N cleavage

In contrast to the well-defined photochemical behavior of 1-azirines the thermal reactions of these compounds have been studied less thoroughly (68TL3499). The products formed on photolysis of azirines can best be rationalized in terms of an equilibration of the heterocyclic ring with a transient vinylnitrene. Thus, products formed from the thermolysis of azirines are generally consistent with C—N cleavage. For example, the vinylnitrene generated from the thermolysis of azirine (149) can be trapped with phosphines (72CCS6S). 

Practically all diaziridines (151) can be hydrolyzed by acids to a carbonyl compound and a hydrazine derivative. The only exceptions are diaziridines derived from formaldehyde, in which acid catalyzed N—N cleavage successfully competes with slow hydrolysis. Monoalkylhydrazines are formed in 80-95% yield, A/,A/ -dialkylhydrazines in 65-85% yield (B-67MI50800). 

Acid hydrolysis of (161) yields acetone and methylamine by N—N cleavage and methyl migration. 

Most diaziridines are not sensitive towards alkali. As an exception, diaziridines derived from 2-hydroxyketones are quickly decomposed by heating with aqueous alkali. Acetaldehyde, acetic acid and ammonia are formed from (162). This reaction is not a simple N—N cleavage effected intramolecularly by a deprotonated hydroxy group, since highly purified hydroxydiaziridine (162) is quite stable towards alkali. Addition of small amounts of hydroxybutanone results in fast decomposition. An assumed reaction path — Grob fragmentation of a hydroxyketone-diaziridine adduct (163) — is in accord with these observations (B-67MI50800). 

Intermolecular reactions with typical cycloaddition components are also possible. Phenyl isocyanate in ether converts triisopropyldiaziridinimine (182) to the 1,2,4-triazolidine under mild conditions. Labeling with a deuterated isopropyl group revealed that cycloaddition is not preceded by N—N cleavage, which should have resulted in deuterium randomization (77AG(E)109). 

Metal carbonyls react with diazirines with complex formation at one or both N atoms (75JOM(94)75). The 1 2 complex (187) is converted to (188) by N —N cleavage in acidic media. 

Complexes (191) and (192) are formed from dimethyldiazirine with carbonyls of chromium, molybdenum and tungsten. They show no tendency towards N—N cleavage (80JOM(193)57). Complex (193) is made from a mixed complex by displacement of norbor-nadiene. 

There are some reports on reactions involving complete N—N cleavage in diazirine reactions such as formation of amidine (205) from chlorophenyldiazirine, or on formation of products containing only one nitrogen atom. Betaine (206) was described as a product from difluorodiazirine and triphenylphosphine. Compound (207) is formed from decomposing (204) and cyclohexane (79AHC(24)63). 

Salts of mono-alkylated or arylated sulfur diimide anion [RNSN] (R = aryl, Bu, SiMcs) are prepared by Si-N cleavage of RNSNSiMcs with [(Me2N)3S][Mc3SiF2]. ° ° These anions adopt cis configurations with very short terminal S-N bond lengths (1.44 - 1.49 A) indicative of a thiazylamide anion, [RNS N] (5.21). ... 

The four mechanisms involving alkyl—N cleavage (the AL mechanisms) do not apply to this reaction. They are not possible for unsubstimted amides, since the only N—C bond is the acyl bond. They are possible for N-substituted and N,N-disub-stituted amides, but in these cases they give entirely different products and are not anude hydrolyses at all. 

Harper DB (1977) Microbial metabolism of aromatic nitriles. Enzymology of C-N cleavage by Nocardia sp. (Rhodochrous group) NCIB 11216. Biochem J 165 309-319. 

On treatment with aerated sodium in liquid ammonia, tetrahydroproto-berberine JV-oxides (35a and 35b) afforded the C-14—N bond cleavage products 36 and 37 (Scheme 8) (37). The same trans IV-oxides also gave the C-14—N cleavage products 38 and 39 on photolysis (33). 

N-N cleavage of the 4-proline-substituted 4,5-dihydro-l,2,4-oxadiazoles 188, shown in Equation (31), with formic acid gave the corresponding 4,5-dihydro-l,2,4-oxadiazoles 189 in good yield and with ee up to 91% <1999H(50)995>. 

In the meantime temperature-dependent stopped-flow measurements were conducted on the latter complex in order to determine the activation parameters of the N-N cleavage reaction (24). Plots of the absorption intensity at 418 nm vs. time at T — —35 to +15°C indicate biphasic kinetics with two rate constants 0bs(p and obs(2)> in analogy to our measurements of the tungsten complex. This time, however, both rates depended upon the acid concentration. Interestingly much smaller rate constants 0bs(i) and 0bs(2)> were found for all acid concentrations than given by Henderson et al. for his (single) rate constant kobs (up to 1 order of magnitude). Furthermore plots of 0bs(i) and kohs(2) vs. the acid concentration showed no saturation behavior but linear dependencies with slopes k and k and intercepts k und k, respectively (s — acid dependent and i — acid independent), Eq. (2) ... 

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