diethyl [(E)-4-bromobut-2-en-1-yl]phosphonate | 79521-53-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diethyl [(E)-4-bromobut-2-en-1-yl]phosphonate
• 英文别名: diethyl (E)-(4-bromo-2-butenyl)phosphonate；diethyl (E)-4-bromobut-2-enephosphonate；diethyl (4-bromo-2-butenyl)phosphonate；(E)-1-bromo-4-diethoxyphosphorylbut-2-ene
• CAS: 79521-53-2；140151-17-3
• 化学式: C₈H₁₆BrO₃P
• 分子量: 271.091
• InChiKey: QZBMYHKVNVHMNY-AATRIKPKSA-N

物化性质

• 沸点：
  130-132 °C(Press: 2 Torr)
• 密度：
  1.3528 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  diethyl [(E)-4-bromobut-2-en-1-yl]phosphonate 在 四丁基碘化铵 、 双(三甲基硅烷基)氨基钾 、 potassium carbonate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 25.41h， 生成 diethyl (2E,4E)-deca-2,4-dien-1-ylphosphonate
  参考文献：
  名称：

  Synthesis of Conjugated Polyenes via Sequential Condensation of Sulfonylphosphonates and Aldehydes

  摘要：

  Selective metalation of sulfonylphosphonates results in sufficiently stable carbanions that undergo chemoselective Julia-Kocienski condensation with various aldehydes to provide (E)-allylic phosphonates in good yields and selectivities. The subsequent Horner-Wadsworth-Emmons condensation with aldehydes is used to synthesize various unsymmetrical trans-dienes, trienes, and tetraenes. This methodology is utilized for the concise synthesis of a naturally occurring fluorescent probe for membrane properties, beta-parinaric acid.

  DOI：

  10.1021/ol203431e
• 作为产物：
  描述：

  1,4-二溴-2-丁烯 、 亚磷酸三乙酯 反应 4.0h， 以62%的产率得到diethyl [(E)-4-bromobut-2-en-1-yl]phosphonate
  参考文献：
  名称：

  Exploration of N-phosphonoalkyl-, N-phosphonoalkenyl-, and N-(phosphonoalkyl)phenyl-spaced .alpha.-amino acids as competitive N-methyl-D-aspartic acid antagonists

  摘要：

  A series of N-substituted alpha-amino acids containing terminal phosphonic acid groups has been synthesized as potential N-methyl-D-aspartate (NMDA) receptor antagonists. NMDA receptor affinity was determined by displacement of a known ligand ([H-3]CPP) from crude rat brain synaptic membranes; an antagonist action was demonstrated by the inhibition of glutamate-induced accumulation of [Ca-45(2+)] in cultured rat cortical neurons. Receptor affinity was significantly correlated with antagonist activity (Figure 1). Moderate affinity (IC50 = 1-2-mu-M) was retained for analogues (31 and 32, Table 1; and 59 and 66, Table II) with reduced flexibility in their phosphonate side chains and is consistent with entropy playing a role in determining receptor affinity. Modeling studies suggest a folded conformation that brings the distal phosphonic acid group into close proximity with the alpha-carboxylate is required for binding. Each of the active analogues possess entropy-limiting features (double bonds, phenyl rings) in their side chains that allows the superposition of their key NH2, alpha-COOH, and distal PO3H2 groups with those of known competitive antagonists. Affinity decreased for analogues with alpha-carbon substitution, presumably because the alpha-substituent inhibits the folding of these structures into a bioactive conformation and occupies receptor-excluded volume. A complete description of the NMDA antagonist pharmacophore model is provided in a companion paper. 1

  DOI：

  10.1021/jm00086a005

文献信息

• Cu-Catalyzed Asymmetric Allylic Alkylation of Phosphonates and Phosphine Oxides with Grignard Reagents
  作者：Valentín Hornillos、Manuel Pérez、Martín Fañanás-Mastral、Ben L. Feringa

  DOI：10.1002/chem.201204364

  日期：2013.4.22

  An efficient and highly enantioselective copper‐catalyzed allylic alkylation of phosphonates and phosphine oxides with Grignard reagents and Taniaphos or phosphoramidites as chiral ligands is reported. Transformation of these products leads to a variety of new phosphorus‐containing chiral intermediates.

