6-iodo-2-methylhex-2-ene | 63588-94-3

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机碘化物
• 英文名称: 6-iodo-2-methylhex-2-ene
• 英文别名: 5-methyl-4-hexenyl iodide；5-methylhex-4-enyl iodide；1-iodo-5-methylhex-4-ene；2-Methyl-6-iodohex-2-ene；6-Iodo-2-methyl-2-hexene；6-iodo-2-methyl-hex-2-ene；2-Hexene, 6-iodo-2-methyl-
• CAS: 63588-94-3
• 化学式: C₇H₁₃I
• 分子量: 224.085
• InChiKey: SUMOPHHECWPZCN-UHFFFAOYSA-N

物化性质

• 沸点：
  80-82 °C(Press: 13 Torr)
• 密度：
  1.433±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  6-iodo-2-methylhex-2-ene 在 [(S)-2,2'-双(二苯基磷)-1,1'-联萘]二氯化钌(II) 三乙基硅烷 、 三氟甲磺酸三甲基硅酯 、 氢气 、 sodium hydride 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 44.34h， 生成 (2S,3S)-tert-butyl 3-benzyloxy-2-icosy-9-methyl-8-decenoate
  参考文献：
  名称：

  Efficient Syntheses of a Series of Trehalose Dimycolate (TDM)/Trehalose Dicorynomycolate (TDCM) Analogues and Their Interleukin-6 Level Enhancement Activity in Mice Sera

  摘要：

  We found an IL-6 level-enhancing compound during our synthetic study of trehalose-6,6'-dimycolate (1, TDM, formerly called cord factor) analogues. TDM is a glycolipid distributed in the cell wall of Mycobacterium tuberculosis and shows significant antitumor activity based on an immunoadjuvant activity. However, due to its significant toxicity, TDM is not yet applicable for practical use. In 1993, Datta and Takayama reported the purification of trehalose-6,6'-dicorynomycolate (2c, TDCM) from Corynebacterium spp. We have previously reported the synthesis of four diastereomeric TDCMs and showed that the synthetic (2R,3R,2'R,3'R)-TDCM (2c, hereafter abbreviated RRRR-TDCM-C-14) is identical to natural TDCM; we also demonstrated that 2c and SSSS-TDCM-C-14 (3c) showed significant antitumor activity as well as inhibitory activity in experimental lung metastasis based on the immunoadjuvant activity. Furthermore, we found that the significant lethal toxicity in mice by TDM (1) was no longer observed with the shorter-chain analogues of TDCMs. Therefore, we have elucidated that the 2,3-antistereochemistry (RR or SS) of the fatty acid residue is promising for biological activities. The chain length of the fatty acid residue should also be important for the biological activity, and thus, we designed a general synthetic procedure for trehalose diesters with 2,3-antistereochemistry and a series of chain lengths by using Noyori's asymmetric reduction of beta,beta-ketoesters followed by antiselective alkylation according to Frater to give beta,beta-hydroxy alcohols as the key steps. Thus, we prepared trehalose diesters (TDCM) 2a-d, 3a-d, and 4a-d as well as monoesters (TMCM) 5a-d and 6a-d. Immunological activities of TDCMs and TMCMs were evaluated by determining IL-6 level enhancement in mouse serum, and we found that RRRR-TDCM-C-14 (2c) and RRSS-TDCM-C-14 (4c) showed significant IL-6 level enhancement activities.

  DOI：

  10.1021/jo062018j
• 作为产物：
  描述：

  2-(3-甲基丁-2-烯基)丙二酸 在 吡啶 、 lithium aluminium tetrahydride 、 对甲苯磺酰氯 、 sodium iodide 作用下， 以 乙醚 、 水 为溶剂， 反应 43.0h， 生成 6-iodo-2-methylhex-2-ene
  参考文献：
  名称：

  Cocker, Wesley; Geraghty, Niall W. A.; McMurry, T. Brian H., Journal of the Chemical Society. Perkin transactions I, 1984, # 10, p. 2245 - 2254

  摘要：

  DOI：

文献信息

• Synthesis of arylcycloalkanes from ω-alkenyl benzylselenides
  作者：Alain Krief、Benoit Kenda、Phillipe Barbeaux、Eric Guittet

  DOI：10.1016/s0040-4020(01)85242-x

  日期：1994.1

  Arylcycloalkanes are produced from ω-alkenyl benzylselenides on reaction with alkyllithiums or on Lewis acid mediated electrophilic cyclisation.

