CN114805083B - Microwave-assisted method for rapidly synthesizing N-1-naphthyl ethylenediamine hydrochloride - Google Patents
Microwave-assisted method for rapidly synthesizing N-1-naphthyl ethylenediamine hydrochloride Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 64
- WZRRZVUZWWMSKH-UHFFFAOYSA-N n'-naphthalen-1-ylethane-1,2-diamine;hydrochloride Chemical compound Cl.C1=CC=C2C(NCCN)=CC=CC2=C1 WZRRZVUZWWMSKH-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 230000002194 synthesizing effect Effects 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- HCFPRFJJTHMING-UHFFFAOYSA-N ethane-1,2-diamine;hydron;chloride Chemical compound [Cl-].NCC[NH3+] HCFPRFJJTHMING-UHFFFAOYSA-N 0.000 claims abstract description 33
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000005507 spraying Methods 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000003809 water extraction Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000005580 one pot reaction Methods 0.000 abstract description 5
- 239000013067 intermediate product Substances 0.000 abstract description 4
- 230000005855 radiation Effects 0.000 abstract description 4
- 239000007921 spray Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 17
- 239000002994 raw material Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 230000009471 action Effects 0.000 description 6
- 239000003595 mist Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- -1 N-1-naphthyl ethylenediamine hydrochloride compound Chemical class 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229940116318 copper carbonate Drugs 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229950000244 sulfanilic acid Drugs 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZCUQOPGIJRGJDA-UHFFFAOYSA-N 1-naphthalen-1-ylethane-1,2-diamine Chemical compound C1=CC=C2C(C(N)CN)=CC=CC2=C1 ZCUQOPGIJRGJDA-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YKLFSQROPDRLQF-UHFFFAOYSA-N NCCN.C1=CC=CC2=CC=CC=C21 Chemical compound NCCN.C1=CC=CC2=CC=CC=C21 YKLFSQROPDRLQF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RLBIQVVOMOPOHC-UHFFFAOYSA-N parathion-methyl Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C=C1 RLBIQVVOMOPOHC-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for rapidly synthesizing N-1-naphthyl ethylenediamine hydrochloride by a microwave-assisted one-pot method. The method adopts a self-made atomizer to spray the liquid 1-chloronaphthalene onto the surface of ethylenediamine hydrochloride solid, so that the liquid 1-chloronaphthalene fully contacts and reacts under microwave radiation, and the method adopts a one-pot method for synthesis, does not produce intermediate products, and has the characteristics of simple reaction equipment, easy operation, high yield and the like. The whole process does not add any catalyst, and has the advantages of green and pollution-free.
Description
Technical Field
The invention relates to the technical field of preparation and purification of organic compounds, in particular to a method for rapidly synthesizing N-1-naphthyl ethylenediamine hydrochloride by a microwave-assisted one-pot method.
Background
N-1-naphthylethylenediamine hydrochloride having formula C 12 H 14 N 2 HCl, molecular weight 222.5, density 1.36g/cm 3 It is generally colorless and crystalline, with a melting point of 188-190 ℃, a boiling point of 370.7 ℃ at 760mmHg, a flash point of 209.7 ℃, and is soluble in hot water, ethanol and dilute hydrochloric acid, and slightly soluble in cold water, acetone and absolute ethanol.
As a detection reagent, N-1-naphthylethylenediamine hydrochloride is widely used in various fields such as environment, medicine, food and the like.
In the environmental field, N-1-naphthylethylThe diamine hydrochloride can be used as an environment-friendly detection reagent for detecting nitrogen oxides, aniline and methyl parathion in air and waste gas, nitrate and nitrite in precipitation, and also can be used for detecting nitrate nitrogen and nitrite nitrogen in water and waste water, and anilines and nitrobenzene compounds. The nitrogen oxides in the atmosphere are mainly a mixture of nitrogen monoxide and nitrogen dioxide. N-1-naphthyl ethylenediamine hydrochloride spectrophotometry is used for monitoring nitrogen oxides in the atmosphere, and the nitrogen oxides in the atmosphere are oxidized into NO through a chromium trioxide oxidation tube 2 Then, the solution absorbs the resulting nitrous acid and nitric acid. The nitrous acid is diazotized with sulfanilic acid in the absorption liquid, and then coupled with N-1-naphthyl ethylenediamine hydrochloride in the absorption liquid to generate rose-red product. And then analyzing the concentration of nitrogen oxides in the atmosphere according to the principle of color shade and colorimetric quantification.
