CN103013532A - Azobenzene photochromic liquid crystal compound and method for synthesizing same - Google Patents

Azobenzene photochromic liquid crystal compound and method for synthesizing same Download PDF

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CN103013532A
CN103013532A CN 201210512555 CN201210512555A CN103013532A CN 103013532 A CN103013532 A CN 103013532A CN 201210512555 CN201210512555 CN 201210512555 CN 201210512555 A CN201210512555 A CN 201210512555A CN 103013532 A CN103013532 A CN 103013532A
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compound
formula
crystal
photochromic
liquid
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陈思
王旭
周云
方晶
张孟欢
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浙江工业大学
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Abstract

The invention discloses an azobenzene photochromic liquid crystal compound and a method for synthesizing the same. The azobenzene photochromic liquid crystal compound has the following structural formula (I). The method comprises the following steps: (1) carrying out a reaction on a compound of formula (II) and a compound of formula (III) to generate a compound of formula (IV); (2) carrying out a reaction on the compound of formula (IV) and propionyl chloride of formula (V) to generate a compound of formula (VI); and (3) carrying out a reaction on the compound of formula (VI) and a nitro-reduction reaction in presence of a reducing agent which is Zn/AlCl3.6H2O by taking acetone or tetrahydrofuran and water as reaction solvents to finally generate the azobenzene photochromic liquid crystal compound of formula (I). The azobenzene photochromic liquid crystal compound of formula (I) can respond to the pH value and the light and can be applied to the fields of photovoltaic devices, recording and storing mediums and holography.

Description

偶氮苯光致变色液晶化合物及其合成方法 The photochromic azobenzene liquid crystal compounds and synthetic methods

(-)技术领域 (-) FIELD

[0001] 本发明涉及有机合成技术领域,尤其是涉及一种含氨基和碳碳双键的偶氮苯液晶化合物的制备方法和用途。 [0001] The present invention relates to the field of organic synthesis techniques, in particular to preparation and use of azobenzene liquid crystal compound containing an amino group and a carbon-carbon double bond.

(二)背景技术 (B) Background Art

[0002] 光致变色液晶化合物同时具有光致变色性能和液晶性已成为信息储存领域研究的热点。 [0002] The photochromic liquid crystal compound having both hot and photochromic properties of the liquid crystal has become a research in the field of information storage. 偶氮苯类液晶由于具有独特的光致顺反异构特性是近几年来最引人关注的光致变色液晶材料,具有良好的光学性能、热稳定性、溶解性等优点。 Azobenzene liquid crystal because of the unique characteristics of the anti-photo-cis isomer is a photochromic liquid crystal material having good optical properties, thermal stability, solubility, etc. In recent years, most attention. 偶氮苯化合物在光作用下会发生可逆的顺反异构,这一特性使其在光储存、光全息技术及光信息处理等许多方面具有巨大的潜在应用性。 Azobenzene compound reversible cis-trans isomerization occurs under the action of light, so the characteristic in optical storage, many aspects of holographic optical information processing technology and has great potential use.

(三)发明内容 (Iii) Disclosure of the Invention

[0003] 本发明的第一个目的是提供一种新型的对pH值和光双重响应的偶氮苯光致变色液晶化合物。 [0003] A first object of the present invention is to provide a novel pH-azobenzene and dual light response of the photochromic liquid crystal compound.

[0004] 本发明的第二个目的是提供一种合成上述偶氮苯光致变色液晶化合物的方法。 [0004] A second object of the present invention is to provide a method of synthesis of the photochromic azobenzene liquid crystal compound.

[0005] 为实现上述发明目的,本发明采用采用如下技术方案: [0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] 本发明提供了一种偶氮苯光致变色液晶化合物,其结构如式(I)所示: [0006] The present invention provides a compound of photochromic azobenzene liquid crystal structure as shown in formula (I):

[0007] [0007]

Figure CN103013532AD00041

[0008] 其中,R为卤素。 [0008] wherein, R is halogen.

[0009] 作为优选,R为Cl、Br或I。 [0009] Advantageously, R is Cl, Br or I.

[0010] 本发明还提供了一种所述的偶氮苯光致变色液晶化合物的合成方法,包括如下步骤: [0010] The present invention further provides a method of synthesizing one of the azobenzene photochromic liquid crystal compound, comprising the steps of:

[0011] ( I)以吡啶作为反应溶剂和缚酸剂,在冰水浴中,式(II)所示的镁试剂和式(ill)所示的对卤代甲基苯甲酰氯发生酰氯反应生成式(IV)所示的4-硝基-2' -羟基-4' -对卤 [0011] generation (I) in a reaction solvent and pyridine as acid-binding agent, in an ice-water bath, of formula (II) and magnesium reagents represented by the formula (ILL) reacting the acid chloride of FIG halomethyl chloride formula (IV) represented by 4-nitro-2 '- hydroxy-4' - halide

代甲基苯甲酰氧基偶氮苯; Generation methylbenzoyloxy azobenzene;

[0012] [0012]

