July 5, 1961
COMMUNICATIONS TO THE TABLE I
ASYMMETRIC
SYXTHESES
OF
fTU?ZS-CYCLOPROPANE-1,2-DI-
CARBOXYLIC
Run
Solvent
1 Toluene 2 Toluene 3 Toluene 4 DMF 5 DMF 6 DhIF 7 Nitrobenzene
ACID
Acid, % yield
[a]?'D,
60.0 41.5 40.1 46.0 46.0 51.0 31.1
-1.5' -1.9" -2.7" S8.6"
H20
f8.7"
+9.3" 4-0.25
Optical yield
1.8 2.2 3.1 10.2 10.3 10.9 0.3
Dimethyl ester ester [ a ] % ~ EtOH
-2.3' -2.8" -4.0" f12.8' +13.0' +13.8' +0.38'
EDITOR
2963
silanola te reacts in anhydrous ethereal solution with trimethylchlorostannane forming insoluble LiCl and hexamethylstannosiloxane in very good yields according to ( CH3)3SiOLi
+ (CH3)aSnCl
4
LiCl
+ ( CH3)aSiOSn(CH&
Dimethyldichlorostannane and niethyltrichlorostannane react under the same conditions forming LiCl and bis-trimethylsiloxy-dimethylstannaneand tris-trimethylsiloxy-methylstannane, respectively 2 (CH3)sSiOLi
+ (CH3)zSnClz
3 (CH&SiOLi
4-CH3SnCla
+
[(CH~)PS~O]ZS~(CH~)Z 2 LiCl [(CHs)aSi0]3SnCH3 f 3 LiCl
-t
-+
investigation and will be the subject of a future publication.
Tatlock and Rochow4 already had studied the reaction of Me$iOK and MezSnClz in 19.52, but reINSTITGTE FOR CHEMICAL RESEARCH Y . INOUYEported only a few analytical data and physical KYOTOUNIVERSITY S.INAMASUconstants of their reaction product. Table I TAKATSUKI, JAPAN, AND M. OHNO shows the physical constants of the new methylDEPARTMENT OF CHEMISTRY FLORIDA STATE UNIVERSITY 'r. SUCITA stannosiloxanes. Hexamethylstannosiloxane shows surprisingly TALLAHASSEE, FLORIDA 11. AI. Lv.4LBORSKY high thermal stability. It may be distilled a t RECEIVED MAY22, 1961 atmospheric pressure without decomposition. Bistrimethylsiloxy-dimethylstannane, in contrast to METHYL-STANNO-SILOXANES AND METHYLthe results of Okawara, et uL,l forms crystals PLUMBO-SILOXANES melting a t 48'. The melt is stable up to 150'. Sir: It may be vacuum distilled (b.p. (11 mm.) 74'), A recent article' prompts us to report some re- whereas the distillation under atmospheric pressults of our own studies in the field of alkylhetero- sure a t 160' is accompanied by partial decomposisiloxanes. tion, hexamethyldisiloxane and dimethylpolystanTo gain some knowledge on the stability and noxane being formed properties of siloxanes, in which silicon atoms are partly replaced by other IVb elements (Ge, Sn, Pb), we have planned to synthesize heterosiloxanes of low molecular weight and definite composition. Under similar conditions tris-trimethylsiloxyFirst we prepared some alkyl-germanosiloxanes, methylstannane undergoes thermal decomposition e.g., hexamethylgermanosilosane Me&XOGMea, by yielding hexamethyldisiloxane and polymeric the reaction of LiOSiMes with MezGeC1. We methylpolystannoxane, which still contains trihave found that this type of reaction furnishes also methylsiloxy groups attached to tin. the synthesis of the corresponding tin and lead From ethereal solutions of trimethylbromoplumcompounds. bane and sodium trirnethylsilanolate NaBr preExcept for some studies on the tin-dkylsilano- cipitates and high yields of hexamethylplumbolates, compounds without alkyl groups attached to siloxane are recovereds) tin,a145a,sb.6 only few reports on real alkyl-stanno- (CH3)aSiONa (CH3)3PbBr NaBr siloxanes have been p ~ b l i s h e d . ~ Moreover J~~~ (CH&SiOPb( CH3)3 these studies mainly dealt with polymeric materials whereas the first members of those series have not This first member of the lead-siloxane series forms a colorless liquid of high vapor pressure and unbeen described. Okawara, et uL,I failed to obtain hexamethyl- expected thermal stability. I t may be transported staniiosiloxane and bistrirnethylsiloxy-dimethyl- in high vacuum even a t room temperature and stannane by method of transesterification and co- boils without decoinposition a t 172' under athydrolysis. We were able to synthesize these com- mospheric pressure of dry nitrogen. At ternperapounds by a simple method : Lithium trimethyl- tures ebove 150' the vapor reacts with oxygen with explosion forming elementary lead. Under normal (1) R. Okawara, D. G. White, K. Fujitani and H . Sato, J . A m . Chem. conditions the compound is stable against dry Soc., 83, 1342 (1961). (2) H. Schmidbaur and M, Schmidt, Chem. Ber., 94, 1138 (1961); air and the influence of light.
