CN103012098A - Fluorene derivative and preparation method thereof - Google Patents
Fluorene derivative and preparation method thereof Download PDFInfo
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- CN103012098A CN103012098A CN2012105507244A CN201210550724A CN103012098A CN 103012098 A CN103012098 A CN 103012098A CN 2012105507244 A CN2012105507244 A CN 2012105507244A CN 201210550724 A CN201210550724 A CN 201210550724A CN 103012098 A CN103012098 A CN 103012098A
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Abstract
The invention discloses 1 and 4-disubstituted fluorene and synthesis of cyclic derivative thereof. A preparation method of fluorene derivative comprises the following steps: a precursor compound 1 and 3-bis(4-bromine phenyl)-2-acetone or 1 and 3-bis(2-bromine phenyl)-2-acetone and ninhydrin are reacted to synthesize indene cyclopentadiene ketone derivative; and then 1 and 4-disubstituted fluorene derivative generated by a molecular conjugated system is magnified through Diels-Alder cyclic addition. 9-oxo-1 and 4-bis(4-bromine phenyl) fluorene, 9-oxo-1 and 4-bis(2-bromine phenyl) fluorene or 2-phenyl-4, 10-bis(4-bromine phenyl)-fluorene[1 and 2-f] isobenzazole-1, 3 and 5-triketone and 2- thiophene boric acid are reacted through the Suzuki reaction to generate the fluorene derivative containing terminated thiophene. As the fluorine derivative has good heat stability, the novel possibility is provided for exploring novel organic electroluminescence and solar cell materials.
Description
Technical field
The present invention relates to the new Organic Electro Luminescent Materials field, specifically connect the derivative and preparation method thereof of the fluorenes of aromatic nucleus side chain on a kind of fluorenes ring.
Background technology
In recent years because the application of Organic Light Emitting Diode (OLED) and solar cell, people have begun the research to electroluminescent organic material, many factors must be considered so, such as the saturated color of OLED, the driving voltage size, whether quantum yield height and color be complete, the size of volume etc.Conjugated aromatic compound has caused organic field broad research such as organic semiconductor material and organic photoelectrical material because of its superiority, in all known organic semiconductor material and OLED application, fluorenes with and derivative be turned to the electroluminescent material that a class has the rigid plane biphenyl structural, owing to having energy gap length, Heat stability is good and the higher advantages such as electroluminescent efficiency, enjoy the concern of each side, fluorenes and derivative thereof access thiphene ring at molecule, and the material of this two termination thiphene ring can become the potential raw material of solar cell research.
In the field of photovoltaic materials, early be applied to fluorenes micromolecular precursor compound 1,2,3,4,5 (Chardonnens, the L. of illuminator; Chardonnens, H.
Helv.Chim.Acta., 1966,49,1931.)
People (Samuel, the M. such as wang in 2002; Maria, B.; Wang, Z. Y.,
Org.Lett., 2002,4,2157.) synthesized the indenes ［ 1,2-b ］ and the fluorenes series derivates 6,7 that contain phenyl substituted, stop Molecular interaction to put forward high molecular fluorescence efficiency by introducing the phenyl steric group, and have higher fusing point and be expected to become the molecular luminescence material
This seminar had reported again one group of disubstituted indenes [1 in 2005,2-b] and fluorenes series derivates 8a-8d etc., by the Suzuki linked reaction, at indenes [1,2-b] and fluorenes 2,8 are carried out a series of aryl replacements, and test is found through performance characterization, and compound 8a its maximum brightness value under the driving voltage of 10V has reached 1400Cd/m
2
People (Shi, the Yingbo such as Shi in 2011 and Liu; Liu, Qiancai; Wu, Guohong; Rong, Lingling; Tang, Jie;
Tetrahedron,2011,67,1201) synthesize a series of derivatives of two spiral shell fluorenes and indenofluorene and carried out a series of signs, be expected to become promising advanced luminescent material.
People (Yao, the Wen such as Yao in 2012 and Liu; Liu, Qiancai; Shi, Yingbo; Tang, Jie;
Heterocycles2012,85,1077) thiphene ring and fluorene derivatives 11a-d have been synthesized, and it has been carried out spectral characterization, maximum absorption wavelength difference 307 nm of compound 11a-d, 281 nm, 281 nm are found in research, 277 nm, four fluorescence maximum emission wavelength is 442 nm, is expected to be used in the organic field effect transistor, the fields such as organic solar batteries and Organic Light Emitting Diode (OLED).
Summary of the invention
The object of the present invention is to provide derivative of a kind of novel fluorenes that is connected with fragrant cyclic hydrocarbon at the fluorenes ring and preparation method thereof, this compound can be used as electroluminescent organic material; Its preparation method is simple and efficient.
