CN110396109A - A kind of double pyrroles condense the synthetic method of boron naphthazine and its derivative - Google Patents
A kind of double pyrroles condense the synthetic method of boron naphthazine and its derivative Download PDFInfo
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- CN110396109A CN110396109A CN201910830117.5A CN201910830117A CN110396109A CN 110396109 A CN110396109 A CN 110396109A CN 201910830117 A CN201910830117 A CN 201910830117A CN 110396109 A CN110396109 A CN 110396109A
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- compound
- dried
- boron
- pyrroles
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- 150000003233 pyrroles Chemical class 0.000 title claims abstract description 21
- 238000010189 synthetic method Methods 0.000 title claims abstract description 11
- 229910052796 boron Inorganic materials 0.000 title abstract description 39
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title abstract description 34
- RFQDDXWZZVRLKO-UHFFFAOYSA-N benzo[g]quinoline Chemical compound N1=CC=CC2=CC3=CC=CC=C3C=C21 RFQDDXWZZVRLKO-UHFFFAOYSA-N 0.000 title abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims abstract description 6
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006467 substitution reaction Methods 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 150000001336 alkenes Chemical class 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 150000002790 naphthalenes Chemical class 0.000 claims abstract description 4
- 125000002252 acyl group Chemical group 0.000 claims abstract description 3
- 150000001454 anthracenes Chemical class 0.000 claims abstract description 3
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical group [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims abstract description 3
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000002220 fluorenes Chemical class 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 150000002240 furans Chemical class 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 150000002469 indenes Chemical class 0.000 claims abstract description 3
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 claims abstract description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract 2
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 claims abstract 2
- -1 boron azepine anthracene compound Chemical class 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000003786 synthesis reaction Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 17
- 229910000085 borane Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 14
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 239000012044 organic layer Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 229940125904 compound 1 Drugs 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229940125782 compound 2 Drugs 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- 229940125898 compound 5 Drugs 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 150000004816 dichlorobenzenes Chemical class 0.000 claims description 3
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 3
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 3
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 3
- 238000003809 water extraction Methods 0.000 claims description 3
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 2
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 claims description 2
- 241001597008 Nomeidae Species 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 238000009423 ventilation Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 230000005622 photoelectricity Effects 0.000 abstract description 5
- 230000000704 physical effect Effects 0.000 abstract description 5
- 239000011368 organic material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 7
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000011097 chromatography purification Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000005865 alkene metathesis reaction Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CYMHIEKFNUNIBB-UHFFFAOYSA-N N1C=CC=CC=C1.[B] Chemical compound N1C=CC=CC=C1.[B] CYMHIEKFNUNIBB-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- NNTOJPXOCKCMKR-UHFFFAOYSA-N boron;pyridine Chemical class [B].C1=CC=NC=C1 NNTOJPXOCKCMKR-UHFFFAOYSA-N 0.000 description 2
- RKFFUJHJOUYEKT-UHFFFAOYSA-N boron;quinoline Chemical compound [B].N1=CC=CC2=CC=CC=C21 RKFFUJHJOUYEKT-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- XFNJYAKDBJUJAJ-UHFFFAOYSA-N 1,2-dibromopropane Chemical compound CC(Br)CBr XFNJYAKDBJUJAJ-UHFFFAOYSA-N 0.000 description 1
- NHUBNHMFXQNNMV-UHFFFAOYSA-N 2-ethynylpyridine Chemical compound C#CC1=CC=CC=N1 NHUBNHMFXQNNMV-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KYOIPUDHYRWSFO-UHFFFAOYSA-N [Br].[Li] Chemical compound [Br].[Li] KYOIPUDHYRWSFO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 description 1
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UOALEFQKAOQICC-UHFFFAOYSA-N chloroborane Chemical compound ClB UOALEFQKAOQICC-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- IQZPDFORWZTSKT-UHFFFAOYSA-N nitrosulphonic acid Chemical compound OS(=O)(=O)[N+]([O-])=O IQZPDFORWZTSKT-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910000080 stannane Inorganic materials 0.000 description 1
- 238000005797 stannylation reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- PBIMIGNDTBRRPI-UHFFFAOYSA-N trifluoro borate Chemical group FOB(OF)OF PBIMIGNDTBRRPI-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The present invention relates to the synthetic methods that a kind of double pyrroles condense boron naphthazine and its derivative, and testing research is carried out to the photoelectricity physical property of these compounds, inquire into potential using value of such organic material in terms of preparing OLED device, the structural formula of this compound are as follows:Wherein R1, R2, R4, R5Be independent substituted or non-substituted group, including alkyl respectively, aryl (phenyl ring, thiphene ring, furan nucleus, pyrroles, pyridine, benzothiophene, benzofuran, benzopyrrole, benzo pyridine, naphthalene nucleus, anthracene nucleus, that non-alkene, aphthacene, pyrene,Linear or angled pentacene and six, indenes, fluorenes etc.).Wherein R3It can be alkyl, acyl group, nitro, sulfonic group, aldehyde radical, diazonium groups or single substitution halogen atom X:F, Cl, Br, I.
