CN1147561C - Red organic luminous dye and its preparation and application - Google Patents
Red organic luminous dye and its preparation and applicationInfo
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- CN1147561C CN1147561C CNB991073460A CN99107346A CN1147561C CN 1147561 C CN1147561 C CN 1147561C CN B991073460 A CNB991073460 A CN B991073460A CN 99107346 A CN99107346 A CN 99107346A CN 1147561 C CN1147561 C CN 1147561C
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Abstract
The present invention belongs to the technical field of an organic luminescent material which has the structure disclosed in the formula I. The preparation method of the material comprises three steps: step 1, using phosphorus oxychloride, an aryl compound to be formylated and newly distilled and dried dimethyl formamide as raw materials to prepare CHO-R2; step 2, using CHO-R2 and o-hydroxyaryl aryl ethanone as raw materials to prepare 2-hydroxy chalcone by the molar ratio of 1: 1; step 3, using hydrogen peroxide and the 2-hydroxy chalcone as raw materials to prepare 3-hydroxyflavone. The organic luminescent red light domain dye of the present invention can be used for developing electroluminescent devices and manufacturing radiation detectors or can be used as an environmental polarity probe.
Description
The invention belongs to technical field of organic luminescence materials, particularly relate to red organic luminous dye and preparation method thereof and purposes.
It is one of research focus of present material science that development organic light emission compound is used for environment polarity probes, scintillator, electroluminescent information display material.
Luminous organic material is compared with inorganics, is characterized in: be easy to machine-shaping, and with low cost, can prepare the luminescent material that meets particular requirement by molecular designing.People such as Chen Jinxin are in " the new development of organic electric-excitation luminescent material of Taibei city Chinese Chemical Society distribution, chemistry " TaiWan, China the 54 volume first phase of in January, 85 to March, 1997 125 volumes of 140-141 page or leaf and " macromole discussion " 49-58 page or leaf (C.H.Chen, C.W.Tang, J.Shi, K.P.Klubek, Macromol.Symp.125 (1997) are p.49-58) article in report is used in the electroluminescent at the luminous organic dye in ruddiness territory three classes.The first kind is the compound that electron donor(ED)-electron acceptor(EA) group is formed, this compounds luminous because from charge transfer state, glow peak is often wide to loose, and concentration can to form the quencher of intermolecular accumulation body when big luminous, reduce luminous efficiency.Second class is the stiffening ring dyestuff, and as the sour cyanines in side, its rigid structure makes them from Franck-Condon attitude emitting fluorescence, and waveform is sharp-pointed, and colourity is pure.But, can't avoid self-absorption and be difficult to obtain high luminous efficiency because the Stoke displacement is very little.The 3rd class is big conjugated system ring compound, and as phthalocyanines, though their luminescent waveform is narrow, maximum emission wavelength, is difficult to adjust structure from molecular designing for dark red near 700nm.Therefore, fail to obtain satisfied ruddiness territory luminescent dye so far.
The objective of the invention is in order to overcome the defective of above-mentioned luminescent material, provide a class can be in the ruddiness territory luminous have an organic light emission dye well its preparation method that the excited state molecule inner proton shifts (ESPT).This class dyestuff in non-polar solvent or in the solid film luminescent waveform narrow, the Stoke displacement is big, can avoid self-absorption, by changing substituting group, makes the organic light emission dyestuff be adjusted at emission wavelength in the ruddiness territory as required.
Red organic luminous dye structure (3-flavonol) shown in general formula I with excited state molecule inner proton transfer (ESPT) of the present invention:
R wherein
1Be aromatic nucleus and ring type structure, R
2Be aryl.
Of the present invention have the excited state molecule inner proton to shift the synthetic route of red organic luminous dye of (ESPT) as follows:
R wherein
1Be aromatic nucleus and ring type structure, R
2Be aryl.
