CN115108924A - Amine intermediate and preparation method and application thereof - Google Patents
Amine intermediate and preparation method and application thereof Download PDFInfo
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- CN115108924A CN115108924A CN202210722918.1A CN202210722918A CN115108924A CN 115108924 A CN115108924 A CN 115108924A CN 202210722918 A CN202210722918 A CN 202210722918A CN 115108924 A CN115108924 A CN 115108924A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/52—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups or amino groups bound to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention relates to an amine intermediate, a preparation method and application thereof, wherein the amine intermediate comprises N- (2-methoxycyclohexyl) -1, 3-propane diamine, and the preparation method comprises the following steps: performing addition reaction on 2-methoxycyclohexylamine and acrylonitrile at 10-100 ℃ to generate 3- (2-methoxycyclohexyl) -aminopropionitrile; and (3) carrying out hydrogenation reaction on the 3- (2-methoxycyclohexyl) -aminopropionitrile in a hydrogen atmosphere at the temperature of 20-120 ℃ under the action of a catalyst to obtain the compound. The preparation method is simple and efficient to operate.
Description
Technical Field
The invention relates to the technical field of compound preparation, in particular to an amine intermediate and a preparation method and application thereof.
Background
N- (2-methoxycyclohexyl) -1, 3-propane diamine is an important organic chemical intermediate, can be applied to multiple aspects of the field of organic chemical industry, and has less research on synthesis and preparation of N- (2-methoxycyclohexyl) -1, 3-propane diamine at present; therefore, it is highly desirable to provide a method for preparing N- (2-methoxycyclohexyl) -1, 3-propanediamine with simple operation process and high synthesis efficiency.
Disclosure of Invention
Based on the above, there is a need to provide an amine intermediate, and a preparation method and application thereof, so as to provide a preparation method of N- (2-methoxycyclohexyl) -1, 3-propanediamine, which is simple in operation process and high in synthesis efficiency.
A preparation method of an amine intermediate, wherein the amine intermediate comprises N- (2-methoxycyclohexyl) -1, 3-propane diamine, comprises the following steps:
performing addition reaction on 2-methoxycyclohexylamine and acrylonitrile at 10-100 ℃ to generate 3- (2-methoxycyclohexyl) -aminopropionitrile;
and (2) carrying out hydrogenation reaction on the 3- (2-methoxycyclohexyl) -aminopropionitrile at the temperature of 20-120 ℃ in a hydrogen atmosphere under the action of a catalyst to obtain the compound.
In some embodiments, the molar ratio of the 2-methoxycyclohexylamine to the acrylonitrile is 1 (0.8-1.2).
In some embodiments, the addition reaction is carried out for a reaction time of 1 to 10 hours.
In some embodiments, the addition reaction is carried out in a first reaction medium;
optionally, the first reaction medium comprises one or more of methanol, ethanol, isopropanol, and n-butanol; the mass ratio of the first reaction medium to the 2-methoxycyclohexylamine is (0.5-5): 1.
In some embodiments, the hydrogenation reaction is carried out under conditions comprising at least one of:
(1) the reaction time is 2-48 h;
(2) the pressure of the hydrogen atmosphere is 1-10 MPa;
(3) the catalyst is Raney nickel.
In some embodiments, the catalyst is added in an amount of 5% to 50% by mass of the liquid in the system at the start of the hydrogenation reaction.
In some embodiments, the hydrogenation reaction is carried out with the addition of an inhibitor;
optionally, the inhibitor comprises one or more of liquid ammonia, sodium hydroxide, and potassium hydroxide; the addition amount of the inhibitor accounts for 5-100% of the mass percent of the 3- (2-methoxycyclohexyl) -aminopropionitrile.
In some embodiments, the hydrogenation reaction is carried out in a second reaction medium;
optionally, the second reaction medium comprises one or more of methanol, ethanol, isopropanol, and n-butanol; the mass ratio of the second reaction medium to the 3- (2-methoxycyclohexyl) -aminopropionitrile is (0.5-5): 1.
An amine intermediate is prepared by the preparation method of the amine intermediate.
The amine intermediate is applied to the preparation of epoxy resin curing agents, polymerization reaction auxiliaries, rubber additives, medicines and/or pesticides.
