CN101423522A - Diperylene-3,4,6,7:12,13,15,16-octocarboxylic tetraimides compounds and production method thereof - Google Patents
Diperylene-3,4,6,7:12,13,15,16-octocarboxylic tetraimides compounds and production method thereof Download PDFInfo
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- CN101423522A CN101423522A CNA2007101766215A CN200710176621A CN101423522A CN 101423522 A CN101423522 A CN 101423522A CN A2007101766215 A CNA2007101766215 A CN A2007101766215A CN 200710176621 A CN200710176621 A CN 200710176621A CN 101423522 A CN101423522 A CN 101423522A
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Abstract
The invention relates to a bridged dipyrene-3,4,6,7-12, 13, 15, 16-octcarboxylic acid tetraimide compound containing sulphur atoms or selenium atoms and a preparation method thereof. 1,6, 7,12-tetrahalogenated pyrene-3,4-9,10-tetracarboxylic acid diimide compound or 1,9,10,18-tetrahalogenated dipyrene-3,4,6,7-12, 13, 15, 16-octcarboxylic acid tetraimide compound, sodium sulfide or sodium selenide, a catalyst, an amino acid ligand and inorganic base are mixed; then an organic solvent is added; the reaction is carried out under the protection of inert gas; the product is dissolved in the solvent, is washed in sodium chloride aqueous solution, and is dried and filtrated; then the solvent is distilled to dryness; and the bridged dipyrene-3,4,6,7-12, 13, 15, 16-octcarboxylic acid tetraimide compound containing sulphur atoms or selenium atoms in the lateral position showed by formula(I) or (II) is obtained through column chromatography separation. The yield after purification is 10 to 40 percent.
Description
Technical field
The present invention relates to the side position and contain the Er Bing perylene-3,4,6 of sulphur atom or selenium atom bridging, 7:12,13,15,16-eight carboxylic acids four imide analog compounds and preparation method thereof.
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 have the high tinting strength from the redness to the purple (Chem.Commun., 2004,1564～1579; Heterocycles, 1995,40,477～500).Except as dyestuff ， perylene-3,4:9, the 10-tetracarboxylic acid diimide has also obtained widely using aspect functional materials, as (Science, 2001 such as solar cell material, liquid crystal material, organic field-effect tube, luminescent materials, 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.).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.).By advantages of simplicity and high efficiency synthetic method De Dao perylene-3,4:9,10-tetracarboxylic acid diimide analog derivative has important Research Significance and practical value.
In the recent period, we find a kind of efficient activation 1,6,7,12-four Lu Dai perylenes-3,4:9, the transition metal system of 10-tetracarboxylic acid diimide compounds utilizes this system by linked reaction two Fen perylene diimides to be combined along its molecule minor axis, synthesizes the Er Bing perylene-3 of full conjugate, 4,6,7:12,13,15,16-eight carboxylic acids four imide analog compounds (J.Am.Chem.Soc., 2007,129,10664～10665).This compounds has wide range to absorb at visible-range, might be as industrial dye; Electrochemical research shows the electron acceptor(EA) characteristic that it is good simultaneously, is expected to be used widely in the association area of photoelectric device as the novel electronic transport material.In a word, Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide analog compounds are not only the condensed-nuclei aromatics molecule with novel structure, but also are that a class has the functional material that important research was worth and was extensive use of prospect.
In the research of functional materials, people recognize that gradually sulphur atom or the adulterated condensed-nuclei aromatics molecule of selenium atom are one of most promising functional molecular systems.The aromaticity molecule that contains sulphur atom or selenium atom has multiple intermolecular and intramolecular interaction: the effect of Van der Waals that, weak hydrogen bond action, π-π effect and S-S effect or Se-Se effect.In addition, in the condensed-nuclei aromatics system, introduce the character such as stability, solvability and rigidity that sulphur atom or selenium atom will improve molecule, get a good chance of improving the every performance of material.But up to now, also do not see the Er Bing perylene-3,4,6 that contains sulphur atom or selenium atom, 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 the side position to contain the Er Bing perylene-3,4,6 of sulphur atom or selenium atom bridging, 7:12,13,15,16-eight carboxylic acids four imide analog compounds.
Another purpose of the present invention is to provide the 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 are Er Bing perylenes-3,4,6 that sulphur atom or selenium atom bridging are contained in the side position, 7:12,13,15,16-eight carboxylic acids four imide analog compounds, this compound has following structure:
(I) or (II)
Wherein: X is sulphur or selenium; R is selected from hydrogen, C
1～C
30Alkyl, C
1～C
30A kind of in alkoxyl group, replacement or the unsubstituted aryl.
Substituting group in the aryl of described replacement is C
1～C
20Alkyl or C
1～C
20Alkoxyl group.
