2,2,5',5''-tetramethylspiro<1,3,4>oxadithiin>-4-one | 219829-58-0

• 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: 2,2,5',5''-tetramethylspiro<1,3,4>oxadithiin>-4-one
• 英文别名: 2,2,5',5'-tetramethyl-4H,5'H-spiro[chromene-3,2'-[1,3,4]oxadithiino[5,6-c]chromen]-4-one；2,2,5',5'-Tetramethylspiro[chroman-3,2'-2h-chromeno[3,4-e][1,3,4]oxadithiin]-4-one；2',2',5,5-tetramethylspiro[[1,3,4]oxadithiino[5,6-c]chromene-2,3'-chromene]-4'-one
• CAS: 219829-58-0
• 化学式: C₂₂H₂₀O₄S₂
• 分子量: 412.53
• InChiKey: OJIRJWWYRBTKHI-UHFFFAOYSA-N

物化性质

• 熔点：
  145-147 °C
• 沸点：
  570.807±50.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.406±0.10 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  28
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  95.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,2,5',5''-tetramethylspiro<1,3,4>oxadithiin>-4-one 、 天然橡胶 以 苯 为溶剂， 反应 1.0h， 以88%的产率得到2',2',3-trimethyl-spiro(benzopyran-3',6-Δ³-thiapyran)-4'-one
  参考文献：
  名称：

  Thermolysis of Some Spirobenzopyran-3’,2-[1,3,4]oxadithiino- [5,6-c]benzopyran-4’-ones in the Presence of Some Homodienes and Crystallographic Studies of Some Adducts

  摘要：

  非常活泼的α-氧代硫酮衍生物2a-d，通过热解螺苯并吡喃-3’，2-[1,3,4]氧硫代噻吩[5,6-c]苯并吡喃-4’-酮1a-d生成，与2,3-二甲基-1,3-丁二烯和1,3-环己二烯在[4+2]-环加成反应中反应，得到螺苯并吡喃-3’，6-硫代吡喃-4’-酮加合物3a-d和螺苯并吡喃-3’，3-硫代双环[2.2.2]辛-5-烯-4’-酮加合物4a-d。另一方面，α-氧代硫酮2a-d与异戊二烯反应，只选择性地生成3-甲基硫代吡喃衍生物5a-d。4b、4c和5a的单晶X射线衍射研究为已建立的结构提供了良好支持。

  DOI：

  10.1515/znb-2006-1115
• 作为产物：
  描述：

  2,2-二甲基-苯并二氢吡喃-4-酮 在 吗啉 、 氯化亚砜 作用下， 以 四氯化碳 、 乙醚 为溶剂， 生成 2,2,5',5''-tetramethylspiro<1,3,4>oxadithiin>-4-one
  参考文献：
  名称：

  Cycloadditions with 2,2-Dialkyl-3-thioxochroman-4-one S-Sulfides Including an Unprecedented [3 + 5] Cycloaddition

  摘要：

  We report the facile generation of the chroman-4-one-derived thiosulfines 10 under mild conditions by our well-established nucleophilic "unzipping" of the corresponding acetyl alpha-chloroalkyl disulfides 9 which in turn can be prepared from the corresponding alpha-chloro sulfenyl chlorides 8. Spontaneous partial loss of sulfur from 10, most probably by the disproportionation of 10 to 11 and 12, generates the expectedly reactive beta-oxo thioketones 11 which partly dimerize in a precedented Diels-Alder fashion, to give the 1,3,4-oxadithiins 13, and partly cycloadd to 10 to form the 1,2,4-trithiolanes 14 in a well-precedented fashion. Dimerization of 10 can occur in two competing ways: the precedented nonconcerted [3 + 3] cycloaddition (to give 1,2,4,5-tetrathianes 15) and the unprecedented concerted [3 + 5] addition to give 1,3,4,5,6-oxatetrathiocins 16. In the latter interaction one molecule of 10 behaves as a 1,5-dipole and a second molecule as a 1,3-dipole. In one case (10d) extensive sulfur scrambling takes place with formation of the 1,2,3,4,5,6-hexathiepane 17d. It is remarkable how sensitive the reactions of 10 are to minor variations of the simple alkyl substituents in the 2-position. In addition to the usual spectroscopic characterization all isolated key compounds were subjected to X-ray single-crystal structure determinations.

