11-Bromo-1-undecanol → HCID 22625150, Verbindung

Temperatur

80 °C

To a solution of 11-bromo-1-undecanol (10 g, 40 mmol) in DMSO (80 mL) was added thiourea (3.64 g, 48 mmol), and the mixture was allowed to react at room temperature for 21 hr. The mixture was extracted twice with hexane (20 mL) to remove the unreacted bromo alcohol. To the DMSO fraction was added 2N KOH (50 mL) and the mixture was heated at 80° C. for 5 min, releasing the thiol 11-mercapto-undecanol. The mixture was acidified (HCl) and extracted twice with ether (40 ml). The combined ether phases were washed successively with water and brine, dried over MgSO4, and evaporated under reduced pressure. The resulting thiol (≅7.2 g) was caused to react with methyl 5-bromo-pentanoate (7 g, 37 mmol) according to the procedure for compound 1. Crystallization of the product in hexane yielded 5.5 g (18 mmol 48% yield from the thiol) of methyl 17-hydroxy-6-thia-heptadecanoate. TLC (hexane/ether 1:1) showed a single product at Rf=0.3. Without further characterization, the hydroxy-ester (4 g, 12 mmol) was caused to react with Ts-Cl (2.7 g, 12 mmol) and pyridine (14 mmol) in CHCl2(40 mL) at 5° C. for 4 hr. The mixture was acidified with ice-diluted HCl, and the organic layer separated, dried (MgSo4) and evaporated under reduced pressure. The product 3 (2.4 g, 34% yield) was isolated by column chromatography (hexane/ethyl acetate 7:3) and recrystallized in hexane. TLC (hexane/ethyl acetate 7:3) Rf=0.6. Melting point=54° C. 1H-NMR δ1.3 (m, 22H, CH2), 2.38 (t. 2H, C(2)H2), 2.5 (m, 7H, C(5)H2, C(7)H2, (tosyl) CH3), 3.7 (s, 3H, —COO—CH3), 4.0 (t, 2H, C(17)H2), 7.6 (m, 4H, aryl).

1. customto react at room temperature for 21 hr
2. extractionThe mixture was extracted twice with hexane (20 mL)
3. customto remove the unreacted bromo alcohol
4. additionTo the DMSO fraction was added 2N KOH (50 mL)
5. extractionextracted twice with ether (40 ml)
6. washThe combined ether phases were washed successively with water and brine
7. dry with materialdried over MgSO4
8. customevaporated under reduced pressure
9. customCrystallization of the product in hexane

ORD-Eintrag

ord-0f019eaaae834b01afb5cb25db50e0f0

Quelldatensatz

uspto-grants-2002_03

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US06362352B1