An efficient synthesis of substituted benzene-1,2-dicarboxaldehydes

Zhu, Peter C.; Wang, Der-Haw; Lu, Kaitao; Mani, Neelakandha S.

doi:10.1007/s11426-007-0031-y

Cited by 5 publications

(3 citation statements)

References 17 publications

(11 reference statements)

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“…The most diagnostic resonances in the 1 H NMR spectra are those for host protons H n (6.89 ppm) as well as H o and H p (4.93 and 5.12 ppm) which are upfield shifted due to their proximity to the fused aromatic o -xylylene ring. Similar reactions were conducted between 6C and carboxylic acid or nitro-substituted phthalaldehydes 14 and 15 which delivered monofunctionalized CB[6] derivatives 16 and 17 in 56% (641 mg) and 58% (65 mg), respectively . Figure c,d shows their 1 H NMR spectra recorded as their complexes with 11 which reflects the lower C s -symmetry of these CB[6] derivatives.…”

Section: Resultsmentioning

confidence: 99%

Templated Synthesis of Glycoluril Hexamer and Monofunctionalized Cucurbit[6]uril Derivatives

et al. 2011

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We report that the p-xylylenediammonium ion (11) acts as a template in the cucurbit[n]uril forming reaction that biases the reaction toward the production of methylene bridged glycoluril hexamer (6C) and bis-nor-seco-CB[10]. Hexamer 6C is readily available on the gram scale by a one step synthetic procedure that avoids chromatography. Hexamer 6C undergoes macrocylization with (substituted) phthalaldehydes 12, 14, 15, and 18-in 9 M H(2)SO(4) or concd HCl at room temperature to deliver monofunctionalized CB[6] derivatives 13, 16, 17, and 19-that are poised for further functionalization reactions. The kinetics of the macrocyclization reaction between hexamer and formaldehyde or phthalaldehyde depends on the presence and identity of ammonium ions as templates. p-Xylylenediammonium ion (11) which barely fits inside CB[6] sized cavities acts as a negative template which slows down transformation of 6C and paraformaldehyde into CB[6]. In contrast, 11 and hexanediammonium ion (20) act as a positive template that promotes the macrocyclization reaction between 6C and 12 to deliver (±)-21 as a key intermediate along the mechanistic pathway to CB[6] derivatives. Naphthalene-CB[6] derivative 19 which contains both fluorophore and ureidyl C═O metal-ion (e.g., Eu(3+)) binding sites forms the basis for a fluorescence turn-on assay for suitable ammonium ions (e.g., hexanediammonium ion and histamine).

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Section: Resultsmentioning

confidence: 99%

Templated Synthesis of Glycoluril Hexamer and Monofunctionalized Cucurbit[6]uril Derivatives

et al. 2011

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“…O -Phthalaldehyde derivatives with 4-bromo (B-PA) and 4-methyl (M-PA) substituents were synthesized in two steps adapted from literature procedures (see the Supporting Information). , B-PA is synthesized by tetrabenzylic bromination followed by hydrolysis of 4-bromo- o -xylene . M-PA is produced by reduction of 4-methylphthalic anhydride to the corresponding diol, followed by a Swern oxidation to give the product in high yield .…”

Section: Results and Discussionmentioning

confidence: 99%

Dynamic Covalent Macrocyclic Poly(phthalaldehyde)s: Scrambling Cyclic Homopolymer Mixtures Produces Multi-Block and Random Cyclic Copolymers

2013

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We recently reported the cationic polymerization of o-phthalaldehyde to macrocyclic poly(phthalaldehyde) polymers. Resubjecting the cyclic polymers to the polymerization conditions led to a redistribution of the polymer to a new cyclic structure consistent with thermodynamic equilibrium. We now report the synthesis of cyclic poly(phthalaldehyde) derivatives and demonstrate the scrambling of distinct homopolymer mixtures to copolymers under the cationic polymerization conditions. Homopolymer mixtures are found to rapidly redistribute, first to multiblock cyclic copolymers. With extended reaction time, random macrocyclic copolymers are obtained. Evolution of the microstructure was monitored by NMR spectroscopy, MALDI–TOF mass spectrometry, and gel permeation chromatography (GPC). The reported scrambling method leads to the rapid preparation of macrocyclic copolymers of high molecular weight with variable microstructure depending on reaction times and catalyst loadings.

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“…Nevertheless, the synthesis of substituted o ‐PA is not simple, as direct halogenation of o ‐PA is problematic. A different approach was therefore proposed to prepare 4‐chloro and 4‐bromo phthalaldehyde from 4‐chloro and 4‐bromo‐ o ‐xylene respectively‐dibromination and reaction with fuming sulfuric acid ( Scheme a) . These derivatives could both be polymerized by cationic polymerization using BF 3 ·OEt 2 at −78 °C, but could not be polymerized using anionic polymerization, as halogenated aromatics are not compatible with the typically used n BuLi.…”

Section: Functionalized Ppamentioning

confidence: 99%

Polyphthalaldehyde: Synthesis, Derivatives, and Applications

Wang

Diesendruck

2017

Macromol. Rapid Commun.

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o-Phthalaldehyde is, to this day, the only aromatic aldehyde that can be homopolymerized through chain-growth polymerization. The product, polyphthalaldehyde (PPA), is a brittle white solid, and, having a polyacetal main chain, presents the ability to depolymerize quite rapidly in the presence of an acid. This review highlights the unique polymerization chemistry of o-phthalaldehyde since its discovery over half a century ago, describing the different methods for the preparation of PPA and its derivatives, how the polymerization chemistry affects the structure and thermomechanical properties of the obtained PPA, and summarizes recent developments in PPA chemistry as a responsive material. Modern material applications such as the use of PPA as photoresists or in thermal-scanning probe lithography, as well as exploration of judiciously end-capped PPA for its use as self-immolative materials are summarized. In addition, the use of PPA blocks in copolymers is described, leading to the development of films with well-defined nanochannels or nanopores that can serve as a template for the preparation of the microorganization of nanomaterials.

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An efficient synthesis of substituted benzene-1,2-dicarboxaldehydes

Cited by 5 publications

References 17 publications

Templated Synthesis of Glycoluril Hexamer and Monofunctionalized Cucurbit[6]uril Derivatives

Templated Synthesis of Glycoluril Hexamer and Monofunctionalized Cucurbit[6]uril Derivatives

Dynamic Covalent Macrocyclic Poly(phthalaldehyde)s: Scrambling Cyclic Homopolymer Mixtures Produces Multi-Block and Random Cyclic Copolymers

Polyphthalaldehyde: Synthesis, Derivatives, and Applications

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