  芳基环烷烃是由ω-烯基苄基硒化物在与烷基锂反应或路易斯酸介导的亲电环化反应中产生的。
• Effect of Double-Bond Substituents on the Rate of Cyclization of α-Carbomethoxyhex-5-enyl Radicals
  作者：Arthur Han、Tudor Spataru、John Hartung、Gang Li、Jack R. Norton

  DOI：10.1021/jo402499w

  日期：2014.3.7

  the corresponding acrylate esters 1 and the yields of cyclized products compared to the calculated rate constants. (The “cyclized products” include those from cyclohydrogenation, 4, and those from cycloisomerization, 9.) Two phenyl substituents on C6 (2i), or a phenyl and a methyl substituent (2g, 2h), increase the rate of cyclization, but a single phenyl substituent on C6 produces a greater increase

  已经计算出速率常数，并将其与实验结果进行比较，以对在C6上具有各种取代基的1-甲氧基-1-甲基-5-己烯基自由基（2）进行环化。通过DFT在B3LYP / 6-311 ++ G **的理论水平上进行了计算。它们显示了C5和自由基中心之间的相当大的相互作用，即使在所有自由基2的基态下也是如此。在实验上，自由基是通过H •转移至相应的丙烯酸酯1生成的，并将环化产物的产率与计算出的速率常数进行比较。（“环化产物”包括来自环氢化的产物4和来自环异构化的产物9。）C6（2i）上的两个苯基取代基，或苯基和甲基取代基（2g，2h）提高环化率，但C6上的单个苯基取代基产生更大的环化。计算表明，两个苯基取代基在过渡态中被扭曲以进行环化，而单个苯基取代基在该过渡态中保持平坦。C6上的甲基取代基与单个苯基一起导致苯基在过渡态发生扭曲，并使环化的速率常数降低到H / Ph-取代的2e，2f之下。
• Intramolecular [2 + 2]cycloadditions of dialkylketenes with alkenes. Regiochemistry of intramolecular [2+2]cycloadditions of ketenes with alkenes
  作者：Barry B. Snider、Alban J. Allentoff、Marleen B. Walner

  DOI：10.1016/s0040-4020(01)81460-5

  日期：——

  Unsaturated dialkylketenes 7a, 7b and 7c undergo intramolecular [2 + 2]cycloadditions to give 8a (45%), 9b (23%) and 9c (45%). Intramolecular cycloadditions of dialkylketenes give higher yields than intramolecular cycloadditions of monoalkylketenes, even though dialkylketenes are less reactive than monoalkylketenes. An intramolecular competition experiment with ketene 17 establishes that trans-alkenes

  不饱和二烷基烯酮7a，7b和7c经历分子内[2 + 2]环加成，得到8a（45％），9b（23％）和9c（45％）。即使二烷基烯酮的反应性不如单烷基烯酮，二烷基烯酮的分子内环加成比单烷基烯酮的分子内环加成具有更高的产率。乙烯酮17的分子内竞争实验确定，在分子内环加成中，反式烯烃的反应性比顺式烯烃高约33倍。酮36提供预期的双环[3.2.0]庚酮37中的22％和28％的双环[3.1.1]庚酮38。
• Synthesis of the racemic and optically active forms of gizzerosine, the inducer of gizzard erosion in chicks
  作者：Kenji Mori、Takeshi Sugai、Yukari Maeda、Tomomi Okazaki、Tadashi Noguchi、Hiroshi Naito

  DOI：10.1016/s0040-4020(01)96782-1

  日期：1985.1

  The racemate and both the (R)- and (S)-forms of gizzerosine [2-amino-9-(4-imidazolyl)-7-azanonanoic acid] were synthesised, and the (S)-isomer was identified as the toxic substance in fish meal causing severe gizzard erosion (black vomit) in chicks.

  合成了外消旋体和吡咯烷磺酸[2-氨基-9-（4-咪唑基）-7-氮杂壬酸]的（R）-和（S）-形式，并将（S）-异构体鉴定为有毒物质鱼粉中的这种物质会导致小鸡严重的izz侵蚀（黑呕吐物）。
• Evolution of a Polyene Cyclization Cascade for the Total Synthesis of (−)-Cyclosmenospongine
  作者：Klaus Speck、Thomas Magauer

  DOI：10.1002/chem.201605029

  日期：2017.1.23

  We report a full account on the development of a unique cationic polyene cyclization for the total synthesis of the tetracyclic meroterpenoid (−)‐cyclosmenospongine. A highly convergent three‐component coupling strategy enabled rapid access to individual cyclization precursors that were tested for their reactivity. The successful transformation generates three rings and sets four consecutive stereocenters

  我们报告了一个完整的发展为四环甲氧萜（-）-cyclosmenospongine的全合成独特的阳离子多烯环化的完整说明。高度收敛的三组分偶联策略使得能够快速访问经过测试其反应性的各个环化前体。成功的转换生成了三个环，并在一次操作中以高效的方式设置了四个连续的立体中心，从而仅给出了十萘烷的反式构架。此外，我们发现烯醇醚的几何形状以及C3和C8的相对构型对于多烯环化的成功至关重要。