HCID 69497462, compound → HCID 5235856, compound
Reaction equation
[CH3:1][N:2]([CH3:26])[C:3]1[CH:4]=[CH:5][C:6]([N+:23]([O-])=[O:24])=[C:7]([CH:9]([O:16]C(=O)C(Cl)(Cl)Cl)C2C=CC=CC=2)[CH:8]=1.CN(C)C1C=CC([N+]([O-])=O)=C(C=1)COC(=O)C(Cl)(Cl)Cl>>[CH3:1][N:2]([CH3:26])[C:3]1[CH:4]=[CH:5][C:6]([N:23]=[O:24])=[C:7]([CH:8]=1)[CH:9]=[O:16]Participants
Procedure
Photolysis of 5-dimethylamino-2-nitrobenzyltrichloroacetate (41) and α-phenyl-5-dimethylamino-2-nitrobenzyltrichloroacetate (42) appeared to be of particular promise. They have absorption maxima at 395 and 398 nm, respectively, with molar extinction coefficients of around 17000 M.cm−1. The photolysis of compound 41, with no substitution at the α-position, was slower than that of the esters having an α-substitution16,17. Thus irradiation at 0.2% concentration, at 365 nm, gave the expected photoproduct, 5-dimethylamino-2-nitrosobenzaldehyde (53), in 30% yield after 16 min. In addition, the amount of accompanying secondary photoproducts, around 10%, was the highest among the esters evaluated so far. On the other hand, irradiations at lower concentrations indicated that the inner filter effect was diminishing as the photolysis proceeded. This was not the case with any esters tested by us before. Preliminary illuminations of compound 41 with blue light, λ>395 nm, at 0.002% concentration, carried out with the high pressure mercury arc lamp equipped with appropriate filters, gave about 12% photoconversion after 16 min. This result indicates that the development of photolabile esters whose activation would require considerably less expensive sources of visible light is feasible.
Workup
- customabsorption maxima at 395 and 398 nm
- customThus irradiation
- concentrationat 0.2% concentration
Sources & evidence
- ORD record
- ord-c399011d8ee745d2bcde7e936c96c7c5
- Source dataset
- uspto-grants-2007_11
- Patent number
- US07301049B2
Reaction notes
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