5-n-butyl-1,2,3,4-tetramethylcyclopentadiene | 144776-47-6

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 5-n-butyl-1,2,3,4-tetramethylcyclopentadiene
• 英文别名: 5-butyl-1,2,3,4-tetramethylcyclopenta-1,3-diene；1-butyl-2,3,4,5-tetramethylcyclopentadiene
• CAS: 144776-47-6
• 化学式: C₁₃H₂₂
• 分子量: 178.318
• InChiKey: KCTPXSVKZKTAAY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 5-n-butyl-1,2,3,4-tetramethylcyclopentadiene 在 盐酸 作用下， 以 甲醇 为溶剂， 115.0 ℃ 、1.03 MPa 条件下， 反应 1.0h， 以55%的产率得到[Cp*^n-butylIrCl]₂(μ²-Cl)₂
  参考文献：
  名称：

  快速获得衍生化的二聚环取代的二氯（环戊二烯基）铑（III）和铱（III）配合物

  摘要：

  The present work describes the design and synthesis of a series of rhodium and iridium dimers [(eta(5)-ring)MCl](2)(mu(2)-Cl)(2) (where (eta(5)-ring)MCl = (eta(5)-Me4C5R)Rh(III)Cl or (eta(5)-Me4C5R)Ir(III)Cl) using a new and efficient 1 h procedure. Rhodium and iridium dimeric complexes were synthesized via a microwave reaction. The modified HMe4C5R (R = isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, phenyl, benzyl, phenethyl, cyclohexyl, and cyclopentyl) type ligands were synthesized by reaction of 2,3,4,S-tetramethylcyclopent-2-en-1-one with the respective Grignard reagent (RMgX), followed by elimination of water under acidic conditions to produce the tetramethyl(alkyl or aryl)cyclopentadienes in moderate to excellent yields (40-98%). Reaction of the HMe4C5R ligands with [M(COD)](mu(2)-Cl)(2) (M = Rh, Ir; COD = 1,S-cyclooctadiene) gave the dimeric complexes [(eta(5)-Me4C5R)MCl](2)(mu(2)-Cl)(2) in yields ranging from 47% to 96%. The derivatized dimers were tested for antimicrobial activity, showing activity against Mycobacterium smegmatis and improved activity with derivatized R groups against Staphylococcus aureus and MRSA 43300. The characterization of these complexes was completed by NMR spectroscopy, single-crystal X-ray diffraction, high-resolution mass spectrometry, and elemental analysis.

  DOI：

  10.1021/acs.organomet.6b00580
• 作为产物：
  描述：

  正丁基锂 、 2,3,4,5-四甲基-2-环戊烯酮 以76%的产率得到5-n-butyl-1,2,3,4-tetramethylcyclopentadiene
  参考文献：
  名称：

  Pronounced Enhancement Brought in by Substituents on the Cyclopentadienyl Ligand:  Catalyst System (C₅Me₄R)₂Sm(THF)_x/MMAO (R = Et, ⁱPr, ⁿBu, TMS; MMAO = Modified Methylaluminoxane) for 1,4-Cis Stereospecific Polymerization of 1,3-Butadiene in Cyclohexane Solvent

  摘要：

  The C5Me4R-ligated samarocene(II) complexes, (C5Me4R)(2)Sm(THF)(x) (1, R = Me; 2, R = Et; 3, R = Pr-i; 4, R = Bu-n, 5; R = TMS; x = 1 or 2), in combination with modified methylaluminoxane (MMAO) were examined in cyclohexane with respect to their catalytic performances for the polymerization of butadiene. Complexes 2-5 showed considerable promotion in both catalytic activity and regularity of the resulting polymer as compared to parent 1: activity, 3 much greater than 5 similar to 4 > 2 > 1; 1,4-cis selectivity at 50 degreesC, 3 similar to 5 (98.6%) > 4 (97.5%) > 2 (97.1%) > 1 (96.2%). The system 3/MMAO showed an excellent catalytic activity even at very low catalyst concentration ([butadiene](0)/[Sm](0) = 150 000), where the turnover number (TON) reached about 115 600 butadiene-mol/(Sm-mol h) at 50 degreesC (78% polymer yield in 1 h). At room temperature, the polymerization reaction in cyclohexane using 3/MMAO catalyst gave polybutadiene with extremely high 1,4-cis selectivity of 99.1% in reasonable rate (polymer yield = 87%, in 10 min) while the performance by 1/MMAO was 97.8% in 1,4-cis selectivity and 12% in polymer yield under the same reaction conditions.

