CN114685408B - 一种烷基呋喃化合物的制备方法 - Google Patents
一种烷基呋喃化合物的制备方法 Download PDFInfo
- Publication number
- CN114685408B CN114685408B CN202210214245.9A CN202210214245A CN114685408B CN 114685408 B CN114685408 B CN 114685408B CN 202210214245 A CN202210214245 A CN 202210214245A CN 114685408 B CN114685408 B CN 114685408B
- Authority
- CN
- China
- Prior art keywords
- compound
- pdcl
- phosphine
- potassium
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 alkyl furan compound Chemical class 0.000 title claims abstract description 35
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 238000005286 illumination Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 4
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 4
- 235000019800 disodium phosphate Nutrition 0.000 claims description 4
- 229940078552 o-xylene Drugs 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
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- GPORFKPYXATYNX-UHFFFAOYSA-N 6-diphenylphosphanylhexyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 GPORFKPYXATYNX-UHFFFAOYSA-N 0.000 claims description 3
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- UXRZLDREKITWRO-UHFFFAOYSA-N P(c1ccccc1)c1ccccc1.CC1(C)c2ccccc2Oc2ccccc12 Chemical compound P(c1ccccc1)c1ccccc1.CC1(C)c2ccccc2Oc2ccccc12 UXRZLDREKITWRO-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- RYXZOQOZERSHHQ-UHFFFAOYSA-N [2-(2-diphenylphosphanylphenoxy)phenyl]-diphenylphosphane Chemical compound C=1C=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1OC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RYXZOQOZERSHHQ-UHFFFAOYSA-N 0.000 claims description 3
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 claims description 3
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 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
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- LCSNDSFWVKMJCT-UHFFFAOYSA-N dicyclohexyl-(2-phenylphenyl)phosphane Chemical group C1CCCCC1P(C=1C(=CC=CC=1)C=1C=CC=CC=1)C1CCCCC1 LCSNDSFWVKMJCT-UHFFFAOYSA-N 0.000 claims description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 3
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 3
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 3
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 3
- JQKHNBQZGUKYPX-UHFFFAOYSA-N tris(2,4,6-trimethoxyphenyl)phosphane Chemical compound COC1=CC(OC)=CC(OC)=C1P(C=1C(=CC(OC)=CC=1OC)OC)C1=C(OC)C=C(OC)C=C1OC JQKHNBQZGUKYPX-UHFFFAOYSA-N 0.000 claims description 3
- CMLWFCUAXGSMBB-UHFFFAOYSA-N tris(2,6-dimethoxyphenyl)phosphane Chemical compound COC1=CC=CC(OC)=C1P(C=1C(=CC=CC=1OC)OC)C1=C(OC)C=CC=C1OC CMLWFCUAXGSMBB-UHFFFAOYSA-N 0.000 claims description 3
- IIOSDXGZLBPOHD-UHFFFAOYSA-N tris(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC IIOSDXGZLBPOHD-UHFFFAOYSA-N 0.000 claims description 3
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 229910021605 Palladium(II) bromide Inorganic materials 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-L PdCl2(PPh3)2 Substances [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 claims description 2
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 0.000 claims description 2
- UFZJUNYPYMYVIS-UHFFFAOYSA-N dicyclohexyl-(1-methyl-2-phenylindol-3-yl)phosphane Chemical compound C12=CC=CC=C2N(C)C(C=2C=CC=CC=2)=C1P(C1CCCCC1)C1CCCCC1 UFZJUNYPYMYVIS-UHFFFAOYSA-N 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 claims 1
- SBOQCPPINFMCBH-UHFFFAOYSA-N diphenylphosphane;methane Chemical compound C.C=1C=CC=CC=1PC1=CC=CC=C1.C=1C=CC=CC=1PC1=CC=CC=C1 SBOQCPPINFMCBH-UHFFFAOYSA-N 0.000 claims 1
- 125000004185 ester group Chemical group 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 abstract description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 76
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 38
