Citronellsaeuremethylester | 153265-74-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Citronellsaeuremethylester
• 英文别名: Methyl 2,7-dimethyloct-6-enoate
• CAS: 153265-74-8
• 化学式: C₁₁H₂₀O₂
• 分子量: 184.279
• InChiKey: PCSUEYYJYRJKHF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Citronellsaeuremethylester 在 lithium aluminium tetrahydride 、 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 various solvent(s) 为溶剂， 反应 6.25h， 生成 2,7-二甲基辛-6-烯醛
  参考文献：
  名称：

  Intra- and intermolecular hetero-Diels-Alder reactions. 45. Simple and induced diastereoselectivity in intramolecular hetero-Diels-Alder reactions of 1-oxa-1,3-butadienes. Experimental data and calculations

  摘要：

  The simple and induced diastereoselectivity of the intramolecular hetero-Diels-Alder reaction of the alkylidene 1,3-dicarbonyl compounds 7a-e, obtained in situ by Knoevenagel condensation of the aldehydes 5a-e and dimethylbarbituric acid 6, was investigated experimentally and theoretically. In all examples the selectivity is very high; thus the domino reaction of 5a and 6 gives nearly exclusively the trans-fused tricyclic dihydropyran 8 (trans/cis = 98.8:1.2). In the similar reactions of the chiral aldehydes 5b-e and 6 the trans-cycloadducts 28, 33, 36, and 41 are the main products out of four possible diastereomers. The induced diastereoselectivity for the reaction of 5b and 5e with 6 is >99:1 and for the reaction of 5e and Sd-with 6, 95.2:3.6 and 94.1:4.7, respectively. Semiempirical AM1 calculations have been used to locate the transition structures of the intramolecular hetero-Diels-Alder reaction of 7a. The results were employed to create new parameters for the MM2-type force-field to determine the transition structures of 7b-e. The obtained data were compared with the experimental results of the cycloadditions and showed an excellent agreement.

  DOI：

  10.1021/jo00080a030
• 作为产物：
  描述：

  (E/Z)-2,7-Dimethyl-octa-2,6-dienoic acid methyl ester 在 magnesium 作用下， 以 甲醇 为溶剂， 反应 6.0h， 生成 Citronellsaeuremethylester
  参考文献：
  名称：

  Intra- and intermolecular hetero-Diels-Alder reactions. 45. Simple and induced diastereoselectivity in intramolecular hetero-Diels-Alder reactions of 1-oxa-1,3-butadienes. Experimental data and calculations

  摘要：

  The simple and induced diastereoselectivity of the intramolecular hetero-Diels-Alder reaction of the alkylidene 1,3-dicarbonyl compounds 7a-e, obtained in situ by Knoevenagel condensation of the aldehydes 5a-e and dimethylbarbituric acid 6, was investigated experimentally and theoretically. In all examples the selectivity is very high; thus the domino reaction of 5a and 6 gives nearly exclusively the trans-fused tricyclic dihydropyran 8 (trans/cis = 98.8:1.2). In the similar reactions of the chiral aldehydes 5b-e and 6 the trans-cycloadducts 28, 33, 36, and 41 are the main products out of four possible diastereomers. The induced diastereoselectivity for the reaction of 5b and 5e with 6 is >99:1 and for the reaction of 5e and Sd-with 6, 95.2:3.6 and 94.1:4.7, respectively. Semiempirical AM1 calculations have been used to locate the transition structures of the intramolecular hetero-Diels-Alder reaction of 7a. The results were employed to create new parameters for the MM2-type force-field to determine the transition structures of 7b-e. The obtained data were compared with the experimental results of the cycloadditions and showed an excellent agreement.

  DOI：

  10.1021/jo00080a030

文献信息

• GAS–LIQUID CHROMATOGRAPHY OF TERPENES: PART IX. THE VOLATILE OIL OF THE LEAVES OF JUNIPERUS SABINA L.
  作者：E. Von Rudloff

  DOI：10.1139/v63-421

  日期：1963.11.1

  The chemical composition of the volatile oil of the leaves of local savin juniper and of commercial oil of savin was determined by an improved gas chromatographic technique. Both oils contain d-sabinyl acetate (38, 37.5%) and d-sabinene (30.5, 26%) as the major constituents. Smaller amounts of d,α-pinene, d-myrcene, d-limonene, γ-terpinene, p-cymene, d-isothujone, d-terpinen-4-ol, d-sabinol, d-citronellol, d-cadinene, and l-elemol were isolated. Trace amounts of α-thujene, camphene, α-terpinene, 1,8-cineole, terpinolene, thujone, geraniol, a cadinene isomer, and δ-cadinol were tentatively identified. A fraction having the typical pungent odor of juniper leaves was isolated, but it was found to consist mainly of the methyl ester of d-citronellic acid. Several unidentified oxygenated sesquiterpenes and a phenol ether were isolated in trace amounts.Some phylogenetic relationships with other thujone-bearing oils analyzed in this series are discussed.

  通过改进的气相色谱技术，确定了当地青柏叶挥发油和商业青柏油的化学成分。两种油都含有d-香树酸乙酯（38％，37.5％）和d-香树烯（30.5％，26％）作为主要成分。还分离出少量的d，α-蒎烯，d-肉豆蔻烯，d-柠檬烯，γ-松节油烯，对甲酚，d-异硫松油酮，d-松节醇，d-香茅醇，d-卡丁烯，和l-顺-2-己烯醇。尝试鉴定微量的α-油松烯，蒎烯，α-松节油烯，1,8-桉叶醇，松油烯，松脑，香叶醇，卡丁烯同分异构体和δ-卡丁烯醇。分离出具有典型杜松叶辛辣气味的一部分，但发现它主要由d-柠檬酸甲酯组成。还分离了一些未知的含氧倍半萜和酚醚化合物的微量物质。讨论了与本系列中分析的其他含蒎烯油的植物的一些系统发育关系。
• Intra- and intermolecular hetero-Diels-Alder reactions. 45. Simple and induced diastereoselectivity in intramolecular hetero-Diels-Alder reactions of 1-oxa-1,3-butadienes. Experimental data and calculations
  作者：Lutz F. Tietze、Holger Geissler、Jens Fennen、Thomas Brumby、Siegbert Brand、Gerhard Schulz

  DOI：10.1021/jo00080a030

  日期：1994.1

  The simple and induced diastereoselectivity of the intramolecular hetero-Diels-Alder reaction of the alkylidene 1,3-dicarbonyl compounds 7a-e, obtained in situ by Knoevenagel condensation of the aldehydes 5a-e and dimethylbarbituric acid 6, was investigated experimentally and theoretically. In all examples the selectivity is very high; thus the domino reaction of 5a and 6 gives nearly exclusively the trans-fused tricyclic dihydropyran 8 (trans/cis = 98.8:1.2). In the similar reactions of the chiral aldehydes 5b-e and 6 the trans-cycloadducts 28, 33, 36, and 41 are the main products out of four possible diastereomers. The induced diastereoselectivity for the reaction of 5b and 5e with 6 is >99:1 and for the reaction of 5e and Sd-with 6, 95.2:3.6 and 94.1:4.7, respectively. Semiempirical AM1 calculations have been used to locate the transition structures of the intramolecular hetero-Diels-Alder reaction of 7a. The results were employed to create new parameters for the MM2-type force-field to determine the transition structures of 7b-e. The obtained data were compared with the experimental results of the cycloadditions and showed an excellent agreement.