The concrete technical scheme that realizes the object of the invention is:
The derivative of fluorenes, it is characterized in that 1,3-dihalogenated phenyl indenes [a] pentalene-2,8-diketone (2a, 2b) or 1,3-phenylbenzene indenes [a] pentalene-2,8-diketone (2c) and 2,5-norbornadiene reaction is at the Isosorbide-5-Nitrae of fluorenes-position introducing phenyl ring or halo phenyl ring, and its structure is as follows:
Perhaps
With 1,3-dihalogenated phenyl-indenes [a] pentalene-2,8-diketone (2a, 2b) or 1,3-phenylbenzene-indenes [a] pentalene-2,8-diketone (2c) generates indeno isoindoles compound with the reaction of N-phenyl butylene imide, and its structure is as follows:
Again
With 2-thienyl boric acid and above-claimed cpd 3a, 3b be 9-oxo-Isosorbide-5-Nitrae-dihalogenated phenyl fluorenes reaction or with above-claimed cpd 5a be 2-phenyl-4,10-two (4-bromophenyl)-indenes [1,2-f] and isoindole-1,3,9-, three reactive ketones access thienyl group in system, its structure is as follows:
The preparation method of above-mentioned fluorene derivatives comprises following concrete steps:
A, preparation 1,3-two (4-halogenophenyl)-2-acetone and 1,3-two (2-halogenophenyl)-2-acetone
To slowly splash into N to the dichloromethane solution of halogeno-benzene acetic acid or adjacent halogeno-benzene acetic acid, in N '-dicyclohexyl carbimide (DCC) and the dichloromethane solution to Dimethylamino pyridine (DMAP), react 18～32h under the normal temperature, make 1,3-two (4-halogenophenyl)-2-acetone and 1,3-two (2-halogenophenyl)-2-acetone; Wherein to halogeno-benzene acetic acid or adjacent halogeno-benzene acetic acid and N, the ratio of the amount of substance of N '-dicyclohexyl carbimide (DCC) is 1:0.5～0.95; N, N '-dicyclohexyl carbimide (DCC) and be 4:1～2 to the ratio of the amount of substance of Dimethylamino pyridine (DMAP); Ratio to the amount of substance of halogeno-benzene acetic acid or adjacent halogeno-benzene acetic acid and methylene dichloride is 1:20～100;
B, preparation 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone and 1,3-two (2-bromophenyl)-indenes [a] pentalene-2,8-diketone
10% KOH/MeOH solution is added drop-wise in the ethanolic soln of ninidrine and 1,3-two (4-bromophenyl)-2-acetone or 1,3-two (2-bromophenyl)-2-acetone, under 75 ℃, reacted 3～6 hours after dropwising; Make 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone and 1,3-two (2-bromophenyl)-indenes [a] pentalene-2,8-diketone; Ninidrine, 1, the ratio of the amount of substance of 3-two (4-bromophenyl)-2-acetone or 1,3-two (2-bromophenyl)-2-acetone, potassium hydroxide is 1～2.5:1:2～3; 1,3-two (4-bromophenyl)-2-acetone or 1,3-two (2-bromophenyl)-2-acetone are 1:30～100 with the ratio of the amount of substance of ethanol;
C, preparation 9-oxo-Isosorbide-5-Nitrae-two (4-bromophenyl) fluorenes, 9-oxo-Isosorbide-5-Nitrae-two (2-bromophenyl) fluorenes, 9-oxo-Isosorbide-5-Nitrae-diphenylfluorene
With 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone, 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone or 1,3-phenylbenzene-indenes [a] pentalene-2,8-diketone and 2,5-norbornadiene add in the toluene, reflux 12～18 hours makes 9-oxo-Isosorbide-5-Nitrae-two (4-bromophenyl) fluorenes, 9-oxo-1,4-two (2-bromophenyl) fluorenes, the 9-oxo-Isosorbide-5-Nitrae-compounds such as diphenylfluorene; Wherein 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone, 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone or 1,3-phenylbenzene-indenes [a] pentalene-2, the ratio of the amount of substance of 8-diketone and 2,5-norbornadiene is 1:1～5; 1,3-two (4-bromophenyl)-indenes [a] pentalene-2, the 8-diketone, 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone or 1,3-phenylbenzene-indenes [a] pentalene-2, the 8-diketone is 1:10～40 with the ratio of the amount of substance of toluene;
D, preparation N-phenyl-suitable horse imide
