Ammonia → HCID 59152911, compound

HRID 1645141Notes

Reaction equation

HRID 1645141 reaction equation
[CH2:1]([O:3][C:4](=[O:17])[CH2:5][N:6]1[C:14]2[CH2:13][CH2:12][CH2:11][C:10](=[N:15]O)[C:9]=2[CH:8]=[N:7]1)[CH3:2].C([BH3-])#N.[Na+].C([O-])(=O)C.[NH4+].N.[Cl-].[NH4+]>CO.[Cl-].[Ti+3].[Cl-].[Cl-].O>[CH2:1]([O:3][C:4](=[O:17])[CH2:5][N:6]1[C:14]2[CH2:13][CH2:12][CH2:11][CH:10]([NH2:15])[C:9]=2[CH:8]=[N:7]1)[CH3:2]

Participants

9

Reactant 5

HCID 222AmmoniaHCID 25517Ammonium ChlorideHCID 517165Ammonium AcetateHCID 5003444Sodium cyanoborohydrideHCID 72541900HCID 72541900, compound

Product 1

HCID 59152911HCID 59152911, compound

Reagents, catalysts & solvents 3

HCID 10313229titanium(III) trichlorideCatalystHCID 887MethanolSolventHCID 962WaterSolvent

Procedure

To a solution of (4-hydroxyimino-4,5,6,7-tetrahydro-indazol-1-yl)-acetic acid ethyl ester (132 mg, 0.59 mmol), sodium cyanoborohydride (110 mg, 1.76 mmol), and ammonium acetate (0.5 g, 7.2 mmol) in methanol (10 mL) was added titanium (III) chloride (0.99 mL, 20% wt in water, 1.68 mmol) dropwise. The reaction mixture was stirred at room temperature for 2 hours under an argon atmosphere. To the above mixture were added water (10 mL) and a solution of concentrated ammonia and saturated ammonium chloride (10 mL, 1:5, v/v). The resulting mixture was filtered through a pad of Celite® (a diatomite filter from World Minerals Inc.) and washed with dichloromethane (30 mL). The separated aqueous layer was extracted with dichloromethane (20 mL×3). The combined organic layers were washed with brine (30 mL), dried over sodium sulfate and concentrated in vacuo to afford 4-amino-4,5,6,7-tetrahydro-indazol-1-yl)-acetic acid ethyl ester (131 mg, 99%) as a viscous light brown oil. 1H NMR (400 MHz, CD3OD) δ ppm 7.76 (s, 1 H), 5.34 (s, 2 H), 4.60 (m, 2 H), 4.34 (m, 2 H), 2.70 (m, 2 H), 2.20 (m, 1 H), 1.98 (m, 3 H), 1.32 (t, J=7.2 Hz, 3 H). MS calcd. for C11H17N3O2 223, obsd. (ESI+) [(M+H)+] 224.

Workup

  1. filtrationThe resulting mixture was filtered through a pad of Celite® (a diatomite
  2. filtrationfilter from World Minerals Inc
  3. wash) and washed with dichloromethane (30 mL)
  4. extractionThe separated aqueous layer was extracted with dichloromethane (20 mL×3)
  5. washThe combined organic layers were washed with brine (30 mL)
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated in vacuo
  8. customto afford 4-amino-4,5,6,7-tetrahydro-indazol-1-yl)-acetic acid ethyl ester (131 mg, 99%) as a viscous light brown oil

Sources & evidence

ORD record
ord-fe05b539a9154ee5a2f83493eb016715
Source dataset
uspto-grants-2012_02
Patent number
US08124641B2

Reaction notes

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