Cesium carbonate → 4-chloro-N,N-bis(4-methoxybenzyl)-6-methyl-1,3,5-triazin-2-amine

HRID 1621420Notes

Reaction equation

HRID 1621420 reaction equation
[C:1](=[O:4])([O-])[O-].[Cs+].[Cs+].[Cl:7][C:8]1[N:13]=[C:12]([CH3:14])[N:11]=[C:10]([NH2:15])[N:9]=1.Cl[CH2:17][C:18]1[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[CH:20][CH:19]=1>CN(C=O)C.CCOC(C)=O>[Cl:7][C:8]1[N:13]=[C:12]([CH3:14])[N:11]=[C:10]([N:15]([CH2:17][C:18]2[CH:23]=[CH:22][C:21]([O:4][CH3:1])=[CH:20][CH:19]=2)[CH2:17][C:18]2[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[CH:20][CH:19]=2)[N:9]=1

Participants

6

Reactant 3

HCID 10796Cesium carbonate2×HCID 305914-Chloro-6-methyl-1,3,5-triazin-2-amineHCID 699934-Methyloxybenzyl chloride2×

Product 1

HCID 595482094-chloro-N,N-bis(4-methoxybenzyl)-6-methyl-1,3,5-triazin-2-amineYield 115.3%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

Cesium carbonate (0.860 mL, 10.74 mmol) was added to a mixture of 4-chloro-6-methyl-1,3,5-triazin-2-amine (1.10 g, 7.61 mmol) and 1-(chloromethyl)-4-methoxybenzene (1.10 mL, 8.11 mmol) in DMF (8.0 mL) at rt. After 40 min, more 1-(chloromethyl)-4-methoxybenzene (1.10 mL, 8.11 mmol) was added. After another 1 h, more cesium carbonate (0.860 mL, 10.74 mmol) was added. After another 30 min, the mixture was diluted with EtOAc (30 mL) and filtered through a pad of Celite® (diatomaceous earth). The filtrate was transferred to a separatory funnel, diluted with more EtOAc, and washed with water (3×20 mL). The organic layer was dried over Na2SO4 and concentrated. The resulting slurry was filtered and washed with 1:1 hexane-EtOAc. The filtrate was purified by chromatography on silica using 5 to 100% DCM in hexane to give the product as a soft white solid (1.8 g). LCMS (ES, pos.): cacld for C20H21ClN4O2: 384.1. found: 385.1 (M+H)+. 1H NMR (400 MHz, CDCl3) δ 7.16 (t, J=8.12 Hz, 4H); 6.81-6.95 (m, 4H); 4.74 (s, 2H); 4.69 (s, 2H); 3.81 (s, 6H); 2.45 (s, 3H).

Workup

  1. waitAfter another 1 h
  2. waitAfter another 30 min
  3. filtrationfiltered through a pad of Celite® (diatomaceous earth)
  4. customThe filtrate was transferred to a separatory funnel
  5. additiondiluted with more EtOAc
  6. washwashed with water (3×20 mL)
  7. dry with materialThe organic layer was dried over Na2SO4
  8. concentrationconcentrated
  9. filtrationThe resulting slurry was filtered
  10. washwashed with 1:1 hexane-EtOAc
  11. customThe filtrate was purified by chromatography on silica using 5 to 100% DCM in hexane

Sources & evidence

ORD record
ord-bb1f0ba343ce427fb95de466e1c2d474
Source dataset
uspto-grants-2014_07
Patent number
US08772480B2

Reaction notes

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