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

Abstract

The hexadendritic azosiloxane dye disclosed in the present invention has a general structural formula such as formula 1, wherein when _R1 is nitro, _R2 is hydrogen or chlorine; when _R1 is hydrogen, _R2 is nitro. The synthesis method is as follows: 1,1,1-tris(4-hydroxyphenyl)ethane and 3-chloropropyl-1,2-diol are synthesized by Williamson ether to prepare a dendritic nucleus containing propylene glycol, and then combined with 4-[(2-N-Ethylanilino)ethoxy]-4-oxobutanoic acid was subjected to esterification reaction, and then diazo-coupling reaction with phenol derivatives was carried out to obtain six branched bifurcations with hydroxyl groups Nitrogen chromophore, the chromophore is added with isocyanate propyltriethoxysilane to obtain hexadendritic azosiloxane dye. The synthesis method has the advantages of simple process, mild conditions, readily available raw materials and high yield. The six-branched azosiloxane dye has good solubility and film-forming processability, large nonlinear optical performance and high thermal stability. Formula 1

Description

A kind of hexadendritic azosiloxane dye and its synthetic method

technical field

The invention relates to a six-branched azosiloxane dye and a synthesis method thereof.

Background technique

Nonlinear optics plays an important role in the development of optoelectronics and photonics technology. Using different nonlinear optical effects such as frequency mixing, sum frequency, difference frequency, and electro-optic, many optical information such as optical modulation, optical switching, optical storage, and optical limiting can be prepared. Processing components. Therefore, the development of new nonlinear optical materials is of great significance to economic construction and national defense security.

Common nonlinear optical materials mainly include inorganic crystals, organic crystals, and polymer materials. Inorganic crystals are the first class of second-order nonlinear optical materials studied and used by people, such as lithium niobate, gallium arsenide and other inorganic crystals. The development of these inorganic crystal materials has been relatively mature and has already been commercialized. However, there are also obvious shortcomings, such as easy deliquescence, damage caused by dehydration, and can only work in the form of single crystal materials, and it is difficult to realize optical integration. Therefore, these inorganic crystal materials cannot meet a series of requirements required in the rapidly developing fields of optical communication and optical signal processing. In the 1970s, people began to study and explore organic nonlinear optical materials. Compared with inorganic nonlinear materials, organic nonlinear materials have large nonlinear optical coefficients (1-3 orders of magnitude), fast response speed (up to femtoseconds), low dielectric constant, high optical damage threshold, excellent processing performance and A series of advantages such as molecular design can be carried out. In particular, the variability and adjustability of organic molecular structures enable people to realize molecular design and tailoring to meet the practical requirements of devices through the understanding of their structure-performance relationships.

Dendrimers have a unique spherical structure, three-dimensional cavity shape and good monodispersity characteristics, which make them widely used in the field of nonlinear materials. This dendritic structure effectively reduces the strong electrostatic interaction between the chromophore molecules and prevents the intermolecular agglomeration. A large number of three-dimensional cavities can provide the free turning space required for the orderly arrangement of chromophores, improve the polarization efficiency, and achieve the purpose of enhancing nonlinear optical performance. However, organic materials often have low thermal stability and are difficult to be applied in practical devices. Inorganic-organic hybrid materials can combine the high stability and high transparency of inorganic materials and the excellent optical activity and modification of organic materials, and have the advantages of good matching with optical fibers, low coupling loss, adjustable refractive index, and easy integration. Excellent characteristics, has become an emerging hotspot in the field of optoelectronics. The introduction of dendritic structures into inorganic-organic hybrid materials is expected to suppress the strong electrostatic interaction between dipole molecules in inorganic-organic hybrid materials, improve the compatibility of materials and enhance nonlinear optical properties and thermal stability. Sex provides a new and effective way.

Contents of the invention

The purpose of the present invention is to provide a hexabranch azosiloxane dye and its synthesis method. This type of compound has good solubility and film-forming processability, as well as large nonlinear optical properties and high thermal stability, and is expected to be used as a new nonlinear optical material in the fields of electro-optic modulation, optical switches and optical storage. be applied in.

The six-branched azosiloxane dye of the present invention has a general structural formula as follows:

In the formula, when _R1 is nitro, _R2 is hydrogen or chlorine; when _R1 is hydrogen, _R2 is nitro.

