CN107805261A - A kind of self assembly quaternary phosphine salt material - Google Patents
A kind of self assembly quaternary phosphine salt material Download PDFInfo
- Publication number
- CN107805261A CN107805261A CN201710970429.7A CN201710970429A CN107805261A CN 107805261 A CN107805261 A CN 107805261A CN 201710970429 A CN201710970429 A CN 201710970429A CN 107805261 A CN107805261 A CN 107805261A
- Authority
- CN
- China
- Prior art keywords
- butane
- tri
- tetradecyloxyaniline
- phosphonium
- double
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000001338 self-assembly Methods 0.000 title claims abstract description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000001273 butane Substances 0.000 claims abstract description 38
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- OTIVLGJBKUFOEX-UHFFFAOYSA-N n-tetradecoxyaniline Chemical compound CCCCCCCCCCCCCCONC1=CC=CC=C1 OTIVLGJBKUFOEX-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 diphenyl phosphonium halide Chemical class 0.000 claims abstract description 20
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical class P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 36
- 239000012074 organic phase Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- 229940071870 hydroiodic acid Drugs 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 5
- JCBJVAJGLKENNC-UHFFFAOYSA-M potassium ethyl xanthate Chemical compound [K+].CCOC([S-])=S JCBJVAJGLKENNC-UHFFFAOYSA-M 0.000 claims description 5
- 238000007039 two-step reaction Methods 0.000 claims description 5
- WOUIKYKNZGCTCD-UHFFFAOYSA-N [O].CCCCCCCCCCCCCC Chemical compound [O].CCCCCCCCCCCCCC WOUIKYKNZGCTCD-UHFFFAOYSA-N 0.000 claims description 4
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical class C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- XSOTVEGLPNWBPO-UHFFFAOYSA-N diphenylphosphane;hydrobromide Chemical compound [Br-].C=1C=CC=CC=1[PH2+]C1=CC=CC=C1 XSOTVEGLPNWBPO-UHFFFAOYSA-N 0.000 claims description 3
- QMHXNAKMQMEERO-UHFFFAOYSA-N diphenylphosphane;hydroiodide Chemical compound I.C=1C=CC=CC=1PC1=CC=CC=C1 QMHXNAKMQMEERO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 4
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- QKLWAMMQKBOTCD-UHFFFAOYSA-N butane;diphenylphosphane Chemical compound CCCC.C=1C=CC=CC=1PC1=CC=CC=C1 QKLWAMMQKBOTCD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003989 dielectric material Substances 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- LSMAIBOZUPTNBR-UHFFFAOYSA-N phosphanium;iodide Chemical compound [PH4+].[I-] LSMAIBOZUPTNBR-UHFFFAOYSA-N 0.000 abstract description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052794 bromium Inorganic materials 0.000 abstract description 2
- 238000001378 electrochemiluminescence detection Methods 0.000 abstract description 2
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 239000002608 ionic liquid Substances 0.000 description 5
- 150000004714 phosphonium salts Chemical group 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 235000002597 Solanum melongena Nutrition 0.000 description 4
- 244000061458 Solanum melongena Species 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- FNZRBPSACINSCO-UHFFFAOYSA-N C=1C=CC=CC=1ClC1=CC=CC=C1 Chemical compound C=1C=CC=CC=1ClC1=CC=CC=C1 FNZRBPSACINSCO-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000012991 xanthate Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 0 C*c1cc(CP(*)(c2ccccc2)C2=CCCCC=C2)cc(*)c1* Chemical compound C*c1cc(CP(*)(c2ccccc2)C2=CCCCC=C2)cc(*)c1* 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5456—Arylalkanephosphonium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention provides one kind 3, double (diphenyl phosphonium halide) the butane self-assembled materials of 4,5 three (tetradecyloxyaniline) Isosorbide-5-Nitraes, to form the double london dispersion forces between skeleton and chain alkyl of two stronger ionic bonds, the self-assembled structures material of high-sequential is realized；Its synthesis mainly passes through 1,4 pairs of (diphenyl phosphine) butane and 3,4, substitution reaction generation 3 occurs for 5 three (tetradecyloxyaniline) benzyl chlorides, 4,5 three (tetradecyloxyanilines) 1,4 pairs of (Er Ben Ji phosphonium chlorides) butane, and purified by re-crystallizing in ethyl acetate, then using ethoxy-dithioformic acid root as anionite, then with the reaction of hydrogen bromine/acid iodide corresponding 3,4 can be generated, double (hexichol bromide/phosphonium iodide) butane of 5 three (tetradecyloxyaniline) Isosorbide-5-Nitraes.This kind of self assembly quaternary alkylphosphonium salt will provide new dielectric material for applied technical fields such as lithium ion conducting, porphyryl electrogenerated chemiluminescence, template preparation, nano materials.