Synthetic method with red organic luminous dye of excited state molecule inner proton transfer (ESPT) of the present invention is carried out as follows:
The first step: CHO-R
2Synthetic:
Under 0-5 ℃, the phosphoryl chloride (POCl that will newly distill out respectively
3) and the formylated compound aromatic base (R of desire
2H) be dissolved in newly distill out in right amount and exsiccant dimethyl formamide (DMF) in to dissolving fully, R wherein
2H and POCl
3Mol ratio be 1: 1.15～1: 1.2, then above-mentioned two kinds of solution are mixed into reaction soln.Reaction soln is heated to 90～100 ℃, stirs 2～24 hours, and the reaction soln temperature is reduced to room temperature and poured in the frozen water that volume is about 2 times of reaction soln volumes.With saturated weak mineral alkali the reaction system potential of hydrogen is transferred to about pH=7 to there being precipitation to occur, this solution is placed down at 0-4 ℃ spent the night, be approximately 12～24 hours.Then this solution is filtered to such an extent that precipitate, this precipitation is water and non-polar organic solvent washing respectively, and the precipitation after the washing is dissolved in the middle polarity organic solvent, filters insolubles also except that desolvating, and drying obtains CHO-R
2
Or use N, N-methyl formyl radical-aniline prepares starting raw material CHO-R
2With the phosphoryl chloride (POCl that newly distills out
3), the formylated compound aromatic base (R of desire
2H) and N, it is phosphoryl chloride (POCl that N-methyl formyl radical-aniline is dissolved in volume
3) the exsiccant solvent 1,2 of 5 times of volumes, in 4-trichlorobenzene or the toluene, the formylated compound aromatic base (R of desire wherein
2H) and N, the mol ratio of N-methyl formyl radical-aniline is 1: 10; Phosphoryl chloride that newly distills out and N, the mol ratio of N-methyl formyl radical-aniline is 1: 1.1.Reacted 1～4 hour down at 5～10 ℃, stir under the room temperature then and spend the night about 10～24 hours.Add then and the about isopyknic water of reaction mixture, with weight percent concentration be the potential of hydrogen of 10% strong inorganic base aqueous solution conditioned reaction system approximately to pH=8, distilling off solvent 1,2,4-trichlorobenzene or toluene.Reaction residue after filtration, washing, drying, the purification by silica gel column chromatography product obtains CHO-R
2, and reclaim the aromatic compound (R of unnecessary not aldehyde radicalization
2H).
Second step: 2-hydroxyl cinnamophenone synthetic, its structural formula is as follows:
Respectively with formylated compound aromatic base (CHO-R
2), adjacent hydroxyaryl ethyl ketone be dissolved in an amount of polar organic solvent to dissolving fully, wherein formylated compound aromatic base (CHO-R
2) with the mol ratio of adjacent hydroxyaryl ethyl ketone be 1: 1, and to formylated compound aromatic base (CHO-R
2) polar organic solvent in to add volume be 10% the strong inorganic base aqueous solution for the weight percent concentration of 2.5 times of its volumes, then under stirring at room with the polar organic solvent of adjacent hydroxyaryl ethyl ketone, the speed of dripping with about 2 milliliters of per minutes splashes in the polar organic solvent of compound aromatic base, continue under the room temperature to stir 48～60 hours to there being solid to separate out, in reaction soln, add the distilled water that is equivalent to half volume of reaction solution again, being neutralized to neutrality with acid has a large amount of solids to separate out, be further purified, obtain 2-hydroxyl cinnamophenone.
If formylated compound aromatic base (CHO-R
2) poor solubility in single polar organic solvent, reaction can be carried out in phase transition solution.Described phase transition solution is made up of tetrahydrofuran (THF)-water-quaternary ammonium salt-strong inorganic base, and wherein the volumetric molar concentration of quaternary ammonium salt is 2 * 10
-3Mol; The volumetric molar concentration of strong inorganic base is 40 mol; The volume ratio of tetrahydrofuran (THF) and water is 10: 3.Concrete steps are as follows:
With formylated compound aromatic base (CHO-R
2) press 1 mole of formylated compound aromatic base (CHO-R with the phase transition mixing solutions
2): the mixed of 1700 milliliters of phase transition mixing solutionss (being called solution 1); Adjacent hydroxyaryl ethyl ketone and tetrahydrofuran (THF) are by 1 mole of adjacent hydroxyaryl ethyl ketone: the mixed of 700 milliliters of left and right sides tetrahydrofuran (THF)s (being called solution 2).At room temperature, the rate of addition of solution 2 with about 2 milliliters of per minutes splashed in the solution 1, obtain the phase transition mixed reaction solution.The phase transition mixed reaction solution is warming up to gradually and stirred about 50 ℃ 48～50 hours, then the distillation of phase transition mixed reaction solution is removed the tetrahydrofuran (THF) in the reaction system, add with the phase transition mixing solutions in the isopyknic water of tetrahydrofuran (THF), be that the middle polarity organic solvent of 3 times of the volumes of tetrahydrofuran (THF) in the phase transition mixing solutions divides 4 extractions with volume again.Combining extraction liquid is used the siccative drying, filters, and removes and desolvates.Be further purified and obtain 2-hydroxyl cinnamophenone.
