2-benzoylbenzoate geraniol ester | 185062-45-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-benzoylbenzoate geraniol ester
• 英文别名: geranyl 2-benzoylbenzoate；geranyl 2-benzoyl benzoate；[(2E)-3,7-dimethylocta-2,6-dienyl] 2-benzoylbenzoate
• CAS: 185062-45-7
• 化学式: C₂₄H₂₆O₃
• 分子量: 362.469
• InChiKey: ZXSGBSHNNDLPLQ-KNTRCKAVSA-N

物化性质

• 沸点：
  499.0±33.0 °C(Predicted)
• 密度：
  1.063±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  27
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-benzoylbenzoate geraniol ester 在 环己胺 作用下， 以 乙腈 、 苯 为溶剂， 反应 5.0h， 以80%的产率得到3-苯基苯酞
  参考文献：
  名称：

  2-Benzoylbenzoic Acid:  A Photolabile Mask for Alcohols and Thiols

  摘要：

  Photolysis of 2-benzoylbenzoate esters of primary and secondary alcohols 1 in the presence of a hydrogen donor (2-isopropanol) or an electron donor (primary amines) produces the corresponding alcohol in high yield. The fate of the benzoate is dependent on the conditions used for the photoreaction. In 2-propanol, the ketyl radical that derives from photoreduction dimerizes, to afford the benzpinacol product 3,3'-diphenylbiphthalidyl, 5. In the presence of amines the product is 3-phenylphthalide, 6, a benzhydrol derivative which is the result of simple reduction of the ketone followed by lactonization. While the photoproduct of the benzoate-2-propanol reaction results from anticipated free radical chemistry, the amine-promoted reaction appears to result from a second, ''dark'', electron transfer process. We conclude that 2-benzoylbenzoic acid is an effective photolabile protecting group for primary and secondary alcohols, and preliminary studies indicate that thiols can be protected in an analogous way. Studies on the effect of benzophenone substituents and reaction solvent on the benzhydrol:benzpinacol product ratio provide mechanistic insight into the process.

  DOI：

  10.1021/jo961638p
• 作为产物：
  描述：

  邻苯甲酰苯甲酸 、 香叶醇 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 吡啶 为溶剂， 反应 48.0h， 以63%的产率得到2-benzoylbenzoate geraniol ester
  参考文献：
  名称：

  2-Benzoylbenzoic Acid:  A Photolabile Mask for Alcohols and Thiols

  摘要：

  Photolysis of 2-benzoylbenzoate esters of primary and secondary alcohols 1 in the presence of a hydrogen donor (2-isopropanol) or an electron donor (primary amines) produces the corresponding alcohol in high yield. The fate of the benzoate is dependent on the conditions used for the photoreaction. In 2-propanol, the ketyl radical that derives from photoreduction dimerizes, to afford the benzpinacol product 3,3'-diphenylbiphthalidyl, 5. In the presence of amines the product is 3-phenylphthalide, 6, a benzhydrol derivative which is the result of simple reduction of the ketone followed by lactonization. While the photoproduct of the benzoate-2-propanol reaction results from anticipated free radical chemistry, the amine-promoted reaction appears to result from a second, ''dark'', electron transfer process. We conclude that 2-benzoylbenzoic acid is an effective photolabile protecting group for primary and secondary alcohols, and preliminary studies indicate that thiols can be protected in an analogous way. Studies on the effect of benzophenone substituents and reaction solvent on the benzhydrol:benzpinacol product ratio provide mechanistic insight into the process.

  DOI：

  10.1021/jo961638p

文献信息

• Photoenolization as a Means To Release Alcohols
  作者：Jana Pika、Armands Konosonoks、Rachel M. Robinson、Pradeep N. D. Singh、Anna D. Gudmundsdottir

  DOI：10.1021/jo0261193

  日期：2003.3.1

  in applications. Photolysis of 2-(2-isopropylbenzoyl)benzoate ester derivatives 4 in various solvents and in thin films results in the liberation of the alcohol moiety from the ester. The reaction mechanism for the release of the alcohol has been elucidated by time-resolved laser flash photolysis. Upon irradiation the triplet excited state of ketone, 4 is formed, and its lifetime can be estimated to