The amine intermediate comprises N- (2-methoxycyclohexyl) -1, 3-propane diamine, and the preparation method comprises the steps of taking 2-methoxycyclohexylamine as a starting material, and obtaining the N- (2-methoxycyclohexyl) -1, 3-propane diamine through acrylonitrile addition reaction and hydrogenation reaction; the conversion rate of acrylonitrile in the reaction of adding acrylonitrile can reach 100 percent, and the selectivity of 3- (2-methoxycyclohexyl) -aminopropionitrile can reach 99.82 percent; the selectivity of N- (2-methoxycyclohexyl) -1, 3-propane diamine in the hydrogenation reaction can reach 98.36% at most, and the conversion rate of 3- (2-methoxycyclohexyl) -aminopropionitrile can reach 98.42% at most; therefore, the preparation method is simple and efficient to operate.
Detailed Description
The amine intermediate and the preparation method thereof according to the present invention will be described in further detail with reference to the following specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the technical features described in the open-ended form, the closed technical scheme comprising the listed features also comprises the open technical scheme comprising the listed features.
As used herein, "a combination of one or more" refers to any one or a combination of any two or more of the listed items.
As used herein, the term "and/or", "and/or" includes any one of two or more of the associated listed items, as well as any and all combinations of the associated listed items, including any two of the associated listed items, any more of the associated listed items, or all combinations of the associated listed items.
Herein, reference to numerical intervals is deemed continuous within the numerical intervals, unless otherwise stated, and includes the minimum and maximum values of the range, as well as each and every value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
In this context, referring to units of the data range, if only with units after the right end point, the units representing the left end point and the right end point are the same. For example, 2-48 h indicates that the units of the left end point "2" and the right end point "48" are all h.
The terms "first" and "second" are not used herein to limit the order, but to distinguish the reaction medium used in the addition reaction from that used in the hydrogenation reaction.
A method for preparing an amine intermediate, wherein the amine intermediate comprises N- (2-methoxycyclohexyl) -1, 3-propanediamine, comprises the following steps:
performing addition reaction on 2-methoxycyclohexylamine and acrylonitrile at 10-100 ℃ to generate 3- (2-methoxycyclohexyl) -aminopropionitrile;
and (2) carrying out hydrogenation reaction on the 3- (2-methoxycyclohexyl) -aminopropionitrile in a hydrogen atmosphere at the temperature of 20-120 ℃ under the action of a catalyst to obtain the compound.
The reaction process is as follows:
during the addition reaction, the reaction temperature can be 10-100 ℃; for example, it may be 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃ or the like; preferably 50-80 ℃; when the reaction temperature is lower than 50 ℃, the reaction proceeds too slowly, and when the reaction temperature is higher than 80 ℃, acrylonitrile polymer is generated, thereby affecting the selectivity of the target product.
During the hydrogenation reaction, the reaction temperature can be 20-120 ℃; for example, it may be 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃ or the like; preferably 55-75 ℃; when the reaction temperature is too high, the selectivity of the target product is reduced.
The preparation method of the amine intermediate comprises the steps of taking 2-methoxycyclohexylamine as a starting material, and performing acrylonitrile addition reaction and hydrogenation reaction to obtain N- (2-methoxycyclohexyl) -1, 3-propanediamine; the conversion rate of acrylonitrile in the reaction of adding acrylonitrile can reach 100 percent, and the selectivity of 3- (2-methoxycyclohexyl) -aminopropionitrile can reach 99.82 percent; the selectivity of N- (2-methoxycyclohexyl) -1, 3-propane diamine in the hydrogenation reaction can reach 98.36% at most, and the conversion rate of 3- (2-methoxycyclohexyl) -aminopropionitrile can reach 98.42% at most; therefore, the preparation method is simple and efficient to operate.
In some embodiments, the molar ratio of the 2-methoxycyclohexylamine to the acrylonitrile can be 1 (0.8 to 1.2); for example, it may be 1:0.8, 1:0.9, 1:1.0, 1:1.1, or 1:1.2, etc.; preferably 1: (0.95-1.05).
In some embodiments, the reaction time can be 1-10 hours when the addition reaction is performed; for example, it may be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, or 10h, etc.; preferably 4-8 h; too short a reaction time, incomplete reaction, too long a reaction time, and increased time cost.
In some embodiments, the addition reaction may be carried out in a first reaction medium.
In some of these embodiments, the first reaction medium may include one or more of methanol, ethanol, isopropanol, and n-butanol.
