CN101255163A - Soluble tetraalkyl phthalocyanine compound and preparation method thereof - Google Patents
Soluble tetraalkyl phthalocyanine compound and preparation method thereof Download PDFInfo
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- CN101255163A CN101255163A CNA2008100504794A CN200810050479A CN101255163A CN 101255163 A CN101255163 A CN 101255163A CN A2008100504794 A CNA2008100504794 A CN A2008100504794A CN 200810050479 A CN200810050479 A CN 200810050479A CN 101255163 A CN101255163 A CN 101255163A
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Abstract
The invention relates to soluble tetra-alkyl phthalocyanine compounds and a method for making the same. The soluble tetra-alkyl phthalocyanine compounds have the following general structure, wherein Rn represents straight-chain or branching chain alkane, n represents the number of straight-chain or branching chain alkane, M represents center ligand of bivalence or more, L represents axial ligand, X represents the number of L. the soluble tetra-alkyl phthalocyanine compounds uses 4-alkyl phthalonitrile as starting material, have good solubility in organic solvent, have processing characterics in solution, and have potential applications in photoelectron material and information technology fields.
Description
Technical field
The invention belongs to photoelectron material and areas of information technology, relate to soluble tetraalkyl phthalocyanine compound and preparation method thereof.
Technical background
Phthalocyanine compound one comes out, and just with the stability and the tint permanence of its unique color, low production cost, excellence, receives common people's concern.Phthalocyanine ring (Pc) can carry out complexing with 70 kinds of elements so far, and four phenyl ring of phthalocyanine ring (Pc) surrounding edge can be replaced by many atoms or group.These characteristics make phthalocyanine compound have abundant chemical structure and physical properties.The Application Areas of phthalocyanine compound has related to electrocatalysis material in sensitive device, electroluminescent device, photovoltaic material, high mobility material, optical disc information recording materials, electrofax material, liquid crystal display material, nonlinear optical material and the fuel cell in the chemical sensor or the like.Especially having application prospect at aspects such as information demonstration, unicircuit, photovoltaic cell and transmitters in recent years, is the hot fields of international academic community and industrial community research and development.United States Patent (USP) 5,969,376 disclose the p-raceway groove OTFT of employing planar metal phthalocyanine (CuPc (CuPc), Phthalocyanine Zinc (ZnPc), phthalocyanine tin (SnPc)) as semiconductor layer; JACS (J.Am.Chem.Soc., 1998,120,207-208) reported employing planar metal phthalocyanine (ten hexafluoro-metal phthalocyanine (F
16MPc), ten hexachloro-FePC (Cl
16FePc), eight cyano group substituted phthalocyanine copper ((CN)
8CuPc)) as the n-raceway groove OTFT of semiconductor layer; 2006 the Applied Physics wall bulletin (Appl.Phys.Lett., 2006,89,163516) reported employing planar metal phthalocyanine (ten hexachloro-CuPc (Cl
16CuPc)) n-raceway groove OTFT; Chinese patent 02129458.5 discloses the p-raceway groove OTFT that adopts nonplanar metal phthalocyanine (TiOPc (TiOPc), ranadylic phthalocyanine (VOPc)); Chinese patent 200710055258.1 discloses the OTFT that adopts axial substituted phthalocyanine compound; Advanced material (Adv.Mater., 2005,17,66-71) reported the organic solar batteries of employing CuPc as donor material, its energy conversion efficiency reaches 5%, but above-mentioned materials all adopts the working method of vacuum evaporation to prepare organic semiconductor layer, processing method is than solution working method complexity, the condition harshness, the cost height, be needs that further satisfy the organic electronic devices development and the advantage of bringing into play organic semiconductor material, the phthalocyanine compound of preparation solution processable is the inevitable requirement of material and technical development.
Summary of the invention
Consider the photoelectric property of phthalocyanine compound excellence, one of purpose of the present invention provides soluble tetraalkyl phthalocyanine compound; Two of purpose of the present invention provides the preparation method of soluble tetraalkyl phthalocyanine compound.
The present invention is under the prerequisite of the photoelectric property that keeps phthalocyanine compound, by on four phenyl ring of phthalocyanine ring (Pc) surrounding edge, introducing the solvability that alkyl substituent improves phthalocyanine compound, the soluble tetraalkyl phthalocyanine compound that is provided has good solubility at methylene dichloride in the organic solvents commonly used such as trichloromethane and tetrahydrofuran (THF).
