4-Bromostyrene → 2-Phenylethyl 2-oxo-2-(4-vinylphenyl)acetate

HRID 630570

Reaktionsgleichung

Reaktionsgleichung von HRID 630570
Br[C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[CH2:7])=[CH:4][CH:3]=1.[Mg].C1(CCO[C:20](=[O:32])[C:21]([O:23][CH2:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)=[O:22])C=CC=CC=1.[NH4+].[Cl-]>C1COCC1.C(C1C=C(O)C=CC=1O)(C)(C)C.CCCCCCC.C(OCC)(=O)C>[O:32]=[C:20]([C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[CH2:7])=[CH:4][CH:3]=1)[C:21]([O:23][CH2:24][CH2:25][C:26]1[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=1)=[O:22]

Komponenten

8

Edukt 4

HCID 162634-BromostyreneHCID 25517Ammonium ChlorideHCID 5462224MagnesiumHCID 6421929Oxalic acid, di(2-phenylethyl) ester

Produkt 1

HCID 894880472-Phenylethyl 2-oxo-2-(4-vinylphenyl)acetateAusbeute 68,1 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 16043Tert-ButylhydroquinoneKatalysatorHCID 8028TetrahydrofuranLösungsmittel2×HCID 21899848Ethylacetate heptaneLösungsmittel

Versuchsvorschrift

A Grignard reagent prepared from freshly distilled 4-bromostyrene (9.45 g, 51.6 mmol) and magnesium (1.31 g, 54.0 mmol) in THF (70 mL) was added dropwise to a stirred solution of bis(2-phenylethyl)oxalate (14.0 g, 46.9 mmol) in THF (120 mL) at −60° C. The mixture was left warming to room temperature, and then poured onto a mixture of ice (200 g) and a saturated solution of NH4Cl (200 mL). Extraction with diethyl ether (500 mL), washing with a saturated solution of NaCl (300 mL, 3×), re-extraction of the aqueous phase with ether, drying of the combined organic phases (Na2SO4), adding of tert-butyl hydroquinone (TBHQ, ca. 0.3 mg), concentrating and drying under vacuum (0.5 mbar, 0.5 h) afforded 19.40 g of the crude compound. Column chromatography (SiO2, heptane/ethyl acetate 98:2), adding of TBHQ (0.2 mg) to the product fractions, concentrating and drying under vacuum gave 8.95 g (68%) of the desired compound.

Aufarbeitung

  1. waitThe mixture was left
  2. extractionExtraction with diethyl ether (500 mL)
  3. washwashing with a saturated solution of NaCl (300 mL, 3×), re-extraction of the aqueous phase with ether
  4. dry with materialdrying of the combined organic phases (Na2SO4)
  5. additionadding of tert-butyl hydroquinone (TBHQ, ca. 0.3 mg)
  6. concentrationconcentrating
  7. customdrying under vacuum (0.5 mbar, 0.5 h)
  8. customafforded 19.40 g of the crude compound
  9. concentrationconcentrating
  10. customdrying under vacuum

Quellen und Nachweise

ORD-Eintrag
ord-3655e4b7cb7a4ff4b844b76d4115d399
Quelldatensatz
uspto-grants-2016_04
Patentnummer
US09315763B2

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