4-Bromobenzaldehyde → HCID 178501999, compound

HRID 1518047Notes

Reaction equation

HRID 1518047 reaction equation
[NH2:1][C:2]1[C:7]([N+:8]([O-])=O)=[CH:6][C:5]([NH:11][C:12]([O:14][CH3:15])=[O:13])=[CH:4][C:3]=1[N+:16]([O-])=O.C([O-])=O.[NH4+].CN(C(/C=C/C1C[C@H]2C(S([O-])(=O)=O)NC3C=C4OCOC4=CC=3C(=O)N2C=1)=O)C.[Na+].[Br:53][C:54]1[CH:61]=[CH:60][C:57]([CH:58]=O)=[CH:56][CH:55]=1>C(O)C.[Pd]>[NH2:8][C:7]1[C:2]2[NH:1][C:58]([C:57]3[CH:60]=[CH:61][C:54]([Br:53])=[CH:55][CH:56]=3)=[N:16][C:3]=2[CH:4]=[C:5]([NH:11][C:12]([O:14][CH3:15])=[O:13])[CH:6]=1

Participants

7

Reactant 4

HCID 707414-BromobenzaldehydeHCID 2723923Ammonium formateHCID 14762438HCID 14762438, compoundHCID 23678453HCID 23678453, compound

Product 1

HCID 178501999HCID 178501999, compoundYield 201.1%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

To a suspension of 4-amino-3,5-dinitro-1-(methoxycarbonyl)aminobenzene (311 mg, 1.2 mmol) in ethanol (24 mL), was added ammonium formate (1.8 g) and 10% Pd/C (120 mg) under nitrogen. The mixture was stirred at room temperature overnight. The Pd/C and excess ammonium formate were filtered off. The filtrate was treated with the sodium bisulfite adduct of 4-bromobenzaldehyde (715 mg, 0.84 mmol) at 0° C. After the solution was stirred for 12-16 h at room temperature under nitrogen, a trace of insoluble material was removed by filtration and the filtrate was concentrated on a rotary evaporator until approximately 60-70% of the solvent was removed. To the residue an equal volume of ethyl acetate was added, and the mixture was transferred to a separatory funnel. The organic layer was separated, and the water layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo to give the desired product (610 mg, 48% yield) as brown powder: 1H-NMR (300 MHz, CD3OD) δ 3.73 (s, 3H), 6.53 (s, 1H), 7.16 (s, 1H), 7.64 (dd, 2H, J=6.6, 1.8 Hz), 7.88 (dd, 2H, J=6.6, 1.8 Hz); ESI MS m/z 361.0 [M+H]+.

Workup

  1. filtrationThe Pd/C and excess ammonium formate were filtered off
  2. stirringAfter the solution was stirred for 12-16 h at room temperature under nitrogen
  3. customa trace of insoluble material was removed by filtration
  4. concentrationthe filtrate was concentrated on a rotary evaporator until approximately 60-70% of the solvent
  5. customwas removed
  6. additionTo the residue an equal volume of ethyl acetate was added
  7. customthe mixture was transferred to a separatory funnel
  8. customThe organic layer was separated
  9. extractionthe water layer was extracted with ethyl acetate
  10. washThe combined organic layers were washed with brine
  11. dry with materialdried over anhydrous sodium sulfate
  12. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-d130f4c76b9e4effabce6891ccf0fd79
Source dataset
uspto-grants-2012_07
Patent number
US08232410B2

Reaction notes

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