CN102219656A - Symmetric bifluorenylidene derivative having characteristic of multi-photon absorption, and synthesis method and application thereof - Google Patents
Symmetric bifluorenylidene derivative having characteristic of multi-photon absorption, and synthesis method and application thereof Download PDFInfo
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- CN102219656A CN102219656A CN2011101146685A CN201110114668A CN102219656A CN 102219656 A CN102219656 A CN 102219656A CN 2011101146685 A CN2011101146685 A CN 2011101146685A CN 201110114668 A CN201110114668 A CN 201110114668A CN 102219656 A CN102219656 A CN 102219656A
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Abstract
The invention belongs to the technical field of organic synthesis and discloses a symmetric bifluorenylidene derivative having the characteristic of multi-photon absorption, and a synthesis method and application thereof. 2,7-dibromofluorenone is used as a raw material, carbonyl of the 2,7-dibromofluorenone is converted into hydroxyl through reduction, the hydroxyl is then substituted by bromine by means of the reaction with excessive phosphorus tribromide, the resultant product undergoes a coupling reaction under the catalysis of diazabicyclo to obtain 2, 7, 2', 7'-tetrabromo-9, 9'-difluorenyliden, and the target product 2, 7, 2', 7'-tetra(4-methoxystyrene)-9, 9'-bifluorenylidene is obtained through a phase transfer heck reaction of the 2, 7, 2', 7'-tetrabromo-9, 9'-bifluorenylidene and 4-methoxystyrene. The symmetric bifluorenylidene derivative disclosed by the invention has the characteristics of high stability, large multi-photo absorption section and capability of withstanding the laser radiation as strong as 200GW/cm<2>, and can be used in a multi-photon absorption ultrafast laser limiter.
Description
Technical field
The invention belongs to technical field of organic synthesis, the particularly a kind of two inferior fluorene derivativess of symmetric form and synthetic method and application with multiphoton absorption characteristic.
Background technology
1931, Maria G ppert-Mayer foretold multiphoton absorption in its Ph D dissertation, and after 30 years, because the appearance of laser, people have just observed for the first time the phenomenon of multiphoton absorption.Multiphoton absorption refers to that medium absorbs a plurality of photons simultaneously to the high level transition, reference: [1] G ppert-Mayer M., Ann.Phys, 1931,9:275-294.Nineteen ninety-five, the three-photon that Guang S. He group report obtains under the nanosecond laser absorbs, but the possibility that can not get rid of excited state absorption, reference: [2] Guang S.He, Jayant D.Bhawalkar, and Paras N.Prasad, Optics Letters 1,995 20 (14), 1524-1526.2002, diphenyl ethylene derivatives (APSS) three-photon absorbs the appearance of inductive up-conversion lasing, for people provide new LASER Light Source, simultaneously also make short pulse opticfiber communication, bio-imaging become possibility, reference: 3. Guang S. He, Przemyslaw P. Markowicz, Tzu-Chau Lin ﹠amp; Paras N. Prasad, Nature, 2002,415,767-770.The assorted stilbene dye molecule of discovery classes such as Zhan Chuanlang has very strong three-photon absorption characteristic, certain laser amplitude limiting characteristic is arranged, reference: Chuanlang Zhan, Yunjing Li, Dehua Li, Duoyuan Wang, Yuxin Nie, Optical Materials, 2006,28,289-293.Marvin's ripple etc. has synthesized some and has had the dyestuff of multiphoton absorption characteristic, can be used in the multiphoton fluorescence microscope, reference: People's Republic of China's patent 200410018425.1.Thereby research and exploitation have the focus that stability is high, the big organic materials in multiphoton absorption cross section becomes Recent study.
Summary of the invention
The object of the present invention is to provide a kind of two inferior fluorene derivativess of symmetric form and synthetic method and application with multiphoton absorption characteristic.
