CN101798467A - Cholesteryl-contained 2D-pi-A type pyran charge transfer fluorescent dye and synthesizing method thereof - Google Patents
Cholesteryl-contained 2D-pi-A type pyran charge transfer fluorescent dye and synthesizing method thereof Download PDFInfo
- Publication number
- CN101798467A CN101798467A CN 200910214085 CN200910214085A CN101798467A CN 101798467 A CN101798467 A CN 101798467A CN 200910214085 CN200910214085 CN 200910214085 CN 200910214085 A CN200910214085 A CN 200910214085A CN 101798467 A CN101798467 A CN 101798467A
- Authority
- CN
- China
- Prior art keywords
- charge transfer
- cholesteryl
- type
- reaction
- fluorescence dye
- 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.)
- Pending
Links
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 22
- 238000012546 transfer Methods 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 title abstract 3
- 238000000034 method Methods 0.000 title abstract 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol group Chemical group [C@@H]1(CC[C@H]2[C@@H]3CC=C4C[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C)[C@H](C)CCCC(C)C HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims abstract description 52
- -1 C5-C20 cycloalkyl Chemical group 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 238000010992 reflux Methods 0.000 claims description 23
- 150000004880 oxines Chemical class 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 235000012000 cholesterol Nutrition 0.000 claims description 18
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical compound O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 claims description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 10
- 238000005874 Vilsmeier-Haack formylation reaction Methods 0.000 claims description 9
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 238000005401 electroluminescence Methods 0.000 abstract 1
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 231100000614 poison Toxicity 0.000 abstract 1
- 230000007096 poisonous effect Effects 0.000 abstract 1
- 239000000523 sample Substances 0.000 abstract 1
- 125000000542 sulfonic acid group Chemical group 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- 239000007787 solid Substances 0.000 description 21
- 238000001953 recrystallisation Methods 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 239000002223 garnet Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000006399 behavior Effects 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- WVHBHPATSLQXGC-UHFFFAOYSA-N benzene;ethanol Chemical compound CCO.C1=CC=CC=C1 WVHBHPATSLQXGC-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UXTMROKLAAOEQO-UHFFFAOYSA-N chloroform;ethanol Chemical compound CCO.ClC(Cl)Cl UXTMROKLAAOEQO-UHFFFAOYSA-N 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000003637 steroidlike Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Landscapes
- Steroid Compounds (AREA)
Abstract
The invention relates to a cholesteryl-contained 2D-pi-A type pyran charge transfer fluorescent dye containing a cholesterol group and a synthesizing method thereof. The cholesteryl-based pyran dye has a structure shown as the formula (I). The dye can realize the fluorescent chromogenic wavelengths in different solvents by utilizing the interaction of charge transfer, Van der Waals' force, dipole-dipole, and the like in molecules and can be used for the fields of organic electroluminescence, poisonous and organic compound detection, a molecular sensor, biological probe light, light collection, and the like. In the formula (1), each R and R' can be same, can also be different and are one of hydrogen, C1-C16 alkyl, C1-C16 alkoxyl, C5-C20 cycloalkyl, aromatic ring group or a heterocyclic group, halogen, hydroxyl and a sulfonic acid group; X is S or O; and Y is O, C or NH.
Description
Technical field
The present invention relates to a kind of intramolecular charge and shift fluorescence dye and synthetic method thereof, relate to a kind of cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye and synthetic method thereof that contain specifically.