- 239000000203 mixture Substances 0.000 description 20
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- 229910052786 argon Inorganic materials 0.000 description 19
- 238000012512 characterization method Methods 0.000 description 19
- 238000004440 column chromatography Methods 0.000 description 19
- 239000000126 substance Substances 0.000 description 19
- 238000001035 drying Methods 0.000 description 18
- 101150003085 Pdcl gene Proteins 0.000 description 6
- 238000005804 alkylation reaction Methods 0.000 description 6
- 230000029936 alkylation Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002240 furans Chemical class 0.000 description 3
- 150000002390 heteroarenes Chemical class 0.000 description 3
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 2
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 2
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 2
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 2
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 2
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 2
- OJRUSAPKCPIVBY-KQYNXXCUSA-N C1=NC2=C(N=C(N=C2N1[C@H]3[C@@H]([C@@H]([C@H](O3)COP(=O)(CP(=O)(O)O)O)O)O)I)N Chemical compound C1=NC2=C(N=C(N=C2N1[C@H]3[C@@H]([C@@H]([C@H](O3)COP(=O)(CP(=O)(O)O)O)O)O)I)N OJRUSAPKCPIVBY-KQYNXXCUSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229940126657 Compound 17 Drugs 0.000 description 2
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125773 compound 10 Drugs 0.000 description 2
- 229940125797 compound 12 Drugs 0.000 description 2
- 229940126543 compound 14 Drugs 0.000 description 2
- 229940125758 compound 15 Drugs 0.000 description 2
- 229940126142 compound 16 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XGCDBGRZEKYHNV-UHFFFAOYSA-N 1,1-bis(diphenylphosphino)methane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 XGCDBGRZEKYHNV-UHFFFAOYSA-N 0.000 description 1
- CEVMYGZHEJSOHZ-UHFFFAOYSA-N 1-bromo-3-methoxypropane Chemical compound COCCCBr CEVMYGZHEJSOHZ-UHFFFAOYSA-N 0.000 description 1
- VQHPRVYDKRESCL-UHFFFAOYSA-N 1-bromoadamantane Chemical compound C1C(C2)CC3CC2CC1(Br)C3 VQHPRVYDKRESCL-UHFFFAOYSA-N 0.000 description 1
- VOHILFSOWRNVJJ-UHFFFAOYSA-N 2-(bromomethyl)oxolane Chemical compound BrCC1CCCO1 VOHILFSOWRNVJJ-UHFFFAOYSA-N 0.000 description 1
- RCXJARRRXOPXBC-UHFFFAOYSA-N 2-bromoadamantane Chemical compound C1C(C2)CC3CC1C(Br)C2C3 RCXJARRRXOPXBC-UHFFFAOYSA-N 0.000 description 1
- UPSXAPQYNGXVBF-UHFFFAOYSA-N 2-bromobutane Chemical compound CCC(C)Br UPSXAPQYNGXVBF-UHFFFAOYSA-N 0.000 description 1
- LRLQQERNMXHASR-UHFFFAOYSA-N 2-diphenylphosphanylpropan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 LRLQQERNMXHASR-UHFFFAOYSA-N 0.000 description 1
- YXDXXGXWFJCXEB-UHFFFAOYSA-N 2-furonitrile Chemical compound N#CC1=CC=CO1 YXDXXGXWFJCXEB-UHFFFAOYSA-N 0.000 description 1
- RQFUZUMFPRMVDX-UHFFFAOYSA-N 3-Bromo-1-propanol Chemical compound OCCCBr RQFUZUMFPRMVDX-UHFFFAOYSA-N 0.000 description 1
- XMZQWZJMTBCUFT-UHFFFAOYSA-N 3-bromopropylbenzene Chemical compound BrCCCC1=CC=CC=C1 XMZQWZJMTBCUFT-UHFFFAOYSA-N 0.000 description 1
- CQPGDDAKTTWVDD-UHFFFAOYSA-N 4-bromobutanenitrile Chemical compound BrCCCC#N CQPGDDAKTTWVDD-UHFFFAOYSA-N 0.000 description 1
- IVBVKTPDEWDNRW-UHFFFAOYSA-N 4-bromooxane Chemical compound BrC1CCOCC1 IVBVKTPDEWDNRW-UHFFFAOYSA-N 0.000 description 1
- PLOVEYHBGVOMPQ-UHFFFAOYSA-N 5-(oxan-4-yl)furan-2-carbonitrile Chemical compound O1CCC(CC1)C1=CC=C(O1)C#N PLOVEYHBGVOMPQ-UHFFFAOYSA-N 0.000 description 1
- LPNANKDXVBMDKE-UHFFFAOYSA-N 5-bromopent-1-ene Chemical compound BrCCCC=C LPNANKDXVBMDKE-UHFFFAOYSA-N 0.000 description 1
- ZZVSDZISQFEWRA-UHFFFAOYSA-N 5-tert-butylfuran-2-carbonitrile Chemical compound CC(C)(C)C1=CC=C(C#N)O1 ZZVSDZISQFEWRA-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KXVUSQIDCZRUKF-UHFFFAOYSA-N bromocyclobutane Chemical compound BrC1CCC1 KXVUSQIDCZRUKF-UHFFFAOYSA-N 0.000 description 1
