CN106588940A - Synthesis method of benzophenanthrene decyloxy bridged isooctyl alkoxy phenyl porphyrin ternary compound disc-like liquid crystal material - Google Patents
Synthesis method of benzophenanthrene decyloxy bridged isooctyl alkoxy phenyl porphyrin ternary compound disc-like liquid crystal material Download PDFInfo
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Abstract
The invention discloses a synthesis method of benzophenanthrene decyloxy bridged isooctyl alkoxy phenyl porphyrin ternary compound disc-like liquid crystal material. The synthesis method comprises the following steps: firstly, performing synthesis to obtain dipyrrole and bi-isooctyl alkoxy benzaldehyde respectively, then performing synthesis on the dipyrrole and the bi-isooctyl alkoxy benzaldehyde to obtain porphyrinate, so that porphyrin acid is obtained; secondly, generating single hydroxyl-penta-hexyloxy benzophenanthrene, then performing synthesis to obtain alkoxy benzophenanthrene with an omega-bromine branched chain; thirdly, performing synthesis on the intermediates obtained in the above steps to obtain a benzophenanthrene decyloxy bridged isooctyl alkoxy phenyl porphyrin ternary compound. Synthetic raw materials of a benzophenanthrene ramification are easy to get, and a product is easy to refine, and has good optical property and heat stability; a synthesis method of a porphyrin derivative is mature, and has good fluorescene and aromaticity. The benzophenanthrene decyloxy bridged isooctyl alkoxy phenyl porphyrin ternary compound disc-like liquid crystal material can be applied to molecule devices such as organic solar cells, organic photovoltaic materials, liquid crystal materials and the like.
Description
Technical field
The present invention relates to a kind of benzophenanthrene decyloxy bridging isooctane phenyl porphyrin ternary compound discotic mesogenic material
The synthetic method of material.
Background technology
Research is begun to early in century-old prehuman and how to benefit the world using solar energy, thus manufactured the inorganic of silicon materials
Solar cell, but the production due to high-purity silicon material and procedure are more complicated, cause battery cost higher, and giving birth to
Severe contamination can be produced during product.Therefore people turn one's attention to organic solar batteries, at present restriction organic solar electricity
One big major reason of pond photoelectric transformation efficiency is：Lack suitable active layer material.Benzophenanthrene compound is containing conjugated pi
The organic compound of electronics, it is widely paid close attention to as typical semi-conducting material, and benzophenanthrene discotic mesogenic has higher
Electric charge and exciton transfer property, the effect of electric charge transfer is conducive to the formation of columnar phase again, and in addition this kind of liquid-crystal compounds is also
With liquid crystal range width, clearing point is low, the degree of order is good the characteristics of.
If benzophenanthrene disc liquid-crystal compounds want practical application on organic semiconducting materials, various points of research and design is answered
Minor structure, to obtain the liquid crystal material of low melting point, wide in range liquid crystalline phase, while improving quasi-one-dimensional point of post axial direction by design
Sub heap intensity in order, so as to obtain stable columnar phase, forms the electric transmission of one-dimentional structure so as to improve charge transfer efficiency.
Benzophenanthrene compound is a kind of polycyclic aromatic hydrocarbon for possessing planar structure, with good optical property and thermally-stabilised
Property, and synthesize the raw material of such compound and be easy to get, product is easy to purification, therefore rich in the Benzophenanthrene of flexible alkyloxy side chain
Compound can be used as electron donor；And porphin beautiful jade class compound has the big ring of height conjugation, exist in visible-range and absorb
Spectrum, with good light and thermally stable, while be also good electron acceptor, and synthetic method is ripe.In the present invention
Using triphenylene as electron donor unit, derivatives of porphyrin as electron acceptor unit, by electron donor unit and electricity
Sub- receptor unit is connected by flexible bridge chain, and the discotic mesogenic for forming the property with photoinduction cyclic voltammetry method is ternary
Compound.Such compound future can be applied in organic solar batteries, organic photovoltaic material, liquid crystal material equimolecular device
In.
