CN101274933B - Dipyrene-3,4,6,7:12,13,15,16-octacarboxylic tertimide compound and preparation thereof - Google Patents
Dipyrene-3,4,6,7:12,13,15,16-octacarboxylic tertimide compound and preparation thereof Download PDFInfo
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Abstract
The invention relates to a second perylene-3, 4, 6, 7:12, 13, 15, 16-octocarboxylic acid tetraimide compound and a preparation method thereof. The preparation method comprises the steps: 1, 6, 7, 12-tetrahalogenoperylene-3, 4:9, 10-tetra-carboxylic acid diimide compounds, a catalyst, a ligand and an inorganic base are mixed, then dimethylsulfoxide, N, N-dimethylformamide, N-methyl pyrrolidone or the mixing solvent of dimethylsulfoxide, N, N- dimethylformamide and N-methyl pyrrolidone are added, reacting under the protection of inert gas, the product is dissolved by organic solvents such as dichloromethane, ethyl acetate or toluene, etc., washed in sodium chloride solution, dried and filtered, and the solvents are evaporated, column chromatographic separation is carried out so as to obtainthe second perylene-3, 4, 6, 7:12, 13, 15, 16-octocarboxylic acid tetraimide compound shown as the formula above, and the yield after purification is 10 to 50 percent, wherein, X is hydrogen, chlorine or bromine; R<1> and R<2> are respectively hydrogen, C1-C30 alkyl, C1-C30 alkoxy and aryl groups substituted or not substituted.
Description
Technical field
The present invention relates to Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide analog compounds, and the preparation method of this compound.
Background technology
Perylene-3,4:9,10-tetracarboxylic acid diimide are a kind of important industrial dyes, this is because this compounds has good light stability, thermostability and unreactiveness, also has the high tinting strength from the redness to the purple (Heterocycles, 1995,40,477～500).Except as dyestuff ， perylene-3,4:9,10-tetracarboxylic acid diimide have also obtained using widely aspect functional materials, as (Science, 2001,293,1119～1122 such as solar cell material, liquid crystal material, organic field-effect tube, luminescent materials; 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, by advantages of simplicity and high efficiency synthetic method De Dao perylene-3,4:9,10-tetracarboxylic acid diimide compounds has important Research Significance and practical value.
Although domestic and international researcher Tong Guo Dui perylene-3,4:9,10-tetracarboxylic acid diimide compounds synthetic carried out extensive and deep research and obtained Duo Zhong perylene-3,4:9,10-tetracarboxylic acid diimide compounds (Chem.Commun., 2006,4587～4589; Chem.Commun., 2005,4045～4046; J.Mater.Chem., 1998,8,2357～2369 etc.), but up to now, also do not see Er Bing perylene-3,4,6,7:12,13,15, the report of 16-eight carboxylic acids four imide analog compounds and preparation method thereof aspect.
Summary of the invention
The object of the present invention is to provide Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide analog compounds.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned purpose one compound.
Er Bing perylene-3,4,6 of the present invention, 7:12,13,15,16-eight carboxylic acids four imide analog compounds structures as shown in the formula:
Wherein: X is hydrogen, chlorine or bromine; R
1And R
2Be hydrogen, C independently
1～C
30Alkyl, C
1～C
30Alkoxyl group, replacement or unsubstituted aryl.
Described substituting group is C
1～C
20Alkyl or C
1～C
20Alkoxyl group.
Er Bing perylene-3,4,6 of the present invention, 7:12,13,15, the preparation method of 16-eight carboxylic acids four imide analog compounds may further comprise the steps:
(1). with 1,6,7,12-four halogen are for perylene-3,4:9,10-tetracarboxylic acid diimide compounds, catalyzer, part and mineral alkali mix for 1:1～12:1～15:1～16 in molar ratio;
(2). in the mixture of step (1) preparation, add organic solvent, 1,6,7,12-four halogen are for perylene-3,4:9, the ratio of 10-tetracarboxylic acid diimide compounds and organic solvent is 0.01～1.0mmol/ml;
(3). under protection of inert gas, the prepared mixing solutions of step (2) is heated to 30 ℃～150 ℃ reacts, reaction finishes; product is through organic solvent dissolution, and sodium chloride aqueous solution washs, siccative dryings such as anhydrous sodium sulphate; filter, solvent evaporated, silica gel column chromatography separates the Er Bing perylene-3 that obtains being shown below; 4; 6,7:12,13; 15,16-eight carboxylic acids four imide analog compounds.
