Bromide ion → Benzamidine

HRID 1990913Notes

Reaction equation

C=[N:2]O.[Br-].[C:5]([CH2:7][C:8](OC)=O)#[N:6].ClC[C:14](=O)[CH3:15].O1[CH2:21][CH2:20]OC1>>[C:5]([NH2:2])(=[NH:6])[C:7]1[CH:8]=[CH:21][CH:20]=[CH:15][CH:14]=1

Participants

Reactant 5

HCID 259Bromide ion

HCID 6350Nitrone

HCID 6571Chloroacetone

HCID 7747Methyl cyanoacetate

HCID 125861,3-Dioxolane

Product 1

HCID 2332Benzamidine

Procedure

The key intermediate for pyrrolo[2,3-d]pyrimidines with phenoxymethylene, alkoxymethylene or oxime ether moieties at C-6 is the bromide 7, which is prepared in 6 steps from methyl cyanoacetate and chloroacetone (scheme 4). The monoalkylation product 2 is protected as 1,3-dioxolane, then the pyrimidine ring is formed by reaction with a benzamidine. Cyclization of the pyrrole ring occurs on reaction with aqueous HCl, and refluxing with POCl3 yields the chloride 5. Boc-protection of the pyrrole followed by radical bromination with NBS gives the bromide 7.

Sources & evidence

ORD record: ord-9f9cb15987fd4d7783c9923c711e6c18
Source dataset: uspto-grants-2010_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07645754B2

Reaction notes

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