Energetics of the C−Cl Bond in CH3CH(Cl)COOH. Enthalpy of Formation of (S)-(−)-2-Chloropropionic Acid and of the 1-Carboxyethyl Radical,

Lagoa, Ana L. C.; Diogo, Hermı́nio P.; Piedade, Manuel E. Minas da; Amaral, Luı́sa M.P.F.; Guedes, Rita C.; Cabral, Benedito J. Costa; Kulikov, D. V.; Verevkin, Sergey P.; Siedler, Michael; Epple, Matthias

doi:10.1021/jp020412p

Cited by 8 publications

(10 citation statements)

References 43 publications

(52 reference statements)

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“…This pathway is less likely to operate on thermodynamic grounds because the Ti–Cl bond is substantially stronger than the C–Cl bond α to a carbonyl group (typically <80 kcal/mol). 39…”

Section: Resultsmentioning

confidence: 99%

Ti-Catalyzed Radical Alkylation of Secondary and Tertiary Alkyl Chlorides Using Michael Acceptors

Wei

et al. 2018

J. Am. Chem. Soc.

111

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Alkyl chlorides are common functional groups in synthetic organic chemistry. However, the engagement of unactivated alkyl chlorides, especially tertiary alkyl chlorides, in transition-metal-catalyzed C–C bond formation remains challenging. Herein, we describe the development of a TiIII-catalyzed radical addition of 2° and 3° alkyl chlorides to electron-deficient alkenes. Mechanistic data are consistent with inner-sphere activation of the C–Cl bond featuring TiIII-mediated Cl atom abstraction. Evidence suggests that the active TiIII catalyst is generated from the TiIV precursor in a Lewis-acid-assisted electron transfer process.

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“…This pathway is less likely to operate on thermodynamic grounds because the Ti–Cl bond is substantially stronger than the C–Cl bond α to a carbonyl group (typically <80 kcal/mol). 39…”

Section: Resultsmentioning

confidence: 99%

Ti-Catalyzed Radical Alkylation of Secondary and Tertiary Alkyl Chlorides Using Michael Acceptors

Wei

et al. 2018

J. Am. Chem. Soc.

111

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“…For CH 3 CHClCOOH and CH 3 CHBrCOOH, mutual effects on the bond strength and stability of the two different functional groups (COOH and C–X) have been reported previously. The dissociation enthalpy for the C–Cl bond of CH 3 CHClCOOH is found to be ∼297 kJ mol –1 , 54 kJ mol –1 lower than that of CH 3 CH 2 Cl . The PKa° values for CH 3 CH 2 COOH, CH 3 CHBrCOOH, and BrCH 2 CH 2 COOH in aqueous KCl solutions have been reported to be 4.89, 3.01, and 4.07, respectively, showing the deprotonating tendency .…”

Section: Introductionmentioning

confidence: 94%

“…The dissociation enthalpy for the C−Cl bond of CH 3 CHClCOOH is found to be ∼297 kJ mol −1 , 54 kJ mol −1 lower than that of CH 3 CH 2 Cl. 7 The PKa°values for CH 3 CH 2 COOH, CH 3 CHBrCOOH, and BrCH 2 CH 2 COOH in aqueous KCl solutions have been reported to be 4.89, 3.01, and 4.07, respectively, showing the deprotonating tendency. 8 This result indicates that the substituted bromine, an electronwithdrawing atom, assists in the O−H dissociation and therefore increases the acidity.…”

Section: ■ Introductionmentioning

confidence: 99%

Surface Reaction Mechanisms: 3-Bromopropanoic and 2-Bromopropanoic Acids on Cu(100) and O/Cu(100)

Lin

Liu

et al. 2021

J. Phys. Chem. C

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X-ray photoelectron spectroscopy, reflection–absorption infrared spectroscopy, temperature-programmed reaction/desorption, and density functional theory calculations have been performed to investigate the reaction mechanisms and bonding structures of 3- and 2-bromopropanoic acids on Cu(100) and oxygen-precovered Cu(100). On Cu(100), the bond dissociation of C–Br and O–H in BrCH2CH2COOH is accelerated, occurring at 110 K, as compared to the monofunctional molecules. CH2CH2COOH, CH2CH2COO, and CH3CH2COO from the BrCH2CH2COOH reaction coexist on Cu(100) at 180 K. The CH2CH2COOH is not detected at 250 K, and CH3CH2COO predominates at 320 K. The CH2CH2COO is strongly bonded to the surface via the COO and terminal CH2 groups. In the presence of oxygen atoms on Cu(100), the C–Br scission is suppressed and BrCH2CH2COO is found to be predominant at 150 K. CH2CH2COO begins to form at 200 K and further reacts to produce CH3CH2COO and CH2CHCOO at 320 K through disproportionation or sequential H loss at 2CH2 and hydrogenation at 3CH2. The reaction of CH3CHBrCOOH on Cu(100) also generates CH3CH2COO at 300 K via CH3CHCOOH and CH3CHCOO. The latter species could attach to the surface via the CHCOO or COO group. On O/Cu(100), dissociation of CH3CHBrCOOH forms CH3CHCOO between 200 and 400 K. CH3CHCOO on O/Cu(100) dehydrogenates, at 450 K, into CH2CHCOO. A halogen (Cl and Br) effect is observed in the adsorption structure and reaction path of CH3CHCOO on O/Cu(100).

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“…Further collective sources have been used to complement—and compare—the experimental data [ 8 , 14 , 15 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 ]. In addition, vapour-pressure data have been published specifically for various saturated and unsaturated hydrocarbons [ 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 ], alcohols [ 53 , 54 , 55 , 56 , 57 , 58 ], phenols [ 59 , 60 ], alkyl- and arylethers [ 61 , 62 , 63 , 64 ], acetals [ 65 , 66 ], carboxylic acids [ 67 , 68 , 69 , 70 , 71 ], carboxylic halides […”

Section: Sources Of Vapor-pressure Datamentioning

confidence: 99%

Calculation of the Vapour Pressure of Organic Molecules by Means of a Group-Additivity Method and Their Resultant Gibbs Free Energy and Entropy of Vaporization at 298.15 K

Naef

Acree

2021

Molecules

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The calculation of the vapour pressure of organic molecules at 298.15 K is presented using a commonly applicable computer algorithm based on the group-additivity method. The basic principle of this method rests on the complete breakdown of the molecules into their constituting atoms, further characterized by their immediate neighbour atoms. The group contributions are calculated by means of a fast Gauss–Seidel fitting algorithm using the experimental data of 2036 molecules from literature. A ten-fold cross-validation procedure has been carried out to test the applicability of this method, which confirmed excellent quality for the prediction of the vapour pressure, expressed in log(pa), with a cross-validated correlation coefficient Q2 of 0.9938 and a standard deviation σ of 0.26. Based on these data, the molecules’ standard Gibbs free energy ΔG°vap has been calculated. Furthermore, using their enthalpies of vaporization, predicted by an analogous group-additivity approach published earlier, the standard entropy of vaporization ΔS°vap has been determined and compared with experimental data of 1129 molecules, exhibiting excellent conformance with a correlation coefficient R2 of 0.9598, a standard error σ of 8.14 J/mol/ K and a medium absolute deviation of 4.68%.

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Energetics of the C−Cl Bond in CH₃CH(Cl)COOH. Enthalpy of Formation of (S)-(−)-2-Chloropropionic Acid and of the 1-Carboxyethyl Radical^,

Cited by 8 publications

References 43 publications

Ti-Catalyzed Radical Alkylation of Secondary and Tertiary Alkyl Chlorides Using Michael Acceptors

Ti-Catalyzed Radical Alkylation of Secondary and Tertiary Alkyl Chlorides Using Michael Acceptors

Surface Reaction Mechanisms: 3-Bromopropanoic and 2-Bromopropanoic Acids on Cu(100) and O/Cu(100)

Calculation of the Vapour Pressure of Organic Molecules by Means of a Group-Additivity Method and Their Resultant Gibbs Free Energy and Entropy of Vaporization at 298.15 K

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