Organic Electrochemistry in the USSR

Mairanovsky, Victor G.

doi:10.1007/978-3-319-21221-0_9

Victor G. Mairanovsky^2,3

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Abstract

Organic electrochemistry (in the Russian scientific literature “electrochemistry of organic compounds”, “EKhOS”) describes the whole field. In addition to electroorganic chemistry (synthesis, organic reactivity, etc), it includes also mechanisms of electrode processes including kinetics of separate stages, electrode and pre-electrode effects, combined spectral and electrochemical techniques, etc., as applied to a variety of objects—from simple molecules to complex natural compounds. The article provides an overview of works in all of these areas performed in the EKhOS's centres of the former USSR: in Moscow, Kazan, Riga, Tula, Novocherkassk, etc. In the second part of the article the author shares over 30-years experience at the Moscow's All-Union Scientific-Research Institute of Vitamins-from the first work with home-made polarograph, studying the mechanisms of reactions, to large-scale industrial electrosynthesis. Along with biographical material, author describes also the environment in which soviet scientists lived and worked in those years.

An erratum of the original chapter can be found under DOI 10.1007/978-3-319-21221-0_17

An erratum to this chapter can be found at http://dx.doi.org/10.1007/978-3-319-21221-0_17

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The English scientific literature commonly refers to this field as “electroorganic chemistry,” often emphasizing the synthesis and its connection to organic chemistry. The first electrosynthesis of an organic compound—the anodic conversion of acetate to ethane—was conducted 180 years ago by Faraday [1]. Kolbe made a preparative procedure of this [2], which, as “Kolbe electrolysis,” is now considered to be the birth of “electroorganic chemistry” [3, 4]. In the Russian scientific literature, the term “electrochemistry of organic compounds” (“elektrokhimiya organitscheskikch soedineniy” = “EKhOS”) is used for the English “organic electrochemistry.” Both these terms describe the whole field of electrochemistry, which, in addition to electroorganic chemistry, includes determination of mechanism of electrode processes along with kinetic parameters of its stages, studies of electrode and pre-electrode effects (adsorption, electric field, etc.), combined spectral and electrochemical methods, analytical applications, etc. Thus, given the vast range of methods and objects falling under the domain of organic chemistry—from simple molecules to complex natural compounds and macromolecular polymer structures—organic electrochemistry opens very wide fields for research. The work of Fritz Haber [5] may be considered as the beginning of EKhOS. He was the first to recognize the importance of the electrode potential in formation of various products and to conduct electrolysis of an organic substance (nitrobenzene) at controlled electrode potential, establishing the sequence of transformations.

So what is left over from organic electrochemistry in the USSR? More than 20 years after the disintegration of the USSR, those works are now history, as is the era in which we lived and worked. In this article, I will describe the research and also the circumstance under which it was done, and I will share some of my personal experience (Sect. 9.2). The systematic bibliography at the end may be useful for a reader interested in the history of science. As a rule, the references are given to the original Russian sources.

In contrast to applied electrochemistry and fundamental (theoretical) electrochemistry (Frumkin and his disciples), organic electrochemistry was not considered as a priority in the USSR until 60-ies. For example, in the textbook on kinetics of electrode processes [6], published by Frumkin et al. in 1952, only a few pages relate to electrochemical transformations of organic compounds. There were also no state-run programs to develop specialists in the field.

The advances made in polarography in the USSR became a decisive factor for a considerable acceleration of organic electrochemistry. In the early 1950s, first studies were published on organic polarography outside of analytic applications (Мoisei Neiman , Stal’ Mairanovskii , Emmanuil Levin ) (e.g., [7, 8]). This direction was also promoted by the Czech polarographic school on the theory of kinetic and catalytic currents (Koryta , Koutecky , Hanuš ) and by Peter Zuman ’s studies on the relations between the half-wave potential E _1/2 and the structure of compounds. The school of Frumkin and its achievements in detailed studies of the processes on the dropping mercury electrode (DME), including adsorption phenomena, polarographic maxima of the first and second kind, features of the electroreduction of anions, etc., has played an important role (Krjukova , Nikolayeva-Fedorovich , Damaskin , Petrii, et al.).

The beginning of the USSR production of instruments for electrochemical measurements played a major role in further developments. Those instruments were developed primarily by S.B. Tsfasman and I.Ye. Bryksin in the TSLA (Tsentralnaya Laboratoriya Avtomatiki, Moscow) [9]. Advanced equipment from TSLA became available: the polarograph PE-312 with fast recording; the oscillographic polarograph PO-5122 with a recording oscilloscope; the powerful potentiostat P-5827 with an output voltage up to 200 V; the a.c. “vector polarograph” (see Chap. 5, Sect. 5.9). A strong group developing electrochemical equipment has been established at the Kazan's Aviation Institute (R. Sh. Nigmatullin , M. R. Vyaselev, A. I. Miroshnikov et al., oscillographic polarographs with differential mode and with fractional differentiation, etc), Zaretskiy’s and Bruk’s group in Ordzhonikidze, North Ossetia (automatic polarografic analyzers), etc. [10–12].

A series of regular scientific conferences of electrochemists started in the late 1950s; in the spirit of the time, they were called “soveshchanie” (meetings) instead of “konferentsiya” (the Russian word borrowed from foreign languages). The first polarographic conference took place in Kishinev (Moldova) in 1958 (hereinafter “conference” will be used instead of “soveshchanie”). The first conference on EKhOS was held in Moscow the same year in the Institute of Electrochemistry, Academy of Sciences, IELAN. Proceedings of the conferences became available from the fifth EKhOS conference (Moscow 1965) onwards as a series of books Progress of Electrochemistry of Organic Compounds. There were seven such books published prior to 1990; they formed the “EKhOS encyclopedia” [13–20]. Frumkin initiated the EKhOS conferences which he believed of great importance for the future developments in that field. It so happened that he passed away in Tula on the first day of the EKhOS-76 conference which was planned to start with his opening. I remember him on a sunny morning of May 27, 1976, standing by a column in the lobby of a Dom kultury (“house of culture”) of a chemical plant. He felt ill; there were few people around him. In the meantime, it was getting late and the conference participants were ushered into the meeting room. Alexander Naumovich Frumkin was taken to the hospital; a few hours later he passed a way.

By the first half of the 1970s, the Soviet Union had several centers specializing in various areas of organic electrochemistry. At that time, an intensive growth of that field began in many cities of the USSR—in Moscow, Kazan, Riga, Kharkov, Novocherkassk, Tula, Alma-Ata, Karaganda, Kishinev, Tbilisi, and other cities. Here is a brief description of few of these centers, direction of their work, and staff. The information is arranged by “geographical principle.”

9.1 Organic Electrochemistry in the USSR: The Main Centres and Fields of Work

9.1.1 Moscow and the Moscow Region (up to 200 km)

First of all, there were two centers founded and led by Frumkin : the Department of Electrochemistry of Lomonosov Moscow State University (MGU) and the Institute of Electrochemistry of the USSR Academy of Sciences (IELAN). Their role was invaluable in the formation of modern theoretical concepts and also in the developments of applied electrochemistry. Organization of all aspects of EKhOS conferences, from selection of the principal theme to publication of the next volume of Progress of EKhOS, was held under the auspices of IELAN. The Electrochemistry Department of the MGU published a textbook [21] focused on adsorption of organic substances on electrodes—an issue previously not addressed in any textbooks. Important contributions to the study of the adsorption of organic compounds on the electrode were made by G.A. Tedoradze , A.B. Ershler , L.G. Feoktistov , and M.M. Gol’din , all at IELAN (see G.A. Tedoradze [13], p. 23).

Considerable efforts were made to develop new methods applicable to EKhOS: photo-electrochemical methods, photoemission techniques (Yu.V. Pleskov , Z.A. Rotenberg, etc.), chronopotentiometry (A.B. Ershler [17], p. 199), etc. The pioneering work on ring-disk electrode was published by Frumkin and Nekrasov [22]; this technique has proven particularly useful for the study of electroorganic reactions. The two “Frumkin centers” (MGU and IELAN) were also invaluable for specialists from other centers. For instance, I remember with gratitude the regular EKhOS seminars by Leonid Feoktistov . In IELAN, I met and became friends with Alexander Ershler (Fig. 9.1) and Zakhar Rotenberg ; later on we had several joint projects. This book includes a separate article on the contribution of Frumkin ’s school by Oleg Petrii who was one of the leading scholars of that school (Chap. 4).

The Department of Organic Chemistry of MGU cultivated another direction—electrochemistry of organometallic compounds. In the late 1960s, Kim P. Butin investigated systematically mercury-organic compounds by polarography, as part of joint research with Ershler. One of the outcomes was a method for estimation of pK _a of weak CH acids based on the relationship between pK _a and E _1/2 of the “organic calomels” R₂Hg. That method was used to determine the CH acidity of about 50 hydrocarbons starting with methane [23–25]. Later, Butin’s laboratory studied intramolecular charge transfer complexes, electrocatalytic methods, and electrochemical modeling of enzymatic catalysis [26].

There were three research institutes of the USSR Academy of Sciences (USSR AS) in Moscow with groups working in organic electrochemistry. The largest center was at the Institute of Organic Chemistry (IOKH). It all started with Stal’ Grigorievich Mairanovskii who joined the Institute in 1956 as a 30-year-old, already a Ph.D.. Stal’ Mairanovskii (Stal' Mayranovskiy in Russian transcription) is rightfully regarded as belonging to Frumkin ’s school, although he specialized in technology of organic chemistry at the Moscow Lomonosov Institute of Fine Chemical Technologies (MITKhT) during 1943–1948.^{Footnote 1} Numerous papers and books published by him and in cooperation with Soviet and foreign scientists (Frumkin , Levich , Kharkaz, Khaykin, Tedoradze , Ershler , Stradin, V.D. Bezuglyy, Koutecky , Hanuš, et al.) show the breadth of his scientific interests (Fig. 9.2).

Stal’ Mairanovskii started out in organic polarography in 1950 at the chemical pharmaceutical plant “Akrikhin” near Moscow. After an unsuccessful interview attempt for a postgraduate course at Moisei B. Neiman ’s laboratory at the Institute of Chemical Physics of the USSR AS (as an “A” student, he “failed” in the philosophy exam—a common trick in the USSR to block “persons of Jewish nationality” from universities, postgraduate studies, etc.), he continued to work at that plant. He was at Akrikhin from 1948 to 1956 working his way up from being an engineer to head of production facility. During that time, he carried on his research and completed several projects with M.B. Neiman , which Frumkin submitted for publication in the journal Doklady AN SSSR [7, 27, 28]. Almost 20 of Stal’ Mairanovskii’s articles were recommended by Frumkin for publication in the prestigious Doklady AN SSSR in the 1950s–1960s, and Frumkin was highly selective!

Mairanovskii defended his Ph.D. thesis in 1953. The new theory of catalytic hydrogen evolution (B and DH are the catalyst and proton donor) was a part of that thesis:

$$ \begin{array}{l}\mathrm{B}+\mathrm{D}\mathrm{H}\rightleftarrows {\mathrm{BH}}^{+}+{\mathrm{D}}^{\hbox{--}}\\ {}{\mathrm{BH}}^{+}+\mathrm{e}\rightleftarrows {\mathrm{BH}}^{\cdotp}\\ {}2{\mathrm{BH}}^{\cdotp}\to\ 2\mathrm{B}+{\mathrm{H}}_{\mathbf{2}}\end{array} $$

(9.1)

Stal’ Mairanovskii was one of the first to apply the results of Koutecky and Hanuš for investigating electrode processes with chemical stages, and in so doing, he introduced the concepts of “volume” and “surface” chemical stages [29] and demonstrated the role of “surface” reactions. Several studies on the verification of schema (9.1) were carried out in cooperation with Czech scientists [30–32]. This material demonstrating a new approach to the analysis of polarographic waves to find the kinetic parameters taking into consideration adsorption and electrical double layer effects was summarized in [33, 34]. That monograph became one of the first books of Soviet electrochemists translated and published in the West. A number of pioneering ideas were presented in the monograph. Among them were the concept of “inheritance effect” (according to which the product of the electrochemical stage may retain structural elements and the adsorption orientation of the initial reagent), prediction and a proof of significant pH change in pre-electrode layer due to a strong electric field, and application of polarography at hydrostatic pressures up to 3000 kg/cm², in particular for the study of surface chemical reactions [35–37]. Stal’ Mairanovskii himself and in cooperation with other scientists published several other monographs [38–40], which helped to advance EKhOS in the Soviet Union. The first results directly related to electroorganic chemistry included the discovery of a difference in the electroreduction of cis- and trans-1,2-dibromethenes [41], establishment of an activating effect of the nitro group during cathode rupture of the C–halogen bond [42], and determination of electroreductive transformations of polynitroalkanes (PNAs) with regard to α-CH acidity [43–45]. The works of Stal’ Mairanovskii and his associates and postgraduates laid the foundation for the studies of EKhOS at the Institute in years to come. For instance, V.A. Petrosyan and M.E. Niyazymbetov’s study of electrooxidative transformations of PNA led to the discovery of interesting synthetic pathways [46–48]. They found that the intermediate PNA radicals form corresponding nitroalkylaryl arene derivates in the presence of arenes, instead of expected deactivation radicals by a cleavage of C–N bond or by the attaching of H atom from the medium:

(9.2)

Based on that mechanism, the effective anode syntheses of polynitroalkyl arenes [50] and ylides (if heteroarene is taken instead of arene) were developed. The process involved an intermediate arenium cation following path –ea–e–p and –ea–ed, respectively.^{Footnote 2} Vladimir A. Petrosyan ’s group (since 1986, it is the Laboratory of Organic Electrosynthesis) studied other reactions of anodic substitution, S ^H_N reaction, and generation of carbenes [51] (Fig. 9.3). The works on the cathodic de-protonation of weak acids [49, 50], which started in the late 1980s (electrochemical versions of Michaelis–Becker, Wittig–Horner, and Perkin reactions), found interesting preparative applications. A series of original electrosyntheses was performed also by Dr. Michael N. Elinson ’s group, in particular, synthesis using electrochemically induced chain reactions [52]. In 2011, 55 years after the beginning of EKhOS by Stal’ Mairanovskii , the works of these two groups from IOKH were honored with the N.D. Zelinsky Award.

The Institute of Organoelement Compounds of the USSR AS (INEOS) was founded by А.N. Nesmeyanov (1899–1980, the president of the USSR Academy of Sciences from 1951 to 1961 and director of the INEOS AN from 1954 to 1980). The work on EKhOS was conducted in several directions. The polarographic behavior of the tropylium cation [53] was first investigated here in 1957. Active studies of non-benzoid aromatic compounds were started in the laboratory of D.N. Kursanov , corresponding member of the USSR Academy of Sciences, after Mark Еfimovich Vol’pin has joined the laboratory.^{Footnote 3} In connection with research on the catalysis by metal complexes (Vol’pin’s pioneering work on fixation of nitrogen [55]), electrochemical studies on pi-complexes of transition metals and metallocenes were carried out in this laboratory [56–58].

