CN101302219A - Fluorene derivative containing large conjugated molecule and preparation thereof - Google Patents
Fluorene derivative containing large conjugated molecule and preparation thereof Download PDFInfo
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Abstract
The invention relates to a fluorene derivative containing macro conjugated molecules and a method for preparing the same. The macro conjugated molecule fluorene derivative has 2, 3, 6, 7-tetraamino-9, 9'-dialkyl fluorene as a raw material which is added to an organic solvent respectively together with phenanthrenequinone, acenaphthene quinone or bis-carbonyl pyrene derivatives and strong base; under the protection of inert gas, reflux reaction is carried out to the materials, so as to prepare a series of trapezoidal conjugated molecules containing fluorine structures. Alkyl surrounding the molecules helps to overcome solubility reduction caused by the high-plane rigid structure of the molecules, which improves the dissolution processing performance of material molecules. Meanwhile, the conjugation of pi electrons on a skeleton of the trapezoidal conjugated molecules is intensified further, which can reduce the energy gaps of the molecules, increase the nonlinear optical coefficients of the molecules remarkably, play a certain role in overcoming the disadvantages that the prior organic nonlinear micromolecule material is poor in chemical stability and mechanical strength, etc. The fluorene derivative can be widely applied to the organic nonlinear optical material field.
Description
Technical field
The present invention relates to a class and contain fluorene derivatives of big conjugated molecule and preparation method thereof, belong to the preparation and the nonlinear optical organic Application Areas of this quasi-molecule.
Background technology
Along with the development of laser technology, the research as the nonlinear optical material (NLO material) on the important substance basis of laser technology has been become a big focus of contemporary research in new high-tech.In recent years, the research of organic non linear optical material is a very active field.Major cause is that some organic materials has the non-linear susceptibility more much bigger than inorganic materials (hyperpolarizability, nonlinear optical coefficients), from but nonlinear optical material more likely.
P.M.Rentzepis in 1964 etc. use 3 respectively with G.H.Heilmeyer, and the second harmonic that 4-benzene pyrene, 1,2 one benzanthrene and hexamine observe ruby Nd:Yag laser produces (SHG).Nineteen sixty-eight Bell Laboratory S.K.Kurtz etc. studies urea, o-dinitrobenzene, finds the SHG excellent property, and light loss is very little.B.F.Levine in 1979 finds that methyl N-methyl-p-nitroaniline (MNA) crystal has very high x
2From then on organic non linear optical material exploitation is risen, because the organic materials nonlinear optical coefficients are more much higher than inorganic materials, and of a great variety, structurally variable, so obtained large quantities of nonlinear optics crystalline materials since the seventies, mainly contained: oil of mirbane amine, 4-position substituted pyridines one oxygen class, quinones, organic salt.
Organic non linear optical material has been compared following advantage with inorganic materials:
1. the auroral polesization of organic materials derives from the polarization of height delocalized πDian Zi, and the ionic polarization of its polarization ratio inorganic materials is easy, thus its nonlinear optical coefficients than the high 1-2 of an inorganic materials order of magnitude, can be up to 10
-5The esu magnitude;
2. response speed is fast, is bordering on femtosecond, and inorganic materials has only psec;
3. the optics newspaper is hindered the threshold value height, can be up to GW/cm
2Magnitude, and inorganic materials can only reach MW/cm
3Magnitude;
4. can pass through molecular designing, method such as synthetic is optimized molecule performance;
5. can design the control material performance by state of aggregation, satisfy the device needs;
6. can carry out the form design, processing adult material, film and fiber.
But because traditional organic small molecule material poor chemical stability; Be difficult to cultivate the good crystal of the big optical quality of size; The easily aging and performance of crystal has limited it and has been extensive use of on device for non-linear optical with reasons such as sample variation are big.The high molecular polymer that has advantages such as physical strength height, good, the easy processing of chemical stability, structure variation on the contrary obtains more applications in practice.
But the organic low molecular crystal has the high non-linearity optical coefficient again, easy purifying, and non-structure these organic high molecular polymers advantage that is beyond one's reach of lacking, therefore inherit these advantages of organic low molecular material, the organic low molecular nonlinear optical material of designing and developing brand new has crucial meaning.
