1-methoxycarbonyl-2-imidazolidinone | 41730-78-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: 1-methoxycarbonyl-2-imidazolidinone
• 英文别名: N-Methoxycarbonyl-imidazolidon-2；1-Methoxycarbonyl-2-imidazolidinon；Methyl 2-oxoimidazolidine-1-carboxylate
• CAS: 41730-78-3
• 化学式: C₅H₈N₂O₃
• mdl: MFCD19216818
• 分子量: 144.13
• InChiKey: ALAMAKIJRBWNFG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  58.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-methoxycarbonyl-2-imidazolidinone 在 氢氧化钾 作用下， 生成 N-carboxy-2-imidazolidinone
  参考文献：
  名称：

  Comparison of the Structures and Vibrational Modes of Carboxybiotin and N-Carboxy-2-imidazolidone

  摘要：

  The spontaneous decarboxylation of N-carboxy-2-imidazolidone (a model for carboxybiotin) and N(1')carboxybiotin can be followed at high pH by Raman and FTIR spectroscopies, The major bands associated with vibrations of the carboxylate group have been assigned on the basis of quantum mechanical calculations of N-carboxy-2-imidazolidone and N(1')-carboxy-2-methylbiotin. The carboxylate modes are the asymmetric stretch, coupled to the ureido carbonyl stretch, near 1710 cm(-1), the symmetric stretch near 1340 cm(-1), and the -CO2- scissoring motion near 830 cm(-1). In the case of carboxybiotin, the last two modes are strongly coupled with biotin ring modes. All three carboxylate modes disappear as spontaneous decarboxylation occurs, to be replaced by features attributable to the noncarboxylated ring structures. The HF/6-31G* optimized structure of 2-methylbiotin revealed that the ureido ring portion is essentially planar, in accord with a number of X-ray crystallographic structures of biotin compounds. However, calculations at this level and at the B3LYP/631+G(d) level (using density functional theory) predict that the ureido ring in biotin puckers upon carboxylation. Comparison of the structures of carboxybiotin and carboxyimidazolidone, derived at the HF/6-31G* level, indicates that lengths of the ring-nitrogen-to-carboxylate bonds are equal and that the torsional angles about this linkage are very similar. This strong structural similarity provides a rationale for the observation that, at high pH, the spontaneous rates of decarboxylation of these two molecules are very similar.

  DOI：

  10.1021/jp984258b
• 作为产物：
  描述：

  N-氯甲酰基-2-咪唑烷酮 以 甲醇 为溶剂， 以55%的产率得到1-methoxycarbonyl-2-imidazolidinone
  参考文献：
  名称：

  Penicillins

  摘要：

  芳基甲基和环己烯基甲基青霉素，通过侧链的α-碳原子被2,3-二取代咪唑啉基氨基甲酰基或2,3-二取代咪唑啉基硫氨基甲酰基团，或者通过相应的2,3-二取代1,3-二氮杂环己基氨基甲酰基或硫氨基甲酰基团进行取代，是抗菌剂。

  公开号：

  US03983105A1

文献信息

• Reactions of Enolic Biotin Models
  作者：Hiroki Kondo、Katsuhito Miura、Eiji Seki、Junzo Sunamoto

  DOI：10.1246/bcsj.58.2801

  日期：1985.10

  mechanism of biotin-dependent carboxylation reactions, the following model experiments have been carried out. In reactions of carbonate derivatives such as methyl chloroformate with 2-ethoxy-2-imidazoline (1), a putative enolic biotin model, or 2-imidazolidinone (2), the former showed a much higher reactivity to provide the methoxycarbonylated 1 (3). Reactions of 3 with benzenethiolate, cyclohexylamine

  为了描述生物素依赖性羧化反应的机制，进行了以下模型实验。在碳酸酯衍生物（如氯甲酸甲酯）与 2-乙氧基-2-咪唑啉（1）、推定的烯醇生物素模型或 2-咪唑啉酮（2）的反应中，前者显示出更高的反应性以提供甲氧基羰基化的 1（3） . 3 与苯硫醇、环己胺和碳负离子的反应也已被研究作为从 N-羧基生物素到受体底物的羧基转移模型。只有碳负离子攻击 3 的羰基碳，导致 C-O 键断裂，而不是 N-C 键断裂。用 1-甲氧基羰基咪唑 (9) 作为供体底物进行净“羧基”转移。讨论了这些结果对生物素催化的影响。
• A NOVEL SYNTHESIS OF 3-SUBSTITUTED MDAZOLIDIN-2-ONE-1-CARBONYL CHLORIDES
  作者：Weike Su、Kewei Huang、Yongmin Zhang

