CN115286485B - 一种合成仲醇的方法 - Google Patents
一种合成仲醇的方法 Download PDFInfo
- Publication number
- CN115286485B CN115286485B CN202210989398.0A CN202210989398A CN115286485B CN 115286485 B CN115286485 B CN 115286485B CN 202210989398 A CN202210989398 A CN 202210989398A CN 115286485 B CN115286485 B CN 115286485B
- Authority
- CN
- China
- Prior art keywords
- ketone
- hydrogenation
- alpha
- hydrogen
- terpyridine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000003333 secondary alcohols Chemical class 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- 150000002576 ketones Chemical class 0.000 claims abstract description 36
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 13
- -1 ferrous compound Chemical class 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910015475 FeF 2 Inorganic materials 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 14
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 5
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 5
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- YKFKEYKJGVSEIX-UHFFFAOYSA-N cyclohexanone, 4-(1,1-dimethylethyl)- Chemical compound CC(C)(C)C1CCC(=O)CC1 YKFKEYKJGVSEIX-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- PZOTXXRWCKDMBC-UHFFFAOYSA-N [3-(cyclohexylcarbamoyl)phenyl]boronic acid Chemical compound OB(O)C1=CC=CC(C(=O)NC2CCCCC2)=C1 PZOTXXRWCKDMBC-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- DJOFSJDUMIIGMC-UHFFFAOYSA-N 3-methyl-2-[(2-methylpropan-2-yl)oxycarbonylamino]benzoic acid Chemical compound CC1=CC=CC(C(O)=O)=C1NC(=O)OC(C)(C)C DJOFSJDUMIIGMC-UHFFFAOYSA-N 0.000 description 1
- CCOQPGVQAWPUPE-UHFFFAOYSA-N 4-tert-butylcyclohexan-1-ol Chemical compound CC(C)(C)C1CCC(O)CC1 CCOQPGVQAWPUPE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 description 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 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
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- 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
- C07C67/31—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 functional groups containing oxygen only in singly bound form
