CN109232169A - A kind of polyaryl replaces fulvalene compound and its synthetic method - Google Patents
A kind of polyaryl replaces fulvalene compound and its synthetic method Download PDFInfo
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Abstract
The present invention provides a kind of polyaryls to replace fulvalene compound and its synthetic method, i.e., different substituents cyclopentadiene is dissolved in organic solvent, adds catalyst aid, after being stirred to react under the conditions of certain temperature, deionized water is added, benefit is extracted with dichloromethane；Extract liquor is dry, and suction filtration obtains filtrate, will obtain crude product after filtrate concentration, evaporation；Crude product is purified by silica gel column chromatography, obtains product after vacuum drying.Such molecule has big pi-conjugated structure, can be used as electron acceptor material and electron transport material, organic photovoltaic devices and in terms of the application potential that has.
Description
Technical field
The invention belongs to technical field of fine, and in particular to a kind of polyaryl replaces fulvalene compound and its synthesis
Method.
Background technique
Fulvalene and its derivative Synthetic Organic Chemistry, organic electroluminescence device, field effect transistor, laser and
The fields such as photovoltaic cell present broad prospect of application.Prior synthesizing method is usually that cyclopentenone or cyclopentadiene is derivative
Object acts in the solution with lithium reagent, then be added iodine ether or be passed through oxygen carry out reaction obtain fulvalene compound；Also have
Document report vacuum flashing pyrolysis dicyclopentadienyl nickel at 950 DEG C prepares 9,10- dihydro fulvalene.These synthetic methods react item mostly
Part harshness, complex steps, product yield are low, and are difficult to isolate and purify.Also have recently document (Synlett, 2016,27,2085-
2090) report can synthesize aphthacene base fluorenyl tetrathiafulvalene under alkaline condition.It is fast with photoelectricity new material industry
Speed development, design synthesizing new fulvalene compound have attracted people greatly to pay close attention to.
Dicyclopentadienyl is typical fulvalene compound, such molecule has big pi-conjugated structure, can be used as electronics by
Body material and electron transport material, organic photovoltaic devices and in terms of the application potential that has；But by
Limit structure stability is poor, synthesis step is more, the reasons such as complicated for operation, and the synthesis report of such compound is actually rare.Qiu Changlong
It is reported under condition of ice bath with Liu Jifeng (Lanzhou University's journal (natural science edition), 1984,20,276-277), uses tetrachloro
Change titanium, triethylamine reacts with Triphenyl-cyclopentadiene and prepares dicyclopentadienyl compound；Okuda et al. (Chem.Ber.1991,
It 124,1575-1577) is reported at -95 DEG C using iron chloride and 1,2,4- tri- (trimethyl silane) cyclopentadienyl group lithium reaction system
Standby dihydro tetrathiafulvalene.The polyaryl for still lacking high yield so far replaces dicyclopentadienyl class fulvalene compound
Synthetic method is even more to be rarely reported to its structure and property Quality Research.
Summary of the invention
The object of the present invention is to provide a kind of polyaryls to replace fulvalene compound and its synthetic method.
Technical solution of the present invention:
A kind of polyaryl substitution fulvalene compound, structural formula is such as shown in (I):
In formula, R is 4- bromophenyl, 4- methoxyphenyl, 4- aminomethyl phenyl, 4- thiophene -2- phenyl, 3,5- dimethoxy benzene
Base, 3,4,5- trimethoxyphenyl, -1 naphthalene of 2- methoxyl group, -1 naphthalene of 4- methoxyl group, -4 phenyl of 4- pyridyl group, phenyl or 4- connection
Phenyl.
A kind of polyaryl replaces the synthetic method of fulvalene compound, and steps are as follows:
Different substituents cyclopentadiene is dissolved in organic solvent, adds catalyst aid, under the conditions of 60~150 DEG C of temperature
It is stirred to react 2h~10h；After reaction, deionized water is added, benefit is extracted with dichloromethane；It is added in extract liquor anhydrous
MgSO4Dry, suction filtration obtains filtrate, will obtain crude product after filtrate concentration, evaporation；Use the mixing of petroleum ether and methylene chloride
As eluant, eluent, crude product is purified by silica gel column chromatography and obtains product after being dried in vacuo solvent.
