3-Chlorobenzaldehyde → HCID 74763784, compound

HRID 1054327Notes

Reaction equation

HRID 1054327 reaction equation
[Br:1][C:2]1[C:3]([NH2:9])=[N:4][CH:5]=[C:6]([Cl:8])[CH:7]=1.[Cl:10][C:11]1[CH:12]=[C:13]([CH:16]=[CH:17][CH:18]=1)[CH:14]=O.O.C1(C)C=CC(S(O)(=O)=O)=CC=1.[N+:31]([C:33]([CH3:36])([CH3:35])[CH3:34])#[C-:32]>CO>[Br:1][C:2]1[C:3]2[N:4]([C:32]([NH:31][C:33]([CH3:36])([CH3:35])[CH3:34])=[C:14]([C:13]3[CH:16]=[CH:17][CH:18]=[C:11]([Cl:10])[CH:12]=3)[N:9]=2)[CH:5]=[C:6]([Cl:8])[CH:7]=1

Participants

6

Reactant 4

HCID 114773-ChlorobenzaldehydeHCID 23577Tert-Butyl isocyanideHCID 521998p-Toluenesulfonic acid monohydrateHCID 27639713-Bromo-5-chloropyridin-2-amine

Product 1

HCID 74763784HCID 74763784, compoundYield 12.1%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

3-bromo-5-chloropyridin-2-amine (200 mg, 964 μmol, Eq: 1.00), 3-chlorobenzaldehyde (142 mg, 115 μl, 1.01 mmol, Eq: 1.05) and p-toluenesulfonic acid monohydrate (55.0 mg, 289 μmol, Eq: 0.3) were dissolved in MeOH (1.5 mL) and the intensive yellow solution was stirred for 5 min. To this yellow solution was added dropwise 2-isocyano-2-methylpropane (80.1 mg, 110 μL, 964 μmol, Eq: 1.00) and the corresponding yellow solution was stirred for 3 h. The solvent was removed and the oily residue was treated with dichloromethane and filtered over a cartridge. Two fractions were taken. From fraction 1 the product crystallized after treatment with DMSO-d6. The crystals were filtered off, washed with water and dried under high vacuum to yield the product (48 mg, 12.1%). LC/MS (acid polar): 413.0 [M]+; 1H-NMR (CDCl3): δ 8.62 (s, 1H), 8.26 (s, 1H), 8.17 (d, 1H), 7.65 (s, 1H), 7.43 (t, 1H), 7.34 (d, 1H), 4.91 (s, 1H), 1.03 (s, 9H).

Workup

  1. stirringthe corresponding yellow solution was stirred for 3 h
  2. customThe solvent was removed
  3. additionthe oily residue was treated with dichloromethane
  4. filtrationfiltered over a cartridge
  5. customFrom fraction 1 the product crystallized after treatment with DMSO-d6
  6. filtrationThe crystals were filtered off
  7. washwashed with water
  8. customdried under high vacuum

Sources & evidence

ORD record
ord-7f3c852c8dae4902b6bb6b660595ed1b
Source dataset
uspto-grants-2016_07
Patent number
US09394304B2

Reaction notes

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