The synthetic method of hexapodil azosiloxane dye of the present invention, its step is as follows:

(1) Dissolve 1 mole of 1,1,1-tris(4-hydroxyphenyl)ethane in ethanol solution, add dropwise into alkali solution containing 2-5 moles, reflux and stir for half an hour, then add 3- 5 moles of 3-chloropropyl-1,2-diol, continued to reflux for 4 hours, cooled after the reaction, poured the solution into water, extracted with ethyl acetate, and distilled off the solvent under reduced pressure to obtain propylene glycol dendritic nucleus;

(2) Dissolve 1 mole of 2-( N -ethylanilino)ethanol and 1-2 moles of succinic anhydride in dichloromethane, add an organic base and p-dimethylaminopyridine as a catalyst, and stir at room temperature for 12 hours , then add ammonium chloride aqueous solution, continue stirring at room temperature for half an hour, pour into water after the reaction is over, extract with dichloromethane and purify with column chromatography to obtain 4-[(2- N -ethylanilino) ethyl Oxy]-4-oxobutanoic acid;

(3) 1 mole of the propylene glycol-containing dendritic core prepared in step (1) and 6-9 moles of 4-[(2- N -ethylanilino) ethoxy]-4 prepared in step (2) -Oxobutanoic acid was dissolved in an organic solvent, and 9 moles of carbodiimide compound and 2 moles of p-dimethylaminopyridine were added as catalysts, stirred and reacted at room temperature for 48 hours, poured into ice water after the reaction was completed, and dichloromethane Extraction and purification by column chromatography;

(4) Dissolve 1 mole of 2-chloroethanol and 1.2 moles of phenol derivatives in N , N -dimethylformamide, add 1.25 moles of inorganic salts, reflux and stir for 12 hours, after the reaction, pour In ice water, extracted with dichloromethane and purified by column chromatography;

(5) Dissolve 1-2 moles of the product obtained in step (4) in acid, cool to 0 ^o C, slowly add sodium nitrite aqueous solution dropwise, and add 1 mole of the product obtained in step (3) after reacting for half an hour , after stirring for 1 hour, adjust the pH value to 6-7 with potassium carbonate solution, pour into ice water after the reaction, extract with dichloromethane and purify with column chromatography to obtain hexabranches with hydroxyl groups Azo chromophore;

(6) Dissolve 1 mole of the obtained six-branched azo chromophore and 6-8 moles of isocyanatopropyl triethoxysilane in tetrahydrofuran, add catalyst, reflux and stir for 24-72 hours, then pour the reaction solution into n-hexane, filter the precipitate and purify by column chromatography to obtain six branched azosiloxane dyes.

In the above-mentioned synthetic method, the said alkali solution of step (1) is sodium hydroxide, the aqueous solution of potassium hydroxide or sodium carbonate; The said organic base of step (2) is triethylamine or pyridine; The said step (3) The organic solvent is one or a mixed solution of tetrahydrofuran, dichloromethane, ethyl acetate and N , N -dimethylformamide; the carbodiimide compound in step (3) is N , N' -di Cyclohexylcarbodiimide or 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride; the phenol derivative in step (4) is 2-amino-5-nitrophenol , 2-amino-4-chloro-5-nitrophenol or 2-amino-4-nitrophenol; the said inorganic salt of step (4) is potassium carbonate, potassium bicarbonate, sodium carbonate or sodium bicarbonate; step (5) said acid is concentrated hydrochloric acid or concentrated sulfuric acid; said catalyst of step (6) is triethylamine, pyridine, stannous octoate or dibutyltin dilaurate.

The beneficial effects of the present invention are:

1. The synthesis process of the six-branched azosiloxane dye of the invention is simple, the conditions are mild, the raw materials are easily available, and the yield is high.

2. The dendritic structure of the hexadendritic azosiloxane dye of the present invention can significantly reduce the electrostatic interaction between chromophores, improve the effective chromophore loading concentration and polarization efficiency of the material, thereby effectively enhancing the macroscopic non-toxicity of the material. Linear optical performance. Moreover, the hexadendritic structure is expected to increase the steric hindrance effect of the chromophore rotation, thereby improving the thermal stability of the polarized orientation of the chromophore.

3. Compared with simple organic chromophore molecules, the six-branched azosiloxane dye of the present invention has good solubility, film-forming processability, and good silicon-based compatibility, and can be directly applied on glass or silicon wafers. It can be used as a precursor to prepare inorganic-organic hybrid thin films through sol-gel reactions. It is expected to be used as a new type of nonlinear optical material in the fields of electro-optic modulation, optical switching and optical storage.

