Hydrochloric Acid → Ranisen

HRID 434783Notes

Reaction equation

HRID 434783 reaction equation
O1CCO[CH:2]1[C:6]1[O:10][C:9]([CH2:11][S:12][CH2:13][CH2:14][NH:15][C:16]([NH:21][CH3:22])=[CH:17][N+:18]([O-:20])=[O:19])=[CH:8][CH:7]=1.Cl.[CH3:24][NH:25][CH3:26].Cl.CNC.C([BH3-])#N.[Na+]>O.C(O)C>[CH3:24][N:25]([CH2:2][C:6]1[O:10][C:9]([CH2:11][S:12][CH2:13][CH2:14][NH:15][C:16]([NH:21][CH3:22])=[CH:17][N+:18]([O-:20])=[O:19])=[CH:8][CH:7]=1)[CH3:26]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 674DimethylamineHCID 10473Dimethylamine, hydrochlorideHCID 5003444Sodium cyanoborohydrideHCID 70483416HCID 70483416, compound

Product 1

HCID 5039RanisenYield 107.9%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent3×

Procedure

To a stirred solution of N-[2-[[5-(1,3-dioxolan-2-yl)-2-furanylmethyl]thio]ethyl]-N'-methyl-2-nitro-1,1-ethenediamine (1.65 g) and dimethylamine hydrochloride (16.3 g) in water (3.74 ml) and ethanol (6.2 ml) was added 2 N hydrochloric acid (3.74 ml). After 15 min. at room temperature, a solution of dimethylamine in water (40%) (0.85 ml) was added followed by a solution of sodium cyanoborohydride (0.156 g) in water (1 ml). After 1h, the solution was evaporated in vacuo and to the oily residue was added acetic acid (0.5 ml). After 10 min., tetrahydrofuran (100 ml) and an excess of anhydrous sodium carbonate were added, the mixture heated to boiling and allowed to cool to room temperature. After standing for 3 h, the mixture was filtered and the combined filtrate and washings evaporated to low bulk in vacuo. Decolourising charcoal was added to the hot solution and after 1h, the mixture was filtered. The filtrate was evaporated to give an oil (1.7 g) which was chromatographed on silica using methanol:0.88 ammonia (79:1) to give an oil which was dissolved in ethanol. The solution was filtered and evaporated to give an oil (0.75 g) which was crystallised from methyl isobutyl ketone to yield the title compound (0.27 g), m.p. 68°-69.5° which was not depressed on admixture with a sample prepared according to the method of Example 15 in British Patent Specification No. 1,565,966.

Workup

  1. customAfter 1h, the solution was evaporated in vacuo and to the oily residue
  2. additionwas added acetic acid (0.5 ml)
  3. waitAfter 10 min.
  4. additiontetrahydrofuran (100 ml) and an excess of anhydrous sodium carbonate were added
  5. temperaturethe mixture heated
  6. waitAfter standing for 3 h
  7. filtrationthe mixture was filtered
  8. customthe combined filtrate and washings evaporated to low bulk in vacuo
  9. additionDecolourising charcoal was added to the hot solution
  10. filtrationafter 1h, the mixture was filtered
  11. customThe filtrate was evaporated

Sources & evidence

ORD record
ord-17ee50c35de14a84b75a6e306336cafe
Source dataset
uspto-grants-1983_08
Patent number
US04399294

Reaction notes

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