CN100551922C - The preparation method and the application of photochromic 1-thiophene-asymmetric perfluoro-cyclopentene compound of 2-phenyl hexatomic ring series-parallel type - Google Patents
The preparation method and the application of photochromic 1-thiophene-asymmetric perfluoro-cyclopentene compound of 2-phenyl hexatomic ring series-parallel type Download PDFInfo
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Abstract
The invention discloses a kind of photochromic 1-thiophene-asymmetric perfluoro-cyclopentene compound of 2-phenyl hexatomic ring series-parallel type and preparation method thereof and purposes, this photochromic material all can keep the good photochromic performance in solution or film, and open loop attitude (colourless attitude) and closed loop attitude (colour generation attitude) be good chemistry of tool and thermostability all, high-performances such as higher cyclisation quantum yield and good sensitivity, the fatigue resistance of this compound is very poor, photochromic cycle index is less than 10, utilize this characteristic, can be used for the storage media of limited read-around number CD, as be used to prepare anti-pirate CD-disc; Simultaneously it has specified absorbing wavelength, and the absorption spectrum of colour generation attitude is positioned at 500-700nm, can with wavelength be 532 or the laser apparatus of 650nm be complementary, carry out the development of organic photochromic photon type recording medium.
Description
Technical field
The invention belongs to the organic photochromic material field, the preparation method and the application of especially a kind of photochromic 1-thiophene-asymmetric perfluoro-cyclopentene compound of 2-phenyl hexatomic ring series-parallel type.
Background technology
Along with the high speed development of information storage technology, more and more higher to the requirement of optical storage material.Current, explore especially noticeablely as wiping the rewrite information material with photochromic compounds, because photochromic material is with photon mode recorded information, in case practicability, it will realize high-speed, the jumbo characteristic of optical storage that people expect.
The Heat stability is good of photochromic compound, antifatigue, noise spectra of semiconductor lasers sensitivity and response speed are fast.Therefore, in high-density, can wipe and rewrite photon type optical information field of storage and receive much concern.In numerous photochromic compounds, perfluoro cycolpenfene photochrmism compounds is because the tool application potential of advantages such as its good thermostability, resistance to fatigue, high cyclisation quantum yield and sensitivity.This compounds is after spiro-pyrans, fulgide, on overall performance near application level, make it in erasable optical memory material and photoswitch material, have good application prospects and become the focus of research, very likely become the photochromic material of photon storage media one class of new generation.At present, in the Perfluorocyclopentene diaryl ethylene compounds, the aromatic ring that the ethylene double bond two ends are connected mainly is thiophene and two kinds of aromatic base (Irie of thionaphthene, M.Chem.Rev.100 (2000) 1685), small part is also arranged with heterocyclic substituted thiophene such as thiazole, pyrroles, indoles and cumarone or thionaphthene and form new Diarene compound.Make a general survey of all documents and patent, the fragrant heterocycle of the Diarene compound of being reported all is to be molecular skeleton with the five-ring.
Summary of the invention
Purpose of the present invention just provides the preparation method and the application of a kind of photochromic 1-thiophene-asymmetric perfluoro-cyclopentene compound of 2-phenyl hexatomic ring series-parallel type.
The general formula of molecular structure of photochromic 1-thiophene of the present invention-asymmetric perfluoro-cyclopentene compound of 2-phenyl hexatomic ring series-parallel type is as follows:
R wherein
1Be alkyl (methyl, ethyl), alkoxyl group (as methoxyl group, oxyethyl group etc.), halogen, cyano group etc.; R
2For being in the various substituted radicals of different positions, linking to each other with phenyl ring can group more composed as follows:
Photochromic 1-thiophene of the present invention-asymmetric perfluoro-cyclopentene compound universal synthesis method of 2-phenyl hexatomic ring series-parallel type is: (1), be raw material with the 2-thiotolene, bromination under condition of ice bath at first, then by n-Butyl Lithium and tributyl borate reaction, generate 2-methyl-3-bromo-5-boronate thiophene, make catalyzer with tetrakis triphenylphosphine palladium again, benzene and thiphene ring are coupled together by linked reaction; (2), under the n-Butyl Lithium effect, further generate mono-substituted Perfluorocyclopentene; (3), under the n-Butyl Lithium effect, the reaction of adjacent bromobenzene compound and mono-substituted Perfluorocyclopentene is obtained the target molecule product.
The purposes of photochromic 1-thiophene of the present invention-asymmetric perfluoro-cyclopentene compound of 2-phenyl hexatomic ring series-parallel type: mix up macromolecular material or make diaphragm, be useful for super-high density, erasable organic photon type information storage material; Be used to prepare the photoswitch element; Be used to prepare photochromic luminescent device etc.