Soluble tetraalkyl phthalocyanine compound provided by the invention, its expression formula are ML
xPc-4Rn, its general structure is as follows:
In the general structure, Rn represents the alkane of straight chain or branched chain, and n represents the number of the alkane of straight chain or branched chain, and n is the integer of 4-18; The arbitrary position of the position of substitution of Rn in 2 or 3, the arbitrary position in 9 or 10, the arbitrary position in 16 or 17, the arbitrary position in 23 or 24; M represents divalence or the above center part of divalence, and M is magnesium (Mg), aluminium (Al), silicon (Si), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), indium (In) or tin (Sn); L represents axial ligand, and it is chlorine (Cl), fluorine (F) or oxygen (O), and L is connected with center part M; X represents the number of L, and X is the integer of 0-2.
Soluble tetraalkyl phthalocyanine compound provided by the invention is preferably:
2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine magnesium (MgPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine iron (FePc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine cobalts (CoPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine nickel (NiPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine copper (CuPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine zinc (ZnPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine tin (SnPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine aluminium chlorine (AlClPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine silicon dichloro (SiCl
2Pc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine titanium dichloro (TiCl
2Pc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine manganese chlorine (MnClPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine iron chlorine (FeClPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine gallium chlorine (GaClPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine indium chlorine (InClPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine tin dichloro (SnCl
2Pc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine aluminium fluorine (AlFPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine silicon difluoro (SiF
2Pc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine titanium difluoro (TiF
2Pc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine manganese fluorine (MnFPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine iron fluorine (FeFPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine gallium fluorine (GaFPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine indium fluorine (InFPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine tin difluoro (SnF
2Pc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine oxygen titaniums (TiOPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine vanadyl (VOPc-4Rn) or 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine oxygen tin (SnOPc-4Rn).
The preparation method of soluble tetraalkyl phthalocyanine compound provided by the invention is:
I.4-the preparation of iodine phthalic nitrile: according to inferior chemical journal (Denmark) (the Acta.Chemica Scandinavica.1999 of this dimension of bearing, 53, the preparation of 714-720) currently known methods: with the amino phthalic nitrile of commerce product 4-after diazotization reaction, filter, with frozen water washing leaching cake twice, merging filtrate, under the ice bath cooling, in this filtrate, splash into excessive KI solution, stir half an hour, use ethyl acetate extraction, organic layer is through Na
2CO
3, Na
2S
2O
3With saturated aqueous common salt continuous washing, anhydrous magnesium sulfate drying, be that eluent carries out column chromatography for separation with chloroform, obtain 4-iodine phthalic nitrile;
The preparation of II.4-(1-alkyl alkynyl) phthalic nitrile: with 4-iodine phthalic nitrile is matching criterion, with 4-iodine phthalic nitrile, and four (triphenylphosphine closes palladium) (Pd (PPh of the cuprous iodide of 0.4 times of molar weight (CuI) and 0.04 times of molar weight
3)
4) join in the mixed solvent that the dry volume ratio of crossing is 4: 1 triethylamine and tetrahydrofuran (THF), the concentration of 4-iodine phthalic nitrile is the 0.05-0.1 mol, the alkyl alkynes that adds 1-2 times of molar weight at last, stirring at room 12 to 24 hours, stopped reaction, pour in the ether, is 7 with the ammonium chloride solution washing until organic layer pH value, use the saturated common salt water washing, use anhydrous magnesium sulfate drying, the mixed solvent that with volume ratio is 10: 1 petrol ether/ethyl acetate is that eluent carries out column chromatography for separation, obtains 4-(1-alkyl alkynyl) phthalic nitrile;
Described alkyl alkynes is that carbon atom number is the straight chain of 4-18 or the alkyl alkynes of branched chain;
