2-hydroxymethyl-1,2,3-propanetriol | 2972-19-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-hydroxymethyl-1,2,3-propanetriol
• 英文别名: 2-C-(hydroxymethyl)glycerol；2-(hydroxymethyl)glycerol；2-hydroxymethylglycerol；i-erythritol；2-hydroxymethyl-propane-1,2,3-triol；isoerythritol；2-(Hydroxymethyl)propane-1,2,3-triol
• CAS: 2972-19-2
• 化学式: C₄H₁₀O₄
• 分子量: 122.121
• InChiKey: HXYJZJOQRLOUPP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.6
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  80.9
• 氢给体数：
  4
• 氢受体数：
  4

安全信息

• 海关编码：
  2905499000

反应信息

• 作为反应物：
  描述：

  2-hydroxymethyl-1,2,3-propanetriol 、 乙酸酐 在 4-二甲氨基吡啶 作用下， 以 吡啶 为溶剂， 反应 24.0h， 以78%的产率得到1,2,3-Triacetoxy-2-acetoxymethylpropan
  参考文献：
  名称：

  Synthesis of Carbohydrates in Mineral-Guided Prebiotic Cycles

  摘要：

  One present obstacle to the "RNA-first" model for the origin of life is an inability to generate reasonable "hands off" scenarios for the formation of carbohydrates under conditions where they might have survived for reasonable times once formed. Such scenarios would be especially compelling if they deliver pent(ul)oses, five-carbon sugars found in terran genetics, and exclude other carbohydrates (e.g., aldotetroses) that may also be able to function in genetic systems. Here, we provide detailed chemical analyses of carbohydrate premetabolisin, showing how borate, molybdate, and calcium minerals guide the formation of tetroses (C(4)H(8)O(4)), heptoses (C(7)H(14),O(7)), and pentoses (C(5)H(10)O(5)), including the ribose found in RNA, in "hands off" experiments, starting with formaldehyde and glycoaldehyde. These results show that pent(ul)oses would almost certainly have formed as stable borate complexes on the surface of an early Earth beneath a humid CO(2) atmosphere suffering electrical discharge. While aldotetroses form extremely stable complexes with borate, they are not accessible by pathways plausible under the most likely early Earth scenarios. The stabilization by borate is not, however, absolute. Over longer times, material is expected to have passed from borate-bound pent(ul)oses to a branched heptulose, which is susceptible to Cannizzaro reduction to give dead end products. We show how this fate might be avoided using molybdate-catalyzed rearrangement of a branched pentose that is central to borate-moderated cycles that fix carbon from formaldehyde. Our emerging understanding of the nature of the early Earth, including the presence of hydrated rocks undergoing subduction to form felsic magmas in the early Hadean eon, may have made borate and molydate species available to prebiotic chemistry, despite the overall "reduced" state of the planet.

  DOI：

  10.1021/ja201769f
• 作为产物：
  描述：

  (5-(ethoxymethoxy)-2,2-dimethyl-1,3-dioxan-5-yl)methanol 在 Dowex 50WX₈ ion exchange resin 作用下， 以 水 为溶剂， 反应 1.0h， 生成 2-hydroxymethyl-1,2,3-propanetriol
  参考文献：
  名称：

