CN117645546A - Preparation method of naphthalene ethylenediamine - Google Patents
Preparation method of naphthalene ethylenediamine Download PDFInfo
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- CN117645546A CN117645546A CN202410118577.6A CN202410118577A CN117645546A CN 117645546 A CN117645546 A CN 117645546A CN 202410118577 A CN202410118577 A CN 202410118577A CN 117645546 A CN117645546 A CN 117645546A
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- YKLFSQROPDRLQF-UHFFFAOYSA-N NCCN.C1=CC=CC2=CC=CC=C21 Chemical compound NCCN.C1=CC=CC2=CC=CC=C21 YKLFSQROPDRLQF-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000010992 reflux Methods 0.000 claims abstract description 23
- LYIIBVSRGJSHAV-UHFFFAOYSA-N 2-aminoacetaldehyde Chemical compound NCC=O LYIIBVSRGJSHAV-UHFFFAOYSA-N 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 15
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 14
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 14
- 238000004821 distillation Methods 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 14
- 229940033123 tannic acid Drugs 0.000 claims abstract description 14
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 14
- 229920002258 tannic acid Polymers 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 230000035484 reaction time Effects 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 238000005273 aeration Methods 0.000 claims description 6
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 4
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000009423 ventilation Methods 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Abstract
The invention discloses a preparation method of naphthalene ethylenediamine, which belongs to the technical field of naphthalene ethylenediamine preparation and comprises the following steps: s1, adding 1-naphthylamine, ethanol, aminoacetaldehyde and tannic acid into a reaction container, and carrying out reflux reaction; s2, distilling at normal pressure to recover ethanol; s3, stopping atmospheric distillation when the temperature of the reaction vessel reaches 90 ℃; s4, after proper cooling, adding nickel powder, and introducing hydrogen, and controlling the reaction temperature to be between 80 and 100 ℃; s5, distilling the reaction liquid under reduced pressure, and collecting fractions at 200-220 ℃ to obtain naphthalene ethylenediamine. According to the preparation method of the naphthalene ethylenediamine, the reaction is carried out at a lower temperature, so that the purity of the naphthalene ethylenediamine is further improved, and the yield is improved.
Description
Technical Field
The invention relates to a preparation method of naphthalene ethylenediamine, and belongs to the technical field of naphthalene ethylenediamine preparation.
Background
Naphthalene ethylenediamine (Naphthyl ethylenediamine): CBNumber: CB31129817; molecular formula C 12 H 14 N 2 The method comprises the steps of carrying out a first treatment on the surface of the Molecular weight 186.25296.
The preparation method of naphthalene ethylenediamine comprises the following steps:
bromonaphthalene and ethylenediamine are mixed, refluxed for 6-10 hours at the temperature of 110-130 ℃, and then cooled to 70-80 ℃; adding a copper-containing catalyst into the reactant, refluxing for 6-10 hours, and naturally cooling; distilling under reduced pressure and recovering excess ethylenediamine; extracting the reactant with an organic solvent, filtering, and distilling under reduced pressure to obtain the product naphthalene ethylenediamine.
Objective drawbacks of the prior art: the bromonaphthalene and ethylenediamine reaction belongs to Huffman alkylation reaction, which needs to be carried out under high temperature condition, and is easy to cause the decomposition of reactants and the occurrence of side reaction, and the purity and yield of the product are affected; naphthalene ethylenediamine obtained by the reaction of bromonaphthalene and ethylenediamine is easily decomposed during distillation, and once this process is produced, the yield is almost 0, and the main impurity content is several times that of naphthalene ethylenediamine.
Therefore, developing a preparation method of naphthalene ethylenediamine, which adopts a reaction at a lower temperature, further improves the purity of naphthalene ethylenediamine, and the yield can reach more than 85%, becomes a technical problem to be solved in the technical field.
Disclosure of Invention
The invention aims to provide a preparation method of naphthalene ethylenediamine, which adopts a reaction at a lower temperature to further improve the purity and the yield of naphthalene ethylenediamine.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of naphthalene ethylenediamine comprises the following steps:
s1, adding 1-naphthylamine, ethanol, aminoacetaldehyde and tannic acid into a reaction container, and carrying out reflux reaction;
s2, distilling at normal pressure to recover ethanol;
s3, stopping atmospheric distillation when the temperature of the reaction vessel reaches 90 ℃;
s4, after cooling, adding nickel powder, and introducing hydrogen, and controlling the reaction temperature to be between 80 and 100 ℃;
s5, distilling the reaction liquid under reduced pressure, and collecting fractions at 200-220 ℃ to obtain naphthalene ethylenediamine.