For achieving the above object, the present invention has taked following technical scheme:
A kind of two inferior fluorene derivativess of symmetric form with multiphoton absorption characteristic, this derivative has following structure:
A kind of synthetic method with two inferior fluorene derivativess of symmetric form of multiphoton absorption characteristic, step is as follows:
(1) with 2,7-dibromo fluorenone, zinc powder join in the Glacial acetic acid, behind heating reflux reaction 20 ~ 30min, filter, filtrate adds water (amount of water is generally 1 ~ 5 times of filtrate volume) and precipitates the thick product of gained normal hexane recrystallization purifying, get 2,7-two bromo-9-hydroxyphenyl fluorenes; Wherein, 2, the mol ratio of 7-dibromo fluorenone, zinc powder is 1:1 ~ 4, and the addition of Glacial acetic acid is every mmole 2, and the 7-dibromo fluorenone adds 10 ~ 50ml;
(2) with 2,7-two bromo-9-hydroxyphenyl fluorene and PBr
3After being heated to 100 ~ 155 ℃ of reaction 20 ~ 120min, adjust pH is used dichloromethane extraction then to neutral, concentrated extract, and the thick product of gained recrystallizing methanol purifying gets 2,7,9-tribromo fluorenes; Wherein, 2,7-two bromo-9-hydroxyphenyl fluorenes, PBr
3Mol ratio be 1:5 ~ 100;
(3) under protection of inert gas, with 2,7,9-tribromo fluorenes, diazabicylo, acetonitrile filter, with 50 ~ 70 ℃ hot acetonitrile flush cake after being heated to 55 ~ 65 ℃ of reaction 2 ~ 3h, merging filtrate and washings, concentrate, the thick product of gained toluene recrystallization purifying gets 2,7,2 ', 7 '-tetrabromo-9,9 '-two inferior fluorenes; Wherein, 2,7, the mol ratio of 9-tribromo fluorenes, diazabicylo is 1:1 ~ 2, and the addition of acetonitrile is every mmole 2,7, and 9-tribromo fluorenes adds 80 ~ 120ml;
(4) under the protection of rare gas element, with 2,7,2 ', 7 '-tetrabromo-9,9 '-two inferior fluorenes, 4-methoxy styrene, palladium, salt of wormwood, Tetrabutyl amonium bromide, N, dinethylformamide are heated to 80 ~ 150 ℃ by after the heck reaction 1 ~ 7 day, filter, wash with water filtrate, concentrated, column chromatography, get target product 2,7,2 ', 7 '-four (4-methoxy styrene)-9,9 '-two inferior fluorenes; Wherein, 2,7,2 ', 7 '-tetrabromo-9, the mol ratio of 9 '-two inferior fluorenes, 4-methoxy styrene is 1:4 ~ 10, and palladium, salt of wormwood, Tetrabutyl amonium bromide, N, the addition of dinethylformamide are every mmole 2,7,2 ', 7 '-tetrabromo-9,9 '-two inferior fluorenes add 0.04 ~ 0.2mmol, 2 ~ 20mmol, 0.5 ~ 5mmol, 100 ~ 1000ml respectively.
Preferably, adjust pH to neutral process is preferably in the step (2): reaction is cooled to room temperature with reaction solution after finishing, and pours 20 ~ 200 times in the water of reaction solution volume, adds solid state N aHCO then
3Adjust pH is to neutral.
For improving concentrated speed, preferably, in the step (4), after washing with water, can add siccative earlier and carry out drying, reconcentration afterwards.
Described siccative is anhydrous magnesium sulfate, anhydrous sodium sulphate or calcium chloride.
The two application of inferior fluorene derivatives in multiphoton absorption ultrafast laser limiter of symmetric form with multiphoton absorption characteristic.
The synthetic route of the two inferior fluorene derivativess of symmetric form of the present invention:
With 2, the 7-dibromo fluorenone is a raw material, by reduction, makes 2, and the carbonyl of 7-dibromo fluorenone becomes hydroxyl, and then with the reaction of excessive phosphorus tribromide, with the bromine substituted hydroxy, products therefrom is coupled with diazabicylo catalysis, obtains 2,7,2 ', 7 '-tetrabromo-9,9 '-two inferior fluorenes.Again with 2,7,2 ', 7 '-tetrabromo-9,9 '-two inferior fluorenes and 4-methoxy styrene react by heck, promptly obtain target product 2,7,2 ', 7 '-four (4-methoxy styrene)-9,9 '-two inferior fluorenes.
Concrete route is:
The reduction of (1) 2,7-dibromo fluorenone, its reaction formula is:
(2) 2,7, the generation of 9-tribromo fluorenes, its reaction formula is:
(3) 2,7,2 ', 7 '-tetrabromo-9, the generation of 9 '-two inferior fluorenes, its reaction formula is:
(4) target product 2,7,2 ', 7 '-four (4-methoxy styrenes)-9, and the acquisition of 9 '-two inferior fluorenes, its reaction formula is:
The two inferior fluorene derivativess of symmetric form of the present invention can be used in the multiphoton absorption ultrafast laser limiter.
Beneficial effect of the present invention: synthetic method of the present invention is reasonable in design, and the two inferior fluorene derivatives stability of the symmetric form that synthesizes are high, the multiphoton absorption cross section is big, can stand 200 GW/cm
2Above intense laser radiation can be used in the multiphoton absorption ultrafast laser limiter.
Description of drawings
Fig. 1 is 2,7,2 ', 7 '-four (4-methoxy styrenes)-9, the absorption spectrum of the chloroformic solution of 9 '-two inferior fluorenes.
Fig. 2 is the relation that sees through pulse energy and incident pulse energy.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is done into a ground and introduce in detail, but protection scope of the present invention is not limited thereto.
Embodiment 1
2,7,2 ', 7 '-four (4-methoxy styrenes)-9, the synthesis step of 9 '-two inferior fluorenes:
(1), in the 300ml Glacial acetic acid, add 15mmol(5.227g) dibromo fluorenone, be heated to backflow, add 60mmol(3.90g) zinc powder, continue heating reflux reaction 20min, reaction solution is filtered on diatomite, add with the isopyknic water of filtrate and precipitate, the thick product of gained normal hexane recrystallization purifying, promptly get solid 2,7-two bromo-9-hydroxyphenyl fluorenes, yield 70%;
1H-NMR (400MHz, CDCl
3): δ ppm 7.76(s, 2H), 7.53 (dd, 2H, J
1=1.2Hz, J
2=1.6Hz), 7.48 (d, 2H, 8Hz), 5.54 (d, 1H, J=9.6), 1.93 (d, 1H, J=10);
(2), get 8mmol(2.768g) 2,7-two bromo-9-hydroxyphenyl fluorenes add 80mmol(7.519ml) PBr
3, behind mixture heating up to 150 ℃ reaction 40min, be cooled to room temperature, pour 50 times in the water of reaction solution volume, add solid state N aHCO
3Regulate the pH value up to neutrality, use dichloromethane extraction then, rotation underpressure distillation concentrated extract, the thick product of gained recrystallizing methanol purifying gets 2,7,9-tribromo fluorenes, yield 60%;
1H-NMR (400MHz, CDCl
3): δ ppm 7.77 (s, 2H), 7.54 (dd, 2H, J
1=1.6Hz, J
2=1.6Hz), 7.51 (d, 2H, J=8Hz), 5.9 (s, 1H);
(3), in there-necked flask, under argon shield, with 2.5mmol(1.007g) 2,7,9-tribromo fluorenes is added in the 250ml acetonitrile, be heated to 60 ℃, add 3.0mmol(450mg) diazabicylo, reaction 2h after-filtration mixture, with 60 ℃ hot acetonitrile flush cake, rotate underpressure distillation after merging filtrate and the washings and concentrate the thick product of gained toluene recrystallization purifying, get 2,7,2 ', 7 '-tetrabromo-9,9 '-two inferior fluorenes, yield 55%;
1H-NMR (400MHz, CDCl
3): δ ppm 8.41 (d, 4H, J=1.6Hz), 7.54 (d, 4H, J=8Hz), 7.50 (dd, 4H, J
1=2Hz, J
2=1.6Hz);
(4), under the protection of argon gas, in there-necked flask, add 0.493mmol(308mg respectively) 2,7,2 ', 7 '-tetrabromo-9,9 '-two inferior fluorenes, 3.2mmol(434mg) the 4-methoxy styrene, 0.0308mmol(9.7mg) palladium, 3.2mmol(420mg) salt of wormwood, 1.36mmol(323mg) Tetrabutyl amonium bromide, 500mlN, dinethylformamide, 100 ℃ were reacted 6 days down, filter, wash filtrate with water, add anhydrous magnesium sulfate drying, the rotation underpressure distillation concentrates, column chromatography (solvent: chloroform) separate, promptly get target product 2,7,2 ', 7 '-four (4-methoxy styrenes)-9,9 '-two inferior fluorenes, yield 40%;
1H-NMR (400MHz, CDCl
3): δ ppm 7.87 (s, 4H), 7.64 (d, 4H, J=8Hz), 7.49 (d, 8H, J=8.4Hz), 7.10 (d, 8H, J=18.4Hz), 6.92 (d, 8H, J=8.8Hz), 6.16 (s, 4H), 3.85 (s, 12H).MS(ESI)?m/z:?896?[M+K]
+。
Fig. 1 is 2,7,2 ', 7 '-four (4-methoxy styrene)-9,9 '-two inferior fluorenes concentration 8 * 10
-4The absorption spectrum of the chloroformic solution of mol/L does not absorb at 460 ~ 1100nm from figure as can be seen, has intensive to absorb between 312 ~ 460nm.Single photon energy (1064nm) and two-photon energy (532nm) at exciting light are located not absorb, and the energy (355nm) of three photons of exciting light drops on the strongly absorbing region just, in addition, owing to be to use ultrashort pulse, discharged the possibility of excited state absorption, the 1064nm ultra-short pulse laser has been had three-photon absorb light amplitude limiting characteristic so can draw product.
