CN106117220A - The synthetic method of benzophenanthrene dodecyloxy bridging isobutyltrimethylmethane. phenyl porphyrin metal Zn coordination compound - Google Patents
The synthetic method of benzophenanthrene dodecyloxy bridging isobutyltrimethylmethane. phenyl porphyrin metal Zn coordination compound Download PDFInfo
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Abstract
The invention discloses the synthetic method of a kind of benzophenanthrene dodecyloxy bridging isobutyltrimethylmethane. 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, synthesis obtains benzophenanthrene dodecyloxy bridging isobutyltrimethylmethane. phenyl porphyrin metal Zn coordination compound and can apply 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 conjunction of a kind of benzophenanthrene dodecyloxy bridging isobutyltrimethylmethane. phenyl porphyrin metal Zn coordination compound
One-tenth method.
Background technology
Symmetry according to molecular structure divides, and porphyrin can be divided into symmetry porphyrin and asymmetric porphyrin, if symmetrical, takes
Certainly on pyrrole ring, atom with meso carbon is the most consistent with group.According to whether the character being dissolved in water divides, porphyrin can divide
For water-soluble porphyrin and water-insoluble porphyrin, wherein water-soluble porphyrin refers to be dissolved in the hydrophilic solvent such as water, methanol, and non-aqueous
Dissolubility porphyrin refers to be dissolved in the oil loving solvents such as dichloromethane, dimethylbenzene, chloroform and benzene.Porphyrin is a class heat stability
Well compound, and its solution has the strongest fluorescent effect, and porphyrin is a kind of dystectic dark solid compound, most
Water insoluble and alkali, but mineral acid can be dissolved in.Structurally, in porphyrin ring, on four nitrogen-atoms, have four pairs of lone pair electrons, and
And two hydrogen atoms connected on nitrogen-atoms are easily lost thus obtain dianion, therefore porphyrin easily with positive charge
Metallic ion coordination forms metal complex.
The research history of porphyrin chemistry has reached more than 100 year, and structure and the character of current porphyrin compound are ground by people
Deeply, and the research in the field such as its synthetic method and application is also favored by researcher deeply in the comparison studied carefully.All the time,
Synthetic porphyrin is used to simulate the various performances of natural porphyrin compound, and this is always interested and important the grinding of people
Study carefully.When the thirties in 20th century, Rothemund is using benzaldehyde and pyrroles as primary raw material, and pyridine is as solvent, at 150 DEG C
After down and having reacted 24 hours in sealing pipe, tetraphenylporphyrin is synthesized, thus the prelude quilt of synthetic porphyrin compound
Open.Hereafter, synthetic porphyrin (the most immobilized porphyrin and metalloporphyrin) is widely used in each field.And synthetic
The method of porphyrin mainly has Rothemund method, microwave induced method, Adler method, Lindsey method, Guo Can city method and Macdonald
The methods such as method.
Benzophenanthrene dodecyloxy bridging isobutyltrimethylmethane. phenyl porphyrin metal Zn coordination compound has the photoelectric property of uniqueness,
Such compou nd synthesis method is simple, and the response time is shorter, and productivity is high, has stronger absorption in visible region, has and become
The potentiality of photoelectric material, can apply at organic photovoltaic material, liquid crystal 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 dodecyloxy bridging isobutyltrimethylmethane. phenyl porphyrin metal Zn to join
The synthetic method of compound.
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, 1,12-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, the porphyrin ester obtained hydrolysis, acidifying are obtained porphin
Quinoline acid;Part III be intermediate that above-mentioned two parts are obtained by phase-transfer-catalyzed reactions synthesis alkoxyl bridging porphyrin-
Benzophenanthrene binary compound reacts in the mixed solvent of DMF and chloroform with slaine, and then
Obtain metal complex.
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
There are strong absorption, photochemistry and Heat stability is good and synthetic method ripe, there is good liquid crystal property, the metal combination of porphyrin
Thing suffers from more superior chemical property in every respect, is worth us to go to inquire into.The present invention is by designing and synthesizing containing electricity
The discotic mesogenic binary compound of sub-donor (D)-bridge (B)-receptor (A) structure, this compounds can be applied at organic photovoltaic
Material, liquid crystal material, organic solar batteries, Organic Light Emitting Diode equimolecular device.
