CN105503897A - Asymmetric benzophenanthrene tri-furan/thiophene, derivate thereof and preparation method - Google Patents

Asymmetric benzophenanthrene tri-furan/thiophene, derivate thereof and preparation method Download PDF

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CN105503897A
CN105503897A CN201610058245.9A CN201610058245A CN105503897A CN 105503897 A CN105503897 A CN 105503897A CN 201610058245 A CN201610058245 A CN 201610058245A CN 105503897 A CN105503897 A CN 105503897A
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benzophenanthrene
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刘乾才
李秋云
白中胜
叶培珺
董坤
安康
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East China Normal University
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Abstract

The invention discloses an asymmetric benzophenanthrene tri-furan/thiophene and a derivate thereof. Three furan/thiophene rings of the derivate are distributed at the asymmetric positions and are of the structure shown in the following formula, wherein R = hydrogen, C8 and a linear chain or an alkyl group or phenyl group comprising branch chains. A preparation method of the asymmetric benzophenanthrene tri-furan/thiophene comprises the steps that o-bromophenol methyl ether/chloroanisole is used as a raw material, asymmetric 2,6,11-tribromo-3,7,10-triethoxy benzophenanthrene or 2,6,11-tribromo-3,7,10-trichlorine benzophenanthrene is synthesized in one step under the effect of ferric trichloride; a methyl protecting group is removed under the effect of boron tribromide, the obtained product reacts with acetic anhydride and trifluoromethanesulfonic anhydride, then is subjected to a Sonogashira coupled reaction with alkyne under the palladium catalysis to obtain a series of 3,7,10-trialkynyl-2,6,11 tri(ethoxycarbonyl) benzophenanthrene and 3,7,10-trichlorine-2,6,11-trialkynyl benzophenanthrene; finally under the effect of cesium carbonate and sodium sulfide, cyclization is carried out to obtain the asymmetric benzophenanthrene tri-furan/thiophene and the derivate thereof. The range of organic electroluminescence materials is broadened through a series of organic compounds.

Description

Asymmetric benzo phenanthro-three furans/thiophene and derivatives and preparation method
Technical field
The present invention relates to novel organic photoelectrical material field, specifically a kind of asymmetric benzo phenanthro-three furans/thiophene and derivatives and preparation method and application.
Background technology
There is the molecule of larger Pi-conjugated systems, as the inert material in organic electro-optic device, be widely used in organic semiconductor in recent years.As Organic Light Emitting Diode (OLEDs), organic field effect tube (OFETs), organic solar batteries (OPVs) and sensor.Diversified aromatic structure or heterocycle structure obtain application in organic semi-conductor development.Such as, linear polyphenyl division center, namely so-called polycyclic aromatic hydrocarbon, shows very high performance in the application of organic field effect tube.
Recently, in the development of successful semiconductor material, furans and thiophene, as representational heterocycle structure, compare pyrrole ring structure, want more less to their research.This point may be the unstable chemcial property due to furans and thiophene; Such as, furans in [4+2] Diels-Alder reacts as reaction conditions during diene, many than pyrroles's gentleness.But meanwhile, the aromaticity that furans is lower also may make it in the photoelectric material of structure based on furans, produces different Electronic Performances.Scott in 2015 reports and synthesize polysubstituted asymmetric triphenylene (H.Cho by O-methoxy bromobenzene under DDQ effect, L.T.Scott, TetrahedronLett.2015,56,3458-3462), Zhao in 2005 can be clear etc. reports discotic mesogenic derivative (K.-Q.Zhao, B.Q.Wang, the P.Hu of the symmetrical and asymmetric benzophenanthrene structure of synthesis under iron(ic) chloride effect, Q.Li, Chin.J.Chem.2005,23,767-774).Takimiya in 2012 etc. report the synthetic method of benzo two furans and thiophene, naphtho-two furans and thiophene and anthra two furans and thiophene etc., and it is applied to the performance study (M.Nakano of materials chemistry aspect, H.Mori, S.Shinamura, K.Takimiya, Chem.Mater.2012,24,190-198), equally report two molecule aphthofurans by furan nucleus at Takimiya in 2012 etc. to connect, its building-up process, and the research (K.Niimi of application in organic semiconductor and performance, H.Mori, E.Miyazaki, I.Osaka, H.Kakizoe, K.Takimiya, C.Adachi, Chem.Commun.2012, 48, 5892-5894), Takimiya in 2011 etc. report again aphthothiophenes and building-up process thereof, and the research (S.Shinamura of application in organic semiconductor and performance, I.Osaka, E.Miyazaki, A.Nakao, M.Yamagishi, J.Takeya, J.Am.Chem.Soc.2011, 133, 5024-5035), Takimiya etc. there was reported anthra [2,3-b:6,7-b'] direct synthesis method of two furans, and it is as application and properties research (M.Nakano, the K.Niimi of active material in organic field effect tube device, E.Miyazaki, I.Osaka, K.Takimiya, J.Org.Chem.2012,77,8099-8111).
To sum up, can learn, linear polyphenyl division center, namely so-called polycyclic aromatic hydrocarbon, shows very high performance in the application of organic field effect tube.And in fused heterocycle, the research for furan nucleus and thiphene ring also gets more and more.And the synthesis of asymmetric benzophenanthrene three furans and asymmetric benzo phenanthro-three thiophene and application thereof, yet there are no report.
Summary of the invention
The object of the invention is to synthesize a kind of novel asymmetric benzo phenanthro-three furans/thiophene and derivatives, and provides the preparation method of asymmetric benzo phenanthro-three furans/thiophene and derivatives.This compound can be used for luminous organic material, and preparation process is simple, and aftertreatment is convenient, mild condition.
The concrete technical scheme realizing the object of the invention is:
A kind of asymmetric benzo phenanthro-three furans/thiophene and derivatives, feature be the ortho position of furans/thiphene ring in this derivant structure with substituting group, the distribution of three furans/thiphene ring is in asymmetric position; Its structure is as follows:
R=hydrogen, alkyl (C8 and following straight chain or the alkyl containing side chain) or phenyl.
A preparation method for said derivative, the method comprises following concrete steps:
A, trimerization
Join in methylene dichloride by iron(ic) chloride under room temperature, add the vitriol oil under nitrogen protection, 2-bromoanisole or 2-chloroneb are slowly added dropwise in ferric chloride Solution, after stirring 2.5h-4.0h, add methyl alcohol, filtering reacting liquid, obtain asymmetrical 2,6,11-tri-bromo-3,7,10-trimethoxy benzo phenanthrene or 2,6, chloro-3,7, the 10-trimethoxy benzos of 11-tri-are luxuriant and rich with fragrance, wherein, the amount of substance ratio of 2-bromoanisole or 2-chloroneb, the vitriol oil and iron(ic) chloride is 1 ︰ 0.08-0.15 ︰ 3.0-5.0;
B, demethylation
2,6,11-tri-bromo-3 is added, 7 in methylene dichloride, 10-trimethoxy benzo phenanthrene or 2,6,11-tri-chloro-3,7,10-trimethoxy benzo is luxuriant and rich with fragrance, argon shield, add boron tribromide at-78 DEG C, room temperature reaction 2h, at 0 DEG C, add saturated sodium bicarbonate solution, filtration obtains 3,7,10-tri-bromo-2,6,11-trihydroxy-benzophenanthrene or 3,7, chloro-2,6, the 11-trihydroxy-benzophenanthrenes of 10-tri-, wherein 2,6,11-tri-bromo-3,7,10-trimethoxy benzo phenanthrene or 2,6, chloro-3,7, the 10-trimethoxy benzos of 11-tri-amount of substance ratio that is luxuriant and rich with fragrance and boron tribromide is 1 ︰ 3.0-7.0;
C, hydroxyl protection:
3,7,10-tri-bromo-2 is added, 6 in methylene dichloride, 11-trihydroxy-benzophenanthrene, adds diacetyl oxide at 0 DEG C, pyridine, room temperature reaction 24h, then the hydrochloric acid reaction that concentration is 4mol/L is added, dichloromethane extraction, removal of solvent under reduced pressure, sherwood oil: ethyl acetate=10:1 column chromatography, obtain 3,7,10-tri-bromo-2,6,11-triacetoxyl group benzophenanthrene, wherein, 3,7, the amount of substance ratio of bromo-2,6, the 11-trihydroxy-benzophenanthrenes of 10-tri-, diacetyl oxide and pyridine is 1 ︰ 50-60 ︰ 30-40; Or by chloro-for 3,7,10-tri-2,6,11-trihydroxy-benzophenanthrene is dissolved in methylene dichloride, adds triethylamine at 0 DEG C, stir, slowly instill trifluoromethanesulfanhydride anhydride under argon gas, room temperature reaction 19h, add water, hydrochloric acid, dichloromethane extraction that concentration is 1mol/L, removal of solvent under reduced pressure, P:A=20:1 column chromatography, obtain 3,7,10-tri-chloro-2,6,11-tri-(trifluoromethanesulfonic acid) benzophenanthrene, wherein, 3,7,10-tri-chloro-2,6,11-trihydroxy-benzophenanthrene, the amount of substance ratio of trifluoromethanesulfanhydride anhydride and triethylamine is 1 ︰ 5.0-7.0:10.0-15.0.
D, Sonogashira linked reaction
Under argon shield, by 3,7, bromo-2,6,11-tri-(acetoxyl group) benzophenanthrenes of 10-tri-or 3,7,10-tri-chloro-2,6,11-tri-(trifluoromethanesulfonic acid) benzophenanthrene, alkynyl, two (triphenyl phosphorus) palladium chloride and cuprous iodide join the N that volume ratio is 1:1, in the mixing solutions of dinethylformamide and Diisopropylamine, mixing solutions concentration is 0.1mol/L, and 80 DEG C of reactions are spent the night, and obtain 3,7,10-tri-alkynyl-2,6,11 3 (ethoxycarbonyl) benzophenanthrene or 3,7, chloro-2,6, the 11-tri-alkynyl benzophenanthrenes of 10-tri-; Wherein, 3,7, bromo-2,6,11-tri-(acetoxyl group) benzophenanthrenes of 10-tri-or 3,7, the amount of substance ratio of 10-tri-chloro-2,6,11-tri-(trifluoromethanesulfonic acid) benzophenanthrene, alkynyl, two (triphenyl phosphorus) palladium chloride and cuprous iodide is 1 ︰ 4.0-6.0 ︰ 0.05-0.25 ︰ 0.1-0.4; The structure of 3,7,10-tri-alkynyl-2,6,11 3 (acetoxyl group) benzophenanthrene is as follows:
The structure of chloro-2,6, the 11-tri-alkynyl benzophenanthrenes of 3,7,10-tri-is as follows:
Trimethyl silicon based, the C8 of R=and following straight chain or the alkyl or phenyl containing side chain in formula;
E, Guan Huan
By 3,7,10-tri-alkynyl-2, it is in the DMF of 20:1 and the mixing solutions of water that 6,11 3 (acetoxyl group) benzophenanthrene joins volume ratio, mixing solutions concentration is 0.2mol/L, add cesium carbonate, 80 DEG C of reaction 18h, obtain asymmetric benzo phenanthro-three Furan and its derivatives; Wherein the amount of substance ratio of 3,7,10-tri-alkynyl-2,6,11 3 (ethoxycarbonyl) benzophenanthrenes and cesium carbonate is 1 ︰ 4.0-10.0;
Or by Na 2s.9H 2o is dissolved in N-Methyl pyrrolidone, and concentration is 0.2-0.4mol/L, stirring at room temperature 15min, adds chloro-2,6, the 11-tri-alkynyl benzophenanthrenes of 3,7,10-tri-, and 80 DEG C are stirred 18h, obtain asymmetric benzo phenanthro-three thiophene and derivatives; Wherein 3,7,10-tri-chloro-2,6,11-tri-alkynyl benzophenanthrene and Na 2s.9H 2the amount of substance ratio of O is 1 ︰ 6.0-15.0;
Asymmetric benzo phenanthro-three Furan and its derivatives has following structure:
Asymmetric benzo phenanthro-three thiophene and derivatives has following structure:
R=hydrogen, C8 and following straight chain or the alkyl or phenyl containing side chain in formula; Described alkynyl is trimethylsilyl acetylene base, 1-pentynyl, 1-hexin base, 1-n-heptylacetylene base, 1-decynyl, 3,3-dimethyl-ethyl acetylene base, phenylacetylene base, 1-cyclopropyl acethlene base.
The synthesis of the above-mentioned trimerization benzophenanthrene related to can reference (C.P.Umesh, A.T.M.Marcelis, H.Zuilhof, LiquidCrystals, 2015, 42, 1269-1279), the synthesis of asymmetric benzo phenanthro-three Furan and its derivatives can reference (M.Nakano, K.Niimi, E.Miyazaki, I.Osaka, K.Takimiya, J.Org.Chem.2012, 77, 8099-8111), the synthesis of asymmetric benzo phenanthro-three thiophene and derivatives can reference (ShojiShinamura, EigoMiyazaki, KazuoTakimiya, J.Org.Chem.2010, 75, 1228 – 1234).Be that starting raw material synthesizes asymmetric benzo phenanthro-three furans/thiophene and derivatives not only process is simple by 2-bromoanisole/2-chloroneb, convenient post-treatment, and also productive rate is high.
