synthesis via, orgilnomereury compounds,
BOOK REVIEWS
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A Textbook of Pharmaceutical Analysis
reactions of orgitnogallium substances,
Methods of Elemenloorganic Chemistry.
Volume 1, The Organic Compounds of
Boron, Aluminum, Gallium, Indium and
Thallium
A. N. Nesmeyanm and R. A . Sokolik,
both of t,he Institute of Elementa-
Organic Compounds, USSR Academy of
Sciences, Moscow. Translated from
the Russian hy Seripta Technica, Ine.
The World Publishing Company, Cleve-
+
land & New York, 1967. xiii 628 pp.
Figs. and tahles. 16.5 X 25 cm. $24.
Eighteen years ago, A. N. Nesmeyanov
and H.A. Kocheshkov published a baok
entitled "Synthetic Methods for Organo-
metallic Compounds of Elements of
Group 111." Shortly after that time, an
enormous expansion in the organic ehem-
istry of bornn and aluminum took place,
enlarging the field so much that a new
book had t,o be written. The present.
volume was published in Russian in 1964,
then translated by Scripta Technica,
Incorporated (under the translation edi-
torship of Paul G. Stecher of Merck,
Sharo Q Dohme Research Lshoratories).
and published by the North Holland Pub:
lishing Co. in Amqterditm in 1967.
Sixty percent of the book is devoted to
arganoboron compounds, with the subject
material divided into sixteen chapters
wveringsynthefiisfrom other organometal-
lic compounds, synthesis via organic com-
pounds of the heavy metals, synt,hesis via
addition of boron hydrides and halides to
unsat~lrated compounds, synthesis by
direct boration of organic compounds,
symmetrizat,ion reactions and isomeriza-
tions, transalkylations, dealkylstion and
dearylation reactions, conversions of func-
tional groups, heterocyclic orgsnoboron
compo~rnds, mmplexes, hydrogenolysis,
reactions of organic subst,it,nents, and
analysis.
The seet,ion on organoaluminum com-
pounds, which is much shorter (24y0 of the
book), is based principally on the work of
Ziegler and the corresponding Russian
work. There are nine ehapt,ers, dealing
with synthesis of organoalmninum eom-
pounds by reaction of alkyl and sryl
halides with aluminum, synthesis via
Grignard reagents, synthesis via organa-
mei.cmy campo~mds,synthcnis via at,her
organometallic compounds, synthesis of
alkyl derivatives by addition of aluminum
h?-dride and its derivatives to carbon-
carhon mukiple bonds, synthesis by
alumination, maet,ions of organoalnminum
compounds, ~ynthesisof orgsnoaluminum
compounds containing aluminom-oxygen
bonds, and analysis.
The organometallie chemistry of gsl-
lium, iudium, and thallium has not changed
m ~ ~ duriue
ch -
the same eiehleen "
vesrs., and
the scarcity of our knowledge is reflected
iu the sections devoted to these elements.
The part on orgmogsllium eompounds
constitutes only 3.3% of the book, and
comprises only four topics: synthesis of
organogallitm compounds by means of
magnesium, aluminum, and sino reagents,
.A64 / Journal of Chemical Education
and analysis. The part devoted to indium
occupies only 2.7% of the boak, and deals
with analogous topies. The part on
organothallium compounds reflects an
earlier interest in the possible chemother-
apy of such substances; it comprises 10%
of the book and deals with synthesis via all
of the cust,omary orgsnometallic reagents,
direct synthesis, synthesis via aryldisso-
nium and diphenylhalonium salts, then
reactions and analysis.
All of the material on structure and
reactions is well organised and useful, of
course, but the strong point of this boak
lies in the complete directions for the
preparation of about 700 compounds.
There is no register of compounds, but
all of them are listed in the subject index;
physical properties and references to the
original literature are given right in with
the directions for preparation. The fol-
lowing example from page 118 is qnoted
in its entirety so that the reader may form
a clearer idea, about this baok: "Synthesis
of organoborm of the RRCL type via
reactions of olefins with boron trichloride
[222]. An autoclave is charged with 90 g
of BCh, 20 g of Al powder, 0.5 g of C H J
and 0.5 g of AICL: the entire mixture is
then heated to 120°C. Ethylene is then
added in eight 4 g portions, and the mix-
ture is kept a t 1 2 0 T for 3 hours. I t is
then cooled to 50DC and the volatile
products distilled off s t this temperature
and about 3 mm into a cold steel cylinder.
The autoclave is cooled to 2 5 T , and the
sludge remaining in it is removed and
filtered. The filtrate is added to the
fraction boiling a t 50°C/5 mm. Distil-
lation of this fraction yields 14 g of
C.H6BC1%,bp 52.5'C; the structure of this
product can be demonstrated by I R
spectra and by hydrolysis to C1HaB(OH)2.
Analysis of the remaining fractions (30 g,
contaminated with hydrocarbons) shows
t,he presence of C4HsBCln(hp 100°C) and
ClrHlnBCll(bp 10'J0C/30 mm).
"Boron triehlaride and propylene (55
g) react analogously. The liquid re~idue
is filtered after collecting the volatile
products. Distillation of the crrtde or-
ganoboron material (about 140 g) yields
fractions bailing a t 65 to lXOoC/4 mm;
t,hese contain about 6 g of n-propylbaron
dichloride (bp 78"C), whose presence
may be confirmed by I R spectrnscopy.
The remaining fractions contain a mir-
ture of alkylbaron halides a ~ ~ hydro-
d systematic pH ealculrttians, the analytical
carbons (confirmed by mass-rpectro-
metric analysis).
"Similar reactions occur between BCI3
and 1- and 2-butenes."
For anyone wit,h research interests in
organnmetsllie chemistry, this volume is a
very handy new addition to the standard
reference works, especially since it brings
so much of the less readily-available
Russian work into sharp focus and con-
venient summary. The diagrams and
the photo offset printing are clear, and
the complete anthor and subject indexes
(SO often missing in Rossian books) are a n
extra dividend.
EUGENE G. Rocnow
Haward University
Cambridge, Massachusetts
K a n e l h A. Connors, University of
Wisconsin, Madison. John Wiley &
Sons, Inc., New York, 1967. xvii +
614 pp. Figs. and tables. 16 X 23.5
em. $12.50.
Thi? boak is intended as a. text for a
drug assay course based an one semester of
introductory quantitative analysis, one
year of organic chemistry, and, if possible,
some physical chemistry. I t is a func-
tional texthook-not a catalog of specific
drug assays-organized into six parts:
(1) Fundamental Titrimetric Analysis,
(2) Physical Methods of Analysis, (3)
Separation Techniques, (4) Elemental
Analysis, (5) Functional Group Analysis,
and (6) Additional Topics.
Part One consists of 8, conventional
snslyticd treatment of aqueous and non-
aqueous ncid-base titrations,,precipitatian,
complexometric, and redox tltrations; this
-
oart is l a r d "v n comorehensive review of
topics nsudly included in introductory
quantitative chemistry, except for the wel-
come chapter on non-aqueous titrimetry.
Systematic pH calculations, including
those for polyfunctionsl acids, are past-
poned until Part Six. Part Two contains
reasonably detailed discussions of several
physical techniques, incloding potenti-
ometry, voltammetry, absorption spec-
troscopy (UV, visible, IR), fluorescence
analysis, refrsctametry, palarimetry,
phase solubility analysis, and density
messurements. The general treatment in
this part is considerably more detailed
t h a n in the first, although still rather
limited in same aspects, such as infrared
soeetroscoov and ouantitative aoolications
chromatography, ion exchange, and malec-
ular sieve processes, while Part Four dis-
cusses only nitrogen and mercury in detail
(the analytical chemistry of several other
metals and nowmetals of pharmaceutical
interest is briefly outlined in introduction
and summary of this part, however).
Part Five contains chapters an hydroxy
compounds, carbanyl compounds, carbox-
ylic acids and esters, amines, smides and
related compounds, and other classes of
compounds, as well as rather strangely
placed (though vsluable) chapters on
water and on enzymes as anslytical re-
agents. Additional topics in Part Six are
problem (including sampling and statisti-
cal interpretation of data), the analytical
literature, and the selection of methods.
Appendixes include procedures for pre-
paring potassium chromate spectropho-
tometer~bsorhancestandards(whichmight
have been induded in the chapter on ah-
sorption spectroscopy), a list of "name"
reagents, tests, and methods which will be
useful to students, as will the solution of
quadratic equations, answers to about one-
fourth of t.he 200-odd problems appearing
throughout the boak, four-place logn-
rithms and an adequate index.
The text is. in eeneral. well written and
(Continued on page A681

BOOK REVIEWS
which tend to establish perspective and
m i f y the whole. Each chapter contains a
well-chosen reference list ss well as, in
several eases, appropriat,ely selected works
for further reading by the serious student
desiring more extensive or intensive
irrformet,ion. The instructions for per-
forming a broad selection of laboratory ex-
periments are concise, clear, and accurate
enough to enhance efficient student work.
The parts on separation and funct,ianal
A68 / Journol of Chemical Educofion
group analysis will be particularly attrac-
tive to many instructors.
The overall impression given by this
book is that of a solid, readable, and ionc-
tional textbook, ngto-date in coverage
and well thought out in execution. I t
should be equally useful as a text or refer-
ence book far students of pharmaceutical
analysis or advanced undergraduate ana-
lytical chemistry.
ROBERTE. T ~ ATT N \
Simthern Illinois University
Carbondale. Illinois
Kinatier and Thermodynamics in
Biochemistry
H . Geoffrey Bray and Kennelh White,
both of the University of Birmingham.
2nd ed. Academic Press, Inc., S e w
York, 1966. xi +
418 pp. Figs. and
tables. 16 X 23.5 em. $15.
I n the preface to the first (195i) editiou
of this book, the authors ststed that they
hoped to provide a. "systematic develop-
ment of the basic ideas of kinetics and
thermodynamics as they are applied to
biochemistry." As snch, the book is lint
very useful because most of the material
covered is eit,her already familiar lo
most readers, or is not explained at all
t,horoughly.
There are, for example, fundamental de-
velopments of thermodynamics, kinetics,
and enzyme kinetics; every one of these
subjects deserves exposition by a specialist
who takes pains with the definitions,
hammers at the fundamentals, and points
oot the difficulties. Here one gets a
smattering. Part of the problem is
probably th& the authors are trying to
put into chapters material which requires
books; in any case, it is poor pedagogy.
As examples of material which is overly
familiar, one may cite the numerous
metabolio pathways reviewed in Chapter
10 (Free Energy and Metabolism), and
the discussion of buffee in Chapter 4
(Equilibria in Aq~teous Solution). In-
cidentally, ii ane wishes to teach about
equilibria, some problems would be very
helpful.
The book is not ~~seless, however. Be-
cause it covers an extraordinarily wide
range of topics, and presents numerous
illustrative examples, a perusal of this
work is bound to make one aware of many
facts and even some fields with which he
was previously unacquainted. Further-
more, numerous excellent references are
given, so that the book may be recom-
mended as a bibliographicsl tool for one
who wishes to find out where to learn
about a given subject. For these reasons,
it might be particularly helpful to a teacher
planning a, course, heeanse it would both
furnish useful ideas as to what topics
might be included, and also suggest
1iterat.ure to cover these t,opirs.
Some subjects are treated quite well.
The discussion of react,ian aystems, and
open versus closed systems, is excellent,
although even here it would have been
better if the authors had not made the
mathematics very detailed as long as it
was simple, and then written down the
solutions to the equations when they be-
came difficult. The ~ t n d e n tshould either
be allowed to fallow the mathematics, or
else have it given to him, b ~ i not
t some of
both.
Very few erroneoos stnlemeots were
detected, and there were f e a misprints.
A more detailed table of contents would
be helpful; t,he list of chapter headings
does not tell what subjects are covered,
and to find a subject again after reading
it once is difficult and frmtrating.
PETER OESPER
Haknemann Medical College
Philadelphia, Pennsylvania
(Continued a page A70)