CN109384645B - 一种合成仲醇的方法 - Google Patents
一种合成仲醇的方法 Download PDFInfo
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- CN109384645B CN109384645B CN201710683910.8A CN201710683910A CN109384645B CN 109384645 B CN109384645 B CN 109384645B CN 201710683910 A CN201710683910 A CN 201710683910A CN 109384645 B CN109384645 B CN 109384645B
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- isopropanol
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- 238000000034 method Methods 0.000 title claims abstract description 15
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- 230000002194 synthesizing effect Effects 0.000 title abstract description 6
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- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical group [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- -1 methoxyphenyl Chemical group 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 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
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 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
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000005059 halophenyl group Chemical group 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
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- 150000001875 compounds Chemical class 0.000 description 26
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 24
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- IUUULXXWNYKJSL-UHFFFAOYSA-N 4-methoxy-alpha-methylbenzyl alcohol Chemical compound COC1=CC=C(C(C)O)C=C1 IUUULXXWNYKJSL-UHFFFAOYSA-N 0.000 description 2
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- 239000002585 base Substances 0.000 description 2
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- XSWSEQPWKOWORN-UHFFFAOYSA-N dodecan-2-ol Chemical compound CCCCCCCCCCC(C)O XSWSEQPWKOWORN-UHFFFAOYSA-N 0.000 description 2
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- VZTGSONNNMGQNQ-UHFFFAOYSA-N 1-(3,4-dichlorophenyl)ethanol Chemical compound CC(O)C1=CC=C(Cl)C(Cl)=C1 VZTGSONNNMGQNQ-UHFFFAOYSA-N 0.000 description 1
- WBPAOUHWPONFEQ-UHFFFAOYSA-N 1-(3,4-dichlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C(Cl)=C1 WBPAOUHWPONFEQ-UHFFFAOYSA-N 0.000 description 1
- ULMJQMDYAOJNCC-UHFFFAOYSA-N 1-(3-bromophenyl)ethanol Chemical compound CC(O)C1=CC=CC(Br)=C1 ULMJQMDYAOJNCC-UHFFFAOYSA-N 0.000 description 1
- JYAQYXOVOHJRCS-UHFFFAOYSA-N 1-(3-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(Br)=C1 JYAQYXOVOHJRCS-UHFFFAOYSA-N 0.000 description 1
- XTDTYSBVMBQIBT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanol Chemical compound CC(O)C1=CC=C(Br)C=C1 XTDTYSBVMBQIBT-UHFFFAOYSA-N 0.000 description 1
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 1
- QLMFTKHAIDWIDC-UHFFFAOYSA-N 1-(4-bromophenyl)propan-1-ol Chemical compound CCC(O)C1=CC=C(Br)C=C1 QLMFTKHAIDWIDC-UHFFFAOYSA-N 0.000 description 1
