CN117210833A - Method for preparing 3-benzylamino-2-butenenitrile - Google Patents
Method for preparing 3-benzylamino-2-butenenitrile Download PDFInfo
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- CN117210833A CN117210833A CN202311319533.1A CN202311319533A CN117210833A CN 117210833 A CN117210833 A CN 117210833A CN 202311319533 A CN202311319533 A CN 202311319533A CN 117210833 A CN117210833 A CN 117210833A
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- butenenitrile
- benzylamino
- electrolysis
- benzylamine
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- BYRVBQQUFLOHRK-UHFFFAOYSA-N 3-(benzylamino)but-2-enenitrile Chemical compound N#CC=C(C)NCC1=CC=CC=C1 BYRVBQQUFLOHRK-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 99
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 92
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 51
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 45
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 19
- 238000005341 cation exchange Methods 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 14
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 28
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 claims description 3
- -1 tetraethylammonium tetrafluoroborate Chemical compound 0.000 claims description 3
- WGHUNMFFLAMBJD-UHFFFAOYSA-M tetraethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-M 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 description 65
- 238000012360 testing method Methods 0.000 description 63
- 238000002360 preparation method Methods 0.000 description 31
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- 238000004949 mass spectrometry Methods 0.000 description 17
- 238000001514 detection method Methods 0.000 description 16
- 238000004128 high performance liquid chromatography Methods 0.000 description 16
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 15
- 238000002329 infrared spectrum Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010626 work up procedure Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZJRCIQAMTAINCB-UHFFFAOYSA-N benzoylacetonitrile Chemical compound N#CCC(=O)C1=CC=CC=C1 ZJRCIQAMTAINCB-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical class N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- DELJOESCKJGFML-DUXPYHPUSA-N (e)-3-aminobut-2-enenitrile Chemical compound C\C(N)=C/C#N DELJOESCKJGFML-DUXPYHPUSA-N 0.000 description 1
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical class C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 description 1
- 239000010963 304 stainless steel Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 3-benzylamino-2-butenenitrile, which comprises the following steps: the cation exchange membrane isolates an anode chamber and a cathode chamber of the electrolytic cell, and a graphite electrode is used as an anode, and a metal electrode is used as a cathode; the anolyte is acetonitrile solution of 0.1-1.0 mol/L quaternary ammonium salt; the catholyte is acetonitrile solution of quaternary ammonium salt and benzylamine, wherein the concentration of the quaternary ammonium salt is 0.05-0.5 mol/L, and the concentration of the benzylamine is 0.05-0.5 mol/L; introducing N into the cathode chamber at 0-35 DEG C 2 To saturation of 12-18 mA/cm 2 Constant current density electrolysis of (2); the electrifying amount of the benzylamine is 1.0-2.5F per mole; removing acetonitrile by rotary evaporation of liquid in a cathode chamber under reduced pressure after electrolysis; adding 0.5-1 times volume of saturated sodium bicarbonate solution, adding diethyl ether for extraction, drying, filtering, and removing diethyl ether from the filtrate to obtain 3-benzylamino-2-butenenitrile. The method is simple, economical and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing 3-benzylamino-2-butenenitrile.
Background
Beta-aminonitriles include 3-amino-2-butenenitrile and N-substituted derivatives thereof. Beta-aminonitriles have very good reactivity and are widely used as important synthons for the synthesis of various heterocyclic compounds, in particular nitrogen-containing heterocycles. Such as: and (3) synthesizing heterocyclic compounds such as substituted pyridine, dihydropyridine, quinoline and the like. At present, the preparation of beta-aminonitrile mainly comprises the following two methods:
1) Acetonitrile dimerization under the action of metallic sodium
Early days, dimerization of acetonitrile using sodium in an organic solvent was the most common method for synthesizing β -aminonitrile. By this route, a quantifiable yield of β -aminocrotonenitrile can be obtained, but a highly toxic material NaCN is produced in the reaction.
