CN113307726B - 一种丙炔芳基醚类化合物的制备方法和应用 - Google Patents
一种丙炔芳基醚类化合物的制备方法和应用 Download PDFInfo
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- CN113307726B CN113307726B CN202110569282.7A CN202110569282A CN113307726B CN 113307726 B CN113307726 B CN 113307726B CN 202110569282 A CN202110569282 A CN 202110569282A CN 113307726 B CN113307726 B CN 113307726B
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- propyne
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- sodium
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- -1 propyne aryl ether compound Chemical class 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 104
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 81
- 125000001072 heteroaryl group Chemical group 0.000 claims description 12
- 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 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000001624 naphthyl group 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
- 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
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 125000002015 acyclic group Chemical group 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 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
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 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
- 125000004076 pyridyl group Chemical group 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
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000011282 treatment Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical class CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 116
- 239000000047 product Substances 0.000 description 29
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 28
- 239000003480 eluent Substances 0.000 description 25
- 239000003208 petroleum Substances 0.000 description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- 239000000741 silica gel Substances 0.000 description 23
- 229910002027 silica gel Inorganic materials 0.000 description 23
- 238000010898 silica gel chromatography Methods 0.000 description 23
- XXFUZSHTIOFGNV-UHFFFAOYSA-N 1-bromoprop-1-yne Chemical compound CC#CBr XXFUZSHTIOFGNV-UHFFFAOYSA-N 0.000 description 19
- 238000001035 drying Methods 0.000 description 17
- 238000003760 magnetic stirring Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- LOFXCXMHDNGNRQ-UHFFFAOYSA-N prop-1-ynoxybenzene Chemical compound CC#COC1=CC=CC=C1 LOFXCXMHDNGNRQ-UHFFFAOYSA-N 0.000 description 7