  Synthesis of Carbohydrates in Mineral-Guided Prebiotic Cycles

  摘要：

  One present obstacle to the "RNA-first" model for the origin of life is an inability to generate reasonable "hands off" scenarios for the formation of carbohydrates under conditions where they might have survived for reasonable times once formed. Such scenarios would be especially compelling if they deliver pent(ul)oses, five-carbon sugars found in terran genetics, and exclude other carbohydrates (e.g., aldotetroses) that may also be able to function in genetic systems. Here, we provide detailed chemical analyses of carbohydrate premetabolisin, showing how borate, molybdate, and calcium minerals guide the formation of tetroses (C(4)H(8)O(4)), heptoses (C(7)H(14),O(7)), and pentoses (C(5)H(10)O(5)), including the ribose found in RNA, in "hands off" experiments, starting with formaldehyde and glycoaldehyde. These results show that pent(ul)oses would almost certainly have formed as stable borate complexes on the surface of an early Earth beneath a humid CO(2) atmosphere suffering electrical discharge. While aldotetroses form extremely stable complexes with borate, they are not accessible by pathways plausible under the most likely early Earth scenarios. The stabilization by borate is not, however, absolute. Over longer times, material is expected to have passed from borate-bound pent(ul)oses to a branched heptulose, which is susceptible to Cannizzaro reduction to give dead end products. We show how this fate might be avoided using molybdate-catalyzed rearrangement of a branched pentose that is central to borate-moderated cycles that fix carbon from formaldehyde. Our emerging understanding of the nature of the early Earth, including the presence of hydrated rocks undergoing subduction to form felsic magmas in the early Hadean eon, may have made borate and molydate species available to prebiotic chemistry, despite the overall "reduced" state of the planet.

  DOI：

  10.1021/ja201769f
• 作为试剂：
  描述：

  methyl 4-(3-(cyclopropylamino)-2-(4-methylphenyl)-3-oxoprop-1-en-1-yl)benzoic acid 在 sodium hydroxide 、 水 、 2-hydroxymethyl-1,2,3-propanetriol 作用下， 以 甲醇 、 水 为溶剂， 反应 2.0h， 以83%的产率得到4-(3-(cyclopropylamino)-2-(4-methylphenyl)-3-oxoprop-1-en-1-yl)benzoic acid
  参考文献：
  名称：

  [EN] HISTONE DEACETYLASE INHIBITORS
  [FR] INHIBITEURS D'HISTONE DÉSACÉTYLASE

  摘要：

  公开号：

  WO2009053808A3

文献信息

• SELECTIVE FORMOSE REACTION CATALYZED BY DIETHYLAMINOETHANOL
  作者：Toshihiko Matsumoto、Makoto Komiyama、Shohei Inoue

  DOI：10.1246/cl.1980.839

  日期：1980.7.5

  Selective formose reactions were achieved by diethylaminoethanol as catalyst at 100°C in the presence and the absence of D-fructose as co-catalyst. The reaction in the presence of the co-catalyst g...

  在存在和不存在 D-果糖作为助催化剂的情况下，通过二乙氨基乙醇作为催化剂在 100°C 下实现选择性甲糖反应。在助催化剂存在下反应...
• Formose Reactions. XXVIII. Selective Formation of 2,4-Bis(hydroxymethyl)-3-pentulose in<i>N</i>,<i>N</i>-Dimethylformamide–Water Mixed Solvent
  作者：Yoshihiro Shigemasa、Takaaki Ueda、Hiroyuki Saimoto

  DOI：10.1246/bcsj.63.389

  日期：1990.2

  Dihydroxyacetone, DL-glycero-tetrulose, and 2,4-bis(hydroxymethyl)-3-pentulose (2,4-BH-3-P) were favorably formed in a formose reaction by choosing a suitable ratio of water to N,N-dimethylformamide used as solvent or a suitable [thiamine·HCl]/[HCHO] ratio. The formose reaction was strongly affected by the concentration of formaldehyde in the water layer. Under the reaction conditions studied, thiamine

  通过选择合适的水与 N,N 的比例，二羟基丙酮、DL-甘油四糖和 2,4-双(羟甲基)-3-戊酮糖 (2,4-BH-3-P) 在甲糖反应中有利地形成-二甲基甲酰胺用作溶剂或合适的[硫胺素·HCl]/[HCHO]比率。甲糖反应受水层中甲醛浓度的强烈影响。在研究的反应条件下，硫胺迅速分解。从反应混合物中分离出 2,4-BH-3-P，并通过 MS、IR 和 NMR 技术进行表征。还提出了形成 2,4-BH-3-P 的途径。
• Formose Reactions. XIV. A Selective Formose Reaction in the Presence of a Slight Amount of Calcium Ions
  作者：Yoshihiro Shigemasa、Tsuyoshi Taji、Eiichi Waki、Ruka Nakashima