The content of the invention
It is an object of the invention to provide a kind of benzophenanthrene decyloxy bridging isooctane phenyl porphyrin ternary compound disk
The synthetic method of shape liquid crystal material.
Synthetic route of the present invention is divided into three below part：Part I is first to be with p formylbenzoic acid methyl esters and pyrroles
The pyrroles of Material synthesis two, then be Material synthesis to isooctane epoxide benzaldehyde with parahydroxyben-zaldehyde and 1- bromo-iso-octanes, so
Afterwards two pyrroles obtain porphyrin acid with porphyrin ester, porphyrin ester hydrolysis, acidifying are synthesized to isooctane epoxide benzaldehyde；Part II
Under the oxidation of ferric trichloride there is the own oxygen of coupling reaction generation monohydroxy-five in adjacent hexyloxy-phenol and adjacent two hexyloxies benzene
Base benzophenanthrene, then be that Material synthesis have a ω-bromine side chain by the hexyloxy of monohydroxy-five benzophenanthrene and 1,10- dibromo-decane
Alkoxyl benzophenanthrene；Intermediate synthesis alkoxyl bridging benzophenanthrene-porphyrin-benzo that Part III obtains above-mentioned two parts
Luxuriant and rich with fragrance ternary compound.
Benzophenanthrene and its derivative possess good liquid crystal property, with electric charge transmission and energy transfer in one-dimensional square
Performance, and synthesize Benzophenanthrene compound raw material be easy to get, product be easy to purification；And derivatives of porphyrin molecular property and structure are steady
Fixed, with good fluorescence and armaticity, while being also good electron acceptor, its synthetic method is ripe, possesses liquid crystal
Property.In the present invention using triphenylene as electron donor unit, derivatives of porphyrin as electron acceptor unit, by it
Connected by flexible bridge chain, formed with photoinduction cyclic voltammetry method property discotic mesogenic ternary compound.This
Class compound future can be applied in organic solar batteries, organic photovoltaic material, liquid crystal material equimolecular device.
Description of the drawings
Fig. 1 is benzophenanthrene decyloxy bridging isooctane phenyl porphyrin ternary compound discotic mesogenic material of the present invention knot
Structure formula.
Fig. 2 is the chemical equation of synthetic route of the present invention.
In figure：R=C6H13。
Specific embodiment
Embodiment：
It is pure that chemical reagent and solvent used in embodiment is analysis.
(1) two pyrroles（Compound 1）Synthesis：
Taking lucifuge under 0.22 milliliter of trifluoroacetic acid room temperature, to drop to 35 milliliters of pyrroles containing 6 grams of p formylbenzoic acid methyl esters molten
In liquid, it is added dropwise under nitrogen atmosphere and finishes for 30 minutes, after then lucifuge is reacted 4 hours under room temperature, adds 400 milliliters of dichloromethane,
100 milliliters of concentration of reactant mixture is that the sodium hydrate aqueous solution of 0.1 mol/L is washed three times, then with 100 milliliters of distilled waters
Washing three times, separates organic layer, and after adding anhydrous sodium sulfate drying eliminating water, vacuum rotary steam removes solvent, and the crude product for obtaining is used
