REACTIONS OF CARBON SUBOXlDPi: WITH HYDROXYLAMINES BY FRED W. SACKETT THESIS FOR THE DEGREE OF BACHELOR OF SCIENCE CHEMISTRY COLLEGE OF LIBERAL ARTS AND SCIENCES UNIVERSITY OF ILLINOIS 1922 ti" 'V it: I I 3 2 2 Sa / UNIVERSITY OF ILLINOIS THIS IS TO CERTIFY THx\T THE THESIS PREPARED UNDER MY SUPERVISION BY FPJ^B UAPD SACKUTT ENTITLED REACTIONS OF CARBON STOOXIDE Y.MTTT Tr>DRn>P,HC-YIINFS IS APPROVED BY ME AS FULFILLING THIS PART OF THE REOUIREMENTS FOR THE DEGREE OF M^IHELOR Instructor in Charge Approved ACTINO HEAD OF DEPARTMENT OF __QHSMIS[CEy_L 5;;o2«4 ?IOV!UJI YTI2^3V1WJ YH >ioiar/;i3«iua ym *mmTiarar amr s * ■/ ' "' 31 ^ * •I T '.ii/ n C 3 fl 3 . ' V. % # I ■ ;> ‘■f . ' 1 ).. 3 -I. >i. >*r V.'. ' >,■ , - .‘.r 'i..^ --^i ■ -~j. Ja ’"^'■is 64 » Jf,'" 3 H 1 ; f 10 M '. I 5 |»nriVai|',l.^i. n ?j 3 '« Y^fl^Oa'PlA El' '*• 4 '*• i '.| ■ - V . ! , « 4 | T .1 , } . \ 1 . ’ ii e. I » t. * . *1 . . i \y :Jc&28ik«iaa ' ^o THH.vn' >1^130 ^aoAin c«itca .i ■»' - ir # • "SAtil,-. 1 ':^.:i.- AcloioviTleilsement This opportunity is taken to express appreciation for the suggestions and criticisns of Dr. Charles D. Hurd which were of material assistance to the experiment. Digitized by the Internet Archive in 2015 https://archive.org/details/reactionsofcarboOOsack CONTENTS Page I. Introduction 1 II. Experiuental 4 III. Sumnary 9 IV. Bililiograpliy 10 I REACTIONS OF CARBON SUBOXIDE FITII HYDROXYL AJ.IINES . ! 1 I . INTRODUCTION . | i Among the classes of organic compounds which have been | ! I brought to light more or less recently are the ketenes, compounds | ! containing the atomic grouping, :C:C :0 . They were discovered in ; (1) I 1005 by Staudinger wBo prepared diphenyl ketene, (CqII|5)2:C:C:0 , I by distilling (CgH^ )2C1C-C0C1 Virith zinc, in ether solution. The ( 2 ) nex^ year Diels and Wolf prepared carbon suboxide, 0 ;C:C:C :0 . | Subsequently more than a dozen other ketenes have been formed with I a consecpient investigation of many of their characteristic reac- tions. As may be expected from the unsaturated nature of the charac- teristic grouping, ketenes enter into addition reactions readily. Witli ketenes water produces carboxylic acids, alcohols give esters, and acids yield anhydrides . With basic compounds the following reactions are characteristic: (1) Ammonia produces amides, HgC : C : 0 t- NII3 CH3CONII2 (2) Aniline gives anilides, (CH3)2C:C:0 tH2N(GgH5) — ^ H (CH3 )2C-C0NH (C6H5 ) An interesting parallel may be found in the case of the iso- cyanates which possess a characteristic grouping similar to that of the ketenes, namely RN:C ;0 . -V- . . '■ /^ '^r-.T- *’'■ ■ I. ,'»1 m- ■ •I fa«?r::> jwmTH mif joitos'^^- ^<0 ;'^v' V . * .} 5 oi?^vranfl:fxi .r ^ > \ ^f»;j^(f ►iY 4 trl iXojt’lw al>ntwt 7 moo *lo waaj^C'T'-^if.J p? ;?f«rii^»rrf j»>‘j ,k> •7T''i4'iaJ nif^ o-ta tX-llR 'f<* *)»i^«ii 4»la^X ^ ni YodT- . v?tnl:ft»-'''tn 6t:n).jfl nd^' tn ‘ ■■ ‘-■'r.- - , ; 3 : *: t -j(rf> 4 u^/ Cxnod^XlJ !♦ Oi!i» 'Y': 'T'? odl* .-^rtlir^Ic^H 'TodJo MX.oui'.^ diXYf V 3 ) "w’.' F i:l» ^iUU^^:odM^I rtodoo^ ^ 7 *<*V ' ' JS ' ., : ‘r^ "ft •• ’ ^ 1 , 7 ^"' V . '* / ^ jyymolt ft^joJ ova*? «or I’iiiJu u nMlJ orjott ^IJIiS0f»pc>^iia , 1^ -nRO*» t»XXei''to;r3rt'fa!f'f' *iX.u<<4^ In r,n«i4 no f;^.X4ayml Xiroiin&anon 4f» “Vi I ' -tt : «ri .. ;lt f)rfi *lu ^'iT b 946 *f>crxo 'a." *>■4 •'iia: » 3 A^jjairbj;»w -v. i ' .vlibji^j't imni J rj«a‘i tfaiiJt'iWR iTdfnfX 3 ii*dai:*j <>4 _ ^ eloftooCa >n ff?Iij?!‘ fi^')t, 7 vvnf idJ&in HortA 4 rt» 3 t, 44 ' ^iijivoIXol 0(14 MlWim'i. (f»i iiXoXT ' . V . , * '*. • 1 uai|(^ toa 61 />j(i .ilnoi-fiaA 't(X) ^ / .'-f .rtJ t /j ♦. ’ M * A Xirta j«X|ft?tA ( 2 ) . ' ° V ' \ \ii ^ I W' ff,l!Q 3 )Ki< 0 J- 0 ;',(j.Up)H ♦- ( 38 ^ 0)^90 f flrSiDjfgjO);'^ >t?}^i oif.i To ojirfio ot'Jf <>i it/TiiQ''t |»ff 7i^f( t,1«*o*io4aX I JftdJ (iJ ,**ff 4 :fil'o*t^ o b.laX'To^oiB'fajia r eejOBao*! ifnltiK ao 4 i,irw/.d! I*' ,j «* , .:^<;;iirV 4 . :^il* A;' 0 : ?) : KJI f op»(y r Q;oa 5 ( 4 i 4 iC *^b r. ^ I ' - 2 - (1) With annionia, CoIl5N:C:0 NHp, -- CpH5NIir0XIl2 (2) T.^ith aniline, CgII^N:C:0 HoNCgHs CgllgNIICONHCgHg Ilydroxylamine has also been allov/ed to react with isocyanates Thus the reaction: (3) i + HNHOH CgHr^N-gO 6 5 6 oJ-j Nil on Until last year, a siniilar reaction ^vith the ketenes had never been studied. On the Tjasis of the addition of hydro xj-lariines to the isocj'anates, however, it could have been predicted that ketenes (4) would respond similarly. Jones and Hurd found this to be the case with diphenyl ketene. The addition product was diphenj’-l-acet- < hydroxamic acid: (CgH5)C:C:0 ITNIIOH (CfiH,;)C“CO H NIIOH In order to develop this" work’ further carbon suboxide was chosen as the keteiie. Its structure, 0;C:C:C:0, makes it partic- ularly interesting, possessing as it does, essentially two charac- teristic ketene groups in the molecule. Diels and Wolf first formed it by treating diethyl malonate with |Jhosphorus pentoxide. (5) Later Diels and Meyerheim prepared it by similar treatment of malonic acid and a variety’ of malonic acid derivatives. Stauding- ( 6 ) er and St. Bereza are responsible for the development of the preparation of the suboxide in a manner characteristic of the •i'vr , r o' *,;J ”i''r .i r . - .1 •>v •r •; t;7 *' • ,'i iOX ’ ’ t -J ' ’ r i’i '■•JL. . V. -Jit. '■ ; ■: ; Ir:/ ; U •’ V o'! I A'f’f /'iq J ■> '-Mu : » . 0 .,v '' •.tt'-.Vl) :P , •> p. rj>: 'f k rtX ^ ■ i« i \ >.s « ♦) ao ioif^ ,, ii • ' ^ !i » ►. * M i' I . f» * j '■* ‘.'t ' ' ') f 1 ' t>r 'i r , • j ,\ ■X . I vi'r'>r;r ' • * > f .1 ■•»! > ■ <;••. • •■I'l'-. , *■■> 0/ ; ■' '» T'.l ^ A \ vc>; ’ ‘ »rfr? OJ J si ;jJ. rr •: 'I * •'• v? ,a ,»u*i • T 1' f , ; ..«• I , ’ rj *i.o / Tj. :‘j' 'i ■ ' "•>■' I's >' •: j'r.