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I so0 H A U S E R , PltWETT, .%SI) ASHBURN VOL. 26pension was adde d, wit.h stirring, 50 g. (0.415 mole) of aceto-phenone followed, af te r 30 m in., by 52 g. (0.415 mole) ofbenzyl chloride in 75 ml. of dry toluene. Th e mixture becam ewarm reaching approximately 80". The euspension wasst ir red unti l i t had cooled to room ternpcrature (abou t 2 h r . )and worked up as in A to g ive 15.7 g. (31%) of aceto phen one, (14) I. Heilbron, Dict ionary of Organic Compounds,h.p. 75-77 ' a t 10 .3 mm . ( repor ted1 ' b .p . 83-85" a t 12 mm .) ,

38 .5 g. ( 4 6 % ) of X, and 32 .8 g. 2 3%) of SI. Both of thesederivatives crystallized, and were shown to be identical withthose prepared in A by mixed melting points.D ~ ~ ~ ~ ~ ,,C.

Oxford, New York, 1953, Vol. 1, p. 16.

( C O N T R I B U T I O N FROM DUKE NIVERSITY .4ND U N I O N C A R B I D E CORP.]Mannich Reaction of Acetylferrocene with Formaldehyde and Secondary

Amines's2C H A R L E S R . H A U S E R , R O Y L. P R U E T T , 3 A N D T. A R T H U R M A S H B U R N , JR.

Received September 15, 1960Acetylferrocene w as condensed with form aldehyd e and d imethylamine hydrochlor ide or diethylamine hydrochlor ide to

form Mannich type sal ts , which were conver ted to the f ree amines and to acry loylferrocene. One of the sal ts was cyclized withphenylhydrazine to form a pyrazoline. One of the f ree amines was hydrogenated t o g ive the hydroxyamine.Rausch and Coleman4have recently reported the

aldehyde and dimethylamine hydrochloride toform salt I1 (Equation 1) his salt was pyrolyzedby steam distillation to give a polymeric ma-terial.

Mannich reaction of acetylferrocene (I) with form- ~ c o c H z c H z N R 2CHOH CHzCH2N (CH3)?eI FeI VIIV. R = C H Bg C O C H 3 HCHO q C O C H z C H z N R z * H C l V. R = C z H 6

Another reaction of salts I1 and I11 involvedheating aqueous solutions of them on th e steambath for one hour, under which condition the ele-ments of the secondary amine were eliminate toform the a,$unsaturated ketone VII. Good yieldsof VI1 were isolated, how ever, only un der carefullycontrolled conditions since this product tends t oundergo polymerization. Th e product was shown tohave structure VI1 not only by analysis but also

-b (1)I 11.R = CH3111. R= Cz Hs

In the present investigation, which was initiatedsome t ime ag o,2 I was found to undergo the Man-nich reaction with certain secondary amines, andthe products were shown to exhibit reactions th atare typical of ordinary Mannich salts.5 Thus, saltsI1 and I11 were prepared in good yields as indi-cated in Equation 1, and aqueous solutions ofthem were treated with sodium bicarbonate toliberate the free bases IV (80%) and V, respec-tively. Th e use of sodium hyd roxide instead ofbicarbonate brought about decomposition. Freebase IT. was then hydrogenated over Raney nickelto give the hydroxyamine VI in 80% yield.

(1) Su p p o r ted in p ar t b y Gran t CY-4 4 5 5 f ro m th e Na-t ional Inst i tu tes of Heal th .( 2 ) A portion of this work was completed in 1955 byI< L.1'. a t I h d e A ir P r o d u ct s C o m p an y , T on a w a n d a, N . Y.(3 ) l'wwnt address: Research Dept. , Union CarbideC'liemicals Company, South Charleston, W. Va.( 4 ) 31. 11. Rau sch an d L. E. Coleman, Jr . , J. Org.Chem.,2 3 , 107 (1958).( 5 ) I;.F. Blicke, Org. X ~ a c l z o n s , ,30 3 (1942) .

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by its infrared Spectrum, which exhibited strongbands a t 6.04 and 6 . 2 2 ~or the carbonyl group6and conjugated carbon-carbon double bond,7 re-spectively. nWCOCHiCHZe1 VI1Still another reaction of salt I11 involved itscyclization with phenylhydrazine to form the py-razoline V I11 in 49y0 ield. Tw o or more courses ofreaction app ear possible in th e formation of such acompound.*Th e struc ture of th e product was sup-ported by analysis and by i ts infrared spectrum,( 6 ) See L. J . Bellamy, The In frared Spectra of ComplezMolecules, Wiley and Sons, New York, 1958, p. 136.(7 ) See Ref . 6 p. 24 .(8 ) See Ref. 5, p . 320.

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w1iic.h showed n o Imid fo r a carbonyl group and,bowed htrong bands a t 6.25 and 6.64 1.1, which ma ytw nttr ibii tcd to a carbon-nitrogen douhle bond.g

N-N-C,H,q-J?..JFe' VI11l k s i d e s I1 and 111, the corresponding salt (m.p.l.i8-16Oo dec.) was evidently obtained from thereaction of I with morpholine hydrochloride; i tsanalysis was satisfactory for iron, nitrogen, andhydrogen but not for carbon. Also, bisacetylferro-( m e produced a s imilar sa lt (m.p. 176-179" dec.)

wit.h four molecular equivalents each of formalde-hyde an d diniethylamine hydrochloride. The analy-sis for iron and hydroge n fitt,ed th e bis-salt, bu taiinlyses for carbon an d nitrogen d id not fit the bis-o r mono-salt. Like I1 and 111,these s alts were verysolithle i n water, moderately soluble in et 'hanol,a i d insoliihle in diethyl et 'her.

E XP E R I M E KT AL ~ ~p-Uiinethylaminopropionylferrocene hydrochloride (11)..2 niiu ture of 13 .7 g. (0.06 mole) of acety lferrocen e (I),3.6 g.(ahoi i t 0.12 mole) of paraformaldehyde, and 9.8 g. (0.12mole j of dimeth ylam ine hydrochloride, 150 ml. of abso lute

vthanol , and 0. 5 ml . of con cd. hydroch loric acid w as refluxedfo r 2.5 hr. The resll l t ing solution was allowed to cool sonie-what : ind nn addi t ional 3 .6 g. of paraformaldehyde was:ldtlctl . Th e mix turr was the n refluxed fo r ano th e r 2 .5 h r . and:illowed to st an d ov ernight . On cool ing in an ice-sal t ba th,the rcd solut ion deposi ted brown crystals, which were col-lected a nd recrysta l lizrd from a minimum of isopropyl alco-hol to givc 8.0 g . (4770 ) of orange-yellow salt 11, m.p . 170-171' dcc; reporte d4 n1.p. 170-172". In a noth er experim entthe p roduc t was ob ta ined in 92% yield, m.p. 168-171" clec.( r rcrysta l l izrd from a minimum of abso lute e thanol) .Ilyctrochloride I1 was vcry soluble in water , mo derate lysoluble in e thanol , a nd insoluble in die thy l e ther .Z'reatnwd of sal( I1 to li6erate f r e e base I V . T o a cold solu-tion of 1 g . of sa lt I1 i n a minimum of water was added acold, sa tnr a ted solut ion of so dium bicarbonate t o precipi ta teth e free base IV , which was collected o n a funnel and a i r-dr ied. Th e crude sol id (1.2 g. ) was s t i r red wi th ho t n -hep tanennd th e mixture f i l tered. T he f i l t ra te was cooled t o give 0.70g. 8 0 % ) of IV (f luffy orange crysta ls) , m.p. 72-73 and at 72-;2.,5' aft r r another recrysta l l iza t ion from n-heptane..trial. C a lc d . fo r C l j H l g F e N O :C, 63.2; H, 6 .7; Fe , 19.6;S ,4.9. Foun d: C , 63 .2 ; H, 6 .3 ; Fe , 19 .8 ;N, 4.7.I ie tone-amine IV was soluble in chloroform an d in d i luteh!,drochloric acid an d moderatc,ly soliihle in wa ter .Hyrlrogeitnlion 0.f I V to f o r m hydroqanzine V I . A solut ionof 2 g. of krtonc-amine I V in 150 ml . of abso lu t r e thano l wassh:iken with 8 n l l . of W-7 Ra ne y nickell1 in a P a r r low-pres-s i i r i ? hydrogcnat inn apparat i i s under 57 p.s . i .g . Within 5

( 1 , ) ) See ref . 6, p. 286.( 1 0 ) hle l t ing points are uncorrected. Infrared spect ra\ver t%o1)tairir.d o n Pcrkin-Elmer LIodrl 21 recording infra-

rctl sl)ectroy)liotonietcr.( I I ) .I.A. 1';tvIir nnt l T I . .\dliiris, J . ' I I I~ .'hein. Soc., 68 ,1471.

mill. th e theoretical ab sorption uf h ydrog en had occ urrcd.Th e pressure was the n re leased a nd th e ca ta lyst was removedby f i lt r at i on unde r a rgon . Th e f i l t r a t e was evapora t ed todryness in an a i r blast t o give 1.6 g. (8070) of VI (yellowsolid), m.p. 82-83.5'. Re cry stalli zatio n f r o m n-hcp tane gavea light yellow solid, m.p. 81-81.5'.Anal . Calcd. fo r ClsH21F eSO: C, 62.7; H, 7.3; Fe , 19.4;N, . 9 . Found : C, 62.6; H , 6.8; Fe , 19.5; X, 5.2.Infra red ban ds: 2.8, 3.5, 6.8, 9.0, 9.4, and 9 . 9 8 ~ .Conversion of salt I1 to acryloylferrocene ( V I I ) . 4 solut ionof 3. 5 g. (0.0109 mole) of s alt I1 n 15m . of m ater was heatedo n t h e s t e am b a t h f o r 50 min . Th e res t ing red mixture waswhich was collected on a funnel and a i r-dr ied. Th e sol id wasst i r red wi th hot n-hexane and the mixture f i l tered. The f i l -t r a t e was reduced in vo lume ( s t eam b a th ) and coo led t o g ivered crystals of acryloylferrocene (V II ), m.p . 71-72", Aftertw o recrystall izations from n-hexane, 1.0 g. (42 7,) of V I1 wasobta ined, mel t ing at 73.5-74".Anal.12 Calcd. for C13H12Fe0:C, 65.0; H, 5 ,O ; Fe, 23.1Fo un d: C, 65.0, 65.2; H , 5.2, 5.1; Fe , 22.5, 22.7.Infrared band s: 6.04, 6.22, 6.89,9.04, a nd 10.0 1.

In cer ta in other experiments th e yie ld of VI 1 was some-wha t l ower t han tha t r epor t ed above and a considerableam ou nt of polymeric material was obtained..4lthough VI 1 appeared t o be stable at room temperature ,i t underw ent thermal polymerizat ion, as m ight be expected.@-Diethylaminopropwnylferrocene hydrochloride (111).T h i s s a l t was prepare d fr om 0.0 6 mole of acetylferrocene,0.19 mole of pa raform aldehy de an d 0.12 mole of dieth yl-amine hydrochloride essentially as descr ibed above for sa l t11, except tha t only 60 ml . of absolute e thanol were used.Th ere was obta ined 14.4 g. (69%) of crude 111. Afte r tworecrystall izations from ab solu te isopropyl alcohol, th e orange-brown crystals me lted a t 159-160'.A 7 ~ u l . ~ ~ , ~ ~a l cd . fo r C17Hn4FeXO C1:, 58.4; H, 6 .9; X,4 .0 . Found : C, 58.7, 58.8; H, 7.3, 7.4; X, 3.7, 3.8.Infrared bands: 6.0, 6.86, 8.04, 9.04, 10.0, and 12.22 M .Hydrochlor ide I11 was very soluble i n water , m oderate lysoluble in e thanol , a nd insoluble in die thyl e ther .Treatrnenf of salt I11 to liberate f r e e base V. To a cold solu-tion of 1.5 g. of sa l t I11 was added cold aqueous sodium bi-carbonate . Since no precipi ta te was obta ined, the solut ionFas extracted twice wi th chloroform. Th e red ext racts werecombined, and the solut ion washed wi th smal l amounts ofcold water. Removal of the solvent left a dark red liquid,which failed t o crystall ize.Anal. Calcd. for C17H23FeNO: C, 6 5.0; H, 7.3; Fe, 17.8;9,. 5 . Found : C , 64 .8 ; H , 8.0; Fe, 18.0; X, 4.7.Conversion of salt I11 to acryloylferrocene (V I I ) . Th i s r eac-tion was carried out essentially as described above wi th s a l tI1 to produce 47y0 of 1'71, s red needles, m .p . 73.5-74" (re-crystall ized from n-hexane). .4dmixture with a sample ofVI1 f rom sa l t I1 did not dcpress the mel t ing point .Cyclization of salt 111 with phenylhydrazine to f o r m V I I I .A solut ion of 1.5 g. of sa l t 111, 1.5 g. of phenylhydrazine , in10 ml. each of absolute e thanol and glacia l acet ic ac id wasrefluxed for 6 hr . On standing overnight : it room temp eratu reth e red solut ion deposi ted orange needles, which were col-'lected on a funnel and recrystal lized from ab solute e thanolto g ive 0 .7 g. (49y070) of 1-phenyl-3-ferrocenylpyrazoline(V II I) , (orange pla tes) , m .p. 142-144" .Anal.12Calcd. fo r C I S H I B F c S ~ :, 69 .1 ; H , 5 .5 ; Fe , 16 .9;PiT, 8 .5 . Found : C, 68.8, 69.1; H, 5.8, 6.0; Fe, 16.6, 16.8;9,.6, 8.7.

coo led in an i ce b a th t o p rec ip i ta t e aiasty red-brown solid

Infrared ban ds: 6 .25, 6.64, 7.72, 9.04, 8.96, a n d 1 4 . 5 ~ .DURHAM,. C.SOUTH CHARLESTON,IT-. krA .(12) Analysis by Galhra i th Lahoratory, Knoxvi l le , Tenn.(13) The values for i ron and chlorine Ivere low by 1.5and 0.7354 but high i n another dct t rminnt ion by 0 . 6 3 and0.46c;, respectively.