Ammonia → AC-7739 free base

HRID 585319Notes

Reaction equation

HRID 585319 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5](/[CH:13]=[CH:14]\[C:15]2[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[C:17]([N+:23]([O-])=O)[CH:16]=2)[CH:6]=[C:7]([O:11][CH3:12])[C:8]=1[O:9][CH3:10].N.C([O-])=O.[NH4+]>C(#N)C.[Pd]>[CH3:22][O:21][C:18]1[CH:19]=[CH:20][C:15](/[CH:14]=[CH:13]\[C:5]2[CH:6]=[C:7]([O:11][CH3:12])[C:8]([O:9][CH3:10])=[C:3]([O:2][CH3:1])[CH:4]=2)=[CH:16][C:17]=1[NH2:23]

Participants

6

Reactant 3

HCID 222AmmoniaHCID 2723923Ammonium formateHCID 10617491(Z)-1,2,3-trimethoxy-5-(4-methoxy-3-nitrostyryl)benzene5×

Product 1

HCID 9796936AC-7739 free base

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 6342AcetonitrileSolvent

Procedure

A solution was prepared by dissolving (Z)-3,4,4′,5-tetramethoxy-3′-nitrostilbene (raw material 5) represented by the above formula (5) (5.0 g, 14.5 mmol in total including 14% of the trans-isomer) in acetonitrile (58 mL) followed by addition of 10% palladium on carbon (water-content: 51.3%, 633 mg, 0.29 mmol as palladium), aqueous ammonia (29%, 0.85 g, 14.5 mmol) and ammonium formate (95%, 2.88 g, 43.4 mmol, 300 mole % to the total of the above nitrostilbene derivative (raw material 5) and the trans-isomer thereof) to be subjected to a reaction at 30° C. for 28 hours. At the conclusion of the reaction, the catalyst and the insoluble matter were separated by filtration followed by analysis of the filtrate by HPLC. The resultant peak areas shown at a detection wavelength of 242 nm were 72%, 13%, 1.3%, 0.6%, 11% and 1.6%, respectively, for the (Z)-2-methoxy-5-[2-(3,4,5-trimethoxyphenyl)vinyl]aniline as the objective substance (objective substance 6; represented by the above formula (6)), by-products (E)-2-methoxy-5-[2-(3,4,5-trimethoxyphenyl)vinyl]aniline (by-product 7; represented by the above formula (7)), 2-methoxy-5-[2-(3,4,5-trimethoxyphenyl)ethyl]aniline (by-product 8; represented by the above formula (8)) and 2-(4-methoxy-3-nitrophenyl)-1-(3,4,5-trimethoxyphenyl)ethane (by-product 9; represented by the above formula (9)), the nitrostilbene derivative as the starting material (raw material 5), and the trans-isomer of the raw material 5. In consideration that the starting material contained 14% of the trans-isomer, it was understood that isomerization from the cis-isomer to the trans-isomer was trifling during the reaction.

Workup

  1. customA solution was prepared
  2. customthe trans-isomer thereof) to be subjected to a reaction at 30° C. for 28 hours
  3. customAt the conclusion of the reaction
  4. customthe catalyst and the insoluble matter were separated by filtration
  5. customwas trifling during the reaction

Sources & evidence

ORD record
ord-14867075a95a498c9fc35bac1f9d2444
Source dataset
uspto-grants-2005_08
Patent number
US06930205B2

Reaction notes

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