The cleavage of ethers, and the dehydration of alcohols, by boron trifluoride

Mooney, E.F.; Qaseem, M.A.

doi:10.1039/c19670000230

Cited by 4 publications

(2 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The ether bond on the polymer chain is most likely due to the etherification reaction between hydroxyl end groups of two polymer chains (as shown Scheme ) because it is well known that etherification reactions of primary alcohols have an S N 2 mechanism catalyzed by strong acids. BF 3 is a strong Lewis acid and is also recognized as a strong dehydration agent,26, 27 making etherification reactions very likely.…”

Section: Resultsmentioning

confidence: 99%

Mechanistic study of boron trifluoride catalyzed ε‐caprolactone polymerization in the presence of glycerol

Jiang

Walker

Jones

et al. 2006

J of Applied Polymer Sci

View full text Add to dashboard Cite

Boron trifluoride catalyzed e-caprolactone polymerization in the presence of glycerol can produce poly(e-caprolactone) with a high weight-average molecular weight and a broad molecular weight distribution. This article reports an investigation of the polymerization mechanism to determine the formation of these molecular weight features through a study of the polymerization kinetics and the molecular structure with NMR. The polymerization proceeds via an activated monomer mechanism, resulting in polymer molecules with hydroxyl chain ends. The broad molecular weight distribution can be attributed to the etherification reactions between hydroxyl chain ends.

show abstract

Section: Resultsmentioning

confidence: 99%

Mechanistic study of boron trifluoride catalyzed ε‐caprolactone polymerization in the presence of glycerol

Jiang

Walker

Jones

et al. 2006

J of Applied Polymer Sci

View full text Add to dashboard Cite

show abstract

“…From the perspective of its reaction in the gas phase, representative examples of such studies include its reaction with (i) catecholate and related anions [2], (ii) the gas phase ion chemistry of BF 3 /CH 4 mixtures [3], and (iii) the reaction of ammonia and methylamine [4,5]. From the perspective of the reactions of BF 3 in solution (where it is often used in the form of its etherate adduct), it has been shown to play a role in facilitating various polymerization reactions [6][7][8], dehydration reactions of alcohols [9,10], esterification reactions [11][12][13], alkylation reactions [14,15], as well as the synthesis of syn-fluorohydrins from epoxides [16]. It has also been reported that triplet diphenylcarbene could be inserted into the B-F bond of BF 3 [17].…”

Section: Introductionmentioning

confidence: 99%

A Systematic Exploration of B–F Bond Dissociation Enthalpies of Fluoroborane-Type Molecules at the CCSD(T)/CBS Level

O'Reilly

Karton

2023

Molecules

View full text Add to dashboard Cite

Fluoroborane-type molecules (R1R2B–F) are of interest in synthetic chemistry, but to date, apart from a handful of small species (such as H2BF, HBF2, and BF3), little is known concerning the effect of substituents in governing the strength of the B–F bonds of such species toward homolytic dissociation in the gas phase. In this study, we have calculated the bond dissociation enthalpies (BDEs) of thirty unique B–F bonds at the CCSD(T)/CBS level using the high-level W1w thermochemical protocol. The B–F bonds in all species considered are very strong, ranging from 545.9 kJ mol−1 in (H2B)2B–F to 729.2 kJ mol−1 HBF2. Nevertheless, these BDEs still vary over a wide range of 183.3 kJ mol−1. The structural properties that affect the BDEs are examined in detail, and the homolytic BDEs are rationalized based on molecule stabilization enthalpies and radical stabilization enthalpies. Since polar B–F bonds may represent a challenging test case for density functional theory (DFT) methods, we proceed to examine the performance of a wide range of DFT methods across the rungs of Jacob′s Ladder for their ability to compute B–F BDEs. We find that only a handful of DFT methods can reproduce the CCSD(T)/CBS BDEs with mean absolute deviations (MADs) below the threshold of chemical accuracy (i.e., with average deviations below 4.2 kJ mol−1). The only functionals capable of achieving this feat were (MADs given in parentheses): ωB97M-V (4.0), BMK (3.5), DSD-BLYP (3.8), and DSD-PBEB95 (1.8 kJ mol−1).

show abstract

Synthesen und Strukturen von Aluminium‐Fluor‐Sauerstoff‐Clustern

Waezsada¹,

Liu²,

Barnes³

et al. 1997

Angewandte Chemie

View full text Add to dashboard Cite

Je nach Größe der Substituenten R und R′ erhält man beim Umkristallisieren von (2,6‐R2C6H3)[Si(R′)‐Me2]NAlF2 · THF nur die Ausgangsverbindungen zurück ‐ oder aber größere Cluster. Deren Ecken sind mit Aluminiumatomen, die Kanten mit Fluoratomen besetzt (Teil einer Clusterstruktur im Kristall siehe rechts). Im Zentrum des Tetrakishexaeders befindet sich, umgeben von sechs Aluminiumatomen, ein Sauerstoffatom; dieser Strukturtyp war bei Molekülverbindungen bisher nur von d‐ und f‐Elementen bekannt.magnified image

show abstract

The cleavage of ethers, and the dehydration of alcohols, by boron trifluoride

Cited by 4 publications

References 0 publications

Mechanistic study of boron trifluoride catalyzed ε‐caprolactone polymerization in the presence of glycerol

Mechanistic study of boron trifluoride catalyzed ε‐caprolactone polymerization in the presence of glycerol

A Systematic Exploration of B–F Bond Dissociation Enthalpies of Fluoroborane-Type Molecules at the CCSD(T)/CBS Level

Synthesen und Strukturen von Aluminium‐Fluor‐Sauerstoff‐Clustern

Contact Info

Product

Resources

About