In the field of foods, N-1-naphthylethylenediamine hydrochloride can detect the content of nitrite in foods. The mechanism is that nitrite and sulfanilic acid are diazotized under weak acid condition, and then N-1-naphthyl ethylenediamine hydrochloride is coupled to form purplish red dye, which is compared with standard and quantified. In the field of medicine, N-1-naphthylethylenediamine hydrochloride can be used as a reagent for measuring sulfonamides.
Currently, there are few reports in the prior art on the synthesis of N-1-naphthylethylenediamine hydrochloride. Yan Rulian, zhenggong and He Jin in the paper synthesis of N-1-naphthylethylenediamine hydrochloride, a synthesis method of N-1-naphthylethylenediamine hydrochloride is described, which uses bromonaphthalene and ethylenediamine as raw materials, and copper catalyst as auxiliary material to prepare naphthylethylenediamine hydrochloride. Patent CN101397257 and patent CN102173996 also respectively disclose a synthesis method of N-1-naphthyl ethylenediamine hydrochloride, wherein bromonaphthalene and ethylenediamine are subjected to alkylation reaction under the action of a copper-copper oxide catalyst (the former is basic copper carbonate), naphthalene ethylenediamine is generated, benzene, ethanol and other organic solvents are used for purifying reaction products, and the purified products are dissolved in hydrochloric acid, so that N-1-naphthyl ethylenediamine hydrochloride is generated. The synthesis method can synthesize the target product by two steps of reactions, generates intermediate products, and has more operation steps and is complicated. In addition, the reaction time is longer, and the reaction period is longer. And the catalyst copper-copper oxide or basic copper carbonate used in the reaction is high in price and high in cost. In addition, the reaction raw material ethylenediamine is inflammable, has the danger of causing combustion explosion when contacting with open fire, high heat or oxidizing agent, has strong corrosiveness and strong irritation, and can cause burn of human body, so that the operation is dangerous, and is not suitable for industrial production.
Therefore, how to research and design a synthetic method of N-1-naphthyl ethylenediamine hydrochloride, so that the preparation of N-1-naphthyl ethylenediamine hydrochloride can be completed quickly, conveniently, efficiently, environmentally-friendly and at low cost, and the method is necessary for reducing the production cost of N-1-naphthyl ethylenediamine hydrochloride and expanding the application range of N-1-naphthyl ethylenediamine hydrochloride.
Disclosure of Invention
The technical purpose of the invention is as follows: under the condition of no catalyst and reaction solvent, 1-chloronaphthalene and ethylenediamine hydrochloride are used as raw materials, and a microwave auxiliary reaction mode is adopted to prepare the target product N-1-naphthylethylenediamine hydrochloride in a one-step method rapidly, efficiently and high yield. The process has simple steps, is convenient to operate, does not generate any intermediate product or byproducts, thereby greatly reducing the loss of raw materials, avoiding waste and reducing the process cost.
The invention adopts the technical proposal for realizing the technical purpose that: the microwave-assisted method for rapidly synthesizing the N-1-naphthyl ethylenediamine hydrochloride comprises the following steps:
step one, according to 1: (1.2-2), respectively weighing 1-chloronaphthalene and ethylenediamine hydrochloride, then, firstly placing the weighed solid ethylenediamine hydrochloride into a reaction container, and then, adding the weighed liquid 1-chloronaphthalene to the surface of the ethylenediamine hydrochloride in a spraying manner to fully mix the two to prepare a mixed material for later use;
step two, placing the reaction vessel in a microwave reactor under the condition of sealing the reaction vessel, setting the microwave frequency to be 300-500 MHz and the rated power to be 450W, performing microwave-assisted reaction for 0.5-1 h, and naturally cooling to room temperature after the reaction is finished;
step three, performing reduced pressure distillation on the reaction product obtained in the step two to separate and recover ethylenediamine hydrochloride therein, and performing reduced pressure distillation on the residual liquid for later use;
adding hot water into the residual liquid prepared in the step III, extracting a product by adopting a hot water extraction mode, and then standing, cooling and filtering a water layer obtained after extraction to obtain filter residues, namely crude N-1-naphthylethylenediamine hydrochloride;
and step five, purifying the crude N-1-naphthyl ethylenediamine hydrochloride prepared in the step four by adopting an ethanol recrystallization mode, and drying the obtained crystal to obtain the finished product N-1-naphthyl ethylenediamine hydrochloride.
