27958-83-4Relevant articles and documents
A laser flash photolysis study on 2-azido-N,N-diethylbenzylamine - The reactivity of iminoquinone methides in solution
Bucher, Goetz
, p. 2463 - 2475 (2007/10/03)
Photolysis of 2-azido-N,N-diethylbenzylamine (1) in acetonitrile solution in the presence of various quenchers yields products of common nitrene chemistry (that is, derived from a didehydroazepine or a triplet nitrene), together with products arising from trapping of stereoisomeric iminoquinone methides. These intermediates are formed in a monophotonic process, by dediazotation of the precursor combined with a 1,4-hydrogen shift. The reactivity of the iminoquinone methides (IQM) towards a variety of quenchers, including dienophiles and various nucleophiles, has been explored, using acetonitrile, DMF, and n-hexane as solvents. IQM reacts efficiently with electron deficient dienophiles [kq(maleic anhydride) = 2.4·107 M-1 s-1], but not with simple olefins such as cyclohexene. IQM shows low to medium reactivity towards simple primary or secondary amines [kq(n-propylamine) = 6.4·104 M-1 s-1], medium reactivity with sterically unhindered simple alcohols [kq(methanol) = 4.6·106 M-1 s-1], and high to very high reactivity towards thiols [kq(n-dodecanethiol) = 1.1·109 M-1 s-1], diols, and triols [kq(glycerol) = 1.5·108 M-1 s-1], and sugars [kq(D-glucose) = 1.0·109 M-1 s-1]. IQM also reacts rapidly with cytosine: kq(cytosine) = 3.4·108 M-1 s-1, while the reaction with adenine or thymine is less efficient [kq(adenine) = 6.4·107 M-1 s-1, kq(thymine) = 7.7·106 M-1 s-1].
