CN1752079A - 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the synthetic method of 5-dihydrofuran - Google Patents
2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the synthetic method of 5-dihydrofuran Download PDFInfo
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- CN1752079A CN1752079A CN 200410009586 CN200410009586A CN1752079A CN 1752079 A CN1752079 A CN 1752079A CN 200410009586 CN200410009586 CN 200410009586 CN 200410009586 A CN200410009586 A CN 200410009586A CN 1752079 A CN1752079 A CN 1752079A
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Abstract
The present invention relates to the preparation field of organic optical function material intermediate, particularly electron acceptor(EA) 2-dicyano methylene radical-3-cyano group-4,5 in the organic second-order non-linear molecule, 5-trimethylammonium-2, the synthetic method of 5-dihydrofuran (TCF).This synthetic method is: is that 1: 2～3 ratio is mixed in organic solvent with 3-hydroxy-3-methyl-2-butanone and propane dinitrile with mol ratio, the lithium ethoxide that adds mole number and be 3-hydroxy-3-methyl-2-butanone mole number 5～50% is as catalyzer, condensation reaction, obtain 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2,5-dihydrofuran, productive rate 80～83%.The present invention is owing to adopting new synthesis condition, and more convenient operation is simple, and productive rate improves greatly simultaneously, and is therefore significant for further synthesizing the electrooptical material or other functional materials that contain the TCF acceptor.
Description
Technical field
The present invention relates to the preparation field of organic optical function material intermediate, particularly electron acceptor(EA) 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the synthetic method of 5-dihydrofuran (TCF).
Background technology
Compare with inorganic materials, the organic second-order non-linear optical material has that nonlinear factor is big, the speed of response is fast, laser damage threshold is high, dielectric coefficient is low, bandwidth greatly, easily synthetic and modify, with existing microelectronics planar technology compatibility, can be on various substrates advantage such as fabricate devices.The organic second-order non-linear optical material can be made devices such as electrooptic modulator, photoswitch, has broad application prospects in optical communication and light interconnection.Macroscopical second order nonlinear coefficient of material is by single order hyperpolarizability (β) decision of molecule, and the organic second-order non-linear chromophore molecule has D-π-A structure usually, and promptly by electron donor(ED), conjugated electrons bridge and electron acceptor(EA) three parts are formed.The general electron donor(ED) that strengthens helps flowing of intramolecularly electronics, thereby can increase the single order hyperpolarizability (β) of chromophore molecule, the response of strongthener second nonlinear to the ability of electronics, ability, the suitable electronic bridge of employing that electron acceptor(EA) is accepted electronics.
2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2,5-dihydrofuran (TCF) makes TCF become strong electron acceptor(EA) owing to have the cyano group of three strong electrophilics in same plane.So just improved the non-linear hyperpolarizability (β) as the chromophore molecule of electron acceptor(EA) widely, and then increased macroscopical second nonlinear optic character of material with TCF.Simultaneously, this receptor also has good stability, therefore comes into one's own.At present, (Volumn 158,2002:1-86) all adopt TCF as acceptor for Larry Dalton, Advances in Polymer Science for two class chromophore molecule FTC that two class β values are the highest and CLD.
Preparation method such as the U.S.Patent:6067186 of existing TCF are disclosed, its preparation method adopts with the sodium ethylate of hydroxyketone equimolar amount and makees catalyzer, 20 hours reaction times, be transferred to the crude product that obtains after the acidity with hydrochloric acid and usually be the more oily matter of foreign matter content, restive with separate, and productive rate only is 36%.
Summary of the invention
The purpose of this invention is to provide a kind of simple, the convenient and synthetic non-linear chromophoric Electrons acceptor 2-dicyano methylene radical of high yield-3-cyano group-4,5,5-trimethylammonium-2, the preparation method of 5-dihydrofuran (TCF).
The preparation method of electron acceptor(EA) TCF of the present invention is: is that 1: 2～3 ratio is mixed in organic solvent with 3-hydroxy-3-methyl-2-butanone and propane dinitrile with mol ratio, the lithium ethoxide that adds mole number and be 3-hydroxy-3-methyl-2-butanone mole number 5～50% is as catalyzer, condensation reaction time 5～20 hours, temperature of reaction is 20 a ℃～solvent refluxing temperature, obtain 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2,5-dihydrofuran (TCF), the productive rate of product are 80～83%.