The 3rd step: 3-flavonol synthetic, its structural formula is as follows:
In 0-5 ℃ of temperature range, 2-hydroxyl cinnamophenone is dissolved in an amount of polar organic solvent to dissolving fully, with weight percent concentration is that 20% the strong inorganic base aqueous solution adds wherein, speed with about 0.2 milliliter of per minute is 30% superoxol to wherein dripping weight percent concentration then, wherein to add 500 milliliters of weight percent concentration be 20% the strong inorganic base aqueous solution for every mole of 2-hydroxyl cinnamophenone, and the mol ratio of hydrogen peroxide and 2-hydroxyl cinnamophenone is 5: 1.Reaction solution at room temperature continues to stir separated out to solid in 24～30 hours, was neutralized to neutrality with acid, was further purified and obtained the 3-flavonol.
Wherein, described weak mineral alkali is a sodium-acetate etc.; Non-polar organic solvent is sherwood oil, hexanaphthene, normal hexane or normal heptane etc.; The middle polarity organic solvent is ether, tetrahydrofuran (THF) or dioxane etc.; Polar organic solvent is alcohols or acetonitrile etc.; Strong inorganic base is sodium hydroxide or potassium hydroxide etc.; Acid is Glacial acetic acid or dilute hydrochloric acid etc.; Siccative is anhydrous magnesium sulfate, anhydrous sodium sulphate or calcium chloride etc.; Quaternary ammonium salt is cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride.
The principle of luminosity of 3-flavonol of the present invention is as follows:
In the normal excited state excited state molecule of molecule
The prototropy body
Red organic luminous dye of the present invention has the following character:
Base-the 3-flavonol is an example with embodiment 1 described 2-Buddhist nun sieve of a specified duration pyridine:
1. the luminous behavior of vacuum evaporation coating:
With vacuum vapour deposition 2-Buddhist nun sieve of a specified duration pyridine base-3-flavonol is made the uniform thin film that thickness is 150 nanometers, measured its absorption and emission, as shown in Figure 1.As can be seen from Figure 1, its maximum absorption spectrum peak position (λ
AMax) be 448 nanometers, be not affected by the external environment around the molecule in film, compound exists with intramolecularly prototropy attitude, therefore can not the normal excited state fluorescence of emitting molecule, fluorescence shifts body emission, its maximum fluorescence spectrum peak position (λ by the excited state molecule inner proton
EMax) be 618 nanometers, be ruddiness.Two peak positions of absorption spectrum and fluorescence spectrum have the poor of 170 nanometers, therefore can ignore the interference of dyestuff self-absorption to luminous efficiency.Because it is 173310cm that compound excited state molecule inner proton of the present invention shifts body glow peak peak width at half height
-1More than " the new development of organic electric-excitation luminescent material of people such as Chen Jinxin in the distribution of Taibei city Chinese Chemical Society, chemistry ", the intramolecularly that TaiWan, China is reported in the volume first phase article in January, 85 to March the 54 or the peak width at half height (105596cm of intermolecular charge transfer (CT) attitude
-1) narrow, so red organic luminous dye of the present invention is beneficial to colourity control, the film made from this organic light emission dyestuff can be used for making radiation detector and electroluminescent device.
2. the luminous behavior in the opposed polarity:
2-Buddhist nun sieve of a specified duration pyridine base-3-flavonol, structural formula is as follows:
Make the 2-Buddhist nun sieve of a specified duration pyridine base-fluorescence spectrum of 3-flavonol in the opposed polarity solvent, the normal excited state emitting fluorescence of the molecule wavelength of 2-Buddhist nun sieve of a specified duration pyridine base-3-flavones increases and red shift with environment polarity as can be seen from Figure 2, according to table 1, and the λ of its fluorescence spectrum
EMax is (with wave number υ
EmExpression) with solvent dielectric parameter (E
T(30)) mapping meets linear relation, as shown in Figure 3.Therefore, red organic luminous dye of the present invention can be used as fluorescent probe.
