KR102529865B1 - Amide and nitrile compounds and methods of making and using them - Google Patents

Abstract

The application provides other compounds that can be prepared from acrylamide and acrylonitrile and hydroxy amide and/or lactones. Methods and systems for preparing such compounds are provided herein.

Description

Amide and nitrile compounds and methods of making and using them

Cross reference to related applications

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

Field

The present invention relates generally to the production of amide products and/or nitrile products, and more particularly to the production from at least epoxides, beta-lactones and/or beta-hydroxy amides.

Nitrogen containing compounds such as amides and nitriles are valuable compounds that can be used for a variety of commercial and industrial applications. For example, acrylonitrile can be used as a starting material in the manufacture of polymers and monomer precursors. Various methods for industrial production of acrylonitrile are known in the art. For example, acrylonitrile can be produced by the catalytic ammoxidation of propylene where propylene, ammonia and air are contacted with a catalyst under elevated temperature and pressure. However, this process generally requires harsh reaction conditions and the use of expensive reagents.

The present invention provides systems and methods for the industrial production of nitriles and other compounds desirable in the art, including precursors for the production of certain nitriles and derivatives made from nitriles, and methods for the production of such compounds, partially or completely, from renewable sources. The problems of the prior art are addressed by providing a system and method.

The present disclosure provides methods and systems for making amide products and/or nitrile products. Advantageously, certain preferred methods and systems provided are biobased alternatives to conventional methods and systems for producing nitriles and amides with reduced cost and reduced damage to the environment.

Preferred embodiments of the present invention relate to systems and methods for preparing amide products and/or nitrile products from epoxides and/or beta-lactones. In certain preferred embodiments, the systems and methods of the present invention can produce amide products and/or nitrile products from biobased epoxides and/or biobased beta-lactones. In certain embodiments, the systems and methods can be modified to selectively produce a desired amide product or nitrile product in greater yield relative to one or more other products. Advantageously, incorporating the systems and methods of the present invention into conventional systems and processes can reduce the environmental impact of making many commercial products.

For example, in some embodiments, a method for preparing an amide compound of formula (3-I) and/or a nitrile compound of formula (3) or an isomer thereof is provided,

(3-I) 또는

(3)

(3-I) or

(3)

In the above formula, R ¹ is H or alkyl;

The method,

combining an amide compound of formula (2) with a dehydrating agent to prepare a nitrile compound of formula (3-I) and/or an amide compound of formula (3), or an isomer thereof,

이고, 상기 식에서 R¹은 화학식 (3-I) 및 (3)에 대해 상기 정의된 바와 같다.The amide compound of formula (2) is

, wherein R ¹ is as defined above for formulas (3-I) and (3).

In certain embodiments of the foregoing, the process further comprises combining a beta-lactone compound of formula (1) with ammonia to prepare a compound of formula (2):

이고, 상기 식에서 R¹은 화학식 (3-I) 및 (3)에 대해 상기 정의된 바와 같다.The beta-lactone compound of formula (1) is

, wherein R ¹ is as defined above for formulas (3-I) and (3).

In some variations of the methods described above, the dehydrating agent comprises a phosphorus pentoxide, an organophosphorus compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a mixed oxide, a transition metal complex, or an aluminum complex, or any combination thereof. In one variation, the dehydrating agent comprises a 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 variations of the methods described above, the dehydrating agent is titanic acid, metal oxide hydrate, metal sulfate, metal oxide sulfate, metal phosphate, metal oxide phosphate, mineral acid, carboxylic acid or salt thereof, acidic resin, acidic zeolite, clay ), or any combination thereof. In certain variations of the methods and systems described above, the dehydrating agent includes a zeolite.

In another aspect, there is provided a method comprising preparing a compound of formula (2) by combining a compound of formula (1) and ammonia in a reactor,

이고,The compound of formula (1) is

ego,

이며,The compound of formula (2) is

is,

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

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

In some embodiments, a compound of formula (1) and ammonia are combined in a reactor to produce a compound of formula (2), a compound of formula (3-I), and/or a compound of formula (3) A method is provided that includes doing,

이고,The compound of formula (1) is

ego,

이며,The compound of formula (2) is

is,

이고, The compound of formula (3-I) is

ego,

이며,The compound of formula (3) is

is,

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

In certain variations of the foregoing, the selectivity for formula (2) is greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%; the selectivity for formula (3) is greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%; The selectivity for Formula (3-I) is greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%.

In some variations of the foregoing, the compound of formula (3-I) is an amide, such as acrylamide, and the compound of formula (3) is a nitrile, such as acrylonitrile. In certain embodiments, preparing an amide, such as acrylamide, according to any of the methods herein; and a method comprising polymerizing the amide. In one variant where the amide is acrylamide, the polymer is polyacrylamide. In another aspect, preparing a nitrile, such as acrylonitrile, according to any of the methods herein; and a method comprising polymerizing the nitrile. In one variation where the nitrile is acrylonitrile, the polymer is polyacrylonitrile. In another aspect, preparing a polyacrylonitrile according to any of the methods herein; and making carbon fibers from polyacrylonitrile.

In another aspect, a system for making amide products and/or nitrile products from at least beta-lactones and/or beta-hydroxy amides is provided. In certain embodiments, provided systems include one or more reactors of a size, shape, and configuration for producing amide products and/or nitrile products. In certain embodiments, one or more reactors may be configured as a continuous stirred tank reactor, a fixed catalyst bed reactor, or a fluidized catalyst bed reactor. In certain embodiments, the system may be configured for use with a heterogeneous catalyst. In other embodiments, the system may be configured for use with homogeneous catalysts.

In various variations of the foregoing, the compounds of the present invention have a biobased content greater than 0% and less than 100%. In certain variations of the foregoing, the compounds of the present invention have a biobased content of at least 10%, at least 20%, at least 50%, at least 70%, at least 95%, or 100%.

In some variations, biobased content can be determined based on: % biobased content = [bio (organic) carbon]/[total (organic) carbon]*100%, which is based on ASTM D6866 (using radiocarbon analysis). as determined by Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gas Samples).

The biobased content of the compositions of the present invention may depend on the biobased content of the beta-lactone used. For example, in some variations of the methods described herein, the beta-lactones used to make the amide products and/or nitrile products described herein may have a biobased content greater than 0% and less than 100%. In certain variations of the methods described herein, the beta-lactone used to make the amide products 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 99.5%, at least 99.9%, at least 99.99%, or 100% of biobased content. In certain variations, beta-lactones derived from renewable sources are used. In another variant, at least a portion of the beta-lactone used is derived from renewable sources and at least a portion of the beta-lactone is derived from non-renewable sources.

The biobased-content of beta-lactone may depend, for example, on the biobased content of carbon monoxide and the epoxide used. In some variations, both the epoxide and carbon monoxide are derived from renewable sources.

This application can be best understood by referring to the following description taken in conjunction with the accompanying drawings in which like parts may be referred to by like numerals.
1, 2, 3, 4, and 6 show exemplary reaction schemes for preparing compounds of formula (3).
5 depicts an exemplary reaction scheme for preparing compounds of formula (3-I).
7A shows a reaction scheme showing how ammonia water contains a dynamically balanced mixture of ammonia gas/water and ammonium.
7B shows an exemplary reaction scheme involving beta-propiolactone and ammonium/ammonia.
8 is from experiments performed in Example 9, involving the preparation of acrylonitrile by dehydration of 3-hydroxypropanamide (abbreviated as “3-HP amide”) with alumina (Al ₂ O ₃ ). It is a graph showing the result of

The following description describes example methods, parameters, and the like. However, it should be appreciated that this description is not intended to limit the scope of the present invention, but instead is provided as a description of exemplary embodiments.

Provided herein are methods and systems for preparing amide products and/or nitrile products from at least beta-lactones and/or beta-hydroxy amides. In certain preferred embodiments, the amide product comprises acrylamide and the nitrile product comprises acrylonitrile. In certain variations, beta-lactones can be prepared by carbonylating an epoxide with carbon monoxide.

In some embodiments, methods for preparing acrylonitrile compounds and other nitrile compounds from beta-hydroxy amides are provided. For example, referring to Figure 1 , beta-hydroxy amide of formula (2) is combined with a dehydrating agent to produce an acrylonitrile compound of formula (3) or another nitrile compound, or an isomer thereof.

In another aspect, a method for preparing an acrylonitrile compound or other nitrile compound from a lactone is provided. For example, referring to FIG. 2 , the beta-lactone of formula (1) can be combined with ammonia to produce the beta-hydroxy amide of formula (2), which is then shown in the example shown in FIG . The compound of formula (3), or an isomer thereof, is prepared by undergoing a reaction.

In another example, referring to FIG. 3 , beta-lactone of formula (1) is combined with ammonia in water (also referred to as ammonia water) and a dehydrating agent to obtain an acrylonitrile compound of formula (3) or another nitrile compound, or its Isomers can be prepared.

In another example, referring to FIG. 4 , the conversion of a beta-lactone of formula (1) to a nitrile compound of formula (3), or an isomer thereof, of formulas (2) and (3) that can be dehydrated to produce nitriles. -I) is shown to represent the intermediate compound. In one aspect, a process is provided comprising combining a compound of formula (1) and ammonia in a reactor to produce a compound of formula (2), each with a selectivity greater than 80%. In another embodiment, a compound of Formula (1) and ammonia are combined in a reactor to obtain a compound of Formula (2), a compound of Formula (3-I), and/or a compound of Formula (3) with a selectivity greater than 80%. A method comprising preparing is provided.

In some variations of the foregoing, the selectivity is 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85%, 90%, 95%, 96%, 97%, 98%. %, or greater than 99%. Selectivity can be controlled by one or more parameters. For example, in some variations, the temperature of the reactor is maintained at an average temperature of -20°C to 50°C, or 10°C to 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 to the reactor containing the ammonia.

In another variation, providing a first part of a compound of formula (1) to a reactor; adding ammonia; and maintaining the average temperature of the reactor to produce the compound of formula (2). In one variation, the method further comprises isolating the compound of formula (2). In certain embodiments, the step to maintain the average temperature occurs between -20°C and 50°C.

In another variation, co-feeding 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). In one variation, the method further comprises isolating the compound of formula (2). In certain embodiments, the compound of formula (1) is supplied as a liquid to the reactor and contacted with the heterogeneous catalyst. In certain variations, the flow rates of the compound of formula (1) and ammonia are controlled separately. In certain variations, ammonia is present in excess in the reactor. In another embodiment, the process further comprises collecting from the reactor a product stream comprising a compound of formula (2) and excess ammonia. In one variant, the compound of formula (2) is collected in liquid form. In another embodiment, the method comprises separating excess ammonia from the product stream; and recycling the separated ammonia to the reactor. In another variation, the heterogeneous catalyst bed includes any of the heterogeneous dehydrating agents described herein. For example, in one variation, the heterogeneous catalyst bed comprises a metal oxide, a basic zeolite, an alkali metal exchanged zeolite, a base modified alumina, or a solid “super base”. In another variation, the temperature of the reactor is maintained within the range of 10°C to 100°C, or 65°C to 75°C, or room temperature. In one variant, the reactor is maintained at a temperature at which the compound of formula (2) is a gas. In another variant, the compound of formula (2) is prepared anhydrous.

