CN106000465A - Method for oxidative coupling reaction of aldehyde and secondary amide - Google Patents
Method for oxidative coupling reaction of aldehyde and secondary amide Download PDFInfo
- Publication number
- CN106000465A CN106000465A CN201610292240.2A CN201610292240A CN106000465A CN 106000465 A CN106000465 A CN 106000465A CN 201610292240 A CN201610292240 A CN 201610292240A CN 106000465 A CN106000465 A CN 106000465A
- Authority
- CN
- China
- Prior art keywords
- aldehyde
- amide
- reaction
- acetamide
- product
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000005691 oxidative coupling reaction Methods 0.000 title claims abstract description 38
- 150000003334 secondary amides Chemical class 0.000 title abstract 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- -1 imidazole cation Chemical class 0.000 claims abstract description 34
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 24
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 58
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 51
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 50
- 150000001408 amides Chemical class 0.000 claims description 33
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 29
- 238000004440 column chromatography Methods 0.000 claims description 26
- 229910052786 argon Inorganic materials 0.000 claims description 25
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000460 chlorine Substances 0.000 claims description 19
- 238000007306 functionalization reaction Methods 0.000 claims description 19
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 16
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000284 extract Substances 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- FBMIRBWQIPKRAB-UHFFFAOYSA-N n-[2,6-di(propan-2-yl)phenyl]acetamide Chemical compound CC(C)C1=CC=CC(C(C)C)=C1NC(C)=O FBMIRBWQIPKRAB-UHFFFAOYSA-N 0.000 claims description 8
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 claims description 4
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- ZTHRQJQJODGZHV-UHFFFAOYSA-N n-phenylpropanamide Chemical compound CCC(=O)NC1=CC=CC=C1 ZTHRQJQJODGZHV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052756 noble gas Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- FEIOASZZURHTHB-UHFFFAOYSA-N methyl 4-formylbenzoate Chemical compound COC(=O)C1=CC=C(C=O)C=C1 FEIOASZZURHTHB-UHFFFAOYSA-N 0.000 claims description 3
- XKDIHMBJSHIWSK-UHFFFAOYSA-N n-[2,6-di(propan-2-yl)phenyl]propanamide Chemical compound CCC(=O)NC1=C(C(C)C)C=CC=C1C(C)C XKDIHMBJSHIWSK-UHFFFAOYSA-N 0.000 claims description 3
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- QVTPWONEVZJCCS-UHFFFAOYSA-N 2-formylbenzonitrile Chemical compound O=CC1=CC=CC=C1C#N QVTPWONEVZJCCS-UHFFFAOYSA-N 0.000 claims description 2
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 claims description 2
- IFFXLDGALJZGHF-UHFFFAOYSA-N N-(4-methoxyphenyl)acetamide Chemical compound C(C)(=O)NC1=CC=C(OC)C=C1.C(C)(=O)NC1=CC=C(C=C1)OC IFFXLDGALJZGHF-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- XVAIDCNLVLTVFM-UHFFFAOYSA-N methyl ether of paracetamol Natural products COC1=CC=C(NC(C)=O)C=C1 XVAIDCNLVLTVFM-UHFFFAOYSA-N 0.000 claims description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 28
- 239000000758 substrate Substances 0.000 abstract description 19
- 150000003934 aromatic aldehydes Chemical class 0.000 abstract description 9
- 150000003949 imides Chemical class 0.000 abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 126
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 78
- 239000000047 product Substances 0.000 description 61
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 50
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 46
- 239000002904 solvent Substances 0.000 description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- 238000005160 1H NMR spectroscopy Methods 0.000 description 26
- 238000005481 NMR spectroscopy Methods 0.000 description 26
- 238000007789 sealing Methods 0.000 description 26
- 239000012046 mixed solvent Substances 0.000 description 25
- 239000003208 petroleum Substances 0.000 description 22
- 238000004458 analytical method Methods 0.000 description 20
- 150000001793 charged compounds Chemical class 0.000 description 18
- 239000007788 liquid Substances 0.000 description 12
- UZJLYRRDVFWSGA-UHFFFAOYSA-N n-benzylacetamide Chemical compound CC(=O)NCC1=CC=CC=C1 UZJLYRRDVFWSGA-UHFFFAOYSA-N 0.000 description 12
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000001819 mass spectrum Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000002505 iron Chemical class 0.000 description 5
- 208000035126 Facies Diseases 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002192 fatty aldehydes Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 3
- RBIGKSZIQCTIJF-UHFFFAOYSA-N 3-formylthiophene Chemical compound O=CC=1C=CSC=1 RBIGKSZIQCTIJF-UHFFFAOYSA-N 0.000 description 3
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009432 framing Methods 0.000 description 3
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- LQWWZVZGPVVZOB-UHFFFAOYSA-N n-(2,4,6-trimethylphenyl)acetamide Chemical compound CC(=O)NC1=C(C)C=C(C)C=C1C LQWWZVZGPVVZOB-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- JRMAQQQTXDJDNC-UHFFFAOYSA-M 2-ethoxy-2-oxoacetate Chemical compound CCOC(=O)C([O-])=O JRMAQQQTXDJDNC-UHFFFAOYSA-M 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-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
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- IVVMNEWWVJXCLX-UHFFFAOYSA-N 2-amino-4,6-ditert-butylphenol Chemical class CC(C)(C)C1=CC(N)=C(O)C(C(C)(C)C)=C1 IVVMNEWWVJXCLX-UHFFFAOYSA-N 0.000 description 1
- GUGQQGROXHPINL-UHFFFAOYSA-N 2-oxobutanoyl chloride Chemical compound CCC(=O)C(Cl)=O GUGQQGROXHPINL-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- WRAGCBBWIYQMRF-UHFFFAOYSA-N N-Cyclohexylacetamide Chemical compound CC(=O)NC1CCCCC1 WRAGCBBWIYQMRF-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- ZYPGADGCNXOUJP-CXVPHVKISA-N Variotin Chemical compound CCCC[C@@H](O)\C=C(/C)\C=C\C=C\C(=O)N1CCCC1=O ZYPGADGCNXOUJP-CXVPHVKISA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- ZXNRTKGTQJPIJK-UHFFFAOYSA-N aniracetam Chemical compound C1=CC(OC)=CC=C1C(=O)N1C(=O)CCC1 ZXNRTKGTQJPIJK-UHFFFAOYSA-N 0.000 description 1
- 229960000793 aniracetam Drugs 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZYPGADGCNXOUJP-UHFFFAOYSA-N dl-Variotin Natural products CCCCC(O)C=C(C)C=CC=CC(=O)N1CCCC1=O ZYPGADGCNXOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 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
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Abstract
The invention discloses a method for an oxidative coupling reaction of aldehyde and secondary amide. An ionic iron (III) complex containing a monophenol functional imidazole cation serves as a catalyst to efficiently catalyze the oxidative coupling reaction of aldehyde and secondary amide to prepare imide for the first time; not only can oxidative coupling of aromatic aldehyde, aliphatic aldehyde and secondary amide be efficiently catalyzed, but also an oxidative coupling reaction taking aromatic heterocyclic aldehyde and large steric hindrance secondary amide as substrates can be efficiently catalyzed, and the catalytic activity and substrate applicability are superior to those in the prior art.
Description
The present invention is Application No. 2015104452411, filing date on July 27th, 2015, invention entitled " contains
Ionic iron (III) coordination compound of single phenol functionalization Imidazole cation and preparation method and application " patent application point
Case application.
Technical field
The invention belongs to technical field of organic synthesis, a kind of ion-type containing single phenol functionalization Imidazole cation
Aldehyde that ferrum (III) is complex-catalyzed and the method for the oxidative coupling reaction of two grades of amide.
Background technology
Acid imide is present in many natural products as an important construction unit, is also effective knot of a lot of medicine
Structure unit, such as: aniracetam, variotin etc..Therefore, build imide structure the most efficiently and receive increasing pass
Note (see: Y. J. Wang, C. Y. Chen, Z. Z. Huang,Chem. Eur. J., 2013,19,1129).
The coupling reaction of carboxylic acid derivates and amide is to build one of imido traditional mainstay, but this method is the most restricted
Unstability and poor Atom economy in carboxylic acid derivates (such as: acyl chlorides).(see C. A. G. N.
Montalbetti, V. Falque, Tetrahedron, 2005,61,10827).Along with people's day to Green Chemistry
Benefit is paid attention to, and the substitute finding carboxylic acid derivates becomes a focus in this research field.
Compared with carboxylic acid derivates, aldehyde compound has metastable chemical property, higher Atom economy
Etc. advantage, this makes people start as the succedaneum of carboxylic acid derivates to be incorporated in imido structure.Such as, with
Under conditions of NBS (N-bromo-succinimide) is oxidant, cuprous bromide can be catalyzed aromatic aldehyde and amide (one-level efficiently
Amide and two grades of amide) oxidative coupling generate acid imide and (see L. Wang, H. Fu, Y. Y. Jiang, Y. F.
Zhao, Chem. Eur. J., 2008,14,10772);With tert-butyl hydroperoxide as oxidant, two (triphenylphosphines) two
Palladium can be catalyzed two grades of amide of aromatic aldehyde and pyridine ring modification and carry out oxidative coupling reaction, thus prepares acid imide
(see Y. J. Wang, C. Y. Chen, Z. Z. Huang,Chem. Eur. J., 2013,19,1129).These
Result shows to replace carboxylic acid derivates to have good application prospect in imido synthesis with aldehyde, but, existing method is also
Some defects are had to have to be overcome, such as expensive price, the toxicity etc. of Cu-series catalyst of palladium series catalyst.Therefore, develop inexpensive, low
Malicious or nontoxic novel green catalyst is clearly the most required.
The advantages such as Fe-series catalyst has inexpensively, low toxicity or nontoxic, preferable biocompatibility, develop Fe-series catalyst
Be considered as develop the economy and environment-friendly catalyst a Critical policies (Correa, A., Manche o, O. G.,
Bolm, C., Chem. Soc. Rev.,2008,37,1108).With tert-butyl hydroperoxide as oxidant, dibrominated is ferrous
The oxidative coupling of aromatic aldehyde, fatty aldehyde and two grades of amide can be catalyzed carry out synthesizing imide and (see J. Wang, C. Liu, J.
W. Yuan, A. W. Lei, Chem. Commun., 2014,50,4736).The method can be catalyzed aldehyde and two grades of amide
Oxidative coupling to prepare acid imide, but there is obvious drawback, mainly have: (1) dibrominated ferrous iron is unstable, in atmosphere
Easily oxidation, deliquescence, operation inconvenience;(2) purity of these iron salt is often mixed with its of denier by its commercial source difference
Its metal (such as copper) thus cause the instability of catalytic performance;(3) substrate applicability need to expand further, as due to virtue
Fragrant heterocyclic aldehydes hetero atom is the reason such as bigger with the steric hindrance of metal-complexing and big two grades of amide of steric hindrance, causes these substrates to have
Effect carries out above-mentioned reaction.
In present inventor's research work previously, once design synthesized containing bisphenol functionalized imidazoles (quinoline) sun from
Ionic iron (III) coordination compound of son, finds that they can be with effective catalyst aryl grignard reagent and the halogenated alkyl hydrocarbon containing b-H
Cross-coupling reaction (see: (1) C. L. Xia, C. F. Xie, Y. F. Wu, H. M. Sun, Q. Shen, Y.
Zhang, Org. Biomol. Chem., 2013, 11, 8135;(2) ZL201210397111.1).Up to now, the most not
See the oxidation between ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation and catalysis aldehyde and two grades of amide
The report of coupling reaction.
Summary of the invention
It is an object of the invention to provide a kind of ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation,
Its stable storage, is possible not only to the oxidative coupling being catalyzed aromatic aldehyde, aliphatic aldehyde and two grades of amide efficiently sub-to synthesize acyl
Amine, it is also possible to the oxidative coupling reaction that efficient catalytic aromatic heterocycle aldehyde and two grades of amide of big steric hindrance participate in, its catalysis activity and
Substrate applicability is all significantly better than prior art.
For reaching above-mentioned purpose, the technical solution used in the present invention is: the coordination compound of formula I is catalyzed as single-component catalyst
Aldehyde and two grades of amide carry out the application of oxidative coupling reaction;
Formula I;
Wherein R1For methyl or isopropyl;R2For hydrogen or methyl;R3For hydrogen or the tert-butyl group;X is chlorine or bromine.
In technique scheme, catalyst amount is the 2%~5% of two grades of amide moles.Catalyst amount is less than existing
Technology, but product yield is high, it is convenient to purify.
Ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation that above-mentioned formula I represents is as one-component
The method of the oxidative coupling reaction of catalyst aldehyde and two grades of amide, comprises the following steps: under room temperature, at inert gas atmosphere
In, in reactor, add catalyst, two grades of amide, organic solvents, stirring successively;Then proceed to be sequentially added in reactor
Aldehyde, tert-butyl hydroperoxide aqueous solution, in 60~80 DEG C of stirring reactions 18~36 hours, i.e. obtain product.
In technique scheme, reaction terminates reaction with water after terminating;Product is extracted with ethyl acetate, by post layer
Analysis (with ethyl acetate/petroleum ether volume ratio for 1: the mixed solvent of (5~20) is as developing solvent) i.e. obtains product.
In technique scheme, described noble gas is nitrogen or argon;Organic solvent 1,2-dichloroethanes.
In technique scheme, described aldehyde is aromatic aldehyde, fatty aldehyde or aromatic heterocycle aldehyde, and the structure of aldehyde is RCHO, its
Middle aromatic aldehyde R is substituted-phenyl, and fatty aldehyde R is open chain aliphatic substitution, and aromatic heterocycle aldehyde R is heterocyclic substituent;Two grades of acyls
Amine is chain amide, R4CONHR5, wherein R4For methyl or ethyl, R5For substituted-phenyl or alkyl substituent;And lactams.