Background technology
(D-π-A) compound becomes the focus of research in recent years to have the electron donor(ED)-electron acceptor(EA) of conjugated structure, this compounds of major cause has important use at device for non-linear optical, laser dyes laser apparatus, organic electroluminescent (OLED), toxic organic compound detection, bioprobe, molecular switch and transmitter, dye sensitization solar battery etc. and is worth (Analytical Chemistry, 2006; 78 (11): 3591-600; Angew.Chem.Int.Ed.2007,46,5549-5553; J.AM.CHEM.SOC.2005,127,17799-17802).In this numerous class organic compound, electron donor(ED)-electron acceptor(EA) pyrans class charge transfer functional dye with conjugated structure, because variation and medium pH variation to solvent polarity have high susceptibility, be the fluorescent chromophore (Macromolecules that has potentiality, 2009,42,1733-1738; Dyes and Pigments, 2008,78:25-33).Yet this class dyestuff has big two dimensional structure, forms state of aggregation easily, causes fluorescent quenching.A kind of effective way that overcomes this phenomenon is the gathering behavior that changes molecule by chemically modified, as control molecular configuration, conformation, reduce forming the tendency of ordered aggregation each other and weakening intermolecular ground state and the excited state interaction, thereby eliminate the self-quenching phenomenon effectively.Cholesterol is the important steroidal compounds of a class, can utilize the intermolecular Van der Waals force of cholesterol to realize intermolecular self-assembly, change the parcel and the arrangement of molecule, thereby change molecule photochemistry and optical physics behavior (as: Chem.Eur.J.2007 in solution and solid, 13,8231-8239; Angew.Chem.Int.Ed.2007,46,8005-8009; J.Phys.Chem.B, 2007,111,2000-2007).By appropriate molecular designing, utilize the self-assembly behavior regulation and control pyrans chromophoric luminescent properties of cholesterol group in solvent, the behavior of control molecule self aggregation realizes effective regulation and control of fluorescence.Given this, the technical issues that need to address of the present invention are: design and synthesize a kind of novel cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye that contains.
Summary of the invention
The objective of the invention is to remedy the deficiency that prior art exists, a kind of cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye that contains is provided;
Another object of the present invention provides the synthetic method that contains cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye.
For achieving the above object, the cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye that contains of the present invention, its general structure is as follows:
In the formula (I), each R and R ' can be identical, also can be different.They are hydrogen, C
1～C
16Alkyl, C
1～C
16Alkoxyl group, C
5～C
20Cycloalkyl, aromatic ring yl or heterocyclic radical, halogen, hydroxyl, sulfonic group; X is S, and O's is a kind of; Y is O, and C's is a kind of.
Each R and R ' can be identical, also can be different, be hydrogen, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, C
5～C
10Cycloalkyl, aromatic ring yl or C
4～C
10Heterocyclic radical; X is S or O; Y is O or C.
Each R is identical with R ', is hydrogen, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, C
5～C
10Cycloalkyl, aromatic ring yl or C
4～C
10Heterocyclic radical; X is S or O; The Y atom is O.
Each R is identical with R ', is hydrogen, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, C
5～C
10Cycloalkyl, aromatic ring yl or C
4～C
10Heterocyclic radical; X is S or O; The Y atom is C.
Each R is identical with R ', is hydrogen, methyl, methoxyl group, cyclohexyl, phenyl or ferrocenyl; X is O; The Y atom is O.
Each R is identical with R ', is hydrogen, methyl, methoxyl group, cyclohexyl, phenyl or ferrocenyl; X is S; The Y atom is O.
This fluorescence dye has different fluorescent emission wavelength in different solvents.
In a preferred design of the present invention, each R is identical with R ', and they are hydrogen, C
1～C
16Alkyl, C
1～C
16Alkoxyl group, C
5～C
20Cycloalkyl, aromatic ring yl or heterocyclic radical, X are S, and O's is a kind of; Y is O, one kind of C.
More preferably: R is identical with R ', and they are C
1～C
6Alkyl, C
1～C
6Alkoxyl group, C
5～C
10Cycloalkyl, aromatic ring yl or heterocyclic radical, X are S, and O's is a kind of; Y is O, one kind of C.
Best R=R ' is ethyl, oxyethyl group, and cyclohexyl, phenyl, X are S; Y is O.
A kind of synthetic method that contains cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye, with N, N-diethanolaniline, cholesterol acyl chlorides are raw material, through the synthetic key intermediate (II) of over-churning, Vilsmeier-Haack reaction or with aniline and vinylformic acid condensation, then with cholesterol generation esterification, the synthetic key intermediate of Vilsmeier-Haack reaction (II ') further takes place obtain target compound then with after the reaction such as pyrans class chromophoric group (III) condensation condensation.