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical compound BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 description 1
- BRTFVKHPEHKBQF-UHFFFAOYSA-N bromocyclopentane Chemical compound BrC1CCCC1 BRTFVKHPEHKBQF-UHFFFAOYSA-N 0.000 description 1
- UUWSLBWDFJMSFP-UHFFFAOYSA-N bromomethylcyclohexane Chemical compound BrCC1CCCCC1 UUWSLBWDFJMSFP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003446 ligand Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QAWFLJGZSZIZHO-UHFFFAOYSA-N methyl 4-bromobutanoate Chemical compound COC(=O)CCCBr QAWFLJGZSZIZHO-UHFFFAOYSA-N 0.000 description 1
- UBRPDRSWIRZWQG-UHFFFAOYSA-N methyl 5-tert-butylfuran-2-carboxylate Chemical compound COC(=O)C1=CC=C(C(C)(C)C)O1 UBRPDRSWIRZWQG-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供一种烷基呋喃化合物的制备方法,包括以下步骤:将式I化合物R2‑Br、碱、催化剂和稳定剂加入有机溶剂中,光照下反应得到式II烷基呋喃化合物
Description
技术领域
本发明属于有机合成技术领域,尤其涉及一种烷基呋喃化合物的制备方法。
背景技术
芳烃的烷基化在有机合成中具有重大意义,烷基取代的杂芳烃支架也常见于天然产物、药物分子和其它应用材料中。在这些杂芳烃中,α-烷基呋喃作为药物研究中的重要结构,引起了化学家们长久的关注。传统呋喃的直接烷基化反应分为两种类型:1.傅克烷基化,这通常需要路易斯酸或者使用对环境有害的溶剂,并且对呋喃的选择性不专一,产率低;2.亲核取代反应,这需要极低的温度和强碱来形成和稳定呋喃阴离子。这两种反应都受到官能团相容性的限制。近年来,随着有机金属化学的飞速发展,经历自由基途径的呋喃衍生物的直接烷基化反应有了一些进展。最近,过渡金属催化的碳氢官能化已成为芳烃直接烷基化的强大而可靠的工具,作为典型的富电子杂芳烃,过渡金属催化的碳氢键官能团化用于呋喃直接烷基化的报道比较少。在已有的报道中,有的需要使用昂贵的催化剂且反应条件苛刻,有的涉及危险的过氧化物,需要高温的反应条件,有的呋喃底物受限且过量使用。因此,急需开发一种方便、实用、对环境友好的呋喃直接烷基化方法。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此,本发明提出一种烷基呋喃化合物的制备方法,该方法不需要昂贵的催化剂,也不需要使用过氧化物,制备条件温和,在室温下光照反应即可完成。
本发明提出了一种烷基呋喃化合物的制备方法,包括以下步骤:将式I化合物R2-Br、碱、催化剂和稳定剂加入有机溶剂中,光照下反应得到式II烷基呋喃化合物/>
其中,R1为吸电子基;R2为烷基或取代烷基。
本发明中,使用溴代烷烃R2-Br作为烷基化试剂,由于钯和配体形成络合物吸收光子形成的光激发态与溴代烷烃经历单电子转移过程可以使C-Br键断裂产生碳自由基,因而反应能在可见光照射下即可成功进行。
在本发明的一些实施方式中,所述式I化合物与所述R2-Br的摩尔比为100:1~1:100。
在本发明的一些优选的实施方式中,所述式I化合物与所述碱的摩尔比为100:1~1:100。
在本发明的一些更优选的实施方式中,所述式I化合物与所述稳定剂的摩尔比为1:100~1:1。
在本发明的一些更优选的实施方式中,所述式I化合物与所述稳定剂的摩尔比为1:100~1:1。
在本发明的一些更优选的实施方式中,所述制备方法的反应温度为10℃~35℃,即为在室温下即可进行。
在本发明的一些更优选的实施方式中,所述制备方法的反应时间为1~60小时。
在本发明的一些更优选的实施方式中,所述制备方法的反应环境为惰性氛围。
在本发明的一些更优选的实施方式中,所述有机溶剂选自苯、甲苯、邻二甲苯、氯苯、氟苯、二氯甲烷、二氯乙烷、乙腈、二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、乙酸乙酯、乙酸叔丁酯、四氢呋喃、乙醚、1,4-二氧六环、六氟异丙醇、1-甲基2-吡咯烷酮、丁酸甲酯中的至少一种。
在本发明的一些更优选的实施方式中,所述碱选自醋酸钾、醋酸钠、醋酸铯、碳酸钾、碳酸钠、碳酸铯、叔丁醇钾、叔丁醇钠、碳酸氢钾、碳酸氢钠、磷酸钠、氟化钾、磷酸钾、磷酸氢钠、磷酸氢钾、三乙胺、吡啶、二异丙基乙基胺或N-甲基吗啡啉中的至少一种。
在本发明的一些更优选的实施方式中,所述的稳定剂选自三苯基膦、4,5-双(二苯基膦)-9,9-二甲基氧杂蒽、双(2-二苯基磷苯基)醚、联萘二苯膦、2-(二环己基膦基)联苯、2-(二叔丁基膦)联苯、2-二环己基磷-2',4',6'-三异丙基联苯、三(2-甲氧基苯基)膦、三(4-甲氧基-苯基)膦、三(4-甲基-苯基)膦、三(2,6-二甲氧基-苯基)膦、三(2,4,6-三甲氧基-苯基)膦、三环己基膦、三叔丁基膦四氟硼酸盐苄基二苯膦、双二苯基膦甲烷、1,6-双(二苯基膦基)己烷、4,5-二(二叔丁基膦)-9,9-二甲基氧杂蒽、3-(二环己基膦基)-1-甲基-2-苯基-1H-吲哚、双二苯基膦乙烷或双二苯基膦丙烷的至少一种。
在本发明的一些更优选的实施方式中,所述催化剂选自Pd(OAc)2、Pd(PPh3)4、PdCl2、PdBr2、PdCl2(PPh3)2、Pd(O2CCF3)2、Pd(PdCl2(PhCN)2、PdCl2(CH3CN)2、Pd2(dba)3、PdCl2(dppf)、PdCl2(COD)、Pd(acac)2、Pd(dba)2、(allylPdCl)2、Pd(OPiv)2、Pd(BF4)2(MeCN)4、PdCl2(dtbpf)、IPrPdCl2或PdBr2(COD)中的至少一种。
在本发明的一些更优选的实施方式中,R1为吸电子基,所述吸电子基选自氰基、酯基或酰基。
在本发明的一些更优选的实施方式中,R2为烷基或取代烷基,所述取代烷基可为醚基、卤素、羟基、氰基或酯基取代的烷基。
在本发明的一些更优选的实施方式中,所述烷基呋喃化合物选自以下:
本发明的有益效果为:
1.本发明的制备方法不需要严格的无水条件和低温高温操作,光照下室温反应即可进行,高效节省了能量、不需要使用危险的过氧化物,操作简单安全,成本低廉,具有环境友好绿色可持续性。
2.本发明的制备方法不需要昂贵的催化剂,使用价格低廉、经济易得的溴代烷烃做烷基化试剂,底物兼容性强。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述,以充分地理解本发明的目的、特征和效果。显然,所描述的实施例只是本发明的一部分实施例,而不是全部实施例,基于本发明的实施例,本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例,均属于本发明保护的范围。
实施例1
本实施例制备了化合物1(化学名:5-(3-甲氧基丙基)呋喃-2-甲腈),化合物1的结构式如下:
具体过程为:在100mL Schlenk反应管中加入0.05mmol Pd(OAc)2、0.05mmol三苯基膦、50.0mmol醋酸钾、5.0mmol50.0mmol 3-溴丙基甲基醚,抽除空气并且充入氩气,如此反复三次后,加入苯50.0mL,光照下室温反应48小时停止反应。然后减压滤,旋干,柱层析分离纯化,得到目标产物371.4mg(产率为45%)。
产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.01(d,J=3.6Hz,1H),6.15(d,J=3.6Hz,1H),3.40(t,J=6.0Hz,2H),3.34(s,3H),2.77(t,J=7.6Hz,2H),1.96-1.89(m,2H).13C NMR(100MHz,CDCl3)δ161.86,124.54,123.12,111.95,107.29,71.18,58.64,27.62,24.94.