2) Reaction of benzoylacetonitrile with an amine
In 2008, malkov et al reported that β -enamine nitrile was prepared by stirring and reacting benzoylacetonitrile, aniline and acetic acid for 6h under argon protection in an oil bath at 80 ℃ (Malkov, a.v. chem. Eur. J.2008,14, 8082-8085). Wherein, the benzoyl acetonitrile is prepared by reacting ethyl benzoate with acetonitrile. The method is carried out in two steps, and the operation is complex.
Disclosure of Invention
The purpose of the invention is as follows: a process for producing 3-benzylamino-2-butenenitrile is provided which is free from the formation of cyanide by-products and which is simple to operate.
The technical scheme of the invention is as follows:
a process for preparing 3-benzylamino-2-butenenitrile comprising the steps of:
step one, preparing electrolysis:
isolating an anode chamber and a cathode chamber of the electrolytic cell by using a cation exchange membrane; graphite electrode is used as anode, and metal electrode is used as cathode; the anolyte is acetonitrile solution of 0.1-1.0 mol/L quaternary ammonium salt; the catholyte is acetonitrile solution of quaternary ammonium salt and benzylamine, wherein the concentration of the quaternary ammonium salt is 0.05-0.5 mol/L, and the concentration of the benzylamine is 0.05-0.5 mol/L; the ratio of the amounts of the substances of the quaternary ammonium salt in the catholyte and the anodic electrolyte is 1:2;
step two, electrolysis:
introducing N into the cathode chamber at normal pressure and at a temperature of between 0 and 35 DEG C 2 To saturation of 12-18 mA/cm 2 Electrolysis is carried out at constant current density; the electrifying capacity of each mole of benzylamine is 1.0-2.5F, and F is Faraday constant;
step three, post-treatment:
taking out the liquid in the cathode chamber after the electrolysis is finished, and removing acetonitrile by reduced pressure rotary evaporation; adding saturated sodium bicarbonate solution, wherein the addition amount is 0.5-1 times of the volume of the liquid taken out from the cathode chamber; and then adding diethyl ether for extraction, adding anhydrous magnesium sulfate into the obtained ether layer liquid for drying, filtering, and performing secondary rotary evaporation on the filtrate to remove diethyl ether, thus obtaining the 3-benzylamino-2-butenenitrile.
Preferably, the quaternary ammonium salt is one of tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium tetrafluoroborate, tetra-n-butyl ammonium iodide and tetraethylammonium perchlorate.
Preferably, the cation exchange membrane is an FKS-50 cation exchange membrane.
Preferably, the cathode is made of copper, nickel, titanium, stainless steel, platinum or silver.
Preferably, the constant current density in the second step is 13.5mA/cm 2 。
Preferably, the temperature of the electrolysis in the second step is 15 ℃.
Preferably, the energization amount per mole of benzylamine in the second step is 2.2F.
Preferably, the ratio of the amounts of the substances of the quaternary ammonium salt in the catholyte and the anolyte in the step one is 1:2.
the beneficial effects of the invention are as follows:
the method for preparing 3-benzylamino-2-butenenitrile is simple, does not generate toxic and harmful byproducts such as cyanide and the like, and is economical and environment-friendly.
Drawings
FIG. 1 is a schematic diagram of 3-benzylamino-2-butenenitrile prepared in example 1 1 H-NMR spectrum.
FIG. 2 is an infrared spectrum of 3-benzylamino-2-butenenitrile prepared in example 1.
FIG. 3 is a schematic diagram of 3-benzylamino-2-butenenitrile prepared in example 1 13 C-NMR spectrum.
FIG. 4 is a liquid mass spectrum of 3-benzylamino-2-butenenitrile prepared in example 1.
FIG. 5 is a liquid chromatogram of the product obtained in comparative example 1.