The different substituents cyclopentadiene is 1,2- diphenyl -4- (4- bromophenyl) -1,3- cyclopentadiene, 1,2- bis-
Phenyl -4- (4- methoxyl group) phenyl -1,3- cyclopentadiene, 1,2- diphenyl -4- (4- methyl) phenyl -1,3- cyclopentadiene, 1,
2- diphenyl -4- (4- thiophene -2- phenyl) -1,3- cyclopentadiene, 1,2- diphenyl -4- (3,5- Dimethoxyphenyl) -1,3-
Cyclopentadiene, 1,2- diphenyl -4- (3,4,5- trimethoxyphenyl) -1,3- cyclopentadiene, 1,2- diphenyl -4- (2- methoxy
- 1 naphthalene of base) -1,3- cyclopentadiene, 1,2- diphenyl -4- (4- methoxy-1-naphthyl) -1,3- cyclopentadiene, 1,2- hexichol
Base -4- (4- pyridyl group -4- phenyl) -1,3- cyclopentadiene, 1,2,4- triphenyl -1,3- cyclopentadiene, 1,2- diphenyl -4-
One of (4- xenyl) -1,3- cyclopentadiene.
The organic solvent is acetonitrile, benzene, toluene, N, N '-dimethyl formamide, dimethyl sulfoxide, in tetrahydrofuran
One kind.
The catalyst aid is nickel chloride, aluminium chloride, titanium chloride, copper chloride, stannic chloride, manganese chloride, triphenylphosphine, two
The mixing of one or more of Phenylphosphine, Phenylphosphine, tetrakis triphenylphosphine palladium, bis- (triphenylphosphine) palladium chlorides.
The molar ratio of the different substituents cyclopentadiene and catalyst aid is 1:0.005~0.35.
Advantages of the present invention and effect are easy can to synthesize more phenyl using catalyst aid to replace fulvalene compound, tool
Have the characteristics that reaction condition mild, green, easy, yield is high, cost of material, process flow, in terms of have
Significant advantage.The compound structure invented is stablized, and suffers from fields such as medicine, organic synthesis intermediate, photoelectric materials good
Good application prospect.
Detailed description of the invention
Fig. 1 is the crystal structure of two (p-bromophenyl) fulvalene of 3,7- dihydro -1,2,5,6- tetraphenyl -4,8-.
Specific embodiment
A specific embodiment of the invention is described below in conjunction with attached drawing and technical solution, but is not limited the scope of the invention.
Embodiment 1
In the round-bottomed flask of 100mL be added 1.0mmol 1,2- diphenyl -4- (4- bromophenyl) -1,3 cyclopentadiene,
0.13mmol NiCl2, 5mL DMF is then added, is persistently stirred to react 5h under the conditions of 90 DEG C, is cooled to room temperature, obtain orange red
Color solution.Solution is added in separatory funnel, 40mL deionized water is added, shakes up, adds 50mL methylene chloride, shake up,
Layering, separates lower layer's organic phase, anhydrous MgSO is added4Dry, suction filtration obtains filtrate；Methylene chloride is filtered using Rotary Evaporators
Orange-yellow crude product is obtained after liquid concentration, evaporation.Using methylene chloride/petroleum ether (1:100) as eluant, eluent, silica gel column chromatography
Method purifies it, be dried in vacuo after obtain product.Yield: 74.2%.Characterize data: MS (API-ES): 742.8；1H NMR
(400MHz,CDCl3)δ(ppm):7.19–6.96(m,24H),6.69(d,4H),3.83(s,4H).13C NMR(500MHz,
CDCl3)δ(ppm):144.06,140.38,140.29,140.12,135.98,135.82,135.47,131.37,129.29,
128.11,128.01,127.60,126.60,126.57,120.39,44.52；Product is four benzene of 3,7- dihydro -1,2,5,6-
Base -4,8- two (p-bromophenyl) fulvalene.Monocrystalline is obtained using solvent diffusion method, and utilizes X-ray single crystal diffraction analysis card
Its structure (Fig. 1) is illustrated.
