Dichloromethane → tert-Butyl (5-(aminomethyl)benzo[d]isoxazol-3-yl)carbamate

HRID 1171050Notes

Reaction equation

HRID 1171050 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]1[C:13]2[CH:14]=[C:15]([CH2:18][N:19]3C(=O)C4C(=CC=CC=4)C3=O)[CH:16]=[CH:17][C:12]=2[O:11][N:10]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].O.NN.C(Cl)Cl.CCOC(C)=O>C(O)CCC>[C:1]([O:5][C:6](=[O:7])[NH:8][C:9]1[C:13]2[CH:14]=[C:15]([CH2:18][NH2:19])[CH:16]=[CH:17][C:12]=2[O:11][N:10]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 8857Ethyl AcetateHCID 24654Hydrazine hydrate (1:1)HCID 687689652-[3-(Tert-butoxycarbonyl)amino-benzo[d]isoxazol-5-ylmethyl]-isoindole-1,3-dione

Product 1

HCID 58972904tert-Butyl (5-(aminomethyl)benzo[d]isoxazol-3-yl)carbamate

Reagents, catalysts & solvents 1

HCID 2631-ButanolSolvent

Procedure

A mixture of 2-[3-(tert-butoxycarbonyl)amino-benzo[d]isoxazol-5-ylmethyl]-isoindole-1,3-dione (1.31 g) and hydrazine hydrate (2.52 mL, 52 mmol) in 1-butanol (10 mL) was stirred at room temperature. The mixture turned into a translucent orange solution. After stirring for about 1 hr, white precipitate formed. The mixture was then heated to reflux for 5 min and all solid dissolved. After cooling, DCM was added, after which time white precipitate formed. The solid was filtered off and washed with DCM. Rotary evaporation afforded a yellow oil. The oily residue was taken up with EtOAc (100 mL) and washed with water (3×30 mL), brine (30 mL) and dried over anhydrous sodium sulfate. Most solvent was removed on a rotary evaporator and the remainder was loaded onto a 20 g ISOLUTE silica cartridge. The product was eluted with (2 M ammonia in methanol)/DCM (4:96). A light yellow solid was obtained (330 mg). 1H-NMR (300 MHz, CDCl3) δ 8.05 (s, 1H), 7.53 (d, 1H), 7.45 (d, 1H), 7.31 (s, 1H), 3.40 (s, 2H), 1.57 (s, 9H).

Workup

  1. stirringAfter stirring for about 1 hr
  2. customwhite precipitate formed
  3. temperatureThe mixture was then heated
  4. temperatureto reflux for 5 min
  5. dissolutionall solid dissolved
  6. temperatureAfter cooling
  7. customafter which time white precipitate formed
  8. filtrationThe solid was filtered off
  9. washwashed with DCM
  10. customRotary evaporation
  11. customafforded a yellow oil
  12. washwashed with water (3×30 mL), brine (30 mL)
  13. dry with materialdried over anhydrous sodium sulfate
  14. customMost solvent was removed on a rotary evaporator
  15. washThe product was eluted with (2 M ammonia in methanol)/DCM (4:96)
  16. customA light yellow solid was obtained (330 mg)

Sources & evidence

ORD record
ord-aef9f22877b94d79a9a5ae7685fd460d
Source dataset
uspto-grants-2010_11
Patent number
US07829584B2

Reaction notes

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