Description
Technical field
The present invention relates to technical field of organic chemistry, and in particular to a kind of quaternary phosphonium salt ionic liquid self-assembled material.
Background technology
Ionic liquid and supercritical CO2, aqueous two-phase be listed as three big " green " solvents.Quaternary phosphonium salt ionic liquid has steam
The advantages that forcing down, be nonflammable, be hot good with chemical stability, corrosivity is low, electrical conductivity is high, electrochemical window is big, and by conduct
A kind of new self assembly dielectric material is applied to chemical, electrochemistry, new material, electron and information technology, biology and doctor
The new industry field of the current strategic emphasis development of numerous China such as medicine.Quaternary alkylphosphonium salt possesses the structure similar to quaternary ammonium salt and materialization
Property, but quaternary alkylphosphonium salt is lower compared to quaternary ammonium salt fusing point, physical property and chemical property are all more stable.At present, both at home and abroad
There are many researchs for ammonium salt to report, but the research for quaternary alkylphosphonium salt is then relatively less, especially at home on quaternary alkylphosphonium salt
Property Quality Research is just started to walk.Quaternary alkylphosphonium salt relies on the good characteristic of itself, as what it was studied deepens continuously, will have more
Good application prospect and huge development potentiality.
Quaternary phosphonium salt ionic liquid molecule rely primarily on the Coulomb force between negative ions, the london dispersion force between chain alkyl,
It is and anisotropic caused by the factors such as microsegregation between ion (polarity) and chain alkyl (nonpolar) region
Self assembly arrangement architecture, therefore molecules align has high-sequential.Just because of this design feature, MOLECULE DESIGN can be used
Method, change is purposefully carried out to high molecular arrangement mode and changes and adjusts, so as to improve the performance of material.At present, ion
Liquid self-assembled material has been widely used in fields such as biological medicine, nanometer technologies, many important biochemical reactions and height
The processing procedure of technology content is all to utilize barrier film, vesica, monofilm or micella caused by molecular self-assembling.Self-assembled nanometer
Grain is more and more paid attention to, and this kind of nano material shows unique excellent performance, quilt in optics and electronic applications
In depth apply extensively, and obtained certain achievement.Because nano-particle just can be with when as single entity
Quantum size effect is produced, when forming self-assembled structures between particle, its optics, magnetics and electricity significant interaction carry
It is high so that material is obviously improved in physical and chemical performance macroscopically.
The content of the invention
It is an object of the invention to provide a kind of double (diphenyl phosphonium halide) butane of 3,4,5- tri- (tetradecyloxyaniline) 1,4-
Self assembly quaternary phosphine salt material.
