CN103319492A - Method for preparing metallic perfluorophthalocyanine derivative - Google Patents
Method for preparing metallic perfluorophthalocyanine derivative Download PDFInfo
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- CN103319492A CN103319492A CN2013102915049A CN201310291504A CN103319492A CN 103319492 A CN103319492 A CN 103319492A CN 2013102915049 A CN2013102915049 A CN 2013102915049A CN 201310291504 A CN201310291504 A CN 201310291504A CN 103319492 A CN103319492 A CN 103319492A
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- phthalocyanine
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Abstract
The invention discloses a method for preparing a metallic perfluorophthalocyanine derivative. The structure of the above compound is represented by formula I. The preparation method of the compound comprises a step that the compound of the formula I is obtained through reacting tetrafluorophthalonitrile with a metal chloride (titanium tetrachloride or vanadium trichloride) in the inert atmosphere. The above synthetic route provided in the invention has the advantages of simplicity, high efficiency, small environmental pollution, cheap raw materials, low synthesis cost, very good universality, very good repeatability and the like, and can be popularized to the synthesis of perfluorophthalocyanine derivatives having different central metals.
Description
Technical field
The present invention relates to a kind of method for preparing containing metal perfluor phthalocyanine derivates.
Background technology
1907, Braun and Tchemiac two people found this compound of phthalocyanine accidentally, and numerous phthalocyanines derivates are synthesized out subsequently, and are widely used in pigment and dyestuffs industries.In recent years, continuous development along with material and life science, phthalocyanine compound is endowed how new application, for example: chemical sensor, electroluminescent device, solar cell, information-recording material, sense electronics luminescent material, liquid crystal display material, nonlinear optical material and photodynamics medicine etc.Wherein, phthalocyanine also is applied to the organic field effect tube field as the good organic semiconductor material of a class.Because the phthalocyanine kind is numerous, thin film-forming method can be regulated and control according to the peripheral modification group of its different aromatic nucleus, thereby aspect the screening field effect transistor material very big selection space is being arranged, and can be used as p-type material or modification becomes n section bar material, and this is that the other types material hardly matches.Most of phthalocyanine compounds all are the p-type materials, and n section bar material is less relatively, and subject matter is that they are very responsive to oxygen and humidity, and is extremely unstable in environment.Therefore but high performance n section bar material can prepare p-n junction and complementary logic circuit, and synthetic and research high-performance and the good n section bar material of environmental stability have important use to be worth.Bao Zhenan etc. introduce strong electron-withdrawing group group as F by the modification to the phthalocyanine ring, and groups such as CN reduce the lumo energy of phthalocyanine molecule, make it more to be conducive to electronics and inject, thereby make phthalocyanine become n section bar material from the p-type material.This n section bar material ten hexafluoro substituted phthalocyanine copper (F to air-stable
16CuPc) mobility is up to 0.03cm
2/ Vs.Civilian equal utilization numerator self-assembly technique has prepared ten hexafluoro substituted phthalocyanine copper single crystal nanotubes recklessly, and with the gold and silvery be equipped with asymmetric source/drain electrode (Au/Ag), the mobility that records the monocrystalline micro-nano device with this field-effect transistor with novel structure is 0.2cm
2/ Vs.By The above results as can be known, introducing effective injection that fluoro substituents is conducive to electronics in molecule, is an effective way that organic semiconductor material is transformed into the n type from p-type.So, synthetic and study fluorine-containing phthalocyanine compound and have very important significance.
But up to now, the perfluor phthalocyanine derivates kind that can buy seldom, and purity is not high (generally all to be lower than 90% purity, be difficult to satisfy semiconductor grade purity), major cause is: (a) method of synthetic perfluor phthalocyanine derivates is very limited, and productive rate is low; (b) major product accompanies difficult separating impurity (impurities mainly is the by product that the fluorine atom of perfluor phthalocyanine is replaced by other negatively charged ion), and purifying is very difficult.Therefore, it is very necessary developing a kind of new synthetic method, make the perfluor phthalocyanine derivates productive rate height that obtains, purity is high and it is easy to separate, thereby solve the difficult problem in high purity perfluor phthalocyanine organic semiconductor material source, have very high using value and commercial promise.
Summary of the invention
Technical problem to be solved by this invention is to overcome the weak point that containing metal perfluor phthalocyanine derivates preparation method in the prior art exists, and develops that a kind of technology is easy, favorable reproducibility and the higher method for preparing containing metal perfluor phthalocyanine derivates of productive rate efficient.
