CN1911929A - Meso position-tetra phenyl tetra phenanthro porphyrin derivetive and its preparation method - Google Patents
Meso position-tetra phenyl tetra phenanthro porphyrin derivetive and its preparation method Download PDFInfo
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- CN1911929A CN1911929A CN200510041390.8A CN200510041390A CN1911929A CN 1911929 A CN1911929 A CN 1911929A CN 200510041390 A CN200510041390 A CN 200510041390A CN 1911929 A CN1911929 A CN 1911929A
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- phenanthro
- porphyrin
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- 238000002360 preparation method Methods 0.000 title claims description 20
- 150000004032 porphyrins Chemical class 0.000 title abstract description 29
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title abstract description 3
- -1 phenanthryl pyrrole Chemical compound 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000013375 chromatographic separation Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 230000006698 induction Effects 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- 125000001424 substituent group Chemical group 0.000 abstract description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 abstract description 3
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 abstract 1
- 150000004033 porphyrin derivatives Chemical class 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 14
- 238000000862 absorption spectrum Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 238000001819 mass spectrum Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 8
- 150000003233 pyrroles Chemical class 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000021615 conjugation Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 229950003776 protoporphyrin Drugs 0.000 description 5
- KSFOVUSSGSKXFI-GAQDCDSVSA-N CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O Chemical compound CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O KSFOVUSSGSKXFI-GAQDCDSVSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 description 1
- QVTPWONEVZJCCS-UHFFFAOYSA-N 2-formylbenzonitrile Chemical compound O=CC1=CC=CC=C1C#N QVTPWONEVZJCCS-UHFFFAOYSA-N 0.000 description 1
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 1
- NDZXVMFFUZCSMU-UHFFFAOYSA-N C(C1=CC=CC=C1)=O.[I] Chemical compound C(C1=CC=CC=C1)=O.[I] NDZXVMFFUZCSMU-UHFFFAOYSA-N 0.000 description 1
- 235000014493 Crataegus Nutrition 0.000 description 1
- 241001092040 Crataegus Species 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004802 cyanophenyl group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000006303 iodophenyl group Chemical group 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001254 matrix assisted laser desorption--ionisation time-of-flight mass spectrum Methods 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- 150000002987 phenanthrenes Chemical class 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000006049 ring expansion reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Images
Abstract
The present invention discloses tetraphenanthryl porphyrin derivative with different substituents in the mid position benzene ring and prepared through the BF3.Et2O catalyzed reaction of phenanthryl pyrrole and benzaldedyde with with different substituents in the para position at low temperature and in no-oxygen atmosphere. These conjugated porphyrin compounds have Soret band in 577-603 nm, red shifted by over 160 nm compared with that of no-aromatic ring conjugated beta-tetraphenyl porphyrin and red shifted by near 100 nm compared with that of phenanthrene ring conjugated porphyrin without substituent in the mid position. These conjugated porphyrin compounds have wide application foreground in OFETs, molecular antenna, light-to-energy converter, medicine and other fields.
Description
One, technical field
The present invention relates to meta-tetraphenyl four phenanthro-derivatives of porphyrin and preparation method thereof.
Two, background technology
Porphyrins has the photoelectric properties of many uniquenesses, good light and thermally stable, bigger molar absorptivity is arranged in visible-range, thereby obtained paying close attention to widely and using in fields such as biological chemistry, medicine and pharmacology, analytical chemistry, photochemical catalysis and Materials science.In recent years, utilize the electronic structure and the photoelectric properties of porphyrin molecule uniqueness, the aspects such as development of design and synthetic photoelectric functional material and photoelectric device have become domestic and international ten minutes active research field, for example aspect the quantity of photogenerated charge and energy transfer of the biological photosynthetic reaction centre of simulation, the porphyrin molecule is as the light absorption units in the model compound, can realize that the photoinduction charge separation is [referring to (a) Gust D., Moore T.A.Science, 1989,244,35. (b) .Wasielewski M.R.Chem.Review, 1992,92,435. (c) Moore T.A., Gust D., et al.Nature, 1984,307,630. (d) Liddell P.A.; Kuciauskas D., Sumida J.P., et al.J.Am.Chem.Soc .1997,119,1400. (e) Kuciauskas D.; Liddell P.A.; Moore A.L., et al J.Am.Chem.Soc.1998,120,10880. (f) Y froah G.S., Liddell P.A.Nature, 1997,385,239. (g) Yfroah G.S., Liddell P.A.et al.Nature, 1998,392,497.]; In addition, porphyrin compound at organic effect electron tube (OFETs) [referring to Aramaki S., Sakai Y., Ono N.Appl.Phy.Let., 2004,84,2085.], the branch sub antenna [referring to: (a) Li J., Ambroise A., Yang S.I., Diers J.R., SethJ., Wack C.R., Bocian D.F., Holten D., Lindsey J.S.J.Am.Chem.Soc., 1999,121,8927. (b) .Choi M.S., Aida T., Yamazaki T.et al.Angew.Chem.Int.Ed., 2001,40,3194.], light-energy transmodulator [referring to: Gust D., Moore T.A., Moore A.L.Acc.Chem.Res.2001,34,40.], photoelectric conversion material [referring to: Crossley M.J., burn P.L.Chem.Commun., 1991,21,1569.], molecular switch [referring to: Wasielewiski M.R., Goszrola D.Z.Science, 1992,257,63.], the molecule logical gate [referring to: Wagner R.W., Lindsey J.S.J.Am.Chem.Soc., 1996,119,3996.], molecular wire [referring to: Richard W., Wagner R.W., Lindsey J.S.J.Am.Chem.Soc.1994,116,9759.], organic solar batteries [referring to: (a) Antohe S., Tugulea L.Phys.Stat.Sol (A), 1996,1153,581. (b) Takahashi K., Kuraya N., et al.Solar Enegy Materials﹠amp; SolarCell, 2000,61,403.], organic electroluminescent [referring to: Baldo M.A., O ' Bren D.F.et al.Nature, 1998,395,151.], nonlinear optical material [referring to: Lidzey D.G., Bradley D.C., et al.Nature, 1998,395,53.], optical storage [referring to: (a) Tyler B.N., Neil R.B.Adv.Mater, 2001,13 (5), 347. (b) Liu Z.M., Amir A., Yasseri J., Lindsey J.S., et al Science2003,302 (28), 1543.], molecular recognition and medicine [referring to: Yang Jizhang, Chinese Journal of New Drugs, 1995,4 (3), 59] etc. the aspect has a wide range of applications.
The characteristic spectrum of general protoporphyrin mainly is to be absorbed in Soret bands of a spectrum very strong about 400nm or to claim B peak (S by one
0→ S
2Transition) and four be absorbed in Q bands of a spectrum (S more weak more than the 500nm
0→ S
1Transition) constitutes.Except the porphyrin system of ring expansion, the feature electron absorption band of porphyrin molecule seldom has above more than the 500nm.The synthetic electron absorption of design as seen/porphyrins of near infrared region is the field, forward position of current international research.They not only can be used as the photosensitizers and the near infrared sensor of optical therapeutic, or the nonmetal electronic conductor of potential, catalysis and solar energy converting material.The method that increases porphyrin ring conjugation degree mainly contains: 1) introduce alkynyl [referring to Piet J.J., Taylor P.N., Anderson H.L., OsukaA., Warman J.M.J.Am.Chem.Soc., 2000,122,1749.] at the meta of porphyrin ring; 2) introduce aromatic ring in the β position of porphyrin ring [referring to Lash T.D., in ThePorphyrin Handbook, ed.Kadish, K.M.; Smith, K.M.; Guilard, R., Academic Press, San Diego, 2000, vol.2, p.125]; 3) increase pyrroles's number of rings on the porphyrin ring [referring to Sessler J.L., Seidel D.Angew.Chem.Int.Ed.Engl.2003,42,5134.]; 4) synthetic porphyrin polymer is [referring to Screen T.E.O., Thorne J.R.G., Dnning R.G., Bunall D.G., Anderson H.L.J.Am.Chem.Soc.2002,124,9712..
