CN106008346B - 一种常压下钯催化合成芳醛的方法 - Google Patents
一种常压下钯催化合成芳醛的方法 Download PDFInfo
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- CN106008346B CN106008346B CN201610446905.0A CN201610446905A CN106008346B CN 106008346 B CN106008346 B CN 106008346B CN 201610446905 A CN201610446905 A CN 201610446905A CN 106008346 B CN106008346 B CN 106008346B
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- palladium
- aromatic aldehyde
- reaction
- sodium
- normal pressure
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 35
- 150000003934 aromatic aldehydes Chemical class 0.000 title claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- 239000002904 solvent Substances 0.000 claims abstract description 37
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 34
- 239000003446 ligand Substances 0.000 claims abstract description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 12
- 150000001502 aryl halides Chemical class 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000005859 coupling reaction Methods 0.000 claims abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 42
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 27
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 21
- -1 hydrogen siloxane Chemical class 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 9
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 8
- 239000001488 sodium phosphate Substances 0.000 claims description 8
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 4
- 238000006880 cross-coupling reaction Methods 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 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
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 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
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 3
- WTXXSZUATXIAJO-OWBHPGMISA-N (Z)-14-methylpentadec-2-enoic acid Chemical compound CC(CCCCCCCCCC\C=C/C(=O)O)C WTXXSZUATXIAJO-OWBHPGMISA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- ZGYICYBLPGRURT-UHFFFAOYSA-N tri(propan-2-yl)silicon Chemical compound CC(C)[Si](C(C)C)C(C)C ZGYICYBLPGRURT-UHFFFAOYSA-N 0.000 claims description 3
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 125000000842 isoxazolyl group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000002971 oxazolyl group Chemical group 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride 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