In order to achieve the above object, the technical scheme that first aspect present invention provides is as follows：(the tetradecane oxygen of 3,4,5- tri-
Base) Isosorbide-5-Nitrae-bis- (diphenyl phosphonium halide) butane self assembly quaternary phosphine salt material, its molecular structure is shown in formula I：
The second aspect of the present invention provides the preparation method of previously described formula I chlorination phosphonium compounds, and it comprises the following steps：
(1) Isosorbide-5-Nitrae-bis- (diphenyl phosphine) butane and 3,4,5- tri- (tetradecyloxyaniline) benzyl chlorides are put into chloroform solvent,
Backflow is stirred and heated under anaerobic state；After reaction stops, chloroform solvent is spin-dried for, crystallization obtains 3,4,5- tri- (tetradecane oxygen
Base) Isosorbide-5-Nitrae-bis- (Er Ben Ji phosphonium chlorides) butane, i.e. Formula II compound；
(2) double (Er Ben Ji phosphonium chlorides) butane (Formula II) of 3,4,5- tri- (tetradecyloxyaniline) 1,4- for obtaining above-mentioned reaction
With ehtyl potassium xanthate mixed dissolution in chloroform, stir and be filtrated to get organic phase, then add hydrobromic acid or hydroiodic acid,
Stirring reaction obtains double (the diphenyl-ethyl Huang Yuan Suan Phosphonium) butane of 3,4,5- tri- (tetradecyloxyaniline) 1,4-；
(3) after reaction terminates, washing layering obtains organic phase, and revolving removes chloroform, and crystallization obtains：3,4,5- tri- (14
Alkoxy) Isosorbide-5-Nitrae-bis- (diphenyl phosphonium bromide) butane, formula III compound, and 3,4,5- tri- (tetradecyloxyaniline) Isosorbide-5-Nitraes-bis- (hexichol
Base phosphonium iodide) butane, formula IV compound.
Preferably, in step (1), Isosorbide-5-Nitrae-bis- (diphenyl phosphine) butane and 3,4,5- tri- (tetradecyloxyaniline) benzyl chlorides mole
Than for 1：2.5-3.5.
Preferably, in step (1), at room temperature, by Isosorbide-5-Nitrae-bis- (diphenyl phosphine) butane and 3,4,5- tri- (tetradecane oxygen
Base) benzyl chloride is put into chloroform solvent rapidly under nitrogen protection, and is passed through N2Residual air in solution is removed, under anaerobic state
It is stirred and heated to backflow 60-72h.
Preferably, in step (2), by 3,4,5- tri- (tetradecyloxyaniline) Isosorbide-5-Nitraes-bis- (Er Ben Ji phosphonium chlorides) butane (II) with
The ehtyl potassium xanthate of 3.0-4.0 times of molar equivalent, mixed dissolution is in chloroform.
Preferably, in step (3), the hydrobromic acid or hydroiodic acid of 4.0-6.0 times of molar equivalent are added, stirring reaction under normal temperature
6-10 hours.
Preferably, step (2) and step (3), the gross production rate of two-step reaction is 84-85%.
Preferably, the crystallization in step (1), step (3) crystallizes to obtain associated products to add ethyl acetate.
The preparation method of 3,4,5- tri- (tetradecyloxyaniline) Isosorbide-5-Nitraes-bis- (diphenyl phosphonium halides) butane of the Formulas I of the present invention,
Its chemical equation is as follows：
3,4,5- tri- (tetradecyloxyaniline) 1,4- that the second aspect of the present invention provides previously described formula I is double (diphenyl phosphonium halide)
The preparation method of butane, it comprises the following steps：
(1) at room temperature, it is 1 by mol ratio：Double (diphenyl phosphine) butane of 2.5-3.5 1,4- and 3,4,5- tri- (14
Alkoxy) benzyl chloride is put into chloroform solvent rapidly under nitrogen protection, and is passed through N2Remove residual air in solution, anaerobic shape
Backflow 60-72h is stirred and heated under state；After reaction stops, chloroform solvent is spin-dried for, and appropriate acetic acid second is added into product
Ester, it is heated to after being completely dissolved, stands still for crystals 10-12h at 4 DEG C and obtain white solid：3,4,5- tri- (tetradecyloxyaniline) 1,
