Ethyl Acetate → HCID 23374174, compound

HRID 865622Notes

Reaction equation

HRID 865622 reaction equation
[CH2:1]([N:8]([C:12]1[CH:17]=[CH:16][C:15]([N+:18]([O-])=O)=[CH:14][CH:13]=1)[C:9]([NH2:11])=[S:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.O.O.Cl[Sn]Cl.CCOC(C)=O>CO>[NH2:18][C:15]1[CH:14]=[CH:13][C:12]([N:8]([CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[C:9]([NH2:11])=[S:10])=[CH:17][CH:16]=1

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 61436Stannous chloride dihydrateHCID 57169013HCID 57169013, compound

Product 1

HCID 23374174HCID 23374174, compoundYield 75%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

In Example 107, reduction of the nitro group in compound 342 by reaction with stannous chloride in methanol proceeded selectively and resulted in the formation of amino derivative 343 in high yield, as follows: A mixture of thiourea 342 (0.287 g, 1 mmol) and SnCl2.2H2O (0.5 g, 2.2 mmol) in MeOH (25 mL) was refluxed for 4 hours, cooled to room temperature, then poured into EtOAc (150 mL. The mixture was sequentially washed with saturated NaHCO3 (5×20 mL) and H2O (3×20 mL), dried over MgSO4, then evaporated. The residue was chromatographed over silica gel (2×15 cm, eluant: 1% MeOH in CHCl3) to produce (4-aminophenyl)-benzyl thiourea 343 (0.192 g, 75% yield) as a white powder. Relevant data: mp 153°-155° C. (from EtOAc); 1H NMR (DMSO-d6): δ4.65 (d, 2H, J=5.7 Hz), 5.05 (br.s., 2H, NH2), 6.50 (d, 2H, J=9 Hz), 6.85 (d, 2H, J=9Hz), 7.25 (m, 5H), 7.61 (br.s., 1H, NH), 9.15 (s, 1H, NH); 13C NMR (DMSO-d6) δ47.50, 114.72, 126.96, 127.23, 127.51, 128.66, 139.57, 146.88, 181.305; MS m/e (1%): 257 (M+, 42), 256 (17), 182 (25), 165 (6), 150 (100), 108 (75), 107 (37), 106 (47), 91 (92).

Workup

  1. temperaturewas refluxed for 4 hours
  2. washThe mixture was sequentially washed with saturated NaHCO3 (5×20 mL) and H2O (3×20 mL)
  3. dry with materialdried over MgSO4
  4. customevaporated
  5. customThe residue was chromatographed over silica gel (2×15 cm, eluant: 1% MeOH in CHCl3)

Sources & evidence

ORD record
ord-ad896dba35284a808d79ce72adf7e910
Source dataset
uspto-grants-1996_10
Patent number
US05567411

Reaction notes

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