2-methoxycarbonyl-1,1,3,3-tetramethyl-1,3,2λ(4)-diazaborolidinium bromide | 167999-56-6

• 英文名称: 2-methoxycarbonyl-1,1,3,3-tetramethyl-1,3,2λ(4)-diazaborolidinium bromide
• 英文别名: [(N,N,N',N'-tetramethylethylenediamine)(methoxycarbonyl)hydroboron] bromide
• CAS: 167999-56-6
• 化学式: Br*C₈H₂₀BN₂O₂
• 分子量: 266.974
• InChiKey: OSSTZCWSPFCUIJ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  2-methoxycarbonyl-1,1,3,3-tetramethyl-1,3,2λ(4)-diazaborolidinium bromide 在 氢氧化钾 作用下， 以 水 为溶剂， 生成 [(N,N,N',N'-tetramethylethylenediamine)BH(COO)]
  参考文献：
  名称：

  对称和不对称的双（胺）羧基氢硼（+1）和双（胺）氰基氢硼（+1）阳离子：合成与性能

  摘要：

  摘要通过用过量的叔胺（四甲基乙二胺，TMEDA；喹啉， Q）以及吡啶碱（吡啶，Py; 4-甲基吡啶，4-Pic; 4-二甲基氨基吡啶，DMAP）在更高的温度下。在4-Pic·BH 2 COOMe和DMAP·BH 2 COOMe与胺过溴化物的反应中，以高收率合成了含有手性硼原子的不对称双（胺）（甲氧基羰基）氢硼（+1）阳离子。在室温下在CH 2 Cl 2中进行（L·Br 2，L ＝ Q，Py，4-Pic，DMAP）。除这些新型阳离子羧基硼化合物外，还利用胺-过溴酸盐（L·Br 2； L = Py，4-Pic，DMAP）的有效方法，制备了几种具有[LL'BH（CN）] +组成的新型阳离子氰基硼龙配合物。 ）和胺-氰基硼烷（L'·BH 2 CN，L'= 4-Pic，DMAP）。已经制备了双（胺）硼阳离子，并通过IR，1 H和11 B NMR谱表征为PF 6盐。对水溶性双（胺）（甲氧基羰基）氢硼（

  DOI：

  10.1016/0020-1693(95)04453-g
• 作为产物：
  描述：

  四甲基乙二胺 以 四氢呋喃 、 甲醇 为溶剂， 生成 2-methoxycarbonyl-1,1,3,3-tetramethyl-1,3,2λ(4)-diazaborolidinium bromide
  参考文献：
  名称：

  Synthesis, Characterization, and Bromine Substitution of Diamine Complexes of Carboxyborane and Methoxycarbonylborane. Diazabora Rings Containing B-Carboxyl and B-Carboxylato Groups

  摘要：

  DA . 2BH(2)CN (1) [DA = N,N,N',N'-tetramethylethanediamine (TMEDA, a), N,N,N',N'-tetramethylpropanediamine (TMPDA, b), and N,N,N',N'-tetramethylbutanediamine (TMBDA, c)], (DA . 2BH(2)CNEt)(BF4)(2) (2), and DA . 2BH(2)-COOH (3) complexes were prepared from Me2S solution of (BH2CN)(n) (--> 1 --> 2 --> 3) in fast procedures, differently from those usually applied. in good yields. Dimethyl esters (4) were prepared from 3 with methanol in very fast reactions catalyzed by HBr. 3 and 4 were transformed into DA . BH2COOH (5a,b) and DA . BH2COOMe (6) with DA in THF. Bromination of 3 in aqueous HBr yielded diamine-bis(monobromocarboxyboranes) (7), in vigorous conditions diamine-bis(dibromocarboxyboranes) (9) were produced. N-Bromosuccinimide in methanol transformed 3a,b directly into diamine-bis(bromomethoxycarbonylboranes) (8a,b). BrH . DA . BH(Br)COOH (10a,b) could be prepared from 5a,b with bromine in strongly acidic medium. N-Deprotonated 10a quickly transformed into a five-membered cyclic cation [TMEDA . BHCOOH](+) (cation in 12a) in both water and methanol. Thus, this ion was formed by dissolution of 10a in water, bromination of 5a or destroying one of the borane moieties in 7a by a base. N-Deprotonated 10b in water decomposed with a pH-dependent rate, but in methanol, in the presence of base, it transformed into a six-membered cyclic cation [TMPDA . BHCOOH](+) (cation in 12b). 8a,b could also be transformed into cyclic cations by destroying one of their borane moieties in methanol, (8b in absence of acids only). All cations were prepared as bromide, hexafluorophosphate and tetraphenylborate salts, pK(a) values of 12a,b (pK(a) = 5.5-5.6) are 3 units lower than those of amine-carboxyboranes. Zwitterions (18a,b) formed by their deprotonation were prepared. Cyclic cation [TMEDA . B(Br)COOH](+) (cation in 19a) formed on destroying one dibromocarboxyborane of 9a. This cation, quite a strong acid (pK(a) approximate to 4.2), was prepared as hexafluorophosphate and tetraphenylborate salt. The latter was transformed with aqueous KOH into the corresponding zwitterion (21a).

  DOI：

  10.1021/ic9713442