In some variations of the foregoing, the compound of formula (1) is combined with liquid ammonia. In another variation of the foregoing, the compound of formula (1) is combined with ammonia in the absence of a solvent. In certain variations, the compound of formula (1) is combined with ammonia (or ammonium hydroxide) in water. In other words, in certain variations, the ammonia is aqueous ammonia. Referring to FIG. 7A , it should be generally understood that aqueous ammonia includes a dynamically balanced mixture of ammonia gas/water and ammonium hydroxide. In another variation, the compound of formula (1) is combined with anhydrous ammonia. In one variation, the ammonia is anhydrous gaseous ammonia. Referring to FIG. 7B , when anhydrous ammonia is used, at least one step (eg, removal of water prior to the dehydration reaction) can be avoided. Ammonia can be obtained from any commercially available source or prepared according to any method known in the art.

In another variation, the compound of formula (1) is combined with ammonia under elevated temperature. In another variant, the compound of formula (1) is combined with ammonia and a further basic compound.

In certain variations of the foregoing, as shown in Figure 3 , ammonia is combined with a compound of formula (1) and any dehydrating agent described herein. In another variation, as shown in Figures 2 and 4 , ammonia is combined with a compound of formula (1) to first produce a beta-hydroxy amide of formula (2), followed by any dehydration described herein. I is combined with the beta-hydroxy amide of formula (2) to produce a compound of formula (3-I), and/or a compound of formula (3), or isomers of the foregoing.

In another aspect, referring to FIG. 5 , a method for preparing an amide of formula (3-I), or an isomer thereof, from a beta-hydroxy amide of formula (2) is provided. In another aspect, referring to FIG. 6 , a method for preparing a nitrile of formula (3), or an isomer thereof, from an amide of formula (3-I), or an isomer thereof, is provided. A dehydration reaction is included by the exemplary reactions shown in Figures 5 and 6 , which may use any of the dehydrating agents described herein.

In certain preferred embodiments, for formulas (1), (2), (3-I) and (3), R ¹ is H. In this embodiment, acrylonitrile can be prepared from beta-propiolactone via 3-hydroxypropiamide and acrylamide. In certain variations, the 3-hydroxypropiamide and/or acrylamide may be isolated and optionally further purified.

Amide products and/or nitrile products made according to the methods and systems herein may find use in a variety of subsequent processes. For example, in one variation, acrylamide can be polymerized to form polyacrylamide; Acrylonitrile can be polymerized to form polyacrylonitrile. The polyacrylonitrile produced may be suitable for a variety of applications including carbon fibers.

The method is explored in further detail below, including acrylamide and acrylonitrile compounds and other compounds that can be prepared, as well as amides, lactones and dehydrating agents that can be used.

Acrylonitrile compounds and other nitrile compounds

In one aspect, a method for preparing acrylonitrile and other nitrile compounds, respectively, from beta-propiolactone and other lactones is provided. For example, in one variant, beta-propiolactone can be reacted with ammonia water to obtain a crude 3-hydroxypropanamide aqueous solution. The crude solution is then purified with resin to remove impurities and then water to obtain pure 3-hydroxypropanamide in solid form. Next, pure 3-hydroxypropanamide may be fed continuously to a fixed bed reactor packed with a dehydration catalyst. The 3-hydroxypropanamide solid can be heated above its melting point and then further mixed/evaporated with nitrogen sweep gas in the preheat zone before passing through the catalyst bed. Dehydration of 3-hydroxypropanamide to acrylonitrile in the presence of water can occur on the catalyst surface.

In some embodiments, the acrylonitrile compound and other nitrile compounds prepared according to the methods herein are compounds of formula (3), or an isomer thereof:

(3)

(3)

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

"Alkyl" refers to a monoradical unbranched or branched saturated hydrocarbon chain. In some embodiments, an alkyl is 1 to 10 carbon atoms (ie, C _1-10 alkyl), 1 to 9 carbon atoms (ie, C _1-9 alkyl), 1 to 8 carbon atoms (ie, C _{1 -8} alkyl), 1 to 7 carbon atoms (ie, C _1-7 alkyl), 1 to 6 carbon atoms (ie, C _1-6 alkyl), 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) ) has Examples of alkyl are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, 3-methyl pentyl; and the like. When an alkyl moiety having a certain number of carbon atoms is named, all geometric isomers having that number of carbon atoms may be included; Thus, for example, “butyl” may include n-butyl, sec-butyl, isobutyl, and t-butyl; “Profile” may include n-propyl and isopropyl.

"Alkenyl" refers to an unsaturated linear or branched monovalent hydrocarbon chain or combination thereof having at least one site of olefinic unsaturation (ie, having at least one moiety of the formula C=C). In some embodiments, alkenyl has 2 to 10 carbon atoms (ie, C _2-10 alkenyl). The alkenyl group may be in the "cis" or "trans" configuration, or alternatively in the "E" or "Z" configuration. Examples of alkenyl are ethenyl, allyl, prop-1-enyl, prop-2-enyl, 2-methylprop-1-enyl, but-1-enyl, but-2-enyl, but-3- enyl, its isomers, and the like.

"Cycloalkyl" refers to a carbocyclic non-aromatic group linked through 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 to 18 cyclic carbon atoms having a ring system with a single ring or multiple condensed rings. Examples of aryl include phenyl, naphthyl, and the like.

In some variations, an alkyl, alkenyl, cycloalkyl, or aryl for R ¹ may be optionally substituted. The term “optionally substituted” means that a particular group is unsubstituted or substituted by one or more substituents. In certain variations, 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 , wherein R is independently H, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted aryl. In some embodiments, R is independently unsubstituted alkyl, unsubstituted alkenyl, or unsubstituted aryl. In some embodiments, R is independently H, methyl (Me), ethyl (Et), propyl (Pr), butyl (Bu), benzyl (Bn), allyl, phenyl (Ph), or haloalkyl. In certain embodiments, substituents are F, Cl, -OSO ₂ Me, -OTBS (wherein "TBS" is tert-butyl(dimethyl)silyl), -OMOM (wherein "MOM" is methoxymethyl acetal). ), -OMe, -OEt, -O i Pr, -OPh, -OCH ₂ CHCH ₂ , -OBn, -OCH ₂ (furyl), -OCF ₂ CHF ₂ , -C=CH ₂ , -OC(O) Me, -OC(O) n Pr, -OC(O)Ph, -OC(O)C(Me)CH ₂ , -C(O)OMe, -C(O)O n Pr, -C(O) NMe ₂ , -CN, -Ph, -C ₆ F ₅ , -C ₆ H ₄ OMe, and -OH.

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

(당업계에서는 아크릴로니트릴로도 알려짐)이다.In some variations, R ¹ is H and the compound of formula (3) is

(also known in the art as acrylonitrile).

또는 이의 이성질체(당업계에서는 크로토노니트릴로도 알려짐)이다. R¹이 에틸일 때, 화학식 (3)의 화합물은

또는 이의 이성질체(당업계에서는 2-펜텐니트릴로도 알려짐)이다.In another variation, R ¹ is alkyl. In certain variations, R ¹ is C _1-6 alkyl. In one variation, R ¹ is methyl or ethyl. When R ¹ is methyl, the compound of formula (3) is

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

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

"Alkyl" refers to a monoradical unbranched or branched saturated hydrocarbon chain. In some embodiments, an alkyl is 1 to 6 carbon atoms (ie, C _1-6 alkyl), 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). In other embodiments, the alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, and 3-methylpentyl. When an alkyl moiety having a specific number of carbon atoms is named, all geometric isomers having that number of carbon atoms may be included; Thus, for example, “butyl” may include n-butyl, sec-butyl, isobutyl, and t-butyl; “Profile” may include n-propyl and isopropyl.

Also, when a range of values is recited, it should be understood that each value and sub-ranges within that value are intended to be included. 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 , C _1-6 , C _1-5 , C _1-4 , C _1-3 , C _1-2 , C 2-6 , C _2-5 , C _2-4 , C _2-3 , _{C 3 -6} , C _3-5 , C _3-4 , C _4-6 , C _4-5 , and C _5-6 alkyl.

Acrylamide and other amides

In some embodiments, acrylamide or other amides may be used to prepare acrylonitrile compounds and other nitrile compounds. In some variations, such amides are compounds of formula (3-I):

(3-I)

(3-I)

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

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

(또는 아크릴아마이드)이다. 다른 변형에서, R¹은 알킬이다. 특정 변형에서, R¹은 C_1-6 알킬이다. 일 변형에서, R¹은 메틸 또는 에틸이다. R¹이 메틸일 때, 화학식 (3-I)의 화합물은

또는

(당업계에서는 부트-2-엔아마이드로도 알려짐)이다. R¹이 에틸일 때, 화학식 (2)의 화합물은

또는

(당업계에서는 펜트-2-엔아마이드로도 알려짐)이다.In some variations, R ¹ is H and the compound of formula (3-I)

(or acrylamide). In another variation, R ¹ is alkyl. In certain variations, R ¹ is C _1-6 alkyl. In one variation, R ¹ is methyl or ethyl. When R ¹ is methyl, the compound of formula (3-I) is

or

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

or

(also known in the art as pent-2-enamide).

When a compound of formula (3-I), or an isomer thereof, is used to prepare a compound of formula (3), or an isomer thereof, R ¹ of formula (3-I) is as defined for formula (3). should be generally understood.

Acrylamide and other amides, such as compounds of Formula (3-I), may be obtained from the methods described herein, or from any commercially available source, or prepared according to any method known in the art.

In certain embodiments, compounds of Formula (3-I) prepared according to the methods herein can be isolated. In some variations, a compound of formula (3-I) prepared according to the methods herein can be isolated and purified. Compounds of Formula (3-I) prepared according to the methods herein may be isolated.

Beta-hydroxy amides and other hydroxy amides

In some embodiments, the beta-hydroxy amide or other hydroxy amide that can be used to prepare acrylonitrile compounds and other nitrile compounds according to the methods herein is a compound of formula (2):

(2)

(2)

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

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

(또는 3-하이드록시프로판아마이드)이다. 다른 변형에서, R¹은 알킬이다. 특정 변형에서, R¹은 C_1-6 알킬이다. 일 변형에서, R¹은 메틸 또는 에틸이다. R¹이 메틸일 때, 화학식 (2)의 화합물은

(또는 3-하이드록시부탄아마이드)이다. R¹이 에틸일 때, 화학식 (2)의 화합물은

(또는 3-하이드록시펜탄아마이드)이다.In some variations, R ¹ is H and the compound of formula (2) is

(or 3-hydroxypropanamide). In another variation, R ¹ is alkyl. In certain variations, R ¹ is C _1-6 alkyl. In one variation, R ¹ is methyl or ethyl. When R ¹ is methyl, the compound of formula (2) is

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

(or 3-hydroxypentanamide).

It should be generally understood that when a compound of formula (2) is used to prepare a compound of formula (3), or an isomer thereof, R ¹ in formula (2) is as defined for formula (3).

