CN102382057B - Zwitterion with imidazole cation and malononitrile anion structures as well as preparation method and application thereof - Google Patents
Zwitterion with imidazole cation and malononitrile anion structures as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN102382057B CN102382057B CN201110238570.0A CN201110238570A CN102382057B CN 102382057 B CN102382057 B CN 102382057B CN 201110238570 A CN201110238570 A CN 201110238570A CN 102382057 B CN102382057 B CN 102382057B
- Authority
- CN
- China
- Prior art keywords
- preparation
- zwitterionic
- aryimidazole
- ion
- salt
- 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
Links
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- -1 imidazole cation Chemical class 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 12
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 11
- 150000001447 alkali salts Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 150000004982 aromatic amines Chemical class 0.000 claims description 9
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 5
- 238000010025 steaming Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 239000012312 sodium hydride Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- JJNZXLAFIPKXIG-UHFFFAOYSA-N 2-Chlorobenzylidenemalononitrile Chemical compound ClC1=CC=CC=C1C=C(C#N)C#N JJNZXLAFIPKXIG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 16
- 125000006575 electron-withdrawing group Chemical group 0.000 abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 4
- 238000002834 transmittance Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 26
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- NTMHHCYWWRIYIP-UHFFFAOYSA-N 1,2,4,5-tetraphenylimidazole Chemical class C1=CC=CC=C1C1=C(C=2C=CC=CC=2)N(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=N1 NTMHHCYWWRIYIP-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical class COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- HLUKBNUNRRERNX-UHFFFAOYSA-O 2,4,5-trimethyl-1-phenyl-1H-imidazol-1-ium Chemical compound CC1=C(N=C([NH+]1C1=CC=CC=C1)C)C HLUKBNUNRRERNX-UHFFFAOYSA-O 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- QGLAYJCJLHNIGJ-UHFFFAOYSA-N 4-bromo-2,6-dimethylaniline Chemical compound CC1=CC(Br)=CC(C)=C1N QGLAYJCJLHNIGJ-UHFFFAOYSA-N 0.000 description 2
- 241001274216 Naso Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical class NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- VLVCDUSVTXIWGW-UHFFFAOYSA-N 4-iodoaniline Chemical class NC1=CC=C(I)C=C1 VLVCDUSVTXIWGW-UHFFFAOYSA-N 0.000 description 1
- ARZZLBKNXRIKDD-UHFFFAOYSA-N CC1=C(C)[N+](C2=CC=CC=C2)=C(C)N1.[O-]S(C(F)(F)F)(=O)=O Chemical compound CC1=C(C)[N+](C2=CC=CC=C2)=C(C)N1.[O-]S(C(F)(F)F)(=O)=O ARZZLBKNXRIKDD-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- 241001570511 Oxalis stricta Species 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Zwitterions with imidazole cation and malononitrile anion structures and a preparation method and application thereof. The structural characteristics of the zwitterion are as follows: the group connected with one nitrogen atom in the molecule is imidazole cation of which alkyl forms an electron withdrawing group, the group connected with the other nitrogen atom is benzene ring or aromatic heterocycle, and one end of the benzene ring or the aromatic heterocycle is connected with malononitrile anion as an electron withdrawing group. The zwitterion with the push-pull electronic structure has good optical transmittance and a high nonlinear value, and has a good application prospect in the field of nonlinear optical materials.
Description
Technical field
The present invention relates to organic non linear optical material and zwitter-ion field, be specially a kind of zwitter-ion with glyoxaline cation, propane dinitrile anion structure and its production and use.
Background technology
Along with the develop rapidly of mechanics of communication and IT technology, people have higher requirement to nonlinear optical material.Compare with Inorganic Nonlinear Optical Materials, organic materials has the outstanding advantages such as structure can design, respond soon, optical nonlinearity coefficient is large, cheap.Its shortcoming is that thermostability is lower, absorbing wavelength is larger, thereby has limited the practical application (J.Am.Chem.Soc., 2003,125,15651) of organic non linear optical material.
Organic non linear optical material normally by large conjugated system form (Functional Organic Materials[M] .Wiley-VCH Verlag GmbH & Co.KGaA:Weinheim, 2007), in recent ten years, many have a large nonlinear factor, good optical transmission and resistant to elevated temperatures novel organic non linear optical material are constantly developed (Chem.Commun. by people, 2006, 131), wherein more novel, attractive is organic ion class organic non linear optical material (J.Org.Chem., 1997, 62, 5755, Proc.SPIE., 1999,3803,18, Chem.Mat., 2002,14,3758, Chem.Eur.J., 2003,9,1991, Angew.Chem.Int.Ed., 2005,44,7922, Chem.Mater., 2006,18,1079, J.Am.Chem.Soc., 2007,129,3267, Spectrochimica Acta Part A, 2007,68,1).But these organic ion quasi-nonlinear optical material synthetic routes are loaded down with trivial details, and kind is single.
