CN106117226A - The synthetic method of benzophenanthrene decane epoxide bridging dodecyloxy phenyl porphyrin metal Zn coordination compound - Google Patents
The synthetic method of benzophenanthrene decane epoxide bridging dodecyloxy phenyl porphyrin metal Zn coordination compound Download PDFInfo
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Abstract
The invention discloses the synthetic method of a kind of benzophenanthrene decane epoxide bridging dodecyloxy phenyl porphyrin metal Zn coordination compound.Its synthetic route is: Part I generates monohydroxy five hexyloxy benzophenanthrene；Secondly the synthesis alkoxyl benzophenanthrene containing a ω bromine side chain；Part II obtains porphyrin acid；Part III is that the intermediate obtained by above-mentioned two parts obtains metal complex by phase-transfer-catalyzed reactions synthesis alkoxyl bridging porphyrin benzophenanthrene binary compound with reacting metal salt.Benzophenanthrene is as a kind of common material, because of its there is good photochemistry and heat stability, raw material is easy to get, product is prone to the advantages such as purification, and metalloporphyrin has strong absorption, photochemistry and Heat stability is good and synthetic method ripe in visible region, the benzophenanthrene decane epoxide bridging dodecyloxy phenyl porphyrin metal Zn coordination compound that synthesis obtains can be applied at organic photovoltaic material, liquid crystal material, organic solar batteries, Organic Light Emitting Diode equimolecular device.
Description
Technical field
The present invention relates to the synthesis of a kind of benzophenanthrene decane epoxide bridging dodecyloxy phenyl porphyrin metal Zn coordination compound
Method.
Background technology
The research direction in Benzophenanthrene discotic mesogenic field mainly has the study on the synthesis of novel benzophenanthrene discotic mesogenic material
With self assembly characteristic research and its applied research etc..At present, the electric charge carrier of Benzophenanthrene discotic mesogenic material is dynamic
Mechanical simulation is also by studies in China worker's in-depth study.
Research report, the discotic mesogenic of Benzophenanthrene is applied in the field such as xerography and laser printing.Its
There is the characteristic of higher electric charge and exciton transfer, and the formation of columnar phase can be played again stable by the effect of electric charge transfer
Effect, this discotic mesogenic allowing for Benzophenanthrene becomes the organic semiconducting materials that a class is important.Chirst etc. are it was confirmed benzene
And phenanthrene discotic mesogenic advantageously reduces light activated starting voltage, but also have in the aspect of photodiode to be applied to
To be studied.But, they are at gas molecule sensor, organic solar batteries, Organic Light Emitting Diode, high speed copier and sweep
The application retouching the aspects such as instrument photoconductor drum has the biggest development prospect.First organic solar batteries prepared in 1986, but
Being its transformation efficiency the lowest (1%), basic reason is that charge transport properties is bad, and charge mobility is low.And Benzophenanthrene plate-like
High efficiency charge transfer that liquid crystal has and the characteristic of energy transfer, make this become make organic solar batteries ideal material it
One.On the other hand, Benzophenanthrene molecule can be as electron donor or additive application in organic solar batteries, and this can be obvious
Improve charge transport rate, and photoelectric transformation efficiency can be improved simultaneously.And, introduce in benzophenanthrene aromatic proton
Atom, such as nitrogen and sulphur atom, also have the atom of some functional types, and this can improve the photoelectric properties improving its liquid crystal material.
But Benzophenanthrene discotic mesogenic there is also the problem that fusing point is higher.The increase of the temperature range of liquid crystalline phase, also has
It is exactly that to reduce the fusing point of liquid crystalline phase be that its material can practical first problem to be solved.Moreover, if wanting reality to answer
It is used on organic semiconducting materials, otherwise the various designs of benzophenanthrene disc-shaped liquid crystal molecule are improved axis of a cylinder to standard by open close mistake
One-dimensional molecular assembly piles up property, thus obtains the columnar phase of quite stable with this to improve carrier mobility in columnar phase.
Therefore, the step of research Benzophenanthrene discotic mesogenic is still continuing.
