N-(2-p-toluenesulfonylethyl)-3,5-dimethylpyrazole | 511513-24-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-(2-p-toluenesulfonylethyl)-3,5-dimethylpyrazole
• 英文别名: 3,5-dimethyl-1-[2-(p-tosyl)-ethyl]-1H-pyrazole；3,5-Dimethyl-1-[2-(4-methylphenyl)sulfonylethyl]pyrazole
• CAS: 511513-24-9
• 化学式: C₁₄H₁₈N₂O₂S
• 分子量: 278.375
• InChiKey: AMOPJQREICVLBG-UHFFFAOYSA-N

物化性质

• 沸点：
  464.2±45.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  60.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-(2-p-toluenesulfonylethyl)-3,5-dimethylpyrazole 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 以68%的产率得到3,5-二甲基吡唑
  参考文献：
  名称：

  Synthesis of β-tosylethylhydrazine and its use in preparation of N-protected pyrazoles and 5-aminopyrazoles

  摘要：

  beta-Tosylethylhydrazine (6) can be prepared efficiently in one step from commercially available p-tolyl vinyl sulfone (7) and hydrazine hydrate. This hydrazine reacts with both 1,3-diketones and conjugated ynones in glacial acetic acid to provide a variety of N-tosylethyl-protected (TSE) pyrazoles in good yields. The TSE group can be removed from the pyrazoles using potassium t-butoxide in THF at -30 degreesC-rt. In addition, hydrazine 6 condenses with beta-ketonitriles and beta-aminoacrylonitriles to afford 5-aminopyrazoles, which can be deprotected by brief treatment with NaOEt in EtOR/DMSO at 45 degreesC. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.11.046
• 作为产物：
  描述：

  对甲苯基乙烯基砜 在 一水合肼 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 反应 16.25h， 生成 N-(2-p-toluenesulfonylethyl)-3,5-dimethylpyrazole
  参考文献：
  名称：

  Synthesis of β-tosylethylhydrazine and its use in preparation of N-protected pyrazoles and 5-aminopyrazoles

  摘要：

  beta-Tosylethylhydrazine (6) can be prepared efficiently in one step from commercially available p-tolyl vinyl sulfone (7) and hydrazine hydrate. This hydrazine reacts with both 1,3-diketones and conjugated ynones in glacial acetic acid to provide a variety of N-tosylethyl-protected (TSE) pyrazoles in good yields. The TSE group can be removed from the pyrazoles using potassium t-butoxide in THF at -30 degreesC-rt. In addition, hydrazine 6 condenses with beta-ketonitriles and beta-aminoacrylonitriles to afford 5-aminopyrazoles, which can be deprotected by brief treatment with NaOEt in EtOR/DMSO at 45 degreesC. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.11.046

文献信息

• Coordination capabilities of pyrazolyl containing ligands towards the fac-[Re(CO)3]+ moiety
  作者：Susana Alves、António Paulo、João D. G. Correia、Ângela Domingos、Isabel Santos

  DOI：10.1039/b207164a

  日期：——

  The coordination capabilities of the pyrazolyl containing ligands pz*(CH2)2NH(CH2)2pz*, pz*(CH2)2NH(CH2)2NH2, pz*(CH2)2S(CH2)2pz* and pz*(CH2)2S(CH2)2NH2 (pz* = 3,5-Me2pz) towards the synthon (NEt4)2[ReBr3(CO)3] (1) were studied. Depending on the reaction conditions, neutral or cationic Re(I) tricarbonyl complexes have been isolated: [ReBr(CO)3(κ2-pz*(CH2)2NH(CH2)2pz*)] (2), [ReBr(CO)3(κ2-pz*(CH2)2S(CH2)2pz*)] (3) [Re(CO)3(κ3-pz*(CH2)2NH(CH2)2pz*)]Br (4), [Re(CO)3(κ2-pz*(CH2)2S(CH2)2pz*)MeOH]Br (5), [Re(CO)3(κ3-pz*(CH2)2NH(CH2)2NH2)]Br (6) and [Re(CO)3(κ3-pz*(CH2)2S(CH2)2NH2)]Br (7). Complexes 2–7 have been characterized by the normal techniques, including X-ray crystallographic analysis in the case of 3, 4, 6 and 7. In these complexes the Re atom adopts a distorted octahedral coordination, being one of the triangular faces defined by the three carbonyl groups and the other three remaining coordination positions by the bidentate and the bromide ligands (3), or by the tridentate and neutral pyrazolyl containing ligands (4, 6, 7). Complexes 2–4, 6 and 7 are static in solution and the 1H NMR data indicate clearly a κ2-coordination mode of the ligand in 2 and 3 and a κ3-coordination in 4, 6 and 7, which agrees with the coordination mode found in the solid state. Compound 5 displays a fluxional behaviour in solution as shown by variable temperature 1H NMR studies. No X-ray data exists for this complex but the pattern obtained for the NMR spectrum at 215 K indicates a κ2-coordination mode for the pyrazolyl containing ligand.

