Hydrogen Bonds Involving the C-H Link. The Solubility of Haloforms in Donor Solvents

Zellhoefer, G. F.; Copley, M.; Marvel, C. S.

doi:10.1021/ja01273a018

Cited by 60 publications

(26 citation statements)

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“…" One of the strong indications that hydrogen bonding must occur in the association of bases with chloroform or other C-H containing molecules comes from the comprehensive solubihty studies of Zellhoefer, Copley, and Marvel. For example, they found that the solvent capacities of halomethanes for basic molecules follow the order CH3X < CH2X2 < CHX3 » CX4, where X = C1 or F. The many solutes tested included ethers, thioethers, esters, ketones, and primary and tertiary amines. The failure of alcohols to associate with chloroform was attributed to their strong tendency toward intermolecular self-association [105,106]. The order given above is exactly that predicted on postulating that C-H hydrogen is involved in the bonding and that its activity is progressively enhanced on continued replacement of methane hydrogens by halogen.…”

Section: Carbon Tetrachloride As An Electron Acceptorsupporting

confidence: 57%

Acid-base behavior in aprotic organic solvents

Davis¹

1968

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Butyl hydroperoxide and deuteroperoxide. Deuterium isotope effects on hydrogen bonding by Br0nsted acids 40 4.3. Hydrogen-bonded ion pairs 41 4.3.1. Conductance 41 a. Walden's work 42 b. Wynne-Jones' postulate 42 c. Investigations of Kraus, Fuoss, and associates... 43 d. Summary 45 4.3.2. Dielectric constants 46 a. Dielectric polarization of substituted ammonium picrates and halides in benzene 46 b. Dielectric polarization of other acid-base complexes in benzene 47 4.3.3. CoUigative properties 49 a. Cryoscopy 50 Page b. The differential vapor pressure (DVP) method... 51 104 4.5.6. Homoconjugation of other organic and inorganic acids a. Perchloric acid 105 b. Other acids 105 4.5.7. Heteroconjugate anions 105 a. Chemical behavior 105 b. Physical measurements 108 4.6. Concluding discussion of hydrogen bonding 112 4.6.1. Definition of a hydrogen bond. Systems which form hydrogen bonds 112 4.6.2! Some recent concepts of hydrogen bonding 113 5. Acidity and basicity scales in aprotic organic solvents... 114 5.1. Early attempts to determine relative acidities 114 5.2. Log Kbha scales of acidity and basicity 115 5.3. Methods used in determining values of log A^bha 116 5.4. Tables of log ^bha, and AS obtained using aprotic solvents 118 5.4.1. Aromatic and substituted aromatic hydrocarbons 118 a. Benzene 118 b. Anisole and chlorobenzene 126 5.4.3. Carbon tetrachloride 126 5.4.4. Chloroform 128 5.4.5. Miscellaneous aprotic solvents 129 6. Acid-base titrations in completely aprotic solvents 133 6.1. Introduction 133 6.2. Titrations with indicator dyes in completely aprotic solvents 133 6.3. Instrumental procedures for detecting end-points in completely aprotic solvents 133 6.3.1. Conductance titrations 133 iv Contents -Continued Page 6.3.2. Dielectrometric titrations 133 6.3.3. Photometric titrations 134 6.3.4. Thermometric titrations 135 6.3.5. Titrations by the DVP method 135 6.3.6. Cryoscopic titrations 135 6.3.7. Other possible instrumental procedures 135 a. Refractive index 135 b. Density 135 c. Optical rotation 135 6.4. Reference acids and bases for aprotic organic solvents 135 6.4.1. Acids 135 a. Hydrogen chloride 135

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Section: Carbon Tetrachloride As An Electron Acceptorsupporting

confidence: 57%

Acid-base behavior in aprotic organic solvents

Davis¹

1968

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“…A number of the compounds contain acidic hydrogen. As early as 1938 it was shown that dichloromonofluoromethane produced negative deviations from Raoult's law (increased solubility) in hydrogen bond acceptor solvents [ 5 ] . Since olive oil is composed primarily of a long-chain ester, it is to be expected that the solubility of halogenated hydrocarbon compounds in an anaesthetic phase will exhibit some nonideal behaviour.…”

Section: The Lipid Solubility Theory Of Anaesthesiamentioning

confidence: 99%

A quantitative interpretation of phase effects in anaesthesia

Davies¹,

Bagnall²,

Jones³

2009

Int. J. Quantum Chem.

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lnipwiiil Clicwiicd Iiiclir.strie,r Lld., Pliar.riiac.c~rtricrrls Division, A Ir/er.lc>v P a d , Macdesfield.Chesli ire. England AbstractThe anaesthetic potencies of 45 halogenated hydrocarbons have been fitted to a simple phase distribution model. The model approximates the activity coefficient at infinite dilution as a function of the dominant intermolecular interactions in the given phase. For a series of halogenated hydrocarbons. this function reduces to an empiric balance between the compounds' van der Waal and hydrogen bond donor properties. The strength of the hydrogen bond interaction of CHF, with the anaesthetic phase is estimated to be 1.5 f 0.2 kcal. assuming a 1: I interaction. This is in agreement with theoretical and observed estimates of weak C ~ -H . . . . 0 bonding. It is suggested that theoretical estimates of hydrogen bond donor and acceptor properties in compounds may have a general role to play in evaluating nonspecific biological processes.

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“…14 In addition, data on solubility and heats of mixing had proved the presence of hydrogen bonds in solutions of chlorinated methane and some organics, which can offer acceptor atoms to form hydrogen bonds, 15,16 such as esters, ketones, and alcohols. For polymer solutions like polyether and chlorinated methane, thermodynamic properties were measured using vapor pressure, heat, and volume change on mixing, and revealed significant deviation from normal solution behavior, 17,18 because of the formation of associating molecules.…”

Section: Introductionmentioning

confidence: 99%