Aniline is added drop-wise to along in the diethyl ether solution of horse acyl acid anhydride, at 0 ℃ of reaction 10 min, filter the solid that reaction produces, in solid transfer to 100 ml round-bottomed flask after dropwising, add new steaming acetic anhydride and sodium-acetate at 60 ℃ of reaction 2h, make N-phenyl-suitable horse imide; The ratio of the amount of substance of suitable horse acyl acid anhydride and aniline is 1:1～4; The ratio of the amount of substance of suitable horse acyl acid anhydride and sodium-acetate is 1:0.5～1; The ratio of the amount of substance of suitable horse acyl acid anhydride and ether is 1:10～40; The ratio of the amount of substance of suitable horse acyl acid anhydride and acetic anhydride is 1:50～200;
E, preparation 2-phenyl-4,10-two (4-bromophenyl)-indenes [1,2-f] and isoindole-1,3,9-triketone, 2-phenyl-4,10-two (2-bromophenyl)-indenes [1,2-f] and isoindole-1,3,9-triketone or 2,4,10-triphenyl-indenes [1,2-f] and isoindole-1,3, the 9-triketone
With 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone, 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone or 1,3-phenylbenzene-indenes [a] pentalene-2,8-diketone and N-phenyl-along the horse imide, add in the phenylate solvent, 180 ℃ were reacted 4～12 hours, and made 2-phenyl-4,10-two (4-bromophenyl)-indenes [1,2-f] and isoindole-1,3, the 9-triketone, 2-phenyl-4,10-two (2-bromophenyl)-indenes [1,2-f] and isoindole-1,3, the 9-triketone, 2,4,10-triphenyl-indenes [1,2-f] and isoindole-1,3, the 9-triketone; Wherein 1,3-two (4-bromophenyl)-indenes [a] pentalene-2, the 8-diketone, 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone or 1,3-phenylbenzene-indenes [a] pentalene-2, the 8-diketone is 1:1～2 with the ratio of the amount of substance of N-phenyl-suitable horse acid amides, 3-two (4-bromophenyl)-indenes [a] pentalene-2, the 8-diketone, 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone or 1,3-phenylbenzene-indenes [a] pentalene-2, the 8-diketone is 1:15～25 with the ratio of the amount of substance of phenylate;
F, preparation 9-oxo-Isosorbide-5-Nitrae-two [4-(2-thiophene) phenyl] fluorenes
Under the nitrogen protection with 9-oxo-Isosorbide-5-Nitrae-two (4-bromophenyl) fluorenes, 2-thienyl boric acid, tetra-triphenylphosphine palladium, yellow soda ash join in the mixed solvent of toluene, second alcohol and water, 110 ℃ of lower reactions 5～8 hours, make 9-oxo-Isosorbide-5-Nitrae-two [4-(thiophene) phenyl] fluorenes; 9-oxo-Isosorbide-5-Nitrae-two (4-bromophenyl) fluorenes wherein, the 2-thienyl boric acid, tetra-triphenylphosphine palladium, the ratio of yellow soda ash amount of substance is 1:3～4:0.04～0.10:5～6, and 9-oxo-Isosorbide-5-Nitrae-two (4-bromophenyl) fluorenes is 1:60～100 with the ratio of the amount of substance of toluene; The volume ratio of toluene, second alcohol and water is 10:2:1;
G, preparation 9-oxo-Isosorbide-5-Nitrae-two [2-(2-thiophene) phenyl] fluorenes, 2-phenyl-4,10-two [4-(2-thiophene) phenyl]-indenes [1,2-f] and isoindole-1,3,9-triketone
Under the nitrogen protection with 9-oxo-1; 4-two (2-bromophenyl) fluorenes or 2-phenyl-4; 10-two (4-bromophenyl)-indenes [1; 2-f] and isoindole-1; 3; the 9-triketone; the 2-thienyl boric acid; tetra-triphenylphosphine palladium; yellow soda ash; join in the mixing solutions of tetrahydrofuran (THF) and water back flow reaction 24～36 hours, and made 9-oxo-Isosorbide-5-Nitrae-two [2-(2-thiophene) phenyl] fluorenes or 2-phenyl-4; 10-two [4-(2-thiophene) phenyl]-indenes [1; 2-f] and isoindole-1,3, the 9-triketone; 9-oxo-1 wherein; 4-two (2-bromophenyl) fluorenes or 2-phenyl-4,10-two (4-bromophenyl)-indenes [1,2-f] and isoindole-1; 3; the 9-triketone, 2-thienyl boric acid, tetra-triphenylphosphine palladium; the ratio of the amount of substance of yellow soda ash is 1:3～4:0.04～0.10:5～6; 9-oxo-Isosorbide-5-Nitrae-two (2-bromophenyl) fluorenes or 2-phenyl-4,10-two (4-bromophenyl)-indenes [1; 2-f] and isoindole-1; the ratio of the amount of substance of 3,9-triketone and tetrahydrofuran (THF) is 1:30～100, and the volume ratio of tetrahydrofuran (THF) and water is 10～30:1.
