Hydrochloric Acid → HCID 68008920, compound

HRID 1429092Notes

Reaction equation

HRID 1429092 reaction equation
BrC1C=CC(S([O:11][C@@H:12]2[CH2:45][N:15]3[C:16](=[O:44])[C@@H:17]([NH:36][C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH:23]=[CH:24][C@@H:25]4[CH2:30][C@@:26]4([C:31]([O:33][CH2:34][CH3:35])=[O:32])[NH:27][C:28](=[O:29])[C@@H:14]3[CH2:13]2)(=O)=O)=CC=1.[CH:46]1[C:59]2[C:58]3[C:53](=[CH:54][CH:55]=[CH:56][CH:57]=3)[C:52](=[O:60])[NH:51][C:50]=2[CH:49]=[CH:48][CH:47]=1.C(=O)([O-])[O-].[Cs+].[Cs+].Cl>O.CS(C)=O>[C:40]([O:39][C:37]([NH:36][C@@H:17]1[C:16](=[O:44])[N:15]2[CH2:45][C@H:12]([O:60][C:52]3[N:51]=[C:50]4[C:59](=[C:58]5[C:53]=3[CH:54]=[CH:55][CH:56]=[CH:57]5)[CH:46]=[CH:47][CH:48]=[CH:49]4)[CH2:13][C@H:14]2[C:28](=[O:29])[NH:27][C@:26]2([C:31]([O:33][CH2:34][CH3:35])=[O:32])[CH2:30][C@H:25]2[CH:24]=[CH:23][CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]1)=[O:38])([CH3:43])([CH3:42])[CH3:41].[C:40]([O:39][C:37]([NH:36][C@@H:17]1[C:16](=[O:44])[N:15]2[CH2:45][C@H:12]([O:11][C:46]3[C:59]4[C:50](=[N:51][CH:52]=[C:53]5[C:58]=4[CH:57]=[CH:56][CH:55]=[CH:54]5)[CH:49]=[CH:48][CH:47]=3)[CH2:13][C@H:14]2[C:28](=[O:29])[NH:27][C@:26]2([C:31]([O:33][CH2:34][CH3:35])=[O:32])[CH2:30][C@H:25]2[CH:24]=[CH:23][CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]1)=[O:38])([CH3:43])([CH3:41])[CH3:42]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 18536(5H)-PhenanthridinoneHCID 10796Cesium carbonateHCID 86642249HCID 86642249, compound

Product 2

HCID 68008920HCID 68008920, compoundYield 120%HCID 68499992HCID 68499992, compound

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent

Conditions

Temperature
75 °C

Procedure

To (2S ,6S ,13aS,14aR,16aS,Z)-ethyl 2-(4-bromophenylsulfonyloxy)-6-(tert-butoxycarbonylamino)-5,16-dioxo-1,2,3,5,6,7,8,9,10,11,13a,14,14a,15,16,16a-hexadecahydrocyclopropa[e]pyrrolo[1,2-a][1,4]diazacyclopentadecine-14a-carboxylate (9.00 g, 12.6 mmol) and phenanthridin-6(5H)-one (3.08 g, 15.8 mmol) was added DMSO (50 ml). To this mixture was added cesium carbonate (6.17 g, 18.9 mmol) and the resulting mixture was heated at 75° C. for 3 hr. The reaction mixture was cooled to room temperature, diluted with water (400 ML) and neutralized with HCl (2N, 7.8 mL). The mixture was filtered and the white solid was rinsed with water. The solid was taken up in dichloromethane and filtered to remove insoluble phenanthridinone. The filtrate was concentrated and the residue was purified flash chromatography on silica gel (4:6 hexane/ethyl acetate) to provide the title compound (2R,6S,13aS,14aR,16aS,Z)-ethyl 6-(tert-butoxycarbonylamino)-5,16-dioxo-2-(phenanthridin yloxy)-1,2,3,5,6,7,8,9,10,11,13a,14,14a,15,16,16a-hexadecahydrocyclopropa[e]pyrrolo [1,2-a][1,4]diazacyclopentadecine-14a-carboxylate as a pale yellow solid (5.07g, 60% yield).

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. filtrationThe mixture was filtered
  3. washthe white solid was rinsed with water
  4. filtrationfiltered
  5. customto remove insoluble phenanthridinone
  6. concentrationThe filtrate was concentrated
  7. customthe residue was purified flash chromatography on silica gel (4:6 hexane/ethyl acetate)

Sources & evidence

ORD record
ord-222efaad80464ada84dd154c0b8410b5
Source dataset
uspto-grants-2015_01
Patent number
US08937041B2

Reaction notes

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