  含有吡唑基配体pz*(CH2)2NH(CH2)2pz*、pz*(CH2)2NH(CH2)2NH2、pz*(CH2)2S(CH2)2pz*和pz*(CH2)2S(CH2)2NH2（pz* = 3,5-Me2pz）的配位能力针对合成物(NEt4)2[ReBr3(CO)3]（1）进行了研究。根据反应条件，已分离出中性或阳离子Re(I)三羰基配合物： [ReBr(CO)3(κ2-pz*(CH2)2NH(CH2)2pz*)]（2），[ReBr(CO)3(κ2-pz*(CH2)2S(CH2)2pz*)]（3），[Re(CO)3(κ3-pz*(CH2)2NH(CH2)2pz*)]Br（4），[Re(CO)3(κ2-pz*(CH2)2S(CH2)2pz*)MeOH]Br（5），[Re(CO)3(κ3-pz*(CH2)2NH(CH2)2NH2)]Br（6）和[Re(CO)3(κ3-pz*(CH2)2S(CH2)2NH2)]Br（7）。配合物2–7已通过正常技术进行表征，包括在3、4、6和7的情况下进行的X射线晶体学分析。在这些配合物中，Re原子呈现不规则的八面体配位，三个羰基所定义的三角面和其他三个配位位置分别被双齿和溴离子配体（3）或三齿和中性吡唑基配体（4、6、7）占据。配合物2–4、6和7在溶液中是静态的，1H NMR数据清楚地表明了配体在2和3中的κ2配位模式以及在4、6和7中的κ3配位模式，这与固态中发现的配位模式一致。化合物5在溶液中表现出可变行为，如不同温度下的1H NMR研究所示。该配合物没有X射线数据，但在215 K下获得的NMR谱图模式表明了含吡唑基配体的κ2配位模式。
• [EN] BIFUNCTIONAL TRIDENTATE PYRAZOLYL CONTAINING LIGANDS FOR RE AND TC TRICARBONYL COMPLEXES<br/>[FR] TRIDENTATE PYRAZOLYLE BIFONCTIONNEL CONTENANT DES LIGANDS POUR LES COMPLEXES RE, TC ET MN TRICARBONYLE
  申请人：MALLINCKRODT INC

  公开号：WO2004091669A1

  公开（公告）日：2004-10-28

  The present invention relates to a chelating agent of the general formula: (I), wherein m is 0 or 1; X is NR4 or S; Y is SR5, NHR5 or P(R5)2; R1 and R3 are the same or different and are selected from H, alkyl or aryl; R2 is H, COOH, NHR6 or (CH2)nCOOR6; R4 is H, alkyl, aryl, (CH2)nCOOR6 or (CH2)nOR6; R5 is H, alkyl, aryl, (CH2)nCOOR6 or (CH2)nOR6, R6 is H, alkyl or aryl; n is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; and when R1=R3=CH3, R2, R4 and R5 are not all three H. The invention further relates to a method and kit for the preparation of radiolabeled biomolecules while using the chelating agent.

