CN103819479A - Pyrimidine group contained rigid conjugated macrocyclic compound as well as preparation method and application thereof - Google Patents
Pyrimidine group contained rigid conjugated macrocyclic compound as well as preparation method and application thereof Download PDFInfo
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- CN103819479A CN103819479A CN201410086053.XA CN201410086053A CN103819479A CN 103819479 A CN103819479 A CN 103819479A CN 201410086053 A CN201410086053 A CN 201410086053A CN 103819479 A CN103819479 A CN 103819479A
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- pyrimidine group
- conjugate macrocycle
- macrocycle compound
- containing pyrimidine
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- 125000000714 pyrimidinyl group Chemical group 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000002678 macrocyclic compounds Chemical class 0.000 title abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- PZFMWYNHJFZBPO-UHFFFAOYSA-N 3,5-dibromophenol Chemical compound OC1=CC(Br)=CC(Br)=C1 PZFMWYNHJFZBPO-UHFFFAOYSA-N 0.000 claims abstract description 10
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- ASWYHZXKFSLNLN-UHFFFAOYSA-N 1,3-dibromo-5-fluorobenzene Chemical compound FC1=CC(Br)=CC(Br)=C1 ASWYHZXKFSLNLN-UHFFFAOYSA-N 0.000 claims abstract description 6
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 4
- 238000010520 demethylation reaction Methods 0.000 claims abstract description 4
- -1 macrocycle compound Chemical class 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 10
- 238000001338 self-assembly Methods 0.000 claims description 10
- 230000004043 responsiveness Effects 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 5
- 239000008204 material by function Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- WGLLSSPDPJPLOR-UHFFFAOYSA-N tetramethylethylene Natural products CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 claims description 4
- ZWZWQSKCVXIXQJ-UHFFFAOYSA-N 1,3-dichloro-2-methylprop-1-ene Chemical group ClCC(C)=CCl ZWZWQSKCVXIXQJ-UHFFFAOYSA-N 0.000 claims description 3
- CMAARKUAKYAGAZ-UHFFFAOYSA-N N1=CN=CC=C1.[I] Chemical class N1=CN=CC=C1.[I] CMAARKUAKYAGAZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000006197 hydroboration reaction Methods 0.000 claims description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000011160 research Methods 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 238000007070 tosylation reaction Methods 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- XJFZOSUFGSANIF-UHFFFAOYSA-N 3-chloro-2-(chloromethyl)prop-1-ene Chemical compound ClCC(=C)CCl XJFZOSUFGSANIF-UHFFFAOYSA-N 0.000 abstract description 2
- OQZAQBGJENJMHT-UHFFFAOYSA-N 1,3-dibromo-5-methoxybenzene Chemical compound COC1=CC(Br)=CC(Br)=C1 OQZAQBGJENJMHT-UHFFFAOYSA-N 0.000 abstract 1
- ZEZKXPQIDURFKA-UHFFFAOYSA-N 5-bromo-2-iodopyrimidine Chemical compound BrC1=CN=C(I)N=C1 ZEZKXPQIDURFKA-UHFFFAOYSA-N 0.000 abstract 1
- 238000007006 Miyaura reaction Methods 0.000 abstract 1
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 239000007858 starting material 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 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000012074 organic phase Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 9
- 235000019341 magnesium sulphate Nutrition 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000006392 deoxygenation reaction Methods 0.000 description 7
- 230000008014 freezing Effects 0.000 description 7
- 238000007710 freezing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 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
- 239000007787 solid Substances 0.000 description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000010025 steaming 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
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003786 synthesis 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
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 229940125890 compound Ia Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 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
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 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
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- 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
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- 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
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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- 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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Abstract
The invention relates to a pyrimidine group contained rigid conjugated macrocyclic compound as well as a preparation method and an application thereof. A structure formula of the compound is shown in the specification, wherein n is equal to 1, 2, 3, 4 and 5. The preparation method comprises the steps as follows: for a rigid part, 1, 3-dibromo-5-fluorobenzene is taken as a raw material to synthesize 1, 3-dibromo-5-methoxybenzene, and 3, 5-dibromophenol is synthesized through a boron tribromide demethylation reaction; for a linear part, 3-chloro-2-chloromethyl-1-propene is adopted as a starting material to obtain a linear part intermediate, and then under the alkaline condition, 3, 5-dibromophenol and the linear part intermediate synthesize 3, 5-dibromobenzene long-chain ether which has Miyaura reaction with bis(pinacolato) diboron to synthesize a monomer II; the monomer II and 5-bromo-2-iodopyrimidine have a Suzuki coupled reaction to synthesize a monomer III; and the monomer II and the monomer III are subjected to Suzuki coupling to obtain the compound. The obtained compound is taken as a functional material for application.