Further, in the first step, 1-chloronaphthalene is sprayed on the surface of ethylenediamine hydrochloride in the reaction vessel in a mode of atomization by an atomizer.
Further, in the first step, after 1-chloronaphthalene is added to the surface of ethylenediamine hydrochloride in a spraying manner, the uniform mixing of materials in the reaction vessel is realized in a shaking manner.
Further, in the first step, the purity of the 1-chloronaphthalene and ethylenediamine hydrochloride is not less than 99%.
Further, in the fourth step, the temperature of the hot water used is not lower than 40 ℃.
Further, in step four, the operation of hot water extraction is performed in a separating funnel.
In the fifth step, after the ethanol is recrystallized, the crystals in the ethanol are separated by suction filtration.
The invention has the beneficial effects that:
1. compared with the traditional two-step process for synthesizing the N-1-naphthyl ethylenediamine hydrochloride, the microwave-assisted method for rapidly synthesizing the N-1-naphthyl ethylenediamine hydrochloride provided by the invention has the advantages that 1-chloronaphthalene and ethylenediamine hydrochloride are used as raw materials, a target product is synthesized in one step, no intermediate product is produced in the process, no byproduct is produced, and therefore, the loss of the raw materials is greatly reduced, and the waste is avoided. More importantly, in consideration of the influence of catalyst use and recovery on the environment and the higher cost of the catalyst, the preparation process abandons the use of the catalyst based on the considerations of reducing the production cost and steps, takes 1-chloronaphthalene and ethylenediamine hydrochloride as raw materials, utilizes the characteristic that the 1-chloronaphthalene is liquid, adopts a self-made atomizer, fully contacts the liquid raw material with the solid raw material by a spraying method, and realizes the full contact and complete reaction of the liquid and the solid in the reaction material under the assistance of microwaves. Thus synthesizing the N-1-naphthyl ethylenediamine hydrochloride compound with high efficiency and high yield. The method is simple and easy to operate, can fully complete the reaction without adding any solvent, has good practicability and has good industrial application prospect.
2. Compared with the synthesis method in the prior art, the method for rapidly synthesizing the N-1-naphthyl ethylenediamine hydrochloride by microwave assistance has the advantages of simple process, environmental protection, safety, strong operability, high yield of target products and the like. More important is: the method adopts a microwave radiation auxiliary reaction mode in the synthesis process, microwaves with specific frequency and power realize an efficient internal core 'body heating' effect by coupling microwave energy of the microwaves to molecules of reaction materials, so that the temperature of a reaction solution is uniformly increased, the basic reaction and bonding between raw materials are quicker, more sufficient and more thorough, and the conversion rate of a target product is higher. The test shows that the reaction rate of the process is about 10 times faster than that of the traditional method, the yield of the target compound N-1-naphthyl ethylenediamine hydrochloride can reach more than 85%, the reaction time is greatly saved, and the reaction efficiency and the purity and quality of the finished product compound are improved.
Drawings
FIG. 1 is a single crystal XRD diffraction pattern of the product obtained in example 1 of the present invention;
FIG. 2 is a single crystal diffraction XRD peak pattern of the product prepared in example 1 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the present invention will be further described with reference to specific examples and drawings, but the examples are not intended to be limiting.
The experimental methods and the detection methods described in the following examples are all conventional methods unless otherwise specified; the experimental process is carried out under normal temperature and normal pressure unless indicated; the reagents and materials are commercially available unless otherwise specified.