Zwitter-ion (zwitterion) is the special ionic molecule of a class, and its unique distinction is, in its molecule, one end is with positive charge, and the other end is with negative charge, and externally total charge is zero, is electric neutrality.Zwitter-ion is also referred to as inner salt (inner salts) conventionally.Modal zwitter-ion is amino acid, but amino acid does not have conjugated structure, so do not have non-linear optical property, cannot apply as organic non linear optical material.
Summary of the invention
The invention provides a kind of zwitter-ion with glyoxaline cation, propane dinitrile anion structure and preparation method thereof, to solve the technical problems such as existing organic non linear optical material thermostability is lower, absorbing wavelength is larger.
Technical scheme of the present invention is as follows:
A zwitter-ion with glyoxaline cation, propane dinitrile anion structure, has following structural formula:
Wherein R
1for C
1-C
12any one in straight chained alkyl; R
2, R
3, R
4for hydrogen atom, methyl or phenyl.
This zwitterionic preparation method, comprises the following steps:
(1) prepare N-Aryimidazole; (prepare at present the technique comparative maturity of N-Aryimidazole, pass through dihalogenated aromatic hydrocarbon and imidazoles synthetic N-Aryimidazole under catalyzer condition such as routine.)
(2) at 50-120 DEG C of temperature, in the solvent of a kind of or any several mixing in benzene, toluene, glycol dimethyl ether, the N-Aryimidazole of (1) gained and sodium hydride or hydrolith, propane dinitrile are reacted to 1-10 hour under tetrakis triphenylphosphine palladium or Palladous chloride catalysis; Then remove impurity, then with obtaining 2-arylprop dintrile with rear being dried in hydrochloric acid; The molar content that described N-Aryimidazole, sodium hydride or hydrolith, propane dinitrile, tetrakis triphenylphosphine palladium or Palladous chloride account for respectively these four kinds of component total amounts is 20-24%, 49.6-55%, 20-24%, 2.4-5%;
(3) at 0-60 DEG C of temperature, in aprotic organic solvent, the 2-arylprop dintrile of step (2) gained is reacted to 0.5-5 hour with R-OTf or R-I, obtain imidazol ion salt; The mol ratio of described 2-arylprop dintrile and R-OTf or R-I is 1: 1-1: 3;
(4) at 0-50 DEG C of temperature, in the mixed solvent of any one or a few in water, methyl alcohol, ethanol, the imidazol ion salt of step (3) gained is reacted to 10-120 minute with alkali or basic salt, and the mol ratio of described imidazol ion salt and alkali or basic salt is 1: 1-1: 10; Then purified separation finally obtains zwitter-ion product.
In above-mentioned steps (2) treating processes of reaction after 1-10 hour preferably by product through revolve steam except after desolventizing again with benzene reflux (can remove the impurity such as catalyzer), by water-soluble the solid after refluxing, after filtration, with hydrochloric acid neutralization, refilter, dry.
Alkali described in above-mentioned steps (4) or basic salt are generally selected sodium hydroxide or potassium hydroxide or sodium carbonate or salt of wormwood, preferably sodium hydroxide or potassium hydroxide.
In above-mentioned steps (2) reaction process, pass into nitrogen or argon shield (reaction environment of, anaerobic anhydrous to guarantee, effect is better).
Aprotic organic solvent described in above-mentioned steps (3) is preferably selected any one or a few the mixed solvent in benzene, toluene, glycol dimethyl ether, methylene dichloride.
The process that step of the present invention (1) is prepared N-Aryimidazole can also be following method:
In organic solvent (often adopting methyl alcohol or ethanol), under 40-100 DEG C temperature of reaction, by halogenated aromatic amine, oxalic dialdehyde, formaldehyde reacts 1-20 hour with ammonium chloride or ammoniacal liquor, wherein the halogen element in halogenated aromatic amine is bromine or iodine, and halogenated aromatic amine, oxalic dialdehyde, formaldehyde, ammonium chloride or the ammoniacal liquor molar content that accounts for respectively these four kinds of component total amounts is respectively 17-20%, 17-20%, 34-30%, 36-30%; After reaction, obtain N-Aryimidazole through purifying.
Above-mentioned steps (1) be by halogenated aromatic amine, oxalic dialdehyde, after formaldehyde reacts with ammonium chloride or ammoniacal liquor and finishes for 1-20 hour, by revolving steaming method except desolventizing, then with alkali lye, the pH value of reaction product is adjusted to 9, through extraction, washing, dry, finally obtain N-Aryimidazole by column chromatography purifying again.