Description
Technical field
The invention belongs to Conjugate macrocycle compound and preparation thereof and Application Areas, particularly a kind of containing pyrimidine group rigidity Conjugate macrocycle compound and its preparation method and application.
Background technology
The eighties in last century supramolecular chemistry concept proposition till now, supramolecular chemistry has experienced rapidly development.Wherein, the supramolecular materials of stimuli responsive has become the study hotspot in supramolecular chemistry field to external world, especially utilizes the organic supramolecular of π-electron conjugated system, the material that polymer is essentially consist unit, and its design and development is more and more active.Related to this, the rigid macrocyclic compound and the derivative thereof that have ordered structure, Pi-conjugated systems are just being subject to huge attracting attention.The rich pi-conjugated compound of this class is according to the position of its polar functional group and orientation, the mutual accumulation of extremely strong π-π having by itself is easy to occur self-assembly, thereby make large ring form solid-state one dimension column non covalent bond macromolecule aggregation body structure, solid-state two-dimensional network structure and 3-D nano, structure.The one dimension of this high-sequential, two dimension, three-dimensional structure can be the carrier such as hole, electronics possible moving passage are provided.As the electronics of brand-new demonstration anisotropic properties and photoelectron material material and caused the great interest of scientists.
Containing the heteroatomic Conjugate macrocycle compound of N as the emerging Conjugate macrocycle compound of a class because its potential function and application is subject to extensive concern.Conjugate macrocycle compound containing pyrimidine group is one of representative of this compounds, they have very regular shape and structure, ring diameter is in Nano grade, according to the difference of its stiffening ring skeleton and the upper flexible chain of ring, this class Conjugate macrocycle compound can be piled up or one dimension, two and three dimensions supramolecular structure are constructed in concave-convex interaction self-assembly by self π-π, also can be used together the contained N heteroatoms of pyrimidine has in conjunction with proton, the abilities such as metal ion, study and can respond to the responsiveness functional materials of external stimulus for the preparation of matrix material.Therefore, during this class macrocylc compound is developed to new function material as good self-assembly unit molecular application.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of containing pyrimidine group rigidity Conjugate macrocycle compound and its preparation method and application, and gained compound of the present invention can be used as good self-assembly unit molecular application in new function material exploitation; The present invention can, by self contained N heteroatoms and metal-complexing, present special photoelectric properties, studies for matrix material; The present invention can be by preparing Modulatory character fluorescent material to sour induction.In addition, can there is by the size selectivity induction preparation to guest molecule the matrix material of different optical and electricity.
One of the present invention is containing pyrimidine group rigidity Conjugate macrocycle compound, and the general structure of described compound is:
Described R is independently hydrophobicity long chain alkyl group or hydrophilic long-chain group separately, and compound is:
Described compound is expanded through side chain:
N atom on described compound pyrimidine group and Pt coordination, the structural formula after coordination is:
N atom on described compound pyrimidine group and Pt, Pd or Ru coordination.
A kind of preparation method containing pyrimidine group rigidity Conjugate macrocycle compound of the present invention, comprising:
(1) rigid element is with 3, 5-bis-bromofluoro benzenes are raw material, synthesize 3 by substitution reaction, 5-dibromobenzene methyl ether, again through boron tribromide demethylation reaction synthetic 3, 5-dibromophenol, it is starting raw material that linear portion adopts the chloro-2-chloromethyl propylene of 3-, through three step (condensations, hydroboration oxidation, tosylation) obtain linear portion intermediate, afterwards 3, 5-dibromophenol synthesizes 3 with linear portion intermediate by nucleophilic substitution reaction again under alkaline condition, 5-dibromobenzene long chain ether, utilize 3, 5-dibromobenzene long chain ether and two tetramethyl ethylene ketones close two boron to carry out Miyaura and reacts synthon II,
(2) bromo-2 iodine pyrimidines of monomer II and 5-are by Suzuki linked reaction synthon III;
(3) utilize monomer II and monomer II I synthetic containing pyrimidine group rigidity Conjugate macrocycle compound by Suzuki coupling one step to form the loop method.