Specifically comprise the steps:
A) N, N-diethanolaniline, cholesterol acyl chlorides are raw material, under the organic alkali catalyst condition, obtain compound shown in the intermediate 1 in the refluxing toluene reaction, the Vilsmeier-Haack reaction takes place then obtain key intermediate (II)
B) reaction of aniline and vinylformic acid obtains N, and N-two-propionyloxy aniline obtains key intermediate 2 with lentochol reaction then under catalyst action, Vilsmeier-Haack reaction takes place then obtain key intermediate (II ')
C) under pyrone and barbituric acid or the derivative nitrogen protection condition, diacetyl oxide is made solvent refluxing, obtains key intermediate (III)
D) key intermediate (II) or (II ') are placed acetonitrile with intermediate (III), under condition of nitrogen gas, back flow reaction at least 6 hours (obtaining target product).
Synthetic route is as follows:
Synthesizing of cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye, mainly contain the crucial middle of cholesteryl through prepared in reaction such as esterification, Vilsmeier-Haack, acylations, condensation reaction obtains target product with pyrans class chromophoric group then.
This contains cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye, utilizes interactions such as intramolecular charge transfer, Van der Waals force, dipole-dipole can be implemented in fluorescence color development wavelength in the different solvents.Such dyestuff can be used as fields such as organic electroluminescent, toxic organics detection, molecule sensor, bioprobe light, light collection.
Embodiment
The present invention is further elaborated below by example, and purpose is better to understand content of the present invention, and therefore, the cited case does not limit protection scope of the present invention:
Embodiment 1
In 100ml single port flask; add N, ' N-two-ethanol based aniline 1.81g, cholesterol acyl chlorides 9.856g, 50ml toluene; the 1ml triethylamine; reflux is 5 hours under the nitrogen protection condition, cooling, rotary evaporation; concentrate and remove toluene; ethanol-chloroform recrystallization obtains the 8.5g white crystalline powder, and productive rate is 81.5%.
1H-NMR (400MHz, CDCl3, ppm): δ 1.01-2.38 (m, 90H), 3.75 (t, 4H ,-CH
2N), 4.4 (t, 4H ,-CH
2O), 6.8 (d, 2H), 7.27 (d, 2H); Ultimate analysis: C, 78.52; H, 10.37; N, 1.28; O, 9.83
In the 250ml there-necked flask, add 5.03g and go up the synthetic intermediate 1 that obtains of step, 60mlN, dinethylformamide, ice-water bath are cooled to 0-10 ℃, drip the 0.756g phosphorus oxychloride then, in 0.5 hour, drip off, remove ice-water bath, stirring at room 1 hour, reflux is 1 hour then, reduce to room temperature, mixture is poured in the frozen water, add salt of wormwood and regulate pH value about 10, separate out precipitation, filter, wash 3 times, oven dry, silica gel column chromatography separates (ethyl acetate: chloroform=1: 5), get white crystalline powder 4.13g.Productive rate 80.5%
1H-NMR (400MHz, CDCl
3, ppm): δ 1.03-2.76 (m, 90H), 3.52 (t, 4H ,-CH
2N), 5.3 (t, 4H ,-CH
2O), 7.0 (d, 2H), 7.2 (d, 2H), 9.8 (1,1H ,-CHO); Ultimate analysis: C, 77.69; H, 9.85; N, 1.20; O, 11.26
In 100ml single port flask, add 2,2 '-dimethyl pyrans ketone 2.48g, barbituric acid 2.6g, 30ml diacetyl oxide; reflux is 5 hours under the nitrogen protection condition, and cooling is filtered; get yellow powder shape solid, ethyl alcohol recrystallization obtains 3.98g yellow crystal sprills.Productive rate is 85%.
1H-NMR (400MHz, d-DMSO, ppm): δ 1.85 (s, 6H), 6.9 (s, 2H), 11.8 (s, 2H), ultimate analysis: 57.0; H, 4.30; N, 10.2,28.5.
In the 100ml there-necked flask; add the pyrone intermediate 0.06g that contains barbituric acid; cholesterol intermediate (II) 0.55g; the 20ml acetonitrile drips several Piperazine anhydrous then, under the nitrogen protection condition; reflux 6 hours; reaction is finished postcooling to room temperature, and filtering-depositing obtains the garnet pressed powder.Ethyl alcohol recrystallization obtains red powder shape solid 0.36g.Productive rate 60.5% ultimate analysis: C, 77.00; H, 9.50; N, 1.50; O, 12.00.
Embodiment 2
In 100ml single port flask, add 2,2 '-dimethyl pyrans ketone 1.24g, N, N-dimethyl barbituric acid 1.56g; the 30ml diacetyl oxide, reflux is 5 hours under the nitrogen protection condition, and cooling is filtered; get yellow powder shape solid, ethyl alcohol recrystallization obtains 2.30g yellow crystal sprills.Productive rate is 88%.
1H?NMR(400MHz，CDCl
3，ppm)d：6.67(s，2H，pyran-H)，3.30(s，6H，NCH
3)，1.56(s，6H，CH3)，EI-MS，m/z?262?Elemental?analysis：C，59.49；H，5.30；N，10.59％.C
13H
14N
2O
4?requires：C，59.54；H，5.38；N，10.68％.
In the 100ml there-necked flask; add and contain N; the pyrone intermediate 0.066g of N-dimethyl barbituric acid, cholesterol intermediate (II) 0.55g, 20ml acetonitrile; drip several Piperazine anhydrous then; under the nitrogen protection condition, reflux 8 hours, reaction is finished postcooling to room temperature; filtering-depositing obtains the garnet pressed powder.Ethyl alcohol recrystallization obtains red powder shape solid 0.36g.Productive rate 60.5% ultimate analysis: C, 76.98; H, 9.40; N, 2.12; O, 11.50.
Embodiment 3
In 100ml single port flask, add 2,2 '-dimethyl pyrans ketone 1.24g, N, N-dicyclohexyl barbituric acid 2.92g; the 50ml diacetyl oxide, reflux is 5 hours under the nitrogen protection condition, and cooling is filtered; get yellow powder shape solid, ethyl alcohol recrystallization obtains 3.38g yellow crystal sprills.Productive rate is 85%.Directly be used in next step.
In the 100ml there-necked flask; add N; the pyrone intermediate 0.11g of N-dicyclohexyl barbituric acid, cholesterol intermediate (II) 0.55g, 20ml acetonitrile; drip several Piperazine anhydrous then; under the nitrogen protection condition, reflux 6 hours, reaction is finished postcooling to room temperature; filtering-depositing obtains silent red solid powder.Ethyl alcohol recrystallization obtains red powder shape solid 0.42g.Productive rate 65.0% ultimate analysis: C, 77.58; H, 9.42; N, 2.00; O, 11.00.
Embodiment 4
In 100ml single port flask, add 2,2 '-dimethyl pyrans ketone 1.24g, N, N-two-phenyl barbituric acid 2.80g; the 30ml diacetyl oxide, reflux is 5 hours under the nitrogen protection condition, and cooling is filtered; get yellow powder shape solid, ethyl alcohol recrystallization obtains 3.28g yellow crystal sprills.Productive rate is 85%.Directly carry out next step.
In the 100ml there-necked flask; add N; the pyrone intermediate 0.10g of N-two-phenyl barbituric acid, cholesterol intermediate (II) 0.55g, 20ml acetonitrile; drip several Piperazine anhydrous then; under the nitrogen protection condition, reflux 6 hours, reaction is finished postcooling to room temperature; filtering-depositing obtains the garnet pressed powder.Ethyl alcohol recrystallization obtains red powder shape solid 0.37g.Productive rate 58.0% ultimate analysis: C, 78.00; H, 9.15; N, 2.19; O, 10.66.
Embodiment 5
In 100ml single port flask, add 2,2 '-dimethyl pyrans ketone 1.24g, N, N-diethyl-thiobarbituricacid 2.0g; the 30ml diacetyl oxide, reflux is 5 hours under the nitrogen protection condition, and cooling is filtered; get yellow powder shape solid, ethyl alcohol recrystallization obtains 2.45g yellow crystal sprills.Productive rate is 80%.Be directly used in next step.
In the 100ml there-necked flask; add the pyrone intermediate 0.08g that contains barbituric acid; cholesterol intermediate (II) 0.55g; the 20ml acetonitrile drips several Piperazine anhydrous then, under the nitrogen protection condition; reflux 6 hours; reaction is finished postcooling to room temperature, and filtering-depositing obtains the garnet pressed powder.Ethanol-benzene mixed solvent recrystallization obtains red powder shape solid 0.33g.Productive rate 53.0% ultimate analysis: C, 76.65; H, 9.60; N, 2.07; O, 10.30; S, 1.38.
