CN105713003B - π extends equal San Dan Za guans derivatives and its synthetic method - Google Patents

π extends equal San Dan Za guans derivatives and its synthetic method Download PDF

Info

Publication number
CN105713003B
CN105713003B CN201610041781.8A CN201610041781A CN105713003B CN 105713003 B CN105713003 B CN 105713003B CN 201610041781 A CN201610041781 A CN 201610041781A CN 105713003 B CN105713003 B CN 105713003B
Authority
CN
China
Prior art keywords
derivatives
guan
equal
alkyl
triamidos
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201610041781.8A
Other languages
Chinese (zh)
Other versions
CN105713003A (en
Inventor
魏俊发
刘波
李明
李靖
石先莹
杨明瑜
施东辉
杨奕辉
程昆木
张强
刘恒
鲁瑶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi Normal University
Original Assignee
Shaanxi Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi Normal University filed Critical Shaanxi Normal University
Priority to CN201610041781.8A priority Critical patent/CN105713003B/en
Publication of CN105713003A publication Critical patent/CN105713003A/en
Application granted granted Critical
Publication of CN105713003B publication Critical patent/CN105713003B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/22—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electroluminescent Light Sources (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

Extending equal San Dan Za guans derivatives and its synthetic method, the structural formula of the derivative the invention discloses a kind of π isWherein R represents C1~C10Alkyl, R1、R2、R3Each independent representative H, C1~C4Alkyl, C1~C4Alkoxy, phenyl, C1~C4Any one in alkyl-substituted phenyl, it is with 1,5,9 triamidos 2,3,6,7,10,11 6 alkoxy benzophenanthrenes and salicylide or salicylaldehyde derivatives are raw material, Pictet Spengler reactions are first passed through under acid catalysis, then the nucleophilic substitution one kettle way Jing Guo intramolecular obtains the equal San Dan Za guan derivatives of π extensions in the basic conditions, the reaction condition is gentle, it is easy to operate, product yield high, portion of product yield are a kind of easy methods for synthesizing such compound up to more than 90%.

