Pyridine → 2-Methylpropyl (2R)-4-[(3-chloropropyl)sulfonyloxy]-3,3-dimethyl-2-(phenylmethoxy)butanoate

HRID 1671441Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1671441
[Cl:1][CH2:2][CH2:3][CH2:4][S:5]([O:8][CH2:9][C:10]([CH3:24])([CH3:23])[C@@H:11]([O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:12]([OH:14])=[O:13])(=[O:7])=[O:6].C(Cl)(=O)C(Cl)=O.[CH3:31][CH:32]([CH3:35])[CH2:33]O.N1C=CC=CC=1>ClCCl>[Cl:1][CH2:2][CH2:3][CH2:4][S:5]([O:8][CH2:9][C:10]([CH3:24])([CH3:23])[C@@H:11]([O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:12]([O:14][CH2:31][CH:32]([CH3:35])[CH3:33])=[O:13])(=[O:6])=[O:7]

Komponenten

6

Edukt 4

HCID 1049PyridineHCID 6560IsobutanolHCID 65578Oxalyl chlorideHCID 86628870(2R)-4-[(3-Chloropropyl)sulfonyloxy]-3,3-dimethyl-2-(phenylmethoxy)butanoic acid

Produkt 1

HCID 866290392-Methylpropyl (2R)-4-[(3-chloropropyl)sulfonyloxy]-3,3-dimethyl-2-(phenylmethoxy)butanoateAusbeute 48 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

Following the general procedure for the preparation of carboxylic esters from carboxylic acids of Description 15, (2R)-4-[(3-chloropropyl)sulfonyloxy]-3,3-dimethyl-2-(phenylmethoxy)butanoic acid (11) (1.1 g, 3.1 mmol) dissolved in 30 mL of dichloromethane was reacted with 1.8 mL (3.6 mmol) of oxalyl chloride (2.0 M in DCM). After completion of the reaction, a solution of 2-methylpropanol (0.57 mL, 0.46 g, 6.2 mmol) and 0.50 mL of pyridine (0.49 g, 6.2 mmol) in 20 mL of anhydrous dichloromethane (DCM) was added to the acid chloride. After work-up, the crude material was purified by silica gel column chromatography using a mixture of ethyl acetate (EtOAc) and hexane (Hxn) as eluent (EtOAc/Hxn=1:5) to provide 0.62 g (48% yield) of the title compound (30a) as a colorless oil. Rf=0.69 (EtOAc/Hxn=1:2). 1H NMR (400 MHz, CDCl3): δ=0.98 (d, J=6.4 Hz, 1H), 1.07 (s, 3H), 1.09 (s, 3H), 1.99 (septet, J=6.4 Hz, 1H), 2.25-2.34 (m, 2H), 3.22-3.26 (m, 2H), 3.64 (t, J=6.0 Hz, 2H), 3.86 (s, 1H), 3.89-4.01 (m, 3H), 4.23-4.25 (m, 1H), 4.35 (d, J=11.2 Hz, 1H), 4.64 (d, J=11.2 Hz, 1H), 7.29-7.39 (m, 5H) ppm. MS (ESI) m/z 435.16 (M+H)+, 457.11 (M+Na)+. The analytical data was consistent with the proposed structure.

Aufarbeitung

  1. customAfter completion of the reaction
  2. customAfter work-up, the crude material was purified by silica gel column chromatography
  3. additiona mixture of ethyl acetate (EtOAc) and hexane (Hxn) as eluent (EtOAc/Hxn=1:5)

Quellen und Nachweise

ORD-Eintrag
ord-1440c098488949e6b658233adb96a896
Quelldatensatz
uspto-grants-2011_08
Patentnummer
US07994218B2

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