CN102295838B - Six-branched azosiloxane dye and synthesis method thereof - Google Patents
Six-branched azosiloxane dye and synthesis method thereof Download PDFInfo
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- CN102295838B CN102295838B CN201110188012.8A CN201110188012A CN102295838B CN 102295838 B CN102295838 B CN 102295838B CN 201110188012 A CN201110188012 A CN 201110188012A CN 102295838 B CN102295838 B CN 102295838B
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- azosiloxane
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- 238000001308 synthesis method Methods 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 9
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002989 phenols Chemical class 0.000 claims abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000460 chlorine Chemical group 0.000 claims abstract description 4
- 229910052801 chlorine Chemical group 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 84
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 64
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000975 dye Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- 239000000284 extract Substances 0.000 claims description 28
- 238000004440 column chromatography Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000746 purification Methods 0.000 claims description 18
- 238000010189 synthetic method Methods 0.000 claims description 17
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 235000010288 sodium nitrite Nutrition 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- VLZVIIYRNMWPSN-UHFFFAOYSA-N 2-Amino-4-nitrophenol Chemical compound NC1=CC([N+]([O-])=O)=CC=C1O VLZVIIYRNMWPSN-UHFFFAOYSA-N 0.000 claims description 5
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- -1 carbodiimide compound Chemical class 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 235000011181 potassium carbonates Nutrition 0.000 claims description 5
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- DOPJTDJKZNWLRB-UHFFFAOYSA-N 2-Amino-5-nitrophenol Chemical compound NC1=CC=C([N+]([O-])=O)C=C1O DOPJTDJKZNWLRB-UHFFFAOYSA-N 0.000 claims description 3
- BUMGQSCPTLELLS-UHFFFAOYSA-N 2-chloro-5-nitrophenol Chemical class OC1=CC([N+]([O-])=O)=CC=C1Cl BUMGQSCPTLELLS-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 31
- 238000012545 processing Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 2
- 238000006959 Williamson synthesis reaction Methods 0.000 abstract 1
- 238000007259 addition reaction Methods 0.000 abstract 1
- 238000006149 azo coupling reaction Methods 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 abstract 1
- AZQGFVRDZTUHBU-UHFFFAOYSA-N isocyanic acid;triethoxy(propyl)silane Chemical compound N=C=O.CCC[Si](OCC)(OCC)OCC AZQGFVRDZTUHBU-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 22
- 238000005406 washing Methods 0.000 description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- 238000002242 deionisation method Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000003480 eluent Substances 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 12
- 239000012266 salt solution Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000499 gel Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 230000005526 G1 to G0 transition Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009881 electrostatic interaction Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 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
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- PSVBHJWAIYBPRO-UHFFFAOYSA-N lithium;niobium(5+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[Nb+5] PSVBHJWAIYBPRO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/106—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azo dye
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/008—Dyes containing a substituent, which contains a silicium atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/103—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a diaryl- or triarylmethane dye
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a six-branched azosiloxane dye. The dye has a structural formula represented by a formula 1, wherein R2 is hydrogen or chlorine when R1 is nitro, R2 is nitro when R1 is hydrogen. A synthesis method for the dye is as follow: 1,1,1-tris (4-hydroxyphenyl)ethane and 3-chloropropyl-1,2-diol are subjected to a Williamson ether synthesis reaction to prepare a branched core containing propylene glycol; then the branched core containing the propylene glycol and 4-[(2-N-ethylaniline)ethoxy]-4-oxobutanoic acid are subjected to an esterification reaction, then the reaction product and a phenol derivative are subjected to a diazo coupling reaction to obtain a six-branched azo chromophore coupled with hydroxyl; the chromophore and isocyanate propyl triethoxy silane are subjected to an addition reaction to obtain the six-branched azosiloxane dye. According to the present invention, the synthesis method is simple; the reaction conditions are mild; the raw materials are easy to be obtained; the yield is high; the six-branched azosiloxane dye has characteristics of good solubility, good film forming and processing property, large nonlinear optical property and high thermal stability. The formula 1 is described in the description.
Description
Technical field
The present invention relates to a kind of six branched azosiloxane dyes and synthetic method thereof.
Background technology
Nonlinear optics has vital role to photoelectron, photon technology development, utilizes the different non-linear optical effects such as mixing and frequency, difference frequency, electric light can prepare much as optical information processing components and parts such as optical modulation, photoswitch, light storage and light amplitude limits.Therefore, the nonlinear optical material of development of new to economic construction and national defense safety all tool be of great significance.
