Sodium Hydroxide → 5-Amino-2-[3-(1-adamantyl)-4-benzyloxyphenyl]pyrimidine

HRID 508654Notes

Reaction equation

HRID 508654 reaction equation
[C:1]12([C:11]3[CH:12]=[C:13]([C:25]4[N:30]=[CH:29][C:28]([N+:31]([O-])=O)=[CH:27][N:26]=4)[CH:14]=[CH:15][C:16]=3[O:17][CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2.O.O.Cl[Sn]Cl.[OH-].[Na+].C([O-])(O)=O.[Na+]>CCO.O>[NH2:31][C:28]1[CH:27]=[N:26][C:25]([C:13]2[CH:14]=[CH:15][C:16]([O:17][CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)=[C:11]([C:1]34[CH2:2][CH:3]5[CH2:9][CH:7]([CH2:6][CH:5]([CH2:4]5)[CH2:10]3)[CH2:8]4)[CH:12]=2)=[N:30][CH:29]=1

Participants

7

Reactant 4

HCID 14798Sodium HydroxideHCID 61436Stannous chloride dihydrateHCID 516892Sodium BicarbonateHCID 532600862-[3-(1-Adamantyl)-4-benzyloxyphenyl]-5-nitropyrimidine

Product 1

HCID 532600875-Amino-2-[3-(1-adamantyl)-4-benzyloxyphenyl]pyrimidineYield 35%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

A solution of 2-[3-(1-adamantyl)-4-benzyloxyphenyl]-5-nitropyrimidine (163 mg, 0.37 mmol) and SnCl2.2H2O (418 mg, 1.85 mmol) in anhydrous EtOH (1.7 mL) was heated at 90° C. (oil-bath) for 3.3 h, cooled to room temperature and diluted with H2O (2 mL). After adjustment of the pH to 7-8 by addition of 2 N NaOH (1.6 mL) and 5% NaHCO3 (3 mL), the resulting mixture was stirred for 40 min and extracted with EtOAc (3×30 mL). The extract was washed (brine) and dried. After solvent removal at reduced pressure, the residue was chromatographed (25% EtOAc/hexane) to give 53 mg (35%) of 5-amino-2-[3′-(1-adamantyl)-4′-benzyloxyphenyl]pyrimidine as a light-purple solid, mp 216-219° C. IR 3424, 2900, 1182 cm−1; 1H NMR (CDCl3) 1.76 (bs, 6H, AdCH2), 2.08 (bs, 3H, AdCH), 2.24 (m, 6H, AdCH2), 3.74 (bs, 2H, NH2), 5.21 (s, 2H, C6H5CH2), 7.04 (d, J=8.7 Hz, 1H, 5′-ArH), 7.34-7.56 (m, 5H, C6H5), 8.13 (dd, J=8.7 Hz, 2.4 Hz, 1H, 6′-ArH), 8.28 (d, J=2.4 Hz, 1H, 2′-ArH), 8.43 ppm (s, 2H, 4-ArH, 6-ArH). HRMS calcd C27H29N3O [M+H]+ 412.2389. found 412.2391.

Workup

  1. extractionextracted with EtOAc (3×30 mL)
  2. washThe extract was washed (brine)
  3. customdried
  4. customAfter solvent removal at reduced pressure
  5. customthe residue was chromatographed (25% EtOAc/hexane)

Sources & evidence

ORD record
ord-8edfd9ba436d4800809b19736de31d3c
Source dataset
uspto-grants-2015_08
Patent number
US09096544B2

Reaction notes

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