CN116444459A - Preparation method of functionalized allylamine compound - Google Patents
Preparation method of functionalized allylamine compound Download PDFInfo
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- CN116444459A CN116444459A CN202210969530.1A CN202210969530A CN116444459A CN 116444459 A CN116444459 A CN 116444459A CN 202210969530 A CN202210969530 A CN 202210969530A CN 116444459 A CN116444459 A CN 116444459A
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- functionalized
- allylamine
- copper
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- VVJKKWFAADXIJK-UHFFFAOYSA-N allylamine Natural products NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 allylamine compound Chemical class 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 20
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- GGDYAKVUZMZKRV-UHFFFAOYSA-N 2-fluoroethanol Chemical compound OCCF GGDYAKVUZMZKRV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- FXWFZIRWWNPPOV-UHFFFAOYSA-N 2-aminobenzaldehyde Chemical compound NC1=CC=CC=C1C=O FXWFZIRWWNPPOV-UHFFFAOYSA-N 0.000 claims description 2
- NDOPHXWIAZIXPR-UHFFFAOYSA-N 2-bromobenzaldehyde Chemical compound BrC1=CC=CC=C1C=O NDOPHXWIAZIXPR-UHFFFAOYSA-N 0.000 claims description 2
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 claims description 2
- ZWDVQMVZZYIAHO-UHFFFAOYSA-N 2-fluorobenzaldehyde Chemical compound FC1=CC=CC=C1C=O ZWDVQMVZZYIAHO-UHFFFAOYSA-N 0.000 claims description 2
- WWKKTHALZAYYAI-UHFFFAOYSA-N 2-iodobenzaldehyde Chemical compound IC1=CC=CC=C1C=O WWKKTHALZAYYAI-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 claims description 2
- JIDMEYQIXXJQCC-UHFFFAOYSA-L copper;2,2,2-trifluoroacetate Chemical compound [Cu+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F JIDMEYQIXXJQCC-UHFFFAOYSA-L 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 2
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000005885 boration reaction Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 230000001360 synchronised effect Effects 0.000 abstract description 2
- 238000005990 Petasis reaction Methods 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 32
- 238000001228 spectrum Methods 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000004440 column chromatography Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 150000004658 ketimines Chemical class 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RVDOYUFNRDGYGU-UHFFFAOYSA-N 1-bromo-2-ethynylbenzene Chemical group BrC1=CC=CC=C1C#C RVDOYUFNRDGYGU-UHFFFAOYSA-N 0.000 description 1
- DGLHLIWXYSGYBI-UHFFFAOYSA-N 1-chloro-2-ethynylbenzene Chemical group ClC1=CC=CC=C1C#C DGLHLIWXYSGYBI-UHFFFAOYSA-N 0.000 description 1
- QXSWHQGIEKUBAS-UHFFFAOYSA-N 1-ethynyl-4-fluorobenzene Chemical group FC1=CC=C(C#C)C=C1 QXSWHQGIEKUBAS-UHFFFAOYSA-N 0.000 description 1
- LWISLHRIEATKTM-UHFFFAOYSA-N 2-Ethynylthiophene Chemical group C#CC1=CC=CS1 LWISLHRIEATKTM-UHFFFAOYSA-N 0.000 description 1
- 240000006915 Petasites Species 0.000 description 1
- 102000011011 Sphingosine 1-phosphate receptors Human genes 0.000 description 1
- 108050001083 Sphingosine 1-phosphate receptors Proteins 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000006907 apoptotic process Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000004030 hiv protease inhibitor Substances 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- 229960003444 immunosuppressant agent Drugs 0.000 description 1
- 239000003018 immunosuppressive agent Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000004112 neuroprotection Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- USGIERNETOEMNR-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO.CCCO USGIERNETOEMNR-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/096—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a functionalized allylamine compound, which comprises the steps of dissolving alkyne, pinacol ester biborate, aldehyde derivatives, morpholine, copper catalyst and inorganic salt in an organic solvent, and heating for reaction to obtain a target product. The invention realizes the synchronous reaction of metal catalyzed alkyne boration and Petasis reaction under a mild condition by an atomic economical one-pot method in one step, and compared with the common compound synthesis method, the method has the advantages of few steps, simple operation, mild reaction, good selectivity, high yield, wide substrate application range, large-scale synthesis, simple post-treatment and recycling capability of the solvent.
