CN106905097A - 一种氧化伯醇制备醛的方法 - Google Patents
一种氧化伯醇制备醛的方法 Download PDFInfo
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- CN106905097A CN106905097A CN201710130253.4A CN201710130253A CN106905097A CN 106905097 A CN106905097 A CN 106905097A CN 201710130253 A CN201710130253 A CN 201710130253A CN 106905097 A CN106905097 A CN 106905097A
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 6
- 150000003138 primary alcohols Chemical class 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 72
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 40
- 239000003208 petroleum Substances 0.000 claims description 20
- 239000012043 crude product Substances 0.000 claims description 19
- 238000004440 column chromatography Methods 0.000 claims description 15
- -1 2,2,6,6- tetramethyl piperidines nitrogen oxides Chemical class 0.000 claims description 11
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 9
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000005336 allyloxy group Chemical group 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 4
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 3
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 claims description 3
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 3
- 125000006185 3,4-dimethyl benzyl group Chemical group [H]C1=C(C([H])=C(C(=C1[H])C([H])([H])[H])C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 125000005504 styryl group Chemical group 0.000 claims description 3
- QPHLRCUCFDXGLY-UHFFFAOYSA-N (3,4,5-trimethoxyphenyl)methanol Chemical class COC1=CC(CO)=CC(OC)=C1OC QPHLRCUCFDXGLY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- AKKLAJYCGVIWBS-UHFFFAOYSA-N O=[N].CC1(C)CCCC(C)(C)N1 Chemical class O=[N].CC1(C)CCCC(C)(C)N1 AKKLAJYCGVIWBS-UHFFFAOYSA-N 0.000 claims description 2
- 238000013459 approach Methods 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 230000003244 pro-oxidative effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- 150000001879 copper Chemical class 0.000 abstract description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 72
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 18
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 18
- 230000035484 reaction time Effects 0.000 description 18
- 239000000376 reactant Substances 0.000 description 17
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229960004217 benzyl alcohol Drugs 0.000 description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- WYLYBQSHRJMURN-UHFFFAOYSA-N (2-methoxyphenyl)methanol Chemical compound COC1=CC=CC=C1CO WYLYBQSHRJMURN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- PTHGDVCPCZKZKR-UHFFFAOYSA-N (4-chlorophenyl)methanol Chemical compound OCC1=CC=C(Cl)C=C1 PTHGDVCPCZKZKR-UHFFFAOYSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- JVWACRJCXSYXSJ-UHFFFAOYSA-N 1-phenyl-1-sulfanylethanol Chemical compound CC(O)(S)C1=CC=CC=C1 JVWACRJCXSYXSJ-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- VGHNZWJZFGNSJS-UHFFFAOYSA-N C1(=CC=CC=C1)CO.[I] Chemical group C1(=CC=CC=C1)CO.[I] VGHNZWJZFGNSJS-UHFFFAOYSA-N 0.000 description 1
