2,2-二甲基-3-苯丙醛 | 1009-62-7

• 物质功能分类: 香精与香料 - 合成香料 - 醛类香料
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2,2-二甲基-3-苯丙醛
• 中文别名: 2,2-二甲基-3-苯基丙醛；alpha,alpha-二甲基苯丙醛；海风醛；α,α-二甲基苯丙醛
• 英文名称: 2,2-dimethyl-3-phenylpropionaldehyde
• 英文别名: 2,2-dimethyl-3-phenylpropanal
• CAS: 1009-62-7
• 化学式: C₁₁H₁₄O
• mdl: MFCD00015918
• 分子量: 162.232
• InChiKey: KYUNECWPKRYPJM-UHFFFAOYSA-N

物化性质

• LogP：
  2.545 (est)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.363
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2912299000

反应信息

• 作为反应物：
  描述：

  2,2-二甲基-3-苯丙醛 在 双(三甲基硅基)过氧化物 、 LaLi₃-tris((R)-binaphthoxide) 、 racemic trans-N,N'-bis(p-toluenesulfonyl)cyclohexane-1,2-diamine 、 4 A molecular sieve 、 水 、 四氯化锡 、 双(三甲基硅烷基)氨基钾 作用下， 以 二氯甲烷 为溶剂， 反应 122.33h， 生成 (6S)-6-<(1R)-1-hydroxy-2,2-dimethyl-3-phenylpropyl>-2-pyrone
  参考文献：
  名称：

  Direct Catalytic Asymmetric Aldol Reaction

  摘要：

  The direct catalytic asymmetric aldol reaction using aldehydes and unmodified ketones is described for the first time herein. This reaction was first found to be promoted by 20 mol % of anhydrous (R)-LLB (L = lanthanum, L = lithium, B = (R)-binaphthol moiety) at -20 OC, giving a variety of aldol products in ee's ranging from 44 to 94%. This asymmetric reaction has been greatly improved by developing a new heteropolymetallic asymmetric catalyst [(R)-LLB, KOH, and H2O]. Using 3-8 mol % of this catalyst, a variety of direct catalytic asymmetric aldol reactions were again found to proceed smoothly, affording aldol products in ee's ranging from 30 to 93% and in good to excellent yields. Interestingly, the use of this new heteropolymetallic asymmetric catalyst has realized a diastereoselective and enantioselective aldol reaction using cyclopentanone for the first time. It is also noteworthy that a variety of aldehydes, including hexanal, can be utilized for the current direct catalytic asymmetric aldol reaction. Chiral aldehydes containing alpha-hydrogen including (S)-hydrocinnamaldehyde-alpha-d have been found to produce the corresponding aldol products with negligible racemization (0-4%) at the a-position One of the aldol products has been successfully converted to the key synthetic intermediates of epothilone A and bryostatin 7. The possible structure of the heteropolymetallic catalyst is also discussed. Finally, mechanistic studies have revealed a characteristic reaction pathway, namely that the reaction is kinetically controlled and the rate-determining step is the deprotonation of the ketone. This is consistent with the fact that the reaction rate is independent of the concentration of the aldehyde.

  DOI：

  10.1021/ja990031y
• 作为产物：
  描述：

  2-(2-methyl-1-phenylpropan-2-yl)-1,3-oxathiolane 在 eosin Y disodium salt 作用下， 以 乙腈 为溶剂， 反应 3.0h， 以69%的产率得到2,2-二甲基-3-苯丙醛
  参考文献：
  名称：

  Visible light photoredox catalyzed deprotection of 1,3-oxathiolanes

  摘要：

  公开了一种温和且有效的可见光光氧化还原催化空气氧化的1,3-氧硫杂环戊烷去保护方法，使用曙红Y作为光催化剂。

  DOI：

  10.1039/c9ob02517k

文献信息

• Toward a mild dehydroformylation using base-metal catalysis
  作者：Dylan J. Abrams、Julian G. West、Erik J. Sorensen

  DOI：10.1039/c6sc04607j

  日期：——

  biosynthesis of cholesterol and related sterols under mild conditions using base-metal catalysts. In contrast, chemists have recently developed a non-oxidative dehydroformylation method; however, it requires high temperatures and a precious-metal catalyst. Careful study of both approaches has informed our efforts to design a base-metal catalyzed, mild dehydroformylation method that incorporates benefits from

  脱氢甲酰化或醛类反应生成烯烃，氢气和一氧化碳的反应是一种有力的转化，尽管逆反应加氢甲酰化在工业上具有很高的重要性，但这种转化仍未开发。有趣的是，大自然通常在使用贱金属催化剂的温和条件下，在胆固醇和相关固醇的生物合成中进行相关的转化，即氧化脱氢甲酰化。相反，化学家们最近开发了一种非氧化脱氢甲酰化方法。但是，它需要高温和贵金属催化剂。对这两种方法的仔细研究使我们努力设计一种贱金属催化的轻度脱氢甲酰化方法，该方法综合了每种方法的优点，同时避免了它们各自的缺点。重要的，
• Ketenimines from Isocyanides and Allyl Carbonates: Palladium-Catalyzed Synthesis of β,γ-Unsaturated Amides and Tetrazoles
  作者：Guanyinsheng Qiu、Mathias Mamboury、Qian Wang、Jieping Zhu