The preparation of III.4-alkyl phthalic nitrile: with 4-(1-alkyl alkynyl) phthalic nitrile is matching criterion, 10% palladium carbon (Pd/C) with 4-(1-alkyl alkynyl) phthalic nitrile and 0.07 times of molar weight, join in the dehydrated alcohol, the concentration of 4-(1-alkyl alkynyl) phthalic nitrile is the 0.05-0.1 mol, under the hydrogen atmosphere of 1-2 standard atmospheric pressure stirring reaction 12-36 hour, remove by filter catalyzer, solvent evaporated, with volume ratio is that chloroform/sherwood oil of 1: 1 is that eluent carries out column chromatography for separation, obtains 4-alkyl phthalic nitrile.Its transformation efficiency is near 100%;
Described alkyl alkynyl is that carbon atom number is the straight chain of 4-18 or the alkyl alkynyl of branched chain, and alkyl is that carbon atom number is the straight chain of 4-18 or the alkyl of branched chain;
IV. the preparation of soluble tetraalkyl phthalocyanine compound: (1) meets that M is Mg in the above-mentioned general structure, Fe, Co, Ni, Cu, Zn or Sn do not contain the preparation of the soluble tetraalkyl phthalocyanine compound of axial ligand L: according to the method that " the synthetic and application of phthalocyanine " (Shen Yongjia chief editor Chemical Industry Press 2000) provides, be matching criterion with 4-alkyl phthalic nitrile, with 4-alkyl phthalic nitrile, 0.4 doubly the corresponding metal source of molar weight joins in the n-hexyl alcohol, the concentration of 4-alkyl phthalic nitrile is 0.5 mol, the organic bases 1 that adds 1-1.25 times of molar weight under the condition of protection of inert gas, 8-diazacyclo ring (5,4,0) 7-hendecene (DBU), reaction reflux 13-24 hour, be chilled to room temperature,, filter product sedimentation in methyl alcohol, use earlier chloroform, be that eluent carries out column chromatography for separation with ethyl acetate again, obtain meeting that M is Mg in the general structure, Fe, Co, Ni, Cu, Zn or Sn; The soluble tetraalkyl phthalocyanine compound that does not contain axial ligand L;
Described alkyl is that carbon atom number is the straight chain of 4-18 or the alkyl of branched chain;
(2) method that provides according to " phthalocyanine synthetic with use " (Shen Yongjia chief editor Chemical Industry Press 2000) is a starting raw material with 4-alkyl phthalic nitrile, can prepare to meet that M is Al in the general structure Si, Ti, Mn, Fe, Ga, In or Sn; L is Cl, and X is the soluble tetraalkyl phthalocyanine compound of the integer of 1-2;
Described alkyl is that carbon atom number is the straight chain of 4-18 or the alkyl of branched chain;
(3) M is Al in the general structure with meeting of obtaining in the step (2), Si, Ti, Mn, Fe, Ga, In or Sn; L is Cl, X is the soluble tetraalkyl phthalocyanine compound of the integer of 1-2, refluxing in the mixture of ethanol and ammoniacal liquor and can generating corresponding axially substituting group is dihydric soluble tetraalkyl phthalocyanine compound, can obtain meeting general structure M with hydrogen fluoride trealment again is Al, Si, Ti, Mn, Fe, Ga, In or Sn; L is Cl, and X is the soluble tetraalkyl phthalocyanine compound of the integer of 1-2;
Described alkyl is that carbon atom number is the straight chain of 4-18 or the alkyl of branched chain;
(4) be matching criterion with 4-alkyl phthalic nitrile, with 4-alkyl phthalic nitrile, 0.5 doubly the corresponding vanadium trichloride of molar weight or four titanium butoxide or tin trichloride join in 2-(dimethyl amido) ethanol (DMAE), the concentration of 4-alkyl phthalic nitrile is the 0.5-1 mol, fully after the ventilation, reaction reflux 12-24 hour, cooling, adding volume is DMAE5 water doubly, refluxed 6 hours, product is poured in the water, after the filtration, the water thorough washing, product is dissolved in chloroform, anhydrous magnesium sulfate drying, solvent evaporated is that eluent carries out column chromatography for separation with the mixed solvent of chloroform/sherwood oil, met accordingly that M is Ti in the general structure, V or Sn, L are O, and X is 1 soluble tetraalkyl phthalocyanine compound;
Described alkyl is that carbon atom number is the straight chain of 4-18 or the alkyl of branched chain.
Single stage method synthesizing soluble tetraalkyl phthalocyanine compound, step and condition are: with 4-(1-alkyl alkynyl) phthalic nitrile is matching criterion, 10% palladium carbon (Pd/C) of 4-(1-alkyl alkynyl) phthalic nitrile and 0.07 times of molar weight is joined in anhydrous organic alcohol, the concentration of 4-(1-alkyl alkynyl) phthalic nitrile is the 0.05-0.1 mol, under the hydrogen atmosphere of 1-2 standard atmospheric pressure stirring reaction 12-36 hour, remove by filter the Pd/C catalyzer, filtrate is transferred in another reactor, add the corresponding metal source of 0.3-0.4 times of molar weight and the DBU of 0-1.25 times of molar weight, the reaction reflux is 13-24 hour under the condition of protection of inert gas, be chilled to room temperature, with product sedimentation in methyl alcohol, filtration obtains crude product, carry out column chromatography for separation again, obtain meeting the soluble tetraalkyl phthalocyanine compound of general structure, wherein not comprising L is the tetraalkyl soluble phthalocyanine compound of F;
Described organic alcohol is ethanol, butanols, Pentyl alcohol or 2-(dimethyl amido) ethanol (DMAE);
Described alkyl alkynyl is that carbon atom number is the straight chain of 4-18 or the alkyl alkynyl of branched chain.
