5-碘-2-金刚烷酮 | 133603-22-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 5-碘-2-金刚烷酮
• 英文名称: 5-iodo-2-adamantanone
• 英文别名: 5-iodoadamantan-2-one
• CAS: 133603-22-2
• 化学式: C₁₀H₁₃IO
• 分子量: 276.117
• InChiKey: NBLWJDRFSUXXRW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5-碘-2-金刚烷酮 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 生成 (Z/E)-5-iodoadamantan-2-ol
  参考文献：
  名称：

  Transmission of polar substituent effects in the adamantane ring system as monitored by 19F NMR: hyperconjugation as a stereoinductive factor

  摘要：

  A limited series of (E)- and (Z)-5-substituted adamant-2-yl fluorides 8 and 9, respectively, has been synthesized and characterized, and the F-19 chemical shifts have been measured in several solvents. A wide range of F-19 substituent chemical shifts (SCS, ppm) are obtained for the former system (ca. 9.1 (c-C6H12), 9.6 (CDCl3), and 11.8 (HFIP)) compared to the latter (ca. 0.6 (c-C6H12), 0.7 (CDCl3), and 2.3 (HFIP)). Factorization of the F-19 SCS into polar field (rho-F-sigma-F) and residual contributions (F-19 SCS - rho-F-sigma-F) reveals the predominance of the latter solvent-independent component for the E fluorides (8). Comparison of 8 with a similar dissection of the F-19 SCS of 4-substituted bicyclo[2.2.2]oct-1-yl fluorides 2 strongly suggests that the origin of the large residual contributions for 8 is "through-three-bond" electron delocalization or double hyperconjugation. The importance of this long-range electronic mechanism as a factor governing pi-facial diastereoselection in 2,5-disubstituted adamantanes (1) is discussed. In particular, the assertion that the p-anilino substituent is an electron donor group at remote probe or reaction sites in saturated systems is addressed.

  DOI：

  10.1021/jo00010a012
• 作为产物：
  描述：

  在 三苯基膦 、 lithium iodide 作用下， 以 丙酮 为溶剂， 反应 24.0h， 以89%的产率得到5-碘-2-金刚烷酮
  参考文献：
  名称：

  可见光下碘化锂催化三苯膦催化的烷基化碘脱羧

  摘要：

  在456 nm蓝色发光二极管的照射下，PPh 3用碘化锂作为碘源催化脂肪族羧酸衍生的N-（酰氧基）邻苯二甲酰亚胺的碘脱羧。该反应在丙酮溶剂中提供伯，仲和桥头叔烷基碘化物，该烷基碘化物产物易于用于生成C–N，C–O，C–F和C–S键，从而无需使用各种脱羧转化即可过渡金属或有机染料基光催化剂。

  DOI：

  10.1021/acs.orglett.0c03173

文献信息

• A Novel Approach for the Formation of Carbon−Nitrogen Bonds:  Azidation of Alkyl Radicals with Sulfonyl Azides
  作者：Cyril Ollivier、Philippe Renaud

  DOI：10.1021/ja004129k

  日期：2001.5.1

  Two preparatively attractive methods for the azidation of alkyl radicals are described. Secondary and tertiary alkyl iodides and dithiocarbonates are easily converted into the corresponding azides, either by reaction with ethanesulfonyl azide in the presence of dilauroyl peroxide, or by treatment with benzenesulfonyl azide and hexabutylditin in the presence of a radical initiator. Interestingly, intramolecular

  描述了用于烷基基团叠氮化的两种制备性有吸引力的方法。通过在过氧化二月桂酰存在下与乙磺酰叠氮化物反应，或在自由基引发剂存在下用苯磺酰叠氮化物和六丁基二锡处理，仲和叔烷基碘和二硫代碳酸酯很容易转化为相应的叠氮化物。有趣的是，分子内串联自由基环化-叠氮化过程可以以高产率进行。
• Novel synthesis of alkenes via triethylaluminum-induced free radical reactions of alkyl iodides and β-nitrostyrenes
  作者：Jing-Yuan Liu、Ju-Tsung Liu、Ching-Fa Yao

  DOI：10.1016/s0040-4039(01)00519-6

  日期：2001.5

  Reactions of (E)-β-nitrostyrenes 1 with triethylaluminum (Et3Al) 2 and alkyl iodide (RI) 3, 4, or 5 in the presence of benzoyl peroxide in diethyl ether solution at room temperature to give 60–100% of the different (E)-alkenes 6, 7, or 8. Under similar conditions, 95% of 1-adamantyl-2-(4-methoxyphenyl)ethene 10 or 80% of 1-(4-oxoadamantyl)-2-(4-methoxyphenyl)ethene 12 also can be easily prepared by

  的（反应ë）-β-硝基苯乙烯1用三乙基铝（ET 3 Al）的2和烷基碘（RI）3，4，或5在室温下过氧化苯甲酰在乙醚溶液的存在下，得到60-100％的不同（ë）烯烃6，7，或8。在相似的条件下，也可以通过使用1-轻松制备95％的1-金刚烷基-2-（4-甲氧基苯基）乙烯10或80％的1-（4-氧杂金刚烷基）-2-（4-甲氧基苯基）乙烯12。碘金刚烷9或5-碘-2-金刚烷酮11和2。
• Novel Synthesis of Alkenes via Triethylborane-Induced Free-Radical Reactions of Alkyl Iodides and <i>β</i>-Nitrostyrenes
  作者：Ju-Tsung Liu、Yeong-Jiunn Jang、Yuh-Kuo Shih、Shin-Ru Hu、Cheng-Ming Chu、Ching-Fa Yao

