It’s Not Just the Germans: Russian Contributions to the Development of Organic Chemistry David E....
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Transcript of It’s Not Just the Germans: Russian Contributions to the Development of Organic Chemistry David E....
It’s Not Just the Germans: Russian Contributions to the Development of Organic Chemistry
David E. Lewis
Department 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 RHO
R'R
C ClO
R' RI/Zn/Et2O
C RHO
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
HCO2Et
OHEtI/Zn
CHOOH
Et2Zn
CO2EtBrCO2Et
OH
Zn/Me2CO
CO2EtBr CO2Et
OH
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 NNH2
R
R R
R
H
H
KOH/Δ
CO2HR
Br
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
MeIP
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.
ClCl
+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
R
OH
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
O
CRR
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 R
R CHONH3 /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-Westropp
b. 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