CN107628979B - Method for synthesizing 2H-azacyclo acrylamide - Google Patents
Method for synthesizing 2H-azacyclo acrylamide Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 title claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- IAXWZYXUKABJAN-UHFFFAOYSA-N 1,2-oxazol-5-amine Chemical compound NC1=CC=NO1 IAXWZYXUKABJAN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005286 illumination Methods 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- VQZCMFOELVYEHV-UHFFFAOYSA-N 3-cyclohexyl-1,2-oxazol-5-amine Chemical compound O1C(N)=CC(C2CCCCC2)=N1 VQZCMFOELVYEHV-UHFFFAOYSA-N 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZDJCARGGZRTYFH-UHFFFAOYSA-L [1,3-bis(2-methylphenyl)imidazolidin-2-ylidene]-dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)Cl.CC1=CC=CC=C1N1CCN(C=2C(=CC=CC=2)C)[C]1 ZDJCARGGZRTYFH-UHFFFAOYSA-L 0.000 claims description 6
- -1 3-cinnamyl-5-aminoisoxazole Chemical compound 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- RENBDRDSZNKVPG-UHFFFAOYSA-N 3-(3-phenylpropyl)-1,2-oxazol-5-amine Chemical compound O1C(N)=CC(CCCC=2C=CC=CC=2)=N1 RENBDRDSZNKVPG-UHFFFAOYSA-N 0.000 claims description 3
- HFGPJQSKIRCYSD-UHFFFAOYSA-N N-benzyl-3-phenyl-1,2-oxazol-5-amine Chemical compound C(NC1=CC(=NO1)C1=CC=CC=C1)C1=CC=CC=C1 HFGPJQSKIRCYSD-UHFFFAOYSA-N 0.000 claims description 3
- FXODGYZDVFVJBA-UHFFFAOYSA-N [Ru].ClC1C(C(CCC1)(P(C1CCCCC1)C1CCCCC1)Cl)=CC1=C(C=CC=C1)OC(C)C Chemical group [Ru].ClC1C(C(CCC1)(P(C1CCCCC1)C1CCCCC1)Cl)=CC1=C(C=CC=C1)OC(C)C FXODGYZDVFVJBA-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RKWRDXQHQYRFCX-UHFFFAOYSA-N 3-(4-bromophenyl)-1,2-oxazol-5-amine Chemical compound O1C(N)=CC(C=2C=CC(Br)=CC=2)=N1 RKWRDXQHQYRFCX-UHFFFAOYSA-N 0.000 claims description 2
- KRQFEURBUJROHA-UHFFFAOYSA-N 3-(4-chlorophenyl)-1,2-oxazol-5-amine Chemical compound O1C(N)=CC(C=2C=CC(Cl)=CC=2)=N1 KRQFEURBUJROHA-UHFFFAOYSA-N 0.000 claims description 2
- MKXZGFIJQYOAAA-UHFFFAOYSA-N 3-(furan-2-yl)-1,2-oxazol-5-amine Chemical compound O1C(N)=CC(C=2OC=CC=2)=N1 MKXZGFIJQYOAAA-UHFFFAOYSA-N 0.000 claims description 2
- HTLBMZKXJYNJSK-UHFFFAOYSA-N 3-naphthalen-2-yl-1,2-oxazol-5-amine Chemical compound O1C(N)=CC(C=2C=C3C=CC=CC3=CC=2)=N1 HTLBMZKXJYNJSK-UHFFFAOYSA-N 0.000 claims description 2
- HLOHVVZZMMMDMM-UHFFFAOYSA-N 3-phenyl-1,2-oxazol-5-amine Chemical compound O1C(N)=CC(C=2C=CC=CC=2)=N1 HLOHVVZZMMMDMM-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- ZRPFJAPZDXQHSM-UHFFFAOYSA-L 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole;dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C ZRPFJAPZDXQHSM-UHFFFAOYSA-L 0.000 claims 1
- 239000011987 hoveyda–grubbs catalyst Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 150000001408 amides Chemical class 0.000 abstract description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 2
- 125000002252 acyl group Chemical class 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229930014626 natural product Natural products 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JEOLWVGGGFZWHS-UHFFFAOYSA-N 3-(4-chlorophenyl)-1,2-oxazole Chemical compound C1=CC(Cl)=CC=C1C1=NOC=C1 JEOLWVGGGFZWHS-UHFFFAOYSA-N 0.000 description 1
