CN102491936A - Conjugated compound with yellow-green fluorescence and preparation method and use thereof - Google Patents

Abstract

The invention discloses a conjugated compound with fluorescent properties, a preparation method and application thereof. The general structural formula of the conjugated compound is shown in Formula I. The skeleton of the compound is a conjugated system composed of five aromatic rings fixed by two methylene groups, so it has a large delocalized system, and the system has a helical chirality due to the fixing effect of the methylene group. The push-pull electron effect of methoxy group and substituted aromatic group or heterocycle and the pull electron effect of imide make the ground state electrons more easily excited and can promote fluorescence emission, so it has longer excitation wavelength and emission wavelength. Ar is the phenyl For example, its excitation wavelength in toluene is 420nm, and its emission wavelength is 474nm. It appears bright yellow-green in solution. The method for preparing the above-mentioned conjugated compound provided by the invention has cheap raw materials, simple synthesis, high product yield, easy derivatization, correct structure of the compound obtained through instrument detection, good stability, and good application prospects in the field of photoelectric materials.

Description

A conjugated compound with yellow-green fluorescence and its preparation method and application

technical field

The invention relates to a conjugated compound with yellow-green fluorescence, a preparation method and application thereof.

Background technique

Due to its high application value in photochemical devices, organic electroluminescent devices (ELD) and solar cells (OPV) and other optoelectronic materials, the research of organic optoelectronic materials has always been a hot spot for many scientists. Green and blue primary colors have long been favored by researchers as the basis of fluorescent material research.

Currently in this field, the representative ones mainly contain red light-emitting perylene imide derivatives (P.Wang, H.L.Zhang, L.Zhang, Synthesis and characterization of perylene diimides new style redlight-emitting material, Chemical Industry and Engineering Progress, 2008, 27, 460-463); Green light-emitting coumarin derivatives (H.Tang, X.R.Wang, Y.Li, Green organic light-emittingdiodes with improved stability and efficiency utilizing a wide band gap material as the host, DISPLAYS, 2008, 29, 502-505); blue-emitting pyrazoline derivatives (C.Hao, Xu.Xing, Y.H.Gang, Novel fluorine carzazole based conjugated containing pyrazoline and benzothiazolesegments for blue light-emitting materials , Chin.Chem.Lett., 2007, 18, 1496-1500) etc.

Conjugation effects (such as perylene, helicene, etc.) and push-pull effects (such as coumarin, rhodamine, etc.) are important considerations in the design and synthesis of fluorescent materials, so molecules that combine conjugation effects and intramolecular push-pull electronic effects It is currently a new research hotspot. Therefore, the synthesis of new conjugated compounds with fluorescent properties has high scientific research value and application value.

Contents of the invention

The object of the present invention is to provide a conjugated compound with fluorescent properties and a preparation method thereof.

The conjugated compound provided by the present invention has a general structural formula as shown in formula I:

In the general structural formula of formula I, Ar is selected from any one of phenyl, substituted phenyl and heterocyclic; R is n-propyl or n-dodecyl; R' is methyl.

The heterocyclic group may specifically be 3-thienyl.

The substituted phenyl group may specifically be any one of the following: 4-methylphenyl group, 4-methoxyphenyl group, 4-formylphenyl group and 4-chlorophenyl group.

The method for preparing the conjugated compound shown in formula I, comprises the following steps:

1) 7,7'-dimethoxy-3,4,3',4'-tetrahydro-1,1'-binaphthalene and maleic anhydride are refluxed in an organic solvent to obtain formula II The anhydride addition product A shown;

2) dissolving the obtained acid anhydride addition product A in dichloromethane, and adding liquid bromine acetic acid solution dropwise therein for reaction to obtain the oxidation addition product B shown in formula III;

3) reacting the obtained oxidative addition product B with n-propylamine or n-dodecylamine in an organic solvent to obtain lactim C shown in formula IV;

The definition of R in formula IV is the same as formula I;

4) In the presence of a catalyst triphenylphosphopalladium and a base, react the lactam C with the aromatic boronic acid represented by formula V in an organic solvent to obtain a conjugated compound represented by formula I;

Ar-B(OH) ₂

(Formula V)

The definition of Ar in formula V is the same as that of formula I.