- 125000001725 pyrenyl group Chemical group 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000000335 thiazolyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- JTSVYBPWSSQBEB-UHFFFAOYSA-N azanium;hexanoate Chemical compound [NH4+].CCCCCC([O-])=O JTSVYBPWSSQBEB-UHFFFAOYSA-N 0.000 claims 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims 1
- 229910000024 caesium carbonate Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 32
- 239000000758 substrate Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 239000012429 reaction media Substances 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 238000006578 reductive coupling reaction Methods 0.000 abstract 1
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 46
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- 238000001704 evaporation Methods 0.000 description 30
- 239000012074 organic phase Substances 0.000 description 30
- 239000011541 reaction mixture Substances 0.000 description 30
- 238000004440 column chromatography Methods 0.000 description 29
- 239000012266 salt solution Substances 0.000 description 27
- 229920006395 saturated elastomer Polymers 0.000 description 27
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 26
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 25
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000000284 extract Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- ITCMXBVIXVDAKR-UHFFFAOYSA-M azanium tetrabutylazanium diacetate Chemical compound C(C)(=O)[O-].[NH4+].C(CCC)[N+](CCCC)(CCCC)CCCC.C(C)(=O)[O-] ITCMXBVIXVDAKR-UHFFFAOYSA-M 0.000 description 2
- 229960004424 carbon dioxide Drugs 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 description 1
- 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 1
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- 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 1
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Classifications
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- 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
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
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- C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
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Abstract
本发明公开了一种常压下钯催化合成芳醛的方法,属于催化合成技术领域。本发明在溶剂聚乙二醇或聚乙二醇的水溶液中,在碱和还原剂的作用下,无需配体参与的钯催化芳基卤代物、与常压一氧化碳直接还原偶联制备芳醛。本发明催化还原偶联反应制备芳醛的方法,无需配体且活性好;反应常温常压下进行且选择性高;底物来源广泛且稳定;底物官能团相容性好且底物的适用范围广;反应介质绿色且可以循环回收。在优化的反应条件之下,目标产品分离收率高达92%。
Description
技术领域