Description
Technical Field
The invention belongs to the technical field of organic compound synthesis, and particularly relates to a preparation method of a functional allylamine compound.
Background
Polyfunctional substituted allylamines are a very important class of organic compounds that are widely found in many natural products and drug molecules with important physiological activities. Such as HIV protease inhibitors, ligands for sphingosine-1-phosphate receptors that affect cell growth, apoptosis and immune function, and compounds for neuroprotection, and immunosuppressants, all contain polyfunctional substituted allylamine structures. In addition, the polyfunctional group substituted allylamine is an important organic synthesis intermediate, and can be effectively converted into substances such as beta or gamma-amino acid, piperidine and the like.
At present, two methods exist for preparing the compounds, namely, ketimine and allyl reagent are utilized to carry out nucleophilic addition reaction; secondly, ketone and amine are used for generating ketimine in situ, and then the ketimine is subjected to addition reaction with an allyl reagent. All the methods need active metal organic reagents such as format reagents, organic zinc reagents, organic indium reagents and the like, and the organic metal reagents are not stable enough, are not easy to store, are inconvenient to operate and have high risk, and meanwhile, the reaction needs to be carried out under the low-temperature condition, so that the method is extremely inconvenient.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
One of the purposes of the invention is to provide a preparation method of a functionalized allylamine compound, which has the characteristics of few steps, simple operation, mild reaction, good selectivity, high yield and the like.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a functionalized allylamine compound comprises dissolving alkyne shown in a formula I, pinacol diboronate shown in a formula II, aldehyde derivative shown in a formula III, morpholine shown in a formula IV, copper catalyst and inorganic salt in an organic solvent, and heating for reaction to obtain a compound shown in a formula V;
wherein in the formula I and the formula V, R 1 One of hydrogen atom, alkyl, alkoxy, halogen substituent, cyano, nitro, aldehyde group, ester group and silicon group; r is R 2 One selected from hydrogen atom, alkyl and aryl;
in formula III and formula V, R 3 One selected from hydrogen atom, alkyl group, alkoxy group, halogen substituentA kind of module is assembled in the module and the module is assembled in the module.
As a preferred embodiment of the process for the preparation of the functionalized allylamine-based compounds of the invention, wherein: the molar ratio of alkyne, pinacol biborate, aldehyde derivative, morpholine, copper catalyst, inorganic salt copper catalyst and inorganic salt is 1:1 to 5: 1-5:1-10: 0.01 to 0.5:1 to 5; the preferred molar ratio is 1.0:1.5:2.0:2.0:0.2:1.
As a preferred embodiment of the process for the preparation of the functionalized allylamine-based compounds of the invention, wherein: the alkyne is selected from one of aromatic alkyne, aliphatic alkyne, alkynyl thioether, alkynylamine and alkyne halogen; aromatic alkynes are preferred.
As a preferred embodiment of the process for the preparation of the functionalized allylamine-based compounds of the invention, wherein: the aldehyde derivative is selected from one of benzaldehyde, o-hydroxybenzaldehyde, o-aminobenzaldehyde, o-fluorobenzaldehyde, o-bromobenzaldehyde, o-chlorobenzaldehyde and o-iodobenzaldehyde; preferably o-hydroxybenzaldehyde.
As a preferred embodiment of the process for the preparation of the functionalized allylamine-based compounds of the invention, wherein: the copper catalyst is one of copper powder, copper oxide, cuprous oxide, copper acetate, cuprous chloride, copper trifluoroacetate, copper trifluoromethanesulfonate, copper triphenylphosphonium chloride, copper 2-thiophenecanoate, copper (I) tetraacetonitrile hexafluorophosphate and copper (II) phthalocyanine; copper powder is preferred.
As a preferred embodiment of the process for the preparation of the functionalized allylamine-based compounds of the invention, wherein: the inorganic salt is selected from one of sodium methoxide, potassium methoxide, lithium methoxide, sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, potassium phosphate, sodium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, potassium acetate and sodium acetate; sodium methoxide is preferred.
As a preferred embodiment of the process for the preparation of the functionalized allylamine-based compounds of the invention, wherein: the organic solvent is one or more of methanol, ethanol, propanol, tertiary butanol and 2-fluoroethanol; preferably the solvent is methanol.
