Synthesis and IR spectra of some derivatives of phenanthridine and 4,9-diazapyrene

A number of acylamino- and diacylaminobiphenyls and the corresponding derivatives of phenanthridine and 4, 9-diazapyrene, including the previously unknown 2,2′-dipropionamidobiphenyl, 5, 10-diethyl-4, 9-diazapyrene, 2, 4-dibenzamidobiphenyl, and 3-benzamido-6-phenylphenanthridine, have been synthesized. The IR spectra of all the compounds have been studied and a group of bands characteristic for the phenanthridine ring in the 1570–1620 cm^?1 region and a group of five bands characteristic for the 4, 9-diazapyrene ring in the 1330–1640 cm^?1 region have been identified. The nature of the IR spectra of phenanthridine derivatives containing unsubstituted amide groups has also been established.     

Infrared spectra of cyclic ethers and their derivatives

The IR spectra of six monosubstituted and of four 2,6-disubstituted 1,4-dioxanes have been studied in the 650–1800cm^–1 region. The assignment of the bands due to the vibrations of the 1,4-dioxane ring and to the deformation vibrations of the methylene groups of the ring is given. The appearance of a whole series of new absorption bands on passing from unsubstituted 1,4-dioxane to its derivatives is explained by the change in the symmetry of the molecule and the removal of the prohibition from the vibrations previously inactive in the IR spectra connected with this reduction in symmetry. It is proposed to use, in order to confirm the presence of a 1,4-dioxane ring in a molecule from the results of IR spectroscopy, not only the 1126-cm^–1 band but the whole group of bands lying in the frequency ranges 800–950, 1000–1150, and 1200–1300 cm^–1.For part I, see [3].     

Integral intensities of the absorption bands of the skeletal vibrations of substituted furocoumarins

Conclusions The IR spectra of 5- and 8-hydroxyfurocoumarins and their esters, 5,8-disubstituted furocoumarins containing hydroxyl, methoxyl, and alkoxyl groups, and 4,5-dihydrofurocoumarins differ with respect to the intensity and number of the bands in the 1630–1500 cm^–1 region of the spectrum. The integral intensities of the absorption bands in this frequency region differ markedly in the derivatives mentioned.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 5, pp. 355–359, 1969     

Synthesis and absorption spectra of 3,5-diaryl-1,2,4-triazoles

1,2,4-Triazoles with symmetrical tolyl substituents were obtained from the corresponding 1,3,4-oxadiazoles by reaction with formamide and subsequent hydrolysis of the resulting formyl derivatives; 1,2,4-triazoles with unsymmetrical substituents were obtained from iminoesters and hydrazides of acids. A set of bands of the triazole ring at 1470–1480, 1390, 1270–1290, 1140–1150, and 725–750 cm^–1 and of NH vibrations at 2400–3200, 1580–1620, and 830–900 cm^–1 are characteristic for the IR spectra of these triazoles. The UV spectra of the triazoles are characterized by phenyl ring absorption at about 200 nm and a band of electron transitions between the phenyl and triazole rings at 230–290 nm.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1682–1685, December, 1977.     

Infrared absorption spectra of some C-halogenated 1, 2, 4-triazole derivatives

The IR absorption spectra of 3(5)-halo and 3, 5-dihalo derivatives of 1, 2, 4-triazoles and of their potassium and silver salts as solids in the 3500-400 cm^–1 range were studied. The characteristic absorption bands of the triazole ring and the C-H and N-H bonds were established.     

Über dieIR-Spektren der dinegativen Ionen einiger polycyclischer Mononitrile und Elektronenübergänge zwischen dinegativen Ionen und neutralen Molekülen

Zusammenfassung Die Nitrilgruppe in den dinegativen Ionen (DA) des mit metall. K in Tetrahydrofuran (THF) erhaltenen 1-Cyanpyrens, 9-Cyananthracens, 4-Cyanbiphenyls und 1- und 2-Cyannaphthalins zeigt sehr breite (50–70 cm^–1) und intensive Bandenv _CN zwischen 2020–2070 cm^–1.DieIR-Spektren im Bereich 2000–2250 cm^–1 wurden zur Untersuchung der Elektronenübergänge zwischenDA und einigen neutralen Molekülen herangezogen.