Aforesaid method relates to the preparation of 1,3-two (4-bromophenyl)-2-acetone and 1,3-two (2-bromophenyl)-2-acetone and N-phenyl-suitable horse acid amides, according to (H. Sauriat-Dorizon, T. Maris, J. D. Wuest,
J. Org. Chem. 2003,68,240-246) reach (A. F. Uchoa, K.T. de Oliveira, M. S. Baptista, A. J. Bortoluzzi, Y. Iamamoto, O. A. Serraz,
J. Org. Chem. 2011,76,8824) record method prepare.
Step a of the present invention is in the reaction that replaces the expansion ring fluorenes molecular conjugation degree that indeno diene diketone and norbornadiene or N-phenyl butylene imide generate by the D-A cycloaddition reaction, the characteristics such as have that reaction yield is high, step simply, does not need catalyzer and post-reaction treatment is simple.
Invention step b is synthetic via the method for palladium catalysis Suzuki coupling.The method is take tetra-triphenylphosphine palladium as catalyzer, and yellow soda ash is done alkali, and at toluene, reaction forms in the mixed solvent of the mixed solvent of second alcohol and water or tetrahydrofuran (THF) and water; This step reaction has the characteristics such as the high easily processing of productive rate.
Description of drawings
Fig. 1 is the schema of synthetic compound 3a of the present invention, 3b and 3c;
Fig. 2 is the schema of synthetic compound 5a of the present invention, 5b and 5c;
Fig. 3 is the schema of synthetic compound 4a of the present invention, 4b and 6a.
Embodiment
Consult Fig. 1, Fig. 2 and Fig. 3, preparation method of the present invention carries out in the steps below:
Embodiment
Agents useful for same is the commercially available prod, and solvent is through conventional drying treatment, and the standard vacuum line technology is adopted in the synthetic i.e. operation of sensitive compound; Employing reagent explanation: PE-sherwood oil; DCM-methylene dichloride; THF-tetrahydrofuran (THF).
1,3-two (4-bromophenyl)-2-acetone (
1a) preparation:
DCC (7.7g, 37.3mmol) and DMAP (1.145g, 9.35mmol) are dissolved in the 75ml methylene dichloride, slowly drip the dichloromethane solution 75ml to bromo-acid (8.05g, 37.45mmol).Dropwise rear normal-temperature reaction 24h, leach the solid that reaction produces, methylene dichloride is removed in underpressure distillation, uses ethyl alcohol recrystallization, gets white crystal 4.33g, productive rate 68%; Fusing point: 118-120 ℃.
HNMR(CDCl
3300MHz)：δ：7.46(d，4H,J=8.4Hz),7.02(d,4H,J=8.4Hz),
3.69(s,4H);C NMR(75.4MHz.CDCl3)δ204.2,132.6,131.8,131.2,121.2,48.4。
1,3-two (2-bromophenyl)-2-acetone (
1b) preparation:
Synthetic method and treatment process get white crystal to above-mentioned similar, productive rate 68%.
H NMR(CDCl
3,300 MHz)：δ：7.58(d,J=6Hz,1H),7.26-7.12(m,6H),3.96(s,1H)。
1,3-two (4-bromophenyl)-indenes [a] pentalene-2, the 8-diketone (
2a) make:
With ninidrine (2.86g, 14.65mmol) and 1,3-two (4-bromophenyl)-2-acetone (4.996g, 13.65mmol) be dissolved in the ethanol of 20ml heat, slowly drip 3.5ml10%KOH/MeOH solution, stir 3h at 75 times after dropwising, stopped reaction when treating that solution becomes dark-brown by yellow filters the solid that reaction produces, use ethyl alcohol recrystallization, obtain dark-brown crystal 5 .45g, productive rate 81.5%
R f=0.59 (PE:DCM=1:1), fusing point: 292-294 ℃.
HNMR(CDCl
3, 300MHz)：δ：8.59-8.56(m,2H),8.19-8.11(m，2H),7.81-7.80(m，2H),7.71-7.60(m,6H)。
1,3-two (2-bromophenyl)-indenes [a] pentalene-2, the 8-diketone (
2b) make:
With ninidrine (2.86g, 14.65mmol) and 1,3-two (2-bromophenyl)-2-acetone (4.996g, 13.65mmol) is dissolved in the ethanol of 20ml heat, slowly drips 3.5ml10%KOH/MeOH solution, under 75 ℃, stir 3h after dropwising, stopped reaction when treating that solution becomes scarlet by yellow filters the solid that reaction produces, and uses ethyl alcohol recrystallization, get scarlet crystal 5 .35g, productive rate 80%;
R f=0.57 (PE:DCM=1:1), fusing point: 195-197 ℃.
HNMR(CDCl
3，300MHz)：δ：8.06-8.03(m,1H),7.77-7.70(m,5H),7.50-7.39(m,4H), 7.36-7.28(m,2H)。
9-oxo-Isosorbide-5-Nitrae-two (4-bromophenyl) fluorenes (
3a) preparation:
Add 1,3-two (4-bromophenyl)-indenes [a] pentalene-2 in the 50ml round-bottomed flask, 8-diketone (1.0g, 2.0408mmol) and norbornadiene (0.1878g, 2.0408mmol) add toluene, reflux 12h.After reaction finished, toluene was removed in underpressure distillation, and crude product gets faint yellow solid 0.667g with the PE:DCM=2:1 column chromatography, productive rate 67%,
R f=0.65 (PE:DCM=1:1), fusing point: 198-200 ℃.
