1-苯基-4-(三甲基硅烷基)-1-丁酮 | 17337-21-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 1-苯基-4-(三甲基硅烷基)-1-丁酮
• 英文名称: γ-(trimethylsilyl)butyrophenone
• 英文别名: 1-Phenyl-4-(trimethylsilyl)butan-1-one；1-phenyl-4-trimethylsilylbutan-1-one
• CAS: 17337-21-2
• 化学式: C₁₃H₂₀OSi
• 分子量: 220.387
• InChiKey: YNTOYQPUEOHTNP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.99
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  1-苯基-4-(三甲基硅烷基)-1-丁酮 以 氘代乙腈 为溶剂， 反应 0.58h， 以10%的产率得到1,2-联苯甲酰乙烷
  参考文献：
  名称：

  Exploratory Studies of H-Atom Abstraction and Silyl-Transfer Photoreactions of Silylalkyl Ketones and (Silylalkyl)phthalimides

  摘要：

  Exploratory studies have been conducted to probe competitive H-atom abstraction and SET-promoted, silyl-transfer reactions of excited states of silylalkyl ketones and (silylalkyl)phthalimides. Photochemical investigations with the (silylalkyl)phthalimides have demonstrated that typical gamma-H atom abstraction reactions occur upon irradiation in less polar and less silophilic solvents. In contrast, irradiation of these substances in polar-protic-silophilic solvents results in product formation via pathways involving SET-induced desilylation. Photoreactions of silylamido-aryl ketones in either nonsilophilic or silophilic solvents take place almost exclusively by sequential SET silyl-transfer routes to produce azetidine products. Finally, the chemical selectivities of photochemical reactions of silylpropyl-aryl ketones appear to depend on medium polarity and silophilicity. Irradiation of these substrates in less polar-nonsilophilic solvents leads to almost exclusive formation of acetophenone and vinyltrimethylsilane in essentially equal yields by a reaction pathway initiated by gamma-H atom abstraction and 1,4-biradical fragmentation. However, irradiation of these substances in polar-silophilic solvents produces acetophenone and vinyltrimethylsilane in an ca. 1.7:1 ratio reflecting the fact that a silyl-transfer pathway competes with H-atom abstraction under these conditions.

  DOI：

  10.1021/jo9522623
• 作为产物：
  描述：

  环丙基苯基碳酸酯 在 甲基锂 、 仲丁基锂 作用下， 以 六甲基磷酰三胺 、 乙醚 为溶剂， 反应 50.5h， 生成 1-苯基-4-(三甲基硅烷基)-1-丁酮
  参考文献：
  名称：

  α-环丙基苄醇转化为γ-三甲基甲硅烷基丁苯酮的新机理

  摘要：

  α-环丙基苄醇与甲基锂然后六甲基二硅烷反应的机理研究表明，中间体（4）与三甲基甲硅烷基阴离子作为催化剂的歧化反应提供了环丙基苯基酮。在后一种化合物中原位1,4-加成三甲基甲硅烷基阴离子可得到主要产物γ-三甲基甲硅烷基丁苯酮（2）。

  DOI：

  10.1039/c39850000452

文献信息

• Organometallic photochemistry photochemistry of some acyclic ketosilanes
  作者：Henry G. Kuivila、Perry L. Maxfield

  DOI：10.1016/s0022-328x(00)81715-5

  日期：1967.10

  Photolysis of a series of silyl ketones with the general structure (CH3)3Si(CH2)nCOR with n = 0–4, R = C6H5 and with n = 0–3, R = CH3 has been investigated. When n = 3 or 4 a major course of reaction is the Type II cleavage. When R = CH3 and n = 3 a substantial amount of cyclobutanol formation occurs; none is detected when R = C6H5. If n = 2 and R = C6H5 the only photoreactions established are reductive

  具有通式结构的一系列甲硅烷基酮的光解（CH 3）3 SI（CH 2）ñ COR与Ñ = 0-4，R = C 6 H ^ 5，并用Ñ = 0-3，R = CH 3已经调查。当n = 3或4时，反应的主要过程是II型裂解。当R = CH 3且n = 3时，会形成大量的环丁醇。当R ＝ C 6 H 5时，没有检测到。如果n = 2且R = C 6 H 5唯一建立的光反应是还原性烷基化（通过溶剂环己烷）和羰基亚甲基键的裂解。如果R ＝ CH 3，则可以在羰基-亚甲基键的初始裂解的基础上使所有分离出的产物合理化。在惰性溶剂中，n = 1或0的化合物几乎不会发生光化学分解。但是，每种化合物都容易进行光催化水解以形成三甲基硅烷醇和醛或酮。
• Can relief of ring-strain in a cyclopropylmethyllithium drive the Brook rearrangement?
  作者：Jonathan Clayden、David W. Watson、Mark Chambers

