Studies on the Willgerodt Reaction. VI. A Mechanism for the Primary Thiol Oxidation<sup>1</sup>

McMillan, Freeman H.; King, John A.

doi:10.1021/ja01192a050

Cited by 75 publications

(11 citation statements)

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“…In addition, considering that N -methylpiperidine could also initiate the reaction, a Willgerodt–Kindler mechanism should be taken into account . We suspect that sulfur could be the sole oxidant in the current system, although a combination of sulfur and oxygen could possibly play a role in the synthesis of benzoxazoles. , The released H 2 S from the process could be detected by lead acetate paper, providing a circumstantial evidence of the mechanism.…”

Section: Results and Discussionmentioning

confidence: 90%

Elemental Sulfur-Promoted Benzoxazole/Benzothiazole Formation Using a C═C Double Bond as a One-Carbon Donator

Zhang

Liu

et al. 2021

J. Org. Chem.

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Section: Results and Discussionmentioning

confidence: 90%

Elemental Sulfur-Promoted Benzoxazole/Benzothiazole Formation Using a C═C Double Bond as a One-Carbon Donator

Zhang

Liu

et al. 2021

J. Org. Chem.

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“…This reaction is more vigorous than the analogous reaction with simple thiols discovered by McMillun and King[31]. Hence, one would expect the reaction of Sand NH3 with ketones to yield a , d d i o x odisulfides rather than ~!,3-thiazolines.…”

mentioning

confidence: 87%

“…. ~ chain [20-28,301, and with the irreversible oxidation at the end of the chain [31]. Most frequently, attempts were made to convert hypothetical intermediates into w-aralkylcarboxylic acids or their derivatives or to throw light on the intermediates of the reaction by using special ketones [3,22,25,27,32-381. In 1956, we reported for the first time [39] that the combined action of sulfur and NH3 upon ketones such as cyclohexanone or diethyl ketone, leads to 43thiazolines [l].…”

Section: _ _mentioning

confidence: 99%

The Course of the Willgerodt‐Kindler Reaction of Alkyl Aryl Ketones

Asinger

Schäfer

Halcour

et al. 1964

Angew. Chem. Int. Ed. Engl.

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Fig. 12. log k VA. A pK Dependence for base-catalysed decomposition of nitramide at 15 "C (Bronsted and Pedersen [go]. Catalytically active base = Y (conjugate acid HY). The broken iines denote the extrapolated curves with a and P = 0 ar I . Upper curve: diffusion-controlled limiting value. Ordinate: log k. Abscissa: p K~y .sen for the tautomerization equilibrium of nitramide which precedes decomposition. If the rate constant is based on the concentration of the reactive form, then extrapolation to cc = 0 affords exactly the limiting value for diffusion-controlled reactions.In other systems, such as mutarotation of glucose [93], dehydration of acetaldehyde hydrate [94], constancy of the values of CI is observed over a relatively wide pK range. As expected in these cases, k is relatively small over the entire range. Here, the rate-determining step is not a simple proton transfer but the coupling of several intermediate steps. Such events are particularly important with regard to enzymic processes. They will be the main subject of the discussion presented in Part 11.Ketones react with sulfur and NH3 or amines at room temperature to produce A3-thiazolines, 5-alkylidene-A3-thiazolines, A3-imidazoline-5-thiones, hexathiacycloheptane derivatives, u,u'-dioxodisulfideJideS, bis-(I-aralk-I-yl) disulfides, or thiocarboxamides, depending on the coreactant and on the reaction conditions. It was recognized that the formation of all of these numerous types of compounds can be explained basically by primary thiolations and geminal dithio lations, which in conjunction with their reverse reaction (desulfurization) and the assumption of a thioreductone equilibrium permit a new interpretation of the course of the Willgerodt-Kindler reaction of alkyl aryl ketones.Received, September 9th, 1963 [A 336/135 IE] German version: Angew.Lysozymes are widely distributed enzymes. They split the chemical skeleton of bacterial cell walls by hydrolysing the p ( I + 4 ) linkages between N-acetylmuramic acid and N-acetylglucosamine. The amino acid sequence of lysozyme from hen's egg-white is known (129 amino acid residues). Lysozymes of different origins frequently differ in their primary structures although they exhibit qualitatively the same biological activity. The results obtained from investigations with lysozymes allow conclusions to be drawn regarding the chemical structure of the "backbone" of bacterial cell walls.

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“…Tabelle 1. Abhangigkeit der Ausbeute an Dimethylthioformamid ( I ) [5]. Beim Ruckflusskochen von S:CH,O:HN(CH,), = 1,75:0,5:0,5 erhalt man nach 4 Std.…”

Section: Fjber Die Reaktion Vonunclassified

Über die Reaktion von Schwefel mit Aminen und Formaldehyd. Eine neue Methode zur Herstellung von Thioformamiden und Dithiocarbamaten

Maier

1970

Helvetica Chimica Acta

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Studies on the Willgerodt Reaction. VI. A Mechanism for the Primary Thiol Oxidation¹

Cited by 75 publications

References 0 publications

Elemental Sulfur-Promoted Benzoxazole/Benzothiazole Formation Using a C═C Double Bond as a One-Carbon Donator

Elemental Sulfur-Promoted Benzoxazole/Benzothiazole Formation Using a C═C Double Bond as a One-Carbon Donator

The Course of the Willgerodt‐Kindler Reaction of Alkyl Aryl Ketones

Über die Reaktion von Schwefel mit Aminen und Formaldehyd. Eine neue Methode zur Herstellung von Thioformamiden und Dithiocarbamaten

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Studies on the Willgerodt Reaction. VI. A Mechanism for the Primary Thiol Oxidation1

Cited by 75 publications

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Elemental Sulfur-Promoted Benzoxazole/Benzothiazole Formation Using a C═C Double Bond as a One-Carbon Donator

Elemental Sulfur-Promoted Benzoxazole/Benzothiazole Formation Using a C═C Double Bond as a One-Carbon Donator

The Course of the Willgerodt‐Kindler Reaction of Alkyl Aryl Ketones

Über die Reaktion von Schwefel mit Aminen und Formaldehyd. Eine neue Methode zur Herstellung von Thioformamiden und Dithiocarbamaten

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Studies on the Willgerodt Reaction. VI. A Mechanism for the Primary Thiol Oxidation¹