Wherein: X is hydrogen, chlorine or bromine; R
1And R
2Be hydrogen, C independently
1～C
30Alkyl, C
1～C
30Alkoxyl group, replacement or unsubstituted aryl.
Described substituting group is C
1～C
20Alkyl or C
1～C
20Alkoxyl group.
The described organic solvent of step (2) is dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMF), N-Methyl pyrrolidone (NMP) or their any mixed solvent.
Step (3) is described to be heated to 30 ℃～150 ℃ with mixing solutions and to react, and the reaction times approximately is 6～40 hours.
The described organic solvent of step (3) is methylene dichloride, ethyl acetate or toluene etc.
The described solvent evaporated of step (3) is preferably 60 ℃ of following solvent evaporated.
1,6,7 of the present invention's employing, 12-four Lu Dai perylenes-3,4:9,10-tetracarboxylic acid diimide compounds contains substituting group or does not contain substituting group; Contain substituting group or do not contain substituent 1,6,7,12-four Lu Dai perylenes-3,4:9,10-tetracarboxylic acid diimide compounds is 1,6,7,12-Si Lv perylene-3,4:9,10-tetracarboxylic acid diimide compound, 1,6,7,12-Si Xiu perylene-3,4:9, the mixture of one or more in the 10-tetracarboxylic acid diimide compound etc.Described substituting group is selected from hydrogen, C
1～C
30Alkyl, C
1～C
30Alkoxyl group, C
1～C
20Alkyl or C
1～C
20A kind of in that alkoxyl group replaces or the unsubstituted aryl.
The catalyzer that the present invention adopts is one or more the mixture in positive cuprous salt such as cuprous iodide, cuprous bromide or the cuprous chloride.
The part that the present invention adopts is amino acid such as L-proline(Pro), N-methyl aminoacetic acid or N, the mixture of one or more in the N-dimethylamino acetate etc.
The mineral alkali that the present invention adopts is one or more the mixture etc. in salt of wormwood, yellow soda ash, cesium carbonate, potassium hydroxide, the sodium hydroxide.
Described rare gas element comprises nitrogen or argon gas.
The productive rate of the target product that the present invention obtains after separating purification is 10%～50%.The gained compound through nuclear magnetic resonance map (
1H-NMR,
13C-NMR), mass spectrum (MS) conclusive evidence, structure is errorless.
Raw material of the present invention all can buy or synthesize according to prior art from the market; As 1,6,7,12-four Lu Dai perylenes-3,4:9,10-tetracarboxylic acid diimide compounds are by document (J.Org.Chem., 2002,67,3037～3044; J.Org.Chem., 2004,69,7933～7939) the report method is synthetic.
Er Bing perylene-3,4,6 of the present invention, 7:12,13,15,16-eight carboxylic acids four imide analog compounds can be used as industrial dye, solar cell material, liquid crystal material, organic field-effect tube, luminescent material etc.
The invention has the advantages that:
1. synthetic method is simple, the compound purity height that obtains.
2. this compounds has satisfactory stability, and the solution that is made into is placed the not change of its ultraviolet absorption peak several weeks in air.
3. this compounds is that the visible light of 400nm～700nm has stronger absorption to wavelength.
Description of drawings
Fig. 1. the N of the embodiment of the invention 1, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-1,9,10,18-tetrachloro two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums.
Fig. 2. the N of the embodiment of the invention 1, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-1,9,10,18-tetrachloro two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four are imido
1H-NMR figure.
Fig. 3. the N of the embodiment of the invention 1, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-1,9,10,18-tetrachloro two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four are imido
13C-NMR figure.