本发明属于催化合成技术领域,更具体地说,涉及一种常压下钯催化合成芳醛的方法,是无配体钯催化芳基卤代物与常压一氧化碳还原交叉偶联来制备芳醛的方法。
背景技术
芳醛是一类重要的有机合成中间体,广泛应用于医药、农药、染料和香料等的合成。目前报道的芳醛合成方法中,钯催化的还原羰基化芳卤法引起了广泛的关注,因为该方法具有适用范围广、底物官能团相容性好、选择性和产率高和原子经济性高的优势。虽然该方法已取得了一定的进展,特别是在催化剂设计和底物适用范围上,然而,通常情况下,该方法需要用到高压装置,且反应温度较高,而且还需要适用昂贵而有毒的膦配体来提高反应效果(X.-F.Wu,M.Beller,Transition Metal Catalyzed Carbonylation Reactions-Carbonylative Activation of C–X Bonds,Springer-Verlag Berlin,Heidelberg,2013),这些都限制了该方法的广泛应用。例如,中国专利申请号为200680010029.1,公开日为2008年3月26日的专利申请文件公开了一种芳香醛类的制备方法,该方法需要在特定的单齿磷烷基配体体系的存在下,通过钯催化的还原羰基化从相应的Hal’-取代的(杂)芳香族化合物获得醛类。该反应需要特定的磷配体,而且反应温度较高,限制了其广泛应用。
为了克服反应压力大的不足,计量反应的羰基试剂如COgen(S.Korsager,R.H.Taaning,A.T.Lindhardt,T.Skrydstrup,J.Org.Chem.2013,78,6112)、多聚甲醛(K.Natte,A.Dumrath,H.Neumann,M.Beller,Angew.Chem.Int.Ed.2014,53,10090.)以及N-甲酰亚胺(T.Ueda,H.Konishi,K.Manabe,Angew.Chem.Int.Ed.2013,52,8611)等也相继用于代替一氧化碳或合成气,取得了较好的反应效果,但反应仍旧需要较高的反应温度和膦配体的参与,而且原子经济性较差。到目前为止,尚未有一个通用的常压下、无配体的钯催化还原羰基化芳卤制备芳醛方法的报道。从节能减排和经济的角度看,发明一个常压下、经济的、环境友好的和高效的方法来合成芳醛具有重要的研究意义和应用价值。
发明内容
1.要解决的问题
针对现有的芳醛合成方法存在需要高压、较高的反应温度和膦配体的参与等问题,本发明提供一种常压下钯催化合成芳醛的方法,在无配体条件下钯催化芳卤与常压一氧化碳直接还原偶联合成芳醛,该方法具有显著的优势:反应能在常温常压下进行且选择性高;反应无需配体且活性好;底物来源广泛且稳定;底物官能团相容性好且底物的适用范围广;反应介质绿色且可以循环回收的优势。
2.技术方案
为了解决上述问题,本发明所采用的技术方案如下:
一种常压下钯催化合成芳醛的方法,以醇溶液为溶剂,在碱和还原剂的作用下,钯催化剂催化芳基卤代物与一氧化碳直接还原交叉偶联反应,制得芳醛,反应通式表示如下:
式中:X=I或Br;
Ar-X表示芳基或杂芳基的芳基卤代物;
本发明的方法所合成的芳醛产品的结构通式为:
式中,Ar表示的芳基为取代或非取代的苯基、联苯基、萘基、蒽基、菲基或芘基;Ar表示的杂芳基为含N,O或S的五至十三元环的杂芳基,其中,偶联反应温度为20~200℃,反应时间为0.5~60小时。
进一步地,所述的杂芳基为呋喃基、苯并呋喃基、噻吩基、吡咯基、吲哚基、咔唑基、吡啶基、异恶唑基、吡唑基、咪唑基、恶唑基或噻唑基。
进一步地,所述的Ar上的取代基可以是单取代,也可以是多取代芳环上的氢,所述的取代基任意选自氢、C1~C12直链或支链的烷基、C1~C12直链或支链的烷氧基、C1~C12直链或支链的氟取代烷基、C3~C12的环烷基、苯基、氟、氯、溴、羟基、羧基、甲酯基、乙酯基、丙酯基、氰基、硝基或甲酰基。
进一步地,Ar表示杂芳基吡咯基、咪唑基、吲哚基、吡唑基和咔唑基时,其氮原子上的取代基任意选自氢、C1~C12直链或支链的烷基、C3~C12的环烷基、芳基、対甲苯磺酰基、苄基、乙酰基、苯甲酰基或叔丁氧酰基。
优选地,所述的芳卤类化合物为苯类、联苯类、萘类、蒽类、芘类、呋喃类、苯并呋喃类、噻吩类、吡咯类、吲哚类、咔唑类、吡啶类、异恶唑类、吡唑类、咪唑类、恶唑类或噻唑类的芳碘或芳溴,最优选的芳卤类化合物为芳基碘代物。
进一步地,芳基卤代物、还原剂、碱和钯催化剂的摩尔比为1:(1~10):(1~10):(0.005~0.1)。
进一步地,所述的一氧化碳的压力为常压,芳基卤代物与溶剂的重量比为1:(5~1000)。
进一步地,所述的钯催化剂包括但不限于钯纳米、钯粉、钯碳、醋酸钯、氯化钯、氢氧化钯碳、三(二亚苄基丙酮)二钯、二苯腈氯化钯、二乙腈氯化钯或四氯钯酸钠。
进一步地,所述的还原剂包括但不限于为三乙基硅烷、三乙氧基硅烷、聚甲基氢硅氧烷、三异丙基硅烷、二甲基苯基硅烷、一苯基硅烷、二苯基硅烷、三苯基硅烷或1,1,3,3-四甲基二硅氧烷。
进一步地,所述的碱包括但不限于为碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸铯、醋酸钠、醋酸钾、醋酸铯、特戊酸铯、特戊酸钾、特戊酸钠、特戊酸锂、磷酸钾、磷酸氢钾、磷酸氢二钾、磷酸钠、磷酸氢钠、磷酸氢二钠、氟化钾、氟化铯、甲醇钠、乙醇钠,乙醇钾、叔丁醇锂、叔丁醇钠、叔丁醇钾、四丁基氟化铵、四丁基醋酸铵、三乙胺或二异丙基乙胺中的一种或几种。
进一步地,所述的醇溶液包括但不限于为平均分子量为100~10000的聚乙二醇,或平均分子量为100~10000的聚乙二醇水溶液,其中聚乙二醇与水的体积比为1:(0~100)。
3.有益效果
相比于现有技术,本发明的有益效果为:
(1)本发明提供了一种在聚乙二醇或聚乙二醇的水溶液中无配体钯催化的芳卤与常压一氧化碳的直接还原交叉偶联反应来制备芳醛的新方法,该方法具有无需配体和常压反应的独特优势;反应无需配体且活性好;反应常压进行且选择性高;
