CN106479216A - A kind of two pyrylium dyes of near-infrared aza fluorine boron and its microwave method synthetic method - Google Patents
A kind of two pyrylium dyes of near-infrared aza fluorine boron and its microwave method synthetic method Download PDFInfo
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Abstract
The invention belongs to technical field of organic synthesis, specifically discloses a kind of two pyrroles's fluorescent dye of near-infrared aza fluorine boron and its microwave synthesis method, as shown in Figure of abstract, its synthesis step includes two pyrroles's fluorescent dye compound structural formula of azepine fluorine boron：With parahydroxyacet-ophenone and to cyanobenzaldehyde as raw material, the α containing conjugated double bond, alpha, beta-unsaturated ketone compound 1 is obtained；By compound 1 in the basic conditions, it is heated to reflux occurring Michael addition to carry out nitrosation and obtain compound 2 with nitromethane；Using microwave method, it is 95 DEG C to keep reaction temperature, reacts 6h with ammonium acetate, obtains four aryl azepines, two pyrroles's methine class compound 3；Compound 3 obtains described two pyrylium dyes of near-infrared aza fluorine boron with triethylamine, boron trifluoride reaction.The invention has the advantages that, synthesizing the fluorochrome compared to conventional heating, microwave method can greatly shorten the reaction time, reduce accessory substance, improves reaction yield to a certain extent.
Description
Technical field
The present invention relates to technical field of organic synthesis, and in particular to a kind of two pyrroles's fluorescence of near-infrared aza fluorine boron dye
Material and its microwave synthesis method.
Background technology
Two pyrylium dyes of near-infrared aza fluorine boron, as a kind of new fluorescent dye, because which possesses excellent light
Learn property and the focus of optical function material research can be had become as in recent years, in biology as the characteristic of sensitising agent
Medical domain has boundless application prospect (J.Am.Chem.Soc.2004,126,10619-10631).
Four aryl azepines, two pyrroles's methine class compound and BF2Complexing, prevents bridge nitrogen key connected with pyrrole ring to occur
Isomery, obtains more preferable two pyrylium dyes of near-infrared aza fluorine boron of rigid plane, shows excellent optical property：
Fluorophore emission and absorbing wavelength are all near infrared region；Higher molar absorption coefficient (70000-80000M-1
cm-1) (Org.Lett., 2006,8,3493-3496) and fluorescence quantum yield (0.3-0.6)；Excellent light is stable
Property, less (Org.Lett., 2013,15,3392-3395) etc. is affected by environment, pH value of solution.Wavelength of fluorescence exists
Near infrared region, possesses higher biological tissue's penetrability, can effectively eliminate cell autofluorescence interference
(Org.Lett., 2008,10,4771-4774), reduces the damage (Org. during observation to cell or tissue
Biomol.Chem.,2010,8,522-525).
Except possessing excellent optical property, this kind of dyestuff is also equipped with the characteristic of sensitising agent, for the treatment of cancer
With early diagnosis (RSC Adv., 2012,2,11169-11183).Sensitising agent in vivo, to tumor tissues
Different with normal tissue cell affinity, cause the holdup time different so as to be passively dispersed and be gathered in tumour,
Using specific wavelength light irradiation, sensitising agent is excited from ground state S0Transit to excitation state S1, due to energy be between
Cross over (ISC), cause excitation state S1To excitation state triplet T1, energy is by T1The ground state oxygen being transferred in cell,
The cytotoxic singlet oxygen of tool can be produced, cause Apoptosis (Chem.Commun., 2002,
1862-1863；J.Am.Chem.Soc.2005,127,16360-16361).Because illumination is only to irradiated area
Produce impact so that PDT (Photodynamic therapy photodynamic therapy) has for the treatment of cancer
High selectivity (J.Med.Chem.2010,53,7337-7343).Excellent optical property and as photosensitive
The characteristic of agent causes this kind of dyestuff to have great potential using value in field of biological detection.
Since (J.Chem.Soc.1943,590-596) being reported for the first time from this kind of compound, Donal F.
O ' Shea seminar continues to optimize synthesis condition, and two pyrylium dyes of azepine fluorine boron of difference in functionality are obtained in succession,
Progress (the J.Am.Chem.Soc.2011,133,19618-19621 of this fluorochrome is promoted；Int.
J.Cancer 2011,130,705-715；J.Org.Chem.2012,77,9304-9312；Org.Lett.,2013,
15,3392-3395).The route of conventional two azole compounds of synthesis azepine fluorine boron is as follows at present：
With α, alpha, beta-unsaturated ketone is raw material, through nitromethane nitrosation, adopts the conventional heating methods with absolute ethyl alcohol to be
Solvent is reacted with ammonium acetate, synthesizes four aryl azepines, two pyrroles's methine class compound, is obtained with boron trifluoride complexing
Two pyrroles's molecule of azepine fluorine boron.During synthesis four aryl azepines, two pyrroles's methine class compound, using routine
There is reaction time length (24h 72h), the defect of yield relatively low (12%-47%) in heating so that whole conjunction
Become the route deadline long, low yield.
Content of the invention
For the deficiencies in the prior art, the invention provides a kind of new two pyrroles of near-infrared aza fluorine boron
Dye composition and its microwave method synthetic method, its object is to make up in the existing method for synthesizing such compound
The some shortcomings of presence, compared to traditional conventional heating circumfluence method, can shorten the reaction time, improve reaction
Yield, minimizing accessory substance.
Technical solution
A kind of new two pyrylium dyes of near-infrared aza fluorine boron, structural formula are as follows：
The present invention still further provides a kind of microwave synthesis side of two pyrylium dyes of near-infrared aza fluorine boron
Method, synthetic route are as follows：
Above-mentioned synthetic method is comprised the steps of：
Step one：Parahydroxyacet-ophenone and cyanobenzaldehyde is reacted in the basic conditions, obtain α, β-insatiable hunger
With ketone 1.By 1：The parahydroxyacet-ophenone of 1 mol ratio and absolute ethyl alcohol is dissolved in cyanobenzaldehyde, add 3
The potassium hydroxide of times parahydroxyacet-ophenone mole, is stirred overnight at room temperature, then plus 3 times of parahydroxyacet-ophenones mole
The potassium hydroxide of amount, continues 5h is stirred at room temperature, and reaction terminates.Suction filtration, filtrate are adjusted with 3mol/L hydrochloric acid
, there is Precipitation pH value of solution=4.0, and suction filtration obtains compound 1 for faint yellow solid.
Potassium hydroxide addition and pH adjust most important, if condition is improper, the solid of precipitation may not
It is desired product, or largely reduces yield.
Step 2：(three's mole ratio is 1 to alpha, beta-unsaturated ketone with nitromethane, diethylamine：10：5),
Generation Michael addition reaction carries out nitrosation, obtains compound 2.The heating of compound 1 is dissolved in anhydrous second
Alcohol, adds diethylamine and nitromethane, is heated to reflux 12h.Reaction terminates, and is adjusted with 3mol/L hydrochloric acid
PH value of solution=3.0, are extracted with ethyl acetate, and organic layer dries, and vacuum removes solvent, and column chromatography for separation is purified,
Compound 2 is obtained for white solid.
Step 3：Using microwave method, compound 2 and ammonium acetate reacting generating compound 3.Compound 2 is dissolved in
Absolute ethyl alcohol, adds the ammonium acetate of 35 times of 2 moles of compound, and mixed liquor is added in microwave reaction container,
Microwave reaction 6h at 95 DEG C.Solid is had to separate out, suction filtration, solid are obtained with 0 DEG C of absolute ethanol washing
Compound 3 be with metallic luster bluish violet solid.
Step 4：(mol ratio is 1 to compound 3 with boron trifluoride：17) complexing obtains compound 4.Chemical combination
Thing 3 is dissolved in the toluene for steaming again, adds boron trifluoride ether solution (48%BF3) and triethylamine, stirs at 80 DEG C
Mix overnight, complexing obtains described two pyrylium dyes 4 of near-infrared aza fluorine boron, be red solid with metallic luster
Body.
Post processing is as follows：Mixture after being stirred overnight is cooled to room temperature, vacuum removes solvent, uses acetic acid second
Ester dissolution residual substance, washes 3 times, organic phase anhydrous sodium sulfate drying, removes solvent and obtains dark gray solid,
Use recrystallize with dichloromethane.
Cyano group on two azole compounds of near-infrared aza fluorine boron can make such dyestuff wavelength to a great extent
Upper generation red shift, makes absorption and launch wavelength be located near infrared region, possesses higher biological tissue's penetrability,
Cell autofluorescence interference is effectively eliminated, reduces the damage to cell or tissue during observation in addition.Hydroxyl
The introducing of base, the pH for tumour cell can make the compound become a kind of pH sensitive in acid range
Molecular probe, fluorescence imaging is carried out to tumour cell.
Microwave method of the present invention synthesizes a kind of two pyrylium dyes of near-infrared aza fluorine boron, is also applied for other near-infrared nitrogen
The synthesis of miscellaneous two pyrylium dyes of fluorine boron, advantage are：Microwave method is heated to reflux synthetic method compared to conventional, right
In the fluorochrome is synthesized, the reaction time can be greatly shortened, reduced accessory substance, improve reaction yield.
Description of the drawings
Fig. 1 is compound 1 synthesized by embodiment 11H NMR.
Fig. 2 is compound 1 synthesized by embodiment 113C NMR.
Fig. 3 is compound 2 synthesized by embodiment 11H NMR.
Fig. 4 is compound 2 synthesized by embodiment 113C NMR.
Fig. 5 is compound 3 synthesized by embodiment 11H NMR.
Fig. 6 is compound 3 synthesized by embodiment 113C NMR.
Fig. 7 is compound 4 synthesized by embodiment 11H NMR.
Fig. 8 is compound 4 synthesized by embodiment 113C NMR.
Fig. 9 is compound 4 synthesized by embodiment 119F NMR.
Figure 10 is TIC figure and the high resolution mass spectrum figure of compound 3 synthesized by embodiment 1.Can from figure
Go out, 3 purity of compound for obtaining is high, impurity is few.
Figure 11 is the ultraviolet-visible absorption spectroscopy (10 μM) of compound 4 synthesized by embodiment 1.Maximum absorption wave
A length of 745nm.
Figure 12 is fluorescence of the compound 4 synthesized by embodiment 1 under maximum excitation wavelength 745nm (10 Μ m)
Emission spectrum, maximum emission wavelength is in 779nm.Illustrate the absorption of the dyestuff and launch wavelength all in near-infrared
Region.
The chemical structural formula of a kind of new two pyrylium dyes of near-infrared aza fluorine boron that Figure 13 is provided for the present invention.
Specific embodiment
Technical scheme is described with specific embodiment below, but protection scope of the present invention is not limited to
This：
Microwave reactor in following examples used by microwave reaction is Microwave Synthesis Reactor：
Monowave 300(Anton Paar).
Embodiment 1
The synthesis of two pyrylium dyes compound 4 of near-infrared aza fluorine boron：
1. compound 1 is synthesized：
Parahydroxyacet-ophenone (1.36g, 10mmol) and 50 are dissolved in cyanobenzaldehyde (1.31g, 10mmol)
ML absolute ethyl alcohol, adds KOH (560mg, 30mmol), is stirred overnight at room temperature, is subsequently adding KOH (560
Mg, 30mmol), be stirred at room temperature 5h, suction filtration, filtrate with 3mol/L hydrochloric acid conditioning solution pH=4.0,
There is a Precipitation, suction filtration, filter cake 3mol/L salt acid elution, compound 1 is obtained for faint yellow solid powder
Last (1.80g, yield 72.3%).1H NMR(500MHz,DMSO-d6)δ10.48(s,1H),8.10-8.05
(m, 5H), 7.92 (d, J=5.0Hz, 2H), 7.72-7.69 (d, J=15.0Hz, 1H), 6.91-6.90 (d, J=
5.0Hz,2H).13C NMR(126MHz,DMSO-d6)δ186.89,162.48,140.46,139.48,
132.65,131.38,129.24,128.80,118.65,115.44,112.01.HRMS(ESI+)calcd for
C16H11NO2[M+H]+250.0863,found 250.0848.
2. compound 2 is synthesized：
Compound 1 (120mg, 0.48mmol) is dissolved in 25mL absolute ethyl alcohol, is heated to reflux to solid dissolving.
Nitromethane (0.25mL, 4.8mmol) and diethylamine (0.24mL, 2.4mmol) is added, flow back 12h,
Room temperature is cooled to, with 3mol/L hydrochloric acid conditioning solution pH=3.0.Ethyl acetate is extracted, and organic layer is with anhydrous
Sodium sulphate dries, and vacuum removes solvent, and column chromatography for separation purifies (n-hexane/ethyl acetate=1:1), must change
Compound 2 is white solid (90mg, yield 60.5%).1H NMR(500MHz,DMSO-d6)δ10.40
(s, 1H), 7.82-7.77 (m, 4H), 7.61 (d, J=5.0Hz, 2H), 6.84-6.82 (m, 2H), 5.04-4.90
(m,2H),4.13-4.07(m,1H),3.54-3.41(m,2H).13C NMR(126MHz,DMSO-d6)δ
194.98,162.28,146.15,132.31,130.50,129.05,127.84,118.64,115.22,110.01,
79.02.HRMS(ESI+)calcd for C17H14N2O4[M+H]+311.1026,found 311.1051.
3. compound 3 is synthesized：
Compound 2 (90mg, 0.29mmol) is dissolved in 5mL absolute ethyl alcohol, add ammonium acetate (777m g, 10.1
Mmol), mixed liquor is added in microwave reaction special glass tube, microwave reaction 6h, TLC prison at 95 DEG C
Survey raw material to react completely.Solid is had to separate out, suction filtration, solid are washed with cold ethanol, obtained with metallic luster
Bluish violet solid 3 (40mg, yield 52.6%).1H NMR(500MHz,DMSO-d6)δ10.32(s,2H),
8.23 (d, J=10.0Hz, 4H), 7.99 (d, J=10.0Hz, 4H), 7.93 (d, J=10.0Hz, 4H), 7.72 (s,
2H), 7.01 (d, J=10.0Hz, 4H).13C NMR(126MHz,DMSO-d6)δ160.46,154.82,
148.87,138.54,137.77,132.41,128.85,128.82,122.06,119.11,116.95,116.56,
110.06.HRMS(ESI+)calcd for C34H21N5O2[M+H]+532.1768,found 532.1772.
4. two pyrylium dyes compound 4 of azepine fluorine boron is synthesized：
Compound 3 (15mg, 0.028mmol) is dissolved in 10mL and steams toluene again, stirs 10min, adds three
Ethamine (0.1mL, 0.28mmol), mixed liquor are heated to 80 DEG C, addition boron trifluoride ether solution (0.2mL,
0.48mmol), there are a large amount of blue solid to separate out at once, keep 80 DEG C of reactions overnight, room temperature is cooled to, very
Empty removal solvent, uses ethyl acetate dissolution residual substance, washes 3 times, organic phase anhydrous sodium sulfate drying, go
Except solvent obtains dark gray solid, red metallic luster pressed powder 4 (15 is obtained with recrystallize with dichloromethane
Mg, yield 92.6%).1H NMR(500MHz,DMSO-d6)δ10.60(s,2H),8.32-8.31(d,J
=5.0Hz, 4H), 8.13-8.07 (dd, J=10.0,5.0Hz, 8H), 7.78 (s, 2H), 6.97-6.96 (d, J=
5.0Hz,4H).13C NMR(126MHz,DMSO-d6)δ161.34,157.60,144.46,138.94,
136.03,132.52,132.33,129.23,121.32,121.13,118.77,115.99,111.27.19F NMR
(470MHz,CDCl3) δ -131.05 (q, J=28.2Hz, BF2).HRMS(ESI+)calcd for
C34H20BF2N5O2[M–CN+H]+554.1726,found 554.1733.
Claims (7)
1. a kind of two pyrylium dyes of near-infrared aza fluorine boron, structural formula are as follows：
2. the microwave synthesis method of two pyrylium dyes of near-infrared aza fluorine boron described in a kind of claim 1, step is such as
Under：
Step one：Parahydroxyacet-ophenone and cyanobenzaldehyde is reacted in the basic conditions, obtain α, β-insatiable hunger
And ketone, it is designated as compound 1；
Step 2：In the basic conditions, α, alpha, beta-unsaturated ketone occur Michael addition reaction to enter with nitromethane
Row nitrosation, obtains compound 2；
Step 3：Using microwave method, compound 2 generates four aryl azepines, two pyrroles's methine class with ammonium acetate reaction
Compound 3；
Step 4：In the basic conditions, compound 3 occurs complex reaction to obtain the near-infrared with boron trifluoride
Two pyrylium dyes of azepine fluorine boron.
3. method according to claim 2, it is characterised in that step one concrete operations are as follows：
By 1：The parahydroxyacet-ophenone of 1 mol ratio and be dissolved in absolute ethyl alcohol to cyanobenzaldehyde, add 3 times right
The potassium hydroxide of hydroxy acetophenone mole, is stirred overnight at room temperature, then plus 3 times of parahydroxyacet-ophenone moles
Potassium hydroxide, continues 5h is stirred at room temperature, and reaction terminates, suction filtration, and filtrate uses 3mol/L hydrochloric acid conditioning solution
PH=4.0, has Precipitation, and suction filtration obtains compound 1.
4. method according to claim 2, it is characterised in that the step 2 concrete operations are as follows：
The heating of compound 1 is dissolved in absolute ethyl alcohol, adds diethylamine and nitromethane, compound 1, nitro first
Alkane, diethylamine three mole ratio are 1：10：5,12h is heated to reflux, reaction terminates, and uses 3mol/L
Hydrochloric acid conditioning solution pH=3.0, is extracted with ethyl acetate, and organic layer dries, and vacuum removes solvent, column chromatography
Separating-purifying, obtains compound 2.
5. method according to claim 2, it is characterised in that the step 3 concrete operations are as follows：
Compound 2 is dissolved in absolute ethyl alcohol, the ammonium acetate of 35 times of 2 moles of compound is added, by mixed liquor
Add in microwave reaction container, microwave reaction 6h at 95 DEG C, have solid to separate out, suction filtration, solid is with 0 DEG C
Absolute ethanol washing, obtain compound 3.
6. method according to claim 2, it is characterised in that the step 4 concrete operations are as follows：
Compound 3 is dissolved in the toluene for steaming again, boron trifluoride ether solution and triethylamine is added, stir at 80 DEG C
Overnight, room temperature is subsequently cooled to, vacuum removes solvent, ethyl acetate dissolution residual substance is used, wash 3 times, have
Machine mutually uses anhydrous sodium sulfate drying, removes solvent and obtains dark gray solid, is obtained with recrystallize with dichloromethane described
Two pyrylium dyes of near-infrared aza fluorine boron；
Compound 3 is 1 with boron trifluoride mol ratio in boron trifluoride ether solution：17.
7. method according to claim 2, it is characterised in that：The step is just like claim 3 institute
State；The step 2 is as claimed in claim 4；The step 3 is as claimed in claim 5；The step 4
As claimed in claim 6.
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| CN107602600A (en) * | 2017-08-30 | 2018-01-19 | 平顶山学院 | The pyrroles's near-infrared pH fluorescence probes of amino substituted nitrogen heterocyclic fluorine boron two and its preparation method and purposes |
| CN108102408A (en) * | 2017-12-26 | 2018-06-01 | 南京邮电大学 | A kind of preparation and application of the nir dye based on azepine fluorine borine |
| CN109232621A (en) * | 2018-09-13 | 2019-01-18 | 南京工业大学 | A kind of preparation method of the glimmering nir dye of amino substituted nitrogen heterocyclic fluorine boron |
| CN110467696A (en) * | 2018-05-10 | 2019-11-19 | 南京工业大学 | A kind of preparation method of water-soluble graft polymers photoacoustic contrast agent |
| CN110872312A (en) * | 2019-12-12 | 2020-03-10 | 安徽师范大学 | Benzodiazolone fluoroboric fluorescent dye and preparation method thereof |
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| CN107602600B (en) * | 2017-08-30 | 2020-05-05 | 平顶山学院 | Amino-substituted aza-BODIPY near-infrared pH fluorescent probe and preparation method and application thereof |
| CN108102408A (en) * | 2017-12-26 | 2018-06-01 | 南京邮电大学 | A kind of preparation and application of the nir dye based on azepine fluorine borine |
| CN110467696A (en) * | 2018-05-10 | 2019-11-19 | 南京工业大学 | A kind of preparation method of water-soluble graft polymers photoacoustic contrast agent |
| CN109232621A (en) * | 2018-09-13 | 2019-01-18 | 南京工业大学 | A kind of preparation method of the glimmering nir dye of amino substituted nitrogen heterocyclic fluorine boron |
| US11858950B2 (en) | 2019-11-04 | 2024-01-02 | Samsung Electronics Co., Ltd. | Compound and film and photoelectric diode and organic sensor and electronic device |
| CN110872312A (en) * | 2019-12-12 | 2020-03-10 | 安徽师范大学 | Benzodiazolone fluoroboric fluorescent dye and preparation method thereof |
| CN110872312B (en) * | 2019-12-12 | 2023-04-07 | 安徽师范大学 | Benzodiazolone fluoroboric fluorescent dye and preparation method thereof |
| CN114907393A (en) * | 2022-05-13 | 2022-08-16 | 蚌埠医学院 | Organic conjugated compound with Aza-BODIPY as basic skeleton and preparation method and application thereof |
| CN114907393B (en) * | 2022-05-13 | 2024-05-28 | 蚌埠医科大学 | Organic conjugated compound with Aza-BODIPY as basic skeleton and preparation method and application thereof |
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