CN103193784B - 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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Abstract
The present invention relates to a kind of containing pyrimidine group rigidity Conjugate macrocycle compound and its preparation method and application, the general structure of compound is:
; Wherein, R is independently selected from one or more in hydrophobicity long chain alkyl group, hydrophilic long-chain group, chirality long chain alkyl group, ester group, cyano group, amino, aryl, sulfydryl separately.Preparation method comprises: (1) synthon II; (2) monomer II and bromo-2 iodine pyrimidines of 5-are by Suzuki linked reaction synthon III; (3) monomer II and monomer II I is utilized by the synthesis of Suzuki coupling one step to form the loop method containing pyrimidine group rigidity Conjugate macrocycle compound.The present invention can be used as excellent self-assembly unit molecular application in new function material exploitation; By the N heteroatoms contained by self and metal-complexing, present special photoelectric properties, in matrix material research.
Description
Technical field
The invention belongs to rigidity Conjugate macrocycle compound and its preparation method and application field, particularly one is containing pyrimidine group rigidity Conjugate macrocycle compound and its preparation method and application.
Background technology
In materialogy, chemistry and physics in, one of its most important target is exactly prepare the macrocylc compound that some have the pi-conjugated system of regular shape.Exploitation has the positive develop rapidly of research with the photoelectric device of the inorganic semiconductor material different qualities such as conventional silicon, and especially utilize the organic supramolecular of π-electron-conjugated system, polymer for the material of essentially consist unit, its design and development is more and more active.The preparation of nanometer soft material and the exploitation of function, for the research of the aspects such as solar cell, fuel cell, Organic Light Emitting Diode, molecular device opens theory more clearly.Related to this, have ordered structure, the rigid macrocyclic compound of Pi-conjugated systems and derivative thereof and be just 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 extremely strong mutual accumulation of π-π had by itself is easy to self-assembly occurs, thus make large ring form solid-state one dimension column non covalent bond polyphosphazene polymer aggregate structure, solid state two dimensional reticulated structure and three-dimensional structure.The one dimension of this high-sequential, two dimension, three-dimensional structure can be the moving passage that the carrier such as hole, electronics provides possible.The great interest of scientists is caused as the electronics of brand-new display anisotropic properties and photoelectron material material.
Containing N heteroatomic Conjugate macrocycle compound 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 flexible chain on its stiffening ring skeleton and ring, this kind of Conjugate macrocycle compound piles up by self π-π or one dimension, two and three dimensions supramolecular structure are constructed in concave-convex interaction self-assembly, also by the N heteroatoms contained by self and metal-complexing, special photoelectric characteristic can be presented.Therefore, during this kind of macrocylc compound is developed to new function material as excellent 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 this compound can be used as excellent self-assembly unit molecular application in new function material exploitation; By the N heteroatoms contained by self and metal-complexing, present special photoelectric properties, in matrix material research.
One of the present invention is containing pyrimidine group rigidity Conjugate macrocycle compound, and the general structure of described compound is:
; Wherein, R is independently selected from one or more in hydrophobicity long chain alkyl group, hydrophilic long-chain group, chirality long chain alkyl group, ester group, cyano group, amino, aryl, sulfydryl separately.
Described R group can be hydrophobicity or hydrophilic long-chain group, and described compound can be any one in following compound, but is not limited only to following compound:
In the embodiment of the present invention, described macrocylc compound, its flexible side-chains is dodecyloxy group, but is not only confined to this group.
Described compounds in side chain also can be expanded as any one in following compound, but is not limited only to following compound:
Atom N on described compound pyrimidine group and Pt, Pd or Ru coordination.
Atom N on described compound pyrimidine group and Pt coordination, cited title complex only makes example, is not limited only to following title complex:
in one.
Containing a preparation method for pyrimidine group rigidity Conjugate macrocycle compound, comprising:
(1) with 3,5-bis-bromofluoro benzene is raw material, by substitution reaction synthesis 3,5-dibromobenzene methyl ether, then through boron tribromide demethylation reaction synthesis 3,5-dibromophenol, 3,5-dibromophenols synthesize 3,5-dibromobenzene long chain ether with wetting ability, hydrophobicity or chirality long flexible chain halohydrocarbon by nucleophilic substitution reaction in the basic conditions more afterwards, utilize 3,5-dibromobenzene long chain ether to close two boron with two tetramethyl ethylene ketone and carry out Miyaura Reactive Synthesis monomer II;
(2) monomer II and bromo-2 iodine pyrimidines of 5-are by Suzuki linked reaction synthon III;
(3) monomer II and monomer II I is utilized by the synthesis of Suzuki coupling one step to form the loop method containing pyrimidine group rigidity Conjugate macrocycle compound.
