CN102627869A - Preparation method of near-infrared heptamethine cyanine dye and use of the near-infrared heptamethine cyanine dye in weak polarity-polarity mixed solvent fluorescence spectrum test - Google Patents
Preparation method of near-infrared heptamethine cyanine dye and use of the near-infrared heptamethine cyanine dye in weak polarity-polarity mixed solvent fluorescence spectrum test Download PDFInfo
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Abstract
The invention relates to a near-infrared heptamethine cyanine dye, a preparation method of the near-infrared heptamethine cyanine dye and a use of the near-infrared heptamethine cyanine dye in a weak polarity-polarity mixed solvent fluorescence spectrum test, and belongs to the technical field of chemical-engineering advanced-technology chemistry and biochemical analysis. The near-infrared heptamethine cyanine dye synthesized by the preparation method has excellent spectral properties, such as a large Stokes shift and strong light stability. The preparation method has simple synthesis steps. The near-infrared heptamethine cyanine dye is obviously characterized in that double fluorescence peaks of the near-infrared heptamethine cyanine dye in a weak polarity solvent are produced and an intensity ratio of the double fluorescence peaks and the polarity of the solvent are in a linear relationship. Therefore, the near-infrared heptamethine cyanine dye can be used for detecting a volume ratio of a weak polarity-polarity mixed solvent system. The preparation method does not change a matrix structure of the traditional heptamethine cyanine dye and only improves substituent groups of R1, R2 and R3 of the 4-type heptamethine cyanine dye.
Description
Technical field
The present invention relates to a kind of near infrared seven methine cyanine dyes and preparation method thereof and the application of this dyestuff in the test of low-pole-polarized mixed solvent fluorescence spectrum, belong to chemical industry new and high technology chemistry and biochemical analysis technical field.
Background technology
Cyanine dyes because have that molar extinction coefficient is big, fluorescence property is good, combines fluorescence efficiency increase afterwards with matrix, the maximum absorption wavelength tunable range is big, makes it be widely used in aspects such as spectral sensitization, infrared laser dye, optical disc recording medium, LB film, electrofax, optical nonlinearity material, solar cell, trace metal ion detection.Develop rapidly along with biotechnology and fluorescence labeling technology; Cyanine dyes has become the main fluorescent probe that in DNA, protein and nucleic acid etc. analyses are detected, uses; Especially near infrared seven methine cyanine dyes, its maximum absorption and emission wavelength can effectively be avoided the autofluorescence of biomolecules in the near-infrared region of 600～900nm; Reduce background fluorescence and disturb, obvious superiority is arranged in biological sample analysis.
There are external Patonay group and Waggoner group etc. in the main study group of synthetic exploitation of near infrared seven methine cyanine dyes.The research work that Xiamen University etc. do cyanine dye is more, and they mainly are that the dyestuff that is used for the mark biomacromolecule is synthesized in the work of using for reference people such as Narayanant and Patonay.And its application aspect the CD-R CD media is mainly studied by Yao Zu Guang study group.The invention provides a kind of preparation method of near-infrared cyanine dye; The absorption spectrum of such cyanine dyes is at 650nm; Fluorescence emission spectrum is positioned at the near-infrared region about 800nm, has bigger Stokes shift, has the potential actual application value at the biomolecule analysis detection range.
Summary of the invention
The objective of the invention is to overcome above-mentioned weak point; Provide a kind of novel being used for to detect the preparation method of the near infrared seven methine cyanine dyes of two kinds of polarity-low-pole mixed solvent volume ratio; The synthetic dyestuff has good spectrum property; Big like the stokes displacement, light stability is strong, and synthesis step is simple.Such dyestuff the most significantly characteristic is two fluorescence peaks in weak polar solvent, to occur, has linear relationship between the intensity rate at two peaks and the polarity of solvent, can be used for detecting the ratio of the volume in two kinds of mixed solvent systems of low-pole-polarity.This invention does not change the precursor structure of traditional seven methine cyanine dyes, only to the substituent R of 4 type dyes wherein
1, R
2And R
3Improve.
According to technical scheme provided by the invention, a kind of near infrared seven methine cyanine dyes, skeleton symbol is following:
Wherein, X be O, S or-C (CH
3)
2
R
1For H ,-SO
3H ,-COOH or phenyl ring;
R
2For comprising benzyl CH
2C
6H
5Or the verivate of benzyl,
Wherein M is any one in (a)～(h):
(a) M=H, (b) M=F, (c) M=Cl, (d) M=Br, (e) M=I, (f) M=OCH
3, (g) M=CH
3Or (h) M=COOH;
R
3For O, S ,-CH
2Or-NH;
The certain density dyestuff storing solution of having of equivalent A is joined respectively in the mixed solvent series of different volumes ratio of certain volume; Be mixed with a series of fluorescent reagent mixed solvent B to be detected; Note the fluorescence spectrum figure of certain density fluorescent reagent with XRF continuous sweep; Note the maximum fluorescence emission intensity of two fluorescence emission peaks of each fluorescent reagent; Volume ratio with weak polar solvent and polar solvent is an X-coordinate, and the maximum emission intensity ratio of the fluorescence emission peak of shortwave strong point and long wave strong point is that ordinate zou is figure and is obtained typical curve.With the low-pole and the polarized mixed solvent of unknown volume ratio, under same condition,, survey its fluorescence spectrum figure then, get the maximum fluorescence emission intensity rate of two fluorescence emission peaks, on typical curve, can try to achieve the volume ratio of unknown sample with the dye solution effect.