- 125000005025 alkynylaryl group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000012230 colorless oil Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 4
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 4
- RMPSZEZJKSUNKR-UHFFFAOYSA-N 3-chloroprop-1-ynylbenzene Chemical compound ClCC#CC1=CC=CC=C1 RMPSZEZJKSUNKR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- GGMLTGPNQUTCPG-UHFFFAOYSA-N but-2-ynoxybenzene Chemical compound CC#CCOC1=CC=CC=C1 GGMLTGPNQUTCPG-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- LNNXOEHOXSYWLD-UHFFFAOYSA-N 1-bromobut-2-yne Chemical compound CC#CCBr LNNXOEHOXSYWLD-UHFFFAOYSA-N 0.000 description 2
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- BAVFPEJGAHNTOS-UHFFFAOYSA-N C(#CC)OC1=NC=CC=C1 Chemical compound C(#CC)OC1=NC=CC=C1 BAVFPEJGAHNTOS-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- LHJGJYXLEPZJPM-UHFFFAOYSA-N 2,4,5-trichlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C=C1Cl LHJGJYXLEPZJPM-UHFFFAOYSA-N 0.000 description 1
- VAPDZNUFNKUROY-UHFFFAOYSA-N 2,4,6-triiodophenol Chemical compound OC1=C(I)C=C(I)C=C1I VAPDZNUFNKUROY-UHFFFAOYSA-N 0.000 description 1
- KQDJTBPASNJQFQ-UHFFFAOYSA-N 2-iodophenol Chemical compound OC1=CC=CC=C1I KQDJTBPASNJQFQ-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- VSGACYFHLPVUQM-UHFFFAOYSA-N 4-hydroxyphthalaldehyde Chemical compound OC1=CC=C(C=O)C(C=O)=C1 VSGACYFHLPVUQM-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000006959 Williamson synthesis reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001562 benzopyrans Chemical class 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001907 coumarones Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000004309 pyranyl group Chemical class O1C(C=CC=C1)* 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/36—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/38—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/79—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
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Abstract
本发明具体涉及一种芳基酚与卤代丙炔及其衍生物制备丙炔芳基醚类化合物的方法,属于丙炔芳基醚类化合物的制备技术领域。该方法以卤代炔、芳基酚为原料,按照一定比例加入相转移催化剂和碱,在一定温度下,在水相中搅拌反应,反应结束后对产物进行分离提纯,即得所述丙炔芳基醚。该方法避免了昂贵试剂、有毒易燃的有机溶剂、复杂的氮气保护,以及操作繁琐的后处理过程、反应时间长等缺点。该合成方法试剂廉价易得,溶剂水绿色环保,反应成本低廉,反应条件温和,操作简便,反应产率较高,反应过程绿色环保,适用于工业化生产。
Description
技术领域
本发明属于丙炔芳基醚类化合物的制备技术领域,具体涉及一种芳基酚与卤代丙炔及其衍生物制备丙炔芳基醚类化合物的方法和应用。