Beneficial effect of the present invention: solubility four substituted phthalocyanine compounds provided by the invention are simple in structure, and synthetic method is applied widely, and the reaction conditions gentleness is easy to purify and a large amount of preparation.Such solubility four substituted phthalocyanine compounds have good solubility in organic solvent, make solubility four substituted phthalocyanine compounds have the characteristic of solution processable, have application at photoelectron material and areas of information technology.
Embodiment
Embodiment 1:4-(ethyl acetylene base) phthalic nitrile
To a volume be add in 150 milliliters the peace bottle 4-iodine phthalic nitrile (2.1g, 8.0mmol), CuI (0.61g, 3.2mmol) and Pd (PPh
3)
4(0.23g 0.32mmol) uses high pure nitrogen substitution gas three times, to wherein adding the dry 80 milliliters of triethylamines crossing and the mixed solvent of 20 milliliters of tetrahydrofuran (THF)s.Under cryosel is bathed with ethyl acetylene freezing be liquid, extract ethyl acetylene (0.86g with syringe, 16mmol) join in the above-mentioned peace bottle, tube sealing, stirring at room 24 hours, stopped reaction, pour in 400 milliliters of ether, is 7 with the extraction of capacity ammonium chloride solution until organic layer pH value, the saturated common salt water washing, anhydrous magnesium sulfate drying is that the mixed solvent of 10: 1 petrol ether/ethyl acetate is that eluent carries out column chromatography for separation with volume ratio, obtain 4-(ethyl acetylene base) phthalic nitrile 1.2g, productive rate 85%.The nuclear-magnetism characterization data:
1H NMR (300MHz, CDCl
3) δ (ppm) 7.74 (d, 1H), 7.71 (d, 1H), 7.68 (dd, 1H), 2.40 (t, 2H), 0.87 (t, 3H).
Embodiment 2:4-(1-octyne base) phthalic nitrile
4-iodine phthalic nitrile (2.1g, 8.0mmol), CuI (0.61g, 3.2mmol) and Pd (PPh
3)
4(0.23g 0.32mmol) adds in 150 milliliters of reaction flasks, uses high pure nitrogen substitution gas three times, adds the dry 80 milliliters of triethylamines crossing and the mixed solvent of 20 milliliters of tetrahydrofuran (THF)s in this reaction flask.Add positive octyne (1.5g at last, 10mmol), room temperature reaction 17 hours, stopped reaction was poured in 500 milliliters of ether, is 7 with the extraction of capacity ammonium chloride solution until organic layer pH value, the saturated common salt water washing, anhydrous magnesium sulfate drying is that the mixed solvent of 10: 1 petrol ether/ethyl acetate is that eluent carries out column chromatography for separation with volume ratio, obtain 4-(1-octyne base) phthalic nitrile 1.8g, productive rate 97%.The nuclear-magnetism characterization data:
1H NMR (300MHz, CDCl
3) δ (ppm) 7.75 (d, 1H), 7.70 (d, 1H), 7.66 (dd, 1H), 2.44 (t, 2H), 1.60 (m, 2H), 1.42 (m, 2H), 1.31 (m, 4H), 0.90 (t, 3H).
Embodiment 3:4-(1-dodecyne base) phthalic nitrile
With the positive octyne among the positive dodecyne hydrocarbon replacement embodiment 2, feed ratio, reaction conditions and treatment process obtain 4-(1-dodecyne base) phthalic nitrile, productive rate 95% with embodiment 2.The nuclear-magnetism characterization data:
1H NMR (300MHz, CDCl
3) δ (ppm) 7.75 (d, 1H), 7.69 (d, 1H), 7.64 (dd, 1H), 2.40 (t, 2H), 1.62 (m, 2H), 1.42 (m, 2H), 1.30 (m, 8H), 0.90 (t, 3H).
Embodiment 4:4-octyl group phthalic nitrile
4-(1-octyne base) phthalic nitrile (1.9g, 8.1mmol) and 10% Pd/C (0.43g 0.5mmol) joins in 100 milliliters of dehydrated alcohols, with high pure nitrogen substitution gas three times, under the hydrogen atmosphere of 2 standard atmospheric pressures, stirring at room reaction 21 hours, stopped reaction leaches catalyzer, be spin-dried for solvent, the mixed solvent that with volume ratio is sherwood oil/chloroform of 1: 1 is that eluent carries out column chromatography for separation, obtains 1.67g 4-octyl group phthalic nitrile, productive rate 87%.The nuclear-magnetism characterization data:
1H NMR (300MHz, CDCl
3) δ (ppm) 7.70 (d, 1H), 7.60 (d, 1H), 7.52 (dd, 1H), 2.70 (t, 2H), 1.62 (t, 2H), 1.28 (m, 10H), 0.87 (t, 3H).
