Amide and nitrile compounds and methods for making and using same

Abstract

Systems and methods are provided for the industrial production of nitriles, including precursors for making certain nitriles and derivatives made from nitriles, from partially or fully renewable resources. The present invention provides a method for producing a compound of formula (3-I) and / or a compound of formula (3) by dehydration of a β-hydroxyamide. TIFF2022130492000127.tif18170 TIFF2022130492000128.tif14170 In the formula, R 1 represents H or alkyl.

Description

[Technical field]

[0001] <CROSS REFERENCE TO RELATED APPLICATIONS> 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 by reference in its entirety.

[0002] The present disclosure relates generally to the production of amide and / or nitrile products, and more particularly, to the production from at least epoxides, beta-lactones, and / or beta-hydroxyamides. [Background technology]

[0003] Nitrogen-containing compounds such as amides and nitriles are valuable compounds that can be used in a variety of commercial and industrial applications. For example, acrylonitrile can be used as a starting material in the production of polymer and monomer precursors. Various methods for the industrial production of acrylonitrile are known in the art. For example, acrylonitrile can be prepared by catalytic ammoxidation of propylene, where propylene, ammonia and air are contacted with a catalyst at high temperature and pressure. However, this process generally requires the use of harsh reaction conditions and expensive reagents. Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention solves the problems of the prior art by providing systems and methods for the industrial production of nitriles, including precursors for making certain nitriles and derivatives made from nitriles, from partially or fully renewable resources, as well as systems and methods for the industrial production of such compounds, including systems and methods for producing other compounds desirable in the art.

[0005] Provided herein are methods and systems for producing amide and / or nitrile products. Advantageously, certain preferred methods and systems provided are bio-based alternatives to conventional methods and systems for producing nitriles and amides with reduced cost and environmental harm. [Means for solving the problem]

[0006] Preferred embodiments of the present invention relate to systems and methods for producing amide 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 and / or nitrile products from bio-based epoxides and / or bio-based beta-lactones. In certain embodiments, the systems and methods may be modified to selectively produce a preferred amide or nitrile product in higher yield than one or more other products. Advantageously, the systems and methods of the present invention may be integrated into conventional systems and processes to reduce the environmental impact of producing many commercial products.

[0007] For example, in some embodiments, an amide compound of formula (3-I) and / or a nitrile compound of formula (3)

[0008] [ka]

[0009] [ka] (In the formula, R 1 is H or alkyl) or an isomer thereof, This method is combining an amide compound of formula (2) with a dehydrating agent to produce a nitrile compound of formula (3-I) and / or an amide compound of formula (3), or an isomer thereof; The amide compound of formula (2) is

[0010] [ka] (In the formula, R 1 is as defined above for formula (3-I) and formula (3).

[0011] In certain embodiments of the above, the method further comprises combining the beta-lactone compound of formula (1) with ammonia to produce an amide compound of formula (2): The beta-lactone compound of formula (1) is

[0012] [ka] (In the formula, R 1 is as defined above for formula (3-I) and formula (3).

[0013] In some variations of the above method, the dehydration agent comprises phosphorus pentoxide, an organophosphorus 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 phosphorus pentoxide, an organophosphorus compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex or an aluminum complex, or any combination thereof.

[0014] In some variations of the above methods, the dehydration agent comprises titanic acid, metal oxide hydrate, metal sulfate, metal oxide sulfate, metal phosphate, metal oxide phosphate, mineral acid, carboxylic acid or salt thereof, acidic resin, acidic zeolite, clay, or any combination thereof. In certain variations of the above methods and systems, the dehydration agent comprises a zeolite.

[0015] In another embodiment, combining the compound of formula (1) and ammonia in a reactor to produce a compound of formula (2) A method is provided, comprising: The compound of formula (1)

[0016] [ka] and The compound of formula (2)

[0017] [ka] and In the formula, R 1 is H or alkyl.

[0018] In certain variations of the above, the selectivity of formula (2) is greater than 10%, greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, or greater than 90%.

[0019] In some embodiments, combining the 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). A method is provided, comprising: The compound of formula (1)

[0020] [ka] and The compound of formula (2)

[0021] [ka] and The compound of formula (3-I) is

[0022] [ka] and The compound of formula (3)

[0023] [ka] and In the formula, R 1 is H or alkyl.

[0024] In certain variations of the above, the selectivity of formula (2) is greater than 10%, greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, or greater than 90%; or the selectivity of formula (3) is greater than 10%, greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, or greater than 90%; or the selectivity of formula (3-I) is greater than 10%, greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, or greater than 90%.

[0025] In some variations of the above, 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, a method is provided that includes producing an amide, such as acrylamide, according to any of the methods herein and polymerizing the amide. In one variation in which the amide is acrylamide, the polymer is polyacrylamide. In another aspect, a method is provided that includes producing a nitrile, such as acrylonitrile, according to any of the methods herein and polymerizing the nitrile. In one variation in which the nitrile is acrylonitrile, the polymer is polyacrylonitrile. In yet another aspect, a method is provided for producing carbon fibers, including producing polyacrylonitrile according to any of the methods herein and producing carbon fibers from the polyacrylonitrile.

[0026] In another aspect, a system for producing an amide product and / or a nitrile product from at least a beta-lactone and / or a beta-hydroxyamide is provided. In certain embodiments, the system provided includes one or more reactors sized, shaped, and configured to provide the amide product and / or the nitrile product. In certain embodiments, the one or more reactors may be configured as a continuous stirred tank reactor, a fixed catalyst bed reactor, a fluidized catalyst bed reactor. In certain embodiments, the system may be configured for use with a heterogeneous catalyst. In other embodiments, the system may be configured for use with a homogeneous catalyst.

[0027] In some variations of the above, the compounds of the invention have a biobased content of greater than 0% and less than 100%. In certain variations of the above, the compounds of the invention have a biobased content of at least 10%, at least 20%, at least 50%, at least 70%, at least 95%, or 100%.

[0028] In some variations, biobased content can be determined based on the following: % Biobased Content = [Bio(organic) Carbon] / [Total (organic) Carbon] x 100% as determined by ASTM D6866 (Standard Test Method for Determination of Biobased Content of Solid, Liquid and Gas Samples Using Radiocarbon Analysis).

[0029] The bio-based content of the composition of the present invention may depend on the bio-based content of the beta-lactone used. For example, in some variations of the methods described herein, the beta-lactone used to produce the amide and / or nitrile products described herein may have a bio-based 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 and / or nitrile products described herein may have a bio-based 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, beta-lactone obtained from a renewable resource is used. In other variations, at least a portion of the beta-lactone used is obtained from a renewable resource and at least a portion of the beta-lactone is obtained from a non-renewable resource.

[0030] The biobased content of the beta-lactone can depend, for example, on the biobased content of the epoxide and carbon monoxide used. In some variations, both the epoxide and carbon monoxide are obtained from renewable resources.

[0031] The application can be best understood by referring to the following description in conjunction with the accompanying drawings, in which like parts may be referenced with like numerals, and in which: [Brief description of the drawings]

[0032] [Figure 1] 1 is an exemplary reaction scheme for producing a compound of formula (3). [Diagram 2] 1 is an exemplary reaction scheme for producing a compound of formula (3). [Diagram 3] 1 is an exemplary reaction scheme for producing a compound of formula (3). [Figure 4] 1 is an exemplary reaction scheme for producing a compound of formula (3). [Figure 6] 1 is an exemplary reaction scheme for producing a compound of formula (3). [Diagram 5] 1 is an exemplary reaction scheme for producing a compound of formula (3-I). [Figure 7A] 1 is a reaction scheme showing how aqueous ammonia contains a dynamic equilibrium mixture of ammonia gas / water and ammonium. [Figure 7B] 1 is an exemplary reaction scheme involving beta-propiolactone and ammonium / ammonia. [Figure 8] 1 is a graph showing the results of an experiment conducted in Example 9 involving the dehydration of 3-hydroxypropanamide (abbreviated as "3-HP amide") using alumina (Al2O3) to produce acrylonitrile. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0033] The following description sets forth example methods, parameters, etc., however, it should be recognized that such description is not intended to limit the scope of the present disclosure, but is instead provided as a description of example embodiments.

[0034] Provided herein are methods and systems for producing amide and / or nitrile products from at least a beta-lactone and / or a beta-hydroxyamide. In certain preferred embodiments, the amide product comprises acrylamide and the nitrile product comprises acrylonitrile. In certain variations, the beta-lactone may be produced by carbonylation of an epoxide with carbon monoxide.

[0035] In some embodiments, methods are provided for producing acrylonitrile and other nitrile compounds from beta hydroxyamides. For example, referring to Figure 1, beta hydroxyamides of formula (2) are combined with a dehydrating agent to produce acrylonitrile or other nitrile compounds of formula (3), or isomers thereof.

[0036] In another embodiment, a method is provided for producing acrylonitrile and other nitrile compounds from lactones. For example, referring to Figure 2, a beta-lactone of formula (1) can be combined with ammonia to produce a beta-hydroxyamide of formula (2), which can then be converted to a compound of formula (3), or an isomer thereof, via the exemplary reaction shown in Figure 1.

[0037] In another example, referring to FIG. 3, beta-lactone of formula (1) can be combined with ammonia in water (also called aqueous ammonia) and a dehydrating agent to produce acrylonitrile compounds or other nitrile compounds of formula (3), or isomers thereof.

[0038] In yet another example, referring to Figure 4, there is shown the conversion of a beta-lactone of formula (1) to a nitrile compound of formula (3) or an isomer thereof, where intermediate compounds of formula (2) and (3-I) may undergo dehydration to produce the nitrile. In one aspect, a method is provided that includes combining a compound of formula (1) and ammonia in a reactor to produce a compound of formula (2) with greater than 80% selectivity, respectively. In another aspect, a method is provided that includes 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 greater than 80% selectivity.

[0039] In some variations of the above, the selectivity is greater than 10%, greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 85%, greater than 90%, greater than 95%, greater than 96%, greater than 97%, greater than 98%, or greater than 99%. The selectivity can be controlled by one or more parameters. For example, in some variations, the temperature of the reactor is maintained at an average temperature between -20°C and 50°C, or between 10°C and 35°C. In other variations, the compound of formula (1) is added dropwise to the reactor containing ammonia. In another variation, the compound of formula (1) is added by a single injection to the reactor containing ammonia.