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
本发明提供了一种铁催化酮氢化合成仲醇的方法，其特征在于：基于亚铁化合物与α,α,α‑三联吡啶的联合作用下，催化酮的氢化反应，使其还原为仲醇。该方法产率高选择性高。
Description
技术领域
本发明涉及一种化学、立体选择性地合成仲醇的方法。
背景技术
结构多样的仲醇是有机合成领域中一类用途广泛的基础原料。酮的还原是合成仲醇最直接的方法。
传统的还原剂使用的是化学计量的铝氢和硅氢等金属氢试剂(Reductions bythe Alumino-and Borohydride in Organic Synthesis,2nd ed.,Wiley-VCH,New York,1997)。金属氢试剂的生产、储存和使用要求都比较严格，操作比较危险；另外，金属氢试剂在反应后会产生大量无机盐等副产物，加大了后处理的难度，不符合绿色化学的原则。
相比之下，以氢气作为还原剂的催化氢化方法具有反应操作及后处理简单、原子经济性高、污染小等优点，因而备受学术界和工业界的关注。目前酮的催化氢化使用的催化剂主要基于钌、铑、铱等贵金属(The Handbook of Homogeneous Hydrogenation deVries,J.G.；Elsevier,C.J.Eds.Wiley-VCH,Weinheim,2007)，成本高，因此，发展基于铁等储量丰富价格低廉的丰产金属催化氢化体系具有重要的意义和很好的应用前景。
目前，文献报道的铁催化酮氢化体系主要是用茂基修饰的铁催化剂(Casey,C.P.；Guan,H.J.Am.Chem.Soc.2007,129,5816；Fleischer,S.；Zhou,S.-L.；Junge,K.；Beller,M.Angew.Chem.,Int.Ed.2013,52,5120)或者含磷配体修饰的铁催化剂(Langer,R.；Leitus,G.；Ben-David,Y.；Milstein,D.Angew.Chem.,Int.Ed.2011,50,2120；Lagaditis,P.O.；Sues,P.E.；Sonnenberg,J.F.；Wang,K.Y.；Lough,A.J.；Morris,R.H.J.Am.Chem.Soc.2014,136,1367)。尽管这些催化体系可以表现出一定的催化活性，但这些配体通常需要多步骤合成且稳定性差，还需要经过复杂的步骤预先制备出铁络合物才能进行催化反应，大大降低了它们的实用性。
发明内容
本发明要解决的问题是提供一种有效地铁催化酮氢化合成仲醇的方法，是由FeX2-α,α,α-三联吡啶络合物催化酮的氢化反应，高化学选择性(即、仅还原羰基而分子中其它官能团不还原如酯基、苯环等)和立体选择性(主要针对4-叔丁基环己酮或类似结构化合物的还原，其产物仅为反式产物)合成仲醇的方法。
本发明是通过以下技术方案来实现的：
本发明提供了一种铁催化酮氢化合成仲醇的方法，其特征在于：
基于亚铁化合物与α,α,α-三联吡啶的联合作用下，催化酮的氢化反应，使其还原为仲醇。
进一步地，本发明提供的一种铁催化酮氢化合成仲醇的方法，其特征还在于：
上述亚铁化合物选自FeF2、FeCl2、FeBr2、FeI2、Fe(OAc)2中的一种或几种。
进一步地，本发明提供的一种铁催化酮氢化合成仲醇的方法，其特征还在于：
上述酮选自烷基取代的酮、芳基取代的酮、环烷基酮。
进一步地，本发明提供的一种铁催化酮氢化合成仲醇的方法，其特征还在于：
上述酮的结构式如式A-1或A-2所示：
其中，R1,R2独立地选自C1-C20烷基、C6-C10芳基；
R3为一个或一个以上的取代基，其独立地选自C1-C20烷基、C6-C10芳基；
n选自0-5的自然数。
进一步地，本发明提供的一种铁催化酮氢化合成仲醇的方法，其特征还在于：
上述氢化反应所涉及的还原剂为氢气。
进一步地，本发明提供的一种铁催化酮氢化合成仲醇的方法，其特征还在于：
具体合成方法为：
向高压釜中加入亚铁化合物，α,α,α-三联吡啶，酮后，以1-50大气压的氢气为还原剂0-100℃的温度下，反应1-48小时制得仲醇。
反应温度优选：25-80℃；最优选为60℃以上的温度下进行。
反应时间优选为：24-48小时。
仲醇产物一般经过柱层析、重结晶或减压蒸馏得到。
进一步地，本发明提供的一种铁催化酮氢化合成仲醇的方法，其特征还在于：
上述酮、亚铁化合物、α,α,α-三联吡啶配体的摩尔比为1:0.0005-0.02:0.0005-0.02。
进一步地，本发明提供的一种铁催化酮氢化合成仲醇的方法，其特征还在于：
反应还可在溶剂条件下进行。
进一步地，本发明提供的一种铁催化酮氢化合成仲醇的方法，其特征还在于：
上述溶剂选自烷基苯、苯、环烷基、卤代烷、醚、酯、腈、醇、酰胺中的一种或几种。
