CN101139319A - Substituted quinoline three polyindene derivatives and preparation method thereof - Google Patents

Abstract

The present invention belongs to the technological field of the organic electroluminescent material, specifically relating to the substituted quinoline tripolyphosphate indene derivative and the preparation. In the present invention, the tripolyphosphate indene is used as the raw material; the secondary base is introduced on the fifth, tenth and fifteenth levels to increase the solubility; then the material is acylated with the friedel gram; the acetyl can be introduced on the second, seventh and twelfth levels; the different dosages of the acylating reagent is adjusted to get the single-acylated, double-acylated and wholly acylated tripolyphosphate indene. The intermediates are respectively concentrated with the substituted 2-amido dibenzophenone through the Furuidelande with the acid catalyst to prepare a series of phenyl substituted single-quinoline, double-quinoline, tri-quinoline tripolyphosphate indene derivative. The molecule of the compounds has the good fluorescent characteristics and provides a novel way for the novel electroluminescent material.

Description

Substituted quinoline three polyindene derivatives and preparation method thereof

technical field

The invention relates to the technical field of organic electroluminescent materials, in particular to a class of substituted quinolinetriindene derivatives and a preparation method thereof.

Background technique

Traditional optoelectronic functional materials are mainly metals, metalloids, and some oxides. Due to their structural characteristics, most organic compounds do not have free electrons, so they have long been excluded from optical, electrical, and magnetic functions. With the vigorous development of the optoelectronic information industry, new and higher-level requirements have been put forward for materials. In the past two or three decades, people have also shown strong interest in the optoelectronic properties of organic compounds. Since the 1970s, people have discovered organic conductors, organic superconductors, organic ferromagnets, organic nonlinear optical materials, etc., showing brilliant prospects in both theoretical research and material exploration.

Organic electroluminescence, also known as organic light-emitting diode (OLED), is a major research hotspot in the field of flat panel display in the world in recent years ([1] Tang, C.W; Van Slyke S.A.Appl.Phys.Lett.1987, 51, 91; [ 2] Muller C.D., Falcou A., Reckefuss N.et al.Nature, 2003, 421, 829.), has the advantages of planarization, active light emission, high brightness, high contrast, fast response, low driving voltage and so on. It is a new technology most likely to replace liquid crystal displays in the future ([3] Teng Feng, Hou Yanbing, Yin Shougen, etc., Organic Electroluminescent Materials and Applications, May 2006, Chemical Industry Press). The application of display technology in modern life is also becoming more and more extensive, such as mobile phone screens, instrument display screens, computer terminal monitors, TV sets, and outdoor large-screen display screens. Therefore, no matter from the perspective of technology or business, new high-performance display technology will become a research hotspot in the field of display technology in the world, causing people to pay great attention to organic electroluminescent materials and electroluminescent devices. Therefore, exploration and research New organic luminescent materials have become a hot topic in the research field.

Trisindene is a highly symmetrical condensed ring aromatic hydrocarbon, which has been proved to be one of the ideal compounds for the preparation of liquid crystal materials, fullerene derivatives and C3-type asymmetric catalytic materials. If the trimeric indene can be properly chemically modified and used as a structural unit to construct a new type of organic conjugated functional material, unique optical and optoelectronic behaviors will be produced.

The Laboratory of Organic Solids and Polymer Materials, led by Dr. Pei Jian, Key Laboratory of Bioorganic and Molecular Engineering, Ministry of Education, School of Chemistry and Molecular Engineering, Peking University, introduced the structure of trisindene into the field of organic optoelectronic materials for the first time. They used trisindene as the structure basis, successfully prepared a series of star-shaped oligothiophene substituted triindene derivatives and a new class of conjugated dendrimers based on the triindene structure ([4] J.Pei, J-L Wang, X-Y .Cao, X-H Zhou, W-B.Zhang, J.Am Chem.Soc.2003, 125, p9944-9945.[5]X.Y Cao, W.-B.Zhang, J.-L.Wang, X.H Zhou, J. Pei, J.Am.Chem.Soc.2003, 12340-12341. [6] S.-C.Yuan, H.-B.Chen, Y.Zhang, J.Pei, Org.Lett.2006, 8, 5701 -5704.). This achievement breaks through the traditional limitations of using simple molecules such as benzene, fluorene, and thiophene-phenylene vinylene as building blocks, and provides a new idea for the construction of new organic conjugated functional materials.

The star-shaped oligothiophene-substituted trisindene derivatives synthesized in this research are gradually increased with the thiophene arms, and the ultraviolet and absorption spectra of the compound are red-shifted, which not only suppresses the interaction between the aromatic ring planes p-stacking effect, and at the same time, the morphology of the synthesized material in the solid state is well improved, and it has very excellent optical properties. The prospect of such materials as organic electroluminescent diode devices and organic solar cells is quite promising.

Contents of the invention

The object of the present invention is to provide a class of substituted quinolinetriindene derivatives and a preparation method thereof. The organic compound has a simple structure and can be used as an organic electroluminescence material, and the preparation method is very simple.

The purpose of the present invention is achieved like this:

A class of substituted quinoline triindene derivatives is characterized in that a substituted quinoline group is introduced into the ethylated triindene.

Introduce one substituted quinoline group, two substituted quinoline groups or three substituted quinoline groups on the three indene, respectively 2-monosubstituted quinoline three polyindene, 2,7- Disubstituted quinoline indene or 2,7,12-trisubstituted quinoline indene, its chemical structure is as follows:

Wherein: the substituent X is H, F or Br.

The method for preparing the above-mentioned substituted quinoline three-indene derivatives is: using three-indene as a raw material, introducing ethyl groups at positions 5, 10, and 15, and then undergoing Friedel-Crafts acylation; , the 12-position introduces an acetyl group; these intermediates are condensed with substituted 2-aminobenzophenones under acid catalysis by Friedlander (Friedlander) condensation to prepare phenyl-substituted monoquinoline, bisquinoline, three Quinoline Triindene Derivatives.

The method described above can obtain single acylation through acylation, double acylation, and fully acylated tripolyindene, and its structural formula is as follows:

In the above method, when the molar ratio of the ethylated trisindene to the acylating agent is 1:1.2, the monoacylated trisindene is the main one; Polyindene is mainly used; when the feeding molar ratio is 1:3-4, fully acylated tripolyindene is mainly used.

The single acylated trisindene reacts with substituted 2-aminobenzophenone to obtain monoquinoline substituted trisindene (4d-4f); Ketone reaction to obtain bisquinoline-substituted trisindene (5d-5f); fully acylated trisindene reacted with 2-aminobenzophenone to obtain triquinoline-substituted trisindene (6d-6f).

The acylating agent of the present invention is acetyl chloride or acetic anhydride.

The present invention respectively introduces a phenyl-substituted quinoline group, two phenyl-substituted quinoline groups, and three phenyl-substituted quinoline groups at the 2, 7, and 12 positions of the fully-ethylated triindene , UV and fluorescence tests show that it has good photoelectric properties, and it is expected to become a new type of organic conjugated functional material.

Description of drawings

Accompanying drawing is the flow chart of the present invention

Detailed ways

Further describe the present invention below by embodiment

Reagents used: n-butyllithium, tert-butyllithium and methyllithium analytically pure [Alfa Aisha (Tianjin) Chemical Co., Ltd.]; bromoethane chemically pure [Sinopharm Chemical Reagent Co., Ltd.]; acetic anhydride Chemically pure [Sinopharm Group Chemical Reagent Co., Ltd.]; aluminum trichloride analytically pure [Shanghai Meixing Chemical Co., Ltd.]; 2-aminobenzophenone, 2-amino-4'-fluorobenzophenone, 2 -Amino-4'-bromo-benzophenone chemically pure [Jiangsu Jintan Tianyuan Pharmaceutical Chemical Research Institute] production.

Example

Step 1: Preparation of 5,10,15-hexaethyltriindene 1

Under the protection of N ₂ , 3.42g of tripolyindene (10mmol) was added to 100ml of THF, cooled to 0°C, and 12.6ml of n-butyllithium (36mmol) was slowly added dropwise. Stirring was continued for 0.5 hours. Then cool to 0°C and add 4.9 g of bromoethane (45 mmol) dropwise. After stirring at room temperature for 4 hours, add the same amount of butyllithium as last time under the same conditions. After stirring for 1 hour, add 4.9 g of butyllithium dropwise. g of bromoethane (45mmol), stirred at room temperature for 12 hours, poured the mixture into 70ml of water, extracted with CH ₂ Cl ₂ , removed the solvent under reduced pressure to obtain a light yellow solid, refluxed in ethanol for 1 hour and filtered to obtain a white powder Solid 4.18g (compound 1), yield 82%, mp218-221°C; ¹ HNMR (500Mz, CDCl ₃ , ppm): δ8.4 (1H, d, J=7.2Hz, Tr-H), 7.5 (1H , m, Tr-H), 7.4 (1H, m, Tr-H), 3.0 (2H, m, -CH ₂ -), 2.2 (2H, m, -CH ₂ -), 0.2 (6H, t, J =7.3Hz, -CH ₃ ).

