CN108250153B - Preparation method of trans-disubstituted olefin - Google Patents
Preparation method of trans-disubstituted olefin Download PDFInfo
- Publication number
- CN108250153B CN108250153B CN201810144381.9A CN201810144381A CN108250153B CN 108250153 B CN108250153 B CN 108250153B CN 201810144381 A CN201810144381 A CN 201810144381A CN 108250153 B CN108250153 B CN 108250153B
- Authority
- CN
- China
- Prior art keywords
- pyridine
- trans
- reaction
- cdcl
- nmr
- 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.)
- Expired - Fee Related
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- -1 alkene compound Chemical class 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000006772 olefination reaction Methods 0.000 claims abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 150000003624 transition metals Chemical class 0.000 claims abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 102
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 102
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 70
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 34
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- PSWKVGHKABDSRC-UHFFFAOYSA-N $l^{1}-azanylmethane Chemical compound [N]C PSWKVGHKABDSRC-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 4
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 claims description 2
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 2
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- WDWDWGRYHDPSDS-UHFFFAOYSA-N methanimine Chemical compound N=C WDWDWGRYHDPSDS-UHFFFAOYSA-N 0.000 claims description 2
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical group [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003138 primary alcohols Chemical class 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 4
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 229910016660 Mn2(CO)10 Inorganic materials 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- QFEOTYVTTQCYAZ-UHFFFAOYSA-N dimanganese decacarbonyl Chemical compound [Mn].[Mn].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] QFEOTYVTTQCYAZ-UHFFFAOYSA-N 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000000575 pesticide Substances 0.000 abstract description 2
- 235000013599 spices Nutrition 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 230000005622 photoelectricity Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 128
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 96
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 42
- 239000011572 manganese Substances 0.000 description 37
- 150000001344 alkene derivatives Chemical class 0.000 description 35
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 33
- 238000004440 column chromatography Methods 0.000 description 33
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 32
- 238000005160 1H NMR spectroscopy Methods 0.000 description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 32
- 239000005977 Ethylene Substances 0.000 description 32
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 32
- 239000003208 petroleum Substances 0.000 description 32
- 239000000047 product Substances 0.000 description 32
- 239000007787 solid Substances 0.000 description 32
- 238000003756 stirring Methods 0.000 description 31
- 235000019445 benzyl alcohol Nutrition 0.000 description 11
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical compound CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 description 10
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 208000006673 asthma Diseases 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- NJFDMENHTAYHMA-UHFFFAOYSA-N (4-chlorophenyl)-phenyldiazene Chemical compound C1=CC(Cl)=CC=C1N=NC1=CC=CC=C1 NJFDMENHTAYHMA-UHFFFAOYSA-N 0.000 description 1
- ZYXYMEZEZFQOAK-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-yl)propanenitrile Chemical compound C1=CC=C2SC(CCC#N)=NC2=C1 ZYXYMEZEZFQOAK-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 206010006482 Bronchospasm Diseases 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 238000006130 Horner-Wadsworth-Emmons olefination reaction Methods 0.000 description 1
- UCHDWCPVSPXUMX-TZIWLTJVSA-N Montelukast Chemical class CC(C)(O)C1=CC=CC=C1CC[C@H](C=1C=C(\C=C\C=2N=C3C=C(Cl)C=CC3=CC=2)C=CC=1)SCC1(CC(O)=O)CC1 UCHDWCPVSPXUMX-TZIWLTJVSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 229960001138 acetylsalicylic acid Drugs 0.000 description 1
- 125000002009 alkene group Chemical group 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 150000007854 aminals Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000024695 exercise-induced bronchoconstriction Diseases 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011866 long-term treatment Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229960005127 montelukast Drugs 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- JGOAZQAXRONCCI-UHFFFAOYSA-N n-(benzylideneamino)aniline Chemical compound C=1C=CC=CC=1NN=CC1=CC=CC=C1 JGOAZQAXRONCCI-UHFFFAOYSA-N 0.000 description 1
- 238000005648 named reaction Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D215/14—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/18—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
- C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D237/08—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a preparation method of trans-disubstituted alkene, belonging to the technical field of organic chemical synthesis. The method adopts simple alcohol and methyl nitrogen heterocyclic ring as initial raw materials, and obtains the trans-disubstituted alkene compound through a transition metal catalytic olefination reaction. The reaction raw materials, the catalyst and the additive are cheap and easy to obtain, the synthesis process is simple, and the synthesis cost is greatly reduced; the reaction condition is mild, the yield is high, and the industrialization is easy to realize; the reaction raw materials and the catalyst are clean and nontoxic, and the environmental pollution is small. The trans-disubstituted alkene compound and the derivative thereof are used as important fine chemicals and widely applied to the industries of medicines, pesticides, spices, photoelectricity and the like.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and relates to a preparation method of trans-disubstituted alkene.
Background
Olefin is an important fine chemical, and has wide application in the industries of pesticides, medicines, spices and the like. The alkene group is a common pharmacophore, widely exists in various natural products and synthetic drugs with physiological activities, and is also a fragment constituting various functional materials. For example, the trans disubstituted alkene, montelukast, is useful for the prevention and long-term treatment of asthma in adults over 15 years of age, including the prevention of daytime and nighttime asthmatic symptoms, the treatment of aspirin-sensitive asthmatics, and the prevention of exercise-induced bronchoconstriction. Due to the specific use of these compounds, a number of synthetic methods have been developed in recent years.