Summary of the invention
The objective of the invention is to develop a class with fluorene structured novel big conjugation organic non-linear optical properties as cross structure; And introduce different alkyl substituents at 9 of the intermediate fluorenes, and with the intermolecular accumulation of effective reduction, improve the solubility property of material molecule, use to some extent in the organic non linear optical material field.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the fluorene derivatives that a class contains big conjugated molecule has following chemical molecular general structure:
(1) chemical molecular general structure A:
Among the general formula A:
(1) R
1=C
1~ C
20Straight or branched alkane;
(2) work as R
2During=H, R
3=H, C
1~ C
20Straight or branched alkane, nitro, the tertiary butyl, trityl group, cyano group, C
1~ C
20Straight or branched alkoxyl group, F, Cl, Br, I or-NRR ' wherein: R, R '=H, phenyl, C
1~ C
20Straight or branched alkane;
(3) work as R
3During=H, R
2=H, C
1~ C
20Straight or branched alkane, nitro, cyano group, C
1~ C
20Straight or branched alkoxyl group, F, Cl, Br or I;
(2) chemical molecular general structure B:
In the Formula B:
(1) R
1=C
1~ C
20Straight or branched alkane;
(2) work as R
4During=H, R
5=H, C
1~ C
20Straight or branched alkoxyl group, nitro, F, Cl, Br, I or-NRR ' wherein: R, R '=H, C
1~ C
20Straight or branched alkane, phenyl;
(3) work as R
5During=H, R
4=the tertiary butyl, trityl group, C
1~ C
20Straight or branched alkoxyl group, nitro, F, Cl, Br, I or-NRR ' wherein: R, R '=H, C
1~ C
20Straight or branched alkane, phenyl;
(3) chemical molecular general structure C:
Among the general formula C:
(1) R
1=C
1~ C
20Straight or branched alkane;
(2) R
6=H, the tertiary butyl, trityl group, C
1~ C
20Straight or branched alkoxyl group, F, Cl, Br, I or-NRR ' wherein: R, R '=H, C
1~ C
20Straight or branched alkane, phenyl.
The preparation method that a described class contains big conjugated molecule fluorene derivatives adopts following preparation steps: with raw material 2,3,6,7-tetramino-9,9 '-dialkyl group fluorenes and phenanthrenequione and highly basic, 1: 2.2 in molar ratio ~ 3.5: 0.5 ~ 1.0, join in the organic solvent, the consumption of organic solvent and the ratio of raw material are 15 ~ 25mL: 1g, under nitrogen protection, are heated to reflux temperature, reacted 2 ~ 24 hours, after the cooling, filtration under diminished pressure obtains the yellow solid product of chemical molecular general structure A; Change the phenanthrenequione in the above-mentioned reaction derivative of acenaphthenequinone or dicarbapentaborane pyrene into respectively, under identical material proportion and reaction conditions, obtain the product of chemical molecular general structure B and C respectively.
Described highly basic is selected from salt of wormwood, sodium hydride,, hydrolith, potassium hydroxide, sodium methylate or sodium ethylate.
Described organic solvent is selected from 1,4-dioxane, acetonitrile, N, dinethylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, quinoline, imidazoles, acetate, propionic acid, butyric acid, ethylene glycol monomethyl ether, glycol dimethyl ether, chlorobenzene, orthodichlorobenzene, toluene, tetramethylene sulfone, methyl alcohol or ethanol.
This compounds adopts following synthetic route:
R wherein
1-R
6Implication the same.
The invention has the beneficial effects as follows: the fluorene derivatives that a class contains big conjugated molecule is with 2,3,6,7-tetramino-9,9 '-the dialkyl group fluorenes, the derivative and the highly basic of phenanthrenequione, acenaphthenequinone or dicarbapentaborane pyrene join in the organic solvent, under the protection of rare gas element, back flow reaction makes; Be that 9 alkyl substituted fluorenes that will contain adjacent diamino structure have first synthesized a series of fluorene structured trapezoidal conjugated molecules that contain as intermediate.The alkyl of molecule periphery helps to overcome because the solvability that the high plane rigid structure of molecule causes reduces, and improves the dissolving processing characteristics of material molecule.Simultaneously owing to the conjugation of πDian Zi on the skeleton of such trapezoidal conjugated molecule is further strengthened, not only can reduce molecule energy gap, enlarge markedly the nonlinear optical coefficients of molecule, and can play a role to shortcomings such as the poor chemical stability that overcomes traditional organic non-linear small molecule material, bad mechanical strength, it will be used widely in the organic non linear optical material field.
