Microwave irradiation assisted synthesis, alkylation reaction, and configuration analysis of aryl pyrogallol[4]arenes

Yan, Chao‐Guo; Chen, Weifeng; Chen, Jiao; Jiang, Tiantian; Yao, Yong

doi:10.1016/j.tet.2007.07.043

Cited by 27 publications

(11 citation statements)

References 34 publications

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“…Aryl-substituted pyrogallol [4]arenes are known to be insoluble in most of the common organic solvents, so their hydroxyl groups were acetylated to enhance solubility. 15 We found that 1 exhibited good solubility in DMSO. Crystals were grown from the diffusion of MeOH into the DMSO solution saturated with 1.…”

Section: Resultsmentioning

confidence: 83%

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Synthesis, Crystal Structure, and Spectroscopic Investigation of C-Cyanophenyl Pyrogallol[4]arene

Jeon

Kim²,

Kim³

et al. 2008

Bulletin of the Korean Chemical Society

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Pyrogallol [4]arenes have drawn much attention since their emergence as new hydrogen-bonded hexameric 1 or metalseamed 2,3 capsule-forming molecular receptors. arenes often form a variety of superstructures other than hexameric capsules 4-7 including dimeric capsules 8 and bilayers depending on the selection of solvent conditions. 1,9-12It is well established that the substitution of aryls for alkyls on methine units connecting the pyrogallols of pyrogallol-[4]arene yields a chair conformation, while alkyl-substituted pyrogallol[4]arene mostly adopts a cone conformation. In these reports, the hydroxyl groups of pyrogallols were acetylated to enhance solubility because of the poor solubility of unacetylated forms in common organic solvents. 13Herein, we describe the synthesis, crystal structure, and spectroscopic investigation of C-cyanophenyl pyrogallol-[4]arene (1) without any modification of the hydroxyl groups of pyrogallols, which might be the first crystal structure formed in unacetylated aryl-substituted pyrogallol[4]-arenes. These findings might be useful for the design of receptors based on pyrogallol [4]arenes for the construction of the superstructure derived from hydrogen bonds or metal coordinations. Experimental SectionAll the chemicals were used as received without further purification. The synthesis of pyrogallol[4]arene were performed according to the method in the literature method. 13The 1 H NMR and 13 C NMR spectra were recorded on a Bruker AVANCE II spectrometer at a Larmor frequency of 400.13 MHz. The infrared (IR) spectra were recorded on a MIDAC M series IR spectrometer. MALDI-TOF mass spectra were obtained on a Bruker Reflex III MALDI-TOF mass spectrometer. Data collection for 1 was performed with the beamline (6C1 MXII) at the Pohang Accelerator Laboratory (PAL).Synthesis of 2,8,14,20-cyanophenyl pyrogallol[4]arenes (1). The synthesis of 1 has been reported elswhere.1 Briefly, equimolar amounts of pyrogallol (1.2 g, 10 mmol) and 4-cyanobenzaldehyde (1.3 g, 10 mmol) were mixed in a round-bottom flask containing 30 mL of ethanol and 10 mL of concentrated HCl with a flow of nitrogen; the solution was stirred under a reflux at 70-80 o C for 1 day. The resulting solution was cooled to room temperature. Filtration and washing with water and ethanol several times followed by drying in vacuum gave the desired product (yield = ~65%).

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Section: Resultsmentioning

confidence: 83%

“…This finding is consistent with the previous reports on arylsubstituted pyrogallol [4]arenes. 13,15 Therefore, to the best of our knowledge, it is the first crystal structure of unacetylated aryl-substituted pyrogallol [4]arene. The structure of 1 exhibits C 2 symmetry around the centroid of pyrogallol [4]arene and is also linear.…”

Section: Resultsmentioning

confidence: 93%

Synthesis, Crystal Structure, and Spectroscopic Investigation of C-Cyanophenyl Pyrogallol[4]arene

Jeon

Kim²,

Kim³

et al. 2008

Bulletin of the Korean Chemical Society

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“…The 1 H‐signals of PG ring were observed at 6.06 (s, 2H, H a ) and 5.58 (s, 2H, H a ), indicating that there are two kinds of PG rings with a different conformation, and that thermodynamically stable rctt ( cis‐trans‐trans ) isomer is preferentially formed. Although the 1 H NMR spectral data of aryl pyrogallol[4]arenes have not yet been reported because of the very poor solubility, the reported NMR data of acylated aryl pyrogallol[4]arenes in CDCl 3 resemble those of PGVNC 24. The stable conformation of the PGVNC with rctt configuration was calculated by MM2.…”

