CN105175431A - 一种双官能团光致变色化合物、合成及其应用 - Google Patents
一种双官能团光致变色化合物、合成及其应用 Download PDFInfo
- Publication number
- CN105175431A CN105175431A CN201510694968.3A CN201510694968A CN105175431A CN 105175431 A CN105175431 A CN 105175431A CN 201510694968 A CN201510694968 A CN 201510694968A CN 105175431 A CN105175431 A CN 105175431A
- Authority
- CN
- China
- Prior art keywords
- compound
- photochromic
- oxazine
- application
- spiral shell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 55
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 title abstract description 15
- 238000003786 synthesis reaction Methods 0.000 title abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 21
- 150000001988 diarylethenes Chemical class 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- 125000003387 indolinyl group Chemical class N1(CCC2=CC=CC=C12)* 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 40
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- 125000000524 functional group Chemical group 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000011232 storage material Substances 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 101100391174 Dictyostelium discoideum forC gene Proteins 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- -1 process easy Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JSMMZMYGEVUURX-UHFFFAOYSA-N 2-chloro-5-methylthiophene Chemical compound CC1=CC=C(Cl)S1 JSMMZMYGEVUURX-UHFFFAOYSA-N 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000007149 pericyclic reaction Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YBMDPYAEZDJWNY-UHFFFAOYSA-N 1,2,3,3,4,4,5,5-octafluorocyclopentene Chemical compound FC1=C(F)C(F)(F)C(F)(F)C1(F)F YBMDPYAEZDJWNY-UHFFFAOYSA-N 0.000 description 2
- GWQOOADXMVQEFT-UHFFFAOYSA-N 2,5-dimethyl thiophene Natural products CC1=CC=C(C)S1 GWQOOADXMVQEFT-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000004893 oxazines Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- NDEQNPKLYRVIQI-UHFFFAOYSA-N CC1(C)c2ccccc2N(C)C11OC(c2c(C)[o]c(C)c2)=C(c2c(C)[o]c(C)c2)N=C1 Chemical compound CC1(C)c2ccccc2N(C)C11OC(c2c(C)[o]c(C)c2)=C(c2c(C)[o]c(C)c2)N=C1 NDEQNPKLYRVIQI-UHFFFAOYSA-N 0.000 description 1