The advantage of photochromic 1-thiophene of the present invention-asymmetric perfluoro-cyclopentene compound of 2-phenyl hexatomic ring series-parallel type mainly contains the following aspects:
1, in solution or film, all can keep the good photochromic performance;
2, the equal good high-performances such as chemistry and thermostability, higher cyclisation quantum yield and good sensitivity of tool of open loop attitude of this compound (colourless attitude) and closed loop attitude (colour generation attitude), the fatigue resistance of this compound is very poor, photochromic cycle index is less than 10, utilize this characteristic, can be used for the storage media of limited read-around number CD, as be used to prepare anti-pirate CD-disc;
3, have specified absorbing wavelength, the absorption spectrum of colour generation attitude is positioned at 500-700nm, can with wavelength be 532 or the laser apparatus of 650nm be complementary, carry out the development of organic photochromic photon type recording medium.
4, the open loop attitude of this compound and closed loop attitude all do not have fluorescence, can significantly distinguish over most of five-membered ring two fragrant alkene of having reported and have fluorescent characteristic.
Description of drawings
Fig. 1 is the general formula of molecular structure of compound of the present invention;
The photochromic reactions principle schematic of Fig. 2 compound of the present invention;
The abosrption spectrogram of Fig. 3 compound 1a of the present invention before and after hexane solution medium ultraviolet rayed;
The abosrption spectrogram of Fig. 4 compound 2a of the present invention before and after hexane solution medium ultraviolet rayed;
Colour-change before and after the photoreaction of Fig. 5 compound 1a of the present invention and 2a;
The ORTEP figure of the X-ray diffraction single crystal structure of Fig. 6 compound 2a of the present invention;
The fatigue resistance test of Fig. 7 compound 1a of the present invention in hexane solution;
The fatigue resistance test of Fig. 8 compound 2a of the present invention in hexane solution.
Embodiment
Embodiment 1:[compound 1a]:
In general formula, work as R
1Be methyl, R
2Be hydrogen, promptly constitute photochromic compound 1a, its name is called: [1-(2-methyl-5-phenyl thiene-3-yl-), 2-(2-aminomethyl phenyl-1-yl)] Perfluorocyclopentene (1a), and its structural formula is as follows:
Shown in the synthetic schemes Scheme 1 of this compound:
Scheme?1：
Concrete synthesis step is as described below:
1,3,5-two bromo-2-thiotolenes synthetic:
The glacial acetic acid that 34.6g 2-thiotolene is dissolved in 120mL is in 500mL single port flask; 41.52mL liquid bromine is dissolved in 80mL acetate places constant pressure funnel; Constant pressure funnel is placed on the single port flask,, slowly dropwises, continue ice bath 16h stirring slow dropping liquid bromine under the ice bath.
After finishing, reaction adds 100mL moisture liquid, water Na
2CO
3Be neutralized to neutrality, and (4 * 50mL), the merging organic phase is with the saturated Na of 50mL with extracted with diethyl ether
2CO
3Liquid scrubbing, anhydrous CaCl
2Drying is removed and is desolvated, and underpressure distillation gets product 66.8524g.
Productive rate 73.33%.
Structure is identified:
1H NMR (400MHz, CDCl
3): δ 2.261 (s, 3H ,-CH3), 6.781 (s, 1H, thioph-H); IR (cm
-1): 780.4,810.1,949.8,1010.5,1138.8,1301.7,1450.9,1535.8,2785.8,3080.9.
2,2-methyl-3-bromo-5-boronate thiophene is synthetic:
With 3 of 20.464g (80.0mmol), 5-two bromo-2-thiotolenes are dissolved in the refining ether of 200mL, under the Ar protection, and liquid N
2-acetone is cooled to-78 ℃, and injection n-BuLi 33.33mL (2.4M, 80.0mmol), low-temp reaction 30.0min, disposable by constant pressure funnel dropping B (OBu)
3(2-3min), be raised to room temperature naturally, behind 1h, add 4%HCl 50mL stopped reaction, the separatory phase of anhydrating, organic phase merges organic phase, water 10%HCl acidifying with 4%NaOH extraction three times, up to no longer producing white precipitate, suction filtration, throw out washs with rare HCl, vacuum-drying.Get 14.0001g.
Productive rate 79.18%.
Structure is identified:
1H NMR (400MHz, CDCl
3): δ 2.51 (s, 3H), 4.59 (s, 2H), 7.33 (s, 1H); IR (cm
-1) 690.0,789.9,832.3,1009.9,1132.4,1340.3,1473.5,1528.3,1290.8,3201.5.
3,3-bromo-2-methyl-5-benzene thiophene is synthetic:
Earlier with bromobenzene 4.8670g (31.0mmol) and Pd (PPh
3)
40.5325g (0.46mmol) be dissolved among the refining THF of 100mL, stir 20min; Again 4-bromo-5-thiotolene-2-base-2-boric acid 6.8510g (31.0mmol) is dissolved in 50mL Na
2CO
3In, with above two kinds of solution mixings, the Ar protection is stirring and refluxing 16h down.Stopped reaction is chilled to the room temperature separatory, and lower floor's water merges with organic phase with THF extraction back, and organic phase is used the salt water washing respectively, organic phase MgSO
4Drying is revolved steaming, crosses post with sherwood oil, gets light yellow solid 5.8823g.
Productive rate 75.0%.
Structure is identified:
1H NMR (400MHz, CDCl
3): δ 2.238 (s, 3H ,-CH3), 7.030 (s, H, thioph-H), 7.186-7.223 (t, 2H, J=7.4, benz-H), 7.272-7310 (t, 2H, J=7.6Hz, benz-H), 7.424,7.443 (d, 2H, J=7.6, benz-H).
4, [1-(2-methyl-5 phenyl)] thiene-3-yl-] Perfluorocyclopentene synthetic:
3-bromo-2-methyl-5-benzene thiophene 3.1g (12.25mmol) is dissolved among the refining THF of 200mL, under the Ar protection, liquid N
2-acetone is cooled to-78 ℃, and (2.4M, 12.25mmol), low-temp reaction 30.0min adds the C of 1.67mL (12.25mmol) to injection n-BuLi 5.10mL more fast
5F
8, continue low-temp reaction 2h, rise to room temperature naturally, add 10mL water stopped reaction, revolve steaming and desolventize resistates extracted with diethyl ether, salt water washing, MgSO
4Drying is revolved steaming, crosses post with normal hexane, gets yellow liquid 1.6202g.
Productive rate 36.11%.
Structure is identified:
1HNMR (400MHz, CDCl
3): δ 2.510 (s, 3H ,-CH3), 7.248 (s, 1H, thioph-H), 7.229-7.335 (t, 1H, J=11.4Hz, benz-H), 7.378-7.415 (t, 2H, J=7.4Hz, benz-H), 7.541,7.559 (d, 2H, J=7.2Hz, benz-H);
13C?NMR(100MHz，CDCl
3)：δ14.69，120.45，122.28，125.58，125.63，125.78，128.10，128.80，129.05，133.16，142.59，143.05。
5, [1-(2-methyl-5-phenyl thiene-3-yl-), 2-(2-aminomethyl phenyl-1-yl)] Perfluorocyclopentene (1a) is synthetic:
0.68g (4.0mmol) 2-brooethyl benzene is dissolved in the refining THF of 30mL, under argon shield, liquid N
2-acetone is cooled to-78 ℃, injection n-BuLi 1.60mL (2.5M, 4.0mmol), low-temp reaction 30.0min, add [1-(2-methyl-5 phenyl)] thiene-3-yl-again] Perfluorocyclopentene 1.4652g (4.0mmol), continue low-temp reaction 2h, rise to room temperature naturally, add 10mL water stopped reaction, revolve together with water and to boil off THF, the resistates extracted with diethyl ether, salt water washing, MgSO
4Drying is revolved steaming, crosses post with sherwood oil, gets pale solid 1.0000g.Productive rate 57.02%.m.p.86.4-86.7℃；
Structure is identified:
1H NMR (400MHz, CDCl
3): δ 1.982 (s, 3H ,-CH
3), 1.999 (s, 3H ,-CH
3), 7.136 (s, 1H, thioph-H), 7.161-7.179 (d, 1H, J=7.2Hz, benz-H), and 7.272-7.313 (t, 3H, J=8.0Hz, benz-H), 7.333-7.371 (t, 3H, J=7.6Hz, benz-H), 7.455,7.474 (t, 2H, J=7.6Hz, benz-H);
13C?NMR(400MHz，CDCl
3)：δ13.69，18.65，121.68，124.35，124.57，125.09，126.65，126.80，127.94，128.05，128.92，129.89，132.39，135.96，140.03，140.87。IR(KBr，cm
-1)：461，560，685，748，827，861，895，988，1062，1199，1278，1341，1439，1500，1600，1640，2917。
MS?m/z(M
+)438.1。
Embodiment 2:[compound 2a]:
In general formula, work as R
1Be methoxyl group, R
2Be hydrogen, promptly constitute photochromic compound 2a, its name is called: [1-(2-methyl-5-phenyl thiene-3-yl-), 2-(2-p-methoxy-phenyl-1-yl)] Perfluorocyclopentene (2a), and structural formula is as follows:
Shown in the synthetic schemes Scheme 2 of this compound:
Scheme?2：
Concrete synthesis step is as described below:
Synthesizing of [1-(2-methyl-5-phenyl thiene-3-yl-), 2-(2-p-methoxy-phenyl-1-yl)] Perfluorocyclopentene (2a):
0.94g (5.0mmol) 2-bromine anisole is dissolved in the refining THF of 30mL, under argon shield, liquid N
2-acetone is cooled to-78 ℃, injection n-BuLi 2.00mL (2.5M, 5.0mmol), low-temp reaction 30.0min adds [1-(2-methyl-5 phenyl)] thiene-3-yl-again] Perfluorocyclopentene 1.8310g (5.0mmol) continuation low-temp reaction 2h, naturally rise to room temperature, adding 10mL water stopped reaction and water revolve together and boil off THF, the resistates extracted with diethyl ether, the salt water washing, MgSO
4Drying is revolved steaming, uses sherwood oil: the ethyl acetate volume ratio is crossed post at 5: 1, gets white solid 1.2g, productive rate 52.8%.
