CN103242312A - Method for preparing binary perylene diimide derivative efficiently - Google Patents
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Abstract
The invention discloses a method for preparing binary perylene diimide derivative efficiently. The structural general formula of a compound is shown in the formula I. The preparation method comprises the following steps of: in inert atmosphere, carrying out reaction on the compound shown by a formula II, a copper catalyst, organic small molecule ligand and an organic base so as to obtain the compound shown in the formula I. The method has the advantages of being simple and efficient, light in environment contamination, cheap in raw material price, low in synthesis cost, good in universality and repeatability and the like, and can be promoted and used for synthesis of various other N substituent group binary perylene diimide derivative.
Description
Technical field
The present invention relates to a kind of method of the Bing of preparation Er perylene diimides derivative.
Background technology
The perylene diimides derivative is the common industrial pigment of a class, is widely used in industrial circles such as dyestuff, coating.Be endowed new performance and application along with Materials science constantly develops ， perylene diimides derivative, its photoelectric properties highlight day by day, so in the organic photoelectrical material field consequence and application prospect are arranged.For example, the organic semiconductor field includes field effect transistors, Organic Light Emitting Diode and organic photovoltaic material etc., and organic field effect tube material particularly wherein is because its excellent semiconducting behavior causes the concern of semi-conductor industry circle.The researchist has prepared Yi Xi Lie perylene diimides derivative by different synthetic methods, has developed the organic semiconductor material of a large amount of superior performances.
Yet up to now, the method for synthetic Bing Er perylene diimides precursor skeleton is but very limited, the patent of its application also with regard to following several: CN101423522, WO2010111822 and WO2010112452.
Based on reporting patent, what Bing Er perylene diimides precursor skeleton was synthetic as can be known is difficult for: methodology of organic synthesis is extremely limited, untappedly so far goes out synthetic route efficiently; Reaction yield is very low, below 15%, is unfavorable for industry's enlarging production usually; Severe reaction conditions, very responsive to the oxygen G﹠W to reaction mass purity requirement height, poor repeatability; Reaction times is of a specified duration, and the production cycle is long, can not satisfy High-efficient Production; Reaction raw materials remains in a large number, and by product is various in addition, and the utmost point is unfavorable for separating and purifying, brings a large amount of environmental pollutions and material loss because of aftertreatment easily.
In sum, the source of Bing Er perylene diimides parent compound is the bottleneck step that can not cross over for its application in the material field.Therefore, the new synthesis process that development is green improves its productive rate and purity, shortening production cycle, cuts down the consumption of energy, reduces pollutant emission, is the first step that material preparation must be passed through, for the application of novel material provides basic guarantee.
Summary of the invention
Technical problem to be solved by this invention is to overcome the weak point that Bing Er perylene diimides derivative preparation method in the prior art exists, and develops that a kind of technology is easy, favorable reproducibility and the higher method for preparing Bing Er perylene diimides derivative of productive rate efficient.
The general structure of Bing Er perylene diimides derivative of the present invention is suc as formula shown in the I:
(formula I)
Among the formula I, described R is selected from hydrogen, C
4-C
25In the aryl of alkyl and replacement any one; Substituting group in the aryl of described replacement is C
2-C
12Alkyl; Described X is Cl or Br.
Abovementioned alkyl comprises the alkyl of straight chain and side chain.
The method of the perylene diimides of Bing Er shown in the preparation formula I provided by the present invention derivative, comprise the steps: in inert atmosphere, four Lu Dai perylene diimides derivatives, copper catalyst, organic molecule part and organic bases shown in the formula II reacted, obtain the perylene diimides of Bing Er shown in formula I derivative.
(formula II)
Among the formula II, the definition cotype I of R, X.
In the aforesaid method, described copper catalyst is selected from following at least a: cuprous iodide, cuprous bromide, cuprous chloride and trifluoromethanesulfonic acid are cuprous; Wherein be catalyzer with the cuprous iodide, productive rate the best.
In the aforesaid method, described organic molecule part is selected from following at least a: pyridine-2-formic acid, pyridine-2-sodium formiate, pyridine-2-potassium formiate, thiophene-2-carboxylic acid, thiophene-2-carboxylic acid sodium and thiophene-2-carboxylic acid potassium; Be part with thiophene-2-carboxylic acid potassium wherein, productive rate the best.
In the aforesaid method, described organic bases is selected from least a in sodium ethylate, sodium acetate, Sodium Propionate, trimethylacetic acid sodium, potassium ethylate, trimethyl carbinol lithium, sodium tert-butoxide, potassium tert.-butoxide, potassium acetate, potassium propionate and the trimethylacetic acid potassium; Wherein be alkali with the potassium tert.-butoxide, productive rate the best.
