Phosphorus trichloride → 4-Chloro-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrole-6-carbonitrile

HRID 60249Notes

Reaction equation

HRID 60249 reaction equation
[Cl:1][C:2]1[C:10]2[C:9]3[CH:11]=[C:12]([C:16]#[N:17])[N+:13]([O-])=[CH:14][C:8]=3[N:7]([CH2:18][O:19][CH2:20][CH2:21][Si:22]([CH3:25])([CH3:24])[CH3:23])[C:6]=2[N:5]=[CH:4][CH:3]=1.P(Cl)(Cl)Cl>ClCCl>[Cl:1][C:2]1[C:10]2[C:9]3[CH:11]=[C:12]([C:16]#[N:17])[N:13]=[CH:14][C:8]=3[N:7]([CH2:18][O:19][CH2:20][CH2:21][Si:22]([CH3:25])([CH3:24])[CH3:23])[C:6]=2[N:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 24387Phosphorus trichlorideHCID 670274914-Chloro-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrole-6-carbonitrile-7-oxide

Product 1

HCID 582666684-Chloro-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4',3'-d]pyrrole-6-carbonitrileYield 95%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 4-chloro-9-(2-trimethylsilanyl-ethoxymethyl)-9H-dipyrido[2,3-b;4′,3′-d]pyrrole-6-carbonitrile-7-oxide (1.3 g, 3.52 mmol) in dichloromethane (11 mL) was treated with phosphorus trichloride (2N solution in dichloromethane, 1.9 mL, 3.9 mmol) and the reaction mixture was stirred at ambient temperature for 2 hours. The reaction mixture was concentrated in vacuo and purified by flash chromatography (silica, 40 g, ISCO, 0-40% ethyl acetate in heptane) to afford the title compound as a white solid (1.2 g, 93%). 1H NMR (400 MHz, CDCl3) δ 9.20 (d, J=0.9, 1H), 8.74 (d, J=0.9, 1H), 8.60 (d, J=5.3, 1H), 7.39 (d, J=5.3, 1H), 6.02 (s, 2H), 3.60 (t, J=8.0, 2H), 0.94 (t, J=8.0, 2H), −0.08 (s, 9H).

Workup

  1. concentrationThe reaction mixture was concentrated in vacuo
  2. custompurified by flash chromatography (silica, 40 g, ISCO, 0-40% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-a4019a121dcc4270aed67ba750ef0c7a
Source dataset
uspto-grants-2016_09
Patent number
US09440976B2

Reaction notes

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