- ZTUKGBOUHWYFGC-UHFFFAOYSA-N CC1(C)c2ccccc2N(C)C1=C Chemical compound CC1(C)c2ccccc2N(C)C1=C ZTUKGBOUHWYFGC-UHFFFAOYSA-N 0.000 description 1
- QREUKDJEYYXKMO-YPKPFQOOSA-N Cc1cc(/C(/N=O)=C(\c2c(C)[o]c(C)c2)/O)c(C)[o]1 Chemical compound Cc1cc(/C(/N=O)=C(\c2c(C)[o]c(C)c2)/O)c(C)[o]1 QREUKDJEYYXKMO-YPKPFQOOSA-N 0.000 description 1
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000002910 structure generation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
本发明提供一种双官能团光致变色化合物、合成及其应用。该双官能团光致变色材料含有螺噁嗪与二芳基乙烯两类材料。其典型的制备方法是2-亚硝基,1,2-二芳基乙烯醇与吲哚啉衍生物发生缩合反应得目标化合物。本发明合成的双官能团光致变色化合物具有良好的光致变色响应,此类化合物在光致变色材料以及信息存储方面存在潜在的应用。
Description
技术领域
本发明涉及有机光致变色材料及信息存储领域,尤其涉及一种含有螺噁嗪和二芳基乙烯材料的双官能团光致变色材料。
技术背景
有机光致变色材料是一类具有特殊光化学性质的新型功能材料,在光信息存储、光滤波器、防伪、光致变色涂层等领域均具有广泛的应用前景。尤其是在光的信息存贮领域的应用研究,成为目前科学家研究的焦点。其中,螺噁嗪及二芳基乙烯材料是最有希望达到实用化的有机光致变色材料,由于这两类化合物具有良好的光致变色性能,特别是具有较高的抗疲劳性和成色性,在信息存储方面具有巨大的应用前景和商业价值。
有机光致变色化合物种类繁多,由于具有原料易得、加工简便、化学结构易于修饰的特点,目前已有大量的文献报道,螺噁嗪材料与二芳基乙烯材料是本发明涉及的两类材料。螺噁嗪有很好的光稳定性和抗疲劳性,受到研究者广泛的关注。螺噁嗪的光致变色机理是在紫外光的激发下,分子中的螺C-O键发生异裂,引起分子的结构以及电子的组态发生异构和重排,由螺C原子链接的两个环系由正交变成共平面的部花菁结构,形成一个开环的共轭体系,吸收光谱也随之发生红移,同时也会伴随着颜色的改变。在可见光或热的作用下,部花菁发生关环反应返回到螺噁嗪结构,构成一个典型的光致变色体系。二芳基乙烯化合物具有良好的热稳定性和抗疲劳性,在另一种波长的光源作用下消色。其光致变色机理为周环反应。Irie等人对噻吩取代的二芳基乙烯化合物进行了深入的研究,提出在二芳基乙烯分子中引入环状烯烃可以控制二芳基乙烯的顺反异构。并且在全氟环戊烯桥头二芳烯光致变色化合物的合成、光致变色行为和应用等方面做了大量的研究工作。并指出在二芳基乙烯分子中引入环状烯烃可以控制二芳基乙烯的顺反异构,使光反应效率提高。
在2010年,JACS上报道了一篇关于有机光致变色材料中偶氮苯类化合物的合成,他将其运用到电存储材料中,通过对其电流随着电压变化的改变进行测试,当电流随着电压改变出现两段突变时,这样的材料就可作为三元数据存储材料。2010年Adv.Mater上报道了关于全氟环戊烯桥头二芳烯光致变色化合物,通过测试应用于存储材料中。2014年,JackyChi-HungChan在JACS上报道了关于一类二芳基乙烯材料的合成,他所报道合成的二芳基乙烯有着很好的热稳定和抗疲劳性,在光存储方面存在着潜在的应用。
螺噁嗪与二芳基乙烯材料都是典型的光致变色化合物,有着良好的热稳定性和抗疲劳性,当螺噁嗪与二芳基乙烯化合物链接在一起时,得到一种新型化合物,这样的一类化合物具有多种结构之间的可逆转换,在分子开光,信息存储等方面存在潜在的应用。双官能团光致变色材料在不同光源的激发下具有多种稳定结构,从而在光致变色和电存储材料中存在潜在应用,对于单一的光致变色材料相比,它的转换结构更为丰富,可以实现多位存储器件的应用
本发明中所涉及的这类化合物,是双官能团光致变色化合物,有着较好的稳定性,当用不同波段的光源对其进行激发照射时,化合物会由一种结构转变为另一种结构,并且存在着三种结构之间的转换,当用20W的汞灯对化合物(I)激发时,会导致二芳基乙烯发生周环反应生成化合物(II),这种化合物有望实现三维存储材料的制作。三维存储是最具有希望实现高密度,高性能,低价位存储的存储方式之一。当在溶液中对化合物进行电性能研究时发现其在电存储方面存在潜在的应用。
发明内容
本发明的目的在于提出一种双官能团光致变色化合物、合成及其应用。
