3-Fluorobenzaldehyde → HCID 74763779, compound

HRID 1054322Notes

Reaction equation

HRID 1054322 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][C:5]([NH2:8])=[N:6][CH:7]=1.[F:9][C:10]1[CH:11]=[C:12]([CH:15]=[CH:16][CH:17]=1)[CH:13]=O.O.C1(C)C=CC(S(O)(=O)=O)=CC=1.[N+:30]([CH2:32][C:33]([O:35][CH3:36])=[O:34])#[C-:31]>CO.CCCCCC>[CH3:36][O:35][C:33](=[O:34])[CH2:32][NH:30][C:31]1[N:6]2[CH:7]=[C:2]([F:1])[CH:3]=[CH:4][C:5]2=[N:8][C:13]=1[C:12]1[CH:15]=[CH:16][CH:17]=[C:10]([F:9])[CH:11]=1

Participants

7

Reactant 4

HCID 680093-FluorobenzaldehydeHCID 521998p-Toluenesulfonic acid monohydrateHCID 547815Methyl isocyanoacetateHCID 27377012-Amino-5-fluoropyridine

Product 1

HCID 74763779HCID 74763779, compoundYield 30.5%

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 8058HexaneSolvent

Procedure

5-Fluoropyridin-2-amine (200 mg, 1.78 mmol, Eq: 1.00), 3-fluorobenzaldehyde (240 mg, 205 μL, 1.87 mmol, Eq: 1.05) and p-toluenesulfonic acid monohydrate (102 mg, 535 μmol, Eq: 0.3) were dissolved in MeOH (2.5 mL) and the yellow solution was stirred for 10 min. To this yellow solution was added dropwise methyl 2-isocyanoacetate (182 mg, 167 μL, 1.78 mmol, Eq: 1.00) and the corresponding brown solution was stirred for 90 min. Hexane (2 mL) was added and the solvent was removed to give a beige gummy residue. To this residue, MeOH (2 mL) was added and the precipitate was filtered off, washed with MeOH (4 mL) and dried under vacuum to give the product as an off-white solid (172 mg, 30.4%). MS: 318.2 [M+H]+; 1H-NMR (CDCl3): δ 8.23 (m, 1H), 7.78-7.75 (m, 2H), 7.54 (m, 1H), 7.43 (m, 1H), 7.15-7.00 (m, 2H), 3.84 (d, 2H), 3.77 (s, 3H), 3.73 (m, 1H).

Workup

  1. stirringthe corresponding brown solution was stirred for 90 min
  2. customthe solvent was removed
  3. customto give a beige gummy residue
  4. filtrationthe precipitate was filtered off
  5. washwashed with MeOH (4 mL)
  6. customdried under vacuum

Sources & evidence

ORD record
ord-9708266096f84aff82ba6a18be6779db
Source dataset
uspto-grants-2016_07
Patent number
US09394304B2

Reaction notes

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