- PKZJLOCLABXVMC-UHFFFAOYSA-N COc1ccccc1C=O Chemical compound COc1ccccc1C=O PKZJLOCLABXVMC-UHFFFAOYSA-N 0.000 description 1
- ZVTWZSXLLMNMQC-UHFFFAOYSA-N O=Cc(cc1)ccc1OCc1ccccc1 Chemical compound O=Cc(cc1)ccc1OCc1ccccc1 ZVTWZSXLLMNMQC-UHFFFAOYSA-N 0.000 description 1
- OEBIVOHKFYSBPE-UHFFFAOYSA-N OCc(cc1)ccc1OCc1ccccc1 Chemical compound OCc(cc1)ccc1OCc1ccccc1 OEBIVOHKFYSBPE-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- XJUJXVATKIRSAM-UHFFFAOYSA-N fluoro(phenyl)methanol Chemical compound OC(F)C1=CC=CC=C1 XJUJXVATKIRSAM-UHFFFAOYSA-N 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- XUZLXCQFXTZASF-UHFFFAOYSA-N nitro(phenyl)methanol Chemical compound [O-][N+](=O)C(O)C1=CC=CC=C1 XUZLXCQFXTZASF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- KKHBCIDRVKMURK-UHFFFAOYSA-N phenyl(phenylmethoxy)methanol Chemical compound C=1C=CC=CC=1C(O)OCC1=CC=CC=C1 KKHBCIDRVKMURK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ZPHGMBGIFODUMF-UHFFFAOYSA-N thiophen-2-ylmethanol Chemical compound OCC1=CC=CS1 ZPHGMBGIFODUMF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl 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
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D213/02—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 having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—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 having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—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 having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/46—Oxygen atoms
- C07D213/48—Aldehydo radicals
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- 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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种催化氧化伯醇制备醛的方法,所述方法按如下步骤进行:以式(I)或(III)所示的伯醇为原料,以铜盐为催化剂,以空气为氧化剂,以TEMPO(2,2,6,6‑四甲基哌啶氮氧化物)为助氧化剂,氨水为助催化剂和溶剂,混合均匀于60~120℃下进行反应9~24h,反应结束后,反应液经后处理得到(II)或(IV)所示的醛;本发明反应转化率、收率高,操作方便,成本低,反应安全,整个过程对环境友好,无污染。
Description
(一)技术领域
本发明涉及一种催化氧化伯醇制备醛的方法。
(二)背景技术
醇的选择性氧化是有机化学里最重要的反应之一。特别是一级醇经过氧化转变成醛的反应,对合成类似于香水和食品添加剂的精细化学品是至关重要的。传统由醇氧化制备醛的方法,需要使用到重金属盐或含有贵金属的催化剂,如:钯、铑、钌。通常,这些反应需要在苛刻的条件下进行。
金属铜在地壳中的含量很丰富。因此,铜廉价、易得、绿色的特点使得很多化学研究者去探索了它作为催化剂促进醇氧化的可能性。自从发现铜结合半乳糖的氧化酶,应用到醇的需氧选择性氧化制备羰基化合物的反应中具有很高的活性后,发展一种以金属铜盐作为催化剂,空气或者氧气作为最终氧化剂实现醇选择性氧化的体系成为了有机化学的研究热点。近年来,报道了很多有关铜结合氧气催化醇选择性氧化的方法。但是,这些方法通常都是在有机溶剂或者有机溶剂与水的混合溶液中进行,而在纯水相中反应则很少报道。另外,这些体系中,需要使用到诸如联吡啶、菲罗啉、氮杂卡宾以及他们的类似物配体以促进反应顺利进行。通常这类配体中有些在结构上比较复杂,难以通过商业途径得到,需要繁琐的制备过程得到。因此,发展一类由简单配体促进的,在有氧的水相环境中,通过铜催化醇的选择性氧化,实现一级醇到醛的制备是很有意义的。