- CFMMTXJMIJRUSH-UHFFFAOYSA-N 1-(4-bromophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C(Br)C=C1 CFMMTXJMIJRUSH-UHFFFAOYSA-N 0.000 description 1
- MVOSNPUNXINWAD-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanol Chemical compound CC(O)C1=CC=C(Cl)C=C1 MVOSNPUNXINWAD-UHFFFAOYSA-N 0.000 description 1
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 description 1
- TXAWBKBMGZKBNN-UHFFFAOYSA-N 1-(4-chlorophenyl)propan-1-ol Chemical compound CCC(O)C1=CC=C(Cl)C=C1 TXAWBKBMGZKBNN-UHFFFAOYSA-N 0.000 description 1
- WEJRYKSUUFKMBC-UHFFFAOYSA-N 1-(4-chlorophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C(Cl)C=C1 WEJRYKSUUFKMBC-UHFFFAOYSA-N 0.000 description 1
- HZFBZEOPUXCNHK-UHFFFAOYSA-N 1-(4-ethylphenyl)ethanol Chemical compound CCC1=CC=C(C(C)O)C=C1 HZFBZEOPUXCNHK-UHFFFAOYSA-N 0.000 description 1
- PSDSORRYQPTKSV-UHFFFAOYSA-N 1-(4-fluorophenyl)ethanol Chemical compound CC(O)C1=CC=C(F)C=C1 PSDSORRYQPTKSV-UHFFFAOYSA-N 0.000 description 1
- ZDPAWHACYDRYIW-UHFFFAOYSA-N 1-(4-fluorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(F)C=C1 ZDPAWHACYDRYIW-UHFFFAOYSA-N 0.000 description 1
- YMXIDIAEXNLCFT-UHFFFAOYSA-N 1-[4-(trifluoromethyl)phenyl]ethanol Chemical compound CC(O)C1=CC=C(C(F)(F)F)C=C1 YMXIDIAEXNLCFT-UHFFFAOYSA-N 0.000 description 1
- HHAISVSEJFEWBZ-UHFFFAOYSA-N 1-[4-(trifluoromethyl)phenyl]ethanone Chemical compound CC(=O)C1=CC=C(C(F)(F)F)C=C1 HHAISVSEJFEWBZ-UHFFFAOYSA-N 0.000 description 1
- AXRKCRWZRKETCK-UHFFFAOYSA-N 1-naphthalen-2-ylethanol Chemical compound C1=CC=CC2=CC(C(O)C)=CC=C21 AXRKCRWZRKETCK-UHFFFAOYSA-N 0.000 description 1
- GKDLTXYXODKDEA-UHFFFAOYSA-N 1-phenylbutan-2-one Chemical compound CCC(=O)CC1=CC=CC=C1 GKDLTXYXODKDEA-UHFFFAOYSA-N 0.000 description 1
- DZMNGSPDNIVJMT-UHFFFAOYSA-N 1-tritylpyrazole Chemical compound C1=CC=NN1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 DZMNGSPDNIVJMT-UHFFFAOYSA-N 0.000 description 1
- GITOMJDYNUMCOV-UHFFFAOYSA-N 2-(3,4-dichlorophenyl)ethanol Chemical compound OCCC1=CC=C(Cl)C(Cl)=C1 GITOMJDYNUMCOV-UHFFFAOYSA-N 0.000 description 1
- PTTFLKHCSZSFOL-UHFFFAOYSA-N 2-(3-bromophenyl)ethanol Chemical compound OCCC1=CC=CC(Br)=C1 PTTFLKHCSZSFOL-UHFFFAOYSA-N 0.000 description 1
- PMOSJSPFNDUAFY-UHFFFAOYSA-N 2-(4-bromophenyl)ethanol Chemical compound OCCC1=CC=C(Br)C=C1 PMOSJSPFNDUAFY-UHFFFAOYSA-N 0.000 description 1
- HZFRKZWBVUJYDA-UHFFFAOYSA-N 2-(4-chlorophenyl)ethanol Chemical compound OCCC1=CC=C(Cl)C=C1 HZFRKZWBVUJYDA-UHFFFAOYSA-N 0.000 description 1
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 description 1
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical compound CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 description 1
- XSAYZAUNJMRRIR-UHFFFAOYSA-N 2-acetylnaphthalene Chemical compound C1=CC=CC2=CC(C(=O)C)=CC=C21 XSAYZAUNJMRRIR-UHFFFAOYSA-N 0.000 description 1
