Acetic Anhydride → (5R)-5,6-bis(nitrooxy)hexyl (2Z)-4-(acetyloxy)-3-[4-(methylsulfonyl)phenyl]-2-phenylbut-2-enoate

HRID 1437605Notes

Reaction equation

HRID 1437605 reaction equation
[C:1]([O:4][CH2:5]/[C:6](/[C:17]1[CH:22]=[CH:21][C:20]([S:23]([CH3:26])(=[O:25])=[O:24])=[CH:19][CH:18]=1)=[C:7](/[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)\[C:8]([OH:10])=[O:9])(=[O:3])[CH3:2].[N+:27]([O-:41])([O:29][CH2:30][C@H:31]([O:37][N+:38]([O-:40])=[O:39])[CH2:32][CH2:33][CH2:34][CH2:35]O)=[O:28].CCN=C=NCCCN(C)C.C(OC(=O)C)(=O)C>CN(C1C=CN=CC=1)C.ClCCl>[C:1]([O:4][CH2:5]/[C:6](/[C:17]1[CH:22]=[CH:21][C:20]([S:23]([CH3:26])(=[O:25])=[O:24])=[CH:19][CH:18]=1)=[C:7](/[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)\[C:8]([O:10][CH2:35][CH2:34][CH2:33][CH2:32][C@@H:31]([O:37][N+:38]([O-:40])=[O:39])[CH2:30][O:29][N+:27]([O-:41])=[O:28])=[O:9])(=[O:3])[CH3:2]

Participants

7

Reactant 4

HCID 7918Acetic AnhydrideHCID 159081-Ethyl-3-(3'-dimethylaminopropyl)carbodiimideHCID 11617716(Z)-4-Acetoxy-3-(4-(methylsulfonyl) phenyl)-2-phenylbut-2-enoic acidHCID 59556786(2R)-6-hydroxyhexane-1,2-diyl dinitrate

Product 1

HCID 57941622(5R)-5,6-bis(nitrooxy)hexyl (2Z)-4-(acetyloxy)-3-[4-(methylsulfonyl)phenyl]-2-phenylbut-2-enoateYield 63.6%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

A solution of 3 g of (2Z)-4-(acetyloxy)-3-[4-(methylsulfonyl)phenyl]-2-phenylbut-2-enoic acid, 1.7 g of (2R)-6-hydroxyhexane-1,2-diyl dinitrate, 10 mmol of DMAP and 10 mmol of EDCI was stirred in 40 mL of dichloromethane at rt for 2 h. Then, acetic anhydride (0.5 mL) was added and the mixture was filtered through a pad of silica gel and washed with EtOAc, evaporated, purified by flash chromatography (15-50% EtOAc/hexane) to afford 2.8 g of the desired compound as a white solid. 1H NMR (acetone-d6, 500 MHz): δ 7.79 (d, 2H), 7.45 (d, 2H), 7.21-7.16 (m, 1H), 7.13-7.08 (m, 2H), 5.52-5.44 (m, 1H), 5.21 (s, 1H), 4.98 (dd, 1H), 4.72 (dd, 1H), 4.29 (t, 2H), 3.09 (s, 3H), 1.92 (s, 3H), 1.89-1.74 (m, 4H), 1.60-1.48 (m 2H).

Workup

  1. filtrationthe mixture was filtered through a pad of silica gel
  2. washwashed with EtOAc
  3. customevaporated
  4. custompurified by flash chromatography (15-50% EtOAc/hexane)

Sources & evidence

ORD record
ord-6373a28d4a3a4456969c4840602651ee
Source dataset
uspto-grants-2009_11
Patent number
US07622502B2

Reaction notes

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