3-(2-Methyl-1-propen-3-yl)cyclohexanone | 937-44-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(2-Methyl-1-propen-3-yl)cyclohexanone
• 英文别名: 3-(2-Methyl-2-propenyl)cyclohexanone；3-(2-methylpropenyl)cyclohexanone；3-(2-methylallyl)cyclohexanone；3-(3'-methyl-3'-propenyl)-cyclohexanone；3-(2-methylprop-2-enyl)-cyclohexan-1-one；3-<2-Methyl-allyl>-cyclohexan-1-on；3-(2-Methylprop-2-en-1-yl)cyclohexan-1-one；3-(2-methylprop-2-enyl)cyclohexan-1-one
• CAS: 937-44-0
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: ZQAMIZCYCZELLA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  3-(2-Methyl-1-propen-3-yl)cyclohexanone 在 铂 lithium aluminium tetrahydride 、 氢气 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 2.0h， 生成 (1S,3S)-3-isobutyl-cyclohexanol
  参考文献：
  名称：

  Julia,M.; Descoins,C., Bulletin de la Societe Chimique de France, 1970, p. 1805 - 1815

  摘要：

  DOI：
• 作为产物：
  描述：

  3-(2-methyl-2-propenyl)-1-(trimethylsiloxy)-1-cyclohexene 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 生成 3-(2-Methyl-1-propen-3-yl)cyclohexanone
  参考文献：
  名称：

  Conjugate Addition Reactions of Allylic Copper Species Derived from Grignard Reagents: Synthetic and Spectroscopic Aspects

  摘要：

  A general study on the 1,4-addition chemistry of allyl, methallyl, crotyl, and prenyl Grignard-derived organocopper reagents has been conducted. While diallylic cuprates formed from such species are not effective Michael donors, the 1:1:1 combination of an allylic Grignard, CuBr.SMe(2), and Me(3)SiCl leads to high yields of 1,4-adducts. The stereo- and regiochemistry associated with the allylic ligand, where appropriate, has also been examined. Low temperature C-13 NMR studies provide insight as to the nature of these complexes.

  DOI：

  10.1021/jo00103a042

文献信息

• Transposition oxy-cope assistee par le trifluoroacetate mercurique en quantite stoechiometrique et en quantite catalytique
  作者：Norbert Bluthe、Max Malacria、Jacques Gore

  DOI：10.1016/0040-4020(84)85011-5

  日期：1984.1

  Tertiary 1,5-hexadien-3-ols are transformed at room temperature into δ-ethylenic ketones in 35-90%, yields under two sets of conditions: treatment with one molar equivalent of mercuric trifluoroacetate followed by demercuration of the intermediate α-mercuro ketone with sodium borohydride; and treatment with 0.2 molar equivalent of t of lithium trifluoroacetate or trifluorométhansulfonate. The reactions

  在室温下，将1,5-己二烯-3-醇叔化成35-90％的δ-乙烯酮，在两种条件下收率：用一摩尔当量的三氟乙酸汞处理，然后使中间的α-水银脱汞酮与硼氢化钠；用0.2摩尔当量的三氟乙酸锂或三氟甲磺酸锂处理。反应是高度立体选择性的，酮的E异构体占产物的80-95％。在第二条件下观察到最高的选择性。
• Intramolecular cycloaddition reactions of exocyclic nitrones
  作者：Raymond L. Funk、Gary L. Bolton、Joy Umstead Daggett、Marvin M. Hansen、Linus H.M. Horcher

  DOI：10.1016/s0040-4020(01)96702-x

  日期：1985.1

  Exocyclic nitrones smoothly participate in intramolecular cycloaddition reactions to provide bridged and fused polycarbocycles. The exploitation of this methodology in the total syntheses of the sesquiterpenes (±)-7,12-secoishwaran-12-ol (44), (±)-hirsutene (56), (±)-coriolin (68) is also presented.