Common nonlinear optical material mainly contains mineral crystal, organic crystal and polymer materials etc.Mineral crystal is the class second-order non-linear optical materials that people study the earliest and use, and such as the mineral crystal such as Lithium niobium trioxide, gallium arsenide, these inorganic crystal materials develop comparative maturity, and realizes already commercial applications.But also exist obvious deficiency, as easy deliquescence, dehydration cause damage, and can only be with the work of monocrystal material form, be difficult to realize light integrated etc.Therefore, these inorganic crystal materials cannot meet the required a series of requirements of optical communication, optical signal process field that develop rapidly.20 century 70 people start the research and discovery to organic non linear optical material.Compared with inorganic nonlinear material, organic non-linear optical properties has nonlinear optical coefficients large (1-3 the order of magnitude), fast response time (can reach femtosecond), specific inductivity is low, optical damage threshold is high, processing characteristics is good and can carry out the series of advantages such as molecular designing.Particularly the polytropy of organic molecular structure and controllability make people meet the molecular designing of the practical requirement of device and to cut out by the understanding of its structure-performance relation is realized.
Dendritic macromole has unique globosity, three-dimensional cavity shape and good single dispersing character, makes it in nonlinear material field, obtain more application.This dendritic structure effectively reduces the strong electrostatic interaction between chromophore molecule, stops intermolecular reunion.When a large amount of three-dimensional cavitys can provide chromophore to carry out ordered arrangement, the required space that freely turns to, improves polarization efficiency, reaches the object that strengthens non-linear optical property.But organic materials often thermostability is not high, be difficult to obtain application in practical devices.Inorganic-Organic Hybrid Material comprehensively high stability, high transparent and the organic materials of inorganic materials excellent optical activity, the advantage such as can modify, and have mate with optical fiber well, coupling loss is low, specific refractory power is adjustable, be easy to the good characteristics such as integrated, has become an emerging focus in photoelectronics field.Dendritic structure is incorporated in Inorganic-Organic Hybrid Material, be expected as suppressing the strong electrostatic interaction between dipole molecule in Inorganic-Organic Hybrid Material, the consistency that improves material provides a new effective way with enhancing non-linear optical property and thermostability.
Summary of the invention
The object of the invention is to provide a kind of six branched azosiloxane dyes and synthetic method thereof.This compounds has good solubility and film forming processibility, and large non-linear optical property and high thermostability, is expected to be applied in the fields such as Electro-optical Modulation, photoswitch and optical storage as a kind of new nonlinear optical material.
Six branched azosiloxane dyes of the present invention, its general structure is as follows:
R in formula
1during for nitro, R
2for hydrogen or chlorine; R
1during for hydrogen, R
2for nitro.
The synthetic method of six branched azosiloxane dyes of the present invention, its step is as follows:
(1) by 1 mole 1,1,1-tri-(4-hydroxy phenyl) ethane is dissolved in ethanolic soln, be added dropwise to the alkaline solution containing 2-5 mole, return stirring reacts half an hour, then adds 3-chloropropyl-1 of 3-5 mole, 2-glycol, continue back flow reaction 4 hours, reaction finishes rear coolingly, and solution is poured in water, extracts by ethyl acetate, underpressure distillation, except desolventizing, obtains the dendritic core containing propylene glycol;
(2) by the 2-(of 1 mole
n-ethylbenzene amido) succinyl oxide of ethanol and 1-2 mole is dissolved in methylene dichloride, add organic bases and to Dimethylamino pyridine as catalyzer, stirring at room temperature reaction 12 hours, then add aqueous ammonium chloride solution, continue stirring at room temperature and react half an hour, reaction finishes to fall back, and extracts and with the column chromatography acquisition 4-[(2-that purifies with methylene dichloride
n-ethylbenzene amido) oxyethyl group]-4-ketobutyric acid;
(3) the dendritic core containing propylene glycol 1 mole of step (1) being made and the 4-[(2-that 6-9 mole of step (2) makes
