CN110078653A - A kind of 9- phenyl fluorene derivative and its preparation method and application that indoles replaces - Google Patents
A kind of 9- phenyl fluorene derivative and its preparation method and application that indoles replaces Download PDFInfo
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Abstract
The invention discloses the 9- phenyl fluorene derivative that a kind of indoles replaces, general formula is as follows:Wherein, X is aryl, hydrogen, halogen, alkyl, alkoxy；R2For hydrogen, halogen, alkyl, alkoxy；R3For hydrogen, alkyl, alkoxy；R4For hydrogen, halogen, alkyl, alkoxy；R5For hydrogen, alkyl, alkoxy.The 9- phenyl fluorene derivative that indoles provided by the invention replaces, in the preparation process for the 9- phenyl fluorene derivative that indoles replaces, not only raw material is simple and easy to get, reaction condition is milder, and the application field of the 9- phenyl fluorene derivative of indoles substitution is expanded, the 9- phenyl fluorene derivative for preparing indoles substitution for commercialization is laid a good foundation.
Description
Technical field
The invention belongs to technical field of organic synthesis, specifically, being related to a kind of 9- phenyl fluorene derivative that indoles replaces
And its preparation method and application.
Background technique
Fluorenyl compounds are a kind of electroluminescent materials with rigid plane biphenyl structural, since it is with wider energy
Gap and higher photoluminescence efficiency cause the great interest of region of chemistry.There is certain modifiability again in the structure of fluorenes, it can be with
A series of derivatives are obtained by introducing different groups on 2,7 and 9 carbon, many researchers have succeeded
Synthesize many molecular structures novelties, the organic blue light material of fluorenyl of good performance, and is widely applied in OLED, at
For a kind of compound with application prospect.
Wherein this kind of important aromatic compounds of 9,9- diaryl fluorene, because the aryl moiety on the position C9 of fluorenes can
To provide various functions, solubility is such as improved, increases charge carrier mobility etc..Since this kind of compound is in electronic device
Application value, several their methods of synthesis have been developed, wherein the commonly friedel-craft with 9- aryl fluorenyl cation
Reaction is usually generated by corresponding 9- fluorenol.
2006, Huang et al. reported 9- phenyl -9- fluorenol and Electron rich aromatic under the action of boron trifluoride ether
Race's substrate occur friedel-craft reaction, and by Suzuki coupling reaction synthesized it is a series of have various function substituent groups it is non-
The 9,9- diaryl fluorene compound (Org.Lett.20068,3701-3704) of plane conformation.
The same year, Shu seminar report a kind of novel carbazole for blue phosphorescent OLED material of main part/fluorenes hybrid,
The 9- phenyl carbazole of electron rich is reacted with 9- phenyl -9- fluorenol and 9-Fluorenone, synthesizes a series of carbazole/fluorene compounds
(Org.Lett.2006 8,2799-2802)。
2007, Shu seminar reported a kind of fluorenes-triphenylamine hybrid, this be it is a kind of containing triphenylamine core and its
Periphery contains the material of main part there are three 9- phenyl -9- fluorenyl, is effectively synthesized by friedel-craft substitution reaction
(Adv.Funct.Mater.2007,17,3514–3520)。
2017, Klumpp et al. was reported under this super acids effect of trifluoromethanesulfonic acid, the heterocycle that xenyl replaces
Ketone synthesizes 9,9- diaryl fluorene compound by cyclisation and arylating, and proposes and be related to the mechanism of super electrophilic intermediate
(J.Org.Chem.201782,6044-6053)。
In conclusion 9,9- diaryl fluorene derivatives have widely due to the particularity of its structure in organic electronic device
Application value, polymer also have become a kind of extremely important and are thought most to be hopeful commercialized blue light material by many scholars
Material.
Summary of the invention
The first purpose of the invention is to provide the 9- phenyl fluorene derivatives that a kind of indoles replaces.
A second object of the present invention is to provide a kind of preparation methods of 9- phenyl fluorene derivative that the indoles replaces.
Third object of the present invention is to provide a kind of purposes of 9- phenyl fluorene derivative that the indoles replaces.
To achieve the goals above, The technical solution adopted by the invention is as follows:
The first aspect of the invention provides a kind of 9- phenyl fluorene derivative that indoles replaces, and general formula is shown in formula I:
Wherein,
X is aryl, hydrogen, halogen, alkyl, alkoxy；
R2For hydrogen, halogen, alkyl, alkoxy；
R3For hydrogen, alkyl, alkoxy；
R4For hydrogen, halogen, alkyl, alkoxy；
R5For hydrogen, alkyl, alkoxy.
Preferably, the 9- phenyl fluorene derivative general formula that the indoles replaces is shown in formula I:
Wherein, X be methyl,One of,Indicate link position；
R1For aryl, hydrogen, halogen, alkyl, alkoxy；
R2For hydrogen, halogen, alkyl, alkoxy；
R3For hydrogen, alkyl；
R4For hydrogen, halogen, alkyl, alkoxy；
R5For hydrogen.
It is furthermore preferred that in the Formulas I,
Wherein, X be methyl,One of,Indicate link position；
R1For hydrogen, methyl, methoxyl group, fluorine, chlorine, bromine, phenyl, tert-butyl, trifluoromethyl；
R2For hydrogen, methyl, methoxyl group, fluorine, chlorine, bromine, tert-butyl, trifluoromethyl；
R3For hydrogen, methyl；
R4For hydrogen, fluorine, chlorine, bromine；
R5For hydrogen.
Most preferably, the structure for the 9- phenyl fluorene derivative that the indoles replaces is as follows:
The second aspect of the invention provides a kind of preparation method of 9- phenyl fluorene derivative that the indoles replaces, packet
Include following steps:
X be methyl,One of,Indicate link position；
R1For hydrogen, methyl, methoxyl group, fluorine, chlorine, bromine, phenyl, tert-butyl, trifluoromethyl；
R2For hydrogen, methyl, methoxyl group, fluorine, chlorine, bromine, tert-butyl, trifluoromethyl；
R3For hydrogen, methyl；
R4For hydrogen, fluorine, chlorine, bromine；
R5For hydrogen；
It is 1:(1.1~2 by molar ratio): the compound II of (0.01~0.1), compound III, catalyst trifluoromethanesulfonic acid
Scandium is dissolved in solvent, and 1~48h is reacted under conditions of temperature is 50~80 DEG C, is cooled to room temperature, and removes solvent, and column chromatography mentions
The pure 9- phenyl fluorene derivative for obtaining the indoles and replacing.
The solvent is methylene chloride, methanol.
The compound II, compound III, catalyst trifluoromethanesulfonic acid scandium molar ratio be 1:1.2:0.08.
The third aspect of the invention provides a kind of 9- phenyl fluorene derivative of indoles substitution in organic electronic device
Application in part.
Due to the adoption of the above technical scheme, the present invention has the following advantages and beneficial effects:
The 9- phenyl fluorene derivative that indoles provided by the invention replaces, in the preparation for the 9- phenyl fluorene derivative that indoles replaces
In the process, not only raw material is simple and easy to get, and reaction condition is milder, catalyst trifluoromethanesulfonic acid scandium recoverable, and expands
The application field for the 9- phenyl fluorene derivative that indoles replaces, the 9- phenyl fluorene derivative for preparing indoles substitution for commercialization are established
Basis.
The 9- phenyl fluorene derivative that indoles provided by the invention replaces can be used as the potential organic electroluminescence material of synthesis
Material, and it is easily prepared.
Detailed description of the invention
Fig. 1 is the fluorescence spectrum schematic diagram for the 9- phenyl fluorene derivative that the indoles of preparation of the embodiment of the present invention replaces.
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection scope of invention.
