CN115141073A - Preparation method of aromatic hydrocarbon dimer compound - Google Patents
Preparation method of aromatic hydrocarbon dimer compound Download PDFInfo
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- CN115141073A CN115141073A CN202210859344.2A CN202210859344A CN115141073A CN 115141073 A CN115141073 A CN 115141073A CN 202210859344 A CN202210859344 A CN 202210859344A CN 115141073 A CN115141073 A CN 115141073A
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- aromatic hydrocarbon
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 47
- 239000000539 dimer Substances 0.000 title claims abstract description 24
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- -1 aromatic olefin Chemical class 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 15
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 239000003377 acid catalyst Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 16
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 11
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 11
- 229940045803 cuprous chloride Drugs 0.000 claims description 11
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 10
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229930192627 Naphthoquinone Natural products 0.000 claims description 3
- HIYUMYXSGIKHHE-UHFFFAOYSA-M bismuth trifluoromethanesulfonate Chemical compound [Bi+3].[O-]S(=O)(=O)C(F)(F)F HIYUMYXSGIKHHE-UHFFFAOYSA-M 0.000 claims description 3
- 229960003280 cupric chloride Drugs 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007858 starting material Substances 0.000 abstract description 5
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- CSFWPUWCSPOLJW-UHFFFAOYSA-N lawsone Chemical compound C1=CC=C2C(=O)C(O)=CC(=O)C2=C1 CSFWPUWCSPOLJW-UHFFFAOYSA-N 0.000 description 16
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 238000001514 detection method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003818 flash chromatography Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- GNQWHYWLSGTMSL-OUKQBFOZSA-N [(e)-3-phenylbut-1-enyl]benzene Chemical compound C=1C=CC=CC=1C(C)\C=C\C1=CC=CC=C1 GNQWHYWLSGTMSL-OUKQBFOZSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 1
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 1
- 229940105324 1,2-naphthoquinone Drugs 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- KJOHPBJYGGFYBJ-UHFFFAOYSA-N 2-bromonaphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C(Br)=CC(=O)C2=C1 KJOHPBJYGGFYBJ-UHFFFAOYSA-N 0.000 description 1
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HIHOEGPXVVKJPP-JTQLQIEISA-N 5-fluoro-2-[[(1s)-1-(5-fluoropyridin-2-yl)ethyl]amino]-6-[(5-methyl-1h-pyrazol-3-yl)amino]pyridine-3-carbonitrile Chemical compound N([C@@H](C)C=1N=CC(F)=CC=1)C(C(=CC=1F)C#N)=NC=1NC=1C=C(C)NN=1 HIHOEGPXVVKJPP-JTQLQIEISA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DRIJGEJOLOPSGI-DHZHZOJOSA-N C=1C=C(C)C=CC=1C(C)\C=C\C1=CC=C(C)C=C1 Chemical compound C=1C=C(C)C=CC=1C(C)\C=C\C1=CC=C(C)C=C1 DRIJGEJOLOPSGI-DHZHZOJOSA-N 0.000 description 1
- ZFEYUKOFZMWPGO-NSCUHMNNSA-N C=1C=C(Cl)C=CC=1C(C)\C=C\C1=CC=C(Cl)C=C1 Chemical compound C=1C=C(Cl)C=CC=1C(C)\C=C\C1=CC=C(Cl)C=C1 ZFEYUKOFZMWPGO-NSCUHMNNSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- NYENCOMLZDQKNH-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)bismuthanyl trifluoromethanesulfonate Chemical compound [Bi+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F NYENCOMLZDQKNH-UHFFFAOYSA-K 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000006437 ethyl cyclopropyl group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007803 itching Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 230000007721 medicinal effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
- C07C17/281—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons of only one compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/122—Compounds comprising a halogen and copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/025—Sulfonic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of an aromatic hydrocarbon dimer compound, which comprises the steps of reacting a compound shown in a formula 1, a composite catalyst and an organic solvent under the heating condition to obtain a compound shown in a formula 2; the structural formulas of the compound represented by formula 1 and the compound represented by formula 2 are as follows:
wherein R is H or C 1～10 Alkyl, halogen, etc.; the composite catalyst is a mixture of a copper catalyst and a trifluoromethyl sulfonic acid catalyst. The invention creatively adds the compound shown in the formula 1 and the composite catalyst into an organic solvent, and then the aromatic hydrocarbon is obtained by one-step reaction under the heating conditionThe preparation method of the aromatic olefin dimer compound uses the compound shown in the formula 1 as a starting material, has simple preparation and convenient operation, and can obtain the compound shown in the formula 2 with higher yield by using a very small amount of composite catalyst.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of an aromatic hydrocarbon dimer compound.