n-ethylbenzene amido) oxyethyl group]-4-ketobutyric acid is dissolved in organic solvent, what add the carbodiimide compound of 9 moles and 2 moles is catalyzer to Dimethylamino pyridine, stirring at room temperature reaction 48 hours, reaction is poured in frozen water after finishing, and extracts and carries out purification processes with column chromatography with methylene dichloride;
(4) phenol derivatives of the ethylene chlorhydrin of 1 mole and 1.2 moles is dissolved in
n,
nin-dimethyl formamide, add the inorganic salt of 1.25 moles, return stirring reaction 12 hours, after reaction finishes, pours in frozen water, extracts and carries out purification processes with column chromatography with methylene dichloride;
(5) product 1-2 mole of step (4) being made is dissolved in acid, is cooled to 0
oafter C, slowly drip sodium nitrite in aqueous solution, the product that reaction adds 1 mole of step (3) to make after half an hour, stir after 1 hour, regulate pH value to 6-7 with solution of potassium carbonate, after reaction finishes, pour in frozen water, extract and carry out obtaining after purification processes the six dendritic azo chromophores that are connected with hydroxyl with column chromatography with methylene dichloride;
(6) six dendritic azo chromophores of 1 mole of acquisition and the isocyanate group propyl-triethoxysilicane of 6-8 mole are dissolved in to tetrahydrofuran (THF), add catalyzer, after return stirring reaction 24-72h, reaction solution is poured in normal hexane, filtering-depositing is also purified with column chromatography, obtains six branched azosiloxane dyes.
In above-mentioned synthetic method, the said alkaline solution of step (1) is sodium hydroxide, the aqueous solution of potassium hydroxide or sodium carbonate; The said organic bases of step (2) is triethylamine or pyridine; The said organic solvent of step (3) be tetrahydrofuran (THF), methylene dichloride, ethyl acetate and
n,
none in-dimethyl formamide or mixing solutions; The said carbodiimide compound of step (3) is
n,
n'-dicyclohexylcarbodiimide or 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride; The said phenol derivatives of step (4) is the chloro-5-nitrophenols of 2-Amino-5-nitrophenol, 2-amino-4-or 2-Amino-4-nitrophenol; The said inorganic salt of step (4) are salt of wormwood, saleratus, sodium carbonate or sodium bicarbonate; The said acid of step (5) is concentrated hydrochloric acid or the vitriol oil; The said catalyzer of step (6) is triethylamine, pyridine, stannous octoate or dibutyl tin laurate.
Beneficial effect of the present invention is:
1. six branched azosiloxane dye synthesis techniques of the present invention are simple, mild condition, and raw material is easy to get, and productive rate is higher.
2. the branched structure of six branched azosiloxane dyes of the present invention can significantly reduce the electrostatic interaction between chromophore, improves effective chromophore load concentration and the polarization efficiency of material, thus the macro non-linear optical property of effective strongthener.And six branched structuries are expected to increase the steric effect that chromophore rotates, thereby improve the thermostability of chromophore's polarization orientation.
3. six branched azosiloxane dyes of the present invention are compared with simple organic chromophore molecule, there is good solubility, film forming processibility and good silica-based compatibility, can be on glass or silicon chip direct formation of film at surface, and can be used as precursor and be prepared into inorganic-organic hybridization film by sol gel reaction, be expected to obtain practical application as a kind of novel non-linearity optical material in fields such as Electro-optical Modulation, photoswitch and optical storages.
Embodiment
Embodiment 1:
R
1for nitro, R
2for the synthetic method of six branched azosiloxane dyes of hydrogen, its step is as follows:
(1) get 1 mole 1,1,1-tri-(4-hydroxy phenyl) ethane is dissolved in 600 mL ethanolic solns, is added dropwise to the aqueous solution containing 2 molar sodium hydroxides, return stirring reaction half an hour.Then add 3-chloropropyl-1 of 3 moles, 2-glycol, continues back flow reaction 4 hours.Reaction finishes rear coolingly, and solvent is poured in water, extracts by ethyl acetate, and underpressure distillation, except desolventizing, obtains the dendritic core containing propylene glycol.Its building-up reactions formula is:
Nucleus magnetic resonance:
1h NMR (500 MHz, DMSO-
d 6): δ=2.03 (s, 3H, C
h 3), 3.43 (d, 6H, OC
h 2), 3.80 (m, 6H, O
h), 3.95 (m, 3H, C
h), 4.67 (d, 3H, C
h 2oH), 4.95 (d, 3H, C
h 2oH), 6.82 (d, 6H, Ar
h), 6.91 (d, 6H, Ar
h).