In the present invention, the organic solvent adopting in each step is as reaction environment, according to conventional operation consumption.Such as, in step (1), the volumetric molar concentration of halogenated aromatic amine can consider to get 0.20-0.25mol/L (according to the proportionlity of each component, can determine successively the ratio of other three kinds of components with solvent); For another example, in step (2), the volumetric molar concentration of N-Aryimidazole is 0.20-0.25mol/L (according to the proportionlity of each component, can determine successively the ratio of other three kinds of components with solvent)
Zwitter-ion of the present invention can be used for preparing nonlinear optical material.
The present invention has the following advantages:
1, zwitter-ion of the present invention, as a large class, has multiple specific form; Its preparation technology is easy, reliable.
2, this type of has and pushes away, draws the zwitter-ion of electronic structure to have good optical transmission, higher nonlinear optical coefficients, has good application prospect in nonlinear optical material field.
Brief description of the drawings
Fig. 1 is the zwitterionic absorbing wavelength schematic diagram of embodiment 6.
Fig. 2 is the TGA test result figure of embodiment 6.
Fig. 3 is the Z sweep test result figure of embodiment 6.
Embodiment
Zwitter-ion of the present invention is the zwitter-ion that has conjugated structure and have second-order nonlinear optical property.Its constitutional features for the group connecting on a nitrogen-atoms in: molecule be the glyoxaline cation that alkyl forms electron withdrawing group, the group connecting on another one nitrogen-atoms is phenyl ring or fragrant heterocycle, and phenyl ring or fragrant heterocycle one end are connected with propane dinitrile negatively charged ion as pushing away electronics base.
Its structure of imidazoles zwitter-ion with electron donor-acceptor structure meets molecular design theory (J.Chem.Phys., 1977,66,2664 of organic non linear optical material; Proc.Natl.Acad.Sci.USA, 1993,90,11297; Sceince, 1993,261,186), there is following feature: in (1) molecule, there is larger conjugated system.(2.) conjugated system two ends are connected with respectively and push away electronics base and electron withdrawing group.(3) molecule is inner salt.This type of imidazoles zwitter-ion with push-and-pull electronics based structures is the brand-new zwitter-ion of a class, its special electronic cloud is arranged and is made it have special physics, chemical property, and it has good application prospect in the fields such as organic synthesis, catalysis, separation, nonlinear optical material.
Following examples have been chosen several representational zwitter-ions and preparation technology and test result, and in actually operating, the selection of design parameter can be carried out various reasonable coupling according to art technology general knowledge in proper range.
The complete zwitterionic two kinds of building-up processes of 4-(3-methyl isophthalic acid-imidazoles)-2-phenyl propane dinitrile that embodied of embodiment 1-6; Wherein, for the preparation of intermediate product 4-(3-methyl isophthalic acid-imidazoles)-2-phenyl propane dinitrile, two kinds of route: embodiment 1,3 or embodiment 2, have 4. been provided
Complete 1-methyl-3-(2,6-dimethyl-4-propane dinitrile anion-radicals) phenyl-2, the building-up process of 4,5-tri-methylimidazolium of having embodied of embodiment 7-10;
Complete 1-methyl-3-(2,6-dimethyl-4-propane dinitrile anion-radicals) phenyl-2, the building-up process of 4,5-triphenyl imidazoles of having embodied of embodiment 11-14.
Synthesizing of embodiment 1:1-(4-bromobenzene)-imidazoles
In the there-necked flask of 250ml, add 8.601 grams of (0.050mol) 4-bromanilines, 25ml methyl alcohol, then add the glyoxal water solution (containing oxalic dialdehyde 0.051mol) of 7.383 gram 40%, at room temperature stir 16h.Then add successively 5.349 grams of (0.100mol) NH
4cl, formalin (containing formaldehyde 0.100mol), the 200ml methyl alcohol of 8.108 gram 37%.After stirring and refluxing 1h, exceed 10min and drip 80% H
3pO
47ml, then continue stopped reaction after stirring and refluxing 8h.
Revolve and steam except desolventizing, black residuum is poured in 150g frozen water, the pH value of mixture is adjusted to 9 with 40% KOH solution.With dichloromethane extraction (4 × 100ml), after organic phase difference water, saturated common salt water washing, add anhydrous Na SO
4dry, remove by filter NaSO
4, revolve to steam and remove methylene dichloride, transfer them in beaker.Adopt column chromatography to separate crude product, developping agent is ethyl acetate: the mixed solution that sherwood oil is 1.6: 1, finally obtains 6.77 grams of white solids, yield 61%.
