CN112080156B - Water-soluble dye containing pyrene and preparation method thereof - Google Patents
Water-soluble dye containing pyrene and preparation method thereof Download PDFInfo
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- CN112080156B CN112080156B CN202011078909.0A CN202011078909A CN112080156B CN 112080156 B CN112080156 B CN 112080156B CN 202011078909 A CN202011078909 A CN 202011078909A CN 112080156 B CN112080156 B CN 112080156B
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- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000012300 argon atmosphere Substances 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229940125904 compound 1 Drugs 0.000 claims description 9
- 125000005581 pyrene group Chemical group 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- 229940125782 compound 2 Drugs 0.000 claims description 6
- 229940126214 compound 3 Drugs 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical group CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 claims description 4
- CQFFZJLMPJRACB-UHFFFAOYSA-N pyrene-1,3-dicarbaldehyde Chemical group C(=O)C1=CC(=C2C=CC3=CC=CC4=CC=C1C2=C34)C=O CQFFZJLMPJRACB-UHFFFAOYSA-N 0.000 claims description 3
- BOBUWRDJNRRYSN-UHFFFAOYSA-N pyrene-1,6-dicarbaldehyde Chemical compound C1=C2C(C=O)=CC=C(C=C3)C2=C2C3=C(C=O)C=CC2=C1 BOBUWRDJNRRYSN-UHFFFAOYSA-N 0.000 claims description 3
- BOHZVQYHWJYDDS-UHFFFAOYSA-N pyrene-1,8-dicarbaldehyde Chemical compound C1=C2C(C=O)=CC=C(C=C3)C2=C2C3=CC=C(C=O)C2=C1 BOHZVQYHWJYDDS-UHFFFAOYSA-N 0.000 claims description 3
- YLMXAUXHLGWKOH-UHFFFAOYSA-N pyrene-2,7-dicarbaldehyde Chemical compound C1=C(C=O)C=C2C=CC3=CC(C=O)=CC4=CC=C1C2=C43 YLMXAUXHLGWKOH-UHFFFAOYSA-N 0.000 claims description 3
- ATWLRNODAYAMQS-UHFFFAOYSA-N 1,1-dibromopropane Chemical compound CCC(Br)Br ATWLRNODAYAMQS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 16
- 238000002189 fluorescence spectrum Methods 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 10
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 5
- 229940125773 compound 10 Drugs 0.000 description 5
- 229940125797 compound 12 Drugs 0.000 description 5
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000005598 acylhydrazone group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- KXXXUIKPSVVSAW-UHFFFAOYSA-K pyranine Chemical compound [Na+].[Na+].[Na+].C1=C2C(O)=CC(S([O-])(=O)=O)=C(C=C3)C2=C2C3=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1 KXXXUIKPSVVSAW-UHFFFAOYSA-K 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 1
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 1
- 229960002216 methylparaben Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- RCYFOPUXRMOLQM-UHFFFAOYSA-N pyrene-1-carbaldehyde Chemical compound C1=C2C(C=O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 RCYFOPUXRMOLQM-UHFFFAOYSA-N 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- -1 quaternary ammonium salt compound Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B26/00—Hydrazone dyes; Triazene dyes
- C09B26/02—Hydrazone dyes
- C09B26/04—Hydrazone dyes cationic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a pyrene-containing water-soluble dye, which has a general formula shown as a formula I:
the pyrene-containing water-soluble dye component with broadened fluorescence emission spectrumThe method has the advantages of reasonable sub-design, novel synthetic target, better water solubility, easy control of synthetic conditions, simpler product purification, universality, simple synthetic steps and mild reaction conditions.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a novel pyrene-containing water-soluble dye and a preparation method thereof.
Background
The pyrene unit is widely used as a fluorophore, the fluorescence lifetime is long, the quantum yield is high, when the pyrene unit is stacked in a dimer form, a red-shifted excimer can be generated to emit light, and the pyrene derivative has excellent optical properties and has important application in the aspects of fluorescent probes, fluorescent dyes, fluorescent chemical sensors and the like. However, the absorption spectrum is in the near ultraviolet region, deep blue light is emitted at low concentration, the covered light emitting region is limited, and most organic compounds synthesized based on pyrene are insoluble in water, which undoubtedly limits the use of pyrene-based derivatives. At present, the research on water-soluble pyrene-containing compounds is less, so that the method for simply and efficiently synthesizing the pyrene-containing water-soluble compounds through reasonable molecular design has important research significance and practical value.
Disclosure of Invention
The first purpose of the invention is to provide a pyrene-containing water-soluble dye with broadened fluorescence emission spectrum.
The second purpose of the invention is to provide a preparation method of the pyrene-containing water-soluble dye with broadened fluorescence emission spectrum.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a pyrene-containing water-soluble dye, which has a general formula shown in formula I:
wherein R is1Is composed of
n is a positive integer greater than or equal to 2; r2、R3、R4、R5、R6、R7、R8、R9、R10Are all hydrogen;
or, R1、R3At the same time are
n is a positive integer greater than or equal to 2; r2、R4、R5、R6、R7、R8、R9、R10Are all hydrogen;
or, R1、R6At the same time are
n is a positive integer greater than or equal to 2; r2、R3、R4、R5、R7、R8、R9、R10Are all hydrogen;
or, R1、R8At the same time are
n is a positive integer greater than or equal to 2; r2、R3、R4、R5、R6、R7、R9、R10Are all hydrogen;
or, R2、R7At the same time are
n is a positive integer greater than or equal to 2; r1、R3、R4、R5、R6、R8、R9、R10Are all hydrogen.
More preferably, the pyrene-containing water-soluble dye comprises:
wherein R is1Is one of the following structures:
or, R1、R3And one of the following structures:
or, R1、R6And one of the following structures:
or, R1、R8And one of the following structures:
or, R2、R7And one of the following structures:
More preferably, the pyrene-containing water-soluble dye comprises:
wherein R is1Is composed of
R2、R3、R4、R5、R6、R7、R8、R9、R10Are all hydrogen;
or, R1、R3At the same time are
R2、R4、R5、R6、R7、R8、R9、R10Are all hydrogen;
or, R1、R6At the same time are
R2、R3、R4、R5、R7、R8、R9、R10Are all hydrogen;
or, R1、R8At the same time are
R2、R3、R4、R5、R6、R7、R9、R10Are all hydrogen;
or, R2、R7At the same time are
R1、R3、R4、R5、R6、R8、R9、R10Are all hydrogen.
Most preferably, the structure of the pyrene-containing water-soluble dye is one of the following structures:
the second aspect of the invention provides a preparation method of the pyrene-containing water-soluble dye, which comprises the following steps:
dissolving a compound 1 and potassium carbonate in an acetonitrile solution at room temperature, adding dibromoalkane, and stirring and refluxing for 1-24 hours at the temperature of 70-90 ℃ under an argon atmosphere to obtain a compound 2; the molar ratio of the compound 1 to the potassium carbonate is 1:3, the molar ratio of the compound 1 to the dibromoalkane is 1: 5;
secondly, adding the compound 2 and trimethylamine into ethanol, and stirring and refluxing for 1-24 hours at the temperature of 70-90 ℃ under the argon atmosphere to obtain a compound 3; wherein the molar ratio of the compound 2 to the trimethylamine is 1: 5;
dissolving the compound 3 and hydrazine hydrate in methanol, and stirring and refluxing for 1-24 hours at the temperature of 70-90 ℃ under the argon atmosphere to obtain a compound 4; the molar ratio of the compound 3 to the hydrazine hydrate is 1 (5-50);
fourthly, dissolving the compound 4, 1-pyrene formaldehyde or pyrene substitute and excessive trifluoroacetic acid in ethanol, and stirring and refluxing for 1-24 hours at the temperature of 70-90 ℃ under the argon atmosphere to obtain a compound shown in the formula I, namely a water-soluble dye containing pyrene;
the molar ratio of the compound 4 to the 1-pyrene formaldehyde is 1: 1; the molar ratio of the compound 4 to the pyrene substituent was 2: 1.
The dibromoalkane is dibromoethane or dibromopropane.
The pyrene substitute is 1, 3-pyrene dicarboxaldehyde, 1, 6-pyrene dicarboxaldehyde, 1, 8-pyrene dicarboxaldehyde, 2, 7-pyrene dicarboxaldehyde.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
in order to widen the spectral region, the acylhydrazone groups are introduced into the pyrene units, the pi-conjugated skeleton is prolonged, the fluorescence emission wavelength is red-shifted, and the effect of hydrogen bonds among the acylhydrazone groups can be used as secondary non-covalent interaction to stabilize the primary stacking interaction of the pyrene units. The other end of the acylhydrazone group is covalently modified with a hydrophilic quaternary ammonium salt chain, so that the whole molecule becomes a typical amphiphilic structure and has water solubility. This feature drives the amphiphilic assembly of target molecules in aqueous solution, hydrophobic pyrene units are stacked internally, thus generating excimer emission. The reasonable molecular design ensures that the target compound has water solubility, widens the fluorescence spectrum of the target compound and realizes the synthesis of the pyrene-containing water-soluble dye.
The pyrene-containing water-soluble dye with broadened fluorescence emission spectrum has the advantages of reasonable molecular design, novel synthetic target, better water solubility, easy control of synthetic conditions, simpler product purification, universality, simple synthetic steps and mild reaction conditions.
Drawings
FIG. 1 is a drawing of Compound 8 prepared in example 1 of the present invention1H-NMR chart.
FIG. 2 is a schematic fluorescence spectrum of Compound 8 prepared in example 1 of the present invention.
FIG. 3 is a drawing of Compound 9 prepared in example 2 of the present invention1H-NMR chart.
FIG. 4 is a graph showing the fluorescence spectrum of Compound 9 prepared in example 2 of the present invention.
FIG. 5 is a photograph of Compound 10, prepared according to example 3 of the present invention1H-NMR chart.
FIG. 6 is a schematic fluorescence spectrum of Compound 10 prepared in example 3 of the present invention.
FIG. 7 is a photograph of Compound 11 prepared in example 4 of the present invention1H-NMR chart.
FIG. 8 is a graph showing the fluorescence spectrum of Compound 11 prepared in example 4 of the present invention.
FIG. 9 is a photograph of Compound 12 prepared in example 5 of the present invention1H-NMR chart.
FIG. 10 is a graph showing the fluorescence spectrum of Compound 12 prepared in example 5 of the present invention.
FIG. 11 is a photograph of a clear orange-yellow aqueous solution of Compound 11 prepared in example 4 of the present invention.
FIG. 12 is a graph showing a fluorescence spectrum of trisodium 8-hydroxypyrene-1, 3, 6-trisulfonate, a comparative example compound according to the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The synthetic route of the intermediate compound required by the embodiment of the invention is as follows:
the preparation method of the compound 7 comprises the following steps:
(1) compound 1, methylparaben (5.0g, 33mmol) and potassium carbonate (13.8g, 100mmol) were dissolved in 350mL of acetonitrile solution at room temperature, dibromoethane (30.9g, 165mmol) was added to the solution, and the mixture was stirred and refluxed at 80 ℃ under argon atmosphere for 12 hours to obtain Compound 5 by substitution reaction. Wherein the molar ratio of compound 1 to potassium carbonate is 1: and 3, the molar ratio of the compound 1 to dibromoethane is 1: 5.
(2) adding the compound 5(5.1g, 19.6mmol) and trimethylamine (5.8g, 98mmol) into 200mL ethanol, and stirring and refluxing for 12h at 80 ℃ under an argon atmosphere to obtain the quaternary ammonium salt compound 6, wherein the molar ratio of the compound 5 to the trimethylamine is 1: 5.
(3) mixing the compound 6(4.1g, 12mmol), hydrazine hydrate (3.2g, 60mmol) and 120mL of methanol, and stirring and refluxing the mixture for 12h at the temperature of 70 ℃ under an argon atmosphere to obtain a compound 7, wherein the molar ratio of the compound 6 to the hydrazine hydrate is 1: 5.
example 1
Compound 7(0.1g, 0.31mmol), 1-pyrenecarboxaldehyde (0.07g, 0.31mmol), trifluoroacetic acid (10uL) were mixed with ethanol (40mL), stirred under reflux at 80 ℃ under argon atmosphere for 24 hours, and the reaction was monitored by TLC follow-up until the starting material was consumed. The reaction solution was cooled to room temperature, the solvent was distilled off under reduced pressure, and recrystallization was carried out to obtain 0.1g of compound 8 in a yield of 72%.
The specific synthetic route is as follows:
FIG. 1 is a drawing of Compound 8 prepared in example 1 of the present invention1An H-NMR chart of the sample,1H NMR(400MHz,DMSO-d6)δ＝11.98(s,1H),9.55(s,1H),8.84(d,J＝9.1Hz,1H),8.59(d,J＝8.8Hz,1H),8.39(d,J＝7.8Hz,3H),8.27(dd,J＝18.3,8.9Hz,3H),8.15(m,1H),8.07(d,J＝8.7Hz,2H),7.20(d,J＝8.8Hz,2H),4.60(s,2H),3.84(s,2H),3.21(s,9H).
FIG. 2 is a diagram showing the fluorescence spectrum of Compound 8 prepared in example 1 of the present invention, which has a maximum fluorescence emission wavelength of 460 nm.
Example 2
Compound 7(0.2g, 0.62mmol), 1, 3-pyrenedicarbaldehyde (0.08g, 0.31mmol), trifluoroacetic acid (10uL) were mixed with ethanol (40mL), stirred under reflux at 80 ℃ under argon atmosphere for 24 hours, and the reaction was monitored by TLC follow-up to raw material exhaustion. The reaction solution was cooled to room temperature, the solvent was distilled off under reduced pressure, and recrystallization was carried out to obtain 0.15g of compound 9 in 56% yield.
The specific synthetic route is as follows:
FIG. 3 is a drawing of Compound 9 prepared in example 2 of the present invention1An H-NMR chart of the sample,1H NMR(400MHz,DMSO-d6)δ＝12.03(s,2H),9.58(s,2H),8.91(d,J＝7.8Hz,2H),8.64(d,J＝7.7Hz,2H),8.44(m,4H),8.07(d,J＝8.5Hz,4H),7.20(d,J＝8.7Hz,4H),4.60(s,4H),3.85(s,4H),3.21(s,18H)。
FIG. 4 is a diagram showing a fluorescence spectrum of Compound 9 prepared in example 2 of the present invention, which has a fluorescence maximum emission wavelength of 625 nm.
Example 3
Compound 7(0.2g, 0.62mmol), 1, 6-pyrenedicarbaldehyde (0.08g, 0.31mmol), and trifluoroacetic acid (10uL) were mixed with ethanol (40mL), and stirred under reflux at 80 ℃ under an argon atmosphere for 24 hours. The mixture was cooled to room temperature, the solvent was distilled off under reduced pressure, and recrystallization was carried out to obtain 0.18g of compound 10 in 68% yield.
The specific synthetic route is as follows:
FIG. 5 is a photograph of Compound 10, prepared according to example 3 of the present invention1An H-NMR chart of the sample,1H NMR(400MHz,DMSO-d6)δ＝12.10(s,2H),9.63(s,2H),8.89(d,J＝9.0Hz,2H),8.63(d,J＝7.8Hz,4H),8.33(m,4H),8.06(d,J＝8.7Hz,4H),7.19(d,J＝8.7Hz,4H),4.59(s,4H),3.85(s,4H),3.22(s,18H)。
FIG. 6 is a diagram showing a fluorescence spectrum of Compound 10 prepared in example 3 of the present invention, which has a fluorescence maximum emission wavelength of 625 nm.
Example 4
Compound 7(0.2g, 0.62mmol), 1, 8-pyrenedicarbaldehyde (0.08g, 0.31mmol), and trifluoroacetic acid (10uL) were mixed with ethanol (40mL), and stirred under reflux at 80 ℃ under an argon atmosphere for 24 hours. The mixture was cooled to room temperature, the solvent was distilled off under reduced pressure, and recrystallization was carried out to obtain 0.14g of compound 11 in 53% yield.
The specific synthetic route is as follows:
FIG. 7 is a photograph of Compound 11 prepared in example 4 of the present invention1An H-NMR chart of the sample,1H NMR(400MHz,DMSO-d6)δ＝12.04(s,2H),9.58(s,2H),8.90(d,J＝7.8Hz,2H),8.64(d,J＝7.7Hz,2H),8.44(m,4H),8.07(d,J＝8.6Hz,4H),7.21(d,J＝8.7Hz,4H),4.60(s,4H),3.85(s,4H),3.22(s,18H)。
FIG. 8 is a diagram showing a fluorescence spectrum of Compound 11 prepared in example 4 of the present invention, which has a fluorescence maximum emission wavelength of 625 nm.
Example 5
Compound 7(0.2g, 0.62mmol), 2, 7-pyrenedicarbaldehyde (0.08g, 0.31mmol), and trifluoroacetic acid (10uL) were mixed with ethanol (40mL), and stirred under reflux at 80 ℃ under an argon atmosphere for 24 hours. The mixture was cooled to room temperature, the solvent was distilled off under reduced pressure, and recrystallization was carried out to obtain 0.16g of compound 12 in 60% yield.
The specific synthetic route is as follows:
FIG. 9 is a photograph of Compound 12 prepared in example 5 of the present invention1An H-NMR chart of the sample,1H NMR(400MHz,DMSO-d6)δ＝12.05(s,2H),8.91(s,2H),8.66(s,2H),8.33(s,4H),8.06(d,J＝8.3Hz,4H),7.19(d,J＝8.7Hz,4H),4.59(s,4H),3.85(s,4H),3.22(s,18H)。
FIG. 10 is a diagram showing the fluorescence spectrum of Compound 12 prepared in example 5 of the present invention, which has a maximum fluorescence emission wavelength of 460 nm.
Example 6
36mg of Compound 11 was dissolved in 30mL of water to give an orange-yellow clear aqueous solution having a concentration of 8.33X 10- 4And mol/L shows that the pyrene-containing dye synthesized by the invention has good water solubility. Figure 11 is a yellow-orange clear aqueous solution of compound 11 prepared in example 4 of the present invention.
Comparative example 1
Due to the hydrophobicity of the pyrenyl group, most of the pyrene-containing dyes are insoluble in water at present, 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt is one of the few existing pyrene dyes capable of being dissolved in water, the chemical structural formula of the pyrene-containing trisodium salt is shown as a formula II, and the pyrene-containing dye has strong green light emission near 512 nm.
FIG. 12 is a diagram showing a fluorescence spectrum of trisodium 8-hydroxypyrene-1, 3, 6-trisulfonate in a comparative example of the present invention, the fluorescence maximum emission wavelength of which is 512 nm.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. A pyrene-containing water-soluble dye is characterized in that the water-soluble dye is a compound shown in a formula I:
wherein R is1Is one of the following groups:
or, R1、R3And is one of the following groups:
or, R1、R6And is one of the following groups:
or, R1、R8And is one of the following groups:
or, R2、R7And is one of the following groups:
2. The water-soluble dye according to claim 1, wherein,
R1is composed of
R2、R3、R4、R5、R6、R7、R8、R9、R10Are all hydrogen;
or, R1、R3At the same time are
R2、R4、R5、R6、R7、R8、R9、R10Are all hydrogen;
or, R1、R6At the same time are
R2、R3、R4、R5、R7、R8、R9、R10Are all hydrogen;
or, R1、R8At the same time are
R2、R3、R4、R5、R6、R7、R9、R10Are all hydrogen;
or, R2、R7At the same time are
R1、R3、R4、R5、R6、R8、R9、R10Are all hydrogen.
3. The water-soluble dye according to claim 2, wherein the water-soluble dye is one of the following compounds:
4. a process for preparing the water-soluble dye of claim 1, comprising the steps of:
dissolving a compound 1 and potassium carbonate in an acetonitrile solution at room temperature, adding dibromoalkane, and stirring and refluxing for 1-24 h under the argon atmosphere at the temperature of 70-90 ℃ to obtain a compound 2; the molar ratio of the compound 1 to the potassium carbonate is 1:3, and the molar ratio of the compound 1 to the dibromoalkane is 1: 5;
secondly, adding the compound 2 and trimethylamine into ethanol, and stirring and refluxing for 1-24 h under the argon atmosphere at the temperature of 70-90 ℃ to obtain a compound 3; wherein the molar ratio of the compound 2 to the trimethylamine is 1: 5;
thirdly, dissolving the compound 3 and hydrazine hydrate in methanol, and stirring and refluxing for 1-24 h under the argon atmosphere at the temperature of 70-90 ℃ to obtain a compound 4; the molar ratio of the compound 3 to the hydrazine hydrate is 1 (5-50);
fourthly, dissolving the compound 4, the 1-pyrene formaldehyde or pyrene substitute and excessive trifluoroacetic acid in ethanol, and stirring and refluxing for 1-24 h under the argon atmosphere at the temperature of 70-90 ℃ to obtain a compound shown in the formula I;
the molar ratio of the compound 4 to the 1-pyrene formaldehyde is 1: 1; the molar ratio of the compound 4 to the pyrene substituent is 2:1, and n is 2 or 3.
5. The method of claim 4, wherein the dibromoalkane is dibromoethane or dibromopropane.
6. The method of claim 4, wherein the pyrene substituent is 1, 3-pyrene dicarboxaldehyde, 1, 6-pyrene dicarboxaldehyde, 1, 8-pyrene dicarboxaldehyde or 2, 7-pyrene dicarboxaldehyde.
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