HNMR(CDCl
3,300MHz)：δ：7.80(d,J=8.0Hz,1H),7.71(d,J=8.0Hz,1H)，7.57-7.47(m,3H) ,7.44-7.37(m,3H),7.35-7.26(m,2H),7.22-7.18(m,3H),6.41(d,J=5.3Hz,1H)。
9-oxo-Isosorbide-5-Nitrae-two (2-bromophenyl) fluorenes (
3b) preparation:
Add 1,3-two (2-bromophenyl)-indenes [a] pentalene-2 in the 50ml round-bottomed flask, 8-diketone (1.0g, 2.0408mmol) and norbornadiene (0.1878g, 2.0408mmol) add dimethylbenzene, reflux 12h.After reaction finished, underpressure distillation was except removal xylene, and crude product gets faint yellow solid 0.60g with the PE:DCM=2:1 column chromatography, productive rate 60%,
R f =0.64 (PE:DCM=1:1), fusing point: 235-237 ℃
HNMR(CDCl
3,300mMHz)：δ：7.80(d,J=8.0Hz,1H),7.71(d,J=8.0Hz,1H),7.57-7.55(m,1H),7.50-7.35(m,5H),7.35-7.26(m,3H),7.22-7.18(m,2H),6.41(d, J=5.3Hz ,1H)。
9-oxo-Isosorbide-5-Nitrae-diphenylfluorene (
3c) preparation:
Add 1,3-phenylbenzene-indenes [a] pentalene-2 in the 50ml round-bottomed flask, 8-diketone (1.0g, 2.994mmol) and norbornadiene (0.275g, 2.994mmol) add toluene, reflux 12h.After reaction finished, toluene was removed in underpressure distillation, and crude product gets faint yellow solid 1.0g with the PE:DCM=2:1 column chromatography, productive rate 70%,
R f=0.64 (PE:DCM=1:1), fusing point: 127-129 ℃.
HNMR(CDCl
3,500Hz)：δ：7.12-7.03(m,11H),6.94-6.91(m,1H),6.82-6.75(m,4H)，6.27(d,J=6Hz,1H)。
N-phenyl-suitable imido the preparation of horse:
In the 50ml round-bottomed flask, add along horse acyl acid anhydride (0.392g, 4mmol), add the 16ml ether, drip aniline (0.368g, 4mmol), at 0 ℃ of reaction 10min, filter the solid that reaction produces after dropwising, with ether (2 * 20ml) washings, drain solid transfer to the 100ml round-bottomed flask, adding 40ml newly steams acetic anhydride and sodium-acetate (0.4g) reacts 2h at 60 ℃, after reaction finishes, reaction system is poured in the 200ml frozen water, use dichloromethane extraction, organic phase anhydrous magnesium sulfate drying, suction filtration, underpressure distillation obtains yellow solid 0.51g, productive rate 74%.
HNMR(CDCl
3,300MHz)：δ：7.50-7.45(m,2H),7.39-7.33(m,3H),6.85(s,2H)。
2-phenyl-4,10-two (4-bromophenyl)-indenes [1,2-f] and isoindole-1,3, the 9-triketone (
5a) preparation:
In the 50ml round-bottomed flask, add 9-oxo-Isosorbide-5-Nitrae-two (4-bromophenyl) fluorenes (0.2832g, 0.578mmol), add N-phenyl butylene imide (0.1g, 0.578mmol), add phenylate 10ml, 180 ℃ of reaction 4h treat that solution is stopped reaction by the brown yellow that becomes.Thick solution gets safran solid 0.20g with the PE:DCM=2:1 column chromatography, productive rate 56%,
R f=0.30 (PE:DCM=1:1), fusing point 330-332 ℃.
HNMR(CDCl
3,300MHz)：δ： 7.66(d,J=6.9Hz,2H),7.57-7.54(m,3H),7.31-7.19(m,11H)，6.45(d,J=7.1Hz,1H)。
2-phenyl-4,10-two (2-bromophenyl)-indenes [1,2-f] and isoindole-1,3, the 5-triketone (
5b) preparation:
The preparation method
5aPreparation similar.Add 9-oxo-Isosorbide-5-Nitrae-two (2-bromophenyl) fluorenes (0.2832g, 0.578mmol) in the 50ml round-bottomed flask, N-phenyl butylene imide (0.1g, 0.578mmol) gets faint yellow solid 0.18g, productive rate 50%,
R f=0.31 (PE:DCM=1:1), fusing point＞300 ℃.