Fig. 4. the N of the embodiment of the invention 2, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums.
Fig. 5. the N of the embodiment of the invention 2, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four are imido
1H-NMR figure.
Fig. 6. the N of the embodiment of the invention 1, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-1,9,10,18-tetrachloro two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido ultraviolet-visible absorption spectroscopy figure.
Fig. 7. the N of the embodiment of the invention 2, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido ultraviolet-visible absorption spectroscopy figure.
Fig. 8. the N of the embodiment of the invention 3, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-1,9,10,18-tetrabromo two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums.
Fig. 9. the N of the embodiment of the invention 5, N ', N ", N " and '-four (2-ethylhexyl)-1,9,10,18-tetrachloro two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums.
Figure 10. the N of the embodiment of the invention 7, N ', N ", N " '-tetra-n-butyl-1,9,10,18-tetrachloro two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums.
Figure 11. the N of the embodiment of the invention 7, N ', N ", N " '-tetra-n-butyl-1,9,10,18-tetrachloro two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four are imido
1H-NMR figure.
Figure 12. the N of the embodiment of the invention 8, N ', N ", N " and '-four phenmethyl-1,9,10,18-tetrachloro two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums.
Figure 13. the N of the embodiment of the invention 8, N ', N ", N " and '-four phenmethyl-1,9,10,18-tetrachloro two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four are imido
1H-NMR figure.
Figure 14. the N of the embodiment of the invention 8, N ', N ", N " and '-four phenmethyl-1,9,10,18-tetrachloro two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four are imido
13C-NMR figure.
Embodiment
Embodiment 1 (N, N ', N ", N " '-four (2, the 6-diisopropyl phenyl)-1,9,10,18-tetrachloro Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imides)
Concrete synthesis step is:
1. with 1mmol N, N '-two (2, the 6-diisopropyl phenyl)-1,6,7,12-Si Lv perylene-3,4:9,10-tetracarboxylic acid diimide and 6mmol cuprous chloride, 7mmol L-proline(Pro), 8mmol Anhydrous potassium carbonate mix;
2. in the mixture of step 1 preparation, add the 10ml dimethyl sulfoxide (DMSO);
3. under nitrogen protection, the mixing solutions that step 2 is prepared is heated to 75 ℃, reacts 12 hours; After reaction finished, product was through acetic acid ethyl dissolution, and sodium chloride aqueous solution washs, anhydrous sodium sulfate drying, filter, 60 ℃ of following solvent evaporated, the silica gel column chromatography separation obtains product N, N '; N ", N " and '-four (2, the 6-diisopropyl phenyl)-1,9; 10,18-tetrachloro Er Bing perylene-3,4; 6,7:12,13; 15,16-eight carboxylic acids four imide 124mg, productive rate is 16%.Black powder, and MS (MALDI-TOF, m/z): 1553.3.Anal.Calcd.for:C
96H
74Cl
4N
4O
8(molecular weight: 1553.45);
1H-NMR (CDCl
3, 400MHZ): δ=10.07 (2H, s), 9.30 (2H, s), 9.05 (2H, s), 7.47 (8H, m), 7.30 (2H, m), 7.24 (2H, m), 3.51 (2H, m), 2.93 (2H, m), 2.49 (2H, m), 2.22 (2H, m), 1.58 (6H, d), 1.41 (6H, d), 1.25 (6H, d), 1.07 (6H, d), 0.98 (12H, m), 0.80 (6H, m), 0.78 (6H, d).
13C-NMR(CDCl
3，75MHZ)：δ＝163.2，162.8，162.7，162.5，146.4，146.5，145.2，144.8，136.5，136.4，136.2，132.9，131.3，130.4，130.2，129.7，127.2，126.2，126.1，125.4，124.6，124.4，124.3，124.0，123.6，121.6，121.3，118.7，31.5，30.0，29.3，29.2，29.1，24.6，24.4，24.2，24.0，23.9，23.7，22.6，14.1。
N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-1,9,10,18-tetrachloro Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 1;
1H-NMR figure as shown in Figure 2;
13C-NMR figure as shown in Figure 3; Ultraviolet-visible absorption spectroscopy figure as shown in Figure 6.
