Hydrogen Bonds Involving the C-H Link. IV. The Effect of Solvent Association on Solubility

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

doi:10.1021/ja01278a037

Cited by 25 publications

(16 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: 55%

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: 55%

Acid-base behavior in aprotic organic solvents

Davis¹

1968

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“…We suggest that this difference may be attributed to the coordinative strength of the several ethers, since it has been shown (3) that the hydrogen-bonding capacity of trioxaündecane is greater than that of dioxahexane or dioxaoctane. We believe also that the difference in rate involves the coordinative strenth of triethyl phosphate which has been shown to have a hydrogen-bonding capacity that is comparable with the ethers (4). When this ester is added to the solution of stilbene-disodium adduct an appreciable evolution of heat is observed; the medium becomes more viscous and a colored precipitate is formed immediately.…”

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confidence: 87%

“…54.5-55.5°. The six strongest x-ray diffraction lines are [10] 4.187; [9] 4.480, 4.371; [7] 6.411; [4] Found: C, 91.4; H, 8.76. Regeneration of stilbene from the adduct.…”

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confidence: 99%

Alkylation of the Mono- And Di-Sodium Adducts of Stilbene

Reesor¹,

Smith²,

Wright³

1954

J. Org. Chem.

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This report is a continuation of the investigation into the reactions of the adducts obtained when alkali metals are treated with aryl-substituted alkenes (l), The alkene used in the present study is stilbene, the sodium adduct of which has been treated with triethyl phosphate and with alkyl halides in several reaction media.Although tetrahydrofuran has been used successfully, the most common solvent employed in formation and reaction of the adduct has been 2,5-dioxahexane (1 ,2-dimethoxyethane) (1). Now it has been found that the rate of adduct formation in the latter solvent is closely comparable with the rate in 3 ,G-dioxaoctane. Thus a 50 % yield of adduct is obtained in 20 minutes in the first of these diethers and in 23 minutes in the second, but 35 minutes is required when the stilbenedisodium adduct is prepared in 3,6,9-trioxaundecane. These yields are determined by carbonation.Previously it has been assumed that these adducts were stable in the glycol ether solvents, but we now have found that slow ether-fission does occur. In order to accentuate this tendency the stilbene-disodium adduct is prepared a t 100" in 3,G-dioxaoctane. Carbonation of an aliquot gives a 50 % yield of meso-diphenylsuccinic acid after three minutes, while five minutes after the introduction of the sodium the yield is 74 mole-per cent. However this yield decreases to 37 % after 15 minutes. After three hours a t 100" there is no evidence of stilbene-disodium adduct, but 90 % can be isolated as 1,2-diphenylethane (11). One may presume that this fission of the ether proceeds via an adduct-ether coordination compound such as I, although the possible participation of the R group must be RO H

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“…It was similar to the ice with a complex structure [11]. e interaction of hydrogen bonds in mixture increased the solubility of the solute [12,13]. e results indicated that the DMSO aqueous solution with the antifreeze effect was better than pure DMSO solutions [14].…”

Section: Introductionmentioning

confidence: 99%