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WO2016197585A1 - Nouveau dérivé oligomère cyclique de carbazole, son procédé de préparation et son application - Google Patents

Nouveau dérivé oligomère cyclique de carbazole, son procédé de préparation et son application Download PDF

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Publication number
WO2016197585A1
WO2016197585A1 PCT/CN2015/099716 CN2015099716W WO2016197585A1 WO 2016197585 A1 WO2016197585 A1 WO 2016197585A1 CN 2015099716 W CN2015099716 W CN 2015099716W WO 2016197585 A1 WO2016197585 A1 WO 2016197585A1
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WO
WIPO (PCT)
Prior art keywords
group
yield
600mhz
nmr
cyclic
Prior art date
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Ceased
Application number
PCT/CN2015/099716
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English (en)
Chinese (zh)
Inventor
杨鹏
周雪
李刚
简勇
邓拓
杨诏政
田章民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenyang Pharmaceutical University
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Shenyang Pharmaceutical University
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Filing date
Publication date
Application filed by Shenyang Pharmaceutical University filed Critical Shenyang Pharmaceutical University
Publication of WO2016197585A1 publication Critical patent/WO2016197585A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C07D487/18—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings

Definitions

  • the invention belongs to the technical field of chemical synthesis, and relates to a cyclic oligomeric carbazole derivative and a preparation method and application thereof.
  • Carbazole is a nitrogen-containing aromatic heterocyclic ring having a rigid fused ring structure. Its structure has the following characteristics: (1) carbazole itself is one of coal tar products, raw materials are cheap and easy to obtain; (2) have a large conjugated system in the molecule and strong intramolecular electron transfer; (3) carbazole ring It is easy to carry out structural modification to introduce a variety of functional groups; (4) carbazole is also a class of fluorophores which have been widely studied and used, and has high thermal stability and photochemical stability.
  • carbazole has potential applications in derivatives such as photovoltaic materials, dyes, pharmaceuticals, and supramolecular recognition, and has been extensively researched and developed in recent years.
  • oxazole polymers are often used. It is difficult to synthesize oligomeric macrocycles with carbazole as the parent. Many oligomeric macrocycles are easy to synthesize, but they do not have luminescent properties and are not easily detectable.
  • the technical problem solved by the present invention is to provide a method for synthesizing a cyclic oligocarbazole derivative.
  • This method which has never been reported, can prepare a plurality of new oligomeric macrocycles in a single reaction.
  • the oligomeric carbazole of the invention has good optical properties and can be detected by an ultraviolet meter and a fluorometer.
  • the invention makes the synthetic oligomeric carbazole structure more abundant ⁇ electrons, and can form a host-guest complex based on the "cation- ⁇ " weak interaction force with the positively charged cationic quaternary ammonium salt.
  • the cyclic oligocarbazole derivative of the present invention has the following structural formula:
  • R C1 to C8 carboxylic acid and ester thereof, C1 to C6 amide, benzyl group, N, O, S hetero atom-substituted benzyl group, C1-C8 linear, branched alkyl group or C3 to C8 Cycloalkyl, C1-C8 linear, branched or C3-C8 cycloalkyl substituted with N, O, S heteroatom
  • R 1 H, halogen, hydroxy, C1-C4 ester group, C1-C4 alkyl group, alkoxy group and alkylamino group
  • R 2 H, halogen, hydroxy, C1-C4 ester group, C1-C4 alkyl group, alkoxy group and alkylamino group
  • n an integer of 3-8.
  • the present invention preferably has the following compounds:
  • R -CH 2 C 6 H 5 , -C 6 H 4 CHO, -CH 2 COOH, -CH 2 COOC 2 H 5 , -CH 2 COO(C 2 H 4 O) 3 CH 3 , -CH 2 C 6 H 4 COO(C 2 H 4 O) 3 CH 3 , -CH 2 C 6 H 4 COOC 2 H 5
  • R 1 H, halogen, hydroxy, C1-C4 ester group, C1-C4 alkyl group, alkoxy group and alkylamino group
  • R 2 H, halogen, hydroxy, C1-C4 ester group, C1-C4 alkyl group, alkoxy group and alkylamino group
  • n 3, 4, 5, 6, 7, 8;
  • the present invention also preferably has the following compounds:
  • R -CH 2 C 6 H 5 , -C 6 H 4 CHO, -CH 2 COOH, -CH 2 COOC 2 H 5 , -CH 2 COO(C 2 H 4 O) 3 CH 3 , -CH 2 C 6 H 4 COO(C 2 H 4 O) 3 CH 3 , -CH 2 C 6 H 4 COOC 2 H 5
  • R 1 H, Cl, Br, I, -OH, -OCOCH 3 , -CH 3 , -OCH 3 , -NHCH 3
  • R 2 H, halogen, hydroxy, C1-C4 ester group, C1-C4 alkyl group, alkoxy group and alkylamino group
  • n 3, 4, 5, 6, 7, 8;
  • the present invention also preferably has the following compounds:
  • R -CH 2 C 6 H 5 , -C 6 H 4 CHO, -CH 2 COOH, -CH 2 COOC 2 H 5 , -CH 2 COO(C 2 H 4 O) 3 CH 3 , -CH 2 C 6 H 4 COO(C 2 H 4 O) 3 CH 3 , -CH 2 C 6 H 4 COOC 2 H 5
  • R 1 R 1 : H, Cl, Br, I, -OH, -OCOCH 3 , -CH 3 , -OCH 3 , -NHCH 3
  • R 2 R 1 : H, Cl, Br, I, -OH, -OCOCH 3 , -CH 3 , -OCH 3 , -NHCH 3
  • n 3, 4, 5, 6, 7, 8.
  • the monomer structure of the carbazole derivative used in the present invention is as follows:
  • the concentration of the carbazole derivative monomer solution in the step (2) is from 0.7 g/L to 1.3 g/L, preferably from 1 g/L to 1.1 g/L.
  • the paraformaldehyde of the step (2) is 0.7 to 1.4 times the molar amount of the carbazole derivative monomer, preferably 1.0 to 1.1 times the molar amount thereof.
  • the solvent is selected from the group consisting of dichloromethane, chloroform and 1,2-dichloroethane, preferably dichloromethane; preferably, the Lewis acid is selected from the group consisting of ferric chloride hexahydrate and anhydrous ferric chloride.
  • the Lewis acid is selected from the group consisting of ferric chloride hexahydrate and anhydrous ferric chloride.
  • the Lewis acid concentration of the step (2) is from 0.1 to 0.6 times the mole of the carbazole derivative monomer, preferably from 0.2 to 0.3 times the mole thereof.
  • the mixed solution of the step (2) is carried out at a normal temperature, preferably at 20 to 30 ° C; preferably, the reaction time is 8 h to 79 h, more preferably 9 h to 18 h.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

