Chemistry of N-halo compounds. XXV. Regiospecific synthesis of unsymmetrical azoxy compounds (diazene N-oxides)

Chemistry of N-halo compounds. 30. Regiospecific formation of azoxyaralkanes (diazene N-oxides) from N,N-dibromo compounds and nitrosobenzene

“…(2) N,N-dichloroamines do not react. 3 The progress of the transformation can be followed by observing the dramatic color change which occurs as the initial dark green mixture turns red upon liberation of free bromine. Fortunately, similar high yields of azoxy compounds can be more conveniently obtained by treatment of the readily available , -dichloroamines with 1 molar equiv each of bromide salt and nitrosobenzene in acetonitrile solution under mild conditions.…”

“…Superior yields of azoxy compounds are obtained only with at least a 1:1 molar ratio of CuBr2/RNCl2• XVhen N,N-dichloro-rt-aminoisobutyronitrile is exposed to only 0.5 mol of cupric bromide in the presence of 1 mol of nitrosobenzene, the yield is halved (eq 3). Scheme I sets forth various routes which RNCL + Br" + C6H5NO -0.5RN=N(O)C6H5 + 0.5RNC12 + 0.5C6H5NO + 0.5Br2 + Cl" (3) may account for this result. The suggestion that an intermediate N-chloro-N-bromoamine may be involved is justified since we recently reported isolation of mixtures of N,N-dibromoand N-chloro-A1 -bromoamines under conditions in which a large excess of MA^dichloroamine is used in the halogen exchange reaction.5 Also, since under the conditions used very little halogen exchange occurs between bromine and ALV-dichloroamine (eq 4), reaction cannot be effected by only…”

“…Caled for CieH^NAO: C, 73.28; H. 9.92: N. 10.69. Found: C. 73.03; H, 10.31; N, 10.55. JV-Neopentyl-JV'-phenyldiazene JV'-Oxide: bp 81-83 °C (5 mm); NMR (CDCI3) 8.20 (m, Ph, 2 ), 7.40 (m,Ph,3 H), 3.42 (s, CH2, 2 ), 1.05 (s, f-Bu, 9 H); IR (neat) 1475 (N=N), 1300 (N-O). 765 and 660 (aromatic) cm"1.…”

“…mp 96-97 °C). 3,. This was prepared according to the procedure described by Lwowski and Mattingly:7 bp 90 °C (4.3 mm) (lit.…”

Novel Synthetic Route and Characterization of [1,2,5]oxadiazolo- [3,4-e][1,2,3,4]tetrazine 4,6-Di-N-oxide (FTDO)

“…针对上述合成路线的缺点, 参考文献[16～19], 本 文设计了 FTDO 新的合成路线. 以 3,4-二氨基呋咱(1)为 起始原料, 苯为反应介质, 经 Caro's 酸氧化得到 3-氨 基-4-亚硝基呋咱 (2), 然后与 N,N-二溴-叔丁基胺缩合得 到 3-氨基-4-(叔丁基氧化偶氮基)呋咱 (3), 再用 100%硝 酸硝化得到 3-硝氨基-4-(叔丁基氧化偶氮基)呋咱(4), 最 后用 P 2 O 5 成环成功地获得了 FTDO (5)的高纯样品 (Scheme 2), 并通过 13 C NMR, 14 N NMR, 15 N NMR, 17 O NMR, IR, MS 和元素分析对标题化合物及其中间体结 构进行了表征. 该方法与文献报道的方法相比, 具有反 应步骤较少, 反应条件温和, 产物易于分离和提纯, 试 剂廉价易得等优点, 具有潜在的工业应用前景.…”