FIG. 6 is a liquid chromatogram of the product obtained in comparative example 2.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
1. The preparation method of 3-benzylamino-2-butenenitrile comprises the following steps:
(1) Preparing electrolysis:
the anode chamber and the cathode chamber of the electrolytic cell are separated by using FKS-50 cation exchange membrane, the anode chamber is filled with anolyte, the cathode chamber is filled with catholyte, and the volume of the anolyte and the volume of the catholyte are the same. The anolyte is acetonitrile solution of 1.0mol/L tetraethylammonium chloride; the catholyte is acetonitrile solution of tetraethylammonium chloride and benzylamine, wherein the concentration of the tetraethylammonium chloride is 0.5mol/L, and the concentration of the benzylamine is 0.3mol/L.
(2) And (3) electrolysis:
at 20 ℃ under normal pressure, the cathode chamberIs filled with N 2 To saturation, cu is used as a cathode, graphite is used as an anode, and 13.5mA/cm is used 2 Constant current electrolysis is carried out at constant current density, and the electricity quantity per mole of benzylamine is 2.0F.
(3) Post-treatment:
taking out the liquid in the cathode chamber after the electrolysis is finished, and removing acetonitrile by reduced pressure rotary evaporation; adding saturated sodium bicarbonate solution, wherein the addition amount is 1.0 times of the volume of the liquid taken out from the cathode chamber; and adding diethyl ether for extraction for three times, combining the ether layers, adding anhydrous magnesium sulfate into the obtained ether layer liquid for drying for 2 hours, filtering, and performing second rotary evaporation on the filtrate to remove diethyl ether to obtain the product 3-benzylamino-2-butenenitrile.
2. Product testing
(1) Product warp 1 H-NMR (600 MHz, deuterated chloroform d-CDCH) 3 ) The test results: delta ppm 2.13 (s, 3H, -CH 3 ),3.84(s,1H,＝CH),4.13(d,J＝5.09Hz,2H,PhCH 2 (-), 4.74 (brs, 1H, -NH-), 7.26 (d, j=7.27 hz, 2H), 7.31 (d, j=7.27 hz, 1H), 7.34-7.37 (m, 2H), as shown in fig. 1.
(2) The product was subjected to infrared spectroscopic testing on a Nicolet iS20 Fourier transform infrared spectrometer produced by Thermo Nicolet Inc., FIG. 2 shows the infrared spectrum of the compound, IR (KBr, cm) -1 ):3430,3312,3088,2196,1631,1597,1350。
(3) Product warp 13 C-NMR (deuterated chloroform d-CDCH) 3 ) The test gave delta ppm 20.22,47.84,61.62,121.73,127.65,128.00,128.94,136.44,159.87 as shown in FIG. 3.
(4) The molecular weight of the product was 172.8 as measured by a liquid chromatography-mass spectrometer (LC-MS), and as shown in FIG. 4, the peak of 3-benzylamino-2-butenenitrile appeared at a retention time of 4.95min on the liquid chromatogram.
(5) Yield detection:
the synthesized product was detected by high performance liquid chromatography to give a yield of 30% of 3-benzylamino-2-butenenitrile.
Example 2
1. The preparation method of 3-benzylamino-2-butenenitrile comprises the following steps:
(1) Preparing electrolysis:
the anode chamber and the cathode chamber of the electrolytic cell are separated by using FKS-50 cation exchange membrane, the anode chamber is filled with anolyte, the cathode chamber is filled with catholyte, and the volume of the anolyte and the volume of the catholyte are the same. The anolyte is acetonitrile solution of 0.5mol/L tetraethylammonium chloride; the catholyte is acetonitrile solution of tetraethylammonium chloride and benzylamine, wherein the concentration of the tetraethylammonium chloride is 0.25mol/L, and the concentration of the benzylamine is 0.5mol/L.
(2) And (3) electrolysis:
introducing N into the cathode chamber at 15 deg.C under normal pressure 2 To saturation, cu is used as a cathode, graphite is used as an anode, and then 12.0mA/cm is used 2 Constant current electrolysis is carried out at constant current density, and the electricity quantity per mole of benzylamine is 2.2F.