Double (the Er Ben Ji phosphonium chlorides) butane (II) of 4-, yield 95-97%.1H NMR(500 MHz,CDCl3):δ 0.88 (t, J=
6.22Hz,18H),1.26-1.43(m,132H),1.62-1.64(m,12H),1.69(s,4H),3.55(s,12H),3.84(d,
J=6.28Hz, 4H), 4.59 (s, 4H), 6.15 (s, 4H), 7.62-7.90 (m, 20H)；
(2) double (the Er Ben Ji phosphonium chlorides) butane (II) of 3,4,5- tri- (tetradecyloxyaniline) 1,4- for obtaining above-mentioned reaction with
The ehtyl potassium xanthate mixed dissolution of 3.0-4.0 times of molar equivalent stirs 15-20h in chloroform under normal temperature；Then it is filtrated to get
Lurid clarification organic phase, the hydrobromic acid or hydroiodic acid of 4.0-6.0 times of molar equivalent are then added, stirring reaction 6- under normal temperature
10 hours；Reaction knot is washed twice after terminating using deionized water, and layering obtains organic phase, and revolving removes chloroform, is added appropriate
Ethyl acetate stand still for crystals 10-12h at 4 DEG C and obtain white solid：Double (the diphenyl of 3,4,5- tri- (tetradecyloxyaniline) 1,4-
Phosphonium bromide) butane (III) and 3,4,5- tri- (tetradecyloxyaniline) Isosorbide-5-Nitraes-bis- (diphenyl phosphonium iodides) butane (IV), two-step reaction
Gross production rate is 84-85%.
Patent of the present invention aims to provide a kind of self-assembled structures halogenation quaternary phosphonium salt ionic liquid material, Tong Guo bis- Phosphonium molecules
Design, Shi get Phosphonium cations and halogen anion are alternatively formed two ionic bonds, strengthen self-assembled structures in doping region
The ionic bond skeletal chain in domain, the л-л active forces that each two phenyl of band can be formed between adjacent molecule on Bing Qie Phosphonium cations；It is simultaneously every
Ge Phosphonium ion is all covalently attached to three chain alkyls by phenyl ring, and stronger london dispersion force can be formed between chain alkyl, enhancing
The formation of apolar regions, with polar region forms good microsegregation.Such Molecular Design can more preferable landform
Into the self-assembled structures material of high-sequential.
The invention provides a kind of double (diphenyl phosphonium halide) the butane self assembly materials of 3,4,5- tri- (tetradecyloxyaniline) 1,4-
Material, to form the double london dispersion forces between skeleton and chain alkyl of two stronger ionic bonds, realize the self assembly of high-sequential
Structural material；Synthesis is mainly substituted by double (diphenyl phosphine) butane of 1,4- with 3,4,5- tri- (tetradecyloxyaniline) benzyl chloride
Reaction generation 3,4,5- tri- (tetradecyloxyaniline) Isosorbide-5-Nitraes-bis- (Er Ben Ji phosphonium chlorides) butane, and carried out by re-crystallizing in ethyl acetate
Purifying, then using ethoxy-dithioformic acid root as anionite, then reacted with hydrogen bromine/acid iodide and can generate corresponding 3,4,5-
Double (hexichol bromide/phosphonium iodide) butane of three (tetradecyloxyaniline) 1,4-.This kind of self assembly quaternary alkylphosphonium salt will be lithium ion conducting, porphyrin
The applied technical fields such as base electrogenerated chemiluminescence, template preparation, nano material provide new dielectric material.
Embodiment
Such scheme is described further below in conjunction with specific embodiment.It should be understood that these embodiments are to be used to illustrate
The present invention and be not limited to limit the scope of the present invention.The implementation condition used in embodiment can be done according to the condition of specific producer
Further adjustment, unreceipted implementation condition is usually the condition in normal experiment.
Introduce and summarize
The present invention by way of example rather than provides the mode of limitation to illustrate.It should be noted that in present disclosure
Described " one " or " one kind " embodiment is not necessarily referring to same embodiment, and refers at least a kind of.
