3-Methoxy-4-methylphthalid | 72288-77-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: 3-Methoxy-4-methylphthalid
• 英文别名: 3-methoxy-4-methyl-3H-isobenzofuran-1-one；3-methoxy-4-methyl-3H-2-benzofuran-1-one
• CAS: 72288-77-8
• 化学式: C₁₀H₁₀O₃
• 分子量: 178.188
• InChiKey: YXZJLVOFJQATPR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-Methoxy-4-methylphthalid 在 sodium hydroxide 作用下， 生成 3-methoxy-4-methyl-phthalic acid
  参考文献：
  名称：

  PHTHALIDE FORMATION: II. CONDENSATIONS WITH 3-HYDROXY-4-METHYLBENZOIC ACID

  摘要：

  3-羟基-4-甲基苯甲酸与水甲醛和盐酸的缩合反应产生6-羟甲基-1,3-苯并二噁烷-8-甲基-5-羧酸内酯。这种二噁烷酞环内酯也可以通过类似的缩合反应从5-羟基-4-甲基酞环内酯中制得，后者可以通过氯化铝去甲基化得到。通过逐步打开这些环来证明缩合产物中存在m-二噁烷和酞环。碱性高锰酸盐的作用打开酞环，产生取代酞酸。酸水解然后打开m-二噁烷环，失去甲醛并形成一个新的酞环。对新酞环的脱羧、甲基化和氧化的连续步骤产生已知的3-甲基-4-甲基酞酸。

  DOI：

  10.1139/v53-010
• 作为产物：
  描述：

  2,3-二甲基苯甲酸甲酯 在 palladium on activated charcoal calcium hydroxide 、 N-溴代丁二酰亚胺(NBS) 、 过氧化氢苯甲酰 、 水 、 氢气 作用下， 以 1,4-二氧六环 、 甲醇 、 四氯化碳 、 乙醚 为溶剂， 180.0 ℃ 、275.79 kPa 条件下， 反应 71.0h， 生成 3-Methoxy-4-methylphthalid
  参考文献：
  名称：

  Aromatische Spirane, 21. Mitt: Darstellung von Methylphthalaldehyds�uren und ihren Ethylund Methylestern als Synthone f�r Synthesen von methylierten 2,2?-Spirobiindandionen

  摘要：

  The isomeric methyl phthalaldehydic acids 11 were obtained from phthalides 4 by bromation (NBS) to the 3-bromo derivatives 7 and subsequent hydrolysis with water. 4 in turn were accessible from dimethyl methyl benzoates 1 by dibromination with NBS and subsequent thermical cyclization to the bromo derivatives 3 which, on catalytic dehalogenation, afforded the phthalides 4. Reaction of 11 with methanol or ethanol gave the pseudo-esters 13 and 14, resp. Short treatment of 11 with diazomethane on the other hand yielded the methyl formyl benzoates 15b to 15e. Prolonged reaction (several hours) gave the oxiranyl compounds 17; in addition, the acetonyl derivatives 18 were also found, obviously formed by a double methylene insertion into 15. All reactions proceeded with good to excellent yields.

  DOI：

  10.1007/bf00807401

文献信息

• FRANCIS J. E.; DOEBEL K. J.; SCHUTTE P. M.; SAVARESE E. C.; HOPKINS S. E.+, CAN. J. CHEM., 1979, 57, NO 24, 3320-3331
  作者：FRANCIS J. E.、 DOEBEL K. J.、 SCHUTTE P. M.、 SAVARESE E. C.、 HOPKINS S. E.+

  DOI：——

  日期：——
• Aromatische Spirane, 21. Mitt: Darstellung von Methylphthalaldehyds�uren und ihren Ethylund Methylestern als Synthone f�r Synthesen von methylierten 2,2?-Spirobiindandionen
  作者：H. K. Neudeck

  DOI：10.1007/bf00807401

  日期：1996.2

  The isomeric methyl phthalaldehydic acids 11 were obtained from phthalides 4 by bromation (NBS) to the 3-bromo derivatives 7 and subsequent hydrolysis with water. 4 in turn were accessible from dimethyl methyl benzoates 1 by dibromination with NBS and subsequent thermical cyclization to the bromo derivatives 3 which, on catalytic dehalogenation, afforded the phthalides 4. Reaction of 11 with methanol or ethanol gave the pseudo-esters 13 and 14, resp. Short treatment of 11 with diazomethane on the other hand yielded the methyl formyl benzoates 15b to 15e. Prolonged reaction (several hours) gave the oxiranyl compounds 17; in addition, the acetonyl derivatives 18 were also found, obviously formed by a double methylene insertion into 15. All reactions proceeded with good to excellent yields.
• PHTHALIDE FORMATION: II. CONDENSATIONS WITH 3-HYDROXY-4-METHYLBENZOIC ACID
  作者：E. H. Charlesworth、H. J. Anderson、N. S. Thompson

  DOI：10.1139/v53-010

  日期：1953.1.1

  The condensation of 3-hydroxy-4-methylbenzoic acid with aqueous formaldehyde and hydrochloric acid yields the lactone of 6-hydroxymethyl-1,3-benzodioxane-8-methyl-5-carboxylic acid. This dioxanylphthalide has also been produced in a similar type of condensation from 5-hydroxy-4-methylphthalide which can be obtained by demethylation with aluminum chloride of 5-methoxy-4-methylphthalide.Proof of the presence of the m-dioxane and phthalide rings in the condensation product has been obtained by opening these rings in succession. The action of alkaline permanganate opens the phthalide ring to yield a substituted phthalic acid. Acid hydrolysis then opens the m-dioxane ring with loss of formaldehyde and the formation of a new phthalide ring. Successive steps of decarboxylation, methylation, and oxidation of the new phthalide yield the known 3-methyl-4-methylphthalic acid.

  3-羟基-4-甲基苯甲酸与水甲醛和盐酸的缩合反应产生6-羟甲基-1,3-苯并二噁烷-8-甲基-5-羧酸内酯。这种二噁烷酞环内酯也可以通过类似的缩合反应从5-羟基-4-甲基酞环内酯中制得，后者可以通过氯化铝去甲基化得到。通过逐步打开这些环来证明缩合产物中存在m-二噁烷和酞环。碱性高锰酸盐的作用打开酞环，产生取代酞酸。酸水解然后打开m-二噁烷环，失去甲醛并形成一个新的酞环。对新酞环的脱羧、甲基化和氧化的连续步骤产生已知的3-甲基-4-甲基酞酸。