3-[(R)-2-amino-2-carboxyethylthio]-1,2-dihydroxy-5-methylbenzene | 17054-97-6

• 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: 3-[(R)-2-amino-2-carboxyethylthio]-1,2-dihydroxy-5-methylbenzene
• 英文别名: 3-S-cysteinyl-5-methylcatechol；6-
• CAS: 17054-97-6
• 化学式: C₁₀H₁₃NO₄S
• 分子量: 243.284
• InChiKey: YFCRVIPKLISQJF-LURJTMIESA-N

物化性质

• 熔点：
  192-194 °C (decomp)
• 沸点：
  441.2±45.0 °C(Predicted)
• 密度：
  1.49±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.5
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  129
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-[(R)-2-amino-2-carboxyethylthio]-1,2-dihydroxy-5-methylbenzene 在 盐酸 、 zinc(II) sulfate 作用下， 以 乙醚 、 氯仿 、 水 为溶剂， 反应 1.33h， 生成 2,2'-bi[3-methoxycarbonyl-5-methoxy-7-methyl-4H-1,4-benzothiazine]
  参考文献：
  名称：

  Zinc-Catalyzed Oxidation of 5-S-Cysteinyldopa to 2,2‘-Bi(2H-1,4-benzothiazine):  Tracking the Biosynthetic Pathway of Trichochromes, the Characteristic Pigments of Red Hair

  摘要：

  Trichochromes, the peculiar pigments of red human hair, featuring the Delta (2,2')-bi(2H-1,4-benzothiazine) skeleton, are known to arise from cysteinyldopas, mainly the 5-S-isomer (5). However, the mode of formation and the direct precursors have remained largely undefined. To fill this gap, we investigated the oxidation of 5 in air or with chemical and enzymatic agents under biomimetic conditions. In the presence of zinc ions, which occur in epidermal tissues at significant concentrations, the reaction course is diverted toward the formation of a labile 3-carboxy-2H-1,4-benzothiazine intermediate (11), which was identified by direct NMR analysis. Structural formulation was supported by characterization of the analogous compound 13 isolated from oxidation of the model 5-methyl-3-S-cysteinylcatechol (12) after methylation. In the further stages of the oxidation, diastereomeric 2,2'-bi(2H-1,4-benzothiazine) 15 and 14 were obtained from 5 and 12, respectively, the reaction proceeding at a higher rate and to a greater extent in the presence of acids. The dimers were shown to readily convert to each other in the presence of acids. In the case of the methylated dimers 14, a 2,2'-bi(4H-1,4-benzothiazine) intermediate (16) was isolated and characterized. In acidic media, trichochrome C (1a), the most abundant in red human hair, was smoothly formed from aerial oxidation of 15, and under similar conditions, trichochrome-related products (17 and 18) were obtained from 14 prior to or after methylation. The presence of la and precursors 5 and 15 was investigated by HPLC analysis of red hair samples following mild proteolytic digestion. On the basis of these data, a likely biosynthetic route to trichochrome pigments of red human hair is depicted.

  DOI：

  10.1021/jo010320g
• 作为产物：
  描述：

  L-半胱氨酸 、 4-methylbenzo-1,2-quinone 生成 3-[(R)-2-amino-2-carboxyethylthio]-1,2-dihydroxy-5-methylbenzene
  参考文献：
  名称：

  Prota,G. et al., Gazzetta Chimica Italiana, 1967, vol. 97, p. 1451 - 1478

  摘要：

  DOI：

文献信息

• A Novel Octahydropyridobenzothiazepine Metabolite in Human Urine:  Biomimetic Formation from the Melanogen 5-<i>S</i>-Cysteinyldopa and Formaldehyde via a Peculiar Sulfur-Controlled Double Pictet−Spengler Condensation
  作者：Paola Manini、Marco d'Ischi、Giuseppe Prota

