Benzyl isocyanate → N-(6-Cyano-3,4-dihydro-2,2-dimethyl-2H-1-benzopyran-4-yl)-N'-(phenylmethyl)urea

HRID 129186Notes

Reaction equation

HRID 129186 reaction equation
[C:1]([C:3]1[CH:4]=[CH:5][C:6]2[O:11][C:10]([CH3:13])([CH3:12])[C@@H:9](O)[C@H:8]([N:15](C3C=CN=CC=3)[C:16]([NH2:18])=[O:17])[C:7]=2[CH:25]=1)#[N:2].[CH2:26](N=C=O)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1>C(O)C>[C:1]([C:3]1[CH:4]=[CH:5][C:6]2[O:11][C:10]([CH3:12])([CH3:13])[CH2:9][CH:8]([NH:15][C:16]([NH:18][CH2:26][C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)=[O:17])[C:7]=2[CH:25]=1)#[N:2]

Participants

4

Reactant 2

HCID 76639Benzyl isocyanateHCID 67809575(trans)-1-(6-Cyano-3,4-dihydro-3-hydroxy-2,2-dimethyl-2H-1-benzopyran-4-yl)-(4-pyridinyl)urea

Product 1

HCID 15295557N-(6-Cyano-3,4-dihydro-2,2-dimethyl-2H-1-benzopyran-4-yl)-N'-(phenylmethyl)ureaYield 89.7%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A solution of (-)-4-amino-6-cyano-3,4-dihydro-2,2-dimethyl-2H-1-benzopyran (2.0 g, 9.9 mmole, from Example 19, part B) and benzyl isocyanate (1.32 g, 9.9 mmole) in ethanol (15 ml) under argon was heated at reflux for two hours. The solvent ws recovered under vacuum and the crude product was triturated with isopropyl ether to obtain 2.98 g (89.7%) of the title compound as a pure white solid. m.p.=140°-141° C., [a]D25DMF=-41.2°. 1H NMR (DMSO-d6) δ7.59 (s, 1H), 7.56 (d, J=1.76 Hz, 1H), 7,38-7.22 (m, 5H), 6.89 (d, J=8.21 Hz, 1H), 6.56 (t, J=5.87 Hz, 1H), 6.49 (d, J=8.79 Hz, 1H), 4.94 (m, 1H), 4.30 (d, J=5.87 Hz, 1H), 2.11 (dd, J=6.16 and 13.19 Hz, 1H), 1.74 (d, J=12.32 Hz, 1H), 1.41 (s. 3H), 1.28 (s, 3H). 13C NMR (DMSO-d) δ158.19, 157.27, 140.80, 132.25, 132.15, 128.31, 126.98, 126.69, 126.18, 119.28, 118.13, 102.06. , 77.37, 43.08, 42.01, 37.80, 29.15, 24.47. MS: (M+H)+ @336.

Workup

  1. temperatureat reflux for two hours
  2. customThe solvent ws recovered under vacuum
  3. customthe crude product was triturated with isopropyl ether

Sources & evidence

ORD record
ord-9e11ec84056e44438eda5ca28ff30478
Source dataset
uspto-grants-1995_11
Patent number
US05466817

Reaction notes

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