Acetic Acid → 4-Fluorobenzylamine

HRID 1025529Notes

Reaction equation

HRID 1025529 reaction equation
ClC1C=CC2[N:6]=C(N)N=C(OCC)C=2N=1.[F:16][C:17]1[CH:24]=[CH:23][C:20]([CH:21]=O)=[CH:19][CH:18]=1.C(O)(=O)C.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+]>ClCCCl>[F:16][C:17]1[CH:24]=[CH:23][C:20]([CH2:21][NH2:6])=[CH:19][CH:18]=1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 680234-FluorobenzaldehydeHCID 5049666Sodium triacetoxyborohydrideHCID 597672176-Chloro-4-ethoxypyrido[3,2-d]pyrimidin-2-amine

Product 1

HCID 673264-FluorobenzylamineYield 50%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

A mixture of 6-chloro-4-ethoxy-pyrido[3,2-d]pyrimidin-2-ylamine (0.22 g), 4-fluorobenzaldehyde (2.0 mmol), acetic acid 5.0 mmol) and molecular sieves (10 mg) in DCE (3 mL) was stirred at room temperature for 30 minutes. NaBH(OAc)3 was added portion by portion. The mixture was stirred for 16 hours, and then quenched by adding saturated aqueous NaHCO3. The solution was partitioned with DCM. The organic layer was dried over Na2SO4 and concentrated to afford the crude product which was purified by flash chromatography using hexane/ethyl acetate as eluting solvent. 0.33 g of 6-chloro-4-ethoxy-pyrido[3,2-d]pyrimidin-2-yl)-(4-fluoro-benzyl)-amine (Example 61) was obtained (yield: 50%) as a white solid which was characterized by its mass spectrum as follows: MS (m/z) 333.1 [M+H]+.

Workup

  1. stirringThe mixture was stirred for 16 hours
  2. customquenched
  3. additionby adding saturated aqueous NaHCO3
  4. customThe solution was partitioned with DCM
  5. dry with materialThe organic layer was dried over Na2SO4
  6. concentrationconcentrated
  7. customto afford the crude product which
  8. customwas purified by flash chromatography
  9. washas eluting solvent

Sources & evidence

ORD record
ord-034dc67e77274ae6bd1bbd8f47a7c2d1
Source dataset
uspto-grants-2014_05
Patent number
US08729089B2

Reaction notes

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