Description

π extends equal San Dan Za guans derivatives and its synthetic method
Technical field
The invention belongs to the synthesis field of nano-graphite alkenes compound, and in particular to three nitrogen of a kind of π system expandings The synthetic method of Za guans compound and its derivative.
Background technology
Polycyclic aromatic hydrocarbon (PAHs) with nano-graphene micro-structural is due to its unique physicochemical properties and photo electric Can, it can be widely applied to Organic Light Emitting Diode, field-effect transistor, organic photovoltaic battery and solar cell etc..Therefore, Design and composite structure novelty, the more preferable polycyclic aromatic hydrocarbon of performance cause scientific circles and the great interest of industrial circle.To more cyclophanes Introducing hetero-atoms and to expand its pi-conjugated system be regulation polycyclic aromatic hydrocarbon physicochemical properties and photoelectric properties in hydrocarbon molecule skeleton One of important channel.Heteroatomic introducing can be influenceed in the case where not changing polycyclic aromatic hydrocarbon geometry its characteristic electron from And change its physicochemical properties and supermolecule behavior.π Orbital Overlaps face can be effectively increased by expanding the pi-conjugated system of polycyclic aromatic hydrocarbon Product, the intermolecular pi-pi accumulation effect of enhancing polycyclic aromatic hydrocarbon and self-assembly property, improve its charge transport properties as material.
2010, Wei Jun sent out seminar using 1,2-dimethoxy benzene as raw material, by trimerization, nitrification, reduction and Pictet- Spengler reacts to obtain 2,3,6,7,10,11- hexa methoxy -1,5,9- San Dan Za guans (CN 101967147A； Angew.Chem.Int.Ed.2010,49,8209-8213).Such compound structure is novel, has good electrochemical properties And heat endurance.2015, Pei Jian and Zhang Qichun et al. were respectively from 1,5,9- triamido -2,3,6,7,10,11- hexa methoxy benzene And phenanthrene sets out and the miscellaneous guan derivative of boron nitrogen of unique structure has been efficiently synthesized by electrophilic boranated reaction " one kettle way " (Chem.Commun.2015,51,4368-4371；Org.Lett.2015,17,560-563), there is provided one kind can make boron nitrogen knot Method of the structure unit precise symmetrical ground in Fen Bu guan cores.2016, Tan Qitao et al. reported a kind of succinct four steps structure C3The method (Chem.Commun.2016,52,537-540) of symmetrical San Dan Za guan parent molecules.
Although reported above has contained heteroatomic polycyclic arene compound photoelectric properties compared to full carbon analog Have and be obviously improved, but these azepine polycyclic aromatic hydrocarbon conjugated systems are smaller, Zhi Ju Xian Yu guan cores, and the aryl substituent at its edge Plane is almost vertical (Angew.Chem.Int.Ed.2010,49,8209-8213) Yu guan core plane.This near vertical it is several The conjugation that what relation not only limit edge aryl between guan core, and resulting steric hindrance hinder it is polycyclic Pi-pi accumulation effect and self-assembly property between aromatic hydrocarbon molecule, thus it is unfavorable for the electronic transmission performance and device performance of material Improve.
The content of the invention
The technical problems to be solved by the invention are that providing a kind of new π extends equal San Dan Za guan derivatives, and are it There is provided that a kind of raw material is easy to get, step is succinct, the synthetic method of mild condition and high income.
It is the following institute of structural formula that the π extends equal San Dan Za guan derivatives to solve the technical scheme that above-mentioned technical problem uses Show：
Wherein R represents C1~C10Alkyl, R1、R2、R3Each independent representative H, C1~C4Alkyl, C1~C4Alkoxy, benzene Base, C1~C4Any one in alkyl-substituted phenyl.
Above-mentioned π is extended in the structural formula of equal San Dan Za guan derivatives, and preferably R represents C1~C4Alkyl, R1、R2、R3Each solely Any one in vertical representative H, the tert-butyl group, methoxyl group, 4- tert-butyl-phenyls or 5- tert-butyl-phenyls.
