CN1167768C - 8-oxy-8H acenaphthene (1,2-b) pyrrol-9nitrile fluorescence chromophore and its derivative - Google Patents
8-oxy-8H acenaphthene (1,2-b) pyrrol-9nitrile fluorescence chromophore and its derivative Download PDFInfo
- Publication number
- CN1167768C CN1167768C CNB021484007A CN02148400A CN1167768C CN 1167768 C CN1167768 C CN 1167768C CN B021484007 A CNB021484007 A CN B021484007A CN 02148400 A CN02148400 A CN 02148400A CN 1167768 C CN1167768 C CN 1167768C
- Authority
- CN
- China
- Prior art keywords
- oxygen
- nitrile
- acenaphthene
- fluorescent
- pyrroles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pyrrole Compounds (AREA)
Abstract
The present invention relates to a new fluorescent chromophore which has a rigid coplanar structure and a long conjugated system and contains strong electron suction cyanogen groups and electron supply amino groups, a fluorescent derivative of the new fluorescent chromophore, and a preparation method thereof. The new fluorescent chromophore is 8-oxygen-8H acenaphtho-(1, 2-b) pyrrole-9-nitrile and a fluorescent derivative 3 thereof, and 6-di-substituted group-8-oxygen-8H-acenaphtho-(1, 2-b) pyrrole-9-nitrile. The fluorescent chromophore is prepared by cyclization reaction under the existence of 2-(2-oxygen-2Hacenaphthene) malononitrile and a base catalyst in a solvent. Then, the fluorescent chromophore and a nucleophilic reagent carry out substitution reaction in the solvent to prepare single-substituted or di-substituted-8-oxygenacenaphtho-(1, 2-b) pyrrole-9-nitrile and the fluorescent derivative thereof. The substances have high fluorescence quantum efficiency approaching to 1. The maximal absorption wavelength is from 550 to 570 nm; the maximal fluorescent emission wavelength is from 590 to 620 nm. The new fluorescent chromophore has narrow peak shape and is an ideal fluorescent probe compound.
Description
Technical field
The present invention relates to a class novel fluorescence chromophoric group 8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile and fluorescent derivative and preparation method.
Background technology
In recent years, organic fluorescence materials is used widely in every field of science and technology as functional pigmented.Particularly because fluoroscopic examination highly sensitive, easy and simple to handle, more safer than traditional detection meanss such as isotopic labeling, and the organic fluorescence molecule has stable performance, be easy to advantages such as structural modification, therefore organic fluorescence materials as fluorescent molecular probe and chemical sensor, has become powerful analysis tool in life science, and many traditional textile printing and dyeings are all passed through the suitable structurally-modified well behaved fluorescent probe that becomes with the fluorescence dye parent.But the kind of existing fluorescence dye parent is limited, and each defectiveness of performance can not satisfy the demand to fluorescent material that grows at top speed in the Application Areas.Come out in decades till now from nineteen sixty-eight BODIPY fluorescent chromophore parent, the fluorescent chromophore parent of new texture rarely has report, and excellent property, (such as the fluorescence quantum efficiency height, emission wavelength is long, and spectrum is narrow etc.) fluorescent chromophore then do not occur again.(Molecular ProbeInc USA) is developed to serial fluorescent probe test kit, and successfully realizes commercialization the BODIPY fluorescent chromophore, and the development of fluorescent probe is in recent years had very large pushing effect by molecular probe company.This shows that initiative development of new fluorescent chromophore has extremely important practical value.
It is to have the naphthalene nucleus skeleton to derive out that considerable part is arranged in traditional fluorescent chromophore, because naphthalene nucleus has rigidity coplanarity preferably.Naphthalene is to be no lack of improved seeds in the fluorophore, and have be developed to fluorescent probe into classics.Such as, (Natrue, 1981,292,17) 4-amino-1, famous Lucifer yellow series in the 8-naphthalimide fluorophore is the fluorescent probe of bioprotein spike the most efficiently.The fluorescent probe dansyl amide Dansyl (5-dimethylamino-naphthalene sulfonyl ammonia, US patent 6048975) that extensive use is arranged at biomedical sector for another example, equally.Qian Xuhong and Xiao Yi (Terahedron Lett.2002,43,2991) are reported in the amino of introducing electrophilic cyano group and power supply in the conjugated system of naphthalene series compound recently, obtain the very high novel fluorescence chromophoric group of fluorescence quantum efficiency.But naphthalene is that the absorption and the emission of fluorescent chemicals is positioned at the short zone (350-500nm) of wavelength, because the autofluorescence majority of organism also in this zone, therefore reduces the sensitivity of probe.Avoid the interference of organism autofluorescence, the fluorescent emission of probe is preferably in the long-wavelength region.
Summary of the invention
In order both to keep naphthalene series compound to help the rigidity coplanar structure feature of fluorescent emission, simultaneously spectrum is moved significantly to the long wave direction, the naphtho-heterocycle structure that design has bigger conjugated system is a kind of feasible, effective thinking.Introduce strong power supply simultaneously in the molecular conjugation system, electron-withdrawing group is to form intensive push-and-pull electron system, and it is unimpeded to help the electronics mobile, promotes fluorescent emission.Based on above-mentioned thought, formulated related novel fluorescence chromophoric group and the fluorescent derivative thereof of this patent.
The present invention is that a class is on the conjugated system of rigidity coplanar structure, contain the amino novel fluorescent chromophore 8-oxygen-8H acenaphthene of strong electrophilic cyano group and power supply son also (1,2-b) pyrroles-9-nitrile (molecular structural formula K) and fluorescent derivative 3 thereof, 6-is disubstituted-8-oxygen-8H-acenaphthene also (1,2-b) pyrroles-9-nitrile (general formula of molecular structure A):
Among the general formula A, R
1, R
2Substituting group can be identical or different:
R
1, R
2When identical, R
1=R
2=H is fluorescent chromophore parent K;
R
1, R
2When inequality, (1) R
1=NHR
3, R
2=H:
A, R
3=H, C
1-C
20Straight chained alkyl, cycloalkyl;
B, R
3=-(CH
2)
n-Ar, n=1-3; Ar is a phenyl;
c、R
3＝-(CH
2)
mYH，m＝2-6；Y＝NH、O；
d、R
3＝-(CH
2)
xN(R
5)
2，x＝2，3；R
5＝-CH
3、-C
2H
5；
E, R
3=(CH
2)
yHc, y=2,3; Hc=piperazinyl, N '-methylpiperazine base, morpholine
Base:
(2)R
1＝OH，R
2＝H：
(3)R
2＝H，R
1：
R
1=azacyclo-amino, piperidines, piperazine,
N '-methylpiperazine, morpholine:
The present invention is in structure design, adopted conjugated system bigger, have again that higher to draw 2-(2-oxygen-2H the acenaphthene)-propane dinitrile (as molecular structure S) of electronic capability be starting raw material, in the presence of alkali and solvent, through ring-closure reaction can make fluorescent chromophore parent 8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile (as: molecular structure K):
Its rigidity coplanarity that fluorescent chromophore parent K is structure-reinforced has very strong electron deficiency, has enlarged conjugated system, makes it be very easy to be subjected to the attack of nucleophilic reagent.Primary amine, secondary amine and hydroxyl radical negative ion class nucleophilic reagent and parent 8-oxygen-8H acenaphthene also (1,2-b) atmospheric oxidation type fragrance hydrogen nucleophilic substitution reaction takes place in pyrroles-9-nitrile (molecular structure K), obtain 3,6-is disubstituted-8-oxygen-8H-acenaphthene also (1,2-b) pyrroles-9-nitrile (general formula of molecular structure A):
3,6-is disubstituted-8-oxygen-8H-acenaphthene also (1,2-b) among pyrroles-9-nitrile molecular structure A very strong rigidity coplanarity is arranged, enlarged conjugated system, very strong push-and-pull electron system helps fluorescent emission.
Also (1,2-b) synthetic method of pyrroles-9-nitrile (molecular structure K) is the base catalysis ring-closure reaction to fluorescent chromophore parent 8-oxygen-8H acenaphthene, that is:
With raw material 2-(2-oxygen-2H acenaphthene)-propane dinitrile in solvent (tetrahydrofuran (THF), acetone, pyridine, dimethyl formamide, acetonitrile, methyl alcohol, ethanol, dimethyl sulfoxide (DMSO)), in the presence of basic catalyst (salt of wormwood, triethylamine, pyridine), 40-120 ℃ of cyclization temperature, stirring reaction 10-100 minute, after the cooling, remove partial solvent under reduced pressure, filter, make product.
Also (1,2-b) also (1,2-b) synthetic method of pyrroles-9-nitrile is the nucleophilic substitution reaction of oxidized form fragrance hydrogen to pyrroles-9-nitrile and 3-hydroxyl-8-oxygen-8H acenaphthene, that is: to replace fluorescent derivative 3-substituted-amino-8-oxygen-8H acenaphthene
With 8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile is in solvent (tetrahydrofuran (THF), acetonitrile, pyridine, dimethyl formamide, dimethyl sulfoxide (DMSO)), with etc. primary amine, secondary amine or the hydrogen-oxygen negative ion class nucleophilic reagent of mol ratio, at 20-100 ℃, reacted 0.5-24 hour.After the cooling, remove partial solvent under reduced pressure, filter, obtain one and replace product.
Two replace fluorescent derivative 3,6-disubstituted amido-8-oxygen-8H acenaphthene also (1,2-b) synthetic method of pyrroles-9-nitrile then is: with 8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile is in solvent (tetrahydrofuran (THF), acetonitrile, pyridine, dimethyl formamide, dimethyl sulfoxide (DMSO)), with excess raw material 4-5 secondary amine doubly, reacted 16-48 hour, and temperature 20-100 ℃, obtained two with above-mentioned same aftertreatment and replace product.
The present invention obtain 3,6-is disubstituted-also (1,2-b) pyrroles-9-nitrile (molecular structure A) has very high fluorescence quantum efficiency to 8-oxygen-8H-acenaphthene, near 1.Maximum absorption wavelength is 550-570nm, and maximum emission wavelength is 590-620nm, and the peak type is narrow, is more satisfactory fluorescent probe compounds.
Embodiment
Embodiment 1
1 gram 2-(2-oxygen-2H-acenaphthene) propane dinitrile, 0.2 gram salt of wormwood, 10 milliliters of dimethyl sulfoxide (DMSO) are heated to 100 ℃, stir 15 minutes, and crystal is separated out in cooling.Filter, washing and drying, product yellowish brown crystal 8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile, yield, 99%.
1H?NMR(400M，DMSO)：δ8.71-8.69(d，J＝8.0Hz，1H)，8.67-8.65(d，J＝7.6Hz，1H)，8.64-8.62(d，J＝8.0Hz，1H)，8.42-8.40(d，J＝7.6Hz，1H)，8.04-8.08(t，J＝8.0Hz，1H)，7.99-7.95(t，J＝7.8Hz，1H)；
13C?NMR(100M，DMSO)：δ177.48，138.26，137.73，134.40，132.72，131.82，131.37，128.91，127.94，127.37，126.13，122.22，119.72，113.82，113.38；IR(KBr)cm
-1：2231，1643，1577；ESI-MS：M+Na
+(253，m/z).
Embodiment 2
1 gram 8-oxygen-8H acenaphthene also (1,2-b) add 0.32 gram butylamine in 50 milliliters of acetonitrile solutions of pyrroles-9-nitrile, stirring at normal temperature 30 minutes, the evaporation section solvent, separate out the amino 8-oxygen of product 3-fourth-8H acenaphthene also (1,2-b) pyrroles-9-nitrile Al.Yield 70%.
1H?NMR(400M，DMSO)：δ9.604(br?s，-NH-，1H)，8.95-8.93(d，J＝7.6Hz，1H)，8.60-8.58(d，J＝7.2Hz，1H)，7.98-7.96(d，J＝8.8Hz，1H)，7.88-7.92(t，J＝7.8Hz，1H)，7.04-7.02(d，J＝9.2Hz，1H)，3.60-3.59(br?s，-NHCH
2CH
2-，2H0，1.75-1.71(m，-NHCH
2CH
2CH
2-，2H)，1.43-1.47(m，-CH
2CH
2CH
2CH
3)，0.94-0.98(t，J＝7.2Hz，-CH
2CH
3)；IR(KBr)cm
-1：3284，2217，1619，1562，1529；ESI-MS：[M-H]
-(300m/z).
Embodiment 3
1 gram 8-oxygen-8H acenaphthene also (1,2-b) add 0.43 gram hexahydroaniline in 50 milliliters of acetonitrile solutions of pyrroles-9-nitrile, stirring at normal temperature 30 minutes, the evaporation section solvent, separate out product 3-hexamethylene amino-8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile A2.Yield 68%.
1H?NMR(400M，DMSO)：δ9.13-9.11(d，J＝7.6Hz，-NH-，1H)9.03-9.01(d，J＝7.6Hz，1H)，8.54-8.52(d，J＝7.2Hz，1H)，7.90-7.87(d，J＝9.2Hz，1H)，7.87-7.83(t，J＝8.0Hz，1H)，7.09-7.07(d，J＝9.2Hz，1H)，3.90(br?s，-NHCH-，1H)，2.05-2.02(br?d，-NHCH(CH
2 *CH
2)
2，CH
2，2H)，1.85-1.82(br?d，-NHCH(CH
2 *CH
2)
2CH
2，2H)，1.72-1.69(brd，-NHCH(CH
2CH
2)
2CH
2 *，1H)，1.43-1.58(m，-NHCH(CH
2CH
2)
2CH
2，4H)，1.19-1.23(brd，-NHCH(CH
2CH
2)
2CH
2 *，1H)；IR(KBr)cm
-1：3324，2215，1631，1575，1492；ESI-MS：[M+H]
+(328，m/z).
Embodiment 4
1 gram 8-oxygen-8H acenaphthene also (1,2-b) add 0.48 gram β-phenylethylamine, stirring at normal temperature 30 minutes in 50 of pyrroles 9-nitrile milliliters of acetonitriles, the evaporation section solvent, separate out product 3-(2 '-styroyl) amino 8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile A3, yield 76%.
1H?NMR(400M，DMSO)：δ9.13-9.11(d，J＝7.6Hz，
-NH-，1H)，9.03-9.01(d，J＝7.6Hz，1H)，8.54-8.52(d，J＝7.2HZ，1H)，7.90-7.87(d，J＝9.2Hz，1h)，7.87-7.83(t，J＝8.0Hz，1H)，7.35-7.31(t，J＝8.0Hz，2H)，7.27-7.25(d，J＝8.0Hz，2H)，7.22-7.20(t，J＝8.0Hz，1H)，7.09-7.07(d，J＝9.2Hz，1H)，3.60-3.59(br?s，-NHCH
2CH
2-，2H)，2.80-2.78(d，-NHCH
2CH
2，2H)；ESI-MS：[M+H]
+(350，m/z).
Embodiment 5
Also (1,2-b) adding 0.63 restrains morpholinyl-propylamine, stirring at normal temperature 30 minutes to 1 gram 8-oxygen-8H acenaphthene in 50 milliliters of acetonitriles of pyrroles-9-nitrile, the evaporation section solvent, separate out product 3-(3 '-morpholinyl-propyl group) amino 8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile A4, yield 75%.
1H?NMR(400M，DMSO)；δ9.13-9.11(d，J＝7.6Hz，-NH-，1H)，9.03-9.01(d，J＝7.6Hz，1H)，8.54-8.52(d，J＝7.2Hz，1H)，7.90-7.87(d，J＝9.2Hz，1H)，7.87-7.83(t，J＝8.0Hz，1H)，7.09-7.07(d，J＝9.2Hz，1H)，3.91(br?s，-N(CH
2CH
2)
2O，4H)，3.60-3.59(br?s，-NHCH
2CH
2-，2H)，2.75-2.74(m，-CH
2N(CH
2)
2，6H)，1.75-1.71(m，-NHCH
2CH
2CH
2-，2H)；ESI-MS[M+H]
+(373，m/z).
Embodiment 6
1 gram 8-oxygen-8H acenaphthene also (1,2-b) 50 of pyrroles 9-nitrile milliliters of acetonitrile solutions add 0.2 gram thanomins, stirring at normal temperature 30 minutes, the evaporation section solvent, separate out the amino 8-oxygen of product 3-(hydroxyethyl-)-8H acenaphthene also (1,2-b) pyrroles-9-nitrile A5, yield 80%.
1H?NMR(400M，DMSO)：δ9.545(br?s，-NH-，1H)，8.87-8.85(d，J＝8.0Hz，1H)，8.51-8.49(d，J＝7.6Hz，1H)，7.88-7.85(d，J＝9.2Hz，1H)，7.80-7.84(t，J＝7.8Hz，1H)，6.98-7.00(d，J＝9.2Hz，1H)，4.99(s，-OH，1H)3.755(br?s，-CH
2OH，2H)，3.66-3.69(t，J＝4.2Hz，-NHCH
2-)；
13C?NMR(100M，DMSO)：δ176.14，156.14，138.22，132.12，130.82，129.38，127.72，126.65，125.22，121.89，115.90，114.12，111.14，108.23，103.80，58.94，46.37；IR(KBr)cm
-1：3457，3309，2215，1656，1623，1571，1494；ESI-MS：[N-H]
-(288m/z).
Embodiment 7
1 gram 8-oxygen-8H acenaphthene also (1,2-b) add 0.38 gram N in 50 milliliters of acetonitrile solutions of pyrroles-9-nitrile, the N-dimethyl-ethylenediamine, stirring at normal temperature 30 minutes, the evaporation section solvent is separated out product 3-(N, N-dimethylamino ethylidene-) amino 8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile A6, yield 66%.
1H?NMR(400M，DMSO)：δ9.13-9.11(d，J＝7.6Hz，-NH-，1H)，9.03-9.01(d，J＝7.6Hz，1H)，8.54-8.52(d，J＝7.2Hz，1H)，7.90-7.87(d，J＝9.2Hz，1H)，7.87-7.83(t，J＝8.0Hz，1H)，7.09-7.07(d，J＝9.2Hz，1H)，3.58-3.37(br?s，-NHCH
2CH
2-，2H)，2.71-2.70(brs，-NCH
2CH
2-，2H)，2.35(s，-CH
3，6H)；ESI-MS[M+H]
+(317，m/z).
Embodiment 8
1 gram 8-oxygen-8H acenaphthene also (1,2-b) pyrroles 9-nitrile is suspended among 20 milliliters of DMSO (dimethyl sulfoxide (DMSO)), add 0.2 gram sodium hydroxide, stirring at normal temperature 30 minutes is poured in 50 milliliter of 20% hydrochloric acid and is separated out solid, filter, ethanol is washed, and ether is washed, dry product 3-hydroxyl 8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile A7, yield 65%.
1H?NMR(400MH，DMSO)：δ8.52-8.50(d，J＝8.0Hz，1H)，8.45-8.43(d，J＝8.0Hz，1H)，7.74-7.68(m，2H)，6.39-6.36(d，J＝9.6Hz，1H)；IR(KBr)cm
-1：2206，1627，1567，1508；ESI-MSm/z245(M
-).
Embodiment 9
Also (1,2-b) adding 0.38 restrains piperidines to 1 gram 8-oxygen-8H acenaphthene in 50 milliliters of acetonitrile solutions of pyrroles-9-nitrile, and stirring at room is after 30 minutes, the hydrochloric acid that adds 1 milliliter 20%, decompression steams partial solvent, separates out product 3-piperidyl 8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile A8, yield 60%.
1H?NMR(400M，CHCl
3)：δ8.70-8.68(d，J＝8.0Hz，1H)，8.47-8.45(d，J＝8.4Hz，1H)，8.11-8.09(d，J＝8.4Hz，1H)，7.81-7.78(t，J＝7.8Hz，1H)，7.12-7.10(d，J＝8.2Hz，1H)，3.59-3.62(t，-N(CH
2CH
2)
2CH
2，4H)，1.94(br?s，-N(CH
2CH
2)
2CH
2，4H)，1.94(br?s，-N(CH
2CH
2)
2CH
2，2H)；
13C?NMR(100M，DMSO)：δ176.43，160.38，136.13，134.62，132.31，129.14，128.63，126.58，126.30，123.76，115.24，114.78，113.87，113.28，107.40，54.16，25.72，23.26；IR(KBr)cm
-1：2217，1623，1571，1498；ESI-MS：[M+H]
+(314，m/z).
Embodiment 10
1 gram 8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile is dissolved in 50 milliliters of acetonitriles, adds 1.5 gram piperidines, stirring at normal temperature 16 hours, the evaporation section solvent is separated out product 3,6-dipiperidino-8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile A9.Yield 80%.
1H?NMR(400M，CHCl
3)：δ8.09-8.06(d，J＝9.6Hz，1H)，7.98-7.96(d，J＝8.8Hz，1H)，7.31-7.29(d，J＝9.6Hz，1H)，7.4-7.02(t，J＝8.8Hz，1H)，3.54(br?s，-N(CH
2 *CH
2)
2CH
2，4H)，3.41(br?s，-N(CH
2 *CH
2)
2CH
2，4H)，1.77(br?s，-N(CH
2CH
2 *)
2CH
2 *，12H)；
13CNMR(100M，CHCl
3)：δ173.13，159.19，156.70，133.49，133.21，132.95，126.34，125.02，117.41，117.03，115.83，115.65，114.38，114.06，113.96，55.05，53.41，29.86，26.62，26.37，24.38，24.00；IR(KBr)cm
-1：2215，1598，1542，1506；ESI-MS：[N+H]
+(397m/z).
Claims (4)
1, a class has the conjugated system of rigidity coplanar structure, and the fluorescent chromophore and the derivative thereof that contain strong electrophilic cyano group and the sub amino naphtho-heterocycle structure of power supply, it is characterized in that this fluorescent chromophore is 8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile (molecular structural formula K) and fluorescent derivative 3 thereof, 6-is disubstituted-8-oxygen-8H-acenaphthene also (1,2-b) pyrroles-9-nitrile (general formula of molecular structure A):
Among the general formula A, R
1, R
2Substituting group can be identical or different;
R
1, R
2When identical, R
1=R
2=H is fluorescent chromophore parent K;
R
1, R
2When inequality, (1) R
1=NHR
3, R
2=H;
A, R
3=H, C
1-C
20Straight chained alkyl, cycloalkyl;
B, R
3=-(CH
2)
n-Ar, n=1-3; Ar is a phenyl;
c、R
3＝-(CH
2)
mYH，m＝2-6；Y＝NH、O；
d、R
3＝-(CH
2)
xN(R
5)
2，x＝2，3；R
5＝-CH
3、-C
2H
5；
E, R
3=(CH
2)
yHc, y=2,3; Hc=piperazinyl, N '-methylpiperazine base, morpholine
Base;
(2)R
1＝OH，R
2＝H；
(3)R
2＝H，R
1；
R
1=azacyclo-amino, piperidines, piperazine,
N '-methylpiperazine, morpholine.
2, a class is by the preparation method of the described fluorescent chromophore of claim 1, it is characterized in that fluorescent chromophore parent 8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile is to be starting raw material with 2-(2-oxygen-2H acenaphthene) propane dinitrile, in solvents tetrahydrofurane, acetone, pyridine, dimethyl formamide, acetonitrile, methyl alcohol, ethanol, dimethyl sulfoxide (DMSO), exist down in basic catalyst salt of wormwood, triethylamine, pyridine, 40-120 ℃ of cyclization temperature, stirring reaction 10-100 minute, cooling, underpressure distillation, filter, make product.
3, according to the preparation method of the described fluorescent chromophore derivative of claim 1, it is characterized in that one, to replace fluorescent derivative A be with 8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile is in solvents tetrahydrofurane, acetonitrile, pyridine, dimethyl formamide, dimethyl sulfoxide (DMSO), with etc. primary amine, secondary amine or the hydrogen-oxygen negative ion class nucleophilic reagent of mol ratio, at 20-100 ℃, reacted 0.5-24 hour, cooling, underpressure distillation, filter, make 3-substituted amido 8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile or 3-hydroxyl-8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile.
4, according to the preparation method of the described fluorescent chromophore of claim 2, it is characterized in that two replacement fluorescent derivative A are that also (1,2-b) pyrroles-9-nitrile is in solvents tetrahydrofurane, acetonitrile, pyridine, dimethyl formamide, dimethyl sulfoxide (DMSO), with excess raw material 4-5 secondary amine doubly with 8-oxygen-8H acenaphthene, at 20-100C, reacted 16-48 hour, after the cooling, underpressure distillation, filter, make 3,6-two substituted amidos-8-oxygen-8H acenaphthene also (1,2-b) pyrroles-9-nitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021484007A CN1167768C (en) | 2002-11-14 | 2002-11-14 | 8-oxy-8H acenaphthene (1,2-b) pyrrol-9nitrile fluorescence chromophore and its derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021484007A CN1167768C (en) | 2002-11-14 | 2002-11-14 | 8-oxy-8H acenaphthene (1,2-b) pyrrol-9nitrile fluorescence chromophore and its derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1410507A CN1410507A (en) | 2003-04-16 |
| CN1167768C true CN1167768C (en) | 2004-09-22 |
Family
ID=4751395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021484007A Expired - Fee Related CN1167768C (en) | 2002-11-14 | 2002-11-14 | 8-oxy-8H acenaphthene (1,2-b) pyrrol-9nitrile fluorescence chromophore and its derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1167768C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1940563B (en) * | 2005-09-28 | 2010-04-28 | 华东理工大学 | Fluorescent marking reagent |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304370C (en) * | 2004-09-15 | 2007-03-14 | 大连理工大学 | Acenaphthene heterocyclic compound and its cell fading inducing and anti-tumor use |
| CN104342126B (en) * | 2013-11-11 | 2017-02-15 | 北京阿格蕾雅科技发展有限公司 | Organic electroluminescent material and organic electroluminescent device |
| CN104313594A (en) * | 2014-11-01 | 2015-01-28 | 济南大学 | Nitrogen-oxygen heterocyclic carbon steel seawater corrosion inhibitor and application thereof |
-
2002
- 2002-11-14 CN CNB021484007A patent/CN1167768C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1940563B (en) * | 2005-09-28 | 2010-04-28 | 华东理工大学 | Fluorescent marking reagent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1410507A (en) | 2003-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1896074A (en) | Fluorescent molecular probe and use for inspecting transient metal and heavy metal ion | |
| CN103172650A (en) | Strong fluorescence fluoro-boron dipyrrole compound containing triphenylamine structure as well as preparation method and application thereof | |
| CN109054039B (en) | Synthesis and application of porous covalent organic framework material with imine structure | |
| CN113214672B (en) | Amide substituted azaindole-pentamethine cyanine dye, its synthesis method and application | |
| CN111825634B (en) | Novel compounds, process for their preparation and their use | |
| CN110256218A (en) | A kind of aggregation-induced emission dye molecule and its synthetic method | |
| CN105669529A (en) | Fullerene pyrrolidine derivative and preparation method thereof | |
| CN1167768C (en) | 8-oxy-8H acenaphthene (1,2-b) pyrrol-9nitrile fluorescence chromophore and its derivative | |
| CN113831287A (en) | Naphthalimide compound with active end and preparation method and application thereof | |
| CN105254655A (en) | Fluorescent amino acid based on BODIPY as well as synthetic method and application thereof | |
| Luo et al. | Indolo-quinoline boron difluoride dyes: synthesis and spectroscopic properties | |
| CN112175607B (en) | Organic room temperature phosphorescent material and preparation method and application thereof | |
| CN113321638A (en) | High-performance fluorescent dye suitable for various fluorescence detection scenes and preparation method thereof | |
| CN109734721B (en) | Pyrazine [2,3-g ] quinoxaline-based organic photosensitizer and preparation method and photodynamic application thereof | |
| CN110295040B (en) | 9, 10-thiophene/furyl anthracene aggregation-induced emission compound and preparation method and application thereof | |
| CN112812088A (en) | Near-infrared luminescent triphenylamine derivative fluorescent molecule and preparation method and application thereof | |
| CN113501836A (en) | Star BODIPY near-infrared fluorescent dye and preparation method thereof | |
| CN113880870B (en) | Pyridine fluorine boron fluorescent dye compound and preparation method thereof | |
| CN110003087A (en) | Fullerene chemistry amino benzenes derivates and its preparation method and application | |
| CN112209935A (en) | Preparation method of pyrazino-fused quinazolinone substance | |
| CN1158288C (en) | Process for quickly synthesizing photochromic spirooxazine by microwave | |
| CN112194563B (en) | Compound containing perylene and fluorobenzene and preparation method and application thereof | |
| CN115028562B (en) | Polysulfide aromatic compound, preparation method and application thereof | |
| CN115160292B (en) | Synthesis method of 3-perfluoroalkyl thioflavone | |
| CN108558739A (en) | Small molecule material and preparation method thereof of the one kind based on the high two-photon absorption of naphtho- indenes fluorenes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |