Diazoethane → Papulacandin B

HRID 1277608Notes

Reaction equation

HRID 1277608 reaction equation
[CH3:1][CH2:2][CH:3]([CH2:5][CH2:6]/[CH:7]=[CH:8]/[CH:9]=[C:10](/[CH:12]([OH:64])[CH2:13]/[CH:14]=[CH:15]/[CH:16]=[CH:17]/[C:18]([O:20][C@@H:21]1[C@@H:26]([OH:27])[C@@:25]2([O:37][CH2:36][C:29]3[CH:30]=[C:31]([OH:35])[CH:32]=[C:33]([OH:34])[C:28]2=3)[O:24][C@H:23]([CH2:38][OH:39])[C@H:22]1[O:40][C@@H:41]1[O:46][C@H:45]([CH2:47][O:48][C:49](/[CH:51]=[CH:52]/[CH:53]=[CH:54]/[CH:55]=[CH:56]/[CH:57]([OH:60])[CH2:58][CH3:59])=[O:50])[C@H:44]([OH:61])[C@H:43]([OH:62])[C@H:42]1[OH:63])=[O:19])\[CH3:11])[CH3:4].[N+](=CC)=[N-]>O1CCOCC1.CCOCC>[CH3:1][CH2:2][CH:3]([CH2:5][CH2:6]/[CH:7]=[CH:8]/[CH:9]=[C:10](/[CH:12]([OH:64])[CH2:13]/[CH:14]=[CH:15]/[CH:16]=[CH:17]/[C:18]([O:20][C@@H:21]1[C@@H:26]([OH:27])[C@@:25]2([O:37][CH2:36][C:29]3[CH:30]=[C:31]([OH:35])[CH:32]=[C:33]([OH:34])[C:28]2=3)[O:24][C@H:23]([CH2:38][OH:39])[C@H:22]1[O:40][C@@H:41]1[O:46][C@H:45]([CH2:47][O:48][C:49](/[CH:51]=[CH:52]/[CH:53]=[CH:54]/[CH:55]=[CH:56]/[CH:57]([OH:60])[CH2:58][CH3:59])=[O:50])[C@H:44]([OH:61])[C@H:43]([OH:62])[C@H:42]1[OH:63])=[O:19])\[CH3:11])[CH3:4].[CH3:1][CH2:2][CH:3]([CH2:5][CH2:6]/[CH:7]=[CH:8]/[CH:9]=[C:10](/[CH:12]([OH:64])[CH2:13]/[CH:14]=[CH:15]/[CH:16]=[CH:17]/[C:18]([O:20][C@@H:21]1[C@@H:26]([OH:27])[C@@:25]2([O:37][CH2:36][C:29]3[CH:30]=[C:31]([OH:35])[CH:32]=[C:33]([OH:34])[C:28]2=3)[O:24][C@H:23]([CH2:38][OH:39])[C@H:22]1[O:40][C@@H:41]1[O:46][C@H:45]([CH2:47][O:48][C:49](/[CH:51]=[CH:52]/[CH:53]=[CH:54]/[CH:55]=[CH:56]/[CH:57]([OH:60])[CH2:58][CH3:59])=[O:50])[C@H:44]([OH:61])[C@H:43]([OH:62])[C@H:42]1[OH:63])=[O:19])\[CH3:11])[CH3:4].[CH2:18]([O:20][CH2:21][CH3:22])[CH3:17]

Participants

6

Reactant 2

HCID 70695DiazoethaneHCID 6436198Papulacandin B

Product 2

HCID 6436198Papulacandin BHCID 86737852HCID 86737852, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 312751,4-DioxaneSolvent

Procedure

The ethyl ether of Papulacandin B is prepared as follows: a solution of 1050 mg of Papulacandin B in 30 ml dioxan is allowed to stand at 0° C. for 12 minutes with a solution of diazoethane in ether. After having evaporated off the solvent the residue is chromatographed on a silica gel column (70 g) with chloroform and increasing amounts of methanol (2 to 20%) as eluents. Colorless, amorphous Papulacandin B-monoethyl ether is obtained after precipitation from acetone/ether/hexane. The IR-spectrum (in KBr) shows the following bands: 3500, 2970, 2950, 1710, 1620, 1465, 1380, 1345, 1305, 1265, 1150, 1070, 1035, 1010 cm-1. The UV-spectrum (in ethanol) shows the following maximum values: λmax. (εmax.): 235 (40000), 265 (40000), 294 (shoulder). The 13C-NMR-spectrum shows the presence of an additional ethyl group Papulacandin B-diethylether, in which the 13C-NMR-spectrum shows that two additional ethyl groups are present, is obtained as further product.

Workup

  1. customAfter having evaporated off the solvent the residue
  2. customis chromatographed on a silica gel column (70 g) with chloroform
  3. temperatureincreasing amounts of methanol (2 to 20%) as eluents

Sources & evidence

ORD record
ord-23ee2792a3424bbe851ea0c9e32275ba
Source dataset
uspto-grants-1981_07
Patent number
US04278665

Reaction notes

Loading…