  据报道，使用格氏试剂和三苯氧磷或亚磷酰胺作为手性配体，可有效且高度对映体选择性地催化铜催化的膦酸酯和氧化膦的烯丙基烷基化反应。这些产品的转化产生了各种新的含磷手性中间体。
• ω-haloalkylphosphoryl compounds: Synthesis and properties
  作者：V. V. Ragulin

  DOI：10.1134/s1070363212120055

  日期：2012.12

  A general method of the synthesis of omega-haloalkylphosphoryl compounds was developed, a series of compounds of phosphonic and phosphine oxide type were synthesized. The ability of some omega-haloalkylphosphonates to undergo intramolecular cyclization into the corresponding 1,2-oxaphospholane and 1,2-oxaphosphorine was investigated depending on the solvent polarity, the presence of halogen ions in the solution, and temperature. Tetrahydrofuran was chosen as one of the most suitable solvents for the alkylation of CH acids with omega-haloalkylphosphoryl compounds.
• Exploration of N-phosphonoalkyl-, N-phosphonoalkenyl-, and N-(phosphonoalkyl)phenyl-spaced .alpha.-amino acids as competitive N-methyl-D-aspartic acid antagonists
  作者：Christopher F. Bigge、Graham Johnson、Daniel F. Ortwine、James T. Drummond、Daniel M. Retz、Laura J. Brahce、Linda L. Coughenour、Frank W. Marcoux、Albert W. Probert

  DOI：10.1021/jm00086a005

  日期：1992.4

  A series of N-substituted alpha-amino acids containing terminal phosphonic acid groups has been synthesized as potential N-methyl-D-aspartate (NMDA) receptor antagonists. NMDA receptor affinity was determined by displacement of a known ligand ([H-3]CPP) from crude rat brain synaptic membranes; an antagonist action was demonstrated by the inhibition of glutamate-induced accumulation of [Ca-45(2+)] in cultured rat cortical neurons. Receptor affinity was significantly correlated with antagonist activity (Figure 1). Moderate affinity (IC50 = 1-2-mu-M) was retained for analogues (31 and 32, Table 1; and 59 and 66, Table II) with reduced flexibility in their phosphonate side chains and is consistent with entropy playing a role in determining receptor affinity. Modeling studies suggest a folded conformation that brings the distal phosphonic acid group into close proximity with the alpha-carboxylate is required for binding. Each of the active analogues possess entropy-limiting features (double bonds, phenyl rings) in their side chains that allows the superposition of their key NH2, alpha-COOH, and distal PO3H2 groups with those of known competitive antagonists. Affinity decreased for analogues with alpha-carbon substitution, presumably because the alpha-substituent inhibits the folding of these structures into a bioactive conformation and occupies receptor-excluded volume. A complete description of the NMDA antagonist pharmacophore model is provided in a companion paper. 1
• Synthesis and Biological Activity of Some Unsaturated 6-Azauracil Acyclonucleosides
  作者：Youssef Kabbaj、Hassan Bihi Lazrek、Jean Louis Barascut、Jean Louis Imbach

  DOI：10.1081/ncn-200055695

  日期：2005.3.1

  A useful route is described for obtaining Z and E unsaturated alkylating agents 3 and 4. Coupling 6-azauracits 5 and 6 with unsaturated alkylating agent followed by the deprolection with H' resin gave acyclonucleosides 11-14 in good overall yields. Unsaturated acyclonucleosides phosphonates 19 and 20 were prepared using potassium carbonate as base and 4-bromobut-2-enyl diethyl phosphonate 16 as the alkylating agent. The introduction of a propargyl group at the N-3 position of acyclonucleasides 7, 8, 17, 18, 19, and 20 was achieved using potassium carbonate in DMF.
• Rozhko; Ragulin, Russian Journal of General Chemistry, 1999, vol. 69, # 7, p. 1088 - 1092
  作者：Rozhko、Ragulin

  DOI：——

  日期：——