Embodiment
Embodiment 1
1g 2,3,6,7-tetramino-9, and 9 '-diisooctyl fluorenes, the salt of wormwood of the phenanthrenequione of 3 times of molar weights and 1 times of molar weight joins in the 15mL acetic acid solution, under protection of nitrogen gas, back flow reaction 2h, cooling back filtration under diminished pressure obtains the 0.6g yellow solid.MS：794.4368；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.50(s，2H)，7.19-7.30(s，8H)，1.89-1.92(m，4H，CH
2)，1.02-1.08(m，4H，CH
2)，0.67(t，J(H-H)＝7.4MHz，6H)，0.52-0.63(m，4H，CH
2)。
Embodiment 2
1g 2,3,6,7-tetramino-9; 9 '-diisooctyl fluorenes, 3 of 2.5 times of molar weights, the sodium hydride of 6-dinitrobenzene phenanthrenequione and 1 times of molar weight joins in the 20mL acetic acid solution, under protection of nitrogen gas; back flow reaction 10h, cooling back filtration under diminished pressure obtains the 0.8g yellow solid.MS：974.3766；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.789(s，2H)，6.53(s，2H)，5.17(s，8H)，1.90-1.93(m，4H，CH
2)，1.28-1.33(m，20H，CH2)，1.20-1.25(m，46H，CH
2)，0.88(t，J(H-H)＝7.3MHz，6H)。
Embodiment 3
1g 2,3,6,7-tetramino-9; 9 '-diisooctyl fluorenes, 2 of 2.2 times of molar weights, the hydrolith of 7-dicyano phenanthrenequione and 1.5 times of molar weights joins in the 15mL propionic acid solution, under protection of nitrogen gas; back flow reaction 20h, cooling back filtration under diminished pressure obtains the 0.55g yellow solid.MS：894.4168；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.50(s，2H)，5.19(s，8H)，1.84-1.89(m，4H，CH
2)，1.62-1.70(d，J＝(H-H)＝7.4MHz，1H)，0.91(d，J(H-H)＝7.2MHz，12H)。
Embodiment 4
1g 2,3,6,7-tetramino-9; 9 '-dibutyl fluorenes, 2 of 3.5 times of molar weights, the potassium hydroxide of 7-dimethoxy phenanthrenequione and 1 times of molar weight joins in the 15mL quinoline solution, under protection of nitrogen gas; back flow reaction 2h, cooling back filtration under diminished pressure obtains the g yellow solid.MS：858.4130；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.50(s，2H)，5.19(s，8H)，1.89-1.94(d，J(H-H)＝7.3MHz，4H)，1.59-1.64(m，4H，CH
2)，1.47-1.52(m，2H，CH)1.39-1.43(m，4H，CH
2)，1.30-1.35(m，12H，CH
2)，1.22-1.27(m，44H，CH
2)，0.91(t，J(H-H)＝7.4MHz，6H)，0.87(t，J(H-H)＝7.5MHz，6H)。
Embodiment 5
1g 2; 3; 6,7-tetramino-9,9 '-diisooctyl fluorenes; 3 of 2 times of molar weights; the sodium ethylate of 6-two (hexichol amido) phenanthrenequione and 1 times of molar weight joins in the 15mL N-Methyl pyrrolidone solution, under protection of nitrogen gas, and back flow reaction 12h; cooling back filtration under diminished pressure obtains the 0.72g yellow solid.MS：1462.7293；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.5(s，2H)，7.19-7.40(m，14H)，1.89-1.94(m，2H，CH