Step two:

(1), the preparation of monoacetyltripolyindene 2a

5.1g of compound 1 was added to 50ml of anhydrous CH ₂ Cl ₂ , and 2.8g of anhydrous AlCl ₃ (0.021mol) was added immediately, the mixture was cooled to 0°C, and 1.13g of acetic anhydride (0.01mol) was dissolved in 5ml of CH ₂ Cl ₂ was added dropwise to the above mixed solution, after the dropwise addition was completed, it was raised to room temperature and stirred for 2 hours, then poured into crushed ice containing concentrated hydrochloric acid, extracted with ethyl acetate, washed with Na ₂ CO ₃ solution and saturated brine respectively, The organic phase was dried with MgSO ₄ , the solvent was removed, and the column chromatography gave a light yellow powdery solid with a yield of 81%, mp209-212°C. ¹ HNMR (500Mz, CDCl ₃ , ppm): δ8.38-8.36 (1H, d , J=8.0Hz, Tr-H), 8.29(2H, t, J=6Hz, Tr-H), 8.00(1H, s, Tr-H), 7.95-7.94(1H, m, Tr-H), 2.99-2.90 (1H, m, -CH ₂ -), 2.65 (3H, s, -COCH ₃ ), 2.17-2.09 (6H, m, -CH ₂ -), 0.16-0.12 (18H, m, -CH ₃ ).

(2), the preparation of diacetyltriindene 2b

The preparation method is the same as the second step (1), the amount of acetic anhydride is increased to 2.47g (0.022mol), other amounts remain unchanged, the yield is 72%, mp304-306°C. ¹ HNMR (500Mz, CDCl ₃ , ppm): δ8 .45-8.35(m, 3H, Tr-H), 8.08-8.02(m, 4H, Tr-H), 7.47-7.41(m, 3H, Tr-H), 3.07-2.95(m, 6H, -CH ₂ -), 2.71 (s, 6H, -COCH ₃ ), 2.28-2.17 (m, 6H, -CH ₂ ), 0.22-0.18 (m, 18H, -CH ₃ ).

(3), the preparation of full acetyltripolyindene 2c

The preparation method is the same as the second step (1), the amount of acetic anhydride is increased to 3.94g (0.035mol), other amounts remain unchanged, the yield is 78%, mp226-229°C. ¹ HNMR (500Mz, CDCl ₃ , ppm): δ8 .45(d, 1H, J=9Hz, Tr-H), 8.09(s, 1H, Tr-H), 8.04(d, 1H, J=8Hz, Tr-H), 3.03-2.97(m, 2H, -CH ₂ -), 2.72(s, 3H, -COCH ₃ ), 2.30-2.25(m, 2H, -CH ₂ -), 0.22(m, 6H, -CH ₃ )

third step:

