Desmycosin → 19-Deformyldesmycosin

HRID 1088420노트

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HRID 1088420 반응식
[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]

참가 물질

4

반응물 1

HCID 6437804Desmycosin

생성물 1

HCID 644405819-Deformyldesmycosin수율 73%

시약·촉매·용매 2

HCID 241Benzene용매HCID 8857Ethyl Acetate용매

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온도
90 °C

실험 절차

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)

후처리

  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.)

출처 및 근거

ORD 기록
ord-27af18d1bf8a4de498dc281add7859b4
출처 데이터셋
uspto-grants-1990_10
특허 번호
US04962146

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