CN112250583A - Preparation method of norbornane dimethylamine - Google Patents
Preparation method of norbornane dimethylamine Download PDFInfo
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Abstract
The invention belongs to the field of chemical synthesis, and particularly relates to a preparation method of norbornane dimethylamine. The preparation method provided by the invention comprises the following steps: a) mixing and reacting a compound with a structure shown in a formula (I), paraformaldehyde, acid and ammonium salt in a solvent to obtain a compound with a structure shown in a formula (II); b) and (2) reacting the compound with the structure of the formula (II) with hydrogen in a solvent in the presence of a catalyst to obtain norbornane dimethylamine. The preparation method provided by the invention does not need hydrogen cyanide and expensive catalyst, and has the advantages of high safety, good economy, simple process route, high product yield and very wide market prospect.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a preparation method of norbornane dimethylamine.
Background
Currently, the following two methods are known for producing norbornane dimethylamine:
1) patent CN101443308B provides a method for producing norbornanediamine from norbornane dinitrile, which is synthesized from cyanonorbornene and hydrogen cyanide.
2) Patent CN104781228A provides a method for producing norbornanedimethylamine from formylcyanonorbornane, which is synthesized from cyanonorbornene, rhodium catalyst, carbon monoxide, hydrogen gas and other raw materials under high pressure.
Among the two methods, the first method uses hydrogen cyanide in the process of preparing norbornane dimethylamine, and the hydrogen cyanide is extremely toxic, has a lower boiling point, and has an explosion limit of 5.6-12.8% in the air, so that danger is easily caused; the second method uses an expensive rhodium catalyst in the production of norbornanedimethylamine, and requires the use of a ligand other than the rhodium catalyst, which is complicated. In addition, the above two methods have problems of complicated post-treatment, low yield and complicated operation.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method of norbornane dimethylamine, which does not need to use hydrogen cyanide and expensive catalysts, and has the advantages of simple process route and high product yield.
The invention provides a preparation method of norbornane dimethylamine, which comprises the following steps:
a) mixing and reacting a compound with a structure shown in a formula (I), paraformaldehyde, acid and ammonium salt in a solvent to obtain a compound with a structure shown in a formula (II);
b) and (2) reacting the compound with the structure of the formula (II) with hydrogen in a solvent in the presence of a catalyst to obtain norbornane dimethylamine.
Preferably, in step a), the acid comprises one or more of hydrobromic acid, phosphoric acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid and trifluoroacetic acid;
the mass ratio of the compound with the structure shown in the formula (I) to the acid is 1: (0.2-5).
Preferably, in step a), the ammonium salt includes one or more of ammonium chloride, ammonium bromide, ammonium acetate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, tetrabutylammonium chloride, tetrabutylammonium bromide, ammonium fluoride, ammonium iodide, ammonium sulfate and ammonium bisulfate;
the mass ratio of the compound with the structure shown in the formula (I) to the ammonium salt is 1: (1-5).
Preferably, in step a), the mass ratio of the structural compound of formula (I) to paraformaldehyde is 1: (0.65-5).
Preferably, in step a), the solvent comprises one or more of acrylonitrile, acetonitrile, propionitrile, acetone, methyl ethyl ketone, toluene, ethyl acetate, cyclohexanone and diethyl ether;
the mass ratio of the compound with the structure shown in the formula (I) to the solvent is 1: (3-15).
Preferably, in the step a), the temperature of the mixing reaction is 30-70 ℃; the mixing reaction time is 4-12 h.
Preferably, in step b), the catalyst comprises one or more of palladium carbon, platinum black, platinum carbon, nickel/alumina, ultrafine nickel, raney cobalt and raney copper;
the mass ratio of the compound with the structure of the formula (II) to the catalyst is 1: (0.01-0.35).
Preferably, in step b), the solvent comprises one or more of methanol, toluene, chloroform, o-xylene and m-xylene;
the mass ratio of the compound with the structure of the formula (II) to the solvent is 1: (3-20).
Preferably, in the step b), the reaction temperature is 60-100 ℃; the reaction pressure is 0.5-2 MPa.
Preferably, in the step b), the reaction time is 3-10 h.
