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Water → (+)-Trimethyl 3-nitro-2-(2,4,6-trimethoxyphenyl)propane-1,1,3-tricarboxylate

HRID 553270
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HRID 553270 반응식
[O-]S(C(F)(F)F)(=O)=O.[Mg+2].[O-]S(C(F)(F)F)(=O)=O.O.C1(C2O[C@@H]3CC4C=CC=CC=4[C@@H]3N=2)(C2O[C@@H]3CC4C=CC=CC=4[C@@H]3N=2)CC1.[CH3:46][O:47][C:48](=[O:66])/[C:49](/[N+:63]([O-:65])=[O:64])=[CH:50]\[C:51]1[C:56]([O:57][CH3:58])=[CH:55][C:54]([O:59][CH3:60])=[CH:53][C:52]=1[O:61][CH3:62].[C:67]([O:74][CH3:75])(=[O:73])[CH2:68][C:69]([O:71][CH3:72])=[O:70].CN1CCOCC1>CO.C(Cl)(Cl)Cl>[N+:63]([CH:49]([C:48]([O:47][CH3:46])=[O:66])[CH:50]([C:51]1[C:56]([O:57][CH3:58])=[CH:55][C:54]([O:59][CH3:60])=[CH:53][C:52]=1[O:61][CH3:62])[CH:68]([C:67]([O:74][CH3:75])=[O:73])[C:69]([O:71][CH3:72])=[O:70])([O-:65])=[O:64]
참가 물질반응 조건실험 절차후처리출처 및 근거반응 노트

참가 물질

9

반응물 6

HCID 962WaterHCID 7943Dimethyl malonateHCID 79724-MethylmorpholineHCID 2734125Magnesium trifluoromethanesulfonateHCID 9850233(3aS,3a'S,8aR,8a'R)-2,2'-(Cyclopropane-1,1-diyl)bis(8,8a-dihydro-3aH-indeno[1,2-d]oxazole)HCID 86641484(E)-Methyl-2-nitro-3-(2,4,6-trimethoxyphenyl)acrylate

생성물 1

HCID 72254933(+)-Trimethyl 3-nitro-2-(2,4,6-trimethoxyphenyl)propane-1,1,3-tricarboxylate

시약·촉매·용매 2

HCID 887Methanol용매HCID 6212Chloroform용매2회

반응 조건

온도
40 °C

실험 절차

In a two-necked 500 mL round-bottomed flask maintained under nitrogen, chloroform (10 mL), magnesium triflate (0.161 g, 0.5 mmol) and water (0.036 mL, 2.0 mmol) were added. To this stirred solution, (3aS,3a′S,8aR,8a′R)-2,2′(cyclopropane-1,1-diyl)bis(8,8a-dihydro-3aH-indeno[1,2-d]oxazole) (bis(oxazoline)) (0.196 g, 0.55 mmol) was added and the reaction mixture stirred for 1 hour. At the end of 1 hour, chloroform (30 mL) and molecular sieves (2 g) were added and the mixture stirred for another 90 mins. (E)-Methyl-2-nitro-3-(2,4,6-trimethoxyphenyl)acrylate (3.1 g, 0.01 mol), dimethyl malonate (1.92 g, 0.014 mol) and N-methylmorpholine (0.06 g, 0.6 mmol) were added and the reaction mixture was stirred for 12 hours followed by heating at 40° C. for 4 hours. Petroleum ether (15 mL) was added to the reaction mixture, stirred for 10 mins. and the mixture filtered. The molecular sieves were washed with methyl-t-butyl ether and the combined organic layer was washed with 5% phosphoric acid (10 mL) and brine (15 mL). The organic layer was concentrated under reduced pressure to give an oil. The oil was dissolved in methanol (10 mL), cooled and filtered to give a white crystalline solid.

후처리

  1. temperatureIn a two-necked 500 mL round-bottomed flask maintained under nitrogen
  2. stirringthe mixture stirred for another 90 mins
  3. stirringthe reaction mixture was stirred for 12 hours
  4. stirringstirred for 10 mins
  5. filtrationand the mixture filtered
  6. washThe molecular sieves were washed with methyl-t-butyl ether
  7. washthe combined organic layer was washed with 5% phosphoric acid (10 mL) and brine (15 mL)
  8. concentrationThe organic layer was concentrated under reduced pressure
  9. customto give an oil
  10. temperaturecooled
  11. filtrationfiltered
  12. customto give a white crystalline solid

출처 및 근거

ORD 기록
ord-43f1da2a058c4afea6e3de94f3c9ad80
출처 데이터셋
uspto-grants-2011_05
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US07951961B2

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