The method takes 1-chloronaphthalene and ethylenediamine hydrochloride as raw materials, and realizes the rapid and efficient preparation of the N-1-naphthylethylenediamine hydrochloride by means of the action of microwave-assisted acoustic radiation reaction and uniform heating. The technological method is mainly characterized by material proportion among reaction raw material substances, setting of microwave radiation frequency parameters, separation and purification modes of reaction products and the like. The specific process steps are as follows:
step one: taking 1-chloronaphthalene with purity of 99% purchased in Ala as and ethylenediamine hydrochloride as reaction raw materials, adopting a self-made atomizer, and mixing the liquid 1-chloronaphthalene with solid ethylenediamine hydrochloride in a spraying manner according to a molar ratio of 1: (1.2-2), wherein the excessive amount of ethylenediamine hydrochloride in the reaction materials is larger than that of 1-chloronaphthalene, the 1-chloronaphthalene is sprayed on the surface of ethylenediamine hydrochloride, and after spraying, the materials in the reaction vessel are uniformly mixed in a shaking mode, and the reaction vessel is transferred into a sealed reactor after full mixing, and the reaction is carried out under the assistance of microwaves.
Step two: setting the frequency of the microwave reactor to be 300-500 MHz, the rated power to be 450W, the microwave auxiliary reaction time to be 0.5-1 h, and naturally cooling to room temperature after stopping the reaction;
the reaction equation of this step is:
and step three, distilling under reduced pressure and recovering excessive ethylenediamine hydrochloride.
And step four, adding hot water into the residual liquid prepared in the step three, extracting a product by adopting a hot water extraction mode, standing, naturally cooling and carrying out suction filtration on a water layer obtained after extraction, wherein the temperature of the hot water is not lower than 40 ℃, and the obtained filter residue is crude N-1-naphthyl ethylenediamine hydrochloride.
Step five: recrystallizing the crude N-1-naphthyl ethylenediamine hydrochloride with ethanol to obtain high-purity N-1-naphthyl ethylenediamine hydrochloride.
The structural formula of the obtained target product is as follows:
the method for rapidly synthesizing the N-1-naphthyl ethylenediamine hydrochloride by the microwave-assisted one-pot method provided by the invention adopts a liquid spraying mode to react with solids under the action of microwaves, and has the advantages of simple reaction equipment, higher yield, higher speed, easiness in operation, no other byproducts, no catalyst, low cost, easiness in separation and purification and the like. The microwave auxiliary mode adopted in the process has the advantages of low cost, simple equipment, environmental protection, high reaction speed (within tens of minutes) and the like. Compared with the traditional synthesis method, the microwave technology has the advantages of simple operation, short reaction time, high efficiency, low energy consumption and the like. The method is simple and easy to operate, is convenient to operate, can generate the target product by only one-step reaction, and has good industrial application prospect.
Example 1
The microwave-assisted method for rapidly synthesizing the N-1-naphthyl ethylenediamine hydrochloride comprises the following steps:
1.60g (0.012 mol) of purchased ethylenediamine hydrochloride and 1.63g (0.01 mol) of 1-chloronaphthalene are accurately weighed, the former is put into a round-bottom flask, the latter is put into a self-made atomizer, thick mist of 1-chloronaphthalene is sprayed into the round-bottom flask at regular time, and when the mist is thick, the spraying of 1-chloronaphthalene is continued for a while intermittently until the spraying is completed. And then shaking for a few minutes until the mixture is uniformly mixed, and transferring the mixture into a sealed reactor. Setting a microwave reactor at 300MHz, starting microwave auxiliary reaction under the action of rated power 450W, stopping reaction after 1h of reaction, naturally placing and cooling. Transferring the solution into a distillation device, performing reduced pressure distillation, and distilling out ethylenediamine hydrochloride.
And transferring the residual solution to a separating funnel, adding hot water at 70 ℃ into the separating funnel, immediately and fully vibrating to fully transfer the N-1-naphthyl ethylenediamine hydrochloride into the added solvent, and then standing the separating funnel. After the liquid is layered, separating the liquid, taking a water layer and discarding an organic layer. And standing the water layer, and standing and cooling to obtain the crystalline N-1-naphthyl ethylenediamine hydrochloride. And carrying out suction filtration on the precursor solution to obtain crude N-1-naphthyl ethylenediamine hydrochloride. Dissolving the obtained crystal with ethanol, recrystallizing, precipitating, and vacuum filtering to obtain high-purity N-1-naphthyl ethylenediamine hydrochloride crystal. After drying, 2.97g of the mixture was weighed, and the yield was 89.01% based on ethylenediamine hydrochloride.
