CN101205229B - Diperylene tetracarboxylic acid diimide compound and preparation method thereof - Google Patents

Abstract

The invention relates to diperylenetetracarboxylic acid diimide compounds and a preparation method. Mix the halogenated 3,4,9,10-perylenetetracarboxylic acid diimide compound, catalyst, ligand and inorganic base, then add dimethyl sulfoxide or its derivative solvent, and react under the protection of inert gas , the product is dissolved in an organic solvent such as ethyl acetate or toluene, washed with a saturated aqueous sodium chloride solution, dried, filtered, evaporated to dryness, and separated by column chromatography to obtain diperylenetetracarboxylic acid diimide compounds shown in the following formula , and the yield after purification is between 10% and 50%. R ¹ and R ² are independently hydrogen, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, substituted or unsubstituted aryl, aryloxy, arylthio radical, arylamino, heteroaryloxy or heteroarylthio.

Description

Diperylene tetracarboxylic acid diimide compound and preparation method thereof

technical field

The invention relates to a diperylene tetracarboxylic acid diimide compound and a preparation method of the compound.

Background technique

Perylene tetracarboxylic acid diimide is an important industrial dye, because this kind of compound has good light stability, thermal stability and chemical inertness, and high coloring power from red to purple (Heterocycles , 1995, 40, 477-500). Perylenetetracarboxylic acid diimide is not only used as dyestuff, but perylene tetracarboxylic acid diimide has also been widely used in functional materials, such as solar cell materials, liquid crystal materials, organic field effect tubes, luminescent materials, etc. (Science , 2001, 293, 1119～1122; J.Am.Chem.Soc., 2006, 128, 3870～3871; J.Am.Chem.Soc., 2003, 125, 8625～8638; J.Am.Chem.Soc. ., 2003, 125, 437～443; Angew.Chem.Int.Ed., 2004, 43, 6363～6366; Angew.Chem.Int.Ed., 2002, 41, 1900～1904; Angew.Chem.Int. Ed., 1998, 37, 1434-1437, etc.). Therefore, it has important research significance and practical value to obtain perylene tetracarboxylic acid diimide compounds through simple and efficient synthetic methods.

Although scientific research workers at home and abroad have carried out extensive and in-depth research on the synthesis of perylene tetracarboxylic acid diimide compounds, a variety of perylene tetracarboxylic acid diimide compounds (Chem.Commun., 2006, 4587 ～4589; Chem.Commun., 2005, 4045～4046; J.Mater.Chem., 1998, 8, 2357～2369, etc.), but so far, no diperylenetetracarboxylic acid diimides have been seen Compounds and methods for their preparation.

Contents of the invention

The object of the present invention is to provide diperylenetetracarboxylic acid diimides.

Another object of the present invention is to provide a method for preparing the above-mentioned object compound.

Diperylenetetracarboxylic acid diimide compound structure of the present invention is as follows:

Wherein: R ¹ and R ² are independently hydrogen, C ₁ ~C ₃₀ alkyl, C ₁ ~C ₃₀ alkoxy, C ₁ ~C ₃₀ alkylthio, substituted or unsubstituted aryl, aryloxy, Arylthio, arylamino, heteroaryloxy or heteroarylthio.

The substituent is C ₁ -C ₂₀ alkyl or C ₁ -C ₂₀ alkoxy.

The preparation method of diperylenetetracarboxylic acid diimide compound of the present invention comprises the following steps:

(1). The halogenated 3,4,9,10-perylenetetracarboxylic acid diimide compound, catalyst, ligand and inorganic base are in a molar ratio of 1:1～12:1～15:1～16 Mix together;

(2). Add dimethyl sulfoxide (DMSO), derivatives of dimethyl sulfoxide or their mixed solvents to the mixture prepared in step (1), halogenated 3,4,9,10-perylenetetracarboxylic The ratio of acid diimide compound to dimethyl sulfoxide, derivatives of dimethyl sulfoxide or their mixed solvents is 0.01-1.0 mmol/ml;

(3). Under the protection of an inert gas, heat the mixed solution prepared in step (2) to 50°C to 150°C, react for 1 to 5 days until the end of the reaction, and the product is dissolved in an organic solvent such as ethyl acetate or toluene, saturated Wash with sodium chloride aqueous solution, dry with a desiccant such as anhydrous sodium sulfate, filter, evaporate the solvent to dryness below 60°C, and separate by silica gel column chromatography to obtain diperylenetetracarboxylic diimide compounds shown in the following formula.