200-300 mesh silica gel column chromatography is purified（Leacheate：Petroleum ether/dichloromethane, volume ratio 4:1）, obtain 1,7.20 grams of compound
White solid, yield 70.35%.Mp: 162.1-162.7℃. IR (KBr)ν max (cm-1): 1710, 1610, 1430,
1290, 802. 1H NMR (500 MHz, CDCl3) δ: 8.00 (d, J = 8.2 Hz, 4 H), 7.36-7.26 (m,
2 H), 6.74 (s, 2 H), 6.26-6.14 (m, 2 H), 5.91 (s, 2 H), 5.55 (s, 1 H), 3.93
(s, 3 H)。
(2) to isooctane epoxide benzaldehyde（Compound 2）Synthesis：
Take 2.44 grams of parahydroxyben-zaldehydes, 5.20 grams of bromo-iso-octanes, 5.52 grams of Anhydrous potassium carbonates and 20 millilitersN, N- dimethyl
After formamide, lower 80 DEG C of reactions of nitrogen atmosphere 24 hours, 100 milliliters of water are added, extracted three times with 60 milliliters of ethyl acetate, separated
Organic layer, then with 30 milliliters of saturated common salt water washing organic layers three times, organic layer is separated, add anhydrous sodium sulfate drying eliminating water
Afterwards, vacuum rotary steam removes solvent, and the crude product for obtaining is purified with 200-300 mesh silica gel column chromatography（Leacheate：Petroleum ether/dichloro
Methane, volume ratio 10:1）, obtain 2,4.30 grams of weak yellow liquids of compound, yield 91.88%.Bp:>300℃. IR (KBr)ν max (cm-1): 1610, 1380, 1260, 841. 1H NMR (300 MHz, CDCl3) δ: 9.87 (s, 1 H),
7.68 (t, J = 8.4 Hz, 2 H), 6.89 (d, J = 8.4 Hz, 2 H), 3.99 (t, J = 6.9 Hz, 2
H), 2.13-1.98 (m, 1 H), 1.33-1.25 (m, 8 H), 0.96 (t, J = 6.9 Hz, 6 H)。
(3) 5,15- bis--(4- methoxycarbonyl group phenyl) -10,20- two-(the different octyloxies of 4-) phenyl porphyrin（Compound 3）
Synthesis：
Take 0.28 g of compound 1,0.23 g of compound, 2,0.07 gram of m-Nitrobenzoic Acid and 3 milliliters of dimethylbenzene, 140 DEG C of reactions 1
After hour, room temperature is cooled to, is purified with 200-300 mesh silica gel column chromatography（Leacheate：Petroleum ether/dichloromethane, volume ratio 8:
1）, obtain 3,0.13 gram of violet solid of compound, yield 26.37%.Mp:>200℃. IR(KBr)ν max (cm-1): 1720,
1280, 801. 1H NMR (500 MHz, CDCl3) δ: 8.95 (d, J = 4.5 Hz, 4 H), 8.81 (d, J =
4.5 Hz, 4 H), 8.47 (d, J = 8.0 Hz, 4 H), 8.34 (d, J = 8.0 Hz, 4 H), 8.13 (d,J = 8.0 Hz, 4 H), 7.32 (d, J = 8.0 Hz, 4 H), 4.24-3.90 (m, 10 H), 2.13-1.93
(m, 2 H), 1.66-1.46 (m, 16 H), 1.17-1.06 (m, 6 H), 1.15-0.92 (m, 6 H), -2.73
(s, 2H)。
(4) 5,15- bis--(4- formyl phenyl) -10,20- two-(the different octyloxies of 4-) phenyl porphyrin（Compound 4）'s
Synthesis：
In taking the mixed solution that 0.1 g of compound 3 adds 15 milliliters of tetrahydrofurans and 15 milliliters of absolute methanols, 4 milliliters are added
The aqueous solution containing 0.4 gram of potassium hydroxide, 80 DEG C of condensing refluxes react 10 hours, after being cooled to room temperature, with the hydrochloric acid of 2 mol/L
It is that Buchner funnel suction filtration obtains 4,0.09 gram of dark green solid of compound, yield 92.63% between 2 ~ 3 that solution is acidified to pH.Mp:
>200℃. IR (KBr) ν max (cm-1): 2960, 1720, 1600, 1260, 802。
(5) adjacent hexyloxy-phenol（Compound 5）Synthesis：
Take 30 grams of catechols, 45 grams of 1- bromo n-hexanes, 60 grams of Anhydrous potassium carbonates, 2.28 grams of KIs and 300 milliliters anhydrous
Ethanol, 85 DEG C of condensing refluxes react 12 hours, are cooled to suction filtration after room temperature, and filtrate decompression revolving removes solvent, 0.5 mmHg's