背景技术
丙炔基芳醚可以进一步合成很多有机化合物,在有机合成中是重要的中间产物,有着非常广泛的应用。Sharpless在2005年报道了利用苯基丙炔基醚与叠氮反应合成三唑化合物[J.Chem.Educ.2005,Vol.82No.12,1833],Ishikawa在1997年报道了利用苯基丙炔基醚重排反应生成苯并呋喃以及吡喃[Heterocycles.1997,45(11),2261-2271],Worlikar在2007年报道了利用苯基丙炔基醚与I2或ICl反应生成β-取代苯并吡喃[J.Org.Chem.2007,72,1347-1353.],Wang在2012年报道了利用苯基丙炔基醚合成吡喃酮[Angew Chem Int Ed Engl.2012,51(8),1915-1918]等等。
丙炔基芳醚的反应研究最近引起了化学研究者的广泛关注与浓厚兴趣。Williamson醚合成法是卤代烃与醇/酚碱性条件下生成醚的方法,该方法是合成醚的常用方法。炔基芳醚可以采用取代苯酚与卤代炔烃反应得到。根据文献报道,大多数炔基芳醚合成在碱条件下有机溶剂中进行反应,例如K2CO3/DMF[Org.Lett.2015,17(4),964-967;Tetrahedron.2012,68(45),9179-9185.],K2CO3/actone[Bioorg.Med.Chem.Lett.2011,21(5),1338-1341;J.Agric.Food Chem.1970,18(1),78-80],K2CO3/MeCN[Tetrahedron.2012,68(45),9179-9185;Bioorg.Med.Chem.Lett.2011,21(5),1338-1341;Journal ofAgricultural&Food Chemistry 1970,18(1),78-80],Cs2CO3/DMF[Chem.Commun.2011,47(2),803-805;Eur.J.Org.Chem.2011,(12),2334-2338]或者NaH/DMF[Org.Lett.2011,13(21),5893-5895]等条件下反应。
由于上述已报道的在有机溶剂条件下的方法合成丙炔基芳醚中往往存在反应需要加热回流[J.Agric.Food Chem.1970,18(1),78-80.Chem.Commun.2011,47(2),803-805.Org.Lett.2011,13(21),5893-5895],或者需要氮气保护[Angew.Chem.Int.Edit.2012,51(8),1915-1918,Tetrahedron.2012,68(45),9179-9185.Angew.Chem.Int.Edit.2004,43(30),3928-3932.],条件苛刻,反应时间较长(8-24h)[Tetrahedron.2012,68(45),9179-9185,J.Agric.Food Chem.1970,18(1),78-80;Eur.J.Org.Chem.2011,(12),2334-2338],有的后处理中要使用易燃性液体乙醚[Org.Lett.2011,13(21),5893-5895;Chem.Commun.2012,48(1),55-57;J.HeterocyclicChem.2015,52(3),701-710;Angew.Chem.Int.Edit.2015,54(1),254-257],反应往往有些副产物生成,造成后处理麻烦,操作复杂等等缺点。因此寻找一种原料易得,操作简单、绿色环保的方法制备丙炔基芳醚,进而合成1,2,3-三氮唑类化合物,仍然是国际范围内很多研究者追求的目标。
发明内容
本发明的目的是为了解决上述现有技术的不足,提供一种水相方法制备丙炔芳基醚的方法及应用,本发明的合成方法使用的原料易得,成本低廉,反应条件温和,操作简便,产率高,反应过程绿色环保,适用于工业化生产。
本发明采用的技术方案是提供一种芳基酚与卤代丙炔及其衍生物制备丙炔芳基醚类化合物的方法,具体为以卤代炔与芳基酚为原料,按照一定比例加入相转移催化剂和碱,以水为溶剂,在一定温度下搅拌反应,反应结束后对产物进行分离提纯,即得目标产物,合成路线如下:
进一步地,R1为苯基、取代苯基、苄基、取代苄基、萘基、取代萘基、杂芳香基、取代杂芳香基中的一种。
更进一步地,R1中取代基可以是单取代、二取代以及多取代。
更进一步地,R1中取代基为下列任一基团或其任意组合:烷基、烷氧基、腈基、卤原子、硝基、醛基、酰基。
进一步地,R2为H、烷基、取代烷基、苯基、取代苯基、杂芳香基、取代杂芳香基中的一种。
更进一步地,R2中取代基可以是单取代、二取代以及多取代。
更进一步地,R1中取代基为下列任一基团或其任意组合:烷基、烷氧基、腈基、卤原子、硝基、醛基、酰基。
更进一步地,杂芳香基为呋喃基、噻吩基或吡啶基。
进一步地,X为F、Cl、Br或I。
作为优选的,X为Br或者Cl。
更进一步地,碱为无机碱中的一种:选自醋酸钠、醋酸钾、碳酸钠、碳酸钾、碳酸铯、磷酸钠、磷酸钾、氢氧化锂、氢氧化钠、氢氧化钾、氢氧化钙、甲醇钠、甲醇钾、乙醇钠、乙醇钾、叔丁醇锂、叔丁醇钠、叔丁醇钾、正丁基锂,六甲基二硅基胺基钾(KHMDS)或六甲基二硅基胺基钠(NaHMDS)中的一种。
作为优选的,采用氢氧化钠或者碳酸钾。
进一步地,本发明中相转移催化剂包括:(1)季铵盐类相转移催化剂:四烷基卤化铵(例如四丁基碘化铵(TBAI),四丁基溴化铵(TBAB),四丁基氯化铵(TBAC),四丁基氟化铵(TBAF),四乙基溴化铵(TEAB)等),十六烷基三甲基溴化铵(CTMAB),苄基三乙基氯化铵(BTEAC),三辛基甲基氯化铵(TOMAC),四丁基硫酸氢铵(TBAHS);(2)非环多醚类相转移催化剂:聚乙二醇(例如聚乙二醇-200,聚乙二醇-400,聚乙二醇-600),聚乙二醇脂肪醚(例如聚乙二醇二甲醚)。