Detailed ways

Example 1:

R ₁ is nitro, and R ₂ is the synthetic method of the six-branched azosiloxane dye of hydrogen, and its steps are as follows:

(1) Dissolve 1 mole of 1,1,1-tris(4-hydroxyphenyl)ethane in 600 mL of ethanol solution, add dropwise to an aqueous solution containing 2 moles of sodium hydroxide, reflux and stir for half an hour. Then 3 moles of 3-chloropropyl-1,2-diol were added, and the reflux reaction was continued for 4 hours. Cool after the reaction, pour the solvent into water, extract with ethyl acetate, and distill off the solvent under reduced pressure to obtain a dendritic nucleus containing propylene glycol. Its synthetic reaction formula is:

NMR: ¹ H NMR (500 MHz, DMSO- d ₆ ): δ = 2.03 (s, 3H, CH ₃ ), 3.43 (d, 6H, O CH ₂ ), 3.80 (m, 6H, OH ), 3.95 (m, 3H, CH ), 4.67(d, 3H, CH ₂ OH), 4.95 (d, 3H, CH ₂ OH), 6.82 (d, 6H, Ar H ), 6.91 (d, 6H, ArH ).

¹³ C 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.

Elemental analysis: theoretical value C ₂₉ H ₃₆ O ₉ : C, 65.89; H, 6.86; found value C, 65.52; H 7.06.

Mass spectrum: theoretical value C ₂₉ H ₃₆ O ₉ [M+H] ⁺ , 527.2. Found value: 526.9.

(2) Dissolve 1 mole of 2-( N -ethylanilino)ethanol and 1.2 moles of succinic anhydride in 600 mL of dichloromethane, add 5 mL of pyridine and 0.2 moles of p-dimethylaminopyridine as catalysts, The reaction was stirred at room temperature for 12 hours. Then ammonium chloride aqueous solution was added, and the stirring reaction at room temperature was continued for half an hour. After the reaction, it was poured into water and extracted with dichloromethane. Then washed with brine and deionized water respectively, and the extracted organic layer was dried with anhydrous magnesium sulfate. After filtration, the filtrate was spin-dried, and the precipitate was separated and purified by column chromatography using dichloromethane and ethyl acetate (volume ratio 20:1) as the eluent to obtain 4-[(2-N-ethylanilino)ethoxy ]-4-oxobutanoic acid. Its synthetic reaction formula is:

NMR: ¹ H NMR (500 MHz, CDCl ₃ - d ₆ ): δ = 1.14 (m, 3H, CH ₃ ), 2.59 (m, 2H, OCH ₂ ), 2.65 (m, 2H, OCH ₂ ), 3.37 (m, 2H, CH ₂ CH ₃ ), 3.53(t, 2H, NCH ₂ ), 4.24 (t, 2H, CH ₂ O), 6.67 (m, 3H, Ar H ), 7.21 ( m, 2H, ArH ).

(3) Get 1 mole of the dendritic nucleus containing propylene glycol prepared in step (1) and 4-[(2- N -ethylanilino) ethoxy]-4-oxygen obtained in 6 moles of step (2) Butyric acid was dissolved in a mixed solution of 200 mL tetrahydrofuran and 600 mL methylene chloride, 9 moles of N , N' -dicyclohexylcarbodiimide and 2 moles of p-dimethylaminopyridine were added as catalysts, and the reaction was carried out at room temperature for 48 Hour. After the reaction, it was poured into ice water and extracted with dichloromethane. Wash with brine and deionized water respectively, and dry the organic layer with anhydrous magnesium sulfate. After filtration, the solution was spin-dried, and then purified by column chromatography using 100-200 mesh silica gel as the stationary phase and tetrahydrofuran and dichloromethane (volume ratio 1:40) as the eluent. Its synthetic reaction formula is:

(4) Dissolve 1 mole of 2-chloroethanol and 1.2 moles of 2-amino-5-nitrophenol in 500 mL of N , N -dimethylformamide, and add 1.25 moles of sodium carbonate. The reaction was stirred at reflux for 12 hours. After the reaction, it was poured into ice water and extracted with dichloromethane. Wash with brine and deionized water respectively, and dry the organic layer with anhydrous magnesium sulfate. Filter, spin dry the solution, and then purify by column chromatography using dichloromethane as eluent. Its synthetic reaction formula is:

NMR: ¹ H NMR (500 MHz, CDCl ₃ - d ₆ ): δ = 1.85 (s, 1H, O H ), 4.05 (t, 2H, CH ₂ OH), 4.22 (t, 2H, O 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 ₈ H ₁₀ N ₂ O ₄ [MH] ^－ , 197.18. Measured value: 198.3.