2)，1.77(s，3H)，1.11-1.21(m，2H，CH
2)，0.68(t，J(H-H)＝7.4MHz，3H)，0.52-0.64(m，2H，CH
2)。
Embodiment 6
1g 2,3,6,7-tetramino-9; 9 '-dibutyl fluorenes, 3 of 2.4 times of molar weights, the sodium methylate of 6-di-t-butyl phenanthrenequione and 2 times of molar weights joins in the 15mL propionic acid solution, under protection of nitrogen gas; back flow reaction 6h, cooling back filtration under diminished pressure obtains the 0.4g yellow solid.MS：906.5623；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.5(s，2H)，7.19(s，8H)，1.89-1.94(m，4H，CH
2)，1.65-1.70(m，1H，CH)，1.59-1.63(m，1H，CH)，1.51-1.55(m，2H，CH
2)，0.96(d，J(H-H)＝7.3，3H)，0.91(d，J(H-H)＝7.6，6H)，0.89(t，J(H-H)＝7.4MHz，3H)。
Embodiment 7
1g 2,3,6,7-tetramino-9; 9 '-dibutyl fluorenes, 3 of 2.4 times of molar weights, the sodium methylate of 6-dibromo phenanthrenequione and 2 times of molar weights joins in the 25mL butyric acid solution, under protection of nitrogen gas; back flow reaction 16h, cooling back filtration under diminished pressure obtains the 0.4g yellow solid.MS：1106.0769；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.5(s，2H)，7.19(s，8H)，1.89-1.94(m，4H，CH
2)，1.65-1.70(m，1H，CH)，1.59-1.63(m，1H，CH)，1.51-1.55(m，2H，CH
2)，0.96(d，J(H-H)＝7.3，3H)，0.91(d，J(H-H)＝7.6，6H)，0.89(t，J(H-H)＝7.4MHz，3H)。
Embodiment 8
1g 2,3,6,7-tetramino-9, and 9 '-diisooctyl fluorenes, the sodium hydride of the acenaphthenequinone of 3 times of molar weights and 1.5 times of molar weights joins in the 15mL acetic acid solution, under protection of nitrogen gas, back flow reaction 2h, cooling back filtration under diminished pressure obtains the 0.43g yellow solid.MS：742.4057；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.5(s，2H)，7.20(m，6H)，1.89-1.94(m，4H，CH
2)，1.65-1.70(m，1H，CH)，1.59-1.63(m，1H，CH)，1.51-1.55(m，2H，CH
2)，0.96(d，J(H-H)＝7.3，3H)，0.91(d，J(H-H)＝7.6，6H)，0.89(t，J(H-H)＝7.4MHz，3H)。
Embodiment 9
1g 2,3,6,7-tetramino-9,9 '-diisooctyl fluorenes, 5 of 3 times of molar weights, the sodium ethylate of 6-dinitrobenzene acenaphthenequinone and 2 times of molar weights joins in the 15mL propionic acid solution, under protection of nitrogen gas, back flow reaction 14h, cooling back filtration under diminished pressure obtains 0.56g yellow solid .MS:942.3458;
1H NMR (400M, CD
3OD): (* 10 for δ
-6) 6.79 (s, 2H), 6.5 (s, 2H), 7.20 (s, 6H), 1.89-1.94 (m, 4H, CH
2), 1.65-1.70 (m, 1H, CH), 1.59-1.63 (m, 1H, CH), 1.51-1.55 (m, 2H, CH
2), 0.96 (d, J (H-H)=7.3,3H), 0.91 (d, J (H-H)=7.6,6H), 0.89 (t, J (H-H)=7.4MHz, 3H).