本发明首先设计合成以2-亚硝基-1,2-二芳基乙烯醇与吲哚啉衍生物发生缩合反应得到目标化合物。这样的一种化合物是由螺噁嗪与二芳基乙烯化合物构成的双官能团光致变色化合物,在信息存储等方面存在潜在的应用。本发明中目标化合物反应式如下所示:
本发明所涉及的化合物结构式如下:
通式中R1为-CH3,-CH2CH3,-CH2CH2CH3,-CH2OH,-CH3CH2OH,R2,R3为以下基团的任意组合:
附图说明
图1化合物1,3,3-三甲基-5’,6’-二苯基螺[吲哚-2,2’-[1,4]噁嗪]三种不同结构。
图2化合物1,3,3-三甲基-5’,6’-二苯基螺[吲哚-2,2’-[1,4]噁嗪]在20W汞灯激发下的紫外光谱图。
图3化合物1,3,3-三甲基-5’,6’-二苯基螺[吲哚-2,2’-[1,4]噁嗪]在300W汞灯激发下的紫外光谱图。
图4化合物1,3,3-三甲基-5’,6’-二苯基螺[吲哚-2,2’-[1,4]噁嗪]三种不同结构的紫外光谱图。
图5化合物1,3,3-三甲基-5’,6’-二苯基螺[吲哚-2,2’-[1,4]噁嗪]电性能研究。
具体实施方式
以下具体实施例用来进一步说明本发明。
合成实施例
实施例11,3,3-三甲基-5,6-二苯基螺[吲哚-2,2,-[1,4]噁嗪]的合成
反应式:
在无水无氧的条件下,将(180mg,0.8mmol)的1,2-二苯基-2-亚硝基-乙烯醇投入250mL的三口烧瓶中,加入60mL的甲苯使其溶解,待其溶解后,将溶于20mL甲苯中的(138mg,0.8mmol)的1,3,3-三甲基-2-亚甲基-吲哚啉逐滴滴入反应体系中,回流反应。反应结束后降至室温,减压旋蒸除去溶剂。粗产品通过纯化得到80mg黄色固体,熔点为131.5-133.6℃,收率为26.3%。1HNMR(400MHz,CDCl3):δ7.96(d,J=6.8Hz,3H),7.47(t,J=8.4Hz,5H),7.25(t,J=10.2Hz,3H),7.04(t,J=7.2Hz,2H),6.81(d,J=8Hz,1H),6.02(s,1H).13CNMR(400MHz,CDCl3)δ(ppm):186.96,130.80,128.16,127.84,127.45,122.32,121.92,107.53,91.13,48.39,29.79,23.35.Elementalanalysiscalcd.(%)forC26H24N2O:C,82.07;H,6.36;N,7.36.foundC,82.10;H,6.35;N,7.38.
实施例21-乙基,3,3-二甲基-5,6-二苯基螺[吲哚-2,2,-[1,4]噁嗪]的合成
反应式:
在无水无氧的条件下,将(180mg,0.8mmol)的1,2-二苯基-2-亚硝基-乙烯醇投入250mL的三口烧瓶中,加入60mL的甲苯使其溶解,待其溶解后,将溶于20mL甲苯中的(149mg,0.8mmol)的1-乙基,3,3-二甲基-2-亚甲基-吲哚啉逐滴滴入反应体系中,回流反应。反应结束后降至室温,减压旋蒸除去溶剂,粗产品通过柱层析纯化得到75mg深黄色固体,收率为23.8%。Elementalanalysiscalcd.(%)forC27H26N2O:C,82.20;H,6.64;N,7.10.foundC,82.23;H,6.63;N,7.07.
实施31,3,3-三甲基-5,6-双-(2-氯-5-甲基-噻吩)螺[吲哚-2,2,-[1,4]噁嗪]的合成
反应式:
在无水无氧的条件下,将(501mg,1.5mmol)的1,2-双-(2-氯-5-甲基-噻吩)-2-亚硝基-乙烯醇投入250mL的三口烧瓶中,加入60mL的甲苯使其溶解,待其溶解后,将溶于20mL甲苯中的(258mg,1.5mmol)的1,3,3-三甲基-2-亚甲基-吲哚啉逐滴滴入反应体系中,回流反应。反应结束后降至室温,减压旋蒸除去溶剂。粗产品通过纯化得到96mg黄色固体,收率为13.0%.元素分析:Elementalanalysiscalcd.(%)forC24H22Cl2N2OS2:C,58.89;H,4.53;N,5.72.foundC,58.91;H,4.56;N,5.70.
实施例41,3,3-三甲基-5,6-双(2,5-二甲基-噻吩)螺[吲哚-2,2,-[1,4]噁嗪]的合成
反应式:
在无水无氧的条件下,将(440mg,1.5mmol)的1,2-双-(2-氯-5-甲基-噻吩)-2-亚硝基-乙烯醇投入250mL的三口烧瓶中,加入60mL的甲苯使其溶解,待其溶解后,将溶于20mL甲苯中的(258mg,1.5mmol)的1,3,3-三甲基-2-亚甲基-吲哚啉逐滴滴入反应体系中,回流反应。反应结束后降至室温,减压旋蒸除去溶剂。得到的粗产品通过柱层析纯化,得到108mg黄色固体,收率为16.0%。Elementalanalysiscalcd.(%)forC26H28N2OS2:C,69.61;H,6.29;N,6.24.foundC,69.63;H,6.28;N,6.25.
