Ethanol → HCID 59394995, compound

HRID 383363Notes

Reaction equation

HRID 383363 reaction equation
C(=O)([O-])OC[C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[C:7](Br)=[CH:6][C:5]=1[CH:14]1[CH2:18][CH2:17][CH2:16][CH2:15]1.[CH2:21]([N:23]1[CH2:28][CH2:27][NH:26][CH2:25][CH2:24]1)[CH3:22].C(N(CC)CC)C.Cl[C:37]([O:39][CH3:40])=[O:38].C([OH:43])C>ClCCl>[C:37](=[O:43])([O:39][CH3:40])[O:38][C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[C:7]([N:26]2[CH2:27][CH2:28][N:23]([CH2:21][CH3:22])[CH2:24][CH2:25]2)=[CH:6][C:5]=1[CH:14]1[CH2:15][CH2:16][CH2:17][CH2:18]1

Participants

7

Reactant 5

HCID 702EthanolHCID 6586Methyl chloroformateHCID 8471TriethylamineHCID 791961-EthylpiperazineHCID 67535504HCID 67535504, compound

Product 1

HCID 59394995HCID 59394995, compoundYield 76%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of (4-bromo-2-cyclopentyl-5-nitro-phenyl)methyl carbonate (800 mg, 2.33 mmol) and 1-ethylpiperazine (266 mg, 2.33 mmol) in ethanol (2.4 mL) was heated under microwave irradiation at 150° C. for 6 h, resulting in product formation with loss of the carbonate group. The reaction was concentrated in vacuo and the residue was redissolved in dichloromethane, washed with water, dried over Na2SO4, filtered and reconcentrated. The crude product was dissolved in triethylamine (648 μL, 4.65 mmol) and dichloromethane (2 mL), cooled to 0° C. and methyl chloroformate (180 μL, 2.32 mmol) was added dropwise. The reaction was warmed to room temperature and stirred for 2 h. The reaction was quenched with water and the aqueous layer was extracted with dichloromethane. The combined organics were dried over MgSO4, filtered and concentrated. Purification by silica gel chromatography (0-10% ethyl acetate/hexanes) provided 2-cyclopentyl-4-(4-ethylpiperazin-1-yl)-5-nitrophenyl methyl carbonate (672 mg, 76% yield). NMR (400.0 MHz, DMSO-d6) δ 7.66 (d, J=8.6 Hz, 1H), 7.30 (d, J=8.6 Hz, 1H), 3.88 (s, 3H), 3.08-3.06 (m, 1H), 2.88 (s, 4H), 2.34-2.30 (m, 5H), 1.93-1.90 (m, 3H), 1.75-1.72 (m, 2H), 1.65-1.63 (m, 2H), 1.54-1.51 (m, 2H), 1.00 (t, J=7.1 Hz, 3H).

Workup

  1. customresulting in product formation with loss of the carbonate group
  2. concentrationThe reaction was concentrated in vacuo
  3. dissolutionthe residue was redissolved in dichloromethane
  4. washwashed with water
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. customThe reaction was quenched with water
  8. extractionthe aqueous layer was extracted with dichloromethane
  9. dry with materialThe combined organics were dried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customPurification by silica gel chromatography (0-10% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-9b740066fa98495487015188aa4bde27
Source dataset
uspto-grants-2013_02
Patent number
US08367660B2

Reaction notes

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