CN103819479B - A kind of containing pyrimidine group rigidity Conjugate macrocycle compound and its preparation method and application - Google Patents
A kind of containing pyrimidine group rigidity Conjugate macrocycle compound and its preparation method and application Download PDFInfo
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- CN103819479B CN103819479B CN201410086053.XA CN201410086053A CN103819479B CN 103819479 B CN103819479 B CN 103819479B CN 201410086053 A CN201410086053 A CN 201410086053A CN 103819479 B CN103819479 B CN 103819479B
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- pyrimidine group
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- dibromobenzene
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- -1 macrocycle compound Chemical class 0.000 title claims abstract description 24
- 125000000714 pyrimidinyl group Chemical group 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 230000004044 response Effects 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 239000000178 monomer Substances 0.000 abstract description 10
- PZFMWYNHJFZBPO-UHFFFAOYSA-N 3,5-dibromophenol Chemical class OC1=CC(Br)=CC(Br)=C1 PZFMWYNHJFZBPO-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 6
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052796 boron Inorganic materials 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract description 4
- CMAARKUAKYAGAZ-UHFFFAOYSA-N N1=CN=CC=C1.[I] Chemical class N1=CN=CC=C1.[I] CMAARKUAKYAGAZ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010520 demethylation reaction Methods 0.000 abstract description 3
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 abstract 2
- 150000002170 ethers Chemical class 0.000 abstract 2
- IPWBFGUBXWMIPR-UHFFFAOYSA-N 1-bromo-2-fluorobenzene Chemical class FC1=CC=CC=C1Br IPWBFGUBXWMIPR-UHFFFAOYSA-N 0.000 abstract 1
- FNAKEOXYWBWIRT-UHFFFAOYSA-N 2,3-dibromophenol Chemical class OC1=CC=CC(Br)=C1Br FNAKEOXYWBWIRT-UHFFFAOYSA-N 0.000 abstract 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052794 bromium Inorganic materials 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 17
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 208000035126 Facies Diseases 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 238000001338 self-assembly Methods 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 8
- 235000019341 magnesium sulphate Nutrition 0.000 description 8
- 238000010025 steaming Methods 0.000 description 8
- 238000007710 freezing Methods 0.000 description 7
- 230000008014 freezing Effects 0.000 description 7
- 150000002678 macrocyclic compounds Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000006392 deoxygenation reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- ASWYHZXKFSLNLN-UHFFFAOYSA-N 1,3-dibromo-5-fluorobenzene Chemical compound FC1=CC(Br)=CC(Br)=C1 ASWYHZXKFSLNLN-UHFFFAOYSA-N 0.000 description 3
- XJFZOSUFGSANIF-UHFFFAOYSA-N 3-chloro-2-(chloromethyl)prop-1-ene Chemical group ClCC(=C)CCl XJFZOSUFGSANIF-UHFFFAOYSA-N 0.000 description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000021615 conjugation Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940125890 compound Ia Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000007070 tosylation reaction Methods 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- ZGBSOTLWHZQNLH-UHFFFAOYSA-N [Mg].S(O)(O)(=O)=O Chemical compound [Mg].S(O)(O)(=O)=O ZGBSOTLWHZQNLH-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0013—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- 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
-
- 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
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
-
- 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
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
-
- 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
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to one and contain pyrimidine group rigidity Conjugate macrocycle compound and its preparation method and application, the general structure of compound is: wherein n=1,2,3,4,5.Preparation includes: rigid element is with 3,5 two bromofluoro benzenes are Material synthesis 3,5 dibromobenzene methyl ethers, then synthesize 3 through Boron tribromide demethylation reaction, 5 dibromophenols, linear segment uses 3 chlorine 2 chloromethyl propylenes to be initiation material, obtains linear segment intermediate, and afterwards 3,5 dibromophenols synthesize 3 with linear segment intermediate the most again, 5 dibromobenzene long chain ethers, utilize 3, and 5 dibromobenzene long chain ethers and double pinacols close two boron to carry out Miyaura monomer II is synthesized；Monomer II and 5 bromine 2 iodine pyrimidines are by Suzuki coupling reaction synthon III；Monomer II and monomer III is utilized by Suzuki coupling and to get final product.Gained compound of the present invention is applied as functional material.
Description
Technical field
The invention belongs to Conjugate macrocycle compound and preparation thereof and application, particularly to one rigidity Han pyrimidine group
Conjugate macrocycle compound and its preparation method and application.