The Er Bing perylene-3,4,6 of sulphur atom or selenium atom bridging is contained in side of the present invention position, 7:12, and 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 Lu Dai perylenes-3,4:9,10-tetracarboxylic acid diimide compounds or 1,9,10,18-four halo Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imide analog compounds, sodium sulphite or sodium selenide, catalyzer, part and mineral alkali are 1: 4～20: 1～12: 1～15: 1～16 to mix in molar ratio;
(2). in the mixture of step (1) preparation, add organic solvent, 1,6,7,12-four Lu Dai perylenes-3,4:9,10-tetracarboxylic acid diimide compounds or 1,9,10,18-four halo Er Bing perylenes-3,4,6,7:12,13,15, the ratio of 16-eight carboxylic acids, four imide analog 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, the evaporate to dryness organic solvent, column chromatography for separation obtains the Er Bing perylene-3 that sulphur atom or selenium atom bridging are contained in the side position, 4,6,7:12,13,15,16-eight carboxylic acids four imide analog compounds; Productive rate after the purification is 10%～40%.
(I) or (II)
Wherein: X is sulphur or selenium; R is selected from hydrogen, C
1～C
30Alkyl, C
1～C
30A kind of in alkoxyl group, replacement or the unsubstituted aryl.
Substituting group in the aryl of described replacement 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 the mixed solvent between them.
Step (3) is described to be heated to 60 ℃～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, toluene or the mixed solvent between them.
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
30A kind of in alkoxyl group, replacement or the unsubstituted aryl.Substituting group in the aryl of described replacement is C
1～C
20Alkyl or C
1～C
20Alkoxyl group.
1,9,10 of the present invention's employing, 18-four halo Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imide analog compounds are to contain substituting group or do not contain substituent 1,9,10,18-tetrachloro-Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imides, 1,9,10,18-tetrabromo-Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imides, 1,9,10, the 18-tetraiodo-Er Bing perylenes-3,4,6,7:12,13,15, the mixture of one or more in 16-eight carboxylic acids four imides etc.Described substituting group is selected from hydrogen, C
1～C
30Alkyl, C
1～C
30A kind of in alkoxyl group, replacement or the unsubstituted aryl.Substituting group in the aryl of described replacement is C
1～C
20 alkyl or C
1～C
20Alkoxyl group.
The catalyzer that the present invention adopts is one or more the mixture in positive cuprous salt such as cuprous iodide, cuprous bromide, the cuprous chloride.
The part that the present invention adopts is amino acid such as L-proline(Pro), N-methyl aminoacetic acid, 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.
The Er Bing perylene-3,4,6 of sulphur atom bridging is contained in side of the present invention position, 7:12, and 13,15, the preparation method of 16-eight carboxylic acids four imide analog compounds may further comprise the steps:
1). with 1,9,10,18-four halo two and perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids, four imide analog compounds and catalyzer are 1: 0.1～1.2 mixing in molar ratio, add organic solvent then, 1,9,10,18-four halo Er Bing perylenes-3,4,6,7:12,13,15, the ratio of 16-eight carboxylic acids, four imide analog compounds and organic solvent is 0.001～1.0mmol/ml;
2). under protection of inert gas, in the mixture of step 1) preparation, add the organotin reagent of sulfur-bearing, prepared mixing solutions is heated to 60 ℃～150 ℃ reacts, reacted 5～20 hours, 1,9,10,18-four halo Er Bing perylenes-3,4,6,7:12,13,15, the mol ratio of the organotin reagent of 16-eight carboxylic acids, four imide analog compounds and sulfur-bearing is 1: 2～3; After reaction finishes, 60 ℃ of following solvent evaporated, the solid of gained is after washing with alcohol, and column chromatography for separation obtains containing suc as formula the side position shown in (II) the Er Bing perylene-3 of sulphur atom bridging, 4,6,7:12,13,15,16-eight carboxylic acids four imide analog compounds, the productive rate after the purification is 60%～95%;
Wherein: X is a sulphur; R is selected from hydrogen, C
1～C
30Alkyl, C
1～C
30A kind of in alkoxyl group, replacement or the unsubstituted aryl.
Substituting group in the aryl of described replacement is C
1～C
20Alkyl or C
1～C
20Alkoxyl group.
1,9,10 of the present invention's employing, 18-four halo Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imide analog compounds are to contain substituting group or do not contain substituent 1,9,10,18-tetrachloro-Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imides, 1,9,10,18-tetrabromo-Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imides, 1,9,10, the 18-tetraiodo-Er Bing perylenes-3,4,6,7:12,13,15, the mixture of one or more in 16-eight carboxylic acids four imides.Described substituting group is selected from hydrogen, C
1～C
30Alkyl, C
1～C
30A kind of in alkoxyl group, replacement or the unsubstituted aryl.Substituting group in the aryl of described replacement is C
1～C
20Alkyl or C
1～C
20Alkoxyl group.
The described catalyzer of step 1) is the mixture of four (triphenyl phosphorus) palladiums or cuprous iodide and four (triphenyl phosphorus) Palladous chloride, and the mol ratio of cuprous iodide and four (triphenyl phosphorus) Palladous chloride is preferably 1: 1.
