2,2-Dimethyl-6-phenyl-5-hexen-3-one

• 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: 2,2-Dimethyl-6-phenyl-5-hexen-3-one
• 英文别名: 2-methyl-6-phenyl-hex-5-en-3-one；2,2-dimethyl-6-phenylhex-5-en-3-one
• 化学式: C₁₄H₁₈O
• 分子量: 202.296
• InChiKey: LEAJXRODHPKUDG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.71
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  2,2-Dimethyl-6-phenyl-5-hexen-3-one 在 盐酸 、 2,2,6,6-四甲基哌啶氧化物 、 sodium nitrite 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以55%的产率得到2,2-dimethyl-1-(5-phenylisoxazol-3-yl)propan-1-one
  参考文献：
  名称：

  β,γ-不饱和酮与 NaNO2 的自由基 5-endo trig 环化合成 3-酰基异恶唑

  摘要：

  开发了一种在单锅反应中从容易获得的 β,γ-不饱和酮合成 3-酰基-异恶唑的新策略，并通过自由基 5-内三环化获得不同取代的 3-酰基-异恶唑。底物的范围相当广泛。

  DOI：

  10.1002/ejoc.202101411
• 作为产物：
  描述：

  (E)-β-chlorostyrene 在 iron(II) chloride 频哪酮 、 potassium tert-butylate 作用下， 以 二甲基亚砜 为溶剂， 反应 3.17h， 生成 2,2-Dimethyl-6-phenyl-5-hexen-3-one
  参考文献：
  名称：

  Competition of Mechanisms in Nucleophilic Substitution of Vinyl Halides. An Unequivocal Example of the Vinylic SRN1 Route1

  摘要：

  In a search for an unambiguous example of the vinylic S(RN)1 route, several vinyl bromides and iodides were reacted mostly with (-)CH(2)COCMe(3), and sometimes with (-)CH(2)COPh, (CH)-C--(Me)COEt, and (EtO)(2)PO- ions, under Fe2+- or photostimulation in Me(2)SO. Vinyl halides having vinylic hydrogens, such as beta-bromostyrene, gave acetylenic products, e.g., phenylacetylene or a tertiary PhC=C-substituted alcohol, whereas vinyl halides with allylic hydrogens, such as Me(2)C=C(I)CHMe(2), gave a substituted allene. Reduction products of the halogen, as well as substitution and rearranged substitution products, were also formed. The operation of ionic elimination-addition routes accounts for formation of most of the products, while the reduction products arise from an intermediate vinyl radical. Ph(2)C=C(Br)Ph (20) and Me(2)C=C(Br)Ph (25) gave both substitution and reduction products, but Me(2)C=C(Br)-t-Bu (23) gave only a reduction product. Formation of substitution products from the conjugated 20 and 25 was ascribed to a reaction via a vinylic S(RN)1 route, while lack of substitution in 23 is related to its nonconjugated system and to the consequent higher energy that the radical anion of the substitution product would have. The one here reported seems to be the first case of an exclusive genuine vinylic S(RN)1 process.

  DOI：

  10.1021/jo00101a045

文献信息

• Solvent-dependent copper-catalyzed synthesis of pyrazoles under aerobic conditions
  作者：Florian Pünner、Yoshihiro Sohtome、Mikiko Sodeoka

  DOI：10.1039/c6cc06935e

  日期：——

  present a copper-catalyzed oxidative cyclization of [small beta],[gamma]-unsaturated hydrazones, utilizing molecular oxygen as a stoichiometric oxidant. The methodology provides distinct classes of pyrazoles simply by changing the reaction solvent. Tris-substituted...

  我们提出了利用分子氧作为化学计量的氧化剂的铜催化的小β，γ-不饱和的氧化环化。该方法只需更改反应溶剂即可提供不同种类的吡唑。三取代...
• A One-Pot Synthesis of 2-Aminopyrimidines from Ketones, Arylacetylenes, and Guanidine
  作者：Elena Yu. Schmidt、Inna V. Tatarinova、Nadezhda I. Protsuk、Igor’ A. Ushakov、Boris A. Trofimov

  DOI：10.1021/acs.joc.6b02233

  日期：2017.1.6

  The three-component reaction of ketones, arylacetylenes, and guanidine catalyzed by the KOBut/DMSO system leads to 2-aminopyrimidines in up to 80% yield. Depending on structure of the starting ketones, the aromatization of intermediate dihydropyrimidines occurs either with loss of hydrogen molecules or methylbenzenes. The latter process takes place in the ketones, in which one of the substituents is

