acetone 4-(2-hydroxyethyl)semicarbazone | 98278-63-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: acetone 4-(2-hydroxyethyl)semicarbazone
• 英文别名: 4-(2-Hydroxy-aethyl)-1-isopropyliden-semicarbazid；Aceton-[4-(2-hydroxy-aethyl)-semicarbazon]；1-(2-Hydroxyethyl)-3-(propan-2-ylideneamino)urea
• CAS: 98278-63-8
• 化学式: C₆H₁₃N₃O₂
• 分子量: 159.188
• InChiKey: WCZRSBPUVIRIKP-UHFFFAOYSA-N

物化性质

• 熔点：
  94-96 °C
• 密度：
  1.17±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.1
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  73.7
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  acetone 4-(2-hydroxyethyl)semicarbazone 在 吡啶 、 碘苯二乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 312.0h， 生成 3,3-dimethyl-9-(phenylsulfonyl)-4,6-dioxa-1,2,9-triazaspiro[4.4]non-1-ene
  参考文献：
  名称：

  螺稠合的 2-烷氧基-2-氨基-Δ3-1,3,4-恶二唑啉。合成并热解为相应的氨基氧卡宾

  摘要：

  合成了在 C2 至 C2 处与恶唑烷 (12) 或四氢-1,3-恶嗪 (13) 的 C2 螺环稠合的 Δ3-1,3,4-恶二唑啉。恶二唑啉在苯中在 90 °C 下热解，一级速率常数为 (1.6–50) × 10−5 s−1。这些速率常数对恶二唑啉环上存在的取代基性质的依赖性与涉及羰基叶立德中间体的机制一致。恶唑烷或四氢-1,3-恶嗪部分的 N 上的取代基在确定碎裂途径中起主要作用。具有 N-羰基 (12c-j, 13d,e) 的恶二唑啉提供相应氨基氧卡宾的基本定量收率，而在恶二唑啉与 N-甲基 (12b, 13c) 或 N-磺酰基的情况下，其他断裂反应与卡宾的生成竞争(12k) 组。关键词：

  DOI：

  10.1139/v97-153
• 作为产物：
  描述：

  C.I.酸性橙108 、 N'-isopropylidenehydrazinecarboxylic acid ethyl ester 生成 acetone 4-(2-hydroxyethyl)semicarbazone
  参考文献：
  名称：

  Kashiwara; Imoto, Kogyo Kagaku zasshi / Journal of the Society of Chemical Industry, 1952, vol. 55, p. 593

  摘要：

  DOI：

文献信息

• Reactions of nucleophilic carbenes with enols
  作者：Philippe Couture、David L. Pole、John Warkentin

  DOI：10.1039/a700169j

  日期：——

  The formal insertion of dimethoxycarbene (1a) into the acidic C–H bond of pentane-2,4-dione (9a), methyl acetoacetate (9b), 3-methylpentane-2,4-dione (9c) and 1,3-diphenylpropane-1,3-dione (9d) is reported as well as the insertion of 3-benzoyloxazolidin-2-ylidene (1b) into 9c. The β-dicarbonyl compounds 9 are known to be equilibrated with their corresponding enols in benzene solution and the insertions appear to proceed by proton abstraction from the enol tautomers of 9 to generate enolate anions and either a dimethoxymethyl cation (from 1a) or a 3-benzoyloxazolidin-2-ium cation (from 1b). Collapse of these ion pairs at the carbon atom of the enolate yields the major product. Formal insertion of 1a into the O–H bond of the enol tautomer of anthrone (12) is also reported.

  据报道，二甲氧基羰基（1a）正式插入戊烷-2,4-二酮（9a）、乙酰乙酸甲酯（9b）、3-甲基戊烷-2,4-二酮（9c）和 1,3-二苯基丙烷-1,3-二酮（9d）的酸性 C-H 键，以及 3-苯甲酰恶唑烷-2-亚基（1b）插入 9c。β-二羰基化合物 9 与相应的烯醇在苯溶液中处于平衡状态，插入似乎是通过从 9 的烯醇同系物中抽取质子来生成烯醇阴离子和二甲氧基甲基阳离子（来自 1a）或 3-苯甲酰恶唑啉-2-鎓阳离子（来自 1b）。 这些离子对在烯醇的碳原子上塌缩产生主要产物。此外，还报道了 1a 正式插入蒽酮 (12) 的烯醇同系物的 O-H 键的情况。
• Hydrazine-based and carbonyl-based bifunctional crosslinking reagents
  申请人：Solulink, Inc.

  公开号：EP2295407A1

  公开（公告）日：2011-03-16

  Reagents and methods are provided for crosslinking and immobilizing biomolecules, drugs and synthetic polymers. The reagents of forumula VII or VIII possess (i) a thiol or amino reactive group; and (ii) a oxyamino moiety. Conjugates and immobilized biomolecules are also provided.         B-R-ONH2•HX     VII; or         B-R-ON=C(R1R2)     VIII

  提供了用于交联和固定生物分子、药物和合成聚合物的试剂和方法。第 VII 或 VIII 组试剂具有(i) 硫醇或氨基反应基团；(ii) 氧氨基分子。还提供了共轭物和固定化生物分子。 B-R-onH2-HX VII； 或 b-r-on=c(r1r2) viii
• Saikachi et al., Pharmaceutical Bulletin, 1955, vol. 3, p. 194,198
  作者：Saikachi et al.

  DOI：——

  日期：——
• Iwao, Pharmaceutical Bulletin, 1956, vol. 4, p. 244,246
  作者：Iwao

  DOI：——

  日期：——
• A reinterpretation of the substituent effect on the amide barrier. An experimental and theoretical study
  作者：Alex D. Bain、P. Hazendonk、P. Couture

  DOI：10.1139/cjc-77-8-1340

  日期：——

  Recent theoretical work on amide systems has brought into question the application of the concept of resonance. In particular, the role of the oxygen atom was questioned, since the calculations showed little change in its properties when the amide bond was rotated. This paper investigates, both experimentally and computationally, the effect of a substituent on the carbonyl carbon on the amide barrier, in order to test this view. The barriers to the amide rotation in seven spiro-fused oxazolidines were measured by NMR, to within 1 kJ mol(-1). A subset of three of them was modelled to the 6-31G** level. For all three substituents the computed and measured barriers corresponded to within 7 kJ mol(-1). The electron densities were analyzed using the Atoms in Molecules (AIM) theory. The AIM analysis revealed that the oxazolidines behaved similarly to formamide. The substituent effect was described in terms of the atomic populations and energies of the amide C, O, and N. A substituent on the carbonyl carbon caused electron redistributions between N and C, changing their basin attractive energies. Neither the population nor the energy of oxygen changed significantly. When interactions outside the basin of interest were considered, the energy of C was seen to be more sensitive to changing the substituent than the energy of N. However, the atomic parameters from the AIM analysis did not fully reflect the substituent effects observed. For these molecules, the barrier includes contributions from several sources - there is no single, dominant contribution.