Carbamide Peroxide → 2-(3-Nitrophenyl)oxirane

HRID 1684881Notes

Reaction equation

HRID 1684881 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:9]=[CH:10][CH:11]=1)[CH:7]=[CH2:8])([O-:3])=[O:2].CC1(C)O[C@H]2[C@@H]3OC(C)(C)O[C@]3(C(O)=O)O[C@H]2C[O:14]1.O.OO.NC(N)=O>ClCCl>[N+:1]([C:4]1[CH:5]=[C:6]([CH:7]2[CH2:8][O:14]2)[CH:9]=[CH:10][CH:11]=1)([O-:3])=[O:2]

Participants

5

Reactant 3

HCID 31294Carbamide PeroxideHCID 685143-NitrostyreneHCID 16211407(-)-Diacetone-2-keto-L-gulonic acid monohydrate

Product 1

HCID 112289872-(3-Nitrophenyl)oxiraneYield 75%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
25 °C

Procedure

3-Nitrostyrene (1 g, 6.71 mmol) was taken with 100 mg Immobilized lipase and 2,3:4,6-di-O-isopropylidene-2-keto-L-gulonic acid monohydrate (0.3 g, 1.03 mmol) in dry dichloromethane (15 mL) and stirred at 25° C. and added urea hydrogen peroxide (3 g, 32 mmol) portion-wise at a pH 5 for 20 hours. The reaction was monitored occasionally on TLC. The mixture was filtered and washed the residue with dichloromethane and the filtrate was reduced its volume under reduced pressure using vacuum flash evaporator. The product was purified by preparative TLC with 25% EtOAc/hexane. 75% Yield; Yellow oil (Found: C, 58.22; H, 4.28; N, 8.50. C8H7NO3 requires C, 58.18; H, 4.27; N, 8.48%); Rf (25% EtOAc/hexane) 0.50; [α]D20−1.51 (c 2.0, CHCl3); {lit., [α]D18+2.5 (c 2.8, CHCl3, S}; HPLC analysis using a Chiralpak AD column showed it to be 60% ee [hexane: 2-propanol=9:1, flow rate 0.8 cm3 min−1]; νmax (neat/cm−1) 3113, 2995, 1517, 1343, 1301, 1042, 983, 888, 788, 740; δH (300 MHz; CDCl3) 2.80 (1H, dd, J 2.5 and 4.8, HCOCHH), 3.21 (1H, dd, J 3.9 and 4.8, HCOCHH), 3.97 (1H, dd, J 2.5 and 3.9, PhCHOCH2), 7.40-7.75 (2H, m, 2×CH, arom.) and 8.01-8.24 (2H, m, 2×CH, arom.); δC (300 MHz; CDCl3) 51.7 (CH2), 51.9 (CH), 126.0, 126.4, 145.4 and 148.6 (6×C-Ph); MS m/z (rel. intensity %): 165 (M+, 18), 150(32), 136(68), 120(25), 105(17), 90(100), 77(22), 74(12), 65(52), 63 (59).

Workup

  1. filtrationThe mixture was filtered
  2. washwashed the residue with dichloromethane
  3. customvacuum flash evaporator
  4. customThe product was purified by preparative TLC with 25% EtOAc/hexane

Sources & evidence

ORD record
ord-86c4d892e3db454d831bb2582ec50b2d
Source dataset
uspto-grants-2012_04
Patent number
US08148118B2

Reaction notes

Loading…