Embodiment 10
1g 2,3,6,7-tetramino-9; 9 '-dibutyl fluorenes, 4 of 3 times of molar weights, the sodium methylate of 7-di-t-butyl acenaphthenequinone and 0.5 times of molar weight joins in the 25mL butyric acid solution, under protection of nitrogen gas; back flow reaction 18h, cooling back filtration under diminished pressure obtains the 0.34g yellow solid.MS：854.5299；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.5(s，2H)，7.20(s，6H)，1.89-1.94(m，4H，CH
2)，1.65-1.70(m，1H，CH)，1.59-1.63(m，1H，CH)，1.51-1.55(m，2H，CH
2)，0.96(d，J(H-H)＝7.3，3H)，0.91(d，J(H-H)＝7.6，6H)，0.89(t，J(H-H)＝7.4MHz，3H)。
Embodiment 11
1g 2,3,6,7-tetramino-9; 9 '-dibutyl fluorenes, 4 of 3 times of molar weights, the sodium methylate of 7-dibromo acenaphthenequinone and 0.5 times of molar weight joins in the 20mL N-Methyl pyrrolidone solution, under protection of nitrogen gas; back flow reaction 18h, cooling back filtration under diminished pressure obtains the 0.34g yellow solid.MS：941.9024；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.5(s，2H)，7.20(s，6H)，1.89-1.94(m，4H，CH
2)，1.65-1.70(m，1H，CH)，1.59-1.63(m，1H，CH)，1.51-1.55(m，2H，CH
2)，0.96(d，J(H-H)＝7.3，3H)，0.91(d，J(H-H)＝7.6，6H)，0.89(t，J(H-H)＝7.4MHz，3H)。
Embodiment 12
1g 2,3,6,7-tetramino-9; 9 '-dibutyl fluorenes, 5 of 3 times of molar weights, the sodium methylate of 6-dibromo acenaphthenequinone and 0.5 times of molar weight joins in the 15mL butyric acid solution, under protection of nitrogen gas; back flow reaction 20h, cooling back filtration under diminished pressure obtains the 0.42g yellow solid.MS：941.9024；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.5(s，2H)，7.20(s，6H)，1.89-1.94(m，4H，CH
2)，1.65-1.70(m，1H，CH)，1.59-1.63(m，1H，CH)，1.51-1.55(m，2H，CH
2)，0.96(d，J(H-H)＝7.3，3H)，0.91(d，J(H-H)＝7.6，6H)，0.89(t，J(H-H)＝7.4MHz
Embodiment 13
1g 2,3,6,7-tetramino-9; 9 '-dibutyl fluorenes, the dimethoxy acenaphthenequinone of 3 times of molar weights and the sodium ethylate of 0.5 times of molar weight join in the 25mL ethanolic soln, under protection of nitrogen gas; back flow reaction 24h, cooling back filtration under diminished pressure obtains the 0.42g yellow solid.MS：941.9024；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.5(s，2H)，7.20(s，6H)，1.89-1.94(m，4H，CH
2)，1.65-1.70(m，1H，CH)，1.59-1.63(m，1H，CH)，1.51-1.55(m，2H，CH
2)。
Embodiment 14
1g 2,3,6,7-tetramino-9; 9 '-dibutyl fluorenes, two (N, N-the dimethyl)-acenaphthenequinones of 3 times of molar weights and the sodium methylate of 0.5 times of molar weight join in the 15mL propionic acid solution, under protection of nitrogen gas; back flow reaction 20h, cooling back filtration under diminished pressure obtains the 0.40g yellow solid.MS：941.9024；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.5(s，2H)，7.20(s，6H)，1.89-1.94(m，4H，CH
2)，1.65-1.70(m，1H，CH)，1.59-1.63(m，1H，CH)，1.51-1.55(m，2H，CH
2)，0.96(d，J(H-H)＝7.3，3H)。
Embodiment 15
1g 2,3,6,7-tetramino-9; 9 '-diisooctyl fluorenes, 4 of 3 times of molar weights, the sodium methylate of 5-dicarbapentaborane pyrene and 0.5 times of molar weight joins in the 25mL ethanolic soln, under protection of nitrogen gas; back flow reaction 24h, cooling back filtration under diminished pressure obtains the 0.45g yellow solid.MS：842.4348；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.5(s，2H)，7.30(s，8H)，1.89-1.94(m，4H，CH
2)，1.65-1.70(m，1H，CH)，1.59-1.63(m，1H，CH)，1.51-1.55(m，2H，CH
2)，0.96(d，J(H-H)＝7.3，3H)，0.91(d，J(H-H)＝7.6，6H)，0.89(t，J(H-H)＝7.4MHz，3H)。
Embodiment 16
