SYMMETRICAL N,N’-DISUBSTITUTED PIPERAZINES
July, 1950 CHaCH2NOZ
+ HCHO +CH3CH(CHzOH)NOz (11)
or H~CC(CHZOH)~NOZ +I1
and pentoxazolidines will reveal that the grouping
=N-&-O-C-
HCHO
These compounds then react according to the mechanism suggested by Henry1 to give 2-nitro2,5-dimethyl-4-azahexanolwhich possesses an amino group -NH[CH(CH&] and a hydroxyl group on carbon atoms removed by one carbon atom
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is common to both structures.
Durini the hydrogenation of the oxazolidines,l1 the grouping a t hand is split as shown
I ’ I
EN-C-0-C
+ Hz +=N-CH I + HO-C I I
I
A similar splitting of this grouping in the 5nitropentoxazolidines would be expected to take CHs CH?-NH-CH(CH3)2 place if these compounds were hydrogenated. I+II+ >c< H20 A simultaneous reduction of the nitro group to KO2 CHzOH the amino group should also occur. The hydroI11 genation of these compounds was tried. The Inasmuch as amino alcohols with these structural nitrogen content of the product from each of features are known to yield pentoxazolidines with these reductions agreed with that of the expected aldehydes, i t can be assumed that the final step diamino alcohol. These data furnish additional in any route is the reaction of 2-nitro-2,5-di- support for the proposed structures of the 5methyl-4-azahexanol with formaldehyde to yield nitropentoxazolidines. water and 5-nitro-3-isopropyl-5-methylpentoxazoSummary lidine 5-Nitropentoxazolidines have been prepared CHa CH~--N--CH(CHB)Z by allowing one mole of a primary amine to react III+HCHO+ )CHz Hz0 with three moles of formaldehyde and one mole NO2 CHz-0 of a primary nitroparaffin. The hydrogenation of these new compounds The structures chosen for the new compounds are supported by the analytical data. Further was studied. Each nitro compound yielded a confirmation of their structure was obtained by new diamino alcohol. studying the hydrogenation of these compounds (11) Cope and Hancock, THISJOURNAL, 64, 1503 (1942); Senkus, i b i d . , 67,1515 (1945). and the examination of the reduced products. An examination of the structures of oxazolidines TERREHAUTE,IND. RECEIVED OCTOBER 10, 1949
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