CN102030701B - Fluoradene derivative and preparation method thereof - Google Patents
Fluoradene derivative and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fluoradene derivative and a preparation method thereof. The preparation method comprises the following steps of: introducing fluoradene rings into compounds, namely carbazole, hexyl carbazole, triphenylamine and hexyl triindole; and catalyzing intramolecular carbon-hydrogen bond activation and hydrogen halide elimination reaction through palladium and efficiently constructing a carbon ring or a heterocyclic compound, particularly constructing the carbon ring with a novel structure. The invention aims to synthesize and characterize a fluoradene structural unit-containing large-tension cyclic compound; and the novel fluoradene structural unit-containing compound is expected to be used in the field of organic photoelectric materials.
Description
Technical field
The present invention relates to the organic chemistry synthesis technical field, specifically one type of Fluoradene verivate and preparation method thereof.
Background technology
In Synthetic Organic Chemistry, hightension aromatic nucleus molecule for example fenestrane theoretical or experimentally all be to have very big challenge.And wherein fluoradene (in the accompanying drawing 1 a), two indenes rings are shared quaternary carbons in a kind of acidic molecular and the molecule.Structural analysis to Fluradene is the hydrocarbon polymer C from the unknown
19H
10The C-C key of the aromatic nucleus of (b in the accompanying drawing 1) ([1] A.Streiweiser Jr.Tetrahedron Lett.1960, (6), 23.) gains enlightenment.Up to the present, be that considerably less ([3] are H.Rapoprt (a), and G.Smolinsky, J.Am.Chem.Soc.1958,80,2910 to the report of fluorandene; (b) H.Rapoprt, and G.Smolinsky, J.Am.Chem.Soc.1960,82,934; (c) G.Baum and H.Shecter, J.Org.Chem.1976,41,2120; (d) H.Dietrich, D.Bladauski, M.Grosse, K.Roth and D.Rewichi, Chem.Ber.1975,108,1807; (e) W.Burger, D.Bladauski, M.Grosse and D.Rewicki, Chem.Ber.1982,115,209; (f) S.Murata, T.Sugawara and H.Iwamura, J.Am.Chem.Soc.1985,107,6317.).Fluorandene has characteristic and thereby its interior clearly outside makes it to form stable compound on the structure with metal-complexing.The synthetic of the 7b position substitutive derivative of Fluorandene also was not in the news, up to the present have only two compound 7b-triisopropylsilylfluorandene and 7b-(2,4-dinitrophenyl)-crystalline structure of fluorandene was in the news; But ([4] are A.Xia (a), J.P.Selegue, A.Carrillo not relate to any concrete synthetic details; B.O.Patrick, S.Parkinand C.P.Brock, Acta Crystallographica 2001; B57,507; (b) L.Fabian and A.Kalman, ActaCrystallographica 2004, B60, p548; (c) C.P.Brock, and B.O.Patrick, Mol.Cryst.Liq.Cryst.2002,389,79.).The phenyl derivatives of other fluorandene is phenylfluoradene and its verivate for example; They are considered to and can derive and obtain via tetrabenzo [5.5.5.5] fenestrane, but all are unknown material also never appear in the newspapers (referring to the c and the d of accompanying drawing 1).
Summary of the invention
One type of Fluoradene verivate that the objective of the invention is to be directed against the deficiency of prior art and provide and preparation method thereof; Eliminate reaction through C-H activation and hydrogen halide in the palladium catalytic molecular and can efficiently make up carbocyclic ring or heterogeneous ring compound; Especially the isocyclic of novel structure makes up, and is devoted to contain hightension ring compound synthetic of Fluoradene structural unit and characterizes.
The present invention synthesizes various fluorandene verivates with conventional palladium catalytic molecular intramolecular cyclization arylation methodology of organic synthesis first; Promptly at 3 of carbazole and N-alkyl carbazole; 6; Introduced fluorandene substituted radical structure for 2,7,12 of the 4-position of the phenyl ring of triphenylamine and N-alkyl trimerization indoles.
