Water → (R)-Methyl 2-(2-chlorophenyl)-2-(4-nitrophenylsulfonyloxy)acetate

HRID 1620424Notes

Reaction equation

HRID 1620424 reaction equation
[Cl:1][C:2]1[CH:13]=[CH:12][CH:11]=[CH:10][C:3]=1[C@@H:4]([OH:9])[C:5]([O:7][CH3:8])=[O:6].C(N(CC)CC)C.[N+:21]([C:24]1[CH:29]=[CH:28][C:27]([S:30](Cl)(=[O:32])=[O:31])=[CH:26][CH:25]=1)([O-:23])=[O:22].O>ClCCl.CN(C1C=CN=CC=1)C>[Cl:1][C:2]1[CH:13]=[CH:12][CH:11]=[CH:10][C:3]=1[C@@H:4]([O:9][S:30]([C:27]1[CH:26]=[CH:25][C:24]([N+:21]([O-:23])=[O:22])=[CH:29][CH:28]=1)(=[O:31])=[O:32])[C:5]([O:7][CH3:8])=[O:6]

Participants

7

Reactant 4

HCID 962WaterHCID 74044-Nitrobenzenesulfonyl chlorideHCID 8471TriethylamineHCID 11790232(R)-Methyl 2-(2-chlorophenyl)-2-hydroxyacetate

Product 1

HCID 45114280(R)-Methyl 2-(2-chlorophenyl)-2-(4-nitrophenylsulfonyloxy)acetateYield 82%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Procedure

(R)-Methyl o-chloromandelate (98.4 g, 0.49 mol, ee=99%) was dissolved in 500 ml of anhydrous dichloromethane, and then 91 ml of triethylamine (0.65 mol) and a catalytic amount of DMAP were added. 120 g (0.54 mol) of p-nitrophenylsulfonyl chloride was dissolved in 500 ml of anhydrous dichloromethane, which was added dropwise into the reaction solution at 0° C., and reacted for 4-5 hrs at 0° C. Water (500 ml) was added to the reaction solution and the layers were separated. The aqueous phase was extracted with dichloromethane (150 ml×3), and the organic phases were combined and dried, and dichloromethane was evaporated under reduced pressure to afford 206.5 g of a crude product as a dark red oil, which was recrystallized in methanol to obtain 154.5 g of a solid product (II-1). Yield 82%. 1H-NMR (300 MHz, CDCl3) δ 3.57 (s, 3H), 6.39 (s, 1H), 7.21-7.39 (m, 4H), 8.07 (d, 2H, J=8.9 Hz), 8.30 (d, 2H, J=8.9 Hz); ESI-MS m/z 408.0 [M+Na]+.

Workup

  1. additionwhich was added dropwise into the reaction solution at 0° C.
  2. customreacted for 4-5 hrs at 0° C
  3. customthe layers were separated
  4. extractionThe aqueous phase was extracted with dichloromethane (150 ml×3)
  5. customdried
  6. customdichloromethane was evaporated under reduced pressure
  7. customto afford 206.5 g of a crude product as a dark red oil, which
  8. customwas recrystallized in methanol

Sources & evidence

ORD record
ord-f1ebb5dc1110408a8b6706f2e1829743
Source dataset
uspto-grants-2014_07
Patent number
US08772489B2

Reaction notes

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