CN102286278B - 2,3,5,6,7,8-hexa-substituted imidazole[1,2-a] pyridine fluorescent material and synthesis method thereof - Google Patents
2,3,5,6,7,8-hexa-substituted imidazole[1,2-a] pyridine fluorescent material and synthesis method thereof Download PDFInfo
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- 150000002460 imidazoles Chemical class 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title claims abstract description 20
- VNHBYKHXBCYPBJ-UHFFFAOYSA-N 5-ethynylimidazo[1,2-a]pyridine Chemical compound C#CC1=CC=CC2=NC=CN12 VNHBYKHXBCYPBJ-UHFFFAOYSA-N 0.000 title claims abstract description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title abstract 6
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- FQQOMPOPYZIROF-UHFFFAOYSA-N cyclopenta-2,4-dien-1-one Chemical class O=C1C=CC=C1 FQQOMPOPYZIROF-UHFFFAOYSA-N 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 150000003222 pyridines Chemical class 0.000 claims description 9
- 238000010189 synthetic method Methods 0.000 claims description 9
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000005695 Ammonium acetate Substances 0.000 claims description 6
- 235000019257 ammonium acetate Nutrition 0.000 claims description 6
- 229940043376 ammonium acetate Drugs 0.000 claims description 6
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- -1 2-a] pyridine compound Chemical class 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 28
- 235000011054 acetic acid Nutrition 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- PLGPSDNOLCVGSS-UHFFFAOYSA-N Tetraphenylcyclopentadienone Chemical class O=C1C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PLGPSDNOLCVGSS-UHFFFAOYSA-N 0.000 description 4
- 150000001243 acetic acids Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 4
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- YFKBXYGUSOXJGS-UHFFFAOYSA-N 1,3-Diphenyl-2-propanone Chemical compound C=1C=CC=CC=1CC(=O)CC1=CC=CC=C1 YFKBXYGUSOXJGS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a 2,3,5,6,7,8-hexa-substituted imidazole[1,2-a] pyridine fluorescent material and a synthesis method thereof. The molecular structural formula is shown in the specification. The method comprises the following specific steps: dissolving a cyclopentadienone derivative, a 1,2-dicarbonyl compound and an ammonium salt in an anhydrous solvent, wherein the molar ratio of the cyclopentadienone derivative to the 1,2-dicarbonyl compound to ammonium salt is 1:(0.9-1.1):(4-10); heating to 100-160 DEG C to react for 2-6 hours, performing reduced pressure distillation after the reaction to remove the solvent, and purifying to obtain the solid, namely the fluorescent material 2,3,5,6,7,8-hexa-substituted imidazole[1,2-a] pyridine compound. In the method, the cyclopentadienone derivative and 1,2-dicarbonyl compound are utilized as raw materials and the inorganic ammonium salt is utilized as an ammonia source, thus the source range of the raw materials is wide, the raw materials are easily available, the operations are simple, a one-pot method is adopted for synthesis, the steps are short, the yield is high and the method can be used in mass production easily.
Description
Technical field
The present invention relates to a kind of 2,3,5,6,7,8-six substituted imidazoles [1,2-a] pyridines fluorescent material and synthetic method thereof.
Background technology
21 century is the information age, and the information age be unable to do without information display technology.Organic electroluminescence device (OLED) makes great progress as a kind of new technique of display and demonstration means, is in the edge of industrialization.And playing the part of especially important role as the fluorescent material of its core parts.
The research center of gravity of fluorescent material is the fluorescent material of development of new at present, perhaps improves the preparation method of original fluorescent material, shortens operational path, improves productive rate.Has imidazoles [1,2-a] compound of pyridine mother nucleus structure is the fluorescent material of a class excellent property, original synthetic method, such as EP204 285, EP228 206 and EP308 917, take with substituent PA as raw material, and carbonyl compound 2 reaction, final imidazoles [1, the 2-a] pyridine compounds and their 3 that generates.
Suc as formula shown in:
Wherein the substituting group in 1 can be at 3, and 4,5,6; X in 2 is H, CH
3, or ester group, Y is CH
3, CH
2CH
3Z is leavings group, such as halogen, and methylsulfonyl or tosyl group etc.
