Nitrogen → 2,2-dimethyl-6-cyano-3,4-dihydro-2H-1,3-benzoxazin-4-one

HRID 1087373Notes

Reaction equation

HRID 1087373 reaction equation
N1C=CC=CC1=[O:7].[H-].[Na+].N#N.[CH3:12][C:13]1([CH3:26])[N:18]=[C:17](Cl)[C:16]2[CH:20]=[C:21]([C:24]#[N:25])[CH:22]=[CH:23][C:15]=2[O:14]1.C(C1C=CC(O)=C(C=1)C(N)=O)#N>CN(C=O)C.CC(C)=O>[CH3:12][C:13]1([CH3:26])[NH:18][C:17](=[O:7])[C:16]2[CH:20]=[C:21]([C:24]#[N:25])[CH:22]=[CH:23][C:15]=2[O:14]1

Participants

8

Reactant 5

HCID 947NitrogenHCID 88712-PyridoneHCID 24758Sodium hydrideHCID 147215875-Cyano-2-hydroxybenzamideHCID 147215882,2-dimethyl-4-chloro-6-cyano-2H-1,3-benzoxazine

Product 1

HCID 108219722,2-dimethyl-6-cyano-3,4-dihydro-2H-1,3-benzoxazin-4-one

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 6228DimethylformamideSolvent

Procedure

1.9 g of 1H-2-pyridone are added to a stirred slurry of 741 mg of NaH (80%) in 40 ml of dry DMF while passing N2 into the flask. After the mixture has been stirred for 0.5 hour, 2.2 g of 2,2-dimethyl-4-chloro-6-cyano-2H-1,3-benzoxazine ("IIa"; m.p. 127°-129°; obtainable by condensing 5-cyano-2-hydroxybenzamide with acetone to form 2,2-dimethyl-6-cyano-3,4-dihydro-2H-1,3-benzoxazin-4-one (m.p. 213°-216°) and subsequently reacting the product with POCl3 /PCl5) are added, and the mixture is stirred at 50° for a further 72 hours. Saturated NaCl solution is subsequently added, the mixture is extracted with ethyl acetate, the organic phase is washed with NaCl solution, dried over sodium sulfate and evaporated, and the residue is chromatographed on silica gel (ethyl acetate/petroleum ether). 2,2-Dimethyl-4-(2-pyridyl-oxy)-6-cyano-2H-1,3-benzoxazine ("A"; m.p. 115°- 116°) is obtained as the first fraction, and 2,2-dimethyl-4-(2-oxo-1,2-dihydropyridyl)-6-cyano-2H-1,3-benzoxazine ("B"; m.p. 158°-159°) as the second fraction.

Sources & evidence

ORD record
ord-f5508cfcc2b24faa9a0890c650fb9d9e
Source dataset
uspto-grants-1991_07
Patent number
US05036068

Reaction notes

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