WO2019051184A1

WO2019051184A1 - Amide and nitrile compounds and methods of producing and using thereof

Info

Publication number: WO2019051184A1
Application number: PCT/US2018/049890
Authority: WO
Inventors: Han Lee; Bob Wilson; Yin Liu; Konstantin Pokrovski; Ian MCLENNAN; Sadesh H. SOOKRAJ
Original assignee: Novomer, Inc.
Priority date: 2017-09-09
Filing date: 2018-09-07
Publication date: 2019-03-14
Also published as: CN111094237A; KR102529865B1; KR20200040894A; EP3679011A4; TW201920077A; EP3679011A1; JP7095911B2; JP2022130492A; JP2020533309A

Abstract

Provided herein are acrylamide and acrylonitrile compounds and other compounds that may be produced from hydroxy amides and/or lactones. Provided herein are methods and systems to produce such compounds.

Description

AMIDE AND NITRILE COMPOUNDS AND METHODS OF PRODUCING AND USING

THEREOF

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No.

62/556,355, filed September 9, 2017, and U.S. Provisional Patent Application No.62/690,783, filed June 27, 2018, each of which is incorporated herein by reference in its entirety. FIELD

[0002] The present disclosure relates generally to the production of amide products and/or nitrile products, and more specifically from at least epoxides, beta-lactones and/or beta-hydroxy amides. BACKGROUND

[0003] Nitrogen containing compounds such as amides and nitriles are valuable compounds that can be used for various commercial and industrial applications. For example, acrylonitrile may be used as a starting material in the production of polymers and monomer precursors.

Various methods for the industrial production of acrylonitrile are known in the art. For example, acrylonitrile can be prepared by the catalytic ammoxidation of propylene, in which propylene, ammonia and air are contacted with a catalyst at elevated temperature and pressure. This process, however, generally requires the use of harsh reaction conditions and costly reagents. [0004] The present invention solves the problems of the conventional technology by providing systems and methods for the industrial production of nitriles, including precursors to make certain nitriles and derivatives made from nitriles, and other compounds desired in the art, including systems and methods of producing such compounds, either in part or completely, from renewable sources. BRIEF SUMMARY

[0005] Provided herein are methods and systems for producing amide products and/or nitrile products. Advantageously, certain preferred methods and systems provided are biobased alternatives to conventional methods and systems for producing nitriles and amides at reduced cost and reduced harm to the environment. [0006] Preferred embodiments of the present invention are directed to systems and methods for producing amide products and/or nitrile products from epoxides and/or beta-lactones. In certain preferred embodiments, the systems and methods of the present invention may produce amide products and/or nitrile products from biobased epoxides and/or biobased beta-lactones. In certain embodiments, the systems and methods may be modified to selectively produce a preferred amide product or nitrile product at a greater yield than one or more other products. Advantageously, integrating the systems and methods of the present invention into conventional systems and processes may reduce the environmental impact of producing many commercial products. [0007] For example, in some aspects, provided is a method of producing a amide compound of formula (3-I) and/or a nitrile compound of formula (3):

, or isomers thereof, wherein R¹ is H or alkyl, the method comprising: combining an amide compound of formula (2) with a dehydration agent to produce the nitrile compound of formula (3-I) and/or the amide compound of formula (3), or isomers of the foregoing, wherein:

the amide compound of formula (2) is

, wherein R¹ is as defined above for formulae (3-I) and (3). [0008] In certain embodiments of the foregoing, the method further comprises combining a beta-lactone compound of formula (1) with ammonia to produce the amide compound of formula (2), wherein: the beta-lactone compound of formula (1) is , wherein R¹ is as defined

above for formulae (3-I) and (3). [0009] In some variations of the foregoing methods, the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a mixed oxide, a transition metal complex, or an aluminum complex, or any combination thereof. In one variation, the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof. [0010] In some variations of the foregoing methods, the dehydration agent comprises a titanic acid, a metal oxide hydrate, a metal sulfate, a metal oxide sulfate, a metal phosphate, a metal oxide phosphate, a mineral acid, a carboxylic acid or a salt thereof, an acidic resin, an acidic zeolite, clay, or any combination thereof. In certain variations of the foregoing methods and systems, the dehydration agent comprises a zeolite. [0011] In other aspects, provided is a method, comprising: combining a compound of formula (1) and ammonia in a reactor to produce a compound of formula (2), wherein:

the compound of formula (1) is

the compound of formula (2) is

, wherein R¹ is H or alkyl. [0012] In certain variations of the foregoing, the selectivity for formula (2) is greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%. [0013] In some embodiments, provided is a method, comprising: combining a compound of formula (1) and ammonia in a reactor to produce a compound of formula (2), a compound of formula (3-I), and/or a compound of formula (3), wherein:

the compound of formula (1) is

the compound of formula (2) is

,

the compound of formula (3-I) is

and the compound of formula (3) is

wherein R¹ is H or alkyl. [0014] In certain variations of the foregoing, the selectivity for formula (2) is greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%; or the selectivity for formula (3) is greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%; or the selectivity for formula (3-I) is greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%. [0015] In some variations of the foregoing, the compound of formula (3-I) is an amide, such as acrylamide, and the compound of formula (3) is a nitrile, such as acrylonitrile. In certain aspects, provided is a method, comprising: producing an amide, such as acrylamide, according to any of the methods herein; and polymerizing the amide. In one variation where the amide is acrylamide, the polymer is polyacrylamide. In other aspects, provided is a method, comprising: producing a nitrile, such as acrylonitrile, according to any of the methods herein; and

polymerizing the nitrile. In one variation where the nitrile is acrylonitrile, the polymer is polyacrylonitrile. In yet other aspects, provided is a method of producing a carbon fiber, comprising: producing polyacrylonitrile according to any of the methods herein; and producing a carbon fiber from the polyacrylonitrile. [0016] In other aspects, provided are systems for producing amide products and/or nitrile products from at least beta-lactones and/or beta-hydroxy amides. In certain embodiments, the systems provided comprise one or more reactors sized, shaped, and configured to provide amide products and/or nitrile products. In certain embodiments, the one or more reactors may be configured as continuous stirred tank reactors, fixed catalyst bed reactors, fluidized catalyst bed reactors. In certain embodiments, the systems may be configured for use with heterogenous catalysts. In other embodiments, the systems may be configured for use with homogenous catalysts. [0017] In some variations of the foregoing, the compounds of the present invention have a biobased content of greater than 0%, and less than 100%. In certain variations of the foregoing, the compounds of the present invention have a biobased content of at least 10%, at least 20%, at least 50%, at least 70%, at least 95%, or 100%. [0018] In some variations, biobased content can be determined based on the following: % Biobased content = [Bio (Organic) Carbon]/[Total (Organic) Carbon]*100%, as determined by ASTM D6866 (Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis). [0019] The biobased content of the compositions of the present invention may depend based on the biobased content of the beta-lactone used. For example, in some variations of the methods described herein, the beta-lactone used to produce the amide products and/or nitrile products described herein may have a biobased content of greater than 0%, and less than 100%. In certain variations of the methods described herein, the beta-lactone used to produce the amide products and/or nitrile products described herein may have a biobased content of at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, at least 99.5%, at least 99.9%, at least 99.99%, or 100%. In certain variations, a beta-lactone derived from renewable sources is used. In other variations, at least a portion of the beta-lactone used is derived from renewable sources, and at least a portion of the beta-lactone is derived from non- renewable sources. [0020] The biobased-content of the beta-lactone may depend on, for example, the biobased content of the epoxide and carbon monoxide used. In some variations, both epoxide and carbon monoxide are derived from renewable sources. DESCRIPTION OF THE FIGURES

[0021] The present application can be best understood by reference to the following description taken in conjunction with the accompanying figures, in which like parts may be referred to by like numerals. [0022] FIGS.1, 2, 3, 4, and 6 depict exemplary reaction schemes to produce compounds of formulae (3). [0023] FIG.5 depicts an exemplary reaction scheme to produce compounds of formula (3-I). [0024] FIG.7A depicts a reaction scheme showing how aqueous ammonia involves a dynamic balanced mixture of ammonia gas/water and ammonium . [0025] FIG.7B depicts exemplary reaction schemes that involve beta-propiolactone and ammonium/ammonia. [0026] FIG.8 is a graph depicts the results from the experiment performed in Example 9, involving the production of acrylonitrile by dehydration of 3-hydroxypropanamide (abbreviated as“3-HP amide”) using alumina (Al₂O₃). DETAILED DESCRIPTION

