p-Toluenesulfonic acid → HCID 101025554、化合物

HRID 894475ノート

反応式

HRID 894475 の反応式
[CH3:1][C@@H:2]([CH:22]([OH:24])[CH3:23])[CH:3]1[O:5][CH:4]1[CH2:6][C@H:7]1[C@H:12]([OH:13])[C@H:11]([OH:14])[C@H:10]([CH2:15]/[C:16](/[CH3:21])=[CH:17]/[C:18]([OH:20])=[O:19])[O:9][CH2:8]1.C1(C)C=CC(S(O)(=O)=O)=CC=1.C(=O)(O)[O-].[K+].[Se-]C#N.[K+].C(O)(CC)(C)C.O>COC(OC)(C)C.C(OCC)(=O)C>[CH3:1][C@@H:2]([C@@H:22]([OH:24])[CH3:23])[C:3]1[O:5][C:4]=1[CH2:6][C@@H:7]1[C@@H:12]([OH:13])[C@@H:11]([OH:14])[C@H:10]([CH2:15]/[C:16](/[CH3:21])=[CH:17]/[C:18]([OH:20])=[O:19])[O:9][CH2:8]1

参加物

8

反応物 5

HCID 6101p-Toluenesulfonic acidHCID 76960Selenocyanic acid, potassium salt (1:1)HCID 516893Potassium BicarbonateHCID 6455298HCID 6455298、化合物HCID 129645095HCID 129645095、化合物

生成物 1

HCID 101025554HCID 101025554、化合物

試薬・触媒・溶媒 2

HCID 64952,2-Dimethoxypropane溶媒HCID 8857Ethyl Acetate溶媒2 回

実験手順

Monic acid A (3.44 g) was dissolved in 2,2-dimethoxypropane (30 ml) and ethyl acetate (30 ml) with a few crystals of p-toluene sulphonic acid. After one hour the solution was diluted with ethyl acetate and washed with brine then dried (MgSO4). The solvent was removed in vacuo and the acetonide dissolved in water-methanol (1:1, 40 ml) then treated with potassium bicarbonate (1.0 g, 1 eq). The solution was evaporated to dryness and potassium selenocyanate (4.32 g, 3 eq), tert-amyl alcohol-water (9:1, 150 ml) added and reaction refluxed for 42 hours. After filtering, the reaction mixture was diluted with ethyl acetate and extracted with water (4×25 ml). The combined aqueous phases were acidified (pH2, 5 M-HCl) and extracted with ethyl acetate (4×25 ml) and the combined extracts dried (MgSO4). The solvent was removed in vacuo to give 6,7-O-ispropylidene monic acid C, νmax (CHCl3) 1695, 1640, 1380, 1370, 1220 and 1055 cm-1 ; δ H (CDCl3) 0.98 (3H, d, CH3 -17), 1.13 (3H, d, CH3 -14), 1.33 and 1.48 (6H, d, acetonide CH3 's), 2.17 (3H, s, CH3 -15), 5.45 (2H, m, H-10, H-11), 5.75 (1H, s, H-2), 4.35 (2H, broad, CO2H, OH); δC (CDCl3) 170.5 (C1), 158.3 (C3), 134.9, 128.8 (C10, C11), 117.5 (C2), ##STR7## 76.5 (C5), 75.7 (C7), 74.1 (C6), 71.1 (C13), 66.5 (C16), 44.3 (C12), 36.8 (C8), 34.1 (C9), 28.3, 26.3 (C(CH3)2), 20.1 (C14), 19.3 (C15), 16.3 (C17); m/e (relative intensity) 353 (9) (Found: 353.1995. M+ --CH3 requires 353.2026) 350 (4) (M+ --H2O). The acetonide was dissolved in 80% acetic acid (100 ml) then left overnight. The solution was evaporated to dryness and chromatographed on silica (50 g) eluting with 0-10% methanol-chloroform. The fractions containing pure product (tlc) were combined and evaporated to give monic acid C m.p. 101°-102° C. (2.57 g, 72%) (Found: C, 61.8; H, 8.4. C17H28O6 requires C, 62.2; H, 8.6%).

後処理

  1. washwashed with brine
  2. dry with materialthen dried (MgSO4)
  3. customThe solvent was removed in vacuo
  4. dissolutionthe acetonide dissolved in water-methanol (1:1, 40 ml)
  5. additionadded
  6. customreaction
  7. temperaturerefluxed for 42 hours
  8. filtrationAfter filtering
  9. additionthe reaction mixture was diluted with ethyl acetate
  10. extractionextracted with water (4×25 ml)
  11. extractionextracted with ethyl acetate (4×25 ml)
  12. dry with materialthe combined extracts dried (MgSO4)
  13. customThe solvent was removed in vacuo

出典と根拠

ORDレコード
ord-453b8facfcf141a882438b239767b115
出典データセット
uspto-grants-1981_08
特許番号
US04284570

反応ノート

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