CN115141073B - 一种芳香烃二聚体化合物的制备方法 - Google Patents
一种芳香烃二聚体化合物的制备方法 Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000539 dimer Substances 0.000 title claims abstract description 18
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- -1 aromatic olefin Chemical class 0.000 claims abstract description 19
- 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
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000003377 acid catalyst Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 44
- CSFWPUWCSPOLJW-UHFFFAOYSA-N lawsone Chemical compound C1=CC=C2C(=O)C(O)=CC(=O)C2=C1 CSFWPUWCSPOLJW-UHFFFAOYSA-N 0.000 claims description 18
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 11
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 11
- 229940045803 cuprous chloride Drugs 0.000 claims description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 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
- 239000002994 raw material Substances 0.000 claims description 4
- 150000004053 quinones Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims 2
- 229920001296 polysiloxane Polymers 0.000 claims 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- 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
- 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
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
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- 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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 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
- 230000032798 delamination Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 3
- 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
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000007858 starting material Substances 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
- 229930192627 Naphthoquinone Natural products 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- HIYUMYXSGIKHHE-UHFFFAOYSA-M bismuth trifluoromethanesulfonate Chemical compound [Bi+3].[O-]S(=O)(=O)C(F)(F)F HIYUMYXSGIKHHE-UHFFFAOYSA-M 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- 125000000008 (C1-C10) alkyl group Chemical group 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
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process 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
- 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
- 238000006471 dimerization reaction Methods 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
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- 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
- 239000004519 grease 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
- 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
- 238000006464 oxidative addition reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
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- 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
