Triethyl phosphite → HCID 86627329, compound
Reaction equation
[C:1]([C@H:9]([CH2:13][O:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH3:30])[CH2:10][CH2:11]Br)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[P:31]([O:38]CC)([O:35][CH2:36][CH3:37])[O:32][CH2:33][CH3:34]>>[C:1]([C@H:9]([CH2:13][O:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH3:30])[CH2:10][CH2:11][P:31]([O:35][CH2:36][CH3:37])(=[O:38])[O:32][CH2:33][CH3:34])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1Participants
Procedure
A solution of 4.98 g (10.0 mmol) of bromide 4 in 25 mL (150 mmol) of triethyl phosphite [(EtO)3P] was heated at 150° C. (oil bath temperature) overnight. After the excess of (EtO)3P was removed by using a stream of air, the residue was purified by column chromatography on silica gel (elution with CHCl3/MeOH 25:1) to give 4.39 g (79%) of benzoyl phosphonate 5 as a colorless oil; [α]25D −6.88° (c 5.8, CHCl3); 1H NMR (CDCl3) δ 0.88 (t, 3H, J=6.7 Hz), 1.26 (br s, 26H), 1.28-1.33 (m, 6H), 1.70-2.00 (m, 2H), 3.43-3.62 (m, 4H), 4.06-4.12 (m, 4H), 5.23-5.27 (m, 1H), 7.42-7.46 (m, 2H), 7.54-7.59 (m, 1H), 8.04 (d, 2H, J=7.0 Hz); 13C NMR (CDCl3) δ 14.1, 16.4 (d, J=5.8 Hz), 22.2 (d, J=143.2 Hz), 22.6, 24.3 (d, J=4.0 Hz), 29.3, 29.4, 29.6, 29.7, 31.9, 61.6, 71.3, 71.7, 72.8 (d, J=18.1 Hz), 127.7, 128.3, 129.6, 130.1, 133.0, 166.0; MS (electrospray) MH+m/z calcd for C31H56O6P 555.39, found 555.3.
Workup
- customAfter the excess of (EtO)3P was removed
- customthe residue was purified by column chromatography on silica gel (elution with CHCl3/MeOH 25:1)
Sources & evidence
- ORD record
- ord-a9b80d1d5c5448079573c7700c78db8f
- Source dataset
- uspto-grants-2012_04
- Patent number
- US08153615B2
Reaction notes
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