Methyl 5-formylthiophene-2-carboxylate → methyl (E)-5-[2-(3-hexyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-vinyl]-thiophene-2-carboxylate

HRID 2186551

Reaktionsgleichung

Reaktionsgleichung von HRID 2186551
[Br-].[CH2:2]([C:8]1[C:9]([C:22]2C=CC=CC=2[P+](C)(C2C=CC=CC=2)C2C=CC=CC=2)=[CH:10][C:11]2[C:12]([CH3:21])([CH3:20])[CH2:13][CH2:14][C:15]([CH3:19])([CH3:18])[C:16]=2[CH:17]=1)[CH2:3][CH2:4][CH2:5][CH2:6][CH3:7].C([Li])CCC.[CH:47]([C:49]1[S:53][C:52]([C:54]([O:56][CH3:57])=[O:55])=[CH:51][CH:50]=1)=O.C(OCC)(=O)C.CCCCCC>C1COCC1.CCCCCC.[Cl-].[NH4+]>[CH2:2]([C:8]1[C:9](/[CH:22]=[CH:47]/[C:49]2[S:53][C:52]([C:54]([O:56][CH3:57])=[O:55])=[CH:51][CH:50]=2)=[CH:10][C:11]2[C:12]([CH3:21])([CH3:20])[CH2:13][CH2:14][C:15]([CH3:19])([CH3:18])[C:16]=2[CH:17]=1)[CH2:3][CH2:4][CH2:5][CH2:6][CH3:7]

Komponenten

8

Edukt 4

HCID 818924Methyl 5-formylthiophene-2-carboxylateHCID 21226206Ethyl acetate hexaneHCID 86758176(3-Hexyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-methyl Triphenylphosphonium BromideHCID 178418339Butyllithium

Produkt 1

HCID 86758178methyl (E)-5-[2-(3-hexyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-vinyl]-thiophene-2-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 8028TetrahydrofuranLösungsmittel2×HCID 8058HexaneLösungsmittelHCID 25517Ammonium ChlorideLösungsmittel

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

A suspension of 1.917 g of (3-hexyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-naphthalen-2-yl)-methyl triphenylphosphonium bromide (From Example 7.1) in 40 ml THF was cooled to −78° C. and treated with 1.91 ml of butyllithium 1.6 M in hexane. The mixture was allowed to warm to room temperature for 30 min. then was cooled back to −78° C. A solution of 495 mg of methyl 5-formylthiophene-2-carboxylate in 10 ml THF was added. The mixture was kept at −78° C. for 30 min. then was allowed to warm to room temperature for 30 min. The reaction mixture was diluted with 50 ml of a saturated ammonium chloride solution and extracted with 3 portions of 50 ml of ethyl acetate. The combined organic extracts were dried (MgSO4), filtered and concentrated in vacuo, giving a yellow solid. Flash chromatography (SiO2, 3% ethyl acetate/hexane) gave 1.2 g of a mixture (E/Z) of the desired product. Chromatography on a medium pressure liquid chromatography system (3% ethyl acetate/hexane) provided 1.12 g of the title product without trace of the Z isomer. 1H NMR (CDCl3): 7.69 (d, J=4.5 Hz, 1H), 7.48 (s, 1H), 7.30 (d, J=15.6 Hz, 1H), 7.09 (s, 1H), 7.05 (d, J=4.9 Hz, 1H), 7.04 (d, J=15.6 Hz, 1H), 3.89 (s, 3H), 2.67 (t, J=8.3 Hz, 2H), 1.68 (s, 4H), 1.2-1.5 (m, 8H), 1.32 (s, 6H), 1.28 (s, 6H), 0.90 (t, J=7.0 Hz, 3H).

Aufarbeitung

  1. temperatureto warm to room temperature for 30 min.
  2. temperaturethen was cooled back to −78° C
  3. temperatureto warm to room temperature for 30 min
  4. extractionextracted with 3 portions of 50 ml of ethyl acetate
  5. dry with materialThe combined organic extracts were dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customgiving a yellow solid

Quellen und Nachweise

ORD-Eintrag
ord-d3d734c1f24140519b500b9b4ed9fd11
Quelldatensatz
uspto-grants-2002_06
Patentnummer
US06403810B2

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