1H?NMR(Bruker?DMX?300MHz，CDCl
3，TMS)：δ7.25-7.33(m，4H)，7.61-7.64(d，J＝8.7Hz，2H)，7.98(s，1H)；
13C?NMR(Bruker?DMX?300MHz，CDCl
3，TMS)：δ118.2，121.2，123.0，130.1，133.1，135.4，136.2。
Synthesizing of embodiment 2:1-(4-iodobenzene)-imidazoles
In the there-necked flask of 250ml, add 5.476 grams of (0.025mol) 4-Iodoanilines, 12ml methyl alcohol, then add the glyoxal water solution (containing oxalic dialdehyde 0.025mol) of 4.2ml 40%, at room temperature stir 16h.Then add successively 2.675 grams of (0.050mol) NH
4the formalin (containing formaldehyde 0.050mol) of Cl, 4ml 37%, 100ml methyl alcohol.After stirring and refluxing 1h, 30min drips 80% H
3pO
43.5ml, then continue stopped reaction after stirring and refluxing 8h.
Revolve and steam except desolventizing, black residuum is poured in 75g frozen water, the pH value of mixture is adjusted to 9 with 40% KOH solution.With dichloromethane extraction (4 × 50ml), after organic phase difference water, saturated common salt water washing, add anhydrous Na SO
4dry, remove by filter NaSO
4, revolve to steam and remove methylene dichloride, adopt column chromatography to separate crude product, developping agent is ethyl acetate: the mixed solution that sherwood oil is 1.6: 1, finally obtains 4.59 grams of white solids, yield 68%.
1H?NMR(Bruker?AVA?NCE?III?400MHz，CDCl
3，TMS)δ7.15-7.17(d，J＝8.0Hz，2H)，7.21(s，1H)，7.25(s，1H)，7.79-7.81(d，J＝8.8Hz，2H)，7.83(s，1H)。
Synthesizing of embodiment 3:4-(1-imidazoles)-2-phenyl propane dinitrile
In the there-necked flask of 100ml, add the DME of 8ml, 0.208g is containing the pressed powder (NaH 5.20mmol) of 60%NaH, ice bath, with syringe add 0.167g (2.53mmol) propane dinitrile be dissolved in 2mlDME form solution, after stirring 1h under room temperature, add 0.497g (2.23mmol) 1-(4-bromobenzene)-imidazoles and 0.239g (0.207mmol) tetrakis triphenylphosphine palladium, finally stir 5h at 85 DEG C, all operations is to complete in the process that passes into nitrogen.
DME is removed in decompression, and remaining solid refluxes and washs 10min with the benzene of 20ml, more water-soluble, filter, when the aqueous solution is neutralized to PH=7 with 5% hydrochloric acid, occur precipitation, solid collected by filtration, dry, finally obtain the khaki color pressed powder of 0.40 gram, yield is 87%.
1H?NMR(Bruker?AVA?NCE?III?400MHz，DMSO-d6，TMS)：δ4.50(s，1H)，6.84-6.86(d，J＝8.4Hz，2H)，7.40-7.42(d，J＝8.8Hz，2H)，7.84(s，1H)，8.13(s，1H)，9.49(s，1H)；
13C?NMR(Bruker?AVA?NCE?III?400MHz，DMSO-d6，TMS)：δ29.1，118.1，120.6，121.5，122.1，124.8，128.8，133.4，143.7；MS，m/z：209.1(M+1)，145.1(M+1)；LC＞93％。
Synthesizing of embodiment 4:4-(1-imidazoles)-2-phenyl propane dinitrile
In 100ml there-necked flask, add 8ml DME, 0.202g is containing the pressed powder (NaH 5.05mmol) of 60%NaH, and ice bath adds 0.168g (2.55mmol) propane dinitrile to be dissolved in the solution that 2ml DME forms with syringe; Under room temperature, stir after 1h, add 0.545g (2.02mmol) 1-(4-iodobenzene)-imidazoles and 0.232g (0.200mmol) tetrakis triphenylphosphine palladium, finally stir 5h at 85 DEG C, all operations passes into nitrogen.
Decompression steams DME, and remaining solid refluxes and washs 10min with the benzene of 20ml; Water-soluble again, filter, the aqueous solution neutralizes with 5% hydrochloric acid, occurs precipitation during to PH=7, and solid collected by filtration is dry.Finally obtain the khaki color pressed powder of 0.39 gram, productive rate is 94%.
1H?NMR(Bruker?AVA?NCE?III?400MHz，DMSO-d6，TMS)：δ4.50(s，1H)，6.84-6.86(d，J＝8.4Hz，2H)，7.40-7.42(d，J＝8.8Hz，2H)，7.84(s，1H)，8.13(s，1H)，9.49(s，1H)；
13C?NMR(Bruker?AVA?NCE?III?400MHz，DMSO-d6，TMS)：δ29.1，118.1，120.6，121.5，122.1，124.8，128.8，133.4，143.7；MS，m/z：209.1(M+1)，145.1(M+1)；LC＞93％。
Synthesizing of embodiment 5:4-(3-methyl isophthalic acid-imidazoles)-2-phenyl propane dinitrile
In the single port flask of 100ml, add 0.210g 2-[4-(1-imidazoles)]-phenyl-propane dinitrile (1.01mmol), 6ml CH
2cl
2, 186mg trifluoromethane sulfonic acid methyl esters (MeOTf, 1.13mmol), at room temperature stirs 2 hours, and solution is by the faint yellow sorrel that changes into, stopped reaction.