As a preferred embodiment of the process for the preparation of the functionalized allylamine-based compounds of the invention, wherein: the mass volume ratio of the alkyne to the organic solvent is 1g: 50-100 mL, preferably 1g mass/volume ratio: 60mL.
As a preferred embodiment of the process for the preparation of the functionalized allylamine-based compounds of the invention, wherein: the heating reaction is carried out, the heating temperature is 50-120 ℃, and the heating time is 4-48 h; preferably, the heating temperature is 60 ℃ and the heating time is 12 hours.
As a preferred embodiment of the process for the preparation of the functionalized allylamine-based compounds of the invention, wherein: further comprises the step of purifying the obtained target product.
As a preferred embodiment of the process for the preparation of the functionalized allylamine-based compounds of the invention, wherein: the purification is carried out, the solvent is removed, then the separation and the purification are carried out, the water is added and stirred for 3 to 5min after the organic solvent is removed, the ethyl acetate is used for extraction, and the column chromatography is carried out after the organic phase is dried.
Compared with the prior art, the invention has the following beneficial effects:
the method realizes the synchronous progress of copper-catalyzed alkyne boration and petasites reaction under relatively mild conditions by an atomic economical one-pot method, and has the advantages of fewer steps, simple operation, mild reaction, good selectivity, high yield, wide substrate application range, large-scale synthesis, simple post-treatment and recycling of the solvent compared with the common compound synthesis method.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 2- (1-morpholino-1-styryl) phenol obtained as a product of example 1 of the present invention;
FIG. 2 shows the nuclear magnetic resonance spectrum of 2- (1-morpholino-1-styryl) phenol obtained as a product in example 1 of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Unless otherwise indicated, all starting materials used in the examples were commercially available.
Example 1
10mg (0.1 mmol) of phenylacetylene, 38mg (0.15 mmol) of dipinacol diboronate, 1mg (0.02 mmol) of copper powder and 5mg (0.1 mmol) of sodium methoxide are added into a 10mL reaction bottle, 1mL of methanol is added, the mixture is heated to 60 ℃ and stirred for reaction for 4 hours, a mixture of 24mg (0.2 mmol) of o-hydroxybenzaldehyde and 16mg (0.2 mmol) of morpholine is added for continuous reaction for 8 hours, after the reaction is finished, the mixture is cooled to room temperature, 10mL of ethyl acetate is added, 5mL of water is added for extraction, an organic phase is dried by anhydrous sodium sulfate, and light yellow liquid is obtained through column chromatography.
The weight of the product obtained by column chromatography was weighed and compared with the weight of the raw materials put into the reaction to obtain the yield, yield = weight of the product/mass of the product after the raw materials were completely reacted theoretically. The weight of the obtained product was 24mg, and the yield was 81%.
And (3) performing nuclear magnetic resonance detection on the product, and characterizing the product, wherein a nuclear magnetic resonance hydrogen spectrum and a carbon spectrum are respectively shown in figures 1 and 2:
the nuclear magnetic resonance hydrogen spectrum data are: 1 H NMR(400MHz,CDCl3)δ7.40(d,J＝6.7Hz,2H),7.33(t,J＝6.6Hz,2H),7.27(s,1H),7.20(s,1H),7.05(d,J＝7.3Hz,1H),6.88(d,J＝7.9Hz,1H),6.82(t,J＝6.9Hz,1H),6.64(d,J＝15.8Hz,1H),6.43–6.32(m,1H),4.08(d,J＝8.0Hz,1H),3.79(s,4H),2.72-2.63(b,4H).
the nuclear magnetic resonance carbon spectrum data are: 13 C NMR(101MHz,CDCl 3 )δ156.42,136.14,134.03,129.05,128.75,128.64,128.08,126.61,126.06,124.01,119.77,116.69,74.16,66.96,51.27.
