Methanol → Ammonia

HRID 1020261Notes

Reaction equation

HRID 1020261 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:18]=[CH:19][C:20]=1[Cl:21])[CH2:5][NH:6][C:7]([NH:9][C:10]1[S:11][CH:12]=[C:13]([CH2:15][NH:16][CH3:17])[N:14]=1)=[O:8].[CH3:22][O:23][C:24]1[CH:31]=[C:30]([O:32][CH3:33])[CH:29]=[CH:28][C:25]=1[CH:26]=O.C([BH3-])#N.[Na+].CO>C(Cl)Cl.C(O)(=O)C>[NH3:6].[Cl:1][C:2]1[CH:3]=[C:4]([CH:18]=[CH:19][C:20]=1[Cl:21])[CH2:5][NH:6][C:7]([NH:9][C:10]1[S:11][CH:12]=[C:13]([CH2:15][N:16]([CH2:26][C:25]2[CH:28]=[CH:29][C:30]([O:32][CH3:33])=[CH:31][C:24]=2[O:23][CH3:22])[CH3:17])[N:14]=1)=[O:8]

Participants

8

Reactant 4

HCID 887MethanolHCID 691752,4-DimethoxybenzaldehydeHCID 5003444Sodium cyanoborohydrideHCID 25052051HCID 25052051, compound

Product 2

HCID 222AmmoniaHCID 86622760HCID 86622760, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidCatalystHCID 6344DichloromethaneSolvent3×

Procedure

1-(3,4-Dichloro-benzyl)-3-(4-methylaminomethyl-thiazol-2-yl)-urea (Example 132) was taken up in DCM with 1.5 equivalents of 2,4-Dimethoxy-benzaldehyde and several drops of acetic acid. Reaction was stirred for several hours at ambient temperature. Sodium cyanoborohydride (1.5 equivalents) was added at once and the reaction was stirred overnight at ambient temperature. An aqueous work-up with dichloromethane and chromatography (silica, DCM, 0-10% MeOH saturated with NH3) afforded the title compound. 1H NMR (400 MHz, DMSO-d6): 10.65 (br s, 1H), 7.60 (d, 1H), 7.54 (d, 1H), 7.29 (dd, 1H), 7.27 (br d, 1H), 7.12 (br s, 1H), 6.58 (br s, 1H), 6.56-6.46 (m, 2H), 4.33 (d, 2H), 3.75 (s, 6H), 3.46 (br s, 4H), 2.12 (br s, 3H). MS (ES+): M/Z 495 and 497 (M+1).

Workup

  1. customReaction
  2. stirringwas stirred overnight at ambient temperature

Sources & evidence

ORD record
ord-34ed187ebcf6441aa4d80021bec25bdd
Source dataset
uspto-grants-2014_05
Patent number
US08716320B2

Reaction notes

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