It’s Not Just the Germans: Russian Contributions to the Development of Organic Chemistry

David E. LewisDepartment of Chemistry

University of Wisconsin-Eau Claire

University of Minnesota-Duluth, April 15, 2005

1868

The Chemists

Nikolai Nikolaevich Zinin (1812-1880)(Nikolay Nikolaeviq Zinin)

kandidat Kazan’ 1836 Dr. Chem. St. Petersburg 1841 study abroad (komandirovka) in western Europe

1838-1841 intended for Zinin to learn technology not intended for Zinin to learn “new” chemistry year with Liebig in Giessen

Kazan’ University Professor of Chemical Technology 1841-1848

Medical-Surgical Academy, University of St. Petersburg

Professor of Chemistry 1848-1878

Justus von Liebig (1803-1873)

Aleksandr Mikhailovich Butlerov(Butlerow) (1828-1886)(Aleksandr Mihayloviq Butlerov)

kandidat Kazan’ 1849 (entomology) M. Chem. Kazan’ 1851 (under Klaus) Dr. Chem. Moscow, 1854 (under Klaus) study abroad (komandirovka) in western Europe

1857-1858, 1867-1868 met Erlenmeyer and Kekulé spent six months with Wurtz in Paris not supposed to be a research trip

Kazan’ University Professor of Chemical Technology 1851-1858 Rector twice

University of St. Petersburg Professor of Chemistry 1869-1880

Karl Karlovich Klaus(1796-1864)

Charles-Adolphe Wurtz (1817-1884)

Aleksandr Porfir’evich Borodin(Borodine) (1834-1887)(Aleksandr Porfir¡eviq Borodin)

kandidat St. Petersburg Medical-Surgical Academy 1855

M.D. St. Petersburg Medical-Surgical Academy 1858

study in western Europe 1859-1862 travelled with Mendeleev delegate to 1860 Karlsruhe conference

St. Petersburg Medical-Surgical Academy Extraordinary Professor of Organic Chemistry 1862-1864 Professor of Organic Chemistry 1864-1887

Fedor Fedorevich Beil’shtein(Friedrich Konrad Beilstein) (1838-1906)(Fedor Fedoreviq Beyl¡wteyn)

1853 sent to Germany to study studied with Bunsen & Kekulé at Heidelberg studied with Liebig at Munich studied with Wöhler at Göttingen

Ph.D. Göttingen 1858

University of Göttingen Docent 1860 Extraordinary Professor 1865

Technical Institute, St. Petersburg Chair in Chemistry, 1866-1906

Editor, Zeitschrift für Chemie, 1865-1871 with Hübner and Fittig

Robert Wilhelm Eberhard Bunsen (1811-1899)

Friedrich Wöhler (1800-1882)

LiebigFriedrich August Kekulé (1829-1896)

Vladimir Vasil’evich Markovnikov (Markownikoff) (1838-1904)(Vladimir Vasil¡eviq Markovnikov)

kandidat Kazan’ 1860 (economic science) M. Chem. Kazan’ 1865 Dr. Chem. Kazan’ 1869 study abroad in western Europe 1865-1867

studied with Kolbe at Leipzig studied with Erlenmeyer in Heidelberg

Kazan’ University docent 1867 Extraordinary Professor of Chemistry 1868 Professor of Chemistry 1869-1871

Odessa University Professor of Chemistry 1871-1873

Moscow University Professor of Chemistry 1873-1893

Adolph Wilhelm Hermann Kolbe (1818-1884)

Aleksandr Mikhailovich Zaitsev(Saytzeff) (1841-1910)(Aleksandr Mihayloviq Zaycev)

diplom Kazan’ 1862 (economics) kandidat Kazan’ 1865 Ph.D. Leipzig 1866 M. Chem. Kazan’ 1868 Dr. Chem. Kazan’ 1870

study abroad in western Europe 1862-1865 studied with Kolbe at Marburg 1862-1864 studied with Wurtz in Paris 1864-1865

Kazan’ University unpaid Laboratory Assistant 1865 Assistant in Agronomy 1866-1868 Extraordinary Professor of Chemistry 1869-1870 Professor of Chemistry 1871-1910

Wurtz

Kolbe

Nikolai Aleksandrovich Menshutkin(1842-1907)(Nikolay Aleksandroviq Menwutkin)

kandidat St. Petersburg 1862 M.Chem. St. Petersburg 1866 Dr. Chem. St. Petersburg 1869

study in western Europe 1863-1866 study under Strecker in Tübingen study under Wurtz in Paris study under Kolbe in Leipzig