(3) Post-treatment:
taking out the liquid in the cathode chamber after the electrolysis is finished, and removing acetonitrile by reduced pressure rotary evaporation; adding saturated sodium bicarbonate solution, wherein the addition amount is 0.5 times of the volume of the liquid taken out from the cathode chamber; and adding diethyl ether for extraction for three times, combining the ether layers, adding anhydrous magnesium sulfate into the obtained ether layer liquid for drying for 2 hours, filtering, and performing second rotary evaporation on the filtrate to remove diethyl ether to obtain the 3-benzylamino-2-butenenitrile.
2. Product testing
(1) The product was subjected to the same procedure as in example 1 1 H-NMR test, IR spectrum test, 13 C-NMR and liquid Mass Spectrometry, the product obtained was found to be 3-benzylamino-2-butenenitrile.
(2) Yield detection:
the yield of 3-benzylamino-2-butenenitrile was 17% by High Performance Liquid Chromatography (HPLC).
Example 3
1. The preparation method of 3-benzylamino-2-butenenitrile comprises the following steps:
(1) Preparing electrolysis:
the anode chamber and the cathode chamber of the electrolytic cell are separated by using FKS-50 cation exchange membrane, the anode chamber is filled with anolyte, the cathode chamber is filled with catholyte, and the volume of the anolyte and the volume of the catholyte are the same. The anolyte is acetonitrile solution of 0.1mol/L tetraethylammonium chloride; the catholyte is acetonitrile solution of tetraethyl ammonium chloride and benzylamine, wherein the concentration of the tetraethyl ammonium chloride is 0.05mol/L, and the concentration of the benzylamine is 0.1mol/L.
(2) And (3) electrolysis:
introducing N into the cathode chamber at 0deg.C under normal pressure 2 To saturation, cu is used as a cathode, graphite is used as an anode, and then 15.0mA/cm 2 Constant current electrolysis is carried out at constant current density, and the electricity quantity per mole of benzylamine is 2.5F.
(3) Post-treatment:
taking out the liquid in the cathode chamber after the electrolysis is finished, and removing acetonitrile by reduced pressure rotary evaporation; adding saturated sodium bicarbonate solution, wherein the addition amount is 0.8 times of the volume of the liquid taken out from the cathode chamber; and adding diethyl ether for extraction for three times, combining the ether layers, adding anhydrous magnesium sulfate into the obtained ether layer liquid for drying for 2 hours, filtering, and performing second rotary evaporation on the filtrate to remove diethyl ether to obtain the 3-benzylamino-2-butenenitrile.
2. Product testing
(1) The product was subjected to the same procedure as in example 1 1 H-NMR test, IR spectrum test, 13 C-NMR and liquid Mass Spectrometry, the product obtained was found to be 3-benzylamino-2-butenenitrile.
(2) Yield detection:
the yield of 3-benzylamino-2-butenenitrile was determined to be 24% by High Performance Liquid Chromatography (HPLC).
Example 4
1. The preparation method of 3-benzylamino-2-butenenitrile comprises the following steps:
(1) Preparing electrolysis:
the anode chamber and the cathode chamber of the electrolytic cell are separated by using FKS-50 cation exchange membrane, the anode chamber is filled with anolyte, the cathode chamber is filled with catholyte, and the volume of the anolyte and the volume of the catholyte are the same. The anolyte is acetonitrile solution of 0.80mol/L tetraethylammonium chloride; the catholyte is acetonitrile solution of tetraethylammonium chloride and benzylamine, wherein the concentration of the tetraethylammonium chloride is 0.40mol/L, and the concentration of the benzylamine is 0.20mol/L.
(2) And (3) electrolysis:
introducing N into the cathode chamber at 35deg.C under normal pressure 2 To saturation, cu is used as a cathode, graphite is used as an anode, and then 16.5mA/cm is used 2 Constant current electrolysis is carried out at constant current density, and the electricity quantity per mole of benzylamine is 1.0F.
(3) Post-treatment:
taking out the liquid in the cathode chamber after the electrolysis is finished, and removing acetonitrile by reduced pressure rotary evaporation; adding saturated sodium bicarbonate solution, wherein the addition amount is 1.0 times of the volume of the liquid taken out from the cathode chamber; and adding diethyl ether for extraction for three times, combining the ether layers, adding anhydrous magnesium sulfate into the obtained ether layer liquid for drying for 2 hours, filtering, and performing second rotary evaporation on the filtrate to remove diethyl ether to obtain the 3-benzylamino-2-butenenitrile.