Description
Technical field
The present invention relates to the synthetic method that a kind of double pyrroles condense boron naphthazine and its derivative, 1 can purchase with business,
Fluoro- 2, the 4- dinitrobenzene of 5- bis- is raw material, is oriented to by the nucleophilic substitution of pyrroles, reduction reaction and lewis base electrophilic
Boron cyclization obtains a series of double pyrroles and condenses boron azepine anthracene compound.Operation is simple for this synthetic method, reaction condition
Mildly, reaction rate is fast, and yield is high, and such compound has potential using value in organic photoelectrical material field.
Background technique
Polycyclic aromatic hydrocarbon is rich in carbon atom, has biggish conjugated system and Electronic Performance outstanding, in novel organic photoelectric material
Material aspect receives more and more attention, in Organic Light Emitting Diode, organic semiconducting materials, solar battery (OPVs) and field
It has a wide range of applications in effect transistor (OFETs).(Wang C.-L.；Dong H；Hu W.-P.；Liu, Y.-Q.；Zhu,
D.-B.Chem.Rev.2012,112,2208-2267.) introducing hetero-atoms such as B, N, P, O, S, Si etc. in polycyclic aromatic hydrocarbon skeleton,
Valence electron structure can be effectively finely tuned, the photoelectricity physical property of polycyclic aromatic hydrocarbon is improved, obtains the pi-conjugated organic of required performance
Graphene, the graphene nanobelt etc. of boron material such as Heteroatom doping.
Boron atom is the atom of an electron deficient, has an empty p track, this makes it possible to miscellaneous with other electron riches
Atom combines, and generates the movement of charge in the molecule, and nitrogen-atoms has lone pair electrons, can form B-N unit in conjunction with boron atom；
And boron outermost layer, there are three valence electron, nitrogen outermost layer is there are five valence electron, and there are four valence electrons for carbon outermost layer, so B-N and C
=C key isoelectronic species and equal structural bodies each other.The boron N doping polycyclic aromatic hydrocarbon and its full carbon being bonded to B-N unit substitution C=C
Although molecule structure is similar, there is different photoelectricity physical properties.Therefore, this is that building novel conjugated molecule has efficacious prescriptions
Method.
Nineteen twenty-six, Stock have found and report borazine；Then, Dewar group is distinguished in nineteen sixties
Report the phenanthrene (9,10 phenanthrene replaced) and 1 of boron N doping, 2-BN naphthalene nucleus and 9, the naphthalenes aromatic compound of 10-BN doping；
Dewar and White et al. have synthesized 1,2- boron pyridine using precious metal catalyst dehydrogenation reaction, but such synthetic method is anti-
Answer condition harsher.((a) Dewar, M.J.S.；Dietz, R.J.Org.Chem.1961,26,9,3253-3256. (b)
Dewar, M.J.S., Gleicher G J, Robinson B P.J.Am.Chem.Soc.1964,82 (24): 5698-5699.
(c) Dewar, M.J.S., R Dietz, R.J.Am.Chem.Soc.1959,2728-2730. (d) White D.G.；
J.Am.Chem.Soc.2002,85 (22): 3634-3636.) Ashe et al. reported two kinds of synthesis boron pyridines in 2000
Method, one is alkene cultural care is used, another kind synthesizes boron azepine by DDQ Pd/C oxidative dehydrogenation
Benzene, both methods reaction condition are more mild.Researchers are more and more deep to the research of boron azines aromatic hydrocarbons as a result,.
(Ashe, A.J.；Org.Lett.2000,2 (14): 2089-2091.)