  DOI：10.1080/00304940009356767

  日期：2000.10

  substitute for phosgene in industry.'-'? We found that TCF can replace phosgene in the synthesis of SICs and the reaction is shown in Scheme 1. The role of pyridine is to promote the decomposition of TCF to phosgene and to intercept the by-product HC1. Our experiment showed that without pyridine, the reaction time would be longer and the yield would be lower.

  3-取代的咪唑烷-Zone1 -carbony1 氯化物 (SIC) 是对内酰胺抗生素半合成非常重要的中间体。'-6 SIC 已通过 N-取代的 imidazolidin-2-ones 与光气反应方便地制备。 '-' 然而，光气作为一种常见且有用的试剂在商业上已变得难以获得，因为它是一种剧毒、危险的气体。这种情况促使我们在 SIC 的合成中研究光气的替代品。氯甲酸三氯甲酯 (TCF) 被称为光气二聚体，在工业上用作光气的替代品。'-'？我们发现TCF在SICs的合成中可以代替光气，反应如图1所示。吡啶的作用是促进TCF分解为光气并拦截副产物HCl。
• Acid Catalysis of the Transformation of 1-Methoxycarbonyl-2-imidazoline to 1-Methoxycarbonyl-2-imidazolidinone, a Carboxybiotin Model
  作者：Hiroki Kondo、Katsuhito Miura、Junzo Sunamoto

  DOI：10.1246/bcsj.55.3347

  日期：1982.10

  The transformation of 1-methoxycarbonyl-2-ethoxy-2-imidazoline into 1-methoxycarbonyl-2-imidazolidinone a 1-carboxybiotin model, is facilitated by acid.

  1-甲氧基羰基-2-乙氧基-2-咪唑啉在酸的作用下转化为 1-甲氧基羰基-2-咪唑啉酮，这是一种 1-羧基生物素模型。
• The Reaction of 1-Methoxycarbonyl-2-imidazolidone with Phenylmagnesium Bromide
  作者：Noboru Matsumura、Kimihiro Matsukawa、Yujiro Sakaguchi、Hiroo Inoue

  DOI：10.1246/bcsj.55.1667

  日期：1982.5

  It is found that 1-methoxycarbonyl- or 1-phenoxycarbonyl-2-imidazolidone reacts with phenylmagnesium bromide to afford benzophenone and triphenylmethanol, together with 2-imidazolidone, by nucleophilic attack on the carbonyl group at the side chain.

  发现 1-甲氧羰基-或 1-苯氧羰基-2-咪唑烷酮与溴化苯基镁反应，通过对侧链羰基的亲核攻击，得到二苯甲酮和三苯甲醇以及 2-咪唑烷酮。
• Solvent-Accelerated Decarboxylation of <i>N</i>-Carboxy-2-imidazolidinone. Implications for Stability of Intermediates in Biotin-Dependent Carboxylations
  作者：Jubrail Rahil、Shaochun You、Ronald Kluger

  DOI：10.1021/ja962464w

  日期：1996.1.1

  by association of the substrate and protein. In addition, a report on the decarboxylation of N-carboxy-2-imidazolidinone in organic solvents containing macrocycles (Kluger, R.; Tsao, B. J. Am. Chem. Soc. 1993, 115, 2089−90) must be reinterpreted on the basis of the inherent instability of the substrate under the reaction conditions.

  N-carboxy-2-imidazolidinone 的脱羧以前已被确立为从 N(1')-carboxybiotin 转移二氧化碳的模型。本论文报告了反应的 pH 依赖性以及在甲醇和乙腈中的反应加速。这些结果表明，如果去溶剂化的能量由底物和蛋白质的结合所提供的能量补偿，则 N(1')-羧基生物素在氢键减少的疏水活性位点中的酶促反应可能会很快。此外，一份关于 N-carboxy-2-imidazolidinone 在含有大环的有机溶剂中脱羧的报告 (Kluger, R.; Tsao, BJ Am. Chem. Soc. 1993, 115, 2089-90) 必须基于底物在反应条件下的固有不稳定性。