The synthetic method that π of the present invention extends equal San Dan Za guan derivatives is：With 1-METHYLPYRROLIDONE (NMP) for solvent, By the bigcatkin willow shown in the alkoxy benzophenanthrenes of 1,5,9- triamidos -2,3,6,7,10,11- six shown in Formulas I and salicylide or Formula II Aldehyde derivatives, trifluoromethanesulfonic acid (TfOH) are reacted 12~24 hours at 110~130 DEG C, are cooled to room temperature, add K2CO3Or Na2CO3, continue reaction 6~12 hours at 100~130 DEG C, be cooled to room temperature, isolate and purify product, obtain π and extend equal three azepine Guan derivative, its synthetic route are as follows：
The above-mentioned alkoxy benzophenanthrenes of 1,5,9- triamidos -2,3,6,7,10,11- six and salicylide or salicylaldehyde derivatives, K2CO3Or Na2CO3Mol ratio be 1:3~8:5~10, preferably 1,5,9- triamidos -2,3,6,7,10,11- six alkoxy benzenes And luxuriant and rich with fragrance and salicylide or salicylaldehyde derivatives, K2CO3Or Na2CO3Mol ratio be 1:4.5~6:6~8.
The addition of above-mentioned trifluoromethanesulfonic acid is the alkoxy benzophenanthrene quality of 1,5,9- triamidos -2,3,6,7,10,11- six 0.5%~2%, the preferably addition of trifluoromethanesulfonic acid is 1,5,9- triamidos -2,3,6,7,10,11- six alkoxy benzos The 1% of luxuriant and rich with fragrance quality.
The alkoxy benzophenanthrenes of 1,5,9- triamidos -2,3,6,7,10,11- six of the present invention are with reference to this seminar Shen Qing Publication Number for CN 101967147A, entitled " equal San Dan Za guans compounds and its synthetic method and application " and application publication number For CN 103265436A, entitled " method of the alkoxy triphenylenes of 1,5,9- trinitro-s -2,3,6,7,10,11- six " It is prepared by the method disclosed in application for a patent for invention.
The present invention is derived with the alkoxy benzophenanthrenes of 1,5,9- triamidos -2,3,6,7,10,11- six and salicylide or salicylide Thing is raw material, Pictet-Spengler reactions is first passed through under acid catalysis, then the nucleophilic Jing Guo intramolecular takes in the basic conditions Generation reaction one kettle way obtains π and extends equal San Dan Za guan derivatives, and reaction condition is gentle, low in the pollution of the environment, easy to operate, and product is received Rate is high, and portion of product yield is up to more than 90%.
π of the present invention extends edge aryl substituent in equal San Dan Za guan derivative moleculars Yu guan core copline and received Enter the pi-conjugated system of guan core, not only can effectively expand the pi-conjugated system of the miscellaneous guan molecule of three nitrogen, guan nuclear periphery can be removed to disappear Aryl substituent because of the adverse effect that steric hindrance is acted on molecule pi-pi accumulation and self-assembly property is brought caused by vertical, from And improve its material property and device performance.Test result indicates that π of the present invention extends equal San Dan Za guan derivative ultraviolet-visibles The a length of 423~439nm of maximum absorption wave, edge energy scope is 2.27~2.40nm, displaing yellow fluorescence, fluorescence emission maximum ripple A length of 524~542nm, and their electroluminescent intensity is high, in 250 scanning, intensity is almost unchanged, has electricity well Photoluminescence stability, while heat decomposition temperature has good thermal stability more than 360 DEG C, therefore in electroluminescent There is very big application potential in terms of material.
Embodiment
With reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these realities Apply example.
Embodiment 1
So that the following π of composite structure formula extends equal San Dan Za guan derivatives as an example, specific synthetic method is as follows：