实施例2
本实施例制备了化合物2(化学名:5-(四氢呋喃-2-甲基)呋喃-2-甲腈),化合物2的结构式如下:
具体过程为:在100mL Schlenk反应管中加入0.025mmol Pd(PPh3)4、0.05mmol 4,5-双(二苯基膦)-9,9-二甲基氧杂蒽、0.02mmol醋酸钠、1.0mmol100.0mmol 2-溴甲基四氢呋喃,抽除空气并且充入氩气,如此反复三次后,加入甲苯30.0mL,光照下室温反应12小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物92.8mg(产率为52%)。
产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.02(d,J=3.6Hz,1H),6.25(d,J=3.6Hz,1H),4.20–4.11(m,1H),3.93–3.85(m,1H),3.76(dd,J=15.2,7.0Hz,1H),2.95–2.83(m,2H),2.09–2.01(m,1H),1.96–1.83(m,2H),1.58(m,1H).13C NMR(100MHz,CDCl3)δ159.33,124.77,123.21,111.90,108.58,68.19,34.49,31.19,25.59.
实施例3
本实施例制备了化合物3(化学名:4-(5-氰基呋喃)丁酸甲酯),化合物3的结构式如下:
具体过程为:在25mL Schlenk反应管中加入0.5mmol PdCl2、0.5mmol双(2-二苯基磷苯基)醚、0.5mmol醋酸铯、0.5mmol25.0mmol 4-溴丁酸甲酯,抽除空气并且充入氩气,如此反复三次后,加入氯苯10.0mL,光照下室温反应2小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物49.2mg(产率为51%)。
产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.01(d,J=3.6Hz,1H),6.17(d,J=3.6Hz,1H),3.69(s,3H),2.75(t,J=7.6Hz,2H),2.37(t,J=7.4Hz,2H),2.04–1.97(m,2H).13C NMR(100MHz,CDCl3)δ173.22,161.12,124.74,123.09,111.83,107.58,51.70,32.94,27.44,22.79.
实施例4
本实施例制备了化合物4(化学名:5-(3-氯丙基)呋喃-2-甲腈),化合物4的结构式如下:
具体过程为:在25mL Schlenk反应管中加入0.025mmol PdBr2、0.05mmol联萘二苯膦、50.0mmol醋酸铯、0.5mmol10.0mmol 3-氯丙烷,抽除空气并且充入氩气,如此反复三次后,加入氟苯10.0mL,光照下室温反应10小时停止反应。然后减压干,柱层析分离纯化,得到目标产物38.3mg(产率为45%)。
产物的结构表征物理数:1H NMR(400MHz,CDCl3)δ7.02(d,J=3.6Hz,1H),6.20(d,J=3.6Hz,1H),3.56(t,J=6.4Hz,2H),2.88(t,J=7.4Hz,2H),2.18–2.11(m,2H).13C NMR(100MHz,CDCl3)δ160.38,124.95,123.09,111.75,107.91,43.61,30.22,25.40.
实施例5
本实施例制备了化合物5(化学名:5-(1-戊烯基)呋喃-2-甲腈),化合物5的结构式如下:
具体过程为:在25mL Schlenk反应管中加入0.025mmol PdCl2(PPh3)2、0.5mmol 2-(二环己基膦基)联苯、0.5mmol碳酸钠、0.5mmo1.75mmol 5-溴-1-戊烯,抽除空气并且充入氩气,如此反复三次后,加入二氯甲烷10.0mL,光照下室温反应48小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物32.2mg(产率为40%)。
产物的结构表征物理常数:1H NMR(500MHz,CDCl3)δ7.00(d,J=3.5Hz,1H),6.13(d,J=3.5Hz,1H),5.83–5.75(m,1H),5.09–4.97(m,2H),2.68(t,J=7.5Hz,2H),2.11(q,J=7.0Hz,2H),1.82–1.68(m,2H).13C NMR(125MHz,CDCl3)δ162.17,137.46,124.46,123.11,115.58,112.01,107.17,32.90,27.50,26.66.
