CN106831876B - A kind of synthetic method of benzo phosphene - Google Patents

A kind of synthetic method of benzo phosphene Download PDF

Info

Publication number
CN106831876B
CN106831876B CN201710116743.9A CN201710116743A CN106831876B CN 106831876 B CN106831876 B CN 106831876B CN 201710116743 A CN201710116743 A CN 201710116743A CN 106831876 B CN106831876 B CN 106831876B
Authority
CN
China
Prior art keywords
compound
cdcl
nmr
added
reaction
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
CN201710116743.9A
Other languages
Chinese (zh)
Other versions
CN106831876A (en
Inventor
段征
周洋
王越
王文彪
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.)
Zhengzhou University
Original Assignee
Zhengzhou 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 Zhengzhou University filed Critical Zhengzhou University
Priority to CN201710116743.9A priority Critical patent/CN106831876B/en
Publication of CN106831876A publication Critical patent/CN106831876A/en
Application granted granted Critical
Publication of CN106831876B publication Critical patent/CN106831876B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
    • C07F9/65686—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of an organo-phosphorane
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • 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
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms

Abstract

The invention belongs to organic chemical synthesis fields, and in particular to a kind of synthetic method of benzo phosphene.Using 1- substitution -2- bromos aromatic radical-acetylene as raw material phenyl dichloro phosphorus synthetic intermediate is added, then generate target compound by trace air catalytic in this method.Synthetic method of the present invention is good to different functional groups tolerance it is not necessary that oxidant, catalyst and additive is additionally added, and is a kind of method of the synthesis benzo phosphene class compound of new green environment protection.Yield reaches 40% or more, has good application prospect.

