5,5-Dimethyl-1,3-dithiane | 60311-39-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二噻烷
• 英文名称: 5,5-Dimethyl-1,3-dithiane
• 英文别名: 5,5-Dimethyl-1,3-dithian
• CAS: 60311-39-9
• 化学式: C₆H₁₂S₂
• 分子量: 148.293
• InChiKey: JLECFBOCXIFOFO-UHFFFAOYSA-N

物化性质

• 沸点：
  204.7±23.0 °C(Predicted)
• 密度：
  1.031±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5,5-Dimethyl-1,3-dithiane 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：

  新戊二醇二甲基硫酸酯 在 sodium sulfide 、 lithium aluminium tetrahydride 、 三氟化硼乙醚 作用下， 生成 5,5-Dimethyl-1,3-dithiane
  参考文献：
  名称：

  Aggarwal, Varinder K.; Davies, Ian W.; Franklin, Richard J., Journal of the Chemical Society. Perkin transactions I, 1991, # 3, p. 662 - 664

  摘要：

  DOI：

文献信息

• Spirocyclic nitriles as protease inhibitors
  申请人：Schudok Manfred

  公开号：US20090275523A1

  公开（公告）日：2009-11-05

  The invention relates to substituted carbo- and heterocyclic spiro compounds of the formula Ia which inhibit thiol proteases, to processes for their preparation and to the use thereof as medicaments.

  这项发明涉及公式Ia的取代碳氢和杂环螺环化合物，其抑制硫醇蛋白酶，以及它们的制备方法和用作药物的用途。
• Mono-N-tosylsulfimides, their preparation and their reaction products
  申请人：Polaroid Corporation

  公开号：US04107176A1

  公开（公告）日：1978-08-15

  This application is directed to cycloalkanes containing the moiety --SO.sub.2 --CH.sub.2 --X-- wherein X represents ##STR1## wherein R is hydrogen or alkyl and R' is alkyl and to the preparation of these compounds which find utility as silver halide complexing agents. This application is also concerned with cycloalkanes containing the moiety ##STR2## useful as intermediates in the preparation of the aforementioned compounds. Also included within the confines of this disclosure are the 2-thioether-substituted derivatives of certain of the above-identified cycloalkanes and with the synthesis of all of these compounds.

  本申请涉及含有基团--SO.sub.2 --CH.sub.2 --X--的环烷烃，其中X代表##STR1##其中R为氢或烷基，R'为烷基，以及制备这些化合物，这些化合物可用作银卤化物络合剂。本申请还涉及含有基团##STR2##的环烷烃，可作为制备上述化合物的中间体。此公开范围还包括某些上述环烷烃的2-硫醚取代衍生物以及所有这些化合物的合成。
• SUBSTITUTED CYCLOALKENE DERIVATIVE
  申请人：Kimura Tomio

  公开号：US20090233952A1

  公开（公告）日：2009-09-17

  [Object] To provide a substituted cycloalkene derivative having an action to suppress intracellular signal transduction or cell activation induced by endotoxin and to suppress cell responses due to the intracellular signal transduction and cell activation such as an excess generation of inflammatory mediators such as TNF-α, pharmacologically acceptable salts therefor, a medicament containing them as an active ingredient, a preparation method therefor, and a medicament containing the aforementioned substituted cycloalkene derivative as an active ingredient which is superior in prophylaxis and/or treatment of diseases such as sepsis (septic shock, disseminated intravascular coagulation, multiple organ failure and the like), that are associated with intracellular signal transduction or cell activation induced by endotoxin and to cell responses to the intracellular signal transduction and cell activation. [Solution] A compound represented by the general formula (I): wherein X and Y represent a group in which X and Y together with a carbon atom to which they are bound form ring A (the ring is 3- to 7-membered heterocyclyl ring or 3- to 7-membered cycloalkyl ring), each represents a hydrogen atom, or X and Y together represent a substituent of ring B. l and m, independently from each other, represent an integer of 0 to 3, and l+m is 1 to 3. R 1 is an aliphatic hydrocarbon group and the like which may be substituted with a group selected from Substituent group β and Substituent group γ. n represents an integer of 0 to 3. R 2 is a C 1 -C 6 alkyl group and the like which may be substituted with a group selected from a hydrogen atom and Substituent group β. R 3 is a phenyl group, 5- to 6-membered heteroaryl group and the like which may be substituted with a group selected from Substituent group ε. R 5 is a C 1 -C 6 alkyl group and the like which may be substituted with a group selected from a hydrogen atom and Substituent group β. Provided that in the case where R 3 is a phenyl group which may be substituted with a group selected from Substituent group ε, X and Y represent a group in which X and Y together with a carbon atom to which they are bound form ring A, or X and Y together represent a substituent of ring B.

