Sulfuric Acid → Isopropyltriphenylphosphonium iodide

HRID 2240853

Reaktionsgleichung

Reaktionsgleichung von HRID 2240853
CO[C:3](=O)[CH:4]=[CH:5]C1C=CC=C(OC)C=1.[CH2:15]([O:17][C:18](=[O:29])[CH:19]=[CH:20][C:21]1[CH:26]=[CH:25][CH:24]=[C:23]([O:27][CH3:28])[CH:22]=1)[CH3:16].[I-:30].[CH:31]([P+:34]([C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1)([C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)([CH3:33])[CH3:32].C([Li])CCC.OS(O)(=O)=O>C1COCC1>[I-:30].[CH:31]([P+:34]([C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1)([C:35]1[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=1)[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)([CH3:33])[CH3:32].[CH2:15]([O:17][C:18]([C@H:19]1[C@H:20]([C:21]2[CH:26]=[CH:25][CH:24]=[C:23]([O:27][CH3:28])[CH:22]=2)[C:4]1([CH3:5])[CH3:3])=[O:29])[CH3:16]

Komponenten

8

Edukt 5

HCID 1118Sulfuric AcidHCID 367201Ethyl 3-(3-methoxyphenyl)prop-2-enoateHCID 2723783Isopropyltriphenylphosphonium iodideHCID 54105512Methyl m-methoxycinnamateHCID 178418339Butyllithium

Produkt 2

HCID 2723783Isopropyltriphenylphosphonium iodideHCID 57652816trans-3-(3-Methoxy-phenyl)-2,2-dimethyl-cyclopropanecarboxylic acid ethyl ester

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

Cyclopropanation of 3-methoxy-cinnamic acid methyl ester was carried out following the procedure of Ahmand et al., J Med. Chem 2001, 44, 3302-3310. Isopropyl-triphenylphosphonium iodide was prepared as described by Grieco et al., Tet. Lett. 1972, 36, 3781-3783. Briefly, a solution of 3-methoxy-cinnamic acid ethyl ester (14.6 g, 70.9 mmol) in 300 mL THF was cooled in a dry ice/acetone bath to approximately −78° C., and added dropwise to a −78° C. stirring solution of isopropyl-triphenylphosphonium iodide (51 g. 118 mmol) and n-butyl-lithium (54 mL, 135 mmol) in THF. The reaction mixture was allowed to warm to 0° C. with stirring for two hours, then was stirred at room temperature for 15 hours. The reaction mixture was poured onto ice and the resulting aqueous mixture was adjusted to neutral pH by addition of 1M aqueous H2SO4. The aqueous solution was extracted three times with a 1/1 mixture of hexanes/EtOAc and once with EtOAc. The combined organic layers were filtered through silica, and the filtrate was dried over MgSO4, filtered, and concentrated under reduced pressure to give 15.22 g of crude trans-3-(3-methoxy-phenyl)-2,2-dimethyl-cyclopropanecarboxylic acid ethyl ester.

Aufarbeitung

  1. additionadded dropwise to a −78° C.
  2. stirringwas stirred at room temperature for 15 hours
  3. additionThe reaction mixture was poured onto ice
  4. extractionThe aqueous solution was extracted three times
  5. additionwith a 1/1 mixture of hexanes/EtOAc
  6. filtrationThe combined organic layers were filtered through silica
  7. dry with materialthe filtrate was dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-df5729aae55a4d1ab4ce6f628ad7630b
Quelldatensatz
uspto-grants-2010_05
Patentnummer
US07723391B2

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