Figure CN103013532AD00051

[0013] (2)以无水四氢呋喃作为反应溶剂、三乙胺为缚酸剂,4-硝基-2' -羟基-4' -对卤代甲基苯甲酰氧基偶氮苯与式(V)所示的丙烯酰氯在冰水浴中发生酰氯反应生成式(VI)所示的4-硝基_2' -丙烯酰氧基-4' -对卤代甲基苯甲酰氧基偶氮苯; [0013] (2) in anhydrous tetrahydrofuran as a reaction solvent, triethylamine as acid binding agent, 4-nitro-2 '- hydroxy - 4' - azobenzene halomethyl benzoyloxy of formula (V) acryloyl chloride as shown in place in an ice water bath reacting the acid chloride of formula (VI) represented by 4-nitro _2 '- acryloyloxy-4' - coupling of a halogenated oxy-methylbenzoyl pyridazines;

[0014] [0014]

Figure CN103013532AD00052

[0015] (3)以丙酮或四氢呋喃和水为反应溶剂,4-硝基-2' -丙烯酰氧基-4' -对卤代甲基苯甲酰氧基偶氮苯在还原剂ZnAlCl3 • 6H20的作用下从室温逐步升温到60°C进行逐步的硝基还原反应,最终生成式(I)所示的偶氮苯光致变色液晶化合物; [0015] (3) water and tetrahydrofuran or acetone as the reaction solvent, 4-nitro-2 '- acryloyloxy-4' - methylbenzoyl group, a halogenated azobenzene reducing agent ZnAlCl3 • 6H20 under the action gradually heated from room temperature to 60 ° C stepwise reduction of nitro group, the final formula (I) shown azobenzene photochromic liquid crystal compound;

[0016] [0016]

Figure CN103013532AD00053

[0017] 所述步骤(I)中,所述镁试剂(II)与对卤代甲基苯甲酰氯(III)的摩尔比为1:0. 8 〜I。 [0017] The step (I), the magnesium reagent (II) molar ratio of halomethyl chloride (III) is 1:. 0 8 ~I.

[0018] 作为优选,所述步骤(I)具体按照如下进行:将镁试剂(II)溶于吡啶中,在冰水浴条件下以I〜4秒/滴的速度缓慢滴加对卤代甲基苯甲酰氯(III)的吡啶溶液,滴完后酰氯反应结束,加入少量冰块,用稀盐酸中和,析出大量絮状固体,抽滤,滤饼用蒸馏水洗涤、干燥,最后将反应混合物用柱色谱法分离除去未反应的原料以及副产物,即得到产物(IV)。 [0018] Advantageously, said step (I) specifically performed as follows: The magnesium reagents (II) was dissolved in pyridine, under ice-cooling to I~4 seconds / drop slow dropwise addition of halomethyl benzoyl chloride (III) in pyridine solution of the acid chloride dropwise after completion of the reaction, a small amount of ice, neutralized with dilute hydrochloric acid and the precipitated solid was large flocculent, filtered off with suction, the filter cake was washed with distilled water, dried, and finally the reaction mixture was separation by column chromatography to remove unreacted starting material and by-products, i.e., to obtain the product (IV).

[0019] 所述步骤(2)中,4-硝基-2' -羟基-4' -对卤代甲基苯甲酰氧基偶氮苯(IV)与丙烯酰氯、三乙胺的摩尔比为1:5〜10:5〜8。 [0019] The step (2), 4-nitro-2 '- hydroxy - 4' - methylbenzoyl group, a halogenated azobenzene (IV) with acryloyl chloride, triethylamine in a molar ratio of 1: 5 to 10: 5 ~ 8.

[0020] 作为优选,所述步骤(2)具体按照如下进行:将4-硝基-2'-羟基-4'-对卤代甲基苯甲酰氧基偶氮苯(IV)和三乙胺溶于无水四氢呋喃中,在冰水浴下以I〜5秒/滴的速度缓慢滴加丙烯酰氯的四氢呋喃溶液,滴加完毕后于室温下搅拌反应12〜24h,反应结束,将反应混合物旋干,放入真空烘箱中(50°C )烘干,用二氯甲烷溶解,用蒸馏水洗去三乙胺盐,干燥后柱色谱法分离出产物4-硝基-2' -丙烯酰氧基-4' -对氯甲基苯甲酰氧基偶氮苯。 [0020] Advantageously, the step (2) specifically performed as follows: A mixture of 4-nitro-2'-hydroxy-4'-methylbenzoyl group, a halogenated azobenzene (IV) and triethyl amine was dissolved in anhydrous tetrahydrofuran under ice-cooling to I~5 seconds / drop speed was slowly added dropwise a tetrahydrofuran solution of acryloyl chloride was added dropwise. after completing the reaction was stirred at room temperature 12~24h, completion of the reaction, the reaction mixture was spin dry, placed in a vacuum oven (50 ° C) dried, dissolved in methylene chloride, washed with distilled triethylamine salt, drying the product was isolated by column chromatography of 4-nitro-2 '- acryloyloxy -4 '- benzoyloxy chloromethyl azobenzene.

[0021] 所述步骤(3)中,4-硝基-2' -丙烯酰氧基-4' -对卤代甲基苯甲酰氧基偶氮苯:Zn =AlCl3 ·6Η20的摩尔比为1:8〜10 :0. 33〜O. 41,四氢呋喃或丙酮与水的体积比为4〜5:1。 [0021] The step (3), 4-nitro-2 '- acryloyloxy-4' - methylbenzoyl group, a halogenated azobenzene: molar ratio Zn = AlCl3 · 6Η20 is 1: 8~10:.. 0 33~O 41, the volume ratio of acetone and water or tetrahydrofuran for 4 to 5: 1.