(1), the preparation of monosubstituted quinolinetriindene 4d-4f

Add monoacetyltriindane 2a (5.52g, 0.01mol) and 0.01mol of 2-aminobenzophenone derivatives into a flask containing 30mL of acetic acid, add 0.1mL of concentrated sulfuric acid dropwise, and reflux for 20 hours. The mixture was poured into 40mL aqueous solution of 15mL concentrated ammonia water prepared in advance, there was a yellow precipitate, filtered, and the solid was washed with water to obtain the initial product, which was separated by column chromatography to obtain a light yellow solid. 4d: Yield 56%, mp176-178°C. ¹ HNMR (500Mz, CDCl ₃ , ppm): δ8.54 (d, 1H, J=8Hz) 8.41-8.37 (m, 2H), 8.33-8.25 (m, 3H), 7.97(s, 1H), 7.94(d, 1H, J=8Hz), 7.79-7.76(m, 1H), 7.65-7.56(m, 5H), 7.52-7.40(m, 7H), 3.08( m, 6H, -CH ₂ -), 2.20 (m, 2H, -CH ₂ -), 2.18 (m, 4H, -CH ₂ -), 0.30-0.22 (m, 18H, -CH ₃ ). 4e: close rate, 50%; mp281-283°C. ¹ HNMR (500Mz, CDCl ₃ , ppm): δ8.53(d, 1H, J=9Hz), 8.38(t, 2H, J=8Hz), 8.32-8.24(m , 3H), 7.92(s, 1H), 7.88(d, 1H, J=8Hz), 7.79-7.76(m, 1H), 7.63-7.60(m, 2H), 7.53-7.47(m, 3H), 7.43 -7.40(m, 4H), 7.31-7.26(m, 2H), 3.09-3.02(m, 6H, _-CH2- ), 2.30(m, 2H, _-CH2- ), 2.23-2.17(m, 4H , -CH ₂ -), 0.29-0.21(m, 18H, -CH ₃ ).4f: Yield, 59%; mp291-294°C. ¹ HNMR (500Mz, CDCl ₃ , ppm): δ8.52(d, 1H, J=9Hz), 8.38(t, 2H, J=8Hz), 8.32-8.24(m, 3H), 7.91(s, 1H), 7.87(d, 1H, J=9Hz), 7.79-7.73(m , 3H), 7.52-7.47(m, 5H), 7.43-7.39(m, 4H), 3.05(m, 6H, -CH ₂ -), 2.30(m, 2H, -CH ₂ -), 2.18(m, 4H, -CH ₂ -), 0.29-0.21 (m, 18H, -CH ₃ ).

(2), preparation of disubstituted quinoline tripolyindene 5d-5f

Add diacetyltriindane 2b (5.94g, 0.01mol) and 0.022mol of 2-aminobenzophenone derivatives into a flask containing 30mL of acetic acid, add 0.1mL of concentrated sulfuric acid dropwise, and reflux for 20 hours. The mixture was poured into 40mL aqueous solution of 15mL concentrated ammonia water prepared in advance, there was a yellow precipitate, filtered, and the solid was washed with water to obtain the initial product, which was separated by column chromatography to obtain a light yellow solid. 5d: Yield 51%; mp242°C (bubbles started at 124°C). ¹ H NMR (500Mz, CDCl ₃ , ppm): δ8.56 (m, 2H), 8.42 (d, 1H, J=8Hz), 8.54(m, 4H), 8.27(d, 2H, J=7Hz), 7.98(s, 2H), 7.94(d, 2H, J=8Hz), 7.78(t, 2H, J=8Hz), 7.66-7.56 (m, 10H), 7.51(m, 3H), 7.43(m, 2H), 3.31(m, 6H, -CH ₂ -), 2.37-2.33(m, 4H, -CH ₂ -), 2.23(m, 2H, -CH ₂ -), 0.35-0.25 (m, 18H, -CH ₃ ).5e: Yield 46%, mp 223°C (bubbles started at 177°C). ¹ H NMR (500Mz, CDCl ₃ , ppm) : δ8.55(t, 2H, J=9Hz), 8.40(d, 1H, J=8Hz), 8.33-8.26(m, 6H), 7.93(s, 2H), 7.88(d, 2H, J=8Hz ), 7.77(t, 2H, J=8Hz), 7.62-7.60(m, 4H), 7.53-7.49(m, 3H), 7.45-7.39(m, 2H), 7.29(m, 4H), 3.13-3.07 (m, 6H, -CH ₂ -), 2.36-2.32 (m, 4H, -CH ₂ -), 2.22 (m, 2H), 0.32-0.24 (m, 16H, -CH ₃ ).5f: Yield 54 %.mp 323-325°C. ¹ H NMR (500Mz, CDCl ₃ , ppm): δ8.55(t, 2H, J=9Hz), 8.41(d, 1H, J=8Hz), 8.32-8.30(m, 4H), 8.26(d, 2H, J=6Hz), 7.93(s, 2H), 7.79-7.73(m, 5H), 7.50-7.49(m, 8H), 7.45-7.41(m, 2H), 3.11( m, 6H, -CH ₂ -), 2.34 (m, 4H, -CH ₂ -), 2.22 (m, 2H, -CH ₂ -), 0.32-0.24 (m, 16H, -CH ₃ ).