  DOI：10.1021/jo010213m

  日期：2001.9.1

  iodides 6 and 8 or tertiary alkyl iodides 9, 11, and 13, in the presence of 2 and air as radical initiator. The generation of the only product (E)-alkenes can be explained by the generation of the benzylic radical A and/or B as the intermediate only and the mechanism is similar to Scheme 1. Both (E)- and (Z)-16a-c are generated when (E)- and (Z)-15a-c are used to react with adamantyl radical under similar

  （E）-β-硝基苯乙烯1和三乙基硼烷2或三环己基硼烷4在室温下在空气中存在氧气作为自由基引发剂的条件下的反应产生高产率的反式烯烃（E）-3或（E）- 5，当1与由仲烷基碘化物6和8或叔烷基碘化物9制备的不同基团反应时，也可以制备中等至高产率的不同的（E）-烯烃（E）-5、7、10、12和14。参照图11和13，在2和空气的存在下作为自由基引发剂。唯一产物（E）-烯烃的产生可以通过仅作为中间体的苄基基团A和/或B的产生来解释，其机理与方案1相似。（E）-和（Z）-16a当（E）-和（Z）-15a-c与金刚烷基在相似条件下反应时，生成-c。当使用（E）-或（Z）-15d与金刚烷基自由基反应时，仅观察到（Z）-16d。（E）-和/或（Z）-烯烃的生成可以通过A和/或B自由旋转以生成A'和/或B'来解释，反之亦然，并且该机理被认为是通过NO 2 /烷基取代的自由基反应，如方案2所示。
• One-pot synthesis of malononitriles by free radical reactions of ylidenemalononitrile with Et3B and iodoalkane in a water–ether biphase medium
  作者：Zhijay Tu、Chunchi Lin、Yaochung Jang、Yeong-Jiunn Jang、Shengkai Ko、Hulin Fang、Ju-Tsung Liu、Ching-Fa Yao

  DOI：10.1016/j.tetlet.2006.06.061

  日期：2006.8

  The one-pot synthesis of malononitrile derivatives 4, 6, and 7 in moderate to high yields by the reaction of ylidenemalononitriles 3, prepared in situ from carbonyl compounds 1 and malononitrile 2 in the presence of ammonium acetate in aqueous solution at 50–60 °C, with Et3B or RI 5/Et3B in a water–diethyl ether biphase medium under an atmosphere of room temperature is reported. The reaction of Et3B

  一锅合成丙二腈衍生物的4，6，和7在中度到高收率由ylidenemalononitriles的反应3中，从羰基原位制备化合物1和丙二腈2在乙酸铵的水溶液在50-60存在°据报道，在室温下，在水-乙醚双相介质中，C与Et 3 B或RI 5 / Et 3 B混合。Et 3 B与金刚烷碘化物8和10在相似条件下的反应得到9和11分别高产。然而，当苯甲醛1a与丙二酸二甲酯12缩合，然后在苯溶液中进行平行自由基处理时，单烷基化与二烷基化的丙二酸酯14结合的收率低。
• Nucleophilic Substitution Induced by Electron Transfer at the Bridgehead of Polycyclic Alkanes: Competition between Polar and Radical Pathways
  作者：William Adcock、Christopher I. Clark、Neil A. Trout

  DOI：10.1021/jo001638w

  日期：2001.5.1

  triptycenes react predominantly by a polar mechanism initiated by the formation of a carbanion. In the case of the halo ketones (6, Y = O, X = Br and I), a mechanistic divergence of the reaction was unexpectedly encountered. Whereas the bromo ketone provides the substitution product (6, Y = O, X = SnMe(3)) in good yield (ca. 75%), apparently by a radical pathway, the iodo ketone yields a fragmentation

  一系列2,5（或1,4）-二氢金刚烷胺（4和5，X = Y =卤素）和9,10-二卤代三烯（7，X = Y =卤素）以及两个5-卤代（X）在不存在和存在叔丁胺（TBA）和二环己基膦（DCHP）的情况下，用THF中的Me（3）SnLi处理了金刚烷-2-酮（6，Y = O，X = Br和I）。这些反应的产物分布已通过（13）C和（119）Sn NMR光谱，气相色谱分析和GC / MS建立。前一种化合物（4和5）似乎仅通过自由基链反应（S（RN）1机理）反应生成锡取代产物。相比之下，三联体主要通过形成碳负离子引发的极性机制反应。在卤代酮（6，Y = O，X = Br和I）的情况下，意外地遇到了反应的机理分歧。溴代酮显然可以通过自由基途径以高收率（约75％）提供取代产物（6，Y = O，X = SnMe（3）），而碘代酮则可以产生碎片化产物（约95％）。产量）。这种机械转换突显了离去基团的电负性以