[0022] 作为优选,所述的步骤(3)具体按照如下进行:将4-硝基-2'-丙烯酰氧基-4'-对卤代甲基苯甲酰氧基偶氮苯、还原剂和水加入丙酮或四氢呋喃中,先室温反应广3小时,然后升温至40°C反应f1. 5小时,再升温至50°C反应2. 5〜3小时,最后加热到60°C反应2〜2. 5小时,反应结束后,旋干溶剂,放入真空烘箱里烘干,用乙醇重结晶得到产物(I )。 [0022] Advantageously, said step (3) specifically performed as follows: 4-acryloyloxy-4'-nitro-2'-halo-methylbenzoyl group of azobenzene, reduction and water added to acetone or tetrahydrofuran, at room temperature before extensive reaction was 3 hours and then warmed to 40 ° C the reaction f1. 5 hours, the reaction was warmed to 50 ° C 2. 5~3 hours, and finally heated to 60 ° C for 2 ~ 2. 5 hours. after completion of the reaction, rotary evaporation, drying in a vacuum oven to give the product (I) was recrystallized from ethanol.

[0023] 本发明具体推荐所述的合成方法按照如下步骤进行: Synthesis Method [0023] The present invention is particularly recommended according to the following steps:

[0024] (I)将镁试剂溶于吡啶中,在冰水浴条件下以I〜4秒/滴的速度缓慢滴加对卤代甲基苯甲酰氯的吡啶溶液,滴完后酰氯反应结束,经后处理得到式(IV)所示的4-硝基-2' -羟基-4' -对卤代甲基苯甲酰氧基偶氮苯;所述镁试剂与对卤代甲基苯甲酰氯的摩尔比为1:0. 8〜I ; [0024] (I) magnesium reagent dissolved in pyridine, under ice-cooling to I~4 seconds / drop of pyridine was added dropwise slow halogenated methyl benzoyl chloride, acid chloride end of the dropwise addition, obtained after treatment of formula (IV) represented by 4-nitro-2 '- hydroxy - 4' - benzoyloxy of azobenzene halomethyl; and said magnesium agent on haloalkyl methylbenzonitrile the molar ratio of the acid chloride is 1: 0 8~I;.

[0025] (2)将4-硝基-2' -羟基-4' -对卤代甲基苯甲酰氧基偶氮苯和三乙胺溶于无水四氢呋喃中,在冰水浴条件下以I〜5秒/滴的速度滴加丙烯酰氯的四氢呋喃溶液,滴加完毕后于室温下搅拌反应12〜24h,反应结束后经后处理得到式(VI)所示的4-硝基-2' -丙烯酰氧基_4' -对卤代甲基苯甲酰氧基偶氮苯;所述4-硝基-2' -羟基-4' -对卤代甲基苯甲酰氧基偶氮苯与丙烯酰氯、三乙胺的摩尔比为1:5〜10:5〜8 ; [0025] (2) 4-Nitro-2 '- hydroxy - 4' - methylbenzoyl group, a halogenated azobenzene and triethylamine were dissolved in anhydrous tetrahydrofuran under ice-cooling to tetrahydrofuran I~5 sec / drop rate of acryloyl chloride was added dropwise, with stirring at room temperature after addition was complete the reaction 12~24h, post-treatment after the reaction to give 4-nitro-formula (VI) shown in FIG 2 ' - acryloyloxy _4 '- methylbenzoyl group, a halogenated azobenzene; the 4-nitro-2' - hydroxy - 4 '- azobis a halogenated methylbenzoyloxy benzene with propylene chloride, triethylamine in a molar ratio of 1: 5 to 10: 5 ~ 8;

[0026] (3)将4-硝基-2' -丙烯酰氧基-4' -对卤代甲基苯甲酰氧基偶氮苯、还原剂和水加入丙酮或四氢呋喃中,先室温反应广3小时,然后升温至40°C反应f1. 5小时,再升温至50°C反应2. 5^3小时,最后升温至60°C反应2〜2. 5小时,经分离纯化得到式(I)所示的偶氮苯光致变色液晶化合物;所述4-硝基-2' -丙烯酰氧基-4' -对卤代甲基苯甲酰氧基偶氮苯:Zn =AlCl3 · 6H20的摩尔比为1:8〜10 :0. 33〜O. 41,四氢呋喃或丙酮与水的体积比为4 〜5:1 ο [0026] (3) 4-Nitro-2 '- acryloyloxy-4' - halomethyl benzoyloxy of azobenzene, reducing agent and water were added to acetone or tetrahydrofuran, at room temperature before the reaction Canton 3 hours, then the reaction was warmed to 40 ° C F1 5 hours, the reaction was warmed to 50 ° C 2.5 ^ 3 hours and finally the reaction was warmed to 60 ° C 2~2. 5 hours, was purified by formula ( I) shown azobenzene photochromic liquid crystal compound; the 4-nitro-2 '- acryloyloxy-4' - azobenzene group of halo methylbenzoyl: Zn = AlCl3 · 6H20 molar ratio is 1: 8~10:.. 0 33~O 41, the volume ratio of acetone and water or tetrahydrofuran for 4 ~5: 1 ο

