Methods of making acetal compositions

Abstract

The present invention includes furfural-derived acetals and methods for preparing such acetals. These methods include heating an alcohol in the presence of furfural or a substituted furfural, wherein heating takes place in the absence of solvent and in the absence of catalyst, to afford the resultant furfural acetal. Less than 5 percent (w / w) of the ring-opened furan derivatives or polymerized furan derivatives, relative to the initial amount of unsubstituted / substituted furfural compound form during the heating, thereby advantageously preserving the integrity of the cyclic furan structure, while achieving high levels of monomer conversion and product yield.

Description

[0001]Attorney Docket No.370431-1051WO1 METHODS OF MAKING ACETAL COMPOSITIONS CROSS-REFERENCE TO RELATED APPLICATION This application claims priority to U.S. Provisional Patent Application No. 63 / 538,186 entitled “METHODS OF MAKING ACETAL COMPOSITIONS,” filed September 13, 2023, the disclosure of which is incorporated herein by reference in its entirety. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH This invention was made with government support under W911NF-17-2-0227 awarded by the Army Research Laboratory. The government has certain rights in the invention. BACKGROUND There is increasing demand for high-value platform chemicals that are synthesized from renewable feedstocks and industrial waste streams. Rigid mono- and polycyclic acetals molecules can be so prepared to expand end-of-life options for materials that are fabricated from these bio-based platform chemicals. Furfural and its derivatives are traditionally obtained from fructose by an established acid-catalyzed reaction process. However, the occurrence of the reverse reaction and the self-condensation of furfural molecules have insofar prevented the commercial / industrial use of condensation reactions involving furfural and its derivatives. The present disclosure solves this unmet need by providing methods of acetalizing furan-derived aldehydes while preserving the integrity of the cyclic furan structure, while achieving high levels of monomer conversion and product yield. BRIEF SUMMARY OF THE INVENTION In one aspect, a method for preparing an acetal is provided. The method includes heating at a temperature of about 60 to about 110 ºC an alcohol of formula (I): , and an aldehyde of formula (II) - 1 - 53006853.1 Attorney Docket No.370431-1051WO1 , to provide an acetal of formula , wherein: each bond; R1and R2are each independently selected from the group consisting of H, C1-3alkyl, -OH, OC1-3 alkyl, F, Cl, Br, and C1-3 alkyl substituted by one OH, wherein R1and R2are not simultaneously -OH; R1’and R2’are each independently a bond (absent), -CH2, -CH(CH3)-, or - CH(CH2CH3)-, provided that at least one of R1’and R2’is not a bond; R3and R4are each independently selected from the group consisting of H, C1-3 alkyl, F, Cl, Br, C6-10aryl, and C5heteroaryl; R5, R6, and R7are each independently selected from the group consisting of H, F, Cl, OR, (CH2)1-3OH, OC(O)N(R)2, CN, CF3, OCF3, R, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, and (CH2)0-2N(R)C(O)R; each R is independently H or C1-10 hydrocarbyl optionally substituted by F or Cl; n is 0 or 1, provided that, when n is 0, R1and R2are absent; m is an integer from 1 to 100, provided that when m is greater than 1, R1and R2are H; with the proviso that: i) if m is 1 and one of R1or R2does not comprise an OH group, then Y is -(CHR3)-; Z is -(CHR4)-; and X is -C(R1)(R2)- or a single bond connecting Y and Z; ii) if m is 1 and R1and R2are each independently selected from the group consisting of -OH, -CH2OH, -CH(OH)CH3, and -CH(OH)CH2CH3, then - 2 - 53006853.1 Attorney Docket No.370431-1051WO1 Y is -(CHR3)-; Z is -(CHR4)-; and ; iii) R2is H, then iv) m wherein the heating takes place in the absence of solvent and in the absence of catalyst; and wherein less than 5 % (w / w) of ring-opened furan derivatives and / or polymerized furan derivatives relative to the original amount of (II) form during the heating. Surprisingly and unexpectedly, the method results in reaction products containing less than 5% (w / w) of ring-opened furan derivatives and / or polymerized furan derivatives relative to the initial amount of furan while also being catalyst-free. In another aspect, a compound or a salt, solvate enantiomer, tautomer, or diastereomer thereof, is provided. The compound is selected from the group consisting of: - 3 - 53006853.1 Attorney Docket No.370431-1051WO1 wherein: ; OC1-3 alkyl, F, Cl, and Br; R3and R4are each independently selected from the group consisting of H, C1-3 alkyl, F, Cl, C6-10aryl, C5heteroaryl; R5, R6, and R7are each independently selected from the group consisting of H, F, Cl, Br, OR, (CH2)1-3OH, (CH2)1-3OA, OC(O)N(R)2, CN, CF3, OCF3, R, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, and (CH2)0-2N(R)C(O)R; R9is H, C1-4 alkyl, C6-10 aryl, F, Cl, or Br, wherein the C6-10 aryl is optionally substituted by 1 to 5 substituents selected from the group consisting of F, Cl, Br, OR, (CH2)1-3OH, OC(O)N(R)2, CN, CF3, OCF3, R, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, and (CH2)0-2N(R)C(O)R; p is 0 or 1; R10and R11are each independently selected from the group consisting of H, F, - 4 - 53006853.1 Attorney Docket No.370431-1051WO1 Cl, Br, and C1-4 alkyl; and R is H, A, or C1-10hydrocarbyl optionally substituted by F or Cl. These compounds are useful in producing a variety of resins, such as thermoset resins. BRIEF DESCRIPTION OF THE FIGURES The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments of the present application. FIG.1 depicts reaction mechanisms for acid-catalyzed and uncatalyzed acetalization of furfural derivatives. FIG.2 shows reaction products of glycerol with furfural, in accordance with various embodiments. FIG.3 shows infrared (IR) absorption spectra and elution times for furfural, along with acetal products of furfural, 5-M-2-furfural, and 5-HM-2-furfural, in accordance with various embodiments. FIG.4 shows13C NMR chemical shifts for furfural, furfural acetal, 5-M-2-furfural, and 5-HM-2-furfural, in accordance with various embodiments. FIG.5 shows a synthetic scheme and IR absorption spectra for furfural derivatives HMF-TMP and HMF-Pent, in accordance with various embodiments. FIG.6 shows furfural derivatives synthesized, in accordance with various embodiments. FIG.7 shows some acyclic furfural derivatives, in accordance with various embodiments. FIG.8 shows a DSC (differential scanning calorimetry) analysis of acetals F-Gly, MF-Gly, HMF-Gly, and HMF-Gly. FIG.9 shows results of DMA testing of BisGMA polymers incorporating acetals mF- Gly and mMF-Gly as reactive diluents in the amount of 35 wt%. FIG.10 shows a DSC analysis of BisGMA polymers incorporating acetals mF-Gly and mMF-Gly as reactive diluents in the amount of 35 wt%. FIG.11 shows the effect of temperature on the reaction of alcohols of formula (I) and furfurals of formula (II). FIG.12 shows the IR absorption spectra of dimethacrylate precursors 6m and 7m, according to various embodiments. - 5 - 53006853.1 Attorney Docket No.370431-1051WO1 FIG.13 shows the storage modulus and tan delta signals obtained from thermomechanical measurements on cured compounds 6m and 7m, with or without p-MST and / or MFA additive, in accordance with various embodiments. FIG.14 shows the characterization of 7e by gel permeation chromatography (GPC), in accordance with various embodiments. FIG.15 shows images of thermosets of compound 7e cured with PACM (4,4'- diaminodicyclohexylmethane) and DETA (diethylenetriamine), and DFDA (5,5′- methylenedifurfurylamine), according to various embodiments. FIG.16 shows the IR absorption spectra of the thermosets from FIG.15. FIG.17 shows thermomechanical measurements on the thermosets from FIG.15. DETAILED DESCRIPTION OF THE INVENTION Reference will now be made in detail to certain embodiments of the disclosed subject matter. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter. Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise. Likewise, the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise. In this document, the terms “a,” “an,” or “the” are used to include one or more than one unless the context clearly dictates otherwise. The term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. The statement “at least one of A and B” or “at least one of A or B” has the same meaning as “A, B, or A and B.” In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section. - 6 - 53006853.1 Attorney Docket No.370431-1051WO1 In the methods described herein, the acts can be carried out in any order, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process. Definitions The term “about” as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range, and includes the exact stated value or range. The term “acyl” as used herein refers to a group containing a carbonyl moiety wherein the group is bonded via the carbonyl carbon atom. The carbonyl carbon atom is bonded to a hydrogen forming a “formyl” group or is bonded to another carbon atom, which can be part of an alkyl, aryl, aralkyl cycloalkyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl group or the like. An acyl group can include 0 to about 12, 0 to about 20, or 0 to about 40 additional carbon atoms bonded to the carbonyl group. An acyl group can include double or triple bonds within the meaning herein. An acryloyl group is an example of an acyl group. An acyl group can also include heteroatoms within the meaning herein. A nicotinoyl group (pyridyl-3-carbonyl) is an example of an acyl group within the meaning herein. Other examples include acetyl, benzoyl, phenylacetyl, pyridylacetyl, cinnamoyl, and acryloyl groups and the like. When the group containing the carbon atom that is bonded to the carbonyl carbon atom contains a halogen, the group is termed a “haloacyl” group. An example is a trifluoroacetyl group. The term “alkyl” as used herein refers to straight chain and branched alkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms. Examples of straight chain alkyl groups include those with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n- butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups. As used herein, the term “alkyl” encompasses n-alkyl, isoalkyl, and anteisoalkyl groups as well as other branched chain forms of alkyl. Representative substituted alkyl groups can be substituted one or more times with any of the groups listed herein, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and - 7 - 53006853.1 Attorney Docket No.370431-1051WO1 halogen groups. The term “alkenyl” as used herein refers to straight and branched chain and cyclic alkyl groups as defined herein, except that at least one