(2)本发明提供的芳醛合成方法中,底物来源广泛且稳定;底物官能团相容性好且底物的适用范围广;反应介质绿色且可以循环回收的优势,所述的方法简单易行,一步法直接得到芳醛,在优化的反应条件之下,目标产品分离后收率高达92%,是一种通用、高效、经济、环境友好的合成芳醛的方法;
(3)本发明的方法之所以能够在无配体和常温常压下进行,关键在于选择了聚乙二醇为主体的溶剂,聚乙二醇在本反应中起了多重作用:反应的溶剂、还原剂和稳定剂,聚乙二醇还原剂与稳定剂的作用可以使钯形成具有高催化活性的钯纳米催化剂,从而使反应能在非常温和的条件下进行,并取得理想的催化效果。
具体实施方式
下面结合具体实施例对本发明进一步进行描述。
为更进一步阐述本发明为达成预定发明目的所采取的技术手段及功效,对依据本发明提出的技术方案具体实施方式、特征及其功效,详细说明如后。
实施例1
化合物1:25mL反应瓶中依次加入醋酸钯(0.01mmol),碳酸钠(0.5mmol),碳酸氢钠(0.5mmol),碘苯(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率81%。
实施例2
化合物2:25mL反应瓶中依次加入钯纳米(0.01mmol),碳酸钠(0.5mmol),碳酸氢钠(0.5mmol),4-异丙基碘苯(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率85%。
实施例3
化合物3:25mL反应瓶中依次加入氯化钯(0.01mmol),特戊酸钾(0.5mmol),碳酸氢钠(0.5mmol),4-环己基碘苯(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(1.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应30h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率88%。
实施例4
化合物4:25mL反应瓶中依次加入二乙腈氯化钯(0.01mmol),碳酸钠(1.0mmol),3-乙氧基碘苯(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-200(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应48h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率80%。
实施例5
化合物5:25mL反应瓶中依次加入醋酸钯(0.01mmol),碳酸钠(1.0mmol),碳酸氢钠(0.5mmol),4-硝基碘苯(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在100℃下反应36h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率85%。
实施例6
化合物6:25mL反应瓶中依次加入醋酸钯(0.01mmol),碳酸氢钠(1.0mmol),4-碘苯甲酸(0.5mmol),三异丙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率71%。
实施例7
化合物7:25mL反应瓶中依次加入醋酸钯(0.01mmol),碳酸钠(0.5mmol),碳酸氢钠(0.5mmol),4-碘苯甲酸甲酯(0.5mmol),三乙氧基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率83%。
实施例8
化合物8:25mL反应瓶中依次加入醋酸钯(0.01mmol),碳酸钠(0.5mmol),碳酸氢钠(0.5mmol),1-碘萘(0.5mmol),1,1,3,3-四甲基二硅氧烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应36h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率85%。
实施例9
化合物9:25mL反应瓶中依次加入醋酸钯(0.01mmol),碳酸钠(0.5mmol),碳酸氢钠(0.5mmol),4-碘-1,1’联苯(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-600(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应36h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率86%。
实施例10
化合物10:25mL反应瓶中依次加入醋酸钯(0.01mmol),碳酸钠(0.5mmol),碳酸氢钠(0.5mmol),3-碘苯甲醛(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-1000(2.0g),并引入一个大气压的一氧化碳。反应混合物在60℃下反应12h。冷却到室温,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率80%。
实施例11
化合物11:25mL反应瓶中依次加入醋酸钯(0.01mmol),醋酸钠(1.0mmol),叔丁醇钠(1.0mmol),4-碘苯腈(0.5mmol),聚甲基氢硅氧烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率83%。
实施例12
