CN118373774A - Preparation method of 2-propyne-1-yl-1H-imidazole-1-carboxylic acid ester - Google Patents
Preparation method of 2-propyne-1-yl-1H-imidazole-1-carboxylic acid ester Download PDFInfo
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- -1 2-propyne-1-yl-1H-imidazole-1-carboxylic acid Chemical compound 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 24
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 230000008025 crystallization Effects 0.000 claims abstract description 12
- 238000010612 desalination reaction Methods 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- YWESEXXKFPAOMS-UHFFFAOYSA-N prop-1-ynyl carbonochloridate Chemical compound CC#COC(Cl)=O YWESEXXKFPAOMS-UHFFFAOYSA-N 0.000 claims description 14
- YNCPXBIZAPNQIJ-UHFFFAOYSA-N 1h-imidazole;sodium Chemical compound [Na].C1=CNC=N1 YNCPXBIZAPNQIJ-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 8
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- RBWFVUDBNNXTFZ-UHFFFAOYSA-N 1h-imidazole;potassium Chemical compound [K].C1=CNC=N1 RBWFVUDBNNXTFZ-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- FIGYYXIYTVBRJV-UHFFFAOYSA-N 1h-imidazole;lithium Chemical compound [Li].C1=CNC=N1 FIGYYXIYTVBRJV-UHFFFAOYSA-N 0.000 claims description 3
- YVZGYWUZULOJJH-UHFFFAOYSA-N 1h-imidazole;magnesium Chemical group [Mg].C1=CNC=N1 YVZGYWUZULOJJH-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000002000 Electrolyte additive Substances 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 41
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 12
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 4
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 4
- 239000011343 solid material Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 3
- WVGMDWUHZVQPFN-UHFFFAOYSA-N N1C=NC=C1.C(=O)Cl Chemical compound N1C=NC=C1.C(=O)Cl WVGMDWUHZVQPFN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- KYWMCFOWDYFYLV-UHFFFAOYSA-N 1h-imidazole-2-carboxylic acid Chemical compound OC(=O)C1=NC=CN1 KYWMCFOWDYFYLV-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of 2-propyne-1-yl-1H-imidazole-1-carboxylate, belonging to the technical field of organic synthesis. The preparation method provided by the invention comprises the following steps: under the protection of inert gas, mixing imidazole salt, aprotic solvent and phase transfer catalyst, then dropwise adding propyne chloroformate or organic solution of propyne chloroformate, carrying out nucleophilic substitution reaction, and carrying out post-treatment on the obtained reaction feed liquid to obtain the 2-propyne-1-yl-1H-imidazole-1-carboxylic acid ester; the post-treatment comprises the steps of sequentially performing filtration and desalination, concentration, crystallization, filtration and separation of products and drying. The invention adopts imidazole salt and propiolate chloroformate as main raw materials, does not use acid binding agent, reduces cost, does not need the procedure of removing the hydrochloride of the acid binding agent by water washing in the post-treatment process, avoids the degradation of the product in the water washing process, has high yield and high purity, and can meet the use requirement of the product as an electrolyte additive.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of 2-propyne-1-yl-1H-imidazole-1-carboxylate.
Background
Lithium ion batteries and energy storage batteries have found wide application in such fields as electric vehicles, electrical energy storage, dispensing, and the like. In a battery, an electrolyte plays a role in transporting ions between an anode and a cathode, and has an important influence on safety, capacity, cycle performance, applicability to operating temperature, and the like of the battery.
The 2-propyne-1-yl-1H-imidazole-1-carboxylate contains propynyl and imidazole ring in its molecular structure, and these special functional groups can provide excellent electron transmission channel, and can be used as an imidazole carboxylate additive in cell electrolyte, so that it can improve cell cathode interface, effectively raise safety of cell and high-low temperature circulation property, and is an important electrolyte additive.