This response feature is must be take the itrogenous organic substance PA that replaces as raw material, and raw material sources are restricted.Long reaction time, for example 16-18 hour, productive rate was lower.In addition, because 3,4,5,6-is quaternary-and PA is difficult for obtaining, so that be difficult to full imidazoles [1, the 2-a] pyridine compounds and their that replaces of approach preparation with simple and fast.
Summary of the invention
The raw material that the objective of the invention is to prepare in order to overcome prior art polysubstituted imidazoles [1,2-a] pyridine compounds and their is not easy to obtain complex steps, product yield is low, purity is lower, can not satisfy the defective of the required high purity product of material industry, provides a kind of 2,3,5,6,7,8-six substituted imidazoles [1,2-a] pyridines fluorescent material and synthetic method thereof.
The molecular structural formula of 2,3,5,6,7,8-, six substituted imidazoles [1,2-a] pyridines fluorescent material is:
Described 2,3,5,6, the synthetic method of 7,8-, six substituted imidazoles [1,2-a] pyridines fluorescent material is: with cyclopentadienone derivative, 1,2-dicarbonyl compound and ammonium salt are dissolved in the anhydrous solvent, described cyclopentadienone derivative, 1, the mol ratio of 2-dicarbonyl compound and ammonium salt is 1:(0.9 ~ 1.1): (4 ~ 10) are heated to 100 ~ 160
oC reaction 2 ~ 6 hours, reaction removes solvent under reduced pressure after finishing, and the solid that obtains behind the purifying is fluorescent material 2,3,5,6,7,8-six substituted imidazoles [1,2-a] pyridine compounds and their.
Described anhydrous solvent is one or more in dry acetic acid, toluene, ethylbenzene, dimethylbenzene, trimethylbenzene, chlorobenzene, dichlorobenzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE or the phenyl ether.
Described 1, the 2-dicarbonyl compound is benzil derivative or phenanthrenequione derivative.
Described ammonium salt is one or more in ammonium formiate, ammonium acetate, ammonium chloride or the ammonium oxalate.
Steaming the degree that desolventizes after described reaction finishes is the high boiling solvent that steams at least except 75%.
The present invention is raw material with tetraphenylcyclopentadienone derivative and 1,2-dicarbonyl compound, adopts inorganic ammonium salt as the ammonia source, raw material is easy to get, and is simple to operate, and single stage method has synthesized 2,3,5,6,7,8-six substituted imidazoles [1,2-a] pyridine compounds and their, step is short, productive rate is high, easily is applied to scale operation.This method has no report at present.
Embodiment
The reaction mechanism that present method adopts is:
The invention will be further described below by embodiment, its objective is content for a better understanding of the present invention.But example does not limit protection scope of the present invention.
Embodiment 1: preparation 2,3,4,5-tetraphenylcyclopentadienone
Adopt following steps: (1) adds benzil 2.10 grams in three mouthfuls of reaction flasks of 100ml, add dibenzyl ketone 2.10 grams, add 50 milliliters of ethanol, be heated to slight boiling condition, dropping is dissolved with 10 milliliters of the ethanol of KOH 0.62 gram, dropwises 2 hours (2) reactants of reaction and leaves standstill cool to room temperature.Suction filtration with 85% washing with alcohol filter cake, vacuum-drying, finally obtains black powder shape solid 3.26 grams, and productive rate is 85%.
1H NMR (400 MHz, CDCl
3) δ 7.24 ~ 7.21 (m, 12H), 7.15 (m, 4H), 6.93 (m, 4H).
Embodiment 2: preparation 1,3-phenylbenzene-2H-encircles penta [l] phenanthrene-2-ketone
Step: (1) adds phenanthrenequione 2.08 grams in three mouthfuls of reaction flasks of 100ml, add dibenzyl ketone 2.10 grams, add 50 milliliters of ethanol, be heated to slight boiling condition, dropping is dissolved with 10 milliliters of the ethanol of KOH 0.62 gram, dropwises 2 hours (2) reactants of reaction and leaves standstill cool to room temperature.Suction filtration with 85% washing with alcohol filter cake, vacuum-drying, finally obtains black solid 3.17 grams, and productive rate is 83%.