The table 1 2-Buddhist nun sieve of a specified duration pyridine base-normal excited state maximum fluorescence of 3-flavonol molecule wavelength (with
Wave number υ
EmExpression), the solvent polarity parameter is (with E
T(30) expression), slope and intercept
υ
em E
T(30)
a
Solvent (* 10
3Cm
-1) (kcal/m)
Acetonitrile 19.305 46.0
Acetone 19.685 42.2
1,2-ethylene dichloride 20.012 41.9
Chloroform 20.534 39.1
Bromobenzene 20.644 37.5
Toluene 21.088 33.9
Tetracol phenixin 21.645 32.5
Slope :-0.16671
Intercept: 26.92011
Relation conefficient :-0.98474
Wherein: cm is centimetre;
Kcal/m is a kilocalorie/rice;
E
T(30)
aBe the document measured value, described document is write " organic chemistry for C. Lai Kate
In solvent effect " article of 1979 years New York 242-244 pages or leaves
(C.Reichardt“Solvent?effects?in?organic?chemistry”，
p.242-244.Verlag?Chemie?Weinheim，New?York，1979.)
With υ
EmAnd E
T(30)
aValue input computer is by directly draw Fig. 3 and providing tiltedly of Origin 5.0 programs
Rate, intercept and relation conefficient.
To be example with acetonitrile/toluene different ratios mixed solvent, along with the acetonitrile ratio increases, solvent polarity increases thereupon, the 2-Buddhist nun sieve of a specified duration pyridine base-normal excited state emitting fluorescence of 3-flavonol wavelength (λ
EMax) red shift, as shown in Figure 4.Calculate λ in every kind of mixed solvent
EThe corresponding wave number υ of max
Em,, just can find out solvent polarity parameter E shown on its corresponding X-coordinate from straight line at the ordinate zou capturing position of Fig. 3
T(30), promptly the slope that provides according to the linear relation of Fig. 3, table 1 is-0.16671, and intercept is 26.92011, according to the polarity E that is easy to calculate molecule environment of living in following formula
T(30):
υ
em＝-0.16671×E
T(30)+26.92011
The data of calculating are listed in table 2, can find out the E that calculates according to Fig. 3, table 1
T(30) value is very nearly the same with the data of bibliographical information, and calculating environment polarity with this fluorescent probe method need not complicated expensive instrument, simple.
Table 2 is made fluorescent probe with 2-Buddhist nun sieve of a specified duration pyridine base-3-flavonol
Calculate the polarity of acetonitrile/toluene different ratios mixed solvent
υ
em E
T(30)
Mixed solvent volume ratio (* 10
3Cm
-1) (kcal/m)
Toluene 21.088 34.9 (33.9)
a
Toluene: acetonitrile=90: 10 20.325 39.5
Toluene: acetonitrile=70: 30 19.881 42.2
Acetonitrile 19.305 45.7 (46.0)
a
Wherein, cm is centimetre;
Kcal/m is a kilocalorie/rice;
(33.9)
a(46.0)
aBe the document measured value, described document is write the article (C.Reichardt " Solvent effects in organic chemistry " of " solvent effect in the organic chemistry " 242-244 page or leaf in 1979 for C. Lai Kate, p.242-244Verlag Chemie Weinheim, New York, 1979.).
Principal feature of the present invention is as follows:
1. the absorbing wavelength of luminous organic dye of the present invention is generally in short wavelength's part of ultraviolet or visible region, but their excited state molecule inner proton shifts the luminous in the long wave direction of body.By molecular designing, change substituting group and can in the red light district scope, regulate their emitted fluorescence spectrum maximum wavelength (λ
EMax) position and can be with the position.
2. because the absorption spectrum λ of luminous organic dye of the present invention
AThe λ of max and fluorescence spectrum
EIt is bigger that max differs, and can ignore the interference of dyestuff self-absorption to luminous efficiency.
3. there is not intramolecularly or intermolecular charge transfer (CT) attitude in luminous organic dye of the present invention in non-polar organic solvent or when solid-state, and it is luminous to shift attitude from the excited state molecule inner proton, and the emitted fluorescence peak is not wide to loose, and is beneficial to colourity control.
4. the wavelength of the normal excited state emitting fluorescence of the molecule of luminous organic dye of the present invention increases and red shift with environment polarity, the λ of its fluorescence spectrum
EMax and solvent dielectric parameter E
T(30) the mapping relation of being in line.
The main application of luminous organic dye of the present invention is as follows:
1. can be used for environment polar probe:
The λ of the 3-flavonol fluorescence spectrum in the opposed polarity organic solvent that glows
EMax and solvent dielectric parameter E
T(30) mapping can obtain straight line.Therefore, according to the λ of its fluorescence spectrum
EThe position of max on straight line can calculate the polarity of dye molecule environment of living in.
2. can be used to make radiation detector:
This dyestuff with twinkler of excited state molecule inner proton transfer body, wavelength of fluorescence is red shift significantly, overcomes the dyestuff self-absorption to luminous interference.When it is subjected to the optical excitation meeting effectively luminous, be expected to make plastic scintillator and be used to detect radiation.
