New Methods of Preparative Organic Chemistry. Transfer of Diazo Groups

Abstract

The machine program for the determination of fundamental rings is written in the problem-oriented F O R T R A N language. It has already been tested on the IBM@ 7010,7090, and 360 Model 40 machines (the last with a 64 K core memory). A series of different structural-formula graphs with up to 1 2 condensation points were fed into the machine in the short topological form described by Morganr*l, and the fundamental rings present in each were determined by computer.The results were expressed in the form of a list: a heading line that can accommodate up t o 24 two-digit numbers gives the various ring sizes. Under these, in a fourteen line matrix, the individual ring members are given in the order of their occurrence in the ring (cf. Scheme 6).["I Cf. Section 3, 1121.It may happen that in a highly complicated molecule so many condensation points and fundamental rings exist that the available space in the memory of the computer does not suffice for all steps of the complete ring-recognition process. Then the machine prints a message showing which of the condensation points it was unable to consider. After that the result can easily be completed by intellect~ially completing the algorithm. These limitations can be overcome, if necessary, by using a computer with a larger memory or by writing the program in a machine-oriented language instead of FORTRAN.The authors would like to thank W. Schwier and M . Wildgrube fiv substantial niuthen!atical contributionA.When an arenesulfonyl azide, particularly p-toluenesulfonyl azide, reacts, in the prewnce of a base, with a compound containing an active methylene group, the two hydrogen atoms of the active methylene group are replaced by a diazo group to form a diazo compound and an arenesulfonamide. The method may be used for the synthesis of t h e diazo derivatives

Synthesis of functionalized bicyclo[3.2.1]octa-2,6-dienes by thermal rearrangement of substituted 6-exo-(1-alkenyl)bicyclo[3.1.0]hex-2-ene systems

“…Treatment of each of the P-keto esters 18-21 with p-toluenesulfonyl azide in acetonitrile containing one equivalent of triethylamine (20) afforded, in essentially quantitative yields, the corresponding diazo compounds 22-25, respectively. The latter substances exhibited, in their infrared spectra, an absorption band in the region 2 120-2125 cm-' , typical of the diazo function.…”

“…The combined organic extract was washed once with 1 N hydrochloric acid and three times with brine and then was dried (MgS04). Removal of the solvent, followed by distillation (air-bath temperature 81-85"C/0.1 Torr) of the residual oil, gave the desired product 18 Methyl (E)-6-rnethyl-3-0~0-6,8-nonadienoate (20) This substance was prepared via a procedure very similar to that described above (preparation of 18). From 712 p,L (6.6 mmol) of methyl acetoacetate and 1.06 g (6.6 mmol) of the bromide 16 there was obtained a crude product that was subjected to flash column chromatography (silica gel, elution with 1:4 ether -petroleum ether).…”

Seven-membered ring scaffolds for drug discovery: Access to functionalised azepanes and oxepanes through diazocarbonyl chemistry

“…22 The diazo group can easily be introduced into activated methylene groups via Regitz diazo-transfer using sulfonyl azides as the transfer reagent. 23 Diazocarbonyl compounds generated by this method are bench stable with predictable reactivity that can be attuned to the synthetic task at hand.…”

Crystal Structure of 2-Ethylimidazole-1-sulfonyl Azide: A New Azidation Reagent

“…They can be used in "click chemistry" [3][4][5][6] to introduce heterocyclic structures and serve as a latent amino group [7]. However, most of the reagents commonly used to procure the azides, such as tosyl [8,9], triflyl [10][11][12], mesyl [13], or trisyl azide [14] suffer from hazardous properties and poor shelf life due to thermal instability [15]. Thus a robust and safe alternative is required.…”