Containing an application for pyrimidine group rigidity Conjugate macrocycle compound, as self-assembly unit molecular application in functional materials exploitation.
Containing an application for pyrimidine group rigidity Conjugate macrocycle compound, make with the coordination of metal the performances such as its photoelectricity change, can be used for preparing the matrix material with difference in functionality.
Secondly the present invention provides the research that a kind of utilization is developed for functional materials through self-assembly formation supramolecular structure body containing pyrimidine Conjugate macrocycle compound.Compound of the present invention has regular molecular structure, pore size is in Nano grade, to pile up by self π-π or one dimension, two and three dimensions supramolecular structure are constructed in concave-convex interaction self-assembly, as excellent self-assembly unit molecular application in new function material exploitation; In addition, by the N heteroatoms contained by macrocylc compound self and metal-complexing, special photoelectric properties can also be presented, in matrix material research.
beneficial effect
(1) the invention provides a class novel containing pyrimidine rigidity Conjugate macrocycle compound one step to form the loop synthesis method;
(2) the present invention can be used as excellent self-assembly unit molecular application in new function material exploitation;
(3) the present invention is by the N heteroatoms contained by self and metal-complexing, presents special photoelectric properties, in matrix material research.
Accompanying drawing explanation
Fig. 1 is that the MALDI-TOF Mass of embodiment 6 product schemes;
When Fig. 2 is room temperature, the ultraviolet-visible absorption spectroscopy figure (A) of embodiment 6 product and fluorescence spectrum figure (B).
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Adopt 3, 5-bis-bromofluoro benzene is starting raw material, by substitution reaction synthesis 3, 5-dibromobenzene methyl ether, 3 have been synthesized by boron tribromide demethylation reaction, 5-dibromophenol (Davidson J P, Sarma K, Fishlock D, et al.Synthesis of3, 5-Disubstituted Phenols [J] .Org Process Res Dev, 2010, 14 (2): 477-480.), again by 3, 5-dibromophenol and lauryl bromide synthesize 3 by nucleophilic substitution reaction in the basic conditions, 5-dibromobenzene lauryl ether (Lin C H, Tour J.Hydrogen-Bond-Assisted π-Stacking of Shape-Persistent Cyclophanes [J] .J Org Chem, 2002, 67 (22): 7761-7768.).Utilize 3,5-dibromobenzene lauryl ether closes two boron with two tetramethyl ethylene ketone and carries out Miyaura Reactive Synthesis boric acid ester intermediate monomer 2a, after by bromo-2 iodine pyrimidines of 2a and 5-by Suzuki linked reaction synthon 3a, finally utilize monomer 2a and 3a by Suzuki coupling one step to form the loop method synthesis target macrocylc compound 1a.
Embodiment 1
The synthesis of 3,5-dibromobenzene methyl ether (5)
3 are added in the round-bottomed flask of 500mL, 5-bis-bromofluoro benzene (4) (20.0g, 0.08mol, 1eq.) and dry DMF (350mL) after, in round-bottomed flask, slowly add sodium methylate (5.2g, 0.09mol, 1.2eq.), vigorous stirring overnight under room temperature, then adds 5%HCl neutralization, stopped reaction.CH
2cl
2extraction (50mL × 3), organic phase distillation washing (50mL × 3), anhydrous magnesium sulfate drying organic phase, cross and filter magnesium sulfate, revolve and steam except desolventizing obtains faint yellow solid, silica gel column chromatography is purified (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 2
The synthesis of 3,5-dibromophenol (6)
Add 3,5-dibromobenzene methyl ether (5) (5g, 18.8mmol, 1eq.) in 250mL two mouthfuls of flasks, under Ar gas shielded, add anhydrous CH
2cl
2(80mL), dropwise BBr is added at 0 DEG C
3(3.5mL, 37.6mmol, 2eq.), keeps 0 DEG C to react after 3 hours and rises to room temperature, and lucifuge reacts stopped reaction after trash ice cancellation in 2 days.Reaction solution CH
2cl
2extraction (50mL × 3), merge organic phase, distillation washing (50mL × 3), anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, revolve steaming steaming and desolventize, residuum silica gel column chromatography purifies (eluent: ether/sherwood oil=1/9), 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 3
The synthesis of 3,5-dibromobenzene lauryl ether (7)
Add 3,5-dibromophenol (6) (4g, 15.88mmol, 1eq.) respectively in 250mL two mouthfuls of flasks, lauryl bromide (4g, 16mmol, 1eq.), salt of wormwood (3.5g, 25mmol, 1.6eq.).Substitute gas under argon shield three times, add dry DMF (50mL), after being heated to 80 DEG C of reaction 36h, stopped reaction.Reaction solution is with petroleum ether extraction (50mL × 3), merge organic phase, distillation washing (50mL × 3), anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, revolve steaming steaming and desolventize, residuum silica gel column chromatography purifies (eluent: sherwood oil), obtain white crystal 6g, productive rate 90%.