Lei Ziqiang等人在CH2Cl2中,用运了过氧硫酸四正丁铵盐将苄醇氧化成醛。其缺点还是溶剂不够绿色、安全催化剂比较危险[Lei Ziqiang et al.,Adv.Synth.&Catal.,2006,348(7+8),877.]。Zhang Miao等人通过加入氧气,TiO2,以三氟甲苯作为溶剂,氧化醇为醛。该反应的溶剂成本较高,而且污染较大[Zhang Miao et al.,Angew.Chem.Int.Ed.,2009,48(33),6081.]。Hu Zongmin等人用NaClO2,以含邻二氮菲的二价钌作为催化剂,将苄醇氧化成醛。其缺点还是溶剂不够绿色、安全催化剂比较危险[Hu Zongmin et al.,Chem.Commun.,2012,48(8),1102.]。
综上所述,现有技术合成醛的方法,存在不少缺点与不足,如:成本较高,不够绿色环保,反应温度较高,反应周期较长等等。
(三)发明内容
为解决现有技术训存在的问题,本发明的目的在于提供一种催化氧化制备醛的新方法。
本发明采用的技术方案是:
一种催化氧化制备醛的方法,所述方法按如下步骤进行:
以式(I)或(III)所示的伯醇为原料,以铜盐为催化剂,以空气为氧化剂,以TEMPO(2,2,6,6-四甲基哌啶氮氧化物)为助氧化剂,氨水为助催化剂和溶剂,混合均匀于60~120℃下进行反应9~24h,反应结束后,反应液经后处理得到(II)或(IV)所示的醛;所述式(I)或(III)所示的伯醇与铜盐、TEMPO(2,2,6,6-四甲基哌啶氮氧化物)的物质的量之比为:1:0.03~0.08:0.03~0.08;所述氨水的浓度为1.0×10-2mol/L~3.0×10-2mol/L;所述氨水的体积用量以伯醇的物质的量之比为2.0~5.0mL/mmol,
式(I)、(II)、(III)、(IV)中:
所述R1为氢或氢被甲基、甲氧基、氟、氯、溴、碘、硝基、甲硫基、苄氧基、烯丙氧基单取代或多取代;
所述Het为3-吡啶基、2-呋喃基、2-噻吩基、1-萘基或苯乙烯基。
进一步,所述催化剂为CuI、CuBr、CuCl、CuO、CuBr2、CuCl2、CuSO4、Cu(NO3)2、Cu(OAc)2或Cu(OTf)2。
再进一步,优选所述催化剂为CuI、CuBr或CuCl。
进一步,优选所述R1为氢或氢被甲基、甲氧基、氟、氯、溴、碘、硝基、甲硫基、苄氧基、烯丙氧基单取代。
进一步,优选所述式(I)所示的伯醇为3,4-二甲基苄醇或3,4,5-三甲氧基苄醇。
本发明所述反应液后处理方法为:待反应结束后,反应液冷却至室温,用乙酸乙酯萃取,合并有机层,真空浓缩除去乙酸乙酯得粗产品,所得粗产品经柱色谱纯化,以石油醚:乙酸乙酯=5~10:1为洗脱剂进行洗脱,得到(II)或(IV)所示的醛。
本发明整个反应过程在一个开放的空气气氛中进行。
本发明的有益效果主要体现在:
1、反应转化率、产率较高,底物适用性强,操作方便。
2、原料价廉易得,成本低,反应在常压下进行,反应绿色安全。
3、反应的副产物为水,整个过程对环境友好,不会对环境造成污染。
(四)具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此:
实施例中厚壁耐压管为欣维尔100mL规格。
实施例1:
在150mL的配有磁子搅拌的厚壁耐压管中,在空气气氛中,向体系中加苄醇(即结构式(I)中的R1为H)1.0mmol(108.1mg),氨水(1.6×10-2mol/L)5.0mL,碘化亚铜5mol%(9.5mg),TEMPO 5mol%(7.8mg),100℃下反应12h,待反应结束后,反应液冷却至室温,用乙酸乙酯萃取(3×5.0mL)。合并有机层,真空浓缩除去乙酸乙酯得粗产品。粗产品经柱色谱纯化(石油醚:乙酸乙酯=10:1),得纯的目标产物。得97.6mg收率为92%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ7.53(t,J=7.8Hz,2H),7.61-7.65(m,1H),7.87-7.90(m,2H),10.02(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ128.9,129.7,134.4,136.4,192.3.
实施例2:
所用的反应物为对甲基苄醇(即结构式(I)中的R1为对位CH3)1.0mmol(122.2mg),实验方法和步骤同实施例1,氨水(3.0×10-2mol/L)2.0mL,催化剂溴化亚铜的用量为8mol%(11.5mg),TEMPO的用量为5mol%(7.8mg),反应温度为80℃,反应时间为15h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=10:1),得111.8mg收率93%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ2.44(s,3H),7.34(d,J=8.0Hz,2H),7.78(d,J=8.0Hz,2H),9.97(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ21.8,129.7,129.8,134.2,145.5,191.9.
实施例3:
所用的反应物为邻甲氧基苄醇(即结构式(I)中的R1为邻位OCH3)1.0mmol(138.2mg),实验方法和步骤同实施例1,氨水(2.6×10-2mol/L)5.0mL,催化剂氯化亚铜的用量为8mol%(7.9mg),TEMPO的用量为8mol%(12.5mg),反应温度为120℃,反应时间为24h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=10:1),得123.9mg收率91%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ3.95(s,3H),7.00-7.07(m,2H),7.55-7.60(m,1H),7.84-7.86(q,1H),10.49(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ55.5,111.6,120.6,125.0,128.5,135.9,161.8,189.8.
