Diethyl (ethoxymethylene)malonate → HCID 13188588, 화합물

HRID 851085노트

반응식

HRID 851085 반응식
[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

참가 물질

5

반응물 3

HCID 6871Diethyl (ethoxymethylene)malonateHCID 13188587HCID 13188587, 화합물HCID 17845026Benzoxazines

생성물 1

HCID 13188588HCID 13188588, 화합물수율 67%

시약·촉매·용매 1

HCID 962Water용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-a77555a6d3d346c5811767907dd791fb
출처 데이터셋
uspto-grants-1983_05
특허 번호
US04382892

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