Preferably in technical scheme, described aromatic aldehyde is the aldehyde compound with benzaldehyde framing structure, such as: benzene first
Aldehyde, o-tolualdehyde, 4-chloro-benzaldehyde, o-chlorobenzaldehyde, p-bromobenzaldehyde, 4-Fluorobenzaldehyde, p-tolyl aldehyde, 1-naphthalene
Formaldehyde, p-tolyl aldehyde, P-methoxybenzal-dehyde, paranitrobenzaldehyde, to cyanobenzaldehyde, terephthalaldehydic acid methyl ester
Deng;Described fatty aldehyde is the aldehyde compound with open chain alkane framing structure, such as: n-hexyl aldehyde, hutanal etc.;Described fragrance is miscellaneous
Ring aldehyde is the aldehyde compound with aromatic heterocycle framing structure, such as: 2 thiophene carboxaldehyde, 3-thiophenecarboxaldehyde or 2 furan carboxyaldehyde
Deng;Described chain amide is two grades of amide of replacement with open-chain structure, such as:N-benzylacetamide,N-methylacetamide,N-(2,4,6-trimethylphenyl) acetamide,N-(2,6-diisopropyl phenyl) acetamide,N-(2,6-bis-is different
Propyl group phenyl) propionic acid amide.,N-(4-aminomethyl phenyl) acetamide,N-(4-methoxyphenyl) acetamide,N-(4-chlorphenyl)
Acetamide,N-(4-trifluoromethyl) acetamide,N-cyclohexyl acetamide,N-Phenylpropionamide etc.;Described lactams is
Cyclic amide, such as: caprolactam etc..
In technique scheme, with molar amount, the consumption of aldehyde is 2.4 times of two grades of amide, tert-butyl hydroperoxide
Consumption is 2 times of two grades of amide, and catalyst amount is 2%~5% mol of two grades of amide.Response time is 18 hours, reaction temperature
Degree is 60 DEG C.
Preferably in technical scheme, with molar amount, aldehyde: two grades of amide: tert-butyl hydroperoxide: catalyst is 2.4: 1:
2.0∶0.02;Response time is 18 hours, and reaction temperature is 60 DEG C.
The invention also discloses a kind of ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation, described
The chemical general formula of ionic iron (III) coordination compound is [(Ar1NCH2CH2NAr2)CH][FeX4], wherein Ar1 = 2,6-di-R1-
4-R2-C6H2, Ar2 = 3,5-di-R3-2-(OH)-C6H2, R1One in methyl, isopropyl, R2Selected from hydrogen atom, first
One in base, R3One in hydrogen atom, the tert-butyl group, X is the one in chlorine or bromine;Its structural formula is as shown in formula I:
Formula I.
In technique scheme, described ionic iron (III) coordination compound be containing single phenol functionalization Imidazole cation from
Subtype ferrum (III) coordination compound, it is prepared with iron salt by single phenol functionalization imidazoline villaumite part.
The preparation method of above-mentioned ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation, including following
Step: under the conditions of anhydrous and oxygen-free, in inert gas atmosphere, is dissolved in molten by iron salt system with single phenol functionalization imidazoline villaumite
In agent, react 2~20 hours at 30~70 DEG C;Solvent removed in vacuo, extracts residue with tetrahydrofuran solvent, and it is heavy to remove
Form sediment, be recrystallized to give ferrum (III) coordination compound with the mixed solvent of hexane and oxolane;Described iron salt system be ferric bromide with
The mixture of sodium bromide or ferric chloride.
When X is chlorine when, the method preparing above-mentioned ionic iron (III) coordination compound comprises the following steps:
Under the conditions of anhydrous and oxygen-free, in inert gas atmosphere, ferric chloride is dissolved in molten with single phenol functionalization imidazoline villaumite
In agent, react 2~6 hours at 30~60 DEG C;Solvent removed in vacuo, extracts residue with tetrahydrofuran solvent, removes precipitation,
Being recrystallized to give ferrum (III) coordination compound with the mixed solvent of hexane and oxolane, the ferrum (III) being above-mentioned ion-type coordinates
Thing.
In technique scheme, described noble gas is nitrogen or argon, and the mixing of described hexane and oxolane is molten
In agent, the volume ratio of hexane and oxolane is 1:4~1:15.
Preferably in technical scheme, ferric chloride is 1:1 with the mol ratio of single phenol functionalization imidazoline villaumite, and solvent is four
Hydrogen furan, reaction temperature is 30 DEG C, and the response time is 4 hours.
When X is bromine when, the method for ferrum (III) coordination compound preparing above-mentioned ion-type comprises the following steps:
Under the conditions of anhydrous and oxygen-free, in inert gas atmosphere, by ferric bromide, single phenol functionalization imidazoline villaumite and sodium bromide
It is dissolved in solvent, reacts 10~20 hours at 45~70 DEG C;Solvent removed in vacuo, extracts residue with tetrahydrofuran solvent,
Remove precipitation, be recrystallized to give ferrum (III) coordination compound with the mixed solvent of oxolane and hexane, be above-mentioned ionic iron
(III) coordination compound.
In technique scheme, described noble gas is nitrogen or argon, and the mixing of described hexane and oxolane is molten
In agent, the volume ratio of hexane and oxolane is 1:4~1:15.
Preferably in technical scheme, the mol ratio of ferric bromide, single phenol functionalization imidazoline villaumite and sodium bromide is 1:1:
6, solvent is oxolane, and reaction temperature is 45 DEG C, and the response time is 16 hours.
Owing to technique scheme is used, the present invention compared with prior art has the advantage that
Ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation the most disclosed by the invention can be by imidazoles
The phenol epoxide and the alkyl that introduce different structure on two nitrogen-atoms of quinoline ring respectively realize the space to corresponding ferrum (III) coordination compound
Steric hindrance and the flexible modulation of electronic effect, thus develop the Fe-series catalyst that a class is new and effective.
2. the present invention contains single phenol merit by iron salt system and the reaction preparation at ambient pressure of single phenol functionalization imidazoline villaumite
Can change ionic iron (III) coordination compound of Imidazole cation, react simple to operation, product is easily purified, yield is high, this kind of joins
Laminate structures is clear and definite, and the most also can stable existence.
Ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation the most disclosed by the invention is possible not only to
Be catalyzed aromatic aldehyde, aliphatic aldehyde and the oxidative coupling of two grades of amide efficiently, it is also possible to be catalyzed efficiently with aromatic heterocycle aldehyde,
Big two grades of amide of steric hindrance are the oxidative coupling of substrate, and catalysis activity and substrate applicability are better than prior art;The catalysis of the present invention
Efficiency compared with prior art has clear superiority, and the inventive method solves existing aromatic heterocycle aldehyde, big steric hindrance two grades
Amide cannot effectively participate in the problem of this reaction, and the inventive method need not add other parts, and reaction system is simple, tool
There is higher Atom economy;Be conducive to industrial applications.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
Embodiment one: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 2-(OH)-
C6H4, X=Cl) synthesis
2,6-DIPA (10.0 milliliters, 48 mMs) and triethylamine (7.3 milliliters, 48 mMs) mixing are dissolved in dry
In the oxolane of dry mistake, under ice-water bath, it is slowly added dropwise ethyl oxalyl chloride (5.1 milliliters, 48 mMs), drips complete rear chamber
The lower stirring of temperature 5 hours.Filtering, filtrate washes three times respectively with dilute hydrochloric acid, saturated aqueous common salt respectively, and organic facies anhydrous sodium sulfate is done
Dry 12 hours.Organic facies is concentrated into saturated, adds 100 ml n-hexanes, has solid to separate out, filter, be dried, obtain white solid (N
-(diisopropyl phenyl) ethyl oxalate), productivity 92%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 8.36 (s, 1H), 7.34 (t, 1H), 7.20 (d, 2H),
4.47-4.42 (m, 2H), 3.01 (m, 2H), 1.47 (t, 3H), 1.21 (d, 12H) ppm。
WillN(1.31 grams, 12 in the least for-(diisopropyl phenyl) ethyl oxalate (2.78 grams, 10.0 mMs), Ortho-Aminophenol
Mole) and triethylamine (2.78 milliliters, 20 mMs) mixing be dissolved in toluene, return stirring 12 hours.It is cooled to room temperature, reaction
Liquid is washed three times with dilute hydrochloric acid, saturated common salt respectively, and organic facies anhydrous sodium sulfate is dried 12 hours.Organic facies is concentrated into full
With, add 100 ml n-hexanes, have solid to separate out, filter, be dried, obtain white solid (N-(2,6-diisopropyl phenyl)-N
'-(2-hydroxy phenyl) oxamides), productivity 85%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 9.67 (s, 1H), 8.84 (s, 1H), 8.12 (s, 1H),
7.50 (dd, 1H), 7.37 (t, 1H), 7.23 (d, 1H), 7.16 (dt, 1.5 Hz, 1H), 6.96-6.89
(m, 2H), 3.07-3.00 (m, 2H), 1.22 (d, 12H) ppm。
TakeN-(2,6-diisopropyl phenyl)-N'-(2-hydroxy phenyl) oxamides (0.74 gram, 2.2 mMs), Xiang Qi
In be slowly added to borine tetrahydrofuran solution (17.6 milliliters, 1.0 mol/L, 17.6 mMs) return stirring 12 hours.Cooling
To room temperature, it is slowly added dropwise absolute methanol to not having gas to generate, adds concentrated hydrochloric acid (1.5 milliliters, 36%, 18 mM), reactant liquor
It is spin-dried for obtaining white solid.In white solid, add ethyl orthoformate (10 milliliters), stir 30 minutes at 90 DEG C, have solid to analyse
Going out, filter, filter cake absolute ether is washed three times, is obtained white solid [(Ar1NCH2CH2NAr2) CH] Cl(Ar1=2,6-di-CH
(CH3)2-C6H3, Ar2= 2-(OH)-C6H4), productivity 53%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 9.04 (s, 1H), 7.57 (dd, 1H), 7.44 (t, 1H),
7.22 (d, 2H), 7.15 (d, 1H), 6.97 (dt, 1H), 6.78 (dt, 1H), 4.88 (t, 2H), 4.44
(t, 2H), 3.03-2.96 (m, 2H), 1.25 (d, 6H), 1.16 (d, 6H)ppm。
Product is carried out elementary analysis, and result is as follows:
Elementary analysis
C:(%) | H:(%) | N:(%) | |
Theoretical value | 70.28 | 7.58 | 7.81 |
Actual value | 70.03 | 7.42 | 7.73 |
Compound cation part [(Ar1NCH2CH2NAr2)CH]+Characterized by mass spectrum, found that they are at 323.2122
Having a molecular ion peak, this molecular ion peak is 323.21 in theory, and actual measurement substantially conforms to theory.Prove gained compound
For [(Ar1NCH2CH2NAr2) CH] Cl(Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 2-(OH)-C6H4).
By [(Ar1NCH2CH2NAr2) CH] Cl(0.36 gram, 1.0 mMs) (0.16 gram, 1.0 in the least to join ferric chloride
Mole) tetrahydrofuran solution in, react 4 hours at 30 DEG C, vacuum pumps solvent, and hexane washs, and drains, extracts with oxolane
Taking, centrifugal clear liquid shifts, and adds hexane recrystallization in clear liquid, separates out yellowish-brown crystal, productivity 92% under room temperature.
Product is carried out elementary analysis, and result is as follows:
Elementary analysis
C:(%) | H:(%) | N:(%) | |
Theoretical value | 48.40 | 5.22 | 5.38 |
Actual value | 48.31 | 5.41 | 5.16 |
Owing to the coordination compound of ferrum has paramagnetism, so it not being carried out nuclear-magnetism sign.
This coordination compound [(Ar1NCH2CH2NAr2)CH][FeCl4] presented in ion pair, wherein anion portion
Divide [FeCl4]-Being characterized by Raman spectrum, it is at 333 cm-1There is characteristic peak at place.
The cationic moiety [(Ar of coordination compound1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its
Having a molecular ion peak at 323.2141, this molecular ion peak is 323.21 in theory, and actual measurement substantially conforms to theory.Prove
Gained compound is target compound.
Embodiment two: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 2-
(OH)-C6H4, X=Br) synthesis
Successively by [(Ar1NCH2CH2NAr2) CH] Cl(0.36 gram, 1.0 mMs) and NaBr(0.62 gram, 6.0 mMs) add
In the tetrahydrofuran solution of ferric bromide (0.30 gram, 1.0 mMs), reacting 16 hours at 45 DEG C, vacuum pumps solvent, oneself
Alkane washs, and drains, and extracts with oxolane, and centrifugal clear liquid shifts, and adds hexane recrystallization, separate out reddish brown under room temperature in clear liquid
Color crystal, productivity 93%.
Product is carried out elementary analysis, and result is as follows:
Elementary analysis
C:(%) | H:(%) | N:(%) | |
Theoretical value | 36.09 | 3.89 | 4.01 |
Actual value | 36.32 | 4.15 | 3.92 |
This coordination compound [(Ar1NCH2CH2NAr2)CH][FeBr4] presented in ion pair, wherein anionicsite
[FeBr4]-Being characterized by Raman spectrum, it is at 204 cm-1There is characteristic peak at place.
The cationic moiety [(Ar of coordination compound1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its
Having a molecular ion peak at 323.2118, this molecular ion peak is 323.21 in theory, and actual measurement substantially conforms to theory.Prove
Gained compound is target compound.