In some embodiments thereof, the mass ratio of the first reaction medium to the 2-methoxycyclohexylamine can be (0.5-5): 1; for example, the ratio may be 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1, and the like, and the ratio is not particularly limited. The addition reaction between the 2-methoxycyclohexylamine and the acrylonitrile is carried out in the reaction medium, so that the distribution of the reaction raw materials in the reaction medium is more uniform, the contact between the 2-methoxycyclohexylamine and the acrylonitrile is increased, and the reaction efficiency is improved.
In some embodiments, the hydrogenation reaction is carried out for 2-48 hours; for example, it may be 2h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 48h, or the like; preferably 8-24 h; too short a reaction time, incomplete reaction, too long a reaction time, and increased time cost.
In some embodiments, when the hydrogenation reaction is carried out, the pressure of the hydrogen atmosphere can be 1-10 MPa; for example, the pressure may be 1MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa or 10MPa, and the like, and the pressure is not particularly limited. And in the hydrogenation reaction process, monitoring the hydrogen pressure, and judging that the hydrogenation reaction is finished when the hydrogen pressure is stable.
In some embodiments, the catalyst may be raney nickel.
In some embodiments, the catalyst may be added in an amount of 5-50% by mass of the liquid in the system at the beginning of the hydrogenation reaction; for example, the concentration may be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or the like, and is not particularly limited.
When the hydrogenation reaction does not adopt a reaction medium, the liquid in the system at the beginning of the hydrogenation reaction refers to 3- (2-methoxycyclohexyl) -aminopropionitrile, and the addition amount of the catalyst accounts for 5-50% of the mass percent of the 3- (2-methoxycyclohexyl) -aminopropionitrile; when the hydrogenation reaction is carried out in a reaction medium, the liquid in the system at the beginning of the hydrogenation reaction refers to 3- (2-methoxycyclohexyl) -aminopropionitrile and the reaction medium, and the adding amount of the catalyst accounts for 5-50% of the total mass of the 3- (2-methoxycyclohexyl) -aminopropionitrile and the reaction medium.
In some embodiments, an inhibitor may also be added when the hydrogenation reaction is carried out; the inhibitor is added, so that the occurrence of side reaction can be reduced, and the conversion rate of the 3- (2-methoxycyclohexyl) -aminopropionitrile and the selectivity of the N- (2-methoxycyclohexyl) -1, 3-propanediamine can be improved.
In some of these embodiments, the inhibitor may include one or more of liquid ammonia, sodium hydroxide, and potassium hydroxide.
In some of these embodiments, the inhibitor may be added in an amount of 5% to 100% by weight of the 3- (2-methoxycyclohexyl) -aminopropionitrile; for example, the concentration may be 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, or the like, and is not particularly limited.
In some embodiments, the hydrogenation reaction may be carried out in a second reaction medium; the hydrogenation reaction of the 3- (2-methoxycyclohexyl) -aminopropionitrile is carried out in a reaction medium, which is beneficial to more uniform distribution of reaction raw materials in the reaction medium, increases the contact between the 3- (2-methoxycyclohexyl) -aminopropionitrile and hydrogen and improves the reaction efficiency.
In some of these embodiments, the second reaction medium may include one or more of methanol, ethanol, isopropanol, and n-butanol.
In some of these embodiments, the mass ratio of the second reaction medium to the 3- (2-methoxycyclohexyl) -aminopropionitrile may be (0.5-5): 1; for example, it may be 0.5:1, 1:1, 2:1, 3:1, 4:1 or 5:1, and the like, and is not particularly limited.
An amine intermediate is prepared by the preparation method of the amine intermediate.
The amine intermediate is applied to the preparation of epoxy resin curing agents, polymerization reaction auxiliaries, rubber additives, medicines and/or pesticides.
The following describes the technical solution of the present invention in detail with reference to specific examples.
It should be noted that, in the addition reaction, the calculation formula of the conversion rate of acrylonitrile is: acrylonitrile conversion ═ (molar amount of acrylonitrile-molar amount of unreacted acrylonitrile) ÷ molar amount of acrylonitrile × 100%;
3- (2-methoxycyclohexyl) -aminopropionitrile selectivity ═ 3- (2-methoxycyclohexyl) -aminopropionitrile mole ÷ (mole of acrylonitrile-mole of unreacted acrylonitrile) × 100%.