(5) Dissolve 1 mole of the product obtained in step (4) in 2L of concentrated hydrochloric acid, cool to 0 ^o C, and slowly add 200 mL of sodium nitrite aqueous solution (containing 0.7 mol of sodium nitrite) dropwise. After half an hour of reaction, 1 mole of the product obtained in step (3) was added. After stirring for 1 hour, the pH was adjusted to 7 with potassium carbonate solution. After the reaction, it was poured into ice water, extracted with dichloromethane, washed with brine and deionized water, and the organic layer was dried with anhydrous magnesium sulfate. The solution was filtered, spin-dried, and purified by column chromatography using tetrahydrofuran and dichloromethane (volume ratio 1 : 40) as eluents to obtain a six-branched azo chromophore. Its synthetic reaction formula is:

(6) Dissolve 1 mole of hexadendritic azo chromophore and 6 moles of isocyanatopropyltriethoxysilane in 200 mL of tetrahydrofuran, and add 5 mL of stannous octoate. After heating to reflux for 24 hours, the reaction solution was poured into n-hexane, and the precipitate was filtered to obtain hexabranch azosiloxane dye. Its synthetic reaction formula is:

The molecular weight of the hexadendritic azosiloxane dye prepared in this example is as high as 4751.46, and its active nonlinear optical chromophore content reaches 78.39 wt.%. Preparation of Inorganic-Organic Hybrid Nonlinear Optical Materials by Sol-Gel Reaction.

Example 2:

R ₁ is nitro, and R ₂ is the synthetic method of the six branched azosiloxane dyes of chlorine, and its steps are as follows:

(1) Dissolve 1 mole of 1,1,1-tris(4-hydroxyphenyl)ethane in 600 mL of ethanol solution, add dropwise to an aqueous solution containing 5 moles of potassium hydroxide, reflux and stir for half an hour. Then 4 moles of 3-chloropropyl-1,2-diol were added, and the reflux reaction was continued for 4 hours. Cooling after the reaction is over, the solvent is poured into water, extracted with ethyl acetate, and the solvent is distilled off under reduced pressure to obtain a dendritic nucleus containing propylene glycol; its synthetic reaction formula is:

NMR: ¹ H NMR (500 MHz, DMSO- d ₆ ): δ = 2.03 (s, 3H, CH ₃ ), 3.43 (d, 6H, O CH ₂ ), 3.80 (m, 6H, OH ), 3.95 (m, 3H, CH ), 4.67(d, 3H, CH ₂ OH), 4.95 (d, 3H, CH ₂ OH), 6.82 (d, 6H, Ar H ), 6.91 (d, 6H, ArH ).

¹³ C 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.

Elemental analysis: theoretical value C ₂₉ H ₃₆ O ₉ : C, 65.89; H, 6.86; found value C, 65.52; H 7.06.

Mass spectrum: theoretical value C ₂₉ H ₃₆ O ₉ [M+H] ⁺ , 527.2. Found value: 526.9.

(2) Dissolve 1 mole of 2-(N-ethylanilino)ethanol and 2 moles of succinic anhydride in 600 mL of dichloromethane, add 5 mL of triethylamine and 0.2 moles of p-dimethylaminopyridine as Catalyst, stirred at room temperature for 12 hours. Then ammonium chloride aqueous solution was added, and the stirring reaction at room temperature was continued for half an hour. After the reaction, it was poured into water and extracted with dichloromethane. Then washed with brine and deionized water respectively, and the extracted organic layer was dried with anhydrous magnesium sulfate. After filtration, the filtrate was spin-dried, and the precipitate was separated and purified by column chromatography with dichloromethane and ethyl acetate (volume ratio 20:1) as the eluent to obtain 4-[(2-N-ethylanilino)ethoxy ]-4-oxobutanoic acid. Its synthetic reaction formula is:

NMR: ¹ H NMR (500 MHz, CDCl ₃ - d ₆ ): δ = 1.14 (m, 3H, CH ₃ ), 2.59 (m, 2H, OCH ₂ ), 2.65 (m, 2H, OCH ₂ ), 3.37 (m, 2H, CH ₂ CH ₃ ), 3.53(t, 2H, NCH ₂ ), 4.24 (t, 2H, CH ₂ O), 6.67 (m, 3H, Ar H ), 7.21 ( m, 2H, ArH ).

