4809 CH,OH
CHPOAC
IV, AC COCH3
I11
ammonia in methanol (room temperature), afforded only the cyclic product VII, CBHllN20j,1fi mp 177-178', [ a I z 5-21" ~ (c 0.77, water). VII, which shows no reducing properties, has also been obtained from streptozotocin by treatment with 0.1 N aqueous sulcdmic acid; 1 mole of Nz/mole of I is evolved during this reaction. Treatment of VI with nitrosyl chloride in pyridine" afforded tetraacetylstreptozotocin (11) identical with an authentic sample. Ammonolysis of I1 in methanol (- 10") afforded streptozotocin identical in all respects with that obtained from fermentations. In addition t o streptozotocin, S. achromogeiies produces enteromycin'S~lg and U-15,774,I9 both compounds containing unusual nitrogen functions. Acknowledgments. The authors are grateful to members of the Physical and Analytical Chemistry Department for microanalytical and spectral data.
2.48; three singlets, 3 H each, at 6 1.97, 2.03, and 2.07) of the tetraacetate IV are consistent with the postulation of the presence of an enol acetate grouping in IV. The formation of diazomethane and a positive Liebermann nitroso testg suggested the presence of an N-nitrosomethylamide group i n streptozotocin. The absence of a free amino group in streptozotocin, together with the isolation of carbon dioxide and D-glucosamine from (16) This cyclization of the methyl ureido compound is contrary to thc acid hydrolysis of I11 or IV, indicate the nitrosoamide to results reported by C. J. Morel, Helc. Chim. Actu, 44, 403 (1961), n h o be present as a urea derivative involving the nitrogen of did not obtain the cyclic product during ammoiiolysis of scvcral other alkyl derivatives, but is aiialogous to the results reported by both Morel the glucosamine. This conclusion is consistent with and Micheel's with aryl dcrivativcs. both the ultraviolet ,A,[, 228 mp (e 6360)]'O and the in(17) M. S . Newnian and A. I+
PhCH(OAc)P(OXOMe), bp 74' (003 mm) n ? . 15010 ~ PhCCiP(O)(OMe)? Ph CHCIP(O)( OMe)> I bp 105O (007 mm) HgCl n 2 j o 1.5276 rnp 151' HOAc
1 %
Novel Diazoalkanes and the First Carbene Containing the (MeO)?P(O) Group
Sir : The preparation of diazoalkanes containing heteroatom substituents, e.g., (RS)&N2,' ( P ~ S O ~ ) Z C N ~ , ~ C?,Et ,CO,Et ROCH2Cf3Ne,3 and RS02CHN2,4 their preparative utilization, and their decomposition to carbenes have been of current interest. Diazoalkanes containing phosphorus substituents, PhpP(0)C(Ph)Nz5and R2P(0)H CHNy (R = Ph, PhCH,),6 have been reported also. IV, m p 148.5-149" 111, rnp 170' We have prepared (Me0)eP(0)C(Ph)N2 (I) and (MeO)?P(O) (MeO)?P(O)C(Me)N,(11) because we felt that they would 'C=N-N=PPhJ serve excellently, cili the great variety of reactions diazoPh' alkanes and the carbenes (or carbenoids) derived from mp 126.5-127.5' dec them are capable of undergoing, in the introduction of o rga no p h os p h o r us functiona li t y i n t o diverse or ga n ic and tions of 11. The products of 1,3-dipolar addition of I inorganic compounds. We felt that I and I1 would be and I1 to activated vinyl compounds appear t o be more useful than the PhJ'(O)-substituted diazoalkanes 2-pyrazolines as shown; where two modes of addition since their niethoxy groups represent reactive phosphoare possible, the isomer involving Michael addition of rus functionality which would be useful in further synthe diazo carbon is favored. All 1,3-dipolar adducts thetic steps. showed strong N-H infrared absorption at -3200 Compounds I and I1 were synthesized as shown in cm-l and a broad downfield singlet in the nmr spectrum, eq 1. Compound I is an orange-red, crystalline solid, which was assignable to the N-H proton. Adducts to mp 44--44.5", which could be distilled at reduced presmethyl vinyl ketone and ethyl acrylate showed carbonyl sure and which appears to be stable indefinitely at room absorption corresponding to a,P unsaturation: vcs0 temperature. Compound I1 is a yellow, distillable (cm-I): 111, 1660; V, 1655; VI, 1725. The diethyl liquid, bp 37-38' (0.13 mm), B ? ~ D1.4583, which demaleate adduct I V showed two distinct C=O peaks at composes slowly at room temperature but is quite stable 1725 and 1735 cm-I, demonstrating the presence of on storage at 0". Both compounds show infrared conjugated and unconjugated carbonyl groups.' Of bands characteristic of the diazo group, I at 2080 and I1 special interest in Scheme I1 is the reaction of I1 with at 2075 cm-', iis well SI; P - 0 absorption at 1260 cm-I. phenyl(bromodichloromethy1)mercury in refluxing ben( 1 ) L'. Schollkopf and U. Wiskott, A m . Chem., 694, 44 (1966). ( 2 ) J. Dickmanii, J . Org. Chen?.,28, 2933 (1963). (3) C. Grot, E. l'fdil, E. Wcinrich, a n d 0. Weissel, Ann. Chem., 679, 42 (1964). (4) A . M . Van Lcusen, R . J. Mulder, and J. Strating, Rec. Trau. Chbn., 86, 225 (1967), L i n d erirlicr publications of this research group. ( 5 ) L. Horricr, l i . Hotlm;inii, H . Errel, and G. Klahre, Tetrahedron Letters, 9 (1961). (6) Pi.Kreutzkamp, E. Schmidt-Samoa, and A. IP(O)CHNz to methyl vinyl ketone and dimethyl maleate give I-pyrazolines, e.g., i,
Ph2P(0):H-
:HCOMe i
but unfortunately provided n o spectroscopic evidence in support of their structural assignments, so that their correctness cannot be assessed.
Communications IO the Editor