+
-+
+
94, 1349 (1961).
(3) W. I. Patnode and F. C. Schmidt, J . A m . Chem. Soc.. 61, 2272
(1945).
(4) W. S. Tatlock and E. G . Rochow, J . Org. Chcm., 17, 1555 (1952). (5) (a) K. A. Andrianov and A. A. Zhdanov, Isuecl. Akad. Nauk SSSR, Oldel. K h i m . Nauk, 779 (1958); C . A . , 6 2 , 19916 (1958): (b) K . A. Andrianov, A. A. Zhdanov and E. A. Kashutina, Zhur. Priklad. Khim., 3 2 , 463 (1959); C . A . , 63, 11079 (1959); (c) R. A. Andrianov, T. N. Gamina and E. N. Krushtaleva, lavest. Akad. Nauk S S S R , O l d e l . K h i m . N a u k , 798 (1956), C . A . , 51, 3487 (1957). (6) E. D. Hornbaker and F. Conrad, J . Org. Chem., 24, 1858 (1959). (7) F. A. Henglein, R. Lang and L. Schmack, Makromol. Chem., 24, 103 (1957).
TABLEI MELTING AND BOILINGPOINTS O F METIXYLSTANNOSILOXANES Formula
( CH3)3SiOSn(CH3)o
Fp., OC.
-59 +48 [(CH3)~SiO]~Sn(CH3)~ +34 [(CH&SiO]sSnCHl
O C .
B.p. Mm. OC.
720 35 141 160dec. 720 75 155dec. 720 49
Mm.
11 11 11
(8) LiOSiMea under the same conditions does not form the plumbosiloxane with MeaPbBr, because of the solubility of LiBr in diethyl ether, which prevents the metathetic reaction going to completion.
COMMUIVICATIONS TO THE EDITOR
2964
Hexamethylplumbosiloxane, as well as the tin compounds described above, are very sensitive to water. Even the moisture of the air leads to hydrolysis. The infrared spectra of the new compounds are assigned easily to the structural units of the heterosiloxanes. Together with the analytical data and chemical reactions they unambiguously prove the composition. The wave length of the Si-0-X frequency (X = Si,Ge,Sn,Pb) seems to be of considerable interest. The comparison of the vas Si-0-X values of the hexamethylheterosiloxanes (Table 11) demonstrates a systematic shift of
Vol. 83
of a t least two isomeric zygomycins A. “Diaminohexose I” was shown7 to be identical with neosamine BI1 from neomycin B. The present report establishes the identity of “diaminohexose 11” and neosamine C. Neosamine C and “diaminohexose 11” were converted separately to their N,N’-diacetyl derivatives, the former by a modification of the method employed earlier for the neomycinss and the latter’ by the method of Roseman and L u d ~ w i e g . ~Comparison of the physical properties of the X-acetylated derivatives (needles from acetone) establishes their identity ( c j . Table I).
TARLE I1 TABLE I MELTINGPOINTS,BOILIXGPOISTS AND SI-0-X FREQUEN-PHYSICAL PROPERTIES O F 2,6-DIAcET.4121IDO-2,6-DIDEOX~’CIES IS THE INFRARED SPECTRA OF HEXAMETHYLHETEROSILD-GLUCOSE SAMPLES OXANES
N,S’-DiacetylYS*
Formula
[ CHS)aSiOC(CH,);
(CH3)3SiOSi(CH3). (CH3)3SiOGe(CH3i3 (CH?)%SiOSn( CH3)3 (CH3)3SiOPb(CHa)a
FpiOC.)
-91 -5; -68 -59 -1
“C
3.p.
103.5 ion.5 117 141 172
hIm.
760
760 725 720 720
Si-0-X tI/cm.)
1052 in55 990 980 9%
this band to higher wave length in the sequence Si-GeSn-Pb. Thermal stability as well as reactivity in heterolytic reactions decrease in the same order. The increasing mass, radii and decreasing electronegativity of the heteroatoms are the reasons for these observations. The new methylstanno- and methylplumbosiloxanes are characterized by extremely unpleasant odor. They all a.re highly toxic, mainly because of their good solubility in organic solvents (and in the lipoid) and their sensitivity against hydrolysis.
X p . , OC.
Mix. m.p.e
[a]%e
R\-\o5
Seosamine C 209-215 ... 35. (i 1 . :3:3 “Dianiinohexose 11” 211-216 209-213 37.2 1.32 Syntheticc 207-212 207-215 3t5.8 1 :32 SyntIieticd 209-213 209-217 36.8 L:32 IL Mixture m.p. with S,S’-diacetvlneosamine C. * Kr (sample)/Rr (N-acetylglucosarnine); BA%W415. Present sample. Diaminoglucose sample of Tx’eidmann and Zimmermann,lz acetylated by the standard method.8 e Equilibrium values.
