Hydrochloric Acid → HCID 86641294, compound

HRID 1841908Notes

Reaction equation

HRID 1841908 reaction equation
[N+:1]([C:4]1[CH:31]=[CH:30][C:7]([CH2:8][CH:9]([P:20](=[O:29])([O:25][CH2:26][CH:27]=[CH2:28])[O:21][CH2:22][CH:23]=[CH2:24])[P:10](=[O:19])([O:15][CH2:16][CH:17]=[CH2:18])[O:11][CH2:12][CH:13]=[CH2:14])=[CH:6][CH:5]=1)([O-])=O.[NH4+].[Cl-].Cl.C([O-])(O)=O.[Na+]>CO.[Zn].CCOC(C)=O>[NH2:1][C:4]1[CH:5]=[CH:6][C:7]([CH2:8][CH:9]([P:20](=[O:29])([O:25][CH2:26][CH:27]=[CH2:28])[O:21][CH2:22][CH:23]=[CH2:24])[P:10](=[O:19])([O:15][CH2:16][CH:17]=[CH2:18])[O:11][CH2:12][CH:13]=[CH2:14])=[CH:30][CH:31]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 25517Ammonium ChlorideHCID 516892Sodium BicarbonateHCID 86641293HCID 86641293, compound

Product 1

HCID 86641294HCID 86641294, compoundYield 86.5%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 887MethanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of nitroarene 26 (460 mg, 0.98 mmol) in MeOH (9 mL) was added saturated aqueous NH4Cl solution (3 mL) and zinc powder (319 mg, 4.88 mmol). 15 drops of aqueous 1N HCl were added and the reaction was stirred at room temperature for 18 h. EtOAc and saturated NaHCO3 aqueous solution were added and the mixture was filtered through celite. The filtrate was transferred into an extraction funnel and the layers were separated. The aqueous layer was extracted with EtOAc (2×). The combined organic layers were washed with saturated NaCl solution once, dried over MgSO4, filtered and concentrated. The crude product was purified by flash chromatography on silica gel using a gradient of 0-5% MeOH in CH2Cl2 as eluant to provide aminobenzyl bisphosphonate 27 as a clear yellow oil (374 mg, 86%). 1H NMR (400 MHz, CDCl3) δ 2.69 (tt, J=24.0, 6.1 Hz, 1H), 3.18 (dt, J=16.7, 6.2 Hz, 2H), 4.46-4.60 (m, 8H), 5.19-5.22 (m, 4H), 5.29-5.35 (m, 4H), 5.84-5.94 (m, 4H), 6.60 (d, J=8.6 Hz, 2H), 7.06 (d, J=8.4 Hz, 2H).

Workup

  1. filtrationthe mixture was filtered through celite
  2. customThe filtrate was transferred into an extraction funnel
  3. customthe layers were separated
  4. extractionThe aqueous layer was extracted with EtOAc (2×)
  5. washThe combined organic layers were washed with saturated NaCl solution once
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude product was purified by flash chromatography on silica gel using a gradient of 0-5% MeOH in CH2Cl2 as eluant

Sources & evidence

ORD record
ord-58bf3b13ee6a49fe9058bd20c39858c9
Source dataset
uspto-grants-2015_02
Patent number
US08946144B2

Reaction notes

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