[0040] In yet another variation, a method is provided that includes providing a first portion of a compound of formula (1) to a reactor, adding ammonia, and maintaining an average temperature of the reactor to produce a compound of formula (2). In one variation, the method further includes isolating the compound of formula (2). In certain embodiments, the step of maintaining the average temperature is performed between -20°C and 50°C.

[0041] In yet another variation, a method is provided that includes co-feeding the compound of formula (1) and ammonia to a reactor and maintaining an average temperature of the reactor to produce a compound of formula (2). In one variation, the method further includes isolating the compound of formula (2). In certain embodiments, the compound of formula (1) is fed to the reactor as a liquid in contact with the heterogeneous catalyst. In certain variations, the flow rates of the compound of formula (1) and ammonia are controlled separately. In certain variations, the ammonia is present in excess in the reactor. In other embodiments, the method further includes collecting a product stream from the reactor that includes the compound of formula (2) and excess ammonia. In one variation, the compound of formula (2) is collected in liquid form. In yet another embodiment, the method further includes separating the excess ammonia from the product stream and recycling the separated ammonia to the reactor. In other variations, the heterogeneous catalyst bed includes any of the heterogeneous dehydration 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 "superbase". In other variations, the temperature of the reactor is maintained within the range of 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 at which the compound of formula (2) is a gas. In another variation, the compound of formula (2) is produced anhydrous.

[0042] In some variations of the above, the compound of formula (1) is combined with liquid ammonia. In other variations of the above, the compound of formula (1) is combined with ammonia in the absence of a solvent. In one particular variation, the compound of formula (1) is combined with ammonia (or ammonium hydroxide) in water. In other words, in one particular variation, the ammonia is aqueous ammonia. With reference to FIG. 7A, it should be understood that aqueous ammonia generally comprises a dynamic equilibrium mixture of ammonia gas / water and ammonium hydroxide. In another variation, 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 removing water before the hydration reaction) can be avoided. Ammonia can be obtained from commercially available sources or produced according to any method known in the art.

[0043] In another variation, the compound of formula (1) is combined with ammonia at elevated temperature. In another variation, the compound of formula (1) is combined with ammonia and an additional basic compound.

[0044] In one particular variation of the above, ammonia is combined with a compound of formula (1) along with any of the dehydrating agents described herein, as shown in Figure 3. In another variation, ammonia is combined with a compound of formula (1) to first produce a beta-hydroxyamide of formula (2), and then any of the dehydrating agents described herein is combined with the beta-hydroxyamide of formula (2) to produce a compound of formula (3-I) and / or a compound of formula (3), or an isomer thereof, as shown in Figures 2 and 4.

[0045] In another embodiment, referring to Figure 5, there is provided a method for producing an amide of formula (3-I) or an isomer thereof from a beta hydroxyamide of formula (2). In yet another embodiment, referring to Figure 6, there is provided a method for producing a nitrile of formula (3) or an isomer thereof from an amide of formula (3-I) or an isomer thereof. Exemplary reactions shown in Figures 5 and 6 include dehydration reactions that may use any of the dehydrating agents described herein.

[0046] In certain preferred embodiments, with respect to formulas (1), (2), (3-I) and (3), R 1 is H. In such embodiments, acrylonitrile can be produced from beta-propiolactone via 3-hydroxypropiamide and acrylamide. In certain variations, 3-hydroxypropiamide and / or acrylamide can be isolated and optionally further purified.

[0047] The amide and / or nitrile products produced according to the methods and systems herein can be used in a variety of 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 a variety of applications, including carbon fibers, etc.

[0048] The acrylamide and acrylonitrile compounds, as well as other compounds which may be produced, and the methods including amides, lactones and dehydrating agents which may be used, are discussed in more detail below.

[0049] <Acrylonitrile compounds and other nitrile compounds> In one embodiment, a method is provided for 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 obtain a crude aqueous solution of 3-hydroxypropanamide. The crude solution is then purified with a resin to remove impurities, and then water is removed to obtain pure 3-hydroxypropanamide in solid form. The pure 3-hydroxypropanamide can then be continuously fed to a fixed-bed reactor packed with a dehydration catalyst. The 3-hydroxypropanamide solid can be warmed to a temperature above its melting point and then further mixed / vaporized with a nitrogen sweep gas in a preheat zone before passing through the catalyst bed. The dehydration reaction of 3-hydroxypropanamide to acrylonitrile in the presence of water can occur on the surface of the catalyst.

[0050] In some embodiments, the acrylonitrile compounds and other nitrile compounds produced according to the methods herein are compounds of formula (3):

[0051] [ka] (In the formula, R 1 is H, alkyl, alkenyl, cycloalkyl or aryl) or an isomer thereof.

[0052] "Alkyl" refers to a monoradical unbranched or branched saturated hydrocarbon chain. In some embodiments, alkyl is an alkyl group having 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 1-3alkyl), or 1-2 carbon atoms (i.e. C 1-2 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 can be included. Thus, for example, "butyl" can include n-butyl, sec-butyl, isobutyl, and t-butyl, and "propyl" can include n-propyl and isopropyl.

[0053] "Alkenyl" refers to an unsaturated linear or branched monovalent hydrocarbon chain or combinations 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). Alkenyl groups may be in the "cis" or "trans" configuration, or in the "E" or "Z" configuration. 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.

[0054] "Cycloalkyl" refers to a carbocyclic non-aromatic group bonded via a ring carbon atom. Examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

[0055] "Aryl" refers to a monovalent aromatic carbocyclic group of 6 to 18 ring carbon atoms having a ring system having a single ring or multiple condensed rings. Examples of aryl include phenyl, naphthyl, and the like.

[0056] In some variations, R 1The alkyl, alkenyl, cycloalkyl, or aryl of may be optionally substituted. The term "optionally substituted" means that the specified group is unsubstituted or substituted with one or more substituents. 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, where 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 haloalkyl. In certain embodiments, the 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, -CF5, -CH4OMe, and -OH.

[0057] In certain preferred embodiments, R 1 is H or alkyl.

[0058] In some variations, R 1 is H, and the compound of formula (3) is

[0059] [ka] (also known in the art as acrylonitrile).

[0060] In another variation, R 1 is alkyl. In one particular variation, R 1 is C 1-6 In one variation, R 1 is methyl or ethyl. 1 is methyl, the compound of formula (3)

[0061] [ka] or its isomer (also known in the art as crotononitrile). 1 When is ethyl, the compound of formula (3)

[0062] [ka] or its isomer (also known in the art as 2-pentenenitrile).

[0063] "Alkyl" refers to a monoradical unbranched or branched saturated hydrocarbon chain. In some embodiments, alkyl is an alkyl group having 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 1-2 carbon atoms (i.e. C 1-2 In other embodiments, alkyl groups can 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 can be included. Thus, for example, "butyl" can include n-butyl, sec-butyl, isobutyl, and t-butyl, and "propyl" can include n-propyl and isopropyl.

[0064] Moreover, when a range of values ​​is listed, it is understood that each value and subrange within that range is intended to be encompassed. 1-6 "Alkyl" (which may also be referred to as 1-6C alkyl, C1-C6 alkyl, or C1-6 alkyl) refers to 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 is intended to be encompassed.

[0065] <Acrylamide and other amides> In some embodiments, acrylamide or other amides can be used to produce acrylonitrile and other nitrile compounds. In some variations, such amides have the formula (3-I):

[0066] [ka] (In the formula, R 1 is H, alkyl, alkenyl, cycloalkyl, or aryl.

[0067] In certain preferred embodiments, R 1 is H or alkyl.

[0068] In some variations, R 1 is H, and the compound of formula (3-I) is

[0069] [ka] (or acrylamide). In other variations, R 1 is alkyl. In one particular variation, R 1 is C 1-6 In one variation, R 1 is methyl or ethyl. 1 is methyl, the compound of formula (3-I) is

[0070] [ka] or

[0071] [ka] (also known in the art as but-2-enamide). 1 is ethyl, the compound of formula (2) is

[0072] [ka] or

[0073] [ka] (also known in the art as pent-2-enamide).

[0074] Generally, when a compound of formula (3-I) or an isomer thereof is used to produce a compound of formula (3) or an isomer thereof, R 1 It should be understood that is as defined for equation (3).

[0075] Acrylamides and other amides, such as the compound of formula (3-I), can be obtained as described herein or from any commercial source, or can be produced according to any method known in the art.

[0076] In certain embodiments, the compound of formula (3-I) produced according to the methods herein may be isolated. In some variations, the compound of formula (3-I) produced according to the methods herein may be isolated and purified. The compound of formula (3-I) produced according to the methods herein may be isolated.

[0077] <Beta-hydroxyamides and other hydroxyamides> In some embodiments, the beta hydroxyamides and other hydroxyamides that may be used to produce acrylonitrile and other nitrile compounds according to the methods herein are compounds of formula (2):

[0078] [ka] (In the formula, R 1 is H, alkyl, alkenyl, cycloalkyl, or aryl.

[0079] In certain preferred embodiments, R 1 is H or alkyl.

[0080] In some variations, R 1 is H, and the compound of formula (2) is

[0081] [ka] (or 3-hydroxypropanamide). In another variation, R 1 is alkyl. In one particular variation, R 1 is C 1-6 In one variation, R 1 is methyl or ethyl. 1 is methyl, the compound of formula (2) is

[0082] [ka] (or 3-hydroxybutanamide). 1 When is ethyl, the compound of formula (2) is

[0083] [ka] (or 3-hydroxypentanamide).

[0084] Generally, when a compound of formula (2) is used to produce a compound of formula (3) or an isomer thereof, R 1 It should be understood that is as defined for equation (3).

[0085] Beta hydroxyamides and other amides, such as compounds of formula (2), can be obtained as described herein or from any commercial source, or can be produced according to any method known in the art.