作为优选的,相转移催化剂采用四丁基溴化铵(TBAB)或者四丁基碘化铵(TBAI)。
作为优选的,芳基酚、卤代炔、相转移催化剂和碱的摩尔比为1.0∶1.1∶1.0:1.1。
进一步地,反应时的温度为10-100℃。
作为优选的,反应时的温度为20-60℃。
本发明反应的方式可采用搅拌、微波、超声、紫外或其组合,从操作简单易行以及易于工业化角度,优选搅拌。
本发明还提供所述炔基芳醚在制备防腐剂、材料、药物中间体及化学试剂中间体中的应用。
具体的,丙炔芳基醚类化合物的制备方法制得的丙炔芳基醚类化合物在制备1,2,3-三氮唑类化合物中的应用。
在本发明中,采用TLC监控原料反应完全,反应液用乙酸乙酯或二氯甲烷萃取,有机相经饱和食盐水洗涤,无水硫酸钠干燥后,减压蒸去溶剂,即得粗产品,粗产品经石油醚和乙酸乙酯为洗脱剂进行柱层析分离提纯得到目标产物炔基芳醚类化合物,或者待反应结束后直接经石油醚和乙酸乙酯为洗脱剂进行柱层析分离提纯得到目标产物丙炔芳基醚类化合物。
与现有技术相比,本发明的有益效果:
第一:本发明使用的溶剂为水,价格便宜,来源丰富,无毒无味,绿色环保,对环境无污染;
第二:本发明反应温度温和,绝大多数均可以在室温下反应完全,避免了高温加热的麻烦和节约了能源;
第三:本发明反应可以敞开放在空气中进行,无需要额外的氮气保护;
第四:本发明的反应速度快,反应时间短,绝大多数在0.5h左右反应结束,稍长时间为1.0h-2.0h左右,节约了时间成本;
第五:本发明使用的相转移催化剂价格便宜,来源丰富,易于运输保存;
第六:本发明可以得到唯一的目标产物,反应过程中没有副产物,省去了麻烦的副产物处理过程;
第七:本发明反应后处理简单、后处理中不使用易燃性液体乙醚。
第八:反应产率较高、产物纯度较高,绿色环保,适于大量制备炔基芳醚,有较高的使用价值和社会效益。
具体实施方式
为了进一步高效快速绿色的合成炔基芳醚,本发明提供在水相中碱性条件相转移催化剂(PTC,phase transfer catalyst)催化下卤代炔与取代苯酚室温合成炔基芳醚的简便绿色的新合成方法,该方法避免了碳酸铯等昂贵试剂、有毒易燃的有机溶剂、复杂的氮气保护、操作繁琐的后处理过程,长的反应时间等缺点。该合成方法试剂廉价易得,成本低廉,反应条件温和,操作简便,反应产率较高,反应过程绿色环保,适用于工业化生产。
下面结合实施例对本发明作进一步的详细描述。
本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限定本发明的范围。
实施例1:取一个50mL圆底烧瓶,称取苯酚(0.188g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)反应30min完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基苯基醚,产率为90%。丙炔基苯基醚,无色油状物。1H NMR(400MHz,CDCl3)δ:7.35(t,J=8.0Hz,2H),7.03(t,J=8.4Hz,3H),4.73(d,J=2.4Hz,2H),2.55(t,J=2.0Hz,1H).13C NMR(100MHz,CDCl3)δ:157.6,129.6,121.6,114.9,78.6,75.5,55.7.
在同样的制备和提纯条件下,称取苯酚(1.88g,20mmol),溴代丙炔(2.62g,22mmol),称取四丁基溴化铵(6.45g,20mmol)和氢氧化钠(0.88g,22mmol)进行反应,也即是在实施例1的基础上将各原料扩大到原来的十倍,反应时间45min,同样得到丙炔基苯基醚,无色油状物,产率88%。
实施例2:取一个50mL圆底烧瓶,称取苯酚(0.188g,2.0mmol),1-溴-2-丁炔(0.2926g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)40min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物2-丁炔基苯基醚,产率为88%。2-丁炔基苯基醚,无色油状物。1H NMR(400MHz,CDCl3)δ:7.29(t,J=8.0Hz,2H),6.96(m,3H),4.62(q,J=2.4Hz,2H),1.84(t,J=2.4Hz,3H).13C NMR(100MHz,CDCl3)δ:157.8,129.4,121.3,114.8,83.6,74.1,56.3,3.7.
实施例3:取一个50mL圆底烧瓶,称取苯酚(0.188g,2.0mmol),1-苯基-3-氯-1-丙炔(0.3322g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)80min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物2-丁炔基苯基醚,产率为83%。苯丙炔基苯基醚,浅黄固体,m.p.:42-43℃。:1H NMR(400MHz,CDCl3)δ:7.51-7.49(m,2H),7.40-7.34(m,5H),7.12-7.04(m,3H),4.97(s,2H).13C NMR(100MHz,CDCl3)δ:57.8,131.8,129.5,128.7,128.3,122.3,121.4,115.0,87.1,84.0,56.6.