Description

A kind of synthetic method of benzo phosphene
Technical field
The invention belongs to organic chemical synthesis fields, and in particular to a kind of benzo phosphorus with application value in terms of material The synthetic method of heterocyclic pentylene.
Background technology
Benzo phosphene is visited in photoelectric material (Chem.Soc.Rev.2016,45,5296), bio-imaging, fluorescence Needle (Angew.Chem.Int.Ed.2015,54,4539；), Chem.Commun.2015,51,11880 photochromic molecules switch (Chem.Sci.2017,8,1309) etc. it has a wide range of applications.
The benzo phosphene synthetic method reported includes mainly：I) phenylacetylene of ortho position phosphorus-containing groups is by dividing Annulation generates in son；II) phosphorus-containing compound is generated with another compound by intermolecular radical reaction；III) pass through pass Key step is that transition metal-catalyzed " one pot " multicomponent multistep reaction generates (Org.Biomol.Chem.2016,14,5402； Org.Lett.2016,18,5436).Up to the present, the synthetic method of benzo phosphene is still very limited, and Environmentally protective method is more rare.
Invention content
For current technology present situation, present invention aims at a kind of the new of benzo phosphene class compound of offer The environmentally protective synthetic method of type.
Purpose to realize the present invention, the method generate benzo phosphorus using trace air as catalyst, by intramolecular cyclization Heterocyclic pentylene.
Concrete scheme and route are as follows:
A) compound I-a to I-m is synthesized
R is the group as described in following table：
Modus ponens A raw materials of compound vacuumizes in schlenk, is filled with nitrogen, organic solvent is added, then by system control Temperature is added dropwise n-BuLi, system is restored to reacting at room temperature, referred to as system 1 to -75 DEG C to -78 DEG C.Take another Schlenk is vacuumized, and is filled with nitrogen, and organic solvent is added, PhPCl is then added2, and -75 DEG C to -78 DEG C are cooled to, referred to as System 2.The turbid solution in system 1 is injected into system 2 with syringe, after keep the temperature.Reaction terminates, in open state Under, water reaction is slowly added into reaction system.After reaction, through extraction, merging organic phase, post separation is crossed in vacuum distillation, Obtain list of target object I.
The organic solvent choosing：Anhydrous ether or anhydrous tetrahydro furan.
B) compound II-a to II-m is generated by trace air catalytic
It takes object I in the schlenk pipes with cock, then vacuumizes, be filled with nitrogen, then under nitrogen protection, Anhydrous and oxygen-free organic solvent is added, system is sealed, 110 DEG C of -120 DEG C of reactions.After reaction, it is molten to be evaporated under reduced pressure out reaction Post separation is crossed in agent.
Organic solvent selects toluene or DMF.Above-mentioned markaThe synthesis of compound uses toluene solvant, markbThe conjunction of compound At using DMF solvent.
Compared with prior art, oxidant, catalyst and additive is added without additional in synthetic method of the present invention, It is good to different functional groups tolerance, it is a kind of method of the synthesis benzo phosphene class compound of new green environment protection. Yield reaches 40% or more, and some reaches 80% or more, has good application prospect.
Description of the drawings
Fig. 1 is the thermogravimetric analysis figure of the compounds of this invention II-e；
Fig. 2 is structural schematic diagram of the compounds of this invention as application device.
Specific implementation mode
For the present invention is better described, under embodiment：
Embodiment 1 I-a to I-g, I-j, I-k, the synthetic method of I-m, steps are as follows:
For modus ponens A raw materials of compound 10mmol in 100mL schlenk, three times, anhydrous ether is added in vacuum and exchange nitrogen Then n-BuLi 10mmol are added dropwise to -75 DEG C in system temperature by 50mL, and system is restored to room temperature reaction 1h (system 1). It takes another 100mL schlenk vacuum and exchange nitrogen three times, 20mL anhydrous ethers will be entered, PhPCl is then added211mmol, And it is cooled to -78 DEG C (systems 2).The turbid solution in system 1 is injected into system 2 with syringe, after keep the temperature 10min, Reaction voluntarily restores to room temperature, and reacts 1h.Reaction terminates, and under open state, 5mL water is slowly added into reaction system, React 10min.Reaction terminates, and is extracted with ethyl acetate and water, merges organic phase, after vacuum distillation, with dichloromethane：Acetic acid second Ester=5:1 crosses pillar separation.
