Amine spectroscopy

Amides can be titrated direcdy by perchloric acid ia a nonaqueous solvent (60,61) and by potentiometric titration (62), which gives the sum of amide and amine salts. Infrared spectroscopy has been used to characterize fatty acid amides (63). Mass spectroscopy has been able to iadicate the position of the unsaturation ia unsaturated fatty amides (64). Typical specifications of some primary fatty acid amides and properties of bisamides are shown ia Tables 5 and 6. 

Instmmental methods of analysis provide information about the specific composition and purity of the amines. QuaUtative information about the identity of the product (functional groups present) and quantitative analysis (amount of various components such as nitrile, amide, acid, and deterruination of unsaturation) can be obtained by infrared analysis. Gas chromatography (gc), with a Hquid phase of either Apiezon grease or Carbowax, and high performance Hquid chromatography (hplc), using siHca columns and solvent systems such as isooctane, methyl tert-huty ether, tetrahydrofuran, and methanol, are used for quantitative analysis of fatty amine mixtures. Nuclear magnetic resonance spectroscopy (nmr), both proton ( H) and carbon-13 ( C), which can be used for quaHtative and quantitative analysis, is an important method used to analyze fatty amines (8,81). 

Air Monitoring. The atmosphere in work areas is monitored for worker safety. Volatile amines and related compounds can be detected at low concentrations in the air by a number of methods. Suitable methods include chemical, chromatographic, and spectroscopic techniques. For example, the NIOSH Manual of Analytical Methods has methods based on gas chromatography which are suitable for common aromatic and aHphatic amines as well as ethanolamines (67). Aromatic amines which diazotize readily can also be detected photometrically using a treated paper which changes color (68). Other methods based on infrared spectroscopy (69) and mass spectroscopy (70) have also been reported. 

Nuclear magnetic resonance (nmr) spectroscopy is useful for determining quaternary stmcture. The N-nmr can distinguish between quaternary ammonium compounds and amines, whether primary, secondary, or tertiary, as well as provide information about the molecular stmcture around the nitrogen atom. The C-nmr can distinguish among oleic, tallow, and hydrogenated tallow sources (194). 

These effects can be attributed mainly to the inductive nature of the chlorine atoms, which reduces the electron density at position 4 and increases polarization of the 3,4-double bond. The dual reactivity of the chloropteridines has been further confirmed by the preparation of new adducts and substitution products. The addition reaction competes successfully, in a preparative sense, with the substitution reaction, if the latter is slowed down by a low temperature and a non-polar solvent. Compounds (12) and (13) react with dry ammonia in benzene at 5 °C to yield the 3,4-adducts (IS), which were shown by IR spectroscopy to contain little or none of the corresponding substitution product. The adducts decompose slowly in air and almost instantaneously in water or ethanol to give the original chloropteridine and ammonia. Certain other amines behave similarly, forming adducts which can be stored for a few days at -20 °C. Treatment of (12) and (13) in acetone with hydrogen sulfide or toluene-a-thiol gives adducts of the same type. 

Pyridine, 4-methoxy-3-styryl-photoelectron spectroscopy, 2, 137 Pyridine, 2-methyI-alkylation, 2, 176 amination, 2, 233, 236 carboxylation, 2, 53 chlorination, 2, 201, 331 Claisen condensation, 2, 51 methiodide... 

Further aspects of the reaction of aromatic tertiary hydroxyl amines have been examined by more sophisticated techniques [49]. 2-Methyl-2-nitrosopropane was used as a radical trap, and the endgroups on PMMA resulting from its addition were detectable by ultraviolet spectroscopy. Electron spin resonance results on the same system have also been reported [50]. 

Enamines of several methyl ketones have been prepared and their isomer content estimated by NMR spectroscopy (13,39,43). The reaction of Ti[N(CH3)2l4 as the amine source and 3-methyl-2-butanone gave only 26 (Ri = Rj = CH3), which could be isomerized by prolonged heating to a 1 1 mixture ofthatenamine and enamine 27 (R, = Rj = CH3)(39). The reaction of morpholine and 3-methyl-2-butanone in benzene with a trace of acetic... 

Although the emphasis in this chapter has been on tbe synthesis and mechanism of formation of simple enamines, brief mention will be made of the addition of amines to activated acetylenes to indicate the interest and activity in this area of substituted enamines. Since such additions tend to be stereospecific, inclusion in this section seems apropos. The addition of amines to acetylenes has been much studied 130), but the assigning of the stereochemistry about the newly formed double bond could not be done unequivocally until the techniques of NMR spectroscopy were well developed. In the research efforts described below, NMR spectroscopy was used to determine isomer content and to follow the progress of some of the reactions. 

Another pathway for the aromatization of the cr -adducts was found in the reactions of 3-pyrrolidino-l,2,4-triazine 4-oxide 81 with amines. Thus the treatment of 1,2,4-triazine 4-oxide 81 with ammonia leads to 5-amino-1,2,4-triazine 4-oxides 54—products of the telesubstitution reaction. In this case the cr -adduct 82 formed by the addition of ammonia at position 5 of the heterocycle undergoes a [l,5]sigmatropic shift resulting in 3,4-dihydro-1,2,4-triazine 83, which loses a molecule of pyrrolidine to yield the product 54. This mechanism was supported by the isolation of the key intermediates for the first time in such reactions—the products of the sigmatropic shift in the open-chain tautomeric form of tiiazahexa-triene 84. The structure of the latter was established by NMR spectroscopy and X-ray analysis. In spite of its open-chain character, 84 can be easily aromatized by refluxing in ethanol to form the same product 54 (99TL6099). 

The tautomerism of 2- and 3-aminothiophenes was mentioned by Hartough in his review of thiophenes/ but the first definite evidence became available in 1961 when Hoffman and Gronowitz showed conclusively by nuclear magnetic resonance spectroscopy that these compounds both exist in the amino form. In agreement with this finding, 3-aminothiophene generally behaves as an aromatic amine. ... 

NMR spectroscopy of. 823-824 nucleophilic acyl substitution reactions of, 806-807 reaction with alcohols, 807 reaction with amines, 807... 

Infrared radiation, electromagnetic spectrum and, 419, 422 energy of. 422 frequencies of, 422 wavelengths of, 422 Infrared spectroscopy, 422-431 acid anhydrides, 822-823 acid chlorides, 822-823 alcohols. 428, 632-633 aldehydes, 428. 730-731 alkanes, 426-427 alkenes, 427 alkynes, 427 amides. 822-823 amines, 428, 952 ammonium salts, 952-953 aromatic compound, 427-428, 534 bond stretching in, 422... 

Kuterev, Stoyanov, Bagreev and Zolotov [461] reported on the investigation, using IR spectroscopy, of the composition of niobium and tantalum complexes extracted by amines from fluoride solutions. It was shown that in solutions that contain hydrofluoric acid in concentrations ranging from 1M to 12M, both niobium and tantalum were extracted in the form of NbF6 and TaF6 ... 

Ring inversions of 1H- and 4//-azepines between their two stable boat forms have been studied extensively by HNMR spectroscopy.37,38-40-76 82,85 A coalescence temperature of — 55 7 C and a AG value for ring inversion of 42.7 kJ mol have been determined for the two conformers 10 A and 10 B of A-phenyl-3//-azepin-2-amine.82... 

Treatment of the Z-aldehyde 9 (R1 = R2 = H) with trifluoroacetic acid in dichloromethane at — 10 C, then with l,4-diazabicyclo[2.2.2]octane or /V,/V-diethylpyridin-4-amine, constitutes the first synthesis of 27/-azepine (10, R1 = R2 = H) which was isolated, with great difficulty and in very low yield (1 %), as a highly volatile, unstable oil, the structure of which was confirmed by high field H and 13CNMR spectroscopy.290 Similar treatment of the Z-alkenones 9a-d furnishes the thermally unstable (5)-2/7-azepines lOa-d in much higher yields.291... 

In the case of 6-isopropyl-2-methylphenyl azide a 1 1 mixture (by HNMR spectroscopy) of 3-isopropyl-A%V,7-trimethyl-3//-azepin-2-amine and 7-isopropyl-N,N,3-trimethyl-3//-azepin-2-amine is obtained in 45% yield. 

As expected, similar treatment of 3-nitroarenes furnishes mixtures of 4- and 6-substituted 3H-azepines, 54 and 55, respectively.176 Comparable yields of mixed azepines were also obtained by deoxygenation of 3-nitroarenes with alkylphophorous triamides, formed in situ from hexa-methylphosphorous triamide and excess of a secondary amine.66 In a few cases the 3//-azepines were separated by fractional crystallization of their oxalate salts66 but, in general, pure isomers were not isolated and the yields cited in the table were determined by HNMR spectroscopy. 

Morkovnik et al. (1989) found experimentally that the addition of an equimolar amount of 4-morpholino- or 4-dimethylaminoaniline to a suspension of nitrosyl perchlorate in 100 % acetic acid, dioxan, or acetonitrile yields a mixture of the diazonium perchlorate and the perchlorate salt of the amine radical cation, with liberation of gaseous nitric oxide. Analogous results in benzene, including evidence for radicals by ESR spectroscopy and by spin trapping experiments, were obtained by Reszka et al. (1990). 

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