2009, Liu project was combined into the parent of 1,2- boron pyridine；They also study and report a series of B- and C
(3) stability of-substitution 1,2- azepine borine to oxygen and water, it was demonstrated that 1,2- azepine borine moisture-stable, if B- and C on ring
(3) substituent group on-position is electron-withdrawing group, then 1,2- azepine borine can be enhanced to the stability of air.(Lamm, A.N.；
Liu, S.-Y.Mol.Biosyst.2009,5,1303-1305.) 2011 years, Liu seminar synthesis characterization 1,3- azepine boron
Alkane, first N- methacrylic amine, formaldehyde and 1,2,3- benzotriazole react to obtain intermediate, and then 1,2,3- benzotriazole are made
It is taken off for leaving group, then carries out parental materials, olefin metathesis reaction and oxidation reaction and obtain target compound, research shows that
1,3- azepine borine be it is heat-staple, have strong armaticity.(Xu, S.；Zakharov, L.N.；Liu, S.-
Y.J.Am.Chem.Soc.2011,133,20152-20155.) 2012, Braunschweig and its colleague reported monocycle 1,
The synthesis and separation of 4- azepine borine, the imino group borine (di-t-butyl imino group borine) and alkynes that they are mediated using rhodium
Cyclization, this method is simple and easy, but the synthesis range reported is only limitted to an example, i.e. N-tBu-B-tBu-1,4- nitrogen
Miscellaneous borine.(M；Beattie N.A.；Geetharani K；J.；Ewing, W.C.；Krahfu β, M.；C.；Dewhurst, R.D.；Macgregor, S.A.；Lambert, C.；Braunschweig, H.；
J.Am.Chem.Soc..2016,138 (26): 8212-8220.) 2016 years, Liu seminar reports three steps synthesis Isosorbide-5-Nitrae-boron nitrogen
The method of miscellaneous benzene, methylamine and 2,3- propylene bromide first carry out coupling reaction, then carry out metal halogen exchange, finally use
iPr2NBCl2Quenching, obtains BN heterocycle, finally carries out exocyclic double bond isomerization and obtains target product.They are also prepared for Isosorbide-5-Nitrae-nitrogen
Miscellaneous boryl terphenyl and biphenol compound, and compared with its carbonaceous analog, it was demonstrated that donor and receptor substituting group position
Specific orientation on gained Isosorbide-5-Nitrae-azepine borine optical property have significantly affect.(Liu, X.-Y.；Zhang, Y.-Z.；Li,
B.；Zakharov, L.N.；Vasiliu, M.；Dixon, D.A.；Liu, S.-Y.Angew.Chem.Int.Ed.2016,55,
8333-8337.) after Clark report synthesis diphenyl in 1992 condenses Isosorbide-5-Nitrae-boron azines compound, 2018,
Suga etc., which is reported, has synthesized two thiophenes with Buchward-Hartwig coupling reaction and the reaction of Friedel-Crafts-C-H boronation
Pheno condenses Isosorbide-5-Nitrae-boron azines compound, and they also developed one kind and are intersected occasionally by stannylation and Stille
Connection reaction carries out Dithiophene and condenses the method that Isosorbide-5-Nitrae-boron azines compound π extends.((a) Kranz, M.；Hampel, F.；
Clark, T.J.Chem.Soc., Chem.Commun.1992,1247. (b) Mitsudo, K.；Shigemori, K.；Mandai,
H.；Wakamiya, A.；Suga, S.Org.Lett.2018,22,7336-7340.)
Above-mentioned is mostly research of the researchers to the phenyl ring (monocycle) of boron N doping；In recent years, people were more to boron N doping
The report of cycle compound is also more and more.After Dewar, Paetzold et al. is in nineteen sixty-eight aniline, two chloroborane of aryl
Reagent and phenylacetylene are reacted to obtain 2,1- boron azanaphthalene；2004, Paetzold reported 2,1- that synthesis N- replaces again
Then the method for boron azanaphthalene, i.e. N- substituted aniline elder generation and boron trichloride reaction are added phenylacetylene and are heated to reflux, be eventually adding chlorine
Change 2, the 1- boron azanaphthalene that zinc heating synthesis N- replaces.(Paetzold, P.I.；Stohr, G.；Maisch, H.；Lenz,
H.Chem.Ber.1968,101,2881. (b) Paetzold, P.；Stanescu, C.；Stubenrauch, J.R.；
Bienmuller, M.；Englert, U.Z.Anorg.Allg.Chem.2004,630,2632.) 2013, Liu seminar was in rhodium
Under catalysis, 1, the 2- dihydro-of boron substitution has been synthesized with 1,2- dihydro -1,2- (chlorine) azepine borine and the reaction of trimethyl aryl stannane
1,2- azepine borine.(Rudebusch, G.E.；Zakharov, L.N.；Liu, S.-Y.Angew.Chem.Int.Ed.2013,
52,9316.) 2014, Molander seminar with adjacent aminostyryl and trifluoroborate carry out reaction synthesized it is a series of
2,1- boron azepine naphthalene compounds.(Molander, G.A.；Amani, J.；Wisniewski, S.R.Org.Lett.2014,16,
6024-6027.) then, Liu seminar carries out olefin metathesis reaction and Pd/C oxygen by raw material of boron pyridine chlorinated derivative
Change reaction synthesis 1,9- boron azanaphthalene.(Brown, A.N.；Li, B.；Liu, S.-Y.J.Am.Chem.Soc.2015,137,
8932-8935.)