13C NMR (125 MHz, DMSO-
d 6): δ = 157.167, 141.785, 129.695, 114.142, 70.457, 69.911, 63.207, 50.600, 30.863.
Ultimate analysis: theoretical value C
29h
36o
9: C, 65.89; H, 6.86; Measured value C, 65.52; H 7.06.
Mass spectrum: theoretical value C
29h
36o
9[M+H]
+, 527.2. measured value: 526.9.
(2) get the 2-(of 1 mole
n-ethylbenzene amido) succinyl oxide of ethanol and 1.2 moles is dissolved in 600 mL methylene dichloride, add the pyridine of 5 mL and 0.2 mole to Dimethylamino pyridine as catalyzer, stirring at room temperature reaction 12 hours.Then add aqueous ammonium chloride solution, continue stirring at room temperature and react half an hour.Reaction finishes to fall back, and extracts with methylene dichloride.Then respectively with salt washing and deionization washing, extract organic layer anhydrous magnesium sulfate drying.After filtration, filtrate is spin-dried for, precipitation obtains 4-[(2-N-ethylbenzene amido taking methylene dichloride and ethyl acetate (volume ratio 20: 1) as eluent carries out column chromatography for separation purification) oxyethyl group]-4-ketobutyric acid.Its building-up reactions formula is:
Nucleus magnetic resonance:
1h NMR (500 MHz, CDCl
3-
d 6): δ=1.14 (m, 3H, C
h 3), 2.59 (m, 2H, OC
h 2), 2.65 (m, 2H, OC
h 2), 3.37 (m, 2H, C
h 2cH
3), 3.53 (t, 2H, NC
h 2), 4.24 (t, 2H, C
h 2o), 6.67 (m, 3H, Ar
h), 7.21 (m, 2H, Ar
h).
(3) get the dendritic core containing propylene glycol that 1 mole of step (1) makes and the 4-[(2-that 6 moles of steps (2) make
n-ethylbenzene amido) oxyethyl group]-4-ketobutyric acid is dissolved in the mixing solutions of 200 mL tetrahydrofuran (THF)s and 600 mL methylene dichloride, adds 9 moles
n,
n'-dicyclohexylcarbodiimide and 2 moles to Dimethylamino pyridine as catalyzer, room temperature reaction 48 hours.Reaction is poured in frozen water after finishing, and extracts with methylene dichloride.Respectively with salt solution and deionization washing, organic layer anhydrous magnesium sulfate drying.After filtration, being spin-dried for solution, is then stationary phase with 100-200 object silica gel, and the column chromatography that tetrahydrofuran (THF) and methylene dichloride (volume ratio 1: 40) are eluent carries out purification processes.Its building-up reactions formula is:
(4) get the ethylene chlorhydrin of 1 mole and the 2-Amino-5-nitrophenol of 1.2 moles and be dissolved in 500 mL
n,
nin-dimethyl formamide, add the sodium carbonate of 1.25 moles.Return stirring reaction 12 hours.After reaction finishes, pour in frozen water, extract with methylene dichloride.Respectively with salt solution and deionization washing, organic layer anhydrous magnesium sulfate drying.Filter, be spin-dried for solution, then the column chromatography taking methylene dichloride as eluent carries out purification processes.Its building-up reactions formula is:
Nucleus magnetic resonance:
1h NMR (500 MHz, CDCl
3-
d 6): δ=1.85 (s, 1H, O
h), 4.05 (t, 2H, C
h 2oH), 4.22 (t, 2H, OC
h 2), 4.59 (s, 2H, N
h 2), 6.66 (d, 1H, Ar
h), 7.71 (d, 1H, Ar
h), 7.83 (m, 1H, Ar
h).
Mass spectrum: theoretical value C
8h
10n
2o
4[M-H]
-, 197.18. measured value: 198.3.