Structural formula are as follows:
Compound is dissolved in methylene chloride and is configured to 5 × 10-5Mol/L solution, from UV absorption and fluorescence emission spectrum
In it can be seen that the molecule maximum absorption wave a length of 360nm, fluorescence emission peak 453nm.
Embodiment 2
In the round-bottomed flask of 100mL be added 1.0mmol 1,2- diphenyl -4- (4- bromophenyl) -1,3 cyclopentadiene,
0.15mmol PPh3, 5mL DMF is then added, is persistently stirred to react 6h under the conditions of 90 DEG C, is cooled to room temperature, obtains red
Solution.Solution is added in separatory funnel, 40mL deionized water is added, shakes up, adds 50mL methylene chloride, shake up, point
Layer, separates lower layer's organic phase, anhydrous MgSO is added4Dry, suction filtration obtains filtrate；Using Rotary Evaporators by dichloromethane filtrate
Red crude product is obtained after concentration, evaporation.Using methylene chloride/petroleum ether (1:100) as eluant, eluent, silica gel column chromatography pair
It purifies, obtains product after vacuum drying.Yield: 87.2%.Characterize data: MS (API-ES): 742.8；1H NMR
(400MHz,CDCl3)δ(ppm):7.19–6.96(m,24H),6.69(d,4H),3.83(s,4H).13C NMR(500MHz,
CDCl3)δ(ppm):144.06,140.38,140.29,140.12,135.98,135.82,135.47,131.37,129.29,
128.11,128.01,127.60,126.60,126.57,120.39,44.52；Product is four benzene of 3,7- dihydro -1,2,5,6-
Base -4,8- two (p-bromophenyl) fulvalene.
Structural formula are as follows:
By the dichloromethane solution (5 × 10 of compound-5Mol/L) a length of 360nm of maximum absorption wave, fluorescence emission peak are
453nm。
Embodiment 3
In the round-bottomed flask of 100mL be added 1.0mmol 1,2- diphenyl -4- (4- bromophenyl) -1,3 cyclopentadiene,
0.1mmol NiCl2With 0.10mmol PPh3, 5mL DMF is then added, is persistently stirred to react 6h under the conditions of 90 DEG C, is cooled to
Room temperature obtains dark red oil.Product is added in separatory funnel, 40mL deionized water is added, shakes up, adds 50mL
Methylene chloride shakes up, and layering separates lower layer's organic phase, anhydrous MgSO is added4Dry, suction filtration obtains filtrate；Utilize rotary evaporation
Dichloromethane filtrate is concentrated, obtains peony crude product after evaporation by instrument.Using methylene chloride/petroleum ether (1:100) as washing
De- agent, silica gel column chromatography purify it, and obtain product after being dried in vacuo.Yield: 95%.Characterize data: MS (API-ES):
742.8；1H NMR(400MHz,CDCl3)δ(ppm):7.19–6.96(m,24H),6.69(d,4H),3.83(s,4H).13C
NMR(500MHz,CDCl3)δ(ppm):144.06,140.38,140.29,140.12,135.98,135.82,135.47,
131.37,129.29,128.11,128.01,127.60,126.60,126.57,120.39,44.52；Product is 3,7- dihydro-
1,2,5,6- tetraphenyl -4,8- two (p-bromophenyl) fulvalene.Structural formula are as follows:
By the dichloromethane solution (5 × 10 of compound-5Mol/L) a length of 360nm of maximum absorption wave, fluorescence emission peak are
453nm。
Embodiment 4
1.0mmol 1,2- diphenyl -4- (4- methoxyphenyl) -1,3 ring penta 2 is added in the round-bottomed flask of 100mL
Alkene, 0.10mmol NiCl2With 0.1mmol PPh3, 5mL DMSO is then added, is persistently stirred to react 5h under the conditions of 90 DEG C, it is cold
But to room temperature, red solution is obtained.Solution is added in separatory funnel, 40mL deionized water is added, shakes up, adds 50mL
Methylene chloride shakes up, and layering separates lower layer's organic phase, anhydrous MgSO is added4Dry, suction filtration obtains filtrate；Utilize rotary evaporation
Dichloromethane filtrate is concentrated, obtains peony crude product after evaporation by instrument.Using methylene chloride/petroleum ether (2:5) as elution
Agent, silica gel column chromatography purify it, be dried in vacuo after obtain product.Yield: 85%.Characterize data: MS (API-ES):
646.29；1H NMR(400MHz,CDCl3)δ(ppm):7.41–7.37(m,4H),7.14–6.94(m,16H),6.77–6.67
(m,8H),3.89–3.79(m,4H),3.77(s,6H).13C NMR(500MHz,CDCl3)δ(ppm):158.37,144.77,
140.93,139.72,139.30,136.48,129.86,129.41,128.01,127.77,127.39,126.43,126.04,
113.83,55.23,44.50；Product is 3,7- dihydro -1,2,5,6- tetraphenyl -4,8- two (4- methoxyphenyl) fulvalene.