2. Product testing
(1) The product was subjected to the same procedure as in example 1 1 H-NMR test, IR spectrum test, 13 C-NMR and liquid Mass Spectrometry, the product obtained was found to be 3-benzylamino-2-butenenitrile.
(2) Yield detection:
the yield of 3-benzylamino-2-butenenitrile was determined to be 13% by High Performance Liquid Chromatography (HPLC).
Example 5
1. The preparation method of 3-benzylamino-2-butenenitrile comprises the following steps:
(1) Preparing electrolysis:
the anode chamber and the cathode chamber of the electrolytic cell are separated by using FKS-50 cation exchange membrane, the anode chamber is filled with anolyte, the cathode chamber is filled with catholyte, and the volume of the anolyte and the volume of the catholyte are the same. The anolyte is acetonitrile solution of 1.0mol/L tetraethylammonium chloride; the catholyte is acetonitrile solution of tetraethyl ammonium chloride and benzylamine, wherein the concentration of the tetraethyl ammonium chloride is 0.5mol/L, and the concentration of the benzylamine is 0.05mol/L.
(2) And (3) electrolysis:
introducing N into the cathode chamber at 10deg.C under normal pressure 2 To saturation, cu is used as a cathode, graphite is used as an anode, and then 18.0mA/cm 2 Is carried out at constant current densityConstant current electrolysis, the energization amount of the benzyl amine is 2.2F per mole.
(3) Post-treatment:
taking out the liquid in the cathode chamber after the electrolysis is finished, and removing acetonitrile by reduced pressure rotary evaporation; adding saturated sodium bicarbonate solution, wherein the addition amount is 1.0 times of the volume of the liquid taken out from the cathode chamber; and adding diethyl ether for extraction for three times, combining the ether layers, adding anhydrous magnesium sulfate into the obtained ether layer liquid for drying for 2 hours, filtering, and performing second rotary evaporation on the filtrate to remove diethyl ether to obtain the 3-benzylamino-2-butenenitrile.
2. Product testing
(1) The product was subjected to the same procedure as in example 1 1 H-NMR test, IR spectrum test, 13 C-NMR and liquid Mass Spectrometry, the product obtained was found to be 3-benzylamino-2-butenenitrile.
(2) Yield detection:
the yield of 3-benzylamino-2-butenenitrile was determined to be 18% by High Performance Liquid Chromatography (HPLC).
Example 6
1. Preparation of 3-benzylamino-2-butenenitrile electrolytic preparation, electrolysis and aftertreatment were carried out in exactly the same manner as in example 1 except that Ag was used as a cathode electrode.
2. Product testing
(1) The product was subjected to the same procedure as in example 1 1 H-NMR test, IR spectrum test, 13 C-NMR and liquid Mass Spectrometry, the product obtained was found to be 3-benzylamino-2-butenenitrile.
(2) Yield detection:
the yield of 3-benzylamino-2-butenenitrile was 16% by High Performance Liquid Chromatography (HPLC).
Example 7
1. Preparation of 3-benzylamino-2-butenenitrile electrolytic preparation, electrolysis and aftertreatment were carried out in exactly the same manner as in example 1 except that Ni was used as a cathode electrode.
2. Product testing
(1) The product was subjected to the same procedure as in example 1 1 H-NMR test, IR lightSpectral testing, 13 C-NMR and liquid Mass Spectrometry, the product obtained was found to be 3-benzylamino-2-butenenitrile.
(2) Yield detection:
the yield of 3-benzylamino-2-butenenitrile was determined to be 13% by High Performance Liquid Chromatography (HPLC).
Example 8
1. Preparation of 3-benzylamino-2-butenenitrile electrolytic preparation, electrolysis and aftertreatment were carried out in exactly the same manner as in example 1 except that 304 stainless steel was used as a cathode electrode.
