反式-1-甲基-2-(4-(三氟甲基)苯基)环丙烷 | 89321-49-3

• 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: 反式-1-甲基-2-(4-(三氟甲基)苯基)环丙烷
• 英文名称: trans-1-methyl-2-(4-(trifluoromethyl)phenyl)cyclopropane
• 英文别名: trans-1-methyl-2-p-CF3-phenylcyclopropane；1beta-Methyl-2alpha-[4-(trifluoromethyl)phenyl]cyclopropane；1-[(1R,2R)-2-methylcyclopropyl]-4-(trifluoromethyl)benzene
• CAS: 89321-49-3
• 化学式: C₁₁H₁₁F₃
• 分子量: 200.204
• InChiKey: QMGRIKXSRSSPKW-GMSGAONNSA-N

物化性质

• 沸点：
  208.9±35.0 °C(Predicted)
• 密度：
  1.171±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  反式-1-甲基-2-(4-(三氟甲基)苯基)环丙烷 在 cytochrome P₄₅₀s 2B₁ 、 1,2-二十二酰基-sn-glycero-3-胆碱磷酸 、 还原型辅酶II(NADPH)四钠盐 作用下， 以 phosphate buffer 为溶剂， 生成 1-(4-(三氟甲基)苯基)丁-3-烯-1-醇 、 3-(4-trifluoromethylphenyl)-2,3-methanopropan-1-ol
  参考文献：
  名称：

  细胞色素 P450 酶中氢过氧铁类的羟基化

  摘要：

  用肝细胞色素 P450 酶、P450s 2B1、Delta2B4、Delta2B4、T302A、Delta23E1 和 T302E1 对反式-2-（对三氟甲基苯基）环丙基甲烷 (1) 的对映异构体进行羟基化，测定了分子内和分子间动力学同位素效应 (KIE)。得到两个甲基氧化产物，未重排的反式-2-（对三氟甲基苯基）环丙基甲醇（2）和重排的 1-（对三氟甲基苯基）丁-3-烯-1-醇（3）。在双氘甲基底物 (1-d(2)) 的分子内 KIE 研究和未氘化 (1-d(0)) 和三氘甲基 (1-d(3)) 底物混合物的分子间 KIE 研究中，产物 2 的表观 KIE始终比产品 3 的表观 KIE 大大约一个因子。1.2. 发现与 1-d(2) (k(H)/k(D) = 9-11 在 10 摄氏度） 的大型分子内 KIEs 显示不复杂的隧道效应与两种 P450 酶的变温研究。结果需要在竞争性或顺序性

  DOI：

  10.1021/ja038237t
• 作为产物：
  描述：

  (E)-N-methoxy-N-methyl-3-(4-(trifluoromethyl)phenyl)acrylamide 在 lithium aluminium tetrahydride 、 potassium tert-butylate 、 sodium hydride 、 三乙基硼氢化锂 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 二甲基亚砜 为溶剂， 反应 41.5h， 生成 反式-1-甲基-2-(4-(三氟甲基)苯基)环丙烷
  参考文献：
  名称：

  Picosecond radical kinetics. Rate constants for ring openings of 2-aryl-substituted cyclopropylcarbinyl radicals

  摘要：

  The kinetics of ring openings of a series of eight (trans-2-arylcyclopropyl)methyl radicals (1) were studied by indirect kinetic methods using Barton's PTOC esters as radical precursors and reaction with PhSeH as the competition reaction. The substituents were CF3, F, Me, and OMe located on both the para and meta positions of the aromatic ring. Syntheses of the radical precursors and the products of the radical reactions are described. Kinetics were determined between -43 and 25 degrees C in four cases (CF, and OMe substituents) and at 0 and 25 degrees C in the other four cases. The rate constants at 25 degrees C ranged from 1.0 x 10(11) s(-1) (p-CH3) to 4.1 x 10(11) s(-1) (p-CF,). The relatively large acceleration of the p-CF3 group, ca. 2.5 times as fast as the parent system with Ar = Ph, correlates well with Adam's Delta D substituent parameters but not with other radical substituent parameters. These calibrated radical rearrangements provide a new set of ultrafast reactions that can be applied in mechanistic probe studies.

