四甲基焦磷酸硫代酸酯 | 18764-12-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 中文名称: 四甲基焦磷酸硫代酸酯
• 英文名称: tetramethyl thiodiphosphate
• 英文别名: Thiopyrophosphoric acid, tetramethyl ester；dimethoxyphosphinothioyl dimethyl phosphate
• CAS: 18764-12-0
• 化学式: C₄H₁₂O₆P₂S
• 分子量: 250.149
• InChiKey: YOJYWCJJBFKIRJ-UHFFFAOYSA-N

物化性质

• 沸点：
  65 °C(Press: 0.01 Torr)
• 密度：
  1.370±0.06 g/cm3(Predicted)
• 溶解度：
  可溶于氯仿（少许）

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  95.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  四甲基焦磷酸硫代酸酯 、 碘代三甲硅烷 以 二氯甲烷 为溶剂， 生成 O,O',O'',O'''-Tetrakis-(trimethylsilyl)-thiodiphosphat
  参考文献：
  名称：

  The Selective Displacement ofO-Alkyl by Trialkylsilyl in Some Derivatives of Acids of Phosphorus

  摘要：

  DOI：

  10.1055/s-1978-24891
• 作为产物：
  描述：

  氯磷酸二甲酯 在 吡啶 、 双(三甲基硫化硅) 作用下， 反应 5.0h， 生成 四甲基焦磷酸硫代酸酯
  参考文献：
  名称：

  Lebedev,E.P. et al., Journal of general chemistry of the USSR, 1979, vol. 49, p. 1515 - 1516

  摘要：

  DOI：
• 作为试剂：
  描述：

  碘代三甲硅烷 在 四甲基焦磷酸硫代酸酯 作用下， 反应 6.0h， 生成 O,O,O',S-tetrakis(trimethylsilyl) thiodiphosphate
  参考文献：
  名称：

  Synthesis of (S)-Isoprenoid Thiodiphosphates as Substrates and Inhibitors

  摘要：

  Thiolo thiophosphate analogues of isopentenyl diphosphate (IPP), dimethylallyl. diphosphate (DMAPP), geranyl diphosphate (GPP), farnesyl diphosphate (FPP), and geranylgeranyl diphosphate (GGPP) were synthesized, Inorganic thiopyrophosphate (SPP) was prepared from trimethyl phosphate in four steps. The tris(tetra-n-butylammonium) salt was then used to convert isopentenyl tosylate to (S)-isopentenyl thiodiphosphate (ISPP). (S)-Dimethylallyl (DMASPP), (S)-geranyl (GSPP), (S)-farnesyl (FSPP), and (S)-geranylgeranyl thiodiphosphate (GGSPP) were prepared from the corresponding bromides in a similar manner. ISPP and GSPP were substrates for avian farnesyl diphosphate synthase (FPPase). Incubation of the enzyme with ISPP and GPP gave FSPP, whereas incubation with IPP and GSPP gave FPP. GSPP was a substantially less reactive than GPP in the chain elongation reaction and was an excellent competitive inhibitor, K-I(GSPP) = 24.8 muM, of the enzyme. Thus, when ISPP and DMAPP were incubated with FPPase, GSPP accumulated and was only slowly converted to FSPP.

  DOI：

  10.1021/jo010505n

文献信息

• PREPARATION AND TOXICITY OF SOME ALKYL THIOPYROPHOSPHATES
  作者：R. A. McIvor、G. D. McCarthy、G. A. Grant

  DOI：10.1139/v56-235

  日期：1956.12.1

  Several methods have been investigated for the synthesis of tetraalkyl thiopyrophosphates, including one that can be carried out very rapidly with high yield. Purification of these compounds proved exceedingly difficult, because they were sensitive to traces of acids or bases, and probably to inorganic salts at temperatures above 70 °C. All methods investigated yield only the thiono isomer, there being

  已经研究了几种合成硫代焦磷酸四烷基酯的方法，包括一种可以非常快速且产率高的方法。事实证明，这些化合物的纯化极其困难，因为它们对痕量的酸或碱敏感，并且可能在 70 °C 以上的温度下对无机盐敏感。所有研究的方法仅产生硫代异构体，没有证据表明相应的 P-S-P 异构体。毒理学研究不支持 Fiszer 和工作人员报告的结果。没有一种化合物比焦磷酸四乙酯在静脉内的毒性更大。报道了用于红外研究的几种其他相关化合物的合成。
• Understanding and Engineering the Stereoselectivity of Humulene Synthase
  作者：Carsten Schotte、Peer Lukat、Adrian Deuschmann、Wulf Blankenfeldt、Russell J. Cox