A kind of preparation method of near infrared seven methine cyanine dyes, route is shown below:
The preparation of near infrared seven methine cyanine dyes comprises following three steps: (1) 1 type midbody heterocycle 2,3,3-trimethylammonium 3H-indoles and verivate thereof synthetic; Synthesizing of (2) 2 type midbody heterocyclic quaternary ammonium salts; (3) heterocyclic quaternary ammonium salt and condensing agent condensation get 3 type dyes; (4) preparation of near infrared seven methine cyanine dyes 4;
(1) 1 type midbody heterocycle 2,3,3-trimethylammonium 3H-indoles and verivate thereof synthetic: in the 1 type midbody, when X=O, S, said 1 type midbody is available from market; As X=C (CH
3)
2The time; 1 type midbody heterocycle 2; 3,3-trimethylammonium 3H-indoles and verivate thereof be through the preparation of Fischer method, is raw material with phenylhydrazine or β-naphthylhydrazine, 4-carboxyl phenylhydrazine, 4-sulfonic group phenylhydrazine promptly; Generate corresponding hydrazone with 3-methyl-2-butanone with mol ratio 1: 1～2 reacting by heating, be closed into ring through acid-catalyzed dehydration again; Wherein 2,3, the 3-trimethylammonium-3H-indoline-5-potassium sulfonate will be via 2,3, and 3-trimethylammonium-3H-indoline-5-sulfonic acid and Pottasium Hydroxide prepared in reaction obtain;
The preparation of (2) 2 type midbodys: get step (1) preparation or the 1 type midbody of buying and the substituted halogenation benzylidene derivative of contraposition M
and in organic solvent, heat the generation alkylated reaction, obtain corresponding heterocyclic quaternary ammonium salt with mol ratio 1: 1～5;
The preparation of (3) 3 type dyes:
The preparation of condensing agent 2b (2-chlorine 1-formyl radical-3-hydroxy methylene tetrahydrobenzene): under 0-5 ℃ of ice bath, the Phosphorus Oxychloride of volume ratio 1: 1～1.2 and the mixed liquor A of exsiccant methylene dichloride are added dropwise in the mixed liquid B; Mixed liquor A and mixed liquid B volume ratio are 1: 1.5～2; Mixed liquid B is by exsiccant methylene dichloride and N, and dinethylformamide is l by volume: 1～1.2 forms; And then dropwise add with Phosphorus Oxychloride quality (g) volume (mL) than the pimelinketone that is 3～5: 1; Remove ice bath, reaction solution is heated to backflow, reaction 2～4h postcooling is poured into to place in the trash ice and is spent the night, and promptly obtains yellow solid, filters, and gets condensing agent 2b;
The preparation of 3 type dyes: the 2 type midbody heterocyclic quaternary ammonium salts and the condensing agent 2b that get step (2) preparation are 2: 1～1.2 with mol ratio; Do catalyst reaction with acetate and acid; Temperature of reaction is 60～80 ℃; Reaction times is 20min～60min, and the mol ratio of used acetate and condensing agent 2b is 1～1.2: 1; From solvent, directly separate out or pass through to pour in an amount of sodium halide aqueous solution and separate out solid, collect after filtering, get product 3 type dyes;
(4) preparation of near infrared seven methine cyanine dyes 4:
1: 1 in molar ratio～5 get 3 type dyes and the corresponding hexa-atomic nitrogen heterocyclic ring of step (3) preparation; Heated and stirred 1～5h in organic solvent; 3 type midbodys are 1～20: 1 with the quality mg volume mL ratio of solvent; Remove solvent under reduced pressure, the gained solid is used ethyl alcohol recrystallization, obtains product near infrared seven methine cyanine dyes.
The said organic solvent of step (2) is anhydrous methanol, absolute ethyl alcohol, acetonitrile, toluene, o-Xylol, m-xylene, p-Xylol, orthodichlorobenzene, Meta Dichlorobenzene, santochlor, N, dinethylformamide or N, N-DMSO 99.8MIN.;
(3 said acetate catalysts are sodium-acetate, Potassium ethanoate or Lithium Acetate to step; Described acid is acetic anhydride or acetic acid; Said sodium halide is sodium-chlor, Sodium Bromide, Sodium Fluoride, Soiodin or sodium tetrafluoroborate.
The said organic solvent of step (4) is anhydrous methanol, absolute ethyl alcohol, acetonitrile, N, dinethylformamide or N, N-DMSO 99.8MIN..
The application of said near infrared seven methine cyanine dyes in the test of low-pole-polarized mixed solvent fluorescence spectrum, step is following:
(1) preparation of dyestuff storing solution A: accurate weighing near infrared seven methine cyanine dyes dyestuffs, be dissolved in the organic solvent, be mixed with 1 * 10
-6～1 * 10
-3The dyestuff storing solution A of mol/L places deepfreeze subsequent use;
(2) preparation of mixed solvent B: mixed solvent B is low-pole-polarized mixed solvent, mixes respectively by getting some spots on weak polar solvent and the typical curve of polar solvent with the need drafting;
(3) fluorescence spectrum test: select storing solution 0.0001～2mL for use; Used XRF is commercially available XRF; The slit width value that excites and launch selects 3～20, and selecting the maximum excitation wavelength for use is between 400～620nm, notes the maximum fluorescence intensity value of each scanning; Volume ratio with mixed solvent B is an X-coordinate, and the maximum emission intensity ratio of the fluorescence emission peak of shortwave strong point and long wave strong point is that ordinate zou is figure and is obtained typical curve; With the low-pole and the polarized mixed solvent of unknown volume ratio, under same condition,, survey its fluorescence spectrum figure then, get the maximum fluorescence emission intensity rate of two fluorescence emission peaks, on typical curve, try to achieve the volume ratio of unknown sample with dyestuff storing solution A effect.
The said organic solvent of step (1) is anhydrous methanol, absolute ethyl alcohol, acetonitrile, acetone, acetate, ETHYLE ACETATE, chloroform, N, dinethylformamide or N, N-DMSO 99.8MIN..
The said weak polar solvent of step (2) comprises toluene, o-Xylol, p-Xylol, m-xylene, 1,4-dioxane, hexanaphthene, normal hexane, ether, sherwood oil.
The said polar solvent of step (2) comprises methyl alcohol, ethanol, acetonitrile, acetone, acetate, ETHYLE ACETATE, chloroform, methylene dichloride or 1,2-ethylene dichloride.