- RXWNCMHRJCOWDK-UHFFFAOYSA-N 2-naphthalen-1-ylethanol Chemical compound C1=CC=C2C(CCO)=CC=CC2=C1 RXWNCMHRJCOWDK-UHFFFAOYSA-N 0.000 description 1
- XGAVOODMMBMCKV-UHFFFAOYSA-N 4-(1-hydroxyethyl)benzonitrile Chemical compound CC(O)C1=CC=C(C#N)C=C1 XGAVOODMMBMCKV-UHFFFAOYSA-N 0.000 description 1
- RBSJBNYPTGMZIH-UHFFFAOYSA-N 4-(2-hydroxyethyl)benzonitrile Chemical compound OCCC1=CC=C(C#N)C=C1 RBSJBNYPTGMZIH-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLPHXWGWBKZSJC-UHFFFAOYSA-N 4-acetylbenzonitrile Chemical compound CC(=O)C1=CC=C(C#N)C=C1 NLPHXWGWBKZSJC-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- MWUVGXCUHWKQJE-UHFFFAOYSA-N 4-fluorophenethyl alcohol Chemical compound OCCC1=CC=C(F)C=C1 MWUVGXCUHWKQJE-UHFFFAOYSA-N 0.000 description 1
- YQYGPGKTNQNXMH-UHFFFAOYSA-N 4-nitroacetophenone Chemical compound CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YQYGPGKTNQNXMH-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- AJIPIJNNOJSSQC-NYLIRDPKSA-N estetrol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H]([C@H](O)[C@@H]4O)O)[C@@H]4[C@@H]3CCC2=C1 AJIPIJNNOJSSQC-NYLIRDPKSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- FSPSELPMWGWDRY-UHFFFAOYSA-N m-Methylacetophenone Chemical compound CC(=O)C1=CC=CC(C)=C1 FSPSELPMWGWDRY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ZAJNGDIORYACQU-UHFFFAOYSA-N methyl n-octyl ketone Natural products CCCCCCCCC(C)=O ZAJNGDIORYACQU-UHFFFAOYSA-N 0.000 description 1
- NODGRWCMFMEGJH-UHFFFAOYSA-N p-ethylacetophenone Chemical compound CCC1=CC=C(C(C)=O)C=C1 NODGRWCMFMEGJH-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- 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
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- 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
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种合成仲醇的方法,利用过渡金属催化,使用异丙醇作氢源来合成仲醇,该反应不仅使用廉价、环保的异丙醇作氢源和溶剂,而且具有产率高、环保等优点,因此该反应具有广阔的发展前景。
Description
技术领域
本发明属有机合成化学技术领域,具体涉及一种合成仲醇的方法。
背景技术
仲醇是一类重要的化合物,不仅是重要的有机中间体,而且在药物、农药、香料等精细化工方面应用十分广泛。(a)B.Reduction Reactions with NHC-bearingComplexes.In N-Heterocyclic Carbenes:From Laboratory Curiosities to EfficientSynthetic Tools;Díez-González,S.,Ed.;(b)RSC Catalysis Series No.6,RoyalSociety of Chemistry:Cambridge,2011,pp 366-398.(c)Díez-González,S.;Marion,N.;Nolan,S.P.Chem.Rev.2009,109,3612.(d)Gladiali,S.;Alberico,E.Chem.Soc.Rev.2006,35,226.
传统的方法中,可以使用高温高压加氢,加入硼氢化钠等无机还原剂,或者使用甲酸和甲酸钠来制备仲醇,这些方法存在着反应过程存在安全隐患,以及产生大量的废料,对环境造成一定的污染。(a)S.;Obenauf.J.;Kempe.R.J.Am.Chem.Soc.2015,137,7998-8001.(b)Hodgkinson,R,;Grosso,A.D.;Clarkson,G.;Wills,Martin.DaltonTrans.2016,45,3992-4005.(c)Voisine,A.B.;Wang,D.;Roisnel,T.;Darcel,C.;Sortais,J.B.Catalysis Communications.2017,92,1-4.(d)El-Asaad,B.;Guicheret,B.;Métay,Estell.;Karamé,I.;Lemaire,M.Journal of Molecular Catalysis A:Chemical.2016,411,196-202.Rayati,S.;Bohloulbandi,E.;Zakavi,S.J.Coord.Chem.2015,69,638-649.