double bond exists between two carbon atoms. Thus, alkenyl groups have from 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12 carbon atoms or, in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to vinyl, -CH=C=CCH2, -CH=CH(CH3), - CH=C(CH3)2, -C(CH3)=CH2, -C(CH3)=CH(CH3), -C(CH2CH3)=CH2, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl among others. The term “alkynyl” as used herein refers to straight and branched chain alkyl groups, except that at least one triple bond exists between two carbon atoms. Thus, alkynyl groups have from 2 to 40 carbon atoms, 2 to about 20 carbon atoms, or from 2 to 12 carbons or, in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to – C^CH, -C^C(CH3), -C^C(CH2CH3), -CH2C^CH, -CH2C^C(CH3), and -CH2C^C(CH2CH3) among others. The term “alkoxy” as used herein refers to an oxygen atom connected to an alkyl group, including a cycloalkyl group, as are defined herein. Examples of linear alkoxy groups include but are not limited to methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the like. Examples of branched alkoxy include but are not limited to isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy, isohexyloxy, and the like. Examples of cyclic alkoxy include but are not limited to cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, and the like. An alkoxy group can include about 1 to about 12, about 1 to about 20, or about 1 to about 40 carbon atoms bonded to the oxygen atom, and can further include double or triple bonds, and can also include heteroatoms. For example, an allyloxy group or a methoxyethoxy group is also an alkoxy group within the meaning herein, as is a methylenedioxy group in a context where two adjacent atoms of a structure are substituted therewith. The term “amine” as used herein refers to primary, secondary, and tertiary amines having, e.g., the formula N(group)3 wherein each group can independently be H or non-H, such as alkyl, aryl, and the like. Amines include but are not limited to R-NH2, for example, alkylamines, arylamines, alkylarylamines; R2NH wherein each R is independently selected, such as dialkylamines, diarylamines, aralkylamines, heterocyclylamines and the like; and R3N wherein each R is independently selected, such as trialkylamines, dialkylarylamines, alkyldiarylamines, triarylamines, and the like. The term “amine” also includes ammonium - 8 - 53006853.1 Attorney Docket No.370431-1051WO1 ions as used herein. The term “amino group” as used herein refers to a substituent of the form -NH2, - NHR, -NR2, -NR3+, wherein each R is independently selected, and protonated forms of each, except for -NR3+, which cannot be protonated. Accordingly, any compound substituted with an amino group can be viewed as an amine. An “amino group” within the meaning herein can be a primary, secondary, tertiary, or quaternary amino group. An “alkylamino” group includes a monoalkylamino, dialkylamino, and trialkylamino group. The term “aralkyl” as used herein refers to alkyl groups as defined herein in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to an aryl group as defined herein. Representative aralkyl groups include benzyl and phenylethyl groups and fused (cycloalkylaryl)alkyl groups such as 4-ethyl-indanyl. Aralkenyl groups are alkenyl groups as defined herein in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to an aryl group as defined herein. The term “aryl” as used herein refers to cyclic aromatic hydrocarbon groups that do not contain heteroatoms in the ring. Thus aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups. In some embodiments, aryl groups contain about 6 to about 14 carbons in the ring portions of the groups. Aryl groups can be unsubstituted or substituted, as defined herein. Representative substituted aryl groups can be mono-substituted or substituted more than once, such as, but not limited to, a phenyl group substituted at any one or more of 2-, 3-, 4-, 5-, or 6-positions of the phenyl ring, or a naphthyl group substituted at any one or more of 2- to 8-positions thereof. The term “cycloalkyl” as used herein refers to cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, the cycloalkyl group can have 3 to about 8-12 ring members, whereas in other embodiments the number of ring carbon atoms range from 3 to 4, 5, 6, or 7. Cycloalkyl groups further include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused rings such as, but not limited to, decalinyl, and the like. Cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined herein. Representative substituted cycloalkyl groups can be mono-substituted or substituted more than once, such as, but not limited to, 2,2-, 2,3-, 2,4- 2,5- or 2,6-disubstituted cyclohexyl groups or mono-, di- or tri-substituted norbornyl or cycloheptyl groups, which can be substituted with, for example, - 9 - 53006853.1 Attorney Docket No.370431-1051WO1 amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups. The term “cycloalkenyl” alone or in combination denotes a cyclic alkenyl group. The terms “epoxy-functional” or “epoxy-substituted” as used herein refers to a functional group in which an oxygen atom, the epoxy substituent, is directly attached to two adjacent carbon atoms of a carbon chain or ring system. Examples of epoxy-substituted functional groups include, but are not limited to, 2,3-epoxypropyl, 3,4-epoxybutyl, 4,5- epoxypentyl, 2,3-epoxypropoxy, epoxypropoxypropyl, 2-glycidoxyethyl, 3-glycidoxypropyl, 4-glycidoxybutyl, 2-(glycidoxycarbonyl)propyl, 3-(3,4-epoxycylohexyl)propyl, 2-(3,4- epoxycyclohexyl)ethyl, 2-(2,3-epoxycylopentyl)ethyl, 2-(4-methyl-3,4- epoxycyclohexyl)propyl, 2-(3,4-epoxy-3-methylcylohexyl)-2-methylethyl, and 5,6- epoxyhexyl. The term “functional group” or “substituent” as used herein refers to a group that can be or is substituted onto a molecule or onto an organic group. Examples of substituents or functional groups include, but are not limited to, a halogen (e.g., F, Cl, Br, and I); an oxygen atom in groups such as hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups, carboxyl groups including carboxylic acids, carboxylates, and carboxylate esters; a sulfur atom in groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups; a nitrogen atom in groups such as amines, hydroxyamines, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups. Non-limiting examples of substituents that can be bonded to a substituted carbon (or other) atom include F, Cl, Br, I, OR, OC(O)N(R)2, CN, NO, NO2, ONO2, azido, CF3, OCF3, R, O (oxo), S (thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, (CH2)0-2N(R)C(O)R, (CH2)0-2N(R)N(R)2, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)2, N(R)SO2R, N(R)SO2N(R)2, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)2, N(R)C(S)N(R)2, N(COR)COR, N(OR)R, C(=NH)N(R)2, C(O)N(OR)R, and C(=NOR)R, wherein R can be hydrogen or a carbon-based moiety; for example, R can be hydrogen, (C1-C100)hydrocarbyl, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl; or wherein two R groups bonded to a nitrogen atom or to adjacent nitrogen atoms can together with the nitrogen atom or atoms form a heterocyclyl. The terms “halo,” “halogen,” or “halide” group, as used herein, by themselves or as part of another substituent, mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom. - 10 - 53006853.1 Attorney Docket No.370431-1051WO1 The term “haloalkyl” group, as used herein, includes mono-halo alkyl groups, poly- halo alkyl groups wherein all halo atoms can be the same or different, and per-halo alkyl groups, wherein all hydrogen atoms are replaced by halogen atoms, such as fluoro. Examples of haloalkyl include trifluoromethyl, 1,1-dichloroethyl, 1,2-dichloroethyl, 1,3-dibromo-3,3- difluoropropyl, perfluorobutyl, and the like. The term “heteroaryl” as used herein refers to aromatic ring compounds containing 5 or more ring members, of which, one or more is a heteroatom such as, but not limited to, N, O, and S; for instance, heteroaryl rings can have 5 to about 8-12 ring members. A heteroaryl group is a variety of a heterocyclyl group that possesses an aromatic electronic structure. A heteroaryl group designated as a C2-heteroaryl can be a 5-ring with two carbon atoms and three heteroatoms, a 6-ring with two carbon atoms and four heteroatoms and so forth. Likewise a C4-heteroaryl can be a 5-ring with one heteroatom, a 6-ring with two heteroatoms, and so forth. The number of carbon atoms plus the number of heteroatoms sums up to equal the total number of ring atoms. A heterocyclyl ring designated Cx-ycan be any ring containing 'x' members up to 'y' members, including all intermediate integers between 'x' and 'y' and that contains one or more heteroatoms, as defined herein. In a ring designated Cx-y, all non-heteroatom members are carbon. Heterocyclyl rings designated Cx-y can also be polycyclic ring systems, such as bicyclic or tricyclic ring systems. Heteroaryl groups include, but are not limited to, groups such as pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, thiophenyl, benzothiophenyl, benzofuranyl, indolyl, azaindolyl, indazolyl, benzimidazolyl, azabenzimidazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthalenyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl groups. Heteroaryl groups can be unsubstituted, or can be substituted with groups as is discussed herein. Representative substituted heteroaryl groups can be substituted one or more times with groups such as those listed herein. Additional examples of aryl and heteroaryl groups include but are not limited to phenyl, biphenyl, indenyl, naphthyl (1-naphthyl, 2-naphthyl), N-hydroxytetrazolyl, N- hydroxytriazolyl, N-hydroxyimidazolyl, anthracenyl (1-anthracenyl, 2-anthracenyl, 3- anthracenyl), thiophenyl (2-thienyl, 3-thienyl), furyl (2-furyl, 3-furyl) , indolyl, oxadiazolyl, isoxazolyl, quinazolinyl, fluorenyl, xanthenyl, isoindanyl, benzhydryl, acridinyl, thiazolyl, pyrrolyl (2-pyrrolyl), pyrazolyl (3-pyrazolyl), imidazolyl (1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl), triazolyl (1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl), oxazolyl (2-oxazolyl, 4-oxazolyl, 5-oxazolyl), thiazolyl (2-thiazolyl, 4- - 11 - 53006853.1 Attorney Docket No.370431-1051WO1 thiazolyl, 5-thiazolyl), pyridyl (2-pyridyl, 3-pyridyl, 4-pyridyl), pyrimidinyl (2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 6-pyrimidinyl), pyrazinyl, pyridazinyl (3- pyridazinyl, 4- pyridazinyl, 5-pyridazinyl), quinolyl (2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6- quinolyl, 7-quinolyl, 8-quinolyl), isoquinolyl (1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5- isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl), benzo[b]furanyl (2-benzo[b]furanyl, 3-benzo[b]furanyl, 4-benzo[b]furanyl, 5-benzo[b]furanyl, 6-benzo[b]furanyl, 7- benzo[b]furanyl), 2,3-dihydro-benzo[b]furanyl (2-(2,3-dihydro-benzo[b]furanyl), 3-(2,3- dihydro-benzo[b]furanyl), 4-(2,3-dihydro-benzo[b]furanyl), 5-(2,3-dihydro-benzo[b]furanyl), 6-(2,3-dihydro-benzo[b]furanyl), 7-(2,3-dihydro-benzo[b]furanyl), benzo[b]thiophenyl (2- benzo[b]thiophenyl, 3-benzo[b]thiophenyl, 4-benzo[b]thiophenyl, 5-benzo[b]thiophenyl, 6- benzo[b]thiophenyl, 7-benzo[b]thiophenyl), 2,3-dihydro-benzo[b]thiophenyl, (2-(2,3- dihydro-benzo[b]thiophenyl), 3-(2,3-dihydro-benzo[b]thiophenyl), 4-(2,3-dihydro- benzo[b]thiophenyl), 5-(2,3-dihydro-benzo[b]thiophenyl), 6-(2,3-dihydro- benzo[b]thiophenyl), 7-(2,3-dihydro-benzo[b]thiophenyl), indolyl (1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), indazole (1-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl), benzimidazolyl (1-benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl, 6-benzimidazolyl, 7-benzimidazolyl, 8-benzimidazolyl), benzoxazolyl (1-benzoxazolyl, 2-benzoxazolyl), benzothiazolyl (1- benzothiazolyl, 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), carbazolyl (1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl), 5H-dibenz[b,f]azepine (5H-dibenz[b,f]azepin-1-yl, 5H-dibenz[b,f]azepine-2-yl, 5H-dibenz[b,f]azepine-3-yl, 5H-dibenz[b,f]azepine-4-yl, 5H-dibenz[b,f]azepine-5-yl), 10,11-dihydro-5H-dibenz[b,f]azepine (10,11-dihydro-5H-dibenz[b,f]azepine-1-yl, 10,11-dihydro-5H-dibenz[b,f]azepine-2-yl, 10,11-dihydro-5H-dibenz[b,f]azepine-3-yl, 10,11-dihydro-5H-dibenz[b,f]azepine-4-yl, 10,11-dihydro-5H-dibenz[b,f]azepine-5-yl), and the like. The term “heterocycloalkyl” as used herein refers to a cycloalkyl group as defined herein in which one or more carbon atoms in the ring are replaced by a heteroatom such as O, N, S, P, and the like, each of which may be substituted as described herein if an open valence is present, and each may be in any suitable stable oxidation state. The term “heterocyclyl” as used herein refers to aromatic and non-aromatic ring compounds containing three or more ring members, of which one or more is a heteroatom such as, but not limited to, N, O, and S. Thus, a heterocyclyl can be a cycloheteroalkyl, or a heteroaryl, or if polycyclic, any combination thereof. In some embodiments, heterocyclyl - 12 - 53006853.1 Attorney Docket No.370431-1051WO1 groups include 3 to about 20 ring members, whereas other such groups have 3 to about 15 ring members. The term heterocyclyl includes rings where a CH2group in the ring is replaced by one or more C=O groups, such as found in cyclic ketones, lactones, and lactams. Examples of heterocyclyl groups containing a C=O group include, but are not limited to, β- propiolactam, γ-butyrolactam, δ-valerolactam, and ε-caprolactam, as well as the corresponding lactones. A heterocyclyl group designated as a C2-heterocyclyl can be a 5-ring with two carbon atoms and three heteroatoms, a 6-ring with two carbon atoms and four heteroatoms and so forth. Likewise a C4-heterocyclyl can be a 5-ring with one heteroatom, a 6-ring with two heteroatoms, and so forth. The number of carbon atoms plus the number of heteroatoms equals the total number of ring atoms. A heterocyclyl ring can also include one or more double bonds. A heteroaryl ring is an embodiment of a heterocyclyl group. The phrase “heterocyclyl group” includes fused ring species including those that include fused aromatic and non-aromatic groups. For example, a dioxolanyl ring and a benzdioxolanyl ring system (methylenedioxyphenyl ring system) are both heterocyclyl groups within the meaning herein. The phrase also includes polycyclic ring systems containing a heteroatom such as, but not limited to, quinuclidyl. Heterocyclyl groups can be unsubstituted, or can be substituted as discussed herein. Heterocyclyl groups include, but are not limited to, pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, thiophenyl, benzothiophenyl, benzofuranyl, dihydrobenzofuranyl, indolyl, dihydroindolyl, azaindolyl, indazolyl, benzimidazolyl, azabenzimidazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthalenyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl groups. Representative substituted heterocyclyl groups can be mono-substituted or substituted more than once, such as, but not limited to, piperidinyl or quinolinyl groups, which are 2-, 3-, 4-, 5-, or 6- substituted, or disubstituted with groups such as those listed herein. The term “heterocyclylalkyl” as used herein refers to alkyl groups as defined herein in which a hydrogen or carbon bond of an alkyl group as defined herein is replaced with a bond to a heterocyclyl group as defined herein. Representative heterocyclyl alkyl groups include, but are not limited to, furan-2-yl methyl, furan-3-yl methyl, pyridine-3-yl methyl, tetrahydrofuran-2-yl ethyl, and indol-2-yl propyl. The term “heteroarylalkyl” as used herein refers to alkyl groups as defined herein in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to a heteroaryl group as defined herein. - 13 - 53006853.1 Attorney Docket No.370431-1051WO1 The term “hydrocarbon” or “hydrocarbyl” as used herein refers to a molecule or functional group that includes carbon and hydrogen atoms. The term can also refer to a molecule or functional group that normally includes both carbon and hydrogen atoms but wherein all the hydrogen atoms are substituted with other functional groups. As used herein, the term “hydrocarbyl” refers to a functional group derived from a straight chain, branched, or cyclic hydrocarbon, and can be alkyl, alkenyl, alkynyl, aryl, cycloalkyl, acyl, or any combination thereof. Hydrocarbyl groups can be shown as (Ca- Cb)hydrocarbyl, wherein a and b are integers and mean having any of a to b number of carbon atoms. For example, (C1-C4)hydrocarbyl means the hydrocarbyl group can be methyl (C1), ethyl (C2), propyl (C3), or butyl (C4), and (C0-Cb)hydrocarbyl means in certain embodiments there is no hydrocarbyl group. The term “monovalent” as used herein refers to a substituent connecting via a single bond to a substituted molecule. When a substituent is monovalent, such as, for example, F or Cl, it is bonded to the atom it is substituting by a single bond. The term “independently selected from” as used herein refers to referenced groups being the same, different, or a mixture thereof, unless the context clearly indicates otherwise. Thus, under this definition, the phrase “X1, X2, and X3are independently selected from noble gases” would include the scenario where, for example, X1, X2, and X3are all the same, where X1, X2, and X3are all different, where X1and X2are the same but X3is different, and other analogous permutations. The term “organic group” as used herein refers to any carbon-containing functional group. Examples can include an oxygen-containing group such as an alkoxy group, aryloxy group, aralkyloxy group, oxo(carbonyl) group; a carboxyl group including a carboxylic acid, carboxylate, and a carboxylate ester; a sulfur-containing group such as an alkyl and aryl sulfide group; and other heteroatom-containing groups. Non-limiting examples of organic groups include OR, OOR, OC(O)N(R)2, CN, CF3, OCF3, R, C(O), methylenedioxy, ethylenedioxy, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, (CH2)0-2N(R)C(O)R, (CH2)0-2N(R)N(R)2, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)2, N(R)SO2R, N(R)SO2N(R)2, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)2, N(R)C(S)N(R)2, N(COR)COR, N(OR)R, C(=NH)N(R)2, C(O)N(OR)R, C(=NOR)R, and substituted or unsubstituted (C1-C100)hydrocarbyl, wherein R can be hydrogen (in examples that include other carbon atoms) or a carbon-based moiety, and wherein the carbon-based moiety can be substituted or unsubstituted. - 14 - 53006853.1 Attorney Docket No.370431-1051WO1 The term “room temperature” as used herein refers to a temperature of about 15 °C to 28 °C. The term “solvent” as used herein refers to a liquid that can dissolve a solid, liquid, or gas. Non-limiting examples of solvents are silicones, organic compounds, water, alcohols, ionic liquids, and supercritical fluids. The term “standard temperature and pressure” as used herein refers to 20 °C and 101 kPa. The term “substantially” as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. The term “substantially free of” as used herein can mean having none or having a trivial amount of, such that the amount of material present does not affect the material properties of the composition including the material, such that the composition is about 0 wt% to about 5 wt% of the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less. The term “substantially free of” can mean having a trivial amount of, such that a composition is about 0 wt% to about 5 wt% of the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less, or about 0 wt%. The term “substituted” as used herein in conjunction with a molecule or an organic group as defined herein refers to the state in which one or more hydrogen atoms contained therein are replaced by one or more non-hydrogen atoms. The substitution can be direct substitution, whereby the hydrogen atom is replaced by a functional group or substituent, or an indirect substitution, whereby an intervening linker group replaces the hydrogen atom, and the substituent or functional group is bonded to the intervening linker group. A non-limiting example of direct substitution is: RR-H ^ RR-Cl, wherein RR is an organic moiety / fragment / molecule. A example of indirect substitution is: RR-H ^ RR- (LL)zz-Cl, wherein RR is an organic moiety / fragment / molecule, LL is an linker group, and 'zz' is an integer from 0 to 100 inclusive. When zz is 0, LL is absent, and direct substitution results. The intervening linker group LL is at each occurrence independently selected from the group consisting of -H, -O-, -OR, -S-, -S(=O)-, -S(=O)2-, -SR, -N(R)-, - NR2, -CR=, -C^^^-CH2-, -CHR-, -CR2-, -CH3, -C(=O)-, -C(=NR)-, and combinations thereof. (LL)zzcan be linear, branched, cyclic, acyclic, and combinations thereof. - 15 - 53006853.1 Attorney Docket No.370431-1051WO1 Methods of Preparing Acetals The compounds described herein can be prepared by the general schemes described herein, using the synthetic method known by those skilled in the art. The following examples illustrate non-limiting embodiments of the compound(s) described herein and their preparation. In various embodiments, a method for preparing acetals is provided. The method includes: heating an alcohol of formula (I): , in the presence of an aldehyde , to provide an acetal of formula , wherein: each independently is absent or a single bond; R1and R2are each independently selected from the group consisting of H, C1-3alkyl, -OH, OC1-3 alkyl, F, Cl, Br, and C1-3 alkyl substituted by one OH, wherein R1and R2are not simultaneously -OH; R1’and R2’are each independently a bond (absent), -CH2, -CH(CH3)-, or - CH(CH2CH3)-, provided