3-Chlorobenzaldehyde → HCID 74762708, compound

HRID 1054328Notes

Reaction equation

HRID 1054328 reaction equation
[Br:1][C:2]1[C:3]([CH3:9])=[CH:4][C:5]([NH2:8])=[N:6][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.O>[Br:1][C:2]1[C:3]([CH3:9])=[CH:4][C:5]2[N:6]([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:8]=2)[CH:7]=1

Participants

7

Reactant 4

HCID 114773-ChlorobenzaldehydeHCID 23577Tert-Butyl isocyanideHCID 521998p-Toluenesulfonic acid monohydrateHCID 8176952-Amino-5-bromo-4-methylpyridine

Product 1

HCID 74762708HCID 74762708, compoundYield 35.2%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

5-bromo-4-methylpyridin-2-amine (200 mg, 1.07 mmol, Eq: 1.00), 3-chlorobenzaldehyde (158 mg, 128 μl, 1.12 mmol, Eq: 1.05) and p-toluenesulfonic acid monohydrate (61.0 mg, 321 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 (88.9 mg, 122 μL, 1.07 mmol, Eq: 1.00) and the corresponding yellow solution was stirred for 3 h. To the reaction solution was added water dropwise, leading to a milky suspension (product oiled out). The water/MeOH phase was removed and the oily residue was treated with MeOH (1 mL) and dropwise addition of water. Again a milky suspension was formed and the product oiled out. Upon standing for an hour crystals formed from the oily phase. The crystals were filtered off and washed with water and MeOH, dried under high vacuum to yield the product (148 mg, 35.2%). MS: 394.1 [M+H]+; 1H-NMR (D6-DMSO): δ 8.62 (s, 1H), 8.27 (s, 1H), 8.16 (d, 1H), 7.51 (s, 1H), 7.44 (t, 1H), 7.34 (d, 1H), 4.77 (s, 1H), 2.40 (s, 3H), 1.03 (s, 9H).

Workup

  1. stirringthe corresponding yellow solution was stirred for 3 h
  2. customThe water/MeOH phase was removed
  3. additionthe oily residue was treated with MeOH (1 mL) and dropwise addition of water
  4. customAgain a milky suspension was formed
  5. waitUpon standing for an hour
  6. customcrystals formed from the oily phase
  7. filtrationThe crystals were filtered off
  8. washwashed with water and MeOH
  9. customdried under high vacuum

Sources & evidence

ORD record
ord-fe9ea39d2c3e4496a79cb74212322c0e
Source dataset
uspto-grants-2016_07
Patent number
US09394304B2

Reaction notes

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