1H NMR (400MHz, CDCl
3): δ 7.77 (d,
J=8.4 Hz, 2 H), 7.51 (d,
J=8.4 Hz, 2 H), 7.32 ~ 7.42 (m, 10 H), 7.20 ~ 7.26 (m, 2 H), 6.87 ~ 6.94 (m, 2 H).
13C NMR (100MHz, CDCl
3) δ 199.7,148.2,133.5,132.3,131.4,130.0,129.0,128.6,128.5,128.3,128.2,124.4,123.1.
Embodiment 3: luxuriant and rich with fragrance [9', 10':4,5] imidazoles [1, the 2-a] pyridine of preparation 10,11,12,13-tetraphenyl
Step: (1) adds 2,3,4,5-tetraphenylcyclopentadienone, 0.384 gram in the 25ml tube sealing, and 9,10-phenanthrenequione, 0.188 gram adds ammonium acetate 0.307 gram, 2 milliliters of Glacial acetic acids.Seal pressure regulation with balloon after prolong is installed, be heated to 100 under stirring
oC.(2) reactant is 100
oReaction is 2 hours under the C, and then stopped heating leaves standstill cool to room temperature.Reaction solution is poured in 50 ml deionized water, dichloromethane extraction three times, anhydrous magnesium sulfate drying, suction filtration is removed sal epsom, and filtrate is concentrated.(3) concentrated solution that obtains is separated with silica gel column chromatography, gradient elution, developping agent are that normal hexane and the methylene dichloride of 1:1 is the normal hexane of 1:48:1 to volume ratio from volume ratio, and methylene dichloride and acetic acid finally obtain red solid 0.400 gram, and productive rate is 70%.
1H NMR (400 MHz, CDCl
3) δ 8.67 (d,
J=8.0 Hz, 2H), 8.44 (d,
J=8.2 Hz, 2H), 7.80 (d,
J=7.5 Hz, 1H), 7.69 ~ 7.59 (m, 2H), 7.54 (d,
J=7.5 Hz, 1H), 7.45 (m, 2H), 7.35 ~ 7.30 (m, 3H), 7.28 ~ 7.25 (m, 4H), 7.23 ~ 7.16 (m, 5H), 7.12 ~ 7.04 (m, 3H), 6.96 (t,
J=7.3 Hz, 1H), 6.81 (t,
J=7.8 Hz, 2H), 6.75 (d,
J=7.4 Hz, 2H).MS?(MALDI)?(
m/z):?572.2246?(M+)。
Embodiment 4: luxuriant and rich with fragrance [9', 10':4,5] imidazoles [1, the 2-a] pyridine of preparation 10,11,12,13-tetraphenyl
Step: (1) adds 2,3,4,5-tetraphenylcyclopentadienone, 7.68 grams in the 150ml tube sealing, 9,10-phenanthrenequione, 4.57 grams add ammonium acetate 15.4 grams, each 25 milliliters of dry toluene and Glacial acetic acids seal pressure regulation with balloon behind the installation prolong, are heated to 160 under stirring
oC.(2) reactant reacted 6 hours under reflux state, and then stopped heating leaves standstill cool to room temperature.After removing most of toluene and acetic acid under reduced pressure residuum is poured in 500 ml deionized water, dichloromethane extraction three times, anhydrous magnesium sulfate drying, suction filtration is removed sal epsom, and filtrate is concentrated.(3) concentrated solution that obtains is separated with silica gel column chromatography, gradient elution, developping agent are that normal hexane and the methylene dichloride of 1:1 is the normal hexane of 1:48:1 to volume ratio from volume ratio, and methylene dichloride and acetic acid finally obtain red solid 7.43 grams, and productive rate is 65 %.
1H?NMR?(400?MHz,?CDCl
3)?δ?8.67?(d,?
