2,2-二甲基-1,3-丙二硫醇 | 53555-42-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醇
• 中文名称: 2,2-二甲基-1,3-丙二硫醇
• 英文名称: 2,2-dimethyl-1,3-propanedithiol
• 英文别名: 2,2-dimethylpropane-1,3-dithiol；2,2-Dimethyl-1,3-propandithiol
• CAS: 53555-42-3
• 化学式: C₅H₁₂S₂
• 分子量: 136.282
• InChiKey: SGLYOTGYKDFSSC-UHFFFAOYSA-N

物化性质

• 沸点：
  72 °C(Press: 12 Torr)
• 密度：
  0.978±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  7
• 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：
  2
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2-二甲基-1,3-丙二硫醇 在 N-氯代丁二酰亚胺 、 tetraphosphorus decasulfide 、 N,N-二乙基苯胺 作用下， 以 苯 为溶剂， 反应 18.33h， 生成 5,5-Dimethyl-2--1,3-dithiane
  参考文献：
  名称：

  Conformational Preference in 1,3-Dithianes Containing 2-Phosphoryl, -(thiophosphoryl), and -(selenophosphoryl) groups. Chemical and Crystallographic Implications of the Nature of the Anomeric Effect

  摘要：

  The operation of the anomeric effect in all the title compounds studied was found. The magnitude of the anomeric effect was found to be larger than 10 kJ/mol. Crystallographic, spectroscopic, and thermodynamic data suggest that the n(S)-sigma*(C-P) hyperconjugative interaction is one of the factors responsible for the anomeric effect. The second interaction stabilizing the axial position of phosphorus can be P=Y...H(4 or 6) hydrogen bond formation. Some other interactions are also possible, namely sigma(C(4,6)-S)-sigma*(C(2)-P) (preferring the equatorial position of phosphorus) and sigma(C(4,6)-S)-pi(P=Y) hyperconjugations and the n(S)-n(Y) repulsions. The latter interaction was also proposed as MO counterpart of lone pair-lone pair repulsions suggested by molecular mechanics calculations. It was proved that various conformation probes can afford different equilibrium constants, if weighted average method and conformationally fixed models are applied. Most of the physical quantities are dependent on the alkyl substitution in the 1,3-dithiane ring. Thus, the relevant procedure for the selection of conformational probe was presented. Since the gamma-effect value in C-13 NMR spectra was found to be very sensitive to the position of a substituent connected with the anomeric carbon atom of 1,3-dithianes, it was applied as a conformational probe. A long range (4)J(C-P) coupling constant in the C-13 NMR spectra and P-31 spin-lattice T-1(DD) relaxation times suggest the existence of close contact(s) between a heteroatom Y(Y=O,S,Se) connected with the axial phosphorus P=Y and axial protons H(4,6) in the 1,3-dithiane ring. Crystallographic data show that the distance from Y to one of these protons is usually much smaller than to the other one and smaller than the sum of H,Y van der Waals radii. The possibility of H..Y hydrogen bond formation is discussed.

  DOI：

  10.1021/jo00086a016
• 作为产物：
  描述：

  1,3-二(甲苯磺酰氧基)-2,2-二甲基丙烷 在 sodium sulfide 、 lithium aluminium tetrahydride 、 sulfur 作用下， 生成 2,2-二甲基-1,3-丙二硫醇
  参考文献：
  名称：

  用构象氘同位素效应通过实验探索超共轭

  摘要：

  超共轭作用是许多具有根本和实际重要性的化学现象的基础。由于对端基异构作用的极大兴趣，已经在含氧体系中彻底研究了类似端基的超共轭作用。但是，在第二行和第三行硫族元素中的这种相互作用了解得较少，并引起了一些争议。在这里，我们表明，构象氘同位素效应与桑德斯的同位素摄动方法相结合，可通过可变温度，动态NMR光谱法对二恶烷，二噻吩和二硒烷类似物中的构象平衡进行敏感而直接的实验探测。我们发现，氧，硫和硒类似物的构象氘同位素效应强度分别为252.1、28.3和7.1 J / mol（±10％）。在红外光谱的支持下，并与DFT计算和自然键序分析相一致，在整个过程中x →σC –H（D）相互作用。

  DOI：

  10.1021/jo3017988

文献信息

• Structure-reactivity relations for thiol-disulfide interchange
  作者：Janette Houk、George M. Whitesides

  DOI：10.1021/ja00256a040

  日期：1987.10

  di- and trithiols and the disulfides derived from either 2-mercaptoethanol or dithiothreitol. Reactions were conducted in methanol-d,/aqueous buffer (pH 7) or methanold, at 25 "C, using NMR spectroscopy to follow the reactions. These data were used to rank the dithiols in terms of reduction potential and to infer the structure of the disulfides formed from them on oxidation. There is a general correlation

  平衡常数由 36 个二硫醇和三硫醇与衍生自 2-巯基乙醇或二硫苏糖醇的二硫化物之间的硫醇-二硫化物交换确定。反应在甲醇-d/水性缓冲液 (pH 7) 或甲醇中进行，在 25°C 下，使用 NMR 光谱跟踪反应。这些数据用于根据还原电位对二硫醇进行排序并推断其结构氧化时由它们形成的二硫化物。二硫醇的还原能力与氧化时形成的含二硫化物环的大小之间存在普遍的相关性：形成六元环的二硫醇还原性最强（K = 103-105 M 相对于氧化的 2-巯基乙醇）；五元和七元环的还原性降低约 1 个数量级。类似于 1 的化合物，2-乙二硫醇在相对稀释的溶液 (- 1 mM) 中形成环状双（二硫化物）二聚体，但在较高浓度下聚合。其他类别的二硫醇在氧化时形成聚合物。
• Ferrous Carbonyl Dithiolates as Precursors to FeFe, FeCo, and FeMn Carbonyl Dithiolates
  作者：Maria E. Carroll、Jinzhu Chen、Danielle E. Gray、James C. Lansing、Thomas B. Rauchfuss、David Schilter、Phillip I. Volkers、Scott R. Wilson

  DOI：10.1021/om400752a

  日期：2014.2.24

  Reported are complexes of the formula Fe(dithiolate)(CO)2(diphos) and their use to prepare homo- and heterobimetallic dithiolato derivatives. The starting iron dithiolates were prepared by a one-pot reaction of FeCl2 and CO with chelating diphosphines and dithiolates, where dithiolate = S2(CH2)22– (edt2–), S2(CH2)32– (pdt2–), S2(CH2)2(C(CH3)2)2– (Me2pdt2–) and diphos = cis-C2H2(PPh2)2 (dppv), C2H4(PPh2)2

  报道了式 Fe(dithiolate)(CO) 2 (diphos) 的配合物及其用于制备均和异双金属二硫醇衍生物的用途。起始二硫醇铁是通过 FeCl 2和 CO 与螯合二膦和二硫醇的一锅反应制备的，其中二硫醇= S 2 (CH 2 ) 2 2– (edt 2– ), S 2 (CH 2 ) 3 2– (pdt 2– ), S 2 (CH 2 ) 2 (C(CH 3 ) 2 ) 2– (Me 2 pdt 2–) 和 diphos = cis -C 2 H 2 (PPh 2 ) 2 (dppv), C 2 H 4 (PPh 2 ) 2 (dppe), C 6 H 4 (PPh 2 ) 2 (dppbz), C 2 H 4 [ P(C 6 H 11 ) 2 ] 2 (dcpe)。将57 Fe 掺入这种结构单元复合物始于将57 Fe 转化为57 Fe 2 I 4 (i PrOH) 4，然后用K 2
• A Novel Phenylchromane Derivative Increases the Rate of Glucose Uptake in L6 Myotubes and Augments Insulin Secretion from Pancreatic Beta-Cells by Activating AMPK
  作者：Naomi Rozentul、Yosef Avrahami、Moran Shubely、Laura Levy、Anna Munder、Guy Cohen、Erol Cerasi、Shlomo Sasson、Arie Gruzman

  DOI：10.1007/s11095-017-2271-7

  日期：2017.12

  A series of novel polycyclic aromatic compounds that augment the rate of glucose uptake in L6 myotubes and increase glucose-stimulated insulin secretion from beta-cells were synthesized. Designing these molecules, we have aimed at the two main pathogenic mechanisms of T2D, deficient insulin secretion and diminished glucose clearance. The ultimate purpose of this work was to create a novel antidiabetic drug candidate with bi-functional mode of action. All presented compounds were synthesized, and characterized in house. INS-1E cells and L6 myoblasts were used for the experiments. The rate of glucose uptake, mechanism of action, level of insulin secretion and the druggability of the lead compound were studied. The lead compound (6-(1,3-dithiepan-2-yl)-2-phenylchromane), dose- and time-dependently at the low μM range increased the rate of glucose uptake in L6 myotubes and insulin secretion in INS-1E cells. The compound exerted its effects through the activation of the LKB1 (Liver Kinase B1)-AMPK pathway. In vitro metabolic parameters of this lead compound exhibited good druggability. We anticipate that bi-functionality (increased rate of glucose uptake and augmented insulin secretion) will allow the lead compound to be a starting point for the development of a novel class of antidiabetic drugs.

  一系列新型多环芳香化合物被合成，这些化合物能够提高L6肌管中葡萄糖摄取速率，并增加β细胞中葡萄糖刺激的胰岛素分泌。在设计这些分子时，我们针对T2D的两个主要发病机制：胰岛素分泌不足和葡萄糖清除率降低。这项工作的最终目的是创造一种具有双重作用模式的新型抗糖尿病候选药物。所有介绍的化合物均在内部合成和表征。实验使用了INS-1E细胞和L6肌细胞。研究了葡萄糖摄取速率、作用机制、胰岛素分泌水平及先导化合物的成药性。先导化合物（6-(1,3-二硫杂环戊烷-2-基)-2-苯基色满）在低微摩尔范围内，剂量和时间依赖性地增加L6肌管中葡萄糖摄取速率及INS-1E细胞中胰岛素分泌。该化合物通过激活LKB1（肝激酶B1）-AMPK途径发挥作用。体外代谢参数显示该先导化合物具有良好的成药性。我们预期其双重功能（增加葡萄糖摄取速率和增强胰岛素分泌）将使该先导化合物成为开发新型抗糖尿病药物的起点。
• Catalysts
  申请人：Econic Technologies Ltd

  公开号：US20170210848A1

  公开（公告）日：2017-07-27

  The present invention relates to the field of polymerisation catalysts, and systems comprising said catalysts for polymerising carbon dioxide and an epoxide, a lactide and/or lactone, and/or an epoxide and an anhydride. The catalyst is of formula (I): Wherein M 1 and M 2 are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Ni(II), Mg(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(III)-X, Ni(III)-X, Mn(III)-X, Fe(III)-X, Ca(II), Ge(II), Al(III)-X, Ti(III)-X, V(III)-X, Ge(IV)-(X) 2 or Ti(IV)-(X) 2 . R 3A is different from R 3B ; and/or at least one occurrence of E 3 , E 4 , E 5 and E 6 is different to a remaining occurrence of E 3 , E 4 , E 5 and E 6 . A ligand, a process of asymmetric N-substitution of a symmetrical ligand and a process for the reaction of: (i) carbon dioxide with an epoxide; (ii) an epoxide and an anhydride; and/or (iii) a lactide and/or a lactone, in the presence of a catalyst is also described.

  本发明涉及聚合催化剂领域，以及包括所述催化剂的系统，用于聚合二氧化碳和环氧化物，内酯和/或内酯，以及环氧化物和酸酐。催化剂的化学式为（I）：其中M1和M2分别选自Zn（II）、Cr（II）、Co（II）、Cu（II）、Mn（II）、Ni（II）、Mg（II）、Fe（II）、Ti（II）、V（II）、Cr（III）-X、Co（III）-X、Ni（III）-X、Mn（III）-X、Fe（III）-X、Ca（II）、Ge（II）、Al（III）-X、Ti（III）-X、V（III）-X、Ge（IV）-（X）2或Ti（IV）-（X）2。R3A与R3B不同；和/或至少有一个E3、E4、E5和E6的出现与其余的E3、E4、E5和E6的出现不同。还描述了一种配体、对称配体的不对称N-取代的过程以及在催化剂存在下进行以下反应的过程：（i）二氧化碳与环氧化物；（ii）环氧化物和酸酐；和/或（iii）内酯和/或内酯。
• Molecular Rods Based on Oligo-spiro-thioketals
  作者：P. Wessig、M. Gerngroß、D. Freyse、P. Bruhns、M. Przezdziak、U. Schilde、A. Kelling

  DOI：10.1021/acs.joc.5b02670

  日期：2016.2.5

  on an extension of the previously established concept of oligospiroketal (OSK) rods by replacing a part or all ketal moieties by thioketals leading to oligospirothioketal (OSTK) rods. In this way, some crucial problems arising from the reversible formation of ketals are circumvented. Furthermore, the stability of the rods toward hydrolysis is considerably improved. To successfully implement this concept

  我们报告了以前建立的寡螺酮（OSK）杆的概念的扩展，方法是用硫酮缩酮代替部分或全部缩酮部分，从而形成寡螺硫缩酮（OSTK）杆。以这种方式，避免了由于缩酮的可逆形成而引起的一些关键问题。此外，棒的抗水解稳定性大大提高。为了成功地实现这一概念，我们首先开发了许多新的寡硫醇结构单元，分别改善了已知的寡硫醇的合成可及性。硫缩醛的另一个优点是对苯二甲醛（TAA）套筒（在缩醛的情况下太柔韧）可以用于OSTK棒中。成功制备一些长度为几纳米的OSTK棒证明了OSTK方法的可行性。