CN113248940A - Heptamethine cyanine dye with high-selectivity red light absorption, and synthesis method and application thereof - Google Patents
Heptamethine cyanine dye with high-selectivity red light absorption, and synthesis method and application thereof Download PDFInfo
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- CN113248940A CN113248940A CN202110518903.9A CN202110518903A CN113248940A CN 113248940 A CN113248940 A CN 113248940A CN 202110518903 A CN202110518903 A CN 202110518903A CN 113248940 A CN113248940 A CN 113248940A
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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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/0075—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of an heterocyclic ring
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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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
- C09B23/086—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines more than five >CH- groups
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/30—Camouflage paints
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Abstract
The invention discloses a high-selectivity heptamethine cyanine dye with red light absorption, a synthesis method and application thereof, wherein 2,3, 3-trimethyl-3H-indole-5 sulfonic acid sylvite is used as a raw material, a heptamethine cyanine dye derivative is obtained through amidation reaction and coupling reaction, and then the heptamethine cyanine dye derivative is reacted with N, N-diethyl-3-aminophenol to obtain the heptamethine cyanine dye. The dye has good light stability and molar extinction coefficient of 3.2 multiplied by 105M‑1·cm‑1The half-peak width is 26nm, the red light absorbing performance is good, and the red light absorbing coating can be applied to green camouflage coatings. The color difference value between the appearance color of the prepared coating and the prepared standard color is 0.5-1.2, the emissivity of 3-5 mu m of an infrared band is 0.65-0.68, the emissivity of 8-4 mu m is 0.78-0.79, the reflectivity at the position of 680nm is 10-12%, and meanwhile, the coating can also meet the red edge effect and the red edge effect of green plantsThe spectral channel requirement of GJB7928 and the hyperspectral requirement of GJB 1411A.
Description
Technical Field
The invention relates to the technical field of synthesis of heptamethine cyanine dyes, in particular to a heptamethine cyanine dye with high selective red light absorption, a synthesis method and application thereof.
Background
The maximum absorption wavelength of the heptamethine cyanine dye is generally between 600nm and 1000nm, the heptamethine cyanine dye has good fluorescence performance and a larger molar absorption coefficient, and the absorption wavelength of the cyanine dye can be regulated and controlled by modifying the molecular structure of the heptamethine cyanine dye so as to achieve the purpose of absorption at different wavelengths. Therefore, the method has important significance for exploring the influence factors of the optical-near infrared absorption performance.
Despite the considerable progress that has been made in the research of heptamethine cyanine dyes, much work remains to be done in improving and perfecting the photophysical properties of the dyes. The longer the linear methine chain (i.e., the longer the conjugated chain), the poorer the photostability. The main reason for this phenomenon is that singlet oxygen and a methine bond undergo photo-oxidation, which causes a photo-degradation reaction of the dye. Therefore, the research on how to improve the light stability of the heptamethine cyanine dye is of great significance.
Disclosure of Invention
The invention provides a high-selectivity red light absorption heptamethine cyanine dye, a synthesis method and application thereof, wherein a large aromatic ring structure is introduced into a conjugated chain through reaction, and a large steric hindrance group is introduced near the conjugated chain, so that the dye has good light stability, and has the advantages of large molar extinction coefficient, narrow half-peak width, good absorption performance in a red light region and the like, and can be applied to a green camouflage coating.
In order to achieve the purpose, the invention provides a heptamethine cyanine dye with high selective red light absorption, which has the structural formula:
in order to achieve the above object, the present invention further provides a method for synthesizing the heptamethine cyanine dye with high selective red light absorption, which comprises the following steps:
s1: weighing 2,3, 3-trimethyl-3H-indole-5 potassium sulfonate and p-benzyl bromobenzoic acid according to the molar ratio of 1 (1-1.05), dissolving the potassium sulfonate and the p-benzyl bromobenzoic acid in acetonitrile together, and carrying out reflux reaction under the protection of inert atmosphere to obtain an intermediate product I;
s2: weighing the intermediate product I, diethylamine, N '-dicyclohexylcarbodiimide and 4-dimethylaminopyridine according to a molar ratio of 1:1.2:0.2:0.5, placing the intermediate product I and diethylamine into a three-neck flask containing dichloromethane, adding the N, N' -dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and fully reacting to obtain an intermediate product II;
s3: weighing the intermediate product II and 2-chloro-1-formyl-3-hydroxymethylcyclohexene according to the molar ratio of 1 (1-1.05), placing the intermediate product II and the 2-chloro-1-formyl-3-hydroxymethylcyclohexene into a three-neck flask, adding a toluene/n-butanol mixed solution, and carrying out reflux reaction under the protection of inert atmosphere to obtain a heptamethine cyanine dye derivative;
s4: weighing the heptamethine cyanine dye derivative and N, N-diethyl-3-aminophenol according to the molar ratio of 1 (1-1.05), placing the heptamethine cyanine dye derivative and the N, N-diethyl-3-aminophenol into a three-neck flask, adding anhydrous DMF, stirring and dissolving, adding sodium hydride, and performing reflux reaction under the protection of inert atmosphere to obtain the heptamethine cyanine dye.
In order to achieve the purpose, the invention also provides application of the high-selectivity red light absorption heptamethine cyanine dye, wherein the heptamethine cyanine dye or the heptamethine cyanine dye synthesized by the synthesis method is applied to a green camouflage coating.
Compared with the prior art, the invention has the beneficial effects that:
1. the synthesis method of the high-selectivity red light absorption heptamethine cyanine dye provided by the invention takes 2,3, 3-trimethyl-3H-indole-5 sulfonic acid potassium salt as raw material, firstly reacts with p-benzyl bromobenzoic acid to prepare N-alkylated benzindole derivative (intermediate product I), then carrying out amidation reaction with diethylamine, introducing a larger steric hindrance group to the vicinity of a conjugated chain to obtain an intermediate derivative (an intermediate product II), then adding 2-chloro-1-formyl-3-hydroxymethylcyclohexene to react to obtain a heptamethine conjugated cyanine dye derivative, finally reacting the heptamethine cyanine dye derivative with N, N-diethyl-3-aminophenol, and introducing a large aromatic ring structure into the conjugated chain to obtain a heptamethine cyanine final product. The synthetic method has the advantages of simple process, few byproducts, high yield, good light stability of the synthesized heptamethine cyanine dye, good red light selective absorption performance and capability of being applied to green camouflage coatings.
2. The heptamethine cyanine dye provided by the invention has good selective absorption characteristic at 680nm, and the molar extinction coefficient is 3.2 multiplied by 105M-1·cm-1The half-peak width was 26 nm. The invention discovers that when the heptamethine cyanine dye is applied to a green camouflage coating, the color difference value between the appearance color of the green camouflage coating and the matched standard color is 1.0-1.2, the emissivity of an infrared band of 3-5 microns is 0.65-0.68, the emissivity of 8-4 microns is 0.78-0.79, the reflectivity at 680nm is 10-12%, the requirement that the reflectivity of America army standard dark green is less than or equal to 12% of the reflectivity at 680nm is met, meanwhile, the red edge effect K value of a green plant is more than 5, the near infrared brightness contrast with a typical background color is less than or equal to 0.2, and the spectral channel requirement of GJB7928 and the hyperspectral requirement of GJB1 1411A are met.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a diagram of an absorption spectrum of a heptamethine cyanine dye;
FIG. 2 is a graph of the reflection spectrum of a medium green MG 1151-green camouflage coating;
FIG. 3 is a graph of the dark green DG 0730-green camouflage coating reflection spectrum.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical solutions in the embodiments of the present invention may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination of technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
The drugs/reagents used are all commercially available without specific mention.
The invention provides a heptamethine cyanine dye with high selective red light absorption, which has a structural formula as follows:
red light generally refers to light after 600 nm.
The invention also provides a synthesis method of the heptamethine cyanine dye with high selective red light absorption, which comprises the following steps:
s1: weighing 2,3, 3-trimethyl-3H-indole-5 potassium sulfonate and p-benzyl bromobenzoic acid according to the molar ratio of 1 (1-1.05), dissolving the potassium sulfonate and the p-benzyl bromobenzoic acid in acetonitrile together, and carrying out reflux reaction under the protection of inert atmosphere to obtain an intermediate product I;
s2: weighing the intermediate product I, diethylamine, N '-dicyclohexylcarbodiimide and 4-dimethylaminopyridine according to a molar ratio of 1:1.2:0.2:0.5, placing the intermediate product I and diethylamine into a three-neck flask containing dichloromethane, adding the N, N' -dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and fully reacting to obtain an intermediate product II;
s3: weighing the intermediate product II and 2-chloro-1-formyl-3-hydroxymethylcyclohexene according to the molar ratio of 1 (1-1.05), placing the intermediate product II and the 2-chloro-1-formyl-3-hydroxymethylcyclohexene into a three-neck flask, adding a toluene/n-butanol mixed solution, and carrying out reflux reaction under the protection of inert atmosphere to obtain a heptamethine cyanine dye derivative;
s4: weighing the heptamethine cyanine dye derivative and N, N-diethyl-3-aminophenol according to the molar ratio of 1 (1-1.05), placing the heptamethine cyanine dye derivative and the N, N-diethyl-3-aminophenol into a three-neck flask, adding anhydrous DMF, stirring to dissolve, adding sodium hydride, and performing reflux reaction under the protection of inert atmosphere to obtain the heptamethine cyanine dye.
Preferably, the step S1 is specifically:
accurately weighing 10mmol of 2,3, 3-trimethyl-3H-indole-5 potassium sulfonate and 10-10.5 mmol of p-benzyl bromobenzoic acid, dissolving the two in 50ml of acetonitrile, carrying out reflux reaction for 8H under the protection of nitrogen atmosphere, cooling, carrying out rotary evaporation to remove the acetonitrile, washing with methyl tert-butyl ether or acetone for multiple times, and drying to obtain an intermediate product I. The yield was 78%.
Preferably, the step S2 is specifically:
accurately weighing 10mmol of the intermediate product I and 12mmol of diethylamine, placing the intermediate product I and 12mmol of diethylamine into a three-neck flask containing 100ml of dichloromethane, adding 2mmol of N, N' -dicyclohexylcarbodiimide and 5mmol of 4-dimethylaminopyridine, reacting for 6 hours at 35 ℃, decompressing and drying after the reaction is finished, and precipitating with acetone to obtain an intermediate product II. The yield was 85%.
Preferably, the step S3 is specifically:
accurately weighing 10mmol of the intermediate product II and 10-10.5 mmol of 2-chloro-1-formyl-3-hydroxymethylcyclohexene, placing the intermediate product II and 10-10.5 mmol of 2-chloro-1-formyl-3-hydroxymethylcyclohexene into a 250ml three-necked flask, adding 100ml of toluene/n-butanol mixed solution with the volume ratio of 7:3, heating the mixture from room temperature to 115 ℃ under the protection of nitrogen atmosphere, carrying out reflux reaction at 115 ℃ for 12 hours, filtering the reaction solution under reduced pressure, and repeatedly washing a filter cake with acetone to obtain the heptamethine cyanine dye derivative. The yield was 82%.
Preferably, the step S4 is specifically:
accurately weighing 10mmol of the heptamethine cyanine dye derivative and 10-10.5 mmol of N, N-diethyl-3-aminophenol, placing the heptamethine cyanine dye derivative and 10-10.5 mmol of N, N-diethyl-3-aminophenol in a 250ml three-necked flask, adding 25-50 ml of anhydrous DMF, magnetically stirring, adding 50-100 mg of sodium hydride after dissolution, reacting for 24 hours at 110 ℃ under the protection of nitrogen atmosphere, washing for multiple times by using deionized water, drying, decompressing, rotating and evaporating to dryness to obtain a crude product, and separating and purifying by using a silica gel column chromatography to obtain the heptamethine cyanine dye with the yield of 90%.
Preferably, the reaction formulae of steps S1 to S4 are:
S1：
S2：
S3：
S4：
the invention also provides application of the high-selectivity red light absorption heptamethine cyanine dye, which is applied to a green camouflage coating.
Preferably, the green camouflage coating comprises the following raw materials in parts by weight:
acrylic resin: 10-20;
the heptamethine cyanine dye: 0.2 to 0.5;
flake aluminum powder: 0.1 to 2;
pigment green: 3-5;
pigment yellow: 1-5;
pigment black: 0.5 to 1;
pigment red: 0.5 to 1;
organic solvent: 5-10;
other auxiliary agents: 0.2 to 0.5.
Preferably, the other auxiliary agents include a dispersant, an antifoaming agent, and the like.
Preferably, the flaky aluminum powder is floating aluminum powder, and the particle size is 8-12 microns.
Preferably, the organic solvent is N, N-dimethylformamide, xylene or N-butyl acetate.
Preferably, the preparation method of the green camouflage coating comprises the following steps:
(1) weighing acrylic resin, the heptamethine cyanine dye, the flake aluminum powder, the pigment green, the pigment yellow, the pigment black, the pigment red, the organic solvent and other auxiliaries in parts by weight, and dissolving the heptamethine cyanine dye, the pigment green, the pigment yellow, the pigment black and the pigment red in the organic solvent;
(2) adding the acrylic resin, the flaky aluminum powder and other auxiliaries, and grinding and dispersing at a high speed for 2 hours under the condition of 2500-3000 rmp/min to obtain a coating;
(3) and (3) adjusting the viscosity of the coating to 20-25 s (coating 4 cups, testing at 25 ℃), spraying the coating on a tin plate, and baking the coating at 100 ℃ for 10min to obtain the green camouflage coating.
Example 1
This example provides a heptamethine cyanine dye with highly selective red light absorption, which has the structural formula:
the embodiment also provides a method for synthesizing the high-selectivity heptamethine cyanine dye with red light absorption, which comprises the following steps:
s1: accurately weighing 10mmol of 2,3, 3-trimethyl-3H-indole-5 potassium sulfonate and 10-10.5 mmol of p-benzyl bromobenzoic acid, dissolving the two in 50ml of acetonitrile, carrying out reflux reaction for 8H under the protection of nitrogen atmosphere, cooling, carrying out rotary evaporation to remove the acetonitrile, washing with methyl tert-butyl ether or acetone for multiple times, and drying to obtain an intermediate product I.
S2: accurately weighing 10mmol of the intermediate product I and 12mmol of diethylamine, placing the intermediate product I and 12mmol of diethylamine into a three-neck flask containing 100ml of dichloromethane, adding 2mmol of N, N' -dicyclohexylcarbodiimide and 5mmol of 4-dimethylaminopyridine, reacting for 6 hours at 35 ℃, decompressing and drying after the reaction is finished, and precipitating with acetone to obtain an intermediate product II.
S3: accurately weighing 10mmol of the intermediate product II and 10-10.5 mmol of 2-chloro-1-formyl-3-hydroxymethylcyclohexene, placing the intermediate product II and 10-10.5 mmol of 2-chloro-1-formyl-3-hydroxymethylcyclohexene into a 250ml three-necked flask, adding 100ml of toluene/n-butanol mixed solution with the volume ratio of 7:3, heating the mixture from room temperature to 115 ℃ under the protection of nitrogen atmosphere, carrying out reflux reaction at 115 ℃ for 12 hours, filtering the reaction solution under reduced pressure, and repeatedly washing a filter cake with acetone to obtain the heptamethine cyanine dye derivative.
S4: accurately weighing 10mmol of the heptamethine cyanine dye derivative and 10-10.5 mmol of N, N-diethyl-3-aminophenol, placing the heptamethine cyanine dye derivative and 10-10.5 mmol of N, N-diethyl-3-aminophenol in a 250ml three-necked flask, adding 25-50 ml of anhydrous DMF, magnetically stirring, adding 50-100 mg of sodium hydride after dissolution, reacting for 24 hours at 110 ℃ under the protection of nitrogen atmosphere, washing for multiple times by using deionized water, drying, decompressing, rotating and evaporating to dryness to obtain a crude product, and separating and purifying by silica gel column chromatography (petroleum ether/dichloromethane/methanol is 30:20:1, v/v) to obtain the heptamethine cyanine dye.
The embodiment also provides an application of the high-selectivity red light absorption heptamethine cyanine dye, wherein the heptamethine cyanine dye or the heptamethine cyanine dye synthesized by the synthesis method is applied to a green camouflage coating, and is specifically applied to a medium green MG 1151-green camouflage coating, and the medium green MG 1151-green camouflage coating comprises the following raw materials in parts by mass:
acrylic resin: 10;
the heptamethine cyanine dye: 0.2;
flake aluminum powder: 0.3;
pigment green: 3.8 of the total weight of the mixture;
pigment yellow: 3.5;
pigment black: 0.5;
pigment red: 0.8;
organic solvent: 6;
other auxiliary agents: 0.4 (dispersant: 0.3, defoamer: 0.1).
The embodiment also provides a preparation method of the medium green MG1151- - -green camouflage coating, which comprises the following steps:
(1) weighing acrylic resin, heptamethine cyanine dye, flake aluminum powder, pigment green, pigment yellow, pigment black, pigment red, N-dimethylformamide, a dispersing agent and a defoaming agent in parts by weight, and dissolving the heptamethine cyanine dye, the pigment green, the pigment yellow, the pigment black and the pigment red in the N, N-dimethylformamide;
(2) adding acrylic resin, aluminum flake powder, a dispersing agent and a defoaming agent, and grinding and dispersing zirconium oxide beads in a dispersion machine at a high speed for 2 hours at a rotating speed of 3000rmp/min to obtain a coating;
(3) and (3) adjusting the viscosity of the coating to 20-25 s, spraying the coating on a tin plate, and baking the coating at 100 ℃ for 10min to obtain a medium green MG 1151-green camouflage coating.
The middle green MG1151 green camouflage coating L a b prepared in this example has a value of (40.6, -6.9,16.7) and a color difference Δ E of 1.06 from the standard color MG 1151. The emissivity of the coating at an infrared band of 3-5 mu m is 0.65, the emissivity at 8-14 mu m is 0.78, the reflectivity at 680nm is 10%, the requirement that the reflectivity of green in American military standard is less than or equal to 12% at 680nm is met, meanwhile, the coating can meet the requirement that the red edge effect K value of green plants is more than 5, the contrast with the near-infrared brightness of a typical background color is less than or equal to 0.2, the spectral channel requirement of GJB7928 and the hyperspectral requirement of GJB1411A are met, and a reflected spectrogram is shown in an attached figure 2.
Example 2
The embodiment provides an application of a high-selectivity red light absorption heptamethine cyanine dye, which is applied to a dark green DG 0730-green camouflage coating, wherein the dark green DG 0730-green camouflage coating comprises the following raw materials in parts by mass:
acrylic resin: 10;
the heptamethine cyanine dye: 0.25;
flake aluminum powder: 0.5;
pigment green: 5.0;
pigment yellow: 4.2;
pigment black: 1;
pigment red: 0.6;
organic solvent: 6;
other auxiliary agents: 0.35 (dispersant: 0.25, defoamer: 0.1).
The embodiment also provides a preparation method of the DG 0730-green camouflage coating, which comprises the following steps:
(1) weighing acrylic resin, heptamethine cyanine dye, flake aluminum powder, pigment green, pigment yellow, pigment black, pigment red, xylene, a dispersing agent and a defoaming agent in parts by weight, and dissolving the heptamethine cyanine dye, the pigment green, the pigment yellow, the pigment black and the pigment red in the xylene;
(2) adding acrylic resin, aluminum flake powder, a dispersing agent and a defoaming agent, and grinding and dispersing zirconium oxide beads in a dispersion machine at a high speed for 2 hours at a rotating speed of 2800rmp/min to obtain a coating;
(3) and (3) adjusting the viscosity of the coating to 20-25 s, spraying the coating on a tin plate, and baking the coating at 100 ℃ for 10min to obtain a DG 0730-green camouflage coating.
DG0730 prepared in this example-green camouflage coating L a b value (31.5, -4.6,7.5) and a color difference value of 0.7 with standard color DG 0730. The emissivity of the coating at an infrared band of 3-5 microns is 0.68, the emissivity of 8-14 microns is 0.79, the reflectivity at 680nm is 7.8%, the requirement that the reflectivity of the coating is less than or equal to 8% under the American military standard dark green and 680nm is met, the red edge effect K value of a green plant can be more than 5, the contrast with the near infrared brightness of a typical background color is less than or equal to 0.2, the spectral channel requirement of GJB7928 and the hyperspectral requirement of GJB1411A are met, and a reflected spectrogram is shown in an attached figure 3.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A heptamethine cyanine dye with high-selectivity red light absorption, which is characterized in that the heptamethine cyanine dye has a structural formula as follows:
2. a method for synthesizing a heptamethine cyanine dye with high selectivity for red light absorption according to claim 1, comprising the steps of:
s1: weighing 2,3, 3-trimethyl-3H-indole-5 potassium sulfonate and p-benzyl bromobenzoic acid according to the molar ratio of 1 (1-1.05), dissolving the potassium sulfonate and the p-benzyl bromobenzoic acid in acetonitrile together, and carrying out reflux reaction under the protection of inert atmosphere to obtain an intermediate product I;
s2: weighing the intermediate product I, diethylamine, N '-dicyclohexylcarbodiimide and 4-dimethylaminopyridine according to a molar ratio of 1:1.2:0.2:0.5, placing the intermediate product I and diethylamine into a three-neck flask containing dichloromethane, adding the N, N' -dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and fully reacting to obtain an intermediate product II;
s3: weighing the intermediate product II and 2-chloro-1-formyl-3-hydroxymethylcyclohexene according to the molar ratio of 1 (1-1.05), placing the intermediate product II and the 2-chloro-1-formyl-3-hydroxymethylcyclohexene into a three-neck flask, adding a toluene/n-butanol mixed solution, and carrying out reflux reaction under the protection of inert atmosphere to obtain a heptamethine cyanine dye derivative;
s4: weighing the heptamethine cyanine dye derivative and N, N-diethyl-3-aminophenol according to the molar ratio of 1 (1-1.05), placing the heptamethine cyanine dye derivative and the N, N-diethyl-3-aminophenol into a three-neck flask, adding anhydrous DMF, stirring to dissolve, adding sodium hydride, and performing reflux reaction under the protection of inert atmosphere to obtain the heptamethine cyanine dye.
3. The synthesis method according to claim 2, wherein the step S1 specifically comprises:
accurately weighing 10mmol of 2,3, 3-trimethyl-3H-indole-5 potassium sulfonate and 10-10.5 mmol of p-benzyl bromobenzoic acid, dissolving the two in 50ml of acetonitrile, carrying out reflux reaction for 8H under the protection of nitrogen atmosphere, cooling, carrying out rotary evaporation to remove the acetonitrile, washing with methyl tert-butyl ether or acetone for multiple times, and drying to obtain an intermediate product I.
4. The synthesis method according to claim 2, wherein the step S2 specifically comprises:
accurately weighing 10mmol of the intermediate product I and 12mmol of diethylamine, placing the intermediate product I and 12mmol of diethylamine into a three-neck flask containing 100ml of dichloromethane, adding 2mmol of N, N-dicyclohexylcarbodiimide and 5mmol of 4-dimethylaminopyridine, reacting for 6 hours at 35 ℃, decompressing and spin-drying after the reaction is finished, and precipitating with acetone to obtain an intermediate product II.
5. The synthesis method according to claim 2, wherein the step S3 specifically comprises:
accurately weighing 10mmol of the intermediate product II and 10-10.5 mmol of 2-chloro-1-formyl-3-hydroxymethylcyclohexene, placing the intermediate product II and 10-10.5 mmol of 2-chloro-1-formyl-3-hydroxymethylcyclohexene into a 250ml three-necked flask, adding 100ml of toluene/n-butanol mixed solution with the volume ratio of 7:3, heating the mixture from room temperature to 115 ℃ under the protection of nitrogen atmosphere, carrying out reflux reaction for 12 hours under the condition of the temperature, filtering the reaction solution under reduced pressure, and repeatedly washing a filter cake with acetone to obtain the heptamethine cyanine dye derivative.
6. The synthesis method according to claim 2, wherein the step S4 specifically comprises:
accurately weighing 10mmol of the heptamethine cyanine dye derivative and 10-10.5 mmol of N, N-diethyl-3-aminophenol, placing the heptamethine cyanine dye derivative and the N, N-diethyl-3-aminophenol in a 250ml three-necked flask, adding 25-50 ml of anhydrous DMF, magnetically stirring, adding 50-100 mg of sodium hydride after dissolution, reacting for 24 hours at 110 ℃ under the protection of nitrogen atmosphere, washing for multiple times by using deionized water, drying, decompressing, rotating and evaporating to dryness to obtain a crude product, and separating and purifying by using a silica gel column chromatography to obtain the heptamethine cyanine dye.
7. The synthesis method according to claim 2, wherein the reaction formula of the steps S1-S4 is:
S1：
S2：
S3：
S4：
8. the application of the high-selectivity red light absorption heptamethine cyanine dye is characterized in that the heptamethine cyanine dye in claim 1 or the heptamethine cyanine dye synthesized by the synthesis method in claims 2-8 is applied to a green camouflage coating.
9. The application of the high-selectivity red light absorbing heptamethine cyanine dye of claim 8, wherein the green camouflage coating comprises the following raw materials in parts by weight:
acrylic resin: 10-20;
the heptamethine cyanine dye: 0.2 to 0.5;
flake aluminum powder: 0.1 to 2;
pigment green: 3-5;
pigment yellow: 3.5-5;
pigment black: 0.5 to 1;
pigment red: 0.5 to 1;
organic solvent: 5-10;
other auxiliary agents: 0.2 to 0.5.
10. The use of a highly selective red-absorbing heptamethine cyanine dye according to claim 9, in which the green camouflage coating is prepared by a method comprising:
(1) weighing acrylic resin, the heptamethine cyanine dye, the flake aluminum powder, the pigment green, the pigment yellow, the pigment black, the pigment red, the organic solvent and other auxiliaries in parts by weight, and dissolving the heptamethine cyanine dye, the pigment green, the pigment yellow, the pigment black and the pigment red in the organic solvent;
(2) adding the acrylic resin, the flaky aluminum powder and other auxiliaries, and grinding and dispersing at a high speed for 2 hours under the condition of 2500-3000 rmp/min to obtain a coating;
(3) and (3) adjusting the viscosity of the coating to 20-25 s, spraying the coating on a tin plate, and baking the coating at 100 ℃ for 10min to obtain the green camouflage coating.
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| CN117169182A (en) * | 2023-08-30 | 2023-12-05 | 广州沙艾生物科技有限公司 | In-vitro efficacy detection method for stem cell therapeutic preparation and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796779A (en) * | 2017-11-17 | 2019-05-24 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of seven methines benzindole cyanine dye |
| CN111662568A (en) * | 2019-03-08 | 2020-09-15 | 中国科学院宁波材料技术与工程研究所 | Preparation method of heptamethine indole cyanine dye and application of dye |
| CN111662567A (en) * | 2019-03-08 | 2020-09-15 | 中国科学院宁波材料技术与工程研究所 | Heptamethine carboxyl indole cyanine dye and preparation method and application thereof |
| CN111662563A (en) * | 2019-03-08 | 2020-09-15 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of heptamethine benzindole cyanine dye |
-
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- 2021-05-12 CN CN202110518903.9A patent/CN113248940B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796779A (en) * | 2017-11-17 | 2019-05-24 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of seven methines benzindole cyanine dye |
| CN111662568A (en) * | 2019-03-08 | 2020-09-15 | 中国科学院宁波材料技术与工程研究所 | Preparation method of heptamethine indole cyanine dye and application of dye |
| CN111662567A (en) * | 2019-03-08 | 2020-09-15 | 中国科学院宁波材料技术与工程研究所 | Heptamethine carboxyl indole cyanine dye and preparation method and application thereof |
| CN111662563A (en) * | 2019-03-08 | 2020-09-15 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of heptamethine benzindole cyanine dye |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117169182A (en) * | 2023-08-30 | 2023-12-05 | 广州沙艾生物科技有限公司 | In-vitro efficacy detection method for stem cell therapeutic preparation and application thereof |
| CN117169182B (en) * | 2023-08-30 | 2024-03-15 | 广州沙艾生物科技有限公司 | In-vitro efficacy detection method for stem cell therapeutic preparation and application thereof |
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