实施例51,3,3-三甲基-5,6-(2,5-二甲基-呋喃)螺[吲哚-2,2,-[1,4]噁嗪]的合成
反应式:
在无水无氧的条件下,将(391mg,1.5mmol)的1,2-二-(2,5-二甲基呋喃)-2-亚硝基-乙烯醇投入250mL的三口烧瓶中,加入60mL的甲苯使其溶解,待其溶解后,将溶于20mL甲苯中的(258mg,1.5mmol)的1,3,3-三甲基-2-亚甲基-吲哚啉逐滴滴入反应体系中,回流反应。反应结束后降至室温,减压旋蒸除去溶剂。得到的粗产品通过柱层析纯化,得到110mg黄色固体,收率为17.6%。Elementalanalysiscalcd.(%)forC26H28N2O3:C,74.97;H,6.78;N,6.73.foundC,74.99;H,6.75;N,6.74.
实施例61,3,3-三甲基1,3,3-三甲基-5’-(2,5-二甲基呋喃),6’-(2,5-二甲基噻吩)螺[吲哚-2,2’-[1,4]噁嗪]螺[吲哚-2,2,-[1,4]噁嗪]的合成
反应式:
在无水无氧的条件下,将(416mg,1.5mmol)的1-(2,5-二甲基呋喃),2-(2,5)-2-亚硝基-乙烯醇投入250mL的三口烧瓶中,加入60mL的甲苯使其溶解,待其溶解后,将溶于20mL甲苯中的(258mg,1.5mmol)的1,3,3-三甲基-2-亚甲基-吲哚啉逐滴滴入反应体系中,回流反应。反应结束后降至室温,减压旋蒸除去溶剂。得到的粗产品通过柱层析纯化,得到93mg黄色固体,收率为14.3%。Elementalanalysiscalcd.(%)forC26H28N2O2S:C,72.19;H,6.52;N,6.48.foundC,72.23;H,6.49;N,6.50.
实施例7化合物1,3,3-三甲基-5’,6’-二苯基螺[吲哚-2,2’-[1,4]噁嗪]在20W汞灯激发下的紫外光谱图。
以二氯甲烷为溶剂,将化合物1,3,3-三甲基-5,,6,-二苯基螺[吲哚-2,2,-[1,4]噁嗪]配成浓度为1×10-5mol/L的溶液。在室温条件下,持续通氮气30分钟后,使用Agilent8453型的紫外可见光光度计,用1cm的石英比色皿,在200-800nm波段进行紫外吸收光谱扫描,测量化合物1,3,3-三甲基-5’,6’-二苯基螺[吲哚-2,2’-[1,4]噁嗪]在二氯甲烷溶液中的最大吸收波长及摩尔吸光系数。化合物在光照前,最大吸收波长在381nm,随着光照时间的延长,在381nm处的最大吸收强度在减小,在315nm和361nm处出现新的吸收峰,推断是另一种结构的出现,也就是二芳基乙烯结构发生周环反应,其结构如图1中的结构II所示,测试结果见图2。
实施例8化合物1,3,3-三甲基-5’,6’-二苯基螺[吲哚-2,2’-[1,4]噁嗪]在300W汞灯激发下的紫外光谱图。
以二氯甲烷为溶剂,将化合物1,3,3-三甲基-5’,6’-二苯基螺[吲哚-2,2’-[1,4]噁嗪]配成浓度为1×10-5mol/L的溶液。在室温条件下,持续通氮气30分钟后,使用Agilent8453型的紫外可见光光度计,用1cm的石英比色皿,在200-800nm波段进行紫外吸收光谱扫描,测量化合物1,3,3-三甲基-5’,6’-二苯基螺[吲哚-2,2’-[1,4]噁嗪]在二氯甲烷溶液中的最大吸收波长及摩尔吸光系数,化合物在光照前,最大吸收波长在381nm,随着光照时间的延长,在381nm处的最大吸收强度在减小,在401nm处出现新的吸收峰,推断是碳氧键的断裂从而生成另一种结构,其结构如图1中的结构III所示,结果见图3。
实施例9化合物1,3,3-三甲基-5’,6’-二苯基螺[吲哚-2,2’-[1,4]噁嗪]三种不同结构的紫外光谱图。
以二氯甲烷为溶剂,将化合物1,3,3-三甲基-5’,6’-二苯基螺[吲哚-2,2’-[1,4]噁嗪]配成浓度为1×10-5mol/L的溶液。在室温条件下,持续通氮气30分钟后,使用Agilent8453型的紫外可见光光度计,用不同波长的光对其进行照射,用1cm的石英比色皿,在200-800nm波段进行紫外吸收光谱扫描,可观察到有不同的吸收情况。说明该化合物存在三种互变异构体,从而可以作为光致变色材料与存储材料,结果见图4。
实施例10化合物1,3,3-三甲基-5’,6’-二苯基螺[吲哚-2,2’-[1,4]噁嗪]的电性能研究。
(1)溶液的配制
所有溶液需要进行蒸馏提纯,正四丁基高氯酸铵和二茂铁也分别用无水乙醇重结晶两次提纯。乙腈和二氯甲烷的混合溶液,体积比4∶6。
0.1mol/L的正四丁基高氯酸铵溶液的配制:准确称取正四丁基高氯酸铵(17.096g,0,05mol)用少量乙腈和二氯甲烷混合溶液溶解后转移至500mL规格的容量瓶中,再用乙腈和二氯甲烷的混合溶液定容。
0.001mol/L的二茂铁的配制:准确称取二茂铁(0.0186g,0.10mmol),正四丁基高氯酸铵(3.4192g,10mmol)用少量乙腈和二氯甲烷的混合溶液溶解后转移至100mL规格的棕色容量瓶中,再用乙腈和二氯甲烷的混合溶液定容。
0.1mol/L的硝酸银标准溶液的配制:准确称取硝酸银(1.6987g,10mmol),正四丁基高氯酸铵(3.4192g,10mmol),用少量乙腈和二氯甲烷混合溶液溶解后转移至100mL规格的容量瓶中,再用乙腈和二氯甲烷的混合溶液定容。
0.0001mol/L的1,3,3-三甲基-5’,6’-二苯基螺[吲哚-2,2’-[1,4]噁嗪]化合物溶液的配制:准确称取该化合物(0.0019g,5.0×10-6mol),正四丁基高氯酸铵(1.7096g,5mmol)用少量乙腈和二氯甲烷的混合溶液溶解后转移至50mL规格的棕色容量瓶中,再用乙腈和二氯甲烷的混合溶液定容。
(2)循环伏安测试
本文采用三电极体系(圆盘Pt工作电极,Pt辅助电极,Ag/AgNO3参比电极)循环伏安测试方法进行实验。电解池中的溶液均经过氮气吹扫10-15min,Ag/AgNO3参比电极电位均用二茂铁为内标进行校正。扫描速度为0.1V/s,灵敏度10-5。
