1-(acetylamino)-2-methylpropane-2-thionitrite

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1-(acetylamino)-2-methylpropane-2-thionitrite
• 英文别名: N-(2-methyl-2-nitrososulfanylpropyl)acetamide
• 化学式: C₆H₁₂N₂O₂S
• 分子量: 176.239
• InChiKey: VPGLNCHYYRNXCL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  83.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(acetylamino)-2-methylpropane-2-thionitrite 以 甲醇 为溶剂， 反应 3.0h， 以100%的产率得到N-[2-(2-Acetylamino-1,1-dimethyl-ethyldisulfanyl)-2-methyl-propyl]-acetamide
  参考文献：
  名称：

  Synthesis, characterization, and protonation of octaethylporphyrin osmium nitrosyl complexes containing axial thiolate ligands - X-ray structures of an alkyl thionitrite (RSNO) and its (OEP)Os(NO)(SR) addition product

  摘要：

  (OEP)Os(NO)(SR)化合物（其中R = 甲基，乙基，异丙基，叔丁基）通过前体烷基硫亚硝酸酯（RSNO）在（OEP）Os(CO)金属中心上的形式转加反应，以33-48%的分离收率制备。这些亚硝基硫醇酸盐化合物已通过红外光谱，¹H核磁共振，紫外-可见光谱和FAB质谱进行表征。它们的红外光谱显示在1751-1755 cm^-1（KBr）范围内的吸收峰，表明这类化合物中存在末端N-配位的NO配体。通过（OEP）Os(NO)(O-i-C₅H₁₁)与乙烷-1,2-二硫醇反应，已以70%的分离收率制备了硫醇-硫醇（OEP）Os(NO)(SCH₂CH₂SH)配合物。通过¹H核磁共振光谱，用t-BuONO硝化（OEP）Os(NO)(SCH₂CH₂SH)中的自由-SH基团，然后与（TTP）Ru(CO)反应，得到了[(OEP)Os(NO)](µ-SCH₂CH₂S-S,S')[Ru(NO)(TTP)]，收率为70%。还通过烷氧基-硫醇酸盐交换反应（对于R' = H）或RSNO加成到（OEP）Os(CO)（对于R' = Me）制备了（OEP）Os(NO)(SCR'₂CH₂NHC(O)Me)化合物。通过单晶X射线衍射确定了前体RSNO硫亚硝酸酯（对于R' = Me）和金属衍生物的固态分子结构。这些（OEP）Os(NO)(SCR'₂CH₂NHC(O)Me)配合物的质子化产生了酰胺配位的[(OEP)Os(NO)(O=C(Me)NHCH₂CR'₂SH)]BF₄衍生物。后者阳离子化合物也可通过（OEP）Os(CO)与四氟硼酸亚硝酰盐的顺序反应，然后加入酰胺-硫醇试剂获得。关键词：硫亚硝酸酯，亚硝基硫醇，卟啉，X射线结构，一氧化氮，锇。

  DOI：

  10.1139/v00-168
• 作为产物：
  描述：

  N-Acetyl-1-amino-2-methylpropane-2-thiol 在 acidic medium 、 sodium nitrite 作用下， 以75%的产率得到1-(acetylamino)-2-methylpropane-2-thionitrite
  参考文献：
  名称：

  New Thionitrites: Synthesis, Stability, and Nitric Oxide Generation

  摘要：

  In order to study the influence of substitutions at the alpha and beta carbon atoms on the stability of the S-NO bond, water-soluble thionitrites RSNO have been synthesized by nitrosation of cysteamine and mercaptoethanol derivatives and characterized. H-1 and C-13 NMR spectroscopies have proven to be excellent probes for the nitrosation of thiols. In water, at physiological pH, the compounds decomposed into nitric oxide NO and the corresponding disulfides. The rate at which NO was released was very sensitive to modifications at the alpha and beta carbon atoms. Tertiary thionitrites were more stable than primary thionitrites. The beta-substituents decreased the rates of decomposition in the following order: OH > NHCOCH3 > NH3+. S-Nitrosocysteamine derivatives were greatly stabilized at low pH. The compounds described here might be convenient and useful as vehicles for spontaneous generation of nitric oxide in biological systems, at rates that can be finely tuned and controlled over a wide range.

  DOI：

  10.1021/jo00102a028

文献信息

• Yi, Geun-Bae; Khan, Masood A.; Powell, Douglas R., Inorganic Chemistry, 1998, vol. 37, # 2, p. 208 - 214
  作者：Yi, Geun-Bae、Khan, Masood A.、Powell, Douglas R.、Richter-Addo, George B.

