trans-mono-O-tert-butyl hyponitrite

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: trans-mono-O-tert-butyl hyponitrite
• 英文别名: t-Butyl hyponitrite；N-[(2-methylpropan-2-yl)oxy]nitrous amide
• 化学式: C₄H₁₀N₂O₂
• 分子量: 118.136
• InChiKey: YSCPIQWZZANCAT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  50.7
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trans-mono-O-tert-butyl hyponitrite 在 sodium hydroxide 作用下， 生成 叔丁醇
  参考文献：
  名称：

  Correlation of the Product E/Z Framework Geometry and O/O vs O/N Regioselectivity in the Dialkylation of Hyponitrite

  摘要：

  The products from the alkylation of silver hyponitrite with tert-butyl bromide, tert-amyl bromide, p-tert-butyl benzylbromide, and chlorotriethylsilane have been determined. In the reaction of tert-butyl bromide the formation of three new products, namely, (Z)-N-tert-butyl-N'-tert-butoxydiazene-N-oxide {(CH3)(3)CN(O)NOC(CH3)(3)}, 1D, trans-mono-O-tert-butylhyponitrous acid {(CH3)(3)CONNOH}, 2A, and (Z)-N-tert-butyl-N'-hydroxydiazene-N-oxide {(CH3)(3)CN(O)NNQH}, 2D, is observed together with the formation of the known trans-di-O-tert-butyl hyponitrite {(CH3)(3)CONNOC(CH3)(3)}, 1A. The reaction with tert-amyl bromide also yielded the corresponding tert-amyl derivatives. However, from the reactions of p-tert-butylbenzyl bromide and chlorotriethylsilane with silver hyponitrite, the corresponding trans-di-O-tert-alkylhyponitrites were obtained as the only alkylated products. The differential reactivity of the two sets of halides with silver hyponitrite is explained in terms of the higher stability of the cations generated from the former halides in comparison to those generated from the latter halides. The thermal decomposition data and UV-visible spectroscopic data are reported for all of the products. Crystallographic structural data are reported for two of the products, namely, Q-N-tert-butyl-K-tert-butoxydiazene-N-ox, 1D, as its hyponitrous acid adduct, (CH3)(3)CN(O)NOC(CH3)(3). 1/2HONNOH, and trans-di-O-p-tert-butylbenzyl hyponitrite, {p(CH3)(3)C}C6H4CH2ONNOCH2C6H4-p-{C(CH3)(3)}. Theoretical calculations using ab initio density functional theory (B3LYP) are reported for the hyponitrite dianion, trans-mono-O-methylhyponitrite anion, (Z)-N-methyl-N'-hydroxylatodiazene-N-oxid anion, and for the methylation transition states. On the basis of the products isolated from the reactions of tert-butyl bromide and tert-amyl bromide and the theoretical calculations, a pathway is proposed to account for the observed product distributions where O/O-dialkylation is found in the trans(E) products and O/N-dialkylation is found in the cis(Z) products.

  DOI：

  10.1021/ja994261o
• 作为产物：
  描述：

  溴代叔丁烷 在 silver hyponitrite 作用下， 以 乙醚 为溶剂， 反应 0.75h， 以16%的产率得到反式-二叔丁基连二次硝酸酯
  参考文献：
  名称：

  Correlation of the Product E/Z Framework Geometry and O/O vs O/N Regioselectivity in the Dialkylation of Hyponitrite

  摘要：

  The products from the alkylation of silver hyponitrite with tert-butyl bromide, tert-amyl bromide, p-tert-butyl benzylbromide, and chlorotriethylsilane have been determined. In the reaction of tert-butyl bromide the formation of three new products, namely, (Z)-N-tert-butyl-N'-tert-butoxydiazene-N-oxide {(CH3)(3)CN(O)NOC(CH3)(3)}, 1D, trans-mono-O-tert-butylhyponitrous acid {(CH3)(3)CONNOH}, 2A, and (Z)-N-tert-butyl-N'-hydroxydiazene-N-oxide {(CH3)(3)CN(O)NNQH}, 2D, is observed together with the formation of the known trans-di-O-tert-butyl hyponitrite {(CH3)(3)CONNOC(CH3)(3)}, 1A. The reaction with tert-amyl bromide also yielded the corresponding tert-amyl derivatives. However, from the reactions of p-tert-butylbenzyl bromide and chlorotriethylsilane with silver hyponitrite, the corresponding trans-di-O-tert-alkylhyponitrites were obtained as the only alkylated products. The differential reactivity of the two sets of halides with silver hyponitrite is explained in terms of the higher stability of the cations generated from the former halides in comparison to those generated from the latter halides. The thermal decomposition data and UV-visible spectroscopic data are reported for all of the products. Crystallographic structural data are reported for two of the products, namely, Q-N-tert-butyl-K-tert-butoxydiazene-N-ox, 1D, as its hyponitrous acid adduct, (CH3)(3)CN(O)NOC(CH3)(3). 1/2HONNOH, and trans-di-O-p-tert-butylbenzyl hyponitrite, {p(CH3)(3)C}C6H4CH2ONNOCH2C6H4-p-{C(CH3)(3)}. Theoretical calculations using ab initio density functional theory (B3LYP) are reported for the hyponitrite dianion, trans-mono-O-methylhyponitrite anion, (Z)-N-methyl-N'-hydroxylatodiazene-N-oxid anion, and for the methylation transition states. On the basis of the products isolated from the reactions of tert-butyl bromide and tert-amyl bromide and the theoretical calculations, a pathway is proposed to account for the observed product distributions where O/O-dialkylation is found in the trans(E) products and O/N-dialkylation is found in the cis(Z) products.

  DOI：

  10.1021/ja994261o

文献信息

• Correlation of the Product E/Z Framework Geometry and O/O vs O/N Regioselectivity in the Dialkylation of Hyponitrite
  作者：Navamoney Arulsamy、D. Scott Bohle、Jerome A. Imonigie、Elizabeth S. Sagan

  DOI：10.1021/ja994261o

  日期：2000.6.1

  The products from the alkylation of silver hyponitrite with tert-butyl bromide, tert-amyl bromide, p-tert-butyl benzylbromide, and chlorotriethylsilane have been determined. In the reaction of tert-butyl bromide the formation of three new products, namely, (Z)-N-tert-butyl-N'-tert-butoxydiazene-N-oxide (CH3)(3)CN(O)NOC(CH3)(3)}, 1D, trans-mono-O-tert-butylhyponitrous acid (CH3)(3)CONNOH}, 2A, and (Z)-N-tert-butyl-N'-hydroxydiazene-N-oxide (CH3)(3)CN(O)NNQH}, 2D, is observed together with the formation of the known trans-di-O-tert-butyl hyponitrite (CH3)(3)CONNOC(CH3)(3)}, 1A. The reaction with tert-amyl bromide also yielded the corresponding tert-amyl derivatives. However, from the reactions of p-tert-butylbenzyl bromide and chlorotriethylsilane with silver hyponitrite, the corresponding trans-di-O-tert-alkylhyponitrites were obtained as the only alkylated products. The differential reactivity of the two sets of halides with silver hyponitrite is explained in terms of the higher stability of the cations generated from the former halides in comparison to those generated from the latter halides. The thermal decomposition data and UV-visible spectroscopic data are reported for all of the products. Crystallographic structural data are reported for two of the products, namely, Q-N-tert-butyl-K-tert-butoxydiazene-N-ox, 1D, as its hyponitrous acid adduct, (CH3)(3)CN(O)NOC(CH3)(3). 1/2HONNOH, and trans-di-O-p-tert-butylbenzyl hyponitrite, p(CH3)(3)C}C6H4CH2ONNOCH2C6H4-p-C(CH3)(3)}. Theoretical calculations using ab initio density functional theory (B3LYP) are reported for the hyponitrite dianion, trans-mono-O-methylhyponitrite anion, (Z)-N-methyl-N'-hydroxylatodiazene-N-oxid anion, and for the methylation transition states. On the basis of the products isolated from the reactions of tert-butyl bromide and tert-amyl bromide and the theoretical calculations, a pathway is proposed to account for the observed product distributions where O/O-dialkylation is found in the trans(E) products and O/N-dialkylation is found in the cis(Z) products.