Nitric Acid → HCID 52913599, compound

HRID 1944103Notes

Reaction equation

HRID 1944103 reaction equation
[C:1]([O:4][C@H:5]1[C@H:12]([O:13][C:14](=[O:16])[CH3:15])[C:9]2([CH2:11][CH2:10]2)[O:8][C@@H:7]([C:17]2[CH:22]=[CH:21][C:20]([Cl:23])=[C:19]([CH2:24][C:25]3[CH:30]=[CH:29][C:28]([OH:31])=[CH:27][CH:26]=3)[CH:18]=2)[C@@H:6]1[O:32][C:33](=[O:35])[CH3:34])(=[O:3])[CH3:2].[N+:36]([O-])([OH:38])=[O:37]>ClCCl.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC>[C:1]([O:4][C@H:5]1[C@H:12]([O:13][C:14](=[O:16])[CH3:15])[C:9]2([CH2:10][CH2:11]2)[O:8][C@@H:7]([C:17]2[CH:22]=[CH:21][C:20]([Cl:23])=[C:19]([CH2:24][C:25]3[CH:26]=[CH:27][C:28]([OH:31])=[C:29]([N+:36]([O-:38])=[O:37])[CH:30]=3)[CH:18]=2)[C@@H:6]1[O:32][C:33](=[O:35])[CH3:34])(=[O:3])[CH3:2]

Participants

5

Reactant 2

HCID 944Nitric AcidHCID 52914599HCID 52914599, compound

Product 1

HCID 52913599HCID 52913599, compoundYield 109.5%

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a stirred solution of acetic acid (5S,6S,7R,8S)-7,8-diacetoxy-5-[4-chloro-3-(4-hydroxy-benzyl)-phenyl]-4-oxa-spiro[2.5]oct-6-yl ester (Example 5, 104 mg, 2 mmol) in dichloromethane (25 ml) was added HNO3 (6% aqueous solution, 5.6 ml, 3.8 mmol) in a drop wise fashion, followed by the addition of tetrabutyl ammonium bromide (100 mg). The reaction mixture was stirred at room temperature until the complete conversion. The reaction mixture was diluted with DCM, washed with water, brine, concentrated and purified by silica gel chromatography to give 1.2 g of acetic acid (5S,6S,7R,8S)-7,8-diacetoxy-5-[4-chloro-3-(4-hydroxy-3-nitro-benzyl)-phenyl]-4-oxa-spiro[2.5]oct-6-yl ester.

Workup

  1. washwashed with water, brine
  2. concentrationconcentrated
  3. custompurified by silica gel chromatography

Sources & evidence

ORD record
ord-264590221ddd4378b0096eb910fd62db
Source dataset
uspto-grants-2013_03
Patent number
US08394772B2

Reaction notes

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