Section: Resultsmentioning

confidence: 99%

“…As a result of the spectral analyses of the obtained reaction product, it was found that pyrogallol–vanillin calixarene (PGVNC) mainly composed of guaiacyl pyrogallol[4]arene is formed. Although aryl pyrogallol[4]arenes synthesized by the reactions of PG with benzaldehyde, p ‐methylbenzaldehyde and p ‐methoxybenzaldehyde, and so on are known compounds, their calixarenes have attracted little attention because of the very poor solubility in common solvents [24, 25]. In contrast, the PGVNC can be easily used as building blocks of polymeric materials because of the good solubility to some organic solvents.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization, reactivity ratios by nuclear magnetic resonance spectroscopy, and application of (2,5‐Dichlorophenyl acrylate‐co‐glycidyl methacrylate) polymers as adhesives for the leather industry

Vijayaraghavan

Reddy

2005

J of Applied Polymer Sci

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2,5-Dichlorophenyl acrylate (DPA)-co-glycidyl methacrylate (GMA) polymers having five different compositions were synthesized in 1,4-dioxane using benzoyl peroxide as a free-radical initiator at 70 Ϯ 0.5°C. Using 1 H-NMR spectroscopy, the composition of the two monomers in the copolymers was calculated by comparing the integral values of the aromatic and aliphatic proton peaks. The reactivity ratios were calculated by Fineman-Ross (r 1 ϭ 0.31 and r 2 ϭ 1.08), Kelen-Tudos (r 1 ϭ 0.40 and r 2 ϭ 1.15), and extended Kelen-Tudos (r 1 ϭ 0.39 and r 2 ϭ 1.16) methods. The nonlinear error-in-variables model was used to compare the reactivity ratios. The copolymers were characterized by 1 H and proton decoupled 13 C-NMR spectroscopes. Gel permeation chromatography was performed for estimating the M w and M n and M w /M n of the poly(DPA) and copolymers (DPA-co-GMA: 09 : 91 and 50 : 50). Thermal stability of the homo-and copolymers was estimated using TGA [poly(DPA) Ͼ DPA-co-GMA (50 : 50) Ͼ DPA-co-GMA (09:91)], while DSC was utilized for determining the glass transition temperature. T g increased with increased DPA content in the copolymer. The 50 : 50 mol % copolymer was chosen for curing with diethanolamine in chloroform. The cured resins were tested for the adhesive properties on leather at different temperatures (50, 90, 100, and 110°C). The resin cured at 50°C exhibited a maximum peel strength of 1.6 N/mm, revealing a good adhesive behavior.

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“…A pioneering work, reported by Yan and co-workers in 2007 [106], described the preparation of pyrogallol [4]arenes 280, 281, which have been synthesized by reacting equal molar amounts of pyrogallol (277) and substituted aromatic aldehydes 278 in an acidic medium and under MW-irradiation (130 W) (Scheme 58). The expected calix [4]arenes 279 have been isolated in good yields (66%-89%).…”

Section: Mw-assisted Syntheses Of Calix-type Derivativesmentioning

confidence: 99%

Microwave-Assisted Syntheses of Bioactive Seven-Membered, Macro-Sized Heterocycles and Their Fused Derivatives

et al. 2016

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This review describes the recent advances in the microwave-assisted synthesis of 7-membered and larger heterocyclic compounds. Several types of reaction for the cyclization step are discussed: Ring Closing Metathesis (RCM), Heck and Sonogashira reactions, Suzuki-Miyaura cross-coupling, dipolar cycloadditions, multi-component reactions (Ugi, Passerini), etc. Green syntheses and solvent-free procedures have been introduced whenever possible. The syntheses discussed herein have been selected to illustrate the huge potential of microwave in the synthesis of highly functionalized molecules with potential therapeutic applications, in high yields, enhanced reaction rates and increased chemoselectivity, compared to conventional methods. More than 100 references from the recent literature are listed in this review.

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Microwave irradiation assisted synthesis, alkylation reaction, and configuration analysis of aryl pyrogallol[4]arenes

Cited by 27 publications

References 34 publications

Synthesis, Crystal Structure, and Spectroscopic Investigation of C-Cyanophenyl Pyrogallol[4]arene

Synthesis, Crystal Structure, and Spectroscopic Investigation of C-Cyanophenyl Pyrogallol[4]arene

Synthesis, characterization, reactivity ratios by nuclear magnetic resonance spectroscopy, and application of (2,5‐Dichlorophenyl acrylate‐co‐glycidyl methacrylate) polymers as adhesives for the leather industry

Microwave-Assisted Syntheses of Bioactive Seven-Membered, Macro-Sized Heterocycles and Their Fused Derivatives

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