The objective of the invention is to realize like this:
One type of fluoradene verivate, characteristics are: on compound carbazole, hexyl carbazole, triphenylamine and hexyl trimerization indoles, introduced the fluoradene ring, it has following structure:
A kind of preparation method of said derivative, this method comprises following concrete steps:
A, preparation midbody 9-(2-bromophenyl) fluorenol
(1), o-bromoaniline is dissolved in the 12mol/L hydrochloric acid, place-5～0 ℃, add sodium nitrite solution, reacted 1～2 hour, add liquor kalii iodide again, reacted 2 hours heat temperature raising to 60～70 ℃, obtains adjacent bromo-iodobenzene; Wherein: the mol ratio of o-bromoaniline, Sodium Nitrite and potassiumiodide is 1: (1.2～1.3): (1.4～1.5);
(2), adjacent bromo-iodobenzene that step (1) is obtained is dissolved in the THF, adds sec.-propyl bromination magnesium again ,-50～-40 ℃ of reactions 3 hours add the Fluorenone that is dissolved in THF inward.Get midbody product 9-(2-bromophenyl) fluorenol; Wherein: the mol ratio of adjacent bromo-iodobenzene, sec.-propyl bromination magnesium and Fluorenone is 1: 1: (0.6～1); The quality of adjacent bromo-iodobenzene and the volume ratio 1 of THF: (5～7);
B, Fu Ke alkylated reaction
(1), 9-(2-bromophenyl) fluorenol and triphenylamine be dissolved in solvent earlier, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 3～5 hours; Wherein: when the mol ratio of triphenylamine, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (2～2.5), obtain compound (12); When the mol ratio of triphenylamine, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is (2～2.5): (0.9～1.3): in the time of 1, obtain compound (10);
(2), 9-(2-bromophenyl) fluorenol and carbazole be dissolved in solvent earlier, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 6～8 hours; Wherein: when the mol ratio of carbazole, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (2～3), obtain compound (3);
(3), 9-(2-bromophenyl) fluorenol and hexyl carbazole be dissolved in solvent earlier, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 5～7 hours; Wherein: when the mol ratio of hexyl carbazole, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (2～2.5), obtain compound (8); When the mol ratio of hexyl carbazole, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (0.8～1.2), obtain compound (6);
(4), 9-(2-bromophenyl) fluorenol and hexyl trimerization indoles be dissolved in solvent, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 5～7 hours; When 5,10, the mol ratio of 15-three hexyl trimerization indoles, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (3～3.5), obtain compound (18);
Appearance agent described in b step (1), (2), (3) and (4) is 1,4-dioxane or methylene dichloride; Holding the volume of agent and the mass ratio of 9-(2-bromophenyl) fluorenol is (10～20): 1;
C, synthetic fluoradene verivate
With the synthetic fluoradene ring of arylation in the palladium catalytic molecular, its reaction conditions is:
Pd (OAc)
2/ PPh
3/ Na
2CO
3/ BuEt
3NCl/DMA or Pd (OAc)
2/ PPh
3/ Na
2CO
3/ BuEt
3NCl/DMF;
(1), the compound and palladium, yellow soda ash, triphenyl phosphorus and the benzyl triethyl ammonium ammonia chloride that the b step are obtained are dissolved in the solvent reheat to 140～170 ℃ reaction 4～6 hours; Said solvent is N, dinethylformamide or DMAC N,N;
The mol ratio of compound (3), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.1～0.3): (0.2～0.7): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (3) is (50-60): 1; Obtain compound 3,6-difluoradenyl-9H-carbazole (4);
The mol ratio of compound (6), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.1～0.2): (0.2-0.24): (4-5): (0.5-1); The mass ratio of the volume of solvent and compound (6) is (30-50): 1; Obtain compound 3-fluoradenyl-9-hexylcarbazole (7);
The mol ratio of compound (8), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.1～0.3): (0.2～0.66): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (8) is (30～50): 1; Obtain compound 3,6-difluoradene-9-hexylcarbazole (9);
The mol ratio of compound (10), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.05～0.2): (0.1～0.44): (4～6): (0.5～1); The mass ratio of the volume of solvent and compound (10) is (30～50): 1; Obtain compound tris [(4-fluoradenyl) phenyl] amine (11);
The mol ratio of compound (12), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.1～0.3): (0.2～0.7): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (12) is (40～60): 1; Obtain compound tris [(4,4 '-difluoradene) phenyl] amine (13);
The mol ratio of compound (18), palladium, triphenyl phosphorus, yellow soda ash and benzyl triethyl ammonium ammonia chloride is 1: (0.3～0.5): (0.6～1): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (18) is (40～60): 1; Obtain compound 5,10,15-trihexyl-2,7,12-trifluoradenyl-10,15-dihydro-5H-diindolo [3,2-a; 3 ', 2 '-c] carbazole (19).
The present invention makes the carbon-hydrogen activation on the aromatic nucleus realize intramolecular arylation with palladium catalyst.This catalyzer is common palladium [Pd (OAc)
2], palladium salt such as two (tricyclohexyl phosphine) Palladous chloride [(Cy
3P)
2PdCl
2], two (triphenylphosphine) Palladous chloride [(Ph
3P)
2PdCl
2], tetrakis triphenylphosphine palladium [(Ph
3P)
4Pd] etc., the solvent of using is generally polar solvent such as THF, dioxane, N, dinethylformamide (DMF), DMAC N,N (DMA), preferred N, dinethylformamide (DMF), DMAC N,N (DMA).
The present invention is the reaction of carrying out with 9-(2-bromophenyl)-9-fluorenol and various substrate.For four kinds of substrate N-hexyl carbazoles that relate in the reaction, carbazole, they all contain the N atom triphenylamine and trimerization indoles, and the lone-pair electron on this N atom are participated in conjugation.In final compound (4), contain two fluorandene structures; Contain a fluorandene structure in the compound (7); (9) contain two fluorandene structures; (11) contain a fluorandene structure in, contain two fluorandene structures in (13) and contain three fluorandene structures with (20).All be to carry out the Fu Shi alkylated reaction as catalyzer in the reaction with Lewis acid three fluosulfonic acid; Solvent generally is polar solvent such as THF; 1, first-selection such as 4-dioxane 1,4-dioxane; Heat up again after being added dropwise to complete under the general first normal temperature of operation about 40 ℃-100 ℃ first-selected 70-80 ℃ and reacted 1-10 hour preferred 4-5 hour down.Its solvability variation of increase along with fluoradene substituted radical number; Three [4; 4 ', 4 " three (9-(2-bromophenyl) fluorenyl) phenyl] the via palladium-catalyzed product that obtains of amine can't obtain pure article because of its solvability is too poor, and the bis that three [4; 4 ' two (9-(2-bromophenyl) fluorenyl) phenyl] amine (12) obtains via palladium catalysis [(4,4 '-difluoradene) phenyl] amine (13) also can't pass through because of the solvability extreme difference
13C NMR detects.Sp in the various final fluorandene verivates
3The quaternary carbon of hydridization exists
13Generally about 60ppm, we come final its structure of confirming through the X-single crystal diffraction to data among the C NMR.
Fluoradene verivate provided by the invention is because of having specific luminescent properties and good thermostability, so the compound that contains the Fluoradene structural unit of this type novelty is expected to be used for the organic photoelectrical material field.
Description of drawings
Fig. 1 is several kinds of Fluoradene derivant structure figure, and wherein a is known; B, c and d are unknown compound
Fig. 2-7 is the preparation flow figure of the embodiment of the invention
Fig. 8 is the single crystal structure figure of The compounds of this invention (7)
Embodiment
The invention is further illustrated by the following examples
Adopt reagent: Sodium Nitrite, 1,4-epoxy hexane, absolute ethyl alcohol, THF, analytical pure, Shanghai Shang Si Fine Chemical Co., Ltd; O-bromoaniline, bromohexane, three fluosulfonic acid, isatin, sodium hydride, analytical pure, Shanghai reaches auspicious fine chemistry ltd; Fluorenone, carbazole, triphenylamine, Hydrazine Hydrate 80, oxo phosphorus chloride, triphenyl phosphorus, analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group produces; Yellow soda ash, potassiumiodide, analytical pure, Shanghai reagent one factory; Concentrated hydrochloric acid, analytical pure, Shanghai reagent four Kunshan subsidiary factories of factory; Sec.-propyl bromination magnesium, analytical pure, ladder is uncommon likes that (Shanghai) changes into industrial development ltd; Palladium, analytical pure, chemical industry ltd is reached in Shaanxi; The phenyl triethyl ammonium chloride, analytical pure, Shanghai chemical reagents corporation of Chinese Medicine group.
1), the preparation of 2-bromo iodobenzene (1)
(5g 29.06mmol) is dissolved in the 50mL water, the 15mL concentrated hydrochloric acid is added wherein again, is cooled to 0 ℃ with o-bromoaniline.With NaNO
2(2.41g 34.87mmol) is dissolved in the 50mL water, slowly is added drop-wise in the above-mentioned solution.When solid all after the dissolving, (7.23g 43.59mmol) joins in the above-mentioned solution slowly, and it is blood red that solution is will to be dissolved in the KI of 11mL water.Stir 0.5h under the room temperature.Be warming up to 70 ℃ of stirring 0.5h.Cool off, add the Na of 0.43mol/L
2SO
3Solution 20mL neutralization.Use dichloromethane extraction, organic phase is passed through anhydrous MgSO again with washing
4Dry.Remove behind the suction filtration and desolvate, again underpressure distillation obtain light yellow liquid (3.85g, yield:77.0%).
1H?NMR(CDCl
3，500MHz)：δ7.88-7.86(dd，J＝8.0Hz，J＝1.4Hz?1H)；7.64-7.62(dd，J＝8.0Hz，J＝1.4Hz，1H)；7.30-7.20(td，J＝7.9Hz，J＝1.4Hz?1H)；7.02-6.99(td，J＝7.8Hz，J＝1.4Hz，1H).
2), the preparation of 9-(2-bromophenyl)-9-fluorenol (2)
(6.98g 24.67mmol) is dissolved in the 25mL THF (THF), is cooled to-40 ℃ with adjacent bromo-iodobenzene under the nitrogen protection; Slowly in reaction flask, drip 24mL1.0M sec.-propyl bromination magnesium solution, dropwise the back and keep this temperature to stir 3h, then with Fluorenone (2.88g; 16.00mmol) splash in the above-mentioned solution in THF (15ml); Stir 0.5h, slowly be warming up to the room temperature continued and stir 12h, the gained reaction mixture dilutes with saturated ammonium chloride solution; (3 * 100ml) extractions, organic phase is used anhydrous MgSO with ETHYLE ACETATE
4Drying, suction filtration revolves and does the back resistates and carry out recrystallization with ETHYLE ACETATE and sherwood oil and obtain white solid (3.51g, productive rate: 65.0%) .Mp:142-144 ℃;
1H NMR (CDCl
3, 500MHz): δ 8.48 (br, 1H); 7.56 (d, J=7.6Hz, 2H); 7.50 (s, 1H); 7.45-7.40 (m, 3H); 7.26 (t, J=7.7Hz, 2H); 7.19 (t, J=7.7Hz, 3H); 2.43 (br, 1H).
13C?NMR(CDCl
3，125MHz)：δ：120.24?120.92?124.00?127.07?128.35?129.10?129.23?134.39?140.83141.35?148.69
3) 3, the 6-two (preparation of 9-(2-bromophenyl)-9-fluorenyl carbazole (3)
Under the nitrogen protection with carbazole (0.50g, 2.97mmol) and 9-(2-bromophenyl)-9-fluorenol (2.0g 5.93mmol) is dissolved in 25mL 1, and in the 4-dioxane, (0.89g 5.93mmol) slowly splashes in the above-mentioned solution with three fluosulfonic acid then.Be warming up to 80 ℃ of reacting by heating 7h again.Cooling is poured reaction solution in the water into, suction filtration, oven dry.Use sherwood oil: ETHYLE ACETATE=cross post at 5: 1, obtain crude product (0.36g), directly throw next step.