The product N-1-naphthyl ethylenediamine hydrochloride was subjected to infrared spectrum analysis, and Nicolet 170SX Fourier infrared spectrometer (KBr as tablet). The obtained infrared analysis data is upsilonmax, cm -1 : N-H stretching vibration 3462cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-H stretching vibration 3090cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-H antisymmetric telescopic vibration 2915cm -1 C-H symmetrical telescopic vibration 2843cm -1 C-H deformation and vibration 1468cm -1 The method comprises the steps of carrying out a first treatment on the surface of the 1605cm benzene ring skeleton -1 、1584cm -1 、1508cm -1 、1453cm -1 The method comprises the steps of carrying out a first treatment on the surface of the =c-N stretching vibration 1310cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-N stretching vibration 1210cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-H out-of-plane vibration 769cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-C stretching vibration 732cm -1 And after checking, the standard patterns are basically consistent with the standard patterns.
Elemental analysis was performed on the product N-1-naphthylethylenediamine hydrochloride, and a Perkin-Elmer 1400C type elemental analyzer was used. The data obtained are: c:56.01% (55.62% of theory), H:6.53% (theoretical 6.22%), N:10.52% (10.81% theoretical) Cl:26.94% (theoretical 27.35%). It is seen that the analytical values of the products are substantially identical to the theoretical values.
The target compound prepared in the embodiment is subjected to single crystal X-ray diffraction analysis and detection, a single crystal XRD spectrum is obtained, and a sample perspective view and a diffraction peak diagram are obtained through analysis by using Mercury software and are shown in figures 1 and 2.
Example 2
The microwave-assisted method for rapidly synthesizing the N-1-naphthyl ethylenediamine hydrochloride comprises the following steps:
2.00g (0.015 mol) of purchased ethylenediamine hydrochloride and 1.63g (0.01 mol) of 1-chloronaphthalene are accurately weighed, the former is put into a round-bottom flask, the latter is put into a self-made atomizer, thick mist of 1-chloronaphthalene is sprayed into the round-bottom flask at regular time, and when the mist is thick, the spraying of 1-chloronaphthalene is continued for a while intermittently until the spraying is completed. And then shaking for a few minutes until the mixture is uniformly mixed, and transferring the mixture into a sealed reactor. Setting a microwave reactor at 400MHz, starting microwave auxiliary reaction under the action of rated power 450W, stopping reaction after 0.8h, naturally placing and cooling. Transferring the solution into a distillation device, performing reduced pressure distillation, and distilling out ethylenediamine hydrochloride.
And transferring the residual solution to a separating funnel, adding hot water at 60 ℃ into the separating funnel, immediately and fully vibrating to fully transfer the N-1-naphthyl ethylenediamine hydrochloride into the added solvent, and then standing the separating funnel. After the liquid is layered, separating the liquid, taking a water layer and discarding an organic layer. And standing the water layer, and standing and cooling to obtain the crystalline N-1-naphthyl ethylenediamine hydrochloride. And carrying out suction filtration on the precursor solution to obtain crude N-1-naphthyl ethylenediamine hydrochloride. Dissolving the obtained crystal with ethanol, recrystallizing, precipitating, and vacuum filtering to obtain high-purity N-1-naphthyl ethylenediamine hydrochloride crystal. After drying, 2.94g of the mixture was weighed, and the yield was 88.04% based on ethylenediamine hydrochloride.
The product N-1-naphthyl ethylenediamine hydrochloride was subjected to infrared spectrum analysis, and Nicolet 170SX Fourier infrared spectrometer (KBr as tablet). The obtained infrared analysis data is upsilonmax, cm -1 : N-H stretching vibration 3479cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-H stretching vibration 3133cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-H antisymmetric telescopic vibration 2934cm -1 2847cm of C-H symmetrical telescopic vibration -1 C-H deformation vibration 1456cm -1 The method comprises the steps of carrying out a first treatment on the surface of the 1607cm benzene ring skeleton -1 、1589cm -1 、1503cm -1 、1458cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-N stretching vibration 1335cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-N stretching vibration 1217cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-H out-of-plane vibration 764cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-C telescopic vibration 736cm -1 And checking to be consistent with the standard map.