Embodiment 5:2 (3), 9 (10), 16 (17), 23 (24)-four octyl group Phthalocyanine Zinc (ZnPc-4C8)
With 4-octyl group phthalic nitrile (0.58g, 2.4mmol), (0.16g 0.9mmol) adds reaction flasks with 4.8 milliliters of n-hexyl alcohols to zinc acetate, uses high pure nitrogen substitution gas three times, add DBU (0.44g again, 2.9mmol), reflux is 13 hours under the nitrogen atmosphere, is chilled to room temperature, with product sedimentation in 50 ml methanol, filter.Earlier using chloroform, is that eluent carries out column chromatography for separation with ethyl acetate again, obtains 2 (3), 9 (10), 16 (17), 23 (24)-four octyl group Phthalocyanine Zinc 380mg, and productive rate is 62%.The nuclear-magnetism characterization data:
1H NMR (300MHz, CDCl
3) δ (ppm) 7.57-7.91 (m, 8H), 6.89-7.19 (m, 4H), 2.73 (t, 8H), 1.74 (m, 8H), 1.39 (m, 24H), 0.87 (t, 12H).
Embodiment 6:2 (3), 9 (10), 16 (17), 23 (24)-four octyl group phthalocyanine tin (SnPc-4C8)
With the zinc acetate among the tin protochloride replacement embodiment 5; feed ratio, reaction conditions and treatment process obtain 2 (3) with embodiment 5; 9 (10); 16 (17), 23 (24)-four octyl group phthalocyanine tin dichloros, the adding mol ratio is 1: 3.7 a anhydrous stannous chloride and 2 (3) in quinoline; 9 (10); 16 (17), 23 (24)-four octyl group phthalocyanine tin dichloros reflux under protection of nitrogen gas; can make 2 (3); 9 (10), 16 (17), 23 (24)-four octyl group phthalocyanine tin dichloros revert to 2 (3); 9 (10); 16 (17), 23 (24)-four octyl group phthalocyanine tin, productive rate 80%.The nuclear-magnetism characterization data:
1H NMR (300MHz, CDCl
3) δ (ppm) 7.50-7.86 (m, 8H), 6.80-7.12 (m, 4H), 2.78 (t, 8H), 1.79 (m, 8H), 1.42 (m, 24H), 0.90 (t, 12H).
Embodiment 7:2 (3), 9 (10), 16 (17), 23 (24)-four octyl group phthalocyanine titanium dichloro (TiCl
2Pc-4C8)
With the zinc acetate among the titanous chloride replacement embodiment 5, feed ratio, reaction conditions and treatment process obtain 2 (3), 9 (10), 16 (17), 23 (24)-four octyl group phthalocyanine titanium dichloros, productive rate 40% with embodiment 5.The nuclear-magnetism characterization data:
1H NMR (300MHz, CDCl
3) δ (ppm) 7.48-7.88 (m, 8H), 6.82-7.10 (m, 4H), 2.80 (t, 8H), 1.82 (m, 8H), 1.46 (m, 24H), 0.93 (t, 12H).
Embodiment 8:2 (3), 9 (10), 16 (17), 23 (24)-four octyl group phthalocyanine titanium difluoro (TiF
2Pc-4C8)
0.12g 2 (3), 9 (10), 16 (17), 23 (24)-four octyl group phthalocyanine titanium dichloros refluxed 2 days in the mixed solvent of 6 milliliters of ethanol and 6 milliliters of ammoniacal liquor at 24 ml waters, were cooled to room temperature, filtration obtains filter cake, water and washing with alcohol, 120 ℃ of dryings of vacuum obtain 2 (3), 9 (10), 16 (17), 23 (24)-four octyl group phthalocyanine titanium dihydroxyl, productive rate 95%.In plastic containers, with hydrogen fluoride trealment 2 (3), 9 (10), 16 (17), 23 (24)-four octyl group phthalocyanine titanium dihydroxyl were used pyridine after 30 minutes, and the washing with alcohol solid matter obtains 2 (3), 9 (10), 16 (17), 23 (24)-four octyl group phthalocyanine titanium difluoros, productive rate 88%.The nuclear-magnetism characterization data:
1H NMR (300MHz, CDCl
3) δ (ppm) 7.60-7.94 (m, 8H), 6.90-7.23 (m, 4H), 2.73 (t, 8H), 1.75 (m, 8H), 1.40 (m, 24H), 0.87 (t, 12H).