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IR spectra of some dinegative polycyclic mononitrile ions, and electron transitions between the ions and neutral molecules

The CN group in the dinegative ions of 1-pyrenecarbonitrile, 9-anthracenecarbonitrile, 4-biphenylcarbonitrile, 1- and 2-naphthalenecarbonitriles, resp., obtained with K in tetrahydrofuran (THF), gave rise to very broad (50–70 cm^–1) and intensive bands in the 2020–2070 cm^–1 region.IR spectra in the 2000–2250 cm^–1 region have been used to study the electronic transitions between dinegative ions and some neutral molecules.

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Mit 3 Abbildungen     

Comparative FT infrared study of structural changes occuring on dealumination of zeolite Na-Y with ethylenediaminetetraacetic or hydrochloric acid

IR lattice vibration spectra were used to monitor the changes in the structure of zeolite Na-Y upon its dealumination with ethylenediaminetetraacetic acid (EDTA) or with HCl. The terminal Si-O(H,Na) bonds thus formed (which are detectable by characteristic absorbance at v 900–950 cm^–1) are energetically less uniform when EDTA has been used as the dealuminating agent. This inhomogeneity is connected with the local deformations of zeolite structure which result in lowering the symmetry of silicon-oxygen tetrahedra. As a consequence, two novel bands appear at v 1090 cm^–1 and 1200 cm^–1 in addition to the fundamental absorption bands, v_as (TO₄) (T = Si, Al), at 1030 cm^–1 and 1145 cm^–1. A mechanism of dealumination is proposed, which takes into account the topochemical peculiarities involved in the chelation of the framework aluminum ions with EDTA.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskay, No. 2, pp. 284–287, February, 1993.     

Vibrational spectra of 2-biphenylmethanol. Spectrum simulation and molecular structure

The vibrational spectra of a solid crystalline sample of 2-biphenylmethanol have been measured at room temperature. The IR absorption spectra were recorded in the range 400 cm^–1–3600 cm^–1; Raman spectra were measured in the range 10 cm^–1–1640 cm^–1. The direct mechanical and optoelectronic problems were solved using the fragment method realized as Lev-100 software; the intensity distribution in the IR spectrum of 2-biphenylmethanol was obtained by the same method. The experimental Raman and IR absorption spectra were interpreted by analyzing the calculated data on the frequencies and forms of normal vibrations and their intensities in the IR spectra. IR absorption spectra were simulated for several models of 2-biphenylmethanol conformers that differ in the mutual orientation of fragments. Based on the results of simulation and comparison of the calculated and experimental spectra of conformers we suggested a model for the conformer realized in the solid phase under normal conditions.Original Russian Text Copyright © 2004 by L. M. Babkov, J. Baran, N. A. Davydova, J. I. Kukielskii, and S. V. TrukhachevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 624–631, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

E and Z stereoisomers of compounds of the phthalide series

The stereospecific position of the H⁴ proton in the PMR spectra of 3-benzyl-idenephthalides identifies unambiguously the E and Z isomers in a mixture. The IR spectra of off-planar deformation vibrations of the C=C bond in the 990–970 cm^–1 region have strong absorption bands, assigned to the E and Z isomers. The strong short-wave band (260 nm) for 3-benzylidenephthalides, having only one benzene ring in the indan moiety, suggests the presence of the E form (=28,000). The long-wave absorption band at 390–430 nm belongs to the Z isomers (=21,000–31,000). 3-Benzylidenephthalides which have no carbonyl groups in their molecules, show fluorescence (_f1=540–560 nm in EtOH).N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 309–314, February, 1992.     

Stoichiometry and conformation of the azacrown moiety in sodium complexes of azacrown ethers. A Raman/IR spectroscopic study. Part II: Complexes of 4,13-diaza-15-crown-5

4,13-Diaza-15-crown-5 and three of its sodium complexes (bromide, iodide and thiocyanate) were studied using Raman and IR spectroscopy and normal coordinate calculations, following the corresponding study on the sodium complexes of 4,13-diaza-18-crown-6 in the preceding paper. Complex formation was again accompanied by a characteristic shift of the bands, especially of those in the 800–900 cm^–1 region. The complexes of 4-13-diaza-15-crown-5 were distinct from those of 4-13-diaza-18-crown-6, in that both of the bands at 830 and 890 cm^–1 of the parent azacrown were affected on complex formation and in that only the 11 complex was formed. Normal mode calculations were made to predict conformations of the azacrown ring of the parent 4,13-diaza-15-crown-5 and its sodium complexes. Attention was paid to the different extent of mismatch in size of a sodium ion and azacrown cavities.     

Synthesis and characterization of novel phthalocyanines bearing quaternizable coumarin

The synthesis of novel metal-free and zinc phthalocyanines with four 3-[(2-diethylamino)ethyl]-7-oxo-4-methylcoumarin dye groups on the periphery were prepared by cyclotetramerization of a novel 3-[(2-diethylamino)ethyl]-7-[(3,4-dicyanophenoxy)]-4-methylcoumarin. The novel chromogenic compounds were characterized by elemental analysis, ¹H NMR, ¹³C NMR, MALDI-TOF, IR and UV–Vis spectral data. The electronic spectra exhibit bands of coumarin identity along with characteristic Q and B bands of the phthalocyanine (Pc) core. The IR spectra of all the Pcs showed three characteristic intense bands, at 1704 cm⁻¹ for the lactone carbonyl and two bands at 1489–1604 cm⁻¹ for the conjugated olefinic system.     

Infrared absorption spectra of some derivatives of 1,2,3,4-tetrahydro-Β-carboline

The IR absorption spectra in 3800-1400 cm^–1 region of 1-propyl-, 1-carboxy-, 1-carboxy-1-methyl-, and 1-benzyl-1-carboxy-6-hydroxy-1,-tetrahydro--carbolines, their O-methyl derivatives, and their hydrochlorides are discussed. An assignment of the bands due to the stretching vibrations of NH, NH ₂ ⁺ , OH, COO^–, and COOH groups is proposed. The hypothesis has been put forward that strong intermolecular and intramolecular hydrogen bonds exist in the substances studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 6, pp. 775–778, June, 1970.     

Effect of intermolecular =C–HO interaction on the crystal structure and vibrational properties of 2,6-dimethyl-4-nitropyridine N-oxide

The crystal structure of 2,6-dimethyl-4-nitropyridine N-oxide (DMNPO) has been determined at ambient temperature. The compound crystallizes as a monoclinic structure, space group P2/n, with 12 molecules per unit cell. The unit cell contains three non-equivalent formula units. The nitro group is not coplanar with the pyridine ring. Through a system of =C–HO hydrogen bonds the molecules are arranged into a two-dimensional network of layers parallel to the axc plane.The IR and Raman spectra, measured in the 3500–100 cm⁻¹ region at ambient temperature, are correlated with X-ray structural data. The assignment of IR and Raman bands is given. The appearance of characteristic vibrational features in the spectra of this compound and the observed shifts of the =C–H and N–O IR active stretching modes, when the sample is dissolved in CCl₄, is discussed in terms of the relatively strong =C–HO hydrogen bonds present in this crystal.     

Bromination of spiropyrans and reduction of their nitro derivatives

Depending on the nature of the nitrogen heteroring, either substitution only in the chromene ring (phenanthridine derivatives) or in both fragments of the molecule (indoline derivatives) occurs in the bromination of spiropyrans of the phenanthridine and indoline series with N-bromosuccinimide in low-polarity solvents, in which they are found in the cyclic form. The activity of the chromene fragment in both types of spiropyrans is approximately the same. The corresponding amino derivatives are formed in the catalytic reduction of spiropyran derivatives with a nitro group in the chromene ring in benzene solution. In alcohol solutions the nitro group and the 3–4 double bond of the chromene ring are hydrogenated simultaneously.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1320–1326, October, 1977.     

Calculations of silicooxygen ring vibration frequencies

In the work model calculations of the vibrations of ideally isolated silicooxygen rings (using PM3 method) have been carried out. three-, four-, and six-membered rings have been considered. It has been found that that the three-membered silicooxygen rings are flat and practically undeformed showing D_3h symmetry. The rings of higher number of ring members (i.e. n>3) are deformed to some extent. The deformation reveals itself most significantly in the Si–O–Si bond angles distribution. In the case of all the rings the bridging Si–O–Si bonds are ca. 0.02–0.04 Å shorter than the non-bridging Si–O⁻ bonds. Hypothetical IR spectra for all the rings considered have been also calculated. Analysis of these hypothetical spectra leads to the conclusion that the whole spectrum can be divided into four wavenumbers regions, 1200–1100 cm⁻¹ stretching Si–O(Si) vibrations; 1000–800 cm⁻¹ stretching Si–O⁻ vibrations; 800–600 cm⁻¹; the region in which a band characteristic of silicooxygen rings appears, and below 600 cm⁻¹ bending ⁻O–Si–O⁻ and (Si)O–Si–O(Si). It has been also found that as the number of ring members increases the ‘ring band’ shifts to lower wavenumbers: 725 cm⁻¹ for three-membered rings, 650 cm⁻¹ for four-membered rings and 610 cm⁻¹ for six-membered rings. Calculated spectra have been compared with the experimental spectra of cyclosilicates. They showed good agreement in the 1200–600 cm⁻¹ region. In the experimental spectra as well as in the calculated ones, with increasing the number of ring members the ‘ring band’ shifts towards lower wavenumbers.     

IR spectra and structure of 2-aryl-3-hydroxypyridines

The IR spectra of methyl, chloro, and phenyl derivatives of 3-hydroxypyridines in CCl₄ solutions and in the crystalline state were studied. A comparison of the frequencies, half widths, and integral intensities of the bands of the stretching vibrations of the hydroxyl groups in the spectra of solutions of the 3-hydroxypyridine derivatives in CCl₄ with the characteristic OH bands in the spectra of phenols demonstrates that 3-hydroxypyridines exist practically completely in the hydroxy form in dilute CCl₄ solutions. The shift in the OH bands in the spectra of 2-phenyl-3-hydroxypyridine derivatives indicates that the OH group forms a -hydrogen bond with the phenyl ring. The presence also of a band of a free OH group is evidence for the existence of s-cis and s-trans conformers relative to the C-O bond.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 187–190, February, 1972.     

Alkylation of 4-oxo-3-methyl-4,5,6,7-tetrahydroindazoles

The alkylation of 4-oxo-3,6,6-trimethyl-4,5,6,7-tetrahydroindazole with alkyl halides forms mixtures of 1-alkyl and 2-alkyl derivatives which have been separated by fractional crystallization from n-hexane. The 4-oxo-1-alkyl-,-1-aryl-, and -1-acyl-4,5,6,7-tetrahydroindazoles have characteristic frequencies in their IR spectra at 1540-1530 cm^–1, and the corresponding 2-substituted derivatives have frequencies at 1565-1555 cm^–1. The introduction of an alkyl substituent at a nitrogen atom decreases the basicity of 4,5,6,7-tetrahydroindazole by 0.6 orders of magnitude, the 1-alkyl isomers being somewhat stronger bases than the 2-alkyl isomers.     

Vibrational spectra of mixed (phthalocyaninato)(porphyrinato) yttrium(III) double-decker complexes: Density functional theory calculations

The vibrational (IR and Raman) spectra of neutral and reduced mixed (phthalocyaninato)(porphyrinato) yttrium(III) double-decker complexes Y(Pc)(Por) and [Y(Pc)(Por)]⁻ [the simplified models of mixed (phthalocyaninato)(porphyrinato) rare earth(III) complexes] are studied using density functional theory (DFT) calculations. The simulated IR and Raman spectra of Y(Pc)(Por) are compared with the experimental IR spectrum of Tb(Pc)(TClPP) and Raman spectrum of Y(Pc)(TClPP), respectively, and many bands can acceptably fit in spite of the different species. On the basis of comparison with the simulated spectra of PbPc and PbPor together with the assistance of normal coordinate analysis, the calculated frequencies in their IR and Raman spectra are identified in terms of the vibrational mode of different ligand for the first time. The calculated frequency at 1048 cm⁻¹ in the IR spectrum of [Y(Pc)(Por)]⁻ with contribution from both Pc and Por vibrational modes is the characteristic IR vibrational mode of the reduced double-decker, while the characteristic IR vibrational mode of Y(Pc)(Por) attributed from the vibration of phthalocyanine monoanion radical Pc⁻ appears at 1257 cm⁻¹. In line with our previous experimental findings that the Raman spectra of M(Pc)(TPP) and M(Pc)(TClPP) are dominated by the Pc vibrational modes, theoretical calculations indicate that most of the Raman vibrational modes contributed from Por ring are covered up by those of Pc ring and thus are hard to be recognized in the Raman spectra of [Y(Pc)(Por)]⁻ and Y(Pc)(Por) due to their much weaker intensity in comparison with that of Pc ligand. Comparison in the IR and Raman spectra between [Y(Pc)(Por)]⁻ and Y(Pc)(Por) also suggests the localization of hole on the Pc ring in the neutral double-decker Y(Pc)(Por). The present work, representing the first detailed DFT study on the vibrational spectra of mixed (phthalocyaninato)(porphyrinato) rare earth(III) double-decker complexes, is useful in helping to understand the vibrational spectroscopic properties of this series of mixed tetrapyrrole ring complexes.     

Use of Raman spectroscopy for the establishment of the structure of pyrimidine derivatives

Intense bands of stretching vibrations are characteristic for the ER spectra of compounds of the pyrimidine series, whereas strong polarized bands of the radially symmetrical vibrations of the pyrimidine skeleton are characteristic for the Raman spectra. The band of the radially symmetrical vibration at 1000 cm^–1 is not observed in the Raman spectra of pyrimidines having a substituent in the 5 position.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1399–1401, October, 1975.     

Diffuse-Reflectance IR Spectra of Methane Adsorbed on NaZSM-5 and HZSM-5 Zeolites

Diffuse-reflectance IR spectra of methane adsorbed on high-silica NaZSM-5 and HZSM-5 zeolites point to a stronger adsorption of methane on sodium cations than on protons. For the asymmetric stretching vibration ₃, this form of adsorption is characterized by a doublet with band maxima at 2980 and 3010 cm^–1. For the fully symmetric stretching vibration ₁, it is characterized by a singlet with a maximum at 2880 cm^–1. Methane is also adsorbed on NaZSM-5 in a weaker form, which is characterized by absorption bands with maxima at 3002 (₃) and 2887 (₁) cm^–1. The weaker form of methane adsorption on acidic bridging hydroxy groups of HZSM-5 is characterized by absorption bands at 3001 and 2887 cm^–1 (₃ and ₁, respectively). A difference between this form of adsorption and weak adsorption on sodium-exchanged zeolite reveals itself in the somewhat higher intensity of the band at 2887 cm^–1. For methane adsorbed on NaZSM-5, the frequencies of deformational vibrations and a spectrum in the near IR region are obtained for the first time. It was found that the perturbance of adsorbed methane molecules is seen in the spectrum as in the low-frequency shifts of most of the bands that appear due to composite vibrations and overtones and as new adsorption bands that were not observed for gaseous methane.