1,8-Diazabicyclo(5.4.0)undec-7-ene → HCID 21772275, compound

HRID 1277711Notes

Reaction equation

HRID 1277711 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:22])[C@H:12]2[C@@H:15](OS([O-])(=O)=O)[CH3:16])[C:9]=1[C:23]([O:25][CH2:26][C:27]1[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][CH:28]=1)=[O:24])(=[O:3])[CH3:2].C([N+](C)(C)CCCCCCCCCCCCCCCC)C1C=CC=CC=1.C1CCN2C(=NCCC2)CC1>C(Cl)Cl>[C:1]([NH:4]/[CH:5]=[CH:6]/[S:7][C:8]1[CH2:14][C@H:13]2[N:10]([C:11](=[O:22])/[C:12]/2=[CH:15]\[CH3:16])[C:9]=1[C:23]([O:25][CH2:26][C:27]1[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][CH:28]=1)=[O:24])(=[O:3])[CH3:2].[C:1]([NH:4]/[CH:5]=[CH:6]/[S:7][C:8]1[CH2:14][C@H:13]2[N:10]([C:11](=[O:22])/[C:12]/2=[CH:15]/[CH3:16])[C:9]=1[C:23]([O:25][CH2:26][C:27]1[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][CH:28]=1)=[O:24])(=[O:3])[CH3:2]

Participants

5

Reactant 2

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 131712293HCID 131712293, compound

Product 2

HCID 21772275HCID 21772275, compoundYield 102,732.398%HCID 21772358HCID 21772358, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Benzyldimethyl-n-hexadecylammonium (5R,6R)-3-[(E)-2-acetamidoethenylthio]-6-[(S)-1-sulphonatooxyethyl]-7-oxo-2-p-nitrobenzyloxycarbonyl-1-azabicyclo[3.2.0]hept-2-ene (e46) (1.85 mg) was dissolved in methylene chloride (40 ml) and the solution cooled to -15°. A solution of DBU (0.634 g) in methylene chloride (10 ml) was added, and stirring was continued at -10° for 3.5 hours. The organic solution was washed with 3 portions of brine (20 ml), then dried (MgSO4) and evaporated. The residue was chromatographed on silica gel eluting first with petrol/ethyl acetate (1:4) and then with ethyl acetate to yield p-nitrobenzyl (5R,6Z)-3-[(E)-2-acetamidoethenylthio]-6-ethylidene-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate and p-nitrobenzyl (5R,6E)-3-[(E)-2-acetamidoethenylthio]-6-ethylidene-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (e3 and e6) (0.46 g) in which the E- to Z-isomer ratio was about 1:1.2. Trituration of the mixed products under ethyl acetate gave a pale yellow solid; (Found; C, 55.8; H, 4.5, N, 9.7%, M+, 429.0999. C20H19N3O6S requires C, 55.9; H, 4.5; N, 9.8%, M+ 429.0994). νmax (KBr) 1760, 1690 and 1620 cm-1 ; λmax (EtOH) 340sh (11,000), 310 (13,400) and 268 nm (17,400); δ (DMF-d7) 1.82 and 2.00 (Total 3H, each d, J 7 Hz, CH3CH for E- and Z-isomer, respectively), ca. 1.98 (3H, s, CH3CO), ca. 3.2 (2H, m, CH2C.S), 4.60-5.00 (1H, m, CH.CH2), 5.31 and 5.54 (each 1H, d, J 14, CH2Ar), 5.95 (1H, d, J 13.5, S.CH=CH), 6.12 (dq, J 7 and 0.5 Hz, CH3CH for Z-isomer), 6.38 (dq, J 7 and 1 Hz, CH3CH for E-isomer), 7.15 (1H, dd, J 13.5 and 10.5 Hz; NH.CH=CH), 7.77 and 8.22 (each 2H, d, J 9 Hz, aromatic protons).

Workup

  1. temperaturethe solution cooled to -15°
  2. washThe organic solution was washed with 3 portions of brine (20 ml)
  3. dry with materialdried (MgSO4)
  4. customevaporated
  5. customThe residue was chromatographed on silica gel eluting first with petrol/ethyl acetate (1:4)

Sources & evidence

ORD record
ord-b61f595eceda49c3807f5e0cd71f7b83
Source dataset
uspto-grants-1981_07
Patent number
US04278686

Reaction notes

Loading…