Wherein: R ¹ and R ² are independently hydrogen, C ₁ ~C ₃₀ alkyl, C ₁ ~C ₃₀ alkoxy, C ₁ ~C ₃₀ alkylthio, substituted or unsubstituted aryl, aryloxy, Arylthio, arylamino, heteroaryloxy or heteroarylthio.

The substituent is C ₁ -C ₂₀ alkyl or C ₁ -C ₂₀ alkoxy.

The halogenated 3,4,9,10-perylene tetracarboxylic acid diimide compound used in the present invention contains substituents or does not contain substituents; the halogenated 3,4,9, which contains substituents or does not contain substituents, 10-perylene tetracarboxylic acid diimide compounds are 1,7-dichloro-3,4,9,10-perylene tetracarboxylic acid diimide compounds, 1,6,7-trichloro-3,4 , 9,10-perylene tetracarboxylic acid diimide compound, 1,6,7,12-tetrachloro-3,4,9,10-perylene tetracarboxylic acid diimide compound, 1,7-dibromo -3,4,9,10-perylene tetracarboxylic acid diimide compound, 1,6,7-tribromo-3,4,9,10-perylene tetracarboxylic acid diimide compound, 1,6, 7,12-tetrabromo-3,4,9,10-perylenetetracarboxylic acid diimide compound, 1,7-diiodo-3,4,9,10-perylenetetracarboxylic acid diimide compound, 1,6,7-triiodo-3,4,9,10-perylenetetracarboxylic acid diimide compound or 1,6,7,12-tetraiodo-3,4,9,10-perylenetetracarboxylic acid One or more mixtures of imide compounds, etc. The substituent is hydrogen, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, C ₁ -C ₂₀ alkyl or C ₁ -C ₂₀ alkoxy Substituted or unsubstituted aryl, aryloxy, arylthio, arylamino, heteroaryloxy or heteroarylthio.

The catalyst used in the present invention is a positive monovalent copper salt such as one or more mixtures of cuprous iodide, cuprous bromide or cuprous chloride.

The ligand used in the present invention is one or more mixtures of amino acids such as L-proline, N-methylaminoacetic acid or N, N-dimethylaminoacetic acid.

The alkali used in the present invention is one or more mixtures of potassium carbonate, sodium carbonate, cesium carbonate, potassium hydroxide and sodium hydroxide.

The derivative of dimethyl sulfoxide used in the present invention is one or a mixture of more than one of diethyl sulfoxide, dipropyl sulfoxide or diisopropyl sulfoxide.

The inert gas includes nitrogen or argon.

The yield of the target product obtained by the invention after separation and purification is 10%-50%. The obtained compound was confirmed by nuclear magnetic resonance spectrum ( ¹ H-NMR) and mass spectrum (MS), and the structure was correct.

The raw materials used in the present invention can be purchased from the market or synthesized according to the prior art; as halogenated 3,4,9,10-perylenetetracarboxylic acid diimides are produced according to the literature (J.Org. Chem., 2002, 67, 3037～3044; J.Org.Chem., 2004, 69, 7933～7939) report method synthesis.

The diperylenetetracarboxylic acid diimide compound of the present invention can be used as industrial dyes, solar cell materials, liquid crystal materials, organic field effect tubes, luminescent materials and the like.

The advantages of the present invention are:

1. The synthetic method is simple, and the obtained compound has high purity.

2. This type of compound has good stability, and the UV absorption peak of the prepared solution does not change after being placed in the air for several weeks.

