(229) Urban, W. C., ANAL. CEEM., 43, 800 (1971). (230) Van den Bossche, W., Haemem, A., de Moerloose, P., Pharm. Weekbl. Ned., 104, 445 (1969). (231) Van Leuven, H. C. E., Anal. Chim. Acta, 49, 364 (1970). (232) Vinson, J. A., Fritz, J. S., ANAL. CHEM.,40, 2194 (1968). (233) Vitalina, M. D., Shipulo, G. P., Klimova, --V. A., Mikrochim. Acla, 1971, 513.
(234) Volodina, M. A., Abdukarimova, M., Gorshkova, T. A., Borodina, V. G., Zhardetskaya,,V. N., Vest. Mosk. GOS. Univ., Ser. Khzm., 1968, 114. (235) Volodina, M. A., Abdukarimova, M., Kozlovskaya, L. V., ibid., p 109. (236) Volodina, M. A., Abdukarimova, M., Terent’ev, A. P., Zh. Anal. Khim., 23, 1420 (1968).
(237) Volodina, M. A., Gorshkova, T. A., ibzil., 24, 1437 (1969). (238) Volodina, M. A., Gorshkova, T. A.,
Abdukarimova, M., Borodina, V. G., Kozlovskaya, L. V., Vest. Mosk. Cos. Univ., Set. Khim., 1968, 110. (239) Volodina, M. A., Goshkova, T. A,, Erofeeva, T. A., Zh. Anal. Khzm., 24,
594 (1969). (2.30) Volodina, M. A Gorshkova, T. A., Terent’ev A. P., i b k , p 1121. (241) Volodina, M. A,, Ivin, S. Z., Pal’yanova, M. V., Vest. Mosk. Gos. Univ., Ser. Khim., 1970, 632. (242) Wachberger, E., Dirscherl, A., Pulver, K., Microchem. J., 16, 318 (1971). (243) Watson, G. R., Williams, J. P., Anal. Biochem.. 33. 3Fj6 (1970). (244) Wetten, J. ’H., Smith,‘R. C., ANAL. CHEM.,41, 379 (1969).
(24.5) Wexler, A. S., ibid., 40, 1868 (1968).
(246) Wiele, H., Horak, E., Mikrochim. Acta, 1968, 1324. (247) Wilkniss, P. K., Linnenbom, V. J., Lzmnol. Oceanogr., 13, 530 (1968). (248) Wollin, A., At. Absorption Nmslett., 9, 43 (1970). (249) Woods, A. E., Crowder, R. D., Coates, J. T., Wittrig, J. J., ibid., ‘7, 85 (1968). (250) -Wronski,M., Bald, E., Chem. Anal. (Warsaw), 14, 173 (1969). (251) Yanagisawa, I., Yoshikawa, H., Clin. Chim. Acta, 21, 217 (1968). (252) Yih, C.-M., Mowery, D. F., Jr., Microchem. J., 16, 194 (1971). (253) Zelenina, E. N., Shemyakin, F. M., Zh. Vses. Khim. Obshchest., 13, 464 (1968).
Organic Polarography Donald 1. Piefrzyk, Department of Chemistry, University o f Iowa, Iowa City, Iowa 52240
T
HIS REVIEW SURVEYS articles described in Chemical Abstracts, Analytical Abstracts, Electroanalytical Abstracts, Chemical Titles, and readily available journals ending November 30, 1971. No attempt was made to list all of the organic polarographic references. For example, interest in using polarography as an analytical method to follow the progress of chemical reactions or decomposition of substances appears to be increasing. Similarly, more investigators are using polarographic measurements to complement the usual physical and spectral data that are collected in characterization studies. Often these polarographic data are not given in sufficient detail. For this reason, these references are not included unless some unusual compounds or polarographic behavior is involved. Generally, references dealing with detailed studies of oxidation or reduction mechanisms, studies of experimental variables affecting half-wave potentials, correlation studies, and newer and unusual analytical procedures were selected. Studies dealing strictly with biochemical or pharmaceutical problems are listed in the respective section rather than by functional group. Application of polarography, particularly in the former area, appears to be increasing. Many of these studies deal with a detailed investigation of the oxidation and/or reduction properties of biological model compounds. Kowever, only some of the investigators attempt to relate their data to actual biological systems. Cyclic voltammetry has been used more extensively, particularly when the
investigation is on the mechanism of oxidation or reduction. This approach is identified in this review by the symbols cv; the symbols dc and ac signify the direct current and alternating current polarographic technique, respectively. GENERAL REVIEWS
Several general type reference books have been published. These deal with organic electrode processes (985), organic polarography (988), and inverse polarography and voltammetry (656). Specific topics are polarography of metal complexes (167) and applications in agronomy and biology (664). One particularly interesting book is “Topics in Organic Polarography” by Professor P. Zuman (987). This book is a compilation of Professor Zuman’s and his associates’ past papers dealing with polarography. Recognition of his contributions in polarography in this way is well-deserved. General polarographic reviews which include organic polarography were compiled (462, 664). Other reviews survey electrochemical methods suitable for investigating organic mechanisms at electrodes (986) and identifying organic products in electrolysis studies (647). Applications of polarography in drug technology (505, 958), for the study of proteins and clinical problems (549),and analysis of biological substances (26) were reviewed. Other reviews covered applications in photographic chemistry (381) and establishment of detection limits for sixteen herbicides (525). The electrochemical properties of
azomethine compounds (459, 568), natural resins such as gambage, copal, and mastic resins (55U), flavines (465), and anthraquinone and derivatives (444) were reviewed. Anodic oxidation pathways for aromatic amines and hydrocarbons (2) and for aromatic N compounds in nonaqueous media (187) were surveyed. The dc and ac polarographic responses of twenty-four different pharmaceutical compounds (barbiturates, salicylates, alkaloids, sulphas, and others (969) and singe sweep ocillopolarographic responses for to IO-’M/l. acids and alcohols (42U) were described. Interest in correlations of polarographic data to experimental or physical properties continued. Most of these studies are included in the functional group sections. Those of general interest are correlation of half-wave potentials of antioxidants (anodic data) to antioxidizing properties (789) and a review of the polarographic behavior of aromatic hydrocarbons and the relationships of these data to Hueckel molecular orbital (MO) calculations (354). Half-wave potentials have been correlated to dipole moments with the best fit found for polarographically active carbonyl and halogen compounds (293). The relationship between halfwave potentials and acid-base titration data in pyridine solvent was reviewed (213). Polarographic data for several substituted aromatic halides, tosylates, aldehydes, nitro compounds, and ferrocene derivatives were correlated to ortho substituent values by either of two equations and the ortho effect was suggested to be purely electrical in
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
457R
nature and appeared also to be independent of the medium but strongly dependent on the group being reduced (144)-
Several general studies and reviews deal with the properties of the solvent. Polarographic behavior of a variety of compounds in diglyme, bis(2-methoxyethy1)ether (162), pyridine and liquid SO2 (sal), propylene carbonate (676), glycol solvents a t 200 f 2 O C (931), and in nitromethane (also effect of electrolytes) (32) was described. The techniques for investigating electrochemical reactions of organic compounds (emphasis on aromatic hydrocarbons) in aprotic solvents (41) and the general aspects of the influence of solvent on reaction mechanisms a t the electrode (794) were reviewed. Adsorption and oxidation processes for alcohols, aldehydes, and formic acid on Pt group metals have been reviewed (720). The utility of impregnated carbon electrodes (60) and of solid and paste graphite electrodes in ac oscillographic polarography (601) was described. The preparation and properties of thin gold and platinum films on glass or quartz as optically transparent electrodes (964)and techniques for spectro-electrochemical studies at thin layer electrochemical cells (466) were described. Other studies utilizing the transparent electrode technique are listed in the functional group sections. Square wave polarography (464) and potential step cyclic voltammetry (698) were evaluated with several different organic compounds. The latter technique is most useful when there are two one-electron transfers, each leading to different products. An apparatus for observing electrochemiluminescence during electrolysis (249) and a polarographic cell capable of rigorously excluding H20 and 02 (631) were described. Chromatopolarography in the analysis of organic compounds was reviewed (439), while in high speed liquidchromatography, the polarographic detection limit of effluent for several systems was established to be as low as 10-8M (471). Rate processes (822) and level of surface activity for several surfactants (823) were established by ac polarography. The effect of electrochemical inactive surface active agents (287), a study of surfactants and pyrogenic matter in distilled water (146),a theory detailing the adsorption and orientation of electroactive species on an electrode (636),and a study of adsorption involving multiple bond functional groups by linear potential sweep voltammetry (634) were described. A theory describing the polarographic currents controlled by the kintics of dismutation of the electrode reaction products was presented (433). In a 458R
different study, a theory for a reversible charge transfer followed by a rate controlled adsorption-desorption involving the product of the electrode reaction at a stationary electrode was evaluated (361)
.