The method of the phthalocyanine derivates of containing metal perfluor shown in the preparation formula I provided by the invention comprises the steps: in inert atmosphere, and tetrafluoro phthalic nitrile and metal chloride mixing are carried out condensation reaction, and reaction finishes and obtains compound shown in the formula I;
Among the formula I, described M is Ti or V;
Described metal chloride is titanium tetrachloride or vanadium trichloride.
The synthetic route of aforesaid method as shown in Figure 1.
In this method, the molar ratio of described tetrafluoro phthalic nitrile, metal chloride is followed successively by 4-10:1, is specially 4:1.
In the described step of condensation, temperature is 120-180 ℃, is specially 140-160 ℃, more specifically is 150 ℃;
Time is 24-72 hour, is specially 36-48 hour.
Described condensation reaction is carried out in organic solvent.
Described organic solvent is selected from least a in naphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 1-nitro-naphthalene, 1-naphthol methyl ether, 2-fluoronaphthalene, 2-chloronaphthalene, 2-nitro-naphthalene and the 2-naphthol methyl ether.The consumption of organic solvent is as the criterion with complete solubilizing reaction thing.Solvent is homemade chemical pure rank, need not the strictness drying that dewaters before the reaction.
Described inert atmosphere is nitrogen atmosphere or argon gas atmosphere.
Described method also comprises the steps: after described condensation reaction finishes, reaction mixture is poured in the deionized water, fully stir after-filtration, get filter cake with after the anhydrous methanol washing, at 100 ℃ down after the oven dry, filter cake is dissolved in the vitriol oil, after being stirred well to whole dissolvings, place ice-water bath blue solid precipitation, cross the leaching filter cake with deionized water wash after again with anhydrous methanol washing, oven dry.
The present invention relates to raw material tetrafluoro phthalic nitrile and under the metal chloride effect, condensation reaction takes place, the efficient big π system of copline fragrance that makes up of a step, productive rate is up to 90%.Reaction among the present invention is all not harsh, easy and simple to handle to raw material, reagent and condition, and separation and purifying are easy.
The invention has the advantages that:
1, this serial reaction route has the advantage that simple efficient, environmental friendliness, cost of material cheapness, reagent dosage reduce; Less demanding to raw materials used, reagent and solvent, chemical pure gets final product; Operation need not strict anhydrous and oxygen-free method; The universality height, good reproducibility, productive rate height.
2, provide a kind of basic raw material that is easy to get for organic semiconductor field-effect material.
Description of drawings
Fig. 1 prepares the optimum synthetic route chart of containing metal perfluor phthalocyanine derivates method for the present invention.
Fig. 2 is the perfluor TiOPc (F of embodiment 1 preparation
16TiOPc) fluorine nmr spectrogram.
Fig. 3 is the perfluor ranadylic phthalocyanine (F of embodiment 6 preparations
16VOPc) fluorine nmr spectrogram.
Fig. 4 is the tetrahydrofuran solution UV, visible light optical absorption spectra of perfluor TiOPc and perfluor ranadylic phthalocyanine.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can get from open commercial sources if no special instructions.
In two mouthfuls of round-bottomed flasks of 50mL, vacuumize logical nitrogen.Add then the tetrafluoro phthalic nitrile (2.00g, 10.0mmol).At room temperature inject 1-chloronaphthalene (20mL), (0.47g, 2.5mmol), condensation reaction 36h is carried out in 150 ℃ of stirrings to add titanium tetrachloride again.Stop heating, naturally cooling is poured reaction mixture in the 200mL deionized water into, fully stirs.Filter above-mentioned mixing solutions with B, filter cake with the washing of 50mL anhydrous methanol is once dried down at 100 ℃.At last, filter cake is dissolved in the 50mL vitriol oil, is stirred well to whole dissolvings, and the above-mentioned concentrated sulfuric acid solution that contains the perfluor TiOPc slowly pours in the 200mL ice-water bath then, gets the blue solid precipitation.Filter with B, filter cake with the 200mL deionized water wash once washs once with the 50mL anhydrous methanol, 100 ℃ of oven dry down.Obtain blue-greenish colour solid 1.94g (productive rate: 90%) at last.
The structural confirmation data of this product are as follows:
Mass spectrum: MS (MALDI-TOF): 863.9 (M
+) .HRMS (MALDI): calcd.for C
32F
16N
8O
46Ti (M+): 861.9460; Found:861.9462.
Nucleus magnetic hydrogen spectrum (as shown in Figure 2):
19F NMR (282MHz, D
2SO
4) δ (ppm): δ=-129.9 (d, J=37Hz) ,-135.3 (d, J=37Hz).
