3-methyl-2-thiophenyl lithium | 133374-03-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 3-methyl-2-thiophenyl lithium
• 英文别名: 2-lithio-3-methylthiophene；3-methyl-2-thienyllithium；(3-methyl-2-thienyl)lithium
• CAS: 133374-03-5
• 化学式: C₅H₅LiS
• 分子量: 104.102
• InChiKey: DWGFLRGSHGVZPS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.48
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  28.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-methyl-2-thiophenyl lithium 在 lithium hydroxide monohydrate 、 水 、 potassium carbonate 、 potassium iodide 作用下， 以 四氢呋喃 、 乙醚 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 63.25h， 生成 5-[(3R)-dithiolan-3-yl]pentanoyl 1-[4,4-bis(3-methylthiophen-2-yl)but-3-enyl]piperidine-3-carboxylate
  参考文献：
  名称：

  Compositions and methods for the treatment of epilepsy

  摘要：

  该发明涉及公式I和公式II的化合物或其药用可接受的盐，以及其多晶形、溶剂合物、对映体、立体异构体和水合物。包括有效量的公式I或公式II化合物的药物组合物；以及用于治疗或预防神经系统疾病的方法可以制成口服、颊下、直肠、局部、经皮、经粘膜、静脉、肠道给药、糖浆或注射剂。这种组合物可用于治疗癫痫、躁郁症、三叉神经痛、注意力缺陷多动障碍、部分性癫痫发作、部分、肌阵挛、强直-阵挛性癫痫及精神分裂症、神经性疼痛、癫痫、抽动症、阿尔茨海默病、自闭症、躁郁症和焦虑症、躁郁症、狂躁症、幻肢综合征、复杂性区域性疼痛综合征、发作性极端疼痛综合征、神经肌痉挛、间歇性爆发障碍、边缘型人格障碍、遗传性肌张力过高和创伤后应激障碍的治疗。

  公开号：

  US09290486B1
• 作为产物：
  描述：

  3-methyl-2-trimethylstannyl-thiophene 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 3-methyl-2-thiophenyl lithium
  参考文献：
  名称：

  Solution Structure and Chelation Properties of 2-Thienyllithium Reagents

  摘要：

  The solution and chelation properties of 2-thienyllithium reagents with potential amine and ether chelating groups in the 3-position and related model systems have been investigated using low temperature Li-6, Li-7, C-13, and P-31 NMR spectroscopy, N-15-labeling, and the effect of solvent additives. In THF-ether mixtures at low temperature 3-(N,N-dimethylaminomethyl)-2-thienyllithium (4) is ca. 99% dimer (which is chelated) and 1% monomer (unchelated), whereas 3-(methoxymethyl)-2thienyllithium (5) is < 10% dimer. Compound 5 crystallizes as a THF-solvated dimer, but there is no indication that the ether side chain is chelated in solution. Both 4 and 5 form PMDTA-complexed monomers almost stoichiometrically, similar to the model compound 2, in sharp contrast to phenyl analogues, which show very different behavior. The barriers to dimer interconversion are ca. 2 kcal/mol lower and chelation is significantly weaker in the 2-thienyllithium reagents than in their phenyl analogues.

  DOI：

  10.1021/jo050592+

文献信息

• The tris(2-thienyl)methyl cation problem. NMR spectroscopic study
  作者：Belen Abarca、Gregorio Asensio、Rafael Ballesteros、Teresa Varea

  DOI：10.1021/jo00010a011

  日期：1991.5

  A series of homologues of the trityl cation obtained by total or partial substitution of the phenyl rings for 2- or 3-thienyl groups has been studied by H-1 and C-13 NMR. In general, the spectral parameters found follow the expected trends. However, a most unexpected effect is found in the transformation of tris(2-thienyl)carbinol (1d) into tris(2-thienyl)methyl cation (2d), since the increase of the total chemical shift (DELTA-SIGMA-delta) associated with the ionization is as low as 105 ppm. To account for this observation, several hypotheses are discussed including the possibility of through-space charge delocalization by the three sulfur atoms and the interaction of the thiophene rings in an alternate conformation.
• Highly selective trimerization of ethylene with half-sandwich cyclopentadienyl and indenyl titanium complexes bearing pendant thienyl group
  作者：Yanlu Zhang、Chen Wang、Tianzhi Wu、Haiyan、Ma. Jiling Huang