- SFILZUIMJFKTHM-UHFFFAOYSA-N 3-cyclohexyl-3-oxopropanenitrile Chemical compound N#CCC(=O)C1CCCCC1 SFILZUIMJFKTHM-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention relates to a method for synthesizing 2H-azacyclo-acrylamide, which comprises the steps of adding 5-aminoisoxazole raw materials into a reaction solvent, adding a Holovad-Glabra catalyst, carrying out catalytic reaction under green light illumination, removing the reaction solvent from the obtained reaction liquid, and then purifying to obtain the product. The synthesis method of the invention has the advantages of very mild and green conditions, high yield and wide applicable substrate range, for example, 2-bit of the three-membered ring of the 2H-azaenamide can be various substituted phenyl, heterocyclic ring, olefin and alkane, 3-bit can be methyl, allyl, phenyl and 1-phenylallyl, and the amide can be substituted by aromatic hydrocarbon substituted amine, alkane and acyl.
Description
Technical Field
The invention relates to a method for synthesizing a 2H-azacyclo-acrylamide derivative, belonging to the technical field of organic synthesis methodology.
Background
The 2H-azacyclopropene structure in the 2H-azacyclopropene amide derivative exists in a plurality of natural products and is a common framework of a plurality of natural product drugs. Such as:
2H-azacyclopropene, a class of highly reactive compounds, has its structure in many natural products and drugs. In organic synthesis, 2H-azacyclopropene can be used as a reaction intermediate and also can be used as a reaction precursor to synthesize various useful heterocyclic compounds, such as pyridines, furans, pyrroles and indoles. At present, three methods are mainly used for synthesizing 2H-azacyclo-acrylamide, namely ultraviolet illumination, high-temperature heating and ferrous chloride catalysis of isoxazole shrinkage. 2H-azacyclopropene is synthesized by an ultraviolet illumination method, the yield is very low, and the applicable substrate range is small; the 2H-aziridine is synthesized by a high-temperature heating method, the temperature is higher and is usually between 100 and 300 ℃, and the applicable substrate range is small; the ferrous chloride is used for catalyzing isoxazole to condense and synthesize 2H-azacyclopropene, and although the yield is high, the applicable substrate range is small.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for synthesizing 2H-azacyclo-acrylamide, which has the advantages of mild conditions, wide applicable substrate range and high yield.
Technical scheme
A method for synthesizing 2H-azacyclo acrylamide comprises the following steps: adding 5-aminoisoxazole raw materials into a reaction solvent, adding a Holeda-Glabra catalyst, carrying out catalytic reaction under green light illumination, removing the reaction solvent from the obtained reaction liquid, and then purifying to obtain the product.
Further, the 5-aminoisoxazole starting material is selected from the group consisting of 3-octyliso-5-aminooxazole, 3-cyclohexyl-5-aminoisoxazole
Oxazole, 3-phenylpropyl-5-aminoisoxazole, 3-cinnamyl-5-aminoisoxazole, 3-phenyl-5-aminoisoxazole, 3- (4-chlorophenyl) -5-aminoisoxazole, 3- (4-bromophenyl) -5-aminoisoxazole, 3- (2-naphthyl) -5-aminoisoxazole, 3- (2-furyl) -5-aminoisoxazole, 3-phenyl-4-allyl-5-aminoisoxazole, 3-phenyl-4- (1-phenylallyl) -5-aminoisoxazole, 3-phenyl-5- (N-benzylamino) isoxazole, or 3-phenyl-5- (N-octylamino) isoxazole .
Further, the reaction solvent is selected from any one of absolute ethyl alcohol, acetonitrile, 1, 2-dichloroethane, dichloromethane, toluene or isopropanol. Preferably anhydrous ethanol.
