Anta and its Oxidation Products

1995 ◽  
Vol 418 ◽  
Author(s):  
Kien-Yin Lee ◽  
Richard Gilardi ◽  
Michael A. Hiskey ◽  
James R. Stine
Keyword(s):  
High Explosive ◽  
Ammonium Persulfate ◽  
Nitrogen Molecule ◽  
Heat Of Formation ◽  
Oxidation Products ◽  
Reaction Products ◽  
High Nitrogen ◽  
X Ray ◽  
X Ray Crystallography ◽  
Crystal Density

Abstract5-Amino-3-nitro-lH-1,2,4-triazole (ANTA) is a molecule with high stability. Aside from being an insensitive high explosive (IHE), it is also used as a synthon for other potential new IHEs. The crystal structure of ANTA was resolved by X-ray crystallography. However, when ANTA was recrystallized from 2-butanone, crystals with molecular packing characterized by extended planar sheets were obtained (ß-ANTA). The crystal density of ß-ANTA is 1.73 g/cm3, which is less dense than α-ANTA (p = 1.82g/cm3).The high-nitrogen molecule, 5,5'-dinitro-3,3'-azo-1,2,4-triazole (DNAT) was calculated to have a high density and a positive heat of formation (AHf). In an attempt to prepare DNAT, we have studied the oxidation of ANTA with different oxidizers. It was found that DNAT is the reaction product when the potassium salt of ANTA was oxidized with potassium permanganate. However, when ANTA was oxidized with ammonium persulfate in aqueous medium, one of the reaction products obtained was the azoxy moleclue of DNAT (DNAzT). We are unable to determine the crystal densities of either DNAT and DNAzT because the crystals obtained were solvated with the crystallization solvents.

scholarly journals Reactions of Titanocene- and Zirconocene-Bis(trimethylsilyl)acetylene Complexes with Selected Heterocyclic and Aromatic NH and OH Acid Compounds

2007 ◽  
Vol 72 (4) ◽  
pp. 475-491 ◽  
Author(s):  
Perdita Arndt ◽  
Vladimir V. Burlakov ◽  
Ulrike Jäger-Fiedler ◽  
Marcus Klahn ◽  
Anke Spannenberg ◽  
...  
Keyword(s):  
Bond Activation ◽  
Reaction Pathway ◽  
Reaction Products ◽  
X Ray ◽  
X Ray Crystallography

The titanocene complexes Cp'2Ti(η2-Me3SiC2SiMe3) (Cp' = Cp (1), Cp* (2)) react with pyrrole under the formation of the titanium(III) mono-N-pyrrolides Cp'2Ti(NC4H4) (Cp' = Cp (6), Cp* (7)); whereas the corresponding zirconocene system Cp2Zr(η2-Me3SiC2SiMe3)(thf) (3) forms in a different reaction pathway first the Cp2Zr(NC4H4)[C(SiMe3)=CH(SiMe3)] (8) and then the zirconium(IV) bis-N-pyrrolide Cp2Zr(NC4H4)2 (11). With Cp*2Zr(η2-Me3SiC2SiMe3) (4) and pyrrole, the zirconium(IV) mono-N-pyrrolide with an agostic alkenyl group Cp*2Zr(NC4H4)[C(SiMe3)=CH(SiMe3)] (9) was obtained. In the reaction of the ethylenebistetrahydroindenyl (ebthi) complex rac-(ebthi)Zr(η2-Me3SiC2SiMe3) (5) with 2,3,5,6-tetrafluoroaniline under N-H bond activation, a complex with an agostic alkenyl group rac-(ebthi)Zr(NH-C6HF4)[C(SiMe3)=CH(SiMe3)] (10) was formed. Compound 10 reacts with additional 2,3,5,6-tetrafluoroaniline to give the bisanilide rac-(ebthi)Zr(NH-C6HF4)2 (12) which was obtained directly from 5 with two equivalents of 2,3,5,6-tetrafluoroaniline. In reactions of complex 5 with unsubstituted aniline to rac-(ebthi)Zr(NH-C6H5)2 (13) and with pentafluorophenol to bisphenolate rac-(ebthi)Zr(O-C6F5)2 (14), no intermediates could be isolated. The new reaction products 6, 9, 10, 12, 13 and 14 were investigated by X-ray crystallography.

