Hydrochloric Acid → HCID 68645831, compound

HRID 2367994Notes

Reaction equation

HRID 2367994 reaction equation
C([C:3]1[C:4]([B:21]2[O:25]C(C)(C)[C:23]([CH3:29])(C)[O:22]2)=[C:5]([CH:18]=[CH:19][CH:20]=1)[O:6][CH2:7][CH2:8][CH2:9][NH:10][C:11](=[O:17])[O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=O.C[N+:31]([O-:33])=[O:32].[OH-].[Na+].Cl>CCCCCCCCCCCCCCCC[N+](C)(C)C.[Br-].C1COCC1.O>[OH:25][B:21]1[C:4]2[C:5]([O:6][CH2:7][CH2:8][CH2:9][NH:10][C:11](=[O:17])[O:12][C:13]([CH3:14])([CH3:15])[CH3:16])=[CH:18][CH:19]=[CH:20][C:3]=2[CH:23]([CH2:29][N+:31]([O-:33])=[O:32])[O:22]1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 6375NitromethaneHCID 14798Sodium HydroxideHCID 87111564HCID 87111564, compound

Product 1

HCID 68645831HCID 68645831, compoundYield 64.5%

Reagents, catalysts & solvents 3

HCID 5974Hexadecyltrimethylammonium BromideCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of tert-butyl 3-(3-formyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenoxy)propylcarbamate (3.1 g, 8.47 mmol), MeNO2 (775 mg, 12.7 mmol), CTAB (310 mg, 0.85 mmol) and NaOH (407 mg, 10 mmol) in THF (35 mL) and H2O (8 mL) was stirred at room temperature for 3 h. The mixture was adjusted to pH 2-3 using 2N HCl and then stirred for 30 min. The mixture was extracted with EtOAc (2×80 mL). The organic layer was washed with water (30 mL) and brine (30 mL), dried over anhydrous Na2SO4 and then concentrated. The residue was purified by column chromatography on silica gel (PE/EtOAc=5/1) to give the product (2 g, yield 64.5%). 1H NMR (400 MHz, DMSO-d6) δ 9.05 (s, 1H), 7.47 (t, J=7.8 Hz, 1H), 7.07 (d, J=7.4 Hz, 1H), 6.91 (m, 2H), 5.72 (dd, J=9.0, 2.7 Hz, 1H), 5.31 (dd, J=13.3, 2.7 Hz, 1H), 4.54 (dd, J=13.3, 9.4 Hz, 1H), 4.05 (t, J=6.3 Hz, 2H), 3.09 (m, 2H), 1.83 (m, 2H), 1.37 (s, 9H); MS (ESI) m/z=367 [M+H]+.

Workup

  1. stirringstirred for 30 min
  2. extractionThe mixture was extracted with EtOAc (2×80 mL)
  3. washThe organic layer was washed with water (30 mL) and brine (30 mL)
  4. dry with materialdried over anhydrous Na2SO4
  5. concentrationconcentrated
  6. customThe residue was purified by column chromatography on silica gel (PE/EtOAc=5/1)

Sources & evidence

ORD record
ord-a8e370f43cbf42a2a9b2c43fd71beb22
Source dataset
uspto-grants-2014_04
Patent number
US08703742B2

Reaction notes

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