according to the hydrogen spectrum and the carbon spectrum, the product which can be definitely obtained is 2- (1-morpholinyl-1-styryl) phenol, and the structural formula of the product is as follows:
example 2
Example 2 is essentially the same as example 1, except that the reaction temperature, reaction time, and reaction solvent are different, as shown in table 1 below:
TABLE 1
| Reaction temperature (. Degree. C.) | Reaction time (h) | Solvent(s) | Yield (%) |
| 25 | 12 | Methanol | 41 |
| 80 | 12 | Methanol | 75 |
| 100 | 12 | Methanol | 61 |
| 60 | 4 | Methanol | 32 |
| 60 | 20 | Methanol | 80 |
| 60 | 12 | Ethanol | 77 |
| 60 | 12 | Propanol (propanol) | 58 |
| 60 | 12 | Tert-butanol | 44 |
| 60 | 12 | 2-fluoroethanol | 33 |
As can be seen from Table 1, under the same reaction conditions, the yields were high using solvents such as ethanol, propanol, t-butanol, etc., without using methanol as the solvent. When methanol is used as a solvent, the reaction is insufficient and the efficient reaction can not be realized under the room temperature condition; the highest yield was obtained when the heating temperature was 60 ℃; the reaction temperature should not be too high, and when the reaction temperature reaches 80 ℃, the yield is rather lowered.
When the heating temperature is 60 ℃, the reaction time is properly prolonged, the yield is gradually increased, and when the heating time is set to 12 hours, the yield of the obtained product is highest; however, the reaction time should not be too long, and the yield does not increase significantly when the reaction time reaches 20 hours.
Example 3
Example 3 was identical to example 1, except that the molar ratios of phenylacetylene, dipinacol diboronate, aldehyde, morpholine, copper catalyst, inorganic salts were varied as shown in table 2 below:
TABLE 2
As can be seen from table 2, when other conditions are the same, only the molar ratio of the substances is changed, the molar ratio phenylacetylene used: bis-pinacolato diboronate: aldehyde: morpholine: copper powder: sodium methoxide=1.0:1.5:2.0:2.0:0.2:1.0 is the optimal molar ratio at which the highest yields of product are obtained, which is the preferred starting molar ratio.
Example 4
Taking 12mg (0.1 mmol) of p-tolane, 38mg (0.15 mmol) of dipinacol diboronate, 1mg (0.02 mmol) of copper powder and 5mg (0.1 mmol) of sodium methoxide, adding into a 10mL reaction bottle, adding 1mL of methanol, heating to 60 ℃, stirring for reaction for 4h, adding a mixed solution of 24mg (0.2 mmol) of o-hydroxybenzaldehyde and 16mg (0.2 mmol) of morpholine, continuing to react for 8h, cooling to room temperature after the reaction is finished, adding 10mL of ethyl acetate, extracting with 5mL of water, drying an organic phase with anhydrous sodium sulfate, and obtaining a pale yellow liquid through column chromatography.
The weight of the product obtained by column chromatography was weighed and compared with the weight of the raw materials put into the reaction to obtain the yield, yield = weight of the product/mass of the product after the raw materials were completely reacted theoretically. The weight of the obtained product was 24mg, and the yield was 79%.
Nuclear magnetic resonance detection is performed on the product, and the product is characterized:
the nuclear magnetic resonance hydrogen spectrum data are: 1 H NMR(600MHz,CDCl3)δ7.26(d,J＝8.0Hz,2H),7.16(t,J＝7.8Hz,1H),7.10(d,J＝7.9Hz,2H),7.01(d,J＝7.5Hz,1H),6.84(d,J＝8.1Hz,1H),6.78(t,J＝7.4Hz,1H),6.57(d,J＝15.7Hz,1H),6.29(dd,J＝15.7,8.6Hz,1H),4.03(d,J＝8.6Hz,1H),3.75(s,4H),2.58(b,4H),2.32(s,3H).
the nuclear magnetic resonance carbon spectrum data are: 13 C NMR(100MHz,Chloroform-d)δ156.43,138.01,133.97,133.36,129.33,128.98,128.76,126.52,124.93,124.15,119.73,116.66,74.17,66.98,51.19,21.23.
according to the hydrogen spectrum and the carbon spectrum, the product which can be definitely obtained is 2- (1-morpholinyl-1-p-methylstyrene) phenol, and the structural formula of the product is as follows:
example 5
Taking 12mg (0.1 mmol) of p-fluorophenylacetylene, 38mg (0.15 mmol) of bippinacol diboronate, 1mg (0.02 mmol) of copper powder and 5mg (0.1 mmol) of sodium methoxide, adding into a 10mL reaction bottle, adding 1mL of methanol, heating to 60 ℃, stirring for reaction for 4 hours, adding a mixed solution of 24mg (0.2 mmol) of o-hydroxybenzaldehyde and 16mg (0.2 mmol) of morpholine, continuing to react for 8 hours, cooling to room temperature after the reaction is finished, adding 10mL of ethyl acetate, extracting with 5mL of water, drying an organic phase with anhydrous sodium sulfate, and obtaining a pale yellow liquid through column chromatography.