[0027] 本发明的有益效果在于:本发明所述的含碳碳双键的偶氮苯光致变色液晶化合物是典型的光致异构功能单体,其具有良好的化学稳定性和容易与其他共聚单体聚合的优点。 [0027] Advantageous effects of the present invention is: azobenzene a carbon carbon double bond in the present invention, the photochromic liquid crystal compound is photoisomerization of typical functional monomers, which has good chemical stability and ease of other advantages of the co-monomers are polymerized. 碳碳双键提供的可聚合位点,可通过聚合或接枝到高分子主链得到新型的腰接侧链型液晶高分子或液晶弹性体为后期研究提供可能。 Carbon double bond polymerization sites may be provided, may be obtained by polymerization or waist novel grafted to the polymer main chain type liquid crystal polymer or a side chain connected to the liquid crystal elastomer may be provided Anaphase. 此外化合物中所含的氨基可对外部环境的pH值产生响应。 Further amino compound contained in the pH value may be generated in response to the external environment. 因此,本发明的化合物(I)实现了对pH值和光的双重响应,可用于光电器件,记录存储介质和全息照相等领域,将发展成为一类具有广泛用途的新型的先进功能材料。 Thus, compound (I) of the present invention achieves the dual pH and response to light, can be used for optoelectronic devices, holographic storage medium, and recording fields, to develop into a new class of advanced functional materials having a wide range of applications.

(四)具体实施方式 (IV) DETAILED DESCRIPTION

[0028] 下面以具体实施例对本发明的技术方案做进一步说明,但本发明的保护范围不限于此: [0028] In the following specific examples further illustrate the technical solutions of the present invention, but the scope of the present invention is not limited thereto:

[0029] 实施例1 : [0029] Example 1:

[0030] I)称取镁试剂5. 18g (O. 02mol)溶于IOOml吡啶,加入到250ml三口烧瓶中,称取对氯甲基苯甲酰氯3. 024g (O. 016mol)溶于IOOml吡啶,加入到恒压漏斗中,滴加速度为I秒/滴,反应过程始终保持冰水浴。 [0030] I) weighed magnesium reagents 5. 18g (O. 02mol) was dissolved in pyridine IOOml added to a 250ml three-neck flask, weighed chloromethyl benzoyl chloride 3. 024g (O. 016mol) was dissolved in pyridine IOOml , was added to the constant pressure funnel, dropping of second I / dropping, the reaction procedure remains ice-water bath. 滴完后反应结束,加入少量冰块,用5%的稀盐酸500ml中和,析出大量絮状固体,抽滤,滤饼用蒸馏水洗4遍,放入真空烘箱中(50°C )烘干。 After the dropping end of the reaction, a small amount of ice was added, washed with 5% dilute hydrochloric acid and 500ml, large flocculent solid precipitated, filtered off with suction, the filter cake washed 4 times with distilled water, placed in a vacuum oven (50 ° C) Drying . 将反应混合物用柱色谱法(硅胶柱)除去未反应的原料,展开剂为二氯甲烷:正己烷(体积比)4:1,可得到产物4-硝基-2' -羟基-4' -对氯甲基苯甲酰氧基偶氮苯1. 6g,产率为24. 3%。 The reaction mixture starting material by column chromatography (silica gel) to remove unreacted, eluent, methylene chloride: hexane (volume ratio) of 4: 1, the product obtained 4-nitro-2 '- hydroxy-4' - chloromethyl-benzoyloxy-azobenzene 1. 6g, 24.3% yield.

[0031] 2)称取0.41g (0. OOlmol) 4-硝基-2'-羟基-4'-对氯甲基苯甲酰氧基偶氮苯和0. 51g (0. 005mol)三乙胺溶于15ml四氢呋喃(THF)中,加入到IOOml的三口烧瓶中,再称取0. 45g (0. 005mol)丙稀酰氯溶于IOml四氢呋喃,加入到恒压漏斗中,滴加速度为I秒/滴,滴加过程中为冰水浴,滴加结束后常温下搅拌反应24h。 [0031] 2) Weigh 0.41g (0. OOlmol) 4- nitro-2'-hydroxy -4'- (0. 005mol) of chloro triethyl methylbenzoyloxy azobenzene and 0. 51g amine was dissolved in 15ml of tetrahydrofuran (THF) was added to a three-necked flask IOOml, and then weighed 0. 45g (0. 005mol) IOml acrylic acid chloride was dissolved in tetrahydrofuran, is added to the constant pressure funnel, dropping of second I / dropwise, to an ice water bath during the addition, the reaction was stirred for 24h at room temperature after completion of the dropwise addition. 反应结束,将反应混合物旋干,放入真空烘箱中(50°C)烘干。 End of the reaction, the reaction mixture by rotary evaporation, in a vacuum oven (50 ° C) drying. 用适量的二氯甲烷溶解,用蒸馏水洗去三乙胺盐,干燥后柱色谱法分离出产物4-硝基-2' -丙烯酰氧基_4' -对氯甲基苯甲酰氧基偶氮苯,展开剂为二氯甲烷:正己烷(体积比)4:1,烘干得到产物0. 27g,产率为59. 0%。 An appropriate amount of dichloromethane and washed with distilled triethylamine salt, drying the product was isolated by column chromatography of 4-nitro-2 '- acryloyloxy _4' - chlorobenzoyl methylbenzoyloxy azobenzene, eluent, methylene chloride: hexane (volume ratio) of 4: 1, and drying the product obtained 0. 27g, yield 59.0%.

