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

HRID 1087373ノート

反応式

HRID 1087373 の反応式
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

参加物

8

反応物 5

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 180Acetone溶媒HCID 6228Dimethylformamide溶媒

実験手順

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.

出典と根拠

ORDレコード
ord-f5508cfcc2b24faa9a0890c650fb9d9e
出典データセット
uspto-grants-1991_07
特許番号
US05036068

反応ノート

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