Patent Application
20130090469
This application claims the benefits of Taiwan Patent Application Number 100136163 filed on Oct. 5, 2011 and Taiwan Patent Application Number 101100963 filed on Jan. 10, 2012, the subject matters of which are incorporated herein by reference.
1. Field of the Invention
The present invention relates to zinc porphyrin-based photosensitive compounds exhibiting highly efficient push-pull ability between electrons, in particular, to green zinc porphyrin-based photosensitive compounds. Also, the present invention relates to photosensitive dyes with high absorption coefficient and photoelectric conversion efficiency made from said zinc porphyrin-based photosensitive compounds, which may be employed in solar cells.
2. Description of Related Art
Recently, the increased demands of sustainable and renewable energy resources have attracted much attention to the development of photovoltaic devices. While silicon-based solar cells require high-cost production processes, dye-sensitized solar cells (DSSC) are promising candidates for photovoltaic applications because of the low-cost of raw materials and fabrication. For example, the most efficient polypyridine ruthenium-based DSSC have achieved power conversion efficiency of more than 11%. However, the drawbacks, such as rarity, environmental concern, low absorbance at the near-IR region, etc., limit their applications in DSSC and have lead to burgeoning developments for organic dyes.
Generally, the advantages of organic dyes include, for example, high absorption coefficient, facile modification of molecular structures, easily tuned photophysical properties, etc. Many types of organic dyes, such as coumarines, triphenylamines, perylenes, porphyrins and phthalocyanines, have been investigated. Some organic sensitive dyes may exhibit remarkable conversion efficiency which is comparable to to those of ruthenium complexes in DSSC. All these highly efficient organic dyes have the same moleculars modified with a π-electron push-pull framework.
It is known that Japan Publication Number 2009-132657 published on Jun. 18, 2009 disclosed a porphyrin-based complex with photosensitizing action and a photoelectric transducer using the same, in which a substituent on the porphyrin complex may be present in a form of heterocycle or aromatic ring.
US Patent Publication Number 2010/0125136 A1, which was published on May 20, 2010 and claimed the priority of Taiwan Patent Application Number 97144426, disclosed zinc porphyrin-based photosensitizer dyes. The zinc porphyrin-based photosensitizer dyes have porphyrin rings with anchoring groups for attaching to the semiconductor surface. Those anchoring groups comprise carboxyl group or carboxylate anion, which may provide longer anchoring groups to facilitate electron transfer from the excited dye molecules to the semiconductor surface. Also, the porphyrin rings contain substituents having extended π-conjugated systems to increase the absorption of porphyrin rings within the visible region.
Further, the published reference, H. P. Lu et al. “Design and characterization of highly efficient porphyrin sensitizers for green see-through dye-sensitized solar cells”, Phys. Chem. Chem. Phys., 2009, 11, 10270-10274, refers to dye-sensitized complexes YD11-YD13 which are based on a structure of D-P-B-A wherein D represents an electron-donating diarylamino group, P represents a porphyrin light-harvesting center, B represents π-conjugation bridge and A represents a carboxyl anchoring group.
The published reference, C. W. Lee et al. “Novel Zinc Porphyrin Sensitizers for Dye-Sensitized Solar Cells: Synthesis and Spectral, Electrochemical, and Photovoltaic Properties”, Chem. Eur. J. 2009, 15, 1403-1412, refers to a synthesis of porphyrin-based sensitizer dyes having an electron-donating group (EDG) linked at the meso-position of porphyrin ring.
The published reference, Takeru Bessho et al. “Highly Efficient Mesoscopic Dye-Sensitized Solar Cells Based on Donor-Acceptor-Substituted Porphyrins”, Angew. Chem. Int. ed., 2010, 49, 6646-6649, refers to a porphyrin YD2 having electron-donor and electron-acceptor substituents. For example, attached to the porphyrin ring a diarylamino donor group acts as an electron donor (D), and a ethynylbenzoic acid acts as an electron acceptor (A), thereby constituting a porphyrin chromophore having D-π-A structure.
The published reference, S. L. Wu et al., “Design and Characterization of Porphyrin Sensitizers with a Push-pull Framework for Highly Efficient Dye-sensitized Solar Cells”, Energy Environ. Sci., 2010, 3, 949-955, refers to porphyrin sensitizers YD14-YD17 with push-pull framework and attaching diarylamino and/or triphenyl amino group to different meso-position.
The published reference, C. P. Hsueh et al. “Synthesis and characterization of porphyrin sensitizers with various electron-donating substituents for highly efficient dye-sensitized solar cells”, J. Mater. Chem., 2010, 20, 1127-1134, refers to porphyrin photosensitizer dyes YD1-YD8 for solar cells, attaching an electron-donating group (EDG) at meso-position.
The known dyes stated above easily cause an aggregation of molecules because of their poor solubility, and result in an insufficient injection of electrons into the conduction band (CB) of TiO2 together with a loss of energy.
Also, according to recent advances on zinc porphyrin-based dyes with electron push-pull performance, it is known that the porphyrin ring attaching diarylamino as an electron-push group has a lower power conversion efficiency (η), for example, about 6.0%.
Thus, to resolve the technical problems and drawbacks as mentioned above, the inventors of the present invention design a series of highly efficient push-pull zinc porphyrin-based compounds and a synthesis of the same, to prevent a loss of energy due to the aggregation of molecules, as well as to provide a sufficient injection of electrons into a TiO2 conductive band. Further, the inventors also develop a series of processes of preparation for the zinc porphyrin-based compounds that contain diarylamino groups as electron-donors, and have long alkoxyl chains replacing tert-butyl groups. In addition, to enhance the photoelectric conversion, the absorption range of UV-Vis spectrum is enlarged via a π-conjugated system.
An objective of the present invention is to provide zinc porphyrin-based photosensitive compounds represented by a general formula as follows:
in the formula, L1 and L2 are each independently phenyl or —NRaRb, wherein the phenyl is optionally substituted with one to five substituents selected from the group consisting of C1-12 alkyl, C1-12 alkoxy and phenyl; Ra and Rb are each independently selected from the group consisting of C1-12 alkyl, C1-12 alkoxy and phenyl, where the phenyl is optionally substituted with one to five C1-12 alkyl.
A1 are selected from the group consisting of:
wherein R1, R2, R3 and R4 are each independently selected from the group consisting of C1-12 alkyl, C1-12 alkoxy, phenyl and phenoxy; Y1˜Y23 are each independently zero to one C1-10 alkyl, one to five C2-10 alkenyl or one to five C2-10 alkynyl; Z1˜Z23 are each independently H, alkali metals or quaternary ammonium represented by the following general formula (200):
wherein R4˜R7 are each independently represented by CmH2m+1 where m is an integer of 1 to 12.
D1 is selected from the group consisting of:
wherein R8˜R66 are each independently selected from the group consisting of H, phenyl, phenoxy, CmH2m+1 where m is an integer of 1 to 12, OCpH2p+1 where p is an integer of 1 to 12, CH2(OC2H4)nOCH3 where n is an integer of 1 to 30, and (OC2H4)qOCH3 where q is an integer of 1 to 30.
In the present invention, the zinc porphyrin-based photosensitive compounds bear a diaryl having a strong electron-push group at the meso-position of the porphyrin ring, and a hydrophobic long hydrocarbon chain modified from a tert-butyl on the diaryl group. Accordingly, the increase of stereo hindrance between molecules, the reduction of π-π interaction of the porphyrin ring itself and the enhancement of molecular solubility can be achieved, thereby preventing an aggregation of molecules.
Also, zinc porphyrin-based photosensitive dyes, in particular zinc porphyrin-based photosensitive dyes with green performance, contain the zinc porphyrin-based structure according to the present invention, in which the phenyl groups at the meso-10,20 positions of the porphyrin ring individually include two long alkoxy linked onto the para- or meta-site of phenyl to protect the dye from aggregation. On other side, the dyes exhibit highly efficient push-pull ability between electrons. Thus, the injection of electrons into one surface of the TiO2 anode may be efficiently increased, and the reduction of charge recombination and enhancement of photovoltaic property for the dyes can be achieved.
In the present invention, a triple bond-containing group as a crosslinking group may be linked onto the meso-position of the porphyrin ring. Further, a naphthalene or a anthracene obtained from the modification of benzoic acid may extend the length of the conjugated system in the porphyrin ring and form together with a carboxy group a push-pull system in the whole structure. Accordingly, the absorbance may be shifted to IR region and can obtain a superior effect of charge separation, thereby injecting excited electrons into conductive band (CB) on TiO2 surface through those groups and achieving an increase of photoelectric conversion efficiency.
According to the present invention, the thus-modified zinc porphyrin-based photosensitive compounds, in particular green zinc porphyrin-based photosensitive compounds, may be used as raw materials of photosensitized dye and are suitably employed in the applications of photoelectric conversion cells, such as dye-sensitized solar cells and the like.
Further an objective of the present invention is to provide photosensitized dyes having high absorption coefficient and photoelectric conversion efficiency, in particular a photosensitive dye for solar cells.
A further objective of the present invention is to provide uses of the zinc porphyrin-based photosensitive dyes in solar cells.
These features and advantages of the present invention will be further described and more readily apparent from a review of the detailed description of the preferred embodiments hereinafter.
The following detailed description of the preferred embodiments of the present invention can best be understood when read in connection with the drawings as follows:
In one embodiment of the present invention, the zinc porphyrin-based photosensitive compounds are represented by the following formula (120):
wherein L1 and L2 are each independently a phenyl having two to five substituents selected from the group consisting of C1-12 alkyl and C1-12 alkoxy. Preferably, L1 and L2 are each independently a phenyl having two to three substituents selected from the group consisting of C1-12 alkyl and C1-12 alkoxy. More preferably, L1 and L2 are each independently a phenyl having two to three substituents selected from the group consisting of C1-12 alkoxy. Most preferably, L1 and L2 are each independently a phenyl substituted with two C5-12 alkoxy.
In another embodiment of the present invention, L1 and L2 are each independently —NRaRb, wherein Ra and Rb are each independently C1-12 alkyl, C1-12 alkoxy or substituted phenyl. Preferably, the substituted phenyl has one to five substituents selected from the group consisting of C1-12 alkyl and C1-12 alkoxy; more preferably two to three substituents selected form the group consisting of C1-12 alkyl and C1-12 alkoxy.
In the present invention, Ra and Rb may be identical.
According to the present invention, the phenyl may be substituted with substituent(s) on the meta-, ortho- or para-position of phenyl ring; and preferably the meta- or ortho-position.
Also, in the formula (120) of zinc porphyrin-based photosensitive compounds according to the present invention, L1 and L2 linked on the meso-position of porphyrin ring may be identical, to form a porphyrin with a symmetrical configuration.
A1 may be selected from the group consisting of:
wherein R1, R2, R3 and R4 are each independently selected from the group consisting of H, C1-12 alkyl, C1-12 alkoxy, phenyl and phenoxy; Y1˜Y23 are each independently selected from the group consisting of 0 to one C1-10 alkyl, one to five C2-10 alkenyl and one to five C2-10 alkynyl; Z1˜Z23 are each independently selected from the group consisting of H, alkali metals and quaternary ammonium.
