacuum to afford the dried product, a DiGA tetramide diamine, where the diamines are terminal primary amines. This reaction is depicted schematically in Figure 10.EXAMPLE 11

[0114] A DiGA amide lactone product, as described in example 5, can be reacted in a 1 :2 molar ratio with a primary amine. The molar ratio of DiGA amide lactone to primary amine must be at minimum 1 :2 DiGA amide lactone to primary amine, but the amine may also be used in a slight excess to promote full product conversion. This reaction isconducted by dissolving or diluting the primary amine in 40-50 molar equivalents of a polar, aprotic solvent. The DiGA amide lactone is then dissolved into 40-50 molar equivalents of solvent The mixtures are then combined via slow dropwise addition of the DiGA amide lactone to the primary amine reaction mixture. The reaction is conducted for 24 hours at ambient conditions with constant stirring. After 24 hours have elapsed the reaction may be terminated by addition of the reaction mixture to an excess of an antisolvent such as hexanes. The resultant precipitate or gel is then washed with antisolvents several times and collected via centrifugation or filtration. The solid or gel product is then dried under vacuum to afford the dried product, a DiGA tetraamide. This reaction is depicted schematically in Figure 11 .EXAMPLE 12

[0115] GDL amide diol could be used to prepare polyethers using an acid-catalyzed process at elevated temperature. GDL amide diol could be used to synthesize polyesters by reacting with a diacid / diester under an acidic condition at elevated temperature. This reaction is depicted schematically in Figures 12A and 12B.

[0116] While aspects of the presently disclosed subject matter have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the subject matter. The aspects described herein are exemplary only and are not intended to be limiting. Many variations and modifications of the subject matter disclosed herein are possible and are within the scope of the disclosed subject matter. Where numerical ranges or limitations are expressly stated, such express ranges or limitations should be understood to include iterative ranges or limitations of like magnitude falling within the expressly stated ranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4, etc.; greater than 0.10 includes 0.11 , 0.12, 0.13, etc.). Use of the term "optionally" with respect to any element of a claim is intended to mean that the subject element is required, or alternatively, is not required. Both alternatives are intended to be within the scope of the claim. Use of broader terms such as comprises, includes, having, etc. should be understood to provide support for narrower terms such as consisting of, consisting essentially of, comprised substantially of, etc.

[0117] Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an aspect of the present disclosure. Thus, the claims are a further description andare an addition to the aspects of the presently disclosed subject matter. The discussion of a reference herein is not an admission that it is prior art to the presently disclosed subject matter, especially any reference that may have a publication date after the priority date of this application. The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference, to the extent that they provide exemplary, procedural or other details supplementary to those set forth herein.

Claims

CLAIMSWhat is claimed is:1 . A method, comprising: contacting an amine reactant with a lactone under conditions suitable for the formation of an amide, wherein the lactone comprises glucono-delta lactone (GDL), D-glucaric acid 1 ,4,6,3 dilactone (GAdL), substituted GDL, substituted D-glucaric acid 1 ,4,6,3 dilactone, or combinations thereof.

2. The method of claim 1 , wherein the substituted lactones are generally characterized by Structure I or Structure IIStructure I Structure II where each Z is independently acetate, methyl oxide, trityl or disopropylidine.

3. The method of claim 1 , wherein the amine reactant is an aliphatic compound.

4. The method of claim 1 , wherein the amine reactant is a monoamine.

5. The method of claim 4, wherein the monoamine comprises ethanolamine (EtA); propylamine; butylamine (BuA); sec-butylamine; N,N-diethyl-1 ,3-diaminopropane; isopropylamine; 2-ethylhexylamine; pentylamine (AML); 2-ethyl-hexylamine; hexylamine (HexA); octylamine (OctA); dodecylamine (DodA); oleylamine (Gam); phenethylamine (PHEA); 1-adamanantamine (ADA); cyclohexylamine (cHexA); tertbutylamine (tBuA);2-(aminomethyl)phenol; 2-(aminomethyl)benzyl alcohol; 2- aminophenol; 2-aminobenzyl alcohol; 2-(aminomethyl)benzyl alcohol; 3- (aminomethyl)phenol; 3-(aminomethyl)benzyl alcohol; 4-(aminomethyl)phenol; 4- (aminomethyl)benzyl alcohol; 4-aminophenol; 3-aminophenol; 3-(aminomethyl)benzyl alcohol; 4-(aminomethyl)phenol; 4-(aminomethyl)benzyl alcohol; 4-aminophenol; 3- aminophenol; 3-aminobenzyl alcohol; 4-aminobenzyl alcohol; 2-vinylbenzylamine; 4- vinylaniline; 2-vinylaniline; 3-vinylbenzylamine; 3-vinylaniline; 4-vinylbenzylamine; aminoalkyl acrylamide; aminoalkyl methacrylamide; or combinations thereof.

