Utilization of the hydroxyalkylation reaction to prepare bis(benzocrown ethers)

Zielinski, Matthew E.; Tracy, Adam F.; Klumpp, Douglas A.

doi:10.1016/j.tetlet.2012.01.049

Cited by 12 publications

(1 citation statement)

References 21 publications

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“…Depending on the acid strength and the nature of the carbonyl component monoprotonation, multiple protonation or only hydrogen-bond formation is possible. It is believed that α-diketones are diprotonated in the medium of superacids. ,,,− …”

Section: Resultsmentioning

confidence: 99%

High-T_g Functional Aromatic Polymers

et al. 2015

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A novel series of linear, high-molecular-weight polymers and copolymers were synthesized by one-pot, metal-free superacid-catalyzed polymerization of aliphatic 1,2-diketones (2,3-butanedione (1a), 2,3-hexadione (1b), 3,4-hexadione (1c), 2,3-butanedione monoxime (1d), pyruvic acid (1e), 1,4-dibromo-2,3-butanedione (1f), 2-bromopyruvic acid (1g), and methyl-3,3,3-trifluoropyruvate (1h) with linear, nonactivated, multiring aromatic hydrocarbons terphenyl (A), biphenyl (B), fluorene (C), and N-ethyl carbazole (D). Depending on the reaction system, the polymerizations were carried out as stoichiometric or non stoichiometric, with direct or inverse monomer addition. Copolymers were obtained by polymerization of 1,2-diketones with a mixture of aromatic hydrocarbons. In the course of the polymerization only one carbonyl group of a 1,2-diketone reacts to form C−C bonds with aromatic fragments while the other functional groups (including the second carbonyl group) are incorporated unchanged into polymer chain. The polymerizations performed at room temperature in the Brønsted superacid CF 3 SO 3 H (TFSA) and in a mixture of TFSA with methylene chloride or trifluoroacetic acid (TFA) tolerant of carbonyl, acetyl, N-oxime, carboxy, methoxy, and bromomethyl groups. The polymers obtained were soluble in most common organic solvents, and flexible transparent, colorless films could be cast from the solutions. 1 H and 13 C NMR analyses of the polymers synthesized revealed high regio-selectivity of the polymerizations and yielded linear structures with para-substitution in the phenylene fragments of the main chains. An electron affinity (EA) of the carbonyl component and the heterolytic C−O bond dissociation energy (DE) in carbinol 3 (correlating with the activation energy of carbocation 4 formation) have been used to rationalize the reactivity of carbonyl components. The calculations show the following reactivity order of the diketones. 1f > 1g ≈ 1e> 1a> 1d > 1h> 1b>1c which is totally in agreement with the experimental data. The new functional polymers obtained demonstrate good processability, high T g and thermal stability. Unexpected white light emission was observed for polymer 2gA.

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Section: Resultsmentioning

confidence: 99%

High-T_g Functional Aromatic Polymers

et al. 2015

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ChemInform Abstract: Utilization of the Hydroxyalkylation Reaction to Prepare Bis(benzocrown Ethers).

2012

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Silver(I)‐Catalyzed Syntheses of Triarylmethanes (TRAMs)

Bouteille,

Davies,

Labourdette

et al. 2024

Eur J Org Chem

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The synthesis of triarylmethanes was evaluated in the presence of various Brønsted and Lewis acids under the same stoichiometric conditions. An efficient silver(I)‐catalyzed synthesis of triarylmethanes is reported. The reaction offers low catalyst loadings and quasi‐stoichiometric conditions (1–1.2 equiv. of electrophile) to access to symmetrical and unsymmetrical TRAMs in moderate to excellent yields (35 examples). Broad substrate scope was observed, including compatibility with ester and cyano groups.

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Utilization of the hydroxyalkylation reaction to prepare bis(benzocrown ethers)

Cited by 12 publications

References 21 publications

High-T_g Functional Aromatic Polymers

High-T_g Functional Aromatic Polymers

ChemInform Abstract: Utilization of the Hydroxyalkylation Reaction to Prepare Bis(benzocrown Ethers).

Silver(I)‐Catalyzed Syntheses of Triarylmethanes (TRAMs)

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Utilization of the hydroxyalkylation reaction to prepare bis(benzocrown ethers)

Cited by 12 publications

References 21 publications

High-Tg Functional Aromatic Polymers

High-Tg Functional Aromatic Polymers

ChemInform Abstract: Utilization of the Hydroxyalkylation Reaction to Prepare Bis(benzocrown Ethers).

Silver(I)‐Catalyzed Syntheses of Triarylmethanes (TRAMs)

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High-T_g Functional Aromatic Polymers

High-T_g Functional Aromatic Polymers