Triethylamine → 3,4-Dihydro-2,2-dimethyl-4-(2-oxo-3-phenyl-1-imidazolidinyl)-2H-1-benzopyran-6-carbonitrile

HRID 129189Notes

Reaction equation

HRID 129189 reaction equation
[C:1]([C:3]1[CH:4]=[CH:5][C:6]2[O:11][C:10]([CH3:13])([CH3:12])[CH2:9][CH:8]([NH:14][CH2:15][CH2:16][NH:17][C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[C:7]=2[CH:24]=1)#[N:2].C(N(CC)CC)C.Cl[C:33](OC1C=CC([N+]([O-])=O)=CC=1)=[O:34]>C(Cl)Cl>[CH3:12][C:10]1([CH3:13])[CH2:9][CH:8]([N:14]2[CH2:15][CH2:16][N:17]([C:18]3[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=3)[C:33]2=[O:34])[C:7]2[CH:24]=[C:3]([C:1]#[N:2])[CH:4]=[CH:5][C:6]=2[O:11]1

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 821294-Nitrophenyl chloroformateHCID 19373592N-(6-Cyano-2,2-dimethyl-3,4-dihydro-2H-1-benzopyran-4-yl)-N'-phenylethylenediamine

Product 1

HCID 193735783,4-Dihydro-2,2-dimethyl-4-(2-oxo-3-phenyl-1-imidazolidinyl)-2H-1-benzopyran-6-carbonitrile

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of N-(6-cyano-2,2-dimethyl-3,4-dihydro-2H-1-benzopyran-4yl)-N'-phenylethylene-diamine (0.36 g, 1.12 mmole, from Example 21, part A) and triethylamine (0.12 g, 1.18 mmole) in methylene chloride (4 ml) cooled to 0° C. was added a solution of 4-nitrophenyl chloroformate (0.24 g, 1.18 mmole) dissolved in methylene chloride (3 ml). The reaction mixture was stirred at room temperature for four hours. The solvent was evaporated in vacuo and the residue was partitioned between ethyl acetate and 5% aqueous HCl solution. The organic phase was washed with 2N NaOH solution, saturated NaCl solution, dried over MgSO4 and solvent evaporated to obtain 420 mg of an orange gum. The crude product was chromatographed on silica eluting with hexane/ethyl acetate (4:1) to obtain 0.30 g of the title compound as a pure white solid. m.p.=166°-168° C. 1H NMR (DMSO-d6) δ7.61 (m, 4H), 7.35 (m,2H), 7.03 (m, 1H), 6.95 (d, J=8.21 Hz, 1H), 5.21 (dd, J=6.45 and 11.73 Hz, 1H), 3.88 (m, 2H), 3.36 (m 1H), 3.14 (m, 1H), 2.03 (m, 2H), 1.47 (s, 3H), 1.33 (s, 3H); 13C NMR (DMSO-d6) δ158.08, 157.13, 140.58, 132.86, 131.56, 128.63, 121.86, 121.63, 119.15, 118.52, 117.05, 102.54, 77.31, 44.68, 42.06, 36.56, 34.06, 29.36, 24.01; MS: (M+H)+ @348.

Workup

  1. customThe solvent was evaporated in vacuo
  2. customthe residue was partitioned between ethyl acetate and 5% aqueous HCl solution
  3. washThe organic phase was washed with 2N NaOH solution, saturated NaCl solution
  4. dry with materialdried over MgSO4 and solvent
  5. customevaporated

Sources & evidence

ORD record
ord-14f0bb5bc0274e5f87dea1e3dcc24e82
Source dataset
uspto-grants-1995_11
Patent number
US05466817

Reaction notes

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