Malononitrile → 2-Cyano-thioacetimidic acid 4-methoxy-benzyl ester

HRID 1266350Notes

Reaction equation

HRID 1266350 reaction equation
[OH-].[Na+].[CH3:3][O:4][C:5]1[CH:12]=[CH:11][C:8]([CH2:9][SH:10])=[CH:7][CH:6]=1.[C:13](#[N:17])[CH2:14][C:15]#[N:16]>C(O)C.O.[NH4+].[Cl-].O>[CH3:3][O:4][C:5]1[CH:12]=[CH:11][C:8]([CH2:9][S:10][C:13](=[NH:17])[CH2:14][C:15]#[N:16])=[CH:7][CH:6]=1

Participants

7

Reactant 3

HCID 8010MalononitrileHCID 14798Sodium HydroxideHCID 804074-Methoxy-alpha-toluenethiol

Product 1

HCID 205771932-Cyano-thioacetimidic acid 4-methoxy-benzyl esterYield 60.2%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 25517Ammonium ChlorideSolventHCID 19096565Water ethanolSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of sodium hydroxide (13 g, 0.32 mol) in 750 mL of 1:1 ethanol-water at 0° C. was added 4-methoxybenzylmercaptan (50 g, 0.324 mol) and malononitrile (21 g, 0.324 mol). After stirring for 3 hours at 0° C., the mixture was diluted with 500 mL of saturated aqueous NH4Cl, diluted with 4 l of water and filtered. The solids were washed with ether, and the filtrated was diluted with an equal volume of hexane and filtered. The combined solids were dried in vacuo, affording 43 g (60%) of 2-cyano-thioacetimidic acid 4-methoxy-benzyl ester as a colorless solid. 1H NMR (400 MHz, CDCl3) δ 7.22 (d, 2H, J=7.6 Hz), 6.84 (d, 2H, J=8.8 Hz), 4.74 (bs, 1H), 3.98 (s, 2H), 3.78 (s, 3H) ppm; MS (APCl, m/z): 221 [M+H]+.

Workup

  1. filtrationfiltered
  2. washThe solids were washed with ether
  3. additionthe filtrated was diluted with an equal volume of hexane
  4. filtrationfiltered
  5. customThe combined solids were dried in vacuo

Sources & evidence

ORD record
ord-c18fca4f388846b4b4e0f981dab5909f
Source dataset
uspto-grants-2003_04
Patent number
US06548526B2

Reaction notes

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