Structural formula are as follows:
Compound is dissolved in methylene chloride and is configured to 5 × 10-5Mol/L solution, from ultra-violet absorption spectrum and fluorescent emission
It can be seen that the molecule absorption peak position is set to 351nm, fluorescence emission wavelengths 463nm in spectrum.
Embodiment 5
1.0mmol 1,2- diphenyl -4- (4- methoxyphenyl) -1,3 ring penta 2 is added in the round-bottomed flask of 100mL
Alkene, 0.10mmol CuCl2, 0.2mmol diphenylphosphine, then be added 5mL DMF, be persistently stirred to react 5h under the conditions of 90 DEG C,
It is cooled to room temperature, obtains red solution.Solution is added in separatory funnel, 40mL deionized water is added, shakes up, adds
50mL methylene chloride, shakes up, and layering separates lower layer's organic phase, anhydrous MgSO is added4Dry, suction filtration obtains filtrate；Utilize rotation
Dichloromethane filtrate is concentrated, obtains red crude product after evaporation by evaporimeter.Using methylene chloride/petroleum ether (2:5) as washing
De- agent, silica gel column chromatography purify it, and obtain product after being dried in vacuo.Yield: 80%.Characterize data: MS (API-ES):
646.29；1H NMR(400MHz,CDCl3)δ(ppm):7.41–7.37(m,4H),7.14–6.94(m,16H),6.77–6.67
(m,8H),3.89–3.79(m,4H),3.77(s,6H).13C NMR(500MHz,CDCl3)δ(ppm):158.37,144.77,
140.93,139.72,139.30,136.48,129.86,129.41,128.01,127.77,127.39,126.43,126.04,
113.83,55.23,44.50；Product is 3,7- dihydro -1,2,5,6- tetraphenyl -4,8- two (4- methoxyphenyl) fulvalene.
Structural formula are as follows:
Compound is dissolved in methylene chloride and is configured to 5 × 10-5Mol/L solution, from ultra-violet absorption spectrum and fluorescent emission
It can be seen that the molecule maximum absorption wave a length of 351nm, fluorescence emission peak 463nm in spectrum.
Embodiment 6
1.0mmol 1,2- diphenyl -4- (4- methoxyphenyl) -1,3 ring penta 2 is added in the round-bottomed flask of 100mL
Alkene, 0.10mmol NiCl2With 0.1mmol PPh3, 3mL acetonitrile is then added, is persistently stirred to react 5h under the conditions of 90 DEG C, it is cold
But to room temperature, red solution is obtained.Solution is added in separatory funnel, 40mL deionized water is added, shakes up, adds 50mL
Methylene chloride shakes up, and layering separates lower layer's organic phase, anhydrous MgSO is added4Dry, suction filtration obtains filtrate；Utilize rotary evaporation
Dichloromethane filtrate is concentrated, obtains red crude product after evaporation by instrument.Using methylene chloride/petroleum ether (2:5) as eluant, eluent,
Silica gel column chromatography purifies it, and obtains product after being dried in vacuo.Yield: 79%.Characterize data: MS (API-ES):
646.29；1H NMR(400MHz,CDCl3)δ(ppm):7.41–7.37(m,4H),7.14–6.94(m,16H),6.77–6.67
(m,8H),3.89–3.79(m,4H),3.77(s,6H).13C NMR(500MHz,CDCl3)δ(ppm):158.37,144.77,
140.93,139.72,139.30,136.48,129.86,129.41,128.01,127.77,127.39,126.43,126.04,
113.83,55.23,44.50；Product is 3,7- dihydro -1,2,5,6- tetraphenyl -4,8- two (4- methoxyphenyl) fulvalene.