In the hydrogenation reaction, the conversion of 3- (2-methoxycyclohexyl) -aminopropionitrile is (molar amount of 3- (2-methoxycyclohexyl) -aminopropionitrile-molar amount of unreacted 3- (2-methoxycyclohexyl) -aminopropionitrile) ÷ molar amount of 3- (2-methoxycyclohexyl) -aminopropionitrile × 100%;
selectivity for N- (2-methoxycyclohexyl) -1, 3-propanediamine ═ molar amount of N- (2-methoxycyclohexyl) -1, 3-propanediamine ÷ (molar amount of 3- (2-methoxycyclohexyl) -aminopropionitrile-molar amount of unreacted 3- (2-methoxycyclohexyl) -aminopropionitrile) × 100%.
Example 1
Adding 260g of 2-methoxycyclohexylamine into a three-neck flask, dropwise adding 106g of acrylonitrile into the three-neck flask at the speed of 1g/min, and carrying out stirring reaction at 10-20 ℃ for 2 h; and analyzing the reaction liquid by adopting gas chromatography, analyzing and calculating the conversion rate of acrylonitrile by taking n-propanol as an internal standard substance, and simultaneously analyzing and comparing 3- (2-methoxycyclohexyl) -aminopropionitrile by adopting the gas chromatography to calculate the selectivity of the 3- (2-methoxycyclohexyl) -aminopropionitrile. Wherein the molar ratio of the 2-methoxycyclohexylamine to the acrylonitrile is 1:1.
Example 2
Adding 260g of 2-methoxycyclohexylamine and 200g of ethanol into a three-neck flask, dropwise adding 106g of acrylonitrile into the three-neck flask at the speed of 1g/min, and carrying out stirring reaction at 50 ℃ for 2 h; and analyzing the reaction liquid by adopting gas chromatography, analyzing and calculating the conversion rate of acrylonitrile by taking n-propanol as an internal standard substance, and simultaneously analyzing and comparing 3- (2-methoxycyclohexyl) -aminopropionitrile by adopting the gas chromatography to calculate the selectivity of the 3- (2-methoxycyclohexyl) -aminopropionitrile. Wherein the molar ratio of the 2-methoxycyclohexylamine to the acrylonitrile is 1:1, and the mass ratio of the ethanol to the 2-methoxycyclohexylamine is 0.77: 1.
Example 3
Adding 300g of 2-methoxycyclohexylamine and 200g of ethanol into a three-neck flask, dropwise adding 100g of acrylonitrile into the three-neck flask at the speed of 1g/min, and carrying out stirring reaction at 50 ℃ for 8 h; and analyzing the reaction liquid by adopting gas chromatography, analyzing and calculating the conversion rate of acrylonitrile by taking n-propanol as an internal standard substance, and simultaneously analyzing and comparing 3- (2-methoxycyclohexyl) -aminopropionitrile by adopting the gas chromatography to calculate the selectivity of the 3- (2-methoxycyclohexyl) -aminopropionitrile. Wherein the molar ratio of the 2-methoxycyclohexylamine to the acrylonitrile is 1:0.8, and the mass ratio of the ethanol to the 2-methoxycyclohexylamine is 0.67: 1.
Example 4
Adding 260g of 2-methoxycyclohexylamine and 200g of ethanol into a three-neck flask, dropwise adding 100g of acrylonitrile into the three-neck flask at the speed of 1g/min, and carrying out stirring reaction at 70 ℃ for 8 h; and analyzing the reaction liquid by adopting gas chromatography, analyzing and calculating the conversion rate of acrylonitrile by taking n-propanol as an internal standard substance, and simultaneously analyzing and comparing 3- (2-methoxycyclohexyl) -aminopropionitrile by adopting the gas chromatography to calculate the selectivity of the 3- (2-methoxycyclohexyl) -aminopropionitrile. Wherein the molar ratio of the 2-methoxycyclohexylamine to the acrylonitrile is 1:0.94, and the mass ratio of the ethanol to the 2-methoxycyclohexylamine is 0.77: 1.