There are a number of conventional methods for synthesizing trans-disubstituted olefins: (1) many human name reactions (Witting, Horner-Wadsworth-Emmons, Peterson interference, Julia interference, etc.); (2) catalyzing Heck reaction; (3) carrying out Suzuki coupling reaction; (4) olefin metathesis. Although these methods have high yield, most of the above methods require an equivalent amount of a phosphine reagent, a metal reagent or use of an aldehyde and an equivalent amount of an initiator and various additives, and the practical application is extremely limited.
All the previous reactions are based on the participation of equivalent metal reagents or phosphine ylide reagents, so that a large amount of metal waste and organic phosphine compounds are inevitably generated, the reaction economy is not high, and meanwhile, the environment is greatly stressed, and the requirements of green sustainable development are not met. Due to the utilization of various additives, the development of reaction substrates is severely limited, the compatibility of the functional groups of the reaction substrates is poor, and the economic applicability is not high.
Therefore, the method directly utilizes alcohol without aldehyde to directly carry out an olefination reaction with a methyl heterocyclic compound, the by-products are only water and hydrogen, and the method has important theoretical significance and wide application prospect in preparing the trans-disubstituted olefin derivative with wide substrate applicability range and high atom economy and meets the requirement of green chemistry.
Disclosure of Invention
The invention aims to provide a simple and efficient preparation method of trans-disubstituted olefin.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the method for preparing the trans-disubstituted olefin uses primary alcohol and methyl nitrogen-containing heterocycle as raw materials, and carries out an olefination reaction under the catalysis of a transition metal catalyst to obtain a compound with a trans-disubstituted olefin structure, and the compound is reacted for 23 to 48 hours under nitrogen; after the reaction is finished, pumping out the solvent, and carrying out column chromatography to obtain the trans-disubstituted alkene compound;
the general reaction formula is as follows:
the structural formula of the methyl nitrogen-containing heterocyclic ring is as follows:
x, Y, Z is an independent carbon atom or nitrogen atom, R1Each group is independently selected from hydrogen, halogen or methoxy.
The alcohol derivative has the structure:
R2the radicals being selected from C1~C10Aliphatic radical of (e.g. ethyl, propyl, butyl, benzyl, cyclohexyl, cyclopropyl), C4~C10An aromatic group (e.g., furyl derivative, pyridyl derivative, thienyl derivative, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl).
Or the like, or, alternatively,
the structural formula of the methyl nitrogen-containing heterocyclic ring is as follows:
x 'and Y' are independent carbon atoms or nitrogen atoms, R3Each group is independently selected from hydrogen, halogen or methoxy;
the alcohol derivative has the structure:
R4the radicals being selected from C1~C10Aliphatic radical of (e.g. ethyl, propyl, butyl, benzyl, cyclohexyl, cyclopropyl), C4~C10An aromatic group (e.g., furyl derivative, pyridyl derivative, thienyl derivative, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl).
Or the like, or, alternatively,
the structural formula of the methyl nitrogen-containing heterocyclic ring is as follows:
the condensed amine aldehyde derivative has the structure as follows:
R5the radicals being selected from C1~C10Aliphatic radical of (e.g. ethyl, propyl, butyl, benzyl, cyclohexyl, cyclopropyl), C4~C10An aromatic group (e.g., furyl derivative, pyridyl derivative, thienyl derivative, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl).
The base is potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium hydride, sodium hydride, lithium hydride, potassium carbonate or sodium carbonate; potassium hydroxide, sodium hydroxide or potassium hydride is preferred.
The catalyst is manganese pentacarbonyl bromide (Mn (CO)2Br) or manganese decacarbonyl (Mn)2(CO)10) The dosage of the catalyst is 0.5 to 10 percent of the molar weight of the aminal derivative.
The ligand is (E) -1- (2-pyridyl) -N- (2-picolyl) azomethine
[ (E) -1- (pyridin-2-yl) -N- (pyridin-2-ylmethy l) methanimine ], (E) -1- (2-pyridyl) -N- (2-picolyl) ethylenimine [ (E) -1- (pyridin-2-yl) -N- (pyridin-2-ylmethy l) ethane-1-imine ], (E) -2- ((2- (2-pyridyl) hydrazono) methyl) pyridine [ (E) -2- ((2- (pyridine-2-yl) hydrazono) methyl) pyridine ] or [ (E) -2- (2- (1- (2-pyridyl) ethylidene) hydrazono) pyridine ] [ (E) -2- (2- (1- (pyridine-2-yl) ethylidene) hydrazono) pyridine ].
The organic solvent is one or two of benzene, nitromethane, toluene, benzotrifluoride, xylene, mesitylene, 1, 4-dioxane, acetonitrile, propionitrile, dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, diethyl ether, ethylene glycol dimethyl ether, methyl tert-butyl ether, methyl cyclopentyl ether, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, methanol, ethanol and tert-amyl alcohol. The mixed solvent of tert-amyl alcohol and toluene is preferred.
Compared with the prior art, the invention has the following advantages:
1. the method has the advantages that the alcohol and the methyl nitrogen-containing heterocycle react under the catalysis of the industrially cheap and easily available metal catalyst, the trans-disubstituted alkene compound can be efficiently prepared by one step through the alkenylation method, the reaction raw materials and the catalyst are cheap and easily available, the synthesis process is simple, and the synthesis cost is greatly reduced;
2. the invention can efficiently synthesize the trans-disubstituted alkene by one step, which is to obtain the trans-disubstituted alkene compound by the first time of utilizing alcohol through the alkene reaction.
