Hydrazine hydrate (1:1) → HCID 71270800, compound

HRID 510399Notes

Reaction equation

HRID 510399 reaction equation
[C:1]1([CH2:11][CH:12]([C:15]#[N:16])[C:13]#[N:14])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1.O.[NH2:18][NH2:19]>C(O)C>[C:1]1([CH2:11][C:12]2[C:13]([NH2:14])=[N:18][NH:19][C:15]=2[NH2:16])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1

Participants

4

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 15747440HCID 15747440, compound

Product 1

HCID 71270800HCID 71270800, compoundYield 57.2%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a mixture of malononitrile (1.32 g, 20 mmol) in Ethanol (50 mL) and Water (2.50 mL) was added 1-naphthalenecarbaldehyde (3.12 g, 20 mmol). The reaction was stirred at rt for 7 days. The mixture was cooled to 0° C. in an ice bath. Sodium borohydride (0.204 g, 5.40 mmol) was introduced to the vigorously stirred mixture and the reduction was complete in about 10 min. To the reaction mixture was added water (20 mL). 1N HCl was added in to quench the excess hydride. More water was added in until precipitation was complete. Filtration gave (1-naphthalenylmethyl)propanedinitrile (3.3 g, 80%). To a solution of (1-naphthalenylmethyl)propanedinitrile (3.3 g, 16 mmol) in Ethanol (80 mL) was added hydrazine hydrate (0.785 mL, 16.00 mmol). The mixture was 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 (2.18 g, 57%). 1H NMR (400 MHz, DMSO-d6) δ ppm 3.96 (s, 2H) 7.26 (d, J=7.07 Hz, 1H) 7.31-7.44 (m, 1H) 7.45-7.58 (m, 2H) 7.74 (d, J=8.08 Hz, 1H) 7.85-7.97 (m, 1H) 8.12-8.26 (m, 1H) 10.05 (bs, 1H). LC/MS: MS (ES+) m/e 239.0 [M+H]+.

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux temperature for 8 h
  3. concentrationThe reaction mixture was concentrated
  4. customThe crude material was purified on a silica column (MeOH/DCM: 0˜10%)

Sources & evidence

ORD record
ord-61aa7e12895346f68664d0b34e58ac9e
Source dataset
uspto-grants-2015_08
Patent number
US09096605B2

Reaction notes

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