  [目的] 提供一种替代环烯烃衍生物，具有抑制内毒素诱导的细胞内信号传导或细胞活化并抑制细胞对细胞内信号传导和细胞活化的反应，例如过量生成TNF-α等炎症介质，其药理学上可接受的盐，包含其作为活性成分的药物，其制备方法以及含有上述替代环烯烃衍生物作为活性成分的药物，其在预防和/或治疗与内毒素诱导的细胞内信号传导或细胞活化以及对细胞内信号传导和细胞活化的反应有关的疾病，例如败血症（败血性休克，弥漫性血管内凝血，多器官衰竭等）方面具有优越性。 [解决方案] 一种由通式（I）表示的化合物：其中，X和Y表示与它们结合的碳原子形成环A（环为3-至7成员的杂环或3-至7成员的环烷基环）的基团，每个表示氢原子，或X和Y一起表示环B的取代基。l和m，独立地，表示0至3的整数，且l+m为1至3。R1是脂肪烃基等，可以被从取代基组β和取代基组γ中选择的基团取代。n表示0至3的整数。R2是C1-C6烷基等，可以被从氢原子和取代基组β中选择的基团取代。R3是苯基，5-至6成员的杂环基等，可以被从取代基组ε中选择的基团取代。R5是C1-C6烷基等，可以被从氢原子和取代基组β中选择的基团取代。但在R3是苯基且可以被从取代基组ε中选择的基团取代的情况下，X和Y表示与它们结合的碳原子形成环A的基团，或X和Y一起表示环B的取代基。
• 4-ACYLAMINOPYRAZOLE DERIVATIVES
  申请人：Sankyo Company, Limited

  公开号：EP1329160A2

  公开（公告）日：2003-07-23

  A 4-acylaminopyrazole derivative represented by the following general formula: wherein R1 is a hydrogen atom, an optionally substituted C1-C16 alkyl group or the like,    R2 and R3 are independently a hydrogen atom, a halogen atom, an optionally substituted C1-C6 alkyl group or the like, R4 is a hydrogen atom, a C1-C6 alkyl group or a cyano group, Z is an oxygen atom or a sulfur atom, Ar is an optionally substituted C6-C14 aryl group or an optionally substituted 5-6 membered unsaturated heterocyclic group, B is a hydrogen atom, a halogen atom, an optionally substituted C1-C16 alkyl group or the like.

  由以下通式代表的 4-酰氨基吡唑衍生物： 其中 R1 是氢原子、任选取代的 C1-C16 烷基或类似基团、 R2 和 R3 独立地为氢原子、卤素原子、任选取代的 C1-C6 烷基或类似基团、 R4 是氢原子、C1-C6 烷基或氰基、 Z 是氧原子或硫原子、 Ar 是任选取代的 C6-C14 芳基或任选取代的 5-6 位元不饱和杂环基团、 B 是氢原子、卤素原子、任选取代的 C1-C16 烷基或类似基团。
• Synthesis and Conformational Behavior of 2-Phosphonio- and 2-Phosphinyl-1,3-dithianes. Operation of the Generalized Anomeric Effect in the S-C-P+ System
  作者：Marian Mikolajczyk、Piotr P. Graczyk

  DOI：10.1021/jo00121a043

  日期：1995.8

  A stereoselective preparation of various 2-phosphinyl- and 2-phosphonio-1,3-dithianes by desulfurization of the appropriate 2-thiophosphoryl-1,3-dithianes was described. The structure of the title compounds was studied by means of H-1, C-13, and P-31 NMR methods. Configurational assignments were also based on chemical correlation and X-ray structure determination. Both the NMR studies of conformationally labile models and equilibration of diastereomeric compounds showed an increased preference of the phosphinyl and phosphonium groups for the axial orientation. Magnitude of the anomeric effect found varies in the range from ca. 6 kJ/mol in phosphines to more than 10 kJ/mol in phosphonium salts. The anomeric effect could stem from the n(s)-sigma*(c-p) hyperconjugative interaction. If phenyl groups are connected with phosphorus, overlap repulsion involving lone electron pairs of the endocyclic sulfur atoms and pi-electrons of phenyl rings should also be taken into account. The reverse anomeric effect was not observed. No manifestation of the exo anomeric effect in 2-phosphinyl-1,3-dithianes was found.