diethanolg were isolated in small amounts as byproducts, the quantities increasing when the excess of aminobutanol was decreased. An interesting alternative synthesis, reductive alkylation of 2aminobutanol with glyoxal using sodium borohydride1° as reducing agent, gave good yields. This work has shown that in mice the dextro form of 2,2’-(ethylenediimino)-di-l-butanolis more active and less toxic than streptomycin when administered parenterally and possesses an oral efficacy index (ratio of maximum tolerated dose to median effective dose) a t least equivalent to that of isoniazid. -4 series of papers is in preparation covering studies of numerous homologs and of various analogs and modifications of the functional groups of this chemotherapeutic agent.
I
I
R
R
IIIa, R = CsHj b,R-H
I r a , R = CBH, b, R = H
IIIa
CHIODf
,/CocBH5
(9) meso-Dihydrochloride, m.p. 246.5-247.5O dec. (&)-dihydrochloride, m.p. 238-239’ dec. (10) J . H. Billman and A. C. Diesing, J . Org. Chem., 22, 1068 (1957). used this reagent for reduction of aromatic Schiff bases.
LEDERLE LABORATORIES DIVISIO?; R. G. WILKINSOS R. G. SHEPHERD ORGANIC CHEMICAL RESEARCH J. P. THOMAS AMERICAS CYANAMID COMPANY EXPERWEXTAL THERAPEUTICS RESEARCH C. BAUCHX PEARL RIVER,XEWI’ORK RECEIVED MARCH24, 1961 C-C02CH3
A NEW PHOTOCHEMICAL PRIMARY PROCESS, THE PHOTOCHEMICAL ENOLIZATION OF
V
O-SUBSTITUTED BENZOPHENONES
Sir :
and dimethyl acetylenedicarboxylate (0.06 mole) We wish to report a new type of photochemical in benzene was irradiated with a Hanovia S-SO0 primary process, the photochemical enolization of source a t 15-20’ for 24 hours. After the solvent o-substituted benzophenones. Benzophenone was removed, the residue crystallized and no apreadily is reduced photochemically in the presence preciable amount of polymeric material was formed. of hydrogen donors to give benzopinacol cia a ketyl The residue was recrystallized from benzene-cycloradical intermediate (I). Photochemical pinacol hexane to give I V in 85% yjeld (m.p. 112’; found: reduction is suppressed completely and no ketyl C, 71.25; H, 5.36; A,, 3300 cm.-’, 1 i 2 0 a n . - ‘ ; radical formation is detected if the benzophenone is strong ultraviolet end absorption). The structure substituted a t the ortho position by an alkyl group of IV was established by its conversion to l-phenylcontaining an a-hydrogen. Instead, o-alkylbenzo- naphthalene-2,3-dicarboxylicacid (V) , identical in phenone (11) undergoes intramolecular hydrogen all respects with an authentic sample.3 The quantransfer to give the corresponding enol under the tum yield of this photochemical addition is estiinfluence of ultraviolet light. Photochemical mated a t >0.5. The generality and further apenolization of this type has been demonstrated plications of this reaction are being investigated. unequivocally by these observations. The authors wish to thank Professor 11‘. -1. o-Benzylbenzophenone (IIa) is extremely stable Noyes, Jr., for some valuable discussion and LIr. toward ultraviolet radiation generated by either Richard Atkinson for his assistance in the preparalow pressure or high pressure mercury arcs. The tion of an authentic sample of IT. C. R. is incompound was recovered unchanged after pro- debted to the Petroleum Research Foundation longed irradiation in alcohol solutions and no for a graduate fellowship. pinacol could be detected. When a solution of ( 3 ) A. Michael, Be?., 39, 101% (1906). IIa in CH30D was irradiated with a Hanovia S-200 (4) Alfred P. Sloan Fellow. source, the recovered I I a was found to contain DEPARTMENT OF CHEMISTRY 1.04-1.09 atoms of deuterium per molecule,2 while UNIVERSITY OF CHICAGO x.c . Y A S C 4 no deuterium incorporation took place when the CHICAGO 37, ILLINOIS CARLOS RIVAS same solution was allowed to stand a t ordinary 27, 1961 RECEIVED FEBRUARY laboratory conditions. By n.m.r. spectrometry, all the deuterium atoms were found to be located THE PHOTOCHEMICAL REARRANGEMENT OF a t the benzylic position. HYPOCHLORITES The photo-enol (IIIb) of o-methylbenzophenone Sir : (IIb) reacts smoothly with dimethyl acetyleneI n a recent communication’ we adumbrated a dicarboxylate, a dienophile, to give an adduct (IV) in excellent yield. An equimolar solution of IIb photochemically induced rearrangement of hypohalites of the general type (A) + (B) (X = halo(1) C. S Hammond and W.M. Moore, J . A m . Chem. SOC.,81, 6334 (1959), and references therein. (2) Deuterium analysis by Dr. Josef Semeth of Urbana, Illinois.
(1) D. H. R. Barton, J. M. Beaton, L. E. Geller and M. M. Pechet,
J. A m . Chem. Soc., 82, 2640 (1960).
Vol. 53
BOOKREVIEWS
2214
gen). This reaction has been observed by Proiessor Cheves Walling2 for the hypochlorites of certain aliphatic alcohols. M‘e now wish to report two examples of the reaction in the steroid series. In both cases the chlorhydrins formed have been characterized by base treatment to give the corresponding 1,4-oxides. The photolysis of hypoX
I -
I
c
I€
\ / Cll (A)
c
I
I
c
\ /
c
ether (11, X = H2) and its derived lactone (11, X = 0) have been prepared independently by Cainelli, et d S Similarly 3,B-acetoxy-Ga-methylcholestan-6~-ol (111, R = Ac, X = H)gwas converted to its hypochlorite (111, R = Ac, X = C1) and photolyzed. Base treatment of the product as above afforded Ga-methyl-6,19-oxidocholestari-3~-ol (IV) (5O’%), n1.p. 179-181’, [ a ] D +19’ (in CHCl,) as well as the diol (111, R = X = H). The constitution of (IV) was confirmed by its n.m.r. spectrumlOqll (loss of C19 methyl group).
C. (B)
chlorites to give alkoxy radicals and atomic chlorine is, of course, well known3 3P-Acetoxy-20-methylallopregnan-2O-ol(I, X = H)” was converted to the hypochlorite (I, X = Cl), m.p. 145-147’, [CY]D 0’ (in eel,), 258 and 318 mp (e = 107 and 9.5, respectively) using chlorine m o n o ~ i d e . ~This hypochlorite was photolyzed in dry benzene using a mercury lamp (200 watt, Pyrex filter)’P6 with water cooling. The product, refluxed with 5y0 methanolic potassium hydroxide for 2 hr., gave, on reacetylation and chromatography, 20-methyl-18,2O-oxidoallopregnan-3,B-yl acetate (11, X = H2) (2093, m.p. 152-154’, ID +17” (in CHCl,) as well as starting material (I, X = H). The constitution of the product was shown by its n.m.r. spectrum’ (loss of CISmethyl group) and by vigorous chromic acid oxidation to the y-lactone (11, X = o),s m.p. 209-210’, [ a ] D oo (in CHCIJ, 1757 and 1745 cm.-l. The
,:EY
(2) We thank Professor Walling (Columbia University) for his kind personal communication and for helpful advice. (3) Cheves Walling, “Free Radicals in Solution,” J. Wiley and Sons, Inc., h-ew York, K.Y.,1957, p. 386. (4) A. Butenandt and H. Cobler, Z. pkysiol. Chcm., 234, 218 (1935): B. Koechlin and T . Reichstein, Helo. Ckim. Acta, 27, 549 (1944). (5) M. Anbar and I. Dostrovsky, J . Chem. Soc., 1105 (1954). ( 8 ) D. H. R . Barton and J. M. Beaton, J . A m . Ckcm. Soc., 82, 2641 (1960). (7) We thank Dr. J. W. Lown for kindly determining these n.m.r. spectra. (8) G . Cainelli, B. Kamber, J. KeUer, M. L. MihailoviC, D. Arigoni and 0. Jeger, Hclu. C k i m . Acfa, 44, 518 (1961).
I11
IV
Acknowledgments.-We thank Dr. M. hl. Pechet for his encouragement and the Misses C. Pantuck and L. Gendron for able experimental assistance. (9) L. F. Fieser and J. Rigaudy, J . A m . Chcm. SOC.,7 3 , 4661 (1951); R. A. Sneen, ibid., 80, 3982 (1958). (10) Satisfactory analytical data have been secured for all new compounds except that the hypochlorites were characterized through iodimetry (being thereby reduced to the parent alcohol). (11) The substance of this Communication was given in a lecture by D . H. R . B. at the Annual General Meeting of the Chem. SOC. at Liverpool, U. K., on April 12th 1961. At that time Dr. V. A. Petrov (B.D.H.) informed us by personal communication that he had observed similar results in steroids.
RESEARCH INSTITUTE FOR MEDICINE AND CHEMISTRY M. AKHTAR D. H. R. BARTON CAMBRIDGE 42, MASS. RECEIVED APRIL19, 1961
BOOK REVIEWS The Surface Chemistry of Metals and Semiconductors. A Symposium Sponsored by the Office of Naval Research and the Electrochemical Society, Columbus, Ohio, 1959. Edited by HARRYC. GATOS. With the assistance of J. W. FAUST,Jr., and W. J. LAFLEUR. John Wiley and Sons, Inc., 440 Fourth Avenue, New York 16, N. Y. 1960. xi f526 pp. 16 X 23.5 cm. Price, $12.50. This volume is the record of a symposium on the surface chemistry of metals and semiconductors held under the auspices of the Electrochemical Society and the Office of Naval Research in October, 1959. It contains twenty-two papers which are presented in five sections entitled The Chemistry and Physics of Surfaces, Imperfections and Surface Behavior, Electrode Behavior of Metals and Semiconductors, Surface Reactions in Liquid Media, and Surface Reactions in Gaseous Media, respectively. The character
of the individual contributions varies considerably. There is, for example, a short (11 page) general introduction to the physics and chemistry of surfaces by W. H. Brattain, a report on some recent experimental investigations of oxidation-reduction reactions a t the germanium electrode by H. Gerischer, and lengthy and fairly detailed review articles on the oxidation of metals by K. Hauffe and by Gwathmey and Lawless. This volume is perhaps best described as a collection of elementary review papers and, as such, should be of value to chemists and physicists seeking an introduction to recent research in the areas enumerated above. I t is possible that a surface chemist or electrochemist may find some of the contributions superficial, insufficiently detailed or similar to reviews previously published in the periodical literature. However, the papers are carefully and econod-