Embodiment 2 (N, N ', N ", N " '-four (2, the 6-diisopropyl phenyl)-Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imides)
Concrete synthesis step is:
1. with 1mmol N, N '-two (2, the 6-diisopropyl phenyl)-1,6,7,12-Si Lv perylene-3,4: 9,10-tetracarboxylic acid diimide and 6mmol cuprous chloride, 7mmol L-proline(Pro), 8mmol Anhydrous potassium carbonate mix;
2. in the mixture of step 1 preparation, add the 10ml dimethyl sulfoxide (DMSO);
3. under nitrogen protection, the mixing solutions that step 2 is prepared is heated to 110 ℃, reacts 15 hours; After reaction finished, product was through acetic acid ethyl dissolution, and sodium chloride aqueous solution washs, anhydrous sodium sulfate drying filters 60 ℃ of following solvent evaporated, the silica gel column chromatography separation obtains product N, N ', N "; N " '-four (2, the 6-diisopropyl phenyl)-Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 212mg, productive rate is 30%.The atropurpureus powder, and MS (MALDI-TOF, m/z): 1414.9.Anal.Calcd.for:C
96H
78N
4O
8(molecular weight: 1415.7);
1H-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).
N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 4;
1H-NMR figure as shown in Figure 5; Ultraviolet-visible absorption spectroscopy figure as shown in Figure 7.
Embodiment 3 (N, N ', N ", N " '-four (2, the 6-diisopropyl phenyl)-1,9,10,18-tetrabromo Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imides)
Concrete synthesis step is:
1. with 1mmol N, N '-two (2, the 6-diisopropyl phenyl)-1,6,7,12-Si Xiu perylene-3,4: 9,10-tetracarboxylic acid diimide and 6mmol cuprous chloride, 7mmol L-proline(Pro), 8mmol Anhydrous potassium carbonate mix;
2. in the mixture of step 1 preparation, add the 10ml dimethyl sulfoxide (DMSO);
3. under nitrogen protection, the mixing solutions that step 2 is prepared is heated to 40 ℃, reacts 10 hours; After reaction finished, product was through acetic acid ethyl dissolution, and sodium chloride aqueous solution washs, anhydrous sodium sulfate drying, filter, 60 ℃ of following solvent evaporated, the silica gel column chromatography separation obtains product N, N '; N ", N " and '-four (2, the 6-diisopropyl phenyl)-1,9; 10,18-tetrabromo Er Bing perylene-3,4; 6,7:12,13; 15,16-eight carboxylic acids four imide 242mg, productive rate is 28%.Black powder, and MS (MALDI-TOF, m/z): 1731.0.Anal.Calcd.for:C
96H
74Br
4N
4O
8(molecular weight: 1731.25).
N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-1,9,10,18-tetrabromo Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 8.