实施例6
本实施例制备了化合物6(化学名:5-(4,4,4-三氟丁基)呋喃-2-甲腈),化合物6的结构式如下:
具体过程为:在100mL Schlenk反应管中加入0.025mmol Pd(O2CCF3)2、0.5mmol 2-(二叔丁基膦)联苯、5.0mmol碳酸铯、5.0mmol20.0mmol1-溴-4,4,4-三氟丁烷,抽除空气并且充入氩气,如此反复三次后,加入二氯乙烷40mL,光照下室温反应64小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物487.3mg(产率为48%)。
产物的结构表征物理常数:1H NMR(500MHz,CDCl3)δ7.03(d,J=3.5Hz,1H),6.19(d,J=3.5Hz,1H),2.79(t,J=7.5Hz,2H),2.26–2.07(m,2H),2.03–1.87(m,2H).13C NMR(125MHz,CDCl3)δ160.25,128.58,128.48,127.89,125.77,125.03,123.07,111.68,107.81,67.10,33.23,33.00,32.77,32.54,27.05.
实施例7
本实施例制备了化合物7(化学名:5-(3-苯丙基)呋喃-2-甲腈),化合物7的结构式如下:
具体过程为:在25mL Schlenk反应管中加入0.005mmol Pd(PdCl2(PhCN)2、0.1mmol2-二环己基磷-2',4',6'-三异丙基联苯、0.5mmol叔丁醇钾、0.5mmol1mmol 1-溴-3-苯基丙烷,抽除空气并且充入氩气,如此反复三次后,加入乙腈2mL,光照下室温反应50小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物51.71mg(产率为49%)。
产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.22(t,J=7.4Hz,2H),7.14(d,J=7.4Hz,1H),7.10(d,J=7.2Hz,2H),6.92(d,J=3.6Hz,1H),6.05(d,J=3.6Hz,1H),2.60(dd,J=16.0,8.0Hz,4H),2.09–1.85(m,2H).13C NMR(100MHz,CDCl3)δ162.04,141.15,128.50,128.45,126.13,124.52,123.14,112.01,107.26,77.39,77.07,76.75,35.07,29.08,27.62.
实施例8
本实施例制备了化合物8(化学名:5-(3-氰丙基)呋喃-2-甲腈),化合物8的结构式如下:
具体过程为:在100mL Schlenk反应管中加入0.05mmol PdCl2(CH3CN)2、0.5mmol三(2-甲氧基苯基)膦、0.5mmol叔丁醇钠、5mmol100.0mmol 4-溴丁腈,抽除空气并且充入氩气,如此反复三次后,加入二甲基亚砜10mL,光照下室温反应18小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物384.2mg(产率为48%)。
产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.04(d,J=3.6Hz,1H),6.25(d,J=3.6Hz,1H),2.88(t,J=7.4Hz,2H),2.41(t,J=7.0Hz,2H),2.09–2.02(m,J=7.2Hz,2H).13CNMR(100MHz,CDCl3)δ159.19,125.29,128.50,123.05,118.60,111.53,108.38,26.89,23.45,16.52.
实施例9
本实施例制备了化合物9(化学名:5-(3-羟丙基)呋喃-2-甲腈),化合物9的结构式如下:
具体过程为:在25mL Schlenk反应管中加入0.02mmol Pd2(dba)3、0.01mmol三(4-甲氧基-苯基)膦、0.5mmol碳酸氢钾、0.5mmol3.5mmol 3-溴丙醇,抽除空气并且充入氩气,如此反复三次后,加入二甲基甲酰胺2.5mL,光照下室温反应10小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物37.7mg(产率为50%)。
产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.07(d,J=3.6Hz,1H),6.47(d,J=3.6Hz,1H),4.70(dd,J=9.4,2.8Hz,1H),3.97(dd,J=11.6,2.8Hz,1H),3.93–3.83(m,2H),3.82–3.77(m,1H),3.76–3.67(m,2H).13C NMR(100MHz,CDCl3)δ156.87,125.95,122.63,111.21,109.18,70.77,68.89,66.38.
实施例10
本实施例制备了化合物10(化学名:5-(环己基甲基)呋喃-2-甲腈),化合物10的结构式如下:
具体过程为:在50mL Schlenk反应管中加入0.05mmol PdCl2(dppf)、0.25mmol三(2,6-二甲氧基-苯基)膦、5.0mmol二异丙基乙基胺、2.0mmol20.0mmol溴甲基环己烷,抽除空气,并且充入氩气,如此反复三次后,加入二甲基乙酰胺10.0mL,光照下室温反应64小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物200.3mg(产率为53%)。
产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.00(d,J=3.6Hz,1H),6.11(d,J=3.6Hz,1H),2.54(d,J=6.6Hz,2H),1.70(dd,J=18.4,6.8Hz,6H),1.31–1.11(m,3H),1.03–0.86(m,2H).13C NMR(100MHz,CDCl3)δ161.60,124.40,123.09,112.12,107.92,37.09,36.01,32.98,26.20,26.03.
实施例11
本实施例制备了化合物11(化学名:5-(2-甲基丁基)呋喃-2-甲腈),化合物11的结构式如下:
具体过程为:在25mL Schlenk反应管中加入0.05mmol PdCl2(COD)、0.25mmol三(2,4,6-三甲氧基-苯基)膦、2.5mmol磷酸钠、0.5mmol10.0mmol 2-溴丁烷,抽除空气并且充入氩气,如此反复三次后,加入乙酸乙酯3.0mL,光照下室温反应5小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物32.1mg(产率为43%)。
产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.00(d,J=3.6Hz,1H),6.11(d,J=3.6Hz,1H),3.04–2.56(m,1H),1.77–1.65(m,1H),1.65–1.52(m,1H),1.25(d,J=7.0Hz,3H),0.88(t,J=7.4Hz,3H).13C NMR(100MHz,CDCl3)δ166.65,124.27,122.92,112.10,105.92,35.11,28.27,18.19,11.38.