实施例4:
所用的反应物为对氟苄醇(即结构式(I)中的R1为对位F)1.0mmol(126.1mg),实验方法和步骤同实施例1,氨水(1.6×10-2mol/L)5.0mL,催化剂氧化铜的用量为8mol%(6.4mg),TEMPO的用量为8mol%(7.8mg),反应温度为60℃,反应时间为24h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=10:1),得111.7mg收率90%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ7.16-7.20(m,2H),7.87-7.90(m,2H),9.94(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ116.3,132.4,133.0,164.8,191.6.
实施例5:
所用的反应物为对氯苄醇(即结构式(I)中的R1为对位Cl)1.0mmol(142.6mg),实验方法和步骤同实施例1,氨水(2.6×10-2mol/L)3.0mL,催化剂溴化铜的用量为8mol%(17.9mg),TEMPO的用量为8mol%(12.5mg),反应温度为120℃,反应时间为9h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=10:1),得133.6mg收率95%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ7.49-7.52(m,2H),7.81-7.84(dt,J=4.0Hz,2.5Hz,2H),9.98(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ129.4,130.9,134.7,140.9,190.8.
实施例6:
所用的反应物为对溴苄醇(即结构式(I)中的R1为对位Br)1.0mmol(187.0mg),实验方法和步骤同实施例1,氨水(2.6×10-2mol/L)3.0mL,催化剂氯化铜的用量为8mol%(10.8mg),TEMPO的用量为8mol%(12.5mg),反应温度为100℃,反应时间为15h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=10:1),得173.9mg收率94%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ7.69(d,J=4.3Hz,2H),7.75(d,J=4.3Hz,2H),9.98(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ129.7,130.9,132.4,135.2,190.9.
实施例7:
所用的反应物为邻碘苄醇(即结构式(I)中的R1为邻位I)1.0mmol(234.0mg),实验方法和步骤同实施例1,氨水(1.1×10-2mol/L)5.0mL,催化剂硫酸铜的用量为5mol%(8.0mg),TEMPO的用量为8mol%(12.5mg),反应温度为100℃,反应时间为18h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=10:1),得206.5mg收率89%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ7.30(dd,J=7.6,1.8Hz,1H),7.47(t,J=7.5Hz,1H),7.89(dd,J=7.7,1.8Hz,1H),7.96(dd,J=7.9,0.9Hz,1H),10.07(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ100.6,128.7,130.2,135.1,135.4,140.6,195.7.
实施例8:
所用的反应物为对硝基苄醇(即结构式(I)中的R1为对位NO2)1.0mmol(153.1mg),实验方法和步骤同实施例1,氨水(1.6×10-2mol/L)5.0mL,催化剂硝酸铜的用量为5mol%(9.38mg),TEMPO的用量为8mol%(12.5mg),反应温度为100℃,反应时间为24h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=5:1),得142.0mg收率94%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ8.09(d,J=4.5Hz,2H),8.40(d,J=4.5Hz,2H),10.17(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ124.3,130.5,140.2,151.3,190.2.
实施例9:
所用的反应物为对甲硫基苄醇(即结构式(I)中的R1为对位SCH3)1.0mmol(154.2mg),实验方法和步骤同实施例1,氨水(2.6×10-2mol/L)3.0mL,催化剂醋酸铜的用量为3mol%(5.4mg),TEMPO的用量为8mol%(12.5mg),反应温度为80℃,反应时间为20h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=8:1),得137.0mg收率90%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ2.53(s,3H),7.32(d,J=3.8Hz,2H),7.76(d,J=4.5Hz,2H),9.91(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ14.5,125.2,129.9,133.0,147.9,191.1.
实施例10:
所用的反应物为对苄氧基苄醇(即结构式(I)中的R1为对位OBn)1.0mmol(214.3mg),实验方法和步骤同实施例1,氨水(2.6×10-2mol/L)3.0mL,催化剂三氟甲磺酸铜的用量为3mol%(10.9mg),TEMPO的用量为3mol%(4.7mg),反应温度为60℃,反应时间为20h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=10:1),得201.6mg收率95%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ5.16(s,2H),7.07-7.13(m,2H),7.36-7.48(m,5H),7.83-7.89(m,2H),9.90(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ70.2,115.1,127.4,128.3,128.7,130.1,131.9,135.9,163.7,190.7.