84 DEG C of cut is collected in the case of vacuum distillation, 5,15.46 grams of colourless oil liquids of compound, yield 29.52% is obtained.Bp: 106
±3℃. IR(KBr) ν max (cm-1): 1260, 930. 1H NMR (300MHz, CDCl3) δ: 6.95-6.82 (m,
4 H), 5.68 (s, 1 H), 4.02 (t, J = 6.6 Hz, 2 H), 1.83-1.76 (m, 2 H), 1.48-1.31
(m, 6 H), 0.91 (t, J = 6.9 Hz, 3 H)。
(6) adjacent two hexyloxies benzene（Compound 6）Synthesis：
Take 10 grams of catechols, 45 grams of 1- bromo n-hexanes, 37.26 grams of Anhydrous potassium carbonates, 3.32 grams of KIs and 125 milliliters of nothings
Water-ethanol, 85 DEG C of condensing refluxes react 60 hours, are cooled to suction filtration after room temperature, and filtrate decompression revolving removes solvent, 0.5 mmHg
Vacuum distillation in the case of collect 142 DEG C of cut, obtain 6,24.53 grams of colourless oil liquids of compound, yield 96.96%.Bp:
255±3℃. IR(KBr) νmax (cm-1): 1250, 939. 1H NMR (300MHz, CDCl3) δ: 6.89 (s, 4
H), 3.99 (t, J = 6.9 Hz, 4 H), 1.83-1.76 (m, 4 H), 1.49-1.31 (m, 12 H), 0.90
(t, J = 6.9 Hz, 6 H)。
(7) hexyloxy of monohydroxy-five benzophenanthrene（Compound 7）Synthesis：
Take 1.16 g of compound 5 and 3.32 g of compound 6 are dissolved in 60 milliliters of dichloromethane, Jing constant pressure funnels drop to 80
In dichloromethane solution of the milliliter containing 12.96 grams of anhydrous ferric trichlorides and 8 milliliters of nitromethanes, dropwise addition is finished for 30 minutes, is controlled
Reacting liquid temperature processed after reaction 4 hours, adds 30 milliliters of absolute methanols and 60 milliliters of water terminating reactions between 0 ~ 3 DEG C, separates
Organic layer, with 30 milliliters of dichloromethane aqueous layer extracteds three times, collects all organic layers, then has with 20 milliliters of saturated common salt water washings
Machine layer, separates organic layer, and after adding anhydrous sodium sulfate drying eliminating water, vacuum rotary steam removes solvent, the crude product 200- for obtaining
300 mesh silica gel column chromatographies are purified（Leacheate：Petrol ether/ethyl acetate, volume ratio 50:1）, obtain 7,1.80 grams of whites of compound
Solid, yield 40.45%.Mp: 47.7-50.1℃. IR(KBr)ν max (cm-1): 3040, 1240, 837. 1H NMR
(400MHz, CDCl3) δ: 7.96 (s, 1 H), 7.83 (s, 3 H), 7.82 (s, 1 H), 7.77 (s, 1
H), 5.91 (s, 1 H), 4.31-4.19 (m, 10 H), 1.98-1.90 (m, 10 H), 1.59-1.40 (m, 30
H), 0.96-0.92 (m, 15 H)。
(8) the hexyloxy benzophenanthrene of bromo decyloxy-five（Compound 8）Synthesis：
Take 0.58 g of compound, 7,1.40 grams of 1,10- dibromo-decanes, 0.08 gram of TBAB, 0.17 gram of potassium hydroxide, 7
Milliliter water and 11 milliliters of dichloromethane, after reaction being stirred at room temperature under nitrogen atmosphere 24 hours, separate organic layer, with 10 milliliters of dichloros
Methane aqueous layer extracted three times, collects all organic layers, then with 8 milliliters of saturated common salt water washing organic layers, separates organic layer, adds
After anhydrous sodium sulfate drying eliminating water, vacuum rotary steam removes solvent, and the crude product for obtaining is purified with 200-300 mesh silica gel column chromatography
（Leacheate：Petrol ether/ethyl acetate, volume ratio 100:1）, obtain 8,0.51 gram of Off-white solid of compound, yield 67.82%.