I-b yields：45%, light yellow liquid,1H NMR(300MHz,CDCl3) δ=2.09 (s, 3H, CH3),6.90(d,J =7.8Hz, 2H), 7.06 (d, J=8.1Hz, 2H), 7.18-7.35 (m, 6H)；7.53-7.60(m,2H),7.81-7.88(m, 1H),8.25(d,JPH=496.5Hz, PH),13C NMR(75MHz,CDCl3) δ=21.41 (s, CH3),85.50(d,JCP= 8.6Hz,C),97.24(s,C),118.81(s,C),125.02(d,JCP=9.5Hz, C), 128.32 (d, JCP=11.3Hz, CH),128.59(d,JCP=12.9Hz, 2CH), 129.14 (s, 2CH), 130.62 (d, JCP=11.5Hz, 2CH), 131.26 (s,2CH),131.55(d,JCP=102.6Hz, C), 131.83 (d, JCP=101.6Hz, C), 132.15 (d, JCP=13.4Hz, CH),132.17(s,CH),132.19(s,CH),132.71(d,JCP=8.3Hz, CH), 139.23 (s, C)；31P{1H}NMR (121MHz,CDCl3) δ=16.8；HRMS Calcd.for C21H17OP[M+H+]317.1090,Found:317.1096； Elemental analysis calcd for C21H17OP (%):C 79.73,H 5.42.found:C 79.97,H5.20.
I-c yields：49%, white solid,1H NMR(300MHz,CDCl3) δ=7.18-7.42 (m, 15H), 6.62- 7.69(2H),7.90-7.94(m,1H),8.35(d,JPH=496.2Hz, PH)；13C NMR(75MHz,CDCl3) δ=86.87 (d,JCP=8.4Hz, C), 96.95 (s, C), 120.78 (s, C), 124.90 (d, JCP=9.5Hz, C), 126.89 (s, 2CH), 126.99(s,2CH),127.86(s,CH),128.57(d,JCP=9.8Hz, CH), 128.72 (d, JCP=12.8Hz, 2CH), 128.90(s,2CH),130.73(d,JCP=11.5Hz, 2CH), 131.60 (d, JCP=102.8Hz, C), 131.93 (s, 2CH),132.04(d,JCP=101.2Hz, C), 132.33 (brs, 3CH, overlapped), 132.90 (d, JCP=8.1Hz, CH),139.73(s,C),141.58(s,C)；31P{1H}NMR(121MHz,CDCl3) δ=16.7；HRMS Calcd.for C26H19OP[M+H+]379.1246,Found:379.1251.Elemental analysis calcd for C26H19OP (%):C 82.53,H5.06.found:C 82.90,H 4.99.
I-e yields：47%, yellow solid,1H NMR(400MHz,CDCl3) δ=6.95 (d, JHH=8.8Hz, 2H), 7.05-7.16(m,8H),7.25-7.29(m,4H),7.43-7.56(m,6H),7.73-7.66(m,2H),7.99-8.04(m, 1H),8.44(d,JPH=498.4Hz, PH)；13C NMR(100MHz,CDCl3) δ=85.38 (d, JCP=8.6Hz, C), 97.67 (s,C),114.31,(s,C),121.64(s,2CH),123.97(s,2CH),125.30(s,4CH),125.48(d,JCP= 10.1Hz,C),128.29(d,JCP=11.3Hz, CH), 128.77 (d, JCP=12.7Hz, 2CH), 129.53 (s, 4CH), 130.86(d,JCP=11.5Hz, 2CH), 131.58 (d, JCP=102.3Hz, C), 131.69 (d, JCP=102.4Hz, C), 132.29(s,CH),132.33(d,JCP=7.9Hz CH), 132.37 (s, CH), 132.47 (s, 2CH), 132.78 (d, JCP= 8.3Hz,CH),146.93(s,C),148.68(s,C)；31P{1H}NMR(162MHz,CDCl3) δ=17.0；HRMS Calcd.for C32H24NOP[M+H+]470.1668,Found:470.1669；Elemental analysis calcd for C32H24NOP (%):C 81.86,H 5.15.found:C 81.54,H 5.08.
I-f yields：43%, light yellow liquid,1H NMR(300MHz,CDCl3) δ=6.97-7.00 (m, 2H), 7.02- 7.53(m,8H),7.69-7.77(m,2H),7.98-8.04(m,1H),8.41(d,JPH=495.9Hz, PH)；13C NMR (75MHz,CDCl3) δ=85.76 (d, JCP=8.4Hz, C), 95.77 (s, C), 115.74 (d, JCP=22.0Hz, 2CH), 118.08 (d, J=3.5Hz, C), 124.80 (d, J=9.5Hz, C), 128.63 (d, J=11.3Hz, CH), 128.69 (d, J= 12.8Hz, 2CH), 130.72 (d, J=11.5Hz, 2CH), 131.46 (d, JCP=100.7Hz, C), 131.96 (d, JCP= 101.6Hz, C), 132.28 (s, CH), 132.33 (d, J=1.3Hz, CH), 132.38 (s, CH), 132.85 (d, J=8.3Hz, ), CH 133.43 (d, J=8.6Hz, 2CH), 162.80 (d, JCF=249.5Hz, C)；31P{1H}NMR(121MHz,CDCl3) δ= 17.0；HRMS Calcd.for C20H14FOP[M+H+]321.0839,Found:321.0844；Elemental analysis Calcd for C20H14FOP (%):C 75.00,H 4.41.found:C 75.01,H 4.20.
I-j yields：45%, light yellow liquid,1H NMR(300MHz,CDCl3) δ=7.31-7.55 (m, 10H), 7.64- 7.79(m,4H),7.98-8.05(m,1H),8.11-8.14(1H),8.52(d,JPH=497.1Hz, PH)；13C NMR (75MHz,CDCl3) δ=90.61 (d, JCP=8.5Hz, C), 95.26 (C), 119.63 (s, C), 125.14 (d, JCP= 10.6Hz,C),125.21(s,CH),125.91(s,CH),126.64(s,CH),127.13(s,CH),128.41(s,CH), 128.79(d,JCP=10.0Hz, CH), 128.81 (d, JCP=13.1Hz, 2CH), 129.69 (s, CH), 130.84 (d, JCP= 11.5Hz,2CH),130.87(s,CH),131.28(d,JCP=102.8Hz, C), 131.75 (d, JCP=104.0Hz, C), 132.39(d,JCP=12.8Hz, CH), 132.42 (s, CH), 132.44 (s, CH), 132.97 (s, C), 133.09 (s, C), 133.26(d,JCP=8.3Hz, CH)；31P{1H}NMR(121MHz,CDCl3) δ=17.3；HRMS Calcd.for C24H17OP [M+H+]353.1090,Found:353.11094.Elemental analysis calcd for C24H17OP (%): C81.81,H 4.86.found:C 81.65,H 5.07.
I-k yields：41%, white solid,1H NMR(300MHz,CDCl3) δ=7.34-7.60 (m, 17H), 7.90- 7.97(m,1H),7.99(d,JPH=502.8Hz, PH)；13C NMR(75MHz,CDCl3) δ=88.75 (d, JCP=8.7Hz, C),96.72(s,C),120.61(s,C),124.997(d,JCP=9.9Hz, C), 127.20 (s, CH), 127.88 (s, CH), 128.21(s,2CH),128.53(d,JCP=11.1Hz, CH), 128.62 (d, JCP=12.8Hz, 2CH), 129.283 (s, 2CH),129.30(s,CH),129.63(s,CH),130.68(d,JCP=11.6Hz, 2CH), 131.63 (d, JCP= 102.0Hz,C),131.94(d,JCP=100.8Hz, C), 132.00 (d, JCP=7.7Hz, CH), 132.10 (d, JCP= 2.3Hz,CH),132.25(d,JCP=2.9Hz, CH), 133.00 (d, JCP=8.3Hz, CH), 133.02 (s, CH), 140.34 (s,C),144.02(s,C)；31P{1H}NMR(121MHz,CDCl3) δ=16.1；HRMS Calcd.for C26H19OP[M+H+] 379.1246,Found:379.1251.
I-m yields：52%, colourless liquid,1H NMR(300MHz,CDCl3) δ=0.87 (t, JHH=7.2Hz, 3H), 1.26-1.46(m,4H),2.31(t,JHH=7.2Hz, 2H), 7.45-7.52 (m, 6H), 7.67-7.75 (m, 2H), 7.92- 7.99(m,1H),8.36(d,JPH=498.6Hz, PH)；13C NMR(75MHz,CDCl3) δ=13.54 (s, CH3),19.15(s, CH2),21.97(s,CH2),30.24(s,CH2),77.61(d,JCP=9.0Hz, C), 98.94 (s, C), 125.91 (d, JCP= 10.0Hz,C),127.88(d,JCP=11.4Hz, CH), 128.60 (d, JCP=12.9Hz, 2CH), 130.70 (d, JCP= 11.5Hz,2CH),131.57(d,JCP=102.7Hz, C), 131.75 (d, JCP=102.5Hz, C), 132.10 (d, JCP= 4.1Hz,CH),132.18(s,CH),132.19(d,JCP=4.8Hz, CH), 132.89 (d, JCP=8.6Hz, CH)；31P{1H} NMR(121MHz,CDCl3) δ=17.3；HRMS Calcd.for C18H19OP[M+H+]283.1246,Found:283.1249.