  DOI：10.1002/anie.202106718

  日期：2021.9.6

  cyclized reaction product and thiolodiphosphate reveal a new farnesyl diphosphate binding motif that comprises a unique binuclear Mg2+-cluster and an essential K289 residue that is conserved in all humulene synthases involved in TS formation. Structure-based site-directed mutagenesis of AsR6 and its homologue EupR3 identify a single residue, L285/M261, that controls the production of either 2E,6E,9E-

  非经典萜烯环化酶 AsR6 负责在托酚酮倍半萜 (TS) 异戊烯 A 生物合成过程中形成 2 E ,6 E ,9 E -葎草烯。未配体 AsR6 和与晶体复合的 AsR6 的结构环化反应产物和硫代二磷酸揭示了一个新的法呢基二磷酸结合基序，该基序包含独特的双核 Mg 2+簇和重要的 K289 残基，该残基在参与 TS 形成的所有葎草烯合酶中都是保守的。AsR6 及其同源物 EupR3 的基于结构的定点诱变鉴定出单个残基 L285/M261，其控制 2 E ,6 E ,9 E - 或 2 Z ,6 E ,9 E -humulene的产生。使用不同的类异戊二烯前体研究了观察到的立体选择性的可能机制，结果表明 M261 对产物形成具有把关控制作用。
• Synthesis and Enzymatic Studies of Isoprenoid Thiolo Bisubstrate Analogues
  作者：Gurusankar Ramamoorthy、Richard M. Phan、C. Dale Poulter

  DOI：10.1021/acs.joc.6b00664

  日期：2016.6.17

  isopentenyl diphosphate (IPP) in the primary building reactions in the isoprenoid biosynthetic pathway. Bis-O-diphosphate analogues 3-OPP/OPP, 4-OPP/OPP, and 5-OPP/OPP and bis-thiolodiphosphate bisubstrate analogues 3-SPP/SPP, 4-SPP/SPP, and 5-SPP/SPP were synthesized. The analogues 4-OPP/OPP, 5-OPP/OPP, 4-SPP/SPP, and 5-SPP/SPP were excellent competitive inhibitors of avian farnesyl diphosphate synthase

  链延长异戊二烯基转移酶在异戊二烯生物合成途径的主要构建反应中，催化将烯丙基异戊二烯二磷酸的烃部分加到异戊烯基二磷酸（IPP）中的碳-碳双键中。双- ø二磷酸类似物3- OPP / OPP，4- OPP / OPP，和5-OPP / OPP和双thiolodiphoSPhate双底物类似物3-SPP / SPP，4-SPP / SPP，和5-SPP / SPP合成。类似物4-OPP / OPP，5-OPP / OPP，4-SPP / SPP和5-SPP / SPP分别是K I = 1.0±0.12μM，K I = 0.5±0.2μM，K I = 0.7±0.3μM和K I = 2.9±0.27μM的禽法呢基二磷酸合酶的优异竞争抑制剂，而类似物3- OPP / OPP和3-SPP / SPP分别显示了K I = 1.4μM和K I = 5.5μM的混合型抑制。
• Fiszer et al., Roczniki Chemii, 1953, vol. 27, p. 482,489
  作者：Fiszer et al.

  DOI：——

  日期：——
• Synthesis of Geranyl <i>S</i>-Thiolodiphosphate. A New Alternative Substrate/Inhibitor for Prenyltransferases
  作者：Richard M. Phan、C. Dale Poulter

  DOI：10.1021/ol006055n

  日期：2000.7.1

  [GRAPHICS]The tris(tetra-n-butylammonium) salt of thiopyrophosphate 5 was prepared from trimethyl phosphate in four steps. Treatment of geranyl bromide with 5 gave an 80% yield of geranyl S-thiolodiphosphate (6), Thiolodiphosphate 6 is substantially less reactive than geranyl diphosphate (7) in the prenyl transfer reaction catalyzed by farnesyl diphosphate synthase and is a good inhibitor of the enzyme.