首先开启CHI600C电化学分析工作站,预热二十分钟。以二茂铁为内标进行扫描,校正参比电极电位,然后进行C4溶液的开路电位-时间测定,开路电位稳定后。进入循环伏安法模式,进行参数设定:初始电位设定为开路电位,选取合适的高电位和低电位值和扫描段数,扫描速度0.1V/s,灵敏度10-5.其他参数采用默认值。带扫描的到的循环伏安曲线重现性较好的时候,保存数据,利用Origin8.5作图,进行相关计算和分析。图中出现三处还原氧化峰,说明化合物三种形式的存在,并可应用于存储材料中。结果见图5。
虽然已经用优选实施例详述了本发明,然而其并非用于限定本发明。任何本领域的技术人员,在不脱离本发明的精神和范围的情况下,应当可以作出各种修改与变更。因此本发明的保护范围应当视为所附的权利要求书所限定的范围。
Claims (6)
1.一种双官能团光致变色化合物,其特征在于,含有螺噁嗪和二芳基乙烯两种官能团,其典型结构如下:
结构中R1可以为-CH3,-CH2CH3,-CH2CH2CH3,-CH2OH,-CH3CH2OH,
R2,R3为以下基团的任意组合:
。
2.一种如权利要求1所述的化合物的制备方法,其特征在于:以2-亚硝基,1,2-二芳基乙烯醇与吲哚啉衍生物发生缩合反应得目标化合物。
3.一种如权利要求1所述的化合物的制备方法,其特征在于:反应液为甲醇,苯,或甲苯。
4.一种如权利要求1所述的化合物的制备方法,其特征在于:反应时间为12-16h。
5.一种权利要求1所述的化合物在光致变色材料中的应用。
6.一种权利要求1所述的化合物在信息存储材料中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510694968.3A CN105175431B (zh) | 2015-10-22 | 2015-10-22 | 一种双官能团光致变色化合物、合成及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510694968.3A CN105175431B (zh) | 2015-10-22 | 2015-10-22 | 一种双官能团光致变色化合物、合成及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105175431A true CN105175431A (zh) | 2015-12-23 |
CN105175431B CN105175431B (zh) | 2018-03-30 |
Family
ID=54897942
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510694968.3A Active CN105175431B (zh) | 2015-10-22 | 2015-10-22 | 一种双官能团光致变色化合物、合成及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105175431B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111739563A (zh) * | 2020-06-15 | 2020-10-02 | 上海蔚星科技有限公司 | 超分辨光存储材料 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3964911A (en) * | 1972-12-22 | 1976-06-22 | La Cellophane | Photographic reproduction processes using diazonium salts and substituted spiro[benzopyrane] |
US4405733A (en) * | 1981-08-03 | 1983-09-20 | Xerox Corporation | Composite quasi-crystalline material |
US4705522A (en) * | 1986-08-22 | 1987-11-10 | Eastman Kodak Company | Alkolxy derivative stabilizers for dye-receiving element used in thermal dye transfer |
EP0738728A2 (en) * | 1995-04-20 | 1996-10-23 | Nissho Iwai Bentonite Co.,Ltd. | Ionic spiropyran compound and photochromic material conjugated it with clay |
JP2003301121A (ja) * | 2002-04-11 | 2003-10-21 | Konica Minolta Holdings Inc | 着色組成物、着色微粒子分散物、インクジェット用インク及びインクジェット記録方法 |
CN102363620A (zh) * | 2011-11-10 | 2012-02-29 | 南京工业大学 | 光致变色化合物6’-氮杂环取代-9’-酰氧基酯化螺噁嗪及其合成方法 |
-
2015
- 2015-10-22 CN CN201510694968.3A patent/CN105175431B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3964911A (en) * | 1972-12-22 | 1976-06-22 | La Cellophane | Photographic reproduction processes using diazonium salts and substituted spiro[benzopyrane] |