实施例4:取一个50mL圆底烧瓶,称取对甲基苯酚(0.216g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)25min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基(4-甲基)苯基醚,产率为93%。丙炔基(4-甲基)苯基醚,亮黄色油状物。1H NMR(400MHz,CDCl3)δ:7.14(d,J=8.4Hz,2H),6.92(d,J=7.6Hz,2H),4.69(d,J=2.4Hz,2H),4.54(t,J=2.0Hz,1H),2.34(s,3H).13C NMR(100MHz,CDCl3)δ:155.5,130.9,129.9,114.8,78.8,75.3,55.9,20.5.
实施例5:取一个50mL圆底烧瓶,称取对甲基苯酚(0.216g,2.0mmol),1-苯基-3-氯-1-丙炔(0.3322g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)50min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物苯丙炔基(4-甲基)苯基醚,产率为87%。苯丙炔基(4-甲基)苯基醚,白色固态,m.p.:60-61℃。1H NMR(400MHz,CDCl3)δ:7.35(distorted triplet,2H),7.23-7.19(m,3H),7.03(d,J=8.4Hz,2H),6.85(d,J=7.6Hz,2H),4.79(s,2H),2.21(s,3H).13C NMR(100MHz,CDCl3)δ:155.7,131.8,130.7,129.9,128.6,128.2,122.4,114.9,87.0,84.2,56.8,20.5.
实施例6:取一个50mL圆底烧瓶,称取间甲基苯酚(0.216g,2.0mmol)溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)25min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基(3-甲基)苯基醚,产率为90%。丙炔基(3-甲基)苯基醚,棕黄油状物:1H NMR(400MHz,CDCl3)δ:7.22(t,J=7.6Hz,1H),6.83(t,J=7.6Hz,1H),4.71(d,J=2.4Hz,2H),2.54(t,J=2.4Hz,1H),2.37(s,3H).13CNMR(100MHz,CDCl3)δ:157.6,139.6,129.2,122.4,115.7,111.7,78.7,75.2,55.7,21.5.
实施例7:取一个50mL圆底烧瓶,称取邻甲基苯酚(0.216g,2.0mmol)溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)35min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基(2-甲基)苯基醚,产率为85%。丙炔基(2-甲基)苯基醚,无色油状物1H NMR(400MHz,CDCl3)δ7.30(t,J=7.8Hz,2H),7.05(t,J=8.1Hz,2H),4.81(s,2H),2.61(s,1H),2.40(s,3H).13C NMR(101MHz,CDCl3)δ155.93,131.04,127.36,126.82,121.43,111.82,79.15,75.37,55.99,16.36.
实施例8:取一个50mL圆底烧瓶,称取对甲氧基苯酚(0.248g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)20min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基(4-甲氧基)苯基醚,产率为94%。丙炔基(4-甲氧基)苯基醚,无色油状物:1H NMR(400MHz,CDCl3)δ:6.95(d,J=9.2Hz,2H),6.87(d,J=9.2Hz,2H),4.66(d,J=2.0Hz,2H),3.79(s,3H),2.53(t,J=2.0Hz,1H).13C NMR(100MHz,CDCl3)δ:154.5,151.7,116.1,14.6,78.9,75.2,56.6,55.7.
实施例9:取一个50mL圆底烧瓶,称取对甲氧基苯酚(0.248g,2.0mmol),1-溴-2-丁炔(0.2926g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)43min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物2-丁炔基(4-甲氧基)苯基醚,产率为92%。2-丁炔基(4-甲氧基)苯基醚,无色油状物:1H NMR(400MHz,CDCl3)δ:6.93(d,J=9.2Hz,2H),6.86(d,J=8.8Hz,2H),4.62(s,2H),3.79(s,3H),1.88(s,3H).13C NMR(100MHz,CDCl3)δ:154.2,152.0,115.9,114.5,83.5,74.3,57.1,55.6,3.6.(20170218-3)
实施例10:取一个50mL圆底烧瓶,称取对甲氧基苯酚(0.248g,2.0mmol),1-苯基-3-氯-1-丙炔(0.3322g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)60min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物苯丙炔基(4-甲氧基)苯基醚,产率为86%。苯丙炔基(4-甲氧基)苯基醚,浅黄色固态,m.p.:75-77℃:1H NMR(400MHz,CDCl3)δ:7.46(distorted triplet,2H),7.35-7.32(m,3H),7.02(d,J=8.8Hz,2H),6.90(d,J=8.8Hz,2H),4.89(s,2H),3.81(s,3H).13C NMR(100MHz,CDCl3)δ:154.5,152.0,131.8,128.6,128.3,122.4,116.3,114.6,87.0,84.3,57.6,55.7.
