Synthesis of Cyanobenzaldehydes （m—,o—,p—）by Molecular oxygen Oxidation Methods

Cyanobenzaldehydes (m-,o-,p-) were synthesized by oxidation of corresponding tolunitriles with molecular oxygen,catalyzed by cobalt acetate and sodium bromide.     

邻、间、对-二甲氧基亚甲基苯及衍生物双自由基体系的自旋耦 合规律

采用量子化学abinitio法对具有甲氧基的碳、氧双自由基邻、间、对二甲氧基亚甲基苯及衍生物体系基态自旋耦合规律进行研究,得到非平面共轭体系中自由基之间磁性耦合的拓朴规则:共轭体系中,两个自由基之间以偶数个碳原子耦合,则有效交换积分J~i~j<0,体系具有低自旋基态;两个自由基之间以奇数个碳原子耦合,则J~i~j>0,体系具有高自旋基态。自由基性质对自旋耦合的影响较大,正离子自由基间磁性耦合能力较强,这些结论为有机磁性材料的分子设计与实验合成提供了理论依据。     

Electron impact mass spectrometry of substituted benzyl(1-allylcycloalkyl)amines and their cyclization products

Electron impact mass spectra have been measured for benzyl(1-allylcycloalkyl)amines and α-phenylethyl(1-allylcycloalkyl)amines and for the spiro(benzo-2-azepine-3,1′-cycloalkanes) produced by their cyclization.     

Effect of hydrogen bonding on the polymerization of N-(o-,m-, and p-methoxyphenyl)- and N-(o-,m-, and p-ethoxyphenyl)-methacrylamides

Summary Study of the rates of polymerization of N-(o-, m-, and p-methoxyphenyl)- and N-(o-, m-, and p-ethoxy-phenyl)methacrylamides showed that the ortho isomers of these compounds, in which there is no association between the molecules, polymerize much more rapidly than their meta and para isomers, the molecules of which are associated through hydrogen bonds.     

Tetrazole compounds. 11. electron impact mass spectrometry of 1-aryl-5-(l-acyl-2-dialkylaminovinyl)-1H-tetrazoles

The mass spectrometric behaviour of 1-aryl-5-(1-acyl-2-dialkylaminovinyl)-1H-tetrazoles was studied, especially using 1-phenyl-5-(1-benzoyl-2-dimethylaminovinyl)-1H-tetrazole 1 and its D-and ¹⁵N-labeled derivatives. All tetrazoles investigated showed a clearly observable molecular ion and underwent as the main fragmentation the elimination of nitrogen followed by a number of various subsequent processes. Besides, primary fragments such as [M ? N₃^?]⁺ and [M — ArN₃]^+? were also observed.     

Negative-ion mass spectra of some N-mesyl derivatives of o-(cycloalk-2-enyl)-, o-(cycloalk-1-enyl)-, o-(pent-2-enyl)-, o-dibromopentylanilines and (α-bromoalkyl)indolines

The formation and fragmentation of negative ions of some N-(methylsulfonyl)anilines upon resonance electron capture have been studied. The formation of long-living molecular ions is due to the presence of the mesyl groups in the molecules. The difference in negative-ion mass spectra of isomeric N-(methylsulfonyl)anilines has been revealed.     

5-α-(磷酸基)苄基-2-甲基-4-羟基咪唑衍生物的电子轰击质谱研究

本文报道了六种新的咪唑衍生物的电子轰击质谱,着重讨论了P--C, P--N键的断裂; 产物离子的开环反应;产物离子的H重排反应和失去CO的反应等. 根据高分辨精确质量测量和联动扫描技术, 讨论了化合物的质谱裂解机理.     

Angular heterocycles. A convenient synthesis of 6-N-(acetylanilino)-5H-benzo[a]phenothiazin-5-one, 6-N-(acetylanilino)-5H-benzo[a]phenoxazin-5-ones and their derivatives

The reaction of 2-N-(acetylanilino)-3-chloro-1,4-naphthoquinone ( 2 ) with bifunctional aromatic amines afforded angular heterocycles 6 and 7 . Reductive acetylation of 7 provided o-acyl 9 and O,N-diacyl 10 derivatives depending upon the reaction conditions. The ir, uv, pmr and mass spectral data are also presented.     

Electron impact mass spectrometry of isomeric [(5-N-methyl) and (12-N-methyl)]-11-(o- and p-R-aniline)-5H-dibenzo [b,e] [1,4]diazepines

The mass spectra of twelve isomeric [(5-N-methyl) and (12-N-methyl)]-11-(o- and p-R-aniline)-5H-dibenzo [b, e] [l,4]diazepines which have potentially useful pharmacological properties are presented.     

Synthesis,spectral characterization and electrochemical properties of 1H-3-(o-, m- and p-ferrocenylphenyl)-1-phenylpyrazole-4-carboxaldehydes

New ferrocene derivatives – 1H-1-phenylpyrazole-4-carboxaldehydes containing o-, m- and p-ferrocenylphenyl group at position 3 – were synthesized and characterized. The electrochemical investigation showed that the position of the ferrocenyl group does not affect the redox potential of these compounds. The X-ray crystal structure of the ortho-derivative is also presented. The screening for the in vitro antimicrobial activity against eleven bacterial and three fungal/yeast strains exhibited complete inactivity of these aldehydes, but n-butyl imines of ortho and meta derivatives showed moderate activity compared to those of the used standards.     

The fragmentation of 7-(o- and p-R-benzylidene)-3-(o- and p-R-phenyl)-2-methyl-3,3a,4,5,6,7-hexahydro-2H-indazoles under electron impact. II

The electron impact mass spectrometric fragmentation pathways for several 2-methylindazoles, II, were investigated. Our investigation of the mass spectra of these compounds revealed interesting relationships between the 2-N-methyl-substituent in the framework of II and the fragmentation patterns.     

Pi and sigma-phenylethynyl radicals and their isomers o-, m-, and p-ethynylphenyl: structures, energetics, and electron affinities

Molecular structures, energetics, vibrational frequencies, and electron affinities are predicted for the phenylethynyl radical and its isomers. Electron affinities are computed using density functional theory, -namely, the BHLYP, BLYP, B3LYP, BP86, BPW91, and B3PW91 functionals-, employing the double-zeta plus polarization DZP++ basis set; this level of theory is known to perform well for the computation of electron affinities. Furthermore, ab initio computations employing perturbation theory, coupled cluster with single and double excitations [CCSD], and the inclusion of perturbative triples [CCSD(T)] are performed to determine the relative energies of the isomers. These higher level computations are performed with the correlation consistent family of basis sets cc-pVXZ (X = D, T, Q, 5). Three electronic states are probed for the phenylethynyl radical. In C2v symmetry, the out-of-plane (2B1) radical is predicted to lie about 10 kcal/mol below the in-plane (2B2) radical by DFT methods, which becomes 9.4 kcal/mol with the consideration of the CCSD(T) method. The energy difference between the lowest pi and sigma electronic states of the phenylethynyl radical is also about 10 kcal/mol according to DFT; however, CCSD(T) with the cc-pVQZ basis set shows this energy separation to be just 1.8 kcal/mol. The theoretical electron affinities of the phenylethynyl radical are predicted to be 3.00 eV (B3LYP/DZP++) and 3.03 eV (CCSD(T)/DZP++//MP2/DZP++). The adiabatic electron affinities (EAad) of the three isomers of phenylethynyl, that is, the ortho-, meta-, and para-ethynylphenyl, are predicted to be 1.45, 1.40, and 1.43 eV, respectively. Hence, the phenylethynyl radical binds an electron far more effectively than the three other radicals studied. Thermochemical predictions, such as the bond dissociation energies of the aromatic and ethynyl C-H bonds and the proton affinities of the phenylethynyl and ethynylphenyl anions, are also reported.     

Synthesis and spectral properties of methyl 5-[(o-, m-, and p-R)-phenoxy]-2-benzimidazolecarbamate

The preparation of eleven novel methyl 5-[(o-, m-, p-R)-phenoxy-2-benzimidazolecarbamates with possible pharmacological activity as anthelmintics is described. The structure of all products was corroborated by ir, ¹H-nmr, ¹³C-nmr and mass spectra.     

Differentiation of isomeric 5- and 7-oxo derivatives of tetrahydrothiazolo[3,2-a]pyrimidine by electron impact mass spectrometry

The electron impact mass spectra of two series of 5-oxo-tetrahydro-5H-thiazolo [3,2-a]pyrimidine-6-ethylcarboxylates and 7-oxo-tetrahydro-7H-thiazolo [3,2-a]pyrimidine-6-ethylcarboxylates were measured and fragmentation patterns examined. Structures were assigned from analysis of oxo molecular ion fragmentations. Compounds of the 5-oxo series gave an [M – CO₂C₂H₅]⁺ fragmentation whereas compounds of the 7-oxo series gave three characteristic cleavages. This decomposition was confirmed for one pair of isomers by high-resolution mass spectrometry and unimolecular mass-analysed ion kinetic energy spectrometry. Electron impact mass spectrometry is a convenient method for assigning structures of 5- and 7-oxo regioisomers of tetrahydrothiazolo[3,2-a]pyrimidine-6-carboxylates.