In discotic mesogenic, benzophenanthrene as a kind of common material, because of its have good photochemistry and heat stability,
Raw material is easy to get, product is prone to purification, structure-rich is changeable and has the advantages such as higher charge transport rate at the longitudinal axis, therefore
It it is first-selected donor monomer；And porphyrin has strong absorption, photochemistry and Heat stability is good and synthetic method ripe in visible region,
There is good liquid crystal property, therefore can be as good by body unit.The present invention is by designing and synthesizing containing electron donor
(D) the discotic mesogenic binary compound of-bridge (B)-receptor (A) structure, this compounds can be applied at organic photovoltaic material, liquid
Brilliant material, organic solar batteries, Organic Light Emitting Diode equimolecular device.
Summary of the invention
It is an object of the invention to provide a kind of benzophenanthrene decane epoxide bridging dodecyloxy phenyl porphyrin metal Zn to coordinate
The synthetic method of thing.
The synthetic route of the present invention can be divided into three below part: Part I, first by adjacent two hexyloxy benzene and 2-oneself
Epoxide phenol occurs coupling reaction to generate monohydroxy five hexyloxy benzophenanthrene under the Oxidation of ferric chloride；Secondly, with list
Hydroxyl five hexyloxy benzophenanthrene, 1,10-dibromo-decane are the primary raw material synthesis alkoxyl benzophenanthrene containing a ω-bromine side chain；
Part II be with hydroxy benzaldehyde, Dodecyl Bromide for primary raw material synthesize to dodecyloxy benzaldehyde, then with
P formylbenzoic acid methyl ester, pyrroles synthesize porphyrin ester in dimethylbenzene.Finally, hydrolyzed by the porphyrin ester obtained, acidifying obtains
Porphyrin acid；Part III is that the intermediate obtained by above-mentioned two parts synthesizes a series of alkoxyl bridge by phase-transfer-catalyzed reactions
Even porphyrin-benzophenanthrene binary compound.
Benzophenanthrene as a kind of common material, because of its there is good photochemistry and heat stability, raw material is easy to get, product
Be prone to purification, structure-rich is changeable and has the advantages such as higher charge transport rate at the longitudinal axis, and porphyrin is in visible region
Having strong absorption, photochemistry and Heat stability is good and synthetic method ripe, have good liquid crystal property, the present invention is by design
And synthesizing the discotic mesogenic binary compound containing electron donor (D)-bridge (B)-receptor (A) structure, this compounds can be answered
It is used in organic photovoltaic material, liquid crystal material, organic solar batteries, Organic Light Emitting Diode equimolecular device.
Accompanying drawing explanation
Fig. 1 is benzophenanthrene decane epoxide bridging dodecyloxy phenyl porphyrin metal Zn complex structure formula of the present invention.
Fig. 2 is the chemical equation of synthetic route of the present invention.
In figure: R=C6H13, R1=C12H25。
Detailed description of the invention
Embodiment:
Chemical reagent and solvent used in embodiment are analytical pure.
(1) synthesis of adjacent own alkoxy phenol (compound 1)
20 grams of catechols, 89.9 grams of 1-bromo normal hexane, 73.5 grams of Anhydrous potassium carbonates, 6.0 grams of potassium iodide and 250 milliliters
Dehydrated alcohol, at 85 DEG C, back flow reaction is after 60 hours, sucking filtration under room temperature, after the rotated evaporimeter of filtrate removes solvent,
Collecting the fraction of 84 DEG C in the case of the decompression distillation of 0.5mmHg, obtain 48 grams of colourless oil liquids i.e. compound 1, productivity is
96%.Bp:106±3℃,IR(KBr)νmax(cm-1):1260,930；1H NMR(300MHz,CDCl3)δ:6.89(s,4H),
3.99 (t, J=6.9Hz, 4H), 1.83-1.76 (m, J=6.9Hz, 4H), 1.49-1.31 (m, 12H), 0.9 (t, J=6.9Hz,
6H)。
(2) synthesis of adjacent two own alkoxy benzenes (compound 2)
50 grams of catechols, 75 grams of 1-bromo normal hexane, 100 grams of Anhydrous potassium carbonates, 3.8 grams of potassium iodide and 500 milliliters of nothings
Water-ethanol, 85 DEG C of back flow reaction are after 12 hours, sucking filtration under room temperature, after the rotated evaporimeter of filtrate removes solvent, 0.5mmHg's
Collecting the fraction of 140-143 DEG C in the case of decompression distillation, obtain 25.5 grams of colourless oil liquids i.e. compound 2, productivity is 29%.
