1,2-Dibromoethane → HCID 59643073, compound

HRID 2251094Notes

Reaction equation

HRID 2251094 reaction equation
[Cl:1][C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[CH2:4]Br.BrCCBr.CON(C)[C:17]([C:19]1[N:29]([C:30]2[CH:35]=[CH:34][C:33]([F:36])=[CH:32][CH:31]=2)[C:22]2[N:23]=[C:24]([S:27][CH3:28])[N:25]=[CH:26][C:21]=2[CH:20]=1)=[O:18].[Mg]>C1COCC1.C(OCC)C>[Cl:1][C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[CH2:4][C:17]([C:19]1[N:29]([C:30]2[CH:35]=[CH:34][C:33]([F:36])=[CH:32][CH:31]=2)[C:22]2[N:23]=[C:24]([S:27][CH3:28])[N:25]=[CH:26][C:21]=2[CH:20]=1)=[O:18]

Participants

7

Reactant 4

HCID 78391,2-DibromoethaneHCID 11905alpha-Bromo-o-chlorotolueneHCID 5462224MagnesiumHCID 59643088HCID 59643088, compound

Product 1

HCID 59643073HCID 59643073, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a round bottom flask equipped with a condenser is added Mg powder (0.35 g, 0.02 mmol) and diethyl ether (10 mL). 2-Chlorobenzyl bromide (0.10 mL, 0.76 mmol) and a catalytic amount of 1,2-dibromoethane (5 μL) is added to the reaction mixture. After an initial exotherm, the reaction solution develops a yellow color. 7-(4-Fluoro-phenyl)-2-methylsulfanyl-7H-pyrrolo[2,3-d]pyrimidine-6-carboxylic acid methoxy-methyl-amide, 29, (0.22 g, 0.63 mmol) is dissolved in THF (10 mL) and the Grignard reagent is then carefully transferred dropwise using a cannula using nitrogen to initiate and continue the transfer. The mixture is allowed to stir at room temperature for 2 hours after which the magnesium is removed by filtration and the filtrate concentrated in vacuo. The residue is purified by preparative HPLC to afford 64 mg of the desired product as a pale colored solid: 1H NMR (300 MHz, CDCl3) δ 9.02 (s, 1H), 7.60 (s, 1H), 7.42-7.38 (m, 1H), 7.37-7.22 (m, 5H), 7.18 (t, J=8.7 Hz, 2H), 4.40 (s, 2H), 2.44 (s, 3H); ESI+ MS: m/z (rel intensity) 411.9 (100, M++H).

Workup

  1. customTo a round bottom flask equipped with a condenser
  2. customis removed by filtration
  3. concentrationthe filtrate concentrated in vacuo
  4. customThe residue is purified by preparative HPLC

Sources & evidence

ORD record
ord-0b00c1a2bfd94d178edd65af4e59750f
Source dataset
uspto-grants-2008_01
Patent number
US07319102B1

Reaction notes

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