Bp: >300℃. IR (KBr) ν max (cm-1): 2930, 1620, 1260, 837. 1H NMR (400 MHz, CDCl3)
δ: 7.84 (s, 6 H), 4.23 (t, J = 6.8 Hz, 12 H), 3.40 (t, J = 6.8 Hz, 2 H),
1.98-1.90 (m, 12 H), 1.67-1.50 (m, 16 H), 1.42-1.33 (m, 28 H), 0.94 (t, J =
6.8 Hz, 15 H)。
(9) benzophenanthrene decyloxy bridging isooctane phenyl porphyrin（Compound 9）Synthesis：
Take 0.21 g of compound 4,0.53 g of compound, 8,0.08 gram of potassium carbonate and 12 millilitersN, N- dimethyl formamide solution,
The lower 80 DEG C of back flow reactions of nitrogen atmosphere add 120 milliliters of water after 24 hours, are extracted three times with 60 milliliters of ethyl acetate, separate water
Layer and organic layer, with 20 milliliters of saturated common salt water washing organic layers, separate organic layer, after adding anhydrous sodium sulfate drying eliminating water,
Vacuum rotary steam removes solvent, and the crude product for obtaining is purified with 200-300 mesh silica gel column chromatography（Leacheate：Petroleum ether/dichloromethane
Alkane, volume ratio 5:1）, obtain 9,0.36 gram of violet solid of compound, yield 60.33%.Mp: 22.5±3℃. IR(KBr)ν max (cm-1): 2930, 1720, 1260. 1H NMR (500 MHz, CDCl3) δ: 8.93 (d, J = 4.0 Hz, 4
H), 8.80 (d, J = 4.0 Hz, 4 H), 8.47 (d, J = 8.0 Hz, 4 H), 8.33 (d, J = 8.0
Hz, 4 H), 8.12 (d, J = 8.0 Hz, 4 H), 7.84 (s, 6 H), 7.83 (s, 6 H), 7.30 (d, J
= 8.0 Hz, 4 H), 4.53 (t, J = 6.5 Hz, 4 H), 4.27-4.22 (m, 24 H), 4.15 (d, J =
6.0 Hz, 4 H), 2.01-1.93 (m, 26 H), 1.72-1.40 (m, 104 H), 1.09 (t, J = 7.5 Hz,
6 H), 1.01 (t, J = 7.5 Hz, 6 H), 0.97-0.93 (m, 30 H), -2.77 (s, 2 H).
Elemental analysis calcd for C178H242N4O18 (2726): C, 78.43, H, 8.95, N, 2.06,
Found: C, 77.92, H, 8.91, N, 2.14。
Claims (1)
1. a kind of synthetic method of benzophenanthrene decyloxy bridging isooctane phenyl porphyrin ternary compound discotic mesogenic material,
It is characterized in that concretely comprising the following steps：
(1) two pyrroles is the synthesis of compound 1：
Taking lucifuge under 0.22 milliliter of trifluoroacetic acid room temperature, to drop to 35 milliliters of pyrroles containing 6 grams of p formylbenzoic acid methyl esters molten
In liquid, it is added dropwise under nitrogen atmosphere and finishes for 30 minutes, after then lucifuge is reacted 4 hours under room temperature, adds 400 milliliters of dichloromethane,
The reactant mixture sodium hydrate aqueous solution of 100 milliliter of 0.1 mol/L is washed three times, then washs three with 100 milliliters of distilled waters
It is secondary, organic layer is separated, after adding anhydrous sodium sulfate drying eliminating water, vacuum rotary steam removes solvent, the crude product 200-300 for obtaining
Mesh silica gel column chromatography is purified, leacheate：Petroleum ether/dichloromethane, volume ratio 4:1,1,7.20 grams of white solids of compound are obtained,
Yield 70.35%；Mp: 162.1-162.7℃. IR (KBr)ν max (cm-1): 1710, 1610, 1430, 1290, 802.1H NMR (500 MHz, CDCl3) δ: 8.00 (d, J = 8.2 Hz, 4 H), 7.36-7.26 (m, 2 H), 6.74
(s, 2 H), 6.26-6.14 (m, 2 H), 5.91 (s, 2 H), 5.55 (s, 1 H), 3.93 (s, 3 H)；