The synthetic method of embodiment 2I-h, I-i, I-l：
For modus ponens A raw materials of compound 10mmol in 100mL schlenk, three times, anhydrous second is added in vacuum and exchange nitrogen Ether (with THF when synthesis I-l) 50mL, is then cooled to -75 DEG C by system, n-BuLi 10mmol, and insulation reaction is added dropwise 1h (system 1).It takes another 100mL schlenk vacuum and exchange nitrogen three times, 20mL anhydrous ethers will be entered, be then added PhPCl211mmol, and it is cooled to -78 DEG C (systems 2).The turbid solution in system 1 is injected into system with syringe at -75 DEG C In 2, after keep the temperature 10min, reaction voluntarily restores to room temperature, and reacts 1h.Reaction terminates, under open state, toward reaction 5mL water is added in system, reacts 10min, post-processing approach is consistent with front.
I-i yields:39%, light yellow solid,1H NMR(300MHz,CDCl3) δ=7.26-7.55 (m, 9H), 7.72- 7.80(m,4H),8.03-8.11(m,1H),8.40(d,JPH=497.4Hz, PH)；13C NMR(75MHz,CDCl3) δ=90.52 (s,C),91.25(d,JCP=8.4Hz, C), 121.67 (s, C), 122.07 (s, CH), 124.08 (s, CH), 124.14 (d, JCP =9.8Hz, C), 124.96 (s, CH), 125.92 (s, CH), 128.86 (d, JCP=12.9Hz, 2CH), 129.08 (d, JCP= 11.3Hz,CH),129.72(s,CH),130.83(d,JCP=11.7Hz, 2CH), 131.49 (d, JCP=103.1Hz, C), 132.21(d,JCP=101.3Hz, C), 132.23 (s, CH), 132.37 (d, JCP=11.7Hz, CH), 132.50 (d, JCP= 2.9Hz,CH),132.94(d,JCP=8.6Hz, CH), 138.84 (s, C), 140.52 (s, C)；31P{1H}NMR(121MHz, CDCl3) δ=17.2；HRMS Calcd.for C22H15OPS[M+H+]359.0654,Found:359.0656；Elemental Analysis calcd for C22H15OPS (%):C 73.73,H 4.22.found:C 73.42,H4.21.
I-l yields：37%, white solid,1H NMR(300MHz,CDCl3) δ=7.15-7.58 (m, 9H), 7.65-7.69 (m,1H),7.73-7.78(m,2H),7.98-8.03(m,1H),8.64(d,JPH=501.3Hz, PH)；13C NMR(75MHz, CDCl3) δ=90.11 (d, JCP=8.4Hz, C), 95.07 (s, C), 124.29 (s, C), 124.46 (d, JCP=9.8Hz, C), 125.32(s,C),127.15(s,CH),128.73(d,JCP=12.8Hz, 2CH), 129.06 (d, JCP=11.0Hz, CH), 130.23(s,CH),130.77(d,JCP=11.5Hz, 2CH), 131.48 (d, JCP=102.3Hz, C), 132.14 (d, JCP= 7.8Hz,CH),132.25(d,JCP=2.5Hz, CH), 132.29 (d, JCP=100.7Hz, C), 132.38 (d, JCP=2.9Hz, CH),132.55(s,CH),133.31(d,JCP=8.4Hz, CH), 133.50 (s, CH)；31P{1H}NMR(121MHz,CDCl3)δ =16.1；HRMS Calcd.for C20H14 79BrOP[M+H+]381.0038,Found:381.0045.
The synthesis of embodiment 4II-a to II-m
Above-mentioned markaThe synthesis of compound uses toluene solvant, markbThe synthesis of compound uses DMF solvent.Take target Object I raw material 1mmol raw materials are in the 30mL schlenk pipes with cock, in addition the rubber stopper in ventilation, then vacuumizes and change nitrogen Three times, then under nitrogen protection, anhydrous and oxygen-free toluene 5mL or DMF5mL is added, and change rubber stopper into polytetrafluoroethylene (PTFE) in gas Sealing-plug.System is sealed.It is reacted at 110 DEG C -120 DEG C.After reaction, it is evaporated under reduced pressure out reaction dissolvent, with dichloromethane： Ethyl acetate=5:1 crosses pillar separation.
II-a yields：82%,1H NMR(300MHz,CDCl3) δ=7.28-7.53 (m, 10H), 7.59-7.79 (5H)；13C NMR(75MHz,CDCl3) δ=124.68 (d, JCP=9.5Hz, CH), 126.60 (d, JCP=6.4Hz, 2CH), 128.93 (d,JCP=12.2,2CH), 128.94 (d, JCP=10.9Hz, 2CH), 128.94 (s, 2CH), 129.19 (d, JCP=5.3Hz, CH),129.95(d,JCP=97.7Hz, C), 130.73 (d, JCP=10.7Hz, 2CH), 132.26 (d, JCP=2.9Hz, CH), 132.52(d,JCP=10.4Hz, C), 132.73 (d, JCP=108.2Hz, C), 133.23 (d, JCP=1.8Hz, CH), 136.56 (d,JCP=20.1Hz, CH), 138.72 (d, JCP=94.1Hz, C), 141.62 (d, JCP=28.0Hz, C)；31P{1H}NMR (121MHz,CDCl3) δ=39.1.
II-b yields：81%, white solid, fusing point:145-147℃；1H NMR(300MHz,CDCl3) δ=2.29 (s, CH3),7.11(d,JHH=8.1Hz, 2H), 7.25-7.47 (m, 6H), 7.57-7.61 (m, 4H), 7.71-7.78 (m, 2H)；13C NMR(75MHz,CDCl3) δ=21.36 (s, CH3),124.46(d,JCP=9.6Hz, CH), 126.51 (d, JCP=6.5Hz, 2CH),128.83(d,JCP=10.9Hz, CH), 128.89 (d, JCP=12.2Hz, 2CH), 128.97 (d, JCP=10.7Hz, CH),129.66(s,2CH),129.68(d,JCP=10.5Hz, C), 130.08 (d, JCP=97.5Hz, C), 130.73 (d, JCP =10.7Hz, 2CH), 132.19 (d, JCP=2.9Hz, CH), 132.63 (d, JCP=108.2Hz, C), 133.18 (d, JCP= 2.0Hz,CH),135.49(d,JCP=20.2Hz, CH), 138.62 (d, JCP=93.8Hz, C), 139.01 (s, C), 141.83 (d,JCP=28.1Hz, C)；31P{1H}NMR(121MHz,CDCl3) δ=39.3；HRMS Calcd.for C21H17OP[M+H+] 317.1090,Found:317.1096；Elemental analysis calcd for C21H17OP (%):C 79.73,H 5.42.found:C 79.69,H 5.22.