that at least one of R1’and R2’is not a bond; R3and R4are each independently selected from the group consisting of H, C1-3 alkyl, F, Cl, Br, C6-10aryl, and C5heteroaryl; R5, R6, and R7are each independently selected from the group consisting of H, F, Cl, OR, (CH2)1-3OH, OC(O)N(R)2, CN, CF3, OCF3, R, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, and (CH2)0-2N(R)C(O)R; - 16 - 53006853.1 Attorney Docket No.370431-1051WO1 each R is independently H or C1-10 hydrocarbyl optionally substituted by F or Cl; n is 0 or 1, provided that, when n is 0, R1and R2are absent; m is an integer from 1 to 100, provided that when m is greater than 1, R1and R2are H; with the proviso that: i) if m is 1 and one of R1or R2does not comprise an OH group, then Y is -(CHR3)-; Z is -(CHR4)-; and X is -C(R1)(R2)- or a single bond connecting Y and Z; ii) if m is 1 and R1and R2are each independently selected from the group consisting of -OH, -CH2OH, -CH(OH)CH3, and -CH(OH)CH2CH3, then Y is -(CHR3)-; Z is -(CHR4)-; and iv) if m is greater than 1, then - 17 - 53006853.1 Attorney Docket No.370431-1051WO1 In certain embodiments, the heating takes place in the absence of solvent. In certain embodiments, the heating takes place in the absence of catalyst. In certain embodiments, the heating takes place in the absence of solvent and in the absence of catalyst. In certain embodiments, less than 5 % (w / w) of ring-opened furan derivatives or polymerized furan derivatives, relative to the initial amount of (II), form during the heating. In various embodiments, the alcohol of formula (I) is (ethylene glycol), (1,3-propanediol), (glycerol), (trimethylolpropane) (pentaerythritol). In various occurs at a temperature of at least about 70 ºC, or about 70 to about 90 ºC. In various embodiments, the heating occurs at a temperature of about 60 to about 110 ºC. In various embodiments, the heating occurs at a temperature of at least or equal to about 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 83, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, or about 95 ºC. In various embodiments, the heating occurs at a temperature of about 90 ºC. The heating can take place for a period of 3 to 24 hours, or about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or about 24 hours. The reaction between the compound of formula (I) and formula (II) is, in some embodiments, complete after about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or about 24 hours. The heating can, in certain embodiments, advantageously take place in an apparatus capable of refluxing the mixture of formula (I) and formula (II) at the mixture’s boiling point. The apparatus can be, for example, a Dean-Stark trap for removal of water produced during the reaction. In various embodiments, the heating takes place under an inert atmosphere, such as an atmosphere of nitrogen or argon. In various embodiments, the heating takes place in ambient atmosphere (air). In various embodiments, the isolated yield of the compound of formula (III) is at least, equal to, or greater than about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or about 98% relative to the initial amount of (II). As shown in FIG.11, heating mixtures of formula (I) and formula (II) at temperatures at or greater than 95 ºC unexpectedly and undesirably increases the amount of ring-opened - 18 - 53006853.1 Attorney Docket No.370431-1051WO1 furan derivatives and / or polymerized furan derivatives. In some studies, when low yields are reported for the acetal product, such as yields of 30, 25, 20, or 15%, or lower, it is believed, without being bound by theory, that the balance of the material produced after reaction is a mixture of ring-opened furan derivatives and / or polymerized furan derivatives. These undesirable side products are particularly likely when the acetal is formed (either with or without catalyst) at elevated temperatures, such as 95-100 ºC, or higher. Thus, heating a mixture of the alcohol of formula (I) and the furfural of formula (II) at a temperature at or below 90, 91, or 92 ºC, in some embodiments, is extremely important for obtaining acetal reaction products having less than 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, 0.01, 0.005, or 0.001 % (w / w) of ring-opened furan derivatives and / or polymerized furan derivatives relative to the initial amount of (II). The sensitivity of the reaction to small changes in reaction temperatures such that heating at a temperature as high as 90-92 ºC the reaction proceeded with less than 5% (w / w) of ring-opened furan derivatives and / or polymerized furan derivatives relative to the initial amount of (II), but heating at a temperature of 93-95 ºC resulted in significant levels of side products, was surprising and unexpected. In various embodiments, the compounds of formula (I) and / or formula (II) can contain impurities associated with their production or synthesis, provided that the impurities do not act as catalysts or increase the yield of ring-opened and / or polymerized furans. As used herein, the term “absence of solvent” means no additional solvent is added to a mixture of the compounds of formula (I) and formula (II) while they are heated. As noted herein, the compounds of formula (I) and / or formula (II) can contain impurities, such as solvent impurities, that are present as a result of their production or synthesis. As used herein, the term “absence of catalyst” means no additional catalyst is added to a mixture of the compounds of formula (I) and formula (II). In various embodiments, no detectable catalyst is present in the mixture of the compounds of formula (I) and formula (II). Examples of catalysts include, but are not limited to, heterogeneous catalysts, homogenous catalysts, catalytic resins such as cationic exchange resins, zeolites, and the like. In various embodiments, less than 5 % (w / w) of ring-opened furan derivatives and / or polymerized furan derivatives form during the heating relative to the amount of the aldehyde of formula (II) at any of the temperatures or for any of the periods described herein. In various embodiments, less than 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, 0.01, 0.005, or 0.001 % (w / w) of ring-opened furan derivatives and / or polymerized furan derivatives form during the heating relative to the amount of the aldehyde of formula (II) at - 19 - 53006853.1 Attorney Docket No.370431-1051WO1 any of the temperatures or for any of the periods described herein. In various embodiments, 0.001 to 1, 0.001 to 0.5, or 0.001 to 0.01% (w / w) of ring-opened furan derivatives and / or polymerized furan derivatives form during the heating relative to the amount of the aldehyde of formula (II) at any of the temperatures or for any of the periods described herein. In various embodiments, no detectable amount of ring-opened furan derivatives or polymerized furan derivatives form during the heating relative to the amount of the aldehyde of formula (II) at any of the temperatures or for any of the periods described herein. Suitable methods for detecting the ring-opened furan derivatives or polymerized furan derivatives include IR spectroscopy, HPLC (high performance liquid chromatography), mass spectrometry (MS), and combinations of these analytical methods. In various embodiments, the alcohol of formula (I) is not glycerol (1,2,3-propanetriol) and the aldehyde of formula (II) is not furfural. In various embodiments, the alcohol of formula (I) is not glycerol (1,2,3- propanetriol). In various embodiments, the aldehyde of formula (II) is not furfural. In various embodiments, the acetal of formula (III) is an acetal of formula (III-A), R3R1. In various an acetal of formula (III-B), . In various of formula (III-C), . In various of formula (III-D), - 20 - 53006853.1 Attorney Docket No.370431-1051WO1 R3O R5 O. In the compounds of , formula (III-C), and formula (III-D), the variables are compound of formula (III). In various embodiments, in the compounds of formula (III-A), formula (III-B), formula (III-C), and formula (III-D), R3and R4are H. In various embodiments, in the compounds of formula (III-A), formula (III-B), formula (III-C), and formula (III-D), n is 0. In various embodiments, in the compounds of formula (III-A), formula (III-B), formula (III-C), and formula (III-D), n is 1. In various embodiments, in the compounds of formula (III-A), formula (III-B), formula (III-C), and formula (III-D), R1and R2are H. In various embodiments, in the compounds of formula (III-A), formula (III-B), formula (III-C), and formula (III-D), R1is CH3 and R2is -CH2OH. In various embodiments, in the compounds of formula (III-A), formula (III-B), formula (III-C), and formula (III-D), R1is -CH2OH and R2is -CH2OH. The method of claim 1, wherein R5is H, R6is H, and R7is H. In various embodiments, in the compounds of formula (III-A), formula (III-B), formula (III-C), and formula (III-D), R5is -CH2OH, R6is H, and R7is H. In various embodiments, in the compounds of formula (III-A), formula (III-B), formula (III-C), and formula (III-D), R1’is -CH2-, and R2’is -CH2-. In various embodiments, in the compounds of formula (III-A), formula (III-B), formula (III-C), and formula (III-D), R1’is -CH2- and R2’is -CH2-. In various embodiments, in the compounds of formula (III-A), formula (III-B), formula (III-C), and formula (III-D), m is 1. In various embodiments, in the compound of formula (III-D), m is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100. Acetal Compositions - 21 - 53006853.1 Attorney Docket No.370431-1051WO1 In various embodiments, a compound or a salt, solvate enantiomer, tautomer, or diastereomer thereof, of formula (IV-A), formula (IV-B), or formula (IV-C) is provided: F, Cl, and Br; R3and R4are each independently selected from the group consisting of H, C1-3alkyl, F, Cl, C6-10 aryl, C5 heteroaryl; R5, R6, and R7are each independently selected from the group consisting of H, F, Cl, Br, OR, (CH2)1-3OH, (CH2)1-3OA, OC(O)N(R)2, CN, CF3, OCF3, R, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, and (CH2)0-2N(R)C(O)R; R9is H, C1-4alkyl, C6-10aryl, F, Cl, or Br, wherein the C6-10aryl is optionally substituted by 1 to 5 substituents selected from the group consisting of F, Cl, Br, OR, (CH2)1-3OH, OC(O)N(R)2, CN, CF3, OCF3, R, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, and (CH2)0-2N(R)C(O)R; p is 0 or 1; - 22 - 53006853.1 Attorney Docket No.370431-1051WO1 R10and R11are each independently selected from the group consisting of H, F, Cl, Br, and C1-4alkyl; and R is H, A, or C1-10 hydrocarbyl optionally substituted by F or Cl. In various embodiments, in the compounds of formula (IV-A), formula (IV-B), and formula (IV-C), R3and R4are H. In various embodiments, in the compounds of formula (IV- A), formula (IV-B), and formula (IV-C), R1is H. In various embodiments, in the compounds of formula (IV-A), formula (IV-B), and formula (IV-C), R1is CH3. In various embodiments, in the compounds of formula (IV-A), formula (IV-B), and formula (IV-C), R5is H, R6is H, and R7is H. In various embodiments, in the compounds of formula (IV-A), formula (IV-B), and . In various embodiments, in the compounds of formula (IV-A), formula (IV-B), and . In various embodiments, in (IV-A), formula (IV-B), and . in the compounds of formula (IV-A), formula (IV-B), and . compounds of formula (IV-A), formula (IV-B), and formula (IV-C), R9is methyl. In various embodiments, in the compounds of formula (IV-A), formula (IV-B), and formula (IV-C), R10is H and R11is H. In various embodiments, p is 0. In various embodiments, p is 1. In various embodiments, a resin containing a reaction product of at least one compound of formula (IV-A), formula (IV-B), formula (IV-C), or a combination thereof and at least one additional monomer or polymer is provided. Suitable polymers / monomers with which the compounds of formula (IV-A), formula (IV-B), formula (IV-C), or formula (III) can be used with include, but are not limited to, polyureas, polyurethanes, polyesters, polymethacrylate, and the like. In various embodiments, compounds of formula (IV-A), formula (IV-B), formula (IV-C), or formula (III) can be used as crosslinkers. In various - 23 - 53006853.1 Attorney Docket No.370431-1051WO1 embodiments, the resin can further include an amine additive that is included either before the resin is cured (pre-cure) or after the resin is cured (post-cure). The amine additive can be any suitable amine, or diamine, that reacts with a group in compounds of formula (IV-A), formula (IV-B), formula (IV-C), or formula (III) that is capable of reacting with an amine. Suitable amines or diamines include, but are not limited to, PACM (4,4'- diaminodicyclohexylmethane) and DETA (diethylenetriamine), and DFDA (5,5′- methylenedifurfurylamine), and the like. A non-limiting example of a group that can react or does react with amine or diamine is an epoxide or a Michael acceptor such as an acrylate or acrylic acid. In various embodiments, the compound of formula (IV-A) is . In various is Pent). In (IV-A) is . The compounds stereocenters, and each stereocenter can exist independently in either the (R) or (S) configuration. In certain embodiments, compounds described herein are present in optically active or racemic forms. It is to be understood that the compounds described herein encompass racemic, optically- active, regioisomeric and stereoisomeric forms, or combinations thereof that possess the therapeutically useful properties described herein. Preparation of optically active forms is achieved in any suitable manner, including by way of non-limiting example, by resolution of the racemic form with recrystallization techniques, synthesis from optically-active starting materials, chiral synthesis, or chromatographic separation using a chiral stationary phase. In certain embodiments, a mixture of one or more isomer is utilized as the therapeutic compound described herein. In other embodiments, compounds described herein contain one - 24 - 53006853.1 Attorney Docket No.370431-1051WO1 or more chiral centers. These compounds are prepared by any means, including stereoselective synthesis, enantioselective synthesis and / or separation of a mixture of enantiomers and / or diastereomers. Resolution of compounds and isomers thereof is achieved by any means including, by way of non-limiting example, chemical processes, enzymatic processes, fractional crystallization, distillation, and chromatography. The methods and formulations described herein include the use of N-oxides (if appropriate), crystalline forms (also known as polymorphs), solvates, amorphous phases, and / or pharmaceutically acceptable salts of compounds having the structure of any compound(s) described herein, as well as metabolites and active metabolites of these compounds having the same type of activity. Solvates include water, ether (e.g., tetrahydrofuran, methyl tert-butyl ether) or alcohol (e.g., ethanol) solvates, acetates and the like. In certain embodiments, the compounds described herein exist in solvated forms with pharmaceutically acceptable solvents such as water, and ethanol. In other embodiments, the compounds described herein exist in unsolvated form. In certain embodiments, the compound(s) described herein can exist as tautomers. All tautomers are included within the scope of the compounds presented herein. In certain embodiments, compounds described herein are prepared as prodrugs. A “prodrug” refers to an agent that is converted into the parent drug in vivo. In certain embodiments, upon in vivo administration, a prodrug is chemically converted to the biologically, pharmaceutically or therapeutically active form of the compound. In other embodiments, a prodrug is enzymatically metabolized by one or more steps or processes to the biologically, pharmaceutically or therapeutically active form of the compound. In certain embodiments, sites on, for example, the aromatic ring portion of compound(s) described herein are susceptible to various metabolic reactions. Incorporation of appropriate substituents on the aromatic ring structures may reduce, minimize or eliminate this metabolic pathway. In certain embodiments, the appropriate substituent to decrease or eliminate the susceptibility of the aromatic ring to metabolic reactions is, by way of example only, a deuterium, a halogen, or an alkyl group. Compounds described herein also include isotopically-labeled compounds wherein one or more atoms is replaced by an atom having the same atomic number, but an atomic mass or mass number different from the atomic mass or mass number usually found in nature. Examples of isotopes suitable for inclusion in the compounds described herein include and are not limited to2H,3H,11C,13C,14C,36Cl,18F,123I,125I,13N,15N,15O,17O,18O,32P, and35S. In certain embodiments, isotopically-labeled compounds are useful in drug and / or substrate - 25 - 53006853.1 Attorney Docket No.370431-1051WO1 tissue distribution studies. In other embodiments, substitution with heavier isotopes such as deuterium affords greater metabolic stability (for example, increased in vivo half-life or reduced dosage requirements). In yet other embodiments, substitution with positron emitting isotopes, such as11C,18F,15O and13N, is useful in Positron Emission Topography (PET) studies for examining substrate receptor occupancy. Isotopically-labeled compounds are prepared by any suitable method or by processes using an appropriate isotopically-labeled reagent in place of the non-labeled reagent otherwise employed. In certain embodiments, the compounds described herein are labeled by other means, including, but not limited to, the use of chromophores or fluorescent moieties, bioluminescent labels, or chemiluminescent labels. The compounds described herein, and other related compounds having different substituents are synthesized using techniques and materials described herein and as described, for example, in Fieser & Fieser's Reagents for Organic Synthesis, Volumes 1-17 (John Wiley and Sons, 1991); Rodd's Chemistry of Carbon Compounds, Volumes 1-5 and Supplementals (Elsevier Science Publishers, 1989); Organic Reactions, Volumes 1-40 (John Wiley and Sons, 1991), Larock's Comprehensive Organic Transformations (VCH Publishers Inc., 1989), March, Advanced Organic Chemistry 4thEd., (Wiley 1992); Carey & Sundberg, Advanced Organic Chemistry 4th Ed., Vols. A and B (Plenum 2000,2001), and Green & Wuts, Protective Groups in Organic Synthesis 3rd Ed., (Wiley 1999) (all of which are incorporated by reference for such disclosure). General methods for the preparation of compound as described herein are modified by the use of appropriate reagents and conditions, for the introduction of the various moieties found in the formula as provided herein. Compounds described herein are synthesized using any suitable procedures starting from compounds that are available from commercial sources, or are prepared using procedures described herein. In certain embodiments, reactive functional groups, such as hydroxyl, amino, imino, thio or carboxy groups, are protected in order to avoid their unwanted participation in reactions. Protecting groups are used to block some or all of the reactive moieties and prevent such groups from participating in chemical reactions until the protective group is removed. In other embodiments, each protective group is removable by a different means. Protective groups that are cleaved under totally disparate reaction conditions fulfill the requirement of differential removal. In certain embodiments, protective groups are removed by acid, base, reducing conditions (such as, for example, hydrogenolysis), and / or oxidative conditions. Groups such - 26 - 53006853.1 Attorney Docket No.370431-1051WO1 as trityl, dimethoxytrityl, acetal and t-butyldimethylsilyl are acid labile and are used to protect carboxy and hydroxy reactive moieties in the presence of amino groups protected with Cbz groups, which are removable by hydrogenolysis, and Fmoc groups, which are base labile. Carboxylic acid and hydroxy reactive moieties are blocked with base labile groups such as, but not limited to, methyl, ethyl, and acetyl, in the presence of amines that are blocked with acid labile groups, such as t-butyl carbamate, or with carbamates that are both acid and base stable but hydrolytically removable. In certain embodiments, carboxylic acid and hydroxy reactive moieties are blocked with hydrolytically removable protective groups such as the benzyl group, while amine groups capable of hydrogen bonding with acids are blocked with base labile groups such as Fmoc. Carboxylic acid reactive moieties are protected by conversion to simple ester compounds as exemplified herein, which include conversion to alkyl esters, or are blocked with oxidatively-removable protective groups such as 2,4-dimethoxybenzyl, while co- existing amino groups are blocked with fluoride labile silyl carbamates. Allyl blocking groups are useful in the presence of acid- and base- protecting groups since the former are stable and are subsequently removed by metal or pi-acid catalysts. For example, an allyl-blocked carboxylic acid is deprotected with a palladium-catalyzed reaction in the presence of acid labile t-butyl carbamate or base-labile acetate amine protecting groups. Yet another form of protecting group is a resin to which a compound or intermediate is attached. As long as the residue is attached to the resin, that functional group is blocked and does not react. Once released from the resin, the functional group is available to react. Typically blocking / protecting