bis(dimethylamino)[(E)-2,4-pentadienyl]borane | 150194-10-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 英文名称: bis(dimethylamino)[(E)-2,4-pentadienyl]borane
• 英文别名: (E)-bis(dimethylamino)-2,4-pentadienylborane；N-[dimethylamino-[(2E)-penta-2,4-dienyl]boranyl]-N-methylmethanamine
• CAS: 150194-10-8
• 化学式: C₉H₁₉BN₂
• 分子量: 166.074
• InChiKey: VXOPJPVRIVMZFV-BQYQJAHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.34
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  反-1,3-戊二烯 、 二(二甲氨基)氯化硼 在 氢化钾 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 以75%的产率得到bis(dimethylamino)[(Z)-2,4-pentadienyl]borane
  参考文献：
  名称：

  Borabenzene Derivatives. 22. Synthesis of Boratabenzene Salts from 2,4-Pentadienylboranes. Structure of [NMe3Ph][C5H5BMe]

  摘要：

  Borylation of potassium pentadienide with BCl(NR(2))(2) and subsequent alcoholysis produce 2,4-pentadienylboranes C5H7B(NR(2))(2) (4a-c: R = Me, Et, Pr-i), C5H7B(OR)(2) (4e,f: R = Et, Bu(t)), and C5H7B(OCR(2))(2) with 1,3,2-dioxaborolane rings (4g,h: R = H, Me) as mixtures of E and Z isomers. Metalation of 4a,b in THF by lithium dialkylamides LiNR'(2) (R' = Me, Et, Pr-i) in the presence of TMEDA. results fi) in a nonproductive deborylation via primary attack at the boron center, (ii) in ring closure to produce boratabenzene salts [Li(TMEDA)][C5H5-BNR(2)] (10a,b: R = Me, Et), and (iii) in substitution of B-dialkylamino groups when NR(2) is bulkier than NR'(2). 10a is obtained in 26.5% yield. Metalation of 4h in THF by the sterically demanding lithium dialkylamides LDA and LiTMP affords a precipitate of the spiroborate [Li(THF][C5H6B(OCMe(2))(2)] (13) in 63% yield in equilibrium with the presumed isomer Li-[C5H5BO(CMe(2))(2)OH] (Li(Sg)) in the THF solution. 13 can be transformed into boratabenzenes by several methods. (i) Treatment with Me(3)SiCl produces a 1:1 mixture of isomeric boracyclohexadienes C(5)H(6)BOCMe(2)CMe(2)OSiMe(3) (15a, 2,4-isomer; 15b, 2,5-isomer) which, on subsequent low-temperature metalation, give Li[C5H5BO(CMe(2))OSiMe(3)] (Li(3h)). (ii) Metalation of 13 at -78 degrees C affords Li-2[C5H5BO(CMe(2))O] (Li-2(3i)) and, after treatment with Me(3)SiCl, the bora-2,4-cyclohexadiene (5-Me(3)Si)C(5)H(5)BOCMe(2)CMe(2)OSiMe(3) (16). (iii) Treatment of 13 with Al(2)Me(6) in toluene at -78 degrees C affords Li[C(5)H(5)BMe] (Li(3b)) in 79% yield as a white solid. This salt is also obtained from Li(3h) and Al(2)Me(6). (iv) Addition of 15 to LiBu(t) in pentane/hexane produces Li[C(5)H(5)BBu(t)] (Li(3c)) in 53% yield. Combining strongly alkaline aqueous solutions of[NMe(3)Ph]I and Li(3b) affords [NMe(3)Ph][C(5)H(5)BMe] (18). 18 crystallizes in the monoclinic space group P2(1)/n with a = 935.4(1) pm, b = 1557.4(4) pm, c = 988.8(1) pm, beta = 95.47(1)degrees, and Z = 4. The 1-methylboratabenzene ion of 18 displays nearly perfect C-2 nu symmetry with intra-ring bond distances of 150.1, 138.8, and 139.2 pm (average) for B-C1 (B-C5), C1-C2 (C4-C5), and C2-C3 (C3-C4), respectively.

  DOI：

  10.1021/om00001a064

文献信息

• Borabenzene Derivatives. 22. Synthesis of Boratabenzene Salts from 2,4-Pentadienylboranes. Structure of [NMe3Ph][C5H5BMe]
  作者：Gerhard E. Herberich、Bernd Schmidt、Ulli Englert

  DOI：10.1021/om00001a064

  日期：1995.1

  Borylation of potassium pentadienide with BCl(NR(2))(2) and subsequent alcoholysis produce 2,4-pentadienylboranes C5H7B(NR(2))(2) (4a-c: R = Me, Et, Pr-i), C5H7B(OR)(2) (4e,f: R = Et, Bu(t)), and C5H7B(OCR(2))(2) with 1,3,2-dioxaborolane rings (4g,h: R = H, Me) as mixtures of E and Z isomers. Metalation of 4a,b in THF by lithium dialkylamides LiNR'(2) (R' = Me, Et, Pr-i) in the presence of TMEDA. results fi) in a nonproductive deborylation via primary attack at the boron center, (ii) in ring closure to produce boratabenzene salts [Li(TMEDA)][C5H5-BNR(2)] (10a,b: R = Me, Et), and (iii) in substitution of B-dialkylamino groups when NR(2) is bulkier than NR'(2). 10a is obtained in 26.5% yield. Metalation of 4h in THF by the sterically demanding lithium dialkylamides LDA and LiTMP affords a precipitate of the spiroborate [Li(THF][C5H6B(OCMe(2))(2)] (13) in 63% yield in equilibrium with the presumed isomer Li-[C5H5BO(CMe(2))(2)OH] (Li(Sg)) in the THF solution. 13 can be transformed into boratabenzenes by several methods. (i) Treatment with Me(3)SiCl produces a 1:1 mixture of isomeric boracyclohexadienes C(5)H(6)BOCMe(2)CMe(2)OSiMe(3) (15a, 2,4-isomer; 15b, 2,5-isomer) which, on subsequent low-temperature metalation, give Li[C5H5BO(CMe(2))OSiMe(3)] (Li(3h)). (ii) Metalation of 13 at -78 degrees C affords Li-2[C5H5BO(CMe(2))O] (Li-2(3i)) and, after treatment with Me(3)SiCl, the bora-2,4-cyclohexadiene (5-Me(3)Si)C(5)H(5)BOCMe(2)CMe(2)OSiMe(3) (16). (iii) Treatment of 13 with Al(2)Me(6) in toluene at -78 degrees C affords Li[C(5)H(5)BMe] (Li(3b)) in 79% yield as a white solid. This salt is also obtained from Li(3h) and Al(2)Me(6). (iv) Addition of 15 to LiBu(t) in pentane/hexane produces Li[C(5)H(5)BBu(t)] (Li(3c)) in 53% yield. Combining strongly alkaline aqueous solutions of[NMe(3)Ph]I and Li(3b) affords [NMe(3)Ph][C(5)H(5)BMe] (18). 18 crystallizes in the monoclinic space group P2(1)/n with a = 935.4(1) pm, b = 1557.4(4) pm, c = 988.8(1) pm, beta = 95.47(1)degrees, and Z = 4. The 1-methylboratabenzene ion of 18 displays nearly perfect C-2 nu symmetry with intra-ring bond distances of 150.1, 138.8, and 139.2 pm (average) for B-C1 (B-C5), C1-C2 (C4-C5), and C2-C3 (C3-C4), respectively.