(7-甲基-1,4-二氧杂螺[4.5]癸-7-烯-8-基)甲醇 | 29915-82-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: (7-甲基-1,4-二氧杂螺[4.5]癸-7-烯-8-基)甲醇
• 英文名称: 4,4-(ethylenedioxy)-2-methylcyclohex-1-ene-1-methanol
• 英文别名: (7-methyl-1,4-dioxa-spiro[4.5]dec-7-en-8-yl)-methanol；(+/-)-3-Methyl-4-hydroxymethyl-cyclohex-3-en-1-on-aethylenketal；3-Methyl-4-hydroxymethyl-cyclohex-3-en-1-on-aethylenketal；1-Hydroxymethyl-2-methyl-4-ethylendioxy-1-cyclohexen；4,4-Ethylendioxy-1-hydroxymethyl-2-methyl-cyclohexen；(7-Methyl-1,4-dioxaspiro[4.5]dec-7-en-8-yl)methanol
• CAS: 29915-82-0
• 化学式: C₁₀H₁₆O₃
• 分子量: 184.235
• InChiKey: JFXPWIJAKDCJTJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (7-甲基-1,4-二氧杂螺[4.5]癸-7-烯-8-基)甲醇 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 生成 7-甲基-1,4-二氧杂螺[4.5]癸-7-烯-8-甲醛
  参考文献：
  名称：

  Oxyanion Orientation in Anionic Oxy-Cope Rearrangements

  摘要：

  Efficiency of chirality transfer in anionic oxy-Cope rearrangement depends solely on the orientational preference of the oxyanionic bond in the substrates with a single carbinol carbon chiral center. In chairlike transition-state conformations for the rearrangement of simplest substrates like anions generated from (E)-1-phenyl-1,5-hexadien-3-ol and (E)-1,5-heptadien-4-ol, the oxyanionic bond is more prone to adopt the pseudoaxial orientation. On the other hand, anions generated from (E)-2-methyl-1,5-heptadien-4-ol, (E)-5-tert-butyl-1-phenyl-1,5-hexadien-3-ol, and 4-(2'-methyl-1'-cyclohexenyl)-1-buten-3-ol undergo rearrangement via chairlike transition states in which the pseudoequatorial oxyanionic bond is favored. It can thus be surmized that there is a slight stereoelectronic preference for the pseudoaxial oxyanionic bond in the chairlike transition states for the rearrangement of substrates without steric constraints. Substitution at C5 of the basic 1,5-hexadien-3-ol framework of substrates, however, leads to 1,3-diaxial steric interaction in the chairlike transition states with pseudoaxial oxyanionic bond, and pseudoequatorial disposition of oxyanionic bond becomes more favorable.

  DOI：

  10.1021/jo00085a037
• 作为产物：
  描述：

  7-甲基-1,4-二噁螺[4.5]-7-癸烯-8-羧酸乙酯 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以90%的产率得到(7-甲基-1,4-二氧杂螺[4.5]癸-7-烯-8-基)甲醇
  参考文献：
  名称：

  通过BF 3 .Et 2 O介导的分子内重氮酮插入反应区域选择性合成双环[4.2.1]壬烷-2,8-二酮

  摘要：

  用三氟化硼二乙基醚化物处理重氮二酮11a-d以高度区域选择性的方式提供了双环[4.2.1]壬烷-2,8-二酮15a-d。

  DOI：

  10.1016/s0040-4039(98)02656-2

文献信息

• Nonracemic, Chiral Homoenolate Reagents Derived from (Cycloalk-1-enyl)methyl Carbamates and Evaluation of Their Configurational Stabilities
  作者：Mustafa Özlügedik、Jesper Kristensen、Birgit Wibbeling、Roland Fröhlich、Dieter Hoppe

  DOI：10.1002/1099-0690(20022)2002:3<414::aid-ejoc414>3.0.co;2-2

  日期：2002.2

  2-unsubstituted (cyclopent-1-enyl)methyl carbamates, such as 11a or 11h, epimerise rapidly at −78 °C and the thermodynamically controlled ratio is opposite to the kinetically achieved ratio. High configurational stability was found for the 2-methylcycloalk-1-enyl derivatives 11d, 11e and 11j. These turned out to be valuable reagents for enantioselective homoaldol reaction; er values of up to 96:4 could be achieved