[0027] The following description sets forth exemplary methods, parameters and the like. It should be recognized, however, that such description is not intended as a limitation on the scope of the present disclosure but is instead provided as a description of exemplary embodiments. [0028] Provided herein are methods and systems to produce amide products and/or nitrile products from at least beta-lactones and/or beta-hydroxy amides. In certain preferred embodiments, the amide products include acrylamide, and the nitrile products include acrylonitrile. In certain variations, the beta-lactones may be produced by carbonylation of an epoxide with carbon monoxide. [0029] In some aspects, provided are methods of producing acrylonitrile compounds and other nitrile compounds from beta-hydroxy amides. For example, with reference to FIG.1, a beta-hydroxy amide of formula (2) is combined with a dehydration agent to produce an acrylonitrile compound or other nitrile compounds of formula (3), or isomers thereof. [0030] In other aspects, provided are methods of producing acrylonitrile compounds and other nitrile compounds from lactones. For example, with reference to FIG.2, a beta-lactone of formula (1) may be combined with ammonia to produce the beta-hydroxy amide of formula (2), which then may undergo the exemplary reaction depicted in FIG.1 to the produce the compound of formula (3), or isomers thereof. [0031] In another example, with reference to FIG.3, a beta-lactone of formula (1) may be combined with ammonia in water (also referred to aqueous ammonia) and a dehydration agent to produce an acrylonitrile compound or other nitrile compounds of formula (3), or isomers thereof. [0032] In yet another example, with reference to FIG.4, the conversion from a beta-lactone of formula (1) to a nitrile compound of formula (3), or isomers thereof, is depicted, showing intermediate compounds of formulae (2) and (3-I) that can undergo dehydration to produce the nitrile. In one aspect, provided is method, comprising: combining a compound of formula (1) and ammonia in a reactor to produce a compound of formula (2), respectively, with a selectivity of greater than 80%. In another aspect, provided is a method, comprising: combining a compound of formula (1) and ammonia in a reactor to produce a compound of formula (2), a compound of formula (3-I), and/or a compound of formula (3), with a selectivity of greater than 80%. [0033] In some variations of the foregoing, the selectivity is greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, or 99%. The selectivity may be controlled by one or more parameters. For example, in some variations, the temperature of the reactor is maintained at an average temperature of between -20 °C to 50 °C, or between 10 °C to 35 °C. In other variations, the compound of formula (1) is added drop-wise to the reactor containing the ammonia. In another variation, the compound of formula (1) is added by single injection to the reactor containing the ammonia. [0034] In yet another variation, provided is a method, comprising: providing a first portion of a compound of formula (1) to a reactor; adding ammonia; and maintaining the average temperature of the reactor to produce a compound of formula (2). In one variation, the method further comprises isolating the compound of formula (2). In certain embodiments, the step for maintaining an average temperature occurs between -20 °C to 50 °C. [0035] In yet another variation, provided is a method, comprising: cofeeding a compound of formula (1) and ammonia to a reactor; and maintaining the average temperature of the reactor to produce a compound of formula (2). In one variation, the method further comprises isolating the compound of formula (2). In certain embodiments, the compound of formula (1) is fed to the reactor as a liquid to contact a heterogenous catalyst. In certain variations, the flow rates of the compound of formula (1) and the ammonia are controlled separately. In certain variations, the ammonia is present in the reactor at an excess. In other embodiments, the method further comprises collecting a product stream comprising the compound of formula (2) and excess ammonia from the reactor. In one variation, the compound of formula (2) is collected in liquid form In yet other embodiments, the method further comprises separating excess ammonia from the product stream; and recycling the separated ammonia to the reactor. In other variations, the heterogeneous catalyst bed comprises any of the heterogeneous dehydrating agents described herein. For example, in one variation, the heterogeneous catalyst bed comprises a metal oxide, a basic zeolite, an alkali metal exchanged zeolite, a base modified alumina, or a solid“super base”. In other variations, the temperature of the reactor is maintained in the range from 10 °C to 100 °C, or 65 °C to 75 °C, or at room temperature. In one variation, the reactor is maintained at a temperature where the compound of formula (2) is a gas. In another variation, the compound of formula (2) is produced anhydrously. [0036] In some variations of the foregoing, the compound of formula (1) is combined with liquid ammonia. In other variations of the foregoing, the compound of formula (1) is combined with ammonia in the absence of solvent. In certain variations, the compound of formula (1) is combined with ammonia in water (or ammonium hydroxide). In other words, in certain variations, the ammonia is aqueous ammonia. With reference to FIG.7A, it should generally be understood that aqueous ammonia involves a dynamic balanced mixture of ammonia gas/water and ammonium hydroxide. In other variations, the compound of formula (1) is combined with anhydrous ammonia. In one variation, the ammonia is anhydrous gaseous ammonia. With reference to FIG.7B, when anhydrous ammonia is used, at least one step (such as the removal of water prior to the hydration reaction) may be avoided. The ammonia may be obtained from any commercially available sources or produced according to any methods known in the art. [0037] In other variations, the compound of formula (1) is combined with ammonia at elevated temperatures. In other variations, the compound of formula (1) is combined with ammonia and additional basic compounds. [0038] In certain variations of the foregoing, the ammonia is combined with the compound of formula (1) with any of the dehydration agents described herein, as depicted in FIG.3. In other variations, the ammonia is combined with the compound of formula (1) to produce the beta-hydroxy amide of formula (2) first, and then any of the dehydration agents described herein is combined with the beta-hydroxy amide of formula (2) to produce the compound of formula (3- I), and/or the compound of formula (3), or isomers of the foregoing, as depicted in FIGS.2 and 4. [0039] In other aspects, with reference to FIG.5, provided is a method of producing an amide of formula (3-I), or isomers thereof, from a beta-hydroxy amide of formula (2). In yet other aspects, with reference to FIG.6, provided is a method of producing a nitrile of formula (3), or isomers thereof, from an amide of formula (3-I), or isomers thereof. By exemplary reactions depicted in FIGS.5 and 6 involve dehydration reactions, which may employ any of the dehydrating agents described herein. [0040] In certain preferred embodiments, with respect to formulae (1), (2), (3-I) and (3), R¹ is H. In such embodiments, acrylonitrile may be produced from beta-propiolactone, through 3- hydroxypropiamide and acrylamide. In certain variations, 3-hydroxypropiamide and/or acrylamide may be isolated, and optionally further purified. [0041] The amide products and/or nitrile products produced according to the methods and systems herein may have uses in various downstream processes. For example, in one variation, acrylamide may be polymerized to form polyacrylamide; and acrylonitrile may be polymerized to form polyacrylonitrile. The resulting polyacrylonitrile may be suitable for various uses, including as carbon fiber. [0042] The methods are explored in further detail below, including the acrylamide and acrylonitrile compounds and other compounds that may be produced, as well as the amides, lactones and dehydration agents that may be used. Acrylonitrile Compounds and Other Nitrile Compounds [0043] In one aspect, provided is a method of producing acrylonitrile and other nitrile compounds from beta-propiolactone and other lactones, respectively. For example, in one variation, beta-propiolactone may be reacted with aqueous ammonia to get a crude 3- hydroxypropanamide aqueous solution. Then, crude solution is purified by resin to remove the impurities and then water is removed to get neat 3-hydroxypropanamide in solid form. Then, neat 3-hydroxypropanamide may be continuously fed to a fixed bed reactor which is packed with dehydration catalyst. The 3-hydroxypropanamide solid may be warmed above its melting point and then further mixed/vaporized with nitrogen sweep gas in the preheat zone before passing through a catalyst bed. The dehydration reaction of 3-hydroxypropanamide to acrylonitrile in the presence of water may occur on the surface of the catalyst. [0044] In some embodiments, the acrylonitrile compounds and other nitrile compounds produced according to the methods herein are compounds of formula (3):

or isomers thereof, wherein R¹ is H, alkyl, alkenyl, cycloalkyl, or aryl. [0045] “Alkyl” refers to a monoradical unbranched or branched saturated hydrocarbon chain. In some embodiments, alkyl has 1 to 10 carbon atoms (i.e., C_1-10 alkyl), 1 to 9 carbon atoms (i.e., C_1-9 alkyl), 1 to 8 carbon atoms (i.e., C_1-8 alkyl), 1 to 7 carbon atoms (i.e., C_1-7 alkyl), 1 to 6 carbon atoms (i.e., C_1-6 alkyl), 1 to 5 carbon atoms (i.e., C_1-5 alkyl), 1 to 4 carbon atoms (i.e., C_1-4 alkyl), 1 to 3 carbon atoms (i.e., C_1-3 alkyl), or 1 to 2 carbon atoms (i.e., C_1-2 alkyl). Examples of alkyl include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, 3-methylpentyl, and the like. When an alkyl residue having a specific number of carbon atoms is named, all geometric isomers having that number of carbon atoms may be encompassed; thus, for example,“butyl” can include n-butyl, sec-butyl, isobutyl and t-butyl;“propyl” can include n-propyl and isopropyl. [0046] “Alkenyl” refers to an unsaturated linear or branched monovalent hydrocarbon chain or combination thereof, having at least one site of olefinic unsaturation (i.e., having at least one moiety of the formula C=C). In some embodiments, alkenyl has 2 to 10 carbon atoms (i.e., C_2-10 alkenyl). The alkenyl group may be in“cis” or“trans” configurations, or alternatively in“E” or “Z” configurations. Examples of alkenyl include ethenyl, allyl, prop-1-enyl, prop-2-enyl, 2- methylprop-1-enyl, but-1-enyl, but-2-enyl, but-3-enyl, isomers thereof, and the like. [0047] “Cycloalkyl” refers to a carbocyclic non-aromatic group that is connected via a ring carbon atom. Examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. [0048] “Aryl” refers to a monovalent aromatic carbocyclic group of from 6 to 18 annular carbon atoms having a single ring or a ring system having multiple condensed rings. Examples of aryl include phenyl, naphthyl and the like. [0049] In some variations, the alkyl, alkenyl, cycloalkyl, or aryl for R¹ may be optionally substituted. The term“optionally substituted” means that the specified group is unsubstituted or substituted by one or more substituent groups. In certain variations, the optional substituents may include halo, -OSO₂R₂, -OSiR₄, -OR, C=CR₂, -R, -OC(O)R, -C(O)OR, and -C(O)NR₂, wherein R is independently H, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted aryl. In some embodiments, R is independently unsubstituted alkyl, unsubstituted alkenyl, or unsubstituted aryl. In some embodiments, R is independently H, methyl (Me), ethyl (Et), propyl (Pr), butyl (Bu), benzyl (Bn), allyl, phenyl (Ph), or a haloalkyl. In certain embodiments, substituents may include F, Cl, -OSO₂Me, -OTBS (where“TBS” is tert- butyl(dimethyl)silyl)), -OMOM (where“MOM” is methoxymethyl acetal), -OMe, -OEt, -OiPr, - OPh, -OCH₂CHCH₂, -OBn, -OCH₂(furyl), -OCF₂CHF₂, -C=CH₂, -OC(O)Me, -OC(O)nPr, - OC(O)Ph, -OC(O)C(Me)CH₂, -C(O)OMe, -C(O)OnPr, -C(O)NMe₂, -CN, -Ph, -C₆F₅, - C₆H₄OMe, and -OH. [0050] In certain preferred embodiments, R¹ is H or alkyl. [0051] In some variations, R¹ is H, and the compound of formula (3) is (also known

in the art as acrylonitrile). [0052] In other variations, R¹ is alkyl. In certain variations, R¹ is C_1-6 alkyl. In one variation, R¹ is methyl or ethyl. When R¹ is methyl, the compound of formula (3) is

or isomers thereof (also known in the art as crotononitrile). When R¹ is ethyl, the compound of formula (3) is or isomers thereof (also known in the art as 2-pentenenitrile).

[0053] “Alkyl” refers to a monoradical unbranched or branched saturated hydrocarbon chain. In some embodiments, alkyl has 1 to 6 carbon atoms (i.e., C_1-6 alkyl), 1 to 5 carbon atoms (i.e., C_1-5 alkyl), 1 to 4 carbon atoms (i.e., C_1-4 alkyl), 1 to 3 carbon atoms (i.e., C_1-3 alkyl), or 1 to 2 carbon atoms (i.e., C_1-2 alkyl). In other embodiments, alkyl groups may include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2- hexyl, 3-hexyl, and 3-methylpentyl. When an alkyl residue having a specific number of carbons is named, all geometric isomers having that number of carbons may be encompassed; thus, for example,“butyl” can include n-butyl, sec-butyl, isobutyl and t-butyl;“propyl” can include n- propyl and isopropyl. [0054] Further, it should be understood that when a range of values is listed, it is intended to encompass each value and sub-range within the range. For example,“C_1–6 alkyl” (which may also be referred to as 1-6C alkyl, C1-C6 alkyl, or C1-6 alkyl) is intended to encompass, C₁, C₂, C₃, C₄, C₅, C₆, C_1–6, C_1–5, C_1–4, C_1–3, C_1–2, C_2–6, C_2–5, C_2–4, C_2–3, C_3–6, C_3–5, C_3–4, C_4–6, C_4–5, and C_5–6 alkyl. Acrylamides and Other Amides [0055] In some embodiments, acrylamide or other amides may be used to produce the acrylonitrile compounds and other nitrile compounds. In some variations, such amides are compounds of formula (3-I):

wherein R¹ is H, alkyl, alkenyl, cycloalkyl, or aryl [0056] In certain preferred embodiments, R¹ is H or alkyl.

[0057] In some variations, R¹ is H, and the compound of formula (3-I) is (or

acrylamide). In other variations, R¹ is alkyl. In certain variations, R¹ is C_1-6 alkyl. In one variation R¹ is methyl or ethyl. When R¹ is methyl, the compound of formula (3-I) is

or (also known in the art as but-2-enamide). When R¹ is ethyl, the compound of formula (2) is (also known in the art as pent-2-

enamide). [0058] It should generally be understood that when a compound of formula (3-I), or isomers thereof, is used to produce a compound of formula (3), or isomers thereof, R¹ of formula (3-I) is as defined for formula (3). [0059] Acrylamides and other amides, such as the compounds of formula (3-I) may be obtained from the methods described herein, or any commercially available sources, or produced according to any methods known in the art. [0060] In certain aspects, the compounds of formula (3-I) produced according to the methods herein may be isolated. In some variations, the compounds of formula (3-I) produced according to the methods herein may be isolated and purified. The compounds of formula (3-I) produced according to the methods herein may be isolated. Beta-Hydroxy Amides and Other Hydroxy Amides [0061] In some embodiments, the beta-hydroxy amides and other hydroxy amides that may be used to produce the acrylonitrile compounds and other nitrile compounds according to the methods herein are compounds of formula (2):

wherein R¹ is H, alkyl, alkenyl, cycloalkyl, or aryl [0062] In certain preferred embodiments, R¹ is H or alkyl.