Uv-vis spectra such as Fig. 4 are Soret band absorption peaks of metal phthalocyanine about 400 nanometers, are Q band absorption peaks of metal phthalocyanine about 700 nanometers.
As from the foregoing, this product structure is correct, is perfluor TiOPc (F
16TiOPc), its structural formula is as follows:
Embodiment 2, preparation perfluor TiOPc (F
16TiOPc)
Substantially with embodiment 1, difference is the preparation method: condensation reaction 36h is carried out in 150 ℃ of stirrings among the embodiment 1 replace with 120 ℃ of stirrings and carry out condensation reaction 72h, obtain blue-greenish colour solid 0.60g (productive rate: 28%).
The structural confirmation data of this product and embodiment 1 no substantive difference repeat no more.
Embodiment 3, preparation perfluor TiOPc (F
16TiOPc)
Substantially with embodiment 1, difference is the preparation method: condensation reaction 36h is carried out in 150 ℃ of stirrings among the embodiment 1 replace with 180 ℃ of stirrings and carry out condensation reaction 24h, obtain blue-greenish colour solid 1.32g (productive rate: 61%).
The structural confirmation data of this product and embodiment 1 no substantive difference repeat no more.
Embodiment 4, preparation perfluor TiOPc (F
16TiOPc)
Substantially with embodiment 1, difference is the preparation method: the 1-chloronaphthalene (20mL) among the embodiment 1 is replaced with 1-nitro-naphthalene (20mL).Obtain blue-greenish colour solid 1.70g (productive rate: 79%).
The structural confirmation data of this product and embodiment 1 no substantive difference repeat no more.
Embodiment 5, preparation perfluor TiOPc (F
16TiOPc)
Substantially with embodiment 1, difference is the preparation method: the 1-chloronaphthalene (20mL) among the embodiment 1 is replaced with 2-naphthol methyl ether (20mL).Obtain blue-greenish colour solid 1.36g (productive rate: 63%).
The structural confirmation data of this product and embodiment 1 no substantive difference repeat no more.
Embodiment 6, preparation perfluor ranadylic phthalocyanine (F
16VOPc)
In two mouthfuls of round-bottomed flasks of 50mL, vacuumize logical nitrogen.Add then the tetrafluoro phthalic nitrile (2.00g, 10.0mmol).At room temperature inject 1-chloronaphthalene (20mL), (0.39g, 2.5mmol), condensation reaction 36h is carried out in 150 ℃ of stirrings to add vanadium trichloride again.Stop heating, naturally cooling is poured reaction mixture in the 200mL deionized water into, fully stirs.Filter above-mentioned mixing solutions with B, filter cake with the washing of 50mL anhydrous methanol is once dried down at 100 ℃.At last, filter cake is dissolved in the 50mL vitriol oil, is stirred well to whole dissolvings, and the above-mentioned concentrated sulfuric acid solution that contains the perfluor ranadylic phthalocyanine slowly pours in the 200mL ice-water bath then, gets the blue solid precipitation.Filter with B, filter cake with the 200mL deionized water wash once washs once with the 50mL anhydrous methanol, 100 ℃ of oven dry down.Obtain blue-greenish colour solid 1.13g (productive rate: 52%) at last.
The structural confirmation data of this product are as follows:
Mass spectrum: MS (MALDI-TOF): 866.9 (M
+) .HRMS (MALDI): calcd.for C
32F
16N
8O
50V (M+): 865.9406; Found:865.9409.
Nucleus magnetic hydrogen spectrum (as shown in Figure 3):
19F NMR (282MHz, D
2SO
4) δ (ppm): δ=-110.0 (d, J=26Hz) ,-115.3 (d, J=26Hz).
Uv-vis spectra is Soret band absorption peaks of metal phthalocyanine about 400 nanometers as shown in Figure 4, is Q band absorption peaks of metal phthalocyanine about 700 nanometers.
As from the foregoing, this product structure is correct, is perfluor TiOPc (F
16VOPc), its structural formula is as follows:
Embodiment 7, preparation perfluor ranadylic phthalocyanine (F
16VOPc)
Substantially with embodiment 6, difference is the preparation method: condensation reaction 36h is carried out in 150 ℃ of stirrings among the embodiment 1 replace with 120 ℃ of stirrings and carry out condensation reaction 72h, obtain blue-greenish colour solid 0.24g (productive rate: 11%).
The structural confirmation data of this product and embodiment 6 no substantive differences repeat no more.
