Muss spectral fragmentation pattern of 2,2′-bipyridyis. Part VI. 2,2′- thiodipyridine

The mass spectral fragmentation of 2,2′-thiodipyridine is reported. The base peak is due to the M? I ion. The principal fragmentation routes involve loss of H, CS, CHCS and HCN from the molecular ion and CS, HCN and S from the. M-I species. Rupture of the central bonds is also an important disintegration pathway.     

Mass spectral fragmentation pattern of 2,2′-bipyridyls. Part XII. 2,2′-Selenodipyridine

The mass spectrum of 2,2′-selenodipyridine obtained by electron impact is reported. The base peak in the spectrum is due to the C₅H₄N⁺ ion formed principally by rupture of the central bonds. The molecular ion gives rise to a peak of 50% of the intensity of the base peak. Other fragmentations include loss of H, Se and CSe from the molecular ion and HCN from the M-1 ion.     

Mass spectral fragmentation pattern of 2,2′-bipyridyls. Part VIII. 2,2′-Bipyridyl-5-carboxylic Acid and 2,2′-bipyridyl-5-sulphonic acid

The mass spectra of 2,2′-bipyridyl-5-carboxylic acid and 2,2′-bipyridyl-5-sulphonic acid obtained by electron impact are described. The principal initial fragmentation routes from the molecular ion of the carboxylic acid involve loss of CO, CN^˙, HCN, CO₂, OH^˙ and H₂O. From the molecular ion of the sulphonic acid the principal fragmentations are accompanied by loss of HCN, O₃, SO₂ and SO₃.     

Mass spectral fragmentation pattern of 2,2′-bipyridyls Part XI. 2,2′-Iminodipyridine

The base peak in the mass spectrum of 2,2′-iminodipyridine is due to the M-1 ion. There are several minor fragmentation routes from the molecular ion but the principal pathway involves rupture of the central bonds. J. Heterocyclic Chem., 14, 1103 (1977)     

Mass spectral fragmentation pattern of 2,2′-Bipyridyls. Part IX. 6-Alkoxy-2,2′-bipyridyls

The mass spectral fragmentation patterns of 6-methoxy-, 6-ethoxy- and 6-propoxy-2,2 ′-bipyridyls are reported. The base peaks in the spectra of both the 6-methoxy and 6-ethoxy compounds are due to the M-lion of 6-methoxy-2,2′-bipyridyl, while the base peak with 6-propoxy-2,2- bipyridyl is due to a species formed by loss of C₃H₆ from the molecular ion.     

Mass spectral fragmentation pattern of 2,2′-Bipyridyls. Part X. trans-1,2-Di-(2-pyridyl)ethylene

The base peak in the mass spectrum of trans-1,2-di-(2-pyridyl)ethylene is due to the M-1 ion. A major fragmentation route involves loss of HCN from the M-1 ion. Another important pathway involves rupture of one of the bonds linking a pyridine ring with the central CH?CH group.     

Mass spectral fragmentation pattern of 2,2′-bipyridyls. Part VII 2,2′-dithiodipyridine

The mass spectral fragmentation of 2,2′ -dithiodipyridine involves loss of the elements S, SH and S₂ from the molecular ion in addition to rupture of the central bonds. Molecular rearrangements accompany the disintegration.     

Bis(3‐amino­pyridine‐κN)(4,4′‐di­methyl‐2,2′‐bipyridine‐κ2N,N′)(per­chlorato‐κO)copper(II) per­chlorate

The title compound, [Cu(ClO₄)(C₅H₆N₂)₂(C₁₂H₁₂N₂)]ClO₄, was prepared by in situ partial ligand substitution between 3‐amino­pyridine and 4,4′‐dimethyl‐2,2′‐bipyridine at room temperature. The central copper(II) ion is five‐coordinated by one bidentate 4,4′‐dimethyl‐2,2′‐bipyridine mol­ecule, two monodentate pyridine‐coordinated 3‐amino­pyridine mol­ecules and one apical O atom from the perchlorate counter‐ion. Inter­molecular N—H⋯O and C—H⋯O hydrogen‐bonding inter­actions form a hydrogen‐bond‐sustained network.     

