Reactions of Ethylenimines. II. With Thiophenol. A Rate Study

Meguerian, G. H.; Clapp, Leallyn B.

doi:10.1021/ja01149a062

Cited by 22 publications

(5 citation statements)

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“…When acetoacetanilide as a model compound was heated directly in a Claisen flask at 180-200°u nder reduced pressure, a 60% yield of aniline was obtained along with a small amount of acetone and sym-diphenylurea via equation (1). The temperature was kept at the stated degree because acetoacetanilide decomposes at about 180°.…”

Section: R-nh-co-chscoch -mentioning

confidence: 99%

“…It is noteworthy that the three aliphatic jV-substituted acetoacetamides also give the corresponding aliphatic isocyanates in somewhat reduced yields. In the case of A-cyclohexylacetoacetamide, 0.4 g. of cyclohexene is formed by the above mentioned thermal decom-R-NH, + 0=C=CH COCH, (1) R-N=C=0 + CH,COCHi (2) position along with 0.9 g. of cyclohexyl isocyanate and 0.4 g. of acetone. with a small amount of acetone under the same condition, and p-nitrophenyl isocyanate and pcarboethoxyphenyl isocyanate, though expected theoretically, could not be obtained, presumably because of technical deficiencies.…”

Section: R-nh-co-chscoch -mentioning

confidence: 99%

See 1 more Smart Citation

Novel Method for the Preparation of Organic Isocyanates¹

Mukaiyama¹,

Tokizawa²,

Nohira³

et al. 1961

J. Org. Chem.

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Section: R-nh-co-chscoch -mentioning

confidence: 99%

Section: R-nh-co-chscoch -mentioning

confidence: 99%

Novel Method for the Preparation of Organic Isocyanates¹

Mukaiyama¹,

Tokizawa²,

Nohira³

et al. 1961

J. Org. Chem.

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“…6 On the basis of these data plus elemental analysis, the formula C4H5? Similarly, A-1 gave A-2 on solution in excess boiling water and very slow cooling.…”

Section: I11mentioning

confidence: 99%

The Reaction of Guanazole and Diformylhydrazine¹

Hauser¹,

Logush²

1964

J. Org. Chem.

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972 NOTESVOL. 29 deuterium isotope effect, I c~~o / k m~, is, therefore, 0.45, a value similar to those found for related reactionsI4 and nearly identical with the value found by DeWolfe and Jensen for the hydrolysis of ethyl orthobenzoate.1° This solvent deuterium isotope effect is consistent with either pre-equilibrium substrate protonation or with general acid catalysis by the hydrated proton, provided that, in the transition state, the proton is largely transferred to the substrate.I5 This condition appears t o be met in the present case since Kwart and Price have observed a Br@nsted a value of 0.74 for general acid catalysis of methyl orthobenzoate hydroly~is.~ The observation that methyl orthobenzoate hydrolysis is subject to general acid catalysis9~1O suggests, but does not prove, that the specific acid-catalyzed reaction is, in fact, general acid catalysis by the hydrated proton. ExperimentalMaterials.-Methyl orthobenzoate was prepared from benzotrichloride as previously described.16 Other reagents were recrystallized or redistilled before use. Distilled water was employed throughout.Kinetic measurements were carried out spectrophotometrically with a Zeiss PMQ I1 spectrophotometer equipped with a thermostated cell holder as previously described.l'*lB At the conclusion of several runs involving the hydrolysis df methyl orthobenzoate in the presence of hydroxylamine or semicarbazide, the amount of methyl benzoate produced was determined by the ferric chloridehydroxylamine method of Lipmann and Tuttle.19 Ionic strength was adjusted to 0.50 with potassium chloride in all kinetic runs.Measurements of pH were made with the glass electrode and a Radiometer Model P H M 4c pH meter. Values of pD were obtained from measured pH values and the relationship pD = pH + 0.40.20 This relationship was verified for our pH meter using carefully neutralized acetate buffers.Activation parameters were obtained from second-order rate constants measured at several temperatures and the Eyring equation, In k = In ekT/h + AS*/R -E,/RT.21 (11) K. Wiberg, Chem. Rev.. 6 6 , 713 (1955). (15) C. A . Bunton and V.

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“…That hydroxylic compounds form hydrogen bonds with olefin oxides (13,16) and other cyclic ethers has been reported (9)(10)(11)(12)(13)(14)(15)(16)(17). The ethylenimines have also been discussed (18) relative to their reaction by way of an intermediate involving hydrogen bonds. In considering the data in Table I it is important to bear in mind that excess phenol was present in most of the runs, so actually a composite effect of excess phenol and added solvent was being observed in these instances.…”

Section: Oh Ocehs I Iimentioning

confidence: 99%

The Effect of Solvent and Temperature on the Base-Catalyzed Reaction of Styrene Oxide with Phenol

Guss¹,

Williams²

1951

J. Org. Chem.

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Reactions of Ethylenimines. II. With Thiophenol. A Rate Study

Cited by 22 publications

References 0 publications

Novel Method for the Preparation of Organic Isocyanates¹

Novel Method for the Preparation of Organic Isocyanates¹

The Reaction of Guanazole and Diformylhydrazine¹

The Effect of Solvent and Temperature on the Base-Catalyzed Reaction of Styrene Oxide with Phenol

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Reactions of Ethylenimines. II. With Thiophenol. A Rate Study

Cited by 22 publications

References 0 publications

Novel Method for the Preparation of Organic Isocyanates1

Novel Method for the Preparation of Organic Isocyanates1

The Reaction of Guanazole and Diformylhydrazine1

The Effect of Solvent and Temperature on the Base-Catalyzed Reaction of Styrene Oxide with Phenol

Contact Info

Product

Resources

About

Novel Method for the Preparation of Organic Isocyanates¹

Novel Method for the Preparation of Organic Isocyanates¹

The Reaction of Guanazole and Diformylhydrazine¹