4) 3, the preparation of 6-difluoradenyl-9H-carbazole (4)
Under the nitrogen protection with 3,6-two (9-(2-bromophenyl)-9 fluorenyl carbazoles (0.36g, 0.45mmol); Palladium (30mg, 0.13mmol), triphenyl phosphorus (70mg; 0.29mmol) and yellow soda ash (240mg, 2.25mmol), triethylbenzene ammonium chloride (100mg; 0.45mmol) be dissolved in the 20mL DMAC N,N, be heated to 140 ℃ of about 5h of reaction.After the cooling reaction solution is poured in the water, (3 * 30mL) extractions, organic phase is used MgSO with methylene dichloride
4Drying, suction filtration revolves dried.Use sherwood oil: ETHYLE ACETATE=cross post obtain white solid (0.16g, productive rate 55.2%) at 1: 1.Mp＞350℃。
1H?NMR(DMSO，500MHz)：δ11.01(s，1H)；8.25(d，J＝7.5Hz，4H)；7.74(d，J＝7.5Hz，4H)；7.69(s，2H)；7.56(d，J＝7.5Hz，4H)；7.48(d，J＝7.5Hz，2H)；7.38-7.34(m，6H)；7.28(t，J＝7.5Hz，4H)；7.17(d，J＝7.5Hz，2H).
13C?NMR(DMSO，125MHz)：δ66.10?110.93?115.96?119.68?121.54?122.00?124.27?126.19?126.50127.84?130.94?134.95?138.65?139.78?143.30?152.23?165.78.
1) with (1) among the embodiment 1
2) with (2) among the embodiment 1
3) preparation of 9-hexyl carbazole (5)
Under the nitrogen protection with NaH (1.74g, 60%w/w dispersion in mineral oil 44.0mmol) pour in 20mLN is housed, in the round-bottomed flask of N-N,N-DIMETHYLACETAMIDE, N
2Protection.(5.52g 33.0mmol) is dissolved in the 60mL DMAC N,N and splashes in the above-mentioned solution and stir 0.5h with carbazole.Drip inside again hexyl bromide 1 bromohexane (6.54g, 39.6mmol), reflux 5h.During cooling was fallen back, (3 * 50mL) extractions, organic phase was used MgSO with methylene dichloride
4Drying, suction filtration revolves dried.Use ethyl alcohol recrystallization, obtain white solid (6.39g, productive rate 77.0%).Mp：64-66℃
4) preparation of 3-(9-(2-bromophenyl) fluorenyl)-9-hexyl carbazole (6)
Under the nitrogen protection with N-hexyl carbazole (2.80g, 11.12mmol) (0.67g 4.45mmol) is dissolved in 10mL1 with three fluosulfonic acid; In the 4-dioxane; Then with 9-(2-bromophenyl)-9-fluorenol (1.5g 4.45mmol) is dissolved in 10mL 1, in the 4-dioxane in; And splash into slowly in the above-mentioned solution, and then be warming up to 90 ℃ of reacting by heating 5h.After the cooling reaction solution is poured in the water, (3 * 100mL) extractions, organic phase is used MgSO with methylene dichloride
4Drying is revolved dried behind the suction filtration.Use sherwood oil: ETHYLE ACETATE=cross post obtain white solid (2.8g, productive rate 51.2%) at 40: 1.Mp：181-183℃
1H?NMR(CDCl
3?500MHz)：δ7.89(d，J＝7.9Hz，1H)；7.84(s，1H)；7.77(d，J＝6.2Hz，2H)；7.71(br，1H)；7.62(br，1H)；7.55(d，J＝7.9Hz，1H)；7.42(d，J＝8.8Hz，1H)；7.40-7.36(m，3H)；7.33(d，J＝8.3Hz，1H)；7.28(br，1H)；7.25(t，J＝4.3Hz，2H)；7.20(d，J＝7.7Hz，1H)；7.13-7.10(m，2H)；7.08-7.05(m，1H)；4.22(t，J＝7.3Hz，2H)；1.84-1.79(m，2H)；1.37-1.35(m，2H)；1.29-1.25(m，4H)；0.85(t，J＝6.8Hz，3H).
13C?NMR(CDCl
3，125MHz)：δ13.98?22.51?26.93?28.92?31.52?43.12?66.39?108.44?108.58?118.51119.04?120.25?120.31?122.57?122.80?123.54?125.43?126.13?126.21?126.31?126.92?127.49?128.30134.56?135.83?139.28?140.69?144.32?151.40
5) preparation of 3-fluoradenyl-9-hexylcarbazole (7)
Under the nitrogen protection with 3-(9-(2-bromophenyl) fluorenyl)-9-hexyl carbazole (0.57g, 1.00mmol), palladium (50mg; 0.20mmol), triphenyl phosphorus (120mg, 0.44mmol) and yellow soda ash (530mg; 5mmol); (110mg 0.5mmol) is dissolved in 20mLN to the phenyl triethyl ammonium chloride, is heated to 140 ℃ of about 5h in the N-N,N-DIMETHYLACETAMIDE.After the cooling reaction solution is poured in the water, (3 * 30mL) extractions, organic phase is used MgSO with methylene dichloride
4Drying, suction filtration revolves dried.Use sherwood oil: ETHYLE ACETATE=cross post at 20: 1 obtains white solid (0.4g, productive rate 81.8%).Mp：206-208℃
1H?NMR(DMSO，500MHz)：δ8.33(d，J＝7.5Hz，2H)；8.10(s，1H)；7.99(d，J＝7.8Hz，1H)；7.74(d，J＝7.4Hz，2H)；7.58(d，J＝7.4Hz，2H)；7.51-7.46(m，3H)；7.39-7.31(m，4H)；7.28(t，J＝7.4Hz，2H)；7.11(t，J＝7.4Hz，1H)；4.22(t，J＝7.0Hz，2H)；1.63-1.61(m，2H)；1.17-1.14(m，6H)；0.75(t，J＝6.8Hz，3H)；
13C?NMR(CDCl
3，125MHz)：δ：13.97?22.45?26.86?28.87?31.51?42.99?66.62?108.48?117.63?118.43119.29.120.26?121.88?122.43?122.69?124.59?125.38?126.01?126.37?127.77?130.64?134.46?139.05140.14?140.69?144.31?152.52?167.23
1) with (1) among the embodiment 1
2) with (2) among the embodiment 1
3) with (3) among the embodiment 2
4) 3, the preparation of 6-two [9-(2-bromophenyl) fluorenyl]-9-hexyl carbazole (8)
Under the nitrogen protection with N-hexyl carbazole (1.29g, 5.19mmol) and 9-(2-bromophenyl)-9-fluorenol (3.5g 10.37mmol) is dissolved in 50mL 1; In the 4-dioxane, (1.48g 9.86mmol) splashes in the above-mentioned solution slowly with three fluosulfonic acid then; Be warming up to 80 ℃ again, heating 5h.Cooling is poured reaction solution in the water into, suction filtration, oven dry.Use sherwood oil: methylene dichloride=cross post at 4: 1 obtains white solid (2.0g, productive rate 43.3%).
1H?NMR(CDCl
3?500MHz)：δ7.75(s，4H)；7.69(br，2H)；7.59(s，2H)；7.51(d，J＝7.0Hz，4H)；7.40-7.36(m，6H)；7.25(t，J＝7.5Hz，4H)；7.19(d，J＝9.0Hz，2H)；7.12-7.08(m，4H)；7.06-7.03(m，2H)；4.14(t，J＝7.5Hz，2H)；1.76-1.72(m，2H)；1.30-1.23(m，6H)；0.83(t，J＝7.0Hz，3H).
13C?NMR(CDCl
3，125MHz)：δ13.97?22.49?26.90?28.93?31.49?43.18?66.31?108.39?119.15?120.24122.60?126.31?126.88?127.39?128.26?132.14?134.27?135.69?139.56?140.69?144.26?148.08?151.17151.79.
5) 3, the preparation of 6-difluoradene-9-hexylcarbazole (9)
Under the nitrogen protection with 3,6-two [9-(2-bromophenyl) fluorenyl]-9-hexyl carbazole (0.50g, 0.56mmol), palladium (40mg; 0.17mmol), triphenyl phosphorus (100mg, 0.37mmol) and yellow soda ash (240mg; 2.24mmol), (130mg 0.56mmol) is dissolved in 20mL N to the phenyl triethyl ammonium chloride; In the N-N,N-DIMETHYLACETAMIDE, be heated to 140 ℃, about 5h.After the cooling reaction solution is poured in the water, (3 * 30mL) extractions, organic phase is used MgSO with methylene dichloride
4Drying, suction filtration revolves dried.Use sherwood oil: methylene dichloride=cross post at 2: 1 obtains white solid (0.29g, productive rate 71.3%).Mp(dec)：325℃
1H?NMR(DMSO-d
6，500MHz)：δ8.24(d，J＝7.5Hz，4H)；7.75(d，J＝7.5Hz，4H)；7.68(S，2H)；7.57(d，J＝7.4Hz，4H)；7.49(t，J＝7.4Hz，2H)；7.36(t，J＝7.6Hz，6H)；7.28(t，J＝7.4Hz，4H)；7.20(d，J＝8.8Hz，2H)；4.06(t，J＝7.2Hz，2H)；1.50(m，2H)；1.08(m，6H)；0.70(t，J＝6.5Hz，3H).
13C?NMR(CDCl
3，125MHz)：δ13.96?22.39?26.73?28.79?31.45?42.83?66.64?108.35?117.50?119.27121.82?122.18?124.42?126.13?126.29?127.73?130.58?133.93139.16?140.05?144.34?152.47?167.31
1) with (1) among the embodiment 1
2) with (2) among the embodiment 1
3) preparation of three [4-(9-(2-bromophenyl) fluorenyl) phenyl] amine (10)
Under the nitrogen protection with triphenylamine (6.51mmol, 1.60) and three fluosulfonic acid (0.44g 2.96mmol) is dissolved in 10mL 1, in the 4-dioxane, N
2Protection.With 9-(2-bromophenyl)-9-fluorenol (1.0g 2.96mmol) is dissolved in 10mL 1, in the 4-dioxane in, and splash into slowly in the above-mentioned solution, be warming up to 90 ℃ again, heating 5h.Cooling is poured reaction solution in the water into, and (3 * 50mL) extractions, organic phase is used MgSO with methylene dichloride
4Drying, suction filtration revolves dried.Use sherwood oil: ETHYLE ACETATE=cross post at 40: 1 obtains white solid (1.01g, productive rate 60.5%).
