Triphenylphosphine → 2-(1-Azidoethyl)-3-phenylbenzo[b]thiophene

HRID 242852Notes

Reaction equation

HRID 242852 reaction equation
CC(OC(/N=N/C(OC(C)C)=O)=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:34]1([C:40]2[C:41]3[CH:51]=[CH:50][CH:49]=[CH:48][C:42]=3[S:43][C:44]=2[CH:45](O)[CH3:46])[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1.C1(P([N:66]=[N+:67]=[N-:68])(C2C=CC=CC=2)=O)C=CC=CC=1>O1CCOCC1>[N:66]([CH:45]([C:44]1[S:43][C:42]2[CH:48]=[CH:49][CH:50]=[CH:51][C:41]=2[C:40]=1[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)[CH3:46])=[N+:67]=[N-:68]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 199401P,P-Diphenylphosphinic azideHCID 5363146Diisopropyl azodicarboxylateHCID 584591571-(3-Phenylbenzo[b]thiophen-2-yl)ethanol

Product 1

HCID 866688692-(1-Azidoethyl)-3-phenylbenzo[b]thiopheneYield 55.1%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

DIAD (556 mg, 2.75 mmol) was added to a solution of triphenylphosphine (722 mg, 2.75 mmol) in dioxane (5 mL) at 0° C. under a nitrogen atmosphere. After 10 min stirring, 1-(3-phenylbenzo[b]thiophen-2-yl)ethanol (350 mg, 1.37 mmol) was added followed by diphenylphosphoryl azide (454 mg, 1.65 mmol). Stirring at 20° C. was continued for 16 h and then volatiles were concentrated in vacuo. The crude reaction mixture was purified by column chromatography (Si—PCC, gradient 0-20% DCM in cyclohexane) affording 2-(1-Azidoethyl)-3-phenylbenzo[b]thiophene as a colourless oil (211 mg, 55%). 1H NMR (CDCl3, 400 MHz): δ 7.88 (1H, d, J=7.87 Hz), 7.54-7.42 (4H, m), 7.41-7.29 (4H, m), 4.97 (1H, q, J=6.80 Hz), 1.58 (3H, d, J=6.80 Hz).

Workup

  1. stirringStirring at 20° C.
  2. waitwas continued for 16 h
  3. concentrationvolatiles were concentrated in vacuo
  4. customThe crude reaction mixture
  5. customwas purified by column chromatography (Si—PCC, gradient 0-20% DCM in cyclohexane)

Sources & evidence

ORD record
ord-67dc41b91d994387a499aa7bd5b42c22
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

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