近几年来,使用异丙醇作氢源来制备,异丙醇是一种廉价、安全、无毒的氢给体,这种方法受到了广泛的关注。但是在反应过程中需要加入强碱或者弱碱。(a)Yu,Z.;Zeng,F.;Sun,X.;Deng,H.;Dong,J.;Chen,J.;Wang,H.;Pei,C.J.Organometallic.Chem.2007,692,2306-2313.(b)Bigler,R.;Huber,R.;Mezzetti,A.Angew.Chem.Int.Ed.2015,54,1-5.Moore,C.M.;(c)Szymczak,N.K.Chem.Commun.,2013,49,400-402.(d)Sakaguchi,S.;Yamaga,T.Ishii Y.J.Org.Chem.2001,66,4710-4712.(e)Fernández,F.E.;Puerta,M.C.;Valerga,P.Organometallics 2012,31,6868-6879.(f)Li,K.;Niu,J.;Yang,M.;Li,Z.;Wu,L.;Hao,X.;Song,M.Organometallics 2015,34,1170-1176.
因此,从有机合成的角度,发展一类新的有机金属催化剂,通过使用廉价、安全、无毒的异丙醇作氢源和溶剂,反应中不需要加入碱,能够在环境友好和温和的状态下来催化这类反应有重要的意义。
发明内容
本发明的目的在于提供一种合成仲醇的方法。
本发明通过下述技术方案实现:合成仲醇(式Ⅰ)的方法,
由酮(式Ⅱ)在过渡金属催化剂存在下,
经加氢反应得到目标产物。
反应是在过渡金属催化剂存在下发生,其反应通式为
其中,R1选自烷基、芳基、单或多取代芳基,单或多取代芳基优选甲基苯基、甲氧基苯基、三氟甲基苯基、卤代苯基;
R2代表一个取代基,选自甲基、乙基或C9烷基,苯基、苯甲基。
本发明合成仲醇的方法通过下述具体步骤实现:
在反应容器中,加入酮,过渡金属催化剂铱的络合物和溶剂异丙醇;反应混合物在油浴中加热,反应数小时后,冷却到室温,旋转蒸发除去溶剂,然后通过柱分离,得到目标化合物。
进一步地,所述反应中,铱的络合物结构为:
进一步地,所述反应中,铱的络合物用量为酮的0.2mol%。
进一步地,所述反应中,反应时间不少于6小时。
进一步地,所述反应中,反应温度不低于82℃。
同现有技术相比,本发明用酮做原料,使用异丙醇作氢源和溶剂,在过渡金属催化剂的参与下,通过氢转移,生成伯醇。反应展现出三个显著的优点:1)不加碱;2)反应温度低;3)催化剂用量低,反应原子经济;所以,该反应符合绿色化学的要求,具有广阔的发展前景。
具体实施方式
展示一下实例来说明本发明的某些实施例,且不应解释为限制本发明的范围。对本发明公开的内容可以同时从材料,方法和反应条件上进行许多改进,变化和改变。所有这些改进,变化和改变均确定地落入本发明的精神和范围之内。
实施例1:1-苯乙醇
1-phenylethanol
将苯乙酮(120mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:95%
1H NMR(500MHz,CDCl3)δ7.39-7.34(m,4H),7.29-7.28(m,1H),4.93-4.89(m,1H),1.80(br s,1H),1.51(d,J=6.5Hz,3H);13C NMR(125MHz,CDCl3)δ145.8,128.4,127.4,125.3,70.3,25.1.
实施例2:3-甲基苯乙醇
1-m-tolylethanol
将3-甲基苯乙酮(134mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:95%
1H NMR(500MHz,CDCl3)δ7.24(t,J=7.4Hz,1H),7.19(s,1H),7.17(d,J=7.6Hz,1H),7.09(d,J=7.5Hz,1H),4.87(q,J=6.4Hz,1H),2.36(s,1H),1.82(br s,1H),1.49(d,J=6.5Hz,3H);13C NMR(125MHz,CDCl3)δ145.8,138.1,128.4,128.2,126.1,122.4,70.4,25.1,21.4.
