dimenthyl methylphosphonate | 900537-07-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: dimenthyl methylphosphonate
• 英文别名: (1S,2R,4R)-4-methyl-2-[methyl-[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]oxy-oxidophosphaniumyl]oxy-1-propan-2-ylcyclohexane
• CAS: 900537-07-7
• 化学式: C₂₁H₄₁O₃P
• 分子量: 372.529
• InChiKey: OGOHLIZRGYEUEH-OKAKVDCISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  41.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  dimenthyl methylphosphonate 在 正丁基锂 、 偶氮二异丁腈 、 sodium ethanolate 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 为溶剂， 反应 24.0h， 生成 (-)-dimenthyl 3-iodo-1-methyl-n-heptylphosphonate
  参考文献：
  名称：

  The difference in reactivity of (−)-mono and dimenthyl vs. diethyl alkylphosphonates in the α-lithiation reaction: Carbanionic synthesis of unknown (−)-dimenthyl 1-iodoalkylphosphonates and their first use in the radical iodine atom transfer addition (I-ATRA) and cyclisation (I-ATRC) reactions

  摘要：

  Unknown (-)-dimenthyl and ethyl (-)-menthyl 1-iodoethylphosphonates were synthesized via I-lithio derivatives in 85-87% yields. Starting (-)-dimenthyl alkylphosphonates (R = Me, Et, i-Pr) were obtained in the Michaelis-Becker reaction (75-81% yields) and/or in the methylation reaction of the corresponding 1-lithio-alkylphosphonates (78-92% yields). An interesting concentration and time correlations, never observed for diethyl alkylphosphonates, were found for the metalation of bulky (-)-menthyl alkylphosphonates with /IBuLi and general reaction conditions for the carbanion generation were elaborated. The first example of the I-ATRA reaction of (-)-dimenthyl 1-iodoethylphosphonate with 1-hexene (AIBN) gave four diastereomers (1.6:1:1:0.4), separated into two pairs. The 1-ATRC reaction was not effective due to a steric hindrance around the reactive center. The X-ray analysis of (-)-dimenthyl methylphosphonate confirmed a considerable steric hindrance in higher (-)-dimenthyl alkylphosphonate esters in comparison to their diethyl analogs. (c) 2006 Published by Elsevier B.V.

  DOI：

  10.1016/j.jorganchem.2006.10.069
• 作为产物：
  描述：

  (-)-dimenthyl chlorophosphite 在 水 、 sodium hydride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 27.0h， 生成 dimenthyl methylphosphonate
  参考文献：
  名称：

  The difference in reactivity of (−)-mono and dimenthyl vs. diethyl alkylphosphonates in the α-lithiation reaction: Carbanionic synthesis of unknown (−)-dimenthyl 1-iodoalkylphosphonates and their first use in the radical iodine atom transfer addition (I-ATRA) and cyclisation (I-ATRC) reactions

  摘要：

  Unknown (-)-dimenthyl and ethyl (-)-menthyl 1-iodoethylphosphonates were synthesized via I-lithio derivatives in 85-87% yields. Starting (-)-dimenthyl alkylphosphonates (R = Me, Et, i-Pr) were obtained in the Michaelis-Becker reaction (75-81% yields) and/or in the methylation reaction of the corresponding 1-lithio-alkylphosphonates (78-92% yields). An interesting concentration and time correlations, never observed for diethyl alkylphosphonates, were found for the metalation of bulky (-)-menthyl alkylphosphonates with /IBuLi and general reaction conditions for the carbanion generation were elaborated. The first example of the I-ATRA reaction of (-)-dimenthyl 1-iodoethylphosphonate with 1-hexene (AIBN) gave four diastereomers (1.6:1:1:0.4), separated into two pairs. The 1-ATRC reaction was not effective due to a steric hindrance around the reactive center. The X-ray analysis of (-)-dimenthyl methylphosphonate confirmed a considerable steric hindrance in higher (-)-dimenthyl alkylphosphonate esters in comparison to their diethyl analogs. (c) 2006 Published by Elsevier B.V.

  DOI：

  10.1016/j.jorganchem.2006.10.069

文献信息

• Efficient method for the asymmetric reduction of α- and β-ketophosphonates
  作者：V.V. Nesterov、O.I. Kolodiazhnyi

  DOI：10.1016/j.tet.2007.04.101

  日期：2007.7

  versatile method for the asymmetric reduction of α- and β-ketophosphonates using chiral reactant derived from sodium borohydride and l-(+)- or d-(−)-tartaric acid is developed. The methodology was used for the preparation of a number of biologically interesting enantiomerically pure products: including 2,3-epoxypropylphosphonate 11, 2-hydroxy-3-aminopropylphosphonic acid 14 (phospho-GABOB), phospho-carnitine

