2-(Ethoxymethylene)propanedinitrile → HCID 57438663, compound

HRID 1098211Notes

Reaction equation

HRID 1098211 reaction equation
Cl.[Br:2][C:3]1[CH:4]=[CH:5][C:6]([CH3:11])=[C:7]([NH:9][NH2:10])[CH:8]=1.C(O[CH:15]=[C:16]([C:19]#[N:20])[C:17]#[N:18])C>CO>[NH2:20][C:19]1[N:9]([C:7]2[CH:8]=[C:3]([Br:2])[CH:4]=[CH:5][C:6]=2[CH3:11])[N:10]=[CH:15][C:16]=1[C:17]#[N:18]

Participants

4

Reactant 2

HCID 671522-(Ethoxymethylene)propanedinitrileHCID 22279963(5-Bromo-2-methylphenyl)hydrazine--hydrogen chloride (1/1)

Product 1

HCID 57438663HCID 57438663, compoundYield 94%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

5 (5-Bromo-2-methylphenyl)hydrazine hydrochloride (CAS no. 214915-80-7) (5 g, 21.05 mmol) was partitioned between EtOAc (50 mL) and NaOH (2M, aq) (30 mL). The organic layer separated and washed with water (50 mL), brine (50 mL), dried (MgSO4), filtered and concentrated to afford free base of the starting material. The resultant oil was suspended in MeOH (50 mL) under nitrogen at −5° C. 2-(ethoxymethylene)malononitrile (2.57 g, 21.05 mmol) added portionwise over 5 mins and the mixture stirred at ˜0° C. for 30 mins. The reaction mixture was allowed to warm to room temperature and then heated at reflux under nitrogen for 2 hours. The reaction mixture was allowed to cool and evaporated to dryness to afford the product (5.48 g, 94%). 1H NMR (400 MHz, DMSO) 1.99 (3H, s), 6.59 (2H, s), 7.36 (1H, d), 7.49 (1H, d), 7.60-7.63 (1H, m), 7.76 (1H, s); m/z (ES+) (M+H)+=277+279; HPLC tR=2.01 min.

Workup

  1. custom214915-80-7) (5 g, 21.05 mmol) was partitioned between EtOAc (50 mL) and NaOH (2M, aq) (30 mL)
  2. customThe organic layer separated
  3. washwashed with water (50 mL), brine (50 mL)
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto afford free base of the starting material
  8. temperatureto warm to room temperature
  9. temperatureheated
  10. temperatureat reflux under nitrogen for 2 hours
  11. temperatureto cool
  12. customevaporated to dryness

Sources & evidence

ORD record
ord-a2c3e0dc57ef42d9a890f6c31c1e685f
Source dataset
uspto-grants-2012_03
Patent number
US08143263B2

Reaction notes

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