化合物12:25mL反应瓶中依次加入醋酸钯(0.001mmol),特戊酸钾(1.0mmol),三乙胺(0.5mmol),4-碘苯酚(0.5mmol),一苯基硅烷(2.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率65%。
实施例13
化合物13:25mL反应瓶中依次加入醋酸钯(0.01mmol),磷酸钠(1.0mmol),1-氟-3-氯-4-碘苯(0.5mmol),三乙氧基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应12h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率83%。
实施例14
化合物14:25mL反应瓶中依次加入醋酸钯(0.01mmol),四丁基氟化铵(1.0mmol),4-三氟甲基碘苯(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应12h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率82%。
实施例15
化合物15:25mL反应瓶中依次加入醋酸钯(0.01mmol),碳酸钠(1.0mmol),4-碘吡啶(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在100℃下反应24h。冷却到室温,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率72%。
实施例16
化合物16:25mL反应瓶中依次加入醋酸钯(0.01mmol),碳酸钠(0.5mmol),碳酸氢钠(0.5mmol),3-碘噻吩(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。冷却到室温,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率90%。
实施例17
化合物17:25mL反应瓶中依次加入三(二亚苄基丙酮)二钯(0.005mmol),碳酸钠(0.5mmol),碳酸氢钠(0.5mmol),3,5-二甲基碘异恶唑(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率88%。
实施例18
化合物18:25mL反应瓶中依次加入钯碳(0.01mmol),碳酸钠(0.5mmol),磷酸氢钠(0.5mmol),3-碘苯并呋喃(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在80℃下反应24h。冷却到室温,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率89%。
实施例19
化合物19:25mL反应瓶中依次加入二苯腈氯化钯(0.01mmol),碳酸钠(0.5mmol),碳酸氢钠(0.5mmol),4-碘噻唑(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在室温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率80%。
实施例20
化合物20:25mL反应瓶中依次加入二苯腈氯化钯(0.005mmol),碳酸钠(1.0mmol),2,4-二碘恶唑(0.5mmol),三乙基硅烷(1.0mmol),聚乙二醇-400(1.0g)和水(0.1g),并引入一个大气压的一氧化碳。反应混合物在100℃下反应24h。冷却到室温,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率77%。
实施例21
化合物21:25mL反应瓶中依次加入氯化钯(0.01mmol),碳酸钠(1.0mmol),1-苄基-2-碘噻唑(0.5mmol),一苯基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率89%。
实施例22
化合物22:25mL反应瓶中依次加入醋酸钯(0.01mmol),醋酸铯(1.0mmol),1,4-二碘苯(0.5mmol),三乙基硅烷(1.0mmol),聚乙二醇-8000(2.0g)和水(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率61%。
实施例23
化合物23:25mL反应瓶中依次加入醋酸化钯(0.01mmol),磷酸钠(1.0mmol),2-碘吡咯(0.5mmol),二苯基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在80℃下反应24h。反应冷却到室温,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率71%。
实施例24
化合物24:25mL反应瓶中依次加入氯化钯(0.01mmol),四丁基醋酸铵(1.0mmol),1-苯基-2-碘吡咯(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率80%。
实施例25
化合物25:25mL反应瓶中依次加入醋酸钯(0.01mmol),碳酸钠(0.5mmol),碳酸氢钠(0.5mmol),1-戊基-3-碘吲哚(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率86%。
实施例26
化合物26:25mL反应瓶中依次加入醋酸钯(0.01mmol),碳酸钠(0.5mmol),碳酸氢钠(0.5mmol),1-环丙基-3-碘吲哚(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率85%。