2. Product testing
(1) The product was subjected to 1H-NMR test, infrared spectroscopic test, 13C-NMR test and liquid phase mass spectrometry test in the same manner as in example 1, and it was found that the obtained product was 3-benzylamino-2-butenenitrile.
(2) Yield detection:
the yield of 3-benzylamino-2-butenenitrile was determined to be 15% by High Performance Liquid Chromatography (HPLC).
Example 9
1. Preparation of 3-benzylamino-2-butenenitrile electrolytic preparation, electrolysis and aftertreatment were carried out in exactly the same manner as in example 1 except that a platinum electrode was used as a cathode electrode.
2. Product testing
(1) The product was subjected to 1H-NMR test, infrared spectroscopic test, 13C-NMR test and liquid phase mass spectrometry test in the same manner as in example 1, and it was found that the obtained product was 3-benzylamino-2-butenenitrile.
(2) Yield detection:
the yield of 3-benzylamino-2-butenenitrile was determined to be 26% by High Performance Liquid Chromatography (HPLC).
Example 10
1. Preparation of 3-benzylamino-2-butenenitrile electrolytic preparation, electrolysis and aftertreatment were carried out in exactly the same manner as in example 1 except that Ti was used as a cathode electrode.
2. Product testing
(1) The product was subjected to the same procedure as in example 1 1 H-NMR test, infrared Spectrometry test, 13 C-NMR and liquid Mass Spectrometry, the product obtained was found to be 3-benzylamino-2-butenenitrile.
(2) Yield detection:
the yield of 3-benzylamino-2-butenenitrile was determined to be 10% by High Performance Liquid Chromatography (HPLC).
Example 11
1. Preparation of 3-benzylamino-2-butenenitrile electrolytic preparation, electrolysis and work-up were carried out in exactly the same manner as in example 1 except that tetraethylammonium bromide was used instead of tetraethylammonium chloride.
2. Product testing
(1) The product was subjected to 1H-NMR test, infrared spectroscopic test, 13C-NMR test and liquid phase mass spectrometry test in the same manner as in example 1, and it was found that the obtained product was 3-benzylamino-2-butenenitrile.
(2) Yield detection:
the yield of 3-benzylamino-2-butenenitrile was determined to be 14% by High Performance Liquid Chromatography (HPLC).
Example 12
1. Preparation of 3-benzylamino-2-butenenitrile electrolytic preparation, electrolysis and work-up were carried out in exactly the same manner as in example 1 except that tetraethylammonium iodide was used instead of tetraethylammonium chloride.
2. Product testing
(1) The product was subjected to the same procedure as in example 1 1 H-NMR test, IR spectrum test, 13 C-NMR and liquid Mass Spectrometry, the product obtained was found to be 3-benzylamino-2-butenenitrile.
(2) Yield detection:
the yield of 3-benzylamino-2-butenenitrile was determined to be 18% by High Performance Liquid Chromatography (HPLC).
Example 13
1. Preparation of 3-benzylamino-2-butenenitrile electrolytic preparation, electrolysis and work-up were carried out in exactly the same manner as in example 1 except that tetraethylammonium tetrafluoroborate was used instead of tetraethylammonium chloride.
2. Product testing
(1) The product was subjected to the same procedure as in example 1 1 H-NMR test, IR spectrum test, 13 C-NMR and liquid Mass Spectrometry, the product obtained was found to be 3-benzylamino-2-butenenitrile.
(2) Yield detection:
the yield of 3-benzylamino-2-butenenitrile was determined to be 51% by High Performance Liquid Chromatography (HPLC).
Example 14
1. Preparation of 3-benzylamino-2-butenenitrile electrolytic preparation, electrolysis and work-up were carried out in exactly the same manner as in example 1 except that tetra-n-butylammonium iodide was used instead of tetraethylammonium chloride.
2. Product testing
(1) The product was subjected to the same procedure as in example 1 1 H-NMR test, IR spectrum test, 13 C-NMR and liquid Mass Spectrometry, the product obtained was found to be 3-benzylamino-2-butenenitrile.