Be reflected at described in the aforesaid method in the organic solvent and carry out, the mixed solvent of described organic solvent dimethyl sulfoxide (DMSO), tetramethylene sulfone, N,N-dimethylacetamide, N-Methyl pyrrolidone or these solvents; Be solvent with dimethyl sulfoxide (DMSO) or tetramethylene sulfone wherein, productive rate the best.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.
In the aforesaid method, the molar ratio of four Lu Dai perylene diimides derivatives shown in the described raw material formula II, copper catalyst, organic molecule part, organic bases is followed successively by 1: 1-10: 1-10: 1-10, preferred 1: 2.5: 2.5: 2.5.
In the aforesaid method, the temperature of reaction of described reaction is 70-120 ℃, and preferred 70-90 ℃, the reaction times is 8-15 hour, preferred 10-12 hour.Optimum reaction condition was: 90 ℃ of reactions 12 hours.
The present invention relates to raw material four halogen for perylene diimides derivative (as four chlorine for perylene diimides) in copper catalyst (as cuprous iodide) and organic molecule part (as thiophene-2-carboxylic acid potassium) effect generation bimolecular linked reaction down, and be organic bases with the potassium tert.-butoxide, the efficient copline dimer that makes up by three singly-bound bridgings of one step, productive rate is up to 56%.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; And enlarged the range of choice of catalyzer and part, therefore, avoided the defective of patent CN101423522, WO2010111822 and WO2010112452 effectively.
2, the different alkyl that replace or aromatic group can so that and the physicals variation of two perylene diimides and derivative thereof, for example long alkyl group has certain liquid crystal property, has expanded its range of application.
3, 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 Bing Er perylene diimides derivative method for the present invention.
Fig. 2 is the single crystal structure figure of the C4-4CldiPBI of embodiment 1 preparation.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Method is ordinary method if no special instructions described in the following embodiment.Described starting material all can get from open commercial sources if no special instructions.
Embodiment 1, preparation C4-4CldiPBI (2a) (R=C among the formula I
4H
9, X=Cl compound)
In two mouthfuls of round-bottomed flasks of 100mL, vacuumize logical argon gas.Add Si Lv perylene diimides raw material (1a) (R=C among the formula II then
4H
9, X=Cl compound) (1.28g, 2.0mmol), cuprous iodide (0.95g, 5.0mmol), thiophene-2-carboxylic acid potassium (0.83g, 5.0mmol), potassium tert.-butoxide (0.56g, 5.0mmol).At room temperature inject dimethyl sulfoxide (DMSO) (40mL), 90 ℃ are stirred 12h.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 is removed a large amount of cupric ions with the water washing of 100mL saturated ammonia.Filter cake is used the 300mL deionized water wash again, the washing of 100mL anhydrous methanol, 100 ℃ of oven dry down.At last, filter cake is dissolved in the 100mL methylene dichloride, mixes sample with diatomite and makes dry powder, and (leacheate is sherwood oil: methylene dichloride=1: 2 volume ratio), obtain atropurpureus solid 0.48g (productive rate: 43%) by chromatographic column then.
The structural confirmation data of this product are as follows:
Mass spectrum: MS (MALDI-TOF): cacld for M
-, 1134.2; Found, 1134.2.
Nucleus magnetic hydrogen spectrum:
1H NMR (400MHz, CDCl
3) δ (ppm): δ=10.04 (s, 2H, perylene-H), 9.24 (s, 2H, perylene-H), 8.99 (s, 2H, perylene-H), 4.42 (t, 4H, alkyl-H), 4.30 (t, 4H, alkyl-H), 1.98-1.90 (m, 4H, alkyl-H), 1.84-1.80 (m, 4H, alkyl-H), 1.61-1.51 (m, 8H, alkyl-H), 1.09-1.00 (m, 12H, methyl-H).
Nuclear-magnetism carbon spectrum:
13C NMR (101MHz, CDCl
3) δ (ppm): δ=164.4,163.5,162.9,162.6,136.2,136.1,135.5,134.1,132.4,131.1,130.2,129.1,127.2,126.3,125.9,124.8,124.6,124.3,123.8,122.2,121.2,119.3,41.9,41.1,30.6,30.5,20.8,20.6,14.1,14.0.
Single crystal structure is seen Fig. 2.As from the foregoing, this compound structure is correct, is target compound C4-4CldiPBI (2a).
Embodiment 2, preparation C4-4CldiPBI (2a)
Substantially with embodiment 1, difference is the preparation method: stir 12h with 90 ℃ among the embodiment 1 and replace with 70 ℃ of stirring 15h, obtain atropurpureus solid 0.43g (productive rate: 38%).
Embodiment 3, preparation C4-4CldiPBI (2a)
Substantially with embodiment 1, difference is the preparation method: stir 12h with 90 ℃ among the embodiment 1 and replace with 120 ℃ of stirring 8h, obtain atropurpureus solid 0.35g (productive rate: 31%).