Compared with the prior art, the invention provides a preparation method of norbornane dimethylamine. The preparation method provided by the invention comprises the following steps: a) mixing and reacting a compound with a structure shown in a formula (I), paraformaldehyde, acid and ammonium salt in a solvent to obtain a compound with a structure shown in a formula (II); b) and (2) reacting the compound with the structure of the formula (II) with hydrogen in a solvent in the presence of a catalyst to obtain norbornane dimethylamine. The preparation method provided by the invention does not need hydrogen cyanide and expensive catalyst, and has the advantages of high safety, good economy, simple process route, high product yield and very wide market prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a scheme for the synthesis of norbornanemethylamine according to an embodiment of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of norbornanedimethylamine provided in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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 and reacting a compound with a structure shown in a formula (I), paraformaldehyde, acid and ammonium salt in a solvent to obtain a compound with a structure shown in a formula (II);
b) and (2) reacting the compound with the structure of the formula (II) with hydrogen in a solvent in the presence of a catalyst to obtain norbornane dimethylamine.
In the preparation method provided by the invention, firstly, the compound with the structure shown in the formula (I), paraformaldehyde, acid and ammonium salt are mixed and reacted in a solvent. The polymerization degree of the paraformaldehyde is preferably 10-100; the mass ratio of the compound with the structure of the formula (I) to the paraformaldehyde is 1: (0.65-5), more preferably 1: (0.82 to 1.3), specifically 1:0.65, 1:0.67, 1:0.7, 1:0.72, 1:0.75, 1:0.78, 1:0.8, 1:0.82, 1:0.85, 1:0.87, 1:0.9, 1:0.92, 1:0.95, 1:0.98, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.7, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1: 5; the acid preferably comprises one or more of hydrobromic acid, phosphoric acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid and trifluoroacetic acid, more preferably acetic acid, sulfuric acid or hydrobromic acid; the mass ratio of the compound of the formula (I) to the acid is preferably 1: (0.2 to 5), more preferably 1: (0.2 to 1), most preferably 1: (0.2-0.7), specifically 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or 1: 1; the ammonium salt preferably comprises one or more of ammonium chloride, ammonium bromide, ammonium acetate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, tetrabutylammonium chloride, tetrabutylammonium bromide, ammonium fluoride, ammonium iodide, ammonium sulfate and ammonium bisulfate; the mass ratio of the compound with the structure of the formula (I) to the ammonium salt is preferably 1: (1-5), more preferably 1: (2-4), specifically 1:2, 1:2.5, 1:3, 1:3.5, 1: 4; the solvent preferably comprises one or more of acrylonitrile, acetonitrile, propionitrile, acetone, methyl ethyl ketone, toluene, ethyl acetate, cyclohexanone and diethyl ether, more preferably acetonitrile or toluene; the mass ratio of the compound with the structure of the formula (I) to the solvent is preferably 1: (3-15), more preferably 1: (3-13), most preferably 1: (5-8), specifically 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12 or 1: 13; the temperature of the mixing reaction is preferably 30-70 ℃, more preferably 45-65 ℃, and specifically can be 45 ℃, 50 ℃, 55 ℃, 60 ℃ or 65 ℃; the mixing reaction time is preferably 4-12 h, more preferably 6-10 h, and specifically can be 6h, 7h, 8h, 9h or 10 h. And after the mixing reaction is finished, carrying out post-treatment on the obtained reaction product to obtain the compound with the structure shown in the formula (II). In the present invention, the post-processing specifically includes: adjusting the pH value of the reaction product to be neutral, filtering, and separating liquid to obtain an organic phase; and then removing the solvent in the organic phase to obtain the compound with the structure shown in the formula (II). Wherein, the reagent used for pH adjustment is preferably sodium carbonate or sodium bicarbonate; the solvent is preferably removed by rotary evaporation.
In the preparation method provided by the invention, after the compound with the structure of the formula (II) is obtained, the compound with the structure of the formula (II) and hydrogen react in a solvent in the presence of a catalyst. Wherein, the catalyst preferably comprises one or more of palladium carbon, platinum black, platinum carbon, nickel/alumina, ultrafine nickel, raney cobalt and raney copper, and more preferably palladium carbon, platinum carbon and raney nickel; the mass ratio of the compound of the structure of formula (II) to the catalyst is preferably 1: (0.01 to 0.35), more preferably 1: (0.05-0.17), specifically 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, 1:0.1, 1:0.11, 1:0.12, 1:0.13, 1:0.14, 1:0.15, 1:0.16 or 1: 0.17; the solvent preferably comprises one or more of methanol, toluene, chloroform, o-xylene and m-xylene, more preferably methanol or toluene; the mass ratio of the compound with the structure of the formula (II) to the solvent is preferably 1: (3-20), more preferably 1: (3-13), most preferably 1: (6-10), specifically 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5 or 1: 10; the reaction temperature is preferably 60-100 ℃, more preferably 80-90 ℃, and specifically can be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃; the pressure of the reaction is preferably 0.5 to 2MPa, more preferably 0.8 to 1.3MPa, and specifically may be 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa or 2 MPa; the reaction time is preferably 3-10 h, more preferably 5-7 h, and specifically can be 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10 h. After the reaction is finished, the obtained reaction product is subjected to post-treatment to obtain norbornane dimethylamine. In the present invention, the post-processing specifically includes: filtering the reaction product to obtain a filtrate; then, the solvent in the filtrate was removed to obtain norbornanedimethylamine. The solvent is preferably removed by rotary evaporation.