II-c yields：83%, white solid, fusing point:194-196℃；1H NMR(300MHz,CDCl3) δ=7.27-7.70 (m,15H),7.77-7.84(m,4H)；13C NMR(75MHz,CDCl3) δ=124.74 (d, JCP=9.6Hz, CH), 126.93 (s,2CH),127.05(d,JCP=6.5Hz, 2CH), 127.59 (s, 2CH), 127.64 (s, CH), 128.85 (s, 2CH), 129.00(d,JCP=4.4Hz, CH), 129.01 (d, JCP=12.4Hz, 2CH), 129.13 (d, JCP=5.5Hz, CH), 129.88(d,JCP=97.8Hz, C), 130.77 (d, JCP=10.8Hz, 2CH), 131.45 (d, JCP=10.7Hz, C), 132.36(d,JCP=2.9Hz, CH), 132.62 (d, JCP=106.9Hz, C), 133.32 (d, JCP=1.9Hz, CH), 136.41 (d,JCP=20.0Hz, CH), 138.20 (d, JCP=94.1Hz, C), 140.20 (s, C), 141.50 (s, C), 141.71 (d, JCP =28.1Hz, C)；31P{1H}NMR(121MHz,CDCl3) δ=39.3；HRMS Calcd.for C26H19OP[M+H+] 379.1246,Found:379.1251.
II-d yields 80%, white solid,1H NMR(300MHz,CDCl3) δ=3.75 (OCH3),6.83(d,JHH= 8.7Hz,2H),7.24-7.51(m,7H),7.56-7.66(m,3H),7.72-7.79(m,2H)；13C NMR(75MHz,CDCl3) δ=55.27 (s, OCH3),114.40(s,2CH),124.26(d,JCP=9.7Hz, CH), 125.18 (d, JCP=10.8Hz, C), 128.04(d,JCP=6.5Hz, 2CH), 128.57 (d, JCP=10.5Hz, CH), 128.89 (d, JCP=12.4Hz, 2CH), 128.94(d,JCP=10.3Hz, CH), 130.20 (d, JCP=97.4Hz, C), 130.72 (d, JCP=10.7Hz, 2CH), 132.17(d,JCP=2.9Hz, CH), 132.41 (d, JCP=108.4Hz, C), 133.18 (d, JCP=2.0Hz, CH), 134.15 (d,JCP=20.1Hz, CH), 138.23 (d, JCP=93.9Hz, C), 142.02 (d, JCP=28.2Hz, C), 160.12 (s, C) ；31P{1H}NMR(121MHz,CDCl3) δ=39.3.
II-e yields：79%, yellow solid, fusing point:128-130℃；1H NMR(400MHz,CDCl3) δ=6.94 (d, JHH=8.4Hz, 2H), 6.99-7.06 (m, 6H), 7.19-7.24 (m, 5H), 7.37-7.58 (m, 9H), 7.74-7.79 (m, 2H)；13C NMR(100MHz,CDCl3) δ=122.51 (s, 2CH), 123.63 (s, 2CH), 124.27 (d, JCP=9.6Hz, CH),125.07(s,4CH),125.79(d,JCP=10.8Hz, C), 127.58 (d, JCP=6.6Hz, 2CH), 128.57 (d, JCP =10.5Hz, CH), 128.96 (d, JCP=12.1Hz, 2CH), 129.02 (s, CH), 129.39 (s, 4CH), 130.38 (d, JCP =96.7Hz, C), 130.81 (d, JCP=10.8Hz, 2CH), 132.19 (d, JCP=2.6Hz, CH), 132.54 (d, JCP= 108.3Hz,C),133.22(s,CH),133.98(d,JCP=20.2Hz, CH), 138.34 (d, JCP=93.9Hz, C), 142.16(d,JCP=28.0Hz, C), 147.08 (s, C), 148.44 (s, C)；31P{1H}NMR(162MHz,CDCl3) δ= 39.3；HRMS Calcd.for C32H24NOP[M+H+]470.1668,Found:470.1671.
II-f yields：77%, light yellow solid, fusing point:213-215℃；1H NMR(300MHz,CDCl3) δ=6.96- 7.01(m,2H),7.27-7.48(m,6H),7.57-7.77(m,6H)；13C NMR(75MHz,CDCl3) δ=116.03 (d, J= 21.8Hz,2CH),124.68(d,JCP=9.6Hz, CH), 128.40 (dd, J1=8.1Hz, J2=6.3Hz, 2CH), 128.78 (dd,J1=3.5Hz, J2=10.7Hz, C), 128.98 (d, JCP=12.2Hz, 2CH), 129.03 (d, J=10.3Hz, CH), 129.09 (d, J=10.5Hz, CH), 129.68 (d, JCP=96.1Hz, C), 130.69 (d, J=10.7Hz, 2CH), 132.37 (d,JCP=2.9Hz, CH), 132.41 (d, J=108.5Hz, C), 133.31 (d, J=2.0Hz, CH), 136.25 (dd, J1= 19.8Hz,J2=2.2Hz, CH), 137.66 (d, JCP=94.1Hz, C), 141.56 (d, J=28.1Hz, C), 162.92 (d, JCF =248.2Hz, C)；31P{1H}NMR(121MHz,CDCl3) δ=39.2；HRMS Calcd.for C20H14FOP[M+H+] 321.0839,Found:321.0841；Elemental analysis calcd for C20H14FOP (%):C 75.00,H 4.41.found:C 75.16,H 4.19.
II-g yields：75%,1H NMR(400MHz,CDCl3) δ=7.31-7.53 (m, 8H), 7.60-7.66 (m, 2H), 7.72-7.77 (m, 2H), 7.81 (d, J=8.0Hz, 2H)；13C NMR(100MHz,CDCl3) δ=123.92 (q, JCF= 272Hz,C),125.23(d,JCP=9.4Hz, CH), 125.82 (q, JCF=3.8Hz, 2CH), 126.75 (d, JCP=6.2Hz, 2CH),129.06(d,JCP=12.3Hz, 2CH), 129.12 (s, CH), 129.30 (d, JCP=98.2Hz, C), 129.68 (d, JCP=10.6Hz, CH), 130.27 (q, JCF=32.3Hz, C), 130.66 (d, JCP=10.8,2CH), 132.53 (d, JCP= 2.7Hz,CH),132.63(d,JCP=108.7Hz, C), 133.42 (d, JCP=1.4Hz, CH), 136.05 (d, JCP= 10.1Hz,C),137.36(d,JCP=94.6Hz, C), 138.88 (d, JCP=19.5Hz, CH), 141.13 (d, JCP= 27.6Hz,C)；31P{1H}NMR(162MHz,CDCl3) δ=38.1.
II-h yields：79%,1H NMR(400MHz,CDCl3) δ=6.91-6.93 (m, 1H), 7.22 (d, JHH= 5.2Hz,1H),7.27-7.41(m,6H),7.45-7.48(m,2H),7.57-7.61(m,1H),7.74-7.79(m,2H)；13C NMR(100MHz,CDCl3) δ=124.49 (d, JCP=9.8Hz, CH), 126.37 (s, CH), 127.73 (d, JCP=3.7Hz, CH),128.22(s,CH),128.84(d,JCP=10.7Hz, CH), 128.96 (d, JCP=12.4Hz, 2CH), 129.14 (d, JCP=10.3Hz, CH), 129.67 (d, JCP=96.6Hz, C), 130.85 (d, JCP=10.9Hz, 2CH), 131.90 (d, JCP= 105.2Hz,C),132.44(d,JCP=2.9Hz, CH), 133.39 (d, JCP=1.7Hz, CH), 133.59 (d, JCP= 94.1Hz,C),134.19(d,JCP=19.1Hz, CH), 136.06 (d, JCP=14.6Hz, C), 142.01 (d, JCP= 27.6Hz,C)；31P{1H}NMR(162MHz,CDCl3) δ=38.1.
II-i yields：64%,1H NMR(300MHz,CDCl3) δ=7.23-7.47 (m, 9H), 7.59-7.71 (m, 4H), 7.76-7.83(m,2H)；13C NMR(75MHz,CDCl3) δ=122.06 (s, CH), 124.36 (s, CH), 124.72 (s, CH), 124.92(d,JCP=12.4Hz, CH), 124.96 (s, CH), 125.60 (s, CH), 129.06 (d, JCP=12.5Hz, 2CH), 129.14(d,JCP=5.3Hz, CH), 129.28 (d, JCP=5.7Hz, CH), 129.56 (d, JCP=99.4Hz, C), 130.77 (d,JCP=10.9Hz, 2CH), 132.30 (d, JCP=108.7Hz, C), 132.56 (d, JCP=2.9Hz, CH), 133.44 (d, JCP=2.0Hz, CH), 133.76 (d, JCP=93.9Hz, C), 136.03 (d, JCP=14.5Hz, C), 136.61 (d, JCP= 19.0Hz,CH),139.15(s,C),140.11(s,C),141.60(d,JCP=27.4Hz, C)；31P{1H}NMR(121MHz, CDCl3) δ=38.1.
II-j yields：45%, light yellow solid, fusing point:150-152℃；1H NMR(400MHz,CDCl3) δ=7.24- 7.28(m,2H),7.33-7.51(m,8H),7.65-7.78(m,6H),8.17-8.19(m,1H)；13C NMR(100MHz, CDCl3) δ=124.81 (d, JCP=9.6Hz, CH), 125.33 (s, CH), 125.39 (s, CH), 126.03 (s, CH), 126.33 (d,JCP=4.3Hz, CH), 126.54 (s, CH), 128.54 (s, CH), 128.81 (d, JCP=12.3Hz, 2CH), 128.81 (s,CH),129.23(d,JCP=96.5Hz, C), 129.28 (d, JCP=1.3Hz, CH), 129.38 (d, JCP=1.2Hz, CH), 130.89(d,JCP=10.5Hz, 2CH), 131.12 (d, JCP=9.0Hz, C), 131.56 (d, JCP=5.4Hz, C), 131.96 (d,JCP=106.8Hz, C), 132.32 (d, JCP=2.7Hz, CH), 133.34 (d, JCP=1.7Hz, CH), 134.00 (s, C), 138.85(d,JCP=91.2Hz, C), 141.94 (d, JCP=28.3Hz, C), 142.14 (d, JCP=20.6Hz, CH)；31P{1H} NMR(162MHz,CDCl3) δ=39.9.HRMS Calcd.for C24H17OP[M+H+]353.1090,Found:353.1092.