Structural formula are as follows:
Compound is dissolved in methylene chloride and is configured to 5 × 10-5Mol/L solution, from ultra-violet absorption spectrum and fluorescent emission
It can be seen that the molecule maximum absorption band is 351nm in spectrum, fluorescence maximum emission wavelength is 463nm.
Embodiment 7
In the round-bottomed flask of 100mL be added 1.0mmol 1,2- diphenyl -4- (4- aminomethyl phenyl) -1,3 cyclopentadiene,
0.10mmol NiCl2、0.10mmol Pd(PPh3)4, 5mL DMSO is then added, is persistently stirred to react 4h under the conditions of 90 DEG C,
It is cooled to room temperature, obtains orange solution.Solution is added in separatory funnel, 40mL deionized water is added, shakes up, adds
50mL methylene chloride, shakes up, and layering separates lower layer's organic phase, anhydrous MgSO is added4Dry, suction filtration obtains filtrate；Utilize rotation
Dichloromethane filtrate is concentrated, obtains orange-yellow crude product after evaporation by evaporimeter.Using methylene chloride/petroleum ether (1:50) as
Eluant, eluent, silica gel column chromatography purify it, and obtain product after being dried in vacuo.Yield: 78%.Characterize data: MS (API-
ES): 614.30；1H NMR(400MHz,CDCl3)δ(ppm):7.40–7.00(m,24H),6.69(d,4H),3.95–3.77(m,
4H),2.28(s,6H).13C NMR(500MHz,CDCl3)δ(ppm):144.73,141.12,139.68,138.79,136.44,
136.28,134.09,129.51,129.12,128.04,127.47,126.53,126.13,44.52,21.19；Product is 3,
Two (4- aminomethyl phenyl) fulvalene of 7- dihydro -1,2,5,6- tetraphenyl -4,8-.
Structural formula are as follows:
Compound is dissolved in methylene chloride and is configured to 5 × 10-5Mol/L solution, from ultra-violet absorption spectrum and fluorescent emission
It can be seen that a length of 352nm of the molecule maximum absorption wave, fluorescence emission peak is 455nm in methylene chloride in spectrum.
Embodiment 8
In the round-bottomed flask of 100mL be added 1.0mmol 1,2- diphenyl -4- (4- aminomethyl phenyl) -1,3 cyclopentadiene,
0.10mmol NiCl2With 0.20mmol PPh3, 5mL DMF is then added, is persistently stirred to react 2h under the conditions of 90 DEG C, it is cooling
To room temperature, orange solution is obtained.Solution is added in separatory funnel, 40mL deionized water is added, shakes up, adds 50mL
Methylene chloride shakes up, and layering separates lower layer's organic phase, anhydrous MgSO is added4Dry, suction filtration obtains filtrate；Utilize rotary evaporation
Dichloromethane filtrate is concentrated, obtains orange-yellow crude product after evaporation by instrument.Using methylene chloride/petroleum ether (1:50) as elution
Agent, silica gel column chromatography purify it, and obtain product after being dried in vacuo.Yield: 75%.Characterize data: MS (API-ES):
614.30；1H NMR(400MHz,CDCl3)δ(ppm):7.40–7.00(m,24H),6.69(d,4H),3.95–3.77(m,4H),
2.28(s,6H).13C NMR(500MHz,CDCl3)δ(ppm):144.73,141.12,139.68,138.79,136.44,
136.28,134.09,129.51,129.12,128.04,127.47,126.53,126.13,44.52,21.19；Product is 3,
Two (4- aminomethyl phenyl) fulvalene of 7- dihydro -1,2,5,6- tetraphenyl -4,8-.