For synthesizing of porphyrin compound, existing a lot of methods reports [referring to: Benjamin J.L., Yangzhen Ciringh, Lindsey J.S.J.Org.Chem., 1999,64:2864.].Porphyrin ring normally by four pyrrole rings and tetramolecular aromatic aldehydes derivative under acidic conditions, obtain by condensation, oxidizing reaction, again owing to ring-opening polymerization and oxidizing reaction easily take place pyrroles under catalyst action, so by product is more, and complicated, it is difficult to generate the big ring of porphyrin, and productive rate is lower, be generally 10～20%, have in addition be lower than 10%.Although just begun the porphyrin study on the synthesis as far back as the thirties in last century, but the study on the synthesis to high conjugation porphyrin compound is only developed rapidly in recent years [referring to (a) Manley J.M., Roper T.J., Lash T.D.J.Org.Chem., 2005,70,874. (b) Lash T.D.J.Porphyrins Phthalocyanines 2001,5,267. (c) Vicente M.G., Smith K.M.J.PorphyrinsPhthalocyanines 2004,8,26.].Nineteen ninety-five Lash successfully synthesizes meta does not have substituent four phenanthro-porphyrins [referring to Lash T.D., Novak B.H.Angew.Chem.Int.Ed.Engl.1995,34,683.], and the phenanthro-porphyrin of centering substd only detects the molecular weight of meta tetraphenyl four phenanthro-porphyrins with FAB-MS, some investigators think this compounds since big sterically hindered causing can not copline, thereby be to be difficult to syntheticly or even can not to synthesize [referring to Spence J.D., Lash T.D.J.Org.Chem.2000,65,1530.].
Three, summary of the invention
The purpose of this invention is to provide meta-tetraphenyl four phenanthro-derivatives of porphyrin and preparation method thereof.
Technical scheme of the present invention is as follows:
Meta-tetraphenyl four phenanthro-derivatives of porphyrin, its general structure is seen accompanying drawing 1.R is H or other substituting groups.
A kind of method for preparing above-mentioned meta-tetraphenyl four phenanthro-derivatives of porphyrin, chemical equation is seen accompanying drawing 2:
In reaction vessel, add phenanthro-pyrroles and anhydrous methylene chloride, putting into magneton begins to stir, under oxygen free condition, reaction flask put into cryogenic unit and lucifuge, control under the temperature that is reflected at the oxypolymerization that suppresses the pyrroles and carry out, generally be below 0 ℃, temperature is below-20 ℃ preferably, best temperature range is between-40 ± 10 ℃, add the phenyl aldehyde or derivatives thereof, the mol ratio of phenanthro-pyrroles and phenyl aldehyde or derivatives thereof is 2: 1 to 1: 2, dropwise adds the Lewis acid BF of catalytic amount then with microsyringe
3Et
2O, make it react 2 hours at low temperatures after, allow it be warming up to room temperature naturally again and continue reaction 48 hours.To join in the reaction soln with the oxygenant of mole number with the phenanthro-pyrroles, react after 1 hour, drip the alkaline matter neutralization reactant.The pressure reducing and steaming solvent gets reaction product, carries out chromatographic separation with 100-140 order silica gel dress post, chloroform-sherwood oil as eluent, obtains meta-tetraphenyl four phenanthro-derivatives of porphyrin powders after the solvent evaporated.Behind methyl alcohol and chloroform recrystallization, obtain meta-tetraphenyl four phenanthro-derivatives of porphyrin crystal.
Catalyzer and temperature of reaction have fundamental influence for generating this step of protoporphyrin.The BF of synthetic protoporphyrin
3Et
2The O catalyzed reaction must be carried out under oxygen free condition, and this is in order to suppress pyrroles's oxypolymerization, thereby improves the productive rate of protoporphyrin.Adopting low-temp reaction in addition mainly is because in initial reaction stage, and pyrroles's concentration is very high, and polymerization easily takes place under catalyst action.After reacting for some time at low temperatures, material concentration decreases, and helps improving final reaction yield.
With
1H-NMR, IR, UV-Vis and MALDI-TOF MASS characterize and have confirmed the structure (seeing accompanying drawing) of these derivatives of porphyrin.Detecting used instrument is: (TMS is interior mark to Bruker ARX500 type nuclear magnetic resonance analyser, CDCl
3, deuterium is solvent for DMF or DMSO), (KBr salt sheet scans sweep limit 400～4000cm 20 times to the Bruker Fourier transformation infrared spectrometer
-1), Tianjin, island UV-3100 type ultraviolet-visible spectrophotometer is (with sample ligand into about 1 * 10
-5Solution about mol/L, sweep limit 400～1000nm, light path slit 2nm), the micro-fusing point instrument of X-4 digital display, U.S. Amico Bowman Series2Luminescence Spectrometer, U.S. Voyager Maldi-TOF mass spectrum workstation.
Beneficial effect of the present invention
The present invention compared with prior art, its remarkable advantage is: having synthesized meta first is that phenyl replaces, the β position is the derivatives of porphyrin of phenanthrene ring conjugation, the Soret bands of a spectrum of this class conjugation porphyrin compound appear at 577nm～603nm (seeing Table 1), the tetraphenylporphyrin that does not have kinds of aromatic ring conjugation with the β position has compared its Soret bands of a spectrum red shift more than the 160nm, than the unsubstituted phenanthrene of meta of prior art report
The ir data of table 1. compound 3a-h
| Compound | υ N-H (pyrroles) | δ N-H (pyrroles) | υ N-C (pyrroles) | υ C-C (aromatic ring) | v C-X (aromatic ring) | υ C-H (aromatic ring) | δ C-H (aromatic ring) | Other |
| 1 a | 34 | 10 48s | 13 52m | 16 29s， 1443s | 30 81w | 75 9s，726 s | ||
| 1 b | 34 | 10 47m | 13 52s | 16 04s， 1445s | 10 79m | 30 86w | 75 8s，728 s | |
| 1 c | 34 | 10 47m | 13 50s | 15 86s， 1447s | 10 92s | 30 84w | 75 8s，726 s | |
| 1 d | 34 | 10 47m | 13 50s | 16 30s， 1442s | 10 77m | 30 82w | 75 9s，725 s | |
| 1 e | 34 | 10 60s | 13 48s | 15 76s， 14 46s | 61 | 30 80w | 75 8s，727 s |
| 1 f | 34 | 10 47s | 13 50s | 16 01s， 1448s | 12 44m | 30 82w | 75 8s， 72 6s | υ C-O 1176 m |
| 1 g | 33 | 10 45m | 13 43m | 15 99s， 1446s | 11 66m | 30 84w | 75 9s，725 s | υ C≡ N 222 5s |
| 1 h | 34 17w | 10 46m | 13 54w | 15 88s | 85 2m | 30 84w | 75 8s，727 s | υ NO2 151 5s，1337 s |
The Soret bands of a spectrum red shift of ring conjugation porphyrin nearly 100nm, this is the protoporphyrin compound of absorbing wavelength maximum up to now.Under acidic conditions, their molar absorptivity increases significantly.When this compounds has a wide range of applications at aspects such as organic effect electron tube (OFETs), branch sub antenna, light-energy transmodulator, photoelectric conversion material, molecular switch, molecule logical gate, molecular wire, organic solar batteries, organic electroluminescent, nonlinear optical material, optical storage, molecular recognition and medicine.
Four, description of drawings
Fig. 1 is meta-tetraphenyl four phenanthro-derivatives of porphyrin general structures;
Fig. 2 is the chemical equation of preparation meta-tetraphenyl four phenanthro-derivatives of porphyrin;
Fig. 3 is the mass spectrum of the embodiment of the invention 1;
Fig. 4 is the hydrogen spectrum of the embodiment of the invention 1;
Fig. 5 is the ultra-violet absorption spectrum of the embodiment of the invention 1;
Fig. 6 is the mass spectrum of the embodiment of the invention 4;
Fig. 7 is the hydrogen spectrum of the embodiment of the invention 4;
Fig. 8 is the ultra-violet absorption spectrum of the embodiment of the invention 4;
Fig. 9 is the mass spectrum of the embodiment of the invention 5;
Figure 10 is the hydrogen spectrum of the embodiment of the invention 5;
Figure 11 is the ultra-violet absorption spectrum of the embodiment of the invention 5;
Figure 12 is the mass spectrum of the embodiment of the invention 6;
Figure 13 is the hydrogen spectrum of the embodiment of the invention 6;
Figure 14 is the ultra-violet absorption spectrum of the embodiment of the invention 6;
Figure 15 is the mass spectrum of the embodiment of the invention 7;
Figure 16 is the hydrogen spectrum of the embodiment of the invention 7;
Figure 17 is the ultra-violet absorption spectrum of the embodiment of the invention 7;
Figure 18 is the mass spectrum of the embodiment of the invention 8;
Figure 19 is the hydrogen spectrum of the embodiment of the invention 8;
Figure 20 is the ultra-violet absorption spectrum of the embodiment of the invention 8;
Figure 21 is the mass spectrum of the embodiment of the invention 9;
Figure 22 is the hydrogen spectrum of the embodiment of the invention 9;
Figure 23 is the ultra-violet absorption spectrum of the embodiment of the invention 9;
Figure 24 is the mass spectrum of the embodiment of the invention 10;
Figure 25 is the hydrogen spectrum of the embodiment of the invention 10;
Figure 26 is the ultra-violet absorption spectrum of the embodiment of the invention 10;
Figure 27 is the mass spectrum of the embodiment of the invention 11;
Figure 28 is the ultra-violet absorption spectrum of the embodiment of the invention 11;
Figure 29 position embodiment of the invention 12 (dotted line) contrasts with the ultra-violet absorption spectrum of the embodiment of the invention 1 (solid line).
Five, embodiment
Further specify the present invention by the following examples:
Embodiment 1:5,10,15,20-tetraphenyl four phenanthro-porphyrins (1a) synthetic
In the 500ml round-bottomed flask, add 1mmol (217mg) phenanthro-pyrroles and 350ml anhydrous methylene chloride; putting into magneton begins to stir; under the argon shield reaction flask put into cryogenic unit and lucifuge; with liquid nitrogen and acetone control reaction temperature at-40 ± 10 ℃; add the 1mmol phenyl aldehyde with syringe, dropwise add the BF that total amount is 40 μ l with microsyringe then
3Et
2O, make it react 2 hours at low temperatures after, allow it be warming up to room temperature naturally again and continue reaction 48 hours.1mmolDDQ (227mg) joins in the reaction soln, reacts after 1 hour, drips the triethylamine neutralization reactant.The pressure reducing and steaming solvent gets the black powder, carries out chromatographic separation with 100-140 order silica gel dress post, chloroform-sherwood oil as eluent, collects bright red colour band solution, and evaporate to dryness obtains red powder.Behind methyl alcohol and chloroform recrystallization, obtain the scarlet crystal.Productive rate: 19%; Molten point:＞250 ℃; MALDI-TOF MASS:calcd for C
92H
54N
41215.44, found:1216.38 (M+H
+) (Fig. 3); 500MHz
1H-NMR (d-DMF) δ 6.86 (8H, m), 7.36 (8H, m), 7.74 (8H, m), 7.96 (12H, m), 8.98 (8H, m), 10.10 (8H, m) (Fig. 4); UV-vis:577nm, 718nm, 795nm (Fig. 5).
Embodiment 2:5,10,15,20-tetraphenyl four phenanthro-porphyrins (1a) synthetic
The preparation method just adds the 1.2mmol phenyl aldehyde with embodiment 1.Productive rate: 24%.
Embodiment 3:5,10,15,20-tetraphenyl four phenanthro-porphyrins (1a) synthetic
The preparation method just adds the 2mmol phenyl aldehyde with embodiment 1.Productive rate: 22%.
Embodiment 4:5,10,15,20-four (p-methylphenyl) four phenanthro-porphyrins (1b)
The preparation method of 1b just is changed to p-tolyl aldehyde with phenyl aldehyde with embodiment 1.Productive rate: 15%; Fusing point:＞250 ℃; MALDI-TOF MASS:calcd for C
96H
62N
41271.5, found:1272.41 (M+H
+) (Fig. 6); 500MHz
1H-NMR (d-DMF) δ ppm 2.82 (12H, s), 6.83 (8H, m), 7.26 (8H, m), 7.48-7.50 (8H, m), 8.27 (8H, m), 8.47 (8H, m), 8.73 (8H, m) (Fig. 7); UV-vis:577nm, 724nm, 807nm (Fig. 8).
Embodiment 5:5,10,15,20-four (to fluorophenyl) four phenanthro-porphyrins (1c)
The preparation method of 1c just is changed to p-Fluorobenzenecarboxaldehyde with phenyl aldehyde with embodiment 1.Productive rate: 9%; Fusing point:＞250 ℃; MALDI-TOF-MASS:calcd for C
92H
50F
4N
41287.4, found:1288.1 (M+H
+) (Fig. 9); 500MHz 1H-NMR (d-DMF) δ ppm 6.87-6.97 (8H, m), 7.43-7.50 (8H, m), 7.57-7.64 (8H, m), 7.78-7.95 (8H, m), 8.66 (8H, m), 8.82-8.98 (8H, m) (Figure 10); UV-vis:576nm, 720nm, 795nm (Figure 11).
Embodiment 6:5,10,15,20-four (rubigan) four phenanthro-porphyrins (1d)
The preparation method of 1d just is changed to 4-chloro-benzaldehyde with phenyl aldehyde with embodiment 1.Productive rate: 11%; Fusing point:＞250 ℃; MALDI-TOF MASS:calcd for C
92H
50Cl
4N
41352.28, found:1353.85 (M+H
+) (Figure 12); 500MHz
1H-NMR (d-DMF) δ ppm 7.04 (8H, m), 7.43 (8H, m), 7.58 (8H, m), 7.80 (8H, d), 8.69 (8H, d), 8.93 (8H, d) (Figure 13); UV-vis:582nm, 723nm, 799nm (Figure 14).
Embodiment 7:5,10,15,20-four (to bromophenyl) four phenanthro-porphyrins (1e)
The preparation method of 1e just is changed to p-bromobenzaldehyde with phenyl aldehyde with embodiment 1.Productive rate: 11%; Fusing point:＞250 ℃; MALDI-TOF MASS:calcd for C
92H
50Br
4N
41531.08, found:1531.95 (M+H
+) (Figure 15); 500MHz
1H-NMR (d-DMF) δ ppm 6.96-7.20 (8H, m), 7.42 (8H, m), 7.56 (8H, m), 7.82-7.88 (8H, m), 8.67-8.79 (8H, m), 8.86-8.87 (8H, m) (Figure 16); UV-vis:584nm, 726nm, 801nm (Figure 17).
Embodiment 8:5,10,15,20-four (to iodophenyl) four phenanthro-porphyrins (1f)
The 1f preparation method just is changed to phenyl aldehyde to benzaldehyde iodine with embodiment 1.Productive rate: 12%; Fusing point:＞250 ℃; MALDI-TOF MASS:calcd for C
92H
50I4N
41719.02, found:1719.99 (M+H
+) (Figure 18); 500MHz
1H-NMR (d-DMF) δ ppm 7.00 (8H, m), 7.22 (8H, m), 7.43 (8H, m), 7.61 (8H, m), 8.64 (8H, m), 8.69 (8H, m) (Figure 19); UV-vis:585nm, 802nm, 857nm (Figure 20).
Embodiment 9:5,10,15,20-four (to cyano-phenyl) four phenanthro-porphyrins (1g)
The preparation method of 1g just is changed to phenyl aldehyde to cyanobenzaldehyde with embodiment 1.Productive rate: 14.3%; Fusing point:＞250 ℃; MALDI-TOF-MASS:calcd for C
96H
50N
81315.42, found:1316.3 (M+H
+) (Figure 21); 500MHz
1H-NMR (d-TFA-CDCl
3) δ ppm 6.06 (8H, m), 7.19 (8H, d), 7.27 (8H, m), 7.42 (8H, m), 8.48 (8H, d), 8.89 (8H, d) (Figure 22); UV-vis:597nm, 802nm, 860nm (Figure 23).
Embodiment 10:5,10,15,20-four (p-nitrophenyl) four phenanthro-porphyrins (1h)
The preparation method of 1h just is changed to paranitrobenzaldehyde with phenyl aldehyde with embodiment 1.Productive rate: 9%; Fusing point:＞250 ℃; MALDI-TOF MASS:calcd for C
92H
50N
8O
81395.38, found:1395.45 (M
+) (Figure 24); 500MHz
1H-NMR (d-DMF) δ ppm 7.01 (8H, m), 7.21 (8H, m), 7.51 (8H, m), 8.53 (8H, m), 8.69 (8H, m), 9.25 (8H, d) (Figure 25); UV-vis:602nm, 713nm, 803nm, 857nm (Figure 26).
Embodiment 11:5,10,15,20-four (p-methoxyphenyl) four phenanthro-porphyrins (1i)
The preparation method of 1i just is changed to aubepine with phenyl aldehyde with embodiment 1.Productive rate: 7%; Fusing point:＞250 ℃; MALDI-TOF MASS:calcd for C
96H
62O
4N
41334.48, found:1335.57 (M+H
+) (Figure 27); UV-vis:581nm, 746nm, 838nm (Figure 28).
Embodiment 12:1a is dissolved in the chloroformic solution that contains 1%TFA, and the molar absorptivity at its Soret peak enlarges markedly (Figure 29).
Embodiment 13:5,10,15,20-tetraphenyl four phenanthro-porphyrins (1a) synthetic
The preparation method is with embodiment 1, and just temperature of reaction is 0 ℃.Productive rate: 2%.
Embodiment 14:5,10,15,20-tetraphenyl four phenanthro-porphyrins (1a) synthetic
The preparation method is with embodiment 1, and just oxygenant is p-chlorane.Productive rate: 14%.
Claims (5)
1, meta-tetraphenyl four phenanthro-porphyrin compounds, its structural formula is as follows:
R is H, or CH
3, F, Cl, Br, I, CN, NO
2, OCH
3
2, the preparation method of the compound of claim 1, concrete steps are as follows:
(1) in reaction vessel, adds phenanthro-pyrroles and anhydrous methylene chloride, induction stirring, under oxygen free condition, reaction flask put into cryogenic unit and lucifuge, control reaction temperature is below 0 ℃, add the phenyl aldehyde or derivatives thereof, the mol ratio of phenanthro-pyrroles and phenyl aldehyde or derivatives thereof is 2: 1 to 1: 2, drips the Lewis acid BF of catalytic amount then
3Et
2O, make it react 2 hours at low temperatures after, allow it be warming up to room temperature naturally again and continue reaction 48 hours;
(2) to join in the reaction soln of step (1) with the oxygenant of mole number with the phenanthro-pyrroles, react after 1 hour, drip the alkaline matter neutralization reactant, the pressure reducing and steaming solvent gets reaction product;
(3) reaction product that step (2) is obtained is carried out chromatographic separation with 100-140 order silica gel dress post, chloroform-sherwood oil as eluent, obtain meta-tetraphenyl four phenanthro-porphyrin compound powders after the solvent evaporated, behind methyl alcohol and chloroform recrystallization, obtain meta-tetraphenyl four phenanthro-porphyrin compound crystal.
3, preparation method according to claim 2 is characterized in that control reaction temperature is between-40 ± 10 ℃ in the step (1).
4, preparation method according to claim 2 is characterized in that oxygenant is DDQ in the step (2).
5, the purposes of the compound of claim 1 is characterized in that: under acidic conditions, the molar absorptivity of the compound of claim 1 increases significantly.
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| CN102653541A (en) * | 2011-03-04 | 2012-09-05 | 国家纳米科学中心 | Porphyrin compound as well as preparation method and application of porphyrin compound |
| CN102786526A (en) * | 2011-05-20 | 2012-11-21 | 国家纳米科学中心 | Porphyrin-phthalocyanine dimer and preparation method and application thereof |
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| CN102653541A (en) * | 2011-03-04 | 2012-09-05 | 国家纳米科学中心 | Porphyrin compound as well as preparation method and application of porphyrin compound |
| CN102653541B (en) * | 2011-03-04 | 2014-01-15 | 国家纳米科学中心 | Porphyrin compound as well as preparation method and application of porphyrin compound |
| CN102786526A (en) * | 2011-05-20 | 2012-11-21 | 国家纳米科学中心 | Porphyrin-phthalocyanine dimer and preparation method and application thereof |
| CN102786526B (en) * | 2011-05-20 | 2014-07-16 | 国家纳米科学中心 | Porphyrin-phthalocyanine dimer and preparation method and application thereof |
| CN104725388A (en) * | 2015-03-25 | 2015-06-24 | 南京林业大学 | Meso site arylamino monosubstituted porphyrin derivative and preparation method thereof |
| CN104725388B (en) * | 2015-03-25 | 2017-03-15 | 南京林业大学 | Monosubstituted derivatives of porphyrin of a kind of meso positions aryl amine and preparation method thereof |
| CN105481882A (en) * | 2015-11-20 | 2016-04-13 | 南京林业大学 | Meso-position p-tert-butylphenyldiphenanthrene ring conjugated heterocyclic porphyrin derivative and preparation method thereof |
| CN105777764A (en) * | 2016-04-13 | 2016-07-20 | 南京工业大学 | Method for preparing tetraphenylporphyrin through micro reaction device |
| CN105777764B (en) * | 2016-04-13 | 2018-06-29 | 南京工业大学 | A kind of method that tetraphenylporphyrin is prepared using micro-reaction device |
| CN111445930A (en) * | 2020-03-10 | 2020-07-24 | 昆明理工大学 | Method for high-density information storage by using tetraphenylporphyrin molecules |
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