[0032] 3)称取0. 39g 4-硝基_2' -丙烯酰氧基_4' -对氯甲基苯甲酰氧基偶氮苯、0. 45g锌粉、0. 064g AlCl3 • 6H20溶于IOml四氢呋喃中,再量取2. 5ml蒸馏水,加入到IOOml的单口烧瓶中,接上回流管。 [0032] 3) Weigh 0. 39g 4- nitro _2 '- acryloyloxy _4' -. Chloromethyl-benzoyloxy-azobenzene, 0 45g zinc, 0 064g AlCl3 • IOml 6H20 was dissolved in tetrahydrofuran, 2. 5ml distilled water was weighed and then added to a single neck flask IOOml, a return conduit connected. 先室温下搅拌反应lh,然后升温至40°C反应lh,再升温至50°C反应3h,最后升温至60°C反应2. 5h。 The reaction was stirred to room temperature lh, and then warmed to 40 ° C the reaction lh, and then the reaction was warmed to 50 ° C 3h, and finally the reaction was warmed to 60 ° C 2. 5h. 反应结束后,旋干溶剂,放入真空烘箱里烘干,最后用乙醇重结晶得到产物4-氨基_2' -丙烯酰氧基-4' -对氯甲基苯甲酰氧基偶氮苯。 After completion of the reaction, rotary evaporation, drying in a vacuum oven, to give the final product was recrystallized from ethanol with 4-amino-_2 '- acryloyloxy-4' - chloro-methylbenzoyl group of azobenzene .

[0033] 实施例2 [0033] Example 2

[0034] I)称取镁试剂2. 59g (0. Olmol)溶于60ml吡啶,加入到250ml三口烧瓶中,称取1. 89g (0. Olmol)对氯甲基苯甲酰氯溶于60ml吡啶于IOOml恒压漏斗中,控制滴速为3秒/滴,反应温度为0°C冰水浴。 [0034] I) weighed magnesium reagent 2. 59g (0. Olmol) was dissolved in 60ml pyridine was added to a 250ml three-neck flask, weighed 1. 89g (0. Olmol) p-chlorobenzoyl chloride in 60ml of pyridine Methyl IOOml at constant pressure funnel, controlled drip rate of 3 sec / drop, the reaction temperature of 0 ° C ice water bath. 滴完反应结束,加入少量冰块,用7%的稀盐酸250ml中和,析出大量絮状固体,抽滤,滤饼用蒸馏水洗五遍,放入真空烘箱中(50°C)烘干。 After completion of the reaction dropping, adding a small amount of ice, diluted with 250ml of 7% hydrochloric acid and the precipitated solid was large flocculent, filtered off with suction, the filter cake was washed five times with distilled water, placed in a vacuum oven (50 ° C) drying. 将反应混合物用柱色谱法除去副产物,展开剂为二氯甲烷,可得到产物4-硝基-2' -羟基-4' -对氯甲基苯甲酰氧基偶氮苯1. 35g,产率为32. 8%。 The reaction mixture was purified by column chromatography to remove by-products, eluent, methylene chloride, the product obtained 4-nitro-2 '- hydroxy - 4' - chloro-methylbenzoyl group of azobenzene 1. 35g, The yield was 32.8%.

[0035] 2)称取0. 33g (0. 0008mol)4-硝基_2' -羟基_4' -对氯甲基苯甲酰氧基偶氮苯和0. 65g (0. 0064mol)三乙胺溶于15ml四氢呋喃(THF)中,加入到IOOml的三口烧瓶中,再称取0. 72g (0. 008mol)丙稀酰氯溶于30ml四氢呋喃,加入到50ml恒压漏斗中,控制滴速为3秒/滴,滴加过程温度为0°C冰水浴,滴加结束后常温下搅拌反应12h。 [0035] 2) Weigh 0. 33g (0. 0008mol) 4- nitro _2 '- hydroxy _4' - chloromethyl benzoyloxy azobenzene and 0. 65g (0. 0064mol) three triethylamine were dissolved in 15ml of tetrahydrofuran (THF) was added to a three-necked flask IOOml, and then weighed 0. 72g (0. 008mol) acrylic acid chloride was dissolved in 30ml of tetrahydrofuran, 50ml was added to the constant pressure funnel, is controlled drip rate 3 seconds / drops, the temperature during the dropwise addition of 0 ° C ice bath, the reaction was stirred for 12h at room temperature after completion of the dropwise addition. 反应结束后,加大量的四氢呋喃,析出三乙胺盐,过滤得滤液,再加大量的水,析出红色絮状固体,过滤,将红色固体烘干即所要的产物4-硝基-2' -丙烯酰氧基-4' -对氯甲基苯甲酰氧基偶氮苯0. 26g,产率为70. 2%。 After completion of the reaction, a large amount of tetrahydrofuran to precipitate triethylamine salt, filtering to obtain filtrate, together with a large amount of water, flocculent precipitate a red solid which was filtered, dried red solid was the desired product i.e. 4-nitro-2 '- acryloyloxy-4 '- chlorobenzoyl methylbenzoyloxy azobenzene 0. 26g, yield 70.2%.

