Can. J. Chem. 56, 1657Chem. 56, (1978.Decompositions of tetramethyl-2-tetrazene (TMT) under acidic conditions were investigated by product analysis and by nmr and esr spectroscopic monitors. Photolysis in acetonitrile containing trifluoroacetic acid generated the dimethylaminium radical which added efficiently to an olefinic double bond. Some adducts contained a (CH3),NCH2-moiety, the immediate precursor of which could be CH2=N(CH3),+ species. Photolytic addition of TMT to norbornenes generated 2-norbornyl radicals that underwent coupling through the exo or endo side to give the dimers. Thermal decomposition in sulfuric acid in the presence of toluene gave N,N-dimethyltoluidines, N-methylphenethylamine, benzyltoluenes, and a plethora of other minor products in addition to a large amount of formylidene methylamine. The last compound was the major product when thermal decomposition of T M T was carried out in trifluoroacetic acid in the presence of toluene or anisol; amination products of aromatic substrates were low and contained only ortllo and porn isomers. TMT dissolved in these solvents exhibited the esr signal of the stable T M T t (the tetrazene cation radical) which did not react with cyclohexene. In concentrated sulfuric acid, T M T was decomposed in less than 15 min giving formylidene methylamine and dimethylamine as shown by nmr. In trifluoroacetic acid, the esr signal of tetramethylhydrazine cation radical ( T M H t ) emerged after the TMT solution was irradiated ; no dimethylaminium radical signal could be detected. The relationship of TMTf and TMHC with formation of the observed products remains unclear. Chem. 56, 1657Chem. 56, (1978.On a Ctudie, a I'aide de I'analyse des produits et par etudes spectroscopiques rmn et rpe la decomposition de la tetrarnethyltetrazene-2 (TMT) dans des conditions acides. La photolyse dans I'acetonitrile contenant de I'acide trifluoroacetique conduit a la formation de radical dimethylaminium qui s'additionne d'une f a~o n efficace a la double liaison olkfinique. Quelques produits contenaient une portion (CH3),NCH2-dont le prkcurseur immkdiat serait I'espece CH2N(CH3),+. L'addition photolytique du TMT aux norbornenes conduit a des radicaux norbornyl-2 qui subissent des couplages par les faces exo ou erldo pour conduire a des dimeres. La decomposition thermique dans I'acide sulfurique en presence de toluene conduit aux N,N-dimethyltoluidines, a la N-methylphenethylamine, aux benzyltoluenes et a toute une strie d'autres produits mineurs en plus d'une grande quantitt de formylidene methylamine. Ce dernier conrposk est le produit majeur lorsque la dCcomposition therrnique du TMT est effectuee dans I'acide trifluoroacetique en presence du toluene ou d'anisol; les produits d'amination des substrats aromatiques sont faibles et contiennent uniquement les isomeres orflro et pnrn. Lorsque le TMT est dissous dans ces solvants, il presente un signal rpe correspondant a I'entite T M T t (le radical cation tetraztne) qui ne rtagit pas avec le cyclohexene. Dans l'acide sulfurique co...

No abstract

Photolysis of nitramines in a neutral solvent generated nitrogen dioxide and aminyl radicals which abstracted a hydrogen but did not add to a π-bond. In dilute acidic solution, the aminyl radicals generated from the photolysis were protonated to the corresponding aminium radicals that preferentially added to π-bonds rather than abstracted a hydrogen. However, complex mixtures of addition products were obtained when nitramines were photolysed in the presence of cyclohexene under nitrogen. The plethora of the products is believed to arise from the complex behavior of nitrogen dioxide in solution; for example, (i) nitrogen dioxide may react as O- or N-radical, (ii) nitrogen dioxide exists in equilibrium with nitrogen tetraoxide, and (iii) both oxides can react as oxidizing or radical trapping agents. Under oxygen, the oxidative addition of nitramines to cyclohexene gave 1-dialkylamino-2-nitratocyclohexenes which could be treated with lithium aluminium hydride to give good yields of the corresponding amino alcohols. The quantum yields of nitramine disappearance indicated that the photolysis followed short chain processes either in neutral or acidic conditions. The decrease in quantum yield at >2 N H2SO4 is believed to be due to a reduced reactivity of aminium radicals in a highly acidic environment. The probable mechanisms of these photolytic radical chain processes are discussed.