At present, the synthetic routes of 2-propyn-1-yl-1H-imidazole-1-carboxylic acid ester mainly comprise the following steps:
The scheme one reaction is as follows:
Patent document CN202210213854.2 discloses a method for synthesizing 2-propyn-1-yl-1H-imidazole-1-carboxylate: n, N' -carbonyl diimidazole and propargyl alcohol are used as raw materials, the raw materials react under the catalysis of a mixed catalyst of aluminum oxide and zinc oxide, the catalyst is removed by post-treatment and filtration, and then the product is obtained by acid washing, concentration and rectification, and the main problems of the route are as follows: raw material N, N' -carbonyl diimidazole is high in price, and propargyl alcohol is a highly toxic product; the post-treatment requires acid washing, and the acid washing or water washing step results in reduced product yield and purity due to decomposition of the product upon water.
The second scheme is as follows:
Patent document CN201911074787.5 discloses a preparation method of 2-propyn-1-yl-1H-imidazole-1-carboxylate, wherein phosgene and propargyl alcohol are selected to react as raw materials, and distilled and purified to generate propynyl chloroformate; and secondly, reacting the chloric acid propyne with imidazole by using triethylamine as an acid binding agent, and filtering, alkaline washing, drying and distilling under reduced pressure to obtain the target product. The synthesis route uses highly toxic phosgene, which belongs to the elimination technology; and triethylamine is used as an acid binding agent in the reaction process, and triethylamine hydrochloride is also required to be removed by alkali washing in the post-treatment process, so that the product is degraded.
The route three reaction formula is as follows:
Patent document CN202110935166.2 discloses a preparation method of 2-propyne-1-yl-1H-imidazole-1-carboxylate, which uses imidazole formyl chloride and propargyl alcohol as raw materials, triethylamine as acid-binding agent, after synthesis, the target product is obtained through post-treatment procedures such as washing with water to remove triethylamine hydrochloride, drying, concentrating, crystallizing and the like. The imidazole formyl chloride which is the initial raw material of the synthetic route is difficult to obtain, and the propargyl alcohol is a highly toxic product; at the same time, triethylamine is also used as an acid binding agent in the reaction, and triethylamine hydrochloride needs to be removed through water washing in the post-treatment process, which can lead to degradation of products.
To sum up, the prior art process for preparing 2-propyn-1-yl-1H-imidazole-1-carboxylate has the following problems: the starting material propargyl alcohol and phosgene belong to highly toxic chemicals, and the materials are not friendly to production personnel and environment; in the reaction process, an organic amine acid-binding agent is used, and in the post-treatment process, in order to remove the organic amine hydrochloride generated by the acid-binding agent, a water washing process is required, so that the degradation of the product is caused, the yield and purity of the product are reduced, the high-yield and high-purity product is difficult to obtain, and the use requirement of an electrolyte additive cannot be met.
Disclosure of Invention
The invention aims to provide a preparation method of 2-propyn-1-yl-1H-imidazole-1-carboxylic acid ester. According to the invention, imidazole salt and propiolate chloroformate are used as main raw materials, an acid binding agent is not required in the process of preparing 2-propiolate-1-yl-1H-imidazole-1-carboxylate, and a washing operation is not required after the reaction, so that the product is prevented from being washed and degraded, the obtained product is high in yield and purity, and the use requirement of the product as an electrolyte additive can be met.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a preparation method of 2-propyne-1-yl-1H-imidazole-1-carboxylate, which does not use an acid binding agent, does not need water washing in the post-treatment process, and comprises the following steps:
Under the protection of inert gas, mixing imidazole salt, aprotic solvent and phase transfer catalyst, then dropwise adding propyne chloroformate or organic solution of propyne chloroformate, carrying out nucleophilic substitution reaction, and carrying out post-treatment on the obtained reaction feed liquid to obtain the 2-propyne-1-yl-1H-imidazole-1-carboxylic acid ester;
the post-treatment comprises the steps of sequentially performing filtration and desalination, concentration, crystallization, filtration and separation of products and drying.
Preferably, the imidazole salt is an alkali metal salt of imidazole or an alkaline earth metal salt of imidazole.