St. Petersburg University Professor of Chemistry 1869-1902 Chair in Organic Chemistry 1885-1902

Petersburg Polytechnic Institute Professor of Chemistry 1902-1907

Wurtz

Kolbe

Egor Egorevich Vagner (Georg Wagner) (1849-1903)(Egor Egoreviq Vagner)

kandidat Kazan’ 1874 M. Chem. St. Petersburg 1885 Dr. Chem. Warsaw 1888

St. Petersburg University Assistant under Menshutkin 1876-1882

Novo-Aleksandriya Institute of Agrigulture and Forestry

Professor of Chemistry 1882-1886

Warsaw University Professor of Organic Chemistry 1886-1892

Warsaw Polytechnic Institute Professor of Organic Chemistry 1889-1903 Dean of the Chemistry School 1889-1903

Sergei Nikolaevich Reformatskii(Reformatsky) (1860-1934)(Sergey Nikolaeviq Reformatskiy)

graduatedKostroma Spiritual Seminary 1878 kandidat Kazan’ 1882 M. Chem. Kazan’ 1889 Dr. Chem. Warsaw 1890 study abroad in western Europe 1889-1890

studied with Viktor Meyer at Heidelberg and Göttingen studied with Wilhelm Ostwald at Leipzig

Kazan’ University curator of museum 1882-1889

Kiev University Professor of Chemistry 1891-1934

USSR Academy of Sciences Corresponding Member 1928

Aleksei Evgrafovich Favorskii(Favorsky) (1860-1945)(Aleksey Evgrafoviq Favorskiy)

kandidat St. Petersburg 1883 M. Chem. St. Petersburg 1890 Dr. Chem. St. Petersburg 1895

St. Petersburg Technical Institute Professor of Chemistry 1896-1907

St. Petersburg University Professor of Chemistry 1908-1929

USSR Academy of Sciences Associate Member 1921 Academician 1929

Institute of Organic Chemistry, USSR Academy of Science, St. Petersburg and Moscow.

Professor, 1929-1945

Vyacheslav Evgen’evich Tishchenko(1861-1941)(Våqeslav Evgen¡eviq Tixenko)

M. Chem. St. Petersburg 1899 Dr. Chem. St. Petersburg 1906

travel abroad to report on technology Chicago World’s Fair 1893 Paris Exposition 1900

St. Petersburg University Professor 1901-1941

Nikolai Dmitr’evich Zelinskii (Zelinsky) (1861-1853)(Nikolay Dmitrieviq Zelinskiy)

kandidat Odessa 1884 M.Chem. Odessa 1889 Dr. Chem. Odessa 1891

study in western Europe 1885-1887 Wislicenus at Leipzig Viktor Meyer at Göttingen

Moscow University Professor of Chemistry 1893-1953

St. Petersburg Technical Institute Professor of Chemistry 1911-1917

USSR Academy of Sciences Corresponding Member 1926 Academician 1929 Head, N.D. Zelinskii Institute 1934

Nikolai Yakovlevich Demyanov(Demjanov) (1861-1938)(Nikolay Åkovleviq Dem¡ånov)

kandidat Moscow 1886 M. Chem. Moscow 1895 Dr. Chem. Moscow 1899

Petrine Forestry and Agricultural Academy, Moscow

Assistant in Chemistry 1887-1893 Adjunct Professor of Chemistry 1894-1898 Professor of Chemistry 1898-1938

Institute of Organic Chemistry, USSR Academy of Science

Director 1935-1938

Nikolai Matveyevich Kizhner (Kishner) (1867-1935)(Nikolay Matveeviq Kijner)

kandidat Moscow 1890 M. Chem. St. Petersburg 1895 Dr. Chem. Moscow 1900

Tomsk Technological Institute Professor of Chemistry 1901-1913

Shanyavskii Popular University, Moscow Professor of Chemistry 1914-1917

Aniline Trust Research Institute Director 1918-1934

Corresponding Member, USSR Academy of Sciences 1929-1934

Aleksei Evgen’evich Chichibabin(Alexis Tchitchibabine) (1871-1945)(Aleksey Evgen¡eviq Qiqibabin)

kandidat Moscow 1892 M. Chem. Moscow 1904 Dr. Chem. St. Petersburg 1912

Moscow University Docent 1901, 1906-1908

University of Warsaw Adjunct Professor 1905-1906

Moscow Higher Technical School Director 1908-1929 Dean, Chemistry Faculty (intermittent) 1909-1929