(3), the preparation of trisubstituted quinolinetriindene 6d-6f

Add peracetyltriindane 2c (6.36g, 0.01mol) and 0.035mol of 2-aminobenzophenone derivatives into a flask containing 30mL of acetic acid, add 0.1mL of concentrated sulfuric acid dropwise, and reflux for 20 hours. The mixture was poured into 40mL aqueous solution of 15mL concentrated ammonia water prepared in advance, there was a yellow precipitate, filtered, and the solid was washed with water to obtain the initial product, which was separated by column chromatography to obtain a light yellow solid. 6d: Yield 55%, mp 290°C (bubbles started at 209°C). ¹ H NMR (500Mz, CDCl ₃ , ppm): δ8.58 (d, 1H, J=9Hz), 8.36-8.29 (m, 3H ), 7.98(s, 1H), 7.34(d, 1H, J=8Hz), 7.77(t, 1H, J=8Hz), 7.65-7.54(m, 5H), 7.51(m, 1H), 3.15(m , 2H, -CH ₂ -), 2.37(m, 2H, -CH ₂ -), 0.32(m, 6H, -CH ₃ ).6e: Yield 51%, mp270-272℃. ¹ HNMR (500Mz, CDCl ₃ , ppm): δ8.57(d, 1H, J=8Hz), 8.35-8.30(m, 3H), 7.94(s, 1H), 7.88(d, 1H, J=8Hz), 7.77(m, 1H ), 7.62-7.60 (m, 2H), 7.53-7.49 (m, 1H), 7.29 (t, 2H, J=8.6Hz), 3.18-3.11 (m, 2H, -CH ₂ -), 2.42-2.35 ( m, 2H, -CH ₂ -), 0.34-0.31 (m, 6H, -CH ₃ ).6f: Yield 60%, mp263-266°C. ¹ H NMR (500Mz, CDCl ₃ , ppm): δ8.57 (d, 1H, J=8.3Hz), 8.34-8.29(m, 3H), 7.93(s, 1H), 7.87(d, 1H, J=8.3Hz), 7.78(m, 1H), 7.73(d, 1H, J=8.2Hz), 7.52-7.50(m, 3H), 3.17-3.10(m, 2H, -CH ₂ -), 2.42-2.35(m, 2H, -CH ₂ -), 0.35-0.32(m , 6H, -CH ₃ ).

Claims (6)

1. a class substituted quinoline trimer indene derivative is characterized in that on ethylating three polyindenes, has introduced the quinoline group that replaces.

2. substituted quinoline trimer indene derivative according to claim 1, it is characterized in that on described three polyindenes, introducing quinoline group, the quinoline group of two replacements or the quinoline group of three replacements of a replacement, it is respectively the single substituted quinoline trimer indene, 2 of 2-, the two substituted quinoline trimer indenes or 2 of 7-, 7,12-three substituted quinoline trimer indenes, its chemical structural formula is as follows:

4d-4f 5d-5f 6d-6f

Wherein: substituent X is H, F or Br.

3. a method for preparing claim 1 or 2 described substituted quinoline trimer indene derivatives is characterized in that with three polyindenes be raw material, introduces ethyl at its 5,10,15 earlier, then through friedel-crafts acylation, 2,7, introduces ethanoyl for 12; These intermediates respectively with the 2-aminobenzophenone that replaces under acid catalysis through the blue moral condensation of Fred, single quinoline that the preparation phenyl replaces, two quinoline, three quinoline trimer indene derivatives.

4. preparation method according to claim 3 is characterized in that can obtaining single acidylate through acylations, two acidylates, and three polyindenes of full acidylate, its structural formula is as follows:

2a 2b 2c

5. preparation method according to claim 4 is characterized in that ethylating three polyindenes and acylting agent molar ratio are at 1: 1.2 o'clock, and three polyindenes of single acidylate are main; Molar ratio is 1: during 1.9-2.5, three polyindenes of two acidylates are main; Molar ratio is 1: during 3-4, three polyindenes of full acidylate are main.

6. preparation method according to claim 5 is characterized in that three polyindenes of single acidylate and the 2-aminobenzophenone reaction of replacement, obtains three polyindenes (4d-4f) that single quinoline replaces; Three polyindenes of two acidylates and the reaction of 2-aminobenzophenone obtain three polyindenes (5d-5f) that two quinoline replace; Three polyindenes of full acidylate and the reaction of 2-aminobenzophenone obtain three polyindenes (6d-6f) that three quinoline replace.

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