The limiting potentials for four tetraalkylammonium salts in five different organic solvents was reported (362). The kinetics for exchange of the (Bu),Nf and H f on cation resins was followed by polarography (67). I n other general studies, reactions of organic compounds with electrochemically generated diatomic oxygen anions were followed a t an electrode (182), cathode ray polarography was used to determine polarographically active compounds after separation by sheet methods (366), and the sodium salt of polystyrenesulfonic acid was shown to be useful as a maxima suppressor (169). QUINONES
The effect of proton donors on the benzoquinone/hydroquinone reduction and oxidation, respectively, in methanol (42f), on quinone reduction a t platinum electrodes in aprotic solvents (399), and on several quinone/hydroquinone couples in aprotic solvents (209) were evaluated. Cyclic voltammetry was used in another study of the role of proton donors on the electrochemical behavior of the quinone/ hydroquinone system in organic media (68). The height of the pre-wave in the reduction of benzoquinone was shown to be proportional to the presence of an acid and could be used for the analysis of the acid (891). The reduction of benzoquinone in LiClOrmethanol was suggested to be complicated by ion pairing (207). Oxidation of hydroquinone in acetonitrile was investigated (704). A flowing quinone/hydroquinone system containing an electrolyte was investigated electrochemically (290). Effect of proton donors on the reduction of methyl substituted benzoquinones in aqueous and methyl cellosolve solutions was reported (892). Reduction of alkylated diphenylquinones (721) and benzoquinones substituted in the 2 and 6 positions by alkyi groups (789) were studied by cv and dc polarography. 2-Ethylquinone reduction was studied a t vitreous carbon electrodes (403), while the redox properties for seventeen methyl substituted benzoquinones and their hydroquinones (106) and for bis(trimethy1-p-quinon-2yl)methane, 1,2-bis(trimethyl-p-quinon2-yl)ethane, and 1,3-bis(trimethy1-pquinon-2-y1)propane (267) were measured polarographically. Attempts a t correlating half-wave potentials with additive substituent effects were carried out in the latter study. Six different bisaminated benzo-
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
quinones were studied polarographically as a function of pH (126). The electrochemical behavior of twenty-six aminoquinones and quinone thioethers in aqueous-ethanol mixtures as a function of pH was reported (363). In addition, half-wave potentials and electron transfer rates were compared to ESR hyperfme splitting constants. The redox potentials for forty-three benzoquinones were determined polarographically (24.49) Products from the reaction of C102 and phenol, o-cresol, oi- 3,5xylenol, which were the corresponding methyl and/or chlorinated quinones, were analyzed by ac polarography (286). The polarographic behavior of the photographic developers, hydroquinone/l-phenol-3pyrazolidone and hydroquinonelp-Nmethylaminophenol a t a stationary Ag disk electrode (103) and for hydroquinone and for 4,4’-and 5,5’-phenidone oxidation (104) were reported. Several studies with anthraquinone and its derivatives were reported. The effect of electrolyte and proton donors on the polarographic behaviors of anthraquinone and its hydroxy derivatives was described (446). In other studies, phenolic derivatives in D M F (448) and carboxylic acids in D M F and methanol (447) were used as proton donors in studies with anthraquinone. In the latter study half-wave potentials were correlated to K, for the acids. Reduction of anthraquinone in formamide mixed with methanol, DMSO, or pyridine was described (791, 792). The voltammetric oxidation of seven anthraquinones to the singly-charged radical cation was investigated in acetonitrile and nitromethane (93). I n other studies the polarographic behavior of 1,4di- and 1,4,5,8-tetra-aminoanthraquinone in acetate buffer (333),of fifteen heterocyclic derivatives of anthraquinone (660), and for 1-hydroxy-9,lOanthraquinone and its conjugate base in DMF and acetonitrile (730) were reborted. The effect of nonionic surfactants on polarographic limiting currents for anthraquinone derivatives was described (336). The influence of solvent mixtures, electrolytes, and viscosity on limiting currents in a study of the polarographic determination of 2-ethylanthraquinone was reported (402). Half-wave potentials for fourteen a and p substituted anthraquinones were correlated to Taft constants and to calculated energies of lower vacant p-orbitals (992). Half-wave potential-calculated energy correlations were also reported for other substituted anthraquinones (972). Polarographic data for 2-(R-~ubstituted)anthrahydroquinones were correlated to Hammett constants ( 9 8 ) , while data for anthraquinone type dispersive dyes were correlated to IR spectral characteristics (886). The reduction of 1,2- and 1,4-naph-
thoquinone in aprotic solvents and the effect of metal ions ($66), cathodic and anodic data for 5,&dihydroxy-l,4naphthoquinone, jugolone, hydrojugolone, and lawsone (46$), and oxidation of diphosphate esters of 2-methyl-1,Pnaphthohydroquinone (616) were measured polarographically. 2-Methyl-l14-naphthoquinone was determined by cv and dc polarography (709). Half-wave potentials for a series of l14-naphthoquinones containing fused rings in 2,3 positions were correlated to Hueckel calculations (765, 766). Reduction potential for the quinonoiddihydropterin-tetrahydropterin couple was determined by polarography (16). The oxidation of I to the quinone
OH 1
polarographically was used as evidence for antiaromaticity of cyclobutadiene (102).
Two and three waves were reported, in mechanistic studies for alizarin and alizarin S, respectively (1, 217). The reduction path and influence of post wave and adsorption for fluorescein was described (40, 947, 948). A two-step pH-controlled reduction process for eosin (633) and procedure for the analysis of eosine and phloxine (636) was proposed. Polarographic data for the dibenzoquinomethane compounds, fuchsone, and aurine were reported (332). ALCOHOLS. GLYCOLS, AND PHENOLS
Polarographic data for eight phenols substituted in the 2,6 position as a function of pH (481) and for thirty phenols with substituents in the 2,4, and 6 position (949) were reported. Cyclic voltammetry was used to investigate the redox properties of 2,6-dialkyl4-alkoxy phenols in acetonitrile (sat?),of catechol in H&Od (916), and of [3,4-(CH30)& H&H2]2 (705). Phenolic antioxidants such as propylgallate, and 2,6-di-tertbutyl-p-cresol in fats were determined voltammetrically at a graphite electrode (261). Anodic data for methoxybenzene derivatives were correlated to rate of photooxidation (790). Polarographic behavior of %alkoxy4,6-di-tert-butylphenoxy dimers (763) and several hydroxy derivatives of naphthalene in 70% methanol and DMF (449) were reported. The adsorption of n-amyl alcohol (52) and of cyclohexanol (818) in the presence of several different supporting electrolytes was studied by tensammetry. Polarographic techniques were used to investigate the influence of carboxylic acids and their salts on the measurement of CH,0H2+
(701). A procedure for the measurement of short lived organic radical ( 7 and in the presence of camphor and aprotic solvents was discussed (912). Radicals derived from nitrobenzene (46), 2,Pdinitrobenzene (284, and Cnitropyridine N-oxide (634) were studied by polarographic and other instrumental methods. Several nitrobenzene derivatives were polarographically studied in order to explain the polarographic behavior of phenylhydroxylamines (169). Half-wave potentials for S-substituted nitrobenzenes were correlated to ESCA shifts (electron binding energies) (658). Hammett constantrhalf-wave potential correlations were considered for S-substituted nitrobenzenes (557), p-substituted nitrobenzenes and benzaldehydes (629) and for nitrobenzene derivatives (866). Hueckel MO calculations were used to interpret substituent effects in polarographic behavior of aromatic nitro and azo compounds (507) and were correlated to data for six mononitro and nine dinitro derivatives of phenyl benzoate (pH effect also reported) (716). Polarographic oxidation and reduction halfwave potentials for a series of 4 and 5substituted 2-nitrophenols were recorded in 10% ethanol as a function of pH and the data were correlated to substituent constants and to frequency of the longest wavelength maximum (771). Half-wave potentials for twenty-four nitro and benzaldehyde derivatives were related to a solvatochromic effect (239)*
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
