VLAD~IIR IIIKHAILOVICH RODIONOV ton the Hundredth Anniversary

of His Birth)*

K. Ts. Elagina and N. A. Kravchenko

Vladimir Mikhailovich Rodionov

The date October 28, 1978, marks the 100th anniversary of the birth of the outstanding Soviet chemist Academician Vladimir Mikhailovich Rodionov. His entire life was an example of honest, selfless service to science, people, and his country. His motto was work, truth, and justice.

Vladimir Rodionov belonged to the group of people who are generously and versatilely gifted by nature. The talents of a scholar, engineer, pedagogue, and public servant with unlimited human charm, modesty, nobility, and sincerity were wonderfully combined in him~ Still, those who knew Vladimir Rodionov well recall his exceptional kindness and sympathy, as well as his accessibility and the simplicity in his greetings. Being irreproachably honest in questions of scientific ethics, Vladimir Rodionov willingly shared his knowledge with all and was truly happy with the success of others. Rodionov sometimes gave advice with-

*This paper was printed according to a decision of the editorial board of the journal on

November 17, 1977.

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No i0, pp. 2201- 2211, October, 1978.

0568-5230/78/2710-1943507~50 �9 1979 Plenum Publishing Corporation 1943

out ever making the receiver sense his superiority, and he taught without "lecturing. ~'

Vladimir Mikhailovich Rodionov was born on October 28 (16), 1878, in Moscow. He com- pleted the lloscow Trade School, and he obtained his further education first at the Dresden Polytechnic Institute and then at the Hoscow Higher Technical School.

The nature of the activity of the scientist Rodionov was determined to a considerable extent by the problems with which the engineer Rodionov had to deal and his enthusiasm to create and develop the Russian industry of organic chemistry. Hany of its theoretical investigations originated during his engineering activity on enterprises for the chemical industry. Furthermore, this engineering activity left its mark on all of his scientific endeavors. IIis theoretical investigations were always closely related to life and the vital needs of his fatherland and were dictated by the requirements for industrial development.

The beginning of the Rodionov's activity (1906) was associated with the chemistry and technology of the production of dyes. The main result of this work was the creation of especially chlorine-resistant azo dyes, as well as an original method for the synthesis of thioindigo.

At that time the chemical industry in Russian was represented only by foreign companies, and Vladimir Rodionov had to work at the Bayer company. World War I required the quick organization of a number of chemical production lines, including those for intermediates and dyes.

After release from the active army because of an injury, Rodionov was employed as a technical manager and then as a director at the Trigor plant. There he quickly set straight the production of such strategic raw materials as nitrobenzene, dimethylamine, diphenylamine, and dinitronaphthalene, as well as some intermediates and dyes, viz., a-naphthol, a-naphthol, sulfanilic acid, 2-naphthylamine, Methyl Violet, Methylene Blue, Sulfur Black, Acid Orange, and many others.

Vladimir Rodionov made daily visits in the morning and in the evening to all the de- partments of the plant and solved the problems which had arisen directly at the equipment. At the same time, he directed the research work which was conducted in the laboratory.

In 1916 Rodionov was summoned to work on the War-Industry Committee as the chief engineer of the chemical section, and soon he was also called to work on the Commission on the Transmobilization of the Military Industry. The circumstances in the country at that time (war, devastation, and famine) urgently called for the development of the production of drugs, and the Russian industry at that time had not gone beyond the obtaining of extracts from plants. Rodionov together with A. E. Chichibabin organized a workshop for drugs at the Moscow Higher Technical School in 1915. In 1916 he established the first department for the chemistry and chemical engineering of pharmaceutical preparations in Russia at the same institute. This provided the base for the development of production methods for the synthe- sis of such valuable alkaloids and pharmaceuticals as morphine, narcotine, papaverine, codeine, theobromine, and so forth.

Rodionov's practical work was accompanied by scientific investigations, especially in the field of the chemistry of alkaloids. The development of an original and efficient method for the synthesis of codeine by the methylation of morphine and of methods for the isolation and purification of the opium alkaloids, as well as the creation of new methods for the synthesis of narceine and heroin, date back to that time.