Various aspects of the invention are described below.However, as will be readily apparent to one of skill in the art, can
Implement the present invention according to the only some or all of aspects of the present invention.For purposes of illustration, provide herein specific numbering, material and
Configuration, enables one to thoroughly understand the present invention.However, be evident that for those of skill in the art,
The present invention can be implemented without concrete details.In other examples, not make the present invention is obscure many institutes have been omitted or simplified
Known feature.
Various operations are described successively as multiple discrete steps, and with most helpful in the side for understanding the present invention
Formula illustrates；However, in-order description should not be construed as to imply that these operations are necessarily dependent on order.
Reactant according to type species is illustrated to various embodiments.To show for those of skill in the art and
It is clear to, any number of different types of reactant can be used to implement for the present invention, and be more than those for the purpose of illustration
And the reactant provided herein.In addition, also it is evident that, the invention is not limited in any specific mixing is shown
Example.
Material and method
Specific embodiment
Example 1：
By (tetradecyloxyaniline) benzyl chlorides of 16.2g (21.2mmol) 3,4,5- tri- and 2.8g (6.6mmol) 1,4- under normal temperature
(double diphenylphosphines) butane is dissolved into 60mL chloroforms, is stirred vigorously in there-necked flask (100mL) and is thoroughly sloughed oxygen (nitrogen
Protection).It is heated to 61 DEG C of back flow reaction 65h.Reaction is cooled to room temperature after terminating, and reaction solution is transferred in eggplant-shape bottle, with rotation
Turn evaporimeter concentration organic phase, then add 80mL ethyl acetate, be heated to being completely dissolved, 4 are transferred to after being cooled to room temperature
DEG C refrigerator in crystallized, filter and the 3 of 12.4g obtained after drying, 4,5- tri- (tetradecyloxyaniline) Isosorbide-5-Nitraes-bis- (diphenyl chlorine
Hua Phosphonium) butane, yield 97%.
Example 2：
By (tetradecyloxyaniline) benzyl chlorides of 11.0g (14.4mmol) 3,4,5- tri- and 2.2g (5.2mmol) 1,4- under normal temperature
(double diphenylphosphines) butane is dissolved into 50mL chloroforms, is stirred vigorously in there-necked flask (100mL) and is thoroughly sloughed oxygen (nitrogen
Protection).It is heated to 61 DEG C of back flow reaction 60h.Reaction is cooled to room temperature after terminating, and reaction solution is transferred in eggplant-shape bottle, with rotation
Turn evaporimeter concentration organic phase, then add 60mL ethyl acetate, be heated to being completely dissolved, 4 are transferred to after being cooled to room temperature
DEG C refrigerator in crystallized, filter and the 3 of 9.6g obtained after drying, 4,5- tri- (tetradecyloxyaniline) Isosorbide-5-Nitraes-bis- (diphenyl chlorine
Hua Phosphonium) butane, yield 95%.
9.6g obtained above (4.9mmol) 3,4,5- tri- (14 is separately added into 150mL eggplant type flasks at room temperature
Alkoxy) Isosorbide-5-Nitrae-bis- (Er Ben Ji phosphonium chlorides) butane, 2.5g (15.6mmol) ehtyl potassium xanthates and 45mL chloroform solvents, stirring
Reaction 16 hours.After reaction terminates, it is filtered to remove suspension insoluble matter and obtains lurid clarification organic phase.Then filtrate is turned
Into 100mL eggplant type flasks, and 2.9mL (19.8mmol) 40wt% hydrobromic acid aqueous solutions are added, stirring reaction 6 is small under normal temperature
When.After question response terminates, reaction solution is cleaned twice using 40mL distilled water, layering obtains organic phase and rotates removal.Then
60mL ethyl acetate is added, dissolves by heating, is cooled to after room temperature the crystallization purifying in refrigerator (4 DEG C).Last filtering vacuum is dried
The 3 of 8.4g, 4,5- tri- (tetradecyloxyaniline) Isosorbide-5-Nitraes-bis- (diphenyl phosphonium bromides) butane are obtained afterwards, and two-step reaction gross production rate is
84%.