4,4′‐Methylenediphenol–4,4′‐bipyridine (2/3): decarboxylation of 5,5′‐methylenedisalicylic acid under hydrothermal conditions

Reaction of 5,5′‐methylenedisalicylic acid (5,5′‐H₄mdsa) with 4,4′‐bipyridine (4,4′‐bipy) and manganese(II) acetate under hydrothermal conditions led to the unexpected 2:3 binary cocrystal 4,4′‐methylenediphenol–4,4′‐bipyridine (2/3), C₁₃H₁₂O₂·1.5C₁₀H₈N₂ or (4,4′‐H₂dhdp)(4,4′‐bipy)_1.5, which is formed with a concomitant decarboxylation. The asymmetric unit contains one and a half 4,4′‐bipy molecules, one of which straddles a centre of inversion, and one 4,4′‐H₂dhdp molecule. O—H...N interactions between the hydroxy and pyridyl groups lead to a discrete ribbon motif with an unusual 2:3 stoichiometric ratio of strong hydrogen‐bonding donors and acceptors. One of the pyridyl N‐atom donors is not involved in hydrogen‐bond formation. Additional weak C—H...O interactions between 4,4′‐bipy and 4,4′‐H₂dhdp molecules complete a two‐dimensional bilayer supramolecular structure.     

Mass spectral fragmentation pattern of 2,2′-bipyridyls Part IV. Di-2-pyridly ketone

The fragmentation of di-2-pyridyl ketone on electron impact involves elimination of neutral CO from the molecular ion and rearrangement to the 2,2′-l>ipyridyl molecular ion in addition to rupture of the central bonds to form C₅H₄N⁺ and C₆H₄NO⁺ ions.     

Synthesis and mass spectrum of 3,3′-thiobispyridine and polarographic reduction of 1,1′-dimethyl-3,3′-thiobispyridinediium diiodide

3,3′-Thiobispyridine is prepared by reaction of pyridine-3-thiol with 3-bromopyridine. The base peak in the mass spectrum of 3,3′-thiobispyridine is due to the molecular ion which fragments by loss of H, HCN and CS as well as by central bond rupture. The 1,1′-dimethyl diquaternary salt of 3,3′-thiobispyridine is reduced polarographically by a one electron transfer not involving hydrogen to an unstable radical cation at a potential (E_o) of −0.72 V in the pH range 7.4–11.2.     

Mass spectral fragmentation pattern of 2,2′-bipyridyls. Part XIII. 6-Chloro- and 6-bromo-2,2′-bipyridyls

The mass spectra of 6-chloro- and 6-bromo-2,2′-bipyridyls are reported. The principal fragmentation route from the molecular ions involves loss of the halogen group to give the M-1 ion of 2,2′-bipyridyl which gives rise to the base peak in the spectra. Loss of HCN before loss of Cl occurs to a small extent with 6-chloro-2,2′-bipyridyl.     

Ortho effects of a nitro group in 2′,3′ and 4′monosubstituted-trans-2,4-dinitrostilbenes on electron impact. IV

The mass spectral fragmentation patterns of thirteen 2′,3′ and 4′-R-trans-2,4-dinitrostilbenes obtained by electron impact have been studied. The main routes of fragmentation involves loss from the molecular ion due to the ortho effects of the 2-nitro substituents. Substitution on positions 2′,3′ and 4′ of stilbene moiety does not influence the fragmentation patterns.     

Substituted 2,2′‐Bis(2‐oxidobenzylideneamino)‐4,4′‐dimethyl‐1,1′‐biphenyl Complexes of Zinc

The condensation reaction of 2,2′‐diamino‐4,4′‐dimethyl‐6,6'‐dibromo‐1,1′‐biphenyl with 2‐hydroxybenzaldehyde as well as 5‐methoxy‐, 4‐methoxy‐, and 3‐methoxy‐2‐hydroxybenzaldehyde yields 2,2′‐bis(salicylideneamino)‐4,4′‐dimethyl‐6,6′‐dibromo‐1,1′‐biphenyl ( 1a ) as well as the 5‐, 4‐, and 3‐methoxy‐substituted derivatives 1b , 1c , and 1d , respectively. Deprotonation of substituted 2,2′‐bis(salicylideneamino)‐4,4′‐dimethyl‐1,1′‐biphenyls with diethylzinc yields the corresponding substituted zinc 2,2′‐bis(2‐oxidobenzylideneamino)‐4,4′‐dimethyl‐1,1′‐biphenyls ( 2 ) or zinc 2,2′‐bis(2‐oxidobenzylideneamino)‐4,4′‐dimethyl‐6,6′‐dibromo‐1,1′‐biphenyls ( 3 ). Recrystallization from a mixture of CH₂Cl₂ and methanol can lead to the formation of methanol adducts. The methanol ligands can either bind as Lewis base to the central zinc atom or as Lewis acid via a weak O–H ··· O hydrogen bridge to a phenoxide moiety. Methanol‐free complexes precipitate as dimers with central Zn₂O₂ rings.     

The cocrystal of 3‐hydroxy‐2‐naphthoic acid and 4,4′‐bipyridine

4,4′‐Bipyridine cocrystallizes with 3‐hydroxy‐2‐naphthoic acid in a 1:2 ratio to give a centrosymmetric three‐component supra­molecular adduct, namely 3‐hydroxy‐2‐naphthoic acid–4,4′‐bipyridine (2/1), C₁₁H₈O₃·0.5C₁₀H₈N₂, in which 4,4′‐bipyridine is located on an inversion center. The pyridine–carboxylic acid heterosynthon generates an infinite one‐dimensional hydrogen‐bonded chain viaπ–π inter­actions between naphthyl and 4,4′‐bipyridine groups. The one‐dimensional chains are further assembled into a three‐dimensional network by weak C—H⋯π inter­actions between pyridyl and naphthyl rings, and C—H⋯O inter­actions between 3‐hydroxy‐2‐naphthoic acid mol­ecules.     

Cocrystallization of adamantane‐1,3‐dicarboxylic acid and 4,4′‐bipyridine

The cocrystallization of adamantane‐1,3‐dicarboxylic acid (adc) and 4,4′‐bipyridine (4,4′‐bpy) yields a unique 1:1 cocrystal, C₁₂H₁₆O₄·C₁₀H₈N₂, in the C2/c space group, with half of each molecule in the asymmetric unit. The mid‐point of the central C—C bond of the 4,4′‐bpy molecule rests on a center of inversion, while the adc molecule straddles a twofold rotation axis that passes through two of the adamantyl C atoms. The constituents of this cocrystal are joined by hydrogen bonds, the stronger of which are O—H...N hydrogen bonds [O...N = 2.6801 (17) Å] and the weaker of which are C—H...O hydrogen bonds [C...O = 3.367 (2) Å]. Alternate adc and 4,4′‐bpy molecules engage in these hydrogen bonds to form zigzag chains. In turn, these chains are linked through π–π interactions along the c axis to generate two‐dimensional layers. These layers are neatly packed into a stable crystalline three‐dimensional form via weak C—H...O hydrogen bonds [C...O = 3.2744 (19) Å] and van der Waals attractions.     

Co‐crystallization of hemimellitic acid with 4,4′‐bipyridine forming a pillar‐layered hydrogen‐bonded network

Co‐crystallization of hemimellitic acid (benzene‐1,2,3‐tricarboxylic acid) dihydrate (H₃HMA·2H₂O) with 4,4′‐bipyridine (4,4′‐bpy) affords the 1:1 co‐crystal benzene‐1,2,3‐tricarboxylic acid–4,4′‐bipyridine (1/1), H₃HMA·4,4′‐bpy or C₉H₆O₆·C₁₀H₈N₂. Strong O—H⋯O hydrogen bonds connect the acid mol­ecules to form a one‐dimensional zigzag chain, around which the 4,4′‐bpy components are fixed as arms via O—H⋯N inter­actions, resulting in a ladder motif. Through weak C—H⋯O non‐covalent forces, the resulting acid layers are extended into a three‐dimensional pillar‐layered architecture supported by rod‐like 4,4′‐bpy components. The influence on hydrogen‐bonding models is also discussed, with the discovery of an unexpected inter­action motif that does not follow the routine hydrogen‐bonded hierarchical rule in the construction of an acid–base co‐crystal.     

Mass spectral fragmentation pattern of 5-methyl-4-[(phenylamino)methylene]-2,4-dihydro-3h-pyrazol-3-one and its 2-methyl and 2-phenyl derivatives

The mass spectral fragmentation patterns of 5-methyl-4-[(phenylamino)methylene]-2,4-dihydro-3H-pyrazol-3-one and its 2-methyl and 2-phenyl derivatives have been elucidated. The principal initial fragmentation route involves rupture of the exocyclic CH-NH bond. Minor routes involve loss of H, OH and C₆H₅ from the molecular ion and rupture of the pyrazolone ring.     

Mass spectral fragmentation pattern of 3-methyl-4-arylaminomethyleneisoxazol-5-ones

The mass spectral fragmentation patterns of 3-methyl-4-arylaminomethyleneisoxazol-5-ones obtained by electron impact have been elucidated. The base peaks are due to the molecular ions. The main fragmentation routes involve loss of H, OH, H₂O, CO₂ and COOH from the molecular ions as well as rupture of the exocyclic CH-NH bond.     

Mass spectral fragmentation pattern of 2,2-bipyridyls. Part V. 2,2′-oxydipyridine

The mass spectrum of 2,2′-oxydipyridine obtained by electron impact is reported. The principal fragmentations involve loss of C₂IIO and CO in addition to rupture of the central bonds. Molecular rearrangements accompany the fragmentations.