JP7095911B2 - Amide and nitrile compounds and their production and usage - Google Patents

Description

<Cross-reference of related applications>
This application is prioritized by US Provisional Patent Application No. 62 / 556,355 filed September 9, 2017, and US Provisional Patent Application No. 62 / 690,783 filed June 27, 2018. Claiming rights, each of which is incorporated herein by reference in its entirety.

The present disclosure relates generally to the formation of amide products and / or nitrile products, and more particularly to the formation of at least epoxides, beta lactones and / or beta hydroxyamides.

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 polymers 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, in which case propylene, ammonia and air come into contact with the catalyst at high temperatures and pressures. However, this process generally requires the use of harsh reaction conditions and expensive reagents.

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

As used herein, methods and systems for producing amide products and / or nitrile products are provided. Advantageously, the particular preferred methods and systems provided are bio-based alternatives to conventional methods and systems for producing nitriles and amides with reduced costs and reduced environmental hazards.

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 invention can produce amide and / or nitrile products from bio-based epoxides and / or bio-based beta lactones. In certain embodiments, the system and method can be modified to selectively produce the preferred amide or nitrile product in higher yields than one or more other products. Advantageously, by integrating the systems and methods of the present invention into conventional systems and processes, the environmental impact of producing many commercial products can be reduced.

For example, in some embodiments, the amide compound of formula (3-I) and / or the nitrile compound of formula (3).

（式中、Ｒ^１は、Ｈ又はアルキルである）又はその異性体の生成方法が提供され、
この方法は、
式（２）のアミド化合物を脱水剤と組み合わせて、式（３－Ｉ）のニトリル化合物及び／若しくは式（３）のアミド化合物、又はそれらの異性体を生成するステップを含み、
式（２）のアミド化合物は、

(In the formula, R ¹ is H or alkyl) or a method for producing an isomer thereof is provided.
This method
The step comprises combining the 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 the formula (2) is

（式中、Ｒ^１は、式（３－Ｉ）及び式（３）について上記で定義した通りである）である。

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

In certain embodiments described above, the method further comprises the step of combining the beta lactone compound of formula (1) with ammonia to produce the amide compound of formula (2).
The beta lactone compound of formula (1) is

（式中、Ｒ^１は、式（３－Ｉ）及び式（３）について上記で定義した通りである）である。

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

In some variants of the above method, the dehydrating agent comprises phosphorus pentoxide, an organic phosphorus compound, a carbodiimide compound, a triazine compound, an organic silicon compound, a mixed oxide, a transition metal complex or an aluminum complex, or any combination thereof. include. In one variant, 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.

In some variants of the above method, the dehydrating agent is a titanic acid, a metal oxide hydrate, a metal sulfate, a metal oxide sulfate, a metal phosphate, a metal oxide phosphate, a mineral acid, a carboxylic acid or a salt thereof, an acid. Includes resins, acidic zeolites, clays, or any combination thereof. In certain variants of the method and system, the dehydrating agent comprises zeolite.

In other embodiments
A method comprising the step of combining a compound of formula (1) and ammonia to produce a compound of formula (2) in a reactor is provided.
The compound of formula (1) is

であり、
式（２）の化合物は、

And
The compound of formula (2) is

であり、
式中、Ｒ^１は、Ｈ又はアルキルである。

And
In the formula, R ¹ is H or alkyl.

In the above specific variant, 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 more than 90%.

In some embodiments
A method comprising the steps 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) is provided. ,
The compound of formula (1) is

であり、
式（２）の化合物は、

And
The compound of formula (2) is

であり、
式（３－Ｉ）の化合物は、

And
The compound of formula (3-I) is

であり、
式（３）の化合物は、

And
The compound of formula (3) is

であり、
式中、Ｒ^１は、Ｈ又はアルキルである。

And
In the formula, R ¹ is H or alkyl.

In the above specific variant, 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 more than 90%, or the selectivity of the formula (3) is more than 10%, more than 20%, more than 30%, more than 40%, more than 50%, more than 60%, more than 70%, more than 80%, Or more than 90%, or the selectivity of formula (3-I) is more than 10%, more than 20%, more than 30%, more than 40%, more than 50%, more than 60%, more than 70%, 80%. Super or over 90%.

In some of the above variants, 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 embodiments, there is provided a method comprising the step of producing an amide such as acrylamide and the step of polymerizing the amide according to any of the methods herein. In one variant where the amide is acrylamide, the polymer is polyacrylamide. In another embodiment, there is provided a method comprising the step of producing a nitrile such as acrylonitrile and the step of polymerizing the nitrile according to any of the methods herein. In one variant where the nitrile is acrylonitrile, the polymer is polyacrylonitrile. In yet another embodiment, there is provided a method for producing carbon fibers, comprising the steps of producing polyacrylonitrile according to any of the methods herein and the step of producing carbon fibers from polyacrylonitrile.

In other embodiments, a system for producing amide and / or nitrile products from at least beta lactones and / or beta hydroxyamides is provided. In certain embodiments, the provided system comprises one or more reactors of a size, shape and configuration that provide an amide product and / or a nitrile product. In certain embodiments, the one or more reactors may be configured as a continuous stirring tank reactor, a fixed catalyst bed reactor, a flow 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 uniform catalyst.

In some of the above variants, the compounds of the invention have a biobase content of greater than 0% and less than 100%. In certain variants described above, the compounds of the invention have a biobase content of at least 10%, at least 20%, at least 50%, at least 70%, at least 95%, or 100%.

In some variants, the biobase content can be determined based on: ATM D6866 (standard test method for determining the biobase content of solid, liquid and gas samples using radioactive carbon analysis). % Biobase content = [bio (organic) carbon] / [total (organic) carbon] x 100%.

The bio-based content of the compositions of the invention may depend on the bio-based content of the beta lactone used. For example, in some variants of the methods described herein, the beta lactones used to produce the amide and / or nitrile products described herein are greater than 0% and 100%. Can have a biobase content of less than. In certain variations of the methods described herein, the beta lactone used to produce the amide and / or nitrile products described herein is 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 It can have a biobase content of 5.5%, at least 99.9%, at least 99.99%, or 100%. In certain variants, beta lactones obtained from renewable resources are used. In other variants, at least some of the beta lactones used are derived from renewable resources and at least some of the beta lactones are obtained from non-renewable resources.

The biobase content of the beta lactone can depend, for example, on the biobase content of the epoxides and carbon monoxide used. In some variants, both epoxides and carbon monoxide are obtained from renewable resources.

The present application can be best understood by reference to the following description in conjunction with the accompanying drawings, in which similar parts may be referred to by similar numbers.

It is an exemplary reaction scheme for producing the compound of formula (3). It is an exemplary reaction scheme for producing the compound of formula (3). It is an exemplary reaction scheme for producing the compound of formula (3). It is an exemplary reaction scheme for producing the compound of formula (3). It is an exemplary reaction scheme for producing the compound of formula (3). It is an exemplary reaction scheme for producing the compound of formula (3-I). A reaction scheme showing how ammonia water contains a dynamic equilibrium mixture of ammonia gas / water and ammonium. An exemplary reaction scheme involving beta-propiolactone and ammonium / ammonia. In a graph showing the results of experiments performed in Example 9, including the production of acrylonitrile by dehydration of 3-hydroxypropaneamide (abbreviated as "3-HP amide") using alumina (Al ₂ O ₃ ). be.

The following description shows exemplary methods, parameters and the like. However, it should be noted that such description is not intended to limit the scope of the present disclosure and is instead provided as a description of an exemplary embodiment.

Provided herein are methods and systems for producing amide and / or nitrile products from at least beta lactones and / or beta hydroxyamides. In certain preferred embodiments, the amide product comprises acrylamide and the nitrile product comprises acrylonitrile. In certain variants, beta lactones can be produced by carbonylation of epoxides with carbon monoxide.

In some embodiments, methods are provided for producing acrylonitrile compounds and other nitrile compounds from beta hydroxyamides. For example, referring to FIG. 1, the beta hydroxyamide of formula (2) is combined with a dehydrating agent to produce an acrylonitrile compound, another nitrile compound of formula (3), or an isomer thereof.

In another embodiment, a method for producing an acrylonitrile compound and other nitrile compounds from a lactone is provided. For example, referring to FIG. 2, the beta-lactone of formula (1) is combined with ammonia to form the beta hydroxyamide of formula (2), which is then subjected to the exemplary reaction shown in FIG. 1 to formula (3). ), Or an isomer thereof.

In another example, with reference to FIG. 3, the beta lactone of formula (1) is combined with ammonia (also referred to as aqueous ammonia) and a dehydrating agent in water to form an acrylonitrile compound or another nitrile compound of formula (3). Or it may produce an isomer thereof.

In yet another example, reference to FIG. 4 shows the conversion of the beta lactone of formula (1) to the nitrile compound of formula (3) or an isomer thereof, formulas (2) and (3-I). Intermediate compounds can undergo dehydration to form nitriles. In one embodiment, there is provided a method comprising combining a compound of formula (1) and ammonia in a reactor to produce a compound of formula (2) with a selectivity of greater than 80%, respectively. In another embodiment, the compound of formula (1) and ammonia are combined in the reactor to give the compound of formula (2), the compound of formula (3-I) and / or the formula (3) with greater than 80% selectivity. A method comprising the steps of producing the compound of is provided.

In some of the above variants, 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%, 90. More than%, more than 95%, more than 96%, more than 97%, more than 98%, or more than 99%. Selectivity can be controlled by one or more parameters. For example, in some variants, the reactor temperature is maintained at an average temperature between −20 ° C. and 50 ° C., or between 10 ° C. and 35 ° C. In another variant, the compound of formula (1) is added dropwise to a reactor containing ammonia. In another variant, the compound of formula (1) is added by a single injection into a reactor containing ammonia.

In yet another variant, the compound of formula (2) is provided with the first portion of the compound of formula (1) to the reactor, the step of adding ammonia, and the average temperature of the reactor is maintained. A method is provided that includes a step to generate. In one variant, the method further comprises isolating the compound of formula (2). In certain embodiments, the steps of maintaining average temperature are performed between −20 ° C. and 50 ° C.

In yet another modification, a method comprising simultaneously supplying the compound of formula (1) and ammonia to the reactor and maintaining the average temperature of the reactor to produce the compound of formula (2). Provided. In one variant, the method further comprises isolating the compound of formula (2). In certain embodiments, the compound of formula (1) is fed to the reactor as a liquid in contact with the heterogeneous catalyst. In a particular variant, the flow rates of the compound of formula (1) and ammonia are controlled separately. In certain variants, ammonia is in excess in the reactor. In another embodiment, the method further comprises collecting a product stream containing the compound of formula (2) and excess ammonia from the reactor. In one variant, the compound of formula (2) is collected in liquid form. In yet another embodiment, the method further comprises the steps of separating excess ammonia from the product stream and recycling the separated ammonia into a reactor. In other variants, the heterogeneous catalyst bed comprises any of the heterogeneous dehydrating agents described herein. For example, in one variant, the heterogeneous catalyst bed comprises a metal oxide, a basic zeolite, an alkali metal exchange zeolite, a base modified alumina, or a solid "superbase". In other variants, the temperature of the reactor is maintained in the range of 10 ° C to 100 ° C or 65 ° C to 75 ° C, or at room temperature. In one variant, the reactor is maintained at a temperature at which the compound of formula (2) is gaseous. In another variant, the compound of formula (2) is produced anhydrous.

