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Book Review Elektronenstruktur organischer Molekle. Grundbegriffe quantenchemischer Betrachtungsweisen. By Martin Klessinger

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With the lower analogues 1 and 2, N a f ions do not
show any significant effect on the CT absorption; for the
higher analogue 4 (/lcr=442 nm, ~ = 2 1 3 )the complexation effect of N a + with A&= 162 is significantly smaller
than for 3. K + ions change the CT absorption of 1 and 2
scarcely at all, and that of 3 significantly less than Na+
ions; with 4, however, they result in an enhancement of
the intensity by A&= 139 and in a bathochromic shift of 23
nm. It seems to us that in compounds 1-4 a principle of
cation-selective ligands with a “built-in CT indicator” is
realized which may be of some general interest.
Received: December 8, 1982;
supplemented: February 14, 1983 [Z 219 IE]
German version. Angew Chem 95 (1983) 330
CAS Registry numbers:
1, 85083-46-1 ; 2, 85083-47-2; 3, 85083-48-3; 4, 85083-49-4; 4 . N a + , 8508344-9; 4 . K ’ . 85083 45-0; 5, 85083-50-7; 6, 85083-51-8; 7, 85083-52-9; 8,
85083-53-0: 9, 85083-54.1.
[ I ] Electron Donor-Acceptor Compounds, Part 34.-Part 33: H. A. Staab, C.
P. H e n , C . Krieger, M. Rentea, Chem. Ber.. in press.
[2] H. A. Staab, W. Rebafka, Chem. Ber. 110 (1977) 3333; H. A. Staab, C. P.
H e n , Angew. Chem. 89 (1977) 839; Angew. Chem. Int. Ed. Engl. 16 (1977)
799; H. A. Staab, A. Dohling, C. Krieger, Liebigs Ann. Chem. 1981, 1052,
and references cited therein.
131 a) Elemental analyses and spectroscopic data correspond to the structure
suggested; b) 1 : orange-red crystals, m.p. 120-122°C (from ethyl acetate/cyclohexane, 2 : l ) ; MS: m/z=416 (IOOYo, M + ) ; ‘H-NMR (CDCI,,
80 MHz): 6=2.00-3.25 (m, 6H), 3.62-3.82 (m, 14H), 4.33 (d, J = 2 Hz,
2H), 4.23, and 4.62 (AB, J = 1 3 Hz, 2H), 6.17 ( s , l H ) , 6.35 (t. J = 2 Hz,
1 H), 6.45 ( s, 1 H), 6.68 (s, 1 H).-c) 2 : orange-red crystals, m. p. 68-70°C
(from etherln-heptane); MS: m/z=460 (lOOo/o, M + ) ; ‘H-NMR (CDCI,,
80 MHz): 6=2.00-2.80 (m, 6H), 3.69 ( s , 18H), 4.27 (d, J = 2 Hz, 2H),
4.48(~,2H),6.13(t,J=lHz,1H),6.41(t,J=2Hz,lH),6.46(~,
IH),6.68
( s , 1 H).-d) 3 : orange-red prisms, m.p. 71-72°C (from ether/n-heptane);
MS: rn/z=504 (100%, M + ) ; ’H-NMR (CDCI,, 80 MHz): 6 = 1.80-2.25
(m. 2H),2.25-2.80(m, 4H), 3.50-3.85 (m, 22HL4.31 (d, J = 2 Hz, 2H),
4.52 (S, 2H), 6.31 (Y’, J = 1 Hz, I H), 6.54 (s, 1 H), 6.60 (t, J = 2 Hz, 1 H),
6.81 ( s , 1 H).-e) 4 : orange-yellow crystals, m.p. 88-90°C (from ethyl
acetate/cyclohexane, 3 : 1); MS: m/z=548 (lo%, M + ) , 177 (IOOYo); ‘HNMR (CDC12, 80 MHz): 6 = 1.91 (quint., J = 7 Hz, 2H), 2.42 (t, J = 7 Hz,
2H),2.86(t,J=7Hz,2H),3.58-3.70(m,20H),3.71(s,3H),3.74(s,3H),
4.34(d,J=2Hz,ZH),4.52(~,2H),6.42(t,J=l Hz,lH),6.59(s,IH),
6.74 (t, J = 2 Hz, 1 H), 6.87 (s, 1 H).