Example 5
Adding 260g of 2-methoxycyclohexylamine and 200g of methanol into a three-neck flask, dropwise adding 100g of acrylonitrile into the three-neck flask at the speed of 1g/min, and carrying out stirring reaction at 70 ℃ for 8 h; and analyzing the reaction liquid by adopting gas chromatography, analyzing and calculating the conversion rate of acrylonitrile by taking n-propanol as an internal standard substance, and simultaneously analyzing and comparing 3- (2-methoxycyclohexyl) -aminopropionitrile by adopting the gas chromatography to calculate the selectivity of the 3- (2-methoxycyclohexyl) -aminopropionitrile. Wherein the molar ratio of the 2-methoxycyclohexylamine to the acrylonitrile is 1:0.94, and the mass ratio of the methanol to the 2-methoxycyclohexylamine is 0.77: 1.
Example 6
Adding 260g of 2-methoxycyclohexylamine and 200g of isopropanol into a three-neck flask, dropwise adding 100g of acrylonitrile into the three-neck flask at the speed of 1g/min, and carrying out stirring reaction at 70 ℃ for 8 h; and analyzing the reaction liquid by adopting gas chromatography, analyzing and calculating the conversion rate of acrylonitrile by taking n-propanol as an internal standard substance, and simultaneously analyzing and comparing 3- (2-methoxycyclohexyl) -aminopropionitrile by adopting the gas chromatography to calculate the selectivity of the 3- (2-methoxycyclohexyl) -aminopropionitrile. Wherein the molar ratio of the 2-methoxycyclohexylamine to the acrylonitrile is 1:0.94, and the mass ratio of the isopropanol to the 2-methoxycyclohexylamine is 0.77: 1.
Example 7
Adding 260g of 2-methoxycyclohexylamine and 200g of ethanol into a three-neck flask, dropwise adding 106g of acrylonitrile into the three-neck flask at the speed of 1g/min, and carrying out stirring reaction at 50 ℃ for 8 h; and (3) analyzing the reaction liquid by adopting gas chromatography, analyzing and calculating the conversion rate of acrylonitrile by taking n-propanol as an internal standard substance, and analyzing and comparing 3- (2-methoxycyclohexyl) -aminopropionitrile by adopting the gas chromatography to calculate the selectivity of the 3- (2-methoxycyclohexyl) -aminopropionitrile. Wherein the molar ratio of the 2-methoxycyclohexylamine to the acrylonitrile is 1:1, and the mass ratio of the ethanol to the 2-methoxycyclohexylamine is 0.77: 1.
Example 8
Adding 260g of 2-methoxycyclohexylamine and 200g of ethanol into a three-neck flask, dropwise adding 106g of acrylonitrile into the three-neck flask at the speed of 1g/min, and carrying out stirring reaction at 50 ℃ for 4 h; and analyzing the reaction liquid by adopting gas chromatography, analyzing and calculating the conversion rate of acrylonitrile by taking n-propanol as an internal standard substance, and simultaneously analyzing and comparing 3- (2-methoxycyclohexyl) -aminopropionitrile by adopting the gas chromatography to calculate the selectivity of the 3- (2-methoxycyclohexyl) -aminopropionitrile. Wherein the molar ratio of the 2-methoxycyclohexylamine to the acrylonitrile is 1:1, and the mass ratio of the ethanol to the 2-methoxycyclohexylamine is 0.77: 1.
Example 9
Adding 260g of 2-methoxycyclohexylamine into a three-neck flask, dropwise adding 106g of acrylonitrile into the three-neck flask at the speed of 1g/min, and carrying out stirring reaction at 50 ℃ for 4 h; and analyzing the reaction liquid by adopting gas chromatography, analyzing and calculating the conversion rate of acrylonitrile by taking n-propanol as an internal standard substance, and simultaneously analyzing and comparing 3- (2-methoxycyclohexyl) -aminopropionitrile by adopting the gas chromatography to calculate the selectivity of the 3- (2-methoxycyclohexyl) -aminopropionitrile. Wherein the molar ratio of the 2-methoxycyclohexylamine to the acrylonitrile is 1:1.