[0086] In certain embodiments, the compound of formula (2) produced according to the methods herein may be isolated. In some variations, the compound of formula (2) produced according to the methods herein may be isolated and purified. The compound of formula (2) produced according to the methods herein may be isolated.

[0087] <Beta-lactone and other lactones> In some embodiments, beta-lactones can be used to produce beta-hydroxyamides, acrylamides, acrylonitrile and other compounds according to the methods herein. In certain embodiments, beta-lactones have the formula (1):

[0088] [ka] (In the formula, R 1 is H, alkyl, alkenyl, cycloalkyl, or aryl.

[0089] In certain preferred embodiments, R 1 is H or alkyl.

[0090] In some variations, R 1 is H, and the compound of formula (1) is

[0091] [ka] (also known in the art as beta-propiolactone).

[0092] In another variation, R 1 is alkyl. In one particular variation, R 1 is C 1-6 In one variation, R 1 is methyl or ethyl. 1 is methyl, the compound of formula (1) is

[0093] [ka] (also known in the art as beta-butyrolactone). 1 is ethyl, the compound of formula (1) is

[0094] [ka] (also known in the art as beta valerolactone).

[0095] Generally, when a compound of formula (1) is used to produce a compound of formula (2) or a compound of formula (3), or an isomer thereof, R 1 It should be understood that is as defined for formula (2) or formula (3).

[0096] Beta-lactones, such as the compound of formula (1), can be obtained from any commercially available source or produced according to any method known in the art. For example, beta-propiolactone can be obtained by reacting ethylene oxide and carbon monoxide under appropriate conditions. In some variations, the amide and / or nitrile products can 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 can be produced from the corresponding epoxides in column A of the table.

[0097] Table A.

[0098] [Table 1] TIFF0007634279000030.tif220170TIFF0007634279000031.tif228170TIFF0007634279000032.t if233170TIFF0007634279000033.tif222170TIFF0007634279000034.tif223170TIFF00076342790 00035.tif236170TIFF0007634279000036.tif191170TIFF0007634279000037.tif237170TIFF000 7634279000038.tif233170TIFF0007634279000039.tif238170TIFF0007634279000040.tif222170

[0099] Beta-lactones, such as the compounds of formula (1), can be obtained from renewable raw materials. For example, when beta-propiolactone is produced from ethylene oxide and carbon monoxide, either or both of the ethylene oxide and carbon monoxide can be obtained from renewable raw materials using methods known in the art. When beta-lactones, such as the compounds of formula (1), are partially or completely obtained from renewable raw materials, polyamides produced from such beta-lactones according to the methods described herein have a bio-content greater than 0%.

[0100] Various techniques for determining the biocontent of a material are known in the art. For example, in some variations, the biocontent of a material may be measured using the ASTM D6866 method, which allows for the determination of the biocontent of a material using accelerator mass spectrometry, liquid scintillation counting, and radiocarbon analysis by isotopic mass spectrometry. A biocontent result may be derived by assigning 100% to 107.5 pMC (percent modern carbon) and 0% to 0 pMC. For example, a sample measuring 99 pMC would yield an equivalent biocontent result of 93%. In one variation, the biocontent may be determined according to ASTM D6866 revision 12 (i.e., ASTM D6866-12). In another variation, the biocontent may be determined according to the procedure of method B of ASTM-D6866-12. Other techniques for assessing the biocontent of a material 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 WO 2009 / 155086.

[0101] <Dehydrating agent> Dehydration generally involves the conversion of a carbon-carbon single bond to a carbon-carbon double bond to produce a water molecule. The dehydration reactions described herein may occur in the presence of a suitable homogeneous or heterogeneous catalyst.

[0102] In some embodiments, suitable dehydration catalysts may include acids, bases, and oxides. Examples of suitable acids may include H2SO4, HCl, titanic acid, metal oxide hydrates, metal sulfates (MSO4, where M can be Zn, Sn, Ca, Ba, Ni, Co, or other transition metals), metal oxide sulfates, metal phosphates (e.g., M3(PO4)2, where M can be Ca, Ba), metal phosphates, metal oxide phosphates, carbon (e.g., transition metals on carbon supports), mineral acids, carboxylic acids, their salts, acidic resins, acidic zeolites, clays, SiO2 / H3PO4, fluorinated Al2O3, phosphotungstic acid, phosphomolybdic acid, silicomolybdic acid, silicotungstic acid, 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, Al2O3, SiO2, ZnO2, SnO2, WO3, MnO2, Fe2O3, and V2O5.

[0103] In some embodiments, the dehydrating agent used in the methods described herein comprises phosphorus pentoxide, an organophosphorus compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a mixed oxide, a transition metal complex, or an aluminum complex.

[0104] In certain embodiments, the dehydrating agent used in the methods described herein may further comprise a solid carrier. Suitable solid carriers may include, for example, hydrotalcite.

[0105] The dehydrating agents can be obtained from commercially available sources or prepared according to methods known in the art.

[0106] <Phosphorus compounds> In certain embodiments, the dehydrating agent used in the methods described herein comprises a phosphorus compound.

[0107] In one variation, the dehydrating agent includes phosphorus pentoxide.

[0108] In some variations, the dehydrating agent comprises an organophosphorus compound. In one particular variation, the organophosphorus compound is an organophosphate. In one particular variation, the organophosphorus compound is an alkyl halophosphate or a cycloalkyl halophosphate. In one variation, the alkyl halophosphate is an alkyl dihalophosphate or a dialkyl halophosphate. In another variation, the cycloalkyl halophosphate is a cycloalkyl dihalophosphate or a dicycloalkyl halophosphate. In some variations of the above organophosphorus compounds, the alkyl is C1-C 10 In another variation of the above organophosphorus compound, cycloalkyl is C3-C 10 It is cycloalkyl.

[0109] "Cycloalkyl" refers to a carbocyclic, non-aromatic group bonded via a ring carbon atom, and if unsubstituted, contains only C and H. Cycloalkyls can consist of one ring or multiple rings. In some variations, cycloalkyls having two or more rings can be linked together by a C-C bond, fused, spiro or bridged, or combinations thereof. In some embodiments, cycloalkyls are C3-C4 10 Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclohexyl, adamantyl and decahydronaphthalenyl.

[0110] In yet another variation of the organophosphorus compound, the halophosphate is a chlorophosphate.In yet another variation of the organophosphorus compound, the halophosphate is a fluorophosphate.

[0111] Suitable organophosphorus compounds for use 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.

[0112] <Carbodiimide compound> In certain embodiments, the dehydrating agent comprises a carbodiimide compound.

[0113] In some variations, the carbodiimide compound is

[0114] [ka] where each R 4 and R 5 is independently alkyl or cycloalkyl. In certain variations of the above, R 4 and R 5 In another variation of the above, R 4 and R 5 are the same. In another variation, each R 4 and R 5 is independently cycloalkyl.

[0115] In one particular variation, each R 4 and R 5 is independently alkyl. In one particular variation, each R 4 and R 5 is independently C 1-6 In one variation, each R 4 and R 5 is independently methyl, ethyl, or propyl. 4 and R 5 are both methyl, ethyl, or propyl. 4 and R 5are both cyclohexyl. In yet another variation, R 4 is alkyl, R 5 is cycloalkyl.

[0116] Suitable carbodiimide compounds for use in the methods described herein include, for example,

[0117] [ka] (also known in the art as N,N'-dicyclohexylcarbodiimide), where R 4 and R 5 are both cyclohexyl.

[0118] <Triazine compounds> In certain embodiments, the dehydrating agent comprises a triazine compound. In one variation, the triazine compound is a 1,3,5-triazine and has the following structure:

[0119] [ka]

[0120] The triazine compounds described herein may be optionally substituted with one or more substituents. In some variations, the triazine compounds are substituted with one, two or three substituents. In certain variations, the substituents may be halo groups. For example, in certain variations, the triazine compounds are halo-substituted triazine compounds. In certain variations, the triazine compounds are 1,3,5-triazines substituted with one, two or three halo groups. In one variation, the triazine compounds are halo-substituted 1,3,5-triazines.

[0121] Suitable triazine compounds for use in the methods described herein include, for example:

[0122] [ka] (also known in the art as cyanuric chloride).

[0123] <Organosilicon compounds> In certain embodiments, the dehydrating 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 an aryl, halo, alkyl, alkoxy, or amino group.

[0124] In certain embodiments, the organosilicon compound is

[0125] [ka] where each R 6 , R 7 , R 8 and R 9 is (at each occurrence) independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy.

[0126] In another variation, the organosilicon compound is a silane. The silane may be unsubstituted (e.g., 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 an aryl, halo, alkyl, alkoxy, or amino group.

[0127] In certain embodiments, the organosilicon compound is

[0128] [ka] And each R 6 , R 7 , R 8 and R 9is independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy.

[0129] In one embodiment, the organosilicon compound is an arylsilane. In some variations, the arylsilane comprises 1, 2 or 3 aryl groups. In the above variations, the aryl group is phenyl. Suitable arylsilanes can include, for example, diphenylsilane and phenylsilane. In one variation, the organosilicon compound is Ph2SiH2. In another variation, the organosilicon compound is PhSiH3.

[0130] 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 includes one, two, or three 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 one, two, or three substituents (other than halo). In the above variations, the substituents of the halosilane are independently alkyl or aryl. In one variation of the above, the alkyl substituents of the halosilane are C 1-6 In another variation, the substituents of the halosilane are independently methyl or phenyl. Suitable halosilanes may include, for example, dialkyldihalosilanes, aryltrihalosilanes, arylalkyldihalosilanes, or aryltrihalosilanes. In one particular variation, the halosilane is a chlorosilane. Suitable chlorosilanes may include, for example, dimethyldichlorosilane, phenyltrichlorosilane, or phenylmethyldichlorosilane.

[0131] In another embodiment, the organosilicon compound is an alkoxysilane. In one particular variation, the alkoxysilane comprises an alkyl silicate. In one variation, the alkoxysilane is 1-6Suitable alkyl silicates include, for example, n-butyl silicate. In other variations, the alkoxysilane includes 1, 2, or 3 alkoxy groups. In certain variations of the above, 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 above, the alkyl substituents of the alkoxysilane are C 1-6 In another variation, the substituents of the alkoxysilane are independently methyl or phenyl. Suitable alkoxysilanes can include, for example, dimethoxy(methyl)phenylsilane.