实施例3:4-甲基苯乙醇
1-p-tolylethanol
将4-甲基苯乙酮(134mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:93%
1H NMR(500MHz,CDCl3)δ7.28(d,J=8.3Hz,2H),7.17(d,J=7.9Hz,2H),4.88(q,J=6.4Hz,1H),3.34(s,3H),1.75(br s,1H),1.49(d,J=6.5Hz,3H);13C NMR(125MHz,CDCl3)δ142.8,137.0,129.1,125.3,70.1,25.0,21.0.
实施例4:4-乙基苯乙醇
1-(4-ethylphenyl)ethanol
将4-乙基苯乙酮(148mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:97%
1H NMR(500MHz,CDCl3)δ7.29(d,J=8.1Hz,2H),7.19(d,J=8.0Hz,2H),4.87(q,J=6.4,Hz,1H),2.65(q,J=7.6Hz,2H),1.88(br s,1H),1.49(d,J=6.5Hz,3H),1.23(t,J=5.1Hz,3H);13C NMR(125MHz,CDCl3)δ143.5,143.1,127.9,125.4,70.2,28.5,25.0,15.6.
实施例5:4-甲氧基苯乙醇
1-(4-methoxyphenyl)ethanol
将4-甲氧基苯乙酮(150mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:86%
1H NMR(500MHz,CDCl3)δ7.31(d,J=8.6Hz,2H),6.90(d,J=8.7Hz,2H),4.87(q,J=6.4Hz,1H),3.81(s,3H),1.73(br s,1H),1.49(d,J=6.5Hz,3H);13C NMR(125MHz,CDCl3)δ158.9,138.0,126.6,113.8,69.9,55.2,25.0.
实施例6:4-氟苯乙醇
1-(4-fluorophenyl)ethanol
将4-氟苯乙酮(138mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:96%
1H NMR(500MHz,CDCl3)δ7.34-7.32(m,2H),7.02(t,J=8.7Hz,2H),4.88(q,J=6.4Hz,1H),2.01(br s,1H),1.47(dd,J=2,1and 6.5Hz,3H);13C NMR(125MHz,CDCl3)δ163.1(d,JC-F=243.8Hz),141.5(d,JC-F=2.7Hz),127.1(d,JC-F=8.0Hz),115.3,(d,JC-F=21.3Hz),69.7,25.2.
实施例7:4-氯苯乙醇
1-(4-chlorophenyl)ethanol
将4-氯苯乙酮(155mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:95%
1H NMR(500MHz,CDCl3)δ7.32-7.28(m,4H),4.87(q,J=6.5Hz,1H),2.04(br s,1H),1.47(d,J=6.5Hz,3H);13C NMR(125MHz,CDCl3)δ144.2,133.0,128.6,126.8,69.7,25.2.
实施例8:3,4-二氯苯乙醇
1-(3,4-dichlorophenyl)ethanol
将3,4-二氯苯乙酮(189mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:97%
1H NMR(500MHz,CDCl3)δ7.54(d,J=8.4Hz,1H),7.34(d,J=2.0Hz,1H),7.28(m,1H),5.24(q,J=6.3Hz,1H),2.09(br s,1H),1.47(d,J=6.5Hz,3H);13C NMR(125MHz,CDCl3)δ141.7,133.3.132.1,129.1,127.5,127.4,66.5,23.6.
实施例9:3-溴苯乙醇
1-(3-bromophenyl)ethanol
将3-溴苯乙酮(199mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:99%
1H NMR(500MHz,CDCl3)δ7.54(d,J=1.6Hz,1H),7.40(d,J=7.7Hz,1H),7.29(d,J=7.7Hz,1H),7.21(t,J=7.7Hz,1H),4.87(q,J=6.3Hz,1H),1.87(br s,1H),1.49(dd,J=2.0and 6.3Hz,3H);13C NMR(125MHz,CDCl3)δ148.1,130.5,130.1,128.6,124.0,122.6,69.8,25.2.