(5) get the product that 1 mole of step (4) makes and be dissolved in 2L concentrated hydrochloric acid, be cooled to 0
oafter C, slowly drip 200mL sodium nitrite in aqueous solution (containing 0.7mol Sodium Nitrite).The product that reaction adds 1 mole of step (3) to make after half an hour.Stir after 1 hour, by solution of potassium carbonate adjusting pH value to 7.After reaction finishes, pour in frozen water, extract rear with salt solution and deionization washing, organic layer anhydrous magnesium sulfate drying with methylene dichloride.Filter, be spin-dried for solution, then obtain six dendritic azo chromophores taking tetrahydrofuran (THF) and methylene dichloride (volume ratio 1: 40) as the column chromatography of eluent carries out purification processes.Its building-up reactions formula is:
(6) get the six dendritic azo chromophores of 1 mole and the isocyanate group propyl-triethoxysilicane of 6 moles and be dissolved in 200mL tetrahydrofuran (THF), add 5mL stannous octoate.After heating reflux reaction 24 hours, reaction solution is poured in normal hexane, filtering-depositing obtains six branched azosiloxane dyes.Its building-up reactions formula is:
The six branched azosiloxane dye molecular weight that this example makes are up to 4751.46, its active non-linear optical chromophore content reaches 78.39 wt.%, and spin-coating film is prepared into nonlinear optical material or prepares organic-inorganic hybridized non-linear optical material as precursor by sol gel reaction separately.
Embodiment 2:
R
1for nitro, R
2for the synthetic method of six branched azosiloxane dyes of chlorine, its step is as follows:
(1) get 1 mole 1,1,1-tri-(4-hydroxy phenyl) ethane is dissolved in 600 mL ethanolic solns, is added dropwise to the aqueous solution containing 5 moles of hydrogen potassium oxides, return stirring reaction half an hour.Then add 3-chloropropyl-1 of 4 moles, 2-glycol, continues back flow reaction 4 hours.Reaction finishes rear coolingly, and solvent is poured in water, extracts by ethyl acetate, and underpressure distillation, except desolventizing, obtains the dendritic core containing propylene glycol; Its building-up reactions formula is:
Nucleus magnetic resonance:
1h NMR (500 MHz, DMSO-
d 6): δ=2.03 (s, 3H, C
h 3), 3.43 (d, 6H, OC
h 2), 3.80 (m, 6H, O
h), 3.95 (m, 3H, C
h), 4.67 (d, 3H, C
h 2oH), 4.95 (d, 3H, C
h 2oH), 6.82 (d, 6H, Ar
h), 6.91 (d, 6H, Ar
h).
13C NMR (125 MHz, DMSO-
d 6): δ = 157.167, 141.785, 129.695, 114.142, 70.457, 69.911, 63.207, 50.600, 30.863.
Ultimate analysis: theoretical value C
29h
36o
9: C, 65.89; H, 6.86; Measured value C, 65.52; H 7.06.
Mass spectrum: theoretical value C
29h
36o
9[M+H]
+, 527.2. measured value: 526.9.
(2) get the 2-(N-ethylbenzene amido of 1 mole) succinyl oxide of ethanol and 2 moles is dissolved in 600 mL methylene dichloride, add the triethylamine of 5 mL and 0.2 mole to Dimethylamino pyridine as catalyzer, stirring at room temperature reaction 12 hours.Then add aqueous ammonium chloride solution, continue stirring at room temperature and react half an hour.Reaction finishes to fall back, and extracts with methylene dichloride.Then respectively with salt washing and deionization washing, extract organic layer anhydrous magnesium sulfate drying.After filtration, filtrate is spin-dried for, precipitation obtains 4-[(2-N-ethylbenzene amido taking methylene dichloride and ethyl acetate (volume ratio 20: 1) as eluent carries out column chromatography for separation purification) oxyethyl group]-4-ketobutyric acid.Its building-up reactions formula is:
Nucleus magnetic resonance:
1h NMR (500 MHz, CDCl
3-
d 6): δ=1.14 (m, 3H, C
h 3), 2.59 (m, 2H, OC
h 2), 2.65 (m, 2H, OC
h 2), 3.37 (m, 2H, C
h 2cH
3), 3.53 (t, 2H, NC
h 2), 4.24 (t, 2H, C
h 2o), 6.67 (m, 3H, Ar
h), 7.21 (m, 2H, Ar
h).