(2) be to isooctane epoxide benzaldehyde compound 2 synthesis：
Take 2.44 grams of parahydroxyben-zaldehydes, 5.20 grams of bromo-iso-octanes, 5.52 grams of Anhydrous potassium carbonates and 20 millilitersN, N- dimethyl
After formamide, lower 80 DEG C of reactions of nitrogen atmosphere 24 hours, 100 milliliters of water are added, extracted three times with 60 milliliters of ethyl acetate, separated
Organic layer, then with 30 milliliters of saturated common salt water washing organic layers three times, organic layer is separated, add anhydrous sodium sulfate drying eliminating water
Afterwards, vacuum rotary steam removes solvent, and the crude product for obtaining is purified with 200-300 mesh silica gel column chromatography, leacheate：Petroleum ether/dichloro
Methane, volume ratio 10:1, obtain 2,4.30 grams of weak yellow liquids of compound, yield 91.88%；Bp:>300℃. IR (KBr)ν max (cm-1): 1610, 1380, 1260, 841. 1H NMR (300 MHz, CDCl3) δ: 9.87 (s, 1 H),
7.68 (t, J = 8.4 Hz, 2 H), 6.89 (d, J = 8.4 Hz, 2 H), 3.99 (t, J = 6.9 Hz, 2
H), 2.13-1.98 (m, 1 H), 1.33-1.25 (m, 8 H), 0.96 (t, J= 6.9 Hz, 6 H)；
(3) 5,15- bis--(4- methoxycarbonyl group phenyl) -10,20- two-(the different octyloxies of 4-) phenyl porphyrin is the conjunction of compound 3
Into：
Take 0.28 g of compound 1,0.23 g of compound, 2,0.07 gram of m-Nitrobenzoic Acid and 3 milliliters of dimethylbenzene, 140 DEG C of reactions 1
After hour, room temperature is cooled to, is purified with 200-300 mesh silica gel column chromatography, leacheate：Petroleum ether/dichloromethane, volume ratio 8:1,
Obtain 3,0.13 gram of violet solid of compound, yield 26.37%；Mp:>200℃. IR(KBr)ν max (cm-1): 1720,
1280, 801. 1H NMR (500 MHz, CDCl3) δ: 8.95 (d, J = 4.5 Hz, 4 H), 8.81 (d, J =
4.5 Hz, 4 H), 8.47 (d, J = 8.0 Hz, 4 H), 8.34 (d, J = 8.0 Hz, 4 H), 8.13 (d,J = 8.0 Hz, 4 H), 7.32 (d, J = 8.0 Hz, 4 H), 4.24-3.90 (m, 10 H), 2.13-1.93
(m, 2 H), 1.66-1.46 (m, 16 H), 1.17-1.06 (m, 6 H), 1.15-0.92 (m, 6 H), -2.73
(s, 2H)；
(4) 5,15- bis--(4- formyl phenyl) -10,20- two-(the different octyloxies of 4-) phenyl porphyrin is the conjunction of compound 4
Into：
In taking the mixed solution that 0.1 g of compound 3 adds 15 milliliters of tetrahydrofurans and 15 milliliters of absolute methanols, 4 milliliters are added
The aqueous solution containing 0.4 gram of potassium hydroxide, 80 DEG C of condensing refluxes react 10 hours, after being cooled to room temperature, with the hydrochloric acid of 2 mol/L
It is that Buchner funnel suction filtration obtains 4,0.09 gram of dark green solid of compound, yield 92.63% between 2 ~ 3 that solution is acidified to pH；Mp:
>200℃. IR (KBr) ν max (cm-1): 2960, 1720, 1600, 1260, 802；
(5) adjacent hexyloxy-phenol is the synthesis of compound 5：
Take 30 grams of catechols, 45 grams of 1- bromo n-hexanes, 60 grams of Anhydrous potassium carbonates, 2.28 grams of KIs and 300 milliliters anhydrous
Ethanol, 85 DEG C of condensing refluxes react 12 hours, are cooled to suction filtration after room temperature, and filtrate decompression revolving removes solvent, 0.5 mmHg's
