4-Nitroaniline → HCID 57169013, compound

HRID 865621Notes

Reaction equation

HRID 865621 reaction equation
[N-:1]=[C:2]=[S:3].[N+:4]([C:7]1[CH:13]=[CH:12][C:10]([NH2:11])=[CH:9][CH:8]=1)([O-:6])=[O:5].N[CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>>[CH2:15]([N:11]([C:10]1[CH:12]=[CH:13][C:7]([N+:4]([O-:6])=[O:5])=[CH:8][CH:9]=1)[C:2]([NH2:1])=[S:3])[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1

Participants

4

Reactant 3

HCID 74754-NitroanilineHCID 7504BenzylamineHCID 178418790HCID 178418790, compound

Product 1

HCID 57169013HCID 57169013, compoundYield 76%

Procedure

In Example 106, reaction of compound 340 with aminomethylbenzene 341 yielded the model compound 342 containing a thiourea linkage, as follows: To a solution of isothiocyanate 340 (1.80 g, 10 mol, prepared in Example 105 from the p-nitro aniline 339), benzylamine 341 (1.64 mL, 15 mmol) was added dropwise. The resulting mixture was stirred for 16 hours, then evaporated. The solid residue was washed on a filter sequentially with 2N HCl (5×10 mL), and H2O (5×5 mL), then dried in vacuo to produce a crude product that was crystallized from EtOAc to yield 2.190 g (76% yield) of benzyl-(4-nitrophenyl) thiourea 342 as an orange powder. Relevant data: mp 151°-152° C. (from EtOAc); 1H NMR (DMSO-d6): δ4.74 (s, 2H), 7.34 (m, 5H), 7.84 (d, 2H, J=9 Hz), 8.15 (d, 2H, J=9 Hz), 8.65 (s, 1H, NH), 10.21 (s, 1H, NH); 13C NMR (DMSO-d6): δ48.17, 121.62, 125.34, 128.04, 128.55, 129.30, 139.11, 142.92, 147.28, 181.36; MS m/e (1%): 287 (M+, 22), 180 (100), 150 (51), 138 (21), 122 (43), 106 (81), 107 (56), 91 (95).

Workup

  1. additionwas added dropwise
  2. customevaporated
  3. washThe solid residue was washed on
  4. filtrationa filter sequentially with 2N HCl (5×10 mL), and H2O (5×5 mL)
  5. customdried in vacuo
  6. customto produce a crude product that
  7. customwas crystallized from EtOAc

Sources & evidence

ORD record
ord-db374d1610da4b05a4c4574910e2c75c
Source dataset
uspto-grants-1996_10
Patent number
US05567411

Reaction notes

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