Preferably, in step S1, the reaction temperature is 60 ℃ to 80 ℃.
Preferably, in step S1, the ethanol is replaced by isopropanol.
Preferably, in step S1, the ethanol is replaced by methanol.
Preferably, step S4 is replaced with: and (3) adding borohydride after cooling, and controlling the reaction temperature to be between 80 and 100 ℃.
Preferably, step S4 is replaced with: after cooling, adding lithium aluminum hydride, and controlling the reaction temperature between 80 ℃ and 100 ℃.
Preferably, in step S4, the aeration reaction time is controlled to be 2-2.5 hours.
Compared with the prior art, the invention has the advantages that:
according to the preparation method of the naphthalene ethylenediamine, the reaction is carried out at a lower temperature, so that the purity of the naphthalene ethylenediamine is further improved, and the yield is improved.
The invention is described in detail below with reference to the drawings and the detailed description. It is to be understood that the examples described relate only to the preferred embodiments of the present invention and that various changes and modifications of the components and contents are possible without departing from the spirit and scope of the present invention.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a molecular structural reaction formula of the preparation method of naphthalene ethylenediamine provided by the invention.
FIG. 2 shows the Infrared (IR) spectrum of naphthalene ethylenediamine prepared in example 9 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The following examples are illustrative of the invention but are not intended to limit the scope of the invention.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the embodiments of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Unless otherwise specified, the starting materials required in the following examples are all conventional starting materials commercially available in the art, and the reaction vessel and the controlled reaction conditions used are all conventional reaction vessels and reaction conditions; the instruments required for product confirmation are all conventional instruments in the field, and the test conditions are all conventional conditions; the units are all weight units.
Example 1
A preparation method of naphthalene ethylenediamine comprises the following reaction processes:
as shown in figure 1, the molecular structure reaction formula of the preparation method of naphthalene ethylenediamine provided by the invention.
The method comprises the following specific steps:
1. 145g of 1-naphthylamine, 800g of ethanol, 65g of aminoacetaldehyde and 1g of tannic acid are added into a three-mouth bottle, stirred, heated to 79 ℃, refluxed at 78 ℃, and reacted for 7 hours at 81+/-1 ℃ after the reaction;
2. distilling at normal pressure to recover ethanol;
3. stopping atmospheric distillation when the temperature in the three-mouth bottle reaches 90 ℃;
4. adding 0.5g of nickel powder, introducing hydrogen, controlling the aeration reaction time to be 2 hours, and controlling the reaction temperature to be 90 ℃;
5. the reaction solution was distilled under reduced pressure, and a fraction at 200℃to 220℃was collected to obtain 159 g of naphthalene ethylenediamine, the content of which was 94.64%, and the yield was 85.20%.
The liquid chromatography detection is adopted, and the specific operation is as follows:
the detection method of naphthalene ethylenediamine comprises the following steps:
chromatographic column: c (C) 18 ；
Mobile phase: 0.1% triethylamine (ph=6.5): acetonitrile=23:77;
detection wavelength: 220nm;
column temperature: 30 ℃;
flow rate: 1.0ml/min.
The invention adopts the reaction of 1-naphthylamine and aminoacetaldehyde, and has low reaction temperature and less byproducts.
Example 2
A preparation method of naphthalene ethylenediamine comprises the following preparation steps:
1. 145g of 1-naphthylamine, 800g of ethanol, 55g of aminoacetaldehyde and 1g of tannic acid are added into a three-mouth bottle, stirring is carried out, the temperature is raised to 79 ℃, reflux is generated when the temperature is 78 ℃, and when the reaction is finished, the temperature is controlled to 81+/-1 ℃, and the reflux reaction is carried out for 7 hours;
2. distilling at normal pressure to recover ethanol;
3. stopping atmospheric distillation when the temperature in the three-mouth bottle reaches 90 ℃;
4. adding 0.5g of nickel powder, introducing hydrogen, controlling the aeration reaction time to be 2 hours, and controlling the reaction temperature to be 90 ℃;
5. the reaction solution is distilled under reduced pressure, and fractions with the temperature of 200 ℃ to 220 ℃ are collected to obtain 135.8 g of naphthalene ethylenediamine with the content of 90.35 percent and the yield of 72.80 percent.