Bp 255±3℃,IR(KBr)νmax(cm-1):1250,939；1H NMR(300MHz,CDCl3)δ:6.95-6.82(m,4H),
5.68 (s, 1H), 4.02 (t, J=6.9Hz, 2H), 1.83-1.76 (m, 2H), 1.48-1.31 (m, 6H), 0.91 (t, J=
6.9Hz,3H)。
(3) synthesis of monohydroxy-five hexyloxy benzophenanthrene (compound 3)
Take 4.44 g of compound 1 and 1.56 g of compound 2 to be dissolved in 60 milliliters of dichloromethane solutions through constant pressure funnel
Drop in 80 milliliters of dichloromethane solutions containing 12.96 grams of anhydrous ferric trichlorides and 8 milliliters of nitromethanes, dropping in 30 minutes
Complete；Then in the range of the temperature of reaction being maintained at 0 DEG C-3 DEG C after isothermal reaction 3 hours, add 50 milliliters of absolute methanols and
25 milliliters of water terminate reaction, and the mixture of reaction is that 2mol/L dilute hydrochloric acid washes twice by 15 milliliters of concentration, saturated with 15 milliliters
Brine It once, separates organic layer, and after addition anhydrous sodium sulfate is dried except water, rotated evaporimeter removes solvent, obtains
Crude product purified by silica gel (200-300 mesh) column chromatography purify (leacheate be ethyl acetate/petroleum ether volume ratio be 1:30-1:
15), obtaining 2.14 grams of brown yellow solid i.e. compound 3, productivity is 36%.Mp 47.7-50.1℃,IR(KBr)νmax(cm-1):
3040,1240,837；1H NMR(400MHz,CDCl3)δ:7.96(s,1H),7.83(s,3H),7.82(s,1H),7.77(s,
1H),5.91(s,1H),4.31-4.19(m,10H),1.98-1.90(m,10H),1.59-1.40(m,30H),0.96-0.92
(m,15H)。
(4) synthesis of bromo decyloxy-five hexyloxy benzophenanthrene (compound 4)
Under nitrogen protection, by 1.23 g of compound 3,2.97 gram 1,10-dibromo-decane, 0.43 gram of potassium hydroxide and 0.16 gram
Tetrabutyl ammonium bromide joins in the mixture of 10 milliliters of dichloromethane and 6.5 milliliters of water, after stirring 24 hours under room temperature, with 30
Milliliter water washes twice, and washed once with 15 milliliters of saturated aqueous common salts, separates organic layer, adds anhydrous sodium sulfate and is dried except water
After, rotated evaporimeter removes solvent, and with the purification of silica gel (200-300 mesh) column chromatography, (leacheate is ethyl acetate/petroleum ether body
Long-pending ratio is 1:30-1:20), obtaining colorless solid 1.41 grams is compound 4, and productivity is 89%.Mp:62±3℃IR(KBr)νmax
(cm-1):1390,1260,837.1H NMR(400MHz,CDCl3) δ: 7.83 (s, 6H), 4.23 (t, J=6.8Hz, 12H),
3.38 (t, J=6.8Hz, 2H), 1.95 (m, 14H), 1.6-1.51 (m, 16H), 1.45-1.35 (m, 20H), 0.93 (t, J=
6.8Hz,15H)。
(5) synthesis to dodecyloxy benzaldehyde (compound 5)
100 milliliters of single port flasks after being dried 1 hour add 2.44 grams of hydroxy benzaldehydes, 6.725 grams of bromos ten
Dioxane and 5.52 grams of Anhydrous potassium carbonates, be eventually adding 20 milliliters through CaH2The DMF solvent being dried, device exists
In nitrogen atmosphere after 80 DEG C of reactions 12 hours, adds 200 milliliters of water and 20 milliliters of dichloromethane extraction three times, use anhydrous sodium sulfate
Being dried, rotated evaporimeter removes solvent, and with the purification of silica gel (200-300 mesh) column chromatography, (leacheate is dichloromethane: stone
Oil ether volume ratio is 1:5-1:2), obtain 5.75 grams of weak yellow liquids i.e. compound 5, productivity is 98%.bp>300℃,IR
(KBr)νmax(cm-1):1610,1380,1260,841；1H NMR(300MHz,CDCl3) δ: 9.87 (s, H), 7.68 (t, J=
6.8Hz, 2H), 6.89 (d, J=8.6Hz, 2H), 3.99 (t, J=6.9Hz, 2H), 1.83-1.76 (m, J=6.9Hz, 4H),
0.96-1.31 (m, J=5.6Hz, 10H).