In an embodiment of the present invention, R1, R2, and R3 are each independently selected from the group consisting of C1-12 alkyl, C2-10 monoalkenyl, C2-10 dialkenyl, phenyl, C1-6 alkyl-substituted phenyl, C1-6 monoalkenyl-substituted phenyl, C1-6 dialkenyl-substituted phenyl, C2-6 alkynyl-substituted phenyl, naphthyl, anthranyl and thienyl, wherein the C2-10 monoalkenyl is optionally substituted with cyano, phenyl or naphthyl, and the phenyl or C1-6 alkyl-substituted phenyl is optionally substituted with —NO2 or halogen.
In the present invention, the quaternary ammonium is represented by a general formula (200) as follows:
wherein R4˜R7 are each independently represented by a general formula of CmH2m+1 where m is an integer of 1 to 12.
D1 may be selected from the group consisting of:
wherein R8˜R66 are each independently selected from the group consisting of H, phenyl, phenoxy, CmH2m+1 where m is an integer of 1 to 12, OCpH2p+1 where p is an integer of 1 to 12, CH2(OC2H4)pOCH3 where n is an integer of 1 to 30, and (OC2H4)qOCH3 where q is an integer of 1 to 30.
According to a preferred embodiment of the present invention, L1 and L2 each independently represent a phenyl having two substituents selected from the group consisting of C1-12 alkyl and C1-12 alkoxy; D1 is —NRaRb, wherein Ra and Rb represent identical groups selected from the group consisting of C1-12 alkyl and C1-12 alkoxy; and A1 represents a functional group having C2-6 alkynyl in which the functional group is a phenyl optionally substituted with substituent(s) selected from the group consisting of carboxy, C2-6 alkenyl substituted with cyano, NO2, C2-5 alkynyl,
or fluoro.
In the present invention, the exemplary compounds of the zinc porphyrin-based photosensitized dyes are listed below:
Hereinafter, reference will now be made in detail to preferred embodiments of the present invention, which constitute the best modes of practicing the present invention. However, it is to be understood that the disclosed embodiments are merely exemplary of the present invention that may be embodied in various and alternative forms, but are not intended to limit the scope of the present invention.
To a solution of resorcinol (60.0 g, 0.5 mol) dissolved in acetone (2500 mL) was added K2CO3 (24.5 g, 2.5 mol). The solution was heated and stirred under nitrogen atmosphere for 20 minutes; and then 1-bromo-3-methyl butane (251.7 mL, 2.0 mol) was introduced, to obtain a mixture. After the mixture was refluxed for six days, the mixture was filtered; and then the solvent was removed under concentration. The residue was extracted with dichloromethane; and the extracts in the organic layer were combined and dried over anhydrous MgSO4. The resulting crude product was purified by Silica Gel Column Chromatography using n-hexane, to give Compound 2 as a white liquid (113.75 g, 91%).
The white liquid was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=7.16 (t, J=8.0 Hz, 1H), 6.53-6.43 (m, 3H), 3.97 (t, J=6.8 Hz, 4H), 1.90-1.77 (m, 2H), 1.72-1.62 (m, 4H), 1.00-0.92 (m, 12H).
A three-necked flask was equipped with an addition funnel and charged with a solution of Compound 2 (25 g, 0.1 mol) and tetramethyl ethylene diamine TMEDA (0.125 mol) in tetrahydrofuran THF. The solution was degassed with nitrogen gas for 15 minutes; cooled to 0° C.; and then n-butyl lithium (93.7 mL, 1.6M in n-hexane) was added dropwise over 20 minutes. After stirring the solution for 3 hours, the solution was warmed to room temperature. To the solution was added dropwise dimethyl methanamine DMF (0.25 mol); and allowed to stir and react for an additional 2 hours. The reaction was quenched with water; and the mixture obtained therefrom was extracted with ether. The extracts were combined and dried over anhydrous MgSO4; and the solvent was removed under reduced pressure. The resulting crude product was recrystallized from hexane, to yield Compound 3 as a white solid (22.8 g, 82%).
The white solid was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz): δH=10.52 (s, 1H), 7.38 (t, J=8.4 Hz, 1H), 6.54 (d, J=8.8 Hz, 2H), 4.06 (t, J=6.4 Hz, 4H), 1.90-1.80 (m, 2H), 1.80-1.60 (m, 4H), 1.20-0.80 (m, 12H); 13C NMR (CdCl3, 100 MHz): δC=189.3, 161.7, 135.5, 104.5, 67.3, 37.7, 25.0, 22.5. MALDI-TOF: m/z calcd for C17H26O3 278. found 279 [M+1]+.
To a degassed solution of dipyrromethane (41.0 mmol) and Compound 3 (41.0 mmol) in dichloromethane DCM (5.4 L) was added trifluoroacetic acid (37.3 mmol); and the solution was stirred at 23° C. for 4 hours. To the solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone DDQ (14.1 g, 62.1 mmol) to form a mixture; and the mixture was stirred for an additional 1 hour and then filtered through silica SiO2. The solvent was removed from the residue under reduced pressure. The residue was purified by Silica Gel Column Chromatography using dichloromethane DCM/n-hexane (1:2), to obtain a crude product. The crude product was then recrystallized from MeOH/CH2Cl2, to yield Compound 4 as a purple powder (5.31 g, 32%).
The purple powder was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz): δH=10.16 (s, 2H), 9.27 (d, J=4.4 Hz, 4H), 8.98 (d, J=4.4 Hz, 4H), 7.72 (t, J=8.4 Hz, 2H), 7.03 (d, J=8.4 Hz, 4H), 3.87 (t, J=6.4 Hz, 8H), 0.87-0.64 (m, 12H), 0.25 (d, J=6.8 Hz, 24H), −3.03 (s, 2H); 13C NMR (CdCl3, 100 MHz): δC=160.2, 147.7, 145.0, 130.7, 130.5, 130.0, 119.9, 111.6, 105.3, 103.9, 67.1, 37.3, 24.2, 22.0. MALDI-TOF: m/z calcd for C52H62N4O4 806. found 806 [M]+.
To a stirred solution of Compound 4 (1.24 mmol) in DCM (400 mL) was added slowly a solution of N-bromosuccinimide NBS (1.12 mmol) in DCM (50 mL) at 0° C. under nitrogen atmosphere over 6 hours. Subsequently, the solvents were removed under reduced pressure to obtain a residue. The residue was purified by Silica Gel Column Chromatography using DCM/n-hexane (1:2) to obtain a crude product. The crude product was recrystallized from MeOH/CH2Cl2, to yield an intermediate product 5-bromo-10,20-bis(2,6-bis(3-methylbutoxy)phenyl)porphyrin as a purple powder (0.61 g, 56%).
The intermediate product was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz): δH=10.03 (s, 1H), 9.63 (d, J=4.8 Hz, 2H), 9.18 (d, J=4.4 Hz, 2H), 8.92-8.84 (m, 4H), 7.72 (t, J=8.4 Hz, 2H), 7.02 (d, J=8.0 Hz, 4H), 3.88 (t, J=6.4 Hz, 8H), 0.85 (dd, J=6.8 Hz, J=13.6 Hz, 8H), 0.82-0.71 (m, 4H), 0.26 (d, J=6.4 Hz, 24H), −2.87 (s, 2H); 13C NMR (CdCl3, 100 MHz): δC=160.1, 131.7, 131.2, 130.8, 130.3, 130.1, 119.9, 112.9, 105.1, 104.2, 102.0, 67.1, 37.2, 24.2, 22.0. MALDI-TOF: m/z calcd for C52H61BrN4O4 886. found 886 [M]+.
A suspension of the thus-prepared intermediate product 5-bromo-10,20-bis(2,6-bis(3-methylbutoxy)phenyl)porphyrin (1.0 g, 1.13 mmol) and Zn(OAc)2.2H2O (2.5 g, 11.3 mmol) in a solvent mixture of dichloromethane and methanol was stirred and reacted at room temperature for 3 hours. The reaction was quenched with water; and the resulting mixture was extracted with dichloromethane. The extracts were combined; and the combined extracts were washed with water and dried over anhydrous MgSO4. After removing the solvents under reduced pressure, Compound 5 was recovered (1.03 g, 96%).
Compound 5 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz): δH=10.09 (s, 1H), 9.71 (d, J=4.8 Hz, 2H), 9.26 (d, J=4.8 Hz, 2H), 9.04-8.90 (m, 4H), 7.72 (t, J=8.0 Hz, 2H), 7.02 (d, J=8.4 Hz, 4H), 3.87 (t, J=6.4 Hz, 8H), 0.93-0.75 (m, 8H), 0.75-0.60 (m, 4H), 0.30-0.10 (m, 24H); 13C NMR (CdCl3, 100 MHz): δC=160.0, 150.9, 150.8, 149.9, 148.8, 132.2, 132.1, 132.0, 131.5, 129.8, 121.1, 113.2, 105.2, 103.3, 67.1, 37.2, 24.1, 21.9. MALDI-TOF: m/z: calcd for C52H59BrN4O4Zn 948. found 948 [M]+.
A mixture of Compound 5 (1.0 g, 1.05 mmol), triisopropylacetylene (0.28 mL, 1.26 mmol), bis(triphenylphosphine)palladium(II) dichloride Pd(PPh3)2Cl2 (74.0 mg, 1.26 mmol), CuI(I) (20.1 mg, 0.11 mmol), tetrahydrofuran (32.8 mL) and triethylamine NEt3 (6.5 mL) was gently refluxed and reacted under nitrogen atmosphere for 4 hours. Then, the solvents were removed under vacuum to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane (1:2), to yield Compound 6 as a purple solid (1.01 g, 92%).
The purple solid was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz): δH=10.03 (s, 1H), 9.72 (d, J=4.4 Hz, 2H), 9.21 (d, J=4.4 Hz, 2H), 8.94 (d, J=4.4 Hz, 2H), 8.92 (d, J=4.4 Hz, 2H), 7.69 (t, J=8.8 Hz, 2H), 7.00 (d, J=8.8 Hz, 4H), 3.86 (t, J=6.4 Hz, 8H), 1.56-1.34 (m, 21H), 0.84-0.66 (m, 12H), 0.24 (d, J=6.4 Hz, 24H); 13C NMR (CdCl3, 100 MHz): δC=160.1, 151.9, 150.8, 150.2, 148.8, 131.7, 131.2, 131.0, 129.5, 121.3, 113.2, 105.9, 105.0, 67.0, 37.3, 24.3, 22.0, 19.1, 12.0. MALDI-TOF: m/z calcd for C63H80N4O4SiZn 1050. found 1050 [M]+.
To a stirred solution of Compound 6 (0.48 mmol) in DCM (265 mL) and pyridine (26.5 mL) was added NBS (0.71 mmol) at 23° C.; and stirred for 0.5 hour. The solvent was removed under reduced pressure to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane (1:2), to yield Compound 7 (0.51 g, 93%).
Compound 7 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz): δH=9.63 (d, J=4.4 Hz, 2H), 9.57 (d, J=4.4 Hz, 2H), 8.84 (d, J=4.4 Hz, 2H), 8.82 (d, J=4.8 Hz, 2H), 7.68 (t, J=8.4 Hz, 2H), 6.99 (d, J=8.4 Hz, 4H), 3.87 (t, J=6.4 Hz, 8H), 1.47-1.35 (m, 21H), 0.92-0.70 (m, 12H), 0.50-0.14 (m, 24H); 13C NMR (CdCl3, 100 MHz): δC=160.0, 152.8, 151.3, 150.6, 148.7, 143.7, 132.2, 131.9, 130.7, 129.7, 121.9, 120.9, 114.6, 104.9, 98.7, 96.0, 67.0, 39.3, 24.2, 22.0, 19.1, 11.9. MALDI-TOF: m/z calcd for C63H79BrN4O4SiZn 1128. found 1128 [M]+.