In some of the above variants, the compound of formula (1) is combined with liquid ammonia. In the other variant described above, the compound of formula (1) is combined with ammonia in the absence of a solvent. In certain variants, the compound of formula (1) is combined with ammonia (or ammonium hydroxide) in water. In other words, in certain variants, ammonia is aqueous ammonia. With reference to FIG. 7A, it should be understood that in general, ammonia water contains a dynamic equilibrium mixture of ammonia gas / water and ammonium hydroxide. In another variant, the compound of formula (1) is combined with anhydrous ammonia. In one variant, the ammonia is anhydrous gaseous ammonia. Referring to FIG. 7B, when anhydrous ammonia is used, at least one step (such as removal of water prior to the hydration reaction) can be avoided. Ammonia can be obtained from commercially available sources or can be produced according to any method known in the art.

In another variant, the compound of formula (1) is combined with ammonia at elevated temperatures. In other variants, the compound of formula (1) is combined with ammonia and additional basic compounds.

In certain variants described above, ammonia is combined with a compound of formula (1), along with any of the dehydrating agents described herein, as shown in FIG. In other variants, as shown in FIGS. 2 and 4, ammonia is combined with the compound of formula (1) to first produce the beta-hydroxyamide of formula (2), which is then described herein. Any of the dehydrating agents of the formula (2) is combined with the beta-hydroxyamide of the formula (2) to form a compound of the formula (3-I) and / or a compound of the formula (3), or an isomer thereof.

In another embodiment, referring to FIG. 5, a method for producing an amide of formula (3-I) or an isomer thereof from a beta hydroxyamide of formula (2) is provided. In still another embodiment, referring to FIG. 6, a method for producing a nitrile of formula (3) or an isomer thereof from an amide of formula (3-I) or an isomer thereof is provided. The exemplary reactions shown in FIGS. 5 and 6 include dehydration reactions in which any of the dehydrating agents described herein can be used.

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

The amide and / or nitrile products produced according to the methods and systems herein can be used in a variety of downstream steps. For example, in certain variants, acrylamide may be polymerized to form polyacrylamide, or acrylonitrile may be polymerized to form polyacrylonitrile. The obtained polyacrylonitrile can be suitable for various uses including carbon fibers and the like.

Methods including acrylamide and acrylonitrile compounds, as well as other compounds that can be produced, as well as amides, lactones and dehydrating agents that can be used are discussed in more detail below.

<Acrylonitrile compounds and other nitrile compounds>
In one aspect, a method of producing acrylonitrile and other nitrile compounds from beta-propiolactone and other lactones, respectively, is provided. For example, in one modified form, beta-propiolactone may be reacted with aqueous ammonia to obtain a crude 3-hydroxypropaneamide aqueous solution. The crude solution is then purified with a resin to remove impurities and then water is removed to give a solid form of pure 3-hydroxypropaneamide. Pure 3-hydroxypropaneamide can then be continuously fed to a fixed bed reactor packed with a dehydration catalyst. The 3-hydroxypropaneamide solid can be warmed to a temperature above its melting point and then further mixed / vaporized with the nitrogen sweep gas in the preheating zone before passing through the catalyst bed. The dehydration reaction of 3-hydroxypropaneamide to acrylonitrile in the presence of water can occur on the surface of the catalyst.

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

（式中、Ｒ^１は、Ｈ、アルキル、アルケニル、シクロアルキル若しくはアリールである）又はその異性体である。

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

"Alkyl" refers to a non-branched or branched saturated hydrocarbon chain of monoradicals. In some embodiments, the alkyl is 1-10 carbon atoms (ie C _1-10 alkyl), 1-9 carbon atoms (ie C _1-9 alkyl), 1-8 carbon atoms (ie C 1-9 alkyl). That is, C _1-8 alkyl, 1 to 7 carbon atoms (ie, C _1-7 alkyl), 1 to 6 carbon atoms (ie, C _1-6 alkyl), and 1 to 5 carbon atoms (ie, C). _1-5 alkyl), 1 to 4 carbon atoms (ie, C _1-4 alkyl), 1 to 3 carbon atoms (ie, C _1-3 alkyl), or 1 to 2 carbon atoms (ie, C ₁ ). _-2 Alkyl). Examples of alkyls 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. including. When an alkyl residue with a certain number of carbon atoms is named, all geometric isomers with that number of carbon atoms can be included. Thus, for example, "butyl" may include n-butyl, sec-butyl, isobutyl and t-butyl, and "propyl" may include n-propyl and isopropyl.

"Alkene" refers to an unsaturated linear or branched monovalent hydrocarbon chain having at least one olefinic unsaturated moiety (ie, having at least one portion of the formula C = C) or a combination thereof. In some embodiments, the alkenyl has 2-10 carbon atoms (ie, C _2-10 alkenyl). The alkenyl group may have a "cis" or "trans" configuration, or an "E" or "Z" configuration. Examples of alkenyl are ethenyl, allyl, propa-1-enyl, propa-2-enyl, 2-methylpropa-1-enyl, porcine-1-enyl, porcine-2-enyl, porcine-3-enyl, isomers thereof. Including body etc.

"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.

"Aryl" refers to a monovalent aromatic carbocyclic group of 6-18 cyclic carbon atoms having a ring system with a single ring or multiple fused rings. Examples of aryls include phenyl, naphthyl and the like.

In some variants, the alkyl, alkenyl, cycloalkyl, or aryl of R ¹ may be optionally substituted. The term "optionally substituted" means that the specified group is unsubstituted or substituted with one or more substituents. In certain variants, the optional substituents are halo, -OSO ₂ R ₂ , -OSiR ₄ , -OR, C = CR ₂ , -R, -OC (O) R, -C (O) OR. And -C (O) NR ₂ may be included, in which R is independently H, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted aryl. be. In some embodiments, R is independently an 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. Is. In certain embodiments, the substituents are F, Cl, -OSO ₂ Me, -OTBS ("TBS" is tert-butyl (dimethyl) silyl), -OMOM ("MOM" is methoxymethyl acetal). ), -OME, -OEt, -OiPr, -OPh, -OCH ₂ CHCH ₂ , -OBn, -OCH ₂ (frill), -OCF ₂ CHF ₂ , -C = CH ₂ , -OC (O) Me,- OC (O) nPr, -OC (O) Ph, -OC (O) C (Me) CH ₂ , -C (O) OME, -C (O) OnPr, -C (O) NMe ₂ , -CN, It may include -Ph, -C ₆ F ₅ , -C ₆ H ₄ OME and -OH.

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

In some variants, R ¹ is H and the compound of formula (3) is

（当技術分野ではアクリロニトリルとしても知られている）である。

(Also known in the art as acrylonitrile).

In other variants, R ¹ is alkyl. In certain variants, R ¹ is C _1-6 alkyl. In one variant, R ¹ is methyl or ethyl. When R ¹ is methyl, the compound of formula (3) is

又はその異性体（当技術分野ではクロトノニトリルとしても知られている）である。Ｒ^１がエチルである場合、式（３）の化合物は

Or an isomer thereof (also known in the art as crotononitrile). When R ¹ is ethyl, the compound of formula (3) is

又はその異性体（当技術分野では２－ペンテンニトリルとしても知られている）である。

Or an isomer thereof (also known in the art as 2-pentenenitrile).

"Alkyl" refers to a non-branched or branched saturated hydrocarbon chain of monoradicals. In some embodiments, the alkyl is 1 to 6 carbon atoms (ie, C _1-6 alkyl), 1 to 5 carbon atoms (ie, C _1-5 alkyl), and 1 to 4 carbon atoms (ie, C 1-5 alkyl). That is, it has 1 to _{3 carbon atoms (that is, C 1-3 alkyl} ), or 1 to 2 carbon atoms (that is, C _1-2 alkyl). In other embodiments, the alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl and May include 3-methylpentyl. When an alkyl residue with a particular number of carbons is named, all geometric isomers with that number of carbons can be included. Thus, for example, "butyl" may include n-butyl, sec-butyl, isobutyl and t-butyl, and "propyl" may include n-propyl and isopropyl.

Further, it should be understood that when a range of values is listed, it is intended to include each value and a subrange within that range. For example, "C _1-6 alkyl" (which may also be referred to as 1-6C alkyl, C1-C6 alkyl, or C1-6 alkyl) is C ₁ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ , 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 , It is intended to include C _3-5 , C _3-4 , C _4-6 , C _4-5 and C _5-6 alkyl.

<Acrylamide and other amides>
In some embodiments, acrylamide or other amides can be used to produce acrylonitrile compounds and other nitrile compounds. In some variants, such amides are in formula (3-I).

（式中、Ｒ^１は、Ｈ、アルキル、アルケニル、シクロアルキル、又はアリールである）の化合物である。

(In the formula, R ¹ is H, alkyl, alkenyl, cycloalkyl, or aryl).

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

In some variants, R ¹ is H and the compound of formula (3-I) is

（又はアクリルアミド）である。他の変形形態において、Ｒ^１は、アルキルである。ある特定の変形形態において、Ｒ^１は、Ｃ_１－６アルキルである。一変形形態において、Ｒ^１は、メチル又はエチルである。Ｒ^１がメチルである場合、式（３－Ｉ）の化合物は、

(Or acrylamide). In other variants, R ¹ is alkyl. In certain variants, R ¹ is C _1-6 alkyl. In one variant, R ¹ is methyl or ethyl. When R ¹ is methyl, the compound of formula (3-I) is

又は

Or

（当技術分野ではブタ－２－エンアミドとしても知られている）である。Ｒ^１がエチルである場合、式（２）の化合物は、

(Also known in the art as pig-2-enamide). When R ¹ is ethyl, the compound of formula (2) is

又は

Or

（当技術分野ではペンタ－２－エンアミドとしても知られている）である。

(Also known in the art as penta-2-enamide).

In general, 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 of formula (3-I) is defined with respect to formula (3). Please understand that it is exactly what you did.

Acrylamides and other amides, such as compounds of formula (3-I), can be obtained from the methods described herein, or from any commercially available source, or any known in the art. It can be generated according to the method.

In certain embodiments, the compounds of formula (3-I) produced according to the methods herein may be isolated. In some variants, the compounds of formula (3-I) produced according to the methods herein may be isolated and purified. Compounds of formula (3-I) produced according to the methods herein may be isolated.

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

（式中、Ｒ^１は、Ｈ、アルキル、アルケニル、シクロアルキル、又はアリールである）である。

(In the formula, R ¹ is H, alkyl, alkenyl, cycloalkyl, or aryl).

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

In some variants, R ¹ is H and the compound of formula (2) is

（又は３－ヒドロキシプロパンアミド）である。他の変形形態において、Ｒ^１は、アルキルである。ある特定の変形形態において、Ｒ^１は、Ｃ_１－６アルキルである。一変形形態において、Ｒ^１は、メチル又はエチルである。Ｒ^１がメチルである場合、式（２）の化合物は、

(Or 3-hydroxypropaneamide). In other variants, R ¹ is alkyl. In certain variants, R ¹ is C _1-6 alkyl. In one variant, R ¹ is methyl or ethyl. When R ¹ is methyl, the compound of formula (2) is

（又は３－ヒドロキシブタンアミド）である。Ｒ^１がエチルの場合、式（２）の化合物は、

(Or 3-hydroxybutaneamide). When R ¹ is ethyl, the compound of formula (2) is

（又は３－ヒドロキシペンタンアミド）である。

(Or 3-hydroxypentane amide).

