N-bromobutanimide → (5r)-2-Bromo-4-[(4-methoxyphenyl)sulfonyl]-5-methyl-4,5-dihydrothieno[3,2-c]isoquinoline

HRID 641627Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 641627
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([S:9]([N:12]2[C:21]3[CH:22]=[CH:23][S:24][C:20]=3[C:19]3[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=3[C@H:13]2[CH3:25])(=[O:11])=[O:10])=[CH:5][CH:4]=1.C(O)(=O)C.C(Cl)(Cl)Cl.[Br:34]N1C(=O)CCC1=O>C(Cl)Cl.CCCCCC>[Br:34][C:23]1[S:24][C:20]2[C:19]3[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=3[C@@H:13]([CH3:25])[N:12]([S:9]([C:6]3[CH:5]=[CH:4][C:3]([O:2][CH3:1])=[CH:8][CH:7]=3)(=[O:11])=[O:10])[C:21]=2[CH:22]=1

Komponenten

5

Edukt 3

HCID 67184N-bromobutanimideHCID 21584526Acetic acid chloroformHCID 68578560(5r)4-[(4-Methoxyphenyl)sulfonyl]-5-methyl-4,5-dihydrothieno[3,2-c]isoquinoline

Produkt 1

HCID 68579033(5r)-2-Bromo-4-[(4-methoxyphenyl)sulfonyl]-5-methyl-4,5-dihydrothieno[3,2-c]isoquinolineAusbeute 98,6 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 21226440Methylenechloride HexaneLösungsmittel

Reaktionsbedingungen

Temperatur
23 °C

Versuchsvorschrift

A solution of (5R)4-[(4-methoxyphenyl)sulfonyl]-5-methyl-4,5-dihydrothieno[3,2-c]isoquinoline (12.7 g, 34 mmol) in 1:1 acetic acid-chloroform (300 mL) was treated with N-bromosuccinimide (6.1 g, 34 mmol) at −10° C. After ca. 5 min., the cooling bath was removed and the mixture was warmed to 23° C. After 18 h the resulting solution was poured into water (1.2 L) and extracted with methylene chloride (4×400 mL). The organic solution was washed with 25% aqueous potassium hydroxide and brine (1 L each), dried (K2CO3), and concentrated in vacuo to give the crude product (15.5 g) as a green solid which was loaded onto a column of silica gel (100 g) in warm 25% methylene chloride-hexane. Flash chromatography eluting 25-, then 50-, and then 75% methylene chloride-hexane gave the title compound (15.1 g, 98%, m.p. 136-38° C.) as a white solid. [α]D=+219.4. 1H NMR (400 MHz) δ 1.21 (d, J=7 Hz, CHCH3), 3.64 (s, 3H, OCH3), 5.40 (m, 1H, CHCH3), 6.69 (d, J=9 Hz, 2H, ArH), 6.98 (d, J=7.5 Hz, 1H, ArH), 7.08 (m, 1H, ArH), 7.14 (m, 1H, ArH), 7.16-7.23 (overlapping m, 3H, ArH), 7.36 (s, 1H, ArH). MS (ESI) m/z 450 [M+H]+ Analysis calc. for C19H16BrNO3S2: C, 50.67: H, 3.58; N, 3.11. Found: C, 50.68; H, 3.37; N, 3.04

Aufarbeitung

  1. customthe cooling bath was removed
  2. additionAfter 18 h the resulting solution was poured into water (1.2 L)
  3. extractionextracted with methylene chloride (4×400 mL)
  4. washThe organic solution was washed with 25% aqueous potassium hydroxide and brine (1 L each)
  5. dry with materialdried (K2CO3)
  6. concentrationconcentrated in vacuo
  7. customto give the crude product (15.5 g) as a green solid which
  8. washFlash chromatography eluting 25-

Quellen und Nachweise

ORD-Eintrag
ord-bbfe838577c2433e9779aa602e34e7a4
Quelldatensatz
uspto-grants-2010_04
Patentnummer
US07696221B2

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