methyl thionitrite | 22223-61-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: methyl thionitrite
• 英文别名: Methylthionitrit；trans-methyl S-nitrosothiol；nitrososulfanylmethane
• CAS: 22223-61-6
• 化学式: CH₃NOS
• 分子量: 77.1069
• InChiKey: SNTSCLGUSUAXSO-UHFFFAOYSA-N

物化性质

• 沸点：
  73.3±23.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  4
• 可旋转键数：
  0
• 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：

  methyl thionitrite 生成 二甲基二硫
  参考文献：
  名称：

  甲基亚硫氰酸盐（CH3SNO）的光谱和光化学性质

  摘要：

  DOI：

  10.1021/j100224a003
• 作为产物：
  描述：

  methylthio radical 在 氧化亚氮 作用下， 生成 methyl thionitrite
  参考文献：
  名称：

  甲硫基和（甲硫基）二氧基与臭氧，二氧化氮和一氧化氮的反应

  摘要：

  The atmospherically important reactions of both CH3S and CH3SOO were examined using the technique of pulsed laser photolysis/laser-induced fluorescence. Rate coefficients for the reactions CH3S + 03 --> products (1) and CH3S + NO2 --> CH3SO + NO (2) were measured to be k1(T) = (1.98 +/- 0.38) X 10(-12) exp[(290 +/-40)/T] cm3 molecule-1 s-1 and k2(T) = (2.06 +/- 0.44) x 10(-11) exp[(320 +/- 40)/T] cm3 MolecUle-1 s-1. The reactions of the weakly bound CH3SOO adduct with O3, NO2, and NO were studied at low temperatures. The rate coefficients for the adduct reactions are as follows: CH3SOO + 03 --> products (4), k4 < 8 X 10(-13) CM3 molecule-1 s-1 at T = 227 K; CH3SOO + NO2 --> products (5), k5 = (2.2 +/- 0.6) X 10(-11) CM3 molecule-1 s-1 at T = 227-246 K; and CH3SOO + NO --> products (6), k6 = (1.1 +/- 0.4) x 10(-11) CM3 Molecule-1 s-1 from T = 227-256 K. The measured values of k5 and k6 were independent of temperature and pressure over the limited ranges employed. The atmospheric implications of these findings are discussed.

  DOI：

  10.1021/j100124a025

文献信息

• 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。
• Kinetics of the reaction of CH3S with NO, NO2 and O2
  作者：R.Jeffrey Balla、H.H. Nelson、J.R. McDonald

  DOI：10.1016/0301-0104(86)80188-4

  日期：1986.11

  We have used the laser-induced fluorescence technique to study the reactions of the methyl thiyl radical (CH3S) with NO, NO2, and O2 as a function of pressure (1–400 Torr N2 or SF6) and temperature (25–238°C). Rate constants for the reaction with NO are in the transition region between the low- and high-pressure limits and are fit using an expression developed by Troe. The resulting Arrhenius expression

  我们已经使用激光诱导荧光技术研究了甲基噻吩基（CH 3 S）与NO，NO 2和O 2随压力（1-400 Torr N 2或SF 6）和温度变化的反应。 （25–238°C）。与NO反应的速率常数位于低压和高压极限之间的过渡区域，并使用Troe开发的表达式进行拟合。将得到的阿累尼乌斯表达是ķ ∞（±2σ）=（1.81±0.84）×10 -12 EXP [（1800±320卡/摩尔）/ RT ]厘米3 /秒。CH 3 S与NO 2反应的速率常数基本上与压力无关，并且产率为k =（8.3±1.4）×10 -11 exp [（160±120 cal / mol）/ RT ] cm 3 / s。与O 2的反应太慢，无法在我们的系统中进行测量。我们估计ķ ⩽2×10 -17厘米3 /秒在室温下。
• Vibrational spectra and normal coordinate analysis of methyl thionitrite and isotopic analogs
  作者：D.Michael Byler、Heino Susi

  DOI：10.1016/0022-2860(81)85264-7

  日期：1981.11

  fundamentals of methyl thionitrite (CH 3 SNO) and its d 3 -, 13 C-, and 15 N-substituted analogs have been used to calculate a nineteen-parameter symmetry valence force field. The final refinement resulted in an average error of less than 4 cm −1 (~0.5%) between the calculated and observed frequencies for the four isotopomers. Contrary to earlier reports, relative intensities, isotopic frequency shifts

  摘要 观测到的亚硝酸甲酯 (CH 3 SNO) 及其 d 3 -、 13 C- 和 15 N-取代类似物的 44 种基本成分的气相红外频率已被用于计算 19 参数对称价力场. 最终的改进导致四种同位素异构体的计算频率和观察频率之间的平均误差小于 4 cm -1 (~0.5%)。与早期的报告相反，相对强度、同位素频率偏移以及计算出的势能分布都支持将 v (CS) 分配给比 v (SN) 更高的频率。对于正常分子，在 735 cm -1 处观察到 v (CS) 为弱带；相比之下，v (SN) 在 646 cm -1 处强烈吸收。在未取代分子的气相光谱中，NO 伸缩基波发生在 1535 cm -1 处，但当 15 N 取代正常同位素时转移到 1507 cm -1 处。与 CH 3 SNO 的骨架振动相关的五个基本谱带与 CF 3 SNO 和 CH 3 ONO 光谱中的类似吸收进行了比较。
• Curtius-Type Rearrangement of Sulfinyl Azides: A Matrix Isolation and Computational Study
  作者：Zhuang Wu、Xiaoqing Zeng

  DOI：10.1021/acs.jpca.2c02469

  日期：2022.7.14

  characterized with matrix-isolation IR and UV–vis spectroscopy. Prolonged irradiation at 266 nm causes Curtius rearrangement of the nitrene to form N-sulfinylamine CH3NSO and S-nitrosothiol CH3SNO. By high-vacuum flash pyrolysis (HVFP) at 800 K, CH3S(O)N3 also decomposes and furnishes CH3S(O)N with minor fragmentation products HNSO and CH2 in the gas phase. A similar photo-induced Curtius-type rearrangement of

  首次合成并表征了高度不稳定的甲基亚磺酰基叠氮化物CH 3 S(O)N 3 。在气相中，CH 3 S(O)N 3在室温 (300 K) 下快速​​分解，估计半衰期 ( t 1/2 ) 为 7 分钟。在低温 Ar (10 K) 和 Ne (3 K) 基质中以 266 nm 照射时，叠氮化物通过产生闭壳单重态基态的新型亚磺酰基氮烯中间体 CH 3 S(O)N 挤出分子氮，其具有用基质分离红外和紫外-可见光谱表征。266 nm 的长时间照射导致氮烯的 Curtius 重排形成N-亚磺胺 CH 3NSO 和S-亚硝基硫醇 CH 3 SNO。通过 800 K 的高真空闪蒸热解 (HVFP)，CH 3 S(O)N 3也分解并提供 CH 3 S(O)N 以及气相中的少量碎片产物 HNSO 和 CH 2。在基质中也观察到类似的光诱导的三氟甲基亚磺酰基叠氮化物 CF 3 S(O)N 3到 CF 3 NSO 和
• 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.