Water → 7-(acetyloxy)-3-(3-chloro-4-bromo-1-methylbutyl)-3a,4,5,6,7,7a-hexahydro-3a-methyl-1H-indene

HRID 6283

Reaktionsgleichung

Reaktionsgleichung von HRID 6283
[C:1]([O:4][CH:5]1[CH:13]2[C:9]([CH3:21])([C:10]([CH:14]([CH3:20])[CH2:15][CH:16]([Cl:19])[CH2:17]O)=[CH:11][CH2:12]2)[CH2:8][CH2:7][CH2:6]1)(=[O:3])[CH3:2].C1(C)C=CC(S(Cl)(=O)=O)=CC=1.O.[Br-:34].[Li+]>ClCCl.N1C=CC=CC=1>[C:1]([O:4][CH:5]1[CH:13]2[C:9]([CH3:21])([C:10]([CH:14]([CH3:20])[CH2:15][CH:16]([Cl:19])[CH2:17][Br:34])=[CH:11][CH2:12]2)[CH2:8][CH2:7][CH2:6]1)(=[O:3])[CH3:2]

Komponenten

7

Edukt 4

HCID 962WaterHCID 73974-Toluenesulfonyl chlorideHCID 82050Lithium BromideHCID 148012777-(acetyloxy)-beta-chloro-3a,4,5,6,7,7a-hexahydro-delta,3a-dimethyl-1H-indene-3-butanol

Produkt 1

HCID 148012797-(acetyloxy)-3-(3-chloro-4-bromo-1-methylbutyl)-3a,4,5,6,7,7a-hexahydro-3a-methyl-1H-indene

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 1049PyridineLösungsmittelHCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A solution of 1.50 g (4.76 mmol) of [3aS-[3(βS*,δR*), 3aα,7β,7aβ]]-7-(acetyloxy)-β-chloro-3a,4,5,6,7,7a-hexahydro-δ,3a-dimethyl-1H-indene-3-butanol in 20 mL of dichloromethane and 20 mL of pyridine was treated at 0° C. and under argon with 4.50 g (23.60 mmol) of p-toluenesulfonyl chloride and then stirred overnight at 0° C. Water (8 mL) was then added and, after stirring the resulting mixture for 1 hour at room temperature, the solvents were removed in vacuo and the residue diluted with water and extracted with ethyl acetate. The combined organic extracts were subsequently washed with 1N hydrochloric acid, water, 2N aqueous potassium bicarbonate solution and brine and dried. The residue obtained after evaporation of the ethyl acetate (weighing 2.10 g) was dissolved in 40 mL of N,N-dimethylformamide and heated under argon at 50° C. with 4.00 g (46.06 mmol) of anhydrous lithium bromide for 17 hours. After cooling, the reaction mixture was diluted with ice water and extracted with ethyl acetate. The combined organic extracts were washed several times with water, dried and evaporated to dryness to give 1.62 g (90% overall yield) of the title compound. 1H NMR (60 MHz, CDCl3) δ0.88 (s, 3H), 1.07 (d, J=6.4 Hz, 3H), 2.03 (s, 3H), 3.60 (br AB q, J=10.2 Hz, Δγ=14.0 Hz, 2H), 5.00 (br m, 1H), 5.33 (br s, 1H) ppm.

Aufarbeitung

  1. stirringafter stirring the resulting mixture for 1 hour at room temperature
  2. customthe solvents were removed in vacuo
  3. additionthe residue diluted with water
  4. extractionextracted with ethyl acetate
  5. washThe combined organic extracts were subsequently washed with 1N hydrochloric acid, water, 2N aqueous potassium bicarbonate solution and brine
  6. customdried
  7. customThe residue obtained
  8. customafter evaporation of the ethyl acetate (weighing 2.10 g)
  9. dissolutionwas dissolved in 40 mL of N,N-dimethylformamide
  10. temperatureAfter cooling
  11. extractionextracted with ethyl acetate
  12. washThe combined organic extracts were washed several times with water
  13. customdried
  14. customevaporated to dryness
  15. customto give

Quellen und Nachweise

ORD-Eintrag
ord-df8f3ff397084a7f9ec3233d739fea5e
Quelldatensatz
uspto-grants-1993_09
Patentnummer
US05247123

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