Background
At present, the catalytic dimer reaction of aryl olefin is one of important methods for constructing C-C bond; in petrochemical industry, it is widely used for synthesizing long-chain olefins; in addition, the diaryl skeleton structure is common in important drugs and bioactive compounds, for example, dimetindedine has medical effects of relieving itching, diminishing inflammation and the like, so that the research on a synthetic method of an aromatic olefin dimer compound is very necessary. Aromatic olefin dimers are mainly classified into three polymerization forms, i.e., head-to-head, head-to-tail, and tail-to-tail. In general, synthesis of such arylalkene dimer compounds is largely mediated by transition metal catalysis, such as palladium catalysis, indium catalysis, ruthenium catalysis, cobalt catalysis, and the like; although these methods are very efficient, they have certain limitations: for example, the metal catalysts used are expensive, some require the use of expensive phosphine ligands and additives, the metals used are not renewable, more waste is generated, etc., which is not in accordance with the green chemistry concept.
Therefore, it is necessary to develop a novel method for preparing dimer aromatic hydrocarbon compounds.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. To this end, the first aspect of the present invention provides a process for producing an aromatic dimer compound.
According to the preparation method of the aromatic hydrocarbon dimer compound of the first aspect of the invention, the compound shown in formula 1, the composite catalyst and the organic solvent are reacted under heating condition to obtain the compound shown in formula 2;
the structural formulas of the compound represented by formula 1 and the compound represented by formula 2 are as follows:
wherein R is H or C 1～10 Alkyl, halogen, substituted or unsubstituted phenyl;
the composite catalyst is a copper catalyst and a trifluoromethyl sulfonic acid catalyst.
The preparation method of the aromatic hydrocarbon dimer compound according to the embodiment of the invention has at least the following beneficial effects:
the compound shown in the formula 1 and the cheap and easily-obtained composite catalyst are creatively added into an organic solvent, and the aromatic olefin dimer compound is obtained through one-step reaction under a heating condition, so that the whole reaction process is safe and convenient to operate, the post-treatment is simple, the expensive metal catalyst and phosphine ligand are not needed, the compound shown in the formula 2 can be obtained in high yield only by using a small amount of composite catalyst, and the atom economy is high. In addition, the mechanism of the synthesis route is clear, a copper catalyst and a trifluoromethyl sulfonic acid catalyst form a composite metal catalyst in the reaction, and a compound shown in a formula 1 migrates and is inserted into two ends of the composite metal catalyst to form a compound B; carrying out oxidation addition on another molecule of the compound shown in the formula 1 and the compound B to form a compound C; finally, the compound shown in the formula 2 is obtained through reduction elimination.
According to some embodiments of the invention, the copper catalyst comprises at least one of cuprous iodide, cuprous bromide, cuprous chloride, or cupric chloride. Therefore, when the copper catalyst is selected from at least one of cuprous iodide, cuprous bromide, cuprous chloride or cupric chloride, the catalytic effect is better.
According to some embodiments of the invention, the triflic acid based catalyst comprises at least one of triflic acid, bismuth triflate, trimethylsilyl triflate. Therefore, when the trifluoromethanesulfonic acid catalyst is selected from at least one of trifluoromethanesulfonic acid, bismuth trifluoromethanesulfonate and trimethylsilyl trifluoromethanesulfonate, a composite catalyst can be formed with the copper catalyst to promote the reaction.