  开发了一种高效且通用的方法，该方法使用衍生自硼氢化钠和1-（+）-或d-（-）-酒石酸的手性反应物不对称还原α-和β-酮膦酸酯。该方法被用于许多生物有趣对映体纯产品的制备：含2,3- epoxypropylphosphonate 11，2-羟基-3-氨基丙基膦酸14（磷酸- GABOB），磷酸-肉碱19，和其他在多克规模。
• Di(1<i>R</i>,2<i>S</i>,5<i>R</i>)-menthyl 2-Hydroxy-3-chloropropylphosphonate as a Useful Chiral Synthon for the Preparation of Enantiomerically Pure Phosphonic Acids
  作者：Oleg Kolodiazhnyi、Vitaly Nesterov

  DOI：10.1055/s-2007-985589

  日期：2007.9

  Stereochemically pure di(1 R,2 S,5 R)-menthyl ( S)- and ( R)-2-hydroxy-3-chloropropylphosphonates were synthesized by reaction of di(1 R,2 S,5 R)-menthyl ketophosphonate with chiral complexes prepared from sodium borohydride and ( R, R) -( +)-tartaric acid or with ( S, S)-(-)-tartaric acid. Dimenthyl 2-hydroxy-3-chloropropylphosphonate was utilized as a chiron for the preparation of biologically active

  通过二(1R,2S,5R)-薄荷基酮膦酸酯反应合成立体化学纯的二(1R,2S,5R)-薄荷酯(S)-和(R)-2-羟基-3-氯丙基膦酸酯与由硼氢化钠和（R，R）-（+）-酒石酸或与（S，S）-（-）-酒石酸制备的手性配合物。2-羟基-3-氯丙基膦酸二甲酯被用作制备生物活性产品的chiron。
• Synthesis of 3-Methylidene-1-tosyl-2,3-dihydroquinolin-4(1<i>H</i> )-ones as Potent Cytotoxic Agents
  作者：Jacek Koszuk、Tomasz Bartosik、Jakub Wojciechowski、Wojciech M. Wolf、Anna Janecka、Joanna Drogosz、Angelika Długosz、Urszula Krajewska、Marek Mirowski、Tomasz Janecki

  DOI：10.1002/cbdv.201800242

  日期：2018.9

  An efficient synthetic strategy to 3-methylidene-2,3-dihydroquinolin-4(1H)-ones variously substituted in position 2 has been developed. The title compounds were synthesized in the reaction sequence involving reaction of diethyl methylphosphonate with methyl 2-(tosylamino)benzoate, condensation of thus formed diethyl 2-oxo-2-(2-N-tosylphenyl)ethylphosphonate with various aldehydes followed by successful

  已经开发出一种有效的合成策略，以合成在位置2处被不同取代的3-亚甲基-2,3-二氢喹啉-4（1H）-。以反应顺序合成标题化合物，该反应顺序包括甲基膦酸二乙酯与2-（甲苯磺酰基氨基）苯甲酸甲酯的反应，由此形成的2-氧代-2-（2-甲苯磺酰基苯基）乙基膦酸二乙酯与各种醛的缩合，然后成功应用获得的3-（二乙氧基磷酰基）-1，2-二氢喹啉-4-醇作为霍纳-沃兹沃思-埃蒙斯试剂用于甲醛的烯化。另外，已经使用3-二甲氧基磷酰基作为手性助剂评估了对目标化合物的对映选择性方法。（2S）-3-（dimenthoxyphosphoryl）-2-phenyl-1-tosyldihydroquinolin-4-ol的单X射线晶体分析表明存在强共振辅助氢键（RAHB）。然后测试所获得的3-亚甲基-2，3-二氢喹啉-4（1H）-对两种白血病细胞系NALM-6和HL-60以及乳腺癌MCF-7细胞系的细胞毒活性。所有化合
• New method for the asymmetric hydroboration of ketophosphonates and the synthesis of phospho-carnitine
  作者：Vitaly V. Nesterov、Oleg I. Kolodiazhnyi

  DOI：10.1016/j.tetasy.2006.03.025

  日期：2006.4

  The reduction of alpha- or beta-ketophosphonates with a chiral reactant 1, prepared from sodium borohydride and (R)- or (S)-tartaric acids, led to the formation of both (S)- and (R)-alpha- or beta-hydroxyphosphonates in high yields. The stereoselectivity of the reaction depended on the absolute configurations of 1 and the ketophosphonates. The reduction of di(1R,2S,5R)-menthyl ketophosphonates with (R)-1 proceeded with matched double asymmetric induction to give high diastereomeric excesses of hydroxyphosphonates (up to 96% de). This methodology was used for the preparation of enantiomerically pure phosphonate modified carnitine on a multigram scale. (c) 2006 Elsevier Ltd. All rights reserved.