具体如：甲苯、苯、正己烷、环己烷、二氯甲烷、四氢呋喃、乙醚、甲基叔丁基醚、二氧六环、乙二醇二甲醚、乙酸乙酯、乙腈、甲醇、乙醇、异丙醇、N,N-二甲基甲酰胺中的任意一种。
本发明还涉及一种催化剂，其特征在于：
上述催化剂包括亚铁化合物与α,α,α-三联吡啶；
上述催化剂用于催化氢化还原反应；
上述亚铁化合物与α,α,α-三联吡啶的摩尔比为0.0005-0.02:0.0005-0.02。
本发明提供的方法与现有方法相比：反应条件温和，操作简便，原子经济性100％，且反应无需使用价格昂贵的贵金属和配体，催化剂可现场生成无需预制备，有较大的实际应用价值。反应的官能团兼容性好，化学选择性和立体选择性高。
具体实施方式
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在上述的实施例范围之中。
下述实施例采用的通用方法为：向高压釜中加入亚铁化合物FeX2，α,α,α-三联吡啶，各类酮后，以1-50大气压的氢气为还原剂0-100℃的温度下，反应24-48小时制得仲醇。
上述酮、亚铁化合物、α,α,α-三联吡啶配体的摩尔比为1:0.0005-0.02:0.0005-0.02。
优选实施例如下：
实施例1-5：FeX2催化的苯乙酮的氢化
向一125毫升高压釜中加入FeX2(0.01mmol)，α,α,α-三联吡啶(2.3mg,0.01mmol)，四氢呋喃1mL，苯乙酮(120mg,1mmol)，将高压釜封好后，置换氢气3次后，充入氢气20大气压。将高压釜至于60度油浴中反应24小时。冷却至室温后，小心放掉氢气，柱层析(石油醚：乙酸乙酯＝5:1)分离得到1-苯乙醇。1HN MR(400MHz,CDCl3)δ7.39-7.33(m,4H),7.29-7.26(m,1H),4.90(q,J＝6.4Hz,1H),1.50(d,J＝6.4Hz,3H).。
| 实施例 | X | Yield(％)/纯度(％) |
| 1 | OAc | 96/99.4 |
| 2 | Cl | 92/99.5 |
| 3 | Br | 92/99.4 |
| 4 | F | 87/99.7 |
| 5 | I | 81/99.4 |
实施例6-10：Fe(OAc)2催化的苯乙酮的氢化-氢气压力影响
向一125毫升高压釜中加入Fe(OAc)2(1.7mg，0.01mmol)，α,α,α-三联吡啶(2.3mg,0.01mmol)，四氢呋喃1mL，苯乙酮(120mg,1mmol)，将高压釜封好后，置换氢气3次后，充入氢气5-50大气压。将高压釜至于60度油浴中反应24小时。冷却至室温后，小心放掉氢气，柱层析(石油醚：乙酸乙酯＝5:1)分离得到1-苯乙醇。1HNMR(400MHz,CDCl3)δ7.39-7.33(m,4H),7.29-7.26(m,1H),4.90(q,J＝6.4Hz,1H),1.50(d,J＝6.4Hz,3H).。
| 实施例 | 氢气压力(大气压) | Yield(％)/纯度(％) |
| 6 | 5 | 93/99.5 |
| 7 | 10 | 96/99.6 |
| 8 | 20 | 96/99.5 |
| 9 | 30 | 97/99.4 |
| 10 | 50 | 97/99.5 |
实施例11-15：Fe(OAc)2催化的苯乙酮的氢化-溶剂的影响
向一125毫升高压釜中加入Fe(OAc)2(1.7mg，0.01mmol)，α,α,α-三联吡啶(2.3mg,0.01mmol)，溶剂1mL，苯乙酮(120mg,1mmol)，将高压釜封好后，置换氢气3次后，充入氢气20大气压。将高压釜至于60度油浴中反应24小时。冷却至室温后，小心放掉氢气，柱层析(石油醚：乙酸乙酯＝5:1)分离得到1-苯乙醇。1H NMR(400MHz,CDCl3)δ7.39-7.33(m,4H),7.29-7.26(m,1H),4.90(q,J＝6.4Hz,1H),1.50(d,J＝6.4Hz,3H).
| 实施例 | 溶剂 | Yield(％)/纯度(％) |
| 11 | 甲苯 | 80/99.6 |
| 12 | 四氢呋喃 | 96/99.5 |
| 13 | 二氯甲烷 | 76/99.5 |
| 14 | 甲醇 | 90/99.3 |
| 15 | 乙酸乙酯 | 88/99.5 |
实施例16-18：Fe(OAc)2催化的苯乙酮的氢化-溶剂的影响
向一125毫升高压釜中加入Fe(OAc)2(1.7mg，0.01mmol)，α,α,α-三联吡啶(2.3mg,0.01mmol)，四氢呋喃1mL，苯乙酮(120mg,1mmol)，将高压釜封好后，置换氢气3次后，充入氢气20大气压。将高压釜置于25-80度油浴中反应24小时。冷却至室温后，小心放掉氢气，柱层析(石油醚：乙酸乙酯＝5:1)分离得到1-苯乙醇。1H NMR(400MHz,CDCl3)δ7.39-7.33(m,4H),7.29-7.26(m,1H),4.90(q,J＝6.4Hz,1H),1.50(d,J＝6.4Hz,3H).