Example 3
A preparation method of naphthalene ethylenediamine comprises the following preparation steps:
1. 145g of 1-naphthylamine, 800g of ethanol, 60g of aminoacetaldehyde and 1g of tannic acid are added into a three-mouth bottle, stirring is carried out, the temperature is raised to 79 ℃, reflux is generated when the temperature is 78 ℃, and when the reaction is finished, the temperature is controlled to 81+/-1 ℃, and the reflux reaction is carried out for 7 hours;
2. distilling at normal pressure to recover ethanol;
3. stopping atmospheric distillation when the temperature in the three-mouth bottle reaches 90 ℃;
4. adding 0.5g of nickel powder, introducing hydrogen, controlling the aeration reaction time to be 2 hours, and controlling the reaction temperature to be 90 ℃;
5. the reaction solution is distilled under reduced pressure, and fractions with the temperature of 200 ℃ to 220 ℃ are collected to obtain 162.3 g of naphthalene ethylenediamine with the content of 98.76 percent and the yield of 86.95 percent.
Example 4
A preparation method of naphthalene ethylenediamine comprises the following preparation steps:
1. 145g of 1-naphthylamine, 800g of ethanol, 63g of aminoacetaldehyde and 1g of tannic acid are added into a three-mouth bottle, stirring is carried out, the temperature is raised to 79 ℃, reflux is generated when the temperature is 78 ℃, and when the reaction is finished, the temperature is controlled to 81+/-1 ℃, and the reflux reaction is carried out for 7 hours;
2. distilling at normal pressure to recover ethanol;
3. stopping atmospheric distillation when the temperature in the three-mouth bottle reaches 90 ℃;
4. adding 0.5g of nickel powder, introducing hydrogen, controlling the aeration reaction time to be 2 hours, and controlling the reaction temperature to be 90 ℃;
5. the reaction solution is distilled under reduced pressure, and fractions with the temperature of 200-220 ℃ are collected to obtain 160.2 g of naphthalene ethylenediamine with the content of 97.23 percent and the yield of 85.82 percent.
Example 5
A preparation method of naphthalene ethylenediamine comprises the following preparation steps:
1. 145g of 1-naphthylamine, 800g of ethanol, 60g of aminoacetaldehyde and 1g of tannic acid are added into a three-mouth bottle, stirring is carried out, the temperature is raised to 79 ℃, reflux is generated when the temperature is 78 ℃, and when the reaction is finished, the temperature is controlled to 81+/-1 ℃, and the reflux reaction is carried out for 7 hours;
2. distilling at normal pressure to recover ethanol;
3. stopping atmospheric distillation when the temperature in the three-mouth bottle reaches 90 ℃;
4. after properly cooling to 80 ℃, adding 0.5g of nickel powder, introducing hydrogen, controlling the ventilation reaction time to be 2.5 hours, and controlling the reaction temperature to be 80 ℃;
5. the reaction solution is distilled under reduced pressure, and fractions with the temperature of 200 ℃ to 220 ℃ are collected to obtain 164.5 g of naphthalene ethylenediamine with the content of 98.84 percent and the yield of 88.13 percent.
Example 6
A preparation method of naphthalene ethylenediamine comprises the following preparation steps:
1. 145g of 1-naphthylamine, 800g of ethanol, 60g of aminoacetaldehyde and 1g of tannic acid are added into a three-mouth bottle, stirring is carried out, the temperature is raised to 79 ℃, reflux is generated when the temperature is 78 ℃, and when the reaction is finished, the temperature is controlled to 81+/-1 ℃, and the reflux reaction is carried out for 8 hours;
2. distilling at normal pressure to recover ethanol;
3. stopping atmospheric distillation when the temperature in the three-mouth bottle reaches 90 ℃;
4. after properly cooling to 85 ℃, adding 0.5g of nickel powder, introducing hydrogen, controlling the ventilation reaction time to be 2.5 hours, and controlling the reaction temperature to be 85 ℃;
5. the reaction solution is distilled under reduced pressure, and fractions with the temperature of 200 ℃ to 220 ℃ are collected to obtain 164.9 g of naphthalene ethylenediamine with the content of 98.53 percent and the yield of 88.34 percent.
