Nitric Acid → HCID 53864010, compound

HRID 1830990Notes

Reaction equation

HRID 1830990 reaction equation
C(OC([NH:8][CH2:9][CH2:10][CH2:11][O:12][C:13]1[CH:22]=[CH:21][C:16]([C:17]([O:19][CH3:20])=[O:18])=[CH:15][C:14]=1[O:23][CH3:24])=O)(C)(C)C.[N+:25]([O-])([OH:27])=[O:26].C(Cl)(Cl)Cl>O>[NH2:8][CH2:9][CH2:10][CH2:11][O:12][C:13]1[C:14]([O:23][CH3:24])=[CH:15][C:16]([C:17]([O:19][CH3:20])=[O:18])=[C:21]([N+:25]([O-:27])=[O:26])[CH:22]=1

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 6212ChloroformHCID 21584656HCID 21584656, compound

Product 1

HCID 53864010HCID 53864010, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

The ester 198 (4.0 g, 11.8 mmol) was added in small portions to a stirred solution of 70% HNO3 (2 mL acid/g of substrate) at room temperature and the reaction mixture was allowed to stir overnight. After 16 hours TLC (CHCl3) revealed the complete loss of starting material. The reaction mixture was cooled in an ice bath, and 15 g of iced water was added, precipitating the product. The precipitate was collected by vacuum filtration and washed with small amount of iced water. The filtrate was cooled and a second crop of precipitate was collected by vacuum filtration and washed with iced water. The combined precipitate was dried in vacuo to provide compound 199 as a yellow solid, which was not purified further, but used directly in the subsequent reaction (2.3 g, 70%). mp=101-103° C.; 1H-NMR (CDCl3/DMSO-d6, 270 MHz): δ2.31 (m, 2H, H2′), 3.20 (br, 2H, H3′), 3.95 (s, 3H, OCH3ether), 3.98 (s, 3H, OCH3ester), 4.24 (t, 2H, J=5.95 Hz, H1′), 7.11 (s, 1H, H6), 7.49 (s, 1H, H3), 8.21 (s, 3H, NH); 13C-NMR (CDCl3, 68.7 MHz): δ26.5 (C2′), 37.0 (C3′), 53.0 (OCH3ester), 56.0 (OCH3ether), 66.7 (C1′), 108.3 (C3), 111.0 (C6), 121.6 (Carom), 140.9 (C2), 149.3 (Carom), 152.6 (Carom), 166.8 (C═O); MS (E/I) m/z (relative intensity): 284 (M+., 90), 237 (70), 227 (93), 196 (47), 181 (38), 137 (100), 122 (81), 93 (52), 79 (44); HRMS (E/I) exact mass calcd for C12H17N2O6: m/e 284.1008, obsd m/e 284.1018; IR (Nujolò) n: (cm−1) 3472, 2937, 2911, 2855, 1733, 1532, 1516, 1462, 1377, 1292, 1224, 1143, 1052, 884, 812, 792, 773, 756, 724, 646.

Workup

  1. temperatureThe reaction mixture was cooled in an ice bath
  2. customprecipitating the product
  3. filtrationThe precipitate was collected by vacuum filtration
  4. washwashed with small amount of iced water
  5. temperatureThe filtrate was cooled
  6. filtrationa second crop of precipitate was collected by vacuum filtration
  7. washwashed with iced water
  8. customThe combined precipitate was dried in vacuo

Sources & evidence

ORD record
ord-19196174e3844820ba2655be58cc17d1
Source dataset
uspto-grants-2006_06
Patent number
US07067511B2

Reaction notes

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