Infrared spectral

D. Dolphin, A. Wick, Thbulation of Infrared Spectral Data, Wley, New York, 1977. 

Bromine Trifluoride. Bromine trifluoride is a colorless Hquid. The commercial grade is usually amber to red because of slight bromine contamination. The molecule has a distorted T stmeture (26). Infrared spectral data (26—30), the uv-absorption spectmm (31), and vapor pressure data (32) may be found in the Hterature. 

A solubihty parameter of 24.5-24.7 MPa / [12.0-12.1 (cal/cm ) ] has been calculated for PVF using room temperature swelling data (69). The polymer lost solvent to evaporation more rapidly than free solvent alone when exposed to air. This was ascribed to reestabUshment of favorable dipole—dipole interactions within the polymer. Infrared spectral shifts for poly(methyl methacrylate) in PVF have been interpreted as evidence of favorable acid—base interactions involving the H from CHF units (70). This is consistent with the greater absorption of pyridine than methyl acetate despite a closer solubihty parameter match with methyl acetate. 

Optical Properties. The optical transmission of vitreous siUca is influenced by impurities and the forming process. Ultrapure vitreous siUca has the abihty to transmit from the deep ultraviolet, through the visible, and into the near-infrared spectral range. 

B. J. ZwoHnski and co-workers. Catalog of Selected Infrared Spectral Data, Serial No. 321, Thermodynamics Research Center Data Project, Texas A M University, College Station, Tex., 1967. 

In the infrared spectral range in general Fourier transform (FT) interferometers are used. In comparison with dispersive spectrometers FTIR enables higher optical throughput and the multiplex advantage at equivalent high spectral resolution. In... 

As mentioned in Section II,B, solutions of y9-hydroxypyridines in the nonpolar solvents chloroform and carbon tetrachloride show sharp infrared absorption bands near 3600 cm indicating that they exist in the hydroxy form. Infrared spectral data also led Mason to conclude that -hydroxypyridines probably exist largely as such in the solid state and exhibit O— 0 hydrogen bonding, a conclusion which is contrary to an earlier proposal favoring a zwitterion structure. 

In the isoquinoline series, infrared spectral data favor nonaromatic forms of type 50 for homophthalimide," a series of substituted homo-phthalimides, and certain iV-hydroxyhomophthalimides the predominance of this structure type gains support from the ultraviolet spectra of homophthalimide and A"-ethylhomophthalimide. ... 

Although cytosine was assigned structure 109 on the basis of early infrared spectral studies,and other infrared and ultraviolet spectral... 

Tanner,from infrared spectral work, tentatively concluded that 4,6- and 4,5-dihydroxy- and 4,5,6-trihydroxy-pyrimidines exist in the monooxo forms 117, 118 (X = H), and 118 (X — OH), respectively these conclusions are supported by ultraviolet spectral data and chemical evidence. " 2,4,5,6-Tetrahydroxypyrimidine has been isolated in two forms—dialuric acid and isodialuric acid, usually formulated as 119 and 120, respectively, on the basis of rather convincing chemical evidence [for a review see reference 109(f) cf. reference 178]. Isodialuric acid is converted into dialuric acid by base as would be expected if structures 119 and 120 are correct. On the basis of its infrared spectrum, dialuric acid has been concluded to exist in the tetrahydroxy form, but the correctness of this conclusion appears very doubtful. 

Little work has been reported on pyrazine-2,3-diones, however spectral evidence has been advanced by HonzL to support the dioxo formulation 126. Dioxo structures have been assigned to quin-oxaline-2,3-dione (127) and its 1-methyl analog on the basis of ultraviolet and infrared spectral data, and according to... 

In a preliminary communication, the dihydroxy-1,2,4-triazine derivative 163 has been assigned the structure shown on the basis of infrared evidence. The pK and ultraviolet and infrared spectral data support the formulation of 6-azauracil (164) as a dioxo compound. 

Tautomerism of type 197 198 has been postulated to occur in flavin derivatives on the basis of infrared spectral data. ... 

In 1939, the ultraviolet spectrum of 4-methylquinol-2-thione was reported to differ from that of the 2-alkylthio analog, and the former compound was concluded to exist in the thione form. However, other investigators were unable to reach any conclusions from ultraviolet and infrared spectral data concerning the tautomerism of quinol-2- and -4-thione. A definitive pK and ultraviolet spectral investigation by Albert and Barlin has recently established that the thione forms of quinol-2- and -4-thione and of isoquinol-1- and -3-thione (cf. 202) greatly predominate (Table V). The infrared... 

Pyrimidine-2-thiones (e.g., 206) have been shown to exist as such by comparison of their ultraviolet spectra with those of both alkylated forms.The ultraviolet spectra of pyrimidine-4-thiones are different from those of 4-alkylthiopyrimidines, therefore the former compounds exist as 207 and/or 208, the predominant form not having been determined. Infrared spectral evidence suggests that quinazoline-4-thione exists as 209 and/or 210 and has been used recently to demonstrate the thione formulation for pyrimidine-2- and -4-thione, pyrazine-2-thione, and quinoxaline-2-thione. In view of this work, the report that X-ray crystallographic evidence supports the mer-... 

The infrared spectral method has been used to show that certain amino-l,2,4-triazines exist as such (Table VI). Although the separate isolation of 263 and 264 was claimed in 1940, this report is probably erroneous,... 

Anhydrous quinazoline hydrochloride absorbs one molecule of water readily, and. the product is difficult to dehydrate completely even in a high vacuum at 60°. Infrared spectral data suggest that this water is covalently bound because of (o) the absence of several bands in the spectrum of the hydrate which are present in the spectrum of the anhydrous hydrochloride and (6) the presence of extra bands at 1474 and 1240 cm that have been attributed to C— H and O— H bending vibrations of the — CHOH group. 

Many individual compound reports contain infrared spectral information, but there is only one in which detailed analysis appears. The 3-hydroxytriazolopyri-dine 125 used as a catalyst for peptide coupling (Section IV.J) has been studied in the solid and in solution, in association with a crystallographic study, and shown to exist as a dimer in solution (99MI1). 

Chemical evidence has been advanced for the formulation of p nitrosoindoles as either 115 or 116 (sec reference 119 and references therein), but ultraviolet spectral comparison with both methylated forms clearly indicated that 116 was favored. Infrared spectral data are also considered to support structure 116. °... 

K = Me) and especially infrared spectral data indicated that 3-phenylisoxazol-5-one exists in the CH form (45, R —H)." The... 

Infrared spectral evidence indicates that indazol 3-one probably exists in the oxo form (cf. 77). 4-Monosubstituted-l,3-diphenylpyrazol-5-ones have been assigned an oxo structure (cf. 78) on the basis of infrared (presence of a v C=N band) and ultraviolet spectral data. The structure of certain iV-acylated pyrazolones has been discussed on the basis of their infrared spectra, but in these cases the possibility of acyl migration is a complicating factor. 

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