实施例10:4-溴苯乙醇
1-(4-bromophenyl)ethanol
将4-溴苯乙酮(199mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:98%
1H NMR(500MHz,CDCl3)δ7.47(d,J=8.4Hz,2H),7.25(d,J=8.4Hz,2H),4.86(q,J=6.5Hz,1H),1.96(br s,1H),1.47(d,J=6.5Hz,3H);13C NMR(125MHz,CDCl3)δ144.8,131.5,127.1,121.3,69.7,25.2.
实施例11:4-硝基苯乙醇
1-(4-nitrophenyl)ethanol
将4-硝基苯乙酮(165mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:96%
1H NMR(500MHz,CDCl3)δ8.22(d,J=8.8Hz,2H),7.56(d,J=8.6Hz,2H),5.03(t,J=6.5Hz,1H),2.00(br s,1H),1.53(d,J=6.5Hz,3H);13C NMR(125MHz,CDCl3)δ153.1,147.1,126.1,123.7,69.4,25.4.
实施例12:4-氰基苯乙醇
4-(1-hydroxyethyl)benzonitrile
将4-氰基苯乙酮(145mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:95%
1H NMR(500MHz,CDCl3)δ7.64(d,J=7.8Hz,2H),7.50(d,J=8.2Hz,2H),4.97(q,J=6.4Hz,1H),2.19(br s,1H),1.50(d,J=6.5Hz,3H);13C NMR(125MHz,CDCl3)δ151.1,132.3,126.0,118.8,111.0,69.6,25.4.
实施例13:4-三氟甲基苯乙醇
将4-三氟甲基苯乙酮(188mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:94%
1H NMR(500MHz,CDCl3)δ7.61(d,J=8.1Hz,2H),7.48(d,J=8.1Hz,2H),4.96(q,J=6.5Hz,1H),2.09(br s,1H),1.50(d,J=6.5Hz,3H);13C NMR(125MHz,CDCl3)δ149.7,129.7(q,JC-F=32.1Hz),125.6,125.4(d,JC-F=3.4Hz),125.2(q,JC-F=270.3Hz),69.8,25.3.
实施例14:1-(2-噻吩基)乙醇
1-(thiophen-2-yl)ethanol
将1-(2-噻吩基)乙酮(126mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:91%
1H NMR(500MHz,CDCl3)δ7.24(d,J=4.9Hz,1H),6.98-6.95(m,2H),5.15-5.11(m,1H),2.10(br s,1H),1.61(dd,J=1.9and 6.4Hz,3H);13C NMR(125MHz,CDCl3)δ149.8,126.6,124.3,123.1,66.1,25.2.
实施例15:2-(1-羟乙基)吡啶
1-(pyridin-2-yl)ethanol
将2-乙酰基吡啶(121mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:93%
1H NMR(500MHz,CDCl3)δ8.55(d,J=4.9Hz,1H),7.69(td,J=1.7and 7.7Hz,1H),7.29(d,J=8.0Hz,1H),7.22-7.19(m,1H),4.90(q,J=6.5Hz,1H),4.28(br s,1H),1.52(d,J=6.6Hz,3H);13C NMR(125MHz,CDCl3)δ163.1,148.1,136.7,122.1,119.7,68.9,24.1.
实施例16:二苯甲醇
Diphenylmethanol
将二苯甲酮(182mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:95%
1H NMR(500MHz,CDCl3)δ7.38(d,d,J=7.3Hz,4H),7.34-7.31(m,4H),7.26(t,d,J=7.7Hz,2H),5.83(s,1H),2.26(br s,1H);13C NMR(125MHz,CDCl3)δ143.8,128.5,127.6,126.5,76.2.
实施例17:2-萘乙醇
1-(naphthalen-2-yl)ethanol
将2-萘乙酮(170mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:98%
1H NMR(500MHz,CDCl3)δ7.83-7.79(m,4H),7.50-7.44(m,3H),5.06(q,J=6.4Hz,1H),1.99(br s,1H),1.58(d,J=6.5Hz,3H);13C NMR(125MHz,CDCl3)δ143.2,133.3,132.9,128.3,127.9,127.7,126.1,125.8,123.8,70.5,25.1.