本发明公开了一种芳香烃二聚体化合物的制备方法,将式1所示的化合物、复合催化剂和有机溶剂在加热条件下进行反应得到式2所示的化合物;式1所示的化合物和式2所示的化合物的结构式如下:其中,R为H、C1~10的烷基、卤素等;所述复合催化剂为铜催化剂和三氟甲基磺酸类催化剂的混合。本发明创造性的将式1所示的化合物和复合催化剂加入到有机溶剂中,在加热条件下一步反应得到芳香烯烃二聚体类化合物,该制备方法利用式1所示的化合物作为起始原料,制备简单,操作方便,且使用极少量的复合催化剂,便可得到较高产率的式2所示的化合物。
Description
技术领域
本发明涉及有机合成技术领域,尤其是涉及一种芳香烃二聚体化合物的制备方法。
背景技术
目前,芳基烯烃的催化二聚体反应是构建C-C键的重要方法之一;在石油化工中,它广泛应用于合成长链的烯烃;除此之外这种二芳基骨架结构,在重要的药物和生物活性化合物中也较为常见,例如二甲茚定具有止痒、消炎等的医疗功效,由此可见研究一种芳香烯烃二聚体化合物的合成方法是非常必要的。芳香烯烃二聚体主要分为三种聚合形式,分别为头头相接、头尾相接和尾尾相接。通常,合成这类芳基烯烃二聚体化合物多使用到过渡金属催化,例如钯催化、铟催化、钌催化、钴催化等;尽管这些方法非常高效,但是它们存在一定的局限性:例如所使用的金属催化剂价格昂贵,有些需要使用昂贵的膦配体和添加剂,所用金属不可再生,产生较多浪费等,这不符合绿色化学理念。
因此,有必要开发一种新的芳香烃二聚体化合物的制备方法。
发明内容
本发明旨在至少解决现有技术中存在的技术问题之一。为此,本发明的第一方面提出一种芳香烃二聚体化合物的制备方法。
根据本发明的第一方面实施例的一种芳香烃二聚体化合物的制备方法,将式1所示的化合物、复合催化剂和有机溶剂在加热条件下进行反应得到式2所示的化合物;
式1所示的化合物和式2所示的化合物的结构式如下:
其中,R为H、C1~10的烷基、卤素、取代或未取代的苯基;
所述复合催化剂为铜催化剂和三氟甲基磺酸类催化剂。
根据本发明实施例的芳香烃二聚体化合物的制备方法,至少具有如下有益效果:
本发明创造性的将式1所示的化合物和廉价易得的复合催化剂加入到有机溶剂中,在加热条件下一步反应得到芳香烯烃二聚体类化合物,整个反应过程操作安全、方便,后处理简单,无需使用昂贵的金属催化剂以及膦配体,仅使用少量的复合催化剂,便可得到高产率的式2所示的化合物,有很高的原子经济性。除此之外,该合成路径的机理较为明晰,在反应中铜催化剂和三氟甲基磺酸类催化剂形成一种复合型金属催化剂,一分子式1所示化合物迁移***到复合型催化剂两端,形成化合物B;另一分子的式1所示化合物与化合物B发生氧化加成,形成化合物C;最后还原消除得到式2所示的化合物。
根据本发明的一些实施例,所述铜催化剂包括碘化亚铜、溴化亚铜、氯化亚铜或氯化铜中的至少一种。由此,当铜催化剂选自碘化亚铜、溴化亚铜、氯化亚铜或氯化铜中的至少一种时,具有较好的催化效果。
根据本发明的一些实施例,所述三氟甲基磺酸类催化剂包括三氟甲烷磺酸、三氟甲烷磺酸铋、三氟甲磺酸三甲基硅酯中的至少一种。由此,当三氟甲基磺酸类催化剂选自三氟甲烷磺酸、三氟甲烷磺酸铋、三氟甲磺酸三甲基硅酯中的至少一种时,可以更好的与铜催化剂形成复合催化剂,促进反应的进行。
根据本发明的一些实施例,所述制备方法还包括在制备原料中加入醌类化合物进行反应。由此,醌类化合物的加入能够促进复合催化剂的催化效果,提升反应的产率。
根据本发明的一些实施例,所述醌类化合物包括苯醌类化合物或萘醌类化合物中至少一种。
根据本发明的一些实施例,所述苯醌类化合物包括1,4-苯醌、甲基苯醌、2,3-二氯-5,6-二氰基-1,4-苯醌或四氯苯醌中的至少一种。
根据本发明的一些实施例,所述萘醌类化合物包括2-羟基-1,4-萘醌、1,4-萘醌中、1,2-萘醌或2-溴-1,4-萘醌中的至少一种。由此,反应产率进一步提升。
根据本发明的一些实施例,所述铜催化剂和所述三氟甲基磺酸类催化剂的摩尔比为1:(10~30)。
根据本发明的一些实施例,所述式1所示的化合物、复合催化剂和醌类化合物的摩尔比为1:(0.025~0.05):(0.02~0.05)。
根据本发明的一些实施例,所述加热的温度为50℃~70℃。由此,进一步促进反应的进行。
根据本发明的一些实施例,所述加热的时间为8h~12h。由此,加热的时间在这个范围内使得反应完全。
根据本发明的一些实施例,所述有机溶剂包括二甲基亚砜、四氢呋喃、乙腈或1,4-二氧六环中的至少一种。
根据本发明的一些实施例,所述R选自H、C1~6的烷基、卤素。
定义和一般术语
“C1~10的烷基”表示碳原子总数为1-10的烷基,包括C1-10的直链烷基、C1-10的支链烷基和C3-10的环烷基,例如可以为碳原子总数为1、2、3、4、5、6、7、8、9或10的直链烷基、碳原子总数为1、2、3、4、5、6、7、8、9或10的支链烷基或者碳原子总数为3、4、5、6、7、8、9或10的环烷基,例如可以为甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、环丙基、甲基环丙基、乙基环丙基、环戊基、甲基环戊基、环己基等。针对“C1-6的烷基”具有与此相似的解释,所不同的是,碳原子数不同。
“卤素”表示为氟、氯、溴、碘中的任意一个或两个以上。
“取代或未取代的苯基”表示苯基中至少有一个H原子被本文所定义的基团取代。例如可以被卤素、C1~10的烷基取代。
本发明的其它特征和优点将在随后的说明书中阐述,并且,部分地从说明书中变得显而易见,或者通过实施本发明而了解。
具体实施方式
以下是本发明的具体实施例,并结合实施例对本发明的技术方案作进一步的描述,但本发明并不限于这些实施例。
本发明所采用的试剂、方法和设备,如无特殊说明,均为本技术领域常规试剂、方法和设备。
实施例和对比例用到的原料如下:
化合物1a、化合物1b、化合物1c、化合物1d购自安耐吉化学试剂公司。
实施例1
实施例1提供一种芳香烃二聚体化合物的制备方法,反应式如下,步骤如下:
在干燥的反应管中依次加入氯化亚铜(2.5mg,2.5mo1%)、2-羟基-1,4-萘醌(3.5mg,2mo1%)、苯乙烯(104mg,1.0mmol)和三氟甲磺酸三甲基硅酯(56mg,0.25当量),1.5毫升1,4-二氧六环,60℃电磁搅拌反应12个小时。反应完成后,向反应管中加入适量的乙酸乙酯和水,使其静置分层,取上层有机相于旋蒸瓶中,真空浓缩反应液,通过快速色谱法分离产物,得到(E)-1,3-二苯基-1-丁烯油状透明液体(98mg,94%)。
产物检测数据如下:
1H 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).13C NMR(126MHz,Chloroform-d)δ145.71,137.64,135.31,128.61,127.42,127.16,126.34,126.25,42.67,21.33.
实施例2
实施例2提供一种芳香烃二聚体化合物的制备方法,反应式如下,步骤如下:
在干燥的反应管中依次加入氯化亚铜(2.5mg,2.5mo1%)、2-羟基-1,4-萘醌(3.5mg,2mo1%)、苯乙烯(104mg,1.0mmol)和三氟甲磺酸三甲基硅酯(112mg,0.5当量),1.5毫升1,4-二氧六环,60℃电磁搅拌反应12个小时。反应完成后,向反应管中加入适量的乙酸乙酯和水,使其静置分层,取上层有机相于旋蒸瓶中,真空浓缩反应液,通过快速色谱法分离产物,得到(E)-1,3-二苯基-1-丁烯油状透明液体(102mg,98%)。
产物检测数据如下:
1H 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).13C NMR(126MHz,Chloroform-d)δ145.71,137.64,135.31,128.61,127.42,127.16,126.34,126.25,42.67,21.33.
实施例3
实施例3提供一种芳香烃二聚体化合物的制备方法,反应式如下,步骤如下:
在干燥的反应管中依次加入氯化亚铜(2.5mg,2.5mo1%)、2-羟基-1,4-萘醌(3.5mg,2mo1%)、4-甲基苯乙烯(118mg,1mmol)和三氟甲磺酸三甲基硅酯(56mg,0.25当量),1.5毫升1,4-二氧六环,60℃电磁搅拌反应12个小时。反应完成后,向反应管中适量的乙酸乙酯和水,使其静置分层,取上层有机相于旋蒸瓶中,真空浓缩反应液,通过快速色谱法分离产物,得到(E)-1,3-二(4-甲基苯基)-1-丁烯为油状透明液体(117mg,99%)。
产物检测数据如下:
1H 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).13C 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.
实施例4
实施例4提供一种芳香烃二聚体化合物的制备方法,反应式如下,步骤如下:
在干燥的反应管中依次加入氯化亚铜(2.5mg,2.5mo1%)、2-羟基-1,4-萘醌(3.5mg,2mo1%)、4-叔丁基苯乙烯(161mg,1mmol)和三氟甲磺酸三甲基硅酯(56mg,0.25当量),1.5m1 1,4-二氧六环,60℃电磁搅拌反应12个小时。反应完成后,向反应管中适量的乙酸乙酯和水,使其静置分层,取上层有机相于旋蒸瓶中,真空浓缩反应液,通过快速色谱法分离产物,得到(E)-1,3-二(4-叔丁基苯基)-1-丁烯为油状透明液体(159mg,99%)。
产物检测数据如下:
1H 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).13C 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.
实施例5
实施例5提供一种芳香烃二聚体化合物的制备方法,反应式如下,步骤如下:
在干燥的反应管中依次加入氯化亚铜(2.5mg,2.5mo1%)、2-羟基-1,4-萘醌(3.5mg,2mo1%)、4-氯苯乙烯(138mg,1.0mmol)和三氟甲磺酸三甲基硅酯(56mg,0.25当量),1.5m11,4-二氧六环,60℃电磁搅拌反应12个小时。反应完成后,向反应管中适量的乙酸乙酯和水,使其静置分层,取上层有机相于旋蒸瓶中,真空浓缩反应液,通过快速色谱法分离产物,(E)-1,3-二(4-氯苯基)-1-丁烯为油状透明液体(88mg,64%)。
产物检测数据如下:
1H 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).13C 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.
实施例6
实施例6提供一种芳香烃二聚体化合物的制备方法,反应式如下,步骤如下:
在干燥的反应管中依次加入氯化亚铜(2.5mg,2.5mo1%)、苯乙烯(104mg,1.0mmol)和三氟甲磺酸三甲基硅酯(56mg,0.25当量),1.5毫升1,4-二氧六环,60℃电磁搅拌反应12个小时。反应完成后,向反应管中加入适量的乙酸乙酯和水,使其静置分层,取上层有机相于旋蒸瓶中,真空浓缩反应液,通过快速色谱法分离产物,得到(E)-1,3-二苯基-1-丁烯油状透明液体(77mg,74%)。
产物检测数据如下:
1H 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).13C NMR(126MHz,Chloroform-d)δ145.71,137.64,135.31,128.61,127.42,127.16,126.34,126.25,42.67,21.33.
实施例7~9
实施例7~9与实施例2的原料和制备方法相同,其区别在于,实施例7~9选择了不同铜催化剂,具体见表1。
表1
铜催化剂 | 产率% | |
实施例7 | 碘化亚铜 | 78% |
实施例8 | 溴化亚铜 | 82% |
实施例9 | 氯化铜 | 72% |
实施例10~11
实施例10~11与实施例2的原料和制备方法相同,其区别在于,实施例10~11选择了不同种类的三氟甲基磺酸类化合物,具体见表2。
表2
三氟甲基磺酸类化合物 | 产率% | |
实施例10 | 三氟甲烷磺酸 | 89% |
实施例11 | 三氟甲烷磺酸铋 | 63% |
实施例12~14
实施例12~14与实施例2的原料和制备方法相同,其区别在于,实施例12~14选择了不同种类的醌类化合物,具体见表3。
表3
对比例1
对比例1提供一种芳香烃二聚体化合物的制备方法,反应式如下,步骤如下:
在干燥的反应管中依次加入氯化亚铜(2.5mg,2.5mo1%)、2-羟基-1,4-萘醌(3.5mg,2mo1%)、苯乙烯(104mg,1.0mmol)和1.5毫升1,4-二氧六环,60℃电磁搅拌反应12个小时。经过检测,发现无产物产生,没有发生反应。
对比例2
对比例2提供一种芳香烃二聚体化合物的制备方法,其原料和制备方法与实施例1相同,其区别在于,对比例2采用三氟乙酸替代三氟甲磺酸三甲基硅脂。
在干燥的反应管中依次加入氯化亚铜(2.5mg,2.5mo1%)、2-羟基-1,4-萘醌(3.5mg,2mo1%)、苯乙烯(104mg,1.0mmol)和三氟乙酸(28.5mg,0.25当量),1.5毫升1,4-二氧六环,60℃电磁搅拌反应12个小时。经过检测,发现无产物产生,没有发生反应。
上面结合本发明实施例作了详细说明,但本发明不限于上述实施例,在所属技术领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。
Claims (4)
1.一种芳香烃二聚体化合物的制备方法,其特征在于,将式1所示的化合物、复合催化剂和有机溶剂在加热条件下进行反应得到式2所示的化合物;
式1所示的化合物和式2所示的化合物的结构式如下:
;
其中,R为H、C1~10的烷基;
所述复合催化剂为铜催化剂和三氟甲基磺酸类催化剂的混合;所述加热的温度为50℃~70℃;所述加热的时间为8h~12h;
所述铜催化剂为氯化亚铜;所述三氟甲基磺酸类催化剂为三氟甲磺酸三甲基硅酯;
所述制备方法还包括在制备原料中加入醌类化合物进行反应;
所述醌类化合物选自2-羟基-1,4-萘醌或1,4-萘醌。
2.根据权利要求1所述的芳香烃二聚体化合物的制备方法,其特征在于,所述铜催化剂和所述三氟甲基磺酸类催化剂的摩尔比为1:(10~30)。
3.根据权利要求1所述的芳香烃二聚体化合物的制备方法,其特征在于,所述式1所示的化合物、复合催化剂和醌类化合物的摩尔比为1:(0.025~0.05):(0.02~0.05)。
4.根据权利要求1所述的芳香烃二聚体化合物的制备方法,其特征在于,所述有机溶剂选自二甲基亚砜、四氢呋喃、乙腈或1,4-二氧六环中的至少一种。
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