Azadirachtin b(SH) → Azadirachtin

HRID 1199733Notes

Reaction equation

HRID 1199733 reaction equation
[CH3:1]/[CH:2]=[C:3](/[C:5]([O:7][C@@H:8]1[C@:16]23[C@H:20]([C@@:21]([C@:25]45[O:30][C@@:29]4([CH3:31])[C@H:28]4[C@:32]6([OH:38])[C@H:36]([O:37][C@@H:26]5[CH2:27]4)[O:35][CH:34]=[CH:33]6)([CH3:24])[C@H:22]([OH:23])[C@H:14]4[C@H:15]2[C@:11]([C:44]([O:46][CH3:47])=[O:45])([CH2:12][O:13]4)[C@H:10]([O:48][C:49]([CH3:51])=[O:50])[CH2:9]1)[C@@:19]([OH:43])([C:39]([O:41][CH3:42])=[O:40])[O:18][CH2:17]3)=[O:6])\[CH3:4].C/C=C(/C(O[C@H]1[C@@]2(C(OC)=O)CO[C@@H]3[C@@H]2[C@@]2([C@H]([C@@]([C@]45O[C@@]4(C)[C@@H]4[C@]6(O)[C@H](O[C@H]5C4)OC=C6)(C)[C@@H]3O)[C@@H](C(OC)=O)OC2)[C@@H](O)C1)=O)\C>>[CH3:1]/[CH:2]=[C:3](/[C:5]([O:7][C@@H:8]1[C@:16]23[C@H:20]([C@@:21]([C@:25]45[O:30][C@@:29]4([CH3:31])[C@@H:28]4[C@:32]6([OH:38])[C@H:36]([O:37][C@H:26]5[CH2:27]4)[O:35][CH:34]=[CH:33]6)([CH3:24])[C@H:22]([OH:23])[C@H:14]4[C@H:15]2[C@:11]([C:44]([O:46][CH3:47])=[O:45])([CH2:12][O:13]4)[C@H:10]([O:48][C:49]([CH3:51])=[O:50])[CH2:9]1)[C@@:19]([OH:43])([C:39]([O:41][CH3:42])=[O:40])[O:18][CH2:17]3)=[O:6])\[CH3:4]

Participants

3

Reactant 2

HCID 21725521Azadirachtin b(SH)3×HCID 44584063HCID 44584063, compound

Product 1

HCID 5281303Azadirachtin

Procedure

The fractions around the two maxima were constituted by, in all, 8 portions. 15.5 g. azadirachtin A fraction, as well as 8.3 g. azadirachtin B fraction, were obtained. However, the azadirachtin A fraction still contained a large amount of azadirachtin B, whereas the azadirachtin B fraction still contained other substances in almost the same amount as azadirachtin B. Preparative HPLC was used in order to separate azadirachtin A and B. For this purpose, there was used a Latek column filled with silica gel-RP-18 material with a length of 540 mm. and an internal diameter of 54 mm. The separation was optimised. The flowthrough rate was 55 ml./minute with methanol/water (43:57 v/v) as elution agent. For each run, about 5 g. of the azadirachtin A fraction from the column chromatography on silica gel-RP-8 were applied to the column. Every 9 minutes, the receiver was changed at a volume of about 500 ml. The maximum of azadirachtin A was eluted after 284 minutes and the maximum of azadirachtin B appeared after 397 minutes. FIG. 2 of the accompanying drawings shows a preparative HPLC chromatography of the azadirachtin A fraction in the case of chromatography on RP-8. Pure azadirachtin A and azadirachtin B was only contained in the fractions round the peak maximum. Five further azadirachtins were also separated on a smaller scale in side fractions of the preparative HPLC with thin layer chromatography or semi-preparative HPLC. The various azadirachtin derivatives were prepared from azadirachtin A and azadirachtin B.

Workup

  1. customto separate azadirachtin A and B
  2. additionfilled with silica gel-RP-18 material with a length of 540 mm
  3. customThe separation
  4. wash/minute with methanol/water (43:57 v/v) as elution agent
  5. customEvery 9 minutes
  6. washThe maximum of azadirachtin A was eluted after 284 minutes
  7. customFive further azadirachtins were also separated on a smaller scale in side fractions of the preparative HPLC with thin layer chromatography or semi-preparative HPLC

Sources & evidence

ORD record
ord-353b8b217d5a47b39bfc16bac1a1a07b
Source dataset
uspto-grants-1990_02
Patent number
US04902713

Reaction notes

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