By the butoxy benzophenanthrenes of 0.14g (0.2mmol) 1,5,9- triamidos -2,3,6,7,10,11- six and 0.15g (1.2mmol) salicylide is added in 5mL 1-METHYLPYRROLIDONEs (NMP), is stirred at room temperature uniformly, 0.0014g trifluoros are then added dropwise Methanesulfonic acid, 120 DEG C are warming up to, with TLC tracing detections, react and terminate after 12 hours, be cooled to room temperature, add 0.16g (1.2mmol) anhydrous K2CO3, 120 DEG C are warming up under agitation, and reaction is cooled to room temperature after 12 hours, add 20mL distillations Water dilutes, and is extracted with chloroform (20mL × 3 time), then is washed repeatedly repeatedly with water and saturated aqueous common salt, finally by the organic phase of merging Use anhydrous Na2SO4Be dried overnight, concentrated by rotary evaporation, and column chromatography carried out with chloroform, obtained crude product chloroform and ethanol it is mixed Close solution to be recrystallized, obtain salmon pink pulverulent solids, be i.e. π extends equal San Dan Za guan derivatives, and its yield is 83%, is melted Point is more than 300 DEG C.
Products therefrom with Avance type superconduction Fourier digitizings nuclear magnetic resonance spectrometer (Switzerland, Bruker companies) and MALDI-TOF mass spectrographs (Germany, BurkerDaltonics) are characterized, and characterize data is as follows：
1H NMR (400MHz, CDCl3+TMS)δ(ppm)：8.61 (d, J=6.6Hz, 3H), 7.48 (t, J=12.0Hz, 3H), 7.37 (d, J=7.7Hz, 3H), 7.29 (s, 3H), 4.73 (s, 6H), 2.06 (d, J=6.6Hz, 6H), 1.87 (dd, J= 14.5,7.4Hz, 6H), 1.18 (t, J=7.2Hz, 9H)；MALDI-TOF-MS(C51H39N3O6)m/z：Theoretical value 789.3, actual measurement It is worth ([M+1]+)790.3。
Embodiment 2
So that the following π of composite structure formula extends equal San Dan Za guan derivatives as an example, specific synthetic method is as follows：
Salicylide used in embodiment 1 is replaced with equimolar 5- tert-butyl groups salicylide, other steps and the phase of embodiment 1 Together, Chinese red solid is obtained, i.e. π extends equal San Dan Za guan derivatives, and its yield is 96%, and fusing point is more than 300 DEG C.
Products therefrom with Avance type superconduction Fourier digitizings nuclear magnetic resonance spectrometer (Switzerland, Bruker companies) and MALDI-TOF mass spectrographs (Germany, BurkerDaltonics) are characterized, and characterize data is as follows：
1H NMR (400MHz, CDCl3+TMS)δ(ppm)：8.93 (s, 3H), 7.56 (dd, J=8.2,2.4Hz, 3H), 7.13 (d, J=8.6Hz, 3H), 4.84 (t, J=6.1Hz, 6H), 2.20-2.13 (m, 6H), 2.03-1.94 (m, 6H), 1.63 (s, 27H), 1.20 (t, J=7.3Hz, 9H)；13C NMR (75MHz, CDCl3+TMS)δ(ppm)：153.2,148.0,146.6, 144.5,141.6,137.0,129.6,121.3,120.9,118.3,117.5,110.4,108.4,74.2,34.8,33.1, 31.2,19.9,14.4；MALDI-TOF-MS(C63H63N3O6)m/z：Theoretical value 957.5, measured value ([M+1]+)958.4。
Embodiment 3
So that the following π of composite structure formula extends equal San Dan Za guan derivatives as an example, specific synthetic method is as follows：
Salicylide used in embodiment 1 is replaced with equimolar 4-methoxysalicylaldehyde, other steps and the phase of embodiment 1 Together, Chinese red solid is obtained, i.e. π extends equal San Dan Za guan derivatives, and its yield is 85%, and fusing point is more than 300 DEG C.
Products therefrom with Avance type superconduction Fourier digitizings nuclear magnetic resonance spectrometer (Switzerland, Bruker companies) and MALDI-TOF mass spectrographs (Germany, BurkerDaltonics) are characterized, and characterize data is as follows：
1H NMR (300MHz, CDCl3+TMS)δ(ppm)：8.17 (d, J=8.6Hz, 3H), 6.68 (d, J=6.9Hz, 3H), 6.43 (s, 3H), 4.53 (t, J=6.0Hz, 6H), 3.87 (s, 9H), 1.96-1.89 (m, 6H), 1.81-1.74 (m, 6H), 1.15 (t, J=7.2Hz, 9H)；13C NMR (75MHz, CDCl3+TMS)δ(ppm)：161.4,155.3,145.8, 142.5,139.8,135.4,125.1,116.3,113.9,110.5,108.6,106.1,99.9,72.8,54.3,31.9, 18.6 13.4；MALDI-TOF-MS(C54H45N3O9)m/z：Theoretical value 879.3, measured value ([M+1]+)880.3。
Embodiment 4
So that the following π of composite structure formula extends equal San Dan Za guan derivatives as an example, specific synthetic method is as follows：
Salicylide used in embodiment 1 is replaced with equimolar 4- to tert-butylphenyl salicylate aldehyde, other steps and reality It is identical to apply example 1, obtains Chinese red solid, be i.e. π extends equal San Dan Za guan derivatives, and its yield is 82%, and fusing point is more than 300 DEG C.
Products therefrom with Avance type superconduction Fourier digitizings nuclear magnetic resonance spectrometer (Switzerland, Bruker companies) and MALDI-TOF mass spectrographs (Germany, BurkerDaltonics) are characterized, and characterize data is as follows：
