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Chemistry. "(hi a c' -li'lrdnnlhiiliiiiii'ridini-.'^ By Pi-oC. A. P. X. 



FHA^'('Hl.^ro^■T and Di'. II. Fuikd.mann. 



(Communicated in \\\v meeting of September 24, 1904). 



This siiltslance, wliicli was ()l»taiiiO(l in iSSo hy ('anzonfri and 

 Spica Init in an iin|nnv ('(tmlilion. was prepared l»y ns in another 

 manner, namely, by rednelio]» of 7-brom()tetranietliyl|>ipej-idine with 

 a copper-zinc conple (Gladstone-Tribe's metliod) in absobile alcoholic 

 solntion. 



It is a li(inid boiling at lo5,°5 — i56°5 at 7()() ni.ni. ])ressnre having 

 a sp. gr. of 0.8867. With water it yields a crystalline coniponnd 

 which melts at 28'' and loses its water totally or partially in a dry 

 atmosphere. The componnds witli hydrogen chloride, hydrogen bro- 

 mide and sulj)luiric acid form very beantiful crystals; lliose with the 

 two first-named acids snblime on heating without previous fusion, 

 those with sn1|)hnric acid melt : the acid one at 174'', the neutral 

 one at 270°. 



Compared witli pijteridine, this amine reacts remarkably slowly 



on acid chlorides sucli as benzoyl chloride, chloro-formic esters, 



picrvlchloride etc. In a(|ne<)us solutions the reaction takes jdace 



hardly at all, in ethereal solutions extremely slowly. However, there 



were obtained : methylurethane as a liquid with a strong mint-like 



odour boiling at 227^ at a pressui-e of 7<30 m.m. ; s|). gr. 0.9848 



and the benzoyl dei-ivalive as crystals melting at 41°— 42 ; the i)ici'yl 



derivative melts at 225'. An ellbrt to ju-epare a urea from the hydrogen 



chloride compound and ])otassium isocyanate has resulted as yet in 



failure. This j-eminds us of experiments of Dr. K. H. van dek Zandk 



in 1889 with di-isopropylamine, where urea could oidy be obtaijied 



Avith difficulty and in very small amount, whereas dinormalpropylamine 



j)resented no difiiculties ^). If we com|)are the formulae of di-isopro- 



pvlamine and ft ^/-letramelhyl[>iperidine we notice that they oidy 



CH, 



/\^ 

 H,C CH„ 



H H 11 



(CHO.. C C (CH,)., (CHJ.,C C(CH,)., 



' \ /" ' \/ 



N N 



H H 



Ï) Some years before, I had already noticed an analogous phenomenon when 

 treating propyl- and isopropylmalonic acid with nitric acid; the first compound is 

 much more readilv attacked than the second. 