Embodiment 8, preparation perfluor ranadylic phthalocyanine (F
16VOPc)
Substantially with embodiment 6, difference is the preparation method: condensation reaction 36h is carried out in 150 ℃ of stirrings among the embodiment 1 replace with 180 ℃ of stirrings and carry out condensation reaction 24h, obtain blue-greenish colour solid 0.87g (productive rate: 40%).
The structural confirmation data of this product and embodiment 6 no substantive differences repeat no more.
Embodiment 9, preparation perfluor ranadylic phthalocyanine (F
16VOPc)
Substantially with embodiment 6, difference is the preparation method: the 1-chloronaphthalene (20mL) among the embodiment 1 is replaced with 1-nitro-naphthalene (20mL).Obtain blue-greenish colour solid 0.69g (productive rate: 32%).
The structural confirmation data of this product and embodiment 6 no substantive differences repeat no more.
Embodiment 10, preparation perfluor ranadylic phthalocyanine (F
16VOPc)
Substantially with embodiment 6, difference is the preparation method: the 1-chloronaphthalene (20mL) among the embodiment 1 is replaced with 2-naphthol methyl ether (20mL).Obtain blue-greenish colour solid 0.58g (productive rate: 27%).
The structural confirmation data of this product and embodiment 6 no substantive differences repeat no more.
Claims (7)
1. the method for compound shown in the preparation formula I comprises the steps: in inert atmosphere, and tetrafluoro phthalic nitrile and metal chloride mixing are carried out condensation reaction, and reaction finishes and obtains compound shown in the formula I;
Among the formula I, described M is Ti or V;
Described metal chloride is titanium tetrachloride or vanadium trichloride.
2. method according to claim 1, it is characterized in that: the molar ratio of described tetrafluoro phthalic nitrile, metal chloride is followed successively by 4-10:1, is specially 4:1.
3. method according to claim 1 and 2, it is characterized in that: in the described step of condensation, temperature is 120-180 ℃, is specially 140-160 ℃, more specifically is 150 ℃;
Time is 24-72 hour, is specially 36-48 hour.
4. according to the arbitrary described method of claim 1-3, it is characterized in that: described condensation reaction is carried out in organic solvent.
5. method according to claim 4 is characterized in that: described organic solvent is selected from least a in naphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 1-nitro-naphthalene, 1-naphthol methyl ether, 2-fluoronaphthalene, 2-chloronaphthalene, 2-nitro-naphthalene and the 2-naphthol methyl ether.
6. according to the arbitrary described method of claim 1-5, it is characterized in that: described inert atmosphere is nitrogen atmosphere or argon gas atmosphere.
7. according to the arbitrary described method of claim 1-6, it is characterized in that: described method also comprises the steps: after described condensation reaction finishes, reaction mixture is poured in the deionized water, fully stirred after-filtration, get filter cake with after the anhydrous methanol washing, after 100 ℃ of oven dry, filter cake is dissolved in the vitriol oil, be stirred well to whole dissolvings after, place ice-water bath blue solid precipitation, cross the leaching filter cake with deionized water wash after again with anhydrous methanol washing, oven dry.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4701396A (en) * | 1986-05-06 | 1987-10-20 | Eastman Kodak Company | Photoconductive phthalocyanine pigments, electrophotographic elements containing them and a method of use |
| CN1680380A (en) * | 2004-03-15 | 2005-10-12 | 日本触媒股份有限公司 | Method for production of halogen-containing phthalocyanine compound |
| WO2008038679A1 (en) * | 2006-09-27 | 2008-04-03 | Nippon Shokubai Co., Ltd. | Phthalocyanine compound and process for production thereof |
-
2013
- 2013-07-11 CN CN2013102915049A patent/CN103319492A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4701396A (en) * | 1986-05-06 | 1987-10-20 | Eastman Kodak Company | Photoconductive phthalocyanine pigments, electrophotographic elements containing them and a method of use |
| CN1680380A (en) * | 2004-03-15 | 2005-10-12 | 日本触媒股份有限公司 | Method for production of halogen-containing phthalocyanine compound |
| WO2008038679A1 (en) * | 2006-09-27 | 2008-04-03 | Nippon Shokubai Co., Ltd. | Phthalocyanine compound and process for production thereof |
Non-Patent Citations (2)
| Title |
|---|
| 马锋: "全氟金属酞菁的合成与性能研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
| 高丽丽等: "全氟取代的钛酞菁衍生物的非线性光学和光限辐性能研究", 《光学学报》 * |
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Application publication date: 20130925 |