84 DEG C of cut is collected in the case of vacuum distillation, 5,15.46 grams of colourless oil liquids of compound, yield 29.52% is obtained；Bp: 106
±3℃. IR(KBr) ν max (cm-1): 1260, 930. 1H NMR (300MHz, CDCl3) δ: 6.95-6.82 (m,
4 H), 5.68 (s, 1 H), 4.02 (t, J = 6.6 Hz, 2 H), 1.83-1.76 (m, 2 H), 1.48-1.31
(m, 6 H), 0.91 (t, J = 6.9 Hz, 3 H)；
(6) adjacent two hexyloxies benzene is the synthesis of compound 6：
Take 10 grams of catechols, 45 grams of 1- bromo n-hexanes, 37.26 grams of Anhydrous potassium carbonates, 3.32 grams of KIs and 125 milliliters of nothings
Water-ethanol, 85 DEG C of condensing refluxes react 60 hours, are cooled to suction filtration after room temperature, and filtrate decompression revolving removes solvent, 0.5 mmHg
Vacuum distillation in the case of collect 142 DEG C of cut, obtain 6,24.53 grams of colourless oil liquids of compound, yield 96.96%；Bp:
255±3℃. IR(KBr) νmax (cm-1): 1250, 939. 1H NMR (300MHz, CDCl3) δ: 6.89 (s, 4
H), 3.99 (t, J = 6.9 Hz, 4 H), 1.83-1.76 (m, 4 H), 1.49-1.31 (m, 12 H), 0.90
(t, J = 6.9 Hz, 6 H)；
(7) hexyloxy of monohydroxy-five benzophenanthrene is the synthesis of compound 7：
Take 1.16 g of compound 5 and 3.32 g of compound 6 are dissolved in 60 milliliters of dichloromethane, Jing constant pressure funnels drop to 80
In dichloromethane solution of the milliliter containing 12.96 grams of anhydrous ferric trichlorides and 8 milliliters of nitromethanes, dropwise addition is finished for 30 minutes, is controlled
Reacting liquid temperature processed after reaction 4 hours, adds 30 milliliters of absolute methanols and 60 milliliters of water terminating reactions between 0 ~ 3 DEG C, separates
Organic layer, with 30 milliliters of dichloromethane aqueous layer extracteds three times, collects all organic layers, then has with 20 milliliters of saturated common salt water washings
Machine layer, separates organic layer, and after adding anhydrous sodium sulfate drying eliminating water, vacuum rotary steam removes solvent, the crude product 200- for obtaining
300 mesh silica gel column chromatographies are purified, leacheate：Petrol ether/ethyl acetate, volume ratio 50:1, obtain 7,1.80 grams of whites of compound
Solid, yield 40.45%；Mp: 47.7-50.1℃. IR(KBr)ν max (cm-1): 3040, 1240, 837. 1H NMR
(400MHz, CDCl3) δ: 7.96 (s, 1 H), 7.83 (s, 3 H), 7.82 (s, 1 H), 7.77 (s, 1
H), 5.91 (s, 1 H), 4.31-4.19 (m, 10 H), 1.98-1.90 (m, 10 H), 1.59-1.40 (m, 30
H), 0.96-0.92 (m, 15 H)；
(8) the hexyloxy benzophenanthrene of bromo decyloxy-five is the synthesis of compound 8：
Take 0.58 g of compound, 7,1.40 grams of 1,10- dibromo-decanes, 0.08 gram of TBAB, 0.17 gram of potassium hydroxide, 7
Milliliter water and 11 milliliters of dichloromethane, after reaction being stirred at room temperature under nitrogen atmosphere 24 hours, separate organic layer, with 10 milliliters of dichloros
Methane aqueous layer extracted three times, collects all organic layers, then with 8 milliliters of saturated common salt water washing organic layers, separates organic layer, adds
