ethylene glycol dimethyl ether-d₁₀ | 107975-86-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethylene glycol dimethyl ether-d₁₀
• 英文别名: d₁₀-DME；tetradeuterio-1,2-bis-trideuteriomethoxy-ethane；Tetradeuterio-1,2-bis-trideuteriomethoxy-aethan；decadeuterio-1,2-dimethoxy-ethane；Glyme (1,2-dimethoxyethane-d10)；1,1,2,2-tetradeuterio-1,2-bis(trideuteriomethoxy)ethane
• CAS: 107975-86-0
• 化学式: C₄H₁₀O₂
• 分子量: 100.043
• InChiKey: XTHFKEDIFFGKHM-MWUKXHIBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  6
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  {(neopentylidene)(2,6-diisopropylphenylimido)((OC(CH3)(CF3)2)2) molybdenum} 、 乙烯 、 ethylene glycol dimethyl ether-d₁₀ 以 further solvent(s) 为溶剂， 生成
  参考文献：
  名称：

  Synthesis of five- and six-coordinate alkylidene complexes of the type Mo(CHR)(NAr)[OCMe(CF3)2]2Sx and their use as living ROMP initiators or Wittig reagents

  摘要：

  Addition of a slight excess of 4-methoxy-1-hexene to Mo(CHCMe2Ph)(NAr)(ORF6)2 (1a) or Mo(CHCMe3)(NAr)(ORF6)2 (1b) in pentane (ORF6 = OCMe(CF3)2) yielded crystalline, red-orange anti-Mo[CHCH2CH(OMe)CH2CH3](NAr)(ORF6)2 (2). A similar reaction was used to prepare the difunctional complex anti-[(ArN)(ORF6)2Mo=CHCH2CH(OMe)]2C6H4(3). Styrene reacts with la or lb in DME over a period of 12 h to afford orange syn-Mo(CHPh)(NAr)-(ORF6)2(DME) (4) in good yield. 4-(Dimethylamino)styrene and 2,4,6-trimethoxystyrene react analogously to yield dark red syn-Mo(CH-4-C6H4-NMe2)(NAr)(ORF6)2 (DME) (5) and red anti-Mo[CH-2,4,6-C6H2-(OMe)3](NAr)(ORF6)2(DME) (6). 4 also can be synthesized from Mo(NAr)2Cl2(DME) via Mo(NAr)2(CH2Ph)2 and Mo(CHPh)(NAr)(OTf)2(DME). The reaction between 1 and 0.5 equiv of octatetraene in DME afforded syn-(DME)(RF60)2(ArN)Mo(CH)6-Mo(NAr)(ORF6)2(DME) (9a). A related complex, syn-(Et2O)(RF60)2(ArN)Mo(CH)6Mo(NAr)-(ORF6)2(Et2O) (9b), could be prepared directly in diethyl ether or by dissolving 9a in diethyl ether. anti-(THF)(RF60)2(ArN)Mo(CH)6Mo(NAr)(ORF6)2(THF) (9c) was observed upon dissolving 9a in THF. Addition of 4 equiv of LiO-t-Bu and 2 equiv of quinuclidine (quin) to 9a yields metallic green (quin)(t-BuO)2(ArN)Mo(CH)6Mo(NAr)(0-t-Bu)2(quin) (9d). 1,4-Divinylbenzene reacts smoothly with la or lb to give another conjugated difunctional alkylidene complex, 1,4-[(DME)(RF60)2(ArN)MoCH]2C6H4 (10a). Mo(CH2)(NAr)(ORF6)2(DME) (11a) could be generated and observed by H-1 NMR upon adding an excess of ethylene to a solution of lb in DME-d10 in a septum-sealed NMR tube. Addition of 2,2'-bipyridine (bpy) to 11a yielded isolable Mo(CH2)(NAr)(ORF6)2(bpy) (11b). 2,3-Dicarbomethoxynorbornadiene (100 equiv) could be polymerized in a living manner in DME using lb, 4, 5, 9a, 9b, or 10a as the initiator. 2,3-Bis(trifluoromethyl)norbomadiene (100 equiv) was also polymerized in a living manner by la in DME. Addition of an excess of LiO-t-Bu (8 equiv) to a solution of 3 in toluene, followed by 200 equiv of methyltetracyclododecene (MTD), gave low-polydispersity poly-MTD (M(W)/M(n) = 1.03) in 93% yield. Complexes 4,5,9a, 9b, and 10a react cleanly with pivaldehyde or benzaldehyde in CD2Cl2 or DME. A combination of Wittig reactions was used to prepare the di-tert-butyl-capped polyenes(t-Bu)(CH=CH)n(t-Bu)(n=4,6,8). The techniques described here should expand the opportunities for making polymers via living ROMP reactions and, in particular, should allow one to introduce conjugated sequences with a known, fixed length into a variety of polymers and to attach functional groups to both ends of a polymer.