-'. I ; :>ir i ‘v 1 •’’.d ! ’ ■ V \ . I-’’ J ^ 'I. I. '"3 O Mi of)i;rod|iv^ ■•'» n ‘ i '^"1 J Ta:v * - - •••- - - *4?: ? . k ' l<. ..... X :.vrr; .nj-.jr .c ' f '■•' •■ '- ' . .. preparation of ketenes in general . They prepared it in ether sol- ution, dehalogenating dihron-malonyl chloride by distillation of an ether solution of the acid halide with zinc turnings. This method of preparation has been followed in this work. At ordinary temp- \ eratiires cai*bon suboxide is a gas, b.p. 7°; m.p. -107®, and there- f ! fore the preparation of the pjii'e compound involves several diffi- | ! culties which are avoided in the method used. The compound in eth-! er solution sufficed for the reactions carried out. | Diels and ^ITolf found that its general behavior follov/s that which is characteristic of all ketenes. It reacts with water to form malonic acid: 0 : C : C : C : 0 -f- 2n0H COgll -CH^COgH It is considered as the anliydride of the acid inasmuch as the true anhydride, C-CH 2 -C, has never been isolated. It adds ammonia to form the amide, and aniline to give malon 3 "l anilide. With hydrox- j’^l^amine, as brought out by Jones and ITurd, the reaction should lead to the formation of the hydroxamic acid of malonie acid: 0:C:C:C:0-r2NHo0H ) NIIOIl"' NIIOH Were the ketene to be reacted with an hj^droxamic acid, inter- est arises as to the manner in which the reaction would proceed. There are several possibilities open, and if we consider both of the ketene groups as taking part in the reaction the two most like- ly reactions are: ( 1 ) V/itli the alpha hydrogen of the hydroxamic acid, thus: Q. 0 H 0 0 0 0:C;C:C:0f HONHC-n —i n-C-S-O-C-CHo-d-O-NII-C-R i I ’ • 1 T ' ' J f 1 ’ t ' 1 ) . ' * 1 ' r 7 , 3 f(" 1 ^'^' '*{■< 1 . iV; . ' fj' t .''f- iii • ‘ ' \i . ' ''I'l.t ' rv it 1 - •■••.. ’ * .'- ' . ’r’ S'' ”■■.«*. ■ i . . - !•:•: * ! .' i /. *'! r ''ft' (.' ! / • , - ' .1 '• ' r ' ■' ‘1 V »?! i '.1 * • i :• «.-i, :, :‘>r • ‘ , ff ■; n :'ra, i' ■1 . > I ' '.1 mTo } I' /•J '1 / 0 1. ? 'v'» " i »i,: ; i.fi '•■ ;■..«• uni'.- ^ «V»' ■■* -’-v ' - . . * i. J .1 i J. ■ V ■ -t j. r . ,,f - ^ Yjy,., - I • / » • ^ V’?' : ' U 1 1 !.■• ' ■ L , ’ ji,.,i./ ■<• , ’: 'v,f jd.itir,' , '>.;?■:} .••i*. V , >• !.., ; ‘a ■.,4 ;>■'»•; / ;•■? ,, ' '' v! t ■•r. • • It . 1 ; *'f •' . ' , * :’ r • 1 . 1 ' J tf *1 1: ''■ . i ' Ifi/ • 'I>J f r . i;rf»r * • ft' • :y, > .--^a i-x-i J.rj .,• i '-‘'V.v ,1 , !;•■)*. ‘ / '•’■i" ”0 I ;or'-nX» ••!.’' '' ' ; i ■ (J ' r -4- (2) With the beta hydrogen, thus: no 0 0 0:C:C:C:0 i-HONHCOR -> R-C-N-C-CHg-C-N-C-R on on Of these two possibilities the first seems more probable in the light of the manner in which hydroxamic acids are known to react with acyl groups. If one acyl group is added, there are no cases on record where the beta hydrogen is acetylated before the alpha in an hj-droxamic acid. Kith acetic anhydride we have: OH 0 0 0 R-C-.Til0Ht(CH3-C0)20 R-C-N- 0 -C-Cn 3 1 CIIg-C-OH II. EXPERBIENT AL . Malonic acid was used as the starting point in the prepara- tion of the ketene, bromination of the acid to form dibrom-malonj'^l (7) chloride being the first step as described by Conrad and Reinbach. One mole of the acid reacts with two moles of bromine, thus: COgH-CHo-COgH -h 2Br^ COoH-CErp-COgH -f 2HEr 72 g. of moist malonic acid was dissolved in 60 c.c. of di- lute HCl in a round bottom flask immersed in an ice bath and 182 g. of bromine introduced slowly with constant agitation of the flask. The amount of halogen added was the amount computed to be necessary to brominate 60 g. of pure acid(the amount of acid estimated to be contained in the original 72 g.) After all the bromine was run in, the dibrom compound crystallized out and was filtered with suction. (i i '’.i , ' ' 1 ' -i ri ti ui;‘j ' '■ ' L:. "vut i' ' u'jjli? ^oJAia ,rT;?^ •, ; :v,j ->v.fP tr t , J.'"' •V • •>•-/ r. . ;-.i A' • »■• b.". !! V *' I. Ad tiiiia . -L)- It was then dried in a vacuum desiccator. 130 g. of dry, white crystals resulted. The dihrom-malonylchloride was prepared according to the ( 8 ) method of Staudinger and St.Eereza in which 130 g. of the dibrom compound dissolved in 400 c.c. of absolute ether is added to 230 g. of phosphorus pentachloride at such a rate as the reaction permits. The reaction is: COgH-CBr^-CO^Ht 2PC1^ —V COCl-CBr^-COCl -f 2P0Clg -f 2HC1 The 130 g. of dibrom-malonic acid was dissolved in a proportionate amount of absolute ether and run into a flask containing the PCl^ with a condenser attached and the mixture refluxed for two hours. The ether was then distilled and the portion remaining was fractionjf ated at a pressure of 15-20 mm., the fraction coming over from 70-80 degrees being saved and redistilled. 40 g. of the acid chloride was obtained as contrasted to the yield of 144 g. report- ed by the originators of the method. This preparation was used for the generation of the suboxide ( 9 ) according to the method developed by Staudinger and St. Bereza who report that 30 g. of the acid halide dissolved in 300 c.c. of absolute etlier was added to 20 g. of zinc turnings in a liter flask at such a rate that the solution boiled briskly. The ether solution containing the ketene was collected by means of an ice cooled condenser and receiver. 10 g. of the halide was dissolved in a proportionate amount of absolute ether and a portion of the s solution dropped upon zinc turnings in a flask by means of a drop- ping funnel . The reaction was rather slow in starting but soon ^ ‘ :'W' ’" 'r'- , . ;.v'''*-M . ' '"•^f -■ y ^pp-F •p 4 ' >y';v ^ Lr»,ll. Kr*i t*^ tt M jrt V ' A I^Y ^«ir4* t “i A .. if .;.' *m ■m \} vT™ V‘ Sfc . \V ’ , ■■ I'.v' ■S T ■.., If . 11 .^' - ■i**^ '. » :■- f^Jru €.'i ,j^,irvv-< ' ^ ., , V 'T^-, ' 'i ' ' i' ‘ .1 M..; , V- ^ vjr>3f 9^B; ■ . 4i'^* p^'.' V 7 ^ ■ frjv **! ^<7 ^in|4fo' r<-o ’/j/i .be- ?f J {>.i- i^sli ' 0 '' iiltliW'aob't^^ ^ ‘\^'‘L/‘ ■-. V ■' ' ■ > u''V^.' ‘ ,,>:«>• ■*“.•■■ ■ ’ • -..^A’.v.' 3 : i 0 iV ' 4 itt. i bf # I >ri\ <^iU ■ i ^4 .’ li ■ ^$ 4 i"‘ -i.' ■ :"’V ' Kvc^' v'/fr’:' „■■ I r.'.'.S'i.-v . '■ , '.''’iw ‘. ■ '•^ ' ' * *a • < ■ • ■! ^ f \ * Xl I ' ■ ’ . 1 . ,, , ,. -^T" ■f ■ . AT. ■ »V ' ilEyj "1 1 1 . , (j; '.ji ' , . ' *' I ■ .‘.#rt .v.V • ■/, ,' V -, “ ' ' - tJ , .' - 6 - developed with sufficient vigor and heat as t6 cause some of the into ethei* to distil A^he receiver whicli was immersed in an ice hath. The remainder of the acid chloride solution was added as the vigor of the reaction subsided and it was necessary to apply heat to the flask in order to cause the reaction to go beyond a certain stage, most of the ether thereby being distilled into the receiver. The ether distillate (which contained theoretically somewhat more than two grams of the suboxide) was divided into two gqual portions, one portion being shaken with 2 c.c. of water and the other with 2 g. of aniline. The ether was then removed and it was found that a small amount of malonic acid was formed with the water reaction and a trace of the anilide in the case of the solution in- to which aniline was introduced. Such yields were disappointing as it was felt that more of the ketene had been formed than the re- sults would seem to indicate. This conclusion was reached from the ketenoj seeming A’-igor of the reaction wliich produced theA*the sharp odor at times very perceptible during the operations, and the vapor pressure above the ether solution of suboxide vdien the latter was agitated. This last seemed to indicate that considerable of the gas had never dissolved in the solvent or had escaped from solution whentthe ether was agitated. It was concluded that perhaps better results could be obtained by exposing the distillate to the reac- tion Liixtiire directly upon evolution of the suboxide. This was ac- complished by submerging the end of the condenser into t’le solution containing the substance with which it was desired to have the ke- tene react. About 14 g. of the nalonyl chloride was dropped upon the zinc turnings in the second run with the above modification in W'%' ' ;l'vy -'V‘^ v: .^: ,■ ■ ;■ . :,v Vv^ . v/vv ; My r ..ri'^lpv-'^; frarf J’d... {[« ■ T * ^ . i'^J* . \v'. * 'i-^:oifycX'/»l-'» ^ 11- ircMi ' noUo^m't t . /. f . i' ' . ■ ‘ r ■ . V ■ ’ ' ^ ' V , ’ ' •••‘'♦^ . Xtiw,'' " X T y . ■ ■ ' ' ; -a'. ' ■. ...' ■' ■-4' 'h^rl <>*l/ff- i'i'^i'Xi.*k*tJ,iv, ^irVifwr >1 'j ' ^ tti, '^*S o t Pjf ■ ia->t)iiii)9;i<-irxi\>i!W^'' 'W.Hij »i(^i..«ii .'•. ,•' L ■ .' ■ , ' , 11 , ’ ' ‘ J. .‘jv ■'i'*^''' ■ ' 4 * , itr'S j-rvi »JI .f^itiji J «'(irp| Aw V y>,t.-, :tLA. ,\ g' '■' tr. yyy ‘to .7. > iiiiJL?- tn«r U„ I^jcrial r*'. ‘C.,' ■ ^ ' .i ’’ ■ ». •■ .. .: _v ;' '■" .* ■ '^ V'?‘> ’ « '^i- :V „ V. ‘V . N»/i; /,■><« 6ft) 'i<^' otli . :^ JtX^n^ mU- *lf4}ui\^n-S r • ’. s'if’ •^•.. ; • -••» ., ■'. B . ';’ '; 'Jr?.’ ■.■5iii4 ntjoi} Jbis'#--'. l.t ' Jbis'c '-' '1%%^::^,'' , lo - ,&*n *v.t^ ' ^ wrfy.' J-'Xfjl j 9r>4 '. - • ' */i .1 -. '” . ® ■ ’''':, ■ '.’ i jff *' ‘I -» ^ , ‘ ^ ' ’ ' W ^ "' * 1 ' ■ I i>'i ^ m y ^ * Ijfcr I ' «| ,t ■ hXvnit ‘ ., ’ .••"■' ■"" ';■, •(!>'■ , « ’ ' "■ ■'**! -■'If- ' y , . jfa,. '•'»:> ,;3W?^k*.*5T .^jOf^i.^ Si'rti4it3WV^\|V(^> 'ft ' V .'- ‘ '.'v,. . T.* ■ '^1 ’’y^' v'ifV ''' •'A ; ■ -Wv* 4o. .orf4.' ■' ■" _^. V X N' . , ^"''' ' i»,v. » . ■ H'l:'? .■ . .' :'• If. :Ar • ■ ,a . ' ••■■« - ■■ v. 1^. . , • ,• k.A'--' .Ai,' •y/y-i VT ;// v*^ - > ' A< ' '<'4» ty 4 ] 1 '•' ■■t.-ij '< ^ VfX aviH • ■xto t.J.yi|. *-6-; 'ta- li. f ** ■‘■■^.*‘fe''''W 7^'^) 'Tr^^ituinh^p ' '' . A- ij’lr ■'. [ ' f 4?v. t: ■'V.fe?' 1 ' ? t - 1^., '•/' j. T| ' ■ -7- fii" '■<¥‘"', ' 1 ' 'V' ' • w<4'« .. rt«siaiji.0Tr/ rc'^Ari li-,’ rv; 11- ./, .i; 'iXii ' •!,««?! jfi(i(i» :.i('<,'.'jiv ■ iiU''srOi%T/j4«« :■ ' ;.«Li: TT ' ' . ■• ■ ,. ' “ " tj* 'k. -7- procecliire , appro:^iiaatel3f two-thirds of the distillate hein^^ run through a solution of water in ether and the remainder tlirough an ether-aniline solution. O.IO g, of inalonic acid and 0.25 g. of the anilide resulted, proving that the carhon suhoxide liad been gener- ated in some quantity. By computing the amount of ketene necessarjj'' I for the formation of the alaove quantities of compounds it was found that 11.5 o/o of the theoretical yield of ketene had reacted. Staiidinger and St. Bereza report 80 o/o. The suhoxide was then allov/ed to react with hj'droxylajnine. The latter was prepared hy treating its hydrochloride (impure) in methanol solution with the calculated amount of a solution of sod- ium meth 3 ’’late. Approximately 2 c.c. of free hj’droxj’-l^amine was obtained by fractional vacuum distillation. This was introduced into a flask containing 35 c.c. of ether (absolute) . 15 g. of the acid chloride was dropped upon the zinc turnings and the distillate conducted directly into the ether-Iij'droxj^lamine mixture. A vdiite precipitate v/as soon noticeable in the ether as the distillate came over. At the completion of t!ie reaction a considerable por- tion of the hj’’drox 3^1 amine remained in the bottom of the flask, im- miscible v/ith the ether. The flask and contents were allowed to disappeared stand for several hours with occasional shaking. The precipitate ^ and it was concluded that the small quantity of immiscible liquid had extracted the precipitate from the ether layer. The ether was distilled and t!ie remaining solution was placed in a vacuum desic- cator. About 0.25 g. of residue remained