CN106117228A - The synthetic method of benzophenanthrene decane epoxide bridging isobutyltrimethylmethane. phenyl porphyrin metal Ni coordination compound - Google Patents
The synthetic method of benzophenanthrene decane epoxide bridging isobutyltrimethylmethane. phenyl porphyrin metal Ni coordination compound Download PDFInfo
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Abstract
The invention discloses the synthetic method of a kind of benzophenanthrene decane epoxide bridging isobutyltrimethylmethane. phenyl porphyrin metal Ni 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, have 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 isobutyltrimethylmethane. phenyl porphyrin metal Ni 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 isobutyltrimethylmethane. phenyl porphyrin metal Ni coordination compound
Method.
Background technology
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 isobutyltrimethylmethane. phenyl porphyrin metal Ni to coordinate
The synthetic method of thing.
The synthetic route of the present invention is divided into three below part: Part I, first by adjacent two hexyloxy benzene and the own oxygen of 2-
Base phenol occurs coupling reaction to generate monohydroxy five hexyloxy benzophenanthrene under the Oxidation of ferric chloride；Secondly, with single hydroxyl
Base five hexyloxy benzophenanthrene, 1,10-dibromo-decane are the primary raw material synthesis alkoxyl benzophenanthrene containing a ω-bromine side chain；The
Two parts are to synthesize isobutyltrimethylmethane. epoxide benzaldehyde for primary raw material, then with right with hydroxy benzaldehyde, 1-bromo-iso-octane
Acyl radical methyl benzoate, pyrroles synthesize porphyrin ester in dimethylbenzene.Finally, hydrolyzed by the porphyrin ester obtained, acidifying obtains porphin
Quinoline acid；Part III is that the intermediate obtained by above-mentioned two parts synthesizes a series of alkoxyl bridging by phase-transfer-catalyzed reactions
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 isobutyltrimethylmethane. phenyl porphyrin metal Ni complex structure formula of the present invention.
Fig. 2 is the chemical equation of synthetic route of the present invention.
In figure: R=C6H13。
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)
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
Dehydrated alcohol, 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
Decompression distillation in the case of collect the fraction of 140-143 DEG C, 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 with 15 milliliters, and 2mol/L dilute hydrochloric acid washes twice, with 15 milliliters of saturated aqueous common salts
Washed once, separate organic layer, after addition anhydrous sodium sulfate is dried except water, rotated evaporimeter removes solvent, the thick product obtained
Thing silica gel (200-300 mesh) column chromatography purifies (leacheate be ethyl acetate/petroleum ether volume ratio be 1:30-1:15), obtains
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) synthesis of bromo decyloxy-five hexyloxy benzophenanthrene (compound 4)
By 3,2.97 grams of 1,10-dibromo-decanes of 1.23 g of compound, 0.43 gram of potassium hydroxide and 0.16 gram of tetrabutyl phosphonium bromide
Ammonium, joins in the mixture of 10 milliliters of dichloromethane and 6.5 milliliters of water, is stirred at room temperature 24 hours under nitrogen atmosphere, with 30 millis
Rise water to wash twice, washed once with 15 milliliters of saturated aqueous common salts, separate organic layer, after addition anhydrous sodium sulfate is dried except water,
Rotated evaporimeter removes solvent, and with the purification of silica gel (200-300 mesh) column chromatography, (leacheate is ethyl acetate/petroleum ether, volume
Ratio is 1:30-1:20), obtain colorless solid (1.41 grams) i.e. compound 4, productivity is 89%；Bp>300℃,IR(KBr)νmax
(cm-1):1260,837；1H NMR(400MHz,CDCl3) δ: 7.84 (s, 6H), 4.23 (t, J=6.8Hz, 12H), 3.40 (t, J
=6.8Hz, 2H), 1.98-1.91 (m, 12H), 1.85 (t, J=6.8Hz, 2H), 1.62-1.54 (m, 12H), 1.42-1.35
(m, 30H), 0.94 (t, J=6.8Hz, 15H).