The weight of the product obtained by column chromatography was weighed and compared with the weight of the raw materials put into the reaction to obtain the yield, yield = weight of the product/mass of the product after the raw materials were completely reacted theoretically. The weight of the obtained product was 28mg, and the yield was 89%.
Nuclear magnetic resonance detection is performed on the product, and the product is characterized:
the nuclear magnetic resonance hydrogen spectrum data are: 1 H NMR(600MHz,CDCl 3 )δ7.52–7.47(m,1H),7.37–7.32(m,1H),7.22–7.15(m,3H),7.03(dd,J＝13.4,8.4Hz,2H),6.85(d,J＝7.5Hz,1H),6.81(td,J＝7.5,0.9Hz,1H),6.34(dd,J＝15.7,8.6Hz,1H),4.11(d,J＝8.6Hz,1H),3.77(s,4H),2.62(b,4H).
the nuclear magnetic resonance carbon spectrum data are: 13 C NMR(151MHz,CDCl 3 )δ162.54(d,J＝249.1Hz),156.35,132.74,132.31(d,J＝3.4Hz),129.09,128.71,128.17(d,J＝9.0Hz),125.90(d,J＝1.5Hz),123.96,119.81,116.74,115.57(d,J＝21.1Hz),74.17,66.94,51.32.
according to the hydrogen spectrum and the carbon spectrum, the product which can be definitely obtained is 2- (1-morpholinyl-1-p-fluorostyryl) phenol, and the structural formula of the product is as follows:
example 6
18mg (0.1 mmol) of o-bromophenylacetylene, 38mg (0.15 mmol) of bippinacol diboronate, 1mg (0.02 mmol) of copper powder and 5mg (0.1 mmol) of sodium methoxide are taken and added into a 10mL reaction bottle, 1mL of methanol is added, the mixture is heated to 60 ℃ and stirred for reaction for 4 hours, a mixture of 24mg (0.2 mmol) of o-hydroxybenzaldehyde and 16mg (0.2 mmol) of morpholine is added for continuous reaction for 8 hours, after the reaction is finished, the mixture is cooled to room temperature, 10mL of ethyl acetate is added, 5mL of water is added for extraction, an organic phase is dried by anhydrous sodium sulfate, and a pale yellow liquid is obtained through column chromatography.
The weight of the product obtained by column chromatography was weighed and compared with the weight of the raw materials put into the reaction to obtain the yield, yield = weight of the product/mass of the product after the raw materials were completely reacted theoretically. The weight of the obtained product was 27mg, and the yield was 73%.
Nuclear magnetic resonance detection is performed on the product, and the product is characterized:
the nuclear magnetic resonance hydrogen spectrum data are: 1 H NMR(600MHz,CDCl 3 )δ11.02(s,1H),7.53(dd,J＝8.0,1.0Hz,1H),7.47(dd,J＝7.8,1.5Hz,1H),7.22(t,J＝7.3Hz,1H),7.18(td,J＝8.1,1.6Hz,1H),7.09(td,J＝7.8,1.6Hz,1H),7.04(dd,J＝7.6,1.5Hz,1H),6.97(d,J＝15.6Hz,1H),6.85(dd,J＝8.1,0.9Hz,1H),6.81(td,J＝7.4,1.1Hz,1H),6.29(dd,J＝15.6,6.0Hz,1H),4.12(d,J＝6.0Hz,1H),3.76(s,4H),2.60(bs,4H).
the nuclear magnetic resonance carbon spectrum data are: 13 C NMR(151MHz,CDCl 3 )δ156.42,136.05,132.98,132.74,129.31,129.31,129.17,128.85,127.54,127.29,123.67,123.63,119.88,116.75,73.98,66.95,51.28.
according to the hydrogen spectrum and the carbon spectrum, the product which can be definitely obtained is 2- (1-morpholinyl-1-o-bromostyryl) phenol, and the structural formula of the product is as follows:
example 7
14mg (0.1 mmol) of o-chlorophenylacetylene, 38mg (0.15 mmol) of dippinacol diboronate, 1mg (0.02 mmol) of copper powder and 5mg (0.1 mmol) of sodium methoxide are taken and added into a 10mL reaction bottle, 1mL of methanol is added, the mixture is heated to 60 ℃ and stirred for reaction for 4 hours, a mixture of 24mg (0.2 mmol) of o-hydroxybenzaldehyde and 16mg (0.2 mmol) of morpholine is added for continuous reaction for 8 hours, after the reaction is finished, the mixture is cooled to room temperature, 10mL of ethyl acetate is added, 5mL of water is added for extraction, an organic phase is dried by anhydrous sodium sulfate, and light yellow liquid is obtained through column chromatography.