3. can be used as electroluminescent material
The absorbing wavelength of luminous organic dye of the present invention is generally in short wavelength regions, but can make their excited state molecule inner proton shift the luminous in the ruddiness territory of body by molecular designing, and crest is narrower; Also can change substituting group the current potential of dyestuff is changed,, improve luminous efficiency to adapt to the requirement of electroluminescent device.
Description of drawings:
The absorption and the fluorescence spectrum of Fig. 1-2-Buddhist nun sieve pyridine base of a specified duration-3-flavonol plated film
Fig. 2-2-Buddhist nun sieve of a specified duration pyridine base-the fluorescence spectrum of 3-flavonol in the opposed polarity solvent
Fig. 3-2-Buddhist nun sieve of a specified duration pyridine base-normal excited state the maximum fluorescence of 3-flavonol molecule wavelength (with
Wave number υ
EmExpression) to solvent polarity parameter (E
T(30)) Zuo Tu linear relation
Fig. 4-2-Buddhist nun sieve of a specified duration pyridine base-the fluorescence spectrum of 3-flavonol in acetonitrile/toluene mixed solvent
Drawing reference numeral:
1-absorption spectrum 2-fluorescence spectrum 3-acetonitrile 4-1,2-ethylene dichloride 5-bromobenzene
6-toluene 7-toluene: acetonitrile=90: 10 8-toluene: acetonitrile=70: 30
Further specify the present invention below in conjunction with embodiment:
Embodiment 1
Synthesizing of 2-Buddhist nun sieve of a specified duration pyridine base-3-flavonol:
Synthesizing of the first step formyl radical Buddhist nun sieve of a specified duration pyridine:
Reaction scheme is as follows:
0 ℃ of 2 milliliters of phosphoryl chloride (0.023 mole) that will newly distill out down add be equipped with 9 milliliters newly distill out and 50 milliliters of pyriform bottles of exsiccant dimethyl formamide (DMF) in to dissolving fully.3.5 gram (0.02 mole) Buddhist nun sieve pyridines for a long time are dissolved in 3.5 milliliters newly to distill out and exsiccant dimethyl formamide (DMF) and add in the above-mentioned pyriform bottle and make reaction soln.Reaction soln is heated to about 95 ℃, stirs 2 hours, and temperature is reduced to room temperature and poured in 30 milliliters of frozen water.With saturated acetic acid sodium system is transferred to about pH=7, have the light green precipitation to occur, place in the refrigerator and spend the night.Filter and water and normal hexane washing precipitation respectively, precipitation is dissolved in ether, filters insolubles, removes and desolvates, and drying gets formyl radical Buddhist nun sieve of a specified duration pyridine, and weight is 2.8 grams, productive rate 69%, and its proterties is the light green solid.
1H nuclear magnetic resonance data (CDCl
3), chemical shift (ppm): 1.98 (t, 4H, CH
2), 2.78 (t, 4H, CH
2Ar), 3.28 (t, 4H, CH
2N), 7.28 (s, 2H, Ar), 9.58 (s, 1H, CHO); M/z 202 (M+1)
+
Second step: Buddhist nun sieve pyridine base-2-hydroxyl cinnamophenone is synthetic for a long time:
Reaction scheme is as follows:
4 gram (0.02 mole) formyl radicals Buddhist nun sieve of a specified duration pyridine is added in 250 milliliters of there-necked flasks; with 20 milliliters of anhydrous alcohol solutions; and to add 50 milliliters of weight percent concentration be 10% aqueous sodium hydroxide solution; thereafter dripped 20 milliliters of ethanol solutions of 2.94 gram (0.02 mole) o-hydroxyacetophenones in 10 minutes, it is yellow that reaction solution is.At room temperature continue to stir 60 hours, have yellow solid to separate out.Add 45 ml distilled waters in solution, be neutralized to neutrality with Glacial acetic acid, a large amount of red-purple solids are separated out suction filtration and washing.With weight percent concentration is 95% ethyl alcohol recrystallization, the dry Buddhist nun sieve pyridine base of a specified duration-2-hydroxyl cinnamophenone that gets, and weight is 4.29 grams, productive rate 65%.
1H nuclear magnetic resonance data (CDCl
3), chemical shift (ppm): 1.98 (m, 4H, CH
2), 2.77 (t, 4H, CH
2Ar), 3.27 (t, 4H, CH
2N), and 6.9-7.9 (m, 8H, Ar); M/z 320 (M+1)
+
Synthesizing of the 3rd step 2-Buddhist nun sieve of a specified duration pyridine base-3-flavonol:
Reaction scheme is as follows:
About 2 ℃, down 3.3 grams (0.01 mole) Buddhist nun sieve pyridine base of a specified duration-2-hydroxyl cinnamophenone is put into 100 milliliters of there-necked flasks, dissolve with 20 ml methanol, and to add 5 milliliters of weight percent concentration be 20% aqueous sodium hydroxide solution, and Dropwise 5 .5 milliliter weight percent concentration is 30% (0.05 mole) superoxol in about 30 minutes thereafter.Reaction solution at room temperature continued to stir 28 hours, and golden yellow solid is separated out, and is neutralized to neutrality with Glacial acetic acid, suction filtration.Get the yellowish red color solid, recrystallization gets 2-Buddhist nun sieve of a specified duration pyridine base-3-flavonol in dehydrated alcohol, and weight is 2.84 grams, productive rate 82%.
1H nuclear magnetic resonance data (CDCl
3), chemical shift (ppm): 2.00 (m, 4H), 2.75 (t, 4H), 3.31 (t, 4H), 6.5-8.0 (m, 6H); M/z 334 (M+1)
+
Synthesizing of 4-triphenyl amido-3-flavonol:
Synthesizing of the first step formyl radical triphenylamine: reaction scheme is as follows:
In 100 milliliters of round-bottomed flasks, add the N that mixes; (4 milliliters of N-methyl formyl radical-aniline; 0.033 the phosphoryl chloride that newly distills out (2.6 milliliters, 0.03 mole) mole); 13 milliliters of exsiccant 1; 2, the 4-trichlorobenzene adds 80 gram triphenyl ammonia (0.33 mole) again and makes reaction solution; reaction solution reacted 2.5 hours about 8 ℃, stirred 24 hours under the room temperature.The water that adds 20 milliliters then is that 10% aqueous sodium hydroxide solution conditioned reaction liquid acid-basicity makes the pH value of reaction solution be about 8 with weight percent concentration, distilling off solvent 1,2,4-trichlorobenzene.Reaction residue after filtration, washing, drying; (elutriant is sherwood oil (60-90 a ℃) to the purification by silica gel column chromatography product: ethyl acetate=10: 1 (volume: volume)); reclaim 72.6 gram triphenylamines; obtain the formyl radical triphenylamine; weight is 5.3 grams; productive rate: 64.3%, its proterties is a light green.
1H nuclear magnetic resonance data (CDCl
3), chemical shift (ppm): 7.0-7.3 (m, 14H, Ar), 9.64 (s, 1H, CHO); M/z 274 (M+1)
+
Synthesizing of second step triphenyl amido-2-hydroxyl cinnamophenone:
Reaction scheme is as follows:
Prepare tetrahydrofuran (THF)-water-quaternary ammonium salt-strong inorganic base phase transition mixing solutions earlier, wherein the volumetric molar concentration of quaternary ammonium salt is 2 * 10
-3Mol; The volumetric molar concentration of strong inorganic base is 40 mol; The volume ratio of tetrahydrofuran (THF) and water is 10: 3; Specifically: tetrahydrofuran (THF) (40 milliliters)-water (12 milliliters)-cetyl trimethylammonium bromide (36 milligrams, 10
-4Mole)-sodium hydroxide (8 grams, 2 moles).
The formyl radical triphenylamine of 8.2 grams (0.03 mole) is added in 250 milliliters of round-bottomed flasks with 51 milliliters of phase transition mixing solutionss.At room temperature, in above-mentioned reaction solution, drip the tetrahydrofuran solution (volume of tetrahydrofuran (THF) is 21 milliliters) of o-hydroxyacetophenone 4.1 grams (0.03 mole) in 10 minutes.Be warming up to gradually about 50 ℃ and stirred about 48 hours.The tetrahydrofuran (THF) in the system is removed in distillation, adds 40 milliliters water, divides 4 extractions with 120 milliliters ether.Combining extraction liquid is used anhydrous magnesium sulfate drying, filters, and removes and desolvates.Use ethyl alcohol recrystallization, drying gets triphenyl amido-2-hydroxyl cinnamophenone, weight 6.7 grams, and productive rate 57.1%, proterties is a red solid.