(6) the 5-para Toluic Acid carbomethoxy-10,15,20-three synthesis to dodecyloxy phenyl porphyrin (compound 6)
Take 5.88 g of compound 5,1.198 grams to acyl group essence of Niobe and 1.8495 grams of m-Carboxynitrobenzenes, with 32 millis
After liter xylene solution fully dissolves, the 1.91 grams of pyrroles 10 points diluted through 32 milliliters of dimethylbenzene by constant pressure funnel dropping
Clock, back flow reaction 3.5 hours at 140 DEG C；Solvent xylene is distilled off after reaction, obtains dark thick material, use silica gel
(200-300 mesh) column chromatography purifies (leacheate be dichloromethane/petroleum ether volume ratio be 1:2-1:1), with dichloromethane/anhydrous
Methanol=1:1 recrystallization, obtains violet solid compound i.e. compound 6, and productivity is 32.3%.Mp 125.1-126.2℃,IR
(KBr)νmax(cm-1):1720,1350,1240,803；1H NMR(400MHz,CDCl3) δ 8.90 (d, J=6.2Hz, 6H),
8.76 (d, J=4.7Hz, 2H), 8.44 (d, J=8.2Hz, 2H), 8.30 (d, J=8.1Hz, 2H), 8.16-8.05 (m, 6H),
7.29 (d, J=8.5Hz, 6H), 4.15 (d, J=5.6Hz, 6H), 4.11 (s, 3H), 1.93 (dt, J=6.1Hz, 3H), 1.77-
1.54 (m, 12H), 1.51-1.35 (m, 12H), 1.06 (dd, 9H), 1.00 (t, J=6.8Hz, 9H) ,-2.74 (s, 2H).
(7) the 5-para Toluic Acid base-10,15,20-three synthesis to dodecyloxy phenyl porphyrin (compound 7)
Take 1.4 g of compound 6 and 5 milliliters of aqueous solutions containing 1.79 grams of potassium hydroxide, with the oxolanes of 25 milliliters (THF)
After fully dissolving, add the absolute methanol of 5 milliliters, back flow reaction 3 hours at 70 DEG C, after being cooled to room temperature, add commercially available concentrated hydrochloric acid
Between regulation pH to 2-3, sucking filtration obtains the solid i.e. compound 7 of green, productivity 65%.Mp 176.3-177.5℃；IR(KBr)
νmax(cm-1):1710,1490,1260,801.1H NMR(400MHz,CDCl3) δ 8.90 (d, J=6.2Hz, 6H), 8.76 (d, J
=4.7Hz, 2H), 8.44 (d, J=8.2Hz, 2H), 8.30 (d, J=8.1Hz, 2H), 8.16-8.05 (m, 6H), 7.29 (d, J
=8.5Hz, 6H), 4.15 (d, J=5.6Hz, 6H), 4.11 (s, 1H), 1.93 (dt, J=6.1Hz, 3H), 1.77-1.54 (m,
12H), 1.51-1.35 (m, 12H), 1.06 (dd, 9H), 1.00 (t, J=6.8Hz, 9H) ,-2.74 (s, 2H).