  DOI：10.1016/j.tet.2004.10.099

  日期：2005.3

  2]-Brook rearrangement led to α-silyloxy organolithiums which on warming underwent cyclopropane ring opening and [1,5]-retro-Brook rearrangement to yield γ-silyl ketones. Despite the favourability of the cyclopropane ring opening, the Brook rearrangement still required the presence of an anion stabilising group to proceed. β-Silylketones were similarly formed by Brook–retro-Brook rearrangement on warming

  α-环丙基-α-三烷基甲硅烷基醇盐通过将环丙基锂加至酰基硅烷中或将有机锂加至环丙基甲酰基硅烷中而形成。[1,2]-布鲁克重排导致α-甲硅烷氧基有机锂，在加热时会发生环丙烷开环反应，[1,5]-复古布鲁克重排产生γ-甲硅烷基酮。尽管环丙烷开环是有利的，但布鲁克重排仍需要阴离子稳定基团的存在才能进行。β-甲硅酮是通过在温暖的带有硅酸锂的酰基硅烷上进行Brook-retro-Brook重排而形成的。
• Copper‐Catalyzed Cross‐Coupling of Acylzirconocenes and Diaryliodonium Salts: An Efficient Synthesis of Alkyl‐aryl‐ketones from Alkenes
  作者：Simone Grosso、Marcelina Mlynczak、Gwilherm Evano、Olivier Riant

  DOI：10.1002/ejoc.202300938

  日期：2023.12.13

  An efficient cross-coupling between acylzirconocenes, readily prepared by hydrozirconation/carbonylation of alkenes, and diaryliodonium tetrafluoroborates is reported. This procedure enables the synthesis of a variety of alkyl-aryl-ketones upon simple catalysis with copper cyanide without the need of additional ligands and only requires a low pressure of carbon monoxide generated in situ, in a two-chamber

  据报道，通过烯烃的氢化锆化/羰基化容易制备的酰基锆茂和四氟硼酸二芳基碘之间的有效交叉偶联。该方法能够在氰化铜的简单催化下合成各种烷基芳基酮，无需额外的配体，并且仅需要在两室反应器中由 N-甲酰糖精原位产生低压一氧化碳。
• Nickel-Catalyzed Cross-Coupling between Functionalized Primary or Secondary Alkylzinc Halides and Primary Alkyl Halides
  作者：Anne Eeg Jensen、Paul Knochel

  DOI：10.1021/jo0105787

  日期：2002.1.1

  In the presence of Bu4NI (3 equiv) and 4-fluorostyrene (20 mol %), unreactive primary and secondary alkylzinc iodides undergo nickel-catalyzed cross-couplings with various primary alkyl iodides or bromides. More reactive secondary dialkylzincs and the mixed zinc organometallics RZnTMSM undergo the cross-coupling reaction in the absence of Bu4NI. The bicyclic secondary diorganozinc 6 prepared via boron-zinc exchange reacts with high retention of configuration. Free NH-groups are tolerated in the cross-coupling allowing the synthesis of aminated products.
• Cobalt-Catalyzed Intermolecular Hydroacylation of Olefins through Chelation-Assisted Imidoyl C–H Activation
  作者：Junfeng Yang、Yuan Wah Seto、Naohiko Yoshikai

  DOI：10.1021/acscatal.5b00581

  日期：2015.5.1

  A low-valent cobalt catalyst generated from cobalt(II) bromide, a diphosphine ligand, and zinc powder promotes intermolecular hydroacylation of olefins using N-3-picolin-2-yl aldimines as aldehyde equivalents, which affords, upon acidic hydrolysis, ketone products in moderate to good yields with high linear selectivity. The reaction is applicable to styrenes, vinylsilanes, and aliphatic olefins as well as to various aryl and heteroaryl aldimines. The cobalt catalysis features a distinctively lower reaction temperature (60 degrees C) compared with those required for the same type of transformations catalyzed by rhodium complexes (typically 130-150 degrees C).