[4] Starting from 1,3-bis(2,5-dimethoxyphenyl)propane(R. E. Moser, H. G.
Cassidy, J. Org. Chem. 30 (1965) 2602) chloromethylation and hydrolysis
yielded 4,4’-trimethylenebis(2,5-dimethoxybenzylalcohol) [3a]; bromomethylation yielded 1,3-bis(4-brornomethyI-2,5-dimethoxyphenyl)propane [3a].
[5] General procedure for the synthesis of 1-4: A solution of diammonium
hexanitratocerate (0.8 mmol) in 10 m L water was added to a stirred solution of 5, 6 , 7, or 8 (0.4 mmol) in 40 m L acetonitrile at room temperature. After 20 min the reaction mixture was extracted with dichloromethane; the extract was dried on magnesium sulfate, evaporated, and the
residue chromatographed on silica gel using cyclohexane/ethyl acetate.
BOOK R E V I E W S
’Elektronenstruktur organischer Molekule. Grundbegriffe
quantenchernischer Betrachtungsweisen. By Martin Klessinger. Verlag Chemie, Weinheim 1982. xv, 331 pp.,
bound, DM 78.-.
This book by M . Klessinger is the first volume of a sixpart series entitled “Physikalisch Organische Chemie” and
treats the current quantum chemical models of theoretical
organic chemistry in nine chapters and a detailed appendix. The first chapter deals with the orbital concept in
atomic and molecular systems, while the second one introduces the HMO (Hiickel molecular orbital) model for simple systems and the third gives a short introduction to the
basic principles of group theory and symmetry of fermion
systems. The interactions between orbitals in a range of organic molecules are discussed in the fourth chapter and
correlated with experimental results (photoelectron spectroscopy). Then the most important aspects of the application of perturbation theory are discussed. The basics of
SCF (self-consistent field) models and various types of
correlation diagrams (orbital correlation diagrams, configuration and state diagrams) are introduced in the next two
chapters. Finally, important MO models of theoretical
chemistry are treated together with quantum mechanical
aids for the interpretation of such models (population
analysis, energy fragmentation, localization procedures
etc.).
All the chapters are constructed so as to be highly instructive; each time the main points of a theme are presented in a short introduction. The demands on the reader
Angew. Chem. 1111.Ed. Engl. 22 (1983) No. 4
are then increased stepwise, without noticable gaps or
jumps in the discussion. The numerous problems at the
end of each chapter allow a continuous check on the text
that has been worked through. Such an organized layout
should make the volume attractive for a potential readership over and above theoretically and physically oriented
organic chemists. The subject matter covers, on the one
hand, the fundamental principles of quantum mechanics
(the variational method, perturbation theory, HellmannFeynman relation) and, on the other hand, presents almost
all the important models in applied theoretical (organic)
chemistry that have been developed in the last 50 years.
Many topics are treated at a level of intensity which is not
to be found in comparable text books. The explanations of
correlation technique (with many up to date references),
the treatment of reactions in the ground state and photochemical reactions, the comparison of MO and VB results
for reactive systems, together with the discussion of the
various types of reaction hypersurfaces are all particularly
effective. The layout of the text could perhaps have been
made even clearer by combining chapters six and eight.
This textbook can, in any event, be unreservedly recommended to a wide readership. The construction of the
book, the diagrams and the layout of the formulas could
scarcely be more painstaking. This simplifies, in particular,
the working through of the mathematical and quantum
mechanical equations. The price of the book is reasonable
in view of the amount of information it provides. It is to be
hoped that the volumes of “Physikalisch Organische
335
Chemie” that follow maintain the high instructional quality and, thus, help to fill a considerable informational gap
in the chemical literature. A good start has been made with
M . Klessinger’s book, which deserves to find its way into a
large number of textbook collections and private libraries.