groups may be selected from: H H H H H H . - 27 - 53006853.1 Attorney Docket No.370431-1051WO1 Other protecting groups, plus a detailed description of techniques applicable to the creation of protecting groups and their removal are described in Greene & Wuts, Protective Groups in Organic Synthesis, 3rd Ed., John Wiley & Sons, New York, NY, 1999, and Kocienski, Protective Groups, Thieme Verlag, New York, NY, 1994, which are incorporated herein by reference for such disclosure. Examples Various embodiments of the present application can be better understood by reference to the following Examples which are offered by way of illustration. The scope of the present application is not limited to the Examples given herein. Materials & Methods Materials Furfural and its derivatives used in this work included furfural (Sigma Aldrich), 5- methyl-2-furfural (Alfa Aesar), and 5-hydroxymethyl furfural (Sigma Aldrich). Ethylene glycol (VWR), 1,3-propane diol (Sigma Aldrich), glycerol (Sigma Aldrich), trimethylolpropane (Sigma Aldrich), and pentaerythritol. Methacrylic anhydride (Sigma Aldrich) and 4-dimethylaminopyridine (4-DMAP, Sigma Aldrich), epichlorohydrin, TBAB, toluene (VWR), and dichloromethane (VWR), Bisphenol A glycidyl dimethylacrylate (Esstech Inc.), Trigonox, and cobalt naphthalene were all used as obtained from the listed commercial sources without further purification. Synthesis of F-Gly Furfural and glycerol were combined in a 100 mL three-neck round bottom flask. This reaction mixture was continuously stirred at 75°C under nitrogen. A Dean-Stark apparatus was attached to the reactor to collect water which forms as a byproduct of this reaction. The temperature of the oil bath was raised to 90°C, and the contents within the reactor continued to stir for 24 hours, reaching 95% furfural conversion. Methacrylation of F-Gly to mF-Gly was carried out by combining F-Gly with methacrylic anhydride and 4-DMAP at room temperature in dichloromethane. After 24 hours, the contents of this reaction were washed with a 10 wt% NaOH solution. After removal of all residual methacrylic acid, a rotary evaporator was used to extract the product from dichloromethane at 45°C under 200 mmHg vacuum. - 28 - 53006853.1 Attorney Docket No.370431-1051WO1 Synthesis of MF-Gly 5-methyl-2-furfural (MF) and glycerol were combined in a 100 mL three-neck round bottom flask. This reaction mixture was continuously stirred at 75 °C under nitrogen. A Dean-Stark apparatus was attached to the reactor to collect water which forms as a byproduct of this reaction. The temperature of the oil bath was raised to 90 °C, and the contents within the reactor continued to stir for 24 hours, reaching 96.5% furfural conversion. Methacrylation of MF-Gly to mMF-Gly was carried out by combining MF-Gly with methacrylic anhydride and 4-DMAP at room temperature in dichloromethane. After 24 hours, the contents of this reaction were washed with a 10 wt% NaOH solution. After removal of all residual methacrylic acid, a rotary evaporator was used to extract the product from dichloromethane at 45°C under 200 mmHg vacuum. Synthesis of HMF-Gly 5-hydroxymethyl-furfural (HMF) and glycerol were combined in a 100 mL three-neck round bottom flask. This reaction mixture was continuously stirred at 75 °C under nitrogen. A Dean-Stark apparatus was attached to the reactor to collect water which forms as a byproduct of this reaction. The temperature of the oil bath was raised to 90 °C, and the contents within the reactor continued to stir for 24 hours, reaching 85% furfural conversion. Methacrylation of HMF-Gly to mHMF-Gly was carried out by combining HMF-Gly with methacrylic anhydride and 4-DMAP at room temperature in dichloromethane. After 24 hours, the contents of this reaction were washed with a 10 wt% NaOH solution. After removal of all residual methacrylic acid, a rotary evaporator was used to extract the product from dichloromethane at 45 °C under 200 mmHg vacuum. Synthesis of HMF-TMP 5-hydroxymethyl-furfural (5HMF) and trimethylolpropane (TMP) were combined in a 100 mL three-neck round bottom flask. This reaction mixture was continuously stirred at 75°C under nitrogen. A Dean-Stark apparatus was attached to the reactor to collect water which forms as a byproduct of this reaction. The temperature of the oil bath was raised to 90°C, and the contents within the reactor continued to stir for 24 hours, reaching X% furfural conversion. Methacrylation of HMF-TMP to mHMF-TMP was carried out by combining HMF- TMP (7.9 g) with methacrylic anhydride (15 g) and 4-DMAP at room temperature in - 29 - 53006853.1 Attorney Docket No.370431-1051WO1 dichloromethane. After 24 hours, the contents of this reaction were washed with a 10 wt% NaOH solution. After removal of all residual methacrylic acid, a rotary evaporator was used to extract the product from dichloromethane at 45°C under 200 mmHg vacuum. Epoxidation of HMF-TMP to eHMF-TMP was accomplished by combining HMF- TMP (10 g) with epichlorohydrin (48 g) and 20 wt% TBAB (with respect to mass of HMF- TMP) at 60°C for 6 hours. The contents of the reactor were cooled to room temperature. Then, a 10 wt% NaOH solution was added dropwise into the reactor and allowed to mix for 3 hours at room temperature, followed by 2 hours at 40°C. The epoxidized product was extracted from the aqueous solution by addition of dichloromethane. After determining that all the epoxy rings had been closed, a rotary evaporator was used to extract the product from dichloromethane at 45°C under 100 mmHg vacuum. The temperature was then increased to 80°C to remove residual epichlorohydrin. Synthesis of HMF-Pent 5-hydroxymethyl-furfural (5HMF) and pentaerythritol (Pent) were combined in a 100 mL three-neck round bottom flask. This reaction mixture was continuously stirred at 75°C under nitrogen. A Dean-Stark apparatus was attached to the reactor to collect water which forms as a byproduct of this reaction. The temperature of the oil bath was raised to 90°C, and the contents within the reactor continued to stir for 24 hours, reaching X% furfural conversion. Synthesis of F-EG and F-Prop Furfural was combined with either ethylene glycol (EG) or 1,3-propane diol (Prop) in a 100 mL three-neck round bottom flask. This reaction mixture was continuously stirred at 75°C under nitrogen. A Dean-Stark apparatus was attached to the reactor to collect water which forms as a byproduct of this reaction. The temperature of the oil bath was raised to 90°C, and the contents within the reactor continued to stir for 24 hours. Polymer Preparation Monomethacrylate resins were added into BisGMA as reactive diluent components. After combining 35 wt% mF-Gly or mMF-Gly in BisGMA, samples were cured using 1.5 wt% Trigonox and 0.75 wt% CoNap. Dimethacrylate resins mHMF-Gly and mHMF- TMP were cured on their own using 1.5 wt% Trigonox and 0.75 wt% CoNap as well. All test specimens were allowed to set overnight at room temperature in a silicone mold, followed by - 30 - 53006853.1 Attorney Docket No.370431-1051WO1 a post-cure schedule of 140°C for 3 hours. Monomer Characterization A Nicolet 6700 Mid-IR spectrometer set up with a diamond ATR cell was used to obtain FTIR spectra reported in this work. Aliquots of the reactor contents were taken at various time intervals using a glass pipet and placed on the ATR scanner. Spectra were then taken using an average of 32 scans with a resolution of 4 cm-1. The molar mass and purity of reaction products were determined by gel permeation chromatography (GPC) using a refractive index (RI) detector. Proton (1H) and carbon (13C) nuclear magnetic resonance (NMR) were also conducted to define the molecular structure of each reaction product. Spectra were recorded using an Brucker Avance Neo at 400 MHz for1H and blank MHz for13C at room temperature. All samples were dissolved in CDCl3 and referenced to the solvent residue peak. Thermal Properties Differential scanning calorimetry (DSC) conducted on reaction products to determine thermal transitions and overall stability. A TA Instruments Q50 DSC device was used to perform experiments. Specimen were exposed to temperatures ranging from - 50°C to 200°C at a heating rate of 5°C / min. Thermograms shown in the figures throughout this work are oriented “exo up”. Dynamic mechanical analysis (DMA) experiments were performed on cured samples to obtain thermomechanical properties of resultant polymers. A TA Instruments Q800 DMA device was used to perform experiments. Samples with dimensions of 34 mm x 13 mm x 3 mm were used in testing. Specimen were tested at a frequency of 1 Hz while the temperature was ramped from an initial equilibration point of −80 °C to 250 °C at a rate of 2 °C / min. The main tan delta peak for each thermoset is reported as a measure of the glass- transition temperature (Tg) of these materials. Results & Discussion Monomer Synthesis & Characterization - 31 - 53006853.1 Attorney Docket No.370431-1051WO1 Scheme 1 shows an example synthetic pathway that was used to prepare acetals from hydroxymethylfurfural (4) with glycerol (2), trimethylolpropane (5), and pentaerythritol (8), in accordance with various embodiments. Acetal bonds are generally formed by the reaction between an aldehyde with two equivalents of alcohol reactants. Conventional acetalization strategies typically involve the addition of an acid catalyst to drive this condensation reaction forward. Benzylic or fatty acid-derived aldehydes easily remain stable under these reaction conditions to produce the desired acetal products. Furan-based materials, however, have previously been reported to undergo ring-opening and self-condensation reactions in the presence of such catalysts. This heterolysis disrupts the structure of the desired reaction product and instead results in formation of insoluble char that cannot be used toward the desired application. Although many studies have been conducted on finding ideal catalysts for this reaction, oftentimes ineffective or expensive. Removal of the acid catalyst does not hinder the formation of acetal bonds when furfural derivatives are used as reactants. Scheme 2 shows an example synthetic pathway that was used to prepare acetals from furfurals (furfural, methylfurfural, and hydroxyfurfural) and glycerol, in accordance with various embodiments. - 32 - 53006853.1 Attorney Docket No.370431-1051WO1 Polymer Characterization Furfural acetals containing one or two chemical sites can be modified by common polymerizable functionalities to create high-value precursors. In various embodiments, monomethacrylate precursors can be used as reactive diluents in viscous resin systems, and dimethacrylate crosslinkers can take the place of structural units in typical thermosetting formulations. For example, monomethacrylates of F-Gly (mF-Gly) and