Die umsetzung von diazoverbindungen mit azoverbindungen—VII

Contributions to the chemistry of 3‐cyanoacetylhydrazono‐2‐indolinones and X‐ray structure of Z‐3‐cyanoacetylhydrazono‐2‐indolinone monohydrate

“…Cyclic N,O-acetals 3-acyl-1,3,4oxadiazolines are 3-acyl derivatives of the cyclic isomers of aldehyde or ketone acylhydrazones and represent an interesting example for conjugation. They can be prepared by cycloaddition of 3,3disubstituted diazirenes to diacyldiazenes [1][2][3][4][5][6][7][8][9][10][11][12], that of aldehydes to nitrilimines [13], or a ketene to a ketone acylhydrazone [14]. Other methods to prepare such compounds include Pb(OAc) 4 oxidation of aldazines [15], treating silver salt of acylhydrazones with acid chloride [16].…”

Chemistry of 1-aminoazetidin-2-ones and pyrazolidin-3-ones

“…We have previously reported that 2-acetyl-5,5-dimethylpyrazolidin-3-one (1) undergoes photochemical reaction upon irradiation to give 1 -acetamidoazetidin-2-one (2) in 65% yield.1 Since that time, we have found that irradiation of l-acetyl-5,5-dimethylpyrazolidin-3-one (3) gives 2 also, in 30% yield. Furthermore, irradiation of the nitrogen unsubstituted 5,5-dimethylpyrazolidin-3-one (4) gives the parent system l-aminoazetidin-2-one (5) in 15% yield. When amine 5 was acetylated under heterogeneous conditions involving acetyl chloride and solid potassium carbonate in methylene chloride at 25°, the desired /3-lactam 2 was not obtained but rather a mixture of products was produced from which l-acetylpyrazolidin-3-one (3) was isolated as the major product (see Scheme I).…”

“…The mixture was stirred at room temperature for 6 hr, after which it was filtered to remove the precipitated triethylamine hydrochloride salt. Evaporation of the solvent left an oil which was column chromatographed on silicic acid using Et2G-EtOH (90:10 mixture by volume) eluent to give 0.74 g (58%) of a pure oil which was identified as 8: ir (CCI3H) 2970, 1750, 1710, 1375, 1305, 1230 (broad), 1130, 1085, 955, 945 cm-1; NMR (CC13D) 1.10 (t, J = 7 Hz, 3), 1.35 (s, 6), 2.50 (s, 3), 2.52 (s, 2), 3.04 (q, J = 7 Hz, 2); mass spectrum (70 eV) m/e (rel intensity) 184 (trace, M+), 143 (3), 142 (31), 129 (7), 128 (100), 109 (5), 99 (14), 85 (2), 83 (5), 71 (2), 56 (5), 55 (4), 43 (12), 42 (6), 41 (7); uv (EtOH) end absorption 200 nm (e 3200), 227 (3800), 262 (1000).…”

Halomethyl-metal compounds. 70. Reaction of phenyl(trihalomethyl)mercury compounds with azodicarboxylate esters. New route to hydrazonodihalomethanes of type (RO2C)2X2NN = C2

“…Glc (4 ft x 0.25 in., 10% UC W-98, 110°) showed that a single product was present in 87% yield. The product, bp 88°(0.24 mm), n25o 1.4730, was isolated by vacuum distillation in 70% (3.60 g) yield: ir (neat) 2990 m, 2960 w, 2930 w, 1805 m, 1770 s, 1590 m, 1489 w, 1475 w, 1402 w, 1400 w, 1378 m, 1250 s, 1180 w, 1100 s, 1002 w, 970 m, 865 w, 760 cm-1 m; XH nmr (CCU) 1.38 (t, 6, J = 7.0 Hz, OCH2CH3) and 4.40 ppm (q, 4, J = 7.0 Hz, OCH2CH3); 13C nmr (CHCU) -22.2 (C=0), -18.6 (C=N), 63.1 (OCH2CH3), and 113.0 ppm (OCH2CH3) vs. benzene; mass spectrum (70 eV) mje (rel intensity) 221 (6), 184 (4), 148 (40), 138 (19), 121 (77), 112 (35), 82 (27), 45 (38), and 29 (100). The molecular ion was not detected.…”