(2) Yield detection:
the yield of 3-benzylamino-2-butenenitrile was determined to be 20% by High Performance Liquid Chromatography (HPLC).
Example 15
1. Preparation of 3-benzylamino-2-butenenitrile electrolytic preparation, electrolysis and work-up were carried out in exactly the same manner as in example 1, except that tetraethylammonium perchlorate was used instead of tetraethylammonium chloride.
2. Product testing
(1) The product was subjected to the same procedure as in example 1 1 H-NMR test, IR spectrum test, 13 C-NMR and liquid Mass Spectrometry, the product obtained was found to be 3-benzylamino-2-butenenitrile.
(2) Yield detection:
the yield of 3-benzylamino-2-butenenitrile was determined to be 10% by High Performance Liquid Chromatography (HPLC).
Example 16
1. The preparation method of 3-benzylamino-2-butenenitrile comprises the following steps:
(1) The anode chamber and the cathode chamber of the electrolytic cell are separated by using FKS-50 cation exchange membrane, the anode chamber is filled with anolyte, the cathode chamber is filled with catholyte, and the volume of the anolyte and the volume of the catholyte are the same. The anolyte is acetonitrile solution of 0.5mol/L tetraethylammonium chloride; the catholyte is acetonitrile solution of tetraethylammonium chloride and benzylamine, wherein the concentration of the tetraethylammonium chloride is 0.5mol/L, and the concentration of the benzylamine is 0.3mol/L.
The electrolytic preparation, electrolysis and post-treatment were carried out in exactly the same manner as in example 1.
2. Product testing
(1) The product was subjected to the same procedure as in example 1 1 H-NMR test, IR spectrum test, 13 C-NMR and liquid Mass Spectrometry, the product obtained was found to be 3-benzylamino-2-butenenitrile.
(2) Yield detection:
the yield of 3-benzylamino-2-butenenitrile was determined to be 20% by High Performance Liquid Chromatography (HPLC).
Comparative example 1
The electrolytic preparation and electrolysis were carried out in exactly the same manner as in example 1, except that the post-treatment steps were as follows:
taking out the liquid in the cathode chamber after the electrolysis is finished, and removing acetonitrile by reduced pressure rotary evaporation; adding 0.2mol/L hydrochloric acid, wherein the addition amount is 1.0 times of the volume of the liquid taken out from the cathode chamber; and adding diethyl ether for extraction for three times, combining the ether layers, adding anhydrous magnesium sulfate into the obtained ether layer liquid for drying for 2 hours, filtering, and performing second rotary evaporation on the filtrate to remove diethyl ether to obtain the product.
2. Product testing
(1) The product was subjected to the same procedure as in example 1 1 H-NMR test, IR spectrum test, 13 C-NMR and liquid mass spectrometry tests showed that the obtained product was free of 3-benzylamino-2-butenenitrile. FIG. 5 is a liquid chromatogram of the product obtained in this comparative example, as shown in FIG. 5, showing no peaks of 3-benzylamino-2-butenenitrile at a retention time of 4.95min on the liquid chromatogram; while in the liquid phase of the product prepared in example 1In the spectrum of FIG. 4, the peak of 3-benzylamino-2-butenenitrile appears on the liquid chromatogram at a retention time of 4.95 min.
Comparative example 2
1. Preparation
(1) Preparation:
the anode chamber and the cathode chamber of the electrolytic cell are separated by using FKS-50 cation exchange membrane, the anode chamber is filled with anolyte, the cathode chamber is filled with catholyte, and the volume of the anolyte and the volume of the catholyte are the same. The anolyte is acetonitrile solution of 1.0mol/L tetraethylammonium chloride; the catholyte is acetonitrile solution of tetraethylammonium chloride and benzylamine, wherein the concentration of the tetraethylammonium chloride is 0.5mol/L, and the concentration of the benzylamine is 0.3mol/L.
