1,2-Dichloroethane → HCID 87106358, compound

HRID 713697Notes

Reaction equation

HRID 713697 reaction equation
[N+:1]([C:4]1[N:9]=[C:8]([CH2:10][C:11]([OH:13])=O)[CH:7]=[CH:6][CH:5]=1)([O-:3])=[O:2].CCN(C(C)C)C(C)C.C1C=CC2N(O)N=NC=2C=1.Cl.[CH3:34][NH:35][O:36][CH3:37].C(Cl)CCl>ClCCl>[CH3:37][O:36][N:35]([CH3:34])[C:11](=[O:13])[CH2:10][C:8]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:1]([O-:3])=[O:2])[N:9]=1

Participants

7

Reactant 5

HCID 111,2-DichloroethaneHCID 757711-HydroxybenzotriazoleHCID 81138Methanamine, N-methoxy-, hydrochloride (1:1)HCID 81531DiisopropylethylamineHCID 66685143HCID 66685143, compound

Product 1

HCID 87106358HCID 87106358, compoundYield 76.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a suspension of 250 mg (1.37 mmol) of (6-nitropyridin-2-yl) acetic acid in 6 mL of dichloromethane was added DIEA (0.72 mL, 4.12 mmol) which resulted in some exotherming (+5° C.) and the suspension becoming a solution. After 2 min cooling, HOBt (263 mg, 1.72 mmol), N,O-dimethylhydroxylamine HCl (167 mg, 1.72 mmol) was added to the solution followed by EDC (329 mg, 1.72 mmol) and the resulting mixture stirred at room temperature overnight under nitrogen atmosphere. The solution was transferred to a separatory funnel and washed with 1 M HCl which caused an emulsion. Methanol was added to break up the emulsion and the aqueous was partitioned off. The organics were dried over sodium sulfate, filtered and concentrated under vacuum. Purification via preparative TLC plate (2×1000 μM) eluting with 50% ethyl acetatehexane afforded the title compound (236 mg, 76%) as a white solid. LC-MS: C9H11N3O4 calculated 225.20 found m/z (ES) 226 (MH)+. 1HNMR (500 MHz, DMSO) δ:8.56 (d, J=2.0 Hz, 1H), 8.25 (d, J=8.4 Hz, 1H), 8.04 (dd, J=2.0, 8.3 Hz, 1H), 4.02 (br s, 2H), 3.88 (s, 3H), 3.07 (s, 3H).

Workup

  1. customresulted in some exotherming (+5° C.)
  2. temperatureAfter 2 min cooling
  3. customThe solution was transferred to a separatory funnel
  4. washwashed with 1 M HCl which
  5. additionMethanol was added
  6. customthe aqueous was partitioned off
  7. dry with materialThe organics were dried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under vacuum
  10. customPurification via preparative TLC plate (2×1000 μM)
  11. washeluting with 50% ethyl acetatehexane

Sources & evidence

ORD record
ord-e0b31d6b8ff14c768fc8c5b9edea876b
Source dataset
uspto-grants-2015_11
Patent number
US09186354B2

Reaction notes

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