Urea → 3,5-Dichloro-4(4'-methoxy-3'-(6-methoxy-3-pyridylmethyl)phenylthio)benzonitrile

HRID 1761615Notes

Reaction equation

HRID 1761615 reaction equation
N([O-])=O.[Na+].[Cl:5][C:6]1[CH:7]=[C:8]([CH:10]=[C:11]([Cl:31])[C:12]=1[S:13][C:14]1[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[C:16]([CH2:22][C:23]2[CH:24]=[N:25][C:26]([O:29][CH3:30])=[CH:27][CH:28]=2)[CH:15]=1)N.[NH2:32][C:33](N)=O.[C-]#N.[Na+].C([O-])(=O)C.[Na+]>O.C(O)(=O)C.S(=O)(=O)(O)O.C(Cl)(Cl)Cl>[Cl:5][C:6]1[CH:7]=[C:8]([CH:10]=[C:11]([Cl:31])[C:12]=1[S:13][C:14]1[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[C:16]([CH2:22][C:23]2[CH:24]=[N:25][C:26]([O:29][CH3:30])=[CH:27][CH:28]=2)[CH:15]=1)[C:33]#[N:32]

Participants

10

Reactant 5

HCID 1176UreaHCID 8929Sodium CyanideHCID 517045Sodium AcetateHCID 146735393,5-Dichloro-4-(4'-methoxy-3'-(6-methoxy-3-pyridylmethyl)phenylthio) anilineHCID 23668193Sodium Nitrite

Product 1

HCID 146735403,5-Dichloro-4(4'-methoxy-3'-(6-methoxy-3-pyridylmethyl)phenylthio)benzonitrile

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 962WaterSolvent2×HCID 1118Sulfuric AcidSolventHCID 6212ChloroformSolvent

Procedure

A solution of sodium nitrite (2.19 g) in water (20 ml) was added dropwise to a cooled (10°) solution of 3,5-dichloro-4-(4'methoxy-3'-(6-methoxy-3-pyridylmethyl) phenylthio) aniline (8.94 g) in glacial acetic acid (50 ml) and concentrated sulphuric acid (2.6 ml) with stirring. After 10 minutes urea (1.0 g) was added and this cool solution added from a dropping funnel to a cooled (5°) suspension of cuprous cyanide (19.0 g) and sodium cyanide (10.4 g) in water (260 ml) keeping the temperature of the mixture below 10°. This mixture was stirred vigorously whilst allowing to warm to room temperature and then heated at 60° for 0.5 hour. After cooling chloroform (250 ml) and sodium acetate (10 g) were added. The organic layer was separated and the aqueous re-extracted with chloroform. The combined organic extracts were washed with water (four times), dried over anhydrous magnesium sulphate and evaporated to afford a red solid which was chromatographed on silica gel using ethyl acetate-petroleum spirit (60-80, gradient elution) as eluant. 3,5-Dichloro-4(4'-methoxy-3'-(6-methoxy-3-pyridylmethyl)phenylthio)benzonitrile was obtained as a pale yellow solid (4.20 g, 46%), m.p. 147°-150°.

Workup

  1. additionthis cool solution added from a dropping funnel to
  2. temperaturea cooled
  3. customthe temperature of the mixture below 10°
  4. stirringThis mixture was stirred vigorously
  5. temperatureheated at 60° for 0.5 hour
  6. additionwere added
  7. customThe organic layer was separated
  8. extractionthe aqueous re-extracted with chloroform
  9. washThe combined organic extracts were washed with water (four times)
  10. dry with materialdried over anhydrous magnesium sulphate
  11. customevaporated
  12. customto afford a red solid which
  13. customwas chromatographed on silica gel

Sources & evidence

ORD record
ord-b22132b24981434da2f3062eecec2c3c
Source dataset
uspto-grants-1989_05
Patent number
US04826876

Reaction notes

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