1H NMR(400MHz,CDCl
3)：δ7.26(t,J=2Hz,1H),7.02(d,J=2Hz,2H),3.95(t,J=7Hz,2H),1.79(q,J=7Hz,2H),1.30(m,18H)0.92(t,J=7Hz,3H).
Embodiment 4
The synthesis of 3,5-bis-tetramethyl ethylene ketone boron benzene dodecane ether (2a)
Add successively 3,5-dibromobenzene lauryl ether (7) (2g, 4.76mmol, 1eq.) in the 100mL two-mouth bottle that magnetic stir bar and reflux be housed, double frequency alcohol closes two boron (2.68g, 10.5mmol, 2.2eq.), PdCl
2(dppf) (220mg, 0.3mmol, 6%eq.), KOAc (2.8g; 28.5mmol, 6eq.), substitute gas under argon shield three times, add the dry DMF (50mL) of freezing deoxygenation; be heated to 80 DEG C, react 3 hours, stopped reaction.After being chilled to room temperature, use CH
2cl
2extraction (50mL × 3), merge organic phase, distillation washing (50mL × 3), anhydrous magnesium sulfate drying, crosses and filters magnesium sulfate, revolves steaming steaming and desolventizes, residuum silica gel column chromatography purification (eluent: sherwood oil/methylene dichloride=8:1, the triethylamine of 2%), obtain pale yellowish oil product 1.29g, productive rate 53%.
1H NMR(400MHz,CDCl
3)δ7.87(s,1H),7.44(d,J=0.7Hz,2H),4.01(t,J=6.4Hz,2H),1.77(m,2H),1.58(s,2H),1.50-1.41(m,2H),1.35(s,24H),1.29(s,14H),0.91(t,J=6.8Hz,3H).
13C NMR(100MHz,CDCl
3):δ158.19,133.42,123.47,83.73,67.88,31.92,29.67,29.63,29.61,29.44,29.41,29.34,26.08,24.86,22.68,14.10。[M
+]:m/z calcd for C
30H
52B
2O
5:514.35.Found:514.0.
Embodiment 5
The synthesis of compound 3a
Compound 2a (1g, 1.94mmol, 1eq.) is added successively, the bromo-2-iodine pyrimidine (1.66g, 5.82mmol, 3eq.) of 5-, Pd (PPh in the 100mL two-mouth bottle that magnetic stir bar and reflux be housed
3)
4(302mg, 0.194mmol, 10%eq.), substitutes gas 3 times under argon shield, add the toluene 15mL of freezing deoxygenation, the K of freezing deoxygenation
2cO
3the aqueous solution (2mol/L) 8mL, the tetrahydrofuran (THF) 30mL of freezing deoxygenation, is heated to 80 DEG C, back flow reaction 48h, stopped reaction.After being chilled to room temperature, use CH
2cl
2extraction (50mL × 3), merge organic phase, distillation washing (50mL × 3), anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, revolve steaming steaming and desolventize, residuum neutral alumina chromatography column purifies (eluent: sherwood oil/methylene dichloride=4:1), obtain white solid 545mg, productive rate 49%.
1H NMR(400MHz,CDCl
3):δ9.08(s,1H),8.88(s,4H),8.13(d,J=1.1Hz,2H),4.17(t,J=6.4Hz,2H),1.91-1.83(m,2H),1.57-1.24(m,18H),0.90(t,J=6.8Hz,3H).
