4-Nitrophenol → HCID 86632426, compound

HRID 2100237Notes

Reaction equation

HRID 2100237 reaction equation
B(F)(F)F.CCOCC.[N:10]([CH2:13][C@H:14]1[O:23][CH:18]([O:19][C:20](=O)[CH3:21])[C@H:17]([O:24][C:25](=[O:27])[CH3:26])[C@@H:16]([O:28][C:29](=[O:31])[CH3:30])[C@H:15]1[O:32][C:33](=[O:35])[CH3:34])=[N+:11]=[N-:12].[CH:36]1[C:41]([N+:42]([O-:44])=[O:43])=[CH:40][CH:39]=C(O)C=1.CCOCC>C(Cl)Cl>[C:25]([O:24][C@@H:17]1[C@@H:16]([O:28][C:29](=[O:31])[CH3:30])[C@@H:15]([O:32][C:33](=[O:35])[CH3:34])[C@@H:14]([CH2:13][N:10]=[N+:11]=[N-:12])[O:23][C@@H:18]1[O:19][C:20]1[CH:39]=[CH:40][C:41]([N+:42]([O-:44])=[O:43])=[CH:36][CH:21]=1)(=[O:27])[CH3:26]

Participants

6

Reactant 4

HCID 9804-NitrophenolHCID 3283Diethyl EtherHCID 8000Boron trifluoride etherateHCID 56619630HCID 56619630, compound

Product 1

HCID 86632426HCID 86632426, compoundYield 15.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

Boron trifluoride diethyl etherate (80 μl, 0.70 mmol) was added to a stirred solution of 6-azido-6-deoxy-1,2,3,4-tetra-O-acetyl-D-galactopyranose 36 (α:β, 1:1) (52 mg, 0.139 mmol) in DCM (5 mL). The solution was stirred under argon at RT. After 20 min a solution of p-nitrophenol (19 mg, 0.14 mmol) in DCM (5 mL) was added to the reaction mixture and stirring under argon maintained. After 65 min, t.1.c. (DCM:ether, 60:1) indicated formation of two products (Rf 0.1, 0.4) with some remaining starting material (Rf 0.3). The DCM was removed in vacuo. The residue was diluted with chloroform (30 mL), washed with brine (3×30 mL), dried (MgSO4), filtered and concentrated in vacuo. The residue was purified by flash column chromatography (DCM:ether, 60:1) to afford p-nitrophenyl 2,3,4-tri-β-acetyl-6-azido-6-deoxy-α-D-galactopyranoside 40 (9.7 mg, 14%) as a colourless oil; partial data [α]D25 +18.3 (c, 0.5 in CHCl3); νmax (thin film) 3430 (br, OH), 2101 (sh, N3), 1637 (st, C═O)cm−1; δH (500 Mz, CDCl3) 2.05, 2.09, 2.21 (9H, 3 x s, 3 x CH3), 3.13 (1H, dd, J5,6 4.2 Hz, J6,6′ 13.1 Hz, H-6), 3.46 (1H, dd, J5,6′ 8.2 Hz, H-6′), 4.18 (1H, dd, H-5), 5.34 (1H, dd, J2,3 3.7 Hz, J2,3 10.9 Hz, H-2), 5.49 (1H, d, J3,4 3.0 Hz, H-4), 5.57 (1H, dd, H-3), 5.94 (1H, d, H-1) 7.21 (2H, J=9.3 Hz, 2 x CHCHCNO2), 8.26 (2H, 2 x CHCNO2); 5c (125.7 MHz, CDCl3) 19.9, 20.0, 21.0 (3 x q, 3 x CH3), 51.9 (t, C-6), 53.3 (d, C-2), 66.6 (d, C-3), 67.6 (d, C-4), 69.0 (d, C-5), 95.2 (d, C-1), 115.6, 115.7, 125.3 (3 x s, 3 x C═O), 116.9, 117.0 (2 x d, CHCHCNO2), 126.5, 126.6 (2 x d, CHCNO2), 140.8 (s, CNO2), 167.2, 169.9, 170.2, 171.8 (4 x s, 3 x C═O, 1x CCHCHCNO2); m/z (CI+) 470 (M+NH4+, 10%).

Workup

  1. stirringstirring under argon
  2. temperaturemaintained
  3. customThe DCM was removed in vacuo
  4. additionThe residue was diluted with chloroform (30 mL)
  5. washwashed with brine (3×30 mL)
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by flash column chromatography (DCM:ether, 60:1)

Sources & evidence

ORD record
ord-28f8ff4efbae4e9181314404d53db56b
Source dataset
uspto-grants-2009_08
Patent number
US07572604B2

Reaction notes

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