CN105481868B - A kind of phenanthrene ring conjugation derivatives of porphyrin of meso bit lengths chain alkoxy phenyl four and preparation method thereof - Google Patents
A kind of phenanthrene ring conjugation derivatives of porphyrin of meso bit lengths chain alkoxy phenyl four and preparation method thereof Download PDFInfo
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- CN105481868B CN105481868B CN201510828051.8A CN201510828051A CN105481868B CN 105481868 B CN105481868 B CN 105481868B CN 201510828051 A CN201510828051 A CN 201510828051A CN 105481868 B CN105481868 B CN 105481868B
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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Abstract
The invention discloses a kind of structure of porphyrins containing long-chain alkoxy base phenyl and phenanthrene ring group and preparation method thereof.So that containing long-chain alkoxy benzaldehyde and phenanthrene ring conjugation pyrroles, as raw material, by under heated reflux condition, long-chain alkoxy base aromatic aldehyde and phenanthrene ring conjugation pyrroles are in propionic acid catalytic action four phenanthro- derivatives of porphyrin of reaction generation in next step.The preparation method has the advantages that reactions steps are simple, the reaction time is short, selectivity is good, yield is high.
Description
Technical field
The invention belongs to technical field of organic synthesis, is related to a kind of phenanthrene ring conjugation porphyrin of meso bit lengths chain alkoxy phenyl four
The preparation method of derivative.
Background technology
Porphyrins has many unique photoelectric properties, good light and thermally stable, in visible-range
There is larger molar absorption coefficient, thus in fields such as biochemistry, medicine and pharmacology, analytical chemistry, photocatalysis and material science
Extensive concern and application are obtained.In recent years, using the unique electronic structure of Porphyrin Molecule and photoelectric properties, design and synthesize
Development of photoelectric functional material and photoelectric device etc. has turned into domestic and international very active research field, such as is given birth in simulation
In terms of the quantity of photogenerated charge and energy transfer of thing photosynthetic reaction centre, Porphyrin Molecule as the light absorption units in model compound,
It can realize that Photoinduced Charge separates；In addition, porphyrin compound organic effect electron tube (OFETs), light-energy converter,
The side such as molecular switch, Molecular Logic Gates, molecular wire, organic solar batteries, nonlinear optical material, molecular recognition and medicine
Face has a wide range of applications.
Chain alkyl is introduced in the meso positions of porphyrin, can make porphyrin that there is good liquid crystal property.In addition, nir dye
Molecule is in multiple fields such as optical imagery, diagnosing tumor, military surveillance, infrared camouflage, nonlinear optical material and fluorescence labellings
Play remarkable effect.Phenanthrene ring group is introduced in the β positions of porphyrin, can make molecule that there is bigger conjugated system, effectively reduce it
Ground state is poor with excited level, and porphyrin compound can be made to produce strong electronic and fluorescence emission near infrared region
Spectrum.Usual meso bit lengths alkyl group modification and β positions phenanthrene ring conjugation porphyrin synthesis step are more, difficulty is big, separation is relatively difficult, therefore
Such compound synthesis is studied less.
The content of the invention
Goal of the invention：For the deficiencies in the prior art, it is an object of the invention to provide a kind of meso bit lengths alkane
The phenanthrene ring conjugation derivatives of porphyrin of phenyl four.It is a further object of the present invention to provide a kind of above-mentioned meso bit lengths chain alkoxy benzene
Phenanthrene ring conjugation derivatives of porphyrin of base four and preparation method thereof.
Technical scheme：In order to realize foregoing invention purpose, the technical solution adopted by the present invention is：
The phenanthrene ring conjugation derivatives of porphyrin of Meso bit length chain alkoxies phenyl four, its general structure are as follows：
In formula, R is Deng.