Example 10
Adding 260g of 2-methoxycyclohexylamine and 200g of ethanol into a three-neck flask, dropwise adding 106g of acrylonitrile into the three-neck flask at the speed of 1g/min, and carrying out stirring reaction at 50 ℃ for 4 hours; and analyzing the reaction liquid by adopting gas chromatography, analyzing and calculating the conversion rate of acrylonitrile by taking n-propanol as an internal standard substance, and simultaneously analyzing and comparing 3- (2-methoxycyclohexyl) -aminopropionitrile by adopting the gas chromatography to calculate the selectivity of the 3- (2-methoxycyclohexyl) -aminopropionitrile. Wherein the molar ratio of the 2-methoxycyclohexylamine to the acrylonitrile is 1:1, and the mass ratio of the ethanol to the 2-methoxycyclohexylamine is 0.77: 1.
The acrylonitrile conversion and 3- (2-methoxycyclohexyl) -aminopropionitrile selectivities in examples 1 to 10 were combined, and the results are shown in Table 1:
TABLE 1
Comparing the results of example 2, example 7 and example 8, it can be seen that the acrylonitrile conversion and the 3- (2-methoxycyclohexyl) -aminopropionitrile selectivity were higher after 4h and 8h, respectively, of addition reaction compared to 2h under the same conditions; the reaction time is an important factor influencing the efficiency of the addition reaction, and when the reaction time of the addition reaction is 4-8 hours, the acrylonitrile conversion rate and the 3- (2-methoxycyclohexyl) -aminopropionitrile selectivity are both higher, so that the reaction efficiency can be effectively improved.
Comparing the results of examples 1 and 9 with the results of examples 2 to 8 and 10, it can be seen that when the addition reaction is performed in the reaction medium, the conversion rate of acrylonitrile and the selectivity of 3- (2-methoxycyclohexyl) -aminopropionitrile are both higher, which indicates that the addition reaction between 2-methoxycyclohexylamine and acrylonitrile performed in the reaction medium is beneficial to the more uniform distribution of the reaction raw materials in the reaction medium, the increase of the contact between 2-methoxycyclohexylamine and acrylonitrile, and the improvement of the reaction efficiency. Further, as can be seen from comparison of the results of examples 4 to 6, when the addition reaction was carried out using ethanol as a reaction medium under the same conditions, the conversion of acrylonitrile and the selectivity of 3- (2-methoxycyclohexyl) -aminopropionitrile were high, indicating that the addition reaction efficiency was higher when ethanol was used as a reaction medium.
Comparing the results of example 1 and example 9, it can be seen that the conversion of acrylonitrile and the selectivity of 3- (2-methoxycyclohexyl) -aminopropionitrile are higher when the reaction temperature is 60 ℃ than when the reaction temperature is 10 to 20 ℃; indicating that the reaction temperature is an important factor affecting the efficiency of the addition reaction. Moreover, as can be seen from examples 3 to 8 and 10, when the reaction temperature of the addition reaction is 50 to 80 ℃, the acrylonitrile conversion rate and the 3- (2-methoxycyclohexyl) -aminopropionitrile selectivity are both high, and the addition reaction efficiency is higher.
Comparing the results of examples 3 and 7, it can be seen that when the molar ratio of 2-methoxycyclohexylamine to acrylonitrile is 1:1, the acrylonitrile conversion and the 3- (2-methoxycyclohexyl) -aminopropionitrile selectivity are higher than when the molar ratio of 2-methoxycyclohexylamine to acrylonitrile is 1: 0.8; the molar ratio of the 2-methoxycyclohexylamine to the acrylonitrile is shown to be an important factor influencing the efficiency of the addition reaction, and when the molar ratio of the 2-methoxycyclohexylamine to the acrylonitrile is 1: (0.95 to 1.05), the efficiency of the addition reaction is higher.
Example 11
100g of Raney nickel is put into a catalyst frame of a reaction kettle, 400g of 3- (2-methoxycyclohexyl) -aminopropionitrile is put into the reaction kettle, the temperature is raised to 90 ℃, hydrogen is introduced, the pressure of the hydrogen is 3MPa, the stirring reaction is carried out for 6 hours until no pressure drop exists, and the reaction is finished. The product was analyzed by gas chromatography to calculate the conversion of 3- (2-methoxycyclohexyl) -aminopropionitrile and the selectivity to N- (2-methoxycyclohexyl) -1, 3-propanediamine.
Example 12
100g of Raney nickel is put into a catalyst frame of a reaction kettle, 400g of 3- (2-methoxycyclohexyl) -aminopropionitrile is put into the reaction kettle, the temperature is raised to 90 ℃, hydrogen is introduced, the pressure of the hydrogen is 3MPa, the stirring reaction is carried out for 12 hours until no pressure drop exists, and the reaction is finished. The product was analyzed by gas chromatography to calculate the conversion of 3- (2-methoxycyclohexyl) -aminopropionitrile and the selectivity to N- (2-methoxycyclohexyl) -1, 3-propanediamine.