Example 7
A preparation method of naphthalene ethylenediamine comprises the following preparation steps:
1. 145g of 1-naphthylamine, 800g of ethanol, 60g of aminoacetaldehyde and 1g of tannic acid are added into a three-mouth bottle, stirring is carried out, the temperature is raised to 79 ℃, reflux is generated when the temperature is 78 ℃, and when the reaction is finished, the temperature is controlled to 81+/-1 ℃, and the reflux reaction is carried out for 6 hours;
2. distilling at normal pressure to recover ethanol;
3. stopping atmospheric distillation when the temperature in the three-mouth bottle reaches 90 ℃;
4. after properly cooling to 75 ℃, adding 0.5g of nickel powder, introducing hydrogen, controlling the ventilation reaction time to be 2 hours, and controlling the reaction temperature to be 75 ℃;
5. the reaction solution was distilled under reduced pressure, and a fraction at 200℃to 220℃was collected to give 163.2 g of naphthalene ethylenediamine, content 95.36%, yield 84.76%.
Example 8
A preparation method of naphthalene ethylenediamine comprises the following preparation steps:
1. 145g of 1-naphthylamine, 800g of ethanol, 60g of aminoacetaldehyde and 1g of tannic acid are added into a three-mouth bottle, stirring is carried out, the temperature is raised to 79 ℃, reflux is generated when the temperature is 78 ℃, and when the reaction is finished, the temperature is controlled to 81+/-1 ℃, and the reflux reaction is carried out for 7 hours;
2. distilling at normal pressure to recover ethanol;
3. stopping atmospheric distillation when the temperature in the three-mouth bottle reaches 90 ℃;
4. after heating to 95 ℃, adding 0.5g of nickel powder, introducing hydrogen, controlling the ventilation reaction time to be 2.5 hours, and controlling the reaction temperature to be 95 ℃;
5. the reaction solution was distilled under reduced pressure, and a fraction at 200℃to 220℃was collected to obtain 164.1 g of naphthalene ethylenediamine, 98.43% in yield 87.91%.
Example 9
A preparation method of naphthalene ethylenediamine comprises the following preparation steps:
1. 145g of 1-naphthylamine, 800g of ethanol, 60g of aminoacetaldehyde and 1g of tannic acid are added into a three-mouth bottle, stirring is carried out, the temperature is raised to 79 ℃, reflux is generated when the temperature is 78 ℃, and when the reaction is finished, the temperature is controlled to 81+/-1 ℃, and the reflux reaction is carried out for 8 hours;
2. distilling at normal pressure to recover ethanol;
3. stopping atmospheric distillation when the temperature in the three-mouth bottle reaches 90 ℃;
4. after heating to 100 ℃, adding 0.5g of nickel powder, introducing hydrogen, controlling the ventilation reaction time to be 2 hours, and controlling the reaction temperature to be 100 ℃;
5. the reaction solution was distilled under reduced pressure, and a fraction at 200℃to 220℃was collected to obtain 163.5 g of naphthalene ethylenediamine, a content of 98.29%, and a yield of 87.59%.
Product confirmation:
the product prepared in this example 9 was confirmed, including liquid chromatography, infrared spectroscopy, and nuclear magnetic resonance analysis;
the liquid chromatography detection result of the naphthalene ethylenediamine prepared in the embodiment 9 of the invention shows that the retention time is 7.059 and the content is 98.29%; as shown in FIG. 2, the infrared spectrum (IR) results of naphthalene ethylenediamine prepared in example 9 of the present invention are shown; by nuclear magnetic resonance analysis, the finally obtained product is naphthalene ethylenediamine, and specific data are as follows: 1 HNMR:δ2.75(2H,t,J=6.7Hz), 3.21(2H,t,J=6.7Hz),7.12-7.54(5H,7.19(ddd,J=8.1,1.5,0.5Hz),7.24(ddd, J=8.2,7.1,1.4Hz),7.35(dddd,J=8.0,7.1,1.6,0.5Hz),7.35(ddd,J=8.1,7.8,0.5Hz), 7.47(ddq,J=8.2,1.6,0.5Hz)),7.63-7.77(2H,7.70(dddt,J=7.8,2.8,1.5,0.5Hz), 7.70(dddt,J=8.0,2.8,1.4,0.5Hz) )。
example 10
A preparation method of naphthalene ethylenediamine comprises the following preparation steps:
1. 145g of 1-naphthylamine, 800g of ethanol, 60g of aminoacetaldehyde and 1g of tannic acid are added into a three-mouth bottle, stirring is carried out, the temperature is raised to 79 ℃, reflux is generated when the temperature is 78 ℃, and when the reaction is finished, the temperature is controlled to 81+/-1 ℃, and the reflux reaction is carried out for 7 hours;
2. distilling at normal pressure to recover ethanol;
3. stopping atmospheric distillation when the temperature in the three-mouth bottle reaches 90 ℃;
4. after properly cooling to 80 ℃, adding 0.5g of nickel powder, introducing hydrogen, controlling the ventilation reaction time to be 2.5 hours, and controlling the reaction temperature to be 80 ℃;
5. the reaction solution is distilled under reduced pressure, and fractions with the temperature of 200 ℃ to 220 ℃ are collected to obtain 164.6 g of naphthalene ethylenediamine with the content of 98.25 percent and the yield of 88.18 percent.