实施例11:取一个50mL圆底烧瓶,称取对氯苯酚(0.258g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)40min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基(4-氯)苯基醚,产率为90%。丙炔基(4-氯)苯基醚,浅灰绿色油状物:1H NMR(400MHz,CDCl3)δ:7.28(d,J=8.8Hz,2H),6.94(d,J=8.8Hz,2H),4.69(d,J=2.4Hz,2H),2.55(t,J=2.4Hz,1H).13C NMR(100MHz,CDCl3)δ:156.1,129.4,126.6,116.3,78.2,75.8,56.1.
实施例12:取一个50mL圆底烧瓶,称取2,4,5-三氯苯酚(0.396g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)50min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基(2,4,5-三氯)苯基醚,产率为91%。丙炔基(2,4,5-三氯)苯基醚,浅黄色固态,m.p.:60-62℃:1H NMR(400MHz,CDCl3)δ:7.39(s,1H),7.10(s,1H),4.69(d,J=2.4Hz,2H),2.52(t,J=2.4Hz,1H).13C NMR(100MHz,CDCl3)δ:152.1,131.2,131.1,125.4,122.6,115.9,77.1,76.9,57.3.
实施例13:取一个50mL圆底烧瓶,称取邻溴苯酚(0.346g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)40min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基(2-溴)苯基醚,产率为93%。丙炔基(2-溴)苯基醚,浅黄色油状物。1H NMR(400MHz,CDCl3)δ7.58(d,J=8.0Hz,1H),7.30(t,J=8.0Hz,1H),7.09(d,J=8.0Hz,1H),6.91(t,J=7.6Hz,1H),4.80(s,2H),2.57(d,J=1.6Hz,1H).13C NMR(100MHz,CDCl3)δ154.04,133.60,128.39,122.91,114.27,112.46,78.06,76.23,56.87.
实施例14:取一个50mL圆底烧瓶,称取邻溴苯酚(0.346g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)120min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物苯丙炔基(2-溴)苯基醚,产率为84%。苯丙炔基(2-溴)苯基醚,浅黄色油状物。1H NMR(400MHz,CDCl3)δ:1ΗΝΜR:7.61(d,J=7.6Hz,1H),7.46(d,J=7.6Hz,2H),7.34-7.31(m,4H),7.19(d,J=8.4Hz,1H),6.92(t,J=7.6Hz,1H),5.04(s,2H).13C NMR(100MHz,CDCl3)δ:154.3,133.5,131.8,128.8,1284,128.3,122.8,122.2,114.5,112.5,87.8,83.4,57.8.
实施例15:取一个50mL圆底烧瓶,称取邻碘苯酚(0.440g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)40min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基(2-碘)苯基醚,产率为94%。丙炔基(2-碘)苯基醚,浅黄色油状物。1H NMR(400MHz,CDCl3)δ:7.77(dd,J=1.6Hz,J=8.0Hz,1H),7.29(td,J=1.6Hz,J=8.4Hz,1H),6.97(d,J=8.0Hz,1H),6.74(t,J=7.6Hz,1H),4.73(d,J=2.4Hz,2H),2.52(s,1H).13C NMR(100MHz,CDCl3)δ:156.3,139.7,129.4,123.5,113.1,86.6,78.1,76.2,56.9.