实施例11:
所用的反应物为对烯丙氧基苄醇(即结构式(I)中的R1为对位烯丙氧基)1.0mmol(164.2mg),实验方法和步骤同实施例1,氨水(2.6×10-2mol/L)3.0mL,催化剂溴化亚铜的用量为5mol%(7.2mg),TEMPO的用量为8mol%(12.5mg),反应温度为60℃,反应时间为15h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=8:1),得155.7mg收率96%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ4.61-4.66(m,2H),5.34(dd,J=10.5,1.3Hz,1H),5.45(dt,J=17.3,1.5Hz,1H),6.06(ddt,J=17.2,10.5,5.3Hz,1H),7.02(d,J=8.7Hz,2H),7.84(d,J=8.8Hz,2H),9.89(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ69.0,115.0,118.2,130.0,131.9,132.3,163.6,190.7.
实施例12:
所用的反应物为吡啶-3-甲醇(即结构式(III)中的Het为3-吡啶基)1.0mmol(109.1mg),实验方法和步骤同实施例1,氨水(2.6×10-2mol/L)3.0mL,催化剂碘化亚铜的用量为5mol%(9.5mg),TEMPO的用量为5mol%(7.8mg),反应温度为100℃,反应时间为9h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=8:1),得94.2mg收率88%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ7.46-7.50(q,1H),8.15-8.18(m,1H),8.82-8.84(q,1H),9.07(d,J=2.0Hz,1H),10.10(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ124.0,131.4,135.7,151.9,154.6,190.6.
实施例13:
所用的反应物为呋喃-2-甲醇(即结构式(III)中的Het为2-呋喃基)1.0mmol(98.1mg),实验方法和步骤同实施例1,氨水(2.6×10-2mol/L)3.0mL,催化剂碘化亚铜的用量为8mol%(15.2mg),TEMPO的用量为5mol%(7.8mg),反应温度为100℃,反应时间为12h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=8:1),得89.3mg收率93%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ6.53-6.55(q,1H),7.20-7.21(q,1H),7.63(d,J=1.0Hz,1H),9.58(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ112.6,121.2,148.1,152.9,177.8.
实施例14:
所用的反应物为噻吩-2-甲醇(即结构式(III)中的Het为2-噻吩基)1.0mmol(114.2mg),实验方法和步骤同实施例1,氨水(2.6×10-2mol/L)3.0mL,催化剂碘化亚铜的用量为5mol%(9.5mg),TEMPO的用量为5mol%(7.8mg),反应温度为100℃,反应时间为15h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=8:1),得106.5mg收率95%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ7.18-7.20(q,1H),7.74-7.76(m,1H),7.77(dd,J=1.8Hz,1.5Hz,1H),9.92(d,J=1.5Hz,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ128.3,135.0,136.3,143.9,182.9.
实施例15:
所用的反应物为萘-1-甲醇(即结构式(III)中的Het为1-萘基)1.0mmol(158.2mg),实验方法和步骤同实施例1,氨水(1.6×10-2mol/L)5.0mL,催化剂碘化亚铜的用量为3mol%(5.7mg),TEMPO的用量为5mol%(7.8mg),反应温度为100℃,反应时间为18h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=10:1),得153.1mg收率98%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ7.57(t,J=7.5Hz,2H),7.66-7.70(m,1H),7.89(d,J=8.0Hz,1H),7.93(dd,J1=8.0,1.5Hz,1H),9.26(d,J=9.0Hz,1H),10.37(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ124.7,126.8,128.3,128.9,130.3,131.2,133.5,135.1,136.4,193.3.
实施例16:
所用的反应物为3-苯基-2-丙烯醇(即结构式(III)中的Het为苯乙烯基)1.0mmol(134.2mg),实验方法和步骤同实施例1,氨水(1.6×10-2mol/L)5.0mL,催化剂氯化亚铜的用量为8mol%(7.9mg),TEMPO的用量为5mol%(7.8mg),反应温度为100℃,反应时间为18h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=10:1),得122.9mg收率93%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ6.71(q,1H),7.42(d,J=2.0Hz,1H),7.43(d,J=2.0Hz,2H),7.45(d,J=2.5Hz,1H),7.55(d,J=2.5Hz,1H),7.56(d,J=2.0Hz,1H),9.69(d,J=7.0Hz,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ128.5,129.1,131.2,134.0,152.7,193.8.
