Methanol → HCID 69460386, compound

HRID 915704Notes

Reaction equation

HRID 915704 reaction equation
[CH2:1]([O:8][C:9]1[C:24]([O:25][CH3:26])=[CH:23][C:12]([C:13]([N:15]2[CH2:19][C:18](=[CH2:20])[CH2:17][C@H:16]2[CH2:21][OH:22])=[O:14])=[C:11]([N+:27]([O-])=O)[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl[Sn]Cl.CO.C(Cl)(Cl)Cl.CO>CCOC(C)=O>[NH2:27][C:11]1[CH:10]=[C:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[C:24]([O:25][CH3:26])=[CH:23][C:12]=1[C:13]([N:15]1[CH2:19][C:18](=[CH2:20])[CH2:17][C@H:16]1[CH2:21][OH:22])=[O:14]

Participants

6

Reactant 4

HCID 887MethanolHCID 24479Stannous ChlorideHCID 21584188Chloroform methanolHCID 57084567HCID 57084567, compound

Product 1

HCID 69460386HCID 69460386, compoundYield 63%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

The nitro-alcohol 17 (0.637 g, 1.60 mmol), SnCl2 2H2O (1.81 g, 8.0 mmol) and methanol (36 mL) were heated at reflux and monitored by TLC (90% CHCl3/MeOH). After 1 hour the MeOH was evaporated in vacuo and the resulting residue cooled (ice), and treated carefully with saturated NaHCO3 (120 mL). The mixture was diluted with EtOAc (120 mL), and after 16 hours stirring at room temperature the inorganic precipitate was removed by filtration through celite. The organic layer was separated, washed with brine (100 mL), dried (MgSO4), filtered and evaporated in vacuo to give an orange glass. Flash chromatography (EtOAc) afforded the pure amine 18 as a pale yellow glass (0.37 g, 63%): [α]23D=−42.7° (c=3.7, CHCl3); 1H NMR (270 MHz, CDCl3) δ 7.44-7.29 (m, 5Harom), 6.77 (s, 1Harom), 6.27 (s, 1Harom), 5.12 (s, 2H, PhCH2O), 5.06-5.00 (m, 1H, NCH2C═CH2), 4.99-4.92 (m, 1H, NCH2C═CH2), 4.63-4.53 (m, 1H, NCHCH2OH), 4.25-3.60 (m, 10H, NCHCH2OH, NCH2C═CH2, OCH3, OH and NH2), 2.77 (dd, 1H, J=8.52, 15.85 Hz, NCH2C═CH2CH2), 2.43-2.39 (m, 1H, NCH2C═CH2CH2); 13C NMR (67.8 MHz, CDCl3) δ 171.4 (NC═O), 151.0 (Cquat), 143.3 (Cquat), 141.5 (Cquat), 140.6 (Cquat), 136.5 (Cquat), 128.6 and 128.0 (BnC—Harom), 127.8 (Cquat), 127.1 (BnC—Harom), 112.5 (C—Harom), 107.8 (NCH2C═CH2), 103.0 (C—Harom), 70.6 (PhCH2O), 65.9 (NCHCH2OH), 60.0 (NCHCH2OH), 57.1 (OCH3), 53.3 (NCH2C═CH2), 34.4 (NCH2C═CH2CH2); MS (EI), m/z (relative intensity) 368 (M+, 100), 353 (M-CH3, 2), 340 (1), 286 (2), 273 (4), 256 (M-NCH2C═CH2CH2CHCH2OH, 59 ), 249 (8), 226 (4), 200 (2), 196 (2), 166 (5), 138 (17), 112 (NCH2C═CH2CH2CHCH2OH, 39), 91 (PhCH2, 70), 82 (5), 65 (5); IR (NEAT) 3600-3000 (br, NH2 and OH), 3065, 3052, 2932, 2869, 2246, 1668, 1620, 1592, 1513, 1454, 1408, 1264, 1229, 1197, 1176, 1113, 1079, 1002, 909, 733, 698, 645 cm−1; exact mass calcd for C21H24N2O4 m/e 368.1736, obsd m/e 368.1662.

Workup

  1. temperatureat reflux
  2. customAfter 1 hour the MeOH was evaporated in vacuo
  3. temperaturethe resulting residue cooled (ice)
  4. additiontreated carefully with saturated NaHCO3 (120 mL)
  5. additionThe mixture was diluted with EtOAc (120 mL)
  6. customwas removed by filtration through celite
  7. customThe organic layer was separated
  8. washwashed with brine (100 mL)
  9. dry with materialdried (MgSO4)
  10. filtrationfiltered
  11. customevaporated in vacuo
  12. customto give an orange glass

Sources & evidence

ORD record
ord-b9c13a3098bd4980ba3e01eb13759cc0
Source dataset
uspto-grants-2007_09
Patent number
US07265105B2

Reaction notes

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