1H nuclear magnetic resonance data (CDCl
3), chemical shift (ppm): 6.8-8.0 (m, 20H, Ar); M/z 392 (M+1)
+
Synthesizing of the 3rd step 2-triphenyl amido-3-flavonol:
Reaction scheme is as follows:
About 4 ℃, 3.9 gram (0.01 mole) triphenyl amido-2-hydroxyl cinnamophenones are put into 100 milliliters of there-necked flasks, it with 20 milliliters of weight percent concentration 95% dissolve with ethanol, add 5 milliliters of weight percent concentration and be 20% aqueous sodium hydroxide solution, Dropwise 5 .5 milliliter weight percent concentration is 30% (0.05 mole) superoxol in about 30 minutes thereafter.Reaction solution at room temperature continued to stir 24 hours, and yellow solid is separated out, and Glacial acetic acid is neutralized to neutrality, suction filtration.Get the orange solid, recrystallization gets 2-triphenyl amido-3-flavonol in dehydrated alcohol, and weight is 3.3 grams, productive rate 81.1%.
1H nuclear magnetic resonance data (CDCl
3), chemical shift (ppm): 6.7-8.2 (m, 18H); M/z 406 (M+1)
+
Claims (5)
1. red organic luminous dye is characterized in that structure is shown in general formula I:
R wherein
1Be aromatic nucleus and ring type structure, R
2Be aryl.
2. the preparation method of red organic luminous dye as claimed in claim 1 is characterized in that carrying out as follows:
The first step: CHO-R
2Synthetic:
Under 0-5 ℃, respectively the formylated compound aromatic base of phosphoryl chloride that will newly distill out and desire be dissolved in newly distill out in right amount and the exsiccant dimethyl formamide in to fully the dissolving, wherein the mol ratio of formylated compound aromatic base of desire and phosphoryl chloride is 1: 1.15～1: 1.2, then above-mentioned two kinds of solution is mixed into reaction soln; Reaction soln is heated to 90～100 ℃, stirs 2～24 hours, and the reaction soln temperature is reduced to room temperature and poured in the frozen water that volume is about 2 times of reaction soln volumes; With saturated weak mineral alkali the system potential of hydrogen is transferred to about pH=7 to there being precipitation to occur, this solution is placed down at 0-4 ℃ spent the night; Then this solution is filtered to such an extent that precipitate, with water and the non-polar organic solvent washing respectively of this precipitation, the precipitation after the washing is dissolved in the middle polarity organic solvent, filters insolubles also except that desolvating, and drying obtains CHO-R
2
Or
With formylated compound aromatic base of phosphoryl chloride, desire and the N that newly distills out, N-methyl formyl radical-aniline is dissolved in the dry solvent 1 that volume is 5 times of phosphoryl chloride volumes, 2, in 4-trichlorobenzene or the toluene, wherein formylated compound aromatic base of desire and N, the mol ratio of N-methyl formyl radical-aniline is 1: 10; Phosphoryl chloride that newly distills out and N, the mol ratio of N-methyl formyl radical-aniline is 1: 1.1; Reacted 1～4 hour down at 5～10 ℃, stir under the room temperature then and spend the night; Add then and the about isopyknic water of reaction mixture, with weight percent concentration be the potential of hydrogen of 10% strong inorganic base aqueous solution conditioned reaction system approximately to pH=8, distilling off solvent 1,2,4-trichlorobenzene or toluene; Reaction residue after filtration, washing, drying, the purification by silica gel column chromatography product obtains CHO-R
2
Second step: 2-hydroxyl cinnamophenone synthetic:
Respectively with CHO-R
2, adjacent hydroxyaryl ethyl ketone be dissolved in an amount of polar organic solvent to dissolving fully, CHO-R wherein
2With the mol ratio of adjacent hydroxyaryl ethyl ketone be 1: 1, and to CHO-R
2Polar organic solvent in to add volume be 10% the strong inorganic base aqueous solution for the weight percent concentration of 2.5 times of its volumes, then under stirring at room,, splash into CHO-R with the speed of dripping of about 2 milliliters of per minutes with the polar organic solvent of adjacent hydroxyaryl ethyl ketone
2Polar organic solvent in, continue to stir 48～60 hours under the room temperature to there being solid to separate out; Add the distilled water that is equivalent to half volume of reaction solution again in reaction soln, being neutralized to neutrality with acid has a large amount of solids to separate out, and is further purified, and obtains 2-hydroxyl cinnamophenone;
Or
With CHO-R
2Press 1 mole of CHO-R with the phase transition mixing solutions