J?=?8.0?Hz,?2H),?8.44?(d,?
J?=?8.2?Hz,?2H),?7.80?(d,?
J?=?7.5?Hz,?1H),?7.69?~?7.59?(m,?2H),?7.54?(d,?
J?=?7.5?Hz,?1H),?7.45?(m,?2H),?7.35?~?7.30?(m,?3H),?7.28?~7.25?(m,?4H),?7.23?~?7.16?(m,?5H),?7.12?~?7.04?(m,?3H),?6.96?(t,?
J?=?7.3?Hz,?1H),?6.81?(t,?
J?=?7.8?Hz,?2H),?6.75?(d,?
J?=?7.4?Hz,?2H)。MS?(MALDI)?(
m/z):?572.2246?(M+)。
Embodiment 5: preparation 9,11,12,14-tetraphenyl dibenzo [f, h] imidazoles [1,2-b] isoquinoline 99.9
Step: (1) adds 1,3-phenylbenzene-2H-ring penta [l] phenanthrene-2-ketone 0.382 gram in three mouthfuls of reaction flasks of 25ml, add benzil 0.189 gram, ammonium acetate 0.307 gram, 2 milliliters of Glacial acetic acids seal pressure regulation with balloon behind the installation prolong, are heated to 100 under stirring
oC.(2) reactant is 100
oReaction is 2 hours under the C, and then stopped heating leaves standstill cool to room temperature.Reaction solution is poured in 50 ml deionized water, dichloromethane extraction three times, anhydrous magnesium sulfate drying, suction filtration is removed sal epsom, and filtrate is concentrated.(3) concentrated solution that obtains is separated with silica gel column chromatography, gradient elution, developping agent are that normal hexane and the methylene dichloride of 1:1 is the normal hexane of 1:48:1 to volume ratio from volume ratio, and methylene dichloride and acetic acid finally obtain yellow-green colour solid 0.458 gram, and productive rate is 80%.
1H NMR (400MHz, CDCl
3): δ 8.19 ~ 8.17 (dd, 2H), 7.94 ~ 7.92 (dd, 2H), 7.53 ~ 7.47 (m, 3H), 7.48 ~ 7.43 (m, 3H), 7.36 ~ 7.34 (t, 1H), 7.32 ~ 7.28 (t, 1H), 7.22 ~ 7.17 (m, 5H), 7.16 ~ 7.11 (t, 1H), 7.05 ~ 6.99 (m, 4H), 6.96 ~ 6.92 (m, 3H), 6.87 ~ 6.81 (m, 3H).
13C NMR (100MHz, CDCl
3): δ 146.16,146.02, and 138.44,135.43,134.12,133.02,132.78,132.51,132.47,132.33,131.73,131.16,130.78,130.94,129.98,129.43,129.31,129.05,128.89,128.57,128.14,127.98,127.83,127.46,127.07,126.98,126.66,126.19,125.13,124.00,123.73,123.56. MS (MALDI) (
M/z): 572.2253 (M+).
Embodiment 6: preparation 9,11,12,14-tetraphenyl dibenzo [f, h] imidazoles [1,2-b] isoquinoline 99.9
Step: (1) adds 1,3-phenylbenzene-2H-ring penta [l] phenanthrene-2-ketone 3.82 grams in three mouthfuls of reaction flasks of 100ml, add benzil 2.30 grams, ammonium acetate 7.7 grams, each 15 milliliters of dry toluene and Glacial acetic acids seal pressure regulation with balloon behind the installation prolong, are heated to 160 under stirring
oC.(2) reactant is 160
oReaction is 6 hours under the C, and then stopped heating leaves standstill cool to room temperature.After removing most of toluene and acetic acid under reduced pressure residuum is poured in 500 ml deionized water, dichloromethane extraction three times, anhydrous magnesium sulfate drying, suction filtration is removed sal epsom, and filtrate is concentrated.(3) concentrated solution that obtains is separated with silica gel column chromatography, gradient elution, developping agent are that normal hexane and the methylene dichloride of 1:1 is the normal hexane of 1:48:1 to volume ratio from volume ratio, methylene dichloride and acetic acid, finally obtain yellow-green colour solid 4.20 grams, productive rate is 73.4 %.