  DOI：10.1002/anie.201609034

  日期：2016.12.5

  allyl ethyl carbonates with isocyanides in the presence of a catalytic amount of Pd(OAc)2 provided ketenimines through β‐hydride elimination of the allyl imidoylpalladium intermediates. The insertion of the isocyanide into the π‐allyl Pd complex proceeded via an unusual η1‐allyl Pd species. The resulting ketenimines were hydrolyzed to β,γ‐unsaturated carboxamides during purification by flash column chromatography

  在催化量的Pd（OAc）2存在下，碳酸烯丙乙酯与异氰酸酯的反应通过烯丙基酰亚胺基钯中间体的β-氢化物消除，提供了烯酮胺。胩的插入π烯丙基钯配合物经由一个不寻常的η进行1 -烯丙基钯物种。在硅胶上通过快速柱色谱纯化时，将得到的酮亚胺水解成β，γ-不饱和羧酰​​胺，或与酸或三甲基叠氮化硅通过[3 + 2]环加成反应原位转化为1,5-二取代四唑。
• Highly Enantioselective Addition of Me₂Zn to Aldehydes Catalyzed by ClCr(Salen)
  作者：Pier Giorgio Cozzi、Peter Kotrusz

  DOI：10.1021/ja057969d

  日期：2006.4.1

  enantiomeric excesses are obtained in the addition of Me2Zn catalyzed by commercially available ClCr(Salen). Broad scope, simple procedure, room temperature, low catalyst loading are the characteristics of this new enantioselective process, which uses the rather unreactive Me2Zn. Enantiomeric excesses in the range of 71-99% are obtained with all the aldehydes tested.

  在由市售的 ClCr(Salen) 催化的 Me2Zn 的添加中获得高对映体过量。范围广、程序简单、室温、催化剂负载量低是这种新的对映选择性工艺的特点，它使用相当不活泼的 Me2Zn。所有测试的醛都获得了 71-99% 范围内的对映体过量。
• A General Catalytic Allylation Using Allyltrimethoxysilane
  作者：Shingo Yamasaki、Kunihiko Fujii、Reiko Wada、Motomu Kanai、Masakatsu Shibasaki

  DOI：10.1021/ja0262582

  日期：2002.6.1

  mild catalytic allylation of carbonyl compounds, applicable to aldehydes, ketones, and imines is developed using allyltrimethoxysilane as the allylating reagent. The reaction proceeds smoothly with 1-10 mol % of CuCl and TBAT in THF at ambient temperature. Mechanism studies indicated that the copper alkoxide, allylfluorodimethoxysilane, and allyltrimethoxysilane are essential to promote the reaction

  使用烯丙基三甲氧基硅烷作为烯丙基化试剂开发了适用于醛、酮和亚胺的羰基化合物的一般和温和的催化烯丙基化反应。在环境温度下，在 THF 中加入 1-10 mol% 的 CuCl 和 TBAT 使反应顺利进行。机理研究表明，铜醇盐、烯丙基氟二甲氧基硅烷和烯丙基三甲氧基硅烷对于有效促进反应至关重要。使用烯丙基硅烷将反应初步扩展到酮的第一次催化对映选择性烯丙基化，使用 CuCl-p-tol-BINAP-TBAT 催化剂（15 mol%）从苯乙酮中产生了 61% ee 的产物。
• [EN] HYDROLYTICALLY LABILE PRO-FRAGRANCES CONTAINING α,β UNSATURATED ESTERS<br/>[FR] PRO-PARFUMS HYDROLYTIQUEMENT LABILES CONTENANT DES ESTERS α,β INSATURÉS
  申请人：HENKEL AG & CO KGAA

  公开号：WO2020058058A1

  公开（公告）日：2020-03-26

  The present invention pertains to pro-fragrances and relates to a pro-fragrance compound of the formula (I). Furthermore, the invention relates to compositions, a laundry product, a home care product, and an insect repellant, comprising the compound of formula (I). Also encompassed are a method for preparing the compound of formula (I) and uses of a compound of formula (I) for increasing the longlastingness of a fragrance, for increasing the stability and perception of a fragrance, and for improving the adhesion of a fragrance to textiles.

  本发明涉及前香料，涉及公式(I)的前香料化合物。此外，该发明涉及包含公式(I)化合物的组合物、洗涤产品、家用产品和驱虫剂。还包括一种制备公式(I)化合物的方法，以及利用公式(I)化合物增加香气的持久性、增加香气的稳定性和感知性，以及改善香气附着在纺织品上的用途。