  通过三种不同的方法合成了几种（环烷-1-烯基）甲基 N,N-二异丙基氨基甲酸酯 11，并研究了它们通过丁基锂 /（-）-sparteine 进行的不对称去质子化。差向异构离子对 18·4/epi-18·4 的比率通过（立体特异性）三甲基甲硅烷基化确定，形成产物 19/ent-19。锂化的 2-未取代（环戊-1-烯基）甲基氨基甲酸酯，例如 11a 或 11h，在 -78 °C 时会迅速差向异构，并且热力学控制的比率与动力学实现的比率相反。发现 2-甲基环烷-1-烯基衍生物 11d、11e 和 11j 具有高构型稳定性。这些被证明是对映选择性高羟醛反应的有价值的试剂；可以实现高达 96:4 的 er 值。用异常衍射分析 X 射线晶体结构，从含有由（2-甲基环戊烯基）甲基和（2-甲基环己烯基）甲基试剂衍生的产物22、23b、27d和27e的重原子获得，建立了主要锂化合物的（1S）构型。因此，相应
• Ethyl 2- methyl-4-oxocyclohex-2-enecarboxylate (Hagemann's ester) as a precursor to alkyl-substituted 3-methylcyclohexenones
  作者：Bruce A. McAndrew

  DOI：10.1039/p19790001837

  日期：——

  from ethyl 2-methyl-4-oxocyclohex-2-enecarboxylate (Hagemann's ester)via the alkylation of its ethylene glycol acetal. Various routes to 6-alkyl-3-methylcyclohex-2-enones from Hagemann's ester have been explored; a particularly convenient route to these unsaturated ketones utilised the isomeric keto-ester, ethyl 4-methyl-2-oxocyclohex-3-enecarboxylate as starting material. The alkylation of ethyl 2-

  由2-甲基-4-氧代环己基-2-烯基羧酸乙酯（哈格曼酯）经以下步骤制备4-烷基-3-甲基环己基-2-烯酮乙二醇缩醛的烷基化。已经探索了从哈格曼酯制得6-烷基-3-甲基环己-2-烯酮的各种途径。制备这些不饱和酮的一种特别方便的途径是使用异构的酮酯，4-甲基-2-氧代环己基-3-烯丙基羧酸乙酯作为起始原料。2-甲基-4-吡咯烷基环己-1,3-二烯羧酸乙酯（衍生自哈格曼酯的完全共轭二烯胺）的烷基化反应在水解和脱乙氧基羰基化后生成2-烷基-3-甲基环己-2-烯酮。据报道，哈格曼酯的制备方法有所改进。4-烷基-和6-烷基-3-甲基环己-2-烯酮的制备补充了现有方法，以2-烷基-和5-烷基-3-甲基环己-2-烯酮。
• Isomerisation of 1-methylene-2-methyl-2-(2-oxopropyl)-cyclohexanes to 2-methylene-1-methyl-1-(2-oxopropyl)-cyclohexanes by ene and retro-ene reaction
  作者：Adusumilli Srikrishna、Somepalli Venkateswarlu、Sankuratri Nagaraju、Kathiresan Krishnan

  DOI：10.1016/s0040-4020(01)85350-3

  日期：1994.1

  Thermal activation of the normal Claisen products, the enones 4, 7 and 14 in the presence of a catalytic amount of propionic acid generated the isomeric enones 6, 9 and 15 via the sequential intramolecular ene-reaction of the enol tautomer followed by 1,5-hydrogen transfer (or retro ene-reaction) of the resultant acetyl cyclopropane intermediate. Conversion of the enones 9 and 15 into the corresponding

  正常克莱森产物的热活化，烯酮4,7和14中的丙酸催化量的存在所产生同分异构的烯酮6,9和15通过互变异构体，随后1,5烯醇的连续分子内烯反应所得乙酰基环丙烷中间体的-氢转移（或逆烯反应）。将烯酮9和15转化成相应的环己酮10和16，建立了重排产物的结构。
• New approaches to quassinoid synthesis. Structure of a new Michael adduct
  作者：Malcolm Chandler、Enrico Mincione、Philip J. Parsons

  DOI：10.1039/c39850001233

  日期：——

  The structure of a new Michael addition product is reported from intermediates in a projected quassinoid synthesis.

  据报道，拟拟的类胡萝卜素合成中的中间体报道了一种新的迈克尔加成产物的结构。
• Pd(II)-catalyzed deprotection of acetals and ketals containing acid sensitive functional groups
  作者：Francisco Juliá-Hernández、Aurelia Arcas、José Vicente

  DOI：10.1016/j.tetlet.2013.12.067

  日期：2014.2

  The pincer complex [Pd(C-1,O-1,N-1-L)(NCMe)]ClO4 (L = monoanionic ligand resulting from deprotonation of the acetyl group of the dimethyl monoketal of 2,6-diacetylpyridine) is used for the high-yield and selective catalytic hydrolysis of aliphatic, aromatic, cyclic, and acyclic dimethyl-acetals, -ketals, and dioxolanes, even in the presence of large substituents. Other protecting groups, such as THP or TBDMS, or very acid-sensitive alcohols were not affected. The catalyst is easily prepared in high yield from Pd(AcO)(2) and 2,6-diacetylpyridinium perchlorate stable to air and moisture, easily and fully recoverable and reusable. (C) 2013 Elsevier Ltd. All rights reserved.