The specifications and models of agents useful for same of the present invention, purity, purchase producer are as shown in table 1:
Table 1
| Reagent name | Producer | Purity | Specification |
| Petroleum ether | The upper smooth Science and Technology Co., Ltd. of Haitai | AR | 25L |
| Methylene chloride | The upper smooth Science and Technology Co., Ltd. of Haitai | >=99.5% | 25L |
| Ethyl acetate | Sai Mo flies scientific and technological (China) Co., Ltd of generation that | 99%+ | 25L |
| Indoles | The upper smooth Science and Technology Co., Ltd. of Haitai | 99% | 25g |
| 7- bromine Fluorenone | Shanghai Di Bai chemicals Technology Co., Ltd. | 97% | 1g |
| 6- bromo indole | Shanghai Bepharm Science & Technology Co., Ltd. | 98% | 1g |
| 4- chloro-indole | Shanghai Bepharm Science & Technology Co., Ltd. | 98% | 1g |
| 5- trifluoro methyl indole | Shanghai Bepharm Science & Technology Co., Ltd. | 97% | 250mg |
| 4- fluoro indole | Chinese mugwort lookes at (Shanghai) Chemical Industry Science Co., Ltd | 98% | 1g |
| 5- methyl indol | The upper smooth Science and Technology Co., Ltd. of Haitai | 98%+ | 1g |
| 7- methyl indol | Shanghai Di Bai chemicals Technology Co., Ltd. | >=98% | 1g |
| N- methyl indol | The upper smooth Science and Technology Co., Ltd. of Haitai | 98%+ | 5g |
| 5- bromo indole | The upper smooth Science and Technology Co., Ltd. of Haitai | 98%+ | 25g |
Compound used therefor II-1~II-6 of the present invention, II-8, II-10 preparation method the following steps are included:
Substituted phenyl-bromide and magnesium are using anhydrous tetrahydro furan as solvent, using elemental iodine as initiator, under the conditions of temperature is 50 DEG C,
Grignard reagent is made in reaction 4 hours.9-Fluorenone will be replaced to be dissolved in anhydrous tetrahydro furan again, it is slow by constant pressure funnel
It is added in grignard reagent, under the conditions of temperature is 50 DEG C, reacts 12 hours, be cooled to room temperature, remove solvent, column Chromatographic purification obtains
Obtain compound II.
Embodiment 1
By 9- phenyl -9- fluorenol (compound ii -1,0.25mmol, 1 equivalent) and indoles (compound III -1,0.3mmol,
1.2 equivalents) it is placed in the reaction tube of 50mL, while trifluoromethanesulfonic acid scandium ([Sc (OTf) is added3], 0.02mmol, 0.08 works as
Amount), add 2mL methylene chloride (CH2Cl2) as solvent, temperature is reacted 4 hours under conditions of being 60 DEG C, it is cooled to room temperature,
It is spin-dried for solvent, dry method loading post separation purification (eluent: ethyl acetate/petroleum ether=2:100) obtains the production of white solid target
Compounds I-1, melting range: 169-176 DEG C, yield 99%.1H NMR(400MHz,CDCl3)δ7.88(s,1H),7.78(dt,
J=7.6,1.0Hz, 2H), 7.56 (dt, J=7.6,0.9Hz, 2H), 7.38-7.27 (m, 5H), 7.25-7.18 (m, 5H),
7.17-7.04 (m, 2H), 6.98-6.89 (m, 1H), 6.69 (d, J=2.5Hz, 1H)13C NMR(100MHz,CDCl3)δ
151.88,144.38,139.76,137.23,128.24,127.60,127.37,126.60,125.72,123.05,121.94,
121.85,120.59,120.06,119.22,111.30,60.25.HRMS(ESI-TOF)m/z:[M-H]-Calcd for
C27H18N 356.1439；Found 356.1437.
Embodiment 2
With II -1 in -2 alternate embodiment 1 of compound ii, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=2:100) desired product as white solid compound I-2 is obtained, melting range: 180-184 DEG C, yield 99%.1H
NMR(400MHz,CDCl3) δ 7.74-7.59 (m, 3H), 7.51-7.39 (m, 2H), 7.24 (td, J=7.5,1.1Hz, 2H),
7.19-7.10 (m, 3H), 7.10-6.97 (m, 4H), 6.94-6.79 (m, 3H), 6.52 (d, J=2.5Hz, 1H), 2.19 (s,
3H).13C NMR(100MHz,CDCl3)δ152.13,141.37,139.75,137.21,136.14,128.99,127.63,
127.50,127.32,126.51,125.70,123.06,122.00,121.82,120.63,120.06,119.18,111.33,
59.97,21.06.HRMS(ESI-TOF)m/z:[M-H]-Calcd for C28H20N 370.1596；Found 370.1597.
Embodiment 3
With II -1 in -3 alternate embodiment 1 of compound ii, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=5:100) desired product as white solid compound I-3 is obtained, melting range: 104-117 DEG C, yield 98%.1H
NMR(400MHz,CDCl3) δ 7.81-7.71 (m, 3H), 7.52 (dt, J=7.6,0.9Hz, 2H), 7.32 (td, J=7.5,
1.1Hz, 2H), 7.26-7.15 (m, 5H), 7.14-7.07 (m, 2H), 6.93 (ddd, J=8.1,6.9,1.1Hz, 1H), 6.72
(d, J=8.8Hz, 2H), 6.59 (dd, J=2.7,1.6Hz, 1H), 3.71 (s, 3H)13C NMR(100MHz,CDCl3)δ
158.30,152.21,139.67,137.23,136.49,128.69,127.62,127.33,126.48,125.65,123.03,
121.99,121.83,120.72,120.08,119.20,113.58,111.34,59.61,55.20.HRMS(ESI-TOF)m/
z:[M-H]-Calcd for C28H20NO 386.1545；Found 386.1547.
Embodiment 4
With II -1 in -4 alternate embodiment 1 of compound ii, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=2:100) desired product as white solid compound I-4 is obtained, melting range: 188-192 DEG C, yield 88%.1H
NMR(400MHz,CDCl3) δ 7.83-7.68=(m, 3H), 7.59-7.44 (m, 2H), 7.34 (td, J=7.5,1.1Hz, 2H),
7.30-7.17 (m, 5H), 7.16-7.04 (m, 2H), 6.95 (ddd, J=8.0,6.9,1.1Hz, 1H), 6.86 (t, J=
8.7Hz, 2H), 6.59 (d, J=2.5Hz, 1H)13C NMR(100MHz,CDCl3)δ161.79,151.78,140.15,
139.67,137.26,129.17,127.72,127.54,126.30,125.59,123.04,121.91,120.32,120.18,
119.34,115.03,111.45,59.68.19F NMR(376MHz,CDCl3)δ-116.70.HRMS(ESI-TOF)m/z:[M-
H]-Calcd for C27H17NF 374.1345；Found 374.1346.
Embodiment 5
With II -1 in compound II-5 alternate embodiment 1, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=2:100) desired product as white solid compound I-5 is obtained, melting range: 82-90 DEG C, yield 89%.1H NMR
(400MHz,CDCl3) δ 7.78-7.67 (m, 3H), 7.44 (d, J=7.6Hz, 2H), 7.30-7.20 (m, 3H), 7.16-7.02
(m, 8H), 6.93-6.86 (m, 1H), 6.55 (d, J=2.5Hz, 1H)13C NMR(100MHz,CDCl3)δ150.42,
141.99,138.64,136.17,131.40,127.95,127.34,126.68,126.53,125.16,124.49,122.01,
120.94,120.74,119.13,118.88,118.32,110.39,58.70.HRMS(ESI-TOF)m/z:[M-H]-Calcd
for C27H17NCl390.1050；Found 390.1049.
Embodiment 6
With II -1 in -6 alternate embodiment 1 of compound ii, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=2:100) desired product as white solid compound I-6 is obtained, melting range: 103-110 DEG C, yield 99%.1H
NMR(400MHz,CDCl3) δ 7.70 (d, J=7.7Hz, 3H), 7.47 (d, J=7.6Hz, 2H), 7.26 (t, J=7.6Hz,
2H),7.22–7.18(m,1H),7.16–7.10(m,6H),7.03(s,1H),6.94–6.90(m,1H),6.87–6.79(m,
1H), 6.63-6.59 (m, 1H), 1.18 (t, J=0.9Hz, 9H)13C NMR(100MHz,CDCl3)δ150.99,148.19,
140.11,138.71,136.09,126.45,126.24,126.14,125.44,124.78,124.02,122.11,120.82,
120.71,119.69,118.96,118.07,110.18,58.80,33.29,30.32.HRMS(ESI-TOF)m/z:[M-H]-
Calcd for C31H26N412.2065；Found 412.2064.
Embodiment 7
With II -1 in -7 alternate embodiment 1 of compound ii, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=2:100) desired product as white solid compound I-7 is obtained, melting range: 120-130 DEG C, yield 95%.1H
NMR(400MHz,DMSO-d6) δ 10.92-10.84 (m, 1H), 8.02 (d, J=7.6Hz, 2H), 7.87 (dd, J=8.3,
5.4Hz, 3H), 7.69-7.48 (m, 2H), 7.45-7.23 (m, 7H), 7.20 (d, J=7.3Hz, 2H), 7.08-6.97 (m,
2H), 6.86-6.76 (m, 1H), 6.41 (d, J=15.8Hz, 1H)13C NMR(100MHz,DMSO-d6)δ144.12,
142.56,139.76,134.11,133.66,132.77,131.11,130.31,130.15,130.14,126.29,126.08,
125.07,123.68,117.26,66.12.HRMS(ESI-TOF)m/z:[M-H]-Calcd for C31H20N 406.1596；
Found 406.1597.
Embodiment 8
With II -1 in -8 alternate embodiment 1 of compound ii, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=3:100) desired product as white solid compound I-8 is obtained, melting range: 97-104 DEG C, yield 37%.1H
NMR(400MHz,DMSO-d6) δ 10.99 (d, J=2.6Hz, 1H), 7.95 (dd, J=16.9,7.8Hz, 2H), 7.65-7.56
(m, 2H), 7.49 (d, J=7.6Hz, 1H), 7.44-7.35 (m, 2H), 7.33-7.16 (m, 6H), 7.06-7.00 (m, 1H),
6.83–6.77(m,1H),6.75–6.68(m,2H).13C NMR(100MHz,DMSO-d6)δ159.04,156.52,148.94,
143.85,143.25,142.45,135.77,133.66,133.38,133.29,132.93,132.27,132.12,130.77,
130.64,128.93,127.72,126.27,125.99,125.59,125.48,123.78,122.75,117.27,
65.19.HRMS(ESI-TOF)m/z:[M-H]-Calcd for C27H17NBr 434.0544；Found 434.0545.
Embodiment 9
With II -1 in -9 alternate embodiment 1 of compound ii, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=2:100) desired product as white solid compound I-9 is obtained, melting range: 180-187 DEG C, yield 75%.1H
NMR(400MHz,CDCl3) δ 7.97 (s, 1H), 7.83 (d, J=7.6Hz, 2H), 7.41 (d, J=2.5Hz, 1H), 7.37-
7.32(m,2H),7.25–7.22(m,3H),7.21–7.15(m,2H),7.02–6.95(m,1H),6.67–6.61(m,1H),
6.29 (d, J=8.1Hz, 1H), 1.89 (s, 3H)13C NMR(100MHz,CDCl3)δ153.08,139.55,136.81,
127.56,127.16,125.60,123.95,121.81,121.78,120.21,120.08,119.98,119.18,110.84,
50.28,26.71.HRMS(ESI-TOF)m/z:[M-H]-Calcd for C22H16N 294.1283；Found 294.1281.
Embodiment 10
With II -1 in -10 alternate embodiment 1 of compound ii, other reaction steps, dosage are same as Example 1, temperature
It after being reacted 4 hours under conditions of being 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid
Ethyl ester/petroleum ether=2:100) desired product as white solid compound I-10 is obtained, melting range: 116-126 DEG C, yield 98%.1H NMR(400MHz,CDCl3)δ7.80–7.70(m,3H),7.57–7.50(m,2H),7.36–7.29(m,2H),7.27–7.17
(m, 3H), 7.13-7.03 (m, 3H), 7.00-6.88 (m, 3H), 6.62 (d, J=2.5Hz, 1H), 2.18 (s, 3H), 2.09 (s,
3H).13C NMR(100MHz,CDCl3)δ152.20,141.71,139.73,137.17,136.25,134.78,129.50,
128.54,127.59,127.26,126.55,125.74,125.29,123.04,122.04,121.76,120.77,120.01,
119.13,111.25,59.96,20.02,19.41.HRMS(ESI-TOF)m/z:[M-H]-Calcd for C29H22N
384.1752；Found384.1753.
Embodiment 11
With III -1 in -2 alternate embodiment 1 of compound III, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=2:100) desired product as white solid compound I-11 is obtained, melting range: 221-224 DEG C, yield 99%.1H
NMR(400MHz,CDCl3) δ 7.79-7.76 (m, 2H), 7.75-7.70 (m, 1H), 7.49 (d, J=7.6Hz, 2H), 7.40 (d,
J=1.7Hz, 1H), 7.37-7.32 (m, 2H), 7.26-7.22 (m, 3H), 7.22-7.19 (m, 4H), 7.02 (dd, J=8.6,
1.8Hz, 1H), 6.88 (d, J=8.6Hz, 1H), 6.59 (d, J=2.5Hz, 1H)13C NMR(100MHz,CDCl3)δ
151.55,144.07,139.75,137.98,128.35,127.69,127.57,127.54,126.81,125.61,125.36,
123.62,123.03,122.62,120.93,120.20,115.53,114.25,60.06.HRMS(ESI-TOF)m/z:[M-
H]-Calcd for C27H17NBr 434.0544；Found 434.0542.
Embodiment 12
With III -1 in -3 alternate embodiment 1 of compound III, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=2:100) desired product as white solid compound I-12 is obtained, melting range: 258-262 DEG C, yield 98%.1H
NMR(400MHz,DMSO-d6) δ 11.32 (s, 1H), 7.93 (d, J=7.5Hz, 2H), 7.79-7.60 (m, 1H), 7.44-7.33
(m, 4H), 7.29 (t, J=7.4Hz, 2H), 7.08 (d, J=53.5Hz, 7H), 6.71-6.59 (m, 1H)13C NMR
(100MHz,DMSO-d6)δ151.81,139.59,128.16,127.71,127.25,126.30,126.10,125.62,
124.26,122.58,121.97,121.24,120.34,117.69,111.34,60.27.HRMS(ESI-TOF)m/z:[M-
H]-Calcd for C27H17NCl 390.1050；Found 390.1051.
Embodiment 13
With III -1 in -4 alternate embodiment 1 of compound III, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=2:100) desired product as white solid compound I-13 is obtained, melting range: 249-253 DEG C, yield 99%.1H
NMR(400MHz,DMSO-d6) δ 11.44 (d, J=2.6Hz, 1H), 7.97 (dd, J=7.6,1.1Hz, 2H), 7.55 (d, J=
8.5Hz, 1H), 7.50-7.38 (m, 4H), 7.33-7.22 (m, 8H), 6.96 (d, J=2.5Hz, 1H), 6.87 (s, 1H)13C
NMR(100MHz,DMSO-d6)δ150.96,144.15,139.21,138.56,128.33,127.75,127.68,127.10,
126.84,126.61,126.06,125.38,124.91,123.92,120.51,119.69,119.26,118.95,112.70,
59.51.19F NMR(376MHz,DMSO-d6)δ-58.77.HRMS(ESI-TOF)m/z:[M-H]-Calcd for
C28H17NF3424.1313；Found 424.1312.
Embodiment 14
With III -1 in -5 alternate embodiment 1 of compound III, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=1:100) desired product as white solid compound I-14 is obtained, melting range: 137-147 DEG C, yield: 99%.1H
NMR(400MHz,CDCl3) δ 7.80-7.67 (m, 3H), 7.56-7.52 (m, 2H), 7.34 (td, J=7.5,1.1Hz, 2H),
7.29-7.25 (m, 2H), 7.25-7.22 (m, 1H), 7.22-7.19 (m, 4H), 7.18 (d, J=3.8Hz, 1H), 6.95 (dd, J
=8.3,1.6Hz, 1H), 6.85-6.81 (m, 1H), 6.61 (d, J=2.5Hz, 1H), 2.28 (s, 3H)13C NMR(100MHz,
CDCl3)δ152.04,144.40,139.76,135.57,131.53,130.83,129.82,128.23,127.59,127.33,
126.70,126.56,125.76,123.51,123.23,121.57,120.04,110.96,60.29,21.71.HRMS(EI)
Calcd for C28H21N[M]+m/z:371.1674；Found 371.1678.
Embodiment 15
With III -1 in -6 alternate embodiment 1 of compound III, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=2:100) desired product as white solid compound I-15 is obtained, melting range: 228-229 DEG C, yield 99%.1H
NMR(400MHz,CDCl3) δ 7.83 (s, 1H), 7.79-7.75 (m, 2H), 7.59 (d, J=7.6Hz, 2H), 7.37-7.31 (m,
2H), 7.26 (d, J=1.3Hz, 1H), 7.17 (s, 6H), 7.11-7.06 (m, 2H), 6.74-6.67 (m, 1H), 6.52 (d, J=
2.6Hz,1H).13C NMR(100MHz,CDCl3)δ156.01,151.82,145.78,140.16,139.83,128.13,
127.79,127.35,126.62,126.25,126.01,123.39,122.86,120.05,119.25,115.22,107.53,
105.64,60.16.19F NMR(376MHz,CDCl3)δ-111.68.HRMS(ESI-TOF)m/z:[M-H]-Calcd for
C27H17NF 374.1345；Found 374.1347.
Embodiment 16
With III -1 in -7 alternate embodiment 1 of compound III, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=1:100) desired product as white solid compound I-16 is obtained, melting range: 65-80 DEG C, yield 99%.1H
NMR(400MHz,CDCl3)δ7.80–7.68(m,3H),7.57–7.52(m,2H),7.36–7.31(m,2H),7.30–7.26
(m,2H),7.24–7.22(m,1H),7.22–7.19(m,3H),7.18(s,1H),6.95–6.90(m,2H),6.89–6.83
(m, 1H), 6.64 (d, J=2.5Hz, 1H), 2.40 (s, 3H)13C NMR(100MHz,CDCl3)δ151.92,144.43,
139.77,136.75,128.23,127.62,127.36,126.59,125.97,125.74,122.75,122.42,121.06,
120.40,120.06,119.77,119.41,60.31,16.59.HRMS(ESI-TOF)m/z:[M-H]-Calcd for
C28H20N 370.1596；Found 370.1595.
Embodiment 17
With III -1 in -8 alternate embodiment 1 of compound III, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=2:100) desired product as white solid compound I-17 is obtained, melting range: 220-223 DEG C, yield 99%.1H
NMR(400MHz,CDCl3)δ7.84–7.73(m,3H),7.52–7.46(m,2H),7.38–7.31(m,2H),7.25–7.17
(m, 8H), 7.12 (dd, J=5.2,3.3Hz, 1H), 6.62 (d, J=2.6Hz, 1H)13C NMR(100MHz,CDCl3)δ
151.56,143.82,139.73,135.80,128.40,128.17,127.72,127.56,127.49,126.90,125.65,
124.84,124.27,124.17,120.44,120.18,112.76,112.63,60.07.HRMS(ESI-TOF)m/z:[M-
H]-Calcd for C27H17NBr 434.0544；Found434.0546.
Embodiment 18
With III -1 in -9 alternate embodiment 1 of compound III, other reaction steps, dosage are same as Example 1, and temperature is
It after being reacted 4 hours under conditions of 60 DEG C, is cooled to room temperature, is spin-dried for solvent, dry method loading post separation purifies (eluent: acetic acid second
Ester/petroleum ether=1:100) desired product as white solid compound I-18 is obtained, melting range: 190-196 DEG C, yield 99%.1H
NMR(400MHz,CDCl3)δ7.81–7.74(m,2H),7.59–7.53(m,2H),7.37–7.32(m,2H),7.31–7.27
(m,2H),7.25–7.14(m,7H),7.10–7.05(m,1H),6.97–6.90(m,1H),6.50(s,1H),3.59(s,3H)
.13C NMR(100MHz,CDCl3)δ152.09,144.49,139.72,137.96,128.23,127.72,127.63,
127.34,126.91,126.58,125.75,122.04,121.38,120.06,118.81,118.69,109.41,60.26,
32.64.HRMS(EI)Calcd for C28H21N[M]+m/z:371.1674；Found 371.1676.
Fig. 1 is the fluorescence spectrum schematic diagram for the 9- phenyl fluorene derivative that the indoles of preparation of the embodiment of the present invention replaces, and is chosen
The embodiment of the present invention preparation compound I-1, I-2, I-3, I-4, I-14, I-16, I-17 fluorometric investigation in, excitation wavelength choosing
It is selected as 266nm, surface sweeping range is 200-650nm, sweep spacing 5nm.It can be seen from the figure that all products are near 380nm
There will be a very strong fluorescence emission peak, and peak intensity can be due to the functional group of compound or position of functional group be different
Difference.
The 9- phenyl fluorene derivative that the indoles that the present invention designs and synthesizes replaces is a kind of novel 9,9- diaryl fluorene
Object is closed, as the organic blue light material of fluorenyl and can be applied in OLED organic assembly after modifying, in electroluminescent organic material
There is potential application value.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this patent
Member without departing from the scope of the present invention, when the technology contents using above-mentioned prompt make it is a little change or be modified to
The equivalent embodiment of equivalent variations, but anything that does not depart from the technical scheme of the invention content, it is right according to the technical essence of the invention
Any simple modification, equivalent change and modification made by above embodiments, in the range of still falling within the present invention program.
Claims (8)
1. the 9- phenyl fluorene derivative that a kind of indoles replaces, which is characterized in that general formula is shown in formula I:
Wherein,
X is aryl, hydrogen, halogen, alkyl, alkoxy；
R2For hydrogen, halogen, alkyl, alkoxy；
R3For hydrogen, alkyl, alkoxy；
R4For hydrogen, halogen, alkyl, alkoxy；
R5For hydrogen, alkyl, alkoxy.
2. the 9- phenyl fluorene derivative that indoles according to claim 1 replaces, which is characterized in that the 9- that the indoles replaces
Phenyl fluorene derivative general formula is shown in formula I:
Wherein, X be methyl,One of,Indicate link position；
R1For aryl, hydrogen, halogen, alkyl, alkoxy；
R2For hydrogen, halogen, alkyl, alkoxy；
R3For hydrogen, alkyl；
R4For hydrogen, halogen, alkyl, alkoxy；
R5For hydrogen.
3. the 9- phenyl fluorene derivative that indoles according to claim 2 replaces, which is characterized in that the 9- that the indoles replaces
Phenyl fluorene derivative general formula is shown in formula I:
Wherein, X be methyl,One of,Indicate link position；
R1For hydrogen, methyl, methoxyl group, fluorine, chlorine, bromine, phenyl, tert-butyl, trifluoromethyl；
R2For hydrogen, methyl, methoxyl group, fluorine, chlorine, bromine, tert-butyl, trifluoromethyl；
R3For hydrogen, methyl；
R4For hydrogen, fluorine, chlorine, bromine；
R5For hydrogen.
4. the 9- phenyl fluorene derivative that indoles according to claim 3 replaces, which is characterized in that the 9- that the indoles replaces
The structure of phenyl fluorene derivative is as follows:
5. a kind of preparation method for the 9- phenyl fluorene derivative that the described in any item indoles of Claims 1-4 replace, feature exist
In, comprising the following steps:
X be methyl,One of,Indicate link position；
R1For hydrogen, methyl, methoxyl group, fluorine, chlorine, bromine, phenyl, tert-butyl, trifluoromethyl；
R2For hydrogen, methyl, methoxyl group, fluorine, chlorine, bromine, tert-butyl, trifluoromethyl；
R3For hydrogen, methyl；
R4For hydrogen, fluorine, chlorine, bromine；
R5For hydrogen；
It is 1:(1.1~2 by molar ratio): compound II, compound III, the catalyst trifluoromethanesulfonic acid scandium of (0.01~0.1) are molten
In solvent, 1~48h being reacted under conditions of temperature is 50~80 DEG C, is cooled to room temperature, remove solvent, column Chromatographic purification obtains
Obtain the 9- phenyl fluorene derivative that the indoles replaces.
6. the preparation method for the 9- phenyl fluorene derivative that indoles according to claim 5 replaces, which is characterized in that described molten
Agent is methylene chloride, methanol.
7. the preparation method for the 9- phenyl fluorene derivative that indoles according to claim 5 replaces, which is characterized in that describedization
Close object II, compound III, catalyst trifluoromethanesulfonic acid scandium molar ratio be 1:1.2:0.08.
8. a kind of 9- phenyl fluorene derivative that the described in any item indoles of Claims 1-4 replace is in organic electronic device
Using.
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| CN115611713A (en) * | 2022-07-25 | 2023-01-17 | 广东工业大学 | Synthesis method of 9-benzylated fluorenol derivative |
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| KR20150070928A (en) * | 2013-12-17 | 2015-06-25 | 에스에프씨 주식회사 | An electroluminescent compound and an electroluminescent device comprising the same |
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| CN113072518A (en) * | 2021-04-06 | 2021-07-06 | 上海兆维科技发展有限公司 | Dibenzo azepine derivative and preparation method thereof |
| CN113072518B (en) * | 2021-04-06 | 2022-10-21 | 上海兆维科技发展有限公司 | Dibenzo azepine derivative and preparation method thereof |
| CN115611713A (en) * | 2022-07-25 | 2023-01-17 | 广东工业大学 | Synthesis method of 9-benzylated fluorenol derivative |
| CN115611713B (en) * | 2022-07-25 | 2024-04-02 | 广东工业大学 | Synthesis method of 9-benzylated fluorenol derivative |
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