5512
fin..
s..->.vr.
I ...7,,,XYC.
TABLEI EFFECTSOF LITHIUMPERCHLORATE O N IONIZATION OF I Solvent ACOH~~ 50% AcOH-AcnO hIe2SO HCOL-IIe? Ac.0 1 2 . 5 % AcOH-Dioxane Me2CO n-CiHiaCOOH EtOAc~ THF~ Et20
Temp., OC. 50.0 50.0 75.0 75.0 75.0 75.1 75.1 75.0 75.0 75.0
RO.0
lO5ko sec-1
Av, fit
% of k
b
11.9 0.43
12.P 13.1b
0.6 1.0
18.2 4.96 3.41 1.22
0.oc 1.4c 47 I b
0.3
0.857 0 434 0 113 0.0817 0.000G~
a , ii
4G2$ .t7.0c 4Glb,e 553b 482'
2.9s*** x
106
2 ,3 0,5 I .6 3 .6 3.1 1.3
(LiC104) range: 0 0 4 . 0 6 M: 0-0.10 M ; 0-0.05 .If; 0-0.07 Af. e Equation 2; c = 1184. J Tetrahydro0.005 a t 75". Equation 2 ; c = 2.65 X lo6. furan.
, TO THE EDITOR
VOl. 81
results are given in Table I. These salts were also equilibrated a t higher temperatures with excess metal, quenched, arid analyzed. For PrC13, X,/hl values for (5 runs a t 978' averaged 2.34 f 0.03; for NdC13, G a t 9 X o , 2.00 i- 0.04; for N d h , 2 a t 970') 1.99 5 0.05; incomplete separation of metal may make the X111 ratios somewhat low. ,Although phase equilihrium studies with PrI3 are a t present incomplete, powder patterns of the product from reaction with excess metal a t >74O0 show a new phase and little PrI?to be present. The bronze product has an I Pr ratio less than 2 6 and does not appear to be the diiodide. TABLEI
Q
competing ionization of the organic substrate and make it p r e d ~ r n i n a n t . ~ ( 3 ) S. Smith, J . Gall and D. Darwish, ~ ~ n p u b l i s h ework. d
System
7---Eutect~c-X,/M 7 , "C
--Reduction
limit
T, 'C
X/hI
2 50 & 0 . 0 4 W 4 i j 2 . 5 0 =k 0 . 0 ) f i 4 1 zt
N+YdCk
2.511 zk
f
3 2 01
+
Solid phase
.>
Pr, PrCId 0 0:i 811 =t2 SdClz 560 i 5 S d I ?
Pr-YrCl?
01 t i l 0
-
DEPARTMENT OF CHEMISTRY S. WISSTEIS Nd-SdIr 2 . 1 2 rz .o'? 492 i 2 ( 2 . 0 ) UXIVERSITY OF CALIFORXIA S. SMITH LOSANGELES 24, CALIF. D. DARWISH The dark green SdClz has been further identified RECEIVED SEPTEMBER 21, 1959 from powder pattern data as isomorphous with the RARE EARTH METAL-METAL HALIDE SYSTEMS. T H E PREPARATION OF NEODYMIUM(I1) HALIDES Sir :
I t has been suggested previously that the apparent solution of a number of metals in their molten halides is a result of the formation of a slightly stable, lower halide.' Although the suhhalide is frequently stable only in dilute solution. in some systems the amount of reduction is sufficient to exceed the normal salt-lower salt eutectic composition so that the latter can be obtained as a stable solid.* These metal-metal halide studies are presently being extended to the rare earth systems, where knowledge of the reduction characteristics under these conditions has been limited to the Ce-CeC13 system. Here the reduction limit recently has been reported to be about 9 mole % Ce (CeC12T3)in a solution in equilibrium with liquid Ce and solid CeC13a t 777°,3 in contrast to an earlier value of 327G.4 Although evidence for an oxidation state lower than three for neodymium in aqueous solution has been doubtful,jm6 and in liquid ammonia, inconcl~sive,~ reduction of the molten trichloride and triiodide by metal has been found to yield the corresponding neodymium (11) halide. \Xrith praseodymium, reduction only in solution is observed with the chloride, while a new phase is obtained with the iodide. The chlorides and iodides were prepared from the metalsS and their reactions with metal studied in tantalum containers both by cooling curves and by analysis of salt phases in equilibrium with excess metal. The essentials of the phase diagram (1) J D. Corbett, S. 17 Winhush and F. C . .4lbers, THISJ O U R N A L , 79, 3020 (1957). ( 2 ) J , D. Corhett and .\. Hershaft, ibid., 8 0 , 1530 (1058). (3) G. Mellors and S . Senderoff,J . P h y s . C h e m . , 63, 1110 (l9S9). (4) D. Cubicciotti, THISJ O C R N A L , 71, 4119 (1949). (5) C. Estee and G. Glocker, i b i d . , 7 0 , 1844 (1948).