[0132] In yet another embodiment, the organosilicon compound is an aminosilane. In one particular variation, the aminosilane is an alkylaminosilane. In one particular variation of the above, the aminosilane may be further substituted with one, two or three substituents (e.g., other than an amino group, including an alkylamino group). In one variation, the substituent of the aminosilane is an alkoxy group. In one variation of the above, the alkoxy substituent of the aminosilane is C 1-6 In another variation, the substituents of the aminosilane are independently methoxy or ethoxy. Suitable aminosilanes can include, for example, (3-aminopropyl)triethoxysilane.

[0133] In other embodiments, the organosilicon compound is a bis(trialkylsilyl)amine. In one variation, the organosilicon compound is a bis(trimethylsilyl)amine.

[0134] In some variations above, the silane described herein can be used in combination with alkylammonium halide as dehydrating agent.In one variation, the alkylammonium halide is tetrabutylammonium halide, such as tetrabutylammonium chloride or tetrabutylammonium fluoride.In a particular variation, the organosilicon compound and alkylammonium halide are provided as a mixture (e.g., in a solvent) or combined separately.

[0135] <Transition metal complexes> In certain embodiments, the dehydrating 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 bonded or complexed to the transition metal.

[0136] In certain variations of the above, the transition metal complex is provided in a solvent, hi other variations, the transition metal complex is provided in water or acetonitrile, or a mixture thereof.

[0137] In one embodiment, the transition metal complex is a metal halide. In some variations, the metal halide includes a group 10 metal or a group 12 metal. In one particular variation, the metal halide includes palladium or zinc. In one particular variation, the metal halide includes chloro. Suitable metal halides can include, for example, palladium chloride or zinc chloride.

[0138] In some variations of the above, 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.

[0139] In another embodiment, the transition metal complex comprises a Group 5 metal. In some variations, the transition metal complex comprises vanadium oxide. In one variation, the vanadium oxide is monomeric vanadium oxide. In one particular variation, the dehydrating agent comprises vanadium oxide and hydrotalcite. In one variation, the dehydrating agent comprises monomeric vanadium oxide and hydrotalcite. The vanadium oxide (including, for example, monomeric vanadium oxide) may be incorporated into the surface of the hydrotalcite.

[0140] <Aluminum complex> In certain embodiments, the dehydrating 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.

[0141] <Other heterogeneous dehydrating agents> In some variations, the dehydration agent is 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.

[0142] 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.

[0143] In certain variations, the dehydration agent comprises titanic acid, metal oxide hydrate, metal sulfate, metal oxide sulfate, metal phosphate, metal oxide phosphate, mineral acid, carboxylic acid or its salt, acidic resin, acidic zeolite, clay, or any combination thereof. In certain variations, the dehydration agent comprises H3PO4 / SiO2, fluorinated Al2O3, Nb2O3 / PO4 -3 , Nb2O3 / SO4 -2 , Nb2O5, H3PO4, phosphates, phosphotungstic acid, phosphomolybdic acid, silicomolybdic acid, silicotungstic acid, Mg2P2O7, MgHPO4, or any combination thereof.

[0144] In some variations, the dehydration agent comprises a zeolite. In certain variations, the zeolite is in the hydrogen or ammonia form, or is a metal-exchanged zeolite. In one variation, the metal-exchanged zeolite comprises Li, Na, K, Ca, Mg, or Cu. In another variation, the zeolite has a pore size in the range of 1-10 angstroms in diameter. In one variation, the zeolite is a medium pore zeolite. In some variations, the zeolite has a pore size of about 5-6 angstroms, or about 5.6*6.0 angstroms, or about 5.1*5.5-5.3*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.

[0145] In variations in which a heterogeneous dehydration agent is used as described above, the compound of formula (2) in the gas phase is passed through a heated reactor containing the dehydration agent, whereby the compound of formula (2) is dehydrated to produce a compound of formula (3-I) or a compound of formula (3), or a combination thereof. In one variation, the reactor is a packed bed reactor, a fluidized bed reactor, or a moving bed reactor.

[0146] <Dehydrating agent combination> 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 dehydration agents as described herein may be used.

[0147] In some embodiments, the dehydrating agent comprises a combination of an organosilicon compound and a transition metal complex. In a particular variation of the above combination, the organosilicon compound is N-methyl-N-(trimethylsilyl)trifluoroacetamide. In some variations of the above 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.

[0148] In other embodiments, the dehydration agent comprises a combination of a silane and a transition metal complex. In one particular variation of the above 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.

[0149] In another variation of the combination of silane and transition metal complex, the transition metal complex is a metal carbonate. In one particular variation, the metal carbonate includes iron. In one particular variation, the metal carbonate is iron carbonate. Suitable metal carbonates include, for example, Fe2(CO)9. In some variations of the above combination, the organosilicon compound is an alkoxyalkylsilane. In one particular variation, the alkoxyalkylsilane is diethoxymethylsilane. In one variation, the dehydrating agent includes a combination of iron carbonate and an alkoxyalkylsilane.

[0150] Exemplary combinations of dehydrating agents that can 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.

[0151] <Downstream Use> The acrylamide, acrylonitrile and other compounds produced according to the methods described herein can be used, in some variations, as monomers for the industrial production of polymers.

[0152] The compound of formula (3-I) produced according to the method herein can be used to produce one or more downstream products. For example, referring to FIG. 8B, the acrylamide produced according to the method herein can be used to produce polyacrylamide. Thus, in certain embodiments, a method is provided that includes 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, a method is provided for producing polyacrylamide, including producing acrylamide according to any of the methods herein and polymerizing acrylamide to produce polyacrylamide.

[0153] The compound of formula (2) produced according to the method herein can be used to produce one or more downstream products. For example, referring again to FIG. 8B, the acrylonitrile produced according to the method herein can be used to produce polyacrylonitrile. Thus, in certain embodiments, a method is provided that includes producing a compound of formula (2) according to any of the methods herein and polymerizing the compound of formula (2). In one variation, a method is provided for producing polyacrylonitrile, including producing acrylonitrile according to any of the methods herein and polymerizing the acrylonitrile to produce polyacrylonitrile. Polyacrylonitrile can be suitable for a variety of applications, including carbon fiber.

[0154] In another embodiment, the acrylonitrile produced according to the methods described herein may be used in the production of acrylic acid and / or acrylamide.

[0155] <Composition> In some embodiments, Compound of formula (2):

[0156] [ka] (In the formula, R 1 is H or alkyl; Dehydrating agent and A composition comprising:

[0157] In certain embodiments, the composition comprises a compound of formula (3):

[0158] [ka] (In the formula, R 1 is as defined above for formula (2)) or an isomer thereof.

[0159] In some variations of the above, the composition comprises: Compounds of formula (1):

[0160] [ka] (In the formula, R 1 is as defined above for equation (2)) and and ammonia.

[0161] In another embodiment, Compound of formula (1)

[0162] [ka] (In the formula, R 1 is H or alkyl; Ammonia and; Dehydrating agent and A composition comprising:

[0163] In some variations of the above, the composition comprises a compound of formula (3-I) and / or a compound of formula (3):

[0164] [ka] (In the formula, R 1 is as defined above for formula (1)) or an isomer thereof.

[0165] In certain variations of the above, the compound, dehydrating agent (including combinations of dehydrating agents), and ammonia present in the composition are as described herein for the method.

[0166] <System> In some embodiments, a continuous stirred tank reactor is provided comprising:

[0167] [ka] (In the formula, R 1a first inlet configured to receive a radical (R) (R is H or alkyl); a second inlet configured to receive ammonia, the reactor being configured to add the compound of formula (1) to the ammonia to achieve a ratio of ammonia to the compound of formula (1) such that ammonia is present in excess, the reactor being configured to add the compound of formula (1) to the ammonia at a rate suitable to maintain a temperature, the reactor being configured to receive the ammonia and the compound of formula (1) in liquid form; a jacket configured to maintain a constant temperature within the reactor; a vent configured to release excess ammonia from the reactor; an outlet configured to discharge a product stream comprising a compound of formula (2) produced from the compound of formula (1) and ammonia; and the compound of formula (2)

[0168] [ka] (In the formula, R 1 is as defined above for formula (1).

[0169] In another embodiment, a reactor is provided 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, the compound of formula (1) being:

[0170] [ka] (In the formula, R 1 is H or alkyl; A heterogeneous catalyst bed comprising: the reactor is configured to co-feed ammonia and a compound of formula (1) to a heterogeneous catalyst bed; the reactor is configured to separately control the flow rates of ammonia and the compound of formula (1); a heterogeneous catalyst bed, the reactor configured to add a compound of formula (1) to ammonia to achieve a ratio of ammonia to the compound of formula (1) such that ammonia is present in excess; a jacket configured to maintain a constant temperature within the reactor; a vent configured to release excess ammonia from the reactor; an outlet configured to discharge a product stream comprising a compound of formula (2) produced from the compound of formula (1) and ammonia; and the compound of formula (2)

[0171] [ka] (In the formula, R 1 is as defined above for formula (1).

[0172] In yet another embodiment, 1. A tube-shell reactor comprising: one or more tubes having catalyst particles packed therebetween and around the one or more tubes, the one or more tubes being configured to receive ammonia in gaseous form; an inlet on the shell side of the reactor configured to receive the compound of formula (1) in liquid form, the reactor configured to maintain an excess of ammonia in the reactor relative to the compound of formula (1); a reactor configured at a temperature to produce a compound of formula (2) from a compound of formula (1) and ammonia; and an inlet; an outlet configured to discharge a product stream comprising the compound of formula (2) and excess ammonia; A system is provided that includes a tube-shell reactor comprising:

[0173] In some variations of the above, the compound of formula (2) is provided in a molten form.

[0174] <Enumerated embodiments> The embodiments listed below are representative of some aspects of the present invention.