Cyclic Alkyl(aryl)boranes for 1,1-Carboboration of Monoalkynyltin Compounds

2013 ◽  
Vol 68 (5-6) ◽  
pp. 493-502 ◽  
Author(s):  
Bernd Wrackmeyer ◽  
Peter Thoma ◽  
Wolfgang Milius
Keyword(s):  
Solid State ◽  
High Selectivity ◽  
Ring Expansion ◽  
Membered Ring ◽  
Reaction Products ◽  
State Structure ◽  
Alkyl Aryl ◽  
X Ray ◽  
X Ray Crystallography ◽  
Nmr Techniques

Two cyclic alkyl(aryl)boranes, a 1-bora-indane derivative 1, and a tricyclic derivative 4, containing the boron atom in a six-membered ring, were structurally characterized by NMR techniques in solution. The solid-state structure of the 1-bora-indane 1 was determined by X-ray crystallography. The reactivity of these cyclic alkyl(aryl)boranes towards monoalkynyltin compounds, Me3Sn-C≡C-Me and Me3Sn-C C-Fc (Fc=ferrocenyl), was studied using multinuclear magnetic resonance methods (1H, 11B, 13C, 119Sn NMR). Novel alkenylboranes were formed by 1,1-carboboration reactions. This process involves an expansion of both five- and six-membered rings. Insertion into the respective B-C(aryl) bond was preferred with high selectivity. In the case of the six-membered ring in 4, the ring expansion to seven-membered rings proved to be readily reversible, and the thermodynamically stable reaction products were formed by ring contraction and concomitant transfer of the exocyclic B-nPr group

The scope of the β-halogenation of triarylcorroles

2016 ◽  
Vol 20 (01n04) ◽  
pp. 465-474 ◽  
Author(s):  
Sara Nardis ◽  
Giuseppe Pomarico ◽  
Manuela Stefanelli ◽  
Sara Lentini ◽  
Daniel O. Cicero ◽  
...  
Keyword(s):  
Inner Core ◽  
2D Nmr ◽  
Silver Ion ◽  
Free Base ◽  
Reaction Products ◽  
Nmr Analysis ◽  
X Ray ◽  
X Ray Crystallography ◽  
Halogen Atoms

Functionalization of corrole at its peripheral positions is an intriguing field of research, since the unusual reactivity of this macrocycle usually makes it difficult to predict the reaction products. We have investigated the introduction of halogen atoms at the corrole β-positions by using haloacids as reagents. Different behavior, in terms of number and position of the units introduced, was observed: chlorination yielded mono and disubstituted corrole, whereas bromination only afforded mono-substitution, even if on different positions. Iodination did not occur on the corrole free base, while the protection of the inner core by chelation with silver ion gave better results and a symmetric diiodinated corrole was isolated. 2D NMR analysis and X-ray crystallography provided useful information about the site of these corrole functionalizations.

Oxidations of 12-Deoxy-, 12-Hydroxy-, 12-Methoxy-, and 12-Hydroxy-13-methoxy-podocarpa-8,11,13-triene Derivatives

1998 ◽  
Vol 51 (1) ◽  
pp. 37 ◽  
Author(s):  
Richard C. Cambie ◽  
Maria do Céu Costa ◽  
Paul D. Woodgate ◽  
Peter S. Rutledge ◽  
Ni Na Kong ◽  
...  
Keyword(s):  
Oxidation Products ◽  
The Novel ◽  
Keto Ester ◽  
X Ray ◽  
X Ray Crystallography ◽  
Benzylic Oxidation ◽  
Nitro Derivatives ◽  
Derivatives Of ◽  
Cerium Iv Ammonium Nitrate ◽  
Ruthenium Tetraoxide

Methods for the oxidation of the aryl ring of derivatives of podocarpic acid have been examined. Oxidation of methyl 12-hydroxypodocarpa-8,11,13-trien-19-oate (2) with phenyliodonium diacetate in various solvents gives 8β-substituted dienones. An 8β-chloro dienone is formed during oxidation of the phenol (2) with t-butyl hypochlorite. Oxidation of (2) with dimethyldioxiran gives mainly the 7-ketone (13) but also affords the novel ε-lactone (26), while treatment with ruthenium tetraoxide also affords products of benzylic oxidation. Oxidation of methyl podocarpa-8,11,13-trien-19-oate (4) with m-chloroperbenzoic acid affords a B-ring lactone (29) and, unexpectedly, a 6α-chloro 7-ketone (30). The action of cerium(IV) ammonium nitrate on (2) gives nitro derivatives rather than oxidation products. Oxidation of methyl 12-hydroxy-13-methoxypodocarpa-8,11,13-trien-19-oate (22) with m-chloroperbenzoic acid gives a low yield of a 7-oxo derivative (17) while treatment with ozone gives an unusual α,β-unsaturated γ-lactone (31), the hydroxy lactone (33), the unsaturated keto ester (34), and the substituted furan (35). Oxidation of (22) with Fremy"s salt gives products of ring B oxidation. The structure of (31) has been confirmed by X-ray crystallography.