| 实施例 | 温度(℃) | Yield(％)/纯度(％) |
| 16 | 25 | 63/99.1 |
| 17 | 60 | 95/99.6 |
| 18 | 80 | 96/99.1 |
实施例19：Fe(OAc)2催化的苯乙酮的氢化
向一125毫升高压釜中加入Fe(OAc)2(1.7mg，0.01mmol)，α,α,α-三联吡啶(2.3mg,0.01mmol)，四氢呋喃10mL，苯乙酮(2.40g,20mmol)，将高压釜封好后，置换氢气3次后，充入氢气40大气压。将高压釜置于80度油浴中反应48小时。冷却至室温后，小心放掉氢气，除去溶剂，残余物进行减压蒸馏得到1-苯乙醇2.26g，产率93％(纯度99.6％)。1HNMR(400MHz,CDCl3)δ7.39-7.33(m,4H),7.29-7.26(m,1H),4.90(q,J＝6.4Hz,1H),1.50(d,J＝6.4Hz,3H).
实施例20：Fe(OAc)2催化的2-己酮的氢化
向一125毫升高压釜中加入Fe(OAc)2(1.7mg，0.01mmol)，α,α,α-三联吡啶(2.3mg,0.01mmol)，四氢呋喃1mL，2-己酮(100mg,1mmol)，将高压釜封好后，置换氢气3次后，充入氢气20大气压。将高压釜置于60度油浴中反应24小时。冷却至室温后，小心放掉氢气，柱层析(石油醚：乙酸乙酯＝6:1)分离得到2-己醇99mg，产率97％(纯度99.5％)。1HNMR(400MHz,CDCl3)δ3.74(dq,J＝11.8,6.2Hz,1H),2.23(brs,1H),1.45-1.40(m,6H),1.14(d,J＝6.2Hz,3H),0.86(d,J＝7.2Hz,3H)。
实施例21：Fe(OAc)2催化的二苯甲酮的氢化
向一125毫升高压釜中加入Fe(OAc)2(1.7mg，0.01mmol)，α,α,α-三联吡啶(2.3mg,0.01mmol)，四氢呋喃1mL，二苯甲酮(182mg,1mmol)，将高压釜封好后，置换氢气3次后，充入氢气20大气压。将高压釜置于60度油浴中反应24小时。冷却至室温后，小心放掉氢气，柱层析(石油醚：乙酸乙酯＝6:1)分离得到二苯甲醇162mg，产率88％(纯度99.6％)。1H NMR(400MHz,CDCl3)δ7.48-7.20(m,10H),5.82(s,1H),2.52(br,1H)。
实施例22：Fe(OAc)2催化的4-叔丁基环己酮的氢化
向一125毫升高压釜中加入Fe(OAc)2(1.7mg，0.01mmol)，α,α,α-三联吡啶(2.3mg,0.01mmol)，四氢呋喃10mL，4-叔丁基环己酮(1.54g,10mmol)，将高压釜封好后，置换氢气3次后，充入氢气20大气压。将高压釜置于60度油浴中反应24小时。冷却至室温后，小心放掉氢气，除去溶剂，残余物经重结晶(二氯甲烷/正己烷＝1/5)后得到反式4-叔丁基环己醇1.36g，产率87％(纯度99.4％)。1H NMR(400MHz,CDCl3)δ3.51(tt,J＝10.9,4.4Hz,1H),2.07-1.94(m,2H),1.82-1.71(m,2H),1.29-1.13(m,2H),1.10-0.91(m,3H),0.84(s,9H)。
实施例23：Fe(OAc)2催化的4-乙酰基苯甲酸甲酯的氢化
向一125毫升高压釜中加入Fe(OAc)2(1.7mg，0.01mmol)，α,α,α-三联吡啶(2.3mg,0.01mmol)，四氢呋喃10mL，4-乙酰基苯甲酸甲酯(890mg,5mmol)，将高压釜封好后，置换氢气3次后，充入氢气20大气压。将高压釜置于60度油浴中反应24小时。冷却至室温后，小心放掉氢气，除去溶剂，残余物经柱层析(石油醚：乙酸乙酯＝4:1)分离得到4-(1-羟乙基)苯甲酸甲酯846mg，产率94％(纯度99.5％)。1H NMR(400MHz,CDCl3)δ7.95(d,J＝8.3Hz,2H),7.39(d,J＝8.2Hz,2H),4.90(q,J＝5.9Hz,1H),3.88(s,3H),2.91(brs,1H),1.46(d,J＝6.5Hz,3H)。
Claims (5)
1.一种铁催化酮氢化合成仲醇的方法，其特征在于：
基于亚铁化合物与α,α,α-三联吡啶的联合作用下，催化酮的氢化反应，使其还原为仲醇；
所述亚铁化合物选自FeF2、FeCl2、FeBr2、FeI2、Fe(OAc)2中的一种或几种；
所述氢化反应所涉及的还原剂为氢气；
所述酮的结构式如式A-1或A-2所示：
其中，R1,R2独立地选自C1-C20烷基、C6-C10芳基；
R3为一个或一个以上的取代基，其独立地选自C1-C20烷基、C6-C10芳基；
n选自0-5的自然数。
2.如权利要求书1所述的一种铁催化酮氢化合成仲醇的方法，其特征在于：
具体合成方法为：
向高压釜中加入亚铁化合物，α,α,α-三联吡啶，酮后，以1-50大气压的氢气为还原剂0-100℃的温度下，反应1-48小时制得仲醇。
3.如权利要求书2所述的一种铁催化酮氢化合成仲醇的方法，其特征在于：
所述酮、亚铁化合物、α,α,α-三联吡啶配体的摩尔比为1:0.0005-0.02:0.0005-0.02。
4.如权利要求书2所述的一种铁催化酮氢化合成仲醇的方法，其特征在于：
反应在溶剂条件下进行。
5.如权利要求书4所述的一种铁催化酮氢化合成仲醇的方法，其特征在于：
所述溶剂选自烷基苯、苯、卤代烷、醚、酯、腈、醇、酰胺中的一种或几种。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210989398.0A CN115286485B (zh) | 2022-08-17 | 2022-08-17 | 一种合成仲醇的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210989398.0A CN115286485B (zh) | 2022-08-17 | 2022-08-17 | 一种合成仲醇的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115286485A CN115286485A (zh) | 2022-11-04 |
| CN115286485B true CN115286485B (zh) | 2023-11-07 |
Family
ID=83830920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210989398.0A Active CN115286485B (zh) | 2022-08-17 | 2022-08-17 | 一种合成仲醇的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115286485B (zh) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110423190A (zh) * | 2019-07-19 | 2019-11-08 | 荆楚理工学院 | 一种铁配合物催化酮α-烷基化的方法 |
| CN113173859A (zh) * | 2021-04-28 | 2021-07-27 | 温州大学 | 一种合成手性α-胺基醇化合物的方法 |
| CN114436949A (zh) * | 2022-01-25 | 2022-05-06 | 上海巽田科技股份有限公司 | 一种四齿配体及金属络合物及其制备方法和应用 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10014646A1 (de) * | 2000-03-24 | 2001-09-27 | Basf Ag | Verfahren zur Herstellung von Alkoholen an rheniumhaltigen Aktivkohle-Trägerkatalysatoren |
| CN102951981A (zh) * | 2011-08-22 | 2013-03-06 | 上海交通大学 | 一种酮类化合物的不对称氢化方法 |
-
2022
- 2022-08-17 CN CN202210989398.0A patent/CN115286485B/zh active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110423190A (zh) * | 2019-07-19 | 2019-11-08 | 荆楚理工学院 | 一种铁配合物催化酮α-烷基化的方法 |
| CN113173859A (zh) * | 2021-04-28 | 2021-07-27 | 温州大学 | 一种合成手性α-胺基醇化合物的方法 |
| CN114436949A (zh) * | 2022-01-25 | 2022-05-06 | 上海巽田科技股份有限公司 | 一种四齿配体及金属络合物及其制备方法和应用 |
Non-Patent Citations (4)
| Title |
|---|
| An environmentally benign process for the hydrogenation of ketones with homogeneous iron catalysts;Stephan Enthaler, et al.;Chemistry An Asian Journal;第1卷(第4期);第598-604页 * |
| Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol over Nitrogen-Doped Carbon-Supported Iron Catalysts;Jiang Li, et al.;ChemSusChem;第9卷(第11期);第1339-1347页 * |
| Jiang Li, et al..Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol over Nitrogen-Doped Carbon-Supported Iron Catalysts.ChemSusChem.2016,第9卷(第11期),第1339-1347页. * |
| Stephan Enthaler, et al..An environmentally benign process for the hydrogenation of ketones with homogeneous iron catalysts.Chemistry An Asian Journal.2006,第1卷(第4期),第598-604页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115286485A (zh) | 2022-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Alonso et al. | Highly selective hydrogenation of multiple carbon–carbon bonds promoted by nickel (0) nanoparticles | |
| EP3135681B1 (en) | Ruthenium complex, method for producing same, and use of same | |
| US8642812B2 (en) | Frustrated Lewis pair compositions | |
| US20040063966A1 (en) | Catalytic hydrogenation processes | |
| Geiger et al. | Cobalt (II)‐Azabis (oxazoline)‐Catalyzed Conjugate Reduction of α, β‐Unsaturated Carbonyl Compounds | |
| Aitali et al. | Enantioselective reduction of aromatic ketones catalysed by chiral ruthenium (II) complexes | |
| US11708316B2 (en) | Hydrogenation of esters to alcohols in the presence of a Ru-PNN complex | |
| CN112824422A (zh) | 一种手性二茂铁-吲哚双膦配体及其制备方法和其应用 | |
| Szőri et al. | Study of enantioselective hydrogenation of bulky esters of phenylglyoxylic acid on Pt-CD and Pt-β-ICN chiral catalysts: Steric effect of ester groups and inversion of enantioselectivity | |
| Kawatsura et al. | Regioselective synthesis of trifluoromethyl group substituted allylic amines via palladium-catalyzed allylic amination | |
| CN115286485B (zh) | 一种合成仲醇的方法 | |
| Maj et al. | Asymmetric hydrogenation of 2, 3-dihydro-1H-inden-1-one oxime and derivatives | |
| Couturier et al. | The use of borane–amine adducts as versatile palladium-catalyzed hydrogen-transfer reagents in methanol | |
| Wang et al. | Ambient-pressure highly active hydrogenation of ketones and aldehydes catalyzed by a metal-ligand bifunctional iridium catalyst under base-free conditions in water | |
| CA2253888C (en) | Process for manufacture of trans-(r,r)-actinol | |
| CN114644662A (zh) | 一种基于二茂铁结构的手性膦氮氮三齿配体及其应用 | |
| US20130281696A1 (en) | Process for preparing branched alcohols | |
| JP2006188492A (ja) | テトラヒドロピラン化合物の製造方法及び該製造方法で製造されるテトラヒドロピラン化合物 | |
| US10407448B2 (en) | N-N-bis(2-dialkylphosphinoethyl)amine-borane complex and production method therefor, and method for producing ruthenium complex containing N,N-bis(2-dialkylphosphinoethyl)amine as ligand | |
| CN109912467A (zh) | 一种2-芳基苯乙胺衍生物的合成方法 | |
| CN114805344B (zh) | 一种2-苯基咪唑环烯酮类化合物的合成方法 | |
| AU2013248383A1 (en) | Method for producing branched alcohols | |
| EP2948245A1 (en) | Process for the preparation of 4-methylpent-3-en-1-ol derivatives | |
| CN114516796B (zh) | 一种制备5-氧代己酸酯的方法 | |
| CN113105299B (zh) | 一种在水相中合成伯醇的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |