Acetic Acid → 17-Ethyl-1,14-dihydroxy-12-[2'-(4"-(4"'-chlorophenyloxy)-3"-methoxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9]octacos-18-ene-2,3,10,16-tetraone

HRID 1939062노트

반응식

HRID 1939062 반응식
[CH2:1]([CH:3]1[CH:29]=[C:28]([CH3:30])[CH2:27][CH:26]([CH3:31])[CH2:25][CH:24]([O:32][CH3:33])[CH:23]2[O:34][C:19]([OH:38])([CH:20]([CH3:37])[CH2:21][CH:22]2[O:35][CH3:36])[C:18](=[O:39])[C:17](=[O:40])[N:16]2[CH:11]([CH2:12][CH2:13][CH2:14][CH2:15]2)[C:10](=[O:41])[O:9][CH:8]([C:42]([CH3:53])=[CH:43][CH:44]2[CH2:49][CH2:48][CH:47]([OH:50])[CH:46]([O:51][CH3:52])[CH2:45]2)[CH:7]([CH3:54])[CH:6]([OH:55])[CH2:5][C:4]1=[O:56])[CH3:2].C(O)(=O)C.C(O)(=O)C.[Cl:65][C:66]1[CH:71]=[CH:70][C:69]([Bi](C2C=CC(Cl)=CC=2)C2C=CC(Cl)=CC=2)=[CH:68][CH:67]=1.C(O)(=O)C.C(=O)(O)O.ClC1C=CC([Bi](C2C=CC(Cl)=CC=2)C2C=CC(Cl)=CC=2)=CC=1>C(Cl)Cl.C([O-])(O)=O.[Na+].CC([O-])=O.CC([O-])=O.[Cu+2]>[CH2:1]([CH:3]1[CH:29]=[C:28]([CH3:30])[CH2:27][CH:26]([CH3:31])[CH2:25][CH:24]([O:32][CH3:33])[CH:23]2[O:34][C:19]([OH:38])([CH:20]([CH3:37])[CH2:21][CH:22]2[O:35][CH3:36])[C:18](=[O:39])[C:17](=[O:40])[N:16]2[CH:11]([CH2:12][CH2:13][CH2:14][CH2:15]2)[C:10](=[O:41])[O:9][CH:8]([C:42]([CH3:53])=[CH:43][CH:44]2[CH2:49][CH2:48][CH:47]([O:50][C:69]3[CH:70]=[CH:71][C:66]([Cl:65])=[CH:67][CH:68]=3)[CH:46]([O:51][CH3:52])[CH2:45]2)[CH:7]([CH3:54])[CH:6]([OH:55])[CH2:5][C:4]1=[O:56])[CH3:2]

참가 물질

8

반응물 4

HCID 176Acetic AcidHCID 224117-Ethyl-1,14-dihydroxy-12-[1-(4-hydroxy-3-methoxycyclohexyl)prop-1-en-2-yl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9]octacos-18-ene-2,3,10,16-tetroneHCID 86747380Tri(4-chlorophenyl)bismuth diacetateHCID 86747381Tri(4-chlorophenyl)bismuth carbonate

생성물 1

HCID 5702868817-Ethyl-1,14-dihydroxy-12-[2'-(4"-(4"'-chlorophenyloxy)-3"-methoxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9]octacos-18-ene-2,3,10,16-tetraone

시약·촉매·용매 3

HCID 8895Cupric acetate촉매HCID 6344Dichloromethane용매2회HCID 516892Sodium Bicarbonate용매

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온도
40 °C

실험 절차

To a stirred mixture of 17-ethyl-1,14-dihydroxy-12-[2'-(4"-hydroxy-3"-methoxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9 ]octacos-18-ene-2,3,10,16-tetraone (150 mg, 0.189 mmol, 1 eq) and Cu(OAc)2 (6.1 mg, 0.033 mmol, 0.17 eq) in CH2Cl2 (2.5 ml) in a round bottom flask equipped with a magnetic stir-bar was added tri(4-chlorophenyl)-bismuth diacetate [prepared immediately prior to use by addition of acetic acid (0.075 ml, 1.3 mmol, 6.9 eq) to a suspension of tri(4-chlorophenyl)-bismuth carbonate (200 mg, 0.331 mmol, 1.75 eq) in CH2Cl2 (2.5 ml)]. The reaction flask was then fitted with a reflux condenser and the mixture warmed to 40° C. After 20 hours the reaction mixture was cooled, diluted with saturated aqueous NaHCO3 (10 mL) and extracted 4 times with CH2Cl2. The organic extracts were dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The product was separated and purified two times by preparative TLC on silica gel (eluted with 2:1 hexanes/acetone) to give 40 mg 17-ethyl-1,14-dihydroxy-12-[2'-(4"-(4'"-chlorophenyloxy)-3"-methoxycyclohexyl)-1'-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9 ]octacos-18-ene-2,3,10,16-tetraone. (1H NMR, 13C NMR, and mass spectral analysis were consistent with the desired structure).

후처리

  1. customequipped with a magnetic stir-bar
  2. customprepared immediately
  3. customThe reaction flask was then fitted with a reflux condenser
  4. temperatureAfter 20 hours the reaction mixture was cooled
  5. extractionextracted 4 times with CH2Cl2
  6. dry with materialThe organic extracts were dried over anhydrous Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe product was separated
  10. custompurified two times by preparative TLC on silica gel (eluted with 2:1 hexanes/acetone)

출처 및 근거

ORD 기록
ord-3f99d5081352422085eb0619ffb7590a
출처 데이터셋
uspto-grants-1997_12
특허 번호
US05693648

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