[3-(2H-borinin-1-yloxy)-2,3-dimethylbutan-2-yl]oxy-trimethylsilane | 150194-20-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 金属杂环化合物
• 英文名称: [3-(2H-borinin-1-yloxy)-2,3-dimethylbutan-2-yl]oxy-trimethylsilane
• CAS: 150194-20-0
• 化学式: C₁₄H₂₇BO₂Si
• 分子量: 266.264
• InChiKey: VHWGYCVDOYPMBQ-UHFFFAOYSA-N

物化性质

• 沸点：
  291.0±40.0 °C(predicted)
• 密度：
  0.89±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.07
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  [3-(2H-borinin-1-yloxy)-2,3-dimethylbutan-2-yl]oxy-trimethylsilane 、 [3-(4H-borinin-1-yloxy)-2,3-dimethylbutan-2-yl]oxy-trimethylsilane 、 叔丁基锂 以 正己烷 、 正戊烷 为溶剂， 以90%的产率得到
  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
• 作为产物：
  描述：

  三甲基氯硅烷 、 Lithium;oxolane;2,2,3,3-tetramethyl-1,4-dioxa-5-boranuidaspiro[4.5]deca-6,8-diene 以 正戊烷 为溶剂， 生成 [3-(2H-borinin-1-yloxy)-2,3-dimethylbutan-2-yl]oxy-trimethylsilane 、 [3-(4H-borinin-1-yloxy)-2,3-dimethylbutan-2-yl]oxy-trimethylsilane
  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. 21. 2,4-Pentadienylboranes as key intermediates of a novel route to boracyclohexadienes and boratabenzenes. Structure of [Li(TMPDA)](C5H5BNMe2)
  作者：Gerhard E. Herberich、Bernd Schmidt、Ulli Englert、Trixie Wagner

  DOI：10.1021/om00032a008

  日期：1993.8

  Under metalation conditions the 2,4-pentadienylboranes 2,4-C5H7B(NR2)2 (R = Me, Et) and 2,4-C5H7B(O2C2Me4) undergo an electrocyclic ring closure to form borabenzene derivatives. This novel reaction provides a far more efficient access to borabenzene chemistry than previous methods. The dimethylamino derivative [LiMe2N(CH2)3NMe2}](C5H5BNMe2) is the first boratabenzene salt to be structurally characterized.