Hydrochloric Acid → 3alpha,7beta-Ditetrahydropyranyloxy-5beta-cholan-24-ol

HRID 2371861ノート

反応式

HRID 2371861 の反応式
[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][C@@H:8]1[CH2:31][CH2:30][C@@:29]2([CH3:32])[C@H:10]([CH2:11][C@H:12]([O:34][CH:35]3[CH2:40][CH2:39][CH2:38][CH2:37][O:36]3)[C@@H:13]3[C@@H:28]2[CH2:27][CH2:26][C@@:25]2([CH3:33])[C@H:14]3[CH2:15][CH2:16][C@@H:17]2[C@H:18]([CH3:24])[CH2:19][CH2:20][C:21](O)=[O:22])[CH2:9]1.CN1CCOCC1.ClC(OCC(C)C)=O.[BH4-].[Na+].Cl>O1CCCC1.O.C(OCC)(=O)C>[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][C@@H:8]1[CH2:31][CH2:30][C@@:29]2([CH3:32])[C@H:10]([CH2:11][C@H:12]([O:34][CH:35]3[CH2:40][CH2:39][CH2:38][CH2:37][O:36]3)[C@@H:13]3[C@@H:28]2[CH2:27][CH2:26][C@@:25]2([CH3:33])[C@H:14]3[CH2:15][CH2:16][C@@H:17]2[C@H:18]([CH3:24])[CH2:19][CH2:20][CH2:21][OH:22])[CH2:9]1

参加物

9

反応物 5

HCID 313Hydrochloric AcidHCID 79724-MethylmorpholineHCID 62365Isobutyl chloroformateHCID 4311764Sodium borohydrideHCID 228428343alpha,7beta-Ditetrahydropyranyloxy-5beta-cholan-24-oic acid

生成物 1

HCID 228428353alpha,7beta-Ditetrahydropyranyloxy-5beta-cholan-24-ol収率 98.3%

試薬・触媒・溶媒 3

HCID 962Water溶媒2 回HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

実験手順

To a solution of compound (2) (9.80 g; 17.48 mmoles) in anhydrous tetrahydrofuran (250 ml), at -70° C. under magnetic stirring and nitrogen atmosphere, N-methylmorpholine (1.76 g; 17.48 mmoles) and isobutyl chloroformate (2.87 g; 21.0 mmoles) were added. The reaction mixture was left to react for 30 min., the separated solid was then removed by filtration and the filtrate was added to a sodium borohydride solution (1.65 g; 43.6 mmoles) in water (10 ml) kept at -10° C. under magnetic stirring at room temperature, in about 30 min., and the resulting mixture was left to react overnight at r.t. Thereafter the reaction mixture was diluted with ethyl acetate (20 ml) and water (80 ml), acidified with 5% hydrochloric acid and extracted with ethyl acetate (3×50 ml). The combined organic phases were washed with saturated water (1×50 ml), dried over sodium sulfate and concentrated under vacuum. A residue (9.40 g) was obtained which was subjected to flash chromatography on SiO2 (φ=5.5 cm, h=20 cm): eluting with 99/1 chloroform/methanol, 6.8 g of compound (3) were obtained, (71%); 1H-NMR (CDCl3)δ 0,7 (s, 3H, 18-CH3); 0,9-1,0 (m, 6H, 19-CH3, 21-CH3); 2,15-2,3 (s, 1H, --OH); 3,3-4,1 (m, 8H, 3-CH-, 24-CH2 -, 2x-O-CH2 -); 4,4-4,75 (m, 2H, 2x-O-CH-O-).

後処理

  1. waitThe reaction mixture was left
  2. customto react for 30 min.
  3. customthe separated solid was then removed by filtration
  4. customkept at -10° C.
  5. waitthe resulting mixture was left
  6. customto react overnight at r.t
  7. extractionextracted with ethyl acetate (3×50 ml)
  8. washThe combined organic phases were washed with saturated water (1×50 ml)
  9. dry with materialdried over sodium sulfate
  10. concentrationconcentrated under vacuum

出典と根拠

ORDレコード
ord-e495ae356e024ffe92c3d9bbc7e47e5b
出典データセット
uspto-grants-1992_03
特許番号
US05096898

反応ノート

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