Such a combination of scientific and practical activity brought a new spirit to the atmosphere at the Moscow Higher Technical School and gave Rodionov authority among the pro- fessors and great popularity among the students.

Rodionov used the experience he acquired in 1917 during the construction and initial operation of a salicyl plant and the first alkaloid plant in Russia at Blagush, where the production of codeine from powdered tea, theobromine from cacao pods, and omnopon was carried out for the first time in Russia. The production of codeine according to the Rodionov method, which is still the method used to obtain it all over the world, was also set up there. The State Alkaloid Works, where a number of the production lines set up by Rodionov are still functioning, was subsequently built on the basis of this plant. Rodionov maintained a continual connection with this plant throughout his life, and at it he delivered his last

1944

paper shortly before his death, which occurred on February 7, 1954.

World War I and then the civil war resulted in the complete destruction of the rudiments of chemical production, and Rodionov, who was one of the most prominent specialists in the chemical industry in the country at that time, wrote an extremely interesting review in 1920 on the development of the chemical-pharmaceutical and indigo-dye industries in Russia and carried out engineering calculations for the regeneration of the chemical industry as a whole and the production of dyes and drugs in particular.

In 1920 Rodionov was elected to be the professor of the department for the chemical engineering of pharmaceuticals, which he had organized, at the Moscow Higher Technical School, and in the same year he was invited to the Second Moscow State University. There he set up a department for the chemistry of alkaloids. The next 20 years were very fruitful for his activity. Many problems with which he had to deal as an engineer in the production of dyes and drugs were developed.

In 1923 V. H. Rodionov and V. Ko Matveev [i] discovered a new method for the synthesis of aromatic diazo compounds by reacting nitrous acid with phenols, rather than amines, as had usually be done, e.g.,

OH OH OH Ott I ! ! i 0_++ 0=+oo +o,()_+

I N=CI

As it turned out, nitroso compounds form first and are then converted into diazo compounds

under the action of the oxides of nitrogen. It is interesting that in the case of salicylic acid, the diazo group enters at the site of the carboxyl group. This method is still em- ployed in industry.

Together with S. I. Kanevskaya, Rodionov [2] carried out an investigation of the util- ization of opianic acid (I), which is a waste product of the production of opium alkaloids, for the purpose of synthesizing several intermediates and dyes. Acid I was converted by a relatively simple method into two isomeric dimethoxyanthranilic acids (II and III):

CHO COOH

MeO [ COOH MeO 1 COOH OMe OMe (I)

co l MeO I CO

OMe

Acid II was converted into the two indigo derivatives

NH2

. +

/ % / ~ \ M(.O I C00H

O_~ie (H)

COOH

Me0 ] NH~ O,~:e (m)

S S NH NH

\ c = c / \ S % // \ c = c / \ / / "\ MeO R C C I O~Ie MeO ] CO CO [ OMe

Me0 II 11 0Me 0 H OH 0 0

Acids II and III were subsequently [3] used for the synthesis of many azo dyes and vat dyes

of the anthraquinone--acridone series, e.g.,

1945

�9 ~/OMe ~/OMe HN" ~,~ "x, OM e .,)x~ fix

c o f i ~ HN" y >OM~ .//\/'-~ ~ iC0 ~ co I CO

M e O ~ .NH

MeO/ i ' -~ - . . f

A number of Rodionov's studies various halogen-containing compounds:

SH SR

C00H C00H

[4] were denoted to the interaction of thiosalicylic acid with

(iv)

S

C I

o H (v) R = CH~COMe;CH~COPh;CH~CH(0M~);CH~CH(0Et)~;CH~C~H4NO~;CH(Me)C00Et

On the basis of these studies he demonstrated the possibility of the transition from compounds of type IV to derivatives of 3-hydroxythionaphthene (V), which are easily converted into thioindigo.

These, as well as many of Rodionov's other studies in the field of dyes, have found extensive application in the indigo-dye industry and were awarded a State Prize.

In 1925 Rodionov was named the director of Indigo Trust of the Supreme Council of the National Economy, while remaining the director of the Trigor plant. His participation in the construction of the Dorogomilovskii and Derbenevskii plants is related to that time. He maintained scientific relationships with these plants, as well as the Scientific-Research Institute of Organic Intermediates and Dyes until the end of his life. From 1935 to 1944 Rodionov ran the department for the chemical engineering of dyes at the Moscow Textile Insti- tute.

Along with his scientific investigations in the field of intermediates and dyes, Rodionov worked in the field of the chemistry of alkaloids and drugs. As we have already noted, he be- gan these investigations in 1915 in the workshops of the Moscow Higher Technical School and continued them for 20 years at the Second Moscow State University and subsequently (1935-1939) at the All-Union Institute of Experimental Medicine. He thoroughly investigated the methyl- ation of morphine by trimethylphenylammonium chloride and showed that the process is strictly directed: Only the phenol hydroxyl is methylated. In parallel with the study of quaternary bases Rodionov extensively investigated the alkylating properties of esters of aromatic sulfonic acids of the benzene and naphthalene series and discovered that they are excellent alkylating agents for phenols and amines [5, 6].

Rodionov studied the effects of methyl p-toluene sulfonate on various nitrogen-containing heterocyclic compounds, viz., ~-methylmorphimethine, papaverine, brucine, cinchonine, narco- tine, and others. Narcotine (VI) yielded an addition product (VII), from which narceine (VIII) was obtained upon treatment with alkali:

OMe M~ OMdo ~ OMe OMe Me

~aoo rm--o "~ "co ~,o:~ ~ "coo~

\ ~o~2"~.CH~CH~N(Meh (vl) (vIr) (VHI}

This reaction served as an example which demonstrated the possibility of the splitting of a heterocycle during exhaustive methylation by methyl p-toluenesulfonate.

Antipyrine was obtained from methyl p-toluenesulfonate and methylphenylpyrazolone, and

1946

pyramidon was synthesized by reacting aminoantipyrine with methyl p-toluenesulfonate. This method of obtaining pyramidon is still widely used. The same method was used to obtain theo- bromine and caffeine. Esters of aromatic sulfonic acids and quaternary bases are still widely used in various branches of the chemical industry.

Rodionov attached great significance to the study of the accessible alkaloid plants of the temperate zone, viz., celandine and 6~elidoni~ majus. In 1939 he began work on the iso- lation of the celandine alkaloids [7], and together with N. N. Suvorov [8-10] he began synthet- ic studies in this area for the purpose of obtaining the model compound N-methyl-6-hydroxy- hexahydrobenzophenanthridine (IX), which contains the skeleton of the alkaloid chelidonine (x) :

~ ':l~I-' ctt,. ,it z / O ~ C ~ " CHOH

(Ix). (X) o C H z

Rodionov did not lose interest in the investigations in the field of th~ chemistry of alka- loids to the end of his life. Shortly before his death, in 1952 he delivered a paper at the combined session of the Division of Chemical Sciences of the Academy of Sciences of the USSR and of the Academy of Sciences of the Uzbek SSR in Tashkent entitled "The chemistry of alka- loids, its significance and forthcoming tasks" [II], and in 1953 he wrote a review on the development of the chemistry of alkaloids in Russia [12].

Among the numerous papers written by V. M. Rodionov, those devoted to the study of �9 aromatic aldehydic acids and their derivatives occupy an important place. His first investi- gations in the field of aldehydic acids were, as we have already noted, undertaken for the purpose of using 6-formyl-2,3-dimethoxybenzoic acid, or opianic acid (I), which is a by- product of the production of cotarnine and hydrastinine. However, as a result of this investi- gation, there was a series of studies, during which many properties of I and its conversion products were ascertained, and other o-aldehydic acids were studied. An interesting feature of I and its analogs is their ability to react in two tautomeric forms, one being an alde- hydic acid, and the other being a derivative of hydroxyphthalate [13]:

IIOH CHO C

o

MeO MeO r! 0

(I) (Ia)

T h a n k s t o t h i s s p e c i a l f e a t u r e , a c i d I c a n y i e l d two s e r i e s o f d e r i v a t i v e s , w h i c h w e r e o b - t a i n e d b y R o d i o n o v . I n p a r t i c u l a r , h e f o u n d [14] t h a t I r e a c t s i n i t s a l d e h y d e f o r m w i t h w a t e r u n d e r p r e s s u r e t o f o r m i s o v a n i l l i n

CHO

, + MeOH -~- CO z

MeO OH

The reaction of I with KCN results in the formation of cyanomeconin [15]. Introducing i into his modified Cannizzaro reaction, Rodionov [16] obtained meconin with a 90% yield. This is the best method for its synthesis.