(5) synthesis to isobutyltrimethylmethane. epoxide benzaldehyde (compound 5)
By 2.44 grams of hydroxy benzaldehydes, 6.725 grams of bromo-iso-octanes, 5.52 grams of Anhydrous potassium carbonates and 20 milliliters through CaH2
The DMF being dried, reacts after reacting 12 hours and terminate, with 200 milliliters of water and 20 in nitrogen atmosphere at 80 DEG C
Milliliter dichloromethane extraction separates organic layer three times, is dried except water with anhydrous sodium sulfate, and rotated evaporimeter removes solvent,
Crude product 200-300 mesh silica gel column chromatography purifies (eluant is dichloromethane: petroleum ether volume ratio=1:5-1:2), obtains
5.75 grams of i.e. compounds 5 of weak yellow liquid, 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 isobutyltrimethylmethane. 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, dripped 1.91 grams of pyrroles 10 of 32 milliliters of xylene solutions dilutions by constant pressure funnel
Minute, at 140 DEG C, back flow reaction is reacted after 3.5 hours and is terminated, and is removed by distillation xylene solvent, obtains dark thick thing,
Purify (leacheate be dichloromethane/petroleum ether volume ratio be 1:2-1:1) with 200-300 mesh silica gel column chromatography, finally use dichloro
Methane/absolute methanol volume ratio is that 1:1 carries out 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) the 5-para Toluic Acid base-10,15,20-three synthesis to isobutyltrimethylmethane. phenyl porphyrin (compound 7)
Take the oxolane (THF) that 1.4 g of compound 6 and the 5 milliliters aqueous solution containing 1.79 grams of potassium hydroxide is at 25 milliliters
After solution fully dissolves, add the absolute methanol of 5 milliliters, back flow reaction 3 hours at 70 DEG C, add commercially available after being cooled to room temperature
Between concentrated hydrochloric acid regulation pH to 2-3, sucking filtration obtains green solid 5-para Toluic Acid base-10, and 15,20-tri-to isobutyltrimethylmethane. epoxide benzene
Base porphyrin i.e. compound 7, productivity is 65%；Mp176.3-177.5℃；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) ,-2.72 (s, 2H).
(8) synthesis of benzophenanthrene decane epoxide bridging isobutyltrimethylmethane. phenyl porphyrin (compound 8)
0.108 gram takes 4,0.0027 gram of potassium carbonate of compound 7,0.127 g of compound and 0.16 gram of tetrabutyl ammonium bromide, adds
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 isobutyltrimethylmethane. phenyl porphyrin metal Ni coordination compound (compound 9)
Take 8,0.0206 gram of Nickel dichloride hexahydrate of 0.1 g of compound, 15 milliliters of N,N-dimethylformamides and 10 milliliter three
Chloromethanes, reacts after stirring reaction 22 hours and terminate in nitrogen atmosphere at 65 DEG C；Water layer and organic is separated with chloroform extraction
Layer, is dried except water with anhydrous sodium sulfate, and rotated evaporimeter removes solvent, purifies with silica gel (200-300 mesh) column chromatography
(leacheate be ethyl acetate/petroleum ether volume ratio be 1:30-1:20), obtains 0.071 gram of atropurpureus solid i.e. compound 9, produces
Rate 70%；IR(KBr)νmax(cm-1):1720,1360,1240,824；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).
