CN111004132B - Preparation method of norbornane dimethylamine - Google Patents
Preparation method of norbornane dimethylamine Download PDFInfo
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- CN111004132B CN111004132B CN201911308027.6A CN201911308027A CN111004132B CN 111004132 B CN111004132 B CN 111004132B CN 201911308027 A CN201911308027 A CN 201911308027A CN 111004132 B CN111004132 B CN 111004132B
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Abstract
The invention provides a preparation method of norbornane dimethylamine, which comprises the following steps: a) mixing a compound with a structure shown in a formula (I), urotropine, acid and a first solvent, and carrying out a first reaction to obtain a first reaction mixture; neutralizing and filtering the first reaction mixture in sequence for the first time, and purifying the obtained filtrate for the first time to obtain a compound with a structure shown in a formula (II); b) mixing the compound with the structure shown in the formula (II) obtained in the step a) with hydrogen, a catalyst and a second solvent, and carrying out a second reaction to obtain a second reaction mixture; and then carrying out secondary filtration on the second reaction mixture, and carrying out secondary purification on the obtained filtrate to obtain norbornane dimethylamine. Compared with the prior art, the preparation method provided by the invention can avoid using hydrogen cyanide, rhodium catalyst and other ligands, and has the advantages of simple method, easy operation, high product yield and wide application prospect.
Description
Technical Field
The invention relates to the technical field of organic compound synthesis, in particular to a preparation method of norbornane dimethylamine.
Background
Norbornane dimethylamine, also known as norbornane dimethylamine, is commonly used as an epoxy resin curing agent, and has excellent properties of rapid curing even at low temperature, and excellent strength, flexibility, heat distortion resistance, impact resistance, weather resistance, chemical resistance and yellowing resistance of the cured product.
Currently, the preparation method of norbornane dimethylamine in the prior art comprises the following steps:
(1) patent publication No. CN101443308A, which discloses a method for producing dicyanonorbornane and a zero-valent nickel complex catalyst, wherein norbornane dimethylamine is produced from norbornane dinitrile as a raw material; however, norbornane dinitrile is synthesized from cyanonorbornene and hydrogen cyanide.
(2) Patent publication No. CN104781228A, which discloses a process for producing an aldehyde compound, which produces norbornandimethylamine from formylcyanonorbornane as a raw material; however, formylcyanonorbornane is synthesized from cyanonorbornene, a rhodium catalyst, carbon monoxide, hydrogen gas and other raw materials under high pressure.
In the preparation scheme, hydrogen cyanide is used in the process of preparing norbornane dimethylamine by the method (1), and because the hydrogen cyanide is extremely toxic and has a low boiling point, the explosion limit in the air is 5.6-12.8%, and danger is easy to occur; in the method (2), an expensive rhodium catalyst is used in the process of producing norbornanemethylamine, and other ligands need to be used, so that the method is complicated. In addition, the two methods have the problems of relatively complex post-treatment, low yield and complex operation.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing norbornanemethylamine, which can avoid the use of hydrogen cyanide, rhodium catalyst and other ligands, and has the advantages of simple method, easy operation and high product yield.
The invention provides a preparation method of norbornane dimethylamine, which comprises the following steps:
a) mixing a compound with a structure shown in a formula (I), urotropine, acid and a first solvent, and carrying out a first reaction to obtain a first reaction mixture; neutralizing and filtering the first reaction mixture in sequence for the first time, and purifying the obtained filtrate for the first time to obtain a compound with a structure shown in a formula (II);
b) mixing the compound with the structure shown in the formula (II) obtained in the step a) with hydrogen, a catalyst and a second solvent, and carrying out a second reaction to obtain a second reaction mixture; and then carrying out secondary filtration on the second reaction mixture, and carrying out secondary purification on the obtained filtrate to obtain norbornane dimethylamine.
Preferably, the acid in step a) is selected from one or more of hydrobromic acid, oxalic acid, hypochlorous acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid and trifluoroacetic acid.
Preferably, the first solvent in step a) is selected from one or more of acrylonitrile, acetonitrile, propionitrile, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diethyl ether.
Preferably, the molar ratio of the compound represented by the formula (I) in the step a) to the urotropine is 1: (0.25 to 1).
Preferably, the mass ratio of the compound having the structure represented by formula (I), the acid and the first solvent in step a) is 1: (1-10): (5-20).
Preferably, the temperature of the first reaction in the step a) is 30-100 ℃, and the time is 4-17 h.
Preferably, the catalyst in step b) is selected from one or more of palladium carbon, nickel formate, platinum black, platinum carbon, nickel-alumina, ultrafine nickel, raney cobalt and raney copper.
Preferably, the second solvent in step b) is selected from one or more of methanol, toluene, o-xylene, m-xylene and p-xylene.
Preferably, the mass ratio of the structural compound represented by the formula (II) in the step b), the catalyst and the second solvent is 1: (0.01-0.35): (20 to 50).
Preferably, the temperature of the second reaction in the step b) is 60-140 ℃, the pressure is 0.5-2 MPa, and the time is 3-10 h.
The invention provides a preparation method of norbornane dimethylamine, which comprises the following steps: a) mixing a compound with a structure shown in a formula (I), urotropine, acid and a first solvent, and carrying out a first reaction to obtain a first reaction mixture; neutralizing and filtering the first reaction mixture in sequence for the first time, and purifying the obtained filtrate for the first time to obtain a compound with a structure shown in a formula (II); b) mixing the compound with the structure shown in the formula (II) obtained in the step a) with hydrogen, a catalyst and a second solvent, and carrying out a second reaction to obtain a second reaction mixture; and then carrying out secondary filtration on the second reaction mixture, and carrying out secondary purification on the obtained filtrate to obtain norbornane dimethylamine. Compared with the prior art, the preparation method provided by the invention can avoid using hydrogen cyanide, rhodium catalyst and other ligands, and has the advantages of simple method, easy operation, high product yield and wide application prospect.
Drawings
FIG. 1 is a hydrogen spectrum of norbornanediamine provided in example 1 of the present invention;
FIG. 2 shows a high resolution mass spectrum of norbornanedimethylamine provided in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of norbornane dimethylamine, which comprises the following steps:
a) mixing a compound with a structure shown in a formula (I), urotropine, acid and a first solvent, and carrying out a first reaction to obtain a first reaction mixture; neutralizing and filtering the first reaction mixture in sequence for the first time, and purifying the obtained filtrate for the first time to obtain a compound with a structure shown in a formula (II);
b) mixing the compound with the structure shown in the formula (II) obtained in the step a) with hydrogen, a catalyst and a second solvent, and carrying out a second reaction to obtain a second reaction mixture; and then carrying out secondary filtration on the second reaction mixture, and carrying out secondary purification on the obtained filtrate to obtain norbornane dimethylamine.
The invention firstly mixes the compound with the structure shown in the formula (I) with urotropine, acid and a first solvent to carry out a first reaction to obtain a first reaction mixture. In the invention, the compound with the structure shown in the formula (I) is norbornadiene. The sources of the norbornadiene and urotropin are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the present invention, the molar ratio of the compound having the structure represented by formula (I) to urotropin is preferably 1: (0.25 to 1), more preferably 1: (0.35-0.6).
In the present invention, the acid is preferably selected from one or more of hydrobromic acid, oxalic acid, hypochlorous acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid and trifluoroacetic acid, and more preferably sulfuric acid, acetic acid or trifluoroacetic acid. The present invention is not particularly limited in the origin of the acid, and commercially available products of the above-mentioned hydrobromic acid, oxalic acid, hypochlorous acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid and trifluoroacetic acid, which are well known to those skilled in the art, may be used. In the present invention, the mass ratio of the compound having the structure represented by the formula (I) to the acid is preferably 1: (1-10), more preferably 1: (3-6).
In the present invention, the first solvent is an inert organic solvent, preferably one or more selected from the group consisting of acrylonitrile, acetonitrile, propionitrile, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diethyl ether, more preferably acetone, acetonitrile or diethyl ether. The source of the first solvent is not particularly limited in the present invention, and commercially available products of the above-mentioned acrylonitrile, acetonitrile, propionitrile, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diethyl ether, which are well known to those skilled in the art, may be used. In the present invention, the mass ratio of the compound having the structure represented by the formula (I) to the first solvent is preferably 1: (5-20), more preferably 1: (10-15).
The mixing apparatus of the present invention is not particularly limited, and a single-neck flask well known to those skilled in the art may be used.
In the present invention, the temperature of the first reaction is preferably 30 ℃ to 100 ℃, more preferably 30 ℃ to 70 ℃, and is achieved by means of an oil bath well known to those skilled in the art; the time for the first reaction is preferably 4 to 17 hours, and more preferably 5 to 15 hours.
After the first reaction mixture is obtained, the first reaction mixture is neutralized and filtered for the first time in sequence, and the obtained filtrate is purified for the first time to obtain the compound with the structure shown in the formula (II). In the present invention, the neutralization process is preferably carried out by using a saturated sodium carbonate solution or a saturated sodium bicarbonate solution, and the system is adjusted to be neutral.
The process of the first filtration is not particularly limited in the present invention, and the object is to obtain a filtrate containing a compound having a structure represented by the formula (II).
In the present invention, the first purification process is preferably specifically:
and (3) layering the filtrate in a separating funnel to obtain an organic phase, and performing rotary evaporation on the organic phase to obtain the compound with the structure shown in the formula (II).
After the compound with the structure shown in the formula (II) is obtained, the obtained compound with the structure shown in the formula (II) is mixed with hydrogen, a catalyst and a second solvent to carry out a second reaction, so as to obtain a second reaction mixture. The source of the hydrogen gas is not particularly limited in the present invention, and commercially available products or self-products known to those skilled in the art may be used.
In the present invention, the catalyst is preferably selected from one or more of palladium carbon, nickel formate, platinum black, platinum carbon, nickel-alumina, ultrafine nickel, raney cobalt and raney copper, and more preferably palladium carbon or raney nickel. The source of the catalyst in the present invention is not particularly limited, and commercially available products of the above palladium carbon, nickel formate, platinum black, platinum carbon, nickel-alumina, ultrafine nickel, raney cobalt and raney copper known to those skilled in the art may be used. In the present invention, the mass ratio of the structural compound represented by the formula (II) to the catalyst is preferably 1: (0.01 to 0.35), more preferably 1: (0.05-0.15).
In the present invention, the second solvent is an inert organic solvent, preferably one or more selected from methanol, toluene, o-xylene, m-xylene, and p-xylene, more preferably toluene or methanol. The source of the second solvent is not particularly limited in the present invention, and commercially available products of the above-mentioned methanol, toluene, o-xylene, m-xylene and p-xylene, which are well known to those skilled in the art, may be used. In the present invention, the mass ratio of the structural compound represented by the formula (II) to the second solvent is preferably 1: (20 to 50), more preferably 1: (25-35).
In the present invention, the mixing device preferably employs an autoclave well known to those skilled in the art; the amount of the hydrogen used is preferably such an amount that the above autoclave is charged to a reaction pressure of the second reaction.
In the invention, the temperature of the second reaction is preferably 60-140 ℃, more preferably 95-130 ℃; the pressure of the second reaction is preferably 0.5MPa to 2MPa, and more preferably 0.7MPa to 1.7 MPa; the time for the second reaction is preferably 3 to 10 hours, and more preferably 5 to 10 hours.
After the second reaction mixture is obtained, the second reaction mixture is filtered for the second time, and the obtained filtrate is purified for the second time to obtain norbornanedimethylamine. In the present invention, the purpose of the second filtration is to remove solid compounds from the second reaction mixture, and the present invention is not limited to this, and the filtration method known to those skilled in the art can be used.
In the present invention, the second purification process may be performed by a rotary evaporation method well known to those skilled in the art, so as to remove the solvent to obtain pure norbornane dimethylamine.
The preparation method provided by the invention avoids using hydrogen cyanide, and because the hydrogen cyanide is extremely toxic and has a low boiling point, the explosion limit in the air is 5.6-12.8%, so that danger is easily caused; thereby greatly reducing the danger of the preparation method of the invention; meanwhile, the method avoids using expensive rhodium catalyst and other ligands, and combines the two points.
The invention provides a preparation method of norbornane dimethylamine, which comprises the following steps: a) mixing a compound with a structure shown in a formula (I), urotropine, acid and a first solvent, and carrying out a first reaction to obtain a first reaction mixture; neutralizing and filtering the first reaction mixture in sequence for the first time, and purifying the obtained filtrate for the first time to obtain a compound with a structure shown in a formula (II); b) mixing the compound with the structure shown in the formula (II) obtained in the step a) with hydrogen, a catalyst and a second solvent, and carrying out a second reaction to obtain a second reaction mixture; and then carrying out secondary filtration on the second reaction mixture, and carrying out secondary purification on the obtained filtrate to obtain norbornane dimethylamine. Compared with the prior art, the preparation method provided by the invention can avoid using hydrogen cyanide, rhodium catalyst and other ligands, and has the advantages of simple method, easy operation, high product yield and wide application prospect.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials used in the following examples of the present invention are all commercially available products; wherein the norbornadiene has a structure shown in a formula (I);
example 1
(1) Weighing 9.21g of norbornadiene into a 500mL single-neck flask, sequentially adding 9.81g of urotropine, 64.47g of sulfuric acid and 138.15g of acetone, reacting for 15 hours at 70 ℃ in an oil bath T, adjusting the system to be neutral by using a saturated sodium carbonate solution after the reaction is finished, and filtering to obtain a filtrate containing the compound with the structure shown in the formula (II);
then layering the filtrate in a separating funnel to obtain an organic phase, and performing rotary evaporation on the organic phase to obtain 13.82g of norbornene dimethylamine; the above procedure was repeated to obtain more target products, to give 27.63g of norbornene dimethylamine.
(2) Weighing 15.02g of the norbornene dimethylamine obtained in the step (1) in a 500mL autoclave, sequentially adding 1.05g of palladium on carbon and 376.25g of toluene, pressurizing to 0.7MPa with hydrogen and maintaining the pressure during the reaction, heating to 95 ℃ to react for 5h, filtering the system after the reaction is completed, and performing rotary evaporation on the filtrate to obtain 13.88g of norbornane dimethylamine which has the structure shown in the formula (III):
the structure of norbornane dimethylamine prepared by the preparation method provided by the embodiment 1 of the invention is identified, and the result is shown in the figure 1-2; fig. 1 is a hydrogen spectrum of norbornanedimethylamine provided in example 1 of the present invention, and fig. 2 is a high-resolution mass spectrum of norbornanedimethylamine provided in example 1 of the present invention.
Example 2
(1) Weighing 9.21g of norbornadiene into a 250mL single-neck flask, sequentially adding 5.61g of urotropine, 36.84g of acetic acid and 92.1g of acetonitrile, reacting for 10 hours at 50 ℃ in an oil bath T, adjusting the system to be neutral by using a saturated sodium carbonate solution after the reaction is finished, and filtering to obtain a filtrate containing the compound with the structure shown in the formula (II);
then, layering the filtrate in a separating funnel to obtain an organic phase, and performing rotary evaporation on the organic phase to obtain 14.27g of norbornene dimethylamine; the above procedure was repeated to obtain more target products, to give 28.55g of norbornene dimethylamine.
(2) Weighing 15.02g of the norbornene dimethylamine obtained in the step (1) in a 500mL autoclave, sequentially adding 1.05g of Raney nickel and 376.25g of methanol, pressurizing to 0.9MPa with hydrogen, maintaining the pressure during the reaction, heating to 100 ℃ for reaction for 6h, filtering the system after the reaction is finished, and performing rotary evaporation on the filtrate to obtain 14.65g of norbornane dimethylamine.
Example 3
(1) Weighing 9.21g of norbornadiene into a 250mL single-neck flask, sequentially adding 3.51g of urotropine, 27.63g of trifluoroacetic acid and 110.52g of diethyl ether, reacting for 5 hours at an oil bath T ═ 30 ℃, adjusting the system to be neutral by using a saturated sodium carbonate solution after the reaction is finished, and filtering to obtain a filtrate containing the compound with the structure shown in the formula (II);
then layering the filtrate in a separating funnel to obtain an organic phase, and performing rotary evaporation on the organic phase to obtain 13.22g of norbornene dimethylamine; the above procedure was repeated to obtain more target products, to give 26.42g of norbornene dimethylamine.
(2) Weighing 15.02g of the norbornene dimethylamine obtained in the step (1) in a 1000mL autoclave, sequentially adding 1.05g of raney nickel and 450.6g of methanol, pressurizing to 1.7MPa with hydrogen, maintaining the pressure during the reaction, heating to 130 ℃ for reaction for 10h, filtering the system after the reaction is finished, and performing rotary evaporation on the filtrate to obtain 14.03g of norbornane dimethylamine.
Comparative example 1
A50 mL glass round bottom flask equipped with a stirrer, a thermometer, a nitrogen inlet and a condenser was charged with 1.07g (4.5mmol) of nickel chloride hexahydrate, 0.60g (9.2mmol) of zinc, 8.90g (28.7mmol) of triphenyl phosphite containing 0.2 wt% of triphenyl phosphate purified by a known method and 26.5g (22.2mmol) of cyanonorbornene, and nitrogen substitution in the gas phase portion was reliably performed to obtain a tetrakis (triphenyl phosphite) nickel catalyst.
Then, 307.0g (2.58mol) of cyanonorbornene, 90.0g of toluene and the catalyst synthesis solution obtained above were charged in a 1L glass-made flat-bottomed separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, a hydrogen cyanide inlet and a condenser, and after nitrogen substitution in the gas phase portion was sufficiently performed at room temperature, the temperature was raised to 60 ℃.
Then, 69.13g (2.66mol) of liquid hydrogen cyanide was supplied over 3.5 hours, and a cyanato hydrogenation reaction was carried out to obtain 480.7g of crude dicyano norbornane; 480.7g of the crude dicyanonorbornane was bubbled at a flow rate of 500ml/min of nitrogen for 1 hour to degas it, and then insoluble matter was filtered; to the filtrate, 1.9g of 40% sulfuric acid was added, and the mixture was heated at 60 ℃ for 3 hours to decompose the catalyst, and further, 5.5g of 25% sodium hydroxide was added, and the mixture was heated at 40 ℃ for 2 hours to neutralize the resultant, 449.0g of toluene was added to extract dicyanonorbornane to obtain a dicyanonornane toluene solution, and then toluene was distilled off to obtain 447.6g of 85% dicyanonornane.
Then, 287.8g of the obtained dicyanonorbornane, 32.6g of 25% ammonia water and 7.9g of Raney's cobalt catalyst were charged in a 500mL autoclave, and a catalytic hydrogenation reaction was carried out at 120 ℃ under a hydrogen pressure of 3.5MPa for 430 minutes; after cooling to room temperature and removing catalyst Raney cobalt by filtration, 0.5g of 32 wt% caustic soda was added to the filtrate, and ammonia and toluene contained in dicyanonorbornane were distilled off at 2.6KPa and 75 ℃; then, the mixture was distilled under 0.1MPa at an internal temperature of the flask of 150 to 160 ℃ to obtain 204g of norbornanedimethylamine.
As can be seen from comparison of the above examples and comparative examples, the preparation method provided by the invention can avoid using hydrogen cyanide, rhodium catalyst and other ligands, and has the advantages of simple method, easy operation, low risk, easily available raw materials, low cost and high product yield.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A preparation method of norbornane dimethylamine comprises the following steps:
a) mixing a compound with a structure shown in a formula (I), urotropine, acid and a first solvent, and carrying out a first reaction to obtain a first reaction mixture; neutralizing and filtering the first reaction mixture in sequence for the first time, and purifying the obtained filtrate for the first time to obtain a compound with a structure shown in a formula (II); the temperature of the first reaction is 30-70 ℃, and the time is 5-15 h;
b) mixing the compound with the structure shown in the formula (II) obtained in the step a) with hydrogen, a catalyst and a second solvent, and carrying out a second reaction to obtain a second reaction mixture; then, carrying out secondary filtration on the second reaction mixture, and carrying out secondary purification on the obtained filtrate to obtain norbornane dimethylamine; the temperature of the second reaction is 95-130 ℃, the pressure is 0.7-1.7 MPa, and the time is 5-10 h.
2. The method according to claim 1, wherein the acid in step a) is one or more selected from the group consisting of hydrobromic acid, oxalic acid, hypochlorous acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid and trifluoroacetic acid.
3. The method according to claim 1, wherein the first solvent in step a) is selected from one or more of acrylonitrile, acetonitrile, propionitrile, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diethyl ether.
4. The method according to claim 1, wherein the molar ratio of the compound having the structure represented by formula (I) to urotropin in step a) is 1: (0.25 to 1).
5. The method according to claim 1, wherein the mass ratio of the compound having the structure represented by formula (I), the acid and the first solvent in step a) is 1: (1-10): (5-20).
6. The method of claim 1, wherein the catalyst in step b) is selected from one or more of palladium carbon, nickel formate, platinum black, platinum carbon, nickel-alumina, ultra-fine nickel, raney cobalt and raney copper.
7. The method of claim 1, wherein the second solvent in step b) is selected from one or more of methanol, toluene, o-xylene, m-xylene, and p-xylene.
8. The method according to claim 1, wherein the mass ratio of the structural compound represented by the formula (II), the catalyst and the second solvent in step b) is 1: (0.01-0.35): (20 to 50).
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| EP3176151A1 (en) * | 2015-12-01 | 2017-06-07 | Studiengesellschaft Kohle mbH | Process for the catalytic reversible alkene-nitrile interconversion |
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| JP2005179203A (en) * | 2003-12-17 | 2005-07-07 | Mitsubishi Gas Chem Co Inc | Method for preparing amino composition |
| JP2011201952A (en) * | 2010-03-24 | 2011-10-13 | Mitsui Chemicals Inc | Polyimide, process for producing the same, polyamic acid and process for producing the same |
| CN104781228A (en) * | 2012-11-09 | 2015-07-15 | 三井化学株式会社 | Method for producing aldehyde compound |
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