[0175] 1. A compound of formula (3-I) and / or a compound of formula (3):

[0176] [ka] Or

[0177] [ka] (In the formula, R 1 is H or alkyl) or an isomer thereof, combining a compound of formula (2) with a dehydrating agent to produce a compound of formula (3) or an isomer thereof; The compound of formula (2)

[0178] [ka] (In the formula, R 1 is as defined above for formulas (3-I) and (3), the dehydrating agent comprises phosphorus pentoxide, an organophosphorus 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 method wherein 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.

[0179] 2. further comprising the step of combining the compound of formula (1) with ammonia to produce a compound of formula (2); The compound of formula (1)

[0180] [ka] (In the formula, R 1is as defined above for formulas (3-I) and (3).

[0181] 3. The step of combining the compound of formula (1) with ammonia produces a compound of formula (2-I):

[0182] [ka] (In the formula, R 1 is as defined above for formulas (3-I) and (3).

[0183] 4. The method of any one of embodiments 1-3, further comprising the step of isolating the compound of formula (2-I).

[0184] 5. Compounds of formula (3-I) and / or compounds of formula (3):

[0185] [ka] Or

[0186] [ka] (In the formula, R 1 is H or alkyl) or an isomer thereof, combining a compound of formula (1) with ammonia and a dehydrating agent to produce a compound of formula (3-I) and / or a compound of formula (3), or an isomer thereof; The compound of formula (1)

[0187] [ka] (In the formula, R 1 is as defined above for formulas (3-I) and (3), the dehydrating agent comprises phosphorus pentoxide, an organophosphorus 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 method wherein 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.

[0188] 6. The ammonia is aqueous ammonia, or the ammonia is liquid ammonia, or the ammonia is anhydrous ammonia, or The method of embodiment 2 or 3, wherein the gas is anhydrous gaseous ammonia.

[0189] 7.R 1 is H, or R 1 is alkyl, or R 1 The method of any one of embodiments 1-5, wherein is methyl or ethyl.

[0190] 8. The method of any one of embodiments 1-7, further comprising isolating the compound of formula (3-I) or the compound of formula (3), or both.

[0191] 9. The method of any one of the preceding embodiments, wherein the dehydrating agent comprises phosphorus pentoxide.

[0192] 10. The method of any one of embodiments 1-8, wherein the dehydrating agent comprises an organophosphorus compound.

[0193] 11. The method of embodiment 10, wherein the organophosphorus compound is an organophosphate.

[0194] 12. The method of embodiment 10, wherein the organophosphorus compound is an alkyl halophosphate or a cycloalkyl halophosphate.

[0195] 13. The method of embodiment 10, wherein the organophosphorus compound is ethyl dichlorophosphate, diethyl chlorophosphate, methyl dichlorophosphate, dimethyl chlorophosphate, ethyl difluorophosphate, diethyl fluorophosphate, methyl difluorophosphate or dimethyl fluorophosphate, or any combination thereof.

[0196] 14. The method of any one of embodiments 1-8, wherein the dehydrating agent comprises a carbodiimide compound.

[0197] 15. A carbodiimide compound,

[0198] [ka] (In the formula, each R 4 and R 5 and R is independently alkyl or cycloalkyl.

[0199] 16. The method of embodiment 14, wherein the carbodiimide compound is N,N'-dicyclohexylcarbodiimide.

[0200] 17. The method of any one of embodiments 1-8, wherein the dehydrating agent comprises a triazine compound.

[0201] 18. The method of embodiment 17, wherein the triazine compound is a halo-substituted triazine compound.

[0202] 19. The method of embodiment 17 or 18, wherein the triazine compound is 1,3,5-triazine.

[0203] 20. The method of embodiment 17 or 18, wherein the triazine compound is cyanuric chloride.

[0204] 21. The method of any one of embodiments 1-8, wherein the dehydrating agent comprises an organosilicon compound.

[0205] 22. The method of embodiment 21, wherein the organosilicon compound is a silazane or a silane.

[0206] 23. The method of embodiment 21, wherein the organosilicon compound is bis(trimethylsilyl)amine.

[0207] 24. An organosilicon compound is

[0208] [ka] (In the formula, each R 6 , R 7 , R 8 and R 9 is independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy.

[0209] 25. The method of embodiment 21, wherein the organosilicon compound is a hydrosilane.

[0210] 26. The method of embodiment 25, wherein the dehydrating agent further comprises an alkylammonium halide.

[0211] 27. The method of embodiment 26, wherein the alkylammonium halide is tetrabutylammonium fluoride.

[0212] 28. The method of embodiment 21, wherein the organosilicon compound is a silane.

[0213] 29. The method of embodiment 28, wherein the silane is a halosilane, an alkoxysilane, or an aminosilane.

[0214] 30. The method of any one of embodiments 1-8, wherein the dehydrating agent comprises a transition metal complex.

[0215] 31. The method of embodiment 30, wherein the transition metal complex comprises at least one halide or oxide ligand.

[0216] 32. The method of embodiment 30 or 31, wherein the transition metal complex comprises palladium or zinc.

[0217] 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.

[0218] 34. The method of embodiment 30 or 31, wherein the transition metal complex comprises vanadium oxide.

[0219] 35. The method of any one of embodiments 1-8, wherein the dehydrating agent comprises an organosilicon compound and a transition metal complex.

[0220] 36. The method of embodiment 35, wherein the organosilicon compound is N-methyl-N-(trimethylsilyl)trifluoroacetamide.

[0221] 37. The method of embodiment 35 or 36, wherein the transition metal complex is a metal triflate or a metal halide.

[0222] 38. The method of embodiment 35, wherein the organosilicon compound comprises a silane.

[0223] 39. The method of embodiment 35 or 38, wherein the transition metal complex is an iron complex.

[0224] 40. The method of embodiment 35, wherein the organosilicon compound is an alkoxyalkylsilane.

[0225] 41. The method of embodiment 35 or 40, wherein the transition metal complex is a metal carbonate.

[0226] 42. The method of embodiment 41, wherein the metal carbonate is iron carbonate.

[0227] 43. Dehydrating agents, (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 The method of any one of embodiments 1 to 8, comprising:

[0228] 44. The method of any one of embodiments 1-8, wherein the dehydrating agent comprises an aluminum complex.

[0229] 45. The method of embodiment 44, wherein the aluminum complex comprises an aluminum halide.

[0230] 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.

[0231] 47. The method of any one of embodiments 1-8, wherein the dehydrating agent comprises an AlCl3·H2O / KI / H2O / CH3CN system or AlCl3·NaI.

[0232] 48. The method of any one of embodiments 1-47, wherein the dehydrating agent further comprises a solid carrier.

[0233] 49. The method of embodiment 48, wherein the solid support is hydrotalcite.

[0234] 50. The method of any one of embodiments 1-8, wherein the dehydrating agent comprises monomeric vanadium oxide and hydrotalcite.

[0235] 51. The method of any one of embodiments 1-8, 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.

[0236] 52. The method of any one of embodiments 1-8, wherein the dehydrating agent comprises 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, a clay, or any combination thereof.

[0237] 53. The dehydrating agents are H3PO4 / SiO2, fluorinated Al2O3, and Nb2O3 / PO4 -3 , Nb2O3 / SO4 -2 9. The method of any one of the preceding embodiments, comprising: Nb2O5, H3PO4, phosphate, phosphotungstic acid, phosphomolybdic acid, silicomolybdic acid, silicotungstic acid, Mg2P2O7, MgHPO4, or any combination thereof.

[0238] 54. The method of any one of embodiments 1-8, wherein the dehydrating agent comprises a zeolite.

[0239] 55. The method of embodiment 54, wherein the zeolite is in the hydrogen or ammonia form, or is a metal-exchanged zeolite.

[0240] 56. The method of embodiment 54, wherein the metal-exchanged zeolite comprises Li, Na, K, Ca, Mg, or Cu.

[0241] 57. The method of embodiment 54, wherein the zeolite has pore sizes in the range of 1 to 10 angstroms in diameter.

[0242] 58. The method of embodiment 54, wherein the zeolite is a medium pore zeolite.

[0243] 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.

[0244] 60. The method of embodiment 54, wherein the zeolite is a large pore zeolite.

[0245] 61. The method of embodiment 54, wherein the zeolite is ZSM-12, ZSM-5, mordenite, faujasite, or zeolite Y.

[0246] 62. The method of any one of embodiments 1-61, wherein the compound of formula (2) in the gas phase is passed through a heated reactor containing a dehydrating agent, thereby dehydrating the compound of formula (2) to produce a compound of formula (3-1) and / or a compound of formula (3).

[0247] 63. The method of embodiment 62, wherein the reactor is a packed bed reactor, a fluidized bed reactor, or a moving bed reactor.

[0248] 64. A process comprising the steps of combining a compound of formula (1) and ammonia in a reactor at an average temperature suitable to produce a compound of formula (2) with greater than 50% selectivity, The compound of formula (1)

[0249] [ka] and The compound of formula (2)

[0250] [ka] where R 1 is H or alkyl.

[0251] 65. A process comprising the step of 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 isomer thereof (as the case may be), with a selectivity of greater than 50%; The compound of formula (1)

[0252] [ka] and The compound of formula (2)

[0253] [ka] and The compound of formula (3-I) is

[0254] [ka] and The compound of formula (3)

[0255] [ka] That is, (In the formula, R 1 is H or alkyl) method.

[0256] 66. The process of embodiment 64 or 65, wherein the reactor temperature is maintained at an average temperature suitable for producing the compound of formula (2), the compound of formula (3-I) and / or the compound of formula (3), or their isomers (as the case may be), with a selectivity of greater than 50%.

[0257] 67. The method of any one of embodiments 64-66, wherein the compound of formula (1) is added dropwise to the reactor containing ammonia.

[0258] 68. The method of any one of embodiments 64-66, wherein the compound of formula (1) is added by a single injection into the reactor containing ammonia.

[0259] 69. Providing ammonia to a reactor; adding a first portion of a compound of formula (1) to a reactor; The compound of formula (1)

[0260] [ka] (In the formula, R 1 is H or alkyl; controlling the temperature of the reactor after addition of the first portion of the compound of formula (1); adding a second portion of the compound of formula (1) to the reactor; controlling the temperature of the reactor after the addition of the second portion of the compound of formula (1); by addition of a first portion and a second portion of a compound of formula (I) to produce a compound of formula (2):

[0261] [ka] (In the formula, R 1 is defined above), The process wherein the temperature of the reactor is controlled to an average temperature suitable for producing the compound of formula (2).