1g 2,3,6,7-tetramino-9; 9 '-dibutyl fluorenes, 2 of 3 times of molar weights, 7-two bromo-4, the sodium methylate of 5-dicarbapentaborane pyrene and 0.5 times of molar weight join in the 25mL butyric acid solution; under protection of nitrogen gas, back flow reaction 24h, cooling back filtration under diminished pressure obtains the 0.45g yellow solid.MS：842.4348；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.5(s，2H)，7.30(s，8H)，1.89-1.94(m，4H，CH
2)，1.65-1.70(m，1H，CH)，1.59-1.63(m，1H，CH)，1.51-1.55(m，2H，CH
2)，0.96(d，J(H-H)＝7.3，3H)，0.91(d，J(H-H)＝7.6，6H)，0.89(t，J(H-H)＝7.4MHz，3H)。
Embodiment 17
1g 2,3,6,7-tetramino-9; 9 '-diisooctyl fluorenes, 2 of 3 times of molar weights, 7-di-t-butyl-4, the sodium methylate of 5-dicarbapentaborane pyrene and 0.5 times of molar weight join in the 20mL butyric acid solution; under protection of nitrogen gas, back flow reaction 20h, cooling back filtration under diminished pressure obtains the 0.42g yellow solid.MS：1154.0769；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.5(s，2H)，7.30(s，8H)，1.89-1.94(m，4H，CH
2)，1.65-1.70(m，1H，CH)，1.59-1.63(m，1H，CH)，1.51-1.55(m，2H，CH
2)，0.96(d，J(H-H)＝7.3，3H)，0.91(d，J(H-H)＝7.6，6H)，0.89(t，J(H-H)＝7.4MHz，3H)。
Embodiment 18
1g 2; 3,6,7-tetramino-9; 9 '-dibutyl fluorenes; 2 of 3 times of molar weights, 7-two (trityl group)-4, the sodium methylate of 5-dicarbapentaborane pyrene and 0.5 times of molar weight join in the 20mL butyric acid solution; under protection of nitrogen gas; back flow reaction 24h, cooling back filtration under diminished pressure obtains the 0.32g yellow solid.MS：1810.8732；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.5(s，2H)，7.30-7.36(m，22H)，1.89-1.94(m，4H，CH
2)，1.65-1.70(m，1H，CH)，1.59-1.63(m，1H，CH)，1.51-1.55(m，2H，CH
2)，0.96(d，J(H-H)＝7.3，3H)，0.91(d，J(H-H)＝7.6，6H)，0.89(t，J(H-H)＝7.4MHz，3H)。
Embodiment 19
1g 2,3, and 6; 7-tetramino-9; 9 '-dibutyl fluorenes, 2 of 3 times of molar weights, 7-two (N; the N-diphenylamino)-4; the sodium ethylate of 5-dicarbapentaborane pyrene and 0.5 times of molar weight joins in the 25mL propionic acid solution, under protection of nitrogen gas, and back flow reaction 24h; cooling back filtration under diminished pressure obtains the 0.32g yellow solid.MS：1810.8732；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.5(s，2H)，7.30-7.36(m，22H)，1.89-1.94(m，4H，CH
2)，1.65-1.70(m，1H，CH)，1.59-1.63(m，1H，CH)，1.51-1.55(m，2H，CH
2)，0.96(d，J(H-H)＝7.3，3H)，0.91(d，J(H-H)＝7.6，6H)，0.89(t，J(H-H)＝7.4MHz，3H)。
Embodiment 20
1g 2,3,6,7-tetramino-9; 9 '-diethyl fluorenes, 2 of 3 times of molar weights, 7-two-(methoxyl group)-4, the sodium ethylate of 5-dicarbapentaborane pyrene and 0.5 times of molar weight join in the 25mL butyric acid solution; under protection of nitrogen gas, back flow reaction 20h, cooling back filtration under diminished pressure obtains the 0.32g yellow solid.MS：1810.8732；
1H?NMR(400M，CD
3OD)：δ(*10
-6)6.79(s，2H)，6.5(s，2H)，7.30-7.36(m，22H)，1.89-1.94(m，4H，CH
2)，1.65-1.70(m，1H，CH)，1.59-1.63(m，1H，CH)，1.51-1.55(m，2H，CH
2)，0.96(d，J(H-H)＝7.3，3H)，0.91(d，J(H-H)＝7.6，6H)，0.89(t，J(H-H)＝7.4MHz，3H)。
Claims (4)
1, a class contains the fluorene derivatives of big conjugated molecule, it is characterized in that: fluorene derivatives has following chemical molecular general structure:
(1) chemical molecular general structure A:
Among the general formula A:
(1) R
1=C
1～C
20Straight or branched alkane;
(2) work as R
2During=H, R
3=H, C
1～C
20Straight or branched alkane, nitro, the tertiary butyl, trityl group, cyano group, C
1～C
20Straight or branched alkoxyl group, F, Cl, Br, I or-NRR ' wherein: R, R '=H, phenyl, C
1～C
20Straight or branched alkane;
(3) work as R
3During=H, R
2=H, C
1～C
20Straight or branched alkane, nitro, cyano group, C
1～C
20Straight or branched alkoxyl group, F, Cl, Br or I;
(2) chemical molecular general structure B:
In the Formula B:
(1) R
1=C
1～C
20Straight or branched alkane;