  KOBu t / DMSO系统催化的酮，芳基乙炔和胍的三组分反应可产生高达80％收率的2-氨基嘧啶。取决于起始酮的结构，中间体二氢嘧啶的芳构化在氢分子或甲基苯损失的情况下发生。后一种方法发生在酮中，其中一个取代基不是甲基。对于二烷基-，芳基（杂芳基）烷基-和环烷基酮而言，反应条件是容许的。
• Nano copper ferrite: A reusable catalyst for the synthesis of β, γ-unsaturated ketones
  作者：Y L N MURTHY、B S DIWAKAR、B GOVINDH、K NAGALAKSHMI、I V KASI VISWANATH、RAJENDRA SINGH

  DOI：10.1007/s12039-012-0258-9

  日期：2012.5

  Copper ferrite nano material as reusable heterogeneous initiator in the synthesis of β, γ-unsaturated ketones and allylation to acid chlorides are presented. The reaction of allylichalides with various acid chlorides is achieved in the presence of copper ferrite nano powders at room temperature in tetrahydrofuran (THF). The present method is first of its kind in the synthesis of title compounds without

  提出了一种可重复使用的异质引发剂铜铁氧体纳米材料，用于合成β，γ-不饱和酮和烯丙基化为酰氯。在室温下，在四氢呋喃（THF）中，在铜铁氧体纳米粉的存在下，实现烯丙基卤化物与各种酰氯的反应。本方法是在没有任何添加剂/助催化剂的情况下标题化合物的合成中的第一种方法。纳米催化剂易于回收并记录其可重复使用性。 实现了使用铁氧体铜纳米材料合成β，γ-不饱和酮的有效方案。通过光谱技术表征化合物。
• Bifunctional Thiourea-Catalyzed Asymmetric Inverse-Electron-Demand Diels–Alder Reaction of Allyl Ketones and Vinyl 1,2-Diketones via Dienolate Intermediate
  作者：Xinglong Li、Xiangwen Kong、Shuang Yang、Miao Meng、Xinyue Zhan、Min Zeng、Xinqiang Fang

  DOI：10.1021/acs.orglett.9b00035

  日期：2019.4.5

  most employed intermediates to realize such transformation, and the use of dienolate intermediate remains elusive. Reported herein is the asymmetric inverse-electron-demand oxa-Diels–Alder reaction between allyl ketones and alkenyl 1,2-diketones using a bifunctional thiourea catalyst. The reaction afforded various highly functionalized dihydropyrans with good to excellent enantioselectivities under mild

  逆电子需求的Diels-Alder反应吸引了广泛的研究重点。然而，烯醇盐和烯胺是实现这种转化的最常用的中间体，并且二烯醇盐中间体的使用仍然难以实现。本文报道的是使用双官能硫脲催化剂的烯丙基酮和烯基1,2-二酮之间的不对称逆电子要求的oxa-Diels-Alder反应。该反应在温和条件下提供了具有良好至优异对映选择性的各种高度官能化的二氢吡喃，并且还实现了产物的进一步新颖转化。
• An Expedient Access to γ-Ketophosphine Chalcogenides via the Chemo- and Regioselective Addition of Secondary Phosphine Chalcogenides to β,γ-Ethylenic Ketones
  作者：Alexander V. Artem'ev、Svetlana F. Malysheva、Nataliya A. Belogorlova、Nadezhda I. Protzuk、Alexander I. Albanov、Irina Yu. Bagryanskaya、Elena Yu. Schmidt、Nina K. Gusarova、Boris A. Trofimov

  DOI：10.1002/hc.21281

  日期：2015.11

  γ-Ketophosphine chalcogenides, precursors for plethora of novel functionalized phosphine chalcogenides and phosphines, are synthesized by chemo- and regioselective addition of secondary phosphine chalcogenides to β,γ-ethylenic ketones under catalyst- and solvent-free conditions (80–100°C, 8–70 h) in excellent yields. The straightforward superbase-catalyzed synthesis of starting β,γ-ethylenic ketones

  γ-酮膦硫属化物是大量新型官能化膦硫属化物和膦的前体，通过在无催化剂和无溶剂条件（80-100°C， 8-70 小时），产量极佳。由酮和乙炔直接在超碱催化下合成起始 β,γ-烯酮确保了获得目标 γ-酮膦硫属化物的便利。