(3) get the dendritic core containing propylene glycol that 1 mole of step (1) makes and the 4-[(2-N-ethylbenzene amido that 9 moles of steps (2) make) oxyethyl group]-4-ketobutyric acid is dissolved in the mixing solutions of 200 mL tetrahydrofuran (THF)s and 600 mL methylene dichloride, adds 9 moles
n,
n'-dicyclohexylcarbodiimide and 2 moles to Dimethylamino pyridine as catalyzer, room temperature reaction 48 hours.Reaction is poured in frozen water after finishing, and extracts with methylene dichloride.Respectively with salt solution and deionization washing, organic layer anhydrous magnesium sulfate drying.After filtration, being spin-dried for solution, is then stationary phase with 100-200 object silica gel, and the column chromatography that tetrahydrofuran (THF) and methylene dichloride (volume ratio 1: 40) are eluent carries out purification processes.Its building-up reactions formula is:
(4) get the ethylene chlorhydrin of 1 mole and the chloro-5-nitrophenols of 2-amino-4-of 1.2 moles and be dissolved in 500 mL DMFs, add the sodium carbonate of 1.25 moles.Return stirring reaction 12 hours.After reaction finishes, pour in frozen water, extract with methylene dichloride.Respectively with salt solution and deionization washing, organic layer anhydrous magnesium sulfate drying.Filter, be spin-dried for solution, then the column chromatography taking methylene dichloride as eluent carries out purification processes.Its building-up reactions formula is:
(5) get the product that 2 moles of steps (4) make and be dissolved in the 2L vitriol oil, be cooled to 0
oafter C, slowly drip 200mL sodium nitrite in aqueous solution (containing 0.7mol Sodium Nitrite).The product that reaction adds 1 mole of step (3) to make after half an hour.Stir after 1 hour, by solution of potassium carbonate adjusting pH value to 7.After reaction finishes, pour in frozen water, extract rear with salt solution and deionization washing, organic layer anhydrous magnesium sulfate drying with methylene dichloride.Filter, be spin-dried for solution, then obtain six dendritic azo chromophores taking tetrahydrofuran (THF) and methylene dichloride (volume ratio 1: 40) as the column chromatography of eluent carries out purification processes.Its building-up reactions formula is:
(6) get six azo chromophore dyestuffs of 1 mole and the isocyanate group propyl-triethoxysilicane of 7 moles and be dissolved in 200mL tetrahydrofuran (THF), add 5mL pyridine.After heating reflux reaction 60 hours, reaction solution is poured in normal hexane, filtering-depositing obtains six branched azosiloxane dyes.Its building-up reactions formula is:
The six branched azosiloxane dye molecular weight that this example makes are up to 4958.13, its active non-linear optical chromophore content reaches 79.29 wt.%, and spin-coating film is prepared into nonlinear optical material or prepares organic-inorganic hybridized non-linear optical material as precursor by sol gel reaction separately.
Embodiment 3:
R
1for hydrogen, R
2for the synthetic method of six branched azosiloxane dyes of nitro, its step is as follows:
(1) get 1 mole 1,1,1-tri-(4-hydroxy phenyl) ethane is dissolved in 600 mL ethanolic solns, is added dropwise to the aqueous solution containing 5 molar sodium hydroxides, return stirring reaction half an hour.Then add 3-chloropropyl-1 of 5 moles, 2-glycol, continues back flow reaction 4 hours.Reaction finishes rear coolingly, and solvent is poured in water, extracts by ethyl acetate, and underpressure distillation, except desolventizing, obtains the dendritic core containing propylene glycol.Its building-up reactions formula is:
nucleus magnetic resonance:
1h NMR (500 MHz, DMSO-
d 6): δ=2.03 (s, 3H, C
h 3), 3.43 (d, 6H, OC
h 2), 3.80 (m, 6H, O
h), 3.95 (m, 3H, C
h), 4.67 (d, 3H, C
h 2oH), 4.95 (d, 3H, C
h 2oH), 6.82 (d, 6H, Ar
h), 6.91 (d, 6H, Ar
h).
13C NMR (125 MHz, DMSO-
d 6): δ = 157.167, 141.785, 129.695, 114.142, 70.457, 69.911, 63.207, 50.600, 30.863.
Ultimate analysis: theoretical value C
29h
36o
9: C, 65.89; H, 6.86; Measured value C, 65.52; H 7.06.
Mass spectrum: theoretical value C
29h
36o
9[M+H]
+, 527.2. measured value: 526.9.