HNMR(CDCl
3,300MHz)：δ： 7.85,(d,J=7.7Hz,1H),7.75(d,J=7.8Hz,1H),7.63(d,J=6.9Hz,1H),7.59-7.26(m,13H),6.63(d,J=7.4Hz,1H)。
2,4,10-triphenyl-indenes [1,2-f] and isoindole-1,3, the 9-triketone (
5c) preparation:
Synthetic method with
5aPreparation similar, in the 50ml round-bottomed flask, add 9-oxo-Isosorbide-5-Nitrae-diphenylfluorene (0.1930g, 0.578mmol), N-phenyl butylene imide (0.1g, 0.578mmol) gets faint yellow solid 0.160g, productive rate 58%,
R f=0.26 (PE:DCM=1:1), fusing point: 304-306 ℃.
HNMR(CDCl
3,300MHz)：δ：7.56-7.53(m,4H),7.47-7.42(m,7H),7.28-7.14(m,7H)，6.34(d,J=7.0Hz,1H)。
9-oxo-Isosorbide-5-Nitrae-two [4-(2-thiophene) phenyl] fluorenes (
4a) synthetic:
In the 50ml round-bottomed flask, add respectively
3a(0.151g, 0.31mmol), 2-thienyl boric acid (0.0947g, 0.74mmol); yellow soda ash (0.1g), water (3ml), toluene (7ml), ethanol (7ml); four triphenyl phosphorus palladiums (22mg, 0.03mmol), the lower back flow reaction 8h of N2 protection; be cooled to room temperature, reaction solution is poured into water, ethyl acetate extraction; the organic phase anhydrous magnesium sulfate drying, suction filtration, ethyl acetate is removed in underpressure distillation; crude product obtains yellow solid 0.125g with the PE:DCM=2:1 column chromatography, productive rate 81%
R f=0.64 (PE:DCM=1:1), fusing point 233-235 ℃.HNMR(CDCl
3,300MHz)：δ：7.78(d,J=8.4Hz,2H),7.72(d,J=8.5Hz,2H),7.61-7.56(m,3H),7.52-7.49(m,2H),7.46-7.45(m,1H),7.40-7.34（m,3H）,7.32-7.30（m,1H）,7.27-7.24（m,1H）,7.22-7.19（m,2H）,7.16-7.10（m,2H）,6.88-6.85（m,1H）。
2-phenyl-4,10-two [4-(2-thiophene) phenyl]-indenes [1,2-f] and isoindole-1,3, the 9-triketone (
6a) preparation:
With drop into respectively 2-phenyl-4 in the 50ml round-bottomed flask, 10-two ［ 4-bromophenyl ］-indenes [1,2-f] and isoindole-1; 3,9-triketone (0.196g, 0.31mmol); 2-thienyl boric acid (0.095g; 0.74mmol), four triphenyl phosphorus palladiums (22mg, 0.031mmol); 15mlTHF; the aqueous solution 3ml of yellow soda ash (0.1g, 0.93mmol), reflux 36h under the nitrogen protection; after reaction finishes; reaction solution is poured into water ethyl acetate extraction, organic phase anhydrous magnesium sulfate drying; suction filtration; underpressure distillation is removed the ethyl acetate crude product and is obtained brick-red solid 0.157g, productive rate 81% with the PE:DCM=2:1 column chromatography
R f=0.29 (PE:DCM=1:1), fusing point＞350 ℃.
HNMR(CDCl
3,300MHz)：δ： 7.84(d,J=8.0Hz,2H),7.75(d,J=8.0Hz,2H),7.62(d,J=6.7Hz,1H),7.52-7.47(m,5H),7.41-7.09(m,12H),6.61(d,J=7.4Hz,1H)。
9-oxo-Isosorbide-5-Nitrae-two [2-(2-thiophene) phenyl] fluorenes (
4b) synthetic:
With drop into respectively 9-oxo-1 in the 50ml round-bottomed flask; 4-two (2-bromophenyl) fluorenes (0.15g, 0.31mmol), 2-thienyl boric acid (0.095g; 0.74mmol); yellow soda ash (0.1g), four triphenyl phosphorus palladiums (22mg, 0.031mmol); 15mlTHF; the aqueous solution 3ml of yellow soda ash (0.1g, 0.93mmol), reflux 36h under the nitrogen protection; after reaction finishes; reaction solution is poured into water ethyl acetate extraction, organic phase anhydrous magnesium sulfate drying; suction filtration; underpressure distillation is removed the ethyl acetate crude product and is obtained yellow solid 0.116g with the PE:DCM=2:1 column chromatography, productive rate 76%
R f=0.63 (PE:DCM=1:1), fusing point 132-134 ℃.