实施例16:取一个50mL圆底烧瓶,称取2,4,6-三碘苯酚(0.440g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)42min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基(2-碘)苯基醚,产率为82%。丙炔基(2,4,6-三碘)苯基醚,白色固体,m.p.:161-163℃。1H NMR(400MHz,CDCl3)δ8.08(s,2H),4.73(s,2H),2.60(s,1H).13C NMR(100MHz,CDCl3)δ157.06,147.35,92.30,90.12,77.54,76.72,60.67.
实施例17:取一个50mL圆底烧瓶,称取对硝基苯酚(0.278g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在50℃下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)120min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基(4-硝基)苯基醚,产率为78%。丙炔基(4-硝基)苯基醚,黄色固体,m.p.:112-113℃:1H NMR(400MHz,CDCl3)δ:8.15(d,J=9.2Hz,2H),6.98(d,J=9.2Hz,2H),4.73(d,J=2.4Hz,2H),2.51(t,J=2.0Hz,1H).13C NMR(100MHz,CDCl3)δ:162.3,142.2,125.8,114.9,77.1,76.7,56.3.
实施例18:取一个50mL圆底烧瓶,称取对羟基苯甲醛(0.244g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在50℃下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)100min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基(4-甲酰基)苯基醚,产率为86%。丙炔基(4-甲酰基)苯基醚,白色固体,m.p.:74-76℃:1H NMR(400MHz,CDCl3)δ:9.84(s,1H),7.79(d,J=8.8Hz,2H),7.02(d,J=8.4Hz,2H),4.71(d,J=2.4Hz,2H),2.55(t,J=2.4Hz,1H).13C NMR(100MHz,CDCl3)δ:190.7,162.4,131.8,130.6,115.2,77.5,76.3,55.9.(20170103-11)
实施例19:取一个50mL圆底烧瓶,称取邻羟基苯甲醛(0.244g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在60℃下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)120min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基(2-甲酰基)苯基醚,产率为83%。丙炔基(2-甲酰基)苯基醚,白色固体,m.p.:66-68℃:1H NMR(400MHz,CDCl3)δ:10.49(s,1H),7.87(d,J=7.6Hz,1H),7.58(m,1H),7.12-7.07(d,J=7.6Hz,1H),4.84(d,J=2.0Hz,2H),2.58(t,J=2.4Hz,1H).13C NMR(100MHz,CDCl3)δ:189.6,159.7,135.7,128.6,125.5,121.6,113.1,77.6,76.4,56.3.
实施例20:取一个50mL圆底烧瓶,称取对羟基邻甲氧基苯甲醛(0.244g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在50℃下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)80min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基(2-甲氧基-4-甲酰基)苯基醚,产率为88%。丙炔基(2-甲氧基-4-甲酰基)苯基醚,淡黄色固体,m.p.:82-83℃。1HNMR(400MHz,CDCl3)δ:9.88(s,1H),7.46(d,J=8.4Hz,1H),7.44(s,1H),7.15(d,J=8.0Hz,1H),4.86(d,J=2.4Hz,2H),3.95(s,3H),2.57(t,J=2.4Hz,1H).13C NMR(100MHz,CDCl3)δ:190.8,152.4,150.0,130.9,126.2,112.6,109.5,77.4,76.6,56.6,56.1.
实施例21:取一个50mL圆底烧瓶,称取对羟基苯乙酮(0.272g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)50min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基(4-乙酰基)苯基醚,产率为85%。丙炔基(4-乙酰基)苯基醚,淡黄色固体,m.p.:75-76℃。:1H NMR(400MHz,CDCl3)δ7.88(d,J=8.0Hz,2H),6.94(d,J=8.0Hz,2H),4.69(s,2H),2.49(s,4H).13C NMR(101MHz,CDCl3)δ196.71,161.29,131.08,130.52,114.59,77.77,76.15,55.85,26.37.