2015, Cui Chunming etc. was reported using benzyl imines as Material synthesis 1, the method for 2- boron azanaphthalene and to its light object
Rationality matter is studied, and the boronation of neighbouring aromatic C-H bond of the benzyl imines by alkali promotion first reacts to obtain alkene acyl dibromo
Borine, then borane reagent carries out the corresponding boron bromide product of electrophilic substitution reaction to benzyl aromatic hydrocarbons, is finally carried out with lithium reagent
Bromine lithium exchanges to obtain a series of products.(Liu, X.-W.；Wu, P.-B.；Li, J.-F.；Cui, C.-M.J.Org.Chem.2015,
80,3737-3744.) 2017, Liu seminar, which reports, restored the synthesis of four steps comprising olefin metathesis reaction and Lithium Aluminium Hydride
The method of 9,1- boron azanaphthalenes.Four kinds of boron azanaphthalene isomers are compared by they, predict each pair of orientation BN isomers, heating power
It is also more stable to learn the higher compound HOMO energy of stability.(Liu, Z.；Ishibashi, J.S.A.；Darrigan, C.；
Dargelos, A.；Chrostowska, A.；Li, B.；Vasiliu, M.；Dixon, D.A.；Li u, S.-
Y.J.Am.Chem.Soc.2017,139,6082-6085.)
In recent years, researchers also report the synthetic method of many boron aza-phenanthrenes and anthracene.Boron aza-phenanthrenes is reported after Dewar
Afterwards, Piers seminar reported another isomers of boron aza-phenanthrenes, the chloro- 2- trimethyl silyl of 1- first in 2007
Boron azacyclohexane -2,5- diene reacts to obtain intermediate boron-benzene-pyridine adduct with 2- ethynyl pyridine, then through cycloisomerisation
Reaction obtains final product.(Michael J.D.Bosdet, M.J.D；Jaska, C.A.；Piers, W.E.；Sorensen,
T.S.；Parvez, M.Org.Lett.2007,9 (7): 1395-1398.) 2013 years, Wang Suning seminar by it is photic eliminate it is anti-
Novel boron azepine phenanthrene compound should be synthesized, this photic elimination reaction is suitable for solid substrate and polymer.(Lu, J.-
S.；Ko, S.-B.；Walters, N.R.；Kang, Y.J.；Sauriol, F.；Wang, S.-
N.Angew.Chem.Int.Ed.2013,52,4544-4548.) 2019, Liu Xu light etc. reported two serial boron azepines
Phenanthrene, research shows that they have very strong fluorescence in the solution, Absorption and emission spectra is heavily dependent on the position of BN
The direction and；In addition, two serial BN- phenanthrene are entirely different to the reactivity of electrophilic reagent, these substances can pass through intersection
Coupling reaction is further functionalized.(Zhang, C.；Zhang, L.；Sun, C.；Sun, W.-F.；Liu, X.-
G.Org.Lett.2019,21,10,3476-3480.)
Anthracene compound is a kind of polycyclic aromatic hydrocarbon with very high researching value.Double phenyl condense anthracene compound and double thiophenes
Pheno condenses anthracene compound and has been reported, but its property and potential using value are not reported also.((a) Bonifacio, M.C.；
Robertson, C.R.；Jung, J.-Y.；King, B.T.J.Org.Chem.2005,70,8522. (b) Kar, G.K.；
Haldar, M.K.；Gupta, S.；Pan, D.；Ray, J.K.J.Indian.Chem.Soc.1999,76,569.) Dewar in
Nineteen sixty reports the anthracene class polycyclic aromatic hydrocarbon compounds of double boron N dopings.(Chissick, S.S.；Dewar, M.J.S.；
Maitlis, P.M.Tetrahedron.Lett.1960,1,8-10.) 2014 years, Liu seminar report single boron naphthazine and
The synthesis of double boron naphthazines, and its electronic structure and reactivity worth are studied, introducing boron nitrogen key as the result is shown can make
Compound is more stable.(Ishibashi, J.S.A.；Marshall, J.L.；Maziere, A.；Lovinger, G.J.；Li, B.；
Zakharov, L.N.；Dargelos, A.；Graciaa, A.；Chrostowska, A.；Liu, S.-
Y.J.Am.Chem.Soc.2014,136,15414-15421.) Xinliang Feng project has been combined into double phenyl and has condensed boron nitrogen
It adulterates anthracene compound and double thiophene condenses boron N doping anthracene compound, and its photophysical property is studied, find
They have unique molecules align and electronic property in the solid state, and can be used for manufacturing has the blue organic light emission for improving performance
Diode.(Zhang, W.-Z.；Zhang, F.；Tang, R.-Z.；Fu, Y.-B.；Wang, X.-Y.；Zhuang, X.-D.；He,
G.-F.；Feng, X.-L.Org.Lett.2016,18,3618-3621.)