HNMR(CDCl
3,300MHz)：δ： 7.73(d,J=7.9Hz,1H),7.63(d,J=7.1Hz,1H),7.56-7.35(m,7H),7.19-7.01(m,5H),7.03-7.01(m,1H),6.84-6.77(m,4H),6.47-6.42(m,1H)。
Claims (2)
1. the derivative of fluorenes, it is characterized in that 1,3-dihalogenated phenyl indenes [a] pentalene-2,8-diketone (2a, 2b) or 1,3-phenylbenzene indenes [a] pentalene-2,8-diketone (2c) and 2,5-norbornadiene reaction is at the Isosorbide-5-Nitrae of fluorenes-position introducing phenyl ring or halo phenyl ring, and its structure is as follows:
Perhaps
With 1,3-dihalogenated phenyl-indenes [a] pentalene-2,8-diketone (2a, 2b) or 1,3-phenylbenzene-indenes [a] pentalene-2,8-diketone (2c) generates indeno isoindoles compound with the reaction of N-phenyl butylene imide, and its structure is as follows:
With 2-thienyl boric acid and above-claimed cpd 3a, 3b be again 9-oxo-Isosorbide-5-Nitrae-dihalogenated phenyl fluorenes reaction or with above-claimed cpd 5a be 2-phenyl-4,10-two (4-bromophenyl)-indenes [1,2-f] and isoindole-1,3,9-, three reactive ketones access thienyl group in system, its structure is as follows:
2. the preparation method of the derivative of the described fluorenes of claim 1 is characterized in that the method comprises following concrete steps:
A, preparation 1,3-two (4-halogenophenyl)-2-acetone and 1,3-two (2-halogenophenyl)-2-acetone
To slowly splash into N to the dichloromethane solution of halogeno-benzene acetic acid or adjacent halogeno-benzene acetic acid, in N '-dicyclohexyl carbimide (DCC) and the dichloromethane solution to Dimethylamino pyridine (DMAP), react 18～32h under the normal temperature, make 1,3-two (4-halogenophenyl)-2-acetone and 1,3-two (2-halogenophenyl)-2-acetone; Wherein to halogeno-benzene acetic acid or adjacent halogeno-benzene acetic acid and N, the ratio of the amount of substance of N '-dicyclohexyl carbimide (DCC) is 1:0.5～0.95; N, N '-dicyclohexyl carbimide (DCC) and be 4:1～2 to the ratio of the amount of substance of Dimethylamino pyridine (DMAP); Ratio to the amount of substance of halogeno-benzene acetic acid or adjacent halogeno-benzene acetic acid and methylene dichloride is 1:20～100;
B, preparation 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone and 1,3-two (2-bromophenyl)-indenes [a] pentalene-2,8-diketone
10% KOH/MeOH solution is added drop-wise in the ethanolic soln of ninidrine and 1,3-two (4-bromophenyl)-2-acetone or 1,3-two (2-bromophenyl)-2-acetone, under 75 ℃, reacted 3～6 hours after dropwising; Make 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone and 1,3-two (2-bromophenyl)-indenes [a] pentalene-2,8-diketone; Ninidrine, 1, the ratio of the amount of substance of 3-two (4-bromophenyl)-2-acetone or 1,3-two (2-bromophenyl)-2-acetone, potassium hydroxide is 1～2.5:1:2～3; 1,3-two (4-bromophenyl)-2-acetone or 1,3-two (2-bromophenyl)-2-acetone are 1:30～100 with the ratio of the amount of substance of ethanol;
C, preparation 9-oxo-Isosorbide-5-Nitrae-two (4-bromophenyl) fluorenes, 9-oxo-Isosorbide-5-Nitrae-two (2-bromophenyl) fluorenes, 9-oxo-Isosorbide-5-Nitrae-diphenylfluorene
With 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone, 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone or 1,3-phenylbenzene-indenes [a] pentalene-2,8-diketone and 2,5-norbornadiene add in the toluene, reflux 12～18 hours makes 9-oxo-Isosorbide-5-Nitrae-two (4-bromophenyl) fluorenes, 9-oxo-1,4-two (2-bromophenyl) fluorenes, the 9-oxo-Isosorbide-5-Nitrae-compounds such as diphenylfluorene; Wherein 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone, 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone or 1,3-phenylbenzene-indenes [a] pentalene-2, the ratio of the amount of substance of 8-diketone and 2,5-norbornadiene is 1:1～5; 1,3-two (4-bromophenyl)-indenes [a] pentalene-2, the 8-diketone, 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone or 1,3-phenylbenzene-indenes [a] pentalene-2, the 8-diketone is 1:10～40 with the ratio of the amount of substance of toluene;
D, preparation N-phenyl-suitable horse imide