[0036] 3)称取0.72g 4-硝基-2'-丙烯酰氧基-4'-对氯甲基苯甲酰氧基偶氮苯、0.8Ig锌粉、0. 123g AlCl3 • 6H20溶于20ml丙酮中,再量取5ml蒸馏水,加入到IOOml的单口烧瓶中,接上回流管。 [0036] 3) Weigh 0.72g 4- acryloyloxy-nitro-2'-chloro-4'-methylbenzoyl group of azobenzene, 0.8Ig zinc, 0. 123g AlCl3 • 6H20 dissolved in 20ml of acetone, and then measuring 5ml distilled water was added to a one-necked flask IOOml, a return conduit connected. 先室温下搅拌反应2h,然后升温至40°C反应lh,再升温至50°C反应3h,最后升温至60°C反应2h。 The reaction was stirred at room temperature to 2h, then the reaction was warmed to 40 ° C lh, and then the reaction was warmed to 50 ° C 3h, and finally the reaction was warmed to 60 ° C 2h. 反应结束后,旋干溶剂,放入真空烘箱里烘干,最后用乙醇重结晶得到产物4-氨基_2' -丙烯酰氧基-4' -对氯甲基苯甲酰氧基偶氮苯。 After completion of the reaction, rotary evaporation, drying in a vacuum oven, to give the final product was recrystallized from ethanol with 4-amino-_2 '- acryloyloxy-4' - chloro-methylbenzoyl group of azobenzene .

[0037] 实例I和实例2产物结构式为: [0037] Example I Example 2 and the product of the formula:

[0038] [0038]

Figure CN103013532AD00071

[0039] 通过IH NMR方法对所合成的化合物进行表征,以确认结构。 [0039] The synthesized compounds were characterized by IH NMR method to confirm the structure. [0040] IHNMR (核磁共振氢谱) [0040] IHNMR (H NMR)

[0041] [0041]

Figure CN103013532AD00081

[0042]质子1: δ =6. 71X10-6,2H [0042] Proton 1: δ = 6 71X10-6,2H.

[0043]质子 2 : δ =7. 81Χ 10-6, 2Η [0043] Proton 2: δ = 7 81Χ 10-6, 2Η.

[0044]质子 3: δ =7. 97 X 10-6, IH [0044] Proton 3: δ = 7 97 X 10-6, IH.

[0045]质子 4 : δ =7. 34 X 10-6, 2Η [0045] Proton 4: δ = 7 34 X 10-6, 2Η.

[0046]质子 5 : δ =7. 94Χ 10-6, 2Η [0046] Proton 5: δ = 7 94Χ 10-6, 2Η.

[0047]质子 6 : δ =7. 58 X 10-6, 2Η [0047] Proton 6: δ = 7 58 X 10-6, 2Η.

[0048]质子 7 : δ =4. 68Χ 10-6, 2Η [0048] Proton 7: δ = 4 68Χ 10-6, 2Η.

[0049]质子 8 : δ =6. 73Χ 10-6, IH [0049] Proton 8: δ = 6 73Χ 10-6, IH.

[0050]质子 9 : δ =6. 46Χ 10-6, IH [0050] Proton 9: δ = 6 46Χ 10-6, IH.

[0051]质子 10 : δ =6. 12X10-6,IH [0051] Proton 10: δ = 6 12X10-6, IH.

[0052]质子 11 : δ =5. 1X10-6,2Η [0052] Proton 11: δ = 5 1X10-6,2Η.

[0053] 由此确认所合成的化合物结构与预期一致。 [0053] The same compounds synthesized thereby confirm the expected structure.

Claims (10)