It is generally understood that when a compound of formula (2) is used to produce a compound of formula (3) or an isomer thereof, R ¹ of formula (2) is as defined for formula (3). sea bream.

Beta hydroxyamides and other amides, such as the compounds of formula (2), can be obtained from the methods described herein, or from any commercially available source, or any known in the art. It can be generated according to the method.

In certain embodiments, the compounds of formula (2) produced according to the methods herein may be isolated. In some variants, the compounds of formula (2) produced according to the methods herein may be isolated and purified. The compound of formula (2) produced according to the method herein may be isolated.

<Beta lactones 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, the beta lactone is the formula (1) :.

（式中、Ｒ^１は、Ｈ、アルキル、アルケニル、シクロアルキル、又はアリールである）の化合物である。

(In the formula, R ¹ is H, alkyl, alkenyl, cycloalkyl, or aryl).

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

In some variants, R ¹ is H and the compound of formula (1) is

（当技術分野ではベータプロピオラクトンとしても知られている）である。

(Also known in the art as beta-propiolactone).

In other variants, R ¹ is alkyl. In certain variants, R ¹ is C _1-6 alkyl. In one variant, R ¹ is methyl or ethyl. When R ¹ is methyl, the compound of formula (1) is

（当技術分野ではベータブチロラクトンとしても知られている）である。Ｒ^１がエチルである場合、式（１）の化合物は、

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

（当技術分野ではベータバレロラクトンとしても知られている）である。

(Also known in the art as beta valerolactone).

In general, when a compound of the formula (1) is used to produce a compound of the formula (2), a compound of the formula (3), or an isomer thereof, R ¹ of the formula (1) is the formula (2) or. Please understand that it is as defined for equation (3).

Beta lactones, such as the compounds of formula (1), can be obtained from any commercially available source or can be produced according to any method known in the art. For example, beta-propiolactone can be obtained by reacting ethylene oxide with carbon monoxide under appropriate conditions. In some variants, the amide product and / or the nitrile product 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.

Table A.

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

Various techniques for determining the bio-content of a material are known in the art. For example, in some variants, the bio-content of the material can be measured using the ASTM D6866 method, which allows the material to use radiocarbon analysis with accelerator mass spectrometry, liquid scintillation counting and isotope mass spectrometry. It is possible to determine the bio-content of. Bio-content results can be derived by assigning 100% to 107.5 pMC (percent modern carbon) and 0% to 0 pMC. For example, a sample measuring 99 pMC will give an equivalent bio content result of 93%. In one variant, the bio-content may be determined according to ASTM D6866 revision 12 (ie, ASTM D6866-12). In another variant, the bio-content may be determined according to the procedure of Method B of ASTM-D6866-12. Other techniques for assessing the bio-content of a material include US Pat. Nos. 3,885,155, 4,427,884, 4,973,841, 5,438,194 and 5,661,299, as well as WO2009 / 155086.

<Dehydrating agent>
Dehydration generally involves the conversion of carbon-carbon single bonds to carbon-carbon double bonds to produce water molecules. The dehydration reaction described herein can occur in the presence of a suitable homogeneous or heterogeneous catalyst.

In some embodiments, suitable dehydration catalysts may include acids, bases and oxides. Examples of suitable acids are H ₂ SO ₄ , HCl, titanic acid, metal oxide hydrate, metal sulfate (MSO ₄ , in the formula, M is Zn, Sn, Ca, Ba, Ni, Co, or the like. (May be the transition metal of), metal oxide sulfate, metal phosphate (eg, M ₃ (PO ₄ ) ₂ , in the formula, M may be Ca, Ba), metal phosphate, metal oxide. Phosphate, carbon (eg, transition metal on carbon carrier), mineral acid, carboxylic acid, its salt, acidic resin, acidic zeolite, clay, SiO ₂ / H ₃ PO ₄ , fluorinated Al ₂ O ₃ , phosphotung acid, It may contain phosphomolybdic acid, silicate molybdic acid, silicate tungsten 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 include Nb ₂ O ₅ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SiO ₂ , ZnO ₂ , SnO ₂ , WO ₃ , MnO ₂ , Fe ₂ O ₃ and V ₂ O ₅ . obtain.

In some embodiments, the dehydrating agent used in the methods described herein is phosphorus pentoxide, an organic phosphorus compound, a carbodiimide compound, a triazine compound, an organic silicon compound, a mixed oxide, a transition metal complex, or aluminum. Contains a complex.

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.

Dehydrating agents can be obtained from commercially available sources or prepared according to methods known in the art.

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

In one variant, the dehydrating agent comprises phosphorus pentoxide.

In some variants, the dehydrating agent comprises an organophosphorus compound. In certain variants, the organophosphorus compound is an organic phosphate. In certain variants, the organophosphorus compound is an alkyl halo phosphate or a cycloalkyl halo phosphate. In one variant, the alkyl halo phosphate is an alkyl dihalo phosphate or a dialkyl halo phosphate. In another variant, the cycloalkyl halophosphate is a cycloalkyl dihalophosphate, or a dicycloalkyl halophosphate. _In some variants of the organophosphorus compounds, the alkyl is a C1 _- C10 alkyl. In other variants of the organophosphorus compounds, the cycloalkyl is C ₃ -C ₁₀ cycloalkyl.

"Cycloalkyl" refers to a carbocyclic non-aromatic group bonded via a ring carbon atom and, in the case of unsubstituted, contains only C and H. Cycloalkyl can consist of one ring or multiple rings. In some variants, cycloalkyls with two or more rings can be linked together by CC bonds, fusions, spiros or crosslinks, or a combination thereof. In some embodiments, the cycloalkyl is a C ₃ -C ₁₀ cycloalkyl. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclohexyl, adamantyl and decahydronaphthalenyl.

In yet another variant of the organophosphorus compound, the halophosphate is a chlorophosphate. In yet another variant of the organophosphorus compound, the halophosphate is a fluorophosphate.

Suitable organophosphorus compounds used in the methods described herein are, for example, ethyldichlorophosphate, diethylchlorophosphate, methyldichlorophosphate, dimethylchlorophosphate, ethyldifluorophosphate, diethylfluorophosphate, methyldifluorophosphate or dimethylfluoro. It may include dichloromethane, or any combination thereof.

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

In some variants, the carbodiimide compound is

であり、式中、各Ｒ^４及びＲ^５は、独立して、アルキル又はシクロアルキルである。上記のある特定の変形形態において、Ｒ^４及びＲ^５は異なる。上記の他の変形形態において、Ｒ^４及びＲ^５は同じである。他の変形形態において、各Ｒ^４及びＲ^５は、独立してシクロアルキルである。

And in the formula, each R ⁴ and R ⁵ are independently alkyl or cycloalkyl. ^In certain variants described above, ^R4 and R5 are different. In the other variants described above, ^R4 and R5 are the ^same . In other variants, each R ⁴ and R ⁵ is independently cycloalkyl.

In certain variants, each R ⁴ and R ⁵ is independently alkyl. In certain variants, each R ⁴ and R ⁵ is an independent and independent C _1-6 alkyl. In one variant, each R ⁴ and R ⁵ is independently methyl, ethyl or propyl. ^In another variant, ^R4 and R5 are both methyl, ethyl or propyl. In another variant, R ⁴ and R ⁵ are both cyclohexyl. In yet another variant, R ⁴ is alkyl and R ⁵ is cycloalkyl.

Suitable carbodiimide compounds used in the methods described herein are, for example,

（当技術分野ではＮ、Ｎ’－ジシクロヘキシルカルボジイミドとしても知られている）を含み得、式中、Ｒ^４及びＲ^５は、両方ともシクロヘキシルである。

(Also known in the art as N, N' ^- dicyclohexylcarbodiimide) can be included, in which ^R4 and R5 are both cyclohexyl.

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

The triazine compounds described herein may be optionally substituted with one or more substituents. In some variants, the triazine compound is substituted with 1, 2 or 3 substituents. In certain variants, the substituent may be a halo group. For example, in certain variants, the triazine compound is a halo-substituted triazine compound. In certain variants, the triazine compound is 1,3,5-triazine substituted with 1, 2, or 3 halo groups. In one variant, the triazine compound is halo-substituted 1,3,5-triazine.

Suitable triazine compounds used in the methods described herein are, for example,

（当技術分野では塩化シアヌルとしても知られている）を含み得る。

(Also known in the art as cyanuric chloride).

<Organosilicon compound>
In certain embodiments, the dehydrating agent comprises an organosilicon compound. In some variants, the organosilicon compound is silazane. Cilazan may be unsubstituted or substituted. In one variant, silazane is substituted with aryl, halo, alkyl, alkoxy or amino groups.

In certain embodiments, organosilicon compounds are

であり、式中、各Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、（各出現で）独立して、Ｈ、アルキル、シクロアルキル、ヘテロアルキル、ヘテロシクロアルキル、アリール、ヘテロアリール、ハロ、アミノ、又はアルコキシである。

And in the equation, each R ⁶ , R ⁷ , R ⁸ and R ⁹ independently (at each appearance) H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, Amino or alkoxy.

In another variant, the organosilicon compound is silane. Silanes may be unsubstituted (eg, hydrosilane) or substituted. In some variants, the silane is substituted with 1, 2, 3 or 4 substituents. In one variant, the silane is substituted with aryl, halo, alkyl, alkoxy or amino groups.

In certain embodiments, organosilicon compounds are

であり、各Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、独立して、Ｈ、アルキル、シクロアルキル、ヘテロアルキル、ヘテロシクロアルキル、アリール、ヘテロアリール、ハロ、アミノ又はアルコキシである。

R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino or alkoxy.

In one embodiment, the organosilicon compound is arylsilane. In some variants, arylsilanes contain 1, 2 or 3 aryl groups. In the above modified form, the aryl group is phenyl. Suitable arylsilanes may include, for example, diphenylsilane and phenylsilane. In one variant, the organosilicon compound is Ph ₂ SiH ₂ . In another variant, the organosilicon compound is PhSiH ₃ .

In other embodiments, the organosilicon compound is halosilane, alkoxysilane, or aminosilane. In one embodiment, the organosilicon compound is halosilane. In some variants, halosilanes contain 1, 2 or 3 halo groups. In certain variants, halosilanes may be further substituted with one or more substituents (other than halos). In one variant, halosilane is further substituted with 1, 2 or 3 substituents (other than halo). In the above modified form, the substituent of halosilane is independently alkyl or aryl. In one variant of the above, the alkyl substituent of halosilane is C _1-6 alkyl. In another variant, the substituent of halosilane is independently methyl or phenyl. Suitable halosilanes may include, for example, dialkyldihalosilanes, aryltrihalosilanes, arylalkyldihalosilanes, or aryltrihalosilanes. In certain variants, the halosilane is chlorosilane. Suitable chlorosilanes may include, for example, dimethyldichlorosilane, phenyltrichlorosilane, or phenylmethyldichlorosilane.