1H NMR (400MHz, CDCl
3): δ 8.19 ~ 8.17 (dd, 2H), 7.94 ~ 7.92 (dd, 2H), 7.53 ~ 7.47 (m, 3H), 7.48 ~ 7.43 (m, 3H), 7.36 ~ 7.34 (t, 1H), 7.32 ~ 7.28 (t, 1H), 7.22 ~ 7.17 (m, 5H), 7.16 ~ 7.11 (t, 1H), 7.05 ~ 6.99 (m, 4H), 6.96 ~ 6.92 (m, 3H), 6.87 ~ 6.81 (m, 3H).
13C NMR (100MHz, CDCl
3): δ 146.16,146.02, and 138.44,135.43,134.12,133.02,132.78,132.51,132.47,132.33,131.73,131.16,130.78,130.94,129.98,129.43,129.31,129.05,128.89,128.57,128.14,127.98,127.83,127.46,127.07,126.98,126.66,126.19,125.13,124.00,123.73,123.56. MS (MALDI) (
M/z): 572.2253 (M+).
Claims (4)
1. one kind 2,3,5,6,7,8-, six substituted imidazoles [1,2-a] synthetic method of pyridines fluorescent material, it is characterized in that: with cyclopentadienone derivative, 1,2-dicarbonyl compound and ammonium salt are dissolved in the anhydrous solvent, described cyclopentadienone derivative, the mol ratio of 1,2-dicarbonyl compound and ammonium salt is 1:(0.9 ~ 1.1): (4 ~ 10) are heated to 100 ~ 160
oC reaction 2 ~ 6 hours, reaction removes solvent under reduced pressure after finishing, and the solid that obtains behind the purifying is fluorescent material 2,3,5,6,7,8-six substituted imidazoles [1,2-a] pyridine compounds and their;
Described anhydrous solvent is dry acetic acid or dry acetic acid and toluene.
2. a kind of 2,3,5,6,7 described in claim 1, the synthetic method of 8-six substituted imidazoles [1,2-a] pyridines fluorescent material is characterized in that: described 1, the 2-dicarbonyl compound is benzil or phenanthrenequione.
3. a kind of 2,3,5,6,7 as described in claim 1, the synthetic method of 8-six substituted imidazoles [1,2-a] pyridines fluorescent material, it is characterized in that: described ammonium salt is one or more in ammonium formiate, ammonium acetate, ammonium chloride or the ammonium oxalate.
4. a kind of 2,3,5,6,7 as described in claim 1, the synthetic method of 8-six substituted imidazoles [1,2-a] pyridines fluorescent material is characterized in that: steam the degree that desolventizes after described reaction finishes for steaming at least the high boiling solvent except 75%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110158702 CN102286278B (en) | 2011-06-14 | 2011-06-14 | 2,3,5,6,7,8-hexa-substituted imidazole[1,2-a] pyridine fluorescent material and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110158702 CN102286278B (en) | 2011-06-14 | 2011-06-14 | 2,3,5,6,7,8-hexa-substituted imidazole[1,2-a] pyridine fluorescent material and synthesis method thereof |
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| CN102391854B (en) * | 2011-08-03 | 2013-09-04 | 浙江大学 | Fluorescent chemical sensor for detecting [H plus] and preparation method and usage thereof |
| KR102094942B1 (en) * | 2017-02-24 | 2020-03-30 | 삼성에스디아이 주식회사 | Compound for organic optoelectric device, composition for organic optoelectric device and organic optoelectric device and display device |
| WO2019190184A1 (en) * | 2018-03-29 | 2019-10-03 | Rohm And Haas Electronic Materials Korea Ltd. | Organic electroluminescent compound and organic electroluminescent device comprising the same |
| KR20190114778A (en) * | 2018-03-29 | 2019-10-10 | 롬엔드하스전자재료코리아유한회사 | Organic electroluminescent compound and organic electroluminescent device comprising the same |
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