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by air oxidation of 111 aiid provides a clue to the quaternary salt of type B, which is decomposed
nature of veranthridine itsell (vide infra). Huang- by water to produce about 70% of 2-methylcyclo-
Minlon reduction of V regenerated veranthridine, hexanone. Similar alkylation with benzyl chloride
m.p. 228-230' ; mixed m.p. undepressed; ultra- produces 2-benzylcyclohexanone. Functional
violet spectrum identical with that of authentic groups may be present in the halide: Ethyl bromo-
111. acetate leads to ethyl 2-oxo-cyclohexaneacetate in good
The facile oxidation of both cevanthridine and yield. I t may be noted that the conventional
veranthridine under mild conditions to colored synthesis of the latter compound requires five steps
ketobases and the smooth reduction of the latter from cyclohexanone. The mildness of this new
to the parent bases by the very specific method reaction lends itself to the alkylation of substances
employed indicates that these red ketones are containing alkoxide labile groups : 4-hydroxy-
fluorenones and hence that cevanthridine and cyclohexanone benzoate gives 2-methyl-4-hydroxy-
veranthridine are fluorene derivatives." These cyclohexanone benzoate without loss of the benzoyl
results support our earlier conclusion that the non- group in addition to the N-methiodide of the start-
nitrogenous portion of cevine (and the related ing enamine (path I), isolated in llY0 yield. The
polyhydroxy tertiary bases) does not possess a reaction may also be of interest, conversely, in
normal steroid skeleton, but rather has the C-nor/D cases where the halide contains base sensitive func-
homo-steroid type of structure which has been tions. The new reaction is not limited to alkyl
adopted for jervine and veratramine by Winter- halides : Acrylonitrile heated with the pyrrolidine
steiner, et aL6 enamine of cyclohexanone in dioxane solution
( 5 ) Cf the ease of oxidizing fluorene t o fluorenone and of regenera- gives a n yield of 2-cyancethylcyclohexanone,a
ting fluorene by t h e Wolff-Kishner reduction substance which is only obtained with difficulty
(6) For leading references see 0 Wintersteiner a n d R I Moore, by other methods. Methyl vinyl ketone gives
THISJOURNAL, 75, 4938 (1953) directly, after treatment of the intermediate with
THEROCKEFELLER INSTITUTE water, A1-Q-2-octalonein about 3040% yield.
FOR MEDICAIRESEARCH S 1%' PELLETIER Treatment of the enamine from cyclohexanone with
benzoyl chloride gives 2-benzoylcyclohexanone
and with ethyl chlorocarbonate in dioxane solution
2-carbethoxycyclohexanone is ~ b t a i n e d . ~
The monoalkylation obtained with alkyl halides
KETONES is clearly the result of the much lower reactivity
Sir: of the alkylated enamines since the salts of type B
We have discovered a new method for the alkyla- can produce alkylatable enamines by loss of a pro-
tion and acylation of ketones. The condensation ton to the parent enamine
products of ketones and secondary amines are well R
It is evident that these substances can
undergo reaction with proper electron acceptors
either a t N or C according to path I or 11:

/ R'
H H \ H >?=C-\-H + I

i I1 K'