II-k yields：41%, white solid, fusing point:79-81℃；1H NMR(300MHz,CDCl3) δ=6.42 (d, JHP =37.2Hz, 1H), 6.95-6.99 (m, 1H), 7.06-7.08 (m, 2H), 7.25-7.41 (m, 10H), 7.46-7.69 (m, 4H),7.87-7.89(m,1H)；13C NMR(75MHz,CDCl3) δ=124.55 (d, JCP=9.5Hz, CH), 127.06 (s, CH),127.58(s,CH),128.21(s,CH),128.29(s,2CH),128.78(d,JCP=4.3Hz, CH), 128.83 (d, JCP=12.1Hz, 2CH), 129.03 (d, JCP=5.9Hz, CH), 129.24 (s, 3CH, overlapped), 129.89 (d, JCP =97.7Hz, C), 131.0 (s, CH), 131.05 (d, JCP=12.5Hz, 2CH), 131.06 (d, JCP=107.8Hz, C), 131.42(d,JCP=10.3Hz, C), 132.38 (d, JCP=2.8Hz, CH), 133.19 (d, JCP=1.7Hz, CH), 138.02 (d,JCP=92.9Hz, C), 141.50 (s, C), 141.55 (d, JCP=7.5Hz, C), 141.70 (d, JCP=19.5Hz, CH), 142.14(d,JCP=28.7Hz, C)；31P{1H}NMR(121MHz,CDCl3) δ=39.3；HRMS Calcd.for C26H19OP [M+H+]379.1246,Found:379.1250.
II-l yields：52%, white solid, fusing point：60-61℃1H NMR(300MHz,CDCl3) δ=6.97-7.03 (m, 1H),7.17-7.22(m,1H),7.28-7.52(m,7H),7.57-7.76(m,4H),7.82-7.85(m,1H)；13C NMR (75MHz,CDCl3) δ=122.29 (d, JCP=7.4Hz, C), 125.18 (d, JCP=9.5Hz, CH), 127.52 (s, CH), 128.79(d,JCP=12.5Hz, 2CH), 128.88 (d, JCP=102.6Hz, C), 129.00 (d, JCP=10.3Hz, CH), 129.49(d,JCP=10.4Hz, CH), 129.51 (s, CH), 130.02 (d, JCP=3.5Hz, CH), 130.87 (d, JCP= 10.8Hz,2CH),131,75(d,JCP=107.7Hz, C), 132.38 (d, JCP=2.8Hz, CH), 133.28 (d, JCP= 2.1Hz,CH),133.33(d,JCP=9.9Hz, C), 133.81 (s, CH), 136.82 (d, JCP=94.2Hz, C), 141.21 (d,JCP=28.4Hz, C), 143.29 (d, JCP=19.4Hz, CH)；31P{1H}NMR(121MHz,CDCl3) δ=41.1；HRMS Calcd.for C20H14 79BrOP[M+H+]381.0038,Found:381.0040.
II-m yields：39%, colourless liquid,1H NMR(300MHz,CDCl3) δ=0.80 (t, JHH=7.5Hz, 3H), 1.25-1.29(m,2H),1.43-1.53(m,2H),2.26-2.42(m,2H),6.96(d,JPH=38.1Hz, 1H), 7.20- 7.27(m,2H),7.39-7.55(m,5H),7.61-7.68(m,2H)；13C NMR(75MHz,CDCl3) δ=13.70 (s, CH3),22.30(s,CH2),27.25(d,JCP=10.1Hz, CH2),29.78(d,JCP=5.0Hz, CH2),123.66(d,JCP =9.8Hz, CH), 128.31 (d, JCP=10.3Hz, CH), 128.79 (d, JCP=12.2Hz, 2CH), 128.94 (d, JCP= 10.5Hz,CH),129.38(d,JCP=95.9Hz, C), 130.80 (d, JCP=10.7Hz, 2CH), 132.08 (d, JCP= 106.1Hz,C),132.15(d,JCP=2.8Hz, CH), 133.05 (d, JCP=1.9Hz, CH), 137.67 (d, JCP= 21.0Hz,CH),142.43(d,JCP=90.5Hz, C), 142.53 (d, JCP=29.6Hz, C)；31P{1H}NMR(121MHz, CDCl3) δ=40.6；HRMS Calcd.for C18H19OP[M+H+]283.1246,Found:283.1248.。
Here is the application of the compounds of this invention
Application examples 1
Using the compounds of this invention II-e as the luminescent material in OLED device, in addition select Alq3 right as the present invention Photoelectric properties measurement is carried out than material, the device architecture of implementation is as follows：
ITO/MoO3(1nm)/NPB (40nm)/luminescent material (10nm)/TPBi (30nm)/LiF (1.0nm)/Al (100nm)
The structural formula of some materials used is as follows：
Method：Tin indium oxide (ITO) glass substrate (China Nanbo Group Co) uses ultrasonic cleaning machine, according to Secondary to use detergent, deionized water, acetone, isopropanol is cleaned by ultrasonic 15min, later in the N of clean dry2Flow down drying.Then, Substrate is transferred to vacuum thermal evaporation room and further removes surface blot.MoO is crossed in vacuum steaming3, form the hole injection layer of 1nm thickness. NPB is crossed in steaming, forms the hole transmission layer of 40nm thickness.The luminescent layer for crossing 10nm thickness is steamed on the hole transport layer.It steams on the light-emitting layer The TPBi of 30nm thickness is crossed as electron transfer layer.Finally, it is electron injecting layer and 100nm Al cloudy as device that 1nm LiF are crossed in steaming Pole.The Keithley2400source meter and Topcon that Current density-voltage-brightness (J-V-L) characteristic is controlled by software BM-7A Luminance Colorimeter are measured, and electroluminescent spectrum is measured by Lab sphere CDS-610.Device is electroluminescent Luminescent spectrum is measured by Lab sphere CDS-610.The photoelectric properties of device are as follows：
Table 1：The photoelectric property of device
As can be seen from the above table, as current density is in 200-500mA.cm-2When section, using the compounds of this invention II-e The launch wavelength of organic electroluminescence device as luminescent layer preparation is almost without changing, under the same conditions, base It is apparently higher than Alq3 in the efficiency of the organic electroluminescence device of the compounds of this invention II-e.It can therefore be seen that the present invention Organic electroluminescence device prepared by compound has high efficiency.