According to some embodiments of the present invention, the preparation method further comprises adding a quinone compound to the preparation raw material to perform a reaction. Therefore, the addition of the quinone compound can promote the catalytic effect of the composite catalyst and improve the yield of the reaction.
According to some embodiments of the invention, the quinone compound comprises at least one of a benzoquinone compound or a naphthoquinone compound.
According to some embodiments of the invention, the benzoquinone based compound comprises at least one of 1, 4-benzoquinone, methylbenzoquinone, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone or tetrachlorobenzoquinone.
According to some embodiments of the invention, the naphthoquinone compound includes at least one of 2-hydroxy-1, 4-naphthoquinone, 1, 2-naphthoquinone, or 2-bromo-1, 4-naphthoquinone. Thereby, the reaction yield is further improved.
According to some embodiments of the invention, the molar ratio of the copper catalyst to the triflic acid based catalyst is 1: (10 to 30).
According to some embodiments of the present invention, the compound represented by formula 1, the hybrid catalyst and the quinone compound are present in a molar ratio of 1: (0.025 to 0.05): (0.02-0.05).
According to some embodiments of the invention, the heating is at a temperature of 50 ℃ to 70 ℃. This further accelerates the reaction.
According to some embodiments of the invention, the heating time is 8h to 12h. Thus, the heating time is in this range so that the reaction is complete.
According to some embodiments of the invention, the organic solvent comprises at least one of dimethylsulfoxide, tetrahydrofuran, acetonitrile, or 1, 4-dioxane.
According to some embodiments of the invention, R is selected from H, C 1～6 Alkyl, halogen.
Definitions and general terms
“C 1～10 The "alkyl group" represents an alkyl group having a total number of carbon atoms of 1 to 10, including C 1-10 Straight chain alkyl group of (1), C 1-10 Branched alkyl and C 3-10 The cycloalkyl group of (b) may be, for example, one having a total number of carbon atoms of 1,2. A straight-chain alkyl group of 3, 4, 5,6, 7, 8, 9 or 10, a branched-chain alkyl group having a total number of carbon atoms of 1,2, 3, 4, 5,6, 7, 8, 9 or 10, or a cyclic alkyl group having a total number of carbon atoms of 3, 4, 5,6, 7, 8, 9 or 10, and may be, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a cyclopropyl group, a methylcyclopropyl group, an ethylcyclopropyl group, a cyclopentyl group, a methylcyclopentyl group, a cyclohexyl group, or the like. For "C 1-6 The "alkyl group" of (1) has a similar explanation except that the number of carbon atoms is different.
"halogen" represents any one or two or more of fluorine, chlorine, bromine and iodine.
"substituted or unsubstituted phenyl" means that at least one H atom of the phenyl group is substituted by a group as defined herein. For example, may be substituted by halogen, C 1～10 Alkyl substitution of (2).
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described with reference to the examples, but the present invention is not limited to the examples.
The reagents, methods and equipment used in the invention are conventional in the technical field unless otherwise specified.
The raw materials used in the examples and comparative examples were as follows:
compound 1a, compound 1b, compound 1c, compound 1d were purchased from annaiji chemicals.
Example 1
Example 1 provides a method for preparing an aromatic dimer compound, having the following reaction formula:
cuprous chloride (2.5mg, 2.5mo 1%), 2-hydroxy-1, 4-naphthoquinone (3.5mg, 2mo 1%), styrene (104mg, 1.0mmol) and trimethylsilyl trifluoromethanesulfonate (56mg, 0.25 equivalent) were sequentially added to a dry reaction tube, and 1.5 ml of 1, 4-dioxane was reacted at 60 ℃ with electromagnetic stirring for 12 hours. After completion of the reaction, an appropriate amount of ethyl acetate and water were added to the reaction tube, allowed to stand for layering, the upper organic phase was taken in a rotary evaporator, the reaction solution was concentrated in vacuo, and the product was isolated by flash chromatography to give (E) -1, 3-diphenyl-1-butene as an oily transparent liquid (98mg, 94%).