13CNMR(100MHz,CDCl
3):δ162.29,160.05,157.76,138.18,120.47,118.56,116.79,68.40,31.92,29.69,29.65,29.62,29.43,29.36,29.33,26.08,22.69,14.12。[M+]:m/z Cacld for C
26H
32Br
2O:576.37.Found:576.9556.Anal.Calcd.for C
26H
32Br
2O:C,54.18;H,5.60;N,9.72.Found:C,54.16;H,5.563;N,9.734。
Embodiment 6
The synthesis of compound 1a be separated
Compound 2a (100mg, 0.17mmol, 1eq.), compound 3a (90mg, 0.17mmol, 1eq.), Pd (PPh is added successively in the 25mL two-mouth bottle that magnetic stir bar and reflux be housed
3)
4(30mg, 0.019mmol, 11%eq.), substitutes gas three times under argon shield, add the toluene 3mL of freezing deoxygenation, the K of freezing deoxygenation
2cO
3the aqueous solution (2mol/L) 1mL, the tetrahydrofuran (THF) 6mL of freezing deoxygenation, is heated to 80 DEG C, back flow reaction 48h, stopped reaction.After being chilled to room temperature, use CH
2cl
2extract (50mL × 3), merge organic phase, distillation washing (50mL × 3), anhydrous magnesium sulfate drying, cross and filter magnesium sulfate, revolve steaming steaming and desolventize, residuum silica gel column chromatography is purified and (is used pure CH successively
2cl
2, EA, THF be eluent), collect the elutriant of THF section, revolve and steam steaming and desolventize, residuum is purified further through preparing gel permeation chromatography (GPC), and obtain target compound 10mg, productive rate is 8.7%.MALDI-TOF Mass:Calcd.For C
132H
180N
12O
6[M]
+:m/z=2029.41;Found:2029.6699。
Claims (1)
1., containing a preparation method for pyrimidine group rigidity Conjugate macrocycle compound, comprising:
(1) with 3,5-bis-bromofluoro benzene is raw material, by substitution reaction synthesis 3,5-dibromobenzene methyl ether, then through boron tribromide demethylation reaction synthesis 3,5-dibromophenol, 3,5-dibromophenols synthesize 3,5-dibromobenzene long chain ether with wetting ability, hydrophobicity or chirality long flexible chain halohydrocarbon by nucleophilic substitution reaction in the basic conditions more afterwards, utilize 3,5-dibromobenzene long chain ether to close two boron with two tetramethyl ethylene ketone and carry out Miyaura Reactive Synthesis monomer II
(2) monomer II and bromo-2 iodine pyrimidines of 5-are by Suzuki linked reaction synthon III
(3) monomer II and monomer II I is utilized by the synthesis of Suzuki coupling one step to form the loop method containing pyrimidine group rigidity Conjugate macrocycle compound
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Citations (3)
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|---|---|---|---|---|
| EP0560567A1 (en) * | 1992-03-09 | 1993-09-15 | Texaco Development Corporation | Calix-arene encapsulation of s-triazines and their use for reducing nitrogen oxides in Diesel fuel exhaust |
| WO2001042228A1 (en) * | 1999-12-10 | 2001-06-14 | Prometic Biosciences Ltd. | Macrocyclic compounds and their use |
| CN101747286A (en) * | 2009-12-24 | 2010-06-23 | 南京信息工程大学 | Nano-aperture 30-element triphenylamine rigid macrocyclic compound and preparation method thereof |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0560567A1 (en) * | 1992-03-09 | 1993-09-15 | Texaco Development Corporation | Calix-arene encapsulation of s-triazines and their use for reducing nitrogen oxides in Diesel fuel exhaust |
| WO2001042228A1 (en) * | 1999-12-10 | 2001-06-14 | Prometic Biosciences Ltd. | Macrocyclic compounds and their use |
| CN101747286A (en) * | 2009-12-24 | 2010-06-23 | 南京信息工程大学 | Nano-aperture 30-element triphenylamine rigid macrocyclic compound and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| A Cyclotetraicosaphenylene;Volker Hensel,等;《Chemistry - A European Journal》;19991231;第5卷(第2期);第421-429页 * |
| Synthesis of macrocyclic, triazine-based receptor molecules;Dennis W. P. M. Löwik,等;《European Journal of Organic Chemistry》;20011231(第15期);第2825-2839页 * |
| Volker Hensel，等.Building blocks for the construction of large chloro-functionalized,hexagonal oligophenylene cycles.《European Journal of Organic Chemistry》.1999,(第2期),第451-458页. * |
| Volker Hensel,等.Repetitive construction of macrocyclic oligophenylenes.《Angewandte Chemie》.1997,第36卷(第23期),第2654-2656页. * |
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