In another embodiment, the organosilicon compound is alkoxysilane. In certain variants, alkoxysilanes include alkyl silicates. In one variant, the alkoxysilane comprises a C _1-6 alkyl silicate. Suitable alkyl silicates include, for example, n-butyl silicates. In other variants, the alkoxysilane contains 1, 2 or 3 alkoxy groups. In certain modifications described above, the alkoxysilane may be further substituted with 1, 2 or 3 substituents (other than alkoxy). In one variant, the substituent of alkoxysilane is independently alkyl or aryl. In one variant of the above, the alkyl substituent of alkoxysilane is C _1-6 alkyl. In another variant, the substituent of alkoxysilane is independently methyl or phenyl. Suitable alkoxysilanes may include, for example, dimethoxy (methyl) phenylsilane.

In yet another embodiment, the organosilicon compound is aminosilane. In certain variants, the aminosilane is an alkylaminosilane. In certain modifications described above, aminosilanes may be further substituted with 1, 2 or 3 substituents (eg, other than amino groups containing alkylamino groups). In one variant, the substituent of aminosilane is an alkoxy group. In one variant of the above, the alkoxy substituent of aminosilane is C _1-6 alkoxy. In another variant, the substituent of aminosilane is independently methoxy or ethoxy. Suitable aminosilanes may include, for example, (3-aminopropyl) triethoxysilane.

In another embodiment, the organosilicon compound is a bis (trialkylsilyl) amine. In one variant, the organosilicon compound is a bis (trimethylsilyl) amine.

In some of the above variants, the silanes described herein can be used in combination with alkylammonium halides as a dehydrating agent. In one variant, the alkylammonium halide is tetrabutylammonium halide, such as tetrabutylammonium chloride or tetrabutylammonium fluoride. In certain variants, organosilicon compounds and alkylammonium halides are provided as mixtures (eg, in solvents) or in combination separately.

<Transition metal complex>
In certain embodiments, the dehydrating agent comprises a transition metal complex. In some variants, the transition metal complex comprises at least one halide or oxide ligand. The halide or oxide ligand may be bonded or complexed with the transition metal.

In certain variants described above, the transition metal complex is provided in a solvent. In other variants, the transition metal complex is provided in water or acetonitrile, or a mixture thereof.

In one embodiment, the transition metal complex is a metal halide. In some variants, the metal halide comprises a Group 10 or Group 12 metal. In certain variants, the metal halide comprises palladium or zinc. In certain variants, the metal halide comprises chloro. Suitable metal halides may include, for example, palladium chloride or zinc chloride.

In some of the above variants, the metal halide is provided in the solvent. In one variant, 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 mixtures thereof.

In another embodiment, the transition metal complex comprises a Group 5 metal. In some variants, the transition metal complex comprises vanadium oxide. In one variant, vanadium oxide is a monomeric vanadium oxide. In certain variants, the dehydrating agent comprises vanadium oxide and hydrotalcite. In one variant, the dehydrating agent comprises the monomers vanadium oxide and hydrotalcite. Vanadium oxide (including, for example, the monomeric vanadium oxide) may be incorporated on the surface of hydrotalcite.

<Aluminum complex>
In certain embodiments, the dehydrating agent comprises an aluminum complex. In some variants, the aluminum complex comprises aluminum halide. In certain variants, the aluminum complex is complexed with water, acetonitrile or alkali metal salts, or mixtures thereof. In some variants, the alkali metal salt is a sodium salt or a potassium salt. In some variants, the alkali metal salt is an alkali metal halide salt. In some variants, the alkali metal halide salt is an alkali metal iodide salt. In some variants, the alkali metal halide salt is sodium iodide or potassium iodide. In some variants, the aluminum complex is AlCl ₃ · H ₂ O / KI / H ₂ O / CH ₃ CN. _In some variants, the aluminum complex is AlCl3 · NaI.

<Other non-uniform dehydrating agents>
In some variants, the dehydrating agent is non-uniform. For example, in certain variants, 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 any combination thereof.

In certain variants, the dehydrating agent comprises a solid metal oxide. In one variant, the dehydrating agents are thio ₂ , ZrO ₂ , Al ₂ O ₃ , SiO ₂ , ZnO ₂ , SnO ₂ , WO ₃ , MnO ₂ , Fe ₂ O ₃ , SiO ₂ / Al ₂ O ₃ , ZrO ₂ . Includes / WO ₃ , ZrO ₂ / Fe ₂ O ₃ , or ZrO ₂ / MnO ₂ , or any combination thereof.

In certain variants, the dehydrating agent is a titanic acid, a metal oxide hydrate, a metal sulfate, a metal oxide sulfate, a metal phosphate, a metal oxide phosphate, a mineral acid, a carboxylic acid or a salt thereof, an acidic resin, an acid. Includes zeolite, clay, or any combination thereof. _In certain variants, the dehydrating agent is H ₃ PO ₄ / SiO ₂ , fluorinated Al ₂ O ₃ , Nb ₂ O ₃ / PO ₄ ^-3 , Nb ₂ O ₃ / SO _4-2 , Nb ² O ₅ , H ₃ PO ₄ , Phosphate, Phosphate Tung Acid, Phosphor Molybdic Acid, Phosphate Molybic Acid, Phosphate Tung Acid, Mg ₂ P ₂ O ₇ , Mg HPO ₄ , or any combination thereof.

In some variants, the dehydrating agent comprises zeolite. In certain variants, the zeolite is hydrogen or ammonia type, or is a metal exchange zeolite. In one variant, the metal exchange zeolite comprises Li, Na, K, Ca, Mg, or Cu. In another variant, the zeolite has a pore diameter in the range of 1-10 angstroms in diameter. In one variant, the zeolite is a medium pore size zeolite. In some variants, 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 variant, the zeolite is a large pore size zeolite. Suitable zeolites may include, for example, ZSM-12, ZSM-5, mordenite, faujasite, or zeolite Y.

In the modified form in which the non-uniform dehydrating agent is used as described above, the compound of the gas phase formula (2) is passed through a heated reactor containing the dehydrating agent to obtain the compound of the formula (2). Dehydration produces a compound of formula (3-I), a compound of formula (3), or a combination thereof. In one variant, the reactor is a packed bed reactor, a fluidized bed reactor, or a moving bed reactor.

<Combination of dehydrating agents>
It should be understood that in some variants, the term "dehydrating agent" may include combinations of agents. In some variants of the methods described herein, combinations of dehydrating agents described herein may be used.

In some embodiments, the dehydrating agent comprises a combination of an organosilicon compound and a transition metal complex. In certain variants of the above combinations, the organosilicon compound is N-methyl-N- (trimethylsilyl) trifluoroacetamide. In some variants of the above combinations, the transition metal complex is a metal trifurate or metal halide. In one variant, the metal triflate is a zinc triflate. In another variant, the metal halide is copper chloride.

In other embodiments, the dehydrating agent comprises a combination of silane and a transition metal complex. In certain variants of the above combinations, the transition metal complex is an iron complex. In one variant, the dehydrating agent comprises a combination of silane and iron complex.

In another variant of the combination of silane and transition metal complex, the transition metal complex is a metal carbonate. In certain variants, the metal carbonate comprises iron. In certain variants, the metal carbonate is iron carbonate. Suitable metal carbonates include, for example, Fe ₂ (CO) ₉ . In some variants of the above combinations, the organosilicon compound is an alkoxyalkylsilane. In certain variants, the alkoxyalkylsilane is a diethoxymethylsilane. In one variant, the dehydrating agent comprises a combination of iron carbonate and alkoxyalkylsilane.

Exemplary combinations of dehydrating agents that can be used in the methods described herein are zinc triflate and N-methyl-N- (trimethylsilyl) trifluoroacetamide; copper chloride and N-methyl-N- (trimethylsilyl) trifluoro. Acetamide; iron complex and silane; as well as iron carbonate and diethoxymethylsilane.

<Use downstream>
Acrylamide, acrylonitrile and other compounds produced according to the methods described herein can be used as monomers for industrial production of polymers in some variants.

The compounds of formula (3-I) produced according to the methods herein can be used to produce one or more downstream products. For example, referring to FIG. 8B, acrylamide produced according to the method described herein can be used to produce polyacrylamide. Accordingly, in certain embodiments, there is provided a method comprising the steps of producing a compound of formula (3-I) and polymerizing the compound of formula (3-I) according to any of the methods herein. To. In one variant, there is provided a method of producing polyacrylamide, comprising the steps of producing acrylamide according to any of the methods herein and the step of polymerizing acrylamide to produce polyacrylamide.

The compounds of formula (2) produced according to the methods herein can be used to produce one or more downstream products. For example, referring again to FIG. 8B, acrylonitrile produced according to the method described herein can be used to produce polyacrylonitrile. Accordingly, in certain embodiments, there is provided a method comprising the steps of producing a compound of formula (2) and polymerizing the compound of formula (2) according to any of the methods herein. In one variant, there is provided a method of producing polyacrylonitrile comprising the steps of producing acrylonitrile according to any of the methods herein and the step of polymerizing acrylonitrile to produce polyacrylonitrile. Polyacrylonitrile may be suitable for a variety of applications, including carbon fiber.

In other embodiments, acrylonitrile produced according to the methods described herein can be used to produce acrylic acid and / or acrylamide.

<Composition>
In some embodiments
Compound of formula (2):

（式中、Ｒ^１は、Ｈ又はアルキルである）と；
脱水剤と
を含む組成物が提供される。

(In the formula, R ¹ is H or alkyl) and;
A composition comprising a dehydrating agent is provided.

In certain embodiments, the composition comprises the compound of formula (3):

（式中、Ｒ^１は、式（２）について上記で定義された通りである）又はその異性体をさらに含む。

(In the formula, R ¹ is as defined above for formula (2)) or further comprises an isomer thereof.

In some of the above variants, the composition is
Compound of formula (1):

（式中、Ｒ^１は、式（２）について上記で定義された通りである）と；
アンモニアとをさらに含む。

(In the equation, R ¹ is as defined above for equation (2));
Further contains with ammonia.

In other embodiments
Compound of formula (1)

（式中、Ｒ^１は、Ｈ又はアルキルである）と；
アンモニアと；
脱水剤と
を含む組成物が提供される。

(In the formula, R ¹ is H or alkyl) and;
With ammonia;
A composition comprising a dehydrating agent is provided.

In some of the above variants, the composition is a compound of formula (3-I) and / or a compound of formula (3):

（式中、Ｒ^１は、式（１）について上記で定義された通りである）又はそれらの異性体をさらに含む。

(In the formula, R ¹ is as defined above for formula (1)) or further comprises isomers thereof.

In certain variants described above, the compounds, dehydrating agents (including combinations of dehydrating agents) and ammonia present in the composition are as described herein for the method.

