CN114716454A - Nitrogen and oxa condensed ring aromatic hydrocarbon and synthetic method thereof - Google Patents
Nitrogen and oxa condensed ring aromatic hydrocarbon and synthetic method thereof Download PDFInfo
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- CN114716454A CN114716454A CN202210557098.5A CN202210557098A CN114716454A CN 114716454 A CN114716454 A CN 114716454A CN 202210557098 A CN202210557098 A CN 202210557098A CN 114716454 A CN114716454 A CN 114716454A
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- nitrogen
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- ring aromatic
- condensed ring
- oxa
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 29
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 22
- 238000010189 synthetic method Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 150000008049 diazo compounds Chemical class 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940125904 compound 1 Drugs 0.000 claims abstract description 5
- 229940125782 compound 2 Drugs 0.000 claims abstract description 5
- 229940126214 compound 3 Drugs 0.000 claims abstract description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 18
- -1 hexafluoroantimonate Chemical compound 0.000 claims description 13
- 239000010948 rhodium Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- QVLTVILSYOWFRM-UHFFFAOYSA-L CC1=C(C)C(C)([Rh](Cl)Cl)C(C)=C1C Chemical class CC1=C(C)C(C)([Rh](Cl)Cl)C(C)=C1C QVLTVILSYOWFRM-UHFFFAOYSA-L 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000001555 benzenes Chemical group 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- FFFIRKXTFQCCKJ-UHFFFAOYSA-N 2,4,6-trimethylbenzoic acid Chemical compound CC1=CC(C)=C(C(O)=O)C(C)=C1 FFFIRKXTFQCCKJ-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GFCVQYCZHGSRMA-UHFFFAOYSA-L C(C)(=O)[O-].CC1=C(C(=C(C1([Rh+2])C)C)C)C.C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].CC1=C(C(=C(C1([Rh+2])C)C)C)C.C(C)(=O)[O-] GFCVQYCZHGSRMA-UHFFFAOYSA-L 0.000 claims description 2
- SAXQOYZKDFVDTH-UHFFFAOYSA-N CC1=C(C(=C(C1(C)[Rh])C)C)C Chemical compound CC1=C(C(=C(C1(C)[Rh])C)C)C SAXQOYZKDFVDTH-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 2
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical compound [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 claims description 2
- HSYLTRBDKXZSGS-UHFFFAOYSA-N silver;bis(trifluoromethylsulfonyl)azanide Chemical compound [Ag+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HSYLTRBDKXZSGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 235000013904 zinc acetate Nutrition 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 12
- 238000001308 synthesis method Methods 0.000 abstract description 8
- 125000005842 heteroatom Chemical group 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 125000004429 atom Chemical group 0.000 abstract description 2
- 229930014626 natural product Natural products 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- 150000001875 compounds Chemical class 0.000 description 31
- 238000001228 spectrum Methods 0.000 description 29
- 230000005311 nuclear magnetism Effects 0.000 description 26
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 238000012512 characterization method Methods 0.000 description 15
- 239000003480 eluent Substances 0.000 description 15
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 description 15
- 239000003208 petroleum Substances 0.000 description 15
- 239000000741 silica gel Substances 0.000 description 15
- 229910002027 silica gel Inorganic materials 0.000 description 15
- 229910001544 silver hexafluoroantimonate(V) Inorganic materials 0.000 description 15
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 12
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 6
- WLWNRAWQDZRXMB-YLFCFFPRSA-N (2r,3r,4r,5s)-n,3,4,5-tetrahydroxy-1-(4-phenoxyphenyl)sulfonylpiperidine-2-carboxamide Chemical compound ONC(=O)[C@H]1[C@@H](O)[C@H](O)[C@@H](O)CN1S(=O)(=O)C(C=C1)=CC=C1OC1=CC=CC=C1 WLWNRAWQDZRXMB-YLFCFFPRSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000004585 polycyclic heterocycle group Chemical group 0.000 description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000010499 C–H functionalization reaction Methods 0.000 description 2
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000004893 oxazines Chemical class 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 1
- JNPGUXGVLNJQSQ-BGGMYYEUSA-M (e,3r,5s)-7-[4-(4-fluorophenyl)-1,2-di(propan-2-yl)pyrrol-3-yl]-3,5-dihydroxyhept-6-enoate Chemical compound CC(C)N1C(C(C)C)=C(\C=C\[C@@H](O)C[C@@H](O)CC([O-])=O)C(C=2C=CC(F)=CC=2)=C1 JNPGUXGVLNJQSQ-BGGMYYEUSA-M 0.000 description 1
- VAVHMEQFYYBAPR-ITWZMISCSA-N (e,3r,5s)-7-[4-(4-fluorophenyl)-1-phenyl-2-propan-2-ylpyrrol-3-yl]-3,5-dihydroxyhept-6-enoic acid Chemical compound CC(C)C1=C(\C=C\[C@@H](O)C[C@@H](O)CC(O)=O)C(C=2C=CC(F)=CC=2)=CN1C1=CC=CC=C1 VAVHMEQFYYBAPR-ITWZMISCSA-N 0.000 description 1
- FZTLLUYFWAOGGB-UHFFFAOYSA-N 1,4-dioxane dioxane Chemical compound C1COCCO1.C1COCCO1 FZTLLUYFWAOGGB-UHFFFAOYSA-N 0.000 description 1
- RAIKREKWRHXJRW-UHFFFAOYSA-N 2H-naphtho[1,2-h]quinolin-1-one Chemical class C1(CC=NC=2C3=C(C=CC1=2)C1=CC=CC=C1C=C3)=O RAIKREKWRHXJRW-UHFFFAOYSA-N 0.000 description 1
- HIHOEGPXVVKJPP-JTQLQIEISA-N 5-fluoro-2-[[(1s)-1-(5-fluoropyridin-2-yl)ethyl]amino]-6-[(5-methyl-1h-pyrazol-3-yl)amino]pyridine-3-carbonitrile Chemical compound N([C@@H](C)C=1N=CC(F)=CC=1)C(C(=CC=1F)C#N)=NC=1NC=1C=C(C)NN=1 HIHOEGPXVVKJPP-JTQLQIEISA-N 0.000 description 1
- DGJMHKMYSDYOFP-MRXNPFEDSA-N C=CC(N(CCC1)C[C@@H]1N1N=C(C2=CN(CC(C3=CC=CC=C3)(F)F)N=N2)C2=C(N)N=CN=C12)=O Chemical compound C=CC(N(CCC1)C[C@@H]1N1N=C(C2=CN(CC(C3=CC=CC=C3)(F)F)N=N2)C2=C(N)N=CN=C12)=O DGJMHKMYSDYOFP-MRXNPFEDSA-N 0.000 description 1
- HGDWHTASNMRJMP-UHFFFAOYSA-N [1-(hydroxyamino)-1-oxo-5-(3-phenoxyphenyl)pentan-2-yl]phosphonic acid Chemical compound ONC(=O)C(P(O)(O)=O)CCCC1=CC=CC(OC=2C=CC=CC=2)=C1 HGDWHTASNMRJMP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention provides nitrogen and oxa condensed ring aromatic hydrocarbons and a synthesis method thereof, which are used for solving the technical problems of single synthesis method of the existing condensed ring aromatic hydrocarbons, complex substrate synthesis, limited product structure and the like. The synthesis method comprises the following steps: adding the oxazine compound 1, the diazo compound 2, the catalyst and the additive into a solvent in an inert atmosphere, reacting in the inert atmosphere, and obtaining the hetero-condensed ring aromatic compound 3 after the reaction is finished. The invention provides a simple and effective synthesis method for the synthesis of polycyclic aromatic hydrocarbon containing multiple heteroatoms, and the method has the characteristics of mild reaction conditions, simple operation, atom economy, economic steps, strong functional group tolerance, good yield and the like. The obtained product has wide industrial application prospect, and provides a new idea and a new method for the fields of medicine, natural product synthesis, luminescent materials and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthetic chemistry, and particularly relates to nitrogen and oxa condensed ring aromatic hydrocarbon and a synthetic method thereof.
Background
Polycyclic aromatic hydrocarbons refer to polycyclic aromatic hydrocarbon compounds composed of two or more aromatic hydrocarbons and are widely used in the industries of medicines, dyes and the like. The crystal arrangement of the polycyclic aromatic hydrocarbon has pi-pi interaction, and molecules form ordered accumulation, so the polycyclic aromatic hydrocarbon has wide application prospects in the fields of Organic photoelectric devices (including Organic Field-Effect transistors (OFETs), Organic Solar Cells (OSCs), Organic Light-Emitting diodes (OLEDs) and the like), Organic semiconductor materials and the like (chem.Rev.,2007,107,926; chem.Soc.Rev.,2010,39, 1489; chem.Soc.Rev.,2012,41, 4245; Nature,2004,428,911). Compared with the traditional inorganic photoelectric material, the large-size conjugated molecule has the structural adjustment of molecular level; the solubility is good, and the processing is easy; the material is light and flexible, and can realize the preparation of large-area devices. Therefore, designing and synthesizing novel organic polycyclic aromatic hydrocarbons, and researching their properties and applications have been one of the research hotspots of scientists in the fields of chemistry, materials, biology and the like. In particular, the heteroatom is used for replacing part of carbon atoms in the polycyclic compound to form conjugated skeleton molecules containing the heteroatom, namely hetero-polycyclic aromatic hydrocarbon, so that the stability and the assembly performance of the material can be obviously improved, and the photoelectric performance and the versatility of the organic photoelectric material can be obviously improved (Angew. chem., int. Ed.,2010,49, 8209; chem. Mater.,2015,28, 3). Meanwhile, multifunctional modification of polycyclic aromatic hydrocarbon is also an important means for endowing organic photoelectric molecules with controllability and diversity.
The direct functionalization of inert C-H bonds is now undisputed as the ideal synthetic approach for chemists because of the superiority of the high atomic economy and the economic process, and it is called "Saint glass of chemistry". Indeed, transition metal catalyzed C — H activation reactions have achieved significant success over the last 20 years, achieving conversions not achievable by many traditional chemistries. Wherein, rhodium is catalyzed and guided to C-H bond activation 1: 2, the synthesis of polycyclic aromatic hydrocarbon constructed by coupling is rapidly developed, and a large number of novel polycyclic aromatic hydrocarbon frameworks with important application prospects in the fields of organic photoelectric materials and medicines are prepared. And the diazo compound is used as an important intermediate in organic synthesis and applied to transition metal catalysis 1: 2 coupling and constructing fused heterocyclic aromatic hydrocarbon is still in the initial stage. To date, rhodium catalyzed directed C-H activation 1: 2 coupling construction of fused ring arene molecules there is only one report (org. lett.2017,19,2294) and the study is relatively slow. The method takes a strongly coordinated pyridine compound as a guide group, and realizes the reaction with a diazo compound of 1: 2, coupling to construct a series of naphthoquinolinone skeletons.
On one hand, the guide group used by the existing synthesis means is pyridine with strong coordination capacity, the substrate synthesis is complex, the product type is single, and the obtained skeleton is only aza polycyclic aromatic hydrocarbon. On the other hand, the benzoxazine imine is used as a key intermediate in organic synthesis, and has simple synthesis and wide sources. It was applied as a weak directing group to rhodium-catalyzed carbene 1: 2 coupling studies have not been reported. According to the reports of the prior documents, the hetero-polycyclic aromatic hydrocarbon can obviously improve the stability and the assembly performance of the material, thereby obviously improving the photoelectric performance and the versatility of the organic photoelectric material (Angew. chem., int.Ed.,2010,49, 8209; chem. Mater.,2015,28,3), and the application of the hetero-polycyclic aromatic hydrocarbon in the aspect of the organic photoelectric material has wide prospect; therefore, a new method for synthesizing hetero-polycyclic aromatic hydrocarbons is urgently needed.
Disclosure of Invention
The invention provides nitrogen and oxa polycyclic aromatic hydrocarbon and a synthesis method thereof, and provides a simple and effective synthesis method for synthesis of polycyclic aromatic hydrocarbon containing multiple heteroatoms, aiming at the technical problems of single synthesis method of fused heterocyclic aromatic hydrocarbon, complex substrate synthesis, limited product structure and the like.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a nitrogen and oxygen fused ring aromatic hydrocarbon has a structural formula as follows:
wherein R is any one of H, Me, OMe, F, Cl or Br; r1Any one of Me, n-Pr or Ph; r2Is n-Am oriPr; ar is Me, OMe, F, Cl, Br, Ph or CF3Any substituted benzene ring.
The synthesis method of the nitrogen and oxa condensed ring aromatic hydrocarbon comprises the following steps: adding an oxazine compound 1, a diazo compound 2, a catalyst and an additive into a solvent under an inert atmosphere for reaction, and obtaining a fused heterocyclic aromatic compound 3 after the reaction is finished, wherein the reaction equation is as follows:
wherein R is any one of H, Me, OMe, F, Cl or Br; r1Any one of Me, n-Pr or Ph; r2Is n-Am oriPr; ar is Me, OMe, F, Cl, Br, Ph or CF3Any one substituted benzene ring; wherein Rh (III) is a catalyst.
And after the reaction is finished, separating and purifying the solution after the reaction is finished to obtain the hetero-condensed ring aromatic hydrocarbon compound 3.
The reaction temperature is 80-120 ℃ in the reaction process, and the reaction time is 6-12 h.
The catalyst comprises a rhodium catalyst and a silver salt; the molar ratio of rhodium catalyst to silver salt is 1: 4; the rhodium catalyst is any one or combination of dichloro (pentamethylcyclopentadienyl) rhodium dimer, pentamethylcyclopentadienyl rhodium acetate or bis (hexafluoroantimonate) triethylenenitrile (pentamethylcyclopentadienyl) rhodium; the silver salt is any one or combination of silver hexafluoroantimonate, silver tetrafluoroborate, silver bistrifluoromethanesulfonimide, silver trifluoromethanesulfonate, silver sulfate, silver acetate and silver trifluoroacetate.
The catalyst consists of dichloro (pentamethyl cyclopentadienyl) rhodium dimer and silver hexafluoroantimonate; the molar ratio of dichloro (pentamethylcyclopentadienyl) rhodium dimer to silver hexafluoroantimonate was 1: 4.
the additive is any one or combination of 2,4, 6-trimethyl benzoic acid, pivalic acid, acetic acid, 1-adamantane formic acid, zinc acetate, sodium carbonate, potassium acetate and potassium carbonate.
The solvent is any one or combination of Dichloroethane (DCE), methanol (MeOH), acetonitrile (MeCN), 1,4-dioxane (1,4-dioxane) or toluene (tolumene).
The inert atmosphere is nitrogen atmosphere, and helium, neon, argon and other gas atmospheres can also be used.
The molar ratio of the oxazine compound 1, the diazo compound 2, the catalyst, the additive and the solvent is as follows: 1:(2-3):(0.02-0.04):(0.08-0.16).
The concentration of the reaction system in the solvent is 0.05M-0.2M.
The reaction mode of this reaction is shown in FIG. 31: firstly, a cyclometal intermediate A is obtained through the action of a substrate 1a and a catalyst, then a nitrogen-filled compound and the intermediate A act to obtain an intermediate B, the intermediate B is subjected to carbene migration and insertion to obtain an intermediate C, then metal removal is carried out to obtain an intermediate D, the intermediate D is subjected to the above process again to obtain a double-alkylated intermediate E, the intermediate E is rapidly converted into an enol form F, hydroxyl in the intermediate F attacks an imine bond to obtain an intermediate G, NH in the intermediate G carries out nucleophilic addition-elimination on carbonyl of another molecule to obtain an intermediate I, and then the intermediate I is subjected to continuous conversion such as acidification-ring opening-ring closing-dehydration to obtain the target nitrogen and oxa-condensed ring aromatic hydrocarbon 3 aa.
The invention has the beneficial effects that: the invention creatively selects simple and easily obtained oxazine compounds and diazo compounds as reactants, takes imine in the oxazine compounds as weak reactive type positioning group under the action of a metal rhodium catalyst, and realizes the construction of novel nitrogen and oxygen fused ring aromatic hydrocarbon frameworks in one step by a continuous [4+2] series strategy, the method has simple operation, obvious atom economy and step economy, provides a simple and effective method for the synthesis of hetero fused ring aromatic hydrocarbon, and the method has mild reaction conditions and the reaction temperature of 80-120 ℃; in addition, the yield of the prepared nitrogen and oxygen-containing polycyclic aromatic hydrocarbon is good, and the yield is generally over 80 percent and reaches 98 percent at most. The obtained product has wide industrial application prospect, and provides a new idea and a new method for the fields of medicine, natural product synthesis, luminescent materials and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is nuclear magnetism of Compound 3aa1H, spectrogram; FIG. 2 nuclear magnetism of Compound 3aa13And C, spectrum.
FIG. 3 nuclear magnetism of Compound 3ba1H, spectrogram; FIG. 4 nuclear magnetism of Compound 3ba13And C, spectrum.
FIG. 5 shows nuclear magnetism of Compound 3ca1H, spectrogram; FIG. 6 shows nuclear magnetism of Compound 3ca13And C, spectrum.
FIG. 7 nuclear magnetism of Compound 3da1H, spectrogram; FIG. 8 nuclear magnetism of Compound 3da13And C, spectrum.
FIG. 9 is nuclear magnetism of Compound 3ea1H, spectrogram; FIG. 10 is nuclear magnetism of Compound 3ea13And C, spectrum.
FIG. 11 is nuclear magnetism of compound 3fa1H, spectrogram; FIG. 12 nuclear magnetism of Compound 3fa13And C, spectrum.
FIG. 13 nuclear magnetism of Compound 3ga1H, spectrogram; FIG. 14 nuclear magnetism of Compound 3ga13And C, spectrum.
FIG. 15 is nuclear magnetism of compound 3ha1H, spectrogram; FIG. 16 is nuclear magnetism of compound 3ha13And C, spectrum.
FIG. 17 is nuclear magnetism of Compound 3ia1H, spectrogram; FIG. 18 is nuclear magnetism of Compound 3ia13And C, spectrum.
FIG. 19 Nuclear magnetism of Compound 3ja1H, spectrogram; FIG. 20 Nuclear magnetism of Compound 3ja13And C, spectrum.
FIG. 21 nuclear magnetism of Compound 3ka1H, spectrogram; FIG. 22 is nuclear magnetism of compound 3ka13And C, spectrum.
FIG. 23 NMR of Compound 3ab1H, spectrogram; FIG. 24 NMR of Compound 3ab13And C, spectrum.
FIG. 25 nuclear magnetism of Compound 3ac1H, spectrogram; FIG. 26 nuclear magnetism of Compound 3ac13And C, spectrum.
FIG. 27 NMR of Compound 3ad1H, spectrogram; FIG. 28 is nuclear magnetism of Compound 3ad13And C, spectrum.
FIG. 29 Nuclear magnetism of Compound 3ae1H, spectrogram; FIG. 30 NMR of Compound 3ae13And C, spectrum.
FIG. 31 is a diagram showing the reaction mechanism of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without inventive step, are within the scope of the present invention.
Example 1
Under the condition of nitrogen, 3-aryl benzoxazine compound 1a (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in an 80 ℃ reaction block for 10h, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 5, 12-dimethylisoquinoline [2,1,8-mna ], was isolated on a silica gel column]Diethylphenoxazine-4, 13-dicarboxylate (3aa), all eluents were petroleum ether ethyl acetate and dichloromethane at 30: 1: 1, is prepared according to the proportion of 1. And (3) product data characterization: tan liquid, 78% yield. The nuclear magnetic spectrum of the product is shown in figures 1 and 2,1H NMR(400MHz,CDCl3)δ7.23(d,J＝8.6Hz,1H),7.11(t,J＝8.0Hz,1H),7.03–6.97(m,1H),6.94(t,J＝7.6Hz,1H),6.89(d,J＝7.7Hz,1H),6.82(d,J＝7.9Hz,1H),6.77(d,J＝7.3Hz,1H),4.49–4.38(m,4H),2.33(s,6H),1.45–1.40(m,6H).13CNMR(101MHz,CDCl3)δ168.6,167.7,150.6,138.6,137.1,131.2,130.2,129.1,128.4,127.7,125.8,125.7,125.0,123.9,123.6,120.1,119.6,117.1,116.8,115.2,61.1,61.0,19.0,14.4,14.3,13.2.HRMS：[M+H]+calculated for C26H24NO5 +：430.1649,found：430.1635.
example 2
Under the condition of nitrogen, 3-aryl benzoxazine compound 1b (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in a 80 ℃ reaction block for 10h, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 7-bromo-5, 12-dimethylisoquinoline [2,1,8-mna ], was isolated on a silica gel column]Diethylphenoxazine-4, 13-dicarboxylate (3ba) all eluents were petroleum ether ethyl acetate and dichloromethane at 30: 1: 1, is prepared according to the proportion of 1. And (3) product data characterization: tan solid, 98% yield, melting range: 119-120 ℃. The nuclear magnetic spectrum of the product is shown in figures 3 and 4,1H NMR(400MHz,CDCl3)δ7.26(t,J＝8.3Hz,2H),7.14(t,J＝8.0Hz,1H),6.86(t,J＝8.0Hz,1H),6.79(dd,J＝7.5,4.6Hz,2H),4.49–4.39(m,4H),2.44(s,3H),2.33(s,3H),1.45–1.40(m,6H).13C NMR(101MHz,CDCl3)δ168.6,167.6,147.7,138.0,137.1,132.0,131.0,129.2,128.8,128.7,128.0,126.3,124.7,124.6,124.0,120.6,118.5,117.6,115.7,111.2,61.3,61.2,19.0,14.4,14.4,13.5.HRMS：[M+H]+calculated for C26H23BrNO5 +：508.0754,found：508.0717.
example 3
Under the condition of nitrogen, 3-aryl benzoxazine compound 1c (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in a 80 ℃ reaction block for 10h, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 8-fluoro-5, 12-dimethylisoquinoline [2,1,8-mna ], was isolated on a silica gel column]Diethylphenoxazine-4, 13-dicarboxylate (3ca) was added to the eluent petroleum ether ethyl acetate and dichloromethane at 30: 1: 1, is prepared according to the proportion of 1. Product data characterization: yellow solid, 89% yield, melting range: 104-105 ℃. The nuclear magnetic spectrum of the product is shown in figures 5 and 6,1H NMR(400MHz,CDCl3)δ7.26(t,J＝8.3Hz,2H),7.14(t,J＝8.0Hz,1H),6.86(t,J＝8.0Hz,1H),6.79(dd,J＝7.5,4.6Hz,2H),4.49–4.39(m,4H),2.44(s,3H),2.33(s,3H),1.45–1.40(m,6H).13C NMR(101MHz,CDCl3)δ168.6,167.6,147.7,138.0,137.1,132.0,131.0,129.2,128.8,128.7,128.0,126.3,124.7,124.6,124.0,120.6,118.5,117.6,115.7,111.2,61.3,61.2,19.0,14.4,14.4,13.5.HRMS：[M+Na]+calculated for C26H22FNNaO5 +：470.1374,found：470.1371.
example 4
Under the condition of nitrogen, 3-aryl benzoxazine compound 1d (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in an 80 ℃ reaction block for 10h, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 8-chloro-5, 12-dimethylisoquinoline [2,1,8-mna ], was isolated on a silica gel column]Diethylphenoxazine-4, 13-dicarboxylate (3da), all eluents were petroleum ether ethyl acetate and dichloromethane at 30: 1: 1, is prepared according to the proportion of 1. And (3) product data characterization: tan solid, 82% yield, melting range: 127 ℃ and 128 ℃. Nuclear magnetic resonance of the productThe maps are shown in figures 7 and 8,1H NMR(400MHz,CDCl3)δ7.21(d,J＝8.6Hz,1H),7.15–7.06(m,1H),6.98–6.89(m,2H),6.74(t,J＝7.6Hz,2H),4.46–4.36(m,4H),2.30(s,3H),2.29(s,3H),1.43-1.38(m,6H).13C NMR(101MHz,CDCl3)13C NMR(101MHz,CDCl3)δ168.6,167.7,151.2,138.0,136.8,131.1,130.9,129.2,128.9,128.6,128.0,125.9,124.9,124.0,123.9,120.4,119.9,117.7,117.3,115.6,61.4,61.2,19.0,14.5,14.4,13.3.HRMS：[M+H]+calculated for C26H23ClNO5 +：464.1259,found：464.1244.
example 5
Under the condition of nitrogen, 3-aryl benzoxazine compound 1e (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in a 80 ℃ reaction block for 10h, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 8-bromo-5, 12-dimethylisoquinoline [2,1,8-mna ], was isolated on a silica gel column]Diethylphenoxazine-4, 13-dicarboxylate (3ea), all eluents were petroleum ether ethyl acetate and dichloromethane at 30: 1: 1, is prepared according to the proportion of 1. And (3) product data characterization: yellow solid, 89% yield, melting range: 144 ℃ and 145 ℃. The nuclear magnetic spectrum of the product is shown in figures 9 and 10,1H NMR(400MHz,CDCl3)δ7.20(d,J＝8.6Hz,1H),7.13–7.00(m,3H),6.74(d,J＝7.2Hz,1H),6.64(d,J＝8.4Hz,1H),4.46–4.35(m,4H),2.28(s,3H),2.27(s,3H),1.40(td,J＝7.1,5.2Hz,6H).13C NMR(101MHz,CDCl3)δ168.5,167.6,151.2,137.9,136.8,130.8,129.6,128.8,128.5,127.9,126.9,125.8,124.8,123.9,120.4,120.4,120.2,118.3,117.3,115.6,61.3,61.2,18.9,14.4,14.4,13.2.HRMS：[M+Na]+calculated for C26H22BrNNaO5 +＝530.0574,found：530.0564.
example 6
Under the condition of nitrogen, 3-aryl benzoxazine compound 1f (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in an 80 ℃ reaction block for 10h, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 8-methyl-5, 12-dimethylisoquinoline [2,1,8-mna ], was isolated on a silica gel column]Diethylphenoxazine-4, 13-dicarboxylate (3fa), all eluents were petroleum ether ethyl acetate and dichloromethane at 30: 1: 1, is prepared according to the proportion of 1. And (3) product data characterization: yellow solid, 77% yield, melting range: 100-101 ℃. The nuclear magnetic spectrum of the product is shown in figures 11 and 12,1H NMR(400MHz,CDCl3)δ7.18(d,J＝8.6Hz,1H),7.08(t,J＝8.0Hz,1H),6.78–6.68(m,4H),4.48–4.34(m,4H),2.31(s,3H),2.31(s,3H),2.26(s,3H),1.40(td,J＝7.1,3.7Hz,6H).13C NMR(101MHz,CDCl3)δ168.8,168.0,150.6,139.0,137.1,136.1,131.4,129.3,128.4,127.8,127.5,125.9,125.1,124.4,123.4,120.0,119.4,117.9,116.2,115.1,61.2,61.0,20.7,19.2,14.5,14.4,13.3.HRMS：[M+Na]+calculated for C27H25NNaO5 +＝466.1625,found：466.1617.
example 7
Under the nitrogen condition, 1g (0.20mmol) of 3-aryl benzoxazine compound, 2a (0.44mmol) of diazo compound, [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in a 80 ℃ reaction block for 10h, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 9-bromo-5, 12-dimethylisoquinoline [2,1,8-mna ], was isolated on a silica gel column]Phenoxazine-4, 13-dicarboxylic acid diethyl ester(3ga), all eluents were petroleum ether ethyl acetate and dichloromethane at 30: 1: 1, is prepared according to the proportion of 1. And (3) product data characterization: yellow solid, 91% yield, melting range: 132 ℃ and 133 ℃. The nuclear magnetic spectrum of the product is shown in figures 13 and 14,1H NMR(400MHz,CDCl3)δ7.21(d,J＝8.6Hz,1H),7.13–7.08(m,2H),6.94(d,J＝1.6Hz,1H),6.77–6.74(m,2H),4.45–4.37(m,4H),2.31(s,3H),2.30(s,3H),1.43–1.39(m,6H).13C NMR(101MHz,CDCl3)δ168.6,167.6,149.8,137.6,137.1,131.8,130.7,128.7,128.4,128.4,128.0,125.9,124.8,124.2,122.3,120.6,118.3,117.9,116.3,115.8,61.4,61.3,18.9,14.5,14.4,13.3.HRMS：[M+H]+calculated for C26H23BrNO5 +＝508.0754,found：508.0747.
example 8
Under the nitrogen condition, 1h (0.20mmol) of 3-aryl benzoxazine compound, 2a (0.44mmol) of diazo compound and [ Cp & RhCl ] are added2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in an 80 ℃ reaction block for 10h, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 9-methoxy-5, 12-dimethylisoquinoline [2,1,8-mna ], was isolated on a silica gel column]Diethylphenoxazine-4, 13-dicarboxylate (3ha) was added to all eluents petroleum ether ethyl acetate and dichloromethane at 30: 1: 1 in proportion. And (3) product data characterization: yellow solid, 53% yield, melting range: 162 ℃ and 163 ℃. The nuclear magnetic spectrum of the product is shown in figures 15 and 16,1H NMR(400MHz,CDCl3)δ7.20(d,J＝8.3Hz,1H),7.14–7.04(m,1H),6.80(d,J＝8.8Hz,1H),6.74(d,J＝7.0Hz,1H),6.52(dd,J＝8.8,2.6Hz,1H),6.39(d,J＝2.7Hz,1H),4.46–4.36(m,4H),2.34(s,3H),2.31(s,3H),1.42–1.38(m,6H).13C NMR(101MHz,CDCl3)δ168.7,167.8,156.2,144.2,138.4,137.6,131.0,130.9,128.9,128.2,127.6,125.9,125.0,123.7,120.3,117.0,115.3,109.4,106.6,61.2,61.1,55.9,19.2,14.4,14.4,13.3.HRMS：[M+H]+calculated for C27H26NO6 +＝460.1755,found：460.1753.
example 9
Under the condition of nitrogen, 3-aryl benzoxazine compound 1i (0.20mmol), diazo compound 2a (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) are added into a 10mL sealed tube, the mixture reacts in a reaction module of 80 ℃ for 10h, the solvent is removed under reduced pressure after the reaction is finished, and the target product 2-fluoro-5, 12-dimethylisoquinoline [2,1,8-mna ] is obtained by silica gel column separation]Diethylphenoxazine-4, 13-dicarboxylate (3ia), all eluents were petroleum ether ethyl acetate and dichloromethane at 30: 1: 1, is prepared according to the proportion of 1. Product data characterization: yellow solid, 82% yield, melting range: 162 ℃ and 163 ℃. The nuclear magnetic spectrum of the product is shown in figures 17 and 18,1H NMR(400MHz,CDCl3)δ7.07–7.03(m,1H),7.00–6.96(m,1H),6.92(dd,J＝7.9,1.5Hz,1H),6.88(dd,J＝11.4,2.0Hz,1H),6.85(dd,J＝8.0,1.2Hz,1H),6.61(dd,J＝10.2,2.0Hz,1H),4.46–4.37(m,4H),2.37(s,3H),2.32(s,3H),1.43–1.39(m,6H).13C NMR(101MHz,CDCl3)δ168.2,167.1,162.6(d,J＝243.1Hz),150.7,140.8,136.6,131.9(d,J＝11.2Hz),131.3,129.6,129.5,127.3,126.2,123.9,122.8(d,J＝5.4Hz),122.2,120.0,117.3,115.5,105.4(d,J＝29.2Hz),103.8(d,J＝24.6Hz),61.2,61.2,19.4,14.4,14.3,13.4.HRMS：[M+H]+calculated for C26H23FNO5 +＝448.1555,found：448.1539.
example 10
Under the condition of nitrogen, 3-aryl benzoxazine compound 1j (0.20mmol), diazo compound 2a (0.44mmol), [ Cp ] RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) are added into a 10mL sealed tube, the mixture reacts in a reaction module of 80 ℃ for 10h, the solvent is removed under reduced pressure after the reaction is finished, and the target product 2-bromo-5, 12-dimethylisoquinoline [2,1,8-mna ] is obtained by silica gel column separation]Phenoxazine-4, 13-dicarboxylic acid diethyl ester (3ja), all eluents were petroleum ether ethyl acetate and dichloromethane at 30: 1: 1, is prepared according to the proportion of 1. And (3) product data characterization: yellow solid, 87% yield, melting range: 142 ℃ and 143 ℃. The nuclear magnetic spectrum of the product is shown in figures 19 and 20,1H NMR(400MHz,CDCl3)δ7.39d,J＝1.5Hz,1H),7.10–7.05(m,1H),7.03–7.01(m,1H),6.94(dd,J＝7.8,1.5Hz,1H),6.89–6.84(m,2H),4.49–4.39(m,4H),2.38(s,3H),2.34(s,3H),1.45–1.42(m,6H).13C NMR(101MHz,CDCl3)δ168.1,167.2,150.7,140.5,137.4,131.3,131.0,129.7,129.4,127.0,126.3,124.2,123.6,122.8,122.1,120.0,118.4,117.4,115.4,77.2,61.4,61.3,19.4,14.4,14.4,13.4.HRMS：[M+H]+calculated for C26H23BrNO5 +＝508.0754,found：508.0742.
example 11
Under the nitrogen condition, 3-aryl benzoxazine compound 1k (0.20mmol), diazo compound 2a (0.44mmol), [ Cp × RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) are added into a 10mL sealed tube, the mixture reacts in a reaction module of 80 ℃ for 10h, the solvent is removed under reduced pressure after the reaction is finished, and the target product, 2-methoxy-5, 12-dimethyl isoquinoline [2,1,8-mna ], is obtained by silica gel column separation]Phenoxazine-4, 13-dicarboxylic acid diethyl ester (3ka), all eluents were petroleum ether ethyl acetate and dichloromethane at 30: 1: 1, is prepared according to the proportion of 1. And (3) product data characterization: red solid, 77% yield, melting range: 172 ℃ and 173 ℃. The nuclear magnetic spectrum of the product is shown in figures 21 and 22,1H NMR(400MHz,CDCl3)δ7.52(s,1H),7.08(t,J＝7.7Hz,1H),7.03–6.99(m,1H),6.95–6.93(m,2H),6.88–6.86(d,J＝7.4Hz,1H),4.49(q,J＝7.1Hz,1H),4.43(q,J＝7.2Hz,1H),2.39(s,3H),2.36(s,3H),1.45–1.41(m,6H).13C NMR(101MHz,CDCl3)δ167.9,167.2,150.5,140.9,138.7,131.1,130.7,129.7(q,J＝31.8Hz),129.5,127.3,126.3,126.2,124.7,124.3,124.2(q,J＝272.7Hz),120.0,117.7(dd,J＝9.2),117.7(d,J＝4.7Hz),117.4,115.7,110.8(d,J＝3.2Hz).61.5,61.3,19.5,14.3,14.3,13.3.HRMS：[M+H]+calculated for C27H23F3NO5 +＝498.1523,found：498.1508.
example 12
Under the condition of nitrogen, 3-aryl benzoxazine compound 1a (0.20mmol), diazo compound 2b (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in an 80 ℃ reaction block for 10h, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 5, 12-dimethylisoquinoline [2,1,8-mna ], was isolated on a silica gel column]Phenoxazine-4, 13-dicarboxylic acid dipentyl ester (3ab) with all eluents petroleum ether ethyl acetate and dichloromethane at 30: 1: 1 in proportion. And (3) product data characterization: yellow liquid, 96% yield. The nuclear magnetic spectrum of the product is shown in figures 23 and 24,1H NMR(400MHz,CDCl3)δ7.23–7.15(m,1H),7.09(t,J＝7.9Hz,1H),7.03(t,J＝7.4Hz,1H),6.99–6.95(m,1H),6.91(dd,J＝7.7,1.6Hz,1H),6.84(d,J＝7.7Hz,1H),6.79–6.67(m,1H),4.36(t,J＝6.7Hz,3H),4.31(t,J＝6.8Hz,3H),2.32(s,3H),2.31(s,3H),1.80–1.73(m,4H),1.43–1.36(m,8H),0.95–0.90(m,6H).13C NMR(101MHz,CDCl3)δ168.9,168.0,150.7,138.6,137.2,131.3,130.3,129.2,128.4,127.8,125.9,125.8,125.1,124.0,123.7,120.2,119.7,117.2,116.9,115.3,65.4,65.3,28.5,28.4,28.3,28.3,22.4,22.4,19.1,14.1,14.1,13.3.HRMS：[M+H]+calculated for C32H36NO5 +＝514.2588,found：514.2577.
example 13
Under the condition of nitrogen, 3-aryl benzoxazine compound 1a (0.20mmol), diazo compound 2c (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in an 80 ℃ reaction block for 10h, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 5, 12-dimethylisoquinoline [2,1,8-mna ], was isolated on a silica gel column]Phenoxazine-4, 13-dicarboxylic acid diisopropyl ester (3ac) and all eluents were petroleum ether ethyl acetate and dichloromethane at 30: 1: 1 in proportion. Product data characterization: red liquid, 80% yield. The nuclear magnetic spectrum of the product is shown in figures 25 and 26,1H NMR(400MHz,CDCl3)δ7.24(d,J＝23.1Hz,1H),7.16–7.07(m,1H),7.02–6.89(m,3H),6.84–6.80(m,1H),6.75–6.70(m,1H),5.39–5.28(m,2H),2.33(s,6H),1.44–1.36(m,12H).13C NMR(101MHz,CD Cl3)δ168.1,167.2,150.5,137.9,137.1,131.1,130.2,129.1,128.2,127.7,125.6,125.4,125.0,123.9,119.9,119.5,117.1,114.9,68.8,68.7,22.0,21.9,18.9,13.1.HRMS：[M+H]+calculated for C28H28NO5 +＝458.1962,found：458.1943.
example 14
Under the condition of nitrogen, 3-aryl benzoxazine compound 1a (0.20mmol), diazo compound 2d (0.44mmol), [ Cp + RhCl2]2(4mol％)，AgSbF6(16mol percent), MesCOOH (0.4mmol) and a solvent DCE (2.0mL) are added into a 10mL sealed tube and reacted for 10 hours in a reaction module with the temperature of 80 ℃, the solvent is removed under reduced pressure after the reaction is finished, and the target product 5, 12-diethylisoquinoline is obtained by silica gel column separationQuinoline [2,1,8-mna ]]Phenoxazine-4, 13-dicarboxylic acid dimethyl ester (3ad), all eluents were petroleum ether ethyl acetate and dichloromethane at 30: 1: 1, is prepared according to the proportion of 1. And (3) product data characterization: yellow liquid, 60% yield. The nuclear magnetic spectrum of the product is shown in figures 27 and 28,1H NMR(400MHz,CDCl3)δ7.17(t,J＝8.5Hz,1H),7.13–7.08(m,1H),7.07–7.03(m,1H),7.01–6.95(m,1H),6.94–6.88(m,2H),6.70(d,J＝7.1Hz,1H),3.94(s,3H),3.91(s,3H),2.81–2.74(m,2H),2.69(dd,J＝8.7,6.8Hz,2H),1.71–1.52(m,4H),0.99(t,J＝7.4Hz,3H),0.94(t,J＝7.3Hz,3H).13C NMR(101MHz,CDCl3)δ169.3,168.5,150.7,142.8,137.4,132.2,131.6,130.9,129.0,128.5,127.8,125.7,124.9,124.1,123.1,120.8,119.3,118.2,117.3,115.6,52.2,52.2,32.4,30.2,23.9,22.8,14.5,13.9.HRMS：[M+H]+calculated for C28H28NO5 +＝458.1962,found：458.1949.
example 15
Under the nitrogen condition, 3-aryl benzoxazine compound 1a (0.20mmol), diazo compound 2e (0.44mmol), [ Cp × RhCl2]2(4mol％)，AgSbF6(16 mol%), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, reacted in a 80 ℃ reaction block for 10h, after the reaction was completed, the solvent was removed under reduced pressure, and the desired product, 5, 12-dipropylisoquinoline [2,1,8-mna ], was isolated by silica gel column]Phenoxazine-4, 13-dicarboxylic acid dimethyl ester (3ae), all eluents were petroleum ether ethyl acetate and dichloromethane at 30: 1: 1, is prepared according to the proportion of 1. And (3) product data characterization: yellow liquid, 63% yield. The nuclear magnetic spectrum of the product is shown in figures 29 and 30,1H NMR(400MHz,CDCl3)δ7.19(dd,J＝8.6,0.7Hz,1H),7.13–7.09(m,1H),7.07–7.03(m,1H),7.00–6.96(m,1H),6.93(dd,J＝7.8,1.5Hz,0H),6.90(dd,J＝7.9,1.4Hz,1H),6.70(dd,J＝7.2,0.7Hz,1H),3.94(s,3H),3.91(s,3H),2.82–2.79(m,2H),2.76–2.65(m,2H),1.65–1.51(m,4H),1.48–1.39(m,2H),1.37–1.32(m,2H),0.96(t,J＝7.3Hz,3H),0.85(t,J＝7.3Hz,3H).13C NMR(101MHz,CDCl3)δ169.3,168.5,150.7,143.1,137.4,132.2,131.6,131.2,129.1,128.5,127.7,125.7,124.8,124.1,123.0,120.7,119.3,118.1,117.2,115.5,52.2,52.1,32.7,31.5,30.1,27.9,23.0,22.4,14.1,13.8.HRMS：[M+H]+calculated for C30H32NO5 +＝486.2275,found：486.2266.
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A nitrogen and oxygen fused ring aromatic hydrocarbon is characterized in that the structural formula is as follows:
wherein R is any one of H, Me, OMe, F, Cl or Br; r1Any one of Me, n-Pr or Ph; r2Is n-Am oriPr; ar is Me, OMe, F, Cl, Br, Ph or CF3Any substituted benzene ring.
2. A process for the synthesis of nitrogen and oxa-fused ring aromatic hydrocarbons as claimed in claim 1, comprising the steps of: adding an oxazine compound 1, a diazo compound 2, a catalyst and an additive into a solvent in an inert atmosphere for reaction to obtain a hetero-condensed ring aromatic compound 3 after the reaction is finished, wherein the reaction equation is as follows:
wherein R is any one of H, Me, OMe, F, Cl or Br; r1Any one of Me, n-Pr or Ph; r2Is n-Am oriPr；Ar is Me, OMe, F, Cl, Br, Ph or CF3Any substituted benzene ring.
3. The method for synthesizing nitrogen-and oxa-condensed ring aromatic hydrocarbons according to claim 2, wherein: the reaction temperature is 80-120 ℃ in the reaction process, and the reaction time is 6-12 h.
4. A method for synthesizing nitrogen-and oxa-condensed ring aromatic hydrocarbons according to claim 2 or 3, wherein: the catalyst comprises a rhodium catalyst and a silver salt; the molar ratio of rhodium catalyst to silver salt is 1: 4; the rhodium catalyst is any one or combination of dichloro (pentamethylcyclopentadienyl) rhodium dimer, pentamethylcyclopentadienyl rhodium acetate or bis (hexafluoroantimonate) triethylenenitrile (pentamethylcyclopentadienyl) rhodium; the silver salt is any one or combination of silver hexafluoroantimonate, silver tetrafluoroborate, silver bistrifluoromethanesulfonimide, silver trifluoromethanesulfonate, silver sulfate, silver acetate and silver trifluoroacetate.
5. The method for synthesizing nitrogen-and oxa-condensed ring aromatic hydrocarbons according to claim 4, wherein: the catalyst consists of dichloro (pentamethyl cyclopentadienyl) rhodium dimer and silver hexafluoroantimonate; the molar ratio of dichloro (pentamethylcyclopentadienyl) rhodium dimer to silver hexafluoroantimonate was 1: 4.
6. the method for synthesizing nitrogen-and oxa-condensed ring aromatic hydrocarbons according to claim 5, wherein: the additive is any one or combination of 2,4, 6-trimethyl benzoic acid, pivalic acid, acetic acid, 1-adamantane formic acid, zinc acetate, sodium carbonate, potassium acetate or potassium carbonate.
7. The method for synthesizing nitrogen-and oxa-condensed ring aromatic hydrocarbons according to claim 6, wherein: the solvent is any one or combination of dichloroethane, methanol, acetonitrile, 1,4-dioxane or toluene.
8. A method of synthesizing nitrogen and oxa-polycyclic aromatic hydrocarbons according to any one of claims 5 to 7, wherein: the inert atmosphere is nitrogen atmosphere.
9. The method as recited in claim 8, wherein the nitrogen-and oxygen-containing condensed ring aromatic hydrocarbon is synthesized by: the molar ratio of the oxazine compound 1, the diazo compound 2, the catalyst, the additive and the solvent is as follows: 1:(2-3):(0.02-0.04):(0.08-0.16).
10. The method for synthesizing nitrogen-and oxa-condensed ring aromatic hydrocarbons according to claim 9, wherein: the concentration of the reaction system in the solvent is 0.05M-0.2M.
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