US4405733A (en) * | 1981-08-03 | 1983-09-20 | Xerox Corporation | Composite quasi-crystalline material |
US4705522A (en) * | 1986-08-22 | 1987-11-10 | Eastman Kodak Company | Alkolxy derivative stabilizers for dye-receiving element used in thermal dye transfer |
EP0738728A2 (en) * | 1995-04-20 | 1996-10-23 | Nissho Iwai Bentonite Co.,Ltd. | Ionic spiropyran compound and photochromic material conjugated it with clay |
JP2003301121A (ja) * | 2002-04-11 | 2003-10-21 | Konica Minolta Holdings Inc | 着色組成物、着色微粒子分散物、インクジェット用インク及びインクジェット記録方法 |
CN102363620A (zh) * | 2011-11-10 | 2012-02-29 | 南京工业大学 | 光致变色化合物6’-氮杂环取代-9’-酰氧基酯化螺噁嗪及其合成方法 |
Non-Patent Citations (3)
Title |
---|
吕博 等: "吲哚啉螺噁嗪光致变色化合物的研究进展", 《化工新型材料》 * |
张长瑞: "双功能光致变色螺噁嗪分子的设计、合成与性质", 《中国博士学位论文全文数据库 工程科技I辑》 * |
杨素华 等: "双功能螺吡喃螺噁嗪类光致变色化合物研究进展", 《有机化学》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111739563A (zh) * | 2020-06-15 | 2020-10-02 | 上海蔚星科技有限公司 | 超分辨光存储材料 |
CN111739563B (zh) * | 2020-06-15 | 2021-09-07 | 上海蔚星科技有限公司 | 超分辨光存储材料 |
Also Published As
Publication number | Publication date |
---|---|
CN105175431B (zh) | 2018-03-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Kawai et al. | Novel photochromic molecules based on 4, 5-dithienyl thiazole with fast thermal bleaching rate | |
Xin et al. | Aggregation-induced emissive copper (I) complexes for living cell imaging | |
Ordronneau et al. | Photochromic metal complexes: Photoregulation of both the nonlinear optical and luminescent properties | |
Shoji et al. | Synthesis of 2‐Azulenyl‐1, 1, 4, 4‐tetracyano‐3‐ferrocenyl‐1, 3‐butadienes by [2+ 2] Cycloaddition of (Ferrocenylethynyl) azulenes with Tetracyanoethylene | |
Han et al. | Third-order nonlinear optical properties of cyanine dyes with click chemistry modification | |
Gao et al. | Luminescence switching property of cycloplatinated (II) complexes bearing 2-phenylpyridine derivatives and the application for data security storage | |
Li et al. | Dithienylethenes functionalized by triphenylethene and difluoroboron β-diketonate fragments: Synthesis, optical switching behavior and fluorescent turn-on sensing for volatile organic amines | |
Su et al. | The triple-stimuli-responsive luminescence switching properties and application of a square-planar platinum (II) complex | |
Zúñiga et al. | Synthesis, characterization, spectroscopic and electrochemical studies of donor–acceptor ruthenium (II) polypyridine ligand derivatives with potential NLO applications | |
