Sodium Hydroxide → 2-(beta-Cyanoethylaminocarbonyl)-4'-methylbiphenyl

HRID 2352033Notes

Reaction equation

HRID 2352033 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9]([C:14]([OH:16])=O)=[CH:10][CH:11]=[CH:12][CH:13]=2)=[CH:4][CH:3]=1.S(Cl)(Cl)=O.[OH-].[Na+].C(O)(=O)/C=C/C(O)=O.[NH2:31][CH2:32][CH2:33][C:34]#[N:35]>O.C(Cl)(Cl)Cl>[C:32]([CH2:33][CH2:34][NH:35][C:14]([C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][C:8]=1[C:5]1[CH:4]=[CH:3][C:2]([CH3:1])=[CH:7][CH:6]=1)=[O:16])#[N:31]

Participants

7

Reactant 4

HCID 14798Sodium Hydroxide2×HCID 24386Thionyl ChlorideHCID 815682-(4-Methylphenyl)benzoic acidHCID 6433176Propanenitrile, 3-amino-, (2E)-2-butenedioate (1:1)

Product 1

HCID 144256702-(beta-Cyanoethylaminocarbonyl)-4'-methylbiphenylYield 85.8%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6212ChloroformSolvent

Procedure

4'-methylbiphenyl-2-carboxylic acid (50.00 g, 0.236 mol,), thionyl chloride (87.5 ml, 1.20 mol) and chloroform (500 ml) were mixed and refluxed for 4 hours. The thionyl chloride and solvent were removed in vacuo, and the residue suspended in toluene (300 ml). The mixture was evaporated in vacuo and the residue suspended once more in toluene and evaporated to insure removal of traces of thionyl chloride. The resultant acid chloride was dissolved in tetrahydrofuran (100 ml) and slowly added in five equal portions alternatingly with five equal portions of 1.0N NaOH (236.0 ml, 0.236 mol) to a solution of β-aminopropionitrile fumarate (30.3 g, 0.236 mol) in 1.0N NaOH (236.0 ml, 0.236 mol) at 0° with stirring. The reaction was allowed to warm slowly to room temperature. After 24 hrs, water (500 ml) was added and the aqueous mixture extracted with ethyl acetate (3×500 ml). The organic layers were combined and dried (MgSO4), and the solvent removed in vacuo to yield a crude solid which, after recrystallization from methylcyclohexane/butyl chloride, yielded 53.5 g of a white solid. M.P.=102.0°-103.5°. NMR (200MH2, CDCl3) δ:7.68 (d, 1H, J=7Hz); 7.56-7.19 (m, 7H); 5.65 (bm, 1H); 3.43 (d of t, 2H); 2.39 (t, 2H, J=7Hz). Anal. calcd. for C17H16N2O; C, 77.25; H, 6.10; N, 10.60. Found; C, 77.42; H, 6.40; N, 10.68.

Workup

  1. temperaturerefluxed for 4 hours
  2. customThe thionyl chloride and solvent were removed in vacuo
  3. customThe mixture was evaporated in vacuo
  4. customevaporated
  5. customremoval of traces of thionyl chloride
  6. dissolutionThe resultant acid chloride was dissolved in tetrahydrofuran (100 ml)
  7. extractionthe aqueous mixture extracted with ethyl acetate (3×500 ml)
  8. dry with materialdried (MgSO4)
  9. customthe solvent removed in vacuo
  10. customto yield a crude solid which
  11. customafter recrystallization from methylcyclohexane/butyl chloride

Sources & evidence

ORD record
ord-ef650c75cbba49ecaad3c1269420608a
Source dataset
uspto-grants-1989_10
Patent number
US04874867

Reaction notes

Loading…