( 0 ) H. Laitinen and E. Blodgett, ibid., 71, 2260 11949). ( 7 ) P. S. Gentile, Ph.D. Thesis, University of Texas, Austin. T e x n s , 1955. (8) a'e are indebted t o Drs. P. H . Spedding and A . H. Daane f o r the generous supply of pure metal and the benefit of their experience i n experimental techniques.
orthorhombic PbClz structure reported for SmClz and EuCla by Dijll and Klemm,g with lattice (SniC12: 4.49, constants of 4.31, 7.5s and 9.07 r (.d, 9.97 -4.). Such a comparison has not yet been made for the dark purple NdIz. Phase diagram and X-ray data for the NdCla-NdClp system also show the existence of an intermediate phase near SdC12.:rin composition, melting prohably incongruently near 703'. Contribution S o . ;98. IYork was performed in the h i e s Laboratory of the 1:. S. .ltomic Energy Commission. - I
( 0 ) \T'. (1939)
Doll and \V, Klemm, Z . n l i o r e . ail,qe,ii. Cht't~z., 241, 2 1 6
INSTITUTE FOR ATOMICRESEARCH ~ S D LEOSARDF. DRUDISG DEPARTMEKT OF CHEMISTRY JOFIS D . CORBETT IOXYA S T A T E 1-TIYERSI.fY ANES, TOIT'A RECEIVED AUGVST7 , 1959 CARBENOID AND CATIONOID DECOMPOSITION OF DIAZO HYDROCARBONS DERIVED FROM TOSYLHYDRAZONES
S,ir: Tosylhydrazones (p-toluenesulfonylhydrazones) of aromatic aldehydes and ketones react with sodium in ethylene glycol to give aryldiazoalkanes ; tosy-lhydrazones of benzyl methyl ketone (equation l ) and cyclohexanone yield olefins and nitrogen. C8H,CH,C(Ci-I, I=.SSHO.SC;H~ + SaOCH2CH20H--+ C~II:CT-I-crrcF-rI+ s? i-ao.sc71f: -L ]
-
HOCH?CHI.OH i1 1
Carbon-skeleton rearrangements occur in decomposition of pinacolone and camphor tosylhydrazones' to give ".:~-dinieth?;l-'7-hutene and camphene.' .in investigation has now been made of reactions of arylsulfonylhydrazones with bases in protonic and aprotic solvents. The experimental condi(1) W. R . Bamford and T. S Stevens, J . Chew? SOL., 473,5 (1952). ( 2 ) See also R . Hirschmann, E . S . S n o d d y , J r , C. F. Iliskey and A'. L. Wender, Tms J O T , R K . A L , 7 6 , 1-013 f l 9 i 4 ) a n d G . H . Phillips, D. A. H. Tayloi and L. J . \\'yrnan, J . Chem. Soc., 1739 (1!454).