Embodiment 6:4-(3-methyl isophthalic acid-imidazoles)-2-phenyl propane dinitrile is zwitterionic synthetic
By reacted embodiment 5 mixture pressure reducing and steaming solvent, be 10% NaOH aqueous solution 5ml toward adding mass percent in the solid obtaining, filter after at room temperature stirring 30min, after washing, obtain crude product.
With column chromatography separating-purifying crude product, select the acetone of 1: 1 and alcohol mixeding liquid as developping agent, separate, finally obtain 179.4mg yellow solid, yield 80%.
1H?NMR(Bruker?DMX?300MHz，DMSO-d6，TMS)：δ3.90(s，3H)，6.83-6.86(d，J＝8.4Hz，2H)，7.34-7.37(d，J＝8.7Hz，2H)，7.84(s，1H)，8.10(s，1H)，9.54(s，1H)；
13C?NMR(Bruker?DMX?300MHz，DMSO-d6，TMS)：δ29.1，35.9，118.1，120.8，121.9，124.0，124.4，124.8，134.8，144.0；MS，m/z：223.1(M+1)。
The zwitter-ion product that embodiment 6 is made, adopts ultraviolet-visible spectrophotometer to test maximum absorption wavelength result in its ethanolic soln as shown in Figure 1, and instrument model is Jasco V570.As can be seen from Figure 1, synthetic zwitterionic maximum absorption wavelength λ
maxvalue is 344nm.
The zwitter-ion product heat decomposition temperature (Td) that embodiment 6 makes is 302 DEG C, specifically as shown in Figure 2.Testing TGA model used is NETZSCH STA 449C, and in the atmosphere of nitrogen, temperature rise rate is 20 DEG C/min.
Adopt Z scanner to test the nonlinear refractive index n of zwitter-ion at acetone soln
2, the wavelength of testing femto-second laser used is 800nm, pulse width is 1ps, repetition rate 20Hz.Attenuator, speculum, grating, semi-transparent semi-reflecting lens, convex lens and stepper-motor used are Zolix product.Energy meter used is produced by Laser-Probe company of the U.S..The thickness of cuvette internal diameter is 2mm, and reference substance is selected dithiocarbonic anhydride (nonlinear refractive index n
2be 1.17 × 10
-11esu), zwitterionic concentration range is 10
-4-10
-5mol/L.
Zwitterionic n
2value be on the occasion of, Z scanning curve is as shown in Figure 3.
Zwitterionic Δ T
p-vbe that 0.380, n is 1.36, transmitance is 90%, calculates its n
2value is 2.22 × 10
-12esu, second hyperpolarizabilitieof γ value is 2.29 × 10
-30esu.
From above-mentioned data, this type of zwitter-ion with electron donor-acceptor structure has good optical transmission, higher non-linear value, has good application prospect in nonlinear optical material field.
Embodiment 7:1-(2,6-dimethyl-4-bromine) phenyl-2,4,5-tri-methylimidazolium synthetic
In the there-necked flask of 250ml, add 9.95 grams of (0.050mol) 2,6-dimethyl-4-bromaniline, 25ml methyl alcohol, then add 4.30 gram 2,3-dimethyl diketone (0.050mol), at room temperature stirs 16h.Then add successively 5.35 grams of (0.100mol) NH
4cl, acetaldehyde solution (containing acetaldehyde 0.100mol), the 200ml methyl alcohol of 11.01 gram 40%.After stirring and refluxing 1h, exceed 10min and drip 80% H
3pO
47ml, then continue stopped reaction after stirring and refluxing 8h.
Aftertreatment, with embodiment 1, obtains 3.36 grams of white solids, yield 23%.
Embodiment 8:1-(2,6-dimethyl-4-malononitrile group) phenyl-2,4,5-tri-methylimidazolium synthetic
In the there-necked flask of 100ml, add the DME of 8ml, 0.200g is containing the pressed powder (NaH 5.0mmol) of 60%NaH, ice bath, with syringe add 0.165g (2.50mmol) propane dinitrile be dissolved in 2mlDME form solution, after stirring 1h under room temperature, add 0.584g (2.00mmol) 1-(2,6-dimethyl-4-bromine) phenyl-2,4,5-tri-methylimidazolium and 0.232g (0.200mmol) tetrakis triphenylphosphine palladium, finally stir 5h at 85 DEG C, all operations is to complete in the process that passes into nitrogen.
Aftertreatment, with embodiment 3, obtains 0.467 gram of white solid, yield 84%.
