Hydrochloric Acid → HCID 58204645, compound

HRID 2044352Notes

Reaction equation

HRID 2044352 reaction equation
[F:1][C:2]([F:26])([F:25])[CH2:3][N:4]1[C:8]([C:9]2[CH:10]=[C:11]3[N:17]([N:18]=2)[C:16]2[CH:19]=[C:20]([CH:23]=O)[CH:21]=[CH:22][C:15]=2[O:14][CH2:13][CH2:12]3)=[N:7][CH:6]=[N:5]1.[N:27]1([CH2:33][CH2:34][OH:35])[CH2:32][CH2:31][NH:30][CH2:29][CH2:28]1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].Cl.C(OCC)C>ClCCCl.C(Cl)Cl.CO.C(O)(=O)C>[F:26][C:2]([F:1])([F:25])[CH2:3][N:4]1[C:8]([C:9]2[CH:10]=[C:11]3[N:17]([C:16]4[CH:19]=[C:20]([CH2:23][N:30]5[CH2:31][CH2:32][N:27]([CH2:33][CH2:34][OH:35])[CH2:28][CH2:29]5)[CH:21]=[CH:22][C:15]=4[O:14][CH2:13][CH2:12]3)[N:18]=2)=[N:7][CH:6]=[N:5]1

Participants

10

Reactant 5

HCID 313Hydrochloric AcidHCID 3283Diethyl EtherHCID 76771-(2-Hydroxyethyl)piperazineHCID 5049666Sodium triacetoxyborohydrideHCID 58204289HCID 58204289, compound

Product 1

HCID 58204645HCID 58204645, compound

Reagents, catalysts & solvents 4

HCID 111,2-DichloroethaneSolventHCID 176Acetic AcidSolventHCID 887MethanolSolventHCID 6344DichloromethaneSolvent2×

Procedure

A solution of 2-[2-(2,2,2-trifluoro-ethyl)-2H-[1,2,4]triazol-3-yl]-4,5-dihydro-6-oxa-1,10b-diaza-benzo[e]azulene-9-carbaldehyde (175 mg, 0.48 mmol) and piperazine ethanol in DCE (15 mL) was treated with sodium triacetoxyborohydride (153 mg, 0.72 mmol) and catalytic acetic acid and then stirred at RT for 72 h. The resultant mixture was diluted with DCM and washed with saturated aqueous sodium hydrogen carbonate then dried (Na2SO4), filtered and concentrated in vacuo to give a colourless gum which was subjected to flash chromatography (SiO2, gradient 0-10% MeOH in DCM). The appropriate fractions were combined, concentrated in vacuo and the resultant residue dissolved in diethyl ether and treated with 1M HCl in diethyl ether (2 mL, 2 mmol). The resultant precipitate was filtered off, washed with ether and dried in vacuo to give 128 as a white solid. 1H NMR (DMSO-d6 plus deuterated TFA, 400 MHz): δ 8.22 (s, 1H); 8.16-8.12 (m, 1H); 7.66-7.60 (m, 1H); 7.39 (d, J=8.3 Hz, 1H); 7.02 (s, 1H); 5.75 (q, J=8.7 Hz, 2H); 4.57 (t, J=5.9 Hz, 2H); 4.52 (s, 2H); 3.76 (t, J=5.0 Hz, 2H); 3.61 (br s, 8H); 3.32 (s, 2H); 3.24 (t, J=5.9 Hz, 2H). 1 Exchangeable not observed. LCMS: RT=6.56 min, M+H+=478

Workup

  1. washwashed with saturated aqueous sodium hydrogen carbonate
  2. dry with materialthen dried (Na2SO4)
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customto give a colourless gum which
  6. concentrationconcentrated in vacuo
  7. dissolutionthe resultant residue dissolved in diethyl ether
  8. filtrationThe resultant precipitate was filtered off
  9. washwashed with ether
  10. customdried in vacuo

Sources & evidence

ORD record
ord-8c3931e8215f40b4bb708dd3e698726b
Source dataset
uspto-grants-2013_11
Patent number
US08586574B2

Reaction notes

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