The structure of described electron acceptor(EA) TCF is:
Concrete synthetic route is as follows:
Described organic solvent is dehydrated alcohol, anhydrous methanol, 1,4-dioxane, anhydrous tetrahydro furan or their any mixture etc.
Described lithium ethoxide catalyzer is obtained by lithium band and absolute ethanol prepared in reaction, and wherein the concentration of lithium ethoxide can be 0.1～5 mol.
The preparation method of electron acceptor(EA) TCF of the present invention is simple, and 3-hydroxy-3-methyl-2-butanone and propane dinitrile condensation use lithium ethoxide as catalyzer, and reaction finishes and obtains a large amount of crystal, through washing, recrystallization obtains product after the extraction simple process, and the productive rate height can make TCF synthetic in a large number.The present invention compares with the synthetic method of patent announcement in the past, the reaction conditions of product and the easier control of operation, and productive rate significantly improves, and good reproducibility.
TCF can be used in non-linear chromophoric synthetic, is used for the preparation of opto-electronic devices such as electrooptic modulator and photoswitch.TCF also is a kind of important pharmaceutical intermediate simultaneously.
Embodiment
Embodiment 1
Add 9.0 gram propane dinitrile (0.115mol) in 100 milliliters the single port bottle, 60 milliliters of anhydrous tetrahydro furans, 6 milliliters of 3-hydroxy-3-methyl-2-butanone (5.6 grams 0.055mol), add the lithium ethoxide of 4 milliliter of 2 mol, solution by colourless become light yellow.Reflux 15 hours, solution becomes sorrel, and has a large amount of precipitations to generate.Cooling back rotary evaporation is removed tetrahydrofuran (THF), obtains the tawny precipitation, behind 200 milliliters of methylene dichloride dissolution precipitations, washs organic layer with saturated sodium-chloride water solution.Dry organic layer after-filtration revolves behind the methylene dichloride with dehydrated alcohol recrystallization solid.Obtain pale yellow crystals 9.0 grams (0.046mol), productive rate 83%, 197～198 ℃ of fusing points (bibliographical information: 198 ℃).IR：2995cm
-1(CH
3)、2235cm
-1(CN)、2227cm
-1(CN)、1618cm
-1(C＝C)、1591cm
-1(C＝C)、1420cm
-1(CH3)、1345cm
-1(CH3)、1212cm
-1(C-O-C)。1H?NMR(CDCl
3)：2.37(3H)，1.64(2H)
The preparation of lithium ethoxide: add the thick lithium band of about 0.8 gram in 50 milliliters absolute ethanol, a large amount of bubbles and exothermic heat of reaction are arranged, 1 hour postcooling of reflux is waited to precipitate the sedimentation hypsokinesis and is gone out the upper solution use to room temperature.
Embodiment 2.
Add 8.0 gram propane dinitrile (0.102mol) in 100 milliliters the single port bottle, 50 milliliters of absolute ethanol, 5.5 milliliters of 3-hydroxy-3-methyl-2-butanone (5.1 grams 0.05mol), add the lithium ethoxide of 2 milliliter of 2 mol, solution by colourless become light yellow.Reflux 10 hours, solution becomes sorrel, and has a large amount of precipitations to generate.Cooling back rotary evaporation is removed ethanol, obtains the tawny precipitation, behind 200 milliliters of methylene dichloride dissolution precipitations, washs organic layer with saturated sodium-chloride water solution.Dry organic layer after-filtration revolves behind the methylene dichloride with dehydrated alcohol recrystallization solid.Obtain pale yellow crystals 7.9 grams (0.040mol), productive rate 80%, 197～198 ℃ of fusing points.Spectroscopic data is with embodiment 1.
Embodiment 3.