The weight of the product obtained by column chromatography was weighed and compared with the weight of the raw materials put into the reaction to obtain the yield, yield = weight of the product/mass of the product after the raw materials were completely reacted theoretically. The weight of the obtained product was 27mg, and the yield was 81%.
Nuclear magnetic resonance detection is performed on the product, and the product is characterized:
the nuclear magnetic resonance hydrogen spectrum data are: 1 H NMR(600MHz,CDCl 3 )δ11.02(s,1H),7.53(dd,J＝8.0,1.0Hz,1H),7.47(dd,J＝7.8,1.5Hz,1H),7.22(t,J＝7.3Hz,1H),7.18(td,J＝8.1,1.6Hz,1H),7.09(td,J＝7.8,1.6Hz,1H),7.04(dd,J＝7.6,1.5Hz,1H),6.97(d,J＝15.6Hz,1H),6.85(dd,J＝8.1,0.9Hz,1H),6.81(td,J＝7.4,1.1Hz,1H),6.29(dd,J＝15.6,6.0Hz,1H),4.12(d,J＝6.0Hz,1H),3.76(s,4H),2.60(bs,4H).
the nuclear magnetic resonance carbon spectrum data are: 13 C NMR(151MHz,CDCl 3 )δ156.42,136.05,132.98,132.74,129.31,129.31,129.17,128.85,127.54,127.29,123.67,123.63,119.88,116.75,73.98,66.95,51.28.
according to the hydrogen spectrum and the carbon spectrum, the product which can be definitely obtained is 2- (1-morpholinyl-1-o-chlorostyryl) phenol, and the structural formula of the product is as follows:
example 8
18mg (0.1 mmol) of 2-thiophenylacetylene, 38mg (0.15 mmol) of bippinacol diboronate, 1mg (0.02 mmol) of copper powder and 5mg (0.1 mmol) of sodium methoxide are added into a 10mL reaction bottle, 1mL of methanol is added, the mixture is heated to 60 ℃ and stirred for reaction for 4 hours, a mixture of 24mg (0.2 mmol) of o-hydroxybenzaldehyde and 16mg (0.2 mmol) of morpholine is added for continuous reaction for 8 hours, after the reaction is finished, the mixture is cooled to room temperature, 10mL of ethyl acetate is added, 5mL of water is added for extraction, the organic phase is dried by anhydrous sodium sulfate, and light yellow liquid is obtained through column chromatography.
The weight of the product obtained by column chromatography was weighed and compared with the weight of the raw materials put into the reaction to obtain the yield, yield = weight of the product/mass of the product after the raw materials were completely reacted theoretically. The weight of the obtained product was 23mg, and the yield was 78%.
Nuclear magnetic resonance detection is performed on the product, and the product is characterized:
the nuclear magnetic resonance hydrogen spectrum data are: 1 H NMR(600MHz,CDCl 3 )δ7.19–7.14(m,2H),7.00(d,J＝6.7Hz,1H),6.97(d,J＝1.8Hz,1H),6.96–6.93(m,1H),6.85(d,J＝8.1Hz,1H),6.79(t,J＝7.4Hz,1H),6.73(d,J＝15.5Hz,1H),6.16(dd,J＝15.5,9.6Hz,1H),4.00(d,J＝9.6Hz,1H),3.76(s,4H),2.57(bs,4H).
the nuclear magnetic resonance carbon spectrum data are: 13 C NMR(151MHz,CDCl 3 )δ156.40,141.14,129.10,128.73,127.42,127.11,126.33,125.43,124.89,123.78,119.78,116.73,73.94,66.95,51.20.
according to the hydrogen spectrum and the carbon spectrum, the product which can be definitely obtained is 2- (1-morpholinyl-1-thiophenvinyl) phenol, and the structural formula of the product is as follows:
the preparation method provided by the invention has the capability of synthesizing at least one functionalized allylamine compound. According to the data of the examples, under the condition that different reaction conditions are selected, the prepared products are identical, relatively the same product can be prepared through different reaction conditions, more reaction conditions are suitable for a certain continuous target product, and a plurality of synthetic routes are provided for the generation of one product.