<System>
In some embodiments, it is a continuous stirring tank reactor, wherein the compound of formula (1):

（式中、Ｒ^１は、Ｈ又はアルキルである）を受容するように構成された第１の入口と；
アンモニアを受容するように構成された第２の入口であって、反応器が、式（１）の化合物をアンモニアに添加して、アンモニアが過剰に存在するような式（１）の化合物に対するアンモニアの比を達成するように構成され、反応器が、温度を維持するのに適した速度で式（１）の化合物をアンモニアに添加するように構成され、反応器が、液体形態のアンモニア及び式（１）の化合物を受容するように構成される、第２の入口と；
反応器内の温度を一定に保つように構成されたジャケットと；
過剰なアンモニアを反応器から放出するように構成されたベントと；
式（１）の化合物及びアンモニアから生成された式（２）の化合物を含む生成物ストリームを放出するように構成された出口と
を備え、式（２）の化合物は、

With a first inlet configured to receive (in the formula, R ¹ is H or alkyl);
Ammonia for a compound of formula (1) such that the reactor is a second inlet configured to receive ammonia and the reactor adds the compound of formula (1) to ammonia and is in excess of ammonia. The reactor is configured to add the compound of formula (1) to ammonia at a rate suitable for maintaining the temperature, and the reactor is configured to add ammonia in liquid form and the formula. With a second entrance configured to receive the compound of (1);
With a jacket configured to keep the temperature inside the reactor constant;
With a vent configured to release excess ammonia from the reactor;
The compound of formula (2) comprises an outlet configured to release a product stream containing the compound of formula (1) and the compound of formula (2) produced from ammonia.

（式中、Ｒ^１は、式（１）について上記で定義された通りである）である連続撹拌槽反応器を含むシステムが提供される。

(In the formula, R ¹ is as defined above for formula (1)). A system including a continuous stirring tank reactor is provided.

In other embodiments, the reactor is
An inlet configured to receive ammonia and the compound of formula (1), the ammonia is gaseous, the compound of formula (1) is liquid, and the compound of formula (1) is.

（式中、Ｒ^１は、Ｈ又はアルキルである）である、入口と；
不均一触媒床であって、
反応器が、アンモニア及び式（１）の化合物を不均一触媒床に同時供給するように構成され、
反応器が、アンモニア及び式（１）の化合物の流速を別々に制御するように構成され、
反応器が、式（１）の化合物をアンモニアに添加して、アンモニアが過剰に存在するような式（１）の化合物に対するアンモニアの比を達成するように構成される、不均一触媒床と；
反応器内の温度を一定に維持するように構成されたジャケットと；
過剰なアンモニアを反応器から放出するように構成されたベントと；
式（１）の化合物及びアンモニアから生成された式（２）の化合物を含む生成物ストリームを放出するように構成された出口と
を備え、式（２）の化合物は、

(In the formula, R ¹ is H or alkyl), with the inlet;
Heterogeneous catalyst bed
The reactor is configured to simultaneously supply ammonia and the compound of formula (1) to the heterogeneous catalyst bed.
The reactor is configured to control the flow rates of ammonia and the compound of formula (1) separately.
With a heterogeneous catalyst bed, the reactor is configured to add the compound of formula (1) to ammonia to achieve the ratio of ammonia to the compound of formula (1) such that ammonia is in excess.
With a jacket configured to keep the temperature inside the reactor constant;
With a vent configured to release excess ammonia from the reactor;
The compound of formula (2) comprises an outlet configured to release a product stream containing the compound of formula (1) and the compound of formula (2) produced from ammonia.

（式中、Ｒ^１は、式（１）について上記で定義された通りである）である反応器を含むシステムが提供される。

(In the equation, R ¹ is as defined above for equation (1)), a system comprising a reactor is provided.

In yet another embodiment
It ’s a tube shell reactor.
One or more tubes in which the catalyst particles are packed between and around one or more tubes; with one or more tubes configured to receive ammonia in gaseous form;
A shell-side inlet of the reactor configured to receive the compound of formula (1) in liquid form, where the reactor produces excess ammonia in the reactor compared to the compound of formula (1). Configured to maintain,
With an inlet, the reactor is configured at a temperature that produces the compound of formula (2) from the compound of formula (1) and ammonia;
A system comprising a tube shell reactor is provided with an outlet configured to release a product stream containing the compound of formula (2) and excess ammonia.

In some of the above variants, the compound of formula (2) is provided in melted form.

<Listed embodiments>
The embodiments listed below are representative of some aspects of the invention.

1. 1. Compounds of formula (3-I) and / or compounds of formula (3):

若しくは

Or

（式中、Ｒ^１は、Ｈ若しくはアルキルである）又はその異性体の生成方法であって、
式（２）の化合物を脱水剤と組み合わせて、式（３）の化合物又はその異性体を生成するステップを含み、
式（２）の化合物は、

(In the formula, R ¹ is H or alkyl) or a method for producing an isomer thereof.
Including the step of combining the compound of formula (2) with a dehydrating agent to produce the compound of formula (3) or an isomer thereof.
The compound of formula (2) is

（式中、Ｒ^１は、式（３－Ｉ）及び（３）について上記で定義した通りである）であり、
脱水剤は、五酸化リン、有機リン化合物、カルボジイミド化合物、トリアジン化合物、有機ケイ素化合物、混合酸化物、遷移金属錯体若しくはアルミニウム錯体、又はそれらの任意の組合せを含む；又は
脱水剤は、固体金属酸化物、固体酸、酸、弱酸、強酸、イオン交換樹脂、アルミノケイ酸塩、又はそれらの任意の組合せを含む方法。

(In the formula, R ¹ is as defined above for the formulas (3-I) and (3)).
Dehydrating agents include phosphorus pentoxide, organic phosphorus compounds, carbodiimide compounds, triazine compounds, organic silicon compounds, mixed oxides, transition metal complexes or aluminum complexes, or any combination thereof; or dehydrating agents solid metal oxidation. A method comprising a substance, a solid acid, an acid, a weak acid, a strong acid, an ion exchange resin, an aluminosilicate, or any combination thereof.

2. 2. Further comprising the step of combining the compound of formula (1) with ammonia to produce the compound of formula (2).
The compound of formula (1) is

（式中、Ｒ^１は、式（３－Ｉ）及び（３）について上記で定義した通りである）である、実施形態１の方法。

(In the formula, R ¹ is as defined above for formulas (3-I) and (3)), the method of embodiment 1.

3. 3. The step of combining the compound of formula (1) with ammonia is the compound of formula (2-I):

（式中、Ｒ^１は、式（３－Ｉ）及び（３）について上記で定義した通りである）をさらに生成する、実施形態２の方法。

The method of embodiment 2, further generating (in the formula, R ¹ is as defined above for formulas (3-I) and (3)).

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

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

若しくは

Or

（式中、Ｒ^１は、Ｈ若しくはアルキルである）又はその異性体の生成方法であって、
式（１）の化合物をアンモニア及び脱水剤と組み合わせて、式（３－Ｉ）の化合物及び／若しくは式（３）の化合物、又はそれらの異性体を生成するステップを含み、
式（１）の化合物は、

(In the formula, R ¹ is H or alkyl) or a method for producing an isomer thereof.
The step comprising combining the 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) is

（式中、Ｒ^１は、式（３－Ｉ）及び（３）について上記で定義した通りである）であり、
脱水剤は、五酸化リン、有機リン化合物、カルボジイミド化合物、トリアジン化合物、有機ケイ素化合物、混合酸化物、遷移金属錯体若しくはアルミニウム錯体、又はそれらの任意の組合せを含む；又は
前記脱水剤は、固体金属酸化物、固体酸、酸、弱酸、強酸、イオン交換樹脂、アルミノケイ酸塩、又はそれらの任意の組み合わせを含む方法。

(In the formula, R ¹ is as defined above for the formulas (3-I) and (3)).
Dehydrating agents include phosphorus pentoxide, organic phosphorus compounds, carbodiimide compounds, triazine compounds, organic silicon compounds, mixed oxides, transition metal complexes or aluminum complexes, or any combination thereof; or said dehydrating agents are solid metals. A method comprising an oxide, a solid acid, an acid, a weak acid, a strong acid, an ion exchange resin, an aluminosilicate, or any combination thereof.

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

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

8. The method of any one of embodiments 1-7, further comprising the step of isolating the compound of formula (3-I) and / or the compound of formula (3).

9. The method of any one of embodiments 1-8, wherein the dehydrating agent comprises phosphorus pentoxide.

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

11. The method of embodiment 10, wherein the organophosphorus compound is an organic phosphate.

12. The method of embodiment 10, wherein the organophosphorus compound is an alkyl halo phosphate or a cycloalkyl halo phosphate.

13. The tenth embodiment, wherein the organophosphorus compound is ethyldichlorophosphate, diethylchlorophosphate, methyldichlorophosphate, dimethylchlorophosphate, ethyldifluorophosphate, diethylfluorophosphate, methyldifluorophosphate or dimethylfluorophosphate, or any combination thereof. Method.

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

15. The carbodiimide compound is

（式中、各Ｒ^４及びＲ^５は、独立して、アルキル又はシクロアルキルである）である、実施形態１４の方法。

The method of embodiment 14, wherein each R ⁴ and R ⁵ are independently alkyl or cycloalkyl in the formula.

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

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

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

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

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

21. The method according to any one of embodiments 1 to 8, wherein the dehydrating agent comprises an organosilicon compound.

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

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

24. Organosilicon compounds

（式中、各Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、独立して、Ｈ、アルキル、シクロアルキル、ヘテロアルキル、ヘテロシクロアルキル、アリール、ヘテロアリール、ハロ、アミノ、又はアルコキシである）である、実施形態２１の方法。

(In the formula, each R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy). 21.

25. 21. The method of embodiment 21, wherein the organosilicon compound is hydrosilane.

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

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

28. 21. The method of embodiment 21, wherein the organosilicon compound is silane.

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

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

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

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

33. The method of embodiment 30 or 31, wherein the transition metal complex is palladium chloride or zinc chloride provided in water, acetonitrile or a mixture thereof.

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

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

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

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

38. The method of embodiment 35, wherein the organosilicon compound comprises silane.

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

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

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

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

43. The dehydrating agent
(I) Zinc triflate and N-methyl-N- (trimethylsilyl) trifluoroacetamide; or (ii) Copper chloride and N-methyl-N- (trimethylsilyl) trifluoroacetamide; or (iii) Iron complex and silane; or (ii) iv) The method of any one of embodiments 1-8, comprising iron carbonate and diethoxymethylsilane.

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

45. The method of embodiment 44, wherein the aluminum complex comprises aluminum halide.

46. The method of embodiment 44 or 45, wherein the aluminum complex is complexed with water, acetonitrile or alkali metal salts, or mixtures thereof.

47. The method of any one of embodiments 1-8, wherein the dehydrating agent comprises AlCl ₃ · H ₂ O / KI / H ₂ O / CH ₃ CN system or AlCl ₃ · NaI.

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

49. The method of embodiment 48, wherein the solid carrier is hydrotalcite.

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

51. Dehydrating agents are TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SiO ₂ , ZnO ₂ , SnO ₂ , WO ₃ , MnO ₂ , Nb ₂ O ₅ , P ₂ O ₅ , Fe ₂ O ₃ , SiO ₂ / Al ₂ . One of embodiments 1-8, comprising O ₃ , ZrO ₂ / WO ₃ , ZrO ₂ / Fe ₂ O ₃ or ZrO ₂ / MnO ₂ , or any combination thereof.