A mixture of bis(4-hexylphenyl)amine (0.598 mg, 1.77 mmol) and 60% NaH (70.9 g, 1.77 mmol), Compound 7 (0.5 g, 0.44 mmol), bis(2-diphenylphosphino)phenyl ether DPEphos (95.4 mg, 0.177 mmol) and palladium acetate(II) Pd(OAc)2 (27.1 mg, 0.11 mmol) in dry tetrahydrofuran was gently refluxed and reacted under nitrogen atmosphere for 4 hours. The solvent was removed under vacuum to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane (1:2), to yield Compound 8 (0.31 g, 51%).
Compound 8 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz): δH=9.71 (d, J=4.8 Hz, 2H), 9.21 (d, J=4.8 Hz, 2H), 8.91 (d, J=4.4 Hz, 2H), 8.72 (d, J=4.8 Hz, 2H), 7.68 (t, J=8.4 Hz, 2H), 7.25 (t, J=7.2 Hz, 4H), 7.10-6.90 (m, 8H), 3.97-3.82 (m, 8H), 2.49 (t, J=7.2 Hz, 4H), 1.51-1.40 (m, 21H), 1.40-1.21 (m, 16H), 0.97-0.81 (m, 14H), 0.72-0.57 (m, 4H), 0.35-0.14 (m, 24H); 13C NMR (CdCl3, 100 MHz): δC=159.9, 152.4, 152.0, 150.5, 150.2, 134.6, 132.0, 130.5, 130.4, 129.8, 128.7, 122.9, 121.9, 120.7, 114.2, 110.1, 105.1, 99.1, 96.4, 67.0, 37.3, 35.2, 31.7, 31.6, 29.1, 24.0, 22.6, 22.0, 19.1, 14.1, 11.9. MALDI-TOF: m/z calcd for C87H113N5O4SiZn 1385. found 1385 [M]+.
To a solution of Compound 8 (0.072 mmol) in dry tetrahydrofuran (10 mL) was added tetrabutylammonium fluoride TBAF (0.72 mL, 1M in THF); and stirred and reacted at 23° C. under nitrogen atmosphere for 30 minutes. The reaction was quenched with water; and the resulting solution was extracted with dichloromethane. The extracts in the organic layer were combined and dried over anhydrous MgSO4. The solvent was removed under reduced pressure to obtain a residue. A mixture of the residue and 4-iodobenzoic acid (0.29 mmol) was dissolved in a solvent mixture of dry tetrahydrofuran (35.5 mL) and NEt3 (7.1 mL); and then was degassed with nitrogen gas for 10 minutes, to obtain a degassed solution. To the degassed solution was added tris(dibenzylideneacetone)dipalladium(0) Pd2(dba)3 (0.014 mmol) and triphenyl arsine AsPh3 (0.14 mmol); and subsequently was refluxed and reacted under nitrogen atmosphere for 4 hours. The solvent was removed under reduced pressure to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/methanol (20:1); and then recrystallized from n-hexane/ethanol, to yield Compound 9 as a green solid (79.8 g, 82%).
Compound 9 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz): δH=9.68 (d, J=4.8 Hz, 2H), 9.17 (d, J=4.4 Hz, 2H), 8.92 (d, J=4.4 Hz, 2H), 8.68 (d, J=4.8 Hz, 2H), 8.17 (d, J=7.2 Hz, 2H), 8.08 (d, J=8.0 Hz, 2H), 7.68 (t, J=8.8 Hz, 2H), 7.21 (d, J=8.4 Hz, 4H), 6.99 (d, J=8.4 Hz, 4H), 6.95 (d, J=8.8 Hz, 4H), 3.98-3.90 (m, 8H), 2.45 (t, J=15.6 Hz, 4H), 1.40-1.18 (m, 16H), 0.97-0.79 (m, 12H), 0.76-0.60 (m, 6H), 0.38-0.14 (m, 24H); 13C NMR (CdCl3, 100 MHz): δC=170.0, 159.8, 152.0, 151.9, 150.6, 150.4, 150.2, 134.5, 132.1, 131.8, 131.1, 130.4, 130.3, 130.0, 129.8, 128.7, 128.1, 123.3, 121.9, 121.1, 114.0, 105.3, 97.6, 97.3, 94.6, 67.1, 37.3, 35.2, 31.7, 31.5, 29.1, 24.0, 22.6, 22.0, 14.1; ESI-MS: m/z calcd for C85H97N5O6Zn 1349. found 1349 [M]+.
A suspension of dipyrromethane (6.00 g, 41.1 mmol) and 3,5-di(isopentyloxy)benzaldehyde (11.4 g, 41.1 mmol) was added to dichloromethane (5.4 L) and stirred under nitrogen atmosphere; and then deoxidized with nitrogen for 30 minutes. Trifluoroacetic acid TFA (2.75 mL, 37.0 mmol) was charged. The reaction was carried out for 3.5 hours; and then 2,3-dichloro-5,6-dicyano-1,4-benzoquinone DDQ (13.99 g, 61.6 mmol) was added. After the reaction was performed for 1 hour, the solvents were removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane (1:1), and then was recrystallized from methanol/dichloromethane, to give Compound 11 as a purple solid (4.9 g, 30%).
The purple solid was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=10.32 (d, J=12.8 Hz, 2H), 9.39 (d, J=5.2 Hz, 4H), 9.20 (d, J=4.4 Hz, 4H), 7.43 (d, J=2.4 Hz, 4H), 6.92 (t, J=2 Hz, 2H), 4.19 (t, J=6.8 Hz, 8H), 1.96-1.86 (m, 4H), 1.82-1.77 (m, 8H), 1 (d, J=6.8 Hz, 24H).
Compound 11 (1 g, 1.24 mmol) was added to dichloromethane (638 mL) and stirred under nitrogen atmosphere. The solution was placed in an ice bath for 20 minutes. To the thus-prepared solution of Compound 11 was added dropwise a solution of N-bromosuccinimide NBS (198 mg, 1.24 mmol) which was completely dissolved in dichloromethane (80 mL); and was reacted. The reaction was traced by spotting the solution on a thin layer chromatography (TLC) plate and quenched with acetone. The resulting crude product was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane (1:2), to give an intermediate product as a purple-red solid (581 mg, 53%).
The intermediate product was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=10.16 (s, 1H), 9.73 (d, J=5.2 Hz, 2H), 9.28 (d, J=4.4 Hz, 2H), 9.09-9.07 (m, 4H), 7.38 (d, J=2.4 Hz, 4H), 6.92 (s, 2H), 4.18 (t, J=6.4 Hz, 8H), 1.94-1.87 (m, 4H), 1.87-1.76 (m, 8H), 1.00 (d, J=6.4 Hz, 24H), −3.03 (s, 2H).
Compound 12 was prepared under the reaction conditions described on Y. Xie et al, J. Phys. Chem. C 2008, 112, 10559, and K. Nakamura et al Chem. Lett. 2003, 32, 694.
In the organic layer, the intermediate product was dissolved in dichloromethane (270 mL); and then Zn(OAc)2.2H2O (1.45 g, 6.56 mmol) dissolved in methanol (54 mL) was added, to obtain a solution. Sequentially, the solution was stirred for 3 hours and extracted with water (200 mL). The extracts in the organic layer were combined and dried over anhydrous MgSO4. The solvent was removed under concentration, to give Compound 12 (572 mg, 92%).
Compound 12 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=10.18 (s, 1H), 9.79 (d, J=4.4 Hz, 2H), 9.34 (d, J=4.0 Hz, 2H), 9.25-9.10 (m, 4H), 7.36 (d, J=2.0 Hz, 4H), 6.89 (t, J=2.0 Hz, 2H), 4.16 (t, J=6.8 Hz, 8H), 1.96-1.83 (m, 4H), 1.83-1.73 (m, 8H), 0.99 (d, J=6.8 Hz, 24H). 13C NMR (CdCl3, 100 MHz) δC=158.1, 150.3, 150.1, 149.2, 143.9, 133.1, 132.9, 132.7, 131.9, 120.9, 114.5, 106.3, 104.8, 101.0, 66.8, 38.1, 25.1, 22.7. MALDI-TOF: m/z calcd for C52H59BrN4O4Zn 948. found 948 [M]+.
A mixture of Compound 12 (1.05 mmol), triisopropylacetylene (1.26 mmol), Pd(PPh3)2Cl2 (0.11 mmol), CuI(I) (0.11 mmol), tetrahydrofuran (32.8 mL) and triethylamine (6.5 mL) was gently stirred, refluxed and reacted under nitrogen atmosphere for 4 hours. Then, the solvent was removed under vacuum to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane (1:2), to yield Compound 13 as a purple solid (0.97 g, 88%).
Compound 13 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz): δH=10.20 (s, 1H), 9.85 (d, J=4.4 Hz, 2H), 9.34 (d, J=4.4 Hz, 2H), 9.17 (d, J=4.4 Hz, 2H), 9.15 (d, J=4.4 Hz, 2H), 7.38 (d, J=2.0 Hz, 4H), 6.89 (t, J=2.4 Hz, 2H), 4.16 (d, J=6.8 Hz, 8H), 1.98-1.83 (m, 4H), 1.83-1.72 (m, 8H), 1.54-1.37 (m, 21H), 0.99 (d, J=6.8 Hz, 24H); 13C NMR (CdCl3, 100 MHz): δC=158.2, 152.4, 150.2, 149.7, 149.6, 144.0, 133.0, 132.5, 131.8, 131.0, 121.3, 114.4, 109.6, 107.3, 101.0, 100.5, 66.8, 38.1, 25.1, 22.7, 19.1, 11.9. MALDI-TOF: m/z calcd for C63H80N4O4SiZn 1050. found 1050 [M]+.
To a stirred solution of Compound 13 (0.48 mmol) in dichloromethane (265 mL) and pyridine (26.5 mL) was added N-bromosuccinimide (127.0 mg, 0.71 mmol) and stirred for 0.5 hour at 23° C. The solvent was removed under reduced pressure to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane, to yield Compound 14 (0.48 g, 90%).
Compound 14 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz): δH=9.74 (d, J=4.8 Hz, 2H), 9.68 (d, J=4.8 Hz, 2H), 9.05 (d, J=4.8 Hz, 2H), 9.02 (d, J=4.8 Hz, 2H), 7.32 (d, J=2.4 Hz, 4H), 6.87 (t, J=2.4 Hz, 2H), 4.15 (t, J=6.8 Hz, 8H), 1.98-1.82 (m, 4H), 1.82-1.72 (m, 8H), 1.55-1.36 (m, 21H), 0.99 (d, J=6.4 Hz, 24H); 13C NMR (CdCl3, 100 MHz): δC=158.2, 153.2, 150.7, 150.0, 149.5, 143.8, 133.3, 133.1, 132.9, 131.3, 122.3, 114.4, 101.0, 66.8, 38.1, 25.1, 22.7, 19.1, 11.9. MALDI-TOF: m/z calcd for C63H79BrN4O4SiZn 1128. found 1128 [M]+.
