Methanesulfonyl chloride → (1S,9S) t-Butyl 6,10-dioxo-9-methylsulphonylamino-1,2,3,4,7,8,9,10-octahydro-6H-pyridazino-[1,2-a][1,2]diazepine-1-carboxylate

HRID 363855Notes

Reaction equation

HRID 363855 reaction equation
[NH2:1][CH:2]1[C:8](=[O:9])[N:7]2[CH:10]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:11][CH2:12][CH2:13][N:6]2[C:5](=[O:21])[CH2:4][CH2:3]1.C(N(C(C)C)CC)(C)C.[CH3:31][S:32](Cl)(=[O:34])=[O:33]>C(Cl)Cl.CCOC(C)=O>[O:21]=[C:5]1[CH2:4][CH2:3][C@H:2]([NH:1][S:32]([CH3:31])(=[O:34])=[O:33])[C:8](=[O:9])[N:7]2[C@H:10]([C:14]([O:16][C:17]([CH3:18])([CH3:20])[CH3:19])=[O:15])[CH2:11][CH2:12][CH2:13][N:6]12

Participants

6

Reactant 3

HCID 31297Methanesulfonyl chlorideHCID 81531DiisopropylethylamineHCID 11174000HCID 11174000, compound

Product 1

HCID 57132364(1S,9S) t-Butyl 6,10-dioxo-9-methylsulphonylamino-1,2,3,4,7,8,9,10-octahydro-6H-pyridazino-[1,2-a][1,2]diazepine-1-carboxylateYield 77%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of t-butyl 9-amino-6,10-dioxo-1,2,3,4,7,8,9,10-octahydro-6H-pyridazino[1,2-a][1,2]diazepine-1-carboxylate (GB 2,128,984; 831mg, 2.79 mmol) and diisopropylethylamine (1.22 ml, 6.99 mmol, 2.5 equiv) in CH2Cl2 (10 ml) under dry nitrogen was treated with methanesulphonyl chloride (237 μl, 3.07 mmol 1.1 equiv). The mixture was stirred for 1 h, diluted with EtOAc (75 ml) and washed with saturated NaHCO3 (50 ml) and saturated aqueous sodium chloride (30 ml), dried (MgSO4) and concentrated. Flash chromatography (10-35% EtOAc in CH2C12) afforded 211b (806 mg, 77%) as a colourless solid: mp 68°-70 ° C.; [α]D23 -109 (c 1.09, CH2Cl2) ; IR (KBr) 3270, 2980, 2939, 1735, 1677, 1458, 1447, 1418, 1396, 1370, 1328, 1272, 1252, 1232, 1222, 1156, 1131, 991; 1H NMR (CDCl3) δ6.15 (1H, d), 5.31 (1H, m), 4.65-4.11 (2H, m), 3.47 (1H, m) 2.99 (3H, s), 2.89 (1H, m), 2.72-2.51 (2H, m), 2.34 (1H, m), 2.26 (1H, m), 2.05-1.62 (4H, m), 1.47 (9H, s); Anal. Calcd for C15H23N3O6S: C, 47.97; H, 6.71; N, 11.19; S, 8.54. Found: C, 48.28; H, 6.68; N, 10.86; S, 8.28. MS (+FAB) 376 (M+ +1, 66%), 320 (100).

Workup

  1. washwashed with saturated NaHCO3 (50 ml) and saturated aqueous sodium chloride (30 ml)
  2. dry with materialdried (MgSO4)
  3. concentrationconcentrated

Sources & evidence

ORD record
ord-919316780dd44d39bef9e26e7e5f8de7
Source dataset
uspto-grants-1999_02
Patent number
US05874424

Reaction notes

Loading…