A kind of application containing pyrimidine group rigidity Conjugate macrocycle compound of the present invention, the described pyrimidine group rigidity Conjugate macrocycle compound that contains is developed in functional materials as self-assembly unit molecular application.
A kind of application containing pyrimidine group rigidity Conjugate macrocycle compound of the present invention, the described coordination containing pyrimidine group rigidity Conjugate macrocycle compound and metal is for the preparation of the matrix material with difference in functionality.
A kind of application containing pyrimidine group rigidity Conjugate macrocycle compound of the present invention, described have reversibility containing pyrimidine group rigidity Conjugate macrocycle compound to the responsiveness of PH, for regulating and controlling fluorescent material research.
A kind of application containing pyrimidine group rigidity Conjugate macrocycle compound of the present invention, prepares the matrix material with different optical and electricity by the size selectivity induction to guest molecule.
Secondly the present invention provides a kind of and has formed the research of supramolecular structure body for functional materials exploitation containing pyrimidine group rigidity Conjugate macrocycle compound through self-assembly.Compound of the present invention has regular molecular structure, pore size is in Nano grade, can pile up or one dimension, two and three dimensions supramolecular structure are constructed in concave-convex interaction self-assembly by self π-π, as good self-assembly unit molecular application in new function material exploitation; In addition, can also utilize the contained N heteroatoms of pyrimidine to have in conjunction with proton, the abilities such as metal ion, study and can respond to the responsiveness functional materials of external stimulus for the preparation of matrix material.
beneficial effect
(1) the invention provides series of new containing pyrimidine group rigidity Conjugate macrocycle compound one step to form the loop synthesis method, possess raw material synthetic method simple, mature preparation process, productive rate is compared with advantages of higher;
(2) the present invention can be used as good self-assembly unit molecular application in new function material exploitation;
(3) the present invention can, by self contained N heteroatoms and metal-complexing, present special photoelectric properties, studies for matrix material;
(4) the present invention can be by preparing Modulatory character fluorescent material and electronically active material (transfer transport or energy shift) to sour induction;
(5) the present invention can have by the size selectivity induction preparation to guest molecule the matrix material of different optical and electricity.
Accompanying drawing explanation
Fig. 1 is the GPC separation graph of embodiment 9 products;
Fig. 2 is target product I in embodiment 9
1, I
2, I
3mALDI-TOF Mass figure;
Fig. 3 is the middle I of embodiment 9 products
1to the fluorescence spectrum figure of sour responsiveness, the responsiveness fluorescence spectrum figure (b) to alkali to sour responsiveness fluorescence spectrum figure (a) and continuation.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Rigid element adopts 3, 5-bis-bromofluoro benzenes are starting raw material, synthesize 3 by substitution reaction, 5-dibromobenzene methyl ether, synthesize 3 by boron tribromide demethylation reaction, 5-dibromophenol (Davidson J P, Sarma K, Fishlock D, et al.Synthesis of 3, 5-Disubstituted Phenols[J] .Org Process Res Dev, 2010, 14 (2): 477-480.), in addition, it is starting raw material that linear portion adopts the chloro-2-chloromethyl propylene of 3-, through three step (condensations, hydroboration oxidation, tosylation) can obtain smoothly (Davies, P.J., 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-dibromophenol and linear portion intermediate 7 synthesize 11 by nucleophilic substitution reaction.Utilize 11 to close two boron with two tetramethyl ethylene ketones and carry out Miyaura and react synthetic boric acid ester centre monomer 2a, after by 2a and bromo-2 iodine pyrimidines of 5-by Suzuki linked reaction synthon 3a, finally utilize monomer 2a and 3a by the synthetic target macrocylc compound Ia of Suzuki coupling one step to form the loop method.
