Desmycosin → 19-Deformyldesmycosin

HRID 1088420ノート

反応式

HRID 1088420 の反応式
[CH3:1][CH2:2][C@H:3]1[O:20][C:18](=[O:19])[CH2:17][C@@H:16]([OH:21])[C@H:15]([CH3:22])[C@@H:14]([O:23][C@@H:24]2[O:29][C@H:28]([CH3:30])[C@@H:27]([OH:31])[C@H:26]([N:32]([CH3:34])[CH3:33])[C@H:25]2[OH:35])[C@@H:13]([CH2:36]C=O)[CH2:12][C@@H:11]([CH3:39])[C:9](=[O:10])[CH:8]=[CH:7][C:6]([CH3:40])=[CH:5][C@@H:4]1[CH2:41][O:42][C@@H:43]1[O:48][C@H:47]([CH3:49])[C@@H:46]([OH:50])[C@@H:45]([O:51][CH3:52])[C@H:44]1[O:53][CH3:54]>C1C=CC=CC=1.C(OCC)(=O)C>[CH3:1][CH2:2][CH:3]1[O:20][C:18](=[O:19])[CH2:17][CH:16]([OH:21])[CH:15]([CH3:22])[CH:14]([O:23][CH:24]2[O:29][CH:28]([CH3:30])[CH:27]([OH:31])[CH:26]([N:32]([CH3:33])[CH3:34])[CH:25]2[OH:35])[CH:13]([CH3:36])[CH2:12][CH:11]([CH3:39])[C:9](=[O:10])[CH:8]=[CH:7][C:6]([CH3:40])=[CH:5][CH:4]1[CH2:41][O:42][CH:43]1[O:48][CH:47]([CH3:49])[CH:46]([OH:50])[CH:45]([O:51][CH3:52])[CH:44]1[O:53][CH3:54]

参加物

4

反応物 1

HCID 6437804Desmycosin

生成物 1

HCID 644405819-Deformyldesmycosin収率 73%

試薬・触媒・溶媒 2

HCID 241Benzene溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
90 °C

実験手順

Desmycosin (Merck Index, Tenth Edition p. 1405) (18.9 o) was dissolved in degassed benzene (580 mL) and tris(triphenYlphospbine)rhodium chloride (29.5 g.) was added. The mixture was heated under dry nitrogen at 90° C. for 16 h. The mixture was diluted with ethyl acetate and extracted twice with 0.2N hydrochloric acid. The aqueous acid layer was adjusted to pH 10 and extracted with dichloromethane. The latter was dried (MgSO4), filtered and evaporated to dryness. The residue was chromatographed on a silica gel column (60×5 cm.) using 5% methanol in chloroform (v/v) as the eluant to give 19deformyldesmycosin (13.2 g., 73%) as a colorless amorphous solid (Anal.: found: C, 57.05; H, 7.99; N, 1.62%. C38H65NO13. 0.5 CHCl3 requires C, 56.79; H, 8.15; N, 1.74%); MS: m/z 744 (MH+); Rotation: [α]D26 0° (CHCl3); UV: λmax (CH3OH) 282 nm (ε20,676); IR: νmax (CDCl3) 3540, 3450, 1705, 1670, 1590, 1185, 1163, 1055 cm-1 ; 1H-NMR: δH (CDCl3) 0.92 (3H,tJ16,17-CH3 7 Hz, 17-CH3), 1.02 (3H,d,J 7 Hz, CH3), 1.03 (3 H,d,J 7 Hz, CH3), 1.18 (3H,d,J 7 Hz, CH3), 1.26 (3H,d,J 7 Hz, CH3), 1.30 (3H,d,J 7 Hz, CH3), 1.78 (3H,d,J12 -CH3,13 1 Hz, 12-CH3), 2.53 (6H,s,3'-N(CH3)2), 3.48 (3H,s,2"-OCH3), 3.60 (3H,s,3"-OCH3), 4.28 (1H,d,J1'ax,2'ax 8 Hz, H1'ax), 4.55 (1H,d,J1"ax,2"ax 8 Hz, H1"ax), 4.97 (1H,m,H15), 5.82 (1H,dc,J12-CH3,13 1 Hz, J13,14 10 Hz, H13), 6.24 (1H,d,J10,11 16 Hz, H10), and 7.24 (1H,d,J10,11 16 Hz, H11)

後処理

  1. extractionextracted twice with 0.2N hydrochloric acid
  2. extractionextracted with dichloromethane
  3. dry with materialThe latter was dried (MgSO4)
  4. filtrationfiltered
  5. customevaporated to dryness
  6. customThe residue was chromatographed on a silica gel column (60×5 cm.)

出典と根拠

ORDレコード
ord-27af18d1bf8a4de498dc281add7859b4
出典データセット
uspto-grants-1990_10
特許番号
US04962146

反応ノート

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