Extrusion of nitrogen

The addition of phthalimidylnitrene (374) to simple alkynes affords 1-azirines in yields of 1-15% (Scheme 10). In this reaction, which is of no real preparative value, the symmetrical 2-azirines (375) were suggested as the most plausible intermediates and unequivocal proof of the existence of such species was demonstrated from a series of 1,2,3-triazole pyrolysis reactions <71CC1518). Extrusion of nitrogen from the regioisomeric 4,5-disubstituted 1,2,3-triazoles (376) during flash vacuum pyrolysis furnished identical product mixtures which included both regioisomeric 1-azirines (377). 

Aziridinimine derivatives are also accessible by the photochemically induced extrusion of nitrogen and ring contraction of simple alkylidene tetrazolines (424) <75AG(E)428). Thus, Pyrex-filtered photolysis of (424) at -60 °C quantitatively afforded the aziridinimines (425). 

Oxiranes have been made by extrusion of nitrogen from oxadiazolenes (Scheme 81) (B-73MI50502), by flash thermolysis of dioxazolones (Scheme 82) (81JA5414), and (cc-lactones) by photolysis of l,2-dioxole-3,5-diones (Scheme 83) (73JOC2269). 

Oxidation of A-aminoazetidines (19), deoxygenation of A-nitrosoazetidines (20) and direct deamination of azetidines (21) with difluoroamine leads to cyclopropanes (23) by extrusion of nitrogen from a diazine intermediate (22) (63JA97). A further interesting ring contraction occurs in the Ag" catalysed solvolysis of the A-chloroazetidine (24), which appears to involve the intermediate cation (2S) (7ITLI09). 

Perhaps the most firmly based report for the formation of an azete involves flash pyrolysis of tris(dimethylamino)triazine (303). This gave a red pyrolysate believed to contain the highly stabilized azete (304) on the basis of spectroscopic data. The putative azete decomposed only slowly at room temperature, but all attempts to trap it failed (73AG(E)847). Flash pyrolysis of other 1,2,3-triazines gives only acetylenes and nitriles and it is not possible to tell whether these are formed by direct <,2-l-<,2-l-<,2 fragmentation of the triazine or by prior extrusion of nitrogen and collapse to an azete (81JCR(S)162). 

An intramolecular version of an azide cycloaddition of 221 and 222 provided cyclopropylimines 224 and 225 via formation of triazoline 223 followed by extrusion of nitrogen with concomitant 1,2-hydrogen shift (Scheme 36) [58], The cyclization was found to be solvent dependent polar solvents such as DMF gave the best yields, whereas benzene gave several side products. 

Nitrotetrazolo[l,5-/]furazano[4,5- ]pyridine 1-oxide 340 (NFP) was prepared by the extrusion of nitrogen from 2,6-diazido-3,5-dinitropyridine followed by ring closure (Scheme 85) <2005JEM99>. 

The glutamic moiety of TNP-351, a pyrrolo[2,3-d]pyrimidine glutamic acid derivative, and related compounds have been transformed into their A-co-masked ornithine analogs which show remarkable antifolate activity <00CPB1270>. The reaction of the heterocyclic enamine 77 with tosyl azide leads to the tosylimino derivative of 1,2,4-triazolo[l, 5-a]pyrimidine 79. Extrusion of nitrogen from the primary adduct 78 is followed by a 1,2-shift of a methyl group to yield 79 <00JHC195>. 

When l,4-dihydronaphthalen-l,4-imine (2) was first obtained via the hydrobromide (113), it was shown to react with phenyl azide to give an adduct (127). The analogous phenyl azide adduct (128) from compound 103 has been better characterized. Naphthalen-l,4-imines also add diazomethane across the 2,3-double bond, forming pyrazolines, e.g., 104 -> 129, two of which have been photolyzed to give the corresponding cyclopropane derivatives (130) with extrusion of nitrogen. ... 

JCS(P1)1587], In some case, depending on substituents, a concomitant pathway proceeds via extrusion of nitrogen from the azido species 470. In this way, the resulting nitrene 472, and then the rearranged carbodiimide species, would explain the concomitant formation of aminotriazoles 473... 