  DOI：

  10.1021/ma034899r

文献信息

• Highly Efficient One-Step Direct Synthesis of Monocyclopentadienyltitanium Complexes
  作者：Yuetao Zhang、Ying Mu

  DOI：10.1021/om0508738

  日期：2006.1.1

  This report describes a highly efficient one-step synthetic strategy for monocyclopentadienyltitanium complexes by the direct reaction of TiCl4 with substituted cyclopentadienes, without adding any other reagents. This new synthetic method is particularly efficient for cyclopentadienes with a pendant group that can bond or coordinate to the Ti atom.

  该报告描述了单环戊二烯基钛配合物的高效一步合成策略，该方法通过使TiCl 4与取代的环戊二烯直接反应而无需添加任何其他试剂。对于具有可与Ti原子键合或配位的侧基的环戊二烯，这种新的合成方法特别有效。
• Pronounced Enhancement Brought in by Substituents on the Cyclopentadienyl Ligand:  Catalyst System (C₅Me₄R)₂Sm(THF)<i>_x</i>/MMAO (R = Et, <i>ⁱ</i>Pr, <i>ⁿ</i>Bu, TMS; MMAO = Modified Methylaluminoxane) for 1,4-Cis Stereospecific Polymerization of 1,3-Butadiene in Cyclohexane Solvent
  作者：Shojiro Kaita、Yuko Takeguchi、Zhaomin Hou、Masayoshi Nishiura、Yoshiharu Doi、Yasuo Wakatsuki

  DOI：10.1021/ma034899r

  日期：2003.10.1

  The C5Me4R-ligated samarocene(II) complexes, (C5Me4R)(2)Sm(THF)(x) (1, R = Me; 2, R = Et; 3, R = Pr-i; 4, R = Bu-n, 5; R = TMS; x = 1 or 2), in combination with modified methylaluminoxane (MMAO) were examined in cyclohexane with respect to their catalytic performances for the polymerization of butadiene. Complexes 2-5 showed considerable promotion in both catalytic activity and regularity of the resulting polymer as compared to parent 1: activity, 3 much greater than 5 similar to 4 > 2 > 1; 1,4-cis selectivity at 50 degreesC, 3 similar to 5 (98.6%) > 4 (97.5%) > 2 (97.1%) > 1 (96.2%). The system 3/MMAO showed an excellent catalytic activity even at very low catalyst concentration ([butadiene](0)/[Sm](0) = 150 000), where the turnover number (TON) reached about 115 600 butadiene-mol/(Sm-mol h) at 50 degreesC (78% polymer yield in 1 h). At room temperature, the polymerization reaction in cyclohexane using 3/MMAO catalyst gave polybutadiene with extremely high 1,4-cis selectivity of 99.1% in reasonable rate (polymer yield = 87%, in 10 min) while the performance by 1/MMAO was 97.8% in 1,4-cis selectivity and 12% in polymer yield under the same reaction conditions.
• Rapid Access to Derivatized, Dimeric, Ring-Substituted Dichloro(cyclopentadienyl)rhodium(III) and Iridium(III) Complexes
  作者：Loren C. Brown、Emily Ressegue、Joseph S. Merola

  DOI：10.1021/acs.organomet.6b00580

  日期：2016.12.27

  The present work describes the design and synthesis of a series of rhodium and iridium dimers [(eta(5)-ring)MCl](2)(mu(2)-Cl)(2) (where (eta(5)-ring)MCl = (eta(5)-Me4C5R)Rh(III)Cl or (eta(5)-Me4C5R)Ir(III)Cl) using a new and efficient 1 h procedure. Rhodium and iridium dimeric complexes were synthesized via a microwave reaction. The modified HMe4C5R (R = isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, phenyl, benzyl, phenethyl, cyclohexyl, and cyclopentyl) type ligands were synthesized by reaction of 2,3,4,S-tetramethylcyclopent-2-en-1-one with the respective Grignard reagent (RMgX), followed by elimination of water under acidic conditions to produce the tetramethyl(alkyl or aryl)cyclopentadienes in moderate to excellent yields (40-98%). Reaction of the HMe4C5R ligands with [M(COD)](mu(2)-Cl)(2) (M = Rh, Ir; COD = 1,S-cyclooctadiene) gave the dimeric complexes [(eta(5)-Me4C5R)MCl](2)(mu(2)-Cl)(2) in yields ranging from 47% to 96%. The derivatized dimers were tested for antimicrobial activity, showing activity against Mycobacterium smegmatis and improved activity with derivatized R groups against Staphylococcus aureus and MRSA 43300. The characterization of these complexes was completed by NMR spectroscopy, single-crystal X-ray diffraction, high-resolution mass spectrometry, and elemental analysis.