Preferably, the alkali metal salt of imidazole includes at least one of sodium imidazole, potassium imidazole and lithium imidazole; the alkaline earth metal salt of imidazole is magnesium imidazole.
Preferably, the aprotic solvent comprises one or a mixture of several of aliphatic hydrocarbon, halogenated aliphatic hydrocarbon, aromatic hydrocarbon, halogenated aromatic hydrocarbon and ether solvent; the mass ratio of the aprotic solvent to the imidazole salt is 5-20: 1.
Preferably, the aliphatic hydrocarbon includes at least one of n-hexane, cyclohexane and n-heptane; the halogenated aliphatic hydrocarbon comprises methylene dichloride; the aromatic hydrocarbon comprises at least one of toluene and xylene; the halogenated aromatic hydrocarbon comprises chlorobenzene; the ethers include at least one of isopropyl ether, methyl tert-butyl ether and tetrahydrofuran.
Preferably, the mole ratio of the imidazole salt to the propynyl chloroformate is 0.8-1: 0.8 to 1.2.
Preferably, the phase transfer catalyst is a quaternary ammonium salt catalyst; the mole ratio of the phase transfer catalyst to the imidazole salt is 0.001-0.02: 1.
Preferably, the quaternary ammonium salt catalyst includes at least one of tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium bisulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, and tetradecyltrimethylammonium chloride.
Preferably, the temperature of the nucleophilic substitution reaction is 0 ℃ to the boiling point temperature of the aprotic solvent, and the heat preservation time is 2-10 h.
Preferably, the concentration is normal pressure concentration or reduced pressure concentration; the drying is reduced pressure drying, the drying temperature is 15-35 ℃, the time is 4-12 h, and the vacuum degree is less than or equal to minus 0.09MPa.
The invention provides a preparation method of 2-propyne-1-yl-1H-imidazole-1-carboxylate, which does not use an acid binding agent, does not need water washing in the post-treatment process, and comprises the following steps: under the protection of inert gas, mixing imidazole salt, aprotic solvent and phase transfer catalyst, then dropwise adding propyne chloroformate or organic solution of propyne chloroformate, carrying out nucleophilic substitution reaction, and carrying out post-treatment on the obtained reaction feed liquid to obtain the 2-propyne-1-yl-1H-imidazole-1-carboxylic acid ester; the post-treatment comprises the steps of sequentially performing filtration and desalination, concentration, crystallization, filtration and separation of products and drying. The invention does not adopt the virulent chemicals such as propargyl alcohol, phosgene and the like as raw materials, but adopts imidazole salt and chloroformate propinyl ester as raw materials, and does not need to use acid binding agent; nucleophilic substitution reaction is carried out on the raw materials in the presence of a phase transfer catalyst to prepare 2-propyne-1-yl-1H-imidazole-1-carboxylate; the reaction is carried out without washing operation, and only simple filtration desalting and concentration crystallization operation are needed, so that the degradation of the product is avoided, and the high-purity 2-propyne-1-yl-1H-imidazole-1-carboxylate can be obtained in high yield. The preparation method provided by the invention is simple and feasible, low in cost, and the obtained product has good yield and quality, can meet the use requirement of the electrolyte additive, and is suitable for industrial production.
Drawings
FIG. 1 is a gas chromatogram of the product obtained in example 1.
Detailed Description
The invention provides a preparation method of 2-propyne-1-yl-1H-imidazole-1-carboxylate, which does not use an acid binding agent, does not need water washing in the post-treatment process, and comprises the following steps:
Under the protection of inert gas, mixing imidazole salt, aprotic solvent and phase transfer catalyst, then dropwise adding propyne chloroformate or organic solution of propyne chloroformate, carrying out nucleophilic substitution reaction, and carrying out post-treatment on the obtained reaction feed liquid to obtain the 2-propyne-1-yl-1H-imidazole-1-carboxylic acid ester;
the post-treatment comprises the steps of sequentially performing filtration and desalination, concentration, crystallization, filtration and separation of products and drying.
