Benzyl chloroformate → 3-[3-(Naphthalene-1-sulfonylmethyl)-4-nitro-phenoxy]-pyrrolidine-1-carboxylic acid benzyl ester

HRID 1711394Notes

Reaction equation

HRID 1711394 reaction equation
C([N:8]1[CH2:12][CH2:11][CH:10]([O:13][C:14]2[CH:19]=[CH:18][C:17]([N+:20]([O-:22])=[O:21])=[C:16]([CH2:23][S:24]([C:27]3[C:36]4[C:31](=[CH:32][CH:33]=[CH:34][CH:35]=4)[CH:30]=[CH:29][CH:28]=3)(=[O:26])=[O:25])[CH:15]=2)[CH2:9]1)C1C=CC=CC=1.[CH2:37]([O:44][C:45](Cl)=[O:46])[C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1.[OH-].[Na+]>C1C=CC=CC=1>[CH2:37]([O:44][C:45]([N:8]1[CH2:12][CH2:11][CH:10]([O:13][C:14]2[CH:19]=[CH:18][C:17]([N+:20]([O-:22])=[O:21])=[C:16]([CH2:23][S:24]([C:27]3[C:36]4[C:31](=[CH:32][CH:33]=[CH:34][CH:35]=4)[CH:30]=[CH:29][CH:28]=3)(=[O:26])=[O:25])[CH:15]=2)[CH2:9]1)=[O:46])[C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1

Participants

5

Reactant 3

HCID 10387Benzyl chloroformateHCID 14798Sodium HydroxideHCID 588286161-Benzyl-3-[3-(naphthalene-1-sulfonylmethyl)-4-nitro-phenoxy]-pyrrolidine

Product 1

HCID 588286253-[3-(Naphthalene-1-sulfonylmethyl)-4-nitro-phenoxy]-pyrrolidine-1-carboxylic acid benzyl esterYield 70%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A solution of 1-benzyl-3-[3-(naphthalene-1-sulfonylmethyl)-4-nitro-phenoxy]-pyrrolidine (4.2 g, 8.4 mmol) and benzylchloroformate (12.0 mL, 84 mmol in 2 equal portions) in benzene was heated at reflux temperature, under nitrogen, for 3 hours, cooled to ambient temperatures, poured into 2.5 N sodium hydroxide and extracted with ethyl acetate. The extracts were combined, washed sequentially with water and brine, dried over anhydrous magnesium sulfate and concentrated in vacuo. The resultant residue was purified by flash chromatography using 40-50% ethyl acetate in hexane to afford 3-[3-(naphthalene-1-sulfonylmethyl)-4-nitro-phenoxy]-pyrrolidine-1-carboxylic acid benzyl ester as a buff foam, 3.2 g (70% yield), Mass spectrum (+EI, [M+H]+) m/z 547. 1HNMR (500 MHz, DMSO-d6): δ8.46 (d, 1H, J=7.44 Hz), 8.27 (d, 1H, J=8.06 Hz), 8.06-8.08 (m, 1H), 7.94-7.99 (m, 2H), 7.57-7.68 (m, 3H), 7.26-7.39 (m, 5H), 7.09 (dd, 1H, J=9.15 Hz and 2.68 Hz), 6.77 (s, 1H), 5.19-5.26 (m, 2H), 5.01-5.10 (m, 2H), 4.90 (s, 1H), 3.42-3.59 (m, 2H), 3.31-3.36 (m, 1H), 1.98-2.10 (m, 1H), 1.79-1.86 ppm (m, 1H).

Workup

  1. temperatureat reflux temperature
  2. temperaturecooled to ambient temperatures
  3. extractionextracted with ethyl acetate
  4. washwashed sequentially with water and brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe resultant residue was purified by flash chromatography

Sources & evidence

ORD record
ord-ff7824d770f14d898ac6455f897fda26
Source dataset
uspto-grants-2010_09
Patent number
US07790751B2

Reaction notes

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