Left Russia 1930• worked with Tiffeneau at Hôtel Dieu; worked at Collège de France• Director, Scientific Departmenht, Kuhlman Co. 1930-1945; technical advisor, Schering and

Rooseve;t Co. 1930-1945

Lev Aleksandrovich Chugaev (Tschugaeff) (1873-1922)(Lev Aleksandroviq Qugaev)

M.Chem. Moscow 1903 Dr. Chem. Moscow 1906

Moscow University Adjunct in Bacteriological Institute 1904-1908

St. Petersburg University Professor of Inorganic Chemistry 1908-1922

Sergei Semenovich Nametkin(1876-1950)(Sergey Semenoviq Nametkin)

M. Chem. Moscow 1911 Dr. Chem. Moscow 1916

Moscow University Extraordinary Professor 1910-1911, 1938-1950

Moscow University Higher Women’s Courses (Second Moscow University 1917)

Ordinary Professor 1911-1924 Rector 1919-1924

Moscow Institute of Fine Chemical Technology Professor 1924-1938

Moscow Mining Academy (later Moscow Petroleum Institute)

Professor of organic chemistry and petrochemistry 1927-1950 Rector 1919-1924

Aleksandr Erminingel’dovich Arbuzov(Arbusow) (1877-1968)(Aleksandr Erminingel¡doviq Arbuzov)

diplom Kazan’ 1900 M. Chem. Kazan’ 1905 Dr. Chem. Warsaw 1914

Novo-Aleksandriya Institute of Agriculture and Forestry

Assistant in Chemistry 1901-1905 Professor of Chemistry 1906-1911

Kazan’ University Professor of Chemistry 1911-1930 Deputy Dean, Physics-Mathematics Faculty 1922-1930

Kazan’ Technical Institute, USSR Academy of Sciences

Professor and Director 1930-1944

Ivan Nikolaevich Nazarov(1906-1957)(Ivan Nikolaeviq Nazarov)

kandidat Timiryazev Agricultural Academy 1931 Dr. Chem. St. Petersburg (Leningrad) 1934

Institute of Organic Chemistry, USSR Academy of Science

Associate 1934-1947

Lomonosov Institute of Fine Chemicals (Moscow) Professor 1947-1957

USSR Academy of Sciences Corresponding Member 1946 Member 1953

Butlerov Centenary, Kazan’ 1928

The Chemistry

Major Contributions Zinin — the first Russian organic chemistry of

note; “father of Russian organic chemistry” structural theory of organic chemistry synthesis using organozinc reagents carbocation chemistry chemistry of amines and other amino

compounds chemistry involving enols and enolates textbooks of organic chemistry

The “Father” of Russian Organic Chemistry

CHO O

OH

KCN

Ann. Chem. Pharm. 1840, 34, 186.

NO2 NH2NH3/H2S

Bull. Acad. Sci. St. Petersburg 1842, 18.Bull. Phys.-Math. Acad. St. Petersburg 1852, 348.Ann. Chem. Pharm. 1842, 44, 283; 1844, 25, 361; 1853, 85, 328.

“Even if Zinin had not done anything besides the conversion of nitrobenzene into aniline, his name would have, nevertheless, been inscribed in golden letters into the history of organic chemistry.” — August Wilhelm von Hofmann

N.N. Zinin

Structural theory of organic chemistry

• A.M. Butlerov– Ann. Chem. Pharm. 1859, 111, 5146.

• V.V. Markovnikov• first synthesis of a cyclobutane

– Ann. Chem. Pharm. 1881, 208, 333.• first synthesis of cycloheptane

– Comptes rend. 1892, 110, 466; 115, 462.

HO2C CO2H

Empirical rules that are still taught

• Markovnikov’s (Markownikoff’s) Rule (addition)

– Ann. Chem. Pharm. 1870, 133, 228.– Comptes rend. 1875, 82, 668, 728, 776.

• Zaitsev’s (Saytzeff’s) Rule (elimination)– Ann. Chem. Pharm. 1875, 179, 296.

Organozinc chemistry

C OCl

H3C (CH3)2Zn/ΔC OH

H3C

H3CH3C

• A.M. Butlerov

Bull. Soc. Chim. Paris 1863, 5, 582; 1864, 2, 106.Jahresb. 1863, 475; 1864, 496.Ann. Chem. Pharm. 1867, 144, 132

C ClO

R' R2Zn/Δ C R

HO

R'R

C ClO

R' RI/Zn/Et2O C R

HO

R'R

• A.M. Zaitsev

– Ann. Chem. Pharm. 1875, 175, 351, 374; 1877, 185, 148, 151, 175.– J. prakt. Chem. 1885, 31, 319.