Embodiment 4 (N, N ', N ", N " '-four (2, the 6-diisopropyl phenyl)-Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imides)
Concrete synthesis step is:
1. with 1mmol N, N '-two (2, the 6-diisopropyl phenyl)-1,6,7,12-Si Xiu perylene-3,4: 9,10-tetracarboxylic acid diimide and 6mmol cuprous chloride, 7mmol L-proline(Pro), 8mmol Anhydrous potassium carbonate mix;
2. in the mixture of step 1 preparation, add the 10ml dimethyl sulfoxide (DMSO);
3. under nitrogen protection, the mixing solutions that step 2 is prepared is heated to 110 ℃, reacts 16 hours; After reaction finished, product was through acetic acid ethyl dissolution, and sodium chloride aqueous solution washs, anhydrous sodium sulfate drying filters 60 ℃ of following solvent evaporated, the silica gel column chromatography separation obtains product N, N ', N "; N " '-four (2, the 6-diisopropyl phenyl)-Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 260mg, productive rate is 37%.The atropurpureus powder, and MS (MALDI-TOF, m/z): 1414.9.Anal.Calcd.for:C
96H
78N
4O
8(molecular weight: 1415.7);
1H-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 5 (N, N ', N ", N " '-four (2-ethylhexyl)-1,9,10,18-tetrachloro Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imides)
Concrete synthesis step is:
1. with 1mmol N, N '-two (2-ethylhexyl)-1,6,7,12-Si Lv perylene-3,4:9,10-tetracarboxylic acid diimide and 5mmol cuprous iodide, 8mmol N-methyl aminoacetic acid, 10mmol anhydrous sodium carbonate mix;
2. in the mixture of step 1 preparation, add the 9ml dimethyl sulfoxide (DMSO);
3. under nitrogen protection, the mixing solutions that step 2 is prepared is heated to 70 ℃, reacts 20 hours; After reaction finished, product dissolved through methylene dichloride, sodium chloride aqueous solution washing, anhydrous sodium sulfate drying, filter, 60 ℃ of following solvent evaporated, the silica gel column chromatography separation obtains N, N '; N ", N " and '-four (2-ethylhexyl)-1,9; 10,18-tetrachloro Er Bing perylene-3,4; 6,7:12,13; 15,16-eight carboxylic acids four imide 170mg, productive rate is 25%.Black powder, and MS (MALDI-TOF, m/z): 1361.8.Anal.Calcd.for:C
80H
74Cl
4N
4O
8(molecular weight: 1361.28).
N, N ', N ", N " and '-four (2-ethylhexyl)-1,9,10,18-tetrachloro Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 9.
Embodiment 6 (N, N ', N ", N " '-four (2-ethylhexyl)-Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imides)
Concrete synthesis step is:
1. with 1mmol N, N '-two (2-ethylhexyl)-1,6,7,12-Si Lv perylene-3,4:9,10-tetracarboxylic acid diimide and 5mmol cuprous iodide, 8mmol N-methyl aminoacetic acid, 10mmol anhydrous sodium carbonate mix;
2. in the mixture of step 1 preparation, add the 9ml dimethyl sulfoxide (DMSO);
3. under nitrogen protection, the mixing solutions that step 2 is prepared is heated to 120 ℃, reacts 24 hours; After reaction finished, product dissolved through methylene dichloride, the sodium chloride aqueous solution washing, anhydrous sodium sulfate drying filters 60 ℃ of following solvent evaporated, the silica gel column chromatography separation obtains N, N ', N "; N " '-four (2-ethylhexyl)-Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 160mg, productive rate is 26%.The atropurpureus powder, and MS (MALDI-TOF, m/z): 1222.8.Anal.Calcd.for:C
80H
78N
4O
8(molecular weight: 1223.5).
Embodiment 7 (N, N ', N ", N " '-tetra-n-butyl-1,9,10,18-tetrachloro Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imides)
Concrete synthesis step is:
1. with 1mmol N, N '-di-n-butyl-1,6,7,12-four chlorine perylenes-3,4:9,10-tetracarboxylic acid diimide and 10mmol cuprous bromide, 11mmolN, N-dimethylamino acetate, 10mmol cesium carbonate mix;
2. in the mixture of step 1 preparation, add the 12ml N-Methyl pyrrolidone;
3. under argon shield, the mixing solutions that step 2 is prepared is heated to 60 ℃, reacts 24 hours; After reaction finished, product dissolved through methylene dichloride, sodium chloride aqueous solution washing, anhydrous sodium sulfate drying, filter, 60 ℃ of following solvent evaporated, the silica gel column chromatography separation obtains N, N '; N ", N " '-tetra-n-butyl-1,9; 10,18-tetrachloro Er Bing perylene-3,4; 6,7:12,13; 15,16-eight carboxylic acids four imide 142mg, productive rate is 25%.Black powder, and MS (MALDI-TOF, m/z): 1137.1.Anal.Calcd.for:C
64H
42Cl
4N
4O
8(molecular weight: 1136.8);
1H-NMR (CDCl
3, 400MHZ): δ=10.05 (2H, s), 9.25 (2H, s), 9.00 (2H, s), 4.43 (4H, t), 4.30 (4H, t), 1.96 (4H, m), 1.80 (4H, m), 1.58 (8H, m), 1.05 (12H, m).
N, N ', N ", N " '-tetra-n-butyl-1,9,10,18-tetrachloro Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in figure 10;
1H-NMR figure as shown in figure 11.
Embodiment 8 (N, N ', N ", N " '-four phenmethyl-1,9,10,18-tetrachloro Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imides)
Concrete synthesis step is:
1. with 1mmol N, N '-diphenyl-methyl-1,6,7,12-Si Lv perylene-3,4:9,10-tetracarboxylic acid diimide and 10mmol cuprous iodide, 11mmolL-proline(Pro), 10mmol salt of wormwood mix;
2. in the mixture of step 1 preparation, add the 12ml dimethyl sulfoxide (DMSO);
3. under argon shield, the mixing solutions that step 2 is prepared is heated to 75 ℃, reacts 12 hours; After reaction finished, product was through acetic acid ethyl dissolution, and sodium chloride aqueous solution washs, anhydrous sodium sulfate drying, filter, 60 ℃ of following solvent evaporated, the silica gel column chromatography separation obtains N, N '; N ", N " and '-four phenmethyl-1,9; 10,18-tetrachloro Er Bing perylene-3,4; 6,7:12,13; 15,16-eight carboxylic acids four imide 134mg, productive rate is 21%.Black powder, and MS (MALDI-TOF, m/z): 1272.4.Anal.Calcd.for:C
76H
34Cl
4N
4O
8(molecular weight: 1272.9);
1H-NMR (CDCl
3, 400MHZ): δ=10.00 (2H, s), 9.14 (2H, s), 8.90 (2H, s), 7.65 (4H, m), 7.56 (4H, m), 7.34 (4H, m), 7.20 (8H, m), 5.58 (2H, d), 5.40 (6H, d).
13C-NMR(CDCl
3，75MHZ)：δ＝164.0，163.2，162.7，162.2，136.7，136.6，136.0，135.9，129.9，129.7，129.3，128.9，128.8，128.5，126.9，125.7，124.5，124.2，124.1，123.4，121.9，120.8，118.9，44.7，44.1。
N, N ', N ", N " and '-four phenmethyl-1,9,10,18-tetrachloro Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in figure 12;
1H-NMR figure as shown in figure 13;
13C-NMR figure as shown in figure 14;
Embodiment 9 (N, N ', N ", N " '-tetraphenyl-1,9,10,18-tetrachloro Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imides)
Concrete synthesis step is:
1. with 1mmol N, N '-diphenyl-methyl-1,6,7,12-Si Lv perylene-3,4:9,10-tetracarboxylic acid diimide and 3mmol cuprous chloride, 4mmol L-proline(Pro), 5mmol Anhydrous potassium carbonate mix;
2. in the mixture of step 1 preparation, add the 12ml dimethyl sulfoxide (DMSO);
3. under argon shield, the mixing solutions that step 2 is prepared is heated to 75 ℃, reacts 12 hours; After reaction finished, product was through acetic acid ethyl dissolution, and sodium chloride aqueous solution washs, anhydrous sodium sulfate drying, filter, 60 ℃ of following solvent evaporated, the silica gel column chromatography separation obtains N, N '; N ", N " '-tetraphenyl-1,9; 10,18-tetrachloro Er Bing perylene-3,4; 6,7:12,13; 15,16-eight carboxylic acids four imide 110mg, productive rate is 18%.Black powder, and MS (MALDI-TOF, m/z): 1217.1Anal.Calcd.for:C
72H
26Cl
4N
4O
8(molecular weight: 1216.8).
Embodiment 10 (N, N ', N ", N " '-four (3,4, the 5-trimethoxyphenyl)-1,9,10,18-tetrachloro Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imides)
Concrete synthesis step is:
1. with 1mmol N, N '-two (3,4, the 5-trimethoxyphenyl)-1,6,7,12-tetrachloro-3,4:9,10-perylene tetracarboxylic acid diimides and 10mmol cuprous chloride, 11mmol L-proline(Pro), 12mmol sodium hydroxide mix;
2. in the mixture of step 1 preparation, add 10ml N, dinethylformamide;
3. under nitrogen protection, the mixing solutions that step 2 is prepared is heated to 80 ℃, reacts 8 hours; After reaction finished, product dissolved through toluene, sodium chloride aqueous solution washing, anhydrous sodium sulfate drying, filter, 60 ℃ of following solvent evaporated, the silica gel column chromatography separation obtains N, N '; N ", N " and '-four (3,4, the 5-trimethoxyphenyl)-1; 9,10,18-tetrachloro Er Bing perylene-3,4; 6,7:12,13; 15,16-eight carboxylic acids four imide 181mg, productive rate is 23%.Black powder, and MS (MALDI-TOF, m/z): 1577.3Anal.Calcd.for:C
84H
54Cl
4N
4O
20(molecular weight: 1577.1).
Embodiment 11 (N, N '-two (2-ethylhexyl)-N ", N " '-two (2, the 6-diisopropyl phenyl)-1,9,10,18-tetrachloro Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imides)
Concrete synthesis step is:
1. with 0.5mmol N, N '-two (2-ethylhexyl)-1,6,7,12-tetrachloro-3,4:9, the 10-perylene tetracarboxylic acid diimides, 0.5mmol N, N '-two (2, the 6-diisopropyl phenyl)-1,6,7,12-tetrachloro-3,4:9,10-perylene tetracarboxylic acid diimides and 7mmol cuprous chloride, 8mmolL-proline(Pro), 9mmol Anhydrous potassium carbonate mix;
2. in the mixture of step 1 preparation, add the 10ml dimethyl sulfoxide (DMSO);
3. under nitrogen protection, the mixing solutions that step 2 is prepared is heated to 80 ℃, reacts 16 hours; After reaction finished, product was through acetic acid ethyl dissolution, and sodium chloride aqueous solution washs, anhydrous sodium sulfate drying, filter, 60 ℃ of following solvent evaporated, the silica gel column chromatography separation obtains N, N '-two (2-ethylhexyl)-N "; N " '-two (2, the 6-diisopropyl phenyl)-1,9,10,18-tetrachloro Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 72mg, productive rate is 10%.Black powder, and MS (MALDI-TOF, m/z): 1457.6 Anal.Calcd.for:C
88H
74Cl
4N
4O
8(molecular weight: 1457.36).
Embodiment 12 (N, N ', N ", N " '-four (diethylene glycol monomethyl ether base)-1,9,10,18-tetrachloro Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imides)
Concrete synthesis step is:
1. with 1mmol N, N '-two (diethylene glycol monomethyl ether base)-1,6,7,12-tetrachloro-3,4:9,10-perylene tetracarboxylic acid diimides and 9mmol cuprous chloride, 10mmol L-proline(Pro), 11mmol potassium hydroxide mix;
2. in the mixture of step 1 preparation, add the 10ml dimethyl sulfoxide (DMSO);
3. under nitrogen protection, the mixing solutions that step 2 is prepared is heated to 80 ℃, reacts 10 hours; After reaction finished, product dissolved through toluene, filtered 60 ℃ of following solvent evaporated.The silica gel column chromatography separation obtains N, N ', N ", N " '-four (diethylene glycol monomethyl ether base)-1,9,10,18-tetrachloro Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 139mg, productive rate is 21%.Black powder, and MS (MALDI-TOF, m/z): 1321.1Anal.Calcd.for:C
68H
54Cl
4N
4O
16(molecular weight: 1320.95).
Claims (5)
1. one kind two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide analog compounds is characterized in that the structural formula of this compound is:
Wherein:
X is hydrogen, chlorine or bromine; R
1And R
2Be hydrogen, C independently
1～C
30Alkyl, C
1～C
30Alkoxyl group, replacement or unsubstituted aryl;
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 1,6,7,12-four halogen are for perylene-3, and 4:9,10-tetracarboxylic acid diimide compounds, catalyzer, part and mineral alkali 1: 1～12: 1～15: 1～16 mix;
(2). in the mixture of step (1) preparation, add organic solvent, 1,6,7,12-four halogen are for perylene-3,4:9, the ratio of 10-tetracarboxylic acid diimide compounds and organic solvent is 0.01～1.0mmol/ml;
(3). under protection of inert gas, the prepared mixing solutions of step (2) is heated to 30 ℃～150 ℃ reacts, reaction finishes, product is through organic solvent dissolution, and sodium chloride aqueous solution washs, drying, filter, solvent evaporated, column chromatography for separation obtain Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide analog compounds;
Described part is an amino acid; Described catalyzer is positive cuprous salt;
Described amino acid is L-proline(Pro), N-methyl aminoacetic acid or N, the mixture of one or more in the N-dimethylamino acetate;
The described organic solvent of step (2) is dimethyl sulfoxide (DMSO), N, dinethylformamide, N-Methyl pyrrolidone or their any mixed solvent;
The described organic solvent of step (3) is methylene dichloride, ethyl acetate or toluene.
3. method according to claim 2 is characterized in that: described 1,6,7,12-four Lu Dai perylenes-3,4:9,10-tetracarboxylic acid diimide compounds is to contain substituting group or do not contain substituent 1,6,7,12-Si Lv perylene-3,4:9,10-tetracarboxylic acid diimide compound, 1,6,7,12-Si Xiu perylene-3,4:9, the mixture of one or more in the 10-tetracarboxylic acid diimide compound;
Described substituting group is selected from hydrogen, C
1～C
30Alkyl, C
1～C
30Alkoxyl group, C
1～C
20Alkyl or C
1～C
20A kind of in that alkoxyl group replaces or the unsubstituted aryl.
4. method according to claim 2 is characterized in that: described positive cuprous salt is one or more the mixture in cuprous iodide, cuprous bromide or the cuprous chloride.
5. method according to claim 2 is characterized in that: described mineral alkali is one or more the mixture in salt of wormwood, yellow soda ash, cesium carbonate, potassium hydroxide, the sodium hydroxide.
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| CN101205229B (en) * | 2006-12-20 | 2010-04-14 | 中国科学院化学研究所 | Dizotetracarboxylic dianiline compositions and preparation thereof |
| WO2010111822A1 (en) * | 2009-03-30 | 2010-10-07 | Basf Se | Oligocondensed perylene bisimides |
| CN103193777B (en) * | 2013-03-26 | 2015-04-29 | 中国科学院化学研究所 | Method for preparing zodi-perylene tetracarboxylic acid diimide derivative |
| CN103242312B (en) * | 2013-05-23 | 2015-09-02 | 中国科学院化学研究所 | A kind of efficient method preparing Bing bis-perylene diimides derivative |
| CN108047221B (en) * | 2017-12-19 | 2023-08-01 | 山东省医学科学院药物研究所 | Perylene diimide compound, synthesis method thereof and application thereof in H 2 O 2 Application in detection |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326934A (en) * | 1995-12-18 | 2001-12-19 | Basf公司 | 1,7-twice substituted perylene-3,4,9.10-tetracarboxylic acid diimide |
| WO2005076815A2 (en) * | 2004-01-26 | 2005-08-25 | Northwestern University | PERYLENE n-TYPE SEMICONDUCTORS AND RELATED DEVICES |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326934A (en) * | 1995-12-18 | 2001-12-19 | Basf公司 | 1,7-twice substituted perylene-3,4,9.10-tetracarboxylic acid diimide |
| WO2005076815A2 (en) * | 2004-01-26 | 2005-08-25 | Northwestern University | PERYLENE n-TYPE SEMICONDUCTORS AND RELATED DEVICES |
Non-Patent Citations (1)
| Title |
|---|
| QIAN, H. L.等.Exceptional Coupling of Tetrachloroperylene Bisimide:Combination of Ullmann Reaction and C-H Transformation..J. AM. CHEM. SOC.129 35.2007,129(35),10664-10665. * |
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