Correlation of the Rates of Solvolysis of i-Butyl Fluoroformate and a Consideration of Leaving-Group Effects

Lee, Yelin; Park, Kyoung-Ho; Seong, Mi Hye; Kyong, Jin Burm; Kevill, Dennis N.

doi:10.3390/ijms12117806

Cited by 5 publications

(4 citation statements)

References 34 publications

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“…This pathway leads to a relatively low l value and a relatively high m value, such that the l/ m ratio is typically appreciably below unity ( l/m = 0.45). The l and m values of 2 in Table 4 are very similar to those for the earlier studied halogenoformate esters, which have been shown to solvolyze with the additional step of an addition–elimination pathway being rate determining (Equation (4)) and an ionization pathway (Equation (5)) [24,25,26].…”

Section: Resultssupporting

confidence: 68%

The Effect of the ortho Nitro Group in the Solvolysis of Benzyl and Benzoyl Halides

Park

Rhu

Kyong

et al. 2019

IJMS

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A kinetic study was carried out on the solvolysis of o-nitrobenzyl bromide (o-isomer, 1) and p-nitrobenzyl bromide (p-isomer, 3), and o-nitrobenzoyl chloride (o-isomer, 2) in a wide range of solvents under various temperatures. In all of the solvents without aqueous fluoroalcohol, the reactions of 1 were solvolyzed at a similar rate to those observed for 3, and the reaction rates of 2 were about ten times slower than those of the previously studied p-nitrobenzoyl chloride (p-isomer, 4). For solvolysis in aqueous fluoroalcohol, the reactivity of 2 was kinetically more reactive than 4. The l/m values of the extended Grunwald–Winstein (G–W) equation for solvolysis of 1 and 2 in solvents without fluoroalcohol content are all significantly larger than unity while those in all the fluoroalcohol solvents are less than unity. The role of the ortho-nitro group as an intramolecular nucleophilic assistant (internal nucleophile) in the solvolytic reaction of 1 and 2 was discussed. The results are also compared with those reported earlier for o-carbomethoxybenzyl bromide (5) and o-nitrobenzyl p-toluenesulfonate (7). From the product studies and the activation parameters for solvolyses of 1 and 2 in several organic hydroxylic solvents, mechanistic conclusions are drawn.

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Section: Resultssupporting

confidence: 68%

The Effect of the ortho Nitro Group in the Solvolysis of Benzyl and Benzoyl Halides

Park

Rhu

Kyong

et al. 2019

IJMS

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“…For example, HFIP and TFE have been compared with nonfluorinated alcohols such as MeOH and EtOH for their ability to influence the mechanism of solvolysis of various chloroformates and their analogue A change in the course of solvolytic mechanism was observed for certain chloroformate substrates when the fluorinated alcohols were used either as pure solvents or as aqueous binary mixtures (Scheme ). Previous studies had shown that solvolyses of phenyl chloroformate universally proceed via addition–elimination mechanisms. , Similar to phenyl chloroformate, the solvolyses of propargyl chloroformate and isobutyl fluoroformate proceeded via bimolecular addition–elimination processes across all solvents tested (MeOH, EtOH, acetone, TFE, and HFIP) and various binary mixtures. In contrast, alkenyl chloroformates such as isopropenyl chloroformate predominantly proceeded via bimolecular addition–elimination mechanisms in all solvents except for aqueous HFIP mixtures (97–70% HFIP) and 97% TFE, for which superimposed unimolecular (S N 1) type ionization pathways were suggested .…”

Section: Solvolysis Reactionsmentioning

confidence: 87%

HFIP in Organic Synthesis

et al. 2022

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1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a polar, strongly hydrogen bond-donating solvent that has found numerous uses in organic synthesis due to its ability to stabilize ionic species, transfer protons, and engage in a range of other intermolecular interactions. The use of this solvent has exponentially increased in the past decade and has become a solvent of choice in some areas, such as C–H functionalization chemistry. In this review, following a brief history of HFIP in organic synthesis and an overview of its physical properties, literature examples of organic reactions using HFIP as a solvent or an additive are presented, emphasizing the effect of solvent of each reaction.

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“…This ratio is consistent with the addition step of carbonyl-addition process being rate determining. Multiple studies contrasting other alkyl haloformate esters [46–50] show that the fluoroformates that have a stronger carbon-fluorine bond solvolyze faster than their corresponding chloroformate esters and such a high F:Cl ratio also endures in benzoyl halides [33,51,52]. …”

Section: Introductionmentioning

confidence: 99%

Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters

D’Souza

Givens

Lorchak

et al. 2013

IJMS

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At 25.0 °C the specific rates of solvolysis for allyl and vinyl chloroformates have been determined in a wide mix of pure and aqueous organic mixtures. In all the solvents studied, vinyl chloroformate was found to react significantly faster than allyl chloroformate. Multiple correlation analyses of these rates are completed using the extended (two-term) Grunwald-Winstein equation with incorporation of literature values for solvent nucleophilicity (NT) and solvent ionizing power (YCl). Both substrates were found to solvolyze by similar dual bimolecular carbonyl-addition and unimolecular ionization channels, each heavily dependent upon the solvents nucleophilicity and ionizing ability.

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Correlation of the Rates of Solvolysis of i-Butyl Fluoroformate and a Consideration of Leaving-Group Effects

Cited by 5 publications

References 34 publications

The Effect of the ortho Nitro Group in the Solvolysis of Benzyl and Benzoyl Halides

The Effect of the ortho Nitro Group in the Solvolysis of Benzyl and Benzoyl Halides

HFIP in Organic Synthesis

Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters

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