Thermal or photochemical extrusion of nitrogen from 1-arylbenzotriazoles (114) leads to the formation of carbazoles (Scheme 14). The mechanism is believed to involve cyclization of a diradical (115) or an iminocarbene (116) to the 4a/f-carbazole (117) followed by an aromatizing hydrogen... 

Irradiation is very effective in the extrusion of nitrogen from triazole and benzotriazoles. Many of the thermal reactions described in Section 4.01.5.1.2 also take place photochemically. The photolysis of benzotriazole in alcoholic glass at 254 nm is studied by UV absorption, emission, IR, and mass spectroscopies. Scission of the N—NH bond originates from the Si(7t,7t ) state to give the azo compound <87jpci793>. 

As a contrast to this, when 5-phenylamino-l,2,3,4-thiatriazole (42) and an equimolar amount of HMPA in toluene at — 78°C is treated with 1 equivalent of solid lithium bases, LiOH, MeOLi, LiNH2, /-PrjNLi or BuLi dissolved in hexane, extrusion of nitrogen and sulfur is observed on heating to room temperature, resulting in formation of PhNCNLi, HMPA complex (101) (Equation (11)) <93AG1801>. 

L abbe and Vermeulen have proposed salts of type (105) as key intermediates in the reactions of 5-aminothiatriazole (10) with acyl chlorides (Scheme 19) <81BSB89>. The intermediate is expected to undergo cyclization to 3-imino-A -l,2,4-oxathiazoline (106) followed by reaction with a second molecule of acyl chloride to give the corresponding thiapentalene (107). The formation of the 1,2,4-thiadiazole (104) was explained as a result of an addition of V-acetylcyanamide (108), formed by extrusion of nitrogen and loss of sulfur from 5-acetamido-1,2,3,4-thiatriazole, to the key intermediate... 

Photolysis of l-methylnaphtho[l,8-de]triazine (32, R = Me) also results in extrusion of nitrogen and formation of a diradical intermediate (167). Thus, reaction in cyclohexane as solvent gives, among other products, bicyclohexyl and 1-methylaminonaphthalene, while 8-phenyl-1-methylaminonaphthalene is the only product formed when benzene is used as solvent. Photochemical decomposition of 32, R = Me, in the presence of olefins results in an unusual ring transformation, and with a-methylstyrene, for example, the triazine is converted into the dihydroazaphenalene derivative (168). When vinyl bromide and trans-... 

Reaction with acetylenic dipolarophiles represents an efficient method for the preparation of 2,5-dUiydrothiophenes. These products can be either isolated or directly converted to thiophene derivatives by dehydration procedures. The most frequently used dipolarophile is dimethyl acetylenedicarboxylate (DMAD), which easily combines with thiocarbonyl yhdes generated by the extrusion of nitrogen from 2,5-dihydro-1,3,4-thiadiazoles (8,25,28,36,41,92,94,152). Other methods involve the desUylation (31,53,129) protocol as well as the reaction with 1,3-dithiohum-4-olates and l,3-thiazolium-4-olates (153-158). Cycloaddition of (5)-methylides formed by the N2-extmsion or desilylation method leads to stable 2,5-dUiydrothiophenes of type 98 and 99. In contrast, bicyclic cycloadducts of type 100 usually decompose to give thiophene (101) or pyridine derivatives (102) (Scheme 5.37). 

Dipolar cycloaddition occurred preferentially at the electron-rich double bond of 22 to give the unstable triazoline 23, which on thermolysis led to extrusion of nitrogen and rearrangement to give the cyclopentenoid compound 25. The 1,3-dipolar cycloaddition-rearrangement sequence was subsequently extended to ultrasonic conditions. 

Ogawa et al. (12) used an intramolecular azide-alkene cycloaddition strategy to synthesize the oxygen-bridged aza[15]annulene 52 and the aza[15]annulene dicar-boxylate 55 (Scheme 9.12). 1,3-Dipolar cycloaddition of vinyl azide to the acrylate moiety followed by extrusion of nitrogen gave the aziridine 51. Rearrangement of 51 afforded the aza[15]annulene 52. The same approach was used to synthesize the aza[15]annulene 55. 

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