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

In certain embodiments, compounds of formula (2) prepared according to the methods herein can be isolated. In some variations, compounds of formula (2) prepared according to the methods herein may be isolated and purified. Compounds of formula (2) prepared according to the methods herein may be isolated.

Beta-lactones and other lactones

In some embodiments, beta-lactones can be used to prepare beta-hydroxy amides, acrylamides, acrylonitriles and other compounds according to the methods herein. In certain embodiments, the beta-lactone is a compound of formula (1):

(1)

(One)

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

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

(당업계에서는 베타-프로피오락톤으로도 알려짐)이다. In some variations, R ¹ is H and the compound of formula (1) is

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

(당업계에서는 베타-부티로락톤으로도 알려짐)이다. R¹이 에틸일 때, 화학식 (1)의 화합물은

(당업계에서는 베타-발레로락톤으로도 알려짐)이다.In another variation, R ¹ is alkyl. In certain variations, R ¹ is C _1-6 alkyl. In one variation, R ¹ is methyl or ethyl. When R ¹ is methyl, the compound of formula (1) is

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

(also known in the art as beta-valerolactone).

When a compound of formula (1) is used to prepare a compound of formula (2), a compound of formula (3), or an isomer thereof, R ¹ of formula (1) is for formula (2) or formula (3) It should be generally understood that as defined.

Beta-lactones, such as compounds of formula (1), can be obtained from any commercially available source or prepared according to any method known in the art. For example, beta-propiolactone can be obtained by reacting ethylene oxide with carbon monoxide under suitable conditions. In some variations, the amide product and/or nitrile product can be prepared from any of the beta-lactones provided in column B of Table A below. As shown in Table A, these beta-lactones of column B can be prepared from the corresponding epoxides from column A of the table.

Beta-lactones, such as compounds of formula (1), can be obtained from renewable feedstock. For example, when beta-propiolactone is prepared from ethylene oxide and carbon monoxide, one or both of the ethylene oxide and carbon monoxide may be obtained from renewable feedstocks using methods known in the art. When beta-lactones, such as compounds of formula (1), are partially or completely obtained from renewable feedstocks, polyamides prepared according to the methods described herein from such beta-lactones have a biocontent greater than 0%. have

A variety of techniques for determining the biocontent of a material are known in the art. For example, in some variations, the biocontent of a material can be determined using the ASTM D6866 method, which allows determination of the biocontent of a material using radiocarbon analysis by accelerator mass spectrometry, liquid scintillation counting, and isotope mass spectrometry. . Biocontent results can be derived by assigning 100% equal to 107.5 percent modern carbon (pMC) and 0% equal to 0 pMC. For example, a sample measuring 99 pMC will give an equivalent biocontent result of 93%. In one variant, biocontent can be determined according to ASTM D6866 Revision 12 (ie, ASTM D6866-12). In another variant, biocontent can be determined according to the procedure in Method B of ASTM-D6866-12. Other techniques for assessing the biological content of materials are described in U.S. Pat. Nos. 3,885,155, 4,427,884, 4,973,841, 5,438,194, and 5,661,299, as well as WO2009/155086.

dehydrator

Dehydration generally involves converting carbon-carbon single bonds to carbon-carbon double bonds, producing water molecules. The dehydration reactions described herein can occur in the presence of suitable homogeneous or heterogeneous catalysts.

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 hydrates, metal sulfates (MSO ₄ , where M can be Zn, Sn, Ca, Ba, Ni, Co, or other transition metal), metal oxide sulfates, metal phosphates (eg, M ₃ (PO ₄ ) ₂ , where M can be Ca or Ba), metal phosphates, metal oxide phosphates, carbon (eg, transition metals on a carbon support), may include mineral acids, carboxylic acids, their salts, acidic resins, acidic zeolites, clays, SiO ₂ /H ₃ PO ₄ , fluorinated Al ₂ O ₃ , phosphotungstic acid, phosphomolybdic acid, silicolybdic acid, silicotungstic acid and carbon dioxide. there is. Examples of suitable bases may include NaOH, ammonia, polyvinylpyridine, metal hydroxides, Zr(OH) ₄ , and substituted amines. Examples of suitable oxides may 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 there is.

In some embodiments, the dehydrating agent used in the methods described herein includes phosphorus pentoxide, organophosphorus compounds, carbodiimide compounds, triazine compounds, organosilicon compounds, mixed oxides, transition metal complexes, or aluminum complexes.

In certain embodiments, the dehydrating agent used in the methods described herein may further comprise a solid support. A suitable solid support may include, for example, hydrotalcite.

The dehydrating agent may be obtained from commercially available sources or prepared according to any method known in the art.

phosphorus compound

In certain embodiments, the dehydrating agent used in the methods described herein includes a phosphorus compound.

In one variation, the dehydrating agent includes phosphorus pentoxide.

In some variations, the dehydrating agent includes an organophosphorus compound. In certain variations, the organophosphorus compound is an organophosphate. In certain variations, the organophosphorus compound is an alkyl halophosphate or cycloalkyl halophosphate. In one variation, the alkyl halophosphate is an alkyl dihalophosphate or a dialkyl halophosphate. In another variation, the cycloalkyl halophosphate is a cycloalkyl dihalophosphate, or a dicycloalkyl halophosphate. In some variations of the aforementioned organophosphorus compounds, the alkyl is a C ₁ -C ₁₀ alkyl. In another variation of the aforementioned organophosphorus compounds, the cycloalkyl is C ₃ -C ₁₀ cycloalkyl.

"Cycloalkyl" refers to a carbocyclic non-aromatic group linked through a ring carbon atom containing only C and H when unsubstituted. Cycloalkyls can consist of a single ring or multiple rings. In some variations, cycloalkyls having more than one ring may be linked together by C-C bonds, fusions, spiro or bridges, or combinations thereof. In some embodiments, cycloalkyl is C ₃ -C ₁₀ cycloalkyl. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclohexyl, adamantyl, and decahydronaphthalenyl.

In another variation of the aforementioned organophosphorus compounds, the halophosphate is a chlorophosphate. In another variation of the aforementioned organophosphorus compounds, the halophosphate is a fluorophosphate.

Suitable organophosphorus compounds for use in the methods described herein include, for example, ethyl dichlorophosphate, diethyl chlorophosphate, methyl dichlorophosphate, dimethyl chlorophosphate, ethyl difluorophosphate, diethyl fluorophosphate, methyl difluorophosphate , or dimethyl fluorophosphate, or any combination thereof.

carbodiimide compounds

In certain embodiments, the dehydrating agent includes a carbodiimide compound.

이되, 상기 식에서 각각의 R⁴ 및 R⁵는 독립적으로 알킬 또는 사이클로알킬이다. 상술한 것의 특정 변형에서, R⁴ 및 R⁵는 상이하다. 상술한 것의 다른 변형에서, R⁴ 및 R⁵는 동일하다. 다른 변형에서, 각각의 R⁴ 및 R⁵는 독립적으로 사이클로알킬이다.In some variations, the carbodiimide compound is

wherein each of R ⁴ and R ⁵ in the above formula is independently alkyl or cycloalkyl. In certain variations of the foregoing, R ⁴ and R ⁵ are different. In another variation of the foregoing, R ⁴ and R ⁵ are the same. In another variation, each of R ⁴ and R ⁵ is independently cycloalkyl.

In certain variations, each of R ⁴ and R ⁵ is independently alkyl. In certain variations, each of R ⁴ and R ⁵ is independently C _1-6 alkyl. In one variation, each of R ⁴ and R ⁵ is independently methyl, ethyl or propyl. In another variation, R ⁴ and R ⁵ are both methyl, ethyl or propyl. In another variation, R ⁴ and R ⁵ are both cyclohexyl. In another variation, R ⁴ is alkyl and R ⁵ is cycloalkyl.

(당업계에서는 N,N'-디사이클로헥실카르보디이미드로도 알려짐)를 포함할 수 있되, 상기 식에서 R⁴ 및 R⁵는 둘 다 사이클로헥실이다.Suitable carbodiimide compounds for use in the methods described herein include, for example,

(also known in the art as N,N' -dicyclohexylcarbodiimide), wherein R ⁴ and R ⁵ are both cyclohexyl.

triazine compounds

.In certain embodiments, the dehydrating agent includes a triazine compound. In one variation, the triazine compound is a 1, 3, 5-triazine and has the structure:

.

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

(당업계에서는 시아누르산 염화물로도 알려짐)을 포함할 수 있다.Suitable triazine compounds for use in the methods described herein include, for example,

(also known in the art as cyanuric acid chloride).

organosilicon compounds

In certain embodiments, the dehydrating agent includes an organosilicon compound. In some variations, the organosilicon compound is a silazane. Silazanes may be unsubstituted or substituted. In one variation, the silazanes are substituted with aryl, halo, alkyl, alkoxy or amino groups.

이되, 상기 식에서 각각의 R⁶, R⁷, R⁸ 및 R⁹는 (각각의 경우에) 독립적으로 H, 알킬, 사이클로알킬, 헤테로알킬, 헤테로사이클로알킬, 아릴, 헤테로아릴, 할로, 아미노, 또는 알콕시이다.In certain embodiments, the organosilicon compound

wherein each R ⁶ , R ⁷ , R ⁸ and R ⁹ (in each case) is independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino, or is alkoxy.

In another variant, the organosilicon compound is a silane. Silanes can be unsubstituted (eg hydrosilane) or substituted. In some variations, the silanes are substituted with 1, 2, 3 or 4 substituents. In one variation, the silane is substituted with an aryl, halo, alkyl, alkoxy or amino group.

이되, 상기 식에서 각각의 R⁶, R⁷, R⁸ 및 R⁹는 독립적으로 H, 알킬, 사이클로알킬, 헤테로알킬, 헤테로사이클로알킬, 아릴, 헤테로아릴, 할로, 아미노, 또는 알콕시이다.In certain embodiments, the organosilicon compound

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

In one embodiment, the organosilicon compound is an arylsilane. In some variations, the arylsilane contains 1, 2 or 3 aryl groups. A variation of the aforementioned 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 a halosilane, alkoxysilane, or aminosilane. In one embodiment, the organosilicon compound is a halosilane. In some variations, the halosilane contains 1, 2 or 3 halo groups. In certain variations, halosilanes may be further substituted with one or more substituents (other than halo). In one variation, the halosilane is further substituted with 1, 2 or 3 substituents (other than halo). In variations of the foregoing, the substituents on the halosilanes are independently alkyl or aryl. In one variation of the foregoing, the alkyl substituent of the halosilane is C _1-6 alkyl. In another variation, the substituents of the halosilanes are independently methyl or phenyl. Suitable halosilanes may include, for example, dialkyldihalosilanes, aryltrihalosilanes, arylalkyldihalosilanes, or aryltrihalosilanes. In certain variations, the halosilane is a chlorosilane. Suitable chloro silanes may include, for example, dimethyldichlorosilane, phenyltrichlorosilane, or phenylmethyldichlorosilane.

