Über die Reaktion von S.S‐Dimethyl‐sulfodiimin mit Kaliumamid in flüssigem Ammoniak

Abstract

Die Einwirkung von Kaliumamid auf Dimethylsulfodiimin (1) in fl. NH3 verlauft zwischen -70 und 0" unter Salzbildung. Ein Mono-und ein Dikaliurnsalz von 1 werden isoliert und beschrieben. Im Autoklaven reagieren beide Stoffe zwischen 60 und 100" unter Methanabspaltung. Dabei entsteht das Aza-Analoge der Schwefelsaure, Diaminoschwefeldiimid, das als Trikalium-tetraazasulfat (5) ausfillt.Im Rahmen unserer Untersuchungen iiber die S.S-Dialkyl-sulfodiimine (-schwefeldiimide) wurden bisher nur solche Reaktionen naher studiert, die sich primar an den beiden Stickstoffatomen als den reaktivsten Zentren des Molekuls abspielen. Als Beispiele seien die zahlreichen Substitutionsreaktionen des Iminwasserstoffs durch Acyl-z), Alkyl-2) und Halogenreste3) sowie die Protonierung zu den Sulfodiiminiumsalzen4) erwahnt. Uns interessierte jetzt, ob sich auch an der Schwefel-KohlenstoffBindung Reaktionen durchfiihren lassen und die Alkylgruppen durch anorganische Substituenten ersetzt werden konnen. Besonders interessant war die Substitution durch Aminogruppen, sollte dabei doch das bisher unbekannte Aza-Analoge der Sch~-efelsaure5) gebildet werden.

Sulfondiimines: synthesis, derivatisation and application

“…27 Scheme 14 N-Alkylation of N,N 0 -unsubstituted sulfondiimine 11c with ethyl bromide (39a). 28 Scheme 15 N-Alkylations of N-monosubstituted sulfondiimines 5b with alkyl bromides 39. 29 Scheme 16 N-Acylations of N,N 0 -unsubstituted sulfondiimines 5a with acid chlorides, esters or anhydrides 40.…”

“…The first protocol for N -alkylations of sulfondiimines was described by Appel and Ross in 1967. 28 Accordingly, S , S -dimethylsulfondiimine ( 11c ) was first deprotonated with KNH 2 to form the corresponding sulfondiimine potassium salt. The latter was then reacted with ethyl bromide ( 39a ) to give N -ethyl-substituted sulfondiimine 12b (as one example) in a yield of 83% (Scheme 14).…”

Photocatalytic N-Alkylation of NH-Diaryl Sulfondiimines via Anti-Markovnikov Hydroamination with Styrenes

“…To overcome the limitations of previous methods, − we were intrigued by photocatalytic anti-Markovnikov hydroamination developed by the Nicewicz and Knowles groups, as well as others, which features mild and environmentally benign conditions, cheap and bulk styrenes as alkylating reagents, and a wide substrate scope covering primary, secondary, and even tertiary alkyl substituents . Herein, we report a facile and mild photocatalytic anti-Markovnikov hydroamination of N H-diaryl sulfondiimines with styrenes to synthesize N -alkylated sulfondiimines (Scheme d).…”

“…15 On the other hand, cyclization of commercially available phenylacetic acid and ethyl bromoacetate afforded enol 6, which was then converted to the corresponding triflate 7. The two fragments (5 and 7) merged to generate a NTs,NH-sulfondiimine derivative of Vioxx (8) in 74% yield via Suzuki coupling. Finally, 8 was applied in the newly devised photocatalytic hydroamination with 2a under the optimal condition to produce 9 in 70% yield.…”

A Facile and Mild Alkylation Protocol of NH-Diphenyl Sulfondiimines

“…The first N-alkylation protocol dates back to 1969, when Appel and Ross described a single example of alkylation between dimethyl sulfondiimine potassium and ethyl bromide (Scheme 1a). 8 Since strong and moisture-sensitive KNH 2 was employed as base, the alkylation has to be performed at -20 °C under an N 2 atmosphere. In 2014, Bolm and coworkers introduced a general alkylation method enabled by 'KOH/DMSO' superbase system, and an array of N-alkyl aryl alkyl sulfondiimines, along with an example of N-alkyl dialkyl sulfondiimine, were prepared in good yields (Scheme 1b).…”