3. The method has the advantages of mild reaction conditions, simple operation, high yield, wide substrate applicability range and easy industrialization.
4. The reaction raw material (alcohol) and the catalyst (manganese) are clean, nontoxic, cheap and have little pollution to the environment.
5. The reaction process is clean and meets the requirement of green chemistry.
6. The reaction has high conversion efficiency, can realize gram-scale amplification experiments, and is easy to realize industrialization.
Detailed Description
The present invention is further described below.
Example 1
Preparation of trans-disubstituted alkene derivatives 3a
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylpyrazine 1a (2mmol) and benzyl alcohol 2a (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed on ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 a. The product was a white solid in 81% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.65(s,1H),8.55(s,1H),8.41(d,J=2.3Hz,1H),7.76(d,J=16.1Hz,1H),7.61(d,J=8.1Hz,2H),7.43–7.32(m,3H),7.17(d,J=16.1Hz,1H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=124.0,127.3,128.9,129.0,135.2,136.0,142.8,143.8,144.4,151.3ppm.CAS Registry Number:35782-36-6.
Example 2
Preparation of trans-disubstituted alkene derivatives 3b
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 1a (2mmol) and benzyl alcohol 2b (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed on ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 b. The product was a white solid in 63% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.58(d,J=31.0Hz,2H),8.39(s,1H),7.72(d,J=16.1Hz,1H),7.49(d,J=7.9Hz,2H),7.20(d,J=7.8Hz,2H),7.11(d,J=16.1Hz,1H),2.38(s,3H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=123.0,127.3,129.6,133.3,135.2,139.2,142.5,143.7,144.2,151.5ppm.Elemental analysis calcd for C13H12N2(M:196.10)[%]:C,79.56;H,6.16;N,14.27found:C 79.77,H 6.62,N 13.75.CAS Registry Number:142772-03-0.
Example 3
Preparation of trans-disubstituted alkene derivatives 3c
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) and 1.0mL of toluene, stirring for two hours, adding 2-methylpyrazine 1a (2mmol) and benzyl alcohol 2c (1mmol), reacting at 135 deg.C for 48 hours, stopping the reaction, evaporating the solvent, and performing column chromatography on ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 c. The product was a white solid in 81% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.63(s,1H),8.54(s,1H),8.43(s,1H),7.69(d,J=16.1Hz,1H),7.52(d,J=8.5Hz,2H),7.45(d,J=8.4Hz,2H),7.14(d,J=16.1Hz,1H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=124.4,128.4,129.0,133.7,134.4,134.6,142.9,143.7,144.3,150.8ppm.Elemental analysis calcd for C12H9ClN2(M:216.04)[%]:C,66.52;H,4.19;Cl,16.36;N,12.93found:C 67.00,H 3.73,N 12.57.
Example 4
Preparation of trans-disubstituted alkene derivatives 3d
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) and 1.0mL of toluene, stirring for two hours, adding 2-methylpyrazine 1a (2mmol) and benzyl alcohol 2d (1mmol), reacting at 135 deg.C for 48 hours, stopping the reaction, evaporating the solvent, and performing column chromatography on ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 d. The product was a white solid in 68% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.63(s,1H),8.54(s,1H),8.43(s,1H),7.69(d,J=16.1Hz,1H),7.52(d,J=8.5Hz,2H),7.45(d,J=8.4Hz,2H),7.14(d,J=16.1Hz,1H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=123.0,124.6,128.8,132.0,133.9,135.0,143.0,143.9,144.4ppm.CAS Registry Number:1810802-39-1.
Example 5
Preparation of trans-disubstituted alkene derivatives 3e
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylpyrazine 1a (2 m)mol) and benzyl alcohol 2e (1mmol), reacting at 135 deg.C for 48 hr, stopping reaction, evaporating solvent, and performing column chromatography with ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 e. The product was a white solid in 83% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.54(d,J=17.7Hz,2H),8.39(s,1H),7.89(d,J=15.8Hz,1H),7.31-7.30(m,1H),7.22–7.21(m,1H),7.07–7.03(m,1H),6.95(d,J=15.8Hz,1H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=123.1,126.4,127.9,128.0,128.7,141.6,142.6,143.7,144.3,150.9ppm.Elemental analysis calcd for C10H8N2S(M:188.04)[%]:C,63.80;H,4.28;N,14.88;S,17.03found:C 63.51,H 3.84,N 14.37.CAS:361444-92-0.
Example 6
Preparation of trans-disubstituted alkene derivatives 3f
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 1b (2mmol) and benzyl alcohol 2a (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed on ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 f. The product was a white solid in 80% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=9.05(d,J=4.8Hz,1H),7.69(d,J=16.4Hz,1H),7.64–7.61(m,2H),7.59(s,1H),7.46–7.43(m,1H),7.41–7.36(m,3H),7.33(d,J=5.2Hz,1H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=124.0,125.2,126.4,127.4,128.9,129.1,135.2,135.9,149.7,158.3ppm.CAS:35782-26-4.