Fig. 2 is the relation that sees through pulse energy and incident pulse energy, and wherein D is for only there being solvent (chloroform), and B is 2,7,2 ', 7 '-four (4-methoxy styrene)-9,9 '-two inferior fluorenes concentration 2 * 10
-4The chloroformic solution of mol/L.LASER Light Source is the Nd:YAG laser apparatus that U.S. continuum company produces: PY61-10, laser pulse width are 38ps, and wavelength is 1064nm, and the beam waist radius after the focusing is 25 microns.Sample joins in the 10mm cuvette, places focus.When the incident light pulse energy reached 0.00015J, its light intensity was 200GW/cm
2, process is than after the intense laser radiation, and thin-layer chromatography, absorption spectrum, fluorescence Spectra are not all found 2,7,2 ', 7 '-four (4-methoxy styrenes)-9, the decomposition of 9 '-two inferior fluorenes.By The Fitting Calculation, its three-photon absorption cross is up to 81.3 * 10
-76Cm
6s
2, approximating method adopts document OPTICS EXPRESS, 2008,16 (7), the method among the 4739-4776.
Embodiment 2
2,7,2 ', 7 '-four (4-methoxy styrenes)-9, the synthetic method of 9 '-two inferior fluorenes are with embodiment 1, and difference is proportioning raw materials and the reaction conditions in each step:
(1) 2,7-dibromo fluorenone 15mmol, zinc powder 15mmol, Glacial acetic acid 150ml, reaction 25min; During precipitation, the amount of water is 2 times of filtrate volumes;
(2) 2,7-two bromo-9-hydroxyphenyl fluorene 8mmol, PBr
340mmol, 100 ℃ of reaction 20min; During adjust pH, the amount of water is 20 times of reaction solution volumes;
(3) 2,7,9-tribromo fluorenes 2.5mmol, diazabicylo 2.5 mmol, acetonitrile 200ml, 55 ℃ of reaction 2.5h; 50 ℃ hot acetonitrile flushing;
(4) 2,7,2 ', 7 '-tetrabromo-9,9 '-two inferior fluorenes 0.493mmol, 4-methoxy styrene 2mmol, palladium 0.02mmol, salt of wormwood 1mmol, Tetrabutyl amonium bromide 0.25mmol, N, dinethylformamide 50ml, 80 ℃ of heck reacted 7 days; Siccative is an anhydrous sodium sulphate.
Embodiment 3
2,7,2 ', 7 '-four (4-methoxy styrenes)-9, the synthetic method of 9 '-two inferior fluorenes are with embodiment 1, and difference is proportioning raw materials and the reaction conditions in each step:
(1) 2,7-dibromo fluorenone 15mmol, zinc powder 45mmol, Glacial acetic acid 750ml, reaction 30min; During precipitation, the amount of water is 5 times of filtrate volumes;
(2) 2,7-two bromo-9-hydroxyphenyl fluorene 8mmol, PBr
3800mmol, 155 ℃ of reaction 120min; During adjust pH, the amount of water is 200 times of reaction solution volumes;
(3) 2,7,9-tribromo fluorenes 2.5mmol, diazabicylo 5mmol, acetonitrile 300ml, 65 ℃ of reaction 3h; 70 ℃ hot acetonitrile flushing;
(4) 2,7,2 ', 7 '-tetrabromo-9,9 '-two inferior fluorenes 0.493mmol, 4-methoxy styrene 5mmol, palladium 0.1mmol, salt of wormwood 10mmol, Tetrabutyl amonium bromide 2.5mmol, N, dinethylformamide 250ml, 150 ℃ of heck reacted 1 day; Siccative is a calcium chloride.
