Boron trifluoride etherate → 2,2,7,7-Tetramethyl-1-(2',4',6'-triisopropylbiphenyl-2-yl)phosphepan-4-one

HRID 78983

反応式

HRID 78983 の反応式
[CH3:1][C:2]1([CH3:32])[CH2:7][C:6](=O)[CH2:5][C:4](C)([CH3:9])[P:3]1[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[C:17]1[C:22]([CH:23]([CH3:25])[CH3:24])=[CH:21][C:20]([CH:26]([CH3:28])[CH3:27])=[CH:19][C:18]=1[CH:29]([CH3:31])[CH3:30].B(F)(F)F.CC[O:39][CH2:40][CH3:41].P.C[Si](C=[N+]=[N-])(C)C>Cl>[CH3:9][C:4]1([CH3:5])[CH2:41][C:40](=[O:39])[CH2:6][CH2:7][C:2]([CH3:32])([CH3:1])[P:3]1[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[C:17]1[C:18]([CH:29]([CH3:31])[CH3:30])=[CH:19][C:20]([CH:26]([CH3:28])[CH3:27])=[CH:21][C:22]=1[CH:23]([CH3:25])[CH3:24]

参加物

6

反応物 4

HCID 8000Boron trifluoride etherateHCID 24404PhosphineHCID 167693TrimethylsilyldiazomethaneHCID 580672642,2,6,6-Tetramethyl-1-(2',4',6'-triisopropylbiphenyl-2-yl)phosphinan-4-one

生成物 1

HCID 580672702,2,7,7-Tetramethyl-1-(2',4',6'-triisopropylbiphenyl-2-yl)phosphepan-4-one収率 63.3%

試薬・触媒・溶媒 1

HCID 313Hydrochloric Acid溶媒

反応条件

温度
-78 °C

実験手順

To a 40-mL scintillation vial equipped with a magnetic stir bar was added 2,2,6,6-tetramethyl-1-(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphinan-4-one (1.38 g, 3.06 mmol, 1 equiv). The vial was sealed with a septa-top cap and then purged with nitrogen gas for 10 minutes The solid was then dissolved with anhydrous, degassed dichloromethane (10 mL). In a separate 250-mL round bottom flask was added anhydrous, degassed dichloromethane (36 mL) which was cooled to −78° C. Boron trifluoride diethyl etherate (582 μL, 4.59 mmol, 1.5 equiv) was then added to the flask. The phosphine solution was transferred by cannula to the reaction flask over the course of 3 minutes using a positive pressure of nitrogen gas. After stirring the solution for 5 minutes, (trimethylsilyl)diazomethane (2.3 mL, 4.59 mmol, 1.5 equiv, 2 Min hexane) was added slowly over 3 minutes The bright yellow solution was stirred at −78° C. for an hour, then diluted with 1 M aqueous hydrochloric acid (50 mL). The slurry was warmed to room temperature overnight. The solution was charged into a separatory funnel and the phases were partitioned. The organic layer was collected and washed with aqueous saturated sodium bicarbonate (50 mL), dried over sodium sulfate, filtered, and concentrated in a rotary evaporator. Purification of the crude colorless oil by silica gel column chromatography on an Isco CombiFlash system (120-g column; gradient: 1.5 column volumes heptane, ramp up to 98:2 heptane:methyl tert-butyl ether over 0.5 column volumes, hold at 98:2 for 2 column volumes, ramp up to 80:20 heptane:methyl tert-butyl ether over 8 column volumes, hold at 80:20 for 2 column volumes) afforded the title compound as a white solid (900 mg, 90 area % by HPLC, 63% yield). 1H NMR (400 MHz, CDCl3) δ ppm 8.00-7.90 (m, 1H), 7.43-7.29 (m, 2H), 7.28-7.21 (m, 1H), 7.00 (s, 2H), 3.10-2.86 (m, 2H), 2.73-2.37 (m, 5H), 2.34-2.18 (m, 1H), 1.95-1.77 (m, 1H), 1.31 (d, J=6.9 Hz, 5H), 1.23 (d, J=6.8 Hz, 3H), 1.20 (d, J=6.8 Hz, 3H), 1.15 (d, J=6.6 Hz, 3H), 1.10 (d, J=6.4 Hz, 3H), 1.08-1.03 (m, 4H), 1.02-0.98 (m, 4H), 0.95 (d, J=6.7 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ ppm 211.3, 148.6 (d, J=35 Hz), 147.5, 145.8 (d, J=16 Hz), 136.1 (d, J=6 Hz), 135.5 (d, J=31 Hz), 134.3 (d, J=2 Hz), 132.6 (d, J=7 Hz), 127.8, 125.5, 120.1 (d, J=5 Hz), 56.5 (d, J=10 Hz), 41.5, 36.3 (d, J=10 Hz), 35.0 (d, J=24 Hz), 34.3, 33.3 (d, J=27 Hz), 32.2 (d, J=31 Hz), 31.9 (dd, J=6, 2 Hz), 30.7, 29.5 (d, J=5 Hz), 29.3 (d, J=3 Hz), 26.7 (d, J=33 Hz), 24.3 (d, J=8 Hz), 22.9 (d, J=9 Hz). 31P NMR (CDCl3, 202 MHz) δ ppm 18.3 (s). HRMS (TOF-ESI+) calcd for [M, C31H45OP]+ 464.3208. Found 464.3216.

後処理

  1. customTo a 40-mL scintillation vial equipped with a magnetic stir bar
  2. customThe vial was sealed with
  3. customa septa-top cap
  4. custompurged with nitrogen gas for 10 minutes The solid
  5. dissolutionwas then dissolved with anhydrous,
  6. customdegassed dichloromethane (10 mL)
  7. additionIn a separate 250-mL round bottom flask was added anhydrous
  8. customdegassed dichloromethane (36 mL) which
  9. customwas transferred by cannula to the reaction flask over the course of 3 minutes
  10. stirringwas stirred at −78° C. for an hour
  11. temperatureThe slurry was warmed to room temperature overnight
  12. additionThe solution was charged into a separatory funnel
  13. customthe phases were partitioned
  14. customThe organic layer was collected
  15. washwashed with aqueous saturated sodium bicarbonate (50 mL)
  16. dry with materialdried over sodium sulfate
  17. filtrationfiltered
  18. concentrationconcentrated in a rotary evaporator
  19. customPurification of the crude colorless oil by silica gel column chromatography on an Isco CombiFlash system (120-g column

出典と根拠

ORDレコード
ord-a1fa64b87c7240f5add39447d4d017d4
出典データセット
uspto-grants-2014_09
特許番号
US08841487B2

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