Propargyl bromide → HCID 58078873, compound

HRID 929607Notes

Reaction equation

HRID 929607 reaction equation
[N:1]([CH2:4][CH2:5][O:6][CH2:7][CH2:8][O:9][CH2:10][CH2:11][O:12][CH2:13][CH2:14][O:15][CH2:16][CH2:17][O:18][CH2:19][CH2:20][O:21][CH2:22][CH2:23][O:24][CH2:25][CH2:26][OH:27])=[N+:2]=[N-:3].[H-].[Na+].[CH2:30](Br)[C:31]#[CH:32].CO.C(Cl)Cl>CN(C=O)C.C(Cl)Cl>[N:1]([CH2:4][CH2:5][O:6][CH2:7][CH2:8][O:9][CH2:10][CH2:11][O:12][CH2:13][CH2:14][O:15][CH2:16][CH2:17][O:18][CH2:19][CH2:20][O:21][CH2:22][CH2:23][O:24][CH2:25][CH2:26][O:27][CH2:32][C:31]#[CH:30])=[N+:2]=[N-:3]

Participants

7

Reactant 4

HCID 7842Propargyl bromideHCID 24758Sodium hydrideHCID 10960238O-(2-Azidoethyl)heptaethylene glycolHCID 21226129Dichloromethane methanol

Product 1

HCID 58078873HCID 58078873, compoundYield 78%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Procedure

23-Azido-3,6,9,12,15,18,21-heptaoxatricosan-1-ol (azido-PEG8-ol) (1.1 g, 3.17 mmol, 1.0 equiv.) was dissolved in N,N′-dimethylformamide (6 mL), and sodium hydride (152 mg, 6.34 mmol, 2.0 equiv.) was added, followed by propargyl bromide (80% in PhMe, 683 μL, 6.34 mmol, 2.0 equiv.). The reaction ran for 4 h at rt, at which time it was found complete by NMR aliquot. The reaction was taken up in CH2Cl2 (25 mL) and washed with a saturated aqueous ammonium chloride solution (25 mL). The aqueous solution was back-extracted with dichloromethane (2×10 mL), and combined organics were dried over MgSO4 and concentrated to a brown oil. Chromatography (3 cm×20 cm Silica gel, 3% MeOH/CH2Cl2) yielded azido-PEG8-yne (960 mg, 78% yield). IR (thin film/NaCl) 2874 (m), 2110 (m), 1160 (s), 1105 (s) cm−1; 1HNMR (400 MHz, CDCl3) δ 4.20 (d, J=2.4 Hz, 2H), 3.58 (m, 30H), 3.39 (t, J=5.1 Hz, 2H), 2.43 (t, J=2.4 Hz, 1H), 1.82 (s, 1H); 13CNMR (125 MHz, CDCl3) δ 79.82, 74.72, 70.75, 7022, 68.27, 58.62, 50.84; HRMS (ES+) calc'd for C19H35N3O8 (M+Na) m/z 456.231637. Found 456.23182.

Workup

  1. washwashed with a saturated aqueous ammonium chloride solution (25 mL)
  2. extractionThe aqueous solution was back-extracted with dichloromethane (2×10 mL)
  3. dry with materialcombined organics were dried over MgSO4
  4. concentrationconcentrated to a brown oil

Sources & evidence

ORD record
ord-e28d4f3da1df4d94b9b2da81b53a0371
Source dataset
uspto-grants-2016_03
Patent number
US09296708B2

Reaction notes

Loading…