Hydrochloric Acid → HCID 67241189, compound

HRID 2422941Notes

Reaction equation

HRID 2422941 reaction equation
[CH2:1](Br)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([O-])([O-])=O.[K+].[K+].[Cl:15][C:16]1[CH:21]=[CH:20][C:19]([CH:22]=[CH:23][C:24]([NH:26][C:27]2[CH:36]=[CH:35][C:30]([C:31]([O:33][CH3:34])=[O:32])=[C:29]([OH:37])[CH:28]=2)=[O:25])=[CH:18][CH:17]=1.C1CCN2C(=NCCC2)CC1.Cl.[N+:50]([CH3:53])([O-:52])=[O:51]>CN(C=O)C.O>[CH2:1]([O:37][C:29]1[CH:28]=[C:27]([NH:26][C:24](=[O:25])[CH2:23][CH:22]([C:19]2[CH:18]=[CH:17][C:16]([Cl:15])=[CH:21][CH:20]=2)[CH2:53][N+:50]([O-:52])=[O:51])[CH:36]=[CH:35][C:30]=1[C:31]([O:33][CH3:34])=[O:32])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 6375NitromethaneHCID 7498Benzyl BromideHCID 11430Potassium CarbonateHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 67243346HCID 67243346, compound

Product 1

HCID 67241189HCID 67241189, compoundYield 40%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

Benzyl bromide (0.575 g, 3.36 mmol) and K2CO3 (0.77 g, 5.60 mmol) were added to a stirred solution of 45 (0.9 g, 2.80 mmol) in anhydrous DMF (20 ml) under Ar. The reaction mixture was stirred at room temperature overnight and the mixture was poured in water (20 ml). The product was extracted with ethyl acetate (2×20 ml), dried over Na2SO4 and the solvent removed under reduced pressure. The resultant crude 46 was stirred in the microwave reactor in presence of DBU (0.468 g, 3.08 mmol), and nitromethane (10 mL in the microwave), at 100° C. for 15 min. After cooling to room temperature, the reaction mixture was poured into HCl 1M (15 ml). The product was extracted with ethyl acetate (2×20 ml), dried over Na2SO4 and the solvent removed under reduced pressure. Chromatography on silica gel (80:20, hexanes/ethyl acetate) afforded 50 (0.521 g, 1.10 mmol, 40%) as a white solid, mp 81-83° C. 1H NMR (400 MHz, CDCl3) δ 2.75 (1H, dd, J 6.6, 15.4 Hz), 2.85 (1H, dd, J 7.6, 15.6 Hz), 3.87 (3H, s), 4.07 (1H, quint, J 6.8 Hz), 4.70 (1H, dd, J 7.8, 13.0 Hz), 4.83 (1H, dd, J 6.4, 12.8 Hz), 5.17 (2H, s), 6.77 (1H, dd, J 2.0, 8.4 Hz), 7.19 (3H, d, J 8.0 Hz), 7.32 (3H, d, J 8.8 Hz), 7.39 (2H, t, J 8.0 Hz), 7.51 (2H, d, J 7.2 Hz), 7.55 (1H, bs), 7.82 (1H, d, J 8.0 Hz). 13C NMR (100 MHz, CDCl3) δ39.89, 40.59, 52.18, 70.79, 79.25, 104.96, 111.08, 116.14, 127.20, 128.11, 128.76, 128.92, 129.61, 133.17, 134.28, 136.56, 137.04, 142.50, 159.65, 166.36, 168.17. νmax (pure sample)/(cm−1) 3329, 1695, 1591, 1549, 1530, 1245, 1090. MS (API-ES): m/z 483 [M+H]+ (100%), HRMS (API-ES) m/z found 483.1236 [M+H]+.

Workup

  1. extractionThe product was extracted with ethyl acetate (2×20 ml)
  2. dry with materialdried over Na2SO4
  3. customthe solvent removed under reduced pressure
  4. temperatureAfter cooling to room temperature
  5. extractionThe product was extracted with ethyl acetate (2×20 ml)
  6. dry with materialdried over Na2SO4
  7. customthe solvent removed under reduced pressure

Sources & evidence

ORD record
ord-11ca6027aae640389e00f09facb71bfd
Source dataset
uspto-grants-2011_06
Patent number
US07960434B2

Reaction notes

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