Bromide ion → 1-Carboxymethyl phenazine

HRID 41808Notes

Reaction equation

HRID 41808 reaction equation
[CH3:1][C:2]1[C:15]2[C:6](=[N:7][C:8]3[C:13]([N:14]=2)=[CH:12][CH:11]=[CH:10][CH:9]=3)[CH:5]=[CH:4][CH:3]=1.BrN1C(=O)CCC1=O.[C:24]([O:32]OC(=O)C1C=CC=CC=1)(=[O:31])C1C=CC=CC=1.[Br-].[C-]#N.[K+].C(CC1C2C(=NC3C(N=2)=CC=CC=3)C=CC=1)#N>CN(C=O)C.C(Cl)(Cl)(Cl)Cl>[C:24]([CH2:1][C:2]1[C:15]2[C:6](=[N:7][C:8]3[C:13]([N:14]=2)=[CH:12][CH:11]=[CH:10][CH:9]=3)[CH:5]=[CH:4][CH:3]=1)([OH:32])=[O:31]

Participants

9

Reactant 6

HCID 259Bromide ionHCID 7187Benzoyl PeroxideHCID 9032Potassium CyanideHCID 67184N-bromobutanimideHCID 6066761-MethylphenazineHCID 148016371-Cyanomethyl phenazine2×

Product 1

HCID 148016381-Carboxymethyl phenazine

Reagents, catalysts & solvents 2

HCID 5943Carbon TetrachlorideSolventHCID 6228DimethylformamideSolvent

Procedure

Scheme 9 provides a synthetic route to the 1-carboxymethyl-5-N-ethyl phenazine derivative (42). The bromo derivative (37) is formed by reacting 1-methyl phenazine (36) (available from Apin Chemicals, UK) with N-bromosuccinimide in the presence of benzoyl peroxide and a solvent. Carbon tetrachloride is a particularly suitable solvent for the bromination reaction. Reaction of the bromide (37) with KCN in a suitable solvent, such as, for example, DMF, gives the 1-cyanomethyl phenazine derivative (38). Acid hydrolysis of the cyanophenazine (38) provides the 1-carboxymethyl phenazine (39). The acid group of compound (39) is converted to a methyl ester by reaction with methanol and HCl to give the phenazine ester (40). Ester (40) can be N-alkylated with dimethyl sulfate in the presence of potassium carbonate to give the 5-ethyl phenazine ester (41). Hydrolysis of the ester (41) with dilute hydrochloric acid provides the 5-ethyl-1-carboxymethyl phenazine (42).

Workup

  1. customfor the bromination reaction

Sources & evidence

ORD record
ord-9b48f59c8ccb4782b4a1c19fa4ca5f4b
Source dataset
uspto-grants-2013_09
Patent number
US08535511B2

Reaction notes

Loading…