3. This type of compound has a strong absorption of visible light with a wavelength of 400nm to 700nm.

Description of drawings

Figure 1. 1 H-NMR of N, N', N ", N"'-tetrakis (2,6-diisopropylphenyl)-bis-perylenetetracarboxylic diimide of Example ¹ of the present invention picture.

Fig. 2. the mass spectrogram of N, N', N ", N "'-tetrakis (2,6-diisopropylphenyl)-diperylenetetracarboxylic acid diimide of embodiment 1 of the present invention.

Fig. 3. the N of the present invention embodiment 1, N ', N ", the ultraviolet-visible absorption spectrum of N " '-tetra(2,6-diisopropylphenyl)-bis-perylenetetracarboxylic acid diimide picture.

Detailed ways

Embodiment 1 (N, N ', N ", N " '-four (2,6-diisopropylphenyl)-two perylene tetracarboxylic acid diimides)

Concrete synthetic steps are:

1. 1mmol N, N'-bis(2,6-diisopropylphenyl)-1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic diimide and 6mmol cuprous chloride, 7mmol L-proline, 8mmol anhydrous potassium carbonate are mixed together;

2. Add 10ml dimethyl sulfoxide to the mixture prepared in step 1;

3. Under nitrogen protection, heat the mixed solution prepared in step 2 to 70°C and react for 1.5 days; after the reaction, the product is dissolved in ethyl acetate, washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, filtered, The solvent was evaporated to dryness below 60°C, and the product N, N', N", N"'-tetrakis(2,6-diisopropylphenyl)-diperylenetetracarboxylic acid diimide was obtained by silica gel column chromatography 290 mg, 41% yield. Purple-black powder, MS (MALDI-TOF, m/z): 1414.9. Anal. Calcd for: C ₉₆ H ₇₈ N ₄ O ₈ (molecular weight: 1415.7); ¹ H-NMR (CDCl ₃ , 400MHZ): δ=10.06 (2H,s), 9.47(4H,m), 9.34(2H,d), 9.13(2H,d), 7.52(5H,m), 7.37(7H,m), 1.25(48H,d), 0.83( 8H, m).

^{The 1} H-NMR figure of N, N', N", N"'-tetrakis (2,6-diisopropylphenyl)-diperylenetetracarboxylic acid diimide is shown in Figure 1; the mass spectrum As shown in Figure 2; the UV-Vis absorption spectrum is shown in Figure 3.

Embodiment 2 (N, N', N ", N "'-four (2,6-diisopropylphenyl)-two perylenetetracarboxylic diimides)

Concrete synthetic steps are:

1. 1mmol N, N'-bis(2,6-diisopropylphenyl)-1,6,7,12-tetrabromo-3,4,9,10-perylenetetracarboxylic diimide and 5mmol cuprous chloride, 6mmol L-proline, 9mmol anhydrous potassium carbonate are mixed together;

2. Add 12ml dimethyl sulfoxide to the mixture prepared in step 1;

3. Under nitrogen protection, heat the mixed solution prepared in step 2 to 80°C and react for 1.5 days; after the reaction, the product is dissolved in ethyl acetate, washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, filtered, Evaporate the solvent below 60°C, and separate by silica gel column chromatography to obtain 160 mg of N, N', N", N"'-tetrakis(2,6-diisopropylphenyl)-bisperylenetetracarboxylic acid diimide , the yield was 23%. Purple-black powder, MS (MALDI-TOF, m/z): 1414.9. Anal. Calcd for: C ₉₆ H ₇₈ N ₄ O ₈ (molecular weight: 1415.7); ¹ H-NMR (CDCl ₃ , 400MHZ): δ=10.06 (2H,s), 9.47(4H,m), 9.34(2H,d), 9.13(2H,d), 7.52(5H,m), 7.37(7H,m), 1.25(48H,d), 0.83( 8H, m).