Embodiment 9:1-methyl-3-(2,6-dimethyl-4-malononitrile group) phenyl-2,4,5-tri-methylimidazolium trifluoromethyl sulfonic acid synthetic
In the single port flask of 25ml, add 0.292g 1-(2,6-dimethyl-4-malononitrile group) phenyl-2,4,5-tri-methylimidazolium (1.00mmol), 5ml CH
2cl
2, 180mg trifluoromethane sulfonic acid methyl esters (MeOTf, 1.10mmol), at room temperature stirs stopped reaction after 2 hours.
Embodiment 10:1-methyl-3-(2,6-dimethyl-4-propane dinitrile anion-radicals) phenyl-2,4,5-tri-methylimidazolium synthetic
By reacted embodiment 9 mixture pressure reducing and steaming solvent, be 10% NaOH aqueous solution 5ml toward adding mass percent in the solid obtaining, filter after at room temperature stirring 30min, after washing, obtain 0.248g yellow solid, yield 85%.
The maximum absorption wavelength that adopts spectrophotometer test implementation example 10 to obtain product is 350nm, and heat decomposition temperature (Td) is 305 DEG C, n
2value is 9.23 × 10
-12esu, second hyperpolarizabilitieof γ value is 9.52 × 10
-30esu.
Embodiment 11:1-(2,6-dimethyl-4-bromine) phenyl-2,4,5-triphenyl imidazoles synthetic
In the there-necked flask of 250ml, add 9.95 grams of (0.050mol) 2,6-dimethyl-4-bromaniline, 25ml methyl alcohol, then add 10.50 grams of benzils (0.050mol), at room temperature stir 16h.Then add successively 5.35 grams of (0.100mol) NH
4cl, 10.60 grams of phenyl aldehydes (0.100mol), 200ml methyl alcohol.After stirring and refluxing 1h, exceed 10min and drip 80% H
3pO
47ml, then continue stopped reaction after stirring and refluxing 8h.
Aftertreatment, with embodiment 1, obtains 4.54 grams of white solids, yield 19%.
Embodiment 12:1-(2,6-dimethyl-4-malononitrile group) phenyl-2,4,5-triphenyl imidazoles synthetic
In the there-necked flask of 100ml, add the DME of 8ml, 0.200g is containing the pressed powder (NaH 5.0mmol) of 60%NaH, ice bath, with syringe add 0.165g (2.50mmol) propane dinitrile be dissolved in 2mlDME form solution, after stirring 1h under room temperature, add 0.956g (2.00mmol) 1-(2,6-dimethyl-4-bromine) phenyl-2,4,5-triphenyl imidazoles and 0.232g (0.200mmol) tetrakis triphenylphosphine palladium, finally stir 5h at 85 DEG C, all operations is to complete in the process that passes into nitrogen.
Aftertreatment, with embodiment 3, obtains 0.789 gram of white solid, yield 85%.
Embodiment 13:1-methyl-3-(2,6-dimethyl-4-malononitrile group) phenyl-2,4,5-triphenyl imidazoles trifluoromethyl sulfonic acid synthetic
In the single port flask of 25ml, add 0.464g 1-(2,6-dimethyl-4-malononitrile group) phenyl-2,4,5-triphenyl imidazoles (1.00mmol), 5ml CH
2cl
2, 180mg trifluoromethane sulfonic acid methyl esters (MeOTf, 1.10mmol), at room temperature stirs stopped reaction after 2 hours.
Embodiment 14:1-methyl-3-(2,6-dimethyl-4-propane dinitrile anion-radicals) phenyl-2,4,5-triphenyl imidazoles synthetic
By reacted embodiment 13 mixture pressure reducing and steaming solvent, be 10% NaOH aqueous solution 5ml toward adding mass percent in the solid obtaining, filter after at room temperature stirring 30min, after washing, obtain 0.392g yellow solid, yield 82%.
The maximum absorption wavelength that adopts spectrophotometer test implementation example 14 to obtain product is 352nm, and heat decomposition temperature (Td) is 310 DEG C, n
2value is 5.67 × 10
-12esu, second hyperpolarizabilitieof γ value is 5.85 × 10
-30esu.
Claims (9)
1. a zwitter-ion with glyoxaline cation, propane dinitrile anion structure, has following structural formula:
Wherein R
1for C
1-C
12any one in straight chained alkyl; R
2, R
3, R
4for hydrogen atom, methyl or phenyl.
