Spectra of phosphate esters in the 900–1400 cm−1 region

The vibration frequencies of some phosphate esters have been measured in the 900–1400 cm^–1 region. Only some show a correlation between the P=O vibration frequencies and the Taft polar constants. It is concluded that the polar effect of the substituents is the main factor affecting the P=O vibration frequencies, but not the only one.     

Effect of Trivalent Lanthanide Halide on the Characteristic Vibrational Band of Diacetamide

Abstract

The infrared spectra of a system containing (CH₃CO) ₂NH and LnX₃ (X = C1, Br and I; Ln = lanthanide) were investigated in the region of 4000 to 180 cm ^?1. The observed frequencies assigned to N-H stretching as well as the N-H out of plane vibration have their positions considerably affected by halogen substitution.     

FTIR and Raman spectroscopic study of Fenugreek (<Emphasis Type="Italic">Trigonella foenum graecum L.</Emphasis>) seeds

The composition of Fenugreek seeds in the form of powder, ash, and oil is investigated through FTIR and FT Raman spectra measurements. The results indicate that Fenugreek seeds (powder) are rich in proteins. Fats (lipids) and starch are present in small amounts in the seeds. The FTIR absorption bands of seed powder appeared at: 3365 cm^–1 assigned as N-H stretching vibrations (amide A of protein), 1657 cm^–1 (C=O, amide I), 1540 cm^–1 (N-H bending vibration, amide II), and 1240 cm^–1 (N-H bending, amide III). In the FT Raman spectra the band at 1661 cm^–1 is ascribed to amide I (C=O) of proteins while the band at 1080 cm^–1 indicates the starch. The fenugreek oil Fourier transform infrared absorbance ratios A(3009 cm^–1)/A(2924 cm^–1), A(3009 cm^–1)/A(2854 cm^–1), and A(3009 cm^–1)/A(1740 cm^–1) were considered for measuring the iodine values. These ratios (0.3609, 0.4916, and 0.4129) revealed that the iodine value of fenugreek oil is higher than that of other oils. On the other hand, the ash of fenugreek is very rich in phosphate compounds. The spectra showed absorption bands at frequencies 1082, 1000, 618, and 566 cm^–1, and the FT Raman spectrum showed a strong absorbance band at 793 cm^–1, which is due to phosphate compounds. It could be concluded that the inorganic part of fenugreek consists mainly of phosphate compounds. The Fenugreek seed contains proteins, fat, fiber, and ash, which is in complete harmony with AACC, 1980.__________Published in Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 106–110, January–February, 2005.     

Relationship Between NH Stretching Frequencies and N…O Distances of Crystals Containing NH…O Hydrogen Bonds

Abstract

A relation between NH stretching frequencies and N…O distances is given for 42 N-H…O hydrogen bonds. The NH stretching frequencies vary from 3446 cm^?1 to 2290 cm^?1 and the N…O distances from 3.26 to 2.63 Å. Criteria for identifying the NH stretching fundamentals are discussed.     

Integral intensities of the characteristic bands of vinyl esters. II

Frequencies and integral intensities are determined for the ester C-O stretching bands and for the vinyl C-H stretching and out-of-plane bending bands for the vinyl esters of aromatic and aliphatic acids, and also for the carbonyl C=O and vinyl C=C stretching frequencies. An assignment is given for the ester C-O bands in the 1100–1300 cm^–1 region. It is found that the 1246 and 1260 cm^–1 modes in vinyl benzoate interact.We are indebted to A. F. Rekasheva for providing the compounds and to student N. V. Mel'nikova for assistance in the measurements.     

A Spectroscopic Study of Alkylamine Complexes of Copper(II) Succinimide

Abstract

The vibrational and electronic spectra of eleven complexes of copper(II) succinimide [CuSu²Am₂] (Su = succinimide ion; Am = variously substituted primary aliphatic amines) show that metal-imide co-ordination occurs through the imide nitrogen atom. The electronic effects of the amine substituents on the carbonyl stretching frequencies and on the electronic spectra are used to infer the probable mechanism of metal-imide bonding.     