Kim et al. | Crystalline-state photochromism and thermochromism of new spiroxazine | |
Metelitsa et al. | Chromogenic properties of heterocyclic compounds: barochromic effect of indoline spiropyrans in the gas phase | |
Ahmed et al. | Photochromism of tetrahydroindolizines. Part XIV: synthesis of cis-fixed conjugated photochromic pyridazinopyrrolo [1, 2-b] isoquinolines incorporating carbon-rich linkers | |
CN105175431A (zh) | 一种双官能团光致变色化合物、合成及其应用 | |
Senthilkumar et al. | Synthesis and characterization of d10 metal complexes of 3-Me-5-FcPz: Structural, theoretical and third order nonlinear optical properties | |
Zhang et al. | Positive and negative photochromism of novel spiro [indoline-phenanthrolinoxazines] | |
Lin et al. | Synthesis, characterization, and properties of some bisacetylide and binuclear acetylide gold (I) compounds based on the photochromic dithienylethene unit | |
Dagilienė et al. | Synthesis of 1′, 3, 3′, 4-tetrahydrospiro [chromene-2, 2′-indoles] as a new class of ultrafast light-driven molecular switch | |
Zhou et al. | Crystal structure and photochromism of auxochrome-introduced Spiro [indoline-quinoline] oxazine deriatives | |
Shoji et al. | Synthesis and Properties of Azulene‐Substituted Donor–Acceptor Chromophores Connected by Arylamine Cores | |
Hu et al. | The photocyclization-dependent ratiometric fluorescent switch: Synthesis, characterization and properties of some terpyridyl-based dithienylethenes | |
Benniston et al. | Molecular rotors based on the boron dipyrromethene fluorophore | |
CN106699644B (zh) | 一种新型芘基查尔酮类衍生物及其合成方法 | |
Lee et al. | Synthesis and characteristics of dicyanopyrazine dyes containing spiropyran group | |
Zhang et al. | An Optic/Proton Dual‐Controlled Fluorescence Switch based on Novel Photochromic Bithienylethene Derivatives | |
Ahmed et al. | Photochromism of dihydroindolizines: part XIV. Synthesis and photophysical behavior of photochromic dihydroindolizine‐tripodal linkers toward anchoring sensitizers to semiconductor nanoparticles |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right |
Effective date of registration: 20200511 Address after: No.18-w710, Yinchun Road, science and technology R & D base, Maigaoqiao Venture Park, Qixia District, Nanjing, Jiangsu Province, 210028 Patentee after: NANJING ZHIYAN TECHNOLOGY Co.,Ltd. Address before: 211816 School of chemical and molecular engineering, Nanjing University of Technology, Nanjing, Pukou, Jiangsu province 30 Patentee before: NANJING TECH University |
|
TR01 | Transfer of patent right |