(8) synthesis of benzophenanthrene decane epoxide bridging dodecyloxy phenyl porphyrin (compound 8)
Take 0.108 9,0.0027 gram of potassium carbonate of g of compound 7,0.127 g of compound and 0.16 gram of tetrabutyl ammonium bromide, add
Enter in the mixture of 6 milliliters of chloroform and 12 milliliters of water, the lower 80 DEG C of back flow reaction of nitrogen atmosphere 36 hours；Use chloroform
Extraction separates water layer and organic layer, and organic layer is spin-dried for after drying through anhydrous sodium sulfate, purifies with silica gel (200-300 mesh) column chromatography
(leacheate be ethyl acetate/petroleum ether volume ratio be 1:10-1:5), obtains 0.372 gram, obtains aubergine solid i.e. compound
8, productivity 88%；Mp 50.8±3℃,IR(KBr)νmax(cm-1):1360,1240,803；1H NMR(400MHz,CDCl3)δ
8.89 (s, 8H), 8.77 (s, 2H), 8.44 (d, J=7.6Hz, 2H), 8.30 (d, J=7.5Hz, 2H), 8.10 (d, J=
8.1Hz, 6H), 7.82 (s, 6H), 7.28 (d, J=7.5Hz, 6H), 4.51 (s, 2H), 4.18 (dd, J=34.2,5.8Hz,
18H), 1.92 (s, 22H), 1.42 (d, J=21.3Hz, 44H), 1.27-0.76 (m, 36H) ,-2.75 (s, 2H) .Elemental
analysis calcd for C127H168N4O11(1925):C,79.18,H,8.81,N,2.89,Found:C,79.17,H,
8.79,N,2.91。
(9) synthesis of benzophenanthrene decane epoxide bridging dodecyloxy phenyl porphyrin metal Zn coordination compound (compound 9)
Take 0.1 g of compound 8 and 0.03 gram of zinc chloride, join 15 milliliters of DMFs and 10 milliliters of trichlorines
In the mixture of methane, react after nitrogen atmosphere stirring reaction 3 hours at 65 DEG C and terminate；Separate organic with chloroform extraction
Layer, after anhydrous sodium sulfate is dried except water, rotary evaporation removes solvent, purifies (leacheate with silica gel (200-300 mesh) column chromatography
Be ethyl acetate/petroleum ether volume ratio be 1:10-1:5), obtain 0.087 gram of violet solid i.e. compound 9, productivity 85%；IR
(KBr)νmax(cm-1):1724,1356,1240,804；1H NMR(400MHz,CDCl3)δ8.89(s,8H),8.77(s,2H),
8.44 (d, J=7.6Hz, 2H), 8.30 (d, J=7.5Hz, 2H), 8.10 (d, J=8.1Hz, 6H), 7.82 (s, 6H), 7.28
(d, J=7.5Hz, 6H), 4.51 (s, 2H), 4.18 (dd, J=34.2,5.8Hz, 18H), 1.92 (s, 20H), 1.42 (d, J=
21.3Hz,46H),1.27-0.76(m,36H)。
Claims (1)
1. a synthetic method for benzophenanthrene decane epoxide bridging dodecyloxy phenyl porphyrin metal Zn coordination compound, its feature exists
In concretely comprising the following steps:
(1) the adjacent own alkoxy phenol i.e. synthesis of compound 1:
Take 20 grams of catechols, 89.9 grams of 1-bromo normal hexane, 73.5 grams of Anhydrous potassium carbonates, 6.0 grams of potassium iodide and 250 milliliters of nothings
Water-ethanol, at 85 DEG C, back flow reaction is after 60 hours, sucking filtration under room temperature, after the rotated evaporimeter of filtrate removes solvent,
Collecting the fraction of 84 DEG C in the case of the decompression distillation of 0.5mmHg, obtain 48 grams of colourless oil liquids i.e. compound 1, productivity is
96%；Bp:106±3℃,IR(KBr)νmax(cm-1):1260,930；1H NMR(300MHz,CDCl3)δ:6.89(s,4H),