Embodiment 4, preparation C4-4CldiPBI (2a)
Substantially with embodiment 1, difference is the preparation method: with the cuprous iodide among the embodiment 1 (0.95g, 5.0mmol) replace with cuprous chloride (0.49g, 5.0mmol).90 ℃ of stirring 12h replace with 120 ℃ and stir 8h, obtain atropurpureus solid 0.33g (productive rate: 29%).
Embodiment 5, preparation C4-4CldiPBI (2a)
Substantially with embodiment 1, difference is the preparation method: with the thiophene-2-carboxylic acid potassium among the embodiment 1 (0.83g, 5.0mmol) replace with pyridine-2-potassium formiate (0.80g, 5.0mmol).Obtain atropurpureus solid 0.29g (productive rate: 26%).
Embodiment 6, preparation Cl2-4CldiPBI (2b) (R=C among the formula I
12H
25, X=Cl compound)
In two mouthfuls of round-bottomed flasks of 100mL, vacuumize logical argon gas.Add Si Lv perylene diimides raw material (1b) (R=C among the formula II then
12H
25, X=Cl compound) (1.73g, 2.0mmol), cuprous iodide (0.95g, 5.0mmol), thiophene-2-carboxylic acid potassium (0.83g, 5.0mmol) and potassium tert.-butoxide (0.56g, 5.0mmol).At room temperature inject dimethyl sulfoxide (DMSO) (40mL), 90 ℃ are stirred 12h.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 is removed a large amount of cupric ions with the water washing of 100mL saturated ammonia.Filter cake is used the 300mL deionized water wash again, the washing of 100mL anhydrous methanol, 100 ℃ of oven dry down.At last, filter cake is dissolved in the 100mL methylene dichloride, mixes sample with diatomite and makes dry powder, and (leacheate is sherwood oil: methylene dichloride=1: 1 volume ratio), obtain atropurpureus solid 0.82g (productive rate: 52%) by chromatographic column then.
The structural confirmation data of this product are as follows:
Mass spectrum: MS (MALDI-TOF): cacld for M-, 1582.7; Found, 1582.9.
Nucleus magnetic hydrogen spectrum:
1H NMR (400MHz, CDCl
3) δ (ppm): 10.05 (s, perylene-H, 2H), 9.25 (s, perylene-H, 2H), 9.00 (s, perylene-H, 2H), 4.41 (t, alkyl-H, 4H), 4.29 (t, alkyl-H, 4H), 2.02-1.89 (m, alkyl-H, 8H), 1.49-1.25 (m, alkyl-H, 60H), 0.88-0.83 (m, alkyl-H, 12H).
Nuclear-magnetism carbon spectrum:
13C NMR (101MHz, CDCl
3) δ (ppm): 164.3,163.4,162.8,162.5,136.2,136.1,135.4,134.0,132.3,131.0,130.0,129.0,127.1,126.2,125.8,124.6,124.5,124.2,123.7,122.1,119.2,42.1,41.3,32.1,29.9,29.8,29.7,29.6,29.5,28.4,28.3,27.4,22.8,14.2.
As from the foregoing, this compound structure is correct, is target compound C12-4CldiPBI (2b).
Embodiment 7, preparation C12-4CldiPBI (2b)
Substantially with embodiment 6, difference is the preparation method: stir 12h with 90 ℃ among the embodiment 6 and replace with 70 ℃ of stirring 15h, obtain atropurpureus solid 0.69g (productive rate: 44%).
Embodiment 8, preparation C12-4CldiPBI (2b)
Substantially with embodiment 6, difference is the preparation method: stir 12h with 90 ℃ among the embodiment 6 and replace with 120 ℃ of stirring 8h, obtain atropurpureus solid 0.62g (productive rate: 39%).
Embodiment 9, preparation C12-4CldiPBI (2b)
Substantially with embodiment 6, difference is the preparation method: with the cuprous iodide among the embodiment 6 (0.95g, 5.0mmol) replace with cuprous chloride (0.49g, 5.0mmol).90 ℃ of stirring 12h replace with 120 ℃ and stir 8h, obtain atropurpureus solid 0.47g (productive rate: 30%).
Embodiment 10, preparation C12-4CldiPBI (2b)
Substantially with embodiment 6, difference is the preparation method: with the thiophene-2-carboxylic acid potassium among the embodiment 6 (0.83g, 5.0mmol) replace with pyridine-2-potassium formiate (0.80g, 5.0mmol).Obtain atropurpureus solid 0.49g (productive rate: 31%).
