Ethyl 2-amino-2-(2-(6-(benzo[d]thiazol-6-ylamino)-4-(isopropylamino)nicotinoyl)hydrazono)acetate → N2-(benzo[d]thiazol-6-yl)-N4-isopropyl-5-(4H-1,2,4-triazol-3-yl)pyridine-2,4-diamine

HRID 595390Notes

Reaction equation

HRID 595390 reaction equation
[NH2:1][C:2](=[N:8][NH:9][C:10](=O)[C:11]1[C:16]([NH:17][CH:18]([CH3:20])[CH3:19])=[CH:15][C:14]([NH:21][C:22]2[CH:30]=[CH:29][C:25]3[N:26]=[CH:27][S:28][C:24]=3[CH:23]=2)=[N:13][CH:12]=1)C(OCC)=O>CO>[S:28]1[C:24]2[CH:23]=[C:22]([NH:21][C:14]3[CH:15]=[C:16]([NH:17][CH:18]([CH3:20])[CH3:19])[C:11]([C:10]4[NH:1][CH:2]=[N:8][N:9]=4)=[CH:12][N:13]=3)[CH:30]=[CH:29][C:25]=2[N:26]=[CH:27]1

Participants

3

Reactant 1

HCID 123505650Ethyl 2-amino-2-(2-(6-(benzo[d]thiazol-6-ylamino)-4-(isopropylamino)nicotinoyl)hydrazono)acetate

Product 1

HCID 178456791N2-(benzo[d]thiazol-6-yl)-N4-isopropyl-5-(4H-1,2,4-triazol-3-yl)pyridine-2,4-diamine

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
180 °C

Procedure

Ethyl 2-amino-2-(2-(6-(benzo[d]thiazol-6-ylamino)-4-(isopropylamino)nicotinoyl)hydrazono)acetate (7) (300 mg, 0.679 mmol) was taken in a sealed tube and heated at 180° C. for 1 h. The reaction mass was dissolved in methanol then concentrated. The crude material obtained was purified by flash column chromatography through silica gel and MeOH: CHCl3 as eluting agents. The material was further purified by prep HPLC to obtain N2-(benzo[d]thiazol-6-yl)-N4-isopropyl-5-(4H-1,2,4-triazol-3-yl)pyridine-2,4-diamine. 1H NMR: 400 MHz, CD3OD: δ 1.32 (d, J=4.00 Hz, 6H), 1.43 (t, J=6.80 Hz, 3H), 3.72-3.74 (m, 1H), 4.41 (q, J=6.80 Hz, 2H), 6.17 (s, 1H), 7.48 (dd, J=2.40, 8.8 Hz, 1H), 7.93 (d, J=8.80 Hz, 1H), 8.33 (s, 1H), 8.61 (s, 1H), 9.02 (s, 1H). LC/MS: Ascentis Express C18, 5×2.1 mm-2.7 μm; Solvent A=2% ACN: 98% H2O: 10 mM NH4COOH; Solvent B=98% ACN: 2% H2O: 10 mM NH4COOH; gradient 0-100% B over 3 min; retention time: 1.789 min; LCMS (ES-API), m/z 422.0 (M−H). HPLC: XBridge (150×4.6 mm), 3.5 micron; Solvent A=5% ACN: 95% H2O: 0.05% TFA pH=2.5; Solvent B=95% ACN: 5% H2O: 0.05% TFA pH=2.5; gradient 0-100% B over 15 min (23 min run time); Flow rate: 1.0 μL/min; Retention time: 7.569 min; Purity: 99%.

Workup

  1. concentrationthen concentrated
  2. customThe crude material obtained
  3. customwas purified by flash column chromatography through silica gel and MeOH
  4. washCHCl3 as eluting agents
  5. customThe material was further purified by prep HPLC

Sources & evidence

ORD record
ord-d6e4a5646afd41999575cd49375ca659
Source dataset
uspto-grants-2016_01
Patent number
US09242975B2

Reaction notes

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