1H NMR (300MHz, CDCl3+TMS)δ(ppm)：7.81 (s, 3H), 7.35 (s, 12H), 7.04 (s, 3H), 6.96 (s, 3H), 4.38 (s, 6H), 1.82 (s, 6H), 1.66 (s, 6H), 1.40 (s, 27H), 1.07 (s, 9H)；13C NMR (75MHz, CDCl3+TMS)δ(ppm)：155.0,150.6,146.1,143.5,143.0,140.2,136.7,136.3,126.6,125.6, 124.9,121.6,120.1,116.6,115.1,109.2,107.5,73.7,34.6,32.9,31.4,19.5,14.4； MALDI-TOF-MS(C81H75N3O6)m/z：Theoretical value 1185.6, measured value ([M+1]+)1186.7。
Embodiment 5
So that the following π of composite structure formula extends equal San Dan Za guan derivatives as an example, specific synthetic method is as follows：
Salicylide used in embodiment 1 is replaced with equimolar 5- to tert-butylphenyl salicylate aldehyde, other steps and reality It is identical to apply example 1, obtains Chinese red solid, be i.e. π extends equal San Dan Za guan derivatives, and its yield is 97%, and fusing point is more than 300 DEG C.
Products therefrom with Avance type superconduction Fourier digitizings nuclear magnetic resonance spectrometer (Switzerland, Bruker companies) and MALDI-TOF mass spectrographs (Germany, BurkerDaltonics) are characterized, and characterize data is as follows：
1H NMR (300MHz, CDCl3+TMS)δ(ppm)：8.07 (s, 3H), 7.33 (d, J=7.9Hz, 12H), 7.07 (s, 3H), 6.57 (s, 3H), 4.27 (s, 6H), 1.70 (s, 6H), 1.55 (s, 6H), 1.40 (s, 27H), 0.93 (t, J=6.8Hz, 9H)；13C NMR (75MHz, CDCl3+TMS)δ(ppm)：153.8,149.5,145.7,142.4,139.6,136.9,135.9, 135.0,129.3,126.3,125.4,122.2,121,0,117.5,115.9,108.7,106.9,73.5,34.4,32.9, 31.4,19.6,14.3；MALDI-TOF-MS(C81H75N3O6)m/z：Theoretical value 1185.6, measured value ([M+1]+)1186.6。
Embodiment 6
So that the following π of composite structure formula extends equal San Dan Za guan derivatives as an example, specific synthetic method is as follows：
Salicylide used in embodiment 1 is replaced with equimolar 3,5- di-tert-butyl salicylaldehydes, other steps are with implementing Example 1 is identical, obtains Chinese red solid, i.e. π extends equal San Dan Za guan derivatives, and its yield is 78%, and fusing point is more than 300 DEG C.
Products therefrom with Avance type superconduction Fourier digitizings nuclear magnetic resonance spectrometer (Switzerland, Bruker companies) and MALDI-TOF mass spectrographs (Germany, BurkerDaltonics) are characterized, and characterize data is as follows：
1H NMR (400MHz, CDCl3+TMS)δ(ppm)：8.99 (d, J=2.3Hz, 3H), 7.77 (d, J=2.3Hz, 3H), 4.87 (t, J=6.3Hz, 6H), 2.33-2.26 (m, 6H), 1.99-1.90 (m, 6H), 1.79 (s, 27H), 1.58 (s, 27H), 1.21 (t, J=7.4Hz, 9H)；13C NMR (75MHz, CDCl3+TMS)δ(ppm)：152.6,150.6,149.7, 146.1,142.7,138.5,137.4,128.0,121.5,119.7,111.8,108.8,74.9,35.6,34.9,33.2, 31.6,30.3,20.1,14.5；MALDI-TOF-MS(C75H87N3O6)m/z：Theoretical value 1125.6, measured value ([M+1]+) 1126.7。
Embodiment 7
So that the following π of composite structure formula extends equal San Dan Za guan derivatives as an example, specific synthetic method is as follows：
Salicylide used in embodiment 1 is replaced with equimolar 4- tert-butyl groups salicylide, other steps and the phase of embodiment 1 Together, Chinese red solid is obtained, i.e. π extends equal San Dan Za guan derivatives, and its yield is 87%, and fusing point is more than 300 DEG C.
Products therefrom with Avance type superconduction Fourier digitizings nuclear magnetic resonance spectrometer (Switzerland, Bruker companies) and MALDI-TOF mass spectrographs (Germany, BurkerDaltonics) are characterized, and characterize data is as follows：
1HNMR (300MHz, CDCl3+TMS)δ(ppm)：8.60 (s, 3H), 7.56 (s, 6H), 4.78 (s, 6H), 2.12 (s, 6H), 1.91 (s, 6H), 1.52 (s, 27H), 1.25 (s, 9H)；13C NMR(150MHz,CDCl3+TMS)δ(ppm)：156.6 155.7,148.6,145.1,142.3,137.3,125.1,121.7,119.5,114.9,111.3,109.1,74.5,35.3, 32.8,31.3,19.6,14.3；MALDI-TOF-MS(C63H87N3O6)m/z：Theoretical value 957.5, measured value ([M+1]+) 958.5。
Embodiment 8
So that the following π of composite structure formula extends equal San Dan Za guan derivatives as an example, specific synthetic method is as follows：
By the butoxy benzophenanthrenes of 1,5,9- triamidos -2,3,6,7,10,11- six used in embodiment 1 with equimolar 1, 5,9- triamidos -2,3,6,7,10,11- hexamethoxytriphenylenes are replaced, and salicylide used is with equimolar 4- tert-butyl groups bigcatkin willow Aldehyde is replaced, and other steps are same as Example 1, obtains Chinese red solid, i.e. π extends equal San Dan Za guan derivatives, and its yield is 93%, fusing point is more than 300 DEG C.