Embodiment 6
In 250ml single port flask, add N, ' N-two-propionyloxy aniline 1.0g, cholesterol 3.5g, 60ml tetrahydrofuran (THF), 1.85g dicyclohexyl carbon imide and 0.55g 4-dimethylamine pyridine, room temperature stirring overnight, rotation concentrates, and obtains white solid, adds 100ml methyl alcohol stirring at room, suction filtration obtains the thick product of white solid.Chloroform is done developping agent silica gel group chromatographic separation, obtains pure white powder solid 2.82g, productive rate 68%.
1H-NMR(400MHz，CDCl3，ppm)：δ1.01-2.57(m，90H)，3.68(t，4H)，4.6(t，2H)，5.4(d，2H)，6.72-6.9(d，3H)，7.27(d，2H)。
In the 250ml there-necked flask, add 2.03g and go up the synthetic intermediate that obtains of step, 40mlN, dinethylformamide, ice-water bath are cooled to 0-10 ℃, drip the 0.312g phosphorus oxychloride then, in 0.5 hour, drip off, remove ice-water bath, stirring at room 1 hour, reflux is 1 hour then, reduce to room temperature, mixture is poured in the frozen water, add salt of wormwood and regulate pH value about 10, separate out precipitation, filter, wash 3 times, oven dry, silica gel column chromatography separates (methyl alcohol: chloroform=1: 100), get white crystalline powder 0.82g.Productive rate 40.5%
1H-NMR(400MHz，CDCl
3，ppm)：δ1.03-2.70(m，90H)，3.75(t，4H)，4.6(m，2H)，5.37(d，2H)，6.7(d，2H)7.7(d，2H)，9.8(s，1H)。
In 100ml single port flask, add 2,2 '-dimethyl pyrans ketone 1.24g, N, N-di-t-butyl barbituric acid 2.4g; the 30ml diacetyl oxide, reflux is 5 hours under the nitrogen protection condition, and cooling is filtered; get yellow powder shape solid, ethyl alcohol recrystallization obtains 2.77g yellow crystal sprills.Productive rate is 80%.Be directly used in next step.
In the 100ml there-necked flask; add N; the pyrone intermediate 0.046g of N-di-t-butyl barbituric acid, cholesterol intermediate (II) 0.27g, 10ml acetonitrile; drip several Piperazine anhydrous then; under the nitrogen protection condition, reflux 6 hours, reaction is finished postcooling to room temperature; filtering-depositing obtains the garnet pressed powder.Ethyl alcohol recrystallization obtains red powder shape solid 0.126g.Productive rate 40.0% ultimate analysis: C, 79.68; H, 10.12; N, 2.00; O, 8.20.
Embodiment 7
In 100ml single port flask; add 2; 2 '-dimethyl pyrans ketone 1.24g, N, N-di-t-butyl-thiobarbituricacid 2.56g, 30ml diacetyl oxide; reflux is 5 hours under the nitrogen protection condition; cooling is filtered, and gets yellow powder shape solid; ethyl alcohol recrystallization obtains 2.93g yellow crystal sprills.Productive rate is 81%.Be directly used in next step reaction.
In the 100ml there-necked flask; add the pyrone intermediate 0.047g that contains barbituric acid; cholesterol intermediate (II) 0.27g; the 10ml acetonitrile drips several Piperazine anhydrous then, under the nitrogen protection condition; reflux 6 hours; reaction is finished postcooling to room temperature, and filtering-depositing obtains the garnet pressed powder.Ethanol-benzene mixed solvent recrystallization obtains red powder shape solid 0.14g.Productive rate 45.0% ultimate analysis: C, 78.85; H, 9.92; N, 2.49; O, 7.39; S, 1.35.
Embodiment 8
In 100ml single port flask; add 2,2 '-dimethyl pyrans ketone 1.24g, N; N-two-methyl-thiobarbituricacid 1.72g; the 30ml diacetyl oxide, reflux is 5 hours under the nitrogen protection condition, cooling; filter; get yellow powder shape solid, ethyl alcohol recrystallization obtains 2.22g yellow crystal sprills.Productive rate is 80%.Be directly used in next step reaction.
In the 100ml there-necked flask; add the pyrone intermediate 0.036g that contains barbituric acid; cholesterol intermediate (II) 0.27g; the 20ml acetonitrile drips several Piperazine anhydrous then, under the nitrogen protection condition; reflux 6 hours; reaction is finished postcooling to room temperature, and filtering-depositing obtains the garnet pressed powder.Ethanol-benzene mixed solvent recrystallization obtains red powder shape solid 0.152g.Productive rate 50.5%
Ultimate analysis: C, 78.78; H, 9.82; N, 2.34; O, 7.68; S, 1.38.
Claims (8)
1. one kind contains cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye, and its structure is shown in (I) formula:
In the formula (I), each R and R ' can be identical, also can be different.They are hydrogen, C
1～C
16Alkyl, C
1～C
16Alkoxyl group, C
5～C
20Cycloalkyl, aromatic ring yl or C
4～C
20A kind of in heterocyclic radical, halogen, hydroxyl, the sulfonic group; X is S, and O's is a kind of; Y is O, one kind of C or NH.
2. according to the described cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye that contains of claim 1, it is characterized in that: each R and R ' can be identical, also can be different, be hydrogen, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, C
5～C
10Cycloalkyl, aromatic ring yl or C
4～C
10Heterocyclic radical; X is S, and O's is a kind of; Y is O, one kind of C.
3. according to the described cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye that contains of claim 2, it is characterized in that: each R is identical with R ', is hydrogen, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, C
5～C
10Cycloalkyl, aromatic ring yl or C
4～C
10Heterocyclic radical; X is S, and O's is a kind of; The Y atom is O.
4. according to the described cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye that contains of claim 2, it is characterized in that: each R is identical with R ', is hydrogen, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, C
5～C
10Cycloalkyl, aromatic ring yl or C
4～C
10Heterocyclic radical; X is S, and O's is a kind of; The Y atom is C.
5. according to the described cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye that contains of claim 3, it is characterized in that: each R is identical with R ', for hydrogen, methyl, methoxyl group, cyclohexyl, phenyl or ferrocenyl a kind of; X is O; The Y atom is O.
6. according to the described cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye that contains of claim 3, it is characterized in that: each R is identical with R ', for hydrogen, methyl, methoxyl group, cyclohexyl, phenyl or ferrocenyl a kind of; X is a kind of of S; The Y atom is O.
7. according to any described cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye that contains in the claim 1～6, it is characterized in that: this fluorescence dye has different fluorescent emission wavelength in different solvents.
8. synthetic method that contains cholesteryl 2D-π-A type pyrans class charge transfer fluorescence dye, it is characterized in that: with N, N-diethanolaniline, cholesterol acyl chlorides are raw material, through the synthetic key intermediate (II) of over-churning, Vilsmeier-Haack reaction or with aniline and vinylformic acid condensation, then with cholesterol generation esterification, the synthetic key intermediate of Vilsmeier-Haack reaction (II ') further takes place obtain target compound then with after the reaction such as pyrans class chromophoric group (III) condensation condensation; Comprise the steps:
A) N, N-diethanolaniline, cholesterol acyl chlorides are raw material, under the organic alkali catalyst condition, obtain compound shown in the intermediate 1 in the refluxing toluene reaction, the Vilsmeier-Haack reaction takes place then obtain key intermediate (II);
B) reaction of aniline and vinylformic acid obtains N, and N-two-propionyloxy aniline obtains key intermediate 2 with lentochol reaction then under catalyst action, Vilsmeier-Haack reaction takes place then obtain key intermediate (II ');
C) under pyrone and barbituric acid or the derivative nitrogen protection condition, diacetyl oxide is made solvent refluxing, obtains key intermediate (III);
D) key intermediate (II) or (II ') are placed acetonitrile with intermediate (III), under condition of nitrogen gas, back flow reaction at least 6 hours obtains target product;