Further, the hoveyda-glauber catalyst is dichloro (o-isopropoxyphenylmethylene) (tricyclohexylphosphine) ruthenium or dichloro [1, 3-bis (2-methylphenyl) -2-imidazolidinylidene ] (2-isopropoxybenzylidene) ruthenium.
Further, the catalytic reaction is carried out under a 36w green light lamp, and the reaction time is 24-72 h.
Further, the method for removing the reaction solvent is to use a vacuum rotary evaporator.
Further, the purification adopts column chromatography, and the developing solvent is dichloromethane/ethyl acetate 4: 1.
the invention has the beneficial effects that: the synthesis method of the invention has the advantages of very mild and green conditions, high yield and wide applicable substrate range, for example, 2-bit of the three-membered ring of the 2H-azaenamide can be various substituted phenyl, heterocyclic ring, olefin and alkane, 3-bit can be methyl, allyl, phenyl and 1-phenylallyl, and the amide can be substituted by aromatic hydrocarbon substituted amine, alkane and acyl.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 3-cyclohexyl-5-aminoisoxazole;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of 3-cyclohexyl-5-aminoisoxazole;
FIG. 3 is a NMR spectrum of 2-cyclohexyl-2H-azacyclo-acrylamide obtained in example 1;
FIG. 4 is a NMR carbon spectrum of 2-cyclohexyl-2H-azacyclic acrylamide obtained in example 1.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
Step one, synthesizing a raw material 3-cyclohexyl-5-aminoisoxazole:
sodium acetate (2mmol) and hydroxylamine hydrochloride (2mmol) were added to a 10ml reaction tube, and 1ml of methanol was added thereto with stirring
After stirring for one hour, a solution of cyclohexylformylacetonitrile (1mmol) in methanol (1ml) was added and the mixture was stirred for 12 to 24 hours. After TLC monitoring the reaction was complete, the reaction was transferred to a 100ml round bottom flask, methanol was removed using a vacuum rotary evaporator, 20ml of water was added, extraction was performed three times with ethyl acetate, 10ml of ethyl acetate each time, the organic layers were combined, washed with 20ml of saturated brine, the organic layer was dried over anhydrous sodium sulfate, ethyl acetate was removed using a vacuum rotary evaporator, the product was isolated by column chromatography, and the developing solvent polar petroleum ether/ethyl acetate was 4: 1, product is a pale yellow solid, yield 80%.
The hydrogen nuclear magnetic resonance spectrum of 3-cyclohexyl-5-aminoisoxazole is shown in FIG. 1, and the carbon nuclear magnetic resonance spectrum of 3-cyclohexyl-5-aminoisoxazole is shown in FIG. 2.
Secondly, synthesizing 2-cyclohexyl-2H-azacyclo acrylamide:
to a 10ml reaction tube was added 3-cyclohexyl-5-aminoisoxazole (1mmol), 2ml anhydrous ethanol was added, dichloro [1, 3-bis (2-methylphenyl) -2-imidazolidinylidene ] (2-isopropoxybenzylidene) ruthenium (1 mol%) was added, the mixture was irradiated with a 36W green light for 48 hours, after completion of the reaction was monitored by TLC, the reaction solution was transferred to a 100ml round-bottomed flask, ethanol was removed by a vacuum rotary evaporator, and the product was isolated by column chromatography using dichloromethane/ethyl acetate as a developing solvent 4: 1, product is a white solid in 95% yield.
The hydrogen nuclear magnetic resonance spectrum of the obtained product 2-cyclohexyl-2H-azacyclo-acrylamide is shown in figure 3, and the carbon nuclear magnetic resonance spectrum of the 2-cyclohexyl-2H-azacyclo-acrylamide is shown in figure 4.
Example 2
To a 10ml reaction tube was added 3-phenylpropyl-5-aminoisoxazole (1mmol), 2ml absolute ethanol was added, dichloro (o-isopropoxyphenylmethylene) (tricyclohexylphosphine) ruthenium (1 mol%) was added, and after 36W green light lamp irradiation for 36 hours and TLC monitoring of completion of the reaction, the reaction solution was transferred to a 100ml round-bottomed flask, ethanol was removed using a vacuum rotary evaporator, and the product was isolated by column chromatography using dichloromethane/ethyl acetate as a developing solvent 4: 1, product is a white solid in 89% yield.