  DOI：10.1021/jo991969c

  日期：2000.7.1

  4-thiazepine moiety. Under physiologically relevant conditions, i.e., in 0.1 M phosphate buffer pH 7.4 and at 37 degrees C, the 7,8-tetrahydroisoquinoline 5 was the sole detectable intermediate in the formation of 2. N-Acetylcysteinyldopa (4) reacted likewise with formaldehyde to give the 7, 8-dihydroxytetrahydroisoquinoline 6. The anomalous regiochemistry underlying formation of 5 and 6 was rationalized

  高效液相色谱法的证据表明，在某些人类尿液样品中出现了一种新的儿茶酚代谢产物（3R，7S）-3，7-dicarboxy-10,11-dihydroxy-2,3,4,5,6,7,8， 9-八氢吡啶并[4,3-g] [1，4]苯并硫氮杂pine（2）。该化合物显示为尿黑色素原5-S-半胱氨酰多巴（1）与甲醛的双Pictet-Spengler缩合生成，其中六元环邻位与活化羟基的区域选择性形成有助于随后的封闭七元1,4-硫氮杂moiety部分中的一部分。在生理相关条件下，即在pH 7.4的0.1 M磷酸盐缓冲液中和在37摄氏度下，7,8-四氢异喹啉5是形成2的唯一可检测中间体。N-乙酰半胱氨酸多巴（4）同样与甲醛反应生成7、8-二羟基四氢异喹啉6。借助在模型烷硫基邻苯二酚10上进行的AM1 / PM3计算，合理化了形成5和6的异常区域化学反应，从而预测了在邻位而不是对位活化羟基上更高的HOMO控制反
• Disentangling the Puzzling Regiochemistry of Thiol Addition to <i>o</i>-Quinones
  作者：Maria L. Alfieri、Alice Cariola、Lucia Panzella、Alessandra Napolitano、Marco d’Ischia、Luca Valgimigli、Orlando Crescenzi

  DOI：10.1021/acs.joc.1c02911

  日期：2022.4.1
• Prota,G. et al., Gazzetta Chimica Italiana, 1967, vol. 97, p. 1451 - 1478
  作者：Prota,G. et al.

  DOI：——

  日期：——
• Zinc-Catalyzed Oxidation of 5-<i>S</i>-Cysteinyldopa to 2,2‘-Bi(2<i>H</i>-1,4-benzothiazine):  Tracking the Biosynthetic Pathway of Trichochromes, the Characteristic Pigments of Red Hair
  作者：Alessandra Napolitano、Paola Di Donato、Giuseppe Prota

  DOI：10.1021/jo010320g

  日期：2001.10.1

  Trichochromes, the peculiar pigments of red human hair, featuring the Delta (2,2')-bi(2H-1,4-benzothiazine) skeleton, are known to arise from cysteinyldopas, mainly the 5-S-isomer (5). However, the mode of formation and the direct precursors have remained largely undefined. To fill this gap, we investigated the oxidation of 5 in air or with chemical and enzymatic agents under biomimetic conditions. In the presence of zinc ions, which occur in epidermal tissues at significant concentrations, the reaction course is diverted toward the formation of a labile 3-carboxy-2H-1,4-benzothiazine intermediate (11), which was identified by direct NMR analysis. Structural formulation was supported by characterization of the analogous compound 13 isolated from oxidation of the model 5-methyl-3-S-cysteinylcatechol (12) after methylation. In the further stages of the oxidation, diastereomeric 2,2'-bi(2H-1,4-benzothiazine) 15 and 14 were obtained from 5 and 12, respectively, the reaction proceeding at a higher rate and to a greater extent in the presence of acids. The dimers were shown to readily convert to each other in the presence of acids. In the case of the methylated dimers 14, a 2,2'-bi(4H-1,4-benzothiazine) intermediate (16) was isolated and characterized. In acidic media, trichochrome C (1a), the most abundant in red human hair, was smoothly formed from aerial oxidation of 15, and under similar conditions, trichochrome-related products (17 and 18) were obtained from 14 prior to or after methylation. The presence of la and precursors 5 and 15 was investigated by HPLC analysis of red hair samples following mild proteolytic digestion. On the basis of these data, a likely biosynthetic route to trichochrome pigments of red human hair is depicted.