CN104016996A - 新型苯并吡喃类光致变色衍生物 - Google Patents
新型苯并吡喃类光致变色衍生物 Download PDFInfo
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- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical class OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
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- BIJNHUAPTJVVNQ-UHFFFAOYSA-N 1-Hydroxypyrene Chemical compound C1=C2C(O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 BIJNHUAPTJVVNQ-UHFFFAOYSA-N 0.000 claims description 5
- NOOSWYSQSNNIJC-UHFFFAOYSA-N 9h-carbazole;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C3=CC=CC=C3NC2=C1 NOOSWYSQSNNIJC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- HRDCVMSNCBAMAM-UHFFFAOYSA-N 3-prop-2-ynoxyprop-1-yne Chemical compound C#CCOCC#C HRDCVMSNCBAMAM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005821 Claisen rearrangement reaction Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical compound C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001725 pyrenyl group Chemical group 0.000 claims description 2
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 abstract description 16
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract description 12
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
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- 238000002360 preparation method Methods 0.000 abstract description 2
- 150000001562 benzopyrans Chemical class 0.000 abstract 1
- 239000011232 storage material Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 16
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- 239000000243 solution Substances 0.000 description 11
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- 238000010521 absorption reaction Methods 0.000 description 7
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- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- -1 benzopyrans compounds Chemical class 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
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- PCNKISGLYANZGP-UHFFFAOYSA-N 9-ethylcarbazol-3-ol Chemical compound OC1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PCNKISGLYANZGP-UHFFFAOYSA-N 0.000 description 2
- 0 C*c1ccc(C(C=CC23)(c(cc4)ccc4OC)OC2(C)C=CC2=C3c3ccccc3*2*N)cc1 Chemical compound C*c1ccc(C(C=CC23)(c(cc4)ccc4OC)OC2(C)C=CC2=C3c3ccccc3*2*N)cc1 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
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- 239000012043 crude product Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DQXKOHDUMJLXKH-PHEQNACWSA-N (e)-n-[2-[2-[[(e)-oct-2-enoyl]amino]ethyldisulfanyl]ethyl]oct-2-enamide Chemical compound CCCCC\C=C\C(=O)NCCSSCCNC(=O)\C=C\CCCCC DQXKOHDUMJLXKH-PHEQNACWSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- UEOHATPGKDSULR-UHFFFAOYSA-N 9h-carbazol-4-ol Chemical compound N1C2=CC=CC=C2C2=C1C=CC=C2O UEOHATPGKDSULR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000005286 illumination Methods 0.000 description 1