Wherein, the molar ratio of maleic anhydride to 7,7'-dimethoxy-3,4,3',4'-tetrahydro-1,1'-binaphthyl in step 1) is 1 : 1-1.5: 1, specifically 1: 1; the organic solvent can specifically be xylene; in the reflux reaction, the reaction time is 6-10 hours, specifically 8-10 hours, and the reaction temperature is 130 -160°C, specifically 140-150°C.

In step 2), the molar ratio of the addition product A to liquid bromine is 1:4-8, specifically 1:5; the reaction time of the reaction is 8-12 hours, specifically 10-12 hours, The reaction temperature is room temperature, specifically 15-18°C; the volume ratio of acetic acid to liquid bromine is 5:1-10:1, specifically 8:1-9:1.

In step 3), the organic solvent is dimethylformamide (DMF) or toluene, preferably DMF; the reaction needs to be carried out under the protection of argon;

When the oxidative addition product B reacts with n-propylamine, the molar ratio of the oxidative addition product B to n-propylamine is 1:5-1:10, specifically 1:8; the reaction time of the reaction 12-24 hours, specifically 20-24 hours, the reaction temperature is 30-70°C, specifically 40-60°C;

When the oxidative addition product B reacts with n-dodecylamine, the molar ratio of the oxidative addition product B to n-dodecylamine is 1:1-1:3, specifically 1: 1. The reaction time of the reaction is 12-24 hours, specifically 20-24 hours, and the reaction temperature is 90-110°C, specifically 95-100°C.

In step 4), the alkali can specifically be potassium carbonate; the organic solvent is selected from any one of the following two mixed solutions: 1) toluene, ethanol and water according to the volume ratio of 8-5: 4-3: 3-1 The mixed solvent obtained by mixing, 2) The mixed solvent obtained by mixing xylene, ethanol and water according to the volume ratio of 8-5:4-3:3-1; the reaction needs to be carried out under the protection of argon;

The molar ratio of the triphenylphosphopalladium, lactam C and aromatic boric acid is 0.02-0.1:1:2-3, specifically 0.043:1:3; the reaction time of the reaction is 16-24 hours , specifically for 20-24 hours, and the reaction temperature is 90-110° C., specifically 95-100° C.; the reaction requires argon protection.

Another object of the present invention is to provide the application of the above-mentioned fluorescent conjugated compound in the preparation of organic light-emitting materials or organic fluorescent dyes.

The conjugated compound provided by the present invention has a larger delocalized system because the compound is a conjugated system composed of five aromatic rings fixed by two methylene groups, and the system is made It has helical chirality, and at the same time, due to the push-pull electron effect of methoxy group and substituted aromatic group or heterocycle and the electron-pull effect of imide, the ground state electrons are more easily excited, which can promote fluorescence emission, so it has a longer excitation wavelength and emission wavelength. Taking Ar=phenyl in formula I as an example, its excitation wavelength in toluene is 420 nm, and its emission wavelength is 474 nm. It appears bright yellow-green in solution. The method for preparing the above-mentioned conjugated compound provided by the invention has cheap raw materials, simple synthesis, high product yield, easy derivatization, correct structure of the compound obtained through instrument detection, good stability, and good application prospects in the field of photoelectric materials.

Description of drawings

Fig. 1 is the H NMR spectrum of the conjugated compound prepared in Example 1.

Figure 2 is the carbon NMR spectrum of the conjugated compound prepared in Example 1.

Figure 3 is the single crystal structure of the conjugated compound prepared in Example 1.

FIG. 4 is the excitation spectrum of the conjugated compound prepared in Example 1.

FIG. 5 is the emission spectrum of the conjugated compound prepared in Example 1.

