S-nitrosoethanethiol | 26185-93-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: S-nitrosoethanethiol
• 英文别名: Aethylthionitrit；Ethylthionitrit；Nitrososulfanylethane
• CAS: 26185-93-3
• 化学式: C₂H₅NOS
• 分子量: 91.1338
• InChiKey: QBDXCFHRLOVYBY-UHFFFAOYSA-N

物化性质

• 沸点：
  99.4±23.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  5
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  54.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  S-nitrosoethanethiol 在 氧气 作用下， 生成 乙基磺酸
  参考文献：
  名称：

  Lecher; Siefken, Chemische Berichte, 1926, vol. 59, p. 1321

  摘要：

  DOI：
• 作为产物：
  描述：

  乙硫醇 在 三缩四乙二醇 、 silica gel 、 dinitrogen tetraoxide 作用下， 以 叔丁醇 为溶剂， 生成 S-nitrosoethanethiol
  参考文献：
  名称：

  二氧化硅-聚乙二醇/N 2 O 4 配合物作为多相硝化剂和亚硝化剂

  摘要：

  氯化硅与不同量的 H(OCH 2 CH 2 ) n OH (n = 2-4) 反应以提供基于二氧化硅的线性聚乙二醇和环状聚乙二醇醚。选择了二氧化硅-四甘醇醚 (III) 的 N 2 O 4 络合物，并将其用作一种稳定、廉价且非均相的二氧化硅基试剂，用于苯酚的选择性单硝化和二硝化以及硫醇的亚硝化。

  DOI：

  10.1080/10426500307863

文献信息

• Silica-Acetate Complex of N₂O₄: A Heterogeneous Reagent for the Selective Nitration of Phenols and Nitrosation of Thiols
  作者：N. Iranpoor、H. Firouzabadi、R. Heydari

  DOI：10.1081/scc-120016310

  日期：2003.1.4

  Abstract Complexation of gaseous N2O4 with acylated silica gel affords an addition compound, which is an efficient heterogeneous reagent for the selective mono- and dinitration of phenol, substituted phenols and nitrosation of thiols.

  摘要 气态 N2O4 与酰化硅胶络合得到加成化合物，这是一种有效的多相试剂，用于苯酚、取代苯酚的选择性单硝化和二硝化以及硫醇的亚硝化。
• 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 syntheses of thionitrites and their chemical reactivites
  作者：Shigeru Oae、Yong H. Kim、Daikichi Fukushima、K?ichi Shinhama

  DOI：10.1039/p19780000913

  日期：——

  with other nucleophiles such as thiols, sulphinic acids, alcohols, and secondary amines at ca.–5 °C. Treatment of thionitrites with other thiols or sulphinic acids was found to yield the corresponding unsymmetrical disulphides or thiolsulphonates in good yields. Similar treatment of thionitrites with secondary amines or alcohols gave the corresponding N-nitrosoamines, or disulphides and nitrites.

  通过硫醇与四氧化二氮（N 2 O 4）在温和条件下的反应，定量制备了芳基和烷基亚硫氰酸盐（RSNO）。通过在低温（例如0°C）下的红外光谱或紫外光谱或它们与亲核试剂的进一步反应生成已知的衍生物，鉴定出不稳定的亚硝酸盐。总结了这些亚硝酸盐的光谱数据，发现高反应性亚硝酸盐易于与其他亲核试剂，例如硫醇，亚磺酸，醇和仲胺，在约200℃下反应。–5°C。发现用其他硫醇或亚磺酸处理硫代亚硝酸盐可得到良好产率的相应的不对称二硫化物或硫代磺酸盐。用仲胺或醇类似地处理硫亚硝酸盐，得到相应的N-亚硝基胺或二硫化物和亚硝酸盐。
• Efficient Conversion of Thiols to S-Nitrosothiols with the 18-Crown-6 Complex of N2O4 as a New Nitrosating Agent
  作者：N. Iranpoor、H. Firouzabadi、R. Heydari

  DOI：10.1039/a904784k

  日期：——

  Gaseous N2O4 reacts with 18-crown-6 to afford a stable ionic complex of NO+·18-crown-6·H(NO3)2–; this complex is an efficient nitrosating agent for the conversion of thiols to their corresponding S-nitrosothiols in different organic solvents.

  气态N2O4与18-冠-6反应，形成稳定的离子复合物NO+·18-冠-6·H(NO3)2–；该复合物是有效的亚硝化试剂，可将硫醇转化为相应的S-亚硝基硫醇，适用于不同的有机溶剂。
• Amination of complexed carbon monoxide by N-nitrosamines: syntheses and structures of iron carbonyl and nitrosyl complexes and applications to heterocyclic synthesis
  作者：Peter Bladon、Margaret Dekker、Graham R. Knox、Debra Willison、Ghayoor A. Jaffari、Robert J. Doedens、Kenneth W. Muir

  DOI：10.1021/om00029a034

  日期：1993.5

  Nitrosamines, R2NNO, undergo homolytic cleavage of the N-N bond on reaction with iron carbonyls to give Fe(CO)2(NO)2 and organoiron products containing the ligands R2N, R2NCO, and R2NC, formally derived from amination of complexed carbon monoxide, together with amines and ureas. The major products from dimethyl- and diethylnitrosamine are (OC)4-Fe(mu-CNR2)Fe(CO)2NO (4). The ethyl derivative has been crystallographically characterized: space group Pbca, a = 13.573(5) angstrom, b = 14.675(2) angstrom, c = 16.313(2) angstrom, V = 3249.3 angstrom3, Z = 8, R(F) = 0.057, and R(w) = 0.061 for 1152 reflections with I greater-than-or-equal-to 2sigma(I). These nitrosyls are thermolyzed to the bridging carbyne complexes (OC)3Fe(mu-CNR2)2Fe(CO)3 (9) and trinuclear [(OC)3Fe]3-(mu3-CNR2)2 (21). Other products include (OC)3Fe[(mu-CNR2)(mu-OCNR2)]Fe(CO)3 (5), (OC)3Fe]3-[(mu-NR2)(mu-OCNR2)]Fe(CO)3 (6), and (OC)3Fe[(mu-NR2)(mu-CNR2)]Fe(CO)3 (8). Thermolysis of the carbene complex(Me2N)2CFe(CO)4 gives 5,8,9, and 21. The major product from N-methyl-N-nitrosoaniline and Fe2(CO)9 is the ortho-metalated ferracycle C6H4N(CH3)COFe(CO)4 (7), which has been crystallographically characterized: space group P2(1)/c, a = 6.396(1) angstrom, b = 10.056(2) angstrom, c = 19.025(3) angstrom, beta = 95.17(1)-degrees, V = 1218.7(1) angstrom3, Z = 4, RF = 0.032, and R(w) = 0.042 for 2008 reflections with I greater-than-or-equal-to 3sigma(I). This ferracycle, tetracarbonyl(1-methyl-3-ferra-2-oxindole), undergoes trimethylamine N-oxide induced alkyne insertion to yield 3,4-disubstituted (Et-, MeO2C-) 1-methyl-2-quinolones, while photochemically induced insertion of an alkyne gives a product where the 3,4-alkene bond has been reduced, together with the carbonylation product, N-methylisatin. One of two isomers Of (OC)3Fe[(mu-N(Me)Ph)(mu-OCN(Me)Ph)]Fe(CO)3 has been structurally characterized with psi-anti-Ph and psi-anti-Me groups: P2(1)/n, a = 19.919(7) angstrom, b = 10.122(4) angstrom, c = 22.548(9) angstrom, beta = 98.90(3)-degrees, V = 4491(3) angstrom3, Z = 8, R(F) = 0.045, and R(w) = 0.062 for 4648 reflections with I greater-than-or-equal-to 3sigma(I). Thionitrites, RSNO, react with Fe2(CO)9 to give Fe(CO)2(NO)2 and Roussin's red esters [(ON)2Fe(SR)]2, with Ni(CO)4 to give polymeric [RSNiNO]x, with Hg[CO(CO)4]2 to give CO(CO)3NO and unstable [CH3SCo(NO)2]2, with Mo-(CO)6 to give apolymeric product, with [C5H5Fe(CO)2]2 to give a mixture of [C5H5Fe(CO)SMe]2 and [MeSFe(NO)2]2, and with [C5H5Mo(CO)3]2 to give C5H5Mo(CO)2NO. [PhSNiNO]x reacts with C5H5Na to give C5H5NiNO, while NO reacts with [PhSNiC5H5]2 to give [PhSNiNO]x and C5H5NiNO. Fe(CO)2(NO)2 is synthesized by reacting ethyl nitrite with Fe2(CO)9 and from Fe(CO)4I2 and silver nitrite.