  DOI：10.1246/bcsj.54.1403

  日期：1981.5

  important factor in obtaining the selective formation of the three-branched sugar alcohols. Under these reaction conditions, the α,β-enediol structure is required in an effective co-catalyst for the formose reaction. 2-(Hydroxymethyl)glycerol, 3-(hydroxymethyl)pentitol, and 2,4-bis(hydroxymethyl)pentitol were formed with a high selectivity in the formose reactions catalyzed by KOH, Mg(OH)2, Fe(OH)3

  发现在少量钙和 D-果糖存在下的甲糖反应产生三种产物，2-（羟甲基）甘油、3-（羟甲基）戊醇和 2,4-双（羟甲基）戊醇，具有高选择性。还讨论了影响选择性的各种因素：[Ca]、pH、[D-果糖]、反应温度、助催化剂和金属氢氧化物。相对于 [Ca] 的甲醛量是获得三支链糖醇选择性形成的最重要因素。在这些反应条件下，甲糖反应的有效助催化剂需要α,β-烯二醇结构。2-(羟甲基)甘油、3-(羟甲基)戊醇和2,4-双(羟甲基)戊醇在KOH、Mg(OH)2、Fe(OH)3催化的甲糖反应中以高选择性形成，和氢氧化锂。
• Selective Formation of 2-Hydroxy-3,3-bis(hydroxymethyl)-<b><i>γ</i></b>-butyrolactone from Formaldehyde on Hydrotalcite-Type Catalysts
  作者：Tadashi Mizutani、Yasushi Miki、Ruka Nakashima、Haruo Fujita、Hisanobu Ogoshi

  DOI：10.1246/bcsj.69.425

  日期：1996.2

  As a model for prebiotic sugar formation under neutral to acidic conditions, reactions of formaldehyde over hydrotalcite-type catalysts were investigated. Heating an aqueous solution of formaldehyde at 140—200 °C for 12 h over Ni–Fe hydrotalcite-type catalyst afforded 2-hydroxy-3,3-bis(hydroxymethyl)-γ-butyrolactone selectively, a 5.8% yield based on gas–liquid chromatographic analysis. The structure

  作为在中性至酸性条件下形成益生元糖的模型，研究了甲醛在水滑石型催化剂上的反应。在 Ni-Fe 水滑石型催化剂上将甲醛水溶液在 140-200 °C 下加热 12 小时，选择性地提供 2-羟基-3,3-双（羟甲基）-γ-丁内酯，基于气体的产率为 5.8%液相色谱分析。通过 1H 和 13C NMR 和 1H-13C HSQC、HMBC 和 13C-13C 2D INADEQUATE NMR 实验确定了结构。
• Comparison of the stable products formed by fast atom bombardment and γ-irradiation of glycerol
  作者：T. Keough、F. S. Ezra、A. F. Russell、J. D. Pryne

  DOI：10.1002/oms.1210220503

  日期：1987.5

  AbstractThe major end‐products formed by fast atom bombardment (FAB) and γ‐irradiation of glycerol have been identified using capillary gas chromatography/mass spectrometry. The product distributions differ dramatically. Products resulting from the recombination of either carbon‐centered or oxygen‐centered radicals are evident for both sources of irradiation. However, the major FAB‐generated products are formed by the recombination of carbon‐centered [G – H]· radicals with other carbon‐centered radicals while the major γ‐radiolysis products result from the recombination of oxygen‐centered [G–H]· radicals with lower‐weight carbon‐centered species. γ‐Radiolysis of an N2O‐saturated aqueous solution of glycerol, experimental conditions that strongly favor the formation of carbon‐centered [G – H]· radicals at the expense of the oxygen‐centered species, yielded some products that were identical to those produced by FAB of neat glycerol. Finally, the free radicals produced by γ‐radiolysis of glycerol were investigated by electron spin resonance spectroscopy and spin trapping with 5,5‐dimethyl‐1‐pyrrolne‐TV‐oxide. The presence of only the carbon‐centered free radical was established by this technique. The implications of these results are discussed.