2-(2-氯苯基)-2-甲基丙醛 | 484001-11-8

• 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-氯苯基)-2-甲基丙醛
• 英文名称: 2-(2-Chlorophenyl)-2-methylpropanal
• CAS: 484001-11-8
• 化学式: C₁₀H₁₁ClO
• 分子量: 182.65
• InChiKey: HETBONPDAKNQHA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2913000090

反应信息

• 作为反应物：
  描述：

  2-(2-氯苯基)-2-甲基丙醛 在 硫酸 作用下， 以 正戊烷 为溶剂， 反应 1.5h， 生成 trans-4-Chloro-2,3-dihydro-1,1,2,3-tetramethyl-1H-inden
  参考文献：
  名称：

  Über Umlagerungen bei der Cyclialkylierung von Arylpentanolen zu 2,3-Dihydro-1H-inden-Derivaten, 5. Mitteilung

  摘要：

  The mechanism proposed in [1] to explain the surprising result of the cyclialkylation of 4-(2-chlorophenyl)-2,4-dimethylpentan-2-ol (3, R = Me), which gives not only the 'normal' product, i.e., the 4-chloro-2,3-dihydro-1,1,3,3-tetramethyl- (4), but also the isomer trans-4-chloro-2,3-dihydro-1,1,2,3-tetramethyl-1H-inden (5), could be differentiated in two sections (cf. Scheme 2): the first from 3 to the intermediary ion IIareversible arrowIIb, and the second from the latter ions to the final product 5. For the first section, a sufficiently satisfactory explanation has been given in [1]; the second section has received important support from the mechanisms of the cyclialkylation of 2,4-dimethyl-2-phenylpentan-3-ol (6), the precursor of II'a, the ion IIa without the o-Cl substituent (cf. Schemes 2, 3 and 5 and [4]). The present communication gives an explanation of the influence of the o-Cl substituent: a mechanism is proposed for the very complex cyclialkylation of 2-(2-chlorophenyl)-2,4-dimethylpentan-3-ol (11; cf Scheme 9). Both mechanism may be considered as definitive. It is very surprising that, by the cyclialkylation of the compounds 1, 3, 8, 11, 15, and 17, only compound 1 gives the 'normal' product; the cyclialkylation of all other phenylpentanols follows complex pathways including Et, i-Pr, and Ph migrations, which could not be expected. In addition, it has been established that the transformation of 21 to 22 (cf Scheme 12) and that of 23 to 24 (cf Scheme 13) occur through two consecutive 1,2- and not through a single 1,3-hydride migration or through an elimination-addition process (cf Scheme 13). It can be assumed that the transformation of ion IV (the 2-(2-chlorophenyl)-3,4-dimethylpent-2-ylium ion) to the ion V (the 4-(2-chlorophenyl)-3,4-dimethylpent-2-ylium ion (both shown in Scheme 9 as D-isomers) occurs through the same pathway.

  DOI：

  10.1002/1522-2675(200207)85:7<2089::aid-hlca2089>3.0.co;2-0
• 作为产物：
  描述：

  2-(2-chlorophenyl)-2-methylpropanenitrile 在 lithium aluminium tetrahydride 作用下， 以 乙醚 、 乙酸乙酯 为溶剂， 反应 1.0h， 以60%的产率得到2-(2-氯苯基)-2-甲基丙醛
  参考文献：
  名称：

  Über Umlagerungen bei der Cyclialkylierung von Arylpentanolen zu 2,3-Dihydro-1H-inden-Derivaten, 5. Mitteilung

  摘要：

  The mechanism proposed in [1] to explain the surprising result of the cyclialkylation of 4-(2-chlorophenyl)-2,4-dimethylpentan-2-ol (3, R = Me), which gives not only the 'normal' product, i.e., the 4-chloro-2,3-dihydro-1,1,3,3-tetramethyl- (4), but also the isomer trans-4-chloro-2,3-dihydro-1,1,2,3-tetramethyl-1H-inden (5), could be differentiated in two sections (cf. Scheme 2): the first from 3 to the intermediary ion IIareversible arrowIIb, and the second from the latter ions to the final product 5. For the first section, a sufficiently satisfactory explanation has been given in [1]; the second section has received important support from the mechanisms of the cyclialkylation of 2,4-dimethyl-2-phenylpentan-3-ol (6), the precursor of II'a, the ion IIa without the o-Cl substituent (cf. Schemes 2, 3 and 5 and [4]). The present communication gives an explanation of the influence of the o-Cl substituent: a mechanism is proposed for the very complex cyclialkylation of 2-(2-chlorophenyl)-2,4-dimethylpentan-3-ol (11; cf Scheme 9). Both mechanism may be considered as definitive. It is very surprising that, by the cyclialkylation of the compounds 1, 3, 8, 11, 15, and 17, only compound 1 gives the 'normal' product; the cyclialkylation of all other phenylpentanols follows complex pathways including Et, i-Pr, and Ph migrations, which could not be expected. In addition, it has been established that the transformation of 21 to 22 (cf Scheme 12) and that of 23 to 24 (cf Scheme 13) occur through two consecutive 1,2- and not through a single 1,3-hydride migration or through an elimination-addition process (cf Scheme 13). It can be assumed that the transformation of ion IV (the 2-(2-chlorophenyl)-3,4-dimethylpent-2-ylium ion) to the ion V (the 4-(2-chlorophenyl)-3,4-dimethylpent-2-ylium ion (both shown in Scheme 9 as D-isomers) occurs through the same pathway.

  DOI：

  10.1002/1522-2675(200207)85:7<2089::aid-hlca2089>3.0.co;2-0

文献信息

• Palladium-Catalyzed Site-Selective C(sp³)–H Arylation of Phenylacetaldehydes
  作者：Bo-Bo Gou、Hang-Fan Liu、Jie Chen、Ling Zhou

  DOI：10.1021/acs.orglett.9b02650

  日期：2019.9.6

  describe a Pd-catalyzed selective C-H arylation reaction of phenylacetaldehydes using l-valine as the transient directing group. This process showed a broad substrate scope and excellent selectivity in which a ligand-controlled functionalization of the unactivated β-C(sp3)-H bond. In addition, enantioselective arylation of phenylacetaldehydes was preliminarily explored by utilizing a bulky chiral transient

  我们描述了使用L-缬氨酸作为瞬时导向基团的Pd催化的苯乙醛的选择性CH芳基化反应。此过程显示出广泛的底物范围和出色的选择性，其中未活化的β-C（sp3）-H键的配体控制功能化。此外，通过利用庞大的手性瞬态导向基团初步研究了苯乙醛的对映选择性芳基化。
• Benzocycloheptene derivatives, process for their production and their use as anti-inflammatory agents
  申请人：Rehwinkel Hartmut

  公开号：US20060247292A1

  公开（公告）日：2006-11-02

  The invention relates to polysubstituted 5H-benzocycloheptene derivatives of formula (I) process for their production, and their use as anti-inflammatory agents.

  本发明涉及公式（I）的多取代5H-苯并环庚烯衍生物的制备方法及其作为抗炎药物的用途。
• Cobalt‐Catalyzed Wagner–Meerwein Rearrangements with Concomitant Nucleophilic Hydrofluorination
  作者：Reece H. Hoogesteger、Nicola Murdoch、David B. Cordes、Craig P. Johnston

  DOI：10.1002/anie.202308048

  日期：2023.8.28

  A cobalt-catalyzed reaction has been developed, which proceeds via hydrogen atom transfer and radical-polar crossover steps, to form a phenonium ion under non-acidic conditions. This cationic intermediate can be regioselectively fluorinated by a tetrafluoroborate anion to give 1,2-aryl migrated products. Evaluation of distinctly substituted phenonium ion intermediates demonstrated the constraints for

  已经开发出一种钴催化反应，该反应通过氢原子转移和自由基极性交叉步骤进行，在非酸性条件下形成苯鎓离子。该阳离子中间体可以被四氟硼酸根阴离子区域选择性氟化，得到 1,2-芳基迁移产物。对明显取代的苯鎓离子中间体的评估表明了良好反应性和高选择性的限制。
• Catalyst‐Controlled Divergent Generations and Transformations of <i>α</i>‐Carbonyl Cations from Alkynes**
  作者：Junrui Zhou、Weilin Wang、Fenfang Zuo、Shupeng Liu、Pathan Mosim Amin、Kangbao Zhong、Ruopeng Bai、Youliang Wang

  DOI：10.1002/anie.202302545

  日期：2023.12.4

  Catalyst-controlled divergent generations of α-carbonyl cations from single alkyne functionalities and their divergent further transformations have been established. Broad spectrum of alkynes including aryl alkyne, ynamide, alkynyl ether, and alkynyl sulfide could be utilized. The intermediacy of α-carbonyl cations via the N−O bond cleavage was supported by DFT calculations in both catalytic systems

  已经建立了由单一炔烃官能团产生的催化剂控制的α-羰基阳离子的发散生成及其发散的进一步转化。可以使用广谱的炔烃，包括芳基炔烃、炔酰胺、炔基醚和炔基硫醚。两个催化体系中的 DFT 计算都支持α-羰基阳离子通过 N−O 键断裂的中介作用。
• WO2006/100099
  申请人：——

  公开号：——

  公开（公告）日：——