[0262] 70. A process comprising co-feeding a compound of formula (1) and ammonia to a heterogeneous catalyst bed to produce a compound of formula (2), The compound of formula (1)

[0263] [ka] and The compound of formula (2)

[0264] [ka] That is, (In the formula, R 1 is H or alkyl) method.

[0265] 71. The method of embodiment 70, wherein the compound of formula (1) is fed to the reactor as a liquid.

[0266] 72. The method of embodiment 70 or 71, wherein the flow rates of the compound of formula (1) and ammonia are controlled separately.

[0267] 73. The method of any one of embodiments 70-72, wherein ammonia is present in excess in the reactor.

[0268] 74. The method of any one of embodiments 70-73, further comprising collecting a product stream from the reactor comprising the compound of formula (2) and excess ammonia.

[0269] 75. The method of embodiment 74, wherein the compound of formula (2) is collected in liquid form.

[0270] 76. The method of embodiment 74 or 75, wherein the product stream is collected in a collection flask.

[0271] 77. The method of embodiment 76, wherein the temperature of the collection flask is below the boiling point of the compound of formula (2).

[0272] 78. The method of any one of embodiments 70-77, further comprising separating excess ammonia from the product stream.

[0273] 79. The method of embodiment 78, further comprising recycling the separated ammonia to the reactor.

[0274] 80. The method of any one of embodiments 70-79, wherein the heterogeneous catalyst bed comprises a metal oxide, a basic zeolite, an alkali metal exchanged zeolite, a base modified alumina, or a solid "superbase."

[0275] 81. The method of any one of embodiments 70-80, wherein the reactor is maintained at a temperature at which the compound of formula (2) is a gas.

[0276] 82. The method of any one of embodiments 70-81, wherein the compound of formula (2) is produced anhydrous.

[0277] 83. Ammonia is aqueous ammonia; or the ammonia is liquid ammonia, or the ammonia is anhydrous ammonia, or The method of any one of embodiments 70-82, wherein the ammonia is anhydrous gaseous ammonia.

[0278] 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.

[0279] 85. Producing acrylamide according to the method of embodiment 84; polymerizing acrylamide to form polyacrylamide; 1. A method for producing polyacrylamide, comprising:

[0280] 86. Producing acrylonitrile according to the method of embodiment 84; polymerizing acrylonitrile to form polyacrylonitrile; A method for producing polyacrylonitrile, comprising:

[0281] 87. Producing polyacrylonitrile according to the method of embodiment 86; Producing carbon fibers from polyacrylonitrile; 23. A method for producing carbon fiber comprising:

[0282] 88. A system comprising a continuous stirred tank reactor, The continuous tank reactor comprises: Compounds of formula (1):

[0283] [ka] (In the formula, R 1 a first inlet configured to receive a radical (R) (R is H or alkyl); a second inlet configured to receive ammonia, the reactor being configured to add the compound of formula (1) to the ammonia to achieve a ratio of ammonia to the compound of formula (1) such that ammonia is present in excess; a reactor configured to add a compound of formula (1) to the ammonia at a rate suitable to maintain a temperature; a second inlet, the reactor configured to receive ammonia and the compound of formula (1) in liquid form; a jacket configured to maintain a constant temperature within the reactor; a vent configured to release excess ammonia from the reactor; an outlet configured to discharge a product stream comprising a compound of formula (2) produced from the compound of formula (1) and ammonia; and the compound of formula (2)

[0284] [ka] (In the formula, R 1 is as defined above for equation (1),

[0285] 89. 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, the compound of formula (1) being:

[0286] [ka] (In the formula, R 1 is H or alkyl; a heterogeneous catalyst bed, the reactor being configured to co-feed ammonia and the compound of formula (1) to the heterogeneous catalyst bed; the reactor is configured to separately control the flow rates of ammonia and the compound of formula (1); a heterogeneous catalyst bed, the reactor configured to add a compound of formula (1) to ammonia to achieve a ratio of ammonia to the compound of formula (1) such that ammonia is present in excess; a jacket configured to maintain a constant temperature within the reactor; a vent configured to release excess ammonia from the reactor; an outlet configured to discharge a product stream comprising a compound of formula (2) produced from the compound of formula (1) and ammonia; Equipped with The compound of the formula (2) is

[0287] [ka] (In the formula, R 1 is as defined above for equation (1),

[0288] 90. The system of embodiment 88 or 89, wherein the compound of formula (2) is provided in molten form.

[0289] 91. A compound of formula (3):

[0290] [ka] (In the formula, R 1 is H or alkyl) or an isomer thereof, combining a compound of formula (2) with a dehydrating agent to produce a compound of formula (3) or an isomer thereof; The compound of formula (2)

[0291] [ka] (In the formula, R 1 is as defined above for formula (3), The method wherein the dehydrating agent comprises phosphorus pentoxide, an organophosphorus compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex or an aluminum complex, or any combination thereof.

[0292] 92. The method further comprising the step of combining a compound of formula (1) with ammonia to produce a compound of formula (2): The compound of formula (1)

[0293] [ka] (In the formula, R 1 is as defined above for formula (3).

[0294] 93. A compound of formula (3):

[0295] [ka] (In the formula, R 1 is H or alkyl) or an isomer thereof, combining a compound of formula (1) with ammonia and a dehydrating agent to produce a compound of formula (3) or an isomer thereof; The compound of formula (1)

[0296] [ka] (In the formula, R 1 is as defined above for formula (3), The method wherein the dehydrating agent comprises phosphorus pentoxide, an organophosphorus compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex or an aluminum complex, or any combination thereof.

[0297] 94. The method of embodiment 92 or 93, wherein the ammonia is ammonium hydroxide or aqueous ammonia.

[0298] 95. The method of any one of embodiments 92-94, wherein the compound of formula (1) is combined with ammonia at room temperature.

[0299] 96.R 1 The method of any one of embodiments 91-95, wherein is H.

[0300] 97.R 1The method of any one of embodiments 91-95, wherein is alkyl.

[0301] 98.R 1 The method of any one of embodiments 91-95, wherein is methyl or ethyl.

[0302] 99. The method of any one of embodiments 91 to 98, wherein the dehydrating agent comprises phosphorus pentoxide.

[0303] 100. The method of any one of embodiments 91-98, wherein the dehydrating agent comprises an organophosphorus compound.

[0304] 101. The method of embodiment 100, wherein the organophosphorus compound is an organophosphate.

[0305] 102. The method of embodiment 100, wherein the organophosphorus compound is an alkyl halophosphate or a cycloalkyl halophosphate.

[0306] 103. The method of embodiment 100, wherein the organophosphorus compound is ethyl dichlorophosphate, diethyl chlorophosphate, methyl dichlorophosphate, dimethyl chlorophosphate, ethyl difluorophosphate, diethyl fluorophosphate, methyl difluorophosphate or dimethyl fluorophosphate, or any combination thereof.

[0307] 104. The method of any one of embodiments 91-98, wherein the dehydrating agent comprises a carbodiimide compound.

[0308] 105. A carbodiimide compound,

[0309] [ka] (In the formula, each R 4 and R 5 is independently alkyl or cycloalkyl.

[0310] 106. The method of embodiment 104, wherein the carbodiimide compound is N,N'-dicyclohexylcarbodiimide.

[0311] 107. The method of any one of embodiments 91-98, wherein the dehydrating agent comprises a triazine compound.

[0312] 108. The method of embodiment 107, wherein the triazine compound is a halo-substituted triazine compound.

[0313] 109. The method of embodiment 107 or 108, wherein the triazine compound is 1,3,5-triazine.

[0314] 110. The method of embodiment 107 or 108, wherein the triazine compound is cyanuric chloride.

[0315] 111. The method of any one of embodiments 91-98, wherein the dehydrating agent comprises an organosilicon compound.

[0316] 112. The method of embodiment 111, wherein the organosilicon compound is a silazane or a silane.

[0317] 113. The method of embodiment 111, wherein the organosilicon compound is bis(trimethylsilyl)amine.

[0318] 114. An organosilicon compound is

[0319] [ka] (In the formula, each R 6 , R 7 , R 8 and R 9 is independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy.

[0320] 115. The method of embodiment 111, wherein the organosilicon compound is a hydrosilane.

[0321] 116. The method of embodiment 115, wherein the dehydrating agent further comprises an alkylammonium halide.

[0322] 117. The method of embodiment 116, wherein the alkylammonium halide is tetrabutylammonium fluoride.

[0323] 118. The method of embodiment 111, wherein the organosilicon compound is a silane.

[0324] 119. The method of embodiment 118, wherein the silane is a halosilane, an alkoxysilane, or an aminosilane.

[0325] 120. The method of any one of embodiments 91-98, wherein the dehydrating agent comprises a transition metal complex.

[0326] 121. The method of embodiment 120, wherein the transition metal complex comprises at least one halide or oxide ligand.

[0327] 122. The method of embodiment 120 or 121, wherein the transition metal complex comprises palladium or zinc.

[0328] 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.

[0329] 124. The method of embodiment 120 or 121, wherein the transition metal complex comprises vanadium oxide.

[0330] 125. The method of any one of embodiments 91-98, wherein the dehydrating agent comprises an organosilicon compound and a transition metal complex.

[0331] 126. The method of embodiment 125, wherein the organosilicon compound is N-methyl-N-(trimethylsilyl)trifluoroacetamide.

[0332] 127. The method of embodiment 125 or 126, wherein the transition metal complex is a metal triflate or a metal halide.

[0333] 128. The method of embodiment 125, wherein the organosilicon compound comprises a silane.

[0334] 129. The method of embodiment 125 or 128, wherein the transition metal complex is an iron complex.

[0335] 130. The method of embodiment 125, wherein the organosilicon compound is an alkoxyalkylsilane.

[0336] 131. The method of embodiment 125 or 130, wherein the transition metal complex is a metal carbonate.

[0337] 132. The method of embodiment 131, wherein the metal carbonate is iron carbonate.

[0338] 133. Dehydrating agents, (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) The method of any one of embodiments 91-98, comprising iron carbonate and diethoxymethylsilane.

[0339] 134. The method of any one of embodiments 91-98, wherein the dehydrating agent comprises an aluminum complex.

[0340] 135. The method of embodiment 134, wherein the aluminum complex comprises an aluminum halide.

[0341] 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.

[0342] 137. The method of any one of embodiments 91-98, wherein the dehydrating agent comprises the AlCl3·H2O / KI / H2O / CH3CN system or AlCl3·NaI.

[0343] 138. The method of any one of embodiments 91-137, wherein the dehydrating agent further comprises a solid carrier.

[0344] 139. The method of embodiment 138, wherein the solid support is hydrotalcite.

[0345] 140. The method of any one of embodiments 91-98, wherein the dehydrating agent comprises monomeric vanadium oxide and hydrotalcite.

[0346] 141. A compound of formula (2):

[0347] [ka] (In the formula, R 1 is H or alkyl; a dehydrating agent comprising phosphorus pentoxide, an organophosphorus compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, an aluminum complex, or any combination thereof; A composition comprising:

[0348] 142. Compound of formula (3):

[0349] [ka] (In the formula, R 1 is as defined above for equation (2). or its isomer 142. The composition of embodiment 141, further comprising:

[0350] 143. A compound of formula (1):

[0351] [ka] (In the formula, R1 is as defined above for equation (2)) and Ammonia and 143. The composition of embodiment 141 or 142, further comprising:

[0352] 144. Compound of formula (1):

[0353] [ka] (In the formula, R 1 is H or alkyl; Ammonia and; a dehydrating agent comprising phosphorus pentoxide, an organophosphorus compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, an aluminum complex, or any combination thereof; A composition comprising:

[0354] 145. A compound of formula (3):

[0355] [ka] (In the formula, R 1 is as defined above for formula (1). or its isomer The composition of embodiment 144, further comprising: EXAMPLES

[0356] The following examples are merely illustrative and are not intended to limit any aspect of the present disclosure in any way.

[0357] [Example 1] <Synthesis of anhydrous 3-hydroxypropanamide (3-HP amide)> This example relates to a process for the synthesis of 3-hydroxypropanamide (3-HP amide) from beta propiolactone (BPL), which is highly selective to produce 3-HP amide that is not contaminated with water.

[0358] The synthesis is carried out by adding the BPL in a controlled manner to a liquid pool of ammonia. This is carried out by adding beta-propiolactone and liquid ammonia (anhydrous) to a Parr-type reactor configured to allow the addition of ammonia and BPL as liquids. The reactor is also configured to contain the pressure that may be generated at and during the reaction and is jacketed to maintain a constant temperature. Alternatively, the reactor may be equipped with a condenser suitable for operating under pressure and controlling the temperature within the reactor by condensing the ammonia that boils during the reaction process and returning it to the reactor. The BPL is added to the liquid ammonia at a rate that controls the temperature to the desired set point. The ratio of ammonia to BPL is maintained such that there is always a large excess of ammonia.

[0359] After adding the desired amount of BPL and allowing sufficient time for complete conversion, the reaction is stopped by venting the ammonia, which is recovered and recycled to the next reaction. The remaining material in the reactor, mostly 3-HP amide, is collected and purified.

[0360] In some variations of this process, the temperature of the reaction ranges from 33° C. to room temperature. The aqueous reaction occurs at room temperature. The pressure required for the reaction is set by the vapor pressure of ammonia at the optimum reaction temperature.

[0361] [Example 2] Heterogeneous catalytic process for the production of 3-HP amide This example concerns an alternative synthesis of 3-HP amide from BPL that is highly selective and carried out continuously over a heterogeneous base catalyst.

[0362] The synthesis is carried out by co-feeding BPL and ammonia to a heterogeneous catalyst bed. BPL is fed to the reactor as a liquid and ammonia is fed to the reactor as a gas. This reactor configuration is sometimes called a "trickle bed reactor". The flow rates of liquid BPL and gaseous ammonia are controlled separately. The ratio is controlled so that ammonia is always in excess. The residence time in the catalyst bed is controlled to ensure complete conversion of BPL. The product 3-HP amide is collected in liquid form at the reactor outlet and the gaseous excess ammonia is separated and recycled to the reactor.

[0363] In some variations of the process, the base catalyst used may include metal oxides (e.g., MgO, ZrO), basic zeolites (e.g., the ammonia form of the zeolite precursor NH4ZSM5), alkali metal exchanged zeolites, other modified zeolites, base modified aluminas, solid "superbases" (e.g., lanthanide imides and nitrides on zeolites, metal oxynitrides, and KNH2 / Al2O3).

[0364] In some variations of this process, the temperature of the reaction is in the range of 10° C. to 100° C. The aqueous reaction occurs at room temperature. In one particular variation, this process is carried out at a temperature where 3-HP amide is a gas. In one variation, this process is carried out at 65-75° C.

[0365] The product collection flask is below the boiling point of 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.

[0366] [Example 3] <Reactor design for heterogeneous catalytic production of 3-HP amide> This example describes a reactor design suitable for a highly selective process for the production of 3-HP amide from BPL, such as the process described above in Example 2. The reactor is designed so that ammonia and BPL contact only in the heterogeneous catalyst bed.

[0367] In this example, tubes in a shell reactor are used. Catalyst particles are packed between and around the tubes. One reactant, such as ammonia, is fed through the catalyst bed on the shell side. A second reactant, such as beta-propiolactone, is then fed through the tube, making it porous to that reactant in one of two ways. In one variation, the tube can be drilled through the length of the tube embedded in the catalyst bed. Or, in another variation, the tube can be made of a porous metal tube through the length of the embedded tube. The tube can have a solid non-porous metal header that extends 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.

[0368] In one variation of the above, gaseous ammonia is fed through the tube and liquid BPL is dripped through the shell-side catalyst bed. In this configuration, sintered metal tubes may be used and may be configured to have near zero back diffusion by controlling the pore size.

[0369] [Example 4A] Integrated process for the production of acrylonitrile or acrylamide via 3-HP amide This example describes an integrated process for producing acrylonitrile, acrylamide, or a combination thereof via unisolated 3-HP amide. The integrated process described in this example combines two steps, (1) the synthesis of 3-HP amide from BPL under anhydrous conditions, and (2) the synthesis of acrylonitrile or acrylamide, or a combination thereof, from 3-HP amide, into one continuous unit operation that converts BPL to acrylonitrile or acrylamide, or a combination thereof.

[0370] The following system incorporates the 3-HP amide production process described in Example 1 above. The anhydrous synthesis of 3-HP amide is carried out in a continuous stirred tank reactor (CSTR) producing a solution of 3-HP amide in ammonia at the end of the reaction. This solution is discharged from the CSTR to a holding tank. From the holding tank, the 3-HP amide in ammonia is continuously fed to a fixed bed heterogeneous reactor containing the desired catalyst for the 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 to the desired product with high conversion and high selectivity. The resulting mixture of acrylonitrile / ammonia or acrylamide / ammonia exits the reactor and is collected in a product recovery vessel where the ammonia is separated from the product, condensed, and recycled to the 3-HP amide synthesis vessel. An inhibitor may be added at this stage to prevent polymerization. In one variation, the inhibitor is added before the ammonia is removed. In another variation, the inhibitor is added after the ammonia is removed.

[0371] One advantage of this approach is that acrylonitrile and / or acrylamide are produced continuously, solvent-free from BPL without intermediate separation and purification steps.

[0372] [Example 4B] Integrated process for the production of acrylonitrile or acrylamide via 3-HP amide This example describes an integrated process for producing acrylonitrile, acrylamide, or a combination thereof via unisolated 3-HP amide. The integrated process described in this example combines two steps, (1) the synthesis of 3-HP amide from BPL under anhydrous conditions, and (2) the synthesis of acrylonitrile or acrylamide, or a combination thereof, from 3-HP amide, into one continuous unit operation that converts BPL to acrylonitrile or acrylamide, or a combination thereof.

[0373] The following system incorporates the 3-HP amide production process described in Example 2 and / or Example 3 above. For the processes described in Examples 2 and 3, the output from the 3-HP amide synthesis reactor at the reactor outlet of the trickle bed reactor is a gas phase stream of 3-HP amide mixed with excess ammonia required for optimal yield of 3-HP amide. This gas phase mixture is then fed directly to a fixed bed heterogeneous reactor containing the desired catalyst for the production of the desired product, acrylonitrile or acrylamide, and heated to the desired reaction temperature. In the heterogeneous reactor, the 3-HP amide is converted to the desired product with high conversion and high selectivity. The remainder of the process is as described in Example 4A above.

[0374] One important advantage of this integrated approach is that the amount of unreacted ammonia is smaller and the excess amount required can be optimized simultaneously for both process steps (3-HP amide synthesis and subsequent conversion to the dehydration products acrylonitrile or acrylamide), minimizing the amount of recycled ammonia required. Moreover, since the feed to the 3-HP amide synthesis reactor in this case is gaseous, there is no need to condense recycled ammonia. Moreover, acrylonitrile and / or acrylamide are produced continuously solvent-free from BPL without intermediate separation and purification steps.

[0375] [Example 5] <Synthesis of 3-hydroxypropanamide> This example examines the effect of addition order and solvent on the formation of 3-HP amide.

[0376] [ka]

[0377] BPL and ammonia were combined according to the description in Table 1 below. The yield of 3-HP amide was determined as follows: 1 1 H NMR and LC-MS were used to determine the structure.

[0378] [Table 2]

[0379] [Example 6] [Synthesis of 3-Hydroxypropanamide] This example examines the effect of the amount of ammonium hydroxide used compared to the added BPL.

[0380] BPL and ammonium hydroxide were combined in a 5 L reactor at the NH4OH:BPL molar ratios shown in Table 2 below. The same temperature and BPL feed rate were used in each of the three experiments. The yield of 3-HP amide based on a crude sample of the reaction mixture was measured by 1 1H NMR. The reaction was then carried out. After the reaction stopped, the crude reaction mixture 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 yields of 3-HP amide are summarized in Table 2 below.

[0381] [Table 3]

[0382] [Example 7] [Synthesis of 3-HP Amide by Reaction of BPL with Aqueous Ammonia] This example shows the synthesis of 3-HP amide by the reaction of BPL with aqueous ammonia and evaluates the effect of reaction conditions on the selectivity to 3-HP amide.

[0383] The reaction was carried out in a temperature-controlled reactor with stirring. BPL was fed from a stainless steel cylinder using a metering pump. The reaction system was equipped with a sulfuric acid solution scrubber designed to neutralize the entire contents of the BPL feed vessel.

[0384] The reactor was charged with 2955 grams of 29 wt% ammonia solution and then pressurized to 40 psig with N2 (to provide a positive pressure differential across the BPL metering pump). The agitator was turned on at approximately 400 rpm and cooled to 9°C. 535 grams of BPL was connected to the feed system and pressurized to 16 psig with N2. The BPL feed rate was increased. The reactor temperature was maintained at 9-10°C during the period of continuous BPL feed (120 minutes). Once all the BPL was fed to the reactor, the feed was switched to deionized water. Approximately 100 grams of water was fed to the reactor to clear the BPL from the feed lines and feed pumps. The reaction was sampled 90 minutes after BPL addition and no residual BPL was detected by NMR analysis. The reaction mixture was drained from the reactor for recovery of the final product.

[0385] <Result> The reaction temperature was well controlled by the constant BPL addition. Near instantaneous reaction of BPL with concentrated aqueous ammonia was observed. The slight increase in reactor temperature (about 1°C) after increasing the BPL feed rate was compensated by decreasing the CTB set point. The reactor cooled from about 9-10°C to about 7°C within a few minutes of stopping the BPL feed.

[0386] Tables 3A and 3B show the reaction conditions and the selectivity for 3-HP amide and other compounds produced. The selectivity for 3-HP amide was 89%, with 3-hydroxypropionic acid being detected.

[0387] [Table 4]

[0388] [Table 5]

[0389] The reaction of BPL with aqueous ammonia under well-controlled conditions, such as reaction temperature and BPL addition rate, gave high selectivity to the 3-HP amide product.

[0390] [Example 8] <Effect of NH4OH:BPL ratio on 3-HP amide synthesis> This example evaluates the effect of the NH4OH:BPL ratio on the selectivity to 3-HP amide. In this example, the same materials and procedures as in Example 7 above were used, except that: 2891 grams of 29 wt% ammonia was charged to the reactor, and 704 grams of BPL was fed at a rate of 5.2 g / hour.

[0391] By quantitative BPL addition, the reaction temperature was properly controlled. Similar to Example 7 above, an almost instantaneous reaction between BPL and concentrated aqueous ammonia was observed. Tables 4A and 4B show the reaction conditions and the selectivities to 3-HP amide and other compounds produced. The selectivity to 3-HP amide was 89%.

[0392]

Table 6

[0393]

Table 7

[0394] When the reaction between BPL and aqueous ammonia was carried out under well-controlled conditions such as reaction temperature and BPL addition rate, the selectivity to 3-HP amide increased. The decrease in NH4OH:BPL from 3.3:1 in Example 7 to 2.4:1 in this example did not affect the selectivity to 3-HP amide (ammonia usage was reduced by 25%). 775 grams of crude 3-HP amide was produced.

[0395] [Example 9] <Acrylonitrile synthesis using Al2O3> This example shows the production of acrylonitrile by dehydration of 3-hydroxypropanamide using alumina (Al2O3).

[0396] <Reactor configuration> A continuous tubular reactor was used for the dehydration of 3-hydroxypropanamide to produce acrylonitrile. This example was performed using a uniformly heated GC injection port. A GC glass liner was used in place of the tubular reactor. A small amount of catalyst was placed in the liner, which was packed on both sides with inert glass wool.

[0397] <Preparation of catalyst> The Al2O3 catalyst used was obtained in the form of 1 / 8 inch pellets, which were crushed and sieved (250-600 μm) before being loaded into the reactor.

[0398] <Preparation of raw materials> The raw material 3-HP amide was dissolved in deionized water and injected into the injection port with a microsyringe. The feed was observed to evaporate at the reaction temperature and was forced through the catalyst bed under He carrier gas. Different residence times could be achieved by adjusting the catalyst amount and / or carrier gas flow rate. The injection port could be heated with a heating capacity of 400°C. The effluent from the reaction was sent directly to a GC column for separation and quantitative analysis.

[0399] <General Procedure> 3-HP amide was weighed into an autosampler vial mini insert and distilled water was added. The 3-HP amide dissolved to give an 11.08% solution (w / w). The GC injection port liner (inverted cup design) was packed with a small plug of glass wool just above the cup to support the Al2O3 particles. Sieved Al2O3 was added to obtain a bed of 0.2 cm length. Glass wool was added above the Al2O3 bed to hold it in place. A deactivated open tube liner containing only glass wool was also used for blank testing. A GC coupled with an FID detector was used for product analysis. The total flow rate of helium through the liner was maintained at 42 mL / min with the liner at 400 °C. The dimensions of the GC column used were 15 meters x 0.32 mm x 0.25 um.

[0400] <Result> The thermal stability of 3-HP amide was investigated in the absence of a catalyst. It was observed that 3-HP amide showed considerable stability at high temperatures up to 400 °C for a short time. The formation of acrylamide was less than 1%, and neither 3-HP amide nor ammonia was detected by GC.

[0401] Subsequently, an aqueous solution of 3-HP amide was injected into the reaction at 400 °C through a packed Al2O3 catalyst bed (0.2 cm). The original GC data for 15 injections are listed in Table 5 below, and the compiled results are shown in Figure 9. The conversion of 3-HP amide was observed to be 100% for each injection. The main species found in the product was acrylonitrile (50%).

[0402] [Table 8]

[0403] <Conclusion> This example of 3-HP amide dehydration using an Al2O3 catalyst demonstrated the conversion of 3-HP amide to acrylonitrile. Acrylonitrile was the main product detected by GC.

[0404] [Example 10] <Acrylonitrile synthesis using Nb2O5> This example demonstrates the production of acrylonitrile by dehydration of 3-hydroxypropanamide using Nb2O5. This example was carried out using a GC injection port as described in Example 9 above.

[0405] [Table 9]

[0406] [Table 10]

[0407] [Example 11] <Acrylonitrile synthesis> This example demonstrates the production of acrylonitrile using alumina, where molten 3-HP amide was fed into a vertical tubular reactor in a continuous mode.

[0408] The gas phase catalytic reaction system was configured as follows: 30 g of 3-hydroxypropanamide (99%) was prepared and added to the reaction vessel. The catalytic reactor was loaded with 1 g of 30-60 mesh Al2O3 catalyst and 20 g of silicon carbide as an inert support before and after the catalyst bed. The feed was warmed to less than 80°C and fed to the fixed bed reactor at a rate of about 10 WHSV by a metering pump. The reactor temperature was maintained at 350°C. Samples were collected at approximately 30 minute intervals for 1 hour. The samples were analyzed by NMR and GC-FID for acrylonitrile, acrylamide, acrylic acid, 3-hydroxypropanamide and other potential products. The conversion and selectivity results were calculated using the following equations:

[0409]

number

[0410]

number

[0411] The results showed that the overall conversion of 3-HP amido acid was 100%. The selectivity for acrylonitrile was 13%. Other products detected in the samples included acrylamide and polyamide.

Claims

1. a) contacting carbon monoxide with an epoxide compound to produce a beta propiolactone compound; b) contacting a beta propiolactone compound with an ammonia compound to produce a beta hydroxyamide compound; and c) contacting the beta hydroxyamide compound with a dehydrating agent without isolating the beta hydroxyamide compound between steps b) and c) to produce an amide compound and / or a nitrile compound. A method for producing an amide compound and / or a nitrile compound, comprising: i) contacting the beta propiolactone compound with an ammonia compound in the presence of a heterogeneous catalyst; and The beta propiolactone compound has the formula (1): 【Chemistry 1】 [In the formula, R １ is H or alkyl. A method having the structure of:

2. The beta hydroxyamide compound has the formula (2): 【Chemistry 2】 [In the formula, R １ is H or alkyl. or a geometric isomer thereof.

3. 3. The method of claim 1 or 2, wherein the ammonia compound comprises anhydrous ammonia, aqueous ammonia, or ammonium hydroxide.

4. The method of any one of claims 1 to 3, wherein the ammonia compound comprises anhydrous ammonia.

5. contacting a beta propiolactone compound with an ammonia compound by dropwise addition in the presence of a cooling coil; and The ammonia compound is anhydrous ammonia; The method according to any one of claims 1 to 3.

6. contacting a beta propiolactone compound with an ammonia compound in a single injection; and The ammonia compound is aqueous ammonia; The method according to any one of claims 1 to 3.

7. The amide compound is represented by the following formula (3): 【Chemistry 3】 [In the formula, R １ is H or alkyl. The structure is The nitrile compound is represented by the following formula (3-I): 【Chemistry 4】 [In the formula, R1 is H or alkyl.] The method according to any one of claims 1 to 6, having the structure:

8. the dehydrating agent comprises phosphorus pentoxide, an organophosphorus compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a mixed oxide, a transition metal complex or an aluminum complex, or a combination thereof; or The dehydrating agent comprises a solid metal oxide, a solid acid, an acid, a weak acid, a strong acid, an ion exchange resin, an aluminosilicate, or a combination thereof. The method according to any one of claims 1 to 7.

9. The method of any one of claims 1 to 8, wherein the heterogeneous catalyst comprises one or more of a metal oxide, a basic zeolite, an alkali metal exchanged zeolite, a modified zeolite, a base modified alumina, or a solid "superbase".

10. The process of any one of claims 1 to 9, wherein the heterogeneous catalyst comprises a solid supported heterogeneous catalyst.

11. The method of any of claims 1 to 10, wherein the carbon monoxide and / or epoxide compounds comprise at least 10% bio-based content.

12. The method of any one of claims 1 to 11, further comprising polymerizing the amide compound to form a polyamide.

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