Cyclohexane Compounds: Ii. Synthesis and Structure of Two Stereoisomeric 3-Amino-1,2-Cyclohexanediols

Abstract

The stereoisomeric 1-ethosy-2,:<-eposyc~~clohesanes were prepared from l-ethosycyclohexene-2 via 1-ethosycyclohesene-2 bromohydrin. Ammonolysis of the lower-ancl higherboiling oxides furnished la-ethoxy-2~-hyclrosy-~<a-i~~11i11ocyclohesa11e and la-ethosy-2a-hydroxy-30-an~inocyclohesane respectively. In a similar manner, la-mcthosy-2~-hS.drosy3a-a~~~inocyclohexane and 1a-methosy-2a-hytlrosy-:3~-aminoryclohesi~ne were obtained from 1-methosycyclohesene-2 via 1-~ncthosycyclol~esene-2 bromohydrin ancl the stercoisomeric l-n1ethos~-2,3-eposycyclo11csi~11es. Ether cleavage of la-ethosy-and la-1nethosy-2~-hycIrosy3a-aminocyclohexane gave 3a-an1i~1o-la,2~-cycIol1exi~11ediol hydrobronlide, Iron1 which the free base was obtained. 3~-An1ino-la,2a-cyclohesa11ediol was prepared similarly from l aethosy-and la-rnethosy-2a-hydrosy-3~-arninocyclohesnne. Thc stereochelnistry of the 3-amino-l,2-cyclohesanediols, l-allioxy-2-hydrosy-3-i~1i1i11ocyclohesa11es, and 1-allioxy-2,3-epoxycyclohexanes has been elaborated.In 1947 1, 2, 3). The compound was characterized as the N-9-l~itrobenzoyl derivative, m.p. 201-203", and was converted 011 ether cleavage with hydrobromic acid '11.la~tzrscr.ipt rrceiued April 15, 1958.

Substituent effects on the regioselectivity of carbon-hydrogen insertion arising during stereospecific intramolecular cyclization of 7-norcaranylidenes

“…Insofar as the reactivity consequences of C3 substitution are concerned, the behavior of the inseparable mixture of cis and trans dibromides 38 and 39 (57:43)5e serves to denote the effect of methyl substitution. When treated with methyllithium, the three hydrocarbons 42 (60%), 43 (28%), and 44 (12%) were obtained.…”