Reaktionen CH‐aktiver Verbindungen mit Aziden, XXVI Synthese von α‐Diazo‐iminen und isomeren 1.2.3‐Triazolen sowie deren Umwandlung in α‐Diazo‐immoniumsalze²

Abstract

~~ I-Anilino-3-0x0-indene 6af liefern bei der Diazogruppen-Ubertragung mit p-Toluolsulfonsaure-azid in Athanol/Kaliumathylat 1 -0xo-3-arylimino-2-diazo-indane Sa ~ c bzw. I -0xo-3-aryl-3H.8H-indeno[1.2-d]triazole 9d-f. 8 und 9 addieren Mineralsauren -9 unter Ringoffnungzu I-Oxo-3-arylimmonium-2-diazo-indan-Salzen 10a-f. Mit Kaliumhydroxid erhalt man daraus die a-Diazo-imine Sa, b, e und f. 8c hydrolysiert weiter zu 1.3-Dioxo-2-diazo-indan ; 8d cyclisiert groI3tenteils zum Triazol 9d, ist aber durch dessen direkte thermische Isomerisierung zuganglich. I -Anilino-3-oxo-cyclohexene-(1) 12a-f werden durch Diazogruppen-Ubertragung mit hohen Ausbeuten in 4-0x0-1-aryl-4.5.6.7-tetrahydrobenzotriazole 14a-f umgewandelt. Reactions of CH-Active Compounds with Azides, X X V I I ) . Syntheses of a-Diazo-imines und Isomeric 1,2,3-Triazoles and Their Conversion into a-Diazo-inrmonium Salts1-Anilino-3-0x0-indenes 6a-f are converted into l-oxo-3-arylimino-2-diazo-indanes 8ac or 1-0~0-3-aryl-3H,8H-indeno[l,2-d]triazoles 9df by diazo group transfer with p-toluenesulfonyl azide in ethanol/potassium ethoxide. Both classes of substances add mineral acids to form 1 -oxo-3-arylimmonium-2-diazo-indane-salts 10a-f. Treatment of the immonium salts with potassium hydroxide yields the a-diazo-imines Sa, b, e and f. 8c hydrolyses to give 1,3-dioxo-2-diazo-indane; Sd, which changes largely to 9d by cyclisation, is accessible by thermal ringopeningof thelatter. I-Anilino-3-oxo-cyclohexenes-(l)l2a-f are transformed into 4-oxo-I-aryl-4,5,6,7-tetrahydro-benzotriazoles (14a-f) by diazo group transfer with high yields. a-Diazo-imine 2 galten als nicht existent, seit W o / p aus acyclischen a-Diazo-pdiketonen und Arnrnoniak oder prirnaren Aminen nicht a-Diazo-P-imino-ketone, sondern deren cyclische Isornere, 1.2.3-Triazole, erhielt. Erst in neuerer Zeit wurden Vertreter dieser Stoffklasse aus den Acetylenen 1 ac und Aziden synthetisiert.

Flash Vacuum Pyrolysis of Azides, Triazoles, and Tetrazoles

“…As described under 1,2,3-triazoles, benzotriazoles carrying strongly electron-withdrawing substituents in the 1-position undergo easy thermal ring opening. − Furthermore, 1-arylsulfonylbenzotriazoles undergo a thermal Dimroth-type interconversion, implying the intermedicy of the diazo compound (eq ; Δ G * = 20.8 kcal/mol) …”

“…1,2,3-Triazoles with highly electron-withdrawing substituents in the 1-position (CN, NO 2 , and SO 2 R) undergo ring opening to the diazoimines at ordinary temperatures or exist in equilibrium with these valence tautomers. − In investigations of triazole chemistry, one needs to be aware of the possible occurrence of a type I Dimroth rearrangement, i.e., the ring opening and recyclization of 5-amino-1,2,3-triazole derivatives via diazoimines (eq ). , …”

Alkenediazonium Salts: A New Chapter of Classical Organic Chemistry

“…This gave 2,2-dichloroethylene-1 -diazonium hexachloroantimonate (13) in analytically pure form (yield 40 %)['61.…”

Reactions of Thioacetamide Derivatives with Sulfonyl Azides: An Approach to Active‐Methylene N‐Sulfonylacetamidines

“…Sulfonyl azides, mostly tosyl and mesyl azides, show a wide range of reactivities, and are widely used in organic synthesis 1–3. They serve as diazo‐transfer agents, and allow the synthesis of various types of diazo compounds from C–H‐acidic compounds,4,5 of azides from amines,6 and of N ‐unsubstituted 1,2,3‐triazoles from enamines 7. They can undergo cycloaddition reactions with acetylenes to give 1‐sulfonyl‐1,2,3‐triazoles, in which they are the source of the sulfonyl triaza fragment 8.…”