CN114276252A - Method for preparing 9-amino-10-alkynyl phenanthrene ring derivative - Google Patents
Method for preparing 9-amino-10-alkynyl phenanthrene ring derivative Download PDFInfo
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- CN114276252A CN114276252A CN202111580798.8A CN202111580798A CN114276252A CN 114276252 A CN114276252 A CN 114276252A CN 202111580798 A CN202111580798 A CN 202111580798A CN 114276252 A CN114276252 A CN 114276252A
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- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 138
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 54
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims abstract description 24
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims abstract description 24
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- -1 N-dimethyl Chemical group 0.000 claims description 94
- 239000011521 glass Substances 0.000 claims description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 229910052799 carbon Inorganic materials 0.000 claims description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- 239000001257 hydrogen Substances 0.000 claims description 39
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 38
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 125000003107 substituted aryl group Chemical group 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- WAUVRUBPGUOVEI-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetrahydroxybutane-1,2-diamine Chemical compound CCC(N(O)O)CN(O)O WAUVRUBPGUOVEI-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical group CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- VGGNVBNNVSIGKG-UHFFFAOYSA-N n,n,2-trimethylaziridine-1-carboxamide Chemical compound CC1CN1C(=O)N(C)C VGGNVBNNVSIGKG-UHFFFAOYSA-N 0.000 claims 1
- DCJXBMAAZLWLLK-UHFFFAOYSA-N S(=O)(=O)(C1=CC=C(C)C=C1)NN=CC=1C(=CC=CC=1)C1=C(C=CC=C1)C#N Chemical class S(=O)(=O)(C1=CC=C(C)C=C1)NN=CC=1C(=CC=CC=1)C1=C(C=CC=C1)C#N DCJXBMAAZLWLLK-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002994 raw material Substances 0.000 abstract description 18
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 abstract description 8
- 125000000304 alkynyl group Chemical group 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract 1
- 229910052796 boron Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 102
- 238000001228 spectrum Methods 0.000 description 74
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000000463 material Substances 0.000 description 28
- 239000012299 nitrogen atmosphere Substances 0.000 description 26
- 239000003921 oil Substances 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 25
- 238000001816 cooling Methods 0.000 description 23
- 238000003756 stirring Methods 0.000 description 23
- 238000005303 weighing Methods 0.000 description 23
- 238000007789 sealing Methods 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 17
- 238000004321 preservation Methods 0.000 description 17
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 12
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 6
- 235000003270 potassium fluoride Nutrition 0.000 description 6
- 239000011698 potassium fluoride Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- DAJILHJPFBUYMZ-UHFFFAOYSA-N 2-(2-formylphenyl)benzonitrile Chemical compound O=CC1=CC=CC=C1C1=CC=CC=C1C#N DAJILHJPFBUYMZ-UHFFFAOYSA-N 0.000 description 2
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical group CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 description 2
- QWPHPZPPXNKTJI-UHFFFAOYSA-N C(=O)C1=C(C=CC(=C1)OC)C=1C(=CC=CC=1)C#N Chemical compound C(=O)C1=C(C=CC(=C1)OC)C=1C(=CC=CC=1)C#N QWPHPZPPXNKTJI-UHFFFAOYSA-N 0.000 description 2
- YVAYQSUECRGIFX-UHFFFAOYSA-N ClC1=CC(=C(C=C1)C=1C(=CC=CC=1)C#N)C=O Chemical compound ClC1=CC(=C(C=C1)C=1C(=CC=CC=1)C#N)C=O YVAYQSUECRGIFX-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LZJHACNNMBYMSO-UHFFFAOYSA-N 1,1-dimethyl-3-propylurea Chemical compound CCCNC(=O)N(C)C LZJHACNNMBYMSO-UHFFFAOYSA-N 0.000 description 1
- RVDOYUFNRDGYGU-UHFFFAOYSA-N 1-bromo-2-ethynylbenzene Chemical group BrC1=CC=CC=C1C#C RVDOYUFNRDGYGU-UHFFFAOYSA-N 0.000 description 1
- DGLHLIWXYSGYBI-UHFFFAOYSA-N 1-chloro-2-ethynylbenzene Chemical group ClC1=CC=CC=C1C#C DGLHLIWXYSGYBI-UHFFFAOYSA-N 0.000 description 1
- XTKBMZQCDBHHKY-UHFFFAOYSA-N 1-ethynyl-4-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=C(C#C)C=C1 XTKBMZQCDBHHKY-UHFFFAOYSA-N 0.000 description 1
- CUKSTNNYAHZPRM-UHFFFAOYSA-N 2-bromo-4-(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC=C(C=O)C(Br)=C1 CUKSTNNYAHZPRM-UHFFFAOYSA-N 0.000 description 1
- IIISHLMCTDMUHH-UHFFFAOYSA-N 2-bromo-5-chlorobenzaldehyde Chemical compound ClC1=CC=C(Br)C(C=O)=C1 IIISHLMCTDMUHH-UHFFFAOYSA-N 0.000 description 1
- XNHKTMIWQCNZST-UHFFFAOYSA-N 2-bromo-5-methoxybenzaldehyde Chemical compound COC1=CC=C(Br)C(C=O)=C1 XNHKTMIWQCNZST-UHFFFAOYSA-N 0.000 description 1
- NDOPHXWIAZIXPR-UHFFFAOYSA-N 2-bromobenzaldehyde Chemical compound BrC1=CC=CC=C1C=O NDOPHXWIAZIXPR-UHFFFAOYSA-N 0.000 description 1
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 description 1
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- FWDBZJBJTDRIIY-UHFFFAOYSA-N CC(C)(C)[K] Chemical compound CC(C)(C)[K] FWDBZJBJTDRIIY-UHFFFAOYSA-N 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- IAWCIZWLKMTPLL-UHFFFAOYSA-N fluoroethyne Chemical group FC#C IAWCIZWLKMTPLL-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- FZFLTDNAHASQQC-RVDMUPIBSA-N n-[(e)-benzylideneamino]-4-methylbenzenesulfonamide Chemical compound C1=CC(C)=CC=C1S(=O)(=O)N\N=C\C1=CC=CC=C1 FZFLTDNAHASQQC-RVDMUPIBSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
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Abstract
The invention discloses a novel method for synthesizing a 9-amino-10-alkynyl phenanthrene ring derivative shown in a structural general formula I, and a novel boron and nitrogen doped condensed ring framework prepared based on the method. The method uses substituted 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone or 3-aldehyde-2- (2-cyanophenyl) pyridine p-toluenesulfonylhydrazone as a raw material, tetrahydrofuran as a solvent, cuprous iodide as a catalyst, N' -dimethylethylenediamine as a ligand, and tert-butyllithium as a base to react with alkyne to generate cyclization reaction. Based on the method, the 9-position and the 10-position of the phenanthrene ring framework can be simultaneously introduced with higher reaction activityCompared with the traditional synthetic method, the amino and alkynyl greatly save the experimental steps.
