Dimethylphenyl(chloromethyl)german | 24486-57-5

• 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: Dimethylphenyl(chloromethyl)german
• 英文别名: (chloromethyl)dimethylphenylgermane；(chlromethyl)dimethyl(phenyl)germane；chloromethyl-dimethyl-phenylgermane
• CAS: 24486-57-5
• 化学式: C₉H₁₃ClGe
• 分子量: 229.245
• InChiKey: QDBAGEIVBZZQQA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.38
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  Dimethylphenyl(chloromethyl)german 、 3,6-Diethoxy-2,5-dihydropyridazin 在 盐酸 、 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 以60%的产率得到rac-2-amino-3-(dimethyl(phenyl)germyl)propionic acid ethyl ester
  参考文献：
  名称：

  Syntheses of racemic and non-racemic silicon- and germanium-containing α-amino acids of the formula type H2NCH(CH2ElR3)COOH (El=Si, Ge; R=organyl) and incorporation of d-H2NCH(CH2SiMe3)COOH and d-H2NCH(CH2GeMe3)COOH into biologically active decapeptides: a study on C/Si/Ge bioisosterism

  摘要：

  Two novel efficient methods for the synthesis of racemic silicon- and germanium-containing a-amino acids of the formula type rac-H2NCH(CH2EIR3)COOH (El = Si, Ge; R = organyl), starting from 3,6-diethoxy-2,5-dihydropyrazine, have been developed. Racemic cc-amino acids synthesized: rac-H2NCH(CH2SiMe3)COOH (rac-2), rac-H2NCH(CH2GeMe3)COOH (rac-3), rac-H2NCH(CH2SiMe2Ph)COOH (rac-4), rac-H2NCH(CH2GeMe2Ph)COOH (rac-5), and rac-H2NCH(CH2SiMe2CH=CH2)COOH (rac-6). Preparative liquid-chromatographic resolution of rac-2 and rac-3 [CHIROBIOTIC T (glycopeptide Teicoplanin covalently linked to spherical silica gel) as the stationary phase] yielded the alpha -amino acids (R)-2, (S)-2, (R)-3, and (S)-3. The (R)- and (S)-enantiomers of beta-(trimethylsilyl)alanine [(R)- and (S)-2] and beta-(trimethylgermyl)alanine I(R)- and (S)-3] are sila-analogs and germa-analogs, respectively, of the antipodes of the non-proteinogenic alpha -amino acid beta -tert-butylalanine [(S)- and (R)-H2NCH(CH2CMe3)COOH; (S)- and (R)-1]. Starting from the N-Fmoc-protected C/Si/Ge-analogous (D-configurated) alpha -amino acids (R)-1, (S)-2, and (S)-3, the C/Si/Ge-analogous decapeptides 7-9 [Ac-D-Nal(1)-4-Cl-D-Phe(2)-D-Pal(3)-Ser(4)-N-Me-Tyr(5)-D-Hci(6)- Nle(7)-Arg(8)-Pro(9)-D-Me(3)El-Ala(10)-NH2 (7, El = C; 8, El = Si; 9, El = Ge)] were prepared by sequential solid-phase synthesis. The decapeptides 7-9 were studied in vitro in a functional assay using a recombinant cell line expressing the human GnRH receptor (agonist Triptorelin). Compounds 7-9 behaved as medium-potent GnRH antagonists, the antagonistic potencies of these three C/Si/Ge analogs being very similar. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(01)00783-5
• 作为产物：
  描述：

  dichloro(chloromethyl)phenylgermane 、 甲基锂 生成 Dimethylphenyl(chloromethyl)german
  参考文献：
  名称：

  TACKE, REINHOLD;WIESENBERGER, FRANK, Z. NATURFORSCH. B, 46,(1991) N, C. 275-279

  摘要：

  DOI：

文献信息

• Modularity in the C_sp3 Space─Alkyl Germanes as Orthogonal Molecular Handles for Chemoselective Diversification
  作者：Aymane Selmani、Markus D. Schoetz、Adele E. Queen、Franziska Schoenebeck

  DOI：10.1021/acscatal.2c00852

  日期：2022.5.6

  To meet the need for a rapid, streamlined, and potentially automatable molecule synthesis, modular coupling approaches are highly desired. While the diversification of aromatic molecules, i.e., Csp2 space, has greatly advanced, modular syntheses in the Csp3 space are comparably much less developed. This report explores the potential of alternative functional handles, i.e., alkyl germanes, in this context