Embodiment 1
Synthesizing of compound 5
Add NaH (19.2g to being equipped with in two mouthfuls of flasks of 500mL of magnetic stir bar and reflux; 0.8mol, 7.4eq.), under the protection of Ar gas; substitute gas three times; add anhydrous THF (250mL), add 3-chloro-2-chloromethyl propylene (13.5g, 0.11mol; 1eq.); dropwise add 1-lauryl alcohol (42.3g, 0.227mol, 2.1eq.).At 65 ℃, back flow reaction is spent the night, and is cooled to room temperature, and the cancellation that adds water reaction is revolved to steam and revolved THF, uses CH
2cl
2extraction (50mL × 3), merging organic phase, distillation washing (50mL × 3), anhydrous magnesium sulfate drying organic phase, removes by filter magnesium sulfate, revolves to steam to desolventize silica gel column chromatography purification (eluent: PE/CH for residuum
2cl
2=5/1), obtain colourless liquid 32.4g, productive rate 75%.
1H?NMR(400MHz,CDCl
3):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
Synthesizing of compound 6
In two mouthfuls of flasks of 250mL, add 5 (8.0g, 0.02mmol), under Ar gas protection, substitute gas three times, add anhydrous THF (35mL), the 1mol/L BH that dropwise adds THF to dissolve at 0 ℃
3(28mL), rapid stirring 2 hours, drips 3mol/LNaOH (28mL).Rapid stirring 15 minutes, drips 30%H
2o
2(28mL), under room temperature, rapid stirring adds K for 30 minutes
2cO
3to saturated, CH
2cl
2extraction (50mL × 3), merges organic phase, distillation washing (50mL × 3), and anhydrous magnesium sulfate drying organic phase, removes by filter magnesium sulfate, revolves to steam to desolventize, and residuum is purified with silica gel column chromatography, obtains colourless liquid 6.5g, productive rate 79%.
1H?NMR(400MHz,CDCl
3):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)。
Synthesizing of compound 7
In two mouthfuls of flasks of 500mL, add 6 (3.9g, 9.57mmol, 1eq.), TsCl (9.13g, 47.9mmol, 5eq.), under the protection of Ar gas, substitutes gas three times, adds anhydrous CH
2cl
2(80mL), pyridine (11.4g, 144mmol, 15eq.), at 25 ℃, rapid stirring 5 hours, uses CH
2cl
2extraction (50mL × 30), merge organic phase, organic phase is first washed (50mL × 1) with 1mol/L HCl, with distillation washing (50mL × 3), anhydrous magnesium sulfate drying organic phase, removes by filter magnesium sulfate again, revolve to steam and desolventize, residuum is purified with silica gel column chromatography, obtains weak yellow liquid 4.6g, productive rate 85%.
1H?NMR(400MHz,CDCl
3):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
Synthesizing of 3,5-dibromobenzene methyl ether (9)
In the round-bottomed flask of 500mL, add 3,5-bis-bromofluoro benzenes (8) (20.0g, 0.08mol, 1eq.) and after dry DMF (350mL), in round-bottomed flask, slowly add sodium methylate (5.2g, 0.09mol, 1.2eq.), under room temperature, vigorous stirring is spent the night, and then adds 5%HCl neutralization, stopped reaction.CH
2cl
2extraction (50mL × 3), distillation washing (50mL × 3) for organic phase, anhydrous magnesium sulfate drying organic phase, remove by filter magnesium sulfate, revolve to steam and obtain faint yellow solid except desolventizing, silica gel column chromatography is purified by (eluent: sherwood oil), obtains white solid 30g, productive rate 95%.
1H?NMR(400MHz,CDCl
3):δ7.25(t,J=1.6Hz,1H),6.99(d,J=1.6Hz,2H),3.78(s,3H).
Embodiment 5
Synthesizing of 3,5-dibromophenol (10)
In two mouthfuls of flasks of 250mL, add 3,5-dibromobenzene methyl ether (9) (5g, 18.8mmol, 1eq.), under the protection of Ar gas, add anhydrous CH
2cl
2(80mL), dropwise add BBr at 0 ℃
3(3.5mL, 37.6mmol, 2eq.), keeps 0 ℃ of reaction to rise to room temperature after 3 hours, stopped reaction after lucifuge reaction trash ice cancellation in 2 days.Reaction solution CH
2cl
2extraction (50mL × 3), merge organic phase, distillation washing (50mL × 3), anhydrous magnesium sulfate drying, remove by filter magnesium sulfate, revolve steaming and desolventize, silica gel column chromatography purification (eluent: ether/sherwood oil=1/9) for residuum, obtain white solid 4.2g, productive rate 90%.Mp=86-89℃.