In another embodiment, the organosilicon compound is an alkoxysilane. In certain variations, alkoxysilanes include alkylsilicates. In one variation, the alkoxysilane includes a C _1-6 alkylsilicate. Suitable alkylsilicates include, for example, n -butylsilicate. In another variant, the alkoxysilane contains 1, 2 or 3 alkoxy groups. In certain variations of the foregoing, the alkoxysilane may be further substituted with 1, 2 or 3 substituents (other than alkoxy). In one variation, the substituents of the alkoxysilanes are independently alkyl or aryl. In one variation of the foregoing, the alkyl substituent of the alkoxysilane is C _1-6 alkyl. In another variation, the substituents of the alkoxysilanes are independently methyl or phenyl. A suitable alkoxysilane may include, for example, dimethoxy(methyl)phenylsilane.

In another embodiment, the organosilicon compound is an aminosilane. In certain variations, the aminosilane is an alkylaminosilane. In certain variations of the foregoing, the aminosilane may be further substituted with 1, 2 or 3 substituents (eg, other than amino groups including alkylamino groups). In one variation, the substituent of the aminosilane is an alkoxy group. In one variation of the foregoing, the alkoxy substituent of the aminosilane is C _1-6 alkoxy. In another variation, the substituents of aminosilanes are independently methoxy or ethoxy. A suitable aminosilane may include, for example, (3-aminopropyl)triethoxysilane.

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

In some variations of the foregoing, the silanes described herein may be used in combination with an alkylammonium halide as a dehydrating agent. In one variation, the alkylammonium halide is a tetrabutylammonium halide, such as tetrabutylammonium chloride or tetrabutylammonium fluoride. In certain variations, the organosilicon compound and the alkylammonium halide are provided as a mixture (eg, in a solvent) or combined separately.

transition metal complex

In certain embodiments, the dehydrating agent comprises a transition metal complex. In some variations, the transition metal complex includes at least one halide or oxide ligand. Halide or oxide ligands may be associated or complexed with transition metals.

In certain variations of the foregoing, the transition metal complex is provided in a solvent. In another variation, the transition metal complex is provided in water or acetonitrile, or a combination thereof.

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

In some variations of the foregoing, the metal halide is provided in a solvent. In some variations, the metal halide is provided in water, acetonitrile or mixtures thereof. For example, the transition metal complex used in the methods described herein can be palladium chloride or zinc chloride provided in water, acetonitrile or mixtures thereof.

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

aluminum composite

In certain embodiments, the dehydrating agent includes an aluminum complex. In some variations, the aluminum composite includes an aluminum halide. In certain variations, the aluminum composite is complexed with water, acetonitrile, or an alkali metal salt, or mixtures thereof. In some variations, the alkali metal salt is a sodium salt or potassium salt. In some variations, the alkali metal salt is an alkali metal halide salt. In some variations, the alkali metal halide salt is an alkali metal iodide salt. In some variations, the alkali metal halide salt is sodium iodide or potassium iodide. In some variations, the aluminum composite is AlCl ₃ .H ₂ O/KI/H ₂ O/CH ₃ CN. In some variations, the aluminum complex is AlCl ₃ ·NaI.

other heterogeneous dehydrating agents

In some variations, the dehydrating agent is heterogeneous. For example, in certain variations, the dehydrating agent includes a solid metal oxide, solid acid, acid, weak acid, strong acid, ion-exchange resin, aluminosilicate, or any combination thereof.

In certain variations, the dehydrating agent includes a solid metal oxide. In one variation, the dehydrating agent is TiO 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 /WO ₃ , ZrO ₂ /Fe ₂ O ₃ , or ZrO ₂ /MnO ₂ , or any combination thereof.

In certain variations, the dehydrating agent comprises titanic acid, metal oxide hydrates, metal sulfates, metal oxide sulfates, metal phosphates, metal oxide phosphates, mineral acids, carboxylic acids or salts thereof, acidic resins, acidic zeolites, clays, or any combination thereof. In certain variations, _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, phosphotungstic acid, phosphomolybdic acid, silicolybdic acid, silicotungstic acid, Mg ₂ P ₂ O ₇ or MgHPO ₄ , or any combination thereof.

In some variations, the dehydrating agent includes a zeolite. In certain variations, the zeolite is in the hydrogen form or ammonia form, or is a metal-exchanged zeolite. In one variation, the metal-exchanged zeolite includes Li, Na, K, Ca, Mg, or Cu. In another variation, the zeolite has a pore size ranging from 1 to 10 Angstroms in diameter. In one variation, the zeolite is a mesoporous zeolite. In some variations, the zeolite has a pore size of about 5 to 6 angstroms, or about 5.6*6.0 angstroms, or about 5.1*5.5 to 5.3*5.6 angstroms. In another variant, the zeolite is a large pore zeolite. Suitable zeolites may include, for example, ZSM-12, ZSM-5, mordenite, faujasite, or zeolite Y.

In a variant in which a heterogeneous dehydrating agent such as that described above is used, the compound of formula (2) is dehydrated by passing the compound of formula (2) in vapor phase through a heated reactor containing a dehydrating agent to obtain a compound of formula (3-I). or a compound of formula (3), or a combination thereof. In one variation, the reactor is a packed bed reactor, a fluidized bed reactor, or a moving bed reactor.

combination of dehydrating agents

It should be understood that in some variations, the term “dehydrating agent” may include a combination of agents. In some variations 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 variations of the foregoing combinations, the organosilicon compound is N -methyl- N -(trimethylsilyl)trifluoroacetamide. In some variations of the combinations described above, the transition metal complex is a metal triflate or metal halide. In one variation, the metal triflate is a zinc triflate. In another variation, the metal halide is copper chloride.

In another embodiment, the dehydrating agent comprises a combination of a silane and a transition metal complex. In certain variations of the combinations described above, the transition metal complex is an iron complex. In one variation, the dehydrating agent includes a combination of a silane and an iron complex.

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

Exemplary combinations of dehydrating agents that can be used in the methods described herein include zinc triflate and N -methyl- N- (trimethylsilyl)trifluoroacetamide; copper chloride and N -methyl- N- (trimethylsilyl)trifluoroacetamide; iron complexes and silanes; and iron carbonate and diethoxymethylsilane.

Subsequent use

In some variations, acrylamide, acrylonitrile and other compounds prepared according to the methods described herein can be used as monomers for the industrial production of polymers.

Compounds of formula (3-I) prepared according to the methods herein can be used to prepare one or more subsequent products. For example, referring to Figure 8B , acrylamide prepared according to the methods described herein can be used in the production of polyacrylamide. Thus, in certain embodiments, preparing a compound of Formula (3-I) according to any of the methods herein; and polymerizing a compound of Formula (3-I). In one variation, preparing acrylamide according to any of the methods herein; and polymerizing acrylamide to produce polyacrylamide, a method for producing polyacrylamide is provided.

Compounds of formula (2) prepared according to the methods herein can be used to prepare one or more subsequent products. For example, referring to Figure 8B , acrylonitrile prepared according to the methods described herein can be used in the production of polyacrylonitrile. Thus, in certain embodiments, preparing a compound of formula (2) according to any of the methods herein; and a method comprising polymerizing a compound of formula (2). In one variation, preparing acrylonitrile according to any of the methods herein; and polymerizing acrylonitrile to produce polyacrylonitrile, a method for producing polyacrylonitrile is provided. Polyacrylonitrile may be suitable for a variety of applications including carbon fibers.

In another aspect, acrylonitrile prepared according to the methods described herein can be used in the production of acrylic acid and/or acrylamide.

composition

In some embodiments, a composition comprising a compound of formula (2) and a dehydrating agent is provided,

(2)

(2)

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

In certain embodiments, the composition further comprises a compound of formula (3) or an isomer thereof,

(3)

(3)

In the above formula, R ¹ is as defined above for formula (2).

In some variations of the foregoing, the composition further comprises a compound of formula (1) and ammonia,

In the above formula, R ¹ is as defined above for formula (2).

In another aspect, a composition comprising a compound of formula (1), ammonia, and a dehydrating agent is provided,

(1)

(One)

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

In some variations of the foregoing, the composition further comprises a compound of Formula (3-I), and/or a compound of Formula (3), or an isomer thereof;

(3)

(3)

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

In certain variations of the foregoing, 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, a system is provided comprising a continuous stirred-tank reactor comprising:

A first inlet configured to receive a compound of formula (1),

(1)

(One)

wherein R ¹ is H or alkyl;

A second inlet configured to receive ammonia,

wherein the reactor is configured to add the compound of formula (1) to the ammonia to achieve a ratio of ammonia to the compound of formula (1) such that ammonia is present in excess;

wherein the reactor is configured to add a compound of formula (1) to the ammonia at a rate suitable to maintain the temperature;

a second inlet configured for the reactor to receive ammonia and the compound of formula (1) in liquid form;

A jacket configured to maintain a constant temperature within the reactor;

a vent configured to discharge any excess ammonia from the reactor; and

An outlet configured to discharge a product stream comprising a compound of formula (1) and a compound of formula (2) prepared from ammonia,

이고, 상기 식에서 R¹이 화학식 (1)에 대해 상기 정의된 바와 같은 배출구.The compound of formula (2)

wherein R ¹ is as defined above for formula (1).

In another aspect, a system comprising a reactor comprising:

An inlet configured to receive ammonia and a compound of formula (1), wherein ammonia is in gaseous form and the compound of formula (1) is in liquid form,

이고, 상기 식에서 R¹이 H 또는 알킬인 주입구;The compound of formula (1)

, wherein R ¹ is H or an alkyl inlet;

As a heterogeneous catalytic bed,

wherein the reactor is configured to co-feed ammonia and a compound of formula (1) to the heterogeneous catalyst bed;

The reactor is configured to separately control the flow rates of ammonia and the compound of formula (1),

a heterogeneous catalyst bed configured such that the reactor adds the compound of formula (1) to the ammonia to achieve a ratio of ammonia to compound of formula (1) such that ammonia is present in excess;

a jacket configured to maintain a constant temperature within the reactor;

a vent configured to release any excess ammonia from the reactor; and

An outlet configured to discharge a product stream comprising a compound of formula (1) and a compound of formula (2) prepared from ammonia,

이고, 상기 식에서 R¹이 화학식 (1)에 대해 상기 정의된 바와 같은 배출구.The compound of formula (2)

wherein R ¹ is as defined above for formula (1).

In another aspect, a system is provided comprising a tube shell reactor comprising:

one or more tubes, wherein catalyst particles are packed between and around the one or more tubes, the one or more tubes configured to receive ammonia in gaseous form;

An inlet on the shell side of a reactor configured to receive a compound of formula (1) in liquid form,

wherein the reactor is configured to maintain an excess of ammonia in the reactor compared to the compound of formula (1);

an inlet where the reactor is configured to a temperature to produce a compound of formula (2) from a compound of formula (1) and ammonia; and

An outlet configured to discharge a product stream comprising a compound of formula (2) and excess ammonia.

In some variations of the foregoing, the compound of formula (2) is provided in molten form.

Enumeration Embodiments

The following enumerated embodiments represent some aspects of the present invention.