A mixture of bis(4-hexylphenyl)amine (1.77 mmol) and 60% NaH (1.77 mmol), Compound 14 (0.44 mmol), DPEphos (0.177 mmol) and Pd(OAc)2 (0.11 mmol) in dry tetrahydrofuran (100 mL) was gently refluxed and reacted for 4 hours under nitrogen atmosphere. After the completion of the reaction, the solvent was removed under vacuum to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane, to yield Compound 15 (0.35 g, 57%).
Compound 15 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz): δH=9.73 (d, J=4.4 Hz, 2H), 9.26 (d, J=4.4 Hz, 2H), 9.03 (d, J=4.4 Hz, 2H), 8.87 (d, J=4.8 Hz, 2H), 7.30 (d, J=2.0 Hz, 4H), 7.20 (d, J=8.8 Hz, 4H), 6.96 (d, J=8.4 Hz, 4H), 6.84 (t, J=2.4 Hz, 2H), 4.13 (t, J=6.8 Hz, 8H), 2.47 (t, J=7.6 Hz, 4H), 1.95-1.80 (m, 4H), 1.79-1.70 (m, 8H), 1.58-1.40 (m, 21H), 1.36-1.20 (m, 16H), 0.97 (d, J=6.4 Hz, 24H), 0.92-0.80 (m, 6H); 13C NMR (CdCl3, 100 MHz): δC=158.3, 152.9, 152.7, 150.6, 149.9, 149.4, 143.9, 135.0, 133.0, 130.9, 130.8, 128.9, 124.4, 122.1, 121.7, 114.2, 109.4, 101.0, 100.6, 97.9, 66.8, 38.1, 35.2, 31.7, 31.5, 29.1, 25.1, 22.7, 22.6, 19.1, 14.1, 11.9. MALDI-TOF: m/z calcd for C87H113N5O4SiZn 1385. found 1385 [M]+.
To a solution of Compound 15 (0.072 mmol) in dry tetrahydrofuran (10 mL) was added tetrabutylammonium fluoride TBAF (0.72 mL, 1M in THF); and stirred, reacted at 23° C. under nitrogen atmosphere for 30 minutes. The reaction was quenched with H2O; and then the resulting solution was extracted with dichloromethane. The extracts in the organic layer were combined and dried over anhydrous MgSO4. The solvent was removed under reduced pressure to obtain a residue. A mixture of the residue and 4-iodobenzoic acid (0.29 mmol) was dissolved in a solvent mixture of tetrahydrofuran (35.5 mL) and triethylamine (7.1 mL). After the thus-forming solution was degassed with nitrogen for 10 minutes, tris(dibenzylideneacetone)dipalladium(0) Pd2(dba)3 (0.014 mmol) and AsPh3 (0.14 mmol) were added to the solution. The solution was refluxed for 4 hours under nitrogen atmosphere, and the solvent was removed under reduced pressure to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/methanol (20:1); and then recrystallized from n-hexane/ethanol, to give Compound 16 as a green solid (87 mg, 90%).
Compound 16 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz): δH=9.75 (d, J=4.8 Hz, 2H), 9.26 (d, J=4.4 Hz, 2H), 9.07 (d, J=4.4 Hz, 2H), 8.87 (d, J=4.8 Hz, 2H), 8.29 (d, J=8.4 Hz, 2H), 8.12 (d, J=8.4 Hz, 2H), 7.32 (d, J=2.4 Hz, 4H), 7.2 (d, J=8.8 Hz, 4H), 6.97 (d, J=8.4 Hz, 4H), 6.86 (s, 2H), 4.14 (t, J=6.4 Hz, 8H), 2.48 (t, J=8.0 Hz, 4H), 1.97-1.80 (m, 4H), 1.80-1.70 (m, 8H), 1.36-1.18 (m, 16H), 0.97 (t, J=6.8 Hz, 24H), 0.84 (t, J=6.4 Hz, 6H); 13C NMR (CdCl3, 100 MHz): δC=158.2, 152.7, 152.4, 150.6, 149.8, 149.5, 143.9, 135.0, 133.0, 131.2, 130.9, 130.5, 130.2, 129.2, 128.9, 124.7, 122.1, 121.9, 114.3, 100.9, 99.3, 96.2, 95.6, 66.7, 38.1, 35.2, 31.7, 31.5, 29.7, 29.1, 25.1, 22.6, 14.1; ESI-MS: m/z calcd for C85H97N5O6Zn 1349. found 1349 [M]+.
Compound 23 was prepared in the manner of the preparation for Compound 16 described above.
A mixture of dipyrromethane (6.04 g, 41.4 mmol), 2,6-bis(octyloxy)benzaldehyde (15.0 g, 41.4 mmol) was added to dichloromethane (5.40 L), stirred and was deoxidized with nitrogen for 30 minutes. To the solution was charged TFA (2.75 mL) and reacted for 3.5 hours under nitrogen atmosphere. After charging 2,3-dichloro-5,6-dicyano-1,4-benzoquinone DDQ (14.00 g, 61.7 mmol), the reaction was performed for an additional 1 hour. The solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane (1:2); and recrystallized from methanol/dichloromethane, to give Compound 18 as a purple solid (6.25 g, 30.7%).
Compound 18 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=10.15 (s, 2H), 9.26 (d, J=4.8 Hz, 4H), 8.98 (d, J=4.8 Hz, 4H), 7.71 (t, J=8.4 Hz, 2H), 7.02 (dd, J=2.4 Hz, J=8.4 Hz, 4H), 3.83 (t, J=6.4 Hz, 8H), 0.95-0.88 (m, 8H), 0.87-0.82 (m, 8H), 0.68-0.61 (m, 8H), 0.59-0.54 (m, 28H), 0.49-0.42 (m, 8H), −3.02 (s, 2H). 13C NMR (CdCl3, 100 MHz) δC=160.6, 148.1, 145.4, 131.2, 130.8, 130.4, 120.5, 112.0, 105.8, 104.4, 69.2, 31.7, 29.1, 25.7, 22.7, 14.3. MALDI-TOF-MS: m/z calcd for C64H86N4O4 974. found 975 [M+H]+.
Compound 18 (3.5 g, 3.59 mmol) was added to dichloromethane (1500 mL), stirred and deoxidized with nitrogen for 20 minutes. In an ice bath, to the thus-obtained solution of Compound 18 was added dropwise NBS (671 mg, 3.77 mmol) which was completely dissolved in dichloromethane (400 mL) and reacted. The reaction was traced by spotting the solution on TLC plate; and then quenched with acetone. The solvents were removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane (1:4), to give an intermediate product as a purple-red solid (2.3 g, 61%).
The intermediate product was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=10.01 (s, 1H), 9.62 (d, J=4.8 Hz, 2H), 9.17 (d, J=4.0 Hz, 2H), 8.88 (t, J=4.4 Hz, 4H), 7.70 (t, J=8.0 Hz, 2H), 7.01 (dd, J=3.2 Hz, J=8.4 Hz, 4H), 3.84 (t, J=6.4 Hz, 8H), 0.97-0.90 (m, 8H), 0.86-0.79 (m, 8H), 0.67-0.60 (m, 8H), 0.58-0.49 (m, 28H), 0.47-0.39 (m, 8H), −2.89 (s, 2H). 13C NMR (CdCl3, 100 MHz) δC=160.5, 132.3, 131.8, 130.6, 120.4, 113.3, 105.6, 104.7, 102.6, 69.1, 31.8, 29.1, 29.0, 25.8, 25.7, 22.7, 14.3. MALDI-TOF-MS: m/z calcd for C64H85BrN4O4 1054. found 1054 [M]+.
After the intermediate product was dissolved with CH2Cl2 (450 mL), a solution of Zn(OAc)2.2H2O (4.79 g, 21.82 mmol) in MeOH (450 mL) was added; and then was stirred and reacted for 1 hour. The solvents were removed under concentration to obtain a residue. The residue was added with water and then filtered, to give Compound 19 as a purple-red solid (3.63 g, 98%).
Compound 19 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=10.17 (d, J=2 Hz, 1H), 9.80 (d, J=4.8 Hz, 2H), 9.34 (d, J=4.8 Hz, 2H), 9.07 (t, J=4.4 Hz, 4H), 7.76 (t, J=8.0 Hz, 2H), 7.07 (dd, J=2.4 Hz, J=8.4 Hz, 4H), 3.91 (t, J=6.4 Hz, 8H), 1.03-0.97 (m, 8H), 0.88-0.80 (m, 8H), 0.66-0.40 (m, 44H). 13C NMR (CdCl3, 100 MHz) δ 160.5, 151.5, 151.4, 150.4, 149.3, 132.9, 132.8, 132.7, 132.6, 132.5, 132.1, 130.3, 121.5, 114.1, 105.8, 104.1, 69.1, 31.7, 29.1, 29.0, 25.7, 22.7, 14.3. MALDI-TOF-MS: m/z calcd for C64H83BrN4O4Zn 1116. found 1116 [M]+.
To a solution of Compound 19 (0.91 g, 0.81 mmol) in THF (30.0 mL) and Et3N (5.0 mL) was added Pd(PPh3)2Cl2 (110 mg, 0.16 mmol) and CuI(I) (47.0 mg, 0.24 mmol), and then (triisopropylsilyl)acetylene (0.37 mL, 2.04 mmol). The thus-obtained solution was refluxed for 3.5 hours under heating; and then was cooled to room temperature. The solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using CH2Cl2/n-hexane (1:4) and recrystallized from CH2Cl2/MeOH, to give Compound 20 as a solid (820 mg, 83%).
Compound 20 was identified and assayed, and the result was shown as follows: 1H NMR (CDCl3, 400 MHz) δ 10.20 (s, 1H), 9.91 (d, J=4.4 Hz, 2H), 9.38 (d, J=4.4 Hz, 2H), 9.12 (d, J=4.8 Hz, 2H), 9.09 (d, J=4.8 Hz, 2H), 7.80 (t, J=8.4 Hz, 2H), 7.12 (d, J=8.8 Hz, 4H), 3.96 (t, J=6.4 Hz, 8H), 1.67-1.56 (m, 21H), 1.05-1.02 (m, 8H), 0.91-0.85 (m, 8H), 0.71-0.45 (m, 44H). 13C NMR (CDCl3, 100 MHz) δ 160.5, 152.6, 151.5, 150.9, 149.7, 132.5, 132.1, 131.9, 131.2, 130.3, 121.8, 114.3, 110.9, 106.9, 105.9, 99.6, 96.5, 69.3, 31.8, 29.1, 29.0, 25.7, 22.7, 19.7, 19.6, 19.2, 19.1, 14.3, 12.5, 12.3, 11.9. MALDI-TOF-MS: m/z calcd for C75H104N4O4SiZn 1218. found 1219 [M+H]+.
To a solution of Compound 20 (820 mg, 0.67 mmol) added with CH2Cl2 (250 mL) and pyridine (5.0 mL) was charged NBS (119 mg, 0.67 mmol) through an addition funnel; and was reacted for 30 minutes. The reaction was traced by spotting the solution on TLC plate. The reaction was quenched with acetone. The solvents were removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using CH2Cl2/n-hexane (1:4) and recrystallized from CH2Cl2/MeOH, to give Compound 21 as a solid (690.0 mg, 79%).
Compound 21 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δ 9.72 (d, J=4.8 Hz, 2H), 9.65 (d, J=4.4 Hz, 2H), 8.92 (d, J=4.4 Hz, 2H), 8.89 (d, J=4.4 Hz, 2H), 7.71 (t, J=8.0 Hz, 2H), 7.03 (d, J=8.4 Hz, 4H), 3.88 (t, J=6.4 Hz, 8H), 1.55-1.45 (m, 21H), 1.02-0.95 (m, 8H), 0.89-0.80 (m, 8H), 0.66-0.39 (m, 44H). 13C NMR (CdCl3, 100 MHz) δ 160.4, 153.4, 151.9, 151.1, 149.4, 133.1, 132.9, 132.5, 131.5, 130.4, 121.4, 115.3, 110.4, 105.8, 105.5, 100.0, 97.0, 69.2, 31.8, 31.3, 29.1, 29.0, 25.7, 22.7, 19.6, 19.5, 14.3, 12.4, 12.2. MALDI-TOF-MS: m/z calcd for C75H103BrN4O4SiZn 1296. found 1297 [M+H]+.
To a mixture of Compound 21 (330 mg, 0.25 mmol) dissolved in toluene (44.2 mL), Pd(OAc)2 (14 mg, 0.06 mmol), DPEphos (50.0 mg, 0.09 mmol) and 60% NaH (40.0 mg, 1.02 mmol) in the reaction flask was charged a solution of bis(4-hexylphenyl)amine (340 mg, 1.02 mmol) dissolved in toluene (29.8 mL), and refluxed for 4 hours under heating; and then cooled to room temperature. The solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using CH2Cl2/n-hexane (1:4) and recrystallized from CH2Cl2/MeOH, to give Compound 22 as a solid (330.0 mg, 71%).
Compound 22 was identified and assayed, and the result was shown as follows: 1H NMR (CDCl3, 400 MHz) δ 9.66 (d, J=4.4 Hz, 2H), 9.19 (d, J=4.4 Hz, 2H), 8.86 (d, J=4.4 Hz, 2H), 8.70 (d, J=4.8 Hz, 2H), 7.64 (t, J=8.4 Hz, 2H), 7.22 (t, J=8.8 Hz, 4H), 6.94 (m, 8H), 3.82 (t, J=6.4 Hz, 8H), 2.46 (t, J=7.6 Hz, 4H), 1.55-1.52 (m, 4H), 1.49-1.43 (m, 21H), 1.27 (t, 12H), 1.01-0.94 (m, 8H), 0.88-0.76 (m, 22H), 0.65-0.43 (m, 44H). 13C NMR (CdCl3, 100 MHz) δ 160.3, 152.9, 152.4, 151.0, 150.9, 150.6, 135.1, 132.5, 132.4, 131.0, 130.9, 130.2, 129.1, 123.3, 122.4, 121.4, 114.7, 110.6, 105.7, 99.7, 96.6, 69.1, 35.7, 32.2, 32.0, 31.8, 31.4, 29.6, 29.0, 28.9, 25.6, 23.1, 22.7, 19.6, 19.5, 14.5, 14.2, 14.0, 12.4. MALDI-TOF-MS: m/z calcd for C99H137N5O4SiZn 1553. found 1554 [M+H]+.
To a solution of Compound 22 (0.072 mmol) in dry tetrahydrofuran (10 mL) was added TBAF (0.72 mL, 1M in THF), stirred and reacted for 30 minutes at 23° C. under nitrogen atmosphere. The reaction was quenched with H2O, and the resulting mixture was extracted with CH2Cl2. The extracts in the organic layer were combined and dried over anhydrous MgSO4. The solvent was removed under reduced pressure, to give an Intermediate M.
A mixture of Intermediate M and 4-iodobenzoic acid (0.29 mmol) was dissolved together in a solvent mixture of dry THF (35.5 mL) and NEt3 (7.1 mL); and then was degassed with nitrogen for 10 minutes. To the thus-obtained solution was added Pd2(dba)3 (0.014 mmol) and AsPh3 (0.14 mmol), and refluxed for 4 hours under nitrogen atmosphere. The solvent was removed under reduced pressure to obtain a residue. The residue was purified by Silica Gel Column Chromatography using CH2Cl2/CH3OH (20:1) and recrystallized from n-hexane/ethanol, to yield Compound 23 as a green solid (77%).
Compound 23 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=9.57 (d, J=4.8 Hz, 2H), 9.00 (d, J=4.4 Hz, 2H), 8.79 (d, J=4.4 Hz, 2H), 8.58 (d, J=4.8 Hz, 2H), 8.26 (d, J=8.4 Hz, 2H), 7.99 (d, J=8.0 Hz, 2H), 7.61 (t, J=8.4 Hz, 2H), 6.98 (d, J=8.0 Hz, 4H), 6.93 (d, J=8.4 Hz, 4H), 6.77 (d, J=8.4 Hz, 4H), 3.79 (t, J=6.4 Hz, 8H), 2.38 (t, J=7.6 Hz, 4H), 1.47 (s, 4H), 1.21 (s, 12H), 0.89 (t, J=7.6 Hz, 16H), 0.83-0.71 (m, 14H), 0.71-0.36 (m, 36H). 13C NMR (CdCl3, 100 MHz) δC=160.4, 152.5, 152.4, 151.0, 150.8, 135.1, 132.7, 132.5, 132.0, 131.7, 131.0, 130.8, 130.6, 130.4, 130.3, 129.9, 129.2, 123.8, 122.4, 121.4, 115.0, 109.2, 105.7, 98.4, 97.6, 95.1, 69.1, 35.7, 32.2, 31.9, 31.3, 30.2, 30.0, 29.6, 29.1, 28.9, 25.6, 23.1, 22.7, 14.5, 14.3. MALDI-TOF: m/z calcd for C97H121N5O6Zn 1517. found 1518 [M+1]+.
Compound 24 was prepared under the reaction conditions described on M. J. Plater, S. Aiken, G. Bourhill, Tetrahedron. 2002, 58, 2405.
To 3,5-di-tert-butyl(bromomethyl)benzene (30.0 g, 0.11 mol) was added a solution of MeOH/H2O (120 mL, 1:1), and then charged hexamethylenetetramine (62.0 g, 0.44 mol). The thus-obtained solution was heated and refluxed for 4 hours. To the solution was added concentrated hydrochloric acid (36 mL) in an ice bath. The solution was refluxed for 30 minutes under heating; and then was extracted with CH2Cl2 and recrystallized from EtOH/H2O, to give Compound 24 as a milky white solid (15.0 g, 65%).
Compound 24 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δ 10.00 (s, 1H), 7.72 (d, J=1.6 Hz, 2H), 7.71 (d, J=1.6 Hz, 1H), 1.36 (s, 18H).
Compound 25 was prepared based on the disclosures of Yoshida et al, Chem. Eur. J. 2003, 9, 58 and H. Shinmori et al, Angew. Chem., Int. Ed. 2003, 42, 2754.
A mixture of 3,5-di-tert-butylbenzaldehyde (8.3 g, 38 mmol), dipyrromethane (5.6 g, 38.3 mmol) was added to dichloromethane (5.0 L), and stirred. The thus-obtained solution was deoxidized with nitrogen for 30 minutes. To the solution was added TFA (2.55 mL, 34.3 mmol) under nitrogen atmosphere, and reacted for 3.5 hours. To the reaction solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone DDQ (12.9 g, 56.8 mmol), and reacted for 1 hour. The solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane (1:1) and recrystallized from methanol/dichloromethane, to give Compound 25 as a purple solid (4.1 g, 35%).
Compound 25 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=10.32 (s, 2H), 9.41 (d, J=4.8 Hz, 4H), 9.15 (d, J=4.4 Hz, 4H), 8.16 (d, 4H), 7.84 (t, 2H), 1.58 (s, 36H), −3.02 (s, 2H).
Compound 26 was prepared based on the disclosure of M. J. Plater et al, Tetrahedron. 2002, 58, 2405.
A solution of Compound 25 (1 g, 1.46 mmol) added to dichloromethane (750 mL) was stirred and deoxidized with nitrogen for 20 minutes. In an ice bath, to the solution of Compound 25 was added dropwise N-bromosuccinimide NBS (259 mg, 1.46 mmol) which was dissolved in CH2Cl2 (94 mL), and reacted. The reaction was traced by spotting the solution on TLC plate, and quenched with acetone. The solvents were removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane (1:4), to give an intermediate product as a purple-red solid (600 mg, 54%).
The intermediate product was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=10.19 (s, 1H), 9.76 (d, J=4.8 Hz, 2H), 9.30 (d, J=4.8 Hz, 2H), 9.02 (d, J=4.8 Hz, 4H), 8.09 (d, J=4.8 Hz, 4H), 7.84 (s, 2H), 1.56 (s, 36H), −2.94 (s, 2H).
After the intermediate product was dissolved in CH2Cl2, a solution of Zn(OAc)2.2H2O in MeOH was added. The thus-obtained solution was stirred, heated, refluxed for 1 hour, and concentrated. The resulting solution was shaken with water for 10 minutes and then filtered, to give Compound 26 as a purple-red solid (610 mg, 94%).
Compound 26 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=10.25 (s, 1H), 9.83 (d, J=4.8 Hz, 2H), 9.38 (d, J=4.8 Hz, 2H), 9.10 (dd, J=5.2, 4.4 Hz, 4H), 8.09 (d, 4H), 7.84 (s, 2H), 1.55 (s, 36H).
A solution of Compound 26 (1.63 g, 1.966 mmol) dissolved in tetrahydrofuran (400 mL) and Et3N (45 mL) was deoxidized with nitrogen for 15 minutes. To the solution was added bis(triphenyl phosphine)palladium dichloride (144 mg, 0.20 mmol) and CuI(I) (42 mg, 0.02 mmol); and then charged (triisopropylsilyl)acetylene (2.4 mL, 8.16 mmol). The thus-obtained solution was heated, refluxed for 3.5 hours and then cooled to room temperature. The solvent was removed under concentration to obtained a residue. The residue was purified by Silica Gel Column Chromatography using CH2Cl2/n-hexane (1:4) and recrystallized from dichloromethane/methanol, to give Compound 27 as a solid (1.56 g, 85%).
Compound 27 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=10.22 (s, 1H), 9.86 (d, J=4.8 Hz, 2H), 9.35 (d, J=4.8 Hz, 2H), 9.10 (d, J=4.4 Hz, 4H), 9.08 (d, J=4.4 Hz, 2H), 8.09 (d, J=2.0 Hz, 4H), 7.83 (d, J=2.0 Hz, 2H), 1.57 (s, 36H), 1.46-1.45 (m, 21H).
To a solution of Compound 27 (500 mg, 0.54 mmol) added to CHCl3 (300 mL) and pyridine (30 mL) was charged NBS (143 mg, 0.804 mmol), and reacted for 2 minutes. The reaction was quenched with acetone. The solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using CH2Cl2/n-hexane (1:4) and recrystallized from dichloromethane/methanol, to give Compound 28 as a solid (475 mg, 88%).
Compound 28 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=9.78 (d, J=5.2 Hz, 2H), 9.70 (d, J=4.8 Hz, 2H), 9.00 (d, J=4.8 Hz, 2H), 8.97 (d, J=4.8 Hz, 2H), 8.03 (d, J=2.0 Hz, 4H), 7.82 (d, J=2.0 Hz, 2H), 1.55 (s, 36H), 1.44-1.43 (m, 21H).