After anhydrous sodium sulfate drying eliminating water, vacuum rotary steam removes solvent, and the crude product for obtaining is purified with 200-300 mesh silica gel column chromatography,
Leacheate：Petrol ether/ethyl acetate, volume ratio 100:1, obtain 8,0.51 gram of Off-white solid of compound, yield 67.82%；
Bp: >300℃. IR (KBr) ν max (cm-1): 2930, 1620, 1260, 837. 1H NMR (400 MHz, CDCl3)
δ: 7.84 (s, 6 H), 4.23 (t, J = 6.8 Hz, 12 H), 3.40 (t, J = 6.8 Hz, 2 H),
1.98-1.90 (m, 12 H), 1.67-1.50 (m, 16 H), 1.42-1.33 (m, 28 H), 0.94 (t, J =
6.8 Hz, 15 H)；
(9) benzophenanthrene decyloxy bridging isooctane phenyl porphyrin is the synthesis of compound 9：
Take 0.21 g of compound 4,0.53 g of compound, 8,0.08 gram of potassium carbonate and 12 millilitersN, N- dimethyl formamide solution,
The lower 80 DEG C of back flow reactions of nitrogen atmosphere add 120 milliliters of water after 24 hours, are extracted three times with 60 milliliters of ethyl acetate, separate water
Layer and organic layer, with 20 milliliters of saturated common salt water washing organic layers, separate organic layer, after adding anhydrous sodium sulfate drying eliminating water,
Vacuum rotary steam removes solvent, and the crude product for obtaining is purified with 200-300 mesh silica gel column chromatography, leacheate：Petroleum ether/dichloromethane
Alkane, volume ratio 5:1, obtain 9,0.36 gram of violet solid of compound, yield 60.33%；Mp: 22.5±3℃. IR(KBr)ν max
(cm-1): 2930, 1720, 1260. 1H NMR (500 MHz, CDCl3) δ: 8.93 (d, J = 4.0 Hz, 4 H),
8.80 (d, J = 4.0 Hz, 4 H), 8.47 (d, J = 8.0 Hz, 4 H), 8.33 (d, J = 8.0 Hz, 4
H), 8.12 (d, J = 8.0 Hz, 4 H), 7.84 (s, 6 H), 7.83 (s, 6 H), 7.30 (d, J = 8.0
Hz, 4 H), 4.53 (t, J = 6.5 Hz, 4 H), 4.27-4.22 (m, 24 H), 4.15 (d, J = 6.0
Hz, 4 H), 2.01-1.93 (m, 26 H), 1.72-1.40 (m, 104 H), 1.09 (t, J = 7.5 Hz, 6
H), 1.01 (t, J = 7.5 Hz, 6 H), 0.97-0.93 (m, 30 H), -2.77 (s, 2 H). Elemental
analysis calcd for C178H242N4O18 (2726): C, 78.43, H, 8.95, N, 2.06, Found: C,
77.92, H, 8.91, N, 2.14；
It is pure that the chemical reagent and solvent are analysis.
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| CN1714091A (en) * | 2002-10-21 | 2005-12-28 | L.莫尔特尼及阿利蒂兄弟联合股份公司 | Meso-substituted porphyrins |
| CN106118688A (en) * | 2016-06-27 | 2016-11-16 | 桂林理工大学 | The synthetic method of benzophenanthrene decane epoxide bridging isobutyltrimethylmethane. phenyl porphyrin binary compound discotic mesogenic material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1714091A (en) * | 2002-10-21 | 2005-12-28 | L.莫尔特尼及阿利蒂兄弟联合股份公司 | Meso-substituted porphyrins |
| CN106118688A (en) * | 2016-06-27 | 2016-11-16 | 桂林理工大学 | The synthetic method of benzophenanthrene decane epoxide bridging isobutyltrimethylmethane. phenyl porphyrin binary compound discotic mesogenic material |
Non-Patent Citations (1)
| Title |
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| JIANJUN MIAO等: "Hydrogen Bonding Induced Supramolecular Self-Assembly of Linear Doubly Discotic Triad Supermolecules", 《CHEM. ASIAN J.》 * |
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