Embodiment three: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5-
di-C(CH3)3-2-(OH)-C6H2, X=Cl) synthesis
[(Ar1NCH2CH2NAr2) CH] and the synthesis of Cl with reference to the step of embodiment one, utilize 3,5-di-t-butyl-2-hydroxyanilines
Replace Ortho-Aminophenol.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 8.27 (s, 1H), 7.47 (t, 1H), 7.36 (d, 1H),
7.31 (s, 1H), 7.29 (s, 1H), 6.96 (d, 1H), 4.92 (t, 2H), 4.48 (t, 2H), 3.51-
3.40 (m, 2H), 1.44 (s, 9H), 1.37 (d, 6H), 1.30 (d, 15H)ppm。
Product is carried out elementary analysis, and result is as follows:
Elementary analysis
C:(%) | H:(%) | N:(%) | |
Theoretical value | 73.93 | 9.20 | 5.95 |
Actual value | 73.72 | 8.96 | 5.88 |
Compound cation part [(Ar1NCH2CH2NAr2)CH]+Characterized by mass spectrum, found that they are at 435.3384
Having a molecular ion peak, this molecular ion peak is 435.34 in theory, and actual measurement substantially conforms to theory.Prove gained compound
For [(Ar1NCH2CH2NAr2) CH] Cl(Ar1=2,6-di-CH(CH3)2-C6H3, Ar2= 3,5-di-C(CH3)3-2-(OH)-
C6H2).
By [(Ar1NCH2CH2NAr2) CH] Cl(0.47 gram, 1.0 mMs) (0.16 gram, 1.0 in the least to join ferric chloride
Mole) tetrahydrofuran solution in, react 6 hours at 40 DEG C, vacuum pumps solvent, and hexane washs, and drains, extracts with oxolane
Taking, centrifugal clear liquid shifts, and adds hexane recrystallization in clear liquid, separates out yellowish-brown crystal, productivity 85% under room temperature.
Product is carried out elementary analysis, and result is as follows:
Elementary analysis
C:(%) | H:(%) | N:(%) | |
Theoretical value | 55.00 | 6.84 | 4.42 |
Actual value | 55.36 | 6.53 | 4.63 |
This coordination compound [(Ar1NCH2CH2NAr2)CH][FeCl4] presented in ion pair, wherein anionicsite
[FeCl4]-Being characterized by Raman spectrum, it is at 333 cm-1There is characteristic peak at place.
The cationic moiety [(Ar of coordination compound1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its
Having a molecular ion peak at 435.3380, this molecular ion peak is 435.34 in theory, and actual measurement substantially conforms to theory.Prove
Gained compound is target compound.
Embodiment four: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5-
di-C(CH3)3-2-(OH)-C6H2, X=Br) synthesis
Successively by [(Ar1NCH2CH2NAr2) CH] Cl(0.47 gram, 1.0 mMs) and NaBr(0.62 gram, 6.0 mMs) add
In the tetrahydrofuran solution of ferric bromide (0.30 gram, 1.0 mMs), reacting 20 hours at 60 DEG C, vacuum pumps solvent, oneself
Alkane washs, and drains, and extracts with oxolane, and centrifugal clear liquid shifts, and adds hexane recrystallization, separate out reddish brown under room temperature in clear liquid
Color crystal, productivity 86%.
Product is carried out elementary analysis, and result is as follows:
Elementary analysis
C:(%) | H:(%) | N:(%) | |
Theoretical value | 42.94 | 5.34 | 3.45 |
Actual value | 43.27 | 5.46 | 3.56 |
This coordination compound [(Ar1NCH2CH2NAr2)CH][FeBr4] presented in ion pair, wherein anionicsite
[FeBr4]-Being characterized by Raman spectrum, it is at 204 cm-1There is characteristic peak at place.
The cationic moiety [(Ar of coordination compound1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its
Having a molecular ion peak at 435.3385, this molecular ion peak is 435.34 in theory, and actual measurement substantially conforms to theory.Prove
Gained compound is target compound.
Embodiment five: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1=2,4,6-tri-CH3-C6H2, Ar2=3,5-di-C
(CH3)3-2-(OH)-C6H2, X=Cl) synthesis
[(Ar1NCH2CH2NAr2) CH] and the synthesis of Cl with reference to the step of embodiment one, utilize 2,4,6-trimethyl aniline to replace 2,
6-diisopropyl aniline;3,5-di-t-butyl-2-hydroxyanilines is utilized to replace Ortho-Aminophenol.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 8.40 (s, 1H), 7.47 (t, 1H), 7.36 (d, 1H),
6.98 (s, 2H), 6.93 (d, 1H), 4.83 (t, 2H), 4.45 (t, 2H), 2.51 (s, 6H), 2.31
(s, 3H), 1.44 (s, 9H), 1.30 (s, 9H)ppm。
Product is carried out elementary analysis, and result is as follows:
Elementary analysis
C:(%) | H:(%) | N:(%) | |
Theoretical value | 72.79 | 8.69 | 6.53 |
Actual value | 72.71 | 8.55 | 6.61 |
Compound cation part [(Ar1NCH2CH2NAr2)CH]+Characterized by mass spectrum, found that they are at 393.2907
Having a molecular ion peak, this molecular ion peak is 393.29 in theory, and actual measurement substantially conforms to theory.Prove gained compound
For [(Ar1NCH2CH2NAr2) CH] Cl(Ar1 = 2,4,6-tri-CH3-C6H2, Ar2 = 3,5-di-C(CH3)3-2-(OH)-
C6H2).
By [(Ar1NCH2CH2NAr2) CH] Cl(0.43 gram, 1.0 mMs) (0.16 gram, 1.0 in the least to join ferric chloride
Mole) tetrahydrofuran solution in, react 2 hours at 60 DEG C, vacuum pumps solvent, and hexane washs, and drains, extracts with oxolane
Taking, centrifugal clear liquid shifts, and adds hexane recrystallization in clear liquid, separates out yellowish-brown crystal, productivity 82% under room temperature.
Product is carried out elementary analysis, and result is as follows:
Elementary analysis
C:(%) | H:(%) | N:(%) | |
Theoretical value | 52.82 | 6.31 | 4.74 |
Actual value | 53.11 | 6.45 | 5.01 |
This coordination compound [(Ar1NCH2CH2NAr2)CH][FeCl4] presented in ion pair, wherein anionicsite
[FeCl4]-Being characterized by Raman spectrum, it is at 333 cm-1There is characteristic peak at place.
The cationic moiety [(Ar of coordination compound1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its
Having a molecular ion peak at 393.2906, this molecular ion peak is 393.29 in theory, and actual measurement substantially conforms to theory.Prove
Gained compound is target compound.
Embodiment six: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1=2,4,6-tri-CH3-C6H2, Ar2=3,5-di-C
(CH3)3-2-(OH)-C6H2, X=Br) synthesis
Successively by [(Ar1NCH2CH2NAr2) CH] Cl(0.43 gram, 1.0 mMs) and NaBr(0.62 gram, 6.0 mMs) add
In the tetrahydrofuran solution of ferric bromide (0.30 gram, 1.0 mMs), reacting 10 hours at 70 DEG C, vacuum pumps solvent, oneself
Alkane washs, and drains, and extracts with oxolane, and centrifugal clear liquid shifts, and adds hexane recrystallization, separate out reddish brown under room temperature in clear liquid
Color crystal, productivity 83%.