1. A method for producing a compound of formula (3-I) and/or a compound of formula (3) below, or an isomer thereof,

(3-I) 또는

(3)

(3-I) or

(3)

wherein R ¹ is H or alkyl;

the method,

Combining a compound of formula (2) with a dehydrating agent to prepare a compound of formula (3), or an isomer thereof,

이고, 상기 식에서 R¹이 화학식 (3-I) 및 (3)에 대해 상기 정의된 바와 같으며,The compound of formula (2)

wherein R ¹ is as defined above for formulas (3-I) and (3);

the dehydrating agent comprises phosphorus pentoxide, organophosphorus compounds, carbodiimide compounds, triazine compounds, organosilicon compounds, mixed oxides, transition metal complexes, or aluminum complexes, or any combination thereof;

A method in which the dehydrating agent comprises a solid metal oxide, solid acid, acid, weak acid, strong acid, ion-exchange resin, aluminosilicate, or any combination thereof.

2. According to embodiment 1,

A method further comprising preparing a compound of formula (2) by combining a compound of formula (1) with ammonia,

이고, 상기 식에서 R¹이 화학식 (3-I) 및 (3)에 대해 상기 정의된 바와 같은 방법.The compound of formula (1)

wherein R ¹ is as defined above for formulas (3-I) and (3).

3. according to embodiment 2,

A method in which a combination of a compound of formula (1) and ammonia further produces a compound of formula (2-I),

(2-I)

(2-I)

wherein R ¹ is as defined above for formulas (3-I) and (3).

4. according to any one of embodiments 1 to 3,

The method further comprising isolating the compound of Formula (2-I).

5. A method for producing a compound of formula (3-I) and/or a compound of formula (3) below, or an isomer thereof,

(3-I) 또는

(3)

(3-I) or

(3)

wherein R ¹ is H or alkyl;

the method,

combining a compound of formula (1) with ammonia and a dehydrating agent to prepare a compound of formula (3-I) and/or a compound of formula (3), or an isomer thereof;

이고, 상기 식에서 R¹이 화학식 (3-I) 및 (3)에 대해 상기 정의된 바와 같으며,The compound of formula (1)

wherein R ¹ is as defined above for formulas (3-I) and (3);

the dehydrating agent comprises phosphorus pentoxide, organophosphorus compounds, carbodiimide compounds, triazine compounds, organosilicon compounds, mixed oxides, transition metal complexes, or aluminum complexes, or any combination thereof;

A method in which the dehydrating agent comprises a solid metal oxide, solid acid, acid, weak acid, strong acid, ion-exchange resin, aluminosilicate, or any combination thereof.

6. according to embodiment 2 or 3,

ammonia is ammonia water,

ammonia is liquid ammonia,

Ammonia is anhydrous ammonia; or

Anhydrous gaseous ammonia.

7. according to any one of embodiments 1 to 5,

R ¹ is H;

R ¹ is alkyl;

and wherein R ¹ is methyl or ethyl.

8. according to any one of embodiments 1 to 7,

The method further comprising isolating the compound of formula (3-I) or the compound of formula (3), or both.

9. according to any one of embodiments 1 to 8,

A method in which the dehydrating agent comprises phosphorus pentoxide.

10. according to any one of embodiments 1 to 8,

A method in which the dehydrating agent comprises a compound that is organophosphorus.

11. according to embodiment 10,

A method in which the organophosphorus compound is an organophosphate.

12. according to embodiment 10,

wherein the organophosphorus compound is an alkyl halophosphate or a cycloalkyl halophosphate.

13. according to embodiment 10,

The organophosphorus compound is ethyl dichlorophosphate, diethyl chlorophosphate, methyl dichlorophosphate, dimethyl chlorophosphate, ethyl difluorophosphate, diethyl fluorophosphate, methyl difluorophosphate, or dimethyl fluorophosphate, or any combination thereof. way of being.

14. according to any one of embodiments 1 to 8,

A method in which the dehydrating agent comprises a carbodiimide compound.

15. according to embodiment 14,

이되, 상기 식에서 각각의 R⁴ 및 R⁵가 독립적으로 알킬 또는 사이클로알킬인 방법.carbodiimide compounds

wherein each of R ⁴ and R ⁵ in the above formula is independently alkyl or cycloalkyl.

16. according to embodiment 14,

A method in which the carbodiimide compound is N,N' -dicyclohexylcarbodiimide.

17. according to any one of embodiments 1 to 8,

A method in which the dehydrating agent comprises a triazine compound.

18. according to embodiment 17,

A method wherein the triazine compound is a halo-substituted triazine compound.

19. according to embodiment 17 or 18,

A method in which the triazine compound is a 1, 3, 5-triazine.

20. according to embodiment 17 or 18,

A method in which the triazine compound is cyanuric acid chloride.

21. according to any one of embodiments 1 to 8,

A method in which the dehydrating agent comprises an organosilicon compound.

22. according to embodiment 21,

A method in which the organosilicon compound is a silazane or a silane.

23. according to embodiment 21,

A method wherein the organosilicon compound is bis(trimethylsilyl)amine.

24. according to embodiment 21,

이되, 상기 식에서 각각의 R⁶, R⁷, R⁸ 및 R⁹가 독립적으로 H, 알킬, 사이클로알킬, 헤테로알킬, 헤테로사이클로알킬, 아릴, 헤테로아릴, 할로, 아미노, 또는 알콕시인 방법.organosilicon compounds

wherein each R ⁶ , R ⁷ , R ⁸ and R ⁹ in the above formula is independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy.

25. according to embodiment 21,

A process in which the organosilicon compound is hydrosilane.

26. according to embodiment 25,

The method of claim 1, wherein the dehydrating agent further comprises an alkylammonium halide.

27. according to embodiment 26,

wherein the alkylammonium halide is tetrabutylammonium fluoride.

28. according to embodiment 21,

A method in which the organosilicon compound is silane.

29. according to embodiment 28,

A method in which the silane is a halosilane, an alkoxysilane, or an aminosilane.

30. according to any one of embodiments 1 to 8,

A method in which the dehydrating agent comprises a transition metal complex.

31. according to embodiment 30,

A method in which the transition metal complex includes at least one halide or oxide ligand.

32. according to embodiment 30 or 31,

A method in which the transition metal complex comprises palladium or zinc.

33. according to embodiment 30 or 31,

A process in which the transition metal complex is palladium chloride or zinc chloride provided in water, acetonitrile or mixtures thereof.

34. according to embodiment 30 or 31,

A method in which the transition metal complex includes vanadium oxide.

35. according to any one of embodiments 1 to 8,

A method in which the dehydrating agent comprises an organosilicon compound and a transition metal complex.

36. according to embodiment 35,

wherein the organosilicon compound is N -methyl- N- (trimethylsilyl)trifluoroacetamide.

37. according to embodiment 35 or 36,

A method in which the transition metal complex is a metal triflate or metal halide.

38. according to embodiment 35,

A method in which the organosilicon compound comprises silane.

39. according to embodiment 35 or 38,

A method in which the transition metal complex is an iron complex.

40. according to embodiment 35,

A method wherein the organosilicon compound is an alkoxyalkylsilane.

41. according to embodiment 35 or 40,

A method in which the transition metal complex is a metal carbonate.

42. according to embodiment 41,

A method in which the metal carbonate is iron carbonate.

43. according to any one of embodiments 1 to 8,

dehydrating agent,

(i) zinc triflate and N -methyl- N- (trimethylsilyl)trifluoroacetamide; or

(ii) copper chloride and N -methyl- N- (trimethylsilyl)trifluoroacetamide; or

(iii) iron complexes and silanes; or

(iv) a method comprising iron carbonate and diethoxymethylsilane.

44. according to any one of embodiments 1 to 8,

A method in which the dehydrating agent comprises an aluminum complex.

45. according to embodiment 44,

A method in which an aluminum composite includes an aluminum halide.

46. according to embodiment 44 or 45,

A method in which an aluminum complex is complexed with water, acetonitrile, or an alkali metal salt, or a mixture thereof.

47. according to any one of embodiments 1 to 8,

wherein the dehydrating agent comprises an AlCl ₃ .H ₂ O/KI/H ₂ O/CH ₃ CN system or AlCl ₃ .NaI.

48. according to any one of embodiments 1 to 47,

The method of claim 1, wherein the dehydrating agent further comprises a solid support.

49. according to embodiment 48,

A method wherein the solid support is hydrotalcite.

50. according to any one of embodiments 1 to 8,

A method in which the dehydrating agent comprises monomeric vanadium oxide and hydrotalcite.

51. according to any one of embodiments 1 to 8,

The dehydrating agent is 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 O ₃ , ZrO ₂ /WO ₃ , ZrO ₂ /Fe ₂ O ₃ , or ZrO ₂ /MnO ₂ , or any combination thereof.

52. according to any one of embodiments 1 to 8,

wherein the dehydrating agent comprises titanic acid, metal oxide hydrates, metal sulfates, metal oxide sulfates, metal phosphates, metal oxide phosphates, mineral acids, carboxylic acids or salts thereof, acidic resins, acidic zeolites, clays, or any combination thereof.

53. according to any one of embodiments 1 to 8,

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, tungsten phosphon. an acid, phosphomolybdic acid, silomolybdic acid, silicotungstic acid, Mg ₂ P ₂ O ₇ or MgHPO ₄ , or any combination thereof.

54. according to any one of embodiments 1 to 8,

A method in which the dehydrating agent comprises a zeolite.

55. The method of embodiment 54,

A process in which the zeolite is in hydrogen form or ammonia form, or is a metal-exchanged zeolite.

56. The method of embodiment 54,

A method in which the metal-exchanged zeolite comprises Li, Na, K, Ca, Mg, or Cu.

57. The method of embodiment 54,

The method of claim 1 , wherein the zeolite has a pore size ranging from 1 to 10 Angstroms in diameter.

58. The method of embodiment 54,

A process in which the zeolite is a mesoporous zeolite.

59. The method of embodiment 54,

wherein the zeolite has a pore size of about 5 to 6 angstroms, or about 5.6*6.0 angstroms, or about 5.1*5.5 to 5.3*5.6 angstroms.

60. The method of embodiment 54,

A method in which the zeolite is a large pore zeolite.

61. The method of embodiment 54,

and wherein the zeolite is ZSM-12, ZSM-5, mordenite, faujasite, or zeolite Y.

62. according to any one of embodiments 1 to 61,

The compound of formula (2) is dehydrated by passing the compound of formula (2) in vapor phase through a heated reactor containing a dehydrating agent to produce a compound of formula (3-I) and/or a compound of formula (3). method.

63. according to embodiment 62,

wherein the reactor is a packed bed reactor, a fluidized bed reactor, or a moving bed reactor.

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

이고,The compound of formula (1)

ego,

이며,The compound of formula (2)

is,

wherein R ¹ is H or alkyl.

65. A compound of formula (1) and ammonia are combined in a reactor to obtain a compound of formula (2), a compound of formula (3-I), and/or a compound of formula (3), or ( As the case may be) a process comprising preparing any isomer of the foregoing,

이고,The compound of formula (1)

ego,

이며,The compound of formula (2)

is,

이고, A compound of formula (3-I)

ego,

이며,The compound of formula (3)

is,

wherein R ¹ is H or alkyl.