I n agreement with this view, we have found that the

pyrrolidine enamine from 2-methylcyclohexanone
gives mostly recovered starting material under the
conditions used with cyclohexanone itself.
R' This low reactivity of the fully substituted en-
/ amines is useful in certain cases, e.g., the mono-
A O=C-C-R methylation of 6-tetralones which is usually very
I \
I \
H difficult to achieve by direct methylation: Here
again the reaction is easily applied in the presence
We have found that the synthetically important of base sensitive groups : 5-phthalimido-2-tetralone
path I1 is followed in a number of instance^.^ produces the 1-methyl derivative in about 50-60yo
The pyrrolidine enamine from cyclohexanone reacts yield without interference from the imide function.6
with methyl iodide in boiling methanol to yield a The specially interesting case of the enamines
(1) C. Mannich and H. Davidson, B e r . , 69,2106 (1936) (4) For a theoretically related reaction in the ketene acetal series
(2) An especially convenient synthetic method has recently been see S. M . McElvain and R. V. Mullineaux, THISJOURNAL, 74. 1811
described by F. E . Hey1 and M. E. Herr, THIS J O U R N A L , 75, 1918 (1952).
(1953). (5) I n this special case, the reaction recalls the monoalkylation of
(3) I n a formal sense an electronic archetype for these reactions may acetoacetic ester which may be effected with suficiently reactive
well he the transformation of 1,3,3-trimethyl-2-methyleneindoline alkyl halides win dialkylaminocrotonic ester' R Rohinson. J . Chem.
into 1,3,3-trimethyl-2-isopropylideneindoline on treatment with SOC.,109, 1038 (1918); W. M. Lauer and G. W. Lones, THISJ O U R N A L ,
methyl iodide (C. Zatti and A. Ferratini, B e y . , 93, 2302 (1890); G. 59, 232 (1937); G . Eglinton and hi. C. Whlting, J . Chem. SOC.,3052
Plancher, ibid., 31, 1488 (1898)). (1953).
2030 BOOKREVIEWS Vol. 76

from aldehydes and the factors which determine the N-methylation is the principal result with the
course of the reaction are being investigated, in enamine of testosterone?
particular the effect Of StrLlCtUre O n the extent to (6) Prepared according to reference 2. A number of enamines are
which paths 1 and 11are followed. T h a t there is a known which show simple N-methylation on treatment with methyl-
iodide, cg., 1,6-dimethyl-1,2,3,4-tetrahydropyridine:A. Lipp, A n n . ,
fine balance between these two possibilities is 289, 216 (1896); neostrychnine, 0. Achmatowicz, G.R . Clemo, W. H.
by the fact that the enamine Of Perkin, Jr., and R . Robinson, J. Chem. SOC.,
787 (1932).
whilegives no other
C-alkylation with 2-cyano-
iodide, on the hand i t gives coLUMBIA
ethvlcvcloheptanone with acnilonitrile. Dr. P. C. SEW YORK 27. N. Y. TACOB SZMUSZKOVICZ
Mikharji inAthis Laboratory- has also found that RECEIVED
MARCH17, 1954