(3) Take 1 mole of the dendritic core containing propylene glycol prepared in step (1) and 9 moles of 4-[(2-N-ethylanilino) ethoxy]-4-oxygen obtained in step (2) Butyric acid was dissolved in a mixed solution of 200 mL tetrahydrofuran and 600 mL methylene chloride, 9 moles of N , N' -dicyclohexylcarbodiimide and 2 moles of p-dimethylaminopyridine were added as catalysts, and the reaction was carried out at room temperature for 48 Hour. After the reaction, it was poured into ice water and extracted with dichloromethane. Wash with brine and deionized water respectively, and dry the organic layer with anhydrous magnesium sulfate. After filtration, the solution was spin-dried, and then purified by column chromatography using 100-200 mesh silica gel as the stationary phase and tetrahydrofuran and dichloromethane (volume ratio 1:40) as the eluent. Its synthetic reaction formula is:

(4) Dissolve 1 mole of 2-chloroethanol and 1.2 moles of 2-amino-4-chloro-5-nitrophenol in 500 mL of N,N-dimethylformamide, and add 1.25 moles of sodium carbonate. The reaction was stirred at reflux for 12 hours. After the reaction, it was poured into ice water and extracted with dichloromethane. Wash with brine and deionized water respectively, and dry the organic layer with anhydrous magnesium sulfate. Filter, spin dry the solution, and then purify by column chromatography using dichloromethane as eluent. Its synthetic reaction formula is:

(5) Dissolve 2 mol of the product obtained in step (4) in 2L of concentrated sulfuric acid, cool to 0 ^o C, and slowly add 200mL of sodium nitrite aqueous solution (containing 0.7mol of sodium nitrite) dropwise. After half an hour of reaction, 1 mole of the product obtained in step (3) was added. After stirring for 1 hour, the pH was adjusted to 7 with potassium carbonate solution. After the reaction, it was poured into ice water, extracted with dichloromethane, washed with brine and deionized water, and the organic layer was dried with anhydrous magnesium sulfate. The solution was filtered, spin-dried, and purified by column chromatography using tetrahydrofuran and dichloromethane (volume ratio 1 : 40) as eluents to obtain a six-branched azo chromophore. Its synthetic reaction formula is:

(6) Dissolve 1 mole of hexazochromophore dye and 7 moles of isocyanatopropyltriethoxysilane in 200 mL of tetrahydrofuran, and add 5 mL of pyridine. After heating to reflux for 60 hours, the reaction solution was poured into n-hexane, and the precipitate was filtered to obtain hexabranch azosiloxane dye. Its synthetic reaction formula is:

The molecular weight of the six-branched azosiloxane dye prepared in this example is as high as 4958.13, and its active nonlinear optical chromophore content reaches 79.29 wt.%. Preparation of Inorganic-Organic Hybrid Nonlinear Optical Materials by Sol-Gel Reaction.

Example 3:

R ₁ is hydrogen, and R ₂ is the synthetic method of the six branched azosiloxane dyes of nitro, and its steps are as follows:

(1) Dissolve 1 mole of 1,1,1-tris(4-hydroxyphenyl)ethane in 600 mL of ethanol solution, add dropwise to an aqueous solution containing 5 moles of sodium hydroxide, reflux and stir for half an hour. Then 5 moles of 3-chloropropyl-1,2-diol were added, and the reflux reaction was continued for 4 hours. Cool after the reaction, pour the solvent into water, extract with ethyl acetate, and distill off the solvent under reduced pressure to obtain a dendritic nucleus containing propylene glycol. Its synthetic reaction formula is:

NMR: ¹ H NMR (500 MHz, DMSO- d ₆ ): δ = 2.03 (s, 3H, CH ₃ ), 3.43 (d, 6H, O CH ₂ ), 3.80 (m, 6H, OH ), 3.95 (m, 3H, CH ), 4.67(d, 3H, CH ₂ OH), 4.95 (d, 3H, CH ₂ OH), 6.82 (d, 6H, Ar H ), 6.91 (d, 6H, ArH ).

¹³ C 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.

Elemental analysis: theoretical value C ₂₉ H ₃₆ O ₉ : C, 65.89; H, 6.86; found value C, 65.52; H 7.06.

