Hydrochloric Acid → HCID 69083988, compound

HRID 1396243Notes

Reaction equation

HRID 1396243 reaction equation
[OH:1][CH2:2][C@H:3]1[O:11][C@H:10]2[C@H:6]([N:7]=[C:8]([N:12]([CH3:20])[C:13](=[O:19])[O:14][C:15]([CH3:18])([CH3:17])[CH3:16])[S:9]2)[C@@H:5]([O:21][CH2:22][C:23]2[CH:28]=[CH:27][C:26]([O:29][CH3:30])=[CH:25][CH:24]=2)[C@@H:4]1[O:31][CH2:32][C:33]1[CH:38]=[CH:37][C:36]([O:39][CH3:40])=[CH:35][CH:34]=1.C1C(=O)N(Br)C(=[O:44])C1.Cl>CCCC[N+](CCCC)(CCCC)CCCC.[Br-].ClCCl.O.CC1(C)N([O])C(C)(C)CCC1>[C:15]([O:14][C:13]([N:12]([CH3:20])[C:8]1[S:9][C@H:10]2[O:11][C@H:3]([C:2]([OH:44])=[O:1])[C@@H:4]([O:31][CH2:32][C:33]3[CH:38]=[CH:37][C:36]([O:39][CH3:40])=[CH:35][CH:34]=3)[C@H:5]([O:21][CH2:22][C:23]3[CH:28]=[CH:27][C:26]([O:29][CH3:30])=[CH:25][CH:24]=3)[C@H:6]2[N:7]=1)=[O:19])([CH3:17])([CH3:16])[CH3:18]

Participants

8

Reactant 3

HCID 313Hydrochloric AcidHCID 67184N-bromobutanimideHCID 69280765HCID 69280765, compound

Product 1

HCID 69083988HCID 69083988, compoundYield 58.6%

Reagents, catalysts & solvents 4

HCID 74236Tetrabutylammonium BromideCatalystHCID 2724126TempoCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

A mixture of tert-butyl (3aR,5R,6S,7R,7aR)-5-(hydroxymethyl)-6,7-bis(4-methoxybenzyloxy)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazol-2-yl(methyl)carbamate (1 g, 1.74 mmol), KHCO3 (780 mg, 7.8 mmol), TBAB (28 mg, 0.09 mmol) and TEMPO (14 mg, 0.09 mmol) in dichloromethane (30 mL) and H2O (6 mL) was treated with NBS (620 mg, 3.5 mmol) overnight at room temperature. The reaction mixture was adjusted to acidic (pH at 3) with hydrochloric acid, and then extracted with dichloromethane (3×20 mL). The combined organic layers were dried over anhydrous sodium sulfate and concentrated under vacuum to provide a residue, which was purified by a silica gel column, eluted with 20˜50% ethyl acetate in petroleum ether to give compound 29 as a white solid (600 mg, 58%). (ES, m/z): [M+H]+ 589.0, 1H NMR (300 MHz, CDCl3) δ 7.25-7.32 (m, 2H), 6.85-6.90 (m, 2H), 6.08-6.10 (d, J=6.3 Hz, 1H), 4.50-4.62 (m, 5H), 4.22-4.29 (m, 2H), 3.97 (m, 1H), 3.81 (s, 6H), 3.34 (s, 3H), 1.54 (s, 9H).

Workup

  1. extractionextracted with dichloromethane (3×20 mL)
  2. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  3. concentrationconcentrated under vacuum
  4. customto provide a residue, which
  5. customwas purified by a silica gel column
  6. washeluted with 20˜50% ethyl acetate in petroleum ether

Sources & evidence

ORD record
ord-89187e5580c748e7afd4f1403f980465
Source dataset
uspto-grants-2014_12
Patent number
US08901087B2

Reaction notes

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