Diethyl (ethoxymethylene)malonate → HCID 13188588、化合物

HRID 851085ノート

反応式

HRID 851085 の反応式
[Cl:1][C:2]1[CH:12]=[CH:11][C:5]2[NH:6][CH:7]([CH3:10])[CH2:8][O:9][C:4]=2[C:3]=1[F:13].C([O:16][CH:17]=[C:18]([C:24](OCC)=O)[C:19]([O:21][CH2:22][CH3:23])=[O:20])C.O1C2C=CC=CC=2C=CN1>O>[Cl:1][C:2]1[C:3]([F:13])=[C:4]2[O:9][CH2:8][CH:7]([CH3:10])[N:6]3[CH:24]=[C:18]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[C:17](=[O:16])[C:11]([CH:12]=1)=[C:5]23

参加物

5

反応物 3

HCID 6871Diethyl (ethoxymethylene)malonateHCID 13188587HCID 13188587、化合物HCID 17845026Benzoxazines

生成物 1

HCID 13188588HCID 13188588、化合物収率 67%

試薬・触媒・溶媒 1

HCID 962Water溶媒

実験手順

A mixture of 1.11 g (5.5 mmols) of 7-chloro-8-fluoro-3-methyl-2,3-dihydro-4H-1,4-benzoxazine and 1.4 g (6.2 mmols) of diethyl ethoxymethylenemalonate was stirred for 2 hours while heating at 130°-140° C. (bath temperature). After confirming disappearance of the starting benzoxazine compound by thin-layer chromatography, 5 g of ethyl polyphosphate was added to the reaction mixture and the mixture was again allowed to react for 1 hour at 140° C. (bath temperature). After cooling, 20 ml of water was added to the mixture and the precipitate formed was extracted with 150 ml of chloroform. The chloroform extract was dried with sodium sulfate and chloroform was then distilled off. The resulting residue was purified by silica gel (20 g) column chromatography using methanol-chloroform (5:95 by volume) as an eluant to provide 1.2 g (67.0% yield) of ethyl 9-chloro-10-fluoro-3-methyl-7-oxo-2,3-dihydro-7H-pyrido[1,2,3-de][1,4]benzoxazine-6-carboxylate with m.p. 263°-264° C.

後処理

  1. temperaturewhile heating at 130°-140° C. (bath temperature)
  2. additionwas added to the reaction mixture
  3. customto react for 1 hour at 140° C. (bath temperature)
  4. temperatureAfter cooling
  5. customthe precipitate formed
  6. extractionwas extracted with 150 ml of chloroform
  7. extractionThe chloroform extract
  8. dry with materialwas dried with sodium sulfate and chloroform
  9. distillationwas then distilled off
  10. customThe resulting residue was purified by silica gel (20 g) column chromatography

出典と根拠

ORDレコード
ord-a77555a6d3d346c5811767907dd791fb
出典データセット
uspto-grants-1983_05
特許番号
US04382892

反応ノート

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