A kind of method for preparing the above-mentioned phenanthrene ring conjugation derivatives of porphyrin of meso bit lengths chain alkoxy four, step are as follows：
(1) phenanthrene ring conjugation pyrroles, long-chain alkoxy base aromatic aldehyde and propionic acid are added in reaction vessel, in argon gas protection and lucifuge
Under the conditions of, heating reflux reaction 1-3 hours, then it is cooled to room temperature.
(2) proper amount of methanol is added, overanxious, residue separates through silica gel column chromatography, then through CHCl3-CH3OH is recrystallized, and is obtained
Pure compound.Specific chemical equation is as follows：
In above-mentioned steps (1), long-chain alkoxy base aromatic aldehyde is 1: 1 with phenanthrene ring conjugation azole derivatives mol ratio；
In above-mentioned steps (1), the catalyst is propionic acid；
In above-mentioned steps (1), reaction condition is：Reacted under anaerobic and counterflow condition；
In above-mentioned steps (2), eluant, eluent is dichloromethane-petroleum ether (60-90), chloroform；
In above-mentioned steps (2), recrystallized using diffusion method；
Beneficial effects of the present invention
Compared with prior art, the phenanthrene ring conjugation derivatives of porphyrin preparation method of long-chain alkoxy base phenyl four of the invention has
The advantages of have：(1) it is luxuriant and rich with fragrance that different long-chain alkoxy base phenyl four can be prepared by changing different substituents on phenyl ring in this method
Ring is conjugated derivatives of porphyrin；(2) propionic acid had not only been used as reaction dissolvent but also had been used as catalyst, and usage amount is few；(3) good reaction selectivity,
Yield is high；Also there is economic, pollution easy to operate less；(4) the phenanthrene ring conjugation porphyrin of long-chain alkoxy base phenyl four prepared
Derivative has potential application prospect in near-infrared liquid crystal material field.
Brief description of the drawings
Fig. 1 is 1a of embodiment of the present invention uv-visible absorption spectra；
Fig. 2 is 1a of embodiment of the present invention proton nmr spectra；
The MALDI-TOF-MS that Fig. 3 is 1a of the embodiment of the present invention is composed；
Fig. 4 is 1b of embodiment of the present invention uv-visible absorption spectra；
Fig. 5 is 1b of embodiment of the present invention proton nmr spectra；
The MALDI-TOF-MS that Fig. 6 is 1b of the embodiment of the present invention is composed；
Fig. 7 is 1c of embodiment of the present invention uv-visible absorption spectra；
Fig. 8 is 1c of embodiment of the present invention proton nmr spectra；
The MALDI-TOF-MS that Fig. 9 is 1c of the embodiment of the present invention is composed；
Figure 10 is 1d of embodiment of the present invention uv-visible absorption spectra；
Figure 11 is 1d of embodiment of the present invention proton nmr spectra；
The MALDI-TOF-MS that Figure 12 is 1d of the embodiment of the present invention is composed；
Embodiment
The present invention is further explained with reference to instantiation, specific implementation example does not do any to the present invention
Limit.
With1H-NMR, UV-Vis and MALDI TOFF MASS are characterized and are confirmed the structure of derivatives of porphyrin.Instrument used in detection
Device is：Bruker ARX500 types NMR (TMS is internal standard, and deuterochloroform is solvent), Shimadzu UV-3100 types are ultraviolet-and can
See spectrophotometer (400~800nm of scanning range, light path slit 2nm), German Brooker dalton company Matrix-assisted swashs
Ionization time-of-flight mass spectrometer is analysed in photodissociation.