Precursor compound 3,7,10-tri-alkynyl-2,6,11 3 (ethoxycarbonyl) benzophenanthrene/3, chloro-2,6, the 11-tri-alkynyl benzophenanthrene compounds of 7,10-tri-are obtained by typical Sonogashira linked reaction.Make catalyzer cuprous iodide with two (triphenylphosphine) palladium chloride and make cocatalyst, alkali made by Diisopropylamine, and with DMF jointly as solvent, be obtained by reacting under the condition of 80 DEG C.This reaction has that catalyst levels is few, reaction conditions is gentle, aftertreatment is simple and productive rate high.
Target compound 2, 7, 12-tri-(hydrogen, propyl group, cyclopropyl, butyl, hexyl, octyl group, the tertiary butyl, phenyl) benzo phenanthro-[2, 3-b:6, 7-b':11, 10-b "] preparation of three furans, at 80 DEG C, alkali is made with cesium carbonate, N, dinethylformamide and water as solvent are obtained by reacting, 2, 7, 12-tri-(hydrogen, propyl group, cyclopropyl, butyl, hexyl, octyl group, the tertiary butyl, phenyl) benzo phenanthro-[2, 3-b:6, 7-b':11, 10-b "] three thiophene are that raw material and nine hydrated sodium sulfides react at 80 DEG C, N-Methyl pyrrolidone obtains as solvent.
In sum, the method that present invention employs simple and fast has synthesized asymmetric benzo phenanthro-three furans/thiophene and derivatives.
The invention provides a kind of extremely easy asymmetric benzophenanthrene of method one-step synthesis, and synthesizing asymmetric benzo phenanthro-three furans/thiophene and derivatives further, a series of asymmetric benzo phenanthro-three furans/thiophene and derivatives of synthesis all can play important application in organic photoelectrical material field.
Accompanying drawing explanation
Fig. 1 is the schema that the present invention synthesizes asymmetric benzo phenanthro-three Furan and its derivatives;
Fig. 2 is the schema that the present invention synthesizes asymmetric benzo phenanthro-three thiophene and derivatives.
Embodiment
Agents useful for same is commercially available prod, and solvent is through conventional drying treatment; Employing reagent illustrates: PE-sherwood oil; DCM-methylene dichloride; EA-ethyl acetate; DMF-N, dinethylformamide, NMP-N-methyl-2-pyrrolidone.
Accompanying drawings 1,2, the invention discloses a kind of asymmetric benzo phenanthro-three furans/thiophene and derivatives, feature is with 2-bromoanisole/2-chloroneb for the asymmetric benzophenanthrene of raw material one-step synthesis, and obtains same asymmetrical target compound through a series of synthesis step.Its preparation is carried out as follows:
(1) 2,6,11-tri-bromo-3,7,10-trimethoxy benzos are luxuriant and rich with fragrance
O-bromo-anisole (3.74g, 20mmol) is dissolved in the CH of 28mL drying 2cl 2in, under Ar gas, slowly instill 60mLCH 2cl 2the FeCl dissolved 3in (10.2g, 63mmol), stirred at ambient temperature 3h, slowly instills 80mL methyl alcohol under ice bath, stirs half an hour, places and spend the night, filtering solids, with a large amount of methyl alcohol and washing, obtain greenish yellow solid 2.44g in refrigerator.Productive rate 65%.
P:A＝5:1,Rf＝0.5,M.p292.0-294.3℃。
1HNMR(500MHz,DMSO-d6)δ8.91(s,1H),8.70(s,2H),7.99(s,3H),4.12(s,3H),4.09(s,3H),4.06(s,3H)。
(2) 2,6,11-tri-chloro-3,7,10-trimethoxy benzos are luxuriant and rich with fragrance
O-chloro-anisole (2.84g, 20mmol) is dissolved in the CH of 28mL drying 2cl 2in, under Ar gas, slowly instill 60mLCH 2cl 2the FeCl dissolved 3in (10.2g, 63mmol), stirred at ambient temperature 3.5h, slowly instills 80mL methyl alcohol under ice bath, stirs half an hour, places and spend the night, filtering solids, with a large amount of methyl alcohol and washing, obtain greenish yellow solid 1.62g in refrigerator.Productive rate 57%.
P:A＝3:1,Rf＝0.5,M.p288.6-291.7℃。
1HNMR(500MHz,CDCl 3)δ8.23(s,1H),8.07(s,1H),8.02(s,1H),7.65(s,1H),7.60(s,1H),7.48(s,1H),4.14(s,3H),4.11(s,3H),4.08(s,3H)。
(3) 3,7,10-tri-bromo-2,6,11-trihydroxy-benzophenanthrenes
Bromo-3,7, the 10-trimethoxy benzo phenanthrene of 2.12g (3.82mmol) 2,6,11-tri-are dissolved in the CH of 40mL drying 2cl 2in, under Ar protection, at-78 DEG C, add BBr 3(1.9mL, 20mmol), room temperature reaction 2h, adds the saturated NaHCO of 15mL 3solution cancellation, revolves and steams except desolventizing, filter, obtain black solid 1.82g, productive rate 92.8%.
P:A＝1:2,Rf＝0.68,M.p>300℃。
1HNMR(500MHz,DMSO-d6)δ10.93(s,1H),10.74(s,1H),10.48(s,1H),8.75(s,2H),8.46(s,1H),7.92(s,1H),7.90(s,1H),7.87(s,1H)。
(4) 3,7,10-tri-chloro-2,6,11-trihydroxy-benzophenanthrenes
The luxuriant and rich with fragrance 1.31g (3.12mmol) of chloro-3,7, the 10-trimethoxy benzos of 2,6,11-tri-is dissolved in 30mL methylene dichloride, and add boron tribromide 1.77mL (18.72mmol) at-78 DEG C, stirring at room temperature 16h, TLC monitor.The saturated NaHCO of 15mL is added after reacting completely 3cancellation is reacted, and filters, and washing is dry, obtains black solid 1.15g.
Productive rate 97.4%.
P:A＝1：1,Rf＝0.55,mp>300℃。
1HNMR(500MHz,DMSO)δ10.86(s,1H),10.68(s,1H),10.43(s,1H),8.63(d,J＝14.5Hz,2H),8.32(s,1H),7.96(s,1H),7.93(s,1H),7.89(s,1H)。
(5) 3,7,10-tri-bromo-2,6,11-tri-(acetoxyl group) benzophenanthrene
CH is added in bromo-2,6, the 11-trihydroxy-benzophenanthrenes of 0.205g (0.4mmol) 3,7,10-tri- 2cl 25mL, Ac 2o2.4mL, pyridine 1.2mL, stirring at room temperature 24h, TLC monitor reaction, and after question response is complete, add 5mL4mol/LHCl cancellation reaction, extraction, P:A=10:1 crosses post, obtains white or light yellow solid 0.201g, productive rate 78.5%.
P:A＝1:1,Rf＝0.80,M.p>300℃。
1HNMR(500MHz,CDCl 3)δ8.46(s,1H),8.41(s,1H),8.09(s,1H),7.92(s,1H),7.80(s,1H),7.60(s,1H),2.51(s,3H),2.49(s,3H),2.45(s,3H)。
(6) 3,7,10-tri-chloro-2,6,11-tri-(trifluoromethanesulfonic acid) benzophenanthrene
1.15g (3.12mmol) 3,7,10-tri-chloro-2,6,11-trihydroxy-benzophenanthrene is dissolved in 60mL methylene dichloride, adds triethylamine 4.2mL (35mmol), slowly instillation trifluoromethanesulfanhydride anhydride 3mL (18mmol) at 0 DEG C, stirring at room temperature 19h, TLC monitor, 10ml water is added, 1MHCl10mL, dichloromethane extraction after reacting completely, revolve steaming, P:A=20:1 crosses post, obtains light yellow solid 2.05g, productive rate 85.1%.
P:A＝5:1，Rf＝0.79,M.p196.8-201.3℃。
1HNMR(500MHz,CDCl 3)δ8.62(s,2H),8.53(s,1H),8.41(s,1H),8.33(s,2H).
(7) benzo phenanthro-[2,3-b:6,7-b':11,10-b "] three furans
DMF 20mL is added, Diisopropylamine 20mL in 1.278mg (2mmol) (5), cuprous iodide 56mg (0.3mmol), two (triphenylphosphine) palladium chloride 208mg (0.3mmol), under Ar environment, instillation trimethylsilyl acetylene 1.28mL (9.0mmol), 80 DEG C of reactions, TLC monitors, after question response is complete, be cooled to room temperature, add water 40mL, extraction into ethyl acetate, revolve steaming, cross post, obtain and do not close ring product.
Add DMF10mL, water 1mL, cesium carbonate 3.910g (12mmol) not closing in ring product, back flow reaction 18h, is cooled to room temperature, adds water 10mL, extraction into ethyl acetate, revolves steaming, crosses post.Obtain yellow solid 425mg.Two step productive rates 32.1%.
P：A＝3：1,Rf＝0.42,M.p203-208℃。
1HNMR(500MHz,DMSO)δ7.73–7.36(m,12H).
13CNMR(125MHz,DMSO)δ137.32,136.72,136.64,134.13,133.96.
(8) 2,7,12-tripropyl benzo phenanthro-s [2,3-b:6,7-b':11,10-b "] three furans
DMF 10mL is added, Diisopropylamine 10mL in 639mg (1mmol) (5), cuprous iodide 28mg (0.15mmol), two (triphenylphosphine) palladium chloride 104mg (0.15mmol), under Ar environment, instillation 1-pentyne 0.44mL (4.5mmol), 80 DEG C of reactions, TLC monitors, after question response is complete, be cooled to room temperature, add water 40mL, extraction into ethyl acetate, revolve steaming, cross post, obtain and do not close ring product.
Add DMF10mL, water 1mL, cesium carbonate 3.910g (12mmol) not closing in ring product, back flow reaction 18h, is cooled to room temperature, adds water 10mL, extraction into ethyl acetate, revolves steaming, crosses post.Obtain yellow solid 208mg.Two step productive rates 43.9%.
P:A＝10：1,Rf＝0.44,M.p274-277℃。
1HNMR(500MHz,CDCl 3)δ8.68(s,2H),8.63(s,1H),8.58(s,1H),8.53(s,2H),6.53(s,3H),2.90–2.80(m,6H),1.84(m,6H),0.96(m,9H).
13CNMR(125MHz,CDCl 3)δ161.79,161.74,161.58,154.74,154.63,154.57,129.14,128.85,127.34,126.98,126.34,126.00,114.05,103.82,103.78,101.87,101.84,101.79,31.48,28.70,27.34,22.48,14.04。
(9) 2,7,12-tri-cyclopropyl benzo phenanthro-s [2,3-b:6,7-b':11,10-b "] three furans
DMF 10mL is added, Diisopropylamine 10mL in 639mg (1mmol) (5), cuprous iodide 28mg (0.15mmol), two (triphenylphosphine) palladium chloride 104mg (0.15mmol), under Ar environment, instillation cyclopropyl acethlene 0.35mL (4.5mmol), 80 DEG C of reactions, TLC monitors, after question response is complete, be cooled to room temperature, add water 40mL, extraction into ethyl acetate, revolve steaming, cross post, obtain and do not close ring product.
Add DMF10mL, water 1mL, cesium carbonate 3.910g (12mmol) not closing in ring product, back flow reaction 18h, is cooled to room temperature, adds water 10mL, extraction into ethyl acetate, revolves steaming, crosses post.Obtain yellow solid 312mg.Two step productive rates 66.6%.
P:A＝5：1,Rf＝0.69,M.p155-157℃。
1HNMR(500MHz,CDCl 3)δ8.61(s,2H),8.55(s,1H),8.51(s,1H),8.45(s,2H),6.51(s,3H),2.14–2.08(m,3H),1.07(t,J＝5.8Hz,15H).
13CNMR(125MHz,CDCl 3)δ162.42,162.34,162.17,154.37,154.26,154.21,129.20,128.95,127.17,126.82,126.38,113.72,113.69,103.69,103.65,103.60,100.35,100.32,9.69,7.55,7.53。
(10) 2,7,12-tributyl benzo phenanthro-s [2,3-b:6,7-b':11,10-b "] three furans
DMF 10mL is added, Diisopropylamine 10mL in 639mg (1mmol) (5), cuprous iodide 28mg (0.15mmol), two (triphenylphosphine) palladium chloride 104mg (0.15mmol), under Ar environment, instillation 1-hexin 0.52mL (4.5mmol), 80 DEG C of reactions, TLC monitors, after question response is complete, be cooled to room temperature, add water 40mL, extraction into ethyl acetate, revolve steaming, cross post, obtain and do not close ring product.
Add DMF10mL, water 1mL, cesium carbonate 3.910g (12mmol) not closing in ring product, back flow reaction 18h, is cooled to room temperature, adds water 10mL, extraction into ethyl acetate, revolves steaming, crosses post.Obtain yellow solid 367mg.Two step productive rates 71.1%.
P:A＝5：1,Rf＝0.8,M.p157.3-158.8℃。
1HNMR(500MHz,CDCl 3)δ8.70(s,2H),8.64(s,1H),8.60(s,1H),8.54(s,2H),6.55(d,J＝5.1Hz,3H),2.86(t,J＝7.4Hz,6H),1.88–1.76(m,6H),1.50(dd,J＝14.6,7.3Hz,6H),1.01(t,J＝7.3Hz,9H).
13CNMR(125MHz,CDCl 3)δ169.15,162.74,154.98,150.39,131.01,130.98,130.25,128.43,128.41,126.27,126.10,125.97,125.18,116.91,116.65,116.25,116.22,114.62,104.29,101.89,95.95,95.80,30.85,29.63,28.41,22.38),22.04,20.98,19.40,13.84,13.68。
(11) 2,7,12-tri-tert benzo phenanthro-s [2,3-b:6,7-b':11,10-b "] three furans
N is added in 639mg (1mmol) (5), dinethylformamide 10mL, Diisopropylamine 10mL, cuprous iodide 28mg (0.15mmol), two (triphenylphosphine) palladium chloride 104mg (0.15mmol), under Ar environment, instillation 3,3-dimethyl-ethyl acetylene 0.55mL (4.5mmol), 80 DEG C of reactions, TLC monitors, after question response is complete, be cooled to room temperature, add water 40mL, and extraction into ethyl acetate revolves steaming, cross post, obtain and do not close ring product.
Add DMF10mL, water 1mL, cesium carbonate 3.910g (12mmol) not closing in ring product, back flow reaction 18h, is cooled to room temperature, adds water 10mL, extraction into ethyl acetate, revolves steaming, crosses post.Obtain yellow solid 255mg.Two step productive rates 49.4%.
P:A＝10：1,Rf＝0.44,M.p178-180℃。
1HNMR(500MHz,CDCl 3)δ8.71(s,2H),8.67(s,1H),8.63(s,1H),8.58(s,2H),6.54(s,3H),1.49(s,27H).
13CNMR(125MHz,CDCl 3)δ169.35,169.31,169.13,154.77,154.63,154.59,129.04,128.74,127.46,127.08,126.32,126.29,125.96,114.21,103.90,99.01,33.25,28.89。
(12) 2,7,12-tri-heptyl benzo phenanthro-s [2,3-b:6,7-b':11,10-b "] three furans
DMF 10mL is added, Diisopropylamine 10mL in 639mg (1mmol) (5), cuprous iodide 28mg (0.15mmol), two (triphenylphosphine) palladium chloride 104mg (0.15mmol), under Ar environment, instillation 1-n-heptylacetylene 0.75mL (4.5mmol), 80 DEG C of reactions, TLC monitors, after question response is complete, be cooled to room temperature, add water 40mL, extraction into ethyl acetate, revolve steaming, cross post, obtain and do not close ring product.
Add DMF10mL, water 1mL, cesium carbonate 3.910g (12mmol) not closing in ring product, back flow reaction 18h, is cooled to room temperature, adds water 10mL, extraction into ethyl acetate, revolves steaming, crosses post.Obtain yellow solid 401mg.Two step productive rates 66.8%.
P:A＝40：1,Rf＝0.58,M.p96-98℃
1HNMR(500MHz,CDCl 3)δ8.67(s,2H),8.61(s,1H),8.57(s,1H),8.52(s,2H),6.52(s,3H),2.84(t,J＝7.5Hz,6H),1.86–1.79(m,6H),1.49–1.43(m,6H),1.39(dd,J＝14.4,6.4Hz,6H),1.33(s,6H),0.92(t,J＝6.1Hz,9H).
13CNMR(125MHz,CDCl 3)δ161.78,161.72,161.57,154.74,154.62,154.56,129.13,128.84,127.34,126.98,126.33,125.99,114.02,103.81,103.76,101.85,101.82,101.78,31.81,29.29,29.10,28.73,27.66,27.65,22.69,14.13。
(13) 2,7,12-tri-n-octyl benzo phenanthro-s [2,3-b:6,7-b':11,10-b "] three furans
DMF 10mL is added, Diisopropylamine 10mL in 639mg (1mmol) (5), cuprous iodide 28mg (0.15mmol), two (triphenylphosphine) palladium chloride 104mg (0.15mmol), under Ar environment, instillation 1-decine 0.81mL (4.5mmol), 80 DEG C of reactions, TLC monitors, after question response is complete, be cooled to room temperature, add water 40mL, extraction into ethyl acetate, revolve steaming, cross post, obtain and do not close ring product.
Add DMF10mL, water 1mL, cesium carbonate 3.910g (12mmol) not closing in ring product, back flow reaction 18h, is cooled to room temperature, adds water 10mL, extraction into ethyl acetate, revolves steaming, crosses post.Obtain yellow solid 425mg.Two step productive rates 62.1%.
P:A＝40：1,Rf＝0.78,M.p97.5-98.6℃。
1HNMR(500MHz,CDCl 3)δ8.69(d,J＝4.6Hz,2H),8.63(d,J＝4.0Hz,1H),8.58(s,1H),8.53(d,J＝2.6Hz,2H),6.54(s,3H),2.85(t,J＝7.4Hz,6H),1.88–1.78(m,6H),1.46(t,J＝14.3Hz,6H),1.35(ddd,J＝25.6,13.4,5.7Hz,24H),0.90(t,J＝6.7Hz,9H). 13CNMR(125MHz,CDCl 3)δ161.78,161.73,161.57,154.72,154.61,154.55,129.12,128.83,127.32,126.96,126.32,125.98,114.02,103.80,103.75,101.83,101.81,101.76,31.87,29.36,29.29,29.23,28.71,27.64,22.67,14.10。
(14) 2,7,12-phenyl benzo phenanthro-s [2,3-b:6,7-b':11,10-b "] three furans
DMF 10mL is added, Diisopropylamine 10mL in 639mg (1mmol) (5), cuprous iodide 28mg (0.15mmol), two (triphenylphosphine) palladium chloride 104mg (0.15mmol), under Ar environment, instillation phenylacetylene 0.49mL (4.5mmol), 80 DEG C of reactions, TLC monitors, after question response is complete, be cooled to room temperature, add water 40mL, extraction into ethyl acetate, revolve steaming, cross post, obtain and do not close ring product.
Add DMF10mL, water 1mL, cesium carbonate 3.910g (12mmol) not closing in ring product, back flow reaction 18h, is cooled to room temperature, adds water 10mL, extraction into ethyl acetate, revolves steaming, crosses post.Obtain yellow solid 425mg.Two step productive rates 62.1%.
P:A＝5：1,Rf＝0.74,M.p189-191℃。
1HNMR(500MHz,CDCl 3)δ8.67–8.44(m,6H),7.91(s,5H),7.47(s,5H),7.38(s,5H),7.11(s,1H),7.08(s.1H),7.03(S,1H)。
(15) benzo phenanthro-[2,3-b:6,7-b':11,10-b "] three thiophene
To 774mg (1mmol) 3,7,10-tri-chloro-2, DMF 10mL is added in 6,11-tri-(trifluoromethanesulfonic acid) benzophenanthrene, triethylamine 10mL, two (triphenylphosphine) palladium chloride 104mg (0.15mmol), cuprous iodide 56mg (0.3mmol), slowly adds trimethylsilyl acetylene 0.85mL (6.0mmol) under a nitrogen, 40 DEG C of reaction 20h, TLC monitors, and after reacting completely, adds water 4mL, 1MHCl4mL dichloromethane extraction, revolve steaming, cross post, obtain yellow oil product 147mg.
1.153gNa 2s.9H 2o (4.8mmol) is dissolved in 25mLNMP, stirring at room temperature 15min, adds yellow solid 100mg (0.18mmol), 80 DEG C are stirred 18h, TLC monitoring reaction, after question response is complete, be cooled to room temperature, add 100ml saturated ammonium chloride solution, filter, obtain thick product, thick product is dissolved in ethyl acetate, revolves steaming, cross post, obtain yellow solid 28mg, productive rate 10%.
P:A＝3：1,Rf＝0.34,Mp214-217℃。
1HNMR(500MHz,CDCl 3)δ7.68(dd,J＝11.3,8.0Hz,5H),7.55(t,J＝6.9Hz,3H),7.47(d,J＝6.2Hz,4H)。
(16) 2,7,12-tri-n-propyl benzo phenanthro-s [2,3-b:6,7-b':11,10-b "] three thiophene
To 774mg (1mmol) 3,7, N is added in 10-tri-chloro-2,6,11-tri-(trifluoromethanesulfonic acid) benzophenanthrene, dinethylformamide 10mL, triethylamine 10mL, two (triphenylphosphine) palladium chloride 104mg (0.15mmol), cuprous iodide 56mg (0.3mmol), slowly add 1-pentyne 0.44mL (4.5mmol) under a nitrogen, 40 DEG C of reaction 20h, TLC monitorings, after reacting completely, add water 4mL, 1MHCl4mL, dichloromethane extraction, revolves steaming, cross post, obtain yellow product 398mg.
1.793gNa 2s.9H 2o (7.46mmol) is dissolved in 25mLNMP, stirring at room temperature 15min, adds yellow solid 300mg (0.57mmol), 80 DEG C are stirred 18h, TLC monitoring reaction, after question response is complete, be cooled to room temperature, add 100mL saturated ammonium chloride solution, filter, obtain thick product, thick product is dissolved in ethyl acetate, revolves steaming, cross post, obtain yellow solid 215mg, productive rate 54.5%.
P:A＝10:1,Rf＝0.61,M.p109.3-111.6℃
1HNMR(500MHz,CDCl 3)δ8.86(s,1H),8.82(s,2H),8.75(s,2H),8.71(s,1H),7.10(d,J＝4.6Hz,3H),2.94(t,J＝6.8Hz,6H),1.86(dd,J＝14.2,7.1Hz,6H),1.08(t,J＝7.2Hz,9H).
13CNMR(125MHz,CDCl 3)δ147.92,147.89,147.80,139.67,138.92,138.87,127.34,127.27,127.02,126.76,126.51,126.43,120.45,120.43,116.44,116.34,116.04,115.95,33.17,24.16,13.63。
(17) 2,7,12-tri-cyclopropyl benzo phenanthro-s [2,3-b:6,7-b':11,10-b "] three thiophene
To 326mg (0.42mmol) 3,7, N is added in 10-tri-chloro-2,6,11-tri-(trifluoromethanesulfonic acid) benzophenanthrene, dinethylformamide 5mL, triethylamine 5mL, two (triphenylphosphine) palladium chloride 44mg (0.063mmol), cuprous iodide 23mg (0.126mmol), slowly add cyclopropyl acethlene 0.147mL (1.9mmol) under a nitrogen, 40 DEG C of reaction 20h, TLC monitorings, after reacting completely, add water 2mL, 1MHCl2mL, dichloromethane extraction, revolves steaming, cross post, obtain white solid 102mg.
1.153gNa 2s.9H 2o (4.8mmol) is dissolved in 15mLNMP, stirring at room temperature 15min, adds white solid 102mg (0.19mmol), 80 DEG C are stirred 18h, TLC monitoring reaction, after question response is complete, be cooled to room temperature, add 70mL saturated ammonium chloride solution, filter, obtain thick product, thick product is dissolved in ethyl acetate, revolves steaming, cross post, obtain yellow solid 75mg, productive rate 47.2%.
P:A＝10:1,Rf＝0.40,Mp190.2-194.0℃。
1HNMR(500MHz,CDCl 3)δ8.76(s,1H),8.70(s,2H),8.64(s,2H),8.59(s,1H),7.11–6.98(m,3H),3.72(q,J＝7.0Hz,4H),1.24(t,J＝7.0Hz,6H),1.12(d,J＝7.3Hz,5H).
13CNMR(125MHz,CDCl 3)δ150.74,150.71,150.63,139.72,139.69,139.67,138.11,138.08,138.04,127.40,127.36,127.09,126.73,126.45,126.41,118.69,116.22,116.17,116.03,115.97,18.45,12.39,10.20。
(18) 2,7,12-tributyl benzo phenanthro-s [2,3-b:6,7-b':11,10-b "] three thiophene
To 774mg (1mmol) 3,7, N is added in 10-tri-chloro-2,6,11-tri-(trifluoromethanesulfonic acid) benzophenanthrene, dinethylformamide 10mL, triethylamine 10mL, two (triphenylphosphine) palladium chloride 104mg (0.15mmol), cuprous iodide 56mg (0.3mmol), slowly add 1-hexin 0.51mL (4.5mmol) under a nitrogen, 40 DEG C of reaction 20h, TLC monitorings, after reacting completely, add water 4mL, 1MHCl4mL, dichloromethane extraction, revolves steaming, cross post, obtain yellow solid 433mg.
1.153gNa 2s.9H 2o (4.8mmol) is dissolved in 15mLNMP, stirring at room temperature 15min, adds yellow solid 433mg (0.71mmol), 80 DEG C are stirred 18h, TLC monitoring reaction, after question response is complete, be cooled to room temperature, add 75mL saturated ammonium chloride solution, filter, obtain thick product, thick product is dissolved in ethyl acetate, revolve steaming, cross post, obtain yellow solid 186mg.Productive rate 33%.
P:A＝20:1,Rf＝0.53,mp170.0-172.0℃。
1HNMR(500MHz,CDCl 3)δ8.77(m,6H),7.10(d,J＝1.6Hz,3H),3.04–2.92(m,6H),1.82-1.80(m,6H),1.54–1.46(m,6H),1.02(t,J＝7.2Hz,9H).
13CNMR(125MHz,CDCl 3)δ148.19,139.71,138.88,127.38,127.07,126.80,126.51,120.32,116.38,116.07,99.97,33.10,30.84,22.36,13.91。
(19) 2,7,12-tri-tert benzo phenanthro-s [2,3-b:6,7-b':11,10-b "] three thiophene
To 774mg (1mmol) 3,7,10-tri-chloro-2,6, N is added in 11-tri-(trifluoromethanesulfonic acid) benzophenanthrene, dinethylformamide 10mL, triethylamine 10mL, two (triphenylphosphine) palladium chloride 104mg (0.15mmol), cuprous iodide 56mg (0.3mmol), slowly add 3,3-dimethyl-ethyl acetylene 0.55mL (4.5mmol) under a nitrogen, 40 DEG C of reaction 20h, TLC monitors, after reacting completely, add water 4ml, 1MHCl4mL, dichloromethane extraction, revolve steaming, cross post, obtain yellow product 428mg.1.153gNa 2s.9H 2o (4.8mmol) is dissolved in 20mLNMP, stirring at room temperature 15min, adds yellow solid 82mg (0.14mmol), 80 DEG C are stirred 18h, TLC monitoring reaction, after question response is complete, be cooled to room temperature, add 100ml saturated ammonium chloride solution, filter, obtain thick product, thick product is dissolved in ethyl acetate, revolves steaming, cross post, obtain pale solid 67mg, productive rate 62%.
P:A＝20:1,Rf＝0.69,M.p292.9-293.9℃。
1HNMR(500MHz,CDCl 3)δ8.91(s,1H),8.86(s,2H),8.82(s,2H),8.77(s,1H),7.19(s,3H),1.55(s,27H).
13CNMR(125MHz,CDCl 3)δ159.65,159.54,139.72,139.67,139.65,138.74,138.70,138.65,127.48,127.40,127.14,126.99,126.71,126.64,117.69116.81,116.70,116.17,116.06,35.25,32.15。
(20) 2,7,12-tri-n-heptyl benzo phenanthro-s [2,3-b:6,7-b':11,10-b "] three thiophene
To 354mg (0.46mmol) 3,7, N is added in 10-tri-chloro-2,6,11-tri-(trifluoromethanesulfonic acid) benzophenanthrene, dinethylformamide 5mL, triethylamine 5mL, two (triphenylphosphine) palladium chloride 48mg (0.07mmol), cuprous iodide 26mg (0.14mmol), slowly add 1-n-heptylacetylene 0.34mL (2.1mmol) under a nitrogen, 40 DEG C of reaction 20h, TLC monitorings, after reacting completely, add water 4ml, 1MHCl4mL, dichloromethane extraction, revolves steaming, cross post, obtain yellow oil product 218mg.
1.153gNa 2s.9H 2o (4.8mmol) is dissolved in 15mLNMP, stirring at room temperature 15min, adds yellow solid 218mg (0.32mmol), 80 DEG C are stirred 18h, TLC monitoring reaction, after question response is complete, be cooled to room temperature, add 75mL saturated ammonium chloride solution, filter, obtain thick product, thick product is dissolved in ethyl acetate, revolves steaming, cross post, obtain yellow solid 166mg, productive rate 52%.
P:A＝100:1，Rf＝0.48,mp99.7-100.5℃。
1HNMR(500MHz,CDCl 3)δ8.93–8.62(m,6H),7.09(s,3H),2.97-2.96(m,6H),1.89–1.80(m,6H),1.49-1.46(m,6H),1.42-1.36(m,18H),0.95-0.94(m,9H). 13CNMR(125MHz,CDCl 3)δ148.23,139.66,138.92,127.32,127.01,126.78,126.46,120.31,116.37,116.01,31.86,31.16,31.02,29.27,29.15,22.72,14.15。
(21) 2,7,12-tri-n-octyl benzo phenanthro-s [2,3-b:6,7-b':11,10-b "] three thiophene
To 774mg (1mmol) 3,7, N is added in 10-tri-chloro-2,6,11-tri-(trifluoromethanesulfonic acid) benzophenanthrene, dinethylformamide 10ml, triethylamine 10mL, two (triphenylphosphine) palladium chloride 104mg (0.15mmol), cuprous iodide 56mg (0.3mmol), slowly add 1-decine 0.81mL (4.5mmol) under a nitrogen, 40 DEG C of reaction 20h, TLC monitorings, after reacting completely, add water 4ml, 1MHCl4mL, dichloromethane extraction, revolves steaming, cross post, obtain yellow oil product 607mg.
1.793gNa 2s.9H 2o (7.46mmol) is dissolved in 25mLNMP, stirring at room temperature 15min, adds yellow solid 607mg (0.71mmol), 80 DEG C are stirred 18h, TLC monitoring reaction, after question response is complete, be cooled to room temperature, add 100ml saturated ammonium chloride solution, filter, obtain thick product, thick product is dissolved in ethyl acetate, revolves steaming, cross post, obtain yellow solid 315mg, productive rate 43%.
Pure PERf=0.81, M.p97.9-99.5 DEG C.
1HNMR(500MHz,CDCl 3)δ8.87(s,1H),8.83(s,2H),8.76(s,2H),8.71(s,1H),7.18–7.09(m,3H),2.97-2.95(m6H),1.84-1.82(m,6H),1.48(d,J＝5.8Hz,6H),1.40–1.28(m,24H),0.93(t,J＝6.4Hz,9H).
13CNMR(125MHz,CDCl 3)δ148.20,139.68,138.95,127.38,127.06,126.80,126.51,120.30,116.38,116.08,31.93,31.16,31.02,29.45,29.32,22.72,14.15。
(22) 2,7,12-triphenyl benzo phenanthro-s [2,3-b:6,7-b':11,10-b "] three thiophene
To 387mg (0.5mmol) 3,7, N is added in 10-tri-chloro-2,6,11-tri-(trifluoromethanesulfonic acid) benzophenanthrene, dinethylformamide 5mL, triethylamine 5mL, two (triphenylphosphine) palladium chloride 52mg (0.075mmol), cuprous iodide 28mg (0.15mmol), slowly add phenylacetylene 0.247mL (2.25mmol) under a nitrogen, 40 DEG C of reaction 20h, TLC monitorings, after reacting completely, add water 2mL, 1MHCl2mL, dichloromethane extraction, revolves steaming, cross post, obtain yellow oil product 216mg.
1.793gNa 2s.9H 2o (7.46mmol) is dissolved in 25mLNMP, stirring at room temperature 15min, adds yellow solid 216mg (0.34mmol), 80 DEG C are stirred 18h, TLC monitoring reaction, after question response is complete, be cooled to room temperature, add 100mL saturated ammonium chloride solution, filter, obtain thick product, thick product is dissolved in ethyl acetate, revolves steaming, cross post, obtain yellow solid 155mg, productive rate 49.6%.
P:A＝5：1.Rf＝0.65,Mp149.6-152.1℃。
1HNMR(500MHz,DMSO)δ7.70(d,J＝7.6Hz,8H),7.55(s,4H),7.44(t,J＝7.4Hz,8H),7.33(t,J＝7.3Hz,4H).
