Formaldehyde → HCID 68629339, compound

HRID 1182718Notes

Reaction equation

HRID 1182718 reaction equation
[Br:1][C:2]1[N:11]2[C:5]([CH2:6][NH:7][CH2:8][C:9]3[CH:15]=[C:14]([Cl:16])[CH:13]=[CH:12][C:10]=32)=[N:4][N:3]=1.C=O.[C:19]([BH3-])#N.[Na+]>CO>[Br:1][C:2]1[N:11]2[C:5]([CH2:6][N:7]([CH3:19])[CH2:8][C:9]3[CH:15]=[C:14]([Cl:16])[CH:13]=[CH:12][C:10]=32)=[N:4][N:3]=1

Participants

5

Reactant 3

HCID 712FormaldehydeHCID 5003444Sodium cyanoborohydrideHCID 67363168HCID 67363168, compound

Product 1

HCID 68629339HCID 68629339, compoundYield 30.4%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A mixture of 1-bromo-8-chloro-5,6-dihydro-4H-2,3,5,10b-tetraaza-benzo[e]azulene (1.9 g, 6.4 mmol) and paraformaldehyde (1.5 g, 51 mmol) in methanol (64 ml) was heated at reflux for 16 h. After cooling to 0° C. sodium cyanoborohydride (0.8 g, 13 mmol) was added. The reaction mixture was allowed to warm to room temperature and stirred for 3 h. After quenching with 1 M aqueous sodium hydroxide solution (200 ml) the aqueous layer was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated in vacuo. Flash chromatography over aminopropyl-modified silica gel with n-heptane/ethyl acetate as eluent gave the title compound (0.61 g) as white solid with a purity of ca. 85% as assessed by 1H-NMR. MS m/e: 313 (M+H+).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 16 h
  3. additionwas added
  4. customAfter quenching with 1 M aqueous sodium hydroxide solution (200 ml) the aqueous layer
  5. extractionwas extracted with ethyl acetate
  6. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-f7bd9bd0a989408992d8c0ec69ad584e
Source dataset
uspto-grants-2014_03
Patent number
US08664216B2

Reaction notes

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