66. according to embodiment 64 or 65,

The temperature of the reactor produces a compound of formula (2), a compound of formula (3-I), and/or a compound of formula (3), or (as the case may be) any isomer of the foregoing, with a selectivity of greater than 50%. A method maintained at an average temperature suitable for

67. according to any one of embodiments 64 to 66,

A method in which the compound of formula (1) is added dropwise to a reactor containing ammonia.

68. according to any one of embodiments 64 to 66,

A process in which the compound of formula (1) is added by a single injection to a reactor containing ammonia.

69. providing ammonia to the reactor;

Adding a first part of a compound of formula (1) to a reactor,

이고, 상기 식에서 R¹이 H 또는 알킬인 것;The compound of formula (1)

And, wherein R ¹ is H or alkyl;

adjusting the temperature of the reactor after addition of the first part of the compound of formula (1);

adding a second part of the compound of formula (1) to the reactor; and

A process comprising adjusting the temperature of the reactor after addition of the second part of the compound of formula (1),

Addition of the first part and the second part of the compound of formula (1) produces a compound of formula (2)

wherein R ¹ is as defined above;

A process in which the temperature of the reactor is controlled to an average temperature suitable for producing the compound of formula (2).

70. A process comprising co-feeding a compound of formula (1) and ammonia to a heterogeneous catalyst bed to produce a compound of formula (2):

이고,The compound of formula (1)

ego,

이며,The compound of formula (2)

is,

wherein R ¹ is H or alkyl.

71. The method of embodiment 70,

A process in which the compound of formula (1) is fed to the reactor as a liquid.

72. according to embodiment 70 or 71,

A method in which the flow rates of the compound of formula (1) and ammonia are separately controlled.

73. according to any one of embodiments 70 to 72,

A method in which ammonia is present in excess in the reactor.

74. according to any one of embodiments 70 to 73,

The process further comprising collecting from the reactor a product stream comprising the compound of formula (2) and excess ammonia.

75. according to embodiment 74,

A method in which the compound of formula (2) is collected in liquid form.

76. according to embodiment 74 or 75,

A method in which the product stream is collected in a collection flask.

77. according to embodiment 76,

A method wherein the temperature of the collection flask is below the boiling point of the compound of formula (2).

78. according to any one of embodiments 70 to 77,

The process further comprising separating excess ammonia from the product stream.

79. according to embodiment 78,

The method further comprising recycling the separated ammonia to the reactor.

80. The method according to any one of embodiments 70 to 79,

A method in which the heterogeneous catalyst bed comprises a metal oxide, basic zeolite, alkali metal exchanged zeolite, base modified alumina, or a solid "ultrabasic".

81. The method according to any one of embodiments 70 to 80,

wherein the reactor is maintained at a temperature at which the compound of formula (2) is a gas.

82. according to any one of embodiments 70 to 81,

A process in which the compound of formula (2) is prepared anhydrous.

83. according to any one of embodiments 70 to 82,

ammonia is ammonia water,

ammonia is liquid ammonia,

ammonia is anhydrous ammonia,

A method wherein the ammonia is anhydrous gaseous ammonia.

84. according to any one of embodiments 1 to 83,

A process in which the compound of formula (3-I) is acrylamide and the compound of formula (3) is acrylonitrile.

85. A method for producing polyacrylamide,

preparing acrylamide according to the method of embodiment 84; and

A method comprising polymerizing acrylamide to produce polyacrylamide.

86. A method for producing polyacrylonitrile,

preparing acrylonitrile according to the method of embodiment 84; and

A method comprising polymerizing acrylonitrile to produce polyacrylonitrile.

87. A method for producing carbon fiber,

preparing polyacrylonitrile according to the method of embodiment 86; and

A method comprising making carbon fibers from polyacrylonitrile.

88. A system comprising a continuous stirred-tank reactor comprising:

A first inlet configured to receive a compound of formula (1),

(1)

(One)

wherein R ¹ is H or alkyl;

A second inlet configured to receive ammonia,

wherein the reactor is configured to add the compound of formula (1) to the ammonia to achieve a ratio of ammonia to the compound of formula (1) such that ammonia is present in excess;

wherein the reactor is configured to add a compound of formula (1) to the ammonia at a rate suitable to maintain the temperature;

a second inlet configured for the reactor to receive ammonia and the compound of formula (1) in liquid form;

a jacket configured to maintain a constant temperature within the reactor;

a vent configured to release any excess ammonia from the reactor; and

An outlet configured to discharge a product stream comprising a compound of formula (1) and a compound of formula (2) prepared from ammonia,

이고, 상기 식에서 R¹이 화학식 (1)에 대해 상기 정의된 바와 같은 배출구.The compound of formula (2)

wherein R ¹ is as defined above for formula (1).

89. A system comprising a reactor comprising:

An inlet configured to receive ammonia and a compound of formula (1), wherein ammonia is in gaseous form and the compound of formula (1) is in liquid form,

이고, 상기 식에서 R¹이 H 또는 알킬인 주입구;The compound of formula (1)

, wherein R ¹ is H or an alkyl inlet;

As a heterogeneous catalytic bed,

wherein the reactor is configured to co-feed ammonia and a compound of formula (1) to the heterogeneous catalyst bed;

The reactor is configured to separately control the flow rates of ammonia and the compound of formula (1),

a heterogeneous catalyst bed configured such that the reactor adds the compound of formula (1) to the ammonia to achieve a ratio of ammonia to compound of formula (1) such that ammonia is present in excess;

a jacket configured to maintain a constant temperature within the reactor;

a vent configured to release any excess ammonia from the reactor; and

An outlet configured to discharge a product stream comprising a compound of formula (1) and a compound of formula (2) prepared from ammonia,

이고, 상기 식에서 R¹이 화학식 (1)에 대해 상기 정의된 바와 같은 배출구.The compound of formula (2)

wherein R ¹ is as defined above for formula (1).

90. according to embodiment 88 or 89,

A system in which the compound of formula (2) is provided in molten form.

91. A method for preparing a compound of formula (3) or an isomer thereof,

(3)

(3)

wherein R ¹ is H or alkyl;

the method,

combining a compound of formula (2) with a dehydrating agent to prepare a compound of formula (3), or an isomer thereof;

이고, 상기 식에서 R¹이 화학식 (3)에 대해 상기 정의된 바와 같으며,The compound of formula (2)

, wherein R ¹ is as defined above for formula (3),

wherein the dehydrating agent comprises phosphorus pentoxide, an organophosphorus compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof.

92. according to embodiment 91,

A method further comprising preparing a compound of formula (2) by combining a compound of formula (1) with ammonia,

이고, 상기 식에서 R¹이 화학식 (3)에 대해 상기 정의된 바와 같은 방법.The compound of formula (1)

wherein R ¹ is as defined above for formula (3).

93. A method for preparing a compound of formula (3) or an isomer thereof,

(3)

(3)

wherein R ¹ is H or alkyl;

the method,

combining a compound of formula (1) with ammonia and a dehydrating agent to prepare a compound of formula (3), or an isomer thereof;

이고, 상기 식에서 R¹이 화학식 (3)에 대해 상기 정의된 바와 같으며,The compound of formula (1)

, wherein R ¹ is as defined above for formula (3),

wherein the dehydrating agent comprises phosphorus pentoxide, an organophosphorus compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof.

94. according to embodiment 92 or 93,

A method in which the ammonia is ammonium hydroxide or aqueous ammonia.

95. according to any one of embodiments 92 to 94,

A method in which a compound of formula (1) is combined with ammonia at room temperature.

96. according to any one of embodiments 91 to 95,

and wherein R ¹ is H.

97. according to any one of embodiments 91 to 95,

and wherein R ¹ is alkyl.

98. according to any one of embodiments 91 to 95,

and wherein R ¹ is methyl or ethyl.

99. according to any one of embodiments 91 to 98,

A method in which the dehydrating agent comprises phosphorus pentoxide.

100. according to any one of embodiments 91 to 98,

A method in which the dehydrating agent comprises a compound that is organophosphorus.

101. The method of embodiment 100, wherein

A method in which the organophosphorus compound is an organophosphate.

102. The method of embodiment 100,

wherein the organophosphorus compound is an alkyl halophosphate or a cycloalkyl halophosphate.

103. The method of embodiment 100,

The organophosphorus compound is ethyl dichlorophosphate, diethyl chlorophosphate, methyl dichlorophosphate, dimethyl chlorophosphate, ethyl difluorophosphate, diethyl fluorophosphate, methyl difluorophosphate, or dimethyl fluorophosphate, or any combination thereof. way of being.

104. according to any one of embodiments 91 to 98,

A method in which the dehydrating agent comprises a carbodiimide compound.

105. according to embodiment 104,

이되, 상기 식에서 각각의 R⁴ 및 R⁵가 독립적으로 알킬 또는 사이클로알킬인 방법.carbodiimide compounds

wherein each of R ⁴ and R ⁵ in the above formula is independently alkyl or cycloalkyl.

106. according to embodiment 104,

A method in which the carbodiimide compound is N,N' -dicyclohexylcarbodiimide.

107. according to any one of embodiments 91 to 98,

A method in which the dehydrating agent comprises a triazine compound.

108. according to embodiment 107,

A method wherein the triazine compound is a halo-substituted triazine compound.

109. according to embodiment 107 or 108,

A method in which the triazine compound is a 1, 3, 5-triazine.

110. according to embodiment 107 or 108,

A method in which the triazine compound is cyanuric acid chloride.

111. according to any one of embodiments 91 to 98,

A method in which the dehydrating agent comprises an organosilicon compound.

112. according to embodiment 111,

A method in which the organosilicon compound is a silazane or a silane.

113. according to embodiment 111,

A method in which the organosilicon compound is bis(trimethylsilyl)amine.

114. according to embodiment 111,

이되, 상기 식에서 각각의 R⁶, R⁷, R⁸ 및 R⁹가 독립적으로 H, 알킬, 사이클로알킬, 헤테로알킬, 헤테로사이클로알킬, 아릴, 헤테로아릴, 할로, 아미노, 또는 알콕시인 방법.organosilicon compounds

wherein each R ⁶ , R ⁷ , R ⁸ and R ⁹ in the above formula is independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy.

115. according to embodiment 111,

A process in which the organosilicon compound is hydrosilane.

116. according to embodiment 115,

The method of claim 1, wherein the dehydrating agent further comprises an alkylammonium halide.

117. according to embodiment 116,

wherein the alkylammonium halide is tetrabutylammonium fluoride.

118. according to embodiment 111,

A method in which the organosilicon compound is silane.

119. according to embodiment 118,

A method in which the silane is a halosilane, an alkoxysilane, or an aminosilane.

120. according to any one of embodiments 91 to 98,

A method in which the dehydrating agent comprises a transition metal complex.

121. according to embodiment 120,

A method in which the transition metal complex includes at least one halide or oxide ligand.

122. according to embodiment 120 or 121,

A method in which the transition metal complex comprises palladium or zinc.