Claims (2)

1. a kind of synthetic method of benzo phosphene class compound, which is characterized in that be achieved by the steps of：
(1) compound I-a to I-m is synthesized
R is the group as described in following table：
Modus ponens A raw materials of compound vacuumizes in schlenk, is filled with nitrogen, and organic solvent is added, then by system temperature control to- 75 DEG C to -78 DEG C, n-BuLi is added dropwise, system is restored to reacting at room temperature, referred to as system 1；Another schlenk is taken to take out true Sky is filled with nitrogen, and organic solvent is added, PhPCl is then added2, and -75 DEG C to -78 DEG C are cooled to, referred to as system 2；With injection Turbid solution in system 1 is injected into system 2 by device, after keep the temperature；Reaction terminates, under open state, toward reaction system In be slowly added to water reaction, after reaction, through extraction, merge organic phase, vacuum distillation, cross post separation, obtain list of target object I；
The organic solvent choosing：Anhydrous ether or anhydrous tetrahydro furan；
(2) compound II-a to II-m is generated by trace air catalytic
It takes object I raw materials in the schlenk pipes with cock, then vacuumizes, be filled with nitrogen, then under nitrogen protection, Anhydrous and oxygen-free organic solvent is added, system is sealed, 110 DEG C of -120 DEG C of reactions；After reaction, it is molten to be evaporated under reduced pressure out reaction Post separation is crossed in agent；
The organic solvent selects toluene or DMF, above-mentioned markaThe synthesis of compound uses toluene solvant, markbThe conjunction of compound At using DMF solvent.
2. the synthetic method of benzo phosphene class compound as described in claim 1, which is characterized in that with compound II-a to II-h is object.
CN201710116743.9A 2017-02-28 2017-02-28 A kind of synthetic method of benzo phosphene Expired - Fee Related CN106831876B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710116743.9A CN106831876B (en) 2017-02-28 2017-02-28 A kind of synthetic method of benzo phosphene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710116743.9A CN106831876B (en) 2017-02-28 2017-02-28 A kind of synthetic method of benzo phosphene