Several different aliphatic nitro compounds have been studied. Polarographic data were reported for 2 nitrobutanol (564), tetranitromethane and other nitroalkanes (7$4), a-phenyl(767), and &!-furyl)-fl-nitroethylene and for CH&(NOZ)=C(NOZ)CH~ and CsH&H=CBrNOz ($0). For the latter nitro-bromo derivative the products CsH&H&N and Br- and CeHsCH2(OCH3)CN were identified when using water-dioxane and water-methanol as solvents, respectively. Reduction data were reported for trinitromethane and other aliphatic polynitro compounds a t rotating Pt, Pd, Au, and pyrolytic graphite electrodes (473), for nitrohalogen-alkanes a t a graphite electrode (480), and for tetranitromethane and nitromethane a t Pt, pyrolytic C, graphite, and Hg (518). Alkaline solution was used to investigate the polarographic behavior of Ksalt of trinitromethane (783) and of dinitromethane and 1,ldinitroethane (592). The effect of pH was considered in the reduction of l-pyridyl-2nitropropane and 1-pyridyl-2-nitropropene derivatives (148) and for four nitroalkanes (also effect of water and three solvents) ( 4 9 ) . The mechanism for the reduction of fluoro-containing polynitroalkanes was reported (722). Nitroalkanes and nitroalkyl carboxylic acids were studied by ac polarography (314 ) . The polarography of CeH5CC1=CHN02 and C6H6C(NHCeHb)=CHNOz was compared to results for CaH&H=CHNOz (158). Anion adsorption was considered on the polarographic reduction of l-nitropropane (301). Polarography was used to study the hydrolysis of l-nitrato-propionic and -butyric acid (779). Procedures for the quantitative analysis of l-methoxy-3-(2-nitroimidazol-lyl)propan-2-01 and l-chloro-3(2-methyl5nitroimidazol-l-yl)propan-2-ol in blood and urine (177), p-nitro-2-aceb amido-3-hydroxypropiophenone and 1p-nitro-phenyl-2-amino-1 ,&propanediol (201), 4,6-dinitro-2isopropyl phenol in blood (236), fenitrothion and its hydrolysis product, Pnitro-m-cresol (303), 2 (3-butoxy-2-hydroxypropyl)-5 - n i t r oisoindolinium chloride (360), 1-(5nitro-iso-indoiino)-3-butoxy-i so-propanol in urine (364), 4,5-dinitro-o-cresol in blood (624), and for o-nitrotoluene and nitronaphthalene in o-toluidine and naphthalamine, respectively, (897) were reported. Cholesterol after esterification with dinitrobenzoyl chloride (268), ephedrine after reaction with 2,4dinitrophenyhydrazine (366), and Il'a-salt of p-aminosalicyclic acid after reaction with 5nitrofurfural (476) were determined polarographically. Parathion and methyl parathion in crops (470) and 0,O-dimethyl-0-(4 nitro - 3 - methylpheny1)phosphothioate
(Metation) and analogs (809) were determined polarographically after chromatographic separation. Chloramphenical was shown to undergo a twoelectron reduction of the nitro group followed by a fast two-electron reduction to hydroxylamine and was analyzed in milk (260). Oscillographic polarography was used to determine nitrocellulose and polyvinyl nitrate (742), nitro derivatives used in explosives (770), and dinitro-ocresol in water (878). Nitroglycerine was determined by ac and dc polarography (968), while 1-[5(4-nitrophenyl)fufurylideneaminolhydantoin sodium salt hydrate (Dantrolene Sodium) was analyzed by differential. pulse polarography (166). 2,4-Dichlorophenoxyacetic acid in blood and urine (236), phenazone (393, 676), 4,4'-thiobis(6-tert-butyl-m-cresol) (4729, benzene (607), 4-hydroxybenzoic acid esters (894), and phenothiazine (991) were determined polarographi-
cally after a nitration procedure. Nitroso Compounds. Polarographic data were reported for the reduction of nitrosonaphthols (153), N-nitroso-lmethylamino-ldeoxyalditols and their 0-acetyl derivatives (189), for cupferron (365), and for nitrosated and substituted derivatives of hydrazines (764). Several aliphatic N-nitrosoamines (84), [ONC(CN)zI- and [OZNC (CN),] - (609), dimethylnitrosoamine (666), and di-n-propyl-N-nitrosoamine (751) were studied as a function of pH. The effect of substituents were considered in an ac polarographic investigation of brucine derivatives of isonitroso- and substituted iso-nitroso-acetophenones (697). Radicals from the oxidation of N-(p-nitrosopheny1)Nphenyl hydroxylamine were studied by cv methods (139). Organophosphate insecticides were polarographically determined by a reaction that yielded 8-naphthol which was nitrosated (810). The nitrosation reacwas also used for the analysis of emetine (174). Aliphatic-AromaticAmines. Polarographic data for aliphatic and aromatic amines as their amine oxides (341), for the oxidation of piperidine (46), and for the oxidation (cv data) for twenty-two dimethylamino substituted alkenes (262) were reported. Inhibiting p r o p erties of amines as surfactants and corrosion inhibitors were investigated by ac polarography (237). Reductive degradation of aziridinium salts, XII,
-
CH3CH2
CHICK3
\+/
N
XI1
were shown to follow a different pathway depending on whether the solvent is protic or aprotic (926). Polarographic data were reported for fifteen &quaternary ammonium derivatives in KzSOl solution and their surface activities were correlated to their germicidal effect (877). The electrochemical behavior of aniline in alkaline solutibns a t smooth Pt, platinized Pt, graphite, and Au electrode (176) and for its oxidation (mechanism discussed) a t a rotating disk electrode in acetonitrile (99) was reported. Mechanistic studies for oxidation of N , N d i methylaniline in nonaqueous solvents (327), N,Ndimethylaniline and ring substituted derivatives (326), and for N,Ndimethyl-ptoluidine in acetonitrile and aqueous buffer solutions a t a carbon paste electrode (618) were described. Correlation of inhibitor action and half-wave potentials for the twentythree nuclear alkylated anilines was not successful (280). Coupling moments (571) and Hammett constant (632) correlations were reported for mono- and disubstituted anilines and N,Ndimethyl anilines and for aromatic mono- and diamine derivatives, respectively. 1,4Aminophenol and derivatives (464) and N,N,N ',N '-tetramethyl-p-phenyl ene d iamine (729) were studied by cv methods. The latter was shown to follow a rapid electron transfer followed by pseudofirst order transformation of product a t pH 9.8. The oxidation for twenty aromatic amines (64), for aromatic amines, diamines, and diamino sulfides (Hammett constant correlations) (M),and for sixteen aniline derivatives (56) a t a Pt electrode as a function of pH was reported. Half wave oxidation potentials for forty-four amines were correlated to ionization potentials (528). The electrochemical oxidation of eight aromatic amines was done in molten SbCl3; a pHCl scale was defined through the half wave potential measurements
(60). The anodic behavior for diphenylamine and several of its derivatives was examined in detail (643, 843). Investigation of the oxidation of benzidine by cyclic voltammetry (769) and a t a graphite anode (also alizarin S) (758) was carried out. Cyclic voltamnietric data were used to establish the structure of a stable, solid, ionic free radical, XIII, that was produced in the electrol-
J
L
XIII ysis of 3,3'dimethyl-4,4'diaminobiphenyl(76). Polarographic data were reported for rhodamine B as a function of pH (408)
and for N,N'diphenylbenzamidine (817 ) . The presence of oxoammonium cationic species and of the protonated amine in an acidic solution of di-panisyl nitroxide in electrolysis studies was demonstrated by polarography, and other techniques (140). The reduction (cv data) of nine benzenesulfonamides was studied in acetonitrile where the pathway was suggested to follow a two-electron process to an intermediate which undergoes scission of the S-N bond to produce sulfinate and amide ions (164). Azo Compounds. Polarographic data were reported for azo and azoxy benzene in acid solution (346), for 3aminoazobenzene derivatives (526), 4RCeH&(N2)COR' derivatives (746), and for o- and m-bisazobenzenes in buffered solution (785). p-Dimethylamino-o'-, -mr-, and -p'-substituted azobenzenes (651), 3-diazo- and 3amino-camphor (132), and 3,4-xylyl6-phenylazo-1-d-ribamine (azorilitylamine) (9029 were studied as a function of pH. The reduction of diazonium and diazonesulfonate salts (934), of a series of aromatic azides (976), and for Wdiazoacetophenones (also the effect of adsorption) (35) was investigated. Oscillopolarography and dc polarography were used to study the oxidation mechanism for ldiazo-2,3,4,5-tetraphenylcyclopentadiene and eight other diazo compounds in acetonitrile a t a rotating Pt electrode (747, 748). The oxidation mechanism for 4aminoazobenzene was studied by cv techniques (526). 1-o-Tolylazo-8-naphthol (Orange OT) solubilized in Na dodecyl sulfate solution (336) and arsenazo I (974) were studied polarographically. I n the latter compound, the first wave was a kinetic wave due to the azo group and the second two waves were due to the arsonic group. Three waves were observed for the reduction of w-diazoacetophenone and twelve m- and p-substituted derivatives; the products of the three waves are w-aminoacetophenone, acetophenone, 8-hydroxypropylbenzene, respectively (34). Diazoacetophenones in biological systems were determined polarographically (156). The adsorption of methyl red during reduction was reported (87). Half-wave potentials for p-RC&& (=N2)COCsHs a t a rotating Pt disk electrode (64), p-monosubstituted azobenzenes in acetonitrile (88), azo and azoxy benzene derivatives (208), aromatic mono and bis(ary1 azide) derivatives (479), RC6H&ON=NC& derivatives (532), twenty-six disperse azo dye derivatives (885), and for p-Xazobenzenes and 2-X-5-phenylazopyridines in aprotic solvents (911) were correlated to Hammett and/or Taft substituent constants. A relationship between the energy of the lowest free *-
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
a
463R
molecular orbital and half-wave potentials for six azo hydrocarbons in acetonitrile was reported (627). Polarographic data for derivatives of arylmethoxymethyldiazenium salts were correlated to charge transfer energies (358). Azomethine Group. Reduction a t the C N position in 2-alkylamino-2alkylindandiones was studied as a function of pH (860, 942). The effect of proton donors and intramolecular Hbonding on the polarographic behavior of 2-phenyl-3-phenyliminoindoleninein DMF (18) and azomethine derivatives (929) was studied, respectively. Reduction data for twenty-one different immonium compounds of type XIV were measured in acetonitrile and
R'
(133, 135), violuric acid (436), and methyl hydroxylamine (683) WAS studied as a function of pH. Anodic data were reported for 0-carbamoyl derivatives of N-acyl-N-alkylhydroxylamine (878,874). Three waves totaling thirteen-electrons (first wave is due to the -C= NOH group) were observed for XVII W
W
XVII (114). I n a reduction study of phenylhydroxylamine it was shown that the reducible form of the compound is due to the mono- and di-protonated species rather than the uncharged molecule (338). Compounds of type XVIII,
R
\
+/
C=N
/
\
R2
Ra
R(NCC+NOH X XVIII
XIV