Description
Technical Field
The invention belongs to the technical field of catalytic synthesis of fine chemical products, and particularly relates to a novel method for preparing a 9-amino-10-alkynyl phenanthrene ring derivative.
Background
Phenanthrene rings are used as condensed ring compounds with simpler structures in the fields of material chemistry (Monterde et al. ACS appl. Mater. interfaces 2020,12(13)15108-
et al, organometallics 2005,24, 3219-. However, the construction of phenanthrene rings usually involves Grignard reagents or noble metal catalytic reactions, while the direct functionalization of phenanthrene rings at positions 9 and 10 requires the use of nitration or bromination, and the reaction steps are usually complicated (Selected papers (1) Larock et al J. org. chem.1997,62, 7536-. Therefore, it is an important subject to develop a new organic synthesis method and establish a high-efficiency reaction system with phenanthrene ring 9-site and 10-site functional groups.
Meanwhile, the phenanthrene ring is used as a rigid large-pi conjugated molecular skeleton and has the potential of being applied to the field of organic photoelectricity. Therefore, the phenanthrene ring substrate with the functionalized 9 th site and the functionalized 10 th site prepared based on the technology has potential application prospect in the research of further exploring and constructing luminescent material frameworks.
Disclosure of Invention
The invention aims to provide a novel method for constructing a 9-amino-10-alkynyl phenanthrene ring derivative by a one-step method.
The preparation method of the compound (namely the 9-amino-10-alkynyl phenanthrene ring derivative) shown in the structural general formula of the formula I comprises the following steps: uniformly mixing a compound shown in a formula II, alkyne (a compound shown in a formula II'), alkali, a catalyst and a ligand in a solvent for cyclization reaction, and obtaining a compound shown in a formula I after the reaction is finished:
in the formula I and the formula II, X is carbon or nitrogen;
the R is1Can be selected from hydrogen, halogen (fluorine or chlorine), trifluoromethyl, alkoxy, alkyl and cyano; the R is1May be mono-or polysubstituted; when R is1When polysubstituted, substituents R in different positions1May be the same or different;
the R is2Is aryl, substituted aryl, heteroaryl, cycloalkyl, alkyl, alkylsilyl;
the substituents in the substituted aryl group may be selected from any of the following groups: halogen (fluoro or chloro or bromo), trifluoromethyl, alkyl, alkoxy, cyano, N-dimethyl, phenyl; the substituents in the substituted aryl group may be mono-or polysubstituted;
in the invention, the aryl in the aryl or substituted aryl can be phenyl or phenanthryl;
in the present invention, the heteroaryl group in the heteroaryl group or substituted heteroaryl group may be thienyl, pyridyl;
in the present invention, the alkyl group may be C1-C10Straight or branched alkyl groups of (1), such as methyl, ethyl, t-butyl, etc.;
in the present invention, the alkoxy group may be C1-C10Straight or branched alkoxy groups of (1), such as methoxy, ethoxy, etc.;
in the present invention, the cycloalkyl group may be C6Cycloalkyl groups such as cyclohexyl, cyclohexenyl.
In the present invention, the alkylsilyl group may be C1-C3Such as trimethylsilyl and triisopropylsilyl.
Specifically, the R is2Can be phenyl, o-fluorophenyl or o-chlorobenzeneAnd a phenyl group, an o-bromophenyl group, a p-trifluoromethylphenyl group, a p-methoxyphenyl group, a p-methylphenyl group, a p-cyanophenyl group, a p-tert-butylphenyl group, a p-N, N-dimethylphenyl group, a p-phenylphenyl group, a thienyl group, a cyclohexyl group, an N-butyl group, a triisopropylsilyl group, etc.
The alkyne is: phenylacetylene, mono-substituted phenylacetylene, poly-substituted phenylacetylene, alkyl acetylene, silicon-based acetylene, thienyl acetylene, etc.
In the invention, the alkali is tert-butyl lithium.
In the invention, the catalyst is a copper-containing compound; the copper-containing compound is selected from at least one of cuprous chloride, cuprous bromide and cuprous iodide, preferably cuprous iodide.
In the present invention, the ligand is: pyridine, N, N '-dimethylethylenediamine, ethylenediamine, imidazole, methylimidazole, triethylamine, triphenylphosphine, triethylenediamine, phenanthroline, piperidine, diisopropylamine, N, N, N', N '-tetrahydroxyethylethylenediamine, 1-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, N, N-dimethylpropylurea, etc., with N, N' -dimethylethylenediamine being preferred.
In the invention, the solvent is one or the combination of two or more of 2-methyltetrahydrofuran, dichloroethane, acetonitrile, 1, 2-dimethoxyethane, 1, 4-dioxane and tetrahydrofuran, and tetrahydrofuran is preferred.
In the present invention, the amount of the alkyne is 1 to 10 times, preferably 1.2 times, the molar amount of the compound represented by formula II.
In the present invention, the amount of the base is 1 to 10 times (e.g., 2 or 3 times), preferably 3 times, the molar amount of the compound represented by formula II.
In the present invention, the amount of the catalyst is 5 to 50%, preferably 20%, of the charged molar amount of the compound of formula II.
In the present invention, the ligand is used in an amount of 10 to 100%, preferably 40%, of the charged molar amount of the compound of formula II.
In the cyclization reaction step, the reaction temperature is 25-140 ℃, and preferably 100 ℃; the reaction time is 1 to 12 hours (e.g., 3 hours, 6 hours, 9 hours, 12 hours), preferably 3 hours.
In the present invention, the reaction apparatus for the cyclization reaction is a sealed reaction apparatus, and is preferably a glass-sealed tube.
The method for synthesizing the 9-amino-10-alkynyl phenanthrene ring derivative shown in the formula I is a one-step synthesis method, and has the following characteristics: (1) the catalyst is cheap and easy to obtain, and the reaction operation is simple; (2) the catalytic system has strong universality on substrates, and various alkyne substrates can efficiently react with the compound shown in the formula II; (3) amino and alkynyl with higher reaction activity can be simultaneously introduced into the phenanthrene ring framework, so that compared with the traditional synthetic method, the experimental steps are greatly saved.
Drawings
FIG. 1 is a hydrogen spectrum of a target product obtained in preparation example 1 of a raw material.
FIG. 2 is a carbon spectrum of the objective product obtained in raw material preparation example 1.
FIG. 3 is a hydrogen spectrum of the objective product obtained in raw material preparation example 2.
FIG. 4 is a carbon spectrum of the objective product obtained in raw material preparation example 2.
FIG. 5 is a hydrogen spectrum of the objective product obtained in raw material preparation example 3.
FIG. 6 is a carbon spectrum of the objective product obtained in raw material preparation example 3.
FIG. 7 is a hydrogen spectrum of the objective product obtained in raw material preparation example 4.
FIG. 8 is a carbon spectrum of the objective product obtained in raw material preparation example 4.
FIG. 9 is a hydrogen spectrum of the objective product obtained in raw material preparation example 5.
FIG. 10 is a carbon spectrum of the objective product obtained in raw material preparation example 5.
FIG. 11 is a hydrogen spectrum of the objective product obtained in example 1.
FIG. 12 is a carbon spectrum of the objective product obtained in example 1.
FIG. 13 is a hydrogen spectrum of the objective product obtained in example 2.
FIG. 14 is a carbon spectrum of the objective product obtained in example 2.
FIG. 15 is a hydrogen spectrum of the objective product obtained in example 3.
FIG. 16 is a carbon spectrum of the objective product obtained in example 3.
FIG. 17 is a hydrogen spectrum of the objective product obtained in example 4.
FIG. 18 is a carbon spectrum of the objective product obtained in example 4.
FIG. 19 is a hydrogen spectrum of the objective product obtained in example 5.
FIG. 20 is a carbon spectrum of the objective product obtained in example 5.
FIG. 21 is a hydrogen spectrum of the objective product obtained in example 6.
FIG. 22 is a carbon spectrum of the objective product obtained in example 6.
FIG. 23 is a hydrogen spectrum of the objective product obtained in example 7.
FIG. 24 is a carbon spectrum of the objective product obtained in example 7.
FIG. 25 is a hydrogen spectrum of the objective product obtained in example 8.
FIG. 26 is a carbon spectrum of the objective product obtained in example 8.
FIG. 27 is a hydrogen spectrum of the objective product obtained in example 9.
FIG. 28 is a carbon spectrum of the objective product obtained in example 9.
FIG. 29 is a hydrogen spectrum of the objective product obtained in example 10.
FIG. 30 is a carbon spectrum of the objective product obtained in example 10.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The invention provides a novel catalytic reaction system for one-step synthesis of 9-amino-10-alkynyl phenanthrene ring derivatives by using cheap and easily-obtained copper salts as catalysts and catalyzing p-toluenesulfonylhydrazone derivatives (formula II) and alkynes with high efficiency and high chemoselectivity. The method can be carried out according to the following specific steps: (1) sequentially adding a p-toluenesulfonylhydrazone derivative (formula II), tert-butyllithium, cuprous iodide, N' -dimethylethylenediamine, alkyne and a solvent tetrahydrofuran into a glass reaction tube; (2) sealing the reaction tube under nitrogen atmosphere; (3) heating and stirring the mixture for reaction at a certain temperature; (4) after the reaction was stopped, heating and stirring were stopped, and the reaction mixture was cooled to room temperature and then subjected to product separation by chromatography.
The preparation of the p-toluenesulfonylhydrazone derivative (formula II) used as the raw material comprises the following steps: (1) uniformly mixing a compound shown in a structure of a formula III and a compound shown in a structure of a formula IV, potassium fluoride and dichlorodiphenylene palladium phosphorus in a solvent 1, 4-dioxane and water for coupling reaction, and obtaining a compound shown in a structural general formula of a formula V after the reaction is finished; (2) slowly adding the compound shown in the structural general formula V into a methanol solution of p-toluenesulfonyl hydrazide, reacting at room temperature for 12 hours to obtain a compound shown in the structural general formula II after the reaction is finished, and taking the compound as a raw material for the reaction.
In the formulae II, III and V, X, R1Is as defined in formula I.
Raw material preparation example 1
920mg (5mmol) of o-bromobenzaldehyde, 1.374g (6mmol) of o-cyanobenzene pinacol ester, 870mg (15mmol) of potassium fluoride, 176mg (0.25mmol) of dichlorodiphenylpalladium phosphate, 10mL of 1, 4-dioxane and 1mL of water are respectively weighed and added into a 25mL glass reaction tube with a cover, the reaction tube is sealed under nitrogen atmosphere, the reaction tube is placed in an oil bath to be heated to 100 ℃, the temperature is kept for 12 hours for reaction, and then the reaction tube is cooled to room temperature, so that 2- (2-cyanophenyl) benzaldehyde (formula V: X ═ C; R: C) is obtained1H) was isolated by column chromatography to give 662mg (3.20mmol, 64%) of pure material.
655mg (3.52mmol) of p-toluenesulfonyl hydrazide and 10mL of methanol were weighed respectively, added to a 25mL round-bottomed flask, stirred at room temperature, added 662mg (3.20mmol) of 2- (2-cyanophenyl) benzaldehyde slowly, and stirred at room temperature overnight to obtain a white precipitate, which was identified as 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonyl hydrazone (formula II: X ═ C; R) by its hydrogen spectrum (FIG. 1) and carbon spectrum (FIG. 2)1H), filtration washed with glacial methanol to give pure material 1.14g (3.04mmol, 95%) as starting material for the present invention.
Raw material preparation example 2
Respectively weighing 1.07g (5mmol) of 5-methoxy o-bromobenzaldehyde, 1.374g (6mmol) of o-cyanobenzene boronic acid pinacol ester, 870mg (15mmol) of potassium fluoride, 176mg (0.25mmol) of dichlorodiphenylpalladium phosphate, 10mL of 1, 4-dioxane and 1mL of water, adding the materials into a 25mL glass reaction tube with a cover, sealing the reaction tube under a nitrogen atmosphere, reacting in an oil bath, heating to 100 ℃, preserving heat for 12 hours, and cooling to room temperature to obtain 5-methoxy-2- (2-cyanophenyl) benzaldehyde (formula V: X ═ C; R;, R: -C)15-OMe) was purified by column chromatography to give 794mg (3.35mmol, 67%) of pure material.
686mg (3.69mmol) of p-toluenesulfonyl hydrazide and 10mL of methanol are respectively weighed, added into a 25mL round-bottomed flask, stirred at room temperature, slowly added with 794mg (3.35mmol) of 5-methoxy-2- (2-cyanophenyl) benzaldehyde, and stirred at room temperature overnight to obtain white precipitate, which is identified as 5-methoxy-2- (2-cyanophenyl) benzaldehyde p-toluenesulfonyl hydrazone (formula II: X ═ C; R) by hydrogen spectrum (figure 3) and carbon spectrum (figure 4)15-OMe) filtered and washed with ice methanol to give pure material 1.22g (3.02mmol, 90%) as the starting material for the present invention.
Raw material preparation example 3
Respectively weighing 1.26mg (5mmol) of 4-trifluoromethyl o-bromobenzaldehyde, 1.374g (6mmol) of o-cyanobenzene pinacol ester, 870mg (15mmol) of potassium fluoride, 176mg (0.25mmol) of dichlorodiphenylpalladium phosphate, 10mL of 1, 4-dioxane and 1mL of water, adding the materials into a 25mL glass reaction tube with a cover, sealing the reaction tube under a nitrogen atmosphere, reacting in an oil bath, heating to 100 ℃, preserving heat for 12h, and cooling to room temperature to obtain 4-trifluoromethyl-2- (2-cyanophenyl) benzaldehyde (formula V: X ═ C; R;, R1＝4-CF3) Chromatography column gave 894mg (3.25mmol, 65%) of pure substance.
Separately, 665mg (3.58mmol) of p-toluenesulfonylhydrazide and 10mL of methanol were weighed and added to a 25mL round-bottomed flask, and stirred at room temperature, 894mg (3.25mmol) of 4-trifluoromethyl-2- (2-cyanophenyl) benzaldehyde was slowly added thereto, and stirred at room temperature overnight to obtain a white precipitate, which was identified as 4-trifluoromethyl-2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone (formula I) from its hydrogen spectrum (FIG. 5) and carbon spectrum (FIG. 6)II:X＝C；R1＝4-CF3) Filtration and washing with ice methanol gave pure substance 1.35g (3.01mmol, 94%) as starting material for the present invention.
Raw material preparation example 4
Respectively weighing 1.09g (5mmol) of 5-chloro-o-bromobenzaldehyde, 1.374g (6mmol) of o-cyanobenzene boronic acid pinacol ester, 870mg (15mmol) of potassium fluoride, 176mg (0.25mmol) of dichlorodiphenylpalladium, 10mL of 1, 4-dioxane and 1mL of water, adding the materials into a 25mL glass reaction tube with a cover, sealing the reaction tube under a nitrogen atmosphere, reacting in an oil bath, heating to 100 ℃, preserving heat for 12 hours, and cooling to room temperature to obtain 5-chloro-2- (2-cyanophenyl) benzaldehyde (formula V: X ═ C; R: -C; R: -C)1Separation on a chromatographic column yields 819mg (3.40mmol, 68%) of pure substance.
Respectively weighing 696mg (3.74mmol) of p-toluenesulfonylhydrazide and 10mL of methanol, adding into a 25mL round-bottomed flask, stirring at room temperature, slowly adding 819mg (3.40mmol) of 5-chloro-2- (2-cyanophenyl) benzaldehyde, stirring at room temperature overnight to obtain white precipitate, and identifying as 5-chloro-2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone (formula II: X ═ C; R, C; from its hydrogen spectrum (FIG. 7) and carbon spectrum (FIG. 8)1= 5-Cl), filtration washed with glacial methanol to give pure material 1.29g (3.16mmol, 93%) as the starting material for the invention.
Raw material preparation example 5
925mg (5mmol) of 2-bromo-3-aldehyde pyridine, 1.374g (6mmol) of o-cyanobenzene boronic acid pinacol ester, 870mg (15mmol) of potassium fluoride, 176mg (0.25mmol) of dichlorodiphenylpalladium, 10mL of 1, 4-dioxane and 1mL of water are respectively weighed and added into a 25mL glass reaction tube with a cover, the reaction tube is sealed under nitrogen atmosphere, the reaction tube is placed in an oil bath for heating to 100 ℃, the reaction is kept warm for 12 hours and then is cooled to room temperature, and 3-aldehyde-2- (2-cyanophenyl) pyridine (formula V: X ═ N; R: X;, R: N, R: 2-aldehyde-2- (2-cyanophenyl) pyridine is obtained1H) and chromatographed on a column to give 562mg (2.70mmol, 54%) of pure material.
552mg (2.97mmol) of p-toluenesulfonylhydrazide and 10mL of methanol were weighed respectively, added to a 25mL round-bottomed flask, stirred at room temperature, followed by slow addition of 562mg (2.70mmol) of 3-aldehyde-2- (2-cyanophenyl) pyridine, and stirred at room temperature overnight to give a white precipitate, which was identified from its hydrogen spectrum (FIG. 9) and carbon spectrum (FIG. 10)Identified as 3-formyl-2- (2-cyanophenyl) pyridine p-toluenesulfonylhydrazone (formula II: X ═ N; R1H), filtration washed with glacial methanol to give 884mg (2.35mmol, 87%) of pure material as starting material for the invention.
Example 1
Respectively weighing 94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 33uL (0.30mmol) of phenylacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube in a nitrogen atmosphere, placing the reaction tube in an oil bath, heating to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the target product 9-amino-10-phenylethynylphenanthrene (formula I: X ═ C; R ═ C)1＝H；R2Phenyl). And (3) reaction results: the isolated desired product, 9-amino-10-phenylethynylphenanthrene, was weighed and calculated to give the product in an isolated yield of 78%. Fig. 11 and fig. 12 show the hydrogen spectrum and the carbon spectrum of the target product 9-amino-10-phenylethynylphenanthrene prepared in this example, respectively, and it can be seen that the structure of the compound is correct.
Example 2
Respectively weighing 94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 34uL (0.30mmol) of 2-fluoroacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube in a nitrogen atmosphere, heating the sealed glass reaction tube in an oil bath to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the target product, namely 9-amino-10- (2-fluoroacetylene) phenanthrene (formula I: X;, R;, provided by the invention1＝H；R22-fluorophenyl). And (3) reaction results: the isolated desired product, 9-amino-10- (2-fluorophenylethynyl) phenanthrene, was weighed and calculated to give the product in 69% isolated yield. Fig. 13 and 14 show a hydrogen spectrum and a carbon spectrum of the target product 9-amino-10- (2-fluorophenylethynyl) phenanthrene prepared in this example, respectively, and it can be seen that the structure of the compound is correct.
Example 3
Respectively weighing 2- (2-cyanobenzene)Adding 94mg (0.25mmol) of benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 36uL (0.30mmol) of o-chlorophenyl acetylene and 8mL of tetrahydrofuran into a 25mL glass reaction tube with a cover, sealing the glass reaction tube under a nitrogen atmosphere, placing the reaction tube in an oil bath, heating to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the target product, namely 9-amino-10- (2-chlorophenyl ethynyl) phenanthrene (formula I, wherein X is C; r1＝H；R22-chlorophenyl). And (3) reaction results: the isolated desired product, 9-amino-10- (2-chlorophenylethynyl) phenanthrene, was weighed and calculated to give the product in an isolated yield of 67%. Fig. 15 and 16 show a hydrogen spectrum and a carbon spectrum of the target product 9-amino-10- (2-chlorophenylethynyl) phenanthrene prepared in this example, respectively, and it can be seen that the structure of the compound is correct.
Example 4
Respectively weighing 94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 36uL (0.30mmol) of o-bromophenylacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube under a nitrogen atmosphere, heating the sealed glass reaction tube in an oil bath to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the target product, namely 9-amino-10- (2-bromophenylethynyl) phenanthrene (formula I: X ═ C; R ═ C;, provided by the invention)1＝H；R22-bromophenyl). And (3) reaction results: the isolated desired product, 9-amino-10- (2-bromophenylethynyl) phenanthrene, was weighed and calculated to give the product in 51% isolated yield. FIG. 17 shows a hydrogen spectrum and a carbon spectrum of the target product, 9-amino-10- (2-bromophenylethynyl) phenanthrene, prepared in this example, respectively, and it can be seen that the structure of the compound is correct.
Example 5
94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of t-butyllithium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 69uL (0.30mmol) of triisopropylsilacetylene and 8mL of tetrahydrofuran were weighed respectively and placed in a 25mL glass reaction tube with a lid under a nitrogen atmosphereSealing the glass tube, placing the reaction tube in an oil bath, heating to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and then cooling to room temperature to obtain the target product 9-amino-10- (triisopropylsilylethynyl) phenanthrene (formula I: X ═ C; R)1＝H；R2Triisopropylsilyl). And (3) reaction results: the isolated desired product, 9-amino-10- (triisopropylsilaethynyl) phenanthrene, was weighed and calculated to give the product in 47% isolated yield. Fig. 19 and 20 show the hydrogen spectrum and the carbon spectrum of the target product 9-amino-10- (triisopropylsilylethynyl) phenanthrene prepared in this example, respectively, and it can be seen that the structure of the compound is correct.
Example 6
Respectively weighing 94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 35uL (0.30mmol) of 4-methylphenylacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube in a nitrogen atmosphere, heating the sealed glass reaction tube in an oil bath to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the target product 9-amino-10- (4-methylphenylacetylene) (formula I: X ═ C; R ═ C) phenanthrene provided by the invention1＝H；R24-methylphenyl). And (3) reaction results: the isolated desired product, 9-amino-10- (4-methylphenylethynyl) phenanthrene, was weighed and calculated to give the product an isolated yield of 71%. Fig. 21 and 22 show a hydrogen spectrum and a carbon spectrum of the target product 9-amino-10- (4-methylphenylethynyl) phenanthrene prepared in this example, respectively, and it can be seen that the structure of the compound is correct.
Example 7
Respectively weighing 101mg (0.25mmol) of 5-methoxy-2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 33uL (0.30mmol) of phenylacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube in a nitrogen atmosphere, heating the sealed glass reaction tube in an oil bath to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the target product 2-methoxy-9-amino-10-phenylethynyl phenanthrene (formula I: X ═ C; R ═ C)12-methoxy; r2Phenyl). And (3) reaction results: the isolated objective product, 2-methoxy-9-amino-10-phenylethynylphenanthrene, was weighed out and calculated to give an isolated yield of 64%. Fig. 23 and 24 show a hydrogen spectrum and a carbon spectrum of the target product 2-methoxy-9-amino-10-phenylethynyl phenanthrene prepared in this example, respectively, and it can be seen from the figure that the compound has a correct structure.
Example 8
Respectively weighing 111mg (0.25mmol) of 4-trifluoromethyl-2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 42uL (0.30mmol) of 4-trifluoromethylphenylacetylene and 8mL of tetrahydrofuran, adding the mixture into a 25mL glass reaction tube with a cover, sealing the glass reaction tube in a nitrogen atmosphere, placing the reaction tube in an oil bath, heating to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and then cooling to room temperature to obtain the target product, namely 3-trifluoromethyl-9-amino-10- (4-trifluoromethylphenylethynyl) phenanthrene (formula I: X ═ C; R;, provided by the invention13-trifluoromethyl; r24-trifluoromethylphenyl). And (3) reaction results: the isolated objective product, 3-trifluoromethyl-9-amino-10- (4-trifluoromethylphenylethynyl) phenanthrene, was weighed and calculated to give the product in an isolated yield of 57%. Fig. 25 and 26 show the hydrogen spectrum and the carbon spectrum of the target product 3-trifluoromethyl-9-amino-10- (4-trifluoromethylphenylethynyl) phenanthrene prepared in this example, respectively, and it can be seen from these figures that the compound has a correct structure.
Example 9
Respectively weighing 102mg (0.25mmol) of 5-chloro-2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 33uL (0.30mmol) of phenylacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube in a nitrogen atmosphere, heating the sealed glass reaction tube in an oil bath to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the target product 2-chloro-9-amino-10-phenylethynyl phenanthrene (formula I: X ═ C; R ═ C)12-chloro; r2Phenyl). And (3) reaction results: weighing the separated target product 2-chloro-9-amino-10-phenylethynyl phenanthrene, and calculatingThe isolated yield of the product was 76%. Fig. 27 and 28 show a hydrogen spectrum and a carbon spectrum of the target product 2-chloro-9-amino-10-phenylethynylphenanthrene prepared in this example, respectively, and it can be seen that the compound has a correct structure.
Example 10
Respectively weighing 94mg (0.25mmol) of 3-aldehyde-2- (2-cyanophenyl) pyridine p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 33uL (0.30mmol) of phenylacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube in a nitrogen atmosphere, heating the reaction tube in an oil bath to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the target product 5-phenylethynyl-6-amino-benzo [ b ] provided by the invention]Quinolines (formula I: X ═ N; R)1＝H；R2Phenyl). And (3) reaction results: separating the target product 5-phenylethynyl-6-amino-benzo [ b]Quinoline was weighed and the isolated yield of the product was calculated to be 51%. FIGS. 29 and 30 are views showing the objective product 5-phenylethynyl-6-amino-benzo [ b ] prepared in this example]The hydrogen spectrum and the carbon spectrum of quinoline show that the compound has a correct structure.
Example 11
Respectively weighing 94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 7mg (0.05mmol) of cuprous bromide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 33uL (0.30mmol) of phenylacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube in a nitrogen atmosphere, placing the reaction tube in an oil bath, heating to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the target product 9-amino-10-phenylethynylphenanthrene (formula I: X ═ C; R ═ C)1＝H；R2Phenyl). And (3) reaction results: the isolated desired product, 9-amino-10-phenylethynylphenanthrene, was weighed and calculated to give an isolated yield of 28%. Fig. 11 and fig. 12 show the hydrogen spectrum and the carbon spectrum of the target product 9-amino-10-phenylethynylphenanthrene prepared in this example, respectively, and it can be seen that the structure of the compound is correct.
Example 12
Respectively weighing 94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 33uL (0.30mmol) of phenylacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube in a nitrogen atmosphere, placing the reaction tube in an oil bath, heating to 100 ℃, stirring, carrying out heat preservation reaction for 6 hours, and cooling to room temperature to obtain the target product 9-amino-10-phenylethynylphenanthrene (formula I: X ═ C; R ═ C)1＝H；R2Phenyl). And (3) reaction results: the isolated target product, 9-amino-10-phenylethynylphenanthrene, was weighed and calculated to give an isolated yield of 77%. Fig. 11 and fig. 12 show the hydrogen spectrum and the carbon spectrum of the target product 9-amino-10-phenylethynylphenanthrene prepared in this example, respectively, and it can be seen that the structure of the compound is correct.
Example 13
Respectively weighing 94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 33uL (0.30mmol) of phenylacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube in a nitrogen atmosphere, placing the reaction tube in an oil bath, heating to 100 ℃, stirring, keeping the temperature for reaction for 9 hours, and cooling to room temperature to obtain the target product 9-amino-10-phenylethynylphenanthrene (formula I: X ═ C; R ═ C)1＝H；R2Phenyl). And (3) reaction results: the isolated desired product, 9-amino-10-phenylethynylphenanthrene, was weighed and calculated to give an isolated yield of 76%. Fig. 11 and fig. 12 show the hydrogen spectrum and the carbon spectrum of the target product 9-amino-10-phenylethynylphenanthrene prepared in this example, respectively, and it can be seen that the structure of the compound is correct.
Example 14
94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 33uL (0.30mmol) of phenylacetylene and 8mL of tetrahydrofuran were weighed respectively and added into a 25mL glass reaction tube with a cover, the glass seal tube was sealed under a nitrogen atmosphere, and the reaction tube was placed in an oil bath and heatedStirring the mixture at 100 ℃, keeping the temperature for reaction for 12 hours, and then cooling the mixture to room temperature to obtain the target product 9-amino-10-phenylethynyl phenanthrene (formula I: X ═ C; R)1＝H；R2Phenyl). And (3) reaction results: the isolated target product, 9-amino-10-phenylethynylphenanthrene, was weighed and calculated to give an isolated yield of 77%. Fig. 11 and fig. 12 show the hydrogen spectrum and the carbon spectrum of the target product 9-amino-10-phenylethynylphenanthrene prepared in this example, respectively, and it can be seen that the structure of the compound is correct.
Example 15
Respectively weighing 94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 40mg (0.50mmol) of tert-butyllithium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 33uL (0.30mmol) of phenylacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube in a nitrogen atmosphere, placing the reaction tube in an oil bath, heating to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the target product 9-amino-10-phenylethynylphenanthrene (formula I: X ═ C; R ═ C)1＝H；R2Phenyl). And (3) reaction results: the isolated desired product, 9-amino-10-phenylethynylphenanthrene, was weighed and calculated to give an isolated yield of 70%. Fig. 11 and fig. 12 show the hydrogen spectrum and the carbon spectrum of the target product 9-amino-10-phenylethynylphenanthrene prepared in this example, respectively, and it can be seen that the structure of the compound is correct.
Example 16
Respectively weighing 94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 9mg (0.05mmol) of cuprous iodide, 33ul (0.30mmol) of phenylacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube in a nitrogen atmosphere, heating the glass reaction tube in an oil bath to 100 ℃, stirring, keeping the temperature for reaction for 3 hours, and cooling to room temperature to obtain the target product 9-amino-10-phenylethynyl phenanthrene (formula I: X ═ C; R: the formula I: the R: the formula I: the R: the invention1＝H；R2Phenyl). And (3) reaction results: the isolated desired product, 9-amino-10-phenylethynylphenanthrene, was weighed and calculated to give the product in 47% isolated yield. FIG. 11 and FIG. 12 show the target products obtained in this exampleThe hydrogen spectrum and the carbon spectrum of the 9-amino-10-phenylethynyl phenanthrene show that the compound has a correct structure.
Example 17
Respectively weighing 94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 9mg (0.05mmol) of cuprous iodide, 8uL (0.10mmol) of pyridine, 33uL (0.30mmol) of phenylacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube under the nitrogen atmosphere, placing the reaction tube in an oil bath, heating to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the target product 9-amino-10-phenylethynyl phenanthrene (formula I: X ═ C; R: the target product provided by the invention)1＝H；R2Phenyl). And (3) reaction results: the isolated desired product, 9-amino-10-phenylethynylphenanthrene, was weighed and calculated to give an isolated yield of 63%. Fig. 11 and fig. 12 show the hydrogen spectrum and the carbon spectrum of the target product 9-amino-10-phenylethynylphenanthrene prepared in this example, respectively, and it can be seen that the structure of the compound is correct.
Comparative example 1
94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 33uL (0.30mmol) of phenylacetylene and 8mL of tetrahydrofuran are respectively weighed and added into a 25mL glass reaction tube with a cover, the glass reaction tube is sealed under nitrogen atmosphere, the reaction tube is placed in an oil bath and heated to 100 ℃, stirred, kept for reaction for 3 hours and then cooled to room temperature. And (3) reaction results: the target product cannot be obtained.
Comparative example 2
Respectively weighing 94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 84mg (0.75mmol) of tert-butyl potassium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 33uL (0.30mmol) of phenylacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube in a nitrogen atmosphere, placing the reaction tube in an oil bath, heating to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the target product 9-amino-10-phenylethynylphenanthrene (formula I: X ═ C; R ═ C)1＝H；R2Phenyl). And (3) reaction results: separating the target product 9-amino-10-phenylethynylphenanthrene was weighed and the isolated yield of the product was calculated to be less than 5%.
Comparative example 3
Respectively weighing 94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 72mg (0.75mmol) of tert-butyl sodium, 9mg (0.05mmol) of cuprous iodide, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 33uL (0.30mmol) of phenylacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube in a nitrogen atmosphere, placing the reaction tube in an oil bath, heating to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the target product 9-amino-10-phenylethynylphenanthrene (formula I: X ═ C; R ═ C)1＝H；R2Phenyl). And (3) reaction results: the isolated desired product, 9-amino-10-phenylethynylphenanthrene, was weighed and calculated to give an isolated yield of less than 5%.
Comparative example 4
Respectively weighing 94mg (0.25mmol) of 2- (2-cyanophenyl) benzaldehyde p-toluenesulfonylhydrazone, 60mg (0.75mmol) of tert-butyllithium, 5mg (0.05mmol) of cuprous chloride, 11uL (0.10mmol) of N, N' -dimethylethylenediamine, 33uL (0.30mmol) of phenylacetylene and 8mL of tetrahydrofuran, adding the materials into a 25mL glass reaction tube with a cover, sealing the glass reaction tube in a nitrogen atmosphere, placing the reaction tube in an oil bath, heating to 100 ℃, stirring, carrying out heat preservation reaction for 3 hours, and cooling to room temperature to obtain the target product 9-amino-10-phenylethynylphenanthrene (formula I: X ═ C; R ═ C)1＝H；R2Phenyl). And (3) reaction results: the isolated desired product, 9-amino-10-phenylethynylphenanthrene, was weighed and calculated to give an isolated yield of less than 5%.
Claims (10)
1. A method for preparing a compound shown as a formula I comprises the following steps: uniformly mixing a compound shown in a formula II, alkyne shown in a formula II', alkali, a catalyst and a ligand in a solvent for cyclization reaction, and obtaining the compound shown in the formula I after the reaction is finished:
in the formula I and the formula II, X is carbon or nitrogen;
the R is1Selected from hydrogen, halogen (fluorine or chlorine), trifluoromethyl, alkoxy, alkyl, cyano; the R is1Is mono-or poly-substituted; when R is1When polysubstituted, substituents R in different positions1May be the same or different;
the R is2Is aryl, substituted aryl, heteroaryl, cycloalkyl, alkyl, alkylsilyl.
2. The method of claim 1, wherein: the substituent in the substituted aryl is selected from any one of the following groups: halogen (fluoro or chloro or bromo), trifluoromethyl, alkyl, alkoxy, cyano, N-dimethyl, phenyl; the substituents in the substituted aryl group may be mono-or polysubstituted;
the halogen is fluorine or chlorine or bromine;
the aryl in the aryl or substituted aryl is phenyl or phenanthryl;
heteroaryl in the heteroaryl or substituted heteroaryl is thienyl or pyridyl;
the alkyl group is C1-C10Linear or branched alkyl of (a);
the alkoxy is C1-C10A straight or branched alkoxy group of (a);
said cycloalkyl is C6Cycloalkyl groups such as cyclohexyl, cyclohexenyl;
the alkyl silicon group is C1-C3Such as trimethylsilyl and triisopropylsilyl.
3. The production method according to claim 1 or 2, characterized in that: the solvent is 2-methyltetrahydrofuran, dichloroethane, acetonitrile, 1, 2-dimethoxyethane, 1, 4-dioxane, tetrahydrofuran, etc., preferably tetrahydrofuran.
4. The production method according to any one of claims 1 to 3, characterized in that: the alkyne is phenylacetylene, mono-substituted phenylacetylene, multi-substituted phenylacetylene, alkyl acetylene, silicon-based acetylene or thienyl acetylene.
5. The production method according to any one of claims 1 to 4, characterized in that: the base is tert-butyl lithium.
6. The production method according to any one of claims 1 to 5, characterized in that: the catalyst is a copper-containing compound;
the copper-containing compound is selected from at least one of cuprous chloride, cuprous bromide and cuprous iodide, preferably cuprous iodide.
7. The production method according to any one of claims 1 to 6, characterized in that: the ligand is pyridine, N, N '-dimethylethylenediamine, ethylenediamine, imidazole, methylimidazole, triethylamine, triphenylphosphine, triethylenediamine, phenanthroline, hexahydropyridine, diisopropylamine, N, N, N', N '-tetrahydroxyethylethylenediamine, 1-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, N, N-dimethylpropyleneurea, preferably N, N' -dimethylethylenediamine.
8. The production method according to any one of claims 1 to 7, characterized in that:
the amount of alkyne is 1 to 10 times, preferably 1.2 times, the molar amount of the compound of formula II charged.
The amount of the base used is 1 to 10 times, preferably 3 times, the molar amount of the compound of formula II charged.
The amount of the catalyst is 5 to 50% times, preferably 20% times, the molar amount of the compound of formula II fed.
The ligand is used in an amount of 10 to 100%, preferably 40% times the molar amount of the compound of formula II.
9. The production method according to any one of claims 1 to 8, characterized in that: in the cyclization reaction step, the reaction temperature is 25-140 ℃, and preferably 100 ℃; the time is 1 to 12 hours, preferably 3 hours.
10. The production method according to any one of claims 1 to 9, characterized in that: the reaction device is a sealed reaction device, preferably a glass sealed tube.
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Non-Patent Citations (2)
| Title |
|---|
| YOUNG, BRIAN S.等: "Phenanthrene-Fused Azo-ene-ynes: Synthesis of Dibenzo[f, h]cinnoline and Dibenzo[e, g]isoindazole Derivatives", 《JOURNAL OF ORGANIC CHEMISTRY》, vol. 76, no. 20, pages 8483 - 8487 * |
| ZHANG, SHENG等: "Pd-Catalyzed cascade cyclization of o-alkynylanilines via C-H/C-N bond cleavage leading to dibenzo[a, c]carbazoles", 《ORGANIC&BIOMOLECULAR CHEMISTRY》, vol. 16, no. 29, pages 5236 - 5240 * |
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