The product detection data were as follows:
1 H NMR(500MHz,Chloroform-d)δ7.45–7.32(m,8H),7.31–7.24(m,2H),6.53–6.42(m,2H),3.75–3.67(m,1H),1.54(d,J＝7.0Hz,3H). 13 C NMR(126MHz,Chloroform-d)δ145.71,137.64,135.31,128.61,127.42,127.16,126.34,126.25,42.67,21.33.
example 2
Example 2 provides a method for preparing an aromatic dimer compound, having the following reaction formula:
cuprous chloride (2.5mg, 2.5mo 1%), 2-hydroxy-1, 4-naphthoquinone (3.5mg, 2mo 1%), styrene (104mg, 1.0 mmol) and trimethylsilyl trifluoromethanesulfonate (112mg, 0.5 eq) were added in this order to a dry reaction tube, and 1.5 ml of 1, 4-dioxane was reacted with electromagnetic stirring at 60 ℃ for 12 hours. After completion of the reaction, an appropriate amount of ethyl acetate and water were added to the reaction tube, and allowed to stand for layering, the upper organic phase was taken out in a rotary evaporation bottle, the reaction solution was concentrated in vacuo, and the product was separated by flash chromatography to give (E) -1, 3-diphenyl-1-butene as an oily transparent liquid (102mg, 98%).
The product detection data were as follows:
1 H NMR(500MHz,Chloroform-d)δ7.45–7.32(m,8H),7.31–7.24(m,2H),6.53–6.42(m,2H),3.75–3.67(m,1H),1.54(d,J＝7.0Hz,3H). 13 C NMR(126MHz,Chloroform-d)δ145.71,137.64,135.31,128.61,127.42,127.16,126.34,126.25,42.67,21.33.
example 3
Example 3 provides a method for preparing an aromatic dimer compound, having the following reaction formula:
cuprous chloride (2.5mg, 2.5mo 1%), 2-hydroxy-1, 4-naphthoquinone (3.5mg, 2mo 1%), 4-methylstyrene (118mg, 1mmol) and trimethylsilyl trifluoromethanesulfonate (56mg, 0.25 eq) were added in this order to a dry reaction tube, and 1.5 ml of 1, 4-dioxane was reacted with electromagnetic stirring at 60 ℃ for 12 hours. After completion of the reaction, an appropriate amount of ethyl acetate and water were allowed to stand in a reaction tube for separation, the upper organic phase was taken out in a rotary evaporation flask, the reaction solution was concentrated in vacuo, and the product was isolated by flash chromatography to give (E) -1, 3-bis (4-methylphenyl) -1-butene as an oily transparent liquid (117mg, 99%).
The product detection data were as follows:
1 H NMR(500MHz,Chloroform-d)δ7.37–7.31(m,2H),7.28–7.16(m,6H),6.50–6.38(m,2H),3.72–3.64(m,1H),2.41(d,J＝6.8Hz,6H),1.53(d,J＝7.1Hz,3H). 13 C NMR(126MHz,Chloroform-d)δ142.89,136.79,135.75,134.93,134.51,129.28,129.26,128.25,127.30,126.14,42.23,21.45,21.26,21.12.
example 4
Example 4 provides a method for preparing an aromatic dimer compound, having the following reaction scheme:
cuprous chloride (2.5mg, 2.5mo 1%), 2-hydroxy-1, 4-naphthoquinone (3.5mg, 2mo 1%), 4-t-butylstyrene (161mg, 1mmol), and trimethylsilyl trifluoromethanesulfonate (56mg, 0.25 equivalent) were sequentially added to a dry reaction tube, and 1.5m1, 4-dioxane was reacted with electromagnetic stirring at 60 ℃ for 12 hours. After completion of the reaction, an appropriate amount of ethyl acetate and water were put into a reaction tube, allowed to stand for separation, and the upper organic phase was taken out in a rotary evaporation flask, and the reaction solution was concentrated in vacuo, and the product was isolated by flash chromatography to give (E) -1, 3-bis (4-tert-butylphenyl) -1-butene as an oily transparent liquid (159mg, 99%).
