Hydrochloric Acid → 4-[4-(4-Chlorophenoxy)phenylthiomethyl]tetrahydropyran-4-carboxylic acid ethyl ester

HRID 1584394Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1584394
[CH2:1]([O:3][C:4]([C:6]1([CH2:12]I)[CH2:11][CH2:10][O:9][CH2:8][CH2:7]1)=[O:5])[CH3:2].[Na].[Cl:15][C:16]1[CH:29]=[CH:28][C:19]([O:20][C:21]2[CH:26]=[CH:25][C:24]([SH:27])=[CH:23][CH:22]=2)=[CH:18][CH:17]=1.[H-].[Na+].Cl>CN(C)C=O>[CH2:1]([O:3][C:4]([C:6]1([CH2:12][S:27][C:24]2[CH:25]=[CH:26][C:21]([O:20][C:19]3[CH:28]=[CH:29][C:16]([Cl:15])=[CH:17][CH:18]=3)=[CH:22][CH:23]=2)[CH2:11][CH2:10][O:9][CH2:8][CH2:7]1)=[O:5])[CH3:2]

Komponenten

7

Edukt 5

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 5360545SodiumHCID 185104594-(4-Chlorophenoxy)benzenethiol2×HCID 543351764-(Iodomethyl)tetrahydropyran-4-carboxylic acid ethyl ester

Produkt 1

HCID 154349704-[4-(4-Chlorophenoxy)phenylthiomethyl]tetrahydropyran-4-carboxylic acid ethyl esterAusbeute 91 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

4-(Iodomethyl)tetrahydropyran-4-carboxylic acid ethyl ester (300 mg, 1 mmol) was added to a solution containing the sodium salt of 4-(4-chlorophenoxy)thiophenol (generated by the addition of sodium hydride powder (36 mg, 1.5 mmol) to a solution of 4-(4-chlorophenoxy)thiophenol (262 mg, 1.1 mmol) in N,N-dimethylformamide (2 mL) at 0° C. and stirring for 30 minutes). The mixture was warmed to room temperature over 5 minutes, stirred for an additional 20 minutes, cooled to room temperature, and 1M aqueous hydrochloric acid (5 mL) added. The mixture was then partitioned between ethyl acetate (100 mL) and 2M hydrochloric acid (25 mL). The aqueous layer was separated and washed with additional ethyl acetate (2×50 mL). The organic extracts were combined, washed with 1M sodium hydroxide (2×30 mL), dried over magnesium sulfate, concentrated in vacuo. Chromatography over silica gel, and eluting with 20% ethylacetate/hexanes, yielded pure 4-[4-(4-chlorophenoxy)phenylthiomethyl]-tetrahydropyran-4-carboxylic acid ethyl ester (370 mg, 91%), followed by impure 4-[4-(4-chlorophenoxy)phenylthiomethyl]tetrahydropyran-4-carboxylic acid ethyl ester (40 mg). IR (KBr) 1728 cm-1 ; 1HNMR (CDCl3) 1.23 (q, J=7.1 Hz, 3H), 1.56 (ddd, J=14.6, 10.9, 4.4, 2H), 1.63 (ddd, J=14.6, 5.7, 3.3, 2H), 3.13 (s, 2H), 3.51 (ddd, J=11.8, 11.1, 2.4 Hz, 2H), 3.80 (dt, J=11.8, 4.1 Hz, 2H), 4,07 (q, J=7.1 Hz, 2H), 6.91 (d, J=8.9 Hz, 2H), 6.92 (d, J=8.9 Hz, 2H), 7.29 (d, J=9.0 Hz, 2H), 7.39 (d, J=8.9 Hz, 2H); 13C NMR (CDCl3) δ 14.20 (q), 33.72 (t), 45.72 (t), 46.07 (s), 60.92 (t), 65.06 (t), 119.29 (d), 120.20 (d), 128.43 (s), 129.85 (d), 130.57 (s), 133.05 (s), 155.40 (s), 156.21 (s), 174.02 (s); EIHRMS Calcd. for C21H23SO4Cl (M+): 406.1006. Found: 406.1008. Anal. Calcd. for C21H23SO4Cl: C, 61.98; H, 5.70. Found: C, 61.86; H, 5.68.

Aufarbeitung

  1. stirringstirred for an additional 20 minutes
  2. temperaturecooled to room temperature
  3. customThe mixture was then partitioned between ethyl acetate (100 mL) and 2M hydrochloric acid (25 mL)
  4. customThe aqueous layer was separated
  5. washwashed with additional ethyl acetate (2×50 mL)
  6. washwashed with 1M sodium hydroxide (2×30 mL)
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated in vacuo
  9. washChromatography over silica gel, and eluting with 20% ethylacetate/hexanes

Quellen und Nachweise

ORD-Eintrag
ord-50c667cdc92048efa2e7d52dc2eb11f6
Quelldatensatz
uspto-grants-1999_08
Patentnummer
US05932595

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