实施例12
本实施例制备了化合物12(化学名:5-环丁基呋喃-2-甲腈),化合物12的结构式如下:
具体过程为:在25mL Schlenk反应管中加入0.025mmol Pd(acac)2、0.05mmol三环己基膦、0.5mmolN-甲基吗啡啉、0.5mmol1.75mmol溴代环丁烷,抽除空气并且充入氩气,如此反复三次后,加入乙酸叔丁酯3.0mL,光照下室温反应15小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物44.12mg(产率为60%)。
产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.00(d,J=3.6Hz,1H),6.14(d,J=3.6Hz,1H),3.54(p,J=8.6Hz,1H),2.39–2.31(m,2H),2.31–2.20(m,2H),2.09–1.99(m,1H),1.98–1.86(m,1H).13C NMR(100MHz,CDCl3)δ165.14,124.30,123.09,112.11,105.84,33.49,27.96,18.51.
实施例13
本实施例制备了化合物13(化学名:5-环戊基呋喃-2-甲腈),化合物13的结构式如下:
具体过程为:在25mL Schlenk反应管中加入0.005mmol Pd(dba)2、0.005mmol三叔丁基膦四氟硼酸盐苄基二苯膦、0.05mmol氟化钾、0.5mmol1.0mmol溴代环戊烷,抽除空气并且充入氩气,此反复三次后,加入四氢呋喃3.0mL,光照下室温反应20小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物110.1mg(产率为68%)。
产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ6.99(d,J=3.6Hz,1H),6.11(d,J=3.6Hz,1H),3.31–3.03(m,1H),2.05–2.02(m,2H),1.87–1.56(m,6H).13C NMR(100MHz,CDCl3)δ166.14,124.22,123.00,112.13,105.57,38.86,31.72,25.22.
实施例14
本实施例制备了化合物14(化学名:5-环己基呋喃-2-甲腈),化合物14的结构式如下:
具体过程为:在100mL Schlenk反应管中加入0.05mmol(allylPdCl)2、0.5mmol双二苯基膦甲烷、1.5mmol磷酸钾、5.0mmol1.5mmol溴代环己烷,抽除空气并且充入氩气,如此反复三次后,加入1,4-二氧六环5.0mL,光照下室温反应3小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产551.6mg(产率为63%)。
产物的结构表征物理常数:1H NMR(500MHz,CDCl3)δ7.00(d,J=3.5Hz,1H),6.08(d,J=3.5,1H),2.73–2.61(m,1H),2.01(d,J=10.0Hz,2H),1.81(dd,J=9.0,3.0Hz,2H),1.75–1.69(m,1H),1.46–1.31(m,4H),1.27–1.21(m,1H).13C NMR(125MHz,CDCl3)δ166.76,124.07,122.98,112.18,105.11,37.48,31.07,25.80,25.66.
实施例15
本实施例制备了化合物15(化学名:5-(4-四氢-2H-吡喃基)呋喃-2-甲腈),化合物15的结构式如下:
具体过程为:在25mL Schlenk反应管中加入0.5mmol Pd(OPiv)2、0.5mmol 1,6-双(二苯基膦基)己烷、0.5mmol磷酸氢钠、0.5mmol1.75mmol 4-溴四氢吡喃,抽除空气并且充入氩气,如此反复三次后,加入六氟异丙醇25.0mL,光照下室温反应1小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物44.3mg(产率为50%)。
产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ7.03(d,J=3.6Hz,1H),6.15(d,J=3.6Hz,1H),4.03(ddd,J=11.6,4.0,2.2Hz,2H),3.51(td,J=11.8,2.0Hz,2H),3.14–2.71(m,1H),1.93(dd,J=13.0,2.0Hz,2H),1.85–1.57(m,3H).13C NMR(100MHz,CDCl3)δ164.57,124.60,122.95,111.84,105.69,67.20,34.73,30.67.
实施例16
本实施例制备了化合物16(化学名:5-(2-金刚烷基)呋喃-2-甲腈),化合物16的结构式如下:
具体过程为:在25mL Schlenk反应管中加入0.005mmol Pd(BF4)2(MeCN)4、0.005mmol4,5-二(二叔丁基膦)-9,9-二甲基氧杂蒽、0.5mmol磷酸氢钾、0.5mmol6.0mmol 2-溴金刚烷,抽除空气并且充入氩气,如此反复三次后,加入1-甲基2-吡咯烷酮15.0mL,光照下室温反应3小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物68.1mg(产率为60%)。
产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ6.98(d,J=3.6Hz,1H),6.12(dd,J=3.6,1.4Hz,1H),2.98(s,1H),2.27(s,2H),1.88(d,J=12.8Hz,3H),1.80(d,J=12.4Hz,2H),1.74(s,2H),1.70(s,3H),1.56(d,J=12.0Hz,2H).13C NMR(100MHz,CDCl3)δ165.35,123.89,123.06,112.26,106.89,44.44,38.09,37.50,32.53,30.23,27.56,27.49.