2: the mixed of 1700 milliliters of phase transition mixing solutionss, be called solution 1; Adjacent hydroxyaryl ethyl ketone and tetrahydrofuran (THF) are pressed 1 mole of adjacent hydroxyaryl ethyl ketone: the mixed of 700 milliliters of left and right sides tetrahydrofuran (THF)s, be called solution 2; At room temperature, the rate of addition of solution 2 with about 2 milliliters of per minutes splashed in the solution 1, obtain the phase transition mixed reaction solution; The phase transition mixed reaction solution is warming up to gradually and stirred about 50 ℃ 48～50 hours; Then the distillation of phase transition mixed reaction solution is removed the tetrahydrofuran (THF) in the reaction system, add with the phase transition mixing solutions in the isopyknic water of tetrahydrofuran (THF), be that the middle polarity organic solvent of 3 times of the volumes of tetrahydrofuran (THF) in the phase transition mixing solutions divides 4 extractions with volume again; Combining extraction liquid is used the siccative drying, filters, and removes and desolvates; Be further purified and obtain 2-hydroxyl cinnamophenone;
The 3rd step: 3-flavonol synthetic:
In 0-5 ℃ of temperature range, 2-hydroxyl cinnamophenone is dissolved in an amount of polar organic solvent to dissolving fully, with weight percent concentration is that 20% the strong inorganic base aqueous solution adds wherein, speed with about 0.2 milliliter of per minute is 30% superoxol to wherein dripping weight percent concentration then, wherein to add 500 milliliters of weight percent concentration be 20% the strong inorganic base aqueous solution for every mole of 2-hydroxyl cinnamophenone, and the mol ratio of hydrogen peroxide and 2-hydroxyl cinnamophenone is 5: 1; Reaction solution at room temperature continues to stir separated out to solid in 24～30 hours, was neutralized to neutrality with acid, was further purified and obtained the 3-flavonol.
3. the preparation method of red organic luminous dye as claimed in claim 2 is characterized in that described phase transition mixing solutions is made up of tetrahydrofuran (THF)-water-quaternary ammonium salt-strong inorganic base, and wherein the volumetric molar concentration of quaternary ammonium salt is 2 * 10
-3Mol; The volumetric molar concentration of strong inorganic base is 40 mol; The volume ratio of tetrahydrofuran (THF) and water is 10: 3.
4. the preparation method of red organic luminous dye as claimed in claim 2 is characterized in that described weak mineral alkali is a sodium-acetate; Non-polar organic solvent is sherwood oil, hexanaphthene, normal hexane or normal heptane; The middle polarity organic solvent is ether, tetrahydrofuran (THF) or dioxane; Polar organic solvent is alcohols or acetonitrile; Strong inorganic base is sodium hydroxide or potassium hydroxide; Acid is Glacial acetic acid or dilute hydrochloric acid; Siccative is anhydrous magnesium sulfate, anhydrous sodium sulphate or calcium chloride; Quaternary amine is cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride.
5. the purposes of red organic luminous dye as claimed in claim 1 is characterized in that: be used to develop electroluminescent device, make radiation detector or be used for the environment polarity probes.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB991073460A CN1147561C (en) | 1999-05-19 | 1999-05-19 | Red organic luminous dye and its preparation and application |
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| CNB991073460A CN1147561C (en) | 1999-05-19 | 1999-05-19 | Red organic luminous dye and its preparation and application |
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| CN1147561C true CN1147561C (en) | 2004-04-28 |
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| CN100408651C (en) * | 2001-12-30 | 2008-08-06 | 中国科学院理化技术研究所 | Red fluorescent dye and its systhesis method and use |
| US6680132B2 (en) * | 2002-03-25 | 2004-01-20 | Eastman Kodak Company | Red organic electroluminescent devices |
| CN1305867C (en) * | 2004-05-19 | 2007-03-21 | 陕西师范大学 | Populin-6-sulfonic acid sodium synthesis method and uses in preparaing photoluminescent material |
| TWI385167B (en) * | 2008-11-11 | 2013-02-11 | Ind Tech Res Inst | Dyes applied to polymer solar cells and polymer solar cells comprising the same |
| TW201122079A (en) * | 2009-12-30 | 2011-07-01 | Ind Tech Res Inst | Fluorescent materials and solar cells comprising the same |
| CN107235849B (en) * | 2017-04-20 | 2019-06-25 | 深圳大学 | A kind of chalcone base fluorescent optical sensor and the preparation method and application thereof |
| CN107118193B (en) * | 2017-04-20 | 2019-05-14 | 深圳大学 | A kind of flavonoids fluorescent optical sensor and the preparation method and application thereof |
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