3,6-Bis(dimethylamino)thioxanthon | 7031-01-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫色烯
• 英文名称: 3,6-Bis(dimethylamino)thioxanthon
• 英文别名: 3,6-Bis(dimethylamino)-9H-thioxanthen-9-one；3,6-bis(dimethylamino)thioxanthen-9-one
• CAS: 7031-01-8
• 化学式: C₁₇H₁₈N₂OS
• 分子量: 298.409
• InChiKey: PUCLIMGSMPZGNS-UHFFFAOYSA-N

物化性质

• 熔点：
  292-293 °C
• 沸点：
  487.4±45.0 °C(Predicted)
• 密度：
  1.253±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  48.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N,N-二乙基苯甲酰胺 、 3,6-Bis(dimethylamino)thioxanthon 在 四甲基乙二胺 、 叔丁基锂 、 hexafluorophosphoric acid 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 14.0h， 以42%的产率得到
  参考文献：
  名称：

  Rhodamine Inhibitors of P-Glycoprotein: An Amide/Thioamide “Switch” for ATPase Activity

  摘要：

  We have examined 46 tetramethylrosamine/rhodamine derivatives with structural diversity in the heteroatom of the xanthylium core, the amino substituents of the 3- and 6-positions, and the alkyl, aryl, or heteroaryl group at the 9-substituent. These compounds were examined for affinity and ATPase stimulation in isolated MDR3 CL P-gp and human P-gp-His(10), for their ability to promote uptake of calcein AM and vinblastine in multidrug-resistant MDCKII-MDR1 cells, and for transport in monolayers of MDCKII-MDR1 cells. Thioamide 31-S gave K-M of 0.087 mu M in human P-gp. Small changes in structure among this set of compounds affected affinity as well as transport rate (or flux) even though all derivatives examined were substrates for P-gp. With isolated protein, tertiary amide groups dictate high affinity and high stimulation while tertiary thioamide groups give high affinity and inhibition of ATPase activity. In MDCKII-MDR1 cells, the tertiary thioamide-containing derivatives promote uptake of calcein AM and have very slow passive, absorptive, and secretory rates of transport relative to transport rates for tertiary amide-containing derivatives. Thioamide 31-S promoted uptake of calcein AM and inhibited efflux of vinblastine with IC50's of similar to 2 mu M in MDCKII-MDR1 cells.

  DOI：

  10.1021/jm900253g
• 作为产物：
  描述：

  thiopyronine semiquinone radical 在 sodium hydroxide 、 三氯化铁 作用下， 以 盐酸 、 水 为溶剂， 反应 6.5h， 生成 3,6-Bis(dimethylamino)thioxanthon
  参考文献：
  名称：

  Timpe, Hans-Joachim; Kronfeld, Klaus-Peter; Mahlow, Ralph, Zeitschrift fur Chemie, 1990, vol. 30, # 2, p. 55 - 56

  摘要：

  DOI：

文献信息

• Novel chalcogenoxanthylium dyes for purging blood pathogens and for photodynamic therapy
  申请人：Detty R. Michael

  公开号：US20060040908A1

  公开（公告）日：2006-02-23

  Provided are chalcogenoxanthylium compounds which can effectively be used as sensitizers in photodynamic therapy, virucides in photodynamic antimicrobial chemotherapy and reversal agents of Pgp function in cancer cells. Further provided is a general method for the preparation of chalcogenoxanthylium compounds.

  提供了硫、硒和碲氧杂芴阳离子化合物，可有效用作光动力疗法的增敏剂、光动力抗微生物化疗的病毒灭活剂以及癌细胞Pgp功能的逆转剂。还提供了一种制备硫、硒和碲氧杂芴阳离子化合物的通用方法。
• Generation of 3- and 5-Lithiothiophene-2-carboxylates via Metal−Halogen Exchange and Their Addition Reactions to Chalcogenoxanthones
  作者：Michael K. Gannon、Michael R. Detty

  DOI：10.1021/jo062370x

  日期：2007.3.1

  Deprotonation and lithium−bromine exchange in 5- or 3-bromothiophene-2-carboxylic acids with t-BuLi form the corresponding dianion, which reacts highly regioselectively in the presence of 0.25 equiv of tetramethyl-1,2-ethylenediamine with 3,6-bis(dimethylamino) chalcogenoxanthones to give S- and Se-containing rhodamines. Quenching studies with D2O indicate that an extra equivalent of t-BuLi is not

  在5-或3-溴噻吩-2-羧酸中与t -BuLi进行去质子化和溴化锂交换形成相应的二价阴离子，该二价阴离子在0.25当量的四甲基1,2-乙二胺与3,6-的存在下发生高度区域选择性反应双（二甲基氨基）硫属黄嘌呤，得到含S和Se的罗丹明。用D 2 O进行的淬火研究表明，在这些反应中不必额外添加等价的t -BuLi。使用t -BuLi进行去质子化比用溴噻吩-2-羧酸进行金属-卤素交换要快。
• Novel Rhodamine Dyes via Suzuki Coupling of Xanthone Triflates with Arylboroxins
  作者：Michael Detty、Brandon Calitree

  DOI：10.1055/s-0029-1218535

  日期：2010.1

  Novel rhodamine dyes were prepared from xanthone precursors in a ‘one-pot’ procedure via reaction of the xanthone with trifluoromethanesulfonic anhydride followed by Pd-mediated Suzuki coupling between the xanthone triflate and an arylboroxin. Rhodamines with 9-(3- or 4-carboxyphenyl) and 9-(3-nitrophenyl) substituents were prepared by this procedure. The procedure also works well with thio- and selenoxanthones, but not with telluroxanthones.

  新型罗丹明染料是通过“一锅法”从香豆素前体制备的，该方法涉及香豆素与三氟甲基磺酸酐反应，随后再进行钯介导的铃木耦合，将香豆素三氟甲基磺酸酯与芳基硼烷反应。通过该程序制备了9-(3-或4-羧基苯基)和9-(3-硝基苯基)取代的罗丹明。该方法同样适用于硫香豆素和硒香豆素，但不适用于碲香豆素。
• Importance of Singlet Oxygen in Photocatalytic Reactions of 2-Aryl-1,2,3,4-tetrahydroisoquinolines Using Chalcogenorosamine Photocatalysts
  作者：Jennifer L. Clark、Jackie E. Hill、Irving D. Rettig、Joshua J. Beres、Roman Ziniuk、Tymish Y. Ohulchanskyy、Theresa M. McCormick、Michael R. Detty

  DOI：10.1021/acs.organomet.9b00126

  日期：2019.6.24

  photocatalytic aza-Henry reaction between these substrates and nitromethane was more efficient with selenorosamine and tellurorosamine photocatalysts than with thiorosamine and rosamine photocatalysts, corresponding to the propensity of the photocatalysts to generate singlet oxygen (1O2). Appropriately, yields for the photocatalytic aza-Henry reaction were greatly reduced when the reactions were conducted under

  使用硫族原糖胺光催化剂和LED辐照可实现2-芳基-1,2,3,4-四氢异喹啉的有氧氧化。这些底物与硝基甲烷之间的光催化aza-Henry反应与硒代罗斯明和碲代罗拉明光催化剂相比，比硫代硫胺和罗萨明光催化剂更有效，这与光催化剂产生单线态氧（1 O 2）的倾向相对应。适当地，当反应在氮气氛下进行时，光催化氮杂-亨利反应的产率大大降低。将2-芳基1,2,3,4-四氢异喹啉氧化为相应的2-芳基-3,4-二氢异喹啉酮13a – 13c在2％的乙腈水溶液中加入硒代rosamine和tellurorosamine光催化剂。已表明二-2-芳基-1,2,3,4-四氢异喹啉-1-基过氧化物14a和14b是该反应的中间体。硫代罗拉明光催化剂在辐照时确实会生成1 O 2，但未产生2-芳基-3,4-二氢异喹诺酮类化合物。这些结果表明，1 O 2和硫属元素胺的硫属元素原子（相应的过氧化过氧化物，过氧化过氧化物或过氧化
• Novel thiorhodamines and a novel method of preparation
  申请人：EASTMAN KODAK COMPANY (a New Jersey corporation)

  公开号：EP0330444A2

  公开（公告）日：1989-08-30

  There are disclosed novel thiorhodamines having the following structural formula: wherein R and R₁ are individually H or alkyl of 1 to 5 carbon atoms, and Z is an anion. Also disclosed is the only known, and novel, method for making them, namely a) conducting an addition reaction between a thioxanthone and a compound having the formula: wherein R₂ is alkyl of 1 to 5 carbon atoms; b) dehydrating the resulting compound of step a) in a strong acid to form a 9-[2-oxazolinylphenyl]thioxanthylium salt; c) hydrolyzing the oxazoline ring with acid to the 9-(2-carboxyphenyl)thioxanthylium salt; and d) optionally esterifying the resultant compound of step c) in an alkanol and strong acid, wherein the alkanol contains from 1 to 5 carbon atoms.

  公开了具有以下结构式的新型硫代二胺： 其中 R 和 R₁ 分别为 H 或 1 至 5 个碳原子的烷基，以及 Z 是阴离子。 此外，还公开了唯一已知的新型硫代二胺的制造方法，即 a) 在硫杂蒽酮和具有以下式子的化合物之间进行加成反应： 其中 R₂ 是 1 至 5 个碳原子的烷基； b) 将步骤 a)得到的化合物在强酸中脱水，形成 9-[2-噁唑啉基苯基]硫酮鎓盐； c) 用酸水解噁唑啉环，生成 9-(2-羧基苯基)硫杂蒽鎓盐；以及 d) 在烷醇和强酸中任选酯化步骤 c)得到的化合物，其中烷醇含有 1 至 5 个碳原子。