6. The method of claim 1 , wherein the amine reactant is a diamine.

7. The method of claim 6, wherein the diamine comprises ethylenediamine (EtDA); diaminopropane (DAP); 1 ,2-diaminopropane; 2,2-dimethyl-1 ,3-propanediamine; putrescine (BDA); cadaverine (PDA); 2-methyl-1 ,5-pentanediamine (MPMD); hexamethylenediamine (HMDA); dodecylenediamine (DodDA); 4,4’- diaminodicyclohexylmethane; 2,2-(ethylenedioxy)diethylamine; 2-[2-[2-[2- aminoethoxy]ethoxy]ethoxy]ethylamine; 1 ,3-bis(2-aminoethyl)urea; glucarodiamine (DIG); L-lysine (LYS); isophorone diamine (IPDA); m-xylylene diamine (mXDA); 1 ,5- diaminonapthalene (1 ,5DAN) or combinations thereof.

8. The method of claim 1 , wherein the amine reactant is a triamine, polyamine or combinations thereof.

9. The method of claim 8, wherein the triamine or polyamine comprises diethylenetriamine (DETA); tetraethylenepentamine; 2-aminoethyl ether; triethylene tetramine;melamine (MEL); tris(2-aminoethyl)amine (TREN), polyethylenimine (PEI); amino polypropylene acrylamide; amino polyethylene acrylamide or combinations thereof.

10. The method of claim 1 wherein a monoamine is reacted with GAdL at a ratio of monoamine to GDAdL of about 1 :1 under conditions suitable for the formation of a monoamide glucaric lactone.11 . The method of claim 1 , wherein a monoamine is reacted with GAdL at a ratio of monoamine to GDAdL of about 2:1 under conditions suitable for the formation of a diamide glucaric lactone.

12. The method of claim 1 , wherein a diamine is reacted with GAdL at a ratio of diamine to GDAdL of about 1 :1 under conditions suitable for the formation of a glucaric polyamide.

13. The method of claim 1 , wherein a diamine is reacted with GAdL at a ratio of diamine to GDAdL of about equal to or greater than about 1 :2.1 under conditions suitable for the formation of a straight chain polyamide.

14. The method of claim 1 , wherein a diamine is reacted with GAdL, excess diamine and a crosslinker under conditions suitable for the formation of a crosslinked glucaric polymer.

15. The method of claim 14, wherein the crosslinker is a triamine.

16. The method of claim 1 , wherein a diamine is reacted with GAdL, diamine and a dicarboxylic acid under conditions suitable for the formation of a glucaric acid polymer.

17. The method of claim 1 , wherein a monoamine is reacted with GDL at a molar ratio of monoamine to GDL of equal to or greater than about 1 :2.1 under conditions suitable for the formation a glucoramide product.18 The method of claim 1 , wherein a diamine is reacted with GDL at a molar ratio of monoamine to GDL of equal to or greater than about 1 :1 under conditions suitable for the formation a glucodiamide product.

19. A method of preparing a biobased amide, the method comprising: contacting an amine with a sugar-derived lactone under conditions suitable for the formation of an amide.

20. The method of claim 19, wherein the amide is further reacted to form a polymide.

21. The method of claim 19, wherein the amine is a monoamine selected from the group consisisting essentially of ethylenediamine (EtDA); diaminopropane (DAP); 1 ,2- diaminopropane; 2,2-dimethyl-1 ,3-propanediamine; putrescine (BDA); cadaverine (PDA); 2-methyl-1 ,5-pentanediamine (MPMD); hexamethylenediamine (HMDA); dodecylenediamine (DodDA); 4, 4’ -diaminodicyclohexylmethane; 2,2- (ethylenedioxy)diethylamine; 2-[2-[2-[2-aminoethoxy]ethoxy]ethoxy]ethylamine; 1 ,3- bis(2-aminoethyl)urea; glucarodiamine (DIG); L-lysine (LYS); isophorone diamine(IPDA); m-xylylene diamine (mXDA); 1 ,5-diaminonapthalene (1 ,5DAN) and combinations thereof.

22. The method of claim 19, wherein the lactone comprises glucono-delta lactone (GDL), D-glucaric acid 1 ,4, 6, 3 dilactone (GAdL), substituted lactones or combinations thereof.

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