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- 230000005622 photoelectricity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C07D491/052—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being six-membered
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
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Abstract
本发明涉及一类苯并吡喃类光致变色化合物，其为以芘或咔唑为结构单元的苯并吡喃衍生物。化合物以式I表示，其中R1和R2位置为芘或咔唑。该类化合物在紫外光的照射下，能从无色变为墨绿色，是一类优良的光致变色化合物，可用于高密光子存储和可擦写光存储材料以及光控开关材料的制备。
Description
技术领域
本发明涉及一类新苯并吡喃类光致变色化合物及其制备。
背景技术
光致变色现象(Photochromism)是化学研究领域重要的组成部分，指一个化合物(A)在受到一定波长的光电辐射下，发生特定的化学反应，生成产物(B)，其吸收光谱与(A)有着明显的变化，并能在不同的条件下实现化合物(A)与(B)之间的可逆转换，具有这种性质的材料称为光致变色材料(F.Ercole,et al.Macromolecules2009,42,1500–1511)。
苯并吡喃是一类常见的、性能优良的光致变色化合物。萘并吡喃及其衍生物主要是由相应的酚与炔丙醇衍生物在酸性介质中催化下得到炔丙基醚，再发生Claisen重排反应，然后通过醌式化合物的环化反应合成得到的，常用的酸性介质有对甲苯磺酸、酸性氧化铝等。20世纪90年代初，在室温下具有较好变色性能的2,2-二苯基萘并吡喃类化合物商品化并成为变色树脂镜片中必不可少的组分，使得人们对这类化合物引起了广泛的关注。由于具有较好的光响应性、褪色速度、光稳定性以及在可见光区吸收带宽等优点，苯并吡喃类化合物成为了继螺噁嗪之后，另一类具有实际应用价值的光致变色染料(M.R.di Nunzio,et al.ChemPhysChem2008,9(5):768–775)。
发明内容
本发明的目的是提供一种开环体的热衰减速率降低、具有宽吸收带的苯并吡喃衍生物光致变色剂。
本发明的第一方面是一种苯并吡喃衍生物，其为式I所示化合物：
其中R1和R2位置为式(a)表示的芘基团或式(b)表示的咔唑基团，
其中R3为氢或C1～C12的直链或支链烷基。
优选地，本发明的苯并吡喃衍生物，为I-1所示化合物：
优选地，本发明的苯并吡喃衍生物，其为I-b所示化合物
其中R3为氢、甲基、乙基或C3～C12的直链或支链烷基。
本发明的第二方面是上述苯并吡喃衍生物作为光致变色剂的用途。
本发明的第三方面还提供一种合成上述苯并吡喃衍生物的方法，包括：以与式(a)相应的羟基芘或与式(b)相应咔唑酚为原料，与式E0表示的炔丙醇衍生物在酸性介质中催化下得到炔丙基醚，再发生Claisen重排反应，然后通过醌式化合物的环化反应，得到目标化合物，
优选地，本发明的方法包括：以与式(a)相应的羟基芘或与式(b)相应咔唑酚为原料，和式E0表示的炔丙醇衍生物，在酸性氧化铝存在下，在二甲苯溶剂中，在氩气保护下，避光回流反应至溶液呈墨绿色，冷却至室温，过滤得到的滤液蒸发除去溶剂，得到所述苯并吡喃衍生粗产品。
本发明设计并合成的含芘或咔唑为结构单元的苯并吡喃衍生物，其溶液在特定波长激发下，可在无色体与呈色体间快色转化，并且吸收波长几乎覆盖整个可见光区，是一类优良的光致变色化合物，且合成比较简单、合成步骤较少，而且原料成本低廉和易于大规模的商业化生产等优点。
附图说明
图1.化合物I-1在乙腈溶剂中，分别在紫外光照射下及其后可见光照射下的吸收曲线变化图(10-5mol·L-1)；
图2.化合物I-2在乙腈溶剂中，分别在紫外光照射下及其后可见光照射下的吸收曲线变化图(10-5mol·L-1)；及
图3.化合物I-3在乙腈溶剂中，分别在紫外光照射下及其后可见2光照射下的吸收曲线变化图(10-5mol·L-1)。
具体实施方式
本发明在苯并吡喃类化合物中引入较大的结构单元如芘和咔唑为结构单元，设计并合成了含有芘和咔唑单元的苯并吡喃类光致变色材料，可明显降低开环体的热衰减速率。另外，具有咔唑单元的体系表现出更优的热衰减速率，其半衰期τ1/2达到了48s，并且吸收红移至整个可见光区。
本发明还提供一种合成上述含芘和咔唑为结构单元的苯并吡喃衍生物的方法，其主要步骤是：以相应的含芘和咔唑酚为原料，先与取代的炔丙醇在酸性介质中催化下得到炔丙基醚，再发生Claisen重排反应，然后通过醌式化合物的环化反应，得到目标化合物(式I所示化合物)。
下面通过实例对本发明作进一步的阐述，目的在于更好理解本发明的内容。因此，所举之例并不限制本发明的保护范围；实施例中所说的室温是：25～28℃；所用的原料及试剂均为市售品。
实施例1
光致变色化合物I-1的合成
式中toluene为二甲苯。
在装有分水器的500mL三口烧瓶中，依次加入1-羟基芘(Ea0,623mg,2.85mmol)、炔丙醇衍生物(E0,903mg,3.36mmol)、3.5g酸性氧化铝及300mL二甲苯，在氩气保护下，避光加热90℃反应35h，溶液呈墨绿色。反应液冷却至室温后，抽滤，滤饼用二氯甲烷洗涤，将滤液与洗涤液合并，旋干溶剂后，粗产品柱层析分离，所得粗产物再用无水乙醇重结晶得到淡黄色固体210mg，产率22％。产率55％。
1H-NMR(400MHz,CDCl3,ppm):δ8.47(d,J＝9.2Hz,1H,phenyl-H),8.04(d,J＝7.2Hz,1H,phenyl-H),8.03(d,J＝7.2Hz,1H,phenyl-H),7.98(d,J＝9.2Hz,1H,phenyl-H),7.90(d,J＝7.6Hz,1H,phenyl-H),7.85(dd,J1＝8.4Hz,J2＝8.8Hz,2H,phenyl-H),7.80(s,1H,phenyl-H),7.47(d,J＝8.4Hz,4H,phenyl-H),6.98(d,J＝10.0Hz,1H,phenyl-H),6.83(d,J＝8.8Hz,4H,phenyl-H),6.36(d,J＝9.6Hz,1H,phenyl-H),3.75(s,6H,O-CH3).
