4508
MELVIN
s. N E W M A N AND HllJihlAN s. LOWRIE
that its glucopyranoside rings exist in more than a single ring conformation. There are structural reasons for believing that two boat forms, B1 and 3B, may be the principal conformations involved. The the arconclusion is not entirely gument favoring these particular ring forms. It is recognized that other pairs of ring conformations might account for the behavior of amylose, provided [CONTRIBUTION FROM
THE
hcICI’HERSON
VOl. 76
one of the forms were reactive, the other unreactive with cuprammonium. Acknowledgment.-The author is indebted to Drs. F.R.Senti, A. E. Talley, A. L. Potter alld S. Schwilnnler for advice and criticism during thc preparation of this manuscript. SEW
CHEMICAL
ORLEANS,LOUISIANA
LABORATORY, OHIO
STATE L’SIVERSITY]
Attempted Syntheses of Nitrogen Analogs of Adamantanel B Y hZELVIN
s. r\TE\VhlLIN AND HARhlhN s. LOWRIE~ RECEIVEI) APRIL 15, 1954
Attempts to prepare nitrogen arialogs of aciatn:tiitniic from l , ; ~ , j - t r i i u b s t i t u t c dcyclohexanes failed. cyclohexanes were related in configuration, postulated t o be cis.
The interest shown in adamantane’ and in yuinuclidine4led us to seek a synthesis of the adamantane skeleton which could be modified t o introduce a hetero atom at a bridgehead. The success of triple condensations for preparing bicyclic conipoundsj suggested the use of the cis isomers of 1,3,5-trisubstituted cyclohexanes for this synthesis. IVe therefore attempted the following sequence6 Me02C,,
,C02Me
Q
C02hZc I HOH2C\ /CHLOH
hZeOiC,fl,COlhie
+
+
L) I
CO2hIe I1 R I ~ S O L O H,,,,CH.OSO2hIe ~C
nY -
‘
1
+
CHeOII
I11
‘/ I ( I ) Taken in part frutn thc 1’11.1) tliciis o f 11. S. I.r,wric. Oltiu S h t c University, 135%. (2) Cincinnati Chemical R’orks l;ellow, l K 5 l - l ~ % j 2 (3) C. Prelog and R . Seiwcrth, Ber., 7 4 , 1769 (1