(2) Stirring and mixing:
introducing N into the cathode chamber at 20deg.C under normal pressure 2 To saturation, the catholyte was thoroughly stirred and mixed for 10 hours using a stirrer.
(3) Post-treatment:
taking out the liquid in the cathode chamber, and removing acetonitrile by reduced pressure rotary evaporation; adding saturated sodium bicarbonate solution, wherein the addition amount is 1.0 times of the volume of the liquid taken out from the cathode chamber; and adding diethyl ether for extraction for three times, combining the ether layers, adding anhydrous magnesium sulfate into the obtained ether layer liquid for drying for 2 hours, filtering, and performing second rotary evaporation on the filtrate to remove diethyl ether to obtain the product.
2. Product testing
(1) The product was subjected to the same procedure as in example 1 1 H-NMR test, IR spectrum test, 13 C-NMR and liquid mass spectrometry tests showed that the obtained product was free of 3-benzylamino-2-butenenitrile. FIG. 6 is a liquid chromatogram of the product obtained in this comparative example, showing that the peak of 3-benzylamino-2-butenenitrile was not found at a retention time of 4.95 min.
The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described above may be combined with each other as long as they do not collide with each other. In addition, the foregoing is only a partial embodiment, and not all embodiments, of the present invention, and all other embodiments obtained by those skilled in the art without making any creative effort based on the embodiments of the present invention are within the protection scope of the present invention.
Claims (8)
1. A process for preparing 3-benzylamino-2-butenenitrile, comprising the steps of:
step one, preparing electrolysis:
isolating an anode chamber and a cathode chamber of the electrolytic cell by using a cation exchange membrane; graphite electrode is used as anode, and metal electrode is used as cathode; the anolyte is acetonitrile solution of 0.1-1.0 mol/L quaternary ammonium salt; the catholyte is acetonitrile solution of quaternary ammonium salt and benzylamine, wherein the concentration of the quaternary ammonium salt is 0.05-0.5 mol/L, and the concentration of the benzylamine is 0.05-0.5 mol/L;
step two, electrolysis:
introducing N into the cathode chamber at normal pressure and at a temperature of between 0 and 35 DEG C 2 To saturation of 12.0-18.0 mA/cm 2 Electrolysis is carried out at constant current density; the electrifying capacity of each mole of benzylamine is 1.0-2.5F, and F is Faraday constant;
step three, post-treatment:
taking out the liquid in the cathode chamber after the electrolysis is finished, and removing acetonitrile by reduced pressure rotary evaporation; adding saturated sodium bicarbonate solution, wherein the addition amount is 0.5-1 times of the volume of the liquid taken out from the cathode chamber; and then adding diethyl ether for extraction, adding anhydrous magnesium sulfate into the obtained ether layer liquid for drying, filtering, and performing secondary rotary evaporation on the filtrate to remove diethyl ether, thus obtaining the 3-benzylamino-2-butenenitrile.
2. The method for producing 3-benzylamino-2-butenenitrile according to claim 1, wherein the quaternary ammonium salt is one of tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium tetrafluoroborate, tetra-n-butyl ammonium iodide, and tetraethylammonium perchlorate.
3. The process for preparing 3-benzylamino-2-butenenitrile according to claim 1, wherein the cation exchange membrane is an FKS-50 cation exchange membrane.
4. The method for preparing 3-benzylamino-2-butenenitrile according to claim 1, wherein the cathode is made of copper, nickel, titanium, stainless steel, platinum or silver.
5. The process for preparing 3-benzylamino-2-butenenitrile according to claim 1, wherein the constant current density in the second step is 13.5mA/cm 2 。
6. The process for preparing 3-benzylamino-2-butenenitrile according to claim 1, wherein the temperature of electrolysis in the second step is 15 ℃.
7. The process for preparing 3-benzylamino-2-butenenitrile according to claim 1, wherein the charge per mole of benzylamine in the second step is 2.2F.
8. The method for producing 3-benzylamino-2-butenenitrile according to claim 1, wherein the ratio of the amounts of the substances of the quaternary ammonium salt in the catholyte and the anolyte in step one is 1:2.
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