In connection with this work an authentic sample of 2,6-diamino-2,6-dideoxy-~-glucose has been prepared, starting with the known methyl N-acetylD-glucosaminide (1).lo Treatment of I with p toluenesulfonyl chloride in pyridine gave the amorphous methyl N-acetyl-6-O-tosyl-c-~-glu~0~aminide (11), Rf 0.90 (PEAW:122 = pyridine: ethyl acetate : water, 1 : 2 :2) [*lnal. Found : C, 49.21; H, 6.16: N , 3.45; S, 8.111. The tosylate INSTITUT FUR XNORGASISCHE CHEMIE DER UKIVERSITAT MCNCHES HUBERTSCHMIDBAUR(11) was heated for 24 hr. a t 105’ in saturated methM ~ X C H E2,NMEISERSTRASSE 1 MAXSCHMIDT anolic ammonia to give the crude 6-amino comGERYAXY pound, which was purified by means of its crystalRECEIVED MAY8, 1961 line Y-acetyl derivative (needles from methanol), methyl 2,6-diacetamido-2,6-dideoxy-a-~-glucosaminide (1111, Rr 0.77 (BAW 221),11 m.p. 240IDENTITY OF NEOSAMINE C, LLDIAMINOHEXOSE 242’, [ c Y ] ~ ~ D 119’ (c 0.42, water), [Anal.Found: 11” FROM ZYGOMYCIN A, AND 2,6-DIAMINO-2,6DIDEOXY-D-GLUCOSE K , 10.131. Hydrolysisll of I11 gave 2,6-diaminoSir: 2,6-dideoxy-~-glucosedihydrochloride, [ ff ] 27D Keosamine C,’ one of the four component frag- 61.5’ ( c 0.96, water), Rf 0.17 (BAW 221)”; corments of neomycin C and a fragment wherein responding physical constants for authentic neosneomycin C differs stereochemically from neomy- amine C dihydrochloride are [ f f I z 3 D 69’ (c 0.87, cin B,Zwas shown earlier to be a 2,6-diamino-2,6- water), Rf 0.17 (BAW 221).11 The synthetic dideoxyhexo~e~ and i t was assigned D-glucose stereo- diamine was K-acetylated9 ; identity of the synthetic material and the antibiotic degradation chemistry.’ Recently the antibiotic complex zygomycin A4t5 fragments is established by the data of the table.’? Further confirmation of the identity of the four was characterized. Hydrolysis of the complex gave a mixture of a t least two diaminohexoses (“I” samples was provided by their nearly superirzlposand ‘tII”),6!7 apparently resulting from a mixture able 1i.m.r. spectra, a physical property which has
+
+
+
(1) K . 1,. Rinehart, Jr., 1’. 1%‘. K . Woo, and A . I) Argoudeiis. .I. A m . Cheiih. Soc , 80, 6461 (10.38). ( 2 ) K. L. Rinehart, Jr., A. D . Argoudelis, T. P. Culbertsnn, \V. S Chilton, and K.Striegler, i b i d . , 82, 2970 (1960). ( 3 ) K . L . Rinehart, Jr., and P. Xi’. K . Woo. zbid . 80, 64fi3 (19%) (4) &f. Shibata, E Higashide, T . Kanzaki, H . Yamamoto, and E; S a k a z a w a , A g v . Bioi. Chein. Japari, 25, 171, 1713(1961). ( 5 ) J . Hitomi, S. Horii, T. Yamaguchi, M.Imanishi, and A h i i y a k e , J . A n t i b i o l i c s ( J a p a n ) , S e v . A , 14, 03 (1961). ( 6 ) El. Hitomi, S Horii, ‘r Yamaguchi. and 4 l l i y a k e , Cheiii. Phavm. Bzi11. J a P n i i , in press. (7) (a) S . Horii, 7‘.Yamaguchi, I I . Hitomi, and A hligake, ibrd , [1],9 , 340 (1961): (b) S. Horii, J . A n t z b i o l i r s ( J ~ p a i i )in , press.
( 8 ) K . L.Rinehart. Jr , A. D. Argoudelis, \T. A . Gus.;, A . Sohler, and C . P. Schaffner, .r. .4n7. Chem. S o c , 82, 3938 (1900). (9) S . Roseman and J. Ludowieg, absd., 76, 301 (I9.50 (IO) R . C . G. ltoggridge and A . Seuberger, .i. Ciicw (19:38), (11) K . L Rinehart, J r . . and P 1%‘. K . Woo, J . A r i l (‘itrrii 50,- , 83, 643 11961). (12) A preparation of :!,(i-diamino-2,~-dideoxy-D-glucose by another route a a s reported recently [I%.n’eidmann and H . K . Zimmermann, A>igew. Chem., 72, 750 (1960)l. We have N-acetylated a sample Of the latter diarninohexose preparation igeneronsly provided hy nr. XYeidmann and Zimmermann) and have found it, too, t o be identical with the acetylated derivatives of t h e natural compoiinri (ti. table).
