Ammonia → HCID 86666946, compound

HRID 511025Notes

Reaction equation

HRID 511025 reaction equation
[C:1]([C:4]1[C:5]([O:23][CH3:24])=[C:6]([CH:12]2[CH2:15][N:14]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:13]2)[C:7]([Cl:11])=[C:8]([Cl:10])[CH:9]=1)(=O)[CH3:2].C(O)C.[BH4-].[Na+].[NH3:30]>CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].[Ti+4]>[NH2:30][CH:1]([C:4]1[C:5]([O:23][CH3:24])=[C:6]([CH:12]2[CH2:15][N:14]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:13]2)[C:7]([Cl:11])=[C:8]([Cl:10])[CH:9]=1)[CH3:2]

Participants

6

Reactant 4

HCID 222AmmoniaHCID 702EthanolHCID 4311764Sodium borohydrideHCID 86666945HCID 86666945, compound

Product 1

HCID 86666946HCID 86666946, compoundYield 97%

Reagents, catalysts & solvents 1

HCID 11026Titanium isopropoxideCatalyst

Conditions

Temperature
60 °C

Procedure

A solution of tert-butyl 3-(3-acetyl-5,6-dichloro-2-methoxyphenyl)azetidine-1-carboxylate (1.0 g, 2.7 mmol) in 2.0 M ammonia in ethanol (13 mL, 27 mmol) at 0° C. was treated with titanium tetraisopropoxide (1.6 mL, 5.3 mmol) and stirred at 60° C. overnight. The reaction mixture was treated with sodium tetrahydroborate (0.15 g, 4.0 mmol) at 0° C. and the solution was stirred at room temperature for another 1 hour. The reaction mixture was quenched with 2 M ammonia in water and filtered. The solid was washed with acetonitrile. The filtrate was concentrated and the residue was diluted with dichloromethane, washed with water, dried with magnesium sulfate, filtered, and concentrated to give the desired product (1.0 g, 97%) that was used without further purification. LCMS for C13H14Cl2NO3 (M−[NH2]-[t-Bu]+H)+: m/z=302.0, 304.0. Found: 301.9, 304.0.

Workup

  1. stirringthe solution was stirred at room temperature for another 1 hour
  2. customThe reaction mixture was quenched with 2 M ammonia in water
  3. filtrationfiltered
  4. washThe solid was washed with acetonitrile
  5. concentrationThe filtrate was concentrated
  6. additionthe residue was diluted with dichloromethane
  7. washwashed with water
  8. dry with materialdried with magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-11f842dc2f134659b9fac317111643dc
Source dataset
uspto-grants-2015_08
Patent number
US09096600B2

Reaction notes

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