(2) get the 2-(of 1 mole
n-ethylbenzene amido) succinyl oxide of ethanol and 2 moles is dissolved in 600 mL methylene dichloride, add the pyridine of 5 mL and 0.2 mole to Dimethylamino pyridine as catalyzer, stirring at room temperature reaction 12 hours.Then add aqueous ammonium chloride solution, continue stirring at room temperature and react half an hour.Reaction finishes to fall back, and extracts with methylene dichloride.Then respectively with salt washing and deionization washing, extract organic layer anhydrous magnesium sulfate drying.After filtration, filtrate is spin-dried for, precipitation obtains 4-[(2-taking methylene dichloride and ethyl acetate (volume ratio 20: 1) as eluent carries out column chromatography for separation purification
n-ethylbenzene amido) oxyethyl group]-4-ketobutyric acid.Its building-up reactions formula is:
Nucleus magnetic resonance:
1h NMR (500 MHz, CDCl
3-
d 6): δ=1.14 (m, 3H, C
h 3), 2.59 (m, 2H, OC
h 2), 2.65 (m, 2H, OC
h 2), 3.37 (m, 2H, C
h 2cH
3), 3.53 (t, 2H, NC
h 2), 4.24 (t, 2H, C
h 2o), 6.67 (m, 3H, Ar
h), 7.21 (m, 2H, Ar
h).
(3) get the dendritic core containing propylene glycol that 1 mole of step (1) makes and the 4-[(2-N-ethylbenzene amido that 8 moles of steps (2) make) oxyethyl group]-4-ketobutyric acid is dissolved in the mixing solutions of 200 mL tetrahydrofuran (THF)s and 600 mL methylene dichloride, adds 9 moles
n,
n'-dicyclohexylcarbodiimide and 2 moles to Dimethylamino pyridine as catalyzer, room temperature reaction 48 hours.Reaction is poured in frozen water after finishing, and extracts with methylene dichloride.Respectively with salt solution and deionization washing, organic layer anhydrous magnesium sulfate drying.After filtration, being spin-dried for solution, is then stationary phase with 100-200 object silica gel, and the column chromatography that tetrahydrofuran (THF) and methylene dichloride (volume ratio 1: 40) are eluent carries out purification processes.Its building-up reactions formula is:
(4) get the ethylene chlorhydrin of 1 mole and the 2-Amino-4-nitrophenol of 1.2 moles and be dissolved in 500 mL
n,
nin-dimethyl formamide, add the sodium bicarbonate of 1.25 moles.Return stirring reaction 12 hours.After reaction finishes, pour in frozen water, extract with methylene dichloride.Respectively with salt solution and deionization washing, organic layer anhydrous magnesium sulfate drying.Filter, be spin-dried for solution, then the column chromatography taking methylene dichloride as eluent carries out purification processes.Its building-up reactions formula is:
(5) get the product that 1.5 moles of steps (4) make and be dissolved in 2L concentrated hydrochloric acid, be cooled to 0
oafter C, slowly drip 200mL sodium nitrite in aqueous solution (containing 0.7mol Sodium Nitrite).The product that reaction adds 1 mole of step (3) to make after half an hour.Stir after 1 hour, by solution of potassium carbonate adjusting pH value to 6.After reaction finishes, pour in frozen water, extract rear with salt solution and deionization washing, organic layer anhydrous magnesium sulfate drying with methylene dichloride.Filter, be spin-dried for solution, then obtain six dendritic azo chromophores taking tetrahydrofuran (THF) and methylene dichloride (volume ratio 1: 40) as the column chromatography of eluent carries out purification processes.Its building-up reactions formula is:
(6) get the six dendritic azo chromophores of 1 mole and the isocyanate group propyl-triethoxysilicane of 8 moles and be dissolved in 200mL tetrahydrofuran (THF), add 5mL dibutyl tin laurate.After heating reflux reaction 72 hours, reaction solution is poured in normal hexane, filtering-depositing obtains six branched azosiloxane dyes.Its building-up reactions formula is:
The six branched azosiloxane dye molecular weight that this example makes are up to 4751.46, its active non-linear optical chromophore content reaches 78.39 wt.%, and spin-coating film is prepared into nonlinear optical material or prepares organic-inorganic hybridized non-linear optical material as precursor by sol gel reaction separately.
Claims (10)
1. six branched azosiloxane dyes, its general structure is as follows:
R in formula
1during for nitro, R
2for hydrogen or chlorine; R
1during for hydrogen, R
2for nitro.