Background technology
The eighties in last century supramolecular chemistry concept proposition till now, supramolecular chemistry experienced by and rapidly develops.Its
In, the supramolecular materials of stimuli responsive has become the study hotspot in supramolecular chemistry field to external world, common especially with π-electronics
The organic supramolecular of yoke system, macromolecule are the material of basic component units, and its design and exploitation are more and more active.Related to this
Connection, has ordered structure, the rigid macrocyclic compound of Pi-conjugated systems and derivant thereof and is just attracted attention by huge.This class is rich
Pi-conjugated compound is according to the position of its polar functional group and orientation, the extremely strong mutual sedimentation of π-π being had by itself
It is easy to self assembly, so that macro ring forms solid-state one-dimensional column non-covalent bond polyphosphazene polymer collective structure, solid state two dimensional
Network structure and 3-D nano, structure.One-dimensional, two-dimentional, the three dimensional structure of this high-sequential can be that the carrier such as hole, electronics carries
For possible movable passageway.Science is caused as electronics and the photoelectron material material of brand-new display anisotropic properties
Family great interest.
Containing N heteroatomic Conjugate macrocycle compound as the emerging Conjugate macrocycle compound of a class due to its potential function
Receive significant attention with application.Conjugate macrocycle compound containing pyrimidine group is one of representative of this compounds, and they have
The most regular shape and structure, ring diameter is in Nano grade, according to the difference of flexible chain on its stiffening ring skeleton and ring, this kind of
Conjugate macrocycle compound can be piled up by self π-π or concave-convex interaction self assembly is constructed one-dimensional, two-dimentional
With Magnetic Properties of Three-Dimensional Supramolecular Complex structure, it is also possible to and with N hetero atom contained by pyrimidine, there is abilities such as combining proton, metal ion, it is used for making
Standby composite is studied and can sense the response functional material of environmental stimuli.Therefore, this kind of macrocyclic compound is as excellent
During good self assembly unit molecular application is developed to new function material.
Summary of the invention
The technical problem to be solved is to provide a kind of containing pyrimidine group rigidity Conjugate macrocycle compound and system thereof
Preparation Method and application, gained compound of the present invention can be developed as excellent self assembly unit molecular application to new function material
In；The present invention can pass through self contained N hetero atom and metal-complexing, presents special photoelectric properties, grinds for composite
In studying carefully；The present invention can be by preparing Modulatory character fluorescent material to the sensing of acid.It addition, can be by the size of guest molecule is selected
Select sexuality and should prepare the composite with different optics and electricity.
The one of present invention rigidity Conjugate macrocycle compound Han pyrimidine group, the general structure of described compound is:
Wherein n=1,2,3,4,5；Wherein, R is independently selected from hydrophobicity long-chain base
One or more in group, hydrophilic long-chain group, chirality long chain alkyl group, ester group, cyano group, amino, aryl, sulfydryl.
Described R the most independent for hydrophobicity long chain alkyl group or hydrophilic long-chain group, compound is:
In one；Wherein n=1,2,3,4,5.
Described compound is expanded through side chain:
Wherein n=1,2,3,4,5.
Atom N on described compound pyrimidine group is coordinated with Pt, and the structural formula after coordination is:
In one, wherein n=1,2,3,4,5.
Atom N on described compound pyrimidine group is coordinated with Pt, Pd or Ru.
A kind of preparation method containing pyrimidine group rigidity Conjugate macrocycle compound of the present invention, including:
(1) rigid element is with 3, and 5-bis-bromofluoro benzene is raw material, synthesizes 3 by substitution reaction, 5-dibromobenzene methyl ether, then through three
Boron bromide demethylation reaction synthesis 3,5-dibromophenol, linear segment uses 3-chloro-2-chloromethyl propylene to be initiation material, warp
Cross three steps (condensation, hydroboration-oxidation, tosylation) and obtain linear segment intermediate, afterwards 3,5-dibromophenol is in alkalescence
Under the conditions of again with linear segment intermediate by nucleophilic substitution synthesize 3,5-dibromobenzene long chain ether, utilize 3,5-dibromobenzene is long
Chain ether and double pinacols close two boron to carry out Miyaura monomer II is synthesized；
(2) bromo-2 iodine pyrimidines of monomer II Yu 5-pass through Suzuki coupling reaction synthon III；
(3) monomer II and monomer III is utilized to be conjugated containing pyrimidine group rigidity by the synthesis of Suzuki coupling one step to form the loop method
Macrocyclic compound.
A kind of application containing pyrimidine group rigidity Conjugate macrocycle compound of the present invention, described containing pyrimidine group rigidity conjugation
Macrocyclic compound is developed in functional material as self assembly unit molecular application.
A kind of application containing pyrimidine group rigidity Conjugate macrocycle compound of the present invention, described containing pyrimidine group rigidity conjugation
Macrocyclic compound is coordinated for preparing the composite with difference in functionality with metal.
A kind of application containing pyrimidine group rigidity Conjugate macrocycle compound of the present invention, described containing pyrimidine group rigidity conjugation
Macrocyclic compound has reversibility to the response of PH, studies for controllable fluorescent material.
A kind of application containing pyrimidine group rigidity Conjugate macrocycle compound of the present invention, by selecting the size of guest molecule
Select sexuality and should prepare the composite with different optics and electricity.
It is supramolecular structured through being self-assembly of that secondly the present invention provides a kind of rigidity Conjugate macrocycle compound Han pyrimidine group
Structure body is for the research of functional material exploitation.The compound of the present invention has regular molecular structure, and pore size is in nanometer
Rank, can be piled up by self π-π or one-dimensional, two and three dimensions oversubscription is constructed in concave-convex interaction self assembly
Minor structure, in developing as excellent self assembly unit molecular application to new function material；Furthermore it is also possible to utilize pyrimidine institute
The hetero atom containing N has abilities such as combining proton, metal ion, is used for preparing composite research and can sensing environmental stimuli
Response functional material.
Beneficial effect
(1) the invention provides series of new rigidity Conjugate macrocycle compound one step to form the loop synthetic method Han pyrimidine group,
Possess Material synthesis method simple, mature preparation process, productivity relatively advantages of higher；
(2) during the present invention can develop as excellent self assembly unit molecular application to new function material；
(3) present invention can pass through self contained N hetero atom and metal-complexing, presents special photoelectric properties, for multiple
Condensation material is studied；
(4) present invention can be by preparing Modulatory character fluorescent material and electro-active materials (electron transfer to the sensing of acid
Or energy transfer)；
(5) present invention can be by having being combined of different optics and electricity to the sensing preparation of the size selectivity of guest molecule
Material.
Accompanying drawing explanation
Fig. 1 is the GPC separation graph of embodiment 9 product；
Fig. 2 is target product I in embodiment 91、I2、I3MALDI-TOF Mass figure；
Fig. 3 is the middle I of embodiment 9 product1Fluorescence spectrum figure to acid response, the response fluorescence spectrum figure to acid
(a) and continuation response fluorescence spectrum figure (b) to alkali.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, people in the art
The present invention can be made various changes or modifications by member, and these equivalent form of values fall within the application appended claims equally and limited
Scope.
Rigid element use 3,5-bis-bromofluoro benzene is initiation material, by substitution reaction synthesize 3,5-dibromobenzene methyl ether, after
3,5-dibromophenol (Davidson J P, Sarma K, Fishlock D, et has been synthesized through Boron tribromide demethylation reaction
al.Synthesis of 3,5-Disubstituted Phenols[J].Org Process Res Dev,2010,14(2):
477-480.), it addition, linear segment uses 3-chloro-2-chloromethyl propylene to be initiation material, through three steps (condensation, hydroboration oxygen
Change, tosylation) (Davies, P.J. can be obtained smoothly;Grove,D.M.;van.Koten,G.,Advances in
the synthesis of multimetalllic systems:hydroxyl group protection in
(aryldiamine) platinum species.Organometallics1997,16 (4), 800-802.).3,5-dibromobenzene
Phenol synthesizes 11 with linear segment intermediate 7 by nucleophilic substitution.Utilizing 11 to close two boron with double pinacols, to carry out Miyaura anti-
Borate intermediate monomer 2a should be synthesized, after by bromo-2 iodine pyrimidines of 2a Yu 5-by Suzuki coupling reaction synthon 3a, finally
Monomer 2a and 3a is utilized to synthesize target macrocyclic compound Ia by Suzuki coupling one step to form the loop method.
Embodiment 1
The synthesis of compound 5
To equipped with in two mouthfuls of flasks of 500mL of magnetic stir bar and reflux add NaH (19.2g, 0.8mol,
7.4eq.), under Ar gas shielded, substitute gas three times, add anhydrous THF (250mL), add 3-chloro-2-chloromethyl propylene (13.5g,
0.11mol, 1eq.), it is added dropwise over 1-lauryl alcohol (42.3g, 0.227mol, 2.1eq.).At 65 DEG C, back flow reaction is overnight, cooling
To room temperature, the cancellation that adds water is reacted, and rotation is steamed rotation and removed THF, uses CH2Cl2Extraction (50mL × 3), merges organic facies, distillation washing (50mL
× 3), anhydrous magnesium sulfate is dried organic facies, is filtered to remove magnesium sulfate, and rotation steaming is evaporated off solvent, and residue silica gel column chromatography purifies
(eluant: PE/CH2Cl2=5/1), colourless liquid 32.4g, productivity 75% are obtained.1H NMR(400MHz,CDCl3):δ5.14(s,
2H),3.95(s,4H),3.39(t,J=6.6Hz,4H),1.62–1.48(m,4H),1.25(s,36H),0.87(t,J=6.7Hz,
6H).
Embodiment 2
The synthesis of compound 6
In two mouthfuls of flasks of 250mL, add 5 (8.0g, 0.02mmol), under Ar gas shielded, substitute gas three times, add anhydrous
THF (35mL), is added dropwise over the 1mol/L BH that THF dissolves at 0 DEG C3(28mL), quickly stirring 2 hours, drip 3mol/LNaOH
(28mL).Quickly stirring 15 minutes, drip 30%H2O2(28mL), under room temperature, quickly stirring adds K in 30 minutes2CO3To saturated,
CH2Cl2Extraction (50mL × 3), merges organic facies, and distillation washing (50mL × 3), anhydrous magnesium sulfate is dried organic facies, is filtered to remove
Magnesium sulfate, rotation steaming is evaporated off solvent, and residue silica gel column chromatography purifies, and obtains colourless liquid 6.5g, productivity 79%.1H NMR
(400MHz,CDCl3):δ3.78(d,J=5.1,2.4Hz,1H),δ3.76(d,J=5.0Hz,1H),δ3.68(d,J=6.1Hz,
1H),3.62–3.58(m,2H),3.52(m,J=9.4,6.0Hz,2H),3.47–3.25(m,4H),2.17(s,1H),1.55(d,
J=10.2,3.9Hz,4H),1.46–1.03(m,36H),0.99–0.74(m,6H)。
Embodiment 3
The synthesis of compound 7
6 (3.9g, 9.57mmol, 1eq.), TsCl (9.13g, 47.9mmol, 5eq.) is added in two mouthfuls of flasks of 500mL,
Under Ar gas shielded, substitute gas three times, add anhydrous CH2Cl2(80mL), pyridine (11.4g, 144mmol, 15eq.), at 25 DEG C
Quickly stirring 5 hours, use CH2Cl2Extraction (50mL × 30), merge organic facies, organic facies first with 1mol/L HCl wash (50mL ×
1), then washing (50mL × 3) with distillation, anhydrous magnesium sulfate is dried organic facies, is filtered to remove magnesium sulfate, and rotation steaming is evaporated off solvent, surplus
Excess silica gel column chromatography purifies, and obtains weak yellow liquid 4.6g, productivity 85%.
1H NMR(400MHz,CDCl3):δ7.81(d,J=8.3Hz,2H),7.36(d,J=8.0Hz,2H),4.12(d,J=
5.6Hz,2H),3.46–3.23(m,8H),2.47(s,3H),2.20(q,J=11.5,5.8Hz,1H),1.54–1.40(m,4H),
1.37–1.17(m,36H),0.90(t,J=6.8Hz,6H)。
Embodiment 4
The synthesis of 3,5-dibromobenzene methyl ether (9)
3,5-bis-bromofluoro benzene (8) (20.0g, 0.08mol, 1eq.) and dry DMF is added in the round-bottomed flask of 500mL
(350mL), after, in round-bottomed flask, Feldalat NM (5.2g, 0.09mol, 1.2eq.) it is slowly added to, vigorous stirring overnight under room temperature,
It is subsequently adding 5%HCl to neutralize, stopped reaction.CH2Cl2Extraction (50mL × 3), organic facies distillation washing (50mL × 3), anhydrous
Magnesium sulfate is dried organic facies, is filtered to remove magnesium sulfate, and rotation is evaporated off solvent and obtains faint yellow solid, and silica gel column chromatography purifies (eluting
Agent: petroleum ether), obtain white solid 30g, productivity 95%.1H NMR(400MHz,CDCl3):δ7.25(t,J=1.6Hz,1H),6.99
(d,J=1.6Hz,2H),3.78(s,3H).
Embodiment 5
The synthesis of 3,5-dibromophenol (10)
3,5-dibromobenzene methyl ether (9) (5g, 18.8mmol, 1eq.) is added in two mouthfuls of flasks of 250mL, under Ar gas shielded,
Add anhydrous CH2Cl2(80mL), it is added dropwise over BBr at 0 DEG C3(3.5mL, 37.6mmol, 2eq.), after keeping 0 DEG C of reaction 3 hours
It is warmed to room temperature, stopped reaction after lucifuge reaction trash ice cancellation in 2 days.Reactant liquor CH2Cl2Extraction (50mL × 3), merges organic facies,
Distillation washing (50mL × 3), anhydrous magnesium sulfate is dried, and is filtered to remove magnesium sulfate, and rotation steaming is evaporated off solvent, residue silica gel column chromatography
Post purifies (eluant: ether/petroleum ether=1/9), obtains white solid 4.2g, productivity 90%.Mp=86-89℃.1H NMR
(400MHz,CDCl3): δ 7.28 (t, J=2.0Hz, 1H), 6.97 (t, 2H), 4.95 (s, 1H).
Embodiment 6
The synthesis of compound 11
Addition 7 (4g, 6.7mmol, 1eq.) in two mouthfuls of flasks of 100mL, 3,5-dibromophenols (3g, 13.4mmol,
2eq.), K2CO3(9g, 67mmol, 10eq.), under Ar gas shielded, adds anhydrous THF (50mL), and reflux 48h, stopped reaction.Rotation
THF is evaporated off, uses CH2Cl2Extraction (50mL × 3), merges organic facies, and distillation washing (50mL × 3), anhydrous magnesium sulfate is dried, mistake
Filtering magnesium sulfate, rotate steaming and solvent is evaporated off, residue silica gel column chromatography purifies (eluant: PE/EA=25/1), obtains pale yellow
Color liquid 3.8g, productivity 85%.1H NMR(400MHz,CDCl3):δ7.25(t,J=1.5Hz,1H),7.04(d,J=1.5Hz,
2H),4.02(t,J=10.2Hz,2H),3.57–3.47(m,4H),3.42(t,J=6.6Hz,4H),2.41–2.28(m,1H),
1.56(d,J=13.5,6.7Hz,4H),1.40–1.21(m,36H),0.88(t,J=22.0,7.4Hz,6H).
Embodiment 7
The synthesis of compound 2a
In 50mL two-mouth bottle bottle, be sequentially added into 11 (500mg, 0.74mmol), double pinacols close two boron (413.8mg,
1.63mmol), PdCl2(dppf) (35.56mg, 0.045mmol, 6%), KOAc (435.1mg, 4.44mmol, 6eq.), Ar gas
Substitute gas under protection three times, add dry DMF (freezing deoxygenation) (20mL), be heated to 80 DEG C, react 3 hours, stopped reaction.Cold
To room temperature, CH2Cl2Extraction (50mL × 3), merges organic facies, and distillation washing (50mL × 3), anhydrous magnesium sulfate is dried organic
Phase, is filtered to remove magnesium sulfate, and rotation steaming is evaporated off solvent, and residue silica gel column chromatography purifies (eluant: PE/EA=8/1), and GPC divides
From, give light yellow oil: 319.41mg, productivity 56%.1H NMR(400MHz,CDCl3)δ7.87(s,1H),7.46(s,2H),
4.08(d,J=5.5Hz,2H),3.56(d,J=6.0Hz,4H),3.42(t,J=6.6Hz,4H),2.37(m,J=11.5,5.7Hz,
1H),1.56(q,J=13.1,6.4Hz,4H),1.36(s,24H),1.27(s,36H),0.90(t,J=6.7Hz,6H).
Embodiment 8
The synthesis of compound 3a
Be sequentially added in equipped with the 25mL two-mouth bottle of magnetic agitation and reflux 2a (100mg, 0.13mmol,
1eq.), 5-bromo-2-iodine pyrimidine (112.8mg, 0.40mmol, 3eq.), Pd (PPh3)4(8mg, 0.0066mmol, 5%mol), Ar
Under gas shielded, add THF(freezing deoxygenation)/Toluene(freezing deoxygenation) (10/5mL=2/1), 2mol/L K2CO3(freezing removes
Oxygen) (0.66mL, 10eq.), it is heated to 85 DEG C of backflows, stopped reaction after reacting 24 hours.After being cooled to room temperature, rotation is evaporated off molten
Agent, CH2Cl2Extraction (50mL × 3), merges organic facies, distillation washing (50mL × 3), and anhydrous magnesium sulfate is dried organic facies, filters
Removing magnesium sulfate, rotation steaming is evaporated off solvent, and residue silica gel column chromatography purifies (eluant: PE/EA=30/1), obtains white solid
60mg, productivity 56%.1H NMR(400MHz,CDCl3)δ9.08(s,1H),8.88(s,4H),8.15(d,J=1.4Hz,2H),
4.25(d,J=5.6Hz,2H),3.62(d,J=6.0Hz,4H),3.45(t,J=6.6Hz,4H),2.54–2.38(m,1H),1.59
(m,J=14.6,7.5Hz,4H),1.24(s,36H),0.89(s,6H).
Embodiment 9
The synthesis of compound Ia with separate
To equipped with the 25mL two-mouth bottle of magnetic stir bar and reflux is sequentially added into compound 2a (84mg,
0.1084mmol1eq.), compound 3a (90mg, 0.1084mmol, 1eq.), Pd (PPh3)4(40mg,0.0325mmol,30%
Mmol), substitute gas under argon shield three times, add the oxolane 5mL of freezing deoxygenation, the toluene 2.5mL of freezing deoxygenation, freezing
The K of deoxygenation2CO3Aqueous solution (2mol/L) 1mL, is heated to 80 DEG C, back flow reaction 80h, stopped reaction.After being cooled to room temperature, use
CH2Cl2Extraction (50mL × 3), merges organic facies, and distillation washing (50mL × 3), anhydrous magnesium sulfate is dried, and is filtered to remove sulphuric acid
Magnesium, rotation steaming is evaporated off solvent, and residue silica gel column chromatography purifies (PE:EA=3:1), and residue is through preparing gel permeation chromatography
(GPC) purify further, obtain following target compound:
I1(n=1): productivity is 11.5%.MALDI-TOF Mass:Calcd.For C228H372N12O18[M]+:m/z=
3569.55;Found:3569.6.1H NMR(400MHz,THF)δ9.49(s,1H),9.30(s,4H),8.25(s,2H),7.86
(s,1H),7.47(s,2H),4.33(d,J=5.8Hz,2H),4.29(d,J=5.8Hz,2H),3.66(t,J=5.5Hz,9H),
3.48(t,J=6.5Hz,8H),2.46(d,J=3.1Hz,2H),1.60(dd,J=13.7,6.7Hz,10H),1.37–1.21(m,
79H),0.86(t,J=6.7Hz,14H)。
I2(n=2): productivity is 9.3%.MALDI-TOF Mass:Calcd.For C304H496N16O24[M+Na]+:m/z=
4778.78;Found:4779.5273。
I3(n=3): productivity is 7.7%.MALDI-TOF Mass:Calcd.For C304H496N16O24[M+Na]+:m/z=
5967.76;Found:5968.8779。
Claims (3)
1. a rigidity Conjugate macrocycle compound Han pyrimidine group, it is characterised in that: described compound is:
In one；Wherein n=2,3.
One the most according to claim 1 rigidity Conjugate macrocycle compound Han pyrimidine group, it is characterised in that: described chemical combination
Atom N on thing pyrimidine group and Pt, Pd or Ru metal-complexing.
3. the application containing pyrimidine group rigidity Conjugate macrocycle compound as claimed in claim 1, it is characterised in that: described
Containing pyrimidine group rigidity Conjugate macrocycle compound, the response of acid is had reversibility, study for controllable fluorescent material.
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| WO2001042228A1 (en) * | 1999-12-10 | 2001-06-14 | Prometic Biosciences Ltd. | Macrocyclic compounds and their use |
| WO2012110190A1 (en) * | 2011-02-17 | 2012-08-23 | Affectis Pharmaceuticals Ag | Novel p2x7r antagonists and their use |
| CN103193784A (en) * | 2013-04-07 | 2013-07-10 | 东华大学 | Pyrimidine group-containing rigid conjugated macrocyclic compound, as well as preparation method and application thereof |
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| WO2001042228A1 (en) * | 1999-12-10 | 2001-06-14 | Prometic Biosciences Ltd. | Macrocyclic compounds and their use |
| WO2012110190A1 (en) * | 2011-02-17 | 2012-08-23 | Affectis Pharmaceuticals Ag | Novel p2x7r antagonists and their use |
| CN103193784A (en) * | 2013-04-07 | 2013-07-10 | 东华大学 | Pyrimidine group-containing rigid conjugated macrocyclic compound, as well as preparation method and application thereof |
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