Fourier Transform Vibrational Spectra of Magnesium Hydrogenphosphate Trihydrate. I. The O-H Stretching Region∗

Abstract

The Fourier transform (FT) infrared and Raman spectra of newberyite, MgHPH₄ - 3H₂O are studied in the region where the stretching vibrations of the water molecules (protiated and deuterated) and the O-H/O-D stretches of the hydrogenphosphate anions are expected to appear. The O-H stretching vibrations give rise to a complex feature known as the A,B,C trio. Since neither of the maxima found below 3000 cm^?1 represents a true band arising from a given fundamental, it is pointless to correlate their frequencies with the observed O…O distances. In the water stretching region, the two bands with highest frequencies undoubtedly correspond to the anti symmetric and symmetric stretch of one type of the water molecules. The stretching vibrations of one of the remaining two types of H₂O molecules are clearly uncoupled and the O-H oscillator involved in the weaker hydrogen bond is responsible for a band at 3376 cm^?1 whereas the rest of the water stretchings are apparently overlapped yielding the complex band below 3320 cm^?1. Thus the situation is again complicated and the correlations between the frequencies and the O_w…O distances are inappropriate. The two bands at highest frequencies (3522 and 3483 cm^?1 at RT) exhibit a positive temperature coefficient.

     

FT-IR Study of the Interaction Between H2O,D2O,HOD, and Pyridines

Abstract

The complexes between H₂O, D₂O, HOD and pyridine have been studied in 1,2-dichloroethane by FT-IR spectrometry. Equal splittings of the stretching bands of H₂O and D₂O about their uncoupled vibrations are observed. The coupling between the asymmetric and symmetric vibrations reaches a value of zero when the band separation is greater than 500 cm^?1 for the OH vibrations and 365 cm^?1 for the OD vibrations. The v_OH stretching frequencies of the HOD ‥ complexes and the v_OD stretching frequencies of the DOH‥ complexes increase by complex formation. These features are explained by an electronic reorganization within the hydrogen bond.     

Vibrational Spectroscopic and Theoretical Studies of Urea Derivatives with Biochemical Interest: N,N′-Dimethylurea,N,N,N′,N′-Tetramethylurea,and N,N′-Dimethylpropyleneurea

Abstract

Mid-infrared, far-infrared, and Raman vibrational spectroscopic studies were combined with density functional theory (DFT) calculations and normal coordinate force field analyses for N,N′-dimethylurea (DMU), N,N,N′,N′-tetramethylurea (TMU), and N,N′-dimethylpropyleneurea (DMPU: IUPAC name 1,3-dimethyltetrahydropyrimidin-2(1H)-one). The equilibrium molecular geometry of DMU (all three conformers), TMU, and DMPU and the frequencies, intensities, and depolarization ratios of their fundamental infrared (IR) and Raman vibrational transitions were obtained by DFT calculations. The vibrational spectra were fully analyzed by normal coordinate methods as well. A starting force field for DMPU was obtained by adapting corresponding force constants for DMU and TMU, resulting after refinements in the stretching force constants C=O (7.69, 7.30, 7.68 N·cm^?1), C–N (5.16, 5.55, 5.05 N·cm^?1), and C-Me (5.93, 4.00, 4.22 N·cm^?1) for DMU, TMU, and DMPU, respectively. The dominating conformer of liquid DMU was identified as trans-trans, strong intermolecular hydrogen bonding was verified in solid DMU, and weak dipole–dipole association was found in liquid TMU and in DMPU. Special attention was paid to analyzing the methyl group frequencies, which revealed deviations from local C_3v symmetry. A linear correlation was found between the CH stretching force constants and the inverse of the CH bond lengths (1/r ²). The averaged NH stretching frequencies of gaseous, dissolved, and solid urea and of DMU, with variations for hydrogen bonding of different strength, are linearly correlated to the NH stretching force constants. Characteristic skeletal vibrations were assigned for a broad variety of urea derivatives and also for pyrimidine derivatives, which all contain the N₂C=O entity. The very strong IR bands of C=O stretching (1,676 ± 40 cm^?1) and asymmetric CN₂ stretching (1,478 ± 60 cm^?1), and the very intense Raman feature of symmetric CN₂ stretching or ring breathing (757 ± 80 cm^?1), can be recognized as fingerprint bands also for the pyrimidine derivatives cytosine, thymine, and uracil, which all are nucleobases in DNA and RNA nucleotides.     

