- NEW SYNTHETIC "TRICKS". FROM ALIPHATIC AMINES AND AMIDES TO AZIDES AND/OR HOW TO CONVERT RNHCOR' INTO RNHCOR" AVOIDING DRASTIC HYDROLYSES
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Controlled reduction of N-alkyl-N-nitrosoamides to hydrazides followed by nitrosation and fragmentation affords azides in 80percent overall yields, under mild conditions.This simple idea is the basis of methods for the conversion of alkylamines and N-alkylamides to alkyl azides, of RNHCOR' into RNHCOR" or RN(COR''')2, and of lactames into ω-azido esters or ω-azido acids.
- Garcia, Jordi,Vilarrasa, Jaume
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p. 341 - 342
(2007/10/02)
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- Reactions of NH Radicals. III. Photolysis of HN3 in the Presence of C2H4 at 313 nm
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Photolysis of HN3 vapor in the presence of C2H4 was studied at 313 nm and 30 deg C.The main products were N2, H2, CH4, C2H6, NH4N3, C2H5N * HN3 (salt of C2H5N (azomethines) with HN3), HCN, CH3CN, CH3N3, and C2H5N3.The quantum yields of these products were measured as a function of the light intensity and pressures of HN3 and C2H4.The following mechanism for the main reactions was infered: HN3 + hv(313 nm) -> NH(a1Δ) + N2; NH(a1Δ) + HN3 -> 2N2 + 2H (2a); NH(a1Δ) + HN3 -> NH2 + N3 (2b); NH(a1Δ) + HN3 -> N2 + N2H2* (2c); NH(a1Δ) + C2H4 -> C2H5N* (aziridine and vinylamine) (3); C2H5N* -> CH3 + CH2N (4); C2H5N* -> H2 + CH3CN (5); C2H5N* -> H + C2H4N (6); C2H5N* -> C2H3 + NH2 (7).The rate constant ratios at 30 deg C are: k3/k2 = 1.64; k5/k4 = 0.102; k6/k4 = 0.564; k7/k4 = 0.734.The collisional deactivation from NH(a1Δ) to NH(X3Σ-) by C2H4 was not found.The lifetime of C2H5N* is much shorter than 6.8 * 10-11 s for C2H5NH2*(1Δ) + C2H6)).The relative and absolute rates for the reactions of NH(a1Δ) with HN3, Xe, C2H6, and C2H4 are discussed.
- Kodama, Sukeya
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p. 2363 - 2370
(2007/10/02)
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