1H?NMR(CDCl
3?500MHz)：δ7.75(d，J＝7.5Hz，2H)；7.56(d，J＝7.1Hz，2H)；7.54(d，J＝7.6Hz，1H)；7.37(t，J＝7.4Hz，2H)；7.27(d，J＝7.7Hz，3H)；7.20(t，J＝7.7Hz，4H)；7.14(s，2H)；7.07(dd，J＝8.5Hz，J＝7.7Hz，6H)；6.97(t，J＝7.4Hz，2H)；6.90(d，J＝8.6Hz，2H).
13C?NMR(CDCl
3，125MHz)：δ119.28?121.84?122.65?123.21?124.26?126.00?126.40?127.13?127.86129.07?120.68?137.75?140.00?144.38?146.00?147.57?151.86
4) preparation of tris [(4-fluoradenyl) phenyl] amine (11)
Under the nitrogen protection with three [4-(9-(2-bromophenyl) fluorenyl) phenyl] amine (0.56g, 1.0mmol), palladium (50mg 0.20mmol); Triphenyl phosphorus (120mg, 0.44mmol) and yellow soda ash (530mg, 5.0mmol); Phenyl triethyl ammonium chloride (110mg; 0.50mmol) be dissolved in the 20mL DMAC N,N, be heated to 140 ℃ of about 4h of reaction.After the cooling reaction solution is poured in the water, (3 * 30mL) extractions, organic phase is used MgSO with methylene dichloride
4Drying, suction filtration revolves dried.Use sherwood oil: ETHYLE ACETATE=cross post at 20: 1 obtains white solid (0.18g, productive rate 37.2%).Mp：256-259℃
1H?NMR(CDCl
3?500MHz)：δ7.84(d，J＝7.5Hz，2H)；7.50(d，J＝7.5Hz，2H)；7.35(t，J＝7.5Hz，5H)；7.24(d，J＝7.5Hz，2H)；7.16(t，J＝8.0Hz，4H)；7.03(d，J＝4.3Hz，2H)；6.97-6.92(m，6H)；6.77(d，J＝9.0Hz，2H).
13C?NMR(CDCl
3，125MHz)：δ65.78?120.22?122.66?123.40?123.47?124.25?126.16?126.99?127.54127.58?128.40?128.62?129.13?135.88?137.95?140.66?143.74?146.13?147.66?150.65
1) with (1) among the embodiment 1
2) with (2) among the embodiment 1
3) preparation of three [4,4 '-two (9-(2-bromophenyl) fluorenyl) phenyl] amine (12)
Under the nitrogen protection with triphenylamine (2.04mmol, 0.5g) (0.67g 4.48mmol) is dissolved in 20mL 1 with three fluosulfonic acid; In the 4-dioxane, (1.51g 4.48mmol) is dissolved in 10mL 1 with 9-(2-bromophenyl)-9-fluorenol; In the 4-dioxane; And slowly splash in the above-mentioned solution, be warming up to 90 ℃ again, reacting by heating 5h.Cooling is poured reaction solution in the water into, and (3 * 50mL) extractions, organic phase is used MgSO with methylene dichloride
4Drying, suction filtration revolves dried.Use sherwood oil: methylene dichloride=cross post at 3: 1 obtains white solid (0.62g, productive rate 34.4%).
1H?NMR(CDCl
3，500MHz)：δ7.73(d，J＝7.5Hz，4H)；7.56-7.51(m，6H)；7.35(t，J＝7.3Hz，4H)；7.25(d，J＝7.0Hz，2H)；7.17(t，J＝8.2Hz，2H)；7.11-7.07(m，4H)；7.06-7.01(m，8H)；6.93(t，J＝7.2Hz，1H)；6.87(d，J＝8.7Hz，4H)；
13C?NMR(CDCl
3，125MHz)：δ：65.74?120.19?122.77?123.39?123.44?124.23?124.53?126.13?126.97127.52?127.55?128.37?128.54?129.08?129.12?131.73?135.85?137.89?140.61?143.71?145.93?147.41150.62.
4) preparation of tris [(4,4 '-difluoradene) phenyl] amine (13)
Under the nitrogen protection with three [4,4 '-two (9-(2-bromophenyl) fluorenyl) phenyl] amine (0.50g, 0.57mmol); Palladium (40mg, 0.17mmol), triphenyl phosphorus (100mg; 0.37mmol) and yellow soda ash (240mg, 2.26mmol), phenyl triethyl ammonium chloride (130mg; 0.57mmol) be dissolved in the 20mL DMAC N,N, be heated to 140 ℃ of about 5h of reaction.After the cooling reaction solution is poured in the water, (3 * 30mL) extractions, organic phase is used MgSO with methylene dichloride
4Drying, suction filtration revolves dried.Use sherwood oil: methylene dichloride=cross post at 1: 1 obtains white solid (0.29g, productive rate 71.1%).Mp：346-349℃
1H?NMR(CDCl
3，500MHz)：δ7.78(d，J＝7.5Hz，4H)；7.58(d，J＝7.5Hz，4H)；7.31(t，J＝6.5Hz，10H)；7.20(t，J＝7.5Hz，4H)；7.06(t，J＝8.0Hz，2H)；6.93(d，J＝8.5Hz，4H)；6.87-6.83(m，3H)；6.63(d，J＝8.5Hz，4H).
1) with (1) among the embodiment 1
2) with (2) among the embodiment 1
3) preparation of isatin-3-hydrazone (14)
(3.75g 25.4mmol) is dissolved in the 30mL methyl alcohol isatin, drips 2.91g Hydrazine Hydrate 80 (massfraction 85%) inward.The about 1h of mild heat.In ice-water bath, cool off, suction filtration gets yellow solid (3.68g, productive rate 89.5%).Mp(dec)：225℃
4) preparation of 2-indolone (15)
1.2g Na is dissolved in the ethanol of 30mL, is stirred to complete dissolving.And toward isatin-3-hydrazone (3g slowly drips in 18.6mmol), is warming up to 60-70 ℃, is back to no N
2Till the generation.Cooling adds 10%HCl and is adjusted to pH=1.Use dichloromethane extraction, organic phase is used MgSO
4Drying is revolved dried behind the suction filtration.Get light yellow solid (2.08g, productive rate 69.3%) with methylene dichloride and sherwood oil recrystallization.Mp：125-128℃
5) preparation of trimerization indoles (16)
(1.0g 7.5mmol) adds 4mL POCl toward the 2-indoles down in nitrogen protection
3, be heated to 120 ℃ of reactions and distill away unnecessary POCl behind the 15h
3, resistates is poured in the water, with (3 * 50ml) extractions, organic phase is used MgSO with back ETHYLE ACETATE in the yellow soda ash
4Drying, suction filtration revolves dried.Use P: A=4: 1 crosses post, obtains yellow solid (0.07g, productive rate 8.1%).Mp＞350℃
1H?NMR(DMSO-d
6，500MHz)：δ11.45(s，1H)；7.58(d，J＝8.0Hz，1H)；7.43(d，J＝8.0Hz，1H)；7.15-7.07(m，2H).
6) 5,10, the preparation of 15-three hexyl trimerization indoles (17)
Under the nitrogen protection with NaH (4.06mmol, 60%w/w dispersion in mineral oil 0.16g) is suspended among the 5mLDMF, drip inward three polycarbazoles be dissolved in 15mL DMF (0.4g, 1.16mmol), stirring at normal temperature 0.5h.(0.76g 4.63mmol) is added dropwise to wherein, heating reflux reaction 1h with hexyl bromide 1 bromohexane again.Cooling is poured reaction in the water into, and (3 * 50mL) extractions, organic phase is used MgSO with methylene dichloride
4Drying, suction filtration revolves dried.Use ethyl alcohol recrystallization, obtain yellow solid (0.39g, productive rate 98.1%).Mp：131-133℃
1H?NMR(CDCl
3，500MHz)：δ7.41-7.37(m，6H)；7.19(t，J＝7.6Hz，3H)；7.10(t，J＝7.2Hz，3H)；4.27-4.15(m，6H)；1.48-1.47(m，3H)；1.34-1.32(m，3H)；0.61-0.51(m，18H)；0.44(t，J＝6.3Hz，9H).
13C?NMR(CDCl3，125MHz)：δ：13.80?21.56?25.70?29.17?31.15?44.76?107.14?110.30?118.79119.80?120.96?127.47?137.25?138.29
7) 5,10,15-three hexyls-2,7, the preparation of 12-three [9-bromophenyl) fluorenyl] trimerization indoles (18)
With 5,10, (0.6g, 1.0mmol), (1.18g, 3.5mmol) in 20mL 1,4-dioxy hexamethylene six encircles 9-(bromophenyl) 9-fluorenol 15-three hexyls three polycarbazoles under the nitrogen protection.Drip inward three fluosulfonic acid (0.53g, 3.5mmol).Reflux, reaction 5h.Cooling is poured reaction in the water into, and (3 * 100mL) extractions, organic phase is used MgSO with methylene dichloride
4Drying, suction filtration revolves dried.Use sherwood oil: ETHYLE ACETATE=3: 1, obtain crude product (0.72g), directly throw next step.
8) 5,10,15-trihexyl-2,7,12-trifluoradenyl-10,15-dihydro-5H-diindolo [3,2-a; 3 ', 2 '-c] preparation of carbazole (19)
Under the nitrogen protection with 5,10,15-three hexyls-2,7; 12-three [the 9-bromophenyl) fluorenyl] the trimerization indoles (0.50g, 0.32mmol), palladium (30mg, 0.15mmol); Triphenyl phosphorus (80mg, 0.32mmol) and yellow soda ash (140mg, 1.28mmol), phenyl triethyl ammonium chloride (70mg; 0.32mmol) be dissolved in the 20mL DMAC N,N, be heated to 140 ℃, about 5h.After the cooling reaction solution is poured in the water, (3 * 50mL) extractions, organic phase is used MgSO with methylene dichloride
4Drying, suction filtration revolves dried.Use sherwood oil: methylene dichloride=cross post at 20: 1 obtains yellow solid (0.35g, productive rate 83.3%).
1H?NMR(CDCl3，500MHz)：δ7.81-7.77(m，6H)；7.57(d，J＝7.0Hz，6H)；7.34-7.25(m，48H，CDCl3overlap)；7.16(t，J＝7.0Hz，18H)；6.99(s，3H)；6.80(s，6H)；3.74-3.67(m，6H)；0.97-0.95(m，6H)；0.45-0.24(m，27H).
13C?NMR(CDCl3，125MHz)：δ13.60?21.36?25.13?28.70?30.70?44.26?66.87?106.09?108.02?118.22118.80?119.18?119.21?121.71?125.79?125.91?126.00?126.20?127.67?130.51?136.77?136.85?138.26139.96?140.01?144.39?152.52?167.24.