2. zwitterionic preparation method as claimed in claim 1, comprises the following steps:
(1) prepare N-Aryimidazole;
(2) at 50-120 DEG C of temperature, in the solvent of a kind of or any several mixing in benzene, toluene, glycol dimethyl ether, the N-Aryimidazole of (1) gained and sodium hydride or hydrolith, propane dinitrile are reacted to 1-10 hour under tetrakis triphenylphosphine palladium or Palladous chloride catalysis; Then remove impurity, then with obtaining 2-arylprop dintrile with rear being dried in hydrochloric acid; The molar content that described N-Aryimidazole, sodium hydride or hydrolith, propane dinitrile, tetrakis triphenylphosphine palladium or Palladous chloride account for respectively these four kinds of component total amounts is 20-24%, 49.6-55%, 20-24%, 2.4-5%;
(3) at 0-60 DEG C of temperature, in aprotic organic solvent, the 2-arylprop dintrile of step (2) gained is reacted to 0.5-5 hour with R-OTf or R-I, obtain imidazol ion salt; The mol ratio of described 2-arylprop dintrile and R-OTf or R-I is 1:1-1:3;
(4) at 0-50 DEG C of temperature, in the mixed solvent of any one or a few in water, methyl alcohol, ethanol, the imidazol ion salt of step (3) gained is reacted to 10-120 minute with alkali or basic salt, and the mol ratio of described imidazol ion salt and alkali or basic salt is 1:1-1:10; Then purified separation finally obtains zwitter-ion product.
3. zwitterionic preparation method according to claim 2, it is characterized in that: in step (2), the treating processes of reaction after 1-10 hour is that product is refluxed with benzene through revolving to steam except after desolventizing again, by water-soluble the solid after refluxing, after filtration, neutralize with hydrochloric acid, refilter, dry.
4. zwitterionic preparation method according to claim 2, is characterized in that: the alkali described in step (4) or basic salt are sodium hydroxide or potassium hydroxide or sodium carbonate or salt of wormwood.
5. zwitterionic preparation method according to claim 2, is characterized in that: in step (2) reaction process, pass into nitrogen or argon shield.
6. zwitterionic preparation method according to claim 2, is characterized in that: aprotic organic solvent described in step (3) is any one or a few the mixed solvent in benzene, toluene, glycol dimethyl ether, methylene dichloride.
7. zwitterionic preparation method according to claim 4, is characterized in that: the alkali in step (4) or basic salt adopt sodium hydroxide, potassium hydroxide.
8. according to the arbitrary described zwitterionic preparation method of claim 2 to 7, it is characterized in that, the process that step (1) is prepared N-Aryimidazole is as follows:
In organic solvent, under 40-100 DEG C temperature of reaction, by halogenated aromatic amine, oxalic dialdehyde, formaldehyde reacts 1-20 hour with ammonium chloride or ammoniacal liquor, wherein the halogen element in halogenated aromatic amine is bromine or iodine, and halogenated aromatic amine, oxalic dialdehyde, formaldehyde, ammonium chloride or the ammoniacal liquor molar content that accounts for respectively these four kinds of component total amounts is respectively 17-20%, 17-20%, 34-30%, 36-30%; After reaction, obtain N-Aryimidazole through purifying.
9. zwitterionic preparation method according to claim 8, it is characterized in that: step (1) be by halogenated aromatic amine, oxalic dialdehyde, after formaldehyde reacts with ammonium chloride or ammoniacal liquor and finishes for 1-20 hour, by revolving steaming method except desolventizing, then with alkali lye, the pH value of reaction product is adjusted to 9, through extraction, washing, dry, finally obtain N-Aryimidazole by column chromatography purifying again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110238570.0A CN102382057B (en) | 2011-08-19 | 2011-08-19 | Zwitterion with imidazole cation and malononitrile anion structures as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110238570.0A CN102382057B (en) | 2011-08-19 | 2011-08-19 | Zwitterion with imidazole cation and malononitrile anion structures as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102382057A CN102382057A (en) | 2012-03-21 |
| CN102382057B true CN102382057B (en) | 2014-07-02 |
Family
ID=45821951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110238570.0A Expired - Fee Related CN102382057B (en) | 2011-08-19 | 2011-08-19 | Zwitterion with imidazole cation and malononitrile anion structures as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102382057B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420916A (en) * | 2013-08-26 | 2013-12-04 | 聊城大学 | Rapid preparation method for 1,2,3,4,5-tetra-substituted imidazole compound |
| CN105272918B (en) * | 2015-11-20 | 2018-08-24 | 湘潭大学 | Halogenation -1- alkyl -3- vinyl -2,4,5- triarylimidazoles and preparation method and purposes |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4801713A (en) * | 1987-01-27 | 1989-01-31 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Organic complexes of a cation of a heterocyclic nitrogen compound and an anion of a 2,5-disubstituted-7,7,8,8-tetracyanoquinodiethmane |