3.99 (t, J=6.9Hz, 4H), 1.83-1.76 (m, J=6.9Hz, 4H), 1.49-1.31 (m, 12H), 0.9 (t, J=6.9Hz,
6H)；
(2) the adjacent two own alkoxy benzenes i.e. synthesis of compound 2:
Take 50 grams of catechols, 75 grams of 1-bromo normal hexane, 100 grams of Anhydrous potassium carbonates, 3.8 grams of potassium iodide and 500 milliliters anhydrous
Ethanol, 85 DEG C of back flow reaction are after 12 hours, and sucking filtration under room temperature, after the rotated evaporimeter of filtrate removes solvent, 0.5mmHg subtracts
Collecting the fraction of 140-143 DEG C in the case of pressure distillation, obtain 25.5 grams of colourless oil liquids i.e. compound 2, productivity is 29%；Bp
255±3℃,IR(KBr)νmax(cm-1):1250,939；1H NMR(300MHz,CDCl3)δ:6.95-6.82(m,4H),5.68
(s, 1H), 4.02 (t, J=6.9Hz, 2H), 1.83-1.76 (m, 2H), 1.48-1.31 (m, 6H), 0.91 (t, J=6.9Hz,
3H)；
(3) monohydroxy-five hexyloxy benzophenanthrene i.e. synthesis of compound 3:
Take 4.44 g of compound 1 and 1.56 g of compound 2 to be dissolved in 60 milliliters of dichloromethane solutions through constant pressure funnel dropping
To 80 milliliters of dichloromethane solutions containing 12.96 grams of anhydrous ferric trichlorides and 8 milliliters of nitromethanes, within 30 minutes, drip
Finish；Then, in the range of the temperature of reaction being maintained at 0 DEG C-3 DEG C after isothermal reaction 3 hours, 50 milliliters of absolute methanols and 25 are added
Milliliter water terminates reaction, and the mixture of reaction is that 2mol/L dilute hydrochloric acid washes twice by 15 milliliters of concentration, with 15 milliliters of saturated foods
Saline washed once, and separates organic layer, and after addition anhydrous sodium sulfate is dried except water, rotated evaporimeter removes solvent, obtains
Crude product with 200-300 mesh silica gel column chromatography purify, leacheate be ethyl acetate/petroleum ether volume ratio be 1:30-1:15, obtain
2.14 grams of i.e. compounds 3 of brown yellow solid, productivity is 36%；Mp 47.7-50.1℃,IR(KBr)νmax(cm-1):3040,1240,
837；1H NMR(400MHz,CDCl3)δ:7.96(s,1H),7.83(s,3H),7.82(s,1H),7.77(s,1H),5.91(s,
1H),4.31-4.19(m,10H),1.98-1.90(m,10H),1.59-1.40(m,30H),0.96-0.92(m,15H)；
(4) bromo decyloxy-five hexyloxy benzophenanthrene i.e. synthesis of compound 4:
Under nitrogen protection, by 1.23 g of compound 3,2.97 gram 1,10-dibromo-decane, 0.43 gram of potassium hydroxide and 0.16 gram of four fourth
Base ammonium bromide joins in the mixture of 10 milliliters of dichloromethane and 6.5 milliliters of water, after stirring 24 hours under room temperature, with 30 milliliters
Water washes twice, and washed once with 15 milliliters of saturated aqueous common salts, separates organic layer, after addition anhydrous sodium sulfate is dried except water, and warp
Rotary Evaporators removes solvent, purifies with 200-300 mesh silica gel column chromatography, and leacheate is that ethyl acetate/petroleum ether volume ratio is
1:30-1:20, obtaining colorless solid 1.41 grams is compound 4, and productivity is 89%；Mp:62±3℃IR(KBr)νmax(cm-1):
