2-Methyl-6-nitrobenzoic anhydride → HCID 118199349, compound

HRID 1770377Notes

Reaction equation

HRID 1770377 reaction equation
[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:13][CH2:14][CH2:15][C@H:16]([O:26][CH2:27][CH2:28][CH3:29])[C@H:17]([C@@H:23]([OH:25])[CH3:24])[CH2:18][CH2:19][CH:20]([CH3:22])[CH3:21])[C:10](O)=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].CC1C=CC=C([N+]([O-])=O)C=1C(OC(C1C([N+]([O-])=O)=CC=CC=1C)=O)=O>C(Cl)Cl.CN(C1C=CN=CC=1)C>[CH2:18]([C@H:17]1[C@H:23]([CH3:24])[O:25][C:10](=[O:11])[C@@H:9]([NH:8][C:6](=[O:7])[O:5][C:1]([CH3:4])([CH3:3])[CH3:2])[CH2:13][CH2:14][CH2:15][C@@H:16]1[O:26][CH2:27][CH2:28][CH3:29])[CH2:19][CH:20]([CH3:22])[CH3:21]

Participants

5

Reactant 2

HCID 104726482-Methyl-6-nitrobenzoic anhydrideHCID 118194673HCID 118194673, compound

Product 1

HCID 118199349HCID 118199349, compoundYield 59.2%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Procedure

A solution of (2S,6S,7S)-2-((tert-butoxycarbonyl)amino)-7-((S)-1-hydroxyethyl)-10-methyl-6-propoxyundecanoic acid (627 mg, 1.50 mmol) in anhydrous DCM (80 mL) was added over 12 h using a syringe pump to a stirred solution of MNBA (1.03 g, 3.00 mmol) and DMAP (1.10 g, 9.01 mmol) in DCM (150 mL) at room temperature. Stirring was continued for an additional 7 h then the reaction mixture was treated with Celite® (5 scoopula tip-fulls). The solvent was removed under reduced pressure and the resulting adsorbed material was directly loaded onto a column and purified using flash column chromatography (80 g SiO2, 0→30% EtOAc/hexanes) to afford the title compound (355 mg, 0.888 mmol, 59%) as a colorless oil: 1H NMR (400 MHz, CDCl3) δ 5.06 (d, J=8.2 Hz, 1H), 4.70 (dq, J=10.1, 6.4 Hz, 1H), 4.24-4.14 (m, 1H), 3.50 (app dt, J=9.0, 6.4 Hz, 1H), 3.28-3.19 (m, 1H), 3.13 (app dt, J=8.8, 6.6 Hz, 1H), 2.30-2.18 (m, 1H), 2.11 (dddd, J=15.6, 10.1, 7.9, 5.2 Hz, 1H), 1.87 (app dq, J=13.1, 4.6 Hz, 1H), 1.78-1.35 (m, 16H), 1.31 (d, J=6.3 Hz, 3H), 1.24-1.03 (m, 3H), 0.96-0.75 (m, 10H); 13C NMR (101 MHz, CDCl3) δ 173.11, 154.94, 79.93, 79.70, 73.53, 70.41, 52.46, 46.66, 34.41, 33.63, 29.03, 28.75, 28.33, 26.26, 23.30, 22.61, 22.44, 19.26, 17.80, 10.88; ESIMS m/z 422 ([M+Na]+).

Workup

  1. customat room temperature
  2. additionthe reaction mixture was treated with Celite® (5 scoopula tip-fulls)
  3. customThe solvent was removed under reduced pressure
  4. custompurified

Sources & evidence

ORD record
ord-688a55c08b4f418494f3754571404411
Source dataset
uspto-grants-2016_02
Patent number
US09247741B2

Reaction notes

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