2-重氮基环戊酮 | 14088-61-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2-重氮基环戊酮
• 英文名称: 2-diazocyclopentanone
• 英文别名: α-diazocyclopentanone；2-diazo-1-cyclopentanone；2-Diazocyclopentanon；2-diazo-cyclopentanone；2-Diazo-cyclopentanon；Cyclopentanone, 2-diazo-；2-diazocyclopentan-1-one
• CAS: 14088-61-0
• 化学式: C₅H₆N₂O
• 分子量: 110.115
• InChiKey: LDWKOSPMPJEFHE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  19.1
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2927000090

反应信息

• 作为反应物：
  描述：

  2-重氮基环戊酮 以 solid matrix 为溶剂， 反应 0.17h， 生成 cyclobutylidenemethanone
  参考文献：
  名称：

  Direct observation of .alpha.-oxo ketenes from the photolysis of .alpha.-diazo .beta.-diketones

  摘要：

  Monitoring by IR spectroscopy of the broad-band irradiation of the symmetrically substituted 2-diazo-cyclohexane-1,3-dione (I 1), 3-diazopentane-2,4-dione (19), and 4-diazo-2,2,6,6-tetramethylheptane-3,5-dione (24) in Ar matrices at 12 K showed the formation of 2-carbonylcyclopentanone (s-Z-12), acetyl(methyl)ketene (s-E-20), and tert-butyl(pivaloyl)ketene (s-E-25), respectively, in less than 10 min. On increasing the photolysis time to >3 h, the alpha-oxo ketenes 12,20, and 25 decarbonylated to the corresponding oxocarbenes which underwent Wolff rearrangement to carbonylcyclobutane (15), dimethylketene (23), and di-tert-butylketene (28), respectively. The reaction of 2-carbonylcyclopentanone (12) with CH3OH was monitored by IR spectroscopy. Thus, it was found that the reaction started at ca. 100 K and was essentially complete at 140 K, involving the initial formation of the enol form (9) of methyl 2-oxocyclopentanecarboxylate.

  DOI：

  10.1021/jo00044a019
• 作为产物：
  描述：

  环戊酮 在 potassium tert-butylate 、 甲酸乙酯 、 sodium azide 、 3-氯磺酰基苯甲酸 、 potassium carbonate 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 21.0h， 以76%的产率得到2-重氮基环戊酮
  参考文献：
  名称：

  水性“无磺酰叠氮”（SAFE）重氮转移方案在较少的α-C-H酸性酮和酯中的应用

  摘要：

  抽象的 较早描述的重氮转移至CH酸性1,3-二羰基化合物（及其类似活化的同类物）的``无磺酰叠氮''（``SAFE''）方案已扩展至反应性较低的单羰基底物，以前需要单独的激活步骤。甲酰化原位，然后加入“安全鸡尾酒”的优化量的（通过混合叠氮化钠，碳酸钾，和得到米导致期望的重氮化合物的形成，这是由分离-carboxybenzenesulfonyl氯化物在水中）提取的产率中等至极好，并且在大多数情况下，无需额外纯化。 较早描述的重氮转移至CH酸性1,3-二羰基化合物（及其类似活化的同类物）的``无磺酰叠氮''（``SAFE''）方案已扩展至反应性较低的单羰基底物，以前需要单独的激活步骤。甲酰化原位，然后加入“安全鸡尾酒”的优化量的（通过混合叠氮化钠，碳酸钾，和得到米导致期望的重氮化合物的形成，这是由分离-carboxybenzenesulfonyl氯化物在水中）提取的产率中等至极好，并且在大多数情况下，无需额外纯化。

  DOI：

  10.1055/s-0039-1690613

文献信息

• Regiospecific synthesis of α-(phenylthio)cycloalkenones and of α-phenyl-α-(phenylthio) ketones VIA αα-addition of phenylsulphenyl chloride to ∢-diazoketones
  作者：M.Anthony McKervey、Pinit Ratananukul

  DOI：10.1016/s0040-4039(00)81343-x

  日期：1983.1

  phenylsulphenyl chloride at room temperature to furnish α-chloro-α-(phenylthio)cycloalkanones which undergo ready dehydrochlorination to α-(phenylthio)cycloalkenones when treated with triethylamine; acyclic, terminal α-diazoketones also furnish α-chloro-α-(phenylthio)adducts which are useful electrophiles in the synthesis of α-phenyl-α-(phenylthio)ketones.