Synthetic route is as follows:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910214085 CN101798467A (en) | 2009-12-18 | 2009-12-18 | Cholesteryl-contained 2D-pi-A type pyran charge transfer fluorescent dye and synthesizing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910214085 CN101798467A (en) | 2009-12-18 | 2009-12-18 | Cholesteryl-contained 2D-pi-A type pyran charge transfer fluorescent dye and synthesizing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101798467A true CN101798467A (en) | 2010-08-11 |
Family
ID=42594316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910214085 Pending CN101798467A (en) | 2009-12-18 | 2009-12-18 | Cholesteryl-contained 2D-pi-A type pyran charge transfer fluorescent dye and synthesizing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101798467A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604140A (en) * | 2012-03-21 | 2012-07-25 | 陕西师范大学 | Preparation method of polymer fluorescence sensing film containing cholesterol |
-
2009
- 2009-12-18 CN CN 200910214085 patent/CN101798467A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604140A (en) * | 2012-03-21 | 2012-07-25 | 陕西师范大学 | Preparation method of polymer fluorescence sensing film containing cholesterol |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Color-tunable and ESIPT-inspired solid fluorophores based on benzothiazole derivatives: aggregation-induced emission, strong solvatochromic effect, and white light emission | |
| CN105541660B (en) | A kind of aryl salicylide diphenyl azine connection hydrazine class compound and preparation and application | |
| CN104877665B (en) | Luminescent material having aggregation-induced emission, method of making and application thereof | |
| Zhang et al. | Utilising tetraphenylethene as a dual activator for intramolecular charge transfer and aggregation induced emission | |
| Tayade et al. | Benzimidazole-thiazole based NLOphoric styryl dyes with solid state emission–Synthesis, photophysical, hyperpolarizability and TD-DFT studies | |
| Ge et al. | The synthesis, characterization and optical properties of novel 1, 3, 4-oxadiazole-containing imidazo [1, 5-a] pyridine derivatives | |
| Zhan et al. | Phenothiazine substituted phenanthroimidazole derivatives: Synthesis, photophysical properties and efficient piezochromic luminescence | |
| CN108033940B (en) | A kind of fluorescent material with piezallochromy and solvatochromism | |
| CN102775348A (en) | Naphthalimide derivative and application thereof | |
| CN108864056B (en) | Near infrared fluorescent compound and its preparation method and application with AIE performance | |
| CN103305212B (en) | Wavelength-adjustable diarylethenyl quinoxalinyl pyridazinone organic luminescent material and preparation method thereof | |
| Mathivanan et al. | All-in-one type ESIPT-active multi-stimuli responsive 7-diethylamino-4-hydroxycoumarin-rhodamine B hydrazone as molecular switches and the reversible photochromic features of its zinc ensemble | |
| CN107226783B (en) | A kind of lysosome targeting fluorescent probe and preparation method thereof | |
| Zatsikha et al. | Functionalized bispyridoneannelated BODIPY–Bright long-wavelength fluorophores | |
| CN106632063A (en) | Compound I and compound II based on phenanthroimidazole, and preparation method and applications thereof | |
| CN105367566B (en) | Substituted cumarin-thiazole orange derivative and its preparation method and application | |
| CN106478626A (en) | One class quinacridone derivative and preparation method and application | |
| CN101838476B (en) | A type of organic fluorescent dye compound and synthesis method and application thereof | |
| Wang et al. | New solvatochromic merocyanine dyes based on Barbituric acid and Meldrum's acid | |
| Miao et al. | Design and facile synthesis of quinazolinone-based full color-tunable boron difluoride dyes: Efficient solvent/solid-state emission and bioimaging application | |
| CN113527185A (en) | A D-π-A type tetrastyryl ethynyl phenyl substituted pyridine conjugated luminescent small molecule and its synthesis method | |
| CN104152137A (en) | Fluorine-perylene bisimide molecule internal-energy transferring fluorescence split compound and preparation method thereof | |
| CN101798467A (en) | Cholesteryl-contained 2D-pi-A type pyran charge transfer fluorescent dye and synthesizing method thereof | |
| Fakhfakh et al. | The synthesis and optical properties of novel fluorescent iminocoumarins and bis-iminocoumarins: Investigations in the series of urea derivatives | |
| CN109503550B (en) | 2-azaaryl-6-substituted aminoquinazolone compound and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20100811 |