Products therefrom with Avance type superconduction Fourier digitizings nuclear magnetic resonance spectrometer (Switzerland, Bruker companies) and MALDI-TOF mass spectrographs (Germany, BurkerDaltonics) are characterized, and characterize data is as follows：
1H NMR (400MHz, CDCl3+TMS)δ(ppm)：8.26 (d, J=8.0Hz, 3H), 7.4 (s, 3H), 7.29 (d, J =8.1Hz, 3H), 4.45 (s, 9H), 1.51 (s, 27H)；13C NMR (100MHz, CDCl3+TMS)δ(ppm)：156.4 155.4,147.6,143.7,140.8,137.3,124.8,121.5,119.1,117.9,114.8,110.3,108.3,62.1, 35.3 34.3；MALDI-TOF-MS(C54H45N3O6)m/z：Theoretical value 831.3, measured value ([M+1]+)832.3。
Embodiment 9
So that the following π of composite structure formula extends equal San Dan Za guan derivatives as an example, specific synthetic method is as follows：
By the butoxy benzophenanthrenes of 1,5,9- triamidos -2,3,6,7,10,11- six used in embodiment 1 with equimolar 1, 5,9- triamidos -2,3,6,7,10,11- hexamethoxytriphenylenes are replaced, and salicylide used is with equimolar 5- tert-butyl groups bigcatkin willow Aldehyde is replaced, and other steps are same as Example 1, obtains Chinese red solid, i.e. π extends equal San Dan Za guan derivatives, and its yield is 87%, fusing point is more than 300 DEG C.
Products therefrom with Avance type superconduction Fourier digitizings nuclear magnetic resonance spectrometer (Switzerland, Bruker companies) and MALDI-TOF mass spectrographs (Germany, BurkerDaltonics) are characterized, and characterize data is as follows：
1H NMR (300MHz, CDCl3+TMS)δ(ppm)：8.87 (s, 3H), 7.53 (s, 3H), 7.00 (s, 3H), 4.76 (s, 9H), 1.63 (s, 27H)；MALDI-TOF-MS(C54H45N3O6)m/z：Theoretical value 831.3, measured value ([M+1]+)832.3。
Embodiment 10
So that the following π of composite structure formula extends equal San Dan Za guan derivatives as an example, specific synthetic method is as follows：
By the butoxy benzophenanthrenes of 1,5,9- triamidos -2,3,6,7,10,11- six used in embodiment 1 with equimolar 1, 5,9- triamidos -2,3,6,7,10,11- hexamethoxytriphenylenes are replaced, equimolar 3, the 5- di-t-butyls of salicylide used Salicylide is replaced, and other steps are same as Example 1, obtains Chinese red solid, i.e. π extends equal San Dan Za guan derivatives, and it is produced Rate is 81%, and fusing point is more than 300 DEG C.
Products therefrom with Avance type superconduction Fourier digitizings nuclear magnetic resonance spectrometer (Switzerland, Bruker companies) and MALDI-TOF mass spectrographs (Germany, BurkerDaltonics) are characterized, and characterize data is as follows：
1H NMR (300MHz, CDCl3+TMS)δ(ppm)：8.95 (s, 3H), 7.75 (s, 3H), 4.74 (s, 9H), 1.75 (s, 27H), 1.55 (s, 27)；13C NMR (75MHz, CDCl3+TMS)δ(ppm)：152.5,149.6,146.0,138.6, 137.9,128.1,121.3,119.5,111.4,108.5,62.6,35.6,34.9,31.6,30.2；MALDI-TOF-MS (C66H69N3O6)m/z：Theoretical value 999.5, measured value ([M+1]+)1000.5。
Embodiment 11
So that the following π of composite structure formula extends equal San Dan Za guan derivatives as an example, specific synthetic method is as follows：
By the butoxy benzophenanthrenes of 1,5,9- triamidos -2,3,6,7,10,11- six used in embodiment 1 with equimolar 1, 5,9- triamidos -2,3,6,7,10,11- hexamethoxytriphenylenes are replaced, and salicylide used is with equimolar 5- to tert-butyl benzene Base salicylide is replaced, and other steps are same as Example 1, obtains Chinese red solid, i.e. π extends equal San Dan Za guan derivatives, its Yield is 94%, and fusing point is more than 300 DEG C.
Products therefrom with Avance type superconduction Fourier digitizings nuclear magnetic resonance spectrometer (Switzerland, Bruker companies) and MALDI-TOF mass spectrographs (Germany, BurkerDaltonics) are characterized, and characterize data is as follows：
1H NMR (400MHz, CDCl3+TMS)δ(ppm)：7.24 (s, 3H), 7.04 (s, 6H), 6.83 (s, 6H), 6.39 (s, 3H), 5.88 (s, 3H), 3.60 (s, 9H), 1.23 (s, 27H)；13C NMR (100MHz, CDCl3+TMS)δ(ppm)： 152.9,149.1,144.3,140.4,137.5,136.9,135.4,134.6,129.2,126.0,125.2,121.4, 119.9,117.0,113.8,106.9,105.6,60.8,34.3,31.4；MALDI-TOF-MS(C72H57N3O6)m/z：Theoretical value 1059.4, measured value ([M+1]+)1060.3。

