The Dissociation of 2,2,2-Trinitroethanol in Aqueous Solution<sup>1</sup>

Reinhart, Joan; Meitner, John G.; Dolah, Robert W. Van

doi:10.1021/ja01607a093

Cited by 3 publications

(3 citation statements)

References 1 publication

(1 reference statement)

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“…The acidities of the nitroalcohols have been discussed in the literature (116,162), and values of the dissociation constants determined by Hall (71) are given in Table XXX. Hall states that a dilute solution of trinitroethanol in 0.1 V NaOH has the spectrum and molar extinction coefficient of trinitromethyl anion, showing that it is completely ionized (N02)8CCH20H (N02),C-+ CH2(OH), + H + and suggests that the reason the preparation of 1substituted trinitroethanols from nitroform and acetaldehyde, cyclobutanone, or acetone has not been successful is that these alcohols are too highly dissociated in aqueous solution.…”

Section: Physical Propertiesmentioning

confidence: 99%

Chemistry of the Aliphatic Polynitro Compounds and Their Derivatives

Noble¹,

Borgardt²,

Reed³

1964

Chem. Rev.

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CiHiOCOCHaCOOH70% HNOi CaHiOCOC(NOi)iH n»n 1.4321 11 98 CiHiOCOCH(CHi)COOH 70% HNOi CaHiOCOC(NOa)aCHi 45(0.1); 7i»D 1.4327 17 98 CaHiOCOCH(CaHí)COOH 70% HNOi CaHiOCOC(NOa)aCaHi 50(0.1); n"D 1.4340 17 98 CiH60COCH(t¡-C.Hi)COOH 70% HNOi CaHsOCOC(NOa)aC,Hi 60(0.1); n»D 1.4393 8 Salts op Polynitro Compounds and Halogen Derivatives Nitronate salt Ci NaO,N=CH(NOi) KO,N=CH(NO,) AgO,N=CH(NO,) (0,N),C=N0, "C«HiN +=N C, Na+[C(NO,),CNJ-K+1C(N0,),CN]" Ag + [C

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Section: Physical Propertiesmentioning

confidence: 99%

Chemistry of the Aliphatic Polynitro Compounds and Their Derivatives

Noble¹,

Borgardt²,

Reed³

1964

Chem. Rev.

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“…The geometry optimization in Spartan'18 for this compound's anion both in vacuum and within the aqueous solvent model yielded an abnormally long C−C bond length, suggesting that the anion is not stable. Such instability has been confirmed by Reinhard et al 22 who asserted that the trinitroethoxide anion will convert mostly to the favored nitroformate ion and formaldehyde:…”

Section: ■ Methodsmentioning

confidence: 82%

“…The geometry optimization in Spartan’18 for this compound’s anion both in vacuum and within the aqueous solvent model yielded an abnormally long C–C bond length, suggesting that the anion is not stable. Such instability has been confirmed by Reinhard et al who asserted that the trinitroethoxide anion will convert mostly to the favored nitroformate ion and formaldehyde: Because the dissociation process and the anion of 2,2,2-trinitroethanol differ from those of the other saturated alcohols, this compound was excluded from the QSAR models.…”

Section: Methodsmentioning

confidence: 93%

Computational Estimation of the Aqueous Acidities of Alcohols, Hydrates, and Enols

Baldasare

Seybold

2021

J. Phys. Chem. A

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Alcohols are ubiquitous chemical species, and their acid dissociation constants are critical properties in many applications. It is useful to have a reliable and convenient computational procedure for estimating these acidities. Here we describe a quantitative structure–activity relationship (QSAR) for the pK as of alcohols in aqueous solution employing density functional theory computations at the B3LYP/6-31+G(d,p) level with the CPCM implicit solvent model for the aqueous solutions. For the pK as, the energy difference in solution between the parent compound and the anion, ΔE(H2O), was used as a single descriptor. High quality QSAR equations are obtained both for the gas-phase Gibbs energy changes (ΔG r 0s, R 2 = 0.9764) and the aqueous pK as (R 2 = 0.9594). It is shown that the aqueous equation can also be used to estimate the pK as of fluorinated alcohols, hydrates formed by carbonyl compounds in aqueous solution, and enols that appear as minor components in keto–enol equilibria.

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