Example 7
Preparation of 3g of Trans-disubstituted alkene derivative
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylpyrazine 1c (2mmol) and benzyl alcohol 2a (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, column chromatography was performed using ethyl acetate/petroleum ether (1:10) and 3g of trans-disubstituted olefin derivative. The product was a white solid in 60% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.59(d,J=4.4Hz,2H),7.56-7.54(m,2H),7.40–7.35(m,5H),7.31(d,J=10.7Hz,1H),7.03(d,J=16.3Hz,1H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=120.9,126.0,127.0,128.8,128.9,133.3,136.1,144.7,150.1ppm.CAS:5097-93-8.
Example 8
Preparation of trans-disubstituted alkene derivatives for 3h
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, stirred for two hours, added with 1d (2mmol) and 2a (1mmol), reacted at 135 ℃ for 48 hours, then the reaction was stopped, the solvent was evaporated, and column chromatography was performed on ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative for 3 hours. The product was a white solid in 70% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.10(d,J=8.5Hz,1H),8.06(d,J=8.5Hz,1H),7.77(d,J=8.0Hz,1H),7.70–7.69(m,1H),7.62–7.53(m,2H),7.51–7.48(m,2H),7.30–7.25(m,2H),6.55–6.54(m,1H),6.48–6.47(m,1H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=110.3,113.9,119.8,124.5,125.2,127.5,128.9,129.8,135.1,139.4,142.2,150.4,162.8ppm.CAS:59066-62-5.
Example 9
Preparation of trans-disubstituted alkene derivatives 3i
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 1e (2mmol) and benzyl alcohol 2a (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed on ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 i. The product was a white solid in 57% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.57(d,J=5.6Hz,1H),8.39(d,J=8.4Hz,1H),8.01(s,2H),7.84(d,J=8.2Hz,1H),7.72–7.63(m,4H),7.58(d,J=5.6Hz,1H),7.45–7.40(m,2H),7.37–7.32(m,1H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=112.0,122.9,124.5,127.2,127.4,127.5,128.6,128.8,129.9,135.8,136.8,137.0,142.5,154.6ppm.CAS:59066-57-8.
Example 10
Preparation of trans-disubstituted alkene derivatives 3j
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) and 1.0mL of toluene, stirring for two hours, adding 1f (2mmol) and benzyl alcohol 2a (1mmol), reacting at 135 deg.C for 48 hours, stopping reaction, evaporating solvent, and performing column chromatography to obtain ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefinDerivative 3 j. The product was a white solid in 86% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.06–8.01(m,2H),7.77–7.76(m,1H),7.71(d,J=11.8Hz,1H),7.68–7.63(m,4H),7.44–7.41(m,2H),7.39–7.32(m,2H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=120.2,126.2,127.4,127.9,128.4,128.9,130.7,131.8,135.0,135.5,136.3,146.6,156.2ppm.CAS:1139911-18-4.
Example 11
Preparation of trans-disubstituted alkene derivatives 3k
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 1g (2mmol) of benzyl alcohol 2a (1mmol) was added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed on ethyl acetate/petroleum ether (1:10), trans-disubstituted olefin derivative 3 k. The product was a white solid in 95% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.01(s,1H),7.98(s,1H),7.64(d,J=5.9Hz,2H),7.62–7.59(m,2H),7.42–7.37(m,3H),7.36–7.27(m,2H),7.04(d,J=2.8Hz,1H),3.92(s,3H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=55.6,105.3,119.6,122.4,127.2,128.3,128.4,128.8,130.6,135.2,136.7,153.6,157.7ppm.CAS:59066-58-9.
Example 12
Preparation of trans-disubstituted alkene derivative 3aa
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and benzyl alcohol 2a (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 aa. The product was a white solid in 94% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.15–8.07(m,2H),7.79(d,J=8.0Hz,1H),7.64–7.72(m,5H),7.52–7.47(m,1H),7.45–7.39(m,3H),7.35–7.32(m,1H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=119.3,126.2,127.3,127.5,128.7,128.8,129.0,129.2,129.8,134.5,136.4,136.5,148.3 156.0ppm.CAS Registry Number:38101-69-8.
Example 13
Preparation of trans-disubstituted alkene derivatives 3ab
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2b (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ab. The product was a white solid in 92% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.12(d,J=8.6Hz,1H),8.07(d,J=8.5Hz,1H),7.78(d,J=8.1Hz,1H),7.73–7.68(m,2H),7.65(d,J=5.0Hz,1H),7.55(d,J=8.0Hz,2H),7.52–7.47(m,1H),7.37(d,J=16.3Hz,1H),7.22(d,J=8.0Hz,2H),2.39(s,3H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=21.4,119.2,126.1,127.2,127.3,127.5,128.1,129.2,129.6,129.7,133.8,134.4,136.3,138.8,148.3,156.2ppm.CAS Registry Number:1289213-24-6.
Example 14
Preparation of trans-disubstituted alkene derivatives 3ac
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2c (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ac. The product was a white solid in 94% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.13(d,J=8.6Hz,1H),8.08(d,J=8.5Hz,1H),7.79(d,J=8.1Hz,1H),7.74–7.68(m,2H),7.65(d,J=7.8Hz,1H),7.52–7.38(m,4H),7.30(t,J=7.5Hz,1H),7.15(d,J=7.4Hz,1H),2.41(s,3H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=21.5,119.2,124.5,126.1,127.5,128.0,128.7,128.90,129.2,129.5,129.7,134.5,136.3,136.5,148.3,156.1ppm.CAS Registry Number:1318193-16-6.