Example 3
To a 10ml reaction tube was added 3- (4-chlorophenyl) isoxazole (1mmol), 2ml anhydrous ethanol was added, dichloro [1, 3-bis (2-methylphenyl) -2-imidazolidinylidene ] (2-isopropoxybenzylidene) ruthenium (1 mol%) was added, and after completion of the reaction was monitored by TLC, the reaction solution was transferred to a 100ml round-bottomed flask, ethanol was removed by a vacuum rotary evaporator, and the product was isolated by column chromatography using dichloromethane/ethyl acetate as a developing solvent ═ 4: 1, product is a white solid in 92% yield.
Example 4
To a 10ml reaction tube was added 3-phenyl-4-allyl-5-aminoisoxazole (1mmol), dichloromethane 2ml was added, dichloro [1, 3-bis (2-methylphenyl) -2-imidazolidinylidene ] (2-isopropoxybenzylidene) ruthenium (1 mol%) was added, irradiation was performed with a 36W green light for 40 hours, TLC monitored for completion of the reaction, the reaction solution was transferred to a 100ml round-bottomed flask, ethanol was removed using a vacuum rotary evaporator, and the product was isolated by column chromatography using dichloromethane/ethyl acetate as a developing agent: 1, product is a white solid in 87% yield.
Example 5
To a 10ml reaction tube was added 3-phenyl-5- (N-benzylamino) isoxazole (1mmol), 2ml anhydrous ethanol was added, dichloro [1, 3-bis (2-methylphenyl) -2-imidazolidinylidene ] (2-isopropoxybenzylidene) ruthenium (1 mol%) was added, and after completion of the reaction was monitored by TLC using 36W green light for 30 hours, the reaction solution was transferred to a 100ml round-bottomed flask, ethanol was removed by a vacuum rotary evaporator, and the product was isolated by column chromatography using dichloromethane/ethyl acetate as a developing agent (4: 1, product is a white solid in 90% yield.
Claims (5)
1. A method for synthesizing 2H-azacyclo acrylamide is characterized in that 5-aminoisoxazole raw material is added into a reaction solvent, a Heveda-Glabra catalyst is added, catalytic reaction is carried out under green light illumination, and the obtained reaction solution is purified after the reaction solvent is removed to obtain the product;
the 5-aminoisoxazole is selected from 3-octyliso-5-aminooxazole, 3-cyclohexyl-5-aminoisoxazole, 3-phenylpropyl-5-aminoisoxazole, 3-cinnamyl-5-aminoisoxazole, 3-phenyl-5-aminoisoxazole, 3- (4-chlorophenyl) -5-aminoisoxazole, 3- (4-bromophenyl) -5-aminoisoxazole, 3- (2-naphthyl) -5-aminoisoxazole, 3- (2-furyl) -5-aminoisoxazole, 3-phenyl-4-allyl-5-aminoisoxazole, 3-phenyl-4- (1-phenylallyl) -5-aminoisoxazole, phenylthio-5-, Any one of 3-phenyl-5- (N-benzylamino) isoxazole and 3-phenyl-5- (N-octylamino) isoxazole;
the catalytic reaction is carried out under a 36w green light lamp, and the reaction time is 24-72 h.
2. The method for synthesizing 2H-azacyclo-acrylamide according to claim 1, wherein the reaction solvent is selected from any one of absolute ethanol, acetonitrile, 1, 2-dichloroethane, dichloromethane, toluene or isopropanol.
3. The method of synthesizing 2H-azacyclylamides of claim 1, wherein the hoveyda-grubbs catalyst is dichloro (o-isopropoxyphenylmethylene) (tricyclohexylphosphine) ruthenium or dichloro [1, 3-bis (2-methylphenyl) -2-imidazolidinylidene ] (2-isopropoxybenzylidene) ruthenium.
4. The method of claim 1, wherein the reaction solvent is removed by a vacuum rotary evaporator.
5. The method of any one of claims 1 to 4, wherein the purification is performed by column chromatography using dichloromethane/ethyl acetate 4: 1.
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