Figure 6 is the H NMR spectrum of the conjugated compound prepared in Example 2.

Figure 7 is the carbon NMR spectrum of the conjugated compound prepared in Example 2.

FIG. 8 is the excitation spectrum of the conjugated compound prepared in Example 2.

FIG. 9 is the emission spectrum of the conjugated compound prepared in Example 2.

Figure 10 is the H NMR spectrum of the conjugated compound prepared in Example 3.

Figure 11 is the carbon NMR spectrum of the conjugated compound prepared in Example 3.

Figure 12 is the single crystal structure of the conjugated compound prepared in Example 3.

Figure 13 is the excitation spectrum of the conjugated compound prepared in Example 3.

Figure 14 is the emission spectrum of the conjugated compound prepared in Example 3.

Figure 15 is the H NMR spectrum of the conjugated compound prepared in Example 4.

Figure 16 is the carbon NMR spectrum of the conjugated compound prepared in Example 4.

Figure 17 is the excitation spectrum of the conjugated compound prepared in Example 4.

Figure 18 is the emission spectrum of the conjugated compound prepared in Example 4.

Figure 19 is the H NMR spectrum of the conjugated compound prepared in Example 5.

Figure 20 is the carbon NMR spectrum of the conjugated compound prepared in Example 5.

Figure 21 is the excitation spectrum of the conjugated compound prepared in Example 5.

Figure 22 is the emission spectrum of the conjugated compound prepared in Example 5.

Figure 23 is the H NMR spectrum of the conjugated compound prepared in Example 6.

Figure 24 is the carbon NMR spectrum of the conjugated compound prepared in Example 6.

Figure 25 is the excitation spectrum of the conjugated compound prepared in Example 6.

Figure 26 is the emission spectrum of the conjugated compound prepared in Example 6.

Figure 27 is the H NMR spectrum of the conjugated compound prepared in Example 7.

Figure 28 is the carbon NMR spectrum of the conjugated compound prepared in Example 7.

Figure 29 is the excitation spectrum of the conjugated compound prepared in Example 7.

Figure 30 is the emission spectrum of the conjugated compound prepared in Example 7.

Figure 31 is the H NMR spectrum of the conjugated compound prepared in Example 8.

Figure 32 is the carbon NMR spectrum of the conjugated compound prepared in Example 8.

Figure 33 is the excitation spectrum of the conjugated compound prepared in Example 8.

Figure 34 is the emission spectrum of the conjugated compound prepared in Example 8.

Figure 35 is the H NMR spectrum of the conjugated compound prepared in Example 9.

Figure 36 is the carbon NMR spectrum of the conjugated compound prepared in Example 9.

Figure 37 is the excitation spectrum of the conjugated compound prepared in Example 9.

Figure 38 is the emission spectrum of the conjugated compound prepared in Example 9.

Detailed ways

The present invention will be described below through specific examples, but the present invention is not limited thereto.

The experimental methods described in the following examples, unless otherwise specified, are conventional methods; the reagents and materials, unless otherwise specified, can be obtained from commercial sources.

Example 1. Preparation of a compound of formula I with Ar = phenyl, R = n-propyl, R' = methyl (ie D ₁ )

The reaction formula is as follows:

1) Add 159g (0.5mol) 7,7'-dimethoxy-3,4,3',4'-tetrahydro-1,1'-binaphthyl, 49g (0.5mol) to a 1000ml round bottom flask successively mol) maleic anhydride and 500ml xylene, refluxed at 160°C for 10 hours, the reaction system was steam distilled to remove xylene, after the remaining solid was dried, recrystallized with 500ml acetic anhydride, filtered to obtain 87.8g anhydride addition product A, The yield is 82%;

2) Add 8.3g (0.02mol) of addition product A and 40ml of dichloromethane into a 250ml round bottom flask, take 3ml (0.058mol) of liquid bromine and dissolve it in 50ml of acetic acid, put it in a dropping funnel, and slowly drop it in at room temperature In the flask, after 12 hours, filter and wash with a small amount of dichloromethane to obtain 9.1 g of oxidation addition product B with a yield of 80%;

