Dibutyltin dichloride → 5-Bromo-3-(2,2-dimethyl-[1,3]dioxan-5-ylamino)-thiophene-2-carboxylic acid methyl ester

HRID 1190038

Reaktionsgleichung

Reaktionsgleichung von HRID 1190038
[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([Br:11])=[CH:8][C:9]=1[NH2:10])=[O:4].[CH3:12][C:13]1([CH3:20])[O:18][CH2:17][C:16](=O)[CH2:15][O:14]1.C([Sn](Cl)(Cl)CCCC)CCC.C1([SiH3])C=CC=CC=1>C1COCC1.C(OCC)(=O)C>[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([Br:11])=[CH:8][C:9]=1[NH:10][CH:16]1[CH2:17][O:18][C:13]([CH3:20])([CH3:12])[O:14][CH2:15]1)=[O:4]

Komponenten

7

Edukt 4

HCID 12688Dibutyltin dichlorideHCID 12752PhenylsilaneHCID 27331412,2-Dimethyl-1,3-dioxan-5-oneHCID 20158931Methyl 3-amino-5-bromothiophene-2-carboxylate

Produkt 1

HCID 577954295-Bromo-3-(2,2-dimethyl-[1,3]dioxan-5-ylamino)-thiophene-2-carboxylic acid methyl esterAusbeute 29,6 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

A suspension of 3-amino-5-bromo-thiophene-2-carboxylic acid methyl ester (0.5 g, 2.12 mmol) in dry THF (0.6 mL) was treated with 2,2-dimethyl-[1,3]dioxan-5-one (253 μl, 2.12 mmol), followed by dibutyltin dichloride (32 mg, 0.11 mmol). After 5 min phenyl silane (280 μl, 2.27 mmol) was added and the reaction was stirred at room temperature for 3 days. It was dissolved in ethyl acetate (100 mL), washed with NaHCO3 solution and brine. The organic layer was separated, dried over MgSO4, evaporated and left on vacuum pump overnight. The residue was triturated with hexane-ether (4:1) mixture (2×100 mL). The soluble portion was evaporated and purified by chromatography over silica gel (hexane:ethyl acetate—95:5) yielding pure 5-bromo-3-(2,2-dimethyl-[1,3]dioxan-5-ylamino)-thiophene-2-carboxylic acid methyl ester (220 mg, 29%).

Aufarbeitung

  1. washwashed with NaHCO3 solution and brine
  2. customThe organic layer was separated
  3. dry with materialdried over MgSO4
  4. customevaporated
  5. waitleft on vacuum pump overnight
  6. customThe residue was triturated with hexane-ether (4:1) mixture (2×100 mL)
  7. customThe soluble portion was evaporated
  8. custompurified by chromatography over silica gel (hexane:ethyl acetate—95:5)

Quellen und Nachweise

ORD-Eintrag
ord-311ec1548b37468e8d19becfae88085f
Quelldatensatz
uspto-grants-2014_03
Patentnummer
US08674118B2

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