HRMS-ESI(m/z):[M+H]+Calcd.for(C33H25O3),469.1804,Found:469.1804.
实施例2
光致变色化合物I-2的合成
在装有分水器的250mL三口烧瓶中，依次加入4-羟基咔唑(Eb0,1.0g,5.4mmol)、炔丙醇衍生物(E0,1.6g,6.0mmol)、6.1g酸性氧化铝及180mL甲苯，在氩气保护下，避光回流反应2h。反应液冷却至室温后，抽滤，滤饼用二氯甲烷洗涤，将滤液与洗涤液合并，旋干溶剂后，粗产品柱层析分离，所得粗产物再用无水乙醇重结晶得到红色固体790mg，产率48％。
1H-NMR(400MHz,CDCl3,ppm):δ8.41(d,J＝7.6Hz,1H,phenyl-H),8.00(s,1H,phenyl-H),7.51(d,J＝8.8Hz,4H,phenyl-H),7.38(s,1H,phenyl-H),7.28(s,1H,phenyl-H),7.07(d,J＝8.0Hz,1H,phenyl-H),6.87(d,J＝8.8Hz,4H,phenyl-H),6.73(s,1H,phenyl-H),6.04(s,1H,phenyl-H),3.90(s,1H,N-H),3.78(s,6H,C-H).
HRMS-ESI(m/z):[M+H]+Calcd.for(C29H24NO3),434.1756,Found:434.1753。
实施例3
I-3所示化合物的合成
(1)3-羟基-9-乙基咔唑的合成
将3-氨基-9-乙基咔唑(2.0g,4.76mmol)、冰水(10mL)和浓硫酸(2mL)于冰盐浴下搅拌，呈墨绿色悬浊液。然后将冷却的亚硝酸钠(0.80g,11.6mmol)水溶液滴加搅拌10min，溶液变成黄色。然后将稀酸溶液(6mL浓硫酸于56mL水)加入到反应液中，加热回流3h。反应结束，二氯甲烷萃取，悬干，得到黑色固体0.8g，柱层析，展开剂(DCM:PE＝2:1)，得到黑色固体310mg，产率16％。该中间体不需提纯直接用于下一步。
(2)I-3的合成
在装有分水器的三口烧瓶中，依次加入3-羟基-9-乙基咔唑(110mg,0.5mmol)、炔丙醇衍生物(E0,160mg,0.6mmol)、0.6g酸性氧化铝及150mL甲苯，氩气保护下，避光回流反应5h。反应液冷却至室温后，抽滤，滤饼用二氯甲烷洗涤，将滤液与洗涤液合并，旋干溶剂后，得到黑色固体120mg，粗产品柱层析分离，展开剂(DCM:PE＝1:2)，得到淡黄色固体50mg，产率19％。
1H-NMR(400MHz,CDCl3,ppm):δ8.17(d,J＝8.0Hz,1H,phenyl-H),7.55(d,J＝10.0Hz,1H,phenyl-H),7.41(d,J＝8.8Hz,5H,phenyl-H),7.34(d,J＝8.0Hz,1H,phenyl-H),7.18(d,J＝8.0Hz,1H,phenyl-H),7.15(d,J＝8.8Hz,1H,phenyl-H),7.08(d,J＝8.8Hz,1H,phenyl-H),6.83(d,J＝8.8Hz,4H,phenyl-H),6.31(d,J＝10.0Hz,1H,phenyl-H),4.27(m,J＝7.2Hz,2H,-CH2-),3.76(s,6H,O-CH3),1.36(t,3H,J＝7.2Hz,-CH3).