52. The dehydrating agent is titanium acid, metal oxide hydrate, metal sulfate, metal oxide sulfate, metal phosphate, metal oxide phosphate, mineral acid, carboxylic acid or a salt thereof, acidic resin, acidic zeolite, clay, or any of them. The method of any one of embodiments 1-8, comprising any combination.

53. Dehydrating agents are H ₃ PO ₄ / SiO ₂ , Fluorinated Al ₂ O ₃ , Nb ₂ O ₃ / PO ₄ ^-3 , Nb ₂ O ₃ / SO _4-2 , Nb ² O ₅ , H _{3 PO 4 ,} Phosphorus. The method of any one of embodiments 1-8, comprising acid salt, phosphotungonic acid, phosphomolybdic acid, silicate molybdic acid, silicate didnic acid, Mg ₂ P ₂ O ₇ , Mg HPO ₄ , or any combination thereof.

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

55. The method of embodiment 54, wherein the zeolite is a hydrogen type, an ammonia type, or a metal exchange zeolite.

56. The method of embodiment 54, wherein the metal exchange zeolite comprises Li, Na, K, Ca, Mg, or Cu.

57. The method of embodiment 54, wherein the zeolite has a pore diameter in the range of 1-10 angstroms in diameter.

58. The method of embodiment 54, wherein the zeolite is a medium pore size zeolite.

59. The method of embodiment 54, wherein 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.

60. The method of embodiment 54, wherein the zeolite is a large pore size zeolite.

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

62. By passing the compound of the gas phase formula (2) through a heated reactor containing a dehydrating agent, the compound of the formula (2) is dehydrated and / or the compound of the formula (3-1) and / or the formula (3). The method according to any one of embodiments 1 to 61, which comprises producing the compound of.

63. 62. The method of embodiment 62, wherein the reactor is a packed bed reactor, a fluidized bed reactor, or a mobile bed reactor.

64. A method comprising combining the compound of formula (1) and ammonia in a reactor at an average temperature suitable for producing the compound of formula (2) with a selectivity of greater than 50%.
The compound of formula (1) is

であり、
式（２）の化合物は、

And
The compound of formula (2) is

であり、式中、Ｒ^１は、Ｈ又はアルキルである方法。

And in the formula, R ¹ is H or alkyl.

65. The compound of formula (1) and ammonia can be combined in the reactor to combine the compound of formula (2), the compound of formula (3-I) and / or the compound of formula (3), or any isomer thereof (case). Depending on the method), the method comprising the step of generating with a selectivity of more than 50%.
The compound of formula (1) is

であり、
式（２）の化合物は、

And
The compound of formula (2) is

であり、
式（３－Ｉ）の化合物は、

And
The compound of formula (3-I) is

であり、
式（３）の化合物は、

And
The compound of formula (3) is

である、
（式中、Ｒ^１は、Ｈ又はアルキルである）
方法。

Is,
(In the formula, R ¹ is H or alkyl)
Method.

66. Reactor temperature selectivity greater than 50% selectivity for compounds of formula (2), compounds of formula (3-I) and / or compounds of formula (3), or isomers thereof (as the case may be). The method of embodiment 64 or 65, which is maintained at an average temperature suitable for producing in.

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

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

69. The steps to provide ammonia to the reactor,
A step of adding the first portion of the compound of formula (1) to the reactor.
The compound of formula (1) is

（式中、Ｒ^１は、Ｈ又はアルキルである）であるステップと、
式（１）の化合物の第１の部分の添加後、反応器の温度を制御するステップと、
式（１）の化合物の第２の部分を反応器に添加するステップと、
式（１）の化合物の第２の部分の添加後、反応器の温度を制御するステップと
を含む方法であって、式（Ｉ）の化合物の第１の部分及び第２の部分の添加により、式（２）の化合物：

(In the formula, R ¹ is H or alkyl) and
After the addition of the first portion of the compound of formula (1), the step of controlling the temperature of the reactor and
The step of adding the second portion of the compound of formula (1) to the reactor,
A method comprising the step of controlling the temperature of the reactor after the addition of the second portion of the compound of formula (1) by the addition of the first and second portions of the compound of formula (I). , The compound of formula (2):

（式中、Ｒ^１は、上記で定義した通りである）が生成され、
反応器の温度は、式（２）の化合物を生成するのに適した平均温度に制御される方法。

(In the equation, R ¹ is as defined above) is generated.
A method in which the temperature of the reactor is controlled to an average temperature suitable for producing the compound of the formula (2).

70. A method comprising simultaneously supplying a compound of formula (1) and ammonia to a heterogeneous catalyst bed to produce a compound of formula (2).
The compound of formula (1) is

であり、
式（２）の化合物は、

And
The compound of formula (2) is

である、
（式中、Ｒ^１は、Ｈ又はアルキルである）
方法。

Is,
(In the formula, R ¹ is H or alkyl)
Method.

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

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

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

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

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

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

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

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

79. The method of embodiment 78, further comprising the step of recycling the separated ammonia into a reactor.

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 exchange zeolite, a base modified alumina, or a solid "superbase".

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 gaseous.

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

83. One of embodiments 70-82, wherein the ammonia is aqueous ammonia, or the ammonia is liquid ammonia, or the ammonia is anhydrous ammonia, or the ammonia is anhydrous gaseous ammonia.

84. The method according to any one of embodiments 1 to 83, wherein the compound of formula (3-I) is acrylamide and the compound of formula (3) is acrylonitrile.

85. The step of producing acrylamide according to the method of Embodiment 84, and
A method for producing polyacrylamide, which comprises the steps of polymerizing acrylamide to produce polyacrylamide.

86. The step of producing acrylonitrile according to the method of embodiment 84,
A method for producing polyacrylonitrile, which comprises the steps of polymerizing acrylonitrile to produce polyacrylonitrile.

87. The step of producing polyacrylonitrile according to the method of embodiment 86,
A method for producing carbon fibers, which comprises the steps of producing carbon fibers from polyacrylonitrile.

88. A system that includes a continuous stirring tank reactor,
The continuous tank reactor is
Compound of formula (1):

（式中、Ｒ^１は、Ｈ又はアルキルである）を受容するように構成された第１の入口と；
アンモニアを受容するように構成された第２の入口であって、反応器が、式（１）の化合物をアンモニアに添加して、アンモニアが過剰に存在するような式（１）の化合物に対するアンモニアの比を達成するように構成され、
反応器が、温度を維持するのに適した速度で式（１）の化合物をアンモニアに添加するように構成され、
反応器が、液体形態のアンモニア及び式（１）の化合物を受容するように構成される、第２の入口と；
反応器内の温度を一定に保つように構成されたジャケットと；
過剰なアンモニアを反応器から放出するように構成されたベントと；
式（１）の化合物及びアンモニアから生成された式（２）の化合物を含む生成物ストリームを放出するように構成された出口と
を備え、式（２）の化合物は、

With a first inlet configured to receive (in the formula, R ¹ is H or alkyl);
Ammonia for a compound of formula (1) such that the reactor is a second inlet configured to receive ammonia and the reactor adds the compound of formula (1) to the ammonia and is in excess of ammonia. Is configured to achieve a ratio of
The reactor is configured to add the compound of formula (1) to ammonia at a rate suitable for maintaining temperature.
With a second inlet, the reactor is configured to receive the liquid form of ammonia and the compound of formula (1);
With a jacket configured to keep the temperature inside the reactor constant;
With a vent configured to release excess ammonia from the reactor;
The compound of formula (2) comprises an outlet configured to release a product stream containing the compound of formula (1) and the compound of formula (2) produced from ammonia.

（式中、Ｒ^１は、式（１）について上記で定義された通りである）である、システム。

(In the equation, R ¹ is as defined above for equation (1)).

89. It ’s a reactor,
An inlet configured to receive ammonia and the compound of formula (1), the ammonia is gaseous, the compound of formula (1) is liquid, and the compound of formula (1) is.

（式中、Ｒ^１は、Ｈ又はアルキルである）である、入口と；
不均一触媒床であって、反応器が、アンモニア及び式（１）の化合物を不均一触媒床に同時供給するように構成され、
反応器が、アンモニア及び式（１）の化合物の流速を別々に制御するように構成され、
反応器が、式（１）の化合物をアンモニアに添加して、アンモニアが過剰に存在するような式（１）の化合物に対するアンモニアの比を達成するように構成される、不均一触媒床と；
反応器内の温度を一定に維持するように構成されたジャケットと；
過剰なアンモニアを反応器から放出するように構成されたベントと；
式（１）の化合物及びアンモニアから生成された式（２）の化合物を含む生成物ストリームを放出するように構成された出口と
を備え、
前記式（２）の化合物は、

(In the formula, R ¹ is H or alkyl), with the inlet;
The heterogeneous catalyst bed is configured such that the reactor simultaneously supplies ammonia and the compound of formula (1) to the heterogeneous catalyst bed.
The reactor is configured to control the flow rates of ammonia and the compound of formula (1) separately.
With a heterogeneous catalyst bed, the reactor is configured to add the compound of formula (1) to ammonia to achieve the ratio of ammonia to the compound of formula (1) such that ammonia is in excess.
With a jacket configured to keep the temperature inside the reactor constant;
With a vent configured to release excess ammonia from the reactor;
It comprises an outlet configured to release a product stream containing the compound of formula (1) and the compound of formula (2) produced from ammonia.
The compound of the formula (2) is

（式中、Ｒ^１は、式（１）について上記で定義された通りである）である、システム。

(In the equation, R ¹ is as defined above for equation (1)).

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

91. Compound of formula (3):

（式中、Ｒ^１は、Ｈ若しくはアルキルである）又はその異性体の生成方法であって、
式（２）の化合物を脱水剤と組み合わせて、式（３）の化合物又はその異性体を生成するステップを含み、
式（２）の化合物は、

(In the formula, R ¹ is H or alkyl) or a method for producing an isomer thereof.
Including the step of combining the compound of formula (2) with a dehydrating agent to produce the compound of formula (3) or an isomer thereof.
The compound of formula (2) is

（式中、Ｒ^１は、式（３）について上記で定義した通りである）であり、
脱水剤は、五酸化リン、有機リン化合物、カルボジイミド化合物、トリアジン化合物、有機ケイ素化合物、遷移金属錯体若しくはアルミニウム錯体、又はそれらの任意の組合せを含む方法。

(In the equation, R ¹ is as defined above for equation (3)).
A method comprising a dehydrating agent including phosphorus pentoxide, an organic phosphorus compound, a carbodiimide compound, a triazine compound, an organic silicon compound, a transition metal complex or an aluminum complex, or any combination thereof.

92. Further comprising the step of combining the compound of formula (1) with ammonia to produce the compound of formula (2).
The compound of formula (1) is

（式中、Ｒ^１は、式（３）について上記で定義した通りである）である、実施形態９１の方法。

(In the formula, R ¹ is as defined above for the formula (3)), the method of embodiment 91.