Rodionov's work in the field of aromatic aldehydic acids and their conversion products led to the creation of new methods for the synthesis of methoxylated benzene derivatives, which form the basis of a number of physiologically active compounds and fragrances. These investigations were developed most extensively by Rodionov in the last 15 years of his life, first at the Central Scientific-Research Laboratory of the Main Administration for Perfumes, which subsequently became the All-Union Scientific-Research Institute of Synthetic and Natural Fragrances. Many important problems in the perfume industry were solved there under his

1947

guidance.

Rodionov studied the synthesis of vanillin (as well as vanillal) by th e "glyoxyl" method. He studied the conversion of (4-hydroxy-3-ethoxyphenyl)glycolic acid to 4-hydroxy-3-ethoxy- benzaldehyde (vanillal) [17]:

CH(OH)COOH CHO T I

I og t I OEt OH OH

+ HCOOH

Together with K. S. Polyakova, he developed a method for the synthesis of p-methoxybenzalde- hyde (anisaldehyde) from phenol [18]. The method developed by Vladimir Rodionov [19] for the synthesis of monosubstituted acetoacetates without the use of free acetoacetic ester was of great importance for obtaining intermediates for the synthesis of fragrances. This method was based on the reaction of alkylating agents with sodioacetoacetic ester obtained directly during the ester condensation of ethyl acetate:

E t 0 N a RHal 2 MeCOOEt -~ MeCOCH(Na)COOEt -* MeCOCH(R)COOEt

Benzyl-, cumyl-, phenylethyl-, and other substituted acetoacetic esters were obtained by this method.

Together with V. N. Belov [20], he used monosubstituted acetoacetic esters to synthesize compounds that have the odor of geraniol, citronellol, and other flower and fruit odors. In the series of aliphatic--aromatic aldehydes he synthesized two new fragrances, which are simi" lar to so-called cyclomenaldehyde [21, 22].

The practical significance of Rodionov's work for the development of the Russian perfume industry was soon appreciated, as is evidenced by the awarding of the State Prize to him and a group of co-workers.

One of the most interesting aspects of Rodionov~s work is his fundamental research in the field of B-amino acids. In 1926 Rodionov and E. F. Malevinskaya [26] showed that the reaction of piperonal with malonic acid in the presence of ammonia results in the formation of B-piperonyl-B-aminopropionic acid with the simultaneous formation of the corresponding cinnamic acid:

~i~c--0 HoC--O ,~ H2i~X_ -

CHO -~ CII2(COOH)2 + NH 3 ~ O ~ ~ HCH2 COOH + O H=CHCOOH + CO~ + H.~O

This unusual reaction interested Vladimir Rodionov, and with all his energy he began an extensive series of studies to extend it to various aldehydes, alkyl-substituted malonic acids, esters of malonic acid, and alkylamines [27, 28]. He proposed the following mechanism for the open-chain reaction:

NH /

RCH \

0tI

O /OH / jNH~

RC// + N I - I 3 - , R C H ~ or RC\ )

\ H NH~ \ H / NH~. NH~ I I

+ CH2(COOH)~ --, B.CHCH(COOH)., ---, RCHCH.2COOH + COt + H~O

O f

RC + CH2(COOHh -- RCH=CHCOOH + CO~ + H20 \ H

As was subsequently shown, not only aldehydes of the benzene series, but also naphthalene [29-32], hydroaromatic [32, 33], heterocyclic [34, 35J, and aliphatic [36, 34, 37] aldehydes undergo the Rodionov reaction, which is its modern, widely used name. In 1950 V. M. Rodionov

1948

and A. M. Fedorova [38] were able for the first time to carry out the reaction with a ketone, viz., acenaphthenequinone:

OC--CO I I

J x , 7 ~ . CH,lCOOH):

NH.~ /

OC--C

[ [\CH~COOH

Besides ammonia, it proved possible to use its carbonate and acetate, methyl-, ethyl-, propyl-, and benzylamine as the amino component to carry out the reaction in acetic acid or benzene media. Of the derivatives of malonic acid the reaction was carried out with ethyl- malonic acid, benzylmalonic acid, and its diethyl ester [39].