Claims (5)

1. a kind of π extends equal San Dan Za guan derivatives, it is characterised in that the structural formula of the derivative is as follows：
Wherein R represents C1~C10Alkyl, R1、R2、R3Each independent representative H, C1~C4Alkyl, C1~C4Alkoxy, phenyl, C1 ~C4Any one in alkyl-substituted phenyl.
2. π according to claim 1 extends equal San Dan Za guan derivatives, it is characterised in that：Described R represents C1~C4Alkane Base, R1、R2、R3Each any one in independent representative H, the tert-butyl group, methoxyl group, 4- tert-butyl-phenyls.
3. the π described in a kind of claim 1 extends the synthetic method of equal San Dan Za guan derivatives, it is characterised in that：With N- methyl Pyrrolidones or DMF are solvent, by 1 shown in Formulas I, 5,9- triamidos -2,3,6,7,10,11- six alcoxyls Base benzophenanthrene is small in 110~130 DEG C of reactions 12~24 with the salicylaldehyde derivatives shown in salicylide or Formula II, trifluoromethanesulfonic acid When, after being cooled to room temperature, add K2CO3Or Na2CO3, continue reaction 6~12 hours at 100~130 DEG C, be cooled to room temperature, point From purified product, obtain π and extend equal San Dan Za guan derivatives；The wherein alkoxies of 1,5,9- triamidos -2,3,6,7,10,11- six Benzophenanthrene and salicylide or salicylaldehyde derivatives, K2CO3Or Na2CO3Mol ratio be 1:3~8:5~10, trifluoromethanesulfonic acid Addition is the 0.5%~2% of the alkoxy benzophenanthrene quality of 1,5,9- triamidos -2,3,6,7,10,11- six；
R in Formulas I represents C1~C10Alkyl, the R in Formula II1、R2、R3Each independent representative C1~C4Alkyl, C1~C4Alcoxyl Base, phenyl, C1~C4Any one in alkyl-substituted phenyl.
4. π according to claim 3 extends the synthetic method of equal San Dan Za guan derivatives, it is characterised in that：Described 1, The alkoxy benzophenanthrenes of 5,9- triamidos -2,3,6,7,10,11- six and salicylide or salicylaldehyde derivatives, K2CO3Or Na2CO3's Mol ratio is 1:4.5~6:6~8.
5. the π according to claim 3 or 4 extends the synthetic method of equal San Dan Za guan derivatives, it is characterised in that：Described The addition of trifluoromethanesulfonic acid is the 1% of the alkoxy benzophenanthrene quality of 1,5,9- triamidos -2,3,6,7,10,11- six.
CN201610041781.8A 2016-01-21 2016-01-21 π extends equal San Dan Za guans derivatives and its synthetic method Expired - Fee Related CN105713003B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610041781.8A CN105713003B (en) 2016-01-21 2016-01-21 π extends equal San Dan Za guans derivatives and its synthetic method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610041781.8A CN105713003B (en) 2016-01-21 2016-01-21 π extends equal San Dan Za guans derivatives and its synthetic method