The preparation method provided by the invention does not need hydrogen cyanide and expensive catalyst, and has the advantages of high safety, good economy, simple process route, high product yield and very wide market prospect.
For the sake of clarity, the preparation process provided by the present invention is described in detail below with reference to fig. 1 and the following examples, and fig. 1 is a synthesis scheme of norbornanediamine provided by the examples of the present invention.
Example 1
Weighing 4.605g of norbornadiene into a 100mL single-neck flask, adding 4.5g of paraformaldehyde (with the polymerization degree of 10-100), adding 1.842g of hydrochloric acid with the concentration of 36.5 wt%, adding 13.1g of ammonium chloride, adding 46.05g of toluene, starting reaction at an oil bath T-60 ℃ for 10 hours, adjusting a reaction system to be neutral by using a saturated sodium carbonate solution after the reaction is finished, filtering to obtain filtrate containing norbornene dimethylamine after the adjustment is finished, layering the filtrate in a separating funnel to obtain an organic phase, and performing rotary evaporation on the organic phase to remove the solvent to obtain 7.12g of norbornene dimethylamine; the above procedure was repeated to obtain 14.25g of norbornene dimethylamine (purity 95%).
7.61g of the norbornene dimethylamine obtained above was weighed in a 100mL autoclave, 1.14g of platinum carbon (platinum content: 3 to 20 wt%) was added thereto, 60.9g of toluene was added thereto, then, the pressure was increased to 0.7MPa with hydrogen gas and maintained during the reaction, the temperature was raised to 95 ℃ to react for 10 hours, after the reaction was completed, the reaction system was filtered, and the solvent was removed by rotary evaporation from the filtrate to obtain 7.26g of norbornanediamine (purity: 96%).
The structure of the obtained norbornanedimethylamine was characterized, and the results are shown in fig. 2, and fig. 2 is a nuclear magnetic hydrogen spectrum of norbornanedimethylamine provided in example 1.
Example 2
Weighing 9.21g of norbornadiene into a 250mL single-neck flask, adding 9.1g of paraformaldehyde (with the polymerization degree of 10-100), adding 4.61g of sulfuric acid with the concentration of 98 wt%, adding 41.45g of ammonium sulfate, adding 73.68g of methanol, starting to react for 8 hours at 50 ℃ in an oil bath T, adjusting the reaction system to be neutral by using a saturated sodium bicarbonate solution after the reaction is finished, filtering to obtain a filtrate containing norbornene dimethylamine after the adjustment is finished, layering the filtrate in a separating funnel to obtain an organic phase, and performing rotary evaporation on the organic phase to remove the solvent to obtain 14.72g of norbornene dimethylamine; the above procedure was repeated to obtain a total of 29.44g of norbornene dimethylamine (purity 95.4%).
15.22g of the norbornene dimethylamine obtained above was weighed in a 500mL autoclave, 1.82g of Raney nickel was added thereto, 106.25g of toluene was added, then, the pressure was increased to 1.0MPa with hydrogen gas while maintaining the pressure during the reaction, the temperature was raised to 90 ℃ to react for 6 hours, after the reaction was completed, the reaction system was filtered, and the solvent was removed by rotary evaporation from the filtrate to obtain 14.92g of norbornanediamine (purity: 97.1%).
Example 3
Weighing 92.1g of norbornadiene into a 1000mL single-neck flask, adding 84.1g of paraformaldehyde (with the polymerization degree of 10-100), adding 36.83g of sulfuric acid with the concentration of 98%, adding 349.93g of ammonium acetate, adding 674.18g of acetonitrile, starting to react for 8 hours at an oil bath T-60 ℃, adjusting the reaction system to be neutral by using a saturated sodium carbonate solution after the reaction is finished, filtering to obtain a filtrate containing norbornene dimethylamine after the adjustment is finished, layering the filtrate in a separating funnel to obtain an organic phase, and performing rotary evaporation on the organic phase to remove the solvent to obtain 143.15g of norbornene dimethylamine (with the purity of 94%).
75.11g of the norbornene dimethylamine obtained above was weighed in a 1000mL autoclave, 7.51g of Raney nickel was added thereto, 565.58g of methanol was added, then, the pressure was increased to 1.2MPa with hydrogen and maintained during the reaction, the temperature was raised to 90 ℃ to react for 7 hours, after the reaction was completed, the reaction system was filtered, and the solvent was removed by rotary evaporation from the filtrate to obtain 75.26g of norbornanemethylamine (purity: 95.3%).