Product is carried out elementary analysis, and result is as follows:
Elementary analysis
C:(%) | H:(%) | N:(%) | |
Theoretical value | 40.61 | 4.85 | 3.64 |
Actual value | 40.95 | 4.95 | 3.69 |
This coordination compound [(Ar1NCH2CH2NAr2)CH][FeBr4] presented in ion pair, wherein anionicsite
[FeBr4]-Being characterized by Raman spectrum, it is at 204 cm-1There is characteristic peak at place.
The cationic moiety [(Ar of coordination compound1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its
Having a molecular ion peak at 393.2905, this molecular ion peak is 393.29 in theory, and actual measurement substantially conforms to theory.Prove
Gained compound is target compound.
Embodiment seven: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1=2,6-di-CH(CH3)2-C6H3, Ar2=3,5-di-C
(CH3)3-2-(OH)-C6H2, X=Br) benzaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-benzyl
Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds benzaldehyde (122
Microlitre, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).18 are reacted at 60 DEG C
Hour, terminating reaction with water, product is extracted with ethyl acetate, and column chromatography purifies and (with ethyl acetate/petroleum ether volume ratio is
The mixed solvent of 1: 5 is developing solvent), productivity is 85%, and catalytic efficiency is 0.5974g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.57-7.54 (m, 3H), 7.45-7.42 (m, 2H), 7.28-
7.24 (m, 5H), 5.00 (s, 2H), 2.16 (s, 3H) ppm。
Embodiment eight: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5-
di-C(CH3)3-2-(OH)-C6H2, X=Br) o-tolualdehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-benzyl
Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds o-methyl-benzene first
Aldehyde (139 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).At 60 DEG C instead
Answering 18 hours, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether body
Long-pending than be 1: 10 mixed solvent be developing solvent), productivity is 50%, and catalytic efficiency is 0.3708g/mmol/h.The existing skill of this substrate
Art cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.36-7.10 (m, 9H), 4.92 (s, 2H), 2.27 (s,
3H) , 2.19 (s, 3H) ppm。
Embodiment nine: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5-
di-C(CH3)3-2-(OH)-C6H2, X=Br) 4-chloro-benzaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (12.2 milligrams, 0.015 mM, 3mol%),N-benzyl
Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds 4-chloro-benzaldehyde
(168.7 milligrams, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).At 60 DEG C instead
Answering 18 hours, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether body
Long-pending than be 1: 10 mixed solvent be developing solvent), productivity is 93%, and catalytic efficiency is 0.4943g/mmol/h.The existing skill of this substrate
Art purifies through column chromatography, and productivity is 61%, and catalytic efficiency is 0.2188g/mmol/h, and this method has bright compared to prior art
Aobvious advantage.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.49 (d, 2H), 7.39 (d, 2H), 7.33-7.14 (m,
5H), 4.98 (s, 2H), 2.19 (s, 3H) ppm。
Embodiment ten: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5-
di-C(CH3)3-2-(OH)-C6H2, X=Br) p-bromobenzaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (20.3 milligrams, 0.025 mM, 5 mol%),N-benzyl
Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds p-bromobenzaldehyde
(220.0 milligrams, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).At 60 DEG C
Reacting 18 hours, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether
Volume ratio be the mixed solvent of 1: 20 be developing solvent), productivity is 82%, and catalytic efficiency is 0.3225g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.55 (d, 2H), 7.41 (d, 2H), 7.31 -7.17 (m,
5H), 4.98 (s, 2H), 2.19 (s, 3H) ppm。
Embodiment 11: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,
5-di-C(CH3)3-2-(OH)-C6H2, X=Br) o-chlorobenzaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (20.3 milligrams, 0.025 mM, 5mol%),N-benzyl
Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds o-chlorobenzaldehyde
(135 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).React at 80 DEG C
36 hours, terminating reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether volume
Than be 1: 10 mixed solvent be developing solvent), productivity is 73%, and catalytic efficiency is 0.4029g/mmol/h.This substrate prior art
Purifying through column chromatography, productivity is 43%, and catalytic efficiency is 0.3587g/mmol/h, and this method has substantially compared to prior art
Advantage.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.41-7.31 (m, 2H), 7.27-7.21 (m, 4H), 7.11-
7.07 (m, 3H), 4.90 (s, 2H), 2.41 (s, 3H) ppm。
Embodiment 12: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,
5-di-C(CH3)3-2-(OH)-C6H2, X=Br) 4-Fluorobenzaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (20.3 milligrams, 0.025 mM, 5 mol%),N-benzyl
Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds 4-Fluorobenzaldehyde
(129 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).At 60 DEG C instead
Answering 36 hours, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether body
Long-pending than be 1: 20 mixed solvent be developing solvent), productivity is 86%, and catalytic efficiency is 0.1295g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.60-7.56 (m, 2H), 7.30-7.20 (m, 5H), 7.10
(d, 2H), 4.99 (s, 2H), 2.18 (s, 3H) ppm。
Embodiment 13: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,
5-di-C(CH3)3-2-(OH)-C6H2, X=Br) the 1-naphthaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (20.3 milligrams, 0.025 mM, 5 mol%),N-benzyl
Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds 1-naphthaldehyde
(162 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).36 are reacted at 70 DEG C
Hour, terminating reaction with water, product is extracted with ethyl acetate, and column chromatography purifies and (with ethyl acetate/petroleum ether volume ratio is
The mixed solvent of 1: 10 is developing solvent), productivity is 53%, and catalytic efficiency is 0.1784g/mmol/h.This substrate prior art cannot
Effectively preparation, this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.96-7.92 (m, 2H), 7.88-7.85 (m, 1H), 7.54-
7.53 (m, 2H), 7.41-7.33 (m, 2H), 7.26-6.95 (m, 5H), 4.97 (s, 2H), 2.23 (s,
3H) ppm。
Embodiment 14: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,
5-di-C(CH3)3-2-(OH)-C6H2, X=Br) the terephthalaldehydic acid methyl ester that is catalyzed andNThe oxidation of-benzylacetamide is even
Connection reaction
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-benzyl
Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds aldehyde radical benzene first
Acid methyl ester (197.1 milligrams, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).?