Michael C. Bohm
[NB 583 IE]
Annual Reports in Medicinal Chemistry. Vol. 17. Edited by
H.-J. Hess. Academic Press, New York 1982. xiii, 383
pp., bound, $ 32.00.-ISBN 0-12-040517-2
Proceedings of the First International Symposium on Cyclodextrins. Edited by J. Szejtli. D. Reidel Publishing
Company, Dordrecht 1982. xiii, 544 pp., bound,
Dfl. 195.00.-ISBN 90-277-1433-9
Encyclopedia of the Terpenoids. 2 Volumes: A-H, I-Z.
By J . S . Glasby. John Wiley, Chichester 1982. 2646 pp.
(1-1322, 1323-2646), bound, E 250.00.-ISBN 0-47127986-2 (0-471-90031-1 A-H, 0-471-90032-X I-Z)
Solid Hydrogen. Theory of the Properties of Solid H,, H D ,
and&. ByJ.van Kranendonk. Plenumpress,NewYorkl983.
xv, 306 pp., bound, $ 39.50.--ISBN 0-306-41080-X
Electron-Atom and Electron-MoIecuie Collisions. Edited by
J . Hinze. Plenum Press, New York 1983. viii, 354 pp.,
bound, $ 49.50.--ISBN 0-306-41188-1
Petroanalysis ’81. Advances in Analytical Chemistry in the
Petroleum Industry. Edited by G. B. Crump. John Wiley,
Chichester 1982. xiv, 456 pp., bound, E 36.00.-ISBN 0471-26217-X
Gmelin. Handbuch der Anorganischen Chemie. 8th edit.
Springer-Verlag, Berlin 1983.
Sn-Organotin Compounds. Part 10: Mono- and Diorganotin-Sulfur Compounds. Organotin-Selenium and
Organotin-Tellurium Compounds. xi, 352 pp., bound,
DM 993.00.--ISBN 3-540-93468-5
U-Uranium. Supplement Vol. A 6: General Properties,
Criticality. xvi, 251 pp., bound, DM 950.00.-ISBN 3540-93471-5
Defects in Insulating Crystals. Edited by V. M . Tuchkevich
and K . K . Shvarts. Springer-Verlag, Berlin 1981. 744 pp.,
bound, DM 99.00.--ISBN 3-540-10782-7
Springer Series in Solid-state Sciences: Vol. 28; The Structure and Properties of Matter. Edited by T. Matsubara.
Springer-Verlag, Berlin 1982. xi, 446 pp., bound,
DM 100.00.-ISBN 3-540-11098-4
Physikalische Grundlagen der Verfahrenstechnik. 3rd completely revised edition. By P. Grassmann. Otto Salle Verlag/Verlag Sauerlander AG, Frankfurt 1983. 972 pp.,
bound, DM 280.00.--ISBN 3-7935-5514-3
Comprehensive Treatise of Electrochemistry. Vol. 6: Electrodics: Transport. Edited by E. Yeager. J. O’M. Bockris,
B. E. Conway, and S . Sarangapani. Plenum Press, New
York 1983. xxiii, 522 pp., bound, $ 67.50.--ISBN 0-30640942-9
Umweltforschungskatalog 1981 (UFOKAT ’81). 4th edition. Issued by the Umweltbundesamt. Erich Schmidt
Verlag, Bielefeld 1982. xiii, 1724 pp., boards,
DM 79.00.--ISBN 3503-02188-4
Technologie der Reinen Raume. By W. Tauscher. Verlag fur
Chemische Industrie H. Hiolkowsky KG, Augsburg
1982/83. 441 pp., paperback, DM 48.00.-ISBN 387846-106-2
Nitrat-”itrit-Nitrosamine
in Gewassern. Mitteilung ZZZ
der Kommission fur Wasserforschung in Verbindung mit
der Kommission zur Priifung von Lebensmittelzusatz- und
Znhaltsstoffen. A Deutsche Forschungsgemeinschaft
publication. acta humaniora der Verlag Chemie GmbH,
Weinheim 1982. 240 pp., paperback, DM 70.00.-iSBN
3-527-27305-0
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