  环外硝酮平稳地参与分子内环加成反应，以提供桥连和稠合的多碳环。还介绍了该方法在倍半萜（±）-7,12-secoishwaran-12-ol（44），（±）-hirsutene（56），（±）-coriolin（68）的总合成中的应用。
• Preparation of higher order cyano and “non-ate” allyl copper reagents from the reaction of allyl chlorides with a formal copper anion
  作者：Douglas E. Stack、Walter R. Klein、Reuben D. Rieke

  DOI：10.1016/s0040-4039(00)93380-x

  日期：1993.5

  through the low temperature reaction of allyl chlorides with a formal copper anion. The copper anion is generated via the low temperature reduction of Cu(I) complexes by two equivalents of lithium naphthalenide and then oxidatively adds to allyl chlorides with minimal homocoupling. These allyl organocopper reagents undergo substitution reactions with alkyl chlorides and epoxides as well as 1,4-conjugate

  通过烯丙基氯化物与形式铜阴离子的低温反应，已实现了高阶和“非酸酯化”的烯丙基有机铜试剂的生成。铜阴离子是通过两当量的萘甲酸锂对Cu（I）络合物的低温还原作用而生成的，然后以最小的均偶联度氧化添加到烯丙基氯中。这些烯丙基有机铜试剂与烷基氯化物和环氧化物进行取代反应，并以良好或极好的收率进行1,4-共轭物加成反应。
• Process for the preparation of 8-ethylenic carbonyl compounds
  申请人：Rhone-Poulenc Sante

  公开号：US04421934A1

  公开（公告）日：1983-12-20

  Process for the preparation of .delta.-ethylenic carbonyl compounds of the formula (I) by the oxy-Cope rearrangement of a diethylenic alcohol of the formula (II), in the presence of a mercuric salt: in formulae (I) and (II), R.sub.1, R.sub.2, R.sub.4, R.sub.5 and R.sub.6, which are identical or different, represent a hydrogen atom or an acyclic hydrocarbon radical and R.sub.3 represents an acyclic hydrocarbon radical, it being understood that R.sub.1 and R.sub.3 can together form a trimethylene radical, or alternatively that R.sub.3 and R.sub.4 can together form an alkylene radical containing 3 to 20 carbon atoms. ##STR1##

  以汞盐存在下，通过二乙烯醇的氧-科普重排反应，制备公式(I)的.delta.-烯丙酮化合物的过程：在公式(I)和(II)中，R.sub.1、R.sub.2、R.sub.4、R.sub.5和R.sub.6，它们相同或不同，表示氢原子或无环烃基，R.sub.3表示无环烃基，其中R.sub.1和R.sub.3可以共同形成三亚甲基基团，或者R.sub.3和R.sub.4可以共同形成含3至20个碳原子的烷基基团。##STR1##
• Allylbarium Reagents: Unprecedented Regio- and Stereoselective Allylation Reactions of Carbonyl Compounds
  作者：Akira Yanagisawa、Shigeki Habaue、Katsutaka Yasue、Hisashi Yamamoto

  DOI：10.1021/ja00093a010

  日期：1994.7

  The first direct preparation of allylbarium reagents by reaction of insitu generated reactive barium with various allylic chlorides and their new and unexpected selective allylation reactions with carbonyl compounds are disclosed. Highly reactive barium was readily prepared by the reduction of barium iodide with 2 equiv of lithium biphenylide in dry THF at room temperature. A variety of carbonyl compounds reacted with barium reagents generated from (E)- or (Z)-allylic chlorides in THF at -78 degrees C. All reactions resulted in high yields with remarkable alpha-selectivities not only with aldehydes but also with ketones. The double bond geometry of the starting allylic chloride was completely retained in each case. Stereochemically homogeneous (E)- and (Z)beta,gamma-unsaturated carboxylic acids were easily prepared in good yields by highly alpha-selective carboxylation of allylic barium reagents with carbon dioxide. A selective Michael addition reaction with alpha,beta-unsaturated cycloalkanone was also achieved using an allylbarium reagent. Treatment of 2-cyclopentenone (1 equiv) with allylbarium chloride (2 equiv) in THF at -78 degrees C for 20 min afforded 3-allylcyclopentanone in 94% yield with a 1,4/1,2 ratio of >99/1. Furthermore, the in situ generated barium enolate was efficiently trapped with various kinds of electrophiles (Me(2)C=CHCH2Br, (C5H11CHO)-C-n, and CH3COCl).