  1. 1. 一种偶氮苯光致变色液晶化合物,其结构如式(I)所示: A photochromic azobenzene liquid crystal compound, which structural formula (I) below:
    Figure CN103013532AC00021
    其中,R为卤素。 Wherein, R is halogen.
  2. 2.如权利要求1所述的偶氮苯光致变色液晶化合物,其特征在于:R为Cl、Br或I。 2. azobenzene according to claim 1 photochromic liquid crystal compound, wherein: R is Cl, Br or I.
  3. 3. —种如权利要求1所述的偶氮苯光致变色液晶化合物的合成方法,包括如下步骤: (1)以吡啶作为反应溶剂和缚酸剂,在冰水浴中,式(II)所示的镁试剂和式(III)所示的对卤代甲基苯甲酰氯发生酰氯反应生成式(IV)所示的4-硝基-2,-羟基-4' -对卤代甲基苯甲酰氧基偶氮苯; 3. - The kind of azobenzene according to claim 1 synthesis of cholesteric liquid crystal photochromic compound, comprising the steps of: by (1) in a reaction solvent and pyridine as acid-binding agent, in an ice-water bath, of formula (II) and magnesium reagents of formula (III) shown in FIG methylbenzoyl chloride in a halogenated occurs chloride to form the formula (IV) 4-nitro-2 - hydroxy-4 '- halomethyl benzene formyloxy azobenzene;
    Figure CN103013532AC00022
    (2)以无水四氢呋喃和水作为反应溶剂、三乙胺为缚酸剂,4-硝基-2' -羟基-4' -对卤代甲基苯甲酰氧基偶氮苯与式(V)所示的丙烯酰氯在冰水浴中发生酰氯反应生成式(VI)所示的4-硝基_2' -丙烯酰氧基-4' -对卤代甲基苯甲酰氧基偶氮苯; (2) in anhydrous tetrahydrofuran and water as the reaction solvent, triethylamine as acid binding agent, 4-nitro-2 '- hydroxy - 4' - methylbenzoyl group, a halogenated azobenzene formula ( V shown) acryloyl chloride occurs in an ice chloride of formula (VI) represented by 4-nitro _2 '- acryloyloxy-4' - azobis benzoyloxy of halomethyl benzene;
    Figure CN103013532AC00023
    (3)以丙酮或四氢呋喃为反应溶剂,4-硝基-2' -丙烯酰氧基-4' -对卤代甲基苯甲酰氧基偶氮苯在还原剂Zn/AlC13 · 6H20的作用下从室温逐步升温到60°C进行逐步的硝基还原反应,最终生成式(I)所示的偶氮苯光致变色液晶化合物; (3) in acetone or tetrahydrofuran as the reaction solvent, 4-nitro-2 '- acryloyloxy-4' - halomethyl-benzoyloxy-effect reducing agent azobenzene Zn / AlC13 · 6H20 in under gradually heated from room temperature to 60 ° C stepwise reduction of nitro group, the final formula (I) shown azobenzene photochromic liquid crystal compound;
    Figure CN103013532AC00024
  4. 4.如权利要求3所述的偶氮苯光致变色液晶化合物的合成方法,其特征在于:所述镁试剂与对卤代甲基苯甲酰氯的摩尔比为1:0. 8〜I。 4. azobenzene according to claim 3 synthesis of liquid crystal compounds photoinduced discoloration, wherein: the molar ratio of magnesium reagents halogenated methyl benzoyl chloride is 1:. 0 8~I.
  5. 5.如权利要求4所述的偶氮苯光致变色液晶化合物的合成方法,其特征在于所述步骤(1)具体按照如下进行:将镁试剂溶于吡啶中,在冰水浴条件下以I〜4秒/滴的速度缓慢滴加对卤代甲基苯甲酰氯的吡啶溶液,滴完后酰氯反应结束,经后处理得到式(IV)所示的4-硝基-2,-羟基-4' -对卤代甲基苯甲酰氧基偶氮苯。 5. azobenzene claim 4, wherein the liquid crystal compound synthesis photoinduced discoloration, wherein said step (1) specifically performed as follows: The magnesium reagents dissolved in pyridine, under ice-cooling to I s ~ 4 drops speed / pyridine solution was slowly added dropwise to the halo-methylbenzoyl chloride, and after the end of dropwise chloride there was obtained after treatment of formula (IV) shown in FIG 4-nitro-2 - hydroxy - 4 '- benzoyloxy halomethyl on azobenzene.
  6. 6.如权利要求3所述的偶氮苯光致变色液晶化合物的合成方法,其特征在于:所述4-硝基-2'-羟基-4'-对卤代甲基苯甲酰氧基偶氮苯与丙烯酰氯、三乙胺的摩尔比为1:5 〜10:5 〜8。 6. azobenzene according to claim 3 cholesteric liquid crystal compound synthesis photoluminescence, characterized in that: said pair of 4-nitro-2'-hydroxy-4'-halomethyl-benzoyloxy- azobenzene with acryloyl chloride, triethylamine in a molar ratio of 1: 5 ~ 10: 5 ~ 8.
  7. 7.如权利要求6所述的偶氮苯光致变色液晶化合物的合成方法,其特征在于所述步骤(2)具体按照如下进行:将4-硝基-2' -羟基-4' -对卤代甲基苯甲酰氧基偶氮苯和三乙胺溶于无水四氢呋喃中,在冰水浴条件下以I〜5秒/滴的速度滴加丙烯酰氯的四氢呋喃溶液,滴加完毕后于室温下搅拌反应12〜24h,反应结束后经后处理得到式(VI)所示的4-硝基-2' -丙烯酰氧基-4' -对卤代甲基苯甲酰氧基偶氮苯。 7. azobenzene according to claim 6 synthesis of photochromic liquid crystal compound, wherein said step (2) specifically performed as follows: 4-Nitro-2 '- hydroxy-4' - of tetrahydrofuran halomethyl-benzoyloxy-azobenzene and triethylamine were dissolved in dry tetrahydrofuran to I~5 seconds / drop rate of acrylic acid chloride was added dropwise under ice-cooling, and after the addition was complete the reaction was stirred at room temperature 12~24h, post-treatment after the reaction of formula (VI) represented by 4-nitro-2 '- acryloyloxy-4' - azobis benzoyloxy of halomethyl benzene.