Embodiment 9:2 (3), 9 (10), 16 (17), 23 (24)-four octyl group ranadylic phthalocyanines (VOPc-4C8)
With 4-octyl group phthalic nitrile (0.58g, 2.4mmol), (0.19g 1.2mmol) adds reaction flasks with 4.0 milliliters of DMAE to vanadium trichloride, with high pure nitrogen substitution gas three times, reflux 18 hours, cooling adds 20 ml waters, refluxed six hours, product is poured in 200 ml waters, filters back water thorough washing filter cake, filter cake is dissolved in chloroform, anhydrous magnesium sulfate drying, be spin-dried for solvent, the mixed solvent that with volume ratio is sherwood oil/chloroform of 1: 2 is that eluent carries out column chromatography for separation, gets 2 (3), 9 (10), 16 (17), 23 (24)-four octyl group ranadylic phthalocyanine 264mg, productive rate 42%.The nuclear-magnetism characterization data:
1H NMR (300MHz, CDCl
3) δ (ppm) 9.03-9.05 (m, 2H), 8.90-8.95 (m, 4H), 8.77-8.82 (m, 2H), 7.70-7.99 (m, 4H), 3.30 (m, 8H), 2.04 (m, 8H), 1.70-1.54 (m, 24H), 0.92 (t, 12H).
Embodiment 10:2 (3), 9 (10), 16 (17), 23 (24)-four octyl group TiOPcs (TiOPc-4C8)
With the vanadium trichloride among the four titanium butoxide replacement embodiment 9, feed ratio, reaction conditions and treatment process obtain 2 (3), 9 (10), 16 (17), 23 (24)-four octyl group TiOPcs, productive rate 35% with embodiment 9.The nuclear-magnetism characterization data:
1H NMR (300MHz, CDCl
3) δ (ppm) 9.01-9.07 (m, 2H), 8.88-8.97 (m, 4H), 8.75-8.80 (m, 2H), 7.72-8.01 (m, 4H), 3.29 (m, 8H), 2.01 (m, 8H), 1.68-1.50 (m, 24H), 0.94 (t, 12H).
Embodiment 11:2 (3), 9 (10), 16 (17), 23 (24)-four octyl group Phthalocyanine Zinc (ZnPc-4C8)
4-(1-octyne base) phthalic nitrile (1.9g, 8.1mmol) and 10% Pd/C (0.43g, 0.5mmol) join in 100 milliliters of anhydrous n-hexyl alcohols, with high pure nitrogen substitution gas three times, under the hydrogen atmosphere of 2 standard atmospheric pressures, stirring at room reaction 21 hours, stopped reaction leaches catalyzer, filtrate is transferred in another reaction flask, add zinc acetate (0.16g, 0.9mmol) and DBU (0.44g, 2.9mmol), reflux is 13 hours under the nitrogen atmosphere, be chilled to room temperature,, filter product sedimentation in 80 ml methanol.Earlier using chloroform, is that eluent carries out column chromatography for separation with ethyl acetate again, obtains 2 (3), 9 (10), 16 (17), 23 (24)-four octyl group Phthalocyanine Zinc 340mg, and productive rate is 55%.Nuclear-magnetism characterizes with embodiment 5.
Embodiment 12:2 (3), 9 (10), 16 (17), 23 (24)-four octyl group ranadylic phthalocyanines (VOPc-4C8)
4-(1-octyne base) phthalic nitrile (1.9g, 8.1mmol) and 10% Pd/C (0.43g, 0.5mmol) join among 40 milliliters of anhydrous DMAC, with high pure nitrogen substitution gas three times, under the hydrogen atmosphere of 2 standard atmospheric pressures, stirring at room reaction 21 hours, stopped reaction, leach catalyzer, filtrate is transferred in another reaction flask, and the adding vanadium trichloride (0.19g, 1.2mmol), other reaction conditions is with embodiment 9, obtain 2 (3), 9 (10), 16 (17), 23 (24)-four octyl group ranadylic phthalocyanines (VOPc-4C8), productive rate 35%.Nuclear-magnetism characterizes with embodiment 9.
Claims (4)
1, soluble tetraalkyl phthalocyanine compound is characterized in that, the expression formula of this soluble tetraalkyl phthalocyanine compound is ML
xPc-4Rn, its general structure is as follows:
In the general structure, Rn represents the alkane of straight chain or branched chain, and n represents the number of the alkane of straight chain or branched chain, and n is the integer of 4-18; The arbitrary position of the position of substitution of Rn in 2 or 3, the arbitrary position in 9 or 10, the arbitrary position in 16 or 17, the arbitrary position in 23 or 24; M represents divalence or the above center part of divalence, and M is magnesium (Mg), aluminium (Al), silicon (Si), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), indium (In) or tin (Sn); L represents axial ligand, and it is chlorine (Cl), fluorine (F) or oxygen (O), and L is connected with center part M; X represents the number of L, and X is the integer of 0-2.