实施例18:1-苯丙醇
1-phenylpropan-1-ol
将1-苯丙酮(134mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:92%
1H NMR(500MHz,CDCl3)δ7.35-7.33(m,4H),7.29-7.26(m,1H),4.60(t,J=6.6Hz,1H),1.87(br s,1H),1.87-1.73(m,2H),0.92(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ144.6,128.4,127.5,126.0,31.9,10.1.
实施例19:4-氯苯丙醇
1-(4-chlorophenyl)propan-1-ol
将4-氯苯丙酮(169mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:97%
1H NMR(500MHz,CDCl3)δ7.31-7.29(m,2H),7.27-7.25(m,2H),4.56(t,J=5.8Hz,1H),2.06(br s,1H),1.81-1.66(m,2H),0.89(td,J=1.3and 7.4Hz,3H);13C NMR(125MHz,CDCl3)δ143.0,133.1,128.5,127.3,75.2,31.9,9.9.
实施例20:4-溴苯丙醇
1-(4-bromophenyl)propan-1-ol
将4-溴苯丙酮(213mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:96%
1H NMR(500MHz,CDCl3)δ7.47(d,J=8.4Hz,2H),7.22(d,J=8.4Hz,2H),4.57(t,J=6.5Hz,1H),1.91(br s,1H),1.83-1.67(m,2H),0.90(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ143.5,131.4,127.7,121.1,75.3,31.9,9.9.
实施例21:1-苯丁醇
1-phenylbutan-1-ol
将1-苯丁酮(148mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:93%
1H NMR(500MHz,CDCl3)δ7.35(d,J=4.4Hz,4H),7.29-7.26(m,1H),4.68(t,J=6.7Hz,1H),1.82-1.76(m,2H),1.72-1.65(m,1H),1.49-1.39(m,1H),1.36-1.26(m,1H),0.93(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ144.9,128.4,127.5,125.9,74.4,41.2,19.0,13.9.
实施例22:4-苯基-2-丁醇
4-phenylbutan-2-ol
将4-苯基-2-丁酮(148mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:95%
1H NMR(500MHz,CDCl3)δ7.28(t,J=7.5Hz,2H),7.21-7.17(m,3H),3.85-3.79(m,1H),2.78-2.64(m,2H),1.81-1.74(m,2H),1.53(br s,1H),1.23(d,J=6.2Hz,3H);13C NMR(125MHz,CDCl3)δ142.0,128.4,125.8,67.4,40.8,32.1,23.6.
实施例23:环己醇
Cyclohexanol
将环己酮(98mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:82%
1H NMR(500MHz,CDCl3)δ3.62-3.59(m,1H),1.90-1.86(m,3H),1.75-1.72(m,2H),1.57-1.53(m,1H),1.32-1.46(m,5H);13C NMR(125MHz,CDCl3)δ70.2,35.5,25.4,24.1.
实施例24:2-十二烷醇
dodecan-2-ol
将2-十二烷酮(184mg,1.0mmol)、cat.[Ir](1.1mg,0.002mmol,0.2mol%)和异丙醇(5mL)依次加入到25mL克氏管中,N2保护,82℃反应6h。冷却到室温,旋转蒸发除掉溶剂,然后通过柱层析(展开剂:石油醚/乙酸乙酯)得到纯净的目标化合物,产率:93%
1H NMR(500MHz,CDCl3)δ3.82-3.78(m,1H),1.46-1.27(m,19H),1.20(d,J=6.2Hz,3H),0.89(t,J=6.9Hz,3H);13C NMR(125MHz,CDCl3)δ68.2,39.4,31.9,29.6,29.3,25.8,23.5,22.7,14.1.。
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Surface-assisted transfer hydrogenation catalysis on a γ-Al2O3-supported Ir dimer;Satoshi Muratsugu 等;《Phys. Chem. Chem. Phys.》;20121026;第14卷;第16023-16031页 * |
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