In response to the growing interest in B-alanine, which is the simplest of the B-amino acids and most widely represents this class of compounds in nature, in 1948, V. M. Rodionov and N. G. Yartseva [40] proposed a simple method for the synthesis of this amino acid by the addition of phthalimide to esters of acrylic acid in the presence of trimethylphenylammonium. The reaction proceeds with an almost quantitative yield.

The Rodionov reaction, which requires fairly simple starting compounds, is very simple to carry out and provides for the isolation of the desired products with yields up to 75%~ immediately made D-amino acids readily available and stimulated both the further synthesis of their individual representatives and the study of their various conversions. To Vladimir Rodionov the investigation of the conversion of B-amino acids to heterocyclic compounds of the pyrimidine, imidazole, and 2-oxadiazole series was of the greatest interest.

Pyrimidine derivatives of several types could be obtained. For example, 4-aryl(alkyl)- 2,6-dioxohexahydropyrimidines (dihydrouracils) were obtained by the cyclization of ureido acids [41]:

(R') NH~ NHCONH~ NH--CO

/ / Hcl / \ KCN0 or - . RCH ~ RCH RCH - - NH(W') \ u r e a . \ , \ /

GH~C00H CH2C00H CHz--C0 (a" ')

When substituted reactants are used, it is possible to obtain the corresponding i-, 3-, and 5-substituted pyrimidines; however, the accumulation of radicals, especially aromatic radi- cals, hampers the cyclization. In a joint work with B. I. Kurtev [42] it was shown that 2- thiodihydrouracil is obtained at once with potassium thiocyanate. It proved possible to obtain 4-aryl(alkyl)-2-imino-6-oxohexahydropyrimidines(dihydroisocytosines) through B- guanidino acids [43]:

NH NH // //I NH~ NH N H - - - - - - - - C N t t - - C

/ / / / \ / \ RCH 4- C--NH~ -~ RCH NH2 -~ RCH NH

\ \ \ \ / CH~C00H 0Me CH~--C00H CH2--C0

Finally, pyrimidine derivatives of another type, viz., 2,4-diaryl(alkyl)-6-oxotetrahydro- pyrimidines (XI), were obtained in a joint project with V. K. Zvorykina [44]. These deriva- tives were obtained as a result of the successive treatment of N-benzoylated B-amino acids by thionyl chloride and ammonia, the course of the reaction being dependent on the temperature:

1949

NHCOPh SOCI~

RCH \

CH~00H

Ph Ph / /

N=C N , C / Xx , NH, /

�9 RCH C1 - - ~ RCH NH (xI)

CH~COCI CH2--C0

NHCOPh NHCOPh / ~m /

' RCH - - ~ RCH (XII) \ \

CH~COC1 CIt~CONH~

Interestingly enough, the formation of tetrahydropyrimidine took place only with the N-benzoyl derivatives, but the corresponding derivatives, such as the 2-acetyl derivatives, could be obtained from the amide (XII) by treatment With acetic anhydride: Acyl interchange with the replacement of the 2-benzoyl group by an acetyl group took place simultaneously with the closing of the pyrimidine ring.

The possibility of the simple transition from 6-oxotetrahydropyrimidines to dihydroura- cils by gentle alkali treatment was also demonstrated:

OR' /

N, C NHC00W NH--CO / \ o~- / OH- / \

RCH NH -* RCH -~ RCH NH \ / \ \ /

CH2--CO CHICONHz CH2--C0

When the Hofmann reaction was carried out with amides of acylated B-amino acids in a joint study with V. K. Zvorykina [36], imidazole derivatives, i.e., glyoxalidones, were obtained with the intermediate formation of an isocyanate:

COPh /

i 1 / |_ . / \co RCH K0H / ~CH~.CONHa L CHoN=C=O..I CH~--NH

R C H - - N H

Ko~ ] / \ co ,

C H 2 - - N H

Glyoxalidones, especially acylated glyoxalidones, were obtained more smoothly and with greater yields according to the Curtius reaction from esters of the acylated amino acids, as was shown in a study with N. N. Bezinger [45]:

COPh

//NHCOPh ] / NHCOPh NHCOPh NHCOPh [ RCH--N / NH:~NH, /( HNO~ /" 1 ~

RCH ~ - - R C H - - - - R C t t --~ /RCH [ - ~ [ /CO

k ~CHoN=C=OA \CH2C00Et \CH~CONHNH~ CH2CON3 . CH~--NH

A further study of the Hofmann reaction revealed aninteresting possibility for the transition from B-amino to a-amino acids [46]. Under the action of KOBr, glyoxalidone was oxidized to hydantoin, which was converted in an alkaline medium into a Ureido acid and then into an a- amino acid with a number of carbon atoms one less than in the original a-amino acid:

RCH--NH RCH--NH

1 KOBr I " OH- \CO ~ co - - / /

CH~--NH CO--NH

R=AI k AIkCH--NHCONH2 -~ AIkCH--NH2

COOH COOH

ArC=N KOBr 1 a=Ar ~ [ArCONHCONH2] ~ NH

/ 0--C0

As we see from the scheme, a-amino acids were obtained only from hydantoin with an alkyl substituent. In the case of an aromatic substitute, derivatives of 5-phenyl-l,3,4-oxadiazol- 2-one were obtained by a somewhat more complex route. The possibility of the synthesis of heterocyclic compounds of the isoquinoline, 1,3-oxazine, and other series on the basis of B- amino acids has been studied in recent years by the Bulgarian scientist B. I. Kurtev, who

1950

was a student of Rodionov [47].

A characteristic feature of the experimental work of V. M. Rodionov and his co-workers was that during the study of the conversions of the B-amino acids just mentioned, the structure of all the compounds obtained was irreproachably proved. Furthermore, in many cases; a thorough study of the composition of the reaction mixture was carried out, providing information on the mechanism of the main reaction and the direction of the side reactions. Thanks to these studies, ~-amino acids became one of the accessible and widely studied classes of organic compounds. For this great series of studies Vladimir Mikhailovich Rodionov was also awarded a State Prize.

Teaching, writing, and public activity occupied an important place in Rodionov's life. He prepared groups of qualified engineers and scientists in the various institutions of higher learning of Moscow, heading departments in the Moscow Higher Technical School, the Second Moscow State University, the Second Medical Institute, and the Textile Institute at different timeso In the difficult years of World War II, when Scientific efforts were dis- persed over the entire country, Vladimir Rodionov headed the department of organic Chemistry at the Moscow State University. He did not stop his teaching activity until his death, re- maining the chairman of the department of organic chemistry at the D. I. Mendeleev Moscow Institute of Chemical Engineering. He surrounded himself with a large number of studies, whose works have made a valuable contribution to science and technology.

For many years he was an editor or member of the editorial board of several scientific journals and scientific--technical publishing houses, including this journal. Numerous books, monographs, and collections of papers were published under his editorship.

From 1945 to the end of his life, Rodionov was the vice-chairman of the Technical Council of the Ministry of the Chemical Industry and took an active part in the study and development of the productive capacities of the country. Even at an old age he frequently traveled to the Urals and Siberia in order to verify the possibility of building new chemical enterprises there. In 1939 Rodionov was elected to be a corresponding member of the Academy of Sciences of the USSR, and in 1943 he was promoted to a full member. He took an active part in the work of the D. !. Mendeleev All-Union Chemical Society and as its president from 1949 to the end of his life.

Vladimir Rodionov could be found at work in the very early morning. Despite his enormous work load, he always found time to answer letters from his numerous students and friends, to do his own shopping, and to send new books and journals to various parts of the country. His gentleness and kindness towards people and his irreconcilability to dishonesty and hypocrisy brought him tremendous respect and love.

He brilliantly understood literature, music, and painting, and he loved nature, traveling, and sports. In one of his speeches Vladimir Rodionov quoted Roscoe and said, "Continual work keeps us young and holds back the passage of time."

These words apply completely to Vladimir Rodionov himself. He continually and tirelessly worked his whole life and labored for his homeland, and this may be why he remained sound and energetic to the last day of his life.