m.p.98.3-98.7℃；
Structure is identified:
1H NMR (400MHz, CDCl
3): δ 1.854 (s, 3H ,-CH
3), 3.448 (s, 3H ,-OCH
3), 6.756-6.777 (d, 1H, J=8.4Hz, benz-H), 6.916-6.936 (d, 1H, J=8.0Hz, benz-H), 7.187 (s, 1H, thioph-H), 7.202-7.221 (d, 2H, J=7.6Hz, benz-H), 7.274-7.311 (t, 4H, J=7.2Hz, benz-H), 7.430-7.449 (d, 1H, J=7.6Hz, benz-H);
13C?NMR(400MHz，CDCl
3)：δ13.57，54.72，110.98，111.94，120.31，122.548，124.98，126.17，127.14，128.46，129.45，131.27，133.19，139.24，140.67，156.62；
IR(KBr，cm
-1)：565，692，757，867，894，988，1023，1128，1191，1269，1339，1462，1497，1600，2836，2935；
MS?m/z(M
+)454.1。
Claims (5)
1, a kind of photochromic 1-thiophene-asymmetric perfluoro-cyclopentene compound of 2-phenyl hexatomic ring series-parallel type, its general formula of molecular structure is as follows:
R wherein
1Be methyl or methoxy; R
2Be hydrogen.
2, photochromic 1-thiophene as claimed in claim 1-asymmetric perfluoro-cyclopentene compound of 2-phenyl hexatomic ring series-parallel type, its preparation method is: (1), be raw material with the 2-thiotolene, bromination under condition of ice bath at first, then by n-Butyl Lithium and tributyl borate reaction, generate 2-methyl-3-bromo-5-boronate thiophene, make catalyzer with tetrakis triphenylphosphine palladium again, benzene and thiphene ring are coupled together by linked reaction; (2), under the n-Butyl Lithium effect, further generate mono-substituted Perfluorocyclopentene; (3), under the n-Butyl Lithium effect, the reaction of adjacent bromobenzene compound and mono-substituted Perfluorocyclopentene is obtained the target molecule product.
3, the application of photochromic 1-thiophene as claimed in claim 1-asymmetric perfluoro-cyclopentene compound of 2-phenyl hexatomic ring series-parallel type in preparation super-high density, erasable organic photon type information storage material.
4, the application of photochromic 1-thiophene as claimed in claim 1-asymmetric perfluoro-cyclopentene compound of 2-phenyl hexatomic ring series-parallel type in preparation photoswitch element.
5, the application of photochromic 1-thiophene as claimed in claim 1-asymmetric perfluoro-cyclopentene compound of 2-phenyl hexatomic ring series-parallel type in the photochromic luminescent device of preparation.
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Non-Patent Citations (8)
| Title |
|---|
| Diarylethenes for Memories and Switches. Masahiro Irie,et al.Chemical Reviews,Vol.100 No.5. 2000 |
| Diarylethenes for Memories and Switches. Masahiro Irie,et al.Chemical Reviews,Vol.100 No.5. 2000 * |
| Recent progresses on diarylethene based photochromicswitches. He Tian,et al.Chemical Society Reviews,Vol.33 . 2004 |
| Recent progresses on diarylethene based photochromicswitches. He Tian,et al.Chemical Society Reviews,Vol.33 . 2004 * |
| 二芳基乙烯类光致变色化合物的合成及其光电性质研究. 蒲守智等.精细化工，第22卷第7期. 2005 |
| 二芳基乙烯类光致变色化合物的合成及其光电性质研究. 蒲守智等.精细化工，第22卷第7期. 2005 * |
| 光致变色全氟环戊烯类二芳烯化合物的合成及其性质研究. 李贵珍等.感光科学与光化学，第23卷第3期. 2005 |
| 光致变色全氟环戊烯类二芳烯化合物的合成及其性质研究. 李贵珍等.感光科学与光化学，第23卷第3期. 2005 * |
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