实施例17
本实施例制备了化合物17(化学名:5-(1-金刚烷基)呋喃-2-甲腈),化合物17的结构式如下:
具体过程为:在100mL Schlenk反应管中加入0.25mmol PdCl2(dtbpf)、0.2mmol3-(二环己基膦基)-1-甲基-2-苯基-1H-吲哚、0.5mmol磷酸氢钠、5.0mmol5.0mmol 1-溴金刚烷,抽除空气并且充入氩气,如此反复三次后,加入丁酸甲酯100.0mL,光照下室温反应38小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物726.8mg(产率为64%)。
产物的结构表征物理常数:1H NMR(400MHz,CDCl3)δ6.99(d,J=3.6Hz,1H),6.05(d,J=3.6Hz,1H),2.07(s,3H),1.91(d,J=2.4Hz,6H),1.76(q,J=12.4Hz,6H).13C NMR(100MHz,CDCl3)δ170.16,123.92,122.87,112.25,103.86,40.73,36.46,35.27,27.98.
实施例18
本实施例制备了化合物18(化学名:5-叔丁基呋喃-2-甲腈),化合物18的结构式如下:
具体过程为:在100mL Schlenk反应管中加入0.5mmol IPrPdCl2、0.5mmol 1,6-双二苯基膦乙烷、50.0mmol三乙胺、5.0mmol17.5 mmol溴代叔丁烷,抽除空气并且充入氩气,如此反复三次后,加入邻二甲苯30.0mL,光照下室温反应8小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物44.3mg(产率为68%)。
产物的结构表征物理常数:1H NMR(400 MHz,CDCl3)δ6.98(d,J=3.6 Hz,1H),6.10(d,J=3.6 Hz,1H),1.30(s,9H).13C NMR(100 MHz,CDCl3)δ170.08,124.20,122.90,112.17,104.28,33.35,28.71.
实施例19
本实施例制备了化合物19(化学名:5-(叔丁基)呋喃-2-甲酸甲酯),化合物19的结构式如下:
具体过程为:在100mL Schlenk反应管中加入0.05mmol PdBr2(COD)、0.025 mmol双二苯基膦丙烷、3.0mmol吡啶、3.0mmol20.0 mmol溴代叔丁烷,抽除空气并且充入氩气,如此反复三次后,加入邻二甲苯30.0mL,光照下室温反应4小时停止反应。然后减压抽滤,旋干,柱层析分离纯化,得到目标产物189.1mg(产率为50%)。/>
产物的结构表征物理常数:1H NMR(400 MHz,CDCl3)δ7.08(d,J=3.4 Hz,1H),6.10(d,J=3.4 Hz,1H),3.87(s,3H),1.33(s,9H).13C NMR(100 MHz,CDCl3)δ168.96,159.37,142.75,119.00,104.74,51.59,33.11,28.83.
上面对本发明实施例作了详细说明,但是本发明不限于上述实施例,在所属技术领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。此外,在不冲突的情况下,本发明的实施例及实施例中的特征可以相互组合。
Claims (8)
1.一种烷基呋喃化合物的制备方法,包括以下步骤:将式I化合物、R2-Br、碱、催化剂和稳定剂加入有机溶剂中,光照下反应得到式II烷基呋喃化合物/>;
其中,R1为吸电子基,所述吸电子基选自氰基或酯基;
所述碱选自醋酸钾、醋酸钠、醋酸铯、碳酸钾、碳酸钠、碳酸铯、叔丁醇钾、叔丁醇钠、碳酸氢钾、碳酸氢钠、磷酸钠、氟化钾、磷酸钾、磷酸氢钠、磷酸氢钾、三乙胺、吡啶、二异丙基乙基胺或N-甲基吗啡啉中的至少一种;
所述催化剂选自Pd(OAc)2、Pd(PPh3)4、PdCl2、PdBr2、PdCl2(PPh3)2、Pd(O2CCF3)2、Pd(PdCl2(PhCN)2、PdCl2(CH3CN)2、Pd2(dba)3、PdCl2(dppf)、PdCl2(COD)、Pd(acac)2、Pd(dba)2、(allylPdCl)2、Pd(OPiv)2、Pd(BF4)2(MeCN)4、PdCl2(dtbpf)、IPrPdCl2或PdBr2(COD)中的至少一种;
所述的稳定剂选自三苯基膦、4,5-双(二苯基膦)-9,9-二甲基氧杂蒽、双(2-二苯基磷苯基)醚、联萘二苯膦、2-(二环己基膦基)联苯、2-(二叔丁基膦)联苯、2-二环己基磷-2',4',6'-三异丙基联苯、三(2-甲氧基苯基)膦、三(4-甲氧基-苯基)膦、三(4-甲基-苯基)膦、三(2,6-二甲氧基-苯基)膦、三(2,4,6-三甲氧基-苯基)膦、三环己基膦、三叔丁基膦四氟硼酸盐苄基二苯膦、双二苯基膦甲烷、1,6-双(二苯基膦基)己烷、4,5-二(二叔丁基膦)-9,9-二甲基氧杂蒽、3-(二环己基膦基)-1-甲基-2-苯基-1H-吲哚、双二苯基膦乙烷或双二苯基膦丙烷的至少一种;
所述烷基呋喃化合物选自以下:
、/>、/>、、/>、/>、、/>、/>、/>、或/>。
2.根据权利要求1所述的制备方法,其特征在于:所述制备方法的反应温度为10℃~35℃。
3.根据权利要求1所述的制备方法,其特征在于:所述制备方法的反应时间为1~60小时。
4.根据权利要求1所述的制备方法,其特征在于:所述式I化合物与所述R2-Br的摩尔比为100:1~1:100。
5.根据权利要求1所述的制备方法,其特征在于:所述式I化合物与所述碱的摩尔比为100:1~1:100。
6.根据权利要求1所述的制备方法,其特征在于:所述式I化合物与所述稳定剂的摩尔比为1:100~1:1。
7.根据权利要求1所述的制备方法,其特征在于:所述制备方法的反应环境为惰性氛围。
8.根据权利要求1所述的制备方法,其特征在于:所述有机溶剂选自苯、甲苯、邻二甲苯、氯苯、氟苯、二氯甲烷、二氯乙烷、乙腈、二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、乙酸乙酯、乙酸叔丁酯、四氢呋喃、乙醚、1,4-二氧六环、六氟异丙醇、1-甲基2-吡咯烷酮、丁酸甲酯中的至少一种。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210214245.9A CN114685408B (zh) | 2022-03-04 | 2022-03-04 | 一种烷基呋喃化合物的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210214245.9A CN114685408B (zh) | 2022-03-04 | 2022-03-04 | 一种烷基呋喃化合物的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114685408A CN114685408A (zh) | 2022-07-01 |
CN114685408B true CN114685408B (zh) | 2024-04-23 |
Family
ID=82138111