Add 8.0 gram propane dinitrile (0.102mol) in 100 milliliters the single port bottle, (volume ratio: 1/1), (5.1 grams 0.05mol), add the lithium ethoxide of 2 milliliter of 2 mol to 5.5 milliliters of 3-hydroxy-3-methyl-2-butanone to 60 milliliters of absolute ethanol/tetrahydrofuran solutions.Mixture heating up refluxed 12 hours, and solution becomes sorrel, and had a large amount of precipitations to generate.Cooling back rotary evaporation removes and desolvates, and obtains the tawny precipitation, behind 200 milliliters of methylene dichloride dissolution precipitations, washs organic layer with saturated sodium-chloride water solution.Dry organic layer after-filtration revolves behind the methylene dichloride with dehydrated alcohol recrystallization solid.Obtain pale yellow crystals 8.1 grams (0.041mol), productive rate 80.6%, 197～198 ℃ of fusing points.Spectroscopic data together
Embodiment 1.
Claims (5)
1. 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the synthetic method of 5-dihydrofuran is characterized in that: is that 1: 2～3 ratio is mixed in organic solvent with 3-hydroxyl 3-methyl-2-butanone and propane dinitrile with mol ratio, the lithium ethoxide that adds mole number and be 3-hydroxy-3-methyl-2-butanone mole number 5～50% is as catalyzer, condensation reaction obtains 2-dicyano methylene radical-3-cyano group-4,5,5-trimethylammonium-2, the 5-dihydrofuran.
2. method according to claim 1 is characterized in that: described organic solvent is dehydrated alcohol, anhydrous methanol, 1,4-dioxane, anhydrous tetrahydro furan or their any mixture.
3. method according to claim 1 is characterized in that: described lithium ethoxide catalyst concentration is 0.1～5 mol.
4. method according to claim 1 is characterized in that: described condensation reaction time is 5～20 hours.
5. method according to claim 1 is characterized in that: described setting-up point is 20 a ℃～solvent refluxing temperature.
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| CNB2004100095864A CN1300128C (en) | 2004-09-20 | 2004-09-20 | Synthesis method of 2-dicyano methylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofurane |
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| CNB2004100095864A CN1300128C (en) | 2004-09-20 | 2004-09-20 | Synthesis method of 2-dicyano methylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofurane |
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| CN1300128C CN1300128C (en) | 2007-02-14 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497785B (en) * | 2008-01-28 | 2012-07-04 | 中国科学院理化技术研究所 | Organic second order non-linear optical chromophore group containing dendritic structured tricyano pyrroline receptor, synthesizing method and use thereof |
| CN102875546A (en) * | 2011-07-13 | 2013-01-16 | 中国科学院理化技术研究所 | Second-order nonlinear optical chromophore having D-pi-A structure and treating julolidine derivative as donor, and synthetic method and use thereof |
| CN105294372A (en) * | 2014-07-29 | 2016-02-03 | 中国科学院大连化学物理研究所 | Method for preparing chiral 2-methylene-2, 3-dihydrofuran |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6067186A (en) * | 1998-07-27 | 2000-05-23 | Pacific Wave Industries, Inc. | Class of high hyperpolarizability organic chromophores and process for synthesizing the same |
-
2004
- 2004-09-20 CN CNB2004100095864A patent/CN1300128C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497785B (en) * | 2008-01-28 | 2012-07-04 | 中国科学院理化技术研究所 | Organic second order non-linear optical chromophore group containing dendritic structured tricyano pyrroline receptor, synthesizing method and use thereof |
| CN102875546A (en) * | 2011-07-13 | 2013-01-16 | 中国科学院理化技术研究所 | Second-order nonlinear optical chromophore having D-pi-A structure and treating julolidine derivative as donor, and synthetic method and use thereof |
| CN102875546B (en) * | 2011-07-13 | 2015-11-04 | 中国科学院理化技术研究所 | Julolidine analog derivative is to the second-order nonlinear optical chromophore with D-π-A structure of body and preparation method and use |
| CN105294372A (en) * | 2014-07-29 | 2016-02-03 | 中国科学院大连化学物理研究所 | Method for preparing chiral 2-methylene-2, 3-dihydrofuran |
| CN105294372B (en) * | 2014-07-29 | 2017-03-15 | 中国科学院大连化学物理研究所 | The method that one kind prepares 2,3 dihydrofuran of chiral 2 methylene |
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| CN1300128C (en) | 2007-02-14 |
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