2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane → HCID 11519967, compound

HRID 1624210Notes

Reaction equation

HRID 1624210 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]([CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])([CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH3:23])[C:4]=2[CH:3]=1.C([Li])CCC.C(O[B:41]1[O:45][C:44]([CH3:47])([CH3:46])[C:43]([CH3:49])([CH3:48])[O:42]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:41]4[O:45][C:44]([CH3:47])([CH3:46])[C:43]([CH3:49])([CH3:48])[O:42]4)=[CH:7][C:6]=3[C:5]2([CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH3:23])[CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])=[CH:13][CH:14]=1

Participants

5

Reactant 3

HCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 52153212,7-Dibromo-9,9-di-n-octylfluoreneHCID 178418339Butyllithium

Product 1

HCID 11519967HCID 11519967, compoundYield 65.3%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
-78 °C

Procedure

2,7-Dibromo-9,9-dioctylfluorene (2.00 g, 3.65 mmol, 1 eq.) was dissolved in diethyl ether (30 ml). The solution was cooled to −78° C. and n-butyllithium (2.4 mL of a 1.6 M solution in hexanes, 3.83 mmol, 1.1 eq.) was added drop wise with strong stirring. The resulted white suspension was allowed to warm to −10° C. until a clear-yellow solution 3 was formed. After stirring for another 10 min, the solution was cooled to −78° C. again and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.82 mL, 4.0 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/dichloromethane=4/1 (v/v) as eluent to give 1.42 g of white powder (yield=65%). 1H NMR (500 MHz, CDCl3) δ (ppm): 7.80 (d, J=7.55 Hz, 1H), 7.72 (s, 1H), 7.65 (d, J=7.55 Hz, 1H), 7.57 (d, J=7.80 Hz, 1H), 7.44 (m, 2H), 2.02-1.96 (m, 2H), 1.94-1.88 (m, 2H), 1.39 (s, 12H), 1.23-1.14 (m, 4H), 1.13-1.03 (m, 16H), 0.82 (t, J=7.15 Hz, 6H), 0.57 (m, 4H). 13C NMR (500 MHz, CDCl3) δ (ppm): 153.57, 149.50, 142.98, 139.97, 133.88, 129.89, 128.86, 126.23, 121.52, 121.44, 119.02, 83.78, 55.47, 53.41, 40.12, 31.77, 29.21, 29.18, 24.97, 23.61, 22.59, 14.06.

Workup

  1. customwas formed
  2. temperaturethe 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/dichloromethane=4/1 (v/v) as eluent

Sources & evidence

ORD record
ord-e5d85677c91147eba58294fa43f14629
Source dataset
uspto-grants-2014_07
Patent number
US08779077B2

Reaction notes

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