Embodiment 3 (N, N', N ", N "'-four (2,6-diisopropylphenyl)-two perylenetetracarboxylic diimides)

Concrete synthetic steps are:

1. Mix 1mmol N, N'-bis(2,6-diisopropylphenyl)-1,6,7-tribromo-3,4,9,10-perylenetetracarboxylic diimide and 10mmol chlorine Cuprous chloride, 11mmol L-proline, and 12mmol anhydrous potassium carbonate are mixed together;

2. Add 8ml dimethyl sulfoxide to the mixture prepared in step 1;

3. Under nitrogen protection, heat the mixed solution prepared in step 2 to 100°C and react for 2 days; after the reaction, the product is dissolved in ethyl acetate, washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, filtered, Evaporate the solvent below 60°C and separate by silica gel column chromatography to obtain 100 mg of N, N', N", N"'-tetrakis(2,6-diisopropylphenyl)-bisperylenetetracarboxylic acid diimide , the yield was 14%. Purple-black powder, MS (MALDI-TOF, m/z): 1414.9. Anal. Calcd for: C ₉₆ H ₇₈ N ₄ O ₈ (molecular weight: 1415.7); ¹ H-NMR (CDCl ₃ , 400MHZ): δ=10.06 (2H,s), 9.47(4H,m), 9.34(2H,d), 9.13(2H,d), 7.52(5H,m), 7.37(7H,m), 1.25(48H,d), 0.83( 8H, m).

Embodiment 4 (N, N ', N ", N " '-four (2-ethylhexyl)-two perylene tetracarboxylic acid diimides)

Concrete synthetic steps are:

1. 1mmol N, N'-bis(2-ethylhexyl)-1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic acid diimide and 5mmol cuprous iodide , 8mmol N-methylaminoacetic acid, 10mmol anhydrous sodium carbonate are mixed together;

2. Add 9ml diethyl sulfoxide to the mixture prepared in step 1;

3. Under nitrogen protection, heat the mixed solution prepared in step 2 to 100°C and react for 2 days; after the reaction, the product is dissolved in ethyl acetate, washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, filtered, The solvent was evaporated to dryness below 60°C and separated by silica gel column chromatography to obtain 160 mg of N, N', N", N"'-tetrakis(2-ethylhexyl)-diperylenetetracarboxylic acid diimide with a yield of 26 %. Purple-black powder, MS (MALDI-TOF, m/z): 1222.8. Anal. Calcd for: C ₈₀ H ₇₈ N ₄ O ₈ (molecular weight: 1223.5); ¹ H-NMR (CDCl ₃ , 400MHZ): δ=10.07 (2H, s), 9.49 (4H, m), 9.29 (2H, d), 9.09 (2H, d), 3.30 (8H, d), 2.10 (4H, m), 1.16 (56H, m).

Embodiment 5 (N, N ', N ", N " '-tetra-n-dodecyl-two perylene tetracarboxylic acid diimides)

Concrete synthetic steps are:

1. 1mmol N, N'-didodecyl-1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic acid diimides and 10mmol cuprous bromide , 11mmol N, N-dimethylaminoacetic acid, 10mmol cesium carbonate mixed together;

2. Add 12ml of diisopropyl sulfoxide to the mixture prepared in step 1;

3. Under the protection of argon, heat the mixed solution prepared in step 2 to 110°C and react for 3 days; after the reaction, the product is dissolved in ethyl acetate, washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, and filtered , the solvent was evaporated to dryness below 60°C and separated by silica gel column chromatography to obtain 110 mg of N, N', N", N"'-tetra-n-dodecyl-diperylenetetracarboxylic diimide, with a yield of 15% . Black powder, MS (MALDI-TOF, m/z): 1447.7. Anal. Calcd for: C ₉₆ H ₁₁₀ N ₄ O ₈ (molecular weight: 1448.0); ¹ H-NMR (CDCl ₃ , 400MHZ): δ=10.05 ( 2H, s), 9.40 (4H, m), 9.28 (2H, d), 9.00 (2H, d), 3.16 (8H, t), 1.05 (92H, m).

Example 6 (N, N'-two (2-ethylhexyl)-N ", N "'-two (2,6-diisopropylphenyl)-bis-perylenetetracarboxylic acid diimide)

Concrete synthetic steps are:

1. 0.5mmolN, N'-di(2-ethylhexyl)-1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic acid diimide, 0.5mmolN,N '-bis(2,6-diisopropylphenyl)-1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic acid diimide and 7mmol cuprous chloride, 8mmolL-proline, 9mmol anhydrous potassium carbonate are mixed together;

2. Add 10ml dimethyl sulfoxide to the mixture prepared in step 1;

3. Under nitrogen protection, heat the mixed solution prepared in step 2 to 100°C and react for 2 days; after the reaction, the product is dissolved in ethyl acetate, washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, filtered, The solvent was evaporated to dryness below 60°C and separated by silica gel column chromatography to obtain N, N'-bis(2-ethylhexyl)-N", N"'-bis(2,6-diisopropylphenyl)-diiso Perylenetetracarboxylic diimide 66mg, yield 10%. Black powder, MS (MALDI-TOF, m/z): 1319.0. Anal. Calcd for: C ₈₈ H ₇₈ N ₄ O ₈ (molecular weight: 1319.6).

Embodiment 7 (N, N ', N ", N " '-tetraphenyl-two perylene tetracarboxylic acid diimides)

Concrete synthetic steps are:

1. Mix 1mmol N, N'-diphenyl-1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic acid diimide with 3mmol cuprous chloride, 4mmolL-proline Acid, 5mmol anhydrous potassium carbonate are mixed together;

2. Add 8ml dimethyl sulfoxide to the mixture prepared in step 1;

3. Under the protection of nitrogen, heat the mixed solution prepared in step 2 to 80°C and react for 2 days; after the reaction, the product is dissolved in toluene, washed with saturated aqueous sodium chloride, dried with anhydrous sodium sulfate, filtered, 60°C The solvent was evaporated to dryness and separated by silica gel column chromatography to obtain 86 mg of N, N', N", N"'-tetraphenyl-biperylenetetracarboxylic acid diimide with a yield of 16%. Black powder, MS (MALDI-TOF, m/z): 1078.3. Anal. Calcd for: C ₇₂ H ₃₀ N ₄ O ₈ (molecular weight: 1079.0).

Embodiment 8 (N, N', N ", N "'-four (3,4,5-trimethoxyphenyl)-diperylenetetracarboxylic acid diimide)

Concrete synthetic steps are:

1. 1 mmol N, N'-bis(3,4,5-trimethoxyphenyl)-1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic diimide Mix with 10mmol cuprous chloride, 11mmol L-proline, 12mmol sodium hydroxide;

2. Add 10ml diethyl sulfoxide to the mixture prepared in step 1;

3. Under the protection of nitrogen, heat the mixed solution prepared in step 2 to 100°C and react for 3 days; after the reaction, the product is dissolved in toluene, washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, filtered, 60°C The solvent was evaporated to dryness and separated by silica gel column chromatography to obtain 99 mg of N, N', N", N"'-tetrakis(3,4,5-trimethoxyphenyl)-bisperylenetetracarboxylic acid diimide, The yield was 14%. Black powder, MS (MALDI-TOF, m/z): 1438.6. Anal. Calcd for: C ₈₄ H ₅₄ N ₄ O ₂₀ (molecular weight: 1439.4).

Embodiment 9 (N, N ', N ", N " '-four (diethylene glycol monomethyl ether group)-two perylene tetracarboxylic acid diimides)

Concrete synthetic steps are:

1. Mix 1mmol N, N'-bis(diethylene glycol monomethyl ether)-1,6,7,12-tetrachloro-3,4,9,10-perylenetetracarboxylic diimide and 9mmol chlorine Cuprous chloride, 10mmol L-proline, and 11mmol potassium hydroxide are mixed together;

2. Add 10ml dimethyl sulfoxide to the mixture prepared in step 1;

3. Under the protection of nitrogen, the mixed solution prepared in step 2 was heated to 70°C and reacted for 3 days; after the reaction, the product was dissolved in toluene, filtered, and the solvent was evaporated below 60°C. Silica gel column chromatography separated to obtain 89 mg of N, N', N", N"'-tetrakis(diethylene glycol monomethyl ether)-bisperylenetetracarboxylic acid diimide, with a yield of 15%. Black powder, MS (MALDI-TOF, m/z): 1182.4. Anal. Calcd for: C ₆₈ H ₅₄ N ₄ O ₁₆ (molecular weight: 1183.2).

Claims (5)

1. one kind two and perylene tetracarboxylic acid diimides compounds is characterized in that the structural formula of this compound is:

Wherein:

R ¹And R ²Be hydrogen, C independently ₁～C ₃₀Alkyl, C ₁～C ₃₀Alkoxyl group, C ₁～C ₃₀Alkylthio, replacement or unsubstituted aryl, aryloxy, arylthio or arylamino;

Described substituting group is C ₁～C ₂₀Alkyl or C ₁～C ₂₀Alkoxyl group.

2. the preparation method of a compound according to claim 1 is characterized in that, this preparation method may further comprise the steps:

(1). with halo 3,4,9,10-perylene tetracarboxylic acid diimides compounds, catalyzer, part and mineral alkali are 1: 1～12: 1～15: 1～16 to mix in molar ratio;

Described mineral alkali is more than one in salt of wormwood, yellow soda ash, cesium carbonate, potassium hydroxide, the sodium hydroxide;

(2). in the mixture of step (1) preparation, add the derivative of dimethyl sulfoxide (DMSO), dimethyl sulfoxide (DMSO) or their mixed solvent, halo 3,4,9, the ratio of the derivative of 10-perylene tetracarboxylic acid diimides compounds and dimethyl sulfoxide (DMSO), dimethyl sulfoxide (DMSO) or their mixed solvent is 0.01～1.0mmol/ml;

(3). under protection of inert gas, the prepared mixing solutions of step (2) is heated to 50 ℃～150 ℃, reaction finishes, product is through organic solvent dissolution, and saturated sodium-chloride water solution washs, drying, filter, solvent evaporated, column chromatography for separation obtain Er Bing perylene tetracarboxylic acid diimides compounds;

Described halo 3,4,9,10-perylene tetracarboxylic acid diimides compounds be contain substituting group or do not contain substituent 1,7-two chloro-3,4,9,10-perylene tetracarboxylic acid diimides compound, 1,6,7-three chloro-3,4,9,10-perylene tetracarboxylic acid diimides compound, 1,6,7,12-tetrachloro-3,4,9,10-perylene tetracarboxylic acid diimides compound, 1,7-two bromo-3,4,9,10-perylene tetracarboxylic acid diimides compound, 1,6,7-three bromo-3,4,9,10-perylene tetracarboxylic acid diimides compound, 1,6,7,12-tetrabromo-3,4,9,10-perylene tetracarboxylic acid diimides compound, 1,7-two iodo-3,4,9,10-perylene tetracarboxylic acid diimides compound, 1,6,7-three iodo-3,4,9,10-perylene tetracarboxylic acid diimides compound or 1,6,7, the 12-tetraiodo-3,4,9, more than one in the 10-perylene tetracarboxylic acid diimides compound;

Described substituting group is hydrogen, C ₁～C ₃₀Alkyl, C ₁～C ₃₀Alkoxyl group, C ₁～C ₃₀Alkylthio, replacement or unsubstituted aryl, aryloxy, arylthio or arylamino;

The substituting group of the aryl of described replacement is C ₁～C ₂₀Alkyl or C ₁～C ₂₀Alkoxyl group.

Described catalyzer is positive cuprous salt; Described part is an amino acid.

3. method according to claim 2 is characterized in that: described amino acid is L-proline(Pro), N-methyl aminoacetic acid or N, more than one in the N-dimethylamino acetate.

4. method according to claim 2 is characterized in that: described positive cuprous salt is more than one in cuprous iodide, cuprous bromide or the cuprous chloride.

5. method according to claim 2 is characterized in that: the derivative of described dimethyl sulfoxide (DMSO) is more than one in diethyl sulfoxide, dipropyl sulfoxide or the di-isopropyl sulfoxide.

Images