Embodiment 1
Compound 1a synthesis：By 3,4- bis- (hexadecane epoxide) (1.173g, 2mmol) benzaldehyde and phenanthrene ring conjugation pyrroles
(0.572g, 2mmol) is added in the mono- neck bottles of 50mL, and is added propionic acid (15mL) and dissolved.Under the conditions of argon gas protection and lucifuge,
Heating reflux reaction 2h.It is cooled to room temperature, adds proper amount of methanol, filtering, residue carries out silica gel column chromatography separation, eluant, eluent two
Chloromethanes-petroleum ether, chloroform, peony product is then obtained after methanol and Gossypol recrystallized from chloroform.Yield：28.0%.Mp ＞ 250
℃.UV-vis(CHCl3)λmax nm(ε×10-5) 583 (1.319), 849 (0.378) (Fig. 1)；1H NMR(CDCl3)δ8.53
(s, 8H), 8.34 (m, 4H), 8.21-8.24 (m, 4H), 7.80-7.93 (m, 8H), 7.39 (m, 8H), 7.20-7.23 (m, 4H),
6.98-7.04 (m, 8H), 4.28-4.31 (m, 8H), 4.05-4.12 (m, 8H), 1.70 (m, 16H), 1.45 (s, 208H),
1.03-1.09 (t, 24H), 0.73 (b, 2H) (Fig. 2)；MALDI-TOF MASS cacd for C220H310N4O83138.84
found：3140.28(M+H+) (Fig. 3)
Embodiment 2
Compound 1b synthesis：By 3,4- bis- (hexadecane epoxide) (1.173g, 2mmol) benzaldehyde and phenanthrene ring conjugation pyrroles
(0.572g, 2mmol) is added in the mono- neck bottles of 50mL, and is added propionic acid (15mL) and dissolved.Under the conditions of argon gas protection and lucifuge,
Heating reflux reaction 2h.It is cooled to room temperature, adds proper amount of methanol, filtering, residue carries out silica gel column chromatography separation, eluant, eluent two
Chloromethanes-petroleum ether, chloroform, peony product is then obtained after methanol and Gossypol recrystallized from chloroform.Yield：25.3%.mp 220
℃.UV-vis(CHCl3)λmax nm(ε×10-5) 578 (0.869), 809 (0.161) (Fig. 4)；1H NMR(CDCl3)δ8.36-
8.40 (m, 8H), 7.80-7.83 (m, 4H), 7.72-7.76 (m, 12H), 7.26-7.30 (m, 8H), 6.88-6.95 (m, 8H),
6.60-6.68 (m, 4H), 3.92-4.01 (m, 8H), 3.67-3.68 (m, 4H), 3.57-3.59 (m, 4H), 1.58-1.59 (m,
16H), 1.30-1.32 (s, 210H), 0.90 (t, 24H) (Fig. 5)；MALDI-TOF MASS cacd for C220H310N4O8
3138.84 found：3141.27(M+H+) (Fig. 6).
Embodiment 3
Compound 1c synthesis：Preparation method is the same as embodiment 1, yield：321.9mg, 30.2%.250 DEG C of mp ＞；UV-vis
(CHCl3)λmax nm(ε×10-5) 575 (0.892), 849 (0.226) (Fig. 7)；1H NMR(CDCl3, 500M) and 58.8-8.58
(m, 8H), 8.35-8.40 (m, 8H), 7.66-7.73 (m, 8H), 7.23 (m, 8H), 7.07-7.09 (m, 8H), 6.84-6.86
(m, 8H), 4.13-4.17 (m, 16H), 2.28-2.35 (m, 8H), 1.86-1.88 (t, 8H), 1.66-1.69 (m, 8H), 1.54
(m, 8H), 1.38 (s, 40H), 1.28 (t, 12H), 0.88 (b, 2H) (Fig. 8)；MALDI-TOF MASS cacd for
C144H150N4O122128.75 found：2131.23(M+H+) (Fig. 9).
Embodiment 4
Compound 1d synthesis：Preparation method is the same as embodiment 1, yield：33.5%.200~206 DEG C of .UV-vis of mp
(CHCl3)λmax nm(ε×10-5) 579 (1.054), 808 (0.177) (Figure 10)；1H NMR(CDCl3, 500M) and δ 8.37-8.41
(m, 8H), 7.81-7.83 (m, 4H), 7.65-7.75 (m, 12H), 7.27 (m, 8H), 6.90-6.93 (m, 8H), 6.59-6.69
(m, 4H), 4.06-4.13 (m, 16H), 3.95 (m, 8H), 2.24-2.33 (m, 16H), 1.47-1.60 (m, 32H), 1.20-
1.27 (s, 80H), 1.23 (m, 24H), 0.96 (b, 2H) (Figure 11)；MALDI-TOF MASS cacd for C196H246N4O24
3042.06 found：3042.86(M+H+) (Figure 12).
Embodiment 5
Compound 1a synthesis：Preparation method is with embodiment 1, and it is 1 hour simply to control the reaction time, yield：25%.
Embodiment 6
Compound 1a synthesis：Preparation method is with embodiment 1, and it is 3 hours simply to control the reaction time, yield：29%.
Claims (5)
- A kind of 1. phenanthrene ring conjugation derivatives of porphyrin of long-chain alkoxy base phenyl four, it is characterised in that：Structural formula is as follows：In formula, R is
- 2. a kind of preparation method of the phenanthrene ring conjugation derivatives of porphyrin of long-chain alkoxy base phenyl four, its feature exist described in claim 1 In step is as follows：1) added in reaction vessel to long-chain alkoxy base aromatic aldehyde, phenanthrene ring conjugation azole derivatives and propionic acid, in argon gas protection and Under the conditions of lucifuge, 1-3 hours are heated to reflux；Wherein, long-chain alkoxy base aromatic aldehyde and phenanthro- azole derivatives mol ratio are 1:1；2) be cooled to room temperature, add proper amount of methanol, filtering, the purification of residue by silica gel chromatography post separation, eluant, eluent be dichloromethane- Petroleum ether and chloroform, it is crude product to collect the first lilac band, then through CHCl3-CH3OH is recrystallized to give pure products.
- 3. preparation method according to claim 2, it is characterised in that in the step 1), react and be heated to reflux and lucifuge Condition is carried out, and needs argon gas to protect.
- 4. preparation method according to claim 2, it is characterised in that in the step 1), propionic acid not only as catalyst but also was made For solvent.
- 5. preparation method according to claim 2, it is characterised in that in the step 2), column chromatography for separation eluant, eluent is successively For dichloromethane-petroleum ether and chloroform.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235042A (en) * | 2007-01-30 | 2008-08-06 | 南京大学 | Preparation and application of center modified porphyrin derivatives with two different kinds of aromatic ring conjugation |
| CN104225595A (en) * | 2013-06-06 | 2014-12-24 | 南京大学 | Nanoparticle for integration of breast cancer diagnosis and treatment and preparation method 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 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235042A (en) * | 2007-01-30 | 2008-08-06 | 南京大学 | Preparation and application of center modified porphyrin derivatives with two different kinds of aromatic ring conjugation |
| CN104225595A (en) * | 2013-06-06 | 2014-12-24 | 南京大学 | Nanoparticle for integration of breast cancer diagnosis and treatment and preparation method 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 |
Non-Patent Citations (3)
| Title |
|---|
| "5-(2-羟基-1-萘醛-4-萘基亚胺)-10,15,20-三萘基卟啉及其金属配合物的合成与表征";刘惊宙 等;《化学试剂》;20110228;第33卷(第2期);第121-123,132页 * |
| "A Multifunctional Nanomicelle for Real-Time Targeted Imaging and Precise Near-Infrared Cancer Therapy";Jiangwei Tian et al.;《Angew. Chem. Int. Ed.》;20140715;第53卷;第9544-9549页 * |
| "meso-四(对十六烷氧基苯基)卟啉的非线性吸收研究";姚文杰 等;《光电子·激光》;20070930;第18卷(第9期);第1089-1092页 * |
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Effective date of registration: 20180420 Address after: 224400 No. 13 filter industry park, Jiangsu, Funing Patentee after: JIANGSU RUIDA TECHNOLOGY CO., LTD. Address before: Longpan road Xuanwu District of Nanjing city of Jiangsu Province, No. 159 210037 Patentee before: Nanjing Forestry University |