1390,1260,837.1H NMR(400MHz,CDCl3) δ: 7.83 (s, 6H), 4.23 (t, J=6.8Hz, 12H), 3.38 (t, J=
6.8Hz, 2H), 1.95 (m, 14H), 1.6-1.51 (m, 16H), 1.45-1.35 (m, 20H), 0.93 (t, J=6.8Hz, 15H)；
(5) to the dodecyloxy benzaldehyde i.e. synthesis of compound 5:
100 milliliters of single port flasks after being dried 1 hour add 2.44 grams of hydroxy benzaldehydes, 6.725 grams of bromododecanes
With 5.52 grams of Anhydrous potassium carbonates, it is eventually adding 20 milliliters through CaH2The DMF solvent being dried, device is at nitrogen
In atmosphere after 80 DEG C of reactions 12 hours, adds 200 milliliters of water and 20 milliliters of dichloromethane extraction three times, carry out with anhydrous sodium sulfate
Being dried, rotated evaporimeter removes solvent, purifies with 200-300 mesh silica gel column chromatography, and leacheate is dichloromethane: petroleum ether body
Long-pending ratio is 1:5-1:2, obtains 5.75 grams of weak yellow liquids i.e. compound 5, and productivity is 98%；bp>300℃,IR(KBr)νmax
(cm-1):1610,1380,1260,841；1H NMR(300MHz,CDCl3) δ: 9.87 (s, H), 7.68 (t, J=6.8Hz, 2H),
6.89 (d, J=8.6Hz, 2H), 3.99 (t, J=6.9Hz, 2H), 1.83-1.76 (m, J=6.9Hz, 4H), 0.96-1.31 (m,
J=5.6Hz, 10H)；
(6) 5-para Toluic Acid carbomethoxy-10,15,20-three is to the dodecyloxy phenyl porphyrin i.e. synthesis of compound 6:
Take 5.88 g of compound 5,1.198 grams to acyl group essence of Niobe and 1.8495 grams of m-Carboxynitrobenzenes, with 32 milliliter two
After toluene solution fully dissolves, by constant pressure funnel dropping through 1.91 grams of pyrroles 10 minutes of 32 milliliters of dimethylbenzene dilution,
Back flow reaction 3.5 hours at 140 DEG C；Solvent xylene is distilled off after reaction, obtains dark thick material, use 200-300 mesh
Silica gel column chromatography purifies, leacheate be dichloromethane/petroleum ether volume ratio be 1:2-1:1, with dichloromethane/absolute methanol=1:
1 recrystallization, obtains violet solid i.e. compound 6, and productivity is 32.3%；Mp 125.1-126.2℃,IR(KBr)νmax(cm-1):
1720,1350,1240,803；1H NMR(400MHz,CDCl3) δ 8.90 (d, J=6.2Hz, 6H), 8.76 (d, J=4.7Hz,
2H), 8.44 (d, J=8.2Hz, 2H), 8.30 (d, J=8.1Hz, 2H), 8.16-8.05 (m, 6H), 7.29 (d, J=8.5Hz,
6H), 4.15 (d, J=5.6Hz, 6H), 4.11 (s, 3H), 1.93 (dt, J=6.1Hz, 3H), 1.77-1.54 (m, 12H),
1.51-1.35 (m, 12H), 1.06 (dd, 9H), 1.00 (t, J=6.8Hz, 9H) ,-2.74 (s, 2H)；
(7) 5-para Toluic Acid base-10,15,20-three is to the dodecyloxy phenyl porphyrin i.e. synthesis of compound 7:
Take 1.4 g of compound 6 and 5 milliliters of aqueous solutions containing 1.79 grams of potassium hydroxide, fully dissolve with the oxolane of 25 milliliters
After, add the absolute methanol of 5 milliliters, back flow reaction 3 hours at 70 DEG C, add commercially available concentrated hydrochloric acid regulation pH after being cooled to room temperature extremely
Between 2-3, sucking filtration obtains the solid i.e. compound 7 of green, productivity 65%；Mp 176.3-177.5℃；IR(KBr)νmax(cm-1):1710,1490,1260,801.1H NMR(400MHz,CDCl3) δ 8.90 (d, J=6.2Hz, 6H), 8.76 (d, J=
4.7Hz, 2H), 8.44 (d, J=8.2Hz, 2H), 8.30 (d, J=8.1Hz, 2H), 8.16-8.05 (m, 6H), 7.29 (d, J=
8.5Hz, 6H), 4.15 (d, J=5.6Hz, 6H), 4.11 (s, 1H), 1.93 (dt, J=6.1Hz, 3H), 1.77-1.54 (m,
12H), 1.51-1.35 (m, 12H), 1.06 (dd, 9H), 1.00 (t, J=6.8Hz, 9H) ,-2.74 (s, 2H)；
(8) synthesis of the i.e. compound 8 of benzophenanthrene decane epoxide bridging dodecyloxy phenyl porphyrin:
Take 0.108 9,0.0027 gram of potassium carbonate of g of compound 7,0.127 g of compound and 0.16 gram of tetrabutyl ammonium bromide, join
In the mixture of 6 milliliters of chloroform and 12 milliliters of water, the lower 80 DEG C of back flow reaction of nitrogen atmosphere 36 hours；Use chloroform extraction
Separating water layer and organic layer, organic layer is spin-dried for after drying through anhydrous sodium sulfate, purifies with 200-300 mesh silica gel column chromatography, drip washing
Liquid be ethyl acetate/petroleum ether volume ratio be 1:10-1:5, obtain 0.372 gram, obtain aubergine solid i.e. compound 8, productivity
88%；Mp 50.8±3℃,IR(KBr)νmax(cm-1):1360,1240,803；1H NMR(400MHz,CDCl3)δ8.89(s,
8H), 8.77 (s, 2H), 8.44 (d, J=7.6Hz, 2H), 8.30 (d, J=7.5Hz, 2H), 8.10 (d, J=8.1Hz, 6H),
7.82 (s, 6H), 7.28 (d, J=7.5Hz, 6H), 4.51 (s, 2H), 4.18 (dd, J=34.2,5.8Hz, 18H), 1.92 (s,
22H), 1.42 (d, J=21.3Hz, 44H), 1.27-0.76 (m, 36H) ,-2.75 (s, 2H) .Elemental analysis
calcd for C127H168N4O11(1925):C,79.18,H,8.81,N,2.89,Found:C,79.17,H,8.79,N,2.91；
(9) synthesis of the i.e. compound 9 of benzophenanthrene decane epoxide bridging dodecyloxy phenyl porphyrin metal Zn coordination compound:
Take 0.1 g of compound 8 and 0.03 gram of zinc chloride, join 15 milliliters of DMFs and 10 milliliters of chloroform
Mixture in, in nitrogen atmosphere, at 65 DEG C, stirring reaction was reacted and is terminated after 3 hours；Organic layer is separated with chloroform extraction,
After anhydrous sodium sulfate is dried except water, rotary evaporation removes solvent, purifies with 200-300 mesh silica gel column chromatography, and leacheate is acetic acid
Ethyl ester/petroleum ether volume ratio is 1:10-1:5, obtains 0.087 gram of violet solid i.e. compound 9, productivity 85%；IR(KBr)νmax
(cm-1):1724,1356,1240,804；1H NMR(400MHz,CDCl3)δ8.89(s,8H),8.77(s,2H),8.44(d,J
=7.6Hz, 2H), 8.30 (d, J=7.5Hz, 2H), 8.10 (d, J=8.1Hz, 6H), 7.82 (s, 6H), 7.28 (d, J=
7.5Hz, 6H), 4.51 (s, 2H), 4.18 (dd, J=34.2,5.8Hz, 18H), 1.92 (s, 20H), 1.42 (d, J=21.3Hz,
46H),1.27-0.76(m,36H)；
Described chemical reagent and solvent are analytical pure.
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| ASTERIOS CHARISIADIS，等: "Two new bulky substituted Zn porphyrins bearing carboxylate anchoring groups as promising dyes for DSSCs", 《NEW JOURNAL OF CHEMISTRY》 * |
| JIANJUN MIAO，等: "Hydrogen Bonding Induced Supramolecular Self-Assembly of Linear Doubly Discotic Triad Supermolecules", 《CHEM. ASIAN J.》 * |
| 张云峰，等: "盘装液晶的研究进展", 《广州化工》 * |
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