(2) work as R
4During=H, R
5=H, C
1～C
20Straight or branched alkoxyl group, nitro, F, Cl, Br, I or-NRR ' wherein: R, R '=H, C
1～C
20Straight or branched alkane, phenyl;
(3) work as R
5During=H, R
4=the tertiary butyl, trityl group, C
1～C
20Straight or branched alkoxyl group, nitro, F, Cl, Br, I or-NRR ' wherein: R, R '=H, C
1～C
20Straight or branched alkane, phenyl;
(3) chemical molecular general structure C:
Among the general formula C:
(1) R
1=C
1～C
20Straight or branched alkane;
(2) R
6=H, the tertiary butyl, trityl group, C
1～C
20Straight or branched alkoxyl group, F, Cl, Br, I or-NRR ' wherein: R, R '=H, C
1～C
20Straight or branched alkane, phenyl.
2, a class according to claim 1 contains the preparation method of big conjugated molecule fluorene derivatives, it is characterized in that: this method adopts following preparation steps: with raw material 2,3,6,7-tetramino-9,9 '-dialkyl group fluorenes and phenanthrenequione and highly basic, 1: 2.2 in molar ratio～3.5: 0.5～1.0, join in the organic solvent, the consumption of organic solvent and the ratio of raw material are 15～25mL: 1g, under nitrogen protection, be heated to reflux temperature, reacted 2～24 hours, after the cooling, filtration under diminished pressure obtains the yellow solid product of chemical molecular general structure A; Change the phenanthrenequione in the above-mentioned reaction derivative of acenaphthenequinone or dicarbapentaborane pyrene into respectively, under identical material proportion and reaction conditions, obtain the product of chemical molecular general structure B and C respectively.
3, a class according to claim 2 contains the preparation method of big conjugated molecule fluorene derivatives, it is characterized in that: described highly basic is selected from salt of wormwood, sodium hydride,, hydrolith, potassium hydroxide, sodium methylate or sodium ethylate.
4, a class according to claim 2 contains the preparation method of big conjugated molecule fluorene derivatives, it is characterized in that: described organic solvent is selected from 1,4-dioxane, acetonitrile, N, dinethylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, quinoline, imidazoles, acetate, propionic acid, butyric acid, ethylene glycol monomethyl ether, glycol dimethyl ether, chlorobenzene, orthodichlorobenzene, toluene, tetramethylene sulfone, methyl alcohol or ethanol.
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| CN103819415A (en) * | 2013-12-13 | 2014-05-28 | 上海大学 | Large-conjugation fluoreno pyrazine derivative and preparation method thereof |
| CN104718273A (en) * | 2012-08-10 | 2015-06-17 | 浩思特创新科技公司 | Compositions, apparatus, systems, and methods for resolving electronic excited states |
| CN105441067A (en) * | 2015-11-23 | 2016-03-30 | 中节能万润股份有限公司 | Organic electroluminescent material as well as preparation method and application thereof |
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2008
- 2008-07-02 CN CN2008100121797A patent/CN101302219B/en not_active Expired - Fee Related
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| CN103819415A (en) * | 2013-12-13 | 2014-05-28 | 上海大学 | Large-conjugation fluoreno pyrazine derivative and preparation method thereof |
| CN105441067A (en) * | 2015-11-23 | 2016-03-30 | 中节能万润股份有限公司 | Organic electroluminescent material as well as preparation method and application thereof |
| CN105441067B (en) * | 2015-11-23 | 2017-05-24 | 中节能万润股份有限公司 | Organic electroluminescent material as well as preparation method and application thereof |
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|---|---|
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