Pyridine → 3,4-Dihydro-2,2-dimethyl-4-[2-oxo-3-(phenylmethyl)-1-imidazolidinyl]-2H-1-benzopyran-6-carbonitrile

HRID 1197697Notes

Reaction equation

HRID 1197697 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][CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[C:7]=2[CH:25]=1)#[N:2].Cl[C:27](OC1C=CC([N+]([O-])=O)=CC=1)=[O:28].N1C=CC=CC=1>C(Cl)Cl>[CH3:12][C:10]1([CH3:13])[CH2:9][CH:8]([N:14]2[CH2:15][CH2:16][N:17]([CH2:18][C:19]3[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=3)[C:27]2=[O:28])[C:7]2[CH:25]=[C:3]([C:1]#[N:2])[CH:4]=[CH:5][C:6]=2[O:11]1

Participants

5

Reactant 3

HCID 1049PyridineHCID 821294-Nitrophenyl chloroformateHCID 19373577N-(6-Cyano-2,2-dimethyl-3,4-dihydro-2H-1-benzopyran-4-yl)-N'-benzylethylenediamine

Product 1

HCID 193735823,4-Dihydro-2,2-dimethyl-4-[2-oxo-3-(phenylmethyl)-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-4-yl)-N'-benzylethylenediamine (0.91 g, 2.71 mmole, from Example 22, part A) and 4-nitrophenyl chloroformate (0.57 g, 2.85 mmole) in methylene chloride (22.5 ml) cooled to 0° C. was added pyridine (0.27 g, 3.39 mmole). The reaction mixture was stirred at room temperature for 24 hours, diluted with methylene chloride and washed with 5% aqueous HCl solution, 2N NaOH solution and saturated NaCl solution. The extract was dried over MgSO4 and evaporated in vacuo to obtain 1.32 g of an orange gum. The crude product was chromatographed on silica eluting with hexane/ethyl acetate (3:2) to obtain 0.65 g (66%) of the title compound as a colorless amorphous solid, m.p.=45-48° C. 1H NMR (CDCl3) δ 7.51-7.39 (m, 7H), 6.93 (d, J=9.38 Hz, 1H), 5.43 (dd, J=7.03 and 11.14 Hz, 1H), 4.55 (m, 2H), 3.36-3.20 (m, 3H), 3.05 (m, 1H), 1.99 (m, 2H), 1.59 (s, 3H), 1.45 (S, 3H); 13C NMR (CDCl3) δ 160.77, 158.29, 136.70, 132.49, 131.66, 128.60, 128.03, 127.48, 121.38, 119.16, 118.61, 103.29, 76.94, 48.17, 45.15, 41.90, 37.26, 34.96, 34.67, 29.75, 24.01; MS: (M+H)+ @362.

Workup

  1. washwashed with 5% aqueous HCl solution, 2N NaOH solution and saturated NaCl solution
  2. dry with materialThe extract was dried over MgSO4
  3. customevaporated in vacuo

Sources & evidence

ORD record
ord-1c12fdb6cc634f388bf0292da8c12541
Source dataset
uspto-grants-1994_01
Patent number
US05276168

Reaction notes

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