实施例22:取一个50mL圆底烧瓶,称取2-萘酚(0.288g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)90min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基2-萘基醚,产率为92%。丙炔基2-萘基醚,黄棕色固体,m.p.:70-72℃:1H NMR(400MHz,CDCl3)δ:7.69-7.66(m,3H),7.36(t,J=8.0Hz,1H),7.26(t,J=8.0Hz,1H),7.15(s,1H),7.10(dd,J=2.4Hz,J=9.2Hz,1H),4.71(d,J=2.4Hz 2H),2.46(t,J=2.4Hz 2H).13C NMR(100MHz,CDCl3)δ:155.5,134.3,129.6,129.3,127.7,126.9,126.5,124.0,118.7,107.5,78.5,75.7,55.9.
实施例23:取一个50mL圆底烧瓶,称取2-羟基吡啶(0.190g,2.0mmol),溴代丙炔(0.262g,2.2mmol),量取水2.0mL,称取四丁基溴化铵(0.645g,2.0mmol)和氢氧化钠(0.088g,2.2mmol),然后在室温下磁力搅拌反应(TLC检测,展开剂为PE:EA=8:1)30min反应完成,加入约15.0mL乙酸乙酯,加入适量200~300目硅胶,减压旋干,干法硅胶柱层析(200-300目)分离得(洗脱剂:V石油醚:V乙酸乙酯=8:1)到目标产物丙炔基2-吡啶基醚,产率为90%。丙炔基2-吡啶基醚,浅黄色油状物:1H NMR(400MHz,CDCl3)δ:7.64(d,J=6.8,1H),7.35(m,1H),6.61(d,J=9.2,1H),6.25(t,J=6.8,1H),4.76(d,J=2.4,2H),2.49(t,J=2.4,1H),13C NMR(100MHz,CDCl3)δ:147.5,129.6,121.0,116.6,79.0,73.5,41.2,31.3.
本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (4)
1.一种丙炔芳基醚类化合物的制备方法,其特征在于包括以下步骤:以卤代炔与芳基酚或杂芳香基酚为原料,按照一定比例加入相转移催化剂和碱,以水为溶剂,在一定温度下搅拌反应,反应结束后对产物进行分离提纯,即得所述丙炔芳基醚类化合物,其合成路线如下:
所述R1为苯基、取代苯基、萘基、取代萘基、杂芳香基、取代杂芳香基中的一种;所述X为F、Cl、Br、I中的一种;所述R2为H、烷基、取代烷基、苯基、取代苯基、杂芳香基、取代杂芳香基中的一种;
所述R1中取代基可以是单取代、二取代以及多取代;所述R1中取代基为下列任一基团或其任意组合:烷基、烷氧基、腈基、卤原子、硝基、醛基、酰基;所述R2中取代基可以是单取代;所述杂芳香基为吡啶基;
所述芳基酚或杂芳香基酚、卤代炔、相转移催化剂和碱的物质的量比为1.0∶1.1∶1.0:1.1;
所述反应时的温度为10-100℃;反应时间为20-120min。
2.根据权利要求1所述的丙炔芳基醚类化合物的制备方法,其特征在于:所述碱为醋酸钠、醋酸钾、碳酸钠、碳酸钾、碳酸铯、磷酸钠、磷酸钾、氢氧化锂、氢氧化钠、氢氧化钾、氢氧化钙、甲醇钠、甲醇钾、乙醇钠、乙醇钾、叔丁醇锂、叔丁醇钠、叔丁醇钾、正丁基锂、六甲基二硅基胺基钾(KHMDS)或六甲基二硅基胺基钠(NaHMDS)中的一种。
3.根据权利要求1所述的丙炔芳基醚类化合物的制备方法,其特征在于:所述相转移催化剂为季铵盐类相转移催化剂或非环多醚类相转移催化剂。
4.根据权利要求3所述的丙炔芳基醚类化合物的制备方法,其特征在于:所述季铵盐类相转移催化剂为四烷基卤化铵、苄基三乙基氯化铵(BTEAC);所述非环多醚类相转移催化剂为聚乙二醇或聚乙二醇脂肪醚。
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