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 dicyanonorbornane. 480.7g of the obtained crude dicyanonorbornane was bubbled at a flow rate of nitrogen gas of 500mL/min for 1 hour to degas it, and then insoluble matter was filtered. To this filtrate was added 1.9g of a sulfuric acid solution (concentration: 40 wt%), heated at 60 ℃ for 3 hours to effect acid decomposition of the catalyst, and further added 5.5g of 25% by mass sodium hydroxide, heated at 40 ℃ for 2 hours to effect neutralization, and then added 449.0g of toluene to extract dicyanonorbornane to obtain a dicyanonornane toluene solution, and the toluene was distilled off to obtain 447.6g of dicyanonornane (purity: 85%).
Then, 287.8g of the above-obtained dicyanonorbornane, 32.6g of aqueous ammonia (concentration: 25% by weight) and 7.9g of Raney 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 the catalyst Raney cobalt by filtration, 0.5g of sodium hydroxide was added to the filtrate in a mass fraction of 32%, 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 (purity: 92%).
As can be seen from comparison of the above examples and comparative examples, the production method of the present invention is simple in operation steps, readily available in raw materials, and less dangerous.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of norbornane dimethylamine comprises the following steps:
a) mixing and reacting a compound with a structure shown in a formula (I), paraformaldehyde, acid and ammonium salt in a solvent to obtain a compound with a structure shown in a formula (II);
b) and (2) reacting the compound with the structure of the formula (II) with hydrogen in a solvent in the presence of a catalyst to obtain norbornane dimethylamine.
2. The method of claim 1, wherein in step a), the acid comprises one or more of hydrobromic acid, phosphoric acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid and trifluoroacetic acid;
the mass ratio of the compound with the structure shown in the formula (I) to the acid is 1: (0.2-5).
3. The method of claim 1, wherein in step a), the ammonium salt comprises one or more of ammonium chloride, ammonium bromide, ammonium acetate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, tetrabutylammonium chloride, tetrabutylammonium bromide, ammonium fluoride, ammonium iodide, ammonium sulfate, and ammonium bisulfate;
the mass ratio of the compound with the structure shown in the formula (I) to the ammonium salt is 1: (1-5).
4. The method according to claim 1, wherein in step a), the mass ratio of the compound having a structure represented by formula (I) to paraformaldehyde is 1: (0.65-5).
5. The method according to claim 1, wherein in step a), the solvent comprises one or more of acrylonitrile, acetonitrile, propionitrile, acetone, methyl ethyl ketone, toluene, ethyl acetate, cyclohexanone, and diethyl ether;
the mass ratio of the compound with the structure shown in the formula (I) to the solvent is 1: (3-15).
6. The preparation method according to claim 1, wherein in the step a), the temperature of the mixing reaction is 30-70 ℃; the mixing reaction time is 4-12 h.
7. The method of claim 1, wherein in step b), the catalyst comprises one or more of palladium carbon, platinum black, platinum carbon, nickel/alumina, ultra-fine nickel, raney cobalt and raney copper;
the mass ratio of the compound with the structure of the formula (II) to the catalyst is 1: (0.01-0.35).
8. The method according to claim 1, wherein in step b), the solvent comprises one or more of methanol, toluene, chloroform, o-xylene and m-xylene;
the mass ratio of the compound with the structure of the formula (II) to the solvent is 1: (3-20).
9. The preparation method according to claim 1, wherein in the step b), the reaction temperature is 60-100 ℃; the reaction pressure is 0.5-2 MPa.
10. The preparation method according to claim 9, wherein the reaction time in step b) is 3-10 h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104781228A (en) * | 2012-11-09 | 2015-07-15 | 三井化学株式会社 | Method for producing aldehyde compound |
| CN111004132A (en) * | 2019-12-18 | 2020-04-14 | 山东益丰生化环保股份有限公司 | Preparation method of norbornane dimethylamine |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104781228A (en) * | 2012-11-09 | 2015-07-15 | 三井化学株式会社 | Method for producing aldehyde compound |
| CN111004132A (en) * | 2019-12-18 | 2020-04-14 | 山东益丰生化环保股份有限公司 | Preparation method of norbornane dimethylamine |
Non-Patent Citations (2)
| Title |
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| 任特生: "《硝胺及硝酸酯炸药化学与工艺学》", 31 January 1994 * |
| 徐元贞等: "《新全实用药物手册》", 31 August 2021, 河南科学技术出版社 * |
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Application publication date: 20210122 |