Claims (2)
1. one type of fluoradene verivate, it is characterized in that: on compound carbazole, hexyl carbazole, triphenylamine and hexyl trimerization indoles, introduced the fluoradene ring, it has following structure
2. the preparation method of the said verivate of claim 1 is characterized in that this method comprises following concrete steps:
A, preparation midbody 9-(2-bromophenyl) fluorenol
(1), o-bromoaniline is dissolved in the hydrochloric acid of 12mol/L, place-5～0 ℃, add sodium nitrite solution, reacted 1～2 hour, add liquor kalii iodide again, reacted 2 hours heat temperature raising to 60～70 ℃, obtains adjacent bromo-iodobenzene; Wherein: the mol ratio of o-bromoaniline, Sodium Nitrite and potassiumiodide is 1: (1.2～1.3): (1.4～1.5);
(2), adjacent bromo-iodobenzene that step (1) is obtained is dissolved in the THF, adds sec.-propyl bromination magnesium again, places-50～-40 ℃ of reactions 3 hours, adds the Fluorenone solution that is dissolved in THF more inward, midbody product 9-(2-bromophenyl) fluorenol; Wherein: the mol ratio of adjacent bromo-iodobenzene, sec.-propyl bromination magnesium and Fluorenone is 1: 1: (0.6～1); The quality of adjacent bromo-iodobenzene and the volume ratio 1 of THF: (5～7);
B, Fu Ke alkylated reaction
(1), 9-(2-bromophenyl) fluorenol and triphenylamine be dissolved in solvent earlier, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 3～5 hours; Wherein: when the mol ratio of triphenylamine, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (2～2.5), obtain compound (12); When the mol ratio of triphenylamine, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is (2～2.5): (0.9～1.3): in the time of 1, obtain compound (10);
(2), 9-(2-bromophenyl) fluorenol and carbazole be dissolved in solvent earlier, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 6～8 hours; Wherein: when the mol ratio of carbazole, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (2～3), obtain compound (3);
(3), 9-(2-bromophenyl) fluorenol and hexyl carbazole be dissolved in solvent earlier, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 5～7 hours; Wherein: when the mol ratio of hexyl carbazole, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (2～2.5), obtain compound (8); When the mol ratio of hexyl carbazole, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (0.8～1.2), obtain compound (6);
(4), 9-(2-bromophenyl) fluorenol and hexyl trimerization indoles be dissolved in solvent, adds three fluosulfonic acid, after be warming up to 70～90 ℃ of reactions 5～7 hours; When 5,10, the mol ratio of 15-three hexyl trimerization indoles, three fluosulfonic acid and 9-(2-bromophenyl) fluorenol is 1: (0.9～1.3): when (3～3.5), obtain compound (18);
Solvent described in b step (1), (2), (3) and (4) is 1, the 4-dioxane; The mass ratio of the volume of solvent and 9-(2-bromophenyl) fluorenol is (10～20): 1;
C, synthetic fluoradene verivate
With the synthetic fluoradene ring of arylation in the palladium catalytic molecular, its reaction conditions is:
(1), the compound and palladium, yellow soda ash, triphenyl phosphorus and the benzyltriethylammoinium chloride that the b step are obtained are dissolved in the solvent reheat to 140～170 ℃ reaction 4～6 hours; Said solvent is N, dinethylformamide or DMAC N,N;
The mol ratio of compound (3), palladium, triphenyl phosphorus, yellow soda ash and benzyltriethylammoinium chloride is 1: (0.1～0.3): (0.2～0.7): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (3) is (50-60): 1; Obtain compound 3,6-difluoradenyl-9H-carbazole (4);
The mol ratio of compound (6), palladium, triphenyl phosphorus, yellow soda ash and benzyltriethylammoinium chloride is 1: (0.1～0.2): (0.2-0.24): (4-5): (0.5-1); The mass ratio of the volume of solvent and compound (6) is (30-50): 1; Obtain compound 3-fluoradenyl-9-hexylcarbazole (7);
The mol ratio of compound (8), palladium, triphenyl phosphorus, yellow soda ash and benzyltriethylammoinium chloride is 1: (0.1～0.3): (0.2～0.66): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (8) is (30～50): 1; Obtain compound 3,6-difluoradene-9-hexylcarbazole (9);
The mol ratio of compound (10), palladium, triphenyl phosphorus, yellow soda ash and benzyltriethylammoinium chloride is 1: (0.05～0.2): (0.1～0.44): (4～6): (0.5～1); The mass ratio of the volume of solvent and compound (10) is (30～50): 1; Obtain compound (11);
The mol ratio of compound (12), palladium, triphenyl phosphorus, yellow soda ash and benzyltriethylammoinium chloride is 1: (0.1～0.3): (0.2～0.7): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (12) is (40～60): 1; Obtain compound (13);
The mol ratio of compound (18), palladium, triphenyl phosphorus, yellow soda ash and benzyltriethylammoinium chloride is 1: (0.3～0.5): (0.6～1): (4～5): (0.5～1); The mass ratio of the volume of solvent and compound (18) is (40～60): 1; Obtain compound 5,10,15-trihexyl-2,7,12-trifluoradenyl-10,15-dihydro-5H-diindolo [3,2-a; 3 ', 2 '-c] carbazole (19).
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