Ammonium Hydroxide → HCID 178497453, compound

HRID 406156Notes

Reaction equation

HRID 406156 reaction equation
[OH:1][C:2]1[C:7]2[C@@:8]3([OH:45])[C@@:21]([O:25][CH3:26])([C@H:22]([OH:24])[CH2:23][C:6]=2[CH:5]=[C:4]([CH3:46])[C:3]=1[C:47]([O:49][CH3:50])=[O:48])[C:20](=[O:27])[C:19]1[C:10](=[CH:11][C:12]2[C:13](=[O:43])[C:14]([NH:30][C@@H:31]4[C@H:36]([O:37][CH3:38])[C@H:35]([OH:39])[C@@H:34]([O:40][CH3:41])[C@H:33]([CH3:42])[O:32]4)=[CH:15][C:16](=O)[C:17]=2[C:18]=1[OH:28])[C:9]3=[O:44].[NH4+:51].[OH-]>CO>[OH:1][C:2]1[C:7]2[C@@:8]3([OH:45])[C@@:21]([O:25][CH3:26])([C@H:22]([OH:24])[CH2:23][C:6]=2[CH:5]=[C:4]([CH3:46])[C:3]=1[C:47]([O:49][CH3:50])=[O:48])[C:20](=[O:27])[C:19]1[C:10](=[CH:11][C:12]2[C:13](=[O:43])[C:14]([NH:30][C@@H:31]4[C@H:36]([O:37][CH3:38])[C@H:35]([OH:39])[C@@H:34]([O:40][CH3:41])[C@H:33]([CH3:42])[O:32]4)=[CH:15][C:16](=[NH:51])[C:17]=2[C:18]=1[OH:28])[C:9]3=[O:44]

Participants

4

Reactant 2

HCID 14923Ammonium Hydroxide2×HCID 67121454(6R,6aS,14aR)-methyl 1,6,8,14a-tetrahydroxy-11-((2S,3R,4R,5R,6S)-4-hydroxy-3,5-dimethoxy-6-methyltetrahydro-2H-pyran-2-ylamino)-6a-methoxy-3-methyl-7,9,12,14-tetraoxo-5,6,6a,7,9,12,14,14a-octahydrobenzo[a]tetracene-2-carboxylate

Product 1

HCID 178497453HCID 178497453, compoundYield 52%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of (6R,6aS,14aR)-methyl 1,6,8,14a-tetrahydroxy-11-((2S,3R,4R,5R,6S)-4-hydroxy-3,5-dimethoxy-6-methyltetrahydro-2H-pyran-2-ylamino)-6a-methoxy-3-methyl-7,9,12,14-tetraoxo-5,6,6a,7,9,12,14,14a-octahydrobenzo[a]tetracene-2-carboxylate (100 mg, 0.143 mmol) in methanol (2 mL) was added 29.5% NH4OH (0.1 mL) at room temperature, and the mixture was stirred under nitrogen for 2 h. 29.5% NH4OH (0.1 mL) was refilled and the mixture was stirred for 3 h. The reaction mixture was quenched with a saturated solution of ammonium chloride and extracted with chloroform. The combined extracts were washed with brine, dried (Na2SO4), filtered and concentrated. The residue was purified by preparative TLC (silica gel, 90:10 chloroform/methanol) to afford (6R,6aS,14aR)-methyl 1,6,8,14a-tetrahydroxy-11-((2S,3R,4R,5R,6S)-4-hydroxy-3,5-dimethoxy-6-methyltetrahydro-2H-pyran-2-ylamino)-9-imino-6a-methoxy-3-methyl-7,12,14-trioxo-5,6,6a,7,9,12,14,14a-octahydrobenzo[a]tetracene-2-carboxylate (52 mg, 52%) as a blue solid: 1H NMR (500 MHz, CDCl3) δ 15.80 (br s, 1H), 11.97 (s, 1H), 8.20 (br s, 1H), 7.90 (s, 1H), 6.90 (d, J=9.0 Hz, 1H), 6.49 (s, 1H), 5.27 (s, 1H), 5.00 (br s, 1H), 4.76 (br s, 1H), 4.70 (d, J=9.0 Hz, 1H), 3.84 (s, 3H), 3.79 (s, 3H), 3.75-3.67 (m, 2H), 3.60 (s, 3H), 3.58-3.54 (m, 2H), 3.40 (s, 3H), 3.32-3.28 (m, 2H), 3.12 (t, J=9.5 Hz, 1H), 2.54 (br s, 1H), 2.36 (s, 3H), 1.34 (d, J=5.5 Hz, 3H); MS (ESI+) m/z 697 (M+H); HPLC 96.6% (AUC), tR 10.34 min.

Workup

  1. stirringthe mixture was stirred for 3 h
  2. customThe reaction mixture was quenched with a saturated solution of ammonium chloride
  3. extractionextracted with chloroform
  4. washThe combined extracts were washed with brine
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by preparative TLC (silica gel, 90:10 chloroform/methanol)

Sources & evidence

ORD record
ord-7fb584e842514c60bd9d604faf9e2c42
Source dataset
uspto-grants-2014_06
Patent number
US08754054B2

Reaction notes

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