Mass spectrum: theoretical value C ₂₉ H ₃₆ O ₉ [M+H] ⁺ , 527.2. Found value: 526.9.

(2) Dissolve 1 mole of 2-( N -ethylanilino)ethanol and 2 moles of succinic anhydride in 600 mL of dichloromethane, add 5 mL of pyridine and 0.2 moles of p-dimethylaminopyridine as catalysts, The reaction was stirred at room temperature for 12 hours. Then ammonium chloride aqueous solution was added, and the stirring reaction at room temperature was continued for half an hour. After the reaction, it was poured into water and extracted with dichloromethane. Then washed with brine and deionized water respectively, and the extracted organic layer was dried with anhydrous magnesium sulfate. After filtration, the filtrate was spin-dried, and the precipitate was separated and purified by column chromatography using dichloromethane and ethyl acetate (volume ratio 20:1) as the eluent to obtain 4-[(2- N -ethylanilino)ethoxy ]-4-oxobutanoic acid. Its synthetic reaction formula is:

NMR: ¹ H NMR (500 MHz, CDCl ₃ - d ₆ ): δ = 1.14 (m, 3H, CH ₃ ), 2.59 (m, 2H, OCH ₂ ), 2.65 (m, 2H, OCH ₂ ), 3.37 (m, 2H, CH ₂ CH ₃ ), 3.53(t, 2H, NCH ₂ ), 4.24 (t, 2H, CH ₂ O), 6.67 (m, 3H, Ar H ), 7.21 ( m, 2H, ArH ).

(3) Take 1 mole of the dendritic core containing propylene glycol prepared in step (1) and 8 moles of 4-[(2-N-ethylanilino) ethoxy]-4-oxygen obtained in step (2) Butyric acid was dissolved in a mixed solution of 200 mL tetrahydrofuran and 600 mL methylene chloride, 9 moles of N , N' -dicyclohexylcarbodiimide and 2 moles of p-dimethylaminopyridine were added as catalysts, and the reaction was carried out at room temperature for 48 Hour. After the reaction, it was poured into ice water and extracted with dichloromethane. Wash with brine and deionized water respectively, and dry the organic layer with anhydrous magnesium sulfate. After filtration, the solution was spin-dried, and then purified by column chromatography using 100-200 mesh silica gel as the stationary phase and tetrahydrofuran and dichloromethane (volume ratio 1:40) as the eluent. Its synthetic reaction formula is:

(4) Dissolve 1 mole of 2-chloroethanol and 1.2 moles of 2-amino-4-nitrophenol in 500 mL of N , N -dimethylformamide, and add 1.25 moles of sodium bicarbonate. The reaction was stirred at reflux for 12 hours. After the reaction, it was poured into ice water and extracted with dichloromethane. Wash with brine and deionized water respectively, and dry the organic layer with anhydrous magnesium sulfate. Filter, spin dry the solution, and then purify by column chromatography using dichloromethane as eluent. Its synthetic reaction formula is:

(5) Dissolve 1.5 mol of the product obtained in step (4) in 2L of concentrated hydrochloric acid, cool to 0 ^o C, and slowly add 200mL of sodium nitrite aqueous solution (containing 0.7mol of sodium nitrite) dropwise. After half an hour of reaction, 1 mole of the product obtained in step (3) was added. After stirring for 1 hour, the pH was adjusted to 6 with potassium carbonate solution. After the reaction, it was poured into ice water, extracted with dichloromethane, washed with brine and deionized water, and the organic layer was dried with anhydrous magnesium sulfate. The solution was filtered, spin-dried, and purified by column chromatography using tetrahydrofuran and dichloromethane (volume ratio 1 : 40) as eluents to obtain a six-branched azo chromophore. Its synthetic reaction formula is:

(6) Dissolve 1 mole of hexadendritic azo chromophore and 8 moles of isocyanatopropyltriethoxysilane in 200 mL of tetrahydrofuran, and add 5 mL of dibutyltin dilaurate. After heating to reflux for 72 hours, the reaction solution was poured into n-hexane, and the precipitate was filtered to obtain hexabranch azosiloxane dye. Its synthetic reaction formula is:

The molecular weight of the hexadendritic azosiloxane dye prepared in this example is as high as 4751.46, and its active nonlinear optical chromophore content reaches 78.39 wt.%. Preparation of Inorganic-Organic Hybrid Nonlinear Optical Materials by Sol-Gel Reaction.

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.