Example 3：
By (tetradecyloxyaniline) benzyl chlorides of 13.5g (17.7mmol) 3,4,5- tri- and 2.5g (5.9mmol) 1,4- under normal temperature
(double diphenylphosphines) butane is dissolved into 55mL chloroforms, is stirred vigorously in there-necked flask (100mL) and is thoroughly sloughed oxygen (nitrogen
Protection).It is heated to 61 DEG C of back flow reaction 72h.Reaction is cooled to room temperature after terminating, and reaction solution is transferred in eggplant-shape bottle, with rotation
Turn evaporimeter concentration organic phase, then add 65mL ethyl acetate, be heated to being completely dissolved, 4 are transferred to after being cooled to room temperature
DEG C refrigerator in crystallized, filter and the 3 of 11.0g obtained after drying, 4,5- tri- (tetradecyloxyaniline) Isosorbide-5-Nitraes-bis- (diphenyl chlorine
Hua Phosphonium) butane, yield 96%.
11.0g obtained above (5.6mmol) 3,4,5- tri- (ten is separately added into 150mL eggplant type flasks at room temperature
Tetraalkoxy) Isosorbide-5-Nitrae-bis- (Er Ben Ji phosphonium chlorides) butane, 3.4g (21.2mmol) ehtyl potassium xanthates and 50mL chloroform solvents, is stirred
Mix reaction 20 hours.After reaction terminates, it is filtered to remove suspension insoluble matter and obtains lurid clarification organic phase.Then filtrate
Go in 100mL eggplant type flasks, and add 4.2mL (22.2mmol) 45wt% hydriodic acid aqueous solutions, stirring reaction 10 under normal temperature
Hour.After question response terminates, reaction solution is cleaned twice using 50mL distilled water, layering obtains organic phase and rotates removal.So
70mL ethyl acetate is added afterwards, is dissolved by heating, is cooled to after room temperature the crystallization purifying in refrigerator (4 DEG C).Last filtering vacuum is done
The 3 of 10.2g, 4,5- tri- (tetradecyloxyaniline) Isosorbide-5-Nitraes-bis- (diphenyl phosphonium iodides) butane are obtained after dry, two-step reaction gross production rate is
85%.
Specific embodiment described above is only the preferred embodiment of the present invention, it is noted that for the art
For those of ordinary skill, under the premise without departing from the principles of the invention, some improvement or replacement can also be made, these improvement
Or replace and should also be as being considered as protection scope of the present invention.
Claims (8)
- The self assembly quaternary phosphine salt material of 1.3,4,5- tri- (tetradecyloxyaniline) Isosorbide-5-Nitraes-bis- (diphenyl phosphonium halides) butane, its molecule knot Structure is shown in formula I：
- 2. prepare the method for the self assembly quaternary phosphine salt material of Formulas I as claimed in claim 1, it is characterised in that it includes as follows Step：(1) Isosorbide-5-Nitrae-bis- (diphenyl phosphine) butane and 3,4,5- tri- (tetradecyloxyaniline) benzyl chlorides are put into chloroform solvent, anaerobic Backflow is stirred and heated under state；After reaction stops, chloroform solvent is spin-dried for, crystallization obtains 3,4,5- tri- (tetradecyloxyanilines) 1, Double (the Er Ben Ji phosphonium chlorides) butane of 4-；(2) double (the Er Ben Ji phosphonium chlorides) butane (Formula II) of 3,4,5- tri- (tetradecyloxyaniline) 1,4- for obtaining above-mentioned reaction and second Base potassium xanthate mixed dissolution stirs in chloroform and is filtrated to get organic phase, then adds hydrobromic acid or hydroiodic acid, stirring Reaction obtains double (the diphenyl-ethyl Huang Yuan Suan Phosphonium) butane of 3,4,5- tri- (tetradecyloxyaniline) 1,4-；(3) after reaction terminates, washing layering obtains organic phase, and revolving removes chloroform, and crystallization obtains：(the tetradecane oxygen of 3,4,5- tri- Base) double (diphenyl phosphonium bromide) butane of 1,4- and double (diphenyl phosphonium iodide) butane of 3,4,5- tri- (tetradecyloxyaniline) 1,4-.