  为了满足对快速、流线型和潜在自动化分子合成的需求，非常需要模块化耦合方法。虽然芳族分子的多样化，即​​C sp2空间，已经取得了很大进展，但C sp3空间中的模块合成相对而言发展得少得多。本报告探讨了替代功能手柄的潜力，即烷基锗烷，在这种情况下，它结合了稳定性和可合成性的特征与选择性反应性。我们展示了烷基锗烷 (R-GeEt 3 ) 在光氧化还原条件下（Giese 加成）的化学选择性功能化以及在模块化构建块中的实现，这允许 C 的选择性多样化sp3 -halogen vs C sp3 -Bpin vs C sp3 -GeEt 3个位点。
• Syntheses and Properties of Silicon- and Germanium-Containing <i>α</i>-Amino Acids and Peptides:   A Study on C/Si/Ge Bioisosterism
  作者：Reinhold Tacke、Markus Merget、Rüdiger Bertermann、Michael Bernd、Thomas Beckers、Thomas Reissmann

  DOI：10.1021/om000169l

  日期：2000.9.1

  The unnatural silicon-containing alpha-amino acids (R)- and (S)-H2NCH(CH2SiMe3)COOH [(R)-2 and (S)-2], (R)-H2NCH(CH2SiMe2Ph)COOH [(R)-4], and (R)-H2NCH(CH2SiMe2CH=CH2)COOH [(R)-6] as well as the unnatural germanium-containing alpha-amino acids (R)- and (S)-H2NCH(CH2GeMe3)COOH [(R)-3 and (S)-3] and (R)-H2NCH(CH2GeMe2Ph)COOH [(R)-5] were prepare d in three-step syntheses, starting from (R)-3,6-diethoxy-2-isopropyl-2,5-dihydropyrazine [(R)-10]. All amino acids were isolated as enantiomerically pure (greater than or equal to 99% ee) compounds. The (R)- and (S)-enantiomers of beta-(trimethylsilyl)alanine [(R)-2 and (S)-2] and beta-(trimethylgermyl)alanine [(R)-3 and (S)-3] are sila-analogues and germa-analogues, respectively, of the (S)- and (R)-enantiomers of the nonproteinogenic amino acid beta-tert-butylalanine [(S)- and (R)-H2NCH(CH2CMe3)COOH; (S)-1 and (R)-1]. The C/Si/Ge-analogous (L-configurated) amino acids (S)-1, (R)-2, and (R)-3 mere treated with (fluoren-9-yl)methyl chloroformate to give the corresponding N-Fmoc derivatives (S)-26, (R)-27, and (R)-28. These N-Fmoc-protected amino acids were used as building blocks for the solid-phase syntheses of the C/Si/Ge-analogous decapeptides 7-9 [Ac-D-Nal(1)-4-Cl-D-Phe(2)-D-Pal(3)-Ser(4)-Me(3)El-Ala(5)-D-Cit(6)-Leu(7)-Arg(8)-Pro(9)-D-Ala(10)-NH2 (7, El = C; 8, El = Si; 9, El = Ge)]. The C/Si/Ge analogues 7-9 are derivatives of the GnRH antagonist Cetrorelix(TM), which bears an (S)-tyrosine residue [instead of the (S)-Me3C-Ala, (R)-Me3Si-Ala, or (R)-Me3Ge-Ala residue] in position 5 of its decapeptide backbone. The decapeptides 7-9 were studied in vitro in receptor binding and functional assays using recombinant cell lines expressing the human GnRH receptor. All compounds behaved as potent GnRH antagonists, the binding affinities and antagonistic potencies of the three C/Si/Ge analogues being quite similar. Compounds 7-9 were also studied for their in vivo activities in the male rat after s.c. administration. They produced both a strong testosterone suppression (single-dose treatment, 1.5 mg/kg) and a strong LH suppression (castrated male rat; single-dose treatment, 0.05 mg/kg). For the silicon- and germanium-containing decapeptides 8 and 9 the testosterone and LH suppression lasted for a significantly longer period of time compared with the effects of the carbon analogue 7.
• Tacke, Reinhold; Wiesenberger, Frank, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1991, vol. 46, # 3, p. 275 - 279
  作者：Tacke, Reinhold、Wiesenberger, Frank

  DOI：——

  日期：——
• NINOMIYA SHIN-ICHI; LIU FEN-ZHI; NAKAGAWA HIROAKI; KOHDA KOHFUKU; KAWAZOE+, CHEM. AND PHARM. BULL., 34,(1986) N 8, 3273-3278
  作者：NINOMIYA SHIN-ICHI、 LIU FEN-ZHI、 NAKAGAWA HIROAKI、 KOHDA KOHFUKU、 KAWAZOE+

  DOI：——

  日期：——