2,6-bis(1,1-dimethylethyl)selenopyran-4-one | 104698-68-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 2,6-bis(1,1-dimethylethyl)selenopyran-4-one
• 英文别名: Δ-4H-2,6-di-tert-butylselenopyran-4-one；2,6-di-tert-butyl-4H-selenopyran-4-one；4H-2,6-di-tert-butylselenopyran-4-one；2,6-Di-tert-butylselenopyran-4-one；2.6-bis(1,1-dimethylethyl)-selenopyran-4-one；2.6-bis(1.1-dimethylethyl)selenopyran-4-one；2,6-ditert-butylselenopyran-4-one
• CAS: 104698-68-2
• 化学式: C₁₃H₂₀OSe
• 分子量: 271.261
• InChiKey: VFUCNMKFJVLFMU-UHFFFAOYSA-N

物化性质

• 沸点：
  303.8±35.0 °C(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,6-bis(1,1-dimethylethyl)selenopyran-4-one 在 劳森试剂 、 铜 作用下， 以 甲苯 、 xylene 为溶剂， 反应 24.0h， 生成 Δ^4,4'-2,2',6,6'-tetra-t-butyl-(selenapyranyl)-4H-selenapyran
  参考文献：
  名称：

  Δ4,4' -4-chalcogenapyranyl-4h-chalcogenapyrans

  摘要：

  DOI：

  10.1016/s0040-4020(01)96724-9
• 作为产物：
  描述：

  2,6-di-tert-butyl-4-methylseleninium hexafluorophosphate 在 dipotassium hydrogenphosphate 、 air 作用下， 以 乙腈 为溶剂， 以15%的产率得到2,6-bis(1,1-dimethylethyl)selenopyran-4-one
  参考文献：
  名称：

  Hydrolysis Studies of Chalcogenopyrylium Trimethine Dyes. 1. Product Studies in Alkaline Solution (pH ≥ 8) under Anaerobic and Aerobic Conditions

  摘要：

  Hydrolyses of chalcogenopyrylium dyes 1-9 give product distributions that are both heteroatom and oxygen dependent, Under anaerobic or aerobic conditions at pH 8, hydrolyses of dyes 1-4, which each contain a pyrylium ring, give 2-pentene-1,5-dione 10-13, respectively, in >90% yield from addition of hydroxide to the 2-position of the pyrylium ring followed by ring opening and tautomerization. Telluropyrylium dye 8 under anaerobic conditions over the pH range 6.9-11.0 gives a 1:1 mixture of telluropyranylidene aldehyde 14 and tris(telluropyranylidenemethyl)methane 15 derived from addition of hydroxide to the central carbon of the trimethine bridge. Under aerobic conditions, tellurophene 30(Te,Te) and trace amounts of telluropyranone 29 were also produced via oxidative mechanisms with relative yields of 30(Te,Te) increasing with pH over the pH range 6.9-11.0 and with oxygen concentration. Thiopyrylium dye 9, seleno-/thiopyrylium dye 5, selenopyrylium dye 6, and seleno-/telluropyrylium dye 7 gave hydrolysis products derived from addition of hydroxide to the 2-position of the selenopyrylium ring (thiopyrylium ring for 9) as well as to the central carbon of the trimethine backbone under both anaerobic and aerobic conditions. The resulting seleno- or thio-hemiketals ring-opened to the corresponding seleno ketones, which were then hydrolyzed to the 2-pentene-1,5-diones 11-13 from 5-7, respectively, and 11 from 9. Under aerobic conditions, some oxidation of the seleno-hemiketals from 5 and 6 were observed to give selenophenes 30(Se,S) and 30(SeSe), respectively, as well as oxidation of the telluro-hemiketal from 9 and 8 to give tellurophenes 30(Te,Se) and 30(Te,Te), repectively. Chalcogenopyranones 27-29 were also produced in modest yields in the aerobic reactions.

  DOI：

  10.1021/jo970115u

文献信息

• Chalcogenopyranones from disodium chalcogenide additions to 1,4-pentadiyn-3-ones. The role of enol ethers as intermediates
  作者：Kristi Leonard、Marina Nelen、Madhavi Raghu、Michael R. Detty

  DOI：10.1002/jhet.5570360322

  日期：1999.5

  chalcogenides to give mixtures of products in which the chalcogenopyranones 1 are minor components and the dihydrochalcogenophenes 3 are the major products. The addition of hydrogen sulfide to diynone 2b in ethanol gives a product mixture nearly identical to that observed for the addition of disodium sulfide in sodium ethoxide in ethanol to 2b. Intermediates for the addition of hydrogen chalcogenides and

  通过在乙醇钠/乙醇中将乙醇加成到1，4-戊二炔-3-酮2中，形成E-和Z-异构体的混合物的烯醇醚9。烯醇醚与硫属元素化物二钠反应，以高收率得到相应的带有烷基，芳基或杂芳基取代基的2，6-二取代硫属元素吡喃酮类化合物1，这是反应的唯一杂环产物。二炔酮2与硫属元素化物二钠反应，得到产物混合物，其中硫属元素合吡喃酮类1是次要成分，而二氢硫属元素芴3是主要产物。向二酮2b中添加硫化氢乙醇中的产物混合物与乙醇中乙醇钠中的硫化钠硫化钠加至2b中观察到的几乎相同。描述了用于向2和9二者中添加硫属元素氢和硫属元素二钠的中间体，其导致杂环产物。
• Chalcogenopyrylium Dyes as Differential Modulators of Organic Anion Transport by Multidrug Resistance Protein 1 (MRP1), MRP2, and MRP4
  作者：Robert L. Myette、Gwenaëlle Conseil、Sean P. Ebert、Bryan Wetzel、Michael R. Detty、Susan P. C. Cole

  DOI：10.1124/dmd.112.050831

  日期：2013.6

  Multidrug resistance proteins (MRPs) mediate the ATP-dependent efflux of structurally diverse compounds, including anticancer drugs and physiologic organic anions. Five classes of chalcogenopyrylium dyes (CGPs) were examined for their ability to modulate transport of [3H]estradiol glucuronide (E217 β G; a prototypical MRP substrate) into MRP-enriched inside-out membrane vesicles. Additionally, some CGPs were tested in intact transfected cells using a calcein efflux assay. Sixteen of 34 CGPs inhibited MRP1-mediated E217 β G uptake by >50% (IC50 values: 0.7–7.6 µ M). Of 9 CGPs with IC50 values ≤2 µ M, two belonged to class I, two to class III, and five to class V. When tested in the intact cells, only 4 of 16 CGPs (at 10 µ M) inhibited MRP1-mediated calcein efflux by >50% (III-1, V-3, V-4, V-6), whereas a fifth (I-5) inhibited efflux by just 23%. These five CGPs also inhibited [3H]E217 β G uptake by MRP4. In contrast, their effects on MRP2 varied, with two (V-4, V-6) inhibiting E217 β G transport (IC50 values: 2.0 and 9.2 µ M) and two (V-3, III-1) stimulating transport (>2-fold), whereas CGP I-5 had no effect. Strikingly, although V-3 and V-4 had opposite effects on MRP2 activity, they are structurally identical except for their chalcogen atom (Se versus Te). This study is the first to identify class V CGPs, with their distinctive methine or trimethine linkage between two disubstituted pyrylium moieties, as a particularly potent class of MRP modulators, and to show that, within this core structure, differences in the electronegativity associated with a chalcogen atom can be the sole determinant of whether a compound will stimulate or inhibit MRP2.

  多药耐药蛋白（MRPs）介导结构多样化化合物（包括抗癌药物和生理有机阴离子）的ATP依赖性外排。研究了五类硫族吡啶染料（CGPs）对[3H]雌二醇葡萄糖苷（E217 β G；一种典型的MRP底物）进入富含MRP的内侧外翻膜囊泡的调节能力。此外，某些CGPs在完整的转染细胞中使用钙黄绿素外排测定进行了测试。在34种CGPs中，有16种抑制了MRP1介导的E217 β G摄取超过50%（IC50值：0.7–7.6 µM）。在9种IC50值≤2 µM的CGPs中，两个属于I类，两个属于III类，五个属于V类。在完整细胞测试中，仅有16种CGPs中的4种（在10 µM浓度下）抑制了MRP1介导的钙黄绿素外排超过50%（III-1, V-3, V-4, V-6），而第五种（I-5）仅抑制了23%。这五种CGPs还抑制了MRP4对[3H]E217 β G的摄取。相较之下，它们对MRP2的影响各不相同，其中两种（V-4, V-6）抑制了E217 β G的运输（IC50值：2.0和9.2 µM），两种（V-3, III-1）则刺激了运输（>2倍），而CGP I-5没有任何影响。值得注意的是，尽管V-3和V-4对MRP2活性的影响相反，但它们的结构除了硫族原子（Se与Te）外是完全相同的。本研究首次识别了V类CGPs，它们具有独特的亚甲基或三亚甲基连接两个双取代吡啶基团，作为特别有效的MRP调节剂，并表明在这一核心结构内，与硫族原子相关的电负性差异可以是决定化合物是刺激还是抑制MRP2的唯一因素。
• Method for preparation of an intermediate dye product
  申请人：——

  公开号：US20020022723A1

  公开（公告）日：2002-02-21

  The present invention provides a novel method for the synthesis of an intermediate dye product having the following formula: 1 wherein L is S, Te, or Se; R 1 and R 2 are either the same or different aryl or alkyl compounds; R 3 is hydrogen or a short chain alkyl group; and Z is an anion. The process to formulate this intermediate compound entails reacting an R 1 -acetylene compound with an R 2 -acetylene compound (compounds A) into an enol ether compound with the R 1 and/or R 2 constituents (compound D) And from compound D, it forms into an intermediate dye compound having an L-based cyclic ring with the R 1 and/or R 2 constituents (compound F). With compound F the desired dye can be made with a greater overall yield for mass production.

  本发明提供了一种新型的中间染料合成方法，其具有以下公式：1其中L为S、Te或Se；R1和R2为相同或不同的芳基或烷基化合物；R3为氢或短链烷基；Z为阴离子。制备该中间化合物的过程涉及将R1-乙炔化合物与R2-乙炔化合物（化合物A）反应成具有R1和/或R2成分的烯醚化合物（化合物D），然后从化合物D形成具有基于L的环状环的中间染料化合物，其中包含R1和/或R2成分（化合物F）。使用化合物F可以获得更高的总产量，以进行大规模生产所需的染料。
• Squarylium compounds, and processes and intermediates for the synthesis
  申请人：Polaroid Corporation

  公开号：US05231190A1

  公开（公告）日：1993-07-27

  Squarylium compounds of the formula: ##STR1## wherein Q.sup.1 and Q.sup.2 are each independently a pyrylium, thiopyrylium, selenopyrylium, benzpyrylium, benzthiopyrylium or benzselenopyrylium nucleus, and R.sup.1 and R.sup.2 are each independently an aliphatic or cycloaliphatic group, can be prepared by reacting a squaric acid derivative of the formula: ##STR2## with a compound of the formula Q.sup.2 CH.sub.2 R.sup.2 in the presence of a base. The derivatives of Formula II may be prepared by condensing a 2,3,4,4-tetrahalocyclobut-2-en-1-one with a compound of the formula Q.sup.1 CH.sub.2 R.sup.1 in the presence of a base to produce a compound of the formula: ##STR3## wherein Q.sup.1 and R.sup.1 are as defined above, and X represents chlorine or bromine, and hydrolyzing the compound of Formula III. Alternatively, the derivatives of Formula II may be prepared by reacting a diester, monoacid chloride monoester or diacid chloride of squaric acid with a compound of the formula Q.sup.1 CH.sub.2 R.sup.1 in the presence of a base, followed by hydrolysis of the resultant monoacid chloride or monoester derivative of the compound of Formula II to the parent compound.

  化合物的公式为：##STR1## 其中Q.sup.1和Q.sup.2各自独立地是吡啶、硫代吡啶、硒代吡啶、苯并吡啶、苯并硫代吡啶或苯并硒代吡啶核，而R.sup.1和R.sup.2各自独立地是脂肪或环状脂肪基。可以通过在碱的存在下将化合物Q.sup.2 CH.sub.2 R.sup.2与公式为：##STR2## 的方酸衍生物反应来制备公式为：##STR3## 的化合物，其中Q.sup.1和R.sup.1如上所定义，X代表氯或溴，并水解化合物III。或者，可以通过在碱存在下将方酸的二酯、单酸氯单酯或二酸氯与公式为Q.sup.1 CH.sub.2 R.sup.1的化合物反应，然后水解化合物II的单酸氯或单酯衍生物以得到母体化合物。
• Squarylium compounds, and processes and intermediates for the synthesis of these compounds
  申请人：Polaroid Corporation

  公开号：US06482950B1

  公开（公告）日：2002-11-19

  Squarylium compounds of the formula: wherein Q1 and Q2 are each independently a pyrylium, thiopyrylium, selenopyrylium, benzpyrylium, benzthiopyrylium or benzselenopyrylium nucleus, and R1 and R2 are each independently an aliphatic or cycloaliphatic group, can be prepared by reacting a squaric acid derivative of the formula: with a compound of the formula Q2CH2R2 in the presence of a base. The derivatives of Formula II may be prepared by condensing a 2,3,4,4-tetrahalocyclobut-2-en-1-one with a compound of the formula Q1CH2R1 in the presence of a base to produce a compound of the formula: wherein Q1 and R1 are as defined above, and X represents chlorine or bromine, and hydrolyzing the compound of Formula III. Alternatively, the derivatives of Formula II may be prepared by reacting a diester, monoacid chloride monoester or diacid chloride of squaric acid with a compound of the formula Q1CH2R1 in the presence of a base, followed by hydrolysis of the resultant monoacid chloride or monoester derivative of the compound of Formula II to the parent compound.

  化合物的公式为Squarylium：其中Q1和Q2分别独立地为吡啶、硫代吡啶、硒代吡啶、苯基吡啶、苯基硫代吡啶或苯基硒代吡啶核，R1和R2分别独立地为脂肪基或环状脂肪基。可以通过在碱存在下将公式为的Squaric酸衍生物与公式为Q2CH2R2的化合物反应来制备公式为的Squarylium化合物。公式II的衍生物可通过在碱存在下将2,3,4,4-四卤代环丁-2-烯-1-酮与公式为Q1CH2R1的化合物缩合来制备，从而产生公式为的化合物：其中Q1和R1如上定义，X代表氯或溴，并水解公式III的化合物。或者，公式II的衍生物可以通过在碱存在下将Squaric酸的二酯、单酸氯单酯或二酸氯与公式为Q1CH2R1的化合物反应，随后水解化合物II的单酸氯或单酯衍生物以得到母体化合物。