вход по аккаунту


Book Review Kinetik der Gasereaktionen (Kinetics of Gas Reactions) by E. Cremer and M

код для вставкиСкачать
a$-Acetylenecarboxylic acids can be prepared by a n intramolecular Wittig-synthesis. G . Murk/ has reported that triphenylphosphine carboxymethylene (I) reacts with acid
chlorides as shown in equation ( I ) :
The hydroborination of acetylenes at first yields substituted
vinylboranes according t o H. C. Brown an d G . Zweifel. O n
protonolysis, these are conveted to cis-olefins in high yield
agd purity. Oxidation of the vinylboranes with hydrogen
peroxide in weakly alkaline solution leads t o the correspond(I)
2 iC,H5)3P-;CH -COOCH, + R-COCI
ing ketones or, if terminal acetylenes are used as starting
materials, aldehydes. If the acetylenes are treated with a large
.- ~f (C+Hr)jP=C -COOCH, 4- I ( C ~ H ~ ) , P - C H Z - C O O C H ~ ~ ~ ~ ~ excess of boranes showing no steric hindrance, double hydroI
borination occurs. The two boron atoms attach themselves
predominantly t o the same C-atom: after the addition of the
borane to 1-hexyne, oxidation yields hexanal and only little
Triphenylphosphine acylcarbomethoxymethylenes (11) are
1,2-hexanediol. / J. Amer. chem. SOC.83,3834 (1961). -KO.
colorles:?, well crystallized compounds which are quite resi[Rd 989114 IE]
stant to hydrolysis. Pyrolysis a t 220 to 25OoC yields triphenylphosphine oxide and the substituted methyl esters of propiolic acid:
A new enzymological method for the diagnosis of myocardial
infarction. W. Stich and A . Tsirimbas have examined the
:> 220°C
+ (CsH5)1P-O
activity of the muscle-specific creatinephosphokinase (CPK)
which in heart and skeletal muscle has a concentration 10 t o
CIiem. Wer. 94, 3003 (1961). / -KO.
[Kd 78/41 IE]
30-times higher than in other organs. The authors studied
the activity of CPK in the serum of normal persons and those
suffering from myocardial infarctions and other illnesses.
The cage effect, which in a solvent holds reactive molecules
The normal value was 1.96 t o 0.17 CPK unitslml. of serum
together, was proved by R . K . Lyon and D . H. Levy. Mixtures
in 15 healthy individuals but in myocardial infarction, an
of azomethane and hexadeutero azomethane were photolyzed
increase in the CPK activity of the serum occurs, even after
and the reaction products analyzed by mass spectrometry. I n
a few hours, reaching a maximum after 18 t o 30 hours. The
a random reaction involving methyl and trideutero methyl
increase over the normal value is 3 t o 20-fold. The diagnostiradicals, the expected product ratio is given by the equation:
cally significant increase in CPK occurs practically only in
myocardial infarction and in muscular diseases that can be
clinically distinguished (progressive muscular dystrophy,
Erb-, Crush-syndromes). Consequently, the CPK test - in
contrast t o existing enzyme tests - makes possible the
This value was closely approximated in gas phase photolysis
(Q = 4.1 1 0.8). On the other hand, photolysis in iso-octane
biochemical differentiation between myocardial infarction
and clinically similar diseases such as pulmonary infarction,
solution, yielded practically n o CH3CD3 (less than 0.3 % of
gallbladder and liver diseases, among others. / Klin. Wschr.
the total ethane), but almost exclusively C2H6 and C2D6. / J.
40,115 (1962). / -A.
[Rd 74/36 IE]
[Rd 5/22 IE]
Amer. chem. SOC.83,4290 (1961). / -KO.
Kinetik der Gasreaktionen (Kinetics of Gas Reactions), by E.
Creme,. and M. Pnltl. Walter De Gruyter & Co., Berlin
1961. tst Ed., XVI, 129pp., 48 diagrams, 17 tables. Price
DM 28.-.
This bock originated from a suggestion made by K . F. Bonhoeffer and is dedicated t o the memory of M. Bodenstein,
under whose guidance the author completed, in 1927, her
doctoral thesis on the hydrogen-chlorine reaction. This thesis
discussed mechanisms involving branching chain-reactions
and explosions due to branching chain-reactions before the
publication of Scmenov’s fundamental papers. The fact that
Bodemtern himself did not recognize the full import of the
iesults, was one of the reasons why the implications of
Crenrer’s thesis were not pursued further. In referring t o her
nough not t o mention
previous work, Dr. Cremer I S mode
these facis.
She praises Bodemrein as the “father of reaction kinetics”, a
name he deserves as Far as gas reactions are concerned. Clear
and straightforward experimentation, in which he pioneered,
is one of bhe prerequisites for success in this field, a fact which
I S unfortunately often for8otten today.
His second achievement was the discovery of the “chain
reaction” (a name g k e n to this phenomenon by Cristiansen
7 years later). As liis third achievement, one may mention
his introduction of the concept of the “quasi-stationary
ps typicdl of Bodcnhtein, that the mathematiof his method were wrong (a fact that he
himself came to recognize In later years) but that in this
case, as in others, he never erred In the application of the
mathematical reasoning. This should, perhaps, have been
brought out in the presentation of the subject.
The authors deserve praise for including a few ion-molecule
reactions at the end of the book. In keeping with the introAngew. Chem. internat. Edit. / Vol. 1 (1962) / No. 4
ductory nature of the book, the theoretical discussion of
recent developments is avoided. Thus, for example, in the
case of unimolecular reactions no mention is made of
developments more recent than the work of Lindemann and
The descriptive treatment of reaction mechanisms and a
short discussion of the theoretical principles involved are
followed by a discussion of ‘I few selected examples. The
strength of the book lies in it5 limited scope which is confined
t o a discussion of the principles and the results of the experiments. Probably n o other book is capable of introducing
the reader to practical reaction kinetics in so few pages.
W. Jost
[NB 82518 IE]
The Enzymes, Vols. 4 and 5: Hydrolytic Cleavage (Part A
and B), ediied by P . D . Boyer, H . Lardy, and K . Myrback.
Academic Press, Inc., New York-London, 1960161. 2nd
edition, Vol. 4: XX, 631 pages, price: $18.-, Vol. 5:
XIX, 645 pages, price: $20.-.
While the first three volumes of the revision of “The Enzymes” deal with the fundamentals of enzyme chemistry,
Volumes 4 and 5 discuss certain hydrolytic enzymes, peptide
bond cleavage, other C-N bond clca\ age, glycoside cleavage,
esterases, hydrolysis of ester and amide phosphates, synthesis and cleavage of the C-C bonds, isomerases, hydratases,
and dehydratases. The material is arranged according t o
functions, not by metabolic relationships. For example,
enolase, crotonase, and fumarase aia found among the
hydrolases. Special attention is given t o the catalytic mechanisms and the facts associated with these. Methods of
preparation and activity measurements are mentioned only
in passing since well known, specialized treatises exist for
these. O n the other hand, information about the protein
Без категории
Размер файла
150 Кб
book, reaction, der, kinetika, kinetics, gas, cremer, review, gasereaktionen
Пожаловаться на содержимое документа