Aniline is added drop-wise to along in the diethyl ether solution of horse acyl acid anhydride, at 0 ℃ of reaction 10 min, filter the solid that reaction produces, in solid transfer to 100 ml round-bottomed flask after dropwising, add new steaming acetic anhydride and sodium-acetate at 60 ℃ of reaction 2h, make N-phenyl-suitable horse imide; The ratio of the amount of substance of suitable horse acyl acid anhydride and aniline is 1:1～4; The ratio of the amount of substance of suitable horse acyl acid anhydride and sodium-acetate is 1:0.5～1; The ratio of the amount of substance of suitable horse acyl acid anhydride and ether is 1:10～40; The ratio of the amount of substance of suitable horse acyl acid anhydride and acetic anhydride is 1:50～200;
E, preparation 2-phenyl-4,10-two (4-bromophenyl)-indenes [1,2-f] and isoindole-1,3,9-triketone, 2-phenyl-4,10-two (2-bromophenyl)-indenes [1,2-f] and isoindole-1,3,9-triketone or 2,4,10-triphenyl-indenes [1,2-f] and isoindole-1,3, the 9-triketone
With 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone, 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone or 1,3-phenylbenzene-indenes [a] pentalene-2,8-diketone and N-phenyl-along the horse imide, add in the phenylate solvent, 180 ℃ were reacted 4～12 hours, and made 2-phenyl-4,10-two (4-bromophenyl)-indenes [1,2-f] and isoindole-1,3, the 9-triketone, 2-phenyl-4,10-two (2-bromophenyl)-indenes [1,2-f] and isoindole-1,3, the 9-triketone, 2,4,10-triphenyl-indenes [1,2-f] and isoindole-1,3, the 9-triketone; Wherein 1,3-two (4-bromophenyl)-indenes [a] pentalene-2, the 8-diketone, 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone or 1,3-phenylbenzene-indenes [a] pentalene-2, the 8-diketone is 1:1～2 with the ratio of the amount of substance of N-phenyl-suitable horse acid amides, 3-two (4-bromophenyl)-indenes [a] pentalene-2, the 8-diketone, 1,3-two (4-bromophenyl)-indenes [a] pentalene-2,8-diketone or 1,3-phenylbenzene-indenes [a] pentalene-2, the 8-diketone is 1:15～25 with the ratio of the amount of substance of phenylate;
F, preparation 9-oxo-Isosorbide-5-Nitrae-two [4-(2-thiophene) phenyl] fluorenes
Under the nitrogen protection with 9-oxo-Isosorbide-5-Nitrae-two (4-bromophenyl) fluorenes, 2-thienyl boric acid, tetra-triphenylphosphine palladium, yellow soda ash join in the mixed solvent of toluene, second alcohol and water, 110 ℃ of lower reactions 5～8 hours, make 9-oxo-Isosorbide-5-Nitrae-two [4-(thiophene) phenyl] fluorenes; 9-oxo-Isosorbide-5-Nitrae-two (4-bromophenyl) fluorenes wherein, the 2-thienyl boric acid, tetra-triphenylphosphine palladium, the ratio of yellow soda ash amount of substance is 1:3～4:0.04～0.10:5～6, and 9-oxo-Isosorbide-5-Nitrae-two (4-bromophenyl) fluorenes is 1:60～100 with the ratio of the amount of substance of toluene; The volume ratio of toluene, second alcohol and water is 10:2:1;
G, preparation 9-oxo-Isosorbide-5-Nitrae-two [2-(2-thiophene) phenyl] fluorenes, 2-phenyl-4,10-two [4-(2-thiophene) phenyl]-indenes [1,2-f] and isoindole-1,3,9-triketone
Under the nitrogen protection with 9-oxo-1; 4-two (2-bromophenyl) fluorenes or 2-phenyl-4; 10-two (4-bromophenyl)-indenes [1; 2-f] and isoindole-1; 3; the 9-triketone; the 2-thienyl boric acid; tetra-triphenylphosphine palladium; yellow soda ash; join in the mixing solutions of tetrahydrofuran (THF) and water back flow reaction 24～36 hours, and made 9-oxo-Isosorbide-5-Nitrae-two [2-(2-thiophene) phenyl] fluorenes or 2-phenyl-4; 10-two [4-(2-thiophene) phenyl]-indenes [1; 2-f] and isoindole-1,3, the 9-triketone; 9-oxo-1 wherein; 4-two (2-bromophenyl) fluorenes or 2-phenyl-4,10-two (4-bromophenyl)-indenes [1,2-f] and isoindole-1; 3; the 9-triketone, 2-thienyl boric acid, tetra-triphenylphosphine palladium; the ratio of the amount of substance of yellow soda ash is 1:3～4:0.04～0.10:5～6; 9-oxo-Isosorbide-5-Nitrae-two (2-bromophenyl) fluorenes or 2-phenyl-4,10-two (4-bromophenyl)-indenes [1; 2-f] and isoindole-1; the ratio of the amount of substance of 3,9-triketone and tetrahydrofuran (THF) is 1:30～100, and the volume ratio of tetrahydrofuran (THF) and water is 10～30:1.
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