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Hydrochloric Acid → 4-Methoxybenzyl 1-[di(methoxycarbonyl)methyl]-4-nitronaphthalene-2-carboxylate

HRID 366799
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 366799
[N+:1]([C:4]1[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[C:7](OS(C(F)(F)F)(=O)=O)=[C:6]([C:22]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][C:29]([O:32][CH3:33])=[CH:28][CH:27]=2)=[O:23])[CH:5]=1)([O-:3])=[O:2].[C:34]([O:41][CH3:42])(=[O:40])[CH2:35][C:36]([O:38][CH3:39])=[O:37].C([O-])([O-])=O.[K+].[K+].Cl>CN(C=O)C.C(Cl)Cl>[CH3:39][O:38][C:36]([CH:35]([C:34]([O:41][CH3:42])=[O:40])[C:7]1[C:8]2[C:13](=[CH:12][CH:11]=[CH:10][CH:9]=2)[C:4]([N+:1]([O-:3])=[O:2])=[CH:5][C:6]=1[C:22]([O:24][CH2:25][C:26]1[CH:31]=[CH:30][C:29]([O:32][CH3:33])=[CH:28][CH:27]=1)=[O:23])=[O:37]
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

7

Edukt 4

HCID 313Hydrochloric AcidHCID 7943Dimethyl malonateHCID 11430Potassium CarbonateHCID 105529114-Methoxybenzyl 4-nitro-1-trifluoromethylsulfonyloxynaphthalene-2-carboxylate

Produkt 1

HCID 108140884-Methoxybenzyl 1-[di(methoxycarbonyl)methyl]-4-nitronaphthalene-2-carboxylateAusbeute 84 %

Reagenzien, Katalysatoren, Lösungsmittel

2
HCID 6228DimethylformamideLösungsmittelHCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
20 °C

Versuchsvorschrift

A stirred solution of 4 (13.20 g, 27.2 mmol) and dimethyl malonate (5.39 g, 40.8 mmol) in DMF (85 mL) was cooled to -5° C. and treated with powdered K2CO3 (22.53 g, 163 mmol). The mixture was allowed to warm to 20° C. over a 2 h period, and after stirring for a further 12 h at 20° C. was poured slowly into cold stirred 0.5N HCl (1750 mL). The resulting solid was dissolved in CH2Cl2 and the solution was washed twice with water, dried (Na2SO4) and then evaporated to dryness. The residue was crystallised from CH2Cl2 /iPr2O/petroleum ether to give 4-methoxybenzyl 1-[di(methoxycarbonyl)methyl]-4-nitronaphthalene-2-carboxylate (5) (10.66 g, 84%), suitable for further use. A sample recrystallised from MeOH had mp 124-125° C. 1H NMR (CDCl3) δ 8.62 (s, 1H, H-3), 8.45 (d, J=8.6 Hz, 1H, H-5), 8.21 (d, J=8.7 Hz, 1H, H-8), 7.70 (br t, J=7.7 Hz, 1H, H-6), 7.69 (br t, J=7.8 Hz, 1H, H-7), 7.41 (d, J=8.7 Hz, 2H, H-2',6'), 6.94 (d, J=8.7 Hz, 2H, H-3',5'), 6.62 (s, 1H, ArCH), 5.37 (s, 2H, CH2), 3.83 (s, 3H, PhOCH3), 3.69 (s, 6H, 2×CO2CH3). Anal. Calculated for C24H21NO9 : C, 61.6; H, 4.7; N, 3.1%.

Aufarbeitung

  1. additionwas poured slowly
  2. washthe solution was washed twice with water
  3. dry with materialdried (Na2SO4)
  4. customevaporated to dryness
  5. customThe residue was crystallised from CH2Cl2 /iPr2O/petroleum ether

Quellen und Nachweise

ORD-Eintrag
ord-24c1e6a23edb4edc8c13a6859adee799
Quelldatensatz
uspto-grants-2000_10
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US06130237

Notizen zur Reaktion

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