1678
i v .L. WOLFROM AND
[CONTRIBUTION FROM
THE D E P A R T M E N 1 O F
J. B. MILLER
CHEMISTRY OP
Vol. 80
T H E O H I O STATE
UNIVERSITY ]
The Reduction of Diazornethyl-/@o Acetates ; A New Route to Osone Derivatives BY M. L. ~VOLFROM AND J. I3. ~ I I L L E R ~ RECEIVED NOVEMBER 6, 1957 Reduction of 1-deoxy-1-diazo-keto-o-galacto-heptulose pentaacctate (111) with am~noiiiuinhydrogcn sulfide or sodium dithionite yields 3,4,5,6,7-penta-0-acetyl-~-gu~uc~o-heptosone 1-hydrazone. T h e reaction was applied also to the synthesis of 3,4,5,6-tetra-0-acetyl-~-arebino-hexosone 1-hydrazone (11). Reduction of 111 with aluminum amalgam gave penta-0acetyl-l-deoxy-keto-D-gcl.lacto-heptulose(11.). ll,l-,5,g,i-Penta-n-3cetyl-D-gill:Lcio-lieptos[~rle1-[(2-hydrosy-l-naphthyl11iethylene) -hydrazone] is described.
In 1910, Forster and Ziirimerli found that a diazo group may be reduced to a hydrazone with amnionium sulfide3and thus demonstrated the reversibility of the hydrazone-diazo systems since the oxidation of certain hydrazones had previously been shown to yield diazo compounds.4 The actual reducing agent in this reaction system is most probably the anion HS- since both Stauditigcr and co-workers" and ourselves found that i t i this reaction hydrogcn sulfide will not act as a reducing agent in the absence of ammonium hydroxide (or ammonium sulfide). T h e HS- anion will act as a catalyst in the presence of added hydrogen sulfide as
+ ZHS-
KCOCHN~
----f
+- s
moccr=x--Siid
-t-
tion of amines and hydrocarbons when the 1%'nitroso group is reduced with sodium dithionite.8 The 1.73 p absorption peak characteristic of diazo c o n i p o ~ n d disappears s~~~ upon reduction to the hydrazone, but the 6.1 p absorption9 is retained (Table I). Yates and associates'" have shown that a band in the region 7.2-7.5 + is also characteristic of diazonicthyl ketones and we find this to be true. TABLE I INP'RAliEI)
OF
SPECIRA
rIIAZ0
EIYDRAZOXE
s
cUMIIpOUNUS A N D
THEIR
DERIVATIVES
C~,tII~II~LIII
