Solution infrared spectra

Acetic acid treatment of the transition metal Ge(IV) hydride salt Kb/5-C5H5Mn(CO)2GeH3] yields a red product, b/5-C5H5Mn (CO)2]2Ge, which contains a linear Mn-Ge-Mn system in which the germanium atom occupies a special position with equal Ge-Mn distances of 2.204 A. Solution infrared spectra show four v(CO) stretching absorptions instead of the two expected from the cen-trosymmetric structure in the solid state, implying free rotation about the Ge-Mn bonds. Simple application of the rare-gas rule would favor a double-bonded formulation containing Ge(IV), but a molecular-orbital... 

Fig. 14. Mineral oil mull infrared spectrum of (a) Na3[lr(CO)3] and (b) HMPA solution infrared spectrum of Na3[Rh(CO)3] in the v(CO) region.

The only reference to this ring system describes the heterocycle as a furazono[3,4-h]pyrazine/ The compounds are prepared by condensation of 3,4-diaminofurazan (25) with a-dicarbonyl compounds. Benzil gave the 5,6-diphenyl derivative 26 (R = Ph), and oxalic acid gave the dihydroxy compound 26 (R = OH). The presence of a band at 1695 cm in the solution infrared spectrum of 26 (R = OH) is taken to indicate the presence of the 0x0 tautomer (27). 

The UV-vis-near-IR absorption spectrum of the solution of the protonated polymer exhibits MLCT bands and valence tautomerization similar to those of 1,8-Fc2Aq as shown in Fig. 3.32, indicating the formation of fulvene complexes in the main chain in solution. Infrared spectrum of the protonated polymer also shows the similarity with that of l,8-Fc2Aq, namely, half the CC triple bond remains. 

The study of the infrared spectrum of thiazole under various physical states (solid, liquid, vapor, in solution) by Sbrana et al. (202) and a similar study, extended to isotopically labeled molecules, by Davidovics et al. (203, 204), gave the symmetry properties of the main vibrations of the thiazole molecule. More recently, the calculation of the normal modes of vibration of the molecule defined a force field for it and confirmed quantitatively the preceeding assignments (205, 206). 

In the infrared, 2-hydroxycyclobutanone has a carbonyl band at 1780 cm in chloroform solution. Kept in nitrogen-filled screw-capped vials in the freezing compartment of a refrigerator, 2-hydroxyoyolo-butanone slowly but completely solidifies as its dimer. The infrared spectrum of the solid in a KBr disk shows no carbonyl. However, a chloroform solution of the solid does show the characteristic 1780 em band, indicating rapid equilibration with the monomer. 

In a 250 ml Erlenmeyer flask covered with aluminum foil, 14.3 g (0.0381 mole) of 17a-acetoxy-3j5-hydroxypregn-5-en-20-one is mixed with 50 ml of tetra-hydrofuran, 7 ml ca. 0.076 mole) of dihydropyran, and 0.15 g of p-toluene-sulfonic acid monohydrate. The mixture is warmed to 40 + 5° where upon the steroid dissolves rapidly. The mixture is kept for 45 min and 1 ml of tetra-methylguanidine is added to neutralize the catalyst. Water (100 ml) is added and the organic solvent is removed using a rotary vacuum evaporator. The solid is taken up in ether, the solution is washed with water and saturated salt solution, dried over sodium sulfate, and then treated with Darco and filtered. Removal of the solvent followed by drying at 0.2 mm for 1 hr affords 18.4 g (theory is 17.5 g) of solid having an odor of dihydropyran. The infrared spectrum contains no hydroxyl bands and the crude material is not further purified. This compound has not been described in the literature. 

These structural problems are also insoluble by physical methods alone. The infrared spectrum often gives an unambiguous decision about the structure in the solid state the characteristic bands of the carbonyl or the hydroxyl group decided whether the compound in question is a carbinolamine or an amino-aldehyde. However, tautomeric equilibria occur only in solution or in the liquid or gaseous states. Neither infrared nor ultraviolet spectroscopy are sufficiently sensitive to investigate equilibria in which the concentration of one of the isomers is very small but is still not negligible with respect to the chemical reaction. 

The hydrochloride of (3) holds water rather tenaciously, and the infrared spectrum indicates that the water is covalently bound. Mild oxidation of the cation (3) gives 4-hydroxyquinazoline in high yield and ring-chain tautomerism is excluded on the grounds that quinazo-line does not give a positive aldehyde test in acid solution, 2-Methyl-quinazoline also has an anomalous cationic spectrum and a high basic strength (see Table I), but 2,4-dimethylquinazoline is normal in both these respects, which supports the view that abnormal cation formation entails attack on an unsubstituted 4-position. ... 

Mason has determined the infrared spectrum of pyrido[3,2-d]-pyrimidin-4(3ff)-one (149, N in position 5) in chloroform solution and as a KBr disc and has suggested that the low frequency of th e NH band (3389 cm ) and high frequency of the C=0 band (1745 cm i) in the solution spectra are indicative of a quasi o-quinonoid form. The infrared spectra of the four pyridopyrimidin-4(377)-ones (149), the four 2,4(ljff,3//)-diones (150), and a number of substituted derivatives, have been determined, as Nujol mulls, in these laboratories. ... 

The tautoraerism of certain difunctional derivatives of l-thia-3,4-diazole has received considerable attention. Pala assigned structure 156 to 2,5-dimercapto-l-thia-3,4-diazole on the basis of infrared spectral data, and Thorn" reached the same conclusion by comparing its ultraviolet spectrum (measured in ethanol) with those of the four possible methylated derivatives. However, the infrared spectrum of a chloroform solution of the parent compound showed bands at 2600-2550 cm indicating an SH group and the probable occurrence of form 157 under these conditions, and this conclusion is supported by the occurrence of SH bands in solid state spectra obtained by Swiss investigators. For a summary of earlier work on these compounds, see reference 187. 

Quinoxalin-2-ones are in tautomeric equilibrium with 2-hydroxy-quinoxalines, but physical measurements indicate that both in solution and in the solid state they exist as cyclic amides rather than as hydroxy compounds. Thus quinoxalin-2-one and its A -methyl derivative show practically identical ultraviolet absorption and are bases of similar strength. In contrast, the ultraviolet spectra of quinoxalin-2-one and its 0-methyl derivative (2-methoxyquinoxaIine) are dissimilar. The methoxy compound is also a significantly stronger base (Table II). Similar relationships also exist between the ultraviolet absorption and ionization properties of 3-methylquinoxalin-2-one and its N- and 0-methyl derivatives. The infrared spectrum of 3- (p-methoxy-benzyl)quinoxalin-2-one (77) in methylene chloride shows bands at 3375 and 1565 cm" which are absent in the spectrum of the deuterated... 

B) Acylation of 6-Aminopenicillanic Acid To a solution of the aryl halocarbonyl ketene (0.1 mol) in methylene chloride (sufficient to provide a clear solution and generally from about 5 to 10 ml per gram of ketene) there is added the proper alcohol RjOH (0.1 mol), in this case 5-indanyl alcohol. The reaction mixture is maintained under an atmosphere of nitrogen and stirred for a period of from 20 minutes to 3 hours, care being taken to exclude moisture. The temperature may range from about -70° to about -20°C. The infrared spectrum of the mixture is then taken to determine and confirm the presence of the ketene ester. A solution of 6-aminopenicillanic acid-triethylamine salt (0.1 mol) in methylene chloride (50 ml) is added and the mixture stirred at -70° to -20°C for 10 minutes. The cooling bath is then removed and the reaction mixture stirred continuously and allowed to warm to room temperature. 

After concentrating the filtrate to approximately 400 ml, solids started crystallizing out at which time the filtrate was cooled by refrigerating at 5°C for several hours. Filtration gave 1B.7 g of L-Dopa, MP 284° to 286°C (dec.) [oJd 8.81° (1% solution in aqueous 4% HCI). The infrared spectrum and paper chromatography indicated very good L-Dopa according to U.S. Patent 3,253,023. 

After washing the combined extracts with ammonium chloride solution and water and working up in the usual way a white solid (IV) is obtained which after one recrystalli2ation from aqueous methanol has MP 242° to 243°C. The infrared spectrum of this compound indi-... 

A mixture of 20 g of 1 -bromo-3,5-dimethyladamantane, 75 ml of acetonitrile, and 150 ml of concentrated sulfuric acid was allowed to react overnight at ambient room temperature. The red reaction product mixture was poured over crushed ice, and the white solid which precipitated was taken up in benzene and the benzene solution dried over sodium hydroxide pellets. The benzene solution was filtered from the drying agent and evaporated to dryness in vacuo to yield 1 B.2 g of product having a melting point of about 97°C and identified by infrared spectrum as 1-acetamido-3,5-dimethvladamantane. 

Aero Hydrolysis. A solution of kasugamycin hydrochloride (1.5 grams, 3.46 mmoles) dissolved in 15 ml. of 6N hydrochloric acid was heated at 105°C. for five hours in a sealed tube. The solution was condensed to 5 ml. under a reduced pressure and the addition of 50 ml. of ethyl alcohol afforded a crude solid overnight. It was recrystallized from aqueous ethyl alcohol, showing m.p. 246°-247°C. (dec.). It showed no depression in the mixed-melting point and completely identical infrared spectrum with d-inositol which was supplied by L. Anderson of the University of Wisconsin. The yield was 81% (503 mg., 2.79 mmoles). Anal Calcd. for CgH12Og C, 40.00 H, 6.71 O, 53.29 mol. wt., 180.16. Found C, 40.11 H, 6.67 O, 53.33 mol. wt., 180 (vapor pressure osmometer). 

N-Acetylation of Kasugamycinic Acid (9a). A solution of kasugamycinic acid (225 mg.) dissolved in 10 ml. of water was treated with acetic anhydride (0.3 ml.) under cooling sodium bicarbonate was used to keep the pH 7.2 and stirring continued for 30 minutes. The reaction product was passed through Dowex 50W-X2 (H form) and the column was washed with water. The combined filtrate was subjected to lyophilization to afford 234 mg. of a crude N-acetyl derivative. Its infrared spectrum showed strong absorptions at 1740 cm-1 characteristic of oxamic acid group. The N-acetyl derivative (178 mg.) was treated with 40 ml. 

Plouvier then prepared the previously unknown racemic form of proto-quercitol by mixing equal weights of the two enantiomers. The melting point (237°C.) of the mixture was not depressed, and its (presumably solid state) infrared spectrum reportedly (36) was identical with that of either active form. It thus appears that DL-proto-quercitol exists as a solid solution, not a racemic compound or conglomerate. 

Take some crude cresol mixture (1 g) and dissolve it in cyclohexane (20 mL). Obtain the infrared spectrum for the mixture if necessary, dilute the solution further with cyclohexane to obtain absorbances which will lie on the calibration graphs. From the selected absorption peaks calculate the absorbances for the three individual isomers and use the calibration graphs to calculate the percentage composition of the cresol mixture. 

All attempts to isolate efficient process giving a white solid polymer which appears to have repeating keteneimine units. This assignment is consistent with the very strong absorption at 2140 cm.-1 in the infrared spectrum. ... 

The molecular mass determined osmometrically corresponds to the formula S5O. The SO stretching vibration was observed in the infrared spectrum at 1119 cm (at -65 °G) indicating an exocyclic sulfoxide group similar to the one in SsO (see below). At -50 °G the solution of S5O may be kept for several days without decomposition which usually results in a Tyndall effect caused by a colloidal polymeric sulfuroxide which is the expected decomposition product. At 25 °G some decomposition already occurs within... 

On exposure to air, the initially clear orange crystals of the adduct turn cloudy within 1 min as a result of the loss of CS2, and ultimately form a yellow oil. In CS2 solution the adduct decomposes fairly rapidly at room temperature the decomposition products SOCI2, SO2, Sg, and SbCls are already detectable after 10 min. The SO stretching vibrations of Si202-2SbCl5 occur at 940 cm in the infrared spectrum (in CS2) [61]. Free S12O2 has not been prepared yet. 

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