La présente invention concerne le domaine technique de la synthèse chimique et en particulier un dérivé oligomère cyclique de carbazole, un procédé pour sa préparation et une application correspondante. Une formule développée du dérivé oligomère cyclique de carbazole de la présente invention est représentée par la formule (I), dans laquelle chaque variable est décrite dans la description et les revendications. Le procédé de la présente invention permet de préparer une pluralité de nouveaux cycles oligomères de grande taille au moyen d'une réaction en une seule étape. Le carbazole oligomère de la présente invention présente d'excellentes performances optiques et peut être détecté par un instrument à ultraviolets et un fluoromètre. Grâce à la présente invention, une structure oligomère synthétique de carbazole est plus riche en électrons π et la structure oligomère synthétique de carbazole et un ammonium quaternaire cationique présentant une charge positive peuvent former un composé hôte-invité sur base d'une force d'interaction 'cation-π' faible.
PCT/CN2015/099716 2015-06-08 2015-12-30 Nouveau dérivé oligomère cyclique de carbazole, son procédé de préparation et son application Ceased WO2016197585A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510309211.8A CN106279185B (zh) 2015-06-08 2015-06-08 新型环状寡聚咔唑衍生物及其制备方法与应用
CN2015103092118 2015-06-08

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WO2016197585A1 true WO2016197585A1 (fr) 2016-12-15

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109836429A (zh) * 2017-11-29 2019-06-04 沈阳药科大学 杯[n]咔唑类衍生物及其作为T交叉DNA荧光分子探针的应用
JP2022552684A (ja) * 2019-10-15 2022-12-19 天津師範大学 ビフェニルアレーンに基づく大環とかご状分子並びに誘導化合物、及びその合成方法と応用
CN116640085A (zh) * 2023-05-15 2023-08-25 陕西师范大学 一种合成咔唑衍生物的方法
CN117924297A (zh) * 2022-10-24 2024-04-26 沈阳药科大学 桥亚甲基修饰的杯[3]咔唑衍生物及其合成方法和应用

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* Cited by examiner, † Cited by third party
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CN107663211B (zh) * 2016-07-29 2019-12-10 沈阳药科大学 咔唑杯芳烃四环衍生物及其制备方法和应用
CN110041248B (zh) * 2019-04-18 2022-08-05 上海大学 3,5-双(2,4-二甲氧基苯基)吡啶二元环、其制备方法及应用
CN113620964B (zh) * 2020-05-06 2022-07-01 沈阳药科大学 取代的杯咔唑衍生物及其合成方法和应用
CN113754669B (zh) * 2020-06-01 2022-07-12 沈阳药科大学 杯[3]咔唑衍生物及其合成和应用
CN116554178A (zh) * 2022-01-27 2023-08-08 四川大学 一种亚氨基二苄衍生物大环化合物的合成方法
CN116332939A (zh) * 2023-02-08 2023-06-27 沈阳药科大学 吲哚并咔唑基元及其环状衍生物和制备方法与应用

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109836429A (zh) * 2017-11-29 2019-06-04 沈阳药科大学 杯[n]咔唑类衍生物及其作为T交叉DNA荧光分子探针的应用
CN109836429B (zh) * 2017-11-29 2021-05-07 沈阳药科大学 杯[n]咔唑类衍生物及其作为T交叉DNA荧光分子探针的应用
JP2022552684A (ja) * 2019-10-15 2022-12-19 天津師範大学 ビフェニルアレーンに基づく大環とかご状分子並びに誘導化合物、及びその合成方法と応用
JP7433673B2 (ja) 2019-10-15 2024-02-20 天津師範大学 ビフェニルアレーンに基づく大環とかご状分子並びに誘導化合物、及びその合成方法と応用
CN117924297A (zh) * 2022-10-24 2024-04-26 沈阳药科大学 桥亚甲基修饰的杯[3]咔唑衍生物及其合成方法和应用
CN116640085A (zh) * 2023-05-15 2023-08-25 陕西师范大学 一种合成咔唑衍生物的方法

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CN106279185B (zh) 2019-04-02

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