  本发明涉及一种螯合剂的普遍公式：（I），其中m为0或1；X为NR4或S；Y为SR5，NHR5或P（R5）2；R1和R3相同或不同，选自H，烷基或芳基；R2为H，COOH，NHR6或（CH2）nCOOR6；R4为H，烷基，芳基，（CH2）nCOOR6或（CH2）nOR6；R5为H，烷基，芳基，（CH2）nCOOR6或（CH2）nOR6，R6为H，烷基或芳基；n为1、2、3、4、5、6、7、8、9或10；当R1=R3=CH3时，R2、R4和R5不全为H。本发明还涉及一种利用该螯合剂制备放射标记生物分子的方法和试剂盒。
• Bifunctional tridentate pyrazolyl containing ligands for re and tc tricarbonyl complexes
  申请人：Santos Rego Isabel

  公开号：US20060198785A1

  公开（公告）日：2006-09-07

  The present invention relates to a chelating agent of the general formula: (I), wherein m is 0 or 1; X is NR 4 or S; Y is SR 5 , NHR 5 or P(R 5 ) 2 ; R 1 and R 3 are the same or different and are selected from H, alkyl or aryl; R 2 is H, COOH, NHR 6 or (CH 2 ) n COOR 6 ; R 4 is H, alkyl, aryl, (CH 2 ) n COOR 6 or (CH2) n OR 6 ; R 5 is H, alkyl, aryl, (CH 2 ) n COOR 6 or (CH 2 ) n OR 6 , R 6 is H, alkyl or aryl; n is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; and when R 1 ═R 3 ═CH 3 , R 2 , R 4 and R 5 are not all three H. The invention further relates to a method and kit for the preparation of radiolabeled biomolecules while using the chelating agent.

  本发明涉及一种螯合剂，其一般式为：（I），其中m为0或1；X为NR4或S；Y为SR5，NHR5或P（R5）2；R1和R3相同或不同，选自H、烷基或芳基；R2为H、COOH、NHR6或（CH2）nCOOR6；R4为H、烷基、芳基、（CH2）nCOOR6或（CH2）nOR6；R5为H、烷基、芳基、（CH2）nCOOR6或（CH2）nOR6，R6为H、烷基或芳基；n为1、2、3、4、5、6、7、8、9或10；当R1═R3═CH3时，R2、R4和R5不全为H。本发明还涉及一种使用该螯合剂制备放射性标记生物分子的方法和试剂盒。
• Bifunctional tridentate pyrazolyl containing ligands for RE, TC and MN tricarbonyl complexes
  申请人：Mallinckrodt International Corporation

  公开号：EP1529537A1

  公开（公告）日：2005-05-11

  The present invention relates to new cheating agents to link biomolecules and carbonyl moieties for labeling with technetuim and rhenium. In particular the invention relates to bifunctional tridentate pyrazolyl-polyamines, pyrazolyl-aminothioethers, pyrazolyl-polythioethers, pyrazolyl-aminophosphines and pyrazolyl-thioetherphosphines which stabilize the moieties [M(CO)3]+ (M = Re, Tc, Mn) and bind to biomolecules which accumulate in diseased tissues. The invention relates to the chelators as such, to chelators coupled to a biomolecule and to either of these complexed with carbonyl. In addition the invention relates to a kit for providing radiolabeled biomolecules and to the use of such radiolabeled molecules in diagnosis and therapy.

  本发明涉及连接生物大分子和羰基的新欺骗剂，以便用锝和铼进行标记。特别是本发明涉及双功能三叉吡唑基多胺、吡唑基氨基硫醚、吡唑基多硫醚、吡唑基氨基膦和吡唑基硫醚膦，它们能稳定分子[M(CO)3]+（M = Re、Tc、Mn），并与病变组织中积累的生物大分子结合。本发明涉及螯合剂本身、与生物大分子耦合的螯合剂以及与羰基络合的螯合剂。此外，本发明还涉及一种提供放射性标记生物大分子的试剂盒，以及这种放射性标记分子在诊断和治疗中的应用。
• BIFUNCTIONAL TRIDENTATE PYRAZOLYL CONTAINING LIGANDS FOR RE, TC AND MN TRICARBONYL COMPLEXES
  申请人：MALLINCKRODT INC.

  公开号：EP1644050A1

  公开（公告）日：2006-04-12