methyl 5'-chloro-5-hydroxy-4'-methoxy-7-methyl-4,6'-dioxospiro[4H-1,3-benzodioxine-2,1'-cyclohexa-2',4'-diene]-2'-carboxylate

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: methyl 5'-chloro-5-hydroxy-4'-methoxy-7-methyl-4,6'-dioxospiro[4H-1,3-benzodioxine-2,1'-cyclohexa-2',4'-diene]-2'-carboxylate
• 英文别名: maldoxin；methyl 4'-chloro-5-hydroxy-3'-methoxy-7-methyl-4,5'-dioxospiro[1,3-benzodioxine-2,6'-cyclohexa-1,3-diene]-1'-carboxylate
• 化学式: C₁₇H₁₃ClO₈
• 分子量: 380.738
• InChiKey: WKBDCISNILFJRO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  108
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl 5'-chloro-5-hydroxy-4'-methoxy-7-methyl-4,6'-dioxospiro[4H-1,3-benzodioxine-2,1'-cyclohexa-2',4'-diene]-2'-carboxylate 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 生成 pestheic acid
  参考文献：
  名称：

  Metabolites of the higher fungi. Part 29. Maldoxin, maldoxone, dihydromaldoxin, isodihydromaldoxin and dechlorodihydromaldoxin. A spirocyclohexadienone, a depsidone and three diphenyl ethers: keys in the depsidone biosynthetic pathway from a member of the fungus genus Xylaria

  摘要：

  2-(3'-Chloro-2'-hydroxy-4'-methoxy-6'-methoxycarbonylphenoxy)-6-hydroxy-4-methylbenzoic acid (dihydromaldoxin 1), 2-(3'-chloro-4'-bydroxy-2'-methoxy-6'-methoxycarbonylphenoxy)-6-hydroxy-4-methylbenzoic acid (isodihydromaldoxin 2), dechlorodihydromaldoxin 3, a new chlorinated depsidone (maldoxone 4) and a new spirocyclohexadienone (maldoxin 5) have been isolated from the culture medium of an as yet unidentified Xylaria species, The structures have been determined by physical and chemical methods and the positions of the substituents in dihydromaldoxin 1 have been confirmed by a single crystal X-ray structure determination, Their role in the grisan-depsidone biosynthetic pathway is discussed.

  DOI：

  10.1039/p19960001419
• 作为产物：
  描述：

  2,4-dihydroxy-6-[(phenylmethoxy)methyl]-benzaldehyde 在 sodium chlorite 、 正丁基锂 、 磺酰氯 、 sodium dihydrogenphosphate dihydrate 、 2-甲基-2-丁烯 、 碘苯二乙酸 、 20 % Pd(OH)2/C 、 水 、 氢气 、 potassium carbonate 、 戴斯-马丁氧化剂 、 对甲苯磺酸 、 叔丁胺 、 N,N-二异丙基乙胺 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 、 2,2,2-三氟乙醇 、 水 、 丙酮 、 甲苯 、 叔丁醇 为溶剂， 反应 28.33h， 生成 methyl 5'-chloro-5-hydroxy-4'-methoxy-7-methyl-4,6'-dioxospiro[4H-1,3-benzodioxine-2,1'-cyclohexa-2',4'-diene]-2'-carboxylate
  参考文献：
  名称：

  Syntheses of Chloroisosulochrin and Isosulochrin and Biomimetic Elaboration to Maldoxin, Maldoxone, Dihydromaldoxin, and Dechlorodihydromaldoxin

  摘要：

  An efficient synthesis of chloroisosulochrin was accomplished using a novel ortho-selective chlorination of a phenol with sulfuryl chloride and 2,2,6,6-tetramethylpiperidine as the key step. Further elaboration by a biomimetic route converted chloroisosulochrin to dihydromaldoxin, maldoxone (lactone formed by dehydration of dihydromaldoxin), and maldoxin and isosulochrin to dechlorodihydromaldoxin and dechloromaldoxin.

  DOI：

  10.1021/ol201561w

文献信息

• Diels–Alder reaction of maldoxin with an isopropenylallene
  作者：Min Yu、Barry B. Snider

  DOI：10.1016/j.tet.2011.09.117

  日期：2011.12

  The Diels-Alder reaction of maldoxin with an isopropenylallene at 60-75 degrees C afforded an adduct closely related to chloropestolide A (24%) and a second adduct (0-11%) that underwent an ene reaction to generate the chloropupukeanolide D (11-22%) skeleton. The Diels-Alder reaction occurred with good selectively (>5:1) from a single face of maldoxin under much milder conditions than previously reported for the analogous dimethoxycyclohexadienone. Furthermore, the ene reaction took place under mild conditions, whereas the analogous Diels-Alder adduct from the dimethoxycyclohexadienone did not undergo an ene reaction. (C) 2011 Elsevier Ltd. All rights reserved.