scholarly journals Crystal Structure and Hirshfeld Surface Analysis of Acetoacetanilide Based Reaction Products

Molecules ◽  
2020 ◽  
Vol 25 (9) ◽  
pp. 2235
Author(s):  
Farid N. Naghiyev ◽  
Jonathan Cisterna ◽  
Ali N. Khalilov ◽  
Abel M. Maharramov ◽  
Rizvan K. Askerov ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Surface Analysis ◽  
Multicomponent Reaction ◽  
Hirshfeld Surface ◽  
Hirshfeld Surface Analysis ◽  
High Yield ◽  
Reaction Products ◽  
X Ray ◽  
X Ray Crystallography

We report an unprecedented multicomponent reaction of acetoacetanilide with malononitrile leading to a structurally novel bicyclic product (9) in a high yield. The structure has been confirmed by X-ray crystallography and comparative Hirshfeld surface analysis of 5-cyano-2-hydroxy-2-methyl-N-phenyl-4-(yridine-4-yl)-6-(thiophen-2-yl)-3,4-dihydro-2H-pyran-3-carboxamide 2, 5-cyano-2-hydroxy-2-methyl-6-oxo-N-phenyl-4-(thiophen-2-yl)piperidine-3-carboxamide 4 and 2-(8-amino-7,8a-dicyano-1-imino-4a-methyl-3-oxo-2-phenyl-1,3,4,4a,5,8a-hexahydroisoquinolin-6(2H)-ylidene)-N-phenylacetamide 9.

Gold cluster chemistry with the tin nucleophile stanna-closo-dodecaborate

2010 ◽  
Vol 75 (9) ◽  
pp. 963-970 ◽  
Author(s):  
Hartmut Schubert ◽  
Fritz-Robert Küchle ◽  
Lars Wesemann
Keyword(s):  
Nmr Spectroscopy ◽  
Single Crystal ◽  
Elemental Analysis ◽  
Gold Cluster ◽  
Mixed Valence ◽  
Gold Complex ◽  
Reaction Products ◽  
Cluster Chemistry ◽  
X Ray ◽  
X Ray Crystallography

The tin nucleophile [SnB11H11]2– reacts with the gold cluster [Au9(PPh3)8][NO3]3 under formation of the tin–gold complex [Au8(PPh3)7(SnB11H11)] (1). In reaction with four equivalents of the heteroborate a mixed valence tetrahedral gold cluster [Au4(PPh3)4(SnB11H11)2]2– with two edge bridging tin ligands was isolated. The reaction products were characterized by elemental analysis, NMR spectroscopy and single crystal X-ray crystallography.

Some oxidation products of lycoctonine revisited

2006 ◽  
Vol 84 (9) ◽  
pp. 1167-1173 ◽  
Author(s):  
Doaa Abdelrahman ◽  
Michael Benn ◽  
Ryan Hellyer ◽  
Masood Parvez ◽  
Oliver E Edwards
Keyword(s):  
Oxidation Product ◽  
Chromic Acid ◽  
Oxidation Products ◽  
Acid Oxidation ◽  
Lithium Aluminium Hydride ◽  
X Ray ◽  
X Ray Crystallography ◽  
Chromic Acid Oxidation ◽  
Lithium Aluminium ◽  
Norditerpenoid Alkaloid

The structure of a chromic acid oxidation product of the norditerpenoid alkaloid lycoctonine (1) was established as hydroxylycoctonal (3) by spectrometric analyses and X-ray crystallography of its reduction product, hydroxylycoctonine (5); the structure of lycoxonine, a chromic acid oxidation product of the lactam, lycoctonam (7), was similarly confirmed as N-ethyl-4,7,8-trihydroxy-1α,6β,14α,16β-tetramethoxy-19-oxoaconitane (8). Reduction of lycoxonine with lithium aluminium hydride gave the 1,14-di-O-methyl ether (12) of the bisnorditerpenoid alkaloid delbine (9).Key words: norditerpenoid, bisnorditerpenoid, alkaloids, lycoctonine, lycoctonam, hydroxylycoctonal, lycoxonine. 1,14-di-O-methyldelbine, semisynthesis.

Coordination Chemistry of trans-(NH3)2Pt(II) with Uracil Nucleobases. A Comparison with cis-(NH3)2Pt(II)

1990 ◽  
Vol 45 (6) ◽  
pp. 731-740 ◽  
Author(s):  
Iris Dieter ◽  
Bernhard Lippert ◽  
Helmut Schöllhon ◽  
Ulf Thewalt
Keyword(s):  
Oxidation Products ◽  
Orthorhombic Space Group ◽  
Monoclinic System ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Cell Dimensions ◽  
Rare Tautomers ◽  
Cis Isomer ◽  
Heteronuclear Complex

Protonated and heteronuclear adducts as well as a series of Pt(IV) oxidation products derived from trans-a2PtL2 (a = NH3, NH2CH3, L = 1-methyluracil anion, C5H5N2O2, or uridine anion, C10HnN2O6) have been prepared and studied by spectroscopic methods and in two cases by X-ray crystallography. trans-(NH3)2Pt(C5H5N2O2)2Ag2(NO3)2H2O · H2O (7) crystallizes in the orthorhombic space group Pna21 with cell dimensions a = 13.206(6), b = 7.238(9), c = 22.051(10) Å, U = 2107.7 Å3, Z = 4. 7 forms a polymeric structure with PtAg2 entities linked via O(4) sites of the 1-methyluracilato ligands. Pt is coordinated through N(3), the Ag centers have a mixed O(2),O(4) coordination, trans,trans,trans-[(NH3)2Pt(OH)2(C5H6N2O2)2](NO3)2 (9) contains two N(3)-bound neutral 1-methyluracil ligands, hence rare tautomers of this model nucleobase. 9 crystallizes in the monoclinic system, space group P21/n with cell dimensions a = 7.098(1), b = 10.395(1), c = 13.295(2) Å, U = 980.4 Å3, Z = 2. While the chemistry leading to Pt(IV) oxidation products from trans-a.2PtL2 is similar to that of the cis-isomer, protonation as well as heteronuclear complex formation of trans-a2PtL2 is more difficult to accomplish than with the cis-isomer. This difference appears to be primarily of steric origin.

Synthesis, characterization, redox, and Hg2+ optical ion sensing properties of ferrocenyl-containing maleo- and fumaronitrile derivatives

2014 ◽  
Vol 92 (8) ◽  
pp. 739-749 ◽  
Author(s):  
Michael R. Dahlby ◽  
Anatolii A. Purchel ◽  
Pavlo V. Solntsev ◽  
Gregory T. Rohde ◽  
Yuriy V. Zatsikha ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Charge Transfer Band ◽  
Electrochemical Techniques ◽  
Mixed Valence ◽  
Reaction Products ◽  
Functional Theory ◽  
X Ray ◽  
X Ray Crystallography ◽  
Oxidation Potentials

Mono-((Z)-2-amino-3-((E)-ferrocenylideneamino)butenedinitrile) (1) and bis-((E)-2,3-bis-((E)-ferrocenylideneamino)butenedinitrile) (2) substituted Schiff bases obtained by the reaction between ferrocenecarbaldehyde and diaminomaleonitrile were prepared and characterized by 1H and 13C NMR, IR, and UV-vis-NIR spectroscopy methods, elemental analysis, and X-ray crystallography. Density functional theory and time-dependent density functional theory were used to elucidate the electronic structure and the origin of observed excited states in both compounds. Electrochemical techniques were employed to investigate the possibility for the formation of a mixed-valence state of the iron centers in 2+, which are connected by a conjugated π-system. Two reversible oxidation potentials were observed in cyclic voltammetry, and spectroelectrochemical experiments revealed the presence of a low-energy intervalence charge transfer band in 2+, corresponding to class II of the mixed-valence systems. Both complexes were tested for cation-recognition properties using a variety of main group and transition-metal cations. It was shown that complex 1 can be used as a selective optical sensor in recognition of Hg2+ ions. It was also shown by NMR spectroscopy and X-ray crystallography that one of the final reaction products between Hg2+ ions and complex 1 is 2-ferrocenyl-4,5-dicyanoimidazole (3).

Michael-Michael Aldol Reaction of Chalcones with Cyanoacetylurea and Cyanoacetylpiperidine

1995 ◽  
Vol 60 (4) ◽  
pp. 594-604 ◽  
Author(s):  
Hani D. Tabba ◽  
Nidal M. Yousef ◽  
Mohammad M. Al-Arab
Keyword(s):  
Room Temperature ◽  
Reaction Products ◽  
One Pot ◽  
X Ray ◽  
X Ray Crystallography ◽  
Anhydrous Alcohol ◽  
One Pot Condensation ◽  
The One ◽  
Sodium Alkoxide ◽  
C Nmr

Several highly substituted cyclohexane derivatives were synthesized by the one-pot condensation of chalcones and cyanoacetylurea (2 : 1) using sodium alkoxide in anhydrous alcohol at room temperature. The structure of the reaction products was established by infrared, 1H and 13C NMR spectroscopy as well as by their elemental analysis. Single crystal X-ray crystallography shows the presence of the cyclohexane moiety.

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