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2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane → HCID 70664548、化合物

HRID 1624211
ノート
印刷プレビュー

反応式

HRID 1624211 の反応式
[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8](Br)=[CH:9][CH:10]=3)[C:5]([CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][Br:29])([CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][Br:22])[C:4]=2[CH:3]=1.C([Li])(C)(C)C.C(O[B:39]1[O:43][C:42]([CH3:45])([CH3:44])[C:41]([CH3:47])([CH3:46])[O:40]1)(C)C>C(OCC)C>[Br:1][C:2]1[CH:3]=[C:4]2[C:12]([C:11]3[CH:10]=[CH:9][C:8]([B:39]4[O:40][C:41]([CH3:46])([CH3:47])[C:42]([CH3:44])([CH3:45])[O:43]4)=[CH:7][C:6]=3[C:5]2([CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][Br:29])[CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][Br:22])=[CH:13][CH:14]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

5

反応物 3

HCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 218679302,7-Dibromo-9,9-bis(6-bromohexyl)-9H-fluoreneHCID 178418306HCID 178418306、化合物

生成物 1

HCID 70664548HCID 70664548、化合物収率 55%

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒

反応条件

温度
-78 °C

実験手順

2,7-Dibromo-9,9-bis(6-bromohexyl)fluorene (2.00 g, 3.08 mmol, 1 eq.) was dissolved in diethyl ether (25 ml). The solution was cooled to −78° C. and t-butyllithium (2.0 mL of a 1.7 mole/L solution in hexanes, 3.38 mmol, 1.1 eq.) was added drop wise with strong stirring. The resulted white suspension was allowed to warm to −10° C. and stirred for 10 min. Then the solution was cooled to −78° C. again and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.69 mL, 3.38 mmol, 1.1 eq.) was added in one time. The mixture was stirring for another 1 h at −78° C. and was allowed to warm to 25° C. and stirred for 24 h, and then the reaction was quenched by 10 mL of water. The organic layer was washed thoroughly by water and was dried by anhydrous Na2SO4. After the solvent was removed under reduced pressure, the crude oil was separated by column chromatography with hexane/chloroform=3/1 (v/v) as eluent to give 1.18 g of white powder (yield=50%). 1H NMR (500 MHz, CDCl3) δ (ppm): 7.81 (d, J=7.55 Hz, 1H), 7.72 (s, 1H), 7.66 (d, J=7.55 Hz, 1H), 7.58 (dd, J=1.90 and 6.70 Hz, 1H), 7.46 (dd, J=1.80 and 6.70 Hz), 3.27 (t, J=6.85 Hz, 4H), 2.03-1.95 (m, 2H), 1.94-1.91 (m, 2H), 1.67-1.62 (m, 4H), 1.39 (s, 12H), 1.19-1.14 (m, 4H), 1.09-1.04 (m, 4H), 0.61-0.55 (m, 4H). 13C NMR (500 MHz, CDCl3) δ (ppm): 153.19, 149.12, 142.97, 139.98, 134.06, 130.09, 128.75, 126.14, 121.64, 121.56, 119.14, 83.85, 55.35, 40.00, 33.88, 32.65, 28.97, 27.76, 24.98, 23.44.

後処理

  1. temperatureto warm to −10° C.
  2. temperatureThen the solution was cooled to −78° C. again
  3. stirringThe mixture was stirring for another 1 h at −78° C.
  4. temperatureto warm to 25° C.
  5. stirringstirred for 24 h
  6. customthe reaction was quenched by 10 mL of water
  7. washThe organic layer was washed thoroughly by water
  8. dry with materialwas dried by anhydrous Na2SO4
  9. customAfter the solvent was removed under reduced pressure
  10. customthe crude oil was separated by column chromatography with hexane/chloroform=3/1 (v/v) as eluent

出典と根拠

ORDレコード
ord-52b445447dfb4d4aa463c25f0079da16
出典データセット
uspto-grants-2014_07
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08779077B2

反応ノート

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