(4988) Tyihak, E.; Ferenczi, S.; Hazai, I.; Zoltan, S.; Patthy, A,, J. Chromatogr. 1974, 102, 257-62. (4998) Tykva, Richard: Votruba. Ivan, J. Chromatogr. 1974, 93(2). 399-404.
(5008)Ueda. Hiroshi; Ito, Kiichi: Tejirna. Toyohiko: Kano, Montonari; Tadano, Hisataro, Rinsho Kensa 1975, 19(6), 639-43; Chem. Abstr. 1975, 83. 1283542. (5018) Upadhyay, R. K.; Singh, V. P.; Vajpai, Usha, J. Chromatogr. 1974, 93(2), 494-8. (5028) Van Buren, J.; De Vos, L.; Pilnik, W.. J. Fd. Sci. 1974, 38(4), 656-8. (5038) Van den Berg, H.; Hornrnes, F. A,, J. Chrometogr. 1975, 104(1), 219-22. (5048) Van den Eijnden, D. H., Anal. Biochem. 1974, 57(1), 321-2. (5058) Varadi, Andras, J. Chromatogr. 1975, 110(1), 166-70. (5068) Vidrine, Drouet W.; Nicholas, Harold J., J. Chromatogr. 1974, 89(1),92-5. (5078) Viricei, M.: Gonnet. C.: Larnotte, A,, Chromatographia 1974, 7(7). 345-50. (5088) Vitek, Richard K.; Seul, Clifford J.; Baier. Margaret; Lau, Edward, Am. Lab. 1974, 6(2), 109-10, 112-16. (5098) Vladovska-Yukhnovska, Y.; Ivanov, Ch. P.; Malgrand, M.. J. Chromatogr. 1974, 90(1), 181-4.
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Functional Group Analysis Walter T. Smith, Jr.,* and John M. Patterson Department of Chemistry, University of Kentucky, Lexington, Ky. 40506
The analytical methods discussed in this review have been selected from the literature which has become available to the reviewers from December 1973 through November 1975. In addition to specific topics discussed under the appropriate headings which follow, some articles of more general interest should be called to the attention of organic analysts. These cover such topics as voltammetry ( I I ) , coulometric titrations (39), fusion reaction gas chromatography (84), quantitative NMR (59, 60), and purification of reference standards ( 7 ) . Acids. Colorimetric determinations of acids as the Fe(II1) complex of their hydroxamic acid derivatives is facilitated by using dicyclohexylcarbodiimide and hydroxylamine to form the hydroxamic acids (33, 64). Esters are reported not to react under the conditions used. For the conversion of acids to more volatile esters for gas chromatographic determinations either dicyclohexylcarbodiimide with a pyridine catalyst (12) or tetramethylammonium hydroxide and methyl iodide (83) in DMF-methanol have been used. In the latter case, the quaternary hydroxide in methanol can be used for saponification of lipids and other esters and the resulting acid products can be converted directly to methyl esters by treatment with methyl iodide. Formic acid is converted to its benzyl ester for gc determination by treatment with phenyldiazomethane (9). Acid anhydrides behave as monoprotic acids when titrated in pyridine with tetrabutylammonium hydroxide in 10:1 benzene-methanol (44). Thymol blue or azo violet is a suitable indicator. The technique permits the determination of both acids and anhydrides in the same sample with a single titration. The active hydrogen of fatty acids (and alcohols) has been determined by tritiation with tritiated water, followed by extraction into benzene for liquid scintillation counting (74).
Alcohols. Chemical, infrared, and NMR spectral methods for the determination of the hydroxyl group have been discussed (72).
Alcohols in concentrations down to M can be determined photometrically as alkyl 2,4-dinitrobenzenesulfenates. The esters, formed from the reaction of 2,4-dinitrobenzenesulfenyl chloride with the alcohols, are contaminated with unreacted sulfenyl chloride and disulfide by-product. Purification is accomplished by thin-layer chromatography on Silufol using 9:l cyclohexane-ethyl acetate as eluent (53). Adduct formation between alcohols and hexafluoroacetone allows the determination of hydroxyl groups ( f 2 % recovery) by the use of I9F NMR (22). The method is particularly attractive because mixtures of protic species, such as mixtures of different alcohols or mixtures of alcohols and water can be determined simultaneously (24). The results of water analyses are comparable t o those obtained by the Karl Fischer method. The hydroxyl group content in ethanol and in various di-, tri-, and tetrols has been determined to a sensitivity of 0.02% by first forming a complex between the hydroxy compound and (NH&Ce(NO& and then measuring the absorbance a t 440 nm (51). An infrared spectral method has been utilized to estimate the percentage of hydroxyl groups in methyl and ethyl cellulose. The absorbance of the 3470 cm-' band obtained from methylene chloride solutions of the celluloses is related to the hydroxyl group content (46). Most of the analytical procedures for the determination of vicinal glycols depend upon oxidation with periodate and usually differ in the way the extent of reaction is measured. One such measurement depends upon the observation that a perchlorate ion selective electrode responds to periodate ion. The time required for a known amount of periodate to react with a sample is related to the concentration of glycol (10).Relative errors are ca. 0.7%. In another procedure, the iodate formed in the oxidation of the glycol is precipitated as silver iodate and after separation, filtering, and redissolving in ammonium hydroxide, the silver ion obtained is determined by atomic absorption spectrophotometry ( 5 7 ) . The determination of hydroxy acids by gas chromatograANALYTICAL CHEMISTRY, VOL. 48, NO. 5, APRIL 1976
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phy requires that both the hydroxyl and the carboxylic acid groups be converted into derivatized functions. A modification in which both groups are derivatized simultaneously involves the use of heptafluorobutyric anhydride, pyridine, and ethanol. The anhydride esterifies the hydroxyl group and the ethanol esterifies the carboxyl group (6). Aldehydes and Ketones. Atomic absorption has been used to determine aldehydes in the 1-4 wmol/ml range. The aldehydes are oxidized by a silver-ammonia complex (as in the Tollen's test) and the reduced silver is separated and determined by atomic absorption spectrophotometry. Some substituted benzaldehydes (e.g., p-methoxy-, p-acetamido-, and 4-hydroxy-3-methoxybenzaldehyde) do not give quantitative results (56). 4-Amino-3-hydrazino-5-mercapto-1,2,4-triazole
is a new reagent for the colorimetric determination of aldehydes. The reagent reacts readily with aldehydes to give
R
/IN
N/
"yikp N--1J after aeration of the solution, which has an absorption maximum a t 520-550 nm for simple aliphatic aldehydes (340 nm for benzaldehyde) (30). 1,2-Diaminonaphthalene reacts with aldehydes to give a fluorescent product, 2-substituted naphth[l,2-d]imidazole, thus providing the basis for a fluorometric procedure (54, 88). The products from aromatic aldehydes fluoresce much more strongly than do those from aliphatic aldehydes. Amides. Water-soluble amides are determined colorimetrically by a procedure which starts with the action of bromine on the amide to give the N-bromoamide. After destruction of excess bromine with sodium formate, the bromo amide (or the hypobromous acid formed by its hydrolysis) oxidizes iodide to free iodine. The iodine is determined as its starch iodine complex, measured a t 610 nm (70). Amines. Tertiary amines, or a t least those having an N methyl group are demethylated and converted to the corresponding pentafluorobenzyl carbamate by the action of pentafluorobenzyl chloroformate in the presence of sodium carbonate. These stable derivatives give a very high response in gas chromatography using an electron capture detector and have been used for determinations in the range of 12-120 pg amine/ml (21). Atomic absorption spectrometry has been used in several ways for indirect determination of amines. For secondary amines, the nickel dialkyldithiocarbamate (prepared from the amine, carbon disulfide, and nickel ion) is precipitated and the nickel content is determined by atomic absorption spectrometry ( 5 5 ) , or the aliphatic amine is complexed with copper and the complex is extracted into methyl isobutyl ketone for determination of the copper (50). Primary amines have been determined by treating the sample with a reagent prepared from triethanolamine, 5-nitrosalicylaldehyde, acetaldehyde, and copper sulfate. The copper-aldimine complex formed is removed by filtration and either the copper in the complex or the excess copper in the filtrate is determined by atomic absorption spectrometry (49). In a variation on this last method, the copper complex of the Schiff base with salicylaldehyde is extracted into amyl alcohol and the absorbance a t 420 nm is measured (37). Fluorescamine has been used for the colorimetric determination of primary amines, and for the simultaneous determination of both primary and secondary amines (78, 79). o-Phthalaldehyde has been reported to react with primary amines in the presence of 2-mercaptoethanol to give 84R
ANALYTICAL CHEMISTRY, VOL. 48, NO. 5, APRIL 1976
products of high fluorescence ( 4 ) . The sensitivity is reported to be 4-5 times that of fluorescamine, and substituted phthalaldehydes, such as 4-cyanophthalaldehyde, have been patented as fluorescence reagents for aromatic primary amines (45). A method for all classes of amines depends on the formation of a colored complex with Fe(II1) and the amide formed by reaction of the amine with acetyl chloride a t pH 1.8 and 65 "C. Tertiary amines undergo dealkylation to give amides of secondary amines (66). Primary and secondary amines are reported to react quantitatively with phenyl isothiocyanate in DMF to give substitued thioureas which can be titrated with potassium iodate under acidic conditions (80). Amino Acids. Gas chromatographic methods for the determination of amino acids, amino acid enantiomers, and iodoamino acids have been reviewed (26). Amino acids which form soluble complexes with Cu(I1) can be determined with an average relative error of f0.13% by treatment with a suspension of Cu3(PO4)2. The soluble complex is separated from excess Cu3(P04)Zr converted into C u ( N 0 3 ) ~by nitric acid and the Cu(I1) titrated with EDTA a t pH 7-8 (murexide indicator) (18). An adaptation of the direct titrimetric method (CuSO4 titrant, murexide indicator) of Libicky and Wunsch (42) has been extended to the determination of 22 a-amino acids with an avera e error of &0.1% (19). Cd, Co, Ni, Zn, k g ( I I ) , and Cu(I1) ions form complexes with the ninhydrin-amino acid product and leucine, valine, alanine, and serine may be determined photometrically over the range 0.05-0.25 pM using these complexes (29). A colorimetric method for determining hydroxyproline a t nanogram concentrations has been adapted from the procedure of Woessner (86) in which the proline is oxidized to a pyrrole with chloramine-T and then estimated by reaction with p-dimethylaminobenzaldehyde (41). An improvement in the fluorometric determination of amino acids and proteins has been reported to arise from an increase in fluorescent intensity brought about by addition of cycloheptaamylose to l-dimethylaminonaphthalene-5-sulfonyl (dansyl) derivatives of the amino acids and proteins (34). Aromatic Hydrocarbons. Isomeric polynuclear aromatic hydrocarbons such as benzo[a]- and benzo[e]pyrenes can be separated by gas chromatography by using the liquid phase N,N'-bis(p-methoxybenzylidene)cu,cu/-bi-p-toluidine heated to its nematic region (31). Benzene, toluene, 0-, and p -xylenes have been determined in aromatic hydrocarbon mixtures with an overall relative error of 1 4 % by infrared spectrometry. The absorption bands utilized and the range of concentrations which give satisfactory analyses are presented (76). Through the use of an internal standard, the quasi-linear luminescence spectra (n-alkane solvent a t 77 K) of polynuclear aromatic hydrocarbons can be used to determine these compounds present in mixtures a t trace concentrations (35). Naphthalene and phenanthrene fractions present in hydrocracked coal have been separated by chromatography over alumina deactivated with 4% water (cyclohexane eluent). The characteristic ultraviolet absorption bands for these fractions were identified and their mean absorption coefficients determined (67). Carbohydrates. Uronic acids are converted to fluorescent products by heating with ethylene diamine sulfate in acetate buffer (25). Other carbohydrate materials, including uronides, do not interfere. A new reagent for detection and determination of carbohydrates (and certain aromatic aldehydes) is 2,2,5,5-tetrakis(carboxymethy1thio)-p-dithiane,which can be prepared by the action of concentrated hydrochloric acid on thioglycolic acid.
The reagent (TCD) and 70% HzSO4 give a strong color with carbohydrates and also with hydroxy- and methoxybenzal-
Walter 1. Smith, Jr., professor in the Chemistry Department at the University of Kentucky, Lexington, has had industrial experience with Mallinckrodt Chemical Works and Ethyl Corp. Before joining the Kentucky faculty, he taught at State University of Iowa. His education was obtained at the University of Illinois and Indiana University. He was a Lilly Fellow at Indiana in 1944-46 and a Fels Fund postdoctoral Fellow at Chicago in 1946-47. He is author or coauthor of several publications in scientific journals. During 1963-64, he was visiting professor and chairman of the Department of Chemistry at the University of Libya, Tripoli, and in 1965-66 was a Fuibright-Hays visiting professor at the American University of Beirut, Lebanon.
John M. Patterson, professor in the Department of Chemistry at the University of Kentucky, received a Ph.D. from Northwestern University in 1953, after taking undergraduate work at Virginia Military institute and Wheaton College. His fields of interest include investigations of hightemperature reactions, nitroparaffin chemistry, heterocyclic compounds, and photochemical reactions in solution.
dehydes. The absorbance (usually a t 520 or 550 nm) is proportional to the concentration in the 10-5-10-4 M range. The color formed with carbohydrates apparently depends on the initial formation of furfural derivatives (40). Enzymes have been applied to the determination of sucrose, glucose, and fructose. A series of enzymes (sucrase, hexokinase, phosphohexose isomerase, and glucose-6-phosphate dehydrogenase) are immobilized on agarose, and when a solution of sucrose, or its hydrolysis products, glucose and fructose, are passed over the enzymes, it is converted ultimately to gluconic acid, with concurrent reduction of NADP to NADPH. The increase in the concentration of this last reagent is measured spectrophotometrically (17). N i t r o Compounds. In reaction gas chromatography, carbohydrazide has been recommended for the reduction of nitro and azo compounds to amines (65). Electrochemical generation of Ti(II1) for the reduction of nitro and nitroso groups has been used in several cases (5, 36,47). In the second reference, the water formed in the reduction is determined by Fischer titration. Nitrosamines. A combination of gas chromatography and thermal energy analysis (13) provides a specific and sensitive method for the determination of volatile nitrosamines (14). Another method is based on the pyridinecatalyzed reaction of nitrosamines with heptafluorobutyric anhydride to give derivatives suitable for determination by gas chromatography using a flame ionization detector (20). Organometallic Compounds. Organo-halomercury compounds have been determined by a titrimetric procedure which gives recoveries of 96-100%. The sample, on treatment with a thiol, releases an equivalent of halide which, after extraction with an organic solvent to remove the thiomercury compound, is titrated by the Volhard method (58). Subpicogram quantities of halomercury compounds were analyzed rapidly by gas chromatography using a highly selective microwave emission spectrometric detector (77). The application of the procedure of Sakla and AbuTaleb (68) to the analysis of Ca, Cu, Al, Fe, Bi, and Ni in organic compounds allows the determination of these metals with an average relative error of 1&0.34%. The metals are precipitated with 8-hydroxyquinoline (oxine) after a closed-flask combustion (69). Organometallic compounds which cannot be analyzed quantitatively by combustion methods can be determined by x-ray spectrometry using pressed Borax discs ( 1 ) . Peroxides. A procedure for the determination of peroxybenzoyl nitrate involves the quantitative conversion of the
peroxide to methyl benzoate by basic methanol solution. The methyl benzoate is then analyzed by gas chromatography (2). A glass dioctyl phthalate column a t 71 "C (nitrogen carrier gas) will quantitatively separate mixtures of di-tertbutyl peroxide, tert-butyl cumyl peroxide, tert-butyl ethylphenyl peroxide, tel't- butyl hydroperoxide, and cumene and ethylbenzene hydroperoxides (28). Phenols. Phenols can be converted to cobalt derivatives, extractable with methyl isobutyl ketone, by treatment with Na&o(NO& in dilute acetic acid, and the cobalt in the extract can then be determined by atomic absorption spectrometry (48). For determining the concentration of phenols in water in the ppb range, a uv ratio spectrometric method has been recommended. The method utilizes an instrumental system in which two conventional sealed hollow cathode lamps are used to monitor the uv bathochromic effect which is observed when phenols are converted t o their ions in alkaline solution (15). Most phenols, but not those with bulky ortho alkyl groups or with strong electron-withdrawing substituents, react quantitatively with hexafluoroacetone to give hemiketals which can be determined by 19FNMR (23). Europium shift reagents have been applied to the NMR determination of mixtures containing phenols and cresols (71, 82). A mixture of 1- and 2-naphthols can be analyzed by NMR by using an acetone solution containing 100 ppm of CrOa (75). Most of the methods for phenols based on oxidative coupling reactions are reported to be quantitatively deficient
(8). Q u a t e r n a r y Ammonium Compounds. A study of the two-phase titration of quarternary ammonium compounds with lauryl sulfate, using a methyl yellow indicator, demonstrates the usefulness of the method (32). Silicon Compounds. Methyl groups attached to silicon are converted to methane when silicon compounds are decomposed with sulfuric acid a t 280-300 "C in a stream of carbon dioxide. The methane is measured volumetrically after the carbon dioxide is trapped in potassium hydroxide solution and other cleavage products are absorbed on carbon (16). Sulfonates. In reaction gas chromatography, carbohydrazide has been recommended for the reduction of sulfonates to hydrocarbons (65). Thiols. Various oxidizing agents, such as chloramine-T (63), iodine cyanide, bromine cyanide (62), and phenyl iodosoacetate (81) have been used in oxidative procedures for thiols. Aromatic thiols are titrated to an extent of ca. 3% by sodium o-hydroxymercuribenzoate in strongly alkaline aqueous solution (dithizone indicator) while aliphatic thiols and hydrogen sulfide are titrated completely. When the solvent is changed to aqueous alcohol (dithiofluorescein indicator), the latter compounds as well as aromatic thiols can be titrated, thus providing an estimation of the two kinds of thiols when present together. Organic disulfides can be reduced to thiols by NaAlH2(0CH2CHzOCH3)2 and so can also be determined (87). Aliphatic, aromatic, and heterocyclic thiols have been determined by reaction with a vinyl sulfone (e.g. ethyl, amyl, or 2-hydroxyethyl sulfone) followed by determination of the excess sulfone by reaction with sodium sulfite and titration of the sodium hydroxide formed ( 5 2 ) . RS0&H=CH2
+ R'SH
RSO,CH,CH,SO,H
-
RS02CH2-CH$R'
+ NaOH
Unsaturation. The determination of carbon-carbon double bonds by catalytic hydrogenation has been investigated using palladium-on-barium sulfate and platinum oxide catalysts. An apparatus and procedure was devised for the analysis of substances containing low levels of unsaturation ( 4 3 ) . ANALYTICAL CHEMISTRY, VOL. 48, NO. 5, APRIL 1976
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An ultramicromethod has been developed for the determination of unsaturation by hydrogenation using a palladium-on-paper catalyst (27). The application of the hydroboration reaction to olefins followed by methanolysis can be used to determine unsaturation. The hydrogen released in the methanolysis reaction of the excess hydride was used to calculate the extent of unsaturation in the sample (61). Mixtures of cis and trans unsaturated esters have been determined to within 40.4 mol % using fast Fourier transform NMR spectrometry (3). Conjugated dienes, which do not form stable x-complexes with tetracyanoethylene can be determined by an indiLITERATURE CITED
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86R
rect spectrophotometric method. The absorbance of the x-complex formed between tetracyanoethylene and an aromatic species is diminished by an amount which is proportional to the concentration of diene when a diene sample is added (85). Aromatic and aliphatic unsaturated acids have been analyzed with relative errors of 0.32-0.77% using excess Hg(0Ac)p. The excess Hg(I1) is titrated potentiometrically (38). An analysis of phenylacetylene involves the formation of its silver salt (by reaction with Ag+ in "3) followed by an atomic absorption spectrometric determination of excess Ag in solution or of Ag in the insoluble salt (73).
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