- 3. the preparation method according to profit requires 2, it is characterised in that in step (1), Isosorbide-5-Nitrae-bis- (diphenyl phosphine) butane and 3, (tetradecyloxyaniline) benzyl chlorides of 4,5- tri- mol ratio is 1：2.5-3.5.
- 4. the preparation method according to profit requires 2, it is characterised in that in step (1), at room temperature, by Isosorbide-5-Nitrae-bis- (diphenyl phosphines Base) butane and 3,4,5- tri- (tetradecyloxyaniline) benzyl chlorides are put into chloroform solvent rapidly under nitrogen protection, and are passed through N2Remove Residual air in solution is removed, backflow 60-72h is stirred and heated under anaerobic state.
- 5. the preparation method according to profit requires 2, it is characterised in that in step (2), by 3,4,5- tri- (tetradecyloxyanilines) 1, Double (the Er Ben Ji phosphonium chlorides) butane (II) of 4- and the ehtyl potassium xanthate of 3.0-4.0 times of molar equivalent, mixed dissolution is in chloroform.
- 6. the preparation method according to profit requires 2, it is characterised in that in step (3), 4.0-6.0 times of molar equivalent of addition Hydrobromic acid or hydroiodic acid, stirring reaction 6-10 hours under normal temperature.
- 7. the preparation method according to profit requires 2, it is characterised in that step (2) and the gross production rate of step (3) two-step reaction are 84-85%.
- 8. the preparation method according to profit requires 2, it is characterised in that the crystallization in step (1), step (3) is addition acetic acid Ethyl ester crystallizes to obtain associated products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710970429.7A CN107805261A (en) | 2017-10-18 | 2017-10-18 | A kind of self assembly quaternary phosphine salt material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710970429.7A CN107805261A (en) | 2017-10-18 | 2017-10-18 | A kind of self assembly quaternary phosphine salt material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107805261A true CN107805261A (en) | 2018-03-16 |
Family
ID=61584495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710970429.7A Pending CN107805261A (en) | 2017-10-18 | 2017-10-18 | A kind of self assembly quaternary phosphine salt material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107805261A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113799514A (en) * | 2021-09-24 | 2021-12-17 | 广州松源实业有限公司 | Environment-friendly paper file box with mould-proof and insect-proof functions |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993020087A1 (en) * | 1992-04-03 | 1993-10-14 | Basf Aktiengesellschaft | Phosphonium salts and their use as brighteners for aqueous-acid galvanic nickel baths |
| JP2010132610A (en) * | 2008-12-05 | 2010-06-17 | Univ Of Tokyo | Compound having polymerizability forming bicontinuous cubic liquid crystal structure, and ion conductive polymer having bicontinuous cubic liquid crystal structure |
| CN104876960A (en) * | 2015-05-05 | 2015-09-02 | 南京理工大学 | Quaternary phosphonium salt ionic liquid and anion exchange preparation method thereof |
| JP2016221482A (en) * | 2015-06-02 | 2016-12-28 | 国立大学法人 東京大学 | Composite semipermeable membrane |
-
2017
- 2017-10-18 CN CN201710970429.7A patent/CN107805261A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993020087A1 (en) * | 1992-04-03 | 1993-10-14 | Basf Aktiengesellschaft | Phosphonium salts and their use as brighteners for aqueous-acid galvanic nickel baths |
| JP2010132610A (en) * | 2008-12-05 | 2010-06-17 | Univ Of Tokyo | Compound having polymerizability forming bicontinuous cubic liquid crystal structure, and ion conductive polymer having bicontinuous cubic liquid crystal structure |
| CN104876960A (en) * | 2015-05-05 | 2015-09-02 | 南京理工大学 | Quaternary phosphonium salt ionic liquid and anion exchange preparation method thereof |
| JP2016221482A (en) * | 2015-06-02 | 2016-12-28 | 国立大学法人 東京大学 | Composite semipermeable membrane |
