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

HRID 1584394ノート

反応式

HRID 1584394 の反応式
[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]

参加物

7

反応物 5

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-50c667cdc92048efa2e7d52dc2eb11f6
出典データセット
uspto-grants-1999_08
特許番号
US05932595

反応ノート

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