The described organic solvent of step 1) is benzene, toluene, o-Xylol or the mixed solvent between them.
Step 2) organotin reagent of described sulfur-bearing is sulfuration three positive methyl tin, sulfuration three positive ethyl tin, sulfuration three n-propyl tin, sulfuration tri-n-butyl tin, sulfuration triphenyltin or sulfuration trityl tin.
Above-mentioned rare gas element comprises nitrogen or argon gas.
The target product that the present invention obtains 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, and 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; 1,9,10,18-four halo Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imide analog compounds are synthetic by document (J.Am.Chem.Soc., 2007,129,10664-10665) report method.
The Er Bing perylene-3,4,6 of sulphur atom or selenium atom bridging is contained in side of the present invention position, 7:12, and 13,15,16-eight carboxylic acids four imide analog compounds can be used as industrial dye, solar cell material, liquid crystal material or organic field-effect tube etc.
The invention has the advantages that: institute's synthetic compound has novel chemical structure, and synthetic method is simple, the compound purity height that obtains.
Description of drawings
Fig. 1. the N of the embodiment of the invention 1,3,5,6, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-thia 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 1,3,5,6,12,13, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums.
Fig. 3. the N of the embodiment of the invention 1,3,5,6,12,13, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four are imido
1H-NMR figure.
Fig. 4. the N of the embodiment of the invention 1,3,5,6,12,13, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four are imido
13C-NMR figure.
Fig. 5. the N of the embodiment of the invention 2,4,7,8, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-selenium assorted two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums.
Fig. 6. the N of the embodiment of the invention 2,4,7,8, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-two selenium assorted two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums.
Fig. 7. the N of the embodiment of the invention 9,10,14, N ', N ", N " and '-four (dodecyl)-dithia two and perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums.
Embodiment
Embodiment 1 (N, N ', N ", N " '-four (2, the 6-diisopropyl phenyl)-and thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids, four imides and N, N '; N ", N " and '-four (2,6-two different interior basic phenyl)-dithia 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, 10mmol sodium sulphite, 6mmol cuprous iodide, 7mmol L-proline(Pro) and 12mmol 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 10 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)-thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 72mg, productive rate is 10%.Black solid MS (MALDI-TOF, m/z): 1444.7.Anal.Calcd.for:C
96H
76N
4O
8S (molecular weight: 1444.5); N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 88mg, productive rate is 12%.Black solid MS (MALDI-TOF, m/z): 1474.9.Anal.Calcd.for:C
96H
74N
4O
8S
2(molecular weight: 1474.5);
1H NMR (CDCl
3, 300MHz, 298K): δ=10.89 (s, 2H), 10.21 (s, 2H), 9.93 (s, 2H), 7.54 (m, 4H), 7.40 (d, 8H), 3.15 (b, 4H), 2.90 (m, 4H), 1.28 (m, 24H), 1.13 (d, 12H), 0.86 (d, 12H);
13C NMR (CDCl
3, 150MHz, 298K): δ=164.9,164.7,164.6,163.4,146.2,146.1,140.4,139.7,132.0,131.8,131.6,131.5,131.3,129.3,127.3,125.9,125.8,125.0,124.4,123.3,123.1,121.6,121.5,120.1,119.4,29.9,29.4,24.7,24.3,24.2,24.1.
N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 1; N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 2;
1H-NMR figure as shown in Figure 3;
13C-NMR figure as shown in Figure 4.Embodiment 2 (N, N ', N ", N " '-four (2, the 6-diisopropyl phenyl)-and the assorted Er Bing perylene-3,4,6 of selenium, 7:12,13,15,16-eight carboxylic acids, four imides and N, N '; N ", N " and the assorted Er Bing perylene-3 of '-four (2, the 6-diisopropyl phenyl)-two selenium; 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, 12mmol sodium selenide, 6mmol cuprous iodide, 7mmol L-proline(Pro) and 14mmol 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 100 ℃, 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)-selenium Er Bing perylene-3,4 of mixing, 6,7:12,13,15,16-eight carboxylic acids four imide 82mg, productive rate is 11%.Black powder, and MS (MALDI-TOF, m/z): 1493.4.Anal.Calcd.for:C
96H
76N
4O
8Se (molecular weight: 1493.5); N, N ', N ", N " and the assorted Er Bing perylene-3,4,6 of '-four (2, the 6-diisopropyl phenyl)-two selenium, 7:12,13,15,16-eight carboxylic acids four imide 78mg, productive rate is 10%.Black powder, and MS (MALDI-TOF, m/z): 1572.1.Anal.Calcd.for:C
96H
74N
4O
8Se
2(molecular weight: 1571.4).
N, N ', N ", N " and the assorted Er Bing perylene-3,4,6 of '-four (2, the 6-diisopropyl phenyl)-selenium, 7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 5; N, N ', N ", N " and the assorted Er Bing perylene-3,4,6 of '-four (2, the 6-diisopropyl phenyl)-two selenium, 7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 6.
Embodiment 3 (N, N ', N ", N " '-four (2, the 6-diisopropyl phenyl)-and thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids, four imides and N, N '; N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia 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, 14mmol sodium sulphite, 7mmol cuprous chloride, 8mmol L-proline(Pro) and 11mmol Anhydrous potassium carbonate mix;
2. in the mixture of step 1 preparation, add the 12ml 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 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)-thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 72mg, productive rate is 10%.Black solid MS (MALDI-TOF, m/z): 1444.7.Anal.Calcd.for:C
96H
76N
4O
8S (molecular weight: 1444.5); N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 125mg, productive rate is 17%.Black solid MS (MALDI-TOF, m/z): 1474.9.Anal.Calcd.for:C
96H
74N
4O
8S
2(molecular weight: 1474.5);
1H NMR (CDCl
3, 300MHz, 298K): δ=10.89 (s, 2H), 10.21 (s, 2H), 9.93 (s, 2H), 7.54 (m, 4H), 7.40 (d, 8H), 3.15 (b, 4H), 2.90 (m, 4H), 1.28 (m, 24H), 1.13 (d, 12H), 0.86 (d, 12H);
13C NMR (CDCl
3, 150MHz, 298K): δ=164.9,164.7,164.6,163.4,146.2,146.1,140.4,139.7,132.0,131.8,131.6,131.5,131.3,129.3,127.3,125.9,125.8,125.0,124.4,123.3,123.1,121.6,121.5,120.1,119.4,29.9,29.4,24.7,24.3,24.2,24.1.
N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 1; N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 2;
1H-NMR figure as shown in Figure 3;
13C-NMR figure as shown in Figure 4.
Embodiment 4 (N, N ', N ", N " '-four (2, the 6-diisopropyl phenyl)-and the assorted Er Bing perylene-3,4,6 of selenium, 7:12,13,15,16-eight carboxylic acids, four imides and N, N '; N ", N " and the assorted Er Bing perylene-3 of '-four (2, the 6-diisopropyl phenyl)-two selenium; 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, 13mmol sodium selenide, 7mmol cuprous iodide, 8mmol L-proline(Pro) and 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 12 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)-selenium Er Bing perylene-3,4 of mixing, 6,7:12,13,15,16-eight carboxylic acids four imide 82mg, productive rate is 11%.Black powder, and MS (MALDI-TOF, m/z): 1493.4.Anal.Calcd.for:C
96H
76N
4O
8Se (molecular weight: 1493.5); N, N ', N ", N " and the assorted Er Bing perylene-3,4,6 of '-four (2, the 6-diisopropyl phenyl)-two selenium, 7:12,13,15,16-eight carboxylic acids four imide 138mg, productive rate is 18%.Black powder, and MS (MALDI-TOF, m/z): 1572.1.Anal.Calcd.for:C
96H
74N
4O
8Se
2(molecular weight: 1571.4).
N, N ', N ", N " and the assorted Er Bing perylene-3,4,6 of '-four (2, the 6-diisopropyl phenyl)-selenium, 7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 5; N, N ', N ", N " and the assorted Er Bing perylene-3,4,6 of '-four (2, the 6-diisopropyl phenyl)-two selenium, 7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 6.
Embodiment 5 (N, N ', N ", N " '-four (2, the 6-diisopropyl phenyl)-and thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids, four imides and N, N '; N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia 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 ', 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, 10mmol sodium sulphite, 6mmol cuprous chloride, 7mmol L-proline(Pro) and 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 10 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)-thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 202mg, productive rate is 14%.Black solid MS (MALDI-TOF, m/z): 1444.7.Anal.Calcd.for:C
96H
76N
4O
8S (molecular weight: 1444.5); N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 383mg, productive rate is 26%.Black solid MS (MALDI-TOF, m/z): 1474.9.Anal.Calcd.for:C
96H
74N
4O
8S
2(molecular weight: 1474.5);
1H NMR (CDCl
3, 300MHz, 298K): δ=10.89 (s, 2H), 10.21 (s, 2H), 9.93 (s, 2H), 7.54 (m, 4H), 7.40 (d, 8H), 3.15 (b, 4H), 2.90 (m, 4H), 1.28 (m, 24H), 1.13 (d, 12H), 0.86 (d, 12H);
13C NMR (CDCl
3, 150MHz, 298K): δ=164.9,164.7,164.6,163.4,146.2,146.1,140.4,139.7,132.0,131.8,131.6,131.5,131.3,129.3,127.3,125.9,125.8,125.0,124.4,123.3,123.1,121.6,121.5,120.1,119.4,29.9,29.4,24.7,24.3,24.2,24.1.
N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 1; N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 2;
1H-NMR figure as shown in Figure 3;
13C-NMR figure as shown in Figure 4.Embodiment 6 (N, N ', N ", N " '-four (2, the 6-diisopropyl phenyl)-and thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids, four imides and N, N '; N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia 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 ', 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, 10mmol sodium sulphite, 6mmol cuprous chloride, 7mmol L-proline(Pro) and 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 70 ℃, reacts 10 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)-thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 178mg, productive rate is 12%.Black solid MS (MALDI-TOF, m/z): 1444.7.Anal.Calcd.for:C
96H
76N
4O
8S (molecular weight: 1444.5); N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 410mg, productive rate is 28%.Black solid MS (MALDI-TOF, m/z): 1474.9.Anal.Calcd.for:C
96H
74N
4O
8S
2(molecular weight: 1474.5);
1H NMR (CDCl
3, 300MHz, 298K): δ=10.89 (s, 2H), 10.21 (s, 2H), 9.93 (s, 2H), 7.54 (m, 4H), 7.40 (d, 8H), 3.15 (b, 4H), 2.90 (m, 4H), 1.28 (m, 24H), 1.13 (d, 12H), 0.86 (d, 12H);
13C NMR (CDCl
3, 150MHz, 298K): δ=164.9,164.7,164.6,163.4,146.2,146.1,140.4,139.7,132.0,131.8,131.6,131.5,131.3,129.3,127.3,125.9,125.8,125.0,124.4,123.3,123.1,121.6,121.5,120.1,119.4,29.9,29.4,24.7,24.3,24.2,24.1.
N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 1; N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 2;
1H-NMR figure as shown in Figure 3;
13C-NMR figure as shown in Figure 4.
Embodiment 7 (N, N ', N ", N " '-four (2, the 6-diisopropyl phenyl)-and the assorted Er Bing perylene-3,4,6 of selenium, 7:12,13,15,16-eight carboxylic acids, four imides and N, N '; N ", N " and the assorted Er Bing perylene-3 of '-four (2, the 6-diisopropyl phenyl)-two selenium; 4,6,7:12; 13,15,16-eight carboxylic acids four imides)
Concrete synthesis step is:
1. with 1mmol 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, 10mmol sodium sulphite, 6mmol cuprous bromide, 7mmol L-proline(Pro) and 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 10 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)-selenium Er Bing perylene-3,4 of mixing, 6,7:12,13,15,16-eight carboxylic acids four imide 179mg, productive rate is 12%.Black powder, and MS (MALDI-TOF, m/z): 1493.4.Anal.Calcd.for:C
96H
76N
4O
8Se (molecular weight: 1493.5); N, N ', N ", N " and the assorted Er Bing perylene-3,4,6 of '-four (2, the 6-diisopropyl phenyl)-two selenium, 7:12,13,15,16-eight carboxylic acids four imide 346mg, productive rate is 22%.Black powder, and MS (MALDI-TOF, m/z): 1572.1.Anal.Calcd.for:C
96H
74N
4O
8Se
2(molecular weight: 1571.4).
N, N ', N ", N " and the assorted Er Bing perylene-3,4,6 of '-four (2, the 6-diisopropyl phenyl)-selenium, 7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 5; N, N ', N ", N " and the assorted Er Bing perylene-3,4,6 of '-four (2, the 6-diisopropyl phenyl)-two selenium, 7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 6.
Embodiment 8 (N, N ', N ", N " '-four (2, the 6-diisopropyl phenyl)-and the assorted Er Bing perylene-3,4,6 of selenium, 7:12,13,15,16-eight carboxylic acids, four imides and N, N '; N ", N " and the assorted Er Bing perylene-3 of '-four (2, the 6-diisopropyl phenyl)-two selenium; 4,6,7:12; 13,15,16-eight carboxylic acids four imides)
Concrete synthesis step is:
1. with 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 imides, 10mmol sodium sulphite, 6mmol cuprous iodide, 7mmol L-proline(Pro) and 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 50 ℃, reacts 10 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)-selenium Er Bing perylene-3,4 of mixing, 6,7:12,13,15,16-eight carboxylic acids four imide 149mg, productive rate is 10%.Black powder, and MS (MALDI-TOF, m/z): 1493.4.Anal.Calcd.for:C
96H
76N
4O
8Se (molecular weight: 1493.5); N, N ', N ", N " and the assorted Er Bing perylene-3,4,6 of '-four (2, the 6-diisopropyl phenyl)-two selenium, 7:12,13,15,16-eight carboxylic acids four imide 503mg, productive rate is 32%.Black powder, and MS (MALDI-TOF, m/z): 1572.1.Anal.Calcd.for:C
96H
74N
4O
8Se
2(molecular weight: 1571.4).
N, N ', N ", N " and the assorted Er Bing perylene-3,4,6 of '-four (2, the 6-diisopropyl phenyl)-selenium, 7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 5; N, N ', N ", N " and the assorted Er Bing perylene-3,4,6 of '-four (2, the 6-diisopropyl phenyl)-two selenium, 7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 6.
Embodiment 9 (N, N ', N ", N " '-four (dodecyl)-thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids, four imides and N, N ', N ", N " and '-four (dodecyl)-dithia 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 (dodecyl)-1,6,7,12-Si Lv perylene-3,4:9,10-tetracarboxylic acid diimide and 10mmol sodium sulphite, 6mmol cuprous chloride, 7mmol L-proline(Pro), 8mmol Anhydrous potassium carbonate mix;
2. in the mixture of step 1 preparation, add the 10ml N-Methyl pyrrolidone;
3. under nitrogen protection, the mixing solutions that step 2 is prepared is heated to 110 ℃, reacts 12 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 (dodecyl)-thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 74mg, productive rate is 10%.Black powder, and MS (MALDI-TOF, m/z): 1477.0.Anal.Calcd.for:C
96H
108N
4O
8S (molecular weight: 1476.8).N, N ', N ", N " and '-four (dodecyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 83mg, productive rate is 11%.Black powder, and MS (MALDI-TOF, m/z): 1506.9.Anal.Calcd.for:C
96H
106N
4O
8S
2(molecular weight: 1506.7).
N, N ', N ", N " and '-four (dodecyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 7.
Embodiment 10 (N, N ', N ", N " '-four (dodecyl)-thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids, four imides and N, N ', N ", N " and '-four (dodecyl)-dithia 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 (dodecyl)-1,6,7,12-Si Xiu perylene-3,4:9,10-tetracarboxylic acid diimide, 10mmol sodium sulphite, 6mmol cuprous chloride, 7mmol L-proline(Pro) and 11mmol Anhydrous potassium carbonate mix;
2. in the mixture of step 1 preparation, add the 8ml 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 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 (dodecyl)-thia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 96mg, productive rate is 13%.Black powder, and MS (MALDI-TOF, m/z): 1477.0.Anal.Calcd.for:C
96H
108N
4O
8S (molecular weight: 1476.8).N, N ', N ", N " and '-four (dodecyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide 120mg, productive rate is 16%.Black powder, and MS (MALDI-TOF, m/z): 1506.9.Anal.Calcd.for:C
96H
106N
4O
8S
2(molecular weight: 1506.7).
N, N ', N ", N " and '-four (dodecyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 7.
Embodiment 11 (N, N ', N ", N " the assorted Er Bing perylene-3,4,6 of '-four (dodecyl)-selenium, 7:12,13,15,16-eight carboxylic acids, four imides and N, N ', N ", N " and the assorted Er Bing perylene-3 of '-four (dodecyl)-two selenium, 4,6,7:12,13,15,16-eight carboxylic acids four imides)
Concrete synthesis step is:
1. with 1mmol N, N '-two (dodecyl)-1,6,7,12-Si Lv perylene-3,4:9,10-tetracarboxylic acid diimide, 8mmol sodium selenide, 6mmol cuprous chloride, 7mmol L-proline(Pro) and 10mmol 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 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 (dodecyl)-selenium Er Bing perylene-3,4 of mixing, 6,7:12,13,15,16-eight carboxylic acids four imide 107mg, productive rate is 14%.Black powder, and MS (MALDI-TOF, m/z): 1524.9.Anal.Calcd.for:C
96H
108N
4O
8Se (molecular weight: 1524.7).N, N ', N ", N " and the assorted Er Bing perylene-3,4,6 of '-four (dodecyl)-two selenium, 7:12,13,15,16-eight carboxylic acids four imide 136mg, productive rate is 17%.Black powder, and MS (MALDI-TOF, m/z): 1602.1.Anal.Calcd.for:C
96H
106N
4O
8Se
2(molecular weight: 1602.6).
Embodiment 12 (N, N ', N ", N " '-four (2, the 6-diisopropyl phenyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imides)
1. with 1mmol 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 and 0.2mmol four (triphenyl phosphorus) palladium mix, and add the 150ml toluene solvant then;
2. under argon shield, in the mixture of step 1 preparation, add 2.1mmol sulfuration tri-n-butyl tin, back flow reaction 10 hours.After reaction finishes, 60 ℃ of following solvent evaporated, the solid of gained is after washing with alcohol, the silica gel column chromatography separation obtains product N, N '; N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia Er Bing perylene-3,4,6; 7:12,13,15,16-eight carboxylic acids four imide 1150mg, productive rate is 78%.Black solid MS (MALDI-TOF, m/z): 1474.9.Anal.Calcd.for:C
96H
74N
4O
8S
2(molecular weight: 1474.5);
1H NMR (CDCl
3, 300MHz, 298K): δ=10.89 (s, 2H), 10.21 (s, 2H), 9.93 (s, 2H), 7.54 (m, 4H), 7.40 (d, 8H), 3.15 (b, 4H), 2.90 (m, 4H), 1.28 (m, 24H), 1.13 (d, 12H), 0.86 (d, 12H);
13C NMR (CDCl
3, 150MHz, 298K): δ=164.9,164.7,164.6,163.4,146.2,146.1,140.4,139.7,132.0,131.8,131.6,131.5,131.3,129.3,127.3,125.9,125.8,125.0,124.4,123.3,123.1,121.6,121.5,120.1,119.4,29.9,29.4,24.7,24.3,24.2,24.1.
N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 2;
1H-NMR figure as shown in Figure 3;
13C-NMR figure as shown in Figure 4.
Embodiment 13 (N, N ', N ", N " '-four (2, the 6-diisopropyl phenyl)-and the assorted Er Bing perylene-3,4,6 of selenium, 7:12,13,15,16-eight carboxylic acids, four imides and N, N '; N ", N " and the assorted Er Bing perylene-3 of '-four (2, the 6-diisopropyl phenyl)-two selenium; 4,6,7:12; 13,15,16-eight carboxylic acids four imides)
1. with 1mmol 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 and 0.2mmol four (triphenyl phosphorus) palladium mix, and add the 150ml toluene solvant then;
2. under argon shield, in the mixture of step 1 preparation, add 2.0mmol sulfuration tri-n-butyl tin, back flow reaction 10 hours.After reaction finishes, 60 ℃ of following solvent evaporated, the solid of gained is after washing with alcohol, the silica gel column chromatography separation obtains product N, N '; N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia Er Bing perylene-3,4,6; 7:12,13,15,16-eight carboxylic acids four imide 1209mg, productive rate is 82%.Black solid MS (MALDI-TOF, m/z): 1474.9.Anal.Calcd.for:C
96H
74N
4O
8S
2(molecular weight: 1474.5);
1H NMR (CDCl
3, 300MHz, 298K): δ=10.89 (s, 2H), 10.21 (s, 2H), 9.93 (s, 2H), 7.54 (m, 4H), 7.40 (d, 8H), 3.15 (b, 4H), 2.90 (m, 4H), 1.28 (m, 24H), 1.13 (d, 12H), 0.86 (d, 12H);
13C NMR (CDCl
3, 150MHz, 298K): δ=164.9,164.7,164.6,163.4,146.2,146.1,140.4,139.7,132.0,131.8,131.6,131.5,131.3,129.3,127.3,125.9,125.8,125.0,124.4,123.3,123.1,121.6,121.5,120.1,119.4,29.9,29.4,24.7,24.3,24.2,24.1.
N, N ', N ", N " and '-four (2, the 6-diisopropyl phenyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 2;
1H-NMR figure as shown in Figure 3;
13C-NMR figure as shown in Figure 4.
Embodiment 14 (N, N ', N ", N " '-four (dodecyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imides)
1. with 1mmol N, N ', N ", N " '-four (dodecyl)-1,9,10,18-tetrachloro Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids, four imides and 0.3mmol four (triphenyl phosphorus) palladium mix, and add the 120ml toluene solvant then;
2. under argon shield, in the mixture of step 1 preparation, add 2.0mmol sulfuration tri-n-butyl tin, back flow reaction 10 hours.After reaction finishes, 60 ℃ of following solvent evaporated, the solid of gained is after washing with alcohol, the silica gel column chromatography separation obtains product N, N '; N ", N " and '-four (dodecyl)-dithia Er Bing perylene-3,4,6,7:12; 13,15,16-eight carboxylic acids four imide 1070mg, productive rate is 71%.Black powder, and MS (MALDI-TOF, m/z): 1506.9.Anal.Calcd.for:C
96H
106N
4O
8S
2(molecular weight: 1506.7).
N, N ', N ", N " and '-four (dodecyl)-dithia Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imido mass spectrums are as shown in Figure 7.
Claims (15)
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, described Er Bing perylene-3,4,6,7:12,13,15,16-eight carboxylic acids four imide analog compounds are Er Bing perylenes-3,4 that sulphur atom or selenium atom bridging are contained in the side position, 6,7: 0,12,13,15,16-eight carboxylic acids four imide analog compounds, this compound has following structure:
Wherein:
X is sulphur or selenium; R is selected from hydrogen, C
1～C
30Alkyl, C
1～C
30A kind of in alkoxyl group, replacement or the unsubstituted aryl.
2. compound according to claim 1 is characterized in that: the substituting group in the aryl of described replacement is C
1～C
20Alkyl or C
1～C
20Alkoxyl group.
3. the preparation method according to each described compound of claim 1～2 is characterized in that, this preparation method may further comprise the steps:
1). with 1,6,7,12-four Lu Dai perylenes-3,4: 9,10-tetracarboxylic acid diimide compounds or 1,9,10,18-four halo Er Bing perylenes-3,4,6,7: 12,13,15,16-eight carboxylic acids four imide analog compounds, sodium sulphite or sodium selenide, catalyzer, part and mineral alkali are 1: 4～20: 1～12: 1～15: 1～16 to mix in molar ratio;
2). in the mixture of step 1) preparation, add organic solvent, 1,6,7,12-four Lu Dai perylenes-3,4: 9,10-tetracarboxylic acid diimide compounds or 1,9,10,18-four halo Er Bing perylenes-3,4,6,7: 12,13,15, the ratio of 16-eight carboxylic acids, four imide analog compounds and organic solvent is 0.01～1.0mmol/ml;
3). under protection of inert gas, with step 2) prepared mixing solutions is heated to 30 ℃～150 ℃ and reacts, reaction finishes, product is through organic solvent dissolution, and sodium chloride aqueous solution washs, drying, filter, the evaporate to dryness organic solvent, column chromatography for separation obtains the Er Bing perylene-3 that sulphur atom or selenium atom bridging are contained in the side position, 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.
4. method according to claim 3 is characterized in that: described amino acid is L-proline(Pro), N-methyl aminoacetic acid, N, the mixture of one or more in the N-dimethylamino acetate;
Described positive cuprous salt is one or more the mixture in cuprous iodide, cuprous bromide, the cuprous chloride.
5. method according to claim 3 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 1,9,10,18-four halo Er Bing perylenes-3,4,6,7:12,13,15,16-eight carboxylic acids four imide analog compounds are to contain substituting group or do not contain substituent 1,9,10,18-tetrachloro-Er Bing perylenes-3,4,6,7: 12,13,15,16-eight carboxylic acids four imides, 1,9,10,18-tetrabromo-Er Bing perylenes-3,4,6,7: 12,13,15,16-eight carboxylic acids four imides, 1,9,10, the 18-tetraiodo-Er Bing perylenes-3,4,6,7: 12,13,15, the mixture of one or more in 16-eight carboxylic acids four imides.
6. method according to claim 5 is characterized in that: described substituting group is selected from hydrogen, C
1～C
30Alkyl, C
1～C
30A kind of in alkoxyl group, replacement or the unsubstituted aryl;
Substituting group in the aryl of described replacement is C
1～C
20Alkyl or C
1～C
20Alkoxyl group.
7. method according to claim 3 is characterized in that: step 2) described organic solvent is dimethyl sulfoxide (DMSO), N, dinethylformamide, N-Methyl pyrrolidone or the mixed solvent between them;
The described organic solvent of step 3) is methylene dichloride, ethyl acetate, toluene or the mixed solvent between them.
8. one kind contains the preparation method of the compound of sulphur atom bridging according to each described side position of claim 1～2, it is characterized in that this preparation method may further comprise the steps:
1). with 1,9,10,18-four halo two and perylenes-3,4,6,7: 12,13,15,16-eight carboxylic acids, four imide analog compounds and catalyzer are 1: 0.1～1.2 mixing in molar ratio, add organic solvent then, 1,9,10,18-four halo Er Bing perylenes-3,4,6,7: 12,13,15, the ratio of 16-eight carboxylic acids, four imide analog compounds and organic solvent is 0.001～1.0mmol/ml;
2). under protection of inert gas, in the mixture of step 1) preparation, add the organotin reagent of sulfur-bearing, prepared mixing solutions is heated to 60 ℃～150 ℃ reacts 1,9,10,18-four halo Er Bing perylenes-3,4,6,7: 12,13,15, the mol ratio of the organotin reagent of 16-eight carboxylic acids, four imide analog compounds and sulfur-bearing is 1: 2～3; After reaction finished, product obtained the Er Bing perylene-3,4 that the sulphur atom bridging is contained in the side position through column chromatography for separation, and 6,7: 12,13,15,16-eight carboxylic acids four imide analog compounds; Structure is:
Wherein: X is a sulphur; R is selected from hydrogen, C
1～C
30Alkyl, C
1～C
30A kind of in alkoxyl group, replacement or the unsubstituted aryl;
Substituting group in the aryl of described replacement is C
1～C
20Alkyl or C
1～C
20Alkoxyl group.
9. method according to claim 8 is characterized in that: described 1,9,10,18-four halo Er Bing perylenes-3,4,6,7: 12,13,15,16-eight carboxylic acids four imide analog compounds are to contain substituting group or do not contain substituent 1,9,10,18-tetrachloro-Er Bing perylenes-3,4,6,7: 12,13,15,16-eight carboxylic acids four imides, 1,9,10,18-tetrabromo-Er Bing perylenes-3,4,6,7: 12,13,15,16-eight carboxylic acids four imides, 1,9,10, the 18-tetraiodo-Er Bing perylenes-3,4,6,7: 12,13,15, the mixture of one or more in 16-eight carboxylic acids four imides;
Described substituting group is selected from hydrogen, C
1～C
30Alkyl, C
1～C
30A kind of in alkoxyl group, replacement or the unsubstituted aryl;
Substituting group in the aryl of described replacement is C
1～C
20Alkyl or C
1～C
20Alkoxyl group.
10. method according to claim 8 is characterized in that: the described catalyzer of step 1) is the mixture of four (triphenyl phosphorus) palladiums or cuprous iodide and four (triphenyl phosphorus) Palladous chloride;
Step 2) organotin reagent of described sulfur-bearing is sulfuration three positive methyl tin, sulfuration three positive ethyl tin, sulfuration three n-propyl tin, sulfuration tri-n-butyl tin, sulfuration triphenyltin or sulfuration trityl tin.
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