HRMS-ESI(m/z):[M+H]+Calcd.for(C33H25O3),462.2069,Found:462.2073。
化合物I-1光致变色现象及其荧光开关现象
图1-图3分别表示化合物I-1，I-2，I-3在乙腈溶剂中(10-5mol·L-1)，分别在紫外光照射下及其后可见光照射下的吸收曲线变化图。图中箭头方向表示系列曲线代表的紫外线照射时间从短到长的方向。
以光致变色化合物I-1为例，其在乙腈溶液(5.0×10-5M)中为无色透明溶液，可见光区域没有吸收，在365nm紫外光照射下，溶液变成紫色(附图1)，其吸收光谱在可见光区域产生一个很宽的吸收带，这是由于发生了特征的开环反应，光照前结构经sp3C-O键的断裂，导致平面性的增强，生成了π电子体系更加离域的MC结构，在可见光区域产生新的吸收带，从而发生颜色变化，即光致变色现象。
苯并吡喃类化合物中引入较大的结构单元如芘和咔唑为结构单元，可明显降低开环体的热衰减速率，如具有咔唑单元的体系表现出更优的热衰减速率，其半衰期τ1/2达到了48s，并且吸收红移至整个可见光区。
Claims (7)
1.一种苯并吡喃衍生物，其为式I所示化合物：
其中R1和R2位置为式(a)表示的芘基团或式(b)表示的咔唑基团，
其中R3为氢或C1～C12的直链或支链烷基。
2.如权利要求1所述的苯并吡喃衍生物，其为I-1所示化合物：
3.如权利要求1所述的苯并吡喃衍生物，其为I-2或I-3所示化合物：
4.如权利要求1所述的所述的苯并吡喃衍生物，其为I-b所示化合物：
其中R3为氢、甲基、乙基或C3～C12的直链或支链烷基。
5.权利要求1-4任一项所述的苯并吡喃衍生物作为光致变色剂的用途。
6.一种合成权利要求1-4任一项所述的苯并吡喃衍生物的方法，包括：
以与式(a)相应的羟基芘或与式(b)相应咔唑酚为原料，与式E0表示的炔丙醇衍生物在酸性介质中催化下得到炔丙基醚，再发生Claisen重排反应，然后通过醌式化合物的环化反应，得到目标化合物，
7.如权利要求6所述的方法，包括：以与式(a)相应的羟基芘或与式(b)相应咔唑酚为原料，和式E0表示的炔丙醇衍生物，在酸性氧化铝存在下，在二甲苯溶剂中，在氩气保护下，避光回流反应至溶液呈墨绿色，冷却至室温，过滤得到的滤液蒸发除去溶剂，得到所述苯并吡喃衍生粗产品。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1129450A (zh) * | 1993-08-13 | 1996-08-21 | 皮尔金顿公共有限公司 | 光致变色的杂环苯并吡喃 |
| CN1242009A (zh) * | 1996-12-23 | 2000-01-19 | 康宁股份有限公司 | (苯并呋喃)萘并吡喃、含此类化合物的组合物及(共)聚合物基料 |
| EP1122251A1 (en) * | 1999-06-03 | 2001-08-08 | Tokuyama Corporation | Chromene compounds |
| CN1634916A (zh) * | 2004-10-20 | 2005-07-06 | 南开大学 | 2，2－二芳基萘并吡喃类化合物及其制备方法 |
| CN103030652A (zh) * | 2011-09-29 | 2013-04-10 | 上海甘田光学材料有限公司 | 一种苯并吡喃衍生物、制备方法及应用 |
-
2014
- 2014-06-04 CN CN201410244640.7A patent/CN104016996B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1129450A (zh) * | 1993-08-13 | 1996-08-21 | 皮尔金顿公共有限公司 | 光致变色的杂环苯并吡喃 |
| CN1242009A (zh) * | 1996-12-23 | 2000-01-19 | 康宁股份有限公司 | (苯并呋喃)萘并吡喃、含此类化合物的组合物及(共)聚合物基料 |
| EP1122251A1 (en) * | 1999-06-03 | 2001-08-08 | Tokuyama Corporation | Chromene compounds |
| CN1634916A (zh) * | 2004-10-20 | 2005-07-06 | 南开大学 | 2，2－二芳基萘并吡喃类化合物及其制备方法 |
| CN103030652A (zh) * | 2011-09-29 | 2013-04-10 | 上海甘田光学材料有限公司 | 一种苯并吡喃衍生物、制备方法及应用 |
Non-Patent Citations (2)
| Title |
|---|
| M. MANUEL OLIVEIRA，等: "New benzopyranocarbazoles: synthesis and photochromic behaviour", 《TETRAHEDRON》 * |
| M. MANUEL OLIVEIRA，等: "Remarkable thermally stable open forms of photochromic new N-substituted benzopyranocarbazoles", 《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A: CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI780043B (zh) * | 2016-03-10 | 2022-10-11 | 日商三菱瓦斯化學股份有限公司 | 具有光致變色特性的合成樹脂層合體及使用其之透鏡 |
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Denomination of invention: Benzopyran based photochromic derivatives Granted publication date: 20170111 Pledgee: CITIC Bank Limited by Share Ltd. Shanghai branch Pledgor: SHANGHAI GANTIAN OPTICAL MATERIALS Co.,Ltd. Registration number: Y2024310000757 |