1H?NMR(400MHz,CDCl
3)：δ7.28(t,J=2.0Hz,1H),6.97(t,2H),4.95(s,1H).
Embodiment 6
Synthesizing of compound 11
In two mouthfuls of flasks of 100mL, add 7 (4g, 6.7mmol, 1eq.), 3,5-dibromophenol (3g, 13.4mmol, 2eq.), K
2cO
3(9g, 67mmol, 10eq.), under the protection of Ar gas, adds anhydrous THF (50mL), backflow 48h, stopped reaction.Revolve to steam and remove THF, use CH
2cl
2extraction (50mL × 3), merge organic phase, distillation washing (50mL × 3), anhydrous magnesium sulfate drying, remove by filter magnesium sulfate, rotation is steamed and is desolventized, silica gel column chromatography purification (eluent: PE/EA=25/1) for residuum, obtain light yellow liquid 3.8g, productive rate 85%.
1H?NMR(400MHz,CDCl
3):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
Compound 2a's is synthetic
In 50mL two-mouth bottle bottle, add successively 11 (500mg, 0.74mmol), two tetramethyl ethylene ketones close two boron (413.8mg, 1.63mmol), PdCl
2(dppf) (35.56mg, 0.045mmol, 6%), KOAc (435.1mg; 4.44mmol, 6eq.), under the protection of Ar gas, substitute gas three times, add dry DMF (freezing deoxygenation) (20mL); be heated to 80 ℃, react stopped reaction 3 hours.Be chilled to after room temperature CH
2cl
2extraction (50mL × 3), merge organic phase, distillation washing (50mL × 3), anhydrous magnesium sulfate drying organic phase, removes by filter magnesium sulfate, revolves to steam to desolventize, silica gel column chromatography purification (eluent: PE/EA=8/1) for residuum, GPC separates, and obtains light yellow oil: 319.41mg, productive rate 56%.
1H?NMR(400MHz,CDCl
3)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
Compound 3a's is synthetic
In the 25mL two-mouth bottle that magnetic agitation and reflux are housed, add successively 2a (100mg, 0.13mmol, 1eq.), the bromo-2-iodine pyrimidine of 5-(112.8mg, 0.40mmol, 3eq.), Pd (PPh
3)
4(8mg, 0.0066mmol, 5%mol), under the protection of Ar gas, adds the freezing deoxygenation of THF() the freezing deoxygenation of/Toluene() (10/5mL=2/1), 2mol/L K
2cO
3(freezing deoxygenation) (0.66mL, 10eq.), is heated to 85 ℃ of backflows, reacts stopped reaction after 24 hours.Be chilled to after room temperature, revolve and steam except desolventizing, CH
2cl
2extraction (50mL × 3), merge organic phase, distillation washing (50mL × 3), anhydrous magnesium sulfate drying organic phase, remove by filter magnesium sulfate, revolve steaming and desolventize, silica gel column chromatography purification (eluent: PE/EA=30/1) for residuum, obtain white solid 60mg, productive rate 56%.