Example 15
Preparation of trans-disubstituted alkene derivative 3ad
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2d (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ad. The product was a white solid in 81% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.14(t,J=8.5Hz,2H),7.97(d,J=16.2Hz,1H),7.82–7.69(m,4H),7.55–7.50(m,1H),7.35(d,J=16.2Hz,1H),7.28–7.27(m,1H),2.55(s,3H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=19.9,119.2,125.7,126.1,126.2,127.4,128.4,129.2,129.6,130.1,130.5,132.0,136.2,148.2,156.1ppm.CAS Registry Number:1318193-18-8.
Example 16
Preparation of trans-disubstituted alkene derivative 3ae
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2e (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ae. The product was a white solid in 80% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.15–8.08(m,2H),7.81–7.66(m,4H),7.53–7.48(m,1H),6.98–6.92(m,3H),2.44(s,6H),2.32(s,3H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=21.1,21.3,119.0,126.1,127.4,127.5,129.0,129.3,129.7,132.9,134.1,136.3,136.5,137.0,148.3,156.3ppm.Elemental analysis calcd for C20H19N(M:273.15)[%]:C,87.87;H,7.01;N,5.12found:C 88.04,H 7.11,N 5.55.CAS Registry Number:848232-91-7
Example 17
Preparation of trans-disubstituted alkene derivatives 3af
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2f (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted alkene derivative 3 af. The product was a white solid in 86% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.16(d,J=8.6Hz,1H),8.11(d,J=8.5Hz,1H),7.82(d,J=8.0Hz,1H),7.76–7.68(m,3H),7.62(d,J=8.3Hz,2H),7.55–7.50(m,1H),7.48–7.39(m,3H),1.39(s,9H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=31.3,34.8,119.2,125.8,126.1,127.1,127.3,127.5,128.3,129.2,129.7,133.8,134.3,136.3,148.3,152.0,156.3ppm.Elemental analysis calcd for C20H19N(M:287.17)[%]:C,87.76;H,7.37;N,4.87found:C 87.22,H 7.72,N 5.00.CAS Registry Number:801231-11-8.
Example 18
Preparation of trans-disubstituted alkene derivative 3ag
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2g (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ag. The product was a white solid in 92% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.15(d,J=8.5Hz,1H),8.10(d,J=8.5Hz,1H),7.80(d,J=8.1Hz,1H),7.77–7.72(m,4H),7.69–7.63(m,5H),7.54–7.49(m,2H),7.45(d,J=7.2Hz,2H),7.39–7.34(m,1H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=119.4,126.2,127.0,127.4,127.5,127.6,127.8,128.9,129.0,129.2,129.8,134.0,135.6,136.4,140.5,141.4,148.3,156.0ppm.CAS Registry Number:190437-73-1
Example 19
Preparation of trans-disubstituted alkene derivative 3ah
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2h (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ah. The product was a white solid in 96% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.11(d,J=8.5Hz,1H),8.06(d,J=8.5Hz,1H),7.78(d,J=8.1Hz,1H),7.72–7.67(m,2H),7.64-7.58(m,3H),7.48(t,J=7.4Hz,1H),7.31–7.26(m,2H),6.94(d,J=7.3Hz,2H),3.85(s,3H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=55.4,114.3,119.2,125.9,126.9,127.2,127.5,128.7,129.1,129.3,129.7,134.0,136.2,148.3,156.4,160.1ppm.CAS Registry Number:190437-90-2.
Example 20
Preparation of trans-disubstituted alkene derivative 3ai
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol), 1.0mL of formazan was addedAfter stirring in benzene for two hours, 2-methylquinoline 4(2mmol) and 2i (1mmol) were added, the reaction was stopped after 48 hours at 135 ℃, the solvent was evaporated to dryness, and column chromatography was performed on ethyl acetate/petroleum ether (1:10) and trans-disubstituted alkene derivative 3 ai. The product was a white solid in 93% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.10(t,J=8.0Hz,2H),8.03(d,J=16.6Hz,1H),7.79–7.67(m,4H),7.51–7.41(m,2H),7.34–7.24(m,1H),7.01(t,J=7.5Hz,1H),6.94(d,J=8.3Hz,1H),3.93(s,3H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=55.6,111.0,119.0,120.8,125.5,126.0,127.2,127.3,127.5,129.2,129.3,129.6,129.8,136.2,148.3,156.8,157.4ppm.CAS Registry Number:77669-18-2.
Example 21
Preparation of trans-disubstituted alkene derivative 3aj
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2j (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 aj. The product was a white solid in 85% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.17(d,J=8.5Hz,1H),8.11(d,J=8.5Hz,1H),7.82(d,J=8.1Hz,1H),7.77–7.67(m,3H),7.61–7.51(m,3H),7.42–7.37(m,3H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=119.4,126.3,127.4,127.5,128.4,129.0,129.2,129.5,129.8,133.0,134.3,135.0,136.4,148.3,155.6ppm.CAS Registry Number:38101-91-6.
Example 22
Preparation of trans-disubstituted alkene derivative 3ak
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2k (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ak. The product was a white solid in 86% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.18-8.05(m,2H),7.87–7.72(m,3H),7.54(t,J=7.5Hz,1H),7.47–7.41(m,1H),7.36–7.31(m,1H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=118.9,126.3,126.9,127.0,127.4,129.2,129.4,129.7,129.9,130.1,131.7,134.5,136.3,148.1,155.7ppm.CAS Registry Number:14174-62-0.
Example 23
Preparation of trans-disubstituted alkene derivatives 3al
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2l (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 al. The product was a white solid in 72% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.14(d,J=8.6Hz,1H),8.08(d,J=8.5Hz,1H),7.79(d,J=8.1Hz,1H),7.74-7.69(m,1H),7.66-7.66(m,1H),7.62(d,J=5.8Hz,1H),7.55–7.48(m,5H),7.39(d,J=16.3Hz,1H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=119.3,122.5,126.3,127.4,127.5,128.6,129.1,129.5,129.8,131.9,133.1,135.4,136.5,148.1,155.5ppm.CAS Registry Number:1220212-12-3.
Example 24
Preparation of trans-disubstituted alkene derivative 3am
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2m (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 am. The product was a white solid in 69% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.13(d,J=8.5Hz,1H),8.07(d,J=8.9Hz,1H),7.79(d,J=8.1Hz,1H),7.71(t,J=8.4Hz,3H),7.65–7.59(m,2H),7.50(t,J=7.5Hz,1H),7.42–7.35(m,3H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=119.3,126.2,127.3,127.5,128.3,128.9,129.2,129.4,129.8,132.9,134.2,135.0,136.4,148.2,155.5ppm.CAS Registry Number:1391817-61-0.
Example 25
Preparation of trans-disubstituted alkene derivatives 3an
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) is added into 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and,2n (1mmol), reacting at 135 deg.C for 48 hr, stopping reaction, evaporating solvent, and performing column chromatography with ethyl acetate/petroleum ether (1:10) and trans-disubstituted alkene derivative 3 an. The product was a white solid in 70% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.57(d,J=16.0Hz,1H),8.39(d,J=8.2Hz,1H),8.19(t,J=8.8Hz,2H),7.97–7.89(m,3H),7.85(d,J=8.1Hz,1H),7.80–7.75(m,2H),7.65–7.57(m,3H),7.56–7.49(m,2H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=119.6,123.7,124.2,125.7,125.9,126.2,126.3,127.5,128.6,128.9,129.3,129.7,136.4,148.3,156.0ppm.CAS Registry Number:190437-71-9.
Example 26
Preparation of trans-disubstituted alkene derivative 3ao
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2o (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ao. The product was a white solid in 67% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=7.81(d,J=16.4Hz,1H),7.75–7.71(m,1H),7.63–7.60(m,2H),7.56–7.53(m,1H),7.47–7.39(m,3H),7.36–7.33(m,2H),7.09(d,J=15.7Hz,1H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=111.2,112.0,120.0,121.7,126.0,126.8,127.3,127.5,129.2,129.7,136.3,143.2,148.4,152.9,155.6ppm.CAS Registry Number:1318193-21-3.
EXAMPLE 27 preparation of the Trans-disubstituted alkene derivative 3ap
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2p (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ap. The product was a white solid in 93% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.09(dd,J=14.8,8.5Hz,2H),7.86(d,J=16.1Hz,1H),7.77–7.69(m,2H),7.54(d,J=8.6Hz,1H),7.49(t,J=8.0,3.9Hz,1H),7.30(d,J=5.1Hz,1H),7.25–7.21(m,2H),7.08–7.05(m,1H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=119.2,125.9,125.9,127.1,127.4,127.7,128.0,128.1,129.0,129.6,136.1,141.9,148.1,155.4ppm.CAS Registry Number:73010-95-4.
Example 28
Preparation of trans-disubstituted alkene derivative 3aq
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2q (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 aq. The product was a white solid in 69% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.67–8.64(m,1H),8.19–8.14(m,2H),7.87–7.85(m,2H),7.81–7.79(m,1H),7.75–7.67(m,3H),7.61–7.59(m,1H),7.55–7.50(m,1H),7.25–7.19(m,1H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=109.9,120.3,122.8,122.9,126.6,127.5,123.0,136.7,149.7,154.9,155.1ppm.CAS Registry Number:16552-20-8.
Example 29
Trans-disubstituted alkene derivatives 3ar
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2r (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was carried out using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 ar. The product was a white solid in 74% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.06(d,J=8.5Hz,2H),7.76(d,J=8.1Hz,1H),7.71–7.66(m,1H),7.54(d,J=8.5Hz,1H),7.50–7.45(m,1H),6.85–6.78(m,1H),6.71(d,J=16.1Hz,1H),2.28(s,1H),1.94–1.72(m,5H),1.45–1.23(m,5H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=26.0,26.1,32.5,41.1,118.6,125.7,127.0,127.3,128.6,129.0,129.4,136.0,143.3,148.0,156.7ppm.CAS Registry Number:1318193-26-8.
Example 30
Preparation of trans-disubstituted alkene derivatives 3as
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2s (1mmol) were added theretoAfter 48 hours at 135 ℃, the reaction was stopped, the solvent was evaporated to dryness, and column chromatography was performed on ethyl acetate/petroleum ether (1:10), trans-disubstituted olefin derivative 3 as. The product was a white solid in 85% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.03-7.99(m,2H),7.72(d,J=8.1Hz,1H),7.68–7.62(m,1H),7.53–7.33(m,2H),6.77(d,J=15.7Hz,1H),6.42–6.34(m,1H),1.75–1.63(m,1H),0.95–0.88(m,2H),0.69–0.64(m,2H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=8.1,14.9,118.9,125.6,127.0,127.4,128.3,129.0,129.5,136.1,142.0,148.1,156.2ppm.CAS Registry Number:2042682-91-5.
EXAMPLE 31 preparation of trans-disubstituted alkene derivative 3at
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2t (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was carried out using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 at. The product was a white solid in 70% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.04(d,J=8.5Hz,2H),7.73(d,J=8.1Hz,1H),7.66(t,J=7.7Hz,1H),7.55(d,J=8.7Hz,1H),7.45(t,J=7.5Hz,1H),6.83(d,J=16.2Hz,1H),6.66(d,J=16.3Hz,1H),1.19(s,9H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=29.4,33.8,118.5,125.7,126.4,127.0,127.3,129.0,129.4,136.0,148.0,148.1,156.8ppm.CAS Registry Number:1639897-71-4.
Example 32
Preparation of trans-disubstituted alkene derivative 3au
The synthetic route is as follows:
in a glove box, Mn (CO)5Br (0.005mmol) [ (E) -2- (2- (1- (2-pyridine) ethylene) hydrazino) pyridine](0.006mmol) was added to 1.0mL of toluene, and after stirring for two hours, 2-methylquinoline 4(2mmol) and 2u (1mmol) were added, followed by reaction at 135 ℃ for 48 hours, the reaction was stopped, the solvent was evaporated, and column chromatography was performed using ethyl acetate/petroleum ether (1:10) and trans-disubstituted olefin derivative 3 au. The product was a white solid in 81% yield.
1H NMR(299.86MHz,23.0℃,CDCl3):δ=8.07–8.02(m,2H),7.74(d,J=8.1Hz,1H),7.69–7.64(m,1H),7.56(d,J=8.6Hz,1H),7.48–7.43(m,1H),6.70(d,J=16.0Hz,1H),6.55(dd,J=16.0,8.6Hz,1H),2.15–2.04(m,1H),1.64–1.36(m,4H),0.93(t,J=7.4Hz,6H)ppm;13C NMR(75.41MHz,23.0℃,CDCl3):δ=11.9,27.5,46.9,118.6,125.8,127.2,127.4,129.2,129.5,131.4,136.1,141.9,148.1,156.5ppm.Elemental analysis calcd for C16H19N(M:225.15)[%]:C,85.28;H,8.50;N,6.22found:C 85.12,H 8.99,N 6.70.
Claims (4)
1. A preparation method of trans-disubstituted alkene is characterized in that primary alcohol and methyl nitrogen-containing heterocycle are used as raw materials, and an olefination reaction is carried out under the condition of ligand, alkali and solvent by catalysis of a transition metal catalyst to obtain a compound with a trans-disubstituted alkene structure;
the general reaction formula is as follows:
wherein: x, Y, Z is an independent carbon atom or nitrogen atom, R1And R2Each independently selected from the following groups: hydrogen, halogen, methoxy, straight or branched C1~C20An aromatic group, the aromatic ring represented by the dotted line may be present or absent;
or the like, or, alternatively,
wherein: x 'and Y' are independent carbon atoms or nitrogen atoms, R3And R4Each independently selected from the following groups: hydrogen, halogen, methoxy, straight or branched C1~C20An aromatic group, the aromatic ring represented by the dotted line may be present or absent;
or the like, or, alternatively,
wherein: r5Selected from the following groups: straight or branched C1~C20An aromatic group;
the transition metal catalyst is Mn (CO)2Br or Mn2(CO)10;
The ligand is (E) -1- (2-pyridyl) -N- (2-picolyl) azomethine [ (E) -1- (pyridine-2-yl) -N- (pyridine-2-ylmethyi) methanimine ], (E) -1- (2-pyridyl) -N- (2-picolyl) ethylenimine [ (E) -1- (pyridine-2-yl) -N- (pyridine-2-ylmethyi) ethane-1-imine ], (E) -2- ((2- (2-pyridyl) hydrazono) methyl) pyridine [ (E) -2- ((2- (pyridine-2-yl) hydrazono) methyl) pyridine ] or [ (E) -2- (2- (1- (2-pyridyl) ethylidene) hydrazono) pyridine ] [ (E) -1- (2-pyridyl) ethylidene) pyridine ] (E) ) -2- (2- (1- (pyridine-2-yl) ethylidene) hydrazinyl) pyridine ];
the alkali is inorganic alkali or organic alkali;
the organic solvent is one or two of benzene, nitromethane, toluene, benzotrifluoride, xylene, mesitylene, 1, 4-dioxane, acetonitrile, propionitrile, dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, diethyl ether, ethylene glycol dimethyl ether, methyl tert-butyl ether, methyl cyclopentyl ether, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, methanol, ethanol and tert-amyl alcohol.
2. The method according to claim 1, wherein the linear or branched C is1~C20The group is methyl, ethyl, propyl, isopropyl or butyl.
3. The method according to claim 1, wherein the aromatic group is a phenyl group, a substituted phenyl group, a pyridyl group, a furyl group, a thienyl group, a 1-naphthyl group, a 2-naphthyl group or a substituted naphthyl group.
4. The method according to claim 1, wherein the base is potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium hydride, sodium hydride, lithium hydride, potassium carbonate, or sodium carbonate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810144381.9A CN108250153B (en) | 2018-02-12 | 2018-02-12 | Preparation method of trans-disubstituted olefin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810144381.9A CN108250153B (en) | 2018-02-12 | 2018-02-12 | Preparation method of trans-disubstituted olefin |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108250153A CN108250153A (en) | 2018-07-06 |
CN108250153B true CN108250153B (en) | 2021-03-30 |
Family
ID=62745414
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810144381.9A Expired - Fee Related CN108250153B (en) | 2018-02-12 | 2018-02-12 | Preparation method of trans-disubstituted olefin |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108250153B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111253305B (en) * | 2018-11-30 | 2022-09-02 | 中国科学院大连化学物理研究所 | Alkenyl or alkylation reaction method of alkyl substituted azaarene |
CN109678854B (en) * | 2019-01-22 | 2021-04-09 | 陕西师范大学 | Method for synthesizing pyrido [1,2-a ] indole-6 (1H) -ketone compound by manganese catalysis |
CN110804015B (en) * | 2019-11-12 | 2021-08-20 | 河北科技大学 | Preparation method of trans-disubstituted olefin |
CN112300085A (en) * | 2020-11-17 | 2021-02-02 | 温州大学 | Alkenyl method of methyl heterocyclic compound |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102060639A (en) * | 2010-12-15 | 2011-05-18 | 中国科学院兰州化学物理研究所 | Method for preparing nitrogen-containing heterocyclic olefin derivatives |
-
2018
- 2018-02-12 CN CN201810144381.9A patent/CN108250153B/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102060639A (en) * | 2010-12-15 | 2011-05-18 | 中国科学院兰州化学物理研究所 | Method for preparing nitrogen-containing heterocyclic olefin derivatives |
Non-Patent Citations (3)
Title |
---|
Cobalt-Catalyzed Alkylation of Secondary Alcohols with Primary Alcohols via Borrowing Hydrogen/Hydrogen Autotransfer;Frederik Freitag,et al.;《Chem. Eur.J.》;20171231;第23卷;第12110-12113页 * |
过渡金属催化C—H氧化反应研究;谢叶香等;《有机化学》;20121231;第32卷;第1555-1567页 * |
过渡金属催化芳香烃C—H活化/C—O键偶联反应的研究进展;丁怀伟等;《有机化学》;20171231;第37卷;第3112-3129页 * |
Also Published As
Publication number | Publication date |
---|---|
CN108250153A (en) | 2018-07-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108250153B (en) | Preparation method of trans-disubstituted olefin | |
Meng et al. | Copper-catalyzed remote (δ) C (sp 3)–H bond amination: a practical strategy to construct pyrrolidine derivatives | |
CN108299296B (en) | Preparation method of phenanthridine heterocyclic compound | |
CN102775344B (en) | Method for preparing 2,3,6-trichloro-trichloromethylpyridine from DCTC (dichlorobenzotrichloride) flash bottoms | |
CN111253305B (en) | Alkenyl or alkylation reaction method of alkyl substituted azaarene | |
Samzadeh‐Kermani | Copper catalyzed synthesis of thiomorpholine derivatives: a new entry of multicomponent reaction between terminal Alkynes, isothiocyanates, and aziridines | |
CN107417478B (en) | Method for synthesizing asymmetric disubstituted urea by catalytic oxidation carbonylation | |
CN111285881B (en) | Thieno [3,4-b ] indole derivative and synthetic method thereof | |
Saito et al. | A Macrocyclic Phenanthroline–Copper Complex with Less Steric Hindrance: Synthesis, Structure, and Application to the Synthesis of a [2] Rotaxane | |
CN109020855B (en) | Ultrasonic-assisted method for synthesizing Z-2-halogenated-1-thiocyanatoethylene compound | |
CN110923744A (en) | Method for constructing secondary amine compound through reductive amination reaction of electrochemical aldehyde | |
CN112778347B (en) | Synthetic method of boron nitrogen benzocarbazole derivative | |
CN108314642A (en) | A kind of synthetic method of 2- picolines class compound | |
CN111454226B (en) | Method for synthesizing 2,4, 6-trisubstituted 1,3,5-triazine compound by aromatic aldehyde and ammonium iodide | |
CN110590690B (en) | Sp catalyzed by copper 2 Alkenyl reaction method for hybridized carbon-hydrogen bond | |
KR102231872B1 (en) | Method for site-selective alkylation of Diazine-N-oxide using phosphonium ylides | |
CN112694489B (en) | Preparation method of N-heterocyclic carbene copper catalyst | |
CN109265403B (en) | Synthesis method of benzimidazole and derivatives thereof | |
Wang et al. | Oxime‐derived palladacycle Immobilized in an Ionic Liquid Brush as an Efficient and Reusable Catalyst for Mozoroki‐Heck Reaction in Neat Water | |
CN109651344B (en) | Benzofuran triarylmethane compounds and green catalytic synthesis method thereof | |
CN108690018B (en) | Preparation method of imidazo [1,2-a ] pyridine derivative | |
CN113072517A (en) | Synthetic method of five-membered oxygen heterocyclic compound | |
Shebitha et al. | Synthesis, Characterization and DFT-D Studies of 2-Aminoethoxycalix [4] resorcinarenes: A Novel Heterogeneous Organocatalyst | |
CN110746342B (en) | Preparation method of hydroxy lactam | |
CN110903223A (en) | Preparation method of nitrogen-substituted sulfonamide compound |
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 | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210330 |