Hydrochloric Acid → HCID 60102483, compound

HRID 510409Notes

Reaction equation

HRID 510409 reaction equation
[C:1](#[N:5])[CH2:2][C:3]#[N:4].[Cl:6][C:7]1[C:14]([Cl:15])=[CH:13][CH:12]=[CH:11][C:8]=1[CH:9]=O.[BH4-].[Na+].Cl>C(O)C.O>[Cl:6][C:7]1[C:14]([Cl:15])=[CH:13][CH:12]=[CH:11][C:8]=1[CH2:9][CH:2]([C:1]#[N:5])[C:3]#[N:4]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8010MalononitrileHCID 357452,3-DichlorobenzaldehydeHCID 4311764Sodium borohydride

Product 1

HCID 60102483HCID 60102483, compoundYield 87.3%

Reagents, catalysts & solvents 2

HCID 702EthanolSolvent2×HCID 962WaterSolvent

Procedure

To a mixture of malononitrile (2.64 g, 40 mmol) in 95% Ethanol (50 mL) was added 2,3-dichlorobenzaldehyde (7.00 g, 40.0 mmol). The reaction was stirred at rt for 18 h. EtOH (20 mL) was added and the mixture was stirred at rt for 20 min and cooled to 0° C. in an ice bath. Sodium borohydride (0.424 g, 11.20 mmol) was introduced to the vigorously stirred mixture and the reduction was complete in about 10 min. To the reaction mixture was added water (40 mL). 1N HCl was added in to quench the excess hydride. More water was added in until precipitation was complete. Filtration gave [(2,3-dichlorophenyl)methyl]propanedinitrile (7.86 g, 87%). To a solution of [(2,3-dichlorophenyl)methyl]propanedinitrile (7.86 g, 34.9 mmol) in Ethanol (80 mL) was added hydrazine hydrate (2.57 mL, 52.4 mmol). The mixture is heated at reflux temperature for 8 h. The reaction mixture was concentrated. The crude material was purified on a silica column (MeOH/DCM: 0˜10%) to give the product (4.2 g, 47%). 1H NMR (400 MHz, METHANOL-d4) δ ppm 3.77 (s, 2H) 7.09 (m, 1H) 7.19 (t, J=7.96 Hz, 1H) 7.38 (m, 1H); LC/MS: MS (ES+) m/e 257.0 [M+H]+.

Workup

  1. stirringthe mixture was stirred at rt for 20 min
  2. temperaturecooled to 0° C. in an ice bath
  3. waitthe reduction was complete in about 10 min
  4. customto quench the excess hydride
  5. additionMore water was added in until precipitation
  6. filtrationFiltration

Sources & evidence

ORD record
ord-838d63a27c5f42bca00ad6da576d4342
Source dataset
uspto-grants-2015_08
Patent number
US09096605B2

Reaction notes

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