13CNMR(125MHz,CDCl 3)δ143.00,133.93,129.64,128.23,125.66,125.43。

Claims (2)

1. asymmetric benzo phenanthro-three furans/thiophene and derivatives, it is characterized in that the ortho position of furans/thiphene ring in this derivant structure is with substituting group, the distribution of three furans/thiphene ring is in asymmetric position; It has following structure:
R=hydrogen, C8 and following straight chain or the alkyl or phenyl containing side chain in formula.
2. a preparation method for derivative described in claim 1, is characterized in that the method comprises following concrete steps:
A, trimerization
Join in methylene dichloride by iron(ic) chloride under room temperature, add the vitriol oil under nitrogen protection, 2-bromoanisole or 2-chloroneb are slowly added dropwise in ferric chloride Solution, after stirring 2.5h-4.0h, add methyl alcohol, filtering reacting liquid, obtain asymmetrical 2,6,11-tri-bromo-3,7,10-trimethoxy benzo phenanthrene or 2,6, chloro-3,7, the 10-trimethoxy benzos of 11-tri-are luxuriant and rich with fragrance, wherein, the amount of substance ratio of 2-bromoanisole or 2-chloroneb, the vitriol oil and iron(ic) chloride is 1 ︰ 0.08-0.15 ︰ 3.0-5.0;
B, demethylation
2,6,11-tri-bromo-3 is added, 7 in methylene dichloride, 10-trimethoxy benzo phenanthrene or 2,6,11-tri-chloro-3,7,10-trimethoxy benzo is luxuriant and rich with fragrance, argon shield, add boron tribromide at-78 DEG C, room temperature reaction 2h, at 0 DEG C, add saturated sodium bicarbonate solution, filtration obtains 3,7,10-tri-bromo-2,6,11-trihydroxy-benzophenanthrene or 3,7, chloro-2,6, the 11-trihydroxy-benzophenanthrenes of 10-tri-, wherein 2,6,11-tri-bromo-3,7,10-trimethoxy benzo phenanthrene or 2,6, chloro-3,7, the 10-trimethoxy benzos of 11-tri-amount of substance ratio that is luxuriant and rich with fragrance and boron tribromide is 1 ︰ 3.0-7.0;
C, hydroxyl protection
3,7,10-tri-bromo-2 is added in methylene dichloride, 6,11-trihydroxy-benzophenanthrene, adds diacetyl oxide at 0 DEG C, pyridine, room temperature reaction 24h, then adds the hydrochloric acid reaction that concentration is 4mol/L, dichloromethane extraction, removal of solvent under reduced pressure, sherwood oil: ethyl acetate=10:1 column chromatography, obtain 3,7,10-tri-bromo-2,6,11-triacetoxyl group benzophenanthrene; Wherein, the amount of substance ratio of bromo-2,6, the 11-trihydroxy-benzophenanthrenes of 3,7,10-tri-, diacetyl oxide and pyridine is 1 ︰ 50-60 ︰ 30-40;
Or by chloro-for 3,7,10-tri-2,6,11-trihydroxy-benzophenanthrene is dissolved in methylene dichloride, adds triethylamine at 0 DEG C, stir, slowly instill trifluoromethanesulfanhydride anhydride under argon gas, room temperature reaction 19h, add water, hydrochloric acid, dichloromethane extraction that concentration is 1mol/L, removal of solvent under reduced pressure, P:A=20:1 column chromatography, obtain 3,7,10-tri-chloro-2,6,11-tri-(trifluoromethanesulfonic acid) benzophenanthrene; Wherein, chloro-2,6, the 11-trihydroxy-benzophenanthrenes of 3,7,10-tri-, the amount of substance ratio of trifluoromethanesulfanhydride anhydride and triethylamine is 1 ︰ 5.0-7.0 ︰ 10.0-15.0;
D, Sonogashira linked reaction
Under argon shield, by 3,7, bromo-2,6,11-tri-(acetoxyl group) benzophenanthrenes of 10-tri-or 3,7,10-tri-chloro-2,6,11-tri-(trifluoromethanesulfonic acid) benzophenanthrene, alkynyl, two (triphenyl phosphorus) palladium chloride and cuprous iodide join the N that volume ratio is 1:1, in the mixing solutions of dinethylformamide and Diisopropylamine, mixing solutions concentration is 0.1mol/L, and 80 DEG C of reactions are spent the night, and obtain 3,7,10-tri-alkynyl-2,6,11 3 (ethoxycarbonyl) benzophenanthrene or 3,7, chloro-2,6, the 11-tri-alkynyl benzophenanthrenes of 10-tri-; Wherein, 3,7, bromo-2,6,11-tri-(acetoxyl group) benzophenanthrenes of 10-tri-or 3,7, the amount of substance ratio of 10-tri-chloro-2,6,11-tri-(trifluoromethanesulfonic acid) benzophenanthrene, alkynyl, two (triphenyl phosphorus) palladium chloride and cuprous iodide is 1 ︰ 4.0-6.0 ︰ 0.05-0.25 ︰ 0.1-0.4;
The structure of 3,7,10-tri-alkynyl-2,6,11 3 (acetoxyl group) benzophenanthrene is as follows:
The structure of chloro-2,6, the 11-tri-alkynyl benzophenanthrenes of 3,7,10-tri-is as follows:
Trimethyl silicon based, the C8 of R=and following straight chain or the alkyl or phenyl containing side chain in formula;
E, Guan Huan
By 3,7,10-tri-alkynyl-2, it is in the DMF of 20:1 and the mixing solutions of water that 6,11 3 (acetoxyl group) benzophenanthrene joins volume ratio, mixing solutions concentration is 0.2mol/L, add cesium carbonate, 80 DEG C of reaction 18h, obtain asymmetric benzo phenanthro-three Furan and its derivatives; Wherein the amount of substance ratio of 3,7,10-tri-alkynyl-2,6,11 3 (ethoxycarbonyl) benzophenanthrenes and cesium carbonate is 1 ︰ 4.0-10.0;
Or Na2S.9H2O is dissolved in N-Methyl pyrrolidone, concentration is 0.2-0.4mol/L, stirring at room temperature 15min, adds chloro-2,6, the 11-tri-alkynyl benzophenanthrenes of 3,7,10-tri-, and 80 DEG C are stirred 18h, obtain asymmetric benzo phenanthro-three thiophene and derivatives; Wherein the amount of substance ratio of 3,7,10-tri-chloro-2,6,11-tri-alkynyl benzophenanthrenes and Na2S.9H2O is 1 ︰ 6.0-15.0;
Asymmetric benzo phenanthro-three Furan and its derivatives has following structure:
Asymmetric benzo phenanthro-three thiophene and derivatives has following structure:
R=hydrogen, C8 and following straight chain or the alkyl or phenyl containing side chain in formula; Described alkynyl is trimethylsilyl acetylene base, 1-pentynyl, 1-hexin base, 1-n-heptylacetylene base, 1-decynyl, 3,3-dimethyl-ethyl acetylene base, phenylacetylene base, 1-cyclopropyl acethlene base.
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