4-Nitrobenzoic Acid → Triphenylphosphine Oxide

HRID 1814321Notes

Reaction equation

HRID 1814321 reaction equation
N1([C@@H](C)[C@@H](C)[OH:12])C2C=CC=CC=2N=C1.[C:15]1([P:21]([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[N+:34]([C:37]1[CH:45]=[CH:44][C:40]([C:41]([OH:43])=[O:42])=[CH:39][CH:38]=1)([O-:36])=[O:35].N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[N+:34]([C:37]1[CH:38]=[CH:39][C:40]([C:41]([O-:43])=[O:42])=[CH:44][CH:45]=1)([O-:36])=[O:35].[C:28]1([P:21](=[O:12])([C:15]2[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=2)[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1

Participants

7

Reactant 4

HCID 61084-Nitrobenzoic AcidHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 69691756HCID 69691756, compound

Product 2

HCID 13097Triphenylphosphine OxideHCID 44199404-Nitrobenzoate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To (1R,2S)-2-benzimidazol-1-yl-1-methyl-propanol (1.27 g, 6.68 mmol), triphenylphosphine (1.19 g, 1.1 equiv), and 4-nitrobenzoic acid (1.22 g, 1.1 equiv) in THF (20 mL) was added diethyl azodicarboxylate (1.15 mL, 1.1 equiv). After stirring 12 h, the solvent was removed, and chromatographed on silica gel eluting with ethyl acetate to give the intermediate 4-nitrobenzoate and triphenylphosphine oxide as a mixture. This mixture was directly hydrolyzed with 1.0N sodium hydroxide (20 mL) in THF/methanol for 3 h. The solvent was partially removed and the reaction diluted with water and extracted with ethyl acetate. The crude product was chromatographed on silica gel eluting with 7%(8:1, ethanol/ammonium hydroxide) in dichloromethane. (1S,2S)-2-benzimidazol-1-yl-1-methyl-propanol was isolated as a colorless solid 552 mg (44%). 1H NMR (CDCl3) 8.00(s,1H), 7.69(d,1H), 7.43(d,1H), 7.24(M, 2H), 4.36(m,1H), 4.27(m,1H), 1.33(d,3H), 1.22(d,3H).

Workup

  1. customthe solvent was removed
  2. customchromatographed on silica gel eluting with ethyl acetate

Sources & evidence

ORD record
ord-0e36a48cb1d74ce8abe6678720affab8
Source dataset
uspto-grants-2005_04
Patent number
US06875765B2

Reaction notes

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