| CN101143848A (en) * | 2007-10-19 | 2008-03-19 | 中国科学院上海有机化学研究所 | Imidazole-like ionic salt with electron donor-acceptor structure, preparation method and use thereof |
-
2011
- 2011-08-19 CN CN201110238570.0A patent/CN102382057B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4801713A (en) * | 1987-01-27 | 1989-01-31 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Organic complexes of a cation of a heterocyclic nitrogen compound and an anion of a 2,5-disubstituted-7,7,8,8-tetracyanoquinodiethmane |
| CN101143848A (en) * | 2007-10-19 | 2008-03-19 | 中国科学院上海有机化学研究所 | Imidazole-like ionic salt with electron donor-acceptor structure, preparation method and use thereof |
Non-Patent Citations (4)
| Title |
|---|
| Exceptional Molecular Hyperpolarizabilities in Twisted π-Electron System Chromophores;Hu Kang, Antonio Facchetti, Peiwang Zhu,et.al;《Angew.Chem.int.ed》;Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim;20051209;第44卷(第48期);7922-7925 * |
| Twisted π-Electron System Electrooptic Chromophores. Structural and Electronic Consequences of Relaxing Twist-Inducing Nonbonded Repulsions;Yiliang Wang, David L. Frattarelli, Antonio Facchetti，et.al.;《J. Phys. Chem. C》;American Chemical Society;20080522;第112卷(第21期);8005-8015 * |
| Ultralarge Hyperpolarizability Twisted π-Electron System Electro-Optic Chromophores: Synthesis, Solid-State and Solution-Phase Structural Characteristics, Electronic Structures, Linear and Nonlinear Optical Properties, and Computational Studies;Hu Kang, Antonio Facchetti, Hua Jiang,et.al.;《J. AM. CHEM. SOC》;American Chemical Society;20070220;第129卷(第11期);第3273页式1 * |
| 刘小龙等.1- 芳基取代咪唑及其盐的合成与其生物活性的研究.《云南民族大学学报(自然科学版)》.2007,第16卷(第3期),229. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102382057A (en) | 2012-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101845039B (en) | Second-order nonlinear optical chromophore with D-pi-A structure and synthetic method and application thereof | |
| Shi et al. | Synthesis of Well‐Defined Figure‐of‐Eight‐Shaped Polymers by a Combination of ATRP and Click Chemistry | |
| CN103429594A (en) | Process for preparation of acetals | |
| CN102382057B (en) | Zwitterion with imidazole cation and malononitrile anion structures as well as preparation method and application thereof | |
| Wu et al. | New second-order nonlinear optical (NLO) hyperbranched polymers containing isolation chromophore moieties derived from one-pot “A 2+ B 4” approach via Suzuki coupling reaction | |
| CN101845040A (en) | Organic second-order nonlinear optical chromophore with D-pi-A structure modified by dendritic group, and synthetic method and application thereof | |
| CN113372556A (en) | Polyarylether sulfone copolymer with main chain containing platinum aromatic alkyne groups and preparation method thereof | |
| Wu et al. | Further improvement of the macroscopic NLO coefficient and optical transparency of hyperbranched polymers by enhancing the degree of branching | |
| Wang et al. | A novel post-polymerization modification route to functional poly (disubstituted acetylenes) through phenol–yne click reaction | |
| Wu et al. | Using an isolation chromophore to further improve the comprehensive performance of nonlinear optical (NLO) dendrimers | |
| CN104558541A (en) | Alkyne-ketone intermediate based conjugated high-molecular polymer as well as preparation method and application thereof | |
| Hesse | Synthesis of 5-arylidenerhodanines in L-proline-based deep eutectic solvent | |
| CN103193970A (en) | Preparation method of hyperbranched fluorescent polymer | |
| CN113264843A (en) | Synthetic method of 3-aminobicyclo [1.1.1] pentane-1-carboxylic ester derivative | |
| CN104829848A (en) | Dissoluble nitrogenous hyperbranched polymer and manufacturing method and application therefor | |
| CN104016868A (en) | Chlorinated 2, 4, 6-trinitro-1, 3- distyryl benzene derivatives as well as preparation method and application thereof | |
| JPH1048678A (en) | Nonlinear optical material | |
| CN103739745A (en) | Imidazole group-containing thioxanthone photoinitiator and preparation method thereof | |
| Fang et al. | New soluble unsaturated polyketone derived from diarylidenecycloalketone: synthesis and optical and electrochemical properties of π-conjugated poly (diarylidenecyclohexanone) with long side chains | |
| CN103415523B (en) | A kind of preparation technology of aldehyde alcohol acetal | |
| KR102447937B1 (en) | Preparation method for 2-cyanoethyl group-containing polymer | |
| CN109320691B (en) | Synthetic method and application of polyisocyan | |
| Yan et al. | Preparation and properties of a functional polyacetylene with quinoline-based heterocyclic azo pendants | |
| CN103012087B (en) | Green synthetic method of alpha, alpha'-double benzylidene cycloalkanone compound | |
| CN105541757A (en) | [5-(o-hydroxy phenyl methylene imido)-1,3,4-thiadiazole-2-yl]ethyl thioacetate, preparation method and application of [5-(o-hydroxy phenyl methylene imido)-1,3,4-thiadiazole-2-yl]ethyl thioacetate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140702 Termination date: 20180819 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |