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1.1- Diazene

CAS Registry Numbers N2H2 [3618-05-1], trans-N H [15626-43-4], C/S-N2H2 [15626-42-3], N2D2 [14989-24-3], trans-H D [40712-39-8], cis-N D [66511-78-2], N2HD [14989-15-2], frans-N2HD [40712-38-7], N2T2 [24525-35-7] [Pg.37]

The Preparation, Properties and Reactions of Diimide, Rev. Chem. Intermed. 5 [1984] 293/323. [Pg.37]

Willis, C. Back, R. A. Di-imide. Some Physical and Chemical Properties and the Kinetics and Stoichiometry of the Gas-phase Decomposition, Can. J. Chem. 51 [1973] 3605/ 19. [Pg.37]

Sellmann, D. Diimin und seine Derivate, Chem. Unserer Zeit 7 [1973] 163/70. [Pg.38]

Stedman, G. Reaction Mechanisms of Inorganic Nitrogen Compounds, Adv. Inorg. Chem. Radiochem. 22 [1979] 113/70,121. [Pg.38]


Dia ene deductions. Olefins, acetylenes, and azo-compounds are reduced by hydrazine in the presence of an oxidizing agent. Stereochemical studies of alkene and alkyne reductions suggest that hydrazine is partially oxidized to the transient diazene [3618-05-1] (diimide, diimine) (9) and that the cis-isomer of diazene is the actual hydrogenating agent, acting by a concerted attack on the unsaturated bond ... [Pg.277]

Other examples of [2,3] sigmatropic rearrangements involve amine oxides and diazenes ... [Pg.635]

Lithium silylamides react smoothly with tiifluoronitrosomethane to give diazenes Traces ot water initiate the decomposition of the latter with liberation of a trifluoromethyl carbanion, which is trapped by carbonyl compounds [775] (equation 116) Desilylation of trialkyl(trifluoromethyl)silanes by fluoride ion produces also a trifluoromethyl carbanion, which adds to carbonyl carbon atoms [136, 137] (equations 117 and 118)... [Pg.478]

The reactions of trisilylated benzamidines with benzenechalcogenyl halides are of particular interest. The initially formed trisubstituted derivatives are thermally unstable and decompose by a radical process to generate the dark blue diazenes tran5-PhEN(Ph)CN=NC(Ph)NEPh (E = S, Se) (Scheme 2.3) (Section 15.2)." ... [Pg.24]

Selenium analogues RN=SeCl2 are unknown for R = aryl or alkyl and thermally unstable when R = CE3 or C2E5. The perfluoroalkyl derivatives are prepared by the reaction of dichloroamino compounds and Sc2Cl2 in CCI3E (Eq. 8.18), but they decompose at room temperature to the corresponding diazene and a mixture of selenium chlorides. [Pg.156]

Scheme 12.4 Photochemical isomerization of a C2N4S2 ring into a diazene... Scheme 12.4 Photochemical isomerization of a C2N4S2 ring into a diazene...
The heavier chalcogens are more prone towards secondary interactions than sulfur. In particular, the chemistry of tellurium has numerous examples of intramolecular coordination in derivatives such as diazenes, Schiff bases, pyridines, amines, and carbonylic compounds. The oxidation state of the chalcogen is also influential sulfur(IV) centres engender stronger interactions than sulfur(II). For example, the thiazocine derivative 15.9 displays a S N distance that is markedly longer than that in the corresponding sulfoxide 15.10 (2.97 A V5. 2.75-2.83 A, respectively). ... [Pg.296]

Diazenes of the type REN=C(R )N=NC(R )=NER have a rich structural chemistry. The selenium derivatives 15.11a,b display a cis,trans,cis conformation with two short l,5-Se N contacts (2.65 A). Several sulfur analogues, e.g., 15.1c, have the same structure, but a different cis,trans,cis conformer 15.12 with two 1,4-S N contacts (2.83 A) has also been characterized. A third type of diazene is the trans,trans,trans isomer 15.13a,b with no intramolecular short contacts. ... [Pg.296]

Density functional theory calculations on model diazenes of the type... [Pg.300]

Intramolecular chalcogen interactions may also stabilize reactive functional groups enabling the isolation of otherwise unstable species or their use as transient intermediates, especially in the case of selenium and tellurium. For example, tellurium(II) compounds of the type ArTeCl are unstable with respect to disproportionation in the absence of such interactions. The diazene derivative 15.23 is stabilized by a Te N interaction. Presumably, intramolecular coordination hinders the disproportionation process. Other derivatives of the type RTeX that are stabilized by a Te N interaction include 8-(dimethylamino)-l-(naphthyl)tellurium bromide, 2-(bromotelluro)-A-(p-tolyl)benzylamine, and 2-[(dimethylammo)methyl]phenyltellunum iodide. Intramolecular donation from a nitrogen donor can also be used to stabilize the Se-I functionality in related compounds." ... [Pg.303]

Homogeneous and heterogeneous catalytic activation (in the dark and in the light) of cyclic 1,2-diazenes 97SL1335. [Pg.221]

With a change to non-polar solvent, the reaction of ylides 269 with alkynes and alkenes changed dramatically, as shown in Scheme 10. With DM AD in toluene the ylides give pyrazolopyridines 272 in good yield (91TL4977), and with methyl propiolate (MEP) give indolizines 273 (92H(33)203). The reaction with acrylates is much less clean, but the variety of products is said to be formed from a diazene intermediate, which splits to give a diradical (93H(35)851). [Pg.50]

The acetate (1) and its mosylate analog (79) have been shown to undergo cydoad-dition with the CN double bond of alkyl imines to generate substituted pyrrolidines in the presence of nickel or palladium catalyst [35]. For example, both the phenyl imine (80) and the diazene (81) gave reasonable yields of adducts (82) and (83) respectively (Scheme 2.23). [Pg.73]

Likewise, thermolysis of 4-azidophenyl methyl ketone in methanol yields 5-acetyl-2-methoxy-3//-azepine (60%), compared to only an 8% yield from the photolytic reaction.78 119 The thermolysis of phenyl azide in refluxing cyclohexanol yields no 3H-azepine, only diphenyl-diazene (10%) and aniline (30%).74 In contrast, thermolysis of methyl 2-azidobenzoate in cyclohexanol furnishes a mixture of methyl 2-(cyclohexyloxy)-3//-azepine-3-carboxylate (20 % bp 127°C/0.1 Torr) and methyl 2-aminobenzoate (60%). Thermolysis of the azido ester in methanol under nitrogen in an autoclave at 150 C yields a 7 10 mixture (by 1HNMR spectroscopy) of the amino ester and methyl 2-methoxy-3//-azepine-3-carboxylate, which proved to be difficult to separate, and much tar.74 The acidic medium179 is probably responsible for the failure of methyl 2-azidoberjzoate to yield a 3//-azepine when thermolyzed in 3-methoxyphenol aniline (40%) is the major product.74... [Pg.147]

Dialkyldiazenes (15, R—alkyl) are sources of alkyl radicals. While there is dear evidence for the transient existence of diazcnyl radicals (17 Scheme 3.18) during the decomposition of certain unsymmetrieal diazenes49 51 and of cis-diazenes,54 all isolable products formed in thermolysis or photolysis of dialkyldiazenes (15) are attributable to the reactions of alkyl radicals. [Pg.68]

Multi functional initiators where the radical generating functions are in appropriate proximity may decompose in a concerted manner or in a way such that the intermediate species can neither be observed nor isolated. Examples of such behavior are peroxyoxalate esters (see 3.3.2.3.1) and a-hydroperoxy diazenes (e.g. 31), derived peroxyesters (65)2S3 2S4 and bis- and multi-diazenes such as 66.233,250... [Pg.97]

It has been reported that the a-hydroperoxy diazenes may undergo induced... [Pg.97]

Initiators where the radical generating functions are sufficiently remote from each other break-down in a non-concerted fashion. Examples include the azoperoxide (68) and the bis-diazene (67).261 Their chemistry is often understandable in terms of the chemistry of analogous monofunctional initiators.260 This class also includes the dialkyl peroxyketaLs (see 3.3.2.4) and hydroperoxyketals (see 3.3.2.5). [Pg.97]