At 60 DEG C react 18 hours, with water terminate reaction, product is extracted with ethyl acetate, column chromatography purify (with ethyl acetate/
Petroleum ether volume ratio be the mixed solvent of 1: 10 be developing solvent), productivity is 83%, and catalytic efficiency is 0.7170g/mmol/h.This end
Thing prior art cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 8.07 (d, 2H), 7.56 (d, 2H), 7.28-7.17 (m,
5H), 4.98 (s, 2H), 3.92 (s, 3H), 2.22 (s, 3H) ppm。
Embodiment 15: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,
5-di-C(CH3)3-2-(OH)-C6H2, X=Br) 2 thiophene carboxaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (20.3 milligrams, 0.025 mM, 5 mol%),N-benzyl
Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds 2 thiophene carboxaldehyde
(111 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).At 80 DEG C instead
Answering 30 hours, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether body
Long-pending than be 1: 5 mixed solvent be developing solvent), productivity is 47%, and catalytic efficiency is 0.1122g/mmol/h.The existing skill of this substrate
Art cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.56-7.55 (m, 1H), 7.38-7.37 (d, 1H), 7.24-
7.16 (m, 5H), 6.99-6.97 (m, 1H), 4.99 (s, 2H), 2.18 (s, 3H)。
Embodiment 16: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,
5-di-C(CH3)3-2-(OH)-C6H2, X=Br) the 3-thiophenecarboxaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-benzyl
Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds 3-thiophenecarboxaldehyde
(106 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).At 60 DEG C instead
Answering 18 hours, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether body
Long-pending than be 1: 10 mixed solvent be developing solvent), productivity is 67%, and catalytic efficiency is 0.1928 g/mmol/h.This substrate is existing
Technology cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.74-7.73 (d, 1H), 7.32-7.21 (m, 7H), 5.01
(s, 2H), 2.23 (s, 3H) ppm。
Embodiment 17: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,
5-di-C(CH3)3-2-(OH)-C6H2, X=Br) 2 furan carboxyaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-benzyl
Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds 2 furan carboxyaldehyde
(99 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).36 are reacted at 60 DEG C
Hour, terminating reaction with water, product is extracted with ethyl acetate, and column chromatography purifies and (with ethyl acetate/petroleum ether volume ratio is
The mixed solvent of 1: 10 is developing solvent), productivity is 43%, and catalytic efficiency is 0.2903 g/mmol/h.This substrate prior art without
Method is effectively prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.71-7.70 (m, 1H), 7.58-7.57 (m, 1H), 7.43-
7.41 (d, 1H), 7.31-7.23 (m, 2H), 7.17-7.16 (m, 1H), 6.92-6.91 (m, 1H), 6.55-
6.54 (m, 1H), 5.08 (s, 2H), 2.24 (s, 3H) ppm。
Embodiment 18: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,
5-di-C(CH3)3-2-(OH)-C6H2, X=Br) n-hexyl aldehyde that is catalyzed andNThe oxidative coupling reaction of-benzyl phenyl-acetamides
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-benzyl benzene
Yl acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds n-hexyl aldehyde
(147 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).At 60 DEG C instead
Answering 18 hours, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether body
Long-pending than be 1: 20 mixed solvent be developing solvent), productivity is 71%, and catalytic efficiency is 0.6861g/mmol/h.The existing skill of this substrate
Art purifies through column chromatography, and productivity is 47%, and catalytic efficiency is that 0.1451g/mmol/h this method has substantially compared to prior art
Advantage.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.37-7.28 (m, 3H), 7.16 (d, 2H), 4.99 (s,
2H),2.69 (t, 2H), 2.46 (s, 3H), 1.67-1.63 (m, 2H), 1.31-1.28 (m, 4H), 0.89
(t, 3H) ppm。
Embodiment 19: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,
5-di-C(CH3)3-2-(OH)-C6H2, X=Br) benzaldehyde that is catalyzed andNThe oxidative coupling reaction of-phenyl-acetamides
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-phenyl
Acetamide (67.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds benzaldehyde (122
Microlitre, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).18 are reacted at 60 DEG C
Hour, terminating reaction with water, product is extracted with ethyl acetate, and column chromatography purifies and (with ethyl acetate/petroleum ether volume ratio is
The mixed solvent of 1: 5 is developing solvent), productivity is 80%, and catalytic efficiency is 0.5112g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.64 (d, 2H), 7.43-7.20 (m, 6H), 7.18 (d,
2H) 2.46 (s, 3H) ppm。
Embodiment 20: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,
5-di-C(CH3)3-2-(OH)-C6H2, X=Br) benzaldehyde that is catalyzed andNThe oxidative coupling reaction of-methylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-methyl
Acetamide (36.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds benzaldehyde (122
Microlitre, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).18 are reacted at 60 DEG C
Hour, terminating reaction with water, product is extracted with ethyl acetate, and column chromatography purifies and (with ethyl acetate/petroleum ether volume ratio is
The mixed solvent of 1: 10 is developing solvent), productivity is 85%, and catalytic efficiency is 0.4132g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.64–7.47 (m, 5H), 3.22 (s, 3H), 2.34 (s,
3H) ppm。
Embodiment 21: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 =
3,5-di-C(CH3)3-2-(OH)-C6H2, X=Br) benzaldehyde that is catalyzed andN-(2,4,6-trimethylphenyl) acetamide
Oxidative coupling reaction
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N -(2,4,
6-trimethylphenyl) acetamide (88.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stir 2 minutes, more successively
Add benzaldehyde (122 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).?
At 60 DEG C react 18 hours, with water terminate reaction, product is extracted with ethyl acetate, column chromatography purify (with ethyl acetate/
Petroleum ether volume ratio be the mixed solvent of 1: 10 be developing solvent), productivity is 97%, and catalytic efficiency is 0.7571g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.61-7.59 (m, 2H), 7.42-7.38 (t, 1H), 7.33-
7.30 (d, 3H), 6.89 (s, 2H), 2.24 (s, 3H), 2.20-2.19 (d, 9H) ppm。
Embodiment 22: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 =
3,5-di-C(CH3)3-2-(OH)-C6H2, X=Br) benzaldehyde that is catalyzed andN-(2,6-diisopropyl phenyl) acetamide
Oxidative coupling reaction
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N -(2,6-
Diisopropyl phenyl) acetamide (109.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stir 2 minutes, more successively
Add benzaldehyde (122 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).
Reacting 18 hours at 60 DEG C, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with acetic acid second
Ester/petroleum ether volume ratio be the mixed solvent of 1: 10 be developing solvent), productivity is 97%, and catalytic efficiency is 0.8703g/mmol/h.
This substrate prior art cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.64-7.62 (m, 2H), 7.46-7.35 (m, 4H), 7.24-
7.22 (d, 2H), 3.12-3.02 (m, 2H), 2.13 (s, 3H), 1.25-1.23 (d, 6H) , 1.16-1.14
(d, 6H) ppm。
Embodiment 23: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 =
3,5-di-C(CH3)3-2-(OH)-C6H2, X=Br) benzaldehyde that is catalyzed andN-(2,6-diisopropyl phenyl) propionic acid amide.
Oxidative coupling reaction
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N -(2,6-
Diisopropyl phenyl) propionic acid amide. (117.4 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stir 2 minutes, more successively
Add benzaldehyde (122 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).?