MF-Gly (mMF-Gly) were added to BisGMA (bisphenol A-glycidyl methacrylate) and BisEMA (ethoxylated bisphenol-A dimethacrylate). Dimethacrylates of HMF-Gly, HMF-TMP, and HMF-Pent cured on their own. FIG.6 shows examples of acetals as described herein suitable for use in polymer applications. FIGs.9-10 show results obtained during testing of the compounds in Table 1. Table 1 Diluent E’ at RT Tan Delta Tg In Table 1, 35 wt% of the mMF-Gly or mF-Gly was used, with 65 wt% of BisGMA; RT is room temperature. In Table 1, mF-Gly has the structure - 33 - 53006853.1 Attorney Docket No.370431-1051WO1 O OOand mMF-Gly has the . Methacrylation of the monomers were performed using the same synthesis were at room temperature. Methacrylic anhydride was added to the reactor based on the moles of hydroxyl (OH) groups that are present in the furanic acetal precursors. For monomethacrylates, a 1:1.1 molar ratio of acetal to methacrylic anhydride was used. For dimethacrylates, a 1:2.2 molar ratio of acetal to methacrylic anhydride was used. Dichloromethane was used as a solvent in the amount of 40 wt% and 2 wt% 4-dimethylamino pyridine was used to catalyze the reaction. These weight percentages are calculated with respect to the mass of all reactants. In various embodiments, mF-Gly is a mixture of . . . of 100:0 to 0:100 of the 5- and 6-membered acetals, respectively. mHMF-TMP and mHMF-Pent have the following structures: - 34 - 53006853.1 Attorney Docket No.370431-1051WO1 Pent). Diols 6 and 7 were methacrylated to create difunctional crosslinkers capable of forming thermoset polymers. FIG.12 shows the FTIR spectra of dimethacrylate precursors 6m and 7m. The presence of absorption signals corresponding to ester groups (1720 cm-1) and terminal double bonds (940 cm- 1) confirmed that the methacrylate functionality was successfully grafted onto diols 6 and 7. Additionally, the hydroxyl band (3200-3600 cm- 1) that appears on the spectra of the initial diol precursors is no longer present, indicating a full extent of esterification has taken place. Characterization of Methacrylate Thermosets from 6m and 7m Both methacrylate resins were cured using a common thermal initiator up to 140°C. 6m and 7m were also cured with reactive diluents including para-methyl styrene (p-MST) and methacrylate fatty acid (mfa) using the same curing conditions. The thermomechanical properties of thermosets cured from 6m and 7m were investigated by DMA. FIG.13 shows the storage modulus and tan delta signals obtained from these experiments. Table 2 outlines the storage modulus (E’) at room temperature and glass-transition values that were detected. - 35 - 53006853.1 Attorney Docket No.370431-1051WO1 Table 2. Storage modulus (E’) at room temperature and glass-transition values for thermosets cured from 6m and 7m. Reactive E´ @ 25°C Tan Delta TgDiluent (GPa) (°C) 12 1 Epoxy R Diol 7 was epoxidized to create difunctional crosslinkers capable of forming thermoset polymers. Scheme 3 outlines the synthesis pathway that was followed to create diepoxy monomers (7e) that are discussed in this section. Acetal precursor 7 was epoxidized according to a previously established procedure. First, molecule 7 was combined with epichlorohydrin (1:20 mol ratio) and TBAH (1wt%) catalyst at 70°C. After the contents of this reaction were stirred under these conditions for 4 hours, the temperature of the reactor was lowered to 50°C.200 mL 40 wt% NaOH solution was then dripped into the reactor and the contents were continuously stirred for an additional 2 hours. The final diepoxy product was characterized by gel permeation chromatography (GPC). These results are shown in FIG. 14. The resulting resin was combined with commercial diamines PACM (4,4'- diaminodicyclohexylmethane) and DETA (diethylenetriamine), as well as a furan-based diamine known as DFDA (5,5′-methylenedifurfurylamine) that was synthesized in-house. Samples were cured in an aluminum sample pan. Epoxy-amine thermosets were then cured at - 36 - 53006853.1 Attorney Docket No.370431-1051WO1 80 °C for 3 hours, 100 °C for 3 hours, and finally 120 °C for 2 hours. Thermosets that were fabricated using this procedure are shown in FIG.15. The extent of cure for these materials was determined using near IR spectroscopy. Spectra taken of each thermoset sample are provided in FIG.16. Epoxy (4540 cm-1), and amine (4950 cm-1and 6570 cm-1) peaks are all observable by this method. As the peak intensity of these signals decreases, the concentration of their corresponding functional groups in the cured system is reduced. These results indicate that all epoxy and amine functionalities have been consumed within each thermoset. Thermal and thermomechanical characterization of these furan-based epoxy systems were conducted using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA), respectively. The results of these experiments are shown in FIG.17. The terms and expressions employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the embodiments of the present application. Thus, it should be understood that although the present application describes specific embodiments and optional features, modification and variation of the compositions, methods, and concepts herein disclosed may be resorted to by those of ordinary skill in the art, and that such modifications and variations are considered to be within the scope of embodiments of the present application. Enumerated Embodiments The following enumerated embodiments are provided, the numbering of which is not to be construed as designating levels of importance: Embodiment 1 provides a method for preparing an acetal, the method comprising heating at a temperature of about 60 to about 110 ºC an alcohol of formula (I): , and an aldehyde of formula (II) - 37 - 53006853.1 Attorney Docket No.370431-1051WO1 , to provide an acetal of formula , wherein: each bond; R1and R2are each independently selected from the group consisting of H, C1-3alkyl, -OH, OC1-3 alkyl, F, Cl, Br, and C1-3 alkyl substituted by one OH, wherein R1and R2are not simultaneously -OH; R1’and R2’are each independently a bond (absent), -CH2, -CH(CH3)-, or - CH(CH2CH3)-, provided that at least one of R1’and R2’is not a bond; R3and R4are each independently selected from the group consisting of H, C1-3 alkyl, F, Cl, Br, C6-10aryl, and C5heteroaryl; R5, R6, and R7are each independently selected from the group consisting of H, F, Cl, OR, (CH2)1-3OH, OC(O)N(R)2, CN, CF3, OCF3, R, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, and (CH2)0-2N(R)C(O)R; each R is independently H or C1-10 hydrocarbyl optionally substituted by F or Cl; n is 0 or 1, provided that, when n is 0, R1and R2are absent; m is an integer from 1 to 100, provided that when m is greater than 1, R1and R2are H; with the proviso that: i) if m is 1 and one of R1or R2does not comprise an OH group, then Y is -(CHR3)-; Z is -(CHR4)-; and X is -C(R1)(R2)- or a single bond connecting Y and Z; ii) if m is 1 and R1and R2are each independently selected from the group consisting of -OH, -CH2OH, -CH(OH)CH3, and -CH(OH)CH2CH3, then - 38 - 53006853.1 Attorney Docket No.370431-1051WO1 Y is -(CHR3)-; Z is -(CHR4)-; and ; iii) R2is H, then iv) m wherein the heating takes place in the absence of solvent and in the absence of catalyst; and wherein less than 5 % (w / w) of ring-opened furan derivatives and / or polymerized furan derivatives relative to the original amount of (II) form during the heating. Embodiment 2 provides the method of embodiment 1, wherein R3and R4are H. Embodiment 3 provides the method of any one of embodiments 1-2, wherein n is 0. Embodiment 4 provides the method of any one of embodiments 1-3, wherein n is 1. Embodiment 5 provides the method of any one of embodiments 1-4, wherein R1and R2are each independently selected from the group consisting of H, C1-3 alkyl, -OH, OC1-3 alkyl, F, Cl, Br, -CH2OH, -CH(OH)CH3, and -CH(OH)CH2CH3. Embodiment 6 provides the method of any one of embodiments 1-5, wherein R1and R2are H. Embodiment 7 provides the method of any one of embodiments 1-6, wherein R1is - 39 - 53006853.1 Attorney Docket No.370431-1051WO1 CH3 and R2is -CH2OH. Embodiment 8 provides the method of any one of embodiments 1-7, wherein R1is - CH2OH and R2is -CH2OH. Embodiment 9 provides the method of any one of embodiments 1-8, wherein R5is H, R6is H, and R7is H. Embodiment 10 provides the method of any one of embodiments 1-9, wherein R5is - CH2OH, R6is H, and R7is H. Embodiment 11 provides the method of any one of embodiments 1-10, wherein R1’is -CH2-, and R2’is -CH2-. Embodiment 12 provides the method of any one of embodiments 1-11, wherein R1’is -CH2- and R2’is -CH2-. Embodiment 13 provides a compound or a salt, solvate enantiomer, tautomer, or diastereomer thereof, selected from the group consisting of: wherein: ; OC1-3alkyl, F, Cl, and Br; - 40 - 53006853.1 Attorney Docket No.370431-1051WO1 R3and R4are each independently selected from the group consisting of H, C1-3 alkyl, F, Cl, C6-10aryl, C5heteroaryl; R5, R6, and R7are each independently selected from the group consisting of H, F, Cl, Br, OR, (CH2)1-3OH, (CH2)1-3OA, OC(O)N(R)2, CN, CF3, OCF3, R, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, and (CH2)0-2N(R)C(O)R; R9is H, C1-4 alkyl, C6-10 aryl, F, Cl, or Br, wherein the C6-10 aryl is optionally substituted by 1 to 5 substituents selected from the group consisting of F, Cl, Br, OR, (CH2)1-3OH, OC(O)N(R)2, CN, CF3, OCF3, R, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, and (CH2)0-2N(R)C(O)R; p is 0 or 1; R10and R11are each independently selected from the group consisting of H, F, Cl, Br, and C1-4alkyl; and R is H, A, or C1-10 hydrocarbyl optionally substituted by F or Cl. Embodiment 14 provides the compound of embodiment 13, wherein R3and R4are H. Embodiment 15 provides the compound of any one of embodiments 13-14, wherein R1is H. Embodiment 16 provides the compound of any one of embodiments 13-15, wherein R1is CH3. Embodiment 17 provides the compound of any one of embodiments 13-16, wherein R5is H, R6is H, and R7is H. Embodiment 18 provides the compound of any one of embodiments 13-17, wherein A . 19 provides the compound of any one of embodiments 13-18, wherein A . 20 provides the compound of any one of embodiments 13-19, wherein A . - 41 - 53006853.1 Attorney Docket No.370431-1051WO1 Embodiment 21 provides the compound of any one of embodiments 13-20, wherein R9is methyl. Embodiment 22 provides the compound of any one of embodiments 13-21, wherein R10is H and R11is H. Embodiment 23 provides the compound of any one of embodiments 13-22, wherein R5is CH2OA, R6is H, and R7is H. Embodiment 24 provides a resin comprising a reaction product of at least one compound of any one of embodiments 13-23 and at least one additional monomer or polymer. - 42 - 53006853.1

Claims

Attorney Docket No.370431-1051WO1 CLAIMS What is claimed is:

1. A method for preparing an acetal, the method comprising heating at a temperature of about 60 to about 110 ºC an alcohol of formula (I): , and an aldehyde of formula (II), to provide an acetal of formula, wherein:each independently is absent or a single bond; R1and R2are each independently selected from the group consisting of H, C1-3 alkyl, -OH, OC1-3alkyl, F, Cl, Br, and C1-3alkyl substituted by one OH, wherein R1and R2are not simultaneously -OH; R1’and R2’are each independently a bond (absent), -CH2, -CH(CH3)-, or - CH(CH2CH3)-, provided that at least one of R1’and R2’is not a bond; R3and R4are each independently selected from the group consisting of H, C1-3alkyl, F, Cl, Br, C6-10 aryl, and C5 heteroaryl; R5, R6, and R7are each independently selected from the group consisting of H, F, Cl, OR, (CH2)1-3OH, OC(O)N(R)2, CN, CF3, OCF3, R, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, and (CH2)0-2N(R)C(O)R; each R is independently H or C1-10hydrocarbyl optionally substituted by F or Cl; n is 0 or 1, - 43 - 53006853.1Attorney Docket No.370431-1051WO1 provided that, when n is 0, R1and R2are absent; m is an integer from 1 to 100, provided that when m is greater than 1, R1and R2are H; with the proviso that: i) if m is 1 and one of R1or R2does not comprise an OH group, then Y is -(CHR3)-; Z is -(CHR4)-; and X is -C(R1)(R2)- or a single bond connecting Y and Z; ii) if m is 1 and R1and R2are each independently selected from the group consisting of -OH, -CH2OH, -CH(OH)CH3, and -CH(OH)CH2CH3, then Y is -(CHR3)-; Z is -(CHR4)-; and ; iii) R2is H, theniv) if m is greater than 1, thenwherein the heating takes place in the absence of solvent and in the absence of catalyst; and wherein less than 5 % (w / w) of ring-opened furan derivatives and / or polymerized - 44 - 53006853.1Attorney Docket No.370431-1051WO1 furan derivatives relative to the original amount of (II) form during the heating.

2. The method of claim 1, wherein R3and R4are H.

3. The method of claim 1, wherein n is 0.

4. The method of claim 1, wherein n is 1.

5. The method of claim 1, wherein R1and R2are each independently selected from the group consisting of H, C1-3alkyl, -OH, OC1-3alkyl, F, Cl, Br, -CH2OH, -CH(OH)CH3, and - CH(OH)CH2CH3.

6. The method of claim 5, wherein R1and R2are H.

7. The method of claim 5, wherein R1is CH3 and R2is -CH2OH.

8. The method of claim 5, wherein R1is -CH2OH and R2is -CH2OH.

9. The method of claim 1, wherein R5is H, R6is H, and R7is H.

10. The method of claim 1, wherein R5is -CH2OH, R6is H, and R7is H.

11. The method of claim 10, wherein R1’is -CH2-, and R2’is -CH2-.

12. The method of claim 1, wherein R1’is -CH2- and R2’is -CH2-.

13. A compound or a salt, solvate enantiomer, tautomer, or diastereomer thereof, selected from the group consisting of: ,- 45 - 53006853.1Attorney Docket No.370431-1051WO1 wherein:; OC1-3alkyl, F, Cl,and R3and R4are each independently selected from the group consisting of H, C1-3alkyl, F, Cl, C6-10 aryl, C5 heteroaryl; R5, R6, and R7are each independently selected from the group consisting of H, F, Cl, Br, OR, (CH2)1-3OH, (CH2)1-3OA, OC(O)N(R)2, CN, CF3, OCF3, R, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, and (CH2)0-2N(R)C(O)R; R9is H, C1-4alkyl, C6-10aryl, F, Cl, or Br, wherein the C6-10aryl is optionally substituted by 1 to 5 substituents selected from the group consisting of F, Cl, Br, OR, (CH2)1-3OH, OC(O)N(R)2, CN, CF3, OCF3, R, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, and (CH2)0-2N(R)C(O)R; p is 0 or 1; R10and R11are each independently selected from the group consisting of H, F, Cl, Br, and C1-4 alkyl; and R is H, A, or C1-10 hydrocarbyl optionally substituted by F or Cl.

14. The compound of claim 13, wherein R3and R4are H. - 46 - 53006853.1Attorney Docket No.370431-1051WO1 15. The compound of claim 13, wherein R1is H.

16. The compound of claim 13, wherein R1is CH3.

17. The compound of claim 13, wherein R5is H, R6is H, and R7is H.

18. The compound of claim 13, wherein A is .

19. The compound of claim 13, wherein A is .

20. The compound of claim 13, wherein A .

21. The compound of claim 13, wherein R9is methyl.

22. The compound of claim 13, wherein R10is H and R11is H.

23. The compound of claim 19, wherein R5is CH2OA, R6is H, and R7is H.

24. A resin comprising a reaction product of at least one compound of claim 13 and at least one additional monomer or polymer. - 47 - 53006853.1

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