The present invention has following advantage: the present invention in comprising three kinds of heteroatomic near infrared seven methine cyanine dyes parents of difference, the nitrogenous six-ring and the R of meta methene chain
3Introducing contains not homoatomic such as oxygen, sulphur, nitrogen, carbon, can make dyestuff obtain bigger Stokes shift, improves the absorption spectrum and the fluorescence emission spectrum performance of dyestuff; R
2The bigger benzyl of volume or the verivate of benzyl are introduced in the position, can increase sterically hinderedly, stop the attack of active oxygen such as singlet oxygen, ultra-oxygen anion free radical etc., thereby strengthen the light stability of dyestuff.
Two fluorescence peaks appear in dyestuff in weak polar solvent, dyestuff demonstrates highly sensitive fluorescence response to the variation of solvent polarity.Can be used as the fluorescent probe of low-pole environment.
Description of drawings
Fig. 1 near infrared seven methine cyanine dyes 4-1 were respectively 9: 1 at toluene and methylene chloride volume ratio, and 7.33: 1,7: 1,5.99: 1,4.99: 1,4: 1,3: 1,2: 1,1: 1, the fluorogram in 0.786: 1 the mixed solvent.
Fig. 2 near infrared seven methine cyanine dyes 4-1 were respectively 9: 1 at dioxane and ethanol volume ratio, and 8.09: 1,7.33: 1,5.99: 1,4.99: 1,4: 1,3: 1,2: 1, the fluorogram in 0.67: 1 the mixed solvent.
Fig. 3 near infrared seven methine cyanine dyes 4-2 are 9: 1 at dioxane and ethanol volume ratio, 7.33: 1, and 6.14: 1,4.56: 1,3.17: 1, the fluorogram in 1.94: 1 the mixed solvent.
Fig. 4 near infrared seven methine cyanine dyes 4-2 are 9: 1 at hexanaphthene and ethanol volume ratio, 7.33: 1, and 6.14: 1,5.25: 1,4: 1, the fluorogram in 1.94: 1 the mixed solvent.
Fig. 5 near infrared seven methine cyanine dyes 4-3 are 9: 1 at toluene with the methylene chloride volume ratio, 7.33: 1, and 6.14: 1,5.25: 1,4: 1,1.94: 1, the fluorogram in 1: 1 the mixed solvent.
Fig. 6 near infrared seven methine cyanine dyes 4-3 are 9: 1 at dioxane and ethanol volume ratio, 7.33: 1, and 6.14: 1,4.56: 1,4: 1,3.17: 1,1.94: 1, the fluorogram in 1: 1 the mixed solvent.
Fig. 7 near infrared seven methine cyanine dyes 4-1's
1H NMR nuclear magnetic spectrogram.
Fig. 8 near infrared seven methine cyanine dyes 4-2's
1H NMR nuclear magnetic spectrogram.
Embodiment
In the said 1 type midbody of embodiment, when X=O, S, raw material is purchased in lark prestige Science and Technology Ltd.;
Structural formula is following:
Concrete steps are:
(1) 1 type midbody 2,3,3-trimethylammonium-3H indoles synthetic: weighing 27g phenylhydrazine (0.25mol) joins in two mouthfuls of flasks of 250mL; Stir and slowly drip 3-methyl-2 butanone 21g (0.25mol) down, be heated to 70-80 ℃, reacted 4 hours; Isolating water layer is used extracted with diethyl ether, and the ether layer of oil reservoir and extraction merges, and adds an amount of anhydrous magnesium sulfate drying and filters; Decompression steams solvent, promptly gets rough hydrazone 35g, yield 80%.
The hydrazone 35g (0.4mol) that the last step is rough mixes with the 75mL Glacial acetic acid min. 99.5, and reaction is 3 hours in 90 ℃ of oil baths, is cooled to room temperature; Use saturated aqueous sodium carbonate to be neutralized to water layer and be neutrality, water phase separated and organic phase, water is used extracted with diethyl ether; Extraction liquid and organic phase merge, and anhydrous magnesium sulfate drying steams ether, underpressure distillation again after filtering; Collect the cut of 130-140 ℃ of (0.08-0.09Mp) boiling range, obtain pale yellow oily liquid body 26g.
(2) 2 type midbodys 22,3,3-trimethylammonium-1-benzyl-3H indoles quaternary ammonium salt synthetic: with 1.59 g 2,3,3-trimethylammonium-3H indoles and 1.27g (10.1mmol) Benzyl Chloride join 25mL and contain 10mL1, in the round-bottomed flask of 2-orthodichlorobenzene.After being heated to 110 ℃, reaction stops behind the sustained reaction 12h.Mixture cooled and filtered deposition is also used washing with acetone impurity.Obtain the peach powder of 1.90g after the drying.
The preparation of (3) 3 type dyes:
The preparation of condensing agent 2b (2-chlorine 1-formyl radical-3-hydroxy methylene tetrahydrobenzene): the mixed solution with 37mL Phosphorus Oxychloride and 35mL exsiccant methylene dichloride under ice bath (0-5 ℃) is added dropwise to 80mL by exsiccant methylene dichloride and N; (volume ratio is l to dinethylformamide: in the mixed solution of 1) forming, and then dropwise add the 10g pimelinketone.Remove ice bath, reaction solution is heated to backflow, reaction 3h postcooling is poured in the 200g trash ice.Placement is spent the night, and obtains red solid, filters, and gets thick product 8.2g.
Synthesizing of 3 type dyes: accurate weighing 0.572g (2mmol) 2,3,3-trimethylammonium-1-benzyl-3H indoles quaternary ammonium salt; 0.180g (1mmol) condensing agent 2-chlorine 1-formyl radical-3-hydroxy methylene tetrahydrobenzene and sodium acetate, anhydrous 0.188g (2.1mmol) join in the 25mL round-bottomed flask that contains the 15mL acetic anhydride successively, are heated to 70 ℃; Solution becomes is green, stops behind the reaction 15min, after the cooling green solution is joined in the saturated sodium chloride aqueous solution; Separate out the green colouring material solid, filter the back and collect.Bullion is recrystallization in ethanol, filters after drying and obtains the 0.3g green solid.
(4) near infrared seven methine cyanine dyes 4-1's is synthetic: accurate weighing 67.1mg (0.1mmol) dyestuff 3-1, and piperidines 26mg (0.3mmol) joins in the 50mL round-bottomed flask, adds the 5mL methylene dichloride again; Stir 2h under the room temperature, reaction solution becomes mazarine by green gradually, after reaction stops; Revolve to steam and remove dichloromethane solvent, the gained sticky solid is with 30mL ether stir about 5 hours, triplicate; Filtration obtains powder, uses ethyl alcohol recrystallization, obtains mazarine pressed powder 68mg.
Nuclear-magnetism figure is as shown in Figure 7:
1H NMR (d
6-CDCl
3): δ 1.605 (m, 2H, CH
2), 1.682 (s, 12H, CH
3), 2.227-2.260 (t, 4H, CH
2), 3.096 (s, 4H, CH
2), 3.879 (m, 4H, CH
2), 5.058 (s, 4H, CH
2), 5.576-5.604 (d, 2H, CH), 7.079-7.521 (m, 20H, Ar-H, CH), mass spectrum MS (m/z): 684 [M]
+.
Structural formula is following:
Accurately 3 type midbody 67.1mg (0.1mmol), the morphine quinoline 26mg (0.3mmol) of weighing embodiment 1 preparation join in the 50mL round-bottomed flask, add the 5mL methylene dichloride again; Stir 2h under the room temperature, reaction solution becomes mazarine by green gradually, after reaction stops; Revolve to steam and remove dichloromethane solvent, the gained sticky solid is with 30mL ether stir about 5 hours, triplicate; Filtration obtains powder, uses ethyl alcohol recrystallization, obtains mazarine pressed powder 60mg.
Nuclear-magnetism figure is as shown in Figure 8:
1H-NMR (d
6-DMSO): δ 1.57 (m, 2H, C-CH
2), 1.62 (s, 12H, CH
3), 2.28 (t, 4H, CH
2-C), 2.97 (t, 4H, O-CH
2), 3.69 (t, 4H, N-CH
2) 5.24 (s, 4H, CH
2-Ar), 5.79 (d, 2H, J=12Hz, C=CH), 7.41 (d, 2H, J=12Hz, CH=C), 7.06-7.51 (m, 18H, Ar-H), mass spectrum MS (m/z): 686 [M]
+.
Structural formula is following:
3 type dye 67.1mg (0.1mmol) of accurate weighing embodiment 1 preparation are dissolved in 2mL alcoholic acid piperazine hexahydrate 87mg (0.5mmol) and join in the 50mL round-bottomed flask, add the 5mL methylene dichloride again, stir 2h under the room temperature; Reaction solution becomes mazarine by green gradually, after reaction stops, revolving to steam to remove and desolvates; The gained solid was with 30mL ether stir about 5 hours, and triplicate filters and obtains powder; Use ethyl alcohol recrystallization, obtain golden needle-like crystal 65mg.
Nuclear-magnetism:
1H NMR (d
6-DMSO): δ 1.59 (m, 2H, CH
2-C), 1.64 (s, 12H, CH
3), 2.30 (t, 4H, C-CH
2), 3.70 (t, 4H, N-CH
2), 3.83 (t, 4H, N-CH
2) 5.29 (s, 4H, CH
2-Ar), 5.86 (d, 2H, J=12Hz, C=CH), 7.47 (d, 2H, J=12Hz, CH=C), 7.10-7.54 (m, 18H, Ar-H), mass spectrum MS (m/z): 685 [M]
+.
Structural formula is following:
(1) 1 type midbody 2,3,3-trimethylammonium-5-carboxyl-3H indoles synthetic: weighing 4-carboxyl phenylhydrazine 38g (0.25mol) joins in the 50mL absolute ethyl alcohol, is heated to 80 ℃.Stir and slowly drip 3-methyl-2-butanone 21g (0.25mol) down, react 2 hours postcooling, add the 50mL Glacial acetic acid min. 99.5, continue to be heated to 90 ℃ of reactions 3 hours, be cooled to room temperature, steaming desolventizes, and collects pressed powder 35g.
(2) 2 type midbodys 2,3,3-trimethylammonium-1-benzyl-5-carboxyl-3H indoles quaternary ammonium salt synthetic: with 2,3,3-trimethylammonium-5-carboxyl-3H indoles 2.03g and 1.717g (10.1mmol) cylite join 25mL and contain 10mL1, in the round-bottomed flask of 2-orthodichlorobenzene.After being heated to 110 ℃, reaction stops behind the sustained reaction 12h.Mixture cooled and filtered deposition is also used washing with acetone impurity, obtains the 2.8g powder after the drying.
The preparation of (3) 3 type dyes: accurate weighing 0.748g (2mmol) 2,3,3-trimethylammonium-1-benzyl-5-carboxyl-3H indoline salt; 0.180g (1mmol) the condensing agent 2-chlorine 1-formyl radical-3-hydroxy methylene tetrahydrobenzene and the sodium acetate, anhydrous 0.188g (2.1mmol) of embodiment 1 step (3) preparation; Join successively in the 25mL round-bottomed flask that contains the 15mL acetic anhydride, be heated to 70 ℃, solution becomes is green; Stop behind the reaction 15min; After the cooling green solution is joined in the saturated sodium chloride aqueous solution, separate out the green colouring material solid, filter the back and collect.Bullion is recrystallization in ethanol, filters after drying and obtains the 0.5g green solid.
(4) near infrared seven methine cyanine dyes 4-4's is synthetic: accurate weighing 80.4mg (0.1mmol) dyestuff 3-2, and piperidines 26mg (0.3mmol) joins in the 50mL round-bottomed flask, adds the 5mL methylene dichloride again; Stir 2h under the room temperature, reaction solution becomes mazarine by green gradually, after reaction stops; Revolve to steam and remove dichloromethane solvent, the gained sticky solid is with 30mL ether stir about 5 hours, triplicate; Filtration obtains powder, uses ethyl alcohol recrystallization, obtains mazarine pressed powder 85mg.
Nuclear-magnetism
1H NMR (d
6-CDCl
3): δ 1.623 (m, 2H, CH
2), 1.678 (s, 12H, CH
3), 2.232-2.263 (t, 4H, CH
2), 3.124 (s, 4H, CH
2), 3.978 (m, 4H, CH
2), 5.128 (s, 4H, CH
2), 5.587-5.634 (d, 2H, CH), 7.568-7.985 (m, 16H, Ar-H, CH), mass spectrum MS (m/z): 772.1 [M]
+.
Structural formula is following:
Synthesizing of (1) 1 type midbody: 2,3,3-trimethylammonium-3H-indoline-5-potassium sulfonate
2; 3; The preparation of 3-trimethylammonium-3H-indoline-5-sulfonic acid: 2.5g (0.013mol) phenyl hydrazine-p-sulfonic acid, 4.2mL (0.04mol) 3-methyl-2-butanone and 8ml Glacial acetic acid min. 99.5 are joined in the flask, and 90 ℃ of heated and stirred 3 hours are after reaction stops; Remove most glacial acetic acid under reduced pressure, add ETHYLE ACETATE in the residuum and separate out solid.The filtration final vacuum is dry, gets 2,3,3-trimethylammonium-3H-indoline-5-sulphonate 2.0g.
In the 50mL round-bottomed flask, add 5mL methyl alcohol successively, the 5mL Virahol; 4.8g (0.02mol) 2; 3,3-trimethylammonium-3H-indoline-5-sulfonic acid (analytical pure is purchased in lark prestige Science and Technology Ltd.) and 1.23g (0.022mol) KOH mixture heating up reflux; Pink is decorporated, and cooling has a large amount of yellow solids to separate out.Filter, vacuum-drying gets midbody 2,3,3-trimethylammonium-3H-indoline-5-potassium sulfonate 4.2g.
(2) 2 type midbodys 2,3,3-trimethylammonium-1-benzyl-3H-indoline-5-potassium sulfonate synthetic: in the 50mL round-bottomed flask, add 1.56g (0.006mol) 2 successively; 3,3-trimethylammonium-3H-indoline-5-sulfonic acid potassium salt, 0.80g (0.0063mol) Benzyl Chloride; Ethanol 15mL, heating reflux reaction is 5 hours under nitrogen protection, obtains pink solid; Filter, with ETHYLE ACETATE washing, vacuum-drying.Get thick product 1.24g, productive rate 60%.Dyestuff 4-5's is synthetic:
The preparation of (3) 3 type dyes: accurately take by weighing embodiment 1 preparation 0.389g (2.2mmol) 2-chloro-1-formyl radical-3-hydroxyl methyne tetrahydrobenzene 2b successively, 1.415g (4mmol) N-benzyl-2,3; 3-trimethylammonium-3H-indoline-5-potassium sulfonate adds in the 50mL round-bottomed flask, adds 15mL ethanol, adds water trap; Add alcohol solvent in the water trap, under the nitrogen protection, stirring and refluxing 5h; Solution becomes scarlet by light red gradually, becomes green at last.Leave standstill cooling after reaction finishes, suction filtration gets green crystal 0.85g, thick productive rate 49%.Do recrystallization three times with ethanol, get final product pure substance.
(4) near infrared seven methine cyanine dyes 4-5's is synthetic: accurate weighing 80.8mg (0.1mmol) dyestuff 3-2, and piperidines 26mg (0.3mmol) joins in the 50mL round-bottomed flask; Add N again, N-dimethyl--methane amide 5mL stirs 4h under the room temperature; Reaction solution becomes mazarine by green gradually, and after reaction stopped, low-temperature reduced-pressure steamed solvent; Surplus products are used ethyl alcohol recrystallization, obtain mazarine pressed powder 50mg.
Nuclear-magnetism
1H-NMR (d
6-DMSO): δ 1.601 (m, 2H, CH
2), 1.491 (s, 12H, CH
3), 2.245-2.270 (t, 4H, CH
2), 3.126 (s, 4H, CH
2), 3.869 (m, 4H, CH
2), 5.321 (s, 4H, CH
2), 5.587-6.634 (d, 2H, CH), 7.643-7.987 (m, 16H, Ar-H, CH), mass spectrum MS (m/z): 844.1 [M]
+
Structural formula is following:
(1) 1 type midbody 2,3,3-trimethylammonium-3H benzindole synthetic: weighing 40g β-naphthylhydrazine hydrochloride joins and is heated to 80 ℃ in the 50mL absolute ethyl alcohol, slowly drips 3-methyl-2 butanone 21g; Reacted 2 hours, and added the 30mL Glacial acetic acid min. 99.5 and mix, reaction is 3 hours in 90 ℃ of oil baths; Be cooled to room temperature, decompression steams solvent, obtains 18g raw product 2; 3,3-trimethylammonium-3H benzindole, bullion recrystallization in hexanaphthene obtains pure article.
(2) 2 type midbodys 2,3,3-trimethylammonium-1-benzyl-3H benzindole quaternary ammonium salt synthetic: with 1.59g2,3,3-trimethylammonium-3H benzindole and 1.717g (10.1mmol) cylite join 25mL and contain 10mL1, in the round-bottomed flask of 2-orthodichlorobenzene.After being heated to 110 ℃, reaction stops behind the sustained reaction 12h.Mixture cooled and filtered deposition.Obtain the 2.32g powder after the drying.
The preparation of (3) 3 type dyes: accurate weighing 0.760g (2mmol) 2,3,3-trimethylammonium-1-benzyl-3H benzindole quinoline salt; 0.180g (1mmol) 2-chlorine 1-formyl radical-3-hydroxy methylene tetrahydrobenzene 2b and sodium acetate, anhydrous 0.188g (2.1mmol) join in the 25mL round-bottomed flask that contains the 15mL acetic anhydride successively, are heated to 70 ℃; Solution becomes is green, stops behind the reaction 15min, after the cooling green solution is joined in the saturated aqueous sodium bromide; Separate out the green colouring material solid, filter the back and collect.Bullion is recrystallization in ethanol, filters after drying and obtains the 0.5g green solid.
(4) near infrared seven methine cyanine dyes 4-6's is synthetic: accurate weighing 74mg (0.1mmol) dyestuff 3-1, and piperidines 26mg (0.3mmol) joins in the 50mL round-bottomed flask; Add the 5mL methylene dichloride again, stir 2h under the room temperature, reaction solution becomes mazarine by green gradually; After reaction stops; Revolve to steam to remove and desolvate, obtain solid and use ethyl alcohol recrystallization, obtain mazarine pressed powder 57mg.
Nuclear-magnetism
1H NMR (d
6-CDCl
3): δ 1.615 (m, 2H, CH
2), 1.662 (s, 12H, CH
3), 2.217-2.274 (t, 4H, CH
2), 3.138 (s, 4H, CH
2), 3.926 (m, 4H, CH
2), 5.275 (s, 4H, CH
2), 5.569-5.698 (d, 2H, CH), 7.237-7.964 (m, 22H, Ar-H, CH), mass spectrum MS (m/z): 784 [M]
+
Structural formula is following:
(1) 1 type midbody 2-methyl-benzothiazole is purchased for commercial article, purchases in lark prestige Science and Technology Ltd..
(2) 2 type midbody 2-methyl-3-benzyl-benzothiazole quaternary ammonium salts synthetic: 1.49g (10mmol) 2-methyl-benzothiazole and 1.27g (10.1mmol) cylite are joined 25mL contain 10mL1, in the round-bottomed flask of 2-orthodichlorobenzene.After being heated to 110 ℃, reaction stops behind the sustained reaction 10h.Mixture cooled and filtered deposition is also used washing with acetone impurity, obtains the 1.82g pressed powder after the drying.
The preparation of (3) 3 type midbodys: accurate weighing 0.638g (2mmol) 2-methyl-3-benzyl-benzothiazolium salt, 0.180g (1mmol) condensing agent 2-chlorine 1-formyl radical-3-hydroxy methylene tetrahydrobenzene and sodium acetate, anhydrous 0.188g (2.1mmol) joins in the 25mL round-bottomed flask that contains the 15mL acetic anhydride successively; Be heated to 70 ℃; Solution becomes is green, stops behind the reaction 15min, after the cooling green solution is joined in the saturated aqueous sodium bromide; Separate out the green colouring material solid, filter the back and collect.Bullion is recrystallization in acetone, filters after drying and obtains the 0.42g green solid.
(4) near infrared seven methine cyanine dyes 4-7's is synthetic: accurate weighing 69.4mg (0.1mmol) dyestuff 3-4, and piperidines 26mg (0.3mmol) joins in the 50mL round-bottomed flask; Add the 5mL methylene dichloride again, stir 3h under the room temperature, reaction solution becomes mazarine by green gradually; After reaction stops; Revolve to steam and remove dichloromethane solvent, surplus materials is used acetone recrystallization, obtains mazarine pressed powder 75mg.
Nuclear-magnetism
1H NMR (d
6-CDCl
3): δ 1.609 (m, 2H, CH
2), 2.228-2.265 (t, 4H, CH
2), 3.123 (s, 4H, CH
2), 3.890 (m, 4H, CH
2), 5.213 (s, 4H, CH
2), 5.581-5.625 (d, 2H, CH), 7.234-7.567 (m, 18H, Ar-H, CH), mass spectrum MS (m/z): 664 [M]
+
Structural formula is following:
(1) 1 type midbody 2-methyl-benzoxazoles are purchased in lark prestige Science and Technology Ltd..
(2) 2 type midbody 2-methyl-3-benzyl-benzoxazole quaternary ammonium salts synthetic: 1.33g (10mmol) 2-methyl-benzothiazole and 1.27g (10.1mmol) cylite are joined 25mL contain 10mL1, in the round-bottomed flask of 2-orthodichlorobenzene.After being heated to 110 ℃, reaction stops behind the sustained reaction 10h.Mixture cooled and filtered deposition is also used washing with acetone impurity, obtains the 1.75g pressed powder after the drying.
The preparation of (3) 3 type dyes: accurate weighing 0.606g (2mmol) 2-methyl-3-benzyl-benzoxazole salt, 0.180g (1mmol) condensing agent 2-chlorine 1-formyl radical-3-hydroxy methylene tetrahydrobenzene and sodium acetate, anhydrous 0.188g (2.1mmol) joins in the 25mL round-bottomed flask that contains the 15mL acetic anhydride successively; Be heated to 70 ℃; Solution becomes is green, stops behind the reaction 15min, after the cooling green solution is joined in the saturated aqueous sodium bromide; Separate out the green colouring material solid, filter the back and collect.Bullion is recrystallization in acetone, filters after drying and obtains the 0.46g green solid.
(4) near infrared seven methine cyanine dyes 4-8's is synthetic: accurate weighing 66.4mg (0.1mmol) dyestuff 3-5, and piperidines 26mg (0.3mmol) joins in the 50mL round-bottomed flask; Add the 5mL methylene dichloride again, stir 3h under the room temperature, reaction solution becomes mazarine by green gradually; After reaction stops; Revolve to steam and remove dichloromethane solvent, surplus materials is used ethyl alcohol recrystallization, obtains mazarine pressed powder 65mg.
Nuclear-magnetism
1H NMR (d
6-CDCl
3): δ 1.613 (m, 2H, CH
2), 2.243-2.268 (t, 4H, CH
2), 3.152 (s, 4H, CH
2), 3.987 (m, 4H, CH
2), 5.265 (s, 4H, CH
2), 5.589-5.692 (d, 2H, CH), 7.265-7.593 (m, 18H, Ar-H, CH), mass spectrum MS (m/z): 632 [M]
+
The application of embodiment 9 near infrareds, seven methine cyanine dyes in the test of low-pole-polarized mixed solvent fluorescence spectrum
Accurate respectively weighing 6mg dyestuff 4-1,4-2,4-3 use 10mL acetone constant volume respectively, are made into dyestuff storing solution 8.4 * 10
-4Mol/L, for use.Dose volume is that the volume ratio of 20mL is V respectively
1/ V
2=9: 1,7.33: 1,7: 1,6.14: 1,5.99: 1,5.25: 1,4.99: 1,4: 1,3: 1,2: 1,1.94: 1,1: 1,0.786: 1 toluene-methylene dichloride mixed solvent; Respectively part long-pending for the volume ratio of 20mL be V
1/ V
2=9: 1,8.09: 1,7.33: 1,5.99: 1,4.99: 1,4: 1,3: 1,2: 1,0.67: 1 dioxane and alcohol mixed solvent; Respectively part long-pending for the 20mL volume ratio be V
1/ V
2=9: 1,7.33: 1,6.14: 1,5.25: 1,4: 1,1.94: 1 hexanaphthene and alcohol mixed solvent, subsequent use.Get 100 μ L dyestuff storing solutions, the above-mentioned mixed solvent for preparing of 5mL is added in the 10mL tube comparison tubes, shakes up, and is to be measured.It is 560nm that excitation wavelength is set, and exciting slit is 10nm, and the emission slit is 5nm, reads shortwave strong point photoluminescence peak I
1, long wave strong point photoluminescence peak I
2, X-coordinate is V
1/ V
2Value, ordinate zou is I
1/ I
2The value mapping obtains typical curve.
As shown in Figure 1, dyestuff 4-1 was respectively 9: 1 at toluene and methylene chloride volume ratio, and 7.33: 1,7: 1,5.99: 1,4.99: 1,4: 1,3: 1,2: 1,1: 1, the fluorogram in 0.786: 1 the mixed solvent.The X-coordinate of little figure is the volume ratio of toluene and methylene dichloride, and ordinate zou is the ratio of photoluminescence peak of photoluminescence peak and the ICT attitude of LE attitude, and both have good linear relationship (R
2=0.9962).
As shown in Figure 2, dyestuff 4-1 was respectively 9: 1 at dioxane and ethanol volume ratio, and 8.09: 1,7.33: 1,5.99: 1,4.99: 1,4: 1,3: 1,2: 1, the fluorogram in 0.67: 1 the mixed solvent.The X-coordinate of little figure is dioxane and alcoholic acid volume ratio, and ordinate zou is the ratio of photoluminescence peak of photoluminescence peak and the ICT attitude of LE attitude, and both have good linear relationship (R
2=0.9978).
As shown in Figure 3, dyestuff 4-2 is 9: 1 at dioxane and ethanol volume ratio, 7.33: 1, and 6.14: 1,4.56: 1,3.17: 1, the fluorogram in 1.94: 1 the mixed solvent.The X-coordinate of little figure is dioxane and alcoholic acid volume ratio, and ordinate zou is the ratio of photoluminescence peak of photoluminescence peak and the ICT attitude of LE attitude, and both have good linear relationship (R
2=0.97067).
As shown in Figure 4, dyestuff 4-2 is 9: 1 at hexanaphthene and ethanol volume ratio, 7.33: 1, and 6.14: 1,5.25: 1,4: 1, the fluorogram in 1.94: 1 the mixed solvent.
As shown in Figure 5, dyestuff 4-3 is 9: 1 at toluene with the methylene chloride volume ratio, 7.33: 1, and 6.14: 1,5.25: 1,4: 1,1.94: 1, the fluorogram in 1: 1 the mixed solvent.
As shown in Figure 6, dyestuff 4-3 is 9: 1 at dioxane and ethanol volume ratio, 7.33: 1, and 6.14: 1,4.56: 1,4: 1,3.17: 1,1.94: 1, the fluorogram in 1: 1 the mixed solvent.
Claims (9)
1. near infrared seven methine cyanine dyes is characterized in that skeleton symbol is following:
Wherein, X be O, S or-C (CH
3)
2
R
1For H ,-SO
3H ,-COOH or phenyl ring;
R
2For comprising benzyl CH
2C
6H
5Or the verivate of benzyl,
Wherein M is any one in (a)～(h):
(a) M=H, (b) M=F, (c) M=Cl, (d) M=Br, (e) M=I, (f) M=OCH
3, (g) M=CH
3Or (h) M=COOH;
R
3For O, S ,-CH
2Or-NH;
The certain density dyestuff storing solution of having of equivalent A is joined respectively in the mixed solvent series of different volumes ratio of certain volume; Be mixed with a series of fluorescent reagent mixed solvent B to be detected; Noting the fluorescence spectrum figure of certain density fluorescent reagent with XRF continuous sweep, note the maximum fluorescence emission intensity of two fluorescence emission peaks of each fluorescent reagent, is X-coordinate with the volume ratio of weak polar solvent and polar solvent; The maximum emission intensity ratio of the fluorescence emission peak of shortwave strong point and long wave strong point is that ordinate zou is figure and is obtained typical curve; With the low-pole and the polarized mixed solvent of unknown volume ratio, under same condition,, survey its fluorescence spectrum figure then with the dye solution effect; Get the maximum fluorescence emission intensity rate of two fluorescence emission peaks, on typical curve, can try to achieve the volume ratio of unknown sample.
2. the preparation method of near infrared seven methine cyanine dyes is characterized in that route is shown below:
The preparation of near infrared seven methine cyanine dyes comprises following three steps: (1) 1 type midbody heterocycle 2,3,3-trimethylammonium 3H-indoles and verivate thereof synthetic; Synthesizing of (2) 2 type midbody heterocyclic quaternary ammonium salts; (3) heterocyclic quaternary ammonium salt and condensing agent condensation are worth 3 type dyes; (4) preparation of near infrared seven methine cyanine dyes 4;
(1) 1 type midbody heterocycle 2,3,3-trimethylammonium 3H-indoles and verivate thereof synthetic: in the 1 type midbody, when X=O, S, said 1 type midbody is available from market; As X=C (CH
3)
2The time; 1 type midbody heterocycle 2; 3,3-trimethylammonium 3H-indoles and verivate thereof be through the preparation of Fischer method, is raw material with phenylhydrazine or β-naphthylhydrazine, 4-carboxyl phenylhydrazine, 4-sulfonic group phenylhydrazine promptly; Generate corresponding hydrazone with 3-methyl-2-butanone with mol ratio 1: 1～2 reacting by heating, be closed into ring through acid-catalyzed dehydration again; Wherein 2,3, the 3-trimethylammonium-3H-indoline-5-potassium sulfonate will be via 2,3, and 3-trimethylammonium-3H-indoline-5-sulfonic acid and Pottasium Hydroxide prepared in reaction obtain;
The preparation of (2) 2 type midbodys: get step (1) preparation or the 1 type midbody of buying and the substituted halogenation benzylidene derivative of contraposition M
and in organic solvent, heat the generation alkylated reaction, obtain corresponding heterocyclic quaternary ammonium salt with mol ratio 1: 1～5;
The preparation of (3) 3 type dyes:
The preparation of condensing agent 2b (2-chlorine 1-formyl radical-3-hydroxy methylene tetrahydrobenzene): under 0-5 ℃ of ice bath, the Phosphorus Oxychloride of volume ratio 1: 1～1.2 and the mixed liquor A of exsiccant methylene dichloride are added dropwise in the mixed liquid B; Mixed liquor A and mixed liquid B volume ratio are 1: 1.5～2; Mixed liquid B is by exsiccant methylene dichloride and N, and dinethylformamide is 1: 1～1.2 compositions by volume; And then dropwise to add with Phosphorus Oxychloride quality g volume mL ratio be 3～5: 1 pimelinketone; Remove ice bath, reaction solution is heated to backflow, reaction 2～4h postcooling is poured into to place in the trash ice and is spent the night, and promptly obtains yellow solid, filters, and gets condensing agent 2b;
The preparation of 3 type dyes: the 2 type midbody heterocyclic quaternary ammonium salts and the condensing agent 2b that get step (2) preparation are 2: 1～1.2 with mol ratio; Do catalyst reaction with acetate and acid; Temperature of reaction is 60～80 ℃; Reaction times is 20min～60min, and the mol ratio of used acetate and condensing agent 2b is 1～1.2: 1; From solvent, directly separate out or pass through to pour in an amount of sodium halide aqueous solution and separate out solid, collect after filtering, get product 3 type dyes;
(4) preparation of near infrared seven methine cyanine dyes 4:
1: 1 in molar ratio～5 get 3 type dyes and the corresponding hexa-atomic nitrogen heterocyclic ring of step (3) preparation; Heated and stirred 1～5h in organic solvent; 3 type midbodys are 1～20: 1 with the quality mg volume mL ratio of solvent; Remove solvent under reduced pressure, the gained solid is used ethyl alcohol recrystallization, obtains product near infrared seven methine cyanine dyes.
3. like the preparation method of the said near infrared seven methine cyanine dyes of claim 2; It is characterized in that: the said organic solvent of step (2) is anhydrous methanol, absolute ethyl alcohol, acetonitrile, toluene, o-Xylol, m-xylene, p-Xylol, orthodichlorobenzene, Meta Dichlorobenzene, santochlor, N; Dinethylformamide or N, the N-DMSO 99.8MIN..
4. like the preparation method of the said near infrared seven methine cyanine dyes of claim 2, it is characterized in that: (3 said acetate catalysts are sodium-acetate, Potassium ethanoate or Lithium Acetate to step; Described acid is acetic anhydride or acetic acid; Said sodium halide is sodium-chlor, Sodium Bromide, Sodium Fluoride, Soiodin or sodium tetrafluoroborate.
5. like the preparation method of the said near infrared seven methine cyanine dyes of claim 2, it is characterized in that: the said organic solvent of step (4) is anhydrous methanol, absolute ethyl alcohol, acetonitrile, N, dinethylformamide or N, N-DMSO 99.8MIN..
6. the application of the said near infrared seven methine cyanine dyes of claim 1 in the test of low-pole-polarized mixed solvent fluorescence spectrum is characterized in that step is following:
(1) preparation of dyestuff storing solution A: accurate weighing near infrared seven methine cyanine dyes dyestuffs, be dissolved in the organic solvent, be mixed with 1 * 10
-6～1 * 10
-3The dyestuff storing solution A of mol/L places deepfreeze subsequent use;
(2) preparation of mixed solvent B: mixed solvent B is low-pole-polarized mixed solvent, mixes respectively by getting some spots on weak polar solvent and the typical curve of polar solvent with the need drafting;
(3) fluorescence spectrum test: select storing solution 0.0001～2mL for use; Used XRF is commercially available XRF; The slit width value that excites and launch selects 3～20, and selecting the maximum excitation wavelength for use is between 400～620nm, notes the maximum fluorescence intensity value of each scanning; Volume ratio with mixed solvent B is an X-coordinate, and the maximum emission intensity ratio of the fluorescence emission peak of shortwave strong point and long wave strong point is that ordinate zou is figure and is obtained typical curve; With the low-pole and the polarized mixed solvent of unknown volume ratio, under same condition,, survey its fluorescence spectrum figure then, get the maximum fluorescence emission intensity rate of two fluorescence emission peaks, on typical curve, try to achieve the volume ratio of unknown sample with dyestuff storing solution A effect.
7. like the application of the said near infrared seven methine cyanine dyes of claim 6 in the test of low-pole-polarized mixed solvent fluorescence spectrum; It is characterized in that: the said organic solvent of step (1) is anhydrous methanol, absolute ethyl alcohol, acetonitrile, acetone, acetate, ETHYLE ACETATE, chloroform, N; Dinethylformamide or N, the N-DMSO 99.8MIN..
8. like the application of the said near infrared seven methine cyanine dyes of claim 6 in the test of low-pole-polarized mixed solvent fluorescence spectrum; It is characterized in that: the said weak polar solvent of step (2) comprises toluene, o-Xylol, p-Xylol, m-xylene, 1,4-dioxane, hexanaphthene, normal hexane, ether, sherwood oil.
9. like the application of the said near infrared seven methine cyanine dyes of claim 6 in the test of low-pole-polarized mixed solvent fluorescence spectrum; It is characterized in that: the said polar solvent of step (2) comprises methyl alcohol, ethanol, acetonitrile, acetone, acetate, ETHYLE ACETATE, chloroform, methylene dichloride or 1,2-ethylene dichloride.
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