123. according to embodiment 120 or 121,

A process in which the transition metal complex is palladium chloride or zinc chloride provided in water, acetonitrile or mixtures thereof.

124. according to embodiment 120 or 121,

A method in which the transition metal complex includes vanadium oxide.

125. according to any one of embodiments 91 to 98,

A method in which the dehydrating agent comprises an organosilicon compound and a transition metal complex.

126. according to embodiment 125,

wherein the organosilicon compound is N -methyl- N- (trimethylsilyl)trifluoroacetamide.

127. according to embodiment 125 or 126,

A method in which the transition metal complex is a metal triflate or metal halide.

128. according to embodiment 125,

A method in which the organosilicon compound comprises silane.

129. according to embodiment 125 or 128,

A method in which the transition metal complex is an iron complex.

130. according to embodiment 125,

A method wherein the organosilicon compound is an alkoxyalkylsilane.

131. according to embodiment 125 or 130,

A method in which the transition metal complex is a metal carbonate.

132. according to embodiment 131,

A method in which the metal carbonate is iron carbonate.

133. according to any one of embodiments 91 to 98,

dehydrating agent,

(i) zinc triflate and N -methyl- N- (trimethylsilyl)trifluoroacetamide; or

(ii) copper chloride and N -methyl- N- (trimethylsilyl)trifluoroacetamide; or

(iii) iron complexes and silanes; or

(iv) a method comprising iron carbonate and diethoxymethylsilane.

134. according to any one of embodiments 91 to 98,

A method in which the dehydrating agent comprises an aluminum complex.

135. according to embodiment 134,

A method in which an aluminum composite includes an aluminum halide.

136. according to embodiment 134 or 135,

A method in which an aluminum complex is complexed with water, acetonitrile, or an alkali metal salt, or a mixture thereof.

137. according to any one of embodiments 91 to 98,

wherein the dehydrating agent comprises an AlCl ₃ .H ₂ O/KI/H ₂ O/CH ₃ CN system or AlCl ₃ .NaI.

138. according to any one of embodiments 91 to 137,

The method of claim 1, wherein the dehydrating agent further comprises a solid support.

139. according to embodiment 138,

A method wherein the solid support is hydrotalcite.

140. according to any one of embodiments 91 to 98,

A method in which the dehydrating agent comprises monomeric vanadium oxide and hydrotalcite.

141. A compound of formula (2),

(2)

(2)

compounds wherein R ¹ is H or alkyl; and

A composition comprising a dehydrating agent comprising 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.

142. according to embodiment 141,

A composition further comprising a compound of formula (3), or an isomer thereof,

(3)

(3)

A composition wherein R ¹ is as defined above for formula (2).

143. according to embodiment 141 or 142,

As a compound of the following formula (1),

wherein R ¹ is as defined above for formula (2); and

A composition further comprising ammonia.

144. A compound of formula (1),

(1)

(One)

compounds wherein R ¹ is H or alkyl;

ammonia; and

A composition comprising a dehydrating agent comprising 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.

145. according to embodiment 144,

A composition further comprising a compound of formula (3), or an isomer thereof,

(3)

(3)

A composition wherein R ¹ is as defined above for formula (1).

Example

The following examples are illustrative only and are not meant to limit any aspect of the invention in any way.

Example 1

Anhydrous synthesis of 3-hydroxypropanamide (3-HP amide)

This example relates to a process for the synthesis of 3-hydroxypropanamide (3-HP amide) from beta-propiolactone (BPL). This process is highly selective for producing 3-HP amides that are not contaminated with water.

The synthesis is performed by adding BPL to a liquid pool of ammonia in a controlled manner. This is done 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 any pressure that can be produced at the reaction conditions and is jacketed to maintain a constant temperature during the reaction. Alternatively, the reactor may be operated under pressure and equipped with a suitable cooler to control the temperature within the reactor by condensing and returning to the reactor any ammonia evaporated during the reaction process. BPL is added to the liquid ammonia at a rate where the temperature is controlled to the desired set point. The ratio of ammonia to BPL keeps ammonia always in significant excess.

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

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

Example 2

Heterogeneous catalytic process for the production of 3-HP amides

This example relates to another process for the synthesis of 3-HP amide from BPL. This process is highly selective and is carried out continuously over a heterogeneous base catalyst.

The synthesis is carried out by co-feeding BPL and ammonia to a heterogeneous catalyst bed. BPL is supplied to the reactor as a liquid and ammonia is supplied to the reactor as a gas. This reactor arrangement may be referred to as a “trickle bed reactor”. The flow rates of liquid BPL and gaseous ammonia are controlled separately. The ratio is adjusted to ensure that ammonia is always in excess. The residence time in the catalyst bed is controlled to ensure that complete conversion of BPL occurs. 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 variations of the process, the base catalyst used is a metal oxide (eg MgO, ZrO), a basic zeolite (eg the ammonia form of the zeolite precursor NH ₄ ZSM5), an alkali metal exchanged zeolite, another modified zeolite, a base modified zeolite alumina as well as solid “superbases” (eg, lanthanide imides and nitrides on zeolites, metal oxynitrides, and KNH ₂ /Al ₂ O ₃ ).

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

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

Example 3

Reactor design for heterogeneous catalyst production of 3-HP amide

This example describes a reactor design suitable for a process for preparing 3-HP amide with high selectivity from BPL, such as the process described in Example 2 above. The reactor is designed to ensure that ammonia and BPL only come into contact with the heterogeneous catalyst bed.

A tube within a shell reactor is used in this example. Catalyst particles are packed between and around the tubes. One reactant, such as ammonia, is fed to the shell side through a catalyst bed. A second reactant, such as beta-propiolactone, is then fed through the tube, and the tube is made porous to the reactant in one of two ways. In one variation, a hole may be drilled into the tube through the length of the tube buried within the catalyst bed. Alternatively, in another variant, the tube may be made of a porous metal tube through the length of the buried tube. The tube may have a solid, non-porous, metal header that will extend down into or into the catalyst bed. These tubes can be made of a variety of non-reactive metals including stainless steel, Hastelloy, Inconel, and titanium.

In one variation of the above, gaseous ammonia is supplied through a tube and liquid BPL flows through a catalyst bed on the shell side. In this configuration, sintered metal tubes may be used, and by adjusting the pore size, the back diffusion may be configured to be nearly zero.

Example 4A

Integrated Process for Manufacturing Acrylonitrile or Acrylamide via 3-HP Amide

This example describes an integrated process for preparing acrylonitrile, acrylamide, or combinations thereof via unisolated 3-HP amide. The integrated process described in this example combines two processes: (1) a process for synthesizing 3-HP amide from BPL under anhydrous conditions, and (2) converting BPL to acrylonitrile or acrylamide, or combinations thereof. A process for synthesizing acrylonitrile or acrylamide, or a combination thereof, from 3-HP amide in one continuous unit operation, which converts to

The following system includes the 3-HP amide manufacturing process described in Example 1 above. Anhydrous synthesis of 3-HP amide is carried out in a continuous stirred-tank reactor (CSTR) and at the end of the reaction a solution of 3-HP amide in ammonia is prepared. This solution is then drained from the CSTR into a holding tank. From the holding tank, 3-HP amide in ammonia is continuously fed into a fixed bed heterogeneous reactor containing the desired catalyst for the production of the desired product of acrylonitrile or acrylamide and heated to the desired reaction temperature. In the heterogeneous reactor, 3-HP amide is converted to the desired product with high conversion and high selectivity. The prepared mixture of acrylonitrile/ammonia or acrylamide/ammonia exits the reactor and is collected in a product recovery vessel, where ammonia is separated from the product, condensed, and recycled to the 3-HP amide synthesis vessel. Inhibitors to prevent polymerization may be added at this stage. In one variation, the inhibitor is added before the ammonia is removed. In another variant, the inhibitor is added after the ammonia has been removed.

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

Example 4B

Integrated Process for Manufacturing Acrylonitrile or Acrylamide via 3-HP Amide

This example describes an integrated process for preparing acrylonitrile, acrylamide, or combinations thereof via unisolated 3-HP amide. The integrated process described in this example combines two processes: (1) a process for synthesizing 3-HP amide from BPL under anhydrous conditions, and (2) converting BPL to acrylonitrile or acrylamide, or combinations thereof. A process for synthesizing acrylonitrile or acrylamide, or a combination thereof, from 3-HP amide in one continuous unit operation, which converts to

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

One important advantage of this integrated approach is that the amount of unreacted ammonia is low and the excess required is simultaneous for both process steps (3-HP amide synthesis and subsequent conversion of acrylonitrile or acrylamide to dehydrated products). can be optimized and the amount of recycle ammonia required can be minimized. Also, the recycled ammonia does not need to be condensed since the feed to the 3-HP amide synthesis reactor is gaseous in this case. In addition, acrylonitrile and/or acrylamide are produced continuously without a solvent from BPL without intermediate separation and purification steps.

Example 5

Synthesis of 3-hydroxypropanamide

This example explores the effect of addition order and solvent in the preparation of 3-HP amide.

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

Table 1

Example 6

Synthesis of 3-hydroxypropanamide

This example explores the effect of the amount of ammonium hydroxide used on the BPL added.

BPL and ammonium hydroxide were combined in a 5 L reactor in the NH ₄ OH:BPL molar ratios listed 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 was determined by ¹ H NMR based on a raw sample of the reaction mixture. Then, the reaction was allowed to proceed. After the reaction was stopped, the crude reactants were passed through an ion exchange resin. 3-HP amide was recovered from the ion exchange (IX) resin and the overall yield of 3-HP amide (from synthesis and resin purification) was determined. The 3-HP amide yields are summarized in Table 2 below.

Table 2

Example 7

Synthesis of 3-HP amide by reacting BPL with aqueous ammonia

This example demonstrates the synthesis of 3-HP amide by reacting BPL with aqueous ammonia, and evaluates the effect of reaction conditions on the selectivity to 3-HP amide.

The reaction was carried out in an agitated temperature-controlled reactor. 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 feed vessel.

The reactor was charged with 2955 g of a 29 wt % ammonia solution and then pressurized to 40 psig with N ₂ (to provide a static pressure differential across the BPL metering pump). The stirrer was operated at about 400 rpm and cooled to 9°C. 535 g of BPL was connected to the feed system and pressurized to 16 psig with N ₂ . Increased BPL feed rate. The reactor temperature was maintained at 9-10 °C over the continuous BPL feed period (120 minutes). When all the BPL was fed to the reactor, the feed was converted to de-ionized water. About 100 g of water was fed into the reactor to flush the feed line from the BPL and the feed pump. The reaction was sampled 90 min after BPL addition and no residual BPL was detected by NMR analysis. The reaction mixture was drained from the reactor for final product recovery.

result

Metered BPL addition resulted in a well-controlled reaction temperature. An almost instantaneous reaction of BPL with concentrated aqueous ammonia solution was observed. The small reactor temperature increase (˜1° C.) upon increasing the BPL feed rate was compensated by decreasing the CTB set-point. The reactor was cooled from about 9-10 °C to about 7 °C within minutes after stopping the BPL feed.