The product detection data were as follows:
1 H NMR(500MHz,Chloroform-d)δ7.47–7.37(m,6H),7.31(dd,J＝8.3,1.6Hz,2H),6.56–6.41(m,2H),3.76–3.67(m,1H),1.55(dd,J＝7.0,1.5Hz,3H),1.41(dd,J＝5.6,1.6Hz,18H). 13 C NMR(126MHz,Chloroform-d)δ150.08,148.96,142.78,134.93,134.75,128.06,127.00,125.91,125.48,125.44,125.40,42.10,34.59,34.46,31.51,31.45,31.41,21.28.
example 5
Example 5 provides a method for preparing an aromatic dimer compound, having the following reaction scheme:
cuprous chloride (2.5mg, 2.5mo 1%), 2-hydroxy-1, 4-naphthoquinone (3.5mg, 2mo 1%), 4-chlorostyrene (138mg, 1.0mmol) and trimethylsilyl trifluoromethanesulfonate (56mg, 0.25 equivalent) were sequentially added to a dry reaction tube, and the mixture was reacted at 60 ℃ for 12 hours with electromagnetic stirring. After completion of the reaction, an appropriate amount of ethyl acetate and water were put into a reaction tube, allowed to stand for layer separation, the upper organic phase was taken out in a rotary evaporation bottle, the reaction solution was concentrated in vacuo, and the product, (E) -1, 3-bis (4-chlorophenyl) -1-butene was isolated by flash chromatography as an oily transparent liquid (88mg, 64%).
The product detection data were as follows:
1 H NMR(500MHz,Chloroform-d)δ7.34–7.26(m,6H),7.25–7.19(m,2H),6.41–6.31(m,2H),3.68–3.60(m,1H),1.48(d,J＝7.1Hz,3H). 13 C NMR(126MHz,Chloroform-d)δ143.79,135.86,135.34,132.79,132.03,128.71,128.69,128.67,127.77,127.41,41.98,21.10.
example 6
Example 6 provides a method for preparing an aromatic dimer compound, having the following reaction scheme:
cuprous chloride (2.5 mg,2.5mo 1%), styrene (104mg, 1.0 mmol) and trimethylsilyl trifluoromethanesulfonate (56mg, 0.25 eq) were sequentially added to a dry reaction tube, and 1.5 ml of 1, 4-dioxane was reacted with electromagnetic stirring at 60 ℃ for 12 hours. After completion of the reaction, an appropriate amount of ethyl acetate and water were added to the reaction tube, allowed to stand for layering, the upper organic phase was taken out in a rotary evaporation bottle, the reaction solution was concentrated in vacuo, and the product was isolated by flash chromatography to give (E) -1, 3-diphenyl-1-butene as an oily transparent liquid (77mg, 74%).
The product detection data were as follows:
1 H NMR(500MHz,Chloroform-d)δ7.45–7.32(m,8H),7.31–7.24(m,2H),6.53–6.42(m,2H),3.75–3.67(m,1H),1.54(d,J＝7.0Hz,3H). 13 C NMR(126MHz,Chloroform-d)δ145.71,137.64,135.31,128.61,127.42,127.16,126.34,126.25,42.67,21.33.
examples 7 to 9
Examples 7-9 were the same as example 2 in terms of starting materials and preparation, except that examples 7-9 selected different copper catalysts, as detailed in table 1.
TABLE 1
| Copper catalyst | Yield% | |
| Example 7 | Cuprous iodide | 78％ |
| Example 8 | Cuprous bromide | 82％ |
| Example 9 | Copper chloride | 72％ |
Examples 10 to 11
Examples 10 to 11 were identical to example 2 in terms of the starting materials and the production method, except that different types of trifluoromethanesulfonic acid compounds were selected in examples 10 to 11, and are specifically shown in table 2.
TABLE 2
| Trifluoromethanesulfonic acid compound | Yield% | |
| Example 10 | Trifluoromethanesulfonic acid | 89％ |
| Example 11 | Bismuth trifluoromethanesulfonate | 63％ |
Examples 12 to 14
Examples 12 to 14 were the same as example 2 in terms of the starting materials and production method, except that different kinds of quinone compounds were selected in examples 12 to 14, as shown in Table 3.
TABLE 3
Comparative example 1
Comparative example 1 provides a method for preparing an aromatic dimer compound, having the following reaction formula, comprising the steps of:
cuprous chloride (2.5mg, 2.5mo 1%), 2-hydroxy-1, 4-naphthoquinone (3.5mg, 2mo 1%), styrene (104mg, 1.0mmol) and 1.5 ml of 1, 4-dioxane were sequentially added to a dry reaction tube, and the reaction was carried out with electromagnetic stirring at 60 ℃ for 12 hours. No product is generated and no reaction occurs after detection.
Comparative example 2
Comparative example 2 provides a method for preparing an aromatic hydrocarbon dimer compound, the starting materials and the preparation method of which are the same as those of example 1, except that in comparative example 2, trifluoroacetic acid is used instead of trimethylsilyl trifluoromethanesulfonate.
Cuprous chloride (2.5mg, 2.5mo 1%), 2-hydroxy-1, 4-naphthoquinone (3.5mg, 2mo 1%), styrene (104mg, 1.0 mmol) and trifluoroacetic acid (28.5mg, 0.25 equivalent) were sequentially added to a dry reaction tube, and 1.5 ml of 1, 4-dioxane was reacted with electromagnetic stirring at 60 ℃ for 12 hours. No product is generated and no reaction occurs after detection.
The present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. A preparation method of an aromatic hydrocarbon dimer compound is characterized in that a compound shown in a formula 1, a composite catalyst and an organic solvent are reacted under the heating condition to obtain a compound shown in a formula 2;
the structural formulas of the compound represented by formula 1 and the compound represented by formula 2 are as follows:
wherein R is H or C 1～10 Alkyl, halogen, substituted or unsubstituted phenyl;
the composite catalyst is a mixture of a copper catalyst and a trifluoromethyl sulfonic acid catalyst.
2. The method for preparing an aromatic hydrocarbon dimer compound according to claim 1, wherein said copper catalyst comprises at least one of cuprous iodide, cuprous bromide, cuprous chloride or cupric chloride.
3. The method for producing an aromatic hydrocarbon dimer compound according to claim 1, wherein the trifluoromethanesulfonic acid-based catalyst comprises at least one of trifluoromethanesulfonic acid, bismuth trifluoromethanesulfonate, and trimethylsilyl trifluoromethanesulfonate.
4. The method for producing an aromatic hydrocarbon dimer compound according to any one of claims 1 to 3, further comprising adding a quinone compound to the raw materials for the production to carry out the reaction.
5. The method for producing an aromatic hydrocarbon dimer compound according to claim 4, wherein the quinone compound comprises at least one of a benzoquinone compound and a naphthoquinone compound.
6. The method for producing an aromatic hydrocarbon dimer compound according to claim 1, wherein the molar ratio of the copper catalyst to the trifluoromethanesulfonic acid-based catalyst is 1: (10 to 30).
7. The method of preparing an aromatic hydrocarbon dimer compound according to claim 4, wherein the molar ratio of the compound represented by formula 1, the composite catalyst, and the quinone compound is 1: (0.025 to 0.05): (0.02-0.05).
8. The method for producing an aromatic hydrocarbon dimer compound according to any one of claims 1 to 7, wherein the heating temperature is 50 ℃ to 70 ℃.
9. The method for producing an aromatic hydrocarbon dimer compound according to any one of claims 1 to 7, wherein the heating is carried out for a period of time of 8 to 12 hours.
10. The method for preparing an aromatic hydrocarbon dimer compound according to claim 1, wherein the organic solvent comprises at least one of dimethyl sulfoxide, tetrahydrofuran, acetonitrile or 1, 4-dioxane.
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