2231
NO,~ES
VOl. 76
,
&I.IJ., OC.
E t h y l ester.HCl----C1 Anal., Calcd.
'b Fou11d
or the acid, m.p. 198-2011'
c:it:ily.st rcstep yields of ~-substitutetl-aniitioi,entanenitriles cthcr solution ovcr 770 ~~:illatliu~ii-ijii-charcoal in cju;intitative conversions t o :i-s~l~stittiteti-;ll~iii~iomuch improved over the yields obtaiiied when direct sulted I)L~iit:tiieiiitrilcs. Table I lists Iihysicai constnllti a i i t l :in:tlydistillation of the 3-substituted-a1~iino-:~-~)eiiteiie.cs for these conipounds. nitriles was followed by low pressure hydrogenation. High Pressure Hydrogenation of 5-Substituted-aminoThe unsaturated addition products were hydro- pentanenitri1es.-These h~-drogenations\\-ere carried out i i i solution s,itur:itctl irith :imtnoni,L ovcr 1iaiic.y iiickel genated at low pressure to ~-substituted-nmino- vthaiiol catalyst :it initial presstires of 800-1400 1) peiitanenitriles. These compounds in turn were tures of 90-100". The products were scp hydrogenated a t high pressure in the presence of distillatioii . Table I lists the physicnl ccln~,l:ititsa n t l arnnionia. In the high pressure hylrogenations if -aininoiicntaui~s the amine grouping WLIS tcrti:uy, high yields of only iubstituted-;iiiiino-l Hydrolyses of 5-Substituted-aminopentanenitriles (5-Sub.i-~lialkyluir,ino-l-aiiiinol,entaiies were obtained. stituted-aminopentanoic Acids).--IIytlrolyscs were c:irriet! However, when the aiiiiiie grouping w a s secondary, o u t in coiictl. hydrochloric :tcitl-heuting t h r iitixturcs on ii ;in intramolecular rctluctii dkylation took place to ste:iin-b:tth for ?-:I hours. T h e resulting wlution \ v c thc 11 a large extent to gix-c: S-substituted piperidines in eareful1~-ev:iporatc.tl to dry1 , a n d the solitl rciitluc !vas e\rtractetl tlrice \\.it11 hot a one or lrith cold ahsolute addition to ~-alk~-latiiino-l-alniiiopetit~iiies. Thus, ethanol. Acetone proved more satisf:ictory, since it did not from the 5-cthylaiiiino-, 3-isopropylariiiiio-, 5 - w tiisiolve the li!--product amiriotiiutn chloride :is rc,arlily RS butylamino-, 3-s-butylami1io- and 5-cycloliexyl- did the ethaiiol. 111 aclditioii, in sonic e x e s i n which etli\vas used :tiid the inistures w r e \vnriiietl, thc, acids w r e aniinopentaneriitriles were obtained the K-ethyl-, aanol t least partly converted to their ethyl esters. The hydroS-isopropyl-, S-it-butyl-, S-s-butyl- antl N-cyclo- chlorides of the .i-suh~titutetl-airiiiiopcntnnoic :tcids were 1iel;ylijiI)eridiries. -1similar reductive cyclization precipitated by :iddition of ether t o the acetone or cthanol has been reported recently by Boekelheide, et nl.,g solutions niitl could be recrystallized fi-om either :~cetoneor mixtures. Acetone rccrj..jt:illizntion apI)c:ircd in the reductioii of ~-(_"-pyridyl)-butanenitriles.etha.no1-ethertali of soine\vhat higher iiieltitig p o i n t . 'rxhlc The 3-substituted-atiiiriopentntieiiitriles were also pliysiciil coristuiits :inti aiial hydrolyzed t o 5-substituted-a1iiiiiol,entanoic acids, which were isolated as their hydrochloride s:dts. TA13LE I11 The ethyl esters of these acids usually forined A o u r ~ ~ o 1'r~or)ucrs s o F ~ , . ~ - ~ ' ~ S . ~ ~ ~ I ) I I ~\ y~ mI i~ ~ I , ~ rather easily on heating the acid hytlrochlorides iri Tno 1 f o i . m OF !LMINE absolute ethanol. Cpd T3.p. R p f . iiiilcu, S : ~ i i t cqiiib,., Experimental Carbon, hytlrogcn :tnd nitrogcli alia1 1)erfornied ljy t h e Clark 3licro:iiialytical Laboratory, 1-rbnna, Illinois. LZelting points are uncorrected. 2,4-Pentadienenitrile and Amine Addition Reactions. ( 5 -Substituted- amino-3 - pentenenitriles) .-The 2,1 -pentadienenitrile6 was added t o a slight molar cscess of amine in a prcsiurc bottle, and the bottle 11-a~ flushed out with argon liefore vnliiig. If no imtnet1i:ite esothermic reaction en-iietl, t h c niirturc, T W ~ \\-,trincd :it