  DOI：

  10.1021/jo981534+

文献信息

• Novel regioselective synthesis of 3′<i>H</i>,4<i>H</i>-spiro[chromene-3,2′-[1,3,4]thiadiazol]-4-one containing compounds
  作者：Mohamed I. Hegab、Adel S. Girgis、I. S. Ahmed-Farag

  DOI：10.1002/jhet.5570430515

  日期：2006.9

  2′-chromene-3′,2″-[1,3,4]oxadithiino[5,6-c]chromene-5″,1″′-cyclohexan]-4′-one (1) with nitrilimines (generated in situ via triethylamine dehydrohalogenation of the corresponding hydrazonoyl chlorides 2a-c) in refluxing dry toluene. Single crystal X-ray diffraction studies of 3a,b add support for the established structure. Similarly, 3′,5′-diaryl-2,2-dimethyl-3′H,4H-spiro[chromene-3,2′-[1,3,4]thiadiazol]-4-ones

  各种3“，5”-diaryl-3“ ħ，4' ħ -dispiro [环己烷-1,2'-色烯-3'，2” - [1,3,4]噻二唑] -4'-酮图3A-C是通过4'反应区域选择性合成ħ，5 ħ [1,3,4] oxadithiino [5,6- - -trispiro [环己烷-1,2'-色烯-3'，2“ ç ]苯并吡喃-5″，1″′-环己基] -4 ′-（1）与亚硝胺（通过相应的酰肼基氯2a-c的三乙胺脱卤化氢原位产生）在回流的干燥甲苯中。3a，b的单晶X射线衍射研究为已建立的结构提供了支持。同样地，3'，5'-二芳基-2,2-二甲基-3'H，4通过2,2,5'，5'-四甲基-4的反应以区域选择性方式获得H-螺[色烯-3,2'-[1,3,4]噻二唑] -4-酮5a-c。ħ，5' ħ -螺[色烯-3,2' - [1,3,4] oxadithiino [5,6- c ^ ]苯并吡喃] -4-
• [4 + 2]-Cycloaddition Reactions Involving α-Oxo Thioketone Intermediates
  作者：Mohamed I. Hegab、Abd El-Galil A. Amr、Farouk M. E. Abdel-Megeid

  DOI：10.1515/znb-2002-0813

  日期：2002.8.1

  α-Chloro β-oxo sulfenyl chlorides 2 were reduced by iodide ions to the corresponding α-oxo thioketones 3 which dimerized in situ in a hetero-[4 + 2] cycloaddition to give the 1,3,4- oxadithiin derivatives 4. The α-oxo thioketones 3, in situ, cyclized also with 2,3-dimethyl-1,3- butadiene to give the corresponding adducts 5 and only in case of the oxo thioketone intermediate 3d two products 4d and 5d were obtained. Also, The α-oxo thioketones 3a,c, underwent in situ, cycloaddition with furan to give the corresponding adducts 6a,c together with the corresponding thioketone dimers 4a,c. When this reaction was carried out in the presence of diethyl acetylenedicarboxylate or chalcone derivative 8, only the oxo thioketone dimers 4a-d were obtained.

  α-氯β-氧基磺酰氯化物2被碘离子还原为相应的α-氧基硫酮3，在异[4 + 2]环加成中原位二聚形成1,3,4-氧硫代噻吩衍生物4。α-氧基硫酮3也在原位与2,3-二甲基-1,3-丁二烯发生环化反应，形成相应的加合物5，仅在氧基硫酮中间体3d的情况下得到两种产物4d和5d。此外，α-氧基硫酮3a、c在原位与呋喃发生环加成反应，形成相应的加合物6a、c以及相应的硫酮二聚体4a、c。当在乙酸二乙酯乙炔二羧酸酯或查尔康衍生物8存在的情况下进行此反应时，仅得到氧基硫酮二聚体4a-d。
• Thermolysis of Some Spirobenzopyran-3’,2-[1,3,4]oxadithiino- [5,6-c]benzopyran-4’-ones in the Presence of Some Homodienes and Crystallographic Studies of Some Adducts
  作者：Mohamed I. Hegab、A. M. Moustafa

  DOI：10.1515/znb-2006-1115

  日期：2006.11.1

  The very reactive α-oxo-thioketone derivatives 2a - d, generated via thermolysis of spirobenzopyran- 3’,2-[1,3,4]oxadithiino[5,6-c]benzopyran-4’-ones 1a - d, reacted with 2,3-dimethyl-1,3-butadiene and 1,3-cyclohexadiene under [4+2]-cycloaddition to afford spirobenzopyran-3’,6-thiapyran-4’-one adducts 3a - d and spirobenzopyran-3’,3-thiabicyclo[2.2.2]oct-5-en-4’-one adducts 4a - d, respectively. On the other hand, the reaction of α-oxo-thioketones 2a - d with isoprene afforded regioselectively only 3-methyl-thiapyran derivatives 5a - d. Single crystal X-ray diffraction studies of 4b, 4c, and 5a give a good support for the established structure.

  非常活泼的α-氧代硫酮衍生物2a-d，通过热解螺苯并吡喃-3’，2-[1,3,4]氧硫代噻吩[5,6-c]苯并吡喃-4’-酮1a-d生成，与2,3-二甲基-1,3-丁二烯和1,3-环己二烯在[4+2]-环加成反应中反应，得到螺苯并吡喃-3’，6-硫代吡喃-4’-酮加合物3a-d和螺苯并吡喃-3’，3-硫代双环[2.2.2]辛-5-烯-4’-酮加合物4a-d。另一方面，α-氧代硫酮2a-d与异戊二烯反应，只选择性地生成3-甲基硫代吡喃衍生物5a-d。4b、4c和5a的单晶X射线衍射研究为已建立的结构提供了良好支持。
• Cycloadditions with 2,2-Dialkyl-3-thioxochroman-4-one <i>S</i>-Sulfides Including an Unprecedented [3 + 5] Cycloaddition
  作者：Farag A. G. El-Essawy、Salah M. Yassin、Ibrahim A. El-Sakka、Ahmed F. Khattab、Inger Søtofte、Jørgen Øgaard Madsen、Alexander Senning

  DOI：10.1021/jo981534+

  日期：1998.12.1

  We report the facile generation of the chroman-4-one-derived thiosulfines 10 under mild conditions by our well-established nucleophilic "unzipping" of the corresponding acetyl alpha-chloroalkyl disulfides 9 which in turn can be prepared from the corresponding alpha-chloro sulfenyl chlorides 8. Spontaneous partial loss of sulfur from 10, most probably by the disproportionation of 10 to 11 and 12, generates the expectedly reactive beta-oxo thioketones 11 which partly dimerize in a precedented Diels-Alder fashion, to give the 1,3,4-oxadithiins 13, and partly cycloadd to 10 to form the 1,2,4-trithiolanes 14 in a well-precedented fashion. Dimerization of 10 can occur in two competing ways: the precedented nonconcerted [3 + 3] cycloaddition (to give 1,2,4,5-tetrathianes 15) and the unprecedented concerted [3 + 5] addition to give 1,3,4,5,6-oxatetrathiocins 16. In the latter interaction one molecule of 10 behaves as a 1,5-dipole and a second molecule as a 1,3-dipole. In one case (10d) extensive sulfur scrambling takes place with formation of the 1,2,3,4,5,6-hexathiepane 17d. It is remarkable how sensitive the reactions of 10 are to minor variations of the simple alkyl substituents in the 2-position. In addition to the usual spectroscopic characterization all isolated key compounds were subjected to X-ray single-crystal structure determinations.