  DOI：10.1016/j.molcata.2014.02.010

  日期：2014.6

  A series of half-sandwich titanium complexes bearing thienyl group [Cp(Ind)-bridge-thienyl]TiCl3 (CS1-CS10) have been synthesized and show high selective ethylene trimerizaion to 1-hexene. The molecular structure of CS8 [Ind-C(cyclo-C5H10)-(5-Me-thienyl)]TiCl3 was confirmed by X-ray. No intramolecular coordination interaction between the sulfur atom on the thienyl group and the titanium center could be observed in the solid state of these complexes. After activated with MAO, the complexes can effectively catalyze ethylene trimerization. For [Cp-bridge-thienyl]TiCl3/MAO system, the best productivity is obtained at 30 degrees C; increasing the bulk of the substituent on the 5-position of the thienyl can improve the productivity for 1-hexene. CS6 [Cp-C(cyclo-C5H10)-(5-SiMe3-thienyl)]TiCl3 upon with MAO can make a productivity of 553 kg/(mol Ti-h) and 1-hexene selectivity of 86% at 30 degrees C, 0.5 MPa ethylene pressure. For [Ind-bridge-thienyl] TiCl3/MAO system, catalysts have more active and more tolerant of temperature comparing to corresponding Cp complexes. For example, CS8 can make the productivity of 697 kg/(mol Ti-h) and 1-hexene selectivity of 95% at 80 degrees C, 0.5 MPa ethylene. (C) 2014 Elsevier B.V. All rights reserved.
• Tazaki Masato, Tanabe Hidetaka, Hieda Toshihiko, Nagahama Shizuo, Inoue K+, Phosph., Sulfur and Silicon and Relat. Elem, 88 (1994) N 1-4, S 189-193
  作者：Tazaki Masato, Tanabe Hidetaka, Hieda Toshihiko, Nagahama Shizuo, Inoue K+

  DOI：——

  日期：——
• Compositions and methods for the treatment of epilepsy
  申请人：Kandula Mahesh

  公开号：US09290486B1

  公开（公告）日：2016-03-22

  The invention relates to the compounds of formula I and formula II or its pharmaceutical acceptable salts, as well as polymorphs, solvates, enantiomers, stereoisomers and hydrates thereof. The pharmaceutical compositions comprising an effective amount of compounds of formula I or formula II; and methods for treating or preventing neurological diseases may be formulated for oral, buccal, rectal, topical, transdermal, transmucosal, intravenous, parenteral administration, syrup, or injection. Such compositions may be used to treatment of epilepsy, bipolar disorder, trigeminal neuralgia, attention-deficit hyperactivity disorder, partial seizures, adjunctive therapy for partial, myoclonic, tonic-clonic seizures and schizophrenia, neuropathic pain, seizures, Tourette syndrome, Alzheimer's disease, autism, bipolar disorder and anxiety disorder, bipolar disorder, mania, phantom limb syndrome, complex regional pain syndrome, paroxysmal extreme pain disorder, neuromyotonia, intermittent explosive disorder, borderline personality disorder, myotonia congenita and post-traumatic stress disorder.

  该发明涉及公式I和公式II的化合物或其药用可接受的盐，以及其多晶形、溶剂合物、对映体、立体异构体和水合物。包括有效量的公式I或公式II化合物的药物组合物；以及用于治疗或预防神经系统疾病的方法可以制成口服、颊下、直肠、局部、经皮、经粘膜、静脉、肠道给药、糖浆或注射剂。这种组合物可用于治疗癫痫、躁郁症、三叉神经痛、注意力缺陷多动障碍、部分性癫痫发作、部分、肌阵挛、强直-阵挛性癫痫及精神分裂症、神经性疼痛、癫痫、抽动症、阿尔茨海默病、自闭症、躁郁症和焦虑症、躁郁症、狂躁症、幻肢综合征、复杂性区域性疼痛综合征、发作性极端疼痛综合征、神经肌痉挛、间歇性爆发障碍、边缘型人格障碍、遗传性肌张力过高和创伤后应激障碍的治疗。
• Solution Structure and Chelation Properties of 2-Thienyllithium Reagents
  作者：Kevin L. Jantzi、Craig L. Puckett、Ilia A. Guzei、Hans J. Reich

  DOI：10.1021/jo050592+

  日期：2005.9.1

  The solution and chelation properties of 2-thienyllithium reagents with potential amine and ether chelating groups in the 3-position and related model systems have been investigated using low temperature Li-6, Li-7, C-13, and P-31 NMR spectroscopy, N-15-labeling, and the effect of solvent additives. In THF-ether mixtures at low temperature 3-(N,N-dimethylaminomethyl)-2-thienyllithium (4) is ca. 99% dimer (which is chelated) and 1% monomer (unchelated), whereas 3-(methoxymethyl)-2thienyllithium (5) is < 10% dimer. Compound 5 crystallizes as a THF-solvated dimer, but there is no indication that the ether side chain is chelated in solution. Both 4 and 5 form PMDTA-complexed monomers almost stoichiometrically, similar to the model compound 2, in sharp contrast to phenyl analogues, which show very different behavior. The barriers to dimer interconversion are ca. 2 kcal/mol lower and chelation is significantly weaker in the 2-thienyllithium reagents than in their phenyl analogues.