3) Add 5.7g (0.01mol) of oxidation addition product B and 5.9g (0.1mol) of n-propylamine in a 250ml round bottom flask, heat to 40°C in 100ml of DMF and react for 24 hours, then spin dry the reaction solution, a small amount of Chloromethane was washed to obtain 4.26g of product C ₁ with a yield of 70%;

4) Add 61mg (0.1mmol) C ₁ and 36.6mg (0.3mmol) phenylboronic acid into a 25ml two-neck flask, add 5ml toluene, 3ml ethanol and 2ml 2mol/L K ₂ CO ₃ aqueous solution with a syringe under the protection of argon, and ventilate Add catalyst triphenylphosphine palladium 5mg (0.004mmol) after 5 minutes, reflux for 12 hours, take organic layer, _MgSO Dry, filter, spin dry, obtain phenyl substituted hydrohelicene D _43.6mg through column chromatography, Yield 72%.

The structure detection result of this compound is as follows:

¹ H NMR (300MHz, CDCl ₃ ) δ7.52(d, J=7.1Hz, 4H), 7.41(t, J=7.3Hz, 4H), 7.36-7.26(m, 4H), 6.87(s, 2H) , 4.17(d, J=15.9Hz, 2H), 3.67(dd, J=8.4, 5.9Hz, 2H), 3.33(s, 6H), 2.93-2.89(m, 4H), 2.65-2.49(m, 2H ), 1.70-1.77(m, 2H), 0.98(t, J=7.4Hz, 3H).

MALDI-TOF MS: 605 (M ⁺ ).

From the above detection results, it can be seen that the structure of the compound is correct.

Example 2. Preparation of the compound of formula I (namely D ₂ ) with Ar = p-tolyl, R = n-propyl, R' = methyl

The reaction formula is as follows:

1) The preparation of C1 was prepared according to the method in Example 1;

2) Add 61mg (0.1mmol) C ₁ and 40.8mg (0.3mmol) p-toluene boronic acid into a 25ml two-neck flask, add 5ml toluene, 3ml ethanol and 2ml 2mol/LNa ₂ CO ₃ with a syringe under the protection of argon K ₂ CO ₃ aqueous solution, after aeration for 5 minutes, add 5 mg (0.004 mmol) of catalyst triphenylphosphine palladium, reflux for 12 hours, take the organic layer, dry over MgSO ₄ , filter, spin dry, and obtain p-methylphenyl Substituted hydrogenated helicene D ₂ 47.5 mg, yield 75%.

The structure detection result of this compound is as follows:

¹ H NMR (300MHz, CDCl ₃ ) δ7.42(d, J=8.0Hz, 4H), 7.27(s, 2H), 7.22(d, J=7.9Hz, 4H), 6.85(s, 2H), 4.16 (d, J=15.9Hz, 2H), 3.66(t, J=7.1Hz, 2H), 3.31(s, 6H), 2.98-2.80(m, 4H), 2.65-2.50(m, 2H), 2.39( s, 6H), 1.70-1.77 (m, 2H), 0.98 (t, J=7.4Hz, 3H).

MALDI-TOF MS: 633 (M ⁺ ).

From the above detection results, it can be seen that the structure of the compound is correct.

Example 3. Preparation of the compound of formula I with Ar = p-methoxyphenyl, R = n-propyl, R' = methyl (ie D ₃ )

The reaction formula is as follows:

1) The preparation of C1 was prepared according to the method in Example 1;

2) Add 61mg (0.1mmol) of C ₁ and 45.6mg (0.3mmol) of p-methoxyphenylboronic acid into a 25ml two-necked flask, and add 5ml of toluene, 3ml of ethanol and 2ml of 2mol/L K ₂ CO with a syringe under the protection of argon ₃ aqueous solution, after ventilating for 5 minutes, add catalyst triphenylphosphine palladium 5mg (0.004mmol), reflux for 12 hours, take the organic layer, MgSO ₄ dry, filter, spin dry, obtain p-methoxyphenyl substituted by column chromatography Hydrohelicene D ₃ 53.2 mg, yield 80%.

The structure detection result of this compound is as follows:

¹ H NMR (300MHz, CDCl ₃ ) δ7.47(d, J=8.2Hz, 4H), 6.95(d, J=8.2Hz, 4H), 6.85(s, 2H), 4.16(d, J=16.0Hz , 2H), 3.85(s, 6H), 3.73-3.59(m, 2H), 3.32(s, 6H), 2.86-2.91(m, 4H), 2.69-2.45(m, 2H), 1.79-1.68(m , 2H), 0.98(t, J=7.2Hz, 3H).

MALDI-TOF MS: 665 (M ⁺ ).

From the above detection results, it can be seen that the structure of the compound is correct.

Example 4. Preparation of the compound of formula I with Ar = p-chlorophenyl, R = n-propyl, R' = methyl (ie D ₄ )

The reaction formula is as follows:

1) The preparation of C1 was prepared according to the method in Example 1;

2) Add 61mg (0.1mmol) C ₁ and 46.8mg (0.3mmol) p-chlorophenylboronic acid into a 25ml two-neck flask, add 5ml toluene, 3ml ethanol and 2ml 2mol/L K ₂ CO ₃ aqueous solution with a syringe under the protection of argon After ventilating for 5 minutes, add catalyst triphenylphosphine palladium 5mg (0.004mmol), reflux for 12 hours, take the organic layer, _MgSO Dry, filter, spin dry, obtain p-chlorophenyl substituted hydrospiro _D through column chromatography 40.4 mg, 60% yield.

The structure detection result of this compound is as follows:

¹ H NMR (300MHz, CDCl ₃ ) δ7.46(d, J=8.3Hz, 4H), 7.37(d, J=8.3Hz, 4H), 7.26(s, 2H), 6.84(s, 2H), 4.16 (d, J=15.9Hz, 2H), 3.66(td, J=6.9, 1.9Hz, 2H), 3.35(s, 6H), 2.98-2.81(m, 4H), 2.63-2.49(m, 2H), 1.69-1.77(m, 2H), 0.98(t, J=7.4Hz, 3H).

MALDI-TOF MS: 674 (M ⁺ ).

From the above detection results, it can be seen that the structure of the compound is correct.

Example 5. Preparation of the compound of formula I with Ar = m-thienyl, R = n-propyl, R' = methyl (ie D ₁ )

The reaction formula is as follows:

1) The preparation of C1 was prepared according to the method in Example 1;

2) Add 61mg (0.1mmol) C ₁ and 38.4mg (0.3mmol) m-thiophene boronic acid into a 25ml two-neck flask, add 5ml toluene, 3ml ethanol and 2ml 2mol/L K ₂ CO ₃ aqueous solution with a syringe under argon protection, After ventilating for 5 minutes, 5 mg (0.004 mmol) of catalyst triphenylphosphine palladium was added, refluxed for 12 hours, the organic layer was taken, dried over MgSO ₄ , filtered, spin-dried, separated by column chromatography to obtain 45.7 mg of thiophene-substituted hydrohelicene D ₅ , Yield 74%.

The structure detection result of this compound is as follows:

¹ H NMR (300MHz, CDCl ₃ ) δ7.66(dd, J=2.9, 1.0Hz, 2H), 7.50-7.42(m, 4H), 7.35(dd, J=5.0, 3.0Hz, 2H), 6.86( s, 2H), 4.16(d, J=15.9Hz, 2H), 3.66(td, J=6.9, 1.9Hz, 2H), 3.35(s, 6H), 2.98-2.81(m, 4H), 2.63-2.49 (m, 2H), 1.69-1.77(m, 2H), 0.98(t, J=7.4Hz, 3H).

MALDI-TOF MS: 617 (M ⁺ ).

From the above detection results, it can be seen that the structure of the compound is correct.

Example 6. Preparation of the compound of formula I with Ar = phenyl, R = n-dodecyl, R' = methyl (ie D ₆ )

The reaction formula is as follows:

1) The preparation of B is prepared according to the method in Example 1;

2) Add 5.7g (0.01mol) of oxidative addition product B and 18.5g (0.1mol) of n-dodecyl to a 250ml round-bottomed flask, heat to 100°C in 100ml DMF and react for 24 hours, then spin dry the reaction solution , washed with a small amount of dichloromethane to obtain 6.26g of product C ₂ , with a yield of 85%;

3) Add 74mg of C ₂ (0.1mmol) and 36.6mg (0.3mmol) of phenylboronic acid into a 25ml two-neck flask, add 5ml of toluene, 3ml of ethanol and 2ml of 2mol/L K ₂ CO ₃ aqueous solution with a syringe under the protection of argon, and ventilate Add catalyst triphenylphosphine palladium 5mg (0.004mmol) after 5 minutes, reflux for 12 hours, take organic layer, _MgSO Dry, filter, spin dry, obtain phenyl substituted hydrohelicene D _58.5mg through column chromatography, Yield 80%.

The structure detection result of this compound is as follows:

¹ H NMR (300MHz, CDCl ₃ ) δ7.53(d, J=7.5Hz, 4H), 7.41(t, J=7.3Hz, 4H), 7.37-7.27(m, 4H), 6.87(s, 2H) , 4.17(d, J=15.7Hz, 2H), 3.69(t, J=6.8Hz, 2H), 3.33(s, 6H), 2.88-2.92(m, 4H), 2.55-2.64(m, 2H), 1.68-1.70(m, 2H), 1.29-1.35(m, 19H), 0.88(t, J=5.6Hz, 3H).

MALDI-TOF MS: 731 (M ⁺ ).

From the above detection results, it can be seen that the structure of the compound is correct.

Example 7. Preparation of the compound of formula I with Ar = p-formylphenyl, R = n-dodecyl, R' = methyl (ie D ₇ )

The reaction formula is as follows:

1) The preparation of _C2 is prepared according to the method in Example 6;

2) Add 74mg C ₂ (0.1mmol) and 45mg (0.3mmol) p-formylphenylboronic acid into a 25ml two-neck flask, add 5ml toluene, 3ml ethanol and 2ml 2mol/L K ₂ CO ₃ aqueous solution with a syringe under argon protection , add catalyst triphenylphosphine palladium 5mg (0.004mmol) after ventilating for 5 minutes, reflux 12 hours, take organic layer, _MgSO Dry, filter, spin dry, obtain p-formylphenyl substituted hydrogenated helicene through column chromatography D ₇ 23.6 mg, yield 43%.

The structure detection result of this compound is as follows:

¹ H NMR (300MHz, CDCl ₃ ) δ10.05(s, 2H), 7.92(d, J=8.2Hz, 4H), 7.71(d, J=8.1Hz, 4H), 7.34(s, 2H), 6.88 (s, 2H), 4.19 (d, J = 15.9Hz, 2H), 3.69 (t, J = 6.6Hz, 2H), 3.35 (s, 6H), 3.02-2.83 (m, 4H), 2.66-2.45 ( m, 2H), 1.77-1.64(m, 2H), 1.26-1.34(m, 18H), 0.88(t, J=6.6Hz, 3H).

MALDI-TOF MS: 787 (M ⁺ ).

From the above detection results, it can be seen that the structure of the compound is correct.

Example 8. Preparation of the compound of formula I with Ar = p-methoxyphenyl, R = n-dodecyl, R' = methyl (ie D ₈ )

The reaction formula is as follows:

1) The preparation of _C2 is prepared according to the method in Example 6;

2) Add 74mg C ₂ (0.1mmol) and 45.6mg (0.3mmol) p-methoxyphenylboronic acid into a 25ml two-neck flask, add 5ml toluene, 3ml ethanol and 2ml 2mol/L K ₂ CO with a syringe under argon protection ₃ aqueous solution, after ventilating for 5 minutes, add catalyst triphenylphosphine palladium 5mg (0.004mmol), reflux for 12 hours, take the organic layer, MgSO ₄ dry, filter, spin dry, obtain p-methoxyphenyl substituted by column chromatography Hydrogenated helicene D ₈ 65.7 mg, yield 83%.

The structure detection result of this compound is as follows:

¹ H NMR (300MHz, CDCl ₃ ) δ7.47(d, J=8.7Hz, 4H), 7.26(s, 2H), 6.95(d, J=8.7Hz, 4H), 6.85(s, 2H), 4.15 (d, J=15.8Hz, 2H), 3.85(s, 6H), 3.68(t, J=6.4Hz, 2H), 3.32(s, 6H), 2.98-2.76(m, 4H), 2.66-2.45( m, 2H), 1.75-1.61(m, 2H), 1.26-1.34(m, 18H), 0.87(t, J=6.6Hz, 3H).

MALDI-TOF MS: 791 (M ⁺ ).

From the above detection results, it can be seen that the structure of the compound is correct.

Example 9. Preparation of the compound of formula I with Ar = p-chlorophenyl, R = n-dodecyl, R' = methyl (ie D ₉ )

The reaction formula is as follows:

1) The preparation of _C2 is prepared according to the method in Example 6;

2) Add 74mg C ₂ (0.1mmol) and 46.8mg (0.3mmol) p-chlorophenylboronic acid into a 25ml two-neck flask, add 5ml toluene, 3ml ethanol and 2ml 2mol/L K ₂ CO ₃ aqueous solution with a syringe under argon protection , add catalyst triphenylphosphine palladium 5mg (0.004mmol) after ventilating for 5 minutes, reflux 12 hours, take organic layer, MgSO _4Dry , filter, spin dry, obtain p-chlorophenyl substituted hydrogenated helicene D through column chromatography ₉ 51.2 mg, 64% yield.

The structure detection result of this compound is as follows:

¹ H NMR (300MHz, CDCl ₃ ) δ7.46(d, J=8.3Hz, 4H), 7.37(d, J=8.3Hz, 4H), 7.26(s, 2H), 6.84(s, 2H), 4.17 (d, J=16.1Hz, 2H), 3.68(t, J=6.2Hz, 2H), 3.31(s, 6H), 2.92-2.87(m, 4H), 2.67-2.47(m, 2H), 1.76- 1.62(m, 2H), 1.25-1.34(m, 18H), 0.87(t, J=5.9Hz, 3H).

MALDI-TOF MS: 800 (M ⁺ ).

From the above detection results, it can be seen that the structure of the compound is correct.

The measurement of the optical properties of the conjugated compound prepared in embodiment 10 and embodiment 1-9

The analyte was measured with toluene as solvent for UV-Vis absorption spectrum and fluorescence spectrum, and the data in Table 1 were obtained.

Table 1, list of optical properties of conjugated compounds prepared in Examples 1-9

The excitation wavelengths and emission wavelengths of the conjugated compounds prepared in Examples 1-9 in Table 1 were measured in toluene solvent. This series of compounds also has fluorescence in the solid state, and fluorescence also exists when this series of compounds are made into organic thin films, which provides a basis for the application of this type of molecules in light-emitting materials.

The conjugated compounds prepared in Examples 1-9 all appear yellow-green in toluene solvent.

Claims (10)

1. general structure is suc as formula the conjugated compound shown in the I:

Among the said formula I, Ar is selected from any one in phenyl, substituted phenyl and the heterocyclic radical; R is n-propyl or dodecyl; R ' is a methyl.

2. conjugated compound according to claim 1 is characterized in that: said heterocyclic radical is the 3-thienyl;

Said substituted phenyl be following any one: 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-formyl radical phenyl and 4-chloro-phenyl-.

3. prepare the method for conjugated compound shown in the formula I, comprise the steps:

1) with 7,7 '-dimethoxy-3,4,3 ', 4 '-tetrahydrochysene-1,1 '-naphthyl naphthalene and MALEIC ANHYDRIDE carry out back flow reaction in organic solvent, obtain the compound shown in the formula II;

2) compound shown in the formula II is dissolved in the methylene dichloride, and reacts, obtain the compound shown in the formula III to the acetic acid soln of dropping liquid bromine wherein;

3) compound shown in the formula III and Tri N-Propyl Amine or dodecyl amine are reacted in organic solvent, obtain the compound shown in the formula IV;

The definition cotype I of R among the formula IV;

4) under the condition of catalyzer triphenyl phosphorus palladium and alkali existence, the fragrant boric acid shown in compound shown in the formula IV and the formula V is reacted in organic solvent, obtain the conjugated compound shown in the formula I;

Ar-B(OH) ₂

(formula V)

The definition cotype I of Ar among the formula V.

4. method according to claim 3 is characterized in that: in the step 1), and said MALEIC ANHYDRIDE and 7,7 '-dimethoxy-3,4,3 ', 4 '-tetrahydrochysene-1, the mol ratio of 1 '-naphthyl naphthalene is 1: 1-1.5: 1, be specially 1: 1; Said organic solvent is a YLENE; In the said back flow reaction, the reaction times is 6-10 hour, is specially 8-10 hour, and temperature of reaction is 130-160 ℃, is specially 140-150 ℃.

5. according to claim 3 or 4 described methods, it is characterized in that: step 2) in, compound shown in the said formula II and liquid bromine mol ratio are 1: 4-8 was specially 1: 5; The reaction times of said reaction is 8-12 hour, is specially 10-12 hour, and temperature of reaction is a room temperature, is specially 15-18 ℃; Said acetate and liquid bromine volume ratio 5: 1-10: 1, be specially 8: 1-9: 1.

6. according to each described method among the claim 3-5, it is characterized in that: in the step 3), said organic solvent is N or toluene; Said reaction needs is carried out under argon shield.

7. according to each described method among the claim 3-6, it is characterized in that: in the step 3), compound shown in the said formula III and Tri N-Propyl Amine react, and the mol ratio of compound shown in the said formula III and Tri N-Propyl Amine is 1: 5-1: 10, be specially 1: 8; The reaction times of said reaction is 12-24 hour, is specially 20-24 hour, and temperature of reaction is 30-70 ℃, is specially 40-60 ℃.

8. according to each described method among the claim 3-6; It is characterized in that: in the step 3); Compound shown in the said formula III and dodecyl amine react, and the mol ratio of compound shown in the said formula III and dodecyl amine is 1: 1-1: 3, be specially 1: 1; The reaction times of said reaction is 12-24 hour, is specially 20-24 hour, and temperature of reaction is 90-110 ℃, is specially 95-100 ℃.

9. according to each described method among the claim 3-8, it is characterized in that: in the step 4), said alkali is salt of wormwood; Said organic solvent is selected from any one in following two kinds of mixed solutions: 1) toluene, ethanol and the water mixed solvent that mixes to obtain according to volume ratio 8-5: 4-3: 3-1,2) YLENE, ethanol mixes the mixed solvent that obtains with water according to volume ratio 8-5: 4-3: 3-1; Said reaction needs is carried out under argon shield;

The mol ratio of the fragrant boric acid shown in compound shown in said triphenyl phosphorus palladium, the formula IV and the formula V is 0.02-0.1: 1: 2-3 was specially 0.043: 1: 3; The reaction times of said reaction is 16-24 hour, is specially 20-24 hour, and temperature of reaction is 90-110 ℃, is specially 95-100 ℃.

10. claim 1 or 2 described conjugations are combined in the application in preparation luminous organic material or the organic fluorescent dye.

Images