93. Compound of formula (3):

（式中、Ｒ^１は、Ｈ若しくはアルキルである）又はその異性体の生成方法であって、
式（１）の化合物をアンモニア及び脱水剤と組み合わせて、式（３）の化合物又はその異性体を生成するステップを含み、
式（１）の化合物は、

(In the formula, R ¹ is H or alkyl) or a method for producing an isomer thereof.
Including the step of combining the compound of formula (1) with ammonia and a dehydrating agent to produce the compound of formula (3) or an isomer thereof.
The compound of formula (1) is

（式中、Ｒ^１は、式（３）について上記で定義した通りである）であり、
脱水剤は、五酸化リン、有機リン化合物、カルボジイミド化合物、トリアジン化合物、有機ケイ素化合物、遷移金属錯体若しくはアルミニウム錯体、又はそれらの任意の組合せを含む方法。

(In the equation, R ¹ is as defined above for equation (3)).
A method comprising a dehydrating agent including phosphorus pentoxide, an organic phosphorus compound, a carbodiimide compound, a triazine compound, an organic silicon compound, a transition metal complex or an aluminum complex, or any combination thereof.

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

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

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

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

98. The method of any one of embodiments 91-95, wherein ^R1 is methyl or ethyl.

99. The method of any one of embodiments 91-98, wherein the dehydrating agent comprises phosphorus pentoxide.

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

101. The method of embodiment 100, wherein the organophosphorus compound is an organic phosphate.

102. The method of embodiment 100, wherein the organophosphorus compound is an alkyl halo phosphate or a cycloalkyl halo phosphate.

103. The 100 of Embodiment 100, wherein the organophosphorus compound is ethyldichlorophosphate, diethylchlorophosphate, methyldichlorophosphate, dimethylchlorophosphate, ethyldifluorophosphate, diethylfluorophosphate, methyldifluorophosphate or dimethylfluorophosphate, or any combination thereof. Method.

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

105. The carbodiimide compound is

（式中、各Ｒ^４及びＲ^５は、独立して、アルキル又はシクロアルキルである）である、実施形態１０４の方法。

The method of embodiment 104, wherein each R ⁴ and R ⁵ are independently alkyl or cycloalkyl in the formula.

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

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

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

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

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

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

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

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

114. Organosilicon compounds

（式中、各Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、独立して、Ｈ、アルキル、シクロアルキル、ヘテロアルキル、ヘテロシクロアルキル、アリール、ヘテロアリール、ハロ、アミノ、又はアルコキシである）である、実施形態１１１の方法。

(In the formula, each R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy). The method of embodiment 111.

115. The method of embodiment 111, wherein the organosilicon compound is hydrosilane.

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

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

118. The method of embodiment 111, wherein the organosilicon compound is silane.

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

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

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

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

123. The method of embodiment 120 or 121, wherein the transition metal complex is palladium chloride or zinc chloride provided in water, acetonitrile or a mixture thereof.

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

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

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

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

128. The method of embodiment 125, wherein the organosilicon compound comprises silane.

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

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

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

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

133. The dehydrating agent
(I) Zinc triflate and N-methyl-N- (trimethylsilyl) trifluoroacetamide; or (ii) Copper chloride and N-methyl-N- (trimethylsilyl) trifluoroacetamide; or (iii) Iron complex and silane; or (ii) iv) The method of any one of embodiments 91-98 comprising iron carbonate and diethoxymethylsilane.

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

135. The method of embodiment 134, wherein the aluminum complex comprises aluminum halide.

136. The method of embodiment 134 or 135, wherein the aluminum complex is complexed with water, acetonitrile or alkali metal salts, or mixtures thereof.

137. The method of any one of embodiments 91-98, wherein the dehydrating agent comprises an AlCl ₃ · H ₂ O / KI / H ₂ O / CH ₃ CN system or an AlCl ₃ · NaI.

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

139. 138. The method of embodiment 138, wherein the solid carrier is hydrotalcite.

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

141. Compound of formula (2):

（式中、Ｒ^１は、Ｈ又はアルキルである）と；
五酸化リン、有機リン化合物、カルボジイミド化合物、トリアジン化合物、有機ケイ素化合物、遷移金属錯体若しくはアルミニウム錯体、又はそれらの任意の組合せを含む脱水剤と
を含む組成物。

(In the formula, R ¹ is H or alkyl) and;
A composition comprising phosphorus pentoxide, an organophosphorus compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex or an aluminum complex, or a dehydrating agent containing any combination thereof.

142. Compound of formula (3):

（式中、Ｒ^１は、式（２）について上記で定義した通りである）
又はその異性体
をさらに含む、実施形態１４１の組成物。

(In the equation, R ¹ is as defined above for equation (2))
Or the composition of embodiment 141 further comprising an isomer thereof.

143. Compound of formula (1):

（式中、Ｒ^１は、式（２）について上記で定義された通りである）と；
アンモニアと
をさらに含む、実施形態１４１又は１４２に記載の組成物。

(In the equation, R ¹ is as defined above for equation (2));
The composition according to embodiment 141 or 142, further comprising ammonia.

144. Compound of formula (1):

（式中、Ｒ^１は、Ｈ又はアルキルである）と；
アンモニアと；
五酸化リン、有機リン化合物、カルボジイミド化合物、トリアジン化合物、有機ケイ素化合物、遷移金属錯体若しくはアルミニウム錯体、又はそれらの任意の組合せを含む脱水剤と
を含む組成物。

(In the formula, R ¹ is H or alkyl) and;
With ammonia;
A composition comprising phosphorus pentoxide, an organophosphorus compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex or an aluminum complex, or a dehydrating agent containing any combination thereof.

145. Compound of formula (3):

（式中、Ｒ^１は、式（１）について上記で定義した通りである）
又はその異性体
をさらに含む、実施形態１４４の組成物。

(In the equation, R ¹ is as defined above for equation (1))
Or the composition of embodiment 144 further comprising an isomer thereof.

The following examples are merely exemplary and are by no means limiting in any aspect of the present disclosure.

[Example 1]
<Anhydrous synthesis of 3-hydroxypropaneamide (3-HP amide)>
This example relates to a step for synthesizing 3-hydroxypropaneamide (3-HP amide) from beta propiolactone (BPL). This step is highly selective to produce a 3-HP amide that is not contaminated with water.

The synthesis is carried out by adding the BPL to a liquid pool of ammonia in a controlled manner. This is performed 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 pressures that may be generated under reaction conditions 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 inside the reactor by condensing boiling ammonia during the reaction process and returning it to the reactor. BPL is added to the liquid ammonia at a rate at which the temperature is controlled to the desired set value. The ratio of ammonia to BPL is always maintained so that the ammonia is extremely excessive.

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

In some variants of this step, the temperature of this reaction is in the range of 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.

[Example 2]
<Heterogeneous catalyst process for the production of 3-HP amide>
This example relates to another step of synthesizing 3-HP amide from BPL. This step is highly selective and is performed continuously on a heterogeneous base catalyst.

The synthesis is carried out by simultaneously supplying BPL and ammonia to the heterogeneous catalyst bed. BPL is supplied to the reactor as a liquid and ammonia is supplied to the reactor as a gas. This reactor configuration is sometimes referred to as 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 outlet of the reactor and the excess gaseous ammonia is separated and recycled to the reactor.

In some variants of the process, the base catalysts used are metal oxides (eg MgO, ZrO), basic zeolites (eg zeolite precursor NH ₄ ZSM5 in ammonia form), alkali metal exchange zeolites, and other modifications. Zeolites, base-modified aluminas, solid "superbases" (eg, lanthanideimides and nitrides on zeolites, metallic acid nitrides _, and KNH ₂ / Al ₂ O3) can be included.

In some variants of this step, the temperature of this reaction is in the range of 10 ° C to 100 ° C. The aqueous reaction occurs at room temperature. In certain variants, this step is performed at a temperature at which the 3-HP amide is gaseous. In one variant, this step is performed at 65-75 ° C.

The product collection flask is below the boiling point of 3-HP amide but above the boiling point of ammonia. In some variants, the collection temperature is −30 ° C. to 65 ° C. In one variant, the collection temperature is about 0 ° C.

[Example 3]
<Reactor design for heterogeneous catalyst production of 3-HP amide>
This example describes the design of a reactor suitable for the process of producing a 3-HP amide from a BPL with a high degree of selectivity, as in the process described in Example 2 above. This reactor is designed so that ammonia and BPL are in contact only in the heterogeneous catalyst bed.

In this example, a tube inside the shell reactor is used. The catalyst particles are filled between the tubes and around the tubes. One reactant, such as ammonia, is supplied to the shell side via a catalyst bed. A second reactant, such as beta propiolactone, is then fed through the tube, making the tube porous with respect to the reactant in one of two modes. In one variant, the tube can be pierced through the length of the tube embedded in the catalyst bed. Alternatively, in another variant, the tube may be made of a porous metal tube through the length of the embedded tube. The tube may have a solid non-porous metal header that extends to or within the catalyst bed. These tubes may be made of various non-reactive metals, including stainless steel, Hastelloy, Inconel and titanium.

In one variant of the above, gaseous ammonia is supplied through the tube and liquid BPL is dropped through the catalyst bed on the shell side. In this configuration, a sintered metal tube may be used, or the pore diameter may be controlled so that the backward diffusion becomes almost zero.

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

The following system incorporates the 3-HP amide production step described in Example 1 above. Anhydrous synthesis of 3-HP amide is carried out in a continuous stirred tank reactor (CSPR), producing a solution of 3-HP amide in ammonia at the end of the reaction. This solution is drained from the CSTR into the holding tank. From the retention tank, 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 of either acrylonitrile or acrylamide and heated to the desired reaction temperature. Will be done. In a heterogeneous reactor, the 3-HP amide is converted to the desired product with high conversion and high selectivity. The resulting acrylonitrile / ammonia or acrylamide / ammonia mixture exits the reactor and is collected in a product recovery vessel, where ammonia is separated from the product, condensed and recycled into a 3-HP amide synthesis vessel. .. Inhibitors may be added at this stage to prevent polymerization. In one variant, the inhibitor is added before the ammonia is removed. In another variant, the inhibitor is added after the ammonia has been removed.

One of the advantages of this approach is that acrylonitrile and / or acrylamide is continuously produced from the BPL solvent-free without intermediate separation and purification steps.

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

The following system incorporates the 3-HP amide production step described in Example 2 and / or Example 3 above. For the steps 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 with excess ammonia required for the optimum yield of 3-HP amide. A mixed 3-HP amide gas phase stream. The 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 a heterogeneous reactor, the 3-HP amide is converted to the desired product with high conversion and high selectivity. The rest of the steps are as described in Example 4A above.

One of the key advantages of this integrated approach is that the amount of unreacted ammonia is lower and the required excess is converted to both step steps (3-HP amide synthesis and subsequent dehydration product acrylonitrile or acrylamide). ) Can be optimized at the same time, and the amount of recycled ammonia required can be minimized. Further, since the feed to the 3-HP amide synthesis reactor in this case is a gas, it is not necessary to condense the recycled ammonia. In addition, acrylonitrile and / or acrylamide is continuously produced from the BPL solvent-free without intermediate separation and purification steps.

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

BPL and ammonia were combined according to the instructions shown in Table 1 below. The yield of 3-HP amide was measured by ¹ H NMR and LC-MS.

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

BPL and ammonium hydroxide were combined in a 5 L reactor at the NH ₄ OH: BPL molar ratio 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 the crude sample of the reaction mixture was measured by ¹ H NMR. The reaction was then run. After the reaction was stopped, the crude reaction measurement material 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 amides are summarized in Table 2 below.

