thiochromone | 6005-15-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: thiochromone
• 英文别名: 4H-1-benzopyran-4-thione；4H-1-benzopyrane-4-thione；chromene-4-thione
• CAS: 6005-15-8
• 化学式: C₉H₆OS
• 分子量: 162.212
• InChiKey: FLGZHHJNRZUPIL-UHFFFAOYSA-N

物化性质

• 熔点：
  91 °C
• 沸点：
  241.7±43.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  41.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  thiochromone 在 cis-(2,2'-bipyridine)dinitratopalladium(II) 、 硝酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 8.5h， 以70%的产率得到色酮
  参考文献：
  名称：

  钯催化剂在室温下一锅法裂解C DoubleS双键

  摘要：

  在CS中的C = S双键2和硫酮进行催化由钯二聚配合[（N裂解∧ N）2的Pd 2（NO 3）2 ]（NO 3）2（N ∧ N，2,2'-联吡啶，在室温下在一锅中4,4'-二甲基联吡啶或4,4'-双（三氟甲基））产生CO 2和酮，分别是第一次。通过动力学NMR，同位素标记的实验，原位ESI-MS和DFT计算对机理进行了全面研究。该反应涉及水解脱硫过程以生成C═O双键和三核簇，这在催化循环中以HNO 3再生二聚催化剂起着关键作用。此外，催化剂配体的电子性质对反应速率和动力学参数具有重要影响。在相同温度下，反应速率随N的电负性的顺序一致∧N个配体（4,4'-双（三氟甲基）> 2,2'-联吡啶> 4,4'-二甲基联吡啶）。这种均相催化反应具有温和的条件，宽泛的底物范围和操作简便性，可深入了解碳硫键的催化活化机理。

  DOI：

  10.1021/acs.inorgchem.8b01275
• 作为产物：
  描述：

  色酮 在 劳森试剂 作用下， 以 苯 为溶剂， 反应 0.25h， 以85%的产率得到thiochromone
  参考文献：
  名称：

  光敏剂：香豆素，色酮，其同系物和硫酮类似物的综合光物理/光化学和理论

  摘要：

  对于22种羰基和硫酮中的许多化合物，已确定其光物理-光化学行为，包括吸收光谱，荧光光谱和寿命，磷光光谱，三重态-三重态瞬态光谱，三重态寿命和量子产率以及敏化的单重态氧的形成和产率。化合物。这些包括香豆素，补骨脂素，色酮和呋喃色酮及其硫酮。许多硫酮是首次合成的。对大多数化合物进行了两种类型的理论计算。硫酮研究的主要目标是（1）在体内产生或提高化合物的光敏剂能力，（2）将化合物的光谱移动到更长的波长，（3）增加三重态和单重态氧的量子产率。其中大多数已基本实现。已经使用一种独特的测试技术评估了两种硫酮的光敏能力，该测试技术采用了一系列基因工程细菌。

  DOI：

  10.1039/ft9938901007

文献信息

• Spin adducts of group IVB organometallic radicals with Thioketones. an esr study
  作者：Angelo Albert、Francesco Paolo Colonna、Maurizio Guerra、Bianca F. Bonini、Germana Mazzanti、Zoltàn Dinya、Gian Franco Pedulli

  DOI：10.1016/s0022-328x(00)81027-x

  日期：1981.11

  The radical adducts resulting from the reaction between group IVB organometallic radicals MR3 (M = Si, Ge, Sn; R = alkyl or aryl) and a number of thioketones of the chromone and flavone series have been investigated by ESR spectroscopy. The spectral parameters obtained for these species have been compared with those of similar adducts of the corresponding ketones. Both classes of radicals adopt an

  已经通过ESR光谱研究了IVB族有机金属自由基MR 3（M ＝ Si，Ge，Sn； R ＝烷基或芳基）与许多色酮和黄酮系列的硫酮之间的反应产生的自由基加合物。已将针对这些物质获得的光谱参数与相应酮的类似加合物的光谱参数进行了比较。这两类自由基均采用正交构象，并且前者和后者的顺磁性物种之间的差异可以通过氧和硫的不同电负性来解释。同样解释了用硫或硒原子取代杂环氧对自旋密度分布的影响。在模型系统CH 2 XSiH上进行了INDO计算3（X = O，S）。
• Reaction of vinylcarbenoids with thioketones: formation of vinylthiocarbonyl ylides followed by ring closure to thiiranes and dihydrothiophenes
  作者：Masashi Hamaguchi、Nao Funakoshi、Takumi Oshima

  DOI：10.1016/s0040-4039(99)01716-5

  日期：1999.11

  Reactions were carried out on thioketones with vinylcarbenoids. Rh2(OAc)4-catalyzed reaction of vinyldiazo compounds 1a,b with xanthione 2 and thiochromone 3 gave thiiranes 4b and olefins 5 and 6, desulfurization products from thiiranes, while the reaction of 1c with 2 and 3 afforded dihydrothiophenes 7, 8 and 9.

  在硫酮上与乙烯基类化合物反应。的Rh 2（OAc）4 vinyldiazo化合物的催化的反应1A，B与xanthione 2和thiochromone 3给硫杂丙环4B和烯烃5和6，从硫杂丙环脱硫产物，而该反应1C与2个3，得到dihydrothiophenes 7,8和9。
• [EN] PYRROLOPYRIMIDINE DERIVATIVES USEFUL AS MODULATORS OF MULTIDRUG RESISTANCE<br/>[FR] DERIVES DE PYRROLOPYRIMIDINE POUVANT ETRE UTILISES EN TANT QUE MODULATEURS DE LA MULTIRESISTANCE AUX MEDICAMENTS
  申请人：XENOVA LTD

  公开号：WO2004065389A1

  公开（公告）日：2004-08-05

  A compound which is a pyrrolopyrimidine of formula (I) wherein: R1 is selected from R9 and halogen; R2 is NR6R7; R3 is selected from H, C1-C6 alkyl which is unsubstituted or substituted and -(CH2) nAr; R4 is selected from H, C1-C6 alkyl and -(CH2)„ Ar; or R3 and R4 form, together with the N and C atoms to which they are attached, a fused five-, six-, seven- or eight-membered N-containing saturated ring which is unsubstituted or substituted; R5 is selected from CN, C02R9, C(O)NR10R11, -(CH2)nOH, -(CH2)nR10Rn, -C=CH, -C(S)NR10R11, -C(NH2)=NOR9, -C(R9)=NOR9, -C(NH2)NH, -C(O)R9 and an unsaturated 5- or 6-membered heterocyclic group which contains 1, 2 or 3 heteroatoms selected from N, O and S and which is unsubstituted or substituted; R6 and R7, which are the same or different, are selected from C1-C6 alkyl which is unsubstituted or substituted, -(CH2)nX and -(CH2)nAr; or R6 and R7 form, together with the nitrogen atom to which they are attached, a saturated five-, six-, seven- or eight-membered heterocyclic group which contains one nitrogen atom and 0 or from 1 to 3 additional heteroatoms selected from N, O and S, which is unsubstituted or substituted and which optionally contains one or two bridgehead atoms; R10 and R11, which are the same or different, are selected from H, C1-C6 alkyl which is unsubstituted or substituted, -(CH2)nC3-C10 cycloalkyl and -(CH2) nAr; or R10 and R11 form, together with the nitrogen atom to which they are attached, a saturated five or six membered heterocyclic group which contains a nitrogen atom and 0 or from to 3 additional heteroatoms selected from O, S and N, which is unsubstituted or substituted and which is optionally fused to a benzene ring which is unsubstituted or substituted; n is the same or different when more than one is present within a given substituent group and is 0 or an integer of from 1 to 6; X is selected from -CN, -C02R9 and -NR10R11; R9 is the same or different when more than one is present within a given substituent group and is selected from -H, -QAr, -(CH2) nAr, C1-C6 alkyl which is unsubstituted or substituted and -(CH2) nC3-C10cycloalkyl, wherein the cycloalkyl moiety is optionally fused to a benzene ring which is unsubstituted or substituted; Q is C2-C6 alkenylene or alkynylene; and Ar is an unsaturated C6-C10 membered carbocyclic group or an unsaturated 5-11 membered heterocyclic group, which groups are unsubstituted or substituted; or a pharmaceutically acceptable salt thereof. These compounds have activity as inhibitors of MRP (multidrug resistant protein) and may thus be used to modulate multidrug resistance, for instance in potentiating the cytotoxicity of a chemotherapeutic agent.

  一种具有以下结构式(I)的吡咯吡嘧啶化合物，其中：R1从R9和卤素中选择；R2为NR6R7；R3从H、未取代或取代的C1-C6烷基和-(CH2) nAr中选择；R4从H、C1-C6烷基和-(CH2) nAr中选择；或者R3和R4与它们连接的N和C原子一起形成未取代或取代的融合的含氮饱和环，该环为五、六、七或八元环；R5从CN、C02R9、C(O)NR10R11、-(CH2)nOH、-(CH2)nR10Rn、-C=CH、-C(S)NR10R11、-C(NH2)=NOR9、-C(R9)=NOR9、-C(NH2)NH、-C(O)R9和一个含有1、2或3个异原子（N、O和S）且未取代或取代的不饱和5-或6元杂环基中选择；R6和R7相同或不同，从未取代或取代的C1-C6烷基、-(CH2)nX和-(CH2)nAr中选择；或者R6和R7与它们连接的氮原子一起形成含有一个氮原子和0或1至3个额外异原子（N、O和S）的饱和五、六、七或八元杂环基，该环未取代或取代，可选地包含一个或两个桥头原子；R10和R11相同或不同，从未取代或取代的H、C1-C6烷基、-(CH2)nC3-C10环烷基和-(CH2)nAr中选择；或者R10和R11与它们连接的氮原子一起形成含有一个氮原子和0或1至3个额外异原子（O、S和N）的饱和五或六元杂环基，该环未取代或取代，可选地与未取代或取代的苯环融合；n在给定取代基中的多个存在时相同或不同，为0或1至6的整数；X从-CN、-C02R9和-NR10R11中选择；R9在给定取代基中的多个存在时相同或不同，从-H、-QAr、-(CH2)nAr、未取代或取代的C1-C6烷基和-(CH2)nC3-C10环烷基中选择，其中环烷基部分可选地与未取代或取代的苯环融合；Q为C2-C6烯基或炔基；Ar为未取代或取代的不饱和C6-C10环烷基或不饱和5-11元杂环基，或其药学上可接受的盐。这些化合物具有作为MRP（多药耐药蛋白）抑制剂的活性，因此可用于调节多药耐药性，例如增强化疗药物的细胞毒性。
• Photophysical triplet state processes of 4-H-1-benzopyrane-4-thione in a perfluoroalkane. Part 1.—Temperature dependence of unimolecular triplet decay
  作者：Heike Eisenberger、Bernhard Nickel

  DOI：10.1039/ft9969200733

  日期：——

  The rate constant k0T for the unimolecular decay of the lowest triplet state, T1, of 4-H-1-benzopyrane-4-thione (BPT) in perfluoro-1,3-dimethylcyclohexane was determined between 230 and 300 K. By assuming a very fast and virtually complete thermal equilibration T1⇌ S1 of the relative population of T1 and the lowest excited singlet state S1, three parameters can be calculated from the temperature dependence

  速率常数ķ 0 Ť对于最低三重态的单分子衰变，T 1，4- ħ -1-苯并吡喃-4-硫酮230和300 K.之间确定（BPT）中的全氟-1,3-二甲基环己烷通过假设一个非常快的和几乎完全的热平衡Ť 1 ⇌š 1 T的相对群体的1和最低激发单重态S 1，三个参数，可以从与温度的关系计算ķ 0 Ť：个人速率常数β s =（4.0±0.2）×10 6 s –1（S衰减）1至S 0和β ž Ť =（8.2±2）×10 4个小号-1为的衰减的强磷光三重子状态Ť Ž 1至S 0，并且能量差Δ ë（š 1，T ž 1） = T z 1和S 1之间的hc ×（757±13）cm –1。Δ的值ë（S 1，T Ž 1）与T的位置协议1,0和S 1,0在吸收光谱中。估计了S 0 →S 1跃迁的频谱。
• Benzpyrylium squarylium and croconylium dyes, and processes for their
  申请人：Polaroid Corporation

  公开号：US05627014A1

  公开（公告）日：1997-05-06

  Dyes comprising an inner salt of a compound of the formula: Q.sup.1 =Z-Q.sup.2 wherein: Q.sup.1 is a 4-(benz[b]-4H-pyrylium)methylidene, 4-(benz[b]-4H-thiopyrylium)methylidene or 4-(benz[b]-4H-selenopyrylium)methylidene grouping; Z is a 1,3-(2-hydroxy-4-oxo-2-cyclobutylidene) hydroxide or 1,3-(2-hydroxy-4,5-dioxo-2-cyclopentylidene) hydroxide ring; and Q.sup.2 is a 4-(benz[b]-4H-pyran-4-ylidene)methyl, 4-(benz[b]-4H-thiopyran-4-ylidene)methyl or 4-(benz[b]-4H-selenopyran-4-ylidene)methyl grouping; wherein at least one of the groupings Q.sup.1 and Q.sup.2 carries at its 2-position a substituent in which a non-aromatic carbon atom is bonded directly to the benzpyrylium, benzthiopyrylium or benzselenopyrylium nucleus, subject to the proviso that if this 2-substituent contains an aromatic nucleus, this aromatic nucleus is not conjugated with the benzpyrylium, benzthiopyrylium or benzselenopyrylium nucleus to which it is attached, are useful as visible and near infra-red absorbers, having high extinction coefficients and improved solubility in polymeric media.

  染料包括一个化合物内盐的内部的一种，其公式为：Q.sup.1 = Z-Q.sup.2，其中：Q.sup.1是4-（苯[b]-4H-吡啶）甲基亚甲基，4-（苯[b]-4H-噻吩）甲基亚甲基或4-（苯[b]-4H-硒吡啶）甲基亚甲基基团；Z是1,3-（2-羟基-4-氧代-2-环丁基亚甲基）羟基或1,3-（2-羟基-4,5-二氧代-2-环戊基亚甲基）羟基环；Q.sup.2是4-（苯[b]-4H-吡喃-4-亚甲基）甲基，4-（苯[b]-4H-噻喃-4-亚甲基）甲基或4-（苯[b]-4H-硒喃-4-亚甲基）甲基基团；其中至少一个基团Q.sup.1和Q.sup.2在其2位上携带一个取代基，在该取代基中，一个非芳香碳原子直接与苯吡啶，苯噻吩或苯硒吡啶核相连，但前提是如果该2-取代基含有芳香核，则该芳香核不与其相连的苯吡啶，苯噻吩或苯硒吡啶核共轭。这些染料可用作可见光和近红外吸收剂，具有高消光系数和在聚合介质中改善的溶解度。

表征谱图