Example 13
100g of Raney nickel is put into a catalyst frame of a reaction kettle, 255g of 3- (2-methoxycyclohexyl) -aminopropionitrile, 50g of liquid ammonia and 400g of ethanol are put into the reaction kettle, the temperature is raised to 50 ℃, hydrogen is introduced, the pressure of the hydrogen is 4MPa, the mixture is stirred and reacts for 24 hours until no pressure drop exists, and the reaction is finished. The product was analyzed by gas chromatography to calculate the conversion of 3- (2-methoxycyclohexyl) -aminopropionitrile and the selectivity to N- (2-methoxycyclohexyl) -1, 3-propanediamine.
Example 14
100g of Raney nickel is put into a catalyst frame of a reaction kettle, 255g of 3- (2-methoxycyclohexyl) -aminopropionitrile, 50g of liquid ammonia and 400g of ethanol are put into the reaction kettle, the temperature is raised to 75 ℃, hydrogen is introduced, the pressure of the hydrogen is 4MPa, the mixture is stirred and reacts for 24 hours until no pressure drop exists, and the reaction is finished. The product was analyzed by gas chromatography to calculate the conversion of 3- (2-methoxycyclohexyl) -aminopropionitrile and the selectivity to N- (2-methoxycyclohexyl) -1, 3-propanediamine.
Example 15
100g of Raney nickel is put into a catalyst frame of a reaction kettle, 190g of 3- (2-methoxycyclohexyl) -aminopropionitrile, 100g of liquid ammonia and 500g of ethanol are put into the reaction kettle, the temperature is raised to 60 ℃, hydrogen is introduced, the pressure of the hydrogen is 2MPa, the stirring reaction is carried out for 15 hours until no pressure drop exists, and the reaction is finished. The product was analyzed by gas chromatography to calculate the conversion of 3- (2-methoxycyclohexyl) -aminopropionitrile and the selectivity to N- (2-methoxycyclohexyl) -1, 3-propanediamine.
Example 16
100g of Raney nickel is filled into a catalyst frame of a reaction kettle, 190g of 3- (2-methoxycyclohexyl) -aminopropionitrile, 100g of liquid ammonia and 50g of ethanol are put into the reaction kettle, the temperature is raised to 60 ℃, hydrogen is introduced, the pressure of the hydrogen is 2MPa, the reaction is stirred for 15 hours until no pressure drop exists, and the reaction is finished. The product was analyzed by gas chromatography to calculate the conversion of 3- (2-methoxycyclohexyl) -aminopropionitrile and the selectivity to N- (2-methoxycyclohexyl) -1, 3-propanediamine.
The results of a summary of the conversion of 3- (2-methoxycyclohexyl) -aminopropionitrile and the selectivity for N- (2-methoxycyclohexyl) -1, 3-propanediamine in examples 11-16 are shown in Table 2:
TABLE 2
Comparing the results of example 11 and example 12, it can be seen that the conversion of 3- (2-methoxycyclohexyl) -aminopropionitrile and the selectivity for N- (2-methoxycyclohexyl) -1, 3-propanediamine were both higher when the hydrogenation was carried out for 12h compared to 6h when the hydrogenation was carried out under the same conditions; the reaction time is an important factor influencing the hydrogenation reaction efficiency, and when the reaction time of the hydrogenation reaction is 8-24 hours, the hydrogenation reaction efficiency is higher.
Comparing the results of example 13 and example 14, it can be seen that under the same conditions, the conversion of 3- (2-methoxycyclohexyl) -aminopropionitrile and the selectivity of N- (2-methoxycyclohexyl) -1, 3-propanediamine are higher when the reaction temperature of the hydrogenation reaction is 75 ℃ than when the reaction temperature of the hydrogenation reaction is 50 ℃; the reaction temperature is an important factor influencing the hydrogenation reaction efficiency, and when the reaction temperature of the hydrogenation reaction is 55-75 ℃, the hydrogenation reaction efficiency is higher.
Comparing the results of examples 11-12 with those of examples 13-16, it can be seen that when the hydrogenation reaction is carried out in the reaction medium with the addition of the inhibitor, the conversion of 3- (2-methoxycyclohexyl) -aminopropionitrile and the selectivity of N- (2-methoxycyclohexyl) -1, 3-propanediamine are both higher, indicating that the addition of the inhibitor can reduce the occurrence of side reactions and improve the reaction efficiency; the hydrogenation reaction of the 3- (2-methoxycyclohexyl) -aminopropionitrile is carried out in a reaction medium, which is beneficial to more uniform distribution of reaction raw materials in the reaction medium, increases the contact between the 3- (2-methoxycyclohexyl) -aminopropionitrile and hydrogen, and further improves the reaction efficiency. Further, as can be seen from a comparison of the results of examples 12 and 13, the conversion of 3- (2-methoxycyclohexyl) -aminopropionitrile and the selectivity for N- (2-methoxycyclohexyl) -1, 3-propanediamine were high and the hydrogenation efficiency was higher as the mass ratio of the reaction medium to 3- (2-methoxycyclohexyl) -aminopropionitrile was higher under the same conditions.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of an amine intermediate, which is characterized in that the amine intermediate comprises N- (2-methoxycyclohexyl) -1, 3-propane diamine, and the preparation method comprises the following steps:
performing addition reaction on 2-methoxycyclohexylamine and acrylonitrile at 10-100 ℃ to generate 3- (2-methoxycyclohexyl) -aminopropionitrile;
and (2) carrying out hydrogenation reaction on the 3- (2-methoxycyclohexyl) -aminopropionitrile in a hydrogen atmosphere at the temperature of 20-120 ℃ under the action of a catalyst to obtain the compound.
2. The preparation method of amine intermediate according to claim 1, wherein the molar ratio of the 2-methoxycyclohexylamine to the acrylonitrile is 1 (0.8-1.2).
3. The method for preparing an amine intermediate according to claim 1, wherein the reaction time is 1 to 10 hours when the addition reaction is performed.
4. The method for preparing amine intermediate according to any one of claims 1 to 3, wherein the addition reaction is carried out in a first reaction medium;
optionally, the first reaction medium comprises one or more of methanol, ethanol, isopropanol, and n-butanol; the mass ratio of the first reaction medium to the 2-methoxycyclohexylamine is (0.5-5): 1.
5. The process for producing amine intermediates according to claim 1, wherein the hydrogenation reaction is carried out under at least one of the following conditions:
(1) the reaction time is 2-48 h;
(2) the pressure of the hydrogen atmosphere is 1-10 MPa;
(3) the catalyst is Raney nickel.
6. The method for preparing amine intermediates according to claim 5, wherein the amount of the catalyst is 5 to 50% by mass of the liquid in the system at the start of the hydrogenation reaction.
7. The process for producing an amine intermediate according to claim 1, wherein an inhibitor is further added during the hydrogenation reaction;
optionally, the inhibitor comprises one or more of liquid ammonia, sodium hydroxide, and potassium hydroxide; the addition amount of the inhibitor accounts for 5-100% of the mass percent of the 3- (2-methoxycyclohexyl) -aminopropionitrile.
8. The method for preparing amine intermediates according to any one of claims 1 and 5 to 7, wherein the hydrogenation reaction is carried out in a second reaction medium;
optionally, the second reaction medium comprises one or more of methanol, ethanol, isopropanol, and n-butanol; the mass ratio of the second reaction medium to the 3- (2-methoxycyclohexyl) -aminopropionitrile is (0.5-5): 1.
9. An amine intermediate, characterized by being prepared by the method for preparing the amine intermediate according to any one of claims 1 to 8.
10. Use of the amine intermediate of claim 9 for the preparation of epoxy resin curing agents, polymerization aids, rubber additives, pharmaceuticals and/or pesticides.
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| US20040180967A1 (en) * | 2001-07-05 | 2004-09-16 | Norberto Bilbeny Lojo | Compounds used to treat alcoholism |
| CN106866431A (en) * | 2017-02-22 | 2017-06-20 | 浙江新化化工股份有限公司 | A kind of production method of 1,3 propane diamine of N (2 methoxycyclohexyl) |
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| CN116003268A (en) * | 2022-12-30 | 2023-04-25 | 同创化学(南京)有限公司 | Amine compound and preparation and application thereof |
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