  在室温下，环状α-二氮酮与苯磺酰氯反应生成α-氯-α-（苯硫基）环链烷酮，当用三乙胺处理时，α-氯代-α-（苯硫基）环烯酮易于脱氯化氢成α-（苯硫基）环烯酮。无环末端α-二氮酮还提供α-氯代-α-（苯硫基）加合物，它们在合成α-苯基-α-（苯硫基）酮中是有用的亲电子试剂。
• Bio-Inspired Fragmentations: Rapid Assembly of Indolones, 2-Quinolinones, and (−)-Goniomitine
  作者：Haokun Li、Peng Cheng、Long Jiang、Jin-Liang Yang、Liansuo Zu

  DOI：10.1002/anie.201611830

  日期：2017.3.1

  goniomitine, new synthetic bio‐inspired fragmentation strategies for the synthesis of functionalized 2‐quinolinones and indolones have been developed. Remarkable synthetic efficiency was achieved by telescoping several transformations into one‐pot reactions, allowing for the direct coupling of 2‐alkynyl‐anilines and diazo ketones. The synthetic utility was demonstrated by the 5‐step asymmetric total synthesis

  受淋菌素的生物遗传学启发，开发了用于功能化的2-喹啉酮和吲哚酮合成的新的合成方法。通过将多次转化转化为一锅反应，从而实现了2-炔基苯胺和重氮酮的直接偶联，从而获得了显着的合成效率。由2-乙基-环戊酮通过5步不对称全合成（-）-goniomitine证明了该合成的实用性。
• A new synthesis of α-fluoro-α,β-unsaturated ketones and esters based on organoselenium methodology
  作者：Yoshinosuke Usuki、Michio Iwaoka、Shuji Tomoda

  DOI：10.1039/c39920001148

  日期：——

  Fluoroselenenylation of α-diazoketones and α-diazoesters using a phenylselenenyl fluoride equivalent, generated in situ from phenylselenenyl bromide and AgF, followed by oxidation with hydrogen peroxide, provided α-fluoro-α,β-unsaturated ketones and ester, respectively, in moderate yields.

  使用由苯基硒烯基溴和AgF原位生成的苯基硒烯基氟当量，对α-重氮酮和α-二重氮酯进行氟烯化，然后用过氧化氢氧化分别以中等收率提供α-氟-α，β-不饱和酮和酯。
• Palladium-Catalyzed Cross-Coupling Reaction of Diazo Compounds and Vinyl Boronic Acids: An Approach to 1,3-Diene Compounds
  作者：Yamu Xia、Ying Xia、Zhen Liu、Yan Zhang、Jianbo Wang

  DOI：10.1021/jo5012703

  日期：2014.8.15

  A palladium-catalyzed oxidative cross-coupling of vinyl boronic acids and cyclic α-diazocarbonyl compounds has been reported. The reaction constitutes an efficient method for the synthesis of 1,3-diene compounds bearing a ring structure. Mechanistically, the reaction involves migratory insertion of palladium carbene as the key step.

  已经报道了钯催化的乙烯基硼酸和环状α-重氮羰基化合物的氧化交叉偶联。该反应构成合成具有环结构的1，3-二烯化合物的有效方法。从机理上讲，该反应涉及钯卡宾的迁移插入是关键步骤。
• Reactions of α-diazoketones with phenylselenenyl chloride. A new synthesis of α-chloro- and α-phenylselenenyl-αβ-unsaturated ketones
  作者：Daniel J. Buckley、Sunanta Kulkowit、Anthony McKervey

  DOI：10.1039/c39800000506

  日期：——

  α-Diazoketones react with phenylselenenyl chloride at room temperature giving α-chloro-α-phenylselenenyl ketones; where structural considerations permit these adducts can be transformed via elimination reactions into α-chloro- or α-phenylselenenyl-α,β-unsaturated ketones.

  在室温下，α-重氮酮与苯基硒烯基氯反应，得到α-氯-α-苯基硒烯基酮；在结构上允许的情况下，这些加合物可以通过消除反应转化为α-氯代或α-苯基硒烯基-α，β-不饱和酮。