[0063] In some variations, R¹ is H, and the compound of formula (2) is

3-hydroxypropanamide). In other variations, R¹ is alkyl. In certain variations, R¹ is C_1-6 alkyl. In one variation, R¹ is methyl or ethyl. When R¹ is methyl, the compound of formula (2) is (or 3-hydroxybutanamide). When R¹ is ethyl, the compound of formula (2) is

(or 3-hydroxypentanamide). [0064] It should generally be understood that when a compound of formula (2) is used to produce a compound of formula (3), or isomers thereof, R¹ of formula (2) is as defined for formula (3). [0065] The beta-hydroxy amides and other amides, such as the compounds of formula (2) may be obtained from the methods described herein, or any commercially available sources, or produced according to any methods known in the art. [0066] In certain aspects, the compounds of formula (2) produced according to the methods herein may be isolated. In some variations, the compounds of formula (2) produced according to the methods herein may be isolated and purified. The compounds of formula (2) produced according to the methods herein may be isolated. Beta-Lactones and Other Lactones [0067] In some embodiments, the beta-lactones may be used to produce beta-hydroxy amides, acrylamide, acrylonitrile and other compounds according to the methods herein. In certain embodiments, the beta-lactones are compounds of formula (1):

wherein R¹ is H, alkyl, alkenyl, cycloalkyl, or aryl. [0068] In certain preferred embodiments, R¹ is H or alkyl.

[0069] In some variations, R¹ is H, and the compound of formula (1) is (also known

in the art as beta-propiolactone). [0070] In other variations, R¹ is alkyl. In certain variations, R¹ is C_1-6 alkyl. In one

variation, R¹ is methyl or ethyl. When R¹ is methyl, the compound of formula (1) is

(also known in the art as beta-butyrolactone). When R¹ is ethyl, the compound of formula (1) is

(also known in the art as beta-valerolactone). [0071] It should generally be understood that when a compound of formula (1) is used to produce a compound of formula (2) or a compound of formula (3), or isomers thereof, R¹ of formula (1) is as defined for formula (2) or formula (3). [0072] The beta-lactones, such as the compounds of formula (1), may be obtained from any commercially available sources or produced according to any methods known in the art. For example, beta-propiolactone may be obtained by reacting ethylene oxide and carbon monoxide under suitable conditions. In some variations, the amide products and/or nitrile products may be produced from any of the beta-lactones provided in Column B of Table A below. As shown in Table A, such beta-lactones in Column B may be produced from the corresponding epoxide from Column A of the table.

[0073] The beta-lactones, such as the compounds of formula (1), may be obtained from renewable feedstock. For example, when beta-propiolactone is produced from ethylene oxide and carbon monoxide, either or both the ethylene oxide and carbon monoxide may be obtained from renewable feedstock using methods known in the art. When the beta-lactone, such as the compound of formula (1), is obtained in part or completely from renewable feedstock, the polyamide produced according to the methods described herein from such beta-lactone has a biocontent greater than 0%. [0074] Various techniques are known in the art to determine biocontent of a material. For example, in some variations, biocontent of a material may be measured using the ASTM D6866 method, which allows the determination of the biocontent of materials using radiocarbon analysis by accelerator mass spectrometry, liquid scintillation counting, and isotope mass spectrometry. A biocontent result may be derived by assigning 100% equal to 107.5 pMC (percent modern carbon) and 0% equal to 0 pMC. For example, a sample measuring 99 pMC will give an equivalent biocontent result of 93%. In one variation, biocontent may be determined in accordance with ASTM D6866 revision 12 (i.e., ASTM D6866-12). In another variation, biocontent may be determined in accordance with the procedures of Method B of ASTM-D6866- 12. Other techniques for assessing the biocontent of materials are described in U.S. Patent Nos. 3,885,155, 4,427,884, 4,973,841, 5,438,194, and 5,661,299, as well as WO2009/155086. Dehydration Agents [0075] Dehydration generally involves converting a carbon-carbon single bond to a carbon- carbon double bond, and produces a water molecule. The dehydration reactions described herein may take place in the presence of a suitable homogeneous or heterogeneous catalyst. [0076] In some embodiments, suitable dehydration catalysts may include acids, bases and oxides. Examples of suitable acids may include H₂SO₄, HCl, titanic acids, metal oxide hydrates, metal sulfates (MSO₄, where M may be Zn, Sn, Ca, Ba, Ni, Co, or other transition metals), metal oxide sulfates, metal phosphates (e.g., M₃(PO₄)₂, where M may be Ca, Ba), metal phosphates, metal oxide phosphates, carbon (e. g., transition metals on a carbon support), mineral acids, carboxylic acids, salts thereof, acidic resins, acidic zeolites, clays, SiO₂/H₃PO₄, fluorinated Al₂O₃, phosphotungstic acids, phosphomolybdic acids, silicomolybdic acids, silico tungstic acids and carbon dioxide. Examples of suitable bases may include NaOH, ammonia,

polyvinylpyridine, metal hydroxides, Zr(OH)₄, and substituted amines. Examples of suitable oxides may include Nb₂O₅, TiO₂, ZrO₂, A1₂O₃, SiO₂, ZnO₂, SnO₂, WO₃, MnO₂, Fe₂O₃, and V₂O₅. [0077] In some embodiments, the dehydration agents used in the methods described herein include phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a mixed oxide, a transition metal complex, or an aluminum complex. [0078] In certain embodiments, the dehydration agents used in the methods described herein may further comprise a solid support. Suitable solid supports may include, for example, hydrotalcite. [0079] The dehydration agents may be obtained from any commercially available sources or prepared according to any methods known in the art. Phosphorous Compounds [0080] In certain embodiments, the dehydration agent used in the methods described herein comprises phosphorous compounds. [0081] In one variation, the dehydration agent comprises phosphorous pentoxide. [0082] In some variations, the dehydration agent comprises an organophosphorous compound. In certain variations, the organophosphorous compound is an organophosphate. In certain variations, the organophosphorous compound is an alkyl halophosphate or a cycloalkyl halophosphate. In one variation, the alkyl halophosphate is alkyl dihalophosphate or dialkyl halophosphate. In another variation, the cycloalkyl halophosphate is cycloalkyl dihalophosphate, or dicycloalkyl halophosphate. In some variations of the foregoing organophosphorous compounds, the alkyl is a C₁-C₁₀ alkyl. In other variations of the foregoing organophosphorous compounds, the cycloalkyl is a C₃-C₁₀ cycloalkyl. [0083] “Cycloalkyl” refers to a carbocyclic, non-aromatic group that is connected via a ring carbon atom, which contains only C and H when unsubstituted. The cycloalkyl can consist of one ring or multiple rings. In some variations, a cycloalkyl with more than one ring may be linked together by a C-C bond, fused, spiro or bridged, or combinations thereof. In some embodiments, cycloalkyl is a C₃-C₁₀ cycloalkyl. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclohexyl, adamantyl, and

decahydronaphthalenyl. [0084] In yet other variations of the foregoing organophosphorous compounds, the halophosphate is chlorophosphate. In yet other variations of the foregoing organophosphorous compounds, the halophosphate is fluorophosphate. [0085] Suitable organophosphorous compounds used in the methods described herein may include, for example, ethyl dichlorophosphate, diethyl chlorophosphate, methyl

dichlorophosphate, dimethyl chlorophosphate, ethyl difluorophosphate, diethyl fluorophosphate, methyl difluorophosphate, or dimethyl fluorophosphate, or any combination thereof. Carbodiimide Compounds [0086] In certain embodiments, the dehydration agent comprises a carbodiimide compound. [0087] In some variations, the carbodiimide compound is wherein each R⁴

and R⁵ is independently alkyl or cycloalkyl. In certain variations of the foregoing, R⁴ and R⁵ are different. In other variations of the foregoing, R⁴ and R⁵ are the same. In other variations, each R⁴ and R⁵ is independently cycloalkyl. [0088] In certain variations, each R⁴ and R⁵ is independently alkyl. In certain variations, each R⁴ and R⁵ is independently is independently C_1-6 alkyl. In one variation, each R⁴ and R⁵ is independently is methyl, ethyl or propyl. In another variation, R⁴ and R⁵ are both methyl, ethyl or propyl. In another variation, R⁴ and R⁵ are both cyclohexyl. In yet other variations, R⁴ is alkyl, and R⁵ is cycloalkyl. [0089] Suitable carbodiimide compounds used in the methods described herein may include, for example, (also known in the art as N,N’-

dicyclohexylcarbodiimide), in which R⁴ and R⁵ are both cyclohexyl. Triazine Compounds [0090] In certain embodiments, the dehydration agent comprises a triazine compound. In one variation, the triazine compound is 1, 3, 5-triazine, which has the following structure:

[0091] The triazine compounds described herein may be optionally substituted with one or more substituents. In some variations, the triazine compound is substituted with 1, 2 or 3 substituents. In certain variations, the substituents may be halo groups. For example, in certain variations, the triazine compound is a halo-substituted triazine compound. In certain variations, the triazine compound is 1, 3, 5-triazine substituted with 1, 2, or 3 halo groups. In one variation, the triazine compound is a halo-substituted 1, 3, 5-triazine. [0092] Suitable triazine compounds used in the methods described herein may include, for

example, (also known in the art as cyanuric chloride).

Organosilicon Compounds [0093] In certain embodiments, the dehydration agent comprises an organosilicon compound. In some variations, the organosilicon compound is a silazane. The silazane may be unsubstituted or substituted. In one variation, the silazane is substituted with aryl, halo, alkyl, alkoxy or amino groups. [0094] In certain embodiments, the organosilicon compound is , wherein each

R⁶, R⁷, R⁸ and R⁹ (at each occurrence) is independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy. [0095] In other variations, the organosilicon compound is a silane. The silane may be unsubstituted (e.g., a hydrosilane) or substituted. In some variations, the silane is substituted with 1, 2, 3 or 4 substituents. In one variation, the silane is substituted with aryl, halo, alkyl, alkoxy or amino groups.

[0096] In certain embodiments, the organosilicon compound is wherein each R⁶,

R⁷, R⁸ and R⁹ is independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy. [0097] In one embodiment, the organosilicon compound is an arylsilane. In some variations, the arylsilane comprises 1, 2 or 3 aryl groups. The variations of the foregoing, the aryl group is phenyl. Suitable arylsilanes may include, for example, diphenylsilane and phenylsilane. In one variation, the organosilicon compound is Ph₂SiH₂. In another variation, the organosilicon compound is PhSiH₃. [0098] In other embodiments, the organosilicon compound is a halosilane, an alkoxysilane, or an aminosilane. In one embodiment, the organosilicon compound is a halosilane. In some variations, the halosilane comprises 1, 2 or 3 halo groups. In certain variations, the halosilane may be further substituted with one or more substituents (other than halo). In one variation, the halosilane is further substituted with 1, 2 or 3 substituents (other than halo). In variations of the foregoing, the substituents of the halosilane are independently alkyl or aryl. In one variation of the foregoing, the alkyl substituent of the halosilane is C_1-6 alkyl. In another variation, the substituents of the halosilane are independently methyl or phenyl. Suitable halosilanes may include, for example, dialkyldihalosilane, aryltrihalosilane, arylalkyldihalosilane, or

aryltrihalosilane. In certain variations, the halosilane is a chlorosilane. Suitable chlorosilanes may include, for example, dimethyldichlorosilane, phenyltrichlorosilane, or

phenylmethyldichlorosilane. [0099] In another embodiment, the organosilicon compound is an alkoxysilane. In certain variations, the alkoxysilane comprises an alkylsilicate. In one variation, the alkoxysilane comprises a C_1-6 alkylsilicate. Suitable alkylsilicates include, for example, n-butylsilicate. In other variations, the alkoxysilane comprises 1, 2 or 3 alkoxy groups. In certain variations of the foregoing, the alkoxysilane may be further substituted with 1, 2 or 3 substituents (other than alkoxy). In one variation, the substituents of the alkoxysilane are independently alkyl or aryl. In one variation of the foregoing, the alkyl substituent of the alkoxysilane is C_1-6 alkyl. In another variation, the substituents of the alkoxysilane are independently methyl or phenyl. Suitable alkoxysilanes may include, for example, dimethoxy(methyl)phenylsilane. [0100] In yet another embodiment, the organosilicon compound is an aminosilane. In certain variations, the aminosilane is an alkylaminosilane. In certain variations of the foregoing, the aminosilane may be further substituted with 1, 2 or 3 substituents (other than an amino group, including, for example, an alkylamino group). In one variation, the substituents of the aminosilane are alkoxy groups. In one variation of the foregoing, the alkoxy substituent of the aminosilane is C_1-6 alkoxy. In another variation, the substituents of the aminosilane are independently methoxy or ethoxy. Suitable aminosilanes may include, for example, (3- aminopropyl)triethoxysilane. [0101] In other embodiments, the organosilicon compound is bis(trialkylsilyl)amine In one variation, the organosilicon compound is bis(trimethylsilyl)amine. [0102] In some variations of the foregoing, the silanes described herein may be used in combination with an alkylammonium halide as the dehydration agent. In one variation, the alkylammonium halide is tetrabutylammonium halide, such as tetrabutylammonium chloride or tetrabutylammonium fluoride. In certain variations, the organosilicon compound and the alkylammonium halide are provided as a mixture (e.g., in a solvent) or separately combined. Transition Metal Complexes [0103] In certain embodiments, the dehydration agent comprises a transition metal complex. In some variations, the transition metal complex comprises at least one halide or oxide ligand. The halide or oxide ligand may be associated or complexed with the transition metal. [0104] In certain variations of the foregoing, the transition metal complex is provided in a solvent. In other variations, the transition metal complex is provided in water or acetonitrile, or a mixture thereof. [0105] In one embodiment, the transition metal complex is a metal halide. In some variations, the metal halide comprises a Group 10 metal or a Group 12 metal. In certain variations, the metal halide comprises palladium or zinc. In certain variations, the metal halide comprises chloro. Suitable metal halides may include, for example, palladium chloride or zinc chloride. [0106] In some variations of the foregoing, the metal halide is provided in a solvent. In one variation, the metal halide is provided in water, acetonitrile or a mixture thereof. For example, the transition metal complex used in the methods described herein may be palladium chloride or zinc chloride provided in water, acetonitrile or a mixture thereof. [0107] In another embodiment, the transition metal complex comprises a Group 5 metal. In some variations, the transition metal complex comprises a vanadium oxide. In one variation, the vanadium oxide is monomeric vanadium oxide. In a certain variation, the dehydration agent comprises vanadium oxide and hydrotalcite. In one variation, the dehydration agent comprises monomeric vanadium oxide and hydrotalcite. The vanadium oxide (including, for example, monomeric vanadium oxide) may be incorporated on the surface of hydrotalcite. Aluminum Complexes [0108] In certain embodiments, the dehydration agent comprises an aluminum complex. In some variations, the aluminum complex comprises an aluminum halide. In certain variations, the aluminum complex is complexed with water, acetonitrile, or an alkali metal salt, or a mixture thereof. In some variations, the alkali metal salt is a sodium salt or a potassium salt. In some variations, the alkali metal salt is an alkali metal halide salt. In some variations, the alkali metal halide salt is an alkali metal iodide salt. In some variations, the alkali metal halide salt is sodium iodide or potassium iodide. In some variations, the aluminum complex is

AlCl₃•H₂O/KI/H₂O/CH₃CN. In some variations, the aluminum complex is AlCl₃•NaI. Other Heterogeneous Dehydrating Agents [0109] In some variations, the dehydrating agents are heterogeneous. For example, in certain variations, the dehydration agent comprises a solid metal oxide, a solid acid, an acid, a weak acid, a strong acid, an ion-exchange resin, an aluminosilicate, or any combination thereof. [0110] In certain variations, the dehydration agent comprises a solid metal oxide. In one variation, the dehydration agent comprises TiO₂, ZrO₂, Al₂O₃, SiO₂, ZnO₂, SnO₂, WO₃, MnO₂, Fe₂O₃, SiO₂/Al₂O₃, ZrO₂/ WO₃, ZrO₂/Fe₂O₃, or ZrO₂/MnO₂, or any combination thereof. [0111] In certain variations, the dehydration agent comprises a titanic acid, a metal oxide hydrate, a metal sulfate, a metal oxide sulfate, a metal phosphate, a metal oxide phosphate, a mineral acid, a carboxylic acid or a salt thereof, an acidic resin, an acidic zeolite, clay, or any combination thereof. In certain variations, the dehydration agent comprises H₃PO₄/SiO₂, fluorinated Al₂O₃, Nb₂O₃/PO ^-3

4 , Nb₂O₃/SO ^-2

4 , Nb₂O₅, H₃PO₄, a phosphate salt, a

phosphotungstic acid, a phosphomolybdic acid, a silicomolybdic acid, a silicotungstic acid, Mg₂P₂O₇ or MgHPO₄, or any combination thereof. [0112] In some variations, the dehydration agent comprises a zeolite. In certain variations, the zeolite is in hydrogen form or ammonia form, or is a metal-exchanged zeolite. In one variation, the metal-exchange zeolite comprises Li, Na, K, Ca, Mg, or Cu. In another variations, the zeolite has a pore size ranging from 1 to 10 angstroms in diameter. In one variation, the zeolite is a medium pore zeolite. In some variations, the zeolite has a pore size of about 5 to 6 angstroms, or about 5.6*6.0 angstroms, or about 5.1* 5.5 to 5.3*5.6 angstroms. In another variation, the zeolite is a large pore zeolite. Suitable zeolites may include, for example, ZSM-12, ZSM-5, mordenite, faujasite, or zeolite Y. [0113] In variations where a heterogeneous dehydration agent, like the ones described above, are used, the compound of formula (2) undergoes dehydration to produce the compound of formula (3-I) or the compound of formula (3), or a combination thereof, by passing the compound of formula (2) in the vapor phase through a heated reactor containing the dehydration agent. In one variation, reactor is a packed bed reactor, a fluidized bed reactor, or a moving bed reactor. Combinations of Dehydration Agents [0114] It should be understood that, in some variations, the term“dehydration agent” may include a combination of agents. In some variations of the methods described herein, a combination of the dehydration agents described herein may be used. [0115] In some embodiments, the dehydration agent comprises a combination of an organosilicon compound and a transition metal complex. In certain variations of the foregoing combination, the organosilicon compound is N-methyl-N-(trimethylsilyl)trifluoroacetamide. In some variations of the foregoing combination, the transition metal complex is a metal triflate or a metal halide. In one variation, the metal triflate is zinc triflate. In another variation, the metal halide is copper chloride. [0116] In other embodiments, the dehydration agent comprises a combination of a silane and a transition metal complex. In certain variations of the foregoing combination, the transition metal complex is an iron complex. In one variation, the dehydration agent comprises a combination of a silane and an iron complex. [0117] In other variations of the combination of a silane and a transition metal complex, the transition metal complex is metal carbonate. In certain variations, the metal carbonate comprises iron. In certain variations, the metal carbonate is an iron carbonate. Suitable metal carbonates include, for example, Fe₂(CO)₉. In some variations of the foregoing combination, the organosilicon compound is an alkoxyalkylsilane. In certain variations, the alkoxyalkylsilane is diethoxymethylsilane. In one variation, the dehydration agent comprises a combination of iron carbonate and an alkoxyalkylsilane. [0118] Exemplary combinations of dehydration agents that may be used in the methods described herein include zinc triflate and N-methyl-N-(trimethylsilyl)trifluoroacetamide; copper chloride and N-methyl-N-(trimethylsilyl)trifluoroacetamide; an iron complex and a silane; and iron carbonate and diethoxymethylsilane. Downstream Uses [0119] The acrylamide, acrylonitrile and other compounds produced according to the methods described herein may, in some variations, be used as a monomer for the industrial production of polymers. [0120] The compounds of formulae (3-I) produced according to the methods herein may be used to produce one or more downstream products. For example, with reference to FIG.8B, acrylamide produced according to the methods described herein may be used in the production of polyacrylamide. Thus, in certain aspects, provided is a method, comprising: producing a compound of formula (3-I) according to any of the methods herein; and polymerizing the compound of formula (3-I). In one variation, provided is a method of producing polyacrylamide, comprising: producing acrylamide according to any of the methods herein; and polymerizing the acrylamide to produce polyacrylamide. [0121] The compounds of formula (2) produced according to the methods herein may be used to produce one or more downstream products. For example, with reference again to FIG. 8B, acrylonitrile produced according to the methods described herein may be used in the production of polyacrylonitrile. Thus, in certain aspects, provided is a method, comprising: producing a compound of formula (2) according to any of the methods herein; and polymerizing the compound of formula (2). In one variation, provided is a method of producing

polyacrylonitrile, comprising: producing acrylonitrile according to any of the methods herein; and polymerizing the acrylonitrile to produce polyacrylonitrile. The polyacrylonitrile may be suitable for various uses, including carbon fibers. [0122] In other aspects, acrylonitrile produced according to the methods described herein may be used in the production of acrylic acid and/or acrylamide. Compositions [0123] In some aspects, provided is a composition, comprising: a compound of formula (2): wherein R¹ is H or alkyl; and

a dehydration agent.

[0124] In certain aspects, the composition further comprises a compound of formula (3):

or isomers thereof, wherein R¹ is as defined above for formula (2).

[0125] In some variations of the foregoing, the composition further comprises:

a compound of formula (1):

wherein R¹ is as defined above for formula (2); and

ammonia.

[0126] In other aspects, provided is a composition, comprising:

a compound of formula (1)

wherein R¹ is H or alkyl;

ammonia; and

a dehydration agent. [0127] In some variations of the foregoing, the composition further comprises a compound of formula (3-I), and/or a compound of formula (3):

or isomers thereof, wherein R¹ is as defined above for formula (1). [0128] In certain variations of the foregoing, the compounds, the dehydration agent (including combination of dehydration agents), and the ammonia present in the composition are as described herein for the methods. Systems [0129] In some aspects, provided is a system, comprising a continuous stirred-tank reactor comprising: a first inlet configured to receive a compound of formula (1):

wherein R¹ is H or alkyl; a second inlet configured to receive ammonia; wherein the reactor is configured to add the compound of formula (1) to the ammonia to achieve a ratio of ammonia to compound of formula (1) such that the ammonia is present in excess, wherein the reactor is configured to add the compound of formula (1) to the ammonia at a rate suitable for maintaining the temperature, and wherein the reactor is configured to receive the ammonia and the compound of formula (1) in liquid form; a jacket configured to maintain constant temperature in the reactor; a vent configured to release any excess ammonia from the reactor; and an outlet configured to release a product stream comprising a compound of formula (2) produced from the compound of formula (1) and the ammonia,

wherein the compound of formula (2) is: wherein R¹ is as defined above for formula (1).

[0130] In other aspects, provided is a system, comprising: a reactor, comprising: an inlet configured to receive ammonia and a compound of formula (1), wherein the ammonia is in gaseous form and the compound of formula (1) is in liquid form,

wherein the compound of formula (1) is , wherein R¹ is H or alkyl;

a heterogeneous catalyst bed; wherein the reactor is configured to co-feed the ammonia and the compound of formula (1) to the heterogeneous catalyst bed, wherein the reactor is configured to control the flow rate of the ammonia and the compound of formula (1) separately, wherein the reactor is configured to add the compound of formula (1) to the ammonia to achieve a ratio of ammonia to compound of formula (1) such that the ammonia is present in excess, a jacket configured to maintain constant temperature in the reactor; a vent configured to release any excess ammonia from the reactor; and an outlet configured to release a product stream comprising a compound of formula (2) produced from the compound of formula (1) and the ammonia,

wherein the compound of formula (2) is wherein R¹ is as defined above for formula (1).

[0131] In yet other aspects, provided is a system, comprising: a tube shell reactor comprising: one or more tubes, wherein catalyst particles are packed between and around the one or more tubes, and wherein the one or more tubes are configured to receive ammonia is gaseous form; an inlet on the shell side of the reactor configured to receive a compound of formula (1) in liquid form, wherein the reactor is configured to maintain an excess of ammonia in the reactor as compared to the compound of formula (1), wherein the reactor is configured to a temperature to produce a compound of formula (2) from the compound of formula (1) and the ammonia; and an outlet configured to release a product stream comprising the compound of formula (2) and excess ammonia. [0132] In some variations of the foregoing, the compound of formula (2) is provided in molten form. ENUMERATED EMBODIMENTS [0133] The following enumerated embodiments are representative of some aspects of the invention. 1. A method of producing a compound of formula (3-I) and/or a compound of formula (3):

or isomers thereof, wherein R¹ is H or alkyl, the method comprising: combining a compound of formula (2) with a dehydration agent to produce the compound of formula (3), or isomers thereof, wherein:

the compound of formula (2) is

wherein R¹ is as defined above for formulae (3-I) and (3), and the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a mixed oxide, a transition metal complex, or an aluminum complex, or any combination thereof; or the dehydration agent comprises a solid metal oxide, a solid acid, an acid, a weak acid, a strong acid, an ion-exchange resin, an aluminosilicate, or any combination thereof. 2. The method of embodiment 1, further comprising combining a compound of formula (1) with ammonia to produce the compound of formula (2), wherein: the compound of formula (1) is , wherein R¹ is as defined above for

formulae (3-I) and (3). 3. The method of embodiment 2, wherein the combining of the compound of formula (1) with ammonia further produces a compound of formula (2-I):

wherein R¹ is as defined above for formulae (3-I) and (3). 4. The method of any one of embodiments 1 to 3, further comprising isolating the compound of formula (2-I). 5. A method of producing a compound of formula (3-I) and/or a compound of formula (3):

or isomers thereof, wherein R¹ is H or alkyl, the method comprising: combining a compound of formula (1) with ammonia and a dehydration agent to produce the compound of formula (3-I) and/or the compound of formula (3), or isomers thereof, wherein:

the compound of formula (1) is

, wherein R¹ is as defined above for formulae (3-I) and (3), and the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a mixed oxide, a transition metal complex, or an aluminum complex, or any combination thereof; or the dehydration agent comprises a solid metal oxide, a solid acid, an acid, a weak acid, a strong acid, an ion-exchange resin, an aluminosilicate, or any combination thereof. 6. The method of embodiment 2 or 3, wherein: the ammonia is aqueous ammonia, or the ammonia is liquid ammonia, or the ammonia is anhydrous ammonia; or anhydrous gaseous ammonia. 7. The method of any one of embodiments 1 to 5, wherein: R¹ is H; or R¹ is alkyl; or R¹ is methyl or ethyl. 8. The method of any one of embodiments 1 to 7, further comprising isolating the compound of formula (3-I) or the compound of formula (3), or both. 9. The method of any one of embodiments 1 to 8, wherein the dehydration agent comprises phosphorous pentoxide. 10. The method of any one of embodiments 1 to 8, wherein the dehydration agent comprises an organophosphorous compound. 11. The method of embodiment 10, wherein the organophosphorous compound is an organophosphate. 12. The method of embodiment 10, wherein the organophosphorous compound is an alkyl halophosphate or a cycloalkyl halophosphate. 13. The method of embodiment 10, wherein the organophosphorous compound is ethyl dichlorophosphate, diethyl chlorophosphate, methyl dichlorophosphate, dimethyl

chlorophosphate, ethyl difluorophosphate, diethyl fluorophosphate, methyl difluorophosphate, or dimethyl fluorophosphate, or any combination thereof. 14. The method of any one of embodiments 1 to 8, wherein the dehydration agent comprises a carbodiimide compound. 15. The method of embodiment 14, wherein the carbodiimide compound is ^{R4 N C N R5}

, wherein each R⁴ and R⁵ is independently alkyl or cycloalkyl. 16. The method of embodiment 14, wherein the carbodiimide compound is N,N’- dicyclohexylcarbodiimide. 17. The method of any one of embodiments 1 to 8, wherein the dehydration agent comprises a triazine compound. 18. The method of embodiment 17, wherein the triazine compound is a halo-substituted triazine compound. 19. The method of embodiment 17 or 18, wherein the triazine compound is 1, 3, 5-triazine. 20. The method of embodiment 17 or 18, wherein the triazine compound is cyanuric chloride. 21. The method of any one of embodiments 1 to 8, wherein the dehydration agent comprises an organosilicon compound. 22. The method of embodiment 21, wherein the organosilicon compound is a silazane or a silane. 23. The method of embodiment 21, wherein the organosilicon compound is

bis(trimethylsilyl)amine. 24. The method of embodiment 21, wherein the organosilicon compound is

wherein each R⁶, R⁷, R⁸ and R⁹ is independently H, alkyl, cycloalkyl, heteroalkyl,

heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy. 25. The method of embodiment 21, wherein the organosilicon compound is a hydrosilane. 26. The method of embodiment 25, wherein the dehydration agent further comprises an alkylammonium halide. 27. The method of embodiment 26, wherein the alkylammonium halide is

tetrabutylammonium fluoride. 28. The method of embodiment 21, wherein the organosilicon compound is a silane. 29. The method of embodiment 28, wherein the silane is a halosilane, an alkoxysilane, or an aminosilane. 30. The method of any one of embodiments 1 to 8, wherein the dehydration agent comprises a transition metal complex. 31. The method of embodiment 30, wherein the transition metal complex comprises at least one halide or oxide ligand. 32. The method of embodiment 30 or 31, wherein the transition metal complex comprises palladium or zinc. 33. The method of embodiment 30 or 31, wherein the transition metal complex is palladium chloride or zinc chloride provided in water, acetonitrile or a mixture thereof. 34. The method of embodiment 30 or 31, wherein the transition metal complex comprises a vanadium oxide. 35. The method of any one of embodiments 1 to 8, wherein the dehydration agent comprises an organosilicon compound and a transition metal complex. 36. The method of embodiment 35, wherein the organosilicon compound is N-methyl-N- (trimethylsilyl)trifluoroacetamide. 37. The method of embodiment 35 or 36, wherein the transition metal complex is a metal triflate or a metal halide. 38. The method of embodiment 35, wherein the organosilicon compound comprises a silane. 39. The method of embodiment 35 or 38, wherein the transition metal complex is an iron complex. 40. The method of embodiment 35, wherein the organosilicon compound is an

alkoxyalkylsilane. 41. The method of embodiment 35 or 40, wherein the transition metal complex is metal carbonate. 42. The method of embodiment 41, wherein the metal carbonate is an iron carbonate. 43. The method of any one of embodiments 1 to 8, wherein the dehydration agent comprises: (i) zinc triflate and N-methyl-N-(trimethylsilyl)trifluoroacetamide; or (ii) copper chloride and N-methyl-N-(trimethylsilyl)trifluoroacetamide; or (iii) an iron complex and a silane; or (iv) iron carbonate and diethoxymethylsilane. 44. The method of any one of embodiments 1 to 8, wherein the dehydration agent comprises an aluminum complex. 45. The method of embodiment 44, wherein the aluminum complex comprises an aluminum halide. 46. The method of embodiment 44 or 45, wherein the aluminum complex is complexed with water, acetonitrile, or an alkali metal salt, or a mixture thereof. 47. The method of any one of embodiments 1 to 8, wherein the dehydration agent comprises a AlCl₃•H₂O/KI/H₂O/CH₃CN system or AlCl₃•NaI. 48. The method of any one of embodiments 1 to 47, wherein the dehydration agent further comprises a solid support. 49. The method of embodiment 48, wherein the solid support is hydrotalcite. 50. The method of any one of embodiments 1 to 8, wherein the dehydration agent comprises monomeric vanadium oxide and hydrotalcite. 51. The method of any one of embodiments 1 to 8, wherein the dehydration agent comprises TiO₂, ZrO₂, Al₂O₃, SiO₂, ZnO₂, SnO₂, WO₃, MnO₂, Nb₂O₅, P₂O₅, Fe₂O₃, SiO₂/Al₂O₃, ZrO₂/ WO₃, ZrO₂/Fe₂O₃, or ZrO₂/MnO₂, or any combination thereof. 52. The method of any one of embodiments 1 to 8, wherein the dehydration agent comprises a titanic acid, a metal oxide hydrate, a metal sulfate, a metal oxide sulfate, a metal phosphate, a metal oxide phosphate, a mineral acid, a carboxylic acid or a salt thereof, an acidic resin, an acidic zeolite, clay, or any combination thereof. 53. The method of any one of embodiments 1 to 8, wherein the dehydration agent comprises H₃PO₄/SiO₂, fluorinated Al₂O₃, Nb₂O ^-3

3/PO₄ , Nb₂O₃/SO ^-2

4 , Nb₂O₅, H₃PO₄, a phosphate salt, a phosphotungstic acid, a phosphomolybdic acid, a silicomolybdic acid, a silicotungstic acid, Mg₂P₂O₇ or MgHPO₄, or any combination thereof. 54. The method of any one of embodiments 1 to 8, wherein the dehydration agent comprises a zeolite. 55. The method of embodiment 54, wherein the zeolite is in hydrogen form or ammonia form, or is a metal-exchanged zeolite. 56. The method of embodiment 54, wherein the metal-exchange zeolite comprises Li, Na, K, Ca, Mg, or Cu. 57. The method of embodiment 54, wherein the zeolite has a pore size ranging from 1 to 10 angstroms in diameter. 58. The method of embodiment 54, wherein the zeolite is a medium pore zeolite. 59. The method of embodiment 54, wherein the zeolite has a pore size of about 5 to 6 angstroms, or about 5.6*6.0 angstroms, or about 5.1* 5.5 to 5.3*5.6 angstroms. 60. The method of embodiment 54, wherein the zeolite is a large pore zeolite. 61. The method of embodiment 54, wherein the zeolite is ZSM-12, ZSM-5, mordenite, faujasite, or zeolite Y. 62. The method of any one of embodiments 1 to 61, wherein the compound of formula (2) undergoes dehydration to produce the compound of formula (3-I) and/or the compound of formula (3), by passing the compound of formula (2) in the vapor phase through a heated reactor containing the dehydration agent. 63. The method of embodiment 62, wherein the reactor is a packed bed reactor, a fluidized bed reactor, or a moving bed reactor. 64. A method, comprising: combining a compound of formula (1) and ammonia in a reactor at an average temperature suitable to produce a compound of formula (2) with a selectivity of greater than 50%, wherein:

the compound of formula (1) is

the compound of formula (2) is

, wherein R¹ is H or alkyl. 65. A method, comprising: combining a compound of formula (1) and ammonia in a reactor to produce a compound of formula (2), a compound of formula (3-I), and/or a compound of formula (3), or any isomers of the foregoing (as the case may be), with a selectivity of greater than 50%, wherein:

the compound of formula (1) is

,

the compound of formula (2) is

,

the compound of formula (3-I) is

, and the compound of formula (3) is

wherein R¹ is H or alkyl. 66. The method of embodiment 64 or 65, wherein the temperature of the reactor is maintained at an average temperature suitable to produce the compound of formula (2), the compound of formula (3-I), and/or the compound of formula (3), or any isomers of the foregoing (as the case may be), with the selectivity of greater than 50%. 67. The method of any one of embodiments 64 to 66, wherein the compound of formula (1) is added drop-wise to the reactor containing the ammonia. 68. The method of any one of embodiments 64 to 66, wherein the compound of formula (1) is added by single injection to the reactor containing the ammonia. 69. A method, comprising: providing ammonia to a reactor; adding a first portion of a compound of formula (1) to the reactor, wherein: the compound of formula (1) is wherein R¹ is H or alkyl;

controlling the temperature of the reactor after the addition of the first portion of the compound of formula (1); adding a second portion of a compound of formula (1) to the reactor; and controlling the temperature of the reactor after the addition of the second portion of the compound of formula (1), wherein the addition of the first portion and the second portion of the compound of formula (I) produces a compound of formula (2):

, wherein R¹ is as defined above, and wherein the temperature of the reactor is controlled to an average temperature suitable to produce the compound of formula (2). 70. A method, comprising: cofeeding a compound of formula (1) and ammonia to a heterogeneous catalyst bed to produce a compound of formula (2), wherein:

the compound of formula (1) is

the compound of formula (2) is

wherein R¹ is H or alkyl 71. The method of embodiment 70, wherein the compound of formula (1) is fed to the reactor as a liquid. 72. The method of embodiment 70 or 71, wherein the flow rates of the compound of formula (1) and the ammonia are controlled separately. 73. The method of any one of embodiments 70 to 72, wherein the ammonia is present in the reactor at an excess. 74. The method of any one of embodiments 70 to 73, further comprising collecting a product stream comprising the compound of formula (2) and excess ammonia from the reactor. 75. The method of embodiment 74, wherein the compound of formula (2) is collected in liquid form. 76. The method of embodiment 74 or 75, wherein the product stream is collected in a collection flask. 77. The method of embodiment 76, wherein the temperature of the collection flask is below the boiling point of the compound of formula (2). 78. The method of any one of embodiments 70 to 77, further comprising separating excess ammonia from the product stream. 79. The method of embodiment 78, further comprising recycling the separated ammonia to the reactor. 80. The method of any one of embodiments 70 to 79, wherein the heterogeneous catalyst bed comprises a metal oxide, a basic zeolite, an alkali metal exchanged zeolite, a base modified alumina, or a solid“super base”. 81. The method of any one of embodiments 70 to 80, wherein the reactor is maintained at a temperature where the compound of formula (2) is a gas. 82. The method of any one of embodiments 70 to 81, wherein the compound of formula (2) is produced anhydrously. 83. The method of any one of embodiments 70 to 82, wherein: the ammonia is aqueous ammonia, or the ammonia is liquid ammonia, or the ammonia is anhydrous ammonia, or the ammonia is anhydrous gaseous ammonia. 84. The method of any one of the preceding embodiments, wherein the compound of formula (3-I) is acrylamide, and the compound of formula (3) is acrylonitrile. 85. A method of producing polyacrylamide, comprising: producing acrylamide according to the method of embodiment 84; and polymerizing the acrylamide to produce polyacrylamide. 86. A method of producing polyacrylonitrile, comprising: producing acrylonitrile according to the method of embodiment 84; and polymerizing the acrylonitrile to produce polyacrylonitrile. 87. A method of producing a carbon fiber, comprising: producing polyacrylonitrile according to the method of embodiment 86; and producing a carbon fiber from the polyacrylonitrile. 88. A system, comprising a continuous stirred-tank reactor comprising: a first inlet configured to receive a compound of formula (1):

89. A system, comprising: a reactor, comprising: an inlet configured to receive ammonia and a compound of formula (1), wherein the ammonia is in gaseous form and the compound of formula (1) is in liquid form, wherein the compound of formula (1) is wherein R¹ is H or

alkyl; a heterogeneous catalyst bed; wherein the reactor is configured to co-feed the ammonia and the compound of formula (1) to the heterogeneous catalyst bed, wherein the reactor is configured to control the flow rate of the ammonia and the compound of formula (1) separately, wherein the reactor is configured to add the compound of formula (1) to the ammonia to achieve a ratio of ammonia to compound of formula (1) such that the ammonia is present in excess, a jacket configured to maintain constant temperature in the reactor; a vent configured to release any excess ammonia from the reactor; and an outlet configured to release a product stream comprising a compound of formula (2) produced from the compound of formula (1) and the ammonia,

wherein the compound of formula (2) is

wherein R¹ is as defined above for formula (1). 90. The system of embodiment 88 or 89, wherein the compound of formula (2) is provided in molten form. 91. A method of producing a compound of formula (3):

wherein R¹ is H or alkyl, or isomers thereof, the method comprising: combining a compound of formula (2) with a dehydration agent to produce the compound of formula (3), or isomers thereof, wherein:

the compound of formula (2) is wherein R¹ is as defined above for formula (3), and

the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof. 92. The method of embodiment 91, further comprising combining a compound of formula (1) with ammonia to produce the compound of formula (2), wherein:

the compound of formula (1) is wherein R¹ is as defined above for

formula (3). 93. A method of producing a compound of formula (3):

wherein R¹ is H or alkyl, or isomers thereof, the method comprising: combining a compound of formula (1) with ammonia and a dehydration agent to produce the compound of formula (3), or isomers thereof, wherein: the compound of formula (1) is

wherein R¹ is as defined above for formula (3), and the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof. 94. The method of embodiment 92 or 93, wherein the ammonia is ammonium hydroxide or aqueous ammonia. 95. The method of any one of embodiments 92 to 94, wherein the compound of formula (1) is combined with ammonia at room temperature. 96. The method of any one of embodiments 91 to 95, wherein R¹ is H. 97. The method of any one of embodiments 91 to 95, wherein R¹ is alkyl. 98. The method of any one of embodiments 91 to 95, wherein R¹ is methyl or ethyl. 99. The method of any one of embodiments 91 to 98, wherein the dehydration agent comprises phosphorous pentoxide. 100. The method of any one of embodiments 91 to 98, wherein the dehydration agent comprises an organophosphorous compound. 101. The method of embodiment 100, wherein the organophosphorous compound is an organophosphate. 102. The method of embodiment 100, wherein the organophosphorous compound is an alkyl halophosphate or a cycloalkyl halophosphate. 103. The method of embodiment 100, wherein the organophosphorous compound is ethyl dichlorophosphate, diethyl chlorophosphate, methyl dichlorophosphate, dimethyl chlorophosphate, ethyl difluorophosphate, diethyl fluorophosphate, methyl difluorophosphate, or dimethyl fluorophosphate, or any combination thereof. 104. The method of any one of embodiments 91 to 98, wherein the dehydration agent comprises a carbodiimide compound. 105. The method of embodiment 104, wherein the carbodiimide compound is

wherein each R⁴ and R⁵ is independently alkyl or cycloalkyl. 106. The method of embodiment 104, wherein the carbodiimide compound is N,N’- dicyclohexylcarbodiimide. 107. The method of any one of embodiments 91 to 98, wherein the dehydration agent comprises a triazine compound. 108. The method of embodiment 107, wherein the triazine compound is a halo-substituted triazine compound. 109. The method of embodiment 107 or 108, wherein the triazine compound is 1, 3, 5-triazine. 110. The method of embodiment 107 or 108, wherein the triazine compound is cyanuric chloride. 111. The method of any one of embodiments 91 to 98, wherein the dehydration agent comprises an organosilicon compound. 112. The method of embodiment 111, wherein the organosilicon compound is a silazane or a silane. 113. The method of embodiment 111, wherein the organosilicon compound is

bis(trimethylsilyl)amine. 114. The method of embodiment 111, wherein the organosilicon compound is

heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy. 115. The method of embodiment 111, wherein the organosilicon compound is a hydrosilane. 116. The method of embodiment 115, wherein the dehydration agent further comprises an alkylammonium halide. 117. The method of embodiment 116, wherein the alkylammonium halide is

tetrabutylammonium fluoride. 118. The method of embodiment 111, wherein the organosilicon compound is a silane. 119. The method of embodiment 118, wherein the silane is a halosilane, an alkoxysilane, or an aminosilane. 120. The method of any one of embodiments 91 to 98, wherein the dehydration agent comprises a transition metal complex. 121. The method of embodiment 120, wherein the transition metal complex comprises at least one halide or oxide ligand. 122. The method of embodiment 120 or 121, wherein the transition metal complex comprises palladium or zinc. 123. The method of embodiment 120 or 121, wherein the transition metal complex is palladium chloride or zinc chloride provided in water, acetonitrile or a mixture thereof. 124. The method of embodiment 120 or 121, wherein the transition metal complex comprises a vanadium oxide. 125. The method of any one of embodiments 91 to 98, wherein the dehydration agent comprises an organosilicon compound and a transition metal complex. 126. The method of embodiment 125, wherein the organosilicon compound is N-methyl-N- (trimethylsilyl)trifluoroacetamide. 127. The method of embodiment 125 or 126, wherein the transition metal complex is a metal triflate or a metal halide. 128. The method of embodiment 125, wherein the organosilicon compound comprises a silane. 129. The method of embodiment 125 or 128, wherein the transition metal complex is an iron complex. 130. The method of embodiment 125, wherein the organosilicon compound is an

alkoxyalkylsilane. 131. The method of embodiment 125 or 130, wherein the transition metal complex is metal carbonate. 132. The method of embodiment 131, wherein the metal carbonate is an iron carbonate. 133. The method of any one of embodiments 91 to 98, wherein the dehydration agent comprises: (i) zinc triflate and N-methyl-N-(trimethylsilyl)trifluoroacetamide; or (ii) copper chloride and N-methyl-N-(trimethylsilyl)trifluoroacetamide; or (iii) an iron complex and a silane; or (iv) iron carbonate and diethoxymethylsilane. 134. The method of any one of embodiments 91 to 98, wherein the dehydration agent comprises an aluminum complex. 135. The method of embodiment 134, wherein the aluminum complex comprises an aluminum halide. 136. The method of embodiment 134 or 135, wherein the aluminum complex is complexed with water, acetonitrile, or an alkali metal salt, or a mixture thereof. 137. The method of any one of embodiments 91 to 98, wherein the dehydration agent comprises a AlCl₃•H₂O/KI/H₂O/CH₃CN system or AlCl₃•NaI. 138. The method of any one of embodiments 91 to 137, wherein the dehydration agent further comprises a solid support. 139. The method of embodiment 138, wherein the solid support is hydrotalcite. 140. The method of any one of embodiments 91 to 98, wherein the dehydration agent comprises monomeric vanadium oxide and hydrotalcite. 141. A composition, comprising: a compound of formula (2):

wherein R¹ is H or alkyl; and

a dehydration agent comprising phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof. 142. The composition of embodiment 141, further comprising a compound of formula (3):

wherein R¹ is as defined above for formula (2), or isomers thereof. 143. The composition of embodiment 141 or 142, further comprising: a compound of formula (1):

, wherein R¹ is as defined above for formula (2); and ammonia. 144. A composition, comprising: a compound of formula (1)

wherein R¹ is H or alkyl; ammonia; and a dehydration agent comprising phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof. 145. The composition of embodiment 144, further comprising a compound of formula (3):

wherein R¹ is as defined above for formula (1), or isomers thereof. EXAMPLES [0134] The following Examples are merely illustrative and are not meant to limit any aspects of the present disclosure in any way. Example 1 Anhydrous Synthesis of 3-Hydroxypropanamide (3-HP amide) [0135] This example is directed to a process for the synthesis of 3-hydroxypropanamide (3- HP amide) from beta-propiolactone (BPL). This process is highly selective to produce 3-HP amide that is not contaminated with water. [0136] The synthesis is performed by addition of BPL in a controlled manner to a liquid pool of ammonia. This is executed by adding beta-propiolactone and liquid ammonia (anhydrous) to a Parr type reactor configured to allow addition of the ammonia and BPL as liquids. The reactor is also configured to contain any pressure that might be produced at the reaction conditions, and during the reaction, and is jacketed to maintain constant temperature. Alternatively, the reactor may be fit with a condenser suitable to operate under pressure and to control the temperature in the reactor by condensing and returning to the reactor any ammonia boiling off during the reaction process. BPL is added to the liquid ammonia at a rate at which the temperature is controlled at the desired set point. The ratio of ammonia to BPL is maintained such that ammonia is always in considerable excess. [0137] After the desired quantity of BPL is added and sufficient time is allowed for complete conversion the reaction is stopped by venting the ammonia, which is collected and recycled to the next reaction. The remaining material in the reactor is mostly 3-HP amide that is collected and purified. [0138] In some variations of this process, the temperature for this reaction is in the range from 33 °C to room temperature. The aqueous reaction occurs at room temperature. The required pressure for the reaction is set by the vapor pressure of ammonia at the optimum reaction temperature. Example 2 Heterogeneous Catalytic Process for the Production of 3-HP Amide [0139] This example is directed to another process for the synthesis of 3-HP amide from BPL. This process is highly selective, and performed continuously over a heterogeneous base catalyst. [0140] The synthesis is performed by cofeeding BPL and ammonia to a heterogeneous catalyst bed. The BPL is fed to the reactor as a liquid, and the ammonia is fed to the reactor as a gas. This reactor configuration may be referred to as a“trickle bed reactor”. The flow rates of the liquid BPL and the gaseous ammonia are controlled separately. The ratios are controlled to ensure that the ammonia is always in excess. The residence time in the catalyst bed is controlled to ensure that complete conversion of the BPL occurs. The product 3-HP amide is collected at the exit of the reactor in liquid form, and the gaseous excess ammonia is separated and recycled to the reactor. [0141] In some variations of the process, the base catalyst used may include metal oxides (such as MgO, ZrO), basic zeolites (such as an ammonia form of zeolite precursor NH₄ZSM5), alkali metal exchanged zeolites, other modified zeolites, base modified alumina, as well as solid “super bases” (such as lanthanide imide and nitride on zeolite, metal oxynitrides, and

KNH₂/Al₂O₃). [0142] In some variations of this process, the temperature for this reaction is in the range from 10 °C to 100 °C. The aqueous reaction occurs at room temperature. In certain variations, this process is performed at a temperature where the 3-HP amide is a gas. In one variation, this process is performed at 65 °C to 75 °C. [0143] The product collection flask is below the boiling point of the 3-HP amide, but above the boiling point of ammonia. In some variations, the collection temperature is between -30 °C and 65 °C. In one variation, the collection temperature is about 0 °C. Example 3 Reactor Design for Heterogeneous Catalytic Production of 3-HP Amide [0144] The example describes the reactor design suitable for the process to produce 3-HP amide with a high degree of selectivity from BPL, such as the process described in Example 2 above. The reactor is designed to ensure that the ammonia and BPL only come into contact in the heterogeneous catalyst bed. [0145] A tube in shell reactor is used in this example. The catalyst particles are packed between and around the tubes. One reactant, such as ammonia, is fed to the shell side and through the catalyst bed. The second reactant, such as beta-propiolactone, is then fed through the tubes and the tubes are made porous to that reactant in one of two ways. In one variation, holes can be drilled in the tubes through the length of the tubes that are buried in the catalyst bed. Alternatively, in another variation, the tubes can be made of porous metal tubes through the length of the tube that is buried. The tubes may have a solid, non-porous, metal header that would extend down to or into the catalyst bed. These tubes can be made of a variety of non- reactive metals, including stainless steel, Hastelloy, Inconel, and titanium. [0146] In one variation of the foregoing, gaseous ammonia is fed through the tubes and liquid BPL is trickled through the catalyst bed on the shell side. In this configuration, sintered metal tubes may be used, and may be configured so that the back diffusion is nearly zero by controlling pore size. Example 4A Integrated Process for the Production Acrylonitrile or Acrylamide via 3-HP Amide [0147] This example describes an integrated process for producing acrylonitrile, acrylamide, or a combination thereof, via 3-HP amide that is not isolated. The integrated process described in this example combines two process: (1) the process for synthesizing 3-HP amide from BPL under anhydrous conditions, and (2) the process for synthesizing acrylonitrile or acrylamide, or a combination thereof, from the 3-HP amide into one continuous unit operation that converts BPL to acrylonitrile or acrylamide, or a combination thereof. [0148] The following system incorporates the 3-HP amide production process described in Example 1 above. The anhydrous synthesis of 3-HP amide is performed in a continuous stirred- tank reactor (CSTR) and produces a solution of 3-HP amide in ammonia at the end of the reaction. This solution is then drained from the CSTR into a holding tank. From the holding tank, the 3-HP amide in ammonia is continuously fed to the fixed bed heterogeneous reactor containing the desired catalyst for production of the desired product, either acrylonitrile or acrylamide, and heated to the desired reaction temperature. In the heterogeneous reactor, the 3- HP amide is converted with high conversions and high selectivity to the desired product. The resulting mixture of either acrylonitrile/ammonia or acrylamide/ammonia exits the reactor, and is collect in a product recovery vessel where the ammonia is separated from the product, condensed, and recycled to the 3-HP amide synthesis vessel. Inhibitor, to prevent

polymerization, may be added at this stage. In one variation, the inhibitor is added before the ammonia is removed. In another variation, the inhibitor is added after the ammonia is removed. [0149] One advantage of this approach is that acrylonitrile and/or acrylamide are produced continuously and without solvent from the BPL without intermediate separation and purification processes. Example 4B Integrated Process for the Production Acrylonitrile or Acrylamide via 3-HP amide [0150] This example describes an integrated process for producing acrylonitrile, acrylamide, or a combination thereof, via 3-HP amide that is not isolated. The integrated process described in this example combines two process: (1) the process for synthesizing 3-HP amide from BPL under anhydrous conditions, and (2) the process for synthesizing acrylonitrile or acrylamide, or a combination thereof, from the 3-HP amide into one continuous unit operation that converts BPL to acrylonitrile or acrylamide, or a combination thereof. [0151] The following system incorporates the 3-HP amide production process described in Example 2 and/or Example 3 above. With respect to the process described in Examples 2 and 3, the output from the 3-HP amide synthesis reactor at the reactor exit of the trickle bed reactor is a gas-phase stream of 3-HP amide mixed with the ammonia excess required for the optimum yield of 3-HP amide. This gas-phase mixture is then directly fed to the fixed bed heterogeneous reactor containing the desired catalyst for production of the desired product, either acrylonitrile or acrylamide, and heated to the desired reaction temperature. In the heterogeneous reactor, the 3-HP amide is converted with high conversions and high selectivity to the desired product. The rest of the process is just as described above in Example 4A. [0152] One key advantage of this integrated approach is that the amount of unreacted ammonia is less and the amount of excess required can be optimized for both process steps (3-HP amide synthesis and subsequent conversion to the dehydrated product either acrylonitrile or acrylamide) simultaneously and the amount of recycle ammonia required minimized. In addition, the recycle ammonia does not need to be condensed since the feed to the 3-HP amide synthesis reactor in this case is gaseous. Moreover, acrylonitrile and/or acrylamide are produced continuously and without solvent from the BPL without intermediate separation and purification processes. Example 5

3-Hydroxypropanamide Synthesis

[0153] This example explores the impact of the addition order and solvent in the production of 3-HP amide.

[0154] BPL and ammonia were combined in accordance with the description provided in Table 1 below. The yield of 3-HP amide was measured by ¹H NMR and LC-MS.

Example 6

3-Hydroxypropanamide Synthesis

[0155] This example explores the impact of the amount of ammonium hydroxide used relative to the BPL added. [0156] BPL and ammonium hydroxide were combined in a 5L reactor at the NH₄OH:BPL molar ratio set forth in Table 2 below. The same temperature and BPL feed rate was used in each of the three experiments. The yield of 3-HP amide, based on a crude sample of the reaction mixture, was measured by¹H NMR. The reaction was then allowed to run. After the reaction was stopped, the crude reaction measure was passed through an ion exchange resin. The 3-HP amide was recovered from the ion exchange (IX) resin, and the overall yield of 3-HP amide (from synthesis and resin purification) was determined . The 3-HP amide yields are summarized in Table 2 below.

Example 7

3-HP Amide Synthesis By Reacting BPL with Aqueous Ammonia

[0157] This example demonstrates the synthesis of 3-HP amide by reacting BPL with aqueous ammonia, and evaluates the effect of reaction conditions on the selectivity to 3-HP amide. [0158] The reaction was conducted in an agitated temperature-controlled reactor. BPL was fed using a metering pump from a stainless steel cylinder. The reaction system was equipped with sulfuric acid solution scrubber designed to neutralize entire contents of BPL feed vessel. [0159] A reactor was charged with 2955 grams of 29wt% ammonia solution and then pressurized to 40 psig with N₂ (to provide positive pressure differential across the BPL metering pump). The agitator was turned on at about 400 rpm and chilled to 9°C. 535 grams of BPL was connected to the feed system, and pressurized to 16 psig with N₂. BPL feed rate was increased. The reactor temperature was maintained at 9-10°C throughout the duration of continuous BPL feed (120 minutes). Once all the BPL was fed to the reactor, the feed was switched to de-ionized water. About 100 grams of water were fed into the reactor to clear the feed line and feed pump from BPL. The reaction was sampled 90 minutes after BPL addition and residual BPL was not detected by NMR analysis. The reaction mixture was drained from the reactor for final product recovery. Results [0160] The metered BPL addition resulted in well-controlled reaction temperature. Near- instantaneous reaction of BPL with concentrated aqueous ammonia solution was observed. Minor reactor temperature increase (~1°C) upon an increase of BPL feed rate was compensated by decreasing CTB set-point. The reactor cooled down from about 9-10°C to about 7°C within several minutes after BPL feed was stopped. [0161] Tables 3A and 3B present reaction conditions and selectivity to 3-HP amide and other compounds produced. The selectivity to 3-HP amide was 89%, and 3-hydroxypropionic acid was detected. Table 3A. Quantities of materials and reaction conditions for the synthesis of 3-HP amide

Table 3B. Selectivity to 3-HP amide and other products observed

[0162] Conducting reaction of BPL with aqueous ammonia at well-controlled conditions, such as reaction temperature and rate of BPL addition, resulted in higher selectivity to 3-HP amide product. Example 8

Effect of NH₄OH:BPL Ratio on 3-HP Amide Synthesis

[0163] This example evaluates the effect of the NH₄OH:BPL ratio on the selectivity to 3-HP amide. The same materials and procedures were used in this example as in Example 7 above, except the following: 2891 grams of 29wt% ammonia were charged to reactor and 704 grams of BPL were fed at the rate of 5.2 g/hr. [0164] The metered BPL addition resulted in well-controlled reaction temperature. Similar to Example 7 above, near-instantaneous reaction of BPL with concentrated aqueous ammonia solution was observed. Tables 4A and 4B present reaction conditions and selectivity’s to 3-HP amide and other compounds produced. The selectivity to 3-HP amide was 89%.