Tables 3a and 3b show reaction conditions and selectivities for 3-HP amide and other compounds produced. The selectivity for 3-HP amide was 89%, and 3-hydroxypropionic acid was detected.

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

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

Performing the reaction of ammonia water and BPL under well-controlled conditions, such as reaction temperature and BPL addition rate, resulted in high selectivity for 3-HP amide.

Example 8

NH for 3-HP amide synthesis ₄ Effect of OH:BPL Ratio

This example evaluates the effect of the NH ₄ OH:BPL ratio on selectivity to 3-HP amide. The same materials and procedures were used in this example as in Example 7 above, except for the following: 2891 g of 29 wt % ammonia was charged to the reactor and 704 g of BPL was fed at a rate of 5.2 g/hour.

Metered BPL addition resulted in a well-controlled reaction temperature. Similar to Example 7, an almost instantaneous reaction of BPL with a concentrated aqueous ammonia solution was observed. Tables 4A and 4B show reaction conditions and selectivities for 3-HP amide and other compounds produced. The selectivity for 3-HP amide was 89%.

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

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

Performing the reaction of ammonia water and BPL under well-controlled conditions, such as reaction temperature and BPL addition rate, resulted in high selectivity for 3-HP amide. Reduction of NH ₄ OH:BPL from 3.3:1 in Example 7 to 2.4:1 in this Example did not affect selectivity to 3-HP amide (reduction in ammonia use by 25%). 775 g of crude 3-HP amide was prepared.

Example 9

Al ₂ O ₃ Acrylonitrile synthesis using

This example shows the preparation of acrylonitrile by dehydration of 3-hydroxypropanamide with alumina (Al ₂ O ₃ ).

Reactor setup

A continuous tubular reactor was used for the production of acrylonitrile by dehydration of 3-hydroxypropanamide. This example was performed using a GC injection port that can be heated non-uniformly. A glass liner in the GC was used as a substitute for the tubular reactor. A small amount of catalyst was placed in a liner filled with inert glass wool on both sides.

catalyst manufacturing

The Al ₂ O ₃ catalyst used was contained in the form of 1/8-inch pellets. It was crushed and sieved (250-600 μm) before loading into the reactor.

Feedstock manufacturing

The feedstock 3-HP amide was dissolved in ultrapure water and injected into the injection port by means of a micro-syringe. The feed liquid was observed to evaporate under the reaction temperature and was forced through the catalyst bed under a He carrier gas. For adjustment of catalyst amount and/or carrier gas flow rate, different residence times can be realized. The injection port can be heated with a heating capacity up to 400°C. The eluate from the reaction was sent directly to the GC column for separation and quantification.

General procedure

3-HP amide was weighed into an autosampler vial mini insert and distilled water was added. Dissolved 3-HP amide resulted in an 11.08% solution (w/w). A GC injection port liner (inverted cup design) was filled with a small plug of glass wool just on top of the cup to support the Al ₂ O ₃ particles. Sifted Al ₂ O ₃ was added to give a bed 0.2 cm long. Additional glass wool was added on the Al ₂ O ₃ bed to hold it in place. An inactivated open tube liner containing only glass wool was also used for the blank test. For product analysis, a GC coupled with an FID detector was used. The total helium flow through the liner was maintained at 42 mL/min with the liner at 400°C. The GC column used had a size of 15 m*0.32 mm*0.25 um.

result

The thermal stability of 3-HP amide was investigated without the presence of a catalyst. It was observed that 3-HP amide had reasonable stability under elevated temperatures up to 400 °C in a short period of time. Formation of acrylamide was less than 1% and no 3-HP amide or ammonia was detected by GC.

Then, an aqueous solution of 3-HP amide was injected into the reaction with a packed Al ₂ O ₃ catalyst bed (0.2 cm) under 400 °C. Raw GC data for 15 injections are listed in Table 5 below, and the compiled results are shown in FIG. 9 . Conversion of 3-HP amide was observed to be 100% for each injection. The major species found in the product was acrylonitrile (50%).

table 5

conclusion

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

Example 10

Nb ₂ O ₅ Acrylonitrile synthesis using

This example shows the preparation of acrylonitrile by dehydration of 3-hydroxypropanamide with Nb ₂ O ₅ . This example was performed using a GC injection port, as described in Example 9 above.

Table 6. Micro-GC experiments (pulsating injection)

Table 7. Bench-top unit (continuous process)

Example 11

Acrylonitrile synthesis

This example shows the production of acrylonitrile using alumina, wherein molten 3-HP amide is fed through a vertical tubular reactor under continuous mode.

A vapor phase catalytic reaction system was constructed as follows: 30 g of 3-hydroxypropanamide (99%) was prepared and added to the reactor vessel. The catalyst reactor was charged with 1 g of 30-60 mesh Al ₂ O ₃ catalyst and 20 g of silicon carbide as an inert support before and after the catalyst bed. The raw materials were warmed to less than 80° C. and fed to the ebullated bed reactor by a metering pump at a rate of about 10 WHSV. The reactor temperature was maintained at 350°C. Samples were collected in approximately half hour increments over an hour. Samples were analyzed by NMR and GC-FID for acrylonitrile, acrylamide, acrylic acid, 3-hydroxypropanamide, and other potential products. Results for conversion and selectivity were calculated using the formula:

Results indicated a total conversion of 3-HP amide of 100%. The acrylonitrile selectivity was 13%. Other products detected from the samples included acrylamide and polyamide.

Claims (33)

A method for producing a compound of formula (3-I) and/or a compound of formula (3) below, or a geometric isomer thereof,

(3-I) or

(3)
In the above formulas (3-I) and (3), R ¹ is H or alkyl;
the method,
A compound of formula (1) is prepared by combining carbon monoxide and an epoxide compound, and the compound of formula (1) is first reacted with ammonia and then with a dehydrating agent to obtain the compound of formula (3-I) and/or the compound of formula (3-I) Including preparing the compound of (3), or a geometric isomer thereof,
The compound of formula (1)

and R ¹ in formula (1) is as defined above for formulas (3-I) and (3);
or the dehydrating agent comprises phosphorus pentoxide, organophosphorus compounds, carbodiimide compounds, triazine compounds, organosilicon compounds, mixed oxides, transition metal complexes, or aluminum complexes, or any combination thereof;
Wherein the dehydrating agent comprises a solid metal oxide, solid acid, acid, weak acid, strong acid, ion-exchange resin, aluminosilicate, or any combination thereof.
method. According to claim 1,
R ¹ is H;
R ¹ is alkyl;
and wherein R ¹ is methyl or ethyl. According to claim 1,
wherein the dehydrating agent further comprises a solid support of hydrotalcite. According to claim 1,
By passing the compound of formula (2) in the vapor phase through a heated reactor containing the dehydrating agent, the compound of formula (2) is dehydrated to form the compound of formula (3-I) and/or the compound of formula (3-I). ) As a method for producing a compound of,
The compound of formula (2)

and wherein R ¹ in formula (2) is H or alkyl. A compound of formula (1) is prepared by combining carbon monoxide and an epoxide compound, and a solution containing a compound of formula (2) and an excess of ammonia is prepared by combining the compound of formula (1) and ammonia in a first reactor and combining the solution with the catalyst in a second reactor to produce a compound of formula (3-I), and/or a compound of formula (3), or a geometric isomer, with a selectivity of greater than 50%. As a method,
The compound of formula (1)

ego,
The compound of formula (2)

is,
A compound of formula (3-I)

ego,
The compound of formula (3)

is,
In the formulas (1), (2), (3-I) and (3), R ¹ is H or alkyl.
method. According to claim 5,
wherein the temperature of the first and second reactors is greater than 50% to produce a compound of Formula (2), a compound of Formula (3-I), and/or a compound of Formula (3), or a geometric isomer. and maintained at a suitable average temperature. According to claim 6,
wherein the catalyst is a heterogeneous catalyst bed comprising a metal oxide, a basic zeolite, an alkali metal exchanged zeolite, a base modified alumina, or a solid super base. According to any one of claims 4 to 7,
A method wherein the compound of formula (2) is prepared anhydrous. According to any one of claims 1 to 6,
A process in which the compound of formula (3-I) is acrylamide and the compound of formula (3) is acrylonitrile. preparing acrylamide according to the method of claim 9; and
Polymerizing the acrylamide to produce polyacrylamide
Including, a method for producing polyacrylamide. preparing acrylonitrile according to the method of claim 9; and
Polymerizing the acrylonitrile to produce polyacrylonitrile
Including, a method for producing polyacrylonitrile. Systems comprising a continuous stirred-tank reactor and a fixed bed heterogeneous reactor:
The continuous stirred-tank reactor
A first inlet configured to receive a compound of formula (1),

(One)
In Formula (1), R ¹ is H or an alkyl first inlet;
A second inlet configured to receive ammonia,
wherein the reactor is configured to add the compound of formula (1) to the ammonia to achieve a ratio of ammonia to compound of formula (1) such that the ammonia is present in excess;
wherein the reactor is configured to add the compound of formula (1) to the ammonia at a rate suitable to maintain the temperature;
a second inlet configured for the reactor to receive the ammonia and the compound of formula (1) in liquid form;
a jacket configured to maintain a constant temperature within the reactor;
a vent configured to discharge any excess ammonia from the reactor; and
An outlet configured to discharge a product stream comprising the compound of formula (1) and the compound of formula (2) prepared from the ammonia,
The compound of formula (2)

, wherein R ¹ in formula (2) is an outlet as defined above for formula (1)
Including,
The fixed bed heterogeneous reactor contains a catalyst for the production of a compound of formula (3-I) and/or a compound of formula (3), or a geometric isomer thereof.

(3-I) or

(3)
In the above formulas (3-I) and (3), R ¹ is as defined above. An inlet configured to receive ammonia and a compound of formula (1), wherein the ammonia is in gaseous form and the compound of formula (1) is in liquid form,
The compound of formula (1)

And, in Formula (1), R ^One is H or an alkyl inlet;
As a heterogeneous catalytic bed,
a reactor is configured to co-feed the ammonia and the compound of formula (1) to the heterogeneous catalyst bed;
The reactor is configured to separately control the flow rate of the ammonia and the compound of formula (1),
a heterogeneous catalyst bed configured such that the reactor adds the compound of formula (1) to the ammonia to achieve a ratio of ammonia to compound of formula (1) such that the ammonia is present in excess;
a jacket configured to maintain a constant temperature within the reactor;
a vent configured to discharge any excess ammonia from the reactor; and
An outlet configured to discharge a product stream comprising the compound of formula (1) and the compound of formula (2) prepared from the ammonia,
The compound of formula (2)

, wherein R ¹ in formula (2) is an outlet as defined above for formula (1)
A reactor comprising a, and
A fixed bed heterogeneous reactor containing a catalyst for the production of a compound of formula (3-I) and/or a compound of formula (3), or a geometric isomer thereof, comprising:

(3-I) or

(3)
Fixed Bed Heterogeneous Reactors in formulas (3-I) and (3) above, wherein R ¹ is as defined above
A system that includes. According to claim 1 or 5,
A method wherein the carbon monoxide and/or epoxide compound is at least partially biobased. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

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