C k t . ”0, 195!l
COMSIUNICATIONS TO THE EDITOR
5513
tions result in a simple method for generating pounds involving hydrogen migration’” occur diazo compounds in situ and studying their de- more readily than do carbon-skeleton rearrangecomposition by cationoid and carbenoid processes. ments, ( 2 ) carbenoid decomposition of diazo Reaction of camphor tosylhydrazone and sodium compounds results in extensive intramolecular methoxide in diethylene glycol a t 140-180° thus cyclization to give cyclopropane^,^^ and (3) the gives camphene (55gjb) and tricyclene (45%) in secondary carbenes presumably formed as reaction near-quantitative yield ; decomposition of the intermediates are more selective in their decomhydrazone by sodium methoxide in diethyl Carbitol position than are their primary analogs. gives the hydrocarbons ( - l O O ~ c yield) in proporWe wish to acknowledge the assistance of Drs. tions > 49: 1.3 The effects of solvents on such R. R. Hopkins and I. J. Oita, Whiting Research processes are also indicated by reaction of 2- Laboratories, Standard Oil Company (Ind.). methylpropanal tosylhydrazone and sodium meth(7) (a) F. 0. Rice and A. L. Glasebrook, THISJOURNAL, 66, 741 oxide in diethylene glycol to give 2-methylpropene (1934) report that diazoetbane decomposes to ethylene and nitrogen. (G5%), cis-2-butene (4%), trans-2-butene (8yo), (b) For related reactions of methylene see W. von E. Doering, R. G. 1-butene (lo%), and methylcyclopropane (12%) Buttery, R . G. Laughlin and N. Chaudhuri, i b i d . , 78, 3224 (1956). in 3070 yield, whereas in diethyl Carbitol or hexade- DEPARTMENT OF CHEMISTRY L. FRIEDMAN H. SHECHTER UNIVERSITY cane, 2-methylpropene (62, 64%) and methyl- THEOHIO STATE 10, OHIO cyclopropane (37, 36%) are formed in 80 and 787” COLUMBUS RECEIVED AUGUST21, 1959 yields. The initial reaction of 2-methylpropanal tosylhydrazone (and other tosylhydrazones) is formaISOLATION OF CYTIDINE-S’-MONOPHOSPHO-Ntion of its salt and methanol; thermal decomposiACETYLNEU!UMINIC ACID‘ tion of this salt in diethyl Carbitol or hexadecane Sir: gave 2-methylpropene (61, 62%) and methylcycloIn conjunction with s t ~ d i e s 2 ~on3 ~the ~ metabopropane (3937%) in composition essentially identi- lism and structure of the sialic acids, we have now cal with that from the hydrazone and sodium meth- isolated a new nucleotide, cytidine-.5’-monophosoxide in aprotic solvents. I t is suggested that pho-N-acetylneuraminic acid, from Escherichia salts of tosylhydrazones decompose to diazo com- coli K-235, an organism which produces a polymer pounds; the diazo compounds undergo (1) proton Of NAN.’.‘ transfer from donor solvents and cationic deThe nucleotides from sonically disrupted cells composition of the Wagner-Meerwein type in- were fractionated on Dowex-1,Cl- resin using volving hydrogen and carbon-skeleton rearrange- LiCl as eluting agent. A nucleotide, giving characment and (2) carbenic decomposition in aprotic teristic color reactions for sialic acid, was eluted solvents to give olefins by hydrogen migration and slightly behind C5P, but before other nucleoside cyclopropanes by intramolecular insertion. Addi- monophosphates. Paper chromatography of the tional evidence for the carbenic processes is de- material in this peak yielded two major comporived from the observations t h a t diazo compounds are detectable in the aprotic reaction products and nents, C5P and C5P-NAN (RNAN0.36 and 0.61, ; free NAN was not detected.’ that thermal decomposition of 1-diazo-2-methyl- respectively) After elution from the paper, the C5P-NAN propane yields 2-methylpropene (67%) and methyl- yielded these analyses (molar ratios) : NAN, cyclopropane (3370). The carbenoid decomposition of other tosyl- 0.97; cytidine, 1.00; organic phosphate, 1.01. hydrazones in sodium methoxide-diethyl Carbitol The isolated C5P-NAN represented 6% of the total has been investigated.6 The hydrocarbons and nucleotide adsorbed by the ion-exchange resin. their per cent. compositions as obtained from these Evidence t h a t C5P-NAN was a single substance,’ not a mixture of C5P and NAN,Iwas obtained by tosylhydrazones are : (1)propanal; propene (90%) cyclopropane (10%) ; (2) butanal; 1-butene (92%), paper chromatography in three solvent systems, methylcyclopropane (4.6YG),trans-2-butene (2.3%), paper electrophoresis a t pH 5.0 and 7.7, and cis-2-butene (1.2%) ; (3) 2,2-dimethylpropanal; complete resistance to attack by NANaldolase2 and rattlesnake venom 5‘-nucleotidase. The ul1,l-dimethylcyclopropane (9293, 2-methyl-2-butraviolet-absorbing material on the paper chromatotene (7%), 2-methyl-1-butene (1%) ; (4) 2-buta(1) The Rackham Arthritis Research Unit is supported by a grant none; trans-2-butene (67%), cis-2-butene (as%), from the Horace H. Rackham School of Graduate Studies of T h e 1-butene (5%), methylcyclopropane (0.5%) ; and University of Michigan. This investigation was aided by a grant ( 5 ) 3,3-dimethyl-%butanones (pinacolone) ; 3,3- from the American Cancer Society and one from the National Institutes dimethyl-1-butene (52%), 1,1,2-trimethylcyclopro- of Health (A-512). (2) D. G. Comb and S. Roseman, THIS JOURNAL, SO, 497 (1958). pane (47%). It is concluded t h a t (1) rearrangeD. G. Comb and S. Roseman, Biochim. et Biogkys. A c t a , as, ments in carbenoid decomposition of diazo com- 653(3)(1958). ~
(3) For related reactions see H. Meerwein and K. v. Emster, Chem. Ber., 53, 1815 (1920); W. Huckel and F Nerdel, Ann., S!28,57 (1957). (4) The yields of hydrocarbons from proton-donor solvents are considerably smaller than that in aprotic solvents. (5) Cationic decomposition is not totally suppressed in these systems because methanol is formed. (6) Decomposition io diethylene glycol gave 3,3-dimethyl-l-butene (le%), 2,3-dimethyl-2-butene (le%), 2.3-dimethyl-1-butene (56oJ,), 1,1,2-trimethylcyclopropane(1170). The fact that the decomposition of tosylhydrazones of 2-methylpropanal and 3,3-dimethyl-2-butanone in diethylene glycol yields cyclopropanes indicates that carbenoid decomposition occurs competitively with cationoid processes.
(4) S. Roseman and D. G. Comb, THISJOURNAL, 8 0 , 3166 (1958); C. T.Spivak and S. Roseman, i b i d , , 81,2403 (1959). (5) G. T. Barry and W. F. Goebel, Nafu7e. 179, 206 (1957); G. T. Barry, J. E r p . Med., 107, 507 (1958). (6) These abbreviations are used: NAN, N-acetylneuraminic a d d ; C5P, cytidine-5’-monophosphate; C5P-NAN, cytidine-5’-monophospho-N-acetylneuraminic acid; NANaldolase, N-acetylneuraminic acid aldolase. (7) When stored in the dry state a t -16O, C5P-NAN decomposed t o NAN and C5P to the extent of 5 t o 10% per day. Fresh samples of C5P-NAN exhibited trace spots of C5P and NAN on the chromatograms; these became more apparent each day the samples were stored,