LITERATURE CITED*

i. V.M. Rodionov and V. K. Matveev, Ber., 57, 1711 (1924). 2. V. M, Rodionov and S. I. Kanevskaya, Ber., 62, 2663 (1929). 3. V~ I. Rodionov, B. M. Bogoslovskii, and A. S. Chernyshev, Patent No. 61296/35272 (1940). 4. V.M. Rodionov, B. M. Bogoslovskii, and Z. S. Kazakova, Izv. Akad. Nauk SSSR, Otd. Khim.,

536 (1948). 5. V.M. Rodionov and S. !. Kanevskaya, Zh. Nauchn, Khim-Farm. Inst. VSNKh, No. 2, 46 (1921). 6. V.M. Rodionov, Bull. Soc. Chim. France (4), 39, 305 (1926). 7. V.M. Rodionov and Yu. S. Shidovskaya-Ovchinnikova, Zh. Prikl. Khim., 16, Nos. 3-4~ 152

(1943).

*In writing this article we used the material in [48] in addition to ~the original works of V. M. Rodionovo For a complete list of the works of V. M. Rodionov see [48], p. 772.

1951

8. V. M. Rodionov and N. N. Suvorov, Dokl. Akad. Nauk SSSR, 69, 189 (1949). 9. V. M. Rodionov and N. N. Suvorov, Dokl. Akad. Nauk SSSR, 75, 43 (1950).

!0. V. M. Rodionov, N. N. Suvorov, and L. V. Shagalov, Dokl. Akad. Nauk SSSR, 8_22, 731 (1952) ~. ii. V. M. Rodionov, Izv. Akad. Nauk SSSR, Otd. Khim. Nauk, 385 (1953). 12.- V. M. Rodionov, Usp. Khim., 22, 628 (1953). 13. V. M. Rodionov and S. I. Kanevskaya, Bull. Soc. Chim. France [5], !, 655 (1934). 14. V. M. Rodionov and S. I. Kanevskaya , Bull. Soc. Chim. France [5], i, 659 (1934). 15. V. M. Rodionov and A. M. Fedorova, Zh. Obshch. Khim., ii, 264 (1941). 16. V. M. Rodionov and A. M, Fedorova, Zh. Obshch. Khim., ~, 947 (1937). 17. V. M. Rodionov and K. I. Bogacheva, Tr. Vses. Nauchno-Issled. Inst. Sint. Nat. Dushistykh

Veshchestv, ~, 66 (1952). 18. V. M. Rodionov and K. S. Polyakova, Tr. Vses. Nauchno-Issled. Inst. Sint. Nat. Dushistykh

Veshchestv, l, 68 (1952). 19. V. M. Rodionov, V. N. Belov, E. A. Ogorodnikova, and N. N. Shevyakova, Tr. Vses. Nauchno-

Issled. Inst. Sint. Nat. Dushistykh Veshchestv, i, 5 (1952). 20. V. M. Rodionov, V. N. Belov, E. A. Ogorodnikova, and N. N. Shevyakova, Tr. Vses. Nauchno-

Issled. Inst. Sint. Nat. Dushistykh Veshchestv, ~, 6 (1952). 21. V. M. Rodionov, R. Sh. Grigor'eva, and V. N. Belov, Tr. Vses. Nauchno-Issled. Inst. Sint.

Nat. Dushistykh Veshchestv, 2, 19 (1954). 22. V. M. Rodionov, V. N. Belov, and R. Sh. Grigor'eva, Tr. Vses. Nauchno-Issled. Inst.

Sint. Nat. Dushistykh Veshchestv, ~, 33 (1952). 23. V. M. Rodionov, V. N. Belov, E. K. Smol'yaninova, A. A. Bag, and A. A. Bugorkova, Tr.

Vses. Nauchno-Issled. Inst. Sint. Nat. Dushistykh Veshchestv, !, 47 (1952). 24. V. M. Rodionov, E. A. Ogorodnikova, N. N. Shevyakova, and V. N. Belov, Tr. Vses. Nauchno-

Issled. Inst. Sint. Nat. Dushistykh Veshchestv, 2, 27 (1954). 25. V. M. Rodionov, N. A. Solov'eva, E. K. Smol'yaninova, and V. N. Belov, Tr. Vses. Nauchno-

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1952