  DOI：——

  日期：——
• Synthesis, characterization, and protonation of octaethylporphyrin osmium nitrosyl complexes containing axial thiolate ligands - X-ray structures of an alkyl thionitrite (RSNO) and its (OEP)Os(NO)(SR) addition product
  作者：Jonghyuk Lee、Geun-Bae Yi、Douglas R Powell、Masood A Khan、George B Richter-Addo

  DOI：10.1139/v00-168

  日期：2001.5.1

  The (OEP)Os(NO)(SR) compounds (R = Me, Et, i-Pr, t-Bu) have been prepared in 33-48% isolated yields by the formal trans-addition of the precursor alkyl thionitrites (RSNO) across the metal center in (OEP)Os(CO). The nitrosyl thiolate compounds have been characterized by IR,¹H NMR, and UV-vis spectroscopy, and by FAB mass spectrometry. Their IR spectra display bands in the 1751-1755 cm^-1(KBr) range, which is indicative of terminal N-bound NO ligands in this class of compounds. The thiolate-thiol (OEP)Os(NO)(SCH₂CH₂SH) complex has been prepared in 70% isolated yield from the reaction of (OEP)Os(NO)(O-i-C₅H₁₁) with ethane-1,2-dithiol. Nitrosation of the free -SH group in (OEP)Os(NO)(SCH₂CH₂SH) with t-BuONO, followed by reaction with (TTP)Ru(CO) gave [(OEP)Os(NO)](µ-SCH₂CH₂S-S,S')[Ru(NO)(TTP)] in 70% yield by¹H NMR spectroscopy. The (OEP)Os(NO)(SCR'₂CH₂NHC(O)Me) compounds have also been prepared either by an alkoxide-thiolate exchange reaction (for R' = H) or by RSNO addition to (OEP)Os(CO) (for R' = Me). The solid-state molecular structures of the precursor RSNO thionitrite (for R' = Me) and the metalloderivative have been determined by single-crystal X-ray crystallography. Protonation of these (OEP)Os(NO)(SCR'₂CH₂NHC(O)Me) complexes gave the amide-bound [(OEP)Os(NO)(O=C(Me)NHCH₂CR'₂SH)]BF₄derivatives. The latter cationic compounds were also obtained by the sequential reaction of (OEP)Os(CO) with nitrosonium tetrafluoroborate, followed by addition of the amide-thiol reagent. Key words: thionitrite, nitrosothiol, porphyrin, X-ray structure, nitric oxide, osmium.

  (OEP)Os(NO)(SR)化合物（其中R = 甲基，乙基，异丙基，叔丁基）通过前体烷基硫亚硝酸酯（RSNO）在（OEP）Os(CO)金属中心上的形式转加反应，以33-48%的分离收率制备。这些亚硝基硫醇酸盐化合物已通过红外光谱，¹H核磁共振，紫外-可见光谱和FAB质谱进行表征。它们的红外光谱显示在1751-1755 cm^-1（KBr）范围内的吸收峰，表明这类化合物中存在末端N-配位的NO配体。通过（OEP）Os(NO)(O-i-C₅H₁₁)与乙烷-1,2-二硫醇反应，已以70%的分离收率制备了硫醇-硫醇（OEP）Os(NO)(SCH₂CH₂SH)配合物。通过¹H核磁共振光谱，用t-BuONO硝化（OEP）Os(NO)(SCH₂CH₂SH)中的自由-SH基团，然后与（TTP）Ru(CO)反应，得到了[(OEP)Os(NO)](µ-SCH₂CH₂S-S,S')[Ru(NO)(TTP)]，收率为70%。还通过烷氧基-硫醇酸盐交换反应（对于R' = H）或RSNO加成到（OEP）Os(CO)（对于R' = Me）制备了（OEP）Os(NO)(SCR'₂CH₂NHC(O)Me)化合物。通过单晶X射线衍射确定了前体RSNO硫亚硝酸酯（对于R' = Me）和金属衍生物的固态分子结构。这些（OEP）Os(NO)(SCR'₂CH₂NHC(O)Me)配合物的质子化产生了酰胺配位的[(OEP)Os(NO)(O=C(Me)NHCH₂CR'₂SH)]BF₄衍生物。后者阳离子化合物也可通过（OEP）Os(CO)与四氟硼酸亚硝酰盐的顺序反应，然后加入酰胺-硫醇试剂获得。关键词：硫亚硝酸酯，亚硝基硫醇，卟啉，X射线结构，一氧化氮，锇。
• New Thionitrites: Synthesis, Stability, and Nitric Oxide Generation
  作者：Beatrice Roy、A. du Moulinet d'Hardemare、Marc Fontecave

  DOI：10.1021/jo00102a028

  日期：1994.11

  In order to study the influence of substitutions at the alpha and beta carbon atoms on the stability of the S-NO bond, water-soluble thionitrites RSNO have been synthesized by nitrosation of cysteamine and mercaptoethanol derivatives and characterized. H-1 and C-13 NMR spectroscopies have proven to be excellent probes for the nitrosation of thiols. In water, at physiological pH, the compounds decomposed into nitric oxide NO and the corresponding disulfides. The rate at which NO was released was very sensitive to modifications at the alpha and beta carbon atoms. Tertiary thionitrites were more stable than primary thionitrites. The beta-substituents decreased the rates of decomposition in the following order: OH > NHCOCH3 > NH3+. S-Nitrosocysteamine derivatives were greatly stabilized at low pH. The compounds described here might be convenient and useful as vehicles for spontaneous generation of nitric oxide in biological systems, at rates that can be finely tuned and controlled over a wide range.