Organozinc chemistry

HCO2EtOH

EtI/Zn

CHOOH

Et2Zn

CO2EtBr CO2EtOH

Zn/Me2CO

CO2EtBr CO2EtOH

Zn/Me2CHCHO

•E.E. Vagner

–Zh. Russ. Khim. Obshch. Fiz. Obshch. 1876, 8, 290.–Zh. Russ. Fiz.-Khim. Obshch. 1884, 16, 283.–Ann. Chem. Pharm. 1875, 175, 351; 179, 302, 313.–Ber. Deut. chem. Ges. 1894, 27, 2436.

•S.N. Reformatskii

–Ber. Deut. chem. Ges. 1887, 20, 2110; 1895, 28, 2838, 2842, 3262.

Redox chemistry

A.M. Butlerov doctoral dissertation (1854) contains first

report of osmium tetroxide oxidation of an alkene

A.P. Borodin

Z. Chem. 1861, 4, 5; 1869, 12, 342. Ann. Chem. Pharm. 1869, 121, 119

CO2AgRBr2 BrR

Redox chemistry A.M. Zaitsev

Ann. Chem. Pharm. 1866, 139, 354; 1867, 144, 148.

Z. Chem., N.F. 1869, 5, 551; 1870, 6, 105 J. prakt. Chem., N.F. 1871, 3, 76, 427.

E.E. Vagner (G. Wagner)

Deut. chem. Ges. 1888, 21, 1230, 3343, 3347, 3356

C ClO

R'

HOAc HO

R'Na(Hg)/Et2O

SR

R HNO3/H2OS

RO

R

OH

OH

CO2H

OHKMnO4/H2O KMnO4/H2O

Redox chemistry

N.M. Kizhner (N. Kishner)

Zh. Russ. Fiz.-Khim. Obshch. 1911, 43, 582.

N.D. Zelinskii (N.D. Zelinsky)

Ber. Deut. chem. Ges. 1887, 20, 2026.

OR

R NH2NH2 NNH2R

R R

R

HH

KOH/Δ

CO2HRBr

CO2HR

1) Br2/P

2) H2O

Redox chemistry V.E. Tishchenko

Zh. Russ. Fiz.-Khim. Obshch. 1906, 38, 355,482, 540, 547 Chem. Zentr. 1906, II, 1309, 1552, 1555,1556. (c.f. Claisen, L.

Ber. Deut. chem. Ges. 1887, 20, 646.)

A.E. Arbuzov (A.E. Arbusow)

Zh. Russ. Fiz.-Khim. Obshch. 1910, 42, 395, 549. Chem. Zentr. 1910, 11, 453

ArO

H

Al(OEt)3

ArC

O Ar

O

PPhO

PhOPhO MeI P

PhO

PhOO CH3

Carbocation chemistry

E.E. Vagner (G. Wagner)

Ber. Deut. chem. Ges. 1899, 32, 2302; 1900, 33, 2121.

N. Ya. Demyanov (Demjanov)

Zh. Russ. Fiz.-Khim. Obshch. 1903, 35, 26; 1904, 36, 186. Chem. Zentr. 1903, I, 828; 1904, I, 1214. Ber. Deut. chem. Ges. 1907, 40, 4393, 4961; 1908, 41, 43.

Cl Cl+HCl

CH2NH2HONO CH2OH OH+

NH2HONO

OH CH2OH+

Carbocation chemistry S.S. Nametkin

Liebigs Ann. Chem. 1923, 432, 207.

I.N. Nazarov

Zh. Izv. Akad. Nauk SSSR Otd. Khim. Nauk 1942, 200.

prototypical example of a conrotatory electrocyclic reaction

R

H

R

R R

O

acid

OH

R R

O

RR

Enols and enolates:C—C bond formation

N.N. Zinin

Ann. Chem. Pharm. 1840, 34, 186.

A.P. Borodin (Borodine)

Ber. Deut. chem. Ges. 1873, 6, 973.

CHORNaOH

ROH

CHO

R

CHO O

OH

KCN

Other C—C bond-forming reactions

A.E. Chichibabin (Chichibabine)

Ber. Deut. chem. Ges. 1904, 37, 186, 850.

A.E. Favorskii (Favorsky)

Zh. Russ. Fiz.-Khim. Obshch. 1900, 32, 652; 1905, 37, 643. Chem. Zentr. 1905, II, 1018.