Structural formula are as follows:
Compound is dissolved in methylene chloride and is configured to 5 × 10-5Mol/L solution, from ultra-violet absorption spectrum and fluorescent emission
In the spectrum it can be seen that molecule absorption peak is 352nm, and fluorescence emission peak is 455nm in methylene chloride.
Embodiment 9
In the round-bottomed flask of 100mL be added 1.0mmol 1,2- diphenyl -4- (4- aminomethyl phenyl) -1,3 cyclopentadiene,
0.10mmol NiCl2With 0.10mmol PdCl2(PPh3)2, 5mL DMF is then added, persistently stirring is anti-under the conditions of 100 DEG C
4h is answered, is cooled to room temperature, orange-red solution is obtained.Solution is added in separatory funnel, 40mL deionized water is added, shakes up,
50mL methylene chloride is added, is shaken up, is layered, is separated lower layer's organic phase, anhydrous MgSO is added4Dry, suction filtration obtains filtrate；Benefit
With Rotary Evaporators red crude product will be obtained after dichloromethane filtrate concentration, evaporation.It utilizes methylene chloride/petroleum ether (1:50)
It is purified as eluant, eluent, silica gel column chromatography, and obtains product after being dried in vacuo.Yield: 75%.Characterize data: MS
(API-ES): 614.30；1H NMR(400MHz,CDCl3)δ(ppm):7.40–7.00(m,24H),6.69(d,4H),3.95–
3.77(m,4H),2.28(s,6H).13C NMR(500MHz,CDCl3)δ(ppm):144.73,141.12,139.68,138.79,
136.44,136.28,134.09,129.51,129.12,128.04,127.47,126.53,126.13,44.52,21.19；It produces
Object is 3,7- dihydro -1,2,5,6- tetraphenyl -4,8- two (4- aminomethyl phenyl) fulvalene.
Structural formula are as follows:
Compound is dissolved in methylene chloride and is configured to 5 × 10-5Mol/L solution, from ultra-violet absorption spectrum and fluorescent emission
It can be seen that a length of 352nm of the molecule maximum absorption wave, fluorescence emission peak is 455nm in methylene chloride in spectrum.
Embodiment 10
1.0mmol 1,2- diphenyl -4- (4- thiophene -2- phenyl) -1,3 rings penta 2 are added in the round-bottomed flask of 100mL
Alkene, 0.10mmol NiCl2With 0.15mmol PPh3, 5mL DMF is then added, is persistently stirred to react 6h under the conditions of 90 DEG C, it is cold
But to room temperature, orange solution is obtained.Solution is added in separatory funnel, 40mL deionized water is added, shakes up, adds
50mL methylene chloride, shakes up, and layering separates lower layer's organic phase, anhydrous MgSO is added4Dry, suction filtration obtains filtrate；Utilize rotation
Dichloromethane filtrate is concentrated, obtains yellow crude product after evaporation by evaporimeter.Using methylene chloride/petroleum ether (1:30) as washing
De- agent, silica gel column chromatography purify it, and obtain product after being dried in vacuo.Yield: 90%.Characterize data: MS (API-ES):
749.40；1H NMR(400MHz,CDCl3)δ(ppm):7.45(s,8H),7.18-6.96(m,22H),6.73(d,4H),3.91
(s,4H).13C NMR(500MHz,CDCl3)δ(ppm):144.38,140.78,140.55,139.67,136.14,135.88,
132.42,129.43,128.08,127.55,126.95,126.38,125.79,124.56,122.73,44.45；Product is 3,
7- dihydro -1,2,5,6- tetraphenyl -4,8- two (4- thiophene -2- phenyl) fulvalene.
Structural formula are as follows:
Compound is dissolved in methylene chloride and is configured to 5 × 10-5Mol/L solution, from ultra-violet absorption spectrum and fluorescent emission
It can be seen that a length of 358nm of the molecule maximum absorption wave, fluorescence emission peak is 473nm in methylene chloride in spectrum.