In the present invention, unless otherwise specified, all materials are commercially available or prepared by methods well known to those skilled in the art.
In the present invention, the synthetic route of 2-propyn-1-yl-1H-imidazole-1-carboxylate is as follows:
Wherein M + is sodium ion or potassium ion, and M 2+ is magnesium ion.
Under the protection of inert gas, the invention mixes imidazole salt, aprotic solvent and phase transfer catalyst, then drops the organic solution of propynyl chloroformate or propynyl chloroformate to carry out nucleophilic substitution reaction.
In the present invention, the inert gas is preferably nitrogen.
In the present invention, the imidazole salt, the phase transfer catalyst and the aprotic solvent are preferably mixed to obtain an imidazole salt dispersion. In the present invention, the imidazole salt is preferably an alkali metal salt of imidazole or an alkaline earth metal salt of imidazole; the alkali metal salt of imidazole preferably includes at least one of sodium imidazole, potassium imidazole and lithium imidazole, more preferably includes sodium imidazole or potassium imidazole, and still more preferably sodium imidazole; the alkaline earth metal salt of imidazole is preferably magnesium imidazole.
In the present invention, the aprotic solvent preferably includes at least one or a mixed solvent of several of aliphatic hydrocarbon, halogenated aliphatic hydrocarbon, aromatic hydrocarbon, halogenated aromatic hydrocarbon and ether solvent; the aliphatic hydrocarbon preferably includes at least one of n-hexane, cyclohexane and n-heptane; the halogenated aliphatic hydrocarbon preferably comprises methylene chloride; the aromatic hydrocarbon preferably includes at least one of toluene and xylene, more preferably toluene; the halogenated aromatic hydrocarbon preferably comprises chlorobenzene; the ethers preferably include at least one of isopropyl ether, methyl tert-butyl ether and tetrahydrofuran, more preferably tetrahydrofuran. The aprotic solvents according to the invention preferably have a water content of < 0.1%, more preferably a water content of 200ppm or less. The mass ratio of the aprotic solvent to the imidazole salt is preferably 5-20: 1, more preferably 7 to 10:1. the amount of the aprotic solvent used in the present invention is such that the product obtained does not precipitate from the aprotic solvent to a minimum after the nucleophilic substitution reaction is completed.
In the present invention, the phase transfer catalyst is preferably a quaternary ammonium salt catalyst; the quaternary ammonium salt catalyst preferably includes at least one of tetrabutylammonium bromide, benzyltriethylammonium chloride (TEBA), tetrabutylammonium chloride, tetrabutylammonium bisulfate (TBAB), trioctylmethyl ammonium chloride, dodecyltrimethyl ammonium chloride, and tetradecyltrimethylammonium chloride, more preferably tetrabutylammonium chloride or tetrabutylammonium bromide. The molar ratio of the phase transfer catalyst to the imidazole salt is preferably 0.001-0.02: 1, more preferably 0.002 to 0.01:1. in the present invention, the molar ratio of the imidazole salt to the propynyl chloroformate is preferably from 0.8 to 1:0.8 to 1.2, more preferably 0.9 to 1:0.9 to 1.1.
The invention adopts a dripping mode to drop the propinyl chloroformate or the organic solvent containing the propinyl chloroformate into the imidazole salt dispersion liquid. In the present invention, the temperature of the dropping is preferably from 0℃to the boiling point temperature of the aprotic solvent, more preferably from 0 to 20℃and still more preferably from 0 to 5 ℃. After the addition of the propynyl chloroformate or the propynyl chloroformate-containing organic solvent is completed, the invention preferably adjusts the temperature to carry out nucleophilic substitution reaction. In the present invention, the temperature of the nucleophilic substitution reaction is preferably from 0 ℃ to the boiling temperature of the aprotic solvent, more preferably from 15 to 30 ℃; the holding time is preferably 2 to 10 hours, more preferably 2 to 3 hours.