1H?NMR(400MHz,CDCl
3)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
Compound I a synthesizes and separates
Add successively compound 2a (84mg, 0.1084mmol1eq.), compound 3a (90mg, 0.1084mmol, 1eq.), Pd (PPh to being equipped with in the 25mL two-mouth bottle of magnetic stir bar and reflux
3)
4(40mg, 0.0325mmol, 30%mmol), substitutes gas three times under argon shield, add the tetrahydrofuran (THF) 5mL of freezing deoxygenation, the toluene 2.5mL of freezing deoxygenation, the K of freezing deoxygenation
2cO
3the aqueous solution (2mol/L) 1mL, is heated to 80 ℃, back flow reaction 80h, stopped reaction.Be chilled to after room temperature, use CH
2cl
2extraction (50mL × 3), merge organic phase, distillation washing (50mL × 3), anhydrous magnesium sulfate drying, remove by filter magnesium sulfate, revolve steaming and desolventize, silica gel column chromatography purification (PE:EA=3:1) for residuum, residuum is further purified through preparing gel permeation chromatography (GPC), obtains following target compound:
I
1(n=1): productive rate is 11.5%.MALDI-TOF?Mass:Calcd.For?C
228H
372N
12O
18[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)。
I
2(n=2): productive rate is 9.3%.MALDI-TOF?Mass:Calcd.For?C
304H
496N
16O
24[M+Na]
+:m/z=4778.78;Found:4779.5273。
I
3(n=3): productive rate is 7.7%.MALDI-TOF?Mass:Calcd.For?C
304H
496N
16O
24[M+Na]
+:m/z=5967.76;Found:5968.8779。
Claims (10)
1. containing a pyrimidine group rigidity Conjugate macrocycle compound, it is characterized in that: the general structure of described compound is:
2. one according to claim 1, containing pyrimidine group rigidity Conjugate macrocycle compound, is characterized in that: described R is independently hydrophobicity long chain alkyl group or hydrophilic long-chain group separately, and compound is:
3. one according to claim 1, containing pyrimidine group rigidity Conjugate macrocycle compound, is characterized in that: described compound is expanded through side chain and is:
4. one according to claim 1, containing pyrimidine group rigidity Conjugate macrocycle compound, is characterized in that: the N atom on described compound pyrimidine group and Pt coordination, and the structural formula after coordination is:
5. one according to claim 1, containing pyrimidine group rigidity Conjugate macrocycle compound, is characterized in that: the metal-complexing such as N atom and Pt, Pd or Ru on described compound pyrimidine group.
6. the preparation method containing pyrimidine group rigidity Conjugate macrocycle compound as claimed in claim 1, comprising:
(1) rigid element is with 3, 5-bis-bromofluoro benzenes are raw material, synthesize 3 by substitution reaction, 5-dibromobenzene methyl ether, again through boron tribromide demethylation reaction synthetic 3, 5-dibromophenol, it is starting raw material that linear portion adopts the chloro-2-chloromethyl propylene of 3-, through condensation, hydroboration oxidation, tosylation obtains linear portion intermediate, afterwards 3, 5-dibromophenol synthesizes 3 with linear portion intermediate by nucleophilic substitution reaction again under alkaline condition, 5-dibromobenzene long chain ether, utilize 3, 5-dibromobenzene long chain ether and two tetramethyl ethylene ketones close two boron to carry out Miyaura and reacts synthon II,
(2) bromo-2 iodine pyrimidines of monomer II and 5-are by Suzuki linked reaction synthon III;
(3) utilize monomer II and monomer II I synthetic containing pyrimidine group rigidity Conjugate macrocycle compound by Suzuki coupling one step to form the loop method.
7. the application containing pyrimidine group rigidity Conjugate macrocycle compound as claimed in claim 1, is characterized in that: the described pyrimidine group rigidity Conjugate macrocycle compound that contains is developed in functional materials as self-assembly unit molecular application.
8. the application containing pyrimidine group rigidity Conjugate macrocycle compound as claimed in claim 1, is characterized in that: the described coordination containing pyrimidine group rigidity Conjugate macrocycle compound and metal is for the preparation of the matrix material with difference in functionality.
9. the application containing pyrimidine group rigidity Conjugate macrocycle compound as claimed in claim 1, is characterized in that: described have reversibility containing pyrimidine group rigidity Conjugate macrocycle compound to sour responsiveness, for regulating and controlling fluorescent material research.
10. the application containing pyrimidine group rigidity Conjugate macrocycle compound as claimed in claim 1, is characterized in that: the matrix material by the size selectivity induction preparation to guest molecule with different optical and electricity.
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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 |
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| CN109336894A (en) * | 2018-11-07 | 2019-02-15 | 东华大学 | One kind having AIE effect rigidity Conjugate macrocycle compound and its preparation and application |
| CN109336894B (en) * | 2018-11-07 | 2021-08-10 | 东华大学 | Rigid conjugated macrocyclic compound with AIE effect and preparation and application thereof |
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