2. the synthetic method of six branched azosiloxane dyes claimed in claim 1, is characterized in that comprising the following steps:
(1) by 1 mole 1,1,1-tri-(4-hydroxy phenyl) ethane is dissolved in ethanolic soln, be added dropwise to the alkaline solution containing 2-5 mole, return stirring reacts half an hour, then adds 3-chloropropyl-1 of 3-5 mole, 2-glycol, continue back flow reaction 4 hours, reaction finishes rear coolingly, and solution is poured in water, extracts by ethyl acetate, underpressure distillation, except desolventizing, obtains the dendritic core containing propylene glycol;
(2) by the 2-(of 1 mole
n-ethylbenzene amido) succinyl oxide of ethanol and 1-2 mole is dissolved in methylene dichloride, add organic bases and to Dimethylamino pyridine as catalyzer, stirring at room temperature reaction 12 hours, then add aqueous ammonium chloride solution, continue stirring at room temperature and react half an hour, reaction finishes to fall back, and extracts and with the column chromatography acquisition 4-[(2-that purifies with methylene dichloride
n-ethylbenzene amido) oxyethyl group]-4-ketobutyric acid;
(3) the dendritic core containing propylene glycol 1 mole of step (1) being made and the 4-[(2-that 6-9 mole of step (2) makes
n-ethylbenzene amido) oxyethyl group]-4-ketobutyric acid is dissolved in organic solvent, what add the carbodiimide compound of 9 moles and 2 moles is catalyzer to Dimethylamino pyridine, stirring at room temperature reaction 48 hours, reaction is poured in frozen water after finishing, and extracts and carries out purification processes with column chromatography with methylene dichloride;
(4) phenol derivatives of the ethylene chlorhydrin of 1 mole and 1.2 moles is dissolved in
n,
nin-dimethyl formamide, add the inorganic salt of 1.25 moles, return stirring reaction 12 hours, after reaction finishes, pours in frozen water, extracts and carries out purification processes with column chromatography with methylene dichloride;
(5) product 1-2 mole of step (4) being made is dissolved in acid, is cooled to 0
oafter C, slowly drip sodium nitrite in aqueous solution, the product that reaction adds 1 mole of step (3) to make after half an hour, stir after 1 hour, regulate pH value to 6-7 with solution of potassium carbonate, after reaction finishes, pour in frozen water, extract and carry out obtaining after purification processes the six dendritic azo chromophores that are connected with hydroxyl with column chromatography with methylene dichloride;
(6) six dendritic azo chromophores of 1 mole of acquisition and the isocyanate group propyl-triethoxysilicane of 6-8 mole are dissolved in to tetrahydrofuran (THF), add catalyzer, after return stirring reaction 24-72h, reaction solution is poured in normal hexane, filtering-depositing is also purified with column chromatography, obtains six branched azosiloxane dyes.
3. the synthetic method of six branched azosiloxane dyes according to claim 2, is characterized in that the said alkaline solution of step (1) is sodium hydroxide, the aqueous solution of potassium hydroxide or sodium carbonate.
4. the synthetic method of six branched azosiloxane dyes according to claim 2, is characterized in that the said organic bases of step (2) is triethylamine or pyridine.
5. the synthetic method of six branched azosiloxane dyes according to claim 2, it is characterized in that the said organic solvent of step (3) be tetrahydrofuran (THF), methylene dichloride, ethyl acetate and
n,
none in-dimethyl formamide or mixing solutions.
6. the synthetic method of six branched azosiloxane dyes according to claim 2, is characterized in that the said carbodiimide compound of step (3) is
n,
n'-dicyclohexylcarbodiimide or 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride.
7. the synthetic method of six branched azosiloxane dyes according to claim 2, is characterized in that the said phenol derivatives of step (4) is the chloro-5-nitrophenols of 2-Amino-5-nitrophenol, 2-amino-4-or 2-Amino-4-nitrophenol.
8. the synthetic method of six branched azosiloxane dyes according to claim 2, is characterized in that the said inorganic salt of step (4) are salt of wormwood, saleratus, sodium carbonate or sodium bicarbonate.
9. the synthetic method of six branched azosiloxane dyes according to claim 2, is characterized in that the said acid of step (5) is concentrated hydrochloric acid or the vitriol oil.
10. the synthetic method of six branched azosiloxane dyes according to claim 2, is characterized in that the said catalyzer of step (6) is triethylamine, pyridine, stannous octoate or dibutyl tin laurate.
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