Piperonal → HCID 22462985, compound

HRID 1936961Notes

Reaction equation

HRID 1936961 reaction equation
[N+:1]([CH2:3][CH2:4][C:5]1[CH:10]=[CH:9][C:8]([O:11][CH3:12])=[C:7]([O:13][CH3:14])[CH:6]=1)#[C-:2].[CH:15]1[C:20]([CH:21]=O)=[CH:19][C:18]2[O:23][CH2:24][O:25][C:17]=2[CH:16]=1.C([O-])=[O:27].[NH4+:29]>CO>[NH2:29][CH:21]([C:20]1[CH:15]=[CH:16][C:17]2[O:25][CH2:24][O:23][C:18]=2[CH:19]=1)[C:2]([NH:1][CH2:3][CH2:4][C:5]1[CH:10]=[CH:9][C:8]([O:11][CH3:12])=[C:7]([O:13][CH3:14])[CH:6]=1)=[O:27]

Participants

5

Reactant 3

HCID 8438PiperonalHCID 4498002-(3,4-dimethoxyphenyl)ethyl isocyanideHCID 2723923Ammonium formate

Product 1

HCID 22462985HCID 22462985, compoundYield 82%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of 4.78 g (25.0 mmol) 4-(2-isocyano-ethyl)-1,2-dimethoxy-benzene, 4.5 g (30 mmol) piperonal, 3.15 g (50 mmol) ammonium formiate in 25 ml methanol (which has been previously purged by a nitrogen stream) is heated at reflux for 18 hours. The solution is cooled to 0° C. and 10 ml HCl 10M in methanol is added. The reaction mixture is stirred at RT for 10 hours. The mixture is then extracted with 2 fold 150 ml ice-cooled water. The water phase is made basic by the addition of NaOH 2N (pH=14) and is extracted with ethyl acetate. 7.33 g (82%) 2-amino-2-benzo[1,3]dioxol-5-yl-N-[2-(3,4-dimethoxy-phenyl)-ethyl]acetamide is isolated as an orange oil which is further reacted without purification. 1.9 g (5.3 mmol) 2-amino-2-benzo[1,3]dioxol-5-yl-N-[2-(3,4-dimethoxy-phenyl)-ethyl]-acetamide is dissolved in 20 ml THF and cooled to 0° C. 0.8 ml (7.42 mmol) N,N-dimethyl-sulfamoyl chloride and 2.22 ml (15.9 mmol) triethylamine are added and the mixture is stirred 15 hours at RT. After dilution with ethyl acetate, the mixture is extracted with ice-cooled water. Evaporation of the solvent give an oil which is crystallized in toluene to give 1.08 g (44%) 2-benzo[1,3]dioxol-5-yl-N-[2-(3,4-dimethoxy-phenyl)-ethyl]-2-(N′,N′-dimethylsulfamido)-acetamide (cmpd. Tab.14,B.241) as a white solid (m.p. 137.5-139° C.). From the mother liquor 0.85 g (35%) compound is further isolated.

Workup

  1. customhas been previously purged by a nitrogen stream)
  2. temperatureis heated
  3. temperatureat reflux for 18 hours
  4. addition10 ml HCl 10M in methanol is added
  5. extractionThe mixture is then extracted with 2 fold 150 ml ice-
  6. temperaturecooled water
  7. additionThe water phase is made basic by the addition of NaOH 2N (pH=14)
  8. extractionis extracted with ethyl acetate

Sources & evidence

ORD record
ord-032c6ad5aada422bbc9e99ffbd212b7b
Source dataset
uspto-grants-2002_05
Patent number
US06391918B1

Reaction notes

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