A correlation of the ionization energies of water and ethers with the polar and inductive substituent constants

Levitt, Barbara W.; Levitt, L. S.

doi:10.1007/bf01897950

Cited by 20 publications

(6 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Recently, the most extensive work along these lines has been done by Levitt, Levitt, Widing, and Parkanyi who have linearly correlated the first gasphase ionization potentials of seventeen series of aliphatic organic molecules with alkyl cr*(R) and CTI(R) values [9]. We have also found good results for aldehydes [5], Cu and Cr acetylacetonates [10,13], and benzene Cr tricarbonyls [13], as well as for benzene [14], pyridine and thiophene derivatives [15].…”

Section: Molecular Ionization Potentialsmentioning

confidence: 65%

“…Since the G parameters arising from LFER analyses are ultimately a function of the interactions within molecules, it is reasonable to predict that they will be related to spectroscopic data [7], dipole moments [2], bond energies [2], ionization potentials [8][9][10], and many other physical properties [2,11,12].…”

Section: Some Of the New Ci(r) Values Have Recentlymentioning

confidence: 99%

See 1 more Smart Citation

The Alkyl Inductive Effect, II Theoretical Calculation of Inductive Parameters

Widingand

Levitt

1979

Zeitschrift Für Naturforschung B

View full text Add to dashboard Cite

AbstractThree models of alkyl groups, “derealization”, “through-the-bond”, and “electric field” models, are presented, all of which enable the calculation of σI (R) from first principles, and excellent agreement is demonstrated for the calculated and experimental values of σI (R) . For the “delocalization” model it is found that - σI (R) = 0.0455 + 0.0232(1-1/n), where n is the number of C atoms in an n-alkyl group, and for an infinite C-chain R group, σI( R∞) is - 0.0687, identical to the value found b y a different method in Part I of this series. The “through-the-bond” model gives - σI(R) = - 0.0559 +, where Ci is the number of C-atoms in the i th position from X in RX; and for the “electric field” model, we obtain - σI(R) = 0.0463 + 0.0102 , where di is the calculated distance from C1 to Cn in the most probable conformation of the R-group. It is concluded that Taft's σI(R) values have a real significance whether or not the physical and chemical effects of alkyl substitution reside ultimately in an internal induction mechanism, or in alkyl group polarization by charged centers in the molecule, or a combination of the two.

show abstract

Section: Molecular Ionization Potentialsmentioning

confidence: 65%

Section: Some Of the New Ci(r) Values Have Recentlymentioning

confidence: 99%

The Alkyl Inductive Effect, II Theoretical Calculation of Inductive Parameters

Widingand

Levitt

1979

Zeitschrift Für Naturforschung B

View full text Add to dashboard Cite

show abstract

“…The mesitoic acid was extracted from the ether layer with two 25-ml portions of saturated sodium bicarbonate solution and one 25-ml portion of a 10% sodium hydroxide solution. The ether layer was dried over anhydrous magnesium sulfate and filtered, and the solvent was evaporated to yield Received August 16,1976 The recent interest accorded the development of highly hindered hydride reagents capable of stereoselective reduction of ketones to afford one diastereomer preferentially1™5 prompts this discussion of an important factor which is frequently neglected but which subtly affects the product profile of such reductions.6 This effect involves the conformational equilibria present in mobile ketones which is often at least partly responsible for decreasing the apparent stereoselectivity of hydride attacks.…”

Section: Methodsmentioning

confidence: 99%

A general procedure for the base-promoted hydrolysis of hindered esters at ambient temperatures

Gassman¹,

Schenk²

1977

J. Org. Chem.

180

112

View full text Add to dashboard Cite

Recently, we reported that essentially "anhydrous hydroxide" was an excellent reagent for the hydrolysis of tertiary amides at ambient temperatures.1 This reagent was generated via the reaction of 2 equiv of potassium tert-butoxide with 1 equiv of water.2 Mechanistically, it appeared that the relatively unsolvated hydroxide added to the tertiary amide, 1, to produce 2. Removal of a hydroxylic proton from 2 would then produce the dianion, 3. Fragmentation of 3 then produced the most stable pair of anions, which in this case was 4 and 5. Utilizing this concept, a series of tertiary amides was

show abstract

“…(I= 10.714 (6), b = 11.761 (7), c=9.046(4) A, a=92.57(1), 8=71.95(2), Photo-CIDNP in the Vacuum-UV: Di-tert-butyl Ether and 2,"2,5,5-Tetramethyltetrahydrofuran in Aqueous Solution** By Knut Hildenbrand. Heinz-Peter Schuchrnann, and Clernens von Sonntag*…”

mentioning

confidence: 99%

Photo‐CIDNP in the Vacuum‐UV: Di‐tert‐butyl Ether and 2,2,5,5‐Tetramethyltetrahydrofuran in Aqueous Solution

Hildenbrand

Schuchmann

Sonntag

1987

Angew. Chem. Int. Ed. Engl.

View full text Add to dashboard Cite

Homolytic bond cleavages and photoionization occur upon irradiation of the title compounds in O2‐free D2O. In order to monitor the photochemical reactions spectroscopically, photo‐CIDNP experiments with laser excitation were carried out (ArF‐excimer laser, λ = 193 nm). In the case of tBu2O the products CH3D and C2H6 could be detected. This finding enables formulation of a reaction sequence, which starts with formation of the radical cation tBu2O⊙ ⊕. Non‐aqueous solutions of the title compounds and aqueous solutions of primary, secondary and monotertiary ethers showed no polarized NMR signals upon illumination.

show abstract

A correlation of the ionization energies of water and ethers with the polar and inductive substituent constants

Cited by 20 publications

References 0 publications

The Alkyl Inductive Effect, II Theoretical Calculation of Inductive Parameters

The Alkyl Inductive Effect, II Theoretical Calculation of Inductive Parameters

A general procedure for the base-promoted hydrolysis of hindered esters at ambient temperatures

Photo‐CIDNP in the Vacuum‐UV: Di‐tert‐butyl Ether and 2,2,5,5‐Tetramethyltetrahydrofuran in Aqueous Solution

Contact Info

Product

Resources

About