  DOI：

  10.1021/om00027a028
• 作为产物：
  描述：

  氘代乙二醇-d6 、 氘代碘甲烷 在 氨 、 sodium 作用下， -40.0~100.0 ℃ 、13.33 Pa 条件下， 反应 240.0h， 生成 ethylene glycol dimethyl ether-d₁₀
  参考文献：
  名称：

  Palladium-Catalyzed Reductiveortho-Arylation: Evidence for the Decomposition of 1,2-Dimethoxyethane and Subsequent Arylpalladium(II) Reduction

  摘要：

  A palladium-catalyzed crossed biaryl coupling/reduction sequence enables the formation of meta-substituted biaryls via solvent-mediated arylpalladium(II) reduction. Isotope labeling studies determined that the decomposition of 1,2-dimethoxyethane (DME) is indeed involved in the reductive process.

  DOI：

  10.1021/ol1019037
• 作为试剂：
  描述：

  2-溴-5-氯苯甲酸甲酯 、 2-碘-6-硝基甲苯 在 降冰片烯 、 ethylene glycol dimethyl ether-d₁₀ 、 palladium diacetate 、 caesium carbonate 、 三苯基膦 作用下， 反应 12.0h， 以72%的产率得到C₁₅H₁₁⁽²⁾HClNO₄
  参考文献：
  名称：

  Palladium-Catalyzed Reductiveortho-Arylation: Evidence for the Decomposition of 1,2-Dimethoxyethane and Subsequent Arylpalladium(II) Reduction

  摘要：

  A palladium-catalyzed crossed biaryl coupling/reduction sequence enables the formation of meta-substituted biaryls via solvent-mediated arylpalladium(II) reduction. Isotope labeling studies determined that the decomposition of 1,2-dimethoxyethane (DME) is indeed involved in the reductive process.

  DOI：

  10.1021/ol1019037

文献信息

• Notes - Organic Deutrium Compounds. I. 1,2-Dimethoxy-d₆-ethane-d₄ and 2-Methoxy-d₃-ethan-d₄-ol
  作者：Eugene Bissell、Robert Spenger

  DOI：10.1021/jo01363a618

  日期：1957.12.1
• Synthesis of five- and six-coordinate alkylidene complexes of the type Mo(CHR)(NAr)[OCMe(CF3)2]2Sx and their use as living ROMP initiators or Wittig reagents
  作者：Harold H. Fox、Jin Kyu Lee、Lee Y. Park、Richard R. Schrock