Non-Patent Citations (1)
| Title |
|---|
| 徐同强: "季鏻盐自组装的设计及其在卟啉基电致发光材料中的应用", 《硕士学位论文》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113799514A (en) * | 2021-09-24 | 2021-12-17 | 广州松源实业有限公司 | Environment-friendly paper file box with mould-proof and insect-proof functions |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103539805B (en) | A kind of CuCN complex based on flexible dual-triazole ligand and preparation method thereof | |
| Han et al. | A novel nonlinear optically active tubular coordination network based on two distinct homo-chiral helices | |
| WO2022050235A1 (en) | Formate production method, formic acid production method, and antifreezing agent production method | |
| US11532831B1 (en) | Redox-active compounds and uses thereof | |
| CN108129385B (en) | Composite quaternary ammonium salt nonlinear optical crystalline material and preparation method thereof | |
| CN107805261A (en) | A kind of self assembly quaternary phosphine salt material | |
| Wang et al. | Extended structures of three new coordination polymers based on 1, 10-phenanthroline derivatives and 1, 4-benzenedicarboxylate mixed ligands: Preparation, structural characterization and properties | |
| Hao et al. | Visible-light-driven photocatalysts of three nickel (II) coordination polymers with mixed ligands | |
| Lazarou et al. | Synthetic, structural and spectroscopic studies of complexes derived from the copper (II) perchlorate/fumaric acid/N, N′-chelates tertiary reaction systems | |
| CN117587520A (en) | Mixed halogen hybridized chiral perovskite single crystal and preparation method thereof | |
| Feng et al. | Self-assembly of two chiral zinc coordination polymers based on N-benzoyl-l-glutamic acid: Influence of different N-donor ancillary ligands on structural arrangement and photoluminescent properties | |
| Zhang et al. | Solvent-induced copper–lanthanide heterometallic coordination polymers based on pyridine-2, 3-dicarboxylic acid: Syntheses, structures, and electrochemical properties | |
| Zhu et al. | A new 3D transition-metal complex-templated framework based on Wells–Dawson polyoxometalate and copper (I)–pyrazine moieties | |
| Faoro et al. | Synthesis and structure of new aryltellurenyl halides derived from (dmpTe) 2 (dmp= 2, 6-dimethoxyphenyl) | |
| Fang et al. | In situ synthesis of a zwitterionic ligand and formation of a Eu (III) coordination polymer with double-bridged connectors | |
| CN1305555C (en) | Water-soluble ion liquid synthesizing method | |
| Wu et al. | Synthesis, structure and property of a new inorganic–organic hybrid compound [Cu (phen) 2][Cu (phen) H2O] 2 [Mo5P2O23]· 3.5 H2O | |
| Li et al. | Construction of achiral/chiral coordination polymers with helical structures based on an imidazole-based dicarboxylate ligand containing the trifluoromethyl group | |
| Jiang et al. | Infinite chains constructed from flexible bis (benzimidazole)-based ligands | |
| Hu et al. | Photocurrent responsive supramolecular coordination networks with redox-active tetrathiafulvalene cores | |
| CN101210000A (en) | Ionic liquid with high electrochemical stability and preparing method thereof | |
| Yuan et al. | A novel pentanuclear Zn (II) coordination polymer with double helices: Synthesis, structure and luminescent property | |
| CN103933893A (en) | Choline ionic liquid surfactant and preparation method thereof | |
| Zhang et al. | Asymmetric modification of Anderson-type polyoxometalates towards organic–inorganic homo-and hetero-cluster oligomers | |
| Mei et al. | Synthesis, crystal structure and luminescent properties of one 3D Cd (II) coordination polymer [Cd (H3BPTC) 2 (bpy)] n (H4BPTC= 1, 1′-biphenyl-2, 2′, 6, 6′-tetracarboxylic acid, bpy= 4, 4′-bipyridine) |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180316 |
|
| RJ01 | Rejection of invention patent application after publication |