2014, Pei Jian seminar reported the boron N doping polycyclic arene compound containing super benzene, found this kind of
The electronic device of compound production has very high hole mobility.(Wang, X.-Y.；Zhuang, F.-D.；Wang, R.-B.；
Wang, X.-C.；Cao, X.-Y.；Wang, J.-Y.；Pei, J.J.Am.Chem.Soc.2014,13610,3764-3767.)
2018, Liu Xu light etc. synthesized a series of double boron N doping ullazine compounds, and research finds double boron N dopings
Blue shift has occurred relative to full carbon ullazine in the Absorption and emission spectra of ullazines.In addition, double boron N dopings
Ullazines shows double boron N dopings to air and moisture stabilization, this high stability and special photophysical property
Ullazines above has potential value in organic electronic material application.(Li, C.-L.；Liu, Y.-M.；Sun, Z.；Zhang, J.-
Y.；Liu, M.-Y.；Zhang, C.；Zhang, Q.Wang, H.-J.；Liu, X.-G.Org.Lett.2018,20,2806-
2810.)
In conclusion boron N doping polycyclic aromatic hydrocarbon is since its unique photoelectricity physical property receives more and more attention,
It has very big application value in luminous organic material, electronic device etc., compensate for a certain extent inorganic material it is single lack
Point.But the novel boron N doping polycyclic aromatic hydrocarbon of composite structure and its practical application are still a huge challenge.
Summary of the invention
Present invention aims at provide the novel double pyrroles of one kind design synthetic method for condensing boron naphthazine and its derivative
With its photoelectricity physical property, more schemes are provided to obtain more efficient organic photoelectrical material.
In order to achieve the above object, the technical solution adopted by the present invention is that:
A kind of condensed boron naphthazine of double pyrroles, the structural formula of such compound are as follows:
Wherein R1, R2, R4, R5It is independent substituted or non-substituted group, including alkyl, aryl (phenyl ring, thiophene respectively
Ring, furan nucleus, pyrroles, pyridine, benzothiophene, benzofuran, benzopyrrole, benzo pyridine, naphthalene nucleus, anthracene nucleus, that non-alkene and four
Benzene, pyrene,Linear or angled pentacene and six, indenes, fluorenes etc.).Wherein R3It can be alkyl, acyl group, nitro, sulfonic acid
Base, aldehyde radical, diazonium groups or single substitution halogen atom X:F, Cl, Br, I.
The synthetic route that double pyrroles condense boron azepine anthracene compound 1 is as follows:
Particular content is as follows:
1) 6.00g 1, fluoro- 2, the 4- dinitrobenzene (compound 3) of 5- bis-, 2.59g hydroxide are added in 250mL round-bottomed flask
Sodium, then under nitrogen protection be added 50mL dimethyl sulfoxide stirring and dissolving, be added 4487 μ l pyrroles, stirring at normal temperature 12 hours,
After fully reacting, with EA: H2O=1: 1 extraction, organic phase is dry with anhydrous magnesium sulfate, is spin-dried for, column Chromatographic purification obtains yellow
Solid 1, bis- pyrroles -2,4- dinitrobenzene (compound 4) of 5-.
2) 586mg 1 is added in 100mL round-bottomed flask, 20mL is added in bis- pyrroles -2,4- dinitrobenzene (compound 4) of 5-
Bismuth chloride 1.86g, sodium borohydride 2.23g, stirring at normal temperature 12h, after fully reacting, EA: H is added in ethyl alcohol at 0 DEG C2O=1: 1
Extraction, organic phase is dry with anhydrous magnesium sulfate, is spin-dried for, column Chromatographic purification, obtains yellow oily liquid 1, bis- pyrroles -2,4- bis- of 5-
Aminobenzene (compound 1).
3) 1,5-, bis- pyrroles -2,4- diaminobenzene (compound 5) is added in 75mL tube sealing, chlorobenzene is added in glove box
5mL, 701 μ l of triethylamine, 327 μ l of dichloro-benzenes borine are placed in 130 DEG C of heating stirrings, after fully reacting, with EA: H2O=1: 1 extraction
It takes, organic phase is dry with anhydrous magnesium sulfate, is spin-dried for, column Chromatographic purification, obtains yellow solid (compound 1).
The synthetic route that double pyrroles condense boron azepine anthracene derivant is as follows:
Particular content is as follows:
1) 500mg 1, bis- pyrroles -2,4- diaminobenzene (compound 5) of 5- are added in 100mL Schleck bottles, nitrogen is protected
Shield is lower to be added tetrahydrofuran solution 10mL, and n-BuLi 1.76mL is added at -78 DEG C, after stirring 1h at -78 DEG C, bromine is added
Hexane 1.39g is placed in 66 DEG C and is heated to reflux 4 hours, after fully reacting, with EA: H2O=1: 1 extraction, organic phase anhydrous slufuric acid
Magnesium is dry, is spin-dried for, column Chromatographic purification, obtains brownish red oily liquids (compound 6).
2) 511mg compound 6 is added in 120mL tube sealing, chlorobenzene 8mL, 350 μ l of triethylamine, trichlorine are added in glove box
Change boron 3.80mL, after being placed in 130 DEG C of heating stirrings for 24 hours, addition amidino groups magnesium bromide 13.00mL, stirring at normal temperature reaction 12 hours, instead
After answering completely, with EA: H2O=1: 1 extraction, organic phase is dry with anhydrous magnesium sulfate, is spin-dried for, column Chromatographic purification, and it is solid to obtain yellow
Body (compound 2).
Detailed description of the invention
Fig. 1 is the absorption spectrum of compound 1 and compound 2,
Fig. 2 is the emission spectrum of compound 1 and compound 2,
Fig. 3 is the single crystal diffraction structure chart of compound 2.
Specific embodiment
Following instance helps to understand the present invention, but is not limited to the contents of the present invention.
A kind of double pyrroles of the present invention condense the whole synthetic method of boron naphthazine and its derivative, including following synthetic route
And step:
It illustrates to above-mentioned part of compounds, particular content is as follows:
Embodiment 1: the synthesis of compound 1
1) synthesis of compound 4: fluoro- 2, the 4- dinitrobenzene (1.00equiv, 29.40mmol, 6.00g) of 1,5- bis- is weighed
With sodium hydroxide (2.20equiv, 64.68mmol, 2.59g), substitute gas three times, nitrogen protection, be added 50mL dimethyl sulfoxide
Solution adds pyrroles (2.20equiv, 64.68mmol, 4487 μ l), is placed in stirring at normal temperature 12h.After fully reacting, add water and
Ethyl acetate extraction, merges organic layer, is dried, filtered, be spin-dried for anhydrous magnesium sulfate, quickly carried out column chromatography for separation, obtain Huang
Color solid target compound 4 (5.75g, yield 65%).
1H NMR (400MHz, CDCl3): δ 8.47 (s, 1H, Ar), 7.54 (s, 1H, Ar), 6.83 (t, J=2.4Hz, 4H,
Ar), 6.45 (t, J=2.4Hz, 4H, Ar)
2) synthesis of compound 5: 1,5-, bis- pyrroles -2,4- dinitrobenzene (1.0equiv, 1.97mmol, 586mg) is weighed
It is dissolved in 20mL ethanol solution, bismuth chloride (3.00equiv, 5.91mmol, 1.86g) is added at 0 DEG C, sodium borohydride
(20.0equiv, 39.40mmol, 1.49g) is placed in stirring at normal temperature 12h.After fully reacting, it is spin-dried for etoh solvent, adds water and second
Acetoacetic ester extraction, merges organic layer, is dried, filtered, be spin-dried for anhydrous magnesium sulfate, carries out column chromatography for separation, obtains yellow oily
Liquid target compound 5 (293mg, yield 63%).
1H NMR (400MHz, CDCl3): δ 7.00 (s, 1H, Ar), 6.79 (t, J=2.0HZ, 4H, Ar), 6.32 (t, J=
2.0Hz, 4H, Ar), 6.16 (s, 1H, Ar), 3.68 (br, 4H, NH2).
3) synthesis of compound 1: weigh 1,5-, bis- pyrroles -2,4- diaminobenzene (1.00equiv, 0.84mmol,
200mg), chlorobenzene 5mL, triethylamine (6.00equiv, 5.04mmol, 701 μ l), dichloro-benzenes borine are then added in glove box
(3.00equiv, 2.52mmol, 327 μ l) is placed in 130 DEG C of heating stirrings；After fully reacting, adds water and ethyl acetate to extract, close
And organic layer, it is dried, filtered, is spin-dried for anhydrous magnesium sulfate, quickly carry out column chromatography for separation, obtain faint yellow solid target chemical combination
Object 1 (265mg, yield 77%).
1H NMR (400MHz, CDCl3): δ 7.95 (s, 1H, Ar), 7.90-7.04 (m, 4H, Ar), 7.87-7.88 (m, 2H,
Ar), 7.50-7.54 (m, 6H, Ar), 7.22 (dd, J1=1.6Hz, J2=3.2Hz, 2H, Ar), 6.90 (s, 2H, NH), 6.75-
6.77 (m, 3H, Ar)
Embodiment 2: the synthesis of compound 2
5) synthesis of compound 6: weigh 1,5-, bis- pyrroles -2,4- diaminobenzene (1.00equiv, 2.10mmol,
500mg), it substitutes gas 3 times, nitrogen protection, tetrahydrofuran solution 10mL is added, n-BuLi is added at -78 DEG C
(2.10equiv, 4.41mmol, 1.76mL, 2.5mol/L in hexane), 0.68mL), after stirring 1h at -78 DEG C, it is added
Bromohexane (4.00equiv, 8.40mmol, 1.39g) is subsequently placed in 66 DEG C and is heated to reflux 4 hours, after fully reacting, is spin-dried for molten
Agent is added water and ethyl acetate extraction, merges organic layer, dried, filtered, be spin-dried for anhydrous magnesium sulfate, quickly carries out column chromatography
Separation, obtains brownish red oily liquids target compound 6 (436mg, yield 51%).
1H NMR (400MHz, CDCl3): δ 6.97 (s, 1H, Ar), 6.75 (t, J=2.0Hz, 4H, Ar), 6.31 (t, J=
2.0Hz, 4H, Ar), 5.98 (s, 1H, Ar), 3.72 (br, 2H, NH2), 3.12 (t, J=6.8Hz, 4H, CH2), 1.53-1.56
(m, 4H, CH2), 1.28-1.38 (m, 12H, CH2), 0.91 (t, J=6.4Hz, 6H, CH3).
6) synthesis of compound 2: Weigh Compound 6 (1.00equiv, 1.26mmol, 511mg) is added in glove box
Chlorobenzene 8mL, triethylamine (2.00equiv, 2.52mmol, 350 μ l), boron chloride (3.00equiv, 3.80mmol, 3.80mL,
1.0M in toluene), after being placed in 130 DEG C of heating stirrings for 24 hours, addition amidino groups magnesium bromide (10.00equiv, 12.60mmol,
13.00mL, 1.0M in diethyl ether), stirring at normal temperature is reacted 12 hours, and after fully reacting, water and ethyl acetate is added
Extraction merges organic layer, is dried, filtered, be spin-dried for anhydrous magnesium sulfate, quickly carry out column chromatography for separation, obtain yellow solid mesh
It marks compound 2 (634mg, yield 76%).
1H NMR (400MHz, CDCl3): δ 8.28 (s, 1H, Ar), 7.97 (d, J=1.2Hz, 2H, Ar), 7.43 (s, 1H,
Ar), 6.92 (s, 4H, Ar), 6.67 (t, J=3.2Hz, 2H, Ar), 6.60 (d, J=2.4Hz, 2H, Ar), 3.78 (t, J=
8.0Hz, 4H, CH2), 2.37 (s, 6H, CH3), 2.20 (s, 12H, CH3), 1.70-1.78 (m, 4H, CH2), 1.13-1.27 (m,
12H, CH2), 0.81 (t, J=6.4Hz, 6H, CH3).
In order to further study the photophysical property of such compound, we have carried out UV absorption to such compound
The test of (Fig. 1), fluorescent emission (Fig. 2).
Claims (4)
1. a kind of double pyrroles condense boron azepine anthracene compound, structure are as follows:
Wherein R1, R2, R4, R5It is independent substituted or non-substituted group, including alkyl, aryl, R respectively3It can be alkyl, acyl
Base, nitro, sulfonic group, aldehyde radical, diazonium groups or single substitution halogen atom X:F, Cl, Br, I.
2. double pyrroles according to claim 1 condense boron azepine anthracene compound, it is characterised in that the aryl be phenyl ring,
Thiphene ring, furan nucleus, pyrroles, pyridine, benzothiophene, benzofuran, benzopyrrole, benzo pyridine, naphthalene nucleus, anthracene nucleus, that non-alkene,
Aphthacene, pyrene,Linear or angled pentacene and six, indenes or fluorenes.
3. a kind of a kind of synthetic method of the condensed boron azepine anthracene compound of double pyrroles described in claim 1, it is characterized in that: including
Following synthetic route and step:
1) fluoro- 2, the 4- dinitrobenzene (1.00equiv, 29.40mmol, 6.00g) of 1,5- bis- and hydrogen the synthesis of compound 4: are weighed
Sodium oxide molybdena (2.20equiv, 64.68mmol, 2.59g), substitutes gas three times, nitrogen protection, and 50mL dimethyl sulphoxide solution is added,
Pyrroles (2.20equiv, 64.68mmol, 4487 μ l) is added, stirring at normal temperature 12h is placed in.After fully reacting, add water and acetic acid
Ethyl ester extraction, merges organic layer, is dried, filtered, be spin-dried for anhydrous magnesium sulfate, quickly carry out column chromatography for separation, and it is solid to obtain yellow
Body target compound 4.
2) it the synthesis of compound 5: weighs 1,5-, bis- pyrroles -2,4- dinitrobenzene (1.0equiv, 1.97mmol, 586mg) and is dissolved in
In 20mL ethanol solution, bismuth chloride (3.00equiv, 5.91mmol, 1.86g) is added at 0 DEG C, sodium borohydride
(20.0equiv, 39.40mmol, 1.49g) is placed in stirring at normal temperature 12h.After fully reacting, it is spin-dried for etoh solvent, adds water and second
Acetoacetic ester extraction, merges organic layer, is dried, filtered, be spin-dried for anhydrous magnesium sulfate, carries out column chromatography for separation, obtains yellow oily
Liquid target compound 5.
3) synthesis of compound 1: 1,5-, bis- pyrroles -2,4- diaminobenzene (1.00equiv, 0.84mmol, 200mg) is weighed, so
Chlorobenzene 5mL, triethylamine (6.00equiv, 5.04mmol, 701 μ l), dichloro-benzenes borine is added in glove box afterwards
(3.00equiv, 2.52mmol, 327 μ l) is placed in 130 DEG C of heating stirrings；After fully reacting, adds water and ethyl acetate to extract, close
And organic layer, it is dried, filtered, is spin-dried for anhydrous magnesium sulfate, quickly carry out column chromatography for separation, obtain faint yellow solid target chemical combination
Object 1.
4. a kind of double pyrroles described in claim 1 condense the synthetic method of boron azepine anthracene derivant, it is characterized in that: including following
Synthetic route and step
5) synthesis of compound 6: weighing 1,5-, bis- pyrroles -2,4- diaminobenzene (1.00equiv, 2.10mmol, 500mg), takes out
Ventilation 3 times, nitrogen protection, be added tetrahydrofuran solution 10mL, at -78 DEG C be added n-BuLi (2.10equiv,
4.41mmol, 1.76mL, 2.5mol/L in hexane), 0.68mL), after stirring 1h at -78 DEG C, bromohexane is added
(4.00equiv, 8.40mmol, 1.39g) is subsequently placed in 66 DEG C and is heated to reflux 4 hours, after fully reacting, be spin-dried for solvent, is added
Water and ethyl acetate extraction, merge organic layer, are dried, filtered, be spin-dried for anhydrous magnesium sulfate, quickly carried out column chromatography for separation, obtain
To brownish red oily liquids target compound 6.
6) synthesis of compound 2: chlorobenzene is added in Weigh Compound 6 (1.00equiv, 1.26mmol, 511mg) in glove box
8mL, triethylamine (2.00equiv, 2.52mmol, 350 μ l), boron chloride (3.00equiv, 3.80mmol, 3.80mL, 1.0M
In toluene), after being placed in 130 DEG C of heating stirrings for 24 hours, addition amidino groups magnesium bromide (10.00equiv, 12.60mmol,
13.00mL, 1.0M in diethyl ether), stirring at normal temperature is reacted 12 hours, and after fully reacting, water and ethyl acetate is added
Extraction merges organic layer, is dried, filtered, be spin-dried for anhydrous magnesium sulfate, quickly carry out column chromatography for separation, obtain yellow solid mesh
Mark compound 2.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112778347A (en) * | 2021-01-22 | 2021-05-11 | 九江善水科技股份有限公司 | Synthetic method of boron nitrogen benzocarbazole derivative |
| CN115448816A (en) * | 2022-09-16 | 2022-12-09 | 中国石油大学(华东) | Synthesis method of beta fluoro-alkenyl alcohol |
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| CN109456247A (en) * | 2018-11-08 | 2019-03-12 | 烟台九目化学制品有限公司 | A kind of umbrella shape contains the preparation and application of pyrrole structure class advanced luminescent material |
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| CHENGLONG LI ET AL.: ""Synthesis, Characterization, and Properties of Bis-BN Ullazines"", 《ORG. LETT.》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778347A (en) * | 2021-01-22 | 2021-05-11 | 九江善水科技股份有限公司 | Synthetic method of boron nitrogen benzocarbazole derivative |
| CN112778347B (en) * | 2021-01-22 | 2023-03-14 | 九江善水科技股份有限公司 | Synthetic method of boron nitrogen benzocarbazole derivative |
| CN115448816A (en) * | 2022-09-16 | 2022-12-09 | 中国石油大学(华东) | Synthesis method of beta fluoro-alkenyl alcohol |
| CN115448816B (en) * | 2022-09-16 | 2024-04-12 | 中国石油大学(华东) | Synthesis method of beta-fluoro alkenyl alcohol |
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