phthalimidoacetic acid methylthiomethyl ester | 324529-59-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: phthalimidoacetic acid methylthiomethyl ester
• 英文别名: Methylsulfanylmethyl 2-(1,3-dioxoisoindol-2-yl)acetate
• CAS: 324529-59-1
• 化学式: C₁₂H₁₁NO₄S
• 分子量: 265.29
• InChiKey: XZYSMMAUHNCXKI-UHFFFAOYSA-N

物化性质

• 熔点：
  67-69 °C
• 沸点：
  414.5±30.0 °C(Predicted)
• 密度：
  1.391±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  89
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  phthalimidoacetic acid methylthiomethyl ester 以 丙酮 为溶剂， 反应 24.0h， 生成 N-甲基邻苯二甲酰亚胺
  参考文献：
  名称：

  Photochemistry of MTM- and MTE-Esters of ω-Phthalimido Carboxylic Acids:  Macrocyclization versus Deprotection¹

  摘要：

  The photochemistry of five linear methylthiomethyl (MTM)-esters of omega -phthalimido carboxylic acids Pht=N-(CH2)(n)COOCH2SCH3 1a-e (n = 1, 2, 3, 5, and 10), of the two methylthioethyl (MTE)esters Pht=N-(CH2)(n)COOCH2CH2SCH3 2a,b (n = 1, 2), and of the two methyl-substituted MTM/MTE esters 3a and 3b was investigated. Two reaction channels were observed: (i) photocyclization to give medium-sized and macrocyclic rings, (ii) photochemical deprotection to give the free carboxylic acids. Photocyclization of Ib and Ic n = 2, 3) resulted in 4b,c in excellent yields whereas the substrates la and Id,e with shorter as well as longer spacer groups (n = i, 5, 10) gave preferentially the deprotected products Ba,d,e. Subsequent photolysis afforded N-methylphthalimide (6) from 5a. The MTE-esters 2a and 2b gave the macrocyclic lactones 7 and E-8. Thus, the competition between cyclization and deprotection strongly depended on the chain length of the hydrocarbon linker between phthalimido chromophore and ester group. To examine the influence of the position of the ester group in the linker chain the model substrates 3a and 3b with identical number of atoms separating electron donor and acceptor group were investigated. The more flexible MTE-derivative 3b cyclized to give a 4:1 diastereoisomeric mixture of cis/trans-9b, whereas photolysis of the more reluctant MTM-ester 3a resulted in cis-ga only after prolonged irradiation. These results show that MTM can function as a photolabile protecting group whereas MTE cannot be removed photochemically. The distance dependence of the secondary reaction steps indicates that the primary electron transfer is not necessarily induced starting from close contact geometries.

  DOI：

  10.1021/jo001089u
• 作为产物：
  描述：

  邻苯二甲酰甘氨酸 、 二甲基亚砜 在 溴代叔丁烷 、 碳酸氢钠 作用下， 以53%的产率得到phthalimidoacetic acid methylthiomethyl ester
  参考文献：
  名称：

  Photochemistry of MTM- and MTE-Esters of ω-Phthalimido Carboxylic Acids:  Macrocyclization versus Deprotection¹

  摘要：

  The photochemistry of five linear methylthiomethyl (MTM)-esters of omega -phthalimido carboxylic acids Pht=N-(CH2)(n)COOCH2SCH3 1a-e (n = 1, 2, 3, 5, and 10), of the two methylthioethyl (MTE)esters Pht=N-(CH2)(n)COOCH2CH2SCH3 2a,b (n = 1, 2), and of the two methyl-substituted MTM/MTE esters 3a and 3b was investigated. Two reaction channels were observed: (i) photocyclization to give medium-sized and macrocyclic rings, (ii) photochemical deprotection to give the free carboxylic acids. Photocyclization of Ib and Ic n = 2, 3) resulted in 4b,c in excellent yields whereas the substrates la and Id,e with shorter as well as longer spacer groups (n = i, 5, 10) gave preferentially the deprotected products Ba,d,e. Subsequent photolysis afforded N-methylphthalimide (6) from 5a. The MTE-esters 2a and 2b gave the macrocyclic lactones 7 and E-8. Thus, the competition between cyclization and deprotection strongly depended on the chain length of the hydrocarbon linker between phthalimido chromophore and ester group. To examine the influence of the position of the ester group in the linker chain the model substrates 3a and 3b with identical number of atoms separating electron donor and acceptor group were investigated. The more flexible MTE-derivative 3b cyclized to give a 4:1 diastereoisomeric mixture of cis/trans-9b, whereas photolysis of the more reluctant MTM-ester 3a resulted in cis-ga only after prolonged irradiation. These results show that MTM can function as a photolabile protecting group whereas MTE cannot be removed photochemically. The distance dependence of the secondary reaction steps indicates that the primary electron transfer is not necessarily induced starting from close contact geometries.

  DOI：

  10.1021/jo001089u

文献信息

• Photochemistry of MTM- and MTE-Esters of ω-Phthalimido Carboxylic Acids:  Macrocyclization versus Deprotection¹
  作者：Axel G. Griesbeck、Michael Oelgemöller、Johann Lex

  DOI：10.1021/jo001089u

  日期：2000.12.1

  The photochemistry of five linear methylthiomethyl (MTM)-esters of omega -phthalimido carboxylic acids Pht=N-(CH2)(n)COOCH2SCH3 1a-e (n = 1, 2, 3, 5, and 10), of the two methylthioethyl (MTE)esters Pht=N-(CH2)(n)COOCH2CH2SCH3 2a,b (n = 1, 2), and of the two methyl-substituted MTM/MTE esters 3a and 3b was investigated. Two reaction channels were observed: (i) photocyclization to give medium-sized and macrocyclic rings, (ii) photochemical deprotection to give the free carboxylic acids. Photocyclization of Ib and Ic n = 2, 3) resulted in 4b,c in excellent yields whereas the substrates la and Id,e with shorter as well as longer spacer groups (n = i, 5, 10) gave preferentially the deprotected products Ba,d,e. Subsequent photolysis afforded N-methylphthalimide (6) from 5a. The MTE-esters 2a and 2b gave the macrocyclic lactones 7 and E-8. Thus, the competition between cyclization and deprotection strongly depended on the chain length of the hydrocarbon linker between phthalimido chromophore and ester group. To examine the influence of the position of the ester group in the linker chain the model substrates 3a and 3b with identical number of atoms separating electron donor and acceptor group were investigated. The more flexible MTE-derivative 3b cyclized to give a 4:1 diastereoisomeric mixture of cis/trans-9b, whereas photolysis of the more reluctant MTM-ester 3a resulted in cis-ga only after prolonged irradiation. These results show that MTM can function as a photolabile protecting group whereas MTE cannot be removed photochemically. The distance dependence of the secondary reaction steps indicates that the primary electron transfer is not necessarily induced starting from close contact geometries.