X-ray diffraction structural study of 1,7-dimethyl-1,7-dioxa-2,3,5,6-tetraaza-2.5-heptadiene 3,5-dioxide

Cherepinskii-Malov, V. D.; Marchenko, G. A.; Mukhametzyanov, A. S.; Бузыкин, Б. И.

doi:10.1007/bf00948083

Cited by 3 publications

(4 citation statements)

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“…Later, Woodward et al proposed that the two isomers possess the structures shown here, and that one of them ( I ) is thermodynamically unstable whereas the other ( II ) is thermodynamically stable and chemically inert toward both strong acid and base . Since this report, X-ray crystallography has confirmed the structure shown for II , and the structure shown for I is consistent with NMR data for related compounds …”

Section: Resultssupporting

confidence: 82%

Multiplicity Control in the Polygeminal Diazeniumdiolation of Active Hydrogen Bearing Carbons: Chemistry of a New Type of Trianionic Molecular Propeller

and

Bohle

2001

J. Am. Chem. Soc.

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Over a century ago, Traube reported the reaction of four nitric oxides with acetone and sodium ethoxide to yield sodium methanebis(diazene-N-oxide-N'-hydroxylate) and sodium acetate. However, when this reaction is carried out in the presence of nitric oxide at slightly elevated pressures (35-40 psi), a product corresponding to the addition of six nitric oxides, sodium methanetris(diazene-N-oxide-N'-hydroxylate), forms as the main product in addition to a trace of the previously observed sodium methanebis(diazene-N-oxide-N'-hydroxylate) and sodium acetate. The corresponding potassium salts form when potassium hydroxide is employed as the base, while lithium hydroxide results in the formation of lithium methanebis(diazene-N-oxide-N'-hydroxylate) exclusively. Nitric oxide reacts with 3,3-dimethylbutan-2-one in the presence of sodium and potassium hydroxide in methanol to yield sodium and potassium 3,3-dimethylbutan-2-one-1,1,1-tris(diazene-N-oxide-N'-hydroxylate), respectively. In contrast, the reaction in the presence of lithium hydroxide forms lithium methanebis(diazene-N-oxide-N'-hydroxylate) and lithium pivalate. The differential reactivity of nitric oxide with acetone and 3,3-dimethylbutan-2-one in the presence of the three bases is attributed to competing hydrolytic reactions of the acetyl and trimethylacetyl group-containing intermediates. A mechanism is proposed for the nitric oxide addition to active methyl groups in these reactions, where the product distribution between the di- and trisubstituted methanes is under kinetic control of the competing reactions. The products are characterized by NMR and IR spectroscopy, differential scanning calorimetry, and elemental analysis. Two differentially hydrated forms of potassium methanetris(diazene-N-oxide-N'-hydroxylate) are characterized by single-crystal X-ray diffraction. From the metathesis reaction of the silver salt of methanetris(diazene-N-oxide-N'-hydroxylate) with ammonium iodide, the corresponding ammonium salt is isolated in 59% yield, but only trace amounts of methylated products form in the reaction of the silver salt with methyl iodide. Density functional calculations (B3LYP/6-311++G) are used to evaluate the bonding, ground-state structures, and energy landscape for the different conformers of methanetris(diazene-N-oxide-N'-hydroxylate)(3-) trianion, a new type of a molecular propeller, and its corresponding triprotonated acid.

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Section: Resultssupporting

confidence: 82%

Multiplicity Control in the Polygeminal Diazeniumdiolation of Active Hydrogen Bearing Carbons: Chemistry of a New Type of Trianionic Molecular Propeller

and

Bohle

2001

J. Am. Chem. Soc.

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“…The diazenium diolate portion of the structure of 1D indicates that this species adopts a Z geometry with metrical parameters very similar to those reported for the related compounds N -methyl- N ‘-methoxydiazene- N -oxide, methylene-bis( N ‘-methoxydiazene- N -oxide), ethane-1,1-bis( N ‘-methoxydiazene- N -oxide), and propane-2,2-bis( N ‘-methoxydiazene- N -oxide) . In all of these structures the NN bond lengths are longer than those found for the hyponitrous acid cocrystallite and for dialkylhyponitrites.…”

Section: Discussionsupporting

confidence: 68%

“…The observed N−N, N−O butoxy , N−O oxide bond distances of 1.264(1) Å, 1.369(1) Å, and 1.268(1) Å, respectively, indicate delocalized π-bonding over the N 2 O 2 fragment. Four other compounds, namely, N -methyl- N ‘-methoxydiazene- N -oxide, methylene-bis( N ‘-methoxydiazene- N -oxide), ethane-1,1-bis( N ‘-methoxydiazene- N -oxide), and propane-2,2-bis( N ‘-methoxydiazene- N -oxide) 25 also exhibit similar structural features.…”

Section: Resultsmentioning

confidence: 95%

“…As will be described below, we have isolated trans -di- O - tert -butyl hyponitrite ( 1A ), ( Z )- N - tert -butyl- N ‘- tert -butoxydiazene- N -oxide ( 1D ), trans -mono- O - tert -butyl-hyponitrous acid ( 2A ), and ( Z )- N - tert -butyl- N ‘-hydroxydiazene- N -oxide ( 2D ) from the reaction of tert -butyl bromide with silver hyponitrite by the slightly modified procedure of Kiefer et al . Although a number of ( Z )- N -alkyl- N -alkoxydiazene- N -oxides, RN(O)NOR with different organic groups − have been synthesized by other methods, there is only one instance in which an N -alkyl- N -alkoxydiazene- N -oxide has been isolated from the alkylation of silver hyponitrite . In addition, there is no literature data on mono-alkyl hyponitrites resulting from the reaction of alkyl halides with silver hyponitrite.…”

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confidence: 99%

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Correlation of the Product E/Z Framework Geometry and O/O vs O/N Regioselectivity in the Dialkylation of Hyponitrite

et al. 2000

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The products from the alkylation of silver hyponitrite with tert-butyl bromide, tert-amyl bromide, p-tert-butyl benzylbromide, and chlorotriethylsilane have been determined. In the reaction of tert-butyl bromide the formation of three new products, namely, (Z)-N-tert-butyl-N‘-tert-butoxydiazene-N-oxide {(CH3)3CN(O)NOC(CH3)3}, 1D, trans-mono-O-tert-butylhyponitrous acid {(CH3)3CONNOH}, 2A, and (Z)-N-tert-butyl-N‘-hydroxydiazene-N-oxide {(CH3)3CN(O)NNOH}, 2D, is observed together with the formation of the known trans-di-O-tert-butyl hyponitrite {(CH3)3CONNOC(CH3)3}, 1A. The reaction with tert-amyl bromide also yielded the corresponding tert-amyl derivatives. However, from the reactions of p-tert-butylbenzyl bromide and chlorotriethylsilane with silver hyponitrite, the corresponding trans-di-O-tert-alkylhyponitrites were obtained as the only alkylated products. The differential reactivity of the two sets of halides with silver hyponitrite is explained in terms of the higher stability of the cations generated from the former halides in comparison to those generated from the latter halides. The thermal decomposition data and UV−visible spectroscopic data are reported for all of the products. Crystallographic structural data are reported for two of the products, namely, (Z)-N-tert-butyl-N‘-tert-butoxydiazene-N-oxide, 1D, as its hyponitrous acid adduct, (CH3)3CN(O)NOC(CH3)3·1/2HONNOH, and trans-di-O - p-tert-butylbenzyl hyponitrite, {p(CH3)3C}C6H4CH2ONNOCH2C6H4-p-{C(CH3)3}. Theoretical calculations using ab initio density functional theory (B3LYP) are reported for the hyponitrite dianion, trans-mono-O-methylhyponitrite anion, (Z)-N-methyl-N‘-hydroxylatodiazene-N-oxide anion, and for the methylation transition states. On the basis of the products isolated from the reactions of tert-butyl bromide and tert-amyl bromide and the theoretical calculations, a pathway is proposed to account for the observed product distributions where O/O-dialkylation is found in the trans(E) products and O/N-dialkylation is found in the cis(Z) products.

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Chemistry of the Diazeniumdiolates I. Structural and Spectral Characteristics of the [N(O)NO]− Functional Group

et al. 2001

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X-ray diffraction structural study of 1,7-dimethyl-1,7-dioxa-2,3,5,6-tetraaza-2.5-heptadiene 3,5-dioxide

Cited by 3 publications

References 1 publication

Multiplicity Control in the Polygeminal Diazeniumdiolation of Active Hydrogen Bearing Carbons: Chemistry of a New Type of Trianionic Molecular Propeller

Multiplicity Control in the Polygeminal Diazeniumdiolation of Active Hydrogen Bearing Carbons: Chemistry of a New Type of Trianionic Molecular Propeller

Correlation of the Product E/Z Framework Geometry and O/O vs O/N Regioselectivity in the Dialkylation of Hyponitrite

Chemistry of the Diazeniumdiolates I. Structural and Spectral Characteristics of the [N(O)NO]− Functional Group

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