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CN102295838B - Six-branched azosiloxane dye and synthesis method thereof - Google Patents

Six-branched azosiloxane dye and synthesis method thereof Download PDF

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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
reaction
mole
methylene dichloride
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CN102295838A (en
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钱国栋
林文鑫
崔元靖
高俊阔
郁建灿
王智宇
樊先平
王民权
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Zhejiang University ZJU
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00Dyes not provided for by a single group of this subclass
    • C09B69/10Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/106Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azo dye
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/18Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804Compounds having Si-O-C linkages
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00Dyes not provided for by a single group of this subclass
    • C09B69/008Dyes containing a substituent, which contains a silicium atom
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00Dyes not provided for by a single group of this subclass
    • C09B69/10Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/103Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a diaryl- or triarylmethane dye

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  • Organic Chemistry (AREA)
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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

A kind of six branched azosiloxane dyes and synthetic method thereof
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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