where R is a substituted N, S, or 0 heterocyclic group or phenyl and X is a heteroatom or C=C with a substituent, were shown to be reducible a t the oxime group (603). p-Quinone monoxime and dioxime were determined polarographically (496). The effect of 0-alkylation on the xv polarographic behavior of the oximino quinoxaline, 5,6dihydropyr%sine, and group was studied (984). The hyof adiimine compounds as a function drolysis of cyclohexanone oxime was pH; reduction occurs a t the C-N bond followed by polarography (640), while in the system XVI (739). Direct cathode ray polarography was used to study the transformation of Ga-methylI I 17a-acetoxyprogesterone 3-oxime to its -N=&C=N-lactam (830). XVI Oxidation of diphenyl hydrazine (three waves) (138), of 1,l-dimethyl current polarographic and cv data were and hydrazine a t a Au electrode (HI), used in mechanistic studies of mono of hydrazine sulfate a t rotating Pt as imines of benzil and 2,2'-pyridil (19) a function of pH (649) was described. and for several different imines in DMF The reduction mechanism and the ef(264). fect of pH were reported for camphorHalf-wave potentials for Schiff bases quinone 3-hyd razone (134) and isatin a t Pt were correlated to Hammett 3-hydrazone (186). Data were revalues (606). In other studies with ported for six new Nl-isonicotinylaromatic Schiff bases, correlations were (ZOO). N2disubstituted hydrazines found with I R spectra, Hueckel calcuThe effect of substituent, pH, and lations, and Hammett values (71). pK, was noted in studies with seconThe effect of substituents was considered dary hydrazones of benzaldehyde dein studies with XC~H~N=CHC.SH~Y rivatives (457). Two reversible onederivatives (185). electron waves were found for X I X Aromatic diamines and aminonitriles were determined polarographically after reaction with acetone in basic solution I R' (17) while ketones were analyzed after IR reaction with amines (866). The reR action of formaldehyde and 1,bhexaXIX methylenediamine was used for the analysis of microgram amounts of the (359) and reduction at C=N in the aldehyde (568) as well as for the amine ring was found for (11). A de(864). The hydrolysis of asomethine derivatives was followed polarographically (930). Oximes, Hydrazones, Hydrazines, / xx and Semicarbazones. The reduction behavior for bcamphorquinone oxime
benzonitrile (8). Detailed studies were reported for the mechanism of reduction for XV (717) and for derivatives of
qAN-&Jh/ xx
&&
464R
tailed electrochemical study of hydrazine in liquid ammonia a t Pt was reported (695). Sixteen phenylhydrazone derivatives were investigated as a function of pH and the anodic data were correlated to Taft constants (876). Data for dimethyl hydrazones of substituted benzaldehydes and benzylidene-4-imino-l,2,
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
4(4H)-triazoles were correlated to Hammett constants and to energy of vacant orbitals (468). Formation of hydrazones was suggested to be superior to semicarbazide formation in quanititative analysis by polarography (909). The use of hydrazine in analysis (982) and the determination of hydrazine derivatives (604) by polarography were reported. Polarographic data were reported for a series of Ni(II)-diketone bisthiosemicarbazones (36), benzil monosemicarbazone (245), semicarbazones of several acireductone derivatives (263-255), diphenylcarbazone, diphenylcarbazide, and diphenylcarbodiazone as a function of pH (441), and for thiosemicarbazides a t rotating Pt (567). Diphenylcarbasone and diphenylcarbodiazine was studied as a function of pH (769), while diphenylcarbazone oxidation was studied a t a Pt and graphite electrode (376). Carbonyl compounds were separated by gas chromatography, then determined polarographically as Girard-T hydrazones (250). In other studies, aldehydes were determined as Girard-T hydrazones (248), and hydrolysis of the derivatives was followed by polarography (608). Reduction of Girard-T hydrazone derivatives of aliphatic ketones were studied as a function of pH and solvent composition; a procedure for the determination of carbonyl compounds was proposed (83). Carbonyl compounds as semicarbazones were separated by chromatography and then determined by polarography (81). UNSATURATED HYDROCARBONS
Polarographic data were reported for several aromatic hydrocarbons, unsaturated compounds, and thiophene derivatives Pmethoxystyrene (610), eight helicenes (623), p-carotene and derivatives (587) 9,10-di(a-naphthvlhnthracene (698) and for perchiorodecatetraene and perchlorodecapentaene (840). Electrochemical data were for tetranisvlethvlene . ~ recorded ~~~.~ . and tetrakis (p-N,N-dimethylaminopheny1)ethylene oxide (ha), 0- and p quinocyclopropenes of benzene, naphthalene, anthracene, phenanthrene, and fluorene @ I O ) , for several phenylcya-
(as),
noethylenes (373), and for several benzotropone and thienotropone derivatives in nonaqueous solvents (98.9). Cyclic voltammetric and polarographic data were collected in studies of aromatic hydrocarbons (leads to stable cation radicals) (181), p-anisylethylene in anodic acetoxylation studies (206), of trivalent carbon species of the type R+, R-, and R . in HzS04 (856), of 4,4'-dimethoxystilbene (mechanism presented) (703), of reductive coupling of acrylonitrile with other electroreducible substances (7.95), and of tetraphenylethylene, triphenylethylene, stilbene, l ,l-diphenylethylene, and styrene (267). I n the latter studies, it was shown that the radical anions of these compounds were protonated in the medium and are therefore stronger nucleophiles than for polycyclic aromatic hydrocarbons for which similar protonation does not occur. Anodic data were collected for hexamethylbenzene and 1,5-dichloroanthracene (166), for benzo(a)pyrene at Pt (initial oxidation is a one-electron process to a cation radical which is consumed in two pathways) (398), for styrene (suggested that the oxidation product is a dication rather than radical cation) (44.9), and for arylcyclopropanes (8.99). Chemiluminescence was electrogenerated in studies with 9,lO-diphenylanthracene (594, 595), with aromatic hydrocarbons and 1,2-dibromo-l,2diphenylethane (833),and with perylene and anthracene (961). Effect of proton donors and solvent was considered in reduction studies with naphthalene and anthracene (406). Reduction properties of Zmethoxyazocine was compared to the cyclooctatetraene system (7, 700). Polarographic data were reported for chromazurol S as a function of pH (577), for twelve triarylmethane dyes (668), phenol red (81.9, 81.3, triphenylmethyl ion in H2S04 (pathway depends on protonation of radical formed by the first one-electron uptake) (734, 736), several aryl alkyl cations in HzS04 and CHaSOaH (755), and for 4,4',4"substituted triphenylmethyl cations and anions (pK.'s determined) (101). Ten different polynuclear hydrocarbons were studied in the molten system, A1C13--NaC1-KC1 (251). Oneelectron reduction was observed for RCCH~=C(CN)COZC~H where ~ R is an alkyl group ( 3 7 ) . One- or threeelectron reduction was found for fluorene depending on whether proton donors were present or not (404). The mechanism for the polarographic behavior of pyridinium cyclopentadienylide (276) and R1CH=CHCOR2, where R1 and Rt are phenyl or polycyclic aromatic groups, (496) was reported. I n the latter study, two one-electron waves were observed and the effect of sol-
vents, pH, and substituents was considered. Anthracene was used to test a second harmonic ac polarography theory (576). Rate parameters were derived from dc and ac polarographic data for cyclooctatetraene, its anion radical, and 1,3,5-cyclooctatriene (367). An ECE mechanism was identified in anodic substitution reactions of aromatic cation radicals (596). Two successive oneelectron reversible oxidation waves was found for four 1,Bene-diamines in acetonitrile and benzonitrile (10). A cv technique was used to determine whether a nucleophile reacts a t a C center or acts as a base during reaction with anodically generated intermediates using anthracene and lutidine derivatives (70%). Hueckel molecular orbital calculations were correlated to half-wave potentials for tramdipyridylethylene derivatives in presence of proton donors (6.98), fulvene derivatives (895), and for a series of alkyl substituted phenanthrene and biphenyl derivatives (hyperconjugative, inductive, and steric strain effects were also considered) (405). A linear dependence between half-wave potentials for sixteen conjugated polyenes containing from four to twenty-two double bonds and calculated energies of lowest free molecular orbitals (58.9) was found. Electron affinities and half-wave potentials for styrene and eight alkyl substituted derivatives were correlated (485). Polarographic data for nineteen derivatives of malachite green and Hammett constants were related ( 5 9 ) . Electron affinities and ioni~ationpotentials were correlated to reduction and oxidation potentials respectively, for seventy-six aromatic hydrocarbons (179). The relationship between electron spin resonance signal intensity and half-wave potentials for polynuclear aromatic hydrocarbons was used to characterize the oxidizing ability of silica-alumina catalysts (645). Steric hindrance conclusions were drawn from a half-wave potential-energy for the first antibonding orbital for planar systems relationship for several trans-a,P-diarylacrylonitriles (409). Half-wave potentials for several aromatic hydrocarbons in molten SbC& were used to establish a potential scale for the solvent (51). Alternating current polarography was used for the determination of 1- and 2methylnaphthalene (86) and for unsaturation based on a Hg(I1)-olefin addition formation (247). Perchlorohexadiene-1,5 and isomers of perchlorohexatrienes-1,3,5 (839), polyolefins in polymers (184, 851), and vinyl monomers containing bi- and ter-nucloar aromatic systems (72) were determined polarographically. Oscillopolarography was used to determine vitamin A acetate in the presence of vitamin A (932).
PEROXIDES
Polarograpnic data were reported
for di-twt-butyl per esters of peroxy disuccinic and diglutaric acids (382), for CeH&(CH&OOH and (CeHb)&HCH2 OOH (498), for percaprylic, percapric, perlauric, and permyristic acids (832), and for cumyl hydroperoxide and tertbutyl-hydroperoxide (971). Hydroperoxide and its mercury salts in the presence of diacyl peroxides were examined by oscillopolarography (188). Effect of pH, chain length, and correlation to Taft constants were considered in a study of alkyl hydroperoxides (334). Benzoyl peroxide in polyether resins (a&?), furoil and nicotinoil peroxides (641), isopropyltetratin hydroperoxide (719), and of lauryl peroxide and other initiators in waste waters from poly(vinyl chloride) production (6.92) were determined polarographically. Polarographic methods were used in the analysis of 2'-acetonaphtone, Bisopropylnaphthalene hydroperoxide, and bis(2isopropylnaphthalene)peroxide in emulsion oxidation (718), 1,3,5trimethylcyclohexyl hydroperoxide in photooxidation studies (738),and for chloroprene peroxide (550). SULFUR COMPOUNDS
Mercaptans, Sulfides. Polarographic behavior was reported for amercapto-a-phenyl acetic acid (2.9), cysteine, thioglycolate, ethyl xanthate, thioxine, and thiosemicarbazide (66), thiokols of the type H S L ( C H & H ~ C H ~ OCH~CHZS~CH&H~OCH~CH~CH~) S2H with molecular weights above 1000 ( l l S ) , glutathione a t Pt and Au (691), and for the catalytic wave for a Co(I1) and Ni(I1) thioglycolate buffered system (914). The effect of pH and other experimental conditions were considered in studies with thiovanol (666), diNa-dithioloterephthalate (696), 3-mercaptoproprionic acid (796), 3mercapto-1,2-propanediol(798) and for thiolacetic acid (800). Polarographic analysis and Hammett constant correlation were reported for N-benzoyl-threo-8-p-substituted phenylcystine ethyl esters (900). Polarographic data were reported for 5 - ( p - methoxyphenyl) 3H - 1,2-dithiole3-thione (869) and for the analysis of S in its solutions (868). Procedures were reported for the polarographic determination of thiol group after reaction with N-ethylmaleimide (960) and for the insecticides 0,O-diethyl-0- [2- (ethy1thio)ethyllphosphorothionate (300) and dithiophosphoric acid esters (488). Tetramethylthiuram disulfide was studied and determined by cv, dc, and ac polarographic techniques ( 9 5 ) . Polarographic data were reported for twenty-two derivatives of [R(CHz). SI2 where R is a series of amines ( 1 0 4 ,
-
ANALYTICAL CHEMISTRY, VOL. 44, NO, 5, APRIL 1972
0
465R
8,8'diquinolyldisulfide (187), alkyl aryl sulfides in acetonitrile (280), and for diphenyldisulfide in mathanol-benzene (773). Ethyl thioglycollate (796), methoxyethyl mercaptoacetate (797), and methoxyethylthioglycolate (799) were studied. A series of S-substituted-2-thio-substituted barbiturates were studied as a function of pH and substituents; the reduction mechanism was described (846, 847). The electrode process of the benzenethiol-phenyldisulfide system was studied on Pt in D M F and 50% methanol-water (680). Orthothiooxalate, XXI, and bicyclic tetrathioethylene, XXII, was studied by several
XXI
XXII
electrochemical techniques and the electrode reaction was discussed; dicab ion formation was suggested for XXII (128). The catalytic wave for eight different sulfur compounds a t pH of 6 in the presence of Ni(I1) was investigated (781). Sulfur-Oxygen Bonded Compounds. Polarographic data were reported for phenyl methyl sulfoxide in H2S04 (276), p-toluenesulfonic acid and its ester in D M F (COO), and for sixteen phenylsulfonyl derivatives having a vinyl, ethyl, or 2-chloroethyl group (826). Aryl tosylates of the type p-CH3-C&3XG"X were studied and the half-wave potentials in pyridine, DMF, and benzonitrile were correlated to Hammett constants (601, 602). Polarographic data for ethynylalkyl sulfones were correlated to Taft constants (624). The cis isomer of l,Zbis(alkylsulfony1)ethylene was found to be more readily reduced than the trans isomer in ethanol and DMSO (692). Substituent effects were considered in polarographic studies of sulfonamides and carbonamides (561). Alkyl thioaldimines and heterocyclic mercapto compounds were studied in the presence of proton donors (686). The first step in the reduction of methyl benzene sulfenate was found to be a one-electron fission of the S-0 bond with the formation of an intermediate strongly adsorbed on Hg, while the second step was due to a oneelectron reduction of the intermediate (666). Lignosulfonic acids were polarographically determined after reaction with nile blue (222). Micelles of Na decyldodecyl and tetradecyl sulfate containing Cd(I1) were studied (565). Thioamides, Sulfonium Salts, and Miscellaneous Sulfur Compounds. Several studies dealt with the electro466R
chemical behavior and polarographic determination of diethylenedithiocarbamate salts (67, 93, 988). Several electrochemical methods including ac and dc polarography were evaluated for the determination of ethylenebisdithiocarbamic acid (94). A procedure was suggested for the analysis of K-diethyldithiocarbamate in the presence of Kethylxanthogenate (296) and for several dithiocarbamates (Ferbam) (788). The polarography reduction of the group -NH-CSin ethylene-bis-thiurammonosulfide was studied and a procedure developed for the analysis of Maneb, Zineb, and Nabam (214,816,873). Polarographic data were presented for a catalytic wave from a rubeanic acid-RuC13 solution (344), arylsulfenyl chlorides in D M F (416), thiocarbonyls (616), thiocarboxylic acid esters of the type RCOSR' where R is aromatic or aliphatic (64S), and for thiourea and thiooxine a t a Au electrode (980). Oxidation of 1,3-dimethyl-2imidazolidinethione was studied a t a Pt electrode (62)* A method in which simultaneous recording of anodic and cathic waves for Ni(I1) and Co(I1) complexes of thioaemicarbazide, thiosemicarbazone-acetone, thioglycol, cysteine, and others was described (116). The role of the electrode, Pt, Au, Cu, and galena, in the oxidation of ethyl xanthate to diethyl dixanthogen in order to explain mineral flotation with xanthate collectors was reported (967). The first wave for tribenzyl sulfonium hydrogen sulfate was an irreversible one-electron process to tribenzyl sulfonium cation which forms dibenzyl sulfate and dibenzylmercury; the second wave was due to adsorption (3s). Oscillopolarography was used to follow the decomposition of xanthin01 nicotinate in alkaline medium (583). Half-wave potentials for a series of 4'-substituted 4'iso-thiocyanatobiphenyls (14) and for [(CH3CHzO)tP(S)SlJH2-nS02CeH4R derivatives (2S4) were correlated to Hammett constants. ORGANOMETALLIC COMPOUNDS
Polarographic data were reported for Zchloromercury-3-ethoxycyclononene and Zchloromercury-3-ethoxycyclodecene (651) and for several organomercury compounds with substituents on the fl carbon (224). Five different organomercury compounds of the type RHgX and R2Hg were studied to determine whether anodic cleavage of a uC-Hg bond is a general reaction (262). Two one-electron waves were found for several olefin-Hg(I1) acetate addition compounds (246). The reduction process for unsaturated organomercury compounds such as allyl mercury iodide and phenyl mercury hydroxide (2SS) and for bis(2,5-diphenyl-l,3-oxazole-
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
4-yi)mercury a t a Pt disk electrode (846) was reported. The polarographic behavior of organotin compounds as a function of pH (468), trichloro(ethy1)-, dichlorodiethyl-, and chlorotriethyl tin compounds (analytical procedure also given) (86),and for trialkyl SnCl and dialkyl SnC12 compounds in the presence of alcohol (927, 928) was reported. Oscillopolarography was used to study BuSnCL, Bu2SnCl2, B U ~ S ~ ( O A Cand )~, others (278). A two one-electron process was found for the reduction of triphenyl tin compounds in nonaqueous solution (80). A procedure for the determination of trialkyl substituted organotin compounds was described (828). Polarographic data were reported for a series of bridged and nonbridged ferrocenes (298), for ferrocene, acetyl ferrocene, and acetoacetyl ferrocene ( S I I ) , mononitrosyl iron bis(diary1-1,Z dithiolene) complexes (674), for Fe and Co dithiolene complexes (38), benzoyl ferrocene and ferrocenyl aldehyde a t a rotating Au amalgam disk electrode (668), arene-Fe-cyclopentadienyl compounds where arene is bennene, naphthalene, fluorene, diphenyl, and phenanthrene (663), and for the ferrocene-ferricinium system (981). A mechanism for the polarographic behavior of cyclopentadiene carbonylhydridobis(trichlorosilyl)iron(I) in acetonitrile (97) and for cyclopentadienyl (benzene) iron derivatives in 50% ethanol (26) was proposed. Half-wave potentials for twelve 3-ferrocenyl-1(Xsubstituted-phenyl)-2propen-1-one derivatives as a function of pH were correlated to Taft and Hammett constants (826).
Polarographic data were reported for a series of transition metal dithiolene complexes in order to show that the metal is part of a six-membered electron transfer system (963), ?r-allyl complexes of transition metals (egg), and for several vitamin BIZmodel compound complexes (162). The electrochemical behavior of cobaloximes (343), RaPbO2 CC(CHI)=CHz derivatives (469), (r C6H&-Ti-u-R2 derivatives @IO), and for ( T C ~ H ~ ) ~where T ~ XX~is F, C1, Br, and I (SO9) was described. The reduction of monophenyl thallium perchlorate (227) and RzTIX where R is alkyl and X is C1, Br, or OAc (378) was reported. Bis substituted chromium in D M F (879), CeH5Cr(C0)3 derivatives in alcohol (66), and RMn(C0)s and RRe(C0)5 where R is a series of substituted aromatic groups (176) were investigated. Several 0- and m-carborane derivatives were studied in D M F (979). Cyclic voltammetric data were presented for the study of tetraphenylstibonium ion a t wax coated carbon and mercury coated carbon electrodes (966). Data
were reported for RAsO(0H)z where R
is a series of OH and NO2 substituted groups (968) and for eleven psubstituted (CsH&AsO and CsHs(CH3 CHZ)ZASOderivatives (Hammett correlation was found) (426). Detailed studies of the electrode behavior of RlRzRsM, RIRzR~MO,R1R2 RsMS, and RIRzRaPSewhere M is P or As and RI, Rz, and R3 are aromatic groups (6111, [(CaHdrPIRhCl and [(c6 H s ) z P C H ~ ] ~ R (686), ~ C ~ several dialkylaroylphosphonates (778), and for [ ( C B H ~ ) ~ P C H ~ C H ~ C+BrH ~ C N(916) ] were reported. Six reduction waves were reported for substituted (C6Hs)r P=NAr derivatives, where Ar is an arene group, in D M F (714). The effects of triphenyl-phosphine, -arsine, and -stilbene on the catalytic H-wave were described (819). Cleavage a t P-P bond was found in a polarographic study of seventeen cyclopolyphosphines, diphosphines, and their mono and disulfides (610). Data for substituted aroylphosphonates were correlated to Hammett constants in electrolysis studies of these compounds (61). A collaborative study by ten laboratories on the detection and determination of several organophosphorus insecticides by oscillographic polarography was described (270). Dipterex, (0,O-dimethyl - 2,2,2 - trichloro - 1- hydroxyethyl phosphonate) was studied and analyzed by CY and dc polarography as a function of pH and type of supporting electrolyte (282). Procedures for the determination of organically bound phosphorus compounds after formation of quinoline phosphomolybdate ( Y S ) , dithiophosphoric acid ester insecticides in soil (489, ,490) and [(CH3)21C']3P0 (hexanetapol) (271) by polarographic methods were reported. OXYGEN AND SULFUR HETEROCYCLIC COMPOUNDS
Polarographic data were reported for flavone and morin in methanolwater (499),natural-occurring coumarin derivatives (689), thiocyanate derivatives of thiophene (855), and for the reduction of 1,3,5,7-tetramethy1-2thioniaazulene perchlorate (903). Isomeric dithienyl sulfides, XXIII, XXIV, and XV, were investigated and a two-
Q-s-Q XXIII
XXN
xv
electron wave with half-wave potentials becoming more negative in the order
XXIII, XXIV, XXV was found (286). Half-wave potentials for XXVI, XXVII, and XXVIII were X and Y is
XXVI
XXVII
XXVIII
0 or S were correlated to energies of the highest occupied orbitals (805). A procedure utilizing ac and dc polarography was reported for the determination of usnic acid (S19, BO), while ac polarography was used for 3-(a-acetonylbenzyl)-4-'hydroxycoumarin (686). BIOLOGICAL-PHARMACEUTICAL STUDIES
The references in this section are those which emphasize studies with biological and pharmaceutical significant compounds or systems, with biological model compounds, and with the quantitative determination of these compounds. These references were not cited in any of the functional group sections. However, for completeness, the reader should examine the functional group sections for additional references which are of potential interest in the biological and pharmaceutical area. Biological Compounds. Perhaps one of the most interesting and potentially useful developments was the indirect electrochemical reduction of triphosphopyridine nucleotide spectroelectrochemically with a tin oxide optically transparent electrode using electrogenerated methyl viologen radical cation in the presence of the electron carrier, spinach ferrodoxin-TPN-reductase. Thus, it was possible to observe and evaluate the rate and reduction sequence (580). Polarographic data were reported for a variety of vitamin BIZ model compounds (163), amino acids as a function of pH (266), cardiac glycosides (S55), chlorophyll a (455), lysine-vasopressin and vasopressin as a function of pH (505), for the effect of H3B03 on several aldonolactones (615), micelle formation from lecithin as a function of methanol concentration (741), polyadenylic acid in acidic solution (762), and for adenosin-5'-triphosphate in the presence of Cu(I1) ions (843). Cystine in the presence of cysteine was studied by rapid sweep polarography (541). The slow decomposition of cystine in alkaline solution was studied (579). Cystine, cysteine, and coenzyme A were investigated in detail ( 7 4 3 , while cysteine after its injection into rat organs was studied by cv methods (746).
Proteo hormones (288) and vitamin
Ba derivatives and their metabolites (706) were investigated by ac polarography and oscillopolarographic methods, respectively. Cyclic voltammetry was used to determine the oxidation potentials for transition metal complexes of tetraphenylphyrins and phthalocyanines (966), for establishing the electrode reactions for vitamin BIZ (884), and for studying washed suspensions of intact human erythrocytes (6). The reduction of several tetroses in phosphate buffers (219) and for human -yG immunoglobulins (258) was reported. Polarographic data for Gascorbic acid and erythorbic acid after exposure to air (91s) and for scorbamic acid which was compared to ascorbic acid (579) were discussed. Polarographic changes as the results of denaturation and renaturation of tobacco mosaic virus protein were investigated (780). The effect of powerful irritants and biologically active substances on the level of serum sulfhydryl groups (4S2), energy functions of dog lung mitochondria (111), the activity of succinate oxidase from new born rat brain mitochondria (973), and the kinetics of a thiamine reaction in base solution (94s) were examined polarographically. An anodic wave that was observed for fresh mitochondrial suspensions was studied as a function of sample aging (761). Polarographic data for insulin which has been recrystallized ten times were described (642). The level of SH groups and the characteristics of the wave for rat blood serum were correlated to chemical and physical stresses applied to the rat; the larger the stress was, the lower the level of SH group (4S0). I t was suggested that the reactivity of the Co atom in cobalamines and cobinamides as determined by polarography is influenced by the nature of the ligands (342). Denaturated DNA and single stranded polycyclidylic acid were studied by ac, dc, and other polarographic techniques as a function of pH and inert electrolyte (91,92). The polarographic variables for native and denatured calf thymus DNA were described (238). Several detailed electrochemical studies of biological compounds and model systems were presented. Detailed mechanistic studies for the oxidation of NADH analogs (75, S l 7 ) , tyrosine a t a carbon paste electrode (461), uric acid in aqueous solution (the electrode reaction product was uric acid-4,bdiol which fragments rapidly) and methanol (4,5dimethoxyuric acid was the product) (196), and for guanine a t the pyrolytic graphite electrode as a function of pH (199) were reported. Detailed mechanistic studies for the reduction pyrimidine, cytosine, purine, and adenine (197), parabamic acid, methylparabamic acid, and dimethyl
ANALYTICAL CHEMISTRY, VOL. 44,
NO. 5, APRIL 1972
467 R
parabamic acid as a function of pH (198), alloxan, methylalloxan, and dimethylalloxan (Si), adenine nucleosides and nucleotides as a function of pH (adsorption effects were noted) (393), folic acid and its dihydro and tetrahydro derivatives (603),and for C1, Br, and I derivatives of uracil, 1methyluracil, 1,Mimethyluracil, and their corresponding nucleosides or oligonucleotides (970) were reported. Direct current polarographic and cv data compared to previously reported OScillographic data (396). A one-electron reversible wave was observed for pyrimidine in acetonitrile to produce an unstable radical which deactivates via two competitive pathways; the effect of proton donors on the reduction mechanism was also considered (688). The electrochemical behavior of ubiquinone in acetonitrile was studied as a function of pH (600) and in methanol where a two-electron process, complicated by adsorption, was found (676). Droptime controlled polarography was used to study the reduction of pyrimidine as a function of pH (898, 899). Five different porphyrin derivatives were studied in detail in D M F and their reduction paths were identified (726, 727). A detailed electrochemical study of Zthiopurine, and 2,6thiopurine a t pyrolytic graphite electrode and the D M E were reported as a function of pH; the electrode reactions and products formed during the reactions were identified (193-196). A total of eight waves was found for the reduction of purineFourteen 2,6-disulfonic acid (672). amino acids were studied in DMSO; nine gave a one-electron hydrogen wave while the other five gave multiple waves (467). An anomalous wave was observed and discussed while studying 6aminoand 6alkylaminopurines (394). A reduction scheme involving a mixed ferrous-ferric intermediate was suggested to account for the polarographic behavior of ferriheme (411). Enzyme hydrolysis of p-nitrophenyl esters and p-nitroanilides (IS), uptake of 0 2 by living organisms (SO), oxidations of carbohydrates by periodate (160), reduction rate of methylene blue by bacteria (586), and 02- hemoglobin equilibrium (337) was followed by polarographic methods. Respiration of plant mitochondria suspensions were measuyed polarographically (776). Cholinesterase activity in blood (662), dehydrogenase activity in Saccharomices vini (66W),and catalase activity in soil (772) were determined polarographically. Pulse polarography was used for the analysis of nucleic acids (966) and for protein in the range 0.05 to 10 hg/ml (693). Ascorbic acid in a-ray radiation studies (149), in apples (806), in mixtures with erythorbic acid (414), and in mixtures with folic acid 468R
and riboflavine in mono- or polyvitamin mixtures (606)was determined polarographically. Other quantitative polarographic procedures were reported for reducing sugars (IO@, saccharin in nonalcoholic beverages (379), for %keto sugars ( 9 3 ~ 9 ,and for glucose using an 0,electrode and glucose oxidase (401, 418, 683,684). Carbonyl groups in starches and related carbohydrates after reaction with o-phenylenediamine were analyzed polarographically (887-890). Polarographic methods were used to determine albumin, heme, hemoglobin, serum, capillary blood, peroxydase, and H202 (119), polarographic activities of fish protein before and after freezing, pickling, and smoking (180), cystine, N-methyl crystine, and thermoprine (186), cystine in seeds and herbs (186), activity of blood serum (347), and galanthamine (963). An ac polarographic procedure was used for the analysis of SH group in turbid solutions (143). Methylene blue in microbiological stain solutions was analyzed (90). Several applications and detailed studies of the Brdicka wave were described. The effects of ionic strength, concentration, buffer, and surfactants were surveyed in detail using the Co (11)-buffer system and five different S compounds (476) and with a Ni(I1)buf€er-cysteine system (612, 613). Polarographic adsorption currents obtained under Brdicka conditions were theoretically interpreted (633). Two previously unknown type of catalytic H-currents in addition to the Brdicka wave were observed for a Co(I1)thiolate system (678). Proteins in the presence of Co(II), Co(III), and Ni(I1) (383),seven different proteins (6W0), thiamine (663), several mercaptans (61W ) , bilirubin (769), and cystine-cysteine system (983) were investigated under Brdicka conditions. Bacterial a-amylase and polyvinyl alcohol were thiolated and gave the typical Brdicka wave (616). Albumin al-, a2-, 6-, and v-globulin fractions in human serum were separated chromatographically and determined by Brdicka conditions (348). With pulse polarography, the limit of cystine detection under Brdicka conditions was reported to be 5 X 10dgM (281). A catalytic wave in a Cophthlocyanine-thio mixture was studied (614).
Pharmaceutical Compounds. Polarographic characteristic and procedures for analysis were reported for chlordiazepoxide (two two-electron steps) in tablets (386), 1,6bis-(2chloroethylamino)-l,6bisdesoxy-~-mannito~ dihydrochloride derivatives (387-392), tetracycline derivatives (199, 760), and for antibiotic pigments similar in chemical nature to the anthracycline group (191). Analytical procedures were de-
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
veloped in ac polarographic studies of warfarin (4779, dicotinic acid esters and polyethylene glycol fatty alcohol ethers @SI), and of 4,4’discet~xydiphenyl-% pyridylmethane (870). Oxazepam (7-chloml,3,dihydro-3-
hydmxy-5phenyl-2H-l,4bensodia~pinZone) was studied electrochemically as a function of pH, reduction products were identified, and procedures for its analysis were developed (838, 678, 680, 681, 960). Two reduction waves were reported for nitrazepam (a nitro derivative of oxazepam (679). Chlordiazepoxide, diazepam] and diazepam in oxazepam in tablefs (lM), human plasma (63), and medazepam (677) (the latter two are chloro derivatives of oxazepam) were determined ‘polarographically. Polarographic procedures for the determination of thimersol (sodium ethylmercurithiosalicylate) (69, 687), bayluscid (5,2‘dichloro4’-nitrosalicylanilide-ethanol-amine salt) (786), riboflavine, thiamine hydrochloride, and niacinamide content in pharmaceutical preparations (802), rubomycine (190), nicotinamide (64!2), menadione sodium bisulfite in drugs and fodder (637), vitamin Dz in irradiated samples of ergesterol (79), chloramphenicol cinnamate on a syrup (161), glyceryl trinitrate in tablets (244), morphine (671), and for 4-methyl-aesculetin 6,7bis(hydrogen sulfate, sodium salt) (39, 167) were reported. An oscillographic method was used for the analysis of the decomposition of penicillins (206) and for ketophenylbutazone intermediates and derivatives (226). Dienestrol, 4,4’-(diethylidenethylene) diphenol, in creams was determined after conversion to a nitrosophenol derivative (869). Nicotinamide after separation (642), adrenaline after reaction with potassium tetrathiocyanatomercurate (644), dichlorobis-(nicotinamido-Co) (coamid) (646), and for the contraceptive 1-cinnamyl-3,Pdihydro6,7dimethoxy-isoquinoline hydrochloride (667) were determined polarographically. NITROGEN-CONTAINING HETEROCYCLIC COMPOUNDS
Pyridine-Quinoline Derivatives. The effect of electrolyte on the catalytic wave for pyridinium solution was reported (684, 688). Polarographic data were reported for nicotinamide derivatives (666),six dihydropyridines as a function of pH (619), pyridine, quinoline, and acridine derivatives as a function of pH (623, 744), and for pyridyl substituted urea and thiourea derivatives (674). Cyclic voltammetric data were described for 1,l’-polymethylenebis(3-carbamidopyridinium bromide) Stable radical derivatives (678). cations were obtained for the reduction
of 6,7dihydro-6-hydroxydipyrido-( 1, Za:2',1'-c)pyrazinium dibromide and dipyrido(1,Za: 2',1'-c)pyrazinium dibromide (74). Acetyl- and benzoylpyridine N-oxides were found to have the same anomalies as other 2- and 4substituted pyridine N-oxides (637). The polarographic waves from picolinic, nicotinic, and isonicotinic acids were due to protonated species; the kinetic nature of the wave was discussed, and used for analysis (187). Polarographic data for nine l-ethyl2(pX-styryl)pyridinium iodide derivatives were recorded as a function of pH and the substituents' effects were discussed in terms of the Brown-Okamoto equation (888). The mechanism for the reduction of 2,5disubstituted pyridine derivatives was discussed and the data were correlated with Hammett constants, and infrared and ultraviolet spectra (910). Benzyl pyridinium and benzyl quinolinium thiocyanates (608) and nicotinic and isocynchomeronic acids (814) were studied and determined polarographically. Polarographic data were reported for 4-[&(pyridyl)vinyl]quinoline and its ethyl derivative as a function of pH (149), for 1,1'dimethyl-2,2'-biquinolinium dimethsulfate (180), and for methiodides of quinoline, isoquinoline, 3,4-, 5,6-, 7,8-benzoquinoline, and 0 - , m-, and p-phenanthroline derivatives (436-438). I n the latter study, detailed electrochemical measurements were done and the data were correlated to Hueckel MO calculations. A vibrating dropping mercury electrode was used in studies of noncatalytic waves for quinine, quinoline, and 3-aminoquinoline (166). Anodic voltammetric data were reported for phenolic derivatives of isoquinoline (864). Heterocyclic Compounds with Two or M o r e Nitrogens. The effect of substituents and pH on the reduction of substituted quinoxalines was investigated (291, 731). A mathematical model was proposed which described the change of the polarographic waves for quinogaline derivatives (801). Phthalazine derivatives were studied as a function of pH (670). 1-Diethylaminoethyl- 3- (4-methoxybenzyl) quinoxalone was studied a t pH 12 and the wave was used for analysis (728). Several 4substituted quinazolines (628) and substituted quinazolinones (data correlated to pK. values) (620) were studied polarographically. 2Chloromethyl- 4- phenyl-6- chloroquinazoline-3-oxide commercial products was determined polarographically (124). Electrochemical oxidation for 2,4,5triarylimidazol anions was reported and data for substituted derivatives were correlated to Hammett values (866, 867). Oxidation data and a Hammett substituent correlation were found for fifteen triarylimidazolyl free
radical derivatives (1.61). Six derivatives of 2,3dihydro-l ,Miazepinium perchlorates were studied as a function of pH and the reduction was found to eventually lead to ring opening (154). Data for 1,3dihydro-2H-l,4-benzodiazepin-&ne and Zthione derivatives were reported as a function of pH and correlated to Hammett constants (78). Half-wave potentials for substituted porphyrins were correlated to energies of lowest vacant molecular orbital (589), while anodic and cathodic waves for porphyrin and tetrazoporphyrin derivatives were compared to photochemical reactions and energies of the excited states (860). Porphyrin derivatives in petroleum were analyzed by polarography (816). Cyclic voltammetric and dc polarographic data were reported for nineteen different azaaromatic compounds and the data were correlated to CNDO data (964). Mono- and diaza compounds were studied by oscillopolarography (6H). The reduction of azabenzenes, azanaphthalene, azabiphenyl, and N-methylazinium salts in D M F (561) and for Zazaniaazulene salts (904) was investigated. Oxidation of theobromine and caffeine (328), theophylline (330), and other xanthines (319) was studied in detail a t the pyrolytic graphite electrode. The reduction pathway for three barbituric acid derivatives was reported (413). Three waves, adsorption, catalytic, and diffusion controlled, were observed for the reduction of 1,4diphenyl - (3,5- endanil)-dihydro - 1,2,4triazole (161). An oscillographic technique was used for the determination of small amounts of active triazine dyes (611). The effect of light on dl-lupanine was investigated (48). The reduction mechanism for 1,2dimethyl-3-arylpyrazolium perchlorate (906) and for oxadiazoles in D M F and in the presence of proton donors (844) was described. 3-Carboxy4oxo-6,7 ,8,9-tetrahydro-homo-pyrimidazol was studied as a function of pH (306). Hammett substituent correlations were possible with ac and dc polarographic data for 1- and 2-substituted phenazines (652). Derivatives of ~-triazolo-[d]pyrimidine were studied and the data were correlated to energies of lowest vacant orbitals (682) Oscillopolarography was used for the determination of pyrimidine triazoles (294). The mechanism for the reduction of 2chloro-, 2,4-dichloro-, and 2,4,6-trichloropyrimidine was investigated as a function of pH (168). Several pyrimidine derivatives were determined polarographically (68). Nitrogen, Nitrogen-Sulfur, Nitrogen-Oxygen Heterocyclic Compounds. Polarographic data were reported for eight acridine derivatives as a function of pH (160), for morphine oxidation a t
a Pt electrode (764), and for benzoxazone and quinazoline derivatives in DMF (178). The reduction behavior for several isatogen derivatives, XXIX, 0'
R 0XXIX was suggested to follow a quinone type reduction (117). The reduction mechanisms were reported for diaza-aromatics in D M F and in the presence of proton donors (936, 937). Polarographic determinations of l-phenyl-4-amino-5-chloropyridamne and its impurities (308) and piperazine in animal feeds (577) were reported. Polarographic data for 2,3,4,5-tetraphenylpyrrole in anhydrous nitromethane (663) and for 4,3',5'-trimethyl-3, 4'-diacetyl- 5- carbethoxydipyrrylmetha n e H B r and other pyrrole derivatives (617) were reported. Electron affinities and ionization potentials of twenty photosensitive cyanine dyes were calculated from II-electron energy potentials and half-wave potentials (896, 896). Polarographic data and a procedure for the analysis of 9-methyl%acetyl carbazole was reported (384). The polarographic behavior of benzoxazole, benzothiazole, and benzodithiol (368), 2,5-disubstituted-4-oxazolidinones (374), isoxazoline N-oxides (648), and of 3H-phenoxazine-3-one (884) was reported. Z(1-Naphthyl)&phenyland 2,5diphenyloxazole were studied in detail in the presence and absence of proton donors (304). Oscillopolarographic data were reported for a series of gallocyanine dyes (497). Analytical procedures for the analysis of 1,5diphenyl-3- styrylpyrazoline and di[Z(&phenyl)- oxyazolyll- benzene (443) and for dubinidine after chromatographic separation (763) were described. The polarographic behavior of 347methylbenzylideneamino) 4 phenylthiazoline-sthione (690), benzoxazolinone, benzoxazoline, and derivatives (876), and for methylene blue (96, 696) were reported. Eighteen phenothiazine derivatives were analyzed by ac and dc polarography (289). The reduction of diazaphenothiazine derivatives was described (699). Derivatives of iminooxo- and iminodioxo-thiazolidines (881) and of thiazole and 1,3,4thiadiazole (834) were studied. The effect of substituents in the 3 and 5 position were considered in an investigation of thiazolidine derivatives (283).
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ACKNOWLEDGMENT
The author thanks Sherlock Swann, Jr., and Stanley Wawzonek for their valuable assistance in scanning Chemkal Abstractn.
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
469R
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Polarographic Theory, Instrumentation, and Methodology Richard S. Nicholson, National Science Foundation, Washington, D.C. 20550
T
m v m w FOLLOWS the pattern of the previous one (238), selectively covering literature from December 1969 to December 1971. The scope is defined by my interpretation of the assigned title, but in any case “polarographic” is taken to include the other major techniques. Papers involving only applications generally are not cited. Books and Reviews. Several books related to the topics of this review have been published in English or translated into English. The textbook on electrochemistry by Koryta, Dvorak, and Bohackova, which was first published in Czechoslovakia in 1966, can now be read in English (188). HIS
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Two books by Zuman have been published (338,333). One of these (333) is a set of reprints covering the past twenty years, and the other (332) is based on a 1967 series of lectures. Both deal with organic polarography. The electrochemistry of organic compounds also is the subject of a book by Mann and Barnes (212). And speaking of adsorption, the authoritative book by Damaskin, Petril, and Batrakov has been translated from Russian (92). Similarly, the original 1969 “Progress in the Electrochemistry of Organic Compounds” edited by Frumkin and Ershler is now available in English (120). Headridge (139) has written a book
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
which he says is designed to introduce electrochemistry to inorganic chemists. His book does not possess the scope or rigor of some purely electrochemical texts, but it is short and readable, and might be a good place for nonelectrochemical colleagues to get a start. Polarography is the subject of a French book by Pointeau and Bonastre (868), and a chapter by Muller (229). Muller’s contribution is part of two volumes devoted to electrochemistry in the newest version of the famous “techniques” series edited by Weissberger. These two particular volumes (314, 516) are of general interest and additional chapters will be mentioned below.