EtOOEt

OEt

RMgXR

OEt

OEtR CHO

H /H2O

C CR

H R C C

OC

RR

R

ROH

Amine and imine chemistry A.E. Chichibabin

Zh. Russ. Fiz.-Khim. Obshch. 1914, 46, 1216.

Zh. Russ. Fiz.-Khim. Obshch. 1906, 37, 1229. J. prakt. Chem. 1924, 107, 122.

N.D. Zelinskii

Zh. Russ. Fiz-Khim. Obshch. 1906, 38, 722; 1908, 40, 790.

N N NH2

NaNH2

NR

R RR CHO

NH3 /Δ

R CHO + NH4Cl + KCN RNH2

CN

Base-promoted rearrangements

A.E. Favorskii (Favorsky)

Zh. Russ. Fiz.-Khim. Obshch. 1887, 19, 414 Ber. Deut. chem. Ges. 1887, 20, 781.

J. prakt. Chem. 1913, 88, 658.

C CR

H CCH

RC

H

HR C C CH3

O

Br

NaOHCO2H

Other reactions F.F. Beil’shtein (F.K. Beilstein)

halogenation of alkylbenzenes

Ann. Chem. Pharm. 1866, 139, 331.

A.P. Borodin (Borodine) first organic fluorine compound

Compt. rend. 1862, 55, 552. Z. Chem. 1862, 5, 556. Nuov. Cim. 1862, 15, 305. Ann. Chem. Pharm. 1863, 126, 58..

R

Cl

R R

Cl

CO

Cl

KHF2 CO

F

Other reactions N.A. Menshutkin

reaction rate studies in alcohols and amines

Z. phys. Chem. 1890, 5, 589; 1891, 6, 41.

L.A. Chugaev (Tschugaeff)

Ber. Deut. chem. Ges. 1899, 32, 3332.

ROH 1) NaOH/CS2

2) MeI; 3) ΔR

NR

RR R X N R X

R

RR+

Some textbooks, etc. A.M. Butlerov

Introduction to the Study of Organic Chemistry (Kazan’, 1861); Lehrbuch der organischen Chemie zur Einführung in das specielle Studien derselben (Leipzig, 1867)

F.F. Beil’shtein (F.K. Beilstein) Beilsteins Handbuch der organischen Chemie (1881)

second edition 1886 third edition 1893

S.N. Reformatskii A Beginner’s Course of Organic Chemistry (Kiev, 1891)

Some textbooks, etc.

N. Ya. Demyanov Organic Chemistry (3rd. edition: Moscow, 1944)

A.E. Chichibabin Organic Chemistry (Moscow, 1917; went through many

editions)

Borodin: Late and Overdue Recognitions

Tony Award for Musical of the Year Kismet, 1954

Alexander Borodin, composer Luther Davis, Robert Wright: librettists George Forrest, lyricist Charles Lederer, lyricist/producer

Named reaction Borodin-Hunsdiecker reaction

Published by Borodin in 1861 Patented by Heinz and Cläre Hunsdiecker in

1939 (published in Berichte 1942). Borodin’s name slowly attached to it after the mid

1970’s

The speaker

Academic lineage

b. 1951Ph.D. 1980 (Adelaide)

Ph.D. 1958 (Manchester)

David E. Lewis

D. Phil. 1941 (Oxford)

Ralph A. Massy-Westroppb. 1932

Ph.D. 1910 (Manchester)

Arthur J. Birch1915-1995

Ph.D. 1881 (Würzburg)

Robert Robinson1886-1975

Ph.D. 1857 (Zürich)

William H. Perkin, Jr.1860-1929

1885-1902

Ph.D. 1845 (Göttingen)

Johannes A. Wislicenus

M.D. 1823 (Heidelberg)

Georg A.K. Städeler1821-1871

M.D. 1812 (Göttingen)

Friedrich Wöhler1800-1882

M.D. 1800 (Göttingen)

Leopold Gmelin1788-1853

1811-1880Ph.D. 1842 (Berlin)

Ph.D. 1821 (Kiel)

Wilhelm H. Heintz

M.D. 1804 (Upsala)

Heinrich Rose1795-1864

Jöns J. Berzelius1779-1848

Friedrich Stromeyer1776-1835

Ph.D. 1858 (Berlin)

Ph.D. 1830 (Göttingen)

J.F.W. Adolph von Baeyer1835-1917

Robert W.E. Bunsen1811-1899

Ph.D. 1852 (Giessen)

Ph.D. 1822 (Erlangen)

Friedrich A. Kekulé1829-1896

Justus von Liebig1803-1873

doctoral advisor (primary influence)

post-doctoral advisor or other significant secondary influence