Pyridine → HCID 86672876, compound

HRID 1907040Notes

Reaction equation

HRID 1907040 reaction equation
Cl[C:2]([O:4][C:5]1[CH:10]=[CH:9][C:8]([N+:11]([O-:13])=[O:12])=[CH:7][CH:6]=1)=[O:3].N1C=CC=CC=1.[Si:20]([O:27][CH2:28][C:29]1[CH:45]=[CH:44][C:32]([C:33]([NH:35][NH:36][C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])=[O:34])=[C:31]([CH2:46][OH:47])[CH:30]=1)([C:23]([CH3:26])([CH3:25])[CH3:24])([CH3:22])[CH3:21].C(Cl)Cl>C1COCC1>[Si:20]([O:27][CH2:28][C:29]1[CH:45]=[CH:44][C:32]([C:33]([NH:35][NH:36][C:37]([O:39][C:40]([CH3:41])([CH3:43])[CH3:42])=[O:38])=[O:34])=[C:31]([CH2:46][O:47][C:2]([O:4][C:5]2[CH:6]=[CH:7][C:8]([N+:11]([O-:13])=[O:12])=[CH:9][CH:10]=2)=[O:3])[CH:30]=1)([C:23]([CH3:26])([CH3:24])[CH3:25])([CH3:22])[CH3:21]

Participants

6

Reactant 4

HCID 1049PyridineHCID 6344DichloromethaneHCID 821294-Nitrophenyl chloroformateHCID 86672877HCID 86672877, compound

Product 1

HCID 86672876HCID 86672876, compoundYield 97%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 4-nitrophenyl chloroformate (1.10 g, 5.48 mmol) in 40 mL of anhydrous THF was added pyridine (390 μL, 5.48 mmol) at 0° C. After stirring for 15 min, a solution of 5 (1.50 g, 3.65 mmol) in 15 mL of anhydrous THF was added dropwise within 10 min, and the mixture was allowed to warm up. Stirring was continued at room temperature for 16 h after which 50 mL DCM was added. The mixture was washed with 1M HCl (3×60 mL) and brine (1×50 mL), and the aqueous layers were re-extracted with DCM. The combined organic phases were dried over MgSO4 and the volatiles were removed in vacuo. Flash chromatography of the crude product (1:2 EtOAc-hexane) afforded 6 (97%) as a colorless solid: 1H-NMR (400 MHz, CDCl3): δ 0.11 (s, 6H), 0.94 (s, 9H), 1.49 (s, 9H), 4.79 (s, 2H), 5.58 (s, 2H), 6.71 (br s, 1H), 7.37-7.42 (m, 3H), 7.54 (s, 1H), 7.61 (d, J=8.1 Hz, 1H), 7.96 (br s, 1H), 8.23-8.29 (m, 2H); 13C-NMR (100 MHz, CDCl3): δ −5.1, 18.5, 26.0, 28.3, 64.3, 68.5, 82.3, 121.9, 125.4, 126.5, 127.4, 128.3, 131.4, 133.6, 145.5, 145.7, 152.5, 155.5, 155.6, 168.0; MS (TOF) m/z=598.2 (M+Na+, 100).

Workup

  1. temperatureto warm up
  2. stirringStirring
  3. waitwas continued at room temperature for 16 h
  4. washThe mixture was washed with 1M HCl (3×60 mL) and brine (1×50 mL)
  5. extractionthe aqueous layers were re-extracted with DCM
  6. dry with materialThe combined organic phases were dried over MgSO4
  7. customthe volatiles were removed in vacuo

Sources & evidence

ORD record
ord-2cc9acdcff314dfcbee32994d98c11fc
Source dataset
uspto-grants-2013_12
Patent number
US08597631B2

Reaction notes

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