Elemental analysis was performed on the product N-1-naphthylethylenediamine hydrochloride, and a Perkin-Elmer 1400C type elemental analyzer was used. The data obtained are: c:55.91% (55.62% of theory), H:6.32% (theoretical 6.22%), N:10.73% (10.81% theoretical) Cl:27.04% (theoretical 27.35%). It is seen that the analytical values of the products are substantially identical to the theoretical values.
Example 3
The microwave-assisted method for rapidly synthesizing the N-1-naphthyl ethylenediamine hydrochloride comprises the following steps:
2.66g (0.020 mol) of purchased ethylenediamine hydrochloride and 1.63g (0.01 mol) of 1-chloronaphthalene are accurately weighed, the former is put into a round-bottom flask, the latter is put into a self-made atomizer, thick mist of 1-chloronaphthalene is sprayed into the round-bottom flask at regular time, and when the mist is thick, the spraying of 1-chloronaphthalene is continued for a while intermittently until the spraying is finished. And then shaking for a few minutes until the mixture is uniformly mixed, and transferring the mixture into a sealed reactor. Setting a microwave reactor at 500MHz, starting microwave auxiliary reaction under the action of rated power 450W, stopping reaction after 0.5h, naturally placing and cooling. Transferring the solution into a distillation device, performing reduced pressure distillation, and distilling out ethylenediamine hydrochloride. And transferring the residual solution to a separating funnel, adding hot water at 50 ℃ into the separating funnel, immediately and fully vibrating to fully transfer the N-1-naphthyl ethylenediamine hydrochloride into the added solvent, and then standing the separating funnel. After the liquid is layered, separating the liquid, taking a water layer and discarding an organic layer. And standing the water layer, and standing and cooling to obtain the crystalline N-1-naphthyl ethylenediamine hydrochloride. And carrying out suction filtration on the precursor solution to obtain crude N-1-naphthyl ethylenediamine hydrochloride. Dissolving the obtained crystal with ethanol, recrystallizing, precipitating, and vacuum filtering to obtain high-purity N-1-naphthyl ethylenediamine hydrochloride crystal. After drying, 2.87g was weighed, and the yield was 86.08% based on ethylenediamine hydrochloride.
The product N-1-naphthyl ethylenediamine hydrochloride was subjected to infrared spectrum analysis, and Nicolet 170SX Fourier infrared spectrometer (KBr as tablet). The obtained infrared analysis data is upsilonmax, cm -1 : N-H stretching vibration 3459cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-H stretching vibration 3102cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-H antisymmetric telescopic vibration 2923cm -1 C-H symmetrical telescopic vibration 2843cm -1 C-H deformation vibration 1456cm -1 The method comprises the steps of carrying out a first treatment on the surface of the 1613cm benzene ring skeleton -1 、1587cm -1 、1510cm -1 、1455cm -1 The method comprises the steps of carrying out a first treatment on the surface of the =c-N stretching 1296cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-N stretching vibration 1198cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-H surface outward stretching vibration 770cm -1 The method comprises the steps of carrying out a first treatment on the surface of the C-C stretching vibration 754cm -1 And checking to be consistent with the standard map.
Elemental analysis was performed on the product N-1-naphthylethylenediamine hydrochloride, and a Perkin-Elmer 1400C type elemental analyzer was used. The data obtained are: c:56.95% (55.62% of theory), H:6.13% (theoretical 6.22%), N:10.22% (10.81% of theory) Cl:26.39% (theoretical 27.35%). It is seen that the analytical values of the products are substantially identical to the theoretical values.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (7)
1. The method for microwave-assisted rapid synthesis of N-1-naphthyl ethylenediamine hydrochloride is characterized by comprising the following steps:
step one, according to 1: (1.2-2), respectively weighing 1-chloronaphthalene and ethylenediamine hydrochloride, then, firstly placing the weighed solid ethylenediamine hydrochloride into a reaction container, and then, adding the weighed liquid 1-chloronaphthalene to the surface of the ethylenediamine hydrochloride in a spraying manner to fully mix the two to prepare a mixed material for later use;
step two, placing the reaction vessel in a microwave reactor under the condition of sealing the reaction vessel, setting the microwave frequency to be 300-500 MHz and the rated power to be 450W, performing microwave-assisted reaction for 0.5-1 h, and naturally cooling to room temperature after the reaction is finished;
step three, performing reduced pressure distillation on the reaction product obtained in the step two to separate and recover ethylenediamine hydrochloride therein, and performing reduced pressure distillation on the residual liquid for later use;
adding hot water into the residual liquid prepared in the step III, extracting a product by adopting a hot water extraction mode, and then standing, cooling and filtering a water layer obtained after extraction to obtain filter residues, namely crude N-1-naphthylethylenediamine hydrochloride;
and step five, purifying the crude N-1-naphthyl ethylenediamine hydrochloride prepared in the step four by adopting an ethanol recrystallization mode, and drying the obtained crystal to obtain the finished product N-1-naphthyl ethylenediamine hydrochloride.
2. The method for microwave-assisted rapid synthesis of N-1-naphthylethylenediamine hydrochloride according to claim 1, wherein: in the first step, 1-chloronaphthalene is sprayed on the surface of ethylenediamine hydrochloride in a reaction container in an atomizer atomizing mode.
3. The method for microwave-assisted rapid synthesis of N-1-naphthylethylenediamine hydrochloride according to claim 1, wherein: in the first step, after 1-chloronaphthalene is added to the surface of ethylenediamine hydrochloride in a spraying mode, uniform mixing of materials in a reaction container is achieved in a vibration mode.
4. The method for microwave-assisted rapid synthesis of N-1-naphthylethylenediamine hydrochloride according to claim 1, wherein: in the first step, the purity of the 1-chloronaphthalene and ethylenediamine hydrochloride is not less than 99%.
5. The method for microwave-assisted rapid synthesis of N-1-naphthylethylenediamine hydrochloride according to claim 1, wherein: in the fourth step, the temperature of the hot water used is not lower than 40 ℃.
6. The method for microwave-assisted rapid synthesis of N-1-naphthylethylenediamine hydrochloride according to claim 1, wherein: in step four, the operation of hot water extraction is performed in a separating funnel.
7. The method for microwave-assisted rapid synthesis of N-1-naphthylethylenediamine hydrochloride according to claim 1, wherein: in the fifth step, after the ethanol is recrystallized, the crystals in the ethanol are separated by adopting a suction filtration mode.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531924A (en) * | 2010-12-27 | 2012-07-04 | 中国科学院化学研究所 | N-(1-naphthyl) ethylenediamine dinitrate and preparation method and application thereof |
| CN102786496A (en) * | 2012-07-13 | 2012-11-21 | 常州大学 | Microwave synthetic method of substituted piperazine compound |
| CN107548389A (en) * | 2015-05-06 | 2018-01-05 | 阿斯利康(瑞典)有限公司 | Cyclopropanecarboxylacid acid derivative and its pharmaceutical use |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531924A (en) * | 2010-12-27 | 2012-07-04 | 中国科学院化学研究所 | N-(1-naphthyl) ethylenediamine dinitrate and preparation method and application thereof |
| CN102786496A (en) * | 2012-07-13 | 2012-11-21 | 常州大学 | Microwave synthetic method of substituted piperazine compound |
| CN107548389A (en) * | 2015-05-06 | 2018-01-05 | 阿斯利康(瑞典)有限公司 | Cyclopropanecarboxylacid acid derivative and its pharmaceutical use |
Non-Patent Citations (3)
| Title |
|---|
| Novel 4-Aminoquinolines through Microwave-Assisted SNAr Reactions: a Practical Route to Antimalarial Agents;Sergio Melato等;《Eur. J. Org. Chem.》;第6118–6123页 * |
| Tacrine based human cholinesterase inhibitors: Synthesis of peptidic-tethered derivatives and their effect on potency and selectivity;Stefania Butini等;《Bioorganic & Medicinal Chemistry Letters》;第18卷;第5213-5216页 * |
| 盐酸萘乙二胺的合成;阎汝连等;《天津化工》;第31、41页 * |
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