2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane → HCID 70664548, compound

HRID 1624211Notes

Reaction equation

HRID 1624211 reaction equation
[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

Participants

5

Reactant 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, compound

Product 1

HCID 70664548HCID 70664548, compoundYield 55%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
-78 °C

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-52b445447dfb4d4aa463c25f0079da16
Source dataset
uspto-grants-2014_07
Patent number
US08779077B2

Reaction notes

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