Conformational Studies of α-Substituted Carbonyl Compounds by I. R. Spectroscopy. II. α-Heterosubstituted N,N-Diethylacetamides

Abstract

The α-heterosubstituted N, N?diethylacetamides(1–8) cis/gauche conformations population ratio have been estimated through the analysis of the carbonyl group stretching vibration in the carbon tetrachloride and in chloroform. The substituent steric properties determine the cis/gauche ratio which decreases as the substituent size increases. For most of the studied amides, the gauche rotamer carbonyl band exhibits larger shifts to lower frequencies than in the corresponding α-heterosubstituted propanones¹, but for the α-chloro-(4) and for the α-bromo-N,N?diethylacetamide(5) a reverse trend is observed. This behavior can be related to changes in the πC=O C—X Dihedral angle, an hyperconjugative effect being sugges ted to explain the frequency shifts of the gauche rotamers.     

Infrared spectra of S-and R-isomers of biologically active brassinosteroids

Comparative analysis of IR spectra of S-and R-isomers differing in the configuration of OH groups in the side chain of biologically active 24-epi-and 28-homocastasterones and 24-epi-and 28-homobrassinolides is carried out. Stretching vibration frequencies of H-bonded OH groups of isomers of corresponding brassinosteroids practically coincide. The optical density in maxima of these bands is higher in spectra of the R-isomers. Alteration in the configuration of the OH groups weakly influences also the band intensities of CH3, CH₂, and CH groups. Band intensities of stretching vibrations of associated C=O groups of S-and R-isomers also neglibibly differ from each other. Their frequency characteristics do not experience substantial changes. These features differ considerably in IR spectra of castasterones and brassinolides. For castasterones, the difference in frequencies of band maxima of free and bound C=O groups amounts to ∼15 cm⁻¹; for brassinolides, 23 cm⁻¹. Intensities of both bands are approximately equal in spectra of castasterones. The band intensity of free C=O groups of brassinolides is considerably lower than that of H-bonded ones. The above spectral differences can be used to identify these brassinosteroids. Frequencies of both symmetric and antisymmetric deformation vibrations of CH₃ and CH₂ groups are close in spectra of all brassinosteroids studied. The frequency of CH₂ in a CH₂-OC group belongs only to brassinolides; of deformation vibrations of CH in a CH-C=O group, to castasterones. The frequency of stretching vibrations of C-O-C and C-O groups is observed only in spectra of brassinolides. In the region 1130–900 cm⁻¹ of IR spectra of brassinosteroids, stretching vibrations of CC, CCH, and C-OH groups are predominantly observed. In the frequency range 1130–995 cm⁻¹, the optical density of band maxima of S-isomers is higher than that of R-isomers, which can be used to identify isomers. At the same time frequencies of corresponding bands of isomers practically coincide. Differences in the structure of the side chain of brassinosteroids do not influence essentially the frequency characteristics of the IR spectra. The exception is the band related to stretching vibrations ν(C23-OH) of the side chain which features a considerable frequency ν_max ≈ 983 cm⁻¹ only in spectra of R-isomers of homocastasterone and brassinolide. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 623–630, September–October, 2008.     

Infrared Study of the Hydrogen Bond Complexes Between N-Methylsuccinimide and Phenols

Abstract

The hydrogen bonded complexes between N-methylsuccinimide and phenols (pKa = 10.2 → 6) are investigated by infrared spectrometry. The thermodynamic parameters for the 1–1 complexes are determined in carbon tetrachloride-. The formation constants at 298 K range from 15 to 150 dm³ mol^?1, the enthalpies of complex formation from - 20 to - 30 kJ mol^?1, the changes of entropy from - 22 to - 40 J K^?1 mol^?1 and the frequency shifts of the v(OH) stretching vibration from 170 to 340 cm^?1. The complexes are weaker than those involving the monocarbonyl bases. The decrease of the force constant of the bonded carbonyl group ranges from 0.48 to 0.65 N cm^?1. The force constant of the free C=O group slightly increases upon complex formation, in agreement with the cooperatively theory.     

FTIR Spectral Study of Intramolecular Hydrogen Bonding in Thromboxane A2 Receptor Antagonist S-145 and Related Compounds. Part 4

Abstract

An N-methylated compound of S-145, (±)-(5Z)-7-[3-endo-[N-methyl)phenylsulphonyl)amino]bicyclo [2.2.1]hept-2-exo-yl]heptenoic acid 1, its chain analogue 12-[N-methyl(phenylsulphonyl)amino]dodecanoic acid 3, (±)-(5Z)-7-[3-endo-(benzoylamino)bicyclo[2.2.1]hept-2-exo-yl] heptenoic acid 5 and related compounds were synthesized in order to study the formation of a new class of intramolecular hydrogen bond IX (cis-CO₂H…O = Y). Their FTIR spectra were measured in dilute CCl₄ solution and subjected to curve analysis in order to separate overlapping absorption bands. For compounds 1,3 and 5, the intramolecular hydrogen bonds of the IX type involving 14-, 17- and 14-membered rings were found between a carboxyl group, which takes a cis-structure IV, and an oxygen atom of a sulphonyl or benzoylamino group, respectively. The C[dbnd]O stretching vibration bands of these carboxyl groups shifted to lower wavenumbers (ca. 19 cm^?1). The direction of these shifts was contrary to that found for α-keto and α-alkoxycarboxylic acids in which carboxyl groups take a trans-structure III due to the formation of intramolecular hydrogen bonds I and II, respectively.     

Characterization of sodium alginate and its block fractions by surface‐enhanced Raman spectroscopy

The surface‐enhanced Raman scattering (SERS) of sodium alginates and their hetero‐ and homopolymeric fractions obtained from four seaweeds of the Chilean coast was studied. Alginic acid is a copolymer of β‐D ‐mannuronic acid (M) and α‐L guluronic acid (G), linked 1 → 4, forming two homopolymeric fractions (MM and GG) and a heteropolymeric fraction (MG). The SERS spectra were registered on silver colloid with the 632.8 nm line of a He Ne laser. The SERS spectra of sodium alginate and the polyguluronate fraction present various carboxylate bands which are probably due to the coexistence of different molecular conformations. SERS allows to differentiate the hetero‐ and homopolymeric fractions of alginic acid by characteristic bands. In the fingerprint region, all the poly‐D ‐mannuronate samples present a band around 946 cm⁻¹ assigned to C O stretching, and C C H and C O H deformation vibrations, a band at 863 cm⁻¹ assigned to deformation vibration of β‐C₁ H group, and one at 799–788 cm⁻¹ due to the contributions of various vibration modes. Poly‐L ‐guluronate spectra show three characteristic bands, at 928–913 cm⁻¹ assigned to symmetric stretching vibration of C O C group, at 890–889 cm⁻¹ due to C C H, skeletal C C, and C O vibrations, and at 797 cm⁻¹ assigned to α C₁ H deformation vibration. The heteropolymeric fractions present two characteristic bands in the region with the more important one being an intense band at 730 cm⁻¹ due to ring breathing vibration mode. Copyright © 2009 John Wiley & Sons, Ltd.     

Outer-Sphere Interaction in Hexafluorocomplexes of Elements of Group IV with Cations of Alkali Metals and Ammonium

IR-absorption spectra of M²AF⁶hexafluorocomplexes (M-Na, K, Rb, Cs and NH⁴; A=Si, Ge, Sn) were obtained and intergrated intensities of bands assigned to stretching vibrations of AF⁶ ions were measured. The reasons for the influence of exchange of the central atom and an outer-sphere cation on the intergrated intessities of vibration bands are discussed. It was found that the ammonium ion does not fit into the earlier established pattern of intensity dependence on cation size. Analysis of the frequencies v³ (AF⁶) suggeste that this is coused by the presence in (NH⁴)²AF⁶ of hydrogen bonds N-H F of different strength.

The question of the influence of anther-sphere cation on the spectral properties of complex compounds has been treated in the literature ^1-6. The dependence of vibrational frequencies characterizing the anion ^1-3, the integrated intensity vibration bands (IIVB) in IR-absorption spectra ⁴, chemical shiftn in ¹⁹ f NMR apectra ² and the luminescent properties of complexed on cation nature have been established.     

β-DDB及其衍生物的结构与红外光谱特征

总结归属了肉豆寇醚酸甲酯、6－Br肉豆寇醚酸甲酯、β-DDB（6,6′－二甲氧基－4,5,4′,5′－二次甲二氧基－2,2′－二甲氧羰基联苯）及其5种衍生物的主要红外吸收谱带和特征,讨论了其红外吸收频率随化合物结构变化的规律。 结果表明分子中酯基的改变主要对羰基的伸缩振动频率有较大的影响,而对苯环的骨架振动影响较小;当苯环上H原子被其他取代基取代时,羟基及苯环的骨架吸收均发生显著变化。     

Hydrogen-bonded OH and OD overtone bands and potential energy curve of methanol

The absorption spectra of CH₃OH, CH₃OD, CD₃OH, and CD₃OD as pure liquids and as carbon tetrachloride solutions were measured in the 3,850 – 16,600cm^?1 region. In addition to the various combination bands, the higher overtone bands of the hydrogen-bonded OH stretching vibration of self-associated methanols were observed at ～6470, 9300–9700, and 12,200 – 12,700 cm^?1 with broad half-widths of ～700, ～1200, and ～1800 cm^?1, respectively, and those of the OD stretching vibration, at ～4900, 7200–7400, and 9200–9600 cm^?1 with half-widths of ～370, ～700, and ～1200 cm^?1, respectively. With the aid of the observed frequencies, we determined the single minimum potential energy curve for the hydrogen-bonded OH and OD stretching vibrations of self-associated methanols. Furthermore, the absorption band due to double excitation of two neighboring OH groups linked together by a hydrogen bond was quantitatively analyzed by using the isotopic isolation technique. The double excitation band of CH₃OH as pure liquid was found to appear at 6730 cm^?1 with an absorbance of 0.08 at 1 mm light path length.     

Synthesis and characterization of novel nano-size polyreactive yellow 107

The reactive yellow 107 was polymerized by chemical oxidation method using potassium persulfate. The polymer was characterized by UV-VIS and Fourier transform infrared spectroscopy (FTIR) spectral studies. The peaks at 2,922 and 2,852 cm⁻¹ in the FTIR spectrum of polyreactive yellow 107 are assigned to the symmetric and asymmetric stretching vibrations of CH₂. The peak observed at 1,583 cm⁻¹ for polyreactive yellow 107 may be assigned to the stretching vibration of C=O, N=N, and C=C, 1,347 cm⁻¹ stretching vibration of C–N. The stretching vibrations of sulfone and sulfonic acid of S=O groups show a strong broad peak at 1,091 and 1,051 cm⁻¹. The conductivity of the polymer was determined to be 5.57 × 10⁻⁵ S cm⁻¹. The solubility of the chemically polymerized powder was ascertained and polyreactive yellow 107 showed good solubility in N,N-dimethyl formamide and dimethyl sulfoxide. The X-ray diffraction studies revealed the formation of nano-sized (84 nm) crystalline polymer. Using X-ray diffraction, behavior strain and dislocation density was also calculated. Scanning electron microscope analysis showed uniform crystalline nature of the polymer (200 nm). The thermogravimetric analysis, differential thermal analysis, and differential scanning calorimetry studies revealed good thermal stability of the polymer.     

柠檬酸壬基酚聚氧乙烯醚单酯二乙醇酰胺的合成及红外光谱研究

由柠檬酸出发,经过转化制备柠檬酸酐,与壬基酚聚氧乙烯醚反应制备柠檬酸壬基酚聚氧乙烯醚单酯,再与二乙醇胺反应合成了一种具有防锈、润滑双重性能的水基合成切削液新型添加剂-柠檬酸壬基酚聚氧乙烯醚单酯二乙醇酰胺。采用红外光谱法对原料、中间体及最终产物进行了测试。根据1 736.14 cm-1酯中CO双键伸缩振动的特征吸收峰,1 642.39 cm-1酰胺中CO双键伸缩振动的吸收峰,可知所得到的产物为柠檬酸壬基酚聚氧乙烯醚单酯二乙醇酰胺,说明所采用的合成的工艺路线是可行的。     

IR Spectra of Derivatives of Immunotropic 8-Azasteroids

By the method of IR Fourier spectroscopy with the use of numerical differentiation of spectral line profiles we have studied the spectra of some structural and functional derivatives of immunotropic 8-azasteroids in the region of C=O and C=C bonds (1800–1400 cm^–1). We have established the dependence of vibration frequencies of the C=O and C=C groups on the size of the ring D, the presence of heteroatoms (O, S) in the ring D, transformations in the -acyl--aminovinylcarbonyl fragment and in its adjacent positions of the heterosteroid skeleton, and the composite character of the absorption bands that are due to the vibrations of the C=O and C=C groups. The role of the structural and stereoelectronic factors in the observed group frequencies of 8-azasteroids is discussed.