实施例17:
所用的反应物为3,4-二甲基苄醇(即结构式(I)中的R1为对位、间位两个CH3)1.0mmol(136.2mg),实验方法和步骤同实施例1,氨水(2.6×10-2mol/L)3.0mL,催化剂溴化亚铜的用量为5mol%(7.2mg),TEMPO的用量为5mol%(7.8mg),反应温度为80℃,反应时间为20h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=10:1),得128.7mg收率96%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ2.30(d,J=2.0Hz,6H),7.25(d,J=4.0Hz,1H),7.59(t,J=8.0Hz,2H),9.90(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ19.4,20.0,127.6,130.1,130.4,134.5,137.3,144.1,192.0.
实施例18:
所用的反应物为3,4,5-三甲氧基苄醇(即结构式(I)中的R1为3位,4位,5位三个甲氧基)1.0mmol(198.2mg),实验方法和步骤同实施例1,氨水(1.6×10-2mol/L)5.0mL,催化剂溴化亚铜的用量为5mol%(7.2mg),TEMPO的用量为5mol%(7.8mg),反应温度为100℃,反应时间为20h,粗产品经柱色谱纯化(石油醚:乙酸乙酯=10:1),得186.4mg收率95%。
核磁共振氢谱:1H NMR(500MHz,CDCl3):δ3.89(d,J=4.0Hz,9H),7.09(s,2H),9.83(s,1H).
核磁共振碳谱:13C NMR(125MHz,CDCl3):δ56.2,60.8,106.7,131.7,143.6,153.6,190.8。
Claims (6)
1.一种催化氧化制备醛的方法,其特征在于,所述方法按如下步骤进行:
以式(I)或(III)所示的伯醇为原料,以铜盐为催化剂,以空气为氧化剂,以TEMPO(2,2,6,6-四甲基哌啶氮氧化物)为助氧化剂,氨水为助催化剂和溶剂,混合均匀于60~120℃下进行反应9~24h,反应结束后,反应液经后处理得到(II)或(IV)所示的醛;所述式(I)或(III)所示的伯醇与铜盐、TEMPO(2,2,6,6-四甲基哌啶氮氧化物)的物质的量之比为:1:0.03~0.08:0.03~0.08;所述氨水的浓度为1.0×10-2mol/L~3.0×10-2mol/L;所述氨水的体积用量以伯醇的物质的量之比为2.0~5.0mL/mmol,
式(I)、(II)、(III)、(IV)中:
所述R1为氢或氢被甲基、甲氧基、氟、氯、溴、碘、硝基、甲硫基、苄氧基、烯丙氧基单取代或多取代;
所述Het为3-吡啶基、2-呋喃基、2-噻吩基、1-萘基或苯乙烯基。
2.如权利要求1所述的方法,其特征在于,所述催化剂为CuI、CuBr、CuCl、CuO、CuBr2、CuCl2、CuSO4、Cu(NO3)2、Cu(OAc)2或Cu(OTf)2。
3.如权利要求2所述的方法,其特征在于,所述催化剂为CuI、CuBr或CuCl。
4.如权利要求1所述的方法,其特征在于,所述反应液后处理方法为:待反应结束后,反应液冷却至室温,用乙酸乙酯萃取,合并有机层,真空浓缩除去乙酸乙酯得粗产品,所得粗产品经柱色谱纯化,以石油醚:乙酸乙酯=5~10:1为洗脱剂进行洗脱,得到(II)或(IV)所示的醛。
5.如权利要求1所述的方法,其特征在于,所述R1为氢或氢被甲基、甲氧基、氟、氯、溴、碘、硝基、甲硫基、苄氧基、烯丙氧基单取代。
6.如权利要求1所述的方法,其特征在于,所述式(I)所示的伯醇为3,4-二甲基苄醇或3,4,5-三甲氧基苄醇。
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