Electrosynthesis works performed in the laboratory headed by academician Ivan Ludvigovich Knunyants deserve special mention. First of all, it is the reaction of acrylonitrile hydrodimerization (the term “hydrodimerization” was suggested by Knunyants and N.T. Gambaryan [59]). Using an electrochemically generated sodium amalgam, Knunyants and N.S. Vyazankin were first to get adipodinitrile, an intermediate in the caprolactam production, with reasonable yield [60, 61]. Direct electrosynthesis later proposed by Baizer [62] was implemented by Monsanto and became the world’s largest industrial organic electrosynthesis [63]. The ea ₂ p schema with dimerization of an intermediate anion radical was adopted for this process (DH is a proton donator)^{Footnote 4}:

$$ {\mathrm{CH}}_2=\mathrm{CHCN} + {\mathrm{e}}^{-} + \mathrm{D}\mathrm{H}\overset{{\mathrm{e}\mathrm{a}}_2\mathrm{p}}{\to }\ \frac{1}{2}\mathrm{N}\mathrm{C}{\left({\mathrm{CH}}_2\right)}_4\mathrm{C}\mathrm{N} $$

(9.3)

Another pioneering electrosynthesis was the “soft” fluorination developed by I.N. Rozhkov , I.L. Knunyants, etc. [64, 65]. Unlike the known “hard” fluorination in liquid HF [66], which leads to perfluorinated compounds, often accompanied by side reactions, the “soft” fluorination is a selective electrosynthesis. The process is performed on a Pt anode in MeCN at the oxidation potential of the substrate RH. The –ea _N –e–p mechanism is suggested for this reaction [67–69] (Figs. 9.4 and 9.5):

$$ \mathrm{R}\mathrm{H}\ \overset{-{\mathrm{e}}^{-}}{\to} {\mathrm{RH}}^{\cdotp +}\ \overset{{\mathrm{F}}^{-}}{\to} {\mathrm{RH}\mathrm{F}}^{\cdotp }\ \overset{-{\mathrm{e}}^{-}}{\to} {\mathrm{RH}\mathrm{F}}^{+}\ \overset{-\mathrm{p}}{\to} \mathrm{R}\mathrm{F} $$

(9.4)

The direction of F⁻ anion attack is consistent with the distribution of the density of positive charge [64, 65]. The “soft” electrochemical fluorination very soon attracted attention in the West and is extensively used and developed [70]. Ionic liquids [71], alkali metal fluorides in poly(ethylene glycol) [72], etc., were proposed to be used instead of organic solvents. Just as the “hard” electrochemical fluorination was called the “Simons process,” the “soft” fluorination should be referred rightfully to as the “ Rozhkov – Knunyants reaction.”^{Footnote 5}

As it happened, Knunyants became the opponent of my doctoral thesis. When Igor’ Rozhkov found out that I had prepared a doctoral thesis, he advised me to ask Knunyants to be the opponent. Rozhkov said that one of the research fields of Knunyants is the chemistry of natural compounds, and he is interested in electrosynthesis. Igor’ warned me, however, that he might decline—“Knunyants is known to be fastidious and now rarely examines dissertations.” Ivan Ludvigovich met me quite coldly and silently looked through the thesis. When he reached the section on the electrosynthesis of the oxytocin hormone, he perked up; he was previously involved in the chemical synthesis of this compound. Two weeks later, he agreed to be my opponent. Knunyants came to the Academic Council of Moscow State University wearing his general’s uniform and began his speech with an apology that he was due to have a meeting at the military academy later. He praised my thesis in his statement.

Ivan Ludvigovich was an outstanding scientist and an extraordinary person. In addition, to the well-known brilliant scientific achievements, in the narrow circles, he was also known for his so-called Knunyants absences (as per S.M.). Unlike many other prominent academicians, Knunyants did not sign condemning political letters in the Soviet newspaper Pravda. Every time he learned of a letter being prepared, he took a business trip and only few trusted people were privy to his whereabouts. On the contrary, Knunyants signed what became known as the “Letter of 13” against Stalin’s rehabilitation (1966). Along with academicians A.D. Sakharov and P.l. Kapitsa , in 1970, he also signed the “petition in support of Zhores Medvedev ”—a scholar and a writer persecuted for his revelatory book on T.D. Lysenko .

The Institute of Chemical Physics of the USSR AS in Chernogolovka. Dr. Vladimir Vasiljevitch Strelets (see Fig. 9.20) must be mentioned here as a renowned scholar in the field of electrochemistry of organometallic compounds and electrocatalysis by metal complexes. Dr. Strelets and coauthors performed pioneering studies on electroreduction of carbon oxide to methane with vanadocene as catalyst (electrochemical equivalent of Fischer–Tropsch process) as well as investigated the mechanism of transformation [73, 74]. Of great interest are also his other works on the electrochemistry of metallocenes including those carried out in post-Soviet period, e.g., studies on сomplexation of ferrocenes by cyclodextrins [75], generation of cobaltocene cations and anions over an extremely wide 6-volt potential range ±3 V SCE [76], etc. I first met Vladimir in 1963 in Alexander Ershler ’s laboratory (IELAN) and we kept in touch for many years until Vladimir Strelets , an original scholar and excellent experimentalist, passed away in Chernogolovka on October 7, 2014.

In the 1970s, a scientific group devoted to photoemission methods was established in the same institute under the direction of V. A. Benderskiy . An original laser photoemission technique (LPE) was developed and pioneering studies of short-lived intermediates of organic electrode reactions were undertaken (V.A. Benderskiy , A.G. Krivenko , V.A. Kurmaz , A.S. Kotkin, etc.); and the LPE was supplemented by classical electrochemical methods [77]. Using the LPE-measurements the рK _a values of weak acids (alkanes, benzene and their halogen derivatives) have been determined [77]. Both the direct generation of intermediates by solvated electrons (εc schema, the analogy to the usual ec reaction) and indirect generation by interaction of reagents with OH^·, H^· and other radicals (εсc schema) were developed. The photoemission measurements were supplemented by classical electrochemical methods. The results of more recent studies show the prospect of that approach for thermodynamic and kinetic characterization of short-lived intermediates [78, 79].

Among Moscow-based organizations, which successfully worked on EKhOS, were Moscow D. I. Mendeleev Institute of Chemical Technology (MKHTI) and a number of branch institutes. These organizations concentrated mainly on electrosynthesis for industrial applications.

The MKHTI’s Faculty of Technology of Electrochemical Productions was established in 1933, but research focused on electroorganic chemistry started in the 1950s–1960s by Mikhail Yakovlevich Fioshin and colleagues; Fioshin has also headed the new “EKhOS Laboratory” of MKHTI. Fioshin ’s team was first to use Brown–Walker synthesis and “additive dimerization” for sebacic acid and highly unsaturated dicarboxylic acid production [80–82]. The manufacturing of sebacic acid, an effective plasticizer for polymer materials, was established on a large scale by G.N. Freydlin (see Sect. 9.1.2) subsequently. Leonid Aleksandrovich Mirkind , M.Ya. Fioshin , and coworkers developed a technology for the production of drying oils implemented on a large industrial plant [83, 84]. In the course of these works, adsorption of neutral molecules at high positive potentials was unexpectedly revealed. This phenomenon was studied in detail by a number of electrochemical methods including radioactive indicator measurements [83, 84] and was registered as a discovery by the USSR State Committee on Inventions and Discoveries (no. 149, L.A. Mirkind , M.Ya. Fioshin , 1963) (Fig. 9.6).

Fioshin and coworkers also proposed the electrochemical synthesis of calcium gluconate [85] and diacetone-2-keto-l-gulonic acid (intermediate product in vitamin C synthesis [86, 87], see Sect. 9.2.7, “Electrosynthesis of Diacetone-2-Keto-l-Gulonic Acid in the Vitamin C Production”). In collaboration with electrochemists in Khar’kov (the group of Dr. Vasiliy Danilovich Bezuglyy, Sect. 9.1.6), they developed the technology for the production of salicylaldehyde [88]. M.Ya. Fioshin lectured applied electrochemistry to students, and a large number of specialists trained in his department continued to work in EKhOS.

A significant contribution to the development of technology of organic electrosynthesis was made by Dr. Andrey Petrovich Tomilov and his group at the State Scientific Research Institute of Organic Chemistry and Technology (GOSNIIOKHT).^{Footnote 6} A.P. Tomilov (Fig. 9.7), similarly to M.Ya. Fioshin , graduated from MKHTI, and the topic of his diploma thesis was the determination of the conditions for production of pinacol by cathodic hydrodimerization of acetone (1952). This electrosynthesis continuously improved by Tomilov and coworkers was developed on an industrial scale of 3000 ton/year in Stalingrad (1970). This work was distinguished by the highest award, the Lenin Prize (1971); however, the production was soon stopped after signing the Chemical Weapons Convention [89]. Another process also on the order from the military department was the synthesis of 4,4′-dimethyl dipyridyl (broad spectrum herbicide “Edil”) by cathodic dimerization of methylpyridinium chloride [90]. This process followed the classical ea ₂ schema and was implemented on a pilot plant [89]. A pilot-plant testing of electrosynthesis of adiponitrile was also performed by Tomilov and coworkers [91]. This process was more profitable than the initial version of the Baizer [62] synthesis because of significantly lower energy requirement. In 1964, the Belgian pharmaceutical company UCB became interested and a joint patent was lodged. However, due to unfavorable political circumstances, this method was not implemented despite promising pilot-plant tests. The development of these three processes took almost 40 years (!) of efforts by a large team of scientists and factory workers [89].

Tomilov and collaborators were the first to obtain trialkylphosphates by electrolysis of suspensions of phosphorus in alcohol + HCl [92]. This “direct” electrosynthesis of organophosphorus compounds using elementary phosphorus was further developed by the electrochemists in Kazan (joint publication [93]). It is worth mentioning that although Tomilov worked in a “closed” institute, he participated in many joint activities with electrochemists from “open” institutions in Karaganda, Ufa, Novocherkassk, Kazan, Charkov, and other cities. These contacts continued to post-Soviet times. I would like to mention, as an example, an elegant one-substrate paired electrosynthesis of γ-truxillic acid from the cinnamic acid (a joint work with the group by Е.Sh. Kagan , Novocherkassk Polytechnic Institute [94]). The derivatives of the truxillic acid act as a ligand-activated transcription factor of genes involved in glucose metabolism. The electrosynthesis realized in a diaphragm-less cell involves both anodic and cathodic C–C coupling reactions by the schema A–ea₂ Сeea. Process A on the anode is the dimerization of the electrogenerated cation radicals, and process C on the cathode is the C–C cyclization reaction after two-electron transfer; the alternative (more probable) schema is A↑–e↓a C ea, with the coupling-reaction between cation-radical and started molecul [94].

Tomilov took an active part in organizing and holding EKhOS conferences; he wrote several monographs on organic electrosynthesis in collaboration with Fioshin , S. Mairanovskii, and Smirnov . Some of the episodes from the scientific and organizational activities and memories of meetings with scientists are presented in his book [89].

All-Union Scientific-Research Institute of Vitamins (VNIVI). Electrochemical group headed by Victor G. Mairanovsky (in Russian transcription Viktor Grigorievich Mairanovskii). Main directions: mechanism of electroorganic reactions, homogeneous electrocatalysis, electrosynthesis in the chemistry of natural biologically active compounds incl. industrial processes (see Sect. 9.2).

9.1.2 Moscow Region, Tula

All-Union Research and Project Institute of Monomers (VNIPIM). Here, the initiator and supervisor of EKhOS was Dr. Gilya Naumovich Freydlin (1919–2009). He also enrolled in MKHTI in 1936.^{Footnote 7} In 1937, his father, a political worker of the Communist Party, was arrested as an “enemy of the people” and sentenced to 10 years of “bez prava perepiski” (“incommunicado”); this formulation was given in cases when the prisoner was shot. Gilya refused to formally condemn and abandon his father. The only reason he was not expelled from MKHTI was because of the support from two faculties (one of them was faculty of physical education because Gilya was among the top athletes of MKHTI). After graduating from MKHTI in May 1941, he was sent to work at the plant “Karbolit”—the largest Soviet plant for the production of plastics. The war began a month later and Freydlin was evacuated to Kemerovo, Western Siberia, together with the plant. At this plant, Freydlin was promoted from technologist to the head of the technology department of 700 (!) workers manufacturing a huge assortment of products. Starting from 1952, Freydlin worked in Yerevan at a “polyvinylacetate” plant (Armenia) and, from 1959, at the Severodonetsk branch of GIAP (Gosudarstvennyy Institut Azotnoy Promyshlennosti, “Azot” Association, Ukraine). In 1967, Freydlin came into VNIPIM and began with a team of coworkers to develop the world’s first industrial-scale electrosynthesis of sebacic acid [96, 97]. The process includes condensation of methyl adipate according to Brown–Walker synthesis (−eda ₂ schema), with subsequent hydrolysis:

$$ \mathrm{MeOOC}{\left({\mathrm{CH}}_2\right)}_4{\mathrm{COO}}^{-}\ \overset{-\mathrm{e}\mathrm{d}}{\to} \mathrm{MeOOC}{\left({\mathrm{CH}}_2\right)}_{\overset{\dot{c}}{4}}\ \overset{{\mathrm{a}}_2}{\to }\ \overset{{\mathrm{H}}_2\mathrm{O}}{\to} \mathrm{HOOC}{\left({\mathrm{CH}}_2\right)}_8\mathrm{COOH} $$

(9.5)

Based on the experience by Fioshin et al. [80–82] (Sect. 9.1.1.), Freydlin and his team solved a number of complex technological problems ranging from increase in the yield and current efficiency to the minimization of Pt-anode wear. Studies with ¹⁹⁷Pt isotope were carried out in this connection (Freydlin et al. [18], pp. 28, 49, 74). Freydlin ’s talent and his huge engineering experience were fully revealed here. Freydlin ’s team included E.P. Kovsman , S.S. Glusman , B.G. Soldatov , A.A. Adamov , etc. It became the most powerful engineering-technological group of organic electrosynthesis in the Soviet Union. A pilot plant of sebacic acid with capacity of 1000 tons/year was put into operation in 1974 and worked for about 8 years. The 10,000 ton/year industrial production of sebacic acid was established at the Severodonetsk Industrial Association in 1989 and became the largest organic electrosynthesis process in the history of the USSR. They also proposed an elegant solution for technology of electrosynthesis of the p,p′-azobenzoldicarbon acid HOOCC₆H₄N=NC₆H₄COOH, a valuable monomer for polyamide fiber production. The initial р-nitrobenzoic acid HOOCC₆H₅NO₂ was reduced according to the Haber schema [5]. The continuous process on the pilot plant was performed in two consecutive diaphragm-less electrolytic cells with oppositely directed flows of electrolyte 1[anode → cathode] → 2[cathode → anode]; here 1 and 2 refer to the cell’s numbers. Very high conversion (99.8 %) and product yields (97 %) were achieved (E.I. Kovsman et al. [18], р. 145). Unfortunately, the process has not been realized on an industrial scale.

Freydlin presented the works on the electrosynthesis of sebacic acid at Tula’s EKhOS-76 conference ([18], p. 28). Frumkin knew about these works and he came to Tula’s EKhOS-76. But as I have already said, Frumkin was not able to hear Freydlin ’s report…Following EKhOS-76, Freydlin and I kept meeting at other conferences and grew close over the years. Dr. Gilya Naumovich Freydlin retired in the late 1980s but for many years continued as a consultant at VNIPI. We last met in autumn 1992. I was visiting the Bolokhovskiy chemical plant, 40 km from Tula. My wife, Dr. Bella Lurik , the senior scientist at the All-Union Science Research Institute of Disinfection and Sterilization, had a working trip to the Tula Sanitary Disinfection Center, and our school-age daughter was also with her. Before returning to Moscow, we all met at Freydlin’s dacha (Fig. 9.8). Tula’s VNIPIM no longer exists, and there is no longer a production of sebacic acid in Severodonetsk. And now, as I write these lines, the area of Severodonetsk, Luhansk, and other Ukrainian areas are torn by the fratricidal war.

9.1.3 Kazan

This is the city of the founders of the famous Russian school of organic chemists, starting with N. Zinin and A. Butlerov. This tradition continued also during the Soviet era. Several EKhOS centers grew here: the Kazan State University (KGU) with the A.M. Butlerov Scientific Research Chemical Institute (NIKHI); the Chemical Institute of Kazan Filial of the Academy of Sciences (KHIKFAN) and the Kazan Institute of Organic Chemistry of the Academy of Sciences (KIOKH), from 1965 as the A.E. Arbuzov Institute of Physical and Organic Chemistry (IOFKH); and the Kazan Institute of Chemical Technology (KKHTI). Organic electroanalysis and electroorganic chemistry branches of EKhOS were mainly developed in Kazan. In 1937, the fourth year student of the KGU Vera Fedorovna Toropova (1915–2008) started in the field of polarography on her practical attachment at GIPKh in Leningrad (State Institute of Applied Chemistry) at the laboratory of Evgenia Nikolaevna Varasova, a disciple of J. Heyrovsky (see Chap. 5, Sect. 5.1).^{Footnote 8} Polarography of metallo-complexes with the emphasis on its analytical applications was the main scientific area of Toropova (Ph.D., KGU, 1941; Dr. chem. dissertation 1959) and many of her postgraduate students. As the head of Analytical Chemistry department (1957–1986), she made a great contribution to the training of highly qualified specialists [98].

Polarography gave also the beginning to electroorganic chemistry, and the first investigations were performed in this field by Yuriy Petrovich Kitaev in the late 1950s (Fig. 9.9). In 1941, Yu.P. Kitaev , a student of KGU, went to the front. After the war, he graduated from KGU and tried to attend a postgraduate course, but was blocked as a “member of the family of an enemy of the people.” In 1954, academician Alexander Ermingeldovich Arbuzov took him as a postgraduate student in his Laboratory of Organic Chemistry in KKHTI. This prominent scientist, the founder of the Kazan school of organophosphorus chemistry, set a task to trace tautomeric transformations in a series of aryl hydrazones by polarographic methods. The study of these compounds was a research topic for Kitaev and his disciples in KIOKH for many years [99–104]. His group also carried out studies on electrogenerated particles by the electron spin resonance or ESR. The combined in situ electrochemical (EC)-ESR was performed jointly with V.A. Ilyasov . Anion radicals of para- and ortho-chloronitrobenzene [105] and subsequently anion radicals of nitrophenylhydrazones [106] were taken as objects. These studies were among the first EC-ESR researches in the Soviet Union.^{Footnote 9} Studies performed by the group of Kitaev strengthened the authority of Kazan electrochemists. In 1960, A.E. Arbuzov sent Yu.P. Kitaev on a scientific business trip to the Jaroslav Heyrovský Polarographic Institute, Prague, and this was the beginning of a strong cooperation. Within a few years, G.K. Budnikov (1961 and again in 1972), Yu.M. Kargin (1966), and T.V. Troepolskaya (1972) went on internships to Prague. The insight into the experience of Czechoslovak electrochemists proved very useful for the development of EKhOS in Kazan [98].

The main centers and areas of work were identified from the mid-1960s. Gennadiy Konstantinovich Budnikov (Ph.D. 1962, “Polarographic investigation of semi- and thiosemicarbazones” under Kitaev ; later his works were also on organic polarography [101–103]) went from KIOKH to the Department of Analytical Chemistry, KGU, and focused on electroanalysis. On the other hand, Yuriy Mikhailovich Kargin (Ph.D. 1960, “Determination of low concentrations of some metals by differential oscillopolarography,” under the head Toropova ) moved from KGU to the Laboratory of Organic Chemistry of KIOKH and in 1961 began in organic polarography. Yevgeniy Alexandrovich Berdnikov (the Department of Organic Chemistry of KGU) was also involved in organic electrochemistry (α,β-unsaturated sulfones and sulfoxides, Ph.D. 1968, Dr. chem. 1989).

Gradually, Kargin ’s group became the center of EKhOS in Kazan. As a result of the Prague internships, the Kalousek switch became widely used in addition to the classical polarography. Later, more sophisticated electronic equipment had been utilized, e.g., the TSLA’s alternating current vector polarograph, the oscillographic polarograph with fractional differentiation developed by the R. Sh. Nigmatullin’s group in the Kazan Aviation Institute, etс. In the studies started in Kitaev ’s group [105], the EC-ESR technique became widely applied. Kargin et al. also studied more complex objects producing less stable anion radicals, in particular, the derivatives of aromatic carboxyl acids (joint work with A.V. Il’yasov and Ya.A. Levin [107–109]). After defending his Dr. chem. thesis, Kargin became the head of the Department of Physical Chemistry at KGU and lectured on physical chemistry and organic electrochemistry. The faradaic impedance technique was added to the already established electrochemical methods (L.Z. Manapova , the study of heterogeneous electron transfer in a series of carbonyl and nitro compounds). In 1971, the next EKhOS conference was held in Kazan with the active participation of Kargin [16]^{Footnote 10} (Fig. 9.10).

Along with the systematic study of the mechanisms of electroorganic reactions and electrochemical and chemical reactivity (aromatic nitro, carbonyl, carboxyl acid, S, Sе derivatives, etc., Dr. Venera Zaripovna Latypova ’s group), also synthetic works were started. According to Kazan traditions in organophosphorus chemistry, the applicability of electrosynthesis here was first evaluated. Original synthetic methods were developed in a series of works on electrooxidation of phosphines, esters of phosphorus acids, white phosphorus, etc. (Yu.M. Kargin , E. V. Nikitin [19], р. 115; [93]). Some of these transformations were difficult to implement with classical chemical methods. In addition to direct electrosynthesis, processes with mediators were also deployed (Yu.G. Budnikova , Dr. chem. thesis 1999, see review [110]). Since the 1980s, electrooxidative nitration was developed primarily for military products (nitrocellulose and nitroaromatic derivatives). Here, too, success was achieved, first in studying the oxidation mechanism of oxygen compounds of nitrogen and then in electrosynthesis of nitration agents (А.А. Chichirov , Dr. chem. thesis 1991). This work, which was conducted in NIIKHP (Science Research Institute of Chemical Products, Kazan), was awarded the Prize of the Council of Ministers of the USSR (1988). But because of the changes of the early 1990s and the lack of funding, this work was not completed and implemented.

Kargin created a large and prolific team of experts in organic electrochemistry; 6 doctor’s degree and over 40 PhD dissertations were defended here. And on one of my visits to Kazan, I was invited to the house of the lovely “Kazan EKhOS” couple Yurij Mikhailovich and Nonna Mikhailovna Kargin and their daughter Olga who was then graduating from the university. Since 1995, Dr. Olga Kargin lives and successfully works in Canada. Since 2001, Yurij Mikhailovich Kargin has also lived and worked there and continues his collaboration with his former coworkers in Kazan. An impressive list of joint publications is presented in the book [98]; a series of papers on electrochemical amination are among them (Yu.A. Lisitsyn , review [111]). Several groups headed by the former Yu.M. Kargin ’s postgraduate students, first of all, by Drs. Yu.G. Budnikova and V.V. Yanilkin’s, are actively working now. Thus the Kazan school of organic electrochemistry created by Kargin continues its life.

9.1.4 Riga (Republic of Latvia)

The Organic Synthesis Institute of the Academy of Sciences of the Latvian SSR (“OSI”) was founded there in 1957. The initiator and the first director was academician Solomon Aronovich Giller (1915–1975). In 1957, a young graduate of the Riga’s University Janis Paul Stradins^{Footnote 11} started to work at “OSI.” An article by Ya.P. Stradyn and S.A. Giller , “Mechanism of Polarographic Reduction of the 2-Nitrofuran” [112], was published in 1958. And this was the beginning of EKhOS in this institution. Heteroaromatic and aromatic nitro derivatives were the subject of study. Among them were the original antibacterials solafur, furagin, and furadonin, and others developed at OSI. 2-Nitroselenophene [113] was first investigated allowing to expand the understanding of electronic effect of the ring heteroatoms (N, O, Se, S). Polarographic studies of reduction of nitro compounds and the analysis of structural effects became the subject of Stradyn ’s Ph.D. thesis and of his first book [114]. Ja.P. Stradins and his coworkers used the Hammet and modified Yukawa–Tsuno, Taft, and Palm equations for the separation of inductive, mesomeric, and polar effects to supplement and extend the results of the Czech school (Peter Zuman ). Relations between the E _1/2 with energies of frontier molecular orbitals were also established (Fig. 9.11).

In addition to the nitro compounds, other groups of biologically active compounds such as heteroaromatic carbonyl compounds, diketones, quinoid systems, and phenols were investigated. The evaluation of “heterogeneous” electrode effects (adsorption on the DME, “surface” protonation stages, etc.) was taken as one the goals of these studies. Continuing the studies by Zuman and Lund et al., the activating effect of α-carbonyl group in reactions of cathodic bond dissociation in the series of phenacyl alkylthioethers [115] (process edep, dissociation of the C–S bond) and alkylamino indandiones (process p _s ede with the previous surface protonation, dissociation of the C–N⁺ bond) was found [116]. Thus, for C–S bond:

$$ \mathrm{ArC}\left(\mathrm{O}\right)\mathrm{SAlk} + \mathrm{edep}\ \to \mathrm{ArCHO} + {\mathrm{AlkS}}^{-} $$

(9.6)

This activating effect was first observed in breaking the C–C bond—by the example of bis-2-arylindandiones-1,3 [117]. A series of original papers was related to the electroreduction of 1,4-naphthoquinones and their derivatives [118, 119] as well as to the oxidation of dihydropyridines, dihydropyrimidines [120–122], and phenol derivatives on a carbon electrode [123, 124]. Ya.P. Stradyn and R.A. Gavar were apparently the first in the Soviet Union to use in situ combined EC-ESR for studying organic electrochemical reactions.^{Footnote 12} It was a very new and intriguing direction to compare electrochemical data with the biological activity of compounds. Ya.P. Stradyn and S.A. Giller made a big joint presentation on this at Riga’s EKhOS-73 ([17] p. 282).

Investigations of the electrochemical school in Riga were known in the West, and this group had the opportunity for contacts with foreign colleagues already in the Soviet era. Ya.P. Stradyn and his coworkers participated in many international meetings: in Prague, Liblice, Brno, Bucuresti, Warszawa, Wroclaw, Jena, Leipzig, Rostock, Berlin, Münster, Southampton, Sandbjerg, Uppsala, Lund , Rome, Venice, Tokyo, and Montreal. Ja.P. Stradins became also a highly respected and well-known scientist because of a series of scientific-biographical books and articles on Th. Grotthuss , P. Walden , and W. Ostwald and on the contribution of Baltic scientists and the role of the Baltics as “a mediator between the East and West” [129]. Biographical material on academician Ja.P. Stradins and his intensive and multifaceted scientific, literary, and social activities are presented in the recent book [130].

I shall briefly touch upon some other centers on organic electrochemistry, their staff, and main avenues of work.

9.1.5 Novocherkassk

Novocherkassk Polytechnic Institute (South Russian State Technical University)

1.
Groups of Drs. V.A. Smirnov and M.G. Smirnova . Main areas: amalgam-based synthesis ([13], p. 219) and electrode materials for electrosynthesis ([17], р. 7 and [19], p. 318). Dr. V.A. Smirnov is a coauthor of several books on organic electrochemistry [39, 131].
2.
Group of Dr. E.Sh. Kagan . A number of original electrosyntheses in a series of triacetone amine, piperidines, etc. [94, 132–135] (see also synthesis of γ-truxillic acid in collaboration with Tomilov, Sect. 9.1.1). This group continues now to actively work in the field of organic electrosynthesis.

9.1.6 Kharkov (Republic of Ukraine)

All-Union Research Institute for Single Crystals. Dr. V. D. Bezuglyy . A large number of studies on organic polarography (cf. monograph [40]), electrosynthesis and production technology of salicylaldehyde [88] (see Sect. 9.1), electrochemical polymerization [18] p. 161, [19] p. 265, [136, 137], etc.

9.1.7 Kiev (Republic of Ukraine)

Institute of Macromolecular Chemistry, Academy of Sciences of Ukraine. Dr. G.S. Shapoval . Electrochemical polymerization, electrochemical transformation of polymers, and electroreduction of perfluorocarbons ([19], p. 286; [138–140]).

9.1.8 Alma-Ata (Republic of Kazakhstan)

D.V. Sokolskiy Institute of Organic Catalysis and Electrochemistry. The group of academician D.V. Sokolskiy . Electrocatalytic hydrogenation [141, 142].

9.1.9 Karaganda (Republic of Kazakhstan)

Institute of Organic Chemistry and Carbon Chemistry. Dr. I.V. Kirilyus . Cathodic electrocatalytic hydrogenation processes, electrosynthesis of aliphatic alcohols, etc. [143].

9.1.10 Sverdlovsk

Institute of Chemistry and Metallurgy Ural Branch USSR AS and Tomsk Polytechnic Institute. Dr. A.G. Stromberg . The early works on organic polarography in the USSR [144–146] and polarographic and voltammetric methods for determining the trace of organic substances [147].

9.1.11 Other regions

Several EKhOS-related topics were also studied in Tbilisi (academician of the Georgian AS, Dr. D.I. Dzhaparidze , Dr. V.Sh. Tsveniashvili ), Gor’kiy (Dr. Yu.V. Vodzinskiy ), Leningrad (Dr. V.V. Berenblit ), Krasnoyarsk (Dr. V.L. Kornienko ), Tambov (Dr. А. B. Kilimnik ), Donetsk (Dr. Kh. Z. Brainina , Dr. Ye.М. Royzenblat , Dr. E.Ya. Sapozhnikova ), Kishinev (Yu.S. Lyalikov , Yu.D. Sister , V.V. Senkevich ), L’vov (Dr. М.А. Kovbuz ), etc. Research on issues close to EKhOS is also performed in some of these centers nowadays.

9.2 My Experience: From the End of the “Ottepel’” to the End of “Perestroika”

In this part of the article, I will talk of my experience at the All-Union Scientific Research Institute of Vitamins (Vsesoyuzniy NII Vitamin Institute, VNIVI) from 1961 up to 1993 (Fig. 9.12), i.e., from the end of the “ottepel’” (“thaw”) up to the collapse of the USSR. VNIVI was a midsized institute of the midsized Ministry of Medical Industry. But the “climate” and working conditions which we had there were rather unusual for Soviet research institutes and for big research centers.

My entire electrochemical career was linked to this institute starting with the experiments on a homemade polarograph. I first was introduced to polarography by my older brother, Stal’ Mairanovskii . He gave me the book of Kolthoff and Lingane [148] which explained the basics. After that, Stal’ took me to the analytical lab at IOKH, where he already worked then, demonstrated various instruments, and showed how to handle mercury and a dropping mercury electrode (DME). In 1958, as a fourth year student of MITKhT (Lomonosov Moscow Institute of Fine Chemical Technologies) with Stal’s recommendation, I came to interview Gleb Ivanovich Samokhvalov in the Laboratory of Chemistry of Polyenic Compounds of VNIVI. I was allowed to conduct my experiments in his lab, allocated a place, issued a pass to VNIVI, and provided with a set of electrodes and some tips on the assembly of a polarograph by Stal’. And so began my evening polarographic experiments, after daily studies at MITKhT. This is how my brother destined me for a future in EKhOS.

At that time, VNIVI consisted of several laboratories on the second floor of the building of the Moscow experimental vitamin plant (MEVZ) in the center of Moscow, on Novokuznetskaya Street, only a 15-min walk from the Kremlin. In the late 1950s, the Soviet Union began building large highly productive factories for manufacturing synthetic vitamins; according to the federal plan, the products made on those factories had to satisfy all the needs of the USSR healthcare system. The Belgorod vitamin plant was built in the city of Belgorod and the Bolochovskiy chemical plant in the Tula region. A procedure for the industrial synthesis of vitamin A was developed in a short time in Samokhvalov’s laboratory and debugged on a pilot plant at MEVZ (Fig. 9.13). Most of the control methods of production stages were based on traditional analytical procedures. Samokhvalov initiated the use of instrumental methods of analysis. The chief engineer of MEVZ, M. Ts. Yanotovsky (in Russian transcription Mikhail Tsalevich Yanotovskiy ) was transferred to Samokhvalov’s lab in 1960. He mastered gas chromatography (GC) and developed a set of GC-based analytical procedures, which were included in the regulations of the vitamin A production. My thesis “Polarographic study of the reaction of ketones with amines” was also linked with vitamin A synthesis. The work was conducted under guidance of Dr. Rimma Porfirievna Evstigneeva at the MITKHT’s Department of Chemistry and Technology of Fine Organic Compounds. A professor and member of the USSR Academy of Medical Sciences, Nikolai Alekseevich Preobrazhenskii (1896–1968), a student of the famous Russian chemist Aleksey Ye. Chichibabin , was in charge of that chair.^{Footnote 13}

After my graduation from MITKhT (defending my graduation thesis Fig. 9.14), I was assigned to work at the Samokhvalov’s laboratory and started in polarography in the newly equipped lab room, it was on the territory of the MEVZ; Misha Yanotovsky (PhD, 1965) became my friend for life. In 1962, together we developed the combined GC-polarography method or GC-EC [149–151]: the components separated with a carrier gas (He, Ar, etc.) passed through a heated capillary into a special cell coupled with the oscillographic polarograph PO-5122 TSLA. The GC-EC technique was used for the analysis of carbonyl compounds; both polarographic and GC data (E _1/2 and retention time) were used to identify the components [152]. The system was designed for micro-collection of the separated components [153].

In the beginning of my career at VNIVI, I worked on analytical projects related to the production of vitamins A and D. For the first time, we then managed to produce a well-defined polarogram of polyenes at very negative potentials down to −3 V SCE. In 1964, we published our first articles on polarography of vitamins A and D [154] and the control of vitamin A manufacturing [155]. Two of our analytical methods were implemented at the Bolokhovskiy plant, applying the Hungarian polarograph OH-102 Radelkis. This series of successes was due to several factors: First of all, I had an excellent equipment, the Soviet-made polarograph PE312 TSLA. Well-chosen experimental conditions played also a very important role: in 1962, I started using DME with the dropping control by a hammer and tetraalkylammonium salts in dimethylformamide (DMF) as electrolyte solution. That type of solution was just introduced into polarography by Wawzonek [156, 157] and reagents were Soviet made and readily available. However, the most important was that in Samokhvalov’s laboratory, we felt indispensable and independent at the same time. One of the memorable episodes happened in 1965: I had a newborn son and decided to do a polarographic analysis of vitamin D purchased in the pharmacy for babies. The polarogram had an additional stretched wave typical for peroxides. The drug was produced at the Kiev vitamin plant; the same product of the Leningrad plant was practically free of that wave. My assumption of peroxide presence in vitamin D was confirmed (it forms during vitamin D production by UV irradiation of ergosterin). I informed Samokhvalov about the findings—the situation was complicated because I encroached on someone else’s territory: responsibility for the quality, and standards of vitamin production was the remit of the analytical laboratory under Dr. V.A. Devyatnin . But Samokhvalov was very supportive, and he said: “You present the issue on the Scientific Council, and I will support you if needed.” My report caused quite a commotion considering the toxicity of peroxides; to prove my findings, I demonstrated polarograms. As it turns out, the Kiev plant used UV irradiators with suboptimal spectral parameters. Shortly after, the technology in Kiev was modified, and the changes were also introduced into USSR’s pharmacopeia standard for vitamin D. Following this, we discovered other drug impurities using polarography. These results were presented at the Mendeleev Congress [158]. The polarographic method was refined to become a standard control procedure in the production of vitamin D [159]. Thus, I was rather independent choosing my research topics in VNIVI. It was of course much helped by the fact that most of my associates were synthetic organic chemists, who shared my interest in mechanism of electrochemical transformations of organic compounds. But I had considerable “freedom of choice” virtually throughout all my time at this institute. How was that possible?

In 1964, VNIVI moved into a new beautiful building in the new southwest area of Moscow; even the new address was inspiring—“Scientific Passage, 14-a.” By then, I have accomplished a lot of research, which formed the basis for my Ph.D. In 1966, I defended the thesis “Polarographic study of compounds with conjugated carbon bonds” at the Institute of Electrochemistry (IELAN) under the supervision of Professor Samokhvalov without a postgraduate course. Samokhvalov warned me then that I did not have any opportunity for a career in his lab, and I carried on as a junior researcher. In May 1969, through Alexander Ershler (IELAN), I was unexpectedly invited to the director of the Institute of Bioorganic Chemistry. Academician M.M. Shemyakin (1908–1970), famous scientist, head of the Soviet school of bioorganic chemistry told me of his plans to venture into bio-electrochemistry and offered me a job. It sounded like a dream come true—to work in an exciting novel field and that at an Institute of the Academy of Sciences!^{Footnote 14} I notified Samokhvalov about the job offer, and shortly after, I was called to see the new director of VNIVI, Professor Viktor Andreyevich Yakovlev , a famous scientist in the field of enzyme kinetics (Fig. 9.15). Since his arrival in 1967, the institute received a powerful impetus to development. Yakovlev said he knew of Shemyakin ’s offer but asked me to wait with the final decision: he wanted to apply to the Ministry for approval of a new laboratory of control methods of manufacturing (abbreviated “Met-Co”) with me as a director. I agreed, although I was skeptical that it would be approved, me being a Jew, too young, and not a member of the Communist Party. However, in July 1969, I was appointed as an acting head and soon after confirmed as a head of the new lab. Initially, I have employed several young associates. Naftoliy T. Ioffe was one of the first ones; he was from a postgraduate school at INEOS (he had no offer to stay there) and soon defended his Ph.D. thesis and became my deputy, assistant, and friend. The lab acquired basic equipment (UV and IR spectrometers, gas chromatograph), and by the end of 1970, we completed several useful projects for vitamin plants. The laboratory was gaining momentum, and gradually, we became again engaged in EKhOS along with the analytical chemistry projects.

In 1972, VNIVI was shaken by dramatic events. The head of the physicochemical laboratory, Iosif Moiseyevich Kustanovich, Ph.D., member of the Communist Party, has resigned. It became known that he already had a permit to immigrate to Israel. V.A. Yakovlev , as a head of institute, was severely reprimanded for the “loss of vigilance” by the Communist Party and was temporarily suspended as a director. Yakovlev found himself in the same situation as Frumkin at the IELAN after B. Levich applied for immigration to Israel in the same in 1972; Frumkin ’s situation was even worse because Levich did not resign in advance. After few months of uncertainty, Yakovlev was reinstated. But sadly this incident has taken its toll; Yakovlev prematurely died in spring of 1977, full of plans and ideas. His career was in continuous ascent and he was supposed to rerun for the title of corresponding member of the USSR Academy of Sciences in the near future; his plan was also to make the VNIVI as the institution of dual subordination (under the Ministry and the USSR Academy of Sciences).

But then, in December of 1972, Yakovlev offered me to become the head of the physicochemical laboratory. It is etched in my memory. Yakovlev ’s secretary called me asking to come up to the director’s office. Yakovlev looked tired. I started to congratulate him that the “Kustanovich affair” was finally over, but he, with his characteristic humor, said that it was not over yet: the physicochemical lab was now left without a head. And he offered me the job. At first, I did not understand what was going on. I did not want to tell him directly that I feared it was politically precarious to make me the head of the lab following the “Kustanovich affair.” And I said: “I am a chemist, so, Viktor Andreyevich, you maybe better find a Physicist?” I put a double meaning in that and I knew that he understood; Yakovlev answered very emotionally, with gestures: “We do not need any PHYSICISTS !!!” He asked me to consider the offer and give an answer a day or two later. When I was at the door, Viktor Andreevich, slightly embarrassed, asked, “one more thing, you are not planning to leave anytime soon?” At that time I was able to say “NO” quite confidently. The next day I agreed to move to the new lab but asked to take few employees with me. Misha Yanotovsky took over as the head of “Met-Co” lab.

Kustanovich left a well-equipped and smoothly running laboratory with groups for UV and IR spectroscopy and NMR and mass spectrometry. The main tasks of the laboratory were structural studies to help organic synthetic chemists. The team in Kustanovich’s laboratory was initially wary of our new addition, but after a few years on, we found a common wavelength and formed a united young laboratory. There I worked until I left Russia; but it was not until 1993. Already in early 1973, we received a great chromatography mass spectrometer JMS-01-SG2 (JEOL). That spectrometer was used not only for the needs of VNIVI but also to provide service to other Moscow institutions of the Ministry. Later we got the latest 90-MHz Bruker NMR spectrometer. At that time, I met Uwe and Barbara Eichhoff . This German couple represented the company Bruker, working selflessly in the Soviet Union under extremely difficult conditions for foreigners. Subsequently, the “Bruker report” published our brief communication on the first in situ EC-NMR cell (Sect. 9.2.5, “In Situ Electrochemical NMR”). Nowadays, we enjoy Dr. phys. Uwe and Barbara Eichhoff ’s company when they visit Berlin.

Our work on EKhOS at VNIVI was closely connected to the other projects of the institute, and the main objects of research were natural biologically active compounds. At that time, those compounds were barely studied by electrochemists. That field was new and fascinating. At the same time, we had quite a bit of freedom to deviate from the main course of research and therefore our projects were very diverse. The following overview provides a somewhat arbitrarily grouped list of works. It seems strange now that I never had a joint article with my first teacher—Stal’ Mairanovskii . My beginnings at VNIVI were defined by analytical projects, and my brother helped advise me but did not consider his contribution sufficient to be included as an author. Then I got interested in organic electrochemistry and electrosynthesis. Gradually, my research approached the field where Stal’ was very active, and we were getting very close to working on something interesting together. Some of Stal’s ideas (“inheritance effect,” impact of the strong electric field near the electrode, the activating effect of substituents on cleavage of bond, etc.) were already reflected in my research. But the time allotted to us was too short.

9.2.1 Development of Experimental Techniques and Procedures

9.2.1.1 DME with the Dropping Control

The reduction of the surface tension in passing through the zero charge potential is accompanied by a significant decrease in drop time t of the DME (~20 times at the Е = −3 V SCE, DMF), and the polarograms are distorted due to irregular dropping. The distortions are partially suppressed with the electrode with a trowel for forced drop separation proposed by Skobets and Kavetskiy [162]. The all-glass modification of this electrode proposed by S. Mairanovskii in the early 1960s became widely applied in most polarographic labs of the USSR, and a design with a sliding trowel to change t-values was developed [163]. D.P. Zosimovitsch et al. [164] in 1948 and somewhat later P.N. Teretschenko and V. Čermak and V. Hanuš [165, 166] employed a DME with a hammer for drop time control. This principle was very attractive, and I made an electronic control unit with a range of t = 0.07–7.0 s using my radio-amateur experience in electronics. Distinct polarograms were obtained by this technique even in the farthest cathodic range [154, 155]. It became possible to overcome challenges of analyzing mixtures of vitamins A and D using short drop times in order to reduce the interfering “kinetic” wave of vitamin A [167]. However, the drop time control with a hammer could lead to deviations from the theory. The results published in [168] did not solve the problem as these measurements were rather limited and conducted in the presence of a surfactant. My multiparameter testing showed that, even at the shortest drop time (t = 0.07 s), deviations from the theory of any of the parameters do not exceed ~3 % [169, 170].

It was of interest to further reduce the drop time. At first, it was a simple vibrating electrode with a dropping frequency of 50 Hz [171]. Unexpectedly, I found that, due to accelerated mass transfer, the “classic” polarogram could be produced with as little as 5–10 drops per 1 V, instead of 50–200 drops/V. The recording time of a polarogram was reduced to tenths of a second, and the method was called “express polarography” (Fig. 9.16) [171]. At the same time, the mercury consumption also reduced proportionally at carrying out the polarographic analysis. This technique proved effective in particular in combined gas chromatography-EC because it provided very fast measurements in a stirred liquid [152].

The dropping mercury electrode with adjustable vibrating frequency of 5 Hz up to a record-high value of 1 kHz was then made and studied in detail ([172, 173], p. 76) (cf. Fig. 9.17). This was achieved using wider glass capillaries which were drawn out at the end. With conventional flow rates of mercury (m ≈ 0.002 g/s), this electrode made it possible to lower the time of contact t _c of the mercury with the solution to so low values like in case of the Heyrovský's streaming mercury electrode (t _c from 0.001 to 0.01 s at the m ≈ 0.2 g/s). The convective component of the limiting current depending on the vibrations frequency and amplitude was estimated (diploma thesis by Igor’ Dmitriyev, 1970) [172]. This technique enabled studies of processes involving adsorption and fast chemical stages in a series of carotenes, porphyrins, etc. [174].

9.2.1.2 Accurate Measurement of Half-Wave Potentials on the SCE Scale in Nonaqueous Media

We accomplished this using semiautomatic recording of polarograms with reference potentiometer and a special reference electrode [175]. The E _1/2 values were related to the SCE scale by comparing with E _1/2 of K⁺ ion according to Pleskov -Vlček [176]; the total standard error was less than 1 mV. The difference ΔE ₀ = −3 mV in the values of E ₀ of 15,15′ trans- and cis-isomers of β-carotene was successfully assessed in particular [177] (Sect. 9.2.2, “Natural Polyenes: Vitamins A and D, Carotenes, and Porphyrins”). We regularly used this reference electrode in experiments, and the handy thermostating unit [175] was additionally employed for the most precise measurements (the potential of the electrode had a high temperature coefficient).

9.2.1.3 Voltammetry with the Symmetric Trapezoidal Voltage Pulses (VATZ)

Voltammetry with the symmetric trapezoidal voltage pulses (VATZ) [178] was created advancing the technique of W. Schwarz and I. Shain ([cf. 179]). The VATZ technique was more advantageous because the measurements were carried out at a constant rate of potential change and, hence, at the same contribution to the capacitive current, but with different delay times, Т (the width of the trapezoid). Thus, it is possible to work at very high potential scan rates in both directions (more than 100 V/s) and with Т values up to a few seconds. The VATZ method can be considered intermediate between a reverse-scan chrono-voltammetry and pulse polarography, and the theory of classical voltammetry with a triangular pulse voltage (VATR) was still applicable here. Two methods VATZ and VATR were compared in the study of the fast protonation kinetics of the dianion β-carotene [178] (Sect. 9.2.2, “Natural Polyenes: Vitamins A and D, Carotenes, and Porphyrins”).

9.2.1.4 Electrolysis at a Constant “pH” (“pX”) with Recording Equipment

Maintaining proper acidity of the medium is an important condition for electrosynthesis with special difficulties in nonaqueous media. The main problem is the strong, by a few hundred mV, influence of the electric field in the electrolyzer to the indications of a pH meter.^{Footnote 15} We solved this problem by using a special pH sensor where the end of the electrolyte bridge of the reference electrode was approached directly to the glass-electrode membrane; deviations of the pH meter in the electrolysis with such an electrode did not exceed a few mV [182, 183]. Combining this device with a commercial automatic titrator (Radelkis, Hungary, burette with solenoid valve) gave us a pH stat which reliably maintained the predetermined “pH” value during electrolysis. Some examples of “pH-static” electrosynthesis are given in Sects. 9.2.2, “Natural Polyenes: Vitamins A and D, Carotenes, and Porphyrins” and Sect. 9.2.6, “Electrosynthesis in the Chemistry of Biologically Active Compounds: Electro-deprotection Method”.

A recording apparatus with an integrated homemade titrigraph was also assembled [182, 183]. The amount of titrant was recorded amperometrically by means of “polarographic indication” in a special cell synchronously with the supply of titrant (two Radelkis burettes) [184, 185]. As a result, we were able to trace the progress of electrolysis at a given pH and to find the stoichiometry—the number of electrons n and protons m of the electrode reaction [182, 183]. Thus, values of n = 2.04 and m = 0.94 obtained upon reduction of tricresyl phosphate (Hg cathode, 0.04 M Et4NJ/DMF, titrant HCl in MeCN) indicate that the reaction goes along the path (9.7a) with the cleavage of С–О rather than the path (9.7b) with the cleavage of the Р–О bond:

$$ {\left(\mathrm{A}\mathrm{r}\mathrm{O}\right)}_3\mathrm{P}=\mathrm{O}\ \overset{{\displaystyle \sum 2\mathrm{e}\mathrm{d}\mathrm{p}}}{\to} {\left(\mathrm{A}\mathrm{r}\mathrm{O}\right)}_2\mathrm{P}\left(=\mathrm{O}\right){\mathrm{O}}^{-} + \mathrm{A}\mathrm{r}\mathrm{H} $$

(9.7a)

$$ {\left(\mathrm{A}\mathrm{r}\mathrm{O}\right)}_3\mathrm{P}=\mathrm{O}\ \overset{{\displaystyle \sum 2\mathrm{e}\mathrm{d}2\mathrm{p}}}{\to} {\left(\mathrm{A}\mathrm{r}\mathrm{O}\right)}_2\mathrm{P}\left(=\mathrm{O}\right)\mathrm{H} + \mathrm{ArOH} $$

(9.7b)

Note that another sensor, for example, an ion-selective electrode, can be used instead of the glass electrode, and in general, any combination of an electrolyzer and a “concentration-stat” could be used [182, 183].

9.2.2 Mechanisms of Electroorganic Reactions

9.2.2.1 Natural Polyenes: Vitamins А and D, Carotenes, and Porphyrins

The conclusion of Japanese authors that the reaction proceeds along the “classical” path, i.e., with reduction of conjugated pentaenic vitamin A, derived from electronic spectra of the electrolysis products [186, 187] contradicted our observations, in particular, the abnormally strong effect of substitute Y = -OH, -OAc, and -OMe on E _1/2 [188]. We found that, just as with cinnamic alcohol [189], the process does not run with the reduction of the conjugated system but occurs with the rupture of С–О bond and formation of axerophthene (Y = H). The total schema includes competing p and d reactions of the radical anion according to the e(pep)dep process [190]:

These ideas were utilized for a number of new electrosyntheses. Deuterated axerophthene RCH₂D was obtained using a pH stat system and DCl/D₂O titrant [191]; the different derivatives of ubiquinone (coenzyme Q) [192] and vitamin K in two alternative ways (9.8a) and (9.8b) were obtained by simply changing medium protogenic activity [193]. Studies on electroreduction of cinnamyl derivatives [194, 195] in cooperation with my close friend Sasha Weinberg (1937–2012) gave rise to a new direction—“electro-deprotection” (Sect. 9.2.6, “Electrosynthesis in the Chemistry of Biologically Active Compounds: Electro-deprotection Method”).

A few incidents demonstrate here how little the Western chemists (not only electrochemists) were aware of the research performed in the USSR: just three examples. In 1976, J. Gourcy et al. “rediscovered” the electrosynthesis of axerophthene [196]. At around the same time, H. Lund and coworkers [197] proposed a schema completely reproducing (9.8a)–(9.8b). It seemed particularly odd, and we wrote a letter to the editor of Electrochimica Acta hoping for clarification from the authors. To our surprise, the journal reprinted the full text of our letter [198]; apparently, the editor in chief also considered this case unusual. And finally, the famous scientists E. Corey (Nobel Prize in 1990) and M. Tius proposed cinnamyl as a “new” protecting group [199] pointing out its advantages over known groups—10 years (!) after our works [194, 195]. But unlike us, they used a two-step chemical method for removing cinnamyl first by Hg(OAc)₂ and then by KSCN. Sasha Weinberg and I decided not to send any more letters to the editors, and the “cinnamyl authorship” was never clarified: the articles referring to Corey and Tius (cf. [200]). Although, our papers have been published in Russian, it is still surprising that the Western colleagues did not see them in the English abstracting services.

The mechanism of reduction of the triene structure of vitamin D (D₂ and D₃) also proved to be not a common epep process as we first assumed [201]. The wave had properties of “irreversible” type. At the same time, the subsequent protonation of the anion radical (AR) was not a “special” reaction: its rate constant k _p = 6 × 10⁴ s⁻¹ obtained with high-speed pulse chronopotentiometry (HSCP), the new technique elaborated by A.B. Ershler et al., was in the range where other conjugated trienes gave “reversible” waves [202]. The slow e stage was accounted for by spatial rearrangement of the molecule. Developing this hypothesis further, we proposed a schema erpep with a fast cis- and trans-isomerization of anion radicals AR1 → AR2 [203]. Thus, the rate constant k _p found in [202] should have been assigned to the protonation of the secondary, i.e., trans-anion radical AR2:

(9.9)

Indeed, specially synthesized trans-vitamin D that immediately forms AR2 gave a reversible wave [203]. It was the first example where the cis- and trans-isomerization caused a slowing down of the preceding e stage. This stage “r” should be very fast in accordance with the formula “ultrafast chemical reaction is the cause of slow electron transfer” [204] (Sect. 9.2.2, “Cathodic and Gas-Phase Reactions of the Bond Cleavage”). Thus, it could not be tracked by the high-speed cyclic voltammetry (CVA, v ≤ 1000 V sec⁻¹) and by the HSCP [202]. The major reaction product is dihydrovitamin D (III), but dihydrotachysterol (IV) is also formed, which is effective in hypercalcemia (Sect. 9.2.7, “Dihydrotachysterol”).

For a system of β-carotene (V) (11 conjugated bonds, drawing), we found four cathodic waves with two reversible one-electron steps $ \mathrm{Car} + {\mathrm{e}}^{-}\ \rightleftarrows {\mathrm{Car}}^{\cdotp -} + {\mathrm{e}}^{-}\ \rightleftarrows {\mathrm{Car}}^{2-} $ [177, 205], in contrast to the data presented in [186, 187] and [206, 207]. The EC-ESR experiments curried out proved the formation of Car anion radicals [208]. The process runs along the way $ \mathrm{Car} + \mathrm{epep}\ \to {\mathrm{CarH}}_2 $ in the presence of proton donors [205, 209]. 7,7′-Dihydro-β-carotene was obtained with good yield as CarH₂ by electrolysis with weak proton donator [191]. Carotenes are easily oxidized; the two-electron anodic wave has reversible behavior according to $ \upbeta \hbox{-} \mathrm{carotene} - 2{\mathrm{e}}^{-}\ \rightleftarrows\ \upbeta \hbox{-} {\mathrm{carotene}}^{2+} $ [205] (the cyclovoltammetric experiments with v = 1000 V/s and T = 273 ÷ 213 °K [209]). The alternative schema of the process is ↓-ee _v ↑ with very fast cation radical disproportionation $ 2{\mathrm{Car}}^{\cdotp +}\ \rightleftarrows \mathrm{Car} + {\mathrm{Car}}^{2+} $ ([173], p. 153). High electron-donating activity of carotenes was confirmed by reactions with organic and inorganic electron acceptors [210]. For instance, the [β-carotene ·I]⁺ cation formed according to the reaction of $ \upbeta \hbox{-} \mathrm{carotene} + \mathrm{I}{}_2\ \rightleftarrows\ {\left[\upbeta \hbox{-} \mathrm{carotene}\cdot \mathrm{I}\right]}^{+}{\mathrm{I}}_3^{-} $ was detected by means of differential-pulse polarography [211]. Interestingly, the electroreduction of the complex $ {\left[\upbeta \hbox{-} \mathrm{carotene}\cdot \mathrm{I}\right]}^{+}{\mathrm{I}}_3^{-} $ led to the neo-A-retrodehydro-β-carotene with 12 conjugated bonds, i.e., an unusual cathodic dehydrogenation occurs here. The family of carotenoids, β-carotene, α-carotene, lycopene, etc., was studied with the measurement of kinetic parameters [177, 178, 191, 205, 209]. The relatively high basicity of anion radicals of carotenes observed was used to perform catalytic endoergic electron transfer to β-carotene from anion radicals of chlorophyll and porphyrins [212] (Sect. 9.2.4).

Our first study of the electrochemistry of porphyrins coincided with the beginning of intensive study of these macrocycles [213–216]. In contrast to the conclusion made in [217], the third wave following the reversible $ \mathrm{P} + {\mathrm{e}}^{-}\ \rightleftarrows {\mathrm{P}}^{\cdotp -} + {\mathrm{e}}^{-}\ \rightleftarrows {\mathrm{P}}^{2-} $ waves was found to be accounted for by the transfer of four electrons with formation of porphyrinogen PH₆ via fluorine as an intermediate product PH₂ [174, 218, 219]. The protonation kinetics of anionic particles was studied depending on proton donor strength and concentration; up to eight polarographic waves were observed and identified in these measurements. An additionally discovered prewave was associated with the adsorption of dimers $ {\left(\mathrm{P}\hbox{-} \mathrm{P}\right)}^{\cdotp -} $ of porphyrin and its anion radical on the electrode surface, schema ↑e↓a_s the dimer’s particel size was estimated from polarographic data [174, 218]. Electrosynthesis of the mesomethyl porphyrin and its metallo-complexes [220] and cobalt alkylporphyrins (under EC-ESR control [221]) as well as introduction of Co porphyrins as electrocatalysts in dehydrogenation and radical polymerization processes [222] were among the preparative applications. The results of the electrochemical study of porphyrins are reviewed in the book [223].

9.2.2.2 Cathodic and Gas-Phase Reactions of the Bond Cleavage

The ede mechanism is here considered as a “classical” behavior [224]:

$$ \mathrm{R}\mathrm{X}\ \overset{\mathrm{e}}{\to }\ {\mathrm{R}\mathrm{X}}^{\cdotp -}\ \overset{\mathrm{d}}{\to }\ {\mathrm{R}}^{\cdotp } + {\mathrm{X}}^{-}\ \overset{\mathrm{e}}{\to} {\mathrm{R}}^{-} + {\mathrm{X}}^{-}\ \to \dots $$

(9.10)

For CH₃Cl, it is transformed to the {ed}e with the “ultrafast” cleavage d stage (time of single oscillation, “synchronous” or “concert mechanisms”).^{Footnote 16} The kinetic rather than thermodynamic factors (such as the energy of the lowest unoccupied molecular orbital of the substrate, etc.) became now deciding. We drew attention to the analogy of {ed} reactions with gas-phase dissociative electron capture process and used the results of gas chromatographic measurements with an electron capture detector. The expression for the gas-phase activation energy [225]

$$ {E}_{\mathrm{a}}^{*}=A+\alpha \left({D}_{\mathrm{RX}}-{A}_{\mathrm{X}}\right) $$

(9.11)

obtained by using the Brönsted relation was confirmed by experimental data [226–228]. In Eq. (9.11), А and α are constants (0 < α < 1), D _RX is R–X bond strength, and A _X is the electron affinity of the halogen X. Applying the Wentworth model [226, 227] based on the Morse function for anharmonic vibrations and accepting the Hammond postulate, the gas-phase activation energies E ^*_a,e and E ^*_a,d of е and d stages were calculated for a series of aryl and alkyl halides [204]. Antibate E ^*_a,e and E ^*_a,d changes with an extended straight portion turned out to be observed for a wide range of rate constants of d stages (Fig. 9.18). The dependence

$$ \log {k}_{\mathrm{e}}^{*}=-11+0.0155{E}_{\mathrm{a},\mathrm{d}}^{*} \left(\mathrm{here}, {E}_{\mathrm{a},\mathrm{d}}^{*} \mathrm{in}\ \mathrm{kJ}/\mathrm{mol}\right) $$

(9.12)

therewith is satisfied predicting a slow electron transfer for the “ultrafast” d stage. Within the framework of these approximations, the formula for the inner reorganization energy was derived [204]:

$$ {\lambda}_i={D}_0\left(1-{k}_{\mathrm{R}}\right) $$

(9.13)

where $ 0<{k}_{\mathrm{R}}<1 $ is the Morse function parameter, $ {D}_0={D}_{\mathrm{RX}}+0.5h{v}_0 $, and v ₀ is the fundamental vibration frequency. It was also found the antibate relationship between λ _i and E ^*_a,d [229] is confirmed by quantum-chemical AM1 calculations [230]. These results were applied then also under conditions of polar media (see Sect. 9.2.3, “Cathodic Reactions with Bond Cleavage”). An overview report on this issue was made in 1986 at the 37th ISE Meeting [231].^{Footnote 17}

9.2.3 Chemical, and Electrochemical Reactivity

9.2.3.1 Linear Conjugated Polyenic Hydrocarbons

We tested the Maccoll–Hoijtink relationship between E _1/2 and energies of the lowest unoccupied molecular orbitals (as m _LUMO coefficients) for linear conjugated polyenic hydrocarbons (LCPs) [236]. Using the perturbation theory for the substituent effect, the following simple formula was obtained:

$$ {m}_{\mathrm{LUMO}}=2 \cos \varphi +\frac{2}{n+1}{\displaystyle \sum h{ \sin}^2}\left(r\varphi \right) $$

(9.14)

where $ \varphi =\pi \frac{\left(n+2\right)}{2\left(n+1\right)} $, r is the ordering number of the substituted atom, h is the induction parameter for the substituent, and n is the general number of π-electrons in LCP. The linear dependence

$$ {E}_{1/2}=2.19{m}_{\mathrm{LUMO}}-1.24 \left(\mathrm{S}\mathrm{C}\mathrm{E}\right) $$

(9.15)

is valid for a wide range of LCPs starting from butadiene and up to β-carotene (the number of double bonds is between 2 and 11). Equations (9.14) and (9.15) were proved to be useful for determination of structure to property relationships in the series of LCPs; thus, the electron affinity (ЕА) and ionization potential (IP) of carotenoids were calculated [205].

9.2.3.2 Monofunctional Derivatives of Polyenes and Porphyrins

A universal procedure for prediction of E _1/2 ^RX for different classes of compounds (covering aromatic series, phenyl polyenes, LCP, etc.) was developed based on the E ^RH_1/2 for the corresponding hydrocarbons RH and using the donor–acceptor constants of substituents ([173], p. 101, [237]). The linear correlations $ {E}_{1/2}^{\mathrm{RX}}=f\left({S}_{\mathrm{X}}\right) $ intersecting at the “isopotential point” corresponding to the E _1/2 of the radical RCH₂ lay at the core of this procedure. The slopes of the lines are determined by the electron affinity EA ^RH of hydrocarbon RH, linearly decreasing with increase in EA ^RH. Such correlations are also valid for porphyrins and metalloporphyrins MPO. For M = Ca²⁺, Mg²⁺+, Mn²⁺, Zn²⁺, Cd²⁺, Ni²⁺, Pd²⁺, and Cu²⁺, the effect of the metal M is taken into account by the constant S _М related to the Pauling’s electronegativity [238]. For М = Сo²⁺, Mn³⁺, and Fe³⁺, the accepted electron is localized at the metal atom, and the slopes for $ {E}_{1/2}^{\mathrm{RX}}=f\left({S}_{\mathrm{X}}\right) $ dependencies are much smaller (a weaker effect of substituent X). This fact can be used to elucidate the mechanism of the process. The values of S _X for a large number of substituents are given in ([173], p. 117, [237]). The validity of the classical Maccoll–Hoijtink equation for рorphyrins was established in [219].

9.2.3.3 Cathodic Reactions with Bond Cleavage

A phenomenological approach, Sect. 9.2.2 was implemented for ultrafast reactions (UFR) RX + e → Rċ + X − also in polar media, i.e for the estimation of the cathodic E_1/2 ([173], pp 122–136; [225]). Gas-phase activation energy E ^*_a being also considered as the decisive factor in this case. Assuming that the activation energies $ {E}_{\mathrm{a}}={\alpha}_{\mathrm{m}}{E}^{\ast } $ for the UFR processes in one and same polar media (solvent + electrolyte, coefficient 0 <α_m <1 ) and taking into account Eq. (9.11), we came to the expression:

$$ {E}_{1/2}=A\hbox{'}-\alpha \hbox{'}\left({D}_{\mathrm{RX}}-{A}_{\mathrm{X}}\right) $$

(9.16)

Thus, for UFR, for instance, alkyl halides (RX = AlkX), the values of E _1/2 may be easily predicted based on the available quantities of D _RX and A _X ([173], [225]). It should be noted that the coefficient α′ = 0.018 Vċmol/kJ in Eq. (9.16) is almost the same as the values of slops in a set of particular experimental dependencies $ {E}_{1/2}=C-\beta {D}_{\mathrm{RX}} $ found earlier by Evans and Hush for AlkX with different halogens X = Cl, Br, and I: B = 1048 0.013, 0.0173 and 0.018 Vċmol/kJ, accordingly [239]. For a more detailed evaluation of this phenomenological approach, the values of E _1/2 (or of E _p) were measured in a wide temperature interval, and corresponding measurements in butyronitrile at temperatures down to −100 °С were scheduled. An excellent theoretical basis for this work was at the Faculty of Technology of Semiconductors of MITKhT led by Prof. Viktor Il’ich Fistul (cf. student work [240]). But these plans could not come true.

The reversible e stage takes place in ed process for the SMFR and FR cases, so the influence of the rate constant k _d of the d stage on E ^RX_1/2 is described here in terms of the conventional theory of the ec reactions as a “kinetic correction” ΔE _1/2 [225]. The rigorous approach to the assessment of solvent effects is based on finding the reorganization energy λ ₀. In developing the approach [225] based on the Wentworth’ model and formula 9.13 for λ _i, Saveant calculated also the values of λ ₀ according to Marcus–Hush [232–235]. However, as was shown by Grimshaw et al. on the example of alkyl halides, the Marcus–Hush calculations led to considerable deviations from experimental data in this case [241, 242]. A more rigorous analysis with quantum-chemical PM3 calculation of the λ ₀ for alkyl halides was carried out by A.M. Kuznetsov and coworkers [243, 244].

9.2.3.4 ec Processes: Cross-Correlation Between Parameters of the e and c Stages

As follows from the consideration of slopes of linear dependence of $ {E}_{1/2}^{\mathrm{RX}}=f\left({S}_{\mathrm{X}}\right) $ (Sect. 9.2.3, “Monofunctional Derivatives of Polyenes and Porphyrins”), the easier the system is reduced, the less is the influence of the substituent X on E ^RX_1/2 [237]. This pattern and the decrease of the rate constant k _c of chemical stage upon facilitation of reduction of the system are proved theoretically [245]. For ed processes, this directly stems from the antibate nature of the changes in activation energies E ^*_a,e and E ^*_a,d (Fig. 9.18). For ep processes with subsequent protonation stage, this follows from the results of a quantum-chemical consideration, for example, using Eq. (9.14). This conclusion can also be applied to other processes where the electron transfer is determined by the position of the substrate’s frontier orbitals. In two limiting cases, we have infinitely long, graphite-like system with the delocalized electron (high electron affinity of the substrate M and low reactivity of the product $ {\mathrm{M}}^{\cdotp -} $) and solvated electron (low electron affinity of the substrate S, i.e., solvent, and extremely high reactivity of the product, i.e. e _solv) [245]. The “antibate rule” written as

$$ \Delta \log {k}_{\mathrm{c}}=\pm 0.059{\alpha}_{\mathrm{c}}\Delta {E}_0 $$

(9.17)

we called as the “Brönsted cross relation,” or BCR [246, 247]; here T = 298 K, the minus sign is for cathodic processes, and ΔE ₀ is the difference in the standard potentials of the compounds compared. The BCR rule is fairly general; the conditions for its implementation are given in [245–247]. The experimental values of “cross transfer coefficient” α _с for different ep, ed, and ea (i.e., anionic polymerization) processes lie in the range from 0.1 to 0.5.

9.2.4 Homogeneous Electrocatalysis

The case in point is the reaction [↓e] e _v ↑c with endergonic e _v stage with participation of a homogeneous catalyst regenerated at the electrode and followed the exergonic с stage. These systems became the subject of investigations in the early 1970s independently by three groups of researchers [248–252]. The first publication was the article by Lund and coworkers [248]; our work, fragments of which I reported in Riga’s EKhOS-73 [250], was submitted by Frumkin for publication in Doklady AN SSSR ^{Footnote 18} [251]. The “d” [248–252] and “p” and “r” [250, 251] reaction acted as the follow-up exergonic chemical stages.

The capabilities of the homogeneous electrocatalysis (HOMEC) processes for electrosynthesis and investigations of kinetics of c stages became immediately apparent (the first review [253]). The Koutecky approach for the simple catalytic schema was originally used for kinetic calculations: under certain conditions, the rate constant k _ev can be taken to be the half of the effective constant k _eff [248, 249, 251]. In general, however, this approximation cannot be used. As a general solution, we suggested a hybrid numerical–analytical method that made it possible to obtain a number of approximate formulas as applied to polarography and to voltammetry with rotating disk electrode, including “complicated” НОМЕС cases, for example, with deactivation of catalyst or with other transformations [254, 255]. The new capabilities of HOMEC in studying the heterogeneous stages “e” of electrode kinetics were also shown [256]. This work incorporated later in my report on EKhOS-76 in Tula [253] was also submitted by Frumkin for publication in Doklady AN SSSR. This was in April 1976, 1 month before the death of Frumkin …One example. The increase in the electrolyte concentration and reduction in the size of the cation of the electrolyte in the series of Bu₄N⁺–Et₄N⁺–Me₄N⁺ leads to a strong, up to +150 mV, shift in the E _1/2 of both chlorobenzene and vitamin D, but it has practically no effect on the rate constants of homogeneous electron transfer k _ev. Thus, the heterogeneous factors, in particular, the “compression” of the EDL with decreasing the size of the cation, have a crucial role here. The change in the ratio of heterogeneous/homogeneous reaction products was theoretically estimated for micro-electrolysis on DME [253]. The electron transfer reaction from the porphyrins and chlorophyll anion radicals to β-carotene was performed and studied by HOMEC (Sect. 9.2.2, “Natural Polyenes: Vitamins A and D, Carotenes, and Porphyrins”); other examples of HOMEC application are given in Sects. 9.2.6 “Electrosynthesis as an Investigation Tool: Pre-electrode Tomography”, and “Electrosynthesis in the Chemistry of Biologically Active Compounds: Electro-deprotection Method”. Synthetic and kinetic investigations of HOMEC were extensively carried out then by H. Lund , J.M. Savéant, and coworkers (see reviews [257, 258]).^{Footnote 19}

9.2.5 Combination of Electrochemical and Other Analytical Techniques

By analogy to the chromatopolarography developed by Kemula and Górski [261, 262] in the early 1960s, we developed combined method of GC-EC with a polarographic detector [149–153]. The electrochemical technique being used here is an additional analytical method. On the contrary, in the study of the mechanism of electrochemical reactions, electrolysis is a “primary” process, and it is combined with the methods of studying electrogenerated particles (EGPs). We have used several of these combinations.

9.2.5.1 In Situ Electrochemical ESR

The EC-ESR technique became the “classical” combined method in the USSR from the beginning of the 1960s owing to the electrochemists of Riga and Kazan (see Sects. 9.1.3 and 9.1.4). The method allows, for example, to measure the rate constant k _ex of the symmetric electronic exchange of $ \mathrm{M} + {\mathrm{e}}_{\mathrm{v}}^{-}\ \rightleftarrows\ {\mathrm{M}}^{\cdotp -} $ in the substrate–anion radical pair. In order to study the influence of the structure of the substrate on the value of the rate constant, we measured the rate constants k _ex for a series of substituted nitrobenzenes Х-С₆Н₄NO₂ using an original microcell [263, 264] (symmetrical design, large surface of working electrode, and small currents in the signal acquisition mode). Also EC-NMR measurements were in parallel performed. Earlier proposed theoretical models, including the ellipsoidal model, were proved invalid for aromatic systems containing two or more polar substituents. Good results were obtained with the new “model of the determining specifying group” [263, 264]. The validity of this model was confirmed by quantum-chemical calculations of the solvent reorganization energies λ ₀ [265]. The combined EC-ESR technique was often used in our studies of electrochemical reactions (carotenes, porphyrins, electro-deprotection reactions, etc.).

9.2.5.2 In Situ Electrochemical NMR

Taking into account the large potentials of NMR, we have developed an in situ electrochemical NMR cell [266, 267]. The three-electrode ЕС-NMR cell with divided cathode–anode compartments and with a Hg-working electrode was placed in a standard 5-mm spinning NMR probe practically without distortion of the spectral resolution. Several ЕС-NMR regimes were tested, including continuous potentiostatic electrolysis and current pulse and continuous galvanostatic electrolysis with steady-state concentrations of the EGPs. The capabilities of the EC-NMR method were demonstrated in solving numerous problems [268]. For reasons beyond our control, we could not publish the detailed design of the cell at that time. “The first practicable” EC-NMR cell (cited from [269]), with spinning 10-mm sample tube and a gold film rf-transparent working electrode, was published in the West only in 2000 [269]. Recently, we presented the EC-NMR cell [270], a radically advanced version of the cell developed 40 years ago.

9.2.5.3 Combined Electrochemical Stop-Flow Method

This method of direct study of reaction kinetics of the electrogenerated particles (EGPs) was implemented [271] on the basis of commercial stop-flow spectrophotometer with the EC cell mounted directly inside of the hydraulic system between the working syringe and the mixing camera. One- and two-channel modes were tested. Measurements were carried out for the protonation reaction of the EGPs as well for HOMEC processes. The EC-stop-flow technique is a powerful direct tool for studying the reactions of EGPs, including fast reactions with rate constants as high as 10⁶–10⁸ l/molċs.

9.2.6 Organic Electrosynthesis

9.2.6.1 Electrosynthesis as an Investigation Tool: Pre-electrode Tomography

Results of electrosynthesis are often different from result of a “similar” chemical reaction. These differences are associated with the heterogeneous electrode factors, and they can be used as a tool for studying the phenomena occurring at or near the electrode. In this respect, НОМЕС provides excellent capabilities for selection of a “similar” chemical reaction making it possible to run the process under the same conditions transferring it, however, from the electrode surface to the bulk solution (see Sect. 9.2.4).

We used such an approach in the study of dissociative edep reduction of the β, γ-unsaturated alcohols. Specially synthesized deuterated 2,4-pentadienol and its derivatives CH₂=CHCH=CHCD₂Y, where Y = -OH, -OAc, and -ОMe, was taken as a substrate RY [272, 273]; the deuterium label is necessary to distinguish the 1,5-positions. In contrast to the cases studied earlier (cinnamic alcohol, vitamin A, etc., Sect. 9.2.2, “Natural Polyenes: Vitamins A and D, Carotenes, and Porphyrins”), the reaction proceeds here via the symmetric pentadienyl anion [CH₂-CH-CH-CH-CD₂]⁻. Therefore, two piperylene isomers CH₃-CH=CH-CH=CD₂ (а) and CH₂=CH-CH=CH₂-CD₂H (b) in the strictly equal amounts could be anticipated as products. However, the preferential formation of one isomer, with the r _exp = [a]/[b] > 2, was found experimentally. This anomaly was explained by nonequilibrium asymmetric arrangement of anion near the electrode due to the “orientation inheritance” of the original asymmetric molecule RY. This should lead to the intra-anion charge distribution and to the unequal rates of protonation in 1,5-positions. The situation is similar to the Stal’ Mairanovskii’s effect of “orientation inheritance” on the electrode surface [33, 34] (Sect. 9.1.1). But we were dealing here with the “volume inheritance,” as the absence of adsorption on the electrode substrate was established. Hence, we determined the “effective” pre-electrode orientation of the pentadienyl anion, which was different for different substituents Y = -OH, -OAc, and -OMe in the starting molecule. Therefore, we hypothesized the existence of a “superviscous” pre-electrode layer with the ~10⁴ to 10⁵ times higher viscosity than in bulk [272, 273].^{Footnote 20} The drastic increase in the proportion of thermodynamically less favorable cis-configurations for both isomers a and b has to be mentioned among other revealed features.

The situation has radically changed when we used the НОМЕС. The gradual increase in the НОМЕС contribution in the electrolysis was accompanied by a regular decrease in the r _exp → 1 [272, 273], and the percentage of trans-configurations species increased too [276, 277]. These changes in the structure of the products under layer-by-layer shifting of the process from the electrode surface to the bulk reflects “layered” changes of conditions, including the change of the electric field strength, in the pre-electrode region. The concentration profiles of the products in the pre-electrode layer as a function of HOMEC contribution are to be known for quantitative analysis of the results obtained. An important factor for the application of the method, which we called the “EDL tomography” [276, 277] (more general “pre-electrode tomography” or PELTO), is the choice of model substrate. At the same time, PELTO provides the way to investigate the changes in organic reactivity under the heterogeneous effects: adsorption and chemisorption, high electric field, etc.

9.2.6.2 Electrosynthesis in the Chemistry of Biologically Active Compounds: Electro-deprotection Method

I have already provided examples of syntheses in a series of vitamins A and K, porphyrins, carotenes, etc. A special direction of investigation was the development of methods for electrochemical removal of protecting groups which we called as “electro-deprotection”. Temporarily protecting the definite centers of a molecule is a tactic widely adopted in organic syntheses, especially in peptide and carbohydrate chemistry. Removal of the protecting groups is usually carried out by more or less severe chemical treatments. Mild conditions and the possibility of smooth variation in the strength of “reagent,” i.e., the electrode potential, make electrolysis a very attractive for such conversions. In 1965, Horner and Neumann discovered the removal of Tos (i.e., p-toluenesulfonyl) group at Hg cathode in Me₄NCl/methanol solution. The experiment carried out without potential control was explained by the reaction with electrogenerated amalgam: $ {\mathrm{Me}}_4\mathrm{N}\cdot n\mathrm{H}\mathrm{g} $ [278].

We published almost simultaneously the direct electrochemical deprotection of Cin (cinnamyl, a new group), trityl (triphenylmethyl group), and Z (benzyloxycarbonyl group) groups by electroreduction in Alk₄NX–DMF solution [194, 195]. Later, we propagate this technique to a great number of other groups [279, 280]. In most cases, the process was carried out under рН control (Sect. 9.2.1, “Electrolysis at a Constant “pH” (“pX”) with Recording Equipment”). The HOMEC is also efficient for labile substrates and for difficult reducible (oxydable) groups [279–281]. For example, the HOMEC’s electron transfer beyond the supporting electrolyte discharge region was used to obtain glycine from its Z derivate with quantitative yield. Based on regularities governing the easiness of bond electro-cleavage and taking into account the decrease in the rate of the bond cleavage according to BCR rule (Sects. 9.2.3, “Cathodic Reactions with Bond Cleavage”), and “ec Processes: Cross-Correlation Between Parameters of the e and c Stages”), a method of activation of protecting groups by electron-acceptor substituents was developed. The activation method can be illustrated on benzyloxycarbonyl group (Z). Nonactivated Z cleavages at Е ≈ −2.9 V SCE, the activated (p-NO₂)Z at Е = −1.3 V, i.e., activation shift is as high as +1.6 V (!). The p-(NO₂)phenylsulfonyl derivative is reduced at the lower cathodic potential Е = −1.0 V, but without removal of the protecting group (a slow cleavage of C–N bond, in accordance with the BCR rule; it was demonstrated with the combined EC-ESR) [282, 283]. The theoretically predictable variation of the electrochemical activity, (Sect. 9.2.3), i.e., ease of cleavage of the protecting group is an important merit of the method.

We successfully used electro-deprotection reactions in the synthesis of various classes of natural compounds, such as amino acids, oligopeptides, glycoproteins, phospholipids, saccharides, polysaccharides, etc. [279–283]. Application of the method instead of chemical synthesis of oxytocin and desamino-oxytocins led, for example, to a twofold increase in the yield of these hormones with high degree of hormonal activity (joint work with the Riga’s chemists [284]).

9.2.7 Industrial Electrosynthesis

9.2.7.1 Dihydrotachysterol

This substance is an active agent for treating hypocalcemia and hypoparathyroidism (drugs А.Т. 10, Perlen, etc., daily dose of 0.6–1.1 μg). The known chemical process for its preparation by Birch reduction of vitamin D provides a yield of about 20 %. As was noted above (Sect. 9.2.2, “Natural Polyenes: Vitamins A and D, Carotenes, and Porphyrins”, Eq. 9.9), dihydrotachysterol (IV) is also formed by electroreduction, but the thermodynamically less favorable dihydrovitamin D (III) is the main product in this case too. We found the ratio (IV)/(III) to be independent of the e stage but to decrease sharply with increasing of the protonation rate of the radical anion (AR₂): with increasing temperature (−20 → +50 °C), with a decrease in donor numbers of the solvent (HMFT > DMSO > DMF > THF), with increasing water content in the solvent, and with increasing the acidity of the cation of the electrolyte (Bu₄N⁺ > Et₄N⁺ > Me₄N⁺, НОМЕС experiment). Acceptable conditions (dry DMSO, electrolyte Bu₄NJ, 20 °C, the yield of dihydrotachysterol ~40 %) were selected as a result of these studies [285–287].

The isomerization (III) → (IV) under the action of the strong base dimsyl (dimethylsulfoxide anion) was the second stage of the process, and the total yield of dihydrotachysterol increased to ~70 %. Here, the electrolysis of alkali salt in the dimethylsulfoxide on the graphite or carbon cathode was used to obtain dimsyl instead of the known Corey –Chaykovsky synthesis with sodium hydride [288]. This was our new “intersection” with E. Corey (cf. Sect. 9.2.2 “Natural Polyenes: Vitamins A and D, Carotenes, and Porphyrins”); in addition to safety, the advantage of electrolysis compared with the chemical method is also the possibility to easily produce dimsyl salts of various metals, including of the most active Cs⁺- salt. These three original stages were the basis of manufacturing dihydrotachysterol (VNIVI, since 1977).

9.2.7.2 Electrosynthesis of Diacetone-2-Keto-L-Gulonic Acid in the Vitamin C Production

Vitamin C, ascorbic acid, was the first synthetically made vitamin (Reichstein’s synthesis, ETH Zürich Hoffmann-La Roche 1938). Vitamin C in world production of vitamin products takes the largest share – tens of thousands of tons per year. Diacetone-2-keto-l-gulonic acid (DAG), which is the product of the fourth stage of the Reichstein’s synthesis, is obtained by oxidation of diacetone-l-sorbose (DAS) via the RCH₂OH + Ox → RCOOH reaction. The hypochlorite NaOCl is the oxidant Ox, but for environmental reasons, the more expensive KMnO₄ is used at plants located in urban areas. The direct electrooxidation of the DAS is an attractive alternative here. The first industrial electrosynthesis of DAG was carried out in the “Pharmakon” plant in Leningrad (graphite anodes, current efficiency β ~ 40 % and capacity of 250 ton/year) in 1970 [289]. This technology was later used in the Yerevan vitamin plant (Armenia) and in the Stanke Dimitrov (from 1990 Dupnitsa city) plant (Bulgaria). Around the same time, Fleischmann et al. suggested the mechanisms of electro-oxidation of alcohols on the Ni anodes in alkaline solutions [290] creating the basis for further work.

The main problem here is the low current efficiency due to the side reaction of oxygen evolution. A team of the ETH Zürich and of Hoffmann-La Roche solved the problem of decreasing current by developing the so-called Swiss-roll cell with a very large area surface of the Ni foil anode. A mini-pilot plant with an annual capacity of 750 ton was established on this basis [291, 292]. Simultaneously with the ETH Zürich and Hoffmann-La Roche team, we also attempted to solve the problem but using another approach, namely, by increasing the catalytic activity of the Ni anode. This was really achieved by using amino compounds as Ni ion-complexing agents (cf. Fig. 9.19). The team of young employees, first Isaac Gitlin alone and then with together with Anna Kukushkina and Vladimir Gurevich , established the optimal conditions for electrosynthesis, which were confirmed on a small laboratory installation. Trilon B was used as an amino compound. Based on the experience of I.A. Avrutskaya , M.Ya. Fioshin, etc. [86, 87] (Sect. 9.1.1), the electrolysis was carried out with the addition of Ni²⁺ salt; the process was monitored by an original express spectropolarimetric procedure.

Two years later, the process came into operation in the Yoshkar-Ola vitamin plant [293–296]. The main contribution to the industrial implementation of the process was made by chief engineer Sergej Alexandrovich Rosanov . He found a number of original technical solutions, and the electrosynthesis was brought into use without stopping the running production. The production line of 1500 ton/year with current efficiency of β = 70 % consisted of 10 similar units including the homemade electrolyzer (a simple and reliable bipolar undivided cell with stainless steel electrodes). The DAG electrosynthesis became the one of the largest in the USSR/Russia. And the capacity, 1500 ton/year, determined by the power of the Yoshkar-Ola plant, could be increased by many times. The designing of new plants was started in lates 80 with a capacity of 5,000 and 10,000 ton/year of vitamin C (these projects were not implemented). We informed about our developments only in 1990 [295, 296], and a detailed description has been given in a recent paper [297].

I must say here that our director Viktor Andreyevich Yakovlev persuaded me to carry out research in DAG electrosynthesis back in 1975–1976. He saw the promise of this work, pointing out the true disadvantages of the “graphit anodes”-technology in Leningrad’s “Pharmakon” plant. But I never got around to it then. In 1982, 5 years after the death of Viktor Andreevich, this work was prompted by special circumstances. The sharp deterioration of relations between the USSR and China led to termination of KMnO₄ deliveries from China and threatened vitamin C production in the Yoshkar-Ola vitamin plant. Under these circumstances, an effective electrochemical method was a task of utmost importance.

9.2.7.3 Completion of the History of the Vitamin Institute “ECHO”

The DAG electrosynthesis lasted for 10 years until 1994, when vitamin C production in Yoshkar-Ola has stopped. A few years later, the Institute of Vitamins, VNIVI, ceased to exist. In 1994, the former members of our electrochemical group, I.G. Gitlin and N.T. Ioffe, organized the research and production company “ECHO” (nauchno proizvodstvennaya kompaniya or NPK “ECHO”). This company now produces more than a dozen of drugs, including dihydrotachysterol, β-carotene, etc. And that is all that remains of VNIVI. The name of the company, “ECHO,” composed in memory of the DAG electrosynthesis of “electrochemical oxidation,” sounds today like the echo of the once existing Institute of Vitamins that contributed so much to the vitamin and pharmaceutical industry of the USSR.

9.2.8 Conclusion: Scientists in a Divided World From My Experience

In conclusion, I will say a few words on foreign scientific contacts in the period 1960–1990, i.e., from the end of “ottepel’” until the end of “perestroika.” I will start with the “literary” contacts. All of correspondence, letters, articles, etc., passed through the pervyy otdel (the first department) of the institute.^{Footnote 21} The authors signed a form confirming that the article “does not contain new data representing a scientific or technical interest” (one wonders who needs such an article?). The manuscript was examined by the pervyy otdel and then presented by the director of the institute to the Ministry’s UVS (Upravlenie Vneshnikh Snoshenij, Office of External Relations) for approval. Only articles approved by UVS could be sent for publication abroad. For instance, when one of my reviews [279] was blocked by UVS, V.A. Yakovlev had to petition in person and substantiate the plea emphasizing importance of that publication in the foreign journal Angewandte Chemie.

These obstacles meant that only a small fraction of Soviet scientific articles sipped through into the Western journals, and this led to rather rare citations of the papers of Soviet scientists abroad. I have already mentioned a few episodes from my practice (Sects. 9.2.2, “Natural Polyenes: Vitamins A and D, Carotenes, and Porphyrins” and “Cathodic and Gas-Phase Reactions of the Bond Cleavage”). The comprehensive bibliography of Soviet electroorganic chemistry including the USSR's author certificates compiled by Fritz Beck (Germany) is one the rare cases of fair recognition [3]. On the other hand, we had access to the Western journals in those years, naturally only for “technical” disciplines. Although, even in Moscow, the journals became available in libraries with a considerable time lag, and sometimes with missing pages (traces of censors work). But the infamous campaign against “cosmopolitan bowing to the West” had slowed down by the early 1960s, and even at a brief glance, one can see that the Soviet electrochemists extensively cited the works of foreign authors. Thus, the citation of articles in these years resembles a unidirectional West-to-East permeable membrane.

Significantly greater obstacles stood in the way of direct contacts. During my whole work in VNIVI, I had never been allowed to travel abroad, even not to a “socialist country,” up to 1987. The only exceptions were the trip to GDR (German Democratic Republic) in 1968 at the invitation of friends with whom we, Bella and I, had studied at MITKhT, and to Bulgaria, together with the chief of the Yoshkar-Ola vitamin plant, engineer Sergej Rosanov , to the Stanke Dimitrov's plant, in connection with the electrosynthesis of DAG. “As UNESCO asked me to organize collaboration between organic electrochemists from East and West,” the famous scientist Henning Lund (Aarhus, Denmark) wrote, “Sandbjerg meetings had participants from both sides and from all continents” [298]. But, unfortunately, not “from all continents.” In the late 1970s, I did get indeed a letter from Henning Lund , in which he informed me that I was included in the list of participants of the regular Sandbjerg meetings on organic electrochemistry. But the ministry’s UVS did not allow me to visit any one of them (there were three or four meetings and, therefore, letters from Lund ). Over the time, I accumulated a sadly large pile of invitations from different countries to symposia, conferences, and congresses, none of which I could attend. In my case, the visits were restricted because, first of all, I was Jewish and, secondly, not a member of the Communist Party. I should say that although it was almost mandatory for laboratory heads to be members of the Communist Party, I had, in our institute, the freedom of choice also in this matter, without rigid ultimatums. Of course, in day-to-day life at the Institute the Director had regularly predicaments with the “pervyj otdel”. Once, when I asked Prof. Yakovlev to take a physicist with an “inappropriate” (i.e., Jewish) name in the NMR group, Viktor Andreevich agreed, but after some deliberation he suggested to postpone the issue until the time of his holiday. Ultimately, the application for a job was approved by the acting director, Vladimir Ivanovich Gunar, instead. However, the visits abroad were governed by “external forces,” and Yakovlev was powerless here.

Yet, one foreign contact took place, however, on “our territory.” In 1976, one of the leading scientists in organic electrochemistry, Dr. James Grimshaw from the University of Belfast, came to IELAN, Moscow. I got a call from my friend, Alexander Ershler from IELAN, who said that Dr. Grimshaw would like to visit our laboratory. V.A. Yakovlev gave permission. When Dr. Grimshaw and I first met, we felt mutual respect and sympathy and a 3-day “VNIVI program” was put together. We showed him our experimental techniques (he was, particularly, interested in “pH-static” electrosynthesis) and told him about our works and discussed them. A seminar was organized, and Dr. Grimshaw made a brilliant report on organic electrochemistry and his works to a large audience (translated by Ella Boltyanskaya from our lab). An evening concert in the Great Hall of the Moscow Conservatory was the starting point of our cultural program. There were three of us, along with my 11-year old son, who attended a specialist English language school and was very excited to meet a “real British gentleman.” And on Sunday, on request of Dr. Grimshaw , we took a trip to Zagorsk, to the famous Troitse-Sergiyeva Lavra (Holy Trinity Church-St. Sergius Lavra). It was a risky trip, because Dr. Grimshaw had no permission to leave Moscow. It was dangerous to go by train (70 km from Moscow) as we could be seen by controllers or “vigilant” passenger scammers. V.A. Yakovlev provided the institute minibus for Sunday with a “reliable” driver and gave instructions on how to behave in an event of extraordinary situation. Fortunately, all without incident, we took a tour guide and managed to see a lot of interesting places; among them is the Duchovskaya (Holy Spirit) Church, exactly 500 years after its construction (1496).

I was allowed to attend foreign meeting for first time in 1987, the Symposium in Sopron, Hungary [203]. But fundamentally, the situation with the invitations to the conferences changed only with the beginning of “perestroika.” At once, a vast geography opened: Praha-Liblice (Heyrovský discussions), May 1989 (Fig. 9.20); Stockholm (32nd IUPAC Congress), August 1989; Montreal (177th Meeting of Electrochem. Soc), May 1990; etc. Then, with great joy, I finally met Henning Lund , Norman Weinberg (Electrosynthesis Co., USA), and other electrochemists long known to me by their works. During my second visit to London (summer, 1991), as guest professor at the Queen Mary College (the laboratory of Prof. J.H.P. Utley ), I was invited by Dr. James Grimshaw . In the few days I spent in the hospitable home in Belfast, I met James’s wife, Dr. Jadwiga Grimshaw, also an electrochemist and, as it turned out, a talented artist. I visited their laboratory at Belfast University. As a surprise, James, with a smile, found an article with Boltyanskaya [272, 273] published in Doklady Chemistry, an English edition of Doklady AN SSSR: his university subscribed to this magazine in English! Several copies of the article were made right there, and no permission of the “pervyy otdel” was required.

In 1993, Professor Fritz Beck invited me to the 44th ISE meeting in Berlin [247]. Our documents for emigration to Germany had long been ready. Two weeks after my return to Moscow, on September 23, we all together, with my brother Felix and his family, flew to Germany (Felix, professor of hydraulics, worked as the head of the Hydrology Laboratory of NII VODGEO). In Russia, it was the time of another rampant anti-Semitic wave, this time headed by the “national–patriotic” society “Pamyat” (“Memory”). We were kept at the airport the whole day and finally allowed to board the last leaving airplane. We know firsthand what anti-Semitism is and did not want this for our kids. But that is another story.

Summing up, I can say that isolation from Western scholars has made substantial damage. It is hard to imagine how broad our horizons would have been if we had been able to interact with foreign members of the like-minded scientific community without interference. “We sat outside the fence, having fun in the kitchen, singing in the woods …” is how satirist Mikhail Zhvanetskiy referred to the pre-“perestroika” time in the Soviet Union. Our work in VNIVI was akin to singing in a “small forest.” VNIVI had its own microclimate, which gave a sense of local “freedom” and an excellent opportunity to work. It is a merit of Prof. Viktor Andreevich Yakovlev . Of course, Moscow was exceptional because we had experts of the highest level working in various fields of chemistry and could discuss any topic among ourselves. On the other hand, EKhOS, being an extremely comprehensive field in itself, was the “big woods” covering the vast ranges of the USSR. Regular and lengthy meetings of specialists in organic electrochemistry from many cities and of different schools of thought, as well as the publication of conference proceedings and books on EKhOS, created a special bond and creative and stimulating climate. This is a merit of academician Alexander Naumovich Frumkin and his team of assistants, L.G. Feoktistov , А.P. Тоmilov, М.Ya. Fioshin , S.G. Mairanovskii, Ya.P. Stradyn , Yu.M. Kargin , V.D. Bezuglyy , Yu.S. Lyalikov , Yu.M. Tedoradze , L.I. Krishtalik , А.B. Ershler , D.I. Dzhaparidze , and others. The songs from this “big woods,” the EKhOS, were loud and echoed far although they were not always heard by our colleagues outside the fence.

Notes

1.
He performed the thesis “Study of polarizability of complex molecules” under the supervision of Yakov Kivovich Syrkin, a member of the USSR Academy of Sciences, one of the leading Soviet theoretical chemists. In 1951, Syrkin was accused of “cosmopolitanism and propaganda of ideologically misguided resonance theory” and, together with Frumkin , of underestimation of the “decisive contribution of Russian scientists to physical chemistry” (due to their joint article in the Great Soviet Encyclopedia). This was followed by dismissal of Syrkin from the Karpov Institute of Physical Chemistry and by dismissal of Frumkin as director of the Institute of Physical Chemistry of the USSR Academy of Sciences.
2.
Here and below we use the system of abbreviated notation of electrode reactions (see Appendix). Thus, a complete schema of reactions (9.2) is written as “–e(d)(h)a–e–p,” where “–e,” “h,” and “–p” are transfers of electron, hydrogen, and proton, “d” and “a” are C–N bond dissociation and C–C bond association, and in the brackets (d)(h) are parallel stages.
3.
M.E. Vol’pin (1923–1996) was a Dr. chem. sci. (1959), an academician (1987), and the director of INEOS (1988–1996). Vol’pin got a contract at INEOS only as a result of persistent efforts of Kursanov in 1958, 3 years after he began work unofficially for free in Kursanov ’s laboratory, because of restrictions for persons of Jewish nationality (see [54]). I met them both during my unsuccessful application to INEOS in 1961 (see Sect. 9.2).
4.
Other mechanisms suggested [3, 63] are ↑epe↓ap and ↑e↓apep with the participation of the initial substrate RH in a bimolecular step “a” (for the notation, see Appendix).
5.
The “Knunyants ’s lactone” for acetobutyrolactone and “Knunyants ’s regrouping” are established terms in the literature.
6.
This “closed” organization was also called NII-42: a number is assigned to each “closed” organization and in everyday use they were called “numbered enterprises,” “mailboxes,” or simply “boxes.”
7.
Biographical material is taken from [95].
8.
Biographical data for this section were mainly taken from the book [98].
9.
Recall that the phenomenon itself and the method of ESR were discovered by Ye.K. Zavoysky in Kazan, KGU, in 1944.
10.
According to the memoirs of A.P. Tomilov , Yu.M. Kargin proposed to use an acronym EKhOS in the title of national conferences [89].
11.
Yan Pavlovich Stradyn in Russian transcription.
12.
Ya.P. Stradyn and R.A. Gavar presented this material on the CITCE’s 14th meeting, Moscow, 19–25 August 1963 (as per Dr. V. Glezer). Their work [125, 126] on in situ EC-ESR of nitrofurans has been published about a year before that of the Kazan scientists [105]. Geske and Maki [127] are commonly considered the pioneers of the in situ EC-ESR. However, Alexander Galkin and coworkers in the Kharkov FT I (Kharkov Physics-Technical Institute) in 1957 [128] were the first to carry out in situ electrochemical generation in the ampule of an ESR spectrometer.
13.
In a small room, in front of the cathedral library, we had worked together with Andrey Mirzabekov (1937–2003)—the future academician and director of V.A. Engel’gardt Institute of Molecular Biology USSR AS and future director of Biochip Technology Center at Argonne National Laboratory, USA. I worked on polarograph and Andrej on preparative chromatograph. The room was not equipped with ventilation and Nikolai Alekseevich asked us daily if there was any toxic contamination by mercury or solvent. Understanding our responsibility, Andrey and I worked neatly and carefully.
14.
I had a bad experience with another academic institution, INEOS. In 1961, prior to the work assignment to VNIVI, on the recommendation from my brother, Stal’ Mairanovskii, I was invited for an interview by Dr. Zinaida Naumovna Parnes; she studied hydride transfer reactions. She gave me reprints of her articles and asked me to think about the application of electrochemistry. A few days later, in INEOS, I met Dr. Parnes and Dr. Mark Yefimovitch Vol’pin again to continue our discussion. They were satisfied with my interview and suggested I apply for employment to the Director, acad. A.N. Nesmeyanov and introduced me to D.N. Kursanov , corr. member of USSR AS, the head of their department. Kursanov signed my letter and wished me a bright future in INEOS. Just a week later, I had a call from Dr. Z. Parnes, and she asked me to come: INEOS’s “pervyy otdel” blocked my admission (about the pervyy otdel, or first department, see Sect. 9.2.8).
15.
This forces to interrupt electrolysis during pH measurements [180] or completely abandon pH monitoring. Thus, electrolysis was conducted in a diaphragm-less cell with a platinated Pt anode under hydrogen bubbling to prevent the alkalinization of the catholyte [181].
16.
The electrochemistry of carotenes and porphyrins was the topic of the Ph.D. theses of Askold Anatoliyevich Engovatov (carotenes) (1975) and Ichtior Muradovich Muratov (porphyrins) (1986).
17.
We consider it advisable to divide reactions into three groups: (1) with slow and moderately fast cleavage 0 < k ^*_d < 10³ s^–1 (SMFR) and (2) fast 10³ < k ^*_d < 10¹⁰ s^–1 (FR) and (3) ultrafast cleavage (UFR) k ^*_d ≥ 10¹⁰ s^–1 [225].
18.
Equation (9.13) (without reference to [204, 231]) was later used by J.M. Savéant [232–235].
19.
Publications in Doklady AN SSSR had to be submitted by a member of the Academy of Sciences (academician).
20.
The term “redox catalysis” [258] that is often used instead of HOMEC in the literature is inadequate, because it does not reflect the involvement of the electrode itself in the electrochemical reaction (stage “e”) and the homogeneous character of the ЕТ on the substrate (stage “e _v”). In additions, this term is widely applied to other phenomena. The involvement of the electrode is also not expressed by the term “homo-mediator system” [259]. Starting from Kobozev and Monblanova [260], the term “electrocatalysis” became accepted for heterogeneous electrode reactions, and the “homogeneous electrocatalysis,” HOMEC, involves both e and e _v stages.
21.
These studies are included in the Ph.D. thesis of Leonid Yu. Yusefovich (1978).
22.
This hypothesis is supported by the first results of viscosity measurements in the pre-electrode layer at a distance of δ < 6 nm [274] using an idea of combined EC-AFM method [275]. After the symposium [275], Prof. Dieter Kolb introduced me to a group of scientists from Mainz, they invited me to hold a seminar and we had a joint project. Prof. Kolb followed it with great interest. I fondly and with gratitude remember this outstanding electrochemist (1942–2011).
23.
This work became the basis of Ph.D. dissertation by Nina Fyodorovna Loginova (1977).
24.
The materials given in this section were the object of a large number of “closed” USSR author’s certificates; they entered in the closed (not openly accessible) Ph.D. dissertations by Inna Alekseyevna Titova (1979) and Isaac Grigorjevich Gitlin (1985).
25.
The pervyy otdel (first department) in the Soviet organizations oversaw the hiring of staff, travel abroad, access to information, foreign correspondence and publications, and use of typewriters and copiers (countering the “samizdat,” i.e., reprint of banned literature). The information about employees, their political views, etc., was also filed there.

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Acknowledgments

I am grateful to my wife, Dr. Bella Lurik , for her support during the writing of this work, for advice, and for memories of some events and meetings.

I express my gratitude, to Drs. Galina Bekker, Victor Glezer, Naftolij Ioffe, Vladimir Kurmaz, Emma Malakhova, Feliks Mairanovsky, Irena Mayranovsky, Elena Obol’nikova, Vladimir Petrosyan, Garislav Shkolenok, Igor’ Sirotin, Mikhail Yanotovskiy , and El’sa Zacharova for providing valuable materials and photos; and to Yulia Polyak for her work with photos.

I sincerely thank Dr. Boris Kahn and Dr. Stephan Samvelyan for their assistance with translation and especially my daughter Dr. Elena Boyd for her advice, changes, and corrections.

My special thanks to Dr. Fritz Scholz for his comprehensive help with this article and the whole idea—to write a book about the work of scientists under conditions of a unique historical experiment, which divided mankind in two worlds.

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Victor G. Mairanovsky
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Victor G. Mairanovsky

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Fritz Scholz

Appendix: Symbolization of Electrode Reactions (Based on [299])

Symbols “e,” “e _v,” and “ε” refer, correspondingly, to the heterogeneous, “volume” (without of any electrode interface effects) and solvated electron transfer; “c” and “c _s” refer to the volume and “surface” chemical stages. Designation of chemical stages “c”: according to particle, “p” (proton) and “h” (hydrogen), “minus” for detachment of a particle, and for attachment of a particle the “+” sign is omitted; and according to the type of reaction, “a” (association, bond formation), “d” (dissociation, bond cleavage), and “r” (rearrangement, isomerization). The subscripts N, E, R, and M (nucleophil, electrophil, radical reagents, material of the electrode) are used to indicate the nature of the substances; the subscript “2” is used for the dimerization reaction. The parallel reactions, the reactions of the second substance, and the “concert reactions” are written in the brackets ( ), [ ], and { }, correspondingly. The origin and the carry points of reagents may be indicated by the arrows “↑” and “↓,” correspondingly. Capital А and С letters may precede the reaction schema in order to distinguish between anodic and cathodic processes. The overall number of stages and the transported particles are given with the “∑” sign, for example, ∑2edp [cf. Reaction (9.7a)]. When written compactly, the symbols are entered directly in the reaction equation [cf. Reaction (9.6)].

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Mairanovsky, V.G. (2015). Organic Electrochemistry in the USSR. In: Scholz, F. (eds) Electrochemistry in a Divided World. Springer, Cham. https://doi.org/10.1007/978-3-319-21221-0_9

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Organic Electrochemistry in the USSR

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9.1 Organic Electrochemistry in the USSR: The Main Centres and Fields of Work

9.1.1 Moscow and the Moscow Region (up to 200 km)

9.1.2 Moscow Region, Tula

9.1.3 Kazan

9.1.4 Riga (Republic of Latvia)

9.1.5 Novocherkassk

9.1.6 Kharkov (Republic of Ukraine)

9.1.7 Kiev (Republic of Ukraine)

9.1.8 Alma-Ata (Republic of Kazakhstan)

9.1.9 Karaganda (Republic of Kazakhstan)

9.1.10 Sverdlovsk

9.1.11 Other regions

9.2 My Experience: From the End of the “Ottepel’” to the End of “Perestroika”

9.2.1 Development of Experimental Techniques and Procedures

9.2.1.1 DME with the Dropping Control

9.2.1.2 Accurate Measurement of Half-Wave Potentials on the SCE Scale in Nonaqueous Media

9.2.1.3 Voltammetry with the Symmetric Trapezoidal Voltage Pulses (VATZ)

9.2.1.4 Electrolysis at a Constant “pH” (“pX”) with Recording Equipment

9.2.2 Mechanisms of Electroorganic Reactions

9.2.2.1 Natural Polyenes: Vitamins А and D, Carotenes, and Porphyrins

9.2.2.2 Cathodic and Gas-Phase Reactions of the Bond Cleavage

9.2.3 Chemical, and Electrochemical Reactivity

9.2.3.1 Linear Conjugated Polyenic Hydrocarbons

9.2.3.2 Monofunctional Derivatives of Polyenes and Porphyrins

9.2.3.3 Cathodic Reactions with Bond Cleavage

9.2.3.4 ec Processes: Cross-Correlation Between Parameters of the e and c Stages

9.2.4 Homogeneous Electrocatalysis

9.2.5 Combination of Electrochemical and Other Analytical Techniques

9.2.5.1 In Situ Electrochemical ESR

9.2.5.2 In Situ Electrochemical NMR

9.2.5.3 Combined Electrochemical Stop-Flow Method

9.2.6 Organic Electrosynthesis

9.2.6.1 Electrosynthesis as an Investigation Tool: Pre-electrode Tomography

9.2.6.2 Electrosynthesis in the Chemistry of Biologically Active Compounds: Electro-deprotection Method

9.2.7 Industrial Electrosynthesis

9.2.7.1 Dihydrotachysterol

9.2.7.2 Electrosynthesis of Diacetone-2-Keto-L-Gulonic Acid in the Vitamin C Production

9.2.7.3 Completion of the History of the Vitamin Institute “ECHO”

9.2.8 Conclusion: Scientists in a Divided World From My Experience

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Appendix: Symbolization of Electrode Reactions (Based on [299])

Appendix: Symbolization of Electrode Reactions (Based on [299])

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