  DOI：10.1021/om00027a028

  日期：1993.3

  Addition of a slight excess of 4-methoxy-1-hexene to Mo(CHCMe2Ph)(NAr)(ORF6)2 (1a) or Mo(CHCMe3)(NAr)(ORF6)2 (1b) in pentane (ORF6 = OCMe(CF3)2) yielded crystalline, red-orange anti-Mo[CHCH2CH(OMe)CH2CH3](NAr)(ORF6)2 (2). A similar reaction was used to prepare the difunctional complex anti-[(ArN)(ORF6)2Mo=CHCH2CH(OMe)]2C6H4(3). Styrene reacts with la or lb in DME over a period of 12 h to afford orange syn-Mo(CHPh)(NAr)-(ORF6)2(DME) (4) in good yield. 4-(Dimethylamino)styrene and 2,4,6-trimethoxystyrene react analogously to yield dark red syn-Mo(CH-4-C6H4-NMe2)(NAr)(ORF6)2 (DME) (5) and red anti-Mo[CH-2,4,6-C6H2-(OMe)3](NAr)(ORF6)2(DME) (6). 4 also can be synthesized from Mo(NAr)2Cl2(DME) via Mo(NAr)2(CH2Ph)2 and Mo(CHPh)(NAr)(OTf)2(DME). The reaction between 1 and 0.5 equiv of octatetraene in DME afforded syn-(DME)(RF60)2(ArN)Mo(CH)6-Mo(NAr)(ORF6)2(DME) (9a). A related complex, syn-(Et2O)(RF60)2(ArN)Mo(CH)6Mo(NAr)-(ORF6)2(Et2O) (9b), could be prepared directly in diethyl ether or by dissolving 9a in diethyl ether. anti-(THF)(RF60)2(ArN)Mo(CH)6Mo(NAr)(ORF6)2(THF) (9c) was observed upon dissolving 9a in THF. Addition of 4 equiv of LiO-t-Bu and 2 equiv of quinuclidine (quin) to 9a yields metallic green (quin)(t-BuO)2(ArN)Mo(CH)6Mo(NAr)(0-t-Bu)2(quin) (9d). 1,4-Divinylbenzene reacts smoothly with la or lb to give another conjugated difunctional alkylidene complex, 1,4-[(DME)(RF60)2(ArN)MoCH]2C6H4 (10a). Mo(CH2)(NAr)(ORF6)2(DME) (11a) could be generated and observed by H-1 NMR upon adding an excess of ethylene to a solution of lb in DME-d10 in a septum-sealed NMR tube. Addition of 2,2'-bipyridine (bpy) to 11a yielded isolable Mo(CH2)(NAr)(ORF6)2(bpy) (11b). 2,3-Dicarbomethoxynorbornadiene (100 equiv) could be polymerized in a living manner in DME using lb, 4, 5, 9a, 9b, or 10a as the initiator. 2,3-Bis(trifluoromethyl)norbomadiene (100 equiv) was also polymerized in a living manner by la in DME. Addition of an excess of LiO-t-Bu (8 equiv) to a solution of 3 in toluene, followed by 200 equiv of methyltetracyclododecene (MTD), gave low-polydispersity poly-MTD (M(W)/M(n) = 1.03) in 93% yield. Complexes 4,5,9a, 9b, and 10a react cleanly with pivaldehyde or benzaldehyde in CD2Cl2 or DME. A combination of Wittig reactions was used to prepare the di-tert-butyl-capped polyenes(t-Bu)(CH=CH)n(t-Bu)(n=4,6,8). The techniques described here should expand the opportunities for making polymers via living ROMP reactions and, in particular, should allow one to introduce conjugated sequences with a known, fixed length into a variety of polymers and to attach functional groups to both ends of a polymer.
• Palladium-Catalyzed Reductive<i>ortho</i>-Arylation: Evidence for the Decomposition of 1,2-Dimethoxyethane and Subsequent Arylpalladium(II) Reduction
  作者：Andrew Martins、David A. Candito、Mark Lautens

  DOI：10.1021/ol1019037

  日期：2010.11.19

  A palladium-catalyzed crossed biaryl coupling/reduction sequence enables the formation of meta-substituted biaryls via solvent-mediated arylpalladium(II) reduction. Isotope labeling studies determined that the decomposition of 1,2-dimethoxyethane (DME) is indeed involved in the reductive process.