Publications (2)

Publication Number Publication Date
CN106831876A CN106831876A (en) 2017-06-13
CN106831876B true CN106831876B (en) 2018-11-02

Family

ID=59138314

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710116743.9A Expired - Fee Related CN106831876B (en) 2017-02-28 2017-02-28 A kind of synthetic method of benzo phosphene

Country Status (1)

Country Link
CN (1) CN106831876B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109096337B (en) * 2018-10-08 2019-11-22 苏州大学 A kind of phospha indole derivatives, benzo phospha indole derivatives and preparation method thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109180728A (en) * 2018-10-23 2019-01-11 佛山科学技术学院 A kind of carbazyl benzo phosphene derivative and preparation method thereof
CN109836460A (en) * 2019-04-08 2019-06-04 西安交通大学 Blue-green heat lag fluorescent material based on rigid phosphine oxide group
CN111518136B (en) * 2019-12-13 2021-09-21 华南理工大学 Phosphoro indole derivative, preparation method and chemical and biological application thereof
CN113999264A (en) * 2021-11-25 2022-02-01 郑州大学 Halogenated phosphacenaphthene compound and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009280512A (en) * 2008-05-20 2009-12-03 Japan Science & Technology Agency Polybenzophosphole compound and method for producing the same
CN103214521B (en) * 2013-05-03 2015-06-10 苏州大学 Method for preparing dibenzophosphole derivants
WO2015111647A1 (en) * 2014-01-24 2015-07-30 国立大学法人名古屋大学 Phosphole compound and fluorescent dye containing same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109096337B (en) * 2018-10-08 2019-11-22 苏州大学 A kind of phospha indole derivatives, benzo phospha indole derivatives and preparation method thereof

Also Published As

Publication number Publication date
CN106831876A (en) 2017-06-13

Similar Documents

Publication Publication Date Title
CN106831876B (en) A kind of synthetic method of benzo phosphene
CN104293349B (en) A kind of based on benzene for the luminescent material of phenthazine unit and intermediate thereof and the organic electro-optic device prepared by this luminescent material
CN108586441A (en) A kind of compound, a kind of organic light-emitting display device
CN102224158A (en) Novel heterocyclic compound and use thereof
CN110016053B (en) Asymmetric substituted soluble pyridine derivative, preparation, n-doped electron transport layer and application
CN105051019A (en) Electron transport material and organic electroluminescent device using same
CN108912175A (en) A kind of metal iridium complex and its organic luminescent device
CN109251194A (en) A kind of triaizine compounds and its organic luminescent device of the class formation containing fluorenes
CN109020903A (en) A kind of triarylamine derivative and its organic electroluminescence device
CN103865525B (en) A kind of organic electroluminescent compounds
CN105693773A (en) Organic molecule electron transmission material with high triplet level and preparing method and application thereof
CN104685650A (en) Salts of cyclopentadiene as n-dopants for organic electronics
CN109180526A (en) A kind of anthracene derivative and its organic luminescent device
CN108084197A (en) A kind of bis-carbazole derivative and its organic luminescent device
TW202136246A (en) Compounds for electronic devices
CN108047233A (en) A kind of carbazole analog derivative and its organic luminescent device
CN108084195A (en) A kind of bis-carbazole fused ring compound and its organic luminescent device
Ding et al. Novel spiro-based host materials for application in blue and white phosphorescent organic light-emitting diodes
CN108218891A (en) A kind of electroluminescent compounds and its preparation method and application
US20160155958A1 (en) Bicyclic iridium complex and process for preparing same, organic light emitting device and process for preparing same
CN108558948B (en) Diphospha-containing heterocyclic cyclopentadiene fused ring organic electroluminescent compound and synthesis method thereof
CN109422743A (en) Miscellaneous carbazole derivates of dinitrogen and preparation method thereof and application as electroluminescent material
CN113214167A (en) Benzoquinazoline compound and organic electroluminescent element
CN108623635B (en) 1, 3-azaphospholane compound and synthesis method thereof
CN103887447A (en) Organic electroluminescent device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for 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: 20181102

Termination date: 20190228