Low Temperature Physics. BY CHARLES F. SQUIRE,Pro- In a chapter on thermal energy of solids a t low tcnipera-
fessor of Physics, The Rice Institute, Houston, Texas. tures, cooperative phenomena and rotation of molecules
McGraw-Hill Book Company, Inc., 330 West 42nd and radicals are discussed. These are of especial interest
Street, New York 18, New York, 1953. x + 244 pp. 16 to physical chemists.
X 23.5 cm. Price $6.50. The final chapter of the book is on dielectric properties
a t low temperatures. The most interesting phenomena
This is a very interesting and well-written book, and is here result from the orientation in the solid state of electric-
recommended t o those interested in learning more about dipole molecules and radicals. This gives rise to phenomena
the phenomena of very low temperatures-mostly below of electrical polarization of a solid that are analogous to
4’K. Some of the phenomena discussed in the book are para- and ferromagnetism.
observable only below 50°K. which makes the book not The mathematical parts of the book are a t the lcvel of
only interesting but important for those inclined to physical the graduate physics student. A knowledge of elementary
theory. Those interested in the thermodynamics will find statistical mechanics and quantum theory is presupposed.
many interesting applications of theory to the unusual prop- The M.K.S. system of units has been used. This system
erties of liquid helium, superconductivity, para- and dia- is not uncommon among physicists, but newton as a unit of
magnetism and the liquefaction of gases. There is a good force, and EO = 8.85 X coulomb2/newton-m2and PO =
balance between theory and experiment so that the interested 12.57 X weberpamp-m for the dielectric constant and
non-mathematical reader will find the purchase of the book magnetic permeability of free space will seem strange to
justified. many chemists familiar XTith €0 = PO = 1.
The book begins with a discussion of the liquefaction of This book is pre-eminent among books covering the whole
gases. Only the liquefaction of helium with a S. C. Collins- low temperature field. I t is not to be expected however
type cryostat is discussed in much detail. This may dis- that a book of 250 pages covering so extensive a field could
appoint some but the reviewer approves the author’s treat a subject like superconductivity in such detail as the
choice. The book was written to cover low temperature specialized monographs on superconductivity by F. London
physics not engineering and the Collins-cryostat has been and by D . Shoenberg.
by far the most used liquefier in the U.S.A. for the investiga- The book is recommended to all who are iuterested in
tion of the phenomena discussed in this book. The inclu- reading about a comparatively new field of physics that is
sion of such topics as lubrication of the gas compressor, and not only stimulating but is challenging because more re-
the draining of oil and water traps will point up for the alert mains to be understood than we know about it today.
liquefier operator the kind of information needed for the
operation of other kinds of liquefaction plants. SATIONAL BUREAUOF STANDARDS
There follows a good theoretical discussion of the equation WASHINGTON 25, D. C. F. G BRICKIVEDDE
of state of real gases from the point of view of statistical
niechanics. The quantum-statistical equations of state for
ideal gases a t low temperatures are included. Annual Review of Biochemistry. Volume 22. BY J .
Three chapters on liquid helium follow-really on the MURRAY LUCK,Stanford University (Editor); HUBERT
strange phenomena of liquid helium below 2.2”K. charac- S. LORING,Stanford University; and GORDOSMAC-
terizing a strange state of matter designated Liquid He- KISNEY, Gniversity of California (Associate Editors).
lium(I1). Two chapters are on experimental phenomena- annual Reviews, Inc., Stanford, California. 1953.
one on thermal and the other on flow phenomena-and the
third chapter is on the Theory of Liquid Helium(I1). A-0 ix + 729 pp. 16.5 X 23 cm. Price $6.00.
theory yet proposed really “explains” the strange phenom- The Prefatory Chapter in this volume is an innovatioii
ena of helium(I1) beyond showing that they are undoubtedly i n the series. I n discussing his experiences in the study of
a consequence of a large accumulation of helium atoms in foods and nutrition as a student, a teacher and an investi-
states of low translational energy. gator, Professor E. V . McCollum presents a fascinating ac-
Superconductivity follows; first there is a discussion of count of his early associations in Sew Haven and Madison
the experimental phenomena and then the pertinent theory. with such eminent pioneers in biochemistry as Babcock,
As the author points out there is as yet no adequate theory Chittenden, Hart, Osborne, Mendel and Underhill. Pro-
of superconductivity, though there are a number of equa- fessor McCollum established (1907) the first rat colony in
tions, some empirical and some derived from classical ther- America for the study of nutrition, obtained (1913) the first
modynamics and electrodynamics, tying together otherwise evidence that fats contain an indispensable nutrient (vita-
disjointed properties of superconductors. min A ) , and published (1918) the first edition of his outstand-
There is a chapter on magnetic phenomena with pertinent ing book “The Newer Knowledge of Nutrition.” In 1917
classical and quantum theory. Besides the regularly in- he was appointed to take charge of the department of chem-
cluded topics the authors discussed the newer phenomena of istry in the newly established School of Hygiene and Public
alignment of nuclear magnetic moments, nuclear magnetic Health in Johns Hopkins University, a post Irhich hc fillled
resonance with r.f. fields, anti-ferromagnetism and the pro- with distinctiou for more than three decades.
tluction of lowest attained temperatures (0.002”K.) h y the Half of the topics surveyed in volunie 22--biologic~~lqsi-
:itlial):itic. t1rin:igiietiz:ii i o i i o f n p:it:iiu:igiic*ticsalt. (laiioiis, proteolytic a n d uoii-prolrolytic r~izpines, : i I i l l i i o