Acetic Acid → HCID 57111339, compound

HRID 1655769Notes

Reaction equation

HRID 1655769 reaction equation
[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.[O:65]([C:72]1[CH:77]=[CH:76][C:75]([Bi](C2C=CC(OC3C=CC=CC=3)=CC=2)C2C=CC(OC3C=CC=CC=3)=CC=2)=[CH:74][CH:73]=1)[C:66]1[CH:71]=[CH:70][CH:69]=[CH:68][CH:67]=1.C(O)(=O)C.C(=O)(O)O.O(C1C=CC([Bi](C2C=CC(OC3C=CC=CC=3)=CC=2)C2C=CC(OC3C=CC=CC=3)=CC=2)=CC=1)C1C=CC=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:75]3[CH:76]=[CH:77][C:72]([O:65][C:66]4[CH:71]=[CH:70][CH:69]=[CH:68][CH:67]=4)=[CH:73][CH:74]=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]

Participants

8

Reactant 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 86747269HCID 86747269, compound2×HCID 86747270HCID 86747270, compound

Product 1

HCID 57111339HCID 57111339, compound

Reagents, catalysts & solvents 3

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolvent2×HCID 516892Sodium BicarbonateSolvent

Conditions

Temperature
40 °C

Procedure

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, 0.19 mmol, 1 eq) and Cu(OAc)2 (6.0 mg, 0.033 mmol, 0.17 eq) in CH2Cl2 (2.5 ml) in a round bottom flask equipped with a magnetic stir-bar and reflux condenser was heated to 40° C. then treated with tri(4-phenoxyphenyl)bismuth diacetate [prepared immediately prior to use by addition of acetic acid (0.075 mL, 1.31 mmol, 6.9 eq) to a suspension of tri(4-phenoxyphenyl)bismuth carbonate (225 mg, 0.29 mmol, 1.5 eq) in CH2Cl2 (2.5 ml)]. After 18 hours TLC analysis showed the reaction to be incomplete and additional tri(4-phenoxyphenyl) bismuth diacetate (0.10 mmol) was added. The reaction mixture was stirred with heating for 5 hours then cooled, diluted with saturated aqueous NaHCO3, and extracted 2 times with CH2Cl2. The extracts were combined, dried over Na2SO4, filtered, and concentrated in vacuo. The product was isolated and purified by preparative TLC on silica gel (2:1 hexanes/acetone) to give 66 mg of 17-ethyl-1,14-dihydroxy-12-[2'-(4"-(4'"-penoxyphenyloxy)-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).

Workup

  1. customequipped with a magnetic stir-bar
  2. temperaturereflux condenser
  3. customprepared immediately
  4. customthe reaction
  5. temperaturewith heating for 5 hours
  6. temperaturethen cooled
  7. extractionextracted 2 times with CH2Cl2
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customThe product was isolated
  12. custompurified by preparative TLC on silica gel (2:1 hexanes/acetone)

Sources & evidence

ORD record
ord-848077c7fe1d479e8868fbc0cdc6e051
Source dataset
uspto-grants-1993_10
Patent number
US05250678

Reaction notes

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