Bis(4-hexylphenyl)amine (58.5 mg, 0.173 mmol) and 60% NaH (28 mg, 0.42 mmol) were dissolved in tetrahydrofuran (5 mL), and stirred for 5 minutes. To the solution was added a mixture of Compound 28 (50 mg, 0.0495 mmol), Pd(OAc)2 (2.2 mg, 0.0098 mmol) and DPEphos (8.0 mg, 0.0148 mmol). The resulting solution was refluxed for 5 hours under heating, and then cooled to room temperature. The solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane (1:4) and recrystallized from dichloromethane/methanol, to give Compound 29 as a solid (42 mg, 67%).
Compound 29 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=9.75 (d, J=4.8 Hz, 2H), 9.28 (d, J=4.8 Hz, 2H), 8.95 (d, J=4.8 Hz, 2H), 8.81 (d, J=4.8 Hz, 2H), 8.00 (d, J=1.6 Hz, 2H), 7.77 (d, J=1.6 Hz, 2H), 7.21 (d, J=8.4 Hz, 4H), 6.96 (d, J=8.4 Hz, 2H), 2.46 (t, J=7.6 Hz, 4H), 1.52 (s, 36H), 1.45 (m, 21H), 1.24 (m, 16H), 0.82 (t, J=7.2 Hz, 6H).
To a solution of Compound 29 (25 mg, 0.02 mmol) dissolved in tetrahydrofuran (5 mL) was charged TBAF (1M in THF, 80 μL, 0.10 mmol), and reacted at room temperature for 30 minutes. The solvent was removed under concentration to obtain a residue. The residue was extracted with H2O and dichloromethane. The extracts in the organic layer were combined and dried over anhydrous MgSO4. The solvent was removed under concentration, to give Compound 30 (21.5 mg, 98%).
Compound 30 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=9.67 (d, J=4.8 Hz, 2H), 9.26 (d, J=4.8 Hz, 2H), 8.94 (d, J=4.8 Hz, 2H), 8.80 (d, J=4.8 Hz, 2H), 8.00 (d, J=2.0 Hz, 4H), 7.77 (d, J=2.0 Hz, 2H), 7.22-7.20 (m, 4H), 6.97-6.95 (m, 4H), 4.13 (s, 1H), 2.47 (t, J=7.6 Hz, 4H), 1.52 (s, 36H), 1.24 (m, 16H), 0.82 (t, J=6.4 Hz, 6H).
To a solution of Compound 29 (25 mg, 0.02 mmol) dissolved in THF (5 mL) was charged TBAF (1M in THF, 80 μL, 0.10 mmol); and reacted at room temperature for 30 minutes. The solvent was removed under concentration to obtain a residue. The residue was extracted with H2O and dichloromethane. The extracts in the organic layer were combined and dried over anhydrous MgSO4. The solvent was removed under concentration, to give an intermediate product (21.7 mg, 99%) for being employed in the next reaction step directly.
Compound 30 (21.7 mg) and (E)-2-cyano-3-(4-iodophenyl)acrylic acid (0.2 mmol) were dissolved in a solvent mixture of tetrahydrofuran (50 mL) and triethylamine (2 mL); and the thus-obtained solution was deoxidized with nitrogen for 10 minutes. To the deoxidized solution was added Pd2(dba)3 (0.012 mmol) and AsPPh3 (0.08 mmol); and the solution was refluxed for 4 hours under heating. The reaction was cooled to room temperature; and the solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using CH2Cl2/MeOH (20:1), and recrystallized from CH2Cl2/n-hexane, to give Compound 31 as a solid (36 mg, 70.4%).
Compound 31 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3/pyridine-d5, 400 MHz): δH=9.76 (d, J=4.8 Hz, 2H), 9.27 (d, J=4.8 Hz, 2H), 8.98 (d, J=4.8 Hz, 2H), 8.82 (d, J=4.8 Hz, 2H), 8.13 (d, J=8.4 Hz, 2H), 8.07 (d, J=8.0 Hz, 2H), 8.03 (d, J=2.0 Hz, 4H), 7.78 (t, J=3.6 Hz, 2H), 7.51 (s, 1H), 7.22 (d, J=8.4 Hz, 4H), 6.97 (d, J=8.4 Hz, 4H), 2.48 (t, J=7.6 Hz, 4H), 1.52 (s, 36H), 1.36 (m, 12H), 0.84 (t, J=6.4 Hz, 6H); 13C NMR (CdCl3/pyridine-d5, 100 MHz): δe=165.3, 152.1, 150.4, 150.1, 149.8, 148.2, 141.4, 134.4, 133.0, 132.8, 131.5, 130.9, 130.4, 129.8, 129.5, 128.9, 128.5, 124.0, 121.7, 120.5, 116.3, 114.3, 109.2, 105.1, 98.3, 97.8, 95.3, 35.0, 34.8, 31.5, 31.2, 28.8, 22.4, 13.9; UV-vis (THF): λmax/nm (ε, 103M−1cm−1)=453(90), 587(6), 659(27). MALDI-TOF-MS: m/z calcd for C84H90N6O2Zn 1280. found 1280 ([M]+).
Compound 30 (0.16 mmol) and 4-bromo-2-nitrobenzoic acid (1.6 mmol) were dissolved in a solvent mixture of tetrahydrofuran (45 mL) and Et3N (8 mL); and the solution was deoxidized with nitrogen for 10 minutes. To the deoxidized solution was added Pd2(dba)3 (0.048 mmol) and AsPPh3 (0.32 mmol). The thus-obtained solution was refluxed for 4 hours under heating to perform the reaction. The reaction was cooled to room temperature. The solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/methanol (20:1), to give Compound 32 as a solid (118 mg, 57.9%).
Compound 32 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3/pyridine-d5, 400 MHz): δH=9.66 (d, J=4.8 Hz, 2H), 9.16 (d, J=4.8 Hz, 2H), 8.87 (d, J=4.4 Hz, 2H), 8.70 (d, J=4.4 Hz, 2H), 8.22 (s, 1H), 8.12 (s, 1H), 7.92 (d, J=1.6 Hz, 4H), 7.69 (s, 2H), 7.15 (d, J=8.4 Hz, 4H), 6.90 (d, J=8.4 Hz, 4H), 2.45 (t, J=8.0 Hz, 4H), 1.45 (s, 36H), 1.23 (m, 12H), 0.83 (t, J=6.4 Hz, 6H); 13C NMR (CdCl3/pyridine-d5, 100 MHz): δc=151.9, 150.4, 150.0, 149.6, 148.1, 141.3, 134.3, 133.8, 132.9, 132.7, 131.0, 130.3, 129.8, 129.4, 128.4, 126.0, 124.8, 123.9, 121.6, 120.4, 108.5, 97.4, 96.6, 93.2, 34.8, 34.6, 31.3, 31.1, 29.3, 28.7, 22.2, 13.7; UV-vis (THF): λmax/nm (ε, 103M−1 cm−1)=443(209), 586(10), 649(34). MALDI-TOF-MS: m/z calcd for C81H88N6O4Zn 1272. found 1272 ([M]+).
Compound 30 (0.08 mmol) and 6-bromo-2-naphthenic acid (0.8 mmol) were dissolved in tetrahydrofuran (25 mL) and Et3N (4 mL); and the solution was deoxidized with nitrogen for 10 minutes. To the deoxidized solution was added Pd2(dba)3 (0.024 mmol) and AsPPh3 (0.16 mmol). The resulting solution was refluxed overnight under heating; and then the reaction was cooled to room temperature. The solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/methanol (20:1), to give Compound 33 as a solid (46.4 mg, 45.4%).
Compound 33 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3/pyridine-d5, 400 MHz) δH=9.78 (d, J=4.8 Hz, 2H), 9.17 (d, J=4.4 Hz, 2H), 8.91 (d, J=4.4 Hz, 2H), 8.73 (d, J=4.4 Hz, 2H), 8.56 (s, 1H), 8.52 (s, 1H), 8.27 (dd, J=1.6 Hz, 1H), 8.11 (s, 1H), 8.03 (d, J=8.8 Hz, 1H), 7.96 (d, J=1.6 Hz, 4H), 7.73 (t, J=1.6 Hz, 2H), 7.16 (d, J=8.8 Hz, 4H), 6.91 (d, J=8.8 Hz, 4H), 2.45 (t, J=8.0 Hz, 4H), 1.49 (s, 36H), 1.23 (m, 12H), 0.82 (t, J=6.4 Hz, 6H); 13C NMR (CdCl3/pyridine-d5, 100 MHz) δ 169.2, 152.2, 150.5, 150.2, 149.7, 148.3, 141.6, 135.2, 134.4, 132.8, 131.9, 130.7, 130.4, 130.0, 129.6, 128.9, 128.6, 127.6, 126.6, 124.0, 123.7, 123.0, 121.7, 120.5, 98.7, 95.8, 95.4, 53.2, 35.0, 34.8, 31.6, 31.5, 31.3, 28.9, 22.4, 13.9; UV-Vis (THF): λmax/nm (ε, 103M−1 cm−1)=448(210), 590(10), 651(34). MALDI-TOF-MS: m/z calcd for C85H91N5O2Zn 1279. found 1279 ([M]+).
Compound 30 (0.16 mmol) and 7-iodo-2-oxo-2H-chromene-3-carboxylic acid (0.8 mmol) were dissolved in THF (45 mL) and Et3N (8 mL); and the solution was deoxidized with nitrogen for 10 minutes. To the deoxidized solution was added Pd2(dba)3 (44 mg, 0.048 mmol) and AsPPh3 (0.32 mmol); and the solution was refluxed for 4 hours under heating to perform the reaction. The reaction was cooled to room temperature. The solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/methanol (20:1), to give Compound 34 as a solid (140.4 mg, 67.6%).
Compound 34 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3/pyridine-d5, 400 MHz): δ 9.65 (d, J=4.8 Hz, 2H), 9.17 (d, J=4.8 Hz, 2H), 8.91 (d, J=4.8 Hz, 2H), 8.86 (s, 1H), 8.71 (d, J=4.8 Hz, 2H), 7.97 (t, J=2.4 Hz, 4H), 7.95 (d, J=2.0 Hz, 4H), 7.81 (d, J=8.4 Hz, 1H), 7.74 (s, 2H), 7.15 (d, J=8.4 Hz, 4H), 6.92 (d, J=8.8 Hz, 4H), 2.46 (t, J=7.2 Hz, 4H), 1.50 (s, 36H), 1.23 (m, 12H), 0.83 (t, J=6.4 Hz, 6H); 13C NMR (CdCl3/pyridine-d5, 100 MHz): δ 164.7, 159.8, 155.0, 152.2, 152.1, 150.4, 150.1, 149.9, 148.3, 141.3, 134.5, 133.2, 132.9, 131.0, 130.6, 129.7, 129.5, 128.6, 127.8, 124.6, 123.5, 121.8, 120.6, 118.3, 117.5, 117.1, 100.6, 96.7, 94.6, 35.0, 34.8, 31.5, 31.3, 28.8, 22.4, 13.9; UV-vis (THF): λmax/nm (ε, 103M−1cm−1)=453(125), 587(8), 663(41). MALDI-TOF-MS: m/z calcd for C84H89N5O4Zn 1295. found 1295 ([M]+).
Compound 30 (0.08 mmol) and diethyl 4-iodoisophthalate (0.4 mmol) were dissolved in tetrahydrofuran (25 mL) and Et3N (4 mL); and the solution was deoxidized with nitrogen for 10 minutes. To the deoxidized solution was added Pd2(dba)3 (0.024 mmol) and AsPPh3 (0.16 mmol); and the solution was refluxed for 4 hours under heating to perform the reaction. The reaction was cooled to room temperature. The solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using ethyl acetate/n-hexane (1:4) and recrystallized from acetonitrile/ether, to give Compound 35 as a solid (93.7 mg, 88%).
Compound 35 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=9.75 (d, J=4.4 Hz, 2H), 9.28 (d, J=4.4 Hz, 2H), 8.99 (d, J=4.8 Hz, 2H), 8.82 (d, J=4.8 Hz, 2H), 8.26 (d, J=1.6 Hz, 1H), 8.13 (dd, J=6.0 Hz, 1H), 8.03 (d, J=2.0 Hz, 4H), 7.90 (d, J=7.6 Hz, 1H), 7.79 (t, J=1.6 Hz, 2H), 7.22 (d, J=8.8 Hz, 4H), 6.98 (d, J=8.4 Hz, 4H), 4.47-4.35 (m, 4H), 2.49 (t, J=7.6 Hz, 4H), 1.53 (s, 36H), 1.45-1.38 (m, 6H), 1.30-1.24 (m, 12H), 0.85 (t, J=6.8 Hz, 6H).
To Compound 35 (0.02 mmol) was added a mixture of NaOH (0.02 g), THF (5 mL) and water (1 mL). The solution was refluxed for 24 hours under heating, concentrated and filtered, to obtain a solid. The solid was dissolved in dichloromethane, acidified with an aqueous solution of glacial acetic acid, and then extracted once with water. The resulting solution was dried over anhydrous MgSO4; and the solvents were removed under concentration, to give Compound 36 as a solid (28 mg, 99%).
Compound 36 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3/methanol-d3, 400 MHz) δ 9.73 (d, J=4.8 Hz, 2H), 9.20 (d, J=4.8 Hz, 2H), 8.91 (d, J=4.4 Hz, 3H), 8.75 (d, J=4.4 Hz, 2H), 8.50 (d, J=8.0 Hz, 1H), 8.13 (d, J=9.2 Hz, 1H), 8.00 (s, 4H), 7.75 (s, 2H), 7.21 (d, J=8.4 Hz, 4H), 6.95 (d, J=8.4 Hz, 4H), 2.46 (t, J=7.6 Hz, 4H), 1.51 (s, 36H), 1.23 (m, 12H), 0.83 (t, J=6.4 Hz, 6H). MALDI-TOF-MS: m/z calcd for C82H89N5O4Zn 1271. found 1273 ([M+2H]+).
To a solution of Compound 22 (0.077 mmol) dissolved in tetrahydrofuran (10 mL) was charged TBAF (1M in THF, 0.39 mL), and reacted at room temperature for 30 minutes. The solvent was removed under concentration to obtain a residue. The residue was extracted with H2O and dichloromethane. The extracts in the organic layer were combined and dried over anhydrous MgSO4; and the solvent was removed under concentration, to give an intermediate product (105 mg, 99%) for being employed in the next reaction directly.
A solution of the intermediate product and 2,3,5,6-tetrafluoro-4-iodo-benzoic acid (123.0 mg, 0.38 mmol) dissolved in tetrahydrofuran (18 mL) and Et3N (3.5 mL) was deoxidized with nitrogen for 10 minutes. To the deoxidized solution was added Pd2(dba)3 (0.023 mmol) and AsPPh3 (0.15 mmol); and the solution was refluxed for 24 hours under heating to perform the reaction. The reaction was cooled to room temperature. The solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/methanol (20:1), to give Compound 37 as a solid (24.5 mg, 20%).
Compound 37 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3/pyridine-d5, 400 MHz) δH=9.70 (d, J=4.8 Hz, 2H), 9.17 (d, J=4.4 Hz, 2H), 8.88 (d, J=4.4 Hz, 2H), 8.68 (d, J=4.8 Hz, 2H), 7.66 (t, J=8.4 Hz, 2H), 7.20 (d, J=8.0 Hz, 4H), 6.96 (d, J=8.4 Hz, 8H), 3.82 (t, J=6.4 Hz, 8H), 2.44 (t, J=7.6 Hz, 4H), 1.56 (s, 4H), 1.24 (s, 12H), 0.97 (t, J=7.6 Hz, 16H), 0.83-0.81 (m, 14H), 0.62-0.49 (m, 36H). MALDI-TOF-MS: m/z calcd for C97H117F4N5O6Zn 1589. found 1589 ([M]+).
A mixture of 2-cyano-3-(2,3,5,6-tetrafluoro-4-iodo-phenyl)acrylic acid (141.0 mg, 0.38 mmol) added to Intermediate M prepared in the aforementioned Example 3 was dissolved in tetrahydrofuran (18 mL) and Et3N (3.5 mL); and the mixture solution was deoxidized with nitrogen for 10 minutes. To the deoxidized solution was added Pd2(dba)3 (0.023 mmol) and AsPPh3 (0.15 mmol). The solution was refluxed for 24 hours under heating to perform the reaction. The reaction was cooled to room temperature. The solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/methanol (20:1), to give Compound 38 as a solid (85.9 mg, 68%).
Compound 38 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3/pyridine-d5, 400 MHz) δH=9.62 (d, J=4.4 Hz, 2H), 9.16 (d, J=4.8 Hz, 2H), 8.91 (d, J=4.8 Hz, 2H), 8.66 (d, J=4.8 Hz, 2H), 7.87 (s, 1H), 7.68 (t, J=8.0 Hz, 2H), 7.21 (d, J=8.4 Hz, 4H), 6.99 (d, J=8.4 Hz, 4H), 6.95 (d, J=8.4 Hz, 4H), 3.87 (t, J=6.4 Hz, 8H), 2.47 (t, J=7.6 Hz, 4H), 1.52 (s, 4H), 1.25 (s, 12H), 1.03 (t, J=7.6 Hz, 16H), 0.85-0.79 (m, 14H), 0.66-0.45 (m, 36H); MALDI-TOF-MS: m/z calcd for C100H118F4N6O6Zn 1640. found 1641 ([M+H]+).
A mixture of 3-iodobenzoic acid (0.38 mmol) added to Intermediate M prepared in the aforementioned Example 3 was dissolved in tetrahydrofuran (18 mL) and Et3N (3.5 mL); and the solution was deoxidized with nitrogen for 10 minutes. To the deoxidized solution was added Pd2(dba)3 (0.023 mmol) and AsPPh3 (0.15 mmol). The solution was refluxed for 4 hours under heating to perform the reaction. The reaction was cooled to room temperature. The solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/methanol (20:1), to give Compound 39 as a green solid (88 mg, 77%).
Compound 39 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=9.67 (d, J=4.4 Hz, 2H), 9.17 (d, J=4.8 Hz, 2H), 8.87 (d, J=4.4 Hz, 2H), 8.68 (d, J=4.4 Hz, 3H), 8.19 (dd, J=9.2 Hz, 1H), 7.72 (s, 1H), 7.66 (t, J=8.4 Hz, 2H), 7.54 (d, J=8.4 Hz, 1H), 7.21 (d, J=8.4 Hz, 4H), 6.96 (d, J=8.4 Hz, 4H), 6.93 (d, J=8.8 Hz, 4H), 3.84 (t, J=6.4 Hz, 8H), 2.46 (t, J=7.6 Hz, 4H), 1.53 (s, 4H), 1.24 (s, 12H), 1.01 (t, J=7.6 Hz, 16H), 0.87-0.78 (m, 14H), 0.63-0.45 (m, 36H); 13C NMR (CdCl3/pyridine-d5, 100 MHz) δc=159.8, 151.8, 151.3, 150.3, 149.9, 134.6, 133.9, 132.5, 132.0, 131.5, 130.0, 129.2, 128.8, 128.3, 125.0, 122.3, 121.4, 113.6, 108.6, 105.1, 97.6, 94.7, 93.9, 68.4, 53.2, 35.1, 31.6, 31.3, 29.5, 29.0, 28.5, 25.0, 22.4, 22.2, 13.9, 13.7; UV-vis (THF): λmax/nm (ε, 103M−1 cm−1)=443(200), 580(14), 639(27). MALDI-TOF-MS: m/z calcd for C97H121N5O6Zn 1517. found 1518 ([M+H]+).
A mixture of diethyl 4-iodo-phthalate (112 mg, 0.32 mmol) added to Intermediate M prepared in the aforementioned Example 3 was dissolved in tetrahydrofuran (15 mL) and Et3N (3.2 mL); and the solution was deoxidized with nitrogen for 10 minutes. To the deoxidized solution was added Pd2(dba)3 (17.7 mg, 0.019 mmol) and AsPPh3 (40 mg, 0.13 mmol). The solution was refluxed for 4 hours under heating to perform the reaction. The reaction was cooled to room temperature; and the solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using ethyl acetate/n-hexane (1:4), to yield Compound 40 as a solid (77.7 mg, 75%).
Compound 40 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=9.63 (d, J=4.4 Hz, 2H), 9.17 (d, J=4.4 Hz, 2H), 8.88 (d, J=5.2 Hz, 2H), 8.68 (d, J=4.4 Hz, 3H), 8.25 (d, J=1.2 Hz, 1H), 8.11 (dd, J=1.2 Hz, 1H), 7.96 (d, J=7.6 Hz, 1H), 7.67 (t, J=8.4 Hz, 2H), 7.21 (d, J=8.8 Hz, 4H), 6.96 (d, J=8.4 Hz, 4H), 6.93 (d, J=8.8 Hz, 4H), 4.51-4.41 (m, 4H), 3.84 (t, J=6.4 Hz, 8H), 2.47 (t, J=7.6 Hz, 4H), 1.48-1.42 (m, 6H), 1.30-1.25 (m, 16H), 0.99 (t, J=7.2 Hz, 16H), 0.89-0.76 (m, 14H), 0.65-0.43 (m, 36H).
To Intermediate M (33.0 mg, 0.02 mmol) was added a mixture of NaOH (0.02 g), tetrahydrofuran (5 mL) and water (1 mL). The mixture solution was refluxed for 24 hours under heating, concentrated, and then filtered to obtain a solid. The solid was dissolved in dichloromethane, acidified with an aqueous solution of glacial acetic acid, and then extracted once with water. The extract was dried over anhydrous MgSO4; and the solvents were removed under concentration, to give Compound 41 as a solid (30.2 mg, 95%).
Compound 41 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3/Methanol-d3, 400 MHz) δH=9.58 (d, J=4.8 Hz, 2H), 9.06 (d, J=4.4 Hz, 2H), 8.83 (s, 1H), 8.75 (d, J=4.0 Hz, 2H), 8.56 (d, J=4.4 Hz, 2H), 8.43 (d, J=7.6 Hz, 1H), 8.08 (d, J=8.4 Hz, 1H), 7.64 (t, J=8.0 Hz, 2H), 7.17 (d, J=8.4 Hz, 4H), 6.94 (d, J=8.0 Hz, 4H), 6.88 (d, J=8.8 Hz, 4H), 3.81 (t, J=6.4 Hz, 8H), 2.42 (t, J=7.6 Hz, 4H), 1.47-1.43 (m, 6H), 1.30-1.19 (m, 16H), 0.95 (t, J=6.8 Hz, 16H), 0.89-0.78 (m, 14H), 0.72-0.48 (m, 36H).
To a solution of Compound 22 (26.4 mg, 0.02 mmol) dissolved in tetrahydrofuran (5.0 mL) was added TBAF (1 M in THF, 0.08 mL, 0.08 mmol). After the solution was stirred at 25° C. for 30 minutes, the reaction was quenched with H2O. Then, the solution was extracted with dichloromethane; and the extracts in the organic layer were combined and dried over anhydrous MgSO4. The solvent was removed under concentration to obtain a residue. The residue was employed in the next reaction directly.
A mixture of 9-bromo-perylene-3,4-dicarboxylic anhydride (16.0 mg, 0.04 mmol) added to Pd2(dba)3 (2.2 mg, 2.5 mmol) and AsPh3 (6 mg, 0.02 mmol) was dissolved in tetrahydrofuran (5 mL) and NEt3 (1 mL); and the resulting solution was refluxed for 3 hours under heating to perform the reaction. The reaction was cooled to room temperature; and the solvents were removed under reduced pressure to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane (4:6) and recrystallized from dichloromethane/methanol, to give Compound 42 as a solid (55%).
Compound 42 was identified and assayed, and the result was shown as follows: 1H NMR (CdCl3, 400 MHz) δH=9.77 (d, J=4.4 Hz, 2H), 9.35 (d, J=8.4 Hz, 1H), 9.19 (d, J=4.4 Hz, 2H), 8.97 (d, J=4.4 Hz, 2H), 8.73 (d, J=8.4 Hz, 2H), 8.58 (br, 2H), 8.34 (d, J=5.6 Hz, 1H), 8.00 (s, 4H), 7.96 (t, J=8.0 Hz, 1H), 7.78 (s, 2H), 7.17 (d, J=8.4 Hz, 4H), 6.93 (d, J=8.4 Hz, 4H), 2.47 (t, J=8.0 Hz, 4H), 1.53 (s, 36H), 1.24 (m, 22H), 0.84 (m, 8H); 13C NMR (CdCl3, 100 MHz) δC=158.9, 153.0, 152.1, 150.6, 150.4, 150.2149.0, 141.0, 135.1, 133.7, 132.8, 132.5, 131.4, 130.5, 129.6, 128.9, 128.6, 126.5, 125.8, 124.0, 122.5, 121.2, 117.6, 115.4, 108.7, 105.4, 97.7, 93.1, 35.2, 35.1, 31.7, 31.8, 31.5, 29.7, 29.5, 29.4, 29.2, 22.6, 14.1; UV-Vis (CH2Cl2): λmax/nm (ε/103 M−1 cm−1)=486(114), 679(38); IR (KBr, cm−1): v=2957, 2923, 2854, 2174, 1768, 1719, 1587, 1506, 1451, 1340, 1250, 1018, 800, 711; HRMS: m/z calcd for C90H98N5O3Zn 1360.6956. found 1360.6982 ([M+H]+).
A solution of Compound 18 added to dichloromethane (1500 mL) was stirred and deoxidized with nitrogen for 20 minutes. In an ice bath, a solution of N-bromosuccinimide NBS (2 mol) completely dissolved in dichloromethane (250 mL) was added dropwise to the solution of Compound 18 (975 mg, 1 mol), to perform the reaction. The reaction was traced by spotting the solution on TLC plate. After the reaction was quenched with acetone, the solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane (1:4), to give an intermediate product as a purple-red solid (980 mg, 82%). To a solution of the intermediate product dissolved in dichloromethane was added a solution of Zn(OAc)2.2H2O in MeOH; and the resulting solution was stirred and refluxed for 1 hour under heating. Then, the product solution was concentrated, shaken together with water for 10 minutes and filtered, to give Compound 43 as a purple-red solid.
Compound 43 was identified and assayed, and the result was shown as follows: 1H NMR (400 MHz, cdcl3) δ 9.52 (d, J=4.7 Hz, 4H), 8.81 (d, J=4.5 Hz, 4H), 7.71 (t, J=8.4 Hz, 2H), 7.00 (d, J=8.5 Hz, 4H), 3.85 (t, J=6.4 Hz, 8H), 1.08-0.91 (m, 9H), 0.83 (dd, J=14.5, 7.2 Hz, 9H), 0.72-0.21 (m, 50H), −2.60 (s, 2H).
A solution of Compound 43 (3.3 g, 2.76 mmol) dissolved in tetrahydrofuran (110 mL) and Et3N (33.0 mL) was deoxidized with nitrogen for 15 minutes. To the deoxidized solution was added Pd(PPh3)2Cl2 (0.264 g, 0.376 mmol) and CuI(I) (0.08 g, 0.42 mmol), and then charged triisopropylsilyl acetylene (3.1 mL). The resulting solution was refluxed for 3.5 hours under heating to perform the reaction. The reaction was cooled to room temperature. The solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane (1:2) and recrystallized from dichloromethane/methanol, to give Compound 44 as a solid (1.8 g, 46%).
Compound 44 was identified and assayed, and the result was shown as follows: 1H NMR (400 MHz, cdcl3) δ 9.68 (d, J=4.5 Hz, 4H), 8.88 (d, J=4.5 Hz, 4H), 7.69 (t, J=8.4 Hz, 2H), 7.01 (d, J=8.5 Hz, 4H), 3.85 (t, J=6.4 Hz, 8H), 1.57-1.37 (m, 42H), 1.03-0.90 (m, 9H), 0.83 (dd, J=14.6, 7.3 Hz, 11H), 0.67-0.32 (m, 49H).
iii) Compound 45
To a stirred solution of Compound 44 (1 g, 0.715 mmol) in THF (50 mL) was added TBAF (0.27 mL) at room temperature over 1 hour. The solution was concentrated, and then extracted with CH2Cl2. The extracts in the organic layer were combined and concentrated, to give Compound 45 as a solid (0.75 g, 97%). Compound 45 was employed directly in the next reaction.
To a mixture of 4-iodoanisole (0.70 g, 3.00 mmol), t-BuOK (0.34 g, 3.00 mmol), 2,2′-bipyridine (3 mg, 0.02 mmol) and CuI(I) (4 mg, 0.02 mmol) was added toluene (6 mL) and aniline (0.09 mL, 1.00 mmol). The solution was heated and reacted for 6 hours at 135° C. After the reaction was cooled to room temperature, the solid product was filtered off and washed with toluene. The filtrates were combined, and the solvent was removed therefrom to obtain a residue. The residue was purified by Silica Gel Column Chromatography using n-hexane, to give an intermediate product as a yellow solid (0.21 g, 70%).
The intermediate product was identified and assayed, and the result was shown as follows: 1H NMR (400 MHz, CdCl3) δH=7.15 (t, J=7.6 Hz, 2H), 7.03 (d, J=7.6 Hz, 4H), 6.91 (d, J=7.6 Hz, 2H), 6.72-6.88 (m, 5H), 3.77 (s, 12H).
Chloroform (10 mL) was added to a 25 mL three-necked flask charged with N,N-bis(4-methoxylphenyl)-N-phenylamine (200 mg, 0.66 mmol) and I2 (200 mg, 0.80 mmol). After completely dissolving the solids, PhI2(CF3CO2)2 (172 mg, 0.40 mmol) was added. The reaction was maintained at 50° C. and performed for 1 hour. Subsequently, the reaction was cooled to room temperature, and the resulting product solution was washed with aqueous Na2S2O3 solution and extracted with dichloromethane/water. The extracts in the organic layer were combined and dried over anhydrous MgSO4, to obtain a residue. The residue was purified by Silica Gel Column Chromatography using dichloromethane/n-hexane (1:1) and recrystallized from ethanol/dichloromethane, to give Compound 46 as a pale-yellow solid (270 mg, 95%).
Compound 46 was identified and assayed, and the result was shown as follows: 1H NMR (400 MHz, CdCl3) δH=7.38 8.8 Hz, 2H), 7.01 (d, J=8.8 Hz, 4H), 6.80 (d, J=8.8 Hz, 4H), 6.65 (d, J=8.8 Hz, 2H), 3.77 (s, 12H).
A mixture of Compound 45 (0.75 g, 0.7 mmol), 4-iodobenzoic acid (0.174 g, 0.7 mmol), Compound 46 (0.3 g, 0.7 mmol), Pd2(dba)3 (0.2 g, 0.21 mmol) and AsPh3 (0.54 mg, 1.75 mmol) was dissolved in tetrahydrofuran (80 mL) and Et3N (10 mL). The resulting solution was refluxed for 4.5 hours under heating. The solvent was removed under concentration to obtain a residue. The residue was purified by Silica Gel Column Chromatography using CH2Cl2/CH3OH (9.5:1) and recrystallized from dichloromethane/methanol, to give Compound 47 as a solid (0.45 mg, 43%).
Compound 47 was identified and assayed, and the result was shown as follows: 1H NMR (400 MHz, CdCl3) δ 9.58 (t, J=4.2 Hz, 4H), 8.79 (d, J=4.5 Hz, 2H), 8.75 (d, J=4.5 Hz, 2H), 8.20 (d, J=8.4 Hz, 2H), 8.02 (d, J=8.3 Hz, 2H), 7.76 (d, J=8.6 Hz, 2H), 7.68 (t, J=8.4 Hz, 2H), 7.16 (d, J=8.9 Hz, 4H), 7.02 (dd, J=16.5, 8.6 Hz, 6H), 6.89 (d, J=8.9 Hz, 4H), 3.85 (d, J=6.5 Hz, 8H), 1.02-0.83 (m, 21H), 0.72 (dd, J=14.1, 8.0 Hz, 11H), 0.55 (t, J=7.3 Hz, 36H), 0.52-0.39 (m, 12H).
Reference Compound 48 represented by the following formula was provided as a control example. The photoelectric conversion efficiencies of Compound 9 (Example 1), Compound 23 (Example 3) and Compound 47 (Example 17) are measured under the test conditions as follows:
(1) Glass cell assembly: 1*1 cm2;
(2) Working electrode: FTO/TiO2 (3T+AO+R)/TiCl4, post-treated;
(3) Conditions of dye immersion: adsorption/immersion of dye solutions, 0.2 mM Compound 9, Compound 23, Compound 47/solvents (EtOH/toluene=1:1), at 40° C. for 4.5 hours;
(4) Counter electrode: FTO glass/self-synthesis 4-layered Pt/low-temperature silver wire;
(5) Conditions of electrolyte: 0.1M LiI, 0.05 M I2, 0.5 M TBP, 0.6 M PMII in AN/VN=85/15; and
(6) Working area: 1 cm2, thickness of surlyn film being 30 μm.
The test results are shown on Table 1 and
aVoc: Open Circuit Voltage, volt (V);
bIsc: Short Circuit Current, milliamp (mA);
cFF: Fill Factor;
dη: Photoelectric conversion efficiency; and
eReference Compound 48 represented by the following formula:
Referring to Table 1 and
Also, The absorptions of the porphyrin dyes, such as Compound 9 (Example 1), Compound 16 (Example 2) and Compound 23 (Example 3) prepared according to the present invention, were determined by UV-Vis absorption spectrometry. The results are shown in
Those skilled in the art will recognize that the invention may be performed with variations on the disclosed compounds and processes without departing from the spirit or scope of the present invention as defined in the appended claims. The compounds described in the examples are intended to be representative of the present invention, and it is to be understood that the scope of the invention is not limited by the examples. All publications and patents cited above are incorporated herein by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| 100136163 | Oct 2011 | TW | national |
| 101100963 | Jan 2012 | TW | national |