Claims (8)
1. the method for compound shown in the preparation formula I comprises the steps: in inert atmosphere, and the compound shown in the formula II, copper catalyst, organic molecule part and organic bases are reacted, and obtains compound shown in the formula I;
(formula I) (formula II)
Among the formula I, described R is selected from hydrogen, C
4-C
25In the aryl of alkyl and replacement any one; Substituting group in the aryl of described replacement is C
2-C
12Alkyl; Described X is Cl or Br;
Among the formula II, the definition cotype I of described R, X.
2. method according to claim 1, it is characterized in that: described copper catalyst is selected from following at least a: cuprous iodide, cuprous bromide, cuprous chloride and trifluoromethanesulfonic acid are cuprous; Preferred cuprous iodide.
3. method according to claim 1 and 2, it is characterized in that: described organic molecule part is selected from following at least a: pyridine-2-formic acid, pyridine-2-sodium formiate, pyridine-2-potassium formiate, thiophene-2-carboxylic acid, thiophene-2-carboxylic acid sodium and thiophene-2-carboxylic acid potassium; Preferred thiophene-2-carboxylic acid potassium.
4. according to each described method among the claim 1-3, it is characterized in that: described organic bases is selected from least a in sodium ethylate, sodium acetate, Sodium Propionate, trimethylacetic acid sodium, potassium ethylate, trimethyl carbinol lithium, sodium tert-butoxide, potassium tert.-butoxide, potassium acetate, potassium propionate and the trimethylacetic acid potassium.
5. according to each described method among the claim 1-4, it is characterized in that: described being reflected in the organic solvent carried out, and described organic solvent is selected from following at least a: dimethyl sulfoxide (DMSO), tetramethylene sulfone, N,N-dimethylacetamide and N-Methyl pyrrolidone; Preferred dimethyl sulfoxide (DMSO) and/or tetramethylene sulfone.
6. according to each described method among the claim 1-5, it is characterized in that: the molar ratio of compound shown in the described formula II, copper catalyst, organic molecule part, organic bases is followed successively by 1: 1-10: 1-10: 1-10, preferred 1: 2.5: 2.5: 2.5.
7. according to each described method among the claim 1-6, it is characterized in that: the temperature of reaction of described reaction is 70-120 ℃, and preferred 70-90 ℃, the reaction times is 8-15 hour, preferred 10-12 hour.
8. according to each described method among the claim 1-7, it is characterized in that: described inert atmosphere is nitrogen atmosphere or argon gas atmosphere.
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| CN103819482A (en) * | 2014-03-10 | 2014-05-28 | 山东师范大学 | Cyclopentadiene-bridging dimeric perylene diimide compound and preparation method thereof |
| WO2015171640A1 (en) * | 2014-05-05 | 2015-11-12 | The Trustees Of Columbia University In The City Of New York | Organic semiconductor compounds and methods of use |
| CN106866671A (en) * | 2015-12-11 | 2017-06-20 | 中国科学院化学研究所 | A kind of gear type San Ju perylene diimides compounds and its preparation method and application |
| CN108424413A (en) * | 2017-02-15 | 2018-08-21 | 中国科学院化学研究所 | A kind of synthesis of imide analog compounds and its preparation method and application based on three dish alkene |
| CN108503638A (en) * | 2018-04-25 | 2018-09-07 | 福建师范大学福清分校 | A kind of method of cobalt catalysis polyhalo imidodicarbonic diamide Dehalogenation reduction |
| CN108822107A (en) * | 2018-06-08 | 2018-11-16 | 福建师范大学福清分校 | A kind of method of nickel catalysis polyhalo imidodicarbonic diamide class aromatic hydrocarbons Dehalogenation reduction |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819482A (en) * | 2014-03-10 | 2014-05-28 | 山东师范大学 | Cyclopentadiene-bridging dimeric perylene diimide compound and preparation method thereof |
| WO2015171640A1 (en) * | 2014-05-05 | 2015-11-12 | The Trustees Of Columbia University In The City Of New York | Organic semiconductor compounds and methods of use |
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| CN106866671A (en) * | 2015-12-11 | 2017-06-20 | 中国科学院化学研究所 | A kind of gear type San Ju perylene diimides compounds and its preparation method and application |
| CN106866671B (en) * | 2015-12-11 | 2019-02-22 | 中国科学院化学研究所 | A kind of gear type trimerization imide compound and its preparation method and application |
| CN108424413A (en) * | 2017-02-15 | 2018-08-21 | 中国科学院化学研究所 | A kind of synthesis of imide analog compounds and its preparation method and application based on three dish alkene |
| CN108503638A (en) * | 2018-04-25 | 2018-09-07 | 福建师范大学福清分校 | A kind of method of cobalt catalysis polyhalo imidodicarbonic diamide Dehalogenation reduction |
| CN108822107A (en) * | 2018-06-08 | 2018-11-16 | 福建师范大学福清分校 | A kind of method of nickel catalysis polyhalo imidodicarbonic diamide class aromatic hydrocarbons Dehalogenation reduction |
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