  我们设计了分子，这些分子在暴露于紫外线时会释放醇，而与反应介质无关，从而可以在应用中以受控方式释放醇。2-（2-异丙基苯甲酰基）苯甲酸酯衍生物4在各种溶剂中和薄膜中的光解导致醇部分从酯中释放出来。通过时间分辨的激光闪光光解已经阐明了释放醇的反应机理。辐射后，形成酮的三重激发态4，其寿命估计在0.08到0.8 ns之间。三重态激发态通过有效的分子内H原子抽象作用而衰减，从而形成1,4-双自由基8，其寿命小于17 ns，并被分子氧俘获。在没有氧气的情况下 双自由基8系统间交叉以分别以5：2的比率形成光烯醇（Z）-9和（E）-10。光子醇（Z）-9在质子溶剂中的寿命约为3000 ns，并通过1,5分子内氢转移返回到起始材料。另一个异构体（E）-10的寿命更长（> 1 ms），并通过分子内内酯化作用释放出醇部分。
• SLOW RELEASE OF FRAGRANT COMPOUNDS IN PERFUMERY USING 2-BENZOYL BENZOATES, 2-ALKANOYL BENZOATES OR ALPHA-KETO ESTERS
  申请人：FIRMENICH SA

  公开号：EP1082287A2

  公开（公告）日：2001-03-14
• US6133228A
  申请人：——

  公开号：US6133228A

  公开（公告）日：2000-10-17
• US6369026B1
  申请人：——

  公开号：US6369026B1

  公开（公告）日：2002-04-09
• [EN] SLOW RELEASE OF FRAGRANT COMPOUNDS IN PERFUMERY USING 2-BENZOYL BENZOATES, 2-ALKANOYL BENZOATES OR alpha -KETO ESTERS<br/>[FR] COMPOSES DE PARFUMERIE ODORANTS A LIBERATION LENTE CONTENANT DES BENZOATES DE 2-BENZOYLE, DES BENZOATES DE 2-ALCANOYLE OU DES ALPHA-CETOESTERS
  申请人：——

  公开号：WO1999060990A2

  公开（公告）日：1999-12-02

  [EN] The present invention describes a fragrance delivery system which releases fragrant alcohols upon exposure to light. Said system comprises 2-benzoyl benzoates of general formulae (I) or (II) which can comprise various substituents R>1<-R>5< as defined in the application and a substituent R* which is the organic part of a fragrant alcohol R*OH. In a further embodiment, the present invention describes a fragrance delivery system which releases fragrant aldehydes or ketones and/or fragrant compounds containing an olefin function. This system comprises alpha -keto esters of formula (III) in which R'* and R''* have the meaning as defined in the application and which are generally, in case of R'*, an alkyl group carrying an abstractable hydrogen in gamma -position relative to the alpha -keto function and carrying a moiety from which is derived a fragrant compound containing an olefin function, and, in case of R''*, the organic part of a primary or secondary alcohol from R''*OH which is derived a fragrant aldehyde or ketone.
  [FR] La présente invention concerne un système de libération de parfum qui libère des alcools odorants lorsque ceux-ci sont exposés à la lumière. Ce système comprend des benzoates de 2-benzoyle de la formule générale (I) ou (II) qui peuvent inclure divers substituants R>1<-R>5<, tels que définis dans le mémorandum descriptif, et un substituant R* qui est la composante organique d'un alcool odorant R*OH. Dans une autre forme de réalisation, l'invention concerne un système de libération de parfum qui libère des aldéhydes ou cétones odorants et/ou des composés odorants comprenant une fonction oléfinique. Ce système comprend des alpha-cétoesters de la formule (III) dans laquelle R'* et R''* sont tels que définis dans le mémorandum descriptif. Dans le cas de R'*, les alpha-cétoesters sont un groupe alkyle contenant, d'une part, un hydrogène soustractif à la position gamma relativement à la fonction alpha-cétone et, d'autre part, une fraction de laquelle est extrait un composé odorant comprenant une fonction oléfinique. Dans le cas de R''* les alpha-cétoesters sont la composante organique d'un alcool primaire ou secondaire obtenu de R''*OH duquel est extrait un aldéhyde ou cétone odorant.