[Example 7]
<Synthesis of 3-HP amide by reaction between BPL and 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 for 3-HP amide.

The reaction was carried out in a temperature controlled reactor with stirring. BPL was supplied 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 supply vessel.

The reactor was filled with 2955 grams of 29 wt% ammonia solution and then pressurized to 40 psig with N ₂ (to provide a positive pressure difference across the BPL metering pump). The stirrer was turned on at about 400 rpm and cooled to 9 ° C. A 535 gram BPL was connected to the supply system and pressurized to 16 psig with N ₂ . The BPL supply rate was increased. During the period of continuous BPL feeding (120 minutes), the temperature of the reactor was maintained at 9-10 ° C. Once all BPL had been supplied to the reactor, the supply was switched to deionized water. Approximately 100 grams of water was supplied to the reactor to remove BPL from the supply line and supply pump. 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.

<Result>
The reaction temperature was properly controlled by the addition of quantitative BPL. An almost instantaneous reaction between BPL and the aqueous solution of concentrated ammonia was observed. A slight increase in reactor temperature (about 1 ° C.) after an increase in BPL feed rate was compensated for by a decrease in CTB setpoints. The reactor was cooled from about 9-10 ° C to about 7 ° C within minutes of stopping the BPL supply.

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

When the reaction between BPL and aqueous ammonia was carried out under sufficiently controlled conditions such as the reaction temperature and the BPL addition rate, the selectivity for the 3-HP amide product was increased.

[Example 8]
<Effect of NH ₄ OH: BPL ratio on 3-HP amide synthesis>
This example evaluates the effect of the NH ₄ OH: BPL ratio on the selectivity for 3-HP amides. 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 into the reactor and 704 grams of BPL was fed at a rate of 5.2 g / hour. did.

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

When the reaction between BPL and aqueous ammonia was carried out under sufficiently controlled conditions such as the reaction temperature and the BPL addition rate, the selectivity for 3-HP amide was increased. The decrease in NH ₄ OH: BPL from 3.3: 1 in Example 7 to 2.4: 1 in this example did not affect the selectivity for 3-HP amide (25% reduction in ammonia usage). .. 775 grams of crude 3-HP amide was produced.

[Example 9]
<Acrylonitrile synthesis using Al ₂ O ₃ >
This example shows the formation of acrylonitrile by dehydration of 3-hydroxypropaneamide using alumina (Al ₂ O ₃ ).

<Reactor configuration>
A continuous tube reactor was used to produce acrylonitrile by dehydration of 3-hydroxypropaneamide. This example was made using a GC injection port that can be heated uniformly. GC glass liners were used in place of tubular reactors. A small amount of catalyst was placed in a liner filled with inert glass wool on both sides.

<Catalyst preparation>
The Al ₂ O ₃ catalyst used was obtained in the form of 1/8 inch pellets. This was crushed, sieved (250-600 μm) and loaded into a reactor.

<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 under reaction temperature and was pushed through the catalyst bed under He carrier gas. By adjusting the amount of catalyst and / or the flow rate of the carrier gas, different residence times could be realized. The injection port can be heated with a heating capacity of 400 ° C. The effluent from the reaction was delivered directly to the GC column for separation and quantitative analysis.

<General procedure>
The 3-HP amide was weighed and placed in an autosampler vial mini-insert and distilled water was added. The 3-HP amide was dissolved to give a 11.08% solution (w / w). The GC infusion port liner ₍ reverse cup design) was packed with a small plug of glass wool just above the cup to support the _Al2O3 particles. Sifted Al ₂ O ₃ was added to give a 0.2 cm long bed. Glass wool was added on the Al ₂ O ₃ floor and held in place. An inactivated open tube liner containing only glass wool was also used for the blank test. The GC coupled with the FID detector was used for product analysis. The total flow rate of helium through the liner was maintained at 42 mL / min with a liner at 400 ° C. The dimensions of the GC column used were 15 meters x 0.32 mm x 0.25 um.

<Result>
The thermal stability of 3-HP amide was investigated in the absence of catalyst. It was observed that the 3-HP amide showed considerable stability at high temperatures up to 400 ° C. in a short period of time. Acrylamide formation was less than 1% and 3-HP amide or ammonia was not detected in GC.

Then, a 3-HP amide aqueous solution was injected into the reaction at 400 ° C. with an Al ₂ O ₃ catalyst bed (0.2 cm). The original GC data for the 15 injections are listed in Table 5 below and the compiled results are shown in FIG. The conversion of 3-HP amide was observed to be 100% with each infusion. The main species found in the product was acrylonitrile (50%).

<Conclusion>
This example of 3-HP amide dehydration using an Al ₂ O ₃ catalyst demonstrated the conversion of 3-HP amide to acrylonitrile. Acrylonitrile was the major product detected by GC.

[Example 10]
<Synthesis of acrylonitrile using Nb ₂ O ₅ >
This example demonstrates the production of acrylonitrile by dehydration of 3-hydroxypropaneamide using Nb ₂ O ₅ . This example was done using the GC injection port as described in Example 9 above.

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

The gas-phase catalytic reaction system was constructed as follows: 30 g of 3-hydroxypropaneamide (99%) was prepared and added to the reaction vessel. The catalyst reactor was filled with 1 g of a 30-60 mesh Al ₂ O ₃ catalyst and 20 g of silicon carbide as an inert carrier before and after the catalyst bed. The raw material 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 temperature of the reactor was maintained at 350 ° C. Samples were collected for 1 hour in increments of about 30 minutes. Samples were analyzed by NMR and GC-FID for acrylonitrile, acrylamide, acrylic acid, 3-hydroxypropaneamide and other potential products. The conversion and selectivity results were calculated using the following equations.

The results showed that the total conversion of 3-HP amidoic acid was 100%. The selectivity of acrylonitrile was 13%. Other products detected in the sample include acrylamide and polyamide.

Claims (13)

Compounds of formula (3-I) and / or compounds of formula (3):

(In the formula, R ¹ is H or alkyl)
Or a method for producing its geometric isomers.
The compound of formula (1) is first reacted in combination with ammonia and then with a dehydrating agent to form the compound of formula (3-I) and / or the compound of formula (3), or their geometric isomers. Including the step of producing the body without isolating the intermediate,
The compound of the formula (1) is

(In the equation, R ¹ is as defined above for equations (3-I) and (3)).
And
The dehydrating agent comprises phosphorus pentoxide, an organic phosphorus compound, a carbodiimide compound, a triazine compound, an organic silicon compound, a mixed oxide, a transition metal complex or an aluminum complex, or any combination thereof; or the dehydrating agent is a solid. A method comprising a metal oxide, a solid acid, an acid, a weak acid, a strong acid, an ion exchange resin, an aluminosilicate, or any combination thereof. The method of claim 1, wherein R ¹ is H, or R ¹ is alkyl, or R ¹ is methyl or ethyl. The method of claim 1 or 2, wherein the dehydrating agent further comprises a solid carrier of hydrotalcite. By passing the compound of the gas phase formula (2) through a heated reactor containing a dehydrating agent, the compound of the formula (2) is dehydrated and the compound of the formula (3-1) and / or the formula (3). ) Is the method according to any one of claims 1 to 3, wherein the compound is produced.
The compound of the formula (2) is

(In the formula, R ¹ is H or alkyl)
Is the way. The step of combining the compound of formula (1) and ammonia in a reactor to form a solution containing the compound of formula (2) and excess ammonia in the first reactor, and the isolation of intermediates. Instead, the solution and catalyst can be combined to produce compounds of formula (3-I) and / or compounds of formula (3), or their geometric isomers (as the case may be), with a selectivity of greater than 50%. A method comprising the steps of forming into a second reactor, the method comprising forming into a second reactor.
The compound of the formula (1) is

And
The compound of the formula (2) is

And
The compound of the formula (3-I) is

And
The compound of the formula (3) is

Is,
(In the formula, R ¹ is H or alkyl)
Method. The temperature of the first or second reactor is the compound of formula (2), the compound of formula (3-I) and / or the compound of formula (3), or their geometric isomers (depending on the case). 5. The method of claim 5, wherein is maintained at an average temperature suitable for producing with a selectivity greater than 50%. The method of claim 6, wherein the catalyst is a heterogeneous catalyst bed comprising a metal oxide, a basic zeolite, an alkali metal exchange zeolite, a base modified alumina, or a solid "superbase". The method according to any one of claims 4 to 7 , wherein the compound of the formula (2) is produced anhydrous. The method according to any one of claims 1 to 6, wherein the compound of the formula (3-I) is acrylamide and the compound of the formula (3) is acrylonitrile. The step of producing acrylamide according to the method of claim 9 and
A method for producing polyacrylamide, which comprises the step of polymerizing the acrylamide to produce polyacrylamide. The step of producing acrylonitrile according to the method of claim 9 and
A method for producing polyacrylonitrile, which comprises a step of polymerizing the acrylonitrile to produce polyacrylonitrile. A system that includes a continuous stirring tank reactor,
The continuous stirring tank reactor is
Compound of formula (1):

(In the formula, R ¹ is H or alkyl)
With a first entrance configured to accept;
A second inlet configured to receive ammonia,
The reactor is configured to add the compound of formula (1) to the ammonia to achieve the ratio of the ammonia to the compound of formula (1) such that the ammonia is in excess.
The reactor is configured to add the compound of formula (1) to the ammonia at a rate suitable for maintaining temperature.
With a second inlet, the reactor is configured to receive the ammonia in liquid form and the compound of formula (1);
With a jacket configured to keep the temperature inside the reactor constant;
With a vent configured to release excess ammonia from the reactor;
Formula (2) produced from the compound of the formula (1) and the ammonia:

(In the equation, R ¹ is as defined above for equation (1))
With an outlet configured to release a product stream containing the compound of; as well as the compound of formula (3-I) and / or the compound of formula (3):

(In the equation, R ¹ is as defined above)
Or with a fixed bed heterogeneous reactor containing a catalyst for producing its geometric isomers;
The system. A system that includes a reactor
The reactor is
An inlet configured to receive ammonia and a compound of formula (1), wherein the ammonia is gaseous and the compound of formula (1) is liquid.
The compound of the formula (1) is

(In the formula, R ¹ is H or alkyl), with the inlet;
Heterogeneous catalyst bed
The reactor is configured to simultaneously supply the ammonia and the compound of the formula (1) to the heterogeneous catalyst bed.
The reactor is configured to separately control the flow rates of the ammonia and the compound of formula (1).
The reactor is configured to add the compound of formula (1) to the ammonia to achieve the ratio of the ammonia to the compound of formula (1) such that the ammonia is in excess. With a homogeneous catalyst bed;
With a jacket configured to keep the temperature inside the reactor constant;
With a vent configured to release excess ammonia from the reactor;
Formula (2) produced from the compound of the formula (1) and the ammonia:

(In the equation, R ¹ is as defined above for equation (1))
With an outlet configured to release a product stream containing the compound of; as well as the compound of formula (3-I) and / or the compound of formula (3):

(In the equation, R ¹ is as defined above)
Or with a fixed bed heterogeneous reactor containing a catalyst for producing its geometric isomers;
The system.

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