  8. 8.如权利要求3所述的偶氮苯光致变色液晶化合物的合成方法,其特征在于所述4-硝基-2' -丙烯酰氧基-4' -对卤代甲基苯甲酰氧基偶氮苯:Zn =AlCl3 · 6H20的摩尔比为1:8〜10 :0. 33〜O. 41,四氢呋喃或丙酮与水的体积比为4〜5:1。 8. azobenzene according to claim 3 cholesteric liquid crystal compound synthesis photoluminescence, characterized in that said 4-nitro-2 '- acryloyloxy-4' - benzoyl halomethyl on azobenzene group: Zn = AlCl3 · 6H20 molar ratio of 1: 8~10:.. 0 33~O 41, the volume ratio of acetone and water or tetrahydrofuran for 4 to 5: 1.
  9. 9.如权利要求8所述的偶氮苯光致变色液晶化合物的合成方法,其特征在于所述的步骤(3)具体按照如下进行:将4-硝基-2' -丙烯酰氧基_4' -对卤代甲基苯甲酰氧基偶氮苯、还原剂和水加入丙酮或四氢呋喃中,先室温反应f 3小时,然后升温至40°C反应f1. 5小时,再升温至50°C反应2. 5^3小时,再升温至60°C反应2〜2. 5小时,最后经分离纯化得到式(I)所示的偶氮苯光致变色液晶化合物。 Azobenzene as claimed in claim 8, the photo-synthesis of cholesteric liquid crystal compound, wherein the step (3) according to the specific follows: 4-Nitro-2 '- _ acryloyloxy 4 '- halomethyl benzoyloxy of azobenzene, a reducing agent and water were added tetrahydrofuran or acetone, to the reaction at room temperature f 3 hours and then warmed to 40 ° C the reaction f1 5 hours, warmed to 50. reaction ^ 2.5 ° C for 3 hours, the reaction was warmed to 60 ° C 2~2 5 hours and finally isolated and purified by formula (I) shown azobenzene photochromic liquid crystal compound.
  10. 10.如权利要求3所述的偶氮苯光致变色液晶化合物的合成方法,其特征在于所述的合成方法具体按照如下步骤进行: (I)将镁试剂溶于吡啶中,在冰水浴条件下以I〜4秒/滴的速度缓慢滴加对卤代甲基苯甲酰氯的吡啶溶液,滴完后酰氯反应结束,经后处理得到式(IV)所示的4-硝基-2' -羟基-4'-对卤代甲基苯甲酰氧基偶氮苯;所述镁试剂与对卤代甲基苯甲酰氯的摩尔比为1:0. 8 〜I ; (2 )将4-硝基-2' -羟基-4' -对卤代甲基苯甲酰氧基偶氮苯和三乙胺溶于无水四氢呋喃中,在冰水浴条件下以I〜5秒/滴的速度滴加丙烯酰氯的四氢呋喃溶液,滴加完毕后于室温下搅拌反应12〜24h,反应结束后经后处理得到式(VI)所示的4-硝基-2' -丙烯酰氧基_4' -对卤代甲基苯甲酰氧基偶氮苯;所述4-硝基-2' -羟基-4' -对卤代甲基苯甲酰氧基偶氮苯与丙烯酰氯、三乙胺的摩尔比为1:5〜10:5〜8 ; (3) In an ice conditions (I) was dissolved in pyridine magnesium reagent in: azobenzene 10. The method of claim 3 Synthesis of cholesteric liquid crystal photochromic compound, characterized in that the particular method of synthesis performed according to the following steps in the second I~4 / slow drop of pyridine was added dropwise benzoyl chloride halomethyl, end chloride dropwise addition, to give after treatment of formula (IV) 4- shown nitro-2 ' - 4'-hydroxy-benzoyloxy of azobenzene halomethyl; the molar ratio of magnesium reagent halogenated methyl benzoyl chloride is 1: 0 8 ~I; (2) the 4. - nitro - 2 '- hydroxy - 4' - methylbenzoyl group, a halogenated azobenzene and triethylamine were dissolved in anhydrous tetrahydrofuran under ice-cooling to I~5 seconds / drop rate of tetrahydrofuran was added dropwise acryloyl chloride was added dropwise with stirring at room temperature after completion of the reaction 12~24h, post-treatment after the reaction to give 4-nitro-formula (VI) shown -2 '- acryloyloxy _4' - benzoyloxy of azobenzene halomethyl; the 4-nitro-2 '- hydroxy - 4' - methylbenzoyl group, a halogenated azobenzene with acryloyl chloride, triethylamine molar ratio of 1: 5 to 10: 5 ~ 8; (3) 4-硝基_2'_丙烯酰氧基_4'_对卤代甲基苯甲酰氧基偶氮苯、还原剂和水加入丙酮或四氢呋喃中,先室温反应广3小时,然后升温至40°C反应f1. 5小时,再升温至50°C反应2. 5^3小时,再升温至60°C反应2〜2. 5小时,最后经分离纯化得到式(I)所示的偶氮苯光致变色液晶化合物;所述4-硝基_2'_丙烯酰氧基_4'_对齒代甲基苯甲酰氧基偶氮苯:Zn =AlCl3 ·6Η20的摩尔比为1:8〜10 :0. 33〜O. 41,四氢呋喃或丙酮与水的体积比为4〜5:1。 4-nitro _2'_ acryloyloxy _4'_ of halomethyl-benzoyloxy-azobenzene, reducing agent and water were added to acetone or tetrahydrofuran, at room temperature before extensive reaction was 3 hours and then allowed to warm to 40 ° C the reaction F1 5 hours, the reaction was warmed to 50 ° C 2.5 ^ 3 hours, the reaction was warmed to 60 ° C 2~2 5 hours and finally was purified by formula (I), coupling pyridazines photochromic liquid crystal compound; the 4-nitro group _2'_ acryloxy _4'_ azobenzene tooth substituting methylbenzoyl: molar ratio Zn = AlCl3 · 6Η20 is 1 : 8~10:.. 0 33~O 41, the volume ratio of acetone and water or tetrahydrofuran for 4 to 5: 1.
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CN104031652A (en) * 2014-06-25 2014-09-10 北京大学 Iodine bond liquid crystal with reversible photoinduced phase transition behavior and preparation method thereof
CN106432567A (en) * 2016-09-14 2017-02-22 天津大学 Preparation method of polymer heat-storage material containing both-branch Azobenzene side groups

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