Compounds of the form RN2 X are named by adding the suffix -diazonium to the name of the parent compound RH, the whole being followed by the name of X- (Rule C-931.1, e.g., methanediazonium tetrafluoroborate, benzenediazonium chloride, not phenyldiazonium). Following RC- 82.2.2.3 (IUPAC, 1993), diazonium ions may also be named structurally on the basis of the parent cation diazenylium HNJ, e.g., benzenediazenylium ion. We name the substituent — NJ diazonio (not diazonium) following the same rule. Diazonio describes both mesomeric structures — N = N and — N = N. If one wants to describe one of these structures only, diazyn-l-ium-l-yl or diazen-2-ylium-l-yl has to be used for -N = N or -N = N, respectively. In the General Subject Index of Chemical Abstracts and in Beilstein, diazonium compounds as a class are indexed under this heading. [Pg.5]

In Chemical Abstracts and in Beilstein specific azo compounds are found under the heading diazenes . As their systematic nomenclature may be very complex (polyazo dyes ), it is much easier to search for them with the aid of the Formula Index of Chemical Abstracts. [Pg.7]

A novel application of a phenyl aryldiazosulfone was found by Kessler et al. (1990). l-[4-(7V-Chlorocarbonyl-7V-methylamino)phenyl]-2-(phenylsulfonyl)diazene (6.18) is an acid chloride with a potential diazonio group. The above authors showed that in organic solvents (THF, etc.) this compound reacts easily, as expected, with nucleophiles (HNu), e.g., with aliphatic, aromatic, or heterocyclic amines, with cystine dimethyl ester, or with 4-methoxyphenol at the carbonyl function, yielding... [Pg.118]

In addition, Suehiro et al. (1987) were able to accurately determine the rates of dediazoniation of twenty substituted aryldiazenyl radicals formed from aryl(aryl-thio)diazenes (Scheme 8-36), in cyclopropane and in alkenic solvents at -48 to — 117°C, using a time-resolved ESR method. [Pg.192]

Xu and Li (1989) investigated H — CIDNP spectra of fifteen substituted benzene-diazonium ions during reduction with NaBH4. The spectra are consistent with a mechanism in which the first step is the addition of a hydride ion to the diazonium ion. The diazene formed (Ar - N2 - H) is assumed to dimerize and disproportionate into a radical pair [Ar-N-NH2 N = N — Ar] which loses one equivalent of N2 yielding [Ar—N —NH2 Ar] and recombines to give the diarylhydrazine. A proportion of the aryl radicals escape and form the hydro-de-diazoniation product. [Pg.195]


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1,1-Diazene synthesis

1,1-Diazene via oxidation of 1,1-disubstituted hydrazines

1- Phenyl-2 diazenes

1.1- Diazene, aminonitrenes

Aminonitrenes (1,1-Diazenes)

Azo Compounds and Diazene

Azo compounds (diazenes) as sources of free radicals

Azoalkanes (1,2-Diazenes)

Bis- -diazene

Bismuth Bis diazene

Cis-diazene

Copper diazene complexes

Deamination diazenes

Diazen

Diazen

Diazen-l-oxid

Diazene Fragmentations as Novel Alkane Syntheses

Diazene N-oxide

Diazene anion

Diazene complexes

Diazene complexes conversion

Diazene complexes of nickel

Diazene compounds

Diazene conversion

Diazene dialkyl alkanone

Diazene formation from hydrazines

Diazene fragmentation

Diazene isomers

Diazene ligand

Diazene ligand complexes

Diazene structure

Diazene transition metal

Diazene, dimethyl

Diazene, phenyl

Diazene, propargylic

Diazene-coordinating complex

Diazene-transition metal complexes

Diazenes , synthesis

Diazenes and the isomerization of azo compounds

Diazenes compounds

Diazenes electron transfer

Diazenes, bicyclic

Diazenes, bicyclic vinylcyclopropane

Diazenes, formation

Diazenes, nitroso

Diazenes—

Diazenes—

Diphenyl-diazene

Diylophiles diazenes

Ferrocenyl diazenes

Hydrazido. diazenido. and diazene complexes

Irans-diazene

Iron complexes diazenes

Ligand structures diazenes

Manganese diazene complexes

Molybdenum diazene complexes

Nickel diazene complexes

Nitrogen complexes diazenes

Nitrogen diazene

Olefin, Acetylene, Phosphine, Isocyanide, and Diazene Complexes of Nickel

Photoisomerization of Coordinated Diazene

Poly diazene

Reactions Involving Ligated Diazenes

The Diazene Anion

The Diazene Cation

The Diazene Ligand

Thermodynamics diazene

Trans-diazene

Transition with diazenes

Tungsten diazene complexes

Vinyl diazene

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