CN101704816A - Water-soluble perylene diimide derivatives containing N-pyridine oxide groups and synthetic method thereof - Google Patents
Water-soluble perylene diimide derivatives containing N-pyridine oxide groups and synthetic method thereof Download PDFInfo
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000010189 synthetic method Methods 0.000 title abstract description 3
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical class C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 title abstract 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 36
- -1 pyridyl N-oxide Chemical class 0.000 claims description 35
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 29
- 229910000071 diazene Inorganic materials 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000004440 column chromatography Methods 0.000 claims description 20
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 229960000583 acetic acid Drugs 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical group [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000413 hydrolysate Substances 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000007127 saponification reaction Methods 0.000 claims description 4
- 150000003927 aminopyridines Chemical class 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical group OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006862 quantum yield reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 229960002163 hydrogen peroxide Drugs 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003480 eluent Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- GRFNBEZIAWKNCO-UHFFFAOYSA-N 3-pyridinol Chemical compound OC1=CC=CN=C1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 239000000824 cytostatic agent Substances 0.000 description 1
- 230000001085 cytostatic effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- Pyridine Compounds (AREA)
Abstract
The invention discloses water-soluble perylene diimide derivatives containing N-pyridine oxide groups and a synthetic method thereof. In the general structural formula of the water-soluble perylene diimide derivatives containing N-pyridine oxide group, R'=OR or H, the substituents R are same or different and are independently selected from an N-pyridine oxide group or a hydrocarbon group, and at least one substituent R is an N-pyridine oxide group; and the hydrocarbon group is an alkyl group or aryl group. The water-soluble perylene diimide derivatives are oxidized with oxydol after halogenated perylene diimide derivatives react with a substituent reagent containing hydroxyl groups. The invention has the advantages of easily controlled preparation method and conditions, mild reaction, economical raw materials, small toxicity and high fluorescence quantum yield.
Description
Technical Field
The invention relates to a water-soluble perylene bisimide derivative and a synthesis method thereof, belonging to the technical field of organic synthesis.
Background
The perylene bisimide compound is a rigid, planar and conjugated condensed ring macromolecule, has good photochemical stability and strong fluorescence, and is mainly used as a pigment or a dye in early research. The perylene bisimide compounds are discovered to have good photoelectric activity later, and can be applied to the fields of organic photoconductors, solar energy conversion and the like, so that the interest of researchers in the fields of high-technology application is aroused, and the application of the perylene bisimide compounds can penetrate into the advanced scientific and technological fields of color liquid crystal display, organic photoelectric molecular devices and the like.
In recent years, such compounds have been applied to the biological field, such as antiviral agents, cytostatics and the like, and the application thereof in the biological and pigment fields is directly influenced by poor water solubility, so that the improvement of the water solubility of such compounds and the maintenance of high fluorescence are of great significance. The water solubility of the compounds is mainly solved by introducing water-soluble groups such as sulfonic acid groups, quaternary ammonium ions and the like (the structural formula is shown as the following formula)
Although the water solubility of the compounds is improved to a certain extent, the fluorescence quantum yield of the compounds in water is low, and different problems exist in the synthesis process, such as the use of concentrated sulfuric acid, damage to reaction equipment and serious pollution; the raw materials such as methyl iodide with high price, low boiling point and high toxicity are used, so that the cost of the obtained target compound is too high, and strict labor protection measures are required.
Disclosure of Invention
The invention aims to provide a water-soluble perylene bisimide derivative containing an N-pyridine oxide group, which has low toxicity and high fluorescence quantum yield.
The invention also aims to provide a preparation method of the derivative.
The technical scheme adopted by the invention is as follows:
the water-soluble perylene bisimide derivative containing the pyridine N-oxide group has the following structural general formula:
R′＝ORorH
wherein R' OR H, substituents R are the same OR different and are independently selected from pyridyl N-oxide OR hydrocarbyl, and at least one substituent R is pyridyl N-oxide; the alkyl is alkyl or aromatic alkyl.
The water-soluble perylene imide derivative containing the pyridine N-oxide group preferably has a compound with the following structural formula:
wherein,
the preparation method of the water-soluble perylene bisimide derivative containing the pyridine N-oxide group comprises the following steps:
(1) halogenated N, N' -dicyclohexylperylene-3, 4: preparation of 9, 10-tetracarboxylic acid diimide (the preparation adopts the prior art, N '-dicyclohexyl-3, 4: 9, 10-perylene tetracarboxylic acid diimide such as CN1706842A is synthesized by using 3, 4: 9, 10-perylene tetracarboxylic acid dianhydride and cyclohexylamine, and then the N, N' -dicyclohexyl-3, 4: 9, 10-perylene tetracarboxylic acid diimide is halogenated);
(2) to halogenated N, N' -dicyclohexylperylene-3, 4: adding a certain amount of hydroxyl-containing substituted reagent, potassium carbonate and N-methylpyrrolidone into 9, 10-tetracarboxylic acid diimide, reacting for 24-36 hours at 70-120 ℃, cooling to room temperature, pouring the solution after reaction into a proper amount of HCl solution, standing, performing suction filtration, washing and washing products with water and alcohol, drying, and then performing column chromatography separation;
(3) adding isopropanol and potassium hydroxide into the product obtained in the step (2), stirring, heating and refluxing for 20-30 h, adding glacial acetic acid to stop saponification, adding water into the product, filtering, washing and drying to obtain a hydrolysate, reacting the hydrolysate with p-aminopyridine in quinoline at 130-150 ℃ for 8-12 h under heating and stirring, cooling, pouring the solution after reaction into an HCl solution, carrying out suction filtration, washing and drying, carrying out column chromatography separation to obtain a substituted product, adding acetic acid and hydrogen peroxide into the substituted product, stirring at room temperature for 0.2-1 h, heating to 80-90 ℃, reacting for 15-30 h, adding hydrogen peroxide properly during the reaction, cooling to room temperature, pouring the solution into water, standing, carrying out suction filtration and drying, and carrying out column chromatography separation to obtain a final product; or directly adding acetic acid and hydrogen peroxide into the product obtained in the step (2), stirring at room temperature for 0.2-1 hour, heating to 80-90 ℃, reacting for 15-30 hours, appropriately supplementing hydrogen peroxide during the reaction, cooling to room temperature, pouring the solution into water, standing, filtering, drying, and performing column chromatography separation to obtain the final product.
The halogenated N, N' -dicyclohexyl perylene-3, 4 in the step (1): the 9, 10-tetracarboxylic acid diimide is 1, 7-dibromo-N, N' -dicyclohexyl-3, 4: 9, 10-perylenetetracarboxylic acid diimide or 1, 6, 7, 12-tetrachloro-N, N' -dicyclohexyl-3, 4: 9, 10-tetracarboxylic acid diimides.
The halogenated N, N' -dicyclohexyl perylene-3, 4 in the step (2): the molar ratio of the 9, 10-tetracarboxylic diimide to the hydroxyl substituent-containing reagent is 1: 2-20, preferably 1: 2-10, and the molar ratio of the potassium carbonate to the hydroxyl substituent-containing reagent is 1: 1; the amount of N-methylpyrrolidone is at least such that the molar ratio of N, N' -dicyclohexylperylene-3, 4: dissolving 9, 10-tetracarboxylic acid diimide; the mass concentration of the HCl solution is 5-20%, preferably 5-10%, and the dosage of the HCl solution is 2-20 times, preferably 3-10 times of the volume of the N-methylpyrrolidone; the hydroxyl-containing substituted reagent is hydroxypyridine or phenol or substituted phenol, and the eluting solution is prepared by the column chromatography separation of dichloromethane, acetone and petroleum ether in a ratio of 20 to 1(v/v) or dichloromethane and petroleum ether in a ratio of 1 to 1 (v/v).
The mass ratio of the product obtained in the step (2) to the potassium hydroxide in the step (3) is 1: 1-100, preferably 1: 2-10; the dosage of isobutanol is at least that the isobutanol can be completely dissolved under the heating condition of the product obtained in the step (2); the amount of the glacial acetic acid is 1.2-10 times of that of the potassium hydroxide in terms of mol; the molar ratio of the obtained hydrolysate to the aminopyridine is 1: 1-20, the preferred ratio is 1: 1-5, and the dosage of quinoline is at least to dissolve the obtained hydrolysate; the mass concentration of the HCl solution is 5-20%, preferably 5-10%, and the dosage of the HCl solution is 2-20 times, preferably 3-10 times of the volume of quinoline; the dosage of the acetic acid is at least that the obtained substitution product or the product obtained in the step (2) can be completely dissolved under the heating condition, and the dosage of the hydrogen peroxide is at least that the obtained substitution product or the product obtained in the step (2) can be completely oxidized in the reaction time (TLC detection); the column chromatography uses dichloromethane: acetone (v/v), or dichloromethane: tetrahydrofuran (v/v), or chloroform: tetrahydrofuran (v/v), or methanol (v/v), or chloroform: tetrahydrofuran (v/v), as eluent, or methanol (v/v), or chloroform: tetrahydrofuran (v/v), or methanol (v/v), or chloroform: 10: 3 (v/v).
The beneficial effects of the invention are as follows:
the preparation method has the advantages of easily controlled conditions, mild reaction, economic raw materials, low toxicity of the prepared water-soluble perylene bisimide derivative containing the pyridine N-oxide group and high fluorescence quantum yield.
Drawings
FIG. 1 is a schematic representation of 1, 7-bis (3-pyridyloxy) -N, N' -dicyclohexyl-3, 4: a synthetic scheme for 9, 10-perylene diimide;
FIG. 2 is 1, 6, 7, 12-tetra-p-tert-butylphenoxy-N, N' -bis (4-pyridinyloxy) -3, 4: a synthetic scheme for 9, 10-perylenetetracarboxylic acid diimides;
FIG. 3 is a drawing of 1, 7-bis (3-pyridyloxy) -N, N' -bis (4-pyridyloxy) -3, 4: synthesis scheme for 9, 10-perylenetetracarboxylic acid diimides.
Detailed Description
Example 1
1, 7-bis (3-pyridyloxy) -N, N' -dicyclohexyl-3, 4: preparation of 9, 10-perylene diimide (synthetic route shown in fig. 1):
to a 100 ml reaction flask was added 2.00 g of 3, 4: and (3) heating and refluxing 9, 10-perylene tetracarboxylic dianhydride and 30 ml of cyclohexylamine under vigorous stirring until the solid is completely dissolved, about 40 hours, decompressing and distilling to recover excessive cyclohexylamine, and drying to obtain 2.70 g of a product N, N' -dicyclohexyl-3, 4: 9, 10-perylenetetracarboxylic acid diimide with a yield of 96%;
to a 250 ml reaction flask was added 2.00 g of N, N' -dicyclohexyl-3, 4: 9, 10-perylenetetracarboxylic diimide and 150 ml of dichloromethane, then 30 ml of dichloromethane solution containing 10 g of bromine is dripped in 30 minutes, heated and refluxed for 4 days under the protection of argon, cooled to room temperature, evaporated at normal pressure to obtain a mixed solution of dichloromethane and bromine for recovery, and subjected to column chromatographic separation, wherein dichloromethane is eluent, so that 1.28 g of the product 1, 7-dibromo-N, N' -dicyclohexyl-3, 4: 9, 10-perylenetetracarboxylic acid diimide with a yield of 50%;
to a 25 ml reaction flask was added 0.50 g of 1, 7-dibromo-N, N' -dicyclohexyl-3, 4: 9, 10-perylenetetracarboxylic acid diimide, 0.34 g of m-hydroxypyridine, 0.49 g of potassium carbonate and 10 ml of N-methylpyrrolidone (NMP) are added, the mixture is reacted at 80 ℃ for 30 hours, the reaction product is cooled to room temperature, the solution is poured into 100 ml of 20% (wt%) HCl solution, the solution is stood overnight, filtered, washed to be neutral by water, washed by a small amount of methanol, dried and separated by column chromatography, and dichloromethane and acetone are 20: 1 as leacheate to obtain 311 mg of a product 1, 7-bis (3-pyridyloxy) -N, N' -dicyclohexyl-3, 4: 9, 10-perylene diimide, the yield is 60%;
to a 25 ml reaction flask was added 0.30 g of 1, 7-bis (3-pyridyloxy) -N, N' -dicyclohexyl-3, 4: 9, 10-perylene diimide, 3 ml of acetic acid and 1 ml of hydrogen peroxide, stirring for 0.5 hour at room temperature, heating to 80 ℃, adding 1 ml of hydrogen peroxide after reacting for 3 hours, reacting for 24 hours, cooling to room temperature, pouring the solution into 10 ml of water, standing overnight, performing suction filtration, drying, performing column chromatography separation, and obtaining 100 mg of product 1, 7-di (3-pyridyloxy) -N, N' -dicyclohexyl-3, 4: 9, 10-perylene diimide in 32% yield.
The resulting 1, 7-bis (3-pyridyloxy) -N, N' -dicyclohexyl-3, 4: nuclear magnetic analysis of 9, 10-perylene diimide was as follows:
1H NMR(300MHz，CDCl3，ppm)：δ9.28(2H，d，J＝8.3Hz)，8.65(d，2H，J＝8.3Hz)，8.36(s，2H)，8.12(m，4H)，7.37(m，2H)，7.13(m，2H)，5.00(m，2H)，2.57-2.46(m，2H)，1.90-1.75(m，8H)，1.52-1.24(m，6H)，2.48-2.57(m，4H).
13C NMR(75MHz，CDCl3，ppm)：δ163.143，162.566，152.110，132.125，131.200，131.070，129.051，126.370，125.470，125.163，125.045，123.653，107.866，67.598，54.310，29.145，26.427，25.328，23.898.
example 2
1, 6, 7, 12-tetra-p-tert-butylphenoxy-N, N' -bis (4-pyridinyloxy) -3, 4: preparation of 9, 10-perylenetetracarboxylic acid diimides (see scheme 2):
to a 50 ml reaction flask was added 1.00 g of 1, 6, 7, 12-tetrachloro-N, N' -dicyclohexyl-3, 4: 9, 10-tetracarboxylic acid diimide, 1.74 g of tert-butylphenol, 0.97 g of potassium carbonate and 20 ml of N-methylpyrrolidone (NMP) are added, the mixture is reacted for 24 hours at 110 ℃, the reaction product is cooled to room temperature, the solution is poured into 150 ml of 20% HCl solution, the solution is kept still overnight, the solution is filtered, washed to be neutral by water, washed by a small amount of methanol, dried and separated by column chromatography, dichloromethane and petroleum ether are used as eluent in a ratio of 1: 1, and 1.07 g of a product 1, 6, 7, 12-tetra-p-tert-butylphenoxy-3, 4: 9, 10-perylenetetracarboxylic acid diimide, the yield being 65%;
to a 50 ml reaction flask was added 0.50 g of 1, 6, 7, 12-tetra-p-tert-butylphenoxy-N, N' -dicyclohexyl-3, 4: 9, 10-perylenetetracarboxylic acid diimide, 30 ml of isopropanol, 0.61 g of potassium hydroxide are added, the mixture is stirred for 1 hour at normal temperature, then heated and refluxed for 24 hours, excessive glacial acetic acid is added to stop saponification, the mixture is refluxed for 0.5 hour, cooled to room temperature, reaction liquid is poured into a large amount of water, and the mixture is kept stand overnight, filtered, washed by water and dried to obtain 386 mg of a product 1, 6, 7, 12-tetra-p-tert-butylphenoxy-3, 4: 9, 10-perylene tetracarboxylic dianhydride with a yield of 90%;
to a 25 ml reaction flask was added 0.40 g of 1, 6, 7, 12-tetra-p-tert-butylphenoxy-N, N' -dicyclohexyl-3, 4: 9, 10-perylenetetracarboxylic dianhydride, 0.19 g of para-aminopyridine and 6 ml of quinoline, heating the reaction to 140 ℃, continuously heating and stirring for 10 hours, cooling to room temperature, pouring the solution into 50 ml of 20% (wt%) HCl solution, standing overnight, performing suction filtration, washing to be neutral, drying, performing column chromatography, and obtaining 277 mg of a product 1, 6, 7, 12-tetra-p-tert-butylphenoxy-N, N' -di (4-pyridine) -3, 4: 9, 10-perylenetetracarboxylic acid diimide with a yield of 60%;
to a 25 ml reaction flask was added 0.30 g of 1, 6, 7, 12-tetra-p-tert-butylphenoxy-N, N' -bis (4-pyridine) -3, 4: 9, 10-perylenetetracarboxylic diimide, 3 ml of acetic acid and 1 ml of hydrogen peroxide, stirring for 0.5 hour at room temperature, heating to 80 ℃, reacting for 3 hours, adding 1 ml of hydrogen peroxide, reacting for 24 hours, cooling to room temperature, pouring the solution into 10 ml of water, standing overnight, performing suction filtration, drying, performing column chromatography separation, and obtaining 92 mg of a product 1, 6, 7, 12-tetra-p-tert-butylphenoxy-N, N' -bis (4-nitroxy-pyridyl) -3, 4: 9, 10-perylenetetracarboxylic acid diimide in a yield of 30%. The obtained 1, 6, 7, 12-tetra-p-tert-butylphenoxy-N, N' -bis (4-pyridinyloxy) -3, 4: nuclear magnetic analysis of 9, 10-perylenetetracarboxylic diimide was as follows:
1H NMR(300MHz，CDCl3，ppm)：δ8.71(d，4H，J＝6.3Hz)，8.26(s，4H)，7.58(d，4H，J＝6.3Hz)，7.26(d，8H，J＝8.2Hz)，6.84(d，8H，J＝8.2Hz)，1.29(s，36H).
13C NMR(75MHz，CDCl3，ppm)：δ162.381，156.279，152.460，147.950，139.721，133.127，127.239，126.845，121.579，121.176，120.312，119.499，119.255，31.394.
example 3
1, 7-bis (3-pyridyloxy) -N, N' -bis (4-nitroxy-pyridyl) -3, 4: preparation of 9, 10-perylenetetracarboxylic acid diimides (see FIG. 3 for a synthetic route):
to a 50 ml reaction flask was added 0.70 g of 1, 7-dibromo-N, N' -dicyclohexyl-3, 4: 9, 10-tetracarboxylic acid diimide, 0.55 g of m-hydroxypyridine, 0.81 g of potassium carbonate and 20 ml of N-methylpyrrolidone (NMP) were added, the mixture was reacted at 80 ℃ for 24 hours, cooled to room temperature, poured into 150 ml of 20% (wt%) HCl solution, left to stand overnight and filtered, washed to neutrality with a small amount of methanol, dried, and subjected to column chromatography, and the eluent was dichloromethane/acetone 20: 1 to obtain 702 mg of 1, 7-bis (3-pyridyloxy) -3, 4: 9, 10-perylenetetracarboxylic acid diimide, the yield being 80%;
to a 50 ml reaction flask was added 0.60 g of 1, 7-bis (3-pyridyloxy) -N, N' -dicyclohexyl-3, 4: 9, 10-perylenetetracarboxylic acid diimide, 30 ml of isopropanol, 1.36 g of potassium hydroxide, stirring at normal temperature for 1 hour, heating and refluxing for 24 hours, adding excessive glacial acetic acid to stop saponification, refluxing for 0.5 hour, cooling to room temperature, pouring the reaction solution into a large amount of water, standing overnight, performing suction filtration, washing with water, and drying to obtain 437 mg of a product 1, 7-bis (3-pyridyloxy) -3, 4: 9, 10-perylene tetracarboxylic dianhydride with a yield of 87%;
to a 25 ml reaction flask was added 0.40 g of 1, 7-bis (3-pyridyloxy) -3, 4: 9, 10-perylenetetracarboxylic dianhydride, 0.33 g of aminopyridine and 6 ml of quinoline, heating the reaction to 140 ℃, continuously heating and stirring for 10 hours, cooling to room temperature, pouring the solution into 50 ml of 20% HCl solution, standing overnight, performing suction filtration, washing with water to neutrality, drying, performing column chromatography, and using dichloromethane and tetrahydrofuran which are 10: 1 as leacheate to obtain 281 mg of a product 1, 7-bis (3-pyridyloxy) -N, N' -bis (4-pyridine) -3, 4: 9, 10-perylenetetracarboxylic acid diimide, yield 55%;
to a 25 ml reaction flask was added 0.20 g of 1, 7-bis (3-pyridyloxy) -N, N' -bis (4-pyridine) -3, 4: 9, 10-perylenetetracarboxylic acid diimide, 2 ml of acetic acid and 1 ml of 30% hydrogen peroxide, stirring for 0.5 hour at room temperature, heating to 80 ℃, reacting for 3 hours, adding 1 ml of 30% hydrogen peroxide, reacting for 24 hours, cooling to room temperature, pouring the solution into 10 ml of water, standing overnight, performing suction filtration, drying, performing column chromatography separation, and obtaining 74 mg of a product 1, 7-bis (3-pyridyloxy) -N, N' -bis (4-pyridyloxy) -3, 4: 9, 10-perylenetetracarboxylic acid diimide in a yield of 34%. 1, 7-bis (3-pyridyloxy) -N, N' -bis (4-pyridyloxy) -3, 4: nuclear magnetic analysis of 9, 10-perylenetetracarboxylic diimide was as follows:
1H NMR(300MHz，DMSO-d6，ppm)：δ9.39(d，1H，J＝7.8Hz)，8.60(d，1H，J＝7.8Hz)，8.43(m，5H)，8.32(s，1H)，8.13(d，2H，J＝7.2Hz)，7.75(m，3H)，7.54-7.45(m，5H)，7.21(m，3H)，6.81(d，1H，J＝7.8Hz).
MS(MALDI-TOF)：m/z 762.2(M+)。
Claims (8)
1. The water-soluble perylene bisimide derivative containing the pyridine N-oxide group is characterized by having the following structural general formula:
wherein R' OR H, substituents R are the same OR different and are independently selected from pyridyl N-oxide OR hydrocarbyl, and at least one substituent R is pyridyl N-oxide; the alkyl is alkyl or aromatic alkyl.
2. The water-soluble perylene imide derivative containing a pyridine N-oxide group according to claim 1, wherein the structural formula is:
wherein,
3. the method for producing a water-soluble perylene imide derivative containing a pyridine N-oxide group according to claim 1 or 2, which is characterized by comprising the steps of:
(1) halogenated N, N' -dicyclohexylperylene-3, 4: preparing 9, 10-tetracarboxylic acid diimide;
(2) to halogenated N, N' -dicyclohexylperylene-3, 4: adding a certain amount of hydroxyl-containing substituted reagent, potassium carbonate and N-methylpyrrolidone into 9, 10-tetracarboxylic acid diimide, reacting for 24-36 hours at 70-120 ℃, cooling to room temperature, pouring the solution after reaction into a proper amount of HCl solution, standing, performing suction filtration, washing and washing products with water and alcohol, drying, and then performing column chromatography separation;
(3) adding isopropanol and potassium hydroxide into the product obtained in the step (2), stirring, heating and refluxing for 20-30 hours, adding glacial acetic acid to stop saponification, adding water into the product, filtering, washing and drying to obtain a hydrolysate, reacting the hydrolysate with p-aminopyridine in quinoline at 130-150 ℃ for 8-12 hours under heating and stirring, cooling, pouring the solution after reaction into an HCl solution, carrying out suction filtration, washing and drying, carrying out column chromatography separation to obtain a substituted product, adding acetic acid and hydrogen peroxide into the substituted product, stirring at room temperature for 0.2-1 hour, heating to 80-90 ℃, reacting for 15-30 hours, adding hydrogen peroxide properly during the reaction, cooling to room temperature, pouring the solution into water, standing, carrying out suction filtration and drying, and carrying out column chromatography separation to obtain a final product; or directly adding acetic acid and hydrogen peroxide into the product obtained in the step (2), stirring at room temperature for 0.2-1 hour, heating to 80-90 ℃, reacting for 15-30 hours, appropriately supplementing hydrogen peroxide during the reaction, cooling to room temperature, pouring the solution into water, standing, filtering, drying, and performing column chromatography separation to obtain the final product.
4. The process for producing a water-soluble perylene imide derivative having an N-pyridine oxide group according to claim 3, wherein said halogenated N, N' -dicyclohexylperylene-3, 4: the 9, 10-tetracarboxylic acid diimide is 1, 7-dibromo-N, N' -dicyclohexyl-3, 4: 9, 10-perylenetetracarboxylic acid diimide or 1, 6, 7, 12-tetrachloro-N, N' -dicyclohexyl-3, 4: 9, 10-tetracarboxylic acid diimides.
5. The process for producing a water-soluble perylene imide derivative having an N-pyridine oxide group according to claim 3, wherein said halogenated N, N' -dicyclohexylperylene-3, 4: the molar ratio of the 9, 10-tetracarboxylic diimide to the hydroxyl substituent-containing reagent is 1: 2-20, and the molar ratio of the potassium carbonate to the hydroxyl substituent-containing reagent is 1: 1; the amount of N-methylpyrrolidone is at least such that the molar ratio of N, N' -dicyclohexylperylene-3, 4: dissolving 9, 10-tetracarboxylic acid diimide; the mass concentration of the HCl solution is 5-20%, and the dosage of the HCl solution is 2-20 times of the volume of the N-methylpyrrolidone; the column chromatography uses dichloromethane and acetone as 20: 1 or dichloromethane and petroleum ether as 1: 1 as leacheate.
6. The process for producing a water-soluble perylene imide derivative having an N-pyridine oxide group according to claim 5, wherein said halogenated N, N' -dicyclohexylperylene-3, 4: the molar ratio of the 9, 10-tetracarboxylic diimide to the hydroxyl substituent-containing reagent is 1: 2-10; the hydroxyl-containing substitution reagent is hydroxypyridine or phenol or substituted phenol; the mass concentration of the HCl solution is 5% -10%, and the dosage of the HCl solution is 3-10 times of the volume of the N-methyl pyrrolidone.
7. The preparation method of the water-soluble perylene bisimide derivative containing the pyridine N-oxide group according to claim 3, wherein the mass ratio of the product obtained in the step (2) in the step (3) to potassium hydroxide is 1: 1-100; the dosage of isobutanol is at least that the isobutanol can be completely dissolved under the heating condition of the product obtained in the step (2); the amount of the glacial acetic acid is 1.2-10 times of that of the potassium hydroxide in terms of mol; the molar ratio of the obtained hydrolysate to the aminopyridine is 1: 1-20, and the dosage of quinoline is at least enough to dissolve the obtained hydrolysate; the mass concentration of the HCl solution is 5-20%, and the dosage of the HCl solution is 2-20 times of the volume of quinoline; the dosage of the acetic acid is at least that the obtained substitution product or the product obtained in the step (2) can be completely dissolved under the heating condition, and the dosage of the hydrogen peroxide is at least that the obtained substitution product or the product obtained in the step (2) can be completely oxidized in the reaction time; the column chromatography uses dichloromethane to acetone as 30: 1 or dichloromethane to tetrahydrofuran as 10: 1 or trichloromethane to tetrahydrofuran as methanol as 250: 50: 3 or trichloromethane to tetrahydrofuran as methanol as 30: 10: 1 or trichloromethane to tetrahydrofuran as methanol as 50: 10: 3.
8. The preparation method of the water-soluble perylene bisimide derivative containing the pyridine N-oxide group according to claim 7, wherein the mass ratio of the product obtained in the step (2) in the step (3) to potassium hydroxide is 1: 2-10; the molar ratio of the obtained hydrolysate to the p-aminopyridine is 1: 1-5; the mass concentration of the HCl solution is 5% -10%, and the dosage of the HCl solution is 3-10 times of the volume of quinoline.
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