  DOI：

  10.1139/cjc-77-5-6-1123

文献信息

• Synthesis and spectral characterization of a series of iron and ruthenium benzylidene complexes, Cp(CO)(L)M:CH(C6H4R)+ (M = Fe, Ru; L = CO, PPh3; R = p-H, p-F, p-CH3, p-OCH3). Barriers to aryl rotation and benzylidene transfer reactions
  作者：M. Brookhart、William B. Studabaker、M. Beth Humphrey、G. Ronald Husk

  DOI：10.1021/om00103a016

  日期：1989.1
• A Substituted Hypersensitive Radical Probe for Enzyme-Catalyzed Hydroxylations:  Synthesis of Racemic and Enantiomerically Enriched Forms and Application in a Cytochrome P450-Catalyzed Oxidation
  作者：Patrick H. Toy、Bhavani Dhanabalasingam、Martin Newcomb、Imad H. Hanna、Paul F. Hollenberg

  DOI：10.1021/jo9712097

  日期：1997.12.1

  The syntheses of racemic and enantiomerically enriched trans-1-methyl-2-(4-(trifluoromethyl)phenyl)cyclopropane (3) and the possible oxidation products from enzyme-catalyzed hydroxylation of 3 at the methyl group are reported. The important intermediate in the production of 3 was the Weinreb amide of the 2-arylcyclopropanecarboxylic acid which could be prepared in diastereomerically pure form and which also served as an intermediate for production of the cyclic oxidation products of 3. Hydroxylation of 3 by the cytochrome P450 isozyme CYP2B1 gave cyclic and ring-opened products. The product ratios support an insertion mechanism for the enzyme-catalyzed hydroxylation reaction in which minor amounts of rearranged products are produced by radical fragmentation within the transition structure of the insertion and by a competing reaction involving a cationic species. Formation of cationic rearrangement products by a heterolytic fragmentation reaction of a first-formed protonated alcohol product is suggested on the basis of the apparent amounts of cationic products formed in the hydroxylation of 3. This pathway for cation production appears to re quire that the activated enzyme complex (equivalent to enzyme-substrate-H2O2) oxidizes substrate before water dissociates to give an iron-oxo species.
• Picosecond radical kinetics. Rate constants for ring openings of 2-aryl-substituted cyclopropylcarbinyl radicals
  作者：Martin Newcomb、Seung-Yong Choi、Patrick H. Toy

  DOI：10.1139/cjc-77-5-6-1123

  日期：——

  The kinetics of ring openings of a series of eight (trans-2-arylcyclopropyl)methyl radicals (1) were studied by indirect kinetic methods using Barton's PTOC esters as radical precursors and reaction with PhSeH as the competition reaction. The substituents were CF3, F, Me, and OMe located on both the para and meta positions of the aromatic ring. Syntheses of the radical precursors and the products of the radical reactions are described. Kinetics were determined between -43 and 25 degrees C in four cases (CF, and OMe substituents) and at 0 and 25 degrees C in the other four cases. The rate constants at 25 degrees C ranged from 1.0 x 10(11) s(-1) (p-CH3) to 4.1 x 10(11) s(-1) (p-CF,). The relatively large acceleration of the p-CF3 group, ca. 2.5 times as fast as the parent system with Ar = Ph, correlates well with Adam's Delta D substituent parameters but not with other radical substituent parameters. These calibrated radical rearrangements provide a new set of ultrafast reactions that can be applied in mechanistic probe studies.
• Hydroxylation by the Hydroperoxy-Iron Species in Cytochrome P450 Enzymes
  作者：R. Esala P. Chandrasena、Kostas P. Vatsis、Minor J. Coon、Paul F. Hollenberg、Martin Newcomb

  DOI：10.1021/ja038237t

  日期：2004.1.1

  1-(p-trifluoromethylphenyl)but-3-en-1-ol (3). In intramolecular KIE studies with dideuteriomethyl substrates (1-d(2)) and in intermolecular KIE studies with mixtures of undeuterated (1-d(0)) and trideuteriomethyl (1-d(3)) substrates, the apparent KIE for product 2 was consistently larger than the apparent KIE for product 3 by a factor of ca. 1.2. Large intramolecular KIEs found with 1-d(2) (k(H)/k(D) = 9-11

  用肝细胞色素 P450 酶、P450s 2B1、Delta2B4、Delta2B4、T302A、Delta23E1 和 T302E1 对反式-2-（对三氟甲基苯基）环丙基甲烷 (1) 的对映异构体进行羟基化，测定了分子内和分子间动力学同位素效应 (KIE)。得到两个甲基氧化产物，未重排的反式-2-（对三氟甲基苯基）环丙基甲醇（2）和重排的 1-（对三氟甲基苯基）丁-3-烯-1-醇（3）。在双氘甲基底物 (1-d(2)) 的分子内 KIE 研究和未氘化 (1-d(0)) 和三氘甲基 (1-d(3)) 底物混合物的分子间 KIE 研究中，产物 2 的表观 KIE始终比产品 3 的表观 KIE 大大约一个因子。1.2. 发现与 1-d(2) (k(H)/k(D) = 9-11 在 10 摄氏度） 的大型分子内 KIEs 显示不复杂的隧道效应与两种 P450 酶的变温研究。结果需要在竞争性或顺序性