Product confirmation:
the product prepared in this example 10 was analyzed by liquid chromatography, and the retention time was 7.319 and the content was 98.25%.
Ethanol in the present invention may be replaced with isopropanol or methanol: isopropanol is more expensive than ethanol, and temperature change is also required to be concerned in the reaction; compared with ethanol, the methanol has low price, but the reaction temperature is low, the time for completing the reaction is much longer, the solvent can be recycled, and the ethanol has obvious advantages; nickel hydrogen reduction may be replaced by reduction using borohydride, lithium aluminum hydride, or the like (but at a higher cost).
The invention has the beneficial effects that:
the preparation method of naphthalene ethylenediamine adopts 1-naphthylamine and aminoacetaldehyde as raw materials for reaction, tannic acid is used as a catalyst, hydrogenation reduction is carried out after the reaction is finished, the reaction temperature is controlled at 80-100 ℃, and the reflux reaction time is not less than 6 hours; the invention adopts the reaction of 1-naphthylamine and aminoacetaldehyde, the reaction temperature is low, the byproducts are few, and the yield is further improved.
Although the claimed subject matter has been described in language specific to structural features and/or methodological acts, it is to be understood that the claimed subject matter is not limited to the specific features or acts described in the claims. Rather, the specific structural features and methods described in the claims are merely examples of the invention.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A preparation method of naphthalene ethylenediamine comprises the following steps:
s1, adding 1-naphthylamine, ethanol, aminoacetaldehyde and tannic acid into a reaction container, and carrying out reflux reaction;
s2, distilling at normal pressure to recover ethanol;
s3, stopping atmospheric distillation when the temperature of the reaction vessel reaches 90 ℃;
s4, after cooling, adding nickel powder, and introducing hydrogen, and controlling the reaction temperature to be between 80 and 100 ℃;
s5, distilling the reaction liquid under reduced pressure, and collecting fractions at 200-220 ℃ to obtain naphthalene ethylenediamine.
2. The process for producing naphthalene ethylenediamine as claimed in claim 1, wherein in the step S1, the reaction temperature is 60 ℃ to 80 ℃.
3. The process for producing naphthalene ethylenediamine as claimed in claim 1, wherein in the step S1, the ethanol is replaced with isopropyl alcohol.
4. The process for producing naphthalene ethylenediamine as claimed in claim 1, wherein in the step S1, the ethanol is replaced with methanol.
5. The process for the preparation of naphthalene ethylenediamine as claimed in claim 1, wherein step S4 is replaced by:
and (3) adding borohydride after cooling, and controlling the reaction temperature to be between 80 and 100 ℃.
6. The process for the preparation of naphthalene ethylenediamine as claimed in claim 1, wherein step S4 is replaced by:
after cooling, adding lithium aluminum hydride, and controlling the reaction temperature between 80 ℃ and 100 ℃.
7. The process for producing naphthalene ethylenediamine as claimed in claim 1, wherein in the step S4, the aeration reaction time is controlled to 2 to 2.5 hours.
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Non-Patent Citations (2)
| Title |
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| HUY H.NGUYEN ET AL: ""Microwave-Assisted Synthesis of 3-Nitroindoles from N-Aryl Enamines via Intramolecular Arene-Alkene Coupling"", 《ORGANIC LETTERS》, vol. 15, no. 2, 28 February 2013 (2013-02-28), pages 364 * |
| VANIA H.J.FRADE ET AL: ""Synthesis of short and long-wavelength functionalized probes:amino acids labeling and photophysical studies"", 《TETRAHEDRON》, vol. 63, 23 September 2007 (2007-09-23), pages 12408 * |
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