Table 4A. Quantities of materials and reaction conditions for the synthesis of 3-HP amide

Table 4B. Selectivity to 3-HP amide and other products observed

[0165] Conducting reaction of BPL with aqueous ammonia at well controlled conditions, such as reaction temperature and rate of BPL addition, resulted in higher selectivity to 3-HP amide. Reduction of NH₄OH:BPL from 3.3:1 in Example 7 to 2.4:1 in this example did not affect selectivity to 3-HP amide (reduction of ammonia use by 25%).775 grams of crude 3-HP amide were produced. Example 9

Acrylonitrile Synthesis Using Al₂O₃

[0166] This example demonstrates the production of acrylonitrile by dehydration of 3- hydroxypropanamide using alumina (Al₂O₃). Reactor Setup [0167] A continuous tubular reactor was used for the production of acrylonitrile by dehydration of 3-hydroxypropanamide. This example was conducted using a GC injection port which could be heated uniformly. The glass liner in the GC was used to as a substitution for tubular reactor. Small amount of catalyst was placed in the liner packed with inert glass wool on both sides. Catalyst Preparation [0168] The Al₂O₃ catalyst used was received in a form of 1/8-inch pellets. It was crushed and sieved (250~600 μm) before loading into the reactor. Feedstock preparation [0169] The feedstock 3-HP amide was dissolved in deionized water, and was injected into the injection port by a micro-syringe. The feed liquid was observed to evaporate under reaction temperature, and pushed through the catalyst bed under the He carrier gas. With the adjustment of the catalyst amount and/or carrier gas flow rate, different residence time could be realized. The injection port could be heated with a heating capacity to 400°C. The effluent coming from the reaction directly went to the GC column for separation and quantitative analysis. General Procedure

[0170] 3-HP amide was weighed into an autosampler vial mini insert, and distilled water was added. The 3-HP amide dissolved, resulting in an 11.08% solution (w/w). A GC injection port liner (inverted cup design) was filled with a small plug of glass wool just above the cup to support the Al₂O₃ particles. Sieved Al₂O₃ was added to give a bed 0.2 cm in length. Additional glass wool was added above the Al₂O₃ bed to keep it in place. A deactivated open tube liner containing just glass wool was also used for blank test. A GC coupled with FID detector was used for product analysis. The total Helium flow through the liner was held at 42 mL/min with the liners at 400°C. The GC column used had a dimension of 15 meter*0.32mm*0.25um. Results

[0171] The thermal stability of 3-HP amide was investigated without the presence of catalyst.3-HP amide was observed to have a fair stability under elevated temperature up to the 400°C in a short period time. The formation of acrylamide was less than 1% and no 3-HP amide or ammonia was detected by GC. [0172] After that, 3-HP amide aqueous solution was injected to the reaction with a packed Al₂O₃ catalyst bed (0.2 cm) under 400°C. The original GC data for 15 injections are listed in Table 5 below, and the compiled results are showed in FIG.9. The conversion of 3-HP amide was observed to be 100% for each injection. The major species found in the product was acrylonitrile (50%).

Conclusion

[0173] This example of 3-HP amide dehydration using Al₂O₃ catalyst demonstrated conversion of 3-HP amide to acrylonitrile. Acrylonitrile was the major product detected by GC. Example 10

Acrylonitrile Synthesis Using Nb₂O₅

[0174] This example demonstrates the production of acrylonitrile by dehydration of 3- hydroxypropanamide using Nb₂O₅. This example was conducted using a GC injection port, as described in Example 9 above.

Example 11

Acrylonitrile Synthesis

[0175] This example demonstrates production of acrylonitrile using alumina, in which molten 3-HP amide was fed through a vertical tubular reactor under a continuous mode. [0176] A vapor phase catalytic reaction system was configured as follows: 30 g of 3- hydroxypropanamide (99%) was prepared and added to the reactor vessel. Catalyst reactor was packed with 1 g of a 30-60 mesh Al₂O₃ catalyst and 20 g of silicone carbide as an inert support before and after the catalyst bed. Source material was warmed up under 80°C and fed to a fixed bed reactor by a metering pump at a rate of about 10 WHSV. The reactor temperature was kept at 350° C. Samples were collected in approximately half an hour increment for 1 hour. Samples were analyzed by NMR and GC-FID for acrylonitrile, acrylamide, acrylic acid, 3- hydroxypropanamide, and other potential products. Results for conversion and selectively were calculated using equations below:

[0177] Results showed a total conversion of 3-HP amide acid of 100%. Acrylonitrile selectivity was 13%. Other products detected from the sample include acrylamide and polyamide.

Claims

CLAIMS What is claimed is:

1. A method of producing a compound of formula (3-I) and/or a compound of formula (3):

the compound of formula (2) is

, wherein R¹ is as defined above for formulae (3-I) and (3), and the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a mixed oxide, a transition metal complex, or an aluminum complex, or any combination thereof; or the dehydration agent comprises a solid metal oxide, a solid acid, an acid, a weak acid, a strong acid, an ion-exchange resin, an aluminosilicate, or any combination thereof.

2. The method of claim 1, further comprising combining a compound of formula (1) with ammonia to produce the compound of formula (2), wherein:

the compound of formula (1) is wherein R¹ is as defined above for

formulae (3-I) and (3).

3. The method of claim 2, wherein the combining of the compound of formula (1) with ammonia further produces a compound of formula (2-I):

wherein R¹ is as defined above for formulae (3-I) and (3).

4. The method of any one of claims 1 to 3, further comprising isolating the compound of formula (2-I).

5. A method of producing a compound of formula (3-I) and/or a compound of formula (3):

the compound of formula (1) is

6. The method of claim 2 or 3, wherein: the ammonia is aqueous ammonia, or the ammonia is liquid ammonia, or the ammonia is anhydrous ammonia; or anhydrous gaseous ammonia.

7. The method of any one of claims 1 to 5, wherein: R¹ is H; or R¹ is alkyl; or R¹ is methyl or ethyl.

8. The method of any one of claims 1 to 7, further comprising isolating the compound of formula (3-I) or the compound of formula (3), or both.

9. The method of any one of claims 1 to 8, wherein the dehydration agent comprises phosphorous pentoxide,an organophosphorous compound, a carbodiimide compound, a triazine compound, or an organosilicon compound, or any combinations thereof.

10. The method of any one of claims 1 to 8, wherein the dehydration agent comprises a transition metal complex.

11. The method of claim 10, wherein the transition metal complex comprises at least one halide or oxide ligand.

12. The method of any one of claims 1 to 8, wherein the dehydration agent comprises an aluminum complex.

13. The method of any one of claims 1 to 12, wherein the dehydration agent further comprises a solid support.

14. The method of any one of claims 1 to 8, wherein the dehydration agent comprises a zeolite.

15. The method of any one of claims 1 to 14, wherein the compound of formula (2) undergoes dehydration to produce the compound of formula (3-I) and/or the compound of formula (3), by passing the compound of formula (2) in the vapor phase through a heated reactor containing the dehydration agent.

16. The method of claim 15, wherein the reactor is a packed bed reactor, a fluidized bed reactor, or a moving bed reactor.

17. A method, comprising: combining a compound of formula (1) and ammonia in a reactor at an average temperature suitable to produce a compound of formula (2) with a selectivity of greater than 50%, wherein:

the compound of formula (1) is

the compound of formula (2) is

wherein R¹ is H or alkyl.

18. A method, comprising: combining a compound of formula (1) and ammonia in a reactor to produce a compound of formula (2), a compound of formula (3-I), and/or a compound of formula (3), or any isomers of the foregoing (as the case may be), with a selectivity of greater than 50%, wherein:

the compound of formula (1) is

the compound of formula (2) is

the compound of formula (3-I) is , and

the compound of formula (3) is

wherein R¹ is H or alkyl.

19. The method of claim 17 or 18, wherein the temperature of the reactor is maintained at an average temperature suitable to produce the compound of formula (2), the compound of formula (3-I), and/or the compound of formula (3), or any isomers of the foregoing (as the case may be), with the selectivity of greater than 50%.

20. The method of any one of claims 17 to 19, wherein the compound of formula (1) is added drop-wise to the reactor containing the ammonia.

21. The method of any one of claims 17 to 19, wherein the compound of formula (1) is added by single injection to the reactor containing the ammonia.

22. A method, comprising: providing ammonia to a reactor; adding a first portion of a compound of formula (1) to the reactor, wherein:

the compound of formula (1) is , wherein R¹ is H or alkyl;

wherein R¹ is as defined above, and wherein the temperature of the reactor is controlled to an average temperature suitable to produce the compound of formula (2).

23. A method, comprising: cofeeding a compound of formula (1) and ammonia to a heterogeneous catalyst bed to produce a compound of formula (2), wherein:

the compound of formula (1) is

,

the compound of formula (2) is

wherein R¹ is H or alkyl

24. The method of claim 23, wherein the heterogeneous catalyst bed comprises a metal oxide, a basic zeolite, an alkali metal exchanged zeolite, a base modified alumina, or a solid“super base”.

25. The method of claim 22 or 23, wherein the reactor is maintained at a temperature where the compound of formula (2) is a gas.

26. The method of any one of claims 22 to 25, wherein the compound of formula (2) is produced anhydrously.

27. The method of any one of the preceding claims, wherein the compound of formula (3-I) is acrylamide, and the compound of formula (3) is acrylonitrile.

28. A method of producing polyacrylamide, comprising: producing acrylamide according to the method of claim 27; and polymerizing the acrylamide to produce polyacrylamide.

29. A method of producing polyacrylonitrile, comprising: producing acrylonitrile according to the method of claim 27; and polymerizing the acrylonitrile to produce polyacrylonitrile.

30. A method of producing a carbon fiber, comprising: producing polyacrylonitrile according to the method of claim 27; and producing a carbon fiber from the polyacrylonitrile.

31. A system, comprising a continuous stirred-tank reactor comprising: a first inlet configured to receive a compound of formula (1):

wherein the compound of formula (2) is: , wherein R¹ is as defined above for formula (1).

32. A system, comprising: a reactor, comprising: an inlet configured to receive ammonia and a compound of formula (1), wherein the ammonia is in gaseous form and the compound of formula (1) is in liquid form,

wherein the compound of formula (1) is , wherein R¹ is H or alkyl;

wherein the compound of formula (2) is , wherein R¹ is as

defined above for formula (1). 33. The system of claim 31 or 32, wherein the compound of formula (2) is provided in molten form.