After the nucleophilic substitution reaction is finished, the reaction feed liquid is subjected to post-treatment to obtain the 2-propyne-1-yl-1H-imidazole-1-carboxylate. The post-treatment of the invention comprises the steps of sequentially performing filtration and desalination, concentration, crystallization, filtration and separation of products and drying. In the present invention, the temperature of the filter desalination is preferably from 0 ℃ to the boiling point temperature of the aprotic solvent, more preferably from 15 to 30 ℃. The invention adopts a filtering mode to remove insoluble matters (salts) in the reaction feed liquid, and the obtained filtrate is collected for subsequent concentration, crystallization, filtering and separation of products and drying operation. In the present invention, the concentration is preferably normal pressure concentration or reduced pressure concentration, more preferably reduced pressure concentration. The present invention preferably concentrates until the product (2-propyn-1-yl-1H-imidazole-1-carboxylate) is separated out, stops concentrating, and crystallizes the obtained concentrated feed liquid. In the present invention, the temperature of the crystallization is preferably 0 to 5 ℃; the time is preferably 0.5 to 2 hours, more preferably 1 hour. After the crystallization, the invention preferably filters the obtained crystallization feed liquid and collects solid materials; and drying the solid material to obtain the 2-propyn-1-yl-1H-imidazole-1-carboxylic acid ester. In the present invention, the drying is preferably drying under reduced pressure; the drying temperature is preferably 15-35 ℃, more preferably 20-30 ℃; the time is preferably 4-12 hours, more preferably 4-6 hours; the vacuum degree is preferably less than or equal to-0.09 MPa.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. 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.
Example 1
Under the protection of nitrogen, 90.0 g of sodium imidazole, 630.0 g of dichloromethane and 0.3 g of tetrabutylammonium chloride are put into a reaction bottle to obtain sodium imidazole dispersion liquid;
Cooling the imidazole sodium dispersion liquid to 0-5 ℃, dropwise adding 118.5 g of propiolic chloroformate into the imidazole sodium dispersion liquid at the temperature, raising the temperature to 15-20 ℃ after the dropwise adding is finished, and carrying out heat preservation reaction for 3 hours at the temperature of 15-20 ℃ to obtain reaction liquid;
Keeping the temperature at 15-20 ℃, filtering to remove insoluble matters in the reaction feed liquid, and collecting filtrate; concentrating the filtrate under reduced pressure at 25-30 ℃ until a product is separated out, and stopping concentrating; cooling the obtained concentrated feed liquid to 0-5 ℃ for crystallization for 1h, filtering after finishing, and collecting solid materials (i.e. filter cakes); the solid material was dried under reduced pressure at 30℃for 6 hours to give 142.9 g of a product.
The product obtained in example 1 was subjected to gas chromatography, and the analysis results are shown in Table 1; the gas chromatogram of the product obtained in example 1 is shown in FIG. 1.
TABLE 1 analysis results of the products obtained in example 1
The purity of 2-propyn-1-yl-1H-imidazole-1-carboxylic acid ester in the product obtained in example 1 was 99.89%, and the yield was 95.2%.
Example 2
The reaction materials were adjusted to 90.0 g of sodium imidazole, 720.0 g of methylene chloride, 0.5 g of tetrabutylammonium chloride and 130.3 g of propynyl chloroformate, and the remaining conditions were the same as in example 1 to obtain 142.1 g of a product.
The purity of 2-propyn-1-yl-1H-imidazole-1-carboxylic acid ester in the product obtained in example 2 was 99.67%, and the yield was 94.7%.
Example 3
The reaction materials were adjusted to 90.0 g of sodium imidazole, 720.0 g of methylene chloride, 0.5 g of tetrabutylammonium bromide and 118.5 g of propynylchloroformate, and 139.6 g of a product was obtained under the same conditions as in example 1.
The purity of 2-propyn-1-yl-1H-imidazole-1-carboxylic acid ester in the product obtained in example 3 was 99.65%, and the yield was 93.0%.