Embodiment 11
1.0mmol 1,2- diphenyl -4- (4- thiophene -2- phenyl) -1,3 rings penta 2 are added in the round-bottomed flask of 100mL
Alkene, 0.10mmol AlCl3With 0.20mmol PPh3, 5mL DMF is then added, is persistently stirred to react 5h under the conditions of 70 DEG C, it is cold
But to room temperature, yellow solution is obtained.Solution is added in separatory funnel, 40mL deionized water is added, shakes up, adds 50mL
Methylene chloride shakes up, and layering separates lower layer's organic phase, anhydrous MgSO is added4Dry, suction filtration obtains filtrate；Utilize rotary evaporation
Dichloromethane filtrate is concentrated, obtains yellow crude product after evaporation by instrument.Using methylene chloride/petroleum ether (1:30) as elution
Agent, silica gel column chromatography purify it, be dried in vacuo after obtain product.Yield: 72%.Characterize data: MS (API-ES):
749.40；1H NMR(400MHz,CDCl3)δ(ppm):7.45(s,8H),7.18-6.96(m,22H),6.73(d,4H),3.91
(s,4H).13C NMR(500MHz,CDCl3)δ(ppm):144.38,140.78,140.55,139.67,136.14,135.88,
132.42,129.43,128.08,127.55,126.95,126.38,125.79,124.56,122.73,44.45；Product is 3,
7- dihydro -1,2,5,6- tetraphenyl -4,8- two (4- thiophene -2- phenyl) fulvalene.
Structural formula are as follows:
Compound is dissolved in methylene chloride and is configured to 5 × 10-5Mol/L solution, from ultra-violet absorption spectrum and fluorescent emission
It can be seen that the molecule absorption peak position is set to 358nm in spectrum, fluorescence maximum emission wavelength is 473nm in methylene chloride.
Embodiment 12
1.0mmol 1,2- diphenyl -4- (4- thiophene -2- phenyl) -1,3 rings penta 2 are added in the round-bottomed flask of 100mL
Alkene, 0.10mmol NiCl2、0.20mmol PPh3, 5mL DMF is then added, is persistently stirred to react 4h under the conditions of 90 DEG C, it is cold
But to room temperature, orange solution is obtained.Solution is added in separatory funnel, 40mL deionized water is added, shakes up, adds
50mL methylene chloride, shakes up, and layering separates lower layer's organic phase, anhydrous MgSO is added4Dry, suction filtration obtains filtrate；Utilize rotation
Dichloromethane filtrate is concentrated, obtains yellow crude product after evaporation by evaporimeter.Using methylene chloride/petroleum ether (1:30) as washing
De- agent, silica gel column chromatography purify it, be dried in vacuo after obtain product.Yield: 82%.Characterize data: MS (API-ES):
749.40；1H NMR(400MHz,CDCl3)δ(ppm):7.45(s,8H),7.18-6.96(m,22H),6.73(d,4H),3.91
(s,4H).13C NMR(500MHz,CDCl3)δ(ppm):144.38,140.78,140.55,139.67,136.14,135.88,
132.42,129.43,128.08,127.55,126.95,126.38,125.79,124.56,122.73,44.45；Product is 3,
7- dihydro -1,2,5,6- tetraphenyl -4,8- two (4- thiophene -2- phenyl) fulvalene.
Structural formula are as follows:
Compound is dissolved in methylene chloride and is configured to 5 × 10-5Mol/L solution, from ultra-violet absorption spectrum and fluorescent emission
It can be seen that a length of 358nm of the molecule maximum absorption wave, maximum emission wavelength is 473nm in methylene chloride in spectrum.
Claims (9)
1. a kind of polyaryl replaces fulvalene compound, which is characterized in that the polyaryl replaces fulvalene compound structure
Formula is such as shown in (I):
In formula, R be 4- bromophenyl, 4- methoxyphenyl, 4- aminomethyl phenyl, 4- thiophene -2- phenyl, 3,5- Dimethoxyphenyl,
3,4,5- trimethoxyphenyl, -1 naphthalene of 2- methoxyl group, -1 naphthalene of 4- methoxyl group, -4 phenyl of 4- pyridyl group, phenyl or 4- biphenyl
Base.