2, soluble tetraalkyl phthalocyanine compound as claimed in claim 1 is characterized in that, this soluble tetraalkyl phthalocyanine compound is:
2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine magnesium (MgPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine iron (FePc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine cobalts (CoPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine nickel (NiPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine copper (CuPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine zinc (ZnPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine tin (SnPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine aluminium chlorine (AlClPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine silicon dichloro (SiCl
2Pc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine titanium dichloro (TiCl
2Pc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine manganese chlorine (MnClPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine iron chlorine (FeClPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine gallium chlorine (GaClPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine indium chlorine (InClPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine tin dichloro (SnCl
2Pc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine aluminium fluorine (AlFPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine silicon difluoro (SiF
2Pc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine titanium difluoro (TiF
2Pc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine manganese fluorine (MnFPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine iron fluorine (FeFPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine gallium fluorine (GaFPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine indium fluorine (InFPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine tin difluoro (SnF
2Pc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine oxygen titaniums (TiOPc-4Rn), 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine vanadyl (VOPc-4Rn) or 2 (3), 9 (10), 16 (17), 23 (24)-tetraalkyl phthalocyanine oxygen tin (SnOPc-4Rn).
3, the preparation method of soluble tetraalkyl phthalocyanine compound as claimed in claim 1 is characterized in that, step and condition are as follows:
I.4-the preparation of iodine phthalic nitrile: according to inferior chemical journal (Denmark) (the Acta.Chemica Scandinavica.1999 of this dimension of bearing, 53, the preparation of 714-720) currently known methods: with the amino phthalic nitrile of commerce product 4-after diazotization reaction, filter, with frozen water washing leaching cake twice, merging filtrate, under the ice bath cooling, in this filtrate, splash into excessive KI solution, stir half an hour, use ethyl acetate extraction, organic layer is through Na
2CO
3, Na
2S
2O
3With saturated aqueous common salt continuous washing, anhydrous magnesium sulfate drying, be that eluent carries out column chromatography for separation with chloroform, obtain 4-iodine phthalic nitrile;
The preparation of II.4-(1-alkyl alkynyl) phthalic nitrile: with 4-iodine phthalic nitrile is matching criterion, with 4-iodine phthalic nitrile, and four (triphenylphosphine closes palladium) (Pd (PPh of the cuprous iodide of 0.4 times of molar weight (CuI) and 0.04 times of molar weight
3)
4) join in the mixed solvent that the dry volume ratio of crossing is 4: 1 triethylamine and tetrahydrofuran (THF), the concentration of 4-iodine phthalic nitrile is the 0.05-0.1 mol, the alkyl alkynes that adds 1-2 times of molar weight at last, stirring at room 12 to 24 hours, stopped reaction, pour in the ether, is 7 with the ammonium chloride solution washing until organic layer pH value, use the saturated common salt water washing, use anhydrous magnesium sulfate drying, the mixed solvent that with volume ratio is 10: 1 petrol ether/ethyl acetate is that eluent carries out column chromatography for separation, obtains 4-(1-alkyl alkynyl) phthalic nitrile;
Described alkyl alkynes is that carbon atom number is the straight chain of 4-18 or the alkyl alkynes of branched chain;
The preparation of III.4-alkyl phthalic nitrile: with 4-(1-alkyl alkynyl) phthalic nitrile is matching criterion, 10% palladium carbon (Pd/C) with 4-(1-alkyl alkynyl) phthalic nitrile and 0.07 times of molar weight, join in the dehydrated alcohol, the concentration of 4-(1-alkyl alkynyl) phthalic nitrile is the 0.05-0.1 mol, under the hydrogen atmosphere of 1-2 standard atmospheric pressure stirring reaction 12-36 hour, remove by filter catalyzer, solvent evaporated, with volume ratio is that chloroform/sherwood oil of 1: 1 is that eluent carries out column chromatography for separation, obtains 4-alkyl phthalic nitrile;
Described alkyl alkynyl is that carbon atom number is the straight chain of 4-18 or the alkyl alkynyl of branched chain, and alkyl is that carbon atom number is the straight chain of 4-18 or the alkyl of branched chain;