which gave a pronounced red color with ferric chloride. It was somewhat soluble in water, slightly soluble in alcohol, and insoluble in ether. Aqueous so- - 8 - I liitions and alcoholic-ethcr solutions of the residue tlirev; dov/ii a precipitate when treated with dilute ammonium hydroxide. This was expected since Hantzscli described the insoluble anuiionium acid salt, ( 10 ) HNOn-CO-CIIo-CO-NITONTI^. The precipitate, with no purification, melt' ed at 107-110°, and decomposed at a slightly higher temperature. In order to attempt a reaction with carbon suboxide and an hydroxamic acid, 1 g. of benzhydroxamic acid was dissolved in fjp c. e. of ethyl acetate and the suboxide, generated from 10 g. of the acid chloride, passed into the solution. As the solution still gave a color reaction with ferric chloride, a one-sixth portion of the reaction mixture was taken, and the ketene passed into it until the ferric chloride test showed that no benzhydroxamic acid re- mained. About 8 g. of the acid chloride v;as required for this. To obtain the reaction product the ether and ethyl acetate were removed by evaporation and the residue dissolved in wara alco- hol, and filtered. The filtrate was diluted with water, causing a tardy separation of white crystals. More of these crystals were ''5' That described by Hantzscli melted at 141®. During this experiment It developed that it was probaTble that some of the ketene was being lost through cork connections of the apparatus, so rubber was substituted througliout . This forced all benz of the ketene through the solution in the flask containing the/^^hy- droxamic acid. Apparently this jirecaution was justified by the re- sults V \ V' "Vl w i: V K t*’^‘tt? •• wtA»t,*^ tiii^fc-ytatf ^ '.r*'Jt;fi^-*^ uatii^iu t ^ J. U'' I ' 4 f^-'' ' ' ‘ '■'•™ /• •*''■'■ - “ '*' ■ '’ '* _ L_.'f r<: .1 , \ * _ ^'.n /'• ' . “ '•*-. ,; 'a' , ol£:/l5s- i>|3t^ ''§'>V/ivr«**.*tIt;-'^iU jr»tHJJt*lfJUii^»l/ '^0lXl»r4l^,irf^^\) 2[ ' ■ i9n ^ -s ;:' ft K ^ ii Vi. i ;P r^.t '^ir' no- 14 '»jofe''l ' *.• ^'^' ■ jf ; ^/' -z^ t ■ '• ■' Y . ' J 1'*:'‘ '''* ' (^/Pif- .i^^'th>nfkl> -M'H UXs*a !jii';n 3 rcikiifi^ .-T L !^f : >‘'X*Y ■:i'r6 £/*o 14 ¥i ; ^ f it4^X^ i4il>.i't I v\' ■*. , ■ i "'• ’ ^ -- ' ■/''^' tyo^Soji9M “■ft ???i|L- ■ . -« . ■■> : i''"' ' '■^ 4 , V^''Vi| '■’Ki*®',' '■ i " i '«"'• 1 r^--V' V ■ . ■ ■ ’ ! ■ '-»! OttOfiJ •‘lO; »tOj " . ♦ ??In 4 ?• : vJirfw '‘X •» ,ffO|i«'firr)|^,,;ti^ 5 »i' f"- ’■;•? • ..,K*V ’ ■ • ., .T‘'*?^aiCpdB ’■ !: '^ ' • X />ti. c ' 4 rt 4 ihil ■. L ■' - “ ,v. • . ' . , ^ if- II V -. • "'X ' ' ' '^.' ■ ' • ■ ■ -. A- * ‘ jii. »)^ 5 if 4 i!ro<^i.ol 0 'toi> 41 *>0 '^/rrT^t^ ’4«0r /.//f/vlQtX -*^4 » •'■ • ^ V ' •' . . Jit ?i K [» (!» :H;*. Iiv;»'id'*,!,.xi;rt * SinH’iJtfividim KiiW aaVlTn^r K. u . ^rtfia: # •• ;■ .ifi .. ...■ m > .. 'V'i ll^ H •Mf.t nJt no:tJfU*nf t/ift^•.^t