Accompanying drawing explanation
Fig. 1 is the structure of benzophenanthrene dodecyloxy bridging isobutyltrimethylmethane. phenyl porphyrin metal Zn coordination compound of the present invention
Formula.
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):
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 millis
Rising 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 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 200-300 mesh silica gel 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 bromododecane epoxide-five hexyloxy benzophenanthrene (compound 4):
By 3,2.63 grams of 1,12-dibromo-dodecanes of 1.0 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 200-300 mesh silica gel column chromatography, (leacheate is ethyl acetate/petroleum ether volume ratio
For 1:30-1:10), obtaining weak yellow liquid 1.19 grams is compound 4, productivity 90%;bp>300℃,IR(KBr)νmax(cm-1):
1260,836.1H NMR(400MHz,CDCl3) δ: 7.84 (s, 6H), 4.23 (t, J=6.8Hz, 12H), 3.40 (t, J=
6.8Hz, 2H), 1.98-1.81 (m, 14H), 1.64-1.50 (m, 12H), 1.47-1.20 (m, 34H), 0.93 (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 (DMF) being dried, reacts after reacting 12 hours and terminate, with 200 milliliters in nitrogen atmosphere at 80 DEG C
Water and 20 milliliters of dichloromethane extractions separate organic layer three times, are dried except water with anhydrous sodium sulfate, and rotated evaporimeter removes
Remove solvent, crude product 200-300 mesh silica gel column chromatography purify (eluant is dichloromethane: petroleum ether volume ratio=1:5-1:
2), obtaining 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 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):
The 1.79 grams of potassium hydroxide aqueous solutions taking 1.4 g of compound 6 and 5 milliliters are molten at the oxolane (THF) of 25 milliliters
After liquid fully dissolves, add the absolute methanol of 5 milliliters, back flow reaction 3 hours at 70 DEG C, add commercially available dense after being cooled to room temperature
Salt acid for adjusting pH is between 2-3, and sucking filtration obtains green solid 5-para Toluic Acid base-10, and 15,20-tri-to isobutyltrimethylmethane. phenyl
Porphyrin i.e. compound 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 benzophenanthrene dodecyloxy bridging isobutyltrimethylmethane. phenyl porphyrin (compound 8):
Take 0.25g compound 7,0.217g compound 4,0.037g potassium carbonate and 0.16g tetrabutyl ammonium bromide, join
In the mixture of 6mL chloroform and 12mL water, the lower 80 DEG C of back flow reaction of nitrogen atmosphere 36 hours;Carry out with chloroform and water
Extraction separates water layer and organic layer, and organic layer is spin-dried for after drying through anhydrous sodium sulfate, purifies with 200-300 mesh silica gel column chromatography
(leacheate be ethyl acetate/petroleum ether volume ratio be 1:10-1:5), obtains purple thick solid 0.19g i.e. compound 8, produces
Rate 47%;mp 83±3℃IR(KBr)νmax(cm-1):1380,1240,803;1H NMR(500MHz,CDCl3)δ8.92(d,J
=7.9Hz, 6H), 8.79 (d, J=4.7Hz, 2H), 8.46 (d, J=8.0Hz, 2H), 8.33 (d, J=8.0Hz, 2H), 7.91-
7.76 (m, 6H), 7.39-7.29 (m, 6H), 4.49 (dd, J=44.3,37.7Hz, 4H), 4.31 4.09 (m, 16H), 1.99
(dd, J=49.6,43.7Hz, 16H), 1.81-1.62 (m, 10H), 1.43 (ddd, J=82.0,37.2,35.3Hz, 46H),
1.14–0.69(m,34H),-2.73(s,2H).Elemental analysis calcd for C129H172N4O11(1953):C,
79.23,H,8.88,N,2.89,Found:C,79.26,H,8.87,N,2.87.