IV. the preparation of soluble tetraalkyl phthalocyanine compound: (1) meets that M is Mg in the above-mentioned general structure, Fe, Co, Ni, Cu, Zn or Sn do not contain the preparation of the soluble tetraalkyl phthalocyanine compound of axial ligand L: according to the method that " the synthetic and application of phthalocyanine " (Shen Yongjia chief editor Chemical Industry Press 2000) provides, be matching criterion with 4-alkyl phthalic nitrile, with 4-alkyl phthalic nitrile, 0.4 doubly the corresponding metal source of molar weight joins in the n-hexyl alcohol, the concentration of 4-alkyl phthalic nitrile is 0.5 mol, the organic bases 1 that adds 1-1.25 times of molar weight under the condition of protection of inert gas, 8-diazacyclo ring (5,4,0) 7-hendecene (DBU), reaction reflux 13-24 hour, be chilled to room temperature,, filter product sedimentation in methyl alcohol, use earlier chloroform, be that eluent carries out column chromatography for separation with ethyl acetate again, obtain meeting that M is Mg in the general structure, Fe, Co, Ni, Cu, Zn or Sn; The soluble tetraalkyl phthalocyanine compound that does not contain axial ligand L;
Described alkyl is that carbon atom number is the straight chain of 4-18 or the alkyl of branched chain;
(2) method that provides according to " phthalocyanine synthetic with use " (Shen Yongjia chief editor Chemical Industry Press 2000) is a starting raw material with 4-alkyl phthalic nitrile, can prepare to meet that M is Al in the general structure Si, Ti, Mn, Fe, Ga, In or Sn; L is Cl, and X is the soluble tetraalkyl phthalocyanine compound of the integer of 1-2;
Described alkyl is that carbon atom number is the straight chain of 4-18 or the alkyl of branched chain;
(3) M is Al in the general structure with meeting of obtaining in the step (2), Si, Ti, Mn, Fe, Ga, In or Sn; L is Cl, X is the soluble tetraalkyl phthalocyanine compound of the integer of 1-2, refluxing in the mixture of ethanol and ammoniacal liquor and can generating corresponding axially substituting group is dihydric soluble tetraalkyl phthalocyanine compound, can obtain meeting general structure M with hydrogen fluoride trealment again is Al, Si, Ti, Mn, Fe, Ga, In or Sn; L is Cl, and X is the soluble tetraalkyl phthalocyanine compound of the integer of 1-2;
Described alkyl is that carbon atom number is the straight chain of 4-18 or the alkyl of branched chain;
(4) be matching criterion with 4-alkyl phthalic nitrile, with 4-alkyl phthalic nitrile, 0.5 doubly the corresponding vanadium trichloride of molar weight or four titanium butoxide or tin trichloride join in 2-(dimethyl amido) ethanol (DMAE), the concentration of 4-alkyl phthalic nitrile is the 0.5-1 mol, fully after the ventilation, reaction reflux 12-24 hour, cooling, adding volume is DMAE5 water doubly, refluxed 6 hours, product is poured in the water, after the filtration, the water thorough washing, product is dissolved in chloroform, anhydrous magnesium sulfate drying, solvent evaporated is that eluent carries out column chromatography for separation with the mixed solvent of chloroform/sherwood oil, met accordingly that M is Ti in the general structure, V or Sn, L are O, and X is 1 soluble tetraalkyl phthalocyanine compound;
Described alkyl is that carbon atom number is the straight chain of 4-18 or the alkyl of branched chain.
4, the preparation method of soluble tetraalkyl phthalocyanine compound as claimed in claim 1 is characterized in that, step and condition are as follows:
With 4-(1-alkyl alkynyl) phthalic nitrile is matching criterion, 10% palladium carbon (Pd/C) of 4-(1-alkyl alkynyl) phthalic nitrile and 0.07 times of molar weight is joined in anhydrous organic alcohol, the concentration of 4-(1-alkyl alkynyl) phthalic nitrile is the 0.05-0.1 mol, under the hydrogen atmosphere of 1-2 standard atmospheric pressure stirring reaction 12-36 hour, remove by filter the Pd/C catalyzer, filtrate is transferred in another reactor, add the corresponding metal source of 0.3-0.4 times of molar weight and the DBU of 0-1.25 times of molar weight, the reaction reflux is 13-24 hour under the condition of protection of inert gas, be chilled to room temperature, with product sedimentation in methyl alcohol, filtration obtains crude product, carry out column chromatography for separation again, obtain meeting the soluble tetraalkyl phthalocyanine compound of general structure, wherein not comprising L is the tetraalkyl soluble phthalocyanine compound of F;
Described organic alcohol is ethanol, butanols, Pentyl alcohol or 2-(dimethyl amido) ethanol (DMAE);
Described alkyl alkynyl is that carbon atom number is the straight chain of 4-18 or the alkyl alkynyl of branched chain.
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