实施例27
化合物27:25mL反应瓶中依次加入醋酸钯(0.01mmol),碳酸钠(0.5mmol),碳酸氢钠(0.5mmol),1-对甲苯磺酰基-3-碘吲哚(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率83%。
实施例28
化合物28:25mL反应瓶中依次加入醋酸钯(0.01mmol),醋酸钠(0.5mmol),磷酸钾(0.5mmol),1-乙酰基-3-碘吲哚(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率81%。
实施例29
化合物29:25mL反应瓶中依次加入醋酸钯(0.01mmol),碳酸钠(0.5mmol),乙醇钠(0.5mmol),叔丁氧羰基保护的咔唑碘化物(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率79%。
实施例30
化合物30:25mL反应瓶中依次加入醋酸钯(0.01mmol),磷酸钠(0.5mmol),碳酸氢钠(0.5mmol),1-苯甲酰基-4-碘吡唑(0.5mmol),三乙基硅烷(1.0mmol)和聚乙二醇-400(2.0g),并引入一个大气压的一氧化碳。反应混合物在常温下反应24h。反应结束,加入饱和食盐水10mL,并用***萃取(10mL×3),合并有机相,减压蒸除溶剂后柱层析分离得到产率87%。
实施例1~30涉及具体芳醛的合成方法对应的实验结果列于表1:
表1无配体钯催化的芳醛的合成[a]
[a]反应条件见实施例;[b]柱分离收率。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,本发明中的各种钯催化剂在聚乙二醇或其水溶液中,都能形成高活性的钯纳米催化剂,从而有利于反应的顺利进行;碱是发生芳卤代物羰基化反应所必须的促进剂,利用的是其碱性中和掉反应形成的氢卤酸,本发明给出的各种碱,都应能取得类似之效果;硅烷类的还原剂,利用的是硅-氢键的作用,还原有机钯中间体,形成有机钯-氢关键物,从而使反应顺利形成产品芳醛,本发明提供的具有还原性的氢硅烷都应能取得上述实施例中的效果;芳基卤代物发生反应的化学键是碳-卤键,而其芳环上的取代基影响的是芳环的电子云密度大小以及反应时的空间位阻大小,即取代基的修饰只是一定程度上影响反应,不对反应的发生起决定作用。任何熟悉本专业的技术人员不难理解,在不脱离本发明技术方案范围内,当可进行变动或修饰得到相应的实施例,例如对于所述的取代基可在本发明范围内进行替换、改变或修饰,均可以实现本发明方法。但凡是未脱离本发明技术方案的宗旨,依据本发明的对以上实施例所作的任何修改、修饰或等同与等效的变化,均仍属于本发明技术方案的范围内。
Claims (7)
1.一种常压下钯催化合成芳醛的方法,其特征在于:以醇溶液为溶剂,在碱和还原剂的作用下,钯催化剂催化芳基卤代物与一氧化碳直接还原交叉偶联反应,制得芳醛,反应过程中无配体参与,反应通式表示如下:
式中:X=I或Br;
Ar-X表示芳基或杂芳基的芳基卤代物;Ar表示的芳基为取代或非取代的苯基、联苯基、萘基、蒽基、菲基或芘基;Ar表示的杂芳基为含N,O或S的五至十三元环的杂芳基,
其中,所述的醇溶液为平均分子量为100~10000的聚乙二醇,或平均分子量为100~10000的聚乙二醇水溶液,其中聚乙二醇与水的体积比为1:(0~100);所述的还原剂为三乙基硅烷、三乙氧基硅烷、聚甲基氢硅氧烷、三异丙基硅烷、二甲基苯基硅烷、一苯基硅烷、二苯基硅烷、三苯基硅烷或1,1,3,3-四甲基二硅氧烷;所述的钯催化剂为钯纳米、钯粉、钯碳、醋酸钯、氯化钯、氢氧化钯碳、三(二亚苄基丙酮)二钯、二苯腈氯化钯、二乙腈氯化钯或四氯钯酸钠;偶联反应温度为20~200℃,反应时间为0.5~60小时。
2.根据权利要求1所述的一种常压下钯催化合成芳醛的方法,其特征在于:所述的杂芳基为呋喃基、苯并呋喃基、噻吩基、吡咯基、吲哚基、咔唑基、吡啶基、异恶唑基、吡唑基、咪唑基、恶唑基或噻唑基。
3.根据权利要求1所述的一种常压下钯催化合成芳醛的方法,其特征在于:所述的Ar上的取代基单取代或多取代芳环上的氢,所述的取代基任意选自氢、C1~C12直链或支链的烷基、C1~C12直链或支链的烷氧基、C1~C12直链或支链的氟取代烷基、C3~C12的环烷基、苯基、氟、氯、溴、羟基、羧基、甲酯基、乙酯基、丙酯基、氰基、硝基或甲酰基。
4.根据权利要求2所述的一种常压下钯催化合成芳醛的方法,其特征在于:Ar表示杂芳基吡咯基、咪唑基、吲哚基、吡唑基和咔唑基时,其氮原子上的取代基任意选自氢、C1~C12直链或支链的烷基、C3~C12的环烷基、芳基、対甲苯磺酰基、苄基、乙酰基、苯甲酰基或叔丁氧酰基。
5.根据权利要求1所述的一种常压下钯催化合成芳醛的方法,其特征在于:芳基卤代物、还原剂、碱和钯催化剂的摩尔比为1:(1~10):(1~10):(0.005~0.1)。
6.根据权利要求1所述的一种常压下钯催化合成芳醛的方法,其特征在于:所述的一氧化碳的压力为常压,芳基卤代物与溶剂的重量比为1:(5~1000)。
7.根据权利要求1或5所述的一种常压下钯催化合成芳醛的方法,其特征在于:所述的碱为碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸铯、醋酸钠、醋酸钾、醋酸铯、特戊酸铯、特戊酸钾、特戊酸钠、特戊酸锂、磷酸钾、磷酸氢钾、磷酸氢二钾、磷酸钠、磷酸氢钠、磷酸氢二钠、氟化钾、氟化铯、甲醇钠、乙醇钠,乙醇钾、叔丁醇锂、叔丁醇钠、叔丁醇钾、四丁基氟化铵、四丁基醋酸铵、三乙胺或二异丙基乙胺中的一种或几种。
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