(9) synthesis of benzophenanthrene dodecyloxy bridging isobutyltrimethylmethane. 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, and with the purification of 200-300 mesh silica gel column chromatography, (leacheate is
Ethyl acetate/petroleum ether volume ratio is 1:10-1:5), obtain 0.087 gram of violet solid i.e. compound 9, productivity 85%;Mp
21.4±3℃,IR(KBr)νmax(cm-1):1720,1360,1240,824;1H NMR(400MHz,CDCl3)δ9.16–8.94
(m, 6H), 8.87 (d, J=4.7Hz, 2H), 8.42 (d, J=8.2Hz, 2H), 8.31 (d, J=8.2Hz, 2H), 8.10 (d, J=
8.4Hz, 6H), 7.73 (dt, J=18.3,15.2Hz, 6H), 7.27 (d, J=9.5Hz, 6H), 4.50 (t, J=6.6Hz, 2H),
4.31-3.94 (m, 18H), 2.00-1.83 (m, 16H), 1.75-1.60 (m, 10H), 1.45 (dd, J=25.1,21.7Hz,
46H),1.13-0.81(m,32H)。
Claims (1)
1. a synthetic method for benzophenanthrene dodecyloxy bridging isobutyltrimethylmethane. phenyl porphyrin metal Zn coordination compound, its feature
It is to concretely comprise 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) bromododecane epoxide-five hexyloxy benzophenanthrene i.e. synthesis of compound 4:
By 1.0 g of compound 3,2.63 gram 1,12-dibromo-dodecane, 0.43 gram of potassium hydroxide and 0.16 gram of tetrabutyl ammonium bromide,
Join 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 water
Wash twice, washed once with 15 milliliters of saturated aqueous common salts, separate organic layer, after addition anhydrous sodium sulfate is dried except water, through rotation
Turn evaporimeter remove solvent, with 200-300 mesh silica gel column chromatography purify, leacheate be ethyl acetate/petroleum ether volume ratio be 1:
30-1:10, obtaining weak yellow liquid 1.19 grams is compound 4, productivity 90%;bp>300℃,IR(KBr)νmax(cm-1):1260,
836.1H NMR(400MHz,CDCl3) δ: 7.84 (s, 6H), 4.23 (t, J=6.8Hz, 12H), 3.40 (t, J=6.8Hz, 2H),
1.98-1.81 (m, 14H), 1.64-1.50 (m, 12H), 1.47-1.20 (m, 34H), 0.93 (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:
The 1.79 grams of potassium hydroxide aqueous solutions taking 1.4 g of compound 6 and 5 milliliters fully dissolve in 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 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) the benzophenanthrene dodecyloxy bridging isobutyltrimethylmethane. phenyl porphyrin i.e. synthesis of compound 8:
Take 0.25g compound 7,0.217g compound 4,0.037g potassium carbonate and 0.16g tetrabutyl ammonium bromide, join 6mL tri-
In the mixture of chloromethanes and 12mL water, the lower 80 DEG C of back flow reaction of nitrogen atmosphere 36 hours;Extract with chloroform and water
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 purple thick solid 0.19g i.e. compound 8, productivity
47%;mp 83±3℃IR(KBr)νmax(cm-1):1380,1240,803;1H NMR(500MHz,CDCl3) δ 8.92 (d, J=
7.9Hz, 6H), 8.79 (d, J=4.7Hz, 2H), 8.46 (d, J=8.0Hz, 2H), 8.33 (d, J=8.0Hz, 2H), 7.91-
7.76 (m, 6H), 7.39-7.29 (m, 6H), 4.49 (dd, J=44.3,37.7Hz, 4H), 4.31 4.09 (m, 16H), 1.99
(dd, J=49.6,43.7Hz, 16H), 1.81-1.62 (m, 10H), 1.43 (ddd, J=82.0,37.2,35.3Hz, 46H),
1.14–0.69(m,34H),-2.73(s,2H).Elemental analysis calcd for C129H172N4O11(1953):C,
79.23,H,8.88,N,2.89,Found:C,79.26,H,8.87,N,2.87.
(9) synthesis of the i.e. compound 9 of benzophenanthrene dodecyloxy bridging isobutyltrimethylmethane. 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%;Mp 21.4±3
℃,IR(KBr)νmax(cm-1):1720,1360,1240,824;1H NMR(400MHz,CDCl3)δ9.16–8.94(m,6H),
8.87 (d, J=4.7Hz, 2H), 8.42 (d, J=8.2Hz, 2H), 8.31 (d, J=8.2Hz, 2H), 8.10 (d, J=8.4Hz,
6H), 7.73 (dt, J=18.3,15.2Hz, 6H), 7.27 (d, J=9.5Hz, 6H), 4.50 (t, J=6.6Hz, 2H), 4.31-
3.94 (m, 18H), 2.00-1.83 (m, 16H), 1.75-1.60 (m, 10H), 1.45 (dd, J=25.1,21.7Hz, 46H),
1.13-0.81(m,32H);
Described chemical reagent and solvent are analytical pure.
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