Publications (2)

Publication Number Publication Date
CN105713003A CN105713003A (en) 2016-06-29
CN105713003B true CN105713003B (en) 2018-03-06

Family

ID=56154845

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610041781.8A Expired - Fee Related CN105713003B (en) 2016-01-21 2016-01-21 π extends equal San Dan Za guans derivatives and its synthetic method

Country Status (1)

Country Link
CN (1) CN105713003B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115490688B (en) * 2022-08-29 2024-04-16 南开大学 Two-dimensional conductive metal organic framework material based on triazacoronene, and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101967147B (en) * 2010-09-15 2012-07-04 陕西师范大学 S-triazacoronene compound and synthesis method and application thereof
CN103265436A (en) * 2013-05-27 2013-08-28 陕西师范大学 Method for synthesising 1,5,9-trinitro-2,3,6,7,10,11-hexa-alkoxy triphenylene
US20150255723A1 (en) * 2014-03-05 2015-09-10 Samsung Display Co., Ltd. Compound and organic light-emitting device including the same
CN105203623A (en) * 2015-08-31 2015-12-30 陕西师范大学 Application of 6-tertiary butyl-6-hexyloxy-6-benzo[a,b,de,lm,op,rs,uv]coronene as MALDI-TOF MS matrix in micromolecule detection

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101967147B (en) * 2010-09-15 2012-07-04 陕西师范大学 S-triazacoronene compound and synthesis method and application thereof
CN103265436A (en) * 2013-05-27 2013-08-28 陕西师范大学 Method for synthesising 1,5,9-trinitro-2,3,6,7,10,11-hexa-alkoxy triphenylene
US20150255723A1 (en) * 2014-03-05 2015-09-10 Samsung Display Co., Ltd. Compound and organic light-emitting device including the same
CN105203623A (en) * 2015-08-31 2015-12-30 陕西师范大学 Application of 6-tertiary butyl-6-hexyloxy-6-benzo[a,b,de,lm,op,rs,uv]coronene as MALDI-TOF MS matrix in micromolecule detection

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
1,5,9-Triazacoronenes: A Family of Polycyclic Heteroarenes Synthesized by a Threefold Pictet–Spengler Reaction;Junfa Wei，等;《Angew.Chem.Int.Ed.》;20101231;第8209–8213页，尤其Scheme 2 *

Also Published As

Publication number Publication date
CN105713003A (en) 2016-06-29

Similar Documents

Publication Publication Date Title
Liu et al. C–H activation: making diketopyrrolopyrrole derivatives easily accessible
JP2014517820A (en) Stannyl derivatives of naphthalene diimide and related compositions and methods
CN111978236B (en) Preparation method of N-substituted-3-morpholinyl-4-phenylseleno maleimide compound
CN109593095B (en) X-type hetero-condensed perylene aromatic hydrocarbon double-spiro-alkene functional molecular material and preparation and application thereof
Salim et al. Novel synthesis of oxa [9] helicenes by Lawesson’s reagent-mediated cyclization of helical quinone derivatives
CN112480130A (en) Macrocyclic extended porphyrin compounds and methods of making the same
CN102617466A (en) Top-bottom asymmetrical tert-butyl spirobifluorene compound
CN105713003B (en) π extends equal San Dan Za guans derivatives and its synthetic method
Feng et al. Synthesis of novel star-shaped carbazole-functionalized triazatruxenes
CN104974156B (en) 1, 5, 9-triazanaphthalene coronene compound and synthetic method thereof
CN105061135B (en) A kind of synthesis six vast position six benzos and the method for derivative thereof
CN115260205B (en) Bipyrene-doped extended porphyrin, bipropylar metal complex thereof, preparation method and application thereof
US9000170B2 (en) Process for the preparation of tetracarboxynaphthalenediimide compounds disubstituted with heteroaryl groups
CN114163617B (en) Thermochromic polymer material and application thereof
Liu et al. Synthesis, Characterization and Properties of Novel Star‐Shaped π‐Conjugated Oligomers with Triphenylamine Core
CN114380790B (en) Polysubstituted thiopyran derivative and synthetic method thereof
Ruiren et al. Synthesis, fluorescence properties of Eu (III) complexes with novel carbazole functionalized β-diketone ligand
CN107915730A (en) Quinacridone derivative containing nitrogen donor and its preparation method and application
CN104628753B (en) Meso-triphenylamine-substituted 3,5-aryl-modified boron dipyrromethene fluorophore derivatives and preparation method thereof
CN115991717A (en) Malachite green borate and derivatives, preparation method and application thereof
CN106167708A (en) 2,3 imidodicarbonic diamide benzophenanthrene discotic liquid-crystalline molecules and preparation method thereof
Wu et al. Structural, photoelectrical and thermol properties of ultra-stable Benzo [ghi] perylene trimide dimer anion
Wu et al. Synthesis, structure and photophysical properties of dibenzofuran-fused boron dipyrromethenes
CN105176518A (en) Dithienopyridine zinc coordination compound luminescence material and preparation method thereof
CA2953774A1 (en) New aromatic macrocyclic metal complex dyes and the synthesis thereof with active nano metal powders

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180306

Termination date: 20210121