At 60 DEG C react 18 hours, with water terminate reaction, product is extracted with ethyl acetate, column chromatography purify (with ethyl acetate/
Petroleum ether volume ratio be the mixed solvent of 1: 10 be developing solvent), productivity is 62%, and catalytic efficiency is 0.5804g/mmol/h.This end
Thing prior art cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.63-7.61 (d, 2H), 7.46-7.37 (m, 4H), 7.25-
7.23 (d, 2H), 3.12-3.02 (m, 2H), 2.36-2.31 (m, 2H), 1.24-1.22 (d, 6H) , 1.16-
1.14 (d, 6H) , 1.09-1.05 (t, 3H)ppm。
Embodiment 24: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 =
3,5-di-C(CH3)3-2-(OH)-C6H2, X=Br) and the benzaldehyde that is catalyzed and the oxidative coupling reaction of caprolactam
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%), caprolactam
(56.6 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stir 2 minutes, sequentially add benzaldehyde (122 microlitres,
1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).React 24 hours at 70 DEG C,
Terminating reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether volume ratio for 1: 10
Mixed solvent be developing solvent), productivity is 96%, and catalytic efficiency is 0.4341g/mmol/h.This substrate prior art is through column chromatography
Separating, productivity is 67%, and catalytic efficiency is 0.1817g/mmol/h, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.56-7.53 (m, 2H), 7.46-7.37 (m, 3H), 4.00-
3.97 (m, 2H), 2.71-2.68 (m, 2H), 1.85-1.83 (m, 6H)ppm。
Embodiment 25: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 =
3,5-di-C(CH3)3-2-(OH)-C6H2, X=Br) p-tolyl aldehyde that is catalyzed andN-(2,6-diisopropyl phenyl) second
The oxidative coupling reaction of amide
In reaction bulb, under argon shield, it is sequentially added into catalyst (16.2 milligrams, 0.020 mM, 4 mol%),N -(2,
6-diisopropyl phenyl) acetamide (109.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, then depends on
Secondary addition p-tolyl aldehyde (142 microlitres, 1.2 mMs), and 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0
MM).Reacting 24 hours at 70 DEG C, terminate reaction with water, product is extracted with ethyl acetate, column chromatography purification (with
Ethyl acetate/petroleum ether volume ratio be the mixed solvent of 1: 5 be developing solvent), productivity is 89%, and catalytic efficiency is 0.2995g/
mmol/h。
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.65-7.63 (d, 2H), 7.49-7.45 (t, 1H), 7.32-
7.26 (m, 4H), 3.20-2.10 (m, 2H), 2.45 (s, 3H), 2.22 (s, 3H),1.33-1.31 (d, 6H)
, 1.23-1.22 (d, 6H) ppm。
Embodiment 26: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 =
3,5-di-C(CH3)3-2-(OH)-C6H2, X=Br) the 1-naphthaldehyde that is catalyzed andN-(2,6-diisopropyl phenyl) acetamide
Oxidative coupling reaction
In reaction bulb, under argon shield, it is sequentially added into catalyst (12.2 milligrams, 0.015 mM, 3 mol%),N -(2,6-
Diisopropyl phenyl) acetamide (109.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stir 2 minutes, more successively
Add 1-naphthaldehyde (162 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).
Reacting 28 hours at 80 DEG C, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with acetic acid second
Ester/petroleum ether volume ratio be the mixed solvent of 1: 10 be developing solvent), productivity is 81%, and catalytic efficiency is 0.4441g/mmol/h.
This substrate prior art cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 8.05-8.03 (d, 1H), 7.90-7.85 (q, 1H), 7.58-
7.41 (m, 5H), 7.31 (s, 1H), 7.29 (s, 1H),3.25-3.15 (m, 2H), 1.96 (s, 3H),
1.30-1.27 (t, 12H) ppm。
Embodiment 27: [(Ar1NCH2CH2NAr2)CH][FeX4] (Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 =
3,5-di-C(CH3)3-2-(OH)-C6H2, X=Br) p-bromobenzaldehyde that is catalyzed andN-(2,6-diisopropyl phenyl) acetyl
The oxidative coupling reaction of amine
In reaction bulb, under argon shield, it is sequentially added into catalyst (16.2 milligrams, 0.020 mM, 4 mol%),N -(2,
6-diisopropyl phenyl) acetamide (109.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, then depends on
Secondary addition p-bromobenzaldehyde (220.0 milligrams, 1.2 mMs), and 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0
MM).Reacting 18 hours at 60 DEG C, terminate reaction with water, product is extracted with ethyl acetate, column chromatography purification (with
Ethyl acetate/petroleum ether volume ratio be the mixed solvent of 1: 10 be developing solvent), productivity is 93%, and catalytic efficiency is 0.5193g/
mmol/h.This substrate prior art cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure
Characterize:1H NMR (400 MHz, CDCl3, TMS): 7.55-7.48 (q, 4H), 7.43-7.39 (t, 1H), 7.26-
7.24 (t, 2H), 3.07-2.98 (m, 2H), 2.11 (s, 3H), 1.25-1.24 (d, 6H) , 1.15-1.13
(d, 6H) ppm。
Claims (5)
1. ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation is catalyzed aldehyde and two as single-component catalyst
The method of the oxidative coupling reaction of level amide, comprises the following steps: under room temperature, in inert gas atmosphere, successively to reactor
Middle addition catalyst, two grades of amide, organic solvents, stirring;Then proceed in reactor, be sequentially added into aldehyde, tert-butyl hydroperoxide
Aqueous solution of hydrogen, in 60~80 DEG C of stirring reactions 18~36 hours;Reaction terminates reaction with water after terminating;Product acetic acid second
Ester extracts, and is i.e. obtained product by column chromatography, i.e. obtains product;The described ionic iron containing single phenol functionalization Imidazole cation
(III) coordination compound has a structural formula of formula I:
Formula I;
Wherein R1For methyl or isopropyl;R2For hydrogen or methyl;R3For hydrogen or the tert-butyl group;X is chlorine or bromine.
Method the most according to claim 1, it is characterised in that: described noble gas is nitrogen or argon;Described organic
Solvent is 1,2-dichloroethanes.
Method the most according to claim 1, it is characterised in that: with molar amount, aldehyde: two grades of amide: tert-butyl hydroperoxide
Hydrogen: catalyst is 2.4: 1: 2.0: (0.02~0.05);Response time is 18 hours, and reaction temperature is 60 DEG C.
Method the most according to claim 1, it is characterised in that: with molar amount, aldehyde: two grades of amide: tert-butyl hydroperoxide
Hydrogen: catalyst is 2.4: 1: 2.0: 0.02.
Method the most according to claim 1, it is characterised in that: described aldehyde be benzaldehyde, o-tolualdehyde, to chlorobenzene first
Aldehyde, p-bromobenzaldehyde, o-chlorobenzaldehyde, 4-Fluorobenzaldehyde, terephthalaldehydic acid methyl ester, 1-naphthaldehyde, 2 thiophene carboxaldehyde, 3-thiophene
Fen formaldehyde, 2 furan carboxyaldehyde, p-tolyl aldehyde, P-methoxybenzal-dehyde, paranitrobenzaldehyde, to cyanobenzaldehyde, just oneself
Aldehyde or hutanal;Described two grades of amide areN-benzylacetamide,N-methylacetamide,N-(2,4,6-trimethylphenyl) acetyl
Amine,N-(2,6-diisopropyl phenyl) acetamide,N-(2,6-diisopropyl phenyl) propionic acid amide.,N-(4-aminomethyl phenyl) acetyl
Amine,N-(4-methoxyphenyl) acetamide,N-(4-chlorphenyl) acetamide,N-(4-trifluoromethyl) acetamide,N-hexamethylene
Yl acetamide,N-Phenylpropionamide or caprolactam.
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