Y C .~ L. CHOW, K , SO\I-\SEKHARA?< PILLAY, and H~R V E RTCITARL). Ca1-l. J. Chem. 57.2913Chem. 57. (1979.Nitrosql chloride reacted with :,5-c:.clooctadiene and trcir!. ~,tr.nrir,trr~i~.~-1,5,9-cyc1od~deca-triene i11 methglene chloride by the c,D-addition to g i~e chioronitroso al!tenes u.iik cis a n 2 thi-eo (tintis) configuraiion, respcctikely. These enantionioiphic C-nitrcso colnpounds were isolated as a single compor~iid for the fornier; and a n i i~t u r e io: the latter, of dl arid (or) inero din?ers, the presence of v,hich \\as readily monitored by 13C nn?r spectroscop). The former can assume a coi~ibrrnaiion to place the rc-bonds of the nitroso and olefinic groups in interacting vicir~ity arld undergo a n acid catalyzed intramolecular electrcphiiic cyciization to give bicyclic hjdroxylanlines mliich are readily air oxidized to the co:r.esponding nitroxide radicals. Rearrangement in acetic a n h~d r i d e -rneihjiene chloride afforded good 5ields of the stable bicyciic h y d r o x~l -ainine acetates s\hich cerved as precursors to generale the corresponding nitrovides under mild ccnditions. Photoaddition of.\ -iiitrosopiperidine to I ,5-cqclooctadiene also partlq afforded the ci\-aniinonirroso adduct 14 hich underuent the intrainolecular addition to gi1.e hydrorylamines. The thrco(ti-at!.\)-.chlmitroso alhenes failed to c)c!izc in simiiar fa5hion under comparable conditions. Nitrosylchloride added cxclusi\ely to the ri.iiir,-double bond of ti.o,i.!,cic-1,s-cqclodecadiene ~i i t h o u t i-egiospecificity biii ,"\as belieicd to foliou !he stereospecific cih-addition; this chioroilitroso coillpoiliid aiso undernent the acid catal>zed :-ransanniilar reaction to give simllar hydrox~lanilr~es :hzr were not isolated in pure states. Chem. 57.1923Chem. 57. (1979.Par une additioil cij, le rhiorure de nitrosq!e dans le chlorure de nitthylene se fixe sur le cyclooctadiene-! ,5 st ie cyclociodCcatriene-1,5,9 ri-iit~.r.f;~ans~~ims pour conduire respectivemefit 2ux alcenes chioroni;roses <,is et ri'zi-ho !irnrr.r). Les coinposis ~iiantiomorphes C-nirrosis sont isoles sous foi me de co~irposd unique dans le cas du cyclooctadiene et sous forme d'un melange de ril et ou de din~eres ii?4so dans le second cas. La presence de ces derniers a ete revklee par l'etude des spectres rmn du 'T. i e s composis derikant du cyclooctadiene--1,s adoptent une con5guration qui place ic5 !iaisons n des gl.oupements nitroso et olefines a u voisinage l'un de I'autre. Ceci pennet alors une cyclisation e!ecti.ophile in(ranio!eculaire, cata!ysCe par l'acide, cici conduit ails h>drou)ismines bicqcliques. Ces derniers s'oxSdent facilemcnt B I'zir en i.adicaax iiiri-oso corxspondants. L a transposition dans un r?C!ange a n h~d r e acQtique --ch1ori.il.e tie r:iCthyIi.re foamit avec de iions rendeiiients Ies acCtates d'h~~droxylaminei bicycliilues ~i z h l e s qui dani 2e.; coi~ditions douces serkent de prec~~rseurs aux nitroxydes corresim~?dants. L'addirion photochiniique de :a N-nitroso pipkridine a u cyc1ooc;adiene-i,5 fo~~:-iiit awsi en parti...

The oxidative photoaddition of N-nitrosodimethylamine to various olefins gives products similar to those obtained from N-nitrodimethylamine despite certain dis-similarity in the mechanisms. The oxidative photoaddition to rrans,rrans,rrans-cyclododeca-1,5,9-triene in the presence of an excess of N-nitrosodimethylamine apparently gave good yields of the expected amino-nitrates. These were reduced by lithium aluminium hydride to afford predominantly the open-chain a,o-substituted amino-alcohol. The non-oxidative photoaddition of N-nitrosodimethylamine to hepta-l,6-diene gave small amounts of cyclized pentane derivatives whereas similar addition of bulkier N-nitrosopiperidine gave higher yields of the cyclized products. While photoadditions of N-nitrosodimethylamine to rrans,rrans,rrans-cyclododeca-l,5,9-triene failed to give a cyclization product, similar photoadditions to cis,frans-cyclodeca-1,5-diene gave a pair of epimeric alcohols derived from a stereospecifically cyclized perhydroazulenoid skeleton under oxidative conditions, and the corresponding oximes under non-oxidative conditions. The structures of these azulenoid compounds have been elucidated and the remarkable stereospecificity of addition-cyclization process is discussed.