Claims (6)
1. two inferior fluorene derivativess of the symmetric form with multiphoton absorption characteristic is characterized in that this derivative has following structure:
2. the synthetic method with two inferior fluorene derivativess of symmetric form of multiphoton absorption characteristic as claimed in claim 1 is characterized in that step is as follows:
(1) with 2,7-dibromo fluorenone, zinc powder join in the Glacial acetic acid, behind heating reflux reaction 20 ~ 30min, filter, and filtrate adds water to be precipitated, and the thick product of gained normal hexane recrystallization purifying gets 2,7-two bromo-9-hydroxyphenyl fluorenes; Wherein, 2, the mol ratio of 7-dibromo fluorenone, zinc powder is 1:1 ~ 4, and the addition of Glacial acetic acid is every mmole 2, and the 7-dibromo fluorenone adds 10 ~ 50ml;
(2) with 2,7-two bromo-9-hydroxyphenyl fluorene and PBr
3After being heated to 100 ~ 155 ℃ of reaction 20 ~ 120min, adjust pH is used dichloromethane extraction then to neutral, concentrated extract, and the thick product of gained recrystallizing methanol purifying gets 2,7,9-tribromo fluorenes; Wherein, 2,7-two bromo-9-hydroxyphenyl fluorenes, PBr
3Mol ratio be 1:5 ~ 100;
(3) under protection of inert gas, with 2,7,9-tribromo fluorenes, diazabicylo, acetonitrile filter, with 50 ~ 70 ℃ hot acetonitrile flush cake after being heated to 55 ~ 65 ℃ of reaction 2 ~ 3h, merging filtrate and washings, concentrate, the thick product of gained toluene recrystallization purifying gets 2,7,2 ', 7 '-tetrabromo-9,9 '-two inferior fluorenes; Wherein, 2,7, the mol ratio of 9-tribromo fluorenes, diazabicylo is 1:1 ~ 2, and the addition of acetonitrile is every mmole 2,7, and 9-tribromo fluorenes adds 80 ~ 120ml;
(4) under the protection of rare gas element, with 2,7,2 ', 7 '-tetrabromo-9,9 '-two inferior fluorenes, 4-methoxy styrene, palladium, salt of wormwood, four butyl bromation amine, N, dinethylformamide is heated to 80 ~ 150 ℃ by after the heck reaction 1 ~ 7 day, filter, wash with water filtrate, concentrate, column chromatography, target product 2,7,2 ', 7 '-four (4-methoxy styrene)-9,9 '-two inferior fluorenes; Wherein, 2,7,2 ', 7 '-tetrabromo-9, the mol ratio of 9 '-two inferior fluorenes, 4-methoxy styrene is 1:4 ~ 10, and palladium, salt of wormwood, four butyl bromation amine, N, the addition of dinethylformamide are every mmole 2,7,2 ', 7 '-tetrabromo-9,9 '-two inferior fluorenes add 0.04 ~ 0.2mmol, 2 ~ 20mmol, 0.5 ~ 5mmol, 100 ~ 1000ml respectively.
3. the synthetic method with two inferior fluorene derivativess of symmetric form of multiphoton absorption characteristic as claimed in claim 2, it is characterized in that adjust pH to neutral process is in the step (2): after reaction finishes, reaction solution is cooled to room temperature, pour 20 ~ 200 times in the water of reaction solution volume, add solid state N aHCO then
3Adjust pH is to neutral.
4. as claim 2 or 3 described synthetic methods, it is characterized in that in the step (4), after washing with water, add siccative drying reconcentration afterwards with two inferior fluorene derivativess of symmetric form of multiphoton absorption characteristic.
5. the synthetic method with two inferior fluorene derivativess of symmetric form of multiphoton absorption characteristic as claimed in claim 4, it is characterized in that: described siccative is anhydrous magnesium sulfate, anhydrous sodium sulphate or calcium chloride.
6. the two application of inferior fluorene derivatives in multiphoton absorption ultrafast laser limiter of symmetric form with multiphoton absorption characteristic as claimed in claim 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1154284A (en) * | 1997-08-04 | 1999-02-26 | Canon Inc | Electroluminescent element |
| WO2010038251A1 (en) * | 2008-10-02 | 2010-04-08 | Università Degli Studi Di Roma La Sapienza | Bifluorenylidene derivatives, their preparation and uses thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1154284A (en) * | 1997-08-04 | 1999-02-26 | Canon Inc | Electroluminescent element |
| WO2010038251A1 (en) * | 2008-10-02 | 2010-04-08 | Università Degli Studi Di Roma La Sapienza | Bifluorenylidene derivatives, their preparation and uses thereof |
Non-Patent Citations (2)
| Title |
|---|
| MARINA CHARLOT等: "Optical limiting with soluble two-photon absorbing quadrupoles：Structure-property relationships", 《CHEMICAL PHYSICS LETTERS》 * |
| WENBO MA等: "Two- and three-photon absorption in a novel fluorene-based compound", 《CHINESE OPTICS LETTERS》 * |
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