Triethyl phosphite → HCID 86609186, compound

HRID 249633Notes

Reaction equation

HRID 249633 reaction equation
Br[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][O:7][CH2:8][CH:9]1[CH2:14][CH:13]2[CH2:15][CH:10]1[CH:11]=[CH:12]2.[CH2:16]([O:18][P:19]([O:23]CC)[O:20][CH2:21][CH3:22])[CH3:17]>>[CH2:16]([O:18][P:19]([CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][O:7][CH2:8][CH:9]1[CH2:14][CH:13]2[CH2:15][CH:10]1[CH:11]=[CH:12]2)(=[O:23])[O:20][CH2:21][CH3:22])[CH3:17]

Participants

3

Reactant 2

HCID 31215Triethyl phosphiteHCID 21989304HCID 21989304, compound

Product 1

HCID 86609186HCID 86609186, compound

Conditions

Temperature
160 °C

Procedure

5-[[(5-bromopentyl)oxy]methyl]bicyclo[2.2.1]hept-2-ene 5 (10 g) was added to 50 mL of triethylphosphite and the solution was heated at 160° C. under nitrogen for 20 h. The solution was cooled to room temperature and excess triethylphosphite was removed under reduced pressure. The oily residue was distilled in vacuo to give 6 as a colorless oil, b.p. 145° C., 0.15 Torr. 1H NMR (500 MHz, 25° C., CDCl3): δ (endo isomer, 85%) 6.07-6.05 (m, 1H, olefinic), 5.87-5.85 (m, 1H, olefinic), 4.06-4.00 (m, 4H, POCH2CH3), 3.34-2.94 (m, 6H, CH2), 2.84 (br s, 1H, bridgehead CH), 2.73 (br s, 1H, bridgehead CH), 2.30-2.20 (m, 1H, exo CH), 1.70-1.49 (m, 9H, CH2), 1.27 (t, 6H, POCH2CH3), 0.44-0.41 (m, 1H, endo CH of CH2); (exo isomer, partial) 6.02-6.01 (m, 1H, olefinic), 2.70 (br s, 1H, bridgehead CH). 13C {1H} NMR (125 MHz, 25° C., CDCl3): δ (endo isomer) 137.0 (olefinic CH), 132.5 (olefinic CH), 74.6 (CH—CH2O), 61.4 (d, |2JC-P|=6 Hz, POCH2CH3), 49.4 (CH2 bridge), 44.0 (bridgehead CH), 42.2 (bridgehead CH), 38.9 (CH—CH2O), 29.3 (CH2), 27.4 (CH2), 27.3 (CH2), 25.7 (d, |1JC-P|=140 Hz, CH2P), 22.4 (CH2), 22.3 (CH2), 16.5 (d, |3JC-P|=5.4 Hz, POCH2CH3); (exo isomer, partial) 136.6 (olefinic CH), 75.6 (CH—CH2O), 45.0 (CH), 43.8 (CH), 41.6 (CH), 29.8 (CH2). 31P{1H} NMR (200 MHz, 25° C., CDCl3): δ 32.6

Workup

  1. temperatureThe solution was cooled to room temperature
  2. customexcess triethylphosphite was removed under reduced pressure
  3. distillationThe oily residue was distilled in vacuo

Sources & evidence

ORD record
ord-354e6f62048942e582e0cc99e7c71ed1
Source dataset
uspto-grants-2011_01
Patent number
US07862860B2

Reaction notes

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