Example 4
The reaction materials were adjusted to 90.0 g of sodium imidazole, 720.0 g of methylene chloride, 1g of tetrabutylammonium chloride and 118.5 g of propynylchloroformate, and 140.1 g of a product was obtained under the same conditions as in example 1.
The purity of 2-propyn-1-yl-1H-imidazole-1-carboxylic acid ester in the product obtained in example 4 was 99.57%, and the yield was 93.3%.
Example 5
The reaction materials were adjusted to 90.0 g of sodium imidazole, 720.0 g of methylene chloride, 0.5 g of tetrabutylammonium chloride and 118.5 g of propynylchloroformate, and the remaining conditions were the same as in example 1 to obtain 136.6 g of a product.
The purity of 2-propyn-1-yl-1H-imidazole-1-carboxylic acid ester in the product obtained in example 5 was 99.63%, and the yield was 91.0%.
Compared with the prior art, the preparation method provided by the invention does not use the raw materials such as virulent propargyl alcohol, phosgene and the like; organic amine acid binding agents are not needed in the reaction process; the post-treatment process abandons the water washing process, can effectively prevent the degradation of the product, improves the purity and the yield of the product, shortens the reaction flow and the period, has mild reaction conditions, is a low-cost green synthesis method, and is suitable for industrial production.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. The preparation method of the 2-propyn-1-yl-1H-imidazole-1-carboxylic ester is characterized in that an acid binding agent is not used, and the post-treatment process does not need water washing, and comprises the following steps:
Under the protection of inert gas, mixing imidazole salt, aprotic solvent and phase transfer catalyst, then dropwise adding propynyl chloroformate or organic solution of propynyl chloroformate for nucleophilic substitution reaction, and carrying out post-treatment on the obtained reaction feed liquid to obtain the 2-propynyl-1-yl-1H-imidazole-1-carboxylic acid ester;
the post-treatment comprises the steps of sequentially performing filtration and desalination, concentration, crystallization, filtration and separation of products and drying.
2. The method according to claim 1, wherein the imidazole salt is an alkali metal salt of imidazole or an alkaline earth metal salt of imidazole.
3. The production method according to claim 2, wherein the alkali metal salt of imidazole comprises at least one of sodium imidazole, potassium imidazole and lithium imidazole; the alkaline earth metal salt of imidazole is magnesium imidazole.
4. The production method according to claim 1, wherein the aprotic solvent comprises a mixed solvent of one or more of an aliphatic hydrocarbon, a halogenated aliphatic hydrocarbon, an aromatic hydrocarbon, a halogenated aromatic hydrocarbon, and an ether solvent; the mass ratio of the aprotic solvent to the imidazole salt is 5-20: 1.
5. The production method according to claim 4, wherein the aliphatic hydrocarbon comprises at least one of n-hexane, cyclohexane and n-heptane; the halogenated aliphatic hydrocarbon comprises methylene dichloride; the aromatic hydrocarbon comprises at least one of toluene and xylene; the halogenated aromatic hydrocarbon comprises chlorobenzene; the ethers include at least one of isopropyl ether, methyl tert-butyl ether and tetrahydrofuran.
6. The preparation method according to claim 1, wherein the molar ratio of the imidazole salt to the propynyl chloroformate is 0.8 to 1:0.8 to 1.2.
7. The method of preparation of claim 1, wherein the phase transfer catalyst is a quaternary ammonium salt catalyst; the mole ratio of the phase transfer catalyst to the imidazole salt is 0.001-0.02: 1.
8. The method according to claim 7, wherein the quaternary ammonium salt catalyst comprises at least one of tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium bisulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, and tetradecyltrimethylammonium chloride.
9. The method according to claim 1, wherein the nucleophilic substitution reaction is carried out at a temperature of 0 ℃ to the boiling point temperature of the aprotic solvent for a period of 2 to 10 hours.
10. The method according to claim 1, wherein the concentration is normal pressure concentration or reduced pressure concentration; the drying is reduced pressure drying, the drying temperature is 15-35 ℃, the time is 4-12 h, and the vacuum degree is less than or equal to minus 0.09MPa.
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