4-(2-Amino-aethyldithio)-toluol | 756754-59-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-(2-Amino-aethyldithio)-toluol
• 英文别名: 2-(p-Tolyl-dithio)-aethylamin；2-(p-Tolyldithio)-ethylamin；2-((4-Methylphenyl)dithio)ethanamine；2-[(4-methylphenyl)disulfanyl]ethanamine
• CAS: 756754-59-3
• 化学式: C₉H₁₃NS₂
• 分子量: 199.341
• InChiKey: DWWVFFBDYWJSGK-UHFFFAOYSA-N

物化性质

• 沸点：
  301.7±42.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  76.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-(2-Amino-aethyldithio)-toluol 、 以 四氢呋喃 为溶剂， 以15 mg的产率得到N-[2-[(4-methylphenyl)disulfanyl]ethyl]-4-[[5-[4-[2-[(4-methylphenyl)disulfanyl]ethylamino]-4-oxobutyl]sulfanyl-9,10,14,15,19,20-hexakis(methylsulfanyl)-2,7,12,17,21,22,23,24-octazapentacyclo[16.2.1.13,6.18,11.113,16]tetracosa-1(20),2,4,6(24),7,9,11(23),12,14,16,18-undecaen-4-yl]sulfanyl]butanamide
  参考文献：
  名称：

  Surface-Bound Porphyrazines:  Controlling Reduction Potentials of Self-Assembled Monolayers through Molecular Proximity/Orientation to a Metal Surface

  摘要：

  We report the preparation of two novel H-2[pz(A(n);B4-n)] porphyrazines (pzs) which were designed to position themselves quite differently when attached to a surface: one to form a standard self-assembled monolayer (SAM) roughly perpendicular to a surface, the other to lie horizontally along a surface. As the former, we synthesized a pz, 1, where one pyrrole group is functionalized with two thioethers terminated in mercaptides (SR, R = (CH2)(3)CONH(CH2)(2)S-), each protected as a disulfide, and -S-Me is attached to the other pyrrole sites; the latter is a pz, 2, with dialkoxybenzo groups fused to two trans-pyrroles of the pz ring, and SR groups are attached to the other pair of pyrroles. Nanostructures of 1 and 2 were successfully patterned on gold surfaces via dip-pen nanolithography, and the predicted molecular orientation of the resulting structures was confirmed by topographic AFM images. The two pzs exhibit similar reduction potentials in solution. Both show large shifts in potential upon surface binding, with the magnitude of the shift depending on the proximity/orientation of the pz to the surface. The first reduction potential of the "vertically" aligned 1 shifts by ca. +430 mV when incorporated in a binary pz/hexanethiol SAM, while that for 2, which lies flat, shifts by ca. +800 mV; the potential thus shifts by ca. +370 mV upon taking a given pz that stands atop a two-legged insulating "standoff" in a traditional SAM and "laying it down". We suggest these observed effects can be explained by image-charge energetics, and this is supported by a simple model.

  DOI：

  10.1021/ja045270m
• 作为产物：
  描述：

  4-甲基苯硫代磺酸 S-(4-甲基苯基)酯 、 巯基乙胺 在 air 作用下， 以 乙醇 为溶剂， 反应 18.0h， 以12%的产率得到4-(2-Amino-aethyldithio)-toluol
  参考文献：
  名称：

  通过硫代磺酸盐与硫醇或胺的反应合成不对称的二硫键和亚磺酰胺

  摘要：

  研究了硫代磺酸盐与亲核试剂的反应性。当进行硫代磺酸盐与硫醇的反应时，以优异的产率获得了不对称的二硫化物。该程序可以使用多种芳基或烷基硫醇。另一方面，硫代磺酸盐与胺的反应在铜催化剂的存在下进行。该过程在空气中有效进行，得到相应的亚磺酰胺。

  DOI：

  10.1016/j.tet.2017.02.047

文献信息

• Biologically oriented organic sulfur chemistry. 15. Organic disulfides and related substances. 41. Inhibition of the fungal pathogen Histoplasma capsulatum by some organic disulfides
  作者：Lamar Field、John A. R. Grimaldi、Wayne S. Hanley、Mark W. Holladay、Ramanathan Ravichandran、Lawrence J. Schaad、C. Emory Tate

  DOI：10.1021/jm00218a002

  日期：1977.8

  In an extension of promising inhibitory results in vitro against Histoplasma capsulatum, correlated earlier using substituent constants developed by regression analysis with 77 disulfides, one symmetrical and 14 unsymmetrical disulfides were prepared (3--17). About half were active in vitro against H. capsulatum (and one against Candida albicans). Groups that seemed most to lead to promising inhibition

  为了扩大对荚膜胞浆菌的体外有希望的抑制结果，使用回归分析开发的取代基常数与77种二硫化物进行了较早的关联，制备了一种对称和14种不对称的二硫化物（3--17）。大约一半在体外对荚膜梭菌有活性（另一种对白色念珠菌有活性）。在不对称二硫化物中似乎最有希望导致抑制作用的基团是o-HO2CC6H4，（CH2）4SO2Na，Me2NC（S），p-ClC6H4，也许还有p-CH3C6H4；前两个也可用于增加溶解度。吗啉代基团的早期抑制希望没有实现。3--17组中没有一个在体内具有显着活性。通过硫醇与亚磺酰氯或与无环或环状硫代磺酸盐反应制备不对称二硫化物。通过新颖的环化反应制备了两个六元杂环二硫化物（5和6），其中二硫化碳与（N-烷基氨基）乙基邦特盐反应，然后闭环。建议不存在N-烷基时形成噻唑啉的解释。一种二硫化物极易分散（31;在25摄氏度下为0.3--1小时）。
• Organic Disulfides and Related Substances. IV. Thiolsulfonates and Disulfides Containing 2-Aminoethyl Moieties¹
  作者：Lamar Field、Terence C. Owen、Ronnie R. Crenshaw、Ann W. Bryan

  DOI：10.1021/ja01482a027

  日期：1961.11
• Unsymmetrical disulfide and sulfenamide synthesis via reactions of thiosulfonates with thiols or amines
  作者：Nobukazu Taniguchi

  DOI：10.1016/j.tet.2017.02.047

  日期：2017.4

  The reactivity of thiosulfonates with nucleophilic reagents was investigated. When reactions of thiosulfonates with thiols were performed, unsymmetrical disulfides were obtained in excellent yields. This procedure could employ numerous aryl or alkyl thiols. On the other hand, reactions of thiosulfonates with amines proceeded in the presence of a copper catalyst. The procedure was performed efficiently

  研究了硫代磺酸盐与亲核试剂的反应性。当进行硫代磺酸盐与硫醇的反应时，以优异的产率获得了不对称的二硫化物。该程序可以使用多种芳基或烷基硫醇。另一方面，硫代磺酸盐与胺的反应在铜催化剂的存在下进行。该过程在空气中有效进行，得到相应的亚磺酰胺。
• Surface-Bound Porphyrazines:  Controlling Reduction Potentials of Self-Assembled Monolayers through Molecular Proximity/Orientation to a Metal Surface
  作者：Benjamin J. Vesper、Khalid Salaita、Hong Zong、Chad A. Mirkin、Anthony G. M. Barrett、Brian M. Hoffman

  DOI：10.1021/ja045270m

  日期：2004.12.1

  We report the preparation of two novel H-2[pz(A(n);B4-n)] porphyrazines (pzs) which were designed to position themselves quite differently when attached to a surface: one to form a standard self-assembled monolayer (SAM) roughly perpendicular to a surface, the other to lie horizontally along a surface. As the former, we synthesized a pz, 1, where one pyrrole group is functionalized with two thioethers terminated in mercaptides (SR, R = (CH2)(3)CONH(CH2)(2)S-), each protected as a disulfide, and -S-Me is attached to the other pyrrole sites; the latter is a pz, 2, with dialkoxybenzo groups fused to two trans-pyrroles of the pz ring, and SR groups are attached to the other pair of pyrroles. Nanostructures of 1 and 2 were successfully patterned on gold surfaces via dip-pen nanolithography, and the predicted molecular orientation of the resulting structures was confirmed by topographic AFM images. The two pzs exhibit similar reduction potentials in solution. Both show large shifts in potential upon surface binding, with the magnitude of the shift depending on the proximity/orientation of the pz to the surface. The first reduction potential of the "vertically" aligned 1 shifts by ca. +430 mV when incorporated in a binary pz/hexanethiol SAM, while that for 2, which lies flat, shifts by ca. +800 mV; the potential thus shifts by ca. +370 mV upon taking a given pz that stands atop a two-legged insulating "standoff" in a traditional SAM and "laying it down". We suggest these observed effects can be explained by image-charge energetics, and this is supported by a simple model.