Claims (1)
1. a synthetic method for benzophenanthrene decane epoxide bridging isobutyltrimethylmethane. phenyl porphyrin metal Ni 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 with 15 milliliters, and 2mol/L dilute hydrochloric acid washes twice, with 15 milliliters of saturated common salt washings
Washing once, separate organic layer, after addition anhydrous sodium sulfate is dried except water, rotated evaporimeter removes solvent, the crude product obtained
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
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) bromo decyloxy-five hexyloxy benzophenanthrene i.e. synthesis of compound 4:
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 tetrabutyl ammonium bromide, add
Enter in the mixture of 10 milliliters of dichloromethane and 6.5 milliliters of water, be stirred at room temperature under nitrogen atmosphere 24 hours, with 30 milliliters of washings
Wash twice, washed once with 15 milliliters of saturated aqueous common salts, separate organic layer, after addition anhydrous sodium sulfate is dried except water, rotated
Evaporimeter removes solvent, purifies with 200-300 mesh silica gel column chromatography, and leacheate is ethyl acetate/petroleum ether, and volume ratio is 1:
30-1:20, obtains 1.41 grams of colorless solids i.e. compound 4, and productivity is 89%；Bp>300℃,IR(KBr)νmax(cm-1):1260,
837；1H NMR(400MHz,CDCl3) δ: 7.84 (s, 6H), 4.23 (t, J=6.8Hz, 12H), 3.40 (t, J=6.8Hz, 2H),
1.98-1.91 (m, 12H), 1.85 (t, J=6.8Hz, 2H), 1.62-1.54 (m, 12H), 1.42-1.35 (m, 30H), 0.94
(t, J=6.8Hz, 15H)；
(5) to the isobutyltrimethylmethane. epoxide benzaldehyde i.e. synthesis of compound 5:
By 2.44 grams of hydroxy benzaldehydes, 6.725 grams of bromo-iso-octanes, 5.52 grams of Anhydrous potassium carbonates and 20 milliliters through CaH2It is dried
DMF, react at 80 DEG C to react after 12 hours in nitrogen atmosphere and terminate, with 200 milliliters of water and 20 milliliters
Dichloromethane extraction separates organic layer three times, is dried except water with anhydrous sodium sulfate, and rotated evaporimeter removes solvent, slightly produces
Thing 200-300 mesh silica gel column chromatography purifies, and eluant is dichloromethane: petroleum ether volume ratio=1:5-1:2, obtains 5.75 grams
Weak yellow liquid 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) 5-para Toluic Acid carbomethoxy-10,15,20-three is to the isobutyltrimethylmethane. 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, dripped 1.91 grams of pyrroles 10 points of 32 milliliters of xylene solution dilutions by constant pressure funnel
Clock, at 140 DEG C, back flow reaction is reacted after 3.5 hours and is terminated, and is removed by distillation xylene solvent, obtains dark thick thing, uses
200-300 mesh silica gel column chromatography purify, leacheate be dichloromethane/petroleum ether volume ratio be 1:2-1:1, finally use dichloromethane
Alkane/absolute methanol volume ratio is that 1:1 carries out 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 isobutyltrimethylmethane. phenyl porphyrin i.e. synthesis of compound 7:
Take 1.4 g of compound 6 and 5 milliliters fully to dissolve in the oxolane of 25 milliliters containing 1.79 grams of potassium hydroxide aqueous solutions
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 green solid 5-para Toluic Acid base-10, and 15,20-tri-to the isobutyltrimethylmethane. i.e. compound of phenyl porphyrin
7, productivity is 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) ,-2.72 (s, 2H)；
(8) synthesis of the i.e. compound 8 of benzophenanthrene decane epoxide bridging isobutyltrimethylmethane. phenyl porphyrin:
Take 0.108 gram and take 4,0.0027 gram of potassium carbonate of compound 7,0.127 g of compound and 0.16 gram of tetrabutyl ammonium bromide, add
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；Extract with chloroform
Taking and separate 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, drenches
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, produce
Rate 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 isobutyltrimethylmethane. phenyl porphyrin metal Ni coordination compound:
Take 8,0.0206 gram of Nickel dichloride hexahydrate of 0.1 g of compound, 15 milliliters of N,N-dimethylformamides and 10 milliliter of three chloromethane
Alkane, reacts after stirring reaction 22 hours and terminate in nitrogen atmosphere at 65 DEG C；Separate water layer and organic layer with chloroform extraction, use
Anhydrous sodium sulfate is dried except water, and rotated evaporimeter removes solvent, purifies with 200-300 mesh silica gel column chromatography, leacheate
Be ethyl acetate/petroleum ether volume ratio be 1:30-1:20, obtain 0.071 gram of atropurpureus solid i.e. compound 9, productivity 70%；IR
(KBr)νmax(cm-1):1720,1360,1240,824；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)；
Described chemical reagent and solvent are analytical pure.
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Citations (2)
| 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 |
| CN105541616A (en) * | 2015-12-05 | 2016-05-04 | 桂林理工大学 | Hexaalkoxytriphenylene-flexible bridge-perylenetetracarboxylic acid tetraester binary compound and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105541616A (en) * | 2015-12-05 | 2016-05-04 | 桂林理工大学 | Hexaalkoxytriphenylene-flexible bridge-perylenetetracarboxylic acid tetraester binary compound and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 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.》 * |
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