Acetone → HCID 56618122, compound

HRID 326165Notes

Reaction equation

HRID 326165 reaction equation
[C:1]([NH:4]/[CH:5]=[CH:6]/[S:7][C:8]1[CH2:14][C@H:13]2[N:10]([C:11](=[O:24])[C@H:12]2[C@@H:15]([O:17][S:18]([O:21][CH2:22][CH3:23])(=[O:20])=[O:19])[CH3:16])[C:9]=1[C:25]([O:27][CH3:28])=[O:26])(=[O:3])[CH3:2].CC(C)=O.[Br:33]Br.C(N(CC)CC)C>ClCCl.C(Cl)(Cl)(Cl)Cl>[C:1]([NH:4][CH:5]=[C:6]([Br:33])[S:7][C:8]1[CH2:14][C@H:13]2[N:10]([C:11](=[O:24])[C@H:12]2[C@@H:15]([O:17][S:18]([O:21][CH2:22][CH3:23])(=[O:19])=[O:20])[CH3:16])[C:9]=1[C:25]([O:27][CH3:28])=[O:26])(=[O:3])[CH3:2]

Participants

7

Reactant 4

HCID 180AcetoneHCID 8471TriethylamineHCID 24408BromineHCID 21772260HCID 21772260, compound

Product 1

HCID 56618122HCID 56618122, compound

Reagents, catalysts & solvents 2

HCID 5943Carbon TetrachlorideSolventHCID 6344DichloromethaneSolvent2×

Procedure

Methyl (5R,6R)-3-[(E)-2-acetamidoethenylthio]-6-[(1S)-1-ethoxysulphonyloxy-ethyl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (110 mg) in dry dichloromethane (4 ml) was cooled to -70° (acetone/solid CO2 bath) and bromine (0.25 ml of a 1 M solution in CCl4) was added to the stirred solution. After 20 mins, triethylamine (50 mg) in dichloromethane (0.5 ml) was added and stirring was continued at -70° for 15 min. The mixture was allowed to warm to room temperature over 30 min. The solution was then washed with water (2×), dried (MgSO4) and evaporated in vacuo to give a brown oil (130 mg). This was chromatographed on silica gel (10 g; 230-430 mesh ASTM) eluting with ethyl acetate/cyclohexane (8:2) to give, after combination and evaporation of the appropriate fractions, methyl (5R,6R)-3-(2-acetamido-1-bromoethylthio)- 6-[(1S)-1-ethoxysulphonyloxyethyl]-7-oxo-1-azabicyclo[3.2.0.]hept-2-ene-2-carboxylate (39 mg), λmax (EtOH), 310 and 245 nm, νmax (CH2Cl2) 1790, 1720, 1625 cm-1, δ(CDCl3) 1.40 (3H, t, J 7 Hz, CH3CH), 2.12 (3H, s, CH3CO), 3.07 (1H,dd, J1 19 Hz, J2 10 Hz 4-CHAHBCH), 3.39 (1H,dd, J1 19 Hz, J2 9.5 Hz, 4-CHAHBCH), 3.7-3.9 (4H, s, at δ 3.80 superposed on m, OCH3 6-CH), 4.1.-4.5 (3H, q, J 7 Hz at 4.30, superposed on m, OCH2CH3, 5-CH) 4.7-5.2 (1H,m, CH.CH.CH3), 7.42 (1H, broad d, J 11.5 Hz, CONHCH), 7.70 (1H, d, J 11.5 Hz,=CHNHCO).

Workup

  1. additionwas added to the stirred solution
  2. waitwas continued at -70° for 15 min
  3. washThe solution was then washed with water (2×)
  4. dry with materialdried (MgSO4)
  5. customevaporated in vacuo

Sources & evidence

ORD record
ord-80e489a5f8bd4f0b9b23abc35fc26fd2
Source dataset
uspto-grants-1984_04
Patent number
US04444783

Reaction notes

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