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210214245.9A Active CN114685408B (zh) | 2022-03-04 | 2022-03-04 | 一种烷基呋喃化合物的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114685408B (zh) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20140027591A (ko) * | 2012-07-19 | 2014-03-07 | 한양대학교 에리카산학협력단 | 가시광선 및 광촉매를 이용한 트리플루오로메틸-치환된 헤테로사이클의 제조방법 |
-
2022
- 2022-03-04 CN CN202210214245.9A patent/CN114685408B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20140027591A (ko) * | 2012-07-19 | 2014-03-07 | 한양대학교 에리카산학협력단 | 가시광선 및 광촉매를 이용한 트리플루오로메틸-치환된 헤테로사이클의 제조방법 |
Non-Patent Citations (4)
Title |
---|
De novo Design of Organic Photocatalysts: Bithiophene Derivatives for the Visible-light Induced C-H Functionalization of Heteroarenes;Bottecchia, Cecilia et al.;《Advanced Synthesis & Catalysis》;第361卷(第5期);第 945-950页 * |
Regioselective Pd-catalyzed α-alkylation of furans using alkyl iodides;Yuan, Jiaqi et al.;《RSC Advances》;第11卷(第23期);第13832-13838页 * |
Synthesis of cyclopent-2-enones from furans using a nebulizer-based continuous flow photoreactor;Ioannou, Georgios I. et al.;《Organic & Biomolecular Chemistry 》;第15卷(第48期);第10151-10155页 * |
钯催化卤代烷烃参与的自由基型转化反应;周文俊等;《有机化学》;第37卷(第6期);第1322-1337页 * |
Also Published As
Publication number | Publication date |
---|---|
CN114685408A (zh) | 2022-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5766717B2 (ja) | Rompとrcm反応に対する高効率複分解触媒 | |
Xu et al. | The Chan-Evans-Lam N-arylation of phosphonic/phosphinic amides | |
Jinwei et al. | Visible-light-induced regioselective ortho-c—h phosphonylation of β-naphthols with diarylphosphine oxides | |
Okajima et al. | Generation of diarylcarbenium ion pools via electrochemical C–H bond dissociation | |
CN114685408B (zh) | 一种烷基呋喃化合物的制备方法 | |
EP4116308A1 (en) | Naphthyl silole production method, naphthyl silole having heterocyclic group, and graphene nanoribbons having heterocyclic group | |
JPWO2007105657A1 (ja) | クロスカップリング反応を用いたオリゴマー化合物の合成方法 | |
CN110683926B (zh) | 羧酸芳基酯类化合物的制备方法 | |
CN111454150A (zh) | 一种(s)-2-芳基丙酸酯类化合物的合成方法 | |
Kajanus et al. | Synthesis of bis (phenylethynyl) arylene-linked diporphyrins designed for studies of intramolecular energy transfer | |
JP2004026691A (ja) | 含フッ素スチレン重合性単量体の製造方法及びそれに使用される中間体化合物 | |
CN111675650B (zh) | 一种芳香乙烯基溴衍生物的制备方法 | |
CN109942361B (zh) | 一种芳基取代的三亚苯类化合物的制备方法及其应用 | |
CN107445835B (zh) | 一种1,2-二氢环丁烯并[a]萘衍生物及其前体的合成方法 | |
Kimura et al. | Study on Radical Telomerization of Esters of Methacrylic Acid by Using Bromotrichloromethane and Characteristics of the Resulting Telomers II. Primary Alkyl Methacrylates | |
JP2013519519A (ja) | ブタジエンの短鎖重合に有用なホスフィンに基づく新規触媒 | |
JPS6116376B2 (zh) | ||
CN114805017B (zh) | 一种2-氟-1,5-己二烯类化合物的制备方法 | |
JP6709889B2 (ja) | 多置換芳香族化合物及びその製造方法 | |
CN115925677B (zh) | 一种含噻吩砜-烯烃结构单元的荧光材料及其制备方法 | |
CN110143933B (zh) | 一种由苄溴类化合物直接合成环氧化合物的方法 | |
EP1604949A2 (en) | Sumanene and process for production thereof | |
CN110015946B (zh) | 一种1,5-二芳基-4-戊烯-1-醇化合物的制备方法 | |
CN113620795B (zh) | 苯并环庚烯酮类化合物的合成方法 | |
CN110577556B (zh) | 一种苯并磷杂吲哚衍生物及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |