CN101941949B - Triazole heterocyclic compound and synthesis method thereof - Google Patents
Triazole heterocyclic compound and synthesis method thereof Download PDFInfo
- Publication number
- CN101941949B CN101941949B CN2010102789771A CN201010278977A CN101941949B CN 101941949 B CN101941949 B CN 101941949B CN 2010102789771 A CN2010102789771 A CN 2010102789771A CN 201010278977 A CN201010278977 A CN 201010278977A CN 101941949 B CN101941949 B CN 101941949B
- Authority
- CN
- China
- Prior art keywords
- triazole
- carbonyl
- oxygen
- parts
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- -1 Triazole heterocyclic compound Chemical class 0.000 title abstract description 27
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000001311 chemical methods and process Methods 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 150000003852 triazoles Chemical class 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 10
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical compound C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 9
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 8
- BLFLLBZGZJTVJG-UHFFFAOYSA-N benzocaine Chemical compound CCOC(=O)C1=CC=C(N)C=C1 BLFLLBZGZJTVJG-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 6
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 6
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229960005274 benzocaine Drugs 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- ASWXNYNXAOQCCD-UHFFFAOYSA-N dichloro(triphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Cl)(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ASWXNYNXAOQCCD-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical class [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 2
- 235000010288 sodium nitrite Nutrition 0.000 claims description 2
- 235000019187 sodium-L-ascorbate Nutrition 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 10
- 230000008859 change Effects 0.000 abstract description 3
- MHFFHHOWVDJOSC-UHFFFAOYSA-N benzoyloxy(diazonio)azanide Chemical compound [N-]=[N+]=NOC(=O)C1=CC=CC=C1 MHFFHHOWVDJOSC-UHFFFAOYSA-N 0.000 abstract 1
- OUXAMGADSWZSFV-UHFFFAOYSA-N ethynyl benzoate Chemical compound C#COC(=O)C1=CC=CC=C1 OUXAMGADSWZSFV-UHFFFAOYSA-N 0.000 abstract 1
- 238000004020 luminiscence type Methods 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 description 112
- 239000001301 oxygen Substances 0.000 description 112
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 46
- UEGRWYULHGETCH-UHFFFAOYSA-N O=C=C1CNN=N1 Chemical compound O=C=C1CNN=N1 UEGRWYULHGETCH-UHFFFAOYSA-N 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- JNUDFWIMKSRIJR-UHFFFAOYSA-N C(=O)=C1N=NNC1.[O] Chemical compound C(=O)=C1N=NNC1.[O] JNUDFWIMKSRIJR-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- DDJUWJIXDASYPW-UHFFFAOYSA-N C(=O)=C1N=NNC1.CCCCCCC Chemical compound C(=O)=C1N=NNC1.CCCCCCC DDJUWJIXDASYPW-UHFFFAOYSA-N 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UUGLJVMIFJNVFH-UHFFFAOYSA-N Hexyl benzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1 UUGLJVMIFJNVFH-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LPDDEDLHJGHRJZ-UHFFFAOYSA-N C(=O)OCCCCCC.C(#C)C1=CC=CC=C1 Chemical compound C(=O)OCCCCCC.C(#C)C1=CC=CC=C1 LPDDEDLHJGHRJZ-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000006193 diazotization reaction Methods 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 3
- UBRIHZOFEJHMIT-UHFFFAOYSA-N 4-butoxyaniline Chemical compound CCCCOC1=CC=C(N)C=C1 UBRIHZOFEJHMIT-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 3
- 235000005291 Rumex acetosa Nutrition 0.000 description 3
- 240000007001 Rumex acetosella Species 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 235000003513 sheep sorrel Nutrition 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- OMXUBCXAGLQCRX-UHFFFAOYSA-N 1-azido-4-butoxybenzene Chemical compound CCCCOC1=CC=C(N=[N+]=[N-])C=C1 OMXUBCXAGLQCRX-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- BVLVGYXYGXOSOG-UHFFFAOYSA-N 2-hexoxybenzoic acid Chemical compound CCCCCCOC1=CC=CC=C1C(O)=O BVLVGYXYGXOSOG-UHFFFAOYSA-N 0.000 description 2
- 0 Nc1ccc(*c(cc2)ccc2O)cc1 Chemical compound Nc1ccc(*c(cc2)ccc2O)cc1 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- CTRLRINCMYICJO-UHFFFAOYSA-N phenyl azide Chemical class [N-]=[N+]=NC1=CC=CC=C1 CTRLRINCMYICJO-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- FOYZORGYMUFUBD-UHFFFAOYSA-N 1-(4-chloroquinazolin-2-yl)-n,n-dimethylmethanamine Chemical compound C1=CC=CC2=NC(CN(C)C)=NC(Cl)=C21 FOYZORGYMUFUBD-UHFFFAOYSA-N 0.000 description 1
- SUJLHSOMNWYXHK-UHFFFAOYSA-N 1-azido-2-butoxybenzene Chemical compound C(CCC)OC1=C(C=CC=C1)N=[N+]=[N-] SUJLHSOMNWYXHK-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical group C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- ZXEKNGSPPHUBEJ-UHFFFAOYSA-N C(=O)OCCC.C(#C)C1=CC=CC=C1 Chemical compound C(=O)OCCC.C(#C)C1=CC=CC=C1 ZXEKNGSPPHUBEJ-UHFFFAOYSA-N 0.000 description 1
- SOWBRSFFNSOIEW-UHFFFAOYSA-N C(=O)OCCCC.C(#C)C1=CC=CC=C1 Chemical compound C(=O)OCCCC.C(#C)C1=CC=CC=C1 SOWBRSFFNSOIEW-UHFFFAOYSA-N 0.000 description 1
- CWWNXLZPCJGWPZ-UHFFFAOYSA-N C(=O)OCCCCCCC.C(#C)C1=CC=CC=C1 Chemical compound C(=O)OCCCCCCC.C(#C)C1=CC=CC=C1 CWWNXLZPCJGWPZ-UHFFFAOYSA-N 0.000 description 1
- WWZBPWMTWXOBNE-UHFFFAOYSA-N C(=O)OCCCCCCCC.C(#C)C1=CC=CC=C1 Chemical compound C(=O)OCCCCCCCC.C(#C)C1=CC=CC=C1 WWZBPWMTWXOBNE-UHFFFAOYSA-N 0.000 description 1
- BVUCLAQQBQKEKE-UHFFFAOYSA-N C(=O)OCCCCCCCCC.C(#C)C1=CC=CC=C1 Chemical compound C(=O)OCCCCCCCCC.C(#C)C1=CC=CC=C1 BVUCLAQQBQKEKE-UHFFFAOYSA-N 0.000 description 1
- UBANSPYNNCQJAP-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OCCCC(CCCCCC)N=[N+]=[N-] Chemical compound C(C1=CC=CC=C1)(=O)OCCCC(CCCCCC)N=[N+]=[N-] UBANSPYNNCQJAP-UHFFFAOYSA-N 0.000 description 1
- BDTGOTKWFOHNEK-UHFFFAOYSA-N CCCC(CC)OC1=CC=C(COC(=O)C2(CC=CC=C2)C=2N=NNC2)C=C1 Chemical compound CCCC(CC)OC1=CC=C(COC(=O)C2(CC=CC=C2)C=2N=NNC2)C=C1 BDTGOTKWFOHNEK-UHFFFAOYSA-N 0.000 description 1
- RXZIKEGEXDXSFE-UHFFFAOYSA-N CCCCOC1(CC=CC=C1)C=1N=NNC1 Chemical compound CCCCOC1(CC=CC=C1)C=1N=NNC1 RXZIKEGEXDXSFE-UHFFFAOYSA-N 0.000 description 1
- XEAMDSXSXYAICO-UHFFFAOYSA-N Heptyl formate Chemical compound CCCCCCCOC=O XEAMDSXSXYAICO-UHFFFAOYSA-N 0.000 description 1
- OUGPMNMLWKSBRI-UHFFFAOYSA-N Hexyl formate Chemical compound CCCCCCOC=O OUGPMNMLWKSBRI-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- KFSSLUMKUDMRLD-UHFFFAOYSA-N ethyl formate ethynylbenzene Chemical compound C(=O)OCC.C(#C)C1=CC=CC=C1 KFSSLUMKUDMRLD-UHFFFAOYSA-N 0.000 description 1
- IDPWCJIIGUAMEF-UHFFFAOYSA-N ethynylbenzene pentyl formate Chemical compound C(=O)OCCCCC.C(#C)C1=CC=CC=C1 IDPWCJIIGUAMEF-UHFFFAOYSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000004001 molecular interaction Effects 0.000 description 1
- PNSKQSWNGULNLS-UHFFFAOYSA-N n-butoxyaniline Chemical compound CCCCONC1=CC=CC=C1 PNSKQSWNGULNLS-UHFFFAOYSA-N 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- AVBRYQRTMPHARE-UHFFFAOYSA-N octyl formate Chemical compound CCCCCCCCOC=O AVBRYQRTMPHARE-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention relates to a triazole heterocyclic compound and a synthesis method thereof, belonging to the technical field of organic synthesis of liquid crystal compounds and liquid crystal materials. The triazole heterocyclic compound is synthetized from azido benzoate and acetenyl benzoate by a click chemistry method. The nolinear triazole heterocyclic compound synthetized by a simple, convenient and easily operated method has the advantages of wider SmA phase, good stability and the like; and in addition, the triazole heterocyclic compound also has the obvious advantages of aromaticity, large dipole moment and the like, and can change the dipole moment, the dielectric anisotropy, luminescence and other performances of liquid crystal molecular, thus introduction of the triazole heterocyclic compound into the liquid crystal molecular has great significance for researching the liquid crystal performance of the compound, designing and developing novel function materials, etc.
Description
Technical field
The present invention relates to one type and contain triazole heterogeneous ring compound and compound method thereof, belong to the technical field of organic synthesis of liquid crystalline cpd and liquid crystal material.
Background technology
In recent years, liquid crystalline cpd and liquid crystal material have obtained using widely in each side such as electronics, optics, acoustics, biotechnology, chemical industry, become one of focus of applied chemistry and materials chemistry research.Therefore the novel liquid crystal material is synthetic, and the structure of liquid crystal molecule and the relation between the performance become an integral part of research.
The factor of decision liquid crystal practical application mainly contains the symbol and size, optical anisotropy etc. of mesomorphic phase kind, phase transition temperature, dielectric anisotropy, and the heterocycle liquid crystal these play an important role in nature in raising.
The heteroatomic introducing that polarizability is big can influence the polarity of molecule, thereby the other heteroatoms of phase transition temperature that geometric configuration influences liquid crystal possibly influence molecular interaction, makes mesomorphic phase type (Parra M L, the Saavedra C G of liquid crystal molecule; Hidalgo P I.Liquid Crystals, 2008,35 (1): 55-64.); Dipole moment direction and size, and the symbol of dielectric anisotropy and size (Dingemans T J, Murthy N S; Samulski E T.J.Phys.Chem.B; 2001,105:8845-8860.) grade changes, and also possibly influence the luminous of molecule and other character in addition.Thereby contain the heterocyclic liquid crystal the design synthesizing new functional materials aspect playing an important role.
Contain the compound of [1,2,3]-triazole ring because it has plurality of advantages such as chemicalstability height, dipole moment are big, aromaticity, be widely used in every field such as materials chemistry, organic chemistry, pharmaceutical chemistry and biological chemistry.Can be used as dyestuff, sanitas, photostabilizer and photovaltaic material etc., and triazole ring is less relatively as the research of liquid crystal material.
Summary of the invention
The purpose of this invention is to provide one type and contain triazole heterogeneous ring compound and compound method thereof, should adopt easy, easy-operating method to synthesize non-linear triazole heterogeneous ring compound, this compound should have characteristics such as the SmA phase, good stability of broad; Also should have outstanding advantages such as aromaticity, dipole moment be big, can change the dipole moment, dielectric anisotropy of liquid crystal molecule, various character such as luminous.
Technical scheme of the present invention is: one type of molecular structural formula that contains the triazole heterogeneous ring compound is:
R wherein
1For: the straight chained alkyl of 2-12 carbon atom, branched-chain alkyl or chirality alkyl;
R wherein
2For: the straight chain ester group of 2-12 carbon atom, side chain ester group, chirality ester group, straight chain alkoxyl group, branched alkoxy, chirality alkoxyl group,
Described one type of compound method that contains the triazole heterogeneous ring compound is by synthesizing through the click chemistry method to the triazobenzene manthanoate and to the acetylenylbenzene manthanoate, and its synthesis step is following:
(1) be raw material with para-amino benzoic acid and absolute ethyl alcohol, the vitriol oil is made catalyzer, makes parathesin;
(2) under the ice-water bath condition; In molar ratio 1 part of parathesin is dissolved in 1 part of concentrated hydrochloric acid and the 1 part of water; Add 2 parts of Sodium Nitrites after 10-30 minute, be incubated 0~5 ℃ 1-2 hour, slowly add 2 parts of sodiumazide; Stopped reaction after 10-45 minute, filtration, washing, dry must be to the triazobenzene manthanoate;
(3) be that raw material prepares the parabromobenzoic acid ethyl ester through esterification with the parabromobenzoic acid;
(4) in molar ratio; With 10 parts of parabromobenzoic acid ethyl esters, 12 parts of 2-methyl-3-butyne-2-alcohols, 0.1 part of triphenylphosphine, 0.05 part of cuprous iodide, 0.01 part of bi triphenyl phosphine dichloride palladium and 15 parts of anhydrous triethylamines and 5 parts of pyridines; Nitrogen protection refluxed reaction 1-3 hour; Pour in the water, extract, cross the post separation and obtain 4-(3-hydroxy-3-methyl-1-propine) ethyl benzoate;
(5) in molar ratio, the adding of 10 parts of 4-(3-hydroxy-3-methyl-1-propine) ethyl benzoate is dissolved with in the Virahol of 40 parts of Pottasium Hydroxide, backflow 1-5 hour, filtered while hot got the benzoic sylvite of 4-ethynyl;
(6) in molar ratio; 2 parts of benzoic sylvite of 4-ethynyl are suspended in 5-20 part chloroform; Add 4-10 part sulfur oxychloride under the ice-water bath condition, steamed solvent in room temperature reaction 4-10 hour, add 2 parts of corresponding alcohol; Methylene dichloride is made solvent, makes 4-acetylenylbenzene manthanoate in anhydrous pyridine catalysis refluxed;
(7) with said to the triazobenzene manthanoate with the acetylenylbenzene manthanoate is made title product through the click chemistry method; Mol ratios such as employing to triazobenzene manthanoate and 4-acetylenylbenzene manthanoate in the presence of 1 equivalent cupric sulfate pentahydrate and 3 normal sodium ascorbates; With the THF and the water as solvent of equal-volume ratio, can obtain containing the triazole heterogeneous ring compound in room temperature reaction 8-72 hour.
Concrete synthetic route is following:
Synthetic route 1:
Promptly generate parathesin (II) through esterification, (II) generate triazobenzene ethyl formate (A) with reaction of sodium azide after the diazotization with para-amino benzoic acid (I).Parabromobenzoic acid (III) is a starting raw material, generates parabromobenzoic acid ethyl ester (IV) through esterification; Compound (IV) makes 4-(3-hydroxy-3-methyl-butyl) ethyl benzoate (V) with 2-methyl-3-butyl-2-alcohol through the Sonogashira linked reaction; Compound (V) takes off acetone and obtains the benzoic sylvite of alkynyl (VI) under strong alkaline condition; Compound (VI) generates corresponding ester (B with sulfur oxychloride reaction becoming acyl chlorides (VII), last (VII) with the alcohol reaction
n).(A) and (B
n) through the synthetic end product (T of click chemistry reaction
1 n).
Synthetic route 2:
Be starting raw material promptly, generate butoxy oil of mirbane (b) through etherificate with p-NP (a); Compound (b) is through SnCl
22H
2The O reduction obtains butoxy aniline (c); Generate butoxy phenylazide (C) with reaction of sodium azide after compound (c) diazotization.(C) and (B
n) through the synthetic end product (T of click chemistry reaction
2 n).
Synthetic route 3:
Promptly to be starting raw material to hexyloxybenzoate (i), nitrophenyl-4-hexyloxybenzoate ester (ii) to generate 4-through esterification; Compound is (ii) through SnCl
22H
2O reduction obtains that the 4-aminophenyl-4-hexyloxybenzoate ester (iii); Compound (iii) generates 4-azido-phenyl-4-hexyloxybenzoate ester (D) with reaction of sodium azide after the diazotization.(D) and (B
5) through the synthetic end product (T of click chemistry reaction
3).
Synthetic route 4:
Be starting raw material promptly, generate 1,4-two phenylazides (E) with reaction of sodium azide after the diazotization with Ursol D (1).(E) and (B
5) through the synthetic end product (T of click chemistry reaction
4).
This compounds is measured with POM through DSC has SmA mutually.
Beneficial effect of the present invention: this class contains the triazole heterogeneous ring compound by synthesizing through the click chemistry method to the triazobenzene manthanoate and to the acetylenylbenzene manthanoate.Adopt the non-linear triazole heterogeneous ring compound of easy, easy-operating method synthetic to have the characteristics such as SmA phase, good stability of broad.Contain triazole heterocyclic compound in addition and also have outstanding advantages such as aromaticity, dipole moment be big; Can change the dipole moment, dielectric anisotropy of liquid crystal molecule, various character such as luminous; Thereby in the liquid crystal molecule that the triazole heterogeneous ring compound is introduced, study this compounds liquid crystal property, to design and develop new-type functional material etc. significant.
Embodiment
Below with R
1The n-hexyl that is 6 carbon atoms is an example, and four kinds of compound methods that contain triazole heterocycle liquid crystalline cpd are described.
The structural formula of four kinds of compounds is following:
(1), the preparation of 4-triazobenzene ethyl formate (A):
Add 0.685g (5mmol) para-amino benzoic acid, 5mL ethanol in the 10mL single port bottle, the catalytic amount vitriol oil, temperature rising reflux 3h.Cooling is poured in the water, uses saturated Na
2CO
3Be neutralized to pH=7-8, filtration washing, the dry 0.284g white p-subcutin solid (II) that gets.Productive rate: 42.0%, M.p:18.9-19.3 ℃.
Add 165mg (1mmol) p-subcutin (II) in the 10mL single port bottle, dense HCl of 1.5mL and 1.5mL water, ice-water bath adds water-soluble 104mgNaNO
2, stir 1h, add the 100mgNaN that dissolves water again
3, stir 30min.Filter, natural drying at room temperature gets light yellow solid (A) 70mg.Productive rate: 73.3%, M.p:95.5-97.0 ℃.
Same method can make following compound:
4-triazobenzene propyl formate
4-triazobenzene butyl formate
4-triazobenzene pentyl formate
4-triazobenzene hexyl formate
4-triazobenzene heptyl formate
4-triazobenzene octyl formate
4-triazobenzene nonyl formate
4-azido-n-decyl benzoate
(2), 4-acetylenylbenzene hexyl formate (B
5) preparation:
Add 1.005g (5mmol) parabromobenzoic acid, 10mL ethanol and the catalytic amount vitriol oil in the 25mL single port bottle, backflow 2h.Reaction solution is poured in the frozen water CH into after being cooled to room temperature
2Cl
2(2 * 50mL) extracted organic phase are used 5%NaHCO respectively
3Solution (2 * 30mL), (2 * 50mL) washing organic phases, anhydrous magnesium sulfate drying filters saturated NaCl solution, screws out solvent and gets yellow parabromobenzoic acid ethyl ester (IV) liquid, productive rate 92.8%.
Add 8mg bi triphenyl phosphorus palladium chloride in the 25mL two-mouth bottle, 3mg CuI, 0.645g (3mmol) parabromobenzoic acid ethyl ester, 3mmol 2-methyl-3-butyl-2-alcohol, 4mL triethylamine and 1.5mL pyridine, N
2Protection refluxed 1h.Reaction solution is cooled to room temperature, pours in the water CH into
2Cl
2Extracted organic phase, anhydrous magnesium sulfate drying revolves and did post and get light yellow solid (V), productive rate 85.0%.
Add 0.581g alkynes ester (V), 0.560g KOH, 12mL Virahol in the 25mL single port bottle, backflow 1h cooling is filtered, and the washed with isopropyl alcohol of heat gets white solid (VI), productive rate 85.0% twice.
Add 368mg (VI) in the 25mL single port bottle, 1.5mL SOCl
2, 10mL CHCl
3, room temperature reaction 6h steams solvent, gets compound (VII), does not handle and directly does next step reaction.In former reaction flask, add 400 μ L n-hexyl alcohols, 10mL CHCl
3, 0.5mL pyridine back flow reaction 2h steams solvent, cross post separate light yellow solid (B
5) 377mg, two step productive rates 81.8%.
Use the same method and to make following compound
4-acetylenylbenzene ethyl formate
4-acetylenylbenzene propyl formate
4-acetylenylbenzene butyl formate
4-acetylenylbenzene pentyl formate
4-acetylenylbenzene heptyl formate
4-acetylenylbenzene octyl formate
4-acetylenylbenzene nonyl formate
4-ethynyl n-decyl benzoate
(3), the own oxygen carbonyl-1H-of 4-ethoxycarbonyl-4`-[1,2,3]-triazole
Add 191mg (1mmol) 4-triazobenzene ethyl formate in the 25mL single port bottle, 4-acetylenylbenzene hexyl formate and THF/H
2O (5mL: 3mL).Stir to add down and be dissolved in the 125mg cupric sulfate pentahydrate in the 1mL water and be dissolved in the 300mg sodium ascorbate in the 1mL water, room temperature lucifuge stirring 3d.Pour into and get brown solid in the water, suction filtration, washing, sherwood oil flushing solid, dry light solid 224mg, the productive rate 53.14% of getting.
1H NMR (CDCl
3, 400MHz): δ (ppm): 8.352 (s, 1H, Triazole ring C-
H), 8.253 (d, J=8.8Hz, 2H), 8.151 (d, J=8.4Hz, 2H), 8.006 (d, J=8.4Hz, 2H), 7.918 (d, J=8.8Hz, 2H), J
1=8Hz, J
2=4Hz, 2H), 4.41-4.46 (m, 2H), 1.76-1.83 (m, 2H), 1.30-1.35 (m, 3H), 1.42-1.48 (m, 6H), 0.87-0.91 (m, 3H), TOF MS EI+: experimental value: 421.2290, theoretical value: 421.2002.
Same method can make following compound:
4-ethoxycarbonyl-4`-ethoxycarbonyl-1H-[1,2,3]-triazole
4-ethoxycarbonyl-4`-third oxygen carbonyl-1H-[1,2,3]-triazole
4-ethoxycarbonyl-4`-butoxy carbonyl-1H-[1,2,3]-triazole
4-ethoxycarbonyl-4`-penta oxygen carbonyl-1H-[1,2,3]-triazole
4-ethoxycarbonyl-4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1,2,3] of 4-ethoxycarbonyl-4`--triazole
4-ethoxycarbonyl-4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
4-ethoxycarbonyl-4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
4-third oxygen carbonyl-4`-ethoxycarbonyl-1H-[1,2,3]-triazole
4-third oxygen carbonyl-4`-, third oxygen carbonyl-1H-[1,2,3]-triazole
4-third oxygen carbonyl-4`-butoxy carbonyl-1H-[1,2,3]-triazole
4-third oxygen carbonyl-4`-, penta oxygen carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-1H-of 4-third oxygen carbonyl-4`-[1,2,3]-triazole
4-third oxygen carbonyl-4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1,2,3] of 4-third oxygen carbonyl-4`--triazole
4-third oxygen carbonyl-4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
4-third oxygen carbonyl-4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
4-butoxy carbonyl-4`-ethoxycarbonyl-1H-[1,2,3]-triazole
4-butoxy carbonyl-4`-third oxygen carbonyl-1H-[1,2,3]-triazole
4-butoxy carbonyl-4`-butoxy carbonyl-1H-[1,2,3]-triazole
4-butoxy carbonyl-4`-penta oxygen carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-1H-of 4-butoxy carbonyl-4`-[1,2,3]-triazole
4-butoxy carbonyl-4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1,2,3] of 4-butoxy carbonyl-4`--triazole
4-butoxy carbonyl-4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
4-butoxy carbonyl-4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
4-penta oxygen carbonyl-4`-ethoxycarbonyl-1H-[1,2,3]-triazole
4-penta oxygen carbonyl-4`-, third oxygen carbonyl-1H-[1,2,3]-triazole
4-penta oxygen carbonyl-4`-butoxy carbonyl-1H-[1,2,3]-triazole
4-penta oxygen carbonyl-4`-, penta oxygen carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-1H-of 4-penta oxygen carbonyl-4`-[1,2,3]-triazole
4-penta oxygen carbonyl-4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1,2,3] of 4-penta oxygen carbonyl-4`--triazole
4-penta oxygen carbonyl-4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
4-penta oxygen carbonyl-4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl of 4--4`-ethoxycarbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-4`-third oxygen carbonyl-1H-of 4-[1,2,3]-triazole
The own oxygen carbonyl of 4--4`-butoxy carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-4`-penta oxygen carbonyl-1H-of 4-[1,2,3]-triazole
The own oxygen carbonyl-1H-of the own oxygen carbonyl-4`-of 4-[1,2,3]-triazole
The own oxygen carbonyl of 4--4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1,2,3] of the own oxygen carbonyl of 4--4`--triazole
The own oxygen carbonyl of 4--4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl of 4--4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
4-oxygen in heptan carbonyl-4`-ethoxycarbonyl-1H-[1,2,3]-triazole
4-oxygen in heptan carbonyl-4`-third oxygen carbonyl-1H-[1,2,3]-triazole
4-oxygen in heptan carbonyl-4`-butoxy carbonyl-1H-[1,2,3]-triazole
4-oxygen in heptan carbonyl-4`-penta oxygen carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-1H-of 4-oxygen in heptan carbonyl-4`-[1,2,3]-triazole
4-oxygen in heptan carbonyl-4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1,2,3] of 4-oxygen in heptan carbonyl-4`--triazole
4-oxygen in heptan carbonyl-4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
4-oxygen in heptan carbonyl-4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl of 4--4`-ethoxycarbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-4`-third oxygen carbonyl-1H-[1,2,3] of 4--triazole
The hot oxygen carbonyl of 4--4`-butoxy carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-4`-penta oxygen carbonyl-1H-[1,2,3] of 4--triazole
The hot own oxygen carbonyl-1H-of oxygen carbonyl-4`-[1,2,3] of 4--triazole
The hot oxygen carbonyl of 4--4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl of the 4--hot oxygen carbonyl-1H-[1,2,3] of 4`--triazole
The hot oxygen carbonyl of 4--4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl of 4--4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-ethoxycarbonyl-1H-[1,2,3]-triazole
4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-third oxygen carbonyl-1H-[1,2,3]-triazole
4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-butoxy carbonyl-1H-[1,2,3]-triazole
4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-penta oxygen carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-1H-of 4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-[1,2,3]-triazole
4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1,2,3] of 4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`--triazole
4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
4-oxygen in ninth of the ten Heavenly Stems carbonyl-4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
4-oxygen in last of the ten Heavenly stems carbonyl-4`-ethoxycarbonyl-1H-[1,2,3]-triazole
4-oxygen in last of the ten Heavenly stems carbonyl-4`-third oxygen carbonyl-1H-[1,2,3]-triazole
4-oxygen in last of the ten Heavenly stems carbonyl-4`-butoxy carbonyl-1H-[1,2,3]-triazole
4-oxygen in last of the ten Heavenly stems carbonyl-4`-penta oxygen carbonyl-1H-[1,2,3]-triazole
The own oxygen carbonyl-1H-of 4-oxygen in last of the ten Heavenly stems carbonyl-4`-[1,2,3]-triazole
4-oxygen in last of the ten Heavenly stems carbonyl-4`-oxygen in heptan carbonyl-1H-[1,2,3]-triazole
The hot oxygen carbonyl-1H-[1,2,3] of 4-oxygen in last of the ten Heavenly stems carbonyl-4`--triazole
4-oxygen in last of the ten Heavenly stems carbonyl-4`-oxygen in ninth of the ten Heavenly Stems carbonyl-1H-[1,2,3]-triazole
4-oxygen in last of the ten Heavenly stems carbonyl-4`-oxygen in last of the ten Heavenly stems carbonyl-1H-[1,2,3]-triazole
(1) preparation of 4-butoxy aniline
, the 25mL bottle with two necks of spherical reflux condensing tube and constant pressure funnel adds 278mg (2mmol) p-NP (a) in being housed, 828mg (6mmol) K
2CO
3, 23mg KI, 10mL acetone adds the 302mg bromination of n-butane in the constant pressure funnel.Be warming up to backflow, slowly drip bromination of n-butane, back flow reaction 24h, the some plate reacts completely.Suction filtration, the washing with acetone filter cake revolves dried tawny 4-butoxy oil of mirbane (b) liquid.
Add 1.44mmol 4-butoxy oil of mirbane (b), 1.5g SnCl in the 25mL single port bottle
22H
2O, 10mL ethanol, back flow reaction 24h, the some plate reacts completely.Pour in the water with 1N NaOH solution and transfer pH to neutral, extracted with diethyl ether, organic phase are used saturated aqueous common salt, water washing successively, and anhydrous magnesium sulfate drying screws out solvent and gets sorrel liquid, cross post separate 174mg sorrel 4-butoxy aniline (c) liquid.
(2) preparation of 4-butoxy phenylazide
Add 174mg 4-butoxy aniline (c), 3mL concentrated hydrochloric acid and 3mL water, ice-water bath 30min in the 25mL single port bottle.Add water-soluble 110mg NaNO
2, ice-water bath slowly drips water-soluble 102mgNaN after stirring 1h
3, ice-water bath stirs 30min, CH
2Cl
2Extraction, anhydrous magnesium sulfate drying screws out solvent and gets sorrel 4-butoxy phenylazide (C) liquid.
(3) preparation of 4-acetylenylbenzene hexyl formate is with embodiment 1
(4) 4-(1-(4-butoxy) phenyl)-1H-[1,2,3]-triazol radical hexyl-benzoate (T
2 5) preparation with embodiment 1
1HNMR(CDCl
3,400MHz):δ(ppm):8.191(s,1H,triazole?ring?C-H),8.138(d,J=8.4Hz,2H),7.987(d,J=8.4Hz,2H),7.674(d,J=8.8Hz,2H),7.055(d,J=8.8Hz,2H),4.354(t,J=6.4Hz,2H),4.038(t,J=6.4Hz,2H),1.747-1.853(m,4H),1.476-1.546(m,8H),1.003(t,J=7.4Hz,6H).
TOF MS EI+: experimental value: 421.2372, theoretical value: 421.2365.
(1) preparation of 4-nitrophenyl-4-hexyloxy benzene methyl
, the 25mL single port bottle of tail gas collecting device adds 444mg (2mmol) in being housed to hexyloxybenzoate (i), 5mL SOCl
2, back flow reaction 4-5h, decompression steams SOCl
2Add the 278mg p-NP, 0.5mL pyridine, 5mL CH
2Cl
2Back flow reaction 3h steams solvent, washing, CH
2Cl
2Extraction, anhydrous magnesium sulfate drying screws out solvent and gets (ii) solid 666mg of oyster white 4-nitrophenyl-4-hexyloxy benzene methyl, productive rate 96%.
(2) preparation of 4-aminophenyl-4-hexyloxy benzene methyl
In 10mL single port bottle, add 174mg (0.5mmol) 4-nitrophenyl-4-hexyloxy benzene methyl (ii), 0.55g SnCl
22H
2O, 3mL ethanol, back flow reaction 3h, the some plate reacts completely.Pour in the water and transfer pH=7, get (iii) solid of white 4-aminophenyl-4-hexyloxy benzene methyl, suction filtration vacuum-drying with 10%NaOH solution.
(3) preparation method of 4-azido-phenyl-4-hexyloxy benzene methyl (D) is with embodiment 2
(4) preparation of 4-acetylenylbenzene hexyl formate is with embodiment 1
(5) 4-[1-(4-(4-hexyloxy) carbobenzoxy) phenyl]-1H-[1,2,3]-triazol radical hexyl-benzoate (T
3) preparation with embodiment 1
The preparation of (1) 1,4-two phenylazides is with embodiment 1
(2) preparation of 4-acetylenylbenzene hexyl formate is with embodiment 1
(3) 4,4`-(1-(1H-[1,2,3]-triazol radical)-1, the two phenyl of 4-) hexyl-benzoate (T
4) preparation with embodiment 1
Liquid crystal property is measured:
T
1The phase transition temperature that series compound is measured with DSC
Claims (1)
1. the compound method that contains the triazole heterogeneous ring compound of a formula I is characterized in that: said compound is by synthetic through the click chemistry method to triazobenzene manthanoate and 4-acetylenylbenzene manthanoate, and its synthesis step is following:
I
R wherein
1For: the straight chained alkyl of 2-12 carbon atom or branched-chain alkyl;
(1) be raw material with para-amino benzoic acid and absolute ethyl alcohol, the vitriol oil is made catalyzer, makes parathesin;
(2) under the ice-water bath condition; In molar ratio 1 part of parathesin is dissolved in 1 part of concentrated hydrochloric acid and the 1 part of water; Add 2 parts of Sodium Nitrites after 10-30 minute, be incubated 0~5 ℃ 1-2 hour, slowly add 2 parts of sodiumazide; Stopped reaction after 10-45 minute, filtration, washing, dry must be to the triazobenzene ethyl formate;
(3) be that raw material prepares the parabromobenzoic acid ethyl ester through esterification with the parabromobenzoic acid;
(4) in molar ratio; With 10 parts of parabromobenzoic acid ethyl esters, 12 parts of 2-methyl fourth-3-alkynes-2-alcohol, 0.1 part of triphenylphosphine, 0.05 part of cuprous iodide, 0.01 part of bi triphenyl phosphine dichloride palladium and 15 parts of anhydrous triethylamines and 5 parts of pyridines; Nitrogen protection refluxed reaction 1-3 hour; Pour in the water, extract, cross the post separation and obtain 4-(3-hydroxy-3-methyl fourth-1-alkynyl) ethyl benzoate;
(5) in molar ratio, the adding of 10 parts of 4-(3-hydroxy-3-methyl fourth-1-alkynyl) ethyl benzoate is dissolved with in the Virahol of 40 parts of Pottasium Hydroxide, backflow 1-5 hour, filtered while hot got the benzoic sylvite of 4-ethynyl;
(6) in molar ratio; 2 parts of benzoic sylvite of 4-ethynyl are suspended in 5-20 part chloroform; Add 4-10 part sulfur oxychloride under the ice-water bath condition, steamed solvent in room temperature reaction 4-10 hour, add 2 parts of corresponding alcohol; Methylene dichloride is made solvent, makes 4-acetylenylbenzene manthanoate in anhydrous pyridine catalysis refluxed;
(7) with said to the triazobenzene ethyl formate with the acetylenylbenzene manthanoate is made title product through the click chemistry method; Mol ratios such as employing to triazobenzene ethyl formate and 4-acetylenylbenzene manthanoate in the presence of 1 equivalent cupric sulfate pentahydrate and 3 normal sodium ascorbates; With the THF and the water as solvent of equal-volume ratio, can obtain containing the triazole heterogeneous ring compound in room temperature reaction 8-72 hour.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010102789771A CN101941949B (en) | 2010-09-10 | 2010-09-10 | Triazole heterocyclic compound and synthesis method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010102789771A CN101941949B (en) | 2010-09-10 | 2010-09-10 | Triazole heterocyclic compound and synthesis method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101941949A CN101941949A (en) | 2011-01-12 |
CN101941949B true CN101941949B (en) | 2012-11-14 |
Family
ID=43434185
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2010102789771A Expired - Fee Related CN101941949B (en) | 2010-09-10 | 2010-09-10 | Triazole heterocyclic compound and synthesis method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101941949B (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102391511B (en) * | 2011-09-07 | 2013-09-18 | 华东理工大学 | Novel polytriazole resins with rigid structure and preparation method thereof |
CN102746853B (en) * | 2012-06-18 | 2013-12-11 | 北京科技大学 | Triazole bending rodlike liquid crystal compound and preparation method thereof |
CN103288885B (en) * | 2013-06-09 | 2015-03-11 | 内蒙古大学 | Synthesis method of mono-substituted ferrocene ramification containing 1,2,3-triazole heterocycle |
KR102160489B1 (en) * | 2014-07-25 | 2020-09-29 | 삼성디스플레이 주식회사 | Fabrication method of display device and display device |
CN104212461B (en) * | 2014-08-12 | 2016-07-13 | 北京大学 | Symmetrical triazole type Rod-like liquid crystal compound and preparation method thereof |
CN105062502B (en) * | 2015-08-07 | 2017-08-25 | 华南师范大学 | Liquid-crystal compounds and its preparation method and use containing penta azacyclo |
CN107827829A (en) * | 2017-11-07 | 2018-03-23 | 大连理工大学 | Preparation method of 5 amide groups, 1,4,5 trisubstituted 1,2,3 triazole in aqueous phase and Biomedia |
CN113527267B (en) * | 2021-06-21 | 2022-09-02 | 山东盛安贝新能源有限公司 | C2 symmetric duplex nitrogen heterocyclic ring fluorocarbon surfactant and preparation of aqueous phase micelle thereof |
-
2010
- 2010-09-10 CN CN2010102789771A patent/CN101941949B/en not_active Expired - Fee Related
Non-Patent Citations (4)
Title |
---|
D MARZOTKO, et al.Calorimetric investigation of liquid crystals.《Paramna》.1975,(第增刊第1期),189-213. * |
Theo J. Dingemans, et al.Javelin-, Hockey Stick-, and Boomerang-Shaped Liquid Crystals. Structural Variations on p-Quinquephenyl.《J. Phys. Chem. B》.2001,第105卷(第37期),8845-8860. * |
张智勇 等.α-甲基联苯酯类液晶的合成与性质.《应用化学》.2003,第20卷(第1期),59-64. * |
李晓莲 等.含三氮唑杂环液晶中间体的合成.《液晶与显示》.2010,第25卷(第4期),502-504. * |
Also Published As
Publication number | Publication date |
---|---|
CN101941949A (en) | 2011-01-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101941949B (en) | Triazole heterocyclic compound and synthesis method thereof | |
CN1984898A (en) | Process for production of azulene derivatives and intermediates for the synthesis of the same | |
CN100572378C (en) | The improved preparation method of Cinepazide Maleate | |
CN106831397B (en) | A kind of anthraquinone analog compound and preparation method thereof and medical application | |
CN107674074A (en) | A kind of preparation method and application of amphipathic naphthoyl diimine gelator | |
CN101544591B (en) | (E)-substituted styrene compound and preparation method thereof | |
CN111039876A (en) | Preparation method of 4-amino-2, 6-dimethoxypyrimidine | |
CN103833754B (en) | There is the carbazole of diaza aromatic condensed ring structure and phenanthridines compounds and synthetic method thereof | |
CN102936223A (en) | Synthesis method and purification method of 5-iodo-2-methylbenzimidazole | |
CN107185456B (en) | A kind of synthesis and performance of star-like abietyl terpolymer surfactant of the coupling link containing phenyl ring | |
CN105153013A (en) | Synthesis method of 6-bromoisoindolinyl-1-one | |
CN105384710B (en) | A kind of synthetic method of pharmaceutical intermediate furfuran compound | |
CN105237584B (en) | A kind of preparation method of N, N ' ferrocene diacetyl three (dodecyloxy) benzamide | |
CN103724291A (en) | Synthetic method of pramipexole dihydrochloride related substance B | |
CN101445467B (en) | Chemical synthesis method of N-(4-chlorobenzoyl)-tyramine | |
CN102675064B (en) | Preparation method and application of Z-3,4,4',5-tetramethoxy-2',3'-dihydroxy diphenylethylene | |
CN103193784B (en) | A kind of containing pyrimidine group rigidity Conjugate macrocycle compound and its preparation method and application | |
CN101570519A (en) | Preparation method of 1, 2-benzisothiazolin-3-ketone | |
CN101475614B (en) | Method for preparing 2,3,4,5,6-5-O-benzyl mannose from D-mannitol | |
CN102086147B (en) | Preparation method of substituted phenol | |
CN109988098A (en) | The synthetic method of one kind (R)-N- tertbutyloxycarbonyl -3- hydroxymethyl piperidine | |
CN104086427B (en) | The preparation method of benzoate compounds | |
CN108191887A (en) | A kind of synthetic method of dibenzo spiral shell [4,5] dodecane ketone derivatives | |
CN101948372B (en) | 2-methoxyl-3,4-difluorobenzene, preparation method and application thereof | |
CN106256832B (en) | The synthetic method of indoles nucleoside compound with antiviral activity |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121114 Termination date: 20150910 |
|
EXPY | Termination of patent right or utility model |