The synthetic route provided by the invention has the synthesis capability for various functionalized allylamine compounds, and simultaneously has the synthesis capability for the same target functionalized allylamine compound by using various raw materials, so that the conclusion is that the synthetic route provided by the invention is a functionalized allylamine compound synthesis method which can be applied to the synthesis of various functionalized allylamine compounds and uses various raw materials for synthesis, and compared with the current compound synthesis method, the synthetic route provided by the invention has the advantages of wide substrate application range and various target product types, and the application range of the synthetic route provided by the invention is enlarged.
The preparation method of the target compound has the advantages of simple process, simple and convenient steps, shorter reaction time than the conventional compound synthesis method, milder reaction conditions, simple subsequent treatment, and capability of recycling the solvent, and is suitable for mass production.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (10)
1. A method for preparing a functionalized allylamine compound, which is characterized in that: dissolving alkyne shown in a formula I, pinacol ester of biboronate shown in a formula II, aldehyde derivative shown in a formula III, morpholine shown in a formula IV, copper catalyst and inorganic salt in an organic solvent, and heating for reaction to obtain a compound shown in a formula V;
wherein in the formula I and the formula V, R 1 One of hydrogen atom, alkyl, alkoxy, halogen substituent, cyano, nitro, aldehyde group, ester group and silicon group; r is R 2 One selected from hydrogen atom, alkyl and aryl;
in formula III and formula V, R 3 One selected from hydrogen atom, alkyl, alkoxy and halogen substituent.
2. The process for the preparation of functionalized allylamine-based compounds according to claim 1, wherein: the molar ratio of alkyne, pinacol biborate, salicylaldehyde derivative, morpholine, copper catalyst, inorganic salt copper catalyst and inorganic salt is 1:1 to 5: 1-5:1-10: 0.01 to 0.5:1 to 5.
3. A process for the preparation of a functionalized allylamine-based compound according to claim 1 or 2, characterized in that: the alkyne is selected from one of aromatic alkyne, aliphatic alkyne, alkynyl thioether, alkynylamine and alkyne halogen.
4. A process for the preparation of functionalized allylamine-based compounds according to claim 3, wherein: the aldehyde derivative is selected from one of benzaldehyde, o-hydroxybenzaldehyde, o-aminobenzaldehyde, o-fluorobenzaldehyde, o-bromobenzaldehyde, o-chlorobenzaldehyde and o-iodobenzaldehyde.
5. The process for the preparation of a functionalized allylamine-based compound according to any one of claims 1, 2, 4, wherein: the copper catalyst is selected from one of copper powder, copper oxide, cuprous oxide, copper acetate, cuprous chloride, copper trifluoroacetate, copper trifluoromethanesulfonate, copper triphenylphosphonium chloride, copper 2-thiophenecanoate, copper (I) tetraacetonitrile hexafluorophosphate and copper (II) phthalocyanine.
6. The method for preparing the functionalized allylamine-based compound according to claim 5, wherein the method comprises the steps of: the inorganic salt is selected from one of sodium methoxide, potassium methoxide, lithium methoxide, sodium tert-butoxide, potassium tert-butoxide, lithium tert-butoxide, potassium phosphate, sodium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, potassium acetate and sodium acetate.
7. A process for the preparation of a functionalized allylamine-based compound according to any one of claims 1, 2, 4, 6, wherein: the organic solvent is selected from one or more of methanol, ethanol, propanol, tertiary butanol and 2-fluoroethanol.
8. The method for preparing the functionalized allylamine-based compound according to claim 7, wherein the method comprises the steps of: the mass volume ratio of the alkyne to the organic solvent is 1g: 50-100 mL.
9. A process for the preparation of a functionalized allylamine-based compound according to any one of claims 1, 2, 4, 6, 8, characterized in that: the heating reaction is carried out at the temperature of 50-120 ℃ for 4-48 h.
10. A process for the preparation of a functionalized allylamine-based compound according to any one of claims 1, 2, 4, 6, 8, characterized in that: further comprises the step of purifying the obtained compound represented by formula V.
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