2. the synthetic method that a kind of polyaryl replaces fulvalene compound, which is characterized in that steps are as follows:
Different substituents cyclopentadiene is dissolved in organic solvent, adds catalyst aid, is stirred under the conditions of 60~150 DEG C of temperature
React 2h~10h；After reaction, deionized water is added, benefit is extracted with dichloromethane；Anhydrous MgSO is added in extract liquor4It is dry
Dry, suction filtration obtains filtrate, will obtain crude product after filtrate concentration, evaporation；Made using the mixed solvent of petroleum ether and methylene chloride
For eluant, eluent, crude product is purified by silica gel column chromatography and obtains product after being dried in vacuo.
3. synthetic method according to claim 2, which is characterized in that the different substituents cyclopentadiene and catalysis help
The molar ratio of agent is 1:0.005~0.35.
4. synthetic method according to claim 2 or 3, which is characterized in that the different substituents cyclopentadiene is 1,
2- diphenyl -4- (4- bromophenyl) -1,3- cyclopentadiene, 1,2- diphenyl -4- (4- methoxyl group) phenyl -1,3- cyclopentadiene,
1,2- diphenyl -4- (4- methyl) phenyl -1,3- cyclopentadiene, 1,2- diphenyl -4- (4- thiophene -2- phenyl) -1,3- ring penta
Diene, 1,2- diphenyl -4- (3,5- Dimethoxyphenyl) -1,3- cyclopentadiene, 1,2- diphenyl -4- (3,4,5- trimethoxies
Base phenyl) -1,3- cyclopentadiene, 1,2- diphenyl -4- (- 1 naphthalene of 2- methoxyl group) -1,3- cyclopentadiene, 1,2- diphenyl -4-
(4- methoxy-1-naphthyl) -1,3- cyclopentadiene, 1,2- diphenyl -4- (4- pyridyl group -4- phenyl) -1,3- cyclopentadiene, 1,
One of 2,4- triphenyl -1,3- cyclopentadiene, 1,2- diphenyl -4- (4- xenyl) -1,3- cyclopentadiene.
5. synthetic method according to claim 2 or 3, which is characterized in that the organic solvent be acetonitrile, benzene, toluene,
N, one of N '-dimethyl formamide, dimethyl sulfoxide, tetrahydrofuran.
6. synthetic method according to claim 4, which is characterized in that the organic solvent be acetonitrile, benzene, toluene, N,
One of N '-dimethyl formamide, dimethyl sulfoxide, tetrahydrofuran.
7. according to synthetic method described in claim 2,3 or 6, which is characterized in that the catalyst aid is nickel chloride, chlorination
Aluminium, titanium chloride, copper chloride, stannic chloride, manganese chloride, triphenylphosphine, diphenylphosphine, Phenylphosphine, tetrakis triphenylphosphine palladium, bis- (three
Phenylphosphine) mixing of one or more of palladium chloride.
8. synthetic method according to claim 4, which is characterized in that the catalyst aid is nickel chloride, aluminium chloride, chlorine
Change titanium, copper chloride, stannic chloride, manganese chloride, triphenylphosphine, diphenylphosphine, Phenylphosphine, tetrakis triphenylphosphine palladium, bis- (triphenyls
Phosphine) mixing of one or more of palladium chloride.
9. synthetic method according to claim 5, which is characterized in that the catalyst aid is nickel chloride, aluminium chloride, chlorine
Change titanium, copper chloride, stannic chloride, manganese chloride, triphenylphosphine, diphenylphosphine, Phenylphosphine, tetrakis triphenylphosphine palladium, bis- (triphenyls
Phosphine) mixing of one or more of palladium chloride.
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| CN112331793A (en) * | 2020-11-09 | 2021-02-05 | 中国计量大学 | Light-emitting diode based on zero-dimensional metal